Note: Descriptions are shown in the official language in which they were submitted.
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SOIL RELEASE POLYMERS WITH
FLUORESCENT WHITENING PROPERTIES
CROSS REFERENCE TO RELATED APPLICATIONS
This is a Continuation-In-Part Application of co-pending Application Serial
Number 08/576,243 filed December 21, 1995.
FIELD OF THE INVENTION
The present invention relates to substituted or unsubstituted terephthalate
ester compounds having an oligomeric or polymeric backbone incorporating
particular substituted or unsubstituted polyoxyethylene moieties and having at
least
one fluorescent whitening end capping or fluorescent whitening pendant group.
The
present invention also relates to laundry cleaning compositions comprising
soil
release polymers of the present invention.
BACKGROUND OF THE INVENTION
Products used in laundering operations contain a number of ingredients
which provide certain basic benefits. For example, laundry cleaning products
are
formulated with detergent surfactant systems to remove a variety of soils from
clothes during washing. These laundry products can also include ingredients
which
provide through-the-wash fabric conditioning benefits such as softening and
anti-
static performance. More typically, softening and anti-static benefits are
provided
by other fabric treatment products. These and other fabric products are added
as part
of the rinse cycle or else in the dryer to provide the conditioning benefit.
In addition to standard cleaning, softening and anti-static benefits, laundry
detergent and fabric conditioning products can also impart other desirable
properties.
Of these, conferring desirable soil release and whitening properties to
fabrics woven
from polyester fiber, or in the case of whitening agents, also to natural
fibers, have
been the focus of research for many years. These target synthetic fabrics are
mostly
co-polymers of ethylene glycol and terephthalic acid, and are sold under a
number of
trade names, e.g. Cacron, Fortrei, Kodel and Blue C Polyester.
The hydrophobic character of polyester fabrics makes their laundering
difficult, particularly as regards oily soil and oily stains. The oily soil or
stain
preferentially "wets" the fabric. As a result, the oily soil or stain is
difficult to
remove in an aqueous laundering process. To overcome this difficulty in
removing
such stains and soil, polyesters containing random ethylene
terephthalate/polyethylene glycol (PEG) terephthaiate units (e.g. MILASE T),
have
been used as soil release compounds in laundry detergent products. Although
not
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straightforward, the development of improved soil release polymers having
superior
performance has produced agents that will efficiently absorb onto a given
substrate
(e.g. fabric) from a variety of application matrices (e.g. laundry liquor).
The ability
to readily form a deposited layer upon a fabric surface and to remain affixed
long
after the application process has ended is a desirable quality of both soil
release
agents as well as other laundry additives, in particular fluorescent whitening
agents.
The operation of brightening commercial fabrics is one of the highest value-
added treatments of a laundry detergent aside from the primary role of soil
removal
from the fabric itself. With the aid of fluorescent whitening agents (FWA's),
also
referred to as optical brighteners, optical compensation of the yellow cast
that
develops on substrates such as fabric can be achieved. The yellow cast is
produced
by the absorption of short-wavelength light {violet-to-blue). With fluorescent
whitening agents this lost light is in part replaced, thus a complete white is
attained.
This additional visible light is produced by the brightener by means of
fluorescence.
Optical whitening agents absorb the invisible ultraviolet portion of the
daylight
spectrum and convert this energy into the longer-wavelength visible position
of the
spectra. Fluorescent whitening, therefore, is based on the addition of light,
whereas
the older methods such as "blueing" is achieved by subtraction of light by the
addition of blue or blue-violet dyes to textiles.
One problem encountered with common fluorescent whitening agents in
laundry detergent applications is their lack of inherent affinity for
hydrophobic
fabric or soiled cotton. Typically comprised of small highly fluorescent
molecules,
optical brighteners are primarily modified to promote increased water
solubility of
the core organic structure. Because any molecular substituent added to these
small,
highly conjugated systems may upset the fluorescence emission profile,
structural
changes are made with due caution. In addition, highly planar molecules
inherently
clump, layer and stack instead of spreading out to form a uniform layer.
Surprisingly, the molecules of the present invention allow the formulator to
address this problem of low fabric affinity. By combining fluorescent
whitening
agents into the structure of the soil release polymers, both the desirable
properties of
soil release activity and optical brightening can be introduced
simultaneously.
It is well known to those skilled in the art that the properties which produce
successful soil release agents (SRA's) are a delicate balance of several
important
properties. For example, the backbone of the SR.A is key to providing affinity
for
the targeted fabric surface. When preparing molecules having soil release
properties, a backbone that comprises many of the identical elements of the
target
fabric is not all that is necessary to produce a superior product.
Manipulation of the
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polymer backbone structure as well as the end capping units has led to
advances in
soil release polymer technology. U.S. Patent 3,962,152, Nicol, et alia, issued
June 8,
1976; U.S. Patent 4,721,580, Gosselink issued January 26, 1988 and U.S. Patent
4,877,896, Maldonado, et alia, issued October 31, 1989; U.S. Patent 4,968,451,
Scheibel, et alia, issued November 6, 1990; U.S. Patent 5,041,230; Borcher,
Sr., et
alia, issued August 20, 1991; and U.S. Patent 5,415,807; Gosselink, et alia,
issued
May 16, 1995; all incorporated herein by reference, describe soil release
polymers
having a wide range of utility and applications. Surprisingly, the present
invention
allows the formulator to combine fluorescent whitening agents with known soil
release polymer technology, such as that described hereinabove, to obtain
compounds that contain the desired properties of both molecules.
The choice of suitable end capping unit has been a matter of close technical
scrutiny by those practicing the art of soil release polymer technology. The
selection of proper end capping group lends important properties to the
molecule,
for example, physical state (solid or liquid), solubility properties, and
compatibility
with adjunct materials. Additionally, formulatability (liquid or granular),
hot or cold
water usage are just a few of the modes in which the SRA must have
compatibility.
The present invention combines fluorescent whitening agents and soil release
polymers in a manner that is very practical from a formulator's view point.
The soil
release agents are chosen for their desirable properties and then fluorescent
whitening agents are attached to the molecular chain as end-capping units. The
formulator may choose to terminate one or both ends of the molecule with a
fluorescent end-capping unit. Alternatively, the polymer may comprise a
pendant
fluorescent whitening unit and have non-fluorescent whitening units as main
polymer backbone end caps. In another embodiment, the formulator may have
fluorescent units terminating only one or several branching chains. In
addition,
when the soil release polymer backbone is comprised of units that produce
branching or "star" polymers, these additional "ends" may be capped with any
proportion of fluorescent groups that is necessary to produce the desired
properties
of soil release and fluorescent whitening.
Because the fluorescent whitening units are attached as endcapping groups to
the supporting SRA backbone their addition to the molecule is not accomplished
in a
hapless or "random" manner. Although many SR.A's are assembled via "random
polymerization", attachment of the fluorescent whitening agent is preferably
accomplished in a controlled manner in order to assure the ability to balance
the
level of each functionality (SR.A and FWA) in the molecule. Surprisingly, the
present invention allows the formulator to incorporate along with the
fluorescent
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whitening end-capping units, other suitable end-capping units (e.g. modified
isethionate, sulfoaryl) that together provide for a complete delivery of both
soil
release and fluorescent whitening properties.
The prior art discloses certain hybrids of soil release polymers and
fluorescent whitening agents, in particular U.S. Patent 5,039,782, Larger, et
alia,
issued August 13, 1991; U.S. Patent 5,082,578, Larger, et alia, issued January
? l,
1992 and U.S. Patent 5,164,100, Larger et alia, issued November 17, 1992.
These
patent publications disclose soil release agents that comprise fluorescence
whitening
agents randomly incorporated directly into the main chain of the backbone
portion
of the respective molecules. The lack of control by which these agents are
introduced into the framework of the molecule limits the utility of the
method.
Rardom incorporation of fluorescent whitening agents into SRA's may not be the
most efficient method of delivery on a per weight basis. The random placement
of
FWA units may cause polymer backbone properties that are undesirable and also
non-reproducible. Thirdly, FWA groups that are proximal to one another may
have
the opportunity to quench one another.
It is an object of the present invention to provide soil release properties
and
fluorescent whitening into the same molecules in a direct and controlled way.
It is an object of the present invention to provide soil release and
fluorescent
whitening properties into the same molecule in a manner that allows the
formulator
to chose a wide range of fluorescent whitening groups for use in the present
invention.
It is a further object of the present invention to provide soil release
polymers
that have optionally one or more fluorescent whitening moieties incorporated
into
the molecule.
It is still further an object of the present invention to provide a laundry
detergent composition comprising at least 0.01 % of a detersive surfactant and
at
least 0.01 % of a fluorescent whitening soil release polymer.
It is an object of the present invention to provide fluorescent whitening soil
release polymers that can be formulated into either solid (bar), granular or
liquid
laundry detergent compositions.
SUMMARY OF THE INVENTION
The present invention relates to oligomeric or polymeric substituted or
unsubstituted ethylene terephthalate ester compounds comprising fluorescent
whitening groups, said compounds having the formula:
I(CaP)(R4)tj U~4-R 1-A-R2)u(A-R i-A-R3)v(A-R ~ -A-RS)w
.... i.
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-A-R 1-A-~ [(R~)t(Cap)]
wherein the A moieties are selected from the group consisting of
0 0 o O O o
-O-C- -C-O- -N-C- -C-N- -N-C-O O-C-N-
> >
R6 R6 R6 R6
O O
-N-C-N- -O-C-O-
R6 R6
and combinations thereof, wherein R6 is hydrogen, C I-C4 alkyl, and mixtures
thereof; the Rl moieties are 1,2-phenylene, 1,3-phenylene and 1,4-phenylene,
substituted 1,2-phenylene, 1,3-phenylene, and 1,4-phenylene having the formula
/ \ ~- \ / \
R~ R~ R~
wherein R~ is -OH, -C02H, -S03-M+, branching units of the formula -(A-RI-A-
R2)u{Cap)~ -{A-R1-A-R2)uA(CaP)~ -(A-R1-A-R3)~(CaP), -(A-RI-A-R3)vA{Cap)~ -
{A-R1-A-RS)W(Cap), and -(A-Ri-A-RS)wA{Cap), crosslinking units of the formula
-(A-R 1-A-RZ)u-~ -{A-R 1-A-R2)uA-~ -(A-R 1-A-R3 )v-~ -{A-R 1-A-R3 )vA-~ -{A-R
~ -A_
RS)w , and -(A-R1-A-RS)wA- connecting said R~ moiety to an R1 or RS moiety of
a
second oligomer or polymer chain; substituted and unsubstituted naphthalene,
arylalkylene units having the Formula
/ \ (~2~- / \ (CH2)k- / \ (CH2~-
alkylene units having the formula
-(CH2~-
alkenylene units having the formula
-(CH=CH~-{CH2~-
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and combinations thereof, wherein k is 1 to 12, j is 1 or ?, and M is a
cationic
moiety; the R2 moieties comprise substituted or unsubstituted ethyleneoxy
units
having the formula
'~H(Y)CH20?- or -(CHzCH(Yp)-
wherein (a) Y is a -H, Ct-C4 alkyl, alkoxymethyl, and mixtures thereof; and
(b)
combinations of the foregoing R' moieties with up to 50% of other compatible
R'
moieties wherein Y is a branching unit of the formula -CH20-(CH~CH20)p-
CH~CH2-OR wherein R is C1-C4 alkyl or a crosslinking unit of the formula -CH20-
(CH-,CH20)p-CH~CH2- by which said R2 moiety is crosslinked to an R2 moiety of
a
second oligomer or polymer chain; p is 0 to 50; the R3 ethyleneoxy units are
selected from the moieties -(CH2CH~0)q-CH2CH2- wherein q is from 1 to 99
wherein each R3 unit may have the same or different values of q; the R4 units
are
R2, R3 or RS units; the R5 units having the formula
R9 R9
-Rto-(O-Rto)W
I
R8 Rs
wherein the index i has the value of 0 or 1, R10 is C2-C6 linear alkylene, C3-
C6
branched alkylene, CS-C~ cyclic alkylene, CS-C~ substituted cyclic alkyiene,
CS-C~
heterocyclic alkylene, arylene, substituted arylene, and mixtures thereof;
said R 10
unit is substituted by one or more Rg, R9 unit, and mixtures thereof, wherein
each
Rg is independently selected from the group consisting of hydrogen, R~, and
mixtures thereof; R9 moieties wherein each R9 is independently hydrogen, -Z-
S03-
M+> -Z-(FWU), and mixtures thereof, wherein each Z is a connecting moiety
independently selected from the group consisting of alkylene, alkenylene,
alkoxyalkylene, oxyalkylene, arylene, alkylarylene, alkoxyarylene,
polyalkoxyalkylene units, and mixtures thereof; -(FWU) is a fluorescent
whitening
unit; wherein Rg and R9 when taken together, at least one Rg or R9 moiety is
not a
hydrogen atom; M is a cationic moiety; the value of t is 0 or 1; the value of
a is from
about 0 to about 60; the value of v is from about 0 to about 35; the value of
w is
from 0 to 35; comprising end-capping groups (Cap) independently selected from
the
group consisting of:
(a) fluorescent whitening units; and
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(b) non-(fluorescent whitening) units, said non-(fluorescent whitening)
units are selected from the group consisting of
i) ethoxylated or propoxylated hydroxyethane and
propanesulfonate units of the formula
(M03S)(CH2)m(R< <O)~R11-, where M is a salt forming
cation such as sodium or tetralkylammonium, R~ 1 is ethylene
or propylene or a mixture thereof, m is 0 or 1, and n is from 0
to 20;
ii) sulfoaroyl units of the formula -O{O)C(C6H4)(S03-M+),
wherein M is a salt forming cation;
iii) modified poly(oxyethylene)oxy monoalkyl ether units of the
formula R120(CH~CH20)kCH2CH2-, wherein R12 contains
from 1 to 4 carbon atoms and k is from about 3 to about 100;
and
iv) ethoxylated or propoxyiated phenolsulfonate end-capping
units of the formula M03S(C6H4)(OR13)n-, wherein n is from
1 to 20; M is a salt-forming cation; and R ~ 3 is ethylene,
propylene and mixtures thereof.
The compounds of the present invention are useful in articles which provide
fabric soil release and fluorescent whitening benefits in certain laundry
detergent
compositions. These compositions comprise:
(a) at least 0.01 % by weight, of a detersive surfactant;
(b) at least 0.01% by weight, a soil release polymer comprising a non
hydrolyzable fluorescent whitening end capping moiety; and
(c) carrier and adjunct ingredients.
All percentages, ratios and proportions herein are by weight, unless
otherwise specified. All temperatures are in degrees Celsius (~C). All
documents
cited are incorporated herein by reference.
DETAILED DESCRIPTION OF THE INVENTION
The soil release polymers of the present invention have the formula:
L(Cap)(R4)tJ L(A-R I-A-R2)u(A-R 1-A-R3)v(A-R i-A-RS)w
-A-R ~-A-J ~(R4)t(CaP)~
In this formula, the moiety
-UA-R.1-A-R2)u(A-R 1-A-R3 )v(A-R 1-A-RS )w~-A-R 1-A-
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forms the oligomeric or polymeric backbone of the compound. The capping groups
of the present invention are non-hydroIyzable fluorescent whitening or non-
hydrolyzable non-fluorescent whitening end-capping units, (Cap). The capping
groups of the present invention serve to cap or provide a distinct terminus to
the
ends of the main polymer chain (backbone) as well as serving to terminate any
of the
backbone branches. In addition to the role of truncating chain elongation, the
non-
hydrolyzable end-capping units provide specific properties to the soil release
polymer.
The soil release polymers of the present invention comprise carbonyl linking
A moieties, for example, carboxy linking A moieties having the structure
o O
II II
-~C- or -C-O-
or amide linking A moieties having the structure
-N-O- or
-C-N-
I
R6 R6
or carbamate linking A moieties having the structure
O O
II II
-N-C-O or O-C-N
R6 R6
or urethane or carbonate linking A moieties having the formula
O O
-N-C-N- or -~C-O-.
R6 R6
wherein R6 is hydrogen, CI-C4 alkyl, and mixtures thereof. Preferably, linking
moieties A consist entirely of (i.e., comprise 100%) carboxy moieties
O O
-o-c- -c-o
or
i.e., each A is either
,,
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O o
.-O-C- ~C-o
or
The degree of partial substitution in which carboxy moieties are replaced
with these other linking moieties such as amide, urethane, carbamate and
carbonate,
should be such that the soil release properties of the compounds are not
adversely
affected to any great extent. In addition, the composition of A moieties must
be
consistent with proper chemical bonding, and where applicable, to fluorescent
whitening end capping units, for example, peroxide linkages are not included.
The R~ units are essentially phenylene, naphthalene, substituted phenylene
and substituted naphthalene, as defined herein below, alkylarylene units of
the
formula
-(CH2)k / \ , -(CH2)k / \ -(CHz)k
alkylene units having the formula
-(CH2)k-
alkenylene moieties
(CHz)k-(CH=CH)~
and combinations thereof with other possible R1 groups, inter alia substituted
1,4-
phenylene moieties; wherein k is 1 to 12, j is 1 or 2, M can be H or any
compatible
water-soluble cation. Suitable water-soluble cations include the water-soluble
alkali
metals such as potassium (K+) and especially sodium (Na+), as will as ammonium
(NH4+). Also suitable are substituted ammonium cations having the formula:
R~
R3-N~ R2
R4
where R1 and R2 are each a C1-C2p hydrocarbyl group (e.g. alkylene, hydroxy-
alkylene) or together form a cyclic or hererocyclic ring of from 4 to 6 carbon
atoms
(e.g. piperidine, morpholine); R3 is a CI-C2p hydrocarbyl group; and R4 is H
(ammonium) or a C~-Cep hydrocarbyl group {quaternary amine). Typical
substituted ammonium cationic groups are those where R4 is H (ammonium) or C~-
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C4 alkyl, especially methyl (quaternary amine); R ~ is C 1 p-C 1 g alkyl,
especially C 1 ~-
C 14 alkyl; R'- and R' are each C I-C4 alkyl, especially methyl.
For the purposes of the present invention substituted 1,2-phenylene, 1,3-
phenylene, and 1,4-phenylene units are defined as moieties having essentially
the
formula:
/ \ /. \ / \
R7 R~ R7
wherein one or more R~ moiety, can be present on any one aromatic ring, said
R~
moiety comprises a single functional group, a branching chain or a
crosslinking
chain.
For the purposes of the present invention unsubstituted naphthalene moieties
are defined as naphthalene units having no other substitutions other than the
bonds
linking these units to the polymer chain backbone. Examples of unsubstituted
naphthalene suitable for the present invention include compounds having
essentially
the formula:
/ W / ~ / I ~ /
/ ~ I / ~ / ~ /
/ ( \ / ~ ~ ~ ~ W
/ ~ / ~ / ~ /
/ ~ ~ /
/ ~ /
For the purposes of the present invention substituted naphthalene moieties
are defined as naphthalene units having one or more substitutions. For example
structures having the formula
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S03Na
/ ~ \
\ /
~~a f~a S03Na
are examples of naphthalene units having one or more substitutions. The
preferred
naphthalene moieties of the present invention comprise naphthalene rings
having a
single substitution, for example, naphthalene rings incorporated into the main
chain
of the polymer backbone and having one additional moiety such as hydroxyl or -
S03-M+, or one branching chain or one crosslinking chain.
Preferably R~ is 1,4-phenylene, 2,6-naphthalene, 1,5-naphthalene,
substituted 1,3-phenylene, and substituted 2,6-naphthalene. More preferred R~
are
1,4-phenylene and substituted 1,3-phenylene, most preferred is 1,4-phenylene.
The
Rl moieties can be substituted with various moieties, for example R7 is -OH, -
C02H, -S03-M+, crosslinking units of the formula -(A-RI-A-R2)u-, -(A-R1-A-
R2 )uA-~ -(A-R 1-A-R3 )v-~ -(A-R 1-A-R3 )vA-~ -(A-R 1-A-RS )w-, and -(A-R 1-A-
RS)wA-.
For the purposes of the present invention branching units are defined as
backbone-like chains comprising the units A, Ri, R2, R3, and RS whereby these
branching units terminate in a suitable non-hydrolyzable fluorescent whitening
end
capping group or in a suitable non-hydrolyzable non-fluorescent whitening end
capping group. For the purposes of the present invention the preferred
branching
units comprise the basic branching moieties having the formula -(A-R~-A-
R2)u(CaP)~ -(A-R~-A-R2)uA(Cap)~ -(A-R1-A-R3)v(CaP)~ -(A-R1-A-R3)vA(Cap)~
(A-RI-A-R5)W(Cap), and -(A-Rl-A-RS)WA(Cap) wherein the indices u, v and w
indicate the number of non-end capping units present. For example, a branching
moiety having the formula -(A-R1-A-R2)2(Cap) wherein A is carboxy, R1 is 1,4-
phenylene and R2 is ethyleneoxy, has the structure
O O O O
-O-C ~ ~ C-O-(CH2CH20)-C ~ ~ C-O-(CH2CH20)-(Cap)
Typically the branching chains according to the present invention are
comprised entirely of one type of basic branching unit and a suitable non-
hydrolyzable capping moiety, for example, a branching chain having the
structure
-{A-Rl-A-R3)~(Cap), would anly comprise -(A-RI-A-R3)- units, however,
branching chains can also comprise a mixture of basic branching units, an
example
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of which is a branching chain having the structure -(A-R~-A-R~),~,(A-Rl-A-
R3)~(Cap). Mixed branching units of this type are more suitable for use in
soil
release polymers of the present invention having a "star" polymer branching.
Star
polymers are defined, for the purposes of the present invention, as soil
release
polymers according to the present invention that comprise moieties or other
units in
the polymer backbone that promote the formation of chain branching as well as
soil
release polymers that otherwise comprise multiple branching units.
The length of the branching unit when combined with the longest continuous
portion of the polymer backbone may in some cases have a length that is equal
to the
length of the main continuous substituted or unsubstituted terephthalate
polymer
backbone but preferably the branching moiety is moderate in length, for
example,
the value of the indices u, v, and w of the branching unit are less than about
22,
more preferably the branching moiety is short in length, the value of the
indices u, v,
and w are less than about 6. The branching units are terminated with a non-
hydrolyzable end capping unit. The non-hydrolyzable end capping unit comprises
either a non-fluorescent whitening end capping unit or a fluorescent whitening
end-
capping unit according to the present invention.
The substituted R~ moieties additionally comprise R~ substituents that are
crosslinking moieties having the formula -(A-R1-A-R2)u-, -(A-Rl-A-R2)uA-, -(A-
Rl-A-R3)v-~ -(A-R1-A-R3)vA-~ -(A-Rl-A-RS)w-~ ~d -(A-Rl-A-RS)wA- fat
comprise the basic crosslinking units -(A-Rl-A-R2)-, -(A-Rl-A-R2)A-, -(A-Rl-A-
R3)-, -(A-R1-A-R3)A-, -(A-Rl-A-R~)-, and -{A-Rl-A-RS)A-. For the purposes of
the present invention, a crosslinking moiety may comprise a mixture of units,
for
example, a -(A-R 1-A-RS)- unit and a -(A-R 1-A-R2)- may combine to form a
mixed
crosslinking moiety. This may result from pre-linking these two units or from
the
linking of a -(A-Rl-A-RS)- extending from one chain which chemically combines
with a -{A-Rl-A-R2)- growing or extending from a second 5oi1 release polymer
chain.
For the purpose of the present invention the term "crosslinking units" are
defined as backbone-like chains comprising the units A, R~, R2, R3, and RS and
these crossIinking units thereby connect one polymer or oligomer chain of a
soil
release polymer with a second polymer or oligomer chain. Crosslinking units
may
connect similar moieties on two separate chains. For example an R1 moiety of
one
chain may be connected by a crosslinking unit to an R~ moiety of a second
chain.
Likewise, an R2 moiety can be connected to an RZ moiety of a second chain.
However, crosslinking can occur between two separate moieties, for example, an
R~
unit of one chain can be crosslinked to an R2, R3 or RS unit of a second soil
release
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polymer chain. For the purposes of the present invention the preferred
crosslinking
units are comprised of basic crosslinking moieties having the formula -(A-R~-A-
R2)u ' -(A-RI-A-R2-''~)~-~ -(A-R~-A-R3)v-~ -{A-R1-A-R3)vA-~ -(A-Ri-A-RS)~,-,
and
-(A-R1-A-RS)WA- wherein the indices u, v and w can have the values from 1 to
about 20, preferably from about 2 to about 6.
For the Rt moieties, the degree of partial substitution with moieties other
than 1,4-phenylene should be such that the soil release properties of the
compound
are not adversely affected to any great extent and that there is compatibility
with the
selected particular fluorescent whitening end capping unit. Generally the
degree of
partial substitution which can be tolerated will depend upon the backbone
length of
the compound, i.e., longer backbones can have greater partial substitution for
1,4-
phenylene moieties. Usually compounds where the Rl comprise from about 50 to
100% 1,4-phenylene moieties (from 0 to 50% moieties other than 1,4-phenylene)
have adequate soil release activity and are compatible with any choice of one
or
more fluorescent whitening end capping units.
The R2 moieties are essentially ethylene, -(CH2CH20)p-CH2CH2- or
substituted ethylene moieties of the formula
-(CH(YxH20}- or -(CHZCH(Yp)-
wherein the Y is Cl-C4 alkyl, C1-C4 alkoxymethyl, -CH20-(CH2CH20)p
CHZCH2-OR wherein R is C 1-C4 alkyl or a crosslinking unit of the formula ,
crosslinking units of the formula -(A-R1-A-R2)u-, -{A-R1-A-R2)u-A-, -(A-R1-A-
R3)v-, -(A-RI-A-R3)v-A-, -{A-R1-A-RS)w-, and -(A-R1-A-RS)w-A- which connect
the R2 moiety of one chain to an Rl, R2 or RS moiety of a second oligomer or
polymer chain. As used herein, the term "the R2 moieties are essentially
substituted
ethylene moieties having C ~-C4 alkyl or alkoxymethyl substituents" refers to
compounds of the present invention where the R2 moieties consist entirely of
substituted ethylene moieties, or are partially replaced with other compatible
moieties having the aforementioned Y moieties. Examples of preferred
compatible
moieties include linear C2-C6 alkylene moieties such as ethylene, 1,3-
propylene,
1,4-butylene, 1,5-pentylene or 1,6- hexylene, 1,2-cycloalkylene moieties such
as
1,2-cyclohexylene, 1,4-cycloalkylene moieties such as 1,4-cyciohexylene and
1,4-
dimethylenecyclo-hexylene, polyoxyalkylated 1,2-hydroxyalkylene such as
-CH2CH-
CH20(CH~CH~O)p-R
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14
or alkyleneoxyalkyl moieties such as -CH~CH~O(CH~_CH~_)-, wherein p is from 0
to
20.
For the R2 moieties, the degree of partial replacement with these other
compatible moieties should be such that the soil release, solubility and
fluorescent
whitening properties of the compounds are not adversely affected to any great
extent. Generally, the degree of partial replacement which can be tolerated
will
depend upon the soil release, solubility and fluorescent whitening properties
desired.
the backbone length of the compound, (i.e., longer backbones generally can
have
greater partial replacement), and the type of moiety involved (e.g., greater
partial
substitutions with ethylene moieties generally decreases solubility). Usually,
compounds where the R2 comprise from about 20 to 100% substituted or
unsubstituted ethylene moieties (from 0 to about 80% other compatible
moieties)
have adequate soil release activity. However, it is generally desirable to
minimize
such partial replacement for best soil release activity and solubility
properties.
(During the making of polyesters according to the present invention small
amounts
of polyoxyalkylene moieties (as dialkylene glycols) can be formed from glycols
in
side reactions and then incorporated into the polyesters). Preferably, R2
comprises
from about 80 to 100% substituted or unsubstituted ethylene moieties, and from
0 to
about 20% other compatible moieties. For the R2 moieties, more preferred
substituted moieties include, I,2-ethylene, 1,2-propylene, I,2-butylene, 3-
methoxy-
1,2-propylene and mixtures thereof, most preferred R2 substituted moieties are
essentially 1,2-propylene moieties.
The R3 moieties are essentially the polyoxyethylene moiety -(CH2CH20)q-
CH2CHr or polyalkylene moieties derived from block or random copolymerization
of ethylene oxide with propylene oxide and/or butylene oxide. As used herein,
the
term "the R3 moieties are essentially the polyoxyethylene moiety -{CH2CH~0)q-
CHZCH2-" refers to compounds of the present invention in which the R3 moieties
consist entirely of this polyoxyethylene moiety, or further include other
compatible
moieties. The degree of inclusion of these other moieties should be such that
the
soil release properties of the compounds are not adversely affected to any
great
extent and that these moieties are compatible with the selected fluorescent
whitening
end capping moieties. Usually, in compounds of the present invention, the
polyoxyethylene moiety comprises from about 50 to 100% of each R3 moiety.
(During the making of polyesters according to the present invention, very
small
amounts of oxyalkylene moieties may be attached to the polyoxyethylene moiety
in
side reactions and thus incorporated into the R3 moieties).
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For the polyoxyethylene moiety, the value for q is at least 1, and is
preferably at least about 9, more preferably at least about I 2. The value for
q
usually ranges from about 12 to about 50. Typically the value for q is in the
range
of from about 12 to about 35.
R4 moieties are an optional hydrolyzable fragment which serves to provide
a suitable linking of the non-hydrolyzable end capping units to the oligomeric
or
polymeric backbone. R4 moieties comprise R2, R' or RS units. Any R4 units may
be used provided the rules of chemical bonding are adhered to and that no
peroxide,
-N-O- or azo bonds are formed.
The RS units are essentially the substituted alkylene or alkylene ether
moieties having the structure
R9 R9
-Rio-(p_Rto)i
Rs Rs
wherein the index i has the value of 0 or 1, and Rlo is C2-C6 linear alkylene,
C3-C6
branched alkylene, CS-C~ cyclic alkylene, for example, of the formula;
(CH~)b
wherein the index b is from 1 to 3, however the attachment of the ring is not
limited
to 1,3 linkages as shown but may be 1,2 linkages or 1,4 linkages as well. RIO
is
CS-C~ alkyl substituted cyclic alkylene wherein the alkyl substituents are CI-
C4
alkyl; arylene, substituted arylene, CS-C~ heterocyclic alkylene, for example,
piperidinyl, pyrrolinyl, 2,3-dioxanyl of the formula
and 2,5-morpholinyl of the formula
O
O
N
O
However any mono or di-heteroatomic ring comprising a nitrogen atom, oxygen
atom, or mixtures thereof is suitable as an RIO moiety except those units
forming
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16
peroxide or azo bonds. The R10 units are substituted by Rg and R9 units that
independently selected, wherein Rg is hydrogen, R~, and mixtures thereof; R9
is
hydrogen, -Z-S03-M+, or -Z-(FWU), wherein (FWU) is a fluorescent whitening
unit as described hereinafter, Z is a side chain connecting moiety selected
from the
group consisting of alkylene, alkenylene, alkoxyalkylene, oxyalkylene,
arylene,
alkylaryiene, alkoxyarylene, polyalkoxyalkylene, and mixtures thereof, M is a
cationic moiety as defined further herein above.
Preferred RS moieties are essentially C~-C6 alkylene chains substituted by
one or more R8 and R9 moieties. The RS units comprise either one C~-C6
alkylene
chain substituted by one or more independently selected Rg and R9 moieties
(preferred) or two C~-C6 alkylene chains said alkylene chains joined by an
ether
oxygen linkage, each alkylene chain substituted by one or more independently
selected Rg and R9 moieties, that is RS may comprise two separate R10 units,
each
of which is substituted by one or more independently selected Rg and R9
moieties.
Preferably the R8 units are hydrogen and preferably the R9 units are -Z-S03-
M+;
more preferably all Rg moieties are hydrogen and one R9 moiety is -Z-S03-M+
with
the remaining R9 moieties being hydrogen atoms. When the value of the index i
is
equal to 1 (two R10 units comprise the RS unit), a preferred formula is
R9 R9 R9 ~9
1
_
-C-C-O-C-
C
-
~8 ~8 ~8 ~8
wherein each R10 comprises a C~ alkyiene moiety. Preferably Rg is hydrogen,
one
R9 moiety is -Z-S03-M+, preferably the C2 carbon is substituted by the -Z-S03-
M+
moiety, and the balance are hydrogen atoms, having therefore a formula:
-CHCH2-O-CH2CH2-
CH2(OCH2CH2~S03 M+
wherein Z is a polyethyleneoxymethyl moiety.
As used herein, the term "RS moieties consist essentially of units
R9 R9
-Rlo-(O-Rio)W
R8 Rs
having the index i equal to 0 wherein R8 units are hydrogen and having one R9
equal
to -Z-S03-M+ and having the remaining R9 units equal to hydrogen, wherein Z is
a
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I7
side chain connecting moiety selected from the group consisting of alkylene,
alkenylene, alkoxyalkylene, oxyalkylene, arylene, alkylarylene, alkoxyarylene
and
mixtures thereof', refers to the preferred compounds of the present invention
wherein the Rg moieties consist entirely of hydrogen atoms and R9 moieties
comprise for example a
CH2- C H-
CH~(OCH,CH2)xS03~ Na+
which is capable of inclusion into the polymeric backbone of the soil release
polymers of the present invention as an -A-RS-A- backbone segment. The units
are
easily incorporated into the oligomer or polymer backbone by combining
starting
materials having the general formula
HO-CH2-CH-OH
CH2(OCH2CH2~SO3 Na+
wherein x, for the purposes of the Z moiety of the present invention, is from
0 to 20.
Other suitable monomers capable of inclusion into the backbone of the soil
release polymers of the present invention as RS moieties includes the
alkoxyarylene-
containing monomer having the general formula
HO-C H2-C H-OH
CH2(OCHZCHz~O ~ ~ S03~Na+
wherein x is 0 to 20. A further example of a preferred monomer resulting in a
preferred RS unit wherein i is equal to 0, are the 2-
sodiosulfopoly(ethyleneoxy)-
methyl-1,2-propanediols having the formula
HO-CH2-CH-OH
CHZ(OCHZCH2~SO3 Na+
wherein x is from 0 to about 20; more preferred are the monomers
OH
HO-CH2-CH-CH2-OH or HO-CHI-CH-CHI
OCH2CHZS03 Na+ OCHZCH2S03 Na+
For the oligomer or polymer backbone of the soil release compounds of the
present invention having the formula
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18
-~~A-R ~ -A-R2)u(A-R ~ -A-R' )v(A-R ~ -A-R5 )w-A-R ~ -A]-
the indices u, v and w are defined as follows; the value of a is from about 0
to about
60; the value of v is from about 0 to about 35; the value of w is from 0 to
35.
END CAPPING UNITS
The compounds of the present invention further comprise non-hydrolyzable
end capping units, (Cap). The end capping units are either fluorescent
whitening
units or non-fluorescent whitening units. One role of the end capping units of
the
present invention is to terminate the polymer backbone thereby ending chain
propagation of the backbone and branching units. Also, the end capping units
provide the soil release polymers of the present invention with certain
intrinsic
properties.
The formulator, by selection of the end capping units disclosed herein below,
is able to design and prepare soil release polymers having a wide range of
solubility
and fabric affinity. In addition, the inclusion of the fluorescent whitening
end-
capping units provide to the consumer fabric optical brightening enhancement
in a
more efficient manner. The soil release polymers of the present invention have
a
high affinity for fabric. This high affinity assures the formulator can
deliver the
desired properties of soil release and fluorescent whitening in the most cost
effective
manner. The soil release polymers of the present invention can have an
affinity for
certain fabric surfaces as high as conventional optical brighteners but obtain
this
high affinity by different specificity. This low fabric affinity of
traditional optical
brighteners results in the fact that much of the fluorescent whitening agent
formulated into laundry detergents is carried away in the laundry rinse
liquor.
Fluorescent whitening units (FWU)
Fluorescent whitening units (FWU) can be capping groups or can be
incorporated into RS units as pendant groups. The fluorescent whitening units
can
not be readily hydrolyzed into smaller sub-units or in the case where they
comprise a
pendant group with in RS units, they are not readily hydrolytically cleaved
from the
rest of the RS unit. Preferred non-hydrolyzable fluorescent whitening end-
capping
units of the present invention have the formula
-(L)s-(R~ a h,-(Ri s )_ B-(Ri 6)-(Ri ~)z
wherein the B units are conjugated bridging units, preferably ethylene units
having
the formula
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19
-CH=CH- ,
4,4'-bisphenylethylene units having the formula
CH=CH
1,4-bisethylenephenylene units having the formula
-CH=CH ~ ~ CH=CH-
1,4-naphthylene, and mixtures thereof. More preferred B units are ethylene and
4,4'-
bisphenylethylene, most preferred B unit is ethylene.
The R14 units are 1,4-phenylene or substituted 1,4-phenylene moieties of the
formula
R~8
or triazinyIamino or substituted triazinylamino units of the formula
RI9
N-
--~~ N
N -_-~
NH-
wherein R1g and R19 are independently selected from the group consisting of
hydroxyl, amino, cyano, halogen, -S03-M+, C I-C4 alkylamino, C Z-C4
dialkylamino
and mixtures thereof. Preferred R14 units are unsubstituted 1,4-phenylene and
substituted 1,4-phenylene, more preferred is unsubstituted 1,4-phenylene. The
index
y has the value 0 or 1. When the index y is 0, the non-hydrolyzable
fluorescent end-
capping unit, (Cap), segments L and R15 are bonded directly to one another.
When
the index y is l, and R~4 is a substituted 1,4-phenylene, preferred R~8
moieties are
cyano and -S03-M+, preferably -S03-M+. When R~4 is a substituted
triazinylamino
moiety the preferred R19 are amino, C~-C4 alkylamino, C~-C4 dialkylamino and
mixtures thereof, more preferred are CI-C4 alkylamino or CI-C4 dialkylamino,
most
preferred are dimethylamino, methyl-amino, diethylamino and ethylamino.
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The R~5 and R16 units are each independently 1.4 phenylene moieties or
substituted 1,4-phenylene moieties of the formula
R2o ~ Rz~
wherein the R2~ and R' 1 moieties are each independently selected for the R15
and
R~6 units. R2~ and R21 moieties are selected from the group consisting of
hydrogen, C~-C4 alkyl, amino, Cl-C4 alkylamino, C1-C4 dialkylamino, Cl-C4
alkoxy, anilino, N-methyl-N-hydroxyethylamino, bis(hydroxyethyl)amino,
morpholino, diethylamino, chloro, bromo, iodo, cyano, nitrilo,
sulfophenylamino,
2,5-disulfophenylamino, -(S03-M+), -CO~H, and mixtures thereof. The preferred
embodiments of the non-hydrolyzable fluorescent end-capping units of the
present
invention have R15 and R~6 units that comprise only one substituent, that is
only the
R2~ unit is present in the preferred embodiments (R21 is hydrogen). When the
R2~
and R21 units are both present, the groups are preferably oriented para or
meta
relative to one another on the 1,4-phenylene ring, more preferably R2~ and R21
are
oriented para to one another.
Preferred R2~ and R2 ~ units are amino, C 1-C4 alkylamino, C I-C4
dialkylamino, C~-C4 alkoxy, anilino, N-methyl-N-hydroxyethylamino,
bis(hydroxyethyl)amino, morpholino, diethylamino, sulfophenylamino, 2,5-
disulfophenylamino, and -(S03-M+), more preferred are CI-C4 alkylamino, C~-C4
dialkylamino, N-methyl-N-hydroxyethylamino, bis(hydroxyethyl)amino, and -(S03-
M~), most preferred is -(S03-M+). Most preferred R2~ unit is hydrogen, that
is, R15
and R16 have only one substituent group present.
The R1~ units are selected from the group consisting of hydrogen, hydroxyl,
amino, methylamino, dimethylamino, cyano, -S03-M+, C~-C4 alkyl, C~-C4 alkoxy,
phenyl, substituted phenyl of the formula
Ris
wherein R~ 8 is selected from the group consisting of hydrogen, hydroxyl,
amino,
cyano, halogen, -S03-M+, C~-C4 alkylamino, CI-C4 dialkylamino and mixtures
thereof; triazinylamino, or a substituted triazinylamino or substituted
aniline of the
formulas
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21
R?2
R..4
N
N or -NH
N=-C
NH-R27 Rz3
wherein R22, R23, R'4 and R27 are independently selected from the group
consisting
of hydrogen, hydroxyl, amino, cyano, halogen, -S03-M+, C 1-C4 alkylamino, C I-
C4
dialkylamino and mixtures thereof. The index z has the value 0 or 1. When the
index z is 0, the (Cap) terminates in R ~ 6 units. When the index z is 1, and
R~ ~ is a
substituted 1,4-phenylene, preferred R~8 moieties are amino and -S03-M+,
preferably -S03-M+. When R17 is substituted triazinylamino, preferred R22 is
amino, C1-C4 alkylamino, C1-C4 dialkylamino and mixtures thereof, more
preferred
is C1-C4 alkylamino or C~-C4 dialkylamino, most preferred is dimethylamino,
methyl-amino, diethylamino and ethylamino. When R ~ ~ is substituted
triazinylamino preferred R27 is C 1-C4 alkyl, most preferred is methyl and
ethyl.
When R1~ is a substituted aniline preferred R23 and R24 are amino, C1-C4
alkylamino, C~-C4 dialkylamino and mixtures thereof, more preferred is C~-C4
alkylamino or C1-C4 dialkylamino, most preferred is dimethylamino, methyl-
amino,
diethylamino and ethylamino.
Preferred R~8 units are unsubstituted amino, methylamino, dimethylamino,
cyano, -S03-M+, Ci-C4 alkyl, C~-C4 alkoxy, i,4-phenylene, substituted 1,4-
phenylene, more preferred are dimethylamino, methylamino, diethylamino,
ethylamino, -S03-M+ and unsubstituted 1,4-phenylene. Most preferred R18 are
dimethylamino, diethylamino and -S03-M+.
For the purpose of the present invention, when R ~ ~ is a hydrogen atom, the
value of the index z is 1.
The linking L units of the non-hydrolyzable end-capping units of the present
invention serve to attach the fluorescent portion of the end capping unit to
the
polymer backbone. The L units are selected from the group consisting of A
units,
R2 units, R3 units, RS units, oxygen, C ~ -C4 alkyl, C ~-C4 alkoxy,
alkylamino,
alkoxyamino, alkyldiamino, and mixtures thereof. Preferred linking units are A
units, oxygen, and C1-C4 alkyleneoxy. L linking groups are selected in such a
way
that no non-compatible chemical bonding is present. For example, provided that
when L = A, the A unit is not readily hydrolytically cleaved from the rest of
the end
capping unit. That is, the linkage subject to hydrolysis is between the
linking group
A and the polymer backbone, not between linking group A and the rest of the
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capping group. For the purpose of the present invention "non-hydrolytically
cleaved" refers to "hydrolysis or alcoholysis under acid or base catalyzed
conditions,
especially under the normal conditions of processing or usage by consumers".
An example of an (Cap) moiety attached to a soil release polymer backbone
has the structure:
BACKBON)J-C-O-CH~CH20 ~ \ CH=CH ~ \ S03Na
O
and when this BACKBONE-(Cap) is subjected to the proper hydrolysis conditions,
the unit above fragments into the -(Cap) and BACKBONE- units having the
structure
BACKBONE-C-OH + HOCH2CH2-O ~ ~ CH=CH ~ ~ S03Na
O
In the above cited example, BACKBONE-CO~H represents the hydrolyzed
soil release polymer backbone. The end capping group comprises linking L unit
that
is an ethyleneoxy group, -CH2CH20-, R14 unit is absent (y is equal to 0), RCS
unit
is 1,4-phenylene, bridging unit B is ethylene, Ri6 is 1,4-phenylene and R17 is
-
S03-M+ wherein M is sodium.
Another example of a non-hydrolyzable end-capping unit, wherein the
linking L unit is an A unit (A unit stays with the fluorescent end capping
group and
is part of the non-hydrolyzable end cap); R14 unit is absent (y is equal to
0), R15 unit
is 1,4-phenylene, bridging unit B is ethylene, R~6 is 1,4-phenylene and R1~ is
-
S03-M~ wherein M is sodium has the formula:
-O-O ~ ~ CH=CH ~ ~ S03Na
Further suitable non-hydrolyzable end-capping units of the present invention
have the formula
-L-FWA-R25
wherein linking unit L is the same as defined herein above, FWA is a
fluorescent
whitening unit non-limiting examples of which include substituted and
unsubstituted
stilbenes, coumarins, pyrazoles, naphthalimides, oxadizoles, aryl triazoles,
distyrylbiphenyls, dibenzofiuanyl biphenyls, bis(triazinyl)stilbenes,
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mono(triazinyl)stilbenes, stilbenylnaphthotriazoles,
phenylstilbenylbenzoxazoles,
bis(triazoyl)stilbenes, 1,4-bis(styryl)benzenes, 4,4'-bis(styryl)benzenes, 1,3-
diphenyl-2-pyrazoIines, bis(benzazoyl) derivatives, bis(benzimidizolyl)
derivatives,
2-(benzofuranyl)benzimidazoles, coumarins, carbostyrils, and mixtures thereof;
R25
is a substituent group that modifies the optical or solubility properties or
the FWA
unit.
Examples of non-hydrolyzable end-capping units of the present invention
comprising FWA units are naphthotriazole units having the formula
N
N-
\ N~
wherein the R25 moiety and the linking L unit are attached to the same
aromatic
ring, for example
-L, /\ ,R~
N
NH
or in any other chemically suitable manner.
The FWA units are phenyltriazole units having the formula
N
N-
N
wherein the R25 moiety and the linking L unit are attached to the same
aromatic
ring, for example
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24
- L / R~s
N
NH
~N
or in any other chemically suitable manner. The FWA units are substituted or
un-
substituted conjugated heterocycles having the formula
X
i/ R 76
~Y
Rzs
wherein R25 is C1-C4 alkyl, -C02M, -S03M, wherein M is hydrogen or a water
soluble cation; R26 is hydrogen or C1-C4 alkyl; X is oxygen, -NH-, -CH2-, and
mixtures thereof; Y is -N-, -CH-, and mixtures thereof.
Fused ring FWA units also have the formula
X
~R3o~
~Y
Rzs
wherein R25 is C1-C4 alkyl, -S03M, wherein M is hydrogen or a water soluble
cation; R3~ is a B unit as described herein above, 1,2-phenylene, 1,3-
phenylene,l,4-phenylene, substituted phenylene having the formula:
> >
Rio Rz ~ R2o R2 i Rio R2 i
wherein R2~ and R21 moieties are selected from the group consisting of
hydrogen,
C 1-C4 alkyl, C 1-C4 dialkylamino, C 1-C4 alkoxy, anilino, morpholino,
diethylamino, chloro, bromo, iodo, cyano, nitrilo, sulfophenylamino, 2,5-
disulfophenylamino, -(S03-M+), and mixtures thereof, preferably R2~ and R21
units are hydrogen, C1-C4 dialkylamino, C1-C4 alkoxy, anilino, morpholino,
diethylamino, sulfophenylamino, 2,5-disulfophenylamino, and -(S03-M+), more
preferred are hydrogen, C1-C4 dialkylamino, N-methyl-N-hydroxyethylamino,
bis(hydroxyethyl)amino, and -(S03-M+), most preferred are hydrogen and -(S03-
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M+). Most preferred R21 unit is hydrogen, that is. R~~ has only one
substituent
group present. R3~ is carboxyphenylene having the formula:
R~ 1- -R31
R3 ~- ,
R2o R2 ~ Rzo R2 i R2o z ~
R
wherein R3I is -C02-, -CONH-, -NHCO-, and mixtures thereof; X is oxygen, -NH-,
-CH2-, -CHR2g- wherein R2g is CI-C4 alkyl; and mixtures thereof; Y is -N=, -
CH=, -CR~9= wherein R29 is C1-C4 alkyl; and mixtures thereof. The R3~ unit can
be bonded to the soil release polymer backbone either directly or through a
linking
group L. The same applies when R3~ comprises a carboxy moiety R31, the R31
units can be bonded either directly to the polymer backbone or through a
linking
group. The conjugated heterocycle FWA's are preferably attached to linking L
units
in a manner similar to the naphthalotriazole and phenyltriazole moieties
The following is an example of a benzofuranyl FWA unit according to the
present invention having the formula:
O(CH2CH20~
Na03S O
wherein R25 is -S03Na, X is oxygen, Y is -C(CH3)=, R3~ is 1,3-phenylene, and
the
FWA is bonded to a linking group L which comprises an oxyethyleneoxy unit
having three ethyleneoxy units..
A preferred example of a non-hydrolyzable fluorescent end capping unit of
the present invention having a linking L unit that is an ethylene moiety, R14
is a
substituted triazinyl moiety wherein R19 is bis(hydroxyethyl)amino; R15 is
substituted 1,4-phenylene wherein R2~ is -S03Na, and R21 is hydrogen atom;
bridging B unit is ethylene; R16 is substituted 1,4-phenylene wherein R2~ is -
S03Na, and R21 is hydrogen atom; R1~ is substituted triazinyl wherein R24 is
hydrogen atom, R2~ is methyl has the formula:
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WO 98/59030 PCT/US97/10734
26
-OCH,CH,NH~ Na03S NHCH3
N// N N H ~ ~ H-C H ~ ~ H N \\N
-
(HOCH~CH,)~N S03Na
A preferred example of a non-hydrolyzable fluorescent end capping unit of
the present invention wherein R14 comprises a substituted benzofuranyl moiety;
R25 is -S03Na, R30 is 4-carboxyphenylene, X is oxygen, Y is -CR29= wherein R29
is methyl, has the formula:
C O2-
Na03S
Pendant Fluorescent Whitening Units
The fluorescent whitening units of the present invention may also be present
as pendant groups on RS units to form a "Pendant Fluorescent Whitening Unit".
For
the purposes of the present invention a "Pendant Fluorescent Whitening Unit"
is
defined as a fluorescent whitening unit that is suitably attached as a pendant
group
within a RS unit.
For example an RS moiety having the formula
R9 R9
-Rlo-(p-Rio)W
f
Rg Rg
wherein the index i is equal to 0 or l, R10 is C2-C6 linear alkylene, C3-C6
branched
alkylene, CS-C~ cyclic alkylene, CS-C~ substituted cyclic alkylene, CS-C~
heterocyclic alkylene, arylene, substituted arylene, and mixtures thereof. An
example of an RS moiety comprising a fluorescent whitening unit (FWU) as a
pendant group wherein R10 unit is a branched C3 alkylene moiety having all Rg
units comprise hydrogen atoms, R9 units comprise hydrogen atoms a single -Z-
(FWLJ) unit, herein after referred to as "RS unit comprising a single -Z-(FWU)
pendant group" has the formula
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77
-CH-CH~-
-
CH~-Z-(FWL~
Substituting for the general -(FWU) moiety, Z is oxygen atom, R~4 unit is
absent (y
is equal to 0), Ris unit is 1,4-phenylene, bridging unit B is ethylene, R~6 is
1,2-
phenylene and R ~ ~ is -S03-M+ wherein M is sodium has the formula:
CH,
CH-CH2-O ~ ~ CH=CH
Na03S
The above adduct is an example of a minimal chain length RS unit
comprising a non-hydrolyzable pendant fluorescent whitening unit. This unit
can be
incorporated into the soil release polymer chain through an intermediate
having the
formula
OH
CH2
CH-CH2-O ~ ~ CH=CH
OH
Na03S
A example of a monomer suitable for use as an RS moiety comprising a
fluorescent whitening group which thereby forms a "pendant fluorescent
whitening
group" has the structure
OH OH
OCH2-CH-CH2
S03Na
Na03S
wherein the RS unit is a single chemical unit and the fluorescent whitening
group is
non-hydrolyzable from the backbone of the soil release polymer after
incorporation.
A further example of an RS moiety comprising a fluorescent whitening
group which comprises a "pendant fluorescent whitening group" has the
structure
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28
-O- C H,_- C H-O-
I
C H2-OC HOC H~NH N a03S N HC H3
N N NH ~ \ CH=CH / \ NH N
r"'N N
(HOCHZCHZ~N S03Na
wherein the R~ unit is a single chemical unit and the fluorescent whitening
group is
non-hydrolyzable from the backbone of the soil release polymer after
incorporation.
Non-Fluorescent Whitening End-capping Units
In addition to the non-hydrolyzable fluorescent end-capping units, the soil
release polymers or oligomers of the present invention comprise non
fluorescent
whitening end-capping units. These non-fluorescent whitening end-capping units
serve several purposes. One role is to terminate the polymer backbone thereby
ending chain propagation of the backbone and branching units. Also, the end
capping units provide the soil release polymers of the present invention with
certain
intrinsic properties.
A preferred class of non-fluorescent whitening end-capping units are the
ethoxylated or propoxyiated hydroxyethane and propanesulfonate units of the
formula (M03S)(CH2)m(R~ 10)nRi 1-, wherein M is a salt-forming cation such as
sodium or tetralkylammonium, R11 is ethylene or propylene or a mixture
thereof, m
is 0 or l, and n is 0 to 20. Preferred m is 0, preferred n is 0 to 6,
preferred M is
sodium or potassium, most preferred M is sodium.
Also a preferred class of non-fluorescent whitening end-capping units are the
sulfoaroyl units of the formula -O(O}C(C6H4)(S03-M+), wherein M is a salt
forming cation. Preferred M is sodium or potassium, more preferred is sodium.
Also a preferred class of non-fluorescent whitening end-capping units are the
modified poly(oxyethylene}oxy monoalkyl ether units of the formula Rt20-
(CH2CH20)kCH2CH2-, wherein R12 contains from 1 to 4 carbon atoms and k is
from about 3 to about 100. Preferred Rt2 is methyl and ethyl, more preferred
is
methyl. Preferred k is from about 4 to about 45, more preferred about 5 to
about 35.
A further preferred class of non-fluorescent whitening end-capping units are
the ethoxylated or propoxylated phenolsulfonate end-capping units of the
formula
M03S(C6H4)(OR13)n-, wherein n is from 1 to 20; M is a salt-forming cation; and
R13 is ethylene, propylene or mixtures thereof. Preferred R13 is ethylene.
Preferred
n is 1 to 6, more preferred n is 1 to 3. Preferred M is sodium or potassium,
more
preferred is sodium.
LAUNDRY DETERGENT COMPOSITIONS
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29
The laundry detergent compositions of the present invention in addition to
the fluorescent whitening soil release polymers described herein above also
comprise the following ingredients.
Surfactant - The instant cleaning compositions contain from about 0.1 % to
about 60% by weight of a surfactant selected from the group consisting of
anionic,
nonionic, ampholytic and zwitterionic surface active agents. For liquid
systems,
surfactant is preferably present to the extent of from about 0.1 % to 30% by
weight
of the composition. For solid (i.e. granular) and viscous semi-solid (i.e.
gelatinous,
pastes, etc.) systems, surfactant is preferably present to the extent of from
about
1.5% to 30 % by weight of the composition.
Nonlimiting examples of surfactants useful herein typically at levels from
about 1 % to about 55%, by weight, include the conventional C 11-C 1 g alkyl
benzene
sulfonates ("LAS") and primary, branched-chain and random C10-C20 alkyl
sulfates
("AS"), the C 10-C 1 g secondary (2,3) alkyl sulfates of the formula
CH3(CH2)x(CHOS03 M+) CH3 and CH3 (CH2)y(CHOS03-M+) CH2CH3 where
x and (y + 1 ) are integers of at least about 7, preferably at least about 9,
and M is a
water-solubiIizing canon, especially sodium, unsaturated sulfates such as
oleyl
sulfate, the C 10-C 1 g alkyl alkoxy sulfates ("AEXS"; especially EO 1-7
ethoxy
sulfates), C 10-C 1 g alkyl alkoxy carboxylates (especially the EO I -5
ethoxycarboxylates), the C 10-18 glycerol ethers, the C 1 p-C 1 g alkyl
polyglycosides
and their corresponding sulfated polyglycosides, and C 12-C 1 g alpha-
sulfonated
fatty acid esters. If desired, the conventional nonionic and amphoteric
surfactants
such as the C 12-C 1 g alkyl ethoxylates ("AE") including the so-called narrow
peaked
alkyl ethoxylates and C6-C 12 alkyl phenol alkoxylates (especially ethoxylates
and
mixed ethoxy/propoxy), C 12-C 1 g betaines and sulfobetaines ("sultaines"), C
10-C 18
amine oxides, and the like, can also be included in the overall compositions.
The
C 10-C 18 N-alkyl polyhydroxy fatty acid amides can also be used. Typical
examples include the C 12-C 1 g N-methylglucamides. See WO 9,206,154. Other
sugar-derived surfactants include the N-alkoxy polyhydroxy fatty acid amides,
such
as C 10-C 1 g N-(3-methoxypropyl) glucamide. The N-propyl through N-hexyl C 12-
C 1 g glucamides can be used for low sudsing. C 1 p-C20 conventional soaps may
also be used. If high sudsing is desired, the branched-chain C 1 p-C 16 soaps
may be
used. Mixtures of anionic and nonionic surfactants are especially useful.
Other
conventional useful surfactants are described further herein and are listed in
standard
texts.
Anionic surfactants can be broadly described as the water-soluble salts,
particularly the alkali metal salts, of organic sulfuric reaction products
having in
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their molecular structure an alkyl radical containing from about 8 to about 22
carbon
atoms and a radical selected from the group consisting of sulfonic acid and
sulfuric
acid ester radicals. ( Included in the term alkyl is the alkyl portion of
higher acyl
radicals.) Important examples of the anionic synthetic detergents which can
form
the surfactant component of the compositions of the present invention are the
sodium or potassium alkyl sulfates, especially those obtained by sulfating the
higher
alcohois (C8-18 carbon atoms) produced by reducing the glycerides of tallow or
coconut oil; sodium or potassium alkyl benzene sulfonates, in which the alkyl
group
contains from about 9 to about 15 carbon atoms, (the alkyl radical can be a
straight
or branched aliphatic chain); sodium alkyl glyceryl ether sulfonates,
especially those
ethers of the higher alcohols derived from tallow and coconut oil; sodium
coconut
oil fatty acid monoglyceride sulfates and sulfonates; sodium or potassium
salts of
sulfuric acid ester of the reaction product of one mole of a higher fatty
alcohol (e.g.
tallow or coconut alcohols) and about 1 to about 10 moles of ethylene oxide;
sodium
or potassium salts of alkyl phenol ethylene oxide ether sulfates with about 1
to about
10 units of ethylene oxide per molecule and in which the alkyl radicals
contain from
8 to 12 carbon atoms; the reaction products of fatty acids are derived from
coconut
oil sodium or potassium salts of fatty acid amides of a methyl tauride in
which the
fatty acids, for example, are derived from coconut oil and sodium or potassium
beta-
acetoxy- or beta-acetamido-alkanesulfonates where the alkane has from 8 to 22
carbon atoms.
Additionally, secondary alkyl sulfates may be used by the formulator
exclusively or in conjunction with other surfactant materials and the
following
identifies and illustrates the differences between sulfated surfactants and
otherwise
conventional alkyl sulfate surfactants. Non-limiting examples of such
ingredients
are as follows.
Conventional primary alkyl sulfates (LAS), such as those illustrated above,
have the general formula ROS03-M+ wherein R is typically a linear C8-22
hydrocarbyl group and M is a water solublizing cation. Branched chain primary
alkyl sulfate surfactants (i.e., branched-chain "PAS") having 8-20 carbon
atoms are
also know; see, for example, Eur. Pat. Appl. 439,316, Smith et al., filed
January 21,
1991.
Conventional secondary alkyl sulfate surfactants are those materials which
have the sulfate moiety distributed randomly along the hydrocarbyl "backbone"
of
the molecule. Such materials may be depicted by the structure
CH3(CH2)n(CHOS03-M+)(CH2)mCH3
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31
wherein m and n are integers of 2 of greater and the sum of m + n is typically
about
9 to 17, and M is a water-solubIizing cation.
The aforementioned secondary alkyl sulfates are those prepared by the
addition of H2S04 to olefins. A typical synthesis using alpha olefins and
sulfuric
acid is disclosed in U.S. Pat. No. 3,234,258, Morris, issued February 8, 1966
or in
U.S. Pat. No. 5,075,041, Lutz, issued December 24,1991. See also U.S. Patent
5,349,101, Lutz et al., issued September 20, 1994; U.S. Patent 5,389,277,
Prieto,
issued February 14, 1995.
ADJUNCT INGREDIENTS
Enzymes - 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 surfaces such as textiles or dishes, for the
prevention
of refugee dye transfer, for example in laundering, and for fabric
restoration.
Suitable enzymes include proteases, amylases, lipases, celluiases,
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 optima, 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, hard surface
cleaning or
personal care detergent composition. Preferred detersive enzymes are
hydrolases
such as proteases, amylases and lipases. Preferred enzymes for laundry
purposes
include, but are not limited to, proteases, cellulases, lipases and
peroxidases. Highly
preferred for automatic dishwashing are amylases and/or proteases, including
both
current commercially available types and improved types which, though more and
more bleach compatible though successive improvements, have a remaining degree
of bleach deactivation susceptibility.
Enzymes are normally incorporated into detergent or detergent additive
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, dishware and the like. 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
S%, preferably 0.01 %-1 % by weight of a commercial enzyme preparation.
Protease
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32
enzymes are usually present in such commercial preparations at levels
sufficient to
provide from 0.00 to 0.1 Anson units (AU) of activity per gram of composition.
Higher active levels may also be desirable in highly concentrated detergent
formulations.
Suitable examples of proteases are the subtilisins which are obtained from
particular strains of B. subtilis and B. licheniformis. One suitable protease
is
obtained from a strain of Bacillus, having maximum activity throughout the pH
range of 8-12, developed and sold as ESPERASE~ by Novo Industries A/S of
Denmark, hereinafter "Novo". The preparation of this enzyme and analogous
enzymes is described in GB 1,243,784 to Novo. Other suitable proteases include
ALCALASE~ and SAVINASE~ from Novo and MAXATASE~ from
International Bio-Synthetics, Inc., The Netherlands; as well as Protease A as
disclosed in EP 130,756 A, January 9, 1985 and Protease B as disclosed in EP
303,761 A, April 28, 1987 and EP 130,756 A, 3anuary 9, 1985. See also a high
pH
protease from Bacillus sp. NCIMB 40338 described in WO 9318140 A to Novo.
Enzymatic detergents comprising protease, one or more other enzymes, and a
reversible protease inhibitor are described in WO 9203529 A to Novo. Other
preferred proteases include those of WO 9510591 A to Procter & Gamble . When
desired, a protease having decreased adsorption and increased hydrolysis is
available
as described in WO 9507791 to Procter & Gamble. A recombinant trypsin-like
protease for detergents suitable herein is described in WO 9425583 to Novo.
In more detail, an especially preferred protease, referred to as "Protease D"
is
a carbonyl hydrolase variant having an amino acid sequence not found in
nature,
which is derived from a precursor carbonyl hydrolase by substituting a
different
amino acid for a plurality of amino acid residues at a position in said
carbonyl
hydrolase equivalent to position +76, preferably also in combination with one
or
more amino acid residue positions equivalent to those selected from the group
consisting of +99, +101, +103, +104, +107, +123, +27, +105, +109, +126, +128,
+135, +156, +166, +195, +197, +204, +206, +210, +216, +217, +218, +222, +260,
+265, and/or +274 according to the numbering of Bacillus amyloliquefaciens
subtilisin, as described in the patent applications of A. Baeck, et al,
entitled
"Protease-Containing Cleaning Compositions" having US Serial No. 08/322,676,
and C. Ghosh, et al, "Bleaching Compositions Comprising Protease Enzymes"
having US Serial No. 08/322,677, both filed October 13, 1994.
Amylases suitable herein, especially for, but not limited to automatic
dishwashing purposes, include, for example, a-amylases described in GB
1,296,839
to Novo; R.APIDASE~, International Bio-Synthetics, Inc. and TERMAMYL~,
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33
Novo. FUNGAMYL~ from Novo is especially useful. Engineering of enzymes for
improved stability, e.g., oxidative stability, is known. See, for example J.
Biological
Chem., Vol. 260, No. 1 l, June 1985, pp 6518-6521. These preferred amylases
herein share the characteristic of being "stability-enhanced" amylases,
characterized,
at a minimum, by a measurable improvement in one or more of: oxidative
stability,
e.g., to hydrogen peroxide / tetraacetylethylenediamine in buffered solution
at pH 9-
10; thermal stability, e.g., at common wash temperatures such as about 60oC;
or
alkaline stability, e.g., at a pH from about 8 to about 1 l, measured versus
the above-
identified reference-point amylase. Stability can be measured using any of the
art-
disclosed technical tests. See, for example, references disclosed in WO
9402597.
Stability-enhanced amylases can be obtained from Novo or from Genencor
International. One class of highly preferred amylases herein have the
commonality
of being derived using site-directed mutagenesis from one or more of the
Baccillus
amylases, especialy the Bacillus a-amylases, regardless of whether one, two or
multiple amylase strains are the immediate precursors. Oxidative stability-
enhanced
amylases vs. the above-identified reference amylase are preferred for use,
especially
in bleaching, more preferably oxygen bleaching, as distinct from chlorine
bleaching,
detergent compositions herein. Such preferred amylases include (a) an amylase
according to the hereinbefore incorporated WO 9402597, Novo, Feb. 3, 1994, as
further illustrated by a mutant in which substitution is made, using alanine
or
threonine, preferably threonine, of the methionine residue located in position
197 of
the B.licheniformis alpha-amylase, known as TERMAMYL~, or the homologous
position variation of a similar parent amylase, such as B. amyloliquefaciens,
B.subtilis, or B.stearothermophilus; (b) stability-enhanced amylases as
described by
Genencor International in a paper entitled "Oxidativeiy Resistant alpha-
Amylases"
presented at the 207th American Chemical Society National Meeting, March 13-17
1994, by C. Mitchinson. Methionine (Met) was identified as the most likely
residue
to be modified. Met was substituted, one at a time, in positions 8, 15, 197,
256, 304,
366 and 438 leading to specific mutants, particularly important being M197L
and
M197T with the M197T variant being the most stable expressed variant. Other
particularly preferred oxidative stability enhanced amylase include those
described
in WO 9418314 to Genencor International and WO 9402597 to Novo. Any other
oxidative stability-enhanced amylase can be used, for example as derived by
site-
directed mutagenesis from known chimeric, hybrid or simple mutant parent forms
of
available amylases. Other preferred enzyme modifications are accessible. See
WO
9509909 A to Novo.
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34
Cellulases usable herein include both bacterial and fungal types, preferably
having a pH optimum between ~ and 9.5. U.S. 4,43,307, Barbesgoard et al, March
6, 1984, discloses suitable fungal cellulases from Humicola insolens or
Humicola
strain DSM 1800 or a cellulose 212-producing fungus belonging to the genus
Aeromonas, and cellulose extracted from the hepatopancreas of a marine
mollusk,
Dolabella Auricula Solander. Suitable cellulases are also disclosed in GB-A-
2.075.028; GB-A-2.095.275 and DE-OS-2.247.832. CAREZYME~ (Novo) is
especially useful. See also WO 9117243 to Novo.
Suitable lipase enzymes for detergent usage include those produced by
microorganisms of the Pseudomonas group, such as Pseudomonas stutzeri ATCC
19.154, as disclosed in GB 1,372,034. See also lipases in Japanese Patent
Application 53,20487, laid open Feb. 24, 1978. This lipase is available from
Amano
Pharmaceutical Co. Ltd., Nagoya, Japan, under the trade name Lipase P "Amano,"
or "Amano-P." Other suitable commercial lipases include Amano-CES, lipases ex
Chromobacter viscosum, e.g. Ckromobacter viscosum var. lipolyticum NRRLB
3673 from Toyo Jozo Co., Tagata, Japan; Chromobacter viscosum lipases from
U.S.
Biochemical Corp., U.S.A. and Disoynth Co., The Netherlands, and lipases ex
Pseudomonas gladioli. LIPOLASE~ enzyme derived from Humicola lanuginosa
and commercially available from Novo, see also EP 341,947, is a preferred
lipase
for use herein. Lipase and amylase variants stabilized against peroxidase
enzymes
are described in WO 9414951 A to Novo. See also WO 9205249 and RD
94359044.
Cutinase enzymes suitable for use herein are described in WO 8809367 A to
Genencor.
Peroxidase enzymes may be used in combination with oxygen sources, e.g.,
percarbonate, perborate, hydrogen peroxide, etc., for "solution bleaching" or
prevention of transfer of dyes or pigments removed from substrates during the
wash
to other substrates present in the wash solution. Known peroxidases include
horseradish peroxidase, ligninase, and haloperoxidases such as chloro- or
bromo-
peroxidase. Peroxidase-containing detergent compositions are disclosed in WO
89099813 A, October 19, 1989 to Novo and WO 8909813 A to Novo.
A range of enzyme materials and means for their incorporation into synthetic
detergent compositions is also disclosed in WO 9307263 A and WO 9307260 A to
Genencor International, WO 8908694 A to Novo, and U.S. 3,553,139, January 5,
1971 to McCarty et al. Enzymes are further disclosed in U.S. 4,101,457, Place
et al,
July 18, 1978, and in U.S. 4,507,219, Hughes, March 26, 1985. Enzyme materials
useful for liquid detergent formulations, and their incorporation into such
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formulations, are disclosed in U.S. 4,261,868, Hora et al, April 14, 1981.
Enzymes
for use in detergents can be stabilized by various techniques. Enzyme
stabilization
techniques are disclosed and exemplified in U.S. 3,600,319, August 17, 1971,
Gedge
et al, EP 199,405 and EP 200,586. October 29, 1986, Venegas. Enzyme
stabilization systems are also described, for example, in U.S. 3,519,570. A
useful
Bacillus, sp. AC 13 giving proteases, xylanases and cellulases, is described
in WO
9401532 A to Novo.
Enzyme Stabilizing System - Enzyme-containing, including but not limited to,
liquid compositions, herein may comprise from about 0.00I % 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.
One stabilizing approach is the use of water-soluble sources of calcium and/or
magnesium ions in the finished compositions which provide such ions to the
enzymes. Calcium ions are generally more effective than magnesium ions and are
preferred herein if only one type of cation is being used. Typical detergent
compositions, especially liquids, will comprise from about 1 to about 30,
preferably
from about 2 to about 20, more preferably from about 8 to about I2 millimoles
of
calcium ion per liter of finished detergent composition, though variation is
possible
depending on factors including the multiplicity, type and levels of enzymes
incorporated. Preferably water-soluble calcium or magnesium salts are
employed,
including for example calcium chloride, calcium hydroxide, calcium formate,
calcium malate, calcium maleate, calcium hydroxide and calcium acetate; more
generally, calcium sulfate or magnesium salts corresponding to the exemplified
calcium salts may be used. Further increased levels of Calcium and/or
Magnesium
may of course be useful, for example for promoting the grease-cutting action
of
certain types of surfactant.
Another stabilizing approach is by use of borate species. See Severson, U.S.
4,537,706. Borate stabilizers, when used, may be at levels of up to 10% or
more of
the composition though more typically, levels of up to about 3% by weight of
boric
acid or other borate compounds such as borax or orthoborate are suitable for
liquid
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detergent use. Substituted boric acids such as phenylboronic acid,
butaneboronic
acid, p-bromophenylboronic acid or the like can be used in place of boric acid
and
reduced levels of total boron in detergent compositions may be possible though
the
use of such substituted boron derivatives.
Stabilizing systems of certain cleaning compositions may further comprise
from 0 to about 10%, preferably from about 0.01 % to about 6% by weight, of
chlorine bleach scavengers, added to prevent chlorine bleach species present
in
many water supplies from attacking and inactivating the enzymes, especially
under
alkaline conditions. While chlorine levels in water may be small, typically in
the
range from about 0.5 ppm to about 1.75 ppm, the available chlorine in the
total
volume of water that comes in contact with the enzyme, for example during dish-
or
fabric-washing, can be relatively large; accordingly, enzyme stability to
chlorine m-
use is sometimes problematic. Since perborate or percarbonate, which have the
ability to react with chlorine bleach, may present in certain of the instant
compositions in amounts accounted for separately from the stabilizing system,
the
use of additional stabilizers against chlorine, may, most generally, not be
essential,
though improved results may be obtainable from their use. Suitable chlorine
scavenger anions are widely known and readily available, and, if used, can be
salts
containing ammonium cations with sulfite, bisulfate, thiosulfite, thiosulfate,
iodide,
etc. Antioxidants such as carbamate, ascorbate, etc., organic amines such as
ethylenediaminetetracetic acid (EDTA) or alkali metal salt thereof,
monoethanolamine (MEA), and mixtures thereof can likewise be used. Likewise,
special enzyme inhibition systems can be incorporated such that different
enzymes
have maximum compatibility. Other conventional scavengers such as bisulfate,
nitrate, chloride, sources of hydrogen peroxide such as sodium perborate
tetrahydrate, sodium perborate monohydrate and sodium percarbonate, as well as
phosphate, condensed phosphate, acetate, benzoate, citrate, formate, lactate,
malate,
tartrate, salicylate, etc., and mixtures thereof can be used if desired. In
general, since
the chlorine scavenger function can be performed by ingredients separately
listed
under better recognized functions, (e.g., hydrogen peroxide sources), there is
no
absolute requirement to add a separate chlorine scavenger unless a compound
performing that function to the desired extent is absent from an enzyme-
containing
embodiment of the invention; even then, the scavenger is added only for
optimum
results. Moreover, the formulator will exercise a chemist's normal skill in
avoiding
the use of any enzyme scavenger or stabilizer which is majorly incompatible,
as
formulated, with other reactive ingredients, if used. In relation to the use
of
ammonium salts, such salts can be simply admixed with the detergent
composition
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37
but are prone to adsorb water and/or liberate ammonia during storage.
Accordingly,
such materials, if present, are desirably protected in a particle such as that
described
in US 4,652,392, Baginski et al.
Bleachine Compounds - Bleaching-Agents and Bleach Activators - The
detergent compositions herein may optionally contain bleaching agents or
bleaching
compositions containing a bleaching agent and one or more bleach activators.
When
present, bleaching agents will typically be at levels of from about 1 % to
about 30%,
more typically from about S% to about 20%, of the detergent composition,
especially for fabric laundering. If present, the amount of bleach activators
will
typically be from about 0.1 % to about 60%, more typically from about 0.5% to
about 40% of the bleaching composition comprising the bleaching agent-plus-
bleach
activator.
The bleaching agents used herein can be any of the bleaching agents useful
for detergent compositions in textile cleaning, hard surface cleaning, or
other
cleaning purposes that are now known or become known. These include oxygen
bleaches as well as other bleaching agents. Perborate bleaches, e.g., sodium
perborate (e.g., mono- or tetra-hydrate) can be used herein.
Another category of bleaching agent that can be used without restriction
encompasses percarboxylic acid bleaching agents and salts thereof. Suitable
examples of this class of agents include magnesium monoperoxyphthalate
hexahydrate, the magnesium salt of metachloro perbenzoic acid, 4-nonylamino-4-
oxoperoxybutyric acid and diperoxydodecanedioic acid. Such bleaching agents
are
disclosed in U.S. Patent 4,483,781, Hartman, issued November 20, 1984, U.S.
Patent Application 740,446, Burns et al, filed June 3, 1985, European Patent
Application 0,133,354, 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 as described in U.S.
Patent 4,634,551, issued January 6, 1987 to Burns et al.
Peroxygen bleaching agents can also be used. Suitable peroxygen bleaching
compounds include sodium carbonate peroxyhydrate and equivalent "percarbonate"
bleaches, sodium pyrophosphate peroxyhydrate, urea peroxyhydrate, and sodium
peroxide. Persulfate bleach (e.g., OXONE, manufactured commercially by DuPont)
can also be used.
A preferred percarbonate bleach comprises dry particles having an average
particle size in the range from about 500 micrometers to about 1,000
micrometers,
not more than about 10% by weight of said particles being smaller than about
200
micrometers and not more than about 10% by weight of said particles being
larger
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38
than about 1,250 micrometers. Optionally, the percarbonate can be coated with
silicate, borate or water-soluble surfactants. Percarbonate is available from
various
commercial sources such as FMC, Solvay and Tokai Denka.
Mixtures of bleaching agents can also be used.
Peroxygen bleaching agents, the perborates, the percarbonates, etc., are
preferably combined with bleach activators, which lead to the in situ
production in
aqueous solution (i.e., during the washing process) of the peroxy acid
corresponding
to the bleach activator. Various nonlimiting examples of activators are
disclosed in
U.S. Patent 4,915,854, issued April 10, 1990 to Mao et al, and U.S. Patent
4,412,934. The nonanoyloxybenzene sulfonate (HOBS) and tetraacetyl ethylene
diamine (TAED) activators are typical, and mixtures thereof can also be used.
See
also U.S. 4,634,551 for other typical bleaches and activators useful herein.
Highly preferred amido-derived bleach activators are those of the formulae:
R1N(R5)C(O)R2C(O)L or R1C(O)N(R5)R2C(O)L
wherein Rl 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 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 phenyl sulfonate.
Preferred examples of bleach activators of the above formulae include (6-
octanamido-caproyl)oxybenzenesulfonate, (6-nonanamidocaproyl)oxybenzenesul-
fonate, (6-decanamido-caproyl)oxybenzenesulfonate, and mixtures thereof as
described in U.S. Patent 4,634,551, incorporated herein by reference.
Another class of bleach activators comprises the benzoxazin-type activators
disclosed by Hodge et al in U.S. Patent 4,966,723, issued October 30, 1990,
incorporated herein by reference. A highly preferred activator of the
benzoxazin-
type is:
O
II
I
..~ o
N
Still another class of preferred bleach activators includes the acyl lactam
activators, especially acyl caprolactams and acyl valerolactams of the
formulae:
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39
O O
O
O
C-R6 or C-R6
wherein R6 is H or an alkyl, aryl, alkoxyaryl, or alkaryl group containing
from 1 to
about 12 carbon atoms. Highly preferred lactam activators include benzoyl
caproiactam, octanoyl caprolactam, 3,5,5-trimethylhexanoyl caprolactam,
nonanoyl
caprolactam, decanoyl caprolactam, undecenoyl caprolactam, benzoyl
valerolactam,
octanoyl valerolactam, decanoyl valerolactam, undecenoyl valerolactam,
nonanoyl
valerolactam, 3,5,5-trimethylhexanoyl valerolactam and mixtures thereof. See
also
U.S. Patent 4,545,784, issued to Sanderson, October 8, 1985, incorporated
herein by
reference, which discloses acyl caprolactams, including benzoyl caprolactam,
adsorbed into sodium perborate.
Bleaching agents other than oxygen bleaching agents are also known in the
art and can be utilized herein. One type of non-oxygen bleaching agent of
particular
interest includes photoactivated bleaching agents such as the sulfonated zinc
and/or
aluminum phthalocyanines. See U.S. Patent 4,033,718, issued July 5, 1977 to
Holcombe et al. If used, detergent compositions will typically contain from
about
0.025% to about 1.25%, by weight, of such bleaches, especially sulfonate zinc
phthalocyanine.
If desired, the bleaching compounds can be catalyzed by means of a
manganese compound. Such compounds are well known in the art and include, for
example, the manganese-based catalysts disclosed in U.S. Pat. 5,246,621, U.S.
Pat.
5,244,594; U.S. Pat. 5,194,416; U.S. Pat. 5,114,606; and European Pat. App.
Pub.
Nos. 549,271A1, 549,272A1, 544,440A2, and 544,490A1; Preferred examples of
these catalysts include MnIV2(u-O)3(1,4,7-trimethyl-1,4,7-triazacyclo-
nonane)2(PF6)2, MnIII2(u-O)1(u-OAc)2(1,4,7-trimethyl-1,4,7-triazacyclononane)2-
(CI04)2, MnIV4(u-O)6(1,4,7-triazacyclononane)4(C104)4, MnIII~IV4(u-O)I(u-
OAc)2-(1,4,7-trimethyl-1,4,7-triazacyclononane)2(C104)3, MnIV(1,4,7-trimethyl-
1,4,7-triazacyclononane)- (OCH3)3(PF6), and mixtures thereof. Other metal-
based
bleach catalysts include those disclosed in U.S. Pat. 4,430,243 and U.S. Pat.
5,114,611. The use of manganese with various complex ligands to enhance
bleaching is also reported in the following United States Patents: 4,728,455;
5,284,944; 5,246,612; 5,256,779; 5,280,117; 5,274,147; 5,153,161; and
5,227,084.
As a practical matter, and not by way of limitation, the compositions and
processes herein can be adjusted to provide on the order of at least one part
per ten
million of the active bleach catalyst species in the aqueous washing liquor,
and will
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preferably provide from about 0.1 ppm to about 700 ppm, more preferably from
about 1 ppm to about 500 ppm, of the catalyst species in the laundry liquor.
Builders - Detergent builders can optionally be included in the compositions
herein to assist in controlling mineral hardness. Inorganic as well as organic
builders can be used. Builders are typically used in fabric laundering
compositions
to assist in the removal of particulate soils.
The level of builder can vary widely depending upon the end use of the
composition and its desired physical form. When present, the compositions will
typically comprise at least about 1% builder. Liquid formulations typically
comprise from about 5% to about 50%, more typically about 5% to about 30%, by
weight, of detergent builder. Granular formulations typically comprise from
about
I 0% to about 80%, more typically from about I S% to about 50% by weight, of
the
detergent builder. Lower or higher levels of builder, however, are not meant
to be
excluded.
Inorganic or P-containing detergent builders include, but are not limited to,
the alkali metal, ammonium and alkanolammonium salts of polyphosphates
(exemplified by the tripolyphosphates, pyrophosphates, and glassy polymeric
meta-
phosphates), phosphonates, phytic acid, silicates, carbonates (including
bicarbonates
and sesquicarbonates), sulphates, and aluminosilicates. However, non-phosphate
builders are required in some locales. Importantly, the compositions herein
function
surprisingly well even in the presence of the so-called "weak" builders (as
compared
with phosphates) such as citrate, or in the so-called "underbuilt" situation
that may
occur with zeolite or layered silicate builders.
Examples of silicate builders are the alkali metal silicates, particularly
those
having a Si02:Na20 ratio in the range 1.6:1 to 3.2:1 and layered silicates,
such as
the layered sodium silicates described in U.S. Patent 4,664,839, issued May
12,
1987 to H. P. Rieck. NaSKS-6 is the trademark for a crystalline layered
silicate
marketed by Hoechst (commonly abbreviated herein as "SKS-6"). Unlike zeolite
builders, the Na SKS-6 silicate builder does not contain aluminum. NaSKS-6 has
the delta-Na2Si05 morphology form of layered silicate. It can be prepared by
methods such as those described in German DE-A-3,417,649 and DE-A-3,742,043.
SKS-6 is a highly preferred layered silicate for use herein, but other such
layered
silicates, such as those having the general formula NaMSix02x+1 ~YH20 wherein
M
is sodium or hydrogen, x is a number from 1.9 to 4, preferably 2, and y is a
number
from 0 to 20, preferably 0 can be used herein. Various other layered silicates
from
Hoechst include NaSKS-5, NaSKS-7 and NaSKS-11, as the alpha, beta and gamma
forms. As noted above, the delta-Na2Si05 (NaSKS-6 form) is most preferred for
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41
use herein. Other silicates may also be useful such as for example magnesium
silicate, which can serve as a crispening agent in granular formulations, as a
stabilizing agent for oxygen bleaches, and as a component of suds control
systems.
Examples of carbonate builders are the alkaline earth and alkali metal
carbonates as disclosed in German Patent Application No. 2,321,001 published
on
November 15, 1973.
Aluminosilicate builders are useful in the present invention. Aluminosilicate
builders are of great importance in most currently marketed heavy duty
granular
detergent compositions, and can also be a significant builder ingredient in
liquid
detergent formulations. Aluminosilicate builders include those having the
empirical
formula:
Mz(zA102)y]~xH20
wherein z and y are integers of at least 6, the molar ratio of z to y is in
the range
from 1.0 to about 0.5, and x is an integer from about 1 ~ to about 264.
Useful aluminosilicate ion exchange materials are commercially available.
These aluminosilicates can be crystalline or amorphous in structure and can be
naturally-occurring aluminosilicates or synthetically derived. A method for
producing aIuminosilicate ion exchange materials is disclosed in U.S. Patent
3,985,669, Krummel, et al, issued October 12, 1976. Preferred synthetic
crystalline
aluminosilicate ion exchange materials useful herein are available under the
designations Zeolite A, Zeolite P (B), Zeolite MAP and Zeolite X. In an
especially
preferred embodiment, the crystalline aluminosiiicate ion exchange material
has the
formula:
Nal2~(A102)12(Si02)12~~xH20
wherein x is from about 20 to about 30, especially about 27. This material is
known
as Zeolite A. Dehydrated zeolites (x = 0 - 10) may also be used herein.
Preferably,
the aluminosilicate has a particle size of about 0.1-10 microns in diameter.
Organic detergent builders suitable for the purposes of the present invention
include, but are not restricted to, a wide variety of polycarboxylate
compounds. As
used herein, "polycarboxylate" refers to compounds having a plurality of
carboxylate groups, preferably at least 3 carboxylates. Polycarboxylate
builder can
generally be added to the composition in acid form, but can also be added in
the
form of a neutralized salt. When utilized in salt form, alkali metals, such as
sodium,
potassium, and lithium, or alkanoiammonium salts are preferred.
Included among the polycarboxylate builders are a variety of categories of
useful materials. One important category of polycarboxylate builders
encompasses
the ether polycarboxylates, including oxydisuccinate, as disclosed in Berg,
U.S.
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42
Patent 3,128,287, issued April 7, 1964, and Lamberti et al, U.S. Patent
3,635,830,
issued January 18, 1972. See also "TMS/TDS" builders of U.S. Patent 4,663,071,
issued to Bush et al, on May 5, 1987. Suitable ether polycarboxylates also
include
cyclic compounds, particularly alicyclic compounds, such as those described in
U.S.
Patents 3,923,679; 3,835,163; 4,158,635; 4,120,874 and 4,102,903.
Other useful detergency builders include the ether hydroxypolycarboxylates,
copolymers of malefic anhydride with ethylene or vinyl methyl ether, 1, 3, 5-
trihydroxy benzene-2, 4, 6-trisulphonic acid, and carboxymethyloxysuccinic
acid,
the various alkali metal, ammonium and substituted ammonium salts of
polyacetic
acids such as ethylenediamine tetraacetic acid and nitrilotriacetic acid, as
well as
polycarboxylates such as mellitic acid, succinic acid, oxydisuccinic acid,
polymaleic
acid, benzene 1,3,5-tricarboxylic acid, carboxymethyloxysuccinic acid, and
soluble
salts thereof.
Citrate builders, e.g., citric acid and soluble salts thereof (particularly
sodium
salt), are polycarboxylate builders of particular importance for heavy duty
liquid
detergent formulations due to their availability from renewable resources and
their
biodegradability. Citrates can also be used in granular compositions,
especially in
combination with zeolite and/or layered silicate builders. Oxydisuccinates are
also
especially useful in such compositions and combinations.
Also suitable in the detergent compositions of the present invention are the
3,3-dicarboxy-4-oxa-1,6-hexanedioates and the related compounds disclosed in
U.S.
Patent 4,566,984, Bush, issued January 28, 1986. Useful succinic acid builders
include the C5-C2p alkyl and alkenyl succinic acids and salts thereof. A
particularly
preferred compound of this type is dodecenylsuccinic acid. Specific examples
of
succinate builders include: laurylsuccinate, myristylsuccinate,
palmitylsuccinate, 2-
dodecenylsuccinate (preferred), 2-pentadecenylsuccinate, and the Iike.
Laurylsuccinates are the preferred builders of this group, and are described
in
European Patent Application 86200690.5/0,200,263, published November 5, 1986.
Other suitable polycarboxylates are disclosed in U.S. Patent 4,144,226,
Crutchfield et al, issued March 13, 1979 and in U.S. Patent 3,308,067, Diehl,
issued
March 7, 1967. See also Diehl U.S. Patent 3,723,322.
Fatty acids, e.g., C 12-C 1 g monocarboxylic acids, can also be incorporated
into the compositions alone, or in combination with the aforesaid builders,
especially citrate and/or the succinate builders, to provide additional
builder activity.
Such use of fatty acids will generally result in a diminution of sudsing,
which should
be taken into account by the formulator.
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43
in situations where phosphorus-based builders can be used, and especially in
the formulation of bars used for hand-laundering operations, the various
alkali metal
phosphates such as the well-known sodium tripolyphosphates, sodium
pyrophosphate and sodium orthophosphate can be used. Phosphonate builders such
as ethane-1-hydroxy-1,1-diphosphonate and other known phosphonates (see, for
example, U.S. Patents 3,159,581; 3,213,030; 3,422,021; 3,400,148 and
3,422,137)
can also be used.
Other Polymeric Soil Release Asents - Any polymeric soil release agent
known to those skilled in the art can optionally be employed in the
compositions and
processes of this invention. Polymeric soil release agents are characterized
by
having both hydrophilic segments, to hydrophilize the surface of hydrophobic
fibers,
such as polyester and nylon, and hydrophobic segments, to deposit upon
hydrophobic fibers and remain adhered thereto through completion of washing
and
rinsing cycles and, thus, serve as an anchor for the hydrophilic segments.
This can
enable stains occurring subsequent to treatment with the soil release agent to
be
more easily cleaned in later washing procedures.
The polymeric soil release agents useful herein especially include those soil
release agents having: (a) one or more nonionic hydrophile components
consisting
essentially of (i) polyoxyethylene segments with a degree of polymerization of
at
least 2, or (ii) oxypropylene or polyoxypropylene segments with a degree of
polymerization of from 2 to 10, wherein said hydrophile segment does not
encompass any oxypropylene unit unless it is bonded to adjacent moieties at
each
end by ether linkages, or (iii) a mixture of oxyalkylene units comprising
oxyethylene
and from 1 to about 30 oxypropylene units wherein said mixture contains a
suffi-
cient amount of oxyethylene units such that the hydrophile component has
hydrophilicity great enough to increase the hydrophilicity of conventional
polyester
synthetic fiber surfaces upon deposit of the soil release agent on such
surface, said
hydrophile segments preferably comprising at Ieast about 25% oxyethylene units
and more preferably, especially for such components having about 20 to 30
oxypropylene units, at least about 50% oxyethylene units; or (b) one or more
hydrophobe components comprising (i) C3 oxyalkylene terephthalate segments,
wherein, if said hydrophobe components also comprise oxyethylene
terephthalate,
the ratio of oxyethylene terephthalate:C3 oxyalkylene terephthalate units is
about
2:1 or lower, (ii) C4-C6 alkylene or oxy C4-C6 alkylene segments, or mixtures
therein, (iii) poly (vinyl ester) segments, preferably polyvinyl acetate),
having a
degree of polymerization of at least 2, or (iv) C 1-C4 alkyl ether or C4
hydroxyalkyl
ether substituents, or mixtures therein, wherein said substituents are present
in the
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form of Cl-C4 alkyl ether or C4 hydroxyalkyl ether cellulose derivatives, or
mixtures therein, and such cellulose derivatives are amphiphilic, whereby they
have
a sufficient level of C1-C4 alkyl ether and/or C4 hydroxyalkyl ether units to
deposit
upon conventional polyester synthetic fiber surfaces and retain a sufficient
level of
hydroxyls, once adhered to such conventional synthetic fiber surface, to
increase
fiber surface hydrophilicity, or a combination of (a) and (b).
Typically, the polyoxyethylene segments of (a)(i) will have a degree of
polymerization of up to about 200, although higher levels can be used,
preferably
from 3 to about 150, more preferably from 6 to about 100. Suitable oxy C4-C6
alkylene hydrophobe segments include, but are not limited to, end-caps of
polymeric
soil release agents such as M03S(CH2)nOCH2CH20-, where M is sodium and n is
an integer from 4-6, as disclosed in U.S. Patent 4,721,580, issued January 26,
1988
to Gosselink.
Polymeric soil release agents useful in the present invention also include
cellulosic derivatives such as hydroxyether cellulosic polymers, and the Like.
Such
agents are commercially available and include hydroxyethers of cellulose such
as
METHOCEL (Dow). Cellulosic soil release agents for use herein also include
those
selected from the group consisting of C1-C4 alkyl and C4 hydroxyalkyl
cellulose;
see U.S. Patent 4,000,093, issued December 28, 1976 to Nicol, et al.
Soil release agents characterized by polyvinyl ester) hydrophobe segments
include graft copolymers of polyvinyl ester), e.g., C1-C6 vinyl esters,
preferably
polyvinyl acetate) grafted onto polyalkylene oxide backbones, such as
polyethylene
oxide backbones. See European Patent Application 0 219 048, published April
22,
1987 by Kud, et al. Commercially available soil release agents of this kind
include
the SOKALAN type of material, e.g., SOKALAN HP-22, available from BASF
(Germany).
One type of preferred soil release agent is a copolymer having random
blocks of ethylene terephthalate and polyethylene oxide (PEO) terephthalate.
The
molecular weight of this polymeric soil release agent is in the range of from
about
25,000 to about 55,000. See U.S. Patent 3,959,230 to Hays, issued May 25, 1976
and U.S. Patent 3,893,929 to Basadur issued July 8, 1975.
Another preferred polymeric soil release agent is a polyester with repeat
units of ethylene terephthalate units contains 10-15% by weight of ethylene
terephthalate units together with 90-80% by weight of polyoxyethylene
terephthalate
units, derived from a polyoxyethylene glycol of average molecular weight 300-
5,000. Examples of this polymer include the commercially available material
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ZELCON 5126 (from Dupont) and MILEASE T (from ICI). See also U.S. Patent
4,702,857, issued October 27, 1987 to Gosselink.
Another preferred polymeric soil release agent is a sulfonated product of a
substantially linear ester oligomer comprised of an oligomeric ester backbone
of
terephthaloyl and oxyalkyleneoxy repeat units and terminal moieties covalently
attached to the backbone. These soil release agents are described fully in
U.S.
Patent 4,968,451, issued November 6, 1990 to J.J. Scheibel and E.P. Gosselink.
Other suitable polymeric soil release agents include the terephthalate
polyesters of
U.S. Patent 4,711,730, issued December 8, 1987 to Gosselink et al, the anionic
end-
capped oligomeric esters of U.S. Patent 4,721,580, issued January 26, 1988 to
Gosselink, and the block polyester oiigomeric compounds of U.S. Patent
4,702,87,
issued October 27, 1987 to Gosselink.
Preferred polymeric soil release agents also include the soil release agents
of
U.S. Patent 4,877,896, issued October 31, 1989 to Maldonado et al, which
discloses
anionic, especially sulfoaroyl, end-capped terephthalate esters.
Still another preferred soil release agent is an oligomer with repeat units of
terephthaloyl units, sulfoisoterephthaloyl units, oxyethyleneoxy and oxy-1,2-
propylene units. The repeat units form the backbone of the oligomer and are
preferably terminated with modified isethionate end-caps. A particularly
preferred
soil release agent of this type comprises about one sulfoisophthaloyl unit, 5
terephthaloyl units, oxyethyleneoxy and oxy-l,2-propyleneoxy units in a ratio
of
from about 1.7 to about 1.8, and two end-cap units of sodium 2-(2-
hydroxyethoxy)-
ethanesulfonate. Said soil release agent also comprises from about 0.5% to
about
20%, by weight of the oligomer, of a crystalline-reducing stabilizer,
preferably
selected from the group consisting of xylene sulfonate, cumene sulfonate,
toluene
sulfonate, and mixtures thereof.
If utilized, soil release agents will generally comprise from about 0.01 % to
about 10.0%, by weight, of the detergent compositions herein, typically from
about
0.1% to about 5%, preferably from about 0.2% to about 3.0%.
ChelatinQ A. ents - The detergent compositions herein may also optionally
contain one or more iron and/or manganese chelating agents. Such chelating
agents
can be selected from the group consisting of amino carboxylates, amino
phosphonates, polyfunctionally-substituted aromatic chelating agents and
mixtures
therein, all as hereinafter defined. Without intending to be bound by theory,
it is
believed that the benefit of these materials is due in part to their
exceptional ability
to remove iron and manganese ions from washing solutions by formation of
soluble
chelates.
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Amino carboxylates useful as optional chelating agents include
ethylenediaminetetracetates, N-hydroxyethylethylenediaminetriacetates, nitrilo-
triacetates, ethylenediamine tetraproprionates,
triethylenetetraaminehexacetates,
diethylenetriaminepentaacetates, and ethanoldigiycines, alkali metal,
ammonium,
and substituted ammonium salts therein and mixtures therein.
Amino phosphonates are also suitable for use as chelating agents in the
compositions of the invention when at lease low levels of total phosphorus are
permitted in detergent compositions, and include ethylenediaminetetrakis
(methylenephosphonates) as DEQUEST. Preferred, these amino phosphonates to
not contain alkyl or alkenyl groups with more than about 6 carbon atoms.
Polyfunctionally-substituted aromatic chelating agents are also useful in the
compositions herein. See U.S. Patent 3,812,044, issued May 21, 1974, to Connor
et
al. Preferred compounds of this type in acid form are dihydroxydisulfobenzenes
such as 1,2-dihydroxy-3,5-disulfobenzene.
A preferred biodegradable chelator for use herein is ethylenediamine
disuccinate ("EDDS"), especially the [S,S] isomer as described in U.S. Patent
4,704,233, November 3, 1987, to Hartman and Perkins.
If utilized, these chelating agents will generally comprise from about 0.1% to
about i 0% by weight of the detergent compositions herein. More preferably, if
utilized, the chelating agents will comprise from about 0.1 % to about 3.0% by
weight of such compositions.
Clay Soil RemovallAnti-_ redeposition Agents - The compositions of the
present invention can also optionally contain water-soluble ethoxylated amines
having clay soil removal and antiredeposition properties. Granular detergent
compositions which contain these compounds typically contain from about 0.01 %
to
about 10.0% by weight of the water-soluble ethoxylates amines; liquid
detergent
compositions typically contain about 0.01% to about 5%.
The most preferred soil release and anti-redeposition agent is ethoxylated
tetraethylenepentamine. Exemplary ethoxylated amines are further described in
U.S. Patent 4,597,898, VanderMeer, issued July 1, 1986. Another group of
preferred clay soil removal-antiredeposition agents are the cationic compounds
disclosed in European Patent Application 111,965, Oh and Gosselink, published
3une 27, 1984. Other clay soil removal/antiredeposition agents which can be
used
include the ethoxylated amine polymers disclosed in European Patent
Application
111,984, Gosselink, published June 27, 1984; the zwitterionic polymers
disclosed in
European Patent Application 112,592, Gosselink, published July 4, 1984; and
the
amine oxides disclosed in U.S. Patent 4,548,744, Connor, issued October 22,
1985.
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Other clay soil removal and/or anti redeposition agents known in the art can
also be
utilized in the compositions herein. Another type of preferred
antiredeposition agent
includes the carboxy methyl cellulose (CMC) materials. These materials are
well
known in the art.
Polymeric Dispersing Agents - Polymeric dispersing agents can
advantageously be utilized at levels from about 0.1 % to about 7%, by weight,
in the
compositions herein, especially in the presence of zeolite and/or layered
silicate
builders. Suitable polymeric dispersing agents include polymeric
polycarboxylates
and polyethylene glycols, although others known in the art can also be used.
It is
believed, though it is not intended to be limited by theory, that polymeric
dispersing
agents enhance overall detergent builder performance, when used in combination
with other builders (including lower molecular weight polycarboxylates) by
crystal
growth inhibition, particulate soil release peptization, and anti-
redeposition.
Polymeric polycarboxylate materials can be prepared by polymerizing or
copolymerizing suitable unsaturated monomers, preferably in their acid form.
Unsaturated monomeric acids that can be polymerized to form suitable polymeric
polycarboxylates include acrylic acid, malefic acid (or malefic anhydride),
fumaric
acid, itaconic acid, aconitic acid, mesaconic acid, citraconic acid and
methylenemalonic acid. The presence in the polymeric polycarboxylates herein
or
monomeric segments, containing no carboxylate radicals such as vinylmethyl
ether,
styrene, ethylene, etc. is suitable provided that such segments do not
constitute more
than about 40% by weight.
Particularly suitable polymeric polycarboxylates can be derived from acrylic
acid. Such acrylic acid-based polymers which are useful herein are the water-
soluble salts of polymerized acrylic acid. The average molecular weight of
such
polymers in the acid form preferably ranges from about 2,000 to 10,000, more
preferably from about 4,000 to 7,000 and most preferably from about 4,000 to
5,000.
Water-soluble salts of such acrylic acid polymers can include, for example,
the
alkali metal, ammonium and substituted ammonium salts. Soluble polymers of
this
type are known materials. Use of polyacrylates of this type in detergent
compositions has been disclosed, for example, in Diehl, U.S. Patent 3,308,067,
issued march 7, 1967.
Acrylic/maleic-based copolymers may also be used as a preferred component
of the dispersing/anti-redeposition agent. Such materials include the water-
soluble
salts of copolymers of acrylic acid and malefic acid. The average molecular
weight
of such copolymers in the acid form preferably ranges from about 2,000 to
100,000,
more preferably from about 5,000 to 75,000, most preferably from about 7,000
to
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48 _
65,000. The ratio of acrylate to maleate segments in such copolymers will
generally
range from about 30:1 to about 1:1, more preferably from about 10:1 to 2:1.
Water-
soluble salts of such acrylic acid/maleic acid copolymers can include, for
example,
the alkali metal, ammonium and substituted ammonium salts. Soluble
acrylate/maleate copolymers of this type are known materials which are
described in
European Patent Application No. 66915, published December 15, 1982, as well as
in
EP 193,360, published September 3, 1986, which also describes such polymers
comprising hydroxypropylacrylate. Still other useful dispersing agents include
the
maleic/acrylic/vinyl alcohol terpolymers. Such materials are also disclosed in
EP
193,360, including, for example, the 45/45/10 terpolymer of
acrylic/maleic/vinyl
alcohol.
Another polymeric material which can be included is polyethylene glycol
(PEG). PEG can exhibit dispersing agent performance as well as act as a clay
soil
removal-antiredeposition agent. Typical molecular weight ranges for these
purposes
range from about 500 to about 100,000, preferably from about 1,000 to about
50,000, more preferably from about 1,500 to about 10,000.
Polyaspartate and polyglutamate dispersing agents may also be used,
especially in conjunction with zeolite builders. Dispersing agents such as
polyaspartate preferably have a molecular weight (avg.) of about 10,000.
Suds Suppressors - Compounds for reducing or suppressing the formation of
suds can be incorporated into the compositions of the present invention. Suds
suppression can be of particular importance in the so-called "high
concentration
cleaning process" as described in U.S. 4,489,455 and 4,489,574 and in front-
loading
European-style washing machines.
A wide variety of materials may be used as suds suppressors, and suds
suppressors are well known to those skilled in the art. See, for example, Kirk
Othmer Encyclopedia of Chemical Technology, Third Edition, Volume 7, pages
430-447 (John Wiley & Sons, Inc., 1979). One category of suds suppressor of
particular interest encompasses monocarboxylic fatty acid and soluble salts
therein.
See U.S. Patent 2,954,347, issued September 27, 1960 to Wayne St. John. The
monocarboxylic fatty acids and salts thereof used as suds suppressor typically
have
hydrocarbyl chains of 10 to about 24 carbon atoms, preferably 12 to 18 carbon
atoms. Suitable salts include the alkali metal salts such as sodium,
potassium, and
lithium salts, and ammonium and alkanolammonium salts.
The detergent compositions herein may also contain non-surfactant suds
suppressors. These include, for example: high molecular weight hydrocarbons
such
as paraffin, fatty acid esters (e.g., fatty acid triglycerides), fatty acid
esters of
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monovalent alcohols, aliphatic C 1 g-C4p ketones (e.g., stearone), etc. Other
suds
inhibitors include N-aikylated amino triazines such as tri- to hexa-
alkylmelamines or
di- to tetra-alkyldiamine chlortriazines formed as products of cyanuric
chloride with
two or three moles of a primary or secondary amine containing 1 to 24 carbon
atoms, propylene oxide, and monostearyl phosphates such as monostearyl alcohol
phosphate ester and monostearyl di-alkali metal (e.g., K, Na, and Li)
phosphates and
phosphate esters. The hydrocarbons such as paraffin and haloparaffin can be
utilized in liquid form. The liquid hydrocarbons will be liquid at room
temperature
and atmospheric pressure, and will have a pour point in the range of about -
40°C and
about 50°C, and a minimum boiling point not less than about
110°C (atmospheric
pressure). It is also known to utilize waxy hydrocarbons, preferably having a
melting point below about 100°C. The hydrocarbons constitute a
preferred category
of suds suppressor for detergent compositions. Hydrocarbon suds suppressors
are
described, for example, in U.S. Patent 4,265,779, issued May 5, 1981 to
Gandolfo et
al. The hydrocarbons, thus, include aliphatic, alicyclic, aromatic, and
heterocyclic
saturated or unsaturated hydrocarbons having from about 12 to about 70 carbon
atoms. The term "paraffin," as used in this suds suppressor discussion, is
intended
to include mixtures of true paraffins and cyclic hydrocarbons.
Another preferred category of non-surfactant suds suppressors comprises
silicone suds suppressors. This category includes the use of
polyorganosiloxane
oils, such as polydimethylsiloxane, dispersions or emulsions of
polyorganosiioxane
oils or resins, and combinations of polyorganosiloxane with silica particles
wherein
the polyorganosiloxane is chemisorbed or fused onto the silica. Silicone suds
suppressors are well known in the art and are, for example, disclosed in U.S.
Patent
4,265,779, issued May 5, 1981 to Gandolfo et al and European Patent
Application
No. 89307851.9, published February 7, 1990, by Starch, M. S.
Other silicone suds suppressors are disclosed in U.S. Patent 3,455,839 which
relates to compositions and processes for defoaming aqueous solutions by
incorporating therein small amounts of polydimethylsiloxane fluids.
Mixtures of silicone and silanated silica are described, for instance, in
German Patent Application DOS 2,124,526. Silicone defoamers and suds
controlling agents in granular detergent compositions are disclosed in U.S.
Patent
3,933,672, Bartolotta et al, and in U.S. Patent 4,652,392, Baginski et al,
issued
March 24, 1987.
An exemplary silicone based suds suppressor for use herein is a suds
suppressing amount of a suds controlling agent consisting essentially of:
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(i) polydimethylsiloxane fluid having a viscosity of from about 20 cs. to
about 1,500 cs. at 25°C;
(ii) from about 5 to about 50 parts per 100 parts by weight of (i) of siloxane
resin composed of (CH3)3Si01/2 units of Si02 units in a ratio of from
(CH3)3 Si01/2 units and to Si02 units of from about 0.6:1 to about
I .2:1; and
(iii) from about 1 to about 20 parts per 100 parts by weight of (i) of a solid
silica gel.
In the preferred silicone suds suppressor used herein, the solvent for a
continuous phase is made up of certain polyethylene glycols or polyethylene-
polypropylene glycol copolymers or mixtures thereof (preferred), or
polypropylene
glycol. The primary silicone suds suppressor is branched/crosslinked and
preferably
not linear.
To illustrate this point further, typical liquid laundry detergent
compositions
with controlled suds will optionally comprise from about 0.001 to about 1,
preferably from about 0.01 to about 0.7, most preferably from about 0.05 to
about
0.5, weight % of said silicone suds suppressor, which comprises ( 1 ) a
nonaqueous
emulsion of a primary antifoam agent which is a mixture of (a) a
polyorganosiloxane, (b) a resinous siloxane or a silicone resin-producing
silicone
compound, (c) a finely divided filler material, and (d) a catalyst to promote
the
reaction of mixture components (a), (b) and (c), to form silanolates; (2) at
least one
nonionic silicone surfactant; and (3) polyethylene glycol or a copolymer of
polyethylene-polypropylene glycol having a solubility in water at room
temperature
of more than about 2 weight %; and without polypropylene glycol. Similar
amounts
can be used in granular compositions, gels, etc. See also U.S. Patents
4,978,471,
Starch, issued December 18, 1990, and 4,983,316, Starch, issued 3anuary 8,
1991,
5,288,431, Huber et al., issued February 22, 1994, and U.S. Patents 4,639,489
and
4,749,740, Aizawa et al at column 1, line 46 through column 4, line 35.
The silicone suds suppressor herein preferably comprises polyethylene
glycol and a copolymer of polyethylene glycol/polypropylene glycol, all having
an
average molecular weight of less than about 1,000, preferably between about
100
and 800. The polyethylene glycol and polyethylene/polypropylene glycol
copolymers herein have a solubility in water at room temperature of more than
about
2 weight %, preferably more than about 5 weight %.
The preferred solvent herein is polyethylene glycol having an average
molecular weight of less than about 1,000, more preferably between about 100
and
800, most preferably between 200 and 400, and a copolymer of polyethylene
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glycol/polypropylene glycol, preferably PPG 200/PEG 300. Preferred is a weight
ratio of between about 1: l and 1:10, most preferably between 1:3 and 1:6, of
polyethylene glycol:copolymer of polyethylene-polypropylene glycol.
Other suds suppressors useful herein comprise the secondary alcohols (e.g.,
2-alkyl alkanols) and mixtures of such alcohols with silicone oils, such as
the
silicones disclosed in U.S. 4,798,679, 4,075,118 and EP 150,872. The secondary
alcohols include the C6-C 16 alkyl alcohols having a C 1-C 16 chain. A
preferred
alcohol is 2-butyl octanol, which is available from Condea under the trademark
ISOFOL 12. Mixtures of secondary alcohols are available under the trademark
ISALCHEM 123 from Enichem. Mixed suds suppressors typically comprise
mixtures of alcohol + silicone at a weight ratio of 1:~ to 5:1.
For any detergent compositions to be used in automatic laundry washing
machines, suds should not form to the extent that they overflow the washing
machine. Suds suppressors, when utilized, are preferably present in a "suds
suppressing amount. By "suds suppressing amount" is meant that the formulator
of
the composition can select an amount of this suds controlling agent that will
sufficiently control the suds to result in a low-sudsing laundry detergent for
use in
automatic laundry washing machines.
The compositions herein will generally comprise from 0% to about 5% of
suds suppressor. When utilized as suds suppressors, monocarboxylic fatty
acids,
and salts therein, will be present typically in amounts up to about 5%, by
weight, of
the detergent composition. Preferably, from about 0.5% to about 3% of fatty
monocarboxylate suds suppressor is utilized. Silicone suds suppressors are
typically
utilized in amounts up to about 2.0%, by weight, of the detergent composition,
although higher amounts may be used. This upper limit is practical in nature,
due
primarily to concern with keeping costs minimized and effectiveness of lower
amounts for effectively controlling sudsing. Preferably from about 0.01 % to
about
1% of silicone suds suppressor is used, more preferably from about 0.25% to
about
0.5%. As used herein, these weight percentage values include any silica that
may be
utilized in combination with polyorganosiloxane, as well as any adjunct
materials
that may be utilized. Monostearyl phosphate suds suppressors are generally
utilized
in amounts ranging from about 0.1 % to about 2%, by weight, of the
composition.
Hydrocarbon suds suppressors are typically utilized in amounts ranging from
about
0.01 % to about 5.0%, although higher levels can be used. The alcohol suds
suppressors are typically used at 0.2%-3% by weight of the finished
compositions.
Brig_htener - Any conventional optical brighteners or other brightening or
whitening agents known in the art can be incorporated at levels typically from
about
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J7
0.05% to about 1.2%, by weight, into the detergent compositions herein.
Commercial optical brighteners which may be useful in the present invention
can be
classified into subgroups, which include, but are not necessarily limited to,
derivatives of stilbene, pyrazoline, coumarin, carboxylic acid,
methinecyanines,
dibenzothiphene-5,~-dioxide, azoles, 5- and 6-membered-ring heterocycles, and
other miscellaneous agents. Examples of such brighteners are disclosed in "The
Production and Application of Fluorescent Brightening Agents", M. Zahradnik,
Published by John Wiley & Sons, New York ( 1982).
Specific examples of optical brighteners which are useful in the present
compositions are those identified in U.S. Patent 4,790,856, issued to Wixon on
December 13, 1988. These brighteners include the PHORWHITE series of
brighteners from Verona. Other brighteners disclosed in this reference
include:
Tinopal UNPA, Tinopal CBS and Tinopal SBM; available from Ciba-Geigy; Artic
White CC and Artic White CWD, available from Hilton-Davis, located in Italy;
the
2-(4-stryl-phenyl)-2H-napthol[1,2-d]triazoles; 4,4'-bis- (1,2,3-triazol-2-yl)-
stil-
benes; 4,4'-bis(stryl)bisphenyls; and the aminocoumarins. Specific examples of
these brighteners include 4-methyl-7-diethyl- amino coumarin; 1,2-bis(-
venzimidazol-2-yl)ethylene; 1,3-diphenyl-phrazolines; 2,5-bis(benzoxazol-2-
yI)thiophene; 2-stryl-napth-[1,2-d]oxazole; and 2-(stilbene-4-yl)-2H-naphtho-
[1,2-
d]triazole. See also U.S. Patent 3,646,015, issued February 29, 1972 to
Hamilton.
Anionic brighteners are preferred herein.
Fabric Softeners - Various through-the-wash fabric softeners, especially the
impalpable smectite clays of U.S. Patent 4,062,647, Storm and Nirschl, issued
December 13, 1977, as well as other softener clays known in the art, can
optionally
be used typically at levels of from about 0.5% to about 10% by weight in the
present
compositions to provide fabric softener benefits concurrently with fabric
cleaning.
Clay softeners can be used in combination with amine and cationic softeners as
disclosed, for example, in U.S. Patent 4,375,416, Crisp et al, March 1, 1983
and
U.S. Patent 4,291,071, Hams et al, issued September 22, 1981.
Other Ingredients - A wide variety of other ingredients useful in detergent
compositions can be included in the compositions herein, including other
active
ingredients, carriers, hydrotropes, processing aids, dyes or pigments,
solvents for
liquid formulations, solid fillers for bar compositions, etc. If high sudsing
is desired,
suds boosters such as the C 10-C 16 alkanolamides can be incorporated into the
compositions, typically at 1 %-10% levels. The C 10-C 14 monoethanol and
diethanol amides illustrate a typical class of such suds boosters. Use of such
suds
boosters with high sudsing adjunct surfactants such as the amine oxides,
betaines
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and sultaines noted above is also advantageous. If desired, soluble magnesium
salts
such as MgCl2, MgS04, and the like, can be added at levels of, typically, 0.1
%-2%,
to provide additional suds and to enhance grease removal performance.
Various detersive ingredients employed in the present compositions
optionally can be further stabilized by absorbing said ingredients onto a
porous
hydrophobic substrate, then coating said substrate with a hydrophobic coating.
Preferably, the detersive ingredient is admixed with a surfactant before being
absorbed into the porous substrate. In use, the detersive ingredient is
released from
the substrate into the aqueous washing liquor, where it performs its intended
detersive function.
To illustrate this technique in more detail, a porous hydrophobic silica
(trademark SIPERNAT D 10, DeGussa) is admixed with a proteolytic enzyme
solution containing 3%-5% of C 13-15 ethoxylated alcohol (EO 7) nonionic
surfactant. Typically, the enzyme/surfactant solution is 2.5 X the weight of
silica.
The resulting powder is dispersed with stirring in silicone oil (various
silicone oil
viscosity in the range of 500-12,500 can be used). The resulting silicone oil
dispersion is emulsified or otherwise added to the final detergent matrix. By
this
means, ingredients such as the aforementioned enzymes, bleaches, bleach
activators,
bleach catalysts, photoactivators, dyes, fluorescers, fabric conditioners and
hydrolyzable surfactants can be "protected" for use in detergents, including
liquid
laundry detergent compositions.
Liquid detergent compositions can contain water and other solvents as
carriers. Low molecular weight primary or secondary alcohols exemplified by
methanol, ethanol, propanol, and isopropanol are suitable. Monohydric aicohols
are
preferred for solubilizing surfactant, but polyols such as those containing
from 2 to
about 6 carbon atoms and from 2 to about 6 hydroxy groups (e.g., 1,3-
propanediol,
ethylene glycol, glycerin, and 1,2-propanediol) can also be used. The
compositions
may contain from 5% to 90%, typically 10% to SO% of such carriers.
The detergent compositions herein will preferably be formulated such that,
during use in aqueous cleaning operations, the wash water will have a pH of
between about 6.5 and about 11, preferably between about 7.5 and 10.5. Liquid
dishwashing product formulations preferably have a pH between about 6.8 and
about 9Ø Laundry products are typically at pH 9-11. Techniques for
controlling
pH at recommended usage levels include the use of buffers, alkalis, acids,
etc., and
are well known to those skilled in the art.
Dye Transfer Inhibitint Agents - The compositions of the present invention
may also include one or more materials effective for inhibiting the transfer
of dyes
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from one fabric to another during the cleaning process. Generally, such dye
transfer
inhibiting agents include polyvinyl pyrrolidone polymers, polyamine N-oxide
polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, manganese
phthalocyanine, peroxidases, and mixtures thereof. If used, these agents
typically
comprise from about 0.01% to about 10% by weight of the composition,
preferably
from about 0.01% to about 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-, -O-, -N=; x is 0 or
1; and
R is aliphatic, ethoxylated aliphatics, aromatics, heterocyclic or alicyclic
groups or
any combination thereof to which the nitrogen of the N-O group can be attached
or
the N-O group is part of these groups. Preferred polyamine N-oxides are those
wherein R is a heterocyclic group such as pyridine, pyrrole, imidazole,
pyrrolidine,
piperidine and derivatives thereof.
The N-O group can be represented by the following general structures:
O O
I I
(R~)x- i -~2)y~ =N-(Rac
(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-O group
can be
attached or form part of any of the aforementioned groups. The amine oxide
unit of
the polyamine N-oxides has a pKa <10, preferably pKa <7, more preferred pKa
<6.
Any polymer backbone can be used as long as the amine oxide polymer
formed is water-soluble and has dye transfer inhibiting properties. Examples
of
suitable polymeric backbones are polyvinyls, polyalkylenes, polyesters,
polyethers,
polyamide, polyimides, polyacrylates and mixtures thereof. These polymers
include
random or block copolymers where one monomer type is an amine N-oxide and the
other monomer type is an N-oxide. The amine N-oxide polymers typically have a
ratio of amine to the amine N-oxide of 10:1 to 1:1,000,000. However, the
number of
amine oxide groups present in the polyamine oxide polymer can be varied by
appropriate copolymerization or by an appropriate degree of N-oxidation. The
polyamine oxides can be obtained in almost any degree of polymerization.
Typically, the average molecular weight is within the range of 500 to
1,000,000;
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more preferred 1,000 to 500,000; most preferred 5,000 to 100,000. This
preferred
class of materials can be referred to as "PVNO".
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.
Copolymers of N-vinylpyrrolidone and N-vinylimidazole polymers (referred
to as a class as "PVPVI") are also preferred for use herein. Preferably the
PVPVI
has an average molecular weight range from 5,000 to 1,000,000, more preferably
from 5,000 to 200,000, and most preferably from 10,000 to 20,000. (The average
molecular weight range is determined by light scattering as described in
Barth, et al.,
Chemical Analysis, Vol 113. "Modern Methods of Polymer Characterization", the
disclosures of which are incorporated herein by reference.) The PVPVI
copolymers
typically have a molar ratio of N-vinylimidazole to N-vinylpyrrolidone from
1:1 to
0.2:1, more preferably from 0.8:1 to 0.3:1, most preferably from 0.6:1 to
0.4:1.
These copolymers can be either linear or branched.
The present invention compositions also may employ a polyvinylpyrrolidone
("PVP") having an average molecular weight of from about 5,000 to about
400,000,
preferably from about 5,000 to about 200,000, and more preferably from about
5,000
to about 50,000. PVP's are known to persons skilled in the detergent field;
see, for
example, EP-A-262,897 and EP-A-256,696, incorporated herein by reference.
Compositions containing PVP can also contain polyethylene glycol ("PEG")
having
an average molecular weight from about 500 to about 100,000, preferably from
about 1,000 to about 10,000. Preferably, the ratio of PEG to PVP on a ppm
basis
delivered in wash solutions is from about 2:1 to about 50:1, and more
preferably
from about 3:1 to about 10:1.
The following non-limiting examples illustrate the use of a composition of
the present invention as a soil release agent comprising fluorescent whitening
groups
for the thru-the-wash application to polyester fabrics.
EXAMPLES 1 & 2
The following describe high density liquid detergent compositions according
to the present invention:
weight
Ingredients 1 2
Polyhydroxy Coco-Fatty Acid 3.65 3.50
Amide
C 12-C 13 Alcohol Ethoxylate 3.65 0.80
E9
Sodium C 12-C 15 Alcohol Sulfate6.03 2.50
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Sodium C 12-C 15 Alcohol Ethoxylate9.29 15.10
E2,5
Sulfate
C 1 p Amidopropyl Amine 0 1.30
Citric Acid 2.44 3.0
Fatty Acid (C 12-C 14) 4.23 2.00
Ethanol 3.00 2.81
Monoethanolamine 1.50 0.75
Propanediol 8.00 7.50
Boric Acid 3.50 3.50
Tetraethylenepentamine 0 1.18
Sodium Toluene Sulfonate 2.50 2.25
NaOH 2.08 2.43
Minors * 1.60 1.30
Soil Release Polymer 0.33 0.22
Soil Release Polymer/FWA** 0.50 0.50
Water balance balance
* Minors - includes optical brightener and enzymes (protease, lipase,
cellulase, and amylase).
** Soil release polymer according to Example 12.
Compositions of the present invention are also prepared by preparing high
density granular formulas according to this example utilizing the fluorescent
whitening soil release polymers alone or in combination with other soil
release
polymers.
EXAMPLES 3-6
wed-h~ t
redient 3 4 5 6
Sodium C 11-C 13 alkylbenzenesulfonate13 13.7 10.4 11.1
.3
Sodium C 14-C 15 alcohol sulfate3.9 4. 4.5 11.2
Sodium C 14-C 15 alcohol ethoxylate2.0 2.0 0.0 0.0
(0.5) sulfate
Sodium C 14-C 15 alcohol ethoxylate0.5 0.5 0.5 1.0
(6.5)
Tallow fatty acid 0.0 0.0 0.0 1.1
Sodium tripolyphosphate 0.0 41.0 0.0 0.0
Zeolite A, hydrate (0.1-10 micron26.3 0.0 21.3 28.0
size)
Sodium carbonate 23.9 12.4 25.2 16.1
Sodium Polyacrylate (45%) 3.4 0.0 2.7 3.4
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Sodium silicate (1:6 ratio Na0/Si02)(46%)2.4 6.4 2.1 2.6
Sodium sulfate 10.5 10.9 8.2 1 ~.0
Sodium perborate 1.0 1.0 5.0 0.0
Poly(ethyleneglycol), MW 4000 1.7 0.4 1.0 1.1
(SO%)
Citric acid 0.0 0.0 3.0 0.0
Nonyl ester of sodium p-hydroxybenzene-0.0 0.0 5.9 0.0
sulfonate
Soil release polymer 0.5 0.5 0.5 0.5
Soil release polymer comprising0.5 0.5 0.5 0.5
fluorescent whitening unit according
to
Example 25
Moisture 7.5 3.1 6.1 7.3
l3aiance co 1 uu~~o can, for example, include minors like optical brightener,
perfiune,
suds suppresser, soil dispersant, protease, lipase, cellulase, chelating
agents, dye
transfer inhibiting agents, additional water, and fillers, including CaC03,
talc,
silicates, etc.
Aqueous crutcher mixes of heat and alkali stable components of the
detergent compositions are prepared and spray-dried and the other ingredients
are
admixed so that they contain the ingredients tabulated at the levels shown.
The soil
release agents of the present invention can be, for example, pulverized and
admixed
in an amount sufficient for use at a level of 0.5% by weight in conjunction
with the
detergent compositions.
The detergent granules with fluorescent whitening unit soil release polymers
are added (99.5 parts/0.5 parts by weight, respectively) together with a 6 Ib.
load of
previously laundered fabrics (load composition: 10 wt % polyester fabrics/50
wt
polyester-cotton/40 wt % cotton fabrics) to a Sears KENMORE washing machine.
Actual weights of detergent and soil release agent compositions are take to
provide a
995 ppm concentration of the former and 5 ppm concentration of the latter in
the 17
gallon (65 liter) water-fill machine. The water used has 7 grains/gallon
hardness and
a pH of 7 to 7.5 prior to (abut 9 to about 10.5 after) addition of the
detergent and
ester compositions.
The fabrics are laundered at 35o C (95o F) for a full cycle (12 min.) and
rinsed at 21 o C (70o F). the fabrics are then line dried and are exposed to a
variety
of soils (by wear or controlled application). The entire cycle of laundering
and
soiling is repeated several times for each of the detergent compositions.
Separate
fabric bundles are reserved for use with each of the detergent compositions.
all
polyester-containing fabrics display significantly improved whiteness during
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58
laundering compared with fabrics which have not been exposed to the
compositions
of the invention.
Soil release agents comprising fluorescent whitening units of the present
invention are especially useful in conventional laundry detergent compositions
such
as those typically found in granular detergents or laundry bars. U.S. Patent
3,178,370, Okenfuss, issued April 13, 196$, describes laundry detergent bars
and
processes for making them. Philippine Patent 13,778, Anderson, issued
September
23, 1980, describes synthetic detergent laundry bars. Methods for making
laundry
detergent bars by various extrusion methods are well known in the art.
EXAMPLE 7
Ingredients Weieht
C 12 linear alkyl benzene sulfonate30
Phosphate (as sodium tripolyphosphate)7
Sodium carbonate 2$
Sodium pyrophosphate 7
Coconut monoethanolamide 2
Zeolite A, (0.1-10 micron) $
Carboxycellulose 0.2
EthyIenediamine disuccinate chelant0.4
(EDDS)
Polyacrylate (MW = 1400) 0.2
Nonanolyoxybenzenesulfonate $
Soil release agent comprising
fluorescent whitening unit* 0.$
Soil release agent 0.$
Sodium percarbonate * * $
Brightener, perfume 0.2
Protease 0.3
Calcium sulfate 1
Magnesium sulfate 1
Water 4
Filler*** Balance to 100
*Soil release polymer according to Example 27.
** Average particle size of 400 to 1200 microns.
* * * Can be selected from convenient materials such as Calcium carbonate,
talc,
clay, silicates, and the like.
the detergent bars are processed in conventional soap or detergent bar
making equipment as commonly used in the art. The soil release agent is
pulverized
and admixed in an amount sufficient for use at a level of 0.$% by weight in
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59
conjunction with the detergent compositions. Testing is conducted following
the
test methods in Examples 3-6.
Compositions of the present invention are also prepared by preparing bar
formulas according to Examples 8 and 9.
EXAMPLES 8-9
Laundry bars suitable for hand-washing soiled fabrics are prepared by
standard extrusion processes and comprise the following:
wPiaht ~/
Ingredients g
LAS I 2 6
Soap 44 29
Sodium tripolyphosphate 5 5
Sodium Carbonate 4 6
Optical brightener 0.03 0
Talc 0 35.5
Perfume 0.45 0
Sodium sulfate 0.29 0
Bentonite clay 12.81 0
Sodium chloride 2 2
Soil release agent 0.5 0.5
Soil release agent comprising fluorescent0.5
whitening units, according to Example
27
Soil release agent comprising fluorescent 0,5
whitening units, according to Example
23
Other* 0.42 1.5
Water balance balance
* Can be selected from convenient materials such as Calcium carbonate, talc,
clay,
silicates, and the like.
The following is an example of the preparation of a preferred soil release
polymer comprising a fluorescent whitening unit.
EXAMPLE 10
Trinhenylnhosphonium-(4-carboxymethoxyphenyl)methane
To a 500 mL, three-necked round bottom flask equipped with a magnetic
stirring bar, condenser, and thermometer connected to a temperature
controlling
device (Thermowatch, I2R) is added 4-chloromethylbenzoic acid (Aldrich, 66.7
gm,
0.391 mol), methanol (Baker, 272 gm, 8.5 mol), and Amberlyst~ 15 acidic resin
(12
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gm, 55.2 meq). The solution is heated at reflux overnight. A 1H-NMR (DMSO-d6)
shows the virtual disappearance of the carboxylic acid peak at 11.5 ppm and
the
emergence of a methyl ester peak at --4 ppm. The solution is filtered and
concentrated on the rotary evaporator and Kugelrohr apparatus (Aldrich,
80°C) to
afford 60.7 gm (0.329 mol) of thick white liquid. To this material in a 1 L
three-
necked round bottom flask equipped as described above is added
triphenylphosphine
(TCI, 87.3 gm, 0.333 mol) and toluene (Baker, 300 gm). The initially clear
solution begins to form a white precipitate after a few minutes at reflux and
is
allowed to stir at reflux overnight. A 13C-NMR (DMSO-d6) shows ~15% starting
materials remaining. An additional 18 gm (0.069 mol) of triphenylphosphine is
added, and the mixture is heated at reflux for an additional overnight period.
A
13C-NMR (DMSO-d6) shows the virtual disappearance of the peak at -45 ppm for
starting chloride
(-CH2C1) and the emergence of product peaks at --28.5 ppm and ~29 ppm
[-CH~P(C6H5)3]. The toluene is evaporated on the rotary evaporator and
Kugelrohr
apparatus (~ 100°C) to afford 164 gm of white solid.
EXAMPLE 11
Synthesis of Trans-methyl 2'-Sodiosulfostilbene-4-carboxylate
To 146 gm (0.327 mol) of the adduct prepared in Example I O in a 2L, three-
neck round bottom flask equipped with a magnetic stirnng bar, condenser,
addition
funnel, and thermometer connected to a temperature controlling device
(Thermowatch, I2R), is added 2-formylbenzenesulfonic acid, sodium salt,
hydrate
(Aldrich, 80 gm, 0.35 mol), and methanol (Baker, 900 gm). The solution is
heated to reflux under argon, and sodium methoxide (Aldrich, 80.8 gm of 25%
solution in methanol, 0.374 mol) is added from the addition funnel over ~15
min.
The solution is heated at reflux for 8 hrs. A 13C-NMR (DMSO-d6) shows the
disappearance of the peaks for starting material at 28.5 ppm and 29 ppm [-
CH2P(C6H5)3]. Most of the methanol is removed on the rotary evaporator
(~60°C).
The remaining material is taken up in 500 mL water, forming a milky
suspension.
The mixture is adjusted to pH 7 with a few drops of methanesulfonic acid
(Aldrich).
The mixture is cooled in an ice bath and filtered. A 13C-NMR (DMSO-d6) shows
the isolated solid to be mainly triphenylphosphine oxide. The mother liquor is
concentrated to 800 mL on the rotary evaporator and refrigerated overnight.
The
crystals which form are filtered, dried, and stirred vigorously in hot 50:50
wateraoluene. The water layer is concentrated to afford 20 gm of white powder.
The combination of 13C-NMR, 1H-NMR, C.O.S.Y. and N.O.E. indicates that the
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material is a 60:40 mixture of trans:cis isomers of the substituted stilbene
compound.
EXAMPLE 12
Preparation of an OliQOmer of traps-methyl ~'-sodiosulfostilbene 4 carboxylate
dimethyl terephthalate sodium ~-(2 3-dihydroxyproDOxy)ethanesulfonate~ cerol
propylene ~lycol and ethylene ~Iycol
To a 1 OOmL, three neck, round bottom flask equipped with a magnetic
stirring bar, modified Claisen head, condenser (set for distillation),
thermometer, and
temperature controller (Therm-O-Watch~, I2R) is added traps-methyl 2'-
sodiosulfostilbene-4-carboxylate (5.3 gm, 0.016 mol), dimethyl terephthalate
(7.6
gm, 0.039 mol), sodium 2-(2,3-dihydroxypropoxy)ethanesulfonate (4.4 gm, 0.020
mol), glycerol (Baker, 0.21 gm, 0.0023 mol), ethylene glycol (Baker, 7.3 gm,
0.118
mol), propylene glycol (Baker, 9.1 gm, 0.120 mol), and titanium (IV) propoxide
(0.01 gm, 0.02% of total reaction weight). This mixture is heated to
180°C and
maintained at that temperature overnight under argon as methanol distills from
the
reaction vessel. The material is transferred to a 250 mL, single neck, round
bottom
flask and heated gradually over about 10 minutes to 180°C in a
Kugelrohr apparatus
(Aldrich) at about 50 mm Hg and maintained there for 30 minutes, after which
the
temperature is raised to 230°C for 1 hr. The vacuum is then increased
to about 5
mm Hg, and heating at 230°C is continued for 4 hrs. The reaction flask
is allowed
to air cool quite rapidly to near room temperature under vacuum (~30 min.) The
reaction affords 17.7 gm of the desired oligomer as a brown glass. A ~3C-
NMR(DMSO-d6) shows a resonance for -C(O)OCH2CH20(O)C- at 63.2 ppm
(diester) and a resonance for -C(O)OCH2CH20H at 59.4 ppm (monoester). The
ratio of the peak for the diester resonance to that of the monoester resonance
is
measured to be 10. A resonance at 51.5 ppm representing the sulfoethoxy group
(-CH2S03Na), and resonances at 142 ppm and 146 ppm representing the
sulfonated capping group are also present. A ~H-NMR(DMSO-d6) shows a
resonance at ~7.9 ppm representing terephthalate aromatic hydrogens. Analysis
by
Hydrolysis-GC shows that the mole ratio of incorporated ethylene glycol to
incorporated propylene glycol is 1.75:1
EXAMPLE 13
Preparation of triphen~phosphonium-binhenylmethane
To a 1000 mL, three-necked round bottom flask equipped with a magnetic
stirnng bar, condenser, and thermometer connected to a temperature controlling
device (Thermowatch, I2R) is added 4-chloromethylbiphenyl (Aldrich, 41.7 gm,
0.391 mol), triphenylphosphine (TCI, 87.3 gm, 0.333 mol) and toluene (Baker,
300
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gm). The initially clear solution begins to form a white precipitate after a
few
minutes at reflux and is allowed to stir at reflux overnight. A 13C-NMR (DMSO-
d6) shows ~15% starting materials remaining. An additional 18 gm (0.069 mol)
of
triphenylphosphine is added, and the mixture is heated at reflux for an
additional
overnight period. A 13C-NMR (DMSO-d6) shows the virtual disappearance of the
peak at --45 ppm for starting chloride (-CH2C1) and the emergence of product
peaks
at --28.5 ppm and ~29 ppm [-CH2P(C6H5)3]. The toluene is evaporated on the
rotary evaporator and Kugelrohr apparatus (~ 100°C) to afford
approximately 97 gm
of white solid.
EXAMPLE 14
Preparation of traps methyl 4'-phenylstilbene-4-carboxylate
To a 2 L three-neck round bottom flask equipped with a magnetic stirnng
bar, condenser, addition funnel and thermometer connected to a temperature
controlling device {Thermowatch,12R), is added sequentially with good stirring
4-
carboxybenzaldehyde (Aldrich 52.5 gm, 0.35 mol), sodium methoxide (Aldrich 81
gm of 25% solution in methanol, 0.375 mol), 91 gm (0.327 mol) of the adduct
prepared in Example 13 and methanol (Baker, 900 gm). The solution is heated to
reflux under argon, and sodium methoxide (Aldrich, 80.8 gm of 25% solution in
methanol, 0.374 mol) is added from the addition funnel over ~1 S min. The
solution
is heated at reflux for 8 hrs. A 13C-NMR (DMSO-d6) shows the disappearance of
the peaks for starting material at --28.5 ppm and 29 ppm [-CH2P(C6H5)3]. Most
of
the methanol is removed on the rotary evaporator (~60°C). The remaining
material
is taken up in 500 mL methanol. The mixture is adjusted to pH 8-9 with a few
drops of methanesulfonic acid (Aldrich). The mixture is cooled in an ice bath
and
filtered. A 13C-NMR (DMSO-d6) shows the isolated solid to be mainly
triphenylphosphine oxide. The mother liquor is concentrated to 800 mL on the
rotary evaporator, adjusted to pH of about 3 with methanesulfonic acid and
refrigerated overnight. The solid which forms is broken up and filtered then
dissolved in methanol (Baker, 272 gm, 8.5 mol) and Amberlyst~ 15 acidic resin
(12
gm, 55.2 meq). The solution is refluxed overnight. A 1 H-NMR (DMSO-d6) shows
the virtual disappearance of the carboxylic acid peak at 11.5 ppm and the
emergence of a methyl ester peak at ~4 ppm. The solution is filtered and
concentrated on the rotary evaporator and Kugelrohr apparatus (Aldrich,
80°C) to
afford 17.9 gm of thick paste. The combination of 13C-NMR, 1H-NMR, C.O.S.Y.
and N.O.E. indicates that the material is a mixture of trans:cis isomers of
the
substituted stilbene compound.
EXAMPLE 1 S
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Preparation of an Oli~omer of traps methyl 4' phenylstilbene 4 carboxylate
dimethyl terephthalate sodium 2-(2 3-dih droxypropoxy)ethanesulfonate lycerol
provylene Qlycol and ethylene glycol
To a 250 mL, three neck, round bottom flask equipped with a magnetic
stirring bar, modified Claisen head, condenser (set for distillation),
thermometer, and
temperature controller (Therm-O-Watch TM, I2R) is added, traps methyl 4'-
phenylstilbene-4-carboxylate ( 15.7 gm, 0.05 mole), sodium 2-(2-hydroxy-
ethoxy)ethanesulfonate (9.2 gm, 0.048 mol) (prepared in accordance with U.S.
Patent 5,415,807, Gosselink, issued May 16, 1995), dimethyl terephthalate
(Aldrich,
46.5 gm, 0.24 mole), dimethyl 5-sulfoisophthalate, sodium salt (Aldrich, 14.2
gm,
0.048 mole), ethylene glycol (Baker, 89.2 gm, 1.44 mol), propylene glycol
(Baker,
109.4 g, I .44 mol), hydrated monobutyltin oxide (M&T Chemicals, 0.47 gm, 2%
of
total reaction weight), sodium acetate (MCB, 0.89 gm, 2 mol % of dimethyl 5-
sulfoisophthalate, sodium salt), and silicone oil (Dow-710 TM, 0.08 gm, 0.1%
of
final oligomer weight). This mixture is heated to 180o C and maintained at
that
temperature overnight under argon as methanol and water distill from the
reaction
vessel. The material is transferred to a 1000 mL. single neck, round bottom
Mask
and heated gradually over about 20 minutes to 2400 C, in a Kugelrohr apparatus
(Aldrich) at about 0.5 mm Hg and maintained there for 5 hours. The reaction is
then
allowed to air cool quite rapidly to near room temperature under vacuum
(approximately 30 minutes). The reaction affords 52 gm of the desired oligomer
as
a opaque amber solid.
EXAMPLE 16
Preparation of 2-f3-(2 3-dihydroxypro oxy phenylJ-3-methylbenzofuran
The ester which results from the condensation of 2'-hydroxyacetophenone
and m-anisic acid is converted to 2-(3-methoxyphenyl)-3-methylbenzofuran by
reductive cyclization in dioxane with a titanium tetrachloride/zinc metal
catalyst
according to the method of Banerji and Nayak, J. Chem. Soc., Chem. Comm.,
( 1990), 150. The 2-(3-methoxyphenyl)-3-methylbenzofuran (47.6 gm, 0.198 mol)
is treated with several volumes of pyridine hydrochloride at 200o C for about
6
hours to cleave the methyl ether moiety to the free hydroxyl group. Three
volumes
of water are added to the cooled reaction mixture and the system is extracted
twice
with ether. The ether extracts are combined, washed once with water and then
dried
over sodium sulfate. Removal of solvent by rotary evaporation affords the
desired
product, 2-(3-hydroxyphenyl)-3-methylbenzofuran. 2-(3-hydroxyphenyl)-3-methyl-
benzofuran (22.4 gm 0.1 mol) is dissolved in 100 mL of methanol in a 250 ml
round
bottom flask under an atmosphere of argon . To this well stirred solution is
added
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sodium methoxide (0.54 gm, 0.01 mol). Glycidol (Aldrich, 8.14 gm, 0.11 mol) is
added and the system is gradually heated and held at reflux for i 8 hours. The
solution is neutralized with methanesuifonic acid. The solvent is removed by
rotary
evaporation. The resulting product is heated on a Kugelrohr apparatus at 20(1o
C
under a vacuum of 1 mm Hg, to remove any 3-methoxy-1,2-propanediol by-product,
affording 2-(3-(2,3-dihydroxypropoxy)phenyl)-3-methylbenzofuran having the
structure:
O~~OH
/ ~ / ~ OH
O
EXAMPLE 17
Preparation of ethoxylated 2-(3-hy_droxyphenyt~ 3-methylbenzofuran
To a 3-neck 1000 mL round bottom flask equipped with an overhead
mechanical stirrer, Therm-O-WatchTM temperature controller, fritted glass
inlet tube,
condenser, ethylene oxide source, flow meter for ethylene oxide, acidic
aqueous
traps for scrubbing any excess ethylene oxide from the exit gas, and an argon
supply
inlet is charged 2-(3-hydroxyphenyl)-3-methylbenzofuran (22.4 gm, 0.1 mol) and
100 mL of dry dimethyl sufoxide. Sodium hydride (0.54 gm, 0.01 mol) added and
the solution is gradually heated to 1200 C and held at that temperature until
all of
the sodium hydride has fully reacted. Ethylene oxide (Balchem) is bubbled into
the
reaction mixture below the Level of the liquid until 2.5 moles have been
added. The
reaction mixture is cooled, neutralized by adding methanesulfonic acid, and
solvent
removed by evaporation on a Kugelrohr apparatus under a vacuum of 1 mm Hg at
1800 C. 'H and'3C NMR spectroscopy confirms the formation of ethoxylated 2-(3-
hydroxyphenyl)-3-methylbenzofuran wherein the average degree of ethoxylation
is
20 (n=20) and having the structure:
O(CH2CH,O~H
O
EXAMPLE 18
Preparation of sulfonated 2-(3-metho~phenyl)-3-methylbenzonfuran
To a 3-neck 1000 mL round bottom flask equipped with an overhead
mechanical stirrer, Therm-O-WatchT~1 temperature controller, fritted glass
inlet tube,
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condenser, ethylene oxide source, flow meter for ethylene oxide, acidic
aqueous
traps for scrubbing any excess ethylene oxide from the exit gas, and an argon
supply
inlet is charged 2-(3-hydroxyphenyl)-3-methylbenzofuran (22.4 gm, 0.1 mol) and
100 mL of dry nitrobenzene. Sulfur trioxide-N,N-dimethylformamide (Aldrich,
23.0 gm, 0.15 mol) is added with sufficient stirring and the solution is
gradually
heated to 115o C and held at that temperature for about 2 hours. The reaction
mixture is cooled to 60C° and the pH is adjusted to about 7 with 10%
aqueous
sodium hydroxide solution. The solvents are removed by evaporation on a
Kugelrohr apparatus under a vacuum of 1 mm Hg at 200o C to afford the desired
sulfonated hydroxyphenyl benzofuran as a mixture of sulfonated adducts having
the
structure:
H
R3
R
wherein at least one of the units R1, R2, or R3 is the sulfonate group, -
S03Na, and
wherein the average number of sulfonate groups per molecule is about 1.5.
EXAMPLE 19
Preparation of sulfonated 2-j3-(2 3-dihydroxypropoxy)phenyl] 3
methylbenzonfuran
The mixture of sulfonated benzofurans from Example 18 is dissolved in
methanol and sodium methoxide (0.54 gm, 0.01 mol) is added with sufficient
stirnng. Glycidol (Aldrich, 8.14 gm, 0.11 mole) is added and the solution is
refluxed for 18 hours. The solvent is removed by rotary evaporation and the 3-
methoxy-1,2-propanediol by-product is removed by heating at 200o C on a
Kugelrohr apparatus under a vacuum of 1 mm Hg for 1 hour to afford 2-[3-(2,3-
dihydroxypropoxy)phenyl]-3-methylbenzofuran having the structure:
~OH
OH
R3
R
wherein at least one of the units R1, R2, or R3 is the sulfonate group, -
S03Na, and
wherein the average number of sulfonate groups per molecule is about i .5.
EXAMPLE 20
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Preparation of sulfonated 2-f3-(polvethyleneoxy-E_3)phenvll-3-
methylbenzonfuran
To a 3-neck 1000 mL round bottom flask equipped with an overhead
mechanical stirrer, Therm-O-WatchT"~ temperature controller, fritted glass
inlet tube,
condenser, ethylene oxide source, flow meter for ethylene oxide, acidic
aqueous
traps for scrubbing any excess ethylene oxide from the exit gas, and an argon
supply
inlet is charged the sulfonated hydroxyphenyl benzofuran from Example 18 (0.2
mole) and 100 mL of dry dimethyl sufoxide. Sodium hydride (0.54 gm, 0.01 mol)
added and the solution is gradually heated to 1200 C and held at that
temperature
until all of the sodium hydride has fully reacted. Ethylene oxide (Balchem) is
bubbled into the reaction mixture below the level of the liquid until 3.5
moles have
been added. The reaction mixture is cooled, neutralized by adding
methanesulfonic
acid, and solvent removed by evaporation on a Kugelrohr apparatus under a
vacuum
of 1 mm Hg at 1800 C to afford benzofuran having the structure
HZC:H2U}nH
R3
R1
wherein the average degree of ethoxylation is 3 (n=3) and at least one of the
units
R1, R2, or R3 is the sulfonate group, -S03Na, and wherein the average number
of
sulfonate groups per molecule is about 1.5.
EXAMPLE 21
Preparation of Sodium 2-12-(2-Hvdroxyethoxy)ethoxylethanesulfonate
To a 1000 mL, three neck, round bottom flask equipped with a magnetic
stirring bar, modified Claisen head, condenser (set for distillation),
thermometer, and
temperature controller (Therm-O-WatchT"", I2R) is added isethionic acid,
sodium salt
(Aldrich, 100.0 gm, 0.675 mol) and distilled water (~90 mL). After
dissolution, one
drop of hydrogen peroxide (Aldrich, 30% by wt. in water) is added to oxidize
traces
of bisulfate. The solution is stirred for one hour. A peroxide indicator strip
shows a
very weak positive test. Sodium hydroxide pellets (MCB, 2.5 gm, 0.0625 mol)
are
added, followed by diethylene glycol (Fisher, 303.3 gm, 2.86 mol). The
solution is
heated at 1900 C under argon overnight as water distills from the reaction
mixture.
A 13C-NMR(DMSO-d6) shows that the reaction is complete by the disappearance
of the isethionate peaks at 53.5 ppm and 57.4 ppm. The solution is cooled to
room temperature and neutralized to pH 7 with 57.4g of a 16.4% solution of p-
toluene-sulfonic acid monohydrate in diethylene glycol. (Alternatively,
methanesulfonic acid may be used.) The 13C-NMR spectrum of the product shows
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resonances at --S lppm (-CH2 S03Na) , ~60 ppm (-CH20H), and at ~69 ppm, ~72
ppm, and ~77 ppm for the remaining four methylenes. Small resonances are also
visible for the sodium p-toluenesulfonate which formed during neutralization.
The
reaction affords 451 gm of a 35.3% solution of sodium 2-[2-(2-
hydroxyethoxy)ethoxy]ethanesulfonate in diethylene glycol. The excess
diethylene
glycol is removed by adding 0.8 mol % of monobasic potassium phosphate
(Aldrich) as a buffer and heating on a Kugelrohr apparatus (Aldrich) at I SOo
C for
3 hr. at ~l mm Hg to give an extremely viscous oil or glass.
EXAMPLE 22
Preparation of sodium 2-(2 3-Dihydroxypronoxylethanesulfonate
To a 500 mL, three neck, round bottom flask equipped with a magnetic
stirring bar, modified Claisen head, condenser (set for distillation),
thermometer, and
temperature controller (Therm-O-WatchTM, I2R) was added isethionic acid,
sodium
salt (Aldrich, 50.0 gm, 0.338 mol), sodium hydroxide (2.7g, 0.0675 mol), and
glycerin (Baker, 310.9 gm, 3.38 mol). The solution was heated at 190o C under
argon overnight as water distilled from the reaction mixture. A 13C-NMR(DMSO-
d6) showed that the reaction was complete by the virtual disappearance of the
isethionate peaks at 53.5 ppm and 57.4 ppm, and the emergence of product peaks
at ~51.4 ppm (-CH2S03Na) and 67.5 ppm (CH2CH2S03Na). The solution was
cooled to ~100o C and neutralized to pH 7 with methanesulfonic acid (Aldrich).
The desired, neat material was obtained by adding 0.8 mol % of potassium
phosphate, monobasic and heating on a Kugelrohr apparatus (Aldrich) at 2000 C
for
3 hr. at ~ 1 mm Hg to afford 77 gm of yellow waxy solid.
EXAMPLE 23
Preparation of an Oliaomer of sodium 2-(2-[2-hydroxyethoxy],ethoxy ethane
sulfonate. dimethvl terenhthalate sulfonated 2-[3-(2 3-Dihydroxypropoxyl
phen,~ll
3-methvlbenzofuran with average de- ree of sulfonation of ~ 1 5 ethylene gl cy
of and
propylene Ig ycol
To a 250 mL, three neck, round bottom flask equipped with a magnetic
stirnng bar, modified Claisen head, condenser (set for distillation),
thermometer, and
temperature controller (Therm-O-Watch, I2R) is added sodium 2-(2-[2-hydroxy-
ethoxy]ethoxy)ethanesulfonate(5.33 gm, 0.025 mol) prepared as in Example 22,
dimethyI terephthalate (9.8 gm, 0.050 mol), sulfonated 2-[3-(2,3-
dihydroxypropoxy)-phenyl]-3-methylbenzofiuan with average degree of
sulfonation
of ~1.5 ( 5.86 gm, 0.013 mol, as prepared in Example I 9), glycerin (Baker,
1.2 gm,
0.013 mol) ethylene glycol (Baker, 11.7 gm, 0.189 mol), propylene glycol
(Baker,
14.7 gm, 0.193 mol), and titanium(IV) propoxide (Aldrich, 0.01 gm, 0.02 % of
total
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reaction weight). This mixture is heated to 1800 C and maintained at that
temperature overnight under argon as methanol distills from the reaction
vessel.
The material is transferred to a 250 mL, single neck, round bottom flask and
gradually heated over about 20 minutes to 2400 C in a Kugelrohr apparatus
(Aidrich) at 0.5 mm Hg for I .5 hours. The reaction flask is then allowed to
air cool
quite rapidly to near room temperature under vacuum (--30 min.) The reaction
affords about 20 gm of the desired oligomer as a brown glass. A 13C-
NMR(DMSO-d6) shows a resonance for -C(O)OCH2CH20(O)C- at 63.2 ppm
(diester). A resonance for -C(O)OCH2CH20H at 59.4 ppm (monoester) is at least
8 times smaller than the diester peak.
EXAMPLE 24
Preparation of an oli~omer comprising ethoxylated ~-(3-hydroxyphenyl)-3-
methylbenzofuran having an avera~~ree of ethoxylation of 20 dimeth~
terenhthalate, polyethylene glycol (MW=1500) and 1 2-propanediol
To a 250 mL, three necked, round bottom flask fitted with a magnetic stirrer,
internal thermometer, argon inlet, and modified Claisen head attached to a
condenser and receiving flask, is charged ethoxylated 2-(3-hydroxyphenyl)-3-
methylbenzofuran with an average degree of ethoxylation of 20 ( 14.4 gm, 0.013
moles), prepared as in Example 20, dimethyl terephthalate (20.9 gm, 0.107
moles),
polyethylene glycol (MW= 1500), (48.6 gm, 0.032 moles), 1,2-propanediol
(propylene glycol), (10.3 gm, 0.136 moles), hydrated monobutyltin oxide
catalyst
0.2 gm. The reaction mixture is gradually raised to 1750 C and held there
overnight.
Then the temperature was raised to 1850 C for 4 hours and then to 200o C for
about
24 hr during which time about 6.4 gm of distillate is collected. The reaction
mixture is then transferred to a single neck, round bottom flask and placed on
a Kugelrohr apparatus (Aldrich) at a vacuum of about 1 mm Hg and
the temperature was gradually raised to 2200 C and held there for 2 hours to
give the desired polyester. 13C NMR (CDC13) shows a single peak in the 10-20
ppm region at 16.6 for the methyl of propylene glycol diesters and the near
absence
of a peak at 60.7 ppm for free -(OCH2CH2)nOH end group confirming that the
polyesterification had proceeded to a high degree of completion.
EXAMPLE 25
Preparation of an oli~omer of 2-f2-(2-hydroxyethoxy)ethoxylethanesulfonate
dimethyl tereyhthalate, sodium 2-(2,3-dihydroxypropoxylethanesulfonate 2-f 3-
(2 3
dihydroxynropoxylnhenyll-3-methylbenzofuran ethylene~lycol and~propylene
t IYcol.
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To a 250 mL three neck, round bottom flask equipped with a magnetic
stirring bar, modified Claisen head, condenser (set for distillation),
thermometer, and
temperature controller (Therm-O-Watch~, I2R) is added Sodium 2-[2-(2-
hydroxyethoxy)ethoxy]ethanesulfonate (7.0 gm, 0.030 mol), dimethyl
terephthalate
( 14.4 gm, 0.074 mol), sodium 2-(2,3-dihydroxypropoxy)ethanesulfonate (6.6 gm,
0.030 mol), 2-[3-(2,3-dihydroxypropoxy)phenyl]-3-methylbenzofuran (2.23 gm,
0.0075 mol, prepared as in Example 19) ethylene glycol (Baker, 14.0 gm, 0.225
mol), propylene glycol (Fisher, 18.3 gm, 0.240 mol), and titanium (IV)
propoxide
(0.01 gm, 0.02 % of total reaction weight). This mixture is heated to 1800 C
and
maintained at that temperature overnight under argon as methanol distills from
the
reaction vessel. The material is transferred to a 500 mL, single neck, round
bottom
flask and heated gradually over about 20 minutes to 2400 C in a Kugelrohr
apparatus (Aldrich) at about 0. I mm Hg and maintained there for 110 minutes.
The
reaction flask is then allowed to air cool quite rapidly to near room
temperature
under vacuum (~30 min.) The reaction affords 26.4 gm of the desired oligomer
as a'
brown glass. A 13C-NMR(DMSO-d6) shows a resonance for -
C(O)OCH2CH20(O)C- at 63.2 ppm (diester) and a resonance for -
C(O)OCH2CH20H at 59.4 ppm (monoester). The ratio of the diester peak to
monoester peak is measured to be 8. Analysis by exhaustive basic hydrolysis
followed by gas chromatography of the volatile components shows that the mole
ratio of incorporated ethylene glycol to incorporated propylene glycol is
about 1.6:1.
EXAMPLE 26
Preparation of an oli~omer comprising sulfonated ethoxylated 2 (3
hvdroxynhenyll-3-methylbenzofuran with deeree of ethoxylation of about 3 and
average degree of sulfonation of about 1 5 dimethyl terephthalate sulfonated 2
f3
(2.3-dihydroxyyronoxy)phenyl]-3-methylbenzofuran with average de ree of
sulfonation of ~1.5, ethylene elvcol and propylene ~iycol with hydrotro_pes
included.
To a 250 mL three neck, round bottom flask equipped with a magnetic
stirring bar, modified Claisen head, condenser (set for distillation),
thermometer, and
temperature controller (Therm-O-WatchT"", I2R) is added sulfonated,
ethoxylated 2-
(3-hydroxyphenyl)-3-methylbenzofuran with degree of ethoxylation of about 3
and
average degree of sulfonation of about 1.5 (26.5 gm, 0.052 mol, prepared as in
Example 20), dimethyl terephthalate (Aldrich, 55.5 gm, 0.286 mol), sulfonated
2-[3-
(2,3-dihydroxypropoxy)phenyl]-3-methylbenzofuran with average degree of
sulfonation of ~1.5( 23.5 gm, 0.052 mol, prepared as in Example 19), ethylene
glycol (Baker, 24.2 gm, 0.390 mol), propylene glycol (Baker, 28.7 gm, 0.377
mol),
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hydrated monobutyltin oxide (M&T Chemicals, 0.17 gm, ), sodium
cumenesulfonate (Ruetgers-Nease, 4g, ~4% of final polymer wt.), sodium
xylenesulfonate (Ruetgers-Nease, 4g, ~4% of final polymer wt.), and sodium p-
toluenesulfonate (Ruetgers-Nease, 4g, ~4% of final polymer wt.). This mixture
is
heated to 1800 C and maintained at that temperature overnight under argon as
methanol distills from the reaction vessel. The material is transferred to a
1000 mL,
single neck, round bottom flask and heated gradually over about 20 minutes to
2400
C in a Kugelrohr apparatus (Aldrich) at about 2 mm Hg and maintained there for
3
hours. The reaction flask is then allowed to air cool quite rapidly to near
room
temperature under vacuum (~30 min.) The reaction affords 110 gm of the desired
oiigomer as a crunchy glass. A 13C-NMR(DMSO-d6) shows a resonance for -
C(O)OCH2CH20(O)C- at 63.2 ppm (diester). A resonance for -
C(O)OCH2CH20H at 59.4 ppm (monoester) is at least 10 times smaller than the
diester peak. By exhaustive base hydrolysis and gas chromatography of the
volatile
products, the ratio of incorporated ethylene glycol : propylene glycol is
found to be
about 1.7.
EXAMPLE 27
Preparation of the fluorescent whitening- roup-containigQ soil release went
having the formula:
CHI CHl
O O O O O~ ~ W
so,Ha ° o CHiCHO ~-~ ~o CHiCNO ~ i ~ -cH=cHO~ ~_' O"~i'~SO,Na
5 so,Na
The methyl ester of 4-(chloromethyl)benzoic acid (Aldrich Chemical Co.) is
prepared by heating at reflux the acid dissolved in a large excess of methanol
in the
presence of a catalytic amount of macroreticular ion exchange resin in the
sulfonic
acid form. The resin catalyst is removed by filtration and the solvent is
removed in
vacuo to afford the methyl ester.
2'-hydroxyacetophenone (13.b g, 0.1 mol, Aldrich Chemical Co.) is
dissolved in 100 g of dry DMF and treated with sodium hydride (2.6 g, 0.11 mol
) to
make a solution of the nonosodium salt. To this phenoxide-containing solution
is
added the methyl 4-(chloromethyl)benzoate (18.5 g, O.I mol) and the reaction
mixture is heated with stirnng to 60°C for 4 hours to yield the
intermediate having
the formula:
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WO 98/59030 PCT/US97/10734
71
O
~~.,.,-- Cpp
The solution is cooled to room temperature and sodium t-butoxide ( 1 g, 0.01
mol) is added and with continued stirring the temperature is raised gradually
to
about 80° C and held there for 6 hours to generate the benzofuran
intermediate
having the formula:
\
~O
The benzofuran intermediate is isolated by filtering to remove salts and then
removing the solvent in vacuo. The benzofuran is taken up in 200 ml of
nitrobenzene and treated with sulfur trioxide-DMF complex (17 g, 0.11 mol)
followed by heating the reaction mixture to 115° C for about 2 hours.
The reaction
mixture is cooled to room temperature and neutralized by adding 0.11 moles of
sodium methoxide in methanol. The solvents are removed in vacuo to yield a
sulfonated benzofuran ester having the formula:
\~---,~,--COOCH3
p ~/
This sulfonated benzofuran ester intermediate is used directly as a capping
monomer
in synthesis of an oligomer as follows.
To a 100 mL, three-neck, round bottom flask equipped with a magnetic
stirring bar, modified Claisen head, condenser set for distillation,
thermometer, and
temperature controller (THERM-O-WATCH, I2R~ ) are added the following
monomers: the sulfonated benzofuran ester synthesized above (7.36 g, 0.02
mol),
dimethyl terephthalate (9.7 g, 0.05 mol.), ethylene glycol ( 12.4 g, 0.2 mol),
propylene glycol (15.2 g, 0.2 mol), and dimethyl 5-sodiosulfoisophthate (2.96
g,
0.01 mol). Tetrapropyl titanate (0.1 g) is added as a catalyst. The resulting
mixture
is heated to 180° C with stirring overnight under argon while methanol,
water and
traces of glycols distill out. The contents of the 100 ml, three-neck, round-
bottom
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72
flask is transferred to a 500 ml round-bottom flask and heated gradually (over
ca. 20
min.) to 230° C in a Kugelrohr apparatus (Aldrich) with reduced
pressure of ca. 1
mm Hg for ca. 3 hr. The flask with its contents still under vacuum, is allowed
to
cool quite rapidly to room temperature by exposing the outer surface of the
flask to
convection or forced air flow (ambient air). The cooling takes about 20 min.
The
desired, fluorescent-capped, oligomeric material is obtained as a glassy solid
weighing about 20 g. '3C NMR spectrum (DMSO-d6) indicates polymerization has
occurred by the near absence of a resonance at approximately 59 ppm,
corresponding to the condensed monoesters of ethylene glycol and the presence
of a
substantial resonance at approximately 63 ppm representing diesters of
ethylene
glycol.
