CA2488839A1 - Liquid fabric softening compositions comprising flame retardant - Google Patents

Abstract

Liquid fabric softening compositions comprise a flame retardant. The liquid fabric softening compositions preferably further comprise a fabric softening active.
In another embodiment of the invention, the present compositions comprise a flame retardant, wherein the flame retardant is a phosphorus-containing fabric softener. In another 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. 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.

Description

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.

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

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 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.

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.

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.

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

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.

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 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 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 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 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+

P(OEt)2 ~ P(OEt) of II
° o X
O O
CH3 CHg X
R4CIO~N~OCIR4 H3C-N
CH~O\
Ii (oEt)2 P(ORa)2 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%

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:

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

OPT - ,P O
OCH3 H3 f 2X H3CHCHZC~ (OCH3)2 i i /CHzCHCH3 N + CH H3CHCH2C

I ~ I -O~ i ~H CH2CHCH3 + 3 O CH

H3C0/ OI R40~PIO Oil(OCH3)2 ~~~.OH O II/OCH2CH3 OP~O- II/OH OP~OCHzCH3 II/OCHZCH3 ~- 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

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:

~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:

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:

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:

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.

c) copolymers of ethylenically-a,(3-unsaturated dicarboxylates polymerized with vinyl-containing monomers, wherein the copolymers have the formula:

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:

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-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.

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

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 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 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-.

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:

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 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 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.

(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:

R'-~

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:

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~ 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

R~~ ~ H

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 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

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.

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 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.

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 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.

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-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, 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 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 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.

EXAMPLE

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.

The following are non-limiting examples of the liquid fabric softening compositions of the present invention which are clear compositions.
EXAMPLE

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

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%
' 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.

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

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.

' KATHON~ CG available from Rohm and Haas Co.
' Silicone antifoam agent available from Dow Corning Corp. under the ri~ade name DC2310.
EXAMPLE

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

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 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

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 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

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%

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

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 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

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 ~

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

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%

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

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%

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

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 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

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%

$0 lame Retandant Phosphorylated surfactant12.3$% 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.

The following are non-limiting examples of solid fabric softening compositions for incorporation onto a substrate to form a fabric softening dryer sheet.
EXAMPLE
~

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

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%

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.

Claims

WHAT IS CLAIMED IS:
1. A liquid fabric softening composition comprising an effective amount to reduce the risk of flammability of fluffier fabrics when treated with liquid fabric softening composition of a flame retardant.
2. The composition of Claim 1 wherein said flame retardant is chosen from a phosphorus-containing compound, nitrogen compound, halogenated organic compound, and inorganic compound.
3. The composition of Claim 2 wherein said flame retardant is a phosphorus-containing compound chosen from a phosphoric acid, phosphate salt, phosphate ester, phosphate amide, phosphorus acid, phosphate salt, phosphate salt derivative, phosphonic acid, phosphonate salt, phosphonate ester, phosphonate amide, phosphorus compound containing a nitrogen moiety, phosphorus compound containing a carboxylic acid, phosphorus compound containing a carboxylic ester, phosphonium salt, polyethylene amine polymer comprising a phosphorus substituent, and cationic starch comprising a phosphorus substituent.
4. The composition of Claim 3 wherein said flame retardant is a sodium tripolyphosphate.
5. The composition of Claim 3 wherein said flame retardant comprises the following structure:
6. The composition of Claim 2 wherein said flame retardant is a nitrogen compound.
7. The composition of Claim 6 wherein said flame retardant is a melamine or a melamine derivative.
8. The composition of Claim 2 wherein said flame retardant is a halogenated organic compound.

9. The composition of Claim 8 wherein said flame retardant is a brominated organic compound or a chlorinated organic compound.
10. The composition of Claim 2 wherein said flame retardant is an inorganic compound.
11. The composition of Claim 10 wherein said flame retardant is chosen from a perborate, barium metaborate, and ammoniumfluoroborate.
12. The composition of Claim 10 wherein said flame retardant is chosen from an antimony oxide, antimony pentaoxide, metal antimonate, aluminum oxide, alumina trihydrate, compound that comprises both an alumina and a phosphorus, molybdic oxide, ammonium octamolybdate, zinc molybdate, magnesium hydroxide, zinc stannate, zinc hydroxy stannate, and ammonium sulfamate.
13. The composition of Claim 1 wherein said flame retardant is a diethyl bis(hydroxyethyl)aminomethyl phosphonate.
14. The composition of Claim 1 wherein said flame retardant is a cationic phosphorylated starch.
15. The composition of Claim 1 wherein said flame retardant is a phosphorus-containing fabric softener chosen from 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, N,N-ditallow amidoethyl-N-methyl-N-2-phosphorylethyl ammonium methyl sulfate, linoleamidopropyl PG-dimonium chloride phosphate, cocamidopropyl PG-dimonium chloride phosphate, steramidopropyl PG-dimonium chloride phosphate, linoleamidopropyl PG-dimonium chloride phosphate, 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, diethyl N,N-ditallow amidoethyl-N-methyl-N-2-phosphorylethyl ammonium methyl sulfate, diethyl N,N-di(tallowoyloxyethyl)-N-methyl-N-ethyl-2-phosphonate ammonium chloride, 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, diethyl N,N-ditallow amidoethyl-N-methyl-N-ethyl-2-phosphonate ammonium methyl sulfate, 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, diethyl N,N-ditallow amidoethyl-N-methyl-N-methylphosphonate ammonium methyl sulfate, 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, and disodium N,N-ditallow amidoethyl-N-methyl-N-2-phosphorylethyl ammonium methyl sulfate.
16. The composition of Claim 15 wherein said composition is free of a fabric softening active.
17. The composition of Claim 1 wherein said composition further comprises a fabric softening active.
18. The composition of Claim 17 wherein said composition further comprises a silicone.
19. The composition of Claim 1 wherein said composition further comprises from about 0.001%
to about 10%, by weight of said composition, of a perfume.
20. The composition of Claim 1 wherein said composition further comprises from about 0.001%
to about 10%, by weight of said composition, of an electrolyte.
21. The composition of Claim 1 wherein said composition comprises from about 0.001% to about 60%, by weight of said composition, of said flame retardant.
22. The composition of Claim 21 wherein said composition further comprises a fabric softening active.
23. The composition of Claim 22 wherein said composition comprises from about 2% to about 90%, by weight of said composition, of said fabric softening active.
24. The composition of Claim 1 wherein said composition further comprises a silicone.
25. The composition of Claim 1 wherein said composition comprises from about 0.5% to about 10%, by weight of said composition, of said silicone.

26. A method of softening a fabric comprising the step of contacting said fabric with a composition according to Claim 1.
27. A method of minimizing a risk of flammability of cotton-containing fluffier fabrics comprising the step of contacting said fabric with a composition according to

Claim 1.