CA2149547C - Fabric softening compositions with dye transfer inhibitors for improved fabric appearance - Google Patents

Abstract

The present invention relates to compositions and processes which incorporate water-soluble polymers, other than enzymes, containing = N-C( = O)- (including PVP) and/or N-oxide groups into the wash, rinse, and/or drying cycle of a laundering process (e.g., via fabric softening compositions) for dye transfer inhibition in the subsequent wash cycle. Multiple wash cycles optimize the dye transfer inhibitor performance of these polymers, remove unwanted dye discoloration caused by dye transfer, and provide soil antiredeposition benefits.

Description

2 PCT/US93/10451 .~ X9.547 FABRIC SOFTENING COMPOSITIONS WITH OYE TRANSFER INHIBITORS
FOR IMPROVED FABRIC APPEARANCE
TECHNICAL FIELD
The present invention relates to compositions and processes useful for inhibiting the transfer of dyes, released into laun-dering solution from colored fabrics, from one fabric to another.
BACKGROUND ART
One troublesome and persistent problem during laundering operations is the tendency of some colored fabrics to release dye into the laundering solution which dye is then transferred onto other fabrics.
Manufacturers use many types of dye to color fabrics.
Common fabric dyes include direct dyes used primarily to color cotton and rayon, acid dyes used primarily on nylon, wool, and silk, disperse dyes used primarily on polyester, nylon, and Spandex, azo dyes used primarily on cotton, rayon, and silk, reactive dyes used primarily on cotton and rayon, and vat dyes used primarily on cotton. Direct, acid and disperse dyes are in general readily released into washing solution while azo and vat dyes are not.

Nhen properly applied, reactive dyes chemically bond to cellulose and therefore are not readily solubilized; however, if improperly applied, reactive dyes may also release into the wash solution.

Cotton, nylon, rayon and Spandex fabrics have a strong propensity to pick up solubilized or suspended dyes from solution, while polyester fabrics pick up such dyes to a lesser extent.

In the laundry operation, especially the operation involving automatic washing machines, dye transfer occurs mainly during the ..-~.., wash cycl e, and very sel dom, i f at al 1, duri ng the ri nse cycl a .

Dye transfer during the wash cycle is caused by higher water Z~t~9541 -2- _.
temperature, longer cycle time, and much higher surfactant con-centration in the wash cycle, as compared to the less stringent conditions of the rinse cycle.
Thus, those skilled in the art have focused efforts to inhibit dye transfer by adding dye transfer inhibitors to deter gent compositions. For example, European Patent Application 265,257, Clements et al., published April 27, 1988, discloses detergent compositions which prevent dye transfer, containing a detergent active (mixtures of anionic and nonionic are preferred), a detergent builder, and a polyvinylpyrrolidone (PYP) mixture.
German Pat. No. 3,519,012, Weber et al., published Nov. 27, 1986, teaches a detergent composition comprising nonionic surfactants, PYP components, water-soluble cationic components, and builders, to prevent dye transfer during the wash.
Dye transfer inhibitors (DTI), such as PVP, appear to solu-bilize into the wash water to scavenge the free dye molecules, thus suspending the dyes and preventing them from redepositing onto fabrics.
DTI may interact with some detergent actives. For example, detergent compositions containing PYP and anionic surfactants usually have decreased dye transfer inhibition performance com pared to those detergents containing PYP and nonionic surfactants.
It is believed that anionic surfactants interact with PYP in the wash cycle, and reduce PYP's ability to interact with free dye molecules.
All percentages, ratios, and parts herein are by weight unless otherwise stated.
SUMMARY OF THE INVENTION
The compositions of the present invention preferably incor porate water-soluble polymers containing =N-C(=0)- (including PYP), and/or N-oxide groups into fabric softening compositions to be added to the rinse and/or drying cycles of the laundry opera tion. Surprisingly, these fabric softening compositions provide effective dye transfer inhibition in the subsequent wash cycle.
These water-soluble polymers deposit on fabrics along with soft-ener actives in the rinse or dryer cycle. These DTI polymers WO 94/11482 - ~ ~ ~ g ~ ~ t PCT/US93/10451

-3-remain deposited on fabrics throughout consumer wear so that there is a sufficient concentration, after resolubilization in the subsequent wash solution, to inhibit dye transfer. Non-treated fabrics will also be protected from dye transfer when washed with fabrics previously treated with these softener compositions containing polymeric dye transfer inhibitors. It is also sur-prising that these polymer compounds in softener compositions show improved efficacy when anionic detergents rather than nonionic detergents are used in the subsequent wash cycle.
Thus, the present invention relates primarily to fabric softening compositions, in liquid, solid, or dryer sheet form, for use in the rinse and/or dryer cycles of home laundry operations.
The present invention is based on: (a) the discovery that the incorporation of an effective amount of certain polymeric dye transfer inhibitors (DTI) into liquid, solid, and/or dryer-added fabric softening compositions can effectively inhibit the transfer of dyes from one fabric to another in the subsequent wash cycle;
and/or (b) the discovery of a process of incorporating DTI into fabric softener compositions to provide convenient and/or optimal dye transfer inhibition, remove unwanted dye discoloration resulting from previous dye transfer, and/or provide soil anti-redeposition benefit in the wash cycle.
Preferably, and more specifically, fabric softening com positions are provided in the form of liquid, preferably aqueous, compositions comprising:
I. from about 3x to about 50%, preferably from about 4X to about 30%, of fabric softening agent (fabric softener); and II. frog about 0.03% to about 25%, preferably from about O.1X to about 15x, of water-soluble polymeric dye transfer inhibiting agent (dye transfer inhibitor or DTI) selected from the group consisting of:
(A) polymers with one or more monomeric units containing at least one =N-C(=0)- group, which are not enzymes, having an average molecular weight of from about 500 to about 100,000, preferably about 500 to about 40,000, and more preferably from about 1,000 to about 30,000;

WO 94/11482 ~ ~ PGT/US93/10451

- 4 -(B) polymers with one or more monomeric units containing at least one N-oxide group having an average molecular weight of from about 500 to about 1,000,000, preferably from about 1,000 to about 500,000, more preferably from about 2,000 to about 100,000;
(C) polymers containing both =N-C(=0)- and N-oxide groups of (A) and (B);
(D) mixtures thereof; and III. the balance comprising a liquid carrier, preferably water;
wherein the liquid compositions are essentially free of aerosol propellants. The nitrogen of the =N-C(=0)- group may be bonded to either one or two other atoms (with two single bonds or one double bond).
The present invention also comprises dryer-added fabric softener compositions comprising:
I. from about 50X to about 99X, preferably from about 70X to about 99X, of fabric softening agent;
II. from about 0.2X to about 50X, preferably from about 1X to about 30X, of polymeric dye transfer inhibiting agent selected from (A), (B), (C), and (D), above; and III. optionally, a dispensing means which provides for release of an effective amount of said composition to fabrics.
Solid, particulate fabric softening compositions of the present invention typically comprise:
I, from about 2QX to about 90X, preferably from about 30X to about 70X, of fabric softening agent; and II. from about O.1X to about 80X, preferably from about 0.3X to about 50X, more preferably from about 0.5X to about 25X, of dye transfer inhibiting agent also selected from (A), (B), (C), and (D), above.
jIETAIL -D DESCRIPTION OF THE INVENTION
LIQUID COMPOSITIONS
Liquid, preferably aqueous, fabric softening compositions typically comprise the following components:
I. an effective amount, preferably from about 3X to about 50X, more preferably from about 4X to about 30X, of fabric softening agent;

. , 2149547 wo 9a/ 1 ~ a82 PCT/ US93/ ~ oa51

-5-II. an effective amount, preferably from about 0.03x to about 25%, more preferably from about 0.1% to about 15X, of polymeric dye transfer inhibiting agent; and III. the balance comprising liquid carrier, preferably, selected from the group consisting of water, C1-C4 monohydric alcohols, C2-CS polyhydric alcohols, liquid polyalkylene glycols, and mixtures thereof.
I. Fabric Softening Agents The amount of fabric softening agent (fabric softener) in liquid compositions of this invention is typically from about 3%
to about 50X, preferably from about 4X to about 30'X, by weight of the composition. The lower limits are amounts needed to con tribute effective fabric softening perfonaance when added to laundry rinse baths in the manner which is customary in home laundry practice. The higher limits are suitable for concentrated products which provide the consumer with more economical usage due to a reduction of packaging and distributing costs.
Some preferred compositions are disclosed in U.S. Pat. Ho.
4,661,269, issued April 28, 1987, in the names of Toan Trinh, Errol H. wahl, Donald !1. Swartley, and Ronald L. Hemingway.
Other fabric softeners that can be used herein are disclosed in U.S. Pit. Nos.: 3,861,870, Edwards and Diehl; 4,308,151, Cambre; 3,886,075, Bernardino; 4,233,16~, Davis; 4,401,578, Yerbruggen; 3,974,076, Niersema and Rieke; and 4,237,016, Rudkin, Clint, and Young, One suitable fabric softener (Component I) is a mixture co~prising:
(a) from about 10% to about 80x of the reaction product of higher fatty acids with a polyamine selected from the group consisting of hydroxyalkylalkylenediamines and dialkylenetriamines and mixtures thereof;
(b) from about 3x to about 40x of cationic nitrogenous salts containing only one long chain acyclic aliphatic C15-C22 hydrocarbon group; and B

..
CVO 94/11482 t 2 1 4 9 5 4 7 PCT/US93/10451

-6-(c) from about lOx to about 80X of cationic nitrogenous salts having two or more long chain acyclic aliphatic C15-C22 hydrocarbon groups or one said group and an arylalkyl group;
said (a), (b) and (c) percentages being by weight of Component I.
Following are the general descriptions of the above softener ingredients including certain specific examples. These examples illustrate, but do not limit the present invention.
Comuanent I(a) A preferred softening agent (active) of the present invention is the reaction products of higher fatty acids with a polyamine selected from the group consisting of hydroxyalkylalkylenediamines and dialkylenetriamines and mixtures thereof. These reaction products are mixtures of several compounds in view of the multi-functional structure of the polyamines.
The preferred Component I(a) is a nitrogenous compound selected from the group consisting of the reaction product mix-tures or some selected components of the mixtures. More specif-ically, the preferred Component I(a) is compounds selected from the group consisting of:
(i) the reaction product of higher fatty acids with hydroxy alkylalkylenediamines in a molecular ratio of about 2:1, said reaction product containing a composition having a compound of the formula:
H ~ ~ R20H

wherein R1 is an acyclic aliphatic C15-C21 hydrocarbon group and R2 and R3 are divalent C1-C3 alkylene groups;
(ii) substituted imidazoline compounds having the formula:

R1 - C ~

;:24954 _7-wherein R1 and R2 are defined as above;
(iii) substituted imidazoline compounds having the formula:

R1 - C ' 0 - R2 wherein R1 and R2 are defined as above;
(iv) the reaction product of higher fatty acids with di-alkylenetriamines in a molecular ratio of about 2:1, said reaction product containing a composition having a compound of the formula:

wherein R1, R2 and R3 are defined as above; and (v) substituted imidazoline compounds having the formula:

wherein R1 and R2 are defined as above; and (vi) mixtures thereof.
Component I(a)(i) is commercially available as Mazamidee 6, sold by Mazer Chemicals, or Ceranine~ HC, sold by Sandoz Colors $
Chemicals; here the higher fatty acids are hydrogenated tallow fatty acids and the hydroxyalkylalkylenediamine is N-2-hydroxy-ethylethylenediamine, and RI is an aliphatic C15-C17 hydrocarbon group, and R2 and R3 are divalent ethylene groups.
An example of Component I(a)(ii) is stearic hydroxyethyl imidazoline wherein R1 is an aliphatic C17 hydrocarbon group, R2 is a divalent ethylene group; this chemical is sold under the WO 94/11482 ~ ~ ~ 4 9 5 4 ?
-g_ trade ~ names of Alkazinee ST by Alkaril Chemicals, Inc., or Schercozolines S by Scher Chemicals, Inc.
An example of Component I(a)(iv) is N,N"-ditallowalkoyldi ethylenetriamine where R1 is an aliphatic C15-C17 hydrocarbon group and R2 and R3 are divalent ethylene groups.
An example of Component I(a)(v) is 1-tallowamidoethyl-2-tal-lowimidazoline wherein R1 is an aliphatic C15-C17 hydrocarbon group and R2 is a divalent ethylene group.
The Components I(a)(iii) and I(a)(v) can also be first dispersed in a Bronsted acid dispersing aid having a pKa value of not greater than about 4; provided that the pH of the final composition is not greater than about 5. Some preferred dispers ing aids are hydrochloric acid, phosphoric acid, or methylsulfonic acid.
Both N,N"-ditallowalkoyldiethylenetriamine and 1-tallow(amido-ethyl)-2-tallowimidazoline are reaction products of tallow fatty acids and diethylenetriamine, and are precursors of the cationic fabric softening agent methyl-1-tallowamidoethyl-2-tallowimidazo-linium methylsulfate (see "Cationic Surface Active Agents as Fabric Softeners," R. R. Egan, Journal of the American Oil Chemi-cals' Society, January 1978, pages 118-121). N,N"-ditallow-alkoyldiethylenetriamine and 1-tallowamidoethyl-2-tallowimidazo-line can be obtained from Sherex Chemical Company as experimental chemicals. Methyl-1-tallowamidoethyl-2-tallowimidazolinium meth-ylsulfate is sold by Sherex Chemical Company under the trade name Yarisofte 475.
Component I(bl The preferred Component I(b) is a cationic nitrogenous salt containing one long chain acyclic aliphatic C15-C22 hydrocarbon group selected from the group consisting of:
(i) acyclic quaternary ammonium salts having the formula:

I
R4 _ N _ R5 AA

2 1 4 9 5 4 7 P~/US93/10451 -g_ wherein R4 is an acyclic aliphatic C15-C22 hydrocarbon group, R5 and R6 are C1-C4 saturated alkyl or hydroxy-alkyl groups, and A8 is an anion;
(ii) substituted imidazolinium salts having the formula:
~N - CH2 P
R 1 _ C \ I AA

wherein R1 is an acyclic aliphatic C15-CZ1 hydrocarbon group, R7 is a hydrogen or a C1-C4 saturated alkyl or hydroxyalkyl group, and Ae is an anion;
(iii) substituted imidazolinium salts having the formula:

R1 _ C ~ I AA

wherein R2 is a divalent C1-C3 alkylene group and R1, R5 and Ae are as defined above;
(iv) alkylpyridinium salts having the formula:
~ _ N/ \, A8 wherein R4 is an acyclic aliphatic C16-C22 hydrocarbon group and Aa is an anion; and (v) alkanamide alkylene pyridinium salts having the formula:

R1 - C - NH - R2 - N ~ \ AA

WO 94/ 11482 ~ t 21 4 9 5 wherein R1 is an acyclic aliphatic C15-C21 hydrocarbon group, R2 is a divalent C1-C3 alkylene group, and Ae is an ion group;
(vi) monoester quaternary artmonium compounds having the formula:
I(R)3 - N~ - (CH2)n - Y - R2] AA
wherein each Y - -0-(0)C-, or -C(0)-0-;
each n - 1 to 4;
each R substituent is a short chain C1-C6, preferably C1-C3 alkyl or hydroxyalkyl group, e.g., methyl (most preferred), ethyl, propyl, hydroxyethyl, and the like, benzyl or mixtures thereof;
R2 is a long chain C10-C22 hydrocarbyl, or substituted hydrocarbyl substituent, preferably C15-C1g alkyl and/o'r~
alkenyl, most preferably C15-C18 straight chain alkyl and/or alkenyl; and the counterion, Ae, can be any softener-compatible anion, for example, chloride, bromide, methylsulfate, formats, sulfate, nitrate and the like; and (vii) mixtures thereof.
Examples of Component I(b)(i) are the monoalkyltrimethylanmo-nium salts such as monotallowtrimethylanmonium chloride, mono(hy-drogenated tallow)trimethylartmonium chloride, palmityltrimethyl-ammonium chloride and soyatrimethylanmonium chloride, sold by Sherex Chemical Company under the trade name Adogene 471, Adogens 441, Adogen~ 444, and Adogens 415, respectively. In these salts, R4 is an acyclic aliphatic C16-C18 hydrocarbon group, and R5 and R6 are methyl groups. Mono(hydrogenated tallow)trimethylanmonium chloride and monotallowtrimethylammonium chloride are preferred.
Other examples of Component I(b)(i) are behenyltrimethylanmonium chloride wherein R4 is a C22 hydrocarbon group and sold under the trade name Kemaminee Q2803-C by Humko Chemical Division of Witco Chemical Corporation; soyadimethylethylanmonium ethylsulfate wherei n R4 i s a C16-C18 hydrocarbon group, R5 i s a methyl group, WO 94/11482 ~'~ s ~ ~ ~ ~ j~ 7 PCT/US93/10451 R6 is an ethyl group, and Ae is an ethylsulfate anion, sold under the trade name Jordaquat~ 1033 by Jordan Chemical Company; and methyl-bis(2-hydroxyethyl)octadecylanmonium chloride wherein R4 is a Clg hydrocarbon group, R5 is a 2-hydroxyethyl group and R6 is a methyl group and available under the trade name Ethoquad~ 18/12 from Armak Company.
An example of Component I(b)(iii) is 1-ethyl-1-(2-hydroxy-ethyl)-2-isoheptadecylimidazolinium ethylsulfate wherein R1 is a C17 hydrocarbon group, R2 is an ethylene group, R5 is an ethyl group, and A8 is an ethylsulfate anion. It is available from Mona Industries, Inc., under the trade name Monaquate ISIES.
An example of Component I(b)(vi) is mono(tallowoyloxyethyl)-hydroxyethyldimethylanmonium chloride, i.e., monoester of tallow fatty acid with di(hydroxyethyl)dimethylanmonium chloride, a by-product in the process of making diester of tallow fatty acid with di(hydroxyethyl)dimethylammonium chloride, i.e., di(tallow-oyloxyethyl)dimethylammonium chloride, a I(cj(vii) component (vide infra) .
Comconent I(c) Preferred cationic nitrogenous salts having two or more long chain acyclic aliphatic C15-C22 hydrocarbon groups or one said group and an arylalkyl group which can be used either alone or as part of a mixture are selected from the group consisting of:
(i) acyclic quaternary artmonium salts having the formula:

_ _ wherein R4 is an acyclic aliphatic C15-C22 hydrocarbon group, R5 is a C1-C4 saturated alkyl or hydroxyalkyl group, Rg is selected from the group consisting of R4 and R5 groups, and A8 is an anion defined as above;

WO 94/11482 ~ ~ 7 PCT/US93/10451 (ii) diamido quaternary ammonium salts having the formula:
p R5 p D

R1 C - - - - - C - R1 Ae -Rg wherein R1 is an acyclic aliphatic C15-C21 hydrocarbon group, R2 is a divalent alkylene groua having 1 to 3 carbon atoms, R5 and Rg are C1-C4 saturated alkyl or hydroxyalkyl groups, and Ae is an anion;
(iii) diamino alkoxylated quaternary ammonium salts having the formula:
p R5 p 0 (CH2CH20)nH
wherein n is equal to 1 to about 5, and R1, R2, R5 and A8 are as defined above;
(iv) quaternary anmonium compounds having the formula:

/ ~ AA

wherein R4 is an acyclic aliphatic C15-C22 hydrocarbon group, R5 is a C1-C4 saturated alkyl or hydroxyalkyl group, Ae is an anion;

WO 94/11482 2 1 4 9 5 ~ ~ P~/US93/10451 ..'w - 13 -(v) substituted imidazolinium salts having the formula:
N - CH2 ~ D
R1 _ C ~ I A8 wherein R1 is an acyclic aliphatic C15-C21 hydrocarbon group, R2 is a divalent alkylene group having 1 to 3 carbon atoms, and R5 and Ae are as defined above; and (vi) substituted imidazolinium salts having the formula:
~ N - CH2 R1 - C ~ I A8 wherein R1, R2 and Ae are as defined above;
(vii) diester quaternary anmonium (OEQA) compounds having the fonaul a:
(R)4-m - N~ - [(CH2)n - Y - R2Jm AA
wherein each Y ~ -0-(0)C-, or -C(0)-0-;
n~ ~ 2 or 3;
each n ~ 1 to 4;
each R substituent is a short chain C1-C6, preferably C1-C3 alkyl or hydroxyalkyl group, e.g., methyl (most preferred), ethyl, propyl, hydroxyethyl, and the like, benzyl, or mixtures thereof;
each R2 is a long chain Clp-C22 hydrocarbyl, or substi tuted hydrocarbyl substituent, preferably C15-Clg alkyl and/or alkenyl, most preferably C15-C18 straight chain alkyl and/or alkenyl; and WO 94/ 11482 ~' ~ c PCT/US93/ 10451 M a ~ ~ 1 ~ 9 5 4 the counterion, A8, can be any softener-compatible anion, for example, chloride, bromide, methylsulfate, formate, sulfate, nitrate and the like; and (viii) mixtures thereof.
Examples of Component I(c)(i) are the well-known dialkyldi-methylartmonium salts such as ditallowdimethylartmonium chloride, ditallowdimethylammonium methylsulfate, di(hydrogenated tallow)di-methylanmonium chloride, distearyldimethylanmonium chloride, dibehenyldimethylartmonium chloride. Di(hydrogenated tallow)di-methylammonium chloride and ditallowdimethylammonium chloride are preferred. Examples of cortmercially available dialkyldimethyl-ammonium salts usable in the present invention are di(hydrogenated tallow)dimethylanmonium chloride (trade name Adogene 442), dital-lowdimethylammonium chloride (trade name Adogene 470), distearyl-dimethylammortium chloride (trade name Arosurfs TA-100), all available from Sherex Chemical Company. Dibehenyldimethylartmonium chloride wherein R4 is an acyclic aliphatic C22 hydrocarbon group is sold under the trade name Kemamine Q-2802C by Humko Chemical Division of Witco Chemical Corporation.
Examples of Component I(c)(ii) are methylbis(tallowamido-ethyl)(2-hydroxyethyl)anmonium methylsulfate and methylbis(hy-drogenated tallowamidoethyl)(2-hydroxyethyl)anmonium methylsulfate wherein R1 is an acyclic aliphatic C15-C17 hydrocarbon group, R2 i s an ethyl ene group, R5 i s a methyl group, Rg i s a hydraxyal kyl group and Ae is a methylsulfate anion; these materials are avail-able from Sherex Chemical Company under the trade names Varisoft~
222 and Yarisofte 110, respectively.
An example of Component I(c)(iv) is dimethylstearylbenzyl ammonium chloride wherein R4 is an acyclic aliphatic C18 hydro carbon group, R5 is a methyl group and Ae is a chloride anion, and is sold under the trade names Varisofte SDC by Sherex Chemical Company and Artmonyx~ 490 by Onyx Chemical Company.
Examples 'of Component I(c)(v) are 1-methyl-1-tallowamido ethyl-2-tallowimidazolinium methylsulfate and 1-methyl-1-(hy drogenated tallowamidoethyl)-2-(hydrogenated tallow)imidazolinium methylsulfate wherein R1 is an acyclic aliphatic C15-C17 hydro-WO 94/11482 Z 1 4 9 5 4 ~ PCT/US93/10451 carbon group, R2 is an ethylene group, R5 is a methyl group and Ae is a chloride anion; they are sold under the trade names Varisofta 475 and Varisofte 445, respectively, by Sherex Chemical Company.
It will be understood that for I(c)(vii) above substituents R
and R2 can optionally be substituted with various groups such as alkoxyl or hydroxyl groups, and/or can be saturated, unsaturated, straight, and/or branched so long as the R2 groups maintain their basically hydrophobic character. Preferred softening compounds are biodegradable such as those in Component I(c)(vii). These preferred compounds can be considered to be diester variations of ditallow dimethyl ammonium chloride (OTDMAC), which is a widely used fabric softener.
The following are non-limiting examples of I(c)(vii) (wherein all long-chain alkyl substituents are straight-chain):
[CH3]20N[CH2CH20C(0)R2J C18 [HO-CH(CH3)CH2J[CH3J~N[CH2CH20C(0)C15H31J2 Br0 [C2H5J2~N[CH2CH20C(0)C17H35J2 Clg [CH3][C2H5]~N[CH2CH20C(0)C13H27J2 IA
[C3H7J[C2H5J~N[CH2CH20C(0)C15H31J2 S04eCH3 [CH3J2~N-CH2CH20C(0)C15H31 Cle CH2CH20C(0)C17H35 [CH2CH20H][CH3JgN[CH2CH20C(0)R2J2 Cle where -C(0)R2 is derived from soft tallow and/or hardened tallow fatty acids. Especially preferred is diester of soft and/or hardened tallow fatty acids with di(hydroxyethyl)dimethylammonium chloride, also called di(tallowoyloxyethyl)dimethylartmonium chloride.
Since the foregoing compounds (diesters) are somewhat labile to hydrolysis, they should be handled rather carefully when used to formulate the compositions herein. For example, stable liquid compositions herein are formulated at a pH in the range of about 2 to about 5, preferably from about 2 to about 4.5, more preferably from about 2 to about 4. The pH can be adjusted by the addition of a Bronsted acid. pH ranges for making stable softener compo-sitions containing diester quaternary anmonium fabric softening compounds are disclosed in U.S. Patent No. 4,767,547, Straathof and Konig, issued August 30, 1988.
The diester quaternary ammonium fabric softening compound (DEQA) of I(c)(vii) can also have the general formula:
R2C(O)OCH2 \' CHCH2eNR3 Ae R2C(0)0 wherein each R, R2, and Ae have the same meanings as before. Such compounds include those having the formula:
[CH3]3eN[CH2CH(CH20C[0]R2)OC(O)R2] C1e where -OC(O)R2 is derived from soft tallow and/or hardened tallow fatty acids.
Preferably each R is a methyl or ethyl group and preferably each RZ is in the range of C~5 to C,s. Degrees of branching, substitution and/or non-saturation can be present in the alkyl chains. The anion Ae in the molecule is preferably the anion of a strong acid and can be, for example, chloride, bromide, iodide, sulphate, and methyl sulphate; the anion can carry a double charge in which case Ae represents half a group. These compounds, in general, are more difficult to formulate as stable concentrated liquid compositions.
These types of compounds and general methods of making them are disclosed in U.S. Pat. No. 4,137,180, Naik et al., issued Jan. 30, 1979.
A preferred composition contains Component I(a) at a level of from about 10%
to about 80%, Component I(b) at a level of from about 3% to about 40%, and Component I(c) at a level of from about 10% to about 80%, by weight of said Component I. A more preferred composition contains Component I(c) which is selected from the group consisting of: (I) di(hydrogenated tallow)dimethylammonium chloride; (v) methyl-1-tallowamidoethyl-2-tallowimidazolinium methylsulfate; (vii) diethanol ester dimethylammonium chloride; and mixtures thereof.
An even more preferred composition contains component I(a): the reaction product of about 2 moles of hydrogenated tallow fatty acids with about 1 mole of N-2-hydroxyethylethylenediamine and is WO 94/11482 ' ~ 1 ~ 9 5 4 7 P~/US93/10451 present at a level of from about 20% to about 70% by weight of Component I; Component I(b): mono{hydrogenated tallow)trimethyl-ammonium chloride present at a level of from about 3% to about 30%
by weight of Component I; Component I(c): selected from the group consisting of di(hydrogenated tallow)dimethylanmonium chloride, ditallowdimethylanmonium chloride, methyl-1-tallowamidoethyl-2-tallowimidazolinium methylsulfate, diethanol ester dimethylartmo-nium chloride, and mixtures thereof; wherein Component I{c) is present at a level of from about 20X to about 60% by weight of Component I; and wherein the weight ratio of said di{hydrogenated tallow)dimethylammonium chloride to said methyl-1-tallowamido-ethyl-2-tallowimidazolinium methylsulfate is from about 2:1 to about 6:1.
The above individual components can also be used individu ally, especially those of I(c) (e. g., ditallowdimethylammonium chloride or diethanol ester dimethylammonium chloride).
Anion AaAe In the cationic nitrogenous salts herein, the anion Ae pro vides charge neutrality. Most often, the anion used to provide charge neutrality in these salts is a halide, such as fluoride, chloride, bromide, or iodide. However, other anions can be used, such as methylsulfate, ethylsulfate, hydroxide, acetate, formate, sulfate, carbonate, and the like. Chloride and methylsulfate are preferred herein as anion Ae.
II. ~,olvmer~c Ove Transfer Inhibiting Agents The coa~position of the present invention contains an effective amount of polymeric dye transfer inhibiting agent (dye transfer inhibitor or DTI) or mixtures thereof. An effective amount is typically an amount of DTI which will provide at least about 0.1 ppm, preferably from about 0.1 ppm to about 2,000 ppm, more preferably from about 0.2 ppm to about 1,000 ppm, in the wash or rinse solution. Preferably, the present invention con-tains from about 0.03% to about 25% of dye transfer inhibitor, more preferably from about 0.1% to about 15%, and even more preferably from about 0.2% to about 10% for concentrated liquid softener compositions, and from about 0.01% to about 8X for compositions with softener active of less than about 9%.

h i WO 94/11482 - ;.~ ~ ~ ~ 5 ft ~ PCT/US93/10451 .._ Dye transfer inhibitors useful in the present invention include water-soluble polymers containing nitrogen and oxygen atoms, selected from the group consisting of:
(A) polymers, which are not enzymes, with one or mare monomeric units containing at least one =N-C(=0)- group;
(B) polymers with one or more monomeric units containing at least one N-oxide group;
(C) polymers containing both =N-C(=0)- and N-oxide groups of (A) and (B);
(D) mixtures thereof;
wherein the nitrogen of the =N-C(=0)- group can be bonded to either one or two other atoms (i.e., can have two single bonds or one double band).
Dye transfer inhibitors useful in the present invention include water-soluble polymers having the structure:
P
I
(D)m n wherein each P is selected from homopolymerizable and copolymer-izable moieties which attach to form the polymer backbone, prefer-ably each P being selected from the group consisting of:
vinyl moieties, e.g., [-C(R)2-C(R)2-]; other monomeric moieties, e.g., E[C(R)2)x-L-), wherein each x is an integer from I to 6 and each L is independently selected from the group consisting of:

~, ,~
-N(R)-; -0-; -S-; -0-C-; -C-0-; -S-; -S-; -S-0-; -0-S-; -0-S-0-;

-0-~Si(R2)-0~; -C-; and -0-C-0-; and OTI-active groups P

-N(R)-; -N(R)C-; -C-N(R)-.

., ;, wherein each R is H, C1-12 (Preferably C1_4) alkyl(ene), C6-C12 aryl(ene) and/or D, m is from 0 to 2, and p is from 1 to about 6;
wherein each D contains moieties selected from the group con-sisting of: L moieties; structural moieties selected from the group consisting of linear and cyclic C1-12 (preferably C1-4) alkyl; C1-12 alkylene; C1-12 heterocyclic groups, which can also contain the OTI active groups; aromatic C6_12 groups; and Rs to complete the group, wherein any linking groups which are attached to each other form linkages that are substantially stable under conditions of use; and wherein the nitrogen atoms can be attached to one, two, or three other atoms, the number of =N-C- and/or ~1~! ~ 0 groups present being sufficient to provide dye transfer inhibition, the total molecular weight being from about 500 to about 1,000,000, preferably from about 1,000 to about 500,000, n being selected to provide the indicated molecular weight, and the water solubility being at least about 100 ppm, preferably at least about 300 ppm, and more preferably at least about 1,000 ppm in water at ambient temperature of about 25'C.
A. Polymers with Active =N-C(=O1- Groups One useful group of polymeric DTIs include water-soluble polymers containing active =N-C(=0)- groups, excluding enzymes.
The nitrogen of the =N-C(=0)- group can be bonded to either one or two other atoms.
Examples of polymers containing =N-C(=0)- groups are:
Polyvinylpyrrolidone:
-~-CH2-CH-~-CH N~C~O

WO 94/11482 ~ ,~ ' 21 4 9 5 4 , PCT/US93/10451 '3 ~ t Polyvinyloxazolidone":
--f-CH2-CH-~
I
/N\ 0 Polyvinylmethyloxazolidone:
-f-CH2-CH-~
I
CH/ N~C~O

Polyacrylamide and N-substituted polyacrylamides:
-f-CH2-CH-~-I
C=0 N(Ri)2 wherein each R1 is independently selected from H and C1-C6 alkyl groups, e.g., methyl, ethyl, propyl, or isopropyl, or two R1 groups can form a 5 or 6 member ring structure.
Polymethacrylamide and N-substituted polymethacrylamides:

I
-~-CH2-C-.~-I
C=0 ( N(R1)2 wherein each R1 is as described above.

w 21 495 47 f ,,.-.. - 21 -Poly(N-acrylylglycinamide):
-~-CH2-CH-~-C=0 0 ~
NH - CH2 - C - N(R1)2 Poly(N-methacrylylglycinamide):

-E-CH2 -C -~-C=0 0 NH - CH2 - C - N(R1)2 Poly(2-ethyl-2-oxaZOline):
-~CH2-CH2-N--~-C=0 Polyvinylurethane:
-~-CH2-CH-~-C=0 N(R1)2 wherein each R1 is as described above. Mixtures of these groups can be present in the polymeric DTI groups of (A) and (C) described hereinbefore and hereinafter.
These polymers have an amphiphilic character with polar groups conferring hydrophilic properties and apolar groups con-ferring hydrophobic properties. Preferred polymers are those w, WO 94/11482 . _ ,_ ~ 4 g 5 4 ~ PCT/US93/10451 ,2 _ 22 _ having the nitrogen atoms highly" substituted so that they are shielded to different degrees by the surrounding apolar groups.
Examples of said polymers are polyvinylpyrrolidones, polyvinyl-oxazolidones, N,N-disubstituted polyacrylamides, and N,N-disub-stituted polymethacrylamides. Detailed description of physico-chemical properties of some of these polymers are given in "Water-Soluble Synthetic Polymers: Properties and Behavior,"
Yol. I, Philip Molyneux, CRC Press, 1983.
These polymers are also useful in the present invention in partially hydrolyzed and/or crosslinked forms.
A preferred dye transfer inhibitor is polyvinylpyrrolidone (PYP). This polymer has an amphiphilic character with a highly polar amide group conferring hydrophilic and polar-attracting properties, and also has apolar methylene and methine groups, in the backbone and/or the ring, conferring hydrophobic properties.
The rings may also provide planar alignment with the aromatic rings in the dye molecules. PYP is readily soluble in aqueous and organic solvent systems.
PVP is available from ISP, Wayne, New Jersey, and BASF Corp., Parsippany, New Jersey, as a powder or aqueous solutions in several viscosity grades, designated as, e.g., K-12, K-15, K-25, and K-30. These K-values indicate the viscosity average molecular weight, as shown below:
PYP Viscosity Avg. Mol. Wt. 2,500 10,000 24,000 40,000 PVP K-12, K-15, and K-30 are also available from Polysciences, Inc. Warrington, Pennsylvania, and PYP K-15, K-25, and K-30 and poly(2-ethyl-2-oxazoline) are available from Aldrich Chemical Co., Inc., Milwaukee, Wisconsin.
The average molecular weight for water-soluble polymers with =N-C(=0)- groups useful in the present invention is from about 500 to about 100,000, preferably from about 500 to about 40,000, and more preferably from about 1,000 to about 30,000.
B. Polymers with Active N-Oxide Groins Another useful group of polymeric DTI include water-soluble polymers containing active ~N ~ 0 groups. The nitrogen of the '' -23- 2149547 ;H ~ 0 group can be bonded to either one, two, or three other atoms.
One or more of the ;N ~ 0 groups can be part of the pendant D
group or one or more ~N ~ 0 groups can be part of the polymerizable P unit or a combination of both.
Where the ~N ~ 0 group i s part of the pendant 0 group, pre ferred D groups contain cyclic structures with the nitrogen atom of the ~N ~ 0 group being part of the ring or outside the ring.
The ring in the D group may be saturated, unsaturated, or aro matic.
Examples of D groups containing the nitrogen atom of the ;N -~ 0 group include N-oxides of heterocyclic compounds such as the N-oxides of pyridine, pyrrole, imidazole, pyrazole, pyrazine, pyrimidine, pyridazine, piperidine, pyrrolidone, azolidine, morpholine, and derivatives thereof. A preferred dye transfer inhibitor is poly(4-vinylpyridine N-oxide) (PVNO). Examples of D
groups with the nitrogen atom of the N ~ 0 group being outside the ring include aniline oxide and N-substituted aniline oxides.
An example of a polymer wherein the ~N i 0 group is part of the monomeric P backbone group is polyethyleneimine N-oxide.
Mixtures of these groups can be present in the polymeric DTIs of (B) and (C).
The amine N-oxide polymers of the present invention typically have a ratio of amine N-oxide to the amine of -from about 1:0 to about 1:2. The amount of amine oxide groups present in the polyamine oxide polymer can be varied by appropriate copoly-merization or by appropriate degree of N-oxidation. Preferably, the ratio of amine N-oxide to amine is from about 1:0 to about 1:1, most preferred from 1:0 to about 3:1.
The amine oxide unit of the polyamine N-oxides has a PKa 510, preferably PKa 51~ more preferably PKa 56.
The average molecular weight of (B) useful in the present invention is .from about 500 to about 1,000,000; more preferably from about 1,000 to about 500,000; most preferably from about 2,000 to about 100,000.

WO 94/1148 , ,w ~. ~ ~'~ ~ ~ 5 4 ~ PCT/US93/10451 Any polymer backbone above can be used in (A) or (B) as long as the polyriier 'formed is water soluble and has dye transfer inhib-iting properties. Examples of suitable polymeric backbones are polyvinyls, polyalkylenes, polyesters, polyethers, polyamide, polyimides, polyacrylates, and copolymers and block copolymers thereof, and mixtures thereof.
C. Co~olvmers Including Active =N-C(=01- and/or ~N ~ 0 Grauos Effective polymeric DTI agents can include those formed by copolymerizing mixtures of monomeric, oligomeric, and/or polymeric units containing active =N-C(=0)- and/or active ~1 ~ 0 groups (e. g., copolymers and/or block copolymers of PYP and PYNO). Other suitable DTI copolymers include those in which an effective amount of monomeric, oligomeric, and/or polymeric units containing active =N-C(=0)- groups and/or active ~! ~ 0 groups is copolymerized with "filler" monomeric, oligomeric, and/or polymeric units which do not contain active =N-C(=0)- or ~N ~ 0 groups but which impart other desirable properties to the DTI copolymer, such as increased water solubility or enhanced fabric substantivity [e. g., block copolymer of PVP (Z about 60X) and polyvinylimidazoleJ.
III. Liauid Carriers The liquid carrier is typically selected from the group consisting of water, C1-C4 monohydric alcohols, C2-C6 polyhydric alcohols (e. g., alkylene glycols like propylene glycol), liquid polyalkylene glycols such as polyethylene glycol with an average molecular weight of about 200, and mixtures thereof. water, a preferred carrier, may be distilled, deionized, or tap water.
IY. Optional Ingredients A. Polymeric Soil Release Agents Soil release agents, usually polymers, are especially desir-able additives at levels of from about 0.05X to about 5X, prefer-ably from about O.1X to about 4X, more preferably from about 0.2X
to about 3X. Suitable soil release agents are disclosed in U.S.
Pat. Nos.: 4,702,857, Gosselink, issued Oct. 27, 1987; 4,711,730, Gosselink and Diehl, issued Dec. 8, 1987; 4,713,194, Gosselink issued Dec. l5, 1987; 4,877,896, Maldonado, Trinh, and Gosselink, issued Oct. 31, 1989; 4,956,447, Gosselink, Hardy, and Trinh, issued Sep. 11, 1990; and 4,749,596, Evans, Huntington, Stewart, Wolf, and Zimmerer, issued June 7, 1988.
Especially desirable optional ingredients are polymeric soil release agents comprising block copolymers of polyalkylene tere-phthalate and polyoxyethylene terephthalate, and block copolymers of polyalkylene terephthalate and polyethylene glycol. The polyalkylene terephthalate blocks preferably comprise ethylene and/or propylene groups. Many such soil release polymers are nonionic.
A preferred nonionic soil release polymer has the following average structure:
SRP I: CH30(CH2CHz0)40 [C(0) ~ \ C(0)-OCH2CH(CH3)0 ] 5 -C(0) ~ ~ C(0) ( OCH2CH2 )4o0CH3.
Such slow release polymers are described in U.S. Pat. No. 4,849,257, Borcher, Trinh and Bolich, issued July 18, 1989.
Another highly preferred nonionic soil release polymer is described in copending U.S. Pat. Appln. Ser. No. 07/676,682*, Pan, Gosselink, and Honsa, filed Mar.
28, 1991.
The polymeric soil release agents useful in the present invention can include anionic and cationic polymeric soil release agents. Suitable anionic polymeric or oligomeric soil release agents are disclosed in U.S. Pat. No. 4,018,569, Trinh, Gosselink and Rattinger, issued April 4,1989. Other suitable polymers are disclosed in U.S. Pat.
No. 4,808,086, Evans, Huntington, Stewart, Wolf, and Zimmerer, issued Feb. 24, 1989.
Suitable cationic soil release polymers are described in U.S. Pat. No.
4,956,447, Gosselink, Hardy, and Trinh, issued Sept. 11, 1990.
(* Equivalent to W092/17523 published 15.10.92.) WO 94/11482 2 1 ~ 9 5 ~ 7 PCT/US93/10451 ..
'y., ' - 26 -B. Qther Optional Ingredients A preferred optional ingredient is perfume. Such perfume is preferably present at a level of from about 0.01% to about 5%, preferably from about 0.05% to about 3%, more preferably from about 0.1% to about 2%, by weight of the total composition.
Other adjuvants can be added to the compositions herein for their known purposes. Such adjuvants include, but are not limited to, viscosity control agents, emulsifiers, preservatives, antioxi-dants, bacteriocides, fungicides, brighteners, opacifiers, freeze-thaw control agents, shrinkage control agents, and agents to provide ease of ironing. These adjuvants, if used, are added at their usual levels, generally each at up to about 5% by weight of the composition.
Viscosity control agents can be organic or inorganic in nature. Examples of organic viscosity modifiers (lowering) are aryl carboxylates and sulfonates (e. g., benzoate, 2-hydroxy benzoate, 2-aminobenzoate, benzenesulfonate, 2-hydroxybenzenesul fonate, 2-aminobenzenesulfonate, etc.), fatty acids and esters, fatty alcohols, and water-miscible solvents such as short chain alcohols. Examples of inorganic viscosity control agents are water-soluble ionizable salts. A wide variety of ionizable salts can be used. Exaa~les of suitable salts are the halides of the group IA and IIA metals of the Periodic Table of the Elements, e.g., calcium chloride, magnesium chloride, sodium chloride, potassiua~ bromide, and lithium chloride. Calcium chloride is preferred. The ionizable salts are particularly useful during the process of aixing the ingredients to make the compositions herein, and later to obtain the desired viscosity. The amount of ioniz-able salts used depends on the amount of active ingredients used in the compositions and can be adjusted according to the desire of the formulator. Typical levels of salts used to control the composition viscosity are from 0 to about 10,000 parts per million (ppm), preferably from about 10 to about 6,000 ppm by weight of the composition.
Viscosity modifiers (raising) can be added to increase the ability of the compositions to stably suspend water-insoluble particles, e.g., perfume microcapsules. Such materials include WO 94/11482 ~ PCT/US93/10451 hydroxypropyl substituted guar gum (e. g., Jaguar~ HP200, available from Rhone-Poulenc), polyethylene glycol (e. g., Carbowax 20M from Union Carbide), hydrophobic modified hydroxyethylcellulose (e. g., Natrosol Plus~ from Aqualon), and/or organophilic clays (e. g., Hectorite and/or Bentonite clays such as Bentoness 27, 34 and 38 from Rheox Co.). These viscosity raisers (thickeners) are typic-ally used at levels from about 500 ppm to about 30,000 ppm, preferably from about 1,000 ppm to about 5,000 ppm, more pref-erably from about 1,500 ppm to about 3,500 ppm.
Examples of bacteriocides useful in the compositions of this invention are glutaraldehyde, formaldehyde, 2-bromo-2-nitropro-pane-1,3-diol sold by Inolex Chemicals under the trade name Bronopolm, and a mixture of 5-chloro-2-methyl-4-isothiazoline-3-one and 2-methyl-4-isothiazoline-3-one sold by Rohm and Haas Com-pany under the trade name Kathone CG/ICP. Typical levels of bacteriocides used in the present compositions are from about 1 to about 1,000 ppm by weight of the composition.
Examples of antioxidants that can be added to the compo sitions of this invention are propyl gallate, available from Eastman Chemical Products, Inc., under the trade names Tenoxe PG
and Tenox S-1, and dibutylated hydroxy toluene, available from UOP
Process Division under the trade name Sustanee BHT.
The present compositions can contain silicoses to provide additional benefits such as ease of ironing and improved fabric absorbency. The preferred silicones are polydimethylsiloxanes of viscosity of from about 100 centistokes (cs) to about 100,000 cs, preferably from about 200 cs to about 60,000 cs and/or silicone gums. These silicones can be used in emulsified form, which can be conveniently obtained directly from the suppliers. Examples of these preemulsified silicones are 60% emulsion of polydimethyl-siloxane (350 cs) sold by Dow Corning Corporation under the trade name DOW CORNINGs 1157 Fluid and 50% emulsion of polydimethyl-siloxane (10,000 cs) sold by General Electric Company under the trade name General Electrica SM 2140 Silicones. Microemulsions are preferred, especially when the composition contains a dye.
The optional silicone component can be used in an amount of from about 0.1% to about 6% by weight of the composition.

W094/11482 - ' - 'fi: ,~""~1~,9;'~t.,4 ~ PCT/US93/10451 Silicone foam suppressants can also be used. These are usually not emulsified and typically have viscosities of from about 100 cs to about 10,000 cs, preferably from about 200 cs to . about 5,000 cs. Yery low levels are used, typically from about O.O1X to about 1X, preferably from about 0.02X to about 0.5X.
Another preferred foam suppressant is a silicone/silicate mixture, e.g., Dow Corning's Antifoam Ae.
Any dye can be used in the compositions of the present invention, but nonionic dyes are preferred to decrease interaction with dye transfer inhibitor. Useful acid dyes include: Polar Brilliant Blue, and D&C Yellow X10, both supplied by Hilton Davis, Cincinnati, Ohio. Nonionic Liquitinte dyes supplied by Milliken, Spartanburg, South Carolina, are also useful. Especially pre-ferred Liquitint dyes are selected from the group consisting of:
Blue HP, Blue 65, Experimental Yellow 8949-43, Green HMC, Patent Blue, Royal Blue, Teal, Violet, Yellow II, and mixtures thereof.
A preferred composition contains from OX to about 3X of polydimethylsiloxane, from OX to about 0.4X of CaCl2, and from about 10 ppm to about 100 ppm of dye.
The pH (lOX solution) of the compositions of this invention is generally adjusted to be in the range of from about 2 to about

7, preferably from about 2.4 to about 6.5, more preferably from about 2.6 to about 4. Adjustment of pH is normally carried out by including a small quantity of free acid in the formulation.
Because no strong pH buffers are present, only small amounts of acid are required. Any acidic material can be used; its selection can be made by anyone skilled in the softener arts on the basis of cost, availability, safety, etc. Among the acids that can be used are methyl sulfonic, hydrochloric, sulfuric, phosphoric, citric, malefic, and succinic. For the purposes of this invention, pH is measured by a glass electrode in a lOX solution in water of the softening composition in comparison with a standard calomel reference electrode.
Y. Process of Making Liauid Compositions The liquid fabric softening compositions of the present invention can be prepared by the following methods. A convenient and satisfactory method is to prepare a softening active melt WO 94/11482 . 2 ~ -~-9 5 4 7 PCT/US93/10451 premix (active premix) at from about 100'F (about 38'C) to about 190'F (about 88'C), which is then added with high shear mixing with milling to the hot water seat at from about 100'F (about 38'C) to about 190'F (about 88'C). The dye transfer inhibitor can be added to the water seat, prior to the beginning of the premix transfer, either as a powder or as an aqueous solution. Tempera-ture-sensitive optional components can be added after the fabric softening composition is cooled to a lower temperature. Prefer-ably the liquid softener compositions of the present invention are made by a process comprising the following steps:
(a) Melting and mixing softener active;
(b) Adding the dye transfer inhibitor to the water seat, the water seat having a temperature from about 100'F (about 38'C) to about 190'F (about 88'C);
(c) Adding the mixture of (a) into the water seat with agitation;
(d) Optionally adding a viscosity control agent (e. g., CaCl2); and (e) Cooling the composition.
The dye transfer inhibitor can also be added upon cooling of the composition, during or after Step (e), or into the water seat after premix addition is complete, i.e., after Step (c) but before Step (d).
Surprisingly, adding the dye transfer inhibitor into the water seat prior to premix addition results in products having a better dye transfer inhibition than products with dye transfer inhibitor added after premix addition and cooling.
The liquid fabric softening compositions of this invention are used by adding to the rinse cycle of conventional home laundry operations. Generally, rinse water has a temperature of from about 5'C to about 50'C, more frequently from about 10'C to about 40'C. The concentration of the fabric softener actives of this invention is generally from about 10 ppm to about 200 ppm, prefer-ably from about 25 ppm to about 100 ppm, by weight of the aqueous rinsing bath. The concentration of the dye transfer inhibitor is generally from about 0.3 ppm to about 500 ppm, more preferably from about 1 ppm to about 300 ppm in the rinse solution.

In general, the present invention in its fabric softening method aspect comprises the steps of (1) washing fabrics in a conventional washing machine or hand washing with a detergent composition; and (2) rinsing the fabrics in a bath which contains the above described amounts of the fabric softeners; (3) drying the fabrics in an automatic laundry dryer or line drying; and (4) subsequent washing of fabrics in a conventional washing machine or hand washing with a detergent composition. When multiple rinses are used, the fabric softening composition is preferably added to the final rinse.
DRYER-ADDED FABRIC SOFTENING COMPOSITIONS
The present invention also relates to dryer-added fabric conditioning (softening) compositions and articles of manufacture in which the fabric conditioning (softening) compositions are affixed to a dispensing means, e.g., a substrate.
In preferred embodiments, the present invention encompasses articles of manufacture, adapted for use to provide unique dye transfer inhibition benefits and to soften fabrics in an automatic laundry dryer, of the types disclosed in U.S.
Pat. Nos:
3,989,631 Marsan, issued Nov. 2, 1976; 4,055,248, Marsan, issued Oct. 25, 1977;
4,073,996, Bedenk et al., issued Feb. 14, 1978; 4,022,938, Zaki et al., issued May 10, 1977; 4,764,289, Trinh, issued Aug. 16, 1988; 4,808,086, Evans et al., issued Feb. 28, 1989; 4,103,047, Zaki et al.; issued July 25, 1978; 3,736,668, Dillarstone, issued June 5, 1973; 3,701,202, Compa et al., issued Oct. 31, 1972; 3,634,947, Furgal, issued Jan. 18, 1972; 3,633,538, Hoeflin, issued Jan. 11, 1972; and 3,435,537, Rumsey, issued Apr. 1, 1969; and 4,000,340, Murphy et al., issued Dec. 28, 1976.
Typical articles of manufacture of this type include articles comprising:
1. A fabric conditioning composition comprising:
I. An effective amount, preferably from about 50% to about 99%, more preferably from about 70% to about 99%, of fabric softening agent;
II. An effective amount, preferably from about 0.2% to about 50%, more preferably from about 1 % to about 30%, of polymeric dye transfer inhibiting agent; and III optionally, a dispensing means which provides for release of an effective amount of said composition to fabrics in an automatic laundry dryer at automatic laundry dryer operating temperatures, e.g., from about 35°C to 115°C.
When the dispensing means is a flexible substrate, e.g., in sheet configuration, the fabric conditioning composition is releasably affixed on the substrate to provide a weight ratio of conditioning composition to dry substrate ranging from about 10:1 to about 0.5:1, preferably from about 5:1 to about 1:1.
The term "fabric softening agent" as used herein includes cationic and nonionic fabric softeners used alone and also in combination with each other. A
preferred fabric softening agent of the present invention is a mixture of cationic and nonionic fabric softeners. An effective amount of dye transfer inhibitor is an amount which will provide from about 0.1 ppm to about 500 ppm of DTI in the wash solution.
I. Fabric Softening Agents Examples of fabric softening agents that are especially useful in the substrate articles are the compositions described in U.S. Pat. Nos.: 4,103,047, Zaki et al., issued July 25, 1978; 4,237,155, Kardouche, issued Dec. 2, 1980; 3,686,025, Morton, issued Aug. 22, 1972; 3,849,435, Diery et al., issued Nov. 19, 1974; and U.S. Pat.
No.
4,073,996, Bedenk et al., issued Feb. 14, 1978. Other fabric softening agents are disclosed hereinafter with respect to detergent-compatible fabric conditioning compositions.
Particularly preferred cationic fabric softeners for substrate articles include quaternary ammonium salts such as dialkyl dimethylammonium chlorides, methylsulfates, and ethylsulfates wherein the alkyl groups can be the same or different and contain from about 14 to about 22 carbon atoms. Examples of such preferred materials include ditallowalkyldimethylammonium methylsulfate (DTDMAMS), disterayldimethylammonium methylsulfate, dipalmityldimethylammonium methylsulfate and dibehenyldimethyl-ammonium methylsulfate. Also particularly preferred are the carboxylic acid salts of tertiary alkylamines disclosed in said Kardouche patent.
Examples include stearyldimethylammonium stearate, distearylmethylammonium myristate, stearyldimethylammonium palmitate, distearylmethylammonium palmitate, and distearylmethylammonium laurate. These carboxylic salts can be made in situ by mixing the corresponding amine and carboxylic acid in the molten fabric conditioning composition.
Other preferred types of fabric softener are described in detail in U.S. Pat.
No.
4,661,269, Toan Trinh, Errol H. Wahl, Donald M. Swartley, and Ronald L.
Hemingway, issued April 28, 1987.
Examples of nonionic fabric softeners are the sorbitan esters, C12-C2s fatty alcohols, and fatty amines described herein.
A preferred fabric softening agent for use in substrate articles comprises a mixture of (1) Coo-C2s acyl sorbitan esters and mixtures thereof, (2) quaternary ammonium salt, and (3) tertiary alkylamine. The quaternary ammonium salt is preferably present at a level of from about 5% to about 25%, more preferably from about 7% to about 20% of the fabric conditioning composition. The sorbitan ester is preferably present at a level of from about 10% to about 50%, more preferably from about 20% to about 40%, by weight of the fabric conditioning composition. The tertiary alkylamine is present at a level of from about 5% to about 25%, more preferably from 7% to about 20%
by weight of the fabric conditioning composition. The preferred sorbitan ester comprises a member selected from the group consisting of Coo-C2s acyl sorbitan monoesters and Coo-C2s acyl sorbitan di-esters, and ethoxylates of said esters wherein one or more of the unesterified hydroxyl groups in said esters contain from 1 to about 6 oxyethylene units, and mixtures thereof. The quaternary ammonium salt is preferably in the methylsulfate form. The preferred tertiary alkylamine is selected from the group consisting of alkyldimethylamine and dialkylmethylamine and mixtures thereof, wherein the alkyl groups can be the same or different and contain from about 14 to about 22 carbon atoms.
Yet another preferred fabric softening agent comprises a carboxylic acid salt of a tertiary alkylamine, in combination with a fatty alcohol and a quaternary ammonium salt. The carboxylic acid salt of a tertiary amine is used in the fabric conditioning composition preferably at a level of from about 5% to about 50%, and more preferably, from about 15% to about 35%, by weight of the fabric treatment composition. The quaternary ammonium salt is used preferably at a level of from about 5% to about 25%, and more preferably, from about 7% to about 20%, by weight of the fabric treatment composition. The fatty alcohol can be used preferably at a level of from about 10% to about 25%, and more preferably from about 10%
to about 20%, by weight of the fabric treatment composition. The preferred quaternary ammonium salt is selected from the group consisting of dialkyl dimethylammonium salt wherein the alkyl groups can be the same or different and contain from about 14 to about 22 carbon atoms and wherein the counteranion is selected from the group consisting of chloride, methylsulfate and ethylsulfate, preferably methylsulfate. The preferred carboxylic acid salt of a tertiary alkylamine is selected from the group consisting of fatty acid salts of alkyldimethylamines wherein the alkyl group contains from about 14 to about 22 carbon atoms, and the fatty acid contains from about 14 to about 22 carbon atoms, and mixtures thereof. The preferred fatty alcohol contains from about 14 to about 22 carbon atoms.
More biodegradable fabric softener compounds can be desirable.
Biodegradability can be increased, e.g., by incorporating easily destroyed linkages into hydrophobic groups. Such linkages include ester linkages, amide linkages, and linkages containing unsaturation and/or hydroxy groups. Examples of such fabric softeners can be found in U.S. Pat. Nos: 3,408,361, Mannheimer, issued Oct. 29, 1968;
4,709,045, Kubo et al., issued Nov. 24, 1987; 4,233,451, Pracht et al., issued Nov. 11, 1980;
4,127,489, Pracht et al., issued Nov. 28, 1979; 3,689,424, Berg et al., issued Sept. 5, 1972; 4,128,485, Baumann et al., issued Dec. 5, 1978; 4,161,604, Elster et al., issued July 17, 1979; 4,189,593, Wechsler et al., issued Feb. 19, 1980; and 4,339,391, Hoffman et al., issued July 13, 1982.

WO 94: 2 1 4 9 5 4 7 P~T/L1S93/10451 II. polymeric Dve Transfer Inhibiting Agents Dye transfer inhibiting agents useful for dryer-added fabric softening compositions and articles of the present invention are those described earlier for rinse-added fabric softening compo-sitions. Preferred are solid materials having particle size of about 1 mn or smaller, more preferably about 0.5 mm or smaller, most preferably about 0.2 nm or smaller. Commercial solid poly-vinylpyrrolidones are normally available with particle size of less than about 1 mm.
When the dye transfer inhibiting agent has a larger particle size, the particle size can be conveniently reduced by grinding techniques followed by an appropriate particle size sorting method, e.g., sieving.
It is desirable, for ease of application, to intimately admix the ingredients of the fabric softening composition before appli cation to a substrate dispensing means.
III. ~tional Dispensing Means In the preferred substrate article embodiment, the fabric conditioning compositions are provided as an article of manu facture in combination with a dispensing means such as a flexible substrate which effectively releases the composition in an auto-matic laundry (clothes) dryer. Such dispensing means can be designed for single usage or for multiple uses. The dispensing means can also be a "vanishing substrate material" that releases the fabric conditioning composition and then is dispersed and/or exhausted from the dryer.
The dispensing means will normally carry an effective amount of fabric conditioning composition. Such effective amount typic-ally provides sufficient fabric softening agent and dye transfer inhibitor for at least one treatment of a minimum load in an automatic laundry dryer. Amounts of fabric conditioning composition for multiple uses, e.g., up to about 30, can be used.
Typical amounts for a single article can vary from about 0.25 g to about 100 g, preferably from about 0.5 g to about 10 g, most preferably from about 1 g to about 5 g.
A highly preferred article herein comprises the fabric conditioning composition releasably affixed to a flexible sub-strate in a sheet configuration. Highly preferred paper, woven or nonwoven "absorbent"
substrates useful herein are fully disclosed in U.S. Pat. No. 3,686,025, Morton, issued Aug. 22, 1972.
Nonwoven cloth substrates preferably comprise cellulosic fibers having a length of from about 3/16 inch to about 2 inches and a denire of from about 1.5 to about 5 and the substrates are adhesively bonded together with binder resin.
The flexible substrate preferably has openings sufficient in size and number to reduce restriction by said article of the flow of air through an automatic laundry dryer.
The better openings comprise a plurality of rectilinear slits extended along one dimension of the substrate.
The substrate embodiment of this invention can be used for imparting the above-described fabric conditioning composition to fabric to provide dye transfer inhibition andlor softening and/or antistatic effects to fabric in an automatic laundry dryer in a process comprising: comingling pieces of damp fabric by tumbling said fabric under heat in an automatic clothes dryer with an effective amount of the fabric conditioning composition, at least the continuous phase of said composition having a melting point greater than about 35°C and said composition being mobilized, e.g., flowable, at dryer operating temperature, said composition comprising from about 0.2% to about 50%, preferably from about 1 % to about 30% of a dye transfer inhibitor powder, and from about 50% to about 99%, preferably from about 70% to about 99%, of fabric softening agent selected from the above-defined cationic and nonionic fabric softeners and mixtures thereof.
The method herein is carried out in the following manner. Damp fabrics, usually containing from about 1 to about 3.5 times their weight of water, are placed in the drum of an automatic laundry (clothes) dryer. In practice, such damp fabrics are commonly obtained by laundering, rinsing, and spin-drying the fabrics in a standard washing machine. In a preferred mode, the present process is carried out by fashioning an article comprising the substrate-like dispensing means of the type hereinabove described in releasable combination with a fabric conditioning composition. This article is simply added to a clothes dryer together with the damp fabrics to be treated. The dryer is then operated in standard fashion to dry the fabrics, usually at a temperature of from about 50°C to about 80°C for a period from about 10 minutes to about 60 minutes, depending on the fabric load and type. On removal from the dryer, the dried fabrics have acquired treatment with dye transfer inhibitor and are softened. It is believed that the dye transfer inhibitor deposited on the fabric is resolubilized in the subsequent wash solution to provide a noticeable dye transfer inhibition effect.
IV. Optional Ingredients A. Viscosity Control Agents Very useful ingredients are viscosity control agents, especially particulate clays, which are especially useful in the substrate articles. Examples of the particular clays useful in the present invention are described in U.S. Pat. No. 4,103,047. A
preferred clay viscosity control agent is calcium bentonite clay, available from Southern Clay Products under the trade name Bentolite~ L. The clay viscosity control agent is preferably present at a level of from about 0.5% to about 15%, more preferably from about 1.5% to about 10% by weight of the fabric conditioning composition.
B. Other Optional Ingredients Well known optional components included in the fabric conditioning composition which are useful in the present invention are narrated in U.S. Pat. No.
4,103,047.
A preferred optional ingredient is perfume/cyclodextrin inclusion complex present in the fabric conditioning composition at from about 0.5% to about 50%, preferably from about 1% to about 45%, more preferably from about 5% to about 40%. See U.S.
Pat.
No. 5,094,761, Trinh, Gardlik, Banks, and Benvegnu, issued Mar. 10, 1992; and U.S.
Pat. No. 5,102,564, Gardlik, Trinh, Banks, and Benvegnu, issued Apr. 7, 1992.
Another preferred optional ingredient is free perfume, other than the perfume which is present as the perfumelcyclodextrin inclusion complex, which is also very useful for imparting odor benefits, especially in the product andlor in the dryer. Preferably, such free perfume contains at least about 1 %, more preferably at least about 10% by weight of said free perfume, of substantive perfume materials. Such free perfume is preferably present at a level of from about 0.10% to about 10% by weight of the portion of the composition that is transferred to the fabrics, e.g., everything but the dispensing means in substrate articles.
Other preferred optional ingredients are polymeric soil release agents, described in Section IV.A above of liquid compositions. Preferably, these polymeric soil release agents contain one, or more, negatively charged functional groups such as the sulfonate functional group, preferably as capping groups at the terminal ends of said polymeric soil release agent. The soil release agent is preferably present at a level of from about 1 % to about 50%, more preferably from about 5% to about 45%, and most preferably from about 10% to about 40%, by weight of the fabric conditioning composition.
The polymeric soil release agents preferably become molten at temperatures no higher than about 90°C and have viscosities of less than about 10,000 cps at 85°C.
Other polymeric soil release agents with higher viscosities can be used when they are mixed with a viscosity reducing agent. Examples of some viscosity reducing agents for polymeric soil release agents, useful for the present invention, are given in U.S. Pat.
Nos.: 4,863,619, issued Sept. 5, 1989; 4,925,577, issued May 15, 1990;
5,041,230, issued Aug. 20, 1991, to Borcher, Delgado, and Trinh.
The articles of manufacture disclosed hereinbefore can impart noticeable dye transfer inhibition benefits plus softening and/or antistatic effects to fabrics when used in an automatic laundry dryer.
SOLID, PARTICULATE FABRIC SOFTENER COMPOSITIONS
Solid, particulate fabric softening compositions of the present invention typically comprise:
I. an effective amount, preferably from about 20% to about 90%, more preferably from about 30% to about 70%, of fabric softening agent; and I I. an effective amount, preferably from about 0.1 % to about 80%, more preferably from about 0.3% to about 50%, and even more preferably from about 0.5% to about 25%, of dye transfer inhibiting agent.
An effective amount of DTI is an amount which will provide from about 0.1 ppm to about 500 ppm of DTI in the rinse solution.
Optional, but preferred, ingredients include dispersing agents and perfumes.
Preferred dispersing agents are cationic surfactants such as C~2-C~8 alkyl trimethylammonium halide, choline ester of fatty acids, etc. Such dispersing agents are present at a level of from 0 to about 45%, preferably from about 1 % to about 30%.
Particulate fabric softener compositions for addition in the wash or rinse cycles of an automatic laundering operation have been described in, e.g., U.S. Pat.
Nos.:
3,256,180, Weiss, issued June 14, 1966; 3,351,483, Miner et al., issued Nov.
7, 1967;
4,308,151, Cambre, issued Dec. 29, 1981; 4,589,989, Muller et al., issued May 20, 1986;
and 5,009,800, Foster, issued April 23, 1991; and foreign patent applications:
Jap. Laid Open Appln. No. 8799184, Laid open Jan. 18, 1984; Jap. Appln. No. J62253698-A, Nov.
5, 1987; Jap. Laid Open Appln. No. 1-213476, laid open Aug. 28, 1989; Can.
Appln. No.
CA1232819-A, Feb. 16, 1988; Jap. Appln. No. J63138000-A, June 9, 1988; and European Appln. No. EP-289313-A, Nov. 2, 1988. A granular fabric softener composition which can be used to prepare a liquid composition is disclosed in allowed U.S.
Pat.
Application Ser. No. 07/689,406*, Hartman, Brown, Rusche, and Taylor, filed April 22,1991.
COMPOSITIONAL ADVANTAGES OF THE PRESENT INVENTION
Preferably the softener compositions of the present invention are substantially, preferably, essentially free of aerosol propellants; bleach (especially activated bleach);
sachets containing active ingredient; and anionic surfactants. The liquid softener (* Equivalent to W092/18593 published 29.10.92.) compositions are, in addition, essentially free of large amounts (more than two times the amount of polymeric DTI) of highly ethoxylated and/or propoxylated materials (more than about eight ethoxylated and/or propoxylated units) when the fabric softening agent is methyl-1-oleylamidoethyl-2-oleylimidazolinium metho-sulfate, or analogous agent. The dryer-added compositions are also essentially free of polymer-coated soil release polymers.

The present invention, especially in the fabric softener aspect, can provide improved DTI benefits after multiple laundry operations. In addition, the invention can improve the appearance of fabrics that have previously been stained by dye transfer.

Even after dyes deposit and discolor fabric, the polymeric DTI

will help remove this dye from fabrics, especially, e.g., in fabric softener compositions, when used in multiple cycles.
Also, the invention can provide a soil anti-redeposition benefit in the wash cycle.

The present invention also relates to a laundry method of minimizing dye transfer during the wash cycle of a laundering process by providing an effective amount of dye transfer inhibitor into the wash solution by means other than by adding it as part of a detergent composition. For example, DTI can be added to the wash solution as a powder, an aqueous solution, via a dispensing means (e. g., substrate) which will prevent powder inhalation, etc.

The invention also encompasses a laundry process (method) for imparting dye transfer inhibition plus softening and/or antistatic effects to fabrics comprising: washing a load of fabrics in a wash solution containing a detergent composition; rinsing said load of fabrics with a composition comprising an effective amount of softening active and an effective amount of dye transfer inhibitor and/or tumbling the load of fabrics under heat in the dryer with a dryer-added softener composition comprising an effective amount of dye transfer inhibitor; and subsequently washing all or part of said load of fabrics, together with or without additional fabrics, during which the dye transfer inhibitor is effectively released into the wash solution containing a detergent composition.
A load of fabrics includes one or more fabric articles.

The following are nonlimiting examples of the instant WO 94/114$2 '~ ~ ~ ~ PCT/US93/10451 articles'and methods. The examples presented hereinbefore and hereinafter do not limit the present invention.
Examples of Liauid Fabric Softening Compositions The following liquid softener compositions, when added to the rinse cycle of an automatic laundry operation, show dye transfer inhibition in the subsequent wash cycle.
Examples: 1-33 4 Components (Wt.X) (Wt.X) DTDMAC/MTTMAC* Blend (83X) 4.5 4.5 1-Tallow(amidoethyl)-2-Tallowimidazoline - 3.4 HC1 - 0.2 PVP K-15 1.0 0.5 Perfume - 0.4 Minor Ingredients** 0.5 0.5 Deionized Water Balance Balance 100.00 100.00 *Ditallowdimethylanmonium chloride/monotallowtrimethyl-artmonium chloride.
**Minor ingredients include: Dow Corning polydimethylsiloxane.
emulsion, calcium chloride, Kathone CG/ICP bacteriocide, and Liquitints Blue 65 dye.
XAMP
The compos i ti on of Exampl a 1 i s made by the fol 1 owi ng pro-cedures:
Adding PVP K-15 (average molecular weight of about 10,000, either as a powder or in aqueous solution) with mixing to a vessel containing deionized water, heated to about 65'C. Molten DTDMAC/MTTMAC blend (at about 80'C) is added with high shear mixing to the aqueous solution. After softener incorporation, the mixture is cooled, and the minor ingredients are added during the cooling process.

The composition of Example 2 is made similarly to the pro-cedure of Example 1, except that the PYP is added after about 85X

WO 94/11482 ~ !~ ~ ~ 4: ~ , PCT/US93/10451 r . 41 -of the softener addition is complete. Viscosity is adjusted at this point by adding calcium chloride (0.17X) before PYP addition.

The composition of Example 3 is madesimilarlyto the pro-s cedure of Example 2, except the PVP added that is after all of the softener has been added and the n cooledto room dispersio tem-perature.

Examples: .

Components (Wt.%) (Wt.X) (Wt.X) DTDMAC/MTTMAC* Blend (83X) 10.48 10.48 10.48 1-Tallow(amidoethyl)-2-Tallowimidazoline 14.3 14.3 14.3 HC1 0.85 0.85 0.85 PVP K-15 3.15 - -PVP K-25 ~ - 3.15 -PVP K-12 - - 3.15 Soil Release Polymer - - 2.25 Perfume 1.35 1.35 1.35 Minor Ingredients** 1.52 1.52 1.52 Deionized Water Balance Balance Balance 100.00 100.00 100.00 *Ditallowdimethylammonium chloride/monotallowtrimethyl-ammonium chloride.
**Minor ingredients as given in Example 1.

The compositions of Examples 4, 5, and 6 are made by adding PVP with mixing to a vessel containing deionized water and HC1, heated to about 65'C. DTDMAC/MTTMAC blend and 1-tallow(amido ethyl)-2-tallowimidazoline are then added as a molten blend (at about 80'C) with high shear mixing to the aqueous solution. After softener incorporation, the mixture is cooled, and the minor ingredients are added during the cooling process. Perfume is added when the composition is at about 40-50'C. The PYP used in Example 6 has an average molecular weight of about 25,000 (PVP
K-25).

WO 94/11482 ~ ~' ~ ~ ,~ 9 4 7 PCT/US93/10451 The composition of Example to that 7 is made similarly of Example 4, except that moltensoil releasepolymer added to is the aqueous solution before addition PYP. The of the soil release polymer used is the nonionic ease polymer soil rel SRP I
as described in Section IY.A liquid compositions a). The of (supr PYP

used in Example 7 has an ave rage molecular about 2,500 weight of (PYP K-12).

m les:

to Components (Wt.x) (Wt.%) (Wt.X) DTOMAC/MTTMAC* Blend (83X) 10.48 10.48 10.48 1-Tallow(amidoethyl)-2-Tallowimidazoline 14.3 14.3 14.3 HC1 0.85 0.85 0.85 Poly(2-ethyl-2-oxazoline) 3.15 - -Polyacrylamide (12,000 MW) - 3.15 -Polyacrylamide (22,000 MW) - - 3.15 Perfume 1.35 1.35 1.35 Minor Ingredients** 1.52 1.52 1.52 Deionized Hater Balance Balance Balance 100.00 100.00 100.00 *Ditallowdimethylanmonium chloride/monotallowtrimethyl-ammonium chloride.
**Minor ingredients as given in Example 1.

The composition of Example 8 is made similarly to that of Example 5, except that the PYP is replaced by poly(2-ethyl-2 oxazoline). This dye transfer inhibitor has an average molecular weight of about 50,000, and is available from Aldrich Chemical Company, Milwaukee, Wisconsin.
' EXAMPLES 9-10 The composition of Examples 9 and 10 are made similarly to that of Example 5, except that the PYP is replaced by polyacryl amide. The polyacrylamide used in Example 9 has an average molecular weight of about 12,000, while the polyacrylamide used in WO 94/11482 ; 2;~~~'~.~.9~ 5~;'~ ~ PCT/US93/10451 ,...

Example 10 has an average molecular weight of about 22,000. Both types of polyacrylamide are available from Polysciences, Warring-ton, Pennsylvania.
Example 11 Components (Wt.x) 1-Tallow(amidoethyl)-2-Tallowimidazoline Ester 22.0 PVP K-15 8.0 HC1 1.25 Perfume 1.35 Minor Ingredients** 0.4 Deionized Water Balance 100.00 **Minor ingredients as given in Example 1.

The composition of Example 11 is made similarlyto that of Example 5, except that the softener activeblend replaced is by 1-tallow(amidoethyl)-2-tallowimidazoline ester.

Examples:

Components ~ (Wt.x) (Wt.X) (Wt.x) Hard-tallow DEQA(1) 7.5 - 9 Soft-tallow DEQA(1) - 23.5 -HC1 (25X) 0.112 0.336 0.97 Soil Release Polymer(2) 0.17 0.5 0.5 Perfume 0.4 1.20 1.3 Monoester(3) 0.7 2.2 0.7 Ethanol 1.3 4 1.5 1-Tallow(amidoethyl)-2-Tallowimidazoline Ester - - 14.3 PVP K-30 1 3.15 -PVP K-15 - - 3.0 Minor Ing1~edients(4) 0.32 0.67 0.6 Water Balance Balance Balance 100.00 100.00 100.00 (1) Di(tallowoyloxyethyl)dimethyl anmonium chloride and di(tallowoyloxyethyl)methylamine.

W0 94/11482 ,L ~~2f '~~,.' j~'(~;i 5~, 4 7 PCT/US93/10451 (2) SRP I of Example 7.
(3) Mono(tallowoyloxyethyl)hydroxyethyl dimethylanmonium chloride.
(4) Minor ingredients as given in Example 1, and also including Dow Corning Antifoam 2210s.

The composition of Example 12 is made by adding PVP with mixing to a vessel containing deionized water, HC1, antifoam, and soil release polymer at about 79-85'C. DEQA is heated to about 85-90'C to melt and is then added with high shear mixing to the aqueous solution. Viscosity adjuster (e.g., calcium chloride) is added to the mixture, followed by addition of perfume. The mixture is milled and then cooled to about 18-27'C. Remaining minor ingredients are post-added at ambient temperature.

The composition of Example 13 is made similarly to that of Example 12 except that the aqueous solution to which the PYP is added is at about 77'C and the DEQA is preheated to about 71'C.

The composition of Example 14 is made similarly to that of Example 12, except that molten 1-tallow(amidoethyl)-2-tallowimi-dazoline ester is premixed with the hot DEQA before addition to the aqueous solution.
x m les: ~5 _ 16 Components (Wt.x) (Wt.X) DTOMAC/MTTMAC* Blend (83X) 10.48 10.48 1-Tallow(amidoethyl)-2-Tallowimidazoline 14.3 14.3 PVNO (50,000 MW) 1.0 -PVNO (25,000 MW) - 1.0 HC1 0.85 0.85 Perfume 1.35 1.35 Minor Ingredients** 1.52 1.52 Deionized Water Balance Balance 100.00 100.00 W0 94/11482 ~ ~; 'v 'r' °~ ~ ~'~ ~ ~ ~ ~ ~ PCT/US93/10451 *Ditallowdimethylartmonium chloride/monotallowtrimethyl-anmonium chloride.
**Minor ingredients as given in Example 1.
EXAMPLES 15 and 16 The compositions of Examples 15 and 16 are made similarly to that of Example 5, except that the PYP is replaced by poly(4-vinylpyridine N-oxide) (PYNO).
FYamgleS of Fabric Conditioning Substrate Articles The following fabric conditioning compositions and substrate articles, when added to the tumble dryer with the wet laundry load, show dye transfer inhibition in the subsequent wash cycle.
Example 17 Components (Wt.%) DTDMAC 80.00 Calcium Bentonite Clay 4.00 PYP K-15 16.00 Total 100.00 Preparation of the Coating Mix An approximately 200 gram batch of the coating mix is pre-pared as follows. An amount of about 160 g of ditallowdimethyl-anmonium chloride (OTDMAC) is melted at 80'C. The calcium ben-tonite clay (about 8 g of Bentolite L, available from Southern Clay Co.) is slowly added to the mixture with high shear mixing.
During the mixing, the mixture is kept molten in a boiling water bath. About 32 g of PVP K-15 is then slowly added to the mixture with high shear mixing, and the formula is mixed until the mixture is smooth and homogenous.
p~gp~ration of Fabric Conditioning Sheets The coating mixture is applied to preweighed nonwoven sub-strate sheets of about 9 inch x 11 inch (approximately 23 cm x 28 cm) dimensions. The substrate sheets are comprised of 70%
3-denier, 1-9/16 inch (approximately 4 cm) long rayon fibers with 30% polyvinyl acetate binder. The substrate weight is about 16 g per square yard (about 1.22 g/sheet). A small amount of formula WO 94/11482 ~ '~ '?' ~ ~~ 4 9 5 4 7 pCT/US93/10451 is placed on a heated metal plate with a spatula and then is spread evenly with a wire metal rod. A nonwoven substrate sheet i s pl aced on the metal pl ate to absorb the coati ng mi xture . The sheet is then removed from the heated metal plate and allowed to cool to room temperature so that the coating mix can solidify.
The sheet is weighed to determine the amount of coating mixture on the sheet. The target coating is 2.0 g per sheet. If the weight is in excess of the target weight, the sheet is placed back on the heated metal plate to remelt the coating mixture and remove some of the excess. If the weight is under the target weight, the sheet is also placed on the heated metal plate and more coating mixture is added.
Exam 1 Components (Wt.X) Octadecyldimethylamine 11.89 C12-14 Fatty Acid 8.29 C16-18 Fatty Acid 10.69 DTDMAMS 19.32 Sorbitan Monostearate 19.32 ~ Clay 3.86 PVP K-15 26.62 Total 100.00 Preparation of the Coatinv Mix and Fabric Conditioning Sheets A first blend of about 11.89 parts octadecyldimethylamine (Ethyl Corporation), 8.29 parts C12-14 fatty acid (The Procter 8~
Gamble Co.), and 10.69 parts C16-18 fatty acid (Emery Industries, Inc.) are melted together at 80'C, and a second blend of about 19.32 parts sorbitan monostearate (Mater Chemicals, Inc.) and 19.32 parts ditallowdimethylanmonium methylsulfate, DTDMAMS, (Sherex Chemical Co.) are melted together to form the softener component of the composition, during which time the mixture is kept molten in a boiling water bath. The calcium bentonite clay (3.86 parts Bentolite L, available from Southern Clay Co.) is then WO 94/11482 '4- ~ a~ ag ~ ~~ 7 r~

slowly added to the mixture while high shear mixing. An amount of about 26.62 parts of PYP K-15 is then added in small portions, and the formula is mixed until the mixture is smooth and completely homogenous.
The coating mixture is applied to preweighed nonwoven sub-strate sheets as in Example 17. The target coating is 2.33 g per sheet. Each sheet contains about 1.62 g of softener, about 0.09 g of clay, and about 0.62 g of PYP.
Examples:

Components (Wt.x) (Wt.X) Octadecyldimethylamine 10.88 11.63 C12-14 Fatty acid 7.58 -C16-18 Fatty Acid 9.78 20.59 DTDMAMS 17.67 20.20 Sorbitan Monostearate 17.67 20.20 Clay 3.54 5.99 PVP K-15 15.00 18.93 Perfume/Cyclodextrin Complex 15.44 -Free Perfume 2.44 2.46 Total 100.00 100.00 Coating Wt. per Sheet (g) 2.55 2.52 Prpr,aration of Coating Mix and Fabric Conditioning Sheets The softener mixture of Example 19 is prepared similarly to that of Example 18. However, the coating mixture of Example 19 contains both perfume in the free state and perfume complexed with ~-cyclodextrin. The free perfume provides the initial perfume odor to the dry fabrics, while the complexed perfume is used to provide the freshness impression to the re-wetted fabrics. The target coating is 2.55 g per sheet. Each sheet contains about 1.62 g of softener, about 0.09 g of clay, 0.38 g of PYP, about 0.40 g of perfume/cyclodextrin complex, and about 0.062 g of free perfume.

WO 94/11482 Sk ~ ø~ ~~ ~~ ~ Y~ 7 PCT/US93/10451 Preparation of Coating Mix and Fabric Conditioning Sheets A fabric conditioning composition and a dryer-added fabric conditioning article comprising a rayon nonwoven fabric substrate [having a weight of 1.22 g per 99 sq. in. (approximately 639 cm2)]
are prepared in the following manner.
A premixture is prepared by admixing about 11.63 parts octadecyldimethylamine with about 20.59 parts C16-18 fatty acid at about 75'C. Then about 20.20 parts sorbitan monostearate and about 20.20 parts ditallowdimethylanmonium methylsulfate are added with high shear mixing at about 75'C. After the addition is completed and a sufficient period of mixing time has elapsed, about 5.99 parts of Bentolite L particulate clay is added slowly while maintaining the high shear mixing action. Then about 18.93 parts of PVP powder is added with mixing. Finally about 2.46 parts of perfume is added to complete the preparation of the fabric conditioning composition.
The flexible substrate, comprised of about 70X 3-denier, 1-9/16 inch long (approximately 4 cmj rayon fibers and about 30x polyvinyl acetate binder, is impregnated by coating one side of a continuous length of the substrate and contacting it with a rotating cylindrical member which serves to press the liquified mixture into the interstices of the substrate. The amount of fabric conditioning mixture applied is controlled by the flow rate of the mixture and/or the line speed of the substrate. The substrate is passed over several chilled tension rolls which help solidify the conditioning mixture. The substrate sheet is about 9 inches wide (approximately 23 cm) and is perforated in lines at about 11 inch intervals (approximately 28 cm) to provide detach-able sheets. Each sheet is cut with a set of knives to provide three evenly spaced parallel slits averaging about 4 inches in length (approximately 10 cm). In this Example 18, the application rate is adjusted to apply about 2.52 g of coating mixture per sheet. Each sheet contains about 1.83 g of softener, about 0.15 g of clay, about 0.48 g of PVP and about 0.062 g of perfume.

WO 94/11482 N2 1 4 9 5 ~ ~ r PCT/US93/10451 r~

FYamnlpg of Solid Particulate Fabric Softening Compositions The following solid softener compositions can be reconsti-tuted into liquid compositions. When added to the rinse cycle of an automatic laundering operation, these liquid compositions show dye transfer inhibition in the subsequent wash cycle.
The solid particulate compositions herein effectively dis-perse following simple addition to lukewarm water with gentle agitation (e. g., manual shaking). Improved results are obtained by using higher temperatures and/or effective mixing conditions, e.g., high shear mixing, milling, etc. However, even the mild conditions provide acceptable aqueous compositions.
Example 21 ~omoonents (Wt.%) Sorbitan Monostearate 74.3 Cetyltrimethylammonium Bromide 24.8 PYP K-15 0~9 Total 100.0 A homogeneous mixture of cetyltrimethylammonium bromide (CTAB) and sorbitan monostearate (SMS) is obtained by melting SMS
(about 165 g) and mixing CTAB (about 55 g) therein. The solid softener product is prepared from this "co-melt' by one of two methods: cryogenic grinding (at about -78'C) to form a fine powder, or (b) grilling to form particles of particle size of from about 50 to about 500 fan.
Cryogenic Grinding The molten mixture is frozen in liquid nitrogen and ground in a Waring blender to a fine powder. The powder is placed in a dessicator and allowed to warm to room temperature, yielding a fine, free flowing powder (granule).
.Pr~llina The molten mixture (at about 88'C) falls about 1.5 inches at a rate of about 65g/min. onto a heated (about 150'C) rotating (about 2,000 rpm) disk. As the molten material is spun off the disk and air cooled (as it radiates outward), neat-spherical WO 94/11482 _ _ " ~~ ~~ ~,, 2 1 4 9 5 ~ ~ pL'1'/US93/10451 granule particles form with particle size of from about 50 to about 500 dun.
About 1 g of PVP K-15 powder of average MW of about 10,000 is added to and intimately mixed with about 110 g of the solid particulate softener composition to make the solid, particulate fabric softening composition of Example 21.
This solid, particulate fabric softener can be added directly to the rinse, or can be used to prepare a liquid softener. To make a conventional liquid softener about 111 g of solid particles is dispersed in about 889 g of warm water at about 40'C and vigorously shaken for approximately 5 minutes. Upon cooling, the aqueous product remains in a homogeneous emulsified, or dispersed, state. Addition of this liquid product or the solid, particulate product to the rinse cycle of a washing process provides fabric softening and dye transfer inhibition characteristics.
Example 22 Components (Wt.x) DEQA(1) 60.0 PGMS(2) 17.4 Coconut Choline Ester Chloride 8.6 PVNO 10.5 Minor Ingredients (Perfume; Antifoam) 3.5 Total 100.0 (1) Di(tallowoyloxyethyl)dimethyl anmonium chloride.
(2) Polyglycerol monostearate having a trade name of Radiasurfe 7248.

About 60 parts of molten DEQA is mixed with about 8.6 parts of molten coconut choline ester chloride and about 17.4 parts of molten PGMS. About 10.5 parts of powdered PVNO of average molecular weight of about 50,000 is then added. The active mixture is cooled and solidified by pouring onto a metal plate, and then ground. Trace of solvent is removed by a Rotovapor~
(about 2 hrs. at about 40-50'C at maximum vacuum). The resulting WO 94/11482 2 ~ 4 g 5 ~ 7 PCT/US93/10451 ,.

active powder is ground and sieved to make the solid, particulate fabric softening product. The reconstitution of the powder into a liquid softener product is made as follows: About 900 g of tap water is heated to about 35'C (about 95'F). About 10 g of anti-s foam and about 2.5 g of perfume are added to the water. About 96.5 g of the active powder is sprinkled on the water under continuous agitation. This resulting product is cooled by means of a cooling spiral prior to storage.

Claims (40)

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE PROPERTY OR
PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. A fabric softening composition capable of reducing the transfer of dyes during subsequent wash cycles comprising:
I. an effective amount of fabric softening agent; and II. An effective amount of water-soluble polymeric dye transfer inhibitor selected from the group consisting of:
(A) polymers, which are not enzymes, with one or more monomeric units containing at least one =N-C(=0)- group having an average molecular weight of from about 500 to about 100,000;
(B) polymers with one or more monomeric units containing at least one N-oxide group having an average molecular weight of from about 500 to about 1,000,000;
(C) polymers containing both =N-C(=0)- and N-oxide groups of (A) and (B);
(D) mixtures thereof; and wherein the composition is essentially free of aerosol propellant; bleach;
sachets containing an active ingredient; anionic surfactant; and additionally for liquid compositions, essentially free of large amounts of highly ethoxylated and/or propoxylated material when the fabric softening agent is methyl-1-oleylamidoethyl-2-oleylimidazolinium methosulfate, or analogous agent, and additionally, for dryer-added compositions, essentially free of polymer-coated soil release polymers.

2. The fabric softening composition according to Claim 1 wherein said dye transfer inhibitor is polyvinylpyrrolidone.

3. The fabric softening composition according to Claim 1 wherein said dye transfer inhibitor is poly(4-vinylpyridine N-oxide).

4. A liquid composition according to Claim 1 comprising:
I. From about 3% to about 50% fabric softening agent; and II. From about 0.03% to about 25% of said dye transfer inhibitor.

5. The liquid composition according to Claim 4 wherein said dye transfer inhibitor is (A) having an average molecular weight of from about 500 to about 40,000.

6. The liquid composition according to Claim 5 wherein said dye transfer inhibitor has an average molecular weight of from about 1,000 to about 30,000.

7. The liquid composition according to Claim 4 wherein said dye transfer inhibitor is polyvinylpyrrolidone.

8. The liquid composition according to Claim 4 wherein said dye transfer inhibitor is (B) having an average molecular weight of from about 1,000 to about 100,000.

9. The liquid composition according to Claim 8 wherein said dye transfer inhibitor has an average molecular weight of from about 2,000 to about 100,000.

10. The liquid composition according to Claim 4 wherein said dye transfer inhibitor is poly(4-vinylpyridine N-oxide).

11. A process of making the liquid composition of Claim 4 comprising the following steps:
(a) Melting and mixing the softener active;
(b) Adding dye transfer inhibitor to the water seat, the water seat having a temperature of from about 100'F
to about 190'F;
(c) Adding the mixture of (a) into the water seat with agitation;
(d) Optionally adding a viscosity control agent; and (e) Cooling the composition.

12. The process of Claim 11 wherein the dye transfer inhibitor is added after Step (c) but before Step (d).

13. A method of minimizing dye transfer during the wash cycle of a laundering process comprising the following steps:
(a) washing a load of fabrics in a wash solution containing a detergent composition;
(b) rinsing said load of fabrics with an effective amount of the liquid fabric softening composition of Claim 4;
(c) drying said load of fabrics; and (d) washing all or part of said load of fabrics, together with or without additional fabrics, said load releasing an effective amount of dye transfer inhibitor into a wash solution containing a detergent composition.

14. A dryer-added composition according to Claim 1 comprising:
I. from about 50% to about 99% fabric softening agent;
II. from about 0.2% to about 50% of said dye transfer inhibitor; and III. optionally, a dispensing means which provides for release of an effective amount of the composition to fabrics.

15. The dryer-added composition according to Claim 14 wherein the fabric softening agent is from about 70% to about 99% and said dye transfer inhibitor is from about 1% to about 30%.

16. The dryer-added composition according to Claim 14 wherein said dye transfer inhibitor has a particle size of about 0.5 mm or smaller.

17. The dryer-added composition according to Claim 16 wherein said dye transfer inhibitor has a particle size of about 0.2 mm or smaller.

18. The dryer-added composition according to Claim 14 wherein said dye transfer inhibitor is (A) having an average molecular weight of from about 500 to about 40,000.

19. The dryer-added composition according to Claim 18 wherein said dye transfer inhibitor has an average molecular weight of from about 1,000 to about 30,000.

20. The dryer-added composition according to Claim 14 wherein said dye transfer inhibitor is polyvinylpyrrolidone.

21. The dryer-added composition according to Claim 14 wherein said dye transfer inhibitor is (B) having an average molecular weight of from about 1,000 to about 100,000.

22. The dryer-added composition according to Claim 21 wherein said dye transfer inhibitor has an average molecular weight of from about 2,000 to about 100,000.

23. The dryer-added composition according to Claim 14 wherein said dye transfer inhibitor is poly(4-vinylpyridine N-oxide).

24. The dryer-added composition according to Claim 14 which additionally comprises from about 5% to about 40%
perfume/cyclo/dextrin complex.

25. The dryer-added composition according to Claim 14 additionally containing polymeric soil release agent at a level of from about 10% to about 40%.

26. A method of minimizing dye transfer during the wash cycle of a laundering process comprising the following steps:
(a) washing a load of fabrics in a wash solution containing a detergent composition;
(b) rinsing said load of fabrics;
(c) drying said load of fabrics in a tumble dryer with an effective amount of the dryer-added softening composition of Claim 14; and (d) washing all or part of said load of fabrics, together with or without additional fabrics, said load releasing an effective amount of dye transfer inhibitor into the wash solution containing a detergent composition.

27. A solid particulate composition according to Claim 1 comprising:
I. from about 20% to about 90% fabric softening agent;
II. from about 0.1% to about 80% said dye transfer inhibitor; and III. optionally, from about 0% to about 45% of a dispersing agent.

28. The solid particulate composition according to Claim 27 wherein the fabric softening agent is from about 30% to about 70%
and said dye transfer inhibitor is from about 0.5% to about 25%.

29. The solid, particulate composition according to Claim 27 wherein said dye transfer inhibitor is (A) having an average molecular weight of from about 500 to about 40,000.

30. The solid, particulate composition according to Claim 29 wherein said dye transfer inhibitor has an average molecular weight of from about 1,000 to about 30,000.

31. The solid, particulate composition according to Claim 27 wherein said dye transfer inhibitor is polyvinylpyrrolidone.

32. The solid, particulate composition according to Claim 27 wherein said dye transfer inhibitor is (B) having an average molecular weight of from about 1,000 to about 100,000.

33. The solid, particulate composition according to Claim 32 wherein said dye transfer inhibitor has an average molecular weight of from about 2,000 to about 100,000.

34. The solid, particulate composition according to Claim 27 wherein said dye transfer inhibitor is poly(4-vinylpyridine N-oxide).

35. A method of minimizing dye transfer during the wash cycle of a laundering process comprising the following steps:

(a) washing a load of fabrics in a wash solution containing a detergent composition;
(b) rinsing said load of fabrics with an effective amount of the solid, particulate fabric softening composition of Claim 27;
(c) drying said load of fabrics; and (d) washing all or part of said load of fabrics, together with or without additional fabrics, said load releasing an effective amount of dye transfer inhibitor into a wash solution containing a detergent composition.

36. The method of Claim 35 wherein the solid, particulate softening composition is reconstituted into a liquid composition prior to addition to the rinse solution.

37. A method of minimizing dye transfer during the wash cycle of a laundering process by providing an effective amount of water-soluble polymeric dye transfer inhibitor into the wash solution by means other than by adding it as part of a detergent composition wherein said dye transfer inhibitor is selected from the group consisting of:
(A) polymers, which are not enzymes, with one or more monomeric units containing at least one =N-C(=0)- group having an average molecular weight of from about 500 to about 100,000;
(B) polymers with one or more monomeric units containing at least one N-oxide group having an average molecular weight of from about 500 to about 1,000,000;
(C) polymers containing both =N-C(=0)- and N-oxide groups of (A) and (B); and (D) mixtures thereof.

38. The method according to Claim 37 wherein said wash solution contains at least some colored fabrics which release dyes and contains fabrics which will be discolored by the released dyes.

39. The method according to Claim 37 wherein said dye transfer inhibitor has the structure:
wherein m is from 0 to 2; n is selected to provide a molecular weight of from about 500 to about 1,000,000; each P and each D can contain one or more moieties selected from the group consisting of =N-C(=0)-, ~N ~ 0, and mixtures thereof, such that said structure provides dye transfer inhibition and has a water solubility of at least 100 ppm.

40. A method of improving the appearance of fabrics discolored by dye transfer in a laundering process by providing an effective amount of water-soluble polymeric dye transfer inhibitor into the wash solution by means other than by adding it as part of a detergent composition wherein said dye transfer inhibitor is selected from the group consisting of:
(A) polymers, which are not enzymes, with one or more monomeric units containing at least one =N-C(=0)- group having an average molecular weight of from about 500 to about 100,000;
(B) polymers with one or more monomeric units containing at least one N-oxide group having an average molecular weight of from about 500 to about 1,000,000;
(C) polymers containing both an N-oxide groups of (A) and (B); and (D) mixtures thereof.