Note: Descriptions are shown in the official language in which they were submitted.
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PROCESS FOR DELIVERING CHELANT AGGLOMERATE INTO DETERGENT
COMPOSITION FOR IMPROVING ITS STORAGE STABILITY;
FLOWABILITY AND SCOOPABILITY
TECHNICAL FIELD
The present invention relates to a laundry detergent compositions and more
particularly,
to a process for improving storage stability and scoopability of laundry
detergent compositions by
incorporation of useful levels of a concentrated chelant agglomerate into a
laundry detergent
composition.
BACKGROUND OF THE INVENTION
It has been extremely desirable to have a process for increasing the storage
stability and
scoopability of detergent compositions. This is a characteristic that most
consumers are very
desirous of because consumers do not want to have to deal with detergent
compositions that
"clump" together after the detergent box has been laid open for an extended
period of time due to
the inadvertent absorption of moisture.
It has beer. recognized that the incorporation of a transition metal chelant
into the base
granules of the laundry detergent composition causes the promotion of
interlocking crystalline
needle growth which is suspected to detrimentally affect the resultant
particulate laundry
detergent composition's flowability and scoopability properties. Thus it has
been recognized by
the inventors of this particular invention that it is extremely advantageous
to devise a method of
separating the transition metal chelant from the base granule of the laundry
detergent
composition, so that any useful level of the transition metal chelant may be
incorporated in the
overall laundry detergent composition without adversely affecting its
flowability and scoopability
properties. It has thus been extremely desirable to have a process or a method
whereby any
useful level of a chelant agglomerate can be ad-mixed into a laundry detergent
composition such
that the chelant agglomerate desirably improves the solubility and storage
stability of the
resultant ad-mixed detergent composition formulation and at the very least,
does not
detrimentally affect the laundry detergent composition's flowability and
scoopability
characteristics. The present invention overcomes the problems, as set forth
above.
BACKGROUND ART
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U.S. Patent 5,108,646 discloses a process for making detergent builder
agglomerates by mixing
a detergent builder with a selected binder to form free flowing agglomerates.
International Publication Number WO 97/09415 discloses a non-spray-dried
particulate
detergent composition prepared by mixing and granulating liquid and solid
ingredients in a
high-speed mixer/granulator, containing a builder polymer and/or a soil-
release polymer,
wherein the polymer is incorporated during the mixing and granulating process
in the form of a
non-aqueous premix with a non-aqueous diluent.
SUMMARY OF THE INVENTION
The invention meets the needs above by providing a process for preparation of
a
chelant composition by a non-spray-drying process, a process for improving one
or more of
storage stability, flowability and scoopability of a laundry detergent
composition, and a chelant
agglomerate useful as an ad-mix in a particulate laundry detergent.
In one aspect of the present invention, a process for preparation of a chelant
composition by a non-spray-drying process includes the steps of admixing a
transition metal
chelant and an inorganic compound to form a mixture, agglomerating the mixture
in an aqueous
medium to form a chelant agglomerate and drying the chelant agglomerate.
In another aspect of the invention there is provided a process for preparation
of a
chelant composition by a non-spray-drying process, comprising the steps of:
a)admixing a
transition metal chelant and an inorganic compound to form a mixture; b)
agglomerating said
mixture in an aqueous medium to form a chelant agglomerate; and c) drying said
chelant
agglomerate wherein the inorganic compound is selected from the group
consisting of sulfates,
carbonates, silicates, aluminosilicates and mixtures thereof; and wherein the
transition metal
chelant is selected from the group consisting of
diethylenetriaminepentaacetates;
ethylenediamine disuccinate; and mixtures thereof; and wherein the chelant
agglomerate
resulting from step c) consists of said transition metal chelant and said
inorganic compound.
In a further aspect of the present invention, a process for improving one or
more of
storage stability, flowability and scoopability of a laundry detergent
composition includes the
steps of providing a chelant composition prepared by a non-spray-drying
process and
incorporating the chelant composition into a particulate laundry detergent
material in a weight
ratio in a range of from about 0.05:99.95 to about 2:98, chelant composition
to particulate
laundry detergent material. The non-spray-drying process includes the steps of
admixing a
transition metal chelant and an inorganic compound to form a mixture,
agglomerating the
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2a
mixture in an aqueous medium to form a chelant agglomerate, and drying the
chelant
agglomerate.
In yet another aspect of the present invention, a chelant agglomerate useful
as an ad-
mix in a particulate laundry detergent is disclosed. The chelant agglomerate
has a composition
including a transition metal chelant, an inorganic compound and water. The
chelant
agglomerate is formed by admixing the transition metal chelant and the
inorganic compound to
form a mixture, agglomerating the mixture in the water to form the chelant
agglomerate, and
drying the chelant agglomerate.
These and other objects, features and attendant advantages of the present
invention will
become apparent to those skilled in the art from a reading of the following
detailed description
of the preferred embodiment and the appended claims.
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DETAILED DESCRIPTION OF THE INVENTION
In the preferred embodiment of the present invention, the process for
preparation of a
chelant composition by a non-spray-drying process includes the steps of
admixing a transition
S metal chelant and an inorganic compound to form a mixture, agglomerating the
mixture in an
aqueous medium to form a chelant agglomerate, and drying the chelant
agglomerate. in the
preferred embodiment, the transition metal chelant is sodium
ditriaminepentaacetate and the
inorganic compound is selected from the group consisting of sulfates,
carbonates, silicates,
aluminosilicates and mixtures thereof. Desirably, the inorganic compound is an
aluminosilicate
material and preferably, the inorganic compound is an aluminosilicate ion
exchange material of
the formula. Mm/n[(A10~)m(Si02)y]~xH,p where n is the valence of the cation M,
x is the
number of water molecules per unit cell, m and y are the total number of
tetrahedra per unit cell,
and y/m is 1 to 100, and wherein M is selected from the group consisting of
sodium, potassium,
magnesium, and calcium. Most preferably, the inorganic compound is zeolite.
In the preferred embodiment, the step of admixing includes mixing and
granulating the
transition metal chelant and the inorganic compound in one or more of a high-
speed mixer and
granulator, desirably in a weight ratio in a range of from about 10:90 to
about 80:20 respectively,
preferably in a weight ratio in a range of from about 15:85 to about 60:40
respectively and most
preferably in a weight ratio in a range of from about 25:75 to about 35:65
respectively
2p In the preferred embodiment, the step of agglomerating includes forming a
chelant-
inorganic compound pre-mix with water before agglomerating, desirably in a
weight ratio in a
range of from about 10:90 to about 80:20 respectively, preferably in a weight
ratio in a range of
from about 15:85 to about 60:40 respectively and most preferably in a weight
ratio in a range of
from about 25:75 to about 35:65 respectively
In another preferred embodiment of the present invention, a process for
improving
storage stability and scoopability of a laundry detergent composition is
disclosed. In this
preferred embodiment of the present invention, the process includes the first
step of forming a
chelant agglomerate. It has very surprisingly been found that when the chelant
particles are
separated from the rest of the laundry detergent composition and chelant
agglomerates are formed
and then the chelant agglomerates are incorporated into a particulate laundry
detergent
composition, there is a dramatic increase in the resultant laundry detergent
composition's storage
stability and scoopability when the chelant agglomerate is eventually ad-mixed
with the detergent
powder in a desired weight ratio in a range of from about 0.05:99.95 to about
2:98, a preferred
weight ratio in a range of from about 0.3:99.7 to about 1.5:98.5, and a most
preferred weight ratio
CA 02345737 2004-06-21
in a range of from about 0.1:99.9 chelant agglomerate:laundry detergent
composition. Thus it has
been surprisingly found that by expressly separating the chelant particles
from the laundry
detergent composition and only incorporating a chelant agglomerate into a
laundry detergent
composition, the finish product, i.e., the laundry detergent composition , has
much improved
"lump cake" properties, i.e., that the detergent composition having a chelant,
has improved
storage stability and scoopabiliry. Without being bound to any speciftc
theory, it is believed that
this improvement is achieved as a result of having separated the hygroscopic
transition metal
chelant from the rest of the "sticky" laundry composition.
For the purposes herein, the tern "lump cake" property is meant to include
composition
storage stability and powder sotubiiiry in water. The term "sticky" components
is meant to
include a mixture of one or more of surfactants, polyethylene glycol,
polyacrylates and water.
The term "builder" is intended to mean all materials which tend to remove
calcium ion from
solution, either by ion exchange, complexation, sequestration or
precipitation. The term
"scoopability" is defined on a scale of 1 to 5, I being the least desirable
value and 5 being the
most desirable value, of the ability or characteristic of a laundry
composition to be scooped up in
a spoon without exhibiting tackiness or clumpiness.
Cheiants
The chelaUng agents can be selected from the group consisting of amino
carboxylates, amino
phosphonates, polyfunctionally-substituted aromatic chelating agents, sodium
ditriaminepentaacetate and mixtures thereof Without intending to be bound by
theory, it is
believed that the benefit of these materials is due in pan to their
exceptional ability to remove
iron and manganese ions from washing solutions by formation of soluble
chelates.
Amino carboxylates useful as optional chelating agents include
ethylenediaminetetracetates. N-hydroxyethylethylenediaminetriacetates, nitrilo-
triacetates,
ethylenediamine tetraproprionates, triethylenetetraaminehexacetates,
diethylenetriaminepentaacetates, and ethanoldiglycines, alkali metal,
ammonium, and
substituted ammonium salts therein and mixtures therein.
Amino phosphonates are also suitable for use as chelating agents in the
compositions of
the invention when at lease low levels of total phosphorus are permitted in
detergent
TM
compositions, and include ethylenediaminetetrakis (methylenephosphonates) as
DEQUEST.
Preferred, these amino phosphonates to not contain alkyl or alkenyl groups
with more than
about 6 carbon atoms.
Polyfunetionally-substituted aromatic chelating agents are also useful in the
compositions
herein. See U.S. Patent 3.8 i 2,044, issued May 21, 1974, to Connor et al.
Preferred compounds
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~$-
of this type in acid fotirt are dihydroxydisulfobenzenes such as 1,2-dihydroxy-
3,5-
disulfobenzene.
A preferred biodegradable chelator for use herein is ethylenediamine
disuccinate
("EDDS"), especially the [S,S] isomer as described in U.S. Patent 4,704,233,
November 3,
1987, to Hartman and Perkins.
If utilized, these chelating agents will generally comprise from about 0.05%
to about 10°i°
by weight of the detergent compositions herein. More preferably, if utilized,
the chelating agents
will compnse from about O.OS% to about 3.0°~o by weight of such
compositions.
The most preferred transition metal chelant used to carry out the present
invention is
sodium ditriaminepentaacetate (DTPA). The DTPA is preferably used in a weight
ratio of from
about 0.1:99.9 to about 1.5:98.5. DTPA agglomerate:laundry detergent
composition and most
preferably. in a weight ratio of 0.4:99.6. Preferably the chelant agglomerate
consists of DTPA
and zeolite in a preferred weight ratio ir, a range of from about 15:85 to
about 25:75,
DTPA:zeoiite.
1 s Aluminosilicate material
in the preferred embodiment of the present invention, the structural formula
of an
aluminosiltcate material is based on the crystal unit cell, the smallest unit
of structure
represented by:
Mm/n[(A10,)m(S~O:)y]~xH~O
?0 where n is the valence of the canon M, x is the number of water molecules
per unit cell, m and y
are the total number of tetrahedra per unit cell, and y/m is 1 to 100. Most
preferably, y/m is 1 to
5. The canon M can be Group lA and Group lIA elements, such as sodium,
potassium,
magnesium. and calcium. The preferred aluminosilicate materials are zeolites_
The most
preferred zeolites are zeolite A, zeolite X, zeolite Y, zeolite P, zeolite MAP
and mixtures thereof.
25 The aluminosilicate ion exchange materials used herein for chelant
agglomerates have both a
high calcium ion exchange capacity and a high exchange rate. Without intending
to be limited by
theory, it is believed that such high calcium ion exchange rate and capacity
are a function of several
interrelated factors which derive from the method by which the aluminosilicate
ion exchange
material is produced. In that regard, the aluminosilicate ion exchange
materials used herein are
30 preferably produced in accordance with Corkill et al, U.S. Patent No.
4,605,509 (Procter & Gamble).
Preferably, the aluminosilicate ion exchange material is in "sodium" form
since the
potassium and hydrogen forms of the instant aluminosilicate do not exhibit the
as high of an
exchange rate and capacity as provided by the sodium form. Additionally, the
aluminosilicate ion
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exchange material preferably is in over dried form so as to facilitate
production of crisp chelant
agglomerates as described herein. The aluminosilicate ion exchange materials
used herein
preferably have particle size diameters which optimize their effectiveness as
detergent builders.
The term "particle size diameter" as used herein represents the average
particle size diameter of a
given aluminosilicate ion exchange material as determined by conventional
analytical techniques,
such as microscopic determination and scanning electron microscope (SEM). The
preferred
particle size diameter of the aluminosilicate is from about 0.1 micron to
about 10 microns, more
preferably from about 0.5 microns to about 9 microns. Most preferably, the
particle size diameter
is from about 1 microns to about 8 microns.
l0 In a preferred embodiment, the crystalline aluminosilicate ion exchange
material has the
formula:
Nal2[(A102)12(Si02)12~'xH20
wherein x is from about 20 to about 30, especially about 27. This material is
known as Zeolite
A. Dehydrated zeolites (x = 0 - 10) may also be used herein. Preferably, the
aluminosilicate
1 ~ has a particle size of about 0.1-10 microns in diameter.
Laundry detergent comnosit~on
In the preferred embodiment, the laundry detergent composition has a
composition
including a chelant agglomerate made according to the present invention and
incorporated into
the laundry detergent composition. The laundry detergent composition also
comprises a builder
'0 made by agglomeration or spray dried process, sodium carbonate, sodium
sulfate, sodium
tripolyphosphate, anionic and nonionic surfactants and balance water. Laundry
detergent
compositions are well known in the art and various examples of various laundry
detergent
compositions are disclosed, for example in U.S. Patent No. 5,554,587, issued
to Scott W. Capeci,
and assigned to The Procter & Gamble Company.
25 Chelant aeQlomerates made by aa~lomeration process
In the preferred embodiment of she present invention, the chelant agglomerates
are made
by an agglomeration process.
T_he aaalomeration process
The agglomeration process comprises the steps of:
30 i) admixing one or more ingredients to form a mixture; and
ii) agglomerating the mixture to form agglomerated particles or
"agglomerates", and
iii) drying the agglomerate.
Typically, such an agglomeration process involves mixing the ingredients in
one or more
agglomerators such as a pan agglomerator, a Z-blade mixer or more preferably
in-line mixers,
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_7_
preferably two, such as those manufactured by Schugi (Holland) BV, 29
Chroomstraat 8211 AS,
Lelystad, Netherlands, and Gebruder Lodige Maschinenbau GmbH, D-4790 Paderborn
I,
Elsenerstrasse 7-9, Postfach 2050, Germany. Preferably a high shear mixer is
used, such as a
Lodige CB (Trade Mark). Most preferably, a high shear mixer is used in
combination with a low
shear mixer, such as a Lodige CB (Trade Mark) and a Lodige KM (Trade Mark) or
Schugi KM
(Trade Mark). Optionally, only one or more low shear mixer are used.
Preferably, the
agglomerates are thereafter dried and/ or cooled. An excellent description of
an agglomeration
process is contained in U.S. Patent No. 5,554,587. issued to Scott W. Capeci,
and assigned to The
Procter ZC Gamble Company.
Another agglomeration process involves mixing of various components of the
ftnal
agglomorate in different stages, using an fluidized bed. For example, a
detergent powder can be
agglomerated by spraying on of surfactants and optionally a wax, or mixtures
thereof. to the acid
source in powdered form and other optional ingredients. Then, additional
components, including
the perborate bleach and optionally the alkali source or part thereof, can be
added and
1 ~ agglomerated in one or more stages, thus forming the final agglomerate
particle.
The agglomerates may take the form of flakes, prills, marumes, noodles.
ribbons, but
preferably take the form of granules. A preferred way to process the particles
is by
agelomerating dry material (e_g. aluminosilicate, carbonate) with high active
surfactant pastes
and to control the panicle size of the resulting agglomerates within specified
limits. Typical
?0 particle sizes are from 0.10 mm to 5.0 mm in diameter, preferably from 0.25
mm to 3.0 mm in
diameter, most preferably from 0.40 mm to 1.00 mm in diameter. Typically, the
"agglomerates"
have a bulk density desirably .of at least 700 g/1 and preferably, in a range
of from about 700 g/1
to about 900 g11.
AdLunct Detergent Ingredients
?5 The adjunct ingredients include other detergency builders, bleaches, bleach
activators, suds
boosters or suds suppressers, anti-tarnish and anticorrosion agents, soil
suspending agents, soil
release agents, germicides, pH adjusting agents, non-builder alkalinity
sources, chelating agents,
smecnte clays, enzymes, enzyme-stabilizing agents and perfumes. See U.S.
Patent 3,936,537, issued
February 3, 1976 to Baskerville,1r. et al.
30 Bleaching agents and activators are described in U.S. Patent 4,412,934,
Chung et al.,
issued November 1, 1983, and in U.S. Patent 4,483,781, Hartman, issued
November 20, 1984,
Chelating agents are also described in U.S.
Patent 4,663,071, Bush et al., from Column 17, tine 54 through Column 18, line
68.
Suds modifiers are also optional ingredients and are described in U.S.
CA 02345737 2004-06-21
_$_
Patents 3,933,672, issued 3anuary 20, 1976 to Bartoletta et al., and
4,136,045, issued January 23.
1979 to Gault et al.
Suitable smectite clays for use herein are described in U.S. Patent 4,762,645,
Tucker et al,
issued August 9, 1988, Column 6, line 3 through Column 7, line 24.
Suitable additional detergency builders for use herein are enumerated in the
Baskerville
patent, Column 13, line 54 through Column 16, line 16, and in U.S. Patent
4.663,071, Bush et al,
issued May 5, 1987.
Surfactants
:Anionic Surfactant - The preferred anionic surfactants include C 11-C1 g
alkyl benzene
sulfonates (LAS) and primary, branched-chain and random C10-C20 alkyl sulfates
(AS), the
CIO-Clg secondary (2.3) alky.~l sulfates of the formula CH3(CH2)x(CHOS03 M+)
CH3 and
CH3 (CH2)y(CHOS03 M+) CH2CH3 where x and (y + 1 ) are integers of at least
about 7,
preferably at least about 9, and M is a water-soiubilizing canon, especially
sodium, unsaturated
sulfates such as oleyl sulfate, the C 10-C 1 g alkyl alkoxy sulfates ("AEXS";
especially EO 1-7
1 ~ ethoxy sulfates), C 10-C 1 g allyl alkoxv carboxylates (especially the EO
I-S
ethoxycarboxylates). the C l 0-1 g glycerol ethers, the C 10-C 18 alkyl
polyglycosides and their
corresponding sulfated polyglycosides, and CI~-C18 alpha-sulfonated fatty acid
esters.
Generally speaking, anionic surfactants useful herein are disclosed in U.S.
Patent No.
4.285,841, Barrat et al, issued August 25, 1981, and in U.S. Patent No.
3,919,678, Laughlin et
~0 al. issued December 30, 1975.
Useful anionic surfactants include the water-soluble salts, particularly the
alkali metal,
ammonium and alkylolammonium (e.g., monoethanolammonium or triethanolammonium)
salts,
of organic sulfuric reaction products having in their molecular structure an
alkyl group
containing from about 10 to about 20 carbon atoms and a sulfonic acid or
sulfuric acid ester
?5 group. (Included in the term "alkyl" is the alkyl portion of aryl groups.)
Examples of this group
of synthetic surfactants are the alkyl sulfates, especially those obtained by
sulfating the higher
alcohols (Cg-C 1 g carbon atoms) such as those produced by reducing the
glycerides of tallow or
coconut oil.
Other anionic surfactants herein are the water-soluble salts of alkyl phenol
ethylene oxide
30 ether sulfates containing from about I to about 4 units of ethylene oxide
per molecule and from
about 8 to about 12 carbon atoms in the alkyl group.
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Other useful anionic surfactants herein include the water-soluble salts of
esters of a-
sulfonated fatty acids containing from about 6 to 20 carbon atoms in the fatty
acid group and
from about 1 to 10 carbon atoms in the ester group; water-soluble salts of 2-
acyloxy-alkane-1-
sulfonic acids containing from about 2 to 9 carbon atoms in the acyl group and
from about 9 to
about 23 carbon atoms in the alkane moiety; water-soluble salts of olefin
sulfonates containing
from about 12 to 24 carbon atoms; and b-alkyloxy alkane sulfonates containing
from about 1 to
3 carbon atoms in the alkyl group and from about 8 to 20 carbon atoms in the
alkane moiet)-.
Other useful anionic surfactants herein are the alkyl polyethoxylate sulfates
of the
formula
RO(C~H40)xS03-M+
wherein R is an alkyl chain having from about 10 to about 22 carbon atoms,
saturated or
unsaturated. M is a canon which makes the compound water-soluble, especially
an alkali metal,
ammonium or substituted ammonium canon, and x averages from about 1 to about
15.
Other alkyl sulfate surfactants are the non-ethoxylated C12-15 Pnmary and
secondary.
allyl sulfates. Under cold water washing conditions, i.e., less than abut
65°F (18.3°C), it is
preferred that there be a mixture of such ethoxylated and non-ethoxylated
alkyl sulfates.
Examples of fatty acids include capric, lauric, myristic, palmitic, stearic,
arachidic, and behenic
acid. Other fatty acids include palmitoleic, oleic, linoleic, linolenic, and
ricinoleic acid.
Nonionic Surfactant - Conventional nonionic and amphoteric surfactants include
C 12-C 1 g alkyl
ethoxylates (AE) including the so-called narrow peaked alkyl ethoxylates and
C6-C 12 alkyl
phenol alkoxylates (especially ethoxylates and mixed ethoxy/propoxy). The C 10-
C 1 g N-alkyl
potyhydroxy fatty acid amides can also be used. Typical examples include the C
12-C 1 g N-
methylglucamides. See WO 92/06154. Other sugar-derived surfactants include the
N-alkoxy
polyhydroxy fatty acid amides, such as C 10-C 1 g N-(3-methoxypropyl)
glucamide. The N-
propyl through N-hexyl C 12-C 18 glucamides can be used for low sudsing. C 10-
C20
conventional soaps may also be used. If high sudsing is desired, the branched-
chain C10-C16
soaps may be used. Examples of nonionic surfactants are described in U.S.
Patent No.
4,285.841, Barrat et al, issued August 25, 1981.
Examples of surfactants also include ethoxylated alcohols and ethoxylated
alkyl phenols
of the formula R(OC2H4)nOH, wherein R is selected from the group consisting of
aliphatic
hydrocarbon radicals containing from about 8 to about I S carbon atoms and
alkyl phenyl
radicals in which the alkyl groups contain from about 8 to about 12 carbon
atoms, and the
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average value of n is from about 5 to about 15. These surfactants are more
fully described in
U.S. Patent No. 4,284,532, Leikhim et al, issued August 18, 1981. Other
surfactants include
ethoxylated alcohols having an average of from about 10 to abut 15 carbon
atoms in the alcohol
and an average degree of ethoxylation of from about 6 to about 12 moles of
ethylene oxide per
mole of alcohol. Mixtures of anionic and nonionic surfactants are especially
useful.
Other conventional useful surfactants are listed in standard texts, including
polyhydroxy fatty acid amides, alkyl glucosides, polyalkyl glucosides, C12-Clg
betaines and _
sulfobetaines (sultaines). Examples include the C12-Clg N-methylglucamides.
See WO
9,206,154. Other sugar-derived surfactants include the N-alkoxy polyhydroxy
fatty acid
amides, such as C 10-C I g N-(3-methoxypropyl) glucamide. The N-propyl through
N-hexyl
C 12-C I g glucamides can be used for low sudsing.
Cationic Surfactants
One class of useful cationic surfactants are the mono alkyl quaternary
ammonium surfactants
although any cationic surfactant useful in detergent compositions are suitable
for use herein.
The cationic surfactants which can be used herein include quaternary ammonium
surfactants of the formula:
R4\ / R~
/ \
R3 R2
wherein R 1 and R2 are individually selected from the group consisting of C 1-
C4 alkyl, C 1-C4
hydroxy alkyl, benryl, and -(C2H40)xH where x has a value from about 2 to
about S; X is an
anion; and ( 1 ) R3 and R4 are each a C6-C 14 alkyl or (2) R3 is a C6-C 1 g
alkyl, and R4 is
selected from the group consisting of C I-C l0 alkyl, C I -C 10 hydroxyalkyl,
benryl, and -
(C2H40)xH where x has a value from 2 to 5.
Other useful quaternary ammonium surfactants are the chloride, bromide, and
methylsulfate salts. Examples of desirable mono-long chain alkyl quaternary
ammonium
surfactants are those wherein R I , R2, and R4 are each methyl and R3 is a Cg-
C 16 alkyl; or
wherein R3 is Cg-1 g alkyl and R1, R2, and R4 are selected from methyl and
hydroxyalkyl
moieties. Lauryl trimethyl ammonium chloride, myristyl trimethyl ammonium
chloride,
palmityl trimethyl ammonium chloride, coconut trimethylammonium chloride,
coconut
trimethylammonium methylsulfate, coconut dimethyl-monohydroxy-ethylammonium
chloride,
coconut dimethyl-monohydroxyethylammonium methylsulfate, steryl dimethyl-
monohydroxy-
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ethylammonium chloride, steryl dimethyl-monohydroxyethylammonium
methylsulfate, di- C12-
C 14 alkyl dimethyl ammonium chloride, and mixtures thereof are also
desirable. ADOGEN
412T"", a lauryl trimethyl ammonium chloride commercially available from
Witco, is also
desirable. Other desirable surfactants are lauryl trimethyl ammonium chloride
and myristyl
trimethyl ammonium chloride.
Another group of suitable cationic surfactants are the alkanol amidal
quaternary
surfactants of the formula:
O
R 1-Ci-N-( CH2 ) n-Y-( CH2 ) n-X
R2
wherein RI can be C10-18 alkyl or a substituted or unsubstituted phenyl; R2
can be a C1~
alkyl, H, or (EO)y, wherein y is from about 1 to about 5; Y is O or -
N(R3)(R4); R3 can be H,
C 1 ~ alkyl, or (EO)y, wherein y is from about 1 to about S; R4, if present,
can be C 1 ~ alkyl or
(EO)y, wherein y is from about 1 to about S; each n is independently selected
from about 1 to
about 6, preferably from about 2 to about 4; X is hydroxyl or
-N(RS)(R6)(R~), wherein R5, R6, R~ are independently selected from C1~ alkyl,
H, or (EO)y,
1 > wherein y is from about 1 to about 5.
Amine Oxide Surfactants - The laundry detergent compositions herein also
contain amine oxide
surfactants of the formula:
R1(EO)x(PO)y(BO)zN(O)(CH2R')2.qH2O (I)
In general, it can be seen that the structure (I) provides one long-chain
moiety
Rl(EO)x(PO)y(BO)z and two short chain moieties, CH2R'. R' is preferably
selected from
hydrogen, methyl and -CH20H. In general R1 is a primary or branched
hydrocarbyl moiety
which can be saturated or unsaturated, preferably, Rl is a primary alkyl
moiety. When x+y+z =
0, RI is a hydrocarbyl moiety having chainlength of from about 8 to about 18.
When x+y+z is
different from 0. Rl may be somewhat longer, having a chainlength in the range
C12-C24~ The
general formula also encompasses amine oxides wherein x+y+z = 0, R1 = Cg-C 1
g, R' is H and q
is 0-2, preferably 2. These amine oxides are illustrated by C12-l4
alkyldimethyl amine oxide,
hexadecyl dimethylamine oxide, octadecylamine oxide and their hydrates,
especially the
CA 02345737 2004-06-21
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dehydrates as disclosed in U.S. Patents 5,075,501 and 5,071,594.
The invention also encompasses amine oxides wherein x+y+z is different from
zero,
specifically x+y+z is from about 1 to about 10, R1 is a primary alkyl group
containing 8 to
about 24 carbons, preferably from about 12 to about 16 carbon atoms; in these
embodiments y +
z is preferably 0 and x is preferably from about 1 to about 6, more preferably
from about 2 to
about 4; EO represents ethyleneoxy; PO represents propyleneoxy; and BO
represents
buryleneoxy. Such amine oxides can be prepared by conventional synthetic
methods, e.g., by
the reaction of alkylethoxysulfates with dimethylamine followed by oxidation
of the
ethoxylated amine with hydrogen peroxide.
Desirable amore oxides herein are solids at ambient temperature, more
preferably they
have melting-points in the range 30°C to 90°C. Amine oxides
suitable for use herein are made
commercially by a number of suppliers, including Akzo Chemie, Ethyl Corp., and
Procter &
Gamble. See McCutcheon's compilation and Kirk-Othmer review article for
alternate amine
oxide manufacturers. Other desirable commercially available amine oxides are
the solid,
TM
dehydrate ADMOX 16 and ADMOX 18, ADMOX 12 and especially ADMOX 14 from Ethyl
Corp.
Other embodiments include dodecyldimethylamine oxide dehydrate,
hexadecyldimethylamine oxide dehydrate. octadecyldimethylamine oxide
dehydrate,
hexadecyltris(ethyleneoxy)dimethyl-amine oxide, tetradecyldimethylamine oxide
dehydrate, and
mixtures thereof. Whereas in certain embodiments R' is H, there is some
latitude with respect
to having R' slightly larger than H. Alternate embodiments include wherein R'
is CH20H. such
as hexadecylbis(2- hydroxyethyl)amine oxide, tallowbis(2-hydroxyethyl)amine
oxide,
stearylbis(2-hydroxyethyl)amine oxide and oleylbis(2- hydroxyethyl)amine
oxide.
Enzymes
Enzymes can be included in the formulations herein for a wide variety of
fabric
laundering purposes, including removal of protein-based, carbohydrate-based,
or trigiyceride-
based stains, for example, and for fabric restoration. The enzymes to be
incorporated include
proteases, amylases, lipases, and cellulases, as well as mixtures thereof.
Other types of
enzymes may also be included. 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-activity and/or stability optima, thermostabiliry, stability versus active
detergents, builders
and so on. In this respect bacterial or fungal enzymes are preferred, such as
bacterial amylases
and proteases, and fungal cellulases.
CA 02345737 2004-06-21
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Enzymes are normally incorporated at levels sufficient to provide up to about
5 mg by
weight, more typically about 0.01 mg to about 3 mg, of active enzyme per gram
of the
composition. Stated otherwise, the compositions herein will typically comprise
from about
0.001 % to about 5%, preferably 0.01 % to 1 % by weight of a commercial enzyme
preparation.
Protease enzymes are usually present in such commercial preparations at levels
sufficient to
provide from 0.005 to 0.1 Anson units (AU) of activity per gram of
composition.
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 trademark ESPERASE. 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 trade marks ALCALASE and SAVINASE by
Novo
Industries A/S (Denmark) and MAXATASE by International Bio-Synthetics, Inc.
(The
1 S Netherlands). Other proteases include Protease A (see European Patent
Application 130,756, .
published January 9, 1985) and Protease B (see European Patent Application
251446
published January 7, 1988, and European Patent Application 130,756, Bott et
al,
published January 9, 1985).
Amylases include, for example, a-amylases described in British Patent
Specification No.
TM TM
1,296.839 (Novo), RAP)DASE, International Bio-Synthetics, Inc. and TERMAMYL,
Novo
Industries.
The cellulase 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, which
discloses fungal
cellulase produced from Humicola insolens and Humicola strain DSMI800 or a
cellulase 212-
producing fungus belonging to the genus Aeromonas, and cellulase extracted
from the
hepatopancreas of a marine mollusk (Dolabella Auricuia Solander). Suitable
cellulases are also
TM
disclosed in GB-A-2.075.028; GB-A-2.095.275 and DE-OS-2.247.832, CAREZYME
(Novo) is
especially useful.
Suitable lipase enzymes for detergent usage include those produced by
microorganisms of
the Pseudomonas group, such as Pseudomonas stutzeri ATCC 19.154, as disclosed
in British
Patent 1,372,034. See also lipases in Japanese Patent Application 53,20487,
laid open to public
inspection on February 24, 1978. This lipase is available from Amano
Pharmaceutical Co. Ltd.,
Nagoya, Japan, under the trade mark Lipase P "Amano," hereinafter referred to
as "Amano-P."
CA 02345737 2004-06-21
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Other commercial lipases include Amano-CES, lipases ex Chromobacter viscosum,
e.g.
Chromobacter viscosum var. lipolyticum NRRLB 3673, commercially available from
Toyo
Jozo Co., Tagata, Japan; and further Chromobacter viscosum lipases from U.S.
Biochemical
Corp., U.S.A. and Diosynth Co., The Netherlands, and lipases ex Pseudomonas
gladioli. The
L)pOLASE enzyme derived from Humicola lanuginosa and commercially available
from Novo
(see also EPO 341,947) is a preferred lipase for use herein.
A wide range of enzyme materials and means for their incorporation into
synthetic
detergent compositions are also disclosed in U.S. Patent 3,553,139, issued
January 5, 1971 to
McCarty et al. Enzymes are further disclosed in U.S. Patent 4,101,457, Place
et al, issued July
1 fi, 1978, and in U.S. Patent 4,507,219, Hughes, issued March 26, 1985, both.
Enzyme
materials useful for liquid detergent formulations, and their incorporation
into such
formulations. are disclosed in U.S. Patent 4,261,868, Hora et al, issued April
14, 1981.
Enzymes for use in detergents can be stabilized by various techniques. Enzyme
stabilization
techniques are disclosed and exemplified in U.S. Patent 3,600,319, issued
August 17, 1971 to
I 5 Gedge. et al. and European Patent Application Publication No. 0 199 405,
published October 29, 1986, Venegas. Enzyme stabilization systems are also
described. for example, in U.S. Patent 3,519,570.
The enzymes employed herein may be stabilized by the presence of water-soluble
sources
of calcium and/or magnesium ions in the finished compositions which provide
such ions to the
enzymes. (Calcium ions are generally somewhat more effective than magnesium
ions and are
preferred herein if only one type of canon is being used.) Additional
stability can be provided
by the presence of various other art-disclosed stabilizers, especially borate
species. See
Severson, U.S. 4,537,706. Typical detergents, especially liquids, will
comprise from about 1 to
about 30, preferably from about 2 to about 20, more preferably from about S to
about 15, and
?S most preferably from about 8 to about 12, millimoles of calcium ion per
liter of finished
composition. This can vary somewhat, depending on the amount of enzyme present
and its
response to the calcium or magnesium ions. The level of calcium or magnesium
ions should be
selected so that there is always some minimum level available for the enzyme,
after allowing for
complexation with builders, fatty acids, etc., in the composition. Any water-
soluble calcium or
magnesium salt can be used as the source of calcium or magnesium ions,
including, but not
limited to, calcium chloride, calcium sulfate, calcium malate, calcium
maleate, calcium
hydroxide, calcium formate, and calcium acetate, and the corresponding
magnesium salts. A
small amount of calcium ion, generally from about 0.05 to about 0.4 millimoles
pcr liter, is
often also present in the composition due to calcium in the enzyme slurry and
formula water. In
CA 02345737 2004-06-21
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solid detergent compositions the formulation may include a sufficient quantity
of a water-
soluble calcium ion source to provide such amounts in the laundry liquor. In
the alternative,
natural water hardness may suffice_
It is to be understood that the foregoing levels of calcium and/or magnesium
ions are
sufficient to provide enzyme stability. More calcium and/or magnesium ions can
be added to
the compositions to provide an additional measure of grease removal
performance.
Accordingly, as a general proposition the compositions herein will typically
comprise from
about 0.0$% to about 2% by weight of a water-soluble source of calcium or
magnesium ions, or
both. The amount can vary. of course, with the amount and type of enzyme
employed in the
composition.
The laundry detergent compositions herein may also optionally, but preferably,
contain
various additional stabilizers, especially borate-type stabilizers. Typically,
such stabiEizers will
be used at levels in the compositions from about 0.25% to about 10%,
preferably from about
0.5% to about 5%, more preferably from about 0.75% to about 4%, by weight of
boric acid or
I $ other borate compound capable of forming boric acid in the composition
(calculated on the
basis of boric acid). Boric acid is preferred, although other compounds such
as boric oxide,
borax and other alkali metal borates (e.g., sodium ortho-, meta- and
pyroborate, and sodium
pentaborate) are suitable. Substituted boric acids (e.g., phenylboronic acid,
butane boronic
acid, and p-bromo phenylboronic acid) can also be used in place of boric acid.
Polymeric Soil Release Aeent
Any polymeric soil release agent known to those skilled in the art can
optionally be
employed in the compositions and processes of this invention. Polymeric soil
release agents are
characterized 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 adhcred thereto through completion of washing and rinsing
cycles and, thus,
serve as an anchor for the hydrophilic segments. This can enable stains
occurring subsequent to
treatment with the soil release agent to be more easily cleaned in later
washing procedures.
Examples of polymeric soil release agents useful herein include U.S. Patent
4,721,580,
issued January 26, 1988 to Gosselink; U.S. Patent 4,000,093, issued December
28, 1976 to
Nicol, et al.; European Patent Application 0 219 048, published April 22, 1987
by Kud, et al.;
U.S. Patent 4,702,8$7, issued October 27, 1987 to Gosselink; U.S. Patent
4,968,4$ l, issued
November 6, 1990 to J.J. Scheibel. Commercially available soil release agents
include the
TM
SOKALAN type of material, e.g., SOKALAN HP-22, available from BASF (West
Germany).
Also see U.S. Patent 3,9$9.230 to Hays, issued May ?$, 1976 and U.S. Patent
3,893,929 to
CA 02345737 2004-06-21
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Basadur issued July 8, I 975. Examples of this polymer include the
commercially available
TM TM
material ZELCON 5126 (from Dupont) and MILEASE T (from ICI). Other suitable
polymeric
soil release agents include the terephthalate polyesters of U.S. Patent
4,711,730, issued
December 8, 1987 to Gosselink et al, the anionic end-capped oligomeric esters
of U.S. Patent
4,721,580, issued 3anuary 26, 1988 to Gosselink, and the block polyester
oligomeric
compounds of U.S. Patent 4,702,857, issued October 27, I987 to Gosselink.
Preferred
polymeric soil release agents also include the soil release agents of U.S.
Patent 4,877,896,
issued October 31, 1989 to Maldonado et al.
If utilized, soil release agents will generally comprise from about 0.01% to
about 10.0%,
by weight, of the detergent compositions herein, typically from about 0_I% to
about 5%,
preferably from about 0.2% to about 3_0%.
Clay Soil Removal/Anti-redeposition Agents
The laundry detergent compositions of the present invention can also
optionally contair~
water-soluble ethoxylated amines having clay soil removal and antiredeposition
properties.
IS Liquid detergent compositions typically contain about 0.01% to about S%.
The most preferred soil release and anti-redeposition agent is ethoxylated
tetraethylenepentamine. Exemplary ethoxylated amines are further described in
U.S. Patent
4,597,898, VanderMeer, issued July 1, 1986. Another group of preferred clay
soil removai-
antiredeposition agents are the cationic compounds disclosed in European
Patent Application
1 I 1,965, Oh and Gosselink, published June 27, 1984. Other clay soil
removal/antiredeposition
agents which can be used include the ethoxylated amine polymers disclosed in
European Patent
Application 11 1.984, Gosselink, published June 27, 1984; the zwitterionic
polymers disclosed
in European Patent Application 112,592, Gosselink, published July 4, 1984; and
the amine
oxides disclosed in U.S. Patent 4,548,744, Connor, issued October 22, i98S.
Other clay soil
removal and/or anti redeposition agents known in the art can also be utilized
in the
compositions herein. Another type of preferred antiredeposition agent includes
the carboxy
methyl cellulose (CMC) materials. These materials are well known in the art.
Polymeric Dispersing Agents
Polymeric dispersing agents can advantageously be utilized at levels from
about 0.1°i° to about
7%, by weight, in the compositions herein, especially in the presence of
zeolite and/or layered
silicate builders. Suitable polymeric dispersing agents include polymeric
polycarboxylates and
polyethylene glycols, although others known in the art can also be used. It is
believed, though it
is not intended to be limited by theory, that polymeric dispersing agents
enhance overall
detergent builder performance, when used in combination with other builders
(including lower
CA 02345737 2004-06-21
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molecular weight polycarboxylates) by crystal growth inhibition, particulate
soil release
peptization, and anti-redeposition.
Polymeric polycarboxylate materials can be prepared by polymerizing or
copolymerizing
suitable unsaturated monomers, preferably in their acid form. Unsaturated
monomeric acids
that can be polymerized to form suitable polymeric polycarboxylates include
acrylic acid,
malefic acid (or malefic anhydride), fumaric acid, itaconic acid, aconitic
acid, mesaconic acid,
citraconic acid and methylenemalonic acid. The presence in the polymeric
polycarboxylates .
herein or monomeric segments, containing no carboxylate radicals such as
vinylmethyl 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
preferably ran=es
from about 2,000 to 10,000, more preferably from about 4,000 to 7,000 and most
preferably
1 ~ 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 la~town materials. Use of polyacrylates of this type in
detergent compositions has
been disclosed, for example, in Diehl, U.S. Patent 3,308,067, issued March 7,
1967.
Acrylic/maleic-based copolymers may also be used as a preferred component of
the
d~spersing/anti-redeposition agent. Such materials include the water-soluble
salts of
copolymers of acrylic acid and malefic acid. The average molecular weight of
such copolymers
in the acid form preferably ranges from about 2,000 to 100,000, more
preferably from about
5,000 to 75,000, most preferably from about 7,000 to 65,000. The ratio of
acrylate to maleate
segments in such copolymers will generally range from about 30:1 to about I:1,
more preferably
2S 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 known materials which are
described in European
Patent Application No. 66915, published December 15, 1982, as well as in EP
193,360,
published September 3, 1986, which also describes such polymers comprising
hydroxypropylacrylate. Still other useful dispersing agents include the
maieic/acrylic/.vinyl
alcohol terpolymers. Such materials are also disclosed in EP 193,360,
including, for example,
the 45/45/ 10 terpolymer of acrylic/maleic/vinyl alcohol.
Another polymeric material which can be included is polyethylene glycol (PEG).
PEG
can exhibit dispersing agent performance as well as act as a clay soil removal-
antiredeposition
CA 02345737 2004-06-21
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agent. Typical molecular weight ranges for these purposes range from about S00
to about
100.000, preferably from about 1,000 to about 50,000, more preferably from
about 1,500 to
about 10,000.
Polyaspartate and polyglutamate dispersing agents may also be used, especially
in
conjunction with zeolite builders. Dispersing agents such as polyaspartate
preferably have a
molecular weight (avg.) of about 10,000.
Brightener
Any optical brighteners or other brightening or whitening agents lmown in the
art can be
incorporated at levels typically from about 0.05% to about 1.2%, by weight,
into the detergent
t 0 compositions herein. Commercial optical brighteners which may be useful in
the present
invention 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
I S Application of Fluorescent Brightening Agents", M. Zahradnik, Published by
John Wiley &
Sons. New York ( 1982).
Specific examples of optical brighteners which are useful in the present
compositions are
those identified in U.S. Patcnt 4,790,856, issued to Wixon on December 13,
1988. These
'rM
br~ghteners include the PHORWHITE sencs of brighteners from Verona. Other
brighteners
'rM
20 disclosed in this reference include: Tinopal UNPA, Tinopal CBS and Tinopal
SBM: available
'rM
from Ciba-Geigy; Artic White CC and Artic White CWD, available from Hilton-
Davis, located
in Italy; the 2-(4-stryl-phenyl)-2H-napthol[1,2-dJtriazoles; 4,4'-bis- (1,2,3-
triazol-2-yl)-stil-
benes: 4,4'-bis(stryl)bisphenyls: and the aminocoumarins. Specific examples of
these
brighteners include 4-methyl-7-diethyl- amino coumarin; 1,2-bis(-venzimidazol-
2-yi)ethylene;
25 1,3-Biphenyl-phrazolines; 2,5-bis(benzoxazol-2-yl)thiophene; 2-stryl-napth-
[1,2-dJoxazole; and
2-(stilbene-4-yl)-2H-naphtho- { 1,2-dJtriazole. See also U.S. Patent
3,646,015, issued February
29, 1972 to Hamilton. Anionic brighteners are preferred herein.
Suds Suppressors
Compounds for reducing or suppressing the formation of suds can be
incorporated into
30 the compositions of the present invention. Suds suppression can be of
particular importance in
the so-called "high concentration cleaning process" as described in U.S.
4,489.455 and
4,489,574 and in front-loading European-style washing machines.
A wide variety of materials may be used as suds suppressors, and suds
suppressors are
welt known to those skiiled in the art. See, for example, Kirk Othmer
Encyclopedia of
CA 02345737 2004-06-21
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Chemical Technology, Third Edition, Volume 7, pages 430-447 (John Wiley &
Sons, Inc.,
1979). One category of suds suppressor of particular interest encompasses
monocarboxylic
fatty acid and soluble salts therein. See U.S. Patent 2,954,347, issued
September 27, 1960 to
Wayne St. John. The monocarboxylic fatty acids and salts thereof used as suds
suppressor
typically have hydrocarbyl chains of 10 to about 24 carbon atoms, preferably
12 to 18 carbon
atoms. Suitable salts include the alkali metal salts such as sodium,
potassium, and lithium salts,
and ammonium and alkanolammonium salts.
The laundry detergent compositions herein 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 triglycerides), fatty acid
esters of monovalent alcohols,
aliphatic C 1 g-C40 ketones (e.g., stearone), etc. Other suds inhibitors
include N-alkylated amino
tnazines such as tri- to hexa-alkylmelamines or di- to tetra-alkyldiamine
chlortriazines formed
as products of cyanuric chloride with two or three moles of a primary or
secondary amine
containing 1 to 24 carbon atoms, propylene oxide, and monostearyl phosphates
such as
I ~ monostearyl alcohol phosphate ester and monostearyi di-alkali metal (e.g.,
K, Na, and Li)
phosphates and phosphate esters. The hydrocarbons 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
~l0°C and about SO°C,
and a minimum boiling point not less than about 110°C (atmospheric
pressure). It is also
known to utilize waxy hydrocarbons, preferably having a melting point below
about 100°C.
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. The hydrocarbons, thus,
include aliphatic,
alicyclic, aromatic, and heterocyclic saturated or unsaturated hydrocarbons
having from about
?5 12 to about 70 carbon atoms. The term "paraffin," 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 suppressors comprises
silicone suds
suppressors_ This category includes the use of polyorganosiloxane oils, such
as
polydimethylsiloxane, dispersions or emulsions of polyorganosiloxane oils or
resins, and
combinations of polyorganosiloxane with silica particles wherein the
polyorganosiloxane is
chemisorbed or 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 and
European Patent Application No. 354016, published February 7, 1990, by Starch,
M. S.
CA 02345737 2001-03-28
WO 00/20550 - PCTNS99/22922
-20-
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 siianated silica are described, for instance, in
German Patent
Application DOS 2,124,526.
In the preferred silicone suds suppressor used herein, the solvent for a
continuous phase is
made up of certain polyethylene glycols or polyethylene-polypropylene glycol
copolymers or
mixtures thereof (preferred), or polypropylene glycol. The primary silicone
suds suppressor is
branched/crosslinked and preferably not linear.
To illustrate this point further, typical liquid laundry detergent
compositions with
controlled suds will optionally comprise from about 0.001 to about 1,
preferably from about
0.01 to about 0.7, most preferably from about 0.05 to about 0.5, weight % of
said silicone suds
suppressor, which comprises (1 ) a nonaqueous emulsion of a primary antifoam
agent which is a
mixture of (a) a polyorganosiloxane, (b) a resinous siloxane or a silicone
resin-producing
silicone compound, (c) a finely divided filler material, and (d) a catalyst to
promote the reaction
of mixture components (a), (b) and (c), to form silanolates; (2) at least one
nonionic silicone
surfactant; and (3) polyethylene glycol or a copolymer of polyethylene-
polypropylene glycol
having a solubility in water at room temperature of more than about 2 weight
%; and without
polypropylene glycol. See also U.S. Patents 4,978,471, Starch, issued December
18, 1990, and
4,983,316, Starch, issued January 8, 1991, 5,288,431, Huber et al., issued
February 22, 1994,
and U.S. Patents 4,639,489 and 4,749,740, Aizawa et al at column 1, line 46
through column 4,
line 35.
The silicone suds suppressor herein preferably comprises polyethylene glycol
and a
copolymer of polyethylene glycol/polypropylene glycol, all having an average
molecular weight
of less than about 1,000, preferably between about 100 and 800. The
polyethylene glycol and
polyethylene/polypropylene copolymers herein have a solubility in water at
room temperature
of more than about 2 weight %, preferably more than about 5 weight %.
The preferred solvent herein is polyethylene glycol having an average
molecular weight
of less than about 1,000, more preferably between about 100 and 800, most
preferably between
200 and 400, and a copolymer of polyethylene glycol/polypropylene glycol,
preferably PPG
200/PEG 300. Preferred is a weight ratio of between about 1:1 and 1:10, most
preferably
between 1:3 and 1:6, of polyethylene glycol:copolymer of polyethylene-
polypropylene glycol.
CA 02345737 2004-06-21
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The preferred silicone suds suppressors used herein do not contain
polypropylene glycol,
particularly of 4,000 molecular weight. They also preferably do not contain
block copolymers
T"M
of ethylene oxide and propylene oxide, like PLUROIVIC LI01.
Other suds suppressors useful herein comprise the secondary alcohols (e.g., 2-
alkyl
alkanols) and mixtures of such alcohols with silicone oils, such as the
silicones disclosed in
U.S. 4,798,679, 4,075,118 and EP 150,872. The secondary alcohols include the
C6-C 16 alkyl
alcohols having a C1-C16 chain. A preferred alcohol is 2-butyl octanol, which
is available from
Condea under the trademark ISOFOL 12. Mixtures of secondary alcohols are
available under
the trademark ISALCHEM 123 from Enichem. Mixed suds suppressors typically
comprise
mixtures of alcohol + silicone at a weight ratio of 1:5 to 5.1.
For any detergent compositions to be used in automatic laundry washing
machines, suds
should not form to the extent that they overflow the washing machine. Suds
suppressors, when
utilized, are preferably present in a "suds suppressing amount. By "suds
suppressing amount'~is
meant that the formulator of the composition can select an amount of this suds
controlling agent
that will sufficiently control the suds to result in a low-sudsing laundry
detergent for use in
automatic Laundry washing machines.
The laundry detergent compositions herein will generally comprise from
0°!° to about 5%
of suds suppressor. When utilized as suds suppressors, monocarboxylic fatty
acids, and salts
therein, will be present typically in amounts up to about 5%, by weight, of
the detergent
composition. 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 weight percentage values include any silica that may be utilized
in combination
with polyorganosiloxane, as well as any adjunct materials that may be
utilized. Monostearyl
phosphate suds suppressors are generally utilized in amounts ranging from
about 0.1% to about
2%, by weight, of the composition. Hydrocarbon suds suppressors are typically
utilized in
amounts ranging from about 0.01 % to about 5.0%, although higher levels can be
used. The
alcohol suds suppressors are typically used at 0.2%-3% by weight of the
finished compositions.
Dye Transfer lnhibiting,Aaents
The laundry detergent compositions of the present invention may also include
one or
more materials effective for inhibiting the transfer of dyes from one fabric
to another during the
cleaning process. Generally, such dye transfer inhibiting agents include
polyvinyl pyrrolidone
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polymers, polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-
vinylimidazole, manganese phthalocyanine, peroxidases, and mixtures thereof.
If used, these
agents typically comprise from about 0.01% to about 10% by weight of the
composition,
preferably from about 0.01% to about s%, and more preferably from about O.OS%
to about 2%.
More specifically, the polyamine N-oxide polymers preferred for use herein
contain units
having the following structural formula: R-AX P; wherein P is a polymerizable
unit to which an
N-O group can be attached or the N-O group can form part of the polymerizable
unit or the N-O
group can be attached to both units; A is one of the following structures: -
NC(O)-, -C(O)O-, -S-,
-O-, -N=; x is 0 or 1; and R is aliphatic, ethoxylated aliphatics, aromatics,
heterocyclic or
alicyclic groups or any combination thereof to which the nitrogen of the N-O
group can be
attached or the N-O group is part of these groups. Preferred polyamine N-
oxides are those
wherein R is a heterocyclic group such as pyridine, pyrrole, imidazole,
pyrrolidine, piperidine
and derivatives thereof.
The N-O group can be represented by the following general structures:
O O
I I
(Rt )x- j -~2)y; =N'.'(R~ )x
(R3 )z
is
wherein R1, R2, R3 are aliphatic, aromatic, heterocyclic or alicyclic groups
or combinations
thereof; x, y and z are 0 or 1; and the nitrogen of the N-O group can be
attached or form part of
any of the aforementioned groups. The amine oxide unit of the polyamine N-
oxides has a pKa
<10, preferably pKa <7, more preferred pKa <6.
Any polymer backbone can be used as long as the amine oxide polymer formed is
water-
soluble and has dye transfer inhibiting properties. Examples of suitable
polymeric backbones
are polyvinyls, polyalkylenes, polyesters, polyethers, polyamide, polyimides,
polyacrylates and
mixtures thereof. These polymers include random or block copolymers where one
monomer
type is an amine N-oxide and the other monomer type is an N-oxide. The amine N-
oxide
2s polymers typically have a ratio of amine to the amine N-oxide of 10:1 to
1:1,000,000.
However, the number of amine oxide groups present in the polyamine oxide
polymer can be
varied by appropriate copolymerization or by an appropriate degree of N-
oxidation. The
polyamine oxides can be obtained in almost any degree of polymerization.
Typically, the
average molecular weight is within the range of 500 to 1,000,000; more
preferred 1,000 to
500,000; most preferred 5,000 to 100,000. This preferred class of materials
can be referred to
as "PVNO".
CA 02345737 2004-06-21
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The most preferred polyamine N-oxide useful in the detergent compositions
herein is
poly(4-vinyfpyridine-N-oxide) which as an average molecular weight of about
50,000 and an
amine to amine N-oxide ratio of about 1:4.
Copolymers of N-vinylpyrrolidone and N-vinylimidazole polymers (referred to as
a class
as "PVPVI") are also preferred for use herein. Preferably the PVPVI has an
average molecular
weight range from 5,000 to 1,000,000, more preferably from 5,000 to 200,000,
and most
preferably from 10,000 to 20,000. (The average molecular weight range is
determined by light
scattering as described in Barth, et al., Chemical Analysis, Vol 113. "Modem
Methods of
Polymer Characterization".) The
PVPVI copolymers typically have a molar ratio u: N-vinylimidazole to N-
vinylpyrtolidone from
1:1 to 0.2:1, more preferably from 0.8:1 to 0.3:1, most preferably from 0.6:1
to 0.4:1. These
copolymers can be either linear or branched.
The laundry detergent compositions also may employ a polyvinylpyrrolidone
("PVP")
having an average molecular weight of from about 5,000 to about 400,000,
preferably from
about 5,000 to about 200,000, and more preferably from about 5,000 to about
50,000. PVP's
are known to persons skilled in the detergent field; see, for example, EP-A-
262,897 and EP-A-
256.696. incorporated herein by reference. Compositions containing PVP can
also contain
polyethylene glycol ("PEG") having an average molecular weight from about 500
to about
100,000, preferably from about 1,000 to about 10.000. Preferably, the ratio of
PEG to PVP on a
?0 ppm basis delivered in wash solutions is from about 2:1 to about 50:1, and
more preferably
from about 3:1 to about 10:1.
The laundry detergent compositions herein may also optionally contain from
about
0.005% to S% by weight of certain types of hydrophilic optical brighteners
which also provide a
dye transfer inhibition action. If used, the compositions herein will
preferably comprise from
about 0.01% to 1% by weight of such optical brighteners.
The hydrophilic optical brighteners useful in the present invention are those
having the
structural formula:
R~
~N H Ii N
N N C C N N
~N H H N \
RI, S03M S03M Ry
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wherein R 1 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 marketed under the trademark Tinopal-iJNPA-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 canon such as sodium, the brightener is 4,4'-bis[(4-anilino-6-(N-2-
hydroxyethyl-N-
methylamino)-s-triazine-2-yl)amino]2.2'-stilbenedisulfonic acid disodium salt.
This particular
brightener species is commercially marketed under the trademark Tinopal SBM-GX
by Ciba--
Geigy Corporation.
1 ~ When in the above formula, RI is anilmo, 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'-
sUlbened~sulfonic acid, sodium salt. This particular brightener species is
commercially
marketed udder the trademark Tinopal AMS-GX by Ciba Geigy Corporation.
The specific optical brightener species selected for use in the present
invention provide
?0 especially effective dye transfer inhibition performance benefits when used
in combination with
the selected polymeric dye transfer inhibiting agents hereinbefore described.
The combination
of such selected polymeric materials (e.g., PVNO and/or PVPVI) with such
selected optical
brtghteners (e.g., Tinopal UNPA-GX, Tinopal SBM-GX and/or Tinopal AMS-GX)
provides
significantly better dye transfer inhibition in aqueous wash solutions than
does either of these
25 two detergent composition components when used alone. Without being bound
by theory, it is
believed that such brighteners work this way because they have high affinity
for fabrics in the
wash solution and therefore deposit relatively quick on these fabrics. The
extent to which
brighteners deposit on fabrics in the wash solution can be defined by a
parameter called the
"exhaustion coefficient". The exhaustion coefficient is in general as the
ratio of a) the
30 brightener material deposited on fabric to b) the initial brightener
concentration in the wash
liquor. Brighteners with relatively high exhaustion coefficients are the most
suitable for
inhibiting dye transfer in the context of the present invention.
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Of course, it will be appreciated that other, conventional optical brightener
types of
compounds can optionally be used in the present compositions to provide
conventional fabric
"brightness" benefits, rather than a true dye transfer inhibiting effect. Such
usage is
conventional and well-known to detergent formulations.
Bleaching Compounds - Bleachine Aeents and Bleach Activators
The laundry detergent compositions herein may optionally contain bleaching
agents or
bleaching compositions containing a bleaching agent and one ar more bleach
activators. Whey
present, bleaching agents will typically be at levels of from about I% to
about 30%, more
typically from about 5% to about 20%, of the detergent composition, especially
for fabric
laundering. If present. the amount of 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
comprising the bleaching agent-plus-bleach activator.
The bleaching agents used herein can be any of the bleaching agents useful for
detergent
compositions in textile cleaning, hard surface cleaning, or other cleaning
purposes that are now
1~ known or become irnow~n. These include oxygen bleaches as well as other
bleaching agents.
Perborate bleaches, e.g.. sodium perborate (e.g., mono- or tetra-hydrate) and
percarbonate
bleaches can be used herein.
Another category of bleaching agent that can be used without restriction
encompasses
percarboxylic acid bleaching agents and salts thereof. Suitable examples of
this class of agents
include magnesium monoperoxyphthalate hexahydrate, the magnesium salt of
metachloro
perbenzoic acid. 4-nonyiaminoji-oxoperoxybutyric acid and
diperoxydodecanedioic acid. Such
bleaching agents are disclosed in U_S. Patent 4.483.781, Hartman. issued
November 20, 1984,
U.S. Patent No. 4,634,551 issued January 6, 1987, European Patent Application
0.133.354, Banks et al, published February 20, 1985, and U.S. Patent
4,412,934, Chung et ai,
vssucd November 1, 1983. Highly preferred bleaching agents also include 6-
nonylamino-6-
oxoperoxycapro~c acid as described in U.S. Patent 4.634,551, issued January 6,
1987 to Burns
et al.
Peroxygen bleaching agents can also be used. Suitable peroxygen bleaching
compounds
include sodium carbonate peroxyhydrate and equivalent "percarbonate" bleaches,
sodium
pyrophosphate peroxyhydrate, urea peroxyhydrate, and sodium peroxide.
Persulfate bleach
TM
(e.g., OXONE, manufactured commercially by DuPont) can also be used.
Mixtures of bleaching agents can also be used.
Peroxygen bleaching agents. the perborates. the percarbonates, etc., are
preferably
combined with bleach activators. which lead to the in situ production in
aquec::,s solution (i.e.,
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during the washing process) of the peroxy acid corresponding to the bleach
activator. Various
nonlimiting examples of activators are disclosed in U.S. Patent 4,915,854,
issued April 10, 1990
to Mao et al, and U.S. Patent 4,412,934. The nonanoyloxybenzene sulfonate
(HOBS) and
tetraacetyl ethylene diamine (TAED) activators are typical, and mixtures
thereof can also be
used. See also U.S. 4,634,551 for other typical bleaches and activators useful
herein.
Highly preferred amido-derived bleach activators are those of the formulae:
R1N(R5)C(O)R2C(O)L or RIC(O)N(R5)R2C(O)L
wherein R1 is an alkyl group containing from about 6 to about 12 carbon atoms,
R2 is an
allylene containing from 1 to about 6 carbon atoms, R~ is H or alkyl, aryl, or
alkaryl containing
from about 1 to about f 0 carbon atoms, and L is any suitable leaving group. A
leaving group is
any group that is displaced from the bleach activator as a consequence of the
nucleophilic
attack on the bleach activator by the perhydrolysis anion. A preferred leavins
group is phenyl
sul fonate_
Preferred examples of bleach activators of the above formulae include (6-
I S octanamidocaproyl)oxybenzenesulfonate, (6-nonanamidocaproyl)oxybenzenesul-
fonate, (6-
decanamidocaproyl)oxybenzenesulfonate, and mixtures thereof as described in
U.S. Patent
4.634,551.
Another class of bleach activators comprises the benzoxazin-type activators
disclosed by
Hodge et al in U.S. Patent 4,966,723, issued October 30, 1990.
Still another class of preferred bleach activators includes the acyl lactam
activators.
especially acyl caprolactams and acyl valerolactams. Highly preferred lactam
activators include
benzoyl caprolactam, octanoyl caprolactam, 3,5,5-trimethylhexanoyl
caprolactam, nonanoyl
caprolactam, decanoyl caprolactam, undecenoyl caprolactam, benzoyl
valerolactam, octanoyl
vaieroiactam, decanoyl vaierolactam, undecenoyl valerolactam, nonanoyl
valerolactam, 3,5,5-
trimethylhexanoyl valerolactam and mixtures thereof. See also U.S. Patent
4,545,784, issued to
Sanderson, October 8, 1985, which discloses acyl
caprolactams, including benzoyl caprolactam, adsorbed into sodium perborate.
Bleaching agents other than oxygen bleaching agents are also known in the art
and can be
utilized herein. One type of non-oxygen bleaching agent of particular interest
includes
photoactivated bleaching agents such as the sulfonated zinc and/or aluminum
phthalocyanines_
See U.S. Patent 4,033,718, issued July 5, 1977 to Holcombe et al. If used,
detergent
compositions will typically contain from about 0.025% to about 1.25%, by
weight, of such
bleaches, especially sulfonate zinc phthalocyanine.
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WO 00/20550 PCT/US99/22922
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If desired, the bleaching compounds can be catalyzed by means of a manganese
compound. Such compounds are well known in the art and include, for example,
the
manganese-based catalysts disclosed in U.S. Pat. 5,246,621, U.S. Pat.
5,244,594; U.S. Pat.
5,194,416; U.S. Pat. 5,114,606; and European Pat. App. Pub. Nos. 549,271A1,
549,272A1,
544,440A2, and 544,490A 1. As a practical matter, and not by way of
limitation, the
compositions and processes herein can be adjusted to provide on the order of
at least one part
per ten million of the active bleach catalyst species in the aqueous washing
liquor, and will
preferably provide from about 0.1 ppm to about 700 ppm, more preferably from
about 1 ppm to
about 500 ppm, of the catalyst species in the laundry liquor.
Anti-Static Age., nts
The laundry detergent compositions can also comprise anti-static agents as
illustrated in
U.S. Pat. 4,861.502. Preferred examples of anti-static agents include alkyl
amine-anionic
surfactant ion pairs, such as distearyl amine-cumene sulfonate ion pairs. If
present, anti-static
agents are present in an amount of from about 0.5% to about 20%, preferably
from about 1 % to
about 10°ro, more preferably from about 1% to about 5%, by weight of
the detergent
composition.
In the following Example A, an embodiment of the present invention of a
chelant
agglomerate is exemplified:
p EXAMPLE A
In e, rg-d'~ent Wt%
Zeolite 85.00
DTPA 15.00
Total 100.0%
Accordingly, having thus described the invention in detail, it will be obvious
to those
skilled in the art that various changes may be made without departing from the
scope of the
invention and the invention is not to be considered limited to what is
described in the
specification.
