CA2253399A1

CA2253399A1 - Fabric treatment compositions comprising modified polyamines

Info

Publication number: CA2253399A1
Application number: CA 2253399
Authority: CA
Inventors: Sanjeev Krishnadas Manohar; Frederick Anthony Hartman; Janet Sue Littig; Eugene Paul Gosselink; Randall Alan Watson
Original assignee: Individual
Current assignee: Procter and Gamble Co
Priority date: 1996-05-03
Filing date: 1997-04-25
Publication date: 1997-11-13
Also published as: JPH11509267A; BR9710663A; EP0912679A1; WO1997042289A1; AR006956A1

Abstract

Fabric treatment compositions comprising: a) an effective amount of a fabric conditioning agent; and b) an effective amount of a water-soluble or dispersible, bleach stable, modified polyamine fabric surface modifier comprising a polyamine backbone.

Description

CA 022~3399 1998-10-30 W O 97/42289 PCT~US97/07001 FABRIC TREATMENT COMPOSITIONS
COMPRISING MODIFIED POLYAMINES

FIELD OF THE INVENTION
The present invention relates to fabric treatment compositions comprising modified polyamines and to methods for treating fabric for removal of proteinaceous and greasy stains. The fabric tre~tment compositions can comprise other adjunct ingredients such as fabric conditioning compounds, ble~cll~s, and perfumes. The fabric treatment compositions are effective on cotton as well as conon blends and polyester.
BACKGROUND OF THE INVENTION
The formulation of detergent compositions presents a considerable sh~lltonge, since effective compositions are required to remove a variety of soils and stains from diverse substrates. In particular, the removal of greasy/oily soils quickly and efficiently can be problematic. Additionally, grass stains, once considered to be ruinous to fabric, can be effectively treated with modern laundry compositions.
Pre-tre~tm~ont of fabrics, especi~lly the application of stain removers directly to fabrics before loading in the washing machine or pre-soaking of heavily soiled garments has become a common practice of con~l~mers. It has become standard in the field of laundry detergent art to include ingredients which enh~nce the condition of fabric beyond the single task of soil removal. Some of these adjunct materials are added separately as "tre~tment~" via the wash, rinse or dryer cycle. These ingredients for fabric enhancement have a wide range of benefits, for example, optical bright.on~rs, soil release agents, anti-static agents, softeners, dye enh~nc~rs, and perfumes.
The first wide spread use of fabric surface modification agents occured with theintroduction of soil release polymers to aid in the cle~ninp: of polyester fabrics.
Typically, soil release polymers are applied to polyester fabric via the laundry cycle where the polymers coat the surface of the fabric. This applied layer of soil release agent interdicts greasy and oily dirt and keeps it from "wetting" out across the fabric surface.
Fabric treated in this manner are more easily cleaned with conventional detersive surfactants. To date, soil release agents are generally effective on polyester fabric.
One of the additonal benefits seen due to the fabric substantivity of modern laundry adjuncts is a "through the wash carry over" phenomenon. Stated simply, amolecule capable of mç~ ting laundry wash conditions can be placed onto the surface of fabric during one wash cycle where it will remain until the next wash cycle. During this subsequent wash cycle the full utility of the ingredient is then realized. For example, it CA 022~3399 1998-10-30 WO 97/42289 PCT~US97/07001 has been surprizingly discovered that the modified polyamines of the present invention mediate the tranfer of fugitive dyes from one fabric to another.
Formulators of fabric softeners have long faced the problem of odor formation inthe laundry liquor and the automatic clothes dryer. One cause of these malodors is the possible break down of qua~ ~ y ammonium softening agents whrein volatile aldehydes are formed. It has been surprizingly found that the addition of the polyamines of the present invention to pre-wash, laundry, and laundry rinse formulations decreases the presence of malodor compounds, possibly by chemical reaction of the nitrogenmoieties of the polyamines with the aldehydes.
In additon to the mediation of fugitive dyes and malodor, these fabric substantive modified polyamines also control the ~l~m~ging effects of oxygen bleach on dyed fabric.
It has also been surprisingly found that certain modified polyamines can act as surface modifiying agents specific for cotton and blended cotton fabric. In addition, it has been discovered that the absence or presence of conventional detersive surfactants drarnatically effects the p~el lies of these modified polyamines toward stain-types.
Among the developm~ s of the present invention are fabric treatrnent compositions that when applied to cotton and blended cotton fabric, provide for surprisingly effective removal of greasy/oily stains, especially chocolate. Efficacy is obtained on these lipid-type stains when the modified polyamines described herein are fonntl~te~ in combination with anionic and nonionic detersive surf~rt~nts Several pre-treatrnents up to three, prior to usage of the fabric provides even greater fabric protection.
It has also been surprisingly discovered that the modified polyamines of the present invention used in the absence of detersive surf~rt~ntc provide for enh~nre(l removal of grass stains from all types of fabric. This nil surfactant formulation allows for other fabric L,~ ...cnt adjuncts such as softeners, anti-static agents, bleaches, and perfumes, singly or as an a-lmixtllre, to be effectively combined with the modified poly~minPs It is therefore an object of the present invention to provide compositions that modify the surface of fabric for use in a single or multiple pre-soak formula or in laundry rinse-added compositions.
It is a further object of the present invention to combine the modified polyamines of the present invention with detersive surf~rt~nts and non-cotton soil release agents to provide fabric surface modifying compositions effective against greasy/oily stains.
It is yet a further object of the present invention to combine the modified polyamines of the present invention with non-cotton soil release agents to provide fabric CA 022~3399 1998-10-30 surface modifying compositions effective against grass stains and other proteinaceous SOII.
It is still yet a further object of the present invention to provide a method for protecting fabric against greasy/oily stains or against proteinaceous stains by cont~cting the compositions of the present invention with fabrics that have been exposed to said stains or by pre-treating said fabric up to three times with the compositions described herein.
It is a further object of the present invention to provide a fabric softening composition, comprising at least one fabric softener component, for inhibiting or reducing fabric discoloration.
A further purpose is to provide a method of inhibiting or reclllcing fabric discoloration which comprises the steps of rinsing a fabric with a fabric softener composition comprising a fabric softener component and a modified poly amine of the present invention.
BACKGROUND ART
The following disclose various soil release polymers or modified poly~minlos;
U.S. Patent 4,548,744, Connor, issued October 22, 1985; U.S. Patent 4,597,898, Vander Meer, issued July 1, 1986; U.S. Patent 4,877,896, Maldonado, et al., issued October 31, 1989; U.S. Patent 4,891,160, Vander Meer, issued January 2, 1990; U.S. Patent 4,976,879, Maldonado, et al., issued December 11, 1990; U.S. Patent 5,415,807, Gosselink, issued May 16,1995; U.S. Patent 4,235,735, Marco, et al., issued November 25, 1980; WO 95/32272, published November 30, 1995; U.K. Patent 1,537,288, published Decem~çr 29, 1978; U.K. Patent 1,498,520, published January 18, 1978;
German Patent DE 28 29 022, issued January 10, 1980; J~p~n~sP Kokai JP 06313271,published April 27, 1994.
The following disclose fabric conditioning co~ ,osilions; U.S. Patent 3,944,694,McQueary; U.S. Patent 4,073,996, Bedenk et al.; U.S. Patent 4,237,155, Kardouche; U.S.
Patent 4,711,730, Gosselink et al.; U.S. Patent 4,749,596, Evans et al.; U.S. Patent 4,808,086, Evans et al.; U.S. Patent 4,818,569, Trinh et al.; U.S. Patent 5,041,230, Borcher, Sr. et al.; U.S. Patent 5,094,761, Trinh et al.; U.S. Patent 5,102,564, Gardlik et al.; and U.S. Patent 5,234,610, Gardlik et al.

SUMMARY OF THE INVENTION
The present invention relates to laundry pre-soak, pre-treatment or rinse added compositions that modify the surface of fabric to facilitate the removal of oily/ greasy dirt, lipophilic grime, and proteinaceous soils. The present invention compositions are W O 97/42289 PCT~US97/07001 used to treat fabrics in the presence or the absense of detersive surfactants. The fabric treatment compositions comprise:
a) an effective amount of a fabric conditioning agent;
b) an effective amount of a water-soluble or dispersible, bleach stable, modified polyamine fabric surface modifier comprising a polyamine backbone corresponding to the formula:
,H
[H2N~R]n+l--[N~R]m--~N~R]n~NH2 having a modified polyamine formula V(n+l)wmynz or a polyamine backbone corresponding to the formula:

H I R
[H~N-R]n-k+~[N ~R]m--[N-R]n~N-R]k-NH2 having a modified polyamine formula V(n-k+l )WmYnY kZ, wherein k is less than or equal to n, said polyamine backbone prior to modification has a molecular weight greater than about 200 daltons, wherein i) V units are tPrmin~l units having the formula:

E X O

E E or E--Nl--R
ii) W units are backbone units having the formula:

E X~ ~
--I--R or --Nl--R-- or --I--R
E E E
iii) Y units are br~n~hing units having the formula:

E X~ ~
_7 R --7+ R --7 R
; and iv) Z units are terminal units having the formula:

CA 022~3399 1998-10-30 E X~ O
--I--E or --I--E or --I--E
E E E
wherein backbone linking R units are selected from the group con.cieting of C2-C12 alkylene, C4-C12 alkenylene, C3-C12 hydroxyalkylene, C4-C12 dihydroxy-alkylene, Cg-C12 dialkylarylene, -(RIO)xRl-~ -(Rlo)xR5(oRl)x-~ -(CH2CH(OR2)CH20)z-(Rl o)yR1 (OCH2CH(OR2)CH2)W-, -C(o)(R4)rC(o)-, -CH2CH(OR2)CH2-, and mixtures thereof; wherein Rl is C2-C6 alkylene and mixtures thereof; R2 is hydrogen, -(R10)XB, and mixtures thereof; R3 is Cl-CIg alkyl, C7-C12 arylalkyl, C7-C12 alkyl substituted aryl, C6-C12 aryl, and mixtures thereof; R4 is Cl-Cl2 alkylene, C4-C12 alkenylene, Cg-C12 arylalkylene, C6-CIo arylene, and mixtures thereof; R5 is Cl-C12 alkylene, C3-C12 hydroxyalkylene, C4-C12 dihydroxy-alkylene, Cg-C12 dialkylarylene, -C(O)-, -C(O)NHR6NHC(O)-, -Rl (ORl)-, -C(o)(R4)rc(o)-~ -CH2CH(OH)CH2-, -CH2CH(OH)CH20(RIO)yRl-OCH2CH(OH)CH2-, and mixlules thereof; R6 is C2-C12 alkylene or C6-C12 arylene; E units are selected from the group con~i~ting of hydrogen, C1-C22 alkyl, C3-C22 alkenyl, C7-C22 arylalkyl, C2-C22 hydroxyalkyl, -(CH2)pCO2M, ~(CH2)qSO3M~ -CH(CH2CO2M)CO2M, -(CH2)pPO3M, -(R l O)XB, -C(o)R3, and mixtures thereof; provided that when any E unit of a nitrogen is a hydrogen, said nitrogen is not also an N-oxide; B is hydrogen, Cl-C6 alkyl, -(CH2)qs03M~ -(CH2)pC02M, ~(cH2)q(cHso3M)cH2so3M~ -(CH2)q(CHSO2M)CH2SO3M~ -(CH2)pPO3M, -PO3M, and mixtures thereof; M is hydrogen or a water soluble cation in sufficient amount to satisfy charge balance; X is a water soluble anion; provided at least one backbone nitrogen is q~.at~rni7Pd or oxidized;
m has the value from 4 to about 400; n has the value from 0 to about 200; p has the value from I to 6, q has the value from 0 to 6; r has the value of 0 or 1; w has the value 0 or 1;
x has the value from 1 to 100; y has the value from 0 to 100; z has the value 0 or 1; and c) the balance carrier and adjunct ingredients.
It is a further object of the present invention to provide fabric tres,tment composilions that comprise other suitable fabric enhancement adjunct ingredients or other fabric surface modifying agents.
Is is yet a further object of the present invention to provide methods for treating fabrics to remove greasy/oily dirt, lipophilic grime, and proteinaceous soils and to provide methods for pre-treating fabrics with compositions of the present invention to enh~n~e the removal of greasy/oily dirt, lipophilic grime, and proteinaceous soils.

.. ...

CA 022~3399 1998-10-30 All percentages, ratios and proportions herein are by weight, unless otherwise specified. All temperatures are in degrees Celsius (~ C) unless otherwise specified. All documents cited are in relevant part, incorporated herein by reference.

DETAILED DESCIPTION OF THE l~NVENTION
Fabric surface modification compositions according to the present invention for treatment of proteinaceous soils comprise:
a) from about 0.01% by weight, of a water-soluble or dispersible, bleach stable, modified polyamine fabric surface modifier according to the present invention;
b) from about 0.01% by weight, of a fabric conditioning agent; and c) the balance carrier and adjunct ingredients.
Further prefel~ed fabric surface modification compositions for treatment of proteinaceous soils com~lise:
a) from about 0.01% by weight, of a water-soluble or dispersible, bleach stable, modified polyamine fabric surface modifier according to the present invention;
b) from about 0.01% by weight, of a fabric conditioning agent;
c) from about 0.01% by weight, of a soil release polymer; and d) the balance carrier and adjunct ingredients.
Also preferred fabric surface modification compositions for tre~tm.ont of proteinaceous soils comprise:
a) from about 0.01% by weight, of a water-soluble or dispersible, bleach stable, modified polyamine fabric surface modifier according to the present invention;
b) from about 0.01% by weight, of a fabric conditioning agent;
c) from about 0.01% by weight, of a perfume system; and d) the balance carrier and adjunct ingredients.
More preferred fabric surface modification compositions for tre~tm.?nt of proteinaceous stoils comprise:
a) from about 0.01% by weight, of a water-soluble or dispersible, bleach stable, modified polyamine fabric surface modifier according to the present invention;
b) from about 0.01% by weight, of a fabric conditioning agent;
- c) from about 0.01% by weight, of a soil release agent;
d) from about 0.01% by weight, of a perfume system; and CA 022~3399 1998-10-30 W O 97/42289 PCTrUS97/07001 e) the balance carrier and adjunct ingredients.
Fabric surface modification compositions according to the present invention for treatment of greasy/oily soils and lipophilic grime comprise:
a) from about 0.01% by weight, of a detersive surfactant selected from the group nonionic, anionic, zwitterionic, ampholytic surfactants, and mixtures thereof;
b) from about 0.01% by weight, of a fabric conditioning agent, c) from about 0.01% by weight, of a water-soluble or dispersible, bleach stable, modified polyamine fabric surface modifier according to the present invention; and d) the balance carrier and adjunct ingredients.
Preferred fabric surface modification compositions for tre~tm~nt of proteinaceous soils comprise:
a) from about 0.01% by weight, of a detersive surfactant selected from the group nonionic, anionic, ~will~,.;onic, ampholytic surf~rt~nt~, and mixtures thereof;
b) from about 0.01% by weight, of a fabric conditioning agent;
c) from about 0.01% by weight, of a water-soluble or dispersible, bleach stable, modified polyamine fabric surface modifier according to the present invention;
d) from about 0.01% by weight, of a soil release polymer; and e) the balance carrier and adjunct ingredients.
More preferred fabric surface modification compositions for treatment of proteinaceous soils compri~e a) from about 0.01% by weight, of a detersive surfactant selected from the group nonionic, anionic, zwitterionic, ampholytic surf~st~nt~, and IllixlLues thereof;
b) from about 0.01% by weight, of a water-soluble or dispersible, bleach stable, modified polyamine fabric surface modifier according to the present invention;
c) from about 0.01% by weight, of a fabric conditioning agent;
d) optionally from about 0.001% by weight, of an enzyme (preferably a protease enzyme);
e) from about 0.01% by weight, of a perfume system; and - f) the balance carrier and adjunct ingredients.

CA 022~3399 1998-10-30 The fabric surface modification pre-treatments, pre-soaks. and rinse-added compositions can be granules, flakes or laundry bars. The liquid emboflimPnts can have a wide range of viscosity and may include heavy concentrates, pourable "ready" liquids, or light duty fabric pre-tre~tment~. The surface modification pre-treatments may be in the form of spray-on materials wherein the carrier is water, a low boiling alcohol or other suitable solvent. In addition, pre-tre~tme~t and rinse-added forrnulas may be delivered by a "roll-on" device, disolvable container, or other method that ensures even contact of the active ingredients to the fabric surface.
Similarly, pre-soaks or so~king baths formulations may be in the forrn of highlyconcentrated granules that are dissolved in water or other suitable combination of water and carriers. The dilution of these conce~ es may be carried out by an agent ~Itili7ing the invention, such as fabric m~nllf~ctllrers pre-treating newly m~nllf~ctl~red fabric, or by the consumer.
The compositions of the present invention may optionally comprise protease enzymes which can be admixed with other suitable ingredients to form an enzyme boosted pre-llr~ ..t pre-soak or rinse-added fabric modification composition.
Fabric Surface Modifyin~ Polyamine The fabric surface modifying agents of the present invention are water-soluble or dispersible, modified poly~min~s. These polyamines comprise backbones that can be either linear or cyclic. The polyamine backbones can also comprise polyamine bl,.l-chil-g chains to a greater or lesser degree. In general, the polyamine backbones described herein are modified in such a manner that each nitrogen of the polyamine chain is thereafter described in terms of a unit that is substituted, quaternized, oxidized, or combinations thereof.
For the purposes of the present invention the term "modification" as it relates to the chemical structure of the polyamines is defined as replacing a backbone -NH
hydrogen atom by an E unit (substitution), quaternizing a backbone nitrogen (qu~tetni7~d) or oxidizing a backbone nitrogen to the N-oxide (oxidized). The terms "modification" and "substitution" are used interch~ng~bly when referring to the process of replacing a hydrogen atom attached to a backbone nitrogen with an E unit.
Q~l~t.~rni7~tion or oxidation may take place in some circ.lm~t~r ~es without substitution, but substitution must be acco~llpanied by oxidation or quatelllizalion of at least one backbone nitrogen.
The linear or non-cyclic polyamine backbones that comprise the cotton soil release agents of the present invention have the general formula:

, ~ , CA 022~3399 1998-10-30 H
[H2N ~R]nt I--[N ~R]m--[N ~R]n-NH2 said backbones prior to subsequent modification, comprise primary, secondary andtertiary amine nitrogens connected by R "linking" units. The cyclic polyamine backbones comprising the cotton soil release agents of the present invention have the general formula:

,H I R
[H2N-R]n-k+~[N-R]m--tN-R]n~N-R]k-NH2 said backbones prior to subsequent modification, comprise primary, secondary andtertiary amine nitrogens connected by R "linking" units For the purpose of the present invention, primary amine nitrogens comprising thebackbone or br~nrhing chain once modified are defined as V or Z "t~ rnin~l" units. For exarnple, when a primary amine moiety, located at the end of the main polyamine backbone or br~nrhing chain having the structure H2N-R]-is modified according to the present invention, it is thc.edîl~ defined as a V "l~
unit, or simply a V unit. However, for the purposes of the present invention, some or all of the primary amine moieties can remain unmodified subject to the restrictions further described herein below. These unmodified pnmary amine moieties by virtue of their position in the backbone chain remain "terminal" units. Likewise, when a primary amine moiety, located at the end of the main polyamine backbone having the structure is modified according to the present invention, it is thereafter defined as a Z "tennin~l"
unit, or simply a Z unit. This unit can remain unmodified subject to the restrictions further described herein below.
In a similar manner, secondary amine nitrogens comprising the backbone or branching chain once modified are defined as W "backbone" units. For example, when a secondary arnine moiety, the major constituent of the backbones and br~n~hing chains of the present invention, having the structure ,H
[N-R]--is modified according to the present invention, it is thereafter defined as a W "backbone"
unit, or simply a W unit. However, for the purposes of the present invention, some or all of the secondary amine moieties can remain unmodified. These unrnodified secondary CA 022~3399 1998-10-30 W O 97/42289 PCTrUS97107001 amine moieties by virtue of their position in the backbone chain remain "backbone"
units.
In a further similar manner, tertiary amine nitrogens comprising the backbone orbranching chain once modified are further referred to as Y "br~nching" units. For exarnple, when a tertiary amine moiety, which is a chain branch point of either the polyamine backbone or other branching chains or rings, having the structure I

~ R]--is modified according to the present invention, it is thereafter defined as a Y "br~nrhing"
unit, or simply a Y unit. However, for the purposes of the present invention, some or all or the tertiary amine moieties can remain unrnodified. These unmodified tertiary amine moieties by virtue of their position in the backbone chain remain "br~nrhing" units. The R units associated with the V, W and Y unit nitrogens which serve to connect thepolyamine nitrogens, are described herein below.
The final modified structure of the polyamines of the present invention can be therefore replesellled by the general formula V(n+l )WmYnz for linear polyamine cotton soil release polymers and by the general formu1a V(n k+l)wmYnYkz for cyclic polyamine cotton soil release polymers. For the case of polyamines comprising rings, a Y' unit of the form~lla R
~ R]--serves as a branch point for a backbone or branch ring. For every Y' unit there is a Y unit having the formula -R] -that will form the connection point of the ring to the main polymer chain or branch. In the unique case where the backbone is a complete ring, the polyamine backbone has the formula ,H

[H2N~R]n--[N-R]m--~N-R]rl--therefore comprising no Z terminal unit and having the formula CA 022~3399 1998-10-30 W O 97/42289 PCTrUS97/07001 Il Vn kWmYnY k wherein k is the nurnber of ring forming br~nching units. Preferably the polyamine backbones of the present invention comprise no rings.
In the case of non-cyclic polyarnines, the ratio of the index n to the index m relates to the relative degree of branching. A fully non-branched linear modified polyamine according to the present invention has the formula VWmZ
that is, n is equal to 0. The greater the value of n (the lower the ratio of m to n), the greater the degree of branching in the molecule. Typically the value for m ranges from a minimnm value of 4 to about 400, however larger values of m, especially when the value of the index n is very low or nearly 0, are also preferred.
Each polyamine nitrogen whether primary, secondary or tertiary, once modified according to the present invention, is further defined as being a member of one of three general classes; simple substituted, quaternized or oxidized. Those polyamine nitrogen units not modified are classed into V, W, Y, or Z units depending on whether they are primary, secondary or tertiary nitrogens. That is ~lnmorlified primary amine nitrogens are V or Z units, unrnodified secondary amine nitrogens are W units and unmodified tertiary amine nitrogens are Y units for the purposes of the present invention.
Modified primary amine moieties are defined as V "terminal" units having one of three forms:
a) simple sub~Liluled units having the structure:

E--N--R--E
b) qu~t~rni7~?cl units having the structure:

E--N--R
E

wherein X is a suitable counter ion providing charge balance; and c) oxidized units having the structure:

E--N--R--E
Modified secondary amine moieties are defined as W "backbone" units having one of three fonns:
a) simple substituted units having the structure:

--N-R--b) quaternized units having the structure:

--N--R--E
wherein X is a suitable counter ion providing charge b~l~nre; and c) oxidized units having the structure:

--I--R

Modified tertiary amine moieties are defined as Y "branching" units having one of three forms:
a) unmodified units having the structure:

--Nl -R--b) q~ i7ed units having the structure:

I X---I--R

wherein X is a suitable counter ion providing charge balance; and c) oxidized units having the structure:

~ ... ..

_7 R

Certain modified primary amine moieties are defined as Z "terminal" units havingone of three forms:
a) simple substituted units having the structure:
--N-E
b) qll~t~rni7çd units having the structure:

IE X---N--E
E
wherein X is a suitable counter ion providing charge balance; and c) oxidized units having the structure:

--I--E
E
When any position on a nitrogen is un~ubstituted of unmodified, it is understoodthat hydrogen will substitute for E. For example, a primary amine unit comprising one E
unit in the forrn of a hydroxyethyl moiety is a V termin~l unit having the formula (HOCH2CH2)HN-.
For the purposes of the present invention there are two types of chain terrnin~ting units, the V and Z units. The Z "t~rrnin~l" unit derives from a terminal primary amino moiety of the structure -NH2. Non-cyclic polyamine backbones according to the present invention comprise only one Z unit whereas cyclic polyamines can comprise no Z units.
The Z "termin~l" unit can be substituted with any of the E units described further herein below, except when the Z unit is modifled to form an N-oxide. In the case where the Z
unit nitrogen is oxidized to an N-oxide, the nitrogen must be modified and therefore E
cannot be a hydrogen.

CA 022~3399 1998-10-30 The polyamines of the present invention comprise backbone R "linking" units that serve to connect the nitrogen atoms of the backbone. R units comprise units that for the purposes of the present invention are referred to as "hydrocarbyl R" units and "oxy R" units. The "hydrocarbyl" R units are C2-C 12 alkylene, C4-C 12 alkenylene, C3-C12 hydroxyalkylene wherein the hydroxyl moiety may take any position on the R unit chain except the carbon atoms directly connected to the polyarnine backbone nitrogens; C4-C 12 dihydroxyalkylene wherein the hydroxyl moieties may occupy any two of the carbon atoms of the R unit chain except those carbon atoms directly connected to the polyamine backbone nitrogens; Cg-C 12 dialkylarylene which for the purpose of the present invention are arylene moieties having two alkyl substituent groups as part of the linking chain. For example, a dialkylarylene unit has the formula --(CH2)2~CH2 - --(CH2)4~3(CH2)2--although the unit need not be 1,4-substih~te~l, but can also be 1,2 or 1,3 substitutedC2-Cl2 alkylene, ~ ,fe~ably ethylene, 1,2-propylene, and mixtures thereof, more preferably ethylene. The "oxy" R units comprise -(Rlo)XR5(oRl)x-~ -CH2CH(OR2)CH20)z(RIO)yRI(OCH2CH(OR2)CH2)w~~-CH2CH(OR2)CH2-, (R10)XR1-, and mixtures thereof. Preferred R units are C2-C12 alkylene, C3-C12 hydroxyalkylene, C4-C12 dihydroxyalkylene, Cg-C12 dialkylarylene, -(R10)XRl-, CH2CH(OR2)CH2-,-(CH2CH(OH)CH20)z(RlO)yRl(OCH2CH-(OH)CH2)W-, (R10)xRS(oRl)x-~ more preferred R units are C2-C12 alkylene, C3-C12 hydroxy-alkylene, C4-C12 dihydroxyalkylene, (RlO)XRl, (R1o)xR5(oRl)x-~(CH2CH(OH)CH20)z(RlO)yRl(OCH2CH~(OH)CH2)w~~ and mixtures thereof, even more pr~fcll~d R units are C2-C12 alkylene, C3 hydroxyalkylene, and mixtures thereof, most ~ncf~l~cd are C2-C6 alkylene. The most preferred backbones of the present invention comprise at least 50% R units that are ethylene.
Rl units are C2-C6 alkylene, and mixtures thereof, preferably ethylene. R2 is hydrogen, and -(R10)XB, preferably hydrogen.
R3 is Cl-C1g alkyl, C7-C12 arylalkylene, C7-C12 alkyl substituted aryl, C6-C12 aryl, and mixtures thereof, preferably C1-Cl2 alkyl, C7-C12 arylalkylene, more preferably C 1 -C 12 alkyl, most preferably methyl. R3 units serve as part of E units described herein below.

CA 022~3399 1998-10-30 WO 97/42289 PCT~US97/07001 R4 is Cl-C12 alkylene, C4-C12 alkenylene, Cg-C12 arylalkylene, C6-C1o arylene, preferably Cl-CIo alkylene, Cg-C12 arylalkylene, more preferably C2-Cg alkylene, most preferably ethylene or butylene.
RS is C 1 -C 1 2 alkylene, C3-C 1 2 hydroxyalkylene, C4-C 1 2 dihydroxyalkylene,Cg-C12 dialkylarylene, -C(O)-, -C(O)NHR6NHC(O)-, -C(o)(R4)rC(o)-, -Rl(ORl)-, -CH2CH(OH)CH20(RlO)yRlOCH2CH(OH)CH2~~ -C(o)(R4)rC(o)-, -CH2CH(OH)CH2-, R5 is preferably ethylene, -C(O)-, -C(O)NHR6NHC(O)-, -Rl(ORl)-,-CH2CH(OH)CH2-,-CH2CH(OH)CH20(RlO)yRlOCH2CH~(OH)CH2~~
more preferably -CH2CH(OH)CH2-.
R6 is C2-C12 alkylene or C6-C12 ~rylene.
The preferred "oxy" R units are further defined in terms of the R1, R2, and R5 units. Preferred "oxy" R units comprise the preferred Rl, R2, and R5 units. The preferred cotton soil release agents of the present invention comprise at least 50% Rl units that are ethylene. Preferred R1, R2, and R5 units are combined with the "oxy" R
units to yield the pref~ ;d "oxy" R units in the following manner.

i) Substituting more preferred R5 into -(CH2CH2o)XR5(oCH2CH2)x-yields -(CH2CH20)XCH2CHOHCH2(0CH2CH2~x-.

ii) Substituting ple~.led Rl and R2 into -(CH2CH(OR2)CH20)z-(R I O)yR I O(CH2CH(OR2)CH2)w- yields -(CH2CH(OH)CH20)z-(CH2CH20)yCH2CH20(CH2CH(OH)CH2)w~.

iii) Sub~liluling preferred R2 into -CH2CH(OR2)CH2- yields -CH2CH(OH)CH2--E units are selected from the group con~i~ting of hydrogen, C 1 -C22 alkyl, C3-C22 alkenyl, C7-C22 arylalkyl, C2-C22 hydroxyalkyl, -(CH2)pC02M, -(CH2)qS03M, -CH(CH2C02M)C02M, -(CH2)pP03M, -(R1O)mB, -C(o)R3, preferably hydrogen, C2-C22 hydroxyalkylene, benzyl, Cl-C22 alkylene, -(RlO)mB, -C(o)R3, -(CH2)pC02M, -(CH2)qS03M, -CH(CH2C02M)C02M, more preferably Cl-C22 alkylene, -(R10)XB, -C(o)R3,-(CH2)pCo2M,-(CH2)qSo3M, -CH(CH2C02M)C02M, most preferably Cl-C22 alkylene, -(R10)xB, and -C(o)R3. When no modification or substitution is made on a nitrogen then hydrogen atom will remain as the moiety l~plese~t;.-g E.

CA 022~3399 1998-10-30 E units do not comprise hydrogen atom when the V, W or Z units are oxidized, that is the nitrogens are N-oxides. For exarnple, the backbone chain or br~nrhin~ chains do not comprise units of the following structure:

O~ 0~ 0~
N--R or H--N--R or N--H
H H H
Additionally, E units do not comprise carbonyl moieties directly bonded to a nitrogen atom when the V, W or Z units are oxidized, that is, the nitrogens are N-oxides.
According to the present invention, the E unit -C(o)R3 moiety is not bonded to an N-oxide modified nitrogen, that is, there are no N-oxide amides having the structure O O O
N--R or R3--C--N--R or --N--C-R3 ,C=O E E

or combinations thereof.
B is hydrogen, Cl-C6 alkyl, -(CH2)qS03M, -(CH2)pC02M, ~(CH2)q~
(CHs03M)cH2so3M~ ~(cH2)q(cHso2M)cH2so3M~ -(CH2)pP03M, -P03M, preferably hydrogen, -(CH2)qS03M, -(CH2)q(CHS03M)CH2S03M, ~(CH2)q~
(CHS02M)CH2S03M, more preferably hydrogen or -(CH2)qS03M.
M is hydrogen or a water soluble cation in sufficient amount to satisfy charge balance. For example, a sodium cation equally s~ti~fies -(CH2)pC02M, and (CH2)qS03M, thereby resulting in -(CH2)pC02Na, and -(CH2)qS03Na moieties.
More than one monovalent cation, (sodium, potassium, etc.) can be combined to satisfy the required chemical charge balance. However, more than one anionic group may be charge b~l~nced by a divalent cation, or more than one mono-valent cation may benecec~ry to satisfy the charge requirements of a poly-anionic radical. For example, a -(CH2)pP03M moiety substituted with sodium atoms has the formula -(CH2)pP03Na3.
Divalent cations such as calcium (Ca2+) or m~gnesium (Mg2+) may be substituted for or combined with other suitable mono-valent water soluble cations. Pr~felled cations are sodium and potassiurn, more preferred is sodium.
X is a water soluble anion such as chlorine (Cl-), bromine (Br~) and iodine CA 022~3399 1998-10-30 (1-) or X can be any negatively charged radical such as sulfate (S042-) and methosulfate (CH3SO3-).
The formula indices have the following values: p has the value from 1 to 6, q has the value from 0 to 6; r has the value 0 or 1; w has the value 0 or 1, x has the value from 1 to 100; y has the value from 0 to 100; z has the value 0 or 1; m has the value from 4 to about 400, n has the value from 0 to about 200; m + n has the value of at least 5.
The preferred fabric surface modifiers of the present invention comprise polyarnine backbones wherein less than about 50% of the R groups comprise "oxy" R
units, preferably less than about 20%, more preferably less than 5%, most preferably the R units comprise no "oxy" R units.
The most preferred fabric surface modifiers which comprise no "oxy" R units comprise polyamine backbones wherein less than 50% of the R groups comprise morethan 3 carbon atoms. For example, ethylene, 1,2-propylene, and 1,3-propylene comprise 3 or less carbon atoms and are the preferred "hydrocarbyl" R units. That is whenbackbone R units are C2-C12 alkylene, preferred is C2-C3 alkylene, most preferred is ethylene.
The fabric surface modifiers of the present invention comprise modified homogeneous and non-homogeneous polyamine backbones, wherein 100% or less of the-NH units are modified. For the purpose of the present invention the term "homogeneous polyamine backbone" is defined as a polyamine backbone having R units that are the same (i.e., all ethylene). However, this sameness definition does not exclude polyarnines that comprise other extraneous units comprising the polymer backbone which are present due to an artifact of the chosen method of chemical synthloci~ For example, it is known to those skilled in the art that ethanolamine may be used as an "initiator" in the synthesis of polyethyleneimin~s, therefore a sample of polyethyleneimine that comprises one hydroxyethyl moiety res..lting from the polymerization "initiator" would be considered to comprise a homogeneous polyamine backbone for the purposes of the present invention. A polyarnine backbone comprising all ethylene R units wherein no br~n.~hin~
Y units are present is a homogeneous backbone. A polyamine backbone comprising all ethylene R units is a homogeneous backbone regardless of the degree of br~n~ hing or the number of cyclic branches present.
For the purposes of the present invention the term "non-homogeneous polymer backbone" refers to polyamine backbones that are a composite of various R unit lengths and R unit types. For example, a non-homogeneous backbone comprises R units that are - a mixture of ethylene and I ,2-propylene units. For the purposes of the present invention a mixture of "hydrocarbyl" and "oxy" R units is not n~cçss~ry to provide a non-CA 022~3399 1998-10-30 homogeneous backbone. The proper manipulation of these "R unit chain lengths"
provides the formulator with the ability to modify the solubility and fabric substantivity of the fabric surface modifiers of the present invention Preferred fabric surface modifiers of the present invention comprise homogeneous polyamine backbones that are totally or partially substituted by polyethyleneoxy moieties, totally or partially quaternized amines, nitrogens totally or partially oxidized to N-oxides, and mixtures thereof. However, not all backbone amine nitrogens must be modified in the same manner, the choice of modification being left to the specific needs of the forrn~ tor. The degree of ethoxylation is also determined by the specific requirements of the formulator.
The plcfc,.~d polyamines that comprise the backbone of the compounds of the present invention are generally polyalkylene~mintoc (PAA's), polyalkyleneimines (PAI's), preferably polyethylçne~minP (PEA's), polyethyleneimines (PEI's), or PEA's or PEI's connected by moieties having longer R units than the parent PAA's, PAI's, PEA's or PEI's. A cornmon polyalkyl~ne~min~ (PAA) is tetrabutylenepe.,~ e. PEA's are obtained by reactions involving ammonia and ethylene dichloride, followed by fractional tlictill~tion The cornmon PEA's obtained are triethylenetetramine (TETA) and teraethylen~p.,..l~.,.inP (TEPA). Above the pent~min~c, i.e., the he~c~min~s, hept~min~s, octarnines and possibly llo~ inPs, the cogenerically derived mixture does not appear to separate by f~i~till~tion and can include other materials such as cyclic amines and particularly ~ e~a~ines There can also be present cyclic amines with side chains in which nitrogen atoms appear. See U.S. Patent 2,792,372, Dickinson, issued May 14, 1957, which describes the ~le~ alion of PEA's.
P~ d amine polymer backbones comprise R units that are C2 alkylene (ethylene) units, also known as polyethylenimin~c (PEI's). Preferred PEI's have at least moderate branching, that is the ratio of m to n is less than 4:1, however PEI's having a ratio of m to n of about 2:1 are most preferred. Preferred backbones, prior to modification have the general formula:

,H
[H2NCH2CH2]n--[NcH2cH2]m--[NCH2CH2]n-NH2 wherein m and n are the same as defined herein above. Preferred PEI's, prior to modification, will have a molecular weight greater than about 200 daltons.
The relative proportions of primary, secondary and tertiary amine units in the polyamine backbone, especially in the case of PEI's, will vary, depending on the manner of pl~pardlion. Each hydrogen atom ~ h~d to each nitrogen atom of the polyamine . . . - ' - - t CA 022~3399 1998-10-30 W O 97/42289 PCT~US97107001 backbone chain represents a potential site for subsequent substitution, quaternization or oxidation.
These polyamines can be ~lcpaled, for example, by polymerizing ethyleneimine in the presence of a catalyst such as carbon dioxide, sodium bisulfite, sulfuric acid, hydrogen peroxide, hydrochloric acid, acetic acid, etc. Specific methods for preparing these polyamine backbones are disclosed in U.S. Patent 2,182,306, Ulrich et al., issued December 5, 1939; U.S. Patent 3,033,746, Mayle et al., issued May 8, 1962; U.S. Patent 2,208,095, F.~selm~nn et al., issued July 16, 1940; U.S. Patent 2,806,839, Crowther, issued September 17, 1957; and U.S. Patent 2,553,696, Wilson, issued May 21, 1951; all herein incorporated by reference.
Examples of modified cotton soil release polymers of the present invention comprising PEI's, are illustrated in Formulas I - IV:
Fonnula I depicts a fabric surface modifier comprising a PEI backbone wherein all sub~ ul~ble nitrogens are modified by replacement of hydrogen with a polyoxyalkyleneoxy unit, -(CH2CH2O)7H, having the formula [H(ocH2cH2h]2N N[(CH2CH20hH]2 ~NJ' H(ocH2cH2)7'N~N[(cH2cH2ohHk (CH2CH20~7H ~ ~ (cH2cH2o)7H
tH(ocH2cH2h]2N~N--IN~N N~N N~N IN~N[(CH2CH20)7H]2 (CH2CH20hH (CH2CH20hH ~ (cH2cH2o)7H

~ ~ ~N[(CH2CH20)7H]2 tH(OCH2CH2hkN N
l~,N[(CH2CH20hH]2 Formula I
This is an example of a fabric surface modifier that is fully modified by one type of moiety.
Formula II depicts a fabric surface modifier comprising a PEI backbone wherein all substitutable pl;lll~y amine nitrogens are modified by repl~cem~nt of hydrogen with a polyoxyalkyleneoxy unit, -(CH2CH2O)7H, the molecule is then modified by subsequent oxidation of all oxidizable primary and secondary nitrogens to N-oxides, said fabric surface modifier having the formula ~ .. . . .

[H(~H2CH2)7]2N N~(CH2cH2o)7H]2 ~O(CH~ocH2o)6H
~ ~ ~~ ~N[(cH2cH2o)7Hl2 H(~CHoCH2)6~ ~o (~2CH20)6~J o (~{2CH20)(~H
[H(ocH2cH2hkN ~ - dN ~ oN N~ ~ No - N ~ ( ~N ~ N[(CH2cH2OhH]2 O(cH2cH2o)6H O(cH2cH2o)6H
rH(ocH2cH2)7kN ,~N~N[(cH2cH2ohH]2 ~ ~N[(cH2cH2ohHl2 Formula II
Formula III depicts a fabric surface modifier comprising a PEI backbone wherein all backbone hydrogen atoms are substituted and some backbone amine units are qu~tPrni7~ The substituents are polyoxyalkyleneoxy units, -(CH2CH20)7H, or methyl groups. The modified PEI fabric surface modifier has the formula [H(ocH2cH2hkN~ ~N(cH2cH2o}7H CH3 NJ Cl- CH3~ ~N(cH2cH2o)7H
CH3~ ,CH3 ~ ~ CH3~ CH3 [H(ocH2cH2hl2N~N--N~N--N~N--N~N~ N~N(CH3)2 Cl CH3 CH3 ~ Cl- CH3 ~ 3 Cl-[H(ocH2cH2)7kN N~N(CH3h l~,N(CH3)2 Formula III
Formula IV depicts a fabric surface modifier comprising a PEI backbone wherein the backbone nitrogens are modified by substitution (i.e. by -(CH2CH20)7H or methyl), 4~ ....i7t~r1, oxidized to N-oxides or combinations thereof. The resulting fabric surface modifier has the formula CA 022~3399 1998-10-30 [H(OCH2CH2h]2N~ ~N(CH2CH2OhHH ~ CH3 ~NJ ~N(CH2CH20hH

CH3 CH3 ~ CH3 CH3 ~ CH3 [H(ocH~cH2hl2N~N CH3 N o N ~ Cl- CH3 N(CH3~2 Cl~N--~13 H(OCH2CH2)7]2NJ N~N(CH3h l N(CH3)2 Formula IV
In the above exarnples, not all nitrogens of a unit class comprise the sarne modification. The present invention allows the formulator to have a portion of the secondary amine nitrogens ethoxylated while having other secondary amine nitrogens oxidized to N-oxides. This also applies to the primary amine nitrogens, in that the formulator may choose to modify all or a portion of the primary amine nitrogens with one or more substituents prior to oxidation or q~l~t~mi7~tion. Any possible combination of E groups can be substituted on the primary and secondary amine nitrogens, except for the restrictions described herein above.
For the purposes of the present invention the term "effective amount" when related to the modified polyamines described herein, refers to the amount of polyamine neces~s~. y to modify the surface of a fabric to achieve increased removal of greasy oily dirt, lipophilic grime, and proteinaceQus soils. Typically 0.01% by weight, of polyamine is sufficient to effect an icreased stain or dirt removal.
Cationic Fabric Conditionin~ A~ents Compositions of the present invention can contain from about 5% to about 9S%, preferably from about 15% to about 90%, more preferably from about 25% to about 85%, and even more pl~r~,.dbly from about 25% to about 55%, of biodegradable cationic fabric conditioning agent, preferably an ester quaternary amrnonium compound (EQA).
The fabric conditioning components suitable for use in the compositions of the present invention is preferably a fabric softening compound which is an ester ql~tern~ry ammonium (EQA) compound or its prec~sor amine having the formula:
)4_p N ((CH2)v--Y--*)p ] X
Formula I
wherein Y is a carboxy moiety having the formula CA 022~3399 1998-10-30 WO 97/42289 PCT/~lS97107001 O O
Il 11 0--C or C--0 the index p is from 1 to 3; the index v is from I to 4, and mixtures thereof; R~ is Cl-C6 alkyl, C I -C4 hydroxy alkyl group, or benzyl, preferably C 1 -C3 alkyl, for example, methyl, ethyl, propyl, most preferred is methyl; preferably one Rl moiety is a short chain alkyl group, preferably methyl; R2 is Cg-C30 saturated alkyl or Cg-C30 unsaturated alkyl, Cg-C30 substituted alkyl or Cg-C30 unsubstituted alkyl, preferably C14-Clg saturated alkyl or C14-C1g unsaturated alkyl, Cl4-Clg sub~LiLul~d alkyl or C14-Clg unsubstituted alkyl, more preferably linear C 14-C l 8 saturated alkyl, wherein each R2 moiety suitable for use has an Iodine Value of from about 3 to about 60; the counter ion, X~, can be any softener-compatible anion, preferably methyl~--lf~te, ethyl~ulf~tç, chloride, bromide, formate, sulfate, lactate, nitrate, bt?n7o~te, more preferably methylc--lf~te.
Tallow is a convenient and ineA~ e source of long chain alkyl and alkenyl materials.
It will be understood that sllkstit~lerlt~ Rl and R2 of Formula I can optionally be substituted with various groups such as alkoxyl or hydroxyl groups. The preferred compounds can be considered to be diester (DEQA) variations of ditallow dimethylammonium methyl sulfate (DTDMAMS), which is a widely used fabric softener. At least 80% of the DEQA is in the diester form, and from 0% to about 20%, preferably less than about 10%, more ~l~Ç. ldbly less than about 5%, can be EQA monoester (e.g., only one y-R2 group).
The following are non-limiting examples of EQA Formula I (wherein all long-chain alkyl substituents are straight-chain):
Saturated [c2H5]2+N[cH2cH2oc(o)c 1 7H35]2 (CH3S04) [cH3][c2H5]+N[cH2cH2oc(o)c 1 3H27]2 [HC(0)0]
[c3H7][c2H5]+N[cH2cH2oc(o)cllH23]2 (CH3S04) [cH3]2+N-[cH2cH2oc(o)cl7H35]cH2cH2oc(o)clsH3l (CH3S04)-[CH3]2+N[cH2cH2oc(o)R2]2 (CH3S04)-where -C(O)R2 is derived from saturated tallow.
Unsaturated ~cH3]2+N[cH2cH2oc(o)cl7H33]2 (CH3S04) [c2H5]2+N[cH2cH2oc(o)c 1 7H33]2 C 1 [cH3][c2H5]+N[cH2cH2oc(o)c 1 3H25]2 [C6H5C(O)O]
[CH3]2+N-[CH2CH20C(O)C 1 7H33]CH2CH20C(O)C 1 sH29 (CH3CH2S04)-~. . .... . .

CA 022~3399 1998-10-30 [CH3~2+N[cH2cH2oc(o)R2]2 (CH3SO4)-where -C(O)R2 is derived from partially hydrogenated tallow or modified tallow having the characteristics set forth herein.
Other specific examples of biodegradable Formula I compounds suitable for use in the fabric surface modification compositions herein are:
N-methyl-N,N-di-(2-C 14-C I g-acyloxy ethyl);
N-2-hydroxyethyl ammonium methylsulfate;
[HOcH(cH3)cH2][cH33+N[cH2cH2oc(o)cl 5H3 1]2 Br-;
[HOCH(CH3)CH2] [cH3~+N[cH2cH2oc(o)c 1 5H29]2 [HC(O)O]-; and [CH2CH2OH][CH3]+N[CH2CH2OC(O)R2]2 (CH3SO4)-. Apreferred compound is N-methyl, N,N-di-(2-oleyloxyethyl) N-2-hydroxyethyl ammonium methylsulfate.
Further suitable fabric conditioning agents are qll~tern~ry ammonium compounds having the formula:
N+ ((CH2)V ~'--R2)p ] X
Formula II
wherein Y" is a carboxy moiety having the formula O O O O
~1 ~1 11 11 --NR3-C--;--C-NR3--; --O-C--;--C-O--and mixtures thereof, wherein at least one Y group is --NH-C-- or --C-NH--the index p is from I to 3; the index v is from 1 to 4, and mixtures thereof; Rl is Cl-C6 alkyl or benzyl, p~cf. .ably Cl-C3 alkyl, for example, methyl, ethyl, propyl, most preferred is methyl; preferably one Rl moiety is a short chain alkyl group, preferably methyl; R2 is Cg-C30 saturated alkyl or Cg-C30 unsaturated alkyl, Cg-C30 substituted alkyl or Cg-C30 unsubstituted alkyl, preferably C 1 4-C l 8 saturated alkyl or C 1 4-C l 8 unsaturated alkyl, C 1 4-C l 8 substituted alkyl or C 1 4-C 1 8 unsubstituted alkyl, more preferably linear C14-Clg s~tl~r~ted alkyl, wherein each R2 moiety suitable for use has an lodine Value of from about 3 to about 60; R3 is R or H; the counter ion, X~, can be any softener-compatible anion, preferably methyl~lllf~te, ethyl~..lf~te, chloride, bromide, formate, sulfate, lactate, nitrate, ben70~te, more preferably methylsulfate.

CA 022~3399 1998-10-30 W O 97142289 PCTrUS97/07001 It will be understood that substituents R and R2 of Formula II can optionally besubstituted with various groups such as alkoxyl or hydroxyl groups.
The ~ f~lled ester linked compounds (DEQA) can be considered to be diester variations of ditallow dimethyl ammonium chloride (DTDMAC), which is a widely used fabric softener. Preferably, at least 80% of the DEQA is in the diester form, and from 0% to about 20%, preferably less than about 10%, more preferably less than about 5%, can be DEQA monoester (e.g., only one y R2 group). For optimal ~ntict~tic benefit monoester should be low, preferably less than about 2.5%. The level of monoester can be controlled in the manufacturing of the DEQA.
The qu~tern~ry conditioning agents with at least partially ul~saluldted alkyl or acyl groups have advantages (i.e., ~ltiet~tic benefits) and are highly acceptable for consumer products when certain conditions are met. Antistatic effects are especi~lly important where the fabrics are dried in a tumble dryer, and/or where synthetic materials which generate static are used. Any reference to IV values hereinafter refers to IV of fatty alkyl or acyl groups and not to the resulting q~ , e.g., DEQA compound. As the IV is raised, there is a potential for odor problems.
For unsaturated conditioning actives, the optimum storage temperature for stability and fluidity depends on the specific IV of, e.g., the fatty acid used to make DEQA and/or the level/type of solvent selected. Exposure to oxygen should be rlli~ d to keep the unsaturated groups from oxidizing. It can therefore be important to store the material under a reduced oxygen atmosphere such as a nitrogen blanket. It is important to provide good molten storage stability to provide a commercially feasible raw material that will not degrade noticeably in the normal ~ s~o~ ion/storage/handling of the material in m~nl-f~cturing operations.
The following are non-limiting examples of DEQA Forrnula II (wherein all long-chain alkyl substit~le~te are straight-chain):
Saturated [c2Hs]2(+)N[cH2cH2oc(o)c 1 7H35]2 S04CH3(-) [c3H7][c2H5](+)N[cH2cH2oc(o)c 1 I H23]2 S04( )CH3 [CH3]2(+)N[cH2cH2oc(o)R2]2 S04CH3(-) where -C(O)R2 is derived from saturated tallow.
Unsaturated [CH3]2(+)N[CH2CH20C(0)C 1 7H33~2 S04(-)CH3 [C2H5]2(+)N[CH2CH20C(O)C I 7H33]2 Cl(-) - [CH2CH20H][CH3](+)N[CH2CH20C(O)R2]2 CH3S04(-) [CH3]2(+)N[CH2CH20C(O)R2]2 CH3S04(-) CA 022~3399 1998-10-30 WO 97/42289 PCTrUS97/07001 where -C(O)R2 is derived from partially hydrogenated tallow or modified tallow having the characteristics set forth herein.
Further suitable fabric conditioning compounds according to the present invention are ester quaternary ammonium compounds having the formula:
R
Rl l--(CH2~ ICH-Cl H2 X~
Rl ~ Q

Formula III
wherein Q is a carboxy moiety having the formula O O
O--C- or C--O
the index v is from 1 to 4, and mixtures thereof; Rl is Cl-C4 alkyl, Cl-C4 hydroxy alkyl group, preferably methyl; preferably one R1 moiety is a short chain alkyl group,preferably methyl; R2 is Cg-C30 saturated alkyl or Cg-C30 unsaturated alkyl, Cg-C30 substituted alkyl or Cg-C30 1ln~ubstituted alkyl, preferably C14-C1g saturated alkyl or C14-C1g unsaturated alkyl, C14-CIg substituted alkyl or C14-C1g unsubstituted alkyl, more preferably linear C14-Clg saturated alkyl, wherein each R2 moiety suitable for use has an lodine Value of from about 3 to about 60; the counter ion X- is methyl~ulf~te An example of the above described ester q~ ry ammonium compound which is suitable for use as a fabric conditioning compound in the present invention is 1,2-bis(tallowyloxy)-3-trimethyl amrnoniop~patle methylsulfate (DTTMAPMS). Other suitable exarnples are 1,2-bis(cocoyloxy)-3-ll;ll,~,lhyl ammoniop,opalle methylsulfate, 1,2-bis(lauryloxy)-3-trimethyl amrnoniopropalle methyl~llf~t~, 1,2-bis(oleyloxy)-3-trimethyl ammoniopropane methylsulfate and 1,2-bis(stearyloxy)-3-trimethyl ammoniopn~pane methylsulfate. Replacing one or more or the methyl moieties in the above examples with ethyl, propyl, isopropyl, butyl, isobutyl, or mixtures thereof, result in suitable fabric softening compounds according to the present invention. In addition, other anions other than methylsulfate may be used.
Other examples of suitable Formula III EQA compounds of this invention are obtained by, e.g., replacing "tallowyl" in the above compounds with, for example, cocoyl, lauryl, oleyl, stearyl, palmityl, or the like; replacing "methyl" in the above compounds with ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, or the hydroxy CA 022~3399 1998-10-30 W O 97/42289 PCTnUS97/07001 substituted analogs of these radicals; replacing "methylsulfate" in the above compounds with chloride, ethylc..lf~te, bromide, formate, sulfate, lactate, nitrate, and the like, but methylsulfate is plefe..ed.
Yet still further suitable fabric conditioning compounds according to the present invention are ester quaternary ammonium compounds having the formula:

R--I ((CH2)V-Y--R2)p X~

Formula IV
wherein Y is a carboxy moiety having the formula O O
Il 11 --O--C or --C--O
the index p is 2; the index v is from 1 to 4, and mixtures thereof; Rl is Cl-C4 alkyl or hydroxy alkyl, preferably Cl-C3 alkyl, for example, methyl, ethyl, propyl, most preferred is methyl; R2 is Cg-C30 saturated or unsaturated, substituted or unsubstituted alkyl having an Iodine Value of from about 3 to about 60, preferred R2 is Cg-C 14 linear or branched alkyl, more preferred Cg-C14 linear alkyl; R4 is a Cl-C4 alcohol; the counter ion, X~, can be any softener-co~l.patible anion, preferably methyl.~ulf~t~, ethyl~..lf~te, chloride, bromide, formate, sulfate, lactate, nitrate, bçn7n~te~ more preferably methyl~lllf~te.
Most preferably, the quaternary amrnonium compound is a fully saturated compound, such as dimethyl bis(tallowyloxyethyl) ammonium methyl~ulf~te, derivedfrom hardened tallow . Also suitable are dimethyl bis(acyloxyethyl) ammonium methylsulfate derivatives of Cg-C30 fatty acids, such as dimethyl bis(tallowyloxyethyl) ammonium methyl.~ulf~te; dimethyl bis(oleyloxyethyl) ammonium methylsulfate or dimethyl bis(cocoyloxyethyl) ammonium methylsulfate. The co~"posilion of the present invention may comprise from about 15% to about 90% of these ~"."e, - IAI y amrnonium compounds.
An example of the above described ester q~l~t~ ry ammonium compounds suitable for use as a fabric conditioning compound according to the present invention is N-methyl-N,N-bis-(2-C I 4-C I g-acyloxy)ethyl-N-2-hydroxyethyl ammoniurn methylsulfate. A plefe..~d example is N-methyl-N,N-bis(2-oleyloxyethyl)-N-(2-hydroxyethyl) ammonium methylsulfate.

CA 022~3399 1998-10-30 WO 97/42289 PCTrUS97107001 The fabric conditioning composition can be any of those known in the art and/or previously disclosed by others in patent applications. Compositions that are suitable are disclosed in U.S. Pat. Nos.: 3,944,694, McQueary; 4,073,996, Bedenk et al.; 4,237,155, Kardouche; 4,711,730, Gosselink et al.; 4,749,596, Evans et al.; 4,808,086, Evans et al.;
4,818,569, Trinh et al.; 4,877,896, Maldonado et al.; 4,976,879, Maldonado et al.;
5,041,230, Borcher, Sr. et al.; 5,094,761, Trinh et al.; 5,102,564, Gardlik et al.; and 5,234,610, Gardlik et al., all of said patents being incorporated herein by reference.
The compounds herein can be prepared by standard esterification and quaternization reactions, using readily available starting materials. General methods for preparation are disclosed in U.S. Pat. No. 4,137,180, incorporated herein by reference.
As used herein, when the diester quat is specified, it will include the monoester quat that is norrnally present. For the optimal antistatic benefit the percentage of monoester ~uat should be as low as possible, preferably less than about 20%. The level of monoester quat present can be controlled in the m~n~fActl-ring of the EQA.
EQA compounds prepared with fully saturated acyl groups are rapidly biodegradable and excellent softeners. However, it has been discovered that compounds prepared with at least partially unsaturated acyl groups have advantages (i.e., ~nti.ct~tic benefits) and are highly acceptable for consumer products when certain conditions are met.
Variables that must be adjusted to obtain the benefits of using unsaturated acylgroups include the Iodine Value (IV) of the fatty acids, the odor of fatty acid starting material, and/or the EQA. Any reference to IV values herein refers to IV of fatty acyl groups and not to the resulting EQA compound.
Antistatic effects are especially important where the fabrics are dried in a tumble dryer, and/or where synthetic materials which generate static are used. As the IV is raised, there is a potential for odor problems.
Some highly desirable, readily available sources of fatty acids such as tallow, possess odors that remain with the compound EQA despite the chemical and mech~ni.~l processing steps which convert the raw tallow to fini~he~l EQA. Such sources must be deodorized, e.g., by absorption, ~i~till~tion (including stripping such as steam stripping), etc., as is well known in the art. In addition, care should be taken to minimi7e the - adverse results of contact of the resulting fatty acyl groups with oxygen and/or bacteria by adding antioxi.l~ntc, antibacterial agents, etc. The additional expense and effort associated with the unsaturated fatty acyl groups is justified by the superior performance.
- Generally, hydrogenation of fatty acids to reduce polyunsaturation and to lower IV
to insure good color and odor stability leads to a high degree of trans configuration in the CA 022~3399 1998-10-30 molecule. Therefore, diester compounds derived from fatty acyl groups having low IV
values can be made by mixing fully hydrogenated fatty acid with touch hydrogenated fatty acid at a ratio which provides an IV of from about 3 to about 60. The polyunsaturation content of the touch hardened fatty acid should be less than about 5%, preferably less than about 1%. During touch hardening the cis/trans isomer weight ratios are controlled by methods known in the art such as by optimal mixing, using specific catalysts, providing high H2 availability, etc.
It has also been found that for good chemical stability of the diester qll~t~qrn~ry compound in molten storage, water levels in the raw material must be minimi7ed to preferably less than about 1% and more preferably less than about 0.5%. Storage t~ll,p~ldl lres should be kept as low as possible and still m~int~in a fluid material, ideally in the range of from about 49~C to about 75~C. The optimum storage telllpeldlulc for stability and fluidity depends on the specific IV of the fatty acid used to make the diester ql~tPrn~ry and the level/type of solvent selected. Also, exposure to oxygen should be minimi7~d to keep the unsaturated groups from oxidi_ing. It can therefore be iln~o~
to store the material under a reduced oxygen atmosphere such as a nitrogen blanket. It is important to provide good molten storage stability to provide a commercially feasible raw material that will not degrade noticeably in the normal transportation/storage/h~nllling ofthe material in m~m-f~ ring operations.
Nonionic Conditionin~ Agents An p.~ d conditioning agent of the present invention is a nonionic fabric softener material. Typically, such nonionic fabric softener materials have an HLB of from about 2 to about 9, more typically from about 3 to about 7. In general, the materials selected should be relatively cryst~lline, higher melting, (e.g., >25 ~C).
The level of optional nonionic softener in the solid co..l~o~ilion is typically from about 10% to about 50%, preferably from about 15% to about 40%.
~ cfe..~d nonionic softeners are fatty acid partial esters of polyhydric alcohols, or anhydrides thereof, wherein the alcohol, or anhydride, co~ hls from about 2 to about 18, preferably from about 2 to about 8, carbon atoms, and each fatty acid moiety colll~hls from about 8 to about 30, preferably from about 12 to about 20, carbon atoms. Typically, such softeners contain from about one to about 3, preferably about 2 fatty acid groups per molecule.
The polyhydric alcohol portion of the ester can be ethylene glycol, glycerol, poly (e.g., di-, tri-, tetra, penta-, and/or hexa-) glycerol, xylitol, sucrose, erythritol, penta-- erythritol, sorbitol or sorbitan.

CA 022~3399 1998-10-30 W O 97/42289 PCTrUS97/07001 The fatty acid portion of the ester is norrnally derived from fatty acids having from about 8 to about 30, preferably from about 12 to about 22, carbon atoms. Typicalexamples of said fatty acids being lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, and behenic acid.
Highly preferred optional nonionic softening agents for use in the present invention are C 1 o-C26 acyl sorbitan esters and polyglycerol monostearate. Sorbitan esters are esterified dehydration products of sorbitol. The preferred sorbitan ester comprises a member selected from the group consisting of C1o-C26 acyl sorbitan monoesters and C 1 o-C26 acyl sorbitan diesters 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. For the purpose of the present invention, sorbitan esters cont~ining unsaturation (e.g., sorbitan monooleate) can be utili7P~
Sorbitol, which is typically prepared by the catalytic hydrogenation of glucose, can be dehydrated in well known fashion to form mixtures of 1,4- and 1,5-sorbitol anhydrides and small amounts of isosorbides. (See U.S. Pat. No. 2,322,821, Brown, issued June 29, 1943, incol~n~ ed herein by lc~;rence.) The foregoing types of complex mixtures of anhydrides of sorbitol are collectively referred to herein as "sorbitan." It will be recognized that this "sorbitan" mixture will also contain some free, uncyclized sorbitol.
The preferred sorbitan softening agents of the type employed herein can be cp~d by esterifying the "sorbitan" mixture with a fatty acyl group in standard fashion, e.g., by reaction with a fatty acid halide, fatty acid ester, and/or fatty acid. The esterification reaction can occur at any of the available hydroxyl groups, and various mono-, di-, etc., esters can be pl~ipa~cd. In fact, mixtures of mono-, di-, tri-, etc., esters almost always result from such reactions, and the stoichiometric ratios of the rç~ct~nt~
can be simply adjusted to favor the desired reaction product.
For commercial production of the solbilan ester materials, etherification and esterification are generally accomplished in the sarne proceseing step by reacting sorbitol directly with fatty acids. Such a method of sorbitan ester plepal~lion is described more fully in MacDonald; "F.mulsifiers:" Procescin~ and Quality Control:, Journal of the American Oil Chemists' Society, Vol. 45, October 1968.
Details, including formula, of the pl~"ed sorbitan esters can be found in U.S.
Pat. No. 4,128,484, incorporated hereinbefore by reference.
Certain derivatives of the preferred sorbitan esters herein, especially the "lower"
- ethoxylates thereof (i.e., mono-, di-, and tri-esters wherein one or more of the unesterified -OH groups contain one to about twenty oxyethylene moieties (Tweens(~)) CA 022~3399 1998-10-30 W O 97/42289 PCTrUS97/07001 are also useful in the composition of the present invention. Therefore, for purposes of the present invention, the term "~o~ ester" includes such derivatives.
The material which is sold commercially as sorbitan mono-ester (e.g., monostearate) does in fact contain significant amounts of di- and tri-esters and a typical analysis of sorbitan monostearate indicates that it comprises about 27% mono-, 32% di-and 30% tri- and tetra-esters. Commercial sorbitan monostearate therefore is a preferred material. Mixtures of sorbitan stearate and sorbitan palmitate having stearate/palmitate weight ratios varying between 10:1 and 1:10, and 1,5-sorbitan esters are useful. Both the 1,4- and 1,5-sorbitan esters are useful herein.
Other useful alkyl sorbitan esters for use in the softening compositions herein include sorbitan monolaurate, sorbitan monomyristate, sorbitan monopalmitate, so~
monob~h~n~te, sorbitan monooleate, sorbitan dilaurate, sorbitan dimyristate, sorbitan dipalmitate, sorbitan distearate, sorbitan dibehenate, sorbitan dioleate, and mixtures thereof, and mixed tallowalkyl sorbitan mono- and di-esters. Such mixtures are readily plc~ ed by reacting the foregoing hydroxy-substituted sorbitans, particularly the 1,4-and 1,5-sorbitans, with the co.le~,onding acid, ester, or acid chloride in a simple esterification reaction. It is to be recognized, of course, that commercial materials plcpa~d in this manner will comprise mixtures usually co..~;.i.-ing minor proportions of uncyclized sorbitol, fatty acids, polymers, isosorbide structures, and the like. In the present invention, it is preferred that such impurities are present at as low a level as possible.
The preferred sorbitan esters employed herein can contain up to about 15% by weight of esters of the C20-C26, and higher, fatty acids, as well as minor amounts of Cg, and lower, fatty esters.
Glycerol and polyglycerol esters, especially glycerol, diglycerol, triglycerol, and polyglycerol mono- and/or di- esters, p,cferably mono-, are also prcfell~d herein (e.g., polyglycerol monosle~te with a trade narne of R~ cllrf 7248). Glycerol esters can be prepared from naturally occll~nng triglycerides by normal extraction, purification and/or inter-esterification processes or by esterification processes of the type set forth hereinbefore for soll~ esters. Partial esters of glycerin can also be ethoxylated to form usable derivatives that are included within the term "glycerol esters."
Useful glycerol and polyglycerol esters include mono-esters with stearic, oleic,palmitic, lauric, isostearic, myristic, and/or behenic acids and the diesters of stearic, oleic, palmitic, lauric, isostearic, behenic, and/or myristic acids. It is understood that the - typical mono-ester contains some di- and tri-ester, etc.

, . ~_ ,.

CA 022~3399 1998-10-30 W O 97/42289 PCTrUS97/07001 The "glycerol esters" also include the polyglycerol, e.g., diglycerol through octaglycerol esters. The polyglycerol polyols are formed by con~n~ing glycerin or epichlorohydrin together to link the glycerol moieties via ether linkages. The mono-and/or diesters of the polyglycerol polyols are preferred, the fatty acyl groups typically being those described hereinbefore for the sorbitan and glycerol esters.
The dryer activated fabric softening compositions of the present invention may further includes a co-softener. The co-softener may comprise a carboxylic acid salt of a tertiary amine, tertiary amine ester, or mixtures thereof. The carboxylic acid salt forming anion moiety of the co-softener may be selected from the group consisting of lauric, myristic, palmitic, stearic, oleic and mixtures thereof. The amine salt of the co-softener may be selected from the group consisting of oleyldimethylamine stearate, dioleyl-methylamine stearate, linoleyldimethylamine stearate, dilinoleylmethylamine stearate, stearyldimethylamine stearate, distearylmethylamine myristate, stearyldimethylamine p~lmit~t~, distearylmethylarnine palmitate, distearylmethylamine myristate, distearyl-methylamine p~lmit~ts~ distearylmethylamine laurate, dioleyldistearylmethylamineoleate, distearylmethyl-amine oleate, and mixtures thereof.
Adjunct Fabric Conditioning A~ents Adjunct fabric conditioning compositions employed herein contain as an optional component, at a level of from about 0% to about 95%, preferably from about 20% to about 75%, more preferably from about 20% to about 60%, a carboxylic acid salt of a tertiary amine and/or ester amine which has the formula:
R6 o wherein RS is a long chain aliphatic group col-t~ il-g from about 8 to about 30 carbon atoms; R4 and R6 are the same or different and are independently selected from the group consisting of aliphatic groups cont~ining from about 1 to about 30 carbon atoms, hydroxyalkyl groups of the formula R8OH wherein R8 is an alkylene group of from about 2 to about 30 carbon atoms, and polyalkyleneoxy moieties of the formula R9O(RlOo)m- wherein R9 is hydrogen, C1-C30 alkyl, Cl-C30 alkenyl, and mixtures thereof; R10 is ethylene, 1,2 propylene, 1,3-propylene, and mixtures thereof; m is from about 2 to about 10; wherein further the R4, R5, R6, R8, and R9 chains can be ester interrupted groups; and wherein R7 is selected from the group consisting of C2-C30 linear alkyl, C2-C30 linear alkenyl, Cg-C30 aryl, Cg-C30 alkylaryl, and Cg-C30 CA 022~3399 1998-10-30 arylalkyl; substituted Cl-C30 linear alkyl, Cl-C30 linear alkenyl, Cg-C30 aryl, Cg-C30 alkylaryl, and Cg-C30 arylalkyl wherein the substituents are selected from the group consisting of halogen, carboxyl, and hydroxyl, said composition having a thermalsoftening point of from about 35 ~C to about 100 ~C.
Preferably, R5 is an aliphatic chain collt~ g from about C1 2-C30 linear alkyl, R6 is C12-C30 linear alkyl, and R4 is Cl-C30 linear alkyl.
Examples of preferred tertiary amines as starting material for the reaction between the amine and carboxylic acid to form the tertiary amine salts are: lauryldimethylamine, myristyldimethylamine, stearyl~limethylamine, tallow-dimethylamine, coconutdimethyl-amine, dilaurylmethylamine, distearylmethylamine, ditallowmethylamine, oleyldimethylamine, dioleylmethylamine, lauryldi(3-hydroxypropyl)amine, stearyldi(2-hydroxyethyl)amine, trilaurylamine, laurylethyl-methylamine, and ~(oc2H4)looH
C,8H37N

\(oc2H4)looH
Plefell~d fatty acids are those wherein R7 is Cg-C30 linear alkyl, more preferably C I I -C 17 linear alkyl.
Examples of specific carboxylic acids as a starting material are: formic acid, acetic acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, oxalic acid, adipic acid, 12-hydroxy stearic acid, benzoic acid, 4-hydroxy benzoic acid, 3-chloro benzoic acid, 4-nitro benzoic acid, 4-ethyl benzoic acid, 4-(2-chloroethyl)benzoic acid,phenylacetic acid, (4-chlorophenyl)acetic acid, (4-hydroxyphenyl)acetic acid, and phthalic acid.
Preferred carboxylic acids are stearic, oleic, lauric, myristic, palmitic, and mixtures thereof.
The amine salt can be formed by a simple addition reaction, well known in the art, disclosed in U.S. Pat. No. 4,237,155, Kardouche, issued Dec. 2, 19BO, which is incorporated herein by reference. Excessive levels of free arnines may result in odor problems, and generally free amines provide poorer softening performance than the amine salts.
Preferred amine salts for use herein as optional ingredients are those wherein the amine moiety is a Cg-C30 alkyl or alkenyl dimethyl amine or a di-Cg-C30 alkyl oralkenyl methyl amine, and the acid moiety is a Cg-C30 alkyl or alkenyl monocarboxylic acid. The amine and the acid, respectively, used to form the amine salt will often be of CA 022~3399 1998-10-30 WO 97t42289 PCT/US97/07001 mixed chain lengths rather than single chain lengths, since these materials are normally derived from natural fats and oils, or synthetic processed which produce a mixture of chain lengths. Also, it is often desirable to utilize mixtures of different chain lengths in order to modify the physical or performance characteristics of the softening composition.
Specific preferred amine salts for use in the present invention are oleyldimethylamine stearate, stearyldimethylamine stearate, stearyldimethylarnine myristate, stear~ldimethylarnine oleate, stearyldimethylarnine palmitate, distearylmethylamine p~lmit~t~ distearylmethylamine laurate, and mixtures thereof.
A particularly preferred mixture is oleyldimethylarnine stearate and distearylmethylamine myristate, in a ratio of 1:10 to 10:1, preferably about 1:1.
Other cationic materials with ring structures such as alkyl imit~7oline, imidazolinium, pyridine, and pyridiniurn salts having a single C12-C30 alkyl chain can also be used.
Very low pH is required to stabilize, e.g., imidazoline ring structures.
Some alkyl imi~olinium salts and their imidazoline precursors useful in the present invention have the general forrnula:

~ IC~ \R6 X

wherein y2 is -C(O)-O-, -O-(O)C-, -C(o)-N(R5)-, or -N(R5)-C(o)- in which R5 is hydrogen or a C l-C4 alkyl radical; R6 is a C I -C4 alkyl radical or H (for imidazoline precursors); R7 and R8 are each in~ep~n~ntly selected from R and R2 as defined hereinbefore for the single-long-chain cationic surfactant with only one being R2.
Some alkyl pyridinium salts useful in the present invention have the general formula:
2 +fi~
R N \=~ X

wherein R2 and X- are as defined above. A typical material of this type is cetylpyridiniurn chloride.
~lcf~ ;d Ingredients The following preferred ingredients can be suitably adrnixed with the modified polyamine fabric surface modifiers described herein above to obtain fabric tre~tment compositions useful for providing greasyloily dirt, lipophilic grime, and proteinaceous soil removal.
Anionic Detersive Surfa~t~nt~

CA 022~3399 1998-10-30 The compositions of the present invention comprise at least about 0.01%, preferably at least 0.1%, more preferably from about 1% to about 95%, most preferably from about 1% to about 80% by weight, of an anionic detersive surfactant. Alkyl sulfate surfactants, either primary or secondary, are a type of anionic surfactant of importance for use herein. Alkyl s--lf~tes have the general formula ROSO3M wherein R preferably is a Clo-C24 hydrocarbyl, preferably an alkyl straight or branched chain or hydroxyalkyl having a C 1 0-c20 alkyl component, more preferably a C 1 2-C 18 alkyl or hydroxyalkyl, and M is hydrogen or a water soluble cation, e.g., an alkali metal cation (e.g., sodium potassium, lithium), substituted or unsubstituted ammonium cations such as methyl-, dimethyl-, and trimethyl ammonium and quaternary ammonium cations, e.g., tetramethyl-amrnonium and dimethyl piper~ini lm, and cations derived from alkanol~min-os such as ethanolamine, diethanolamine, triethanolamine, and mixtures thereof, and the like.
Typically, alkyl chains of C 1 2-C 16 are p~cr~lcd for lower wash te,~ dlllres (e.g., below about 50~C) and C16-Clg alkyl chains are preferred for higher wash t~ pc.dl~lres (e.g., about 50~C).
Alkyl alkoxylated sulfate surf~t~nt~ are another category of preferred anionic surfactant. These surf~ct~nt~ are water soluble salts or acids typically of the formula RO(A)mSO3M wherein R is an unsubstituted Clo-C24 alkyl or hydroxyalkyl group having a Clo-C24 alkyl component, preferably a C12-C20 alkyl or hydroxyalkyl, more preferably C 1 2-C 18 alkyl or hydroxyalkyl, A is an ethoxy or propoxy unit, m is greater than zero, typically between about 0.5 and about 6, more preferably between about 0.5 and about 3, and M is hydrogen or a water soluble cation which can be, for example, a metal cation (e.g., sodium, potassium, lithium, calcium, m~gn~sium, etc.), ammonium orsubstituted-ammonium cation. Alkyl ethoxylated sulfates as well as alkyl propoxylated sulfates are cont~ plated herein. Specific examples of substituted ammonium cations include methyl-, dimethyl-, trimethyl-ammonium and quaternary ammoniurn cations, such as tetramethyl-ammonium, dimethyl piperdinium and cations derived from alkanol~min~s, e.g., monoethanolamine, diethanolaminej and triethanolamine, and mixtures thereof.
Exemplary surf~ct~nt~ are C12Clg alkyl polyethoxylate (1.0) sulfate, C12-Clg alkyl polyethoxylate (2.25) sulfate, C12-Clg alkyl polyethoxylate (3.0) sulfate, and C12-Clg alkyl polyethoxylate (4.0) sulfate wherein M is conveniently selected from sodium and potassiurn.
Nonionic Detersive Surf~ct~.-tc The compositions ofthe present invention comprise at least about 0.01%, - preferably at least 0.1%, more preferably from about 1% to about 95%, most preferably from about 1% to about 80% by weight, of an nonionic detersive surfactant. Preferred - ' t CA 022~3399 1998-10-30 W O 97/42289 PCT~US97tO7001 nonionic surfactants such as C 1 2-C 18 alkyl ethoxylates ("AE") including the so-called narrow peaked alkyl ethoxylates and C6-C 12 alkyl phenol alkoxylates (especiallyethoxylates and mixed ethoxy/propoxy), block alkylene oxide conden~te of C6 to C 12 alkyl phenols, alkylene oxide con-lenc~tçs of Cg-C22 alkanols and ethylene oxide/propylene oxide block polymers (PluronicTM-BASF Corp.), as well as semi polar nonionics (e.g., amine oxides and phosphine oxides) can be used in the present compositions. An extensive disclosure of these types of surfactants is found in U.S. Pat.

3,929,678, T ~llghlin et al., issued December 30, 1975, incorporated herein by reference.
Alkylpolysaccharides such as disclosed in U.S. Pat. 4,565,647 Llenado (incorporated herein by reference) are also plefe.,cd nonionic surfactants in the compositions of the invention.
Further preferred nonionic surf~ct~nt~ are the polyhydroxy fatty acid amides having the formula:

wherein R7 is Cs-C3 1 alkyl, preferably straight chain C7-C 1 9 alkyl or alkenyl, more preferably straight chain Cg-C 17 alkyl or alkenyl, most preferably straight chain C 1 1 ~C 15 alkyl or alkenyl, or mixtures thereof; R8 is selected from the group con~isting of hydrogen, C 1 -C4 alkyl, C 1 -C4 hydroxyalkyl, preferably methyl or ethyl, more preferably methyl. Q
is a polyhydroxyalkyl moiety having a linear alkyl chain with at least 3 hydroxyls directly connPcte~l to the chain, or an alkoxylated derivative thereof; plerell~d alkoxy is ethoxy or propoxy, and mixtures thereof. Preferred Q is derived from a reducing sugar in a reductive amination reaction. More preferably Q is a glycityl moiety. Suitable reducing sugars include glucose, fructose, maltose, lactose, galactose, mannose, and xylose. As raw materials, high dextrose corn syrup, high fructose corn syrup, and high maltose corn syrup can be utilized as well as the individual sugars listed above. These corn syrups may yield a mix of sugar components for Q. It should be understood that it is by no means intPn~led to exclude other suitable raw materials. Q is more preferably selected from the group consistingof-CH2(CHOH)nCH20H,-CH(CH20H)(CHOH)n 1CH20H,-CH2(CHOH)2-(CHOR')(CHOH)CH20H, and alkoxylated derivatives thereof, wherein n is an integerfrom 3 to 5, inclusive, and R' is hydrogen or a cyclic or aliphatic monosaccharide. Most preferred substituents for the Q moiety are glycityls wherein n is 4, particularly -CH2(CHOH)4CH20H.
R7Co-N< can be, for example, cocamide, ~le~dlllide, oleamide, lauramide, myristamide, capricamide, palmitamide, tallowamide, etc.

. ... . . . ~

CA 022~3399 1998-10-30 R8 can be, for example, methyl, ethyl, propyl, isopropyl, butyl, 2-hydroxy ethyl7 or 2-hydroxy propyl.
Q can be l-deoxyglucityl, 2-deoxyfructityl, I-deoxymaltityl, l-deoxylactityl, 1-deoxygalactityl, I-deoxymannityl, l-deoxymaltotriotityl, etc.
A particularly desirable surfactant of this type for use in the compositions herein is alkyl-N-methyl glucomide, a compound of the above formula wherein R7 is alkyl (preferably Cl l-C13), R8, is methyl and Q is l-deoxyglucityl.
Other sugar-derived surfactants include the N-alkoxy polyhydroxy fatty acid amides, such as C 1 o-C 18 N-(3-methoxypropyl) gh1c~mi-1~. The N-propyl through N-hexyl C12-C1g glucamides can be used for low su-leing Clo-C20 conventional soapsmay also be used. If high sudsing is desired, the branched-chain C I o-C 16 soaps may be used. Other conventional useful s~ ct~nte are listed in standard texts.
For the purposes of the present invention other detersive surfactants, describedherein below, may be used in the fabric surface modification compositions.
Optional CYclodextrin/Perfurne Complexes & Free Perfume Deliver,v Svstems The products herein can also contain from about 0.5% to about 60%, preferably from about 1% to about 50%, cyclodextrin/~,.rume inclusion complexes and/or freeperfurne, as disclosed in U.S. Pat. Nos. 5,139,687, Borcher et al., issued Aug. 18, 1992;
and 5,234,610, Gardlik et al., to issue Aug. 10, 1993, which are incorporated herein by reference. Perfumes are highly desirable, can usually benefit from protection, and can be complexed with cyclodextrin. Fabric softening products typically contain perfume to provide an olfactory aesthetic benefit and/or to serve as a signal that the product is effective.
Suitable perfurne component for use in the present invention comprise compounds having a ester of a perfurne alcohol. The ester includes at least one free carboxylate group and has the formula O
HOC--R~ClgR3 -- --n n wherein R is selected from the group con~i~ting of substituted or unsubstituted Cl-C30 straight, branched or cyclic alkyl, alkenyl, alkynyl, alkylaryl or aryl group; R' is a perfume alcohol with a boiling point at 760 mm Hg of less than about 300 ~C; and n and - m are individually an integer of 1 or greater.

CA 022~3399 1998-10-30 W O 97142289 PCTrUS97/07001 The perfume component may comprise from about 0.01% to about 10% by weight of the fabric enhancement/fabric modification composition. The perfume component may further comprise an ester of a perfume alcohol wherein the ester has at least one free carboxylate group in admixture with a fully esterified ester of a perfume alcohol.
Preferably, R is selected from the group con.~i~ting of substituted or unsubstituted C I - C20 straight, branched or cyclic alkyl, alkenyl, alkynyl, alkylaryl, aryl group or ring cont~ining a herteroatom. R' is ple~ bly a perfurne alcohol selected from the group con~i~ting of geraniol, nerol, phenoxanol, floralol, ~-citronellol, nonadol, cyclohexyl ethanol, phenyl ethanol, phenoxyethanol, isoborneol, fenchol, isocyclogeraniol, 2-phenyl-l -propanol, 3,7-dimethyl- 1 -octanol, and combinations thereof and the ester is preferably selected from maleate, succinate adipate, phth~l~te, citrate or pyromellitate esters of tbe perfume alcohol. The most ~.~r~ d esters having at least one free carboxylate group are then selected from the group con~i.ctin~ of geranyl succinate, neryl s~1ccin~t~, (,B-citronellyl) maleate, nonadol m~lP~te, phenoxanyl maleate, (3,7-dimetbyl-I-octanyl) succinate, (cyclohexyletbyl) maleate, floralyl succinate, (,B-citronellyl) phth~l~te and (phenylethyl) ~ip~te.
The optional perfume ingredients and compositions of this invention are the conventional ones kno~vn in tbe art. Selection of any perfume component, or amount of perfume, is based solely on aesthetic considerations. Suitable perfume compounds and compositions can be found in the art including U.S. Pat. Nos.: 4,145,184, Brain and C--mmin~, issued Mar. 20, 1979; 4,209,417, Whyte, issued June 24, 1980; 4,515,705, Moeddel, issued May 7, 1985; and 4,152,272, Young, issued May 1, 1979, all of said patents being incol~Joldled herein by lefelence. Many of the art recognized perfume compositions are relatively ~ubsku~ive to rn~ximi7P their odor effect on substrates.
However, it is a special advantage of perfume delivery via the perfume/cyclodextrin complexes that non~ub~ re perfumes are also effective.
If a product contains both free and complexed perfume, the escaped perfume from the complex contributes to the overall perfume odor intensity, giving rise to a longer lasting perfume odor hl~ s~ion.
As disclosed in U.S. Pat. No. 5,234,610, Gardlik/Trinh/Banks/Benvegnu, issued Aug. 3, 1993, said patent being inco~of~led herein by reference, by adjusting the levels of free perfume and perfume/CD complex it is possible to provide a wide range of unique perfume profiles in terms of timing (release) and/or perfume identity (character). Solid, - dryer-activated fabric conditioning compositions are a uniquely desirable way to apply the cyclodextrins, since they are applied at the very end of a fabric treatmPnt regimen .. .. . ... . .

CA 022~3399 1998-10-30 when the fabric is clean and when there are almost no additional tre~tment~ that can remove the cyclodextrin.
METHOD OF USE
The present invention relates to methods for modifiying the surface of fabric bycontacting the fabric with a laundry pre-tre~tment or laundry rinse-added composition thereby enhancing the ability of the fabric to be suitably cleaned during laundring with a detersive surfactant.
Pre-tre~tment~ will effect the current dirt, soils, and grimes as well as providing a modified surface to the fabric for further soil release-type ben.?fit~ Rinse-added compositions will provided the fabric surface with a layer of fabric ~I.b~ ve material which modifies the surface of the fabric and thereby prevents the full wetting out or absorbtion of greasy/oily dirt, lipophilic grime, and protienaceous soil.
The present invention specifically relates to methods for preventing the soiling of fabric by grass stains or other proteinaceous soils, the method of which comprises contacting the fabric to be modified with a composition co~ ,fi~illg the modified polyamines of the presnt invention without detersive surf~t~ntc This method of modifiying fabric for the prevention of grass stain and other proteinaceous soils must be done in the absense of a detersive ~Ul~c~t. Preferably the method involves a pre-tre~tm~nt of the fabric, more preferably two pre-ll~A~...rnt~, most preferably three pre-tre~tment~ Subsequent to the pre-tre~tm~nt detersive surf~ct~ntc can be used to launder the surface modified fabric without loosing the protective benefits against grass stain or protein~ceQus soiling.
The present invention specifically relates to methods for preventing the soiling of fabric by greasy/oily dirt or lipohilic grime, the method of which comprises contacting the fabric to be modified with a composition coml,.;sil-g the modified polyamines of the presnt invention in the presence of a suitable detersive sllrf~ t~nt This method of modifiying fabric for the prevention of greasy/oily dirt or lipohilic grime must be done in the ~resellce of an anionic or nonionic detersive surfactant, or mixtures thereof.
Preferably the method involves a pre-tre~tm~nt of the fabric, more preferably two pre-tre~tm~ntc, most l,.ef~ bly three pre-tre~tment~ Subsequent to the pre-tre~tm~ntdetersive surf~ct~nts can be used to launder the surface modified fabric without loosing the protective benefits against greasy/oily dirt or lipohilic grime.
Accordingly, there is provided a mPtho~l of inhibiting or reducing fabric discoloration which comprises the steps of contacting said fabrics in the rinse cycle with - an aqueous mediurn cont~ining at least 10ppm of a fabric softener composition as defined herein before.

PROCESS
The fabric softening composition can conveniently be made according to well known processes to the skilled person. An examplary disclosure is given in EP-A-0,668,902.
The water-soluble or dispersible, bleach stable, modified polyamine fabric surface modifiers useful herein are suitably prepared by the following methods.

Preparation of PEI 1800 E7 The ethoxylation is con~lcted in a 2 gallon stirred st~inles~ steel autoclave equipped for telnpe,dL~re measurement and control, pressure measurement, vacuum and inert gas purging, sampling, and for introduction of ethylene oxide as a liquid. A ~20 Ib.
net cylinder of ethylene oxide (ARC) is set up to deliver ethylene oxide as a liquid by a pump to the autoclave with the cylinder placed on a scale so that the weight change of the cylinder could be monitored.
A 750 g portion of polyethyleneimine (PEI) (Nippon Shol-..bai, Epomin SP-018 having a listed average molecular weight of 1800 eq~.~ting to about 0.417 moles of polymer and 17.4 moles of nitrogen functions) is added to the autoclave. The autoclave is then sealed and purged of air (by applying vacuum to minus 28" Hg followed bypressurization with nitrogen to 250 psia, then venting to atmospheric ~ s~u,c). The autoclave contents are heated to 130 ~C while applying vacuum. After about one hour, the autoclave is charged with nitrogen to about 250 psia while cooling the autoclave to about 105 ~C. Ethylene oxide is then added to the autoclave incrementally over time while closely monitoring the autoclave pressure, temperature, and ethylene oxide flow rate. The ethylene oxide pump is turned off and cooling is applied to limit any temperature increase resulting from any reaction exotherm. The ten~ alul~ is m~int;7.in~d between 100 and 110 ~C while the total pressure is allowed to gradually increase during the course of the reaction. After a total of 750 grams of ethylene oxide has been charged to the autoclave (roughly equivalent to one mole ethylene oxide per PEI nitrogen function), the t~ e.dllre is increased to 110 ~C and the autoclave is allowed to stir for an additional hour. At this point, vacuum is applied to remove any residual unreacted ethylene oxide Next, vacuum is continuously applied while the autoclave is cooled to about 50 ~C while introducing 376 g of a 25% sodium methoxide in methanol solution (1.74 moles, to achieve a 10% catalyst loading based upon PEI nitrogen functions). The methoxide solution is sucked into the autoclave under vacuum and then the autoclave temperature - controller setpoint is increased to 130 ~C. A device is used to monitor the power con~llmed by the agitator. The agitator power is monitored along with the telllpe.dlule CA 022~3399 1998-10-30 and pressure. Agitator power and temperature values gradually increase as methanol is removed from the autoclave and the viscosity of the mixture increases and stabilizes in about 1 hour indicating that most of the methanol has been removed. The mixture is further heated and agitated under vacuum for an additional 30 minutes.
Vacuum is removed and the autoclave is cooled to 105 ~C while it is being charged with nitrogen to 250 psia and then vented to arnbient pressure. The autoclave is charged to 200 psia with nitrogen. Ethylene oxide is again added to the autoclave incrementally as before while closely monitoring the autoclave pressure, t~lllpelalule, and ethylene oxide flow rate while m~int~ining the temperature between 100 and 110 ~C
and limiting any t~.l,p.,.dlllre increases due to reaction exotherm. After the addition of 4500 g of ethylene oxide (resl~lting in a total of 7 moles of ethylene oxide per mole of PEI nitrogen function) is achieved over several hours, the telllpeid~ is increased to 110 ~C and the mixture stirred for an additional hour.
The reaction mixture is then collected in nitrogen purged conlaille.~ and eventually transferred into a 22 L three neck round bottomed flask equipped with heating and agitation. The strong alkali catalyst is neutralized by adding 167 g methanesulfonic acid (1.74 moles). The reaction mixture is then deodorized by passing about 100 cu. ft. of inert gas (argon or nitrogen) through a gas dispersion frit and through the reaction mixture while agitating and heating the mixture to 130 ~C.
The final reaction product is cooled slightly and collected in glass containfls purged with nitrogen.
In other plel)~alions the neutralization and deodorization is accomplished in the reactor before dischalging the product.

4.7% Ql~ lt~rni7~tion of PEI 1800 E7 To a 500ml erlenmeyer flask e~llipped with a m~gnetjc stirring bar is added poly(ethyle.~ ,.inP), ~W 1800 ethoxylated to a degree of 7 (224g, 0.637 mol nitrogen, pl.,p~d as in Example 1) and acetonitrile (Baker, 150g, 3.65 mol). Dimethyl sulfate (Aldrich, 3.8g, 0.030 mol) is added all at once to the rapidly stirring solution, which is then stoppered and stirred at room temperature overnight. The acetonitrile is e~/~olaled on the rotary evaporator at ~60~C, followed by a Kugelrohr al)p~dlLls (Aldrich) at ~80~C
to afford ~220g of the desired material as a dark brown viscous liquid. A 13C-NMR
(D20) sye.;LIulll shows the ~l sf nce of a peak at ~58ppm cG~ onding to dimethylsulfate. A 1 H-NMR (D2O) spectrum shows the partial shifting of the peak at 2.5ppm - (methylenes ~ cll~d to unql~1f ~.. ;,~d nitrogens) to ~3.0ppm.

_ I

CA 022~3399 1998-10-30 W O 97/42289 PCTrUS97/07001 Oxidation of 4.7% Ouaternized PEI 1800 E7 To a 500ml erlenrneyer flask equipped with a magnetic stirring bar is added poly(ethyleneimine), MW 1800 which has been ethoxylated to a degree of 7, and ~4.7%
quaternized with dimethyl sulfate (121.7g, ~0.32 mol oxidizeable nitrogen, pl~p~ed as in Example 3), hydrogen peroxide (Aldrich, 40g of a 50 wt% solution in water, 0.588 mol), and water (109.4g). The flask is stoppered, and after an initial exotherm the solution is stirred at room temperature overnight. A 1 H-NMR (D2O) spectrum shows the total shifting of the methylene peaks at 2.5-3.0ppm to ~3.5ppm. To the solution is added ~Sg of 0.5% Pd on alumina pellets, and the solution is allowed to stand at room t~ p~ldlure for ~3 days. Peroxide indicator paper shows that no peroxide is left in the system. The material is stored as a 46.5% solution in water.

Formation of amine oxide of PEI 1800 E7 To a 500 mL Erlenrneyer flask equipped with a m~gnetic stirring bar is added polyethyleneimine having a molecular weight of 1800 and ethoxylated to a degree of about 7 ethoxy groups per nitrogen (PEI-1800, E7) (209 g, 0.595 mol nitrogen, p.epaled as in Example I), and hydrogen peroxide (120 g of a 30 wt % solution in water, 1.06 mol). The flask is stoppered, and after an initial exotherm the solution is stirred at room ten~,dlllre overnight. lH-NMR (D20) spectrurn obtained on a sample ofthe reaction mixture indicates complete conversion. The resonances ascribed to methylene protons a~ cer~t to unoxidized nitrogens have shifted from the original position at ~2.5 ppm to ~3.5 ppm. To the reaction solution is added approximately S g of 0.5% Pd on alumina pellets, and the solution is allowed to stand at room tel~pc.dlure for approxim~t~ly 3 days. The solution is tested and found to be negative for peroxide by indicator paper.
The material as obtained is suitably stored as a 51.1 % active solution in water.
EXAMPLE S
Preparation of PEI 1200 E7 The ethoxylation is con-luct~cl in a 2 gallon stirred stainless steel autoclave equipped for t~ll-peldlure measurement and control, ~u~es~ule measurement, vacuum and inert gas purging, sarnpling, and for introduction of ethylene oxide as a liquid. A ~20 Ib.
net cylinder of ethylene oxide (ARC) is set up to deliver ethylene oxide as a liquid by a pump to the autoclave with the cylinder placed on a scale so that the weight change of the cylinder could be monitored.
A 750 g portion of polyethyleneimine (PEI) ( having a listed average molecular - weight of 1200 equating to about 0.625 moles of polymer and 17.4 moles of nitrogen functions) is added to the autoclave. The autoclave is then sealed and purged of air (by CA 022~3399 1998-10-30 applying vacuum to minus 28" Hg followed by pressurization with nitrogen to 250 psia, then venting to atmospheric pressure). The autoclave contents are heated to 130 ~C
while applying vacuum. After about one hour, the autoclave is charged with nitrogen to about 250 psia while cooling the autoclave to about 105 ~C. Ethylene oxide is then added to the autoclave incrementally over time while closely monitoring the autoclave pressure, temperature, and ethylene oxide flow rate. The ethylene oxide pump is turned offand cooling is applied to limit any telllp~lalule increase resulting from any reaction exotherm. The tclllycld~ e is m~int~ined between 100 and 110 ~C while the total yl~;s~ule is allowed to gradually increase during the course of the reaction. After a total of 750 grams of ethylene oxide has been charged to the autoclave (roughly equivalent to one mole ethylene oxide per PEI nitrogen function), the tclll~vc~dl~lre is increased to 110 ~
C and the autoclave is allowed to stir for an additional hour. At this point, vacuum is applied to remove any residual unreacted ethylene oxide.
Next, vacuurn is continuously applied while the autoclave is cooled to about 50 ~
C while introducing 376 g of a 25% sodium methoxide in methanol solution (1.74 moles, to achieve a 10% catalyst loading based upon PEI nitrogen functions). The methoxide solution is sucked into the autoclave under vacuum and then the autoclave telllycldlulc controller setpoint is increased to 130 ~C. A device is used to monitor the power consumed by the agitator. The agitator power is monitored along with the tclllpclalul~:
and pressure. Agitator power and te~nyclalule values gradually increase as methanol is removed from the autoclave and the viscosity of the ~h~lulc increases and stabilizes in about 1 hour inflic~ting that most of the methanol has been removed. The mixture is further heated and agitated under vacuum for an additional 30 minlltes Vacuum is removed and the autoclave is cooled to 105 ~C while it is being charged with nitrogen to 250 psia and then vented to ambient pressure. The autoclave is charged to 200 psia with nitrogen. Ethylene oxide is again added to the autoclave incremPnt~lly as before while closely mo~ h~g the autoclave pleS~ ;, tt;llly~,lalule, and ethylene oxide flow rate while 1~ g the t~ yelalulc b~lween 100 and 110 ~C
and limiting any tellll)~lalulc; increases due to reaction exotherm. After the addition of 4500 g of ethylene oxide (resulting in a total of 7 moles of ethylene oxide per mole of PEI nitrogen function) is achieved over several hours, the te~pc~dlllre is increased to 110 ~C and the mixture stirred for an additional hour.
The reaction mixture is then collected in nitrogen purged containers and eventually trdll~rell~d into a 22 L three neck round bottomed flask equipped ~vith heating and - agitation. The strong alkali catalyst is neutralized by adding 167 g meth~nesulfonic acid (1.74 moles). The reaction mixture is then deodorized by passing about 100 cu. ft. of ,. ..

CA 022~3399 1998-10-30 W O 97/42289 PCT~US97/07001 inert gas (argon or nitrogen) through a gas dispersion frit and through the reaction mixture while agitating and heating the mixture to 130 ~C.
The final reaction product is cooled slightly and collected in glass containers purged with nitrogen.
In other pre~alions the neutralization and deodorization is accomplished in the reactor before discharging the product.
Other preferred examples such as PEI 1200 E15 and PEI 1200 E20 can be plepared by the above method by adjusting the reaction time and the relative amount of ethylene oxide used in the reaction.

9.7% O~terni7~ttion of PEI 1200 E7 To a 500ml erlenmeyer flask equipped with a magnetic stirring bar is added poly(ethyleneimine), MW 1200 ethoxylated to a degree of 7 (248.4g, 0.707 mol nitlogen, prepared as in Example 5) and acetonitrile (Baker, 200 mL). Dimethyl sulfate (Aldrich, 8.48g, 0.067 mol) is added all at once to the rapidly stirring solution, which is then sto~peled and stirred at room t~ e.d~ule overnight. The acetonitrile is evaporated on the rotary evaporator at ~60~C, followed by a Kugelrohr app~lus (Aldrich) at ~80~C to afford ~220g of the desired material as a dark brown viscous liquid. A 13C-NMR (D2O) spectrum shows the absence of a peak at ~58ppm corresponding to dimethyl sulfate. A
1 H-NMR (D2O) spectrum shows the partial shifting of the peak at 2.5ppm (methylenes ~tt~rh~l to unqu~terni7Pd nitrogens) to ~3.0ppm.

4.7% Oxidation of 9.5% Quaternized PEI 1200 E7 To a 500ml erlenmeyer flask equipped with a m~gn~tic stilTing bar is added poly(ethyleneimine), MW 1200 which has been ethoxylated to a degree of 7, and ~9.5%
qu~t~t~;7.o~1 with dimethyl sulfate (144g, ~0.37 mol oxitli7~hle nitrogen, prepared as in Example 6), hydrogen peroxide (Aldrich, 35.4g of a 50 wt% solution in water, 0.52 mol), and water (100g). The flask is stoppered, and after an initial exotherm the solution is stirred at room temperature overnight. A 1H-NMR (D2O) spectrum shows the total shifting of the methylene peaks at 2.5-3.0ppm to ~3.5ppm. To the solution is added just enough sodium bisulfite as a 40% water solution to bring the residual peroxide level down to 1-5ppm. The sodium sulfate which forms causes an aqueous phase to separate which contains salts, but little or no organics. The aqueous salt phase is removed and the desired oxidized polyethyleneimine derivative is obtained and stored as a 52% solution in water.

, . . , ~ . .. . . . .

CA 022~3399 1998-10-30 W O 97/42289 PCTrUS97/07001 The compositions used for the methods of the present invention are those laundrydetergent pre-soaks, pre-treatments or rinse-added compositions described further herein Examples of fabric enhancement compositions include the following:
Weight %
Ingredients 8 9 10 11 12 DEQA 2.6 2.9 18.0 19.0 19.0 Fatty acid 0.3 - 1.0 - -Hydrochloride acid 0.02 0.02 0.02 0.02 0.02 PEG - - 0.6 0.6 0.6 Perfume 1.0 1.0 1.0 1.0 1.0 Silicone antifoam 0.01 0.01 0.01 0.01 0.01 PEI 1200E1 2.0 2.0 1.0 1.5 2.5 Dye (ppm) 10 10 50 50 50 Water and minors balance balance balance balance balance The following examples include the fabric enh~ncemnt poly amines in combination with and without surfactants.

Weight %
Ingredients 13 14 15 16 Polyhydroxy Coco-Fatty Acid 3.65 3.50 --Amide C 1 2-C 13 Alcohol Ethoxylate Eg 3 .65 0.80 -- --Sodium C 1 2-C 1 5 Alcohol Sulfate 6.03 2.50 -- --DTDMAMS 1.00 1.00 3.00 3.00 PEI 1800E1 4.00 4.00 4.00 4.00 Pt:.~l~ 1 1 1 1 Perfume/Cyclodextrin Complex -- 20 -- 20 Digeranyl Succinate 1 0.50 Carriers and minors balance balance balance balance

Claims

WHAT IS CLAIMED IS:

1. A fabric surface treatment composition comprising:
a) an effective amount of a fabric conditioning agent;
b) an effective amount of a water-soluble or dispersible, bleach stable, modified polyamine fabric surface modifier comprising a polyamine backbone corresponding to the formula:

having a modified polyamine formula V(n+1)W m Y n z or a polyamine backbone corresponding to the formula:

having a modified polyamine formula V(n-k+1)W m Y n Y'k Z, wherein k is less than or equal to n, said polyamine backbone prior to modification has a molecular weight greater than 200 daltons, wherein i) V units are terminal units having the formula:

or or ;

ii) W units are backbone units having the formula:

or or ;

iii) Y units are branching units having the formula:

or or ; and iv) Z units are terminal units having the formula:

or or ;
wherein backbone linking R units are selected from the group consisting of C2-C12 alkylene, C4-C12 alkenylene, C3-C12 hydroxyalkylene, C4-C12 dihydroxy-alkylene, C8-C12 dialkylarylene, -(R1O)x R1-, -(R1O)x R5(OR1)x-, -(CH2CH(OR2)CH2O)z-(R1O)y R1(OCH2CH(OR2)CH2)w-, -C(O)(R4)r C(O)-, CH2CH(OR2)CH2-, and mixtures thereof, preferably C2-C12 alkylene, C3-C12 hydroxyalkylene, C4-C12 dihydroxyalkylene, C8-C12 dialkylarylene, -(R10)x R1-, -(R10)x R5(OR1)x-, (CH2CH(OH)CH2O)z(R1O)y R1(OCH2CH(OH)CH2)w-, CH2CH(OR2)CH2-, and mixtures thereof, more preferably C2-C12 alkylene, C3-C12 hydroxyalkylene, C4-C12 dihydroxyalkylene, (R1O)x R1-, -(R1O)x R5-(OR1)x-, -(CH2CH(OH)CH2O)z-(R1O)yR1(OCH2CH(OH)CH2)w-, and mixtures thereof, most preferably C2-C12 alkylene, and mixtures thereof; wherein R1 is C2-C6 alkylene, preferably ethylene, and mixtures thereof; R2 is hydrogen, -(R10)x B, and mixtures thereof, preferably hydrogen; R3 is C1-C18 alkyl, C7-C12 arylalkyl, C7-C12 alkyl substituted aryl, C6-C12 aryl, and mixtures thereof, C1-C6 alkyl and mixtures thereof, more preferably methyl; R4 is C1-C12 alkylene, C4-C12 alkenylene, C8-C12 arylalkylene, C6-C10 arylene, and mixtures thereof, preferably C2-C12 alkylene, C8-C12 arylalkylene, and mixtures thereof, more preferably, ethylene, butylene, and mixtures thereof; R5 is C1-C12 alkylene, C3-C12 hydroxyalkylene, C4-C12 dihydroxy-alkylene, C8-C12 dialkylarylene, -C(O)-, -C(O)NHR6NHC(O)-, -R1(OR1)-, -C(O)(R4)r C(O)-, -CH2CH(OH)CH2-, CH2CH(OH)CH2O(R1O)y R1OCH2CH(OH)CH2-, and mixtures thereof, preferably ethylene, -C(O)-, -C(O)NHR6NHC(O)-, -R1(OR1)y-, -(CH2CH(OH)CH2O)z(R1O)y R1(OCH2CH(OH)-CH2)w-, -CH2CH(OH)CH2-, and mixtures thereof, more preferably -CH2CH(OH)CH2-; R6 is C2-C12 alkylene or C6-C12 arylene; E units are selected from the group consisting of hydrogen, C1-C22 alkyl, C3-C22 alkenyl, C7-C22 arylalkyl, C2-C22 hydroxyalkyl, -(CH2)p CO2M,-(CH2)q SO3M, -CH(CH2CO2M)CO2M, -(CH2)p PO3M,-(R1O)x B, -C(O)R3, and mixtures thereof; preferably hydrogen, C3-C22 hydroxyalkyl, benzyl, C1-C22 alkyl, -(R1O)x B, -C(O)R3, -(CH2)p CO2-M+, -(CH2)q SO3-M+, -CH(CH2CO2M)-CO2M and mixtures thereof, more preferably hydrogen, C1-C22 alkyl, -(R1O)x B, -C(O)R3, and mixtures thereof, most preferably -(R1O)x B; provided that when any E
unit of a nitrogen is a hydrogen, said nitrogen is not also an N-oxide; B is hydrogen, C1-C6 alkyl, -(CH2)q SO3M, -(CH2)p-CO2M, -(CH2)q(CHSO3M)CH2SO3M, -(CH2)q(CHSO2M)CH2-SO3M, -(CH2)p PO3M, -PO3M, and mixtures thereof, preferably hydrogen, C1-C6 alkyl, -(CH2)q SO3M, -(CH2)q(CHSO3M)-CH2SO3M, -(CH2)q(CHSO2M)CH2SO3M, and mixtures thereof, more prefelably hydrogen, -(CH2)q SO3M, and mixtures thereof, most preferably hydrogen; M is hydrogen or a water soluble cation in sufficient amount to satisfy charge balance; X is a water soluble anion; provided at le~t one backbone nitrogen is quaternized or oxidized; m has the value from 4 to 400; n h~ the value from 0 to 200; p has the value from 1 to 6, q has the value from 0 to 6; r has the value of 0 or 1; w has the value 0 or 1; x has the value from 1 to 100; y has the value from 0 to 100; z has the value 0 or 1; and c) the balance carrier and adjunct ingredients.

2. The composition according to Claim 1 wherein the fabric conditioning agent comprises an ester quaternary arnmonium compound selected from the group consisting of:
a) ester quaternary ammonium compounds having the formula wherein Y is -O-(O)C- or -C(O)-O-; p is 1 to 3; v is from 1 to 4; R1 is C1-C6 alkyl C1-C4 hydroxy alkyl group, benzyl, and mixtures thereof;

R2 is C8-C30 saturated alkyl, C8-C30 unsaturated alkyl, C8-C30 substituted alkyl, C8-C30 unsubstituted alkyl, and mixtures thereof; X-is a softener-compatible anion;
b) ester quaternary ammonium compounds having the formula wherein Y" is a carboxy moiety having the formula ; ; ; ;

and mixtures thereof, wherein at least one Y group is or the index p is from 1 to 3; the index v is from 1 to 4, and mixtures thereof;
R1 is C1-C6 alkyl, benzyl, and mixtures thereof; R2 is C8-C30 saturated alkyl, C8-C30 unsaturated alkyl, C8-C30 substituted alkyl, C8-C30 unsubstituted alkyl, and mixtures thereof wherein each R2 moiety suitable for use has an Iodine Value of from 3 to 60; R3 is hydrogen, R, and mixtures thereof; X- is a softener-compatible anion;
c) ester quaternary ammonium compounds having the formula wherein the index v is from 1 to 4, and mixtures thereof; R1 is C1-C4 alkyl, C1-C4 hydroxy alkyl group, and mixtures thereof; R2 is C8-C30 saturated alkyl, C8-C30 unsaturated alkyl, C8-C30 substituted alkyl, C8-C30 unsubstituted alkyl, and mixtures thereof, wherein each R2 moiety has an Iodine Value of from 3 to 60; X- is methylsulfate.
d) ester quaternary ammonium compounds having the formula the index v is from 1 to 4, and mixtures thereof; p has the value 2; R1 is C 1 -C4 alkyl, C l-C4 hydroxy alkyl group, and mixtures thereof; R2 is C8-C30 saturated alkyl, C8-C30 unsaturated alkyl, C8-C30 substituted alkyl, C8-C30 unsubstituted alkyl, and mixtures thereof, wherein each R2 moiety has an Iodine Value of from 3 to 60; wherein each R2 moiety suitable for use has an Iodine Value of from 3 to 60; X~ is a softener-compatible anion; and e) and mixtures thereof.

3. A composition according to either of Claims 1 or 2 further comprising a perfume component having at least 2% by weight of an ester of a perfume alcohol wherein the ester has at least one free carboxylate group, said ester having the formula:

wherein R is selected from the group consisting of substituted or unsubstituted C1 -C30 linear, branched or cyclic alkylene, alkenylene, alkynylene, alkylarylene, arylene, a ring containing a heteroatom, and mixtures thereof; R' is a perfume alcohol having a boiling point at 760 mm Hg of less than 300 °C; the indices m and n are independently integers greater than or equal to 1.

4. A composition according to any of Claims 1-3 in liquid form wherein the adjunct ingredients are selected from the group consisting of builders, optical brighteners, bleaches, bleach boosters, bleach activators, soil release polymers, dye transfer agents, dispersents, enzymes, suppressors, dyes, perfumes, colorants, filler salts, hydrotropes, and mixtures thereof.

5. A method of inhibiting or reducing fabric discoloration, said method comprising the steps of contacting fabrics in the rinse cycle with an aqueous medium containing a fabric surface treatment composition according to any of Claims 1-4.

6. A method of inhibiting or reducing fabric discoloration, said method comprising the steps of contacting fabrics in the rinse cycle with an aqueous medium containing a fabric surface treatment composition according to any of Claims 1-4.

7. A method of inhibiting or reducing fabric discoloration, said method comprising the steps of contacting fabrics in the rinse cycle with an aqueous medium containing a liquid fabric surface treatment composition according to any of Claims 1-4.