Note: Descriptions are shown in the official language in which they were submitted.
CA 02359808 2001-07-25
WO 00/47705 PCT/US00/03472
-1-
LAUNDRY DETERGENT COMPOSITIONS WITH FABRIC ENHANCING COMPONENT
TECHNICAL FIELD
The present invention relates to compositions, in either liquid or granular
form, for use in
laundry applications, wherein the compositions comprise certain fabric
enhancing components,
which can be, for example, a cyclic amine based polymer, oligomer or copolymer
material,
hydrophobically modified carboxy methyl cellulose and mixtures thereof.
Additionally, a contain
for such compositions is provided.
BACKGROUND OF THE INVENTION
It is, of course, well known that alternating 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
CA 02359808 2001-07-25
WO 00/47705 PCT/US00/03472
-2-
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.
Moreover, there is a need for a container for such products. The container
should not only
store the composition but it should also convey to the consumer the benefits
of this new product.
SUMMARY OF THE IN''ENTION
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) from about 0.01 % to about 5.0%, preferably from about 0.1 % to about 4.0%,
by
weight of a fabric enhancing component selected from the group consisting of
cyclic amine based polymers, oligomers or copolymers, hydrophobically modified
cellulosic based polymers or oligomers, and mixtures thereof.
Further, the detergent composition is contained within an interior chamber of
a container, the
container further comprising an exterior surface wherein the exterior surface
contains a
description of the composition comprising language selected from the group
consisting of: helps
clothes look healthier, helps stop wear before it starts, maintains the
appearance of clothes, helps
prevent clothes from looking worn out, strengthens while it cleans for better
looking clothes,
strengthens threads so clothes look better, helps prevent clothes from looking
worn, helps
prevent wear and tear in the washer that can make clothes look old, helps keep
clothes from
aging, helps clothes come out of the washer looking as good as when they went
in, helps
preserve the fabric integrity of clothes, strengthens threads from the inside
out for better looking
clothes, extends the life of clothes, is like a vitamin for clothes, works
like an anti-aging product
on clothes, is like calcium for clothes, is like a supplement for clothes,
after just 10 washes
clothes look better than they would if you washed them with other detergents,
fortifies threads
for healthier looking clothes, helps prevent clothes from looking old before
their time, is like
stopping time for your clothes so they stay looking good.
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:
CA 02359808 2001-07-25
WO 00/47705 PCT/US00/03472
-3-
T W-R2 W-T Ab
x
wherein;
each T is independently selected from the group consisting of H, C 1-C 1 ~
alkyl, substituted alkyl,
C~-C12 alkylaryl,
-(CH2)hCOOM, -(CH2)hS03M, CH2CH(OH)S03M, -(CH2)hOS03M,
COOM
°CH COOM COOM
CH-COOM -CH COOM _CH2~COOM
/ ~COOM
prH CHI-COOM -CH2 COOM
> >
Q .
T , and -R2Q;
-wherein W comprises at least one cyclic constituent selected from the group
consisting of:
~R3~c ~3~ ~ ~ D~ /~3~c ~3~c-
N-D N N D-N Ra
R3 ~)/ R ~N~N~
q 3
and
\N~N~
U
in addition to the at least one cyclic constituent, W may also comprise an
aliphatic or
1 S substituted aliphatic moiety of the general structure;
N-B N-
i
R3 qR3
CA 02359808 2001-07-25
WO 00/47705 PCT/US00/03472
-4-
-each B is independently Cl-C12 alkylene. Cl-C12 substituted alk~~lene, C~-C12
alkenylene, Cg-
C12 dialkylarylene, Cg-C12 dialkylarylenediyl, and -(R50)nR5- ;
-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, C1-Clg 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 Cl-Cg
hydroxyalkyl;
-each R2 is independently selected from the group consisting of C1-C12
alkylene, C1-C12
alkenylene, -CH2-CH(OR1)-CH2, Cg-C12 alkarylene, C4-C12 dihydroxyalkylene,
poly(C2-C4 alkyleneoxy)alkylene, H2CH(OH)CH20R20CH2CH(OH)CH2-, and C3-
C 12 hydrocarbyl moieties;
provided that when Rz is a C3-C12 hydrocarbyl moiety the hydrocarbyl moiety
can
comprise from about 2 to about 4 branching moieties of the general structure:
OH
-ORS ~O-CH2-CH-CH2~W-RZ~--W-T
-each R3 is independently selected from the group consisting of H, O, R2, C1-
C20 hydroxyalkyl,
C1-C20 alkyl, substituted alkyl, C6-C11 aryl, substituted aryl, C~-C11
alkylaryl, C1-C20
aminoalkyl,
-(CH2)hCOOM, -(CH2)hS03M, CH2CH(OH)S03M, -(CH2)hOS03M,
COOM
-CH COOM COOM
CH-COOM -CH COOM _CH2~COOM
/ COO ~ vM
~H CHZ-COOM
-CH2 , and 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;
CA 02359808 2001-07-25
WO 00/47705 PCT/US00/03472
-5-
each c is independently 0 or 1;
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.
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:
R
O
O O
O
O O
I
R
R
wherein each R is selected from the group consisting of R2, R~, and
CH2 CH O RH
I
R2
x
wherein:
- each R2 is independently selected from the group consisting of H and C1-C4
alkyl;
O
I I
- each R~ is ~CH2)y C-OZ,
wherein each Z is independently selected from the group consisting of M, R2,
R~, and RH;
- each RH is independently selected from the group consisting of CS -C20
alkyl, CS-C~
cycloalkyl, C~-C20 alkylaryl, C~-C20 arylalkyl, substituted alkyl,
hydroxyalkyl, C1-C20
alkoxy-2-hydroxyalkyl, C~-C2p alkylaryloxy-2-hydroxyalkyl, (R4)2N-alkyl,
(R4)2N-2-
hydroxyalkyl, (R4)3 N-alkyl, (R4)3 N-2-hydroxyalkyl, C6-C12 aryloxy-2-
hydroxyalkyl,
CA 02359808 2001-07-25
WO 00/47705 PCT/US00/03472
-G-
O RS O RS O RS O
il i II I - II I II
-C CH C CHI -C CHI CH C-OM, and
O RS O
II I II
-C-CH-CH2-C-OM.
each R4 is independently selected from the group consisting of H, C1-C20
alkyl, CS-C7
cycloalkyl, C7-C20 alkylaryl, C~-C20 arylalkyl, aminoalkyl, alkylaminoalkyl,
dialkylaminoalkyl, piperidinoalkyi, morpholinoalkyl, cycloalkylaminoalkyl and
hydroxyalkyl;
each RS is independently selected from the group consisting of H, C 1 -C20
alkyl, CS-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 1 to about 5; and
provided that:
- the Degree of Substitution for group RH is between about 0.001 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 R~ 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
washing solution additive in either granular or liquid form. Alternatively,
they can be admixed to
granular detergents, dissolved in liquid detergent compositions or added to a
fabric softening
composition.
The laundry detergent compositions herein comprise from about 1% to 80% by
weight of a
detersive surfactant, from about 0.01 % to 80% by weight of an organic or
inorganic detergency
builder and from about 0.01% to 5% by weight of the fabric enhancing component
of the present
CA 02359808 2001-07-25
WO 00/47705 PCT/US00/03472
invention. The detersive surfactant and detergency builder materials can be
any of those useful in
conventional laundry detergent products.
Aqueous solutions of the fabric enhancing component of the subject invention
comprise
from about 0.01% to 80% by weight of cyclic amine based polymers, oligomers or
copolymers,
hydrophobically modified cellulosic based polymers or oligomers and mixtures
thereof dissolved
in water and other ingredients such as stabilizers and pH adjusters.
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.
DETAILED DESCRIPTION OF THE INVENTION
As noted, when fabric or textiles are laundered in wash solutions which
comprise the fabric
enhancing component, the present invention fabric appearance and integrity are
enhanced. The
fabric enhancing component, that is, the 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 washing solution.
The 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.
Likewise, the
detergent containers of the present invention include any appropriate type of
detergent
composition container. Non-limiting examples of such containers include boxes,
bags and
bottles, which can be made from paper, plastic, cardboard, laminates, etc.
Those skilled in the art
will lrnow what materials of construction and types of materials are
appropriate for the detergent
compositions of this invention.
The 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 percentages are by weight unless other specified.
CA 02359808 2001-07-25
WO 00/47705 PCT/US00/03472
-s-
A) Cyclic amine Based Polymer, Oli~omer or Copolymer Materials
The compositions of the present invention can comprise 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 these 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 fabric enhancing component comprising cyclic amine based polymers,
oligomers or
copolymers, hydrophobically modified cellulosic based polymers or oligomers
and mixtures
thereof 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 fabric
enhancing
component 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 the fabric enhancing component is not
incorporated into a
CA 02359808 2001-07-25
WO 00/47705 PCT/US00/03472
-9-
detergent composition, the concentration of the fabric enhancing component can
comprise from
about 0.1 % to about 80% by weight of the additive material.
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 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 ~3~e ~3~c ~3~c
~~ ~
N-D N N D-N
I
R~ R
3
~R3)c ~R3~C~ /(R3)C ~3)c
N-D NON D-N Ra
I l
R3 ~N~N~
3
q q , ~ and
\N ~ N~
Even more preferred compounds for the fabric appearance and integrity benefits
are
those:
-wherein each R1 is H; and
1 S -at least one W is selected from the group consisting of:
CA 02359808 2001-07-25
WO 00/47705 PCT/US00/03472
-10-
I_ ~ _I
I D / ~/ \ D N ~ /
N' \ N
(R3)~ (R3)~ R a
and
\NI \-N/
a
And most 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:
R4 R4
\N' \ N/
N N
and
Preferred compounds to be used as the linking group R2 include, but are not
limited to:
polyepoxides, ethylenecarbonate, propylenecarbonate, urea, a, (3-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 polyalkyleneglycols with a, (3-unsaturated carboxylic
acids, esters of a, (3-
unsaturated carboxylic acids, amides of a, (3-unsaturated carboxylic acids and
anhydrides of a, (3-
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
CA 02359808 2001-07-25
WO 00/47705 PCT/US00/03472
-11-
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 one such
polymer is exemplified below.
T
I
. ~2
x
H
HO O OH
T LR2 W_~~O~~O~W-R~T
x
B) Hydrophobically Modified Cellulosic Based Polymers or Oli~omers
The compositions of the present invention can 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 performance 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.
CA 02359808 2001-07-25
WO 00/47705 PCT/US00/03472
-12-
The cellulosic based fabric treatment component of the detergent compositions
herein will
generally comprise from about 0.1% to about 5°io 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
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
O
O O
O
O O
I
R
R
wherein each R is selected from the group consisting of R2, R~, and
CH2 CH O RH
I
R2
x
wherein:
- each R2 is independently selected from the group consisting of H and C 1-C4
alkyl;
O
I I
- each R~ is ~CHZ)y C-OZ~
wherein each Z is independently selected from the group consisting of M, R2,
R~, and RH;
- each R" is independently selected from the group consisting of CS -C20
alkyl, CS-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-C12 aryloxy-2-
hydroxyalkyl,
CA 02359808 2001-07-25
WO 00/47705 PCT/US00/03472
-13-
O RS O R5 O RS O
II i II i II I II
-C CH C CHI -C CHI CH C-OM
and
O RS O
II i II
-C-CH-CHI-C-OM.
- each R4 is independently selected from the group consisting of H, C1-C2p
alkyl, CS-C7
cycloalkyl, C7-C2p alkylaryl, C7-C20 arylalkyl, aminoalkyl, alkylaminoalkyl,
dialkylaminoalkyl, piperidinoalkyl, rnorpholinoalkyl, cycloalkylaminoalkyl and
hydroxyalkyl;
- each RS is independently selected from the group consisting of H, C1 -C2p
alkyl, Cj-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
I/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 0.001 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 R~ 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 R", which is sometimes abbreviated
herein
"DSO", 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 R~, which is sometimes abbreviated
herein
"DSR~", means the number of moles of group R~ 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
CA 02359808 2001-07-25
WO 00/47705 PCT/US00/03472
-14-
resulting polymer is soluble. It is understood that in addition to the
required number of R~
components wherein Z is H or M, there can be, and most preferably are,
additional R
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
S Examples below.
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. All of these patents are incorporated herein by reference. 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 R1 (OC2H4)nOH, wherein
R1 is a
C 10-C 16 alkyl group or a Cg-C 12 alkyl phenyl group, and n is from 3 to
about 80. Particularly
preferred are condensation products of C 12-C 15 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.
CA 02359808 2001-07-25
WO 00/47705 PCT/US00/03472
-15-
Additional suitable surfactants, including polyhydroxy fatty acid amides and
amine based
surfactants, are disclosed in co-pending PCT Application W098! Published
entitled Laundy, Detergent Compositions with Cyclic Amine Based Polymers to
Provide Appearance and Integrity Beneftts to Fabrics Laundered Therewith,
which was filed on
September 15, 1997, in the name of Panandiker et al. [P&G Case No. 6834]. The
entire
disclosure of the Panandiker et al. reference is incorporated herein by
reference.
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., both of which are
incorporated herein by
reference. Particularly preferred polycarboxylate builders are the
oxydisuccinates and the ether
carboxylate builder compositions comprising a combination of tartrate
monosuccinate and
tartrate disuccinate described in U.S. Patent 4,663,071, Bush et al., issued
May 5, 1987, the
disclosure of which is incorporated herein by reference.
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, the
disclosure of which is incorporated herein by reference. 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
CA 02359808 2001-07-25
WO 00/47705 PCT/US00/03472
-16-
In addition to the surfactants, builders and fabric enhancing component
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
suppressers, anti-tarnish
and anticorrosion agents, bleaching agents, soil suspending agents, soil
release agents,
germicides, pH adjusting agents, non-builder alkalinity sources, chelating
agents, organic and
inorganic fillers, solvents, hydrotropes, optical brighteners, dyes and
perfumes. One preferred
additive is carboxy methyl cellulose, most preferably in a concentration of
from about 0.01% to
about 5% by weight of the detergent composition.
pH adjusting agents may be necessary in certain applications where the pH of
the wash
solution is greater than about 10.0 because the fabric integrity benefits of
the defined
compositions begin to diminish at a higher pH. Hence, if the wash solution is
greater than about
10.0 after the addition of the fabric enhancing component of the present
invention a pH adjuster
should be used to reduce the pH of the washing solution to below about 10.0,
preferably to a pH
of below about 9.5 and most preferably below about 7.5. Suitable pH adjusters
will be known to
those skilled in the art.
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 metachloro 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 Burns 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
CA 02359808 2001-07-25
WO 00/47705 PCT/US00/03472
-17-
"percarbonate" bleaches, sodium pyrophosphate peroxyhydrate, urea
peroxyhydrate, and sodium
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 l, 1983 to Chung et al. The nonanoyloxybenzene
sulfonate (HOBS)
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.
Other useful amido-derived bleach activators are those of the formulae:
R1N(RS)C(O)R2C(O)L or R1C(O)N(RS)R2C(O)L
wherein R1 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, RS is H or alkyl, aryl, or alkaryl
containing from
about 1 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.
Preferred 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 the
hereinbefore referenced
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,
incorporated herein
by reference. See also U.S. Patent 4,545,784, Issued to Sanderson, October 8,
1985, incorporated
herein by reference, 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
CA 02359808 2001-07-25
WO 00/47705 PCT/US00/03472
_18_
compositions herein. If utilized, bleach activators can comprise from about 2%
to 10°o 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/ , Published , entitled Lamtdry~ 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. [P&G Case No. 6834]. The entire disclosure of the Panandiker
et al. reference
was incorporated by reference above.
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
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 S 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.
CA 02359808 2001-07-25
WO 00/47705 PCT/US00/03472
-19-
Cellulases usable herein include those disclosed in U.S. Patent No. 4.43,307.
Barbesgoard
et al., March 6, 1984, and GB-A-2.07.028; GB-A-2.095.275 and DE-OS-2.247.832.
CAREZYME~ and CELLUZYMEC (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.
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 fabric enhancing component is
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 fabric enhancing component 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 fabric enhancing component, 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.
CA 02359808 2001-07-25
WO 00/47705 PCT/US00103472
-20-
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
"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 fabric enhancing component to liquid detergent or other
aqueous compositions of
this invention may be accomplished by simply mixing into the liquid solutions
the desired fabric
enhancing component.
G) Fabric Laundering Method
The present invention also provides a method for laundering fabrics in a
manner which
imparts fabric appearance benefits provided by the fabric enhancing component
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.
As discussed above, it is preferred that the washing solution have a pH of
less than about 10.0,
preferably it has a pH of about 9.5 and most preferably it has a pH of about
7.5.
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 fabric enhancing component hereinbefore described as components of the
laundry
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 fabric
enhancing component, or comprising an aqueous solution of the fabric enhancing
component 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.
CA 02359808 2001-07-25
WO 00/47705 PCT/US00/03472
Additional suitable fabric softening agents are disclosed in co-pending PCT
.Application
W098/ , Published , entitled Laundry Detergent Compositions with Cyclic
Amine Based Polymers to Provide Appearance arid Integrity Benefits to Fabrics
Laundered
Therewith, which was filed on September 1~, 1997, in the name of Panandiker et
al. [P&G Case
No. 6834]. The entire disclosure of the Panandiker et al. reference was
incorporated by reference
above
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.
CA 02359808 2001-07-25
WO 00/47705 PCT/US00/03472
-22-
EXAMPLE 1
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
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
CA 02359808 2001-07-25
WO 00/47705 PCT/US00/03472
_23_
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 I-I2O2 (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. PtIC was added,
unreacted H2O2
destroyed and the solution then filtered.
The reaction product is characterized as follows:
water content 58%
pH 5.6
chloride content1.593 mmole/g
EXAMPLE 6
Synthesis of the adduct of imidazole/piperazine/epi, in a ratio 1.0/3.0/4.0
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 H2O2 in water is
added over a period
CA 02359808 2001-07-25
WO 00/47705 PCT/US00/03472
-24-
of 5 hours at 40°C. After that, the mixture is heated to 50-60°C
until the theoretical amount of
H2O2 has been consumed. Unreacted H2O2 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 (GPC): 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
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
monochloroacetic 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 slurry is
filtered to obtain a
hexylether of CMC.
CA 02359808 2001-07-25
WO 00/47705 PCT/US00/03472
_2j_
rv w w ~rnr r i n
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
Polymer Backbone Carboxymethylcellulose
Degree of CarboxymethylationDSR~ = 0.3 - 2.0; preferred DSR~
= 0.5 - 0.70.
Distribution of Even and random distribution of
Carboxymethyls carboxylmethyls
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
carboxymethylation). Mixed cellulose
ether
Level of Modification DS~ = about 0.001 to about 0.1
Table 10 B
Table Specific Polymer Parameters
ID Polymer Type of Types of Chemistry
Modification***
*A Hexyl CMC Hexyl ether Chlorohexane added to CMC
making process
*B Decyl CMC Decyl ether Chlorodecane added to CMC
making process
CA 02359808 2001-07-25
WO 00/47705 PCT/US00/03472
-26-
**C C 12-C 13 alkoxy-2C 12-C 13 alkoxy-2C 12-C 13 alkyl glycidyl
ether
hydroxypropyl CMC hydroxypropyl added to CMC making
ether process
*D Hexadecyl CMC Hexadecyl etherChlorohexadecane added
to
CMC making process
*E Chloride salt of chloride salt 2,3-epoxypropyltrimethyl
3- of 3-
trimethylammonio-2- trimethylammonio-ammonium chloride
added to
hydroxypropyl ether 2-hydroxypropylthe CMC making process
of CMC ether
*F [-(C(O)- Cetyl Ketene Dimer
added to
CH(C16H33)- CMC making process.
C(O)CH2(C16H33) ]
ester of CMC or 1,3-
dioxo-2-
hexadecyloctadecyl
ester of CMC
CMC = Carboxymethylcellulose
* Manufactured by Metsa Specialty Chemicals
** Manufactured by Akzo
***DS~ for these materials was in the range of from about 0.001 to about 0.1
EXAMPLE 11
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 11
Example Material
Adduct
of
Imidazole-epichlorohydrin
(Ratio
of
imidazole:epichlorohydrin
1:1,
Polymer
from
Example
1 1)
N ~~
OH
(Idealized
Structure)
CA 02359808 2001-07-25
WO 00/47705 PCT/US00/03472
-27-
Adduct of Imidazole-epichlorohydrin
(Ratio of imidazole:epichlorohydrin 1.36:1, Polymer from
Example 2)
2 ~n~
L - off
(Idealized Structure)
Adduct of Imidazole-epichlorohydrin
(Ratio of imidazole:epichlorohydrin 1.75:1)
3
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~ ON N
J
Idealized Structure
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~ ON N
J
Adduct of piperazine and epichlorohydrin (ratio 1:1 )
OH
6 N
d
CA 02359808 2001-07-25
WO 00/47705 PCT/US00/03472
-28-
Adduct of piperazine and epichlorohydrin (ratio 1:1), benzyl quat
I
i
~O OH
~~\h+~d
7
Adduct of piperazine and epichlorohydrin (ratio 1:1 ) methyl quat
~~ H30H
N N
~J d
Adduct of piperazine,morpholine and epichlorohydrin (ratio 0.9:
0.4:1.0)
g ~ off
d
U
OH
Adduct of piperazine, piperidine and epichlorohydrin (ratio 0.9:
0.4:1.0)
OH
N~ ~ N
d
1~ OH
Adduct of piperazine, morpholine and epichlorohydrin (ratio 0.9:
0.4:1.0) methyl quat
CH OH ~--~
11 O N N~N~ 3 N/ \O
OH
Adduct of piperazine, piperidine and epichlorohydrin (ratio 0.9:
0.4:1.0) methyl quat
12 ~ CH3
N
OH OH
CA 02359808 2001-07-25
WO 00/47705 PCT/US00/03472
-29-
Adduct of piperazine,morpholine and epichlorohydrin (ratio 0.9:
0.4:1.0) benzyl quat
13 _ _
0 0
OH ~ OH
Adduct of piperazine, piperidine and epichlorohydrin (ratio 0.9:
0.4:1.0) benzyl quat
0
14
NT N~ No
0
OH ~ OH
Adduct of imidazole, piperazine and epichlorohydrin (ratio 2:1:3)
~---~ OH
1S N~~ N/ 'N
OH
Adduct of imidazole, piperazine and epichlorohydrin (ratio 1:1:2)
off
16 N N~
OH
Adduct of imidazole, 1,6 diaminohexane and epichlorohydrin
(ratio 1:1:2)
17
N~ N NH
OH J ~ NH OH J
CA 02359808 2001-07-25
WO 00/47705 PCT/US00/03472
-30-
Adduct of imidazole, dimethylaminopropylamine and
epichlorohydrin (ratio 1.02:0.34:1.0)
OH
N~~N N
18 ''_~ OHJ
N
HaCi wCH3
Adduct of imidazole-epichlorohydrin and chloroacetic acid
(Ratio- 1.36:0.97:0.07)
19
HOOC~N~~ N~~ NON~COOH
OH ~ OH
Adduct of imidazole-epichlorohydrin and chloroacetic acid
(Ratio- 1.36:0.93:0.14)
HOOC~N~ ~ N~~ N~ ~COOH
OH ~ OH
Adduct of imidazole-epichlorohydrin and chloroacetic acid
(Ratio- 1.36:0.83:0.34)
21 ~
HOOC~N~l~ N~~ NON~COOH
OH ~ H
Adduct of imidazole-epichlorohydrin and 3chlorohydroxypropyl
sulfonic acid (ratio: 1.0:0.83:0.34)
22 NaO,S N~ ~ ~~ ~ SO~Na
OH ~ OH
Adduct of imidazole-epichlorohydrin and 3 chlorohydroxypropyl
sulfonic acid (ratio:1.0:0.75:0.5)
23 NaO3S N~ ~ ~~ ~ S03Na
OH ~ OH
CA 02359808 2001-07-25
WO 00/47705 PCT/US00/03472
-31-
Adduct of imidazole, piperazine and
epichlorohydrin (Ratio- 1.0:1.0:2.0) quat with 0.22 moles of
24 chloroacetate
Hooc
OH ~ ~ OH
N~ N N ~N N
OH
L
Adduct of imidazole, piperazine and epichlorohydrin (Ratio-
1.0:3.0:4.0) quat with 0.32 moles of chloroacetate
25 "°°~
OH ~ ~ OH
N N N N
OH
L
Adduct of imidazole, piperazine andepichlorohydrin (Ratio-
1.0:1.0:2.0) quat with 0.45 moles of chloroacetate
26 °~°°c
OH ~ ~ OH
N N N N
Adduct of imidazole and epichlorohdrin, (ratio 1.75:1 ) oxidized
O-N~~ N~~ N~N~O
27 ~ OH ~ O ~ 'H
n
Adduct of piperazine and epichlorohydrin (ratio 1:1 ) 100%
oxidized
2g off
o ~---~ o
~N N
n
Adduct of piperazine and epichlorohydrin (ratio 1:1 ) 50%
oxidized
29
off o ~--~ o off
N~ UN
n
Adduct of piperazine, morpholine and epichlorohydrin (ratio
1:0.2:1 ) 100% oxidized
3 0 O~N N~ O N O
~ ~m
CA 02359808 2001-07-25
WO 00/47705 PCT/US00/03472
-32-
Adduct of piperazine, morpholine and epichlorohydrin (ratio
1:0.2:1)25% methyl quat and oxidized
31 ~ ~~H, ~~~o
/N ~ ~ ~h ~~ ~'~ ~~ N O
~/ OH OH OII
Adduct of imidazole, piperazine and epichlorohydrin (ratio 1:3;4)
100% oxidized
32 [~~o o ~NO OH
OH m ~ n
Adduct of imidazole, piperazine and epichlorohydrin (ration
1:3;4) 50% oxidized
33
0 0 oH, ~ off
N~~ N~N ~ N/ \N
off ~ ~ p
Adduct of imidazole, piperazine and epichlorohydrin (ration
1:1:2) 100% oxidized
34 ~N~~ \N~NO OH
OHJ~ /~
Adduct of imidazole, piperazine and epichlorohydrin (ration
1:5:6) 100% oxidized
OH
N~ O\N~N~O
N'~~ OH~ ~ p
Adduct of imidazole, piperazine and epichlorohydrin (ration
1:10:11 ) 100% oxidized
36 ~O ~ ~NO OH
N'~-~' oHJ~ '--'
Adduct of imidazole, piperazine andepichlorohydrin (Ratio-
1.0:3.0:4.0) quat with 0.32 moles of chloroacetate and oxidized
37 "°°'
OH Q OH
H~ N~ ~ NVN
OH rr~ ~ J P
CA 02359808 2001-07-25
WO 00/47705 PCT/US00/03472
_33_
Adduct of imidazole, piperazine and epichlorohydrin (Ratio-
1.0:1.0:2.0) quat with 0.45 moles of chloroacetate and oxidized
3 8 Hooc\
N~ . N~N~~ ~ / \N/, OH
OHJ U ~~.I~IJI'~~ a ~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 "°°o
~---~ OH p OH
\~/
N~ N+ N/ \ ~~ N N
OHJ~ ~ J n ~ a ~P
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, OH \ '~ O OH
N N N N N
OH m
41 Adduct of imidazole, dimethylaminopropylamine and
epichlorohydrin (ratio 1.02:0.34:1.0) oxidized
OH
N~~ N
OH n
N
H3~~ ~ ~CH3
O
EXAMPLE 12
Granular Detergent Test Composition Preparation
Several heavy duty granular detergent compositions are prepared containing a
fabric
enhancing component. These granular detergent compositions all have the
following basic
formula:
Table 12
Component Wt.
C12 Linear alkyl benzene sulfonate9.31
C14-15 alkyl ether (0.35 EO) 12.74
sulfate
Zeolite Builder 27.79
Sodium Carbonate 27.31
PEG 4000 1.60
CA 02359808 2001-07-25
WO 00/47705 PCT(US00/03472
-34-
Dispersant 2.26
C12-13 Alcohol Ethoxylate (9 1.5
EO)
Sodium Perborate 1.03
Soil Release Polymer 0.41
Enzymes 0.59
Cyclic Amine Based Polymers or 3.0
Oligomers
Hydrophobically Modified Cellulosic1.0
Based
Polymers or Oligomers
Perfume, Brightener, Suds Suppressor,Balance
Other
Minors, Moisture, Sulfate
100%
EXAMPLE 13
Liquid Detergent Test Composition Preparation
Several heavy duty liquid detergent compositions are prepared comprising a
fabric
enhancing component of this invention. These liquid detergent compositions all
have the
following basic formula:
Table 13
Component Wt.
C12-15 alkyl ether (2.5) sulfate38
C12 glucose amide 6.86
Citric Acid 4.75
C12-14 Fatty Acid 2.00
Enzymes 1.02
MEA 1.0
Propanediol 0.36
Borax 6.5 8
Dispersant 1.48
Na Toluene Sulfonate 6.25
Cyclic Amine Based Polymers or 1.0
Oligomers
Hydrophobically Modified Cellulosic0.1
Based
Polymers or Oligomers
CA 02359808 2001-07-25
WO 00/47705 PCT/US00/03472
-3~-
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 fabric
enhancing
component. Such granular detergent compositions all have the following basic
formula:
Table 14
Example Comparative
Component wt. % wt%
Na C12 Linear alkyl benzene 9.40 9.40
sulfonate
Na C14-15 alkyl 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 polyacrylate 2.26 2.26
C12-13 alkyl ethoxylate (E9)1.5 1.5
Sodium Perborate 1.03 1.03
Cyclic Amine Based Polymers 0.8 0
or
Oligomers
Hydrophobically Modified 0.3 0
Cellulosic
Based Polymers or Oligomers
Other Adjunct ingredients Balance Balance
100% 100%
