Note: Descriptions are shown in the official language in which they were submitted.
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LAUNDRY DETERGENT COMPOSITIONS WITH A COMBINATION OF CYCLIC
AMINE BASED POLYMERS AND HYDROPHOBICALLY MODIFIED CARBOXY
METHYL CELLULOSE
TECHNICAL FIELD
The present invention relates to compositions, in either liquid or granular
form, for use in
laundry applications, wherein the compositions comprise certain cyclic amine
based polymer,
oligomer or copolymer materials in combination with hydrophobically modified
carboxy methyl
cellulose. This combination imparts appearance and integrity benefits to
fabrics and textiles
laundered in washing solutions formed from such compositions.
BACKGROUND OF THE INVENTION
It is, of course, well known that altemating cycles of using and laundering
fabrics and
textiles, such as articles of worn clothing and apparel, will inevitably
adversely affect the
appearance and integrity of the fabric and textile items so used and
laundered. Fabrics and
textiles simply wear out over time and with use. Laundering of fabrics and
textiles is necessary
to remove soils and stains which accumulate therein and thereon during
ordinary use. However,
the laundering operation itself, 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. 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
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function. The present invention is directed to the use of a mixture of certain
cyclic amine based
polymer, oligomer or copolymer materials and hydrophobically modified carboxy
methyl
cellulose (CMC) in laundry applications that perform in this desired manner.
SUMMARY OF THE INVENTION
The present invention is directed to a detergent composition comprising:
a) from about 1% to about 80% by weight of surfactants selected from the group
consisting of nonionic, anionic, cationic, amphoteric zwitterionic surfactants
and
mixtures thereof; and
b) at least about 0.01 /a, preferably at least about 0.1%, most preferably at
least
about 0.5% and less than about 50%, preferably less than about 25.0%, most
preferably less than about 5.0%, by weight, of a mixture of cyclic amine based
polymers, oligomers or copolymers and hydrophobically modified
carboxymethylcellulose based polymers.
The cyclic amine based polymer, oligomer or copolymer materials which are
suitable for
use in laundry operations and provide the desired fabric appearance and
integrity benefits 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, C 1-C 12
alkyl, substituted alkyl,
C7-C12 alkylaryl,
-(CH2)hCOOM, -(CH2)hSO3M, CH2CH(OH)SO3M, -(CH2)hOSO3M,
COOM
/ COOM
-CH
CH-COOM _CH OOM COOM -CH2 COOM
/ \ ~
pH CHZ-COOM -CH~COOM
COOM
Rt\ R,
, and -R2Q;
-wherein W comprises at least one cyclic constituent selected from the group
consisting of:
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(R3)c (R3)C D (R3)c (R3)c
I N-D N/ \N D-N R4
R3 (D)/ I R3 N' N
q q , U and
R4
N"
in addition to the at least one cyclic constituent, W may also comprise an
aliphatic or
substituted aliphatic moiety of the general structure;
i 3)c 1R3
N-B N--
I
LR3 JqR3
-each B is independently C 1-C 12 alkylene, C 1-C 12 substituted alkylene, C3-
C 12 alkenylene, Cg-
C 12 dialkylarylene, Cg-C 12 dialkylarylenediyl, and -(R5O)nR5- ;
-each D is independently C2-C6 alkylene;
-each Q is independently selected from the group consisting of hydroxy, C 1-C
18 alkoxy, C2-C 18
hydroxyalkoxy, amino, C 1-C 18 alkylamino, dialkylamino, trialkylamino 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 R2 is independently selected from the group consisting of C 1-C 12
alkylene, C 1-C 12
alkenylene, -CH2-CH(0R l)-CH2, Cg-C 12 alkarylene, C4-C12 dihydroxyalkylene,
poly(C2-C4 alkyleneoxy)alkylene, H2CH(OH)CH2OR2OCH2CH(OH)CH2-, and C3-
C 12 hydrocarbyl moieties;
provided that when R, is a C3-C12 hydrocarbyl moiety the hydrocarbyl moiety
can
comprise from about 2 to about 4 branching moieties of the general structure:
OH
-~-OR5 )F~-CH-)-CH-CHHtW-R21W-T
x
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-each R3 is independently selected from the group consisting of H, 0, R2, Cl-
C20 hydroxyalkyl,
C I-C20 alkyl, substituted alkyl, C6-C I I aryl, substituted aryl, CTC 11
alkylaryl, C I-C20
aminoalkyl,
-(CH2)hCOOM, -(CH2)hSO3M, CH2CH(OH)SO3M, -(CH2)hOSO3M,
COOM
-CH COOM COOM
CH-COOM --CH COOM -CHZCOOM
/ \ COOM
OH CHZ-COOM , -CH2 and COpM
-each R4 is independently selected from the group consisting of H, C 1-C22
alkyl, C I-C22
hydroxyalkyl, aryl and C7-C22 alkylaryl;
-each R5 is independently selected from the group consisting of C2-C8
alkylene, C2-C8 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 1;
each h is independently from about I to about 8;
each q is independently from 0 to about 6;
each n is independently from I to about 20;
each r is independently from 0 to about 20; and
each t is independently from 0 to 1.
Cellulosic based polymer or oligomer materials which are suitable for use in
laundry
operations and provide the desired fabric appearance and integrity benefits
can be characterized
by the following general formula:
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R
Oz
R
O O~ R
O RO
RO O
O
R
R%
wherein each R is selected from the group consisting of R2, Rc, and
CH-) CH O RH
R2 t
wherein:
- each R2 is independently selected from the group consisting of H and C 1-C4
alkyl;
0
11
- each Rc is -(CH2)y-C-OZ
wherein each Z is independently selected from the group consisting of M, R2,
Rc, and RH;
- each RH is independently selected from the group consisting of C5 -C20
alkyl, C5-C7
cycloalkyl, C7-C20 alkylaryl, C7-C20 arylalkyl, substituted alkyl,
hydroxyalkyl, Cl-C20
alkoxy-2-hydroxyalkyl, C7-C20 alkylaryloxy-2-hydroxyalkyl, (R4)2N-alkyl,
(R4)2N-2-
hydroxyalkyl, (R4)3 N-alkyl, (R4)3 N-2-hydroxyalkyl, C6-C12 aryloxy-2-
hydroxyalkyl,
-
O R5 0 R5 0 CH CO-OM
C CH C CH2 - CH
2 , and
O R5 0
-C-CH-CH2-C-0M.
,
- each R4 is independently selected from the group consisting of H, Cl-C20
alkyl, CS-C7
cycloalkyl, C7-C20 alkylaryl, C7-C20 arylalkyl, aminoalkyl, alkylaminoalkyl,
dialkylaminoalkyl, piperidinoalkyl, morpholinoalkyl, cycloalkylaminoalkyl and
hydroxyalkyl;
- each R5 is independently selected from the group consisting of H, Cl -C20
alkyl, C5-C7
cycloalkyl, C7-C20 alkylaryl, CTC20 arylalkyl, substituted alkyl,
hydroxyalkyl,
(R4)2N-alkyl, and (R4)3 N-alkyl;
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wherein:
M is a suitable cation selected from the group consisting of Na, K, 1/2Ca, and
1/2Mg;
each x is from 0 to about 5;
each y is from about 1 to about 5; and
provided that:
- the Degree of Substitution for group RH is between about 0.0005 and 0.1,
more preferably
between about 0.005 and 0.05, and most preferably between about 0.01 and 0.05;
- the Degree of Substitution for group Rc wherein Z is H or M is between about
0.2 and 2.0,
more preferably between about 0.3 and 1.0, and most preferably between about
0.4 and
0.7;
- if any RH bears a positive charge, it is balanced by a suitable anion; and
- two R4's on the same nitrogen can together form a ring structure selected
from the group
consisting of piperidine and morpholine.
The cyclic amine based polymer, oligomer or copolymer materials defined above
can be
used, along with the hydrophobically modified cellulosic based polymers or
oligomers, as a
%vashing solution additive in either granular or liquid form. Alterr-atively,
they can be admixed to
granular detergents, dissolved in liquid detergent compositions or added to a
fabric softening
composition.
The ratio of the hydrophobically modified cellulosic to cvclic amine based
polymer,
oligomer or copolymer materials is within the range of 1000:1 to 1:1000 and is
preferably
between 100:1 to 50:1, more preferably between 50:1 to 1:1, even more
preferably between 10:1
to 1:1.
The laundry detergent compositions herein comprise from about 1% to 80% by
weight of
a detetsive surfactant, optionally from about 0.01% to 80% by weight of an
otganic or inorganic detetgency
builder and from about 0.01% to 5% by weight of the mixture of cyclic amine
based polymers,
oligomers or copolymers and hydrophobically modified cellulosic based polymers
or oligomers
based fabric treatment materials of the present invention. The detersive
surfactant and
detergency builder materials can be any of those useful in conventional
laundry detergent
products.
Aqueous solutions of the mixture of cyclic amine based polymers, oligomers or
copolymers
and hydrophobically modified cellulosic based polymers or oligomers of the
subject invention
comprise from about 0.01% to 80% by weight of the mixture of cyclic amine
based polymers,
oligomers or copolymers and hydrophobically modified cellulosic based polymers
or oligomers
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fabric treatment materials dissolved in water and other ingredients such as
stabilizers and pH
adjusters.
The invention also provides for a laundry additive composition comprising from
1% to 80%
by weight of water and from 0.01% to 5.0%, preferably from 0.1% to 4.0%, by
weight of a mixture
of cyclic amine based polymers, oligomers or copolymers and hydrophobically
modified
carboxymethylcellulose based polymers.
In its method aspect, the present invention relates to the laundering or
treating of fabrics and
textiles in aqueous washing or treating solutions formed from effective
amounts of the detergent
compositions described herein, or formed from the individual components of
such compositions.
Laundering of fabrics and textiles in such washing solutions, followed by
rinsing and drying, imparts
fabric appearance benefits to the fabric and textile articles so treated. Such
benefits can include
improved overall appearance, pill/fuzz reduction, antifading, improved
abrasion resistance, and/or
enhanced softness. It has been surprisingly determined that the mixture of
cyclic amine based
polymers, oligomers or copolymers and hydrophobically modified cellulosic
based polymers or
oligomers according to this invention imparts fabric appearance and integrity
benefits that are greater
than the benefits achieved by a corresponding amount of either component by
itself.
DETAILED DESCRIPTION OF THE INVENTION
As noted, when fabric or textiles are laundered in wash solutions which
comprise the
mixture of cyclic amine based polymers, oligomers or copolymers and
hydrophobically modified
cellulosic based polymers or oligomers of the present invention fabric
appearance and intearity are
enhanced. The mixture of cyclic amine based polymers, oligomers or copolymers
and
hydrophobically modified cellulosic based polymers or oligomers can be added
to wash solutions by
incorporating them into a detergent composition, a fabric softener or by
adding them separately to
the washinQ solution. The mixture of cyclic amine based polymers, oligomers or
copolymers and
hydrophobically modified cellulosic based polymers or oligomers are described
herein primarily as
liquid or granular detergent additives but the present invention is not meant
to be so limited. The
mixture of cyclic amine based polymers, oligomers or copolymers and
hydrophobically modified
cellulosic based polymers or oligomers, detergent composition components,
optional ingredients for
such compositions and methods of using such compositions, are described in
detail below. All
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percentages are by weight unless otherwise specified.
A) Cyclic amine Based Polymer, Oligomer or Copolymer Materials
An essential component of the compositions of the present invention comprises
one or more
cyclic amine based polymer, oligomer or copolymer. Such materials have been
found to impart a
number of appearance benefits to fabrics and textiles laundered in aqueous
washing solutions formed
from detergent compositions which contain a mixture of cyclic amine based
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polymers, oligomers or copolymers and hydrophobically modified cellulosic
based polymers or
oligomers fabric treatment materials. Such fabric appearance benefits can
include, for example,
improved overall appearance of the laundered fabrics, reduction of the
formation of pills and
fuzz, protection against color fading, improved abrasion resistance, etc. The
cyclic amine based
fabric treatment materials used in the compositions and methods herein can
provide such fabric
appearance benefits with acceptably little or no loss in cleaning performance
provided by the
laundry detergent compositions into which such materials are incorporated.
The cyclic amine based polymer, oligomer or copolymer component of the
compositions
herein 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 amine based fabric treatment
materials can vary within
the mixture as is illustrated in the Examples below.
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 are polymers or oligomers wherein two or more
dissimilar monomers
have been simultaneously or sequentially polymerized. Copolymers 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.
The mixture of cyclic amine based polymers, oligomers or copolymers and
hydrophobically
modified cellulosic based polymers or oligomers of the detergent compositions
herein will
generally comprise from about 0.01% to about 5% by the weight of the detergent
composition.
More preferably, the mixture of cyclic amine based polymers, oligomers or
copolymers and
hydrophobically modified cellulosic based polymers or oligomers will comprise
from about 0.1%
to about 4% by weight of the detergent compositions, most preferably from
about 0.75% to about
3%. However, as discussed above, when used as a washing solution additive,
i.e. when mixture
of cyclic amine based polymers, oligomers or copolymers and hydrophobically
modified
cellulosic based polymers or oligomers is not incorporated into a detergent
composition, the
concentration of mixture of cyclic amine based polymers, oligomers or
copolymers and
hydrophobically modified cellulosic based polymers or oligomers can comprise
from about 0.1%
to about 80% by weight of the additive material.
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Cyclic aniine based polymer, oligomer or copolymer materials which are
suitable for use
in laundry operations and provide the desired fabric appearance and integrity
benefits can be
characterized by the general formula given in the Summary of the Invention.
Preferred compounds that fall within this general structure include compounds:
- wherein each R1 is H; and
-at least one W is selected from the group consisting of:
(R3)c (R3)C (R3)C (R3)c
1/~/ I
N-D N N D-N
\-_j 1
R3 R3
q q ,
r(R3)c (R3)C (R3)c (R3)c
N-D NN D-N R4
t J
R3 R3 N N
q q , U and
Ra
N `_N
u
Even more preferred compounds for the fabric appearance and integrity benefits
are
those:
-wherein each R1 is H; and
-at least one W is selected from the group consisting of:
(R3)c (R3)c
I ~~ I R4
1-D D-~3) c ~3)c I N N'/
3 R3 and
R4
N" N'I,-
U
And most preferred compounds for the fabric appearance and integrity benefits
are those:
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-wherein each Rl is H; and
-at least one W is selected from the group consisting of:
R4 Ra
/ N Nl--*'
t~l and
Preferred compounds to be used as the linking group R2 include, but are not
limited to:
polyepoxides, ethylenecarbonate, propylenecarbonate, urea, a, 0-unsaturated
carboxylic acids,
esters of a, P-unsaturated carboxylic acids, amides of a, P-unsaturated
carboxylic acids,
anhydrides of a, P-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, glycidyihalogens, 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 polyalkyleneglycols with a, P-unsaturated carboxylic
acids, esters of a, P-
unsaturated carboxylic acids, amides of a, P-unsaturated carboxylic acids and
anhydrides of a, 0-
unsaturated carboxylic acids provided that the reaction products contain at
least two double
bonds, two carboxylic groups, two amide groups or two ester groups.
Additionally preferred cyclic amine based polymer, oligomer or copolymer
materials 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.
These cyclic amine based polymers can be linear or branched. One specific type
of
branching can be intorduced using a polyfunctional crosslinking agent. An
example of such such
polymer is exemplified below.
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T
i
t(2
x
H
HO O OH
T~R2- W_(~ la~O~,~W - R2 T
1x~'
B) Hydrophobically Modified Cellulosic Based Polymers or Oli ol; mers
The essential component of the compositions of the present invention comprises
one or
more cellulosic based polymer or oligomer. Such materials have been found to
impart a number
of appearance benefits to fabrics and textiles laundered in aqueous washing
solutions formed
from detergent compositions which contain such cellulosic based fabric
treatment materials.
Such fabric appearance benefits can include, for example, improved overall
appearance of the
laundered fabrics, reduction of the formation of pills and fuzz, protection
against color fading,
improved abrasion resistance, etc. The cellulosic based fabric treatment
materials used in the
compositions and methods herein can provide such fabric appearance benefits
with acceptably
little or no loss in cleaning perfonmance provided by the laundry detergent
compositions into
which such materials are incorporated.
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. One suitable type of cellulosic based polymer or oligomer fabric
treatment material
for use herein has an average molecular weight of from about 5,000 to about
2,000,000,
preferably from about 50,000 to about 1,000,000.
The cellulosic based fabric treatment component of the detergent compositions
herein will
generally comprise from about 0.1% to about 5% by the weight of the detergent
composition.
More preferably, such cellulosic based fabric treatment materials will
comprise from about 0.5%
to about 4% by weight of the detergent compositions, most preferably from
about 0.75% to about
3%. However, as discussed above, when used as a washing solution additive,
i.e. when the
cellulosic based fabric treatment component is not incorporated into a
detergent composition, the
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concentration of the cellulosic based component can comprise from about 0.1 %
to about 80% by
weight of the additive material.
One suitable group of cellulosic based polymer or oligomer materials for use
herein is
characterized by the following formula:
R
Oz
R
0 O,, R
O RO
RO O
O
/O
R ;
wherein each R is selected from the group consisting of R2, Rc, and
CH, CH O RH
R,
- t
wherein:
- each R2 is independently selected from the group consisting of H and C1-C4
alkyl;
0
Ii
- each Rc is -(CH2)y-C-OZ,
wherein each Z is independently selected from the group consisting of M, R2,
Rc, and RH;
- each RH is independently selected from the group consisting of C5 -C20
alkyl, C5-C7
cycloalkyl, C7-C20 alkylaryl, C7-C20 arylalkyl, substituted alkyl,
hydroxyalkyl, C1-C20
alkoxy-2-hydroxyalkyl, C7-C20 alkylaryloxy-2-hydroxyalkyl, (R4)2N-alkyl,
(R4)2N-2-
hydroxyalkyl, (R4)3 N-alkyl, (R4)3 N-2-hydroxyalkyl, C6-C 12 aryloxy-2-
hydroxyalkyl,
O RS 0 R5 0 R5 0
-C CH C CH2 -C CH2 CH C-OM
and
O R5 0
-C-CH-CHZ-C-OM.
,
- each R4 is independently selected from the group consisting of H, C1-C20
alkyl, C5-C7
cycloalkyl, C7-C20 alkylaryl, C7-C20 arylalkyl, aminoalkyl, alkylaminoalkyl,
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dialkylaminoalkyl, piperidinoalkyl, morpholinoalkyl, cycloalkylaminoalkyl and
hydroxyalkyl;
- each R5 is independently selected from the group consisting of H, CI -C20
alkyl, C5-C7
cycloalkyl, C7-C20 alkylaryl, C7-C20 arylalkyl, substituted alkyl,.
hydroxyalkyl,
(R4)2N-alkyl, and (R4)3 N-alkyl;
wherein:
M is a suitable cation selected from the group consisting of Na, K, 1/2Ca, and
1/2Mg;
each x is from 0 to about 5;
each y is from about I to about 5; and
provided that:
- the Degree of Substitution for group RH is between about 0.0005 and 0.1,
more preferably
between about 0.005 and 0.05, and most preferably between about 0.01 and 0.05;
- the Degree of Substitution for group Rc wherein Z is H or M is between about
0.2 and 2.0,
more preferably between about 0.3 and 1.0, and most preferably between about
0.4 and
0.7;
- if any RH bears a positive charge, it is balanced by a suitable anion; and
- two R4's on the same nitrogen can together form a ring structure selected
from the group
consisting of piperidine and morpholine.
The "Degree of Substitution" for group RH, which is sometimes abbreviated
herein
"DSRõ", means the number of moles of group RH components that are substituted
per anhydrous
glucose unit, wherein an anhydrous glucose unit is a six membered ring as
shown in the repeating
unit of the general structure above.
The "Degree of Substitution" for group Rc, which is sometimes abbreviated
herein
"DSRC", means the number of moles of group Rc components, wherein Z is H or M,
that are
substituted per anhydrous glucose unit, wherein an anhydrous glucose unit is a
six membered ring
as shown in the repeating unit of the general structure above. The requirement
that Z be H or M
is necessary to insure that there are a sufficient number of carboxy methyl
groups such that the
resulting polymer is soluble. It is understood that in addition to the
required number of Rc
components wherein Z is H or M, there can be, and most preferably are,
additional Rc
components wherein Z is a group other than H or M.
The production of materials according to the present invention is further
defined in the
Examples below.
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C) Detersive Surfactant
The detergent compositions herein comprise from about 1% to 80% by weight of a
detersive surfactant. Preferably such compositions comprise from about 5% to
50% by weight of
surfactant. Detersive surfactants utilized can be of the anionic, nonionic,
zwitterionic,
ampholytic or cationic type or can comprise compatible mixtures of these
types. Detergent
surfactants useful herein are described in U.S. Patent 3,664,961, Norris,
issued May 23, 1972,
U.S. Patent 3,919,678, Laughlin et al., issued December 30, 1975, U.S. Patent
4,222,905,
Cockrell, issued September 16, 1980, and in U.S. Patent 4,239,659, Murphy,
issued December
16, 1980. Of all the surfactants, anionics and nonionics are preferred.
Useful anionic surfactants can themselves be of several different types. For
example,
water-soluble salts of the higher fatty acids, i.e., "soaps", are useful
anionic surfactants in the
compositions herein. This includes alkali metal soaps such as the sodium,
potassium,
ammonium, and alkylolammonium salts of higher fatty acids containing from
about 8 to about 24
carbon atoms, and preferably from about 12 to about 18 carbon atoms.
Additional non-soap anionic surfactants which are suitable for use herein
include the water-
soluble salts, preferably the alkali metal, and ammonium salts, of organic
sulfuric reaction
products having in their molecular structure an alkyl group containing from
about 10 to about 20
carbon atoms and a sulfonic acid or sulfuric acid ester group. (Included in
the term "alkyl" is the
alkyl portion of acyl groups.) Especially valuable are linear straight chain
alkylbenzene
sulfonates in which the average number of carbon atoms in the alkyl group is
from about 11 to
13, abbreviated as C11-13 LAS.
Preferred nonionic surfactants are those of the formula Rl(OC2H4)nOH, wherein
R1 is a
C 10-C 16 alkyl group or a C8-C 12 alkyl phenyl group, and n is from 3 to
about 80. Particularly
preferred are condensation products of C12-C15 alcohols with from about 5 to
about 20 moles of
ethylene oxide per mole of alcohol, e.g., C12-C13 alcohol condensed with about
6.5 moles of
ethylene oxide per mole of alcohol.
Additional suitable surfactants, including polyhydroxy fatty acid amides and
amine based
surfactants, are disclosed in co-pending PCT Application W098/14300, Published
March 25,
1999, entitled Laundry Detergent Compositions with Cyclic Amine Based Polymers
to Provide
Appearance and Integritv Benefits to Fabrics Laundered Therewith, which was
filed on
September 15, 1997, in the name of Panandiker et al.
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D) Detergent Builder
The detergent compositions herein may also comprise from about 0.1% to 80% by
weight
of a detergent builder. Preferably such compositions in liquid form will
comprise from about 1%
to 10% by weight of the builder component. Preferably such compositions in
granular form will
comprise from about 1% to 50% by weight of the builder component. Detergent
builders are
well known in the art and can comprise, for example, phosphate salts as well
as various organic
and inorganic nonphosphorus builders.
Water-soluble, nonphosphorus organic builders useful herein include the
various alkali
metal, ammonium and substituted ammonium polyacetates, carboxylates,
polycarboxylates and
polyhydroxy sulfonates. Suitable polycarboxylates for use herein are the
polyacetal carboxylates
described in U.S. Patent 4,144,226, issued March 13, 1979 to Crutchfield et
al., and U.S. Patent
4,246,495, issued March 27, 1979 to Crutchfield et al. Particularly preferred
polycarboxylate
builders are the oxydisuccinates and the ether
carboxylate builder compositions comprising a combination of tartrate
rnonosuccinate and
tartrate disuccinate described in U.S. Patent 4,663,071, Bush et al., issued
May 5, 1987.
Examples of suitable nonphosphorus, inorganic builders include the silicates,
aluminosilicates, borates and carbonates. Particularly preferred are sodium
and potassium
carbonate, bicarbonate, sesquicarbonate, tetraborate decahydrate, and
silicates having a weight
ratio of Si02 to alkali metal oxide of from about 0.5 to about 4.0, preferably
from about 1.0 to
about 2.4. Also preferred are aluminosilicates including zeolites. Such
materials and their use as
detergent builders are more fully discussed in Corkill et al., U. S. Patent
No. 4,605,509.
Also discussed in U.S. Patent No. 4,605,509 are crystalline layered silicates
which are suitable
for use in the detergent compositions of this invention.
E) Optional Detergent Ingredients
In addition to the surfactants, builders and mixture of cyclic amine based
polymers,
oligomers or copolymers and hydrophobically modified cellulosic based polymers
or oligomers
hereinbefore described, the detergent compositions of the present invention
can also include any
number of additional optional ingredients. These include conventional
detergent composition
components such as enzymes and enzyme stabilizing agents, suds boosters or
suds suppressersõ
anti-tarnish and anticorrosion agents, bleaching agents, soil suspending
agents, soil release
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agents, germicides, pH adjusting agents, non-builder alkalinity sources,
chelating agents, organic
and inorganic fillers, solvents, hydrotropes, optical brighteners, dyes and
perfumes.
A preferred optional ingredients for incorporation into the detergent
compositions herein
comprises a bleaching agent, e.g., a peroxygen bleach. Such peroxygen
bleaching agents may be
organic or inorganic in nature. Inorganic peroxygen bleaching agents are
frequently utilized in
combination with a bleach activator.
Useful organic peroxygen bleaching agents include percarboxylic acid bleaching
agents
and salts thereof. Suitable examples of this class of agents include magnesium
monoperoxyphthalate hexahydrate, the magnesium salt of meiachloro perbenzoic
acid, 4-
nonylamino-4-oxoperoxybutyric acid and diperoxydodecanedioic acid. Such
bleaching agents
are disclosed in U.S. Patent 4,483,781, Hartman, Issued November 20, 1984;
European Patent
Application EP-A-133,354, Banks et al., Published February 20, 1985; and U.S.
Patent
4,412,934, Chung et al., Issued November 1, 1983. Highly preferred bleaching
agents also
include 6-nonylamino-6-oxoperoxycaproic acid (NAPAA) as described in U.S.
Patent 4,634,551,
Issued January 6, 1987 to Bums et al.
Inorganic peroxygen bleaching agents may also be used, generally in
particulate form, in
the detergent compositions herein. Inorganic bleaching agents are in fact
preferred. Such
inorganic peroxygen compounds include alkali metal perborate and percarbonate
materials. For
example, sodium perborate (e.g. mono- or tetra-hydrate) can be used. Suitable
inorganic
bleaching agents can also include sodium or potassium carbonate peroxyhydrate
and equivalent
"percarbonate" bleaches, sodium pyrophosphate peroxyhydrate, urea
peroxyhydrate, and sodium
TM
peroxide. Persulfate bleach (e.g., OXONE, manufactured commercially by DuPont)
can also be
used. Frequently inorganic peroxygen bleaches will be coated with silicate,
borate, sulfate or
water-soluble surfactants. For example, coated percarbonate particles are
available from various
commercial sources such as FMC, Solvay Interox, Tokai Denka and Degussa.
Inorganic peroxygen bleaching agents, e.g., the perborates, the percarbonates,
etc., are
preferably combined with bleach activators, which lead to the in situ
production in aqueous
solution (i.e., during use of the compositions herein for fabric
laundering/bleaching) of the
peroxy acid corresponding to the bleach activator. Various non-limiting
examples of activators
are disclosed in U.S. Patent 4,915,854, Issued April 10, 1990 to Mao et al.;
and U.S. Patent
4,412,934 Issued November 1, 1983 to Chung et al. The nonanoyloxybenzene
sulfonate (NOBS)
and tetraacetyl ethylene diamine (TAED) activators are typical and preferred.
Mixtures thereof
can also be used. See also the hereinbefore referenced U.S. 4,634,551 for
other typical bleaches
and activators useful herein.
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Other useful amido-derived bleach activators are those of the forrnulae:
RIN(R5)C(O)R2C(O)L or RIC(O)N(R5)R2C(O)L
wherein RI is an alkyl group containing from about 6 to about 12 carbon atoms,
R2 is an alkylene
containing from 1 to about 6 carbon atoms, R5 is H or alkyl, aryl, or alkaryl
containing from
about I to about 10 carbon atoms, and L is any suitable leaving group. A
leaving group is any
group that is displaced from the bleach activator as a consequence of the
nucleophilic attack on
the bleach activator by the perhydrolysis anion. A preferred leaving group is
phenol sulfonate.
Prefetred examples of bleach activators of the above formulae include (6-
octanamido-
,.,
caproyl)oxybenzenesulfonate, (6-nonanamidocaproyl) oxybenzene-sul-fonate, (6-
decanamido-
caproyl)oxybenzenesulfonate and mixtures thereof as described in
U.S. Patent 4,634,551.
Another class of useful bleach activators comprises the benzoxazin-type
activators
disclosed by Hodge et al. in U.S. Patent 4,966, 723, Issued October 30, 1990.
See also U.S. Patent 4,545,784, issued to Sanderson, October 8, 1985, 15 which
discloses acyl caprolactams, including benzoyl caprolactam, adsorbed into
sodium
perborate.
If utilized, peroxygen bleaching agent will generally comprise from about 2%
to 30% by
weight of the detergent compositions herein. More preferably, peroxygen
bleaching agent will
comprise from about 2% to 20% by weight of the compositions. Most preferably,
peroxygen
bleaching agent will be present to the extent of from about 3% to 15% by
weight of the
compositions herein. If utilized, bleach activators can comprise from about 2%
to 10% by
weight of the detergent compositions herein. Frequently, activators are
employed such that the
molar ratio of bleaching agent to activator ranges from about 1:1 to 10:1,
more preferably from
about 1.5:1 to 5:1.
Additional suitable bleaching agents and bleach activators are disclosed in co-
pending
PCT Application W098/14300, Published March 25, 1999, entitled Laundry
Detergent
Compositions with Cyclic Amine Based Polymers to Provide Appearance and
Integrity Benefits
to Fabrics Laundered Therewith, which was filed on September 15, 1997, in the
name of
Panandiker et al.
Another highly preferred optional ingredient in the detergent compositions
herein is a
detersive enzyme component. Enzymes can be included in the present detergent
compositions
for a variety of purposes, including removal of protein-based, carbohydrate-
based, or
triglyceride-based stains from substrates, for the prevention of refugee dye
transfer in fabric
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laundering, and for fabric restoration. Suitable enzymes include proteases,
amylases, lipases,
cellulases, peroxidases, and mixtures thereof of any suitable origin, such as
vegetable, animal,
bacterial, fungal and yeast origin. Preferred selections are influenced by
factors such as pH-
activity and/or stability, optimal thermostability, and stability to active
detergents, builders and
the like. In this respect bacterial or fungal enzymes are preferred, such as
bacterial amylases and
proteases, and fungal cellulases.
"Detersive enzyme", as used herein, means any enzyme having a cleaning, stain
removing
or otherwise beneficial effect in a laundry detergent composition. Preferred
enzymes for laundry
purposes include, but are not limited to, proteases, cellulases, lipases,
amylases and peroxidases.
Enzymes are normally incorporated into detergent compositions at levels
sufficient to
provide a "cleaning-effective amount". The term "cleaning-effective amount"
refers to any
amount capable of producing a cleaning, stain removal, soil removal,
whitening, deodorizing, or
freshness improving effect on substrates such as fabrics. In practical terms
for current
commercial preparations, typical amounts are up to about 5 mg by weight, more
typically 0.01
mg to 3 mg, of active enzyme per gram of the detergent composition. Stated
otherwise, the
compositions herein will typically comprise from 0.001% to 5%, preferably
0.01%-1% by weight
of a commercial enzyme preparation. Protease enzymes are usually present in
such commercial
preparations at levels sufficient to provide from 0.005 to 0.1 Anson units
(AU) of activity per
gram of composition. Higher active levels may be desirable in highly
concentrated detergent
formulations.
Cellulases usable herein include those disclosed in U.S. Patent No. 4,435,307,
Barbesgoard
et al., March 6, 1984, and GB-A-2.075.028; GB-A-2.095.275 and DE-OS-2.247.832.
CAREZYME and CELLUZYME (Novo) are especially useful. See also WO 9117243 to
Novo.
The enzyme-containing compositions herein may optionally also comprise from
about
0.001% to about 10%, preferably from about 0.005% to about 8%, most preferably
from about
0.01% to about 6%, by weight of an enzyme stabilizing system. The enzyme
stabilizing system
can be any stabilizing system which is compatible with the detersive enzyme.
Such a system may
be inherently provided by other formulation actives, or be added separately,
e.g., by the
formulator or by a manufacturer of detergent-ready enzymes. Such stabilizing
systems can, for
example, comprise calcium ion, boric acid, propylene glycol, short chain
carboxylic acids,
boronic acids, and mixtures thereof, and are designed to address different
stabilization problems
depending on the type and physical form of the detergent composition.
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The compositions of the present invention may also include dye transfer
inhibiting
agents such as polyvinyl pyrrolidone polymers, polyamine N-oxide polymers,
copolymers of
N-vinylpyrrolidone and N-vinylimidazole, manganese phthalocyanine,
peroxidases, and
mixtures thereof. These agents typically comprise from about 0.01% to about
10% by
weight of the composition, preferably from about 0.01% to about 5%, and more
preferably
from about 0.05% to about 2%.
More specifically, the polyamine N-oxide polymers preferred for use herein
contain
units having the following structural formula: R-Ax-P; wherein P is a
polymerizable unit to
which an N-O group can be attached or the N-O group can form part of the
polymerizable
unit or the N-O group can be attached to both units; A is one of the following
structures: -
NC(O)-, -C(O)O-, -S-, -0-, -N=; x is 0 or 1; and R is aliphatic, ethoxylated
aliphatics,
aromatics, heterocyclic or alicyclic groups or any combination thereof to
which the nitrogen
of the N-0 group can be attached or the N-O group is part of these groups.
Preferred
polyamine N-oxides are those wherein R is a heterocyclic group such as
pyridine, pyrrole,
imidazole, pyrrolidine, piperidine and derivatives thereof.
The N-O group can be represented by the following general structures:
0 0
I 1
(Rt )x i -~2)y; =N-(Rl )x
(R3)Z
wherein R1, R2, R3 are aliphatic, aromatic, heterocyclic or alicyclic groups
or combinations
thereof; x, y and z are 0 or 1; and the nitrogen of the N-0 group can be
attached or form
part of any of the aforementioned groups. The amine oxide unit of the
polyamine N-oxides
has a pKa <10, preferably pKa <7, more preferred pKa <6.
Any polymer backbone can be used as long as the amine oxide polymer formed is
water-soluble and has dye transfer inhibiting properties. Examples of suitable
polymeric
backbones are polyvinyls, polyalkylenes, polyesters, polyethers, polyamide,
polyimides,
polyacrylates and mixtures thereof. These polymers include random or block
copolymers
where one monomer type is an amine N-oxide and the other monomer type is an N-
oxide.
The amine N-oxide polymers typically have a ratio of amine to the amine N-
oxide of 10:1 to
1:1,000,000. However, the number of amine oxide groups present in the
polyamine oxide
polymer can be varied by appropriate copolymerization or by an appropriate
degree of N-
oxidation. The polyamine oxides can be obtained in almost any degree of
polymerization.
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Typically, the average molecular weight is within the range of 500 to
1,000,000; more
preferred 1,000 to 500,000; most preferred 5,000 to 100,000.
The most preferred polyamine N-oxide useful in the detergent compositions
herein
is poly(4-vinylpyridine-N-oxide) which as an average molecular weight of about
50,000 and
an amine to amine N-oxide ratio of about 1:4. This preferred class of
materials can be
referred to as "PVNO".
Further suitable dye transfer inhibitors can be found in U. S. Pat. No.
5,466,802,
issued Nov. 14, 1995 to Panandiker et al.
F) Detergent Composition Preparation
The detergent compositions according to the present invention can be in
liquid, paste or
granular form. Such compositions can be prepared by combining the essential
and optional
components in the requisite concentrations in any suitable order and by any
conventional means.
The forgoing description of uses for the mixture of cyclic amine based
polymers, oligomers or
copolymers and hydrophobically modified cellulosic based polymers or oligomers
defined herein
are intended to be exemplary and other uses will be apparent to those skilled
in the art and are
intended to be within the scope of the present invention.
Granular compositions, for example, are generally made by combining base
granule
ingredients, e.g., surfactants, builders, water, etc., as a slurry, and spray
drying the resulting
slurry to a low level of residual moisture (5-12%). The remaining dry
ingredients, e.g., granules
of the essential mixture of cyclic amine based polymers, oligomers or
copolymers and
hydrophobically modified cellulosic based polymers or oligomers, can be
admixed in granular
powder form with the spray dried granules in a rotary mixing drum. The liquid
ingredients, e.g.,
solutions of the essential mixture of cyclic amine based polymers, oligomers
or copolymers and
hydrophobically modified cellulosic based polymers or oligomers, enzymes,
binders and
perfumes, can be sprayed onto the resulting granules to form the finished
detergent composition.
Granular compositions according to the present invention can also be in
"compact form", i.e. they
may have a relatively higher density than conventional granular detergents,
i.e. from 550 to 950
g/1. In such case, the granular detergent compositions according to the
present invention will
contain a lower amount of "inorganic filler salt", compared to conventional
granular detergents;
typical filler salts are alkaline earth metal salts of sulphates and
chlorides, typically sodium
sulphate; "compact" detergents typically comprise not more than 10% filler
salt.
Liquid detergent compositions can be prepared by admixing the essential and
optional
ingredients thereof in any desired order to provide compositions containing
components in the
requisite concentrations. Liquid compositions according to the present
invention can also be in
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"compact form", in such case, the liquid detergent compositions according to
the present
invention will contain a lower amount of water, compared to conventional
liquid detergents.
Addition of the mixture of cyclic amine based polymers, oligomers or
copolymers and
hydrophobically modified cellulosic based polymers or oligomers to liquid
detergent or other
aqueous compositions of this invention may be accomplished by simply mixing
into the liquid
solutions the desired mixture of cyclic amine based polymers, oligomers or
copolymers and
hydrophobically modified cellulosic based polymers or oligomers.
The methods and compositions heretofore disclosed may also be applied towards
the
production of particles that may be used as one of the component detergent
granules in a granular
detergent composition.
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G) Fabric Launderine Method
The present invention also provides a method for laundering fabrics in a
manner which
imparts fabric appearance benefits provided by the mixture of cyclic amine
based polymers,
oligomers or copolymers and hydrophobically modified cellulosic based polymers
or oligomers
used herein. Such a method employs contacting these fabrics with an aqueous
washing solution
formed from an effective amount of the detergent compositions hereinbefore
described or formed
from the individual components of such compositions. Contacting of fabrics
with washing
solution will generally occur under conditions of agitation although the
compositions of the
present invention may also be used to form aqueous unagitated soaking
solutions for fabric
cleaning and treatment.
Agitation is preferably provided in a washing machine for good cleaning.
Washing is
preferably followed by drying the wet fabric in a conventional clothes dryer.
An effective
amount of a high density liquid or granular detergent composition in the
aqueous wash solution in
the washing machine is preferably from about 500 to about 7000 ppm, more
preferably from
about 1000 to about 3000 ppm.
H) Fabric Conditioning and Softening
The mixture of cyclic amine based polymers, oligomers or copolymers and
hydrophobically
modified cellulosic based polymers or oligomers hereinbefore described as
components of the
faundry detergent compositions herein may also be used to treat and condition
fabrics and textiles
in the absence of the surfactant and builder components of the detergent
composition
embodiments of this invention. Thus, for example, a fabric conditioning
composition comprising
only the mixture of cyclic amine based polymers, oligomers or copolymers and
hydrophobically
modified cellulosic based polymers or oligomers themselves, or comprising an
aqueous solution
of the mixture of cyclic amine based polymers, oligomers or copolymers and
hydrophobically
modified cellulosic based polymers or oligomers, may be added during the rinse
cycle of a
conventional home laundering operation in order to impart the desired fabric
appearance and
integrity benefits hereinbefore described.
Additional suitable fabric softening agents are disclosed in co-pending PCT
Application
W098/14300, Published March 25, 1999, entitled Laundry Detergent Compositions
with Cyclic
Amine Based Polvmers to Provide Appearance and Integrity Benefits to Fabrics
Laundered
Theretivith, which was filed on September 15, 1997, in the name of Panandiker
et al.
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The compositions of the present invention comprise at least about 1%,
preferably from
about 10%, more preferably from about 20% to about 80%, more preferably to
about 60% by
weight, of the composition of one or more fabric softener actives.
EXAMPLES
The following examples illustrate the compositions and methods of the present
invention,
but are not necessarily meant to limit or otherwise define the scope of the
invention.
EXAMPLE I
Synthesis of the adduct of imidazole and epichlorohydin (Ratio of
imidazole:epichlorohydrin 1:1):
The polycationic condensate is prepared by reacting imidazole and
epichlorohydrin. To a
round bottomed flask equipped with a magnatic stirrer, condenser and a
thermometer are added
imidazole (0.68 moles) and 95 mL water. The solution is heated to 50 C
followed by dropwise
addition of epichlorohydrin (0.68 moles). After all the epichlorohydrin is
added, the temperature
is raised to 80 C until all the alkylating agent is consumed. The condensate
produced had
molecular weight of about 12,500.
EXAMPLE 2
Synthesis of the adduct of imidazole and epichlorohydin (Ratio of
imidazole:epichlorohydrin 1.4:1)
To a round bottomed flask equipped with a magnatic stirrer, condenser and a
thermometer are added imidazole (0.68 moles) and 95 mL water. The solution is
heated to 50 C
followed by dropwise addition of epichlorohydrin (0.50 moles). After all the
epichlorohydrin is
added, the temperature is raised to 80 C until all the alkylating agent is
consumed. The
condensate produced had molecular weight of about 2000.
EXAMPLE 3
Synthesis of the adduct of piperazine, morpholine and epichlorohydin (Ratio
1.8/0.8/2.0)
Into a round bottom flask equipped with stirrer, thermometer, dropping funnel
and reflux
condenser 154.8 g (1.8 mole) of piperazine and 69.6 g (0.8 mole) of morpholine
and 220 ml of
water are added. After a clear solution at 40 C is obtained, the solution is
heated to 55-65 C and
with vigorous stirring 185 g (2 mole) of epichlorohydrin is added at such a
rate, that the
temperature does not exceed 80 C. After all the epichlorohydrin is added the
reaction mixture is
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heated to 85 C until all of the alkylating agents is consumed (negative
Preussmann test after 4
hours). 108.8 g (0.68 mole) of 25% NaOH and 40 g of water are added and the
reaction mixture
is stirred for another hour at 85 C. Then an additional 47 g of water is added
and the mixture is
allowed to cool to room temperature.
EXAMPLE 4
Synthesis of the adduct of piperazine/morpholine/epi, in a ratio of
1.8/0.8/2.0
Into a round bottom flask equipped with stirrer, thermometer, dropping funnel
and reflux
condenser 154.8 g (1.8 mole) of piperazine and 69.6 g (0.8 mole) of morpholine
and 220 ml of
water are added. After a clear solution at 40 C is obtained, the solution is
heated to 55-65 C and
with vigorous stirring 185 g (2 mole) of epichlorohydrin is added at such a
rate, that the
temperature does not exceed 80 C. After all the epichlorohydrin is added the
reaction mixture is
heated to 85 C until all of the alkylating agents has been consumed (negative
Preussmann test
after 4 hours). 108.8 g (0.68 mole) of 25% NaOH and 40 g of water is added and
the reaction
mixture is stirred for another hour at 85 C. Then an additional 47 g of water
are added and the
mixture is allowed to cool to room temperature.
EXAMPLE 5
Adduct of piperazine/morpholine/epi from Example 4, 100% oxidized
233.6 g(equivalent to 1,292 mole oxidizable nitrogen atoms) of the material
from
Example 4 above is mixed with 22.1 g (0.276) of 50% NaOH and then heated to 55-
65 C. At
that temperature 102.4 g (1,421 mole) of H202 (47.2%) is added dropwise over a
period of 3.5
hours. After the addition is complete, the reaction mixture is held at the
same temperature for 3
more hours and is then stirred at room temperature overnight. Pt/C was added,
unreacted H202
destroyed and the solution then filtered.
The reaction product is characterized as follows:
water content 58%
pH 5.6
chloride contentl.593 mmole/g
EXAMPLE 6
Synthesis of the adduct of imidazole/piperazine/epi, in a ratio 1.0/3.0/4.0
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68.8g (1.0 mole) of limidazole and 260.6 g (3.0 mole) of piperazine are
dissolved in
700.2 g of water and at a temperature of 50-60 C, 370 g (4.0 mole) of
epichlorhydrin is added
dropwise. After the addition is complete, the reaction mixture is stirred for
additional 5 hours at
80 C.
EXAMPLE 7
Adduct of imidazole/piperazine/epi from Example 6, 100% oxidized
To 237 g of the product from Example 6 above (equivalent to 1,022 mole of
oxidizable
nitrogen atoms) 80.7 g(1.12 mole) of a 47.2% solution of H202 in water is
added over a period
of 5 hours at 40 C. After that, the mixture is heated to 50-60 C until the
theoretical amount of
H202 has been consumed. Unreacted H202 is destroyed by using Pt/C and the
solution is then
filtered.
The reaction product is characterized as follows:
water content: 58.6%
pH: 2.86
chloride content: 3.694 mmole/g
Mn(GPC): 340
Mw (GQC): 940
Mn/Mw: 2.8+/-0.1
EXAMPLE 8
Synthesis of hydrophobically modified CMC Materials
The carboxylation of cellulose to produce CMC is a procedure that is well
known to
those skilled in the art. One method of producing the modified CMC materials
of this invention,
is to add during the CMC making process the material, or materials, to be
substituted. An
example of such as procedure is given below. This same procedure can be
utilized with the other
substituent materials described herein by replacing the hexylchloride with the
substituent
material, or materials, of interest, for example, cetylchloride. The amount of
material that should
be added to the CMC making process to achieve the desired degree of
substitution will be easily
calculated by those skilled in the art in light of the following Examples.
EXAMPLE 9
Synthesis of Hexylether of CMC
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This example illustrates the preparation of a hydrophobically modified
carboxymethyl
cellulose and is representative of preparation of all of the cellulose ether
derivatives of this
invention.
Cellulose (20 g), sodium hydroxide (10 g), water (30 g), and ethanol (150 g)
are charged
into a 500 ml glass reactor. The resulting alkali cellulose is stirred 45
minutes at 25 C. Then
monochioroacetic acid (15 g) and hexylchoride (1 g) are added and the
temperature raised over
time to 95 C and held at 95 C for 150 minutes. The reaction is cooled to 70 C,
and then cooled
to 25 C. Neutralization is accomplished by the addition of a sufficient amount
of nitric
acid/acetic acid to achieve a slurry pH of between 8 and 9. The slunry is
filtered to obtain a
hexylether of CMC.
EXAMPLE 10
Cellulosic Polymers Used in Test Detergent Compositions
Representative modified cellulosic polymers for use in the liquid and granular
detergent
compositions described below are characterized in Tables 10 A and 10 B. The
General Polymer
Parameters are common to all of the polymers, while the specific chemical
structure of the
materials tested are listed under the Specific Polymer Parameters.
Table 10 A
General Polymer Parameters
Molecular Parameters Description
Polvmer Backbone Carbox eth lcellulose
Degree of Carboxvmethvlation DSRC' = 0.3 - 2.0; preferred DSRC = 0.5 - 0.70.
Distribution of Even and random distribution of carboxylmethyls
Carboxvmethvls along the backbone
Molecular Weight Mw: 5,000 - 2,000000. Preferred: medium
(approx 250,000 g/mol)
Type of Modification Ether modification (in addition to
carbox eth lation . Mixed cellulose ether
Level of Modification DSRH = about 0.001 to about 0.I
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Table 10 B
Table Specific Polymer Parameters
ID Polymer Type of Types of Chemistry
Modification***
*A Hexyl CMC Hexyl ether Chlorohexane added to CMC
maldn process
*B Decyl CMC Decyl ether Chlorodecane added to CMC
making process
**C C12-C13 alkoxy-2 C12-C13 alkoxy-2 C12-C13 alkyl glycidyl ether
hydroxypropyl CMC hydroxypropyl added to CMC making
ether process
*D Hexadecyl CMC Hexadecyl ether Chlorohexadecane added to
CMC making process
*E Chloride salt of 3- chloride salt of 3- 2,3-epoxypropyltrimethyl
trimethylammonio-2- trimethylammonio- ammonium chloride added to
hydroxypropyl ether 2-hydroxypropyl the CMC making process
of CMC ether
*F {-(C(O)- Cetyl Ketene Dimer added to
CH(Ci6H3,)- CMC making process.
C(O)CH,(C,6H;~) ]
ester of CMC or 1,3-
dioxo-2-
hexadecyloctadecyl
ester of CMC
CMC = Carboxymethylcellulose
* Manufactured by Metsa Specialty Chemicals
** Manufactured by Akzo
***DSRH for these materials was in the range of from about 0.001 to about 0.1
EXAMPLE l I
The following are idealized chemical structures for certain cyclic amine based
polymers,
oligomers or copolymers of this invention. Side reactions expected to occur
during the
condensation are not shown.
Table 1l
Example Material
Adduct of Imidazole-epichlorohydrin
(Ratio of imidazole:epichlorohydrin 1:1, Polymer from Example
1)
,
OH
(Idealized Structure)
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Adduct of Imidazole-epichlorohydrin
(Ratio of imidazole:epichlorohydrin 1.36:1, Polymer from
Example 2)
2 N
OH
(Idealized Structure)
Adduct of Imidazole-epichlorohydrin
3 (Ratio of imidazole:epichlorohydrin 1.75:1)
f N
~ OH
^~
(Idealized Structure)
Adduct of Imidazole-epichlorohydrin-trisglycidyl ether from
glycerine (Ratio of imidazole:epichlorohydrin: trisglycidylether
2.0:1.76:0.26)
4
H
HO O OH
N N\
0, 1d
Idealized Structure
Adduct of Imidazole-epichlorohydrin- -trisglycidyl ether from
glycerine(Ratio of imidazole:epichlorohydrin: -trisglycidyl ether
from glycerine 2.0:1.9:0.1)
H
HO 0 OH
Adduct of piperazine and epichlorohydrin (ratio 1:1)
6 tNI--\j:~
X
Adduct of piperazine and epichlorohydrin (ratio 1:1), benzyl quat
~
I ~
7
OH
iN + X
Adduct of piperazine and epichlorohydrin (ratio 1:1) methyl quat
8 CH30H
x
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Adduct of piperazine,morpholine and epichlorohydrin (ratio 0.9:
9 0.4:1.0)
OH
~N~J JX
OH
Adduct of piperazine, piperidine and epichlorohydrin (ratio 0.9:
0.4:1.0)
CN OH X0
lON\.~ N
OH
Adduct of piperazine, morpholine and epichlorohydrin (ratio 0.9:
11 0.4:1.0) methyl quat
H3
ON
~N~\ ~+ H N~\O
~N x
OH
Adduct of piperazine, piperidine and epichlorohydrin (ratio 0.9:
12 0.4:1.0) methyl quat
/-~ lOH3
CN No
OH OH
Adduct of piperazine,morpholine and epichlorohydrin (ratio 0.9:
0.4:1.0) benzyl quat
13 O
\_ / OH ~/
OH
Adduct of piperazine, piperidine and epichlorohydrin (ratio 0.9:
0.4:1.0) benzyl quat
14 O
CO H OH
Adduct of imidazole, piperazine and epichlorohydrin (ratio 2:1:3)
~ OH
15 /---\
N,
` N N / N
L\,--d H \--/
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Adduct of imidazole, piperazine and epichlorohydrin (ratio 1:1:2)
16 NIND OH
of imidazole, 1,6 diaminohexane and epichlorohydrin
Adduct
17 (ratio 1:1:2)
fN~j NH
NH
OH OH
Adduct of imidazole, dimethylaminopropylamine and
epichlorohydrin (ratio 1.02:0.34:1.0)
18 N~p OH
OH
N
H3C-' `CH3
Adduct of imidazole-epichlorohydrin and chloroacetic acid
19 (Ratio- 1.36:0.97:0.07)
HOOC---h` , N`~,N^CpOH
=/ H
Adduct of imidazole-epichlorohydrin and chloroacetic acid
20 (Ratio- 1.36:0.93:0.14)
HOOC~~ h\=j H r; `~v ~ `;t~(~ppH
Adduct of imidazole-epichlorohydrin and chloroacetic acid
21 (Ratio- 1.36:0.83:0.34)
HOOC-"N"k, V"'~'N---OOOH
Adduct of imidazole-epichlorohydrin and 3chlorohydroxypropyl
22 sulfonic acid (ratio: 1.0:0.83:0.34)
NaO3S""'T"-"'h^R ~~~SO,Na
OH F{ ~ ~ OH
Adduct of imidazole-epichlorohydrin and 3 chlorohydroxypropyl
23 sulfonic acid (ratio:1.0:0.75:0.5)
NaO,S-"-f'-"N^g 1 / N--,-~SO]Na
OH ~ ~+ H ,~ OH
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Adduct of imidazole, piperazine and
24 epichlorohydrin (Ratio- 1.0:1.0:2.0) quat with 0.22 moles of
chloroacetate
HOOC
OH OH
rc ' N N N N
Adduct of imidazole, piperazine andepichlorohydrin (Ratio-
1.0:3.0:4.0) 1.0:3.0:4.0) quat with 0.32 moles of chloroacetate
Hooc
OH
0" CN
CIP-Y N N Adduct of imidazole, piperazine andepichlorohydrin (Ratio-
26 1.0:1.0:2.0) quat with 0.45 moles of chloroacetate
Hooc
TcflN>CN
OH PP~ Adduct of imidazole and epichlorohdrin, (ratio 1.75:1) oxidized
27 0-N~ OH N~~~~dN-O
JJJn
Adduct of piperazine and epichlorohydrin (ratio 1:1) 100%
28 oxidized
o /--\ o OH
N\ /N
V
n
Adduct of piperazine and epichlorohydrin (ratio 1:1) 50%
29 oxidized
OH 0 N/O OH
N~ \ N N \ / n
Addu~ctJof piperazine, morpholine and epichlorohydrin (ratio
30 1:0.2:1) 100% oxidized
ON i
\---/ oH j m
Adduct of piperazine, morpholine and epichlorohydrin (ratio
31 1:0.2:1)25% methyl quat and oxidized
O
aH OH n \-/
Adduct of imidazole, piperazine and epichlorohydrin (ratio 1:3;4)
32 100% oxidized
O OH
N" `N N ~N
OH
m n
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Adduct of imidazole, piperazine and epichlorohydrin (ration
33 1:3;4) 50% oxidized
o /~ o oH [f-\ oH
~. / \-/
OH P
Adduct of imidazole, piperazine and epichlorohydrin (ration
34 1:1:2) 100% oxidized
N"'` \ ~\ 0 OH
N N
OH \-/
n
Adduct of imidazole, piperazine and epichlorohydrin (ration
35 1:5:6) 100% oxidized
O OH
N ~--~N
~ oH \-/
P
Adduct of imidazole, piperazine and epichlorohydrin (ration
36 1:10:11) 100% oxidized
~` - \ p OH
y
~~---/ 7 N\-~
P
Adduct of imidazole, piperazine andepichlorohydrin (Ratio-
1.0:3.0:4.0) 1.0:3.0:4.0) quat with 0.32 moles of chloroacetate and oxidized
HOCX
o a+
NiQ I-\ ~ "
V N~ N N~~N
" ~J n 1J v
Adduct of imidazole, piperazine and epichlorohydrin (Ratio-
38 1.0:1.0:2.0) quat with 0.45 moles of chloroacetate and oxidized
Hooc
oH 0 a+
~.J N N
OH \__._/
n P
Adduct of imidazole, piperazine and epichlorohydrin (Ratio-
39 1.0:5.0:6.0) quat with 0.32 moles of chloroacetate and oxidized
Hooc
) " o cll~c "
~.J
N N N~ /
n P
Adduct of imidazole, piperazine and epichlorohydrin (Ratio-
40 1=0:1.0:2.0) quat with 0.45 moles of dimethyl sulfate and oxidized
~ N/-~N CH~ ~ 1~\ p oN
1=/ v N\ /N
n ~_/ P
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41 Adduct of imidazole, dimethylaminopropylamine and
epichlorohydrin (ratio 1.02:0.34:1.0) oxidized
OH
N
OH
N
H3C/O\CH,
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EXAMPLE 12
Granular Detergent Test Composition Preparation
Several heavy duty granular detergent compositions are prepared containing a
mixture of
cyclic amine based polymers, oligomers or copolymers and hydrophobically
modified cellulosic
based polymers or oligomers. These granular detergent compositions all have
the following
basic formula:
Table 12
Component Wt. %
C Linear alkvl benzene sulfonate 9.31
C_ alkyl ether 0.35 EO) sulfate 12.74
Zeolite Builder 27.79
Sodium Carbonate 27.31
PEG 4000 1.60
Dispersant 2.26
7-1 Alcohol Ethoxylate 9 EO) 1.5
Sodium Perborate 1.03
Soil Release Polvmer 0.41
Enzvmes 0.59
Cvclic Amine Based Polvmers or Oligomers 3.0
Hydrophobically Modified Cellulosic Based 1.0
Polvmers or Oligomers
Perfume, Brightener, Suds Suppressor, Other Balance
Minors, Moisture, Sulfate
100%
EXAMPLE 13
Liquid Detergent Test Composition Preparation
Several heavy duty liquid detergent compositions are prepared a mixture of
cyclic amine
based polymers, oligomers or copolymers and hydrophobically modified
cellulosic based
polymers or oligomers. These liquid detergent compositions all have the
following basic
formula:
Table 13
Component Wt. %
C_ alkyl ether (2.5) sulfate 38
C 17 glucose amide 6.86
Citric Acid 4.75
C 12_ Fattv Acid 2.00
Enzvmes 1.02
MEA 1.0
Propanediol 0.36
Borax 6.58
Dispersant 1.48
Na Toluene Sulfonate 6.25
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Cvclic Amine Based Polymers or Oligomers 1.0
Hydrophobically Modified Cellulosic Based 0.1
Polvmers or Oligomers
Dye, Perfume, Brighteners, Preservatives, Suds Balance
Suppressor, Other Minors, Water
100%
EXAMPLE 14
Granular Detergent Test Composition Preparation
Several granular detergent compositions are prepared containing a mixture of
cyclic
amine based polymers, oligomers or copolymers and hydrophobically modified
cellulosic based
polymers or oligomers. Such granular detergent compositions all have the
following basic
formula:
Table 14
Example Comparative
Component Wt. % Wt%
Na C Linear alkvl benzene sulfonate 9.40 9.40
Na C_ alkvl sulfonate 11.26 11.26
Zeolite Builder 27.79 27.79
Sodium Carbonate 27.31 27.31
PEG 4000 1.60 1.60
Dispersant. Na polvacrviate 2.26 2.26
C_ alkvl ethoxylate (E9) 1.5 1.5
Sodium Perborate 1.03 1.03
Cyclic Amine Based Polymers or 0.8 0
Oligomers
Hydrophobically Modified Cellulosic 0.3 0
Based Polvmers or Oligomers
Other Ad'unct ingredients Balance Balance
100% 100%
EXAMPLE 15
A detergent agglomerate which may be used as a particulate component in a
detergent
composition is prepared according to the following formulas and ranges. The
granule may be
manufactured by agglomeration methods known to those skilled in the art; some
of which are
described in the present application.
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Ex. 15A Ex.15B
Component Wt % Wt %
Cyclic Amine Based Polymers or 2-7 8-10
Oligomers
Hydrophobically Modified Cellulosic 20-70 80-90
Based Polymers or Oligomers
Zeolite Builder 0-70 0
Dispersant/Binderl 2-6 0
Water and Misc. Balance Balance
100% 100%
1: Dispersant is Na Polyacrylate 4500, Polyethylene Glycol or a mixture of
both.
