Note: Descriptions are shown in the official language in which they were submitted.
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DETERGENT COMPOSITIONS OR COMPONENTS
TECHNICAL FIELD
The present invention relates to compositions or components comprising certain
cyclic amine
based polymers and certain anionic cellulose materials.
BACKGROUND OF THE INVENTION
It is known that fabrics and textiles simply wear out over time and with use.
Also, the laundering
of the fabrics and textiles, over many cycles. can accentuate and contribute
to the deterioration of
the integrity and the appearance of such fabrics and textiles. Deterioration
of fabric integrity and
appearance can manifest itself in several ways. For example, short fibers are
dislodged from
woven and knit fabric/textile structures by the mechanical action of
laundering. These dislodged
fibers may form lint, fuzz or "pills" which are visible on the surface of
fabrics and diminish the
appearance of newness of the fabric. Further, repeated laundering of fabrics
and textiles,
especially with bleach-containing laundry products, can remove dye from
fabrics and textiles and
impart a faded, worn out appearance as a result of diminished color intensity,
and in many cases,
as a result of changes in hues or shades of color.
Given the foregoing, there is clearly an ongoing need to identify materials
which could be added
to laundry detergent products that would associate themselves with the fibers
of the fabrics and
textiles laundered using such detergent products and thereby reduce or
minimize the tendency of
the laundered fabric/textiles to deteriorate in appearance. Any such detergent
product additive
material should, of course, be able to benefit fabric appearance and integrity
without unduly
interfering with the ability of the laundry detergent to perform its fabric
cleaning function. Co-
pending applications PCT/US98/19143 describes the use of certain cyclic amine
based polymers
which are found to provide excellent integrity benefits to fabrics.
The inventor has now found that when these amine based polymers are used in
combination with
specific anionic cellulose material, the fabric care and fabric integrity can
be further improved. It
is believed that these benefits are achieved because the anionic cellulose
material and the amine
based polymers having a positively charged group, interact together in such a
manner that both
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polymeric materials have an improved surface activity, resulting in a better
interaction with or
deposition onto the surface of the fabric. It is believed that when the
polymeric materials are
present in an intimate mixture, such an interaction between the polymeric
materials is even more
likely to occur or even stronger, resulting in a greater benefit obtained when
the polymeric
materials are present in the product as an intimate mixture or in the same
component or granule.
Not only an improved fabric integrity is achieved, but also an improved soil
removal and
whiteness or brightness maintenance is achieved when these compounds are used
together. The
inventor also found that when the anionic cellulose material and the amine
based polymer are
present in an intimate mixture, such as in the form of an agglomerate, a
compacted granule or a
spray dried granule, these benefits are even more apparent.
SUM:~1ARY OF THE INVE1TION
The present invention relates to a detergent composition or component or
additive comprising:
a) from 0.01% to 90% by weight, preferably from 0.05% to 50% by weight, of a
sail of
an anionic cellulose material comprising an anionic substituent group
R - X - Z wherein R is a saturated , unsaturated or aromatic hydrocarbon
spacer
group, X is oxygen, nitrogen or sulphur, Z is carboxylate, sulphonate,
sulphate
or phosphonate group: and
b) from 0.01% to 90% by weight, preferably from about 0.05% to about z0% by
weight
of a cyclic amine based polymer.
The present invention also relates to the laundering or treating of fabrics
and textiles in aqueous
washing or treating solutions formed from effective amounts of the detergent
compositions or
components described herein, or formed from the individual polymeric materials
of such
compositions or components. Laundering of fabrics and textiles in such washing
solutions
imparts fabric appearance benefits to the fabric and textile articles so
treated. Such benefits can
include improved overall appearance, pill/fuu reduction, antifading, improved
abrasion
resistance, and/or enhanced softness and also improved whiteness andl or
brightness maintenance
or even improved cleaning performance
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The cyclic amine based polymers and the cellulose material are preferably in
an intimate mixture
with one another. In one preferred embodiment, the compounds are intimately
mixed prior to
introduction to the composition or component of the invention.
Preferably, the mixture is present in an agglomerated, compacted or spray-
dried particle, when
the composition or component is solid.
Hereby it may be preferred that the compounds are mixed with an anionic
surfactant, preferably
LAS. as described herein after. It may also be preferred that a hydrotrope is
admixed to this
mixture, preferably STS. Also preferably present in the mixture are inorganic
and/or organic salts
and acids and/ or silicates or aluminosilicates, including zeolite, amorphous
silicates, crystalline
layered silicates, carbonate, bicarbonate, phosphate, citric acid, malic acid,
malefic acid, tartaric
acid or salts thereof, or mixtures of these ingredients.
DETAILED DESCRIPTION OF THE INVENTION
~clic amine Based Polymer Materials
An essential component, the compositions or components of the present
invention comprise one
or morc cyclic amine based polymer.
When used herein, 'polymers' include not only polymers, but also oligomers, co-
polymers, co-
oligomers, present in any structural arrangement, also including cross-linked
arrangements. As
will be apparent to those skilled in the art, an oligomer is a molecule
consisting of only a few
monomer units while polymers comprise considerably more monomer units. For the
present
invention, oligomers are defined as molecules having an average molecular
weight below about
1,000 and polymers are molecules having an average molecular weight of greater
than about
1,000; copolymers or co-oligomers are materials wherein two or more dissimilar
monomers have
been simultaneously or sequentially polymerized. Copolymers or co-oligomers of
the present
invention can include, for example, polymers or oligomers polymerized from a
mixture of a
primary cyclic amine based monomer, e.g., piperadine, and a secondary cyclic
amine monomer,
e.g., morpholine.
Depending on the application of the composition or component herein, the
amount of cyclic
amine based polymer may very. The cyclic amine based polymers herein will
generally be about
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0.01% to about 90% by the weight of the detergent composition or component,
more preferably
from 0.05% to 20% or even from 0.05% to~ 15% by weight. In detergent
compositions herein it
may for example be preferred that the polymer is present at a level of from
0.05% to i0% by
weight of the detergent composition, preferably from 0.05% to 5% or even from
0.05% to 3% or
even 0.1% to 2% by weight. In detergent components or additives, the polymer
may preferably be
present at a level of 0.05% to 40% by weight or even from 0.05% to 20% or even
0.1% to 15% or
even 1 % to 10% by weight.
The cyclic amine based polymer herein is preferably present in the composition
or component in
such an amount that the concentration of cyclic amine in the wash is from 100
ppm to 10,000
ppm, preferably from 500 ppm to 7000 ppm or even from 1000 to about 3000 ppm.
The preferred cyclic amine based polymers herein can be characterized by the
following general
formula:
T W- R2 W-T Ab
x
wherein:
each T is independently selected from the group consisting of H, C1-C12 alkyl,
substituted alkyl,
C7-C 12 alkylaryl,
-(CH2)hCOOM. -(CH2)hS03M, CH2CH(OH)S03M, -(CH2)hOS03M,
COOM
-C H C O O M COOM
CH-C001~1 -CH COOM _CHZ~COOM
~H CH,-LOOM -CH~COOM LOOM
ft
and -R2Q;
-wherein W comprises at least one cyclic constituent selected from the group
consisting of:
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~3)c _(R3k~ D\ ~ 3)c ~3)c
N-D N/ \N D-N
R3 ~)c R3 N N
4 . U and
R4
\N ~ N/
U
in addition to the at least one cyclic constituent, W may also comprise an
aliphatic or
substituted aliphatic moiety of the general structure;
N-B N-
I
R3 qR3
-each B is independently C1-C1~ alkylene, Cl-C12 substituted alkylene, C3-C12
alkenylene, Cg-
C 12 dialkylarylene. Cg-C I ~ dialkylarylenediyl, and -(R50)nRS- ;
-each D is independently C2-C6 alkylene;
-each Q is independently selected from the group consisting of hydroxy, C 1-C
1 g alkoxy, C2-C 1 g
hydroxyalkoxy, amino, C 1-C 1 g alkylamino, dialkylamino, trialkyiamino
groups,
heterocyclic monoamino groups and diamino groups;
-each R1 is independently selected from the group consisting of H, C1-Cg alkyl
and C1-Cg
hydroxyalkyl;
-each R~ is independently selected from the group consisting of C 1-C l2
alkylene, C 1-C 12
alkenylene, -CH2-CH(OR1 )-CH2, Cg-C12 alkarylene. C4-C12 dihydroxyalkylene,
poly(C2-C4 alkyleneoxy)alkylene, HoCH(OH)CH20R~OCH2CH(OH)CH2-, and C3-
C12 hydrocarbyl moieties;
provided that when R, is a C3-C 12 hydrocarbyl moiety the hydrocarbyl moiety
can
comprise from about 2 to about 4 branching moieties of the general structure:
OH
-~-ORS ~O-CHI-CH-CH~~W- R~-- W-T
x
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-each R3 is independently selected from the group consisting of H, O, R2, C1-
C20 hydroxyalkyl,
C 1-C2p alkyl, substituted alkyl, C6-C 11 aryl, substituted aryl, C~-C i l
alkylaryl, C 1-C20
aminoalkyl,
-(CH2)hCOOM, -(CH2)hS03M, CH2CH(OH)S03M, -(CH2)hOS03M,
COOM
-CH COOM COOM
C H-C O O M -C H COO LOOM CH2'~ COOM
prH CHa-LOOM -CH' v ~ ~d COOM
-each R4 is independently selected from the group consisting of H, C1-C22
alkyl, C1-C22
hydroxyalkyl, aryl and C~-C22 alkylaryl;
-each RS is independently selected from the group consisting of C2-Cg
alkylene, C2-Cg alkyl
substituted alkylene; and
A is a compatible monovalent or di or polyvalent anion;
M is a compatible cation;
b = number necessary to balance the charge;
each x is independently from 3 to about 1000;
each c is independently 0 or i ;
each h is independently from about 1 to about 8;
each q is independently from 0 to about 6;
each n is independently from 1 to about 20;
each r is independently from 0 to about 20; and
each t is independently from 0 to 1.
The cyclic amine based polymer may comprise combinations of these cyclic amine
based
materials. For example, a mixture of piperadine and epihalohydrin condensates
can be combined
with a mixture of morpholine and epihalohydrin condensates to achieve the
desired fabric
treatment results. Moreover, the molecular weight of cyclic polymers can vary
within the
mixture as is illustrated herein.
Preferred compounds that fall within this general structure include compounds:
- wherein each R 1 is H; and
-at least one W is selected from the group consisting of:
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(R3)c ~3) ~ ~ ~~3x ~3)c
N-D N N D-N
I
R3 R3
q q
~3)c (R3)C\ /(R3x ~3)c
N-D N~N D-N Ra
\N N/
R3
and
R4
~N ~ N/
U
E~~en more preferred compounds are those:
-wherein each RI is H, and
-at least one W is selected from the group consisting of:
( R3 )c (R3 )c
I_ ~ _i
I D /~\ N ~ /
R3 (R3)~ (R3)~ ~ N N
and
~N~N/
U
And most preferred compounds are those:
-wherein each R1 is H: and
-at least one W is selected from the group consisting of:
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-g-
R4
/ \N~N~
and
Preferred compounds to be used as the linking group R2 include, but are not
limited to:
polyepoxides, ethylenecarbonate, propylenecarbonate, urea, a, ~i-unsaturated
carboxylic acids,
esters of a, (3-unsaturated carboxylic acids, amides of a, (3-unsaturated
carboxylic acids,
anhydrides of a, ~3-unsaturated carboxylic acids, di- or polycarboxylic acids,
esters of di- or
polycarboxylic acids, amides of di- or polycarboxylic acids, anhydrides of di-
or polycarboxylic
acids, glycidylhalogens, chloroformic esters, chloroacetic esters, derivatives
of chloroformic
esters, derivatives of chloroacetic esters, epihalohydrins, glycerol
dichlorohydrins, bis-
(halohydrins), polyetherdihalo-compounds, phosgene, polyhalogens,
functionalized glycidyl
ethers and mixtures thereof. Moreover, R2 can also comprise a reaction product
formed by
reacting one or more of polyetherdiamines, alkylenediamines,
polyalkylenepolyamines, alcohols,
alkyleneglycols and polyalkyieneglycols with a, (3-unsaturated carboxylic
acids, esters of a, ~3-
unsaturated carboxylic acids, amides of a, (3-unsaturated carboxylic acids and
anhydrides of a, ~i-
unsaturated carboxylic acids provided that the reaction products contain at
least two double
bonds, two carboxylic groups, two amide groups or two ester groups.
Also preferred cyclic amine based polymers for use herein include adducts of
two or more
compositions selected from the group consisting of piperazine, piperadine,
epichlorohydrin,
epichlorohydrin benzyl quat, epichlorohydrin methyl quat, morpholine and
mixtures thereof.
Highly preferred cyclic amine based polymers herein are referred to as
Imidazole-epi
chlorohydrin copolymers.
These cyclic amine based polymers can be linear or branched. One specific type
of branching
can be introduced using a polyfunctional crosslinking agent. An example of
such such polymer is
exemplified below.
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T
I
~2
X
H
HO O OH
T ~R~ V~~ a~~ W - R2~-- T
-~ x x
Anionic cellulose material
The compositions or components herein comprise a salt of an anionic cellulose
material
comprising an anionic substituent group R - X - Z wherein R is a saturated ,
unsaturated or
aromatic hydrocarbon spacer group, X is oxygen, nitrogen or sulphur, Z is
carboxylate,
sulphonate, sulphate or phosphonate group.
The hydrocarbon spacer group is preferably a C,-C,B, more preferably a C,-C,s,
or even more
preferably a C,-C, saturated , unsaturated or aromatic group, preferably an
alkylene group. The
spacer ~~roup may also be substituted with one or more hydroxy groups.
The group X is preferably a nitrogen, or even more preferably an oxygen atom.
The ~~roup Z is preferably a carboxylate group.
Highly preferred hereon are the so-called salts of carboxyalkyl celluloses,
whereby preferably the
alkylene group (or the so-called alkyl group) comprises from 1 to 4 carbon
atoms. Most preferred
herein is a salt of carboxymethyl cellulose.
The canon of the salt is preferably a potassium ion or more preferably a
sodium ion.
Depending on the application of the composition or component herein, the
amount of cellulose
material may very. The anionic cellulose material herein will generally be
about 0.01% to about
90% by the weight of the detergent composition or component, more preferably
from 0.05% to
SO% or even from 0.05% to 20%. In detergent compositions herein it may for
example be
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preferred that the material is present at a level of from 0.05% to 10% by
weight of the detergent
composition, preferably from 0.05% to 7% or even from 0.05% to 5% or even 0.5%
to 3%. In
components herein, such as detergent additives, the material may preferably be
present at a level
of 0.05% to 40% by weight of the component, or even from 0.05% to 20% or even
0.1 % to 15%
or even 1 % to 10%.
The anionic cellulose material herein is preferably present in the composition
or component in
such an amount that the concentration of cyclic amine in the wash is from 100
ppm to 10,000
ppm, preferably from 500 ppm to 7000 ppm or even from 1000 to about 3000 ppm.
Detergent compositions or components
The compositions or components of the invention are preferably laundry,
compositions,
preferably in the form of granules, extrudates, flakes or tablets, liquids or
pastes.
The compositions or components in accord with the invention may also contain
additional
detergent components. The precise nature of these additional components, and
levels of
incorporation thereof will depend on the physical form of the composition or
component,
and the precise nature of the washing operation for which it is to be used.
They preferably contain one or more additional detergent components selected
from
surfactants, bleaches, bleach catalysts, alkalinity systems, builders,
phosphate-containing
builders, additional organic polymeric compounds, including dispersants, soil
suspension
and anti-redeposition agents soil releasing agents, enzymes, suds suppressors,
lime soap, ,
perfumes, brightners, photobleaching agents and additional corrosion
inhibitors.
Preferred additional ingredients are hydrophobically modified ether and ester
cellulosic
polymers as described in co-pending application PCT/US98/19139 and
PCT/LJS98/19142.
These polymers may be present at a level of from 0.01 % to 10% by weight of
the
composition, more preferably at a level of from 0.05% to 5% by weight or even
form
0.1 % to 2% by weight of the composition, or at a level of from 0.05% to 30%
by weight
of the component, more preferably at a level of from 0.1% to 20% by weight or
even form
0.3% to 10% by weight of the component.
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Also highly preferred are enzymes, cationic softening agents, clay, optionally
together
with polymeric flocculants, dye transfer inhibitors, or preferably mixtures
thereof, as
described herein after.
Surfactant
The components or compositions in accord with the invention preferably contain
one or
more surfactants selected from anionic, nonionic, cationic, ampholytic,
amphoteric and
zwitterionic surfactants and mixtures thereof.
A typical listing of anionic, nonionic, ampholytie, and zwitterionic classes,
and species of
these surfactants, is given in U.S.P. 3,929,678 issued to Laughlin and Heuring
on
December 30, 1975. Further examples are given in "Surface Active Agents and
Detergents" (Vol. I and II by Schwartz, Perry and Berch). A list of suitable
cationic
surfactants is given in U.S.P. 4,259,217 issued to Murphy on March 31, 1981.
Where present, ampholytic, amphoteric and zwitteronic surfactants are
generally used in
combination with one or more anionic and/or nonionic surfactants.
Anionic Surfactant
The components or compositions in accord with the present invention preferably
comprise
an additional anionic surfactant. Essentially any anionic surfactants useful
for detersive
purposes can be comprised in the detergent components or compositions. These
can
include salts (including, for example, sodium, potassium, ammonium, and
substituted
ammonium salts such as mono-, di- and triethanolamine salts) of the anionic
sulfate,
sulfonate, carboxylate and sarcosinate surfactants. Anionic sulfate and
sulfonate
surfactants are preferred.
Highly preferred are surfactants systems comprising a sulfonate and a sulfate
surfactant,
preferably a linear or branched alkyl benzene sulfonate and alkyl
ethoxylsulfates, as
described herein, preferably combined with a cationic surfactants as described
herein.
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Other anionic surfactants include the isethionates such as the acyl
isethionates, N-acyl
taurates, fatty acid amides of methyl tauride, alkyl succinates and
sulfosuccinates,
monoesters of sulfosuccinate (especially saturated and unsaturated C12-C18
monoesters)
diesters of sulfosuccinate (especially saturated and unsaturated C6-C14
diesters), N-acyl
sarcosinates. Resin acids and hydrogenated resin acids are also suitable, such
as rosin,
hydrogenated rosin, and resin acids and hydrogenated resin acids present in or
derived
from tallow oil.
Anionic Sulfate Surfactant
Anionic sulfate surfactants suitable for use herein include the linear and
branched primary
and secondary alkyl sulfates, alkyl ethoxysulfates, fatty oleoyl glycerol
sulfates, alkyl
phenol ethylene oxide ether sulfates, the CS-Cl~ acyl-N-(C1-C4 alkyl) and -N-
(C1-C2
hydroxyalkyi) glucamine sulfates, and sulfates of alkylpolysaccharides such as
the sulfates
of alkylpolyglucoside (the nonionic nonsulfated compounds being described
herein).
Alkyl sulfate surfactants are preferably selected from the linear and branched
primary
C 10-C 1 g alkyl sulfates, more preferably the C 11-C 15 branched chain alkyl
sulfates and
the CI ~-C14 linear chain alkyl sulfates.
Alkyl ethoxysulfate surfactants are preferably selected from the group
consisting of the
C 10-C 1 g alkyl sulfates which have been ethoxylated with from 0.5 to 20
moles of
ethylene oxide per molecule. More preferably, the alkyl ethoxysulfate
surfactant is a C11-
Clg, most preferably C11-C15 alkyl sulfate which has been ethoxylated with
from 0.5 to
7, preferably from 1 to 5, moles of ethylene oxide per molecule.
A particularly preferred aspect of the invention employs mixtures of the
preferred alkyl
sulfate and/ or sulfonate and alkyl ethoxysulfate surfactants. Such mixtures
have been
disclosed in PCT Patent Application No. WO 93/18124.
Anionic Sulfonate Surfactant
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Anionic sulfonate surfactants suitable for use herein include the salts of CS-
C2p linear
alkylbenzene sulfonates, alkyl ester sulfonates, C6-C22 primary or secondary
alkane
sulfonates, C6-C24 olefin sulfonates, sulfonated polycarboxylic acids, alkyl
glycerol
sulfonates, fatty acyi glycerol sulfonates, fatty oleyl glycerol sulfonates,
and any mixtures
thereof.
Anionic Carbox~late Surfactant
Suitable anionic carboxylate surfactants include the alkyl ethoxy
carboxylates, the alkyl
polyethoxy polycarboxylate surfactants and the soaps ('alkyl carboxyls'),
especially certain
secondary soaps as described herein.
Suitable alkyl ethoxy carboxylates include those with the formula RO(CH2CH20)x
CH~C00-M+ wherein R is a C6 to C18 alkyl group, x ranges from O to 10, and the
ethoxylate distribution is such that, on a weight basis, the amount of
material where x is 0
is less than 20 °~o and M is a cation. Suitable alkyl polyethoxy
polycarboxylate surfactants
include those having the formula RO-(CHR1-CHR2-O)-R3 wherein R is a C6 to Clg
alkyl group, x is from 1 to 25, RI and R2 are selected from the group
consisting of
hydrogen, methyl acid radical, succinic acid radical, hydroxysuccinic acid
radical, and
mixtures thereof, and R3 is selected from the group consisting of hydrogen,
substituted or
unsubstituted hydrocarbon having between 1 and 8 carbon atoms, and mixtures
thereof.
Suitable soap surfactants include the secondary soap surfactants which contain
a carboxyl
unit connected to a secondary carbon. Preferred secondary soap surfactants for
use herein
are water-soluble members selected from the group consisting of the water-
soluble salts
of 2-methyl-I-undecanoic acid, 2-ethyl-I-decanoic acid, 2-propyl-1-nonanoic
acid, 2-
butyl-1-octanoic acid and 2-pentyl-1-heptanoic acid.
Certain soaps may also be included as suds suppressers.
Alkali Metal Sarcosinate Surfactant
Other suitable anionic surfactants are the alkali metal sarcosinates of
formula R-CON
(R1 ) CH2 COOM, wherein R is a CS-C1~ linear or branched alkyl or aikenyl
group, R1 is
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a CI-C4 alkyl group and M is an alkali metal ion. Preferred examples are the
myristyl and
oleoyl methyl sarcosinates in the form of their sodium salts.
Alkoxylated Nonionic Surfactant
Essentially any alkoxylated nonionic surfactants are suitable herein. The
ethoxylated and
propoxylated nonionic surfactants are preferred.
Preferred alkoxylated surfactants can be selected from the classes of the
nonionic
condensates of alkyl phenols, nonionic ethoxyiated alcohols, nonionic
ethoxylated/propoxylated fatty alcohols, nonionic ethoxylate/propoxylate
condensates
with propylene glycol, and the nonionic ethoxylate condensation products with
propylene
oxide/ethylene diamine adducts.
Nonionic Alkoxylated Alcohol Surfactant
The condensation products of aliphatic alcohols with from 1 to 25 moles of
aikylene
oxide, particularly ethylene oxide and/or propylene oxide, are suitable for
use herein. The
alkyl chain of the aliphatic alcohol can either be straight or branched,
primary or
secondary, and generally contains from 6 to 22 carbon atoms. Particularly
preferred are
the condensation products of alcohols having an alkyl group containing from 8
to 20
carbon atoms with from 2 to i0 moles of ethylene oxide per mole of alcohol.
Nonionic Pol~ydroxv Fatty Acid Amide Surfactant
Polyhydroxy fatty acid amides suitable for use herein are those having the
structural
formula R2CONR i Z wherein : R 1 is H, C 1-C4 hydrocarbyl, 2-hydroxy ethyl, 2-
hydroxy
propyl, ethoxy, propoxy, or a mixture thereof, preferable CI-C4 alkyl, more
preferably CI
or C2 alkyl, most preferably C i alkyl (i.e., methyl); and R2 is a CS-C3 i
hydrocarbyl,
preferably straight-chain CS-C i 9 alkyl or alkenyl, more preferably straight-
chain Cg-C i 7
alkyl or alkenyl, most preferably straight-chain Cl i-Cl~ alkyl or alkenyl, or
mixture
thereof; and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain
with at least
3 hydroxyls directly connected to the chain, or an alkoxylated derivative
(preferably
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ethoxyiated or propoxylated) thereof. Z preferably will be derived from a
reducing sugar
in a reductive amination reaction; more preferably Z is a glycityl.
Nonionic Fattv Acid Amide Surfactant
Suitable fatty acid amide surfactants include those having the formula:
R6CON(R7)2
wherein R6 is an alkyl group containing from 7 to 21, preferably from 9 to 17
carbon
atoms and each R7 is selected from the group consisting of hydrogen, C1-C4
alkyl, C1-C4
hydroxyalkyl, and -(C2H40)xH, where x is in the range of from 1 to 3.
Nonionic Alkylpolysaccharide Surfactant
Suitable alkylpolysaccharides for use herein are disclosed in U.S. Patent
4,565,647,
Llenado, issued January 21, 1986, having a hydrophobic group containing from 6
to 30
carbon atoms and a polysaccharide, e.g., a polyglycoside, hydrophilic group
containing
from 1.3 to 10 saccharide units.
Preferred alkylpolyglycosides have the formula:
R20(CnH~nO)t(glycosyl)x
wherein R' is selected from the group consisting of alkyl, alkylphenyl,
hydroxyalkyl,
hydroxyalkylphenyl, and mixtures thereof in which the alkyl groups contain
from 10 to 18
carbon atoms; n is 2 or 3; t is from 0 to 10, and x is from 1.3 to 8. The
glycosyl is
preferably derived from glucose.
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Amphoteric Surfactant
Suitable amphoteric surfactants for use herein include the amine oxide
surfactants and the
alkyl amphocarboxylic acids.
Suitable amine oxides include those compounds having the formula
R3(OR4)xN0(RS)2
wherein R3 is selected from an alkyl, hydroxyalkyl, acylamidopropoyl and alkyl
phenyl
group, or mixtures thereof, containing from 8 to 26 carbon atoms; R4 is an
alkylene or
hydroxyalkylene group containing from 2 to 3 carbon atoms, or mixtures
thereof; x is
from 0 to 5, preferably from 0 to 3; and each RS is an alkyl or hydroxyalkyl
group
containing from 1 to 3, or a polyethylene oxide group containing from 1 to 3
ethylene
oxide groups. Preferred are C 10-C 1 g alkyl dimethylamine oxide, and C 10-18
acylamido
alkyl dimethylamine oxide.
A suitable example of an alkyl aphodicarboxylic acid is Miranol(TM) C2M Conc.
manufactured by Miranol, Inc., Dayton, NJ.
Zwitterionic Surfactant
Zwitterionic surfactants can also be incorporated into the detergent
components or
compositionss in accord with the invention. These surfactants can be broadly
described
as derivatives of secondary and tertiary amines, derivatives of heterocyclic
secondary and
tertiary amines, or derivatives of quaternary ammonium, quaternary phosphonium
or
tertiary sulfonium compounds. Betaine and sultaine surfactants are exemplary
zwitterionic
surfactants for use herein.
Suitable betaines are those compounds having the formula R(R')2N+R2C00-
wherein R
is a C6-Cl g hydrocarbyl group, each Rl is typically C1-C3 alkyl, and R2 is a
C1-CS
hydrocarbyl group. Preferred betaines are C12-18 dimethyl-ammonio hexanoate
and the
C 10-18 acylarnidopropane (or ethane) dimethyl (or diethyl) betaines. Complex
betaine
surfactants are also suitable for use herein.
Cationic Surfactants
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Suitable cationic surfactants to be used in the detergent herein include the
quaternary
ammonium surfactants. Preferably the quaternary ammonium surfactant is a mono
C6-
C 16, preferably C6-C 10 N-alkyl or alkenyi ammonium surfactants wherein the
remaining
N positions are substituted by methyl, hydroxyethyl or hydroxypropyl groups.
Preferred
are also the mono-alkoxylated and bis-alkoxylated amine swfactants.
Another suitable group of cationic surfactants which can be used in the
detergent compositions or components thereof herein are cationic ester
surfactants.
The cationic ester surfactant is a, preferably water dispersible, compound
having
surfactant properties comprising at least one ester (i.e. -COO-) linkage and
at least one
cationically charged group.
Suitable cationic ester surfactants, including choline ester surfactants, have
for example
been disclosed in US Patents No.s 4228042, 4239660 and 4260529.
In one preferred aspect the ester linkage and cationically charged group are
separated from
each other in the surfactant molecule by a spacer group consisting of a chain
comprising
at least three atoms (i.e. of three atoms chain length), preferably from three
to eight atoms,
more preferably from three to five atoms, most preferably three atoms. The
atoms forming
the spacer group chain are selected from the group consisting of carbon,
nitrogen and
oxygen atoms and any mixtures thereof, with the proviso that any nitrogen or
oxygen
atom in said chain connects only with carbon atoms in the chain. Thus spacer
groups
having, for example, -O-O- (i.e. peroxide), -N-N-, and -N-O- linkages are
excluded,
whilst spacer groups having, for example -CH2-O- CH2- and -CH2-NH-CH2-
linkages
are included. In a preferred aspect the spacer group chain comprises only
carbon atoms,
most preferably the chain is a hydrocarbyl chain.
Cationic mono-alkoxylated amine surfactants
Highly preferred herein are cationic mono-alkoxylated amine surfactant
preferably of the
general formula I:
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R~ /ApRa
\N+ X
R (n
wherein R1 is an alkyl or alkenyl moiety containing from about 6 to about 18
carbon
atoms, preferably 6 to about 16 carbon atoms, most preferably from about 6 to
about 14
carbon atoms; R2 and R3 are each independently alkyl groups containing from
one to
about three carbon atoms, preferably methyl, most preferably both R2 and R3
are methyl
groups; R4 is selected from hydrogen (preferred), methyl and ethyl; X' is an
anion such as
chloride, bromide, methylsulfate, sulfate, or the like, to provide electrical
neutrality; A is a
alkoxy group, especially a ethoxy, propoxy or butoxy group; and p is from 0 to
about 30,
preferably 2 to about 15, most preferably 2 to about 8.
Preferably the ApR4 group in formula I has p=1 and is a hydroxyalkyl group,
having no
greater than 6 carbon atoms whereby the -OH group is separated from the
quaternary
ammonium nitrogen atom by no more than 3 carbon atoms. Particularly preferred
ApR4
groups are -CH~CH~OH, -CH2CH2CH20H, --CH~CH(CH3)OH and -
CH(CH3)CH~OH, with---CHZCH~OH being particularly preferred. Preferred R1
groups
are linear alkyl groups. Linear R1 groups having from 8 to 14 carbon atoms are
preferred.
Another highly preferred cationic mono-alkoxylated amine surfactants for use
herein are
of the fonmula
(CHZCH20)~-SH
~N+~ XO
CH3/ \CH3
wherein R 1 is C I p-C I g hydrocarbyl and mixtur es thereof, especially C I 0-
C I 4 alkyl,
preferably C I p and C I 2 alkyl, and X is any convenient anion to provide
charge balance,
preferably chloride or bromide.
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As noted, compounds of the foregoing type include those wherein the ethoxy
{CH2CH20) units (EO) are replaced by butoxy, isopropoxy [CH(CH3)CH20] and
[CH2CH(CH30] units (i-Pr) or n-propoxy units (Pr), or mixtures of EO and/or Pr
and/or
i-Pr units.
The levels of the cationic mono-alkoxylated amine surfactants used in
detergent
compositions of the invention is preferably from 0.1 % to 20%, more preferably
from
0.2% to 7%, most preferably from 0.3% to 3.0% by weight of the composition.
Cationic bis-alkoxylated amine surfactant
The cationic bis-alkoxylated amine surfactant preferably has the general
formula II:
R1 / ApR3
R~~ ~A,qRa
wheiein R1 is an alkyl or alkenyl moiety containing from about 8 to about 18
carbon
atoms, preferably 10 to about 16 carbon atoms, most preferably from about 10
to about 14
carbon atoms; R2 is an alkyl group containing from one to three carbon atoms,
preferably
methyl; R3 and R4 can vary independently and are selected from hydrogen
(preferred),
methyl and ethyl, X' is an anion such as chloride, bromide, methyisulfate,
sulfate, or the
like, sufficient to provide electrical neutrality. A and A' can vary
independently and are
each selected from C 1-C4 alkoxy, especially ethoxy, (i.e., -CH2CH20-),
propoxy, butoxy
and mixtures thereof; p is from 1 to about 30, preferably 1 to about 4 and q
is from 1 to
about 30, preferably 1 to about 4, and most preferably both p and q are 1.
Highly preferred cationic bis-alkoxylated amine surfactants for use herein are
of the
formula
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+/CH2CH20H
N X
CH3/ \CHZCH20H
wherein R 1 is C 1 p-C 1 g hydrocarbyl and mixtures thereof, preferably C 1 p,
C 12, C 14 alkyl
and mixtures thereof. X is any convenient anion to provide charge balance,
preferably
chloride. With reference to the general cationic bis-alkoxylated amine
structure noted
above, since in a preferred compound R 1 is derived from (coconut) C 12-C 14
alkyl
fraction fatty acids, R2 is methyl and ApR3 and A'qR4 are each monoethoxy.
Other cationic bis-alkoxylated amine surfactants useful herein include
compounds of the
formula:
I
R~ ~(CHZCH~O}pH
'/N ~ X-
R (CH2CH20)qH
wherein R 1 is C 1 p-C 1 g hydrocarbyl, preferably C 1 p-C 14 alkyl,
independently p is 1 to
about 3 and q is 1 to about 3, R2 is C1-C3 alkyl, preferably methyl, and X is
an anion,
especially chloride or bromide.
Other compounds of the foregoing type include those wherein the ethoxy
(CH2CH20)
units (EO) are replaced by butoxy (Bu) isopropoxy [CH(CH3)CH~OJ and
[CH2CH(CH30] units (i-Pr) or n-propoxy units (Pr), or mixtures of EO and/or Pr
and/or
i-Pr units.
Perhydrate Bleaches
An preferred additional components of the components or compositions is a
perhydrate
bleach, such as metal perborates, metal percarbonates, particularly the sodium
salts.
Perborate can be mono or tetra hydrated. Sodium percarbonate has the formula
corresponding to 2Na2C03.3H202, and is available commercially as a crystalline
solid.
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Potassium peroxymonopersulfate, sodium per is another optional inorganic
perhydrate salt
of use in the detergent components or compositions herein.
Organic Peroxyacid Bleaching Svstem
A preferred feature of the components or compositions is an organic peroxyacid
bleaching
system. In one preferred execution the bleaching system contains a hydrogen
peroxide
source and an organic peroxyacid bleach precursor compound. The production of
the
organic peroxyacid occurs by an in situ reaction of the precursor with a
source of
hydrogen peroxide. Preferred sources of hydrogen peroxide include inorganic
perhydrate
bleaches, such as the perborate bleach of the claimed invention. In an
alternative preferred
execution a preformed organic peroxyacid is incorporated directly into the
components or
compositions. Components or compositions containing mixtures of a hydrogen
peroxide
source and organic peroxyacid precursor in combination with a preformed
organic
peroxyacid are also envisaged.
Peroxyacid Bleach Precursor
Peroxyacid bleach precursors are compounds which react with hydrogen peroxide
in a
perhydrolysis reaction to produce a peroxyacid. Generally peroxyacid bleach
precursors
may be represented as
O
X-C-L
where L is a leaving group and X is essentially any functionality, such that
on
perhydroloysis the structure of the peroxyacid produced is
O
Ji
X-C-OOH
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Peroxyacid bleach precursor compounds are preferably incorporated at a level
of from
0.5% to 20% by weight, more preferably from 1% to 15% by weight, most
preferably
from 1.5% to 10% by weight of the detergent compositions.
Suitable peroxyacid bleach precursor compounds typically contain one or more N-
or O-
acyl groups, which precursors can be selected from a wide range of classes.
Suitable
classes include anhydrides, esters, imides, lactams and acylated derivatives
of imidazoles
and oximes. Examples of useful materials within these classes are disclosed in
GB-A-
1586789. Suitable esters are disclosed in GB-A-836988, 864798, 1147871,
2143231 and
EP-A-0170386.
Leaving Group
The leaving group, hereinafter L group, must be sufficiently reactive for the
perhydrolysis
reaction to occur within the optimum time frame (e.g., a wash cycle). However,
if L is too
reactive. this activator will be difficult to stabilize for use in a bleaching
components or
compositions.
Preferred L groups are selected from the group consisting of:
Y R3 RsY
-O ~ , -O ~ Y , and -O
4
-N-C-R -N N -N-C-CH-R
R3 Y ,
I
Y
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3
R Y
-O-C H=C-C H=C H2 -O-C H=C-C H=C H2
O Y O
O 1 CH2'C NR4 -N~ /NR4
_O-C-R -NwC/ , . wC
O O
3
R O Y
-O-C=C H R4 , and -N-S-C H-R4
R3 O
and mixtures thereof, wherein R1 is an alkyl, aryl, or alkaryi group
containing from t to
14 carbon atoms, R3 is an alkyl chain containing from 1 to 8 carbon atoms, R4
is H or R3,
and Y is H or a solubilizing group. Any of Rl, R3 and R'~ may be substituted
by
essentially any functional group including, for example alkyl, hydroxy,
alkoxy, halogen,
amine, nitrosyl, amide and ammonium or alkyl ammmonium groups.
The preferred solubilizing groups are -S03-M+, -C02-M+, -S04 M+, -N+(R3)4X-
and
O<--N(R3)3 and most preferably -S03 M+ and -CO~ M+ wherein R3 is an alkyl
chain
containing from 1 to 4 carbon atoms, M is a cation which provides solubility
to the bleach
activator and X is an anion which provides solubility to the bleach activator.
Preferably,
M is an alkali metal, ammonium or substituted ammonium cation, with sodium and
potassium being most preferred, and X is a halide, hydroxide, methylsulfate or
acetate
anion.
Alkyl Percarboxylic Acid Bleach Precursors
Alkyl percarboxylic acid bleach precursors form percarboxylic acids on
perhydrolysis.
Preferred precursors of this type provide peracetic acid on perhydrolysis.
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Preferred alkyl percarboxyiic precursor compounds of the imide type include
the N-
,N,N1N1 tetra acetylated alkylene diamines wherein the alkyiene group contains
from 1 to
6 carbon atoms, particularly those compounds in which the alkylene group
contains 1, 2
and 6 carbon atoms. Tetraacetyl ethylene diamine (TAED) is particularly
preferred.
Other preferred alkyl percarboxylic acid precursors include sodium 3,5,5-tri-
methyl
hexanoyloxybenzene sulfonate (iso-NOBS), sodium nonanoyloxybenzene sulfonate
(HOBS), sodium acetoxybenzene sulfonate (ABS) and pentaacetyl glucose.
Amide Substituted Alkyl Peroxyacid Precursors
Amide substituted alkyl peroxyacid precursor compounds are suitable herein,
including
those of the following general formulae:
R~ -C-N-R2-C-L R~ -N-C-R2-C-L
! ~i
~I
O R5 O or R5 O O
wherein R1 is an alkyl group with from 1 to 14 carbon atoms, R' is an alkylene
group
containing from 1 to 14 carbon atoms, and R5 is H or an alkyl group containing
1 to 1.0
carbon atoms and L can be essentially any leaving group. Amide substituted
bleach
activator compounds of this type are described in EP-A-0170386.
Preformed Organic Peroxyacid
The detergent composition may contain, in addition to, or as an alternative
to, an organic
peroxyacid bleach precursor compound, a preformed organic peroxyacid ,
typically at a
level of from 1 % to 15% by weight, more preferably from 1% to 10% by weight
of the
composition.
A preferred class of organic peroxyacid compounds are the amide substituted
compounds
of the following general formulae:
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R~ -C-N-R2-C-OOH R~ -N-C-R2-C-OOH
O R~ O or R5 O O
wherein R1 is an alkyl, aryl or alkaryl group with from 1 to 14 carbon atoms,
R2 is an
alkylene, arylene, and alkarylene group containing from 1 to 14 carbon atoms,
and RS is
H or an alkyl, aryl, or aikaryl group containing 1 to 10 carbon atoms. Amide
substituted
organic peroxyacid compounds of this type are described in EP-A-0170386.
Other organic peroxyacids include diacyl and tetraacylperoxides, especially
diperoxydodecanedioc acid, diperoxytetradecanedioc acid and
diperoxyhexadecanedioc
acid. Mono- and diperazelaic acid, mono- and diperbrassylic acid and N-
phthaloylaminoperoxicaproic acid are also suitable herein.
V1,'ater-Soluble Builder Compound
The components or compositions in accord with the present invention preferably
contain a
water-soluble builder compound, typically present in detergent compositions at
a level of
from 1°,'o to 80% by weight, preferably from 10% to 60% by weight, most
preferably from
15% to 40% by weight of the composition.
The detergent components or compositions of the invention preferably comprise
phosphate-containing builder material. Preferably present at a level of from
0.5% to 60%,
more preferably from 5% to 50%, more preferably from 8% to 40.
The phosphate-containing builder material preferably comprises tetrasodium
pyrophosphate or even more preferably anhydrous sodium tripolyphosphate.
Suitable water-soluble builder compounds include the water soluble monomeric
polycarboxylates, or their acid forms, homo or copolymeric polycarboxylic
acids or their
salts in which the polycarboxylic acid comprises at least two carboxylic
radicals separated
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from each other by not more that two carbon atoms, borates, and mixtures of
any of the
foregoing.
The carboxylate or polycarboxylate builder can be momomeric or oligomeric in
type
although monomeric polycarboxylates are generally preferred for reasons of
cost and
performance.
Suitable carboxylates containing one carboxy group include the water soluble
salts of
lactic acid, glycolic acid and ether derivatives thereof. Polycarboxylates
containing two
carboxy groups include the water-soluble salts of succinic acid, malonic acid,
(ethylenedioxy) diacetic acid, malefic acid, diglycolic acid, tartaric acid,
tartronic acid and
fumaric acid, as well as the ether carboxylates and the sulfinyl carboxylates.
Polycarboxylates or their acids containing three carboxy groups include, in
particular,
water-soluble citrates, aconitrates and citraconates as well as succinate
derivatives such as
the carboxymethyloxysuccinates described in British Patent No. 1,379,241,
lactoxysuccinates described in British Patent No. 1,389,732, and
aminosuccinates
described in Netherlands Application 7205873, and the oxypolycarboxylate
materials
such as 2-oxa-1,1,3-propane tricarboxylates described in British Patent No.
1,387,447.
The most preferred polycarboxylic acid containing three carboxy groups is
citric acid,
preferably present at a level of from 0.1 % to 15%, more preferably from 0.5%
to 8% by
weight of the composition.
Polycarboxylates containing four carboxy groups include oxydisuccinates
disclosed in
British Patent No. 1,261,829, 1,1,2,2-ethane tetracarboxylates, 1,1,3,3-
propane
tetracarboxylates and 1,1,2,3-propane tetracarboxylates. Polycarboxylates
containing
sulfo substituents include the sulfosuccinate derivatives disclosed in British
Patent Nos.
1,398,421 and 1,398,422 and in U.S. Patent No. 3,936,448, and the sulfonated
pyrolysed
citrates described in British Patent No. 1,439,000. Preferred polycarboxylates
are
hydroxycarboxylates containing up to three carboxy groups per molecule, more
particularly citrates.
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The parent acids ~f the monomeric or oligomeric polycarboxylate chelating
agents or
mixtures thereof with their salts, e.g. citric acid or citrate/citric acid
mixtures are also
contemplated as useful builder components.
Borate builders, as well as builders containing borate-forming materials that
can produce
borate under detergent storage or wash conditions are useful water-soluble
builders
herein.
Suitable examples of water-soluble phosphate builders are the alkali metal
tripolyphosphates, sodium, potassium and ammonium pyrophosphate, sodium and
potassium and ammonium pyrophosphate, sodium and potassium orthophosphate,
sodium
polymeta/phosphate in which the degree of polymerization ranges from about 6
to 21, and
salts of phytic acid.
Partially Soluble or Insoluble Builder Compound
The components or compositions in accord with the present invention may
contain a
partially soluble or insoluble builder compound, typically present in
detergent
compositions at a level of from 0.5% to 60% by weight, preferably from S% to
50% by
weight, most preferably from 8% to 40% weight of the composition.
Examples of largely water insoluble builders include the sodium
aluminosilicates.
Suitable aluminosilicate zeolites have the unit cell formula
Naz[(A102)z(Si02)y]. xH20
wherein z and y are at least 6; the molar ratio of z to y is from 1.0 to 0.5
and x is at least S,
preferably from 7.5 to 276, more preferably from 10 to 264. The
aluminosilicate material
are in hydrated form and are preferably crystalline, containing from 10% to
28%, more
preferably from 18% to 22% water in bound form.
The aluminosilicate zeolites can be naturally occurring materials, but are
preferably
synthetically derived. Synthetic crystalline aluminosilicate ion exchange
materials are
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available under the designations Zeolite A, Zeolite B, Zeolite P, Zeolite X,
Zeolite HS and
mixtures thereof. Zeolite A has the formula:
Na 12 (A102) 12 (5102)12. xH20
wherein x is from 20 to 30, especially 27. Zeolite X has the formula Nag6
((A102)86(Si02)106~~ 276 H20.
Another preferred aluminosilicate zeolite is zeolite MAP builder.
The zeolite MAP can be present at a level of from 1% to 80%, more preferably
from
1 S% to 40% by weight of the compositions.
Zeolite MAP is described in EP 384070A (Unilever). It is defined as an alkali
metal alumino-silicate of the zeolite P type having a silicon to aluminium
ratio not
greater than 1.33, preferably within the range from 0.9 to 1.33 and more
preferably
within the range of from 0.9 to 1.2.
Of particular interest is zeolite MAP having a silicon to aluminium ratio not
greater
than 1.15 and, more particularly, not greater than 1.07.
In a preferred aspect the zeolite MAP detergent builder has a particle size,
expressed as a ds0 value of from 1.0 to 10.0 micrometres, more preferably from
2.0
to 7.0 micrometres, most preferably from 2.5 to S.0 micrometres.
The dj0 value indicates that 50% by weight of the particles have a diameter
smaller
than that figure. The particle size may, in particular be determined by
conventional
analytical techniques such as microscopic determination using a scanning
electron
microscope or by means of a laser granulometer. Other methods of establishing
d50
values are disclosed in EP 384070A.
Heav~metal ion sequestrant
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The components or compositions of the invention preferably contain as an
optional
component a heavy metal ion sequestrant. By heavy metal ion sequestrant it is
meant
herein components which act to sequester (chelate) heavy metal ions. These
components
may also have calcium and magnesium chelation capacity, but preferentially
they show
selectivity to binding heavy metal ions such as iron, manganese and copper.
Heavy metal ion sequestrants are generally present at a level of from 0.005%
to 10%,
preferably from 0.1% to 5%, more preferably from 0.25% to 7.5% and most
preferably
from 0.3% to 2% by weight of the compositions or component
Suitable heavy metal ion sequestrants for use herein include organic
phosphonates, such
as the amino alkylene poly (alkylene phosphonates), alkali metal ethane 1-
hydroxy
disphosphonates and nitrilo trimethylene phosphonates.
Preferred among the above species are diethylene triamine penta (methylene
phosphonate), ethylene diamine tri (methylene phosphonate) hexamethylene
diamine tetra
(methylene phosphonate) and hydroxy-ethylene 1,1 diphosphonate, 1,1
hydroxyethane
diphosphonic acid and I .1 hydroxyethane dimethylene phosphonic acid.
Other suitable heavy metal ion sequestrant for use herein include
nitrilotriacetic acid and
polyaminocarboxylic acids such as ethylenediaminotetracetic acid,
ethylenediamine
disuccinic acid, ethylenediamine diglutaric acid, 2-hydroxypropylenediamine
disuccinic
acid or any salts thereof.
Other suitable heavy metal ion sequestrants for use herein are iminodiacetic
acid
derivatives such as 2-hydroxyethyl diacetic acid or glyceryi imino diacetic
acid, described
in EP-A-317,542 and EP-A-399,133. The iminodiacetic acid-N-2-hydroxypropyl
sulfonic
acid and aspartic acid N-carboxymethyl N-2-hydroxypropyl-3-sulfonic acid
sequestrants
described in EP-A-516,102 are also suitable herein. The ~3-alanine-N,N'-
diacetic acid,
aspartic acid-N,N'-diacetic acid, aspartic acid-N-monoacetic acid and
iminodisuccinic
acid sequestrants described in EP-A-509,382 are also suitable.
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EP-A-476,257 describes suitable amino based sequestrants. EP-A-510,331
describes suitable sequestrants derived from collagen, keratin or casein. EP-A-
52$,$59 describes a suitable alkyl iminodiacetic acid sequestrant. Dipicolinic
acid
and 2-phosphonobutane-1,2,4-tricarboxylic acid are alos suitable. Glycinamide-
N,N'-disuccinic acid (GADS), ethylenediamine-N-N'-diglutaric acid (EDDG) and 2-
hydroxypropylenediamine-N-N'-disuccinic acid (HPDDS) are also suitable.
Especially preferred are diethylenetriamine pentacetic acid, ethylenediamine-
N,N'-
disuccinic acid (EDDS) and 1,1 hydroxyethane diphosphonic acid or the alkali
metal, alkaline earth metal, ammonium, or substituted ammonium salts thereof,
or
mixtures thereof.
En_ zyme
Another preferred ingredient useful in the components or compositions herein
is one or
more additional enzymes.
Preferred additional enzymatic materials include the commercially available
lipases,
cutinases, amylases, neutral and alkaline proteases, cellulases, endolases,
esterases,
pectinases, lactases and peroxidases conventionally incorporated into
detergent
components or compositionss. Suitable enzymes are discussed in US Patents
3,519,570
and 3,533,139.
Preferred commercially available protease enzymes include those sold under the
tradenames Alcalase, Savinase, Primase, Durazym, and Esperase by Novo
Industries A/S
(Denmark), those sold under the tradename Maxatase, Maxacal and Maxapem by
Gist-
Brocades, those sold by Genencor International, and those sold under the
tradename
Opticlean and Optimase by Solvay Enzymes. Protease enzyme may be incorporated
into
the compositions in accordance with the invention at a level of from 0.0001 %
to 4%
active enzyme by weight of the composition.
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Preferred amylases include, for example, a-amylases obtained from a special
strain of B
licheniformis, described in more detail in GB-1,269,839 (Novo). Preferred
commercially
available amylases include for example, those sold under the tradename
Rapidase by Gist-
Brocades, and those sold under the tradename Termamyl, Duramyl and BAN by Novo
Industries A/S. Highly preferred amylase enzymes maybe those described in PCT/
US
9703635, and in W095/26397 and W096/23873.
Amylase enzyme may be incorporated into the composition in accordance with the
invention at a level of from 0.0001 % to 2% active enzyme by weight of the
composition.
Lipolytic enzyme may be present at levels of active lipolytic enzyme of from
0.0001% to
''°,% by weight, preferably 0.001 % to 1 % by weight, most preferably
from 0.001 % to 0.5%
by «~eight of the compositions.
The lipase may be fungal or bacterial in origin being obtained, for example,
from a Iipase
producing strain of Humicola sp., Thermomvces sp. or Pseudomonas sp. including
Pseudomonas pseudoalcali eves or Pseudomas fluorescens. Lipase from chemically
or
genetically modified mutants of these strains are also useful herein. A
preferred lipase is
derived from Pseudomonas pseudoalcaliQenes, which is described in Granted
European
Patent, EP-B-0218272.
Another preferred lipase herein is obtained by cloning the gene from Humicola
lanuginosa
and expressing the gene in Asper~illus orna, as host, as described in European
Patent
Application, EP-A-0258 068, which is commercially available from Novo Industri
A/S,
Bagsvaerd, Denmark, under the trade name Lipoiase. This lipase is also
described in U.S.
Patent 4,810,414, Huge-Jensen et al, issued March 7, 1989.
Organic Polymeric Compound
Organic polymeric compounds are preferred additional components of the
components or
compositions herein and are preferably present as components of any
particulate
components where they may act such as to bind the particulate component
together. By
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organic polymeric compound it is meant herein essentially any polymeric
organic
compound commonly used as dispersants, and anti-redeposition and soil
suspension
agents in detergent components or compositionss, including any of the high
molecular
weight organic polymeric compounds described as clay flocculating agents
herein,
including quaternised ethoxylated (poly) amine clay-soil removal/ anti-
redeposition agent
in accord with the invention.
Organic polymeric compound is typically incorporated in the detergent
compositions of
the invention at a level of from 0.01 % to 30%, preferably from 0.1 % to 15%,
most
preferably from 0.5% to 10% by weight of the compositions.
Examples of organic polymeric compounds include the water soluble organic homo-
or
co-polymeric polycarboxylic acids or their salts in which the polycarboxylic
acid
comprises at least two carboxyl radicals separated from each other by not more
than two
carbon atoms. Polymers of the latter type are disclosed in GB-A-1,596,756.
Examples of
such salts are polyacrylates of MWt 1000-5000 and their copolymers with
malefic
anhydride, such copolymers having a molecular weight of from 2000 to 100,000,
especially 40,000 to 80,000.
The polyamino compounds are useful herein including those derived from
aspartic acid
such as those disclosed in EP-A-305282, EP-A-305283 and' EP-A-351629.
Terpolymers containing monomer units selected from malefic acid, acrylic acid,
polyaspartic acid and vinyl alcohol, particularly those having an average
molecular weight
of from 5,000 to 10,000, are also suitable herein.
Other organic polymeric compounds suitable for incorporation in the detergent
components or compositionss herein include cellulose derivatives such as
methylcellulose, carboxymethylcellulose, hydroxypropyimethylcellulose and
hydroxyethylcellulose.
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Further useful organic polymeric compounds are the polyethylene glycols,
particularly
those of molecular weight 1000-10000, more particularly 2000 to 8000 and most
preferably about 4000.
Highly preferred polymeric components herein are cotton and non-cotton soil
release
polymer according to U.S. Patent 4,968,451, Scheibel et al., and U.S. Patent
5,415,807,
Gosselink et al., and in particular according to US application no.60/051517.
Another organic compound, which is a preferred clay dispersant/ anti-
redeposition agent,
for use herein, can be the ethoxylated cationic monoamines and diamines of the
formula:
CH3 CH3
X-(-OCH CH2)n N+-CH2-CH2-~CH2)a N+-CH2CH20~X
2 ~ b
(CH2CH20 ~ X (CH2CH20 ~ X
wherein X is a nonionic group selected from the group consisting of H, C 1-C4
alkyl or
hydroxyalkyl ester or ether groups, and mixtures thereof, a is from 0 to 20,
preferably
from 0 to 4 (e.g. ethylene, propylene, hexamethylene) b is 1 or 0; for
cationic monoamines
(b=0), n is at least 16, with a typical range of from 20 to 35; for cationic
diamines (b=1), n
is at least about 12 with a typical range of from about 12 to about 42.
Other dispersants/ anti-redeposition agents for use herein are described in EP-
B-011965
and US 4,659,802 and US 4,664,848.
Suds Suppressing System
1"he detergent compositions of the invention, when formulated for use in
machine
washing compositions, may comprise a suds suppressing system present at a
level of from
0.01 % to 15%, preferably from 0.02% to 10%, most preferably from 0.05% to 3%
by
weight of the composition.
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Suitable suds suppressing systems for use herein may comprise essentially any
known
antifoam compound, including, for example silicone antifoam compounds and 2-
alkyl
alcanol antifoam compounds.
By antifoam compound it is meant herein any compound or mixtures of compounds
which act such as to depress the foaming or sudsing produced by a solution of
a detergent
composition, particularly in the presence of agitation of that solution.
Particularly preferred antifoam compounds for use herein are silicone antifoam
compounds defined herein as any antifoam compound including a silicone
component.
Such silicone antifoam compounds also t~~pically contain a silica component.
The term
"silicone" as used herein, and in general throughout the industry, encompasses
a variety of
relatively high molecular weight polymers containing siloxane units and
hydrocarbyl
group of various types. Preferred silicone antifoam compounds are the
siloxanes,
particularly the polydimethylsiloxanes having trimethylsilyl~end blocking
units.
Other suitable antifoam compounds include the monocarboxylic fatty acids and
soluble
salts thereof. These materials are described in US Patent 2,954,347, issued
September 27,
1960 to Wavne St. John. The monocarboxylic fatty acids, and salts thereof, for
use as
suds suppressor tyically have hydrocarbyl chains of 10 to 24 carbon atoms,
preferably 12
to 18 carbon atoms. Suitable salts include the alkali metal salts such as
sodium,
potassium, and lithium salts, and ammonium and alkanolammonium salts.
Other suitable antifoam compounds include, for example, high molecular weight
fatty
esters (e.g. fatty acid triglycerides), fatty acid esters of monovalent
alcohols, aliphatic
C 1 g-C4p ketones (e.g. stearone) N-alkylated amino triazines 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, bis stearic acid amide and monostearyl di-
alkali metal
(e.g. sodium, potassium, lithium) phosphates and phosphate esters.
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A preferred suds suppressing system comprises:
(a) antifoam compound, preferably silicone antifoam compound, most preferably
a
silicone antifoam compound comprising in combination
(i) polydimethyl siloxane, at a level of from 50% to 99%,
preferably 75% to 95% by weight of the silicone antifoam
compound; and
(ii) silica, at a level of from 1 % to 50%, preferably 5% to 25% by
weight of the silicone/silica antifoam compound;
wherein said silica/silicone antifoam compound is incorporated at a level of
from
5% to 50%, preferably 10% to 40% by weight;
(b) a dispersant compound, most preferably comprising a silicone glycol rake
copolymer with a polyoxyalkylene content of 72-78% and an ethylene oxide to
propylene oxide ratio of from 1:0.9 to 1:1.1, at a level of from 0.5% to 10%,
preferably 1 % to 10% by weight; a particularly preferred silicone glycol rake
copolymer of this type is DC0544, commercially available from DOW Corning
under the tradename DC0544;
(c) an inert carrier fluid compound, most preferably comprising a C16-C18
ethoxylated alcohol with a degree of ethoxylation of from 5 to S0, preferably
8 to
15, at a level of from 5% to 80%, preferably 10% to 70%, by weight;
A highly preferred particulate suds suppressing system is described in EP-A-
0210731 and
comprises a silicone antifoam compound and an organic carrier material having
a melting
point in the range 50°C to 85°C, wherein the organic carrier
material comprises a
monoester of glycerol and a fatty acid having a carbon chain containing from
12 to 20
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carbon atoms. EP-A-0210721 discloses other preferred particulate suds
suppressing
systems wherein the organic carrier material is' a fatty acid or alcohol
having a carbon
chain containing from 12 to 20 carbon atoms, or a mixture thereof, with a
melting point of
from 45°C to 80°C.
Other highly preferred suds suppressing systems comprise polydimethylsiloxane
or
mixtures of silicone, such as polydimethylsiloxane, aluminosilicate and
polycarboxylic
polymers, such as copolymers of laic and acrylic acid.
p~~~~eric Dye Transfer Inhibitinc Aeents
The compositions herein may also comprise from 0.01% to 10 %, preferably from
0.05%
to 0.5% by weight of polymeric dye transfer inhibiting agents.
The polymeric dye transfer inhibiting agents are preferably selected from
polyamine N-
oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole,
poly~-inylpyrrolidonepolymers or combinations thereof, whereby these polymers
can be
cross-linked polymers.
Optical Bri htg~- ever
The compositions herein also optionally contain from about 0.005% to 5% by
weight of
certain types of hydrophilic optical brighteners.
Hydrophilic optical brighteners useful herein include those having the
structural formula:
R~ R2
N H H N--C
N >--N O C=C O N--CO N
N
N H H
SO M R
R, S03M 3 t
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wherein R1 is selected from anilino, N-2-bis-hydroxyethyl and NH-2-
hydroxyethyl; R2 is
selected from N-2-bis-hydroxyethyl, N-2-hydroxyethyl-N-methylamino,
morphilino,
chloro and amino; and M is a salt-forming cation such as sodium or potassitun.
When in the above formula, RI 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 tradename Tinopal-UNPA-GX by Ciba-
Geigy Corporation. Tinopal-CBS-X and Tinopal-UNPA-GX is the preferred
hydrophilic
optical brightener useful in the detergent compositions herein.
When in the above formula, RI is anilino, R~ is N-2-hydroxyethyl-N-2-
methylamino and
M is a cation such as sodium, the brightener is 4,4'-bis[(4-anilino-6-(N-2-
hydroxyethyl-N-
methylamino)-s-triazine-2-yl)aminoJ2,2'-stilbenedisulfonic acid disodium salt.
This
particular brightener species is commercially marketed under the tradename
Tinopal
SBM-GX by Ciba-Geigy Corporation.
l~Vhen in the above formula, R1 is anilino, R~ is morphilino and M is a cation
such as
sodium, the brightener is 4,4'-bis[(4-anilino-6-morphilino-s-triazine-2-
yl)amino]2,2'-
stilbenedisulfonic acid, sodium salt. This particular brightener species are
commercially
marketed under the tradename Tinopal-DMS-X and Tinopal AMS-GX by Ciba Geigy
Corporation.
Polymeric Soil Release Agent
Additional polymeric soil release agents, hereinaRer "SRA", can optionally be
employed
in the present compositions. If utilized, SRA's will generally comprise from
0.01% to
10.0%, typically from 0.1% to 5%, preferably from 0.2% to 3.0% by weight, of
the
compositions.
The additional SRP's include hydrophivally modified cellulose derivatives,
such as ester
derivatives of CMC. Also included are nonionic cellulose ethers and
derivatives.
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Preferred SRA's typically have 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, thereby serving as an anchor for the hydrophilic segments.
This can enable
stains occurring subsequent to treatment with the SRA to be more easily
cleaned in later
washing procedures.
Preferred SRA's include oligomeric terephthalate esters, typically prepared by
processes
involving at least one transesterification/oligomerization, often with a metal
catalyst such
as a titanium{IV) alkoxide. Such esters may be made using additional monomers
capable
of being incorporated into the ester structure through one, two, three, four
or more
positions, without, of course, forming a densely crosslinked overall
structure.
Suitable SRA's include a sulfonated product of a substantially linear ester
oligomer
comprised of an oligomeric ester backbone of terephthaloyl and oxyalkyleneoxy
repeat
units and allyl-derived sulfonated terminal moieties covalently attached to
the backbone,
for example as described in U.S. 4,968,451, November 6, 1990 to J.1. Scheibel
and E.P.
Gosselink. Such ester oligomers can be prepared by: (a) ethoxylating allyl
alcohol; (b)
reacting the product of (a) with dimethyl terephthalate ("DMT") and 1,2-
propylene glycol
{"PG") in a two-stage transesterification/oligomerization procedure; and (c)
reacting the
product of (b) with sodium metabisulfite in water. Other SRA's include the
nonionic end-
capped 1,2-propylene/polyoxyethylene terephthalate polyesters of U.S.
4,711,730,
December 8, 1987 to Gosselink et al., for example those produced by
transesterification/oligomerization of poly(ethyleneglycol) methyl ether, DMT,
PG and
poly(ethyleneglycol) ("PEG"). Other examples of SR.A's include: the partly-
and fully-
anionic-end-capped oligomeric esters of U.S. 4,721,580, January 26, 1988 to
Gosselink,
such as oligomers from ethylene glycol ("EG"), PG, DMT and Na-3,6-dioxa-8-
hydroxyoctanesulfonate; the nonionic-capped block polyester oligomeric
compounds of
U.S. 4,702,857, October 27, 1987 to Gosselink, for example produced from DMT,
methyl (Me)-capped PEG and EG and/or PG, or a combination of DMT, EG andlor
PG,
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Me-capped PEG and Na-dimethyl-S-sulfoisophthalate; and the anionic, especially
sulfoaroyl, end-capped terephthalate esters of U.S. 4,877,896, October 31,
1989 to
Maldonado, Gosselink et al., the latter being typical of SRA's useful in both
laundry and
fabric conditioning products, an example being an ester composition made from
m-
sulfobenzoic acid monosodium salt, PG and DMT, optionally but preferably
further
comprising added PEG, e.g., PEG 3400.
SRA's also include: simple copolymeric blocks of ethylene terephthalate or
propylene
terephthalate with polyethylene oxide or polypropylene oxide terephthalate,
see U.S.
3,959,230 to Hays, May 25, 1976 and U.S. 3,893,929 to Basadur, July 8, 1975;
cellulosic
derivatives such as the hydroxyether cellulosic polymers available as METHOCEL
from
Dow; the C 1-C4 alkyl celluloses and C4 hydroxyalkyl celluloses, see U.S.
4,000,093,
December 28, 1976 to Nicol, et al.; and the methyl cellulose ethers having an
average
degree of substitution (methyl) per anhydrogiucose unit from about 1.6 to
about 2.3 and a
solution viscosity of from about 80 to about 120 centipoise measured at
20°C as a 2%
aqueous solution. Such materials are available as METOLOSE SM100 and METOLOSE
SM200, which are the trade names of methyl cellulose ethers manufactured by
Shin-etsu
Kagaku Kogyo KK.
Additional classes of SRA's include: (I) nonionic terephthalates using
diisocyanate
coupling agents to link polymeric ester structures, see U.S. 4,201,824,
Violland et al. and
U.S. 4,240,918 Lagasse et al.; and (II) SRA's with carboxylate terminal groups
made by
adding trimellitic anhydride to known SRA's to convert terminal hydroxyl
groups to
trimellitate esters. With the proper selection of catalyst, the trimellitic
anhydride forms
linkages to the terminals of the polymer through an ester of the isolated
carboxylic acid of
trimellitic anhydride rather than by opening of the anhydride linkage. Either
nonionic or
anionic SRA's may be used as starting materials as long as they have hydroxyl
terminal
groups which may be esterified. See U.S. 4,525,524 Tung et al.. Other classes
include:
(iII) anionic terephthalate-based SRA's of the urethane-linked variety, see
U.S. 4,201,824,
Violland et al.;
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Other OQtional Ingredients
Other optional ingredients suitable for inclusion in the components or
compositionss of
the invention include perfumes, colours and filler salts, with sodium sulfate
being a
preferred filler salt.
Highly preferred compositions contain from about 2% to about 10% by weight of
an
organic acid, preferably citric acid. Also, preferably combined with a
carbonate salt,
minor amounts (e.g., less than about 20% by weight) of neutralizing agents,
buffering
agents, phase regulants, hydrotropes, enzyme stabilizing agents, poiyacids,
suds regulants,
opacifiers, anti-oxidants, bactericides and dyes, such as those described in
US Patent
4.285,841 to Barrat et al., issued August 25, 1981 (herein incorporated by
reference), can
be present.
Form of the Components or compositionss
The components or compositions herein can take a variety of physical fonms
including
liquid and solid forms such as tablet, flake, pastille and bar, and preferably
granular
forms. The components or compositions can be made via a variety of methods,
depending
on their product form. The solid compositions or components can be made by
methods
such as dry-mixing, agglomerating, compaction, or spray-drying of the various
compounds comprised in the detergent component, or mixtures of these
techniques.
It is highly preferred that the cyclic amine based polymers and the anionic
cellulose
materials herein are present in an intimate mixture. In solid compositins hor
components
herein, this mixture can be obtained by any mixing method, including
agglomeration. The
intimate mixture are preferably in the foam of a compacted, agglomerated or
spray dried
granule.
Detergent compositions and components herein preferably have a bulk density of
from
300g/litre or even 350g/litre or 450g/litre to preferably 1500g/litre or
1000g/litre or even
to 850g/litre.
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Fabric Laundering_Method
The present invention also provides a method for laundering. Such a method
employs contacting
these fabrics with an aqueous washing solution formed from an effective amount
of the detergent
components or compositions herein before described or formed from the
individual components
of such components or compositions. Contacting of fabrics with washing
solution will generally
occur under conditions of agitation although the components or compositions of
the present
invention may also be used to form aqueous unagitated soaking solutions for
fabric cleaning and
treatment. As discussed above, it is preferred that the washing solution have
a pH of less than
about 11.0, preferably it has a pH of less than 10.5 and most preferably it
has a pH of less than
9.5.
An effective amount of a high density liquid or granular detergent components
or composmons m
the aqueous wash solution in the washing machine is preferably from about 500
to about 10000
ppm or even 7000 ppm, more preferably from about 1000 to about 3000 ppm.
Fabric Conditioning and Softenine
The detergent components or compositions herein may also be used to treat and
condition fabrics
and textiles. Thus, for example, a fabric conditioning components or
compositions comprising the
cyclic amine based polymers and anionic cellulose polymers as described
herein, may be added
during the rinse cycle of a conventional home laundering operation in order to
impart the desired
fabric apacarance and integrity benefits hereinbefore described. Then,
preferably at least about
l %, preferably from about 10%, more preferably from about 20% to about 80%,
more preferably
to about 60% by weight, of the composition or component is one or more fabric
softener actives,
such as cationically charged hydrocarbons, such as C12-C22 dialkyl substitued
quaternary
anv~nonium salts andl or clays, optionaly with a flocculating polymer.
Alternatively, the composition or component herein may be present in or in the
form of a
softening and cleaning composition, such as for example described in EP-B1-
313146 and
W093/ 01267, preferably comprising additional softening ingredients, such as
clay and
optionally a flocculating polymer.
The following are chemical structures for certain cyclic amine based polymers
herein, prepared
as described in co-pending applications PCTIUS98/19143 and PCT/US98/19142.
Side reactions
expected to occur during the condensation are not shown.
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Table I
Example Material
Adduct of Imidazole-epichlorohydrin
(Ratio of imidazole:epichlorohydrin 1:1, Polymer from Example
1 I)
OH
(Idealized Structure)
Adduct of Imidazole-epichlorohydrin
(Ratio of imidazole:epichlorohydrin 1.36:1, Polymer from
Example 2)
2
OH
(Idealized Structure)
Adduct of Imidazole-epichlorohydrin
(Ratio of imidazole:epichlorohydrin 1.75:1 )
3
OH
(Idealized Structure)
Adduct of Imidazole-epichlorohydrin-tnsglycidyl ether from
glycerine (Ratio of imidazole:epichlorohydrin: trisglycidylether
2.0:1.76:0.26)
4 H
110 O OH
o"J
Idealized Structure
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Adduct of Imidazole-epichlorohydrin- -trisglycidyl ether from
glycerine(Ratio of imidazole:epichlorohydrin: -trisglycidyl ether
from glycerine 2.0:1.9:0.1)
S H
HO O OH
N~'~
J
L
Adduct of piperazine and epichlorohydrin (ratio 1:1)
-..J a
6
Adduct of piperazine and epichlorohydrin (ratio l:1), benzyl quat
I
a
7 ~ ~~d
Adduct of piperazine and epichlorohydrin (ratio 1:1) methyl quat
CH3~
' ~ d
Adduct of piperazine,morpholine and epichlorohydrin (ratio 0.9:
0.4:1.0)
g Hi
N~0
d
OH
Adduct of piperazine, piperidine and epichlorohydrin (ratio 0.9:
0.4: t .o)
n H
N N
10 d
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Adduct of piperazine, morpholine and epichlorohydrin (ratio 0.9:
0.4:1.0) methyl quat
11 ~ /-1
N O
d
OH
Adduct of piperazine, piperidine and epichlorohydrin (ratio 0.9:
0.4:1.0) methyl quat
12 ~ CH3
U N~
OH OH
Adduct of piperazine,morpholine and epichlorohydrin (ratio 0.9:
0.4:1.0) benzyl quat
13
o N~ U
'--' H L off J
Adduct of piperazine, piperidine and epichlorohydrin (ratio 0.9:
0.4:1.0) benzyl quat
14 _
U N~.
OH ~ OH
Adduct of imidazole, piperazine and epichlorohydrin (ratio 2:1:3)
OH
1 S NON
H J ~ '-
Adduct of imidazole, piperazine and epichlorohydrin (ratio 1:1:2)
OH
I 6 ~ r~ N
H ~;
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Adduct of imidazole, 1,6 diaminohexane and epichlorohydrin
(ratio 1:1:2)
17
N~ N NH
NH J
OH OH
Adduct of imidazole, dimethylaminopropylamine and
epichlorohydrin (ratio 1.02:0.34:1.0)
OH
N~~ N
18 ~ OH~L
N
H3C~ w CH3
Adduct of imidazole-epichlorohydrin and chloroacetic acid
(Ratio- 1.36:0.97:0.07)
19
Eiooc~ a'~ ~ r~ H~ rr~oooH
H
Adduct of imidazole-epichlorohydrin and chloroacetic acid
(Ratio- 1.36:0.93:0.14)
20
Hood s'~ ~/
H
Adduct of imidazole-epichlorohydrin and chloroacetic acid
(Ratio- 1.36:0.83:0.34)
21
tiooc~"' W ~ ~ ~ cooH
OH
Adduct of imidazole-epichlorohydrin and 3chlorohydroxypropyl
sulfonic acid (ratio: 1.0:0.83:0.34)
22 r:~o,s~''~.,~'Q ~j~r~~so,~.
OH ~ H N6~~I~ ~ OH
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Adduct of imidazole-epichlorohydrin and 3 chlorohydroxypropyl
sulfonic acid (ratio:1.0:0.75:0.5)
23 h~o,s N ~ r~ so,N~
off
Adduct of imidazole, piperazine and
epichlorohydrin (Ratio- 1.0:1.0:2.0) guar with 0.22 moles of
24 chloroacetate
Hoot
r
N'o ~N~ U
Adduct of imidazole, piperazine and epichlorohydrin (Ratio-
1.0:3.0:4.0) guar with 0.32 moles of chloroacetate
25 '~°°c _
N~ ~ ~ ~ ~ ~ °"
L
Adduct of imidazole, piperazine andepichlorohydrin (Ratio-
1.0:1.0:2.0) guar with 0.45 moles of chloroacetate
26 "°°~
off off
~N
JL
Adduct of imidazoie and epichlorohdrin, (ratio 1.75:1 ) oxidized
U_H/C~ rN/'~~ ~ ~N..O
27 V off V off ~/
n
Adduce of piperazine and epichlorohydrin (ratio 1:1 ) 100%
oxidized
28
~O NON O
L V
Adduct of piperazine and epichlorohydrin (ratio 1:1) 50%
oxidized
~1.~, ~--v ,~ °"
N N ~ N N
V ~~ U
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Adduct of piperazine, morpholine and epichlorohydrin (ratio
1:0.2:1 ) 100% oxidized
30 ~ N N~O N O
U ~ ~ ~ Jm
Adduct of piperazine, morpholine and epichlorohydrin (ratio
1:0.2:1 )25% methyl quat and oxidized
31 /--1 /-1 ~", g /~ i /-1
Vh ~ ~ ~h
n
Adduct of imidazole, piperazine and epichlorohydrin (ratio 1:3;4)
100% oxidized
32 ~ ~~ N~NO
off ~
Jm
L
Adduct of imidazole, piperazine and epichlorohydrin (ration
1:3;4) 50% oxidized
33 r ~o~o a, ~ off
N N N N
fi ~'~ oNJ ~ ~,
Adduct of imidazole, piperazine and epichlorohydrin (ration
1:1:2) l00% oxidized
34 ~"~ \ /'~N~ °H
Adduct of imidazole, piperazine and epichlorohydrin (ration
1:5:6) 100% oxidized
35 jo ~ o off
LJ~ ~ ~ UN
~"' J v
Adduct of imidazole, piperazine and e'pichlorohydrin (ration
1:10:11) 100% oxidized
36 r rr~~ N~N~ OH
°" ~ P
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Adduct of imidazole, piperazine andepichlorohydrin (Ratio-
1.0:3.0:4.0) quat with 0.32 moles of chloroacetate and oxidized
3 7 "°°'
N~ ~ ~ N~N ~ (~
~/ ~" U U
n
Adduct of imidazole, piperazine and epichlorohydrin (Ratio-
1.0:1.0:2.0) quat with 0.45 moles of chioroacetate and oxidized
3 8 "°°' ~
N/ 'NO OH
_~, ~J~L~ ~ ~ ~J'P
Adduct of imidazole, piperazine and epichlorohydrin (Ratio-
1.0:5.0:6.0) quat with 0.32 moles of chloroacetate and oxidized
3 9 "°°'
/_1 > off ~ /'~ ° off
N N N N
OH ~~n ~~D
Adduct of imidazole, piperazine and epichlorohydrin (Ratio-
1.0:1.0:2.0) quat with 0.45 moles of dimethyl sulfate and oxidized
40 ~ ~--~ cH, a~ ~ ~ ~ o
N~ ~~N~N
41 Adduct of imidazole, dimethylaminopropylamine and
epichlorohydrin (ratio 1.02:0.34:1.0) oxidized
OH
N ~~ N ~,,
U I
oHJ
rrL ~ J n
N
H~C~ f ~CH~
O
Abbreviations used in the effervescence component and detereent composition
examyles
LAS : Sodium linear C11-13 alkyl benzene sulfonate
LAS (I) . Potassium linear or branched C11-13 alkyl benzene sulfonate
TAS : Sodium tallow alkyl sulfate
CxyAS . Sodium C 1 x - C 1 y alkyl sulfate
C46SAS : Sodium C 14 - C 16 secondary (2,3) alkyl sulfate
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CxyEzS . Sodium C 1 x-C 1 y alkyl sulfate condensed with z moles of ethylene
oxide
CxyEz : C 1 x-C 1. y predominantly linear primary alcohol
condensed with an
average of z moles of ethylene oxide
QAS : R2.N+(CH3)2(C2H40H) with R2 = C12 - C14
QAS 1 : R2.N+(CH3)2(C2H40H) with R2 = C8 - C 11
APA : C8 - C10 amido propyl dimethyl amine
Soap : Sodium linear alkyl carboxylate derived from
an 80/20 mixture of
tallow and coconut fatty acids
Adduct x Adduct with number x according to table I
:
STS : Sodium toluene sulphonate
CFAA . C12-C14 (coco) alkyl N-methyl glucamide
TFAA : C 16-C 18 alkyl N-methyl glucamide
TPKFA : C12-C14 topped whole cut fatty acids
STPP : Anhydrous sodium tripolyphosphate
TSPP . Tetrasodium pyrophosphate
Zeolite A Hydrated sodium aluminosilicate of formula
:
Nal2(AlO2Si02)12.27H20 having a primary particle
size in the
range from 0.1 to 10 micrometers (weight expressed
on an
anhydrous basis)
NaSKS-6 . Crystalline layered silicate of formula d- Na2Si2O5
Citric acid Anhydrous citric acid.
I :
Citric acid Monohydrate citric acid,
II :
Malic acid Anhydrous malic acid, 80% having a particle size
: of from 50
microns to 100 microns, having a volume median
particle size of
75 microns
Malefic acid : Anhydrous malefic acid, 80% having a particle size of from 5
microns to 30 microns, having a volume median particle size of 15
microns
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Tartaric acid : Anhydrous tartaric acid, 80% having a particle size of from 25
microns to 75 microns, having a volume median particle size of 50
microns
Carbonate Anydrous sodium carbonate
.
Bicarbonate Anhydrous sodium bicarbonate
:
Silicate Amorphous sodium silicate (Si02:Na20 = 2.0:1
. )
Sulfate : Anhydrous sodium sulfate
Mg sulfate Anhydrous magnesium sulfate
:
Citrate : Tri-sodium citrate dihydrate of activity 86.4%
with a particle size
distribution between 425um and 850um
MA/AA : Copolymer of 1:4 maleic/acrylic acid, average
molecular weight
about 70,000
MA/AA ( 1 ) Copolymer of 4:6 maleic/acrylic acid, average
: molecular weight
about 10,000
AA . Sodium polyacryiate polymer of average molecular
weight 4,500
CMC : Sodium carboxymethyl cellulose .
Cellulose etherMethyl cellulose ether with a degree of polymerization
: of 650
available from Shin Etsu Chemicals
Protease : Proteolytic enzyme, having 3.3% by weight of
active enzyme, sold
by NOVO Industries A/S under the tradename Savinase
Protease I Proteolytic enzyme, having 4% by weight of active
. enzyme, as
descnbed in WO 95/10591, sold by Genencor Int.
Inc.
Alcalase : Proteolytic enzyme, having 5.3% by weight of
active enzyme, sold
by NOVO Industries A/S
Cellulase : Cellulytic enzyme, having 0.23% by weight of
active enzyme, sold
by NOVO Industries A/S under the tradename Carezyme
Amylase : Amylolytic enzyme, having 1.6% by weight of active
enzyme, sold
by NOVO Industries A/S under the tradename Tennamyl
120T
Lipase : Lipolytic enzyme, having 2.0% by weight of active
enzyme, sold by
NOVO Industries A/S under the tradename Lipolase
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Lipase ( 1 ) : Lipolytic enzyme, having 2.0% by weight of active enzyme, sold
by
NOVO Industries A/S under the tradename Lipolase Ultra
Endolase : Endoglucanase enzyme, having 1.5% by weight of active enzyme,
sold by NOVO Industries A/S
PB4 : Particle containing sodium perborate tetrahydrate of nominal
formula NaB02.3H2 O, the particles having a weight average
particle size of 950 microns, 85% particles having a particle size of
from 850 microns to 950 microns
PB1 : Particle containing anhydrous sodium perborate bleach of nominal
formula Na802.H 202, the particles having a weight average
particle size of 800 microns, 85% particles having a particle size of
from 750 microns to 950 microns
Percarbonate : Particle containing sodium percarbonate of nominal formula
2Na2C03.3H202, the particles having a weight average particle
size of 850 microns, 5% or less having a particle size of less than
600 microns and 2% or less having a particle size of more than
1180 microns
NOBS . Particle comprising nonanoyloxybenzene sulfonate in the form of
the sodium salt, the particles having a weight average particle size
of 750 microns to 900 microns
NAC-OBS . Particle comprising (6-nonamidocaproyl) oxybenzene sulfonate, the
particles having a weight average particle size of from 825 microns
to 875 microns
TAED . Particle containing tetraacetylethylenediamine,
DTPA . ~ Diethylene triamine pentaacetic acid
DTPMP : Diethylene triamine penta (methylene phosphonate), marketed by
Monsanto under the Tradename bequest 2060
Photoactivated : Sulfonated zinc phthlocyanine encapsulated in bleach (1)
dextrin
soluble polymer
Photoactivated : Sulfonated alumino phthlocyanine encapsulated in bleach (2)
dextrin soluble polymer
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Brightener 1 : Disodium 4,4'-bis(2-sulphostyryl)biphenyl
Brightener 2 : Disodium 4,4'-bis(4-anilino-6-morpholino-1.3.5-triazin-2
yl)amino) stilbene-2:2'-disulfonate
EDDS : Ethylenediamine-N,N'-disuccinic acid, (S,S) isomer in the form of
its sodium salt.
HEDP : 1,1-hydroxyethane diphosphonic acid
PEGx : Polyethylene glycol, with a molecular weight
of x (typically 4,000)
PEO : Polyethylene oxide, with an average molecular
weight of 50,000
TEPAE : Tetraethylenepentaamine ethoxylate
PVI : Polyvinyl imidosole, with an average molecular
weight of 20,000
PVP : Polyvinylpvrolidone polymer, with an average
molecular weight of
60,000
PVNO : Polyvinylpyridine N-oxide polymer, with an average
molecular
weight of 50,000
PVPVI : Copolymer of polyvinylpyrolidone and vinylimidazole,
with an
average molecular weight of 20,000
QEA . bis((C2H50)(C2H40)n)(CH3) -N+-C6H12-N+-(CH3)
bis((C2H50)-(C2H4 O))n, wherein n = from 20 to
30
SRP 1 : Anionically end capped poly esters
SRP 2 : Diethoxylated poly (1, 2 propylene terephtalate)
short block
polymer
PEI : Polyethyleneimine with an average molecular weight
of 1800 and
an average ethoxylation degree of 7 ethyleneoxy
residues per
nitrogen
Silicone anti foam . Polydimethylsiloxane foam controller with siloxane-
oxyalkylene copolymer as dispersing agent with a ratio of said
foam controller to said dispersing agent of 10:1 to 100:1
Opacifier : Water based monostyrene latex mixture, sold by BASF
Aktiengesellschaft under the tradename Lytron 621
Wax : Paraffin wax
Effervescence granule: any of the effervescence granules I to XII
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In the following examples all levels are quoted as % by weight of the
composition:
TABLE II
The following compositions are in accordance with the invention.
C ~- F
S ra -dried Granules
AS i 10.0 15,0 5.0 5.0 10.0
0.0
TS 1.0
BAS 5.0 .0
45AS 1.0 2.0 .0
45AE3S 1.0
dduct I or 2 2.0 0.5 1.0 1.0 3.0 5.0 1.0 1.5 0.2
TPA. HEDP and/or.3 .3 0.5 .3
EDDS
gS04 .5 .5 .1
odium citrate .0 .0
odium carbonate 10.0 7.0 15.0 10.0
odium sulphate .0 .0 .0 .0
Sodium silicate .0
1.6R
eolite A 16.0 18.0 0.0 0.0
KS-6 .0 .0
A/AA or AA 1.0 .0 11.0 .0
EG 4000 .0 1.0 1.0
EA 1.0 1.0
rightener .OS .OS .OS .OS
Silicone oil .O1 .O1 .O1 .O1
MC 1.0 .0 2.5 1.5 .5 .0 1.0 2.0 0.5
lomerate
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AS .0 .0
BAS 1.0
45AS .0
3 1.0 .5
arbonate .0 1.0 1.0 1.0
odium citrate .0
FAA
itric acid .0 1.0 1.0
EA .0 .0 1.0
SRP 1.0 1.0 .2
eolite A 15.0 6.0 15.016.0
odium silicate
EG .0
uilder A lomerates
KS-6 6.0 .0 .0 7.0 10.0
AS .0 .0 .0 .0 10.012.0
-add articulate
om onents
ffervescence granule .0 10.0 .0 5 .0 12.0 .0 .0
EA .2 .5
ACAOBS .0 4.5 .5
OBS 1.0 .0 .0 .0
AED I .5 1.5 .5 .5 1.5
BAS 8.0 8.0 .0
AS (flake) 10.0 10.0 8.0
itric acid II
ra -on
rightener .2 .2 .3 .1 .2 .1 .6 .3
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Ye .3 .OS 0.1
7 .5 .7 _
erfume 1.0 0.5 1.1 .8 0.3 .5 .3 .5
-add
itrate 0.0 .0 S.0 15.0 S.0
ercarbonate 15.0 .0 .0 10.0 4.0 18.0 .0
erborate .0 18.0
hotobleach .02 .02 .02 .1 .OS .3 .03
nzymes (cellulase,1.3 .3 .5 .5 .8 .0 .S .16 .2
mylase, protease,
lipase)
arbonate .0 10.0 .0 8.0 10.0 5.0
crfurne (encapsulated) .5 .5 .3 .2
uds suppressor 1.0 .6 .3 .10 .5 1.0 .3 1.2
~oap .5 0.2 .3 .0 .5 .3
uric acid (I or .0 .0 5.0
coarse)
yed carbonate .5 .5 1.0 .0 .5 .5 .5 1.0
(blue,
reen )
~KS-6 0___ .0
Fillers up to
100%
TABLE III
The following compositions are in accordance with the invention.
F G
S ra -Dried Granules
AS or LAS (I) 10.0 10.0 16.0 .0 .0 10.0
AS 1.0
BAS .0 5.0
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45AS 1.0 2.0 .0
4535 1.0
QAS 1.0 1.0
TPA, HEDP and/or .3 .3 0.3 .3
DDS
gS04 .5 .4 .1
Sodium citrate 10.0 12.0 17.0 .0 .0
Sodium carbonate 15.0 8.0 15.0 1 0.0
Sodium sulphate 5.0 .0 .0 .0
Sodium silicate .0
1.6R
eolite A .0
KS-6 .0 .0
A/AA or AA 1.0 .0 10.0 .0
EG 4000 .0 1.0 1.0
EA 1.0 1.0
rightener .OS .OS .OS .OS
ilicone oil .01 .Ol .O1 .O1
ffervescence granule 12
I,
II, IV VII or
VIII
lomerate
AS .0 .0 .0 .0 .0 .0
STS 1.0 1.0 1.0
45AS .0
E3 1.0 .5
arbonate .0 1.0 1.0 1.0
Sodium citrate .0
MC 1.0 1.5 0.8 2.0 1.0 .5 0.3 .8 1.5
itric acid .0 1.0 1.0
EA 1.0 .0 1.0 .0
dduct 1, 2 or .0 .3 1.5 .0 .5 1.0 1.0 .2 .5
3
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Zeolite A 15.0 6.0 5.0 16.0
1
Sodium silicate
EEG 4.0
TAED II 3.0 1.5
uilder A lomerate
SKS-6 .0 5.0 .0 .0 .0 10.0
AS .0 S.0 .0 .0 10.0 12.0
-add articulate
om onents
ffervescence granule 10.0 .0 5 15 8.0 .0 0 .0
ACAOBS .0 1.5 5.5
OBS/ LOBS/ DOBS .0 .0 .0
AED I .5 1.5 .5 .5 1.5
BAS 8.0 8.0 .0
AS (flake) 8.0
ra -on
rightener .2 .2 .3 .1 .2 .1 .6
ye .3 .OS .1
E7 .5 .7
erfume .8 .5 0.8 .5 1.0
-add
EA .2 .5
itrate .0 .0 .0 .0 15.0 .0
ercarbonate 15Ø0 .0 10.0 12.0 18.0 .0
erborate .0 18.0
hotobleach .02 .02 .02 .1 .OS .3 .03
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nzymes (cellulase,1.5 .3 .5 .5 .8 .0 0.5 0.160.2
ylase, protease,
ipase)
arbonate II .0 8.4 10.05.0
erfume (encapsulated).6 .5 .5 .3 .S .2 .1 .6
uds suppressor 1.0 .6 .3 .10 .S 1.0 .3 1.2
oap .5 .2 0.3 .0 .5 .3
itric acid II 5.0 .0
yed carbonate .5 .S .0 .5 .5 .5 1.0
(blue,
een)
SKS-6 .0 .0
fillers up to '
100%
Table IV
The following are high density and bleach-containing detergent formulations
according to
the present invention:
A $ C
Blown Powder
Zeolite A - - I5.0
Sodium sulfate 0.0 S.0 0.0
LAS 3.0 - 3.0
C45AS 3.0 2.0 4.0
QAS - - 1.5
DTPMP 0.4 0.4 0.4
CMC 0.4 0.4 0.4
MA/AA 4.0 2.0 2.0
effervescence granule I or 7.0 - -
VIII
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__ TAED - - 3.0
Agglomerates -'
CMC - 1.0 1.5
Adduct 1 or 2 - 0.5 0.8
LAS - 11.0 7.0
TAS or STS 2.0 2.0 1.0
Silicate 3.0 - 4.0
Zeolite A 8.0 8.0 8.0
Carbonate 8.0 8.0 4.0
Agglomerate
Adduct 1 or 2 1.0 - _
CMC 3.0 - _
Spray On
Perfume 0.3 0.3 0.3
C25E3 2.0 - 2.0
brightener 0.1 0.4
photobleach 0.03 0.05
Dry additives
QEA 1.0 0.5 0.5
Citric acid I 5.0 - 2.0
Bicarbonate I - 3.0 _
Carbonate II 8.0 15.0 10.0
NAC OBS 6.0 - 5.0
Manganese catalyst - - 0.3
TAED I 3.0
NOBS - 2.0 -
Percarbonate 14.0 7.0 10.0
Polyethylene oxide of MW - - 0.2
5,000,000
Bentonite clay - - 10.0
effervescnece granule - 5.5 7.5
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Protease 1.0 ~ 1.0 1.0
Lipase 0.4 0.4 0.4
Amylase 0.6 0.6 0.6
Cellulase 0.6 0.6 0.6
Silicone antifoam 5.0 5.0 5.0
Balance (Moisture and 100.0 100.0 100.0
Miscellaneous)
Density (g/litre) 850 850 850
Table V
The following liquid composition is in accord with the invention
Component Wt. % Wt. % ~~Wt.
~
C12-l5 alkyl ether (2.5) 38 38 38
sulfate
C 12 glucose amide 6.86 6.86 6.86
Citric Acid 4.75 4.75 4.75
C12-14 Fatty Acid 2.00 2.00 2.00
Enrymes 1.02 1.02 i .02
MEA 1.0 1.0 1.0
Propanediol 0.36 0.36 0.36
Borax 6.58 6.58 6.58
Dispersant 1.48 1.48 1.48
Na Toluene Sulfonate 6.25 6.25 6.25
Adduct 1 , 2, 4 or 5 I .0 0.5 2.0
CMC 1.0 2.5 0.5
Dye, Perfume. Brighteners, Balance Balance Balance
Preservatives,
Suds Suppressor, Other Minors,
Water
100% 100% 100%
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Table VI
The following liquid detergent formulations are prepared according to the
present invention
A B C D E
LAS 11.5 9.0 - 4.0 -
C25E2.SS - 3.0 18.0 - 16.0
C45E2.25S 11.5 3.0 - 16.0 -
C23E9 - 3.0 2.0 2.0 1.0
C23E7 3.2 - - - -
CFAA - - 5.0 - 3.0
TPKFA 2.0 - 2.0 0.5 2.0
Citric (50%) 6.5 1.0 2.5 4.0 2.5
Ca formate 0.1 0.06 0.1 - -
Na formate 0.5 0.06 0.1 0.05 0.05
STS 4.0 1.0 3.0 1.2 -
Borate 0.6 - 3.0 2.4 3.0
Na hydroxide 6.0 2.0 3.5 4.0 3.0
Ethanol 2.0 1.0 4.0 4.0 3.0
1.2 Propanediol3.0 2.0 8.0 8.0 5.0
Monoethanolamine3.0 1.5 1.0 2.5 1.0
CMC 2.0 1.0 1.0 3.0 0.4
Adduct 1, 2 0.3 1.0 2.0 0.8 1.0
or 6
Protease 0.03 0.01 0.03 0.02 0.02
Lipase - - 0.002 - -
Amylase - - - 0.00 -
2
Cellulase - - 0.000 0.00 0.0001
2 OS
S~ 0.2 - 0.1 -
DTPA - - 0.3 - -
P~D - - 0.3 - 0.2
Brightener 1 0.2 0.07 0.1 - -
Silicone antifoam0.04 0.02 0.1 0.1 0.1 Miscellaneous
and water
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Table VII
The following liquid detergent formulations are according to the present
invention
A B C D E F G H
LAS 10.0 13.0 9.0 - 25.0 - - -
C25AS 4.0 1.0 2.0 10.0 - 13.0 18.0 15.0
C25E3S 1.0 - - 3.0 - 2.0 2.0 4.0
C25E7 6.0 8.0 13.0 2.5 - - 4.0 4.0
TFAA - - - 4.5 - 6.0 8.0 8.0
APA - 1.4 - - 3.0 1.0 2.0 -
TPKFA 2.0 - 13.0 7.0 - 15.0 11.0 11.0
Citric 2.0 3.0 1.0 1.5 1.0 1.0 1.0 1.0
Dodecenyl12.0 10.0 - - 15.0 - - -
tetradeceny
I succinic
acid
Rapeseed 4.0 2.0 1.0 - 1.0 - 3.5 -
fatty
acid
Ethanol 4.0 4.0 7.0 2.0 7.0 2.0 3.0 2.0
1,2 4.0 4.0 2.0 7.0 6.0 8.0 10.0 13.0
Propanedio
1
Monoethan- - - 5.0 - - 9.0 9.0
olamine
Triethanola- - 8.0 - - - 0.4 0.3
mine
CMC 0.2 2.0 0.5 0.7 2.0 1.2 1.0 4.0
Adduct 0.3 0.4 0.5 1.0 1.0 2.0 0.5 1.0
1
or 2
DETPMP 1.0 1.0 0.5 1.0
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Carbohydra 0.08 0.02 0.01 0.02
se
Protease 0.02 0.02 0.01 .008 - - .003 .003
Lipase - .002 - .002 .004 0.01 0.01 0.01
Amylase .004 .004 0.01 .008 - - .004 .003
Cellulase- - - .002 - - 0.2 0.1
SRP 2 0.3 - 0.3 0.1 1.0 1.5 2.5 2.5
Boric 0.1 0.2 1.0 2.0 4.0 4.0 - -
acid
Ca chloride- 0.02 - 0.01 0.1 0.2 0.3 -
Brightener- 0.4 - - 0.4 - - -
1
Suds 0.1 0.3 - 0.1 0.8 0.7 - -
suppressor
Opacifier0.5 0.4 - 0.3 8.0 7.5 8.0 8.2
NaOH up 8.0 8.0 7.6 7.7
to pH Miscell
aneous
and
water
