EP0907703B1

EP0907703B1 - Detergent compositions comprising modified polyamines as dye transfer inhibitors

Info

Publication number: EP0907703B1
Application number: EP97921413A
Authority: EP
Inventors: Rajan Keshav Panandiker; William Conrad Wertz; Chanchal Kumar Ghosh
Original assignee: Procter and Gamble Co
Current assignee: Procter and Gamble Co
Priority date: 1996-05-03
Filing date: 1997-04-25
Publication date: 2002-06-26
Anticipated expiration: 2017-04-25
Also published as: ZA973756B; ES2176736T3; MA24166A1; AR006951A1; CZ354798A3; DE69713598D1; AU2745597A; BR9710960A; JPH11509268A; HUP9903943A3; DE69713598T2; ATE219788T1; JP3202246B2; WO1997042291A1; MX9809171A; EP0907703A1; MX219071B; HUP9903943A2

Description

FIELD OF THE INVENTION

The present invention relates to laundry detergent compositions which can be used to wash dye-containing colored fabrics and which contain bleach stable, modified polyamine additives that inhibit dye transfer between fabrics during laundering operations. The present invention also relates to methods for inhibiting dye transfer during laundering dye-containing colored fabrics in aqueous solutions formed from laundry compositions comprising fabric surface modifying polyamines.

BACKGROUND OF THE INVENTION

One of the most persistent and troublesome problem-causing events which arises during modem fabric laundering operations is the tendency of some colored fabrics to release dye into the laundering solutions. Such dye is then frequently transferred onto other fabrics being washed in the same aqueous washing solution.
One approach in attacking the dye transfer problem in laundering operations has been to complex or adsorb the fugitive dyes washed out of dyed fabrics before such dyes have the opportunity to become attached to other articles in the wash solution. Certain polymeric materials, for instance, have been suggested as being useful laundry detergent additives which can complex or adsorb fugitive dyes in aqueous washing solutions. For example Abel, U.S. Patent 4,545,919; Issued October 8, 1985 describes the use of carboxyl-containing polymers in fabric laundering operations. Waldhoff et al; DE-A-2 814 329, Published October 11, 1979 discloses the use of N-vinyl-oxazolidone polymers and Cracco et al; GB 1,348,212; Published March 13, 1974 discloses the use of 15-35% of a copolymer of polyvinylpyrrolidone and acrylic acid nitrile or maleic anhydride within a washing powder. Clements et al; EP-A-265 257; Published April 27, 1988 describes detergent compositions comprising an alkali-metal carboxy-metal carboxymethylcellulose, a vinylpyrrolidone polymer and a polycarboxylate polymer.
Notwithstanding prior art attempts to solve the dye transfer problem during fabric laundering, there is a continuing need to identify detergent compositions, detergent composition additives and fabric laundering methods which are especially effective against dye transfer. Accordingly, it is an object of the present invention to provide detergent compositions which contain selected ingredients that eliminate or at least minimize dye transfer between fabrics when such compositions are used in fabric laundering operations.
It has now been surprisingly discovered that a combination of certain dye transfer inhibitors and certain modified polyamines act together to provide an increased dye transfer inhibition benefit. This unexpected result has yielded compositions that provide this benefit to a wide range of fabric type, namely cotton, synthetic, and synthetic-cotton blended fabric.
The present process and compositions, because of the stability of the modified polyamines disclosed herein toward bleaching agents, now provides this dye transfer inhibition to fabric articles in the presence of traditional bleaching agents.
The process or method of the present invention is equally effective when the laundry detergent compositions disclosed herein are solid or liquid. The solid laundry detergents may be in the form of granules, flakes or laundry bars. The liquid detergents can have a wide range of viscosity and may include heavy concentrates, pourable "ready" detergents, or light duty fabric pre-treatments.
The modified polyamines disclosed in the present method are especially compatible with other laundry detergent additives and adjuncts.
It is a further object of the present invention to provide such especially effective dye transfer-inhibiting detergent compositions in either granular or liquid form.
It is a further object of the present invention to provide a method for laundering colored fabrics in aqueous washing solutions which are formed from the detergent compositions herein and which thereby contain materials that eliminate or at least minimize dye transfer between fabrics being washed therein.

BACKGROUND ART

In addition to the above cited art, the following disclose modified polyamines; 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 4,891,160, Vander Meer, issued January 2, 1990; 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 December 29, 1978; U.K. Patent 1,498,520, published January 18, 1978; German Patent DE 28 29 022, issued January 10, 1980; Japanese Kokai JP 06313271, published April 27, 1994; and EP 634,486, published January 18, 1995.

SUMMARY OF THE INVENTION

The present invention relates to laundry detergent compositions which provide especially effective inhibition of dye transfer between fabrics being laundered in aqueous washing solutions that are formed from these detergent compositions.
The laundry detergent compositions of the present invention comprise:
a) at least 0.01% by weight, of a dye transfer inhibition agent;
b) at least 0.1% by weight, of a water-soluble or dispersible, modified polyamine fabric surface modifying agent, said agent comprising a polyamine backbone corresponding to the formula:
having a modified polyamine formula V_(n+1)W_mY_nZ or a polyamine backbone corresponding to the formula:
having a modified polyamine formula V_(n-k+1)W_mY_nY'_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 terminal units having the formula:
ii) W units are backbone units having the formula:
iii) Y units are branching units having the formula:
and
iv) Y' units having the formula:
and
v) Z units are terminal units having the formula:

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c) the balance carrier and adjunct ingredients said adjunct ingredients are selected from the group consisting of builders, optical brighteners, bleaches, bleach boosters, bleach activators, enzymes, enzyme stabilizers, suds suppressors, dyes, perfumes, colorants, filler salts, hydrotropes, and mixtures thereof.
It is a further object of the present invention to provide methods for preventing the transfer of dyes from the laundry liquor to the fabric being laundered.
All percentages, ratios and proportions herein are by weight, unless otherwise specified. All temperatures are in degrees Celsius (° C) unless otherwise specified.

DETAILED DESCRIPTION OF THE INVENTION

The laundry detergent compositions of the present invention comprise:
a) at least 0.01% by weight, of a dye transfer inhibition agent;
b) at least 0.1% by weight, of a water-soluble or dispersible, modified polyamine fabric surface modifying agent according to the present invention; and
c) the balance carriers and adjunct ingredients.
Preferred laundry detergent compositions of the present invention comprise:
a) at least 5% by weight, of an anionic detersive surfactant;
b) at least 1% by weight, of a nonionic detersive surfactant;
c) at least 0.01% by weight, of a dye transfer inhibition agent;
d) at least 0.5% by weight, of a water-soluble or dispersible, modified polyamine fabric surface modifying agent according to the present invention; and
e) the balance carriers and adjunct ingredients.
Further preferred laundry detergent compositions of the present invention comprise:
a) at least 5% by weight, of an anionic detersive surfactant;
b) at least 1% by weight, of a nonionic detersive surfactant;
c) at least 0.01% by weight, of a dye transfer inhibition agent;
d) optionally at least 1% by weight, of a bleach;
e) at least about 0.5 % by weight, of a water-soluble or dispersible, modified polyamine fabric surface modifying agent according to the present invention; and
f) the balance carriers and adjunct ingredients.
A more preferred laundry detergent compositions of the present invention comprise:
a) at least 5% by weight, of an anionic detersive surfactant;
b) at least 1% by weight, of a nonionic detersive surfactant;
c) at least 0.01% by weight, of a dye transfer inhibition agent;
d) optionally at least 1% by weight, of a bleach;
e) at least 0.1% by weight, of a soil release polymer;
f) at least 0.5 % by weight, of a water-soluble or dispersible, modified polyamine fabric surface modifying agent of the composition according to the present invention; and
g) the balance carriers and adjunct ingredients.
A further more preferred laundry detergent compositions of the present invention comprise:
a) at least 5% by weight, of an anionic detersive surfactant selected from the group consisting of alkyl sulfate, alkyl alkoxy sulfate, and mixtures thereof
b) at least 5% by weight, of a nonionic detersive surfactant selected from the group consisting of polyhydroxy fatty acid amides, alcohol ethoxylates, and mixtures thereof;
c) at least 0.01% by weight, of a dye transfer inhibition agent;
d) optionally at least about 1% by weight, of a bleach;
e) at least 0.5% by weight, of a water-soluble or dispersible, modified polyamine fabric surface modifying agent of the composition according to the present invention; and
f) the balance carriers and adjunct ingredients.
Further preferred laundry detergent compositions are described in the dependent claims.
The preferred laundry detergent compositions of the present invention comprise the following preferred materials.

Polymeric Dye Transfer Inhibiting Agents

The detergent compositions herein preferably comprise from about 0.01% to 10% by weight of certain types of polymeric dye transfer inhibiting agents. Preferably the detergent compositions herein comprise from about 0.05% to 0.5% by weight of these polymeric dye transfer inhibiting materials.
The selected dye transfer inhibiting polymeric materials can be certain polyamine N-oxide polymers, certain copolymers of N-vinylpyrrolidone, N-vinylimidazole, polyethoxylated urethanes, acrylamide containing polymers, polyamino acids, and combinations of these materials. Each of these polymer/copolymer types is described in greater detail as follows:

Polyamine N-oxide Polymers

The polyamine N-oxide polymers suitable for use herein contain units having the structural formula:
wherein P is a polymerizable unit to which a N-O group can be attached or the N-O group can form part of the polymerizable unit or the N-O group can be attached to both units; A is one of the following structures:
x is 0 or 1; and, R comprises aliphatic, ethoxylated aliphatic, aromatic, heterocyclic or alicyclic groups or any combination thereof to which the nitrogen of the N-O group can be attached or the N-O group is part of these groups.
The N-O group can be represented by the following general structures:
wherein R₁, R₂, R₃ are aliphatic, aromatic, heterocyclic or alicyclic groups or, combinations thereof; x, y and z are 0 or 1; and, the nitrogen of the N-O group can be attached or form part of any of the aforementioned groups. Further, the N-O group can be part of the polymerizable unit (P) or can be attached to the polymeric backbone or a combination of both.
Suitable polyamine N-oxides wherein the N-O group forms part of the polymerizable unit comprise polyamine N-oxides wherein R is selected from aliphatic, aromatic, alicyclic or heterocyclic groups. One class of such polyamine N-oxides comprises the group of polyamine N-oxides wherein the nitrogen of the N-O group forms part of the R group. Preferred polyamine N-oxides are those wherein R is a heterocyclic group such as pyridine, pyrrole, imidazole, pyrrolidine, piperidine and derivatives thereof.
Another class of the polyamine N-oxides comprises the group of polyamine N-oxides wherein the nitrogen of the N-O group is attached to the R-group. Other suitable polyamine N-oxides are the polyamine oxides in which the N-O group is attached to the polymerizable unit. A preferred class of these polyamine N-oxides are the polyamine N-oxides having the general formula presented above wherein R is an aromatic, heterocyclic or an alicyclic group and the nitrogen of the N-O functional group is part of the R group. Examples of these classes are polyamine oxides wherein R is a heterocyclic compound such as pyridine, pyrrole, imidazole and derivatives thereof.
Another preferred class of polyamine N-oxides are the polyamine oxides having the general formula presented above wherein R is an aromatic, heterocyclic or alicyclic group and the nitrogen of the N-O functional group is attached to the R group(s). Examples of these classes are polyamine oxides wherein R groups can be aromatic such as phenyl. Any polymer backbone can be used as long as the amine oxide polymer formed is water-soluble and has dye transfer inhibiting properties. Examples of suitable polymeric backbones are polyvinyls, polyalkylenes, polyesters, polyethers, polyamide, polyimides, polyacrylates and mixtures thereof.
The amine N-oxide polymers useful in the detergent compositions of the present invention typically have a ratio of amine to the amine N-oxide of 10:1 to 1:1,000,000. However, the number of amine oxide groups present in the polyamine oxide polymer can be varied by appropriate copolymerization or by an appropriate degree of N-oxidation. Preferably, the ratio of amine to amine N-oxide is from 3:1 to 1:1000000. The polymers useful in the detergent compositions of the present invention actually encompass random or block copolymers where one monomer type is an amine N-oxide and the other monomer type is an N-oxide.
The amine oxide unit of the polyamine N-oxides preferably has a pKa 10, preferably pKa 7, more preferred pKa 6. The polyamine oxides can be obtained in almost any degree of polymerization. The degree of polymerization is not critical provided the material has the desired water-solubility and dye-suspending power. Typically, the average molecular weight is within the range of 500 to 1,000,000; more preferred 1,000 to 500,000; most preferred 5,000 to 100,000.
The most preferred polyamine N-oxide useful in the detergent compositions herein is poly(4-vinylpyridine-N-oxide) which has an average molecular weight of about 50,000 and an amine to amine N-oxide ratio of about 1:4. This preferred material can be abbreviated as "PVNO".
The polyamine N-oxides useful in the present invention can be synthesized by polymerizing the amine monomer and oxidizing the resulting polymer with a suitable oxidizing agent or the amine oxide monomer may itself be polymerized to obtain the desired polyamine N-oxide. Such reaction schemes are well known and within the scope of those persons skilled in the art.

Copolymers of N-vinylpyrrolidone and N-vinylimidazole

The detergent compositions of the present invention may also utilize a copolymer of N-vinylpyrrolidone and N-vinylimidazole (also abbreviated herein as "PVPVI"). It has been found that copolymers of N-vinylpyrrolidone and N-vinylimidazole can provide excellent dye transfer inhibiting performance when utilized in the compositions of this invention.
In a preferred embodiment, the copolymer of N-vinylpyrrolidone and N-vinylimidazole polymers has an average molecular weight range from 5,000 to 1,000,000, more preferably from 5,000 to 200,000. A highly preferred copolymer for use in detergent compositions according to the present invention has an average molecular weight range from 5,000 to 50,000, more preferably from 8,000 to 30,000 and, most preferably from 10,000 to 20,000. The average molecular weight range is determined by light scattering as described in Barth J. H. G. and Mays J. W. Chemical Analysis Vol 113. "Modem Methods of Polymer Characterization".
The copolymers of N-vinylpyrrolidone and N-vinylimidazole useful in the present invention can have a molar ratio of N-vinylimidazole to N-vinylpyrrolidone from 1:1 to 0.2:1, more preferably from 0.8:1 to 0.3:1, most preferably from 0.6:1 to 0.4:1. It should be understood that the copolymer of N-vinylpyrrolidone and N-vinylimidazole can be either linear or branched.

Polyethoxylated Urethanes

Polyethoxylated urethanes which are known for use as associative thickeners in latex compositions are condensation polymers of polyether polyols and isocyanates. U.S. Patents 4,079,028 and 4,155,892, describe in detail these polyurethane thickeners, which have been found useful as dye transfer agents when formulated into the present invention in combination with the modified polyamines described herein below.
The polyethoxylated urethane is prepared in a non-aqueous medium and is the reaction product of at least reactants (a) and (c), but the polymer optionally may include reactants (b) and (d) shown below:
(a) at least one water-soluble polyether alcohol containing one or more hydroxyl groups;
(b) at least one water-insoluble organic polyisocyanate;
(c) at least one monofunctional hydrophobic organic compound selected from a monofunctional active hydrogen compound and an organic monoisocyanate; and
(d) at least one polyhydric alcohol or polyhydric alcohol ether.
The polyether alcohol containing one or more functional hydroxyl groups reactant (a), is typically an adduct of an aliphatic, cycloaliphatic, or aromatic polyhydroxy compound such as an adduct of an alkylene oxide and a polyhydric alcohol or polyhydric alcohol ether, a hydroxyl-terminated prepolymer of such adduct and an organic polyisocyanate, or a mixture of such adducts with such prepolymers. Optionally, the polyether alcohol may contain just one hydroxyl group such as an alkyl polyethylene glycol, an alkylaryl polyethylene glycol, or a polycyclic alkyl polyethylene glycol where the alkyl group contains 1 to 20 carbon atoms.
A convenient source of the hydrophilic polyether polyol adducts is a polyalkylene glycol (also known as a polyoxyalkylene diol) such as polyethylene glycol, polypropylene glycol, or polybutylene glycol of about 200 to about 20,000 molecular weight. However, adducts of an alkylene oxide and a monofunctional reactant such as a fatty alcohol, a phenol or an amine, or adducts of an alkylene oxide and a difunctional reactant such as an alkanolamine (e.g., ethanolamine) are also useful. Such adducts are also known as diol ethers and alkanolamine ethers.
Suitable compounds providing polyether segments also include amino-terminated polyoxyethylenes of the formula NH₂(CH₂CH₂O)_xH where x has the value from about 10 to about 200.
Reactant (c), a monofunctional hydrophobic organic compound, reacts with one or both terminal functional groups of the reaction product of reactants (a) and (b). A monofunctional hydrophobic organic compound includes both a monofunctional active hydrogen compound and an organic monoisocyanate.
For the purposes of the present invention, the term "monofunctional active hydrogen compound" is defined as an organic compound having only one group which is reactive with isocyanate, such group containing an active hydrogen atom, where any other functional groups, if present, being substantially unreactive to isocyanate. Such compounds include monohydroxy compounds such as alcohols, alcohol ethers; and monoamines; as well as polyfunctional compounds providing the compound is only monofunctional to isocyanates. Representative of monofunctional active hydrogen compounds may include for example, the fatty (C₁-C₂₄) alcohols such as methanol, ethanol, octanol, decanol, dodecanol, tetradecanol, hexadecanol, and cyclohexanol; phenolics such as phenol, cresol, octylphenol, nonyl, and dodecyl phenol; alcohol ethers such as the monomethyl, monoethyl and monobutyl ethers of ethylene glycol, and the analogous ethers of diethylene glycol; alkyl and alkaryl polyether alcohols such as straight or branched (C₁-C₂₂) alkanol/ethylene oxide and alkyl phenol/ethylene oxide adducts.
Amino compounds may be used in place of all or a portion of the monohydroxy compounds as hydrophobic monofunctional active hydrogen compounds. Amino compounds include primary or secondary aliphatic, cycloaliphatic, or aromatic amines such as the straight or branched chain alkyl amines, or mixtures thereof, containing 1 to 20 carbon atoms in the alkyl group. Suitable amines include n- and t-octyl amine, n-dodecyl amines, C₁₂-C₁₄ or C₁₈-C₂₀ t-alkyl amine mixtures, and secondary amines such as N,N-dibenzyl amine. N,N-dicyclohexyl amine and N,N-diphenyl amine. The amino compounds may contain more than one active hydrogen atom provided that under normal reaction conditions it is only monofunctional towards an isocyanate group. A primary amine is an example of such a compound.
In addition to a monofunctional active hydrogen compound, reactant (c) may be a monoisocyanate. The monoisocyanate may include C₆-C₁₈ straight chain, branched chain, and cyclic isocyanates such as fro example, butyl isocyanate, octyl isocyanate, dodecyl isocyanate, octadecyl isocyanate, and cyclohexyl isocyanate. These isocyanates may be used singly or in mixtures of two or more thereof.
The organic polyisocyanate, reactant (b), include di- and triisocyanates, isocyanate-terminated adducts of such polyhydric alcohols and organic di- or triisocyanates, as well as isocyanate-terminated prepolymers of polyalkylene ether glycols and organic di- or triisocyanates. While it is preferred that reactant (b) be an organic polyisocyanate reactants containing one or more functional groups other than isocyanate are also suitable. The following are examples of monomers which can be used as reactant (b). These monomers may be used singly or in combination with one or more of the reactant (b) monomers:
1,6-hexamethylene diisocyanate (HDI)
1,6- and 2,4-tolylene diisocyanate (TDI)
4,4'- methylene diphenylisocyanate (MDI)
The polyisocyanates also include any polyfunctional isocyanate derived from reaction of any of the foregoing isocyanates and an active hydrogen compound having a functionality of at least two, such that at least one isocyanate group remains unreacted, Such isocyanates are equivalent to chain-extending an isocyanate terminated isocyanate/diol reaction product with a reactant containing at least two active hydrogen atoms in a manner well known in polyurethane synthesis.
The isocyanates may contain any number of carbon atoms effective to provide the required degree of hydrophobic character. Generally, 4 to 30 carbon atoms are sufficient, the selection depending on the proportion of the other hydrophobic groups and hydrophilic polyether in the product.
Reactant (d), a polyhydric alcohol or polyhydric alcohol ether, may be used to terminate isocyanate functionality or to link isocyanate-terminated reaction intermediates. The polyhydric alcohol or polyhydric alcohol ether may be aliphatic, cycloaliphatic or aromatic and may be used singly or in a mixtures of either type or mixtures of the two types.
by appropriate selection of reactants and reaction conditions, including proportions and molecular weights of reactants, a variety of polymeric products may be obtained that may be linear or complex in structure. In summary, the reaction products formed include the following:
i) reaction product of at least one water soluble polyether alcohol containing at least one functional hydroxyl group reactant (a), a water insoluble organic polyisocyanate reactant (b) and organic monoisocyanate reactant (c);
ii) a reaction product of the reaction (a), wherein the water soluble polyether alcohol contains at least one functional hydroxyl group, and the organic monoisocyanate reactant (c);
iii) a reaction product of the reactant (a), the reactant (b), the organic monoisocyanate reactant (c) and a reactant (d) selected from at least one polyhydric alcohol and polyhydric alcohol ether;
iv) a reaction product of the reactant (a), the water insoluble organic polyisocyanate reactant (b) containing two isocyanate groups, and a monofunctional active hydrogen containing compound; and
v) a reaction product of the reactant (a), the water insoluble organic polyisocyanate reactant (b) containing at least three isocyanate groups, and the monofunctional active hydrogen containing compound.
Polyethoxylated urethane useful as dye transfer inhibiting agents, generally will inhibit the transfer of dye during laundry process if:
i) the polyether segment has a molecular weight of at least 200;
ii) the polyethoxylated urethane contains at least one hydrophobic group and at least one water soluble polyether segment;
iii) the sum of the carbon atoms in the hydrophobic groups are at least 4; and
iv) the total molecular weight is at least 300 to 60,000.
The polymers are prepared according to techniques generally known for the synthesis of urethanes preferably such that no isocyanate remains unreacted. Water should be excluded from the reaction since it will consume isocyanate functionality.
If desired the reaction may be run in a solvent medium in order to reduce viscosity in those reactions leading to higher molecular weight products. Generally, a solvent is useful when molecular weights of 30,000 or higher are encountered. The solvent should be inert to isocyanate and capable of dissolving the polyoxyalkylene reactant and the urethane product at reaction temperature.
Order of addition, reactant proportions and other conditions of reaction such as the selection of the catalyst may be varied to control the geometry, molecular weight and other characteristics of the products, in accordance with will-known principles of polyurethane synthesis.

Acrylamide Containing Polymers

Water soluble or water dispersible acrylamide containing polymers, useful for preventing dye deposition, are known for use as thickeners, rheology modifiers, and dispersants.
Generally, the acrylamide containing polymers are prepared by a free radical initiated polymerization process in the presence of a chain transfer agent. The acrylamide containing polymers are formed from (i) at least one acrylamide of N-substituted acrylamide monomer, and optionally (ii) one or more vinyl monomers described as follows:
(i) an acrylamide or N-substituted acrylamide having the following structural formula:
wherein R¹ is hydrogen or C₁-C₆ alkyl, preferably hydrogen and methyl; R² and R³ are independently selected from the group consisting of hydrogen, methyl, ethyl, propyl, isopropyl, butyl, t-butyl, and isobutyl; or R² and R³ together with the nitrogen, to which R² and R³ are attached, to form three to seven membered monoaromatic nitrogen heterocycles.
ii) A vinyl monomer such as a C₁-C₆ alkyl (meth)acrylate, hydroxyalkyl (meth)acrylate, hydroxyaryl (meth)acrylate, alkoxyalkyl (meth)acrylate, polyalkoxyalkyl (meth)acrylate, styrene, vinyltoluene, alkyl vinyl ethers, such as butyl vinyl ether, amino monomers such as amino-substituted alkyl (meth)acrylates amino-alkyl vinyl ethers, and maleic anhydride. Also, vinyl monomers substituted with carboxylic acid may be used, such as for example, maleic acid, fumaric acid, itaconic acid, (meth)acrylic acid or the salts thereof.
For the purposes of the present invention the term "(meth)acrylate" is defined as meaning acrylic or methacrylic acid or ester. Salts of the carboxylic acid substituted vinyl monomer may be formed by partially or completely neutralizing the carboxylic acid substituted vinyl monomers with one or more common base alkali metal or alkaline earth metal, ammonia, low molecular weight amine, or low quaternary salt hydroxides.
The preparation of acrylamide polymers useful in this invention can be prepared by any number of techniques, well known to those skilled in the art. The preferred method is a radical initiated solution polymerization in water or a water and cosolvent mixtures. The co-solvent may be, for example, tert-butanol, monobutyl ether of ethylene glycol, or diethylene glycol. A less preferred method is precipitation polymerization in a polar organic solvent such as methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, isobutanol, tert-butanol, ethylene glycol monoalkyl ether, diethylene glycol ethers, acetone, methyl ethyl ketone, ethyl acetone, acetonitrile, dimethylsulfoxide, or tetrahydrofuran, as well as mixtures of these solvents with or without water. Some of the afore listed solvents function as efficient chain transfer agents and will lower the molecular weight of the product polymer.
Chain transfer agents may be added in an amount of from 0.5 to 12 percent by weight, based on the total weight of reactants added, to the polymerization process to lower the molecular weight of the polymer, or to add hydrophobic groups to the polymer to produce an associative thickener. Chain transfer agents useful for lowering the molecular weight may include for example mercaptans, such as ethyl mercaptan, n-propyl mercaptan, n-amyl mercaptan, hydroxy ethyl mercaptan, mercaptopropionic acid, and mercaptoacetic acid; halogen compounds such as carbon tetrachloride, tetrachloroethylene; some primary alkanols such as benzyl alcohol, ethylene glycol, and diethylene glycol; some secondary alcohols such as isopropanol; and bisulfite such as sodium bisulfate. Chain transfer agents useful in producing an associative thickener are water insoluble, and are preferably a long chain alkyl mercaptan, such as n-dodecyl mercaptan, t-dodecyl mercaptan, octyl mercaptan, tetradecyl mercaptan, and hexadecyl mercaptan. The total amount of chain transfer agent added to the polymerization process depends on the efficiency of the chain transfer agent. For example, if a less efficient chain transfer agent is used, such as sodium bisulfite, from 5 to 12 percent by weight of chain transfer agent may have to be used, where as if an efficient chain transfer agent is used, such as a mercaptan, only 0.5 to 5 weight percent chain transfer agent may have to be used.
The molecular weight range of these polymers are from 2,000 to 300,000. Preferably, the molecular weight is from 20,000 to 60,000. The acrylamide containing polymer is formed from 50 to 100 weight percent of the acrylamide or N-substituted acrylamide monomer (i), and 0 to 50 weight percent of the vinyl monomer (ii). Acrylamide containing polymers particularly useful in preventing dye deposition are polymers formed where the acrylamide or N-substituted acrylamide monomers is dimetylacrylamide, methylacrylamide, and acrylamide, and mixtures thereof, and the vinyl monomer is nonionic, such as for example the hydroxyalkyl (meth)acrylate or alkyl (meth)acrylate.

Polyamino Acids

Polyamino acids such as poly aspartic acid, polysuccinimide, and copolymers of polyamino acids are useful in combination with the modified polyamines as dye transfer inhibitors. Polyamino acids useful in the present invention can be prepared by techniques well know to those skilled in the art.

Modified Polyamines: Surface Modifiers Having Dye Transfer Inhibition Enhancement Benefits -

The modified polyamines are materials having surface modification properties. A result of this surprising property is the ability of these materials to act in conjunction with dye transfer inhibition agents to provided for significantly increased dye transfer inhibition. The dye transfer inhibition enhancing surface modification agents useful in the present invention are water-soluble or dispersible, bleach stable, modified polyamines comprising polyamine backbones that can be either linear or cyclic and comprise nitrogens totally or partially oxidized to N-oxides. The polyamine backbones can also comprise polyamine branching 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" is defined as replacing a backbone -NH hydrogen atom by an E unit (substitution), quaternizing a backbone nitrogen (quaternized) or oxidizing a backbone nitrogen to the N-oxide (oxidized) with the proviso that the polyamine comprises nitrogens totally or partially oxidized to N-oxides. The terms "modification" and "substitution" are used interchangeably when referring to the process of replacing a hydrogen atom attached to a backbone nitrogen with an E unit. Quaternization or oxidation may take place in some circumstances without substitution, but preferably substitution is accompanied by oxidation or quaternization of at least one backbone nitrogen.
The linear or non-cyclic polyamine backbones that comprise the cotton soil release agents have the general formula:
said backbones prior to subsequent modification, comprise primary, secondary and tertiary amine nitrogens connected by R "linking" units. The cyclic polyamine backbones comprising the cotton soil release agents have the general formula:
said backbones prior to subsequent modification, comprise primary, secondary and tertiary amine nitrogens connected by R "linking" units
For the purpose of the present invention, primary amine nitrogens comprising the backbone or branching chain once modified are defined as V or Z "terminal" units. For example, when a primary amine moiety, located at the end of the main polyamine backbone or branching chain having the structure H₂N-R]- is modified according to the present invention, it is thereafter defined as a V "terminal" unit, or simply a V unit. However, for the purposes of the present invention, some or all of the primary amine moieties can remain unmodified subject to the restrictions further described herein below. These unmodified primary amine moieties by virtue of their position in the backbone chain remain "terminal" units. Likewise, when a primary amine moiety, located at the end of the main polyamine backbone having the structure -NH₂ is modified according to the present invention, it is thereafter defined as a Z "terminal" unit, or simply a Z unit. This unit can remain unmodified subject to the restrictions further described herein below.
In a similar manner, secondary amine nitrogens comprising the backbone or branching chain once modified are defined as W "backbone" units. For example, when a secondary amine moiety, the major constituent of the backbones and branching chains, having the structure
is modified according to the present invention, it is thereafter defined as a W "backbone" unit, or simply a W unit. However, for the purposes of the present invention, some or all of the secondary amine moieties can remain unmodified. These unmodified secondary amine moieties by virtue of their position in the backbone chain remain "backbone" units.
In a further similar manner, tertiary amine nitrogens comprising the backbone or branching chain once modified are further referred to as Y "branching" units. For example, when a tertiary amine moiety, which is a chain branch point of either the polyamine backbone or other branching chains or rings, having the structure
is modified according to the present invention, it is thereafter defined as a Y "branching" unit, or simply a Y unit. However, for the purposes of the present invention, some or all or the tertiary amine moieties can remain unmodified. These unmodified tertiary amine moieties by virtue of their position in the backbone chain remain "branching" units. The R units associated with the V, W and Y unit nitrogens which serve to connect the polyamine nitrogens, are described herein below.
The final modified structure of the polyamines can be therefore represented by the general formula V_(n+1)W_mY_nZ for linear polyamine cotton soil release polymers and by the general formula V_(n-k+1)W_mY_nY'_kZ for cyclic polyamine cotton soil release polymers. For the case of polyamines comprising rings, a Y' unit of the formula
serves as a branch point for a backbone or branch ring. For every Y' unit there is a Y unit having the formula
that will form the connection point of the ring to the main polymer chain or branch.
In the case of non-cyclic polyamines, the ratio of the index n to the index m relates to the relative degree of branching. A fully non-branched linear modified polyamine according to the present invention has the formula VW_mZ 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. The value for m ranges from a minimum value of 4 to 400.
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 unmodified primary amine nitrogens are V or Z units, unmodified 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 substituted units having the structure:
b) quaternized units having the structure:
wherein X is a suitable counter ion providing charge balance; and
c) oxidized units having the structure:
Modified secondary amine moieties are defined as W "backbone" units having one of three forms:
a) simple substituted units having the structure:
b) quaternized units having the structure:
wherein X is a suitable counter ion providing charge balance; and
c) oxidized units having the structure:
Modified tertiary amine moieties are defined as Y "branching" units having one of three forms:
a) unmodified units having the structure:
b) quaternized units having the structure:
wherein X is a suitable counter ion providing charge balance; and
c) oxidized units having the structure:
Certain modified primary amine moieties are defined as Z "terminal" units having one of three forms:
a) simple substituted units having the structure:
b) quaternized units having the structure:
wherein X is a suitable counter ion providing charge balance; and
c) oxidized units having the structure:
When any position on a nitrogen is unsubstituted or unmodified, it is understood that hydrogen will substitute for E. For example, a primary amine unit comprising one E unit in the form of a hydroxyethyl moiety is a V terminal unit having the formula (HOCH₂CH₂)HN-.
For the purposes of the present invention there are two types of chain terminating units, the V and Z units. The Z "terminal" unit derives from a terminal primary amino moiety of the structure -NH₂. Non-cyclic polyamine backbones according to the present invention comprise only one Z unit. The Z "terminal" unit can be substituted with any of the E units described further herein below, except when the Z unit is modified to form an N-oxide. In the case where the Z unit nitrogen is oxidized to an N-oxide, the nitrogen must be modified and therefore E cannot be a hydrogen.
The polyamines comprise backbone R "linking" units that serve to connect the nitrogen atoms of the backbone. R units comprise units that for the purposes of the present invention are referred to as "hydrocarbyl R" units and "oxy R" units. The "hydrocarbyl" R units are C₂-C₁₂ alkylene, C₄-C₁₂ alkenylene, C₃-C₁₂ hydroxyalkylene wherein the hydroxyl moiety preferably may take any position on the R unit chain except the carbon atoms directly connected to the polyamine backbone nitrogens; C₄-C₁₂ dihydroxyalkylene wherein the hydroxyl moieties may occupy any two of the carbon atoms of the R unit chain preferably except those carbon atoms directly connected to the polyamine backbone nitrogens; C₈-C₁₂ dialkylarylene which for the purpose of the present invention preferably are arylene moieties having two alkyl substituent groups as part of the linking chain. For example, a dialkylarylene unit has the formula
although the unit need not be 1,4-substituted, but can also be 1,2 or 1,3 substituted C₂-C₁₂ alkylene, preferably ethylene, 1,2-propylene, and mixtures thereof, more preferably ethylene. The "oxy" R units comprise -(R¹O)_xR⁵(OR¹)_x-, -CH₂CH(OR²)CH₂O)_z(R¹O)_yR¹(OCH₂CH(OR²)CH₂)_w-, -CH₂CH(OR²)CH₂-, -(R¹O)_xR¹-, and mixtures thereof. Preferred R units are C₂-C₁₂ alkylene, C₃-C₁₂ hydroxyalkylene, C₄-C₁₂ dihydroxyalkylene, C₈-C₁₂ dialkylarylene, -(R¹O)_xR¹-, -CH₂CH(OR²)CH₂-, -(CH₂CH(OH)CH₂O)_z(R¹O)_yR¹(OCH₂CH-(OH)CH₂)_w-, -(R¹O)_xR⁵(OR¹)_x-, more preferred R units are C₂-C₁₂ alkylene, C₃-C₁₂ hydroxyalkylene, C₄-C₁₂ dihydroxyalkylene, -(R¹O)_xR¹-, -(R¹O)_xR⁵(OR¹)_x-, -(CH₂CH(OH)CH₂O)_z(R¹O)_yR¹(OCH₂CH-(OH)CH₂)_w-, and mixtures thereof, even more preferred R units are C₂-C₁₂ alkylene, C₃ hydroxyalkylene, and mixtures thereof, most preferred are C₂-C₆ alkylene. The most preferred backbones of the present invention comprise at least 50% R units that are ethylene.
R¹ units are C₂-C₆ alkylene, and mixtures thereof, preferably ethylene.
R² is hydrogen, and -(R¹O)_xB, preferably hydrogen.
R³ is C₁-C₁₈ alkyl, C₇-C₁₂ arylalkylene, C₇-C₁₂ alkyl substituted aryl, C₆-C₁₂ aryl, and mixtures thereof, preferably C₁-C₁₂ alkyl, C₇-C₁₂ arylalkylene, more preferably C₁-C₁₂ alkyl, most preferably methyl. R³ units serve as part of E units described herein below.
R⁴ is C₁-C₁₂ alkylene, C₄-C₁₂ alkenylene, C₈-C₁₂ arylalkylene, C₆-C₁₀ arylene, preferably C₁-C₁₀ alkylene, C₈-C₁₂ arylalkylene, more preferably C₂-C₈ alkylene, most preferably ethylene or butylene.
R⁵ is C₁-C₁₂ alkylene, C₃-C₁₂ hydroxyalkylene, C₄-C₁₂ dihydroxyalkylene, C₈-C₁₂ dialkylarylene, -C(O)-, -C(O)NHR⁶NHC(O)-, -C(O)(R⁴)_rC(O)-, -R¹(OR¹)-, -CH₂CH(OH)CH₂O(R¹O)_yR¹OCH₂CH(OH)CH₂-, -C(O)(R⁴)_rC(O)-, -CH₂CH(OH)CH₂-, R⁵ is preferably ethylene, -C(O)-, -C(O)NHR⁶NHC(O)-, -R¹(OR¹)-, -CH₂CH(OH)CH₂-, -CH₂CH(OH)CH₂O(R¹O)_yR¹OCH₂CH-(OH)CH₂-, more preferably -CH₂CH(OH)CH₂-.
R⁶ is C₂-C₁₂ alkylene or C₆-C₁₂ arylene.
The preferred "oxy" R units are further defined in terms of the R¹, R², and R⁵ units. Preferred "oxy" R units comprise the preferred R¹, R², and R⁵ units. The preferred cotton soil release agents comprise at least 50% R¹ units that are ethylene. Preferred R¹, R², and R⁵ units are combined with the "oxy" R units to yield the preferred "oxy" R units in the following manner.
i) Substituting more preferred R⁵ into -(CH₂CH₂O)_xR⁵(OCH₂CH₂)_x- yields -(CH₂CH₂O)_xCH₂CHOHCH₂(OCH₂CH₂)_x-.
ii) Substituting preferred R¹ and R² into -(CH₂CH(OR²)CH₂O)_z-(R¹O)_yR¹O(CH₂CH(OR²)CH₂)_w- yields -(CH₂CH(OH)CH₂O)_z-(CH₂CH₂O)_yCH₂CH₂O(CH₂CH(OH)CH₂)_w-.
iii) Substituting preferred R² into -CH₂CH(OR²)CH₂- yields -CH₂CH(OH)CH₂-.
E units are selected from the group consisting of hydrogen, C₁-C₂₂ alkyl, C₃-C₂₂ alkenyl, C₇-C₂₂ arylalkyl, C₂-C₂₂ hydroxyalkyl, -(CH₂)_pCO₂M, -(CH₂)_qSO₃M, -CH(CH₂CO₂M)CO₂M, -(CH₂)_pPO₃M, -(R¹O)_xB, -C(O)R³, preferably hydrogen, C₂-C₂₂ hydroxyalkylene, benzyl, C₁-C₂₂ alkylene, -(R¹O)_xB, -C(O)R³, -(CH₂)_pCO₂M, -(CH₂)_qSO₃M, -CH(CH₂CO₂M)CO₂M, more preferably C₁-C₂₂ alkylene, -(R¹O)_xB, -C(O)R³, -(CH₂)_pCO₂M, -(CH₂)_qSO₃M, -CH(CH₂CO₂M)CO₂M, most preferably C₁-C₂₂ alkylene, -(R¹O)_xB, and -C(O)R³. When no modification or substitution is made on a nitrogen then hydrogen atom will remain as the moiety representing E.
E units are preferably hydrogen, C₃-C₂₂ hydroxyalkyl, benzyl, C₁-C₂₂ alkyl, -(R¹O)_xB, -C(O)R³, -(CH₂)_pCO_2^-M⁺, -(CH₂)_qSO_3^-M⁺, -CH(CH₂CO₂M)-CO₂M more preferably hydrogen, C₁-C₂₂ alkyl, -(R¹O)_xB, -C(O)R³, most preferably -(R¹O)_xB;
E units preferably do not comprise hydrogen atom when the V, W or Z units are oxidized, preferably that is the nitrogens are N-oxides. For example, the backbone chain or branching chains do not comprise units of the following structure:
Additionally, E units preferably 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
or combinations thereof.
B is hydrogen, C₁-C₆ alkyl, -(CH₂)_qSO₃M, -(CH₂)_pCO₂M, -(CH₂)_q-(CHSO₃M)CH₂SO₃M, -(CH₂)_q(CHSO₂M)CH₂SO₃M, -(CH₂)_pPO₃M, -PO₃M, preferably hydrogen, -(CH₂)_qSO₃M, -(CH₂)_q(CHSO₃M)CH₂SO₃M, -(CH₂)_q-(CHSO₂M)CH₂SO₃M, more preferably hydrogen or -(CH₂)_qSO₃M.
M is hydrogen or a water soluble cation in sufficient amount to satisfy charge balance. For example, a sodium cation equally satisfies -(CH₂)_pCO₂M, and -(CH₂)_qSO₃M, thereby resulting in -(CH₂)_pCO₂Na, and -(CH₂)_qSO₃Na moieties. More than one monovalent cation, (sodium, potassium) can be combined to satisfy the required chemical charge balance. However, more than one anionic group may be charge balanced by a divalent cation, or more than one mono-valent cation may be necessary to satisfy the charge requirements of a poly-anionic radical. For example, a -(CH₂)_pPO₃M moiety substituted with sodium atoms has the formula -(CH₂)_pPO₃Na₃. Divalent cations such as calcium (Ca²⁺) or magnesium (Mg²⁺) may be substituted for or combined with other suitable mono-valent water soluble cations. Preferred cations are sodium and potassium, more preferred is sodium.
X is a water soluble anion such as chlorine (Cl^-), bromine (Br^-) and iodine (I^-) or X can be any negatively charged radical such as sulfate (SO₄ ^2-) 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; k has a value less than n, typically the value of k is less than 20; m has the value from 4 to 400, n has the value from 0 to 200; m + n preferably has the value of at least 5.
The preferred dye transfer inhibition enhancers comprise polyamine 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 dye transfer inhibition enhancers which comprise no "oxy" R units comprise polyamine backbones wherein less than 50% of the R groups comprise more than 3 carbon atoms. For example, ethylene, 1,2-propylene, and 1,3-propylene comprise 3 or less carbon atoms and are the preferred "hydrocarbyl" R units. That is when backbone R units are C₂-C₁₂ alkylene, preferred is C₂-C₃ alkylene, most preferred is ethylene.
The dye transfer inhibition enhancers 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 polyamines that comprise other extraneous units comprising the polymer backbone which are present due to an artifact of the chosen method of chemical synthesis. For example, it is known to those skilled in the art that ethanolamine may be used as an "initiator" in the synthesis of polyethyleneimines, therefore a sample of polyethyleneimine that comprises one hydroxyethyl moiety resulting from the polymerization "initiator" would be considered to comprise a homogeneous polyamine backbone for the purposes of the present invention. A polyamine backbone comprising all ethylene R units wherein no branching Y units are present is a homogeneous backbone. A polyamine backbone comprising all ethylene R units is a homogeneous backbone regardless of the degree of branching or the number of cyclic branches present.
For the purposes of the present invention the term "non-homogeneous polymer backbone" refers to polyamine backbones that are a composite of various R unit lengths and R unit types. For example, a non-homogeneous backbone comprises R units that are a mixture of ethylene and 1,2-propylene units. For the purposes of the present invention a mixture of "hydrocarbyl" and "oxy" R units is not necessary to provide a non-homogeneous backbone. The proper manipulation of these "R unit chain lengths" provides the formulator with the ability to modify the solubility and fabric substantivity of the cotton soil release agents.
Preferred dye transfer inhibition enhancers 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 formulator. The degree of ethoxylation is also determined by the specific requirements of the formulator.
The preferred polyamines that comprise the backbone of the compounds are generally polyalkyleneamines (PAA's), polyalkyleneimines (PAI's), preferably polyethyleneamine (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 common polyalkyleneamine (PAA) is tetrabutylenepentamine. PEA's are obtained by reactions involving ammonia and ethylene dichloride, followed by fractional distillation. The common PEA's obtained are triethylenetetramine (TETA) and teraethylenepentamine (TEPA). Above the pentamines, i.e., the hexamines, heptamines, octamines and possibly nonamines, the cogenerically derived mixture does not appear to separate by distillation and can include other materials such as cyclic amines and particularly piperazines. 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 preparation of PEA's.
Preferred amine polymer backbones comprise R units that are C₂ alkylene (ethylene) units, also known as polyethylenimines (PEI's). Preferred PEI's have at least moderate branching, that is the ratio of m to n is less than 4:1, however PEI's having a ratio of m to n of about 2:1 are most preferred. Preferred backbones, prior to modification have the general formula:
wherein m and n are the same as defined herein above. PEI'S, prior to modification, 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 preparation. Each hydrogen atom attached to each nitrogen atom of the polyamine backbone chain represents a potential site for subsequent substitution, quatemization or oxidation.
These polyamines can be prepared, 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, Esselmann et al., issued July 16, 1940; U.S. Patent 2,806,839, Crowther, issued September 17, 1957; and U.S. Patent 2,553,696, Wilson, issued May 21, 1951.
Examples of dye transfer inhibition enhancers comprising PEI's, are illustrated in Formulas I - IV:
Formula I depicts a dye transfer inhibition enhancement agent comprising a PEI backbone wherein all substitutable nitrogens are modified by replacement of hydrogen with a polyoxyalkyleneoxy unit, -(CH₂CH₂O)₇H, having the formula
This is an example of a cotton soil release polymer that is fully modified by one type of moiety.
Formula II depicts a dye transfer inhibition enhancement agent comprising a PEI backbone wherein all substitutable primary amine nitrogens are modified by replacement 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 dye transfer inhibition enhancement agent having the formula
Formula III depicts a dye transfer inhibition enhancement agent comprising a PEI backbone wherein all backbone hydrogen atoms are substituted and some backbone amine units are quaternized. The substituents are polyoxyalkyleneoxy units, -(CH₂CH₂O)₇H, or methyl groups. The modified PEI dye transfer inhibition enhancement agent has the formula
Formula IV depicts a dye transfer inhibition enhancement agent comprising a PEI backbone wherein the backbone nitrogens are modified by substitution (i.e. by -(CH₂CH₂O)₇H or methyl), quaternized, oxidized to N-oxides or combinations thereof. The resulting dye transfer inhibition enhancement agent has the formula
In the above examples, not all nitrogens of a unit class comprise the same modification. The present invention allows the formulator to have a portion of the secondary amine nitrogens ethoxylated while having other secondary amine nitrogens oxidized to N-oxides. This also applies to the primary amine nitrogens, in that the formulator may choose to modify all or a portion of the primary amine nitrogens with one or more substituents prior to oxidation or quaternization. Any possible combination of E groups can be substituted on the primary and secondary amine nitrogens, except for the restrictions described herein above.

METHOD OF USE

Present invention relates to methods of providing dye transfer inhibition benefits to dyed or colored fabric. The method comprises the step of contacting said dyed or colored fabric with a water-soluble or dispersible, bleach stable, modified polyamine fabric surface modifying agent, said agent comprising a polyamine backbone corresponding to the formula:
having a modified polyamine formula V_(n+1)W_mY_nZ or a polyamine backbone corresponding to the formula:
having a modified polyamine formula V_(n-k+1)W_mY_nY'_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 terminal units having the formula:
ii) W units are backbone units having the formula:
iii) Y units are branching units having the formula:
and
iv) Z units are terminal units having the formula:

₂

₁₂

₄

₁₂

₃

₁₂

₄

₁₂

₈

₁₂

¹

_x

¹

_x

⁵

¹

_x

₂

²

₂

_z

¹

_y

¹

₂

²

₂

_w

⁴

_r

₂

²

₂

¹

₂

₆

²

¹

_x

³

₁

₁₈

₇

₁₂

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₁₂

₆

₁₂

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₁

₁₂

₄

₁₂

₈

₁₂

₆

₁₀

⁵

₁

₁₂

₃

₁₂

₄

₁₂

₈

₁₂

⁶

¹

⁴

_r

₂

¹

_y

¹

₂

⁶

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₁₂

₆

₁₂

₁

₂₂

₃

₂₂

₇

₂₂

₂

₂₂

₂

_p

₂

_q

₃

₂

_p

₃

¹

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³

₁

₆

₂

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₂

_p

₂

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₂

₃

₂

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₂

₃

₂

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₃

The methods of the present invention are suitable for use when the fabric being treated for soil release is also in need of bleaching. Compositions comprising bleaching agents commonly used to clean white fabrics are compatible with the fabric surface modifying agents.
The present invention also provides a method for laundering colored fabrics with little or no dye transfer taking place. Such a method employs contacting these fabrics with an aqueous washing solution formed from an effective amount of the detergent compositions hereinbefore described. Contacting of fabrics with washing solution will generally occur under conditions of agitation.

Detersive surfactants

The detersive surfactants suitable for use in the present invention are cationic, anionic, nonionic, ampholytic, zwitterionic, and mixtures thereof, further described herein below. The laundry detergent composition may be in any suitable form, for example, high density liquids, light liquids or other pourable forms in addition to granules or laundry bars. The cotton soil release polymers can be formulated into any detersive matrix chosen by the formulator.
The laundry detergent compositions according to the present invention may additionally comprise at least about 0.01%, preferably at least about 0.1%, more preferably at least about 1% by weight, of the following detersive surfactants. Nonlimiting examples of surfactants useful herein typically at levels from 1% to 55%, by weight, include the conventional C₁₁-C₁₈ alkyl benzene sulfonates ("LAS") and primary, branched-chain and random C₁₀-C₂₀ alkyl sulfates ("AS"), the C₁₀-C₁₈ secondary (2,3) alkyl sulfates of the formula CH₃(CH₂)_x(CHOSO₃ ^-M⁺) CH₃ and CH₃ (CH₂)_y(CHOSO₃ ^-M⁺) CH₂CH₃ where x and (y + 1) are integers of at least 7, preferably at least 9, and M is a water-solubilizing cation, especially sodium, unsaturated sulfates such as oleyl sulfate, the C₁₀-C₁₈ alkyl alkoxy sulfates ("AE_xS"; especially EO 1-7 ethoxy sulfates), C₁₀-C₁₈ alkyl alkoxy carboxylates (especially the EO 1-5 ethoxycarboxylates), the C_10-18 glycerol ethers, the C₁₀-C₁₈ alkyl polyglycosides and their corresponding sulfated polyglycosides, and C₁₂-C₁₈ alpha-sulfonated fatty acid esters. If desired, the conventional nonionic and amphoteric surfactants such as the C₁₂-C₁₈ alkyl ethoxylates ("AE") including the so-called narrow peaked alkyl ethoxylates and C₆-C₁₂ alkyl phenol alkoxylates (especially ethoxylates and mixed ethoxy/propoxy), C₁₂-C₁₈ betaines and sulfobetaines ("sultaines"), C₁₀-C₁₈ amine oxides, can also be included in the overall compositions. The C₁₀-C₁₈ N-alkyl polyhydroxy fatty acid amides can also be used. Typical examples include the C₁₂-C₁₈ N-methylglucamides. See WO 9,206,154. Other sugar-derived surfactants include the N-alkoxy polyhydroxy fatty acid amides, such as C₁₀-C₁₈ N-(3-methoxypropyl) glucamide. The N-propyl through N-hexyl C₁₂-C₁₈ glucamides can be used for low sudsing. C₁₀-C₂₀ conventional soaps may also be used. If high sudsing is desired, the branched-chain C₁₀-C₁₆ soaps may be used. Mixtures of anionic and nonionic surfactants are especially useful. Other conventional useful surfactants are listed in standard texts.

Anionic Surfactant Component

The detergent compositions herein preferably comprise at least 5% by weight, of an anionic surfactant, preferably from 5% to 60% by weight of an anionic surfactant component. More preferably such compositions comprise from 10% to 40% by weight of this anionic surfactant component.
A substantial portion, i.e., at least 50%, and more preferably at least 75%, of the anionic surfactant component will comprise ethoxylated alkyl sulfate surfactants. Such ethoxylated alkyl sulfates are those which correspond to the formula: R²-O-(C₂H₄O)_n-SO₃M wherein R² is a C₁₀-C₂₂ alkyl group, n is from 1 to 20, and M is a salt-forming cation. Preferably, R² is C₁₂-C₁₈ alkyl, n is from 1 to 15, and M is sodium, potassium, ammonium, alkylammonium or alkanolammonium. Most preferably, R² is C₁₂-C₁₆ n is from 1 to 6 and M is sodium. These materials, also known as alkyl ether sulfates, can provide especially desirable dye transfer inhibition benefits when used in combination with the specific polymeric dye transfer inhibiting agents hereinafter described.
The alkyl ether sulfates will generally be used in the form of mixtures comprising varying R₂ chain lengths and varying degrees of ethoxylation. Frequently such mixtures will inevitably also contain some unethoxylated alkyl sulfate materials, i.e. surfactants of the above ethoxylated alkyl sulfate formula wherein n is equal to 0. Such unethoxylated alkyl sulfate anionic surfactants tend to be less effective than are ethoxylated alkyl sulfates at inhibiting dye transfer in the context of the compositions of the present invention. Accordingly, it is important that anionic surfactant component herein contain no more than 50% by weight of such component of unethoxylated alkyl sulfate materials. Preferably no more than 25% by weight of the anionic surfactant component will comprise unethoxylated alkyl sulfates.
In addition to the essentially utilized ethoxylated alkyl sulfate surfactants, the anionic surfactant component of the compositions herein may also contain additional optional anionic surfactants so long as such additional optional materials are compatible with other composition components and do not substantially adversely effect composition performance, e.g., dye transfer inhibition or composition stability. Optional anionic surfactants which may be employed include in general the carboxylate-type anionics. Carboxylate-type anionics include fatty acid, e.g. C₁₀-C₁₈, soaps, the C₁₀-C₁₈ alkyl alkoxy carboxylates (especially the EO 1 to 5 ethoxycarboxylates) and the C₁₀-C₁₈ sarcosinates, especially oleoyl sarcosinate.
One common type of anionic surfactant which should not be utilized in the anionic surfactant component of the compositions herein comprises the sulfonated anionics which are alkyl benzene sulfonates. It has been found that non-bleach activating sulfonated anionic surfactants like linear alkyl benzene sulfonate (LAS) tend to interfere with the effectiveness of the polymeric dye transfer inhibiting agents used herein to reduce transfer of dyes between fabrics during fabric laundering operations.
Accordingly, the anionic surfactant component of the detergent compositions herein should be substantially free of such alkyl benzene sulfonate anionic surfactant materials.

Nonionic Surfactant Component

The detergent compositions herein also preferably comprise from 5% by weight of a non-ionic surfactant, preferably from 1% to 20% by weight of an nonionic surfactant component. More preferably such compositions will comprise from about 2% to 10% by weight of this nonionic surfactant component.
The nonionic surfactant component essentially comprises one, and preferably both, of two specific types of nonionic surfactant materials. These are polyhydroxy fatty acid amides and alcohol ethoxylates.

1) Polyhydroxy Fatty Acid Amides

Further preferred nonionic surfactants are the polyhydroxy fatty acid amides having the formula:
wherein R⁷ is C₅-C₃₁ alkyl, preferably straight chain C₇-C₁₉ alkyl or alkenyl, more preferably straight chain C₉-C₁₇ alkyl or alkenyl, most preferably straight chain C₁₁-C₁₅ alkyl or alkenyl, or mixtures thereof; R⁸ is selected from the group consisting of hydrogen, C₁-C₄ alkyl, C₁-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 connected to the chain, or an alkoxylated derivative thereof; preferred 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 intended to exclude other suitable raw materials. Q is more preferably selected from the group consisting of -CH₂(CHOH)_nCH₂OH,-CH(CH₂OH)(CHOH)_n-1CH₂OH, -CH₂(CHOH)₂-(CHOR')(CHOH)CH₂OH, and alkoxylated derivatives thereof, wherein n is an integer from 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)₄CH₂OH.
R⁷CO-N< can be, for example, cocamide, stearamide, oleamide, lauramide, myristamide, capricamide, palmitamide, tallowamide.
R⁸ can be, for example, methyl, ethyl, propyl, isopropyl, butyl, 2-hydroxy ethyl, or 2-hydroxy propyl.
Q can be 1-deoxyglucityl, 2-deoxyfructityl, 1-deoxymaltityl, 1-deoxylactityl, 1-deoxygalactityl, 1-deoxymannityl, 1-deoxymaltotriotityl.
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 C₁₁-C₁₃), R⁸, is methyl and Q is 1-deoxyglucityl.
Processes for making polyhydroxy fatty acid amides are known and can be found, for example, in Wilson, U.S. Patent 2,965,576 and Schwartz, U.S. Patent 2,703,798. The materials themselves and their preparation are also described in greater detail in Honsa, U.S. Patent 5,174,937, Issued December 26, 1992, which patent is also incorporated herein by reference.
When polyhydroxy fatty acid amide nonionic is used in the nonionic surfactant component of the detergent compositions herein, it will generally be present to the extent of from 1% to 20% by weight of the composition. More preferably, polyhydroxy fatty acid amide nonionic can comprise from 2% to 10% by weight of the compositions herein.

2) Alcohol Ethoxylates

Another suitable component of the nonionic surfactant used in the compositions herein comprises an ethoxylated fatty alcohol nonionic surfactant. Such materials are those which correspond to the general formula: R¹(C₂H₄O)_nOH wherein R¹ is a C₈ - C₁₆ alkyl group or a C₆ - C₁₂ alkylphenol group and n ranges from about 1 to 80. Preferably R¹ is an alkyl group, which may be primary or secondary, that contains from about 9 to 15 carbon atoms, more preferably from 10 to 14 carbon atoms. Preferably the ethoxylated fatty alcohols will contain from 2 to 12 ethylene oxide moieties per molecule, more preferably from 3 to 10 ethylene oxide moieties per molecule.
The ethoxylated fatty alcohol nonionic surfactant will frequently have a hydrophilic-lipophilic balance (HLB) which ranges from 3 to 17. More preferably, the HLB of this material will range from 6 to 15, most preferably from 10 to 15.
Examples of fatty alcohol ethoxylates useful as the essential liquid nonionic surfactant in the compositions herein will include those which are made from alcohols of 12 to 15 carbon atoms and which contain 7 moles of ethylene oxide. Such materials have been commercially marketed under the trade names Neodol 25-7 and Neodol 23-6.5 by Shell Chemical Company. Other useful Neodols include Neodol 1-5, an ethoxylated fatty alcohol averaging 11 carbon atoms in its alkyl chain with 5 moles of ethylene oxide; Neodol 23-9, an ethoxylated primary C12 - C13 alcohol having 9 moles of ethylene oxide and Neodol 91-10, an ethoxylated C₉ - C₁₁ primary alcohol having about 10 moles of ethylene oxide. Alcohol ethoxylates of this type have also been marketed by Shell Chemical Company under the Dobanol tradename. Dobanol 91-5 is an ethoxylated C₉-C₁₁ fatty alcohol with an average of 5 moles ethylene oxide and Dobanol 25-7 is an ethoxylated C₁₂-C₁₅ fatty alcohol with an average of 7 moles of ethylene oxide per mole of fatty alcohol.
Other examples of suitable ethoxylated alcohol nonionic surfactants include Tergitol 15-S-7 and Tergitol 15-S-9 both of which are linear secondary alcohol ethoxylates that have been commercially marketed by Union Carbide Corporation. The former is a mixed ethoxylation product of C₁₁ to C₁₅ linear secondary alkanol with 7 moles of ethylene oxide and the latter is a similar product but with 9 moles of ethylene oxide being reacted.
Other types of alcohol ethoxylate nonionics useful in the present compositions are higher molecular weight nonionics, such as Neodol 45-11, which are similar ethylene oxide condensation products of higher fatty alcohols, with the higher fatty alcohol being of 14-15 carbon atoms and the number of ethylene oxide groups per mole being about 11. Such products have also been commercially marketed by Shell Chemical Company.
When alcohol ethoxylate nonionic is used in the nonionic surfactant component of the detergent compositions herein, it will generally be present to the extent of from 0.5% to 10% by weight of the composition. More preferably, alcohol ethoxylate nonionic will comprise from 1% to 5% by weight of the compositions herein.

Non-cotton Soil Release Agent

Known polymeric soil release agents, hereinafter "SRA", can optionally be employed in the present detergent compositions. If utilized, SRA's will generally constitute from 0.01% to 10.0%, typically from 0.1% to 5%, preferably from 0.2% to 3.0% by weight, of the compositions.
Preferred SRA's typically have hydrophilic segments to hydrophilize the surface of hydrophobic fibers such as polyester and nylon, and hydrophobic segments to deposit upon hydrophobic fibers and remain adhered thereto through completion of washing and rinsing cycles, thereby serving as an anchor for the hydrophilic segments. This can enable stains occurring subsequent to treatment with the SRA to be more easily cleaned in later washing procedures.
SRA's can include a variety of charged, e.g., anionic or even cationic species, see U.S. 4,956,447, issued September 11, 1990 to Gosselink, et al., as well as noncharged monomer units, and their structures may be linear, branched or even star-shaped. They may include capping moieties which are especially effective in controlling molecular weight or altering the physical or surface-active properties. Structures and charge distributions may be tailored for application to different fiber or textile types and for varied detergent or detergent additive products.
Preferred SRA's include oligomeric terephthalate esters, typically prepared by processes involving at least one transesterification/oligomerization, often with a metal catalyst such as a titanium(IV) alkoxide. Such esters may be made using additional monomers capable of being incorporated into the ester structure through one, two, three, four or more positions, without, of course, forming a densely crosslinked overall structure.
Other SRA's include the nonionic end-capped 1,2-propylene/polyoxyethylene terephthalate polyesters of U.S. 4,711,730, December 8, 1987 to Gosselink et al., for example those produced by transesterification/oligomerization of poly(ethyleneglycol) methyl ether, DMT, PG and poly(ethyleneglycol) ("PEG"). Other examples of SRA's include: the partly- and fully- anionic-end-capped oligomeric esters of U.S. 4,721,580, January 26, 1988 to Gosselink, such as oligomers from ethylene glycol ("EG"), PG, DMT and Na-3,6-dioxa-8-hydroxyoctanesulfonate; and the anionic, especially sulfoaroyl, end-capped terephthalate esters of U.S. 4,877,896, October 31, 1989 to Maldonado, the latter being typical of SRA's useful in both laundry and fabric conditioning products, an example being an ester composition made from m-sulfobenzoic acid monosodium salt, PG and DMT, optionally but preferably further comprising added PEG, e.g., PEG 3400.
SRA's also include: simple copolymeric blocks of ethylene terephthalate or propylene terephthalate with polyethylene oxide or polypropylene oxide terephthalate, see U.S. 3,959,230 to Hays, May 25, 1976 and U.S. 3,893,929 to Basadur, July 8, 1975; cellulosic derivatives such as the hydroxyether cellulosic polymers available as METHOCEL from Dow; the C₁-C₄ alkyl celluloses and C₄ hydroxyalkyl celluloses, see U.S. 4,000,093, December 28, 1976 to Nicol, et al.; and the methyl cellulose ethers having an average degree of substitution (methyl) per anhydroglucose unit from about 1.6 to about 2.3 and a solution viscosity of from about 80 to about 120 centipoise measured at 20°C as a 2% aqueous solution. Such materials are available as METOLOSE SM100 and METOLOSE SM200, which are the trade names of methyl cellulose ethers manufactured by Shin-etsu Kagaku Kogyo KK.
Suitable SRA's characterised by poly(vinyl ester) hydrophobe segments include graft copolymers of poly(vinyl ester), e.g., C₁-C₆ vinyl esters, preferably poly(vinyl acetate), grafted onto polyalkylene oxide backbones. See European Patent Application 0 219 048, published April 22, 1987 by Kud, et al. Commercially available examples include SOKALAN SRA's such as SOKALAN HP-22, available from BASF, Germany. Other SRA's are polyesters with repeat units containing 10-15% by weight of ethylene terephthalate together with 80-90% by weight of polyoxyethylene terephthalate derived from a polyoxyethylene glycol of average molecular weight 300-5,000. Commercial examples include ZELCON 5126 from Dupont and MILEASE T from ICI.
Another preferred SRA is an oligomer having empirical formula (CAP)₂(EG/PG)₅(T)₅(SIP)₁ which comprises terephthaloyl (T), sulfoisophthaloyl (SIP), oxyethyleneoxy and oxy-1,2-propylene (EG/PG) units and which is preferably terminated with end-caps (CAP), preferably modified isethionates, as in an oligomer comprising one sulfoisophthaloyl unit, 5 terephthaloyl units, oxyethyleneoxy and oxy-1,2-propyleneoxy units in a defined ratio, preferably about 0.5:1 to about 10:1, and two end-cap units derived from sodium 2-(2-hydroxyethoxy)-ethanesulfonate. Said SRA preferably further comprises from 0.5% to 20%, by weight of the oligomer, of a crystallinity-reducing stabilizer, for example an anionic surfactant such as linear sodium dodecylbenzenesulfonate or a member selected from xylene-, cumene-, and toluenesulfonates or mixtures thereof, these stabilizers or modifiers being introduced into the synthesis vessel, all as taught in U.S. 5,415,807, Gosselink, Pan, Kellett and Hall, issued May 16, 1995. Suitable monomers for the above SRA include Na-2-(2-hydroxyethoxy)-ethanesulfonate, DMT, Na-dimethyl-5-sulfoisophthalate, EG and PG.
Additional classes of SRA's include: (I) nonionic terephthalates using diisocyanate coupling agents to link polymeric ester structures, see U.S. 4,201,824, Violland et al. and U.S. 4,240,918 Lagasse et al.; and (II) SRA's with carboxylate terminal groups made by adding trimellitic anhydride to known SRA's to convert terminal hydroxyl groups to trimellitate esters. With the proper selection of catalyst, the trimellitic anhydride forms linkages to the terminals of the polymer through an ester of the isolated carboxylic acid of trimellitic anhydride rather than by opening of the anhydride linkage. Either nonionic or anionic SRA's may be used as starting materials as long as they have hydroxyl terminal groups which may be esterified. See U.S. 4,525,524 Tung et al.. Other classes include: (III) anionic terephthalate-based SRA's of the urethane-linked variety, see U.S. 4,201,824, Violland et al.; (IV) poly(vinyl caprolactam) and related co-polymers with monomers such as vinyl pyrrolidone and/or dimethylaminoethyl methacrylate, including both nonionic and cationic polymers, see U.S. 4,579,681, Ruppert et al.; (V) graft copolymers, in addition to the SOKALAN types from BASF, made by grafting acrylic monomers onto sulfonated polyesters. These SRA's assertedly have soil release and anti-redeposition activity similar to known cellulose ethers: see EP 279,134 A, 1988, to Rhone-Poulenc Chemie. Still other classes include: (VI) grafts of vinyl monomers such as acrylic acid and vinyl acetate onto proteins such as caseins, see EP 457,205 A to BASF (1991); and (VII) polyester-polyamide SRA's prepared by condensing adipic acid, caprolactam, and polyethylene glycol, especially for treating polyamide fabrics, see Bevan et al., DE 2,335,044 to Unilever N. V., 1974. Other useful SRA's are described in U.S. Patents 4,240,918, 4,787,989 and 4,525,524.

Preferred Non-cotton Soil Release Agent

Suitable for use in the laundry detergent compositions of the present invention are the following preferred soil release polymers comprising:
a) a backbone comprising:
i) at least one moiety having the formula:
ii) at least one moiety having the formula:
wherein R⁹ is C₂-C₆ linear alkylene, C₃-C₆ branched alkylene, C₅-C₇ cyclic alkylene, and mixtures thereof; R¹⁰ is independently selected from hydrogen or -L-SO₃-M⁺; wherein L is a side chain moiety selected from the group consisting of alkylene, oxyalkylene, alkyleneoxyalkylene, arylene, oxyarylene, alkyleneoxyarylene, poly(oxyalkylene), oxyalkyleneoxyarylene, poly(oxyalkylene)oxyarlyene, alkylenepoly(oxyalkylene),and mixtures thereof; M is hydrogen or a salt forming cation; i has the value of 0 or 1;
iii) at least one trifunctional, ester-forming, branching moiety;
iv) at least one 1,2-oxyalkyleneoxy moiety; and
b) one or more capping units comprising:
i) ethoxylated or propoxylated hydroxyethanesulfonate or ethoxylated or propoxylated hydroxypropanesulfonate units of the formula (MO₃S)(CH₂)_m(R¹¹O)_n-, where M is a salt forming cation such as sodium or tetralkylammonium, R¹¹ is ethylene or propylene or a mixture thereof, m is 0 or 1, and n is from 1 to 20;
ii) sulfoaroyl units of the formula -(O)C(C₆H₄)(SO₃-M⁺), wherein M is a salt forming cation;
iii) modified poly(oxyethylene)oxy monoalkyl ether units of the formula R¹²O(CH₂CH₂O)_k-, wherein R¹² contains from 1 to 4 carbon atoms and k is from 3 to 100; and
iv) ethoxylated or propoxylated phenolsulfonate end-capping units of the formula MO₃S(C₆H₄)(OR¹³)_nO-, wherein n is from 1 to 20; M is a salt-forming cation; and R¹³ is ethylene, propylene and mixtures thereof.
This type of preferred soil release polymer may be described as having the formula [(Cap)(R⁴)_t][(A-R¹-A-R²)_u(A-R¹-A-R³)_v(A-R¹-A-R⁵)_w
-A-R¹-A-][(R⁴)_t(Cap)] wherein A is a carboxy linking moiety having the formula
R¹ is arylene, preferably a 1,4-phenylene moiety having the formula
such that when A units and R¹ units are taken together in the formula A-R¹-A they form a terephthalate unit having the formula
R² units are ethyleneoxy or 1,2-propyleneoxy. R² units are combined with terephthalate moieties to form (A-R¹-A-R²) units having the formula
wherein R' and R" are either hydrogen or methyl provided that R' and R" are not both methyl at the same time.
R³ units are trifunctional, ester-forming, branching moieties having the formula
Preferably R³ units comprise a glycerol moiety which is placed into the soil release polymer backbone to provide a branch point. When R³ units are combined with terephthalate moieties to form units of the polymer backbone, for example, (A-R¹-A-R³)-A-R¹-A units, these units have the formula
or the formula
wherein one terephthalate residue is taken to be a part of the (A-R¹-A-R³) unit while the second terephthalate comprises a part of another backbone unit, such as a (A-R¹-A-R²) unit, a (A-R¹-A-R⁵) unit, a -A-R¹-A-[(R⁴)_t(Cap)] unit or a second (A-R¹-A-R³) unit. The third functional group, which is the beginning of the branching chain, is also typically bonded to a terephthalate residue also a part of a (A-R¹-A-R²) unit, a (A-R¹-A-R⁵) unit, a -A-R¹-A-[(R⁴)_t(Cap)] unit or another (A-R¹-A-R³) unit.
An example of a section of a soil release polymer containing a "trifunctional, ester-forming, branching moiety" R³ unit which comprises a glycerol unit, has the formula
R⁴ units are R², R³ or R⁵ units.
R⁵ units are units having the formula
wherein R⁹ is C₂-C₆ linear alkylene, C₃-C₆ branched alkylene, and mixtures thereof; preferably R¹⁰ is independently selected from hydrogen or -L-SO₃ ^-M⁺; wherein L is a side chain moiety selected from the group consisting of alkylene, oxyalkylene, alkyleneoxyalkylene, arylene, oxyarylene, alkyleneoxyarylene, poly(oxyalkylene), oxyalkyleneoxyarylene, poly(oxyalkylene)oxyarlyene, alkylenepoly(oxyalkylene),and mixtures thereof; M is hydrogen or a salt forming cation; i has the value of 0 or 1;
Each carbon atom of the R⁹ units is substituted by R¹⁰ units that are independently selected from hydrogen or -L-SO₃ ^-M⁺, provided no more than one -L-SO₃ ^-M⁺ units is attached to an R⁹ unit; L is a side chain connecting moiety selected from the group consisting of alkylene, oxyalkylene, alkyleneoxyalkylene, arylene, oxyarylene, alkyleneoxyarylene, poly(oxyalkylene), oxyalkyleneoxyarylene, poly(oxyalkylene)oxyarlyene, alkylenepoly(oxyalkylene),and mixtures thereof.
M is a cationic moiety selected from the group consisting of lithium, sodium, potassium, calcium, and magnesium, preferably sodium and potassium.
Preferred R⁵ moieties are essentially R¹⁰ substituted C₂-C₆ alkylene chains. The R⁵ units comprise either one C₂-C₆ alkylene chain substituted by one or more independently selected R¹⁰ moieties (preferred) or two C₂-C₆ alkylene chains said alkylene chains joined by an ether oxygen linkage, each alkylene chain substituted by one or more independently selected R¹⁰ moieties, that is R⁵ may comprise two separate R⁹ units, each of which is substituted by one or more independently selected R¹⁰ moieties. Preferably only one carbon atom of each R⁹ moiety is substituted by an -L-SO₃-M⁺ unit with the remaining R¹⁰ substituents comprising a hydrogen atom. When the value of the index i is equal to 1 (two R⁹ units comprise the R⁵ unit), a preferred formula is
wherein each R⁹ comprises a C₂ alkylene moiety. Preferably one R¹⁰ moiety is -L-SO₃ ^-M⁺, preferably the C₂ carbon is substituted by the -L-SO₃ ^-M⁺ moiety, and the balance are hydrogen atoms, having therefore a formula:
wherein L is a polyethyleneoxymethyl substituent, x is from 0 to 20.
As used herein, the term "R⁵ moieties consist essentially of units
having the index i equal to 0 wherein R¹⁰ units are hydrogen and one R¹⁰ units is equal to -L-SO₃ ^-M⁺, wherein L is a side chain connecting moiety selected from the group consisting of alkylene, alkenylene, alkoxyalkylene, oxyalkylene, arylene, alkylarylene, alkoxyarylene and mixtures thereof", refers to the preferred compounds wherein the R¹⁰ moieties consist of one -L-SO₃ ^-M⁺ moiety and the rest of the R¹⁰ moieties are hydrogen atoms, for example a
which is capable of inclusion into the polymeric backbone of the soil release polymers of the present invention as an -A-R⁵-A- backbone segment. The units are easily incorporated into the oligomer or polymer backbone by using starting materials having the general formula
wherein x, for the purposes of the L moiety of the present invention, is from 0 to 20.
Other suitable monomers capable of inclusion into the backbone of the type A preferred non-cotton soil release polymers as R⁵ moieties includes the alkylene poly(oxyalkylene)oxyarylene containing monomer having the general formula
wherein x is 0 to 20. A further example of a preferred monomer resulting in a preferred R⁵ unit wherein i is equal to 0, are the sodiosulfopoly(ethyleneoxy)methyl-1,2-propanediols having the formula
wherein x is from 0 to 20; more preferred are the monomers
The preferred soil release agents of the present invention in addition to the aforementioned R¹, R², R³, R⁴, and R⁵ units also comprise one or more capping groups,-(Cap). The capping groups are independently selected from ethoxylated or propoxylated hydroxyethane and propanesulfonate units of the formula (MO₃S)(CH₂)_m(R¹¹O)_n-, where M is a salt forming cation such as sodium or tetralkylammonium as described herein above, R¹¹ is ethylene or propylene or a mixture thereof, m is 0 or 1, and n is from 1 to 20, preferably n is from 1 to 4; sulfoaroyl units of the formula-(O)C(C₆H₄)(SO₃ ^-M⁺), wherein M is a salt forming cation as described herein above; modified poly(oxyethylene)oxy monoalkyl ether units of the formula R¹²O(CH₂CH₂O)_k- wherein R¹² contains from 1 to 4 carbon atoms, R¹² is preferably methyl, and k is from 3 to 100, preferably 3 to 50, more preferably 3 to 30; and ethoxylated or propoxylated phenolsulfonate end-capping units of the formula MO₃S(C₆H₄)(OR¹³)_nO-, wherein n is from to 20; M is a salt-forming cation; and R¹³ is ethylene, propylene and mixtures thereof.
Most preferred end capping unit is the isethionate-type end capping unit which is a hydroxyethane moiety, (MO₃S)(CH₂)_m(R¹¹O)_n-, preferably R¹¹ is ethyl, m is equal to 0, and n is from 2 to 4.
The value of t is 0 or 1; the value of u is from 0 to 60; the value of v is from 0 to 35; the value of w is from 0 to 35.
Preferred soil release polymers having the formula [(Cap)(R⁴)_t][(A-R¹-A-R²)_u(A-R¹-A-R³)_v(A-R¹-A-R⁵)_w
-A-R¹-A-][(R⁴)_t(Cap)] can be conveniently expressed as the following generic structural formula
The following structure is an example of the preferred soil release polymers of the present invention.
The above-described preferred soil release agents are fully described in U.S. Patent Application Serial No. 08/545,351 filed November 22, 1995 which is a continuation-in-part of U.S. Patent Application Serial No. 08/355,938 filed December 14, 1994. Other non-cotton soil release polymers suitable for use in the compositions of the present invention are further described herein below.
The preferred SRA's can be further described as oligomeric esters comprising: (1) a backbone comprising (a) at least one unit selected from the group consisting of dihydroxysulfonates, polyhydroxy sulfonates, a unit which is at least trifunctional whereby ester linkages are formed resulting in a branched oligomer backbone, and combinations thereof; (b) at least one unit which is a terephthaloyl moiety; and (c) at least one unsulfonated unit which is a 1,2-oxyalkyleneoxy moiety; and (2) one or more capping units selected from nonionic capping units, anionic capping units such as alkoxylated, preferably ethoxylated, isethionates, alkoxylated propanesulfonates, alkoxylated propanedisulfonates, alkoxylated phenolsulfonates, sulfoaroyl derivatives and mixtures thereof. Preferred are esters of the empirical formula: {(CAP)x(EG/PG)y'(DEG)y"(PEG)y"'(T)z(SIP)z'(SEG)q(B)m} wherein CAP, EG/PG, PEG, T and SIP are as defined as terephthaloyl (T), sulfoisophthaloyl (SIP), oxyethyleneoxy and oxy-1,2-propylene (EG/PG) units, end-caps (CAP), poly(ethyleneglycol) (PEG), (DEG) represents di(oxyethylene)oxy units, (SEG) represents units derived from the sulfoethyl ether of glycerin and related moiety units, (B) represents branching units which are at least trifunctional whereby ester linkages are formed resulting in a branched oligomer backbone, x is from 1 to 12, y' is from 0.5 to 25, y" is from 0 to 12, y"' is from 0 to 10, y'+y"+y"' totals from 0.5 to 25, z is from 1.5 to 25, z' is from 0 to 12; z + z' totals from 1.5 to 25, q is from 0.05 to 12; m is from 0.01 to 10, and x, y', y", y"', z, z', q and m represent the average number of moles of the corresponding units per mole of said ester and said ester has a molecular weight ranging from 500 to 5,000.
Preferred SEG and CAP monomers for the above esters include Na-2-(2-,3-dihydroxypropoxy)ethanesulfonate ("SEG"), Na-2-{2-(2-hydroxyethoxy) ethoxy} ethanesulfonate ("SE3") and its homologs and mixtures thereof and the products of ethoxylating and sulfonating allyl alcohol. Preferred SRA esters in this class include the product of transesterifying and oligomerizing sodium 2-{2-(2-hydroxyethoxy)ethoxy}ethanesulfonate and/or sodium 2-[2-{2-(2-hydroxyethoxy)ethoxy}-ethoxy]ethanesulfonate, DMT, sodium 2-(2,3-dihydroxypropoxy) ethane sulfonate, EG, and PG using an appropriate Ti(IV) catalyst and can be designated as (CAP)2(T)5(EG/PG)1.4(SEG)2.5(B)0.13 wherein CAP is (Na+-O₃S[CH₂CH₂O]3.5)-and B is a unit from glycerin and the mole ratio EG/PG is 1.7:1 as measured by conventional gas chromatography after complete hydrolysis.

Bleaching Compounds - Bleaching Agents and Bleach Activators

The detergent compositions herein may optionally contain bleaching agents or bleaching compositions containing a bleaching agent and one or more bleach activators. When present, bleaching agents will be at levels of from 0.05% to 30%, more preferably from 1% to 30%, most preferably from 5% to 20%, of the detergent composition, especially for fabric laundering. If present, the amount of bleach activators will typically be from 0.1% to 60%, more typically from 0.5% to 40% of the bleaching composition comprising the bleaching agent-plus-bleach activator.
The bleaching agents used herein can be any of the bleaching agents useful for detergent compositions in textile cleaning that are now known or become known. These include oxygen bleaches as well as other bleaching agents. Perborate bleaches, e.g., sodium perborate (e.g., mono- or tetra-hydrate) can be used herein.
Another category of bleaching agent that can be used without restriction encompasses percarboxylic acid bleaching agents and salts thereof. Suitable examples of this class of agents include magnesium monoperoxyphthalate hexahydrate, the magnesium salt of meta-chloroperbenzoic acid, 4-nonylamino-4-oxoperoxybutyric acid and diperoxydodecanedioic acid. Such bleaching agents are disclosed in U.S. Patent 4,483,781, Hartman, issued November 20, 1984, U.S. Patent Application 740,446, Burns et al, filed June 3, 1985, European Patent Application 0,133,354, Banks et al, published February 20, 1985, and U.S. Patent 4,412,934, Chung et al, issued November 1, 1983. Highly preferred bleaching agents also include 6-nonylamino-6-oxoperoxycaproic acid as described in U.S. Patent 4,634,551, issued January 6, 1987 to Burns et al.
Peroxygen bleaching agents can also be used. Suitable peroxygen bleaching compounds include sodium carbonate peroxyhydrate and equivalent "percarbonate" bleaches, sodium pyrophosphate peroxyhydrate, urea peroxyhydrate, and sodium peroxide. Persulfate bleach (e.g., OXONE, manufactured commercially by DuPont) can also be used.
A preferred percarbonate bleach comprises dry particles having an average particle size in the range from 500 micrometers to 1,000 micrometers, not more than 10% by weight of said particles being smaller than 200 micrometers and not more than 10% by weight of said particles being larger than 1,250 micrometers. Optionally, the percarbonate can be coated with silicate, borate or water-soluble surfactants. Percarbonate is available from various commercial sources such as FMC, Solvay and Tokai Denka.
Mixtures of bleaching agents can also be used.
Peroxygen bleaching agents, the perborates, the percarbonates, etc., are preferably combined with bleach activators, which lead to the in situ production in aqueous solution (i.e., during the washing process) of the peroxy acid corresponding to the bleach activator. Various nonlimiting examples of activators are disclosed in U.S. Patent 4,915,854, issued April 10, 1990 to Mao et al, and U.S. Patent 4,412,934. The nonanoyloxybenzene sulfonate (NOBS) and tetraacetyl ethylene diamine (TAED) activators are typical, and mixtures thereof can also be used. See also U.S. 4,634,551 for other typical bleaches and activators useful herein.
Highly preferred amido-derived bleach activators are those of the formulae: R¹N(R⁵)C(O)R²C(O)L or R¹C(O)N(R⁵)R²C(O)L wherein R¹ is an alkyl group containing from 6 to 12 carbon atoms, R² is an alkylene containing from 1 to 6 carbon atoms, R⁵ is H or alkyl, aryl, or alkaryl containing from 1 to 10 carbon atoms, and L is any suitable leaving group. A leaving group is any group that is displaced from the bleach activator as a consequence of the nucleophilic attack on the bleach activator by the perhydrolysis anion. A preferred leaving group is phenyl sulfonate.
Preferred examples of bleach activators of the above formulae include (6-octanamido-caproyl)oxybenzenesulfonate, (6-nonanamidocaproyl)oxybenzenesulfonate, (6-decanamido-caproyl)oxybenzenesulfonate, and mixtures thereof as described in U.S. Patent 4,634,551.
Another class of bleach activators comprises the benzoxazin-type activators disclosed by Hodge et al in U.S. Patent 4,966,723, issued October 30, 1990. A highly preferred activator of the benzoxazin-type is:
Still another class of preferred bleach activators includes the acyl lactam activators, especially acyl caprolactams and acyl valerolactams of the formulae:
wherein R⁶ is H or an alkyl, aryl, alkoxyaryl, or alkaryl group containing from 1 to 12 carbon atoms. Highly preferred lactam activators include benzoyl caprolactam, octanoyl caprolactam, 3,5,5-trimethylhexanoyl caprolactam, nonanoyl caprolactam, decanoyl caprolactam, undecenoyl caprolactam, benzoyl valerolactam, octanoyl valerolactam, decanoyl valerolactam, undecenoyl valerolactam, nonanoyl valerolactam, 3,5,5-trimethylhexanoyl valerolactam and mixtures thereof. See also U.S. Patent 4,545,784, issued to Sanderson, October 8, 1985, which discloses acyl caprolactams, including benzoyl caprolactam, adsorbed into sodium perborate.
Bleaching agents other than oxygen bleaching agents are also known in the art and can be utilized herein. One type of non-oxygen bleaching agent of particular interest includes photoactivated bleaching agents such as the sulfonated zinc and/or aluminum phthalocyanines. See U.S. Patent 4,033,718, issued July 5, 1977 to Holcombe et al. If used, detergent compositions will typically contain from 0.025% to 1.25%, by weight, of such bleaches, especially sulfonate zinc phthalocyanine.
If desired, the bleaching compounds can be catalyzed by means of a manganese compound. Such compounds are well known in the art and include, for example, the manganese-based catalysts disclosed in U.S. Pat. 5,246,621, U.S. Pat. 5,244,594; U.S. Pat. 5,194,416; U.S. Pat. 5,114,606; and European Pat. App. Pub. Nos. 549,271A1, 549,272A1, 544,440A2, and 544,490A1; Preferred examples of these catalysts include Mn^IV ₂(u-O)₃(1,4,7-trimethyl-1,4,7-triazacyclononane)₂(PF₆)₂, Mn^III ₂(u-O)₁(u-OAc)₂(1,4,7-trimethyl-1,4,7-triazacyclononane)_2-(ClO₄)₂, Mn^IV ₄(u-O)₆(1,4,7-triazacyclononane)₄(ClO₄)₄, Mn^IIIMn^IV ₄(u-O)₁(u-OAc)₂-(1,4,7-trimethyl-1,4,7-triazacyclononane)₂(ClO₄)₃, Mn^IV(1,4,7-trimethyl-1,4,7-triazacyclononane)-(OCH₃)₃(PF₆), and mixtures thereof. Other metal-based bleach catalysts include those disclosed in U.S. Pat. 4,430,243 and U.S. Pat. 5,114,611. The use of manganese with various complex ligands to enhance bleaching is also reported in the following United States Patents: 4,728,455; 5,284,944; 5,246,612; 5,256,779; 5,280,117; 5,274,147; 5,153,161; and 5,227,084.
As a practical matter, and not by way of limitation, the compositions and processes herein can be adjusted to provide on the order of at least one part per ten million of the active bleach catalyst species in the aqueous washing liquor, and will preferably provide from 0.1 ppm to 700 ppm, more preferably from 1 ppm to 500 ppm, of the catalyst species in the laundry liquor.
A wide variety of other ingredients useful in detergent compositions can be included in the compositions herein, including other active ingredients, carriers, hydrotropes, processing aids, dyes or pigments, solvents for liquid formulations, solid fillers for bar compositions. If high sudsing is desired, suds boosters such as the C₁₀-C₁₆ alkanolamides can be incorporated into the compositions, typically at 1%-10% levels. The C₁₀-C₁₄ monoethanol and diethanol amides illustrate a typical class of such suds boosters. Use of such suds boosters with high sudsing adjunct surfactants such as the amine oxides, betaines and sultaines noted above is also advantageous. If desired, soluble magnesium salts such as MgCl₂, MgSO₄, can be added at levels of, typically, 0.1%-2%, to provide additional suds and to enhance grease removal performance.
Various detersive ingredients employed in the present compositions optionally can be further stabilized by absorbing said ingredients onto a porous hydrophobic substrate, then coating said substrate with a hydrophobic coating. Preferably, the detersive ingredient is admixed with a surfactant before being absorbed into the porous substrate. In use, the detersive ingredient is released from the substrate into the aqueous washing liquor, where it performs its intended detersive function.
To illustrate this technique in more detail, a porous hydrophobic silica (trademark SIPERNAT D10, DeGussa) is admixed with a proteolytic enzyme solution containing 3%-5% of C_13-15 ethoxylated alcohol (EO 7) nonionic surfactant. Typically, the enzyme/surfactant solution is 2.5 X the weight of silica. The resulting powder is dispersed with stirring in silicone oil (various silicone oil viscosities in the range of 500-12,500 can be used). The resulting silicone oil dispersion is emulsified or otherwise added to the final detergent matrix. By this means, ingredients such as the aforementioned enzymes, bleaches, bleach activators, bleach catalysts, photoactivators, dyes, fluorescers, fabric conditioners and hydrolyzable surfactants can be "protected" for use in detergents, including liquid laundry detergent compositions.
Liquid detergent compositions can contain water and other solvents as carriers. Low molecular weight primary or secondary alcohols exemplified by methanol, ethanol, propanol, and isopropanol are suitable. Monohydric alcohols are preferred for solubilizing surfactant, but polyols such as those containing from 2 to 6 carbon atoms and from 2 to 6 hydroxy groups (e.g., 1,3-propanediol, ethylene glycol, glycerin, and 1,2-propanediol) can also be used. The compositions may contain from 5% to 90%, typically 10% to 50% of such carriers.
The detergent compositions herein will preferably be formulated such that, during use in aqueous cleaning operations, the wash water will have a pH of between 6.5 and 11, preferably between 7.5 and 10.5. Laundry products are typically at pH 9-11. Techniques for controlling pH at recommended usage levels include the use of buffers, alkalis, acids, and are well known to those skilled in the art.

Enzymes

Enzymes can be included in the present detergent compositions for a variety of purposes, including removal of protein-based, carbohydrate-based, or triglyceride-based stains from surfaces such as textiles, for the prevention of refugee dye transfer, for example in laundering, and for fabric restoration. Suitable enzymes include proteases, amylases, lipases, cellulases, peroxidases, and mixtures thereof of any suitable origin, such as vegetable, animal, bacterial, fungal and yeast origin. Preferred selections are influenced by factors such as pH-activity and/or stability optima, thermostability, and stability to active detergents, builders. In this respect bacterial or fungal enzymes are preferred, such as bacterial amylases and proteases, and fungal cellulases.
"Detersive enzyme", as used herein, means any enzyme having a cleaning, stain removing or otherwise beneficial effect in a laundry, hard surface cleaning or personal care detergent composition. Preferred detersive enzymes are hydrolases such as proteases, amylases and lipases. Preferred enzymes for laundry purposes include, but are not limited to, proteases, cellulases, lipases and peroxidases.
Enzymes are normally incorporated into detergent or detergent additive compositions at levels sufficient to provide a "cleaning-effective amount". The term "cleaning effective amount" refers to any amount capable of producing a cleaning, stain removal, soil removal, whitening, deodorizing, or freshness improving effect on substrates such as fabrics. In practical terms for current commercial preparations, typical amounts are up to about 5 mg by weight, more typically 0.01 mg to 3 mg, of active enzyme per gram of the detergent composition. Stated otherwise, the compositions herein will typically comprise from 0.001% to 5%, preferably 0.01%-1% by weight of a commercial enzyme preparation. Protease enzymes are usually present in such commercial preparations at levels sufficient to provide from 0.005 to 0.1 Anson units (AU) of activity per gram of composition. For certain detergents it may be desirable to increase the active enzyme content of the commercial preparation in order to minimize the total amount of non-catalytically active materials and thereby improve spotting/filming or other end-results. Higher active levels may also be desirable in highly concentrated detergent formulations.
Suitable examples of proteases are the subtilisins which are obtained from particular strains of B. subtilis and B. licheniformis. One suitable protease is obtained from a strain of Bacillus, having maximum activity throughout the pH range of 8-12, developed and sold as ESPERASE® by Novo Industries A/S of Denmark, hereinafter "Novo". The preparation of this enzyme and analogous enzymes is described in GB 1,243,784 to Novo. Other suitable proteases include ALCALASE® and SAVINASE® from Novo and MAXATASE® from International Bio-Synthetics, Inc., The Netherlands; as well as Protease A as disclosed in EP 130,756 A, January 9, 1985 and Protease B as disclosed in EP 303,761 A, April 28, 1987 and EP 130,756 A, January 9, 1985. See also a high pH protease from Bacillus sp. NCIMB 40338 described in WO 9318140 A to Novo. Enzymatic detergents comprising protease, one or more other enzymes, and a reversible protease inhibitor are described in WO 9203529 A to Novo. Other preferred proteases include those of WO 9510591 A to Procter & Gamble . When desired, a protease having decreased adsorption and increased hydrolysis is available as described in WO 9507791 to Procter & Gamble. A recombinant trypsin-like protease for detergents suitable herein is described in WO 9425583 to Novo.
In more detail, an especially preferred protease, referred to as "Protease D" is a carbonyl hydrolase variant having an amino acid sequence not found in nature, which is derived from a precursor carbonyl hydrolase by substituting a different amino acid for a plurality of amino acid residues at a position in said carbonyl hydrolase equivalent to position +76, preferably also in combination with one or more amino acid residue positions equivalent to those selected from the group consisting of +99, +101, +103, +104, +107, +123, +27, +105, +109, +126, +128, +135, +156, +166, +195, +197, +204, +206, +210, +216, +217, +218, +222, +260, +265, and/or +274 according to the numbering of Bacillus amyloliquefaciens subtilisin, as described in WO 95/10615 published April 20, 1995 by Genencor International.
Useful proteases are also described in PCT publications: WO 95/30010 published Novenber 9, 1995 by The Procter & Gamble Company; WO 95/30011 published Novenber 9, 1995 by The Procter & Gamble Company; WO 95/29979 published Novenber 9, 1995 by The Procter & Gamble Company.
Amylases suitable herein include, for example, α-amylases described in GB 1,296,839 to Novo; RAPIDASE®, International Bio-Synthetics, Inc. and TERMAMYL®, Novo. FUNGAMYL® from Novo is especially useful. Engineering of enzymes for improved stability, e.g., oxidative stability, is known. See, for example J. Biological Chem., Vol. 260, No. 11, June 1985, pp 6518-6521. Certain preferred embodiments of the present compositions can make use of amylases having improved stability in detergents, especially improved oxidative stability as measured against a reference-point of TERMAMYL® in commercial use in 1993. These preferred amylases herein share the characteristic of being "stability-enhanced" amylases, characterized, at a minimum, by a measurable improvement in one or more of: oxidative stability, e.g., to hydrogen peroxide / tetraacetylethylenediamine in buffered solution at pH 9-10; thermal stability, e.g., at common wash temperatures such as about 60°C; or alkaline stability, e.g., at a pH from 8 to 11, measured versus the above-identified reference-point amylase. Stability can be measured using any of the art-disclosed technical tests. See, for example, references disclosed in WO 9402597. Stability-enhanced amylases can be obtained from Novo or from Genencor International. One class of highly preferred amylases herein have the commonality of being derived using site-directed mutagenesis from one or more of the Baccillus amylases, especialy the Bacillus α-amylases, regardless of whether one, two or multiple amylase strains are the immediate precursors. Oxidative stability-enhanced amylases vs. the above-identified reference amylase are preferred for use, especially in bleaching, more preferably oxygen bleaching, as distinct from chlorine bleaching, detergent compositions herein. Such preferred amylases include (a) an amylase according to WO 9402597, Novo, Feb. 3, 1994, as further illustrated by a mutant in which substitution is made, using alanine or threonine, preferably threonine, of the methionine residue located in position 197 of the B.licheniformis alpha-amylase, known as TERMAMYL®, or the homologous position variation of a similar parent amylase, such as B. amyloliquefaciens, B.subtilis, or B.stearothermophilus; (b) stability-enhanced amylases as described by Genencor International in a paper entitled "Oxidatively Resistant alpha-Amylases" presented at the 207th American Chemical Society National Meeting, March 13-17 1994, by C. Mitchinson. Therein it was noted that bleaches in automatic dishwashing detergents inactivate alpha-amylases but that improved oxidative stability amylases have been made by Genencor from B.licheniformis NCIB8061. Methionine (Met) was identified as the most likely residue to be modified. Met was substituted, one at a time, in positions 8, 15, 197, 256, 304, 366 and 438 leading to specific mutants, particularly important being M197L and M197T with the M197T variant being the most stable expressed variant. Stability was measured in CASCADE® and SUNLIGHT®; (c) particularly preferred amylases herein include amylase variants having additional modification in the immediate parent as described in WO 9510603 A and are available from the assignee, Novo, as DURAMYL®. Other particularly preferred oxidative stability enhanced amylase include those described in WO 9418314 to Genencor International and WO 9402597 to Novo. Any other oxidative stability-enhanced amylase can be used, for example as derived by site-directed mutagenesis from known chimeric, hybrid or simple mutant parent forms of available amylases. Other preferred enzyme modifications are accessible. See WO 9509909 A to Novo.
Cellulases usable herein include both bacterial and fungal types, preferably having a pH optimum between 5 and 9.5. U.S. 4,435,307, Barbesgoard et al, March 6, 1984, discloses suitable fungal cellulases from Humicola insolens or Humicola strain DSM1800 or a cellulase 212-producing fungus belonging to the genus Aeromonas, and cellulase extracted from the hepatopancreas of a marine mollusk, Dolabella Auricula Solander. Suitable cellulases are also disclosed in GB-A-2.075.028; GB-A-2.095.275 and DE-OS-2.247.832. CAREZYME® (Novo) is especially useful. See also WO 9117243 to Novo.
Suitable lipase enzymes for detergent usage include those produced by microorganisms of the Pseudomonas group, such as Pseudomonas stutzeri ATCC 19.154, as disclosed in GB 1,372,034. See also lipases in Japanese Patent Application 53,20487, laid open Feb. 24, 1978. This lipase is available from Amano Pharmaceutical Co. Ltd., Nagoya, Japan, under the trade name Lipase P "Amano," or "Amano-P." Other suitable commercial lipases include Amano-CES, lipases ex Chromobacter viscosum, e.g. Chromobacter viscosum var. lipolyticum NRRLB 3673 from Toyo Jozo Co., Tagata, Japan; Chromobacter viscosum lipases from U.S. Biochemical Corp., U.S.A. and Disoynth Co., The Netherlands, and lipases ex Pseudomonas gladioli. LIPOLASE® enzyme derived from Humicola lanuginosa and commercially available from Novo, see also EP 341,947, is a preferred lipase for use herein. Lipase and amylase variants stabilized against peroxidase enzymes are described in WO 9414951 A to Novo. See also WO 9205249 and RD 94359044.
Cutinase enzymes suitable for use herein are described in WO 8809367 A to Genencor.
Peroxidase enzymes may be used in combination with oxygen sources, e.g., percarbonate, perborate, hydrogen peroxide, etc., for "solution bleaching" or prevention of transfer of dyes or pigments removed from substrates during the wash to other substrates present in the wash solution. Known peroxidases include horseradish peroxidase, ligninase, and haloperoxidases such as chloro- or bromo-peroxidase. Peroxidase-containing detergent compositions are disclosed in WO 89099813 A, October 19, 1989 to Novo and WO 8909813 A to Novo.
A range of enzyme materials and means for their incorporation into synthetic detergent compositions is also disclosed in WO 9307263 A and WO 9307260 A to Genencor International, WO 8908694 A to Novo, and U.S. 3,553,139, January 5, 1971 to McCarty et al. Enzymes are further disclosed in U.S. 4,101,457, Place et al, July 18, 1978, and in U.S. 4,507,219, Hughes, March 26, 1985. Enzyme materials useful for liquid detergent formulations, and their incorporation into such formulations, are disclosed in U.S. 4,261,868, Hora et al, April 14, 1981. Enzymes for use in detergents can be stabilized by various techniques. Enzyme stabilization techniques are disclosed and exemplified in U.S. 3,600,319, August 17, 1971, Gedge et al, EP 199,405 and EP 200,586, October 29, 1986, Venegas. Enzyme stabilization systems are also described, for example, in U.S. 3,519,570. A useful Bacillus, sp. AC13 giving proteases, xylanases and cellulases, is described in WO 9401532 A to Novo.

Enzyme Stabilizing System

Enzyme-containing, including but not limited to, liquid compositions, herein may comprise from 0.001% to 10%, preferably from 0.005% to 8%, most preferably from 0.01% to 6%, by weight of an enzyme stabilizing system. The enzyme stabilizing system can be any stabilizing system which is compatible with the detersive enzyme. Such a system may be inherently provided by other formulation actives, or be added separately, e.g., by the formulator or by a manufacturer of detergent-ready enzymes. Such stabilizing systems can, for example, comprise calcium ion, boric acid, propylene glycol, short chain carboxylic acids, boronic acids, and mixtures thereof, and are designed to address different stabilization problems depending on the type and physical form of the detergent composition.
One stabilizing approach is the use of water-soluble sources of calcium and/or magnesium ions in the finished compositions which provide such ions to the enzymes. Calcium ions are generally more effective than magnesium ions and are preferred herein if only one type of cation is being used. Typical detergent compositions, especially liquids, will comprise from 1 to 30, preferably from 2 to 20, more preferably from 8 to 12 millimoles of calcium ion per liter of finished detergent composition, though variation is possible depending on factors including the multiplicity, type and levels of enzymes incorporated. Preferably water-soluble calcium or magnesium salts are employed, including for example calcium chloride, calcium hydroxide, calcium formate, calcium malate, calcium maleate, calcium hydroxide and calcium acetate; more generally, calcium sulfate or magnesium salts corresponding to the exemplified calcium salts may be used. Further increased levels of Calcium and/or Magnesium may of course be useful, for example for promoting the grease-cutting action of certain types of surfactant.
Another stabilizing approach is by use of borate species. See Severson, U.S. 4,537,706. Borate stabilizers, when used, may be at levels of up to 10% or more of the composition though more typically, levels of up to 3% by weight of boric acid or other borate compounds such as borax or orthoborate are suitable for liquid detergent use. Substituted boric acids such as phenylboronic acid, butaneboronic acid, p-bromophenylboronic acid can be used in place of boric acid and reduced levels of total boron in detergent compositions may be possible though the use of such substituted boron derivatives.
Stabilizing systems of certain cleaning compositions may further comprise from 0 to 10%, preferably from 0.01% to 6% by weight, of chlorine bleach scavengers, added to prevent chlorine bleach species present in many water supplies from attacking and inactivating the enzymes, especially under alkaline conditions. While chlorine levels in water may be small, typically in the range from 0.5 ppm to 1.75 ppm, the available chlorine in the total volume of water that comes in contact with the enzyme, for example during fabric-washing, can be relatively large; accordingly, enzyme stability to chlorine in-use is sometimes problematic. Since perborate or percarbonate, which have the ability to react with chlorine bleach, may present in certain of the instant compositions in amounts accounted for separately from the stabilizing system, the use of additional stabilizers against chlorine, may, most generally, not be essential, though improved results may be obtainable from their use. Suitable chlorine scavenger anions are widely known and readily available, and, if used, can be salts containing ammonium cations with sulfite, bisulfite, thiosulfite, thiosulfate, iodide. Antioxidants such as carbamate, ascorbate, organic amines such as ethylenediaminetetracetic acid (EDTA) or alkali metal salt thereof, monoethanolamine (MEA), and mixtures thereof can likewise be used. Likewise, special enzyme inhibition systems can be incorporated such that different enzymes have maximum compatibility. Other conventional scavengers such as bisulfate, nitrate, chloride, sources of hydrogen peroxide such as sodium perborate tetrahydrate, sodium perborate monohydrate and sodium percarbonate, as well as phosphate, condensed phosphate, acetate, benzoate, citrate, formate, lactate, malate, tartrate, salicylate, and mixtures thereof can be used if desired. In general, since the chlorine scavenger function can be performed by ingredients separately listed under better recognized functions, (e.g., hydrogen peroxide sources), there is no absolute requirement to add a separate chlorine scavenger unless a compound performing that function to the desired extent is absent from an enzyme-containing embodiment of the invention; even then, the scavenger is added only for optimum results. Moreover, the formulator will exercise a chemist's normal skill in avoiding the use of any enzyme scavenger or stabilizer which is majorly incompatible, as formulated, with other reactive ingredients, if used. In relation to the use of ammonium salts, such salts can be simply admixed with the detergent composition but are prone to adsorb water and/or liberate ammonia during storage. Accordingly, such materials, if present, are desirably protected in a particle such as that described in US 4,652,392, Baginski et al.
The compositions herein can optionally include one or more other detergent adjunct materials or other materials for assisting or enhancing cleaning performance, treatment of the substrate to be cleaned, or to modify the aesthetics of the detergent composition (e.g., perfumes, colorants, dyes). The following are illustrative examples of such adjunct materials.

Builders

Detergent builders can optionally be included in the compositions herein to assist in controlling mineral hardness. Inorganic as well as organic builders can be used. Builders are typically used in fabric laundering compositions to assist in the removal of particulate soils.
The level of builder can vary widely depending upon the end use of the composition and its desired physical form. When present, the compositions will typically comprise at least 1% builder. Liquid formulations typically comprise from 5% to 50%, more typically 5% to 30%, by weight, of detergent builder. Granular formulations typically comprise from 10% to 80%, more typically from 15% to 50% by weight, of the detergent builder. Lower or higher levels of builder, however, are not meant to be excluded.
Inorganic or P-containing detergent builders include, but are not limited to, the alkali metal, ammonium and alkanolammonium salts of polyphosphates (exemplified by the tripolyphosphates, pyrophosphates, and glassy polymeric meta-phosphates), phosphonates, phytic acid, silicates, carbonates (including bicarbonates and sesquicarbonates), sulphates, and aluminosilicates. However, non-phosphate builders are required in some locales. Importantly, the compositions herein function surprisingly well even in the presence of the so-called "weak" builders (as compared with phosphates) such as citrate, or in the so-called "underbuilt" situation that may occur with zeolite or layered silicate builders.
Examples of silicate builders are the alkali metal silicates, particularly those having a SiO₂:Na₂O ratio in the range 1.6:1 to 3.2:1 and layered silicates, such as the layered sodium silicates described in U.S. Patent 4,664,839, issued May 12, 1987 to H. P. Rieck. NaSKS-6 is the trademark for a crystalline layered silicate marketed by Hoechst (commonly abbreviated herein as "SKS-6"). Unlike zeolite builders, the Na SKS-6 silicate builder does not contain aluminum. NaSKS-6 has the delta-Na₂SiO₅ morphology form of layered silicate. It can be prepared by methods such as those described in German DE-A-3,417,649 and DE-A-3,742,043. SKS-6 is a highly preferred layered silicate for use herein, but other such layered silicates, such as those having the general formula NaMSi_xO_2x+1·yH₂O wherein M is sodium or hydrogen, x is a number from 1.9 to 4, preferably 2, and y is a number from 0 to 20, preferably 0 can be used herein. Various other layered silicates from Hoechst include NaSKS-5, NaSKS-7 and NaSKS-11, as the alpha, beta and gamma forms. As noted above, the delta-Na₂SiO₅ (NaSKS-6 form) is most preferred for use herein. Other silicates may also be useful such as for example magnesium silicate, which can serve as a crispening agent in granular formulations, as a stabilizing agent for oxygen bleaches, and as a component of suds control systems.
Examples of carbonate builders are the alkaline earth and alkali metal carbonates as disclosed in German Patent Application No. 2,321,001 published on November 15, 1973.
Aluminosilicate builders are useful in the present invention. Aluminosilicate builders are of great importance in most currently marketed heavy duty granular detergent compositions, and can also be a significant builder ingredient in liquid detergent formulations. Aluminosilicate builders include those having the empirical formula: M_z(zAlO₂)_y]·xH₂O wherein z and y are integers of at least 6, the molar ratio of z to y is in the range from 1.0 to 0.5, and x is an integer from 15 to 264.
Useful aluminosilicate ion exchange materials are commercially available. These aluminosilicates can be crystalline or amorphous in structure and can be naturally-occurring aluminosilicates or synthetically derived. A method for producing aluminosilicate ion exchange materials is disclosed in U.S. Patent 3,985,669, Krummel, et al, issued October 12, 1976. Preferred synthetic crystalline aluminosilicate ion exchange materials useful herein are available under the designations Zeolite A, Zeolite P (B), Zeolite MAP and Zeolite X. In an especially preferred embodiment, the crystalline aluminosilicate ion exchange material has the formula: Na₁₂[(AlO₂)₁₂(SiO₂)₁₂]·xH₂O wherein x is from 20 to 30, especially 27. This material is known as Zeolite A. Dehydrated zeolites (x = 0 - 10) may also be used herein. Preferably, the aluminosilicate has a particle size of 0.1-10 microns in diameter.
Organic detergent builders suitable for the purposes of the present invention include, but are not restricted to, a wide variety of polycarboxylate compounds. As used herein, "polycarboxylate" refers to compounds having a plurality of carboxylate groups, preferably at least 3 carboxylates. Polycarboxylate builder can generally be added to the composition in acid form, but can also be added in the form of a neutralized salt. When utilized in salt form, alkali metals, such as sodium, potassium, and lithium, or alkanolammonium salts are preferred.
Included among the polycarboxylate builders are a variety of categories of useful materials. One important category of polycarboxylate builders encompasses the ether polycarboxylates, including oxydisuccinate, as disclosed in Berg, U.S. Patent 3,128,287, issued April 7, 1964, and Lamberti et al, U.S. Patent 3,635,830, issued January 18, 1972. See also "TMS/TDS" builders of U.S. Patent 4,663,071, issued to Bush et al, on May 5, 1987. Suitable ether polycarboxylates also include cyclic compounds, particularly alicyclic compounds, such as those described in U.S. Patents 3,923,679; 3,835,163; 4,158,635; 4,120,874 and 4,102,903.
Other useful detergency builders include the ether hydroxypolycarboxylates, copolymers of maleic anhydride with ethylene or vinyl methyl ether, 1, 3, 5-trihydroxy benzene-2, 4, 6-trisulphonic acid, and carboxymethyloxysuccinic acid, the various alkali metal, ammonium and substituted ammonium salts of polyacetic acids such as ethylenediamine tetraacetic acid and nitrilotriacetic acid, as well as polycarboxylates such as mellitic acid, succinic acid, oxydisuccinic acid, polymaleic acid, benzene 1,3,5-tricarboxylic acid, carboxymethyloxysuccinic acid, and soluble salts thereof.
Citrate builders, e.g., citric acid and soluble salts thereof (particularly sodium salt), are polycarboxylate builders of particular importance for heavy duty liquid detergent formulations due to their availability from renewable resources and their biodegradability. Citrates can also be used in granular compositions, especially in combination with zeolite and/or layered silicate builders. Oxydisuccinates are also especially useful in such compositions and combinations.
Also suitable in the detergent compositions of the present invention are the 3,3-dicarboxy-4-oxa-1,6-hexanedioates and the related compounds disclosed in U.S. Patent 4,566,984, Bush, issued January 28, 1986. Useful succinic acid builders include the C₅-C₂₀ alkyl and alkenyl succinic acids and salts thereof. A particularly preferred compound of this type is dodecenylsuccinic acid. Specific examples of succinate builders include: laurylsuccinate, myristylsuccinate, palmitylsuccinate, 2-dodecenylsuccinate (preferred), 2-pentadecenylsuccinate. Laurylsuccinates are the preferred builders of this group, and are described in European Patent Application 86200690.5/0,200,263, published November 5, 1986.
Other suitable polycarboxylates are disclosed in U.S. Patent 4,144,226, Crutchfield et al, issued March 13, 1979 and in U.S. Patent 3,308,067, Diehl, issued March 7, 1967. See also Diehl U.S. Patent 3,723,322.
Fatty acids, e.g., C₁₂-C₁₈ monocarboxylic acids, can also be incorporated into the compositions alone, or in combination with the aforesaid builders, especially citrate and/or the succinate builders, to provide additional builder activity. Such use of fatty acids will generally result in a diminution of sudsing, which should be taken into account by the formulator.
In situations where phosphorus-based builders can be used, and especially in the formulation of bars used for hand-laundering operations, the various alkali metal phosphates such as the well-known sodium tripolyphosphates, sodium pyrophosphate and sodium orthophosphate can be used. Phosphonate builders such as ethane-1-hydroxy-1,1-diphosphonate and other known phosphonates (see, for example, U.S. Patents 3,159,581; 3,213,030; 3,422,021; 3,400,148 and 3,422,137) can also be used.

Chelating Agents

The detergent compositions herein may also optionally contain one or more iron and/or manganese chelating agents. Such chelating agents can be selected from the group consisting of amino carboxylates, amino phosphonates, polyfunctionally-substituted aromatic chelating agents and mixtures therein, all as hereinafter defined. Without intending to be bound by theory, it is believed that the benefit of these materials is due in part to their exceptional ability to remove iron and manganese ions from washing solutions by formation of soluble chelates.
Amino carboxylates useful as optional chelating agents include ethylenediaminetetracetates, N-hydroxyethylethylenediaminetriacetates, nitrilotriacetates, ethylenediamine tetraproprionates, triethylenetetraaminehexacetates, diethylenetriaminepentaacetates, and ethanoldiglycines, alkali metal, ammonium, and substituted ammonium salts therein and mixtures therein. Also suitable for use as a chelant is methylglycine di-acetic acid (MGDA).
Amino phosphonates are also suitable for use as chelating agents in the compositions of the invention when at lease low levels of total phosphorus are permitted in detergent compositions, and include ethylenediaminetetrakis (methylenephosphonates) as DEQUEST. Preferred, these amino phosphonates to not contain alkyl or alkenyl groups with more than about 6 carbon atoms.
Polyfunctionally-substituted aromatic chelating agents are also useful in the compositions herein. See U.S. Patent 3,812,044, issued May 21, 1974, to Connor et al. Preferred compounds of this type in acid form are dihydroxydisulfobenzenes such as 1,2-dihydroxy-3,5-disulfobenzene.
A preferred biodegradable chelator for use herein is ethylenediamine disuccinate ("EDDS"), especially the [S,S] isomer as described in U.S. Patent 4,704,233, November 3, 1987, to Hartman and Perkins.
If utilized, these chelating agents will generally constitute from 0.1% to 10% by weight of the detergent compositions herein. More preferably, if utilized, the chelating agents will constitute from 0.1% to 3.0% by weight of such compositions.

Clay Soil Removal/Anti-redeposition Agents

The compositions of the present invention can also optionally contain water-soluble ethoxylated amines having clay soil removal and antiredeposition properties. Granular detergent compositions which contain these compounds typically contain from 0.01% to 10.0% by weight of the water-soluble ethoxylates amines; liquid detergent compositions typically contain 0.01% to 5%.
The most preferred soil release and anti-redeposition agent is ethoxylated tetraethylenepentamine. Exemplary ethoxylated amines are further described in U.S. Patent 4,597,898, VanderMeer, issued July 1, 1986. Another group of preferred clay soil removal-antiredeposition agents are the cationic compounds disclosed in European Patent Application 111,965, Oh and Gosselink, published June 27, 1984. Other clay soil removal/antiredeposition agents which can be used include the ethoxylated amine polymers disclosed in European Patent Application 111,984, Gosselink, published June 27, 1984; the zwitterionic polymers disclosed in European Patent Application 112,592, Gosselink, published July 4, 1984; and the amine oxides disclosed in U.S. Patent 4,548,744, Connor, issued October 22, 1985. Other clay soil removal and/or anti redeposition agents known in the art can also be utilized in the compositions herein. Another type of preferred antiredeposition agent includes the carboxy methyl cellulose (CMC) materials. These materials are well known in the art.

Polymeric Dispersing Agents

Polymeric dispersing agents can advantageously be utilized at levels from 0.1% to about 7%, by weight, in the compositions herein, especially in the presence of zeolite and/or layered silicate builders. Suitable polymeric dispersing agents include polymeric polycarboxylates and polyethylene glycols, although others known in the art can also be used. It is believed, though it is not intended to be limited by theory, that polymeric dispersing agents enhance overall detergent builder performance, when used in combination with other builders (including lower molecular weight polycarboxylates) by crystal growth inhibition, particulate soil release peptization, and anti-redeposition.
Polymeric polycarboxylate materials can be prepared by polymerizing or copolymerizing suitable unsaturated monomers, preferably in their acid form. Unsaturated monomeric acids that can be polymerized to form suitable polymeric polycarboxylates include acrylic acid, maleic acid (or maleic anhydride), fumaric acid, itaconic acid, aconitic acid, mesaconic acid, citraconic acid and methylenemalonic acid. The presence in the polymeric polycarboxylates herein or monomeric segments, containing no carboxylate radicals such as vinylmethyl ether, styrene, ethylene is suitable provided that such segments do not constitute more than about 40% by weight.
Particularly suitable polymeric polycarboxylates can be derived from acrylic acid. Such acrylic acid-based polymers which are useful herein are the water-soluble salts of polymerized acrylic acid. The average molecular weight of such polymers in the acid form preferably ranges from 2,000 to 10,000, more preferably from 4,000 to 7,000 and most preferably from 4,000 to 5,000. Water-soluble salts of such acrylic acid polymers can include, for example, the alkali metal, ammonium and substituted ammonium salts. Soluble polymers of this type are known materials. Use of polyacrylates of this type in detergent compositions has been disclosed, for example, in Diehl, U.S. Patent 3,308,067, issued march 7, 1967.
Acrylic/maleic-based copolymers may also be used as a preferred component of the dispersing/anti-redeposition agent. Such materials include the water-soluble salts of copolymers of acrylic acid and maleic acid. The average molecular weight of such copolymers in the acid form preferably ranges from 2,000 to 100,000, more preferably from 5,000 to 75,000, most preferably from 7,000 to 65,000. The ratio of acrylate to maleate segments in such copolymers will generally range from 30:1 to about 1:1, more preferably from 10:1 to 2:1. Water-soluble salts of such acrylic acid/maleic acid copolymers can include, for example, the alkali metal, ammonium and substituted ammonium salts. Soluble acrylate/maleate copolymers of this type are known materials which are described in European Patent Application No. 66915, published December 15, 1982, as well as in EP 193,360, published September 3, 1986, which also describes such polymers comprising hydroxypropylacrylate. Still other useful dispersing agents include the maleic/acrylic/vinyl alcohol terpolymers. Such materials are also disclosed in EP 193,360, including, for example, the 45/45/10 terpolymer of acrylic/maleic/vinyl alcohol.
Another polymeric material which can be included is polyethylene glycol (PEG). PEG can exhibit dispersing agent performance as well as act as a clay soil removal-antiredeposition agent. Typical molecular weight ranges for these purposes range from 500 to 100,000, preferably from 1,000 to 50,000, more preferably from 1,500 to 10,000.
Polyaspartate and polyglutamate dispersing agents may also be used, especially in conjunction with zeolite builders. Dispersing agents such as polyaspartate preferably have a molecular weight (avg.) of 10,000.

Brightener

Any optical brighteners or other brightening or whitening agents known in the art can be incorporated at levels typically from 0.05% to 1.2%, by weight, into the detergent compositions herein. Commercial optical brighteners which may be useful in the present invention can be classified into subgroups, which include, but are not necessarily limited to, derivatives of stilbene, pyrazoline, coumarin, carboxylic acid, methinecyanines, dibenzothiphene-5,5-dioxide, azoles, 5- and 6-membered-ring heterocycles, and other miscellaneous agents. Examples of such brighteners are disclosed in "The Production and Application of Fluorescent Brightening Agents", M. Zahradnik, Published by John Wiley & Sons, New York (1982).
Specific examples of optical brighteners which are useful in the present compositions are those identified in U.S. Patent 4,790,856, issued to Wixon on December 13, 1988. These brighteners include the PHORWHITE series of brighteners from Verona. Other brighteners disclosed in this reference include: Tinopal UNPA, Tinopal CBS and Tinopal 5BM; available from Ciba-Geigy; Artic White CC and Artic White CWD, available from Hilton-Davis, located in Italy; the 2-(4-stryl-phenyl)-2H-napthol[1,2-d]triazoles; 4,4'-bis- (1,2,3-triazol-2-yl)-stilbenes; 4,4'-bis(stryl)bisphenyls; and the aminocoumarins. Specific examples of these brighteners include 4-methyl-7-diethyl- amino coumarin; 1,2-bis(-venzimidazol-2-yl)ethylene; 1,3-diphenyl-phrazolines; 2,5-bis(benzoxazol-2-yl)thiophene; 2-stryl-napth-[1,2-d]oxazole; and 2-(stilbene-4-yl)-2H-naphtho- [1,2-d]triazole. See also U.S. Patent 3,646,015, issued February 29, 1972 to Hamilton. Anionic brighteners are preferred herein.

Suds Suppressors

Compounds for reducing or suppressing the formation of suds can be incorporated into the compositions of the present invention. Suds suppression can be of particular importance in the so-called "high concentration cleaning process" as described in U.S. 4,489,455 and 4,489,574 and in front-loading European-style washing machines.
A wide variety of materials may be used as suds suppressors, and suds suppressors are well known to those skilled in the art. See, for example, Kirk Othmer Encyclopedia of Chemical Technology, Third Edition, Volume 7, pages 430-447 (John Wiley & Sons, Inc., 1979). One category of suds suppressor of particular interest encompasses monocarboxylic fatty acid and soluble salts therein. See U.S. Patent 2,954,347, issued September 27, 1960 to Wayne St. John. The monocarboxylic fatty acids and salts thereof used as suds suppressor typically have hydrocarbyl chains of 10 to 24 carbon atoms, preferably 12 to 18 carbon atoms. Suitable salts include the alkali metal salts such as sodium, potassium, and lithium salts, and ammonium and alkanolammonium salts.
The detergent compositions herein may also contain non-surfactant suds suppressors. These include, for example: high molecular weight hydrocarbons such as paraffin, fatty acid esters (e.g., fatty acid triglycerides), fatty acid esters of monovalent alcohols, aliphatic C₁₈-C₄₀ ketones (e.g., stearone). Other suds inhibitors include N-alkylated amino triazines such as tri- to hexa-alkylmelamines or di- to tetra-alkyldiamine chlortriazines formed as products of cyanuric chloride with two or three moles of a primary or secondary amine containing 1 to 24 carbon atoms, propylene oxide, and monostearyl phosphates such as monostearyl alcohol phosphate ester and monostearyl di-alkali metal (e.g., K, Na, and Li) phosphates and phosphate esters. The hydrocarbons such as paraffin and haloparaffin can be utilized in liquid form. The liquid hydrocarbons will be liquid at room temperature and atmospheric pressure, and will have a pour point in the range of -40°C and 50°C, and a minimum boiling point not less than about 110°C (atmospheric pressure). It is also known to utilize waxy hydrocarbons, preferably having a melting point below about 100°C. The hydrocarbons constitute a preferred category of suds suppressor for detergent compositions. Hydrocarbon suds suppressors are described, for example, in U.S. Patent 4,265,779, issued May 5, 1981 to Gandolfo et al. The hydrocarbons, thus, include aliphatic, alicyclic, aromatic, and heterocyclic saturated or unsaturated hydrocarbons having from 12 to 70 carbon atoms. The term "paraffin," as used in this suds suppressor discussion, is intended to include mixtures of true paraffins and cyclic hydrocarbons.
Another preferred category of non-surfactant suds suppressors comprises silicone suds suppressors. This category includes the use of polyorganosiloxane oils, such as polydimethylsiloxane, dispersions or emulsions of polyorganosiloxane oils or resins, and combinations of polyorganosiloxane with silica particles wherein the polyorganosiloxane is chemisorbed or fused onto the silica. Silicone suds suppressors are well known in the art and are, for example, disclosed in U.S. Patent 4,265,779, issued May 5, 1981 to Gandolfo et al and European Patent Application No. 89307851.9, published February 7, 1990, by Starch, M. S.
Other silicone suds suppressors are disclosed in U.S. Patent 3,455,839 which relates to compositions and processes for defoaming aqueous solutions by incorporating therein small amounts of polydimethylsiloxane fluids.
Mixtures of silicone and silanated silica are described, for instance, in German Patent Application DOS 2,124,526. Silicone defoamers and suds controlling agents in granular detergent compositions are disclosed in U.S. Patent 3,933,672, Bartolotta et al, and in U.S. Patent 4,652,392, Baginski et al, issued March 24, 1987.
An exemplary silicone based suds suppressor for use herein is a suds suppressing amount of a suds controlling agent consisting essentially of:
(i) polydimethylsiloxane fluid having a viscosity of from 20 cs. to 1,500 cs. at 25°C;
(ii) from 5 to 50 parts per 100 parts by weight of (i) of siloxane resin composed of (CH₃)₃SiO_1/2 units of SiO₂ units in a ratio of from (CH₃)₃ SiO_1/2 units and to SiO₂ units of from 0.6:1 to 1.2:1; and
(iii) from about 1 to about 20 parts per 100 parts by weight of (i) of a solid silica gel.
In the preferred silicone suds suppressor used herein, the solvent for a continuous phase is made up of certain polyethylene glycols or polyethylene-polypropylene glycol copolymers or mixtures thereof (preferred), or polypropylene glycol. The primary silicone suds suppressor is branched/crosslinked and preferably not linear.
To illustrate this point further, typical liquid laundry detergent compositions with controlled suds will optionally comprise from 0.001 to 1, preferably from 0.01 to 0.7, most preferably from 0.05 to 0.5, weight % of said silicone suds suppressor, which comprises (1) a nonaqueous emulsion of a primary antifoam agent which is a mixture of (a) a polyorganosiloxane, (b) a resinous siloxane or a silicone resin-producing silicone compound, (c) a finely divided filler material, and (d) a catalyst to promote the reaction of mixture components (a), (b) and (c), to form silanolates; (2) at least one nonionic silicone surfactant; and (3) polyethylene glycol or a copolymer of polyethylene-polypropylene glycol having a solubility in water at room temperature of more than about 2 weight %; and without polypropylene glycol. Similar amounts can be used in granular compositions, gels, etc. See also U.S. Patents 4,978,471, Starch, issued December 18, 1990, and 4,983,316, Starch, issued January 8, 1991, 5,288,431, Huber et al., issued February 22, 1994, and U.S. Patents 4,639,489 and 4,749,740, Aizawa et al at column 1, line 46 through column 4, line 35.
The silicone suds suppressor herein preferably comprises polyethylene glycol and a copolymer of polyethylene glycol/polypropylene glycol, all having an average molecular weight of less than 1,000, preferably between 100 and 800. The polyethylene glycol and polyethylene/polypropylene copolymers herein have a solubility in water at room temperature of more than 2 weight %, preferably more than 5 weight %.
The preferred solvent herein is polyethylene glycol having an average molecular weight of less than 1,000, more preferably between about 100 and 800, most preferably between 200 and 400, and a copolymer of polyethylene glycol/polypropylene glycol, preferably PPG 200/PEG 300. Preferred is a weight ratio of between 1:1 and 1:10, most preferably between 1:3 and 1:6, of polyethylene glycol:copolymer of polyethylene-polypropylene glycol.
The preferred silicone suds suppressors used herein do not contain polypropylene glycol, particularly of 4,000 molecular weight. They also preferably do not contain block copolymers of ethylene oxide and propylene oxide, like PLURONIC L101.
Other suds suppressors useful herein comprise the secondary alcohols (e.g., 2-alkyl alkanols) and mixtures of such alcohols with silicone oils, such as the silicones disclosed in U.S. 4,798,679, 4,075,118 and EP 150,872. The secondary alcohols include the C₆-C₁₆ alkyl alcohols having a C₁-C₁₆ chain. A preferred alcohol is 2-butyl octanol, which is available from Condea under the trademark ISOFOL 12. Mixtures of secondary alcohols are available under the trademark ISALCHEM 123 from Enichem. Mixed suds suppressors typically comprise mixtures of alcohol + silicone at a weight ratio of 1:5 to 5:1.
For any detergent compositions to be used in automatic laundry washing machines, suds should not form to the extent that they overflow the washing machine. Suds suppressors, when utilized, are preferably present in a "suds suppressing amount. By "suds suppressing amount" is meant that the formulator of the composition can select an amount of this suds controlling agent that will sufficiently control the suds to result in a low-sudsing laundry detergent for use in automatic laundry washing machines.
The compositions herein will generally comprise from 0% to 5% of suds suppressor. When utilized as suds suppressors, monocarboxylic fatty acids, and salts therein, will be present typically in amounts up to 5%, by weight, of the detergent composition. Preferably, from 0.5% to 3% of fatty monocarboxylate suds suppressor is utilized. Silicone suds suppressors are typically utilized in amounts up to 2.0%, by weight, of the detergent composition, although higher amounts may be used. This upper limit is practical in nature, due primarily to concern with keeping costs minimized and effectiveness of lower amounts for effectively controlling sudsing. Preferably from 0.01% to 1% of silicone suds suppressor is used, more preferably from 0.25% to 0.5%. As used herein, these weight percentage values include any silica that may be utilized in combination with polyorganosiloxane, as well as any adjunct materials that may be utilized. Monostearyl phosphate suds suppressors are generally utilized in amounts ranging from 0.1% to 2%, by weight, of the composition. Hydrocarbon suds suppressors are typically utilized in amounts ranging from 0.01% to 5.0%, although higher levels can be used. The alcohol suds suppressors are typically used at 0.2%-3% by weight of the finished compositions.

Fabric Softeners

Various through-the-wash fabric softeners, especially the impalpable smectite clays of U.S. Patent 4,062,647, Storm and Nirschl, issued December 13, 1977, as well as other softener clays known in the art, can optionally be used typically at levels of from 0.5% to 10% by weight in the present compositions to provide fabric softener benefits concurrently with fabric cleaning. Clay softeners can be used in combination with amine and cationic softeners as disclosed, for example, in U.S. Patent 4,375,416, Crisp et al, March 1, 1983 and U.S. Patent 4,291,071, Harris et al, issued September 22, 1981.

Optical Brighteners

The detergent compositions herein may also optionally contain from 0.005% to 5% by weight of certain types of hydrophilic optical brighteners which also provide a dye transfer inhibition action. If used, the compositions herein will preferably comprise from 0.01% to 1% by weight of such optical brighteners.
The hydrophilic optical brighteners useful in the present invention are those having the structural formula:
wherein R₁ is selected from anilino, N-2-bis-hydroxyethyl and NH-2-hydroxyethyl; R₂ is selected from N-2-bis-hydroxyethyl, N-2-hydroxyethyl-N-methylamino, morphilino, chloro and amino; and M is a salt-forming cation such as sodium or potassium.
When in the above formula, R₁ is anilino, R₂ is N-2-bis-hydroxyethyl and M is a cation such as sodium, the brightener is 4,4',-bis[(4-anilino-6-(N-2-bis-hydroxyethyl)-s-triazine-2-yl)amino]-2,2'-stilbenedisulfonic acid and disodium salt. This particular brightener species is commercially marketed under the tradename Tinopal-UNPA-GX by Ciba-Geigy Corporation. Tinopal-UNPA-GX is the preferred hydrophilic optical brightener useful in the detergent compositions herein.
When in the above formula, R₁ is anilino, R₂ is N-2-hydroxyethyl-N-2-methylamino and M is a cation such as sodium, the brightener is 4,4'-bis[(4-anilino-6-(N-2-hydroxyethyl-N-methylamino)-s-triazine-2-yl)amino]2,2'-stilbenedisulfonic acid disodium salt. This particular brightener species is commercially marketed under the tradename Tinopal 5BM-GX by Ciba-Geigy Corporation.
When in the above formula, R₁ is anilino, R₂ is morpholino and M is a cation such as sodium, the brightener is 4,4'-bis[(4-anilino-6-morphilino-s-triazine-2-yl)amino]2,2'-stilbenedisulfonic acid, sodium salt. This particular brightener species is commercially marketed under the tradename Tinopal AMS-GX by Ciba Geigy Corporation.

EXAMPLE 1

Preparation of PEI 1800 E₇

The ethoxylation is conducted in a 2 gallon stirred stainless steel autoclave equipped for temperature measurement and control, pressure measurement, vacuum and inert gas purging, sampling, and for introduction of ethylene oxide as a liquid. A∼9.07 kg (∼20 lb.) net cylinder of ethylene oxide (ARC) is set up to deliver ethylene oxide as a liquid by a pump to the autoclave with the cylinder placed on a scale so that the weight change of the cylinder could be monitored.
A 750 g portion of polyethyleneimine (PEI) (Nippon Shokubai, Epomin SP-018 having a listed average molecular weight of 1800 equating to 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 94,8 kPa (28" Hg) followed by pressurization with nitrogen to 1725 kPa (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 1725 kPa (250 psia) while cooling the autoclave to about 105 °C. Ethylene oxide is then added to the autoclave incrementally over time while closely monitoring the autoclave pressure, temperature, and ethylene oxide flow rate. The ethylene oxide pump is turned off and cooling is applied to limit any temperature increase resulting from any reaction exotherm. The temperature is maintained between 100 and 110 °C while the total pressure is allowed to gradually increase during the course of the reaction. After a total of 750 grams of ethylene oxide has been charged to the autoclave (roughly equivalent to one mole ethylene oxide per PEI nitrogen function), the temperature is increased to 110 °C and the autoclave is allowed to stir for an additional hour. At this point, vacuum is applied to remove any residual unreacted ethylene oxide.
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 consumed by the agitator. The agitator power is monitored along with the temperature and pressure. Agitator power and temperature values gradually increase as methanol is removed from the autoclave and the viscosity of the mixture increases and stabilizes in about 1 hour indicating that most of the methanol has been removed. The mixture is further heated and agitated under vacuum for an additional 30 minutes.
Vacuum is removed and the autoclave is cooled to 105 °C while it is being charged with nitrogen to 1725 kPa (250 psia) and then vented to ambient pressure. The autoclave is charged to 1380 kPa (200 psia) with nitrogen. Ethylene oxide is again added to the autoclave incrementally as before while closely monitoring the autoclave pressure, temperature, and ethylene oxide flow rate while maintaining the temperature between 100 and 110 °C and limiting any temperature increases due to reaction exotherm. After the addition of 4500 g of ethylene oxide (resulting in a total of 7 moles of ethylene oxide per mole of PEI nitrogen function) is achieved over several hours, the temperature is increased to 110 °C and the mixture stirred for an additional hour.
The reaction mixture is then collected in nitrogen purged containers and eventually transferred into a 22 L three neck round bottomed flask equipped with heating and agitation. The strong alkali catalyst is neutralized by adding 167 g methanesulfonic acid (1.74 moles). The reaction mixture is then deodorized by passing about 2.83 m³ (100 cu. ft.) of inert gas (argon or nitrogen) through a gas dispersion frit and through the reaction mixture while agitating and heating the mixture to 130 °C.
The final reaction product is cooled slightly and collected in glass containers purged with nitrogen.
In other preparations the neutralization and deodorization is accomplished in the reactor before discharging the product.

EXAMPLE 2

Quaternization of PEI 1800 E₇

To a 500 mL Erlenmeyer flask equipped with a magnetic stirring bar is added polyethyleneimine having a molecular weight of 1800 which is further modified by ethoxylation to a degree of approximately 7 ethyleneoxy residues per nitrogen (PEI 1800, E₇) (207.3g, 0.590 mol nitrogen, prepared as in Example I) and acetonitrile (120 g). Dimethyl sulfate (28.3g, 0.224 mol) is added in one portion to the rapidly stirring solution, which is then stoppered and stirred at room temperature overnight. The acetonitrile is removed by rotary evaporation at about 60°C, followed by further stripping of solvent using a Kugelrohr apparatus at approximately 80°C to afford 220 g of the desired partially quaternized material as a dark brown viscous liquid. The ¹³C-NMR (D₂O) spectrum obtained on a sample of the reaction product indicates the absence of a carbon resonance at ∼58ppm corresponding to dimethyl sulfate. The ¹H-NMR (D₂O) spectrum shows a partial shifting of the resonance at about 2.5 ppm for methylenes adjacent to unquaternized nitrogen has shifted to approximately 3.0 ppm. This is consistent with the desired quaternization of about 38% of the nitrogens.

EXAMPLE 3

Formation of amine oxide of PEI 1800 E₇

To a 500 mL Erlenmeyer flask equipped with a magnetic 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, prepared 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 temperature overnight. ¹H-NMR (D₂O) spectrum obtained on a sample of the reaction mixture indicates complete conversion. The resonances ascribed to methylene protons adjacent to unoxidized nitrogens have shifted from the original position at ∼2.5 ppm to ∼3.5 ppm. To the reaction solution is added approximately 5 g of 0.5% Pd on alumina pellets, and the solution is allowed to stand at room temperature for approximately 3 days. The solution is tested and found to be negative for peroxide by indicator paper. The material as obtained is suitably stored as a 51.1% active solution in water.

EXAMPLE 4

Oxidation of Quaternized PEI 1800 E₇

To a 500 mL Erlenmeyer flask equipped with a magnetic stirring bar is added polyethyleneimine having a molecular weight of 1800 which is further modified by ethoxylation to a degree of 7 ethyleneoxy residues per nitrogen (PEI 1800 E₇) subsequently quaternized with dimethyl sulfate to approximately 4.7% (121.7 g, ~0.32 mol oxidizeable nitrogen), hydrogen peroxide (40 g of a 50 wt% solution in water, 0.588 mol), and water (109.4 g). The flask is stoppered, and after an initial exotherm the solution is stirred at room temperature overnight. ¹H-NMR (D₂O) spectrum obtained on a sample of the reaction mixture indicates the methylene peaks at 2.5-3.0 ppm have shifted to ∼3.5 ppm. To the reaction solution is added ∼5 g of 0.5 % Pd on alumina pellets, and the solution is allowed to stand at room temperature for ∼3 days. The solution is tested and found to be negative for peroxide by indicator paper. The desired material with ~4.7% of the nitrogens quaternized and ~95.3% of the nitrogens oxidized to the amine oxide is obtained and is suitably stored as a 46.5% solution in water.

EXAMPLE 4A

Preparation of PEI 1200 E₇

The ethoxylation is conducted in a 2 gallon stirred stainless steel autoclave equipped for temperature measurement and control, pressure measurement, vacuum and inert gas purging, sampling, and for introduction of ethylene oxide as a liquid. A∼9.07 kg (~20 lb.) net cylinder of ethylene oxide (ARC) is set up to deliver ethylene oxide as a liquid by a pump to the autoclave with the cylinder placed on a scale so that the weight change of the cylinder could be monitored.
A 750 g portion of polyethyleneimine (PEI) ( having a listed average molecular weight of 1200 equating to about 0.625 moles of polymer and 17.4 moles of nitrogen functions) is added to the autoclave. The autoclave is then sealed and purged of air (by applying vacuum to minus 94.8 kPa (28" Hg) followed by pressurization with nitrogen to 1725 kPa (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 1725 kPa (250 psia) while cooling the autoclave to about 105 °C. Ethylene oxide is then added to the autoclave incrementally over time while closely monitoring the autoclave pressure, temperature, and ethylene oxide flow rate. The ethylene oxide pump is turned off and cooling is applied to limit any temperature increase resulting from any reaction exotherm. The temperature is maintained between 100 and 110 °C while the total pressure is allowed to gradually increase during the course of the reaction. After a total of 750 grams of ethylene oxide has been charged to the autoclave (roughly equivalent to one mole ethylene oxide per PEI nitrogen function), the temperature is increased to 110 ° C and the autoclave is allowed to stir for an additional hour. At this point, vacuum is applied to remove any residual unreacted ethylene oxide.
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 consumed by the agitator. The agitator power is monitored along with the temperature and pressure. Agitator power and temperature values gradually increase as methanol is removed from the autoclave and the viscosity of the mixture increases and stabilizes in about 1 hour indicating that most of the methanol has been removed. The mixture is further heated and agitated under vacuum for an additional 30 minutes.
Vacuum is removed and the autoclave is cooled to 105 °C while it is being charged with nitrogen to 1725 kPa (250 psia) and then vented to ambient pressure. The autoclave is charged to 1380 kPa (200 psia) with nitrogen. Ethylene oxide is again added to the autoclave incrementally as before while closely monitoring the autoclave pressure, temperature, and ethylene oxide flow rate while maintaining the temperature between 100 and 110 °C and limiting any temperature increases due to reaction exotherm. After the addition of 4500 g of ethylene oxide (resulting in a total of 7 moles of ethylene oxide per mole of PEI nitrogen function) is achieved over several hours, the temperature is increased to 110 °C and the mixture stirred for an additional hour.
The reaction mixture is then collected in nitrogen purged containers and eventually transferred into a 22 L three neck round bottomed flask equipped with heating and agitation. The strong alkali catalyst is neutralized by adding 167 g methanesulfonic acid (1.74 moles). The reaction mixture is then deodorized by passing about 2.83 m³ (100 cu. ft.) of inert gas (argon or nitrogen) through a gas dispersion frit and through the reaction mixture while agitating and heating the mixture to 130 °C.
The final reaction product is cooled slightly and collected in glass containers purged with nitrogen.
In other preparations the neutralization and deodorization is accomplished in the reactor before discharging the product.
Other preferred examples such as PEI 1200 E15 and PEI 1200 E20 can be prepared by the above method by adjusting the reaction time and the relative amount of ethylene oxide used in the reaction.

EXAMPLE 4B

9.7% Quaternization 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 nitrogen, 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 stoppered and stirred at room temperature overnight. The acetonitrile is evaporated on the rotary evaporator at ∼60°C, followed by a Kugelrohr apparatus (Aldrich) at ∼80°C to afford ∼220g of the desired material as a dark brown viscous liquid. A ¹³C-NMR (D₂O) spectrum shows the absence of a peak at ∼58ppm corresponding to dimethyl sulfate. A ¹H-NMR (D₂O) spectrum shows the partial shifting of the peak at 2.5ppm (methylenes attached to unquaternized nitrogens) to ∼3.0ppm.

EXAMPLE 5

Preparation of Non-cotton Soil Release Polymers Synthesis of Sodium 2-(2,3-Dihydroxypropoxy)ethanesulfonate Monomer

To a 500ml, three neck, round bottom flask equipped with a magnetic stirring bar, modified Claisen head, condenser (set for distillation), thermometer, and temperature controller (Therm-O-Watch™, I²R) is added isethionic acid, sodium salt (Aldrich, 50.0g, 0.338 mol), sodium hydroxide (2.7g, 0.0675 mol), and glycerin (Baker, 310.9g, 3.38 mol). The solution is heated at 190°C under argon overnight as water distills from the reaction mixture. A ¹³C-NMR(DMSO-d₆) shows that the reaction is complete by the virtual disappearance of the isethionate peaks at ∼53.5 ppm and ∼57.4 ppm, and the emergence of product peaks at ∼51.4 ppm (-CH₂SO₃Na) and ∼67.5 ppm (CH₂CH₂SO₃Na). The solution is cooled to ∼100°C and neutralized to pH 7 with methanesulfonic acid (Aldrich). The desired, neat material is obtained by adding 0.8 mol% of potassium phosphate, monobasic as buffer and heating on a Kugelrohr apparatus (Aldrich) at 200°C for ∼ 3 hrs. at ∼1 mm Hg to afford 77g of yellow waxy solid. As an alternative, not all of the glycerin is removed before use in making the oligomers. The use of glycerin solutions of SEG can be a convenient way of handling this sulfonated monomer.

EXAMPLE 6

Synthesis of Sodium 2-[2-(2-Hydroxyethoxy)ethoxy]ethanesulfonate Monomer

To a 1L, three neck, round bottom flask equipped with a magnetic stirring bar, modified Claisen head, condenser (set for distillation), thermometer, and temperature controller (Therm-O-Watch™, I²R) is added isethionic acid, sodium salt (Aldrich, 100.0g, 0.675 mol) and distilled water (~90 ml). After dissolution, one drop of hydrogen peroxide (Aldrich, 30% by wt. in water) is added to oxidize traces of bisulfite. The solution is stirred for one hour. A peroxide indicator strip shows a very weak positive test. Sodium hydroxide pellets (MCB, 2.5g, 0.0625 mol) are added, followed by diethylene glycol (Fisher, 303.3g, 2.86 mol). The solution is heated at 190°C under argon overnight as water distills from the reaction mixture. A ¹³C-NMR(DMSO-d₆) shows that the reaction is complete by the disappearance of the isethionate peaks at ∼53.5 ppm and ∼57.4 ppm. The solution is cooled to room temperature and neutralized to pH 7 with 57.4g of a 16.4% solution of p-toluenesulfonic acid monohydrate in diethylene glycol. (Alternatively, methanesulfonic acid may be used.) The ¹³C-NMR spectrum of the product shows resonances at ∼51 ppm (-CH₂SO₃Na), ∼60ppm (-CH₂OH), and at ∼69 ppm, ∼72 ppm, and ∼77 ppm for the remaining four methylenes. Small resonances are also visible for the sodium p-toluenesulfonate which formed during neutralization. The reaction affords 451g of a 35.3% solution of sodium 2-[2-(2-hydroxyethoxy)ethoxy]ethanesulfonate in diethylene glycol. The excess diethylene glycol is removed by adding 0.8 mol% of monobasic potassium phosphate (Aldrich) as a buffer and heating on a Kugelrohr apparatus (Aldrich) at 150C° for ~ 3 hrs. at ~1 mm Hg to give the desired "SE₃" (as defined herein above) as an extremely viscous oil or glass.

EXAMPLE 7

Synthesis of Sodium 2-{2-[2-(2-Hydroxyethoxy)ethoxy]ethoxy}ethanesulfonate Monomer

To a 1L, three neck, round bottom flask equipped with a magnetic stirring bar, modified Claisen head, condenser (set for distillation), thermometer, and temperature controller (Therm-O-Watch™, I²R) is added isethionic acid, sodium salt (Aldrich, 205.0g, 1.38 mol) and distilled water (∼200 ml). After dissolution, one drop of hydrogen peroxide (Aldrich, 30% by wt. in water) is added to oxidize traces of bisulfite. The solution is stirred for one hour. A peroxide indicator strip shows a very weak positive test. Sodium hydroxide pellets (MCB, 5.5g, 0.138 mol) are added, followed by triethylene glycol (Aldrich, 448.7g, 3.0 mol). Optionally, the triethylene glycol can be purified by heating with strong base such as NaOH until color stabilizes and then distilling off the purified glycol for use in the synthesis. The solution is heated at 190C° under argon overnight as water distills from the reaction mixture. A ¹³C-NMR(DMSO-d₆) shows that the reaction is complete by the disappearance of the isethionate peaks at ~53.5 ppm and ~57.4 ppm, and the emergence of product peaks at ~51ppm (-CH₂SO₃Na), ~60ppm (-CH₂OH), and at ~67 ppm, ~69 ppm, and ~72 ppm for the remaining methylenes. The solution is cooled to room temperature and neutralized to pH 7 with methanesulfonic acid (Aldrich). The reaction affords 650g of a 59.5% solution of sodium 2-{2-[2-(2-hydroxyethoxy)ethoxy]ethoxy}ethanesulfonate in triethylene glycol. The excess triethylene glycol is removed by adding 0.8 mol% of monobasic potassium phosphate (Aldrich) as a buffer and heating on a Kugelrohr apparatus (Aldrich) at 180C° for ~5.5 hrs. at ~1 mm Hg to give the desired material as a brown solid. It is found that a more soluble buffer can be more effective in controlling pH during the stripping of excess triethylene glycol. One example of such a more soluble buffer is the salt of N-methylmorpholine with methanesulfonic acid. Alternatively, the pH can be controlled by frequent or continuous addition of acid such as methanesulfonic acid to maintain a pH near neutral during the stripping of excess glycol.
The material is believed to contain a low level of the disulfonate arising from reaction of both ends of the triethylene glycol with isethionate. However, the crude material is used without further purification as an anionic capping groups for polymer preparations.
Other preparations use a larger excess of triethylene glycol such as 5 to 10 moles per mole of isethionate.

EXAMPLE 8

Synthesis of an Oligomer of Sodium 2-[2-(2-Hydroxyethoxy)ethoxy]ethanesulfonate. Dimethyl Terephthalate, Sodium 2-(2,3-Dihydroxypropoxy)ethanesulfonate, Glycerin, Ethylene Glycol, and Propylene Glycol)

To a 250ml, three neck, round bottom flask equipped with a magnetic stirring bar, modified Claisen head, condenser (set for distillation), thermometer, and temperature controller (Therm-O-Watch®, I²R) is added sodium 2-[2-(2-hydroxyethoxy)ethoxy]ethanesulfonate (7.0g, 0.030 mol), dimethyl terephthalate (14.4g, 0.074 mol), sodium 2-(2,3-dihydroxypropoxy)ethanesulfonate (3.3g, 0.015 mol), glycerin (Baker, 1.4g, 0.015 mol), ethylene glycol (Baker, 14.0g, 0.225 mol), propylene glycol (Fisher, 17.5g, 0.230 mol), and titanium (IV) propoxide (0.01g, 0.02% of total reaction weight). This mixture is heated to 180°C and maintained at that temperature overnight under argon as methanol and water distill from the reaction vessel. The material is transferred to a 500ml, single neck, round bottom flask and heated gradually over about 20 minutes to 240°C in a Kugelrohr apparatus (Aldrich) at about 2 mm Hg and maintained there for 1.5 hours. The reaction flask is then allowed to air cool quite rapidly to near room temperature under vacuum (~30 min.) The reaction affords 21.3g of the desired oligomer as a brown glass. A ¹³C-NMR(DMSO-d₆) shows a resonance for -C(O)OCH2CH2O(O)C- at ~63.2 ppm (diester) and a resonance for -C(O)OCH2CH2OH at ~59.4 ppm (monoester). The ratio of the diester peak height to the monoester peak height is about 10. Resonances at ~51.5 ppm and ~51.6 ppm representing the sulfoethoxy groups (-CH2SO3Na) are also present. A ¹H-NMR(DMSO-d₆) shows a resonance at ~7.9 ppm representing terephthalate aromatic hydrogens. Analysis by hydrolysis-gas chromatography shows that the mole ratio of incorporated ethylene glycol to incorporated propylene glycol is 1.7:1. It also shows that about 0.9% of the final polymer weight consists of glycerin. If all glycerin monomer has been incorporated as esters of glycerin, it would represent approximately 4% of final oligomer weight. The solubility is tested by weighing a small amount of material into a vial, adding enough distilled water to make a 35% by weight solution, and agitating the vial vigorously. The material is readily soluble under these conditions.

EXAMPLE 9

Synthesis of an Oligomer of Sodium 2-[2-(2-Hydroxyethoxy)ethoxy]ethanesulfonate, Dimethyl Terephthalate, Sodium 2-(2,3-Dihydroxypropoxy)ethanesulfonate, Ethylene Glycol, and Propylene Glycol)

To a 250 ml, three neck, round bottom flask equipped with a magnetic stirring bar, modified Claisen head, condenser (set for distillation), thermometer, and temperature controller (Therm-O-Watch®, I²R) is added sodium 2-[2-(2-hydroxyethoxy)ethoxy]ethanesulfonate (7.0g, 0.030 mol), dimethyl terephthalate (14.4g, 0.074 mol), sodium 2-(2,3-dihydroxypropoxy)ethanesulfonate (6.6g, 0.030 mol), ethylene glycol (Baker, 14.0g, 0.225 mol), propylene glycol (Fisher, 18.3g, 0.240 mol), and titanium (IV) propoxide (0.01g, 0.02% of total reaction weight). This mixture is heated to 180°C and maintained at that temperature overnight under argon as methanol distills from the reaction vessel. The material is transferred to a 500ml, single neck, round bottom flask and heated gradually over about 20 minutes to 240°C in a Kugelrohr apparatus (Aldrich) at about 13 Pa (0.1 mm Hg) and maintained there for 110 minutes. The reaction flask is then allowed to air cool quite rapidly to near room temperature under vacuum (∼30 min.) The reaction affords 24.4g of the desired oligomer as a brown glass. A ¹³C-NMR(DMSO-d₆) shows a resonance for -C(O)OCH2CH2O(O)C- at ∼63.2 ppm (diester) and a resonance for -C(O)OCH2CH2OH at ∼59.4 ppm (monoester). The ratio of the diester peak to monoester peak is measured to be 8. Resonances at ∼51.5 ppm and ∼51.6 ppm representing the sulfoethoxy groups (-CH2SO3Na) are also present. A ¹H-NMR(DMSO-d₆) shows a resonance at ∼7.9 ppm representing terephthalate aromatic hydrogens. Analysis by Hydrolysis-GC shows that the mole ratio of incorporated ethylene glycol to incorporated propylene glycol is 1.6:1. The solubility is tested by weighing a small amount of material into a vial, adding enough distilled water to make a 35% by weight solution, and agitating the vial vigorously. The material is readily soluble under these conditions.

EXAMPLE 10

Synthesis of an Oligomer of Sodium 2-[2-(2-Hydroxyethoxy]ethoxy]ethanesulfonate, Dimethyl Terephthalate, Sodium 2-(2,3-Dihydroxypropoxy)ethanesulfonate, Glycerin, Ethylene Glycol, and Propylene Glycol )

To a 250 ml, three neck, round bottom flask equipped with a magnetic stirring bar, modified Claisen head, condenser (set for distillation), thermometer, and temperature controller (Therm-O-Watch®, I²R) is added sodium 2-[2-(2-hydroxyethoxy)ethoxy]ethanesulfonate (7.0g, 0.030 mol), dimethyl terephthalate (9.6g, 0.049 mol), sodium 2-(2,3-dihydroxypropoxy)ethanesulfonate (2.2g, 0.010 mol), glycerin (Baker, 1.8g, 0.020 mol), ethylene glycol (Baker, 6.1g, 0.100 mol), propylene glycol (Fisher, 7.5g, 0.100 mol), and titanium (IV) propoxide (0.01g, 0.02% of total reaction weight). This mixture is heated to 180°C and maintained at that temperature overnight under argon as methanol distills from the reaction vessel. The material is transferred to a 250 ml, single neck, round bottom flask and heated gradually over about 20 minutes to 240°C in a Kugelrohr apparatus (Aldrich) at about 3 mm Hg and maintained there for 1.5 hours. The reaction flask is then allowed to air cool quite rapidly to near room temperature under vacuum (~30 min.) The reaction affords 18.1g of the desired oligomer as a brown glass. A ¹³C-NMR(DMSO-d₆) shows a resonance for -C(O)OCH2CH2O(O)C- at ~63.2 ppm (diester). A resonance for -C(O)OCH2CH2OH at ~59.4 ppm (monoester) is not detectable and is at least 12 times smaller than the diester peak. Resonances at ~51.5 ppm and ~51.6 ppm representing the sulfoethoxy groups (-CH2SO3Na) are also present. A ¹H-NMR(DMSO-d₆) shows a resonance at ∼7.9 ppm representing terephthalate aromatic hydrogens. Analysis by Hydrolysis-GC shows that the mole ratio of incorporated ethylene glycol to incorporated propylene glycol is 1.6:1. The incorporated glycerin is found to be 0.45 weight % of the final polymer. The solubility is tested by weighing a small amount of material into a vial, adding enough distilled water to make a 35% by weight solution, and agitating the vial vigorously. The material is readily soluble under these conditions.

EXAMPLE 11

Synthesis of an Oligomer of Sodium 2-[2-(2-Hydroxyethoxy)ethoxy]ethanesulfonate. Dimethyl Terephthalate, Sodium 2-(2,3-Dihydroxypropoxy)ethanesulfonate, Glycerol, Ethylene Glycol, and Propylene Glycol)

To a 250 ml, three neck, round bottom flask equipped with a magnetic stirring bar, modified Claisen head, condenser (set for distillation), thermometer, and temperature controller (Therm-O-Watch®, I²R) is added sodium 2-[2-(2-hydroxyethoxy)ethoxy]ethanesulfonate (2.7g, 0.011 mol, as in Example 2), dimethyl terephthalate (12.0g, 0.062 mol, Aldrich), sodium 2-(2,3-dihydroxypropoxy)ethanesulfonate (5.0g, 0.022 mol, as in Example 1), glycerol (Baker, 0.50g, 0.0055 mol), ethylene glycol (Baker, 6.8g, 0.110 mol), propylene glycol (Baker, 8.5g, 0.112 mol), and titanium (IV) propoxide (0.01g, 0.02% of total reaction weight). This mixture is heated to 180°C and maintained at that temperature overnight under argon as methanol and water distill from the reaction vessel. The material is transferred to a 500ml, single neck, round bottom flask and heated gradually over about 20 minutes to 240°C in a Kugelrohr apparatus (Aldrich) at about 67 Pa (0.5 mm Hg) and maintained there for 150 minutes. The reaction flask is then allowed to air cool quite rapidly to near room temperature under vacuum (∼30 min.) The reaction affords 16.7g of the desired oligomer as a brown glass. A ¹³C-NMR(DMSO-d₆) shows a resonance for -C(O)OCH2CH2O(O)C- at ∼63.2 ppm (diester) and a resonance for -C(O)OCH2CH2OH at ∼59.4 ppm (monoester). The ratio of the peak height for the diester resonance to that of the monoester resonance is measured to be 6.1. Resonances at ~51.5 ppm and ~51.6 ppm representing the sulfoethoxy groups (-CH2SO3Na) are also present. A ¹H-NMR(DMSO-d₆) shows a resonance at ~7.9 ppm representing terephthalate aromatic hydrogens. Analysis by hydrolysis-gas chromatography shows that the mole ratio of incorporated ethylene glycol to incorporated propylene glycol is 1.42:1. The solubility is tested by weighing a small amount of material into a vial, adding enough distilled water to make a 35% by weight solution, and agitating the vial vigorously. The material is readily soluble under these conditions. A ∼9g sample of this material is further heated at 240°C in a Kugelrohr apparatus at about 0.5 mm Hg and maintained there for 80 minutes. A ¹³C-NMR(DMSO-d₆) shows no detectable peak for monoester at ~59.4 ppm. The peak for diester at ~63.2 ppm is at least 11 times larger than the monoester peak. The solubility of this material is tested as above and it is also found to be readily soluble under these conditions.
The modified polyamines useful as cotton soil release agents are suitably prepared by the following methods.

Detergent Composition Formulation

The detergent compositions according to the present invention can be in liquid, paste or granular forms. Such compositions can be prepared by combining the essential and optional components in the requisite concentrations in any suitable order and by an conventional means.
Liquid detergent compositions can be prepared by admixing the essential and optional ingredients thereof in any desired order to provide compositions containing components in the requisite concentrations. Liquid compositions according to the present invention can also be in "compact form", in such case, the liquid detergent compositions according to the present invention will contain a lower amount of water, compared to conventional liquid detergents.
The compositions of examples 12 to 24 do not lie within the Scope of Claim 1.
The compositions described in Table I are suitable for laundering colored fabrics in aqueous washing solution while providing excellent dye transfer inhibition benefits. Dye transfer inhibition performance provide by the combination of the PVNO or PVPI with the selected polyamine (PEI 1800 E7) is significantly better than if the dye transfer inhibiting polymers or the polyamine were used alone.
Concentrated built heavy duty liquid detergent compositions are prepared having the formulations set forth in Table III.
Granular compositions, for example, are generally made by combining base granule ingredients (e.g. surfactants, builders, water, etc.) as a slurry, and spray drying the resulting slurry to a low level of residual moisture (5-12%). The remaining dry ingredients can be admixed in granular powder form with the spray dried granules in a rotary mixing drum and the liquid ingredients (e.g. enzymes, binders and perfumes) can be sprayed onto the resulting granules to form the finished detergent composition. Granular compositions according to the present invention can also be in "compact form", i.e. they may have a relatively higher density than conventional granular detergents, i.e. from 550 to 950 g/l. In such case, the granular detergent compositions according to the present invention will contain a lower amount of "inorganic filler salt", compared to conventional granular detergents; typical filler salts are alkaline earth metal salts of sulfates and chlorides, typically sodium sulfate; "compact" detergents typically comprise not more than 10% filler salt.
The compositions described in Table IV are suitable for laundering colored fabrics in aqueous washing solution while providing excellent dye transfer inhibition benefits. Dye transfer inhibition performance provide by the combination of the PVNO or PVPI with the selected polyamine (PEI 1800 E7) is significantly better than if the dye transfer inhibiting polymers or the polyamine were used alone.

Method of Use

The present invention also provides a method for inhibiting dye transfer during laundering colored fabrics. Such a method employs contacting these fabrics with an aqueous washing solution formed from an effective amount of the detergent compositions hereinbefore described. Contacting of fabrics with washing solution will generally occur under conditions of agitation.
Agitation is preferably provided in a washing machine for good cleaning. Washing is preferably followed by drying the wet fabric in a conventional clothes dryer. An effective amount of the liquid or granular detergent composition in the aqueous wash solution in the washing machine is preferably from 500 to 7000 ppm, more preferably from 1000 to 3000 ppm.

Claims

A laundry composition comprising:

a) at least 0.01% by weight, of a dye transfer inhibition agent;

b) at least 0.1% by weight, of a water-soluble or dispersible, modified polyamine fabric surface modifying agent, said agent comprising a polyamine backbone corresponding to the formula:
having a modified polyamine formula V_(n+1)W_mY_nZ or a polyamine backbone corresponding to the formula:
having a modified polyamine formula V_(n-k+1) W_mY_nY'_kZ, 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:

ii) W units are backbone units having the formula:

iii) Y units are branching units having the formula:
and

iv) Y' units have the formula:

v) Z units are terminal units having the formula:
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)_xR¹-, -(R¹O)_xR⁵(OR¹)_x-, -(CH₂CH(OR²)CH₂O)_z-(R¹O)_yR¹(OCH₂CH(OR²)CH₂)_w-, -C(O)(R⁴)_TC(O)-, CH₂CH(OR²)CH₂-, preferably C₂-C₁₂ alkylene, C₃-C₁₂ hydroxyalkylene, C₄-C₁₂ dihydroxyalkylene, C₈-C₁₂ dialkylarylene, -(R¹O)_xR¹-, -(R¹O)_xR⁵(OR¹)_x-, -(CH₂CH(OH)CH₂O)_z(R¹O)_yR¹ (OCH₂CH(OH)CH₂)_w-, -CH₂CH(OR²)CH₂-, more preferably C₂-C₁₂ alkylene, C₃-C₁₂ hydroxyalkylene, C₄-C₁₂ dihydroxyalkylene, -(R¹O)_xR¹-, -(R¹O)_xR⁵-(OR¹)_x-, -(CH₂CH(OH)CH₂O)_z-(R¹O)_yR¹(OCH₂CH(OH)CH₂)_w-, most preferably C₂-C₁₂ alkylene, wherein R¹ is C₂-C₆ alkylene, preferably ethylene; R² is hydrogen, -(R¹O)_xB, preferably hydrogen; R³ is C₁-C₁₈ alkyl, C₇-C₁₂ arylalkyl, C₇-C₁₂ alkyl substituted aryl, C₆-C₁₂ aryl, C₁-C₆ alkyl, more preferably methyl; R⁴ is C₁-C₁₂ alkylene, C₄-C₁₂ alkenylene, C₈-C₁₂ arylalkylene, C₆-C₁₀ arylene, preferably C₂-C₁₂ alkylene, C₈-C₁₂ arylalkylene, more preferably, ethylene, butylene, 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)_rC(O)-, -CH₂CH(OH)CH₂-, -CH₂CH(OH)CH₂O(R¹O)_yR¹OCH₂CH(OH)CH₂-, preferably ethylene, -C(O)-, -C(O)NHR⁶NHC(O)-, -R¹(OR¹)_y-, -(CH₂CH(OH)CH₂O)_z(R¹O)_yR¹(OCH₂CH(OH)-CH₂)_w -, -CH₂CH(OH)CH₂-, 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)_pCO₂M, -(CH₂)_qSO₃M, -CH(CH₂CO₂M)CO₂M, -(CH₂)_pPO₃M, -(R¹O)_xB, -C(O)R³, preferably hydrogen, C₃-C₂₂ hydroxyalkyl, benzyl, C₁-C₂₂ alkyl, -(R¹O)_xB, -C(O)R³, -(CH₂)_pCO₂-M⁺, -(CH2)_qSO₃ ^-M⁺, -CH(CH₂CO₂M)-CO₂M, more preferably hydrogen, C₁-C₂₂ alkyl, -(R¹O)_xB, -C(O)R³, most preferably -(R¹O)_xB; B is hydrogen, C₁-C₆ alkyl, -(CH₂)_qSO₃M, -(CH₂)_p-CO₂M, -(CH₂)_q(CHSO₃M)CH₂SO₃M, -(CH₂)_q(CHSO₂M)CH₂-SO₃M, -(CH₂)_pPO₃M, -PO₃M, preferably hydrogen, C₁-C₆ alkyl, -(CH₂)_qSO₃M, -(CH₂)_q(CHSO₃M)-CH₂SO₃M, -(CH₂)_q(CHSO₂M)CH₂SO₃M, mixtures thereof, more preferably hydrogen, -(CH₂)_qSO₃M, 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; m has the value from 4 to 400; n has 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 I to 100; y has the value from 0 to 100; z has the value 0 or 1 wherein the polyamine comprises nitrogens totally or partially oxidized to N-oxides; and

c) the balance carrier and adjunct ingredients said adjunct ingredients are selected from the group consisting of builders, optical brighteners, bleaches, bleach boosters, bleach activators, enzymes, enzyme stabilizers, suds suppressors, dyes, perfumes, colorants, filler salts, hydrotropes, and mixtures thereof.
A laundry detergent composition according to claim 1, further comprising:

a) at least 3% by weight, of an anionic detersive surfactant said detersive surfactant is an anionic surfactant selected from the group consisting of alkyl alkoxy sulfate, alkyl sulfate, and mixtures thereof;

b) at least 2% by weight, of a nonionic detersive surfactant said detersive surfactant is a nonionic surfactant selected from the group consisting of alkyl alkoxylate, a fatty acid amide having the formula:
wherein R⁷ is C₇-C₂₂ alkyl, R⁸ is independently selected from the group consisting of hydrogen, C₁-C₄ alkyl, C₁-C₄ hydroxyalkyl, -(C₂H₄O)_jH, and mixtures thereof; wherein j is from 1 to 3; and mixtures of said surfactants;
A laundry detergent composition according to any preceding claim, comprising:

a) at least 10% by weight, of an anionic detersive surfactant selected from the group consisting of alkyl sulfate, alkyl alkoxy sulfate, and mixtures thereof

b) at least 3% by weight, of a nonionic detersive surfactant selected from the group consisting of polyhydroxy fatty acid amides, alcohol ethoxylates, and mixtures thereof;

c) optionally at least 1% by weight, of a bleach;

e) at least 0.5% by weight, of the water-soluble or dispersible, modified polyamine fabric surface modifying agent.
A laundry detergent composition according to any preceding claim, comprising:

a) at least 10% by weight, of an anionic detersive surfactant selected from the group consisting of alkyl sulfate, alkyl alkoxy sulfate, and mixtures thereof

b) at least 3% by weight, of a nonionic detersive surfactant selected from the group consisting of polyhydroxy fatty acid amides, alcohol ethoxylates, and mixtures thereof;

c) at least 0.05% by weight, of a dye transfer inhibition agent:

d) optionally at least 1% by weight, of a bleach;

e) at least 0.5% by weight, of the water-soluble or dispersible, modified polyamine fabric surface modifying agent.
A composition according to any of Claims 1-4 wherein said dye transfer inhibition agent is selected from the group consisting of:

a) polyamine N-oxide polymers having the formula:
wherein P is a polymerizable unit to which

i) an N-O group is attached;

ii) an N-O group is a member of the polymerizable unit;

iii) mixtures thereof;

A is a member selected from the group
and mixtures thereof, x is 0 or 1; and
R is aliphatic, ethoxylated aliphatic, aromatic, heterocyclic, alicyclic, and mixtures thereof, to which the

i) a nitrogen of the N-O group is attached;

ii) an N-O group is a moiety within R;

wherein the N-O moiety has the formula
wherein R₁, R₂, and R₃ are aliphatic, aromatic, heterocyclic, alicyclic groups, and mixtures thereof; x, y and z are 0 or 1; the nitrogen atom of the N-O group:

i) is attached to R₁, R₂, or R₃;

ii) is a unit within R₁, R₂, or R₃;

iii) is a unit that comprises a portion of the polymerizable unit P;

iv) is attached to the polymeric backbone comprising P units; and

v) mixtures thereof;

b) a polyethoxylated urethane compound formed by:

i) the reaction product of at least one water soluble polyether alcohol containing at least one functional hydroxyl group, a water insoluble organic polyisocyanate and an organic monoisocyanate;

ii) the reaction product of at least one water-soluble polyether alcohol, wherein the water soluble polyether alcohol contains at least one functional hydroxyl group, and an organic monoisocyanate;

iii) the reaction product of at least one water soluble polyether alcohol containing at least one functional hydroxyl group, a water insoluble organic polyisocyanate, an organic monoisocyanate, at least one polyhydric alcohol and at least one polyhydric alcohol ether;

iv) the reaction product of at least one water soluble polyether alcohol containing at least one functional hydroxyl group, a water insoluble organic polyisocyanate containing two isocyanate groups, and a monofunctional active hydrogen containing compound; and

v) a reaction product of at least one water soluble polyether alcohol containing at least one functional hydroxyl group, the water insoluble organic polyisocyanate containing at least three isocyanate groups. and a monofunctional active hydrogen containing compound;

provided that the polyether segment has a molecular weight of at least 200; the polyethoxylated urethane contains at least one hydrophobic group and at least one water soluble polyether segment; the sum of the carbon atoms in the hydrophobic groups are at least 4; and the total molecular weight is at least 300 to 60,000.

c) an acrylamide polymer comprising:

(i) an N-substituted acrylamide having the formula:
wherein R¹ is hydrogen, C₁-C₆ alkyl; R² and R³ are independently selected from the group consisting of hydrogen, methyl, ethyl, propyl, isopropyl, butyl, t-butyl, isobutyl; or R² and R³ together with the nitrogen, to which R² and R³ are attached, to form three to seven membered monoaromatic nitrogen heterocycles; and

ii) a vinyl monomer selected from the group consisting of C₁-C₆ alkyl (meth)acrylate, hydroxyalkyl (meth)acrylate, hydroxyaryl (meth)acrylate, alkoxyalkyl (meth)acrylate, polyalkoxyalkyl (meth)acrylales styrene, vinyltoluene, alkyl vinyl ethers, amino-substituted alkyl (meth)acrylates, amino-alkyl vinyl ethers, maleic anhydride, maleic acid, fumaric acid, itaconic acid, (meth)acrylic acid, and mixtures thereof;

wherein the acrylamide dye transfer inhibitors are formed from at least one acrylamide of an N-substituted acrylamide monomer, and optionally one or more vinyl monomers; and

d) polyamino acids.
A composition according to any of Claims 1-4 wherein the dye transfer inhibitor is selected from the group consisting of poly(4-vinylpyridine N-oxide), poly(2-vinylpyridine N-oxide), polyvinylpyrrolidone, copolymers of polyvinyl pyrrolidone and vinyl imidazole, and mixtures thereof.
A method for inhibiting dye transfer between dyed or colored fabric during laundering, said method comprising the step of contacting said dyed or colored fabric with a water-soluble or dispersible, bleach stable, modified polyamine fabric surface modifying agent of claim 1.
A method for inhibiting dye transfer between dyed or colored fabric during laundering, said method comprising the step of contacting said dyed or colored fabric with an aqueous solution of a laundry composition according to any of Claims 1-6.