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FABRIC CARE COMPOSITIONS
Meld of the invention
The present invention relates to a fabric softening composition and more
particularly to a method and a composition which reduce the amount of dyes
released from colored fabrics upon subsequent wet treatments such as
those which occur in a laundry operation.
Background of the invention
The domestic treatment of colored fabric is a problem known in the art to the
formulator of laundry compositions. More particularly, the problem of
formulating laundry compositions which reduces the amount of dyes
released from colored fabrics upon wet treatment is a particular challenge to
the formulator. This problem is now even more acute with the trends of
consumers to move towards more colored fabrics.
Numerous solutions have been proposed in the art to solve this problem
such as by treating the fabric with a dye scavenger during the washing
process as exemplified by EP 0,341,205, EP 0,033,815 or with a polyvinyl
substance as exemplified by WO 94/11482. However, all these solutions are
focused on preventing the end result of the dye bleeding, that is the
redeposition of the dye on the fabrics. It is now an object of the invention
to
take the problem of dye at its source, that is to prevent the dye from
bleeding.
Solutions may be found for use in the industrial treatments. However, these
solutions are not usually transposable to domestic treatments. Indeed, in
industrial processes a strict control over parameters such as pH, electrolyte
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concentration, water hardness, temperature, etc. is possible whereas in a
domestic washing machine, such a high level of control is not possible.
In addition, in a domestic process, and in particular in a domestic rinse
process, it is not practical to rely on high treatment temperatures such as
those used in industrial processes, that is of above 40°C. Furthermore,
industrial processes use high concentrations of fixing agents which is
required for industrial scale treatment whilst for domestic treatment a low
level is most preferred for economical reasons.
Accordingly, notwithstanding the advances in the art, there is still a need
for
an efficient and economical composition which provides effective and
durable reduction of the amount of dyes released from colored fabrics upon
subsequent wet domestic treatments.
EP 462806 provides the use of a cationic dye frxing agent in domestic
treatment which assist in binding the loosely held dye to the fabric. However,
the dye fixing agents described in this patent provide the fixation of the dye
via electrostatic interactions with the dye and the cellulose fibre. These
interactions are by definition reversible, and therefore labile.
The Applicant has now found that the use of a composition comprising a
polyamino-functional polymer and a cellulose reactive dye fixing agent
fulfills
such a need. The reactive dye fixing agents used in the present invention
react covalently with cellulose fibers, i.e. form a chemical bond that is more
irreversible than mere ionic interactions, thereby providing more longevity to
the dye frxative treatment.
It has also been advantageousty found that the cellulose reactive dye fixing
agents for use in the present invention even provide better performance
than the dye fixing agents of EP 0,462,806.
By a cellulose reactive dye fixing agent, it is meant that a reactive
functionality, which is grafted on the fixing agent, can form covalent bonds
with cellulose. The reactivity can then further be improved upon heat
treatment. A test method to define which compound are cellulose reactive
dye fixing agent is given hereinafter.
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Not to be bound by any theory, it is believed that dye fixing agents enhance
the bleach damage of fabrics comprising bleach sensitive dye. Accordingly,
it would be expected from more substantive dye fixing agent such as the
cellulose reactive dye fixing agent to provide more bleach damage.
Surprisingly, it has been found that the combination of the invention
overcome such problem.
Accordingly, it is therefore an advantage of the invention to provide
compositions with effective and durable dye fixing properties.
Another advantage of the invention is that such compositions provide an
increase performance of the above mentioned benefit after subjecting the
treated fabrics with a heating source.
A further advantage of the invention is that the treated fabrics will
thereafter
show a reduced tendency in the subsequent wash to release dye. Such
benefit is more particularly seen after multi-wash cycles (e.g. 20 wash
cycles).
~manr of the invention
The present invention relates to a fabric care composition comprising a
polyamino-functional polymer and a cellulose reactive dye fixing agent.
In another aspect of the invention, there is provided a method for the
domestic treatment of a fabric to reduce the amount of dye released from
the fabric during wet treatments and comprising the step of contacting the
fabrics with said composition; and thereafter contacting the treated fabrics
with a heating source in a dry medium.
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Detailed description of the invention
According to one aspect of the invention, there is provided a fabric care
composition with effective and durable dye fixing properties.
Amino-functional a~ymer
An essential component of the invention is an amino-functional polymer. The
amino-functional polymer advantageously provides care to the colors of
fabrics.
The amino-functional polymers of the present invention are water-soluble or
dispersible, polyamines. Typically, the amino-functional polymers for use
herein have a molecular weight between 200 and 106, preferably between
600 and 20,000, most preferably between 1000 and 10,000. These
polyamines comprise backbones that can be either linear or cyclic. The
polyamine backbones can also comprise polyamine branching chains to a
greater or lesser degree. Preferably, the polyamine backbones described
herein are modified in such a manner that at least one, preferably each
nitrogen of the polyamine chain is thereafter described in terms of a unit
that
is substituted, quaternized, oxidized, or combinations thereof.
For the purposes of the present invention the term "modification" as it
relates
to the chemical structure of the polyamines is defined as replacing a
backbone -NH hydrogen atom by an R' unit (substitution), quatemizing a
backbone nitrogen (quaternized) or oxidizing a backbone nitrogen to the N-
oxide (oxidized). The terms "modification" and "substitution" are used
interchangably when referring to the process of replacing a hydrogen atom
attached to a backbone nitrogen with an R' unit. Quatemization or oxidation
may take place in some circumstances without substitution, but substitution
is preferably accompanied by oxidation or quatemization of at least one
backbone nitrogen.
The linear or non-cyclic poiyamine backbones that comprise the amino-
functionaf polymer have the general formula:
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R'
I
(R;N - R]n+ 1-[N - R)rri _~ - R)n-N R;
The cyclic polyamine backbones that comprise the amino-functional polymer
have the general formula:
I
R' I R
~?N-R)n k+1-~-R)rri WR)nWR)k-NR2
The above backbones prior to optional but preferred subsequent
modification, comprise primary, secondary and tertiary amine nitrogens
connected by R "linking" units.
For the purpose of the present invention, primary amine nitrogens
comprising the backbone or branching chain once modified are defined as V
or Z "terminal" units. For example, when a primary amine moiety, located at
the end of the main polyamine backbone or branching chain having the
structure
H2N-[R]-
is modified according to the present invention, it is thereafter defined as a
V
"terminal" unit, or simply a V unit. However, for the purposes of the present
invention, some or all of the primary amine moieties can remain unmodified
subject to the restrictions further described herein below. These unmodified
primary amine moieties by virtue of their position in the backbone chain
remain "terminal" units. Likewise, when a primary amine moiety, located at
the end of the main poiyamine backbone having the structure:
-NH2
is modified according to the present invention, it is thereafter defined as a
Z
"terminal" unit, or simply a Z unit. This unit can remain unmodified subject
to
the restrictions further described herein below.
In a similar manner, secondary amine nitrogens comprising the backbone or
branching chain once modified are defined as W "backbone" units. For
example, when a secondary amine moiety, the major constituent of the
backbones and branching chains of the present invention, having the
structure:
H
-lZ'j _ R]-
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is modified according to the present invention, it is thereafter defined as a
W
"backbone" unit, or simply a W unit. However, for the purposes of the
present invention, some or all of the secondary amine moieties can remain
unmodified. These unmodified secondary amine moieties by virtue of their
position in the backbone chain remain "backbone" units.
In a further similar manner, tertiary amine nitrogens comprising the
backbone or branching chain once modified are further referred to as Y
"branching" units. For example, when a tertiary amine moiety, which is a
chain branch point of either the polyamine backbone or other branching
chains or rings, having the structure:
I
-(N _ RJ-
is modified according to the present invention, it is thereafter defined as a
Y
"branching" unit, or simply a Y unit. However, for the purposes of the
present invention, some or all or the tertiary amine moieties can remain
unmodified. These unmodified tertiary amine moieties by virtue of their
position in the backbone chain remain "branching" units. The R units
associated with the V, W and Y unit nitrogens which serve to connect the
polyamine nitrogens, are described herein below.
The final modified structure of the poiyamines of the present invention can
be therefore represented by the general formula
V(n+1 )WmYnZ
for linear amino-functional polymer and by the general formula:
V(n-k+1 )WmYnY~kZ
for cyclic amino-functional polymer. For the case of polyamines comprising
rings, a Y' unit of the formula
I
R
-fN _ RJ-
serves as a branch point for a backbone or branch ring. For every Y' unit
there is a Y unit having the formula:
I
-(N _ RJ-
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that will form the connection point of the ring to the main polymer chain or
branch. In the unique case where the backbone is a complete ring, the
polyamine backbone has the formula:
R'
[R?N-RJn-[N-RJrri (I'I-RJn
therefore comprising no Z terminal unit and having the formula
Vn-kWmYnY~k
wherein k is the number of ring forming branching units. Preferably the
polyamine backbones of the present invention comprise no rings.
In the case of non-cyclic polyamines, the ratio of the index n to the index m
relates to the relative degree of branching. A fully non-branched linear
modified polyamine according to the present invention has the formula:
VWn.,Z
that is, n is equal to 0. The greater the value of n (the lower the ratio of m
to
n), the greater the degree of branching in the molecule. Typically the value
for m ranges from a minimum value of 2 to 700, preferably 4 to 400,
however larger values of m, especially when the value of the index n is very
low or nearly 0, are also preferred.
Each poiyamine nitrogen whether primary, secondary or tertiary, once
modified according to the present invention, is further defined as being a
member of one of three general classes; simple substituted, quaternized or
oxidized. Those polyamine nitrogen units not modified are classed into V, W,
Y, Y' or Z units depending on whether they are primary, secondary or tertiary
nitrogens. That is unmodified primary amine nitrogens are V or Z units,
unmodified secondary amine nitrogens are W units or Y' units and
unmodified tertiary amine nitrogens are Y units for the purposes of the
present invention.
Modified primary amine moieties are defined as V "terminal" units having
one of three forms:
a) simple substituted units having the structure:
R'-N-R-
I
R'
b) quatemized units having the structure:
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R. X _
I
R'-N~ R-
I
R'
wherein X is a suitable counter ion providing charge balance; and
c) oxidized units having the structure:
0
R'-N-R-
I
R'
Modified secondary amine moieties are defined as W "backbone" units
having one of three forms:
a) simple substituted units having the structure:
-N-R-
R'
b) quaternized units having the structure:
R, X .
-N~ R-
I
R'
wherein X is a suitable counter ion providing charge balance; and
c) oxidized units having the structure:
O
-N-R-
I
R'
Other modified secondary amine moieties are defined as Y' units having one
of three forms:
a) simple substituted units having the structure:
-N-R-
R
b) quaternized units having the structure:
R. X _
-N~ R-
I
R
wherein X is a suitable counter ton providing charge balance; and
c) oxidized units having the structure:
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O
-~_R-
I
R
Modified tertiary amine moieties are defined as Y "branching" units having
one of three forms:
a) unmodified units having the structure:
-N-R-
I ,
b) quaternized units having the structure:
R, X .
-N~ R-
wherein X is a suitable counter ion providing charge balance; and
c) oxidized units having the structure:
O
-N-R-
Certain modified primary amine moieties are defined as Z "terminal" units
having one of three forms:
a) simple substituted units having the structure:
-N-R'
R'
b) quatemized units having the structure:
R'
-N~ R
I
R' ,
wherein X is a suitable counter ion providing charge balance; and
c) oxidized units having the structure:
O
-N-R'
I
R'
When any position on a nitrogen is unsubstituted of unmodified, it is
understood that hydrogen will substitute for R'. For example, a primary
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amine unit comprising one R' unit in the form of a hydroxyethyl moiety is a V
terminal unit having the formula (HOCH2CH2)HN-.
For the purposes of the present invention there are two types of chain
terminating units, the V and Z units. The Z "terminal" unit derives from a
terminal primary amino moiety of the structure -NH2. Non-cyclic polyamine
backbones according to the present invention comprise only one Z unit
whereas cyclic polyamines can comprise no Z units. The Z "terminal" unit
can be substituted with any of the R' units described further herein below,
except when the Z unit is modified to form an N-oxide. In the case where
the Z unit nitrogen is oxidized to an N-oxide, the nitrogen must be modified
and therefore R' cannot be a hydrogen.
The polyamines of the present invention comprise backbone R "linking" units
that serve to connect the nitrogen atoms of the backbone. R units comprise
units that for the purposes of the present invention are referred to as
"hydrocarbyl R" units and "oxy R" units. The "hydrocarbyl" R units are C2-
C12 alkylene, C4-C12 alkenylene, C3-C12 hydroxyalkylene wherein the
hydroxyl moiety may take any position on the R unit chain except the carbon
atoms directly connected to the polyamine backbone nitrogens; C4-C12
dihydroxyalkylene wherein the hydroxyl moieties may occupy any two of the
carbon atoms of the R unit chain except those carbon atoms directly
connected to the polyamine backbone nitrogens; Cg-C12 dialkylarylene
which for the purpose of the present invention are arylene moieties having
two alkyl substituent groups as part of the linking chain. For example, a
dialkylarylene unit has the formula:
-(CH2)2 ~ ~ CH2- -(CH2}4 ~ ~ (CH2~-
or
although the unit need not be 1,4-substituted, but can also be 1,2 or 1,3
substituted C2-C12 alkylene, preferably ethylene, 1,2-propylene, and
mixtures thereof, more preferably ethylene. The "oxy" R units comprise -
(R1O)xR5(OR1)x-, -CH2CH(OR2)CH20)z(R10)yR1(OCH2CH(OR2)CH2}w-
-CH2CH(OR2)CH2-, -(R10)xR1-, and mixtures thereof. Preferred R units
are selected from the group consisting of C2-C12 alkylene, C3-C12
hydroxyalkylene, C4-C12 dihydroxyalkylene, Cg-C12 dialkylarylene, -
(R10)xR1-, -CH2CH(OR2)CH2-, -(CH2CH(OH)CH20}z(R10)yR1(OCH2CH-
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(OH)CH2)w-, -(R10)xR5(OR1)x-, more preferred R units are C2-C12
alkylene, C3-C12 hydroxy-alkylene, C4-C12 dihydroxyalkylene, -(R10)xR1-,
-(R10)xR5(OR1)x-, -(CH2CH(OH)CH20)z(R1O)yR1(OCH2CH-(OH)CH2)w-,
and mixtures thereof, even more preferred R units are C2-C12 alkylene, Cg
hydroxyalkylene, and mixtures thereof, most preferred are C2-Cg alkylene.
The most preferred backbones of the present invention comprise at least
50% R units that are ethylene.
R1 units are C2-Cg alkyfene, and mixtures thereof, preferably ethylene.
R2 is hydrogen, and -(R10)xB, preferably hydrogen.
R3 is C1-C1g alkyl, C7-C12 arylalkylene, C7-C12 alkyl substituted aryl, Cg-
C12 aryl, and mixtures thereof , preferably C1-C12 alkyl, C7-C12
arylalkylene, more preferably C1-C12 alkyl, most preferably methyl. R3
units serve as part of R' units described herein below.
R4 is C1-C12 alkyiene, C4-C12 alkenylene, Cg-C12 arylalkylene, Cg-C10
aryfene, preferably C1-C10 alkylene, Cg-C12 arylalkylene, more preferably
C2-Cg alkylene, most preferably ethylene or butylene.
R5 is C1-C12 alkylene, C3-C12 hydroxyalkylene, C4-C12 dihydroxyalkylene,
Cg-C12 dialkyiarylene, -C(O)-, -C(O)NHR6NHC(O)-, -C(O)(R4)rC(O)-, -
R1(OR1)-, -CH2CH(OH)CH20(R1O)yRIOCH2CH(OH)CH2-, -
C(O)(R4)rC(O)-, -CH2CH(OH)CH2-, R5 is preferably ethylene, -C(O)-, -
C(O)NHR6NHC(O)-, -R1(OR1)-, -CH2CH(OH)CH2-,
CH2CH(OH)CH20(R~O)yR10CH2CH-(OH)CH2-, more preferably -
CH2CH(OH)CH2-.
R6 is C2-C12 alkylene or Cg-C~2 aryfene.
The preferred "oxy" R units are further defined in terms of the R1, R2, and
R5 units. Preferred "oxy" R units comprise the preferred R~, R2, and R5
units. The preferred cotton soil release agents of the present invention
comprise at feast 50% R1 units that are ethylene. Preferred R1, R2, and R5
units are combined with the "oxy" R units to yield the preferred "oxy" R units
in the following manner.
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i) Substituting more preferred R5 into -(CH2CH20)XR~(OCH2CH2)x-
yieids -(CH2CH20)xCH2CHOHCH2(OCH2CH2)x-.
ii) Substituting preferred R1 and R2 into -(CH2CH(OR2)CH20)z-
(R10)yR~O(CH2CH(OR2)CH2)~ yields -(CH2CH(OH)CH20)z-
(CH2CH20)yCH2CH20(CH2CH(OH)CH2)w-.
iii) Substituting preferred R2 into -CH2CH(OR2)CH2- yields
-CH2CH(OH)CH2-.
R' units are selected from the group consisting of hydrogen, C1-C22 alkyl,
C3-C22 alkenyl, C7-C22 arylalkyl, C2-C22 hydroxyalkyl, -(CH2)pC02M, -
(CH2)qS03M, -CH(CH2C02M)C02M, -(CH2)pP03M, -(R10)mB, -C(O)R3,
preferably hydrogen, C2-C22 hydroxyalkyiene, benzyl, C1-C22 alkylene,
(R10)mB, -C(O)R3, -(CH2)pC02M, -(CH2)qS03M, -CH(CH2C02M)C02M,
more preferably C1-C22 alkyiene, -(R10}xB, -C(O)R3, -(CH2)pC02M, -
(CH2)qS03M, -CH(CH2C02M)COZM, most preferably C1-C22 alkyiene, -
(R~O)xB, and -C(O)R3. When no modification or substitution is made on a
nitrogen then hydrogen atom will remain as the moiety representing R'. A
most preferred R' unit is (R10)xB.
R' units do not comprise hydrogen atom when the V, W or Z units are
oxidized, that is the nitrogens are N-oxides. For example, the backbone
chain or branching chains do not comprise units of the following structure:
O O O
-N-R or H-N-R or -N-H
I I I
H H H
Additionally, R' units do not comprise carbonyl moieties directly bonded to a
nitrogen atom when the V, W or Z units are oxidized, that is, the nitrogens
are N-oxides. According to the present invention, the R' unit -C(O)R3
moiety is not bonded to an N-oxide modified nitrogen, that is, there are no
N-oxide amides having the structure
O O O
O O
-N-R or R3-C-N-R or -N-C-R3
I I I
C=O R' R'
~3
R
or combinations thereof.
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B is hydrogen, C1-Cg alkyl, -(CH2)qS03M, -(CH2)pC02M, -(CH2)q-
(CHS03M)CH2S03M, -(CH2)q(CHS02M)CH2S03M, -(CH2)pP03M, -
P03M, preferably hydrogen, -(CH2)qS03M, -(CH2)q(CHS03M)CH2S03M,
-(CH2)q-(CHS02M)CH2S03M, more preferably hydrogen or -(CH2)qS03M.
M is hydrogen or a water soluble cation in sufficient amount to satisfy charge
balance. For example, a sodium cation equally satisfies -(CH2)pC02M,
and -(CH2)qS03M, thereby resulting in -(CH2)pC02Na, and -
(CH2)qS03Na moieties. More than one monovafent cation, (sodium,
potassium, etc.) can be combined to satisfy the required chemical charge
balance. However, more than one anionic group may be charge balanced
by a divalent cation, or more than one mono-valent cation may be necessary
to satisfy the charge requirements of a poly-anionic radical. For example, a
-(CH2)pP03M moiety substituted with sodium atoms has the formula -
(CH2)pP03Na3. Divalent cations such as calcium (Ca2+) or magnesium
(Mg2'~) may be substituted for or combined with other suitable mono-valent
water soluble cations. Preferred cations are sodium and potassium, more
preferred is sodium.
X is a water soluble anion such as chlorine (CI-), bromine (Br) and iodine
(I-) or X can be any negatively charged radical such as sulfate (S042-) and
methosulfate (CH3S03-)
The formula indices have the following values: p has the value from 1 to 6, q
has the value from 0 to 6; r has the value 0 or 1; w has the value 0 or 1, x
has the value from 1 to 100; y has the value from 0 to 100; z has the value 0
or 1; m has the value from 2 to 700, preferably from 4 to 400, n has the
value from 0 to 350, preferably from 0 to 200; m + n has the value of at least
5.
Preferably x has a value lying in the range of from 1 to 20, preferably from 1
to 10.
The preferred amino-functional polymers of the present invention comprise
polyamine backbones wherein less than 50% of the R groups comprise
"oxy" R units, preferably less than 20% , more preferably less than 5%, most
preferably the R units comprise no "oxy" R units.
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The most preferred amino-functional polymers which comprise no "oxy" R
units comprise polyamine backbones wherein less than 50% of the R groups
comprise more than 3 carbon atoms. For example, ethylene, 1.2-propylene,
and 1,3-propylene comprise 3 or less carbon atoms and are the preferred
"hydrocarbyl" R units. That is when backbone R units are C2-C12 alkylene,
preferred is C2-C3 alkylene, most preferred is ethylene.
The amino-functional polymers of the present invention comprise modified
homogeneous and non-homogeneous poiyamine backbones, wherein 100%
or less of the -NH units are modified. For the purpose of the present
invention the term "homogeneous poiyamine backbone" is defined as a
polyamine backbone having R units that are the same (i.e., all ethylene).
However, this sameness definition does not exclude poiyamines that
comprise other extraneous units comprising the polymer backbone which
are present due to an artifact of the chosen method of chemical synthesis.
For example, it is known to those skilled in the art that ethanolamine may be
used as an "initiator" in the synthesis of polyethyieneimines, therefore a
sample of polyethyleneimine that comprises one hydroxyethyl moiety
resulting from the polymerization "initiator" would be considered to comprise
a homogeneous polyamine backbone for the purposes of the present
invention. A polyamine backbone comprising all ethylene R units wherein
no branching Y units are present is a homogeneous backbone. A polyamine
backbone comprising all ethylene R units is a homogeneous backbone
regardless of the degree of branching or the number of cyclic branches
present.
For the purposes of the present invention the term "non-homogeneous
polymer backbone" refers to polyamine backbones that are a composite of
various R unit lengths and R unit types. For example, a non-homogeneous
backbone comprises R units that are a mixture of ethylene and 1,2-
propyfene units. For the purposes of the present invention a mixture of
"hydrocarbyl" and "oxy" R units is not necessary to provide a non-
homogeneous backbone.
Preferred amino-functional polymers of the present invention comprise
homogeneous polyamine backbones that are totally or partially substituted
by polyethyleneoxy moieties, totally or partially quaternized amines,
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nitrogens totally or partially oxidized to N-oxides, and mixtures thereof.
However, not all backbone amine nitrogens must be modified in the same
manner, the choice of modification being left to the specific needs of the
formulator. The degree of ethoxylation is also determined by the specific
requirements of the formulator.
The preferred polyamines that comprise the backbone of the compounds of
the present invention are generally polyalkyleneimines (PAI's), preferably
polyethyleneimines (PEI's), or PEl's connected by moieties having longer R
units than the parent PAI's or PEI's.
Preferred amine polymer backbones comprise R units that are C2 alkylene
(ethylene) units, also known as polyethylenimines (PEI's). Preferred PEI's
have at least moderate branching, that is the ratio of m to n is less than
4:1,
however PEI's having a ratio of m to n of 2:1 are most preferred. Preferred
backbones, prior to modification have the general formula:
R' i
[R~NCH~CH2Jn-[NCH~CH2]m [NCH~CH~Jn NR2
wherein R', m and n are the same as defined herein above. Preferred PEI's
will have a molecular weight greater than 200 daltons.
The relative proportions of primary, secondary and tertiary amine units in the
polyamine backbone, especially in the case of PEI's, will vary, depending on
the manner of preparation. Each hydrogen atom attached to each nitrogen
atom of the poiyamine backbone chain represents a potential site for
subsequent substitution, quaternization or oxidation.
These polyamines can be prepared, for example, by polymerizing
ethyieneimine in the presence of a catalyst such as carbon dioxide, sodium
bisulfate, sulfuric acid, hydrogen peroxide, hydrochloric acid, acetic acid,
etc.
Specific methods for preparing these polyamine backbones are disclosed in
U.S. Patent 2,182,306, Ulrich et al., issued December 5, 1939; U.S. Patent
3,033,746, Mayie et al., issued May 8, 1962; U.S. Patent 2,208,095,
Esselmann et al., issued July 16, 1940; U.S. Patent 2.806,839, Crowther,
issued September 17, 1957; and U.S. Patent 2,553,696, Wilson, issued May
21, 1951; all herein incorporated by reference.
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Examples of amino-functional polymers comprising PEI's, are illustrated in
Formulas I - IV:
Formula I depicts an amino-functional polymer comprising a PEI backbone
wherein all substitutable nitrogens are modified by replacement of hydrogen
with a polyoxyalkyleneoxy unit, -(CH2CH20)H, having the formula
M(OCH=CHz) ~N~ ~N((CHz~zO) Mz
N H(OCHzCHz) .N~NI(~lz~z0) HJz
(CHzCH,O) H ~ (CHzCH,O) H
[H(OC7-lzCHz) ]zN~N~N~N~N~N~N~N~N~N[(CH=CH=O) I-Ilz
(CH=CH=O) H (CHzCHzO) H ~ (CHzCHzO) H
~N~
NON[(CHzCHzO) Hjz
[H(OCH=CHz) ]_N I~N((CH=CHzO) H]z
Formula I
This is an example of an amino-functional polymer that is fully modified by
one type of moiety.
Formula It depicts an amino-functional polymer comprising a PEI backbone
wherein all substitutable primary amine nitrogens are modified by
replacement of hydrogen with a polyoxyalkyleneoxy unit, -(CH2CH20)2H,
the molecule is then modified by subsequent oxidation of all oxidizable
primary and secondary nitrogens to N-oxides, said polymer having the
formula
0 0
[H(OC7-lzCHzh]zN N[(CHzCHzOHH]z «~zp zOhH
t
N O ~~ ~~ N((CHz~zO~Hlz
H(OCtIzo yz ~O o(CHzCH_,Oh~ O O(Cl-1,_CHZO~H
O
t f ~ t N ~ N CH CH O ,
(H(OCHz~zhlzN~Nj~~~~ ~~ 1 ~N~~ ~~~ (( z z ~t'll_
/ ii
O O
«~z~ZO)zH 0(CHzCHzOhH
N
f
t ~ N[(CHzCH20hHJz
[H(oaiZcH,,~ p.~ ~ i ((~~oh~
O
Formula II
Formula III depicts an amino-functional polymer comprising a PEi backbone
wherein all backbone hydrogen atoms are substituted and some backbone
amine units are quaternized. The substituents are polyoxyalkyleneoxy units,
-(CH2CH20)7H, or methyl groups. The modified PEI has the formula
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17
cH;
[Ei(OCH,CHzh]zN N(CH=CH~OpH CH
3
CI' CH;, ~NfCH,CH,OhH
N N -
CH; , CH3 CH3 CH;
II'1(OCH,CHZ?nlzN~ I+~N~N~ N~ N~ N~ N~ N~ N(CH3~Z
CI ~3 ~3 ~ CI'
Cl + _~
s CI_
~~ .~''f(CHs>
(li(OCH,CHzh]=N N
~N(CH3~,
Formula III
Formula IV depicts an amino-functional polymer comprising a PEI backbone
wherein the backbone nitrogens are modified by substitution (i.e. by -
(CH2CH20)gH or methyl), quaternized, oxidized to N-oxides or
combinations thereof. The resulting polymer has the formula
~3
(H(OCH,CHzhJzN N(CH,CHZO~H
~3
I- CH3,N~N(CH,CH,O)3H
CI'
O
CH; , CH3 O ~ ~ ~ ~a CHI
ih
11'1(OCfizCHz)3 )zN~ +1~ N~ i ~N~ N~ N~ N~ N ~ N(CH
CI' ~3 O ~ ~ CI CH3
0
CI '~" _(~-j~
+ CI'
(H(OCHzCHz~]zN N~N(CHlh
N(CH3 y~
Formula IV
In the above examples, not all nitrogens of a unit class comprise the same
modification. The present invention allows the formulator to have a portion of
the secondary amine nitrogens ethoxylated while having other secondary
amine nitrogens oxidized to N-oxides. This also applies to the primary amine
nitrogens, in that the formulator may choose to modify all or a portion of the
primary amine nitrogens with one or more substituents prior to oxidation or
quaternization. Any possible combination of R' groups can be substituted on
the primary and secondary amine nitrogens, except for the restrictions
described herein above.
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Commercially available amino-functional polymer suitable for use herein are
poly(ethyieneimine) with a MW 1200, hydroxyethylated poly(ethyleneimine)
from Polysciences, with a MW 2000, and 80% hydroxyethylated
poly(ethyleneimine) from Aldrich.
A typical amount of amino-functional polymer to be employed in the
composition of the invention is preferably up to 90% by weight, preferably
from 0.01 % to 50% active by weight, more preferably from 0.1 % to 20% by
weight and most preferably from 0.5% to 15% by weight of the composition.
Cellulose reactive dye fixino agents
The other essential component of the invention is a cellulose reactive dye
fixing agent. Typical levels of such agents are from 0.01 % to 50%,
preferably from 0.01 % to 25%, more preferably from 0.05 to 10% by weight,
most preferably from 0.5 to 5% by weight of the composition.
By "cellulose reactive dye fixing agent", it is meant that the agent reacts
with
the cellulose fibers upon heat treatment. The agents suitable for use herein
can be defined by the following test procedure, so called cellulose reactivity
test measurement.
Cellulose rea_ctiv~,~ test mPacurement
Two pieces of bleeding fabrics (e.g. 10 x 10 cm of knitted cotton dyed with
Direct Red 80) are soaked for 20 minutes in an aqueous solution of 1
(wlw) of the cellulose reactive dye fixing agent candidate. The pH of the
solution is as it is obtained at this concentration.
The swatches are then dried. One of the dried swatches as well as an
unsoaked swatch (control 1 ) are passed 10 times trough an ironing calender
set on a linen setting.
A control 2 swatch is also used in this measurement test which is a non-
soaked and non-ironed swatch.
The 4 swatches are washed separately in Launder-o-meter pots under
typical conditions with a commercial detergent used at the recommended
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19
dosage for'/z hour at 60°C, followed by a thorough rinsing of 4 times
200 ml
of cold water and then line dried.
The wash-fastness is then measured on the swatches by determination of
their so-called delta-E values versus a new, untreated swatch. Delta E's are
defined, for instance, in ASTM D2244. Delta E is the computed color
difference as defined in ASTM D2244, i.e the magnitude and direction of the
difference between two psychophysical color stimuli defined by tristimulus
values, or by chromaticity coordinates and luminance factor, as computed
by means of a specified set of color-difference equations defined in the CIE
1976 CIELAB opponent-color space, the Hunter opponent-color space, the
Friele-Mac Adam-Chickering color space or any equivalent color space.
Accordingly, the lower the Delta E versus new, the better the wash fastness
improvement.
If the washfastness improvement of the ironed-soaked swatch is better than
that of the non-ironed soak swatch and also better than the two respective
control 1 and 2, then the candidate is a cellulose reactive dye fixing agent
for the purpose of the invention.
Typical cellulose reactive dye fixing agents are products containing the
reactive group of the reactive dye classes selected from halogeno-triazine
products, vinyl sulphones compounds, epichlorhydrine derivatives,
hydroxyethyiene urea derivatives, formaldehyde condensation products,
polycarboxylates, glyoxal and glutaraldehyde derivatives and mixtures
thereof.
Other reactive functionalities for cellulose can be found in Textile
processing
and properties. Elsevier (1997) from Tyrone L. Vigo at page 120 to 121,
which provides the use of specific electrophilic groups with cellulose
affinity.
Preferred hydroxyethylene urea derivatives include
dimethyloldihydroxyethylene, urea, and dimethyl urea glyoxal.
Preferred formaldehyde condensation products include the condensation
products derived from formaldehyde and a group selected from an amino-
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group, an imino-group, a phenol group, an urea group, a cyanamide group
and an aromatic group. Commercially available compounds among this
class are Sandofix WE 56 from Clariant, Zetex E from Zeneca and l.evogen
BF from Bayer.
Preferred polycarboxylates derivatives include butane tetracarboxilic acid
derivatives, citric acid derivatives, polyacryiates and derivatives thereof.
A most preferred cellulosic reactive dye fixing agents is one of the
hydroxyethylene urea derivatives class commercialized under the
tradename of Indosol CR from Clariant. Still other most preferred cellulosic
reactive dye fixing agents are commercialized under the tradename Rewin
DWR and Rewin WBS from CHT R. Beitlich.
The composition of the invention may also be formulated as a fabric
softening composition. Accordingly, when formulated as a softening
composition, it will comprises a fabric softening compound.
Fabric softening coml o~ and
Typical levels of incorporation of the softening compound in the softening
composition are of from 1 % to 80% by weight, preferably from 5% to 75%,
more preferably from 15% to 70%, and even more preferably from 19% to
65%, by weight of the composition.
The fabric softener compound is preferably selected from a cationic,
nonionic, amphoteric or anionic fabric softening component. Typical of the
cationic softening components are the quaternary ammonium compounds or
amine precursors thereof as defined hereinafter.
Al-Quaternary Ammonium Fabric Softening Active Come oQ and
(1) Preferred quaternary ammonium fabric softening active compound
have the formula
+ _
(R)4-m N (CH2~-Q-R~ X
m
(1)
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21
or the formula:
(R)a", N (~" - ~ -' Cl'1-' _' Q -'
m
Q - R~ (2)
wherein Q is a carbonyl unit having the formula:
2 "'
O O O R O O R=
-O-C- . -C-O- , -O-C-O- , -N -C- , -C-N -
each R unit is independently hydrogen, C1-Cg alkyl, C1-Cg hydroxyalkyl,
and mixtures thereof, preferably methyl or hydroxy alkyl; each R1 unit is
independently linear or branched C11-C22 alkyl, linear or branched C11-
C22 alkenyl, and mixtures thereof, R2 is hydrogen, C1-C4 alkyl, C1-C4
hydroxyalkyi, and mixtures thereof; X is an anion which is compatible with
fabric softener actives and adjunct ingredients; the index m is from 1 to 4,
preferably 2; the index n is from 1 to 4, preferably 2.
An example of a preferred fabric softener active is a mixture of quaternized
amines having the formula:
+ O
R~-N (CH2)n-O-C-R1 X -
2
wherein R is preferably methyl; R1 is a linear or branched alkyl or alkenyl
chain comprising at least 11 atoms, preferably at least 15 atoms. In the
above fabric softener example, the unit -02CR1 represents a fatty acyl unit
which is typically derived from a triglyceride source. The triglyceride source
is preferably derived from tallow, partially hydrogenated tallow, lard,
partially
hydrogenated lard, vegetable oils and/or partially hydrogenated vegetable
oils, such as, canola oil, safflower oil, peanut oil, sunflower oil, corn oil,
soybean oil, tall oil, rice bran oil, etc. and mixtures of these oils.
The preferred fabric softening actives of the present invention are the
Diester and/or Diamide Quaternary Ammonium (DEQA) compounds, the
diesters and diamides having the formula:
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22
(R)4-m N (CH~)n-Q-R1 X -
m
wherein R, R1, X, and n are the same as defined herein above for formulas
(1) and (2), and Q has the formula:
H O
-p-C- or -N-C-
These preferred fabric softening actives are formed from the reaction of an
amine with a fatty acyl unit to form an amine intermediate having the
formula:
R N (CH,)n-Q-R~
wherein R is preferably methyl, Q and R' are as defined herein before;
followed by quaternization to the final softener active.
Non-limiting examples of preferred amines which are used to form the
DEQA fabric softening actives according to the present invention include
methyl bis(2-hydroxyethyl)amine having the formula:
C H3
HON OOH
methyl bis(2-hydroxypropyl)amine having the formula:
CH3
N
HO OH
methyl (3-aminopropyl) (2-hydroxyethyl)amine having the formula:
CH3
HON ~NH2
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23
methyl bis(2-aminoethyl)amine having the formula:
CH3
H2N ~N ~NH2
triethanol amine having the formula:
~OH
HON OOH
di(2-aminoethyl) ethanofamine having the formula:
~OH
N
HEN ~ ~NH~
The counterion, X(-) above, can be any softener-compatible anion,
preferably the anion of a strong acid, for example, chloride, bromide,
methylsulfate, ethylsulfate, sulfate, nitrate and the like, more preferably
chloride or methyl sulfate. The anion can also, but less preferably, carry a
double charge in which case X(-) represents half a group.
Tallow and canola oil are convenient and inexpensive sources of fatty acyl
units which are suitable for use in the present invention as R~ units. The
following are non-limiting examples of quaternary ammonium compounds
suitable for use in the compositions of the present invention. The term
"tallowyl" as used herein below indicates the R~ unit is derived from a tallow
triglyceride source and is a mixture of fatty acyl units. Likewise, the use of
the term canolyl refers to a mixture of fatty acyl units derived from canola
oil.
Table II
Fabric Softener Actives
N,N-di(talfowyl-oxy-ethyl)-N,N-dimethyl ammonium chloride;
N,N-di(canolyl-oxy-ethyl)-N,N-dimethyl ammonium chloride;
N,N-di(tallowyl-oxy-ethyl)-N-methyl, N-(2-hydroxyethyi) ammonium chloride;
N,N-di(canolyl-oxy-ethyl)-N-methyl, N-(2-hydroxyethyl) ammonium chloride;
N,N-di(2-tallowyloxy-2-oxo-ethyl)-N,N-dimethyl ammonium chloride;
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24
N,N-di(2-canolyioxy-2-oxo-ethyl)-N,N-dimethyl ammonium chloride
N,N-di(2-tallowyloxyethylcarbonyloxyethyl)-N,N-dimethyl ammonium
chloride;
N,N-di(2-canolyloxyethylcarbonyloxyethyl)-N,N-dimethyl ammonium
chloride;
N-(2-tallowoyloxy-2-ethyl)-N-(2-talfowyloxy-2-oxo-ethyl)-N, N-d imethy(
ammonium chloride;
N-(2-canolyloxy-2-ethyl)-N-(2-canolyloxy-2-oxo-ethyl)-N, N-dimethyl
ammonium chloride;
N,N,N-tri(tallowyl-oxy-ethyl)-N-methyl ammonium chloride;
N,N,N-tricanolyl-oxy-ethyl)-N-methyl ammonium chloride;
N-(2-tallowyioxy-2-oxoethyl)-N-(tallowyl)-N,N-dimethyl ammonium chloride;
N-(2-canolyioxy-2-oxoethyl)-N-(canolyl)-N,N-dimethyi ammonium chloride;
1,2-ditallowyloxy-3-N,N,N-trimethylammoniopropane chloride; and
1,2-dicanolyloxy-3-N,N,N-trimethylammoniopropane chloride;
and mixtures of the above actives.
Other examples of quaternay ammoniun softening compounds are
methylbis(tallowamidoethyl)(2-hydroxyethyl)ammonium methylsulfate and
methylbis(hydrogenated tallowamidoethyl)(2-hydroxyethyl)ammonium
methylsulfate; these materials are available from Witco Chemical Company
under the trade names Varisoft~ 222 and Varisoft~ 110, respectively.
Particularly preferred is N,N-di(tallowoyl-oxy-ethyl)-N,N-dimethyl ammonium
chloride, where the tallow chains are at least partially unsaturated.
The level of unsaturation contained within the tallow, canola, or other fatty
acyl unit chain can be measured by the Iodine Value (IV) of the
corresponding fatty acid, which in the present case should preferably be in
the range of from 5 to 100 with two categories of compounds being
distinguished, having a IV below or above 25.
Indeed, for compounds having the formula:
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25
(R)4-m N (CH~)n-Q-Rl X
m
derived from tallow fatty acids, when the iodine Value is from 5 to 25,
preferably 15 to 20, it has been found that a cisltrans isomer weight ratio
greater than about 30170, preferably greater than about 50/50 and more
preferably greater than about 70!30 provides optimal concentrability.
For compounds of this type made from tallow fatty acids having a Iodine
Value of above 25, the ratio of cis to traps isomers has been found to be
less critical unless very high concentrations are needed.
Other suitable examples of fabric softener actives are derived from fatty acyl
groups wherein the terms "tallowyl" and canolyl" in the above examples are
replaced by the terms "cocoyl, palmyl, lauryl, oieyl, ricinoleyl, stearyl,
palmityl," which correspond to the triglyceride source from which the fatty
acyl units are derived. These alternative fatty acyl sources can comprise
either fully saturated, or preferably at feast partly unsaturated chains.
As described herein before, R units are preferably methyl, however, suitable
fabric softener actives are described by replacing the term "methyl" in the
above examples in Table II with the units "ethyl, ethoxy, propyl, propoxy,
isopropyl, butyl, isobutyl and t-butyl.
The counter ion, X, in the examples of Table Il can be suitably replaced by
bromide, methylsulfate, formate, sulfate, nitrate, and mixtures thereof. In
fact, the anion, X, is merely present as a counterion of the positively
charged
quaternary ammonium compounds. The scope of this invention is not
considered limited to any particular anion.
For the preceding ester fabric softening agents, the pH of the compositions
herein is an important parameter of the present invention. Indeed, it
influences the stability of the quaternary ammonium or amine precursors
compounds, especially in prolonged storage conditions.
The pH, as defined in the present context, is measured in the neat
compositions at 20 °C. llVhile these compositions are operable at pH of
less
than about 6.0, for optimum hydrolytic stability of these compositions, the
neat pH, measured in the above-mentioned conditions, must preferably be
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26
in the range of from about 2.0 to about 5, preferably in the range of 2.5 to
4.5, preferably about 2.5 to about 3.5. The pH of these compositions herein
can be regulated by the addition of a Bronsted acid.
Examples of suitable acids include the inorganic mineral acids, carboxylic
acids, in particular the low molecular weight (C1-C5) carboxylic acids, and
alkylsulfonic acids. Suitable inorganic acids include HCI, H2S04, HNOg and
H3P04. Suitable organic acids include formic, acetic, citric, methyisulfonic
and ethylsulfonic acid. Preferred acids are citric, hydrochloric, phosphoric,
formic, methylsulfonic acid, and benzoic acids.
As used herein, when the diester is specified, it will include the monoester
that is normally present in manufacture. For softening, under no/low
detergent carry-over laundry conditions the percentage of monoester should
be as low as possible, preferably no more than about 2.5%. However,
under high detergent carry-over conditions, some monoester is preferred.
The overall ratios of diester to monoester are from about 100:1 to about 2:1,
preferably from about 50:1 to about 5:1, more preferably from about 13:1 to
about 8:1. Under high detergent carry-over conditions, the dilmonoester
ratio is preferably about 11:1. The level of monoester present can be
controlled in the manufacturing of the softener compound.
Mixtures of actives of formula (1 ) and (2) may also be prepared.
2)-Still other suitable quaternary ammonium fabric softening compounds for
use herein are cationic nitrogenous salts having two or more long chain
acyclic aliphatic Cg-C22 hydrocarbon groups or one said group and an
arylalkyl group which can be used either alone or as part of a mixture are
selected from the group consisting of:
(i) acyclic quaternary ammonium salts having the formula:
R4 +
R8-N_RS A
~s
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WO 99/27055 PCT/US98/24816
27
wherein R4 is an acyclic aliphatic Cg-C22 hydrocarbon group, R~ is a C1-C4
saturated alkyl or hydroxyalkyl group, R8 is selected from the group
consisting of R4 and R5 groups, and A- is an anion defined as above;
(ii) diamino alkoxylated quaternary ammonium salts having the formula:
O RS O
It I II
R~-C-NH-R2-N-R2-NH-C-R~
I
(CH,CH~O)~H
wherein n is equal to 1 to about 5, and R1, R2, R5 and A- are as defined
above;
(iii) mixtures thereof.
Examples of the above class cationic nitrogenous salts are the well-known
dialkyldi methylammonium salts such as ditallowdimethylammonium
chloride, ditallowdimethylammonium methylsulfate,
di(hydrogenatedtallow)dimethylammonium chloride,
distearyldimethylammonium chloride, dibehenyldirnethylammonium chloride.
Di(hydrogenatedtallow)di methylammonium chloride and
ditallowdimethylammonium chloride are preferred. Examples of
commercially available dialkyidimethyl ammonium salts usable in the
present invention are di(hydrogenatedtallow)dimethylammonium chloride
(trade name Adogen~ 442), ditallowdimethylammonium chloride (trade
name Adogen~ 470, Praepagen~ 3445), distearyl dimethylammonium
chloride (trade name Arosurf~ TA-100), all available from Witco Chemical
Company. Dibehenyldimethylammonium chloride is sold under the trade
name Kemamine Q-2802C by Humko Chemical Division of Witco Chemical
Corporation.
Dimethylstearylbenzyl ammonium chloride is sold under the trade names
Varisoft~ SDC by Witco Chemical Company and Ammonyx~ 490 by Onyx
Chemical Company.
B~-Amine Fabric Softening Active sm~ound
Suitable amine fabric softening compounds for use herein, which may be in
amine form or cationic form are selected from:
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28
(i)- Reaction products of higher fatty acids with a polyamine selected from
the group consisting of hydroxyalkylalkyienediamines and
dialkylenetriamines and mixtures thereof. These reaction products are
mixtures of several compounds in view of the multi-functional structure of the
polyamines.
The preferred Component (i) is a nitrogenous compound selected from the
group consisting of the reaction product mixtures or some selected
components of the mixtures.
One preferred component (i) is a compound selected from the group
consisting of substituted imidazoiine compounds having the formula:
N
R~-'~ ~
N
I
Rx-NH-C-R~
I I
O
wherein R7 is an acyclic aliphatic C15-C21 hydrocarbon group and R$ is a
divalent C1-Cg alkylene group.
Component (i) materials are commercially available as: Mazamide~ 6, sold
by Mazer Chemicals, or Ceranine0 HC, sold by Sandoz Colors &
Chemicals; stearic hydroxyethyl imidazoline sold under the trade names of
Alkazine~ ST by Alkaril Chemicals, Inc., or Schercozofine~ S by Scher
Chemicals, Inc.; N,N"-ditallowalkoyldiethylenetriamine; 1-tallowamidoethyl-2-
tallowimidazoline (wherein in the preceding structure R1 is an aliphatic C15-
C17 hydrocarbon group and R8 is a divalent ethylene group).
Certain of the Components (i) can also be first dispersed in a Bronsted acid
dispersing aid having a pKa value of not greater than about 4; provided that
the pH of the final composition is not greater than about 6. Some preferred
dispersing aids are hydrochloric acid, phosphoric acid, or methylsulfonic
acid.
Both N,N"-ditalfowaikoyldiethylenetriamine and 1-talfow(amidoethyl)-2-
tallowimidazoline are reaction products of tallow fatty acids and
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29
diethyienetriamine, and are precursors of the cationic fabric softening agent
methyl-1-tallowamidoethyl-2-tallowimidazolinium methylsulfate (see
"Cationic Surface Active Agents as Fabric Softeners," R. R. Egan, Journal of
the American Oil Chemicals' Society, January 1978, pages 118-121 ). N,N"-
ditallow alkoyldiethylenetriamine and 1-tallowamidoethyl-2-tallowimidazoline
can be obtained from Witco Chemical Company as experimental chemicals.
Methyl-1-tallowamidoethyl-2-tallowimidazolinium methylsulfate is sold by
Witco Chemical Company under the tradename Varisoft0 475.
(ii)-softener having the formula:
N
R~ C
O N (+) CHI ?Cc-~
Rs
R~ C G R
wherein each R2 is a C1_g alkylene group, preferably an ethylene group;
and G is an oxygen atom or an -NR- group; and each R, R1, R2 and R5
have the definitions given above and A- has the definitions given above for
X-.
An example of Compound (ii) is 1-oleylamidoethyl-2-oleylimidazolinium
chloride wherein R1 is an acyclic aliphatic C15-C17 hydrocarbon group, R2
is an ethylene group, G is a NH group, R5 is a methyl group and A- is a
chloride anion.
(iii)- softener having the formula:
20
H H
\N-R2-N
N -N 2A0
R~ R~
wherein R, R1, R2, and A- are defined as above.
An example of Compound (iii) is the compound having the formula:
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30
X~
--~ ~ H H ~
N-CH~CH2-N I Ci O
i
N~ ~N
~Rl R'
wherein R1 is derived from oleic acid.
Additional fabric softening agents useful herein are described in U.S. Pat.
No. 4.661,269, issued April 28, 1987, in the names of Toan Trinh, Errol H.
Wahl, Donald M. Swartley, and Ronald L. Hemingway; U.S. Pat. No.
4,439,335, Burns, issued March 27, 1984; and in U.S. Pat. Nos.: 3,861,870,
Edwards and Diehl; 4,308,151, Cambre; 3,886,075, Bernardino; 4,233,164,
Davis; 4,401,578, Verbruggen; 3,974,076, Wiersema and Rieke; 4,237,016,
Rudkin, Clint, and Young; and European Patent Application publication No.
472,178, by Yamamura et al., alt of said documents being incorporated
herein by reference.
Of course, the term "softening active" can also encompass mixed softening
active agents.
Preferred among the classes of softener compounds disclosed herein before
are the diester or diamido quaternary ammonium fabric softening active
compound (DEQA).
Fully formulated fabric softening compositions may contain, in addition to the
hereinbefore described components, one or more of the following
ingredients.
~A)Li~luid carrier
Another optional, but preferred, ingredient is a liquid carrier. The liquid
carrier employed in the instant compositions is preferably at least primarily
water due to its low cost, relative availability, safety, and environmental
compatibility. The level of water in the liquid carrier is preferably at least
about 50%, most preferably at least about 60%, by weight of the carrier.
Mixtures of water and low molecular weight, e.g., <about 200, organic
solvent, e.g., lower alcohols such as ethanol, propanol, isopropanol or
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31
butanol are useful as the carrier liquid. Low molecular weight aicohols
include monohydric, dihydric (glycol, etc.) trihydric (glycerol, etc.), and
higher
polyhydric (polyols) alcohols.
(Bl-Additional Solvents
The compositions of the present invention may comprise one or more
solvents which provide increased ease of formulation. These ease of
formulation solvents are all disclosed in WO 97/03169. This is particularly
the case when formulating liquid, clear fabric softening compositions. When
employed, the ease of formulation solvent system preferably comprises less
than about 40%, preferably from about 10% to about 35%, more preferably
from about 12% to about 25%, and even more preferably from about 14% to
about 20%, by weight of the composition. The ease of formulation solvent is
selected to minimize solvent odor impact in the composition and to provide a
low viscosity to the final composition. For example, isopropyl alcohol is not
very effective and has a strong odor. n-Propyl alcohol is more effective, but
also has a distinct odor. Several butyl alcohols also have odors but can be
used for effective claritylstability, especially when used as part of a ease
of
formulation solvent system to minimize their odor. The aicohols are also
selected for optimum low temperature stability, that is they are able to form
compositions that are liquid with acceptable low viscosities and translucent,
preferably clear, down to about 40°F (about 4.4°C) and are able
to recover
after storage down to about 20°F (about 6.7°C).
The suitability of any ease of formulation solvent for the formulation of the
liquid, concentrated, preferably clear, fabric softener compositions herein
with the requisite stability is surprisingly selective. Suitable solvents can
be
selected based upon their octanol/water partition coefficient (P) as defined
in
WO 97/03169.
The ease of formulation solvents herein are selected from those having a
CIogP of from about 0.15 to about 0.64, preferably from about 0.25 to about
0.62, and more preferably from about 0.40 to about 0.60, said ease of
formulation solvent preferably being at feast somewhat asymmetric, and
preferably having a melting, or solidification, point that allows it to be
liquid
at, or near room temperature. Solvents that have a low molecular weight
and are biodegradable are also desirable for some purposes. The more
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assymetric solvents appear to be very desirable, whereas the highly
symmetrical solvents such as 1,7-heptanediol, or 1,4-bis(hydroxymethyl)
cyclohexane, which have a center of symmetry, appear to be unable to
provide the essential clear compositions when used alone, even though their
CIogP values fall in the preferred range.
The most preferred ease of formulation solvents can be identified by the
appearance of the softener vesicles, as observed via cryogenic electron
microscopy of the compositions that have been diluted to the concentration
used in the rinse. These dilute compositions appear to have dispersions of
fabric softener that exhibit a more uni-lamellar appearance than
conventional fabric softener compositions. The closer to uni-lameilar the
appearance, the better the compositions seem to perform. These
compositions provide surprisingly good fabric softening as compared to
similar compositions prepared in the conventional way with the same fabric
softener active.
Operable ease of formulation solvents are disclosed and listed below which
have CIogP values which fall within the requisite range. These include
mono-ols, C6 diols, C7 diols, octanediol isomers, butanediol derivatives,
trimethylpentanediol isomers, ethylmethylpentanediol isomers, propyl
pentanediol isomers, dimethyihexanediol isomers, ethylhexanediol isomers,
methylheptanediol isomers, octanediol isomers, nonanediol isomers, alkyl
glyceryl ethers, di(hydroxy alkyl) ethers, and aryl glyceryl ethers, aromatic
giyceryl ethers, alicyclic diols and derivatives, C3C7 diol alkoxylated
derivatives, aromatic diols, and unsaturated diois. Particularly preferred
ease of formulation solvents include hexanediols such as 1,2-Hexanediol
and 2-Ethyl-1,3-hexanediol and pentanediols such as 2,2,4-Trimethyl-1,3-
pentanediol.
(C) ~isoersibili ~ Aids
Relatively concentrated compositions containing both saturated and
unsaturated diester quaternary ammonium compounds can be prepared that
are stable without the addition of concentration aids. However, the
compositions of the present invention may require organic and/or inorganic
concentration aids to go to even higher concentrations andlor to meet higher
stability standards depending on the other ingredients. These concentration
aids which typically can be viscosity modifiers may be needed, or preferred,
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33
for ensuring stability under extreme conditions when particular softener
active levels are used. The surfactant concentration aids are typically
selected from the group consisting of (1) single long chain alkyl cationic
surfactants; (2) nonionic surfactants; (3) amine oxides; (4) fatty acids: and
(5) mixtures thereof. These aids are described in WO 94/20597, specifically
on page 14, line 12 to page 20, line 12, which is herein incorporated by
reference.
When said dispersibility aids are present , the total level is from 2% to 25%,
preferably from 3% to 17%, more preferably from 4% to 15%, and even
more preferably from 5% to 13% by weight of the composition. These
materials can either be added as part of the active softener raw material,
(I),
e.g., the mono-long chain alkyl cationic surfactant and/or the fatty acid
which
are reactants used to form the biodegradable fabric softener active as
discussed hereinbefore, or added as a separate component. The total level
of dispersibility aid includes any amount that may be present as part of
component (I).
Inorganic viscosity/dispersibiiity control agents which can also act like or
augment the effect of the surfactant concentration aids, include water-
soluble, ionizable salts which can also optionally be incorporated into the
compositions of the present invention. A wide variety of ionizable salts can
be used. Examples of suitable salts are the halides of the Group IA and IIA
metals of the Periodic Table of the Elements, e.g., calcium chloride,
magnesium chloride, sodium chloride, potassium bromide, and lithium
chloride. The ionizable salts are particularly useful during the process of
mixing the ingredients to make the compositions herein, and later to obtain
the desired viscosity. The amount of ionizable salts used depends on the
amount of active ingredients used in the compositions and can be adjusted
according to the desires of the formulator. Typical levels of salts used to
control the composition viscosity are from about 20 to about 20,000 parts
per million (ppm), preferably from about 20 to about 11,000 ppm, by weight
of the composition.
Alkylene polyammonium salts can be incorporated into the composition to
give viscosity control in addition to or in place of the water-soluble,
ionizable
salts above. In addition, these agents can act as scavengers, forming ion
pairs with anionic detergent carried over from the main wash, in the rinse,
and on the fabrics, and may improve softness performance. These agents
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may stabilize the viscosity over a broader range of temperature, especially
at low temperatures, compared to the inorganic electrolytes.
Specific examples of alkyiene polyammonium salts include t-lysine
monohydrochioride and 1,5-diammonium 2-methyl pentane dihydrochloride.
(D)-Stabilizers
Stabilizers can be present in the compositions of the present invention. The
term "stabilizer," as used herein, includes antioxidants and reductive agents.
These agents are present at a level of from 0% to about 2%, preferably from
about 0.01 % to about 0.2%, more preferably from about 0.035% to about
0.1 % for antioxidants, and more preferably from about 0.01 % to about 0.2%
for reductive agents. These assure good odor stability under long term
storage conditions for the compositions and compounds stored in molten
form. The use of antioxidants and reductive agent stabilizers is especially
critical for low scent products (low perfume).
Examples of antioxidants that can be added to the compositions of this
invention include a mixture of ascorbic acid, ascorbic palmitate, propyl
gallate, available from Eastman Chemical Products, Inc., under the trade
names Tenox~ PG and Tenox S-1; a mixture of BHT (butylated
hydroxytoluene), BHA (butylated hydroxyanisole), propyl gallate, and citric
acid, available from Eastman Chemical Products, Inc., under the trade name
Tenox-6; butylated hydroxytoiuene, available from UOP Process Division
under the trade name Sustane~ BHT; tertiary butylhydroquinone, Eastman
Chemical Products, Inc., as Tenox TBHQ; natural tocopherols, Eastman
Chemical Products, Inc., as Tenox GT-11GT-2; and butylated
hydroxyanisole, Eastman Chemical Products, Inc., as BHA; long chain
esters (Cg-C22) of gallic acid, e.g., dodecyi gallate; Irganox~ 1010; irganox
~ 1035; Irganox~ B 1171; Irganox~ 1425; Irganox~ 3114; Irganox~ 3125;
and mixtures thereof; preferably Irganox~ 3125, Irganox~ 1425, Irganox~
3114, and mixtures thereof; more preferably Irganox~ 3125 alone or mixed
with citric acid and/or other chelators such as isopropyl citrate, Dequest~
2010, available from Monsanto with a chemical name of 1-
hydroxyethyiidene-1, 1-diphosphonic acid (etidronic acid), and Tiron~,
available from Kodak with a chemical name of 4,5-dihydroxy-m-benzene-
sulfonic acid/sodium salt, EDDS, and DTPA~, available from Aldrich with a
chemical name of diethylenetriaminepentaacetic acid. The chemical names
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35
and CAS numbers for some of the above stabilizers are listed in Table II
below.
TA II
Antioxidant CAS No. Chemical Name used in Code of Federal
Reg uiations
Irganox~ 1010 6683-19-8 Tetrakis (methylene(3,5-di-tert-butyl-4
hydroxyhydrocinnamate)) methane
Irganox~ 1035 41484-35-9 Thiodiethylene bis(3,5-di-tert-butyl-4-
hydroxyhydrocinnamate
irganox~ 1098 23128-74-7 N,N'-Hexamethyiene bis(3,5-di-tert-butyl-
4-
hydroxyhydrocinnamamide
Irganox~ B 1171 31570-04-4
23128-74-7 1:1 Blend of Irganox~ 1098 and lrgafos~
168
Irganox~ 1425 65140-91-2 Calcium bis(monoethyl(3,5-di-tert-butyl-4-
hydroxybenzyl)phosphonate)
Irganox~ 3114 65140-91-2 Calcium bis(monoethyl(3,5-di-tert-butyl-4-
hydroxybenzyl)phosphonate)
Irganox~ 3125 34137-09-2 3,5-Di-tert-butyl-4-hydroxy-hydrocinnamic
acid
triester with 1,3,5-tris(2-hydroxyethyl)-S-
triazine-2,4,6-(1 H, 3H, 5H)-trione
Irgafos~ 168 31570-04-4 Tris(2,4-di-tert-butyl-phenyi)phosphite
Examples of reductive agents include sodium borohydride,
hypophosphorous acid, Irgafos~ 168, and mixtures thereof.
(E)-Soil Release Agent
Soil Release agents are desirably used in fabric softening compositions of
the instant invention. Any polymeric soil release agent known to those
skilled in the art can optionally be employed in the compositions 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
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segments. This can enable stains occurring subsequent to treatment with
the soil release agent to be more easily cleaned in later washing
procedures.
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%.
The following, all included herein by reference, describe soil release
polymers suitable for use in the present invention. U.S. 3,959,230 Hays,
issued May 25, 1976; U.S. 3,893,929 Basadur, issued July 8, 1975; U.S.
4,000,093, Nicol, et aL, issued December 28, 1976; U.S. Patent 4,702,857
Gosselink, issued October 27, 1987; U.S. 4,968,451, Scheibel ef al., issued
November 6; U.S. 4,702,857, Gosselink, issued October 27, 1987; U.S.
4,711,730, Gosselink et al., issued December 8, 1987; U.S. 4,721,580,
Gossetink, issued January 26, 1988; U.S. 4,877,896, Maldonado et al.,
issued October 31, 1989; U.S. 4,956,447, Gosselink et al., issued
September 11, 1990; U.S. 5,415,807 Gosselink et al., issued May 16, 1995;
European Patent Application 0 219 048, published April 22, 1987 by Kud, et
al..
Further suitable soil release agents are described in U.S. 4,201,824,
Violland et al.; U.S. 4,240,918 Lagasse et al.; U.S. 4,525,524 Tung et al.;
U.S. 4,579,681, Ruppert et al.; U.S. 4,240,918; U.S. 4,787,989; U.S.
4,525,524; EP 279,134 A, 1988, to Rhone-Poulenc Chemie; EP 457,205 A
to BASF (1991); and DE 2,335,044 to Unilever N. V., 1974 all incorporated
herein by reference.
Commercially available soil release agents include the METOLOSE SM100,
METOLOSE SM200 manufactured by Shin-etsu Kagaku Kogyo K. K.,
SOKALAN type of material, e.g., SOKALAN HP-22, available from BASF
(Germany), ZELCON 5126 (from Dupont) and MILEASE T (from ICI).
(F}-Bactericides
Examples of bactericides used in the compositions of this invention include
glutaraldehyde, formaldehyde, 2-bromo-2-vitro-propane-1,3-diol sold by
Inoiex Chemicals, located in Philadelphia, Pennsylvania, under the trade
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name Bronopol~, and a mixture of 5-chioro-2-methyl-4-isothiazoline-3-one
and 2-methyl-4-isothiazoline-3-one sold by Rohm and Haas Company under
the trade name Kathon 1 to 1,000 ppm by weight of the agent.
jS)-Perfume
The present invention can contain a perfume. Suitable perfumes are
disclosed in U.S. Pat. 5,500,138, said patent being incorporated herein by
reference.
As used herein, perfume includes fragrant substance or mixture of
substances including natural (i.e., obtained by extraction of flowers, herbs,
leaves, roots, barks, wood, blossoms or plants), artificial (i.e., a mixture
of
different nature oils or oil constituents) and synthetic (i.e., synthetically
produced) odoriferous substances. Such materials are often accompanied
by auxiliary materials, such as fixatives, extenders, stabilizers and
solvents.
These auxiliaries are also included within the meaning of "perfume", as used
herein. Typically, perfumes are complex mixtures of a plurality of organic
compounds.
The range of the natural raw substances can embrace not only readily-
volatile, but also moderately-volatile and slightly-volatile components and
that of the synthetics can include representatives from practically all
classes
of fragrant substances, as will be evident from the following illustrative
compilation: natural products, such as tree moss absolute, basil oil, citrus
fruit oils (such as bergamot oil, mandarin oil, etc.), mastix absolute, myrtle
oil, palmarosa oil, patchouli oil, petitgrain oil Paraguay, wormwood oil,
alcohols, such as famesol, geraniol, linalool, nerol, phenylethyl alcohol,
rhodinol, cinnamic alcohol, aldehydes, such as citral, HelionaITM, alpha-
hexyl-cinnamaldehyde, hydroxycitronellal, LiliaITM (p-tert-butyl-alpha -
methyldihydrocinnamaldehyde), methyinonyiacetaidehyde, ketones, such as
allylionone, alpha-ionone, beta -ionone, isoraldein (isomethyl- alpha -
ionone), methylionone, esters, such as allyl phenoxyacetate, benzyl
salicylate, cinnamyi propionate, citroneilyl acetate, citronellyl ethoxolate,
decyl acetate, dimethyibenzylcarbinyl acetate, dimethylbenzylcarbinyl
butyrate, ethyl acetoacetate, ethyl acetylacetate, hexenyi isobutyrate,
linalyl
acetate, methyl dihydrojasmonate, styrallyl acetate, vetiveryl acetate, etc.,
lactones, such as gamma-undecalactone, various components often used in
perfumery, such as musk ketone, indole, p-menthane-8-thiol-3-one, and
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methyl-eugenol. Likewise, any conventional fragrant acetal or ketal known
in the art can be added to the present composition as an optional
component of the conventionally formulated perfume (c). Such conventional
fragrant acetals and ketals include the well-known methyl and ethyl acetais
and ketals, as well as acetals or ketals based on benzaldehyde, those
comprising phenylethyl moieties, or more recently developed specialties
such as those described in a United States Patent entitled "Acetals and
Ketals of Oxo-Tetralins and Oxo-Indanes, see U.S. Pat. No. 5 ,084,440,
issued January 28, 1992, assigned to Givaudan Corp. Of course, other
recent synthetic specialties can be included in the perfume compositions for
fully-formulated fabric softening compositions. These include the enol
ethers of alkyl-substituted oxo-tetralins and oxo-indanes as described in
U.S. Pat. 5,332,725, July 26, 1994, assigned to Givaudan; or Schiff Bases
as described in U.S. Pat. 5,264,615, December 9, 1991, assigned to
Givaudan.
The perfumes useful in the present invention compositions are substantially
free of haiogenated materials and nitromusks.
Perfume can be present at a level of from 0% to 10%, preferably from 0.1
to 5%, and more preferably from 0.2% to 3%, by weight of the finished
composition. Fabric softener compositions of the present invention provide
improved fabric perfume deposition.
(H)-Enzyme
The compositions and processes herein can optionally employ one or more
enzymes such as lipases, proteases, cellulase, amylases and peroxidases.
A preferred enzyme for use herein is a cellulase enzyme. Indeed, this type
of enzyme will further provide a color care benefit to the treated fabric.
Cellulases usable herein include both bacterial and fungal types, preferably
having a pH optimum between 5 and 9.5. U.S. 4,435,307 discloses suitable
fungal cellulases from Humicola insolens or Humicola strain DSM1800 or a
cellulase 212-producing fungus belonging to the genus Aeromonas, and
cellulase extracted from the hepatopancreas of a marine mollusk, Dolabella
Auricula Solander. Suitable cellulases are also disclosed in GB-A-
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2.075.028; GB-A-2.095.275 and DE-OS-2.247.832. CAREZYME~ and
CELLUZYME~ (Noun) are especially useful. Other suitable cellulases are
also disclosed in WO 91 /17243 to Novo, WO 96/34092, WO 96/34945 and
EP-A-0,739,982. In practical terms for current commercial preparations,
typical amounts are up to 5 mg by weight, more typically 0.01 mg to 3 mg, of
active enzyme per gram of the detergent composition. Stated otherwise, the
compositions herein will typically comprise from 0.001 % to 5%, preferably
0.01 %-1 % by weight of a commercial enzyme preparation. In the particular
cases where activity of the enzyme preparation can be defined otherwise
such as with cellulases, corresponding activity units are preferred (e.g.
CEVU or cellulase Equivalent Viscosity Units). For instance, the
compositions of the present invention can contain celluiase enzymes at a
level equivalent to an activity from 0.5 to 1000 CEVUlgram of composition.
Cellulase enzyme preparations used for the purpose of formulating the
compositions of this invention typically have an activity comprised between
1,000 and 10,000 CEVU/gram in liquid form, around 1,000 CEVUlgram in
solid form.
Other Optional Ingredients
The present invention can include optional components conventionally used
in textile treatment compositions, for example: brighteners, colorants;
surfactants; anti-shrinkage agents; fabric crisping agents; spotting agents;
germicides; fungicides; anti-oxidants such as butyiated hydroxy toluene,
anti-corrosion agents, antifoam agents, and the like.
The present invention can also include other compatible ingredients,
including those as disclosed in W096/02625, W096/21714, and
W096I21715, and dispersible poiyolefin such as Velustrol~ as disclosed in
co-pending application PCT/US 97/01644, and the like. The present
invention can also contain optional chelating agents.
Form of ~ com os
The fabric care composition can take a variety of physical forms including
liquid such as aqueous or non-aqueous compositions and solid forms such
as solid particulate forms.
Such compositions may be applied onto a substrate such as a dryer sheet
product, used as a rinse added product, or as a spray or foam product.
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Accordingly, in another aspect of the invention, there is provided a method
for providing care to the color of fabrics which comprises the steps of
contacting the fabrics with a composition of the invention.
In a still further aspect of the invention, there is provided a method for the
domestic treatment of a fabric to reduce the amount of dye released from
the fabric during wet treatments and comprising the step of:
a)-contacting the fabrics with a composition of the invention;
b)- thereafter subjecting the treated fabrics to a heating source in a dry
medium.
Preferably, the contacting of the fabrics with a composition of the invention
occurs during the rinse cycle of a washing process.
Preferably, the fabric care composition is a fabric softening composition. The
resulting fabric softening composition is as described herein before.
Preferred heating source for use herein are those in which a temperature of
at least 60°C, more preferably at least 80°C is used, such as
those
commonly known in domestic processes, e.g. in tumble drying processes,
ironing processes or even combination of the above processes.
Dry medium is an important feature of the method aspect of the invention. In
contrast, the use of the heating source in an aqueous medium would not
provide sufficient covalent linkage of the cellulose reactive dye fixing agent
with the dye. It has been found that preferably for the linkage to occur, the
presence of water is to be reduced to a minimum, that is to less than the
moisture regain content of the fabric being treated.
The moisture regain content is defined as in D2654-89a providing Standard
Test Methods for Moisture in Textiles, page 724-733. Of course, the value
for the moisture regain content is specific to the relative humidity, ambient
temperature and type of fabric. In varying at least one of these
characteristics, the moisture regain content value will also vary.
However, what is preferred for the purpose of the invention is that the
content of water in the fabric is below its moisture regain content for a good
chemical linkage to take place.
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Reducing the amount of water, on the fabrics to less than the moisture regain
content is easily achieved by drying the fabrics in a tumble dryer and/or
ironing these dried fabrics.
Process
The fabric softening composition can conveniently be made according to
well known processes to the skilled person. An exemplary disclosure is
given in EP-A-0,668,902.
The invention is illustrated in the following non limiting examples, in which
all
percentages are on a weight basis unless otherwise stated.
In the examples, the abbreviated component identifications have the
following meanings:
DEQA : Di-(tallowyl-oxy-ethyl) dimethyi ammonium chloride
DOEQA : Di-(oleyloxyethyl) dimethyl ammonium methylsulfate
DTDMAC : Ditallow dimethyiammonium chloride
DHEQA : Di-(soft-tailowyl-oxy-ethyl) hydroxyethyl methyl
ammonium
methylsutfate
Fatty acid : tallow fatty acid IV=18
Electrolyte : Calcium chloride
DTDMAMS : Ditallow dimethyl ammonium methylsuifate
SDASA : 1:2 Ratio of stearyldimethyl amineariple-pressed
stearic acid
Glycosperse S-20Polyethoxylated sorbitan monostearate available
: from Lonza
Clay : Calcium Bentonite Ciay, Bentonite L, sold by Southern
Clay
Prod ucts
TAE25 : Tallow alcohol ethoxylated with 25 moles of ethylene
oxide
per mole of alcohol
PEG : Polyethylene Glycol 4000
PEI 1800 E1 : Ethoxylated polyethylene imine (MW 1800, at
50% active) as
synthesised in Synthesis example 1
PEI 1800 E3 : Ethoxylated polyethylene imine (MW 1800, at
50% active) as
synthesised as per Synthesis example 1
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PEI 1800 E7 AO : Amine oxide of ethoxylated polyethylene imine (MW 1800, at
50% active) as synthesised as per Synthesis example 4
PEI 1200 E1 : Ethoxylated polyethylene imine (MW 1200, at 50% active in
water) as synthesised in Synthesis example 5
PEI 1200 E2 : Ethoxylated polyethylene imine (MW 1200, at 50% active in
water) as synthesised per Synthesis example 5
PEI 1200 E7 : Ethoxylated polyethylene imine (MW 1200, at 50% active in
water) as synthesised per Synthesis example 5
PEI 1200 E7 AO : Amine oxide of ethoxylated polyethylene imine (MW 1200, at
50% active) as synthesised as per Synthesis example 5 and
4
Dye Fix 1 : Cellulose reactive dye fixing agent available under the
tradename Indosol CR from Clariant
Dye Fix 2 : Cellulose reactive dye fixing agent available under the
tradename Rewin WBS from CHT R. Beitlich
LAS : Sodium linear C12 alkyl benzene
sulphonate
TAS : Sodium tatfow alcohol sulphate
C25AS : Sodium C12-C15 linear alkyl sulphate
CxyEzS : Sodium C1x-C1y branched alkyl sulphate
condensed with z moles of ethylene oxide
C45E7 : A C14_15 predominantly linear primary
alcohol
condensed with an average of 7 moles of
ethylene oxide
C25 E3 : A C12_15 branched primary alcohol condensed
with an average of 3 moles of ethylene oxide
Cationic : Mixture of C12/C14 choline ester
ester
Soap : Sodium linear alkyl carboxylate derived
from an
80120 mixture of tallow and a coconut oils.
TFAA : C1g-C1g alkyl N-methyl glucamide
TPKFA : C12-C14 topped whole cut fatty acids
Zeolite A : Hydrated Sodium Aluminosilicate of formula
Nal2(A102Si02)12. 27H20
having a primary particle size in the range from
0.1 to 10 micrometers
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Citric acid : Anhydrous citric acid
Carbonate : Anhydrous sodium carbonate with a particle size
between 200pm and 900~m
Silicate : Amorphous Sodium Silicate (Si02:Na20; 2.0
ratio)
Sulphate : Anhydrous sodium sulphate
Citrate : Tri-sodium citrate dihydrate of activity 86.4% with
a particle size distribution between 425~m and 850
pm
MA/AA : Copolymer of 1:4 maleic/acrylic acid, average
molecular weight about 70,000.
CMC : Sodium carboxymethyl cellulose
Savinase : Proteolytic enzyme of activity 4KNPU/g
Carezyme : Cellulytic enzyme of activity 1000 CEVU/g
Termamyi : Amylolytic enzyme of activity 80KNU/g
Lipolase : Lipolytic enzyme of activity 100kLUlg
all sold by NOVO Industries A/S and of activity
mentioned above unless otherwise specified
PB4 : Sodium perborate tetrahydrate of nominal formula
NaB02.3H20.H202
PB1 : Anhydrous sodium perborate bleach of
nominal formula NaB02.H202
TAED : Tetraacetyl ethylene diamine
DTPMP : Diethylene triamine yenta (methylene
phosphonate), marketed by Monsanto under the
Trade name bequest 2060
Photoactivated: Sulphonated Zinc Phthalocyanin encapsulated in
bleach dextrin soluble polymer
Brightener : Disodiurn 4,4'-bis(4-anilino-6-morpholino-1.3.5-
triazin-2-yl)amino) stiibene-2:2'-disulphonate.
Silicone antifoam : Polydimethyldiloxane foam controller with
Siloxane-oxyalkylene copolymer as dispersing
agent with a ratio of said foam controller to said
dispersing agent of 10:1 to 100:1..
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HEDP : 1,1-hydroxyethane diphosphonic acid
~vnthesis Example 1 -Preparation of PE1 1800 E1
Step A)-The ethoxylation is conducted in a 2 gallon stirred stainless steel
autoclave equipped for temperature measurement and control, pressure
measurement, vacuum and inert gas purging, sampling, and for introduction
of ethylene oxide as a liquid. A ~20 Ib. net cylinder of ethylene oxide (ARC)
is set up to deliver ethylene oxide as a liquid by a pump to the autoclave
with the cylinder placed on a scale so that the weight change of the cylinder
could be monitored.
A 750 g portion of polyethyleneimine (PEI) (Nippon Shokubai, Epomin SP-
018 having a listed average molecular weight of 1800 equating to 0.417
moles of polymer and 17.4 moles of nitrogen functions) is added to the
autoclave. The autoclave is then sealed and purged of air (by applying
vacuum to minus 28" Hg followed by pressurization with nitrogen to 250
psia, then venting to atmospheric pressure). The autoclave contents are
heated to 130 °C while applying vacuum. After about one hour, the
autoclave is charged with nitrogen to about 250 psia while cooling the
autoclave to about 105 °C. Ethylene oxide is then added to the
autoclave
incrementally over time while closely monitoring the autoclave pressure,
temperature, and ethylene oxide flow rate. The ethylene oxide pump is
turned off and cooling is applied to limit any temperature increase resulting
from any reaction exotherm. The temperature is maintained between 100
and 110 °C while the total pressure is allowed to gradually increase
during
the course of the reaction. After a total of 750 grams of ethylene oxide has
been charged to the autoclave (roughly equivalent to one mole ethylene
oxide per PEI nitrogen function), the temperature is increased to 110
°C and
the autoclave is allowed to stir for an additional hour. At this point, vacuum
is applied to remove any residual unreacted ethylene oxide.
Step B)- The reaction mixture is then deodorized by passing about 100 cu.
ft. of inert gas (argon or nitrogen) through a gas dispersion frit and through
the reaction mixture while agitating and heating the mixture to 130 °C.
The final reaction product is cooled slightly and collected in glass
containers
purged with nitrogen.
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In other preparations the neutralization and deodorization is accomplished in
the reactor before discharging the product.
If a PEI 1800 E7 is desired, the following step of catalyst addition will be
included between Step A and B.
Vacuum is continuously applied while the autoclave is cooled to about 50
°C
while introducing 376 g of a 25% sodium methoxide in methanol solution
(1.74 moles, to achieve a 10% catalyst loading based upon PEI nitrogen
functions). The methoxide solution is sucked into the autoclave under
vacuum and then the autoclave temperature controller setpoint is increased
to 130 °C. A device is used to monitor the power consumed by the
agitator.
The agitator power is monitored along with the temperature and pressure.
Agitator power and temperature values gradually increase as methanol is
removed from the autoclave and the viscosity of the mixture increases and
stabilizes in about 1 hour indicating that most of the methanol has been
removed. The mixture is further heated and agitated under vacuum for an
additional 30 minutes.
Vacuum is removed and the autoclave is cooled to 105 °C while it
is being
charged with nitrogen to 250 psia and then vented to ambient pressure. The
autoclave is charged to 200 psia with nitrogen. Ethylene oxide is again
added to the autoclave incrementally as before while closely monitoring the
autoclave pressure, temperature, and ethylene oxide flow rate while
maintaining the temperature between 100 and 110 °C and limiting any
temperature increases due to reaction exotherm. After the addition of 4500
g of _ethylene oxide (resulting in a total of 7 moles of ethylene oxide per
mole
of PEI nitrogen function) is achieved over several hours, the temperature is
increased to 110 °C and the mixture stirred for an additional hour.
The reaction mixture is then collected in nitrogen purged containers and
eventually transferred into a 22 L three neck round bottomed flask equipped
with heating and agitation. The strong alkali catalyst is neutralized by
adding 167 g methanesulfonic acid (1.74 moles).
Other preferred examples such as PEI 1800 E2, PEI 1800 E3, PEI 1800
E15 and PEI 1800 E20 can be prepared by the above method by adjusting
the reaction time and the relative amount of ethylene oxide used in the
reaction.
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Synthesis Example 2 -4 7% Ouaternization of PEI 1800 E7
To a 500m1 erlenmeyer flask equipped with a magnetic stirring bar is added
poly(ethyleneimine), MW 1800 ethoxylated to a degree of 7 (2248, 0.637
moi nitrogen, prepared as in Synthesis Example 1 ) and acetonitrile (Baker,
1508, 3.65 mol). Dimethyl sulfate (Aldrich, 3.88, 0.030 mol) is added al! at
once to the rapidly stirring solution, which is then stoppered and stirred at
room temperature overnight. The acetonitrile is evaporated on the rotary
evaporator at -60°C, followed by a Kugelrohr apparatus (Aldrich) at -
80°C
to afford ~220g of the desired material as a dark brown viscous liquid. A
13C_NMR (D20) spectrum shows the absence of a peak at ~58ppm
corresponding to dimethyi sulfate. A 1 H-NMR (D20) spectrum shows the
partial shifting of the peak at 2.5ppm (methylenes attached to unquaternized
nitrogens) to ~3.Oppm.
S~cnthesis Exam_hle 3 Oxidation of 4 7% Quaternized PEI 1800 E7
To a 500m1 erienmeyer flask equipped with a magnetic stirring bar is added
poly(ethyleneimine), MW 1800 which has been ethoxyiated to a degree of 7,
and -4.7% quatemized with dimethyl sulfate (121.78, -0.32 moi oxidizeable
nitrogen, prepared as in Synthesis Example 2), hydrogen peroxide (Aldrich,
408 of a 50 wt% solution in water, 0.588 mol), and water (109.48). The flask
is stoppered, and after an initial exotherm the solution is stirred at room
temperature overnight. A 1 H-NMR (D20) spectrum shows the total shifting
of the methylene peaks at 2.5-3.Oppm to ~3.5ppm. To the solution is added
~5g of 0.5% Pd on alumina pellets, and the solution is allowed to stand at
room temperature for -3 days. Peroxide indicator paper shows that no
peroxide is left in the system. The material is stored as a 46.5% solution in
water.
Synthesis Example 4 -Formation of amine oxide of PEI 1800 E7
To a 500 mL Erlenmeyer flask equipped with a magnetic stirring bar is
added poiyethyleneimine having a molecular weight of 1800 and ethoxylated
to a degree of about 7 ethoxy groups per nitrogen (PEI-1800, E7) (209 g,
0.595 mol nitrogen, prepared as in Synthesis Example I), and hydrogen
peroxide (120 g of a 30 wt % solution in water, 1.06 mol). The flask is
stoppered, and after an initial exotherm the solution is stirred at room
temperature overnight. 1 H-NMR (D20) spectrum obtained on a sample of
the reaction mixture indicates complete conversion. The resonances
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47
ascribed to methyiene protons adjacent to unoxidized nitrogens have shifted
from the original position at -2.5 ppm to -3.5 ppm. To the reaction solution
is added approximately 5 g of 0.5% Pd on alumina pellets, and the solution
is allowed to stand at room temperature for approximately 3 days. The
solution is tested and found to be negative for peroxide by indicator paper.
The material as obtained is suitably stored as a 51.1 % active solution in
water.
~~ynthesis Example 5 -Preparation of PEI 1200 E1
Step A)-The ethoxylation is conducted in a 2 gallon stirred stainless steel
autoclave equipped for temperature measurement and control, pressure
measurement, vacuum and inert gas purging, sampling, and for introduction
of ethylene oxide as a liquid. A -20 Ib. net cylinder of ethylene oxide (ARC)
is set up to deliver ethylene oxide as a liquid by a pump to the autoclave
with the cylinder placed on a scale so that the weight change of the cylinder
could be monitored.
A 750 g portion of polyethyleneimine (PEI) ( having a listed average
molecular weight of 1200 equating to about 0.625 moles of polymer and
17.4 moles of nitrogen functions) is added to the autoclave. The autoclave
is then sealed and purged of air (by applying vacuum to minus 28" Hg
followed by pressurization with nitrogen to 250 psia, then venting to
atmospheric pressure). The autoclave contents are heated to 130 °C
while
applying vacuum. After about one hour, the autoclave is charged with
nitrogen to about 250 psia while cooling the autoclave to about 105 °C.
Ethylene oxide is then added to the autoclave incrementally over time while
closely monitoring the autoclave pressure, temperature, and ethylene oxide
flow rate. The ethylene oxide pump is turned off and cooling is applied to
limit any temperature increase resulting from any reaction exotherm. The
temperature is maintained between 100 and 110 °C while the total
pressure
is allowed to gradually increase during the course of the reaction. After a
total of 750 grams of ethylene oxide has been charged to the autoclave
(roughly equivalent to one mole ethylene oxide per PEI nitrogen function),
the temperature is increased to 110 °C and the autoclave is allowed to
stir
for an additional hour. At this point, vacuum is applied to remove any
residual unreacted ethylene oxide.
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Step B)- The reaction mixture is then deodorized by passing about 100 cu.
ft. of inert gas (argon or nitrogen) through a gas dispersion frit and through
the reaction mixture while agitating and heating the mixture to 130 °C.
The final reaction product is cooled slightly and collected in glass
containers
purged with nitrogen.
In other preparations the neutralization and deodorization is accomplished in
the reactor before discharging the product.
If a PEI 1200 E7 is desired, the following step of catalyst addition will be
included between Step A and B.
Vacuum is continuously applied while the autoclave is cooled to about 50
°C
while introducing 376 g of a 25% sodium methoxide in methanol solution
(1.74 moles, to achieve a 10% catalyst loading based upon PEI nitrogen
functions). The methoxide solution is sucked into the autoclave under
vacuum and then the autoclave temperature controller setpoint is increased
to 130 °C. A device is used to monitor the power consumed by the
agitator.
The agitator power is monitored along with the temperature and pressure.
Agitator power and temperature values gradually increase as methanol is
removed from the autoclave and the viscosity of the mixture increases and
stabilizes in about 1 hour indicating that most of the methanol has been
removed. The mixture is further heated and agitated under vacuum for an
additional 30 minutes.
Vacuum is removed and the autoclave is cooled to 105 °C while it
is being
charged with nitrogen to 250 psia and then vented to ambient pressure. The
autoclave is charged to 200 psia with nitrogen. Ethylene oxide is again
added to the autoclave incrementally as before while closely monitoring the
autoclave pressure, temperature, and ethylene oxide flow rate while
maintaining the temperature between 100 and 110 °C and limiting any
temperature increases due to reaction exotherm. After the addition of 4500
g of ethylene oxide (resulting in a total of 7 moles of ethylene oxide per
mole
of PEI nitrogen function) is achieved over several hours, the temperature is
increased to 110 °C and the mixture stirred for an additional hour.
The reaction mixture is then collected in nitrogen purged containers and
eventually transferred into a 22 L three neck round bottomed flask equipped
with heating and agitation. The strong alkali catalyst is neutralized by
adding 167 g methanesulfonic acid (1.74 moles).
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Other preferred examples such as PEI 1200 E2, PEI 1200 E3, PEl 1200
E15 and PEI 1200 E20 can be prepared by the above method by adjusting
the reaction time and the relative amount of ethylene oxide used in the
reaction.
The corresponding amine oxide of the above ethoxylated PEI can also be
prepared following synthesis Example 4.
S~mthesis Exam;~le 6 -9 7% Quaternization of PEI 1200 E7
To a 500m1 erlenmeyer flask equipped with a magnetic stirring bar is added
poly(ethyieneimine), MW 1200 ethoxylated to a degree of 7 (248.48, 0.707
moi nitrogen, prepared as in Synthesis Example 5) and acetonitrile (Baker,
200 mL). Dimethyl sulfate (Aldrich, 8.488, 0.067 mol) is added all at once to
the rapidly stirring solution, which is then stoppered and stirred at room
temperature overnight. The acetonitrile is evaporated on the rotary
evaporator at -60°C, followed by a Kugelrohr apparatus (Aldrich) at
~80°C
to afford -2208 of the desired material as a dark brown viscous liquid. A
13C-NMR (D20) spectrum shows the absence of a peak at -58ppm
corresponding to dimethyl sulfate. A 1 H-NMR (D20) spectrum shows the
partial shifting of the peak at 2.5ppm (methylenes attached to unquaternized
nitrogens) to -3.Oppm.
synthesis ExamyP 7-4 7% Oxidation of 9.5% Quatemized PEI 1200 E7
To a 500m1 erienmeyer flask equipped with a magnetic stirring bar is added
poiy(ethyleneimine), MW 1200 which has been ethoxyiated to a degree of 7,
and -9.5% quatemized with dimethyl sulfate (1448, -0.37 mo! oxidizeable
nitrogen, prepared as in Example 6), hydrogen peroxide (Aldrich, 35.48 of a
50 wt% solution in water, 0.52 mol), and water (1008). The flask is
stoppered, and after an initial exotherm the solution is stirred at room
temperature overnight. A 1 H-NMR (D20) spectrum shows the total shifting
of the methylene peaks at 2.5-3.Opprn to -3.5ppm. To the solution is added
just enough sodium bisulfite as a 40% water solution to bring the residual
peroxide level down to 1-5ppm. The sodium sulfate which forms causes an
aqueous phase to separate which contains salts, but little or no organics.
The aqueous salt phase is removed and the desired oxidized
polyethyleneimine derivative is obtained and stored as a 52% solution in
water.
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Examl Ip a 1
The following compositions are in accordance with the present invention
Component A B C D E F G H
DEQA 2.6 2.9 18.0 19.019.0 -
TAE25 - 1.0 - - ~ _ _
_
Fatty acid 0.3 - 1.0 - - - - -
Hydrochloride acid 0.0 0.02 0.02 0.02~ 0.02- - -
2
PEG - - 0.6 0.6 0.6 - ~
-
Perfume 1.0 1.0 1.0 1.0 1.0 0.1 0.1 0.1
Silicone antifoam 0.0 0.01 0.01 0.010.01 - - -
1
PEl 1200 E1 3 3 3 3 - 15 - 10
~
PEI 1200 E2 - 3 10 -
Dye fix 1 1.0 0.5 - 1 5.0 - 10 3.0
Dye fix 2 - 0.5 3 2 - 5.0 - -
HEDP 0.2 - - 0.2 - 0.4 - 0.8
Electrolyte (ppm) - - 600 600 1200 - - -
Dye (ppm) 10 10 50 50 50 - -
Water and minors to balance
to 100
160 g of fabrics were treated with composition A. The fabrics were then line
dried and then submitted to an ironing process set on linen. It is then
observed after a further wash cycle that the fabric treated in this manner
exhibit better dye fixing performance than fabrics which have not undergo a
ironing process.
The same results were obtained with compositions B to H.
Similar results are obtained with the following invention compositions:
Component I J K L
DTDMAC - - 15
DEQA 2.6 19.0 - -
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TAE25 0.3 - - -
Fatty acid 0.3 - - -
Hydrochloride0.02 0.02 - 0.02
acid
PEG 0.6 - 0.6
Perfume 1.0 1.0 0.1 1.0
Silicone 0.01 0.01 - 0.01
antifoam
PEI 1800 E1 3 3 10 3
Dye fix 1 1 3.0 10 1
Dye fix 2 2 - - 2
Electrolyte - 600 - 600
(PPm)
Dye (ppm) 10 50 - 50
Water and
minors to
balance to
100
Exam Ip a 2
The following compositions for use as dryer-added sheets are in accordance
with the invention
M N O P Q R
DOEQA 40 25 - - - -
DHEQA - - 20 - - -
DTDMAMS - - - 20 12 60
SDASA 30 30 20 30 20 -
Giycosperse S-20 - 10 - - -
Giycerol - - - 20 10 -
Monostearate
Clay 4 4 3 4 4 -
Perfume 0.7 1.1 0.7 1.6 2.6 1.4
PEI 1800 E1 - 5 - - - -
PEI 1200 E1 - - 4 2.2 - -
PEI 1800 E3 2 - - - 5 7.0
Dye fix 1 2 5 4 2.2 5 3
HEDP 0.2 - 0.5 - - 0.7
Glycolic - 0.2 - 0.2 - -
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Polycarboxyiic - 0.2 ~ - - I 0.4 -
Stearic acid to balance
Exams l~ a 3
The following detergent formulations S and T, are in accordance with the
present invention:
S T
Zeolite A 24.0 23.0
Sulphate 9.0 -
MA/AA 4.0 4.0
LAS 8.0 8.0
TAS - 2.0
Silicate 3.0 3.0
CMC 1.0 0.4
Brightener 0.2 -
Soap 1.0 -
DTPMP 0.4 0.4
C45E7 2.5 2.0
C25E3 2.5 2.0
Silicone antifoam 0.3 5.0
Perfume 0.3 0.3
Carbonate 13.0 16.0
Citrate - 5.0
PB4 18.0 -
PB1 4.0 14.0
TAED 3.0 6.0
Photoactivated bleach0.02% -
Savinase 1.0 1.0
Lipolase 0.4 0.4
Termamyl 0.30 0.6
Carezyme - 0.6
PEI 1800 E7 AO 1.0 -
PEI 1200 E7 AO - 1.0
Dye fix 1 2.0 1.0
HEDP 0.2 -
Glycolic - 0.2
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I Polycarboxylic I - 1 0.2
Balance (Moisture and Miscellaneous) to 100
Exam IQ a 4
The following liquid detergent formulation, according to the present invention
was prepared:
U
C25AS 13
C25E3S 2
TFAA 6
C12-14 alkyl dimethyihydroxy ethyl ammonium 1
chloride
Cationic ester 1.5
TPKFA 15
Citric acid 1
Ethanol 2
1,2 Propanediol 8
NaOH up to pH 7.5
DTPMP 1.2
Savinase 0.5
Termamyl (300 KNU/g) 0.15 '
Boric acid 1.5
Softening clay of the bentonite type 4
Suspending clay SD3 0.3
PEI 1200 E7 1
Dye fix 2
1
Balance (Moisture and Miscellaneous) 100
