Note: Descriptions are shown in the official language in which they were submitted.
CA 02488839 2004-12-02
1
LIQUID FABRIC SOFTENING COMPOSITIONS COMPRISING FLAME
RETARDANT.
FIELD OF INVENTION
The present invention relates to fabric care compositions comprising a flame
retardant.
The present compositions are preferably used to treat fabrics to provide
fabric softening while
minimizing the risk of flammability of certain cotton-containing fluffier
fabrics when treated With
liquid fabric softening compositions.
BACKGROUND OF THE INVENTION
Liquid fabric softening compositions are generally used during the rinse cycle
of a typical
laundry process to provide improved softness and freshness to the fabrics
being laundered.
Some cotton-containing fluffier fabrics, such as fleece and terry cloth, tend
to be more
flammable than other types of fabrics. By increasing the fluffiness of these
types of fabrics, the
use of liquid fabric softening compositions on these types of fabrics may
potentially increase the
flammability of these types of fabrics.
There is thus a need to develop an improved liquid fabric softening
composition that
provides fabric softening and freshness, while minimizing the risk of
flammability of certain
cotton-containing fluffier fabrics when treated with liquid fabric softening
compositions.
SUMMARY OF THE INVENTION
The present invention relates to liquid fabric softening compositions
comprising a fabric
softening active and a flame retardant. Preferred flame retardants for
incorporation in the present
compositions include phosphorus containing materials, phosphorus containing
materials also
comprising an amine moiety or a carboxylate moiety, phosphorus containing
materials capable of
dual functionality as fabric softening components, cationic starch comprising
a phosphorus
moiety, or mixtures thereof. In a first embodiment of the present invention,
the compositions
typically comprise flame retardant at a level of from about 0.001% to about
60%, preferably from
about 0.01 % to about 40%, and more preferably from about 0.1 % to about 10%,
by weight of the
composition. In a second embodiment of the invention, the present compositions
comprise no
greater than about 21%, by weight of the composition, of a fabric softener
active and at least
about 0.5%, by weight of the composition, of a silicone material. In a third
embodiment of the
invention, the present compositions comprise a flame retardant, wherein the
flame retardant is a
phosphorus-containing fabric softener. The present compositions can be used to
treat all types of
fabrics to provide improved fabric softening and freshness, while minimizing
the risk of
flammability associated with cotton-containing fluffier fabrics, such as
fleece and terry cloth,
when treated with liquid fabric softening compositions.
CA 02488839 2004-12-02
2
All documents cited are, in relevant part, incorporated herein by reference;
the citation of
any document is not to be construed as an admission that it is prior art with
respect to the present
invention.
It should be understood that every maximum numerical limitation given
throughout this
specification will include every lower numerical limitation, as if such lower
numerical limitations
were expressly written herein. Every minimum numerical limitation given
throughout this
specification will include every higher numerical limitation, as if such
higher numerical
limitations were expressly written herein. Every numerical range given
throughout this
specification will include every narrower numerical range that falls within
such broader numerical
range, as if such narrower numerical ranges were all expressly written herein.
All parts, ratios, and percentages herein, in the specification, examples, and
claims, are by
weight and all numerical limits are used with the normal degree of accuracy
afforded by the art,
unless otherwise specified.
DETAILED DESCRIPTION OF THE INVENTION
FLAME RETARDANTS
In a preferred embodiment of the invention, the present liquid fabric
softening
compositions comprise a flame retardant typically at a level of from about
0.001% to about 60%,
preferably from about 0.01% to about 40%, and more preferably from about 0.1%
to about 10%,
by weight of the composition. The flame retardant is present at an effective
level to reduce the
burn time of fluffier fabric. Flame retardants can be available as solids,
liquids, solutions,
emulsions, dispersions, slurries, or any form that can be formulated into the
fabric softener
composition.
PHOSPHORUS-CONTAINING COMPOUNDS
A variety of phosphorus-containing compounds are suitable as a flame retardant
in the
present compositions. General classes of phosphorus-containing compounds
suitable as a flame
retardant herein include, but are not limited to, classes and types of
materials as well as individual
materials disclosed in the Kirk-Othrner Encyclopedia of Chemical Technology
4'" Edition Vol. 10
in the subsection "Phosphorus Flame Retardants" under the chapter heading
"Flame Retardants"
and in Vol. 10 in the chapter titled "Flame Retardants for Textiles" and also
in the Handbook of
fiber Science and Technology: 1o1. II Chemical Processing of Fibers and
Fabrics Fur~ctior7al
Finishes Part B, Eds. M. Lewin and S.B. Sello, "Chapter 1 Flame Retardance of
Fabrics"
Industrial Solvents Handbook 4'" Ed. Ed. By E. Flick, Noyes Data Corp., Park
Ridge, NJ 1991,
Section 15.
Phosphorus-containing compounds are typically most effective when the
deposition of the
phosphorus-containing compound onto fabric results in the presence of at least
about 0.001
CA 02488839 2004-12-02
3
milligram ("mg") of phosphorus per gram of treated fabric, preferably at least
about 0.005 mg of
phosphorus per gram of treated fabric, more preferably at least about 0.02 mg
of phosphorus per
gram of treated fabric, even more preferably at least about 0.1 mg of
phosphorus per gram of
treated fabric, still more preferably at least about 0.5 mg of phosphorus per
gram of treated fabric,
and even still more preferably at least about 1 mg of phosphorus per gram of
treated fabric. When
formulating phosphorus-containing compounds in a liquid fabric softening
composition
comprising fabric softening actives, such as di-tail quaternary ammonium
actives, it is preferred
that the phosphorus-containing compounds are neutral or have a positive
charge. Compounds with
a high weight percent of phosphorus are typically preferred. Typically, the
phosphorus-containing
compounds herein will comprise at least about 0.1%, preferably at least about
I%, more
preferably at least about 5%, even more preferably at least about 8%, and
still more preferably at
least about IO% of phosphorus, by weight of the phosphorus-containing
compound. Preferably,
the phosphorus-containing compounds, especially salts, decompose at a
temperature of less than
600°C. To prevent the formation of salts with high decomposition
temperatures, it can be useful
and preferred in some applications to functionalize the oxygens or nitrogens
bonded to
phosphorus with a covalently bonded group that will not exchange with salt to
prevent formation
of salts with high decomposition temperatures.
Phosphorus-containing compounds suitable herein include phosphoric acid,
phosphate
salts, phosphate esters, phosphate amides, phosphorus acid, phosphite salts,
phosphite salt
derivatives, phosphonic acid, phosphonate salts, phosphonate esters,
phosphonate amides,
phosphorus compounds containing nitrogen moieties, phosphorus compounds
containing
carboxylic acids, phosphorus compounds containing carboxylic esters,
phosphonium salts,
polyethylene amine polymers comprising phosphorus substituents, cationic
starch comprising a
phosphorus substituent, or mixtures thereof.
Acids of Phosphorus and Their Salts and Derivatives
Phosphoric
Acid and
the Phosphate
Salts, Esters
and Amides
Phosphorus
acids and
phosphates
have three
general
structures
disclosed
below:
Structure Structure 2 Structure
1 3
0 ~ O O O
RA- I AR RA- I -O-, -AR RA- I -~- ' I I -AR
~0-
AR AR AR AR AR AR
wherein each A is independently an oxygen atom or a nitrogen atom, preferably
an
oxygen atom; and each R is independently selected from the group consisting of
hydrogen.
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4
positively charged metal counterions, moieties comprising amines, moieties
comprising
ammonium ions, and moieties comprising hydrocarbons. Positively charged metal
counterions are
selected from the group consisting of metal ions in groups IA, IIA, IIIA, IVA,
VA, VIA, VIIA,
VIII, IB, and I1B; especially preferred are Na+, K+, and Al3+, and tin ions,
and less preferred but
acceptable are Ca2+ and Mg2+ ions. The above mentioned moieties comprising
amines or
ammonium ions include, but are not limited to, the following structure:
N(R')4+
wherein each R' is independently selected from the group consisting of
hydrogen,
hydrocarbons comprised entirely of carbon and hydrogen, and hydrocarbons
comprising moieties
with atoms more electronegative than carbon, preferably oxygen, nitrogen,
halogens, especially
chlorine and bromine, sulfur, phosphorus, and combinations of electronegative
atoms and wherein
the hydrocarbon comprises one to about 30 carbons. The hydrocarbons can be
linear, branched,
saturated, unsaturated, cyclic, aromatic, or combinations of these structural
configurations; it is
acceptable for moieties comprising electronegative atoms to interrupt the
hydrocabon. It is
acceptable for N(R') to have more than one point of connectivity to a
phosphorus moiety or to
connect more than one phosphorus moiety.
Hydrocarbons suitable for R comprise from about 1 to about 150 carbon atoms.
preferably less than about 100 carbon atoms, and more preferably less than
about 50 carbon
atoms. It is acceptable for the R group to link to a phosphate with more than
one binding site or
bond and it is also acceptable for the R group to link together more than one
phosphate with
multiple binding sites or bonds. It is acceptable for the phosphate-containing
compounds to be
single molecules, oligomers, or polymers. Additionally, the R group can be
neutral or have
positive and/or negative charges.
Nonlimiting examples of phophorus salts and acids acceptable for the present
invention
include orthophosphoric acid, pyrophosphoric acid, sodium orthophosphate,
sodium
pyrophosphate, and sodium tripolyphosphate ("STPP").
Other nonlimiting examples include compounds comprising an ammonium ion as
well as
well as compounds comprising polyammonium ions and/or those compounds that
have more than
one connection to a phosphorus moiety or moieties, such as melamine
orthophosphate,
pentaerythritol phosphate bis melaminium salt or guanidine tripolyphosphates,
as described in JP
52085599 and JP 60259676, and dibromoneopentyl phosphate melamine salt as
described in US
4,373.103. Nonlimiting commercially-available compounds include Antiblaze~ TR,
Antiblaze~
CL available from Rhodia, Melapur~ pyrophosphate, Melapur~ orthophosphate
available from
DSM, melamine pyrophosphate and melamine orthophosphate from Hummel Cronton,
lnc.
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Nonlimiting examples of the present invention include phosphate and
phosphoamide
compounds described in US 3,678;086; US 4,503,002; US 4,336,385; US 4,209,449;
US
4,215.064; US 3,686,368; US 5,650,402; US 5,648,348; and US Application No.
2003/0003358
A1; melamine-phosphate salts derivatized with halogenated organic groups as
described in US
4,373.103; amine salts of phosphates as described in US 6,114;421; and US
5,539,141; and
reaction products as described in US 3,959,156. Nonlimiting commercially-
available compounds
include Phosflex~ 4, Phosflex~ 21L, Phosflex~ 21P, Phosflex~ 31L, Phosflex~
31P, Phosflex~
41L, Phosflex~ 41P, Phosflex~ 61B, Phosflex~ 71B Phosflex~ 72B, Phosflex~ 362,
Phosflex~
370, Phosflex~390, Phosflex~ HF, Phosflex~ Lindol, Phosflex~ Lindol XP Plus,
Phosflex~ T-
BEP, Phosflex~ TPP, and the blends Phosflex~ 314, Phosflex~ 321, Phosflex~ 327
Phosphoflex~ 72B, Fyrol FR-2, and the like available from Akzo Nobel
Phosphorus Chemicals;
Emphos~ CS 1361 from Eastech Chemical, Inc., Arlasilk~ Phospholipid PTC,
Arlasitk~
Phospholipid PTS, Arlasilk~ Phospholipid EFA, Arlatone~ MAP 230T-60 from
Uniqema,
lecithin compounds produced by Archer Daniels Midland, Degussa, Monsanto and
other suppliers
as well as compounds fitting the structure descriptions of
phosphatidylcholines,
phosphatidylethanolamines, and phosphatidylinositols.
Further nonlimiting examples of phosphate-containing compounds herein further
include
polymers disclosed in US 5,274,101. Some non-limiting commercially-available
compounds of
phosphates combined with R groups to form oligomeric or polymeric materials
are Pluracol~ 684
from BASF and Exolit~ 413 from Hoeschst-Celanese, a material that contains a
halogen as well
as phosphorus. Fyroflex~ BDP and Fyrol~ 51, which is a phosphorus-rich
oIigomer made by
reaction of phosphorus containing compounds with ethylene oxide, both
available from Akzo
Nobel. Other phosphorus-containing polymers made by reaction of an alkylene
oxide, especially
polypropylene oxide, with phosphoric or polyphosphoric acid are described in
the Kirk-Othmer
Encyclopedia of Chemical Technology 4'" Edition Vol. 10 in the subsection
"Phosphorus Flame
Retardants" under the chapter heading "Flame Retardants".
Phosphorus Acid and the Phos~hite Salts and Derivatives
Phosphorus acid and the phosphite salts and derivatives have the general
structure below:
AR
-AR
AR
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6
wherein A and R have the same meanings as defined in the previous description
of
phosphoric acid and the phosphate salts herein above. It is acceptable for the
R group to bind or
bond to a phosphate at more than one site or for the R group to connect
several phosphate groups.
It is acceptable for phosphorus acid/ phosphate flame retardants of the
present invention to be
single molecules, oligomers, or polymers. Some non-limiting commercially-
available compounds
include Doverphos~ 4, Doverphos~ HiPure 4, Doverphos~ 8, Doverphos~ 10,
Doverphos ~ 53,
Doverphos~ 613, Doverphos ~ 675, Doverphos~ S-480, all available from Dover
Chemical
Corporation. Doverphos~ S-9228, Doverphos~ S-680, and Doverphos~ 1220, are
examples of
compounds having an R group that bonds to more than one phosphate group.
Phosphonic Acid and the Phosphonate Salts, Esters. and Amides
Phosphonic acid and phosphonate salts and esters have the following general
structure:
Structure 4 Structure 5
O
H-P R"-C-IP-AR
-AR
AR R"' AR
wherein A and R have the same meanings as defined in the previous description
of
phosphoric acid and the phosphate salts herein; each R', R", and R"' are
independently either
hydrogen or R as defined in the previous description of phosphoric acid and
the phosphate salts
herein above. It is acceptable for R, R', R'', and R"' to bind or bond to a
phosphonate at more
than one site or for such groups to connect several phosphonate groups.
Nonlimiting examples of
acceptable compounds include diethylene triamine pentamethyl phosphonic acid,
phosphomaleate, and compounds disclosed in US 4,243,602; US 3;870,771; US
3,812,218; and
US 3,821,263. Some commercially-available compounds include Dequest~ 7000 and
Dequest~
2066S from Solutia, Bayhibit~ AM available from Bayer, and Ecco Flameproof CPE
available
from Eastern Color & Chemical Co and Fyrol~ 6 available from Akzo Nobel
Phosphorus
Chemicals.
Other compounds acceptable for use as flame retardants herein are disclosed in
US
6,309,565.
It is acceptable for the present invention for compounds to comprise mixtures
of the
different types of phosphorus acids and their salts and derivatives. e.g. a
compound could contain
both a phosphate and a phosphate moiety.
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Some non-limiting examples of flame retardants based on phosphorus acids and
salts and
their esters and amides that are preferred include phosphorus compounds
containing nitrogen
moieties and polymers containing phosphorus.
Phosphorus Compounds Containing Nitrogen Moieties
Some preferred types of phosphorus-containing compounds include those
comprising
nitrogen moieties. Nitrogen, especially amines and amides, are surprisingly
found to enhance the
flame retardancy affects of phosphorus-containing compounds. When phosphorus-
containing
compounds comprise quaternary ammonium compounds or amines that can be
protonated, the
deposition of the phosphorus-containing compound onto fabrics during the rinse
cycle of a
laundry washing process is improved.
It can also be preferred to use phosphorus-containing compounds structurally
similar to
current fabric softening actives to enhance deposition of the phosphorus. Most
fabric softening
actives, as described herein, can be functionalized with a phosphorus ester or
amide to improve
deposition of the phosphorus moiety and improve the flame retardancy of the
present
compositions. Phosphorus esters and amides are also useful as divalent linking
moieties between
fatty acids and fabric softener head groups. Most fabric softening actives,
such as quaternary
ammonium compounds, can be substituted with phosphorus and provide a degree of
flame
retardancy either in a single-cycle or multi-cycle use. Phosphorus-containing
compounds that act
as fabric softener actives ("phosphorus-containing fabric softener material")
can be used to
replace the non-phosphorus fabric softening actives, in part or in whole.
Therefore, when such
phosphorus-containing fabric softener materials are utilized as a flame
retardant in the present
compositions, a fabric softening active is an optional, not essential,
component of the
composition. Examples of phosphorus-containing fabric softener materials
suitable as flame
retardants herein are described below, as Structures 6 and 7.
Structure 6
N(R')x
Structure G is an amine or quaternary ammonium compound wherein x is 3 or 4.
R' is
hydrogen; a hydrocarbon with less than about 30 carbons optionally comprising
atoms more
electronegative than carbon including oxygen. nitrogen, sulfur, phosphorus,
halogens, such as
bromine or chlorine, or combinations thereof; -R'-A-P(O)(AR3)~; Rz-A-P(O)(AR')-
OP(O)(AR3)2;
-R''-A-P(O)(AR')-OP(0)(AR3)-OP(O)(AR3)~: -R'P(~)(AR3)2; or -RZ-AP(AR');
wherein A has the
same meaning as above, each R2 multivalent linking group is independently is
selected from an
alkyl or alkyl hydroxy group having four carbons or less; and each R3 is
selected from hydrogen
CA 02488839 2004-12-02
or a hydrocabon having less than 30 atoms, with preferred groups including
CH3, CHzCH~, alkyl,
alkylene oxide or alkyl hydroxy groups with less than 8 carbons, or hydrocabon
groups derived
from fatty acids. including but not limited to tallow, hardened tallow,
stearic, canola, or oleic. At
least one R' must be selected from the group consisting of -Rz-A-P(O)(AR3)z, -
Rz-A-P(O)(AR3)-
OP(O)(AR3)z, -Rz-A-P(O)(AR3)-OP(O)(AR3)-OP(O)(AR3)z, -RzP(O)(AR3)z, and -Rz-
AP(AR3).
When x is 4, the nitrogen has a positive charge and the positive charge is
counterbalance by an
anionic counterion or by the phosphate, phosphite or phosphonate group.
Some non-limiting preferred structures fitting the criteria of Structure 6
above are:
CH2CH20IP(OCH2CH3)z CH CH OIP(OH CH CH OIP OCH CH
z z )z z 2 ( 2 3)2
O O
H3C-N~ CH2CH20P(OCH2CH3)2
H3C-N-CH2CHZOP(OH)y N-CH2CHZOP(OCH2CH3)z
CHZCH20P(OCNzCH3)2
CH2CH20I, (0H)2 CH2CH20ii (OCHZCH3)2
O O
c~
x I+ x
~(~hvi3 I~ Ii C~ ~O(~zChm3
OP(OCI-~CIi3~
oP(oc~cH~h ~.y I ., x
H3C'(' 1C)11/13 N~ O
~~o~P(ocr~cH3)z oll(oc~cH~
OH
O
O
NHCf~ Q
+ X O~Ra
~P OC + x
CI-~ ( ~H3)2 O N O . x
0
R4CIH~C~ OIP(OH~ R4CI~~H~O~IOC!-i~CH3y~
O O I(
NHCI~ O~I R4 NHCRQ
x
O + O
x + X
H I~OIP(OCF~CH-~
F~CH~C~OP(OI-I~ R4CO~CH~OP(OH)2
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OI~ORo OIP,OF~ O~ORa
~OEt ~OEt '\OEt
O
x N x
ICO-J I~OIPOC C " ~I II c~II~I~OIP(OCI~CH3)z
Ra CH3 ( ~ ~)z R4CH~C~ OP(OCt~CH3)z o
OI~ORa OI~O~t OIP/OR4
OEi h'\OC~ ~pCH3
x
0 0
dII~I~OP(OCI-øCF~y~ ~~ /~ N+ x O~pp--~~pIP(OCI-4~y~
o R4CH~~~OP(OCI~)2 R, Io
O N
O CH3 H3C3 ~N + Op~~OH Ra--
RaPI N CH3 OP~OH \ORa N II
ORa X- ~~ ORa ~OP(OEt)2
O
O CI~ o H3 ,+
O 2 NCHZCHZOPOIP-O pl-(OC 'CHCHzN--R4 3+ 3X PI-OcHZ CHCH ~-(CHZ)3N~Rq)3
(RC C~ OH OH OH C OH CH3
HO~N~OH HO~iH~OH
N+
0
P(OEt)2 ~ P(OEt)
2
of II
° o
X
O O
CH3 CHg X
R4CIO~N~OCIR4 H3C-N
CH~O\
Ii (oEt)2 P(ORa)2
0
In the structures above, each Ra is chosen from hydrocarbon groups derived
from fatty
acids. Acceptable fatty acids can be linear or branched, and saturated or
unsaturated. Some non-
limiting preferred fatty acids include hardened tallow, stearic; canola, or
oleic. Each R4 can be the
same or different. Compounds that provide effective softening can be used as
partial or 100%
CA 02488839 2004-12-02
l~
replacement for the fabric softener actives described herein below. X is a
univalent or multi-
valent anion present in the correct amount necessary to balance the cationic
charge.
Structure 7
(R,)XN_Rs_N(R,)v
Structure 7 comprises two nitrogen moieties that can be neutral or protonated.
The value
of x + y is from 4 to 6. RS is a divalent linking group having 1 to about 8
carbons and selected
from alkyl, alkylene, alkylhydroxy, or alkylene oxide. Each R' is the same or
different and has the
same meaning as in Structure 6 above. At least one R' must be selected from
the group consisting
of -Rz-A-P(O)(~3)~~ -RZ-A-P(O)(~3)-OP(O)(AR3)z~ -RZ-A-P(O)(~3)-OP(O)(~3)_
OP(O)(AR3)z, -R'P(O)(AR3)2, or -RZ-AP(AR3) where A, Rz and R3 have the same
meaning as
described herein above for Structure 6. When x + y is 5., Structure 7 has a
positive charge. When x
+ y is 6, Structure 7 has two positive char=es and the compound is
counterbalanced by the
appropriate counterion(s) or by the phosphate, phosphonate or phosphite
groups.
Some non-limiting examples of structures fitting the criteria for Structure 7
above
include:
0
O
(H3CO~lPO
(HO)ZF~ O H3CHCHzC~ i P(OCH3)z
j i H3
i P(OH)y ~N~ /CHyCHCH3 2X
H3CHCHzC~ H3CHCH2C
~ ~N\ H2CHCH3 (H3C0)2 C 3CHzi HCH3
H3CH iQ
iH2C
(HO)zli0CHz i HCH3 l OiI(OCH3)2
O
O Oli(OH)2 O
O
II/OR4
OPT - ,P O
OCH3 H3 f
2X H3CHCHZC~ (OCH3)2
i i
/CHzCHCH3
N + CH H3CHCH2C
3
I ~ I -O~ i ~H CH2CHCH3
+ 3
CH3
O CH
H3C0/ OI R40~PIO Oil(OCH3)2
3 CH
3 O
CA 02488839 2004-12-02
~~~.OH O II/OCH2CH3
OP~O- II/OH OP~OCHzCH3 II/OCHZCH3
OP-O- OP-OCH2CH3
~- I ~ ~-N
CH3 i ~ CH3 N ~ CH3
Ro R. x.
Additional non-limiting examples of compounds comprising phosphorus and amine
include:
I I o II OH O (HacHZCq7z
OH
P(OH)z I .
II PI~OH ~P\O'Na' II P-0 II
PI(OH)z Iv P(OCHyCHa)z ~ P(OCHyCHa)z
P(OH)z ~ - ~O-Nd [
~ l O N2 ~
~ ~ ~
N~/ ~N \N~/ ~N N/~N~N,
/OH
~(OH)2 ~POCHCHa)2
(HO) \ ( z
PJ ~ ~ ~
2 ~NaO~ ' II
I I I (HaCHZCO)z i
II O-Ne
O II I
0 O O O O
0
I I
/P(OEt)z
~'
I
HO~N~
N
~OH
~Ii(OEt)y
O
wherein R~ and X have the same meaning as for Structure 6 herein above.
Polymers Containing Phosphorus
Phosphorus containing polymers useful for the present invention include the
polymeric
reaction products of alkylene amines or alkylene imines and phosphorus
moieties, such as -
((CHZ)xCH(NHz))y or -((CHZ)xCH2NH)y- , wherein x is zero or greater than zero
and y is greater
than 1. Nonlimiting examples include the reaction products of an alkylene
imine or alkylene
amine, such as ethylene imine or ethylene amine, with phosphoric acid, PC13,
PCOCI3, or
PCl(O)(OC2H5)~, or the reaction of already polymerized alkylene amines or
imines, such as the
reaction of polyethylene imine with phosphoric acid. PCl;, PCOCl3, or
PCl(O)(OCZHS)Z. Also
included are reactions of alkoxylated polyethylene imines with phosphoric
acid, PCl3, PCOC13, or
PCI(O)(OCZHS)~. Examples include:
CA 02488839 2004-12-02
12
~CH2CHpO~Y ~CHzCHpO~Y
Y OCHyCHZ \ ~ x I x
/N\ ~ ~ /N\ ~ ~CHyCHyO~Y
N/ ~ ~N~ ~N/ \ / x
IHZCHZ Y IHyCHyO Y (~ H2CH201---Y
x
Y
Y~ OCHZCH~
/x\N
Y~OCHZ~Hp~ ~CHpCHyO~Y
,x ~ x
~N~ ~ 'N\ ~ ~CHpCH20~Y
Y OCHZCHZI~/ ~ \ Nr ~ ~ \ /, 'N
~CH2CHpO~Y
~x
N\ ~ ~CHzCHzO~Y
\N/ \ ~ x
Y~OCHzCH2 ~CHpCHzO~Y
~x
N
~~ HzCH20~Y
~x
wherein x = 1-30 and Y is H, P(O)(OH)~, P(O)(OCH3)~, or P(O)(OCzHS)2,
Also included are phosphorus-containing alkoxylated polyammonium salts, such
as,
~ CHZCHzO~Y
Y~OCHyCH~ M x
N
N\ +
CHZCH20-~-Y
Y~ OCHzCHz x
x
wherein x = 1-30, Y is H, P(O)(OH)z, P(O)(OCH3)2, or P(O)(OC~HS)z, and M is a
suitable counter
ion such as Cl, Br; or CH3S04.
Phosphorus compounds containing carboxylic acids and esters can also be
utilized in the
present compositions as a flame retardant. Such compounds include:
a) homopolymers of ethylenically-a,(3-unsaturated dicarboxylates having the
formula:
CA 02488839 2004-12-02
13
X CH C P R
R~ R3 Q
x
Y
wherein each R is independently selected from H, OH. OM, or a unit having the
formula:
R2
CH C X
R~ R3
z
where X is independently selected from H, OH, or OS03M; R,, R2, R3 are
independently selected
from H, CH3, C, -C,~ alkyl, aryl, CO~M, or (CHZ)"CO~M, wherein n is from 1 to
about 4; M is H
or a salt-forming canon: the indices x, y, and z are each independently >_ 0,
preferably from 0 to
about 4; x + y + z is >_ 1; Q is H, OH, or OM, but not H when both x and z are
greater than or
equal to 1.
b) copolymers of ethylenically-a,(3-unsaturated dicarboxylates having the
formula:
X CH C P R
Rt R3 Q
x
Y
wherein each R is independently H, OH, OM, or a unit having the formula:
R2
CH C X
R~ R3
z
wherein X is independently selected from H, OH, or OS03M; R,, R2, R3 are
independently
selected from H, CH3, C, -C,z alkyl, aryl, CO~M, or (CHz)"CORM, wherein n is
from 1 to about 4;
M is H or a salt-forming cation; the indices x, y, and z are each
independently _> 0, preferably
fi-om 0 to about 4; x + y + z is > 1; Q is H, OH; or OM, but not H when both x
and z are greater
than or equal to 1.
CA 02488839 2004-12-02
14
c) copolymers of ethylenically-a,(3-unsaturated dicarboxylates polymerized
with vinyl-
containing monomers, wherein the copolymers have the formula:
I 2
X H H I R
L Ra R6 Q
x y
z
wherein each R is independently H, OH, OM, or a unit having the formula:
I2 I5
CH C CH C X
Ra
x y
wherein X is independently selected from H, OH, or OS03M; Rl, R2, R3 are
independently
selected from H, CH3, C, ~',~ alkyl, aryl, COZM, or (CHz)"COZM, where n is
from 1 to about 4;
R4_ R5, R6 are independently selected from H, alkyl, aryl, alkenyl; carboxy or
alkylcarboxy, esters.
functionalized esters, anhydride, amide, cyano, urea; alcohol, ether, acetal,
phosphino, phosphono,
sulfonate, sulfonamide, heterocycles (such as imidazole, thiol, thioester), or
mixtures thereof; the
indices x, y, and z are each independently >- 0, preferably from 0 to about 4;
x + y + z is >_ 1; Q is
H, OH, or OM, but not H when both x and z are greater than or equal to 1.
Structures of other suitable phosphorus-containing polymers are disclosed in
Encyclopedia of Polymer Science anal Engineering 2"d Ed., Vol. 11, Pages 96-
126, in the chapter
titled "Phosphorus C011ta1n111g Polymer" by E.D. Weil.
Suitable additional phosphorus-containing polymers include phosphonium salts
as shown
in Structure 8 below:
Structure 8
IR
RA- I AR
AR
wherein A and R have the same meanings as defined in the previous description
of
phosphoric acid and the phosphate salts herein. Acceptable compounds are
disclosed in the Kirk-
CA 02488839 2004-12-02
1$
Othmer Encyclopedia of Chemical Technology 4'~' Edition Vol. l 8 in the
chapter titled "Phosphine
and It's Derivatives" and the Ha~adbook of fiber Science and Technology; Vol.
II Chemical
Processing of Fibers and Fabrics Functional Finishes Part B, Eds. M. Lewin.
Tetrakis(hydroxymethyl)phosphonium (THP) salts are typical, but non-limiting
examples of
Structure 8. THP salts tend to react with other compounds containing active
hydrogens (e.g.
compounds comprising N-methylol, phenols, polybasic acid, and amines) to form
insoluble
polymers. Precondensate of THP salts with compounds containing active hydrogen
like urea,
melamine, and methylolated melamine are also useful for the present invention.
Non-limiting
examples of THP compounds useful as flame retardants in the present invention
are disclosed in
US 5.,688,429 and US 3.888,779. Some non-limiting commercially-available
materials are
Pyroset~ TPO, Pyroset~ TKOW, Pyroset~ TPC and Pyroset~ TKC available from
Cytec
);~dustries, Ine, Proban chemistry from Rhodia, Provatex type chemistry from
Ciba-Geigy.
Starch Com~risine a Phosphorus-Containing Substituent
Cationic starch comprising a phosphorus-containing substituent can be utilized
in the
present compositions as a flame retardant. Cationic starches, such as those
described in detail in
copending U.S. Application No. 60/457,448 (P&G Case 9178P), can be substituted
with a
phosphorus containing substituent, typically an ester or amide of ortho-, pyro-
, or tripoly-
phosphate. In the case of cationic phosphorylated starch, the preferred
cationic starches herein
will have a degree of substitution of cationic substitution plus phosphorus
substitution of from
about 0.01 to about 3, with the degree of cationic substitution ranging
typically from about 0.01 to
about 2.5, preferably from about 0.01 to about 1.5, and more preferably from
about 0.025 to about
0.5. When the cationic starch used herein is cationic maize starch, the
cationic starch preferably
has a degree of substitution of from about 0.04 to about 0.1.
The cationic starch with a phosphorus substituent in present invention can be
incorporated
into the composition in the form of intact starch granules, partially
gelatinized starch,
pregelatinized starch, cold water swelling starch, hydrolyzed starch (acid,
enzyme, alkaline
degradation), or oxidized starch (peroxide, peracid, alkaline; or any other
oxidizing agent). Fully
gelatinized starches can also be used, but at lower levels to prevent fabric
stiffness and limit
viscosity increases.
Non-limiting examples of the types of cationic starches with a phosphorus
containing
substituent that are useful for the present invention are disclosed in US
4,876,336.
Nonionic and ionic versions of phosphorylated starch are acceptable, but less
preferred
for the present fabric softening compositions disclosed herein. Such starches
can be equivalent in
structure to those disclosed above except these lack the cationic charges.
Some non-limiting
examples of such compounds are given in US 4,552,918 and US 5,244,474.
CA 02488839 2004-12-02
16
Polymers which contain saccharides or polysaccharide units as graft co-
polymers, block
polymers, or pendant polymers that are then modified with a phosphate-
containing substituent as
in WO 02/070574 are also acceptable as flame retardants for the present
invention.
NITROGEN COMPOUNDS
Compounds containing only nitrogen functionality typically act independently
to provide
a flame retardancy effect. Melamine and its derivatives are exceptional
nitrogen compounds that
are swprisingly acceptable flame retardants for use in the present
compositions. Melamine salts of
phosphorus acids disclosed above are also acceptable flame retardants for use
in the present
compositions. Melamine and some non-limiting examples of melamine derivatives
acceptable as
flame retardants for the present invention are disclosed in US 4,197,373. Non-
limiting
commercially-available examples include Melapur~200 and Melapur~ P46.
HALOGENATED ORGANIC COMPOUNDS
Although organic compounds comprising fluorine, bromine, chlorine and iodine
are
acceptable flame retardants herein, brominated and chlorinated organic
compounds are preferred
because these halogenated organic compounds are the most effective for the
lowest cost.. A
variety of halogenated flame retardants are described in the Kirk-Othmer
Encyclopedia of
Chemical Technology 4''' Edition Vol. 10; Polymer Handbook, 2"d Ed. John Wiley
Sons, Inc.,
New York, 1975; International Plastics Handbook, Hanser Publishers, Munich,
Germany, 1990,
Flame Retardant Polymeric Materials, Plenum Press, New York, 1975, Bromine
Compounds
Chemistry and Applicatio~zs, Eds. D. Price, B. Iddon, B.J. Wakefield,
Elsevier, Amsterdam, the
Netherlands, 1988 and the Handbook of fiber Science and Technology: Vol. 1l
Chemical
Processing of Fibers and Fabrics Functional Finishes Part B, Eds. M. Lewin and
S.B. Sello,
"Chapter 1 Flame Retardance of Fabrics".
Suitable halogenated organic compounds suitable as flame retardants herein are
described
in US 6,008,283; US 5,565,538; US 5,484,839; US 5,438,096; US 5,296,306; US
5,290,636; US
5,100,986; US 5,066,752; US 5,041,484.
Some non-limiting commercially-available examples of acceptable halogenated
organic
flame retardants of the present invention include Doversperse~ A-1,
Doversperse~ 3, Chlorez~
700, 700-S, 725-S, 760, 700-DD, 700-DF, and 700-SS, Paroil 10, 152, 50, 142-A,
140, 170T, 170
HV, Doverguard~ 8207-A. all available from Dover Chemical Corporation. Other
examples are
commercially-available from Great Lakes Chemical Corp. under the trade names
DBSTM, PDBS-
80T"', FIREMASTER~ PBS-64, FIREMASTER~ CP-44B, GPP-36TM, PHT4~, PHT4-DiolT"',
PHT4-DioU70TM, DP-45TM, BA-59PTM, DE-83RTM, BC-52TM, BC-52HPT'", FF-680T~'.
CARBOXYLATE. POLYCARBOXYLATE. CARBONATE. AND
POLYCARBONATE FLAME RBTARDANT AGENTS
CA 02488839 2004-12-02
17
Compounds with one or more carboxylate or with groups and optionally nitrogen
functionality and free of phosphorus are useful to enhance the activity of the
flame retardants.
Polycarboxylate compounds free of phosphorus that are acceptable are disclosed
in copending
U.S. Application Serial Nos. 10/267;244, 10/267,301, and 10/267,294, published
as WO
03/33812, WO 03/33806, and WO 03/33811, respectively. Other polycarboxylate
compounds free
of phosphorus that are acceptable and some non-limiting examples are disclosed
in WO
00/29662; US 3,957,598; and US 3,957,598. Additional polycarboxylate compounds
and
especially polycarboxylate compounds comprising nitrogen and free of
phosphorus are disclosed
in Kirk-Othmer Encyclopedia of Chemical Technology 4"' Edition Vol. 5 in the
chapters titled
"Chelanting Agents" and "Carboxylic Acids" and also in Vol. 8 in the chapters
titled
"Dispersants" and "Dicarboxylic Acids", as well as acrylate structures and
polymers based on
mono-acrylate structures disclosed in Vol. 15 in the chapter titled "Latex
Technology". Non-
limiting examples include citric acid, 1,2,3,4-butanetetracarboxylic acid
(BTCA), malefic acid,
oxydisuccinic acid, succinic acid, ethylenediaminetetraacetic acid (EDTA); N-
dihydroxyethylglycine, tartaric acid, 5-sulfosalicylic acid,
hydroxyehtylethylenediaminetriacetic
acid (HEDTA), and (DTPA). Both the acid and salt forms of carboxylates are
acceptable for the
present invention, provided the salt form has a decomposition temperature less
than about 600°C.
Carbonate and polycarbonate materials acceptable for the present invention are
disclosed in Kirk-
Othmer Encyclopedia of Chemical Technology 42'' Edition in Vol. 5 in the
chapter title "Carbonic
and Carbonochloridic Esters", in Vol. 10 in the chapter titled "Flame
Retardants", and in Vol. 19
in the chapter titled "Polycarbonates". Both organic carbonates (e.g. propyl
carbonate) and metal
salts of carbonates (e.g. magnesium, carbonate) are acceptable for use in the
present invention.
Some non-limiting examples of carbonates are disclosed in US 3,909,490; US
3,917,559; US
4,506,046; and US 4,391,935.
Polycarboxylate compounds such as HEDTA and DPTA have been previously used in
compositions at low levels to scavenge trace amounts of heavy metals. When
used as a flame
retardant in the present compositions, these materials are used at a level of
at least about 0.05%,
preferably at least about 0.5%, and more preferably at least about 1%, by
weight of the
composition.
INORGANIC FLAME RETARDANTS
1) Compounds Comprisin Boron
Boron and compounds comprising boron can be used independently as flame
retardants
herein or in combination with halogen and halogen synergists, such as antimony
containing
compounds. Additionally, borates, such as sodium borate; are useful as agents
that can be
combined with other agents such as boric acid, cellulosic polymers. or alumina
trihydrate to form
CA 02488839 2004-12-02
18
glass-like substances with low transition temperature to inhibit cellulose
degradation. Perborate,
barium metaborate, and ammoniumfluoroborate are also acceptable flame
retardants herein.
Compounds comprising boron are effective as synergists for halogenated organic
compounds and
some boron containing materials. Compounds comprising boron and halogenated
organic
compounds are a preferred combination. Many examples of flame retardant
compounds that
comprise boron are described in the Kirk-Othmer Ea~c~%clopedia of Chemical
Technology 4'h
Edition Vol. 10.... and Handbook of Fiber Science and Technology: Vol. II
Chemical
Processing of Fibers and Fabrics Functional Finishes Part B, Eds. M. Lewin and
S.B. Sello,
"Chapter 1 Flame Retardance of Fabrics".
Some non-limiting boron-containing materials for use as flame retardants are
disclosed in
US 6;454,968; US 6,156,240; and US 3,837,903.
2) Miscellaneous Inorganic Compounds
Many inorganic salts and oxides are surprising found to provide a degree of
flame
retardancy acceptable for the present invention. Acceptable compounds comprise
antimony,
aluminum, bismuth, zinc, molybdenum, or tin, as well as sulfuric and sulfamic
acid salts. Non-
limiting examples include antimony oxides, antimony pentaoxide, metal
antimonates, aluminum
oxides, alumina trihydrate, compounds that comprise both alumina and
phosphorus, molybdic
oxides. ammonium octamolybdate, zinc molybdate, magnesium hydroxide, zinc
stannates, zinc
hydroxy stannate, and anunonium sulfamate. Alumina trihydrate makes a
preferred combination
when combined with a borate, preferably zinc borate, or a compound comprising
phosphorus.
Antimony and tin compounds, as well as zinc borate, can be synergists for halo-
organics,
especially those that dehalogenate easily (e.g. the nonliminting example of
hexabromocyclododecane). These materials used together with halo-organics
improve the flame
retardancy of halo-organics in liquid fabric softener compositions of the
present invention.
Some organo-silicates can be utilized as a flame retardant in the present
compositions. A
non-limiting example of a linear organo-silicate acceptable for the present
invention is disclosed
in US 6,454,969.
It is recognized that the present compositions can comprise mixtures of two or
more of
anv of the flame retardants described herein.
FABRIC SOFTENING ACTIVES
The present compositions can optionally further comprise a fabric softening
active.
Typical minimum levels of incorporation of the fabric softening active in the
present
compositions are at least about 2%, preferably at least about 5%, more
preferably at least about
10%, and even more preferably at least about 12%. by weight of the
composition, and the typical
maximum levels of incorporation of the fabric softening active in the present
compositions are
CA 02488839 2004-12-02
19
less than about 90%, preferably less than about 40%, more preferably less than
about 30% and
even more preferably less than about 20%, by weight of the composition.
In an embodiment of the present invention wherein the composition is free of a
flame
retardant, the present compositions comprise less than about 21%, by weight of
the composition,
of fabric softening active, and at least about 0.5%, by weight of the
composition, of a silicone
material.
Preferred Diester Quaternary Ammonium (DEOAI Compounds
The fabric softening active herein can preferably be a DEQA compound. The DEQA
compounds encompass a description of diamido fabrics softener actives as well
as fabric softener
actives with mixed amido and ester linkages.
A first type of DEQA ("DEQA (I)") suitable as a fabric softening active in the
present
compositions includes compounds of the formula:
~R4-m - N+ ' UCH2)n ' Y - Rl~mi X-
wherein each R substituent is either hydrogen, a short chain C1-C6, preferably
C1-C3 alkyl or
hydroxyalkyl group, e.g., methyl (most preferred), ethyl, propyl,
hydroxyethyl, and the like, poly
(C2_3 alkoxy), preferably polyethoxy, group, benzyl, or mixtures thereof; each
m is 2 or 3; each
n is from I to about 4, preferably 2; each Y is -O-(O)C-, -C(O)-O-, -NR-C(O)-,
or -C(O)-NR-
and it is acceptable for each Y to be the same or different; the sum of
carbons in each RI, plus
one when Y is -O-(O)C- or -NR-C(O) -, is C12-C22, preferably CI4-C20, mth each
RI being a
hydrocarbyl, or substituted hydrocarbyl group; it is acceptable for RI to be
unsaturated or
saturated and branched or linear and preferably it is linear; it is acceptable
for each RI to be the
same or different and preferably these are the same; and X- can be any
softener-compatible anion,
preferably, chloride, bromide, methylsulfate, ethylsulfate, sulfate,
phosphate, and nitrate, more
preferably chloride or methyl sulfate. Preferred DEQA compounds are typically
made by reacting
alkanolamines such as MDEA (methyldiethanolamine) and TEA (triethanolamine)
with fatty
acids. Some materials that typically result from such reactions include N,N-
di(acyl-oxyethyl)-
N,IV-dimethylammonium chloride or N;N-di(acyl-oxyethyl)-N,N-
methylhydroxyethylamrnonium
methylsulfate wherein the acyl group is derived from animal fats, unsaturated,
and
polyunsaturated, fatty acids. e.g., oleic acid, and/or partially hydrogenated
fatty acids, derived
from 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. lon-limiting examples
of suitable fatty acids are listed in US 5,759,990 at column 4; lines 45-66.
Those skilled in the art
will recognized that materials made from such process can comprise a
combination of mono-. di-.
CA 02488839 2004-12-02
and tri-esters depending on the process and the starting materials. Materials
from this group
prefen-ed for the present invention include those comprising a high Ievel of
diester content,
preferably more than 70% of the total active weight and more preferably at
least about 80% of the
total active weight (as used herein, the "percent of softener active"
containing a given RI group is
based upon taking a percentage of the total active based upon the percentage
that the given R1
group is. of the total R1 groups present.). Non-limiting examples of preferred
diester quats for the
present invention include N,N-di(tallowoyloxyethyl)-N,N-dimethylammonium
chloride (available
from Akzo under the trade name Armosoft~ DEQ) and N.N-di(canola-oyloxyethyl)-
N,N-
dimethylammonium chloride (available from Degussa under the trade name Adogen
CDMC).
Nonlimiting examples of available TEA ester quats suitable for the present
invention include di-
(hydrogenated taltowoyloxyethyl)-N;N-methylhydroxyethylammonium methylsulfate
and di-
(oleoyloxyethyl)-N,N-methylhydroxyethylammonium methylsulfate sold under the
trade names
Rewoquat~ WE 15 and Varisoft~ WE 16 ; both available from Degussa.
Additional preferred DEQA (1) actives include compounds comprising different Y
structures such as the those having the structure below where one Y = -C(O)-O-
and the other Y =
-NH-C(O)-:
Rr-C(O)O-R~-N+(RQ)n-R3-N(H)-C(O)-R' X-
wherein n is 1 or 2; R' is a C6-C22, preferably a C8-CZO, hydrocarbyl group or
substituted
hardrocarbyl groups that are branched or unbranched and saturated or
unsaturated; RZ and R3 are
each C,-C5, preferably C2-C3, alkyl or alkylene groups; and R° is H, or
a Cl-C3 alkyl or
hydroxyalkyI group. A non-limiting example of such softener is N-
tallowoyloxyethyl-N-
tallowoylaminopropyl methyl amine. Additional non-limiting examples of such
softeners are
described in US 5,580,481 and US 5,476,597.
Other suitable fabric softening actives include reaction products of fatty
acids with
dialkylenetriamines in, e.g., a molecular ratio of about 2:1; said reaction
products containing
compounds of the formula:
RI--~(O)--NH-R2 NH R3 NH--~(O)-RI
wherein R1, RZ are defined as above, and each R3 is a CI-6 alkylene group,
preferably an
ethylene group. Examples of these fabric softening actives are reaction
products of tallow acid,
canola acid. or oleic acids with diethylenetriamine in a molecular ratio of
about 2:1, said reaction
product mixture containing N,N"-ditallowoyldiethylenetriamine, N,N"-dicanola-
oyldiethylenetriamine, or N,N"-dioleoyldiethylenetriamine, respectively, with
the formula:
CA 02488839 2004-12-02
21
R1-C(O)-NH-CH2CH2-NH-CH2CH2-NH-C(O)-R1
wherein R2 and R3 are divalent ethylene groups , R1 is defined above and an
acceptable examples
of this structure when R1 is the oleoyl group of a commercially available
oleic acid derived from
a vegetable or animal source, include Emersol~ 223LL or Emersol~ 7021,
available from
Henkel Corporation.
Another fabric softening active for use in the present compositions has the
formula:
[R1-~(O~-~-R2 N(R)2-R3 NR--~(O~--Rl]+ X_
wherein R, R1, R2, R3 and X- are defined as above. Examples of this fabric
softening active are
the di-fatty amidoamines based softener having the formula:
[R1-C(O)-NH-CH2CH2-N(CH3)(CH2CH20H)-CH2CH2-NH-C(O)-R1]+ CH3S04-
wherein RI-C(O) is an oleoyl group, soft tallow group, or a hardened tallow
group available
commercially from Degussa under the trade names Varisoft~ 222LT, Varisoft~
222, and
Varisoft~ 110, respectively.
A second type of DEQA ("DEQA (2)") compound suitable as a fabric softening
active in
the present compositions has the general formula:
[R3N+CH2CH(YRI)(CH2YR1)] X_
wherein each Y, R, R1, and X- have the same meanings as before. Such compounds
include
those having the formula:
[CH3]3 N(+)[CH2CH(CH20(O)CR1)O(O)CR1] C1(-)
wherein each R is a methyl or ethyl group and preferably each R1 is in the
range of C15 to C19
As used herein, when the diester is specified, it can include the monoester
that is present. The
amount of monoester that can be present is the same as in DEQA (1).
These types of agents and general methods of making them are disclosed in U.S.
Pat. No.
4;137,180; vTaik et al., issued Jan. 30, 1979, which is incorporated herein by
reference. An
example of a preferred DEQA (2) is the "propyl" ester quaternary ammonium
fabric softener
active having the formula l,2-di(acyloxy)-3-trimethylammoniopropane chloride.
While it is acceptable to use fabric softening compounds with any transition
temperature:
preferably, for the present invention, the fabric softening compound has a
transition temperature
of equal to or less than about 50°C. While it is acceptable for fabric
softening compounds to be
CA 02488839 2004-12-02
22
made with fatty acid precursors with a range of Iodine Values (herein refer-ed
to as IV) from zero
to about 140, it is preferred for some aspects of the present invention to use
softening compounds
made with fatty acid precursors having an IV of at least about 40. These
aspects include, but are
not limited to, physical characteristics of the fabric softening composition
and static performance.
For other aspects of the present invention, an IV of about 1S to about 40 is
preferable to improve
the softening efficiency.
Fabric softening compositions of the present invention that are clear
preferably contain
highly fluid fabric softening actives with transition temperatures less than
about 35°C. These
materials can be made with fatty acid precursors having high IV (greater than
about SO) or
comprising branching or other structural modifications leading to a low
transition temperature.
Additionally when unsaturated fabric softener actives are used for clear
compositions the
unsaturated moiety preferably has a cisarans isomer ratio of at least 1:1,
preferably about 2:1,
more preferably about 3:1, and even more preferably 4:1 or higher. Some prefen-
ed actives for
clear compositions are disclosed in US 6.369,025; U.S. Application Serial No.
09/554,969, filed
Nov. 24, 1998 by Frankenbach et al. (WO 99/27050); and US 6,486,121.
While it is acceptable for the present invention for the composition to
contain a number of
softening actives, including other fabric softening actives disclosed herein
below, the DEQA
fabric softening actives, and specifically those fabric softener actives with
two ester linkages, are
preferred fabric softening actives for the present invention.
Other Fabric Softening Actives
Instead of, or in addition to, the DEQA fabric softening actives described
hereinbefore,
the present compositions can also comprise a variety of other fabric softening
actives. These other
suitable fabric softening actives include:
( 1 ) compounds having the formula:
~R4_m _ N(-i-) - R 1 m~ A_
wherein each m is 2 or 3, each Rl is a C6-C22, preferably C14-C20: but no more
than one being
less than about C12 and then the other is at least about 16, hydrocarbyl, or
substituted hydrocarbyl
substituent, preferably C10-C20 alkyl or alkenyl (unsaturated alkyl, including
polyunsaturated
alkyl, also referred to sometimes as "alkylene"), most preferably C12-Clg
alkyl or alkenyl, and
branch or unbranced. While it is acceptable for the N of the parent fatty acid
containing the Rl
group to range from zero to about I40, it is prefen-ed for the present
invention to have an IV of at
least about 40. When the fabric softener composition will be clear, it is
preferred for fabric
softner active to be highly fluid by incorporating branching in the
hydrocarbyl group by
CA 02488839 2004-12-02
23
incorporating high unsaturation e.g. the IV of a fatty acid containing this R1
group is from about
70 to about 140. more preferably from about 80 to about 130; and most
preferably from about 90
to about 1 l 5 (as used herein, the term "Iodine Value" means the Iodine Value
of a "parent" fatty
acid, or "corresponding" fatty acid, which is used to define a level of
unsaturation for an R1 group
that is the same as the level of unsaturation that would be present in a fatty
acid containing the
same Rl group) with, preferably, a cis/trans ratio as specified above for
highly unsaturated
compounds; each R is H or a short chain C1-C6, preferably CI-C3 alkyl or
hydroxyalkyl group,
e.g., methyl (most prefewed), ethyl, propyl, hydroxyethyl, and the like,
benzyl, or (R2 O)2_4H
where each R2 is a C1_6 alkylene group; and A- is a softener compatible anion,
preferably,
chloride, bromide, methylsulfate, ethylsulfate, sulfate, phosphate, or
nitrate; more preferably
chloride or methyl sulfate. Examples of these fabric softening actives include
dialkydimethylammonium salts and dialkylenedimethylannnonium salts such as
ditallowdimethylammonium chloride, dicanoladimethylammonium chloride, and
dicanoladimethylammonium methylsulfate. Examples of commercially available
dialkylenedimeihylammonium salts usable in the present invention are di-
hydrogenated tallow
dimethyl ammonium chloride, ditallowdimethyl ammonium chloride, and
dioleyldimethylammonium chloride available from Degussa under the trade names
Adogen~ 442,
Adogen~ 470; and Adogen~ 472, respectively.
CA 02488839 2004-12-02
24
(2) compounds having the formula
1 ~ N CH2 _
G R C I A
N+ CH2
Rl C G R2/ \
R
wherein each R, R1, and A- have the definitions given above; each R2 is a C1-6
allcylene group,
preferably an ethylene group; and G is an oxygen atom or an -IVR- group.
Examples of this fabric
softening active are 1-methyl-1-tallowylamidoethyl-2-oleylimidazolinium
methylsulfate and 1-
methyl-1-oleylamidoethyl-2-oleylimidazolinium methylsulfate wherein Rl is an
acyclic aliphatic
C15-C1~ hydrocarbon group, R2 is an ethylene group, G is a NH group, RS is a
methyl group and
A' is a methyl sulfate anion, available commercially from Degussa under the
trade names
Varisoft~ 475 and Varisoft~ 3690, respectively.
(3) compounds having the formula:
N-CH2
R'-~
N-CH2
RI-C-G-R
wherein R1, R2 and G are defined as above. An example of this fabric softening
active is 1-
oleylamidoethyl-2-oleylimidazoline wherein R1 is an acyclic aliphatic C15-C1~
hydrocarbon
group, R2 is an ethylene group, and G is a NH group.
(4) reaction products of substantially unsaturated and/or branched chain
higher fatty
acid with hydroxyalkylalkylenediamines in a molecular ratio of about 2:1, said
reaction products
containing compounds of the formula:
R 1-C(O)-NH_R2_N(R30H)-C(O)_R 1
wherein R1, R2 and R3 are defined as above. Examples of this fabric softening
active are reaction
products of fatty acids such as tallow fatty acid, oleic fatty acid, or canola
fatty acid with N-2-
hydroxye.thylethylenediamine in a molecular ratio of about 2:1, said reaction
product mixture
containing a compound of the formula:
CA 02488839 2004-12-02
R 1-C(O)-NH-CH2CH2-N(CH2CH20H)-C(O)-R 1
wherein R1-C(O) is oleoyl, tallowyl, or canola-oyl group of a commercially
available fatty acid
derived from a vegetable or animal source. Nonlimiting examples of such
actives include
Emersol~ 223LL or Emersol~ 7021, which are derived from oleic acid and
available from
Henkel Corporation.
(5) compounds having the formula:
R R
N-R2-N
N~ N 2A0
Rl Rl
wherein R, R1, R2, and A- are defined as above.
Other compounds suitable as fabric softening actives herein are acyclic
quaternary
ammonium salts having the formula:
~R1 N(RS)2_R6~+ A_
wherein RS and R6 are C1-C4 alkyl or hydroxyalkyl groups, and R1 and A- are
defined as herein
above. Examples of these fabric softening actives are the
monoalkyltrimethylammonium salts and
the monoalkenyltrimethylammonium salts such as monotallowyltrimethylammonium
chloride,
monostearyltrimethylammonium chloride, monooleyltrimethylammonium chloride,
and
monocanolatrimethylammonium chloride. Commercial examples include
tallowtrimetylammonium chloride and soyatrimethylammonium chloride available
from Degussa
under the trade names Adogen~ 471 and Adogen° 415.
(6) substituted imidazolinium salts having the formula:
O
N-CHZ
R~-C AO
N-CH2
R~~ ~ H
CA 02488839 2004-12-02
26
wherein R7 is hydrogen or a C1-C4 saturated alkyl or hydroxyalkyl group, and
R1 and A- are
defined as hereinabove;
(7) substituted imidazolinium salts having the formula:
_ O+
RFC N CH2 Ao
N-CH2
HO-R2~ \R5
wherein RS is a C1-C4 alkyl or hydroxyalkyl group, and Rl, R2, and A- are as
defined above;
(8) alkylpyridinium salts having the formula:
O+
R4_N ~ AO
wherein R4 is an acyclic aliphatic Cg-C22 hydrocarbon group and A- is an
anion. An example of
this fabric softening active is 1-ethyl-1-(2-hydroxyethyl)-2-
isoheptadecylimidazolinium
ethylsulfate wherein R1 is a C17 hydrocarbon group, R2 is an ethylene group,
RS is an ethyl
group, and A- is an ethylsulfate anion.
(9) alkanamide alkylene pyridinium salts having the formula:
O+
Rl-C-NH-R2-N O A~
wherein R1, R2 and A- are defined as herein above; and mixtures thereof.
Other suitable fabric softening actives for use in the present compositions
include
pentaerythritol compounds. Such compounds are disclosed in more detail in,
e.g., US 6,492,322
US 6,194,374; US 5;358,647; US 5,332,513, US 5;290,459; US 5,750,990, US
5,830,845 US
5,460,736 and US 5,126,060.
Polyquaternary ammonium compounds can also be useful as fabric softening
actives in
the present compositions and are described in more detail in the following
patent documents: EP
CA 02488839 2004-12-02
27
803,498; GB 808.265; GB 1,161,552; DE 4;203,489; EP 221,855; EP 503,155; EP
507.003; EP
803,498; FR 2,523;606; JP 84-273918; JP 2-011,545; US 3,079,436; US 4,418,054;
US
4,721,512; US 4,728,337; US 4,906,413; US 5,194;667; US 5,235,082; US
5,670,472; Weirong
Miao, Wei Hou, Lie Chen, and Zongshi Li, Studies on Multifunctional FinishinE
Agents, Riyong
Huaxue Gonye, No. 2, pp. 8-10, 1992; Yokaeaku, Vol. 41, No. 4 (1992); and
Disinfection,
Sterilization, and Preservation, 4"' Edition, published 1991 by Lea & FebiQer,
Chapter 13, pp.
226-30. The products formed by quaternization of reaction products of fatty
acid with N,N,N',N',
tetraakis(hydroxyethyl)-1,6-diaminohexane are also suitable for use in the
present invention.
Examples of ester and/or amide linked fabric softening actives useful in the
present
invention, especially for concentrated clear compositions, are disclosed in US
5,759,990 and US
5,747,443. Other fabric softening actives for clear liquid fabric softening
compositions are
described in US 6,323.172.
Examples of suitable amine softeners that can be used in the present invention
as fabric
softening actives are disclosed in copending U.S. Application Serial No.
09/463,103, filed Jul. 29,
1997, by Grimm et al., now allowed.
Other suitable fabric softening actives; especially for the present liquid
fabric softening
compositions, include phosphate quaternary compounds as described in US
4;503,002.
Other fabric softening actives that can be used herein are disclosed, at least
generically for
the basic structures, in US 3,861,870; US 4,308,151; US 3,886,075; US
4;233,164; US 4,401,578;
US 3,974,076; and US 4,237,016. Examples of more biodegradable fabric
softeners can be found
in US 3,408,361; US 4,709,045; US 4,233,451; US 4,127,489; US 3,689.424; US
4,128,485; US
4,161,604; US 4,189,593; and US 4,339,391.
The fabric softening active in the present compositions is preferably selected
from the
group consisting of ditallowoyloxyethyl dimethyl ammonium chloride,
dihydrogenated-
tallowoyloxyethyl dimethyl ammonium chloride, dicanola-oyloxyethyl dimethyl
ammonium
chloride, ditallow dimethyl ammonium chloride, tritallow methyl ammonium
chloride, methyl
bis(tallow amidoethyl)2-hydroxyethyl ammonium methyl sulfate, methyl
bis(hydrogenated tallow
amidoethyl)-2-hydroxyethyl ammonim methyl sulfate, methyl bis (oleyl
amidoethyl)-2-
hydroxyethyl ammonium methyl sulfate, ditallowoyloxyethyl dimethyl ammonium
methyl
sulfate, dihydrogenated-tallowoyloxyethyl dimethyl ammonium chloride, dicanola-
oyloxyethyl
dimethyl ammonium chloride, N-tallowoyloxyethyl-N-tallowoylaminopropyl methyl
amine, 1,2-
bis(hardened tallowoyloxy)-3-trimethylammonium propane chloride, and mixtures
thereof.
It will be understood that all combinations of fabric softening actives
disclosed above are
suitable for use in this invention.
CA 02488839 2004-12-02
2 ~
SILICONE MATERIALS
To boost the softening performance and other fabric benefits such as wrinkle
control,
appearance, and ease of ironing, of the present compositions, especially
compositions containing
only low levels of fabric softening actives (e.g. less than about 21% by
weight), silicone materials
such as silicone fluids and/or silicone emulsions can be optionally
incorporated in the present
compositions. In one embodiment of the invention, the present compositions
comprise less than
about 21%, by weight of the composition, of fabric softening active and at
least about 0.5%, by
weight of the composition. of a silicone material. When a silicone material is
used in the present
invention, it is typically used at a level of at least about 0.5%, preferably
at least about 3%, more
preferably at least about 5% and typically less than about 10%, preferably
less than about 8%, and
more preferably less than about 7%, by weight the composition.
The silicone material herein can be either a polydimethyl siloxane
(polydimethyl silicone
or PDMS), or a derivative thereof, e.g., amino silicones; ethoxylated
silicones. etc. The PDMS, is
preferably one with a high molecular weight, e.g.. one having a viscosity of
from about 1,000 to
about 1,000,000 cSt, preferably from about 10;000 to about 600,000 cSt, more
preferably from
about 60,000 to about 300,000 cSt. Silicone emulsions can conveniently be used
to prepare the
compositions of the present invention. However, preferably, the silicone is
one that is, at least
initially, not emulsified. Le.; the silicone should be emulsified in the
composition itself.
Silicone derivatives such as amino-functional silicones, quatemized silicones,
and silicone
derivatives containing Si--OH, Si--H, and/or Si--Cl bonds, can also be used.
Suitable silicone materials for incorporation in the present compositions
include those
described in WO 95/24460; US 6,335,315; US 6;251;850; US 6,358,913; and US
4,661,267.
AQUEOUS CARRIER
The present compositions will generally comprise an aqueous carrier comprising
water, at
a level of from about 0% to about 99%, by weight of the composition. When the
present
compositions are dilute liquid fabric softening compositions, the level of
aqueous carrier will
typically from about 40% to about 98%, preferably from about 70% to about 95%,
and more
preferably from about 60% to about 90%, by weight of the composition. When the
present
compositions are concentrated liquid fabric softening compositions, the level
of aqueous carrier
will typically from about 0% to about 40%, preferably from about 0% to about
30%, and more
preferably from about 0% to about 20%, by weight of the composition.
CATION1C STARCH (FREE OF PHOSPHORUS-CONTAINING SUBSTITUENTS)
The present compositions can optionally further comprise cationic starch that
is free of
phosphorus-containing substituents. These materials can provide additional
softness and other
desirable fabric conditioning benefits (such as wrinkle control, appearance,
anti-abrasion, and
CA 02488839 2004-12-02
29
ease of ironing), without noticeably decreasing the flame resistance of
treated fluffier fabrics, such
as terry fabrics and fleecy fabrics. "Cationic starch'' as used herein refers
to starch that has been
chemically modified to provide the starch with a net positive charge in
aqueous solution, such as
by the addition of amino and/or ammonium groups) into the starch molecules.
The starch can be
selected from the group consisting of tubers, legumes, cereal, and grains; for
example corn starch,
wheat starch, rice starch, waxy corn starch, oat starch; cassava starch, waxy
barley, waxy rice
starch, glutenous rice starch, sweet rice starch, amioca, potato starch,
tapioca starch, oat starch,
sago starch, sweet rice. and mixtures thereof. Preferred cationic starches for
use in the present
compositions include cationic maize starch, tapioca; and cationic potato
starch, with cationic
maize starch being especially preferred.
The cationic starch in present invention can contain more than one
modification in
addition to cationic. For instance, it is possible to use dual modified
starches such as cross-linked
and cationic, stabilized and cationic, and cross-linked, stabilized and
canonized starches.
Further, cationic starch in the present invention can be comprised of
maltodextrins,
having a Dextrose Equivalance ("DE") of from about 0 to about 35. The Dextrose
Equivalence
value is a measure of the reducing equivalence of the hydrolyzed starch
referenced to dextrose
and expressed as a percent (on dry basis). The higher the DE, the more
reducing sugar present.
Completely hydrolyzed starch to dextrose has a DE of 100, while unmodified
starch has a DE of
0. 1n addition to .maltodextrins, the cationic starch in the present invention
can be made from
dextrins. Dextrins are pyrolysis products of starch with a wide range of
molecular weights.
The compositions of the present invention generally comprise cationic starch
at a level of
from about 0.1% to about 5.0%, preferably from about 0.3% to about 3.0%, and
more preferably
from about 0.5% to about 2.0%; by weight of the composition.
The cationic starches of the present invention preferably have a particular
degree of
substitution. The "degree of substitution" of cationic starches is a measure
of the number of
hydroxyl groups on each anhydroglucose unit which are derivitised by
substituent groups. Since
each anhydroglucose unit has three potential hydroxyl groups available for
substitution, the
maximum possible degree of substitution is 3. The degree of substitution is
expressed as the
number of moles of substituent groups per mole of anhydroglucose unit, on a
molar average basis.
The degree of substitution can be determined using proton nuclear magnetic
resonance
spectroscopy ("'H NMR'') methods known in the an. The preferred cationic
starches herein will
have a degree of substitution of from about O.OI to about 2.5, preferably from
about 0.01 to about
1.5, and more preferably from about 0.025 to about 0.5. When the cationic
starch used herein is
cationic maize starch; the cationic starch preferably has a degree of
substitution of from about
0.04 to about 0.06.
CA 02488839 2004-12-02
Cationic starches made from native starches typically contain from about 20%
to about
30% amylose and from about 70% to about 80% amylopectin, by weight of the
cationic starch.
For example, cationic maize starch generally contains from about 0% to about
90% of amylose,
by weight of the cationic starch, depending upon the source of the starch,
while cationic starch
made from waxy maize starch generally contains about 100% amylopectin, by
weight of the
cationic starch. The preferred cationic starches of the present invention will
typically contain
amylose at a level of from about 0% to about 70%, preferably from about 10% to
about 60%, and
more preferably from about 15% to about 50%, by weight of the cationic starch.
When the
cationic starch used herein is cationic maize starch, the cationic starch
preferably comprises from
about 25% to about 30% amylose, by weight of the cationic starch.
The cationic starch in present invention can be incorporated into the
composition in the
form of intact starch granules, partially gelatinized starch, pregelatinized
starch, cold water
swelling starch, hydrolyzed starch (acid, enzyme; alkaline degradation), or
oxidized starch
(peroxide, peracid, alkaline, or any other oxidizing agent). Fully gelatinized
starches can also be
used, but at lower levels to prevent fabric stiffness and limit viscosity
increases.
The cationic starches of the present invention will also preferably contain
starch
components (e.g. amylose and/or amylopectin) having a particular molecular
weight. The
molecular weight of these cationic starch components is preferably from about
50,000 to about
10,000,000. The preferred cationic starches herein will preferably contain
starch components
having a molecular weight of from about 150,000 to about 7,000,000, more
preferably from about
250,000 to about 4,000,000, and even more preferably from about 400,000 to
about 3,000,000. As
used herein, the teen "molecular weight" refers to the weight average
molecular weight of the
cationic starch components. This weight average molecular weight can be
measured according to
the gel permeation chromatography ("GPC") method described in U.S. Application
Serial No.
10/062,393 filed February 1, 2002 by Mackey et al.
Suitable cationic starches for use in the present compositions are
commercially-available
from Cerestar under the trade name C*BOND~ and from National Starch and
Chemical Company
under the trade name CATO~ 2A.
ELECTROLYTE
Electrolyte is an optional, but preferred; additive for compositions of the
present
invention. Electrolyte is especially preferred in compositions comprising at
least 10% fabric
softening active, by weight. Electrolyte is preferably included in dispersion
compositions of the
present invention to achieve preferred viscosity of equal to or less than
about 2000 centipoise,
preferably less than about 200 centipoise. Electrolyte is preferably included
in clear compositions
to modify the viscosity/elasticity profile of the composition on dilution and
to provide lower
CA 02488839 2004-12-02
31
viscosity and/or elasticity to the composition itself. Additionally, for clear
compositions, the
electrolyte is a highly preferred additive enabling the use of lower solvent
levels to achieve an
economically feasible clear composition, while still maintaining a preferred
viscosity of equal to
or less than about 200 centipoise for the composition as well as providing
preferred lower
viscosity upon dilution.
Suitable electrolytes for incorporation in the present compositions include
inorganic salts.
Non-limiting examples of suitable inorganic salts include: MgIz, MgBr2, MgCl2,
Mg(N03)Z,
Mg3(P04)2, Mg2P20~, MgS04, magnesium silicate. IvTah NaBr, NaCI, NaF,
Na3(P04), NaS03,
Na~S04, Na~S03, NaNO;, NaI03, Na3(P04), Na4P~0~. sodium silicate, sodium
metasilicate,
sodium tetrachloroaluminate, sodium tripolyphosphate (STPP), Na2Si30~, sodium
zirconate, CaF2,
CaCh, CaBrz, CaIz, CaS04, Ca(N03)z, Ca, KI, KBr, KCI, KF, KN03, KI03, KZSO4,
K2S03,
K3(P04), K4(P20~), potassium pyrosulfate, potassium pyrosul~te, LiI, Liar,
LiCl, LiF, LiN03,
AIF3, AlCl3, AlBr3, AlI;, Al~(SO4)3, Al(P04), AI(N03)3, aluminum silicate;
including hydrates of
these salts and including combinations of these salts or salts with mixed
cations e.g. potassium
alum A1K(SO4)2 and salts with mixed anions, e.g. potassium
tetrachloroaluminate and sodium
tetrafluoroaluminate. Salts incorporating canons from groups IIIa, IVa, Va,
VIa, VIIa, VIII, Ib,
and IIb on the periodic chart with atomic numbers > 13 are also useful in
reducing dilution
viscosity but less prefen-ed due to their tendency to change oxidation states
and thus they can
adversely affect the odor or color of the formulation or lower weight
efficiency. Salts with
canons from group Ia or IIa with atomic numbers > 20 as well as salts with
canons from the
lactinide or actinide series are useful in reducing dilution viscosity, but
less preferred. Mixtures
of above salts are also useful.
Other suitable electrolytes for incorporation in the present compositions
include organic
salts. Non-limiting examples of suitable organic salts include, magnesium,
sodium, lithium,
potassium, zinc, and aluminum salts of the carboxylic acids including formate,
acetate,
proprionate, pelargonate, citrate, gluconate, lactate aromatic acids e.g.
benzoates, phenolate and
substituted benzoates or phenolates, such as phenolate, salicylate,
polyaromatic acids
terephthalates, and polyacids e.g. oxylate, adipate, succinate,
benzenedicarboxylate,
benzenetricarboxylate. Other useful organic salts include carbonate and/or
hydrogencarbonate
(HC03-') when the pH is suitable, alkyl and aromatic sulfates and sulfonates
e.g. sodium methyl
sulfate, benzene sulfonates and derivatives such as xylene sulfonate, and
amino acids when the
pH is suitable. Electrolytes can comprise mixed salts of the above, salts
neutralized with mixed
canons such as potassium/sodium tartrate, partially neutralized salts such as
sodium hydrogen
tartrate or potassium hydrogen phthalate, and salts comprising one canon with
mixed anions.
CA 02488839 2004-12-02
32
Generally, inorganic electrolytes are preferred over organic electrolytes for
better weight
efficiency and lower costs. Mixtures of inorganic and organic salts can be
used. Typical levels of
electrolyte in the compositions of the present invention are from about 0.001%
to about 10%, by
weight of the composition. Preferred levels of electrolyte for dispersion
compositions are
typically from about 0.001% to about 3%, preferably from about 0.01% to about
2%, and more
preferably from about 0.05% to about 1%. Preferred levels of electrolyte for
clear compositions
are from about 0.5% to about 5%, preferably from about 0.75% to about 2.5%,
and more
preferably from about 1% to about 2%, by weight of the composition.
PHASE STABILIZING POLYMERS
Optionally, the compositions herein further comprise from 0% to about 10%,
preferably
from about 0.1 % to about 5%, more preferably from about 0.1 % to about 2%, of
a phase
stabilizing polymer. Phase stabilizing polymers useful in the present
invention include
copolymeric blocks of terephthalate and polyethylene oxide or polypropylene
oxide, and the like.
Preferred phase stabilizing polymers comprising cationic functionalities are
disclosed in US
4,956,447.
A preferred phase stabilizing polymer is a copolymer having blocks of
terephthalate and
polyethylene oxide. More specifically, these polymers are comprised of
repeating units of
ethylene and/or propylene terephthalate and polyethylene oxide terephthalate
at a molar ratio of
ethylene terephthalate units to polyethylene oxide terephthalate units of from
about 25:75 to about
35:65, said polyethylene oxide terephthalate containing polyethylene oxide
blocks having
molecular weights of from about 300 to about 2000. The molecular weight of
this phase
stabilizing polymer is in the range of from about 5,000 to about 55,000.
Another preferred phase stabilizing polymer is a crystallizable polyester with
repeat units
of ethylene terephthalate units containing from about 10% to about 15% by
weight of ethylene
terephthalate units together with from about 10% to about 50% by weight of
polyoxyethylene
terephthalate units, derived from a polyoxyethylene glycol of average
molecular weight of from
about 300 to about 6,000, and the molar ratio of ethylene terephthalate units
to polyoxyethylene
terephthalate units in the crystallizable polymeric compound is between 2:1
and 6:1. Examples of
this polymer include the commercially available materials ZELCON~' 4780 (from
DuPont) and
MILEASE~ T (from ICI).
Highly preferred phase stabilizing polymers are described in more detail in US
5;574,179
at col. 14; line 66 to col. 15, line 67; in US 4,861,512; and in US 4,702,857.
ADJUNCT INGREDIENTS
The present compositions optionally, but preferably, comprise additional
adjunct
ingredients, preferably selected from the group consisting of perfume,
nonionic surfactant, non-
CA 02488839 2004-12-02
33
aqueous solvent, fatty acid, dye, preservatives, optical brighteners; antifoam
agents, and mixtures
thereof. The amount of each optional adjunct ingredient is typically up to
about 2.0%, by weight
of the composition, unless otherwise specified.
The present compositions preferably further comprise perfume. Perfume is
typical
incorporated in the present compositions at a level of at least about 0.001%,
preferably at least
about 0.01%, more preferably at least about 0.1%, and no greater than about
10%, preferably no
greater than about S%, more preferably no greater than about 3%, by weight of
the composition.
The present compositions can optionally further comprise a nonionic
surfactant. The
nonionic surfactant is preferably an alkoxylated nonionic surfactant,
especially an ethoxylated
nonionic surfactant. Suitable nonionic surfactants further include nonionic
surfactants derived
from saturated and/or unsaturated primary, secondary, and/or branched, amine,
amide, amine-
oxide fatty alcohol, fatty acid. alkyl phenol, and/or alkyl aryl carboxylic
acid compounds, each
preferably having from about 6 to about 22, more preferably from about 8 to
about 18, carbon
atoms in a hydrophobic chain, more preferably an alkyl or alkylene chain,
wherein at least one
active hydrogen of said compounds is ethoxylated with <_ 50, preferably <_ 30,
more preferably
from about 5 to about 15, and even more preferably from about 8 to about 12,
ethylene oxide
moieties to provide an HLB of from about 8 to about 20, preferably from about
10 to about 18,
and more preferably from about 11 to about 15. Suitable nonionic surfactants
are described in
more detail in US 6,514,931 at col. 8, lines 1-24; US 6,492,322; and U.S.
Application Serial No.
09/554;969, filed Nov. 24, 1998 by Frankenbach et al. (WO 99/27050). When
present, nonionic
surfactants are typically present in the compositions at a level of from about
0.01% to about 5%,
preferably from about 0.05% to about 3%, and more preferably from about 0.1%
to about 2%, by
weight of the composition. Suitable nonionic surfactants include those
commercially-available
from Shell Chemicals under the trade name NEODOL~ 91-8 and from BASF under the
trade
name PLURONIC~ L35.
The present compositions can optionally further comprise solvents. Suitable
solvents can
be water-soluble or water-insoluble and can include ethanol, propanol,
isopropanol, n-butanol, t-
butanol, propylene glycol, ethylene glycol, dipropylene glycol, propylene
carbonate, butyl
carbitol, phenylethyl alcohol, 2-methyl 1,3-propanediol, hexylene glycol,
glycerol, polyethylene
glycol, 1;2-hexanediol, 1,2-pentanediol, 1,2-butanediol, 1,4-cyclohexanediol,
pinacol, 1,5-
hexanediol, 1,6-hexanediol, 2,4-dimethyl-2,4-pentanedioL 2,2,4-trimethyl-1,3-
pentanediol, 2-
ethyl-1;3-hexanediol, phenoxyethanol, or mixtures thereof. Solvents are
typically incorporated in
the present compositions at a level of less than about 40%, preferably from
about 0.5% to about
25%; more preferably from about 1% to about 10%. by weight of the composition.
Preferred
solvents, especially for clear compositions herein, have a ClogP of from about
-2.0 to about 2.6,
CA 02488839 2004-12-02
34
preferably from about -1.7 to about 1.6, and more preferably from about -1.0
to about 1.0, which
are described in detail in U.S. Application Serial No. 09/554,969, filed Nov.
24, 1998 by
Frankenbach et al. (WO 99/27050).
The present compositions can optionally further comprise fatty acid. Suitable
fatty acids
include those containing from about 12 to about 25, preferably from about 13
to about 22, more
preferably from about 16 to about 20, total carbon atoms, with the fatty
moiety containing from
about 10 to about 22, preferably from about 10 to about 18, more preferably
from about 10 to
about 14 (mid cut), carbon atoms. The shorter moiety contains from about 1 to
about 4, preferably
from about 1 to about 2 carbon atoms.
While the present compositions can further comprise additional optional
components such
as oily sugar derivatives, such as those disclosed in WO 01/46361 and US
6,514,931, the
compositions are preferably free of these oily sugar derivatives. The present
compositions can
also further comprise optional anionic surfactants. However, if anionic
surfactants are present,
they are preferably included at a level of less than about 5%, preferably from
about 0.1% to about
l%, by weight of the composition. The present compositions can also be free of
anionic
surfactants.
The liquid fabric softener compositions of the present invention comprising an
effective
level of a flame retardant will typically increase the burn time of fluffier
fabrics treated with said
compositions by at least 10%, preferably by at least 20%, more preferably by
at least 50%, even
more preferably by at least 100%, still more preferably by at least 200%, and
most preferably by
at least 300% versus fluffier fabrics treated with liquid fabric softening
compositions without a
flame retardant.
Liquid fabric softener compositions comprising an effective level of a flame
retardant will
typically increase the burn time of fluffier fabrics treated with said
compositions by at least 1
second, preferably by at least 2 seconds, more preferably by at least 3
seconds, more preferably by
at least 5 seconds, and still more preferably by at least 10 seconds versus
fluffier fabrics treated
with liquid fabric softening compositions without a flame retardant.
A method of testing flame retardancy of fabrics is set forth in the Code of
Federal
Regulations, 16 C.F.R. ~ 1610, entitled "STANDARD FOR THE FLAMMABILITY OF
CLOTHING TEXTILES". Similar test methods include ASTM D1230-94 and AATCC 33-
1962.
The liquid fabric softening compositions of the present invention can be clear
or opaque
(dispersions) compositions. As used herein, "clear composition'' refers to
compositions that are
preferably substantially free of significant color or haze such that the
compositions generally
appear as clear as water. Of course one of ordinary skill in the art will
recognize that a small
amount of color and/or haze may be present in the compositions of the present
invention. The
CA 02488839 2004-12-02
present liquid fabric softening compositions can also be provided in a unit
dose fomn, for
example, as a liquid composition contained in a water-soluble film (e.g.
polyvinyl alcohol film).
The present compositions can also be solid compositions, such as solid fabric
softening
compositions incorporated onto a substrate for use in a laundry dryer as
described in US
5,503,756; US 5,476,599; US 5,578,234; and US 6,169,067.
The flame retardants described herein can also be incorporated in laundry
detergent
compositions, such as those described in detail in, e.g., US 5,981,466; US
5,916,862; US
5,565,145; US 4,537,706; US 4,515,705; and US 4,446,042.
The compositions of the present invention will typically have a viscosity of
less than
about 2000 centipoise, preferably less than about 500 centipoise, more
preferably less than about
200 centipoise, and even more preferably less than about 120 centipoise. For
purposes of the
present invention, the viscosities of the present compositions are measured at
25°C with a
Brookfield~ viscometer using a No. 2 spindle at 60 rpm.
The present compositions will generally have a pH of from about 2 to about 13,
preferably from about 2 to about 7, and more preferably from about 2 to about
5.
The present compositions can be made by mixing together the individual
components of
the composition to form a final finished liquid fabric softening composition
of the present
invention.
EXAMPLES
The following are non-limiting examples of the liquid fabric softening
compositions of
the present invention.
EXAMPLE
INGREDIENTS 1 2 3 4 ~ 5 6
Fabric Softening Active18.51% 18.51% 18.51% 14.50% --- ---
a
Fabric Softening Active--- --- --- --- 18.00% 18.00%
b
Fabric Softening Active--- --- --- --- 3.00% 3.00%
'
Cationic Starch d 0.84% 1.68% 2.52% 1.68% 1.68% 1.68%
Perfume 1.58% 1.28% 1.28% 1.58% 1.30% 1.30%
TMPD e --- --- --- --- 5.00% 5.00%
ODOL~ 91-8 f --- --- --- --- 2.15% 2.15%
PLURON1C~ L35 ~ --- --- --- --- 1.50% 2.00%
Phase Stabilizing 0.25% 0.25% 0.25% 0.25% --- ---
Polymer h
CA 02488839 2004-12-02
36
Calcium Chloride 0.545% 0.545% 0.545% 0.545% --- ---
Magnesium Chloride --- --- --- --- 2.00% 2.00%
DTPA' 0.005% 0.005% 0.005% 0.005% 0.20% 0.20%
Preservative ~ 7.5 ppm 7.5 7.5 ppm 7.5 --- ---
ppm ppm
tifoam k 0.011% 0.011% 0.011% 0.011% --- ---
ye 22 ppm 22 ppm 22 ppm 22 ppm 11 ppm 11 ppm
Ammonium Chloride 0.1% 0.3% 0.1% 0.1% --- ---
ydrochloric Acid --- --- --- --- --- 0.016%
Larne Retardant
Phosphoric Acid 0.042% 1% --- --- 0.042% ---
Tripolyphosphoric --- --- 0.42% --- --- ---
Acid
DEQUEST~ 2066' --- --- --- 3% 2% ---
DEQUEST~ 7000 "' --- --- --- --- --- 1.5%
Deionized Water Bal. Bal. Bal. Bal. Bal. Bal.
a N,N-di(tallowoyloxyethyl)-N,N-dimethylammonium chloride.
b N,N-di(canola-oyloxyethyl)-N,N-dimetlrylammonium chloride.
' Methyl bis(tallow amidoethyl)2-hydroxyethyl ammonium methyl sulfate.
Cationic starch based on common maize starch or potato starch, containing 25%
to 95% amylose and a
degree of substitution of from 0.02 to 0.09. Available from Cerestar under the
trade name C*BOND~ and
National Starch under the trade name CATO~ A2.
2,2,4-trimethyl-1,3-pentanediol.
f C9-C11 alkyl polyethylene oxide having nine EO groups.
E Polyoxypropylene-polyoxyethylene block copolymer with MW approx. = 2000.
Copolymer of ethylene oxide and terephthalate having the formula described in
US 5,574,179 at co1.15,
lines 1-5, wherein each X is methyl, each n is 40, a is 4, each R' is
essentially 1,4-phenylene moieties,
each Rz is essentially ethylene, 1,2-propylene moieties, or mixtures thereof.
' Diethylenetriaminepentaacetic acid.
i KATHON~ CG available from Rohm and Haas Co.
k Silicone antifoam agent available from Dow Corning Corp. under the trade
name DC2310.
~ Diethylenetriamine penta(methylene phosphoric acid).
"' 2-Phosphonobutane-1,2,4-tricarboxylic acid.
The following are non-limiting examples of the liquid fabric softening
compositions of
the present invention which are dispersion (opaque) compositions.
CA 02488839 2004-12-02
37
EXAMPLE
INGREDIENTS 7 8 9 10 11 12 13
Fabric Softening Active 24.7%24.7% 14% 14% 21% 21% 21%
a
Fabric Softening Active --- --- --- 2% --- --- ---
b
Cationic Starch ' --- --- 1.68% --- 1.68%--- 0.84%
Perfume 1-2% 1-2% 1-2% 1-2% 1-2% 1-2% 1-2%
base Stabilizing Polymer 0.25%0.25% 0.25% 0.25% 0.25%0.25% 0.25%
d
Dye 22 22 22 22 ppm 22 11 11 ppm
ppm ppm ppm ppm ppm
Ammonium Chloride 0.1% 0.1% 0.3% 0.1% 0.1% 0.1% 0.1%
lame Retardant
Phosphoric Acid --- --- --- 0.42% --- 0.042%---
DTPA ' 3% ___ ___ ___ ___ ___ ___
Citric Acid -__ ___ 3% ___ ___ ___ -__
ARLATONE~ MAP 230T-60 --- 2% --- --- --- --- ---
DEQUEST 2066 f --- --- --- --- 1% --- ---
iethyl bis (hydroxylethyl)amino --- ---
ethyl --- --- --- --- 1
hosphate
Fyrol~ 6 ~ ___ ___ ___ -__ ___ ___ 1.5%
eionized Water Bal. Bal. Bal. Bal. Bal. Bal. Bal.
a N,N-di(tallowoyloxyethyl)-N,N-dimethylanvnonium chloride.
b Methyl bis(tallow amidoethyl)2-hydroxyethyl arrunonium methyl sulfate.
' Cationic starch based on common maize starch or potato starch, containing
25% to 95% amylose and a
degree of substitution of from 0.02 to 0.09. Available from Cerestar under the
trade name C*BOND~ and
National Starch under the trade name CATO~ A2.
Copolymer of ethylene oxide and terephthalate having the formula described in
US 5,574,179 at co1.15,
lines 1-5, wherein each X is methyl, each n is 40, a is 4, each R' is
essentially 1,4-phenylene moieties,
each R'' is essentially ethylene, 1,2-propylene moieties, or mixtures thereof.
a Diethylenetriaminepentaacetic acid.
f Diethylenetriamine penta(methylene phosphonic acid).
Diethyl N,N, bis(hydoxylethyl)aminomethylphosphonate.
CA 02488839 2004-12-02
38
The following are non-limiting examples of the liquid fabric softening
compositions of
the present invention which are clear compositions.
EXAMPLE
INGREDIENTS 14 15 16 17 18 19
Fabric Softening 12% 12% 12% 18% 30% 35%
Active a
Fabric Softening 3% 3% 3% 7% --- ---
Active
TMPD ' 10% 7.7% 7.6% 2% 3% 3%
Neodol 91-8 6.6% 5% 4.5% 4% 4% 4.5%
Pluronic L-35 ' 1.2% 1.2% 1.2% 1% 1% 2%
MgCl2 2% 2% 2% 2% 2.2% 2.3%
DTPA' 0.02% 0.02% 0.02% 0.02% 0.02% 0.02%
Perfume 1-3% 1-3% 1-3% 1-3% 1-3% 1-3%
HCl 0.016% 0.016% 0.016% 0.016% 0.016% 0.016%
Dye 0.0011% 0.0011%0.0011% 0.0011%0.0011% 0.0011%
Flame Retardant
Fyrol~ 6 g 12% 9% 6% 9% 9% 10%
Deionized Water Bal. Bal. Bal. Bal. Bal. Bal.
a N,N-di(canola-oyloxyethyl)-N,N-dimethylammonium chloride.
b Methyl bis(tallow amidoethyl)2-hydroxyethyl ammonium methyl sulfate.
' 2,2,4-trimethyl-1,3-pentanediol.
d C9-C11 alkyl polyethylene oxide having nine EO groups.
a Polyoxypropylene-polyoxyethylene block copolymer with MW approx. = 2000.
f Diethylenetriaminepentaacetic acid.
Diethyl N,N bis(hydroxyethyl)aminomethyl phosphonate.
The following are non-limiting examples of the liquid fabric softening
compositions of
the present invention which comprise cationic phosphorylated starch as a flame
retardant.
EXAMPLE
INGREDIENTS 20 21 22 23 24 25
Fabric Softening Active18.51 l 8.51 18.51 14.50% --- ---
a % % %
abric Softening Active--- --- --- --- 18.00% 18.00%
b
Fabric Softening Active--- --- --- --- 3.00% 3.00%
'
CA 02488839 2004-12-02
39
Cationic Phosphorylated--- --- 2.52% --- --- 1.68%
Starch d
Cationic Phosphorylated0.84% 1.68% --- 1.68% 1.68% ---
Starch a
erfume 1.58% 1.28% 1.28% 1.58% 1.30% 1.30%
TMPD f --- --- --- --- 5.00% 5.00%
ODOL~' 91-8 g --- --- --- -- 2.15% 2.15%
PLURON1C~ L35 " --- --- --- --- 1.50% 2.00%
hase Stabilizing Polymer'0.25% 0.25% 0.25% 0.25% --- ---
Calcium Chloride 0.545% 0.545% 0.545% 0.545% --- ---
agnesium Chloride --- --- --- --- 2.00% 2.00%
DTPA' 0.005% 0.005% 0.005% 0.005% 0.20% 0.20%
reservative'' 7.5 7.5 ppm 7.5 7.5 ppm --- ---
ppm ppm
Antifoam' 0.011% 0.011% 0.011% 0.011% --- ---
ye 22 ppm 22 ppm 22 ppm 22 ppm 11 ppm 11 ppm
mmonium Chloride 0.1% 0.3% 0.1% 0.1% --- ---
Hydrochloric Acid --- --- --- --- --- 0.016%
eionized Water Bal. Bal. Bal. Bal. Bal. Bal.
a N,N-di(tallowoyloxyethyl)-N,N-dimethylammonium chloride.
" N,N-di(canola-oyloxyethyl)-N,N-dimethylammonium chloride.
' Methyl bis(tallow amidoethyl)2-hydroxyethyl ammonium methyl sulfate.
d Cationic phosphorylated starch based on common potato prepared as disclosed
in US 4,876,336, Table II,
sample A.
a Cationic phosphorylated starch based on common potato prepared as disclosed
in US 4,876,336, Table II,
sample F.
f 2,2,4-trimethyl-1,3-pentanediol.
6 C9-C1 l alkyl polyethylene oxide having nine EO groups.
" Polyoxypropylene-polyoxyethylene block copolymer with MW approx. = 2000.
' Copolymer of ethylene oxide and terephthalate having the formula described
in US 5,574,179 at co1.15,
lines 1-5, wherein each X is methyl, each n is 40, a is 4, each R' is
essentially 1,4-phenylene moieties,
each R' is essentially ethylene, 1,2-propylene moieties, or nvxtures thereof.
Diethylenetriaminepentaacetic acid.
k KATHON~ CG available from Rohm and Haas Co.
~ Silicone antifoam agent available from Dow Coming Cotp. under the trade name
DC2310.
CA 02488839 2004-12-02
The following are non-limiting examples of the liquid fabric softening
compositions of
the present invention which comprise a phosphotylated fabric softening active
that can be utilized
as a flame retardant.
EXAMPLE
INGREDIENTS 26 27 28 29 30 31
abric Softening Active18.5% --- --- --- -- ---
a
Fabric Softening Active--- 18.5% --- --- 9% --
b
Fabric Softening Active--- --- 18.5% --- -- --
'
Fabric Softening Active--- -- -- 18.5% -- 9%
d
Fabric Softening Active--- -- -- -- 9% 9%
'
Cationic Starch f 0.84% 1.68% 2.52% 1.68% 1.68% 1.68%
Perfume 1-2% 1-2% 1-2% 1-2% 1-2% 1-2%
Phase Stabilizing 0.25% 0.25% 0.25% 0.25% 0.25% 0.25%
Polymer ~
Calcium Chloride 0.545% 0.545% 0.545% 0.545% 0.545% 0.545%
DTPA" 0.005% 0.005% 0.005% 0.005% 0.20% 0.20%
reservative ' 7.5 7.5 ppm 7.5 7.5 ppm 7.5 7.5
ppm ppm ppm ppm
Antifoam' 0.011% 0.011% 0.011% 0.011% 0.011% 0.011%
Dye 22 ppm 22 ppm 22 ppm 22 ppm 11 ppm 11 ppm
Ammonium Chloride 0.1% 0.3% 0.1% 0.1% 0.1% 0.1%
Deionized Water Bal. Bal. Bal. Bal. Bal. Bal.
a N,N-di(tallowoyloxyethyl)-N-methyl-N-2-phosphorylethyl ammonium chloride.
" N,N-di(tallowoyloxyethyl)-N-methyl-N-2 phosphorylethyl methyl sulfate.
' N,N-ditallow amidoethyl-N-methyl-N-2-phosphorylethyl ammonium chloride.
d N,N-ditallow amidoethyl-N-methyl-N-2-phosphorylethyl ammonium methyl
sulfate.
N,N-di(tallowoyloxyethyl)-N,N-dimethylammonium chloride.
Cationic starch based on common maize starch or potato starch, containing 25%
to 95% amylose and a
degree of substitution of from 0.02 to 0.09. Available from Cerestar under the
trade name C*BOND~ and
National Starch under the trade name CATO~ A2.
Copolymer of ethylene oxide and terephthalate having the formula described in
US 5,574,179 at co1.15,
lines 1-5, wherein each X is methyl, each n is 40. a is 4, each R~ is
essentially 1,4-phenylene moieties,
each R2 is essentially etliylene, 1,2-propylene moieties, or mixtures thereof.
" Diethylenetrianunepentaacetic acid.
CA 02488839 2004-12-02
41
' KATHON~ CG available from Rohm and Haas Co.
' Silicone antifoam agent available from Dow Corning Corp. under the ri~ade
name DC2310.
EXAMPLE
INGREDIENTS 32 33 34 35 36 37
Arlasilk Phospholipid30% --- --- --- --- ---
EFA a
lasilk Phospholipid --- 24.7% 12.35 --- --- ---
PTC b
lasilk Phospholipid --- --- 12.35 24.7% 14% ---
PTS '
lasilk Phospholipid --- --- --- --- --- ---
PLN a
Lecithin ' --- --- --- --- 10% 24.7%
1,2-Hexanediol 10% --- --- --- --- ---
erfume 1-3% 1-2% 1-2% 1-2% 1-2% 1-2%
Calcium Chloride 0.545% 0.545% 0.545% 0.545% 0.545% 0.545%
DTPA f 0.005% 0.005% 0.005% 0.005% 0.20% 0.20%
eionized Water Bal. Bal. Bal. Bal. Bal. Bal.
a Linoleamidopropyl PG-dimonium chloride phosphate.
b Cocamidopropyl PG-dimonium chloride phosphate.
' Steramidopropyl PG-dimonium chloride phosphate.
Linoleamidopropyl PG-dimonium chloride phosphate.
a The phosphatidyl choline derived from soy-bean oil.
f Diethylenetriaminepentaacetic acid.
The following are non-limiting examples of the liquid fabric softening
compositions of
the present invention which comprise ethyl-capped phosphorylated fabric
softening actives that
can be utilized as flame retardants.
EXAMPLE
INGREDIENTS 38 39 40 41 42 43
Fabric Softening 18.5% --- --- --- -- ---
Active a
Fabric Softening --- 18.5% --- --- 9% --
Active b
Fabric Softening --- --- 18.5% --- -- --
Active '
Fabric Softening --- -- -- 18.5% -- 9%
Active d
CA 02488839 2004-12-02
42
Fabric Softening --- -- -- -- 9% 9%
Active e
Cationic Starch f 0.84% 1.68% 2.52% 1.68% 1.68% 1.68%
erfume 1-2% 1-2% 1-2% 1-2% 1-2% 1-2%
hase Stabilizing 0.25% 0.25% 0.25% 0.25% 0.25% 0.25%
Polymer ~
Calcium Chloride 0.545% 0.545% 0.545% 0.545% 0.545% 0.545%
DTPA h 0.005% 0.005% 0.005% 0.005% 0.20% 0.20%
Preservative' 7.5 ppm 7.5 7.5 ppm 7.5 7.5 7.5 ppm
ppm ppm ppm
Antifoam' 0.011% 0.011% 0.011% 0.011% 0.011% 0.011%
Dye 22 ppm 22 ppm 22 ppm 22 ppm 11 ppm 11 ppm
mmonium Chloride 0.1% 0.3% 0.1% 0.1% 0.1% 0.1%
eionized Water Bal. Bal. Bal. Bal. Bal. Bal.
a diethyl N,N-di(tallowoyloxyethyl)-N-methyl-N-2-phosphorylethyl ammonium
chloride.
b diethyl N,N-di(tallowoyloxyethyl)-N-methyl-N-2-phosphorylethyl methyl
sulfate.
diethyl N,N-ditallow amidoethyl-N-methyl-N-2-phosphorylethyl ammonium
chloride.
d diethyl N,N-ditallow anvdoethyl-N-methyl-N-2-phosphorylethyl ammonium methyl
sulfate.
a N,N-di(tallowoyloxyethyl)-N,N-dimethylammonium chloride.
f Cationic starch based on common maize starch or potato starch, containing
25% to 95% amylose and a
degree of substitution of from 0.02 to 0.09. Available from Cerestar under the
trade name C*BOND~ and
IvTational Starch under the ri-ade name CATO~ A2.
Copolymer of ethylene oxide and terephthalate having the formula described in
US 5,574,179 at co1.15,
lines 1-5, wherein each X is methyl, each n is 40, a is 4, each R' is
essentially 1,4-phenylene moieties,
each Rz is essentially ethylene, 1,2-propylene moieties, or nuxtures thereof.
h Diethylenetrianvnepentaacetic acid.
' KATHON~ CG available from Rohm and Haas Co.
' Silicone antifoam agent available from Dow Corning Coip. under the trade
name DC2310.
EXAMPLE
INGREDIENTS 44 45 46 47 48 49
abric Softening Active24.7% --- --- --- -- ---
a
Fabric Softening Active--- 24.7% --- --- 12.35% --
b
Fabric Softening Active--- --- 24.7 --- -- --
'
Fabric Softening Active--- -- -- 24.7% -- 12.35%
d
abric Softening Active--- -- -- -- 12.35% 12.35%
e
CA 02488839 2004-12-02
43
erfume 1-2% 1-2% 1-2% 1-2% 1-2% 1-2%
Phase Stabilizing 0.25% 0.25% 0.25% 0.25% 0.25% 0.25%
Polymer f
Calcium Chloride 0.545% 0.545% 0.545% 0.545% 0.545% 0.545%
DTPA g 0.005% 0.005% 0.005% 0.005% 0.20% 0.20%
Preservative h 7.5 ppm 7.5 7.5 ppm 7.5 7.5 7.5 ppm
ppm ppm ppm
tifoam' 0.011% 0.011% 0.011% 0.011% 0.011% 0.011%
ye 22 ppm 22 ppm 22 ppm 22 ppm I 1 11 ppm
ppm
Ammonium Chloride 0.1% 0.3% 0.1% 0.1% 0.1% 0.1%
Deionized Water Bal. Bal. Bal. Bal. Bal. Bal.
a Diethyl N,N-di(tallowoyloxyethyl)-N-methyl-N-2-phosphorylethyl ammonium
chloride.
b Diethyl N,N-di(tallowoyloxyethyl)-N-methyl-N-2-phosphorylethyl methyl
sulfate.
' Diethyl N,N-ditallow amidoethyl-N-methyl-N-2-phosphorylethyl anunonium
chloride.
d Diethyl N,N-ditallow amidoethyl-N-methyl-N-2-phosphorylethyl ammonium methyl
sulfate.
a N,N-di(tallowoyloxyethyl)-N,N-dimethylannnonium chloride.
f Copolymer of ethylene oxide and terephthalate having the formula described
in US 5,574,179 at co1.15,
lines 1-5, wherein each X is methyl, each n is 40, a is 4, each R' is
essentially 1,4-phenylene moieties,
each Rz is essentially ethylene, 1,2-propylene moieties, or mixtures thereof.
E Diethylenetriaminepentaacetic acid.
h KATHON~ CG available from Rohm and Haas Co.
' Silicone antifoam agent available from Dow Corning Corp. under the trade
name DC2310.
The following are non-limiting examples of the liquid fabric softening
compositions of
the present invention which comprise phosphonated fabric softening active that
can be utilized as
flame retardants.
EXAMPLE
INGREDIENTS 50 51 52 53 54 55
Fabric Softening 24.7% --- --- --- -- ---
Active a
Fabric Softening --- 24.7% --- --- 12.35% --
Active b
Fabric Softening --- --- 24.7 --- -- --
Active '
Fabric Softening --- -- -- 24.7% -- 12.35%
Active d
Fabric Softening --- -- -- -- 12.35% 12.35%
Active '
Perfume 1-2% 1-2% 1-2% 1-2% 1-2% 1-2%
CA 02488839 2004-12-02
44
Phase Stabilizing 0.25% 0.25% 0.25% 0.25% 0.25% 0.25%
Polymer f
Calcium Chloride 0.545% 0.545% 0.545% 0.545% 0.545% 0.545%
TPA g 0.005% 0.005% 0.005% 0.005% 0.20% 0.20%
Preservative " 7.5 ppm 7.5 7.5 ppm 7.5 7.5 7.5 ppm
ppm ppm ppm
tifoam' 0.011% 0.011% 0.011% 0.011% 0.011% 0.011%
ye 22 ppm 22 ppm 22 ppm 22 ppm 11 ppm 11 ppm
mmonium Chloride 0.1% 0.3% 0.1% 0.1% 0.1% 0.1%
eionized Water Bal. Bal. Bal. Bal. Bal. 8a1.
a Diethyl N,N-di(tallowoyloxyethyl)-N-methyl-N-ethyl-2-phosphonate ammonium
chloride.
b Diethyl N,N-di(tallowoyloxyethyl)-N-methyl-N-ethyl-2-phosphonate methyl
sulfate.
' Diethyl N,N-ditallow amidoethyl-N-methyl-N-ethyl-2-phosphonate ammonium
chloride.
d Diethyl N,N-ditallow anudoethyl-N-methyl-N-ethyl-2-phosphonate ammonium
methyl sulfate.
' N,N-di(tallowoyloxyethyl)-N,N-dimethylammonium chloride.
f Copolymer of ethylene oxide and terephthalate having the formula described
in US 5,574,179 at co1.15,
lines 1-5, wherein each X is methyl, each n is 40, a is 4, each R' is
essentially 1,4-phenylene moieties,
each Rz is essentially ethylene, 1,2-propylene moieties, or mixtures thereof.
b Diethylenetriaminepentaacetic acid.
" KATHON~ CG available from Rohm and Haas Co.
' Silicone antifoam agent available from Dow Corning Corp. under the trade
name DC2310.
EXAMPLE
INGREDIENTS 56 57 58 59 60 61
abric Softening Active18.5% --- --- --- -- ---
a
Fabric Softening Active"--- 18.5% --- --- 9% --
abric Softening Active--- --- 18.5% --- -- --
'
Fabric Softening Active--- -- -- 18.5% -- 9%
abric Softening Active--- -- -- -- 9% 9%
'
Cationic Starch f 0.84% l .68% 2.52% 1.68% 1.68% 1.68%
Perfume 1-2% 1-2% 1-2% 1-2% 1-2% 1-2%
hase Stabilizing Polymer0.25% 0.25% 0.25% 0.25% 0.25% 0.25%
~
Calcium Chloride 0.545% 0.545% 0.545% 0.545% 0.545% 0.545%
TPA" 0.005% 0.005% 0.005% 0.005% 0.20% 0.20%
Preservative' 7.5 7.5 ppm 7.5 7.5 ppm 7.5 7.5
ppm ppm ppm ppm
CA 02488839 2004-12-02
Antifoam' 0.011% 0.011% 0.011% 0.011% 0.011% 0.011%
Dye 22 ppm 22 ppm 22 ppm 22 ppm 11 ppm 11 ppm
Ammonium Chloride 0.1% 0.3% 0.1% 0.1% 0.1% 0.1%
Deionized Water Bal. Bal. Bal. Bal. Bal. Bal.
a Diethyl N,N-di(tallowoyloxyethyl)-N-methyl-N-methylphosphonate ammonium
chloride.
" Diethyl N,N-di(tallowoyloxyethyl)-N-methyl-N-methylphosphonate methyl
sulfate.
' Diethyl N,N-ditallow amidoethyl-N-methyl-N-methylphosphonate ammonium
chloride.
d Diethyl N,N-ditallow amidoethyl-N-methyl-N-methylphosphonate ammonium methyl
sulfate.
N,N-di(tallowoyloxyethyl)-N,N-dimethylammonium chloride.
Cationic starch based on common maize starch or potato starch, containing 25%
to 95% amylose and a
degree of substitution of from 0.02 to 0.09. Available from Cerestar under the
trade name C*BOND~ and
National Starch under the trade name CATO~ A2.
Copolymer of ethylene oxide and terephthalate having the formula described in
US 5,574,179 at co1.15,
lines 1-5, wherein each X is methyl, each n is 40, a is 4; each R' is
essentially 1,4-phenylene moieties,
each RZ is essentially ethylene, 1,2-propylene moieties, or nuxtures thereof.
" Diethylenetriaminepentaacetic acid.
' KATHON~ CG available from Rohm and Haas Co.
' Silicone antifoam agent available from Dow Corning Corp. under the trade
name DC2310.
The following are non-limiting examples of the liquid fabric softening
compositions of
the present invention which comprise sodium salts of phosphorylated fabric
softening actives that
can be utilized as flame retardants.
EXAMPLE
INGREDIENTS 62 63 64 65 66 67
Fabric Softening 18.5% --- --- --- -- ---
Active a
Fabric Softening --- l 8.5% --- --- 9% --
Active b
Fabric Softening --- --- 18.5% --- -- --
Active '
Fabric Softening --- -- -- 18.5% -- 9%
Active d
Fabric Softening --- -- -- -- 9% 9%
Active e
Cationic Starch f 0.84% 1.68% 2.52% 1.68% 1.68% 1.68%
Perfume I-2% 1-2% 1-2% I-2% 1-2% 1-2%
Phase Stabilizing 0.25% 0.25% 0.25% 0.25% 0.25% 0.25%
Polymer ~
CA 02488839 2004-12-02
46
Calcium Chloride 0.545% 0.545% 0.545% 0.545% 0.545% 0.545%
TPA h 0.005% 0.005% 0.005% 0.005% 0.20% 0.20%
Preservative' 7.5 ppm 7.5 7.5 ppm 7.5 7.5 7.5 ppm
ppm ppm ppm
Antifoam' 0.011% 0.011% 0.011% 0.011% 0.011% 0.011%
ye 22 ppm 22 ppm 22 ppm 22 ppm 11 ppm 11 ppm
mmonium Chloride 0.1% 0.3% 0.1% 0.1% 0.1% 0.1%
Deionized Water Bal. Bal. Bal. Bal. Bal. Bal.
' Disodium N,N-di(tallowoyloxyethyl)-N-methyl-N-2-phosphorylethyl ammonium
chloride.
Disodium N,N-di(tallowoyloxyethyl)-N-methyl-N-2-phosphorylethyl methyl
sulfate.
' Disodium N,N-ditallow amidoethyl-N-methyl-N-2-phosphorylethyl ammonium
chloride.
Disodium N,N-ditallow amidoethyl-N-methyl-N-2-phosphorylethyl ammonium methyl
sulfate.
N,N-di(tallowoyloxyethyl)-N,N-dimethylammonium chloride.
f Cationic starch based on common maize starch or potato starch, containing
25% to 95% amylose and a
degree of substitution of from 0.02 to 0.09. Available from Cerestar under the
trade name C*BOND~ and
National Starch under the trade name CATO~ A2.
s Copolymer of ethylene oxide and terephthalate having the formula described
in US 5,574,179 at co1.15,
lines 1-5, wherein each X is methyl, each n is 40, a is 4, each R~ is
essentially 1,4-phenylene moieties,
each RZ is essentially ethylene, 1,2-propylene moieties, or mixtures thereof.
h Diethylenetriaminepentaacetic acid.
' KATHON~ CG available from Rohm and Haas Co.
' Silicone antifoam agent available from Dow Corning Corp. under the trade
name DC2310.
The following are non-limiting examples of clear liquid fabric softening
compositions of
the present invention which comprise modified fabric softening actives that
can be utilized as
flame retardants.
EXAMPLE
INGREDIENTS 68 69 70 71 72 73
Fabric Softening 12% --- --- --- --- 35%
Active'
Fabric Softening --- 12% 25% 15% 30% ---
Active
Fabric Softening 3% --- --- --- --- ---
Active '
Fabric Softening --- 3% --- 5% --- --
Active
TMPD ' 7% 7% 7.2% 7% 7.5% 8%
Neodol9l-8' 6.6% 5% 5% 5% 5.2% 5.2%
CA 02488839 2004-12-02
47
Pluronic L-35 g 1.2% 1.2% 1.2% 1% 1% 2%
MgCl2 2% 2% 2% 2% 2.2% 2.3%
DTPA " 0.02% 0.02% 0.02% 0.02% 0.02% 0.02%
Perfume 1-3% 1-3% 1-3% 1-3% 1-3% 1-3%
HCl 0.016% 0.016% 0.016% 0.016% 0.016% 0.016%
Dye 0.0011%0.0011% 0.0011%0.0011% 0.0011%0.0011%
Deionized Water Bal. Bal. Bal. Bal. Bal. Bal.
a Diethyl N,N-di(canola-oxyethyl)-N-methyl-N-2-phosphorylethyl ammonium
chloride.
b Diethyl N,N-di(oleyloxyethyl)-N-methyl-N-2-phosphorylethyl methyl sulfate.
' Diethyl N,N-dicanola amidoethyl-N-methyl-N-2-phosphorylethyl ammonium
chloride.
d Diethyl N,N-oleyl amidoethyl-N-methyl-N-2-phosphorylethyl ammonium methyl
sulfate.
2,2,4-trimethyl-1,3-pentanediol.
f C9-C11 alkyl polyethylene oxide having nine EO groups.
polyoxypropylene-polyoxyethylene block copolymer with MW approx. = 2000.
'' Diethylenetriaminepentaacetic acid.
The following are non-limiting examples of clear liquid fabric softening
compositions of
the present invention which comprise modified fabric softening actives that
can be utilized as
flame retardants and a separate flame retardant.
EXAMPLE
INGREDIENTS 74 75 76 77 78 79
Fabric Softening 12% --- --- --- --- 35%
Active a
Fabric Softening --- 12% 25% 15% 30% ---
Active
Fabric Softening 3% --- --- --- --- ---
Active '
Fabric Softening --- 3% --- 5% --- --
Active
TMPD ' 3% 6% 6% 5% 7.5% 10%
Neodol 91-8 ' 6.6% 5% 5% 5% 5.2% 5.2%
Pluronic L-35 g 1.2% 1.2% 1.2% 1% 1% 2%
MgCl2 2% 2% 2% 2% 2.2% 2.3%
DTPA " 0.02% 0.02% 0.02% 0.02% 0.02% 0.02%
Perfume I-3% I-3% I-3% 1-3% 1-3% 1-3%
HCI 0.016% 0.016% 0.016% 0.016% 0.016% 0.016%
CA 02488839 2004-12-02
48
Dye 0.0011%0.0011% 0.0011%0.0011% 0.0011%0.0011%
Flame Retardant
Fyrol~ 6 ' 7% 5% 7% 8% 12% 15%
Deionized Water Bal. Bal. Bal. Bal. Bal. Bal.
a Diethyl N,N-di(canola-oxyethyl)-N-methyl-N-2-phosphorylethyammonium
chloride.
b Diethyl N,N-di(oleyloxyethyl)-N-methyl-N-2-phosphorylethymethyl sulfate.
' Diethyl N,N-dicanola anudoethyl-N-methyl-N-2-phosphorylethyammonium
chloride.
d Diethyl N,N-oleyl amidoethyl-N-methyl-N-2-phosphorylethyanunonium methyl
sulfate.
a 2,2,4-trimethyl-1,3-pentanediol.
f C9-CI I alkyl polyethylene oxide having nine EO groups.
Polyoxypropylene-polyoxyethylene block copolymer with MW approx. = 2000.
'' Diethyleneh-iaminepentaacetic acid.
' Diethyl bis(hydroxyehtyl)aminomethyl phosphonate.
The following are non-limiting examples of liquid fabric softening
compositions of the
present invention which comprise ethyl-capped phosphorylated fabric softening
actives that can
be utilized as flame retardants and a separate flame retardant.
EXAMPLE
INGREDIENTS 80 81 82 83 84 85
Fabric Softening 18.5% --- --- --- -- ---
Active a
Fabric Softening --- 18.5% --- --- 9% --
Active b
Fabric Softening --- --- 18.5% --- -- --
Active '
Fabric Softening --- -- -- 18.5% -- 9%
Active d
Fabric Softening --- -- -- -- 9% 9%
Active '
Cationic Starch f 0.84% 1.68% 2.52% 1.68% 1.68% 1.68%
Perfume 1-2% 1-2% 1-2% 1-2% 1-2% 1-2%
Phase Stabilizing 0.25% 0.25% 0.25% 0.25% 0.25% 0.25%
Polymer g
Calcium Chloride 0.545% 0.545% 0.545% 0.545% 0.545% 0.545%
DTPA h 0.005% 0.005% 0.005% 0.005% 0.20% 0.20%
Preservative' 7.5 ppm 7.5 ppm 7.5 7.5 ppm 7.5 7.5
ppm ppm ppm
Antifoam' 0.011% 0.011% 0.011% 0.011% 0.011% 0.011%
Dye 22 ppm 22 ppm 22 ppm 22 ppm 11 ppm 11 ppm
CA 02488839 2004-12-02
49
Ammonium Chloride 0.1% 0.3% 0.1% 0.1% 0.1% 0.1%
lame Retardant
Melamine phosphate 0.5% --- --- --- --- ---
Fyrol~6 ___ 0.75% 0.75% ___ ___ ___
Ammonium Phosphate --- --- --- 2.S% --- ---
Sodium tripolyphoshate--- --- --- --- 0.7% ---
Phosphoric Acid --- --- --- --- --- 1
Deionized Water Bal. Bal. Bal. Bal. Bal. Bal.
a Diethyl N,N-di(tallowoyloxyethyl)-N-methyl-N-2-phosphorylethyl ammonium
chloride.
° Diethyl N,N-di(tallowoyloxyethyl)-N-methyl-N-2-phosphorylethyl methyl
sulfate.
' Diethyl N,N-ditallow amidoethyl-N-methyl-N-2-phosphorylethyl ammonium
chloride.
d Diethyl N,N-ditallow amidoethyl-N-methyl-N-2-phosphorylethyl ammonium methyl
sulfate.
a N,N-di(tallowoyloxyethyl)-N,N-dimethylammonium chloride.
Cationic starch based on common maize starch or potato starch, containing 2S%
to 9S% amylose and a
degree of substitution of from 0.02 to 0.09. Available from Cerestar under the
trade name C*BOND~ and
National Starch under the trade name CATO~ A2.
Copolymer of ethylene oxide and terephthalate having the formula described in
US 5,574,179 at coLlS,
lines 1-S, wherein each X is methyl, each n is 40, a is 4, each R~ is
essentially 1,4-phenylene moieties,
each RZ is essentially ethylene, 1,2-propylene moieties, or mixtures thereof.
h Diethylenetriaminepentaacetic acid.
~ KATHON~ CG available from Rohm and Haas Co.
' Silicone antifoam agent available from Dow Corning Cotp. under the trade
name DC2310.
The following are non-limiting examples of fabric softening compositions
utilizing mono-
tail surfactants as flame retardants.
EXAMPLE
INGREDIENTS 86 87 88 89 90 91
Fabric Softening Active24.7% 18.51 14.50% 24.7% 18.51 14.50%
a % %
Phase Stabilizing 0.25% 0.25% 0.25% 0.25% 0.25% 0.25%
Polymer b
Calcium Chloride O.S4S% O.S4S% 0.545% O.S4S% O.S4S% O.S4S%
TPA ' O.OOS% 0.005% O.OOS% O.OOS% 0.20% 0.20%
Preservative a 7.S 7.S ppm 7.S 7.S ppm 7.S 7.S ppm
ppm ppm ppm
Antifoam a 0.011% 0.011% 0.011% 0.011% 0.011% O.OI
I%
Perfume 1-3% 1-3% 1-3% 1-3% 1-3% 1-3%
CA 02488839 2004-12-02
$0
lame Retandant
Phosphorylated surfactant12.3$% 9.2$ 7.2$ --- --- ---
f
Surfactant Phostphate--- --- --- 12.3$% 9.2$ 7.2$
g
a N,N-di(tallowoyloxyethyl)-N,N-dimethylammonium chloride.
Copolymer of ethylene oxide and terephthalate having the formula described in
US $,574,179 at col.l$,
lines 1-$, wherein each X is methyl, each n is 40, a is 4, each R' is
essentially 1,4-phenylene moieties,
each Rz is essentially ethylene, 1,2-propylene moieties, or mixtures thereof.
' Diethylenetriaminepentaacetic acid.
d KATHON~ CG available from Rohm and Haas Co.
Silicone antifoam agent available from Dow Corning Corp. under the trade name
DC2310.
f Dimethyl sulfate quat of dodecyl/tetradecyl methylethanolanvne diethyl
phosphate.
Arlatone0 MAP 230T-60 (TEA C12-13 alkyl phosphate) from Uniqema.
The following are non-limiting examples of fabric softening compositions
utilizing
lecithins as fabric softening actives can be a flame retardant.
EXAMPLE
INGREDIENTS 92 93 94 9$ 96 97
Lecithin 1 a 24.7% 18.$1% 14.$0% --- --- ---
Lecthin 2 b --- --- --- 24.7% 18.$1% 14.$0%
Phase Stabilizing 0.2$% 0.2$% 0.2$% 0.2$% 0.2$% 0.2$%
Polymer '
DTPA d 0.00$% 0.00$% 0.00$% 0.00$% 0.20% 0.20%
Preservative a 7.$ ppm 7.$ 7.$ ppm 7.$ 7.$ 7.$ ppm
ppm ppm ppm
Antifoam d 0.011% 0.011% 0.011% 0.011% 0.011% 0.011%
Perfume 1-3% 1-3% 1-3% 1-3% 1-3% 1-3%
a Ultralec P (Lecithin) from Archer Daniel Midland Co.
b Yelkin SS (Lecithin) from Archer Daniel Midland Co.
' Copolymer of ethylene oxide and terephthalate having the formula described
in US $,574,179 at col.l$,
lines I-$, wherein each X is methyl, each n is 40, a is 4; each R' is
essentially 1,4-phenylene moieties,
each RZ is essentially ethylene, 1;2-propylene moieties, or nuxtures thereof.
d Diethylenetriaminepentaacetic acid.
a KATHON~ CG available from Rolun and Haas Co.
f Silicone antifoam agent available from Dow Corning Corp. under the trade
name DC2310.
CA 02488839 2004-12-02
51
The following are non-limiting examples of solid fabric softening compositions
for
incorporation onto a substrate to form a fabric softening dryer sheet.
EXAMPLE
~
INGREDIENTS 98 99 100 101 102 103
Fabric Softening Active40.0% 28.0% --- --- 40.0% ---
a
Fabric Softening Active--- --- 40.0% 28.0% --- 31.2%
b
Clay ' 4.00% 4.00% 4.00% 4.00% 4.00% 4.00%
Sorbitan Mono-oleate --- 20.0% -- 26.4% --- 23.2%
Co-softener 45.0% 40.0% 50.0% 40.0% --- ---
Co-softener ' --- --- --- --- 45.0% 40.0%
Perfume 1.6% 1.6% 1.6% 1.6% 1.6% 1.6%
lane Retardant
Ammonium Phosphate 9.4% --- --- --- 9.4% ---
Melamine orthophosphate-__. 6.4% 4.4% ~ -___ ___ ___
~ ~ - ~
a N,N-di(tallowoyloxyethyl)-N,N-dimethylammonium methyl sulfate.
b Diethyl N,N-di(soft tallowoyloxyethyl)-N-methyl-N-2-phosphorylethyl methyl
sulfate.
' Calcium bentonite clay, Bentolite L, sold by Southern Clay Products.
d 1:2 ratio of stearyldimethylamine : ri-iple pressed stearic acid
' 1:2 ratio of stearyldimethylamine : stearic phosphate
EXAMPLE
INGREDIENTS 104 105 106
Fabric Softening Active a 30.0% --- 30.0%
Fabric Softening Active b --- 34.35% ---
Co-softener ' 20.0% 20.0% ---
Co-softener d --- --- 20.0%
Tallow fatty acid a 8.50% 8.50% 8.50%
Perfume/ Cyclodextrin Complex 17.2% 17.2% 17.2%
f
Clay ~ 4.00% 4.00% 4.00%
Glycosperse S20'' 14.5% 14.5% 14.5%
Free Perfume 1.45% 1.45% 1.45%
CA 02488839 2004-12-02
52
lance Retardant
elamine orthophosphate 4.35% --- 4.35%
a N,N-di(tallowoyloxyethyl)-N,N-dimethylammonium methyl sulfate.
b Diethyl N,N-di(soft tallowoyloxyethyl)-N-methyl-N-2-phosphorylethyl methyl
sulfate.
' 1:2 ratio of stearyldimethylamine : triple pressed stearic acid.
d 1:2 ratio of stearyldimethylamine : stearic phosphate.
(C16/l 8 IV =42) added pariway through quaternization of the fabric softener
active
f Cyclodextrin-Perfume inclusion compounds as disclosed in US 5,139,687 and US
5,234,610.
Calcium bentonite clay, Bentolite L, sold by Southern Clay Products.
h Glycosperse S20 is polyethoxyalted sorbitan monostearate, from Lonza, which
contains about 20
ethoxylate moieties per molecule.
While particular embodiments of the present invention have been illustrated
and
described, it would be obvious to those skilled in the art that various other
changes and
modifications can be made without departing from the spirit and scope of the
invention. It is
therefore intended to cover in the appended claims all such changes and
modifications that are
within the scope of this invention.
