Note: Descriptions are shown in the official language in which they were submitted.
W~ ~/07~K PCT/US92/08301
2120491
B~EAC~I~G COMP08rTION8
Field of invention
The present invention relates to compositions that are
useful in the bleaching of stains from soiled articles,
including and of particular use in the bleaching of
carotenoid-containing stains. In one aspect, the invention
relates to such compositions that are in the form of
detergent compositions comprising one or more detersive
surfactants.
Backoround to the invention
It is well known to incorporate into a detergent
composition an inorganic compound that is capable of
yielding hyrdogen peroxide in an aqueous medium, a common
example of such a compound being sodium perbonate. The ~-
resultant compositions are effective in the removal of
certain hydrophilic stains, for example those due to tea,
wine or fruit juice, but, on its own, the bleaching agent ~-
has to be used at a temperature of at least 60C. In order
to render such compositions effective at lower
temperatures, for example 30-40C, it has been proposed to
add an activator, such as tetraacetylethylenediamine
(TAED), such activators being thought to react in solution
with the perbonate and thereby yield peroxyacetic acid.
In order to bleach such hydrophobic stains as those due to
grass, motor oil, paprika and the "dinginess" associated
with repeated laundering of fabrics, it has been proposed
to add monanoyloxybenzene sulfonate (NOBS), which is an
aqueous medium in the presence of perbonate is thought to
produce peroxynonanoic acid. However, there are a number
of common soils that give rise to hydrophobic stains that
are resistant to the NOBS/perbonate system, such stains
being due to carotenoid chromophores, e.g. ~-carotene,
lycopene, zeaxanthin or capsanthin. Typical soils giving
rise to such stains include carrot and tomato, and baby-
SUBSmUTE SHEET
WOg3/070~ 2 1 ~ O ~ 9 1 PCT/US92/08~1 ~ ``
- 2 -
foods and sauces containing or or both of these, as well as
various tropical fruits and saffron.
One proposal for the removing of a wide range of stains,
including such hyrophobic stains as those caused by tomato
sauce, is described in EP-A-0,337,535, which recommends the
use of a bleaching composition that comprises (i) a
peroxygen bleaching compound capable of yielding hydrogen
peroxide in an aqueous medium, preferably sodium perbonate
monohydrate or tetrahydrate, and (ii) a bleach precursor
having the general formula R-CO-L wherein R is one of
certain aromatic or substituted aromatic radicals, e.g. a
(Cl-C6-alkyl)phenyl or unsubstituted phenyl group, and
wherein L is a leaving group, preferably a 4-sulfophenyl
group, the molar ratio of hydrogen peroxide to precursor
being within the range of from 0.l to 2. However, the pH
of the aqueous medium appears to be critical to the
bleaching performance of these compositions, it being
stated in that European application (page 4, lines 20-22)
that the pH must fall between 8.5 and 9.4.
EP-A-O, 106,584 discloses bleaching compositions that are
described as being effective not only against a very wide
class of stains but also over a very wide range of pH of
the bleaching solution. Specifically, these compositions
comprise (a) a halogenated peroxybenzoic acid or a salt
thereof, e.g. p-chloro- (or p-fluoro-) peroxybenzoic acid
or its mangesium salt, and (b) a bleach activator having
the general formula R-CO-L, wherein R is selected from
certain alkyl, alkylene, cycloalkyl, cycloalkylene, aryl,
aromatic heterocyclic or polyarylene groups or groups in
which two or more aryl or arylene substituents are
covalently attached. Also disclosed are bleaching
compositions containing (a) a peroxycarboxylic acid or salt
thereof and tb) a bleach activator having the general
formula R-CO-L wherein R is a Cs-Cl7 alkyl group. In both
cases, L is a leaving group wherein the conjugate acid of
the anion formed on L has a Pka of from 4 to 13 and the
molar ratio of each peroxycarboxyl group of (a) to each
SUBSTITUTE SHEET
W~ ,/07~ 2 1 2 0 4 g 1 PCT/US92/08301
- 3 - ~
carbonyl group of (b) that can potentially generate a `
diacyl peroxide compound is from l0 to 0.05. It is
surmissed in EP-A-O, 106,584 (page 5, lines l - 13) that
the bleaching performance of these compositions is due to
the reaction of the perxycarboxylic acid with the bleach -~
activator within an aqueous medium to from a diacyl
peroxide compound.
Summarv of invention
The present invention relates to the use in bleaching
compositions of urea clathrates of peroxide compounds,
which peroxide compounds are selected from (l) diacyl
peroxides of the general formula:
O O
R~ -oo-C-R2
in which
Rl represents a C6-Cl8 alkyl group containing a linear
chain of at least 5 carbon atoms and optionally containing
one or more substituents (e.g. -N+(CH3)3,-COOH or -CN)
and/or one or more interrupting moieties (e.g. -CONH- or -
CH=CH-) interpolated between adjacent carbon atoms of the
alkyl radical, and
R2 represents an aliphatic or aromatic group compatible
with a peroxide moiety, such that Rl and R2 together
contain a total of 8 to 30 carbon atoms,
and (2) tetraacyl peroxides of the general formula :
O o o o
R3-C-oo-c~(cH2)n~c-oo-c-R3
in which
R3 represents a Cl-Cg alkyl group, and n represents an
integer from 2 to 12 inclusive.
SUBSTITUTE SHEET
W093/07~ 2 1 2 U ~ 9 1 PCT/US92/08301 1`"`
- 4 -
The bleaching compositions comprising t~e urea clathrates
as defined above may find use in essentially any bleaching
process. The bleaching compositions, for example are
useful in the bleaching of cellulosic fibrous material.
The term cellulosic fibrous material as used herein has
reference to wood, cotton, linen, jute and other materials
of a cellulosic nature, and also includes individual
fibres, for example wood pulp or cotton fibre, as well as
yarns, tows, webs, fabrics (woven or non-woven) and other
aggregates of such fibres. The bleaching compositions of
the invention are also useful in the bleaching of synethic
textiles including polyamides, vicose, rayon, and
polyesters.
The bleaching compositions are also useful as components of
detergent compositions. These detergent compositions may
be used in essentially any washing laundering or cleaning
processes in which bleaching is required. Thus, the
detergent compositions may be used in home or industrial
laundering or automatic dishwashing processes, and in any
process involving the cleaning of hard surfaces such at
bottle washing, dairy cleaning and kitchen and bathroom
cleaning processes.
In one of its aspects, the invention provides a detergent
composition useful in the bleaching of stains from soiled
articles which detergent composition comprises (A) an urea
clathrate as defined above and at least one component
selected from (B) a source of hydrogen peroxide selected
from nonionic,ranionic, cationic, ampholytic and
zwitterionic detersive surfactants. Compositions to be
used merely for bleaching may omit component (C) whereas
compositions intended for use in the laundering of bleach-
sensitive coloured fabrics (so-called "colour-care" laundry
compositions) may omit component (B).
In a preferred aspect of the invention there is provided a
composition in the form of a detergent composition
containing both of components (B) and (C) : optional
SUBSTITUTE SHEET
W~ ~/07 ~ 212 0 ~ 91 PCT/US92/08~1
- 5 -
ingredients for such detergent compositions include (D) a
detergent builder compound and (E) a bleach activator.
Description of exemplarv embodimentæ
The diacyl peroxides of the genral formula (1) are known
compounds, of which a number are sold commercially as free-
radical polymerisation initiators and the like, or can be
prepared by methods known in principle. Thus, for example,
it is stated in the Xirk-Othmer Encyclopedia of Chemical
Technology, Third Edition, Volume 9, at page 815, that
diacyl peroxides can be prepared by treating an acid
chloride or anhydride with sodium peroxide or hydrogen
perodxide in the presence of a base. Methods for the
preparation of diacyl peroxides are also described by L. S .
Silbert and D. Swern, J. Amer. Chem. Soc., 81 (1959), 2364.
The diacyl peroxides of the general formula (1) include
those in which R2 i8 selected from optionally substituted
and/or interrupted Cl-C18 alkyl radicals, phenyl and
benzyl.
Examples of such peroxides are :
CgHlg -NHCO-(CH2)4-CO-OO-CO-CH3
CgHlg -NHCO-(CH2)4-CO-OO-CO-C8H17 and
CgC19 -NHCO-(CH2)4-CO-OO-CO-(CH2)2-CO2H
Thus, R2 may be selected from the radicals specified for
Rl, that is to say C6-C18 alkyl radicals containing a
linear chain of at least 5 carbon atoms and optionally
containing one or more substituents and/or one or more
interrupting moieties interpolated between adjacent carbon
atoms of the alkyl radical. Usually, however, the said
alkyl radicals Rl and R2 will be unsubstituted and
uninterrupted and hence will usually have a linear chain of
at least -(CH2)s-, preferably at least -(CH2)9-, straight-
chain alkyl radicals being preferred. Diacyl peroxide~ ofthe formula (1) in which Rl and R2 are identical will
co~monly be used, particularly preferred compounds being
SUBSTITUTE SHEET
WOg3/07~l 2 1 2 0 4 9 1 PCT/USg2/08301 i ~,
dinonanoyl peroxide (also known as dipelargonyl peroxide),
of the formula n-H~7C8-C0-00-C0-C8H17-n,
and dioctanlyl peroxide, which is commercially available as
N . S . Tsvetkov et al, Vysokomol. Soyed., A14, No . 9 ( 1972 ),
2072-2077. Alternatively, tetraacyl peroxides may be
prepared from a diperoxy dicarboxylic acid and an acyl
chloride (e.g. from diperoxyadipic or diperoxyazelaic acid
and acetyl chloride) in the presence of pyridine, as
described by L.S. Silbert and D. Swern, J. Amer. Chem. Soc.
81 (1959), 2364. In the tetraaceytl peroxides of the
formula (2) the R3 radicals will usually be identical,
although they can be different. It is preferred that each
R3 represents n-C8H17-and n is 10.
The diacyl and tetraacyl peroxides are intrisically
unstable above their melting points and are liable to self-
accelerating thermal (and catalytic) decomposition ; they
should generally be handled with great caution in view of
their flammability and their tendency to decompose
explosively when heated or subjected to shock-or friction.
The peroxides commonly have a 10-hour half-life temperature
of less than 100C, a number of peroxides that are
particularly useful in the present invention having 10-hour
half-life temperatures of only 55-65C. It has been found,
however, that the urea clathrates of the peroxides may show
much greater stability : for example, whereas dinonanoyl
peroxide melts, and hence becomes extremely unstable, at
about 20C, a test using differential scanning calorimetry
indicated that an urea clathrate of dinonanoyl peroxide was
stable to at least 125C, which is not far short of the
melting point (133C) of urea itself.
The urea clathrates (also known as urea inclusion
compounds, urea complexes or urea adducts) of diethyl
peroxides and tetraacyl peroxides are known or can be
prepared by methods known in principle, for example by
mixing a solution containing the peroxide in methanol or
propan-2-ol with a solution of urea in methanol, the
peoxide/urea ration correspondinq to the ex~ected
SUBSmUTE SHEET
~ ~`93/07086 21 2 0 ~ 91 PCT/US92/08301
stoichiometry of the clathrate or to an excess of the
peroxide, as described by K.D.M. Harris and J.M. Thomas, J.
Chem. Soc. Faraday Trans., l990, 86 (17), 2985-2996. urea
clathrates of tetraacyl peroxides are described by L.
Heslinga and W. Schwaiger, Recueil, 85 (1986), 75-85, which
authors disclose that such a clathrate may be formed by
mixing te diperoxy acid, e.g. diperoxyadipic,
diperoxyazelaic or diperoxysuccinic acid, with the
calculated amounts of urea and acetic anhydride. As a
general guide, from 2.5 to 3.5, typically about 3, parts by
weight of urea will be required for the clathration of one
part of the weight of the peroxide.
The urea clathrate will be incorporated in the bleaching or
detergent compositions of this invention at a level
corresponding to usually at least O.l percent, preferably
at least 0.25 percent and more preferably at least l
percent and usually up to 20 percent, preferably up to lO
percent and more preferably up to 5 percent by weight of
diacyl or tetraacyl peroxide, based on the total
composition.
When employed in bleaching, cleaning, washing or laundering
processes, the bleaching detergent compositions of the
invention will be used in an aqueous solution such that the
level of diacycl or tetraacyl peroxide is preferably from
0.001% to 0.5% by weight, more preferably from 0.005% to
0.02% by weight of the solution.
The source of hydrogen peroxide used as component ~B~ can
be selected from a wide variety of compounds that are
capable of yielding hydrogen peroxide in an aqueous medium.
Inorganic compounds serving as sources of hydrogen peroxide
and which can be used as component (B) in the present
compositions are well known in the art and include such
persalts as perborates, percarbonates, perphosphates and
persulfonates. The alkali metal persalts are preferred,
especially the sodium persalts. Sodium perborate,
typically as the monohydrate or tetrahydrate, is preferably
used. However, a suitable organic compound may be used,
su~ rrE SHEF~
W093/07086 2 1 2 0 4 9 1 PCT/US92/08~1 ~`1
- 8 -
for example a perhydrate of urea or of an organic acid
salt.
The compound (B), if used, will be present in t~e
composition in an amount of usually at least 0.5 percent,
preferably at least O.l percent and more preferably at
least 0.5 percent and usually up to 60 percent, preferably
up to 30 percent and more preferably up to 20 percent, by
weight of the total composition.
The weight ratio of component (A) to component (B) may be
varied widely. In general, a lower level of H2O2-source,
especially in the presence of one of the more hydrophilic
acyl peroxides, will favour carotenoid bleaching, whereas a
higher level will promote peracid formation and hence will
disfavour carotenoid bleaching.
The detersive surfactant (C) will typically be used in an
amount of from 0 to 50, preferably l to 30 and more
preferably 5 to 20 percent by weig~t.
The compositions of the present invention will normally be
in granular form, which expression herein includes any
solid particulate form that is appropriate for bleaching,
detergent or other cleaning compositions. The compositions
of this invention may be formulated as simple bleaching
compositions, as colour-care detergent compositions that
contain no source of H2O2, or even as dishwashing
compositions or hard-surface, toilet or other household
cleaners. In certain preferred embodients, however, they
are formulated as detergent compositions (typically,
general-purpose or heavy duty compositions) that contain
not only the above-discussed components (A) and (B) but
also (C) a detersive surfactant and, optionally, (D) a
detergent ~uilder and/or (E) a bleach activator. The
composition may also comprise any other component
conventional in the art, for example an enzyme, a polymeric
soil-release agent, a chelating agent, a clay soil
removal/anit-redeposition agent, a polymeric dispersing
agent, a brightener, a suds suppressor, a pH-buffering
agent, a dye or a pigment.
SUBSTITUTE SHEET
2 I 2 01 91 PCT/US92/08~1
g
It will be understood that any of the above mentioned
components, whether essential or optional, may be
constituted, if desired, by a mixture of two or more
compounds of the appropriate description.
Examples of various optional components that come into
consideration for inclusion in the present compositions are
as follows.
Nonionic Surfactants
The detergent compositions of this invention may contain a
nonionic surfactant.
Suitable nonionic surfactants include the polyethylene
oxide condensates of alkly phenols, e.g., the condensation
products of alkyl phenols having an alkyl group containing
from 6 to 8 carbon atoms, in either a straight-chain or
branched-chain configuration, with from 1 to 12 moles of
ethylene oxide per mole of alkyl phenol.
Suitable nonionics also include the condensation products
of aliphatic alcohols containing from 8 to 22, preferably
12 to 18, carbon atoms, in either straight-chain or
branched-configuration, with from 2 to 12, preferably 3 to
7, moles of ethylene oxide per mole of alcohol.
Suitable nonionic surfactants also include the fatty acyl
or alkyl condensation products of carbohydrates and their
derivatives such as glycosides, aminodeoxy forms, and
polyols. Examples include coco-alkyl polyglucosides and
tallow-acyl polyglycerides.
The nonionic surfactants may typically be used in an
amount from 0.5 to 20%, preferably from 3 to 15% and more
preferably from 5 to 10%, by weight of the total detergent
composition.
It should be noted that care will need to be taken in
formulating an urea clathrate with certain liquid
nonionics to obviate the possible replacement of acyl
peroxide by the surfactant in the urea cavities.
Anionic Surfactants
The detergent compositions of the previous invention can
contain, in addition to the ~leaching compositions of the
SUBSTITUTE SHEET
wo 93/07086 PCr/USg2/08301 i ~'
2120491 IO
present invention, one or more anionic surfactants as
described below.
Alkvl Ester Sulfonate Surfactant
Alkyl ester sulfonate surfactants hereof include linear
esters of C8-C20 carboxylic acids (i.e. , fatty acids)
which are sulfonated with gaseouæ SO3 according to "The
Journal of the American Oil Chemists Society^', 52 (1975),
pp 323-329. Suitable starting materials would include
natural fatty substances as derived from tallow, palm oil,
etc.
The preferred alkyl ester sulfonate surfactant, especially
for laundry application, comprise alkyl ester sulfonate
surfactants of the structural formula:
R3 - CH - C - oR4
- - so3M
wherein R3 is a C8-C20 hydrocarbyl, preferably an alkyl,
or combination thereof, R4 is a Cl-C6 hydrocarbyl,
preferably an alkyl, or c~mbination thereof, and M is a
cation which forms a water soluble salt with alkl ester
sulfonate. Suitable salt-forming cations include metals
such as sodium, potassium, and lithium, and substituted or
unsubstituted ammonium cations, such as monoethanolamine,
diethanolamine, and triethanolamine. Preferably, R3 is
C10-C16 alkyl and R4 is methyl, ethyl or isopropyl.
Especially preferred are the methyl ester sulfonates
wherein R3 is C10-C16 alkyl.
~lkyl Sulfonate Surfactant
Alkyl sulfate surfactants hereof are water soluble salts
or acids of the formula ROSO3M wherein R preferably is a
C10-C24 hydrocarbyl, preferably an alkyl or hydroxyalkyl
having a C10-C20 alkyl component, more preferably a C12-
C18 alkyl or hydroxyalkyl, and M is H or a cation, e.g. an
alkali metal cation (e.g., sodium, potassium, lithium), or
ammonium or substituted ammonium (e.g., methyl-, dimethly-
SUBSTITUTE SHEET
w( ~`/07086 21 20~ 91 PCr/USg2/08301
, and trimethyl ammonium cations and quaternary ammoniumcations such as tetramethly-ammonium and dimethyl
piperdinium cations and quaternary ammonium cations
derived from alkylamines such as ethylamine, diethylamine,
triethylamine, and mixtures thereof, and the like).
Alkyl chains 12-16 carbon atoms, more preferably 14-15
carbon atoms are preferred.
Alkyl Alkoxvlated Sulfate Surfactants
Al~yl alkoxylated sulfate surfactants hereof are water
soluble salts or acids of the formula RO(A)mS03M wherein R
is an unsubstituted C10-C24 alkyl or hydroxyalkyl group
having a C10-C24 alkyl component, preferably a C12-C20
alkyl or hydroxyalkyl, more preferably an alkyl group
having from 12 to 18 carbon atoms, especially from 12 to
15 carbon atoms.
A is an ethoxy or propoxy unit, m is greater than zero,
typically between about 0.5 and about 6, more preferably
between O.S and about 3, and M is H or a cation which can
be, for example, a metal cation (e.g., sodium, potassium,
lithium, calcium, magnesium, etc.), ammonium or
substituted ammonium cation. Alkyl ethoxylated sulfates
as well as alkyl propoxylated sulfates are contemplated
herein. Specific examples of substituted ammonium cations
include methyl-, dimethyl-, trimethyl-ammonium cations and
quaternary ammonium cations such as tetramethyl-ammonium
and dimethyl piperdinium cations and those derived from
alkylamines such as ethylamine, diethylamine,
triethylamine, mixtures thereof, and the like.
A preferred surfactant is C12-Cls alkyl polyethoxylate
(3-0) sulfate (C12-ClsE(3.0)~). Other exemplary
surfactants include C12-Clg alkyl polyet~oxylate (1.0)
sulfate (C12-ClgE(l.O)MO, C12-Clg alkyl polyethoxylate
(2.25) ~ulfate (C12-ClgE(2.25)M), C12-Clg alkyl
polyethoxylate (3.0) sulfate (C12-ClgE(3.0)M), and C12-C18
alkyl polyethoxylate (4.0) sulfate (C12-ClgE(4.0)~),
wherein M is conveniently selected from sodium and
potassium.
SUBSTITUTE SHEET
, -- .
W093/07~K 2 1 20 4 9 1 12 - PCT/US92/08301 i `l
Other Anionic Surfactants
Other anionic surfactants useful for detersive purposes
can also be included in the detergent compositions of the
present invention. These can include salts (including,
for example, sodium, potassium, ammonium, and substituted
ammonium salts such as mono-, di- and triethanolamine
salts) of soap, Cg-C20 linQar alkylbenzenesulphonates, C8-
C22 primary or secondary alkanesulphonates, C8-C24
olefinsulphonates, sulphonated polycarboxylic acids
prepared by sulphonation of the pyr~olyzed product of
alkaline earth metal citrates, e.g., as described in
British patent specification No. l,082,179, alkyl glycerol
sulfonates, fatty acyl glycerol sulfonates, fatty oleyl
glycerol sulfates, alkyl phenol ethylene oxide ether
sulfates, paraffin sulfonates, alkyl phosphates,
isethionates such as the acyl isethionates, N-acyl
taurates, fatty acid amides of methyl tauride, alkyl
succinamates and sulfosuccinates, monoesters of
sulfosuccinate (especially saturated and unsaturated Cl2-
Cl8 monoesters) diestérs of sulfosuccinate (especially
saturated and unsaturated C6-Cl4 diesters), N-acyl
sarcosinates, sulfates of alkylpolysaccharides such as the
sulfates of alkylpolyglucoside (the nonionic nonsulfated
compounds being described below), branched primary alkyl
sulfates, alkyl polyethoxy carboxylates such as those of
the formula RO(CH2CH20)kCH2COO-M wherein R is a C8-C22
alkyl, k is an integer fr~m O to lO, and M is a soluble
salt-forming cation1 and fatty acids esterified with
isethionic acid and neutralized with sodium hydroxide.
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 tall oil. Further examples are given in "Surface
Active Agents and Detergents" (Vol. I and II by Schwartz,
SUBSTITUTE SHEET
w~ ~o7~J 2 1 2 0 ~ 9 1 PCT/US92/08301
- 13 -
Perry and Berch). A variety of such surfactants are also
generally disclosed in U.S. Patent 3,929,678, issued
December 30, 1975 to Laughlin, et al. at Column 23, line
58 through Column 29, line 23 (herein incorporated by
reference).
Preffered anionic surfactants systems employed in the
detergent compositions of the invention are free fo alkyl
benzene sulfonate salts. A highly preferred system
comprises a mixture of a major proportion of a C14-C15
primary alkyl sulfate and a minor proportion of a C12-C15
alkyl ethoxysulfate containing an average of three ethoxy
groups per mole of alkyl ethoxy sulfate. The laundry
detergent compositions of the present invention typically
comprise from about 1% to about 20 %, preferably from
about 3% to about 15% and most preferably from 5% to 10%
by weight of anionic surfactants.
Other Surfactants
Tbe detergent compositions of the present invention may
also contain cationic, ampholytic, zwitterionic, and semi-
polar surfactants.
Cationic detersive surfactants suitable for use in the
detergent compositions of the present invention are those
having one long-chain hydrocarbyl group. Examples of such
cationic surfactants include the ammonium surfactants such
as alkyldimethylanium halogenides, and those surfactants
having the formula:
(R2(oR3)y)(R4(OR3)y)2R5N+X
wherein R2 is an alkyl or alkyl benzyl group having from
about 8 to about 18 carbon atoms in the alkyl chain, each
R3 is selected from the group consisting of -CH2CH2-,
CH2CH(CH3)-, -CH2CH(CH2OH~-, - CH2CH2CH2-, and mixtures
thereof; each R4 is selected from the group consisting of
C1-C4 alkyl, Cl-C4 hydroxyalkyl, benzyl ring structures
formed by joining the two R4 groups, - CH2CHOH-
CHOHCOR6CHOHCH20H wherein R6 is any hexose or hexose
SUBSTITUTE SHEE~
W093/07~ Z 1 2 0 4 9 1 l4 Pcr/usg2/o w l~ `~
polymer having a molecular weight less than about lOOO,
and hydrogen when y is not 0; RS is the same as R4 or is
an alkyl chain wherein the total number of carbon atoms of
R2 p~us R5 is not more than about 18 ; each y is from 0 to
about lO and the sum of the y values is from 0 to about
lS; and X i8 any compatible anion.
Other cationic surfactants useful herein are also
described in the U.S. Patent 4,228,044, Cambre, issued
October 14, 1980, incorporated herein by reference.
When included therein, the detergent compositions of the
present invention typically comprise from O% to about 25%,
preferably from about 3% to about 15% by weight of such
cationic surfactants.
Ampholytic surfactants are also suitable for use in the
detergent compositions of the present invention. 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. One of the aliphatic substituents contains at
least about 8 carbon atoms, typically from about 8 to
about 18 carbon atoms, and at least one contains an
anionic water-solubilizing group, e.g., carboxy,
sulfonate, sulfate. See U.S. Patent No. 3,929,678 to
Laughlin et al., issued December 30, 1975 at column 19,
. lines 18-35 (herein incorporated by reference) for
examples of ampholytic surfactants.
When included therein, the detergent compositions of the
present invention typically comprise from 0% to about lS%,
preferably from about 1% to about 10% by weight of such
ampholytic surfactants.
Zwitterionic surfactants are also suitable for use in
detergent compositions . These surfactants can be broadly
described as derivatives of secondary and tertiary amines,
derivative~ of heterocyclic secondary and tertiary amines,
or derivatives of quaternary ammonium, quaternary
phosphonium or tertiary sulfonium compounds. See U.S.
SUBSTITUTE SHEET
- 15 - PCT/US92/08~1
Patent No. 3,929,678 to Lauqhlin et al., issued December
30, 1975 at column 19, line 38 through column 22, line 48
(herein incorporated by reference) for examples of
zwitterionic surfactants.
When included therin, the detergent compositions of the
present invention typically comprise from 0% to about 15%,
preferably from about 1% to about 10% by weight of such
zwittarionic surfactants.
Semi-polar nonionic surfactants are a special category of
nonionic surfactants which include water-soluble amine
oxides containing one alkyl moiety of from about 10 to
about 18 carbon atoms and 2 moieties selected from the
group consisting of alkyl groups and hydroxyalkyl groups
containing from about 1 to about 3 carbon atoms; water-
soluble phosphine oxides containing one alkyl moiety of
from about 10 to about 18 carbon atoms and 2 moieties
selected from the group consisting of alkyl groups and
hydroxyalkyl groups containing from about 1 to about 3
carbon atoms; and water-soluble sulfoxides containing one
alkyl moiety of from about 10 to about 18 carbon atoms and
a moiety selected from the group consisting of alkyl and
hydroxyalkyl moieties of from about 1 to about 3 carbon
atoms.
Semi-polar nonionic detergent surfactants include the
amine oxide surfactants having the formula
o
R (OR )XN(R )~
wherein R3 is an alkyl, hydroxyalkyl, or alkyl phenyl
group or mixtures thereof containing from about 8 to about
22 carbon atoms; R4 is an alkylene or hydroxyalkylene
group containing from about 2 to about 3 carbon atoms or
mixtures thereof; x is from O to about 3; and each R5 is
an alkyl or hydroxyalkyl group containing from about 1 to
.
SU~3ST~T~JTE SHEE~ ~
WOg3/07086 PCr/USg2/08301 1' ',
2 1 2~ 4 9 1 16 -
about 3 carbon atoms or a polyethylene oxide group
conthining from about l to about 3 ethylene oxide groups.
The R5 groups can be attached to each other, e.g., through
an oxygen or nitrogen atom, to form a ring structure.
These amine oxide surfactants in particular include ClO-
Cl8 alkyl dimethyl amine oxides and C8-Cl2 alkoxy ethyl
dihydroxy ethyl amine oxides.
When included therein, the detergent compositions of the
present invention typically comprise from 0% to about 1S%,
preferably from about 1% to about 10% by weight of such
semi-polar nonionic surfactants.
~uilders
The detergent compositions fo the present invention can
comprise inorganic or organic detergent builders to assist
in mineral hardness control. Granular formulations
typically comprise at least about 1% more typically from
about 10% to about 80%, preferably from about 15% to about
50% by weight of the detergent builder. Lower or higher
levles of builder, however, are not meant to be excluded.
Inorganic detergent builders include, but are not limited
to, the alkali metal, ammonium and alkanolammonium salts
of polyphosphates (exemplified by the tripolyphosphates,
pyrophosphates, and glassy polymeric meta-phosphates),
phosphonates, phytic acid, silicates, carbonates
(including bicarbonates and sesquicarbonates), sulphates,
and aluminosilicates. Borate builders, as well as
builders containing borate-forming materials that can
produce borate under de~ergent storage or wash conditions
(hereinafter, collectively "borate builders"), can also be
used but are not preferred at wash conditions less than
about 500C, especially less than about 40C. Prefferd
builder systems are also free of phosphates.
Examples of silicate builders are the alkali metal
silicates, particularly those having a SiO2:Na20 ratio in
the range l.6:l to 3.2:l and layered silicates, such as
SUBSTITUTE SHEET
.
w~ ,0,086 2 1 2 0 ~ 9 1 Pcr/us92/o83ol
- 17 -
the layered sodium silicates described in U.S. Patent
4,664,839, issued May 12, 1987 to H. P. Rieck,
incorporated herein by reference. However, other
silicates may also be useful such as for example magnesium
silicate, which can serve as a crispening agent in
granular formulations, as a stabilizing agent for oxygen
bleaches, and as a component of suds control systems.
Examples of carbonate builders are the alkaline earth and
alkali metal carbonates, including sodium carbonate and
sesquicarbonate and mixtures thereof with ultra-fine
calcium carbonate as disclosed in German Patent
Application No. 2,321,001 published on November 15, 1973,
the disclosure of which is incorporated herein by
reference.
Aluminosilicate builders are useful in the present
invention. Aluminosilicate builders are of great
importance in most currently marketed heavy duty granular
detergent compositions, and can also be a significant
builder ingredient in liquid detergent formulations.
Aluminosilicate builders include those having the
empirical formula:
Mz(zAl02 ySiO2)
wherein M is sodium, potassium, ammonium or substituted
ammonium, z is from about 0.5 to about 2; and y is 1; this
material having a magnesium ion exchange capacity of at
least about 50 milligram equivalents of CaC03 hardness per
gram of anhydrous aluminosilicate. Preferred alumino-
silicates are zeolite builders which have the formula:
Nazt (Alt)2) Z (SiO2)y] xH20
wherein z and y are integers of at least 6, the molar
ratio of z to y is in the range from 1.0 to about 0.5, and
x is an integer from about 15 to about 264.
SUBSmUTE SHEET
W093~07086 PCT/USg2~08~1
~1~0491 18 -
Useful aluminosilicate ion exchange materials are
commercially available. These aluminosilicates can be
crystalline or amorphous in structure and can be
naturally-occurring aluminosilicates or synthetically
derived. A method for producing aluminosilicate ion
exchange materials is disclosed in U.S. Patent 3,985,669,
Krummel, et al., issued October 12, 1976, incorporated
herein by reference. Preferred synthetic crystalline
aluminosilicate ion exchange materials useful herein are
available under the designations Zeolite A, Zeolite P (B),
and Zeolite X. In an especially preferred embodiment, the
crystalline aluminosilicate ion exchange material has the
formula:
Nal2t(A12)12(sio2)12] xH2
wherein x is from about 20 to about 30, especially about
27. This material is known as Zeolite A. Preferably, the
aluminosilicate has a particle size of about 0.1-10
microns in diameter.
Specific examples of polyphosphates 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 about 21, and salts of phytic acid.
Examples of phosphonate builder salts are the water-
soluble salts of ethane l-hydroxy-l, l-diphosphonate
particularly the sodium and potassium salts, the water-
soluble salts of methylene diphosphonic acid e.g. the
trisodium and tripotassium salts and the water-soluble
salts of substituted methylene diphosphonic acids, such as
the trisodium and tripotassium ethylidene, isopyropylidene
benzylmethylidene and halo methylidene phosphonates.
Phosphonate builder salts of the aforementioned types are
disclosed in U.S. Patent Nos. 3,159,581 and 3,2i3,030
SUBSI-ITUTE SHEEr
2 1 2 0 ~ 9 1 Pcr/us92/o83ol
- 19-
issued December 1, 1964 and October 19, 1965, to Diehl;
U.S. Patent No. 3,422,021 issued January 14, 1969, to
- Roy; and U.S. Patent Nos. 3,400,148 and 3,422,137 issued
September 3, 1968, and January 14, 1969 to Quimby, said
disclosures being incorporated herein by reference.
Polycarboxylate builder can generally be added to the
composition in acid form, but can also be added in the
form of a neutralized salt. When utilized in salt form,
alkali metals, such as sodium, potassium, and lithium, or
aLkanola D onium salt~ are preferred.
Included among the polycarboxylate ~uilders are a ~ariety
of categories of useful materials. One important category
of polycarboxylate builders encompasses the ether
polycarboxylates. A number of ether polycarboxylates have
been disclosed for use as detergent builders. Examples of
useful ether polycarboxylates include oxydisuccinate, as
disclosed in Berg, U.S. Patent 3,128,287, issued April 7,
1964, and Lamberti et al., U.S. Patent 3,635,830, issued
January 18, 1972, both of which are incorporated herein by
reference.
A specific type of ether polycarboxylates useful as
builders in the present invention also include those
having the general formula:
CH(A)(COOX)-CH(COOX)-O-CH(COOX)-CH(COOX1(B)
wherein A is H or OH; B is H or -O-CH(COOX)-CH2(COOX); and
X is H or a salt-forming cation. For example, if in the
above general formula A and B are both H, then the
compound is oxydissuccinic acid and its water-soluble
salts. If A is OH and B is H, then the compound is
tartrate monosuccinic acid (TMS) and its water-soluble
salts. If A is H and B is -O-CH~COOX)-CH2(COOX), then the
compound is tartrate disuccinic acid (TDS) and its water-
501Uble salts. Mixtures of these builders are especially
preferred for use herein. Particularly preferred are
mixtures of TMS and TDS in a weight ratio of TMS to TDS
:
SU3STITUTE S~T
W093/07086 2 1 2 0 1 9 1 20 - PCT/US92/08301 `'
of from about 97:3 to about 20:80. These builders are
disclosed in U.S. Patent 4,663,071, issued to Bush et al.,
on May 5, 1987.
Suitable ether polycarboxylates also include cyclic
compounds, particularly alicyclic compounds, such as those
I described in U.S. Patents 3,923,679; 3,835,163; 4,158,635;
¦ 4,120,874 and 4,102,903, all of which are incorporated
herein by reference.
Other useful detergency builders include the ether
hydroxypolycarboxylates represented by the structure:
HO-tC(R)(COOM)-C(R)(COOM)-O]n-H
wherein N is hydrogen or a cation wherein the resultant
salt is water-soluble, preferably an alkali metal,
ammonium or substituted ammonium cation, n is from about 2
to about lS (preferably n is from about 2 to about 10,
more preferably n averages from about 2 to about 4) and
¦ each R is the same or different and selected from
hydrogen, Cl 4 alkyl or CI_4 substituted alkyl (preferably
R is hydrogen).
Still other ether polycarboxylates include copolymers of
maleic anhydride with ethylene or vinyl methyl ether, 1,
3, 5-trihydroxy benzene-2, 4, 6-trisulphonic acid, and
carboxymethyloxysuccinic acid.
Organic polycarboxylate builders also include the various
alkali metal, ammonium and substituted ammonium salts of
polyacetic acids. Examples include the sodium, potassium,
lithium, ammonium and substituted ammonium salts of
ethylenediamine tetraacetic acid, and nitrilotriacetic
acid.
Also included are polycarboxylates such as mellitic acid,
succinic acid, oxydisuccinic acid, polymaleic acid,
benzene 1,3,5-tricarboxylic acid, and
carboxymethyloxysuccinic acid, and soluble salts thereof.
- Citrate builders, e.g., citric acid and soluble salts
thereof (particularly sodium salt), are polycarboxylate
builders of particular importance for heavy duty liquid
detergent formulations, but can also be used ~n granular
SUBSTITUTE SHEET
2 1 2 0 ~ 9 1
- 21 -
compositions. Suitable salts include the metal salts such
as sodium, lithium, and potassium salts, as well as
ammonium and substituted ammonium salts.
- Other carboxylate builders include the carboxylated
carbohydrates disclosed in U.S. Patent 3,723,322, Diehl,
issued March 28, 1973, incorporated herein by reference.
Also suitable in the detergent compositions of the present
invention are the 3,3-dicarboxy-4-oxa-1,6-hexanedioates
and the related compounds disclosed in U.S. Patent
4,566,984, Bush, issued January 28, 1986, incorporated
herein by reference. Useful succinic acid builders
include the C5-C20 alkyl succinic acids and salts thereof.
A particularly preferred compound of this type is
dodecenylsuccinic acid. Alkyl succinic acids typically
are of the general formula
R-CH(COOH)CH2(COOH) i.e., derivatives of succinic acid,
wherein R is hydrocarbon, e.g., C10-C20 alkyl or alkenyl,
preferably C12-C16 or wherein R may be substituted with
hydroxyl, sulfo, sulfoxy or sulfone substituents, all as
described in the above-mentioned patents.
The succinate builders are preferably used in the form of
their water-soluble salts, including the sodium,
potassium, a D onium and alkanolammonium salts.
Specific examples of succinate builders include:
laurylsuccinate, myristylsuccinate, palmitylsuccinate, 2-
dodecenylsuccinate (preferred), 2-pentadecenylsuccinate,
and the like. Laurylsuccinates are the preferred builders
of this group, and are described in European Paten~
Application 86200690.5/0,200,263, published November 5,
1986.
Examples of useful builders also include sodium and
potassium carboxymethyloxymalonate,
carboxymethyloxysuccinate, cis-cyclo-hexane-
hexacarboxylate, cis-cyclopentane-tetracarboxylate, water-
soluble polyacrylates (these polyacrylates having
molecular weig~ts to above about 2,000 can also ba
~rlUTE SHEEr
WOg3/07~ 2 1 2 0 4 Y 1 22 - PCT/US92/0830l '
effectively utilized as dispersants), and the copolymers
of maleic anhydride with vinyl methyl ether or ethylene.
Other suitable polycarboxylates are the polyacetal
carboxylates disclosed in U.S. Patent 4,144,226,
Crutchfield et al., issued March 13, 1979, incorporated
herein by reference. These polyacetal carboxylates can be
prepared by bringing together, under polymerization
conditions, an ester of glyoxylic acid and a
polymerization initiator. The resulting polyacetal
carboxylate ester is then attached to chemically stable
end groups to stabilize the polyacetal carboxylate against
rapid depolymerization in alkaline solution, converted to
the corresponding salt, and added to a surfactant.
Polycarboxylate builders are also disclosed in U.S. Patent
3,308,067, Diehl, issued March 7, 1967, incorporated
herein by reference. Such materials include the water-
soluble salts of homo- and copolymers of aliphatic
carboxylic acids such as maleic acid, itaconic acid,
methylenemalonic acid, fumaric acid, aconitic acid,
citraconic acid and methylenemalonic acid.
Other organic builders known in the art can also be used.
For example, monocarboxylic acids, and soluble salts
thereof, having long chain hydrocarbyls can be utilized.
These would include materials generally referred to as
"soaps.~' Chain lengths of C10-C20 are typically utilized.
The hydrocarbyls can be saturated or unsaturated.
Enzymes
Detersive enzymes can be included in the detergent
compositions of the present invention for a variety of
reasons including removal of protein-based, carbohydrate-
based, or triglyceride-based stains, for example, and
prevention of refugee dye transfer. The enzymes to be
incorporated include proteases, amylases, lipases,
cellulases, and peroxidases, as well as mixtures thereof.
They may be of any suitable origin, such as vegetable,
animal, bacterial, fungal and yeast origin. However,
their choice is governed by several factors such as pH-
SUBSmUrESHEr
w( ~,07086 2 1 2 0 ~ 9 1 Pcr/US92/08301
- 23 -
activity and/or stability optima, thermostability,
stability versus active detergents, builders and so on.
In this respect bacterial or fungal enzymes are preferred,
I such as bacterial amylases and proteases, and fungal
cellulases.
Suitable examples of proteases are the subtilisins which
are obtained from particular strains of B.subtilis and
B.licheniforms. Another suitable protease is obtained
from a strain of Bacillus, having maximum activity
throughout the pH range of 8-12, developed and sold by
Novo Industries A/S under the registered trade name
Esperase0. The preparation of this enzyme and analogous
enzymes is described in British patent specification No.
1,243,784 of Novo. Proteolytic enzymes suitable for
removing protein-based stains that are commercially
available include those sold under the tradenames
ALCALASETM and SAVINASETM by Novo Industries A/S (Denmark)
and-MAXATASETM by International Bio-Synthetics, Inc. (The
Netherlands).
Of interest in the category of proteolytic enzymes,
especially for liquid detergent compositions, are enzymes
referred to herein as Protease A and Protease B. Protease
A and methods for its preparation are described in
European Patent Application 130,756, published January 9,
1985, incorporated herein by reference. Protease B is a
proteolytic enzyme which differs from Protease A in that
it has a leucine substituted for tyrosine in position 217
in its amino acid sequence. Protease B is described in
European Patent Application Serial No. 87303761.8, filed
April 28, 1987, incorporated herein by reference. Methods
for preparation of Protease B are also disclosed in
European Patent Application 130,756, Bott et al.,
published January 9, 1985, incorporated herein by
reference.
Amylases include, for example, a-amylases obtained from a
special strain of B.licheniforms, described in more detai
in British patent specification No. 1,296,839 (Novo),
SUBSTITUTE SHEET
WOg3/07086 PCT~US92/08~1 f )
2120491 24 -
previously incorporated herein by reference. Amylolytic
proteins include, for example RAPIDASETM, ~nternational
Bio-Synthetics, Inc. and TERMAMYLTM, Novo Industries.
The cellulases usable in the present invention include
both bacterial or fungal cellulase. Preferably, they will
have a pH optimum of between 5 and 9.5. Suitable
cellulases are disclosed in U.S. Patent 4, 435, 307,
Barbesgoard et al., issued March 6, 1984, incorporated
herein by reference, which discloses fungal cellulase
produced from Humicola insolens. Suitable cellulases are
also disclosed in GB-A-2.075.028; GB-A-2.095.275 and DE-
OS-2.247.832.
Examples of such cellulases are cellulases produced by a
strain of Humicola insolens (Humicola grisea var.
thermoidea), particularly the Humicola strain DSM 1800,
and cellulases produced by a fungas of ~acillus N or a
cellulase 212-producing fungas belonging to the genus
Aeromonas, and cellulase extracted from the hepatopancreas
of a marine mollusc (Dolabella Auricula Solander).
Suitable lipase enzymes for detergent usage include those
produced by micro-organisms of the of the Pseudomonas
groups, such as ~seudomonas stutzeri ATCC 19.154, as
disclosed in British Patent 1,372,034, incorporated herein
by reference. Suitable lipases include those which show a
positive immunological cross-reaction with the antibody of
the lipase produced by the microorqanism Pseudomonas
fluorescens IAM 1057. This lipase and a method for its
purification have been described in Japanese Patent
Application 53-20487, laid open on February 24, 1978.
This lipase is available from Amano Pharmaceutical Co.
Ltd., Nagoya, Japan, under the trade name Lipase P
"Amano," hereinafter referred to as "Amano-P." Such
lipases should show a positive immunological cross-
reaction with the Amano-P antibody, using the standard and
well-known immunodiffusion procedure according to
Ouchterlony (Acta. Med. Scan., 133, pages 76-79 (1950)).
These lipases, and a method for their immunoloqical cross-
SU8STITUTE SHEET
W~ `/07UK 25 21 2 0~ 91
reaction with Amano-P, are also described in U.S. Patent
4,707,291, Thom et al., issued November 17, 1987,
incorporated herein by reference. Typical examples
thereof are the Amano-P lipase, the lipase ex Pseudomon~s
fragi FERM P 1339 (available under the trade name Amano-
B), lipase ex Pseudomonas nitroreducens var. lipolyticum
FERM P 1338 (available under the trade name Amano-CES),
lipases ex Chro~obacter viscosu~, e.g. Chromob~ç~ç~
viscosum var. li~olvticum NRRLB 3673, commercially
available from Toyo Jozo Co., Tagata, Japan; and further
Chromobacter viscosum lipases from U.S. Biochemical Corp.,
U.S.A. and Disoynth Co., The Netherlands, and lipases ex
Pseudomonas qladioli.
Peroxidase enzymes are used in combination with oxygen
sources, e.g., percarbonate, perbonate, persulfate,
hydrogen peroxide, etc. They are used for "solution
bleaching", i.e. to prevent transfer of dyes of pigments
reaoved from substrates during wash operations to other
substrates in the wash solution. Perodidase enzymes are
known in the art, and include, for example, horseradish
peroxidase, ligninase, and haloperoxidase such as chloro-
and bromo-peroxidase. Peroxidase-containing detergent
compositions are disclosed, for example, in PCT
International Application Wo 89/099813, published October
19, 1g89, by O.Kirk, assigned to Novo Industries A/S,
incorporated herein by reference.
A wide range of enzyme materials and means for their
incorporation into synthetic detergent granules is also
disclosed in U.S. Patent 3,553,139, issued Jaunary 5, 1971
to McCarty et al. (incorporated herein by reference).
Enzymes are further disclosed in U.S. Patent No. 4, 101,
457, Place et al., issued July 18, 1978, and in U.S.
Patent 4,507,219, H~ghes, issued March 26, 1985, both
incorporated herein by reference. Enzyme materials useful
for liquid detergent formulations, and their incorporation
into such formulations, are disclosed in U.S. Patent
,
SUBSmUTE SHEET
WO93/07~K 2 1 2 0 4 9 1 PCT/US92/08301 ``
- 26 -
4,261,868, Hora et al., issued April 14, 1981, also
incorporated herein by reference.
Enzymes are normally incorporated at levels sufficient to
provide up to about 5 mg by weight, more typically about
O.S mg to about 3 mg, of active enz~me per gram of the
composition.
For granular detergents, the enzymes are preferably coated
or prilled with additives inert toward the enzymes to
minimize dust formation and improve storage stability.
Techniques for accomplishing this are well known in the
art.
Polymeric Soil Release Aqent
Any polmeric soil release agents known to those skilled in
the art can be employed in the detergent compositions of
the present invention. Polymeric soil release agents are -
characterîzed by having both hydrophilic segments, to
hydrophilize the surface of hydrophobic fibers, such as
polyester and nylon, and hydrophobic segments, to deposit
upon hydrophobic fibers and remain adhered thereto through
completion of washing and rinsing cycles and, thus, serve
as an anchor for the hydrophilic segments. This can
enable stains occuring subsequent to treatment with the
soil release agent to be more easily cleaned in later
washing procedures.
Polymeric soi~ relese agents include cellulosic
derivatives such as hydroxyether cellulosic polymers,
copolymeric blocks of ethylene terephthalate or propylene
terephthalate with polyethylene oxide or polyrropylene
oxide terep~thalate, and the like.
Cellulosic derivatives that are functional as soil release
agents are commerically available and include
hydroxyethers of cellulose such as MethocelR (Dow).
Cellulosic soil release agents also include those selected
from the group consisting of Cl-C4 al~yl and C4
hydroxyalkyl cellulose such as metbylcellulose,
çthylcellulose, hydroxypropyl methycellulose, and
hydroxybutYl meth~lcellulose. A variety of c~llulos~
SUBSTITUTE SHEET
WC /07086 PCT/US92/08301
27 21 2 0~ 91
derivatives useful as soil release polymers are disclosed
in U.S. Patent 4,000,093, issued December 28, 1976 to
Nicol, et al., incorporated herein by reference.
Soil release agents characterized by poly(vinyl ester)
hydrophobe segments include graft copolymers of poly(vinyl
ester), e.g. Cl-C6 vinyl esters, preferably poly(vinyl ;
acetate) grafted onto polyalkylene oxide backbones, such
as polyethylen oxide backbones. Such materials are known
in the art and are described in European Patent
Application 0 219 048, published April 22, 1987 by Kud, et
al. Suitable commercially available soil release agents
of this kind include the SokalanTM type of material, e.g.,
SokalanTM HP-22, available from BASF (West Germany).
one type of preferred soil release agent is a copolymer
having random blocks of ethylene terephthalate and
polyethylene oxide (PEO) terephthalate. More
specifically, these polymers are comprised of repeating
units of ethylene terephthalate and PE0 terephthalate in a
mole ratio of ethylene terephthalate units to PE0
terephthalate units of from about 25:75 to about 35:65,
said PE0 terephthalate units containing polyethylene
oxide having molecular weights of from about 300 to about
2000. The molecular weight of this polymeric soil release
agent is in the range of from about 25,000 to about
55,000. See U.S. Patent 3,g59,230 to Hays, issued May 25,
1976, which is incorporated by reference. See also U.S.
Patent 3,893,929 to Basadur issued July 8, 1975
(incorporated by reference) which discloses similar
copolymers.
Another preferred polymeric soil release agent is a
polyester with repeat units of ethylene terephthalate
units containing 10-15% by weight of ethylene
terephthalate units together with 90-80% by weight of
polyoxyethlyene terephthalate units, derived from a
polyoxyethylene glycol of average molecular weight
300-5,000, and the mole ratio of ethylene terephthalate
units to polyoxyethylene terepbthalate units in the
SUBSmUTE SHEET
WO 93/07086 PCl`/US92/08301 : i
2120491 28-
polymeric compound is between 2:1 and 6:1. Examples of
this polymer include the commercially available material
ZelconR 5126 (from Dupont) and Milease R T (from ICI).
These polymers and methods of their preparation are more
fully described in U. S. Patent 4, 702, 857, issued October
27, 1987, to Gosselink, which is incorporated herein. '~
Other suitable polymeric soil release agents include the
ethyl or methyl-capped 1,2-propylene terephthalate-
polyoxy- ethylene terephthalate polyesters of U.S. Patent
4 , 711 , ~30 , issued December 8 , 1987 , to Gosselink et al .,
the anionic end-capped oligomeric esters of U.S. Patent
4,721,580, issued January 26, 1988!, to Gosselink, wherein
the anionic end-caps comprise sulfo-polyethoxy groups
derived from polyethylene glycol (PEG), the block
polyester oligomeric compounds of U. S . Patent 4, 702, 857,
issued October 27, 1987 to Gosselink, having polyethox~r :
end-caps of the formula X-(OCH2CH2)n- wherein n is from
12 to about 43 and X is a Cl-C4 alkyl, or preferably
methyl, all of these patents being incorporated herein by
reference.
Additional soil release polymers include soil release
polymers of U.S. Patent 4,877,896, issued October 31, 1989
to Maldonado et al., which discloses anionic, especially
sulfoaroyl, end-capped terephthalate esters, said patent
being incorporated herein by reference. The terephthalate
esters c:ontain unsy~netrically substituted oxy-l,2-
alkyleneoxy units.
If utilized, soil release agents will generally comprise
from about O.01% to about 10.OS, by weight, of the
detergent composi-tions herein, typically from about 0.lS
to about 5%, preferably from about O.2% to about 3.0%.
October 31, 1989 to Maldonado et al. All of these patents
are incorporated herein by reference.
If utilized, soil release agents will generally comprise
from about 0.01% to about lO.OS, by weight, of the
d~tergent'composi-tions herein, typically from about 0.lS
to about 5%, preferably from about O.2% to about 3.0%.
SUBSTITUTE SHEET
w~ ?070s6 212 o ~ g i Pcr/US92/0830
- 29 -
Chelatina Aqents
The detergent compositions of the present invention may
also contain one or more iron and manganese chelating
agents as a builder adjunct material. Such chelating
agents can be selected from the group consisting of amino
carboxylates, amino phosphonates, polyfunctionally-
substituted aromatic chelating agents and mixtures
thereof, all as hereinafter defined. Without intending
to be bound by theory, it is believed that the benefit of
these materials is due in part to their exceptional
ability to remove iron and mangane~e ions from washing
solutions by formation of soluble chelates.
Amino carboxylates useful as optional chelating agents in
compositions of the invention can have one or more,
preferably at least two, units of the substructure
CH2 `A
\
N - (CH2)x - COOM,
wherein M is hydrogen, alkali metal, ammonium or
substituted a o onium (e.g. ethanolamine) and x is from 1
to about 3, pref- erably 1. Preferably, these amino
carboxylates do not contain alkyl or alkenyl groups with
more than about 6 carbon atoms. Operable amine
carboxylates include ethylenediaminetetraacetates, N-
hydroxyethylethylenediaminetriacetates,
nitrilotriacetates, ethylenediamine tetraproprionates,
triethylenetetraaminehexa-acetates,
diethylenetriaminepentaacetates, and ethanoldiglycines,
alkali metal, ammonium, and substituted ammonium salts
thereof and mixtures thereof.
Amino phosphonates are also suitable for use as chelating
agents in the detergent compositions of the invention when
at least low levels of total phosphorus are permitted in
detergent composi- tions. Compounds with one or more,
preferably at least two, units of the substructure
SUBSmUTE SHEET
W093/07086 PCT/US92/08~1 '`
2 1 2 ~ Y1 30
C 2
N (cH2)x P3M2'
wherein M is hydrogen, alkali metal, ammonium or
substituted a o onium and x is from 1 to about 3,
preferably 1, are useful and include
ethylenediaminetetrakis (methylenephosphonates),
nitrilotris (methylenephosphonates) and
diethylenetriaminepentakis (methylenephosphonates).
Preferably, these amino phosphonates do not contain alkyl
or alkenyl groups with more than about 6 carbon atoms.
Alkylene groups can be shared by substructures.
Polyfunctionally - substituted aromatic chelating agents
are also useful in the compositions herein. These
materials can comprise compounds having the general
formula:
OH
R ~ N
R^~ R
R
wherein at least one R is -SO3H or -COOH or soluble salts
thereof and mixtures thereof. U.S. Patent 3,812,044,
issued May 21, 1974, to connor et al., incorporated herein
by reference, discloses polyfunctionally - substituted
aromatic chelating and sequestering agents. Preferred
compounds of this type in acid form are
dihydroxydisulfobensenes such as 1,2-dihydroxy -3,5-
disulfo- benzene. Alkaline detergent compositions can
contain these materials in the form of alkali metal,
SUBSmUTE SHEET
W~ 3/07~6 PCT/US92/08~1
- 31 21 2 01 9l
ammonium or substituted ammonium (e.g. mono-or triethanol-
amine) salts.
If utilized, these chelating agents will generally
comprise from about 0.1% to about 10% by weight of the
detergent composi-tions herein. More preferably chelating
agents will comprise from about 0.1% to about 3.0% by
weight of such compositions.
Clav Soil Removal1Anti-redeDosition Aaents
Clay soil removal/anti-redeposition agents useful in the
detergent compositions of the present invention include
polyethylene glycols and water-soluble ethoxylated amines
having clay soil removal and anti-redeposition properties,
as well as additional polyamino compounds derived from
aspartic acid but not containing glutamic acid.
Polyethylene glycol compounds useful in the detergent
compositions of the present invention typically have a
molecular weight in the range of from to about l,000 to
about 20,000, more preferably from about 2,000 to about
12,000, most preferably from about 4,000 to about 8,000.
Such compunds are commercially available and are sold as
Carbowax~, which is available from Union Carbide, located
in Danbury, Conn.
The water soluble ethoxylated amines are preferably
selected from the group consisting of :
(l) ethoxylated monamines having the
formula :
(X-L)-N R(R2)2
(2) ethoxylated diamines having the
formula :
R2-N-Rl_N_R2 (R2)2-N-Rl-N-(R2)2
L L L
- X X X
or
(X-L)2-N-Rl-N-(R2)2
(3) ethoxylated polyamines baving the
formula :
SUBSTITUTE SHEET
W093107086 2 1 2 0 ~ 9 1 PCT/USg2/0830~
- 32 -
R2
R3-((A1)q~(R4)t~N~L~X)p
(4) ethoxylated amine polymers having the
general formula :
R2
( (R2 ) 2-N) W (Rl-N) X (Rl-N) y ~Rl-N-L-X) z
L
X
and
~5) mixtures thereof; wherein Al is :
O O O O O
-IC-, -NCO-, -NCN~ N-, -O~N-,
R R R R
O O O O O
-CO-, -OCO-, -OC-, -CNC-,
or -0-; R is H or Cl-C4 alkyl or hydroxyalkyl Rl is C2-C12
alkylene, hydroxyalkylene, alkenylene, arylene or
alkarylene, or a C2-C3 oxyalkylene moiety having from 2 to
about 20 oxyalkylene units provided that no O-N bonds are
formed ; each R2 is Cl-C4 or hydroxyalkyl, the moiety -L-
X, or two R2 together form the moiety -(CH2)r, -A2-(CH2)S-
, wherein A2 is -O- or -CH2-, r is 1 or 2, s is 1 or 2,
and r + s is 3 or 4 ; X is a nonionic group, an anionic
group or mixture thereof ; R3 is a substituted C3-C
alkyl, hydroxyalkyl, alkenyl, aryl, or alkaryl group
having substitution sites ; R4 is C1-C12 alkylene,
hydroxyakylene, alkenylene, arylene or alkarylene, or a
C2-C3 oxyalkylene moiety having from 2 to about 20
oxyalkylene units provided that no O-O or O~N bonds are
formed ; L is a hydrophili~ chain which contains the
polyoxyalky}ene moiety ~((R5O)m(CH2CH20)n)-~ wherin R5 is
C3-C4 alkylene or hydroxyalkylene and m and n are numbers
such that the moiety -CH~CH~O) n~ comprises at least about
SU8STITUTE SHEET
W~` ' t/07086 Pcr/uss2/os301
2120491
- 33 -
So% by weight of said polyoxyalkylene moiety ; for said
monamines, m is from 0 to about 3, and n is at least about
6 when Rl is C2-C3 alkylene, hydroxyalkylene, or
alkenylene, and at least about 3 when Rl is other than C2-
C3 alkylene, hydroyalkylene or alkenylene ; for said
polyamines and amine polymers, m is from 0 to about 10 and
n is at least about 3 ; p is from 3 to 8 ; q is 1 or 0 ; t
is 1 or 0, provided that t is 1 when q is 1 ; w is 1 or 0
; x + y + z at least 2 ; and y + z is at least 2.
Tbe most preferred soil release and anti-redeposition
agent are ethoxylated tetraethylenepentamine. Exemplary
ethoxylated amines are further deseribed in U.S. Patent
4,597,898, VanderMeer, issued July 1, 1986,
ineorporated herein by referenee. Another group of
preferred elay soil removallanti-redeposition agents are
the eationie eompounds diselosed in European Patent
Applieation 111,965, Oh and Gosselink, published June 27,
1984, ineorporated herein by referenee. Other elay soil
removal/anti-redeposition agents whieh ean be used inelude
the ethoxylated amine polymers diselosed in European
Patent Applieation 111,984, Gosselink, published June 27,
1984; the zwitterionie polymers diselosed in European
Patent Applieation 112,592, Gosselink, published July 4,
1984; and the amine oxides disclosed in U.S. Patent
4,548,744, Connor, issued Oetober 22, 1985, all of whieh
are ineorporated herein by reference.
The most preferred soil release and anti-deposition agents
are ethoxylated tetraethylenepentamine and the polythylene
glyeols having a moleeular weigbt in the range of from
about 4,000 to about 8,000.
Granular detergent compositions whieh contain such
eompounds typieally contain from about 0.01% to about
10.0% by weight of the elay removal agent.
PolYmerie Dispersina Aaent
Polymerie polyearboxylate dispersing agents ean
advantageouslY be utilized in the detergent eompositions
SUBSmUTE SHEET
WOg3/07~ PCT/US92/08301 f `i
2120491 - 34 -
of the present invention. These materials can aid in
calcium and magnesium hardness control. In addition to
acting as a builder adjunt analogously to the
poycarboxylate described above in the Builder description,
it is believed, though it is not intended to be limited by
theory, that these higher molecular weight dispersing
agents can further enhance overall detergnet builder
performance by inhibiting crystal growth of inorganics, by
particulate soil peptization, and by antiredeposition,
when used in combination with other builders including
lower molecular weight polycarboxylates.
The polycarboxylate materials which can be employed as the
polymeric polycarboxylate dispersing agent are these
polymers or copolymers which contain at least about 60% by
weight of segments with the general formula :
r~C ~
n
wherein X, Y, and Z are each selected from the group
consisting fo hydrogen, methyl, carboxy, carboxmethyl,
hydroxy and hydroxymethyl; a salt forming cationand n is
from about 30 to about 400. Preferably, X si hydrogen or
hydroxy, Y is hydrogent or carboxy, Z is hydrogen and M is
hydrogen, alkali metal, ammonia or substituted ammonium.
Polymeric polycarboxylate materials of this type can be
prepared by polymerizing or copolymerizing suitable
unsaturated monomers, pref2rably in their acid form.
Unsaturated monomeric acids that can be polymerized to
form suitable polymeric polycarxylates include acrylic
acid, maleic acid (or maleic anhydride), fumaric acid,
itaconic acid, aconitic acid, mesaconic acid, citraconic
acid and methylenemalonic acid. The presence in the
polymeric polycarboxylates herein of monomeric segments,
containing no carboxylate radicals such as vinylmethyl
SUBSTITUTE SHEET
:
W~ ~/070~ PCT/US92/08~1
- 3S - 1 ~ O 1 9 1
ether, styrene, ethylene, etc. is suitable provided that
such segments do not constitute more than about 40% by
weight.
Particularly suitable polymeric polycarboxylates can be
derived from acrylic acid. Such acrylic acid-based
polymers which are useful herein are the water soluble
salts of polymerized acrylic acid. The average molecular
weight of such polymers in the acid form ranges from about
2,000 to 10,000, more preferably from about 4,000 to 7,000
and most preferably from about 4,000 to 5,000. Water
soluble salts of such acrylic acid polymers can include,
for example, the alkali metal, ammonium and substituted
ammonium salts. Soluble polymers of this type are known
materials. Use of polyacrylates of this type in detergent
compositions have been disclosed, for example, in Diehl,
U.S. Patent No. 3,308,067, issued March-7, 1967. This
patent is incorporated herein by reference.
Acrylic/maleic-based copolymers may also be used as a
preferred component of the dispersing agent. Such
materials include the water soluble s~lts of copolymers of
acrylic acid and maleic acid. The average molecular
weight of such copolymers in the acid form ranges from
about 5,000 to 100,000, preferably from about 6,000 to
60,000, more preferably from about 7,000 to 60,000. The
ratio of acrylate to maleate segments in such copolymers
will generally ranqe from about 30:1 to about 1:1, moe
preferably from about 10:1 to 2:1. Water-soluble salts of
such acrylic acid/maleic acid copolymers can include, for
example, the alkali metal, ammonium and substituted
ammonium salts~ Soluble acrylate/maleate copolymers of
- this type are knwon materials which are described in
European Patent Application No. 66915, published December
15, 1982, which publication is incorporated herein by
reference~
Polyamino dispersant compounds derived from aspartic acid
but not containing glutamic acid are useful as additional
polyamino disperant compounds in t~e detergent
SUBSTITUTE SHEET
W093/07 ~ ~ 1 2 0 4 9 1 PCT/US92/08~1 f``~
- 36 -
compositions of the invention. Such polyamino dispersant
compounds suitable for inclusion herein are disclosed in
EP-A--305282, EP-A-305283 and EP-A-351629.
If utilized, the polymeric dispersing aqents will
generally comprise from about 0.2% to about 10%,
preferably form about 1% to about 5% by weight of the
laundry detergent compositions.
Bri~htener
Optical brighteners or other brightening or whitening agents
known to those skilled in the art can be incorporated into
the laundry detergent compositions of the present invention.
However, the choice of brightener will depend upon a nu~ber
of factors, such as the type of detergnt, the nature of other
components present in the detergent composition, the
temperatures of wahs wash, the degree of agitation, and the
ratio of the material washed to tub size.
The brightener selection is also dependent upon the type of
material to be cleaned, e.g. cottons, synthetics, etc.
Since most laundry detergent products are used to clean a
variety of fabrics, the detergent compositions should
contain a mixture of brighteners which will be effective
for a variety of fabrics. It is of course necessary that
the individual components of such a brightener mixture be
compatible.
Commercial optical brighteners can be classified into
subgroups which include, but are not necessarily limited
to, derivatives of stilbene, pyrazoline~ coumarin,
carboxylic acid, methinecyanines, dibenzothiphene-5,5-
dioxide, azoles, 5- and 6-membered-ring heterocycles, and
other miscellaneous agents. Examples of such brighteners
are disclosed in "The Production and Application of
Fluorescent Brightening Agents", M. Zahradnik, Published by
John Wiley & Sons, New York (1982), the disclosure of which
is incorporated herein by reference.
Stilbene derivatives include, but are not necessarily
limited to, derivatives of stilbene; triazole derivatives
SUBSmUTE SHEET
W~ ~/07086 2 1 2 0 '1 9 ~CT/US92/0830l
of stilbene; oxadiazole derivatives of stilbene; oxazole
derivatives fo stilbene; and stryl of stilbene.
Certain derivatives of bis(triazinly) aminostilbene may be
prepared from 4,4'-diamine-stilbene-2,2'-disulfonic acid.
Coumarin derivatives inelude, but are not neeessarily
limited to, derivatives substituted in the 3-position, in
the 7-position, and in the 3- and 7-positions.
Carboxylie aeid derivatives inelude, but are not
neeessarily limited to, fumarie aeid derivatives; benzoie
aeid derivatives; p-phenylene-bis-aerylie aeid derivatives;
naphthalenediearboxylie aeid derivatives; heteroeyelie aeid `
derivatives; and einnamie aeid deriyatives.
Cinnamie aeid derivatives ean be further subelassified into -
groups whieh inelude, but are not neeessarily limited to,
einnamie aeid derivatives, styrylazoles, styrylbenzofurans, -
styryloxadiazoles, styryltriazoles, and styrylpolyphenyls,
as diselosed on page 77 of the Zahradnik referenee.
The styrylazoles ean be further subelassified into
styrylbenzoxazoles, styrylimidazoles and styrylthiazoles,
as diselosed on page 78 of the Zahradnik referenee. It
will be understood that these three identified subclasses
may not neeessarily refleet an exhaustive list of subgroups
into whieh styrylazoles may be subelassified.
Other optieal brighteners are the derivatives of
dibenzothiophene-5,5-dioxide disclosed at page 741-749 of
The Kirk-Othmer Eneyelopedia of Chemical Teehnology. Volume
3, pages 737-750 (John Wiley & Son, Inc., 1962), the
disclosure of whieh is ineorporated herein by referenee,
and inelude 3,7-daiminodibenzothiophene-2, 8-disulfonic
aeidS, S dioxide.
Other optieal brighteners are azoles, whieh are derivatives
of 6-membered ring heterocyeles. These can be further
subeategorized into monoazoles and bisazoles. Examples of
monazoles and bisazoles are diselosed in the Kirk-Othmer
referenee.
Examples of sueh eompounds inelude brighteners derived from
pyrazine and brighteners derived from 4-aminonaphthalamide.
SUBSTITUTE SHEET
W~g3/07~ PCT/US92/08301 `~
21 2 04 91 - 38 -
In addition to the brighteners already described,
miscellaneous agents may also be useful as brighteners.
Examples of such miscellaneous agents are disclosed at
pages 93-95 of the Zahradnik reference, and include 1-
hydroxy-3,6,8-pyrenetrisulfonic acid; 2,4-dimethoxy-1,3,5-
triazin-6-yl-pyrene; 4,5-diphenylimidazolonedisulfonic
acid; and derivatives of pyrazolinequinoline.
Other specific examples of optical brightener are those
identified in U.S. Patent 4,790,856, issued to Wixon on
December 13,1988, the disclosure of which is incorporated
herein by reference. Thse brighteners include the
PhorwhiteTM series of brighteners from Verona. Others
brighteners disclosed in this reference include : Tinopal
UNPA, Tinopal CBS adn Tinopal SBM; available from Ciba-
Geigy; Artic White CC and Artic White CND, available from
Hilton-Davis, located in Italy; the 2-(4-styrylphenyl)-2H-
naphthol(l,2-d)triazoles; 4,4'-bis-(1,2,3-triazol-2-yl)-
stilbene; 4,4'-bis(styryl)bisphenyls; and the y-amino-
coumarins. Specific examples of these brighteners include
4-methyl-7-diethylamino coumarin; 1,2-bis(-bensimidazol-2-
yl)-ethylene; 1,3-diphenylphrazolines; 2,5-bis(benzoxazol-
2-yl)-thiophene; 2-styryl-naphth-(1,2-d)-oxazole; and 2-
(stilbene-4-yl)-2H-naphtho(1,2-d)triazole.
Still other optical brighteners include those disclosed in
U.S. Patent 3,646,015, issued February 29, 1972 to
Hamilton, the disclosure of which is incorporated herein by
reference.
If utilized, the optical brighteners will generally
comprise from about 0.05% to about 2.0%, preferably from
about 0.1% to about !.0% by weight of the laundry detergent
compositions.
Suds Su~ressors
Compounds known, or which become known, for reducing or
suppressing the formation of suds can be incorporated into
the detergent compositions of the present in~ention. The
incorporation of such materials , hereafter "suds
supressor", can be desirable because the polyhydroxy fatty
SUBSmUTE SHEET
W~ "/07086 2 1 2 0 4 9 1 PCT/US92/08~1
- 39 -
acid amide surfactants hereof can increase suds stability
of the detergent compositions. Suds suppression can be of
particular importance when the detergent compositons
include a relatively high sudsing surfactant in combination
with the polyhydroxy fatty acid amide surfactant.
Suds suppression is particularly desirable for compositions
intended for use in front loading automatic washing
machines. These machines are typically characterized by
having drums, for containing the laundry and wash water,
which have a horizontal axis and rotary action about the
axis. This type of agitation can result in high suds
formation and, consquently, in reduced cleaning
performance. The use of suds suppressors cna also be of
particular importance under hot water wahsing conditions
and under high surfactant concentration conditions.
A wide variety of materials may be used as suds
suppressors. Suds suppressors are well known to those
skilled in the art. They are generally described, for
example, in Kirk Othmer Encyclopedia of Chemical
Technology, Third Edition, Volume 7, pages 430-447 (John
Wiley & Sons, Inc., 1979). One categroy of suds suppressor
of particular interest encompasses monocarboxylic fatty
acids and soluble salts thereof. These materials are
discussed in U.S. Patent 2,954,347, issued September 27,
1960 to Wayne St. John, said patent being incorporated
herein by reference. The monocarboxylic fatty acids, and
salts thereof, for use as suds suppressors typically have
hydrocarbyl chains of 10 to about 24 carbon atoms,
preferably 12 to 18 carbon atoms. Suitable salts include
alkali metal salts such as sodium, potassium, and lithium
salts, and ammonium and alkanolammonium salts. These
materials are a preferred category of suds suppressor for
detergent compositions.
The detergent compositions of the present invention may
also contain non-surfactant suds suppressors. These
include, for example, high molecular weight hydrocarbons
such as paraffin, fatty acid esters (e.g., fatty acid
SUBSTITUTE SHEET
WO93/07~K 2 120 ~ 1 PCT/US92/08301 `
- 40 -
triglycerides), fatty acid esters of monovalent alcohols,
aliphatic Cl8-C40 ketones (e.g. stearone), etc. Other suds
inhititors include N-alkylated amino triazines such as tri-
to hexa-alkylemlamines or di- to tetra-alkyldaimine
chlortriazines formed as -products of cyanuric choloride
with two or three moles of a primary or secondary amine
containing 1 to 24 carbon atoms, propylene oxide, and
monostearyl phosphates such as monostearyl alcohol
phosphate ester and monostearyl di-alkali metal (e.g.,
sodium, potassium, lithium) phosphates and phosphate
esters. The ~ydrocarbons, such as paraffin and
haloparaffin, can be utilized in liquid form. The liquid
hydrocarbons will be liquid at room temperature and
atmospheric pressure, and will have a pour point in the
range of about -40C and about 5C, and a minimum boiling
point not less than about 100C (atmospheric pressure). It
i8 also known to utilize waxy hydrocarbons, preferably
having a melting point below about 100C. The hydrocarbons
constitute a preferred category of suds suppressor for
detergent compositions. Hydrocarbon suds suppressors are
described for example in U.S. Patent 4,265,779, issued May
5, 1981 to Gandolfo et al., incorporated herein by
reference. The hydrocarbons, thus, include aliphatic,
alicyclic, aromatic, and heterocyclic saturated or
unsaturated hydrocarbons having from about 12 to about 70
carbon atoms. The term "parrafin", as used in this suds
suppressor discussion, is intended to include mixtures of
true paraffins and cyclic hydrocarbons.
Another preferred category of non-surfactant suds comprises
silicone suds suppressors. This category includes the use
fo polyorganosiloxane oils, such as polydimethysiloxane,
dispersions or emulsions fo polyorganosiloxane oils or
resins, and combinations of polyorganosiloxane with silica
particles wherein the polyorganosiloxane is chemisorbed of
fused onto the silica. Silicone suds suppressors are well
known in the art and are, for example disclosed in U.S.
Patent 4,265,779, issued May 5, 1981 to Gandolfo et al.,
SUBSTITUTE SHEET
wc ~/o7~ 2 1 2 0 ~ 9 1 PCTtUS92/08~1
- 41 -
and European Patent Application No. 89307851.9, published
February 7, 1990, by Starch, M.S., both incorporated herein
by reference. ~-
Other silicone suds suppressors are disclosed in U.S.
Patent 3,455,839, which relates to compositions and
processes for defoaming aqueous solutions by incorporating
therein small amounts of polydimethylsiloxane fluids.
Mixtures of silicone and silanated silica are described,
for instance, in German Patent Application DOS 2,124,526.
Silicone defoamers and suds controlling agents in granular
detergent compositions are disclosed in U.S. Patent
3,933,672, Bartolotta et al., and in U.S. Patent
4,652,392, Baginski et al., issued March 24, 1987.
An exemplary silicone based suds suppressor for use herein
i8 a suds suppressing amount of a suds controlling agent
consisting essentially of :
'
(i) Polydimethlsiloxane fluid having a viscosity of
from about 20 cs. to about 1500 cs. at 25C;
(ii) From about 5 to about 50 parts per 100 parts by
weight of :
(i) f siloxane resin composed of (CH3)3 SiOl/2
units of SiO2 units in a ratio of from CH3)3Siol/2
units and to Si02 units of from about 0.6:1 to
about 1.2:1; and
(iii) from about 1 to about 20 parts per 100 parts
by weight of :
(i) of a solid silica gel :
Suds suppressors, when utilized, are present in a "suds
suppressing amoung". By "suds suppressing amount" is meant
that he formulator of the composition can select an amount
of this suds controlling agent that will control the suds
to the extent desired. Teh amount of suds control will
vary with the detergent surfactant selected. Fro example,
SUBSTITUTE SHEET
W093/070~ PCT/US92/08~1
21 2 0~ 9l 42 -
with high sudsing surfactants, relatively more of the suds
controlling agent is used to achieve the desired suds
control than with low foaming surfactants.
The detergent compositions of the present invention will
generally comprise from 0% to about 5% of suds suppressor.
When utilized as suds suppressors, monocarboxylic fatty
acids, and salts thereof, will be present typically in
amounts up to about 5%, by weight, of the detergent
composition. Preferably, from about 0.5% to about 3% of
fatty monocarboxylate suds suppressor is utilized.
Silicone suds suppressors are typically utilized in amounts
up to about 2.0%, by weight, of the detergent composition,
although higher amounts may be used. This upper limit is
practical in nature, due primarily to concern with keeping
costs minimized and effectiveness of lower amounts for
effectively controlling sudsing. Preferably from about
0.01% to about 1% of silicone suds suppressor is used, more
preferably from about 0.25% to about 0.5%. As used herein,
these weigbt percentage values include any silica that may
be utilized in combination with polyorganosiloxane, as well
as any adjunct materials that may be utilized. Monostearyl
phosphates are generally utilized in amounts ranging from
about 0.1% to about 2% by weight of the compositions.
Hydrocarbon suds suppressors are typically utilized in
amounts ranging from about 0.01% to about 5.0%, although
higher levels can be used.
Bleach activators
The detergent compositions of the present invention may
contain one or more bleach activators.
If present, the amountof bleach activators will typically
be from about 0.1% to about 60%, more typically from about
0.5% to about 40%, of the bleaching composition (i.e. the
total of bleaching active plus ~leach activator).
A wide range of bleach activators can be used, examples `
being disclosed in Spadini et al USP 4179390. Preferred
bleacb activators include tetraacetyl alkylene diamines,
SUBSTITUTE SHEET -
W~ !07086 212 0 4 91 PCT/US92/08301
- 43 -
particularly tetraacetyl ethylene diamine (TAED) and
tetraacetyl (TAGU). Other activators that come into
consideration are the compounds of the formula :
R - CO - L
10.5. Techniques for controlling pH at recommended usuage
levels include the use of buffers, alkalis, acids, etc and
wherein R is an alkyl group containing from about 1 to 18
carbon atoms wherein the longest linear alkyl chain
extending from and including the carbonyl carbon containæ
from about 6 to about 10 carbon atoms and L is a leaving
group, the conjugate acid of which has a PKa in the range
of from 4 to about 13. These bleach activators are
described in U.S. Patent 4,915,854, issued April 10, 1990
to Mao, et al., incorporated herein by reference, and U.S.
Patent 4,412,934, whi~h was previously incorporated herein
by reference. Nonanoyloxybenzene sulfonate (NOBS) is
another preferred bleach activator.
The compositions of this invention may be formulated so
that during aqueous cleaning operations the wash water
will have a pH of, for example, 6.5 to 11, typically 7.5
to 10.5. Techniqueæ for controlling pH at recommended
usuage levels include the use of buffers, alkalis, acids,
etc and are well known in the art.
In use, the composition of the present invention will be
dissolved in an aqueous medium, typically tap water, ad
the fabric to be cleaned will be immersed in the resultant
bleaching or washing liquor, with agitation if
appropriate. The compos~tions can be used for soaking,
for washing by hand or in automatic laundry washing
machines. The concentration of actives in the said
liquor, the temperature, the degree of agitation and the
duration of the immersion may be varied, depending upon
the nature of the fabric and the amount of soiling.
Granular bleaching compositions and granular detergent
co~positions, to be effective and acceptable, must be
readily dispersible in aqueous media. }n the article by
;:
SUBSTITUTE SHEET
W093/07~ PCT/US92/08~1
2120~91
L. Heslinga and W. Sehwaiger, Reeueil, 85 (1966), 7s at
page 85, it is stated that eaprylyl peroxide (i.e.
dioetanoyl peroxide) is sparingly soluble in an agueous
perbonate solution (pH 10) at room temperature and that
the perhydrolysis under these eonditions is negligible.
Surprisingly, however, it has been found by the present
applieant that, when employed in the form of their urea
elathrates in aeeordanee with this invention, the
peroxides have a very aeeeptable dispersability in aqueous
media and give exeellent bleaehing performanee. This may
be manifest in various ways : thus, for example, eertain
embodients are very effeetive against earotenoid stains
that have proved resistant to bleaehing systems of the
prior art, whereas eertain other embodiments are
eomparable to or better than eonventional bleaehing
systems even in the absenee of perbonate.
Granular bleaehing eompositions and bleaeh eontaining
granular detergent eompositions should also possess good
bleaeh storage stability. The urea elathrates diaeyl and
tetraaeyl peroxides in aeeord with this invention
demonstrate good storage stability, even in the alkaline
eonditions of a detergent eomposition.
The present compositions have eertain advantages over the
eompositions diselosed in EP-A-O, 106, 584, whieh form
diaeyl peroxide in~ in that the level of diaeyl peroxide
ean be more accurately determined; moreover, the present
invention permits the benefits of diacyl peroxide
bleaehing to be obtained even in sit~ations where the use
of NOBS and/or perbonate is eontraindieated.
A further unexpeeted advan~age of the present invention is
that, although the presence of a bleach activator is not
preeluded, certain compositions aecording to the present
invention ean give exeellent results in the absenee of the
aetivator. Conventionally, the bleaeh aetivator (e.g.
NOBS or TAED) has been ineluded in perbonate-eontaining
eompositions in order to produee a peroxy aeid in~, sueh
aeids being effeetive in the bleaehing of non-earotenoid
SUBSmUTE SHEET
WG /070~ 212 0 4 91 PCT/US92/08301
- 45 -
hydrophobic stains (as in the case of peroxynonanoic acid
produced by NOBS) or hydrophilic stains (as in the case of
peroxyacetic acid produced by TAED). However, and whilst
not wishing to be bound by any theory, it is believed that
the diacyl or tetraacyl peroxide and the perbonate (or
other H2O2 source) present in the compositions will give
rise to a reaction in the aqueous medium to form peroxy
acid, thereby providing a system benefitting from the
bleaching properties of both the diacyl or tetraacyl
peroxide and the peroxy acid, even in the absence of a
conventional bleach activator. For instance, the compound
of the formula :
C9Hl9-NHCO-(CH2)4-CO-OO-CO-CH3
is believed to react with perbonate in sitvto produce two
effective bleaching agents, namely :
CgHlg~NHCO~(CH2)4~C(=O)OOH (NAAPA0 and
CH3C(=O)OOH (peroxyacetic acid).
The present invention is illustrated in and by the
following examples :
~ample 1
Dinonanoyl peroxide was prepared, using the method of L.S.
Silbert and D. Swern, J. Amer. Chem. Soc. 81 (1959) 2364,
as follows. Nonanoyl chloride, 17.6g, was dissolved in
~iethi-~ ether (176 ml) and the solution was cooled to 0C.
60% aqueous hydrogen peroxide (4.25 ml) was added dropwise
followed by pypridine (9.5 g), also added dropwise, with
vigorous stirring and maintenance of the temperature
between 0 and 5C by means of an ice-bath. The ice-bath
was then removed and stirring was continued for 1 hour.
Diethyl ether was added to dilute the reaction mixture
which was then washed with dilute HC1, 5% KHCO3, and
finally water. After drying (Na2SO4), filtration and
rotary evaporation, a product, of melting point 13C, was
islolated, which product analysed as 86.5% diacyl
peroxide.
SUBSTITUTE SHEET
W093/07086 PCT/US92/08~1
2i2049~6
The urea clathrate of dinonanoyl peroxide was prepared as
follows. Dinonanoyl peroxide (10 g) was dissolved in the
minimum volume of warm (40CO methanol. Urea (50 g) was
dissolved in hot methanol (200 ml) and the solutions were
mixed and then cooled to yield an immediate precipitate of
clathrate. Filtration and drying produced a product (31
g) analysed as containing 29% diacyl peroxide.
Exam~le 2
Dioctanoyl peroxide, obtained as the commercial product
Perkadox SE8 from Akzo, was reacted with urea in the
manner described above in Example 1 to yield an urea
clathrate analyses as containing 27~5% diacyl peroxide.
Exam~le 3
Diacetyl azelaic diperoxide was prepared as follows.
Diperoxy azelaic acid (prepared by the method of Parker et
~, J. Amer. Chem. Soc., 79 (1957) 1929) in an amount of 50
g was dissolved in acetic acid (500 ml) in an open beaker
(magnetic stirrer) and cooled to below 20C P~he(~ ~)w~s
added dropwise over a period of 15 min, with extra cooling
to maintain the temperature below 20C. The white
suspension was thus converted to a clear solution;
reaction was continued for a further 30 min at room
temperature. The solution was poured onto ice-water (20
1) with vigorous stirring whereupon a white solid
separated, which was filtered, washed and dried, 51 g,
m.pt. 53C (literature value, 51-53C). Analysis
indicated freedom from peracid and a tetraacyl peroxide
content of 92%.
To form the clathrate, diacetyl azelaic diperoxide (40 g)
was dissolved in the minimum volume of warm ~40) methanol
and was mixed with a hot solution of urea ~120 g) in
methanol tl litre). On cooling, a heavy white precipitate
of clathrate formed, which was filtered and dried, 130 g.
Analysis indicated a tetraacyl peroxide activity of 27.8%.
Exam~le 4
Laundry detergent compositions according to this invention
may be prepared by adding the urea clat~rate of dinonanoyl
SUBSTITUTE SHEET
W(, /07086 2 1 2 0 4 9 1 PCr/USg2~08301
- 47 -
peroxide, the urea elathrate of dioctanoyl peroxide or the
urea elathrate of diacetyl azelaie diperoxide to either of
t~e following base formulations (the amounts being in
parts by weight).
Table 1
Com~onent ~ ~
LAS 7.5 7.8
TAS 2.5 2.4
45E7 4.0 4.0
TAEll 1.35 - -
Silicate 3.0 2.7
MA/AA 2.0 1.0
Polyacylate - 5.6
DETPMP o.3 O.6
CNC 0.48 0.48
Zeolite 23.6 23.0
Silicone Prill 2.75 2.75
The components are as follows :
LAS = sodium linear C12-alkyl benezene sulfonate.
TAS = sodium tallow alcohol sulfonate.
45E7 = synthetic C14jCls alcohol ethoxylated with
7 moles of ethylene oxide per mole of
alcohol.
TAEll = tallow aleohol ethoxylated with 11 moles
of ethylene oxide per mole of alcohol.
Silicate = sodium silicate having an SiO2:Na20
ratio of 1.6.
MA/AA = eopolymer of 1:4 maleic and aerylic aeids
average molecular weight of about 80,000.
Polyacrylate = homopolymer of aerylic acid, molecular
weight of 4~00.
DETPMP = diethylene triamine penta(methylene
phosphonie acid) marketed by Monsanto
under the trade name "Dequest 2060".
CMC = sodium earboxymethylcellulose.
Zeolite = hydrated sodium aluminosilicate of
formula Nal2(Al02-sio2)l2 27H2o and
SUBSTITUTE SHEET
W O 93/07086 '~ 1 2 0 ~ 9 1 PC~r/US92/08301 `
- 48 -
having a primary particle size of l-lOum.
Silicone - 0.14 parts by weight of an 85;15 mixture (by
Prill weight) silanated silica and silicone,
granulated with 1.3 parts of sodium
tripolyphosphate, and 0.56 parts of tallow
alcohol condensed wit~ 80 molar proportions
of ethylene oxide.
The urea clathrates may be added in an amount, for
example, equivalent to 1% by weight acyl peroxide or 1.5S
by weight acyl peroxide, relative to the base formulation.
Sodium perbonate monohydrate may also be added to provide
a content thereof in the compositions of, for example, 16%
by weight.
Example 5
In order to test the effectiveness on carotenoid-type
stains, tw~ test laundry detergent compositions were
prepared by adding the urea clathrate of dinonanoyl
peroxide (the clathrate containing 30% active compound) in
amou~ts of 1 percent by weight and 1.5% percent by weight,
respectively, to a perbonate-containing (16% by weight
perbonate monohydrate) granular detergent composition,
hereinafter referred to as the "base" composition.
Stained fabrics were washed at 30C in a commercially
available domestic washin~ machine using the above
described formulations, and the stain removal was judged
by an expert panel in known manner, the results being
recorded in panel score units ~psu) on the Scheffé scale,
taking the results obtained using the base composition (no
added diacyl peroxide cl~thrate) as the standard. T~e
results are given in the following table :
Table 2
Stain Base Base + 1.5% Base + 1.0%
clathrate clathrate
~ : ; r
Carrot baby food 0.00 + 3.50 + 3.38
Spaghetti sauce 0.00 + 2.88 + 2.44
SUBSTITUTE SHEET
W~ /07086 21 2 0 ~1 91 PCT/US97/08~1
- 4g -
Tomato purée o.Oo + 2.50 + 2.25
Carrot/tomato, 0.00 + l.13 + l.94
dried
The above results show that the addition of the
dinonanoyl peroxide/urea clathrate, at either of the
stated levels of addition, gave rise to a significant
improvement in respect of the cleaning of the above-
identified stains.
Ex~Ple 6
The effectiveness of dioctanoyl peroxide (DOP) and of
diacetyl azelaic diperoxide (DAAP), in both cases in the
form of the urea clathrate, was tested against certain
hydrophilic (specifically, tea/wine), hydrophobic
~specifically, paprika) and carotenoid (specifically,
tomato) stains. For comparison purposes, tests against
the stains were also carried out using
isononanoyloxybenzene sulfonate (i-NOBS),
tetraacetylethylenediamine tTAED) and the compound of the
formula CgHlg - NHCO-(CH2)-CO-OOH (NAPAA).
The test compositions were prepared by adding the DOP,
DAAP, i-NOBS, TAED and NAPAA to respective samples f a
base formulation similar to that disclosed in Example 4B
above, at a level of 5% by weight relative to said base
formulation. Sodium perbonate was also included in
certain of the test compositions.
The tests were carried out under standard conditions ~SPIT
Launderometer, 18H water, 40C and equal weight
bleaches). For the hydrophilic stains, bleaching
effectiveness was evaluated in terms of the reflectance
parameter L in the Hunter "L, a, b" tristimulus system
using a Hunterlab Colormeter: the differences ~L with
respect to the standard are a sufficient indication of
"whiteness" differences. For the other stains, panel
judging was employed, as described in Example 5. The
results, relative to i-NoBs taken as the standard, are
given in the Table which follows :
SUBSTITUTE SHEET
W093/07086 PCT/US92/08301
21~1lg l 50
Table 3
HvdroDhilic~aL~ Hvdrophobic l~suL Carotenoid (psu
i-NoBS O O O
TAED + 2.9 - 2.5 - 4.0
NAPAA - 2.0 + 0.8 - 1.5
DOP + 2.6 + 1.3 (+0.8) + 3.0 (+4.0)
DAAP + 3.0 - 2.5 (-0.4) - 4.0 (-0.9)
. .
The results shown in parenthesis were obtained in the -
absence of perbonate; all other tests were carried out
using the same level of perbonate. The results show that
dioctanoyl peroxide/urea clathrate gave excellent results
against the hydrophobic and, especially the carotenoid `
stains whilst its effectiveness against the hydrophilic
stain was comparable to that obtained using the known
activator TAED.
The results of DAAP in the presence of perbonate are
comparable to those for TAED, which is currently regarded
as a potent ingredient of conventional detergent
compositions. In the absence of perbonate, however, DAAP
gave a score 3.l psu higher than that given by TAED on
carotenoids, which represents a significant improvement in
performance.
It will of course be understood that the present invention
has been described above purely by way of example and that
modifications of detail can be made within the scope of
the invention.
SUBSTITUTE SHEET
