CZ354798A3 - Detergent agents containing modified polyamines as inhibitors of dye transfer - Google Patents

Abstract

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 and a dye transfer inhibition agent. Also methods for laundering dye-containing colored fabrics in aqueous solutions comprising the fabric surface modifying polyamines useful in the present invention compositions.

Description

Technical field

BACKGROUND OF THE INVENTION The present invention relates to laundry detergent compositions which can be used to wash colored fabrics that contain a dye and which contain bleach-stable, modified polyamine additives that inhibit dye transfer between fabrics during laundry processes. The present invention also relates to methods for washing colored, dye-containing fabrics in aqueous solutions prepared from laundry detergent compositions comprising a fabric surface modifying polyamines of the invention.

SUMMARY OF THE INVENTION

One of the most stubborn and difficult issues of concern encountered in modern fabric washing practices is the tendency of some colored fabrics to release dye into the laundry solutions. Such a dye is then often transferred to other fabrics that are washed in the same aqueous wash solution.

One approach to coping with the problem of dye transfer in laundry processes is to form a complex or absorb volatile, dye-washed dyes, before these dyes have the opportunity to settle in the wash solution on other fabrics. For example, certain polymeric materials have been proposed as useful ingredients in laundry detergent compositions that can form complexes or absorb volatile dyes in aqueous laundry solutions. For example, U.S. Pat. U.S. Patent 4,545,919, Abel, issued October 8, 1985 discloses the use of carboxyl-containing polymers in fabric washing processes. DE-A-2 814 329, Waldhoff et al., Dated October 11, 1979, discloses the use of N-vinyloxazolidone polymers, and GB 1,348,212, Cracco et al., Dated March 13, 1974, discloses the use of 15-35% polyvinylpyrrolidone and acrylic nitrile or maleic anhydride in the laundry detergent. EP-A-265 257, Clements et al., Dated April 27, 1988, discloses laundry detergent compositions comprising an alkali metal carboxy metal carboxymethylcellulose, a vinyl pyrrolidone polymer and a polycarboxylate polymer.

Despite the prior art attempts to solve the problem of dye transfer during fabric washing, there remains a need to identify laundry detergents, detergent ingredients, and fabric washing methods that are particularly effective against dye transfer. It is therefore an object of the present invention to provide laundry detergent compositions containing selected ingredients that eliminate

AND

Or at least minimize dye transfer between fabrics when such compositions are used in fabric washing processes.

Surprisingly, it has now been found that a combination of certain dye transfer inhibitors and certain modified polyamines work to improve dye transfer inhibition. This unexpected result is provided by compositions that benefit a wide variety of fabric types, namely, cotton, synthetic, and mixed synthetic-cotton fabrics.

As a result of the stability of the modified polyamines of the present invention against bleaching agents, the presently disclosed methods and compositions provide for inhibiting dye transfer in dye products in the presence of traditional bleaching agents.

The processes or method of the invention are equally effective whether the laundry detergent compositions herein are solid or liquid. The solid laundry compositions may be in the form of granules, flakes or lump detergent compositions. Liquid detergents can have a wide range of viscosities and can include strongly concentrated, ready-to-pour detergents or weak fabric pretreatments.

The modified polyamines mentioned in this process are particularly compatible with other ingredients and additional ingredients in laundry laundry compositions.

It is a further object of the present invention to provide such particularly effective laundry detergents with inhibition of dye transfer either in granular or liquid form.

It is a further object of the present invention to provide a method for washing colored fabrics in aqueous laundry solutions which are prepared from the laundry detergent compositions of the present invention and which therefore comprise materials that eliminate or at least minimize dye transfer between the washed fabrics.

BACKGROUND OF THE INVENTION

In addition to the prior art cited, modified polyamines are disclosed in the following documents: U.S. Pat. No. 4,548,744, Connor, issued Oct. 22, 1985; U.S. Pat. No. 4,597,898, Vander Meer, issued July 1, 1986; U.S. Pat. No. 4,891,160, Vander Meer, issued January 2, 1990;

U.S. Pat. No. 4,235,735, Marco et al., issued Nov. 25, 1980; WO 95/32272, from Nov. 30, 1995; British Patent 1,537,288, issued Dec. 29, 1978; British Patent 1,498,520, issued January 18, 1978; German Patent DE 28 29 022, dated 10/01/1980; Japanese Kakai JP 06313271, from Apr. 27, 1994; and in EP 634,486, from January 18, 1995.

• ·

3. Summary of the Invention

The present invention relates to laundry detergent compositions which provide a particularly effective inhibition of dye transfer between fabrics when washed in aqueous solutions prepared from such laundry detergent compositions.

The detergent compositions of the present invention comprise:

(a) at least 5% by weight of a detersive surfactant;

b) at least 0.01% by weight of a dye transfer inhibiting agent;

(c) at least 0.1% by weight of a water-soluble or dispersible, modifiable polyamine, fabric surface modifying agent comprising an amine backbone poles corresponding to the general formula 1

H

II (1) [H ₂ NR] _{n + 1} - [NR] _m - [NR] _n -NH ₂ which has a modified polyamine of formula 2

V (n + i) W _m Y _n Z (2) or polyamine backbone corresponding to formula 3:

H R

II (3) [H ₂ NR] _n . _{k + 1} - [NR] _m - [NR] _n - [NR] _k -NH ₂ having a modified polyamine of formula 4

V _{(n. K +} i) W _m Y _n Y _'k Z (4) where k is less than or equal to n, said polyamine backbone prior to modification has a molecular weight greater than 200 daltons, wherein

(i) units V are terminal units having the general formulas 5,6,7:

E O

I x 't

ENR- (5) or EN ⁺ -R- (6) or ENR- (7)

(Ii) units W are backbone units having the general formula 8, 9, 10:

E O

I x 'τ

-NR- (8) or -N ⁺ -R- (9) or -NR- (10)

Ε Ε E • ·

• · (13)

(Iiiiii) units Y are branching units having the general formula 11,12,13

E

I ^x '

-NR- (11) or -N ⁺ -R- (12)

O

T or -N-Riv units are terminal units having the general formula 14, 15, 16:

E O

I X 'T

-NE (14) or -N ⁺ -E- (15) or -NE (16)

E; EE wherein the backbone bonding units R are selected from the group consisting of: C 2 -C 12 alkylene, C 3 -C 12 hydroxyalkylene, C 4 -C 12 dihydroxyalkylene, C ₈ -C ₁₂ dialkylarylene, - (R 6 x R ¹ -,

- (R ^ jxr ORV, - _(CH2 CH ^(OR2) CH2O) z (R ¹ O) y R ¹ (OCH 2 CH ^(OR2) CH2) w-, -C (O) (R ⁴⁾ r C (O -, -CH ₂ CH (OR ² ) CH ² - and mixtures thereof, wherein R ¹ is C 2 -C 3 alkylene and mixtures thereof; R is hydrogen, - (RO) XB and mixtures thereof; ₈ alkyl, C7 -C12 arylalkyl, C7 -C12 alkyl substituted aryl, _CO-Ci2 aryl, and mixtures thereof; R ⁴ is C1-C12 alkylene, C4-C12 alkenylene, C8-Cl2 arylalkylene, C-Cjo arylene, and mixtures R ⁵ is C 1 -C 12 alkylene, C 3 -C 12 hydroxyalkylene, C 4 -C 12 dihydroxyalkylene, C 8 -C ₁₂ dialkylarylene, -C (O) -, -C (O) NHR ⁶ NHC (O) -, -R 6 OR ¹ ) -, -C (O) (R ⁴ ) r C (O) -, -CH ² CH (OH) CH 2 -, -CH 2 CH (OH) CH 2 O (R ¹⁰ ) YR ¹⁰ OCH ² CH (OH) CH 2 - and mixtures thereof ; R ⁶ is C ₂ -C ₁₂ alkylene or C 6 -C 12 arylene; the E units are selected from the group consisting of hydrogen, C 1 -C ₂₂ alkyl, C 3 -C ₂₂ alkenyl, C 7 -C ₂₂ arylalkyl, C ₂ -C ₂₂ hydroxyalkyl, - (CH ₂ ) _P CO ₂ M, - (CH _{2) q} SO ₃ M, -CH (CH ₂ CO ₂ M) CO ₂ M, - (CH ₂ ) _p PO ₃ M, - (Ο Ο) _Χ -C, -C (O) R ³ and mixtures thereof; provided that when any nitrogen unit E is hydrogen, that nitrogen is also not an N-oxide; B is hydrogen, Ci-Co alkyl, - _{(CH2) q} SO3 M, - (CH _{2) p} CO ₂ M, - _{(CH2) q} (CHSO3M) _{CH2 SO3} M, - (CH _{2) q} (CHSO ₂ M) CH ₂ SO ₃ M, - (CH ₂ ) _p PO ₃ M, -PO ₃ M and mixtures thereof; M is hydrogen or a water-soluble cation in an amount sufficient to balance the charge; X is a water-soluble anion; m has a value of from 4 to 400; n is from 0 to 200; p is from 1 to 6; q is from 0 to 6; r has a value of 0 or was not; w is 0 or 1; x is from 1 to 100; y is from 0 to 100; z is 0 or 1; and

(d) balance carrier and additives.

It is a further object of the present invention to provide a bleach-stable polyamine dye transfer inhibitor and methods of preventing dye transfer from a laundry solution to laundry fabrics.

All percentages, ratios and proportions are by weight unless otherwise specified. All temperatures are in degrees Celsius (° C) unless otherwise specified. All cited documents are incorporated herein by reference.

• ·

Detailed Description of the Invention

The laundry detergent compositions of the present invention comprise:

(a) at least 5% by weight of a detersive surfactant;

b) at least 0.01% by weight of a dye transfer inhibiting agent;

c) at least 0.1% by weight of a water-soluble or dispersible, modifiable polyamine, fabric surface modifying agent of the invention; and

(d) balance carriers and additives.

Preferably, the 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 inhibiting agent;

d) at least 0.5% by weight of a water-soluble or dispersible, modifiable polyamine, fabric surface modifying agent of the invention; and

(e) balance carriers and additives.

More preferred laundry detergents according to 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 inhibiting agent;

d) optionally at least 1% by weight of a bleaching agent;

e) at least 0.5% by weight of a water-soluble or dispersible, modifiable polyamine, fabric surface modifying agent of the invention; and

(f) balance carriers and additives.

Even more preferred laundry 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 inhibiting agent;

d) optionally at least 1% by weight of a bleaching agent;

e) at least 0.5% by weight of a soil release polymer;

f) at least 0.5% by weight of a water-soluble or dispersible, modifiable polyamine, fabric surface modifying agent of the invention; and

· · · · · · · · · · · · · · · · · · · · · · · · · · · · · ·

(g) balance carriers and additives.

Most preferred detergent compositions of the present invention include:

(a) at least 5% by weight of an anionic detersive surfactant selected from the group consisting of alkyl sulfate, alkyl alkoxysulfate, 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 inhibiting agent;

d) optionally at least 1% by weight of a bleaching agent;

e) at least 0.5% by weight of a water-soluble or dispersible, modifiable polyamine, fabric surface modifying agent of the invention; and

(f) balance carriers and additives.

Preferred laundry compositions of the present invention comprise the following preferred materials:

Polymeric dye transfer inhibiting agents

The laundry detergent compositions of the present invention must contain from 0.01% to 10% by weight of certain types of polymeric dye transfer inhibiting agents. Preferably, the detergent compositions of the present invention comprise from 0.05% to 0.5% by weight of certain types of polymeric dye transfer inhibiting materials.

The selected polymeric dye transfer inhibiting materials may be certain polyamine

N-oxide polymers, certain copolymers of N-vinylpyrrolidone, N-vinylimidazole, polyethoxylated urethanes, acrylamide-containing polyamides, polyamino acids and mixtures thereof. Each of these polymer / copolymer types is described in more detail in the following section:

Polyamine N-oxide polymers

Suitable polyamine N-oxide polymers for use herein include units having the following general formula (17):

P

A _x (17)

Wherein P is a polymerizable unit to which an N-O group may be attached or the N-O group may form part of a polymerizable unit or the N-O group may be attached to both units; A is one of the following formulas 18, 19, 20, 21, 22:

O O

II (19) (20) (21) Italy (22)

N-C--C-O -S- -O- -Nx is 0 or 1; and R includes aliphatic, ethoxylated aliphatic, aromatic, heterocyclic or alicyclic groups or any combination thereof to which an N-O group may be attached or the N-O group is part of these groups.

The N-O group may be represented by the following general formulas 23, 24:

OO (R 1) _x - N - (R ₂ ) _y = N- (R _{0 x)}

I (23) (24) (R 1) z wherein R 1, R ₂ , R ₃ 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 may be attached to form part of any of the aforementioned groups. Further, the N-O group may be part of a polymerizable unit (P) or may be attached to a polymer backbone or a combination of both.

Suitable polyamine N-oxides wherein the N-O groups form part of the polymerizable unit include polyamine N-oxides wherein R is selected from aliphatic, alicyclic or heterocyclic groups. One class of these polyamine N-oxides comprises a 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 compound such as pyridine, pyrrole, imidazole, pyrrolidine, piperidine derivatives thereof.

Another class of polyamine N-oxides includes polyamine N-oxide groups wherein the nitrogen of the N-O group is attached to the R group. Other suitable polyamine N-oxides are 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 above, wherein R is an aromatic, heterocyclic or 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, e.g. pyridine, pyrrole, imidazole and derivatives thereof.

Another preferred class of polyamine N-oxides are polyamine oxides having the general formula given 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 where the R groups may be aromatic, e.g. phenyl. Any polymer backbone may be used as long as:

00 00 • 0 00 000 ·

0 000 00 · 0 · 0

000 0 <·· • 0 · «

The amine oxide polymer formed is water-soluble and has dye transfer inhibiting properties. Examples of suitable polymeric backbones are polyvinyl, polyalkylenes, polyesters, polyethers, polyamides, polyimides, polyacrylates and mixtures thereof.

The amine N-oxides useful in the detergent compositions of the present invention typically have an amine to amine N-oxide ratio of from 10: 1 to 1: 1,000,000. N-oxidation. Preferably, the ratio of amine to amine N-oxide is 3: 1 to 1: 1 000 000. The polymers useful in the detergent compositions of the present invention actually include random or block copolymers wherein one monomer type is an amine N-oxide and the other monomer type is N -oxide.

The amine oxide units of the polyamine N-oxides have a pKa < 10, preferably pKa < 7, even more preferably pKa < 6. The polyamine oxides can be obtained at almost any degree of polymerization. The degree of polymerization is not critical provided the material has the desired water solubility and dye suspension properties. Typically, the average relative molecular weight is within the range of from 500 to 1,000,000; more preferably from 1,000 to 500,000; most preferably from 5,000 to 100,000.

The most preferred polyamine N-oxide useful in the detergent compositions of the present invention is poly (4-vinylpyridine-N-oxide) having an average molecular weight of 50,000 and an amine to amine N-oxide ratio of 1: 4. This preferred material may be abbreviated as &quot; PVNO &quot;.

The polyamine N-oxides useful in the present invention may be synthesized by polymerizing the amine monomer and oxidizing the resulting polymer with a suitable oxidizing agent, or the amine oxide polymer may itself be polymerized to obtain the desired polyamine N-oxide. Such reaction schemes are known in the art and are within the skill of the art.

Copolymers of N-vinylpyrrolidone and N-vinylimidazole

The detergent compositions of the present invention may also employ a copolymer of N-vinylpyrrolidone and N-vinylimidazole (also abbreviated herein as "PVPVI"). It has been found that the copolymers of N-vinylpyrrolidone and N-vinylimidazole can provide excellent dye transfer inhibiting performance when used in the compositions of the present invention.

In a preferred embodiment, the copolymer of N-vinylpyrrolidone and N-vinylimidazole polymers has an average relative molecular weight ranging from 5,000 to 1,000,000, more preferably from 5,000 to 200,000. weight in the range of 5 00 to

4 · · 4

43 4 4 4 4

4 4 4 44 44 444

4 4 4 4

45 «4« ··

-9 4 4 • 4 4 4 4 4 4 4 4 4

The range of average relative molecular weight is given by light scattering as described by Barth J. H. G. and Mays J. W. in Chemical Analysis, Vol. 113, "Modern Methods of Polymer Characterization", the disclosure of which is incorporated herein by reference.

The copolymers of N-vinylpyrrolidone and N-vinylimidazole useful in the present invention may have a molar ratio of N-vinylimidazole to N-vinylpyrrolidone of from 1: 1 to 0.2: 1, more preferably from 0.8: 1 to 0.3: 1. more preferably 0.6: 1 to 0.4: 1. It will be understood that the copolymer of N-vinylpyrrolidone and N-vinyllimidazole may be either branched or linear.

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. Pat. Nos. 4,079,028 and 4,155,892, both incorporated herein by reference, describe in detail these polyurethane thickening agents which have been found to be useful as dye transfer inhibiting agents when incorporated into a composition of the invention in combination with the modified polyamines described hereinbelow.

Polyethoxylated urethane is prepared in a non-aqueous medium and is the reaction product of at least the reactants - (a) and (c), but optionally the polymer may include reactants (b) and (d) 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 an active hydrogen monofunctional compound and an organic monoisocyanate; and (d) at least one polyhydroxy alcohol or polyhydroxy alcohol ether.

The reactant (a), a polyether alcohol containing one or more functional hydroxyl groups, is typically an adduct of an aliphatic, cycloaliphatic or aromatic polyhydroxy compound, e.g. prepolymers. Optionally, the polyether alcohol may contain only one hydroxyl group, e.g., alkylpolyethylene glycol, alkylarylpolyethylene glycol, or a polycyclic alkylpolyethylene glycol, wherein the alkyl group contains 1 to 20 carbon atoms.

A suitable source of hydrophilic polyether polyol adducts is a polyalkylene glycol (also known as polyoxyalkylene diol), e.g., polyethylene glycol, polypropylene glycol, or polyalkylene glycol.

0

00 0 0 0 00 0 00 0 0 0 00 0 0000 polybutylene glycol having a molecular weight of 200 to 20 000. However, adducts of alkylene oxide and a monofunctional reactant, e.g., fatty alcohol, phenol or amine, or adducts of alkylene oxide and a difunctional reactant, e.g. alkanolamine (eg ethanolamine). Such adducts are also known as diol ethers and alkanolamine ethers.

Suitable compounds providing polyether segments also include amino-terminated polyoxyethylenes of Formula 25:

NH ₂ (CH ₂ CH ₂ O) _x H (25) wherein x has a value of from 10 to 200.

Reactant (c), a monofunctional hydrophobic organic compound, reacts with one or two terminal functional groups of the reaction product of reactants (a) and (b). The monofunctional hydrophobic organic compound includes both the monofunctional active hydrogen compound and the organic monoisocyanate.

For the purposes of the present invention, the term "monofunctional compound with active hydrogen" is defined as an organic compound having only one isocyanate-reactive group, which group contains an active hydrogen atom, where any other functional groups, if present, are generally non-reactive with isocyanate. These compounds include monohydroxy compounds such as alcohols, alcohol ethers; and monoamines; as well as polyfunctional compounds, provided that the compound is nonfunctional to isocyanates. Representative monofunctional compounds with active hydrogen include, for example, C 1 -C ₂ fatty alcohols such as methanol, ethanol, octanol, decanol, dodecanol, tetradecanol, hexadecanol and cyclohexanol; phenolic compounds such as phenol, cresol, octylphenol, nonyl- and dodecylphenol; alcohol ethers, e.g., ethylene glycol monomethyl, monoethyl and monobutyl ethers and analogous diethylene glycol ethers; alkyl and alkaryl polyether alcohols, e.g. straight or branched (C 1 -C ₂₂ ) alkanol / ethylene oxide and alkylphenol / ethylene oxide adducts.

The amino compounds may be in place of all or part of the monohydroxy compounds as hydrophobic monofunctional compounds with active hydrogen. Amino compounds include primary or secondary aliphatic, cycloaliphatic or aromatic amines, e.g. straight or branched chain alkylamines or mixtures thereof containing from 1 to 29 carbon atoms in the alkyl group. Suitable amines include n- and t-octylamine, n-dodecylamine, _C-CH2 or C ~ C for ₂ t-alkylamine mixtures, and secondary amines, e.g., N, N-dibenzylamine, Ν, Ν-dicyclohexylamine and Ν, Ν- diphenylamine. Amino compounds may contain more than one active hydrogen atom, provided that under normal reaction conditions it is only monofunctional to the isocyanate group. An example of such a compound is a primary amine.

• · · ········· - 11— ·· ··· · ···· ··········

In addition to the monofunctional compounds with active hydrogen, the reactant (c) may be a monoisocyanate. The monoisocyanate may include straight chained, branched C 8 -C 18 isocyanates and cyclic isocyanates, eg, from the above example, butyl isocyanate, octyl isocyanate, dodecyl isocyanate, octadecyl isocyanate and cyclohexyl isocyanate. These isocyanates may be used alone or in mixtures of two or more.

Organic polyisocyanates, reactant (b), include di- and triisocyanates, isocyanate-terminated adducts of such polyhydroxy alcohols and organic di- or triisocyanates, as well as isocyanate-terminated prepolymers of polyalkylene ether glycols and organic di- or triisocyanates. Although it is preferred that reactant (b) is an organic polyisocyanate, reactants containing one or more functional groups other than isocyanates are also suitable. The following are examples of monomers that can be used as reactant (b). These monomers may be used alone or in combination with one or more monomer reactants (b):

Hexamethylene diisocyanate (HDI)

1,6- and 2,4-tolylendiisocyanate (TDI)

4,4´-methylenediphenylisocyanate (MDI) aliphatic triisocyanate product of hydrolytic trimerization of 1,6-hexamethylenediisocyanate, sold under the brand DESMODUR N.

Polyisocyanates also include any polyfunctional isocyanates derived from the reaction of any of the preceding isocyanates and an active hydrogen compound having at least two functional groups so that at least one isocyanate group remains unreacted. Such isocyanates are equivalent to a chain-extending, isocyanate-terminated isocyanate / diol reaction product with a reactant containing at least two active hydrogen atoms, in a manner known in the synthesis of polyurethanes.

The isocyanates may contain any number of carbon atoms capable of providing the desired degree of hydrophobic character. Generally, 4 to 30 carbon atoms are sufficient, depending on the proportion of other hydrophobic groups and hydrophilic polyether in the product.

The reactant (d), polyhydroxy alcohol or polyhydroxy alcohol ether, can be used to terminate the isocyanate function or to link the isocyanate-terminated reaction intermediates. The polyhydroxy alcohol or polyhydroxy alcohol may be aliphatic, cycloaliphatic or aromatic and may be used alone or in mixtures of one or the other type or in mixtures of two types.

By appropriately selecting the reactants and reaction conditions, including the proportions and relative molecular weights of the reactants, a variety of polymer products can be obtained, which can be linear or have a complex structure. In summary, the reaction products formed include the following:

i) a reaction product of at least one water-soluble polyether alcohol comprising at least one hydroxyl-functional reactant (a), water-insoluble organic polyisocyanate reactants (b) and organic monoisocyanate reactants (c);

ii) the reaction product of reactants (a), wherein the water-soluble polyether alcohol comprises at least one functional hydroxyl group and an organic monoisocyanate reactant (c);

iii) a reaction product of reactants (a), reactants (b), organic monoisocyanate reactants (c), and reactants (d) selected from at least one polyhydroxy alcohol and polyhydroxyalcohol ether;

iv) a reaction product of reactants (a), a water-insoluble organic polyisocyanate reactant (b), comprising two isocyanate groups and a monofunctional active hydrogen-containing compound; and

v) the reaction product of the reactants (a), the water-insoluble organic polyisocyanate reactants (b), comprising at least three isocyanate groups and a monofunctional active hydrogen-containing compound.

Polysethoxylated urethane, useful as a dye transfer inhibiting agent, will generally inhibit dye transfer during the washing process if:

i) the polyether segment has a relative molecular weight of at least 200;

ii) the polyethoxylated urethane comprises at least one hydrophobic group and at least one water-soluble polyether segment;

iii) the total number of carbon atoms in the hydrophobic groups is at least 4; and iv) the total relative molecular weight is at least 300 to 60,000.

The polymers are prepared by techniques generally known for the synthesis of urethanes, preferably such that no unreacted isocyanates remain. Water should be excluded from the reaction as it would consume isocyanate functions.

If desired, the reaction may be carried out in a solvent medium to reduce the viscosity in such reactions that result in higher relative molecular weights of the products. Generally, a solvent is useful when a relative molecular weight of 30,000 or more is present.

The solvent should be inert to the isocyanate and be capable of dissolving the polyoxyalkylene reactant and the urethane product at the reaction temperature.

Φ ΦΦ · · · · ·

Φ φ

φφφ

The order of addition, proportion of reactants, and other reaction conditions, such as catalyst selection, may be varied to control geometry, relative molecular weight, and other product characteristics in accordance with known principles of polyurethane synthesis.

Polymers containing acrylamide

Water-soluble or water-dispersible acrylamide-containing polymers useful for preventing dye deposition are known for use as thickeners, rheological modifiers and dispersants.

In general, acrylamide-containing polymers are prepared by free-radical-initiated polymerization processes in the presence of a chain transfer agent. Acrylamide-containing polymers formed from (i) at least one acrylamide N-substituted acrylamide monomer and optionally (ii) one or more vinyl monomers are described as follows:

(i) acrylamide or N-substituted acrylamide having the general formula 26:

OR ²

CH ₂ = C-C-N (26)

R ¹ R ³ wherein R ¹ is hydrogen or C 1 -C 8 alkyl, preferably hydrogen or methyl; R ² and R ³ are independently selected from the group consisting of hydrogen, methyl, ethyl, propyl, butyl, t-butyl and isobutyl; or R ² and R ³ together with the nitrogen to which R ² and R ^{3 are} attached form three to seven membered monoaromatic nitrogen heterocycles.

(ii) Vinyl monomer, e.g., C 1 -C 6 alkyl (meth) acrylate, hydroxyalkyl (meth) acrylate, hydroxyaryl (meth) acrylate, alkyoxyalkyl (meth) acrylate, polyalkoxyalkyl (meth) acrylate, styrene, vinyltoluene, alkyl vinyl ethers, e.g. butyl vinyl ether amino-monomers such as amino-substituted alkyl (meth) acrylates, amino-alkyl vinyl ethers and maleic anhydride. Carboxylic acid substituted vinyl monomers, such as maleic acid, fumaric acid, itaconic acid, (meth) acrylic acid, or salts thereof, may also be used.

For the purposes of this invention, the term "(meth) acrylate" is defined as an acrylic or methacrylic acid or ester. Carboxylic acid salts substituted with vinyl monomer may be formed by partially or totally neutralizing the carboxylic acid substituted vinyl monomers with one or more conventional alkali metal or alkaline earth metal, ammonium, low molecular weight amine or low quaternary salt hydroxides.

The preparation of acrylamide polymers useful in the present invention is feasible by a variety of techniques known to those skilled in the art. A preferred method is radically initiated solvent polymerization in water or in a mixture of water and co-solvent. The co-solvent may be, for example, tert-butanol, monobutyl ether or 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 ether, acetone, methyl ethyl ketone, ethyl acetate, dimethylsulfoxide or tetrahydrofuran and also in mixtures of these solvents with or without water. Some of the foregoing solvents function as efficient chain transfer agents and will reduce the relative molecular weight of the product polymer.

Chain transfer agents may be added to the polymerization process in an amount of from 0.5 to 12% by weight, based on the total weight of the reactants added, to reduce the relative molecular weight of the polymer or to add hydrophobic groups to the polymer to form an associative thickener. Chain transfer agents useful for reducing the relative molecular weight may include, for example, mercaptans such as ethyl mercaptan, n-propyl mercaptan, n-amyl mercaptan, hydroxyethyl mercaptan, mercaptopropionic acid and mercaptoacetic acid; halogen compounds such as carbon tetrachloride, carbon tetrachloride; certain primary alkanols such as benzyl alcohol, ethylene glycol and diethylene glycol; certain secondary alcohols such as isopropanol; and a bisulfite such as sodium bisulfite. Chain transfer agents useful in forming an associative thickener are water insoluble and are preferably long chain alkyl mercaptans, e.g., 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 is dependent on the efficiency of the chain transfer agent. For example, if a less effective chain transfer agent such as sodium bisulfite is used, it may be necessary to use from 5 to 12% by weight of the chain transfer agent, but when an effective chain transfer agent such as mercaptan is used only 0.5 to 5% by weight of a chain transfer agent.

The relative molecular weight ranges of these polymers are from 2,000 to 300,000. Preferably, the relative molecular weight is from 20,000 to 60,000. The acrylamide-containing polymer is formed from 50 to 100% by weight of acrylamide or N-substituted acrylamide monomer (i) and 0. up to 50% by weight of vinyl monomer (ii). Acrylamide containing polymers particularly useful for preventing dye deposition are formed polymers wherein the acrylamide or N-substituted acrylamide monomer is dimethylacrylamide,

The 4 methyl acrylamide and acrylamide and mixtures thereof and the vinyl monomer is nonionic, for example hydroxyalkyl (meth) acrylate or alkyl (meth) acrylate.

Polyamino acids

Polyamino acids such as polyaspartic acid, polysuccinimide, and polyamino acid copolymers are useful in combination with the modified polyimines of the invention as dye transfer inhibitors. The polyamino acids useful in the present invention may be prepared by techniques known to those skilled in the art.

Modified polyamines: surface modifiers with increased benefit for inhibiting dye transfer

The modified polyamines of this invention are materials having surface-modifying properties. The consequence of these surprising properties is the ability of these materials to act in conjunction with dye transfer inhibiting agents while providing significantly increased dye transfer inhibition. The surface modifying dye transfer inhibiting agents of the present invention are water-soluble or dispersible, bleach-stable, modified polyamines containing polyamine backbones, which may be either linear or cyclic. The polyamine backbones may also comprise polyamine branching chains to a greater or lesser degree. In general, the polyamine backbones described in this invention are modified in such a way that each nitrogen of the polyamine chain is described accordingly in terms of a unit that is substituted, quaternized, oxidized or so combined.

For the purposes of the present invention, the term "modification" is defined as the replacement of a backbone-NH hydrogen atom with an E (substitution), quartemization of the backbone nitrogen (quartemized) or oxidation of the backbone nitrogen to an N-oxide (oxidized). The terms "modification" and "substitution" are used interchangeably when referring to procedures for replacing a hydrogen atom attached to a backbone nitrogen by an E unit. Quaternization or oxidation may occur under certain circumstances without substitution, but preferably the substitution is accompanied by oxidation or quaternization of at least one backbone nitrogen .

The linear or non-cyclic polyamine backbones containing the cotton soil release agents of the present invention have the general formula 1:

H (1) [H ₂ NR] _{n + 1} - [NR] _m - [NR] _n -NH ₂ • 9 9

9 9

9 9

999 999

9

The following spines contain, prior to modification, primary, secondary and tertiary amine nitrogens, joined by "linking" units R. The cyclic polyamine backbones contain the cotton soil release agents of the present invention having the general formula 3:

H R

II (3) [H ₂ NR] '. _{k +} i- [NR] _m - [NR] _n - [NR] _k -NH ₂ These backbones contain, prior to modification, primary, secondary and tertiary amine nitrogen, joined by "linking" units R.

For the purposes of this invention, primary amine nitrogen, folding backbone or branching chain, once modified, are defined as "terminal" units of V or Z. For example, if a primary amine group located at the end of the main polyamine backbone or branching chain having the formula

H ₂ NR 1 - (27) is modified according to the present invention, so it is further defined as a "terminal" unit V or simply unit V. However, for the purposes of the present invention some or all of the primary amine groups remain unmodified due to the limitations below. described below. These unmodified primary amine groups, based on their position in the backbone chain, remain "terminal" units. Similarly, if the primary amine group located at the end of the main polyamine backbone, having the general formula 28

-NH ₂ (28) is modified according to the present invention, further defined as a "terminal" unit Z, or simply a unit Z. This unit will remain unmodified due to the limitations described below.

Similarly, the secondary amine nitrogens, the backbone or the branching chain, once modified, are defined as the "backbone" W units. For example, if the secondary amine group, the main backbone and branching chain component of the present invention, having the general formula 29

H

I (29) - [N - R] - is modified according to the present invention, so it is subsequently defined as a "backbone" unit W or simply unit W. However, for the purposes of the present invention some or all of the secondary amine groups remain unmodified. These unmodified primary amine groups, based on their position in the backbone chain, remain "backbone" units.

In a similar manner, a tertiary amine nitrogen, folding backbone or branching chain, once modified, is hereinafter referred to as "branching" Y units. For example, if a tertiary amine group that is a branching point of either polyamine backbone or other branching chains or rings having the general formula 30

[N-R] - (30) is modified according to the invention, so it is subsequently defined as a "branching" unit Y or simply a unit Y. However, for the purposes of the invention some or all of the tertiary amine groups may remain unmodified. These unmodified primary amine groups, based on their position in the backbone chain, remain "branching" units. The R units associated with the V, W and Y nitrogen units that serve to join the polyamine nitrogen are described hereinbelow.

The final modified structure of the polyamines of the present invention can therefore be represented by the general formula 2

V _(n + 1) W _m YnZ (2) for linear polyamine dirt from cotton releasing polymers and of general formula 4

V _(n . K ₊ i) W _m Y 'Y' _to Z (4) for cyclic polyamine dirt from cotton releasing polymers. In the case of polyamines with rings, the Y 'unit of formula 31 serves

R

I (31)

- [N-R] as a branching point for the spine or branching ring. For each unit Y, there is a unit Y that has the formula 32

I (32)

- [N-R] which will form the ring connection point to the main polymer chain or branch. In a special case, where the spine is a complete ring, the polyamine spine has the general formula 33

H

I (33) Therefore, [H ₂ NR] _n - [NR] _m - [NR] _n contains no terminal unit Z and has the general formula 34

V _n . _k W _m Y _n Y ' _k (34) where k is the number of rings forming the branching units. Preferably, the polyamine backbone of the present invention contains no rings.

• * 9 • 9 • 9

In the case of non-cyclic polyamines, the ratio of index n to index m refers to the relative degree of branching. The fully unbranched linear modified polyamine of the present invention has the general formula 35:

VW _m Z (35) ie not equal to 0. The greater the value of n (the smaller the ratio M to n), the greater the degree of branching in the molecule. Typically, the value for m ranges from a minimum value of 4 to 4000, but larger values of m are also preferred, especially when the value of the index n is very low or nearly 0.

Each polyamine nitrogen, whether primary, secondary or tertiary, once modified according to the present invention, is further defined as a member of one of three general classes; simply substituted, quaternized and oxidized. Non-modified polyamine nitrogen units are classified in V, W, Y or Z units depending on whether they are primary, secondary or tertiary nitrogen. That is, for purposes of the present invention, the unmodified primary amine nitrogen is a unit of V or Z, the unmodified secondary nitrogen is a unit of W, and the unmodified tertiary amine nitrogen is a unit of Y.

Modified primary amino groups are defined as "terminal" V units, having one of three forms:

(a) simple substituted units of formula (5):

E-N-RI

E

(b) quartemised units of formula 6:

O

EX "\ ^t -R (6) wherein X is a suitable counter ion providing charge balance; and

(c) oxidized units having the general formula 7:

O

E-N-R

Modified secondary amine groups are defined as "backbone" W units, which have three forms:

• ·

(-19a) simply substituted units of the general formula (8):

—N — R—

E

(b) quartemised units of formula (9):

E

I —N ⁺ -RI

E wherein X is a suitable counter ion, providing charge balance; and

(c) oxidized units having the general formula (10):

O

T

-N-RI

E

(9)

Modified tertiary amine groups are defined as "branching" units of Y, which have three forms:

(a) simple substituted units of formula 11:

-N-R

(b) quartemised units of formula 12:

X '—N ⁺ -R (12) wherein X is a suitable counter ion providing charge balance; and

(c) oxidized units having the general formula 13:

O í

-N-R-

Certain modified primary amine groups are defined as "terminal" Z units, which have three forms:

(a) simple substituted units of formula 14:

-N-E (14)

(15)

(-20b) Quaternized units of formula 15:

wherein X is a suitable counter ion providing charge balance; and

(c) oxidized units having the general formula 16:

-N-E φφφ (17)

If any position on the nitrogen is unsubstituted from unmodified, it is understood that hydrogen will be substituted for E. For example, a primary amine unit containing one unit of E in the form of a hydroxyethyl group is a terminal unit of V having the formula 36:

(HOCH ₂ CH ₂ ) HN

For the purposes of the present invention, there are two types of chain terminal units, V units and Z units. The "terminal" Z units are derived from the terminal primary amino group of formula -NH ₂ . The non-cyclic polyamine backbones of the present invention contain only one Z unit, while the cyclic polyamines need not contain any Z unit. The "terminal" Z unit can be substituted by any of the E units described herein, except when the Z unit is modified to N-oxide. In the case where the nitrogen of unit Z is oxidized to an N-oxide, the nitrogen must be modified and therefore E cannot be hydrogen.

The polyamines of the present invention include backbone "linking" units R that serve to link backbone nitrogen atoms. The R units comprise units which for the purposes of the present invention are called "hydroxycarbyl R" units and "oxy R" units. "Hydroxycarbyl" R units are C ₂ -C ₁₂ alkylene, C 4 -C ₁₂ alkenylene, C ₂ -C ₁₂ hydroxyalkylene, wherein the hydroxyl group can occupy any position in the chain of the R unit except for the carbon atoms directly linked to the polyamine backbone nitrogen; C4-C ₂ dihydroxyalkylene wherein the hydroxyl moieties may occupy any two of the carbon atoms of the R unit chain except the carbon atoms directly connected to the polyamine nitrogens spine; C ₈ -C ₁₂ dialkylarylene, which for the purposes of the present invention are arylene groups having two alkyl substituent groups as part of a linking chain. For example, a dialkylarylene unit has the formula 37 or 38:

• · «· · · · · · · · · · · · · ·

9

9 9 9

99999999 99

-2199 99

9 9

998 9 99

although the unit need not be 1,4-substituted but may also be 1,2- or 1,3-substituted C 2 -C 12 alkylene, preferably ethylene and mixtures thereof, more preferably ethylene. "Oxy" R units include - (R ¹⁰ ) x R ⁵ (OR) x -, - (CH ₂ CH (OR ² ) CH ² O) z (R ¹⁰ ) y R ¹ (OCH ² CH (OR ² ) CH 2) w-- (R jxr ¹ -, -CH2CH ^(OR2) CH2-, and mixtures thereof. Preferred R units are C2-C12 alkylene, C3-C12 hydroxyalkylene, C4-C12 dihydroxyalkylene, C8-C12 dialkylarylene, - (R ¹ O ) xR ¹ -, - CH ² CH (OR ² ) CH 2 -, - (CH ² CH (OR ² ) CH ² O) _z (R ¹⁰ ) y R ¹ (OCH ² CH (OR ² ) CH 2) w - (R ¹⁰ ) x R ⁵ (OR ¹ ) x -, more preferably, R units are C 2 -C 12 alkylene, C 3 -C 12 hydroxyalkylene, C 4 -C 12 dihydroxyalkylene, - (R 6 x R ¹ -, - (CH ² CH (OR ² ) CH ₂ O) _z (R ¹⁰ ) y R) ¹ (OCH ² CH (OR ² ) CH ₂ ) _w - (R 1, R 1, R 2, OR 2 x) and mixtures thereof, more preferably the R units are C 2 -C 12 alkylene,

C3 hydroxyalkylene and mixtures thereof, most preferably are C2-C6 alkylene. The most preferred backbones of the present invention contain at least 50% R units that are ethylene.

The R ¹ units are C 2 -C 6 alkylene and mixtures thereof, preferably ethylene.

Λ 1

R is hydrogen and - (RO) _X B, preferably hydrogen.

R ³ is C 1 -C ¹⁸ alkyl, C 7 -C 12 arylalkylene, C 7 -C 12 alkyl substituted aryl, C 6 -C 12 aryl and mixtures thereof, preferably C 1 -C 12 alkyl, C 7 -C 12 arylalkylene, more preferably C 4 -C 12 alkyl, most preferably methyl. The R units serve as part of the E units described hereinafter.

R ⁴ is C 1 -C 12 alkylene, C 4 -C 12 alkenylene, C 5 -C 12 arylalkylene, C 6 -C 10 arylene, preferably C 1 -C 10 alkylene, C 5 -C 12 arylalkylene, more preferably C 2 -C 8 alkylene, most preferably ethylene or butylene.

R ⁵ is C 1 -C 12 alkylene, C 3 -C 12 hydroxyalkylene, C 4 -C 12 dihydroxyalkylene, C 8 -C 12 dialkylarylene, -C (O) -, -C (O) NHR ⁶ NHC (O) -, -C (O) (R) ⁴⁾ r C (O) -, -R ^ ^OR1) -CH2CH (OH) CH2O (R ¹ O) y R ¹ OCH 2 CH (OH) CH 2, -CH ₂ CH (OH) CH ₂ - R 5 is preferably ethylene, - C (O) -, -CCO 3 NH 4 HQO) -, -CH ₂ CH (OH) CH ₂ O (R ¹⁰ ) y R ¹⁰ OCH ₂ CH (OH) CH ₂ -, -R 4 OR ¹ ) -, -CH ₂ CH (OH) CH ₂ -, more preferably -CH ₂ CH (OH) CH ₂ -.

R ⁶ is C 2 -C 12 alkylene or C 6 -C 12 arylene.

Preferred "oxy" R units are further defined in terms of R ¹ , R ² and R ⁵ units. Preferred "oxy" R units comprise preferred R ¹ , R ² and R ⁵ units. The preferred cotton soil release agents of the present invention comprise at least 50% of the R ¹ units that are ethylene. Advantageous ·· 0 «00 · 00 ·· • 0 0 0 0 000 0 00 0 • 0 0 0 0 0000 • 0 0 0 0 0 0 000 000

R ¹ , R ² and R ⁵ units are combined with "oxy" R units to give preferred "oxy" R units as follows:

i) substitution of more preferred R ⁵ into ~ (CH2 CH2 O) x R ⁵ (O CH2 _{CH2) x} - gives - (CH ₂ CH ₂ O) _x CH _{2 CHOH-2} (OCH ₂ CH _{2) x} -.

ii) Substitution of preferred R ¹ and R ² to - (CH ² CH (OR ² ) CH ₂ O) _z (R ¹⁰ ) YR ¹⁰ (CH ² CH (OR ² ) CH ₂ ) _W - gives - (CH ₂ CH (OH) CH ₂ O) _z (CH ₂ CH _{2 O} ) _y CH ₂ CH ₂ O (CH ₂ CH (OH) CH ₂ ) _w -.

iii) Substitution of the preferred R ² into -CH ² CH (OR ² ) CH ² - gives -CH ₂ CH (OH) CH ₂ -.

Units E are selected from the group consisting of hydrogen, C 1 -C ₂₂ alkyl, C 3 -C ₂₂ alkenyl,

C ₇ -C ₂₂ arylalkyl, C ₂ -C ₂₂ hydroxyalkyl, - (CH ₂ ) _p CO ₂ M, - (CH 2) _q SO ₃ M, - (CH ₂ ) _p PO 3 M,

-CH (CH ₂ CO ₂ M) CO ₂ M, - (R ¹⁰ ) m _B n -C (O) R ³ , preferably hydrogen, C 2 -C ₂₂ hydroxyalkylene, benzyl, C 1 -C ₂₂ alkylene, JMB, -C (0) ^R3, - (CH2) PCC> 2 M, - (CH2) qSO3M, CH (CH2CO2M) CO2M, more preferably Cl-C22 alkylene, - (^ Ο) ΧΒ, -C (0) R ³ , - (CH 2) _p CO ₂ M, - (CH ₂ ) _q SO ₃ M, -CH (CH ₂ CO ₂ M) CO ₂ M, most preferably C 1 -C ₂₂ alkylene, - (R 6B and -C (0) R ^3rd When no nitrogen to no modification or substitution, so hydrogen atom will remain as the moiety representing E.

The unit does not contain a hydrogen atom if the V, W or Z units are oxidized, i.e., the nitrogen is N-oxides. For example, the backbone or branch chains do not contain units of the following general formulas 39,40,41:

O

T — N — R or (39)

H

O O t ΐ

Η — N — R or —N — H

I (41)

Η H

In addition, the E units do not contain carbonyl groups directly bonded to the nitrogen atom if the V, W or Z units are oxidized, i. Nitrogens are N-oxides. According to the present invention, the -C (O) R ^{3 group of} the E unit is not bound to the N-oxide modified nitrogen, i. that there are no N-oxide amides having the general formula 42,43,44:

O

T

-N-R

C = O

R ³

O O

II τ or R ³ —C — N — R or (42) E (43)

O O

NCR ³ or combinations thereof.

(43) · *

-2300 ·· • 0 · 0

0 0 0

0 0 0 0 0 0 0 0

B is hydrogen, C 1 -C ₆ alkyl, - (CH ₂ ) _q SO ₃ M, - (CH ₂ ) _p CO ₂ M, - (CH ₂ ) _q (CHSO ₃ M) CH ₂ SO ₃ M, - (CH ₂ ) _q (CHSO ₂ M) CH ₂ SO ₃ M, - (CH ₂ ) _p PO ₃ M, -PO ₃ M, preferably hydrogen, - (CH ₂ ) _q SO ₃ M, - (CH ₂ ) _q (CHSO ₃ M) CH ₂ SO ₃ M, - (CH _{2) q} (CHSO ₂ M) CH ₂ SO ₃ M, more preferably hydrogen or a group (CH _{2) q} SO ₃ M.

M is hydrogen or a water-soluble cation in an amount sufficient to achieve a charge balance. For example, the sodium cation satisfies ~ (CH ₂ ) _P CO ₂ M i - (CH ₂ ) _q SO ₃ M equally and therefore results from - (CH ₂ ) _p CO ₂ Na and - (CH ₂ ) _q SO ₃ Na. More than one monovalent cation (sodium, potassium, etc.) may be combined to satisfy the chemical charge balance. However, a divalent cation may charge more than one anionic group or more than one monovalent cation may be needed to balance the charge of polyanionic radicals. For example, the - (CH ₂ ) _p PO ₃ M group substituted with sodium atoms has the formula - (CH ₂ ) _p PO ₃ Na ₃ . A divalent cation, such as calcium (Ca ²⁺ ) or magnesium (Mg ²⁺ ), may be substituted for or combined with other suitable monovalent water-soluble cations. Preferred cations are sodium and potassium, more preferably sodium.

X is a water-soluble anion such as chlorine (Cl), bromine (Br) and iodine (Γ) or X may be a negatively charged radical such as sulfate (SO4 ² ) methsulfate (CH ₃ SO ₃ ).

The indexes in the formulas have the following values: p has a value of 1 to 6; q is from 0 to 6; r is 0 or 1; w is 0 or 1; x is from 1 to 100; y is 0 to 100; z is 0 or 1; k is less than n, typically k is less than 20; m has a value of from 4 to 400; n is from 0 to 200; m + n has a value of at least 5.

Preferred dye transfer inhibiting agents of the present invention include polyamine backbones wherein less than 50% of the R groups contain "oxy" R groups, preferably less than 20%, more preferably less than 5%, most preferably R units contain no "oxy" R units.

The most preferred dye transfer inhibiting agents of the present invention that contain no "oxy" R units include polyamine backbones wherein less than 50% of the R groups contain more than 3 carbon atoms. For example, ethylene, 1,2-propylene and 1,3-propylene contain 3 or less carbon atoms and are preferred "hydrocarbyl" R units. Ie. when the backbone units R are C ₂ -C ₁₂ alkylene, preferably it is C ₂ -C ₃ alkylene, most preferably ethylene.

The dye transfer inhibiting agents of the present invention include modified homogeneous and inhomogeneous polyamine backbones where 100% or less of the -NH units are modified. For the purposes of this invention, the term "homogeneous polyamine backbone" is defined as a polyamine backbone having R units that are the same (eg, all are ethylene). However, this definition of homogeneity does not exclude polyamines containing other external units containing the polymer backbone that are present as a result of the artifact of the chosen chemical method

-24 ·. · «· 24 24 24 24 24 synté.. Zy zy zy zy.... For example, it is known to those skilled in the art that ethanolamine can be used as an "initiator" in the synthesis of polyethyleneimines, therefore a polyethyleneimine sample containing one hydroxyethyl group resulting from the polymerization of the "initiator" would be considered to contain a homogeneous polyamine backbone. The polyamine backbone containing all ethylene units R, where no branching units Y are present, is a homogeneous backbone. The polyamine backbone, containing all ethylene units R, 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 composites of different lengths of R units and types of R units. For the purposes of this invention, a mixture of "hydroxycarbyl" and "oxy" R units is not necessary to provide a non-homogeneous spine. Proper handling of these "R unit chain lengths" will provide the chemist with the ability to modify the solubility and fabric substantivity of the cotton soil release agents of the present invention.

Preferably, the cotton soil release polymers of the present invention comprise homogeneous polyamine backbones which are wholly or partially substituted with polyethylene groups, wholly or partially quaternized amines, wholly or partially oxidized to N-oxides, and mixtures thereof. However, not all amino acids of the main chain must be modified in the same way, the choice of modification being left to the specific needs of the chemist. The degree of ethoxylation is also determined by the specific requirements of the chemist.

Preferred polyamines that contain the backbone of the compounds of this invention are generally polyalkyleneamines (PAA), polyalkylenimines (PAI), preferably polyethyleneamines (PEA), polyethyleneimines (PEI) or PEA or PEI linked to groups having longer R units than the starting PAA, PAI, PEA or PEI. A common polyalkyleneamine (PAA) is tetrabutylenepentaamine. PEAs are obtained by reaction of ammonia and ethylene dichloride followed by fractional distillation. Commonly obtained PEAs are triethylenetetramine (TETA) and teraethylenepentaamine (TEPA). Higher than pentaamines; hexaamines, heptaamines, octaamines and optionally nonaamines, similarly derived mixtures, do not appear separable by distillation and may include other materials such as cyclic amines and especially piperazines. Cyclic amines with side chains in which nitrogen occurs may also be present. See U.S. Pat. No. 2,792,372, Dickinson, issued May 14, 1957, which describes the preparation of PEA.

Preferred amine polymer backbones comprise R units that are C ₂ alkylene (ethylene) units, also known as polyethylenimines (PEI's). Preferred PEIs have at least:

-25 · 4 · 4 · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · to n is at least 4: 1, but PEI having a m to n ratio of 2: 1 is most preferred. Preferred spines have the general formula 45 before modification:

H

II (45) [H ₂ NCH ₂ CH ₂ ] n - [NCH ₂ CH ₂ ] _m - [NCH ₂ CH ₂ ] _n -NH ₂ where m and n are the same as defined above. Preferred PEIs, prior to modification, will have a relative molecular weight of greater than 200 daltons.

The proportions of primary, secondary and tertiary amine units in the polyamine backbone, especially in the case of PEI, will vary depending on the preparation. Each hydrogen atom attached to each nitrogen of the polyamine backbone represents a potential site for subsequent substitution, quaternization, 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 US Patents 2,182,306, Ulrich et al. from 05.12.1939; U.S. Pat. No. 3,033,746, Mayle et al., issued May 8, 1962; U.S. Pat. No. 2,208,095, Esselmann et al., issued July 16, 1940; U.S. Pat. No. 2,806,839, Crowther, issued Sep 17, 1957; and U.S. Pat. No. 2,553,696, Wilson, issued May 21, 1951; all hereby incorporated by reference.

Examples of modified cotton soil release polymers of the present invention containing PEI are shown in Formulas I-IV:

Formula I illustrates a cotton soil release polymer comprising a PEI backbone wherein all substitutable nitrogen is modified by replacing the hydrogen with a polyoxyalkyleneoxy unit - (CH ₂ CH ₂ O) ₇ H:

NKQMJVOMlh

NTrBjVHjOMÍ],

latíCHphK

(Formula I)

-26 • 4 44 44 • 4 · 4 4 44

4 4 4 4

4 4 4

4 * 44444 »» 4 • 44 44

4444

4 4 4 4

4,444 444 • 4 4

444 44 44

This is an example of a cotton soil release polymer that is fully modified by one type of group.

Formula II depicts a cotton soil release polymer containing a PEI backbone wherein all substitutable primary amine nitrogens are modified by replacing hydrogen with a polyoxyalkyleneoxy unit - (Ο ^ ΟΙΕΟ ^ Η), then the molecule is modified by subsequent oxidation of all oxidizable primary and secondary nitrogen to N-oxides and the soil release agent has the formula cotton nacHtCM of O, »} '^ py ťxtUjťUjO Hj? s 1 s 1 i i t * IIK (A? rT' _L {f J ^^ NÍLQIjCIWIL kN · ^u k ^ MOťjai.owKii

T o

N í ň

OOLOLCHN (Formula II)

Formula III depicts a cotton soil release polymer comprising a PEI backbone wherein all substitutable backbone hydrogen atoms are substituted and some backbone amine units are quaternized. The substituents are polyoxyalkylenoxy units - (CH ₂ CH ₂ O) 7 H, or methyl groups. The modified cotton soil-release PEI polymer has the formula [HtOCKtCHMN hKQIjCUjQhH cr

CH 3 ch, ch / zi +

Cl

CWi at,

L ^Cl 'a>, a * L _a , (Formula III)

-2700 00 00 · 00 ·· • 00 «« 0 00 0 0 0 0 • · 0 0 · 0000 • 0 0 0 0 0 0 * 00 000

0 0 0 0 0 0 0000 0000 91 · 00 · 0 ··

Formula IV illustrates a cotton soil release polymer comprising a PEI backbone where the backbone nitrogen is modified by substitution (i.e. - (CH ₂ CH ₂ O) 7 H by a methyl group), quaternized, oxidized to N-oxides, or combined. The resulting cotton soil release polymer has the formula

IkOClHiOhfckN.

CH, _ø Nt <H, _ø o), k

1} KOCH, CH,>,]] N

GI iCa <TIUI, H ^K 'Cl

o t

NKCHjh (Formula IV)

In the above examples, not all unit class nitrogen contains the same modification. The present invention allows a chemist to have a portion of the secondary amine nitrogens being ethoxylated while the other secondary amine nitrogens are oxidized to N-oxides. This also applies to primary amine nitrogen, so the chemist may choose to modify all or part of the primary amine nitrogen by one or more substituents prior to oxidation or quaternization. Any possible combination of the E groups may be substituted on the primary and secondary amine nitrogens, except as described below.

Method of use

The present invention relates to methods providing the benefits of inhibiting dye transfer for dyed or colored fabrics. The method comprises the step of contacting said dyed or dyed fabric with a water-soluble or dispersible, bleach-stable, modified amine poles with a surface modifying agent comprising a polyamine backbone corresponding to the general formula 1:

H

I [HzN-RUHN-RJmHN-R1] which has a modified polyamine of formula 2 in _{(n + 1)} w _m Y 2 or a polyamine backbone corresponding to the formula:

(2)

(3)

-28 [H ₂ NR] _n . _{k +} i- [NR] _m - [NR] n - [NR] r -NH ₂ having a modified polyamine of formula 4

In _(n - _{k + 1)} W _m Y 'Y' _k Z (4) where k is less than or equal to n, this polyamine backbone prior to modification has a relative molecular weight greater than 200 daltons, where

(i) units V are terminal units having the general formula 5, 6, 7:

X ’

ENR- (5) or E-N ⁺ -R- (6) or EN-RI I

E E E (ii) units W are backbone units having the general formula 8, 9,10:

(7)

X

-NR- (8) or -N ⁺ -R- (9)

E or -N-R- (10) (iii) Y units are branching units having the general formula 11,12,13:

I ^x '

-NR- (11) or -N ⁺ -R- (12) or

O

T

-N-R- (13), and iv) Z units are terminal units having the general formula 14,15,16:

-NE (14) or -N ⁺ X ';

O

T

-N-E

E;

wherein the backbone bond units R are selected from the group consisting of C ₂ -C ₁₂ alkylene, C ₄ -C ₁₂ alkenylene, C ₃ -C ₁₂ hydroxy alkylene, C ₄ -C ₁₂ dihydroxyalkylene, C ₈ -C ₁₂ dialkylarylene, - ( jxr R ¹ -, - (R ¹ O) x R ⁵ (OR ¹⁾ x - _(CH2 CH ^(OR2) CH2O) z (R ¹ O) y R ¹ (OCH ₂ CH (OR ²⁾ CH 2) w-, -C (O) (R ⁴ ) r C (O) -, -CH ₂ CH (OR ² ) CH ₂ - and mixtures thereof, wherein R ¹ is a C 2 -C 6 alkylene group and mixtures thereof, R ² is hydrogen, - (R'O) XB group and mixtures thereof R ³ is C 1 -C 18 alkyl, C 7 -C 12 arylalkyl, C 7 -C 12 alkyl substituted aryl, C 6 -C 12 aryl and mixtures thereof R ⁴ is C 1 -C 12 alkylene, C ₄ -C ₁₂ alkenylene, C ₈ -C ₁₂ arylalkylene, C ₆ -C 10 arylene and mixtures thereof, R ⁵ is C 1 -C ₁₂ alkylene, C ₃ -C ₁₂ hydroxyalkylene, C ₄ -C ₁₂ dihydroxyalkylene, C ₈ -C ₁₂ dialkylarylene, -C (O) -, -C (O) NHR ⁶ NHC (O) -, -R 4 OR ¹ ) -, - ··· ···· ·· ··· ··

C (O) (R ⁴ ) _r C (O) -, -CH ₂ CH (OH) CH ₂ - -CH ₂ CH (OH) CH ₂ O (R ¹⁰ ) y R ¹⁰ OCH ² CH (OH) CH ₂ - a mixtures thereof; R ⁶ is C ₂ -C _i2 alkylene or _Ce-Ci2 arylene; the E units are selected from the group consisting of hydrogen, C 1 -C ₂₂ alkyl, C ₃ -C ₂₂ alkenyl, C ₇ -C ₂₂ arylalkyl, C ₂ -C ₂₂ hydroxyalkyl, - (CH ₂ ) _P CO ₂ M, - ( CH ₂ ) qSO ₃ M, -CH (CH ₂ CO ₂ M) CO ₂ M, - (CH ₂ ) _p PO ₃ M, - (R 2B, -C (O) R ³ and mixtures thereof; any unit E of nitrogen is hydrogen, so that nitrogen is also not an N-oxide; B is hydrogen, C 1 -C 6 alkyl, - (CH ₂ ) _q SO ₃ M, - (CH ₂ ) _P CO ₂ M, - (CH ₂ ) _p PO ₃ M, - (CH ₂ ) _q (CHSO ₃ M) CH ₂ SO ₃ M, - (CH ₂ ) _q (CHSO ₂ M) CH ₂ SO ₃ M, -PO ₃ M group and mixtures thereof;

M is hydrogen or a water-soluble cation in an amount sufficient to achieve a charge balance; X is a water-soluble anion; m has a value of from 4 to 400; n is from 0 to 200; p is from 1 to 6; q is from 0 to 6; r is 0 or not; w is 0 or 1; x is from 1 to 100; y is from 0 to 100; z has a value of 0 or 1. These methods may also use the aqueous detergent solution of the present invention.

The methods of the invention are suitable for use when the treated fabric also needs bleaching. Compositions containing bleaching agents typically used to clean white fabrics are compatible with the fabric surface modifying agents of the present invention.

The present invention also provides a method for washing colored fabrics wherein little or no dye transfer occurs. Such a method utilizes contacting the fabrics with an aqueous wash solution formed from an effective amount of the detergent compositions described above. The contacting of the fabrics with the wash solution is usually done under agitation conditions.

Cleaning surfactants

The cleaning surfactants suitable for use in the present invention are cationic, anionic, nonionic, amphoteric, zwitterionic and mixtures thereof, and are further described herein. The laundry detergent composition may be in any suitable form, for example, in the form of high-density liquids, light liquids or other pourable forms, in addition to granules or compositions in lump form. The cotton soil release polymers of the present invention can be formulated into any cleaning matrix selected by a chemist.

The laundry detergent compositions of the present invention may further comprise at least 0.0% 1%, preferably at least 0.1%, more preferably at least 1% by weight of the following cleaning surfactants. Non-limiting examples of surfactants useful herein typically at levels of 1% to 55% by weight include conventional Cn-C 18 alkylbenzene sulfonates ("LAS") and primary, branched chain and random C 10 -C ₂₀ alkylsulfates ("AS"), C 10- Cis secondary (2,3) -alkyl sulfates of formula

_{CH3 (CH2) X} (CHSO ₃ -M ⁺⁾ CH3 and CH3 (CH2) y (CHOSO3-M ⁺⁾ CH2CH3 where x and (y + 1) are integers of ♦ * · ·· · ♦ • «• · · ·

-30 at least 7, preferably at least 9, and M is a water-soluble cation, especially sodium, unsaturated sulfates such as oleyl sulfate, C 10 -C 18 alkyloxy alkoxysulfates ("AE _X S"; especially EO 1-7 ethoxysulfates), C 10 -C 18 alkylalkoxycarboxylates (especially EO) 1-5 ethoxycarboxylates), C 10 -C 18 glycerol ethers, C 10 -C 18 alkyl polyglycosides and their corresponding sulfated polyglycosides and C 12 -C 18 alpha-sulfonated fatty acid esters. If desired, conventional nonionic and amphoteric surfactants such as C12-C18 alkyl ethoxylates ("AE"), including so-called narrow alkyl ethoxylates and C6-C12 alkylphenolalkoxylates (especially ethoxylates and mixed ethoxy / propoxy), can also be incorporated into the resulting compositions, C12-C18 betaines and sulfobetaines ("sultains"), C10-C18 amine oxides and the like. C 10 -C 18 N-alkyl polyhydroxy fatty acid amides may also be used. Typical examples include C12-C18 methylglucamides. See WO 9,206,154. Other sugar-derived surfactants include N-alkoxypolyhydroxy fatty acid amides, e.g., C 10 -C 18 N- (3-methoxypropyl) glucamide. N-propyl to N-hexyl C12-C18 glucamides can be used for low soap suds formation. Conventional C10-C20 soaps can also be used. If high soap suds are desired, branched soaps of C10-C16 can be used.

Mixtures of anionic and nonionic surfactants are particularly useful. Other conventional surfactants are listed in standard assays.

The anionic component of the surfactant

The detergent compositions herein preferably comprise at least 5% by weight of the anionic surfactant, preferably from 5% to 60% by weight of the anionic surfactant component. More preferably, the compositions comprise from 10% to 40% by weight of the anionic surfactant component.

A substantial part, ie. at least 50% and more preferably at least 75% of the anionic surfactant component will be ethoxylated alkyl sulfate surfactants. Such ethoxylated alkyl sulfates correspond to the general formula 46:

R ² -O- (CH ₂ H ⁴ O) n -SO ₃ M (46) wherein R ² is C 10 -C 20 alkyl, n is from 1 to 20 and M is a salt-forming cation. Preferably, R ^{2 is} C 12 -C 18 alkyl, n is from 1-6 alkyl; and M is sodium, potassium, ammonium, alkylammonium or alkanolammonium. Most preferably R ² is C ₁₂ -C ₁₆ , n is from 1 to 6 and M is sodium. These materials, also known as alkyl ether sulfates, may provide particularly desirable benefits for dye transfer inhibition when used in combination with the specific dye transfer inhibiting polymeric agents described herein.

• · • i t

it it

Alkyl ether sulfates will generally be used in the form of mixtures containing different R ₂ chain lengths and varying degrees of ethoxylation. Often, such compositions will inevitably also contain some non-ethoxylated alkylsulfate materials, i.e. surfactants of the above ethoxylated alkylsulfate formula where n is 0. Such nonethoxylated alkylsulfate anionic surfactants tend to be less effective than ethoxylated alkylsulfates in inhibiting transmission in the context of with the compositions of the invention. Therefore, it is important that the anionic surfactant components of the present invention contain no more than 50% by weight of the components of the unethoxylated alkyl sulfate materials. Preferably, no more than 25% by weight of the anionic components of the surfactant component will contain unethoxylated alkyl sulfates.

In addition to the essentially used ethyloxylated alkyl sulfate surfactants, the anionic surfactant component of the compositions herein may also contain additional optional anionic surfactants, provided that such optional optional materials are compatible with the other ingredients of the composition and do not substantially adversely affect performance of the composition, e.g. inhibiting dye transfer or stability of the composition.

Optional anionic surfactants that may be employed include generally carboxylate types of anionic agents. Carboxylate types of anionic substances include fatty acids such as C 10 -C 18 soaps, C 10 -C 18 alkyl alkoxycarboxylates (especially EO 1 to 5 ethoxylates) and C 10 -C 18 sarcosinates, particularly oleyl sarcosinates.

One common type of anionic surfactant that should not be used in the anionic surfactant component of the present invention comprises sulfonated anionic agents, namely alkylbenzene sulfonates. Non-bleach activating sulfonated anionic surfactants, such as linear alkyl benzene sulfonates (LAS), have been found to tend to interfere with the effectiveness of the polymeric dye transfer inhibiting agents used in the present invention to reduce dye transfer between fabrics during fabric washing. Therefore, the anionic components of the detergent surfactant of the present invention should be substantially free of these allylbenzene sulfonate anionic surfactant materials.

Nonionic surfactant components

The detergent compositions herein also preferably comprise from 5% by weight of the nonionic surfactant, preferably from 1% to 20% by weight of the nonionic surfactant component. More preferably, the compositions will comprise from 2% to 10% by weight of the nonionic surfactant component.

ί

-32999 9,999

The nonionic surfactant component essentially comprises one and preferably both of two specific types of nonionic surfactant materials. They are polyhydroxy fatty acid amides and alcohol ethoxylates.

1) Polyhydroxy fatty acid amides

Other preferred nonionic surfactants are polyhydroxy fatty acid amides having the formula 47:

AB ⁸ , II I

R ⁷ -CNQ (47) wherein R ⁷ is C 5 -C 31 alkyl, preferably straight chain C 7 -C 19 alkyl or alkenyl, more preferably C 9 -C 17 alkyl or alkenyl, most preferably C 11 -C 15 alkyl or alkenyl or a mixture thereof; R ⁸ is selected from the group consisting of hydrogen, C 1 -C 4 alkyl, C 1 -C 4 hydroxyalkyl, preferably methyl, ethyl, more preferably methyl, Q is a linear alkyl chain polyhydroxyalkyl group with at least 3 hydroxyl groups directly attached to the chain or some an alkoxylated derivative thereof; preferably alkoxy is ethoxy or propoxy or a mixture thereof. Preferably, Q is derived from a reducing sugar in a reductive amination reaction. More preferably, Q is a glycityl group. Suitable reducing sugars include glucose, fructose, maltose, lactose, galactose, mannose, and xylose. Concentrated dextrose corn syrup, concentrated fructose corn syrup and concentrated maltose corn syrup, as well as the individual sugars listed above, can be used as raw materials. These corn syrups can give a mixture of sugar components for Q. It is to be understood that in no case is it intended to exclude other suitable raw materials. More preferably, Q is selected from the group consisting of -CH 2 (CHOH) _n CH ₂ OH,

-CH ₂ (CHOH) (CHOH) _n CH ₂ OH, -CH ₂ (CHOH) ₂ (CHOR ') (CHOH) CH ₂ OH and their alkoxylated derivatives, wherein n is an integer from 3 to 5 inclusive, and R is hydrogen or a cyclic or aliphatic monosaccharide. The most preferred substituents for Q are glycityls wherein n is 4, especially -CH ₂ (CHOH) ₄ CH ₂ OH.

R CO-N = can be, for example, cocoamide, stearamide, oleaamide, lauramide, myrsitamide, caprinamide, palmitamide, taloamide, etc.

R ⁸ can be, for example, methyl, ethyl, propyl, isopropyl, butyl, 2-hydroxyethyl or 2-hydroxypropyl.

Q may be 1-deoxyglucityl, 2-deoxyfructityl, 1-deoxymaltityl, 1-deoxygalactityl, 1-deoxymannityl, 1-deoxymaltotriotityl etc.

• · · · · · · φ · φ · φ ·

-33φ φφφ • · ·

A particularly desirable surfactant of this type for use in the compositions of this invention is an alkyl-N-methylglucomide, a compound of the above formula wherein R ⁷ is alkyl (preferably C 1 -C ⁸ ), R ⁸ is methyl and Q is 1-deoxyglucityl.

Methods for preparing polyhydroxy fatty acid amides are known and can be found, for example, in U.S. Pat. No. 2,965,576 to Wilson and U.S. Pat. No. 2,703,798, Schwartz, incorporated herein by reference. The materials themselves and their preparation are also described in more detail in U.S. Pat. No. 5,174,937, Honsa, issued Dec. 26, 1992, which is also incorporated herein by reference.

When a nonionic polyhydroxy fatty acid amide is used in the nonionic component of the detergent surfactant of the present invention, it will generally be present in an amount of up to 1% to 20% by weight of the composition. More preferably, the nonionic polyhydroxy fatty acid amide may comprise from 2% to 10% by weight of the composition of the invention.

2) Alcohol ethoxylates

Another suitable nonionic surfactant component used in the compositions of the present invention comprises a nonionic surfactant of an ethoxylated fatty alcohol. Such materials correspond to the general formula 48:

(48) wherein R ¹ is a C 8 -C 16 alkyl group or a C 6 -C 12 alkylphenol group and ranges from 1 to 80. Preferably, R ^{1 is an} alkyl group, which may be primary or secondary, containing from 9 to 15 carbon atoms. atoms, more preferably from 10 to 14 carbon atoms. Ethoxylated fatty alcohols will preferably contain from 2 to 12 ethylene oxide groups per molecule, more preferably from 3 to 10 ethylene oxide groups per molecule.

The nonionic alcohol ethoxylate surfactant will often have a hydrophilic-lyophilic balance (HLB) that ranges from 3 to 17. More preferably, the HLB of these materials will range from 6 to 15, most preferably from 10 to 15.

Examples of ethoxylates of fatty alcohols useful as an essential liquid nonionic surfactant in the compositions of the present invention will include ethoxylates which are prepared from alcohols having 12 to 15 carbon atoms and containing 7 moles of ethylene oxide. Such materials are sold under the trade names Neodol 25-7 and Neodol 23-6.5 by Shell Chemical Company. Other useful Neodols include Neodoll-5, an ethoxylated fatty alcohol having an average of 11 carbon atoms in the 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 10 moles of ethylene oxide.

Alcohol ethoxylates of this type are also sold by Shell Chemical Company under the trade name Dobanol. Dobanol 91-5 is an ethoxylated C9-C11 fatty alcohol with an average of 5 moles of 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 nonionic alcohol ethoxylate surfactants include Tergitol 15-S-7 and Tergitol 15-S-9, both of which are linear secondary alcohol ethoxylates which have been marketed by Union Carbide Corporation. The first is a mixed ethoxylation product of a Cn to C15 linear secondary alkanol with 7 moles of ethylene oxide and the second is a similar product, but with 9 moles of ethylene oxide entering the reaction.

Other types of nonionic alcohol ethoxylates useful in these compositions are high molecular weight nonionic compounds, e.g., Neodol 45-11, which are similar to the ethylene oxide condensation products of higher fatty acids with higher fatty alcohols having 14-15 carbon atoms and 11 ethylene oxide groups per mol. Such products were marketed by Shell Chemical Company.

When a nonionic alcohol ethoxylate is used in the nonionic component of the detergent surfactant of the present invention, it will generally be present in an amount of from 0.5% to 10% by weight of the composition. More preferably, the nonionic alcohol ethoxylate will contain from 1% to 5% by weight of the compositions of the present invention.

Dirt-releasing agent from non-cotton fabrics

The known polymeric soil release agents, hereinafter referred to as &quot; SRAs &quot; in the present invention, may optionally be used in such laundry compositions. When used, SRAs will generally contain from 0.01% to 10.0%, typically from 0.1% % to 5%, preferably from 0.2% to 3.0% by weight of the composition.

Preferred SRAs typically have hydrophilic segments for hydrophilizing the surface of hydrophobic fibers, e.g. % polyester and nylon and hydrophobic segments to be deposited on and retained in the hydrophobic fibers for the duration of the wash and rinse cycles, thereby serving as an anchor for the hydrophilic segments. This allows stains that appear following SRA treatment to be more easily cleaned in later washing procedures.

SRAs may contain a variety of charged, e.g., anionic or even cationic entities, see U.S. Pat. No. 4,956,447, Gosselink et al., Issued September 11, 1990, as well as non-charged monomer units and their structures can be linear, branched or even star-shaped. They may contain capping groups which are particularly effective in controlling the relative molecular

-35Weight or change physical or surfactant properties. The charge structures and distributions can be adapted for applications on different types of fibers or fabrics and for a variety of detergent or laundry additive products.

Preferred SRAs include oligomeric terephthalate esters, typically prepared by processes employing at least one transesterification / oligomerization, often with a metal catalyst such as a titanium (IV) alkoxide. Such esters may be prepared using additional monomers capable of being incorporated into the ester structure via one, two, three, four or more positions, naturally without forming a densely crosslinked overall structure.

Other SRAs include the nonionic end-capped 1,2-propylene / polyoxyethylene terephthalate polyesters of U.S. Pat. No. 4,711,730, Gosselink et al., Issued December 8, 1987, for example, prepared by transesterification / oligomerization of poly (ethylene glycol) methyl ether, DMT, PG and poly (ethylene glycol) ("PEG"). Other examples of SRAs include: partially or fully anionically-terminated oligomeric esters of U.S. Pat. No. 4,721,580, Gosselink, issued Jan. 26, 1988, e.g., oligomers of ethylene glycol ("EG"), PG, DMT, and Nα-3,6-dioxa-8-hydroxyoctane sulfonate; and anionic, especially sufloaroyl, end-capped teratalate esters of U.S. Pat. No. 4,877,896, Maldonado, issued October 31, 1989, the latter of which is typical for the applicability of SRA in both laundry and fabric conditioning products, exemplified by an ester composition prepared from the monosodium salt of m-sulfobenzoic acid, PG and DMT, optionally but preferably further comprising added PEG, eg, PEG 3400.

SRAs also include: single copolymer blocks of ethylene terephthalate or propylene terephthalate with polyethylene oxide or polypropylene oxide terephthalate, see US 3,959,230, Hays, issued May 25, 1976 and US 3,893,929, Basadur, issued July 08, 1975; cellulose derivatives such as hydroxyether cellulose polymers available as METHOCEL from Dow; C1-C4 alkylcelluloses and C4 hydroxyalkylcelluloses, see US 4,000,093, Nicol et al., Issued December 28, 1976; and methylcellulose ethers with an average degree of substitution (methyl) per anhydroglucose unit of 1.6 to 2.3 and a solution viscosity of 0.08 N m ² to 0.12 N s m ^-2 (from 80 to 120 cP) [1 cP = 0.001 N sm ' ² ] measured at 20 ° C in a 2% aqueous solution. Such materials are available as METOLOSE SM100 and METOLOSE SM200, which are trade names of methylcellulose ethers manufactured by Shin-etsu Kagaku Kogyo KK.

Suitable SRAs, characterized by poly (vinyl ester) hydrophobic segments, include graft copolymers of poly (vinyl ester), e.g., C 1 -C 6 vinyl esters, preferably poly (vinyl acetate), grafted onto a polyalkylene oxide backbone. See European Patent Application 0 219 048, Kud et al., Issued April 22, 1987. Commercially available examples include SOKALANS SRA, eg SOKALAN

HP-22, sold by BASF, Germany. Other SRAs are polyesters with repeated «0 0 • ·

-36 • 0 000 »· · 0 0

0 0

0 0 0

0 «

Units containing 10-15% by weight of ethylene terephthalate together with 80-90% by weight of polyoxyethylene glycol-derived polyoxyethylene glycol of an average molecular weight of 300-5,000. Commercial examples include ZELCON 5126 from Dupont and MILEASE T from ICI.

Another preferred SRA is an oligomer having the empirical formula (CAP) 2 (EG / PG) ₅ (T) ₅ (SIP) i, which comprises terephthalate (T), sulfoisophthaloyl (SIP), oxyethyleneoxy and oxy-1,2-propylene (EG / PG) units, which are preferably terminated with terminal capping groups (CAP), preferably modified 2-hydroxyethanesulfonates, such as in an oligomer containing one sulfoisophthaloyl unit, 5 terephthaloyl units, oxyethyleneoxy and oxy-1,2-propylenoxy units in a defined ratio, preferably 0.5: 1 to 10: 1 and two end capping units derived from sodium 2- (2-hydroxyethoxy) ethanesulfonate. Said SRAs preferably further comprise from 0.5% to 20% by weight of an oligomer, a crystallinity-reducing stabilizer, e.g. an anionic surfactant, e.g. a linear sodium dodecylbenzenesulfonate or a member selected from xylene, cumene and toluenesulfonates or mixtures thereof; the modifiers are placed in a synthesis vessel, all as set forth in US document: 5,415,807, Gosselink, Pan, Kellett and Hall, of 16.05.1995. Suitable monomers for the above SRAs include Na-2- (2-hydroxyethoxy) ethanesulfonate, DMT, Na-dimethyl-5-sulfoisophthalate, EG and PG.

The additional class of SRA includes: (I) nonionic terephthalates using diisocyanate binders for coupling polymeric ester structures, see U.S. Pat. No. 4,201,824, Violland et al. and U.S. Pat. 4,240,918 to Lagasse et al .; and (II) SRAs with carboxylate end groups prepared by adding trimellitic anhydrides to known SRAs to convert terminal hydroxyl groups to trimellitate esters. By properly selecting the catalyst, trimellitic anhydride forms bonds to the terminal groups of the polymer via an isolated carboxylic acid ester of trimellitic anhydrides rather than opening the anhydride bonds. Either nonionic or anionic SRAs may be used as starting materials as long as they have hydroxyl end groups that can be esterified. See U.S. Pat. No. 4,525,524, Tung et al. Another class includes: (III) urea bonded anionic SRAs, see U.S. Pat. 4,201,824, Violland et al .; (IV) poly (vinylcaprolactam) and related copolymers with monomers such as vinylpyrrolidone and / or dimethylaminoethyl methacrylate, including both nonionic and cationic polymers, see U.S. Pat. 4,579,681, Ruppert et al .; (V) graft copolymers, by addition to BASF types of SKOLAN, prepared by grafting acrylate monomers onto sulfonated polyesters. These SRAs are intended to have dirt-releasing and anti-redeposition (anti-redeposition) activity similar to known cellulose ethers: see EP 279,134 A, Rhone-Poulenc ··· ftftft ftftft - 3 / - ································

Chemie, 1988. Yet another class includes: (VI) grafted vinyl monomers, e.g., acrylic acid and vinyl acetate on proteins such as caseins, see EP 457,205A, BASF (1991); and (VII) polyester polyamide SRAs prepared by condensation of adipic acid, caprolactam and polyethylene glycol, especially for the treatment of polyamide fabrics, see DE 2,335,044, Bevan et al., Unilever N.V., 1974. Other useful SRAs are described in U.S. Pat. 4,240,918; 4,787,989 and 4,525,524.

A preferred soil release agent from non-cotton fabrics

For use in the detergent compositions of the present invention, the following preferred soil release polymers are:

(a) a spine containing:

(i) at least one group having the general formula 49

O

(Cii) at least one group having the general formula 50

-or ⁹ - (or ⁹ ) -o · (49) (50) 10 where R ⁹ is C ₂ -C 6 linear alkylene, C 3 -C 6 branched alkylene, C 5 -C 7 cyclic alkylene and mixtures thereof; R ¹⁰ is independently selected from hydrogen or -L-SO 3 'M ⁺ ; wherein L is a side chain group selected from the group consisting of alkylene, oxyalkylene, alkyleneoxyalkylene, arylene, oxyarylene, alkyleneoxyarylene, poly (oxyalkylene), oxyalkyleneoxyarylene, poly (oxyalkylene) oxyarylene, alkylene poly (oxyalkylene) and mixtures thereof; M is hydrogen or a salt forming a cation; i is 0 or 1;

iii) at least one trifunctional ester-forming branching group;

iv) at least one 1,2-oxyalkylenoxy group; and

(b) one or more end-capping groups, containing:

(i) ethoxylated or propoxylated hydroxyethanesulfonate or ethoxylated or propoxylated hydroxypropanesulfonate units of the general formula 51

9 4 (51) (ii) ··

-38 (MO ₃ S) (CH ₂ ) _m (R ⁿ O) _n wherein M is a cation-forming salt such as sodium or tetraalkylammonium, R ¹¹ is ethylene or propylene or a mixture thereof, m is 0 or 1 and is from 1 to 20; sulfoaryoyl units of formula 52

- (O) C (C ₆ H ₄ ) (SO ₃ -M ⁺ ) (52) wherein M is a salt forming cation;

iii) modified poly (oxyethylene) oxymonoalkyl ether units of formula 53

R ¹² O (CH ₂ CH ₂ O) _k - (53) wherein R ¹² contains from 1 to 4 carbon atoms and k is from 3 to 100; and iv) ethoxylated or propoxylated phenolsulfonate end-capping units of Formula 54

MO ₃ S (C ₆ H ₄ ) (OR ¹³ ) _n O- (54) wherein n is from 1 to 20; M is a cation-forming salt; R ₁₃ is an ethylene, propylene group and mixtures thereof.

This type of preferred soil release polymer of the present invention can be described as having the general formula 55 [(Cap) (R ⁴ ) t] [(AR ¹ -AR ² ) u (AR ¹ -AR ³ ) v (AR ¹ - AR ⁵ ) wA-R ¹ -A -] [R ⁴ ) t (Cap)] (55) wherein A carboxyl linking group having the formula 56

O

II

-C- (56)

R ¹ is an arylene, preferably 1,4-phenylene group having the formula 57 (57) so that when the A units and the R ¹ units together are in the formula A-R'-A, they form a terephthalate unit having the formula 49

(49)

The R ² units are ethyloenoxy or 1,2-propylenoxy groups. R ² units are combined with terephthalate groups to form (AR ^ AR ² ) units having the formula 58 • ·) 9 9 9

9 9

999 999

9

99

-Ό-c HR CIIir— (58)

-39 ·· ·· ·· · 9 9 9 · · «· 9 · 9 · ·

9 9 9

Where R 'and R' are either hydrogen or methyl, provided that R 'and R' are not both methyl at the same time.

R ³ are trifunctional, ester-forming branching groups having the formula 59

O

I (59)

-O-CH 2 -CH-CH 2 -O < 3

Preferably, the R units contain a glycerol group that is inserted into the soil-releasing polymer backbone to provide a branching point. When R ³ units are combined with terephthalate groups to form polymer backbone units, such as (AR ¹ -AR ³ ) -AR ¹ -A units, these units have the formula 60 or formula 61

(60) (61) wherein one terephthalate residue is used so that the portions (A-R'-AR ³⁾ unit while the second terephthalate comprises a part of another group backbone unit, e.g., unit ^{(Ar 3} -AR). The third functional group, which is the beginning of the branching chain, is also typically attached to the terephthalate moiety as well as part (AR ^ AR ² ) of the unit, unit (A-R'-AR ⁵ ), -AR ¹ -A - [(R ⁴ ) _t (Cap)] or other units (AR * -AR ³ ).

An example of a dirt-releasing polymer section containing a "trifunctional ester-forming, branching group" R ³ that contains a glycerol unit has the formula 62

(62)

-40to · ··· · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · ·

R ⁴ units are R ² , R ³ or R ⁵ units.

R ⁵ units are units having the general formula 50 rIO _r io

-OR ⁹ - (OR ⁹ ) 1-O (50)

R ¹⁰

R ¹⁰ wherein R ⁹ is C 2 -C 6 linear alkylene, C 3-6 branched alkylene, and mixtures thereof; R ¹⁰ is preferably independently selected from hydrogen or -L-SO 3 M ⁺ ; wherein L is a side chain group selected from the group consisting of alkylene, oxyalkylene, alkyleneoxyalkylene, arylene, oxyarylene, alkyleneoxyarylene, poly (oxyalkylene), oxyalkyleneoxyarylene, poly (oxyalkylene) oxyarylene, alkylene poly (oxyalkylene); M is hydrogen or a salt forming a cation; i is 0 or 1.

Each carbon atom of R ⁹ units is substituted with R ¹⁰ units independently selected from hydrogen or -L-SO 3 -M ⁺ ; provided that no more than one -L-SO ₃ 'M ⁺ unit is connected to the R ⁹ unit; L is a side chain linker selected from the group consisting of alkylene, oxyalkylene, alkyleneoxyalkylene, arylene, oxyarylene, alkyleneoxyarylene, poly (oxyalkylene), oxyalkyleneoxyarylene, poly (oxyalkylene) oxyarylene, alkylene poly (oxyalkylene) and mixtures thereof.

M is a cationic group selected from the group consisting of lithium, sodium, potassium, calcium and magnesium, preferably sodium and potassium.

Preferred R ⁵ groups are substantially R ¹⁰ substituted C 2 -C 6 alkylene chains. R ⁵ units contain either one C 2 -C 6 alkylene chain substituted with one or more independently selected R ¹⁰ groups (preferably) or two C 2 -C 6 alkylene chains linked together via ether oxygen bonds, each alkylene chain substituted with one or more independently selected R ¹⁰ groups, thus, R ⁵ may contain two separate R ⁹ units, each of which is substituted with one or more independently selected R ¹⁰ groups. Preferably, only one carbon atom of each R ^{9 is} substituted with a -L-SO ₃ M ⁺ moiety with the other R ¹⁰ substituents containing a hydrogen atom. If the index value i is equal to 1 (two ^R9 units comprise the ^R5 unit) and preferably of the formula _R 63 _R io io r! O R ¹ ®

-O-C — C — O — C — C-O- (63)

R ¹⁰ R ¹⁰

R ¹⁰ R ¹⁰ frfrfrfr frfr frfr wherein each R ⁹ is a C 2 alkylene group. Preferably one R ¹⁰ group is -L-SO 3 M ⁺ ; preferably C ₂ carbon is substituted with -L-SO ₃ -M ⁺ ; and equilibrium is created by hydrogen atoms and the general formula is therefore 64:

-CHCH ₂ -O-CH ₂ CH ₂ (64)

CH ₂ (OCH ₂ CH ₂ ) _x SO ₃ 'M ⁺ where L is a polyethyleneoxymethyl substituent, x is from 0 to 20.

As used herein, the term "R ⁵ group" consists essentially of units of Formula 50

-OR ⁹ - (OR ⁹ ), - O (50) having an index i equal to 0, where R ¹⁰ units are hydrogen and one R ¹⁰ unit is -L-SO 3 ~ M ⁺ ; wherein L is a side chain linking unit selected from the group consisting of alkylene, alkenylene, alkyleneoxyalkylene, oxyalkylene, arylene, alkylarylene, alkoxyarylene and mixtures thereof 'refers to preferred compounds of the invention wherein the R ¹⁰ groups consist of one group -L- SO 3 M ⁺ and the remainder of the group R ¹⁰ are hydrogen atoms, for example of formula 65

-O-CH ₂ -CH-OI

CH ₂ (OCH ₂ CH ₂ ) _x SO ₃ "Na ⁺ which is capable of incorporating into the polymeric backbone the soil release polymers of the present invention as the backbone segment-AR ⁵ -A- The units are readily incorporated into the oligomeric or polymeric backbone using the starting material , which has the general formula 66

HO-CH ₂ -CH-O

CH ₂ (OCH ₂ CH ₂ ) _x SO _{3 7} Sia ⁺ wherein x, for the purposes of the L group of the invention, is from 0 to 20.

Other suitable monomers capable of incorporating into the Type A backbone of the preferred soil release polymers of the present invention as a group R ⁵ include alkylene poly (oxyalkylene) oxyarylene-containing monomer having the general formula 67

HO — CEl — —CH — OH

CHrfQCH.CHfrhO-

(67)

SCKNa »··· · A ·· · • · φ · φ · φ ·

Where x is 0 to 20. Another example of a preferred monomer formed in a preferred unit of R ⁵ where i is 0 is sodium sulfopoly / ethyleneoxy) methyl-1,2-propanediols having the general formula 68

HO-CH ₂ -CH-OI

CH 2 (OCH ₂ CH 2) xSO ₃ T 4a ⁺ wherein x is R ³ , R ⁴ and R ⁵ units also contain one or more terminal capping groups, from 0 to 20; more preferred are monomers of formula 69 or 70

OH

HO-CH 2 -CH-CH 2 -OH HO-CH 2 -CH-CH 2 | (69) or (70)

OCH ₂ CH ₂ SO ₃ ^- Na ⁺ OCH ₂ CH ₂ SO ₃ “Na ⁺

A preferred soil release agent of this invention except in front of said R ^1, R ^2, (Cap). The end capping groups are independently selected from ethoxylated or propoxylated hydroxy ethane and propanesulfonate units of formula (MO 3 S) (CH 2) m (R ¹¹ O) n -, wherein M is a cation-forming salt such as sodium or tetraalkylammonium as described herein, R ¹¹ 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 unit of the formula - (O) C (C6H4) (SO3 ^_ M ^+), wherein M is a salt forming cation as described herein above; poly (oxyethylene) oxymonoalkyl ether modified units of general formula R ¹² O (CH 2 CH 2) k - wherein R ¹² contains from 1 to 4 carbon atoms, R 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 groups of the formula MO3S (C6H4) (OR13) _n O- wherein n is from 20 to 20; M is a cation-forming salt; and R ¹³ is an ethylene, propylene group or a mixture thereof.

Most preferable terminally closing unit is in the end closure unit 2 hydroxypropansulfonatového type which is hydroxyethanoic group of the formula (MO3S) (CH2) m ^(R11 O) _n -, preferably R ¹¹ is ethyl, m is 0 and n is from 2 to 4.

T is 0 or 1; the value is from 0 to 60; v is from 0 to 35; w is from 0 to 35.

Preferred soil release polymers of the present invention having the general formula 55 [(Cap) (R ⁴ ) t] [(AR ¹ -AR ² ) u (AR ¹ -AR ³ ) in (AR ¹ -AR ⁵ ) wA-R ^1- A -] [R ⁴ ) _t (Cap)] (55) can be conveniently expressed by the following generic structural formula 72

43 (72) · · · · · · · · ««

The following formula 73 is an example of the preferred soil release polymers of the present invention.

OCHjCtt- -

2í

OCHiCHiS ^ (74)

The soil release agents described above are fully described in U.S. Pat. patent application Ser. No. 08 / 545,351, filed Nov. 22, 1995, which is a part of U.S. Pat. No. 08 / 355,938, filed Dec. 14, 1994, both of which are hereby incorporated by reference. Other soil release polymers of nonwoven fabrics suitable for use in the compositions of the present invention are further described herein below.

Preferred SRAs may be further described as oligomeric esters comprising: (1) a backbone comprising (a) at least one unit selected from the group consisting of dihydroxysulfonates, polyhydroxysulfonates, a unit that is at least trifunctional, the ester bonds being formed as a result of the branched oligomeric backbone and combinations thereof; (b) at least one unit that is a terephthaloyl group; and (c) at least one non-sulfonated unit which is a 1,2-oxyalkylenoxy unit; and (2) one or more end-capping units selected from nonionic end capping units, anionic end capping units, eg, alkoxylated, preferably ethoxylated, 2-hydroxyethanesulfonates, alkoxylated propanesulfonates,

-44alkoxylated propanedisulfonates, alkoxylated phenolsulfonates, sulfoaroyl derivatives and mixtures thereof. Preferred are esters of empirical formula 74:

{(CAP) x (EG / PG) y (DEG) y ”(PEG) y” '(T) z (SIP) z' (SEEG) q (B) m} (74) where CAP, EG / PG, PEG, T and SIP are defined as terephthaloyl (T), sulfoisophthaloyl (SIP), oxyethyleneoxy and oxy-1,2-propylene (EG / PG) units, terminal capping (CAP), poly (ethylene glycol) (PEG) units, ( DEG) represent di (oxyethylene) oxy units, (SEG) represent units derived from sulfoethyl ether of glycerin and related group units, (B) represent branching units which are at least trifunctional, the ester bonds being formed as a result of branching of the oligomeric backbone, x being from 1 to 12, y is from 0.5 to 2.5, y ”is from 0 to dol2, y” 'is from 0 to 10, y + y ”+ y'” has the sum of 0.5 to 25, z is from 1 5 to 25, z 'is from 0 to 12, the sum of z + z' is 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 ', qam represent the average number of moles of corresponding units per mole of the ester concerned and the ester in question has a relative molecular weight within the range of 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 their homologues and mixtures thereof and products of ethoxylation and sulphonation of allyl alcohol. Preferred SRA esters in this class include the transesterification and oligomerization product of sodium 2- {2- (2-hydroxyethoxy) ethoxy} ethanesulfonate and / or sodium [2- {2- (2-hydroxyethoxy} ethoxy] ethanesulfonate, DMT,

Sodium 2- (2,3-dihydroxypropoxy) ethanesulfonate, EG and PG using the appropriate Ti (IV) catalyst and can be designated as (CAP) 2 (T) 5 (EG / PG) 1,4 (SEG) 2,5 (B) 0.13, where CAP is (Na ⁺ -O 3 S [CH ² CH ² O] 3.5) - and B is a unit of glycerin and the EG / PG molar ratio is 1.7: 1 as measured by conventional gas chromatography after complete hydrolysis.

Bleaching compounds - bleaching agents and bleach activators

The detergent compositions of the present invention may optionally contain bleaching agents or bleaching compounds containing a bleaching agent and one or more bleach activators. If present, the bleaching agents will be at levels from 0.05% to 30%, more preferably from 1% to 30%, most preferably from 5% to 20%, based on the detergent, especially for weaving fabrics. 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 the bleach activator.

The bleaching agents used in the present invention may be any of the bleaching agents useful in fabric cleaning compositions known or will be known.

-450 · ·· • 0 0 0 ·

0 0

They include oxygen bleaches as well as other bleaching agents. Perborate bleaches such as sodium perborate (eg, mono- or tetrahydrate) may be used.

Another category of bleaching agent that can be used without limitation includes poroxocarboxylic acid bleaching agents and salts thereof. Suitable examples of this class of agents include magnesium monoperoxyphthalate hexahydrate, the magnesium salt of metachloroperoxybenzoic acid, 4-nonylamino-4-oxoperoxybutyric acid, and diperoxydodecanedioic acid. Such bleaching agents are disclosed in U.S. Pat. No. 4,483,781, Hartman, issued Nov. 20, 1984; U.S. Patent Application 740,446, Bums et al. filed June 3, 1985, European Patent Application 0,133,354, Banks et al., filed February 20, 1985; patent

No. 4,412,934, Chung et al., From 01.11.1983. Highly preferred bleaching agents also include 6-nonylamino-6-oxoperoxycaproic acid as described in U.S. Pat. No. 4,634,551, Burns et al., issued January 6, 1987.

Peroxygen bleaching agents may also be used. Suitable peroxygen bleach compounds include sodium carbonate peroxyhydrate and equivalent "percarbonate" bleaches, sodium pyrophosphate peroxyhydrate, urea peroxyhydrate, and sodium peroxide. Persulfate bleach (e.g., Foxone, commercially available from DôPont) may also be used. A preferred percarbonate reagent comprises dry particles having an average particle size in the range of 500 μm to 1000 μηι, not more than 10% by weight of said particles being less than 200 μιη and not more than 10% by weight of said particles being greater than 1250 μηι. Optionally, the percarbonate may be coated with a silicate, borate or water-soluble surfactant. Percarbonate is available from various commercial sources such as FMC, Solvay and Tokai Denka.

Mixtures of bleaching agents may also be used.

Peroxygen bleaching agents, perborates, percarbonates, etc. are preferably combined with bleach activators, resulting in in situ formation in an aqueous solution (i.e. during the washing process) of the poroxo acid corresponding to the bleach activator. Various non-limiting examples of activators are disclosed in U.S. Pat. No. 4,915,854, issued April 10, 1990 to Mao et al. and U.S. Pat. patent

4.412.934. Nonanoylbenzenesulfonate (NOBS) and tetraacetylethylenediamine (TAED) activators are typical, and mixtures thereof may also be used. For other typical bleaches and activators useful herein, see also U.S. Pat. 4,634,551.

Highly preferred amide-derived bleach activators are those of formula (a):

R ¹ N (R ⁵ ) C (O) R ² C (O) L (75) or R ¹ C (O) N (R ⁵ ) R ² C (O) L (76) ·· 94

9 4 · 9 4 4

444 444

4

44 • «»

-46 ·· ·· «· · 9

4

4 • 4

Wherein R ¹ is an alkyl group of from 6 to 12 carbon atoms, R ² is an alkylene of from 1 to 6 carbon atoms, R ⁵ is H or an alkyl, aryl or alkaryl of from 1 to 10 carbon atoms and L is any suitable leaving group. A leaving group is any group that is replaced from the bleach activator due to nucleophilic attack by the perhydrolysis anion of the bleach activator. A preferred leaving group is phenylsulfonate.

Preferred examples of bleach activators of the above formula include (6-octaamido-caproyl) oxybenzenesulfonate, (6-nonaamido-caproyl) oxybenzenesulfonate, (6-decaamido-caproyl) oxybenzenesulfonate, and mixtures thereof as described in U.S. Pat. No. 4,634,551, incorporated herein by reference.

Another class of bleach activators include the benzooxazine types of activators disclosed by Hodg et al. in U.S. Pat. No. 4,966,723, issued Oct. 30, 1990, incorporated herein by reference. A highly preferred benzoxazine-type activator has the formula 77:

Yet another class of preferred bleach activators includes acyl lactam activators, particularly acyl caprolactams and acylvalerolactams of formulas 78 and 79:

OC-Cha-Cha _Λ x ni

CHj — CH /

OC-CH3CH3-III

Re-C-N. AND

CH 2 CH 2 (78) (79) wherein R ⁶ is H or an alkyl, aryl, alkoxyaryl or alkaryl group containing from 1 to 12 carbon atoms. Highly preferred lactam activators include benzoylcaprolactam, octanoylcaprolactam, 3,5,5-trimethylhexanoylcaprolactam, nonanoylcaprolactam, decanoylcaprolactam, undecenoylcaprolactam, benzoylvalerolactam, octanoylvalerolactamerolal, dacanoylvalerolactam, dacanoylvalerolactam, dacanoylvalerolactam,

3,55-trimethylhexanoylvalerolactam and mixtures thereof. See also U.S. Pat. Patent 4,545,784,

Sanderson, issued October 8, 1985, incorporated herein by reference, which discloses acyl caprolactams, including benzoyl caprolactam, absorbed into sodium perborate.

Bleaching agents other than oxygen bleaching agents are also known in the art and can be used herein. One type of non-oxygen bleaching agent of particular interest includes light ftft ftft ftftft ftftft ftftft ftftft

-ΊΊ ftft ·ftft sulf ft ft ft ft ft ft ft ftovanáovanáovaná aktiv aktiv aktiv aktiv. Activated bleaching agents such as sulfonated zinc and / or aluminum phthalocyanines. See U.S. Pat. No. 4,033,718 to Holcombe et al., issued July 5, 1977. When used, laundry detergents will typically contain from about 0.025% to about 1.25% by weight of such bleaching agents, especially sulfonatzine phthalocyanine.

If desired, the bleaching compounds can be catalyzed using a manganese compound. Such compounds are known in the art and include, for example, the manganese-based catalysts disclosed in U.S. Pat. U.S. Patent 5,246,621; U.S. Pat. U.S. Patent 5,244,594; U.S. Pat. U.S. Patent 5,194,416; U.S. Pat. No. 5,114,606; and European Patent Applications No. 549,271A1; 549,272A1; 544,440A2 and 544,49OA1. Preferred examples of such catalysts include

Mn ^IV 2 (µO) 3 (1,4,7-trimethyl-1,4,7-triazacyclononane) ₂ (PF 6) ₂ ,

Mn ⁱⁿ 2 (uO) i (u-OAc) ₂ (1,4,7-trimethyl-1,4,7-triazacyclononane) ₂ (ClO4) ₂ ,

Mn ^IV 4 (µO) ₆ (1,4,7-triazacyclononane) 4- (ClO ₄ ) 4,

Mn ⁱⁿ Mn ^IV 4 (µO) i (µ-O Ac) ₂ (1,4,7-trimethyl-1,4,7-triazacyclononane) ₂ (ClO 4) 3,

Mn ^IV (1,4,7-trimethyl-1,4,7-triazacyclononane) (OCH 3) 3 (PF6), and mixtures thereof. Other metal-based catalysts include those disclosed in US Patent 4,430,243 and US Patent 5,114,611. The following US patents also refer to the use of manganese with various complex ligands for enhancing bleaching: 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.

For practical reasons and not for limitation, the compounds and methods of the invention may be adapted to provide at least one part per ten million active bleach catalyst entities in an aqueous wash solution and will preferably provide from 0.1 ppm to 700 ppm, more preferably from 1 ppm. ppm to 500 ppm catalyst entities in the wash solution.

A wide variety of other ingredients useful in detergent compositions can be incorporated into the compositions of the present invention, including other active ingredients, carriers, hydrotropes, processing aids, dyes or pigments, solvents for liquid compositions, solid fillers for bulk compositions, etc. If high soap suds are desired, soap suds enhancing agents such as C 10 -C 16 alkanolamides can be incorporated into the compositions, typically at levels of 1% to 10%. A typical class of such suds boosters is illustrated by the C10-C14 monoethanol and diaethanolamides. Also preferred is the use of such suds boosters with high sudsing adjunct surfactants such as the aforementioned amine oxides, betaines and sultains. If desired, soluble magnesium salts such as MgCl ₂ , MgSCL and the like can be added, typically at levels of 0.1% to 2% to provide additional soap suds and increase grease removal efficiency.

The various cleaning ingredients used in the compositions may optionally be further stabilized by absorbing said ingredients onto the porous hydrophobic substrate, then coating said substrate with a hydrophobic coating. Preferably, the cleaning additive is premixed with a surfactant prior to adsorption onto the porous substrate. In use, the cleaning additive is released from the substrate into an aqueous washing solution, where it performs the intended cleaning function.

To illustrate this technique in more detail, the porous hydrophobic silica (Trade Mark SIPERNAT D10, DeGussa) is premixed with a proteolytic enzyme solution containing 3% to 5% C13-C15 ethoxylated alcohol (EO 7) nonionic surfactant. Typically, the enzyme / surfactant solution is 2.5 times the weight of silica. The resulting powder is dispersed with stirring into silicone oil (various silicone oil viscosities from 500-12500 may be used). The resulting silicone oil dispersion is emulsified or otherwise added to the final surfactant matrix. Additives such as the aforementioned enzymes, bleaching agents, bleach activators, bleach catalysts, photoactivators, dyes, fluorescent agents, fabric conditioners and hydrolyzable surfactants can be "protected" for use in laundry detergents, including liquid laundry detergents.

Liquid laundry compositions may contain water and other solvents as carriers. Suitable are primary and secondary low molecular weight alcohols, exemplified by methanol, ethanol, propanol and isopropanol. Monohydroxy alcohols are preferred for solubilizing surfactants, but polyols such as polyols 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) may also be used ). The compositions may contain from 5% to 90%, typically 10% to 50%, of such carriers.

The detergent compositions of the invention will preferably be formulated such that during use in aqueous cleaning operations the wash solution will have a pH of between 6.5 and 11, preferably between 7.5 and 10.5. Laundry products typically have a pH of 9-11. The technique of controlling pH at recommended levels for use includes the use of buffers, alkalis, acids, etc., and is known to those skilled in the art.

Enzymes

Enzymes can be included in the detergent compositions of the invention for a variety of reasons, including for removing protein, carbohydrate, or triglyceride stains from surfaces such as textiles, to prevent migration of dye transfer, for example, in laundry and fabric renovation. Appropriate

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 optimum activity and / or pH stability, thermal stability, and stability to active detergents, enhancers and the like. In this regard, bacterial and fungal enzymes such as bacterial amylases and proteases and fungal cellulases are preferred.

The term "cleaning enzymes" as used herein means any enzyme having a cleaning, stain-removing or otherwise beneficial effect in laundry, hard surface or personal car wash detergents. Preferred purification enzymes are hydrolases such as proteases, amylases and lipases. Preferred washing enzymes include, but are not limited to, proteases, cellulases, lipases, and peroxidases.

Enzymes are normally incorporated into detergent or laundry additive compositions at levels sufficient to provide "for cleaning an effective amount". The term "effective cleaning amount" refers to any amount that is capable of producing cleansing, stain removing, dirt removing, bleaching, deodorizing or freshness enhancing effects on substrates such as fabrics. Under practical conditions for current commercial formulations, a typical amount of up to 5 mg by weight, more typically 0.01 mg to 3 mg, of active enzyme per gram of detergent is typically stated. In other words, the compositions of this invention will typically contain from 0.001% to 5%, preferably 0.01% - 1% by weight of commercial enzyme preparations. Protease enzymes are usually present in these commercial preparations at levels sufficient to provide 0.005 to 0.1 units of Anson activity (AU) per gram of composition. For certain detergents, it may be desirable to increase the active enzyme content of commercial preparations to minimize the total amount of non-catalytically active materials and thereby improve the formation of film / film formation or other final results. Higher active levels may also be desirable for highly concentrated laundry detergents.

Suitable examples of proteases are subtilisins which are obtained from special strains of B. subtilis and B. licheniformis. One suitable protease, obtained from a Bacillus strain having a maximum activity within the pH range of 8-12, was developed and is marketed as ESPERASE® by Novo Industries A / S, Denmark, hereinafter referred to as "Novo". The preparation of this and similar enzymes is described in GB 1,243,784, 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 of 09/01/1985 and Protesus B as disclosed in EP 303,761 A of 28/04/1987 and EP 130,756 A of 09/01/1985. See also high pH protease from Bacillus sp. NCIMB 40338, described in WO 9318140 A, Novo. Enzyme detergent compositions containing a protease, one or more

Other enzymes and a reversible protease inhibitor are described in WO 9203529 to Novo. Other preferred proteases include proteases of WO 9510591 to Procter & Gamble. If desired, a protease with reduced absorption and increased hydrolysis is available as described in WO 9507791 to Procter & Gamble. Recombinant trypsin proteases for detergent compositions useful in the present invention are described in WO 9425583, Novo.

A particularly preferred protease, elaborated in detail, called "Protease D", is a carbonyl hydrolase variant having a non-natural amino acid sequence that is derived from a carbonyl hydrolase precursor by substituting a different amino acid for a number of amino acid residues to positions in said cyrbonyl hydrolase equivalent to +76, 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, Genencor International, dated 20.04.1995. Useful proteases are also described in PCT publications: WO 95/30010, The Procter & Gamble Company, issued November 9, 1995; From WO 95/30011, The Procter & Gamble Company, from 09.11.1995, WO 95/29979, The Procter & Gamble Company, from 09.11.1995.

Amylases useful in the present invention include, for example, the α-amylases described in GB 1,296,839, Novo; RAPIDASE®, International Bio-Synthetics, Inc. and TERMAMYL®, Novo. FUNGAMYL ® from Novo is particularly useful. Technologies for improving the stability of enzymes, e.g., oxidative stability, are known. See. e.g., J. Biological Chem., Vol. 260, No. 11, June 1985, pages 6518-6521. Certain preferred embodiments of these compositions may utilize amylases which have improved stability in detergent compositions, particularly improved oxidation stability, as compared to the TERMAMYL ® reference point commercially used since 1993. Preferred amylases in this invention share the characteristic of "enhanced stability" amylases, at least characterized by a measurable improvement in one or more of the following properties: oxidation stability, eg, to hydrogen peroxide / tetraacetylethylenediamine in a buffered solution at pH 9-10; thermal stability, e.g. at conventional wash temperatures e.g. 60 ° C; or alkaline stability, e.g. at a pH of from 8 to 11, as measured in comparison to the above-defined reference amylase. Stability can be measured using any technique described in the technical tests. See, for example, the references in WO 9402597. Amylases with increased stability can be obtained from Novo or from Genencor International. One class of highly preferred amylases in this invention has the general feature to be derived using site-directed mutagenesis from one or more Baccillus amylases, in particular Bacillus and amylases, regardless of whether the immediate precursors are

- e fr · · *

- 52 - ...............

one, two or multiple amylase strains. For the detergent compositions of the present invention, amylases of increased stability, especially in bleaching, more preferably in oxygen bleaching, as opposed to chlorine bleaching, are preferred for use as the reference amylase above. Such preferred amylases include (a) the amylase of WO 9402597, Novo, herein incorporated hereinabove, from 03.02.1994, as further illustrated on a mutant in which a substitution is made using alanine or threonine, preferably threonine, from a methionine residue located in position 197 B.licheniformis alpha-amylase, known as TERMAMYL®, or a homologous position variant similar to maternal amylase, for example, B. amylolilquefaciens,

B. subtilis or B. stearothermophilus; (b) Amylases with increased stability as described by Genecor International in a paper entitled "Oxidation resistance of alpha-amylases" presented by C Mitchinson at the 207th American Chemical Society Meeting, 13-17 March 1994. It was noted that bleaching agents in automatic dishwashing detergents inactivate alpha-amylases, but that Genencor prepared amylases with improved oxidation stability from B.licheniformis NCIB8061. The most likely residue to be modified was identified as methionine (Met ). Met was substituted one at a time at positions 8, 15,197,256, 304, 366 and 438, resulting in specific mutants, of which M197L and M197T with M197T variant as the most stably expressed variant were particularly important. Stability was measured in CASCADE® and SUNLIGHT®; (c) particularly preferred amylases in the present invention include amylase variants with additional modifications in the direct parent material as described in WO 9510603 A and available from Novo as DURAMYL®. Other particularly preferred amylases with enhanced oxidation stability include those described in WO 9418314 to Genencor International and WO 9402597 to Novo. Any other amylases with increased oxidative stability, for example, derived by site-directed mutagenesis from known chimeric, hybrid or simply mutant parent forms of available amylases, may be used. Other preferred enzyme modifications are available. See WO 9509909 A, Novo.

Cellulases useful herein include both bacterial and fungal types, preferably having an optimum pH between 5 and 9.5. U.S. Pat. No. 4,435,307 to Barbesgoard et al., Issued March 6, 1984, discloses suitable fungal cellulases from Humicola insolens or from Humicola DSM1800 or from cellulase producing fungus 212 belonging to the genus Aeromonas and cellulase extracted from Dolabella Auricula Solander hepatopancreas. 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 particularly useful. See also WO 9117243, Novo. Suitable lipase enzymes for laundry use include lipases produced by the microorganisms of the Pseudomonas family, e.g., Pseudomonas stutzeri ATCC 19.154, as disclosed in GB 1,372,034. See also lipases in Japanese Patent Application 53,20487, filed February 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 AmanoCES, lipases from Chromobacter viscosum, eg Chromobacter viscosum var. lipolyticum NRRLB 3673 from Toyo Jozo Co., Tagata, Japan; Chromobacter viscosum lipases from U.S. Pat. Biochemical Corp., USA and Disoynth Co., The Netherlands and lipase from Pseudomonas gladioli. LIPOLASE®, derived from Humicola lanuginosa and commercially available from Novo, see also EP 341,947, is a preferred lipase for use in the present invention. Lipase and amylase variants stabilized against peroxidase enzymes are described in WO 9414951 A to Novo. See also WO 9205249 and RD 94359044.

Kutinase enzymes suitable for use in the present invention are described in WO 8809367 A to Genencor.

Peroxidase enzymes can be used in combination with oxygen sources such as percarbonate, perborate, hydrogen peroxide, etc. to "dissolve bleach" or to prevent transfer of dyes or pigments removed from substrates during washing to other substrates present in the wash solution. Known peroxidases include horseradish peroxidase, ligninase and haloperoxidases such as chloro- or bromoperoxidase. Detergent compositions containing peroxidases are disclosed in WO 89099813 A, Novo, dated 19 October 1989, and in WO 8909813 A, Novo.

A variety of enzyme materials and compositions for incorporating them into synthetic laundry detergents are also disclosed in WO 9307263 A and WO 9307260 A, Genencor International, WO 8908694 A, Novo and U.S. Pat. No. 3,553,139, McCarty et al., From January 5, 1971. Enzymes are further disclosed in U.S. Pat. No. 4,101,457, Plače et al., Issued July 18, 1978 and U.S. Pat. No. 4,507,219, Hughes, from 26.03.1985. Enzyme materials useful in liquid detergent compositions and their incorporation into such compositions are disclosed in U.S. Pat. No. 4,261,868, Hora et al., From 14.04.1981. Enzymes for use in detergent compositions can be stabilized by various techniques. Enzyme stabilization systems are exemplified and exemplified in U.S. Pat. No. 3,600,319, Gedge et al., From Aug 17, 1971, EP 199,405 and EP 200,586, Venegas, from Oct. 29, 1986 ,. Enzyme stabilization systems are also described, for example, in U.S. Pat. 3,519,570. Useful Bacillus sp. AC13, which yields proteases, xylenases and cellulases, is described in WO 9401532 A, Novo.

• ·

-53Enzyme stabilization systems

Enzymes containing, including but not limited to, liquid compositions in the present invention may contain from 0.001% to 10%, preferably from 0.005% to 8%, most preferably from 0.01% to 6% by weight of the enzyme stabilization system. The enzyme stabilization system may be any stabilization system that is compatible with the purification enzyme. Such a system may be inherently provided by the other active ingredients of the composition, or may be added separately, eg, by a detergent-forming chemist or by a detergent enzyme manufacturer. Such stabilization systems may, for example, include calcium ion, orthoboric acid, propylene glycol, short chain carboxylic acids, boric acids and mixtures thereof, and are intended to address various stabilization problems depending on the type and physical form of the detergent composition.

One approach to solving stabilization problems is to use water-soluble sources of calcium and / or magnesium ions in the final compositions that provide these ions to the enzymes. Calcium ions are generally more effective than magnesium ions and are preferred in this invention when only one cationic type is used. Typical detergent compositions, especially liquid detergents, will contain from 1 to 30, preferably from 2 to 20, even more preferably from 8 to 12 millimoles of calcium ions per liter of finished detergent, although variations are possible depending on factors including variety, type and levels of incorporated detergents. enzymes. Water-soluble calcium or magnesium salts are preferably used, including, for example, calcium chloride, calcium hydroxide, calcium formate, calcium malate, calcium hydroxide, and calcium acetate; more generally calcium sulfate or magnesium salts corresponding to the calcium salts mentioned in the examples may be used. Furthermore, increased levels of calcium or magnesium may naturally be useful, for example, to promote the greasy penetrating action of certain types of surfactants.

Another approach to solving stabilization problems is the use of boron compounds. See, U.S 4,537,706, Severson. Borate stabilizers, if used, may be at levels up to 10% or more of the composition, although levels up to 3% by weight of boric acid or other boron compounds such as borax or orthoborate are more typically suitable for use in a liquid laundry detergent. Substituted boric acids such as phenylboronic acid, butaneboronic acid, p-bromophenylboronic acid and the like can be used in place of boric acid, and reduced boron levels are possible in laundry detergents, although such substituted boron derivatives are used.

The stabilizer systems of certain detergent compositions may further comprise from 0 to 10%, preferably from 0.01% to 6% by weight, of chlorine bleach scavengers added because of: · · ·

54 to prevent chlorine bleach compounds present in many water sources from attacking and inactivating enzymes, particularly under alkaline conditions. Although chlorine levels in water may be small, typically in the range of from 0.5 ppm to 1.75 ppm, the available chlorine in the total volume of water that comes into contact with the enzyme, for example during fabric washing, may be relatively high; therefore, the stability of the enzyme to chlorine in use is sometimes problematic. Since perborate or percarbonate, which have the ability to react with a chlorine bleaching agent, may be present in certain ready-to-use compositions in amounts calculated separately from the stabilization system, the use of additional chlorine stabilizers may not be essential, more generally, their use may result in improved results. 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, etc. Similarly, antioxidants such as carbamates, ascorbates, etc. can be used. organic amines such as ethylenediaminetetraacetic acid (EDTA) or their alkali metal salts, monoethanolamine (MEA) and mixtures thereof. Similarly, special enzyme inhibition systems may be incorporated to give different enzymes maximum compatibility. If desired, other conventional scavengers such as bicarbonate, nitrate, chloride, hydrogen peroxide sources such as sodium perborate tetrahydrate, sodium perborate monohydrate and sodium percarbonate as well as phosphate, condensed phosphate, acetate, benzoate, citrate, formate, lactate, malat, tartrate, salicylan etc. and mixtures thereof. In general, since the chlorine scavenger function can be performed by additives separately listed under better known functions (eg, hydrogen peroxide sources), there is no absolute requirement to add separate chlorine scavengers unless the compound performing that function to the desired extent is absent in the enzyme containing embodiments of the invention; even then the gripper is added only for optimum results. In addition, the chemist will apply normal chemical knowledge to avoid the use of any enzyme scavenger or stabilizer that is significantly incompatible, in this formulation, with other reactive additives, if used. In relation to the use of ammonium salts, these salts can simply be mixed with the detergent, but tend to absorb water and / or release ammonia during storage. Therefore, such materials, if present, are desirable to protect the particles as described in U.S. Pat. No. 4,652,392, Baginski et al.

The compositions of the present invention may optionally include one or more laundry additive materials or other materials to promote or enhance cleaning performance, treat the substrate to be cleaned, or modify the aesthetic properties of the laundry detergent.

99 999 ·· ·· · · · · · • · ·!

• 9 9 ·· · · · ·

99999999 · formulations (eg perfumes, coloring agents, dyes, etc.) The following are illustrative examples of such additive materials.

Supporting agents

Optionally, detergent builders may be incorporated into the compositions of the present invention to promote mineral hardness control. Inorganic and organic support agents can be used. Supporting agents are typically used in fabric washing compositions to promote particulate soil removal.

The level of support agent may vary within wide limits depending upon the end use of the composition and its physical form. If present, the compositions will typically contain at least 1% of a support agent. The liquid compositions typically comprise from 5% to 50%, more typically 5% to 30% by weight of the laundry aid. Granular compositions typically comprise from about 10% to about 80%, more typically from about 15% to about 50%, by weight of the laundry aid. However, lower or higher levels of support agent are not considered to be excluded.

Inorganic or phosphorus-containing laundry detergent enhancers include, but are not limited to, alkali metal, ammonium, alkanolamine salts, phosphate polyesters (exemplified by tripolyphosphates, pyrophosphates, and glassy polymeric metaphosphates), phosphonates, phytic acid, silicates, carbonates (including carbonates) and sesquicarbonates), sulfates and aluminosilicates. However, non-phosphate enhancers are required in some locations. Importantly, the compositions of the present invention work surprisingly well even in the presence of so-called "weak" excipients (as compared to phosphates) such as citrates, or in so-called "underdimensioned" agents that may occur. zeolite or layered silicate builders.

Examples of silicate builders are alkali metal silicates, especially silicates, wherein the SiO 2: Na 2 O ratio is in the range of 1.6: to 3.2: 1 and layered silicates, such as layered sodium silicates, described in US Patent 4,664,839 to HP Rieck, U.S. Pat. from 12.05.1987. NaSKS-6 is a trade name for crystalline layered silicate, commercially available from Hoechst (commonly abbreviated herein as "SKS-6"). Unlike zeolite builders, Na-SKS-6 silicate builder does not contain aluminum. NaSKS-6 has a delta-Na ₂ SiC> 5 morphological form of layered silicate. It can be prepared by the methods described in DE-A-3,417,649 and DE-A-3,742,043. SKS-6 is a highly preferred layered silicate for use in the present invention, but other embodiments of the present invention may be used.

-560 0

0 0 ·

0 0 0 0 0 0

00 0 0 0 ·

0 0 0

000 000 0 0

Layered silicates, such as those having the general formula NaMSi _x O _{2x +} i.yH ₂ O, where 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. Various other layered silicates from Hoechst include NaSKS-5, NaSKS-7 and NaSKS-11 as alpha, beta and gamma forms. As noted above, delta-Na 2 SiO 5 (form NaSKS-6) is most preferred for use in the present invention. Other silicates may also be useful, such as magnesium silicates, which may serve as brittleness-forming agents in granular compositions, as a stabilizer for oxygen bleaches, and as components of soap suds control systems.

Examples of carbonate builders are alkali earth and alkali metal carbonates as disclosed in German Patent Application No. 2,321,001, filed Nov. 15, 1973.

Aluminosilicate builders are useful in the present invention. Aluminosilicate builders are of great importance in most commercially available high performance granular laundry detergents and can also be important builders in liquid laundry detergents. Aluminosilicate builders include builders having the empirical formula of 80

M _z (zALO ₂ ) _y ] .xH ₂ O (80) wherein z and y are integers at least 6, the molar ratio of z to y is between 1.0 and 0.5 and x is an integer from 15 to 264.

Applicable ion exchange aluminosilicate materials are commercially available. These aluminosilicates may have a crystalline or amorphous structure and may be naturally occurring aluminosilicates or synthetically prepared. A process for preparing ion exchange aluminosilicate materials is disclosed in U.S. Pat. No. 3,985,669, Krummel et al., issued October 12, 1976. Preferred synthetic ion exchange aluminosilicate materials for use in the present invention are available under the designation Zeolite A, Zeolite P (B), Zeolite MAP, and Zeolite X. In particularly preferred embodiments, the crystalline aluminosilicate ion exchange materials have the formula 81:

Nai ₂ [(AlO ₂ ) ₁₂ (SiO ₂ ) i ₂ ] .xH ₂ O (81) wherein x is from 20 to 30, especially 27. This material is known as Zeolite A. Dehydrated zeolites may also be used according to the present invention ( x = 0-10). The aluminosilicates preferably have a particle diameter of 0.1-10 µm.

Organic detergent enhancers suitable for the purposes of this invention include, but are not limited to, a wide variety of polycarboxylate compounds. The term "polycarboxylate" as used herein refers to compounds having multiple carboxylate groups, preferably at least 3 carboxylate groups. Polycarboxylate support agents can mohou ·

Generally, they may be added to the composition in acid form, but may also be added in the form of a neutral salt. When the salt form is used, alkali metal salts such as sodium, potassium and lithium or alkanoammonium salts are preferred.

Among the polycarboxylate builders there are various categories of useful materials. One important category of polycarboxylate builders includes ether polycarboxylates, including oxydisuccinate, as disclosed in U.S. Pat. U.S. Patent 3,128,287 to Berg, issued April 7, 1964; No. 3,635,830 to Lamnerti et al., issued January 18, 1972. See also &quot; TMS / TDS &quot; No. 4,663,071, Bush et al., issued May 5, 1987. Suitable ether polycarboxylates also include cyclic compounds, especially alicyclic compounds such as those described in U.S. Pat. U.S. Patents 3,923,679; 3,835,163; 4,158,635; 4,120,874 and 4,102,903.

Other useful laundry detergent enhancers include etherhydroxypolycarboxylates, copolymers of maleic anhydride with ethylene or vinyl methyl ether, 1,3,5-trihydroxybenzene-2,4,6-trisulfonic acid and carboxymethyloxysuccinic acid, various alkali metal salts, ammonium and substituted ammonium salts of polyacetic acid, e.g., ethylenediaminetetraacetic acid and nitrilotriacetic acid, as well as polycarboxylates such as mellitic acid, succinic acid, oxydisuccinic acid, polymaleic acid, benzene-1,3,5-tricarboxylate acid, carboxymethyloxysuccinic acid, and soluble salts thereof.

Citrate builders, such as citric acid and its soluble salts (especially sodium salt), are polycarboxylate builders of particular importance for high performance liquid detergents for their availability from renewable sources and for their biodegradability. Citrates can also be used in granular compositions, particularly in combination with zeolite and / or layered silicate builders. Oxydisuccinates are also particularly useful in such compositions and combinations.

They are also suitable in the detergent compositions of the present invention

3,3-dicarboxy-4-oxa-1,6-hexanedioates and their related compounds, disclosed in U.S. Pat. No. 4,566,984, Bush, issued Jan. 28, 1986. Useful succinate builders include C5-C20 alkyl and alkenylsuccinic 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 and the like.

• ·

-58 ··· * · ♦ <

· ♦ »0 · ·» 0 0 0

Other suitable polycarboxylates are disclosed in U.S. Pat. No. 4,144,226, Crutchfield et al., issued March 13, 1979; No. 3,308,067, Diehl, issued March 7, 1967. See also, U.S. Pat. U.S. Patent 3,723,322 to Diehl.

Fatty acids, such as C12-C18 monocarboxylic acids, alone or in combination with the aforementioned enhancers, especially citrate and / or succinate enhancers, may also be included in the composition to provide additional enhancement activity. Such use of fatty acids will generally result in a reduction in soap suds formation, which the chemist must take into account.

In situations where phosphorous-based support agents, and especially the lumpy formulations used for hand washing operations, various alkali metal phosphates such as the known sodium tripolyphosphates, sodium diphosphates and sodium orthophosphates may be used. Phosphonate builders such as ethane-1-hydroxy-1,1-diphosphonate and other known phosphonates can also be used (see, e.g., U.S. Patents 3,159,581; 3,213,030; 3,422,021; 3,400,148 and 3,422,137).

Chelating agents

The detergent compositions of the present invention may also optionally contain one or more iron and / or manganese chelating agents. Such chelating agents may be selected from the group consisting of aminocarboxylates, aminophosphonates, polyfunctionally substituted aromatic chelating agents, and mixtures thereof, all as hereinafter defined. Notwithstanding the theory, it is believed that the benefits of these materials are due in part to their exceptional ability to remove iron and manganese ions from washing solutions by forming soluble chelates.

Aminocarboxylates useful as optional chelating agents include ethylenediaminetetraacetates, N-hydroxyethylethylenediamine triacetates, nitrilotriacetates, ethylenediaminetetrapropionates, triethylenetetraamine hexaacetates, diethylenetriaminepentaacetates and ethanediglycines, and mixtures thereof, and the alkali metal salts thereof and their alkali metal salts. Also suitable for use as a chelating agent is methylglycine diacetic acid (MGDA).

Amino phosphonates are also suitable for use as chelating agents in the compositions of the present invention if at least low levels of total phosphorus are acceptable in the detergent compositions and include ethylenediaminetetrakis (methylenephosphonates) such as DEQUEST. Preferably, these aminophosphonates do not contain alkyl or alkenyl groups having more than 6 carbon atoms.

In these means are. useful polyfunctionally substituted aromatic chelating agents. See U.S. Pat. No. 3,812,044, Connor et al., issued May 21, 1974. Preferred compounds of this type in acid form are dihydroxydisulfobenzenes, e.g., 1,2-dihydroxy-3,5-disulfobenzene.

A preferred biodegradable chelating agent for use herein is ethylenediamine disuccinate ("EDDS"), particularly the [S, S] isomer as described in U.S. Pat. No. 4,704,233 to Hartman and Perkins, issued November 3, 1987.

When used, these chelating agents will generally be from 0.1% to 10% by weight of the detergent composition of the present invention. More preferably, if used, these chelating agents will be from 0.1% to 3% by weight of the detergent composition.

Aluminum soil removal / anti-redeposition agents

The compositions of the invention may also optionally contain water-soluble ethoxylated amines having clay soil removal and anti-redeposition (anti-redeposition) properties. Granular detergent compositions containing these compounds typically contain from 0.01% to 10.0% by weight of water-soluble ethoxylated amines; liquid detergents typically contain 0.01% to 5%.

The most preferred aluminum soil removal and anti-deposition agent is ethoxylated tetraethylenepentaamine. Exemplary ethoxylated amines are further described in U.S. Pat. No. 4,597,898, VanderMeer, issued July 1, 1986. Another group of preferred clay soil release releasing agents is cationic compounds disclosed in European Patent Application 111,965, Oh and Gosselink, published June 27, 1984. Other clay soil removal / anti-redeposition agents that may be used include the ethoxylated amine polymers disclosed in European Patent Application 11,984, Gosselink, published June 27. 1984; zwitterionic polymers disclosed in European Patent Application 112,592, Gosselink, published June 4, 1984; and the amine oxides disclosed in U.S. Pat. No. 4,548,744, Connor, issued Oct. 22, 1985. Other clay soil removal and / or anti-redeposition agents known in the art may also be used in the compositions of the present invention. Another type of preferred anti-redeposition agent includes carboxymethylcellulose (CMC) materials. Such materials are known in the art.

Polymeric dispersing agents

Polymeric dispersing agents can advantageously be used in the compositions of the present invention at levels from 0.1% to 7% by weight, especially in the presence of zeolite and / or layered silicate builders. Suitable polymeric dispersing agents include

Polymeric polycarboxylates and polyethylene glycols, although other types known in the art may also be used. Although not intended to be limited to the theory, polymer dispersing agents are believed to enhance the overall performance of laundry detergents when used in combination with other builders (including low molecular weight polycarboxylates) by inhibiting crystal growth, particulate dirt releasing peptization and counteracting re-deposition.

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 of the polymeric polycarboxylates of the present invention or monomeric segments containing non-carboxylate radicals, e.g., vinyl methyl ether, styrene, ethylene, etc. is suitable provided that such segments do not constitute more than 40% by weight. Particularly suitable polymeric polycarboxylates may be derived from acrylic acid. Such acrylic acid-based polymers useful herein are the water-soluble salts of polymerized acrylic acid. The average molecular weight of these polymers in acid form is preferably from 2,000 to 10,000, more preferably from 4,000 to 7,000, and most preferably from 4,000 to 5,000. The water-soluble salts of these acrylic acid polymers may include, for example, alkali- metal, ammonium and substituted ammonium salts. Soluble polymers of this type are known materials. The use of polyacrylates of this type in detergent compositions is disclosed, for example, in U.S. Pat. No. 3,308,067,

From 07.03.19967.

Acrylate / maleic copolymers can also be used as preferred dispersing / anti-redeposition components. Such materials include the water-soluble salts of copolymers of acrylic acid and maleic acid. The average molecular weight of such copolymers in acid form is preferably 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 maleat segments in such copolymers will generally be within the range of 30: 1 to 1: 1, more preferably from 10: 1 to 2: 1. The water-soluble salts of these acrylic / maleic acid copolymers may include, for example, alkali metal, ammonium and substituted ammonium salts. Soluble acrylate / maleate copolymers of this type are known materials as described in European Patent Application No. 66915 published December 15, 1982 as well as in EP 193,360 published September 3, 1986, which also disclose such polymers containing this. <

-61hydroxypropylacrylat. Still other useful agents include maleic / acrylic / vinyl alcohol terpolymers. Such materials are also disclosed in EP 193,360, including, for example, a 45/45/10 acrylic / maleic / vinyl alcohol terpolymer.

Another polymeric material that can be incorporated is polyethylene glycol (PEG). PEG can act as a dispersing agent and also act as an aluminum soil removal and anti-redeposition agent. Typical relative molecular weights for this purpose are from 500 to 100,000, preferably from 1,000 to 50,000, even more preferably from 1,500 to 10,000.

Polyaspartate and polyglutamate dispersing agents can also be used, particularly in conjunction with zeolite builders. Dispersants such as polyaspartate preferably have a relative molecular weight of 10,000.

Optical brightening agents

Any optical brighteners or bleaching or bleaching agents at levels typically from 0.05% to 1.2% by weight can be incorporated into the laundry compositions of the present invention. Commercial optical brighteners that may be useful in the present invention may be classified into subgroups including, but not limited to, stilbene, pyrazoline, coumarin, carboxylic acid, methinkyanines, dibenzothiophene-5,5-dioxide derivatives, azoles. , 5- and 6-membered ring heterocycles and other various reagents. Examples of these optical brighteners are given in "Production and Application of Fluorescent Brightening Agents" by M. Zahradnik, edited by John Wiley & Sons, New York (1982).

Specific examples of optical brighteners useful in such compositions are those disclosed in U.S. Pat. No. 4,790,856, Wixon, issued December 13, 1988. These optical brighteners include a series of PHORWHITE optical brighteners from Verona. Other optical brighteners referred to include: Tinopal UNPA, Tinopal CBS and Tinopal 5BM, supplied by Ciba-Geigy; Artic White CC and Artic White CWD sold by Hilton-Davis from Italy; 2- (4-stryl-phenyl) -2H-naphthol [1,2-d] triazoles;

4,4´-bis (1,2,3-triazol-2-yl) -stilbenes; 4,4´-bis (stryl) bisphenyls; and aminocoumarins. Specific examples of these optical brighteners include 4-methyl-7-diethylaminocoumarin;

1,2-bis (-benzimidazol-2-yl) ethylene; 1,3-diphenyl-pyrazolines; 2,5-bis (benzoxazol-2-yl) thiophene; 2-stryl-naphth- [1,2-d] oxazole; and 2- (stilben-4-yl) -2H-naphtho- [1,2-d] triazole. See also U.S. Pat. No. 3,646,015, Hamilton, issued Feb. 29, 1972. Anionic optical brighteners are preferred herein.

-62 • 0 0 «♦ 0 · ♦ • i i i i i i i i 0

00 «»

• 0 ··

Soap suds suppressors

Compounds for reducing or suppressing soap suds can be incorporated into the compositions of the present invention. Soap suds suppressors may be of particular importance in so-called "high concentration cleaning processes" as described in US documents. 4,489,455 and 4,489,574 and in European style front-loading washers. A wide variety of materials can be used as soap suds suppressors, and soap suds suppressors are known to those skilled in the art. See, eg, the Encyclopedia of Chemical Technology - Kirk Othmer Encyclopedia of Chemical Technology, 3rd Ed., Vol. 7, pages 430-447 (John Wiley &amp; Sons, Inc., 1979). One category of suds suppressors of particular interest includes monocarboxylic fatty acids and soluble salts thereof. See U.S. Pat. U.S. Patent 2,954,347 to Wayne St.; John, from September 27, 1960. The monocarboxylic fatty acids and salts thereof used as suds suppressors typically have hydroxycarbyl chains of 10 to 24 carbon atoms, preferably 12 to 18 carbon atoms. Suitable salts include alkali metal salts such as sodium, potassium and lithium salts, and ammonium and alkanoammonium 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. triglycerides of fatty acids), fatty acid esters of monovalent alcohols, aliphatic C18-C40 ketones (e.g. stearone), etc. Other soap suppressants foams include N-alkylated aminotriazines such as tri- to hexa-alkylmelamines or di- to tetra-alkyldiaminochlorotriazines formed as the products of two or three moles of a primary or secondary amine containing 1 to 24 carbon atoms, propylene oxide and monostearyl phosphates, e.g. monostearyl ester alcohol and monostearyl-di-alkali-metal (e.g., K, Na and Li) phosphates and phosphatesters. Hydrocarbons such as paraffin haloparaffin can be used in liquid form. Liquid hydrocarbons will be liquid at room temperature and atmospheric pressure and will have a melting point between -40 ° C and 50 ° C and a minimum boiling point not less than 110 ° C (atmospheric pressure). It is also known to use waxy hydrocarbons, preferably with a melting point below 100 ° C. Hydrocarbons represent a preferred category of suds suppressor for detergent compositions. Hydrocarbon suds suppressors are described, for example, in U.S. Pat. No. 4,265,779, Gandolfo et al., issued May 5, 1981. The hydrocarbons thus include aliphatic, alicyclic, aromatic and heterocyclic saturated or unsaturated hydrocarbons having up to 12 to 70 carbon atoms. The term "paraffin"

-63 As used in this discussion of soap suds suppressors, it is intended to 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, a dispersion or emulsion of polyorganosiloxane oils or resins, and a combination of polyorganosiloxane with silica particles, wherein the polyorganosiloxane is chemisorbed or fused to silica. Silicone suds suppressors are known in the art, for example, in U.S. Pat. No. 4,265,779 to Gandolfo et al. from 05.05.1981 and European Patent Application No. 89307851.9, Starch, M.S., published 07.02.1990.

Other silicone suds suppressors are disclosed in U.S. Pat. No. 3,455,839, which relates to compositions and processes for defoaming aqueous solutions by incorporating small amounts of polydimethylsiloxane fluids.

Mixtures of silicone and silanized silica are described, for example, in German patent application DOS 2,124,526. Silicone antifoams and suds control agents in granular detergent compositions are disclosed in U.S. Pat. No. 3,933,672 to Bartolott et al. and U.S. Pat. No. 4,652,392, Baginski et al., issued March 24, 1987.

By way of example, a silicone suds suppressor agent for use in the present invention is an amount of soap suds suppressing agent in a soap suds controlling agent consisting essentially of:

(i) a polydimethylsiloxane liquid having a viscosity of 2.10 ^- ^ ^{1 -1} to 1.5.10 ' ³ m ² s ^-1 (from 20 cs to 1 500 es) [1 cSt = 10' ⁶ m ² s ^-1 ] at 25 ° C;

(ii) from 5 to 50 parts per 100 parts by weight of ad (i) siloxane resin, consisting of (CH ₃ ) ₃ SiO ₂ / units and SiO ₂ units in a ratio of (CH ₃ ) ₃ SiO ₂ / units to SiO ₂ units of 0.6: 1 to 1.2: 1; and (iii) from 1 to 2 parts per 100 parts by weight of ad (i) of solid silica gel.

In the preferred suds suppressor used herein, the continuous phase solvent is prepared from certain polyethylene glycols or polyethylene-polypropylene glycol copolymers or mixtures thereof (preferably) or polypropylene glycol. Primary silicone suds suppressor. it is branched / crosslinked and preferably non-linear.

To further illustrate this point, typical liquid soap-controlled liquid detergents will optionally contain from 0.001 to 1.0, preferably 0.01 to 0.7, most preferably

0.05 to 0.5% by weight of said silicone suds suppressor,

99 99

9

9 9 9 9 • Φ ΦΦΦ ΦΦΦ

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99 99

-64φφ ·· • φ φ

Φ · • φ

No. 9999,999 which comprises (1) a non-aqueous emulsion of a primary antifoam agent which is a mixture of (a) a polyoraganosiloxane, (b) a resin siloxane or silicone resin giving silicone compounds, (c) finely divided filler material; (a), (b) and (c), forming silanolates; (2) at least one nonionic silicone surfactant; and (3) polyethylene glycol or a polyethylene-polypropylene glycol copolymer having a water solubility at room temperature of greater than 2% by weight; and without polypropylene glycol. Similar amounts may be used in granular compositions, gels, etc. See also U.S. Pat. 4,978,471, Starch, issued Dec. 18, 1990, and 4,983,316, Starch, issued Jan. 8, 1991; No. 5,288,431 to Huber et al., Issued Feb. 22, 1994; Nos. 4,639,489 and 4,749,740 to Aizawa et al. in a column. 1, line 46 to col. 4, line 35.

The silicone suds suppressors of the present invention preferably comprise polyethylene glycol and a polyethylene glycol / polypropylene glycol copolymer, all having an average relative molecular weight of less than 1,000, preferably between 100 and 800. The polyethylene glycol and polyethylene glycol / polypropylene glycol copolymers of this invention have water solubility at a room temperature of more than 2% by weight, preferably more than 5% by weight.

A preferred solvent in the present invention is polyethylene glycol having an average molecular weight of less than 1,000, more preferably between 100 and 800, most preferably between 200 and 400 and a polyethylene glycol / polypropylene glycol copolymer, preferably PPG 200 / PEG 300. Preferably the weight ratio of polyethylene glycol to polyethylene polypropylene glycol copolymer between 1: 1 and 1:10, most preferably between 1: 3 and 1: 6.

The preferred silicone suds suppressors used in the present invention do not contain polypropylene glycol, especially having a molecular weight of about 4,000. They also preferably do not contain block copolymers of ethylene oxide and propylene oxide, e.g.

PLURONIC L101.

Other suds suppressors useful in the present invention include secondary alcohols (e.g., 2-alkyl alkanols) and mixtures of such alcohols with silicone oils such as the silicones disclosed in US 4,798,679; 4,075,118 and EP 150,872. Secondary alcohols include C ₆ -C ₁₆ alkyl alcohols having a C ₆ -C ₁₆ chain. A preferred alcohol is 2-butyloctanol, sold by Condea under the trade name ISOFOL 12. A mixture of secondary alcohols is sold under the trade name ISALCHEM 123 by Enichem. Mixed soap suds suppressors typically contain mixtures of alcohols + silicone in a weight ratio of 1: 5 to 5: 1.

• · · · · · · · · · · · · · ·

-65-.: ...: ..

For any detergents to be used in automatic washing machines, the soap foam should not be produced in such an amount that the machine overflows. Soap suds suppressors, when used, are preferably present in an "amount soap suds". By &quot; soap suds suppressor &quot; is meant that the chemist builder can select the amount of such soap suds control agent so as to control sufficiently the formation of the resulting soap suds in low sudsing detergents for use in automatic laundry washing machines.

The compositions of the present invention will generally contain from 0% to 5% soap suds suppressor. The monocarboxylic fatty acids and their salts, when used as suds suppressors, will typically be present in amounts up to 5% by weight of the detergent composition. Preferably, from 0.5% to 3% of the monocarboxylate agent is used to suppress soap suds. Silicone suds suppressors are typically used in amounts up to 2.0% by weight of the detergent although higher amounts may be used. This upper limit is of a practical nature, primarily in order to keep costs low and the effectiveness of lower amounts effective to control soap suds formation. Preferably, from 0.01% to 1% of a silicone suds suppressor is used, more preferably from 0.25% to 0.5%. As used herein, these weight percentages include any silica that could be used in combination with a polyorganosiloxane, as well as any additional materials that may be used. Monostearyl phosphate suds suppressors are generally used in amounts ranging from 0.1% to 2% by weight of the composition. Hydrocarbon suds suppressors are typically used in amounts ranging from 0.01% to 5.0%, but higher levels may be used. The alcohol suds suppressors are typically used in amounts of from 0.2% to 3% by weight of the finished compositions.

Fabric softening agents

Optionally, a variety of fabric softening (softening) agents may be used in the compositions, in particular the bentonites (smectites, fuller clays) of U.S. Pat. No. 4,062,647, Storm and Nirschl, dated December 13, 1977, as well as other softening clays known in the art, typically at levels of from about 0.5% to about 10% by weight, to provide fabric softening benefits at the same time as fabric cleaning. Clay softeners can be used in combination with amine and cationic softeners, as disclosed in:

··· ··· • · ·· ··

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for example U.S. Pat. No. 4,375,416, Crisp et al., issued March 1, 1983; U.S. Patent 4,291,071, Harris et al., issued September 22, 1981.

Optical brightening agents

The detergent compositions herein may also optionally contain from about 0.005% to about 5% by weight of certain types of hydrophilic optical brighteners that also act to inhibit dye transfer. When used in the compositions of the present invention, they will preferably contain from 0.01% to 1% by weight of such optical brighteners.

The hydrophilic optical brighteners useful in the present invention have the general formula 82:

wherein R 1 is selected from aniline, N-2-bis-hydroxyethyl and NH-2-hydroxyethyl; R ₂ is selected from N-2-bis-hydroxyethyl, N-2-hydroxyethyl-N-methylamine, morphiline, chlorine and amine; and M is a cation-forming salt such as sodium or potassium.

If in the above formula R 1 is aniline, R ₂ is N-2-bis-hydroxyethyl and M is a sodium cation, then the optical brightener is the disodium salt of the acid

4,4 ', - bis [(4-anilino-6- (N-2-bis-hydroxyethyl) -s-triazin-2-yl) amino] -2,2'-stilbenedisulfonic acid. This specialty type is sold under the trade name Tinopal-UNPA-GX by CibaGeigy Corporation. Tinopal-UNPA-GX is preferably an optical brightener useful in the detergent compositions herein.

If in the above formula R 1 is aniline, R ₂ is N-2-hydroxyethyl-N-methylamine and M is a sodium cation, then the optical brightener is the disodium salt of 4,4 ', - bis [(4-anilino-6 ( N-2-hydroxyethyl-N-methylamino) -s-triazin-2-yl) amino] -2,2'-stilbenedisulfonic acid. This special type is sold under the trade name Tinopal-5BM-GX by Ciba-Geigy Corporation.

If in the above formula R 1 is aniline, R ₂ is morphiline and M is eg a sodium cation, then the optical brightener is the disodium salt of the acid

4,4 ', - bis [(4-anilino-6-morphilino-s-triazin-2-yl) amino] -2,2`-stilbendisulfonic acid. This special type of optical brightener is sold under the trade name Tinopal-AMS-GX by Ciba-Geigy Corporation.

DETAILED DESCRIPTION OF THE INVENTION

EXAMPLE 1 - Preparation of PEI 1800 E7

The ethoxylation is carried out in a 7.6 L (2 gallon) stirred stainless steel autoclave [1 gal (US) = 3.78543 1], equipped with a device for measuring and controlling temperature, measuring vacuum and purging pressure with inert gas, sampling and introducing ethylene oxide as a liquid. A 9 kg (~ 20 lb) net ethylene oxide (ARC) cylinder is designed to supply ethylene oxide as a liquid by pump to an autoclave from a cylinder placed on the scale to record changes in cylinder weight.

A batch of 750 g of polyethyleneimine (PEI) (Nippon Shokubai, Epomin SP018 with a reported average molecular weight of 1800, equal to 0.417 moles of polymer and 17.4 moles of nitrogen functions) was charged into the autoclave. The autoclave is then sealed and purged with air (vacuuming to minus 711.2 torr (28 ”Hg) [1” Hg - 25.4 torr] and then increasing the nitrogen pressure to 1,723.7 kPa (250 psia) [1 psia = 6.8947 kPa], then the pressure is released to atmospheric). The contents of the autoclave were heated to 130 ° C under vacuum. After an hour, the pressure in the autoclave was increased with nitrogen to 250 psia while cooling the autoclave to 105 ° C. Ethylene oxide is then gradually added in portions to the autoclave while closely monitoring the autoclave pressure, temperature and ethylene oxide flow rate. The ethylene oxide pump is turned off and cooling is carried out to limit any temperature increase due to any exothermic reaction. The temperature is maintained between 100 and 110 ° C while the total pressure gradually increases during the reaction. After adding a total amount of 750 g of ethylene oxide to the autoclave (about one mole of ethylene oxide per PEI nitrogen function), the temperature was raised to 110 ° C and the autoclave was allowed to stir for an additional hour. Vacuum is performed at this point to remove any unreacted ethylene oxide residues.

Next, operate continuously under vacuum while cooling the autoclave to 50 ° C while introducing 376 g of 25% sodium methoxide in methanol solution (1.74 moles to achieve a 10% catalyst load based on PEI nitrogen functions). The methoxide solution is sucked into the autoclave under vacuum and then the set temperature of the autoclave is raised to 130 ° C. A device is used to monitor the energy consumed by the mixer. The stirring energy is monitored along with temperature and pressure. By removing the methanol from the autoclave and increasing the viscosity of the mixture, the stirring energy and temperature values gradually increase and stabilize over 1 hour, indicating that most of the methanol has been removed. The mixture was further heated and stirred under vacuum for an additional 30 minutes.

The vacuum was removed and the autoclave cooled to 105 ° C while increasing the pressure with nitrogen to 250 psia and then releasing the pressure to ambient pressure. In an autoclave, the pressure was increased with nitrogen to 200 psia. Ethylene oxide is again added portionwise to the autoclave as first time, while strictly monitoring the autoclave pressure, temperature and ethylene oxide flow rate while maintaining a temperature between 100 and 110 ° C and limiting any temperature increase due to any exothermic reaction. After the addition of a total amount of 4,500 g of ethylene oxide (giving a total of 7 moles of ethylene oxide per PEI nitrogen function) achieved over several hours, the temperature is raised to 110 ° C and the mixture is stirred for an additional hour.

The reaction mixture was then collected in nitrogen purged flasks and optionally transferred to a 22 liter three-necked round bottom flask equipped with heating and stirring. The strongly alkaline catalyst was neutralized by the addition of 167 g of methanesulfonic acid (1.74 moles). The reaction mixture is then deodorized by passing 2 8321 (100 cu.ft) [1ft ³ = 28,321] inert gas / argon or nitrogen) through a gas dispersion frit and reaction mixture while stirring and heating the mixture to 130 ° C.

The final reaction product was cooled somewhat and collected in nitrogen purged glass vessels.

In other preparations, the neutralization and deodorization is carried out in the reactor prior to product discharge.

EXAMPLE 2 - Quaternization of PEI 1800 E7

In a 500 ml Erlenmeyer equipped with a magnetic stir bar, add polyethyleneimine with a relative molecular weight of 1800, which is further modified by ethoxylation to a degree of about 7 ethyleneoxy residues on nitrogen (PEI 1800, E ₇ ) (207.3 g, 0.590 mole of nitrogen, prepared as in Example I) and acetonitrile (120 g). Diemethylsulfate (28.3 g, 0.224 mol) was added in one portion to a rapidly stirred solution, which was then stoppered and stirred at room temperature overnight. Acetonitrile is removed by rotary evaporation at 60 ° C, followed by further stripping of the solvent using a Kugelrohr apparatus at about 80 ° C to give 220 g of the desired partially quaternized material as a dark brown viscous liquid. ¹³ C-NMR (D 2 O) spectrum, obtained from a sample of the reaction product, shows the absence of carbon resonance at 5858ppm, corresponding to dimethyl sulfate. The ¹ H-NMR spectrum ⁽ D 2 O) shows a partial shift of the resonance to 2.5 ppm as the methylenes adjacent to the non-quaternized nitrogen were shifted to about 3.0 ppm. This is consistent with the required quaternization of 38% nitrogen.

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EXAMPLE 3 - Preparation of PEO 1800 E7 amine oxides

In a 500 ml Erlenmeyer equipped with a magnetic stir bar, add polyethyleneimine with a relative molecular weight of 1800, which is further modified by ethoxylation to a degree of about 7 ethoxy groups per nitrogen (PEI 1800, E ₇ ) (209 g, 0.595 mol nitrogen) , prepared as in Example I) and hydrogen peroxide (120 g of a 30% by weight solution in water,

1.6 mol). The flask is stoppered and after initial exothermic reaction is stirred at room temperature overnight. The 1 H-NMR spectrum obtained from a sample of the reaction mixture indicates complete conversion. The resonance attributed to the methylene protons adjacent to the non-oxidized nitrogen has shifted from its original position to ~ 2.5 ppm to -3.5 ppm. About 5 g of 0.5% Pd on alumina pellets was added to the reaction solution and the solution was allowed to stand at room temperature for about 3 days. Solution The solution test with indicator paper is negative for peroxide. The material obtained is conveniently stored as a 51.1% solution of the active ingredient in water.

EXAMPLE 4 - Oxidation of quaternized PEI 1800 E7

In a 500 ml Erlenmeyer equipped with a magnetic stir bar, add polyethyleneimine with a relative molecular weight of 1800, which is further modified by ethoxylation to a degree of about 7 ethyleneoxy residues on nitrogen (PEI 1800, E ₇ ), subsequently quaternized with dimethylsulfate to about 4 7% (121.7 g, -0.32 moles of oxidizable nitrogen), hydrogen peroxide (40 g of a 50% by weight solution in water, 0.588 moles) and water (109.4 g). The flask is stoppered and after initial exothermic reaction is stirred at room temperature overnight. The ¹ H-NMR spectrum (D ₂ O), obtained from a sample of the reaction mixture, shows that methylene peaks at 2.5-3.0 ppm shifted to -3.5 ppm. -5 g of 0.5% Pd on alumina pellets was added to the reaction solution and the solution was allowed to stand at room temperature for -3 days. The solution test with indicator paper is negative for peroxide. The desired material is obtained with -4.7% quaternized nitrogen and -95.3% oxides oxidized to the amine oxide and is conveniently stored as a 46.5% solution in water.

EXAMPLE 4A - Preparation of PEI 1200 E7

The ethoxylation is carried out in a 7,6 L (2 gallon) stirred stainless steel autoclave [1 gal (US) = 3,78543 1], equipped with a device for measuring and controlling temperature, measuring vacuum and purging pressure with inert gas, sampling and introducing ethylene oxide as a liquid. 9 kg (-20 lb) net ethylene oxide (ARC) cylinder is designed to deliver

-70 • ·

of ethylene oxide liquid by pump into an autoclave from a pressure bottle placed on the scale to record changes in bottle weight.

A batch of 750 g of polyethyleneimine (PEI) (with a reported average molecular weight of 1200, equal to 0.625 moles of polymer and 17.4 moles of nitrogen functions) was charged into the autoclave. The autoclave is then sealed and purged with air (minus vacuum)

711.2 torr (28 ”Hg) [1” Hg = 25.4 torr] followed by increasing the nitrogen pressure to 1,723.7 kPa (250 psia) [1 psia = 6.8947 kPa], then relieve the pressure to atmospheric ). The contents of the autoclave were heated to 130 ° C under vacuum. After an hour, the pressure in the autoclave was increased with nitrogen to 250 psia while cooling the autoclave to 105 ° C. Ethylene oxide is then gradually added in portions to the autoclave while closely monitoring the autoclave pressure, temperature and ethylene oxide flow rate. The ethylene oxide pump is turned off and cooling is carried out to limit any temperature increase due to any exothermic reaction. The temperature is maintained between 100 and 110 ° C while the total pressure gradually increases during the reaction. After adding a total amount of 750 g of ethylene oxide to the autoclave (about one mole of ethylene oxide per PEI nitrogen function), the temperature was raised to 110 ° C and the autoclave was allowed to stir for an additional hour. Vacuum is performed at this point to remove any unreacted ethylene oxide residues.

Next, operate continuously under vacuum while cooling the autoclave to 50 ° C while introducing 376 g of 25% sodium methoxide in methanol solution (1.74 moles to achieve a 10% catalyst load based on PEI nitrogen functions). The methoxide solution is sucked into the autoclave under vacuum and then the set temperature of the autoclave is raised to 130 ° C. A device is used to monitor the energy consumed by the mixer. The stirring energy is monitored along with temperature and pressure. By removing the methanol from the autoclave and increasing the viscosity of the mixture, the stirring energy and temperature values gradually increase and stabilize over 1 hour, indicating that most of the methanol has been removed. The mixture was further heated and stirred under vacuum for an additional 30 minutes.

The vacuum was removed and the autoclave cooled to 105 ° C while increasing the pressure with nitrogen to 250 psia and then releasing the pressure to ambient pressure. In an autoclave, nitrogen pressure is increased to 200 psia. Ethylene oxide is again added portionwise to the autoclave as first time, while strictly monitoring the autoclave pressure, temperature and ethylene oxide flow rate while maintaining a temperature between 100 and 110 ° C and limiting any temperature increase due to any exothermic reaction. After adding a total amount of 4,500 g of ethylene oxide (giving a total of 7 moles of ethylene oxide per mole of PEI nitrogen function) achieved over several hours, the temperature is raised to 110 ° C and the mixture is stirred for an additional hour.

The reaction mixture was then collected in nitrogen purged flasks and optionally transferred to a 22 liter three-necked round-bottomed flask equipped with heating and stirring. The strongly alkaline catalyst was neutralized by the addition of 167 g of methanesulfonic acid (1.74 moles).

O

The reaction mixture is then deodorized by passing 2 8321 (100 cu.ft) [1ft = 28,321] of inert gas (argon or nitrogen) through the gas dispersion frit and the reaction mixture while stirring and heating the mixture to 130 ° C.

The final reaction product was cooled somewhat and collected in nitrogen purged glass vessels.

In other preparations, the neutralization and deodorization is carried out in the reactor prior to product discharge.

Other preferred examples, such as PEI 1200 E15 and PEI 1200 E20, can be prepared as described above by adjusting the reaction time and the relative amount of ethylene oxide used in the reaction.

EXAMPLE 4B - 9.7% quartemization of PEI 1200 E7

In a 500 mL Erlenmeyer equipped with a magnetic stir bar, add poly (ethyleneimine), MW 1200 ethoxylated to approximately 7 (248.4 g, 0.707 mol of nitrogen, prepared as in Example 5) and acetonitrile (Baker, 200 mL). ). Diemethylsulfat (Aldrich,

8.48 g (0.067 mol) was added in one portion to a rapidly stirred solution, which was then stoppered and stirred at room temperature overnight. Acetonitrile was removed by rotary evaporation at 6060 ° C, followed by further stripping of the solvent using a Kugelrohr apparatus (Aldrich) at -80 ° C to obtain -220 g of the desired material as a dark brown viscous liquid. ¹³ C-NMR (D 2 O) spectra showed the absence of a peak at 5858ppm, corresponding to dimethyl sulfate. ¹ H-NMR spectrum ⁽ D 2 O) shows a partial shift of the peak to 2.5 ppm (methylenes attached to non-quaternized nitrogen) to -3.0 ppm.

EXAMPLE 5 - Preparation of dirt-releasing polymers from non-cotton fabrics

Synthesis of sodium 2- (2,3-dihydroxypropoxy) ethanesulfonate monomer

To a 500 ml three-necked round-bottomed flask equipped with a magnetic stir bar, modified Claisen distillation head, condenser (distillation kit, thermometer and temperature controller (Thermo-O-Watch ™, I ² R)) was added 2-hydroxyethanesulfonic acid (isethionic) , sodium salt (Aldrich, 50.0 g, 0.338 mol), sodium hydroxide (2.7 g, • · · ·

0.0675 mol) and glycerin (Baker, 310.9 g, 3.38 mol). The solution was heated to 190 ° C under argon overnight while water distilled off the reaction mixture. The C-NMR (DMSO-day) spectrum shows that the reaction is terminated by virtually disappearing the isehionate peaks at -53.5 ppm and -57.4 ppm and the appearance of product peaks at 51.4 ppm (-CH ₂ SO ₃ Na) and -67.5 ppm (CH ₂ CH2SO3Na). The solution was cooled to 100 ° C and neutralized to pH 7 with methanesulfonic acid (Aldrich). The desired pure material was obtained by adding 0.8 mol% monobasic potassium phosphate buffer, and heating on a Kugelrohr apparatus (Aldrich) at 200 ° C for 3 hours at 1 torr (1 mmHg) to yield 77 g of a yellow waxy solid. As an alternative, not all glycerin is removed prior to use in the preparation of oligomers. The use of a SEG glycerin solution may be a convenient way to handle this sulfonated monomer.

EXAMPLE 6 - Synthesis of sodium 2- [2- (2-hydroxyethoxy) ethoxy] ethanesulfonate monomer

To a 1 liter 3-neck round bottom flask equipped with a magnetic stir bar, modified Claisen distillation head, condenser (distillation kit, thermometer and temperature controller (Thermo-O-Watch ™, IR)) is added 2-hydroxyethanesulfonic acid (isethionic), sodium salt (Aldrich, 100.0 g, 0.675 mol) and distilled water (90 mL) After dissolution, one drop of hydrogen peroxide (Aldrich, 30% by weight in water) was added to oxidize traces of bisulfite and the solution was stirred for one hour. peroxide indicator shows a very poorly positive test result. Sodium hydroxide pellets (MCB,

2.5 g, 0.0625 mol) followed by diethylene glycol (Fisher, 303.3 g, 2.86 mol). The solution was heated to 190 ° C under argon overnight while water distilled off the reaction mixture. Spectrum

C-NMR (DMSO-d6) shows that the reaction is terminated by the disappearance of isehionate peaks at -53.5 ppm and -57.4 ppm. The solution was cooled to room temperature and neutralized to pH 7 by the addition of 57.4 g of a 16.4% solution of p-toluenesulfonic acid monohydrate in diethylene glycol. (Alternatively, methanesulfonic acid may be used). ^{The 13} C-NMR spectrum of the product shows resonances at -51 pp (-CH ₂ SO ₃ Na), -60 ppm (-CH ₂ OH) and -69 ppm, -72 ppm and -77 ppm for the remaining four methylene groups. Small resonances are also visible for sodium p-toluenesulfonate, which formed during neutralization. The reaction gives 451 g of a 35.3% solution of sodium 2- [2- (2-hydroxyethoxy) ethoxy] ethanesulfonates in diethylene glycol. Excess ethylene glycol is removed by adding 0.8 mol% monobasic potassium phosphate (Aldrich) as buffer and heating on a Kugelrohr apparatus (Aldrich) at 150 ° C for 3 hours at 1 torr (1 mm Hg) to give the desired "SE ₃ " (as defined above) as a highly viscous oil or enamel.

EXAMPLE 7 - Synthesis of sodium 2- {2- [2- (2-hydroxyethoxy) ethoxy] ethoxy} ethanesulfonate monomer

To a 1 liter 3-neck round bottom flask equipped with a magnetic stir bar, modified Claisen distillation head, condenser (distillation kit, thermometer and temperature controller (Thermo-O-Watch ™, IR)) is added 2-hydroxyethanesulfonic acid (isethionic), sodium salt (Aldrich, 205.0 g, 1.38 mol) and distilled water (200 mL) After dissolution, one drop of hydrogen peroxide (Aldrich, 30% by weight in water) was added to oxidize traces of bisulfite. The strip of peroxide indicator shows a very slightly positive test result, and sodium hydroxide pellets (MCB,

5.5 g, 0.138 mol), followed by triethylene glycol (Aldirch, 448.7 g, 3.0 mol). Optionally, triethylene glycol can be purified by heating with a strong base, e.g., NaOH, until color is stabilized and then distilling off the purified glycol for use in synthesis. The solution was heated to 190 ° C under argon overnight while water distilled off the reaction mixture. ¹³ C-NMR (DMSO-d6) spectrum shows that the reaction is terminated by the disappearance of isehionate peaks at -53.5 ppm and -57.4 ppm and the appearance of product peaks at 51.4 ppm (-CTUSCbNa), -60 ppm ( -CH2OH) and at ~ 67 ppm, -69 ppm and -72 ppm for methylene groups remaining. The solution was cooled to room temperature and neutralized to pH 7 with methanesulfonic acid (Aldrich). The reaction gives 650 g of a 59.5% solution of sodium 2- {2- [2- (2-hydroxyethoxy) ethoxy] ethoxy} ethanesulfonate in triehylene glycol. Excess ethylene glycol was removed by adding 0.8 mol% monobasic potassium phosphate (Aldirch) as a buffer and heating on a Kugelrohr apparatus (Aldrich) at 180 ° C for 5.5 hours at 1 torr (1 mm Hg) to obtain the desired material as brown solid. It is found that a more soluble buffer may be more effective for controlling pH during stripping of excess triethylene glycol. One example of such a more soluble buffer is the methanesulfonic acid salt of N-methylmorpholine. Alternatively, the pH can be controlled by frequent or continuous addition of an acid such as methanesulfonic acid to maintain the pH near neutral during stripping of the excess glycol.

The material is believed to contain a low level of disulfonate resulting from the reaction of both ends of triethylene glycol with isethionate. However, the raw material is used as an anionic end capping group for the preparation of polymers without further purification.

Other preparations use large excesses of triethylene glycol, e.g. 5 to 10 moles per mole of isethionate.

·· φ ΦΦ ·· φ φ φ φφφφ φ φ φ φφφφ

EXAMPLE 8 - Synthesis of oligomers of sodium 2- [2- (2-hydroxyethoxy) ethoxy] ethanesulfonate, dimethyl terephthalate, sodium 2- (2,3-dihydroxypropoxy) ethanesulfonate, glycerine, ethylene glycol and propylene glycol

To a 250 ml three-necked round bottom flask equipped with a magnetic stir bar, modified Claisen distillation head, condenser (distillation kit, thermometer and temperature controller (Thermo-O-Watch ™, I ² R))

Sodium 2- [2- (2-hydroxyethoxy) ethoxy] ethanesulfonate (7.0 g, 0.030 mol), dimethyl terephthalate (14.4 g, 0.074 mol), sodium 2- (2,3-dihydroxypropoxy) ethanesulfonate (3.3 g, 0.015 mol), glycerin (Baker, 1.4 g, 0.015 mol), ethylene glycol (Baker, 14.0 g, 0.225 mol), propylene glycol (Fisher,

17.5 g, 0.230 mol) and titanium (IV) propoxide (0.01 g, 0.02% of total reagent weight).

The mixture was heated to 180 ° C and kept at this temperature under argon overnight while methanol and water distilled off from the reaction vessel. The material was transferred to a 500 ml single-necked round-bottomed flask and gradually warmed to 240 ° C over a period of 20 minutes in a Kugelrohr apparatus (Aldrich) at 2 torr (2 mm Hg) and maintained at room temperature for 1.5 hours. The reaction flask was then allowed to cool fairly quickly in air to near room temperature under vacuum (30 minutes). The reaction yielded 21.3 g of the desired oligomer as a brown enamel. ¹³ C-NMR (DMSO-d 6) spectrum shows the resonance for -C (O) OCH ₂ CH ₂ O (O) C- to -63.2 ppm (diester) and the resonance for -C (O) (OCH ₂ CH ₂₎ The ratio of the height of the diester peak to the height of the monoester peak is approximately 10. Resonances at -51.5 ppm and -51.6 ppm represent sulfoethoxy groups (-QHfeSCbNa) are also represented. -NMR (DMSO-d6) shows a resonance of -7.9 ppm, representing terephthalate aromatic hydrogens, and hydrolysis gas chromatography analysis shows that the molar ratio of incorporated ethylene glycol to incorporated propylene glycol is 1.7: 1. It also shows that about 0.9 If all of the glycerine monomer was incorporated as glycerine ester, this would represent approximately 4% of the final weight of the oligomers The solubility is tested by weighing small amounts of material into the vial, adding enough water to produce a 35% solution by vigorously shaking the vial Under these conditions, the material is readily soluble.

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-75 · »fe ef fe fe fe fe ef f ef f

EXAMPLE 9 - Synthesis of Sodium 2- (2- (2-hydroxyethoxy) ethoxy] ethanesulfonate, dimethyl terephthalate, 2- (2,3-dihydroxypropoxy) ethanesulfonate oligomer, ethylene glycol and propylene glycol oligomer

To a 250 ml three-necked round bottom flask equipped with a magnetic stir bar, modified Claisen distillation head, condenser (distillation kit, thermometer and temperature controller (Thermo-O-Watch ™, I ² R))

Sodium 2- (2- (2-hydroxyethoxy) ethoxy] ethanesulfonate (7.0 g, 0.030 mol), dimethyl terephthalate (14.4 g, 0.074 mol), sodium 2- (2,3-dihydroxypropoxy) ethanesulfonate (6.6 g, 0.030 mol), ethylene glycol (Baker, 14.0 g, 0.225 mol), propylene glycol (Fisher, 18.3 g, 0.240 mol) and titanium (IV) propoxide (0.01 g, 0.02% total weight of reacting This mixture was heated to 180 ° C and kept at that temperature overnight under argon while methanol and water were distilled off from the reaction vessel and transferred to a 500 ml single-necked round-bottomed flask and gradually warmed to 20 ° C over 20 minutes. 240 [deg.] C. in a Kugelrohr apparatus (Aldrich) at 0.1 torr (0.1 mm Hg) and held at 110 [deg.] C. The reaction flask was then allowed to cool in air to near room temperature under vacuum (30 min) quite quickly. The reaction yielded 24.4 g of the desired oligomer as a brown enamel.The ¹³ C-NMR (DMSO-d ₆ ) spectrum shows the resonance for -C (O) OCH 2 CH 2 O (O) C- to -63.2 ppm (diester) and resonance for -C (O) (OCH 2 CH 2 OH at -59.4 ppm (monoester). The ratio of the height of the diester peak to the height of the monoester peak is to be measured 8. Resonances at -51.5 ppm and -51.6 ppm represent sulfoethoxy groups (-CHkSCbNa) are also represented. 1 H-NMR (DMSO-d ₆ ) shows resonance at -7.9 ppm, representing terephthalate aromatic hydrogens. Hydrolysis gas chromatography analysis shows that the molar ratio of incorporated ethylene glycol to incorporated propylene glycol is 1.6: 1. It also shows that about 0.9% of the final polymer weight is glycerin. If all glycerin monomer were incorporated as glycerin ester, this would represent approximately 4% of the final weight of the oligomer. Solubility is tested by weighing small amounts of material into the vial, adding enough water to form a 35% solution by weight, and vigorously shaking the vial. Under these conditions, the material is readily soluble.

-76 • 4 ♦ ·

4 «4

EXAMPLE 10 - Synthesis of sodium 2- [2- (2-hydroxyethoxy) ethoxy] ethanesulfonate, dimethyl terephthalate, sodium 2- (2,3-dihydroxypropoxy) ethanesulfonate oligomer, glycerine, ethylene glycol and propylene glycol

To a 250 ml three-necked round bottom flask equipped with a magnetic stir bar, modified Claisen distillation head, condenser (distillation kit, thermometer and temperature controller (Thermo-O-Watch ™, IR))

Sodium 2- [2- (2-hydroxyethoxy) ethoxy] ethanesulfonate (7.0 g, 0.030 mol), dimethyl terephthalate (9.6 g, 0.049 mol), sodium 2- (2,3-dihydroxypropoxy) ethanesulfonate (2.2 g, 0.010 mol), glycerin (Baker, 1.8 g, 0.020 mol), ethylene glycol (Baker, 6.1 g, 0.100 mol), propylene glycol (Fisher, 7.5 g, 0.100 mol) and titanium (IV) propoxide (0.01 g, 0.02% total reagent weight). The mixture was heated to 180 ° C and kept at this temperature under argon overnight while the methanol was distilled off from the reaction vessel. The material was transferred to a 250 mL single neck round bottom flask and gradually warmed to 240 ° C over a period of 20 minutes in a Kugelrohr apparatus (Aldrich) at 3 torr (3 mm Hg) and maintained at the temperature for 1.5 hours. The reaction flask was then allowed to cool fairly quickly in air to near room temperature under vacuum (30 minutes). The reaction yields 18.1 g of the desired oligomer as a brown enamel. ¹³ C-NMR (DMSO-d 6) spectrum shows the resonance for -C (O) OCH 2 CH 2 O (O) C- at -63.2 ppm (diester). The resonance for -C (O) (OCH 2 CH 2 OH at -59.4 ppm (monoester) is not detectable and is at least 12 times smaller than the diester peak. Resonance at -51.5 ppm and -51.6 ppm representing sulfoethoxy groups (-CFLSCbNa) 1 H-NMR (DMSO-d 6) shows a resonance of -7.9 ppm, representing terephthalate aromatic hydrogens, and hydrolysis gas chromatography analysis shows that the molar ratio of incorporated ethylene glycol to incorporated propylene glycol is 1.6: 1. shows that about 0.45% of the final polymer weight is glycerin If all glycerin monomer was incorporated as glycerine ester, it would represent about 4% of the final oligomer weight. The solubility is tested by weighing small amounts of material into the vial, adding enough water to form 35 Under these conditions the material is readily soluble.

EXAMPLE 11 - Synthesis of sodium 2- [2- (2-hydroxyethoxy) ethoxy] ethanesulfonate, dimethyl terephthalate, sodium 2- (2,3-dihydroxypropoxy) ethanesulfonate oligomer, glycerine, ethylene glycol and propylene glycol

To a 250 ml three-necked round bottom flask equipped with a magnetic stir bar, modified Claisen distillation head, condenser (distillation kit, thermometer and temperature controller (Thermo-O-Watch ™, IR))

Sodium 2- [2- (2-hydroxyethoxy) ethoxy] ethanesulfonate (2.7 g, 0.011 mol, as in Example 2), dimethyl terephthalate (12.0 g, 0.062 mol, Aldrich), 2- (2,3-dihydroxypropoxy) ) sodium ethanesulfonate (5.0 g, 0.022 mol, as in Example 1), glycerin (Baker, 0.50 g, 0.0055 mol), ethylene glycol (Baker,

6.8 g, 0.110 mol), propylene glycol (Baker, 8.5 g, 0.112 mol) and titanium (IV) propoxide (0.01 g, 0.02% total weight of reagents). The mixture was heated to 180 ° C and kept at this temperature under argon overnight while methanol and water distilled off from the reaction vessel. The material was transferred to a 500 ml single-necked round-bottomed flask and gradually warmed to 240 ° C over a period of 20 minutes in a Kugelrohr apparatus (Aldrich) at 0.5 torr (0.5 mm Hg) and maintained at the temperature for 150 minutes. The reaction flask was then allowed to cool fairly quickly in air to near room temperature under vacuum (30 minutes). The reaction yielded 16.7 g of the desired oligomer as a brown enamel. ¹³ C-NMR (DMSO-d 6) spectrum shows the resonance for -C (O) OCH 2 CH 2 O (O) C at -63.2 ppm (diester) and the resonance for -C (O) (OCH 2 CH 2 OH at -59.4 ppm (monoester) The ratio of the height of the diester peak to the height of the monoester peak is to be 6.1. Resonances at -51.5 ppm and -51.6 ppm represent sulfoethoxy groups (-CTLSCbNa) are also represented. ¹ H-NMR (DMSO-d6) Hydrolysis gas chromatography analysis shows that the molar ratio of incorporated ethylene glycol to incorporated propylene glycol is 1.42: 1. The solubility is tested by weighing small amounts of material into the vial, adding enough water to A 9% sample of this material is further heated to 240 ° C at 0.5 torr (0.5 mm Hg) in a Kugelrohr apparatus and maintained at 80 ° C. ¹³ C-NMR spectrum ( DMSO-d ₆₎ shows no detectable peak for monoester at -59.4 ppm. The peak for diester 63.2 is alespoňl 1 times greater than the monomer peak. The solubility of this material is tested as above and it is also found that solubility is easy under these conditions.

The modified polyamines of the invention useful as soil release agents from cotton fabrics are suitably prepared by the following methods.

-78Detergent composition

The detergent compositions of the present invention may be in liquid, paste or granular form. Such compositions may be prepared by combining the essential - optional and optional ingredients at the prescribed concentrations in any suitable order and by any conventional means.

Liquid laundry compositions can be prepared by mixing the base and optional ingredients in any desired order to give the compositions containing the ingredients at the prescribed concentrations. The liquid compositions of the present invention may also be in a &quot; compact form &quot; in which case the liquid detergents of the present invention will contain less water than conventional liquid detergents.

TABLE I Liquid detergents

Folders 12 13 14 15 Dec % by weight C12-C15 alkylsulfate - 19.0 21.0 - C 12 -C 15 alkyl ethoxylated sulfate 23.0 4.0 4.0 25.0 C12-C14 N-methylglucamide 9.0 9.0 9.0 9.0 C12-C14 fatty alcohol ethoxylate 6.0 6.0 6.0 6.0 C12-C16 fatty acid 9.0 6.8 14.0 14.0 citric acid (anhydrous) 6.0 4,5 3.5 3.5 diethylenetriaminpentaethylenephosphonic acid (DPTA) 1.0 1.0 2,0 2,0 monoethanolamine 13.2 12.7 12.8 11.0 propanediol 12.7 14.5 13.1 10.0 ethanol 1,8 1,8 4.7 5.4 enzymes (protease, lipase) 2.4 2.4 2,0 2,0 a soil release agent 0.5 0.5 - - dirt release agent ²⁾ - - 0.5 0.5 boric acid 2.4 2.4 2.8 2.8 2-Butyloctanol 2,0 2,0 2,0 2,0 DC 3421 R 0.3 0.4 - - FF 400 R ⁴⁾ - - 0.3 0.4

0 0 00 00 0 0 0 0 0 0 0

0 0 0 0 0

0 0 000 000

0 0 0 • 0 000 000 00

-790 ·

poly (4-vinylpyridine) -N-oxide - - 0.5 0.5 N-vinylpyrrolidinone / vinylimidazole MW 10,000 copolymer 0.3 0.3 - - PEI 1800 E7 2,0 2,0 2,0 2,0 Tinopal UNPA-GX optical brightener 0,075 0.21 - - Tinopal 5BM-GX Optical Brightening Agent - - 0.21 0,075 water and accompanying components to balancing to balancing to balancing to balancing

A spin-release agent according to U.S. Pat. No. 4,968,451, Scheibel et al., issued November 6, 1990.

2. The soil release agent of Example 11.

3. Silicone oil marketed by Dow Corning.

4. Silicone glycol emulsifier marketed by Dow Corning.

The compositions described in Table I are suitable for washing colored fabrics in aqueous laundry solutions, providing an excellent benefit in inhibiting dye transfer. The dye transfer inhibition performance provided by combining PVNO or PVPI with selected polyamine (PEI 1800 E7) is significantly better than if dye transfer inhibiting polymers were used alone.

TABLE II Liquid detergents

Folders 16 17 18 19 Dec % by weight C12-C15 alkylethoxylated sulfate 18.0 16.0 18, 16.0 C12-C14 N-methylglucamide 4,5 3.1 4,5 3.1 C12-C14 fatty alcohol ethoxylate 2,0 1.0 2,0 1.0 C12-C16 fatty acid 2,0 2,0 2,0 2,0 citric acid (anhydrous) 3.0 2.5 3.0 2.5 monoethanolamine 0.0 0.75 0.0 0.75 propanediol 0.0 5.1 0.0 5.1 NaOH 2.93 2.9 2.93 2.9 ethanol 3.52 2.88 3.52 2.88 enzymes 1,25 0.7 1,25 0.7 dirt release agent ²⁾ 0.2 - 0.2 - dirt release agent ³⁾ - 1.18 - 1.18 sodium formate 0,093 0,058 0,093 0,058 boric acid 3.5 2.5 3.5 2.5

• 0 0 0

00 0 0 000 0 0 0

0 0 0 0 0 0 0

000 · 000 ·· 0 0 · 0 0 ·· - dU— 00000 ··

a silicone suds suppressor 0,119 0,085 0,119 0,085 poly (4-vinylpyridine) N-oxide 0.1 0.2 - - N- copolymer vinylpyrrolidinone / vinylimidazole MW 10,000 - - 0.1 0.2 PEI 1800 E7 2,0 2,0 2,0 2,0 Tinopal UNPA-GX optical brightener 0.05 - 0.05 - water and accompanying components to balancing to balancing to balancing to balancing

Bacillus amyloliquefaciens subtilisin as described in WO 95/10615, Genecor

International, published April 20, 1995.

2. The terephthalate copolymer of U.S. Pat. No. 4,968,451, Scheibel et al., issued November 6, 1990.

3. The soil release polymer of U.S. Pat. No. 4,702,857, Gosselink, issued Oct. 27, 1987. Concentrated high performance liquid detergents are prepared in the compositions of Table III.

TABLE III Liquid detergents

Folders 20 May 21 % by weight C14-C15 alkylpolyethoxylene (2,25) sulfonic acid 23,00 12.50 C12-C13 linear alkylbenzenesulfonic acid - 11.46 1,2-propanediol 10.50 3.97 monoethanolamine 12.50 3.65 C12-C13 alkylpolyethoxylate (6,5) 6.0 1.78 ethanol 3.80 1.75 C12-C14 fatty acid polyhydroxy amide 9.00 - C12-C16 coconut fatty acid 9.00 2.60 citric acid 6.00 6.04 DTPA 0.95 - sodium formate 0.14 - boric acid 2.4 1.0 tetraethylenepentaamine ethoxylate (15-18) 1.00 1.44 soil release agent ^υ 0.5 0.6 PEI 1800 E7 3.00 3.1 enzymes (protease and lipase) 2.55 2.27

silicone antifoam 0.04 0.02 poly (4-vinylpyridine) N-oxide (PVNO) 0.10 0.10 optical brightening agent - Tinopal UNPA-GX 0.20 0.20 water and accompanying components to balancing to balancing

A spin-release polymer according to U.S. Pat. No. 4,702,857, Gosselink, issued Oct. 27, 1987.

Granular compositions, for example, are generally prepared by combining basic granular ingredients (eg, surfactants, builders, water, etc.) as a slurry and spray drying the resulting slurry to a low residual moisture level (5-12%). The remaining dry ingredients may be admixed in a granular powder form with spray dried granules in a rotary mixing drum, and liquid ingredients (eg, enzymes, binders, and perfumes) may be sprayed onto the resulting formulas to form the final laundry detergent. The granular compositions of the invention may also be in a &quot; compact form &quot; that they may have a relatively higher density than conventional granular detergents, i.e. they can be used in a conventional manner. from 550 to 950 g / l. In these cases, the granular detergent compositions of the present invention will contain lower amounts of "inorganic builder salts" as compared to conventional granular detergent compositions; typical builder salts are the alkaline earth metal salts of sulfate and chloride salts, typically sodium sulfate; "Compact" detergents typically do not contain more than 10% of the filler salts.

TABLE IV Granular detergents

Folders 22nd 23 24 % by weight C13-C14 linear alkylbenzenesulfonic acid 11.40 - - C12-C15 alkylethoxylated sulfate - 10.00 - C12-C14 N-methylglucamide - - 13.00 tallow alkyl sulphate 1.80 1.80 1.80 C46 alkylsulfate 3.00 3.00 3.00 C45 alcohol E7 ethoxylate 4.00 4.00 4.00 tallow alcohol E7 ethoxylate 1.80 1.80 1.80 dispersant 0.07 0.07 0.07 silicone fluid 0.80 0.80 0.80 trinatriumcitran 14.00 14.00 14.00

φ φ φ φ φ φ φ φ φ φ φ φ φ φ

Φ Φ ·

I «Φ 1

-82 • φ φ φ φφ · φφφφ φφφφ

citric acid 3.00 3.00 3.00 zeolite 32.50 32.50 32.50 maleic acid / acrylic acid copolymer 5.0 5.0 5.0 cellulose (active protein) 0.03 0.03 0.03 alkalase / BAN 0.60 0.60 0.60 lipase 0.36 0.36 0.36 sodium silicate 2.00 2.00 2.00 sodium sulfate 3.50 3.50 3.50 poly (-vinylpyridine) -N-oxide (PVNO) 0.10 0.10 - N-vinylpyrrolidone / N-vinylimidazole copolymer MW 10,000 (PVPI) - - 0.20 soil release agent ¹ 0.5 - - a soil release agent - 0.5 - dirt release agent ³ - - 0.5 PEI 1800 E7 3.0 3.0 3.0 Tinopal UNPA-GX optical brightener 0.20 - 0.20 Tinopal 5BM-GX Optical Brightening Agent - 0.20 - accompanying components to balancing to balancing to balancing 1. Dirt-releasing polymer from non-cotton fabrics comp le U.S. No. 4,968,451 to Scheibe

et al., .11 06.11.1990.

2. The dirt-releasing polymer of the non-cotton fabrics of U.S. Pat. No. 5,415,807 to Gosselink,

Mr., Kellett and Hall, from 16.05.1995.

3. The dirt-releasing polymer of the non-cotton fabrics of U.S. Pat. No. 4,702,857, Gosselimk, issued Oct. 27, 1987.

The compositions described in Table IV are suitable for washing colored fabrics in aqueous laundry solutions, providing an excellent benefit in inhibiting dye transfer. The dye transfer inhibition performance provided by combining PVNO or PVPI with a selected polyamine (PEI 1800 E7) is significantly better than if dye transfer polymers or polyamine were used alone.

· · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · ·

Industrial applicability

The present invention also provides a method for washing colored fabrics wherein little or no color transfer occurs. The method utilizes contacting these fabrics with an aqueous wash solution formed in an effective amount of the detergent compositions described above. The contacting of the fabrics with the wash solution is usually done under agitation conditions.

Agitation is preferably provided by an automatic washing machine for good cleaning. Washing is preferably followed by drying the wet fabric in a conventional laundry dryer. An effective amount of a liquid or granular detergent in an aqueous solution in an automatic washing machine is preferably from 500 to 7000 ppm, more preferably from 1000 to 3000 ppm.

35V7 - W frfr frfr frfr

Claims (2)

PATENT Claims • · ·) · · frfrfr -84 · A detergent composition comprising: a) at least 0.01% by weight of a dye transfer inhibiting agent; at least 0.01% by weight of a water-soluble or dispersible, modified polyamine dirt dispersing agent comprising a polyamine backbone corresponding to formula 1: H (1) (b) [H ₂ NR] _{n + 1} - [NR] _m - [NR] _n- NH ₂ having a modified polyamine of formula 2 V ("+ i) W _m Y _n Z" or a polyamine backbone corresponding to formula 3: (2) (3) [H ₂ NR] _n . _{k +} i- [NR] _m - [NR] _n - [NR] _k -NH ₂ having a modified polyamine of formula 4 V _{(n. K +} i) W _m Y _n Y _'k Z, (4) where k is less than or equal to n, the polyamine backbone prior to modification has a molecular weight greater than 200 daltons, wherein (i) units V are terminal units having the general formula 5,6,7: E O i, ENR- (5) or EN ⁺ -R- (6) or EN -R (Ό ii) units W are backbone units having the general formula 8, 9,10: -N-R- (8) or -N-R- (9) or -N-R- (10) iii) Y units are branching units having the general formula 11,12,13: E O I x ^- τ -N-R- (11) or -N + -R- (12) or -N-R- (13); 9 9 9 9 9 -85iv) Z units are terminal units having the general formula 14,15,16: -NE (14) or -N ⁺ E; or O í -NE (16) wherein the backbone bond units R are selected from the group consisting of C ₂ -C ₁₂ alkylenes, C ₄ -C ₁₂ alkenylene, C ₃ -C ₁₂ hydroxyalkylene, C ₄ -C ₁₂ dihydroxyalkylene, C ₈ -C ₁₂ dialkylarylene, - (R ¹ R ¹ -, - (R ¹ R ¹ OR ² ), -C (O) (R ⁴ ) r C (O) -CH ₂ CH (OR ² ) CH ₂ -, - (CH ₂ CH (OR ² ) CH ² O) z (R ¹⁰ ) y R ¹ (OCH ² CH (OR ² ) CH 2) and mixtures thereof, preferably from C ₂ -C ₁₂ alkylenes, C ₃ -C ₁₂ hydroxyalkylene, C ₄ -C ₁₂ dihydroxyalkylene, C ₈ -C ₁₂ dialkylarylene, - (R ^ jxR ¹ -, - (R ¹⁰ ) x R ⁵ (OR ¹ ) x -, - (CH ₂ CH (OR ² ) CH 2 -, - (CH ₂ CH (OH) CH ₂ O) _z (R ¹⁰ O) ¹ R ¹ (OCH ₂ CH (OH) CH ₂ ) w and mixtures thereof, more preferably from C ₂ -C ₁₂ alkylenes, C ₃ -C ₁₂ hydroxyalkylene, C ₄ -C ₁₂ dihydroxyalkylene, - (R ¹ -x R ¹ -, - (R ¹ O) x R ⁵ (OR ¹ ) x - (CH 2 CH 2 OH) CH 2 O 2 R ₂ , R 2 OCH 2 CH 2 OH ³ CH ² -, and mixtures thereof, most preferably C 2 -C 12 alkylenes and mixtures wherein R ¹ is C 2 -C 6 alkylene, preferably ethylene, and mixtures thereof, R ² is hydrogen, - (R * O) x B, and mixtures thereof, preferably hydrogen; R ³ is C 1 -C 18 alkyl, C 7 -C 12 arylalkyl, C 7 -C 12 alkyl substituted aryl, C 8 -C 12 aryl and mixtures thereof, C 1 -C 6 alkyl and mixtures thereof, more preferably methyl; R ⁴ is C 1 -C 12 alkylene, C ₄ -C ₁₂ alkenylene, C ₈ -C ₁₂ arylalkylene, C 6 -C 10 arylene and mixtures thereof, preferably C ₂ -C ₁₂ alkylene, C ₈ -C ₁₂ arylalkylene and mixtures thereof, more preferably ethylene, butylene and mixtures thereof; R ⁵ is C 1 -C 12 alkylene, C ₃ - C ₁₂ hydroxyalkylene, C ₄ -C ₁₂ dihydroxyalkylene, C ₈ -C ₂ dialkylarylene, -C (O) -, -QOjNHR HQO ^) -, ^{-R (OR)} -, -C (O) (R ⁴⁾ r C (O) -, -CH2CH (OH) CH2-, -CH2CH (OH) CH2O (R ¹ O) y R ¹ OCH 2 CH (OH) CH 2 group and mixtures thereof; preferably ethylene, -C (O) -, -C (O) NHR ⁶ NHC (O) -, -R (OR ¹ ) 4, -CH 2 H 3 OH 1 CH ₂ O ₂ O ₂ O ₂ CH ₂ OH ₃ CH ₂ -, -CH 2 CH (OH) CH ₂ - and mixtures thereof, more preferably -CH ₂ CH (OH) CH ₂ -; R ⁶ is C 2 -C 12 alkylene or C 6 -C 12 arylene; the E units are selected from the group consisting of hydrogen, C 1 -C 22 alkyl, C 3 -C 22 alkenyl, C 7 -C 22 arylalkyl, C 2 -C 22 hydroxyalkyl, - (CH 2) p CO 2 M, - (CH 2) q SO 3 M, -CH (CH 2 CO 2 M) - (CH 2) pPO 3 M, - (R 6 'xB, -C (O) R ³ and mixtures thereof; preferably hydrogen, C 3 -C ₂₂ hydroxyalkyl, benzyl, C 1 -C ₂₂ alkyl, O) R ³ , - (CH 2) PCO ₂ 'M ⁺ , - (CH 2) _q SO ₃ ' M ⁺ , -CH (CH 2 CO 2 M) CO 2 M and mixtures thereof, more preferably hydrogen, C 1 -C 22 alkyl, - (R'O) XB, -C (O) R ³ and mixtures thereof, most preferably - (R'O) X B; B is hydrogen, C 1 -C ₆ alkyl, - (CH ₂ ) qSO ₃ M, - (CH ₂ ) _p CO ₂ M, - (CH ₂ ) _p PO ₃ M · ft · · · ftft · · · -86- (CH ₂ ) _q (CHSO ₃ M) CH ₂ SO ₃ M, - (CH ₂ ) _q (CHSO ₂ M) CH ₂ SO ₃ M, -PO ₃ M, and mixtures thereof; preferably hydrogen, C 1 -C 6 alkyl, - (CH ₂ ) _q SO ₃ M, - (CH ₂ ) _q (CHSO ₃ M) CH ₂ SO ₃ M, - (CH ₂ ) _q (CHSO ₂ M) CH ₂ SO ₃ M and mixtures thereof, more preferably hydrogen, - (CH ₂ ) _q SO ₃ M, and mixtures thereof, most preferably hydrogen; M is hydrogen or a water-soluble cation in an amount sufficient to achieve a charge balance; X is a water-soluble anion; m has a value of from 4 to 400; n is from 0 to 200; p is from 1 to 6; q is from 0 to 6; r has a value of 0 or was not; w is 0 or 1; x is from 1 to 100; y is from 0 to 100; z has a value of * 0 or 1; and (c) a balance carrier and ancillary ingredients selected from the group consisting of builders, optical brighteners, bleaches, bleach boosters, bleach activators, enzymes, enzyme stabilizers, soap suppressants foam, dyes, perfumes, coloring agents, filler salts, hydrotropes, and mixtures thereof. 2. A detergent composition which provides the benefit of inhibiting dye transfer comprising: (a) at least 3% by weight of an anionic detersive surfactant selected from the group consisting of alkyl alkoxy sulphate, alkyl sulphate and mixtures thereof; (b) at least 2% by weight of a nonionic detersive surfactant selected from the group consisting of alkyl alkoxylate, a fatty acid amide having the general formula 24: OR ⁸ , II I (24) r ⁷ -cnq Wherein R is C 7 -C ₂₂ alkyl, R is independently selected from the group consisting of hydrogen, C 1 -C 4 alkyl, C 4 -C 4 hydroxyalkyl, - (C ₂ H ₄ O) ₃ H and mixtures thereof; wherein j is from 1 to 3; and mixtures of these surfactants; c) at least 0.01% by weight of a dye transfer inhibiting agent; d) at least 0.05% by weight of a water-soluble or dispersible, modified polyamine fabric surface modifying agent comprising a polyamine backbone corresponding to formula 1: H I (1) [H ₂ NR] _wl - [NR] _m - [NR] '- _NH2 having a modified polyamine formula 2 I ·· 99 «· · · · · · · · · · · -87V (n + 1) W _m Y _n Z or polyamine backbone corresponding to general formula 3: • 9 ·· • · (2) VR] _k -NH ₂ (4) [H ₂ NR] _n -k + i- [NR] _m - [NR] _n - [mající having a modified polyamine of formula 4 V _(n . _{K +} i) W _m Y _n Y _{k k} , where k is less than or equal to n, the polyamine backbone prior to modification has a relative molecular weight of greater than 200 daltons, wherein (i) units V are terminal units having the general formula 5, 6, 7: X " ENR- (5) or EN ⁺ -R- (6) or ENR- (7) (ii) units W are backbone units having the general formula 8,9,10: X " -N-R- (8) or -N-R- (9) or -N-R- (10) (iii) units Y are branching units having the general formula 11, 12, 13: X " -N-R- (11) or -N-R- (12) or -N-R- (13), and iv) Z units are terminal units having the general formula 14,15,16: X -NE (14) or -N + -E- (15) or -NE (16), wherein the backbone linking R units are selected from the group consisting of C ₂ -C _i2 alkylene, _C4-Ci2 alkenylene, _C3-Ci2 hydroxyalkylene, C ₄ -C ₁₂ dihydroxyalkylene, C ₈ -C ₁₂ dialkylarylene, - (R ¹ , R ¹ , R ¹ -, - (R ¹ , X ¹ , R ^1, OR ¹ -), -C (O) (R ⁴ ) r C (O) -, -CH2CH ^(OR2) CH2 -, - _(CH2 CH ^(OR2) CH2O) z (R ¹ O) y R ¹ (OCH 2 CH (OR ²⁾ CH 2) _w, and mixtures thereof, preferably from C ₂ -C ₂ alkylene, , C ₃ -C ₁₂ hydroxyalkylene, C ₄ -C ₁₂ dihydroxyalkylene, C ₈ -C ₁₂ dialkylarylene, - (R ¹ , J ¹ R ¹ -, - (R ¹ , J ¹ R ¹ OR ¹ -, - 88). · · · · · · ·· * ·· * ··· *** ·· - (CH ₂ CH (OR ² ) CH ₂ - (CH ₂ CH (OH) CH ₂ O) z (R ¹⁰ O) y R ¹ (OCH ₂ CH (OH) CH ₂ ) _w and mixtures thereof, more preferably from C ₂ -C ₁₂ alkylene, C 3 -C ₂ hydroxyalkylene, C4-C ₂ dihydroxyalkylene, - (R ¹ jxr -, - (R ¹ O) x R ⁵ (OR ^1, - (CHíCHÍOHjCH jzCR ^ ^ ^ OC ^ JYR CHCOHjjCH ^ w-, and mixtures thereof, most preferably C2-CI2 wherein R ¹ is C 2 -C 6 alkylene, preferably ethylene, and mixtures thereof, R is hydrogen, - (R 6) χΒ, and mixtures thereof, preferably hydrogen; R is C 1 -C 18 alkyl, C 7 -C 18 R _{2 is} arylalkyl, C ₇ -C ₁₂ alkyl substituted aryl, C 6 -C ₁₂ aryl and mixtures thereof, C 1 -C 6 alkyl and mixtures thereof, more preferably methyl; R ⁴ is C 1 -C 12 alkylene, C 4 -C 12 alkenylene, C 5 -C 12 arylalkylene, C 6 -C 10 arylene and mixtures thereof, preferably C 2 -C 12 alkylene, C 5 -C 12 arylalkylene and mixtures thereof, more preferably ethylene, butylene and mixtures thereof; R ⁵ is C 1 -C 12 alkylene, C 3 -C ₁₂ hydroxyalkylene, C 4 -C ₂ dihydroxyalkylene C ₈ -C ₁₂ dialkylarylene, -C (O) -, -C (O) NHR ⁶ NHC (O) -, -R 4 OR ¹ ) -, -C (O) (R ⁴ ) r C (O) -, A -CH 2 CH (OH) CH 2 -, -CH 2 CH 2 OH 1 C 2 OCR 4 jy R 4 C 2 CHCOH 3 CH 4 group and mixtures thereof; preferably ethylene, -C (O) -, -C (O) NHR ⁶ NHC (O) -, -R (OR ¹ ) 4 -, -CH ₂ CH (OH) CH ₂ O (R ¹⁰ ) y R ¹⁰ OCH ² CH (OH) - CH ₂ ) _w - -CH ₂ CH (OH) CH ₂ - and mixtures thereof, more preferably -CH ₂ CH (OH) CH ₂ -; R ⁶ is C 2 -C 12 alkylene or C 6 -C 12 arylene; the 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, - (CH 2) pPO 3 M, - (R ⁴ ) ΧΒ, -C (O) R ^3, and mixtures thereof; preferably hydrogen, C 3 -C ₂₂ hydroxyalkyl, benzyl, C 1 -C ₂₂ alkyl, - (R 6, B, -C (O) R ³ , - (CH 2) p CO ₂ 'M ⁺ , ~ (CH 2) _q SO ₃ ' M ^+, -CH (CH2CO2M) CO2M and mixtures thereof, more preferably hydrogen, Ci-C22 alkyl, - (R'O) xB, -C (O) ^R3, and mixtures thereof, most preferably - (R ^^ B, B is hydrogen, C 1 -C 6 alkyl, - (CH ₂ ) qSO ₃ M, - (CH ₂ ) _p CO ₂ M, - (CH ₂ ) _p PO ₃ M - (CH ₂ ) _q (CHSO ₃ M) CH ₂ SO ₃ M, - (CH ₂ ) q (CHSO ₂ M) CH ₂ SO ₃ M, -PO ₃ M and mixtures thereof, preferably hydrogen, C 1 -C 6 alkyl, - (CH ₂ ) _q SO ₃ M, - ( CH ₂ ) _q (CHSO ₃ M) CH ₂ SO ₃ M, - (CH ₂ ) _q (CHSO ₂ M) CH ₂ SO ₃ M and mixtures thereof, more preferably hydrogen, - (CH ₂ ) _q SO ₃ M and mixtures among them, most preferably hydrogen; M is hydrogen or a water-soluble cation in an amount sufficient to achieve a charge balance; X is a water-soluble anion; m has a value of 4 to 400; n has a value of 0 to 200; to 6; q has a value of 0 to 6; r has a value of 0 or 1; w has a value of 0 or 1; x has a value of 1 to 100; y has a value of 0 to 100; has a value of 0 or 1; (e) a balance carrier and ancillary additives which are selected from the group consisting of builders, optical brighteners, bleaches, reagents. -89 ···· · · ·· I · · · · * (b) C) (d) e) booster enhancers, bleach activators, enzymes, enzyme stabilizers, soap suds suppressors, dyes, perfumes, colorants, filler salts, hydrotropes, and mixtures thereof. A detergent composition which provides the benefit of inhibiting dye transfer comprising: (a) at least 10% by weight of an anionic detersive surfactant selected from the group consisting of alkylsulfate, alkylalkoxysulfate, and mixtures thereof; 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; at least 0.05% by weight of a dye transfer inhibiting agent; optionally at least 1% by weight of a bleaching agent; at least 0.5% by weight of a water-soluble or dispersible, modified polyamine fabric surface modifying agent comprising a polyamine backbone corresponding to Formula 1: H [H ₂ NR] _{n + 1} - [NR] _m - [NR] _n -NH ₂ having a modified polyamine of formula 2 V (n + 1) W _m Y _n Z or a polyamine backbone corresponding to formula 3: O) (2) (3) (4) [H ₂ NR] _n . _k + i- [NR] _m - [NR] _n - [NR] _k -NH ₂ having a modified polyamine of formula 4 V ₍ " _{k +} i) W _m Y _n Y ' _k Z, where k is less than or equal to n, the polyamine backbone prior to modification has a relative molecular weight of greater than 200 daltons, where (i) units V are terminal units having the general formula 5, 6, 7: | XE-NR- (5) or E-N ⁺ -R- (6) or ENR- (7) E (ii) units W are backbone units having the general formula 8, 9,10: -90X -N-R- (8) or -N-R- (9) or -N-R- (10) (iii) Y units are branching units having the general formula 11,12,13: X -N-R- (11) or -N-R- (12) or -N-R- (13), and iv) units Z are terminal units having the general formula 14, 15, 16: -N-E (14) or -N ⁺ -E- O í or -N-E (16) E; wherein the backbone bond units R are selected from the group consisting of C ₂ -C ₁₂ alkylene, C 4 -C ₁₂ alkenylene, C 3 -C ₁₂ hydroxyalkylene, C 4 -C ₁₂ dihydroxyalkylene, C ₈ -C ₁₂ dialkylarylene, - (R * O) _X R 1 -, - (R 2 R 4 OR ¹ ), -, -C (O) (R ⁴ ) _r C (O) -C 1 CH 2 CH 2 -CH 2 -CH 2 -CH 2 CH 2 O 2 R ³ R ⁶ O R 2 OCH 2 CH 2 mixtures thereof, preferably from C ₂ -C ₁₂ alkylene, C 3 -C ₁₂ hydroxyalkylene, C 4 -C ₁₂ dihydroxyalkylene, C ₈ -C ₁₂ dialkylarylene, - (R 6 x R ¹ -, - (R ¹⁰ ) x R ⁵ (OR ¹ ) x-, - (CH ² CH (OR ² ) CH 2 -, - (CH ₂ CH (OH) CH ₂ O) _z (R ¹⁰ O) y R ¹ (OCH ₂ CH (OH) CH ₂ ) _w and mixtures thereof, more preferably C ₂ -C ₁₂ alkylene, C 3 -C ₁₂ hydroxyalkylene, C ₄ -C 12 dihydroxyalkylene, - (R ¹ x R ¹ -, - (R ¹⁰ ) x R ⁵ (OR ¹ ) x -, - ₍₂ ϋΗ 0Η (ΟΗ) ϋΗ Ο ₂₎ ζ (^ Ο) Χ ₍₂ θεΗ 0Η (ΟΗ)) ΕΗ ₂₎ ^ -, and mixtures thereof, most preferably C ₂ -C ₂ alkylene, and mixtures thereof; wherein R ¹ is C 2 -C 6 alkylene, preferably ethylene, and mixtures thereof; R ² is hydrogen, - (R ¹⁰ ) xB and mixtures thereof, preferably hydrogen; R ³ is C 1 -C 18 alkyl, C ₇ -C ₁₂ arylalkyl, C ₇ -C ₁₂ alkyl substituted aryl, C 6 -C ₁₂ aryl, and mixtures thereof; C 1 -C 6 alkyl and mixtures thereof, more preferably methyl; R ⁴ is C 1 -C 12 alkylene, C 4 -C 12 alkenylene, C 8 -C 12 arylalkylene, C 6 -C 10 arylene and mixtures thereof, preferably C 2 -C 12 alkylene, C 8 -C 12 arylalkylene and mixtures thereof, more preferably ethylene, butylene and mixtures thereof ; R ⁵ is C 1 -C 12 alkylene, C ₃ -C ₁₂ hydroxyalkylene, C 4 -C ₁₂ dihydroxyalkylene, C ₈ -C ₁₂ dialkylarylene, -C (O) -, -QO (NH 4 H) (O) -, -R (OR ¹ ) -, -C (O) (R ⁴ ) _r C (O) -, -CH ₂ CH ( An OH) CH ₂ -, -CH ₂ CH ₂ OH ₂ CH ₂ OR 2 - group, and mixtures thereof; preferably ethylene, -C (O) -, -C (O, N (R) N (S) (XO) -, -R (OR ¹ ) 2 -, - · · ··· 9 9 · 9 9 9 9 ₉ 9 99 9 9 9 99 * · · · · · · · · · · · -91-CH ₂ CH (OH) CH ₂ O (R ¹ O) y R ¹ OCH 2 CH (OH) CH2) w-, -CH2CH (OH) CH ₂ -A mixtures thereof, more preferably -CH ₂ CH (OH) CH ₂ -; R ^{4 * 6} is C 2 -C 12 alkylene or C 8 -C 12 arylene; the 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, - (R * O) xB, -C (O) ^R3, and mixtures thereof; preferably hydrogen, C3 -C22 hydroxyalkyl, benzyl, C1-C22 alkyl, - (R'O) xB, -C (O) R ^3, - (CH 2) pCO2'M ^+, - (CH 2) _q SO ₃ -M ⁺ , -CH (CH2CO2M) CO2M and mixtures thereof, more preferably hydrogen, C1-C22 alkyl, - (R JXB, -C (O) ^R3, and mixtures thereof, most preferably - ^(R! O) xB; B is hydrogen , C 1 -C ₆ alkyl, -CCH ₂ ) qSO ₃ M, - (CH 2) _p CO ₂ M, - (CH ₂ ) _p PO ₃ M - (CH ₂ ) _q (CHSO ₃ M) CH ₂ SO ₃ M, - ( CH 2) _q (CHSO ₂ M) CH ₂ SO ₃ M, -PO ₃ M, and mixtures thereof; preferably hydrogen, _Ci-C6 alkyl, - (CH _{2) q} SO ₃ M, - (CH _{2) q} (CHSO ₃ M) CH ₂ -SO 3 M, - (CH2) _q (CHSO2M) _CH2 SO3 M, and mixtures thereof, more preferably hydrogen, - (CH ₂ ) _q SO 3 M and mixtures thereof, most preferably hydrogen; M is hydrogen or a water-soluble cation in an amount sufficient to achieve a charge balance; X is a water-soluble anion; m has a value of from 4 to 400; n is from 0 to 200; p is from 1 to 6; q is from 0 to 6; r has a value of 0 or was not; w is 0 or 1; x is from 1 to 100; y is from 0 to 100; z is 0 or 1; and (f) a balance carrier and ancillary ingredients selected from the group consisting of builders, optical brighteners, bleaches, bleach boosters, bleach activators, enzymes, enzyme stabilizers, soap suppressants foam, dyes, perfumes, coloring agents, filler salts, hydrotropes, and mixtures thereof. 4. A detergent composition comprising the benefits of inhibiting dye transfer comprising: (a) at least 10% by weight of an anionic detersive surfactant selected from the group consisting of alkyl sulfate, alkylalkoxysulfate, 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 inhibiting agent; d) optionally at least 1% by weight of a bleaching agent; -92 ···· ···· (e) at least 0,5% by weight of a water-soluble or dispersible, modified polyamine fabric surface modifying agent containing a polyamine backbone corresponding to formula 1: H [H ₂ NR] _{n + 1} - [NR] _m - [NR] _n -NH ₂ having a modified polyamine formula 2 V (n + 1) W _m Y _n Z or a polyamine backbone corresponding to formula 3: HR [H ₂ NR] _n . _{k + 1} - [NR] _m - [NR] _n - [NR] _k -NH ₂ having a modified polyamine formula 4 (1) (2) (3) (4) V ₍ ". K ₊ i) W _m Y" Y ' _k Z, where k is less than or equal to n, the polyamine backbone prior to modification has a relative molecular weight greater than 200 daltons, wherein (i) units V are terminal units having the general formula 5, 6, 7: I XE-N-R- (5) or E-N-R- (6) or E-N-R- (7) (ii) W units are backbone units having the general formula 8, 9, 10: I xN-R- (8) or -N-R- (9) or -N-R- (10) (iii) units Y are branching units having the general formula 11, 12, 13: | X -N-R- (11) or -N-R- (12) or -N-R- (13), and iv) Z units are terminal units having the general formula 14,15, 16: X7 -N-E (14) or -N-E- (15) or -N-E (16) -93- * ♦. ·.:. Wherein the backbone bonding units R are selected from the group consisting of C 2 -C 12 alkylene, C 4 -C 12 alkenylene, C 3 -C 12 hydroxyalkylene, C 4 -C 12 dihydroxyalkylene, C ₈ -C 12 dialkylarylene, - (R 6 x R ¹ -, -) (R jxr ^OR1) x-, -C (O) (R ⁴⁾ r C (O) -, -CH2CH ^(OR2) CH2 -, - _(CH2 CH ^(OR2) CH2O) z (R ¹ O) y R ¹ (OCH ² CH (OR ² ) CH 2) w and mixtures thereof, preferably from C ₂ -C ₁₂ alkylene, C 3 -C ₁₂ hydroxyalkylene, C 4 -C ₁₂ dihydroxyalkylene, C ₈ -C ₁₂ dialkylarylene, - (R 6 x R 6) ^1- , - (R ¹⁰ ) _X R ⁵ (OR ¹ ) _X -, - (CH 3 CH 2 CH 2 -CH 2 -CH 2 CH 2 CH 2 CH 2 CH 2 O) R ⁴ OCH 2 CHCCH 3 CH 2 is a mixture thereof, more preferably C ₂ -C ₁₂ alkylene, C 3 -C ₁₂ hydroxyalkylene, C ₄ -C ₁₂ dihydroxyalkylene, - (R ¹ x R ¹ -, - (R ¹⁰ ) x R ⁵ (OR ¹ ) _x - (CH ₂ CH (OH) CH ₂ O) _z (R ¹⁰ O) y R ¹ (OCH ² CH ( OH)) _{CH2) w} -, and mixtures thereof, most preferably C ₂ -C ₂ alkylene, and mixtures thereof; wherein R ¹ is C ₂ -C 6 alkylene, preferably ethylene and mixtures thereof; R ² is hydrogen, - (R ¹⁰ ) xB and mixtures thereof, preferably hydrogen; R ³ is C 1 -C 18 alkyl, C 7 -C 12 arylalkyl, C 7 -C 12 alkyl substituted aryl, C 6 -C 12 aryl and mixtures thereof; C 1 -C 6 alkyl and mixtures thereof, more preferably methyl; R ⁴ is C 1 -C 12 alkylene, C 4 -C ₁₂ alkenylene, C ₈ -C ₁₂ arylalkylene, C ₈ -C ₁₂ arylene and mixtures thereof, preferably C ₂ -C ₁₂ alkylene, C ₈ -C ₁₂ arylalkylene and mixtures thereof, more preferably ethylene, butylene and mixtures thereof; R ⁵ is C 1 -C ₁₂ alkylene, C 3 -C ₁₂ hydroxyalkylene, C 4 -C ₁₂ dihydroxyalkylene, C ₈ -C ₁₂ dialkylarylene, -C (O) -, -QO (NH 4 (HCl)) -, -R (OR ¹ ) -, -C (O) (R ⁴ ) _r C (O) -, -CH ₂ CH ( OH) CH ₂ -, -CH ₂ CH (OH) CH ₂ O (R ¹⁰ ) y R ¹⁰ OCH ² CH (OH) CH ₂ - group and mixtures thereof; preferably ethylene, -C (O) -, -C (O) NHR ⁶ NHC (O) -, -R ^ OR ^ y CH ₂ CH (OLI) CH ₂ O (R ¹ O) y R ¹ OCII2CH (OH) CH ₂ ) w -, -CH ₂ CH (OH) CH ₂ - and mixtures thereof, more preferably -CH ₂ CH (OH) CH ₂ -; R ⁶ is C 2 -C 12 alkylene or C 6 -C 12 arylene; the 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, - (CH 2) pPO 3 M, - (R 1, X B, -C (O) R ³ and mixtures thereof; preferably hydrogen, C 3 -C ₂₂ hydroxyalkyl, benzyl, C 1 -C ₂₂ alkyl, - (R'O) _X B, -C (O) R ³ , - (CtypCO 4 M *, - (CH 2) qSO _{3 '} M ⁺ , -CH (CH ₂ CO ₂ M) CO ₂ M and mixtures thereof, more preferably hydrogen, C 1 -C ₂₂ alkyl, - ( R'O) _X B, -C (O) R ^3, and mixtures thereof, most preferably - (R'O) _X B; B is hydrogen, C 1 -C ₆ alkyl, - (CH ₂ ) q SO ₃ M, - ( CH _{2) p} CO ₂ M, - (CH _{2) p} PO ₃ M - (CH ₂₎ q (CHSO ₃ M) CH ₂ SO ₃ M, - (CH _{2) q} (CHSO ₂ M) CH ₂ SO ₃ M ,, -PO ₃ M, and mixtures thereof, preferably hydrogen, Ci-Co alkyl, - _{(CH2) q} SO3 M, - _(CH2) q (CHSO3M) _{CH2 SO3} M, - (CH ₂₎ q (CHSO ₂ M) CH ₂ SO ₃ M and mixtures thereof, more preferably hydrogen, - (CH ₂ ) _q SO 3 M and mixtures thereof, most preferably hydrogen; M is hydrogen or a water-soluble cation in an amount sufficient to achieve a charge equilibrium; desolate • • φ * · an an an an an an m has a value of from 4 to 400; n is from 0 to 200; p is from 1 to 6; q is from 0 to 6; r has a value of 0 or was not; w is 0 or 1; x is from 1 to 100; y is from 0 to 100; z is 0 or 1; and (f) balance carrier and additives. A composition according to any one of claims 1 to 4, wherein the dye transfer inhibiting agent is selected from the group consisting of: (a) polyamine N-oxide polymers having the general formula: P A _x AND Where P is a polymerizable unit to which i) an N-O group is attached; ii) the N-O group is a member of the polymerizable unit; iii) a mixture thereof; A is a member selected from the group wherein the members have the general formulas 18,19, 20,21,22: 0 II (19) (20) (21) (22) -C-O -S- -O- -Non mixtures thereof, x is 0 or 1; and R is an aliphatic, ethoxylated aliphatic, aromatic, heterocyclic, alicyclic group and mixtures thereof to which i) nitrogen of the N-O group is attached; ii) N-O is within R; wherein the N-O group has the general formula 23 or 24 OO (R 1) x - N - (R ₂ ) _y = N - (R _x) I (23) (24) (R 5) z wherein r 1, R ₂ and R ₃ are aliphatic, aromatic, heterocyclic, alicyclic groups and mixtures thereof; x, y and z are 0 or 1; nitrogen atom of N-O group: i) is attached to R 1, R ₂ or R ₃ ; (ii) a unit thereof within R 1, R ₂ or R ₃ ; (iii) is a unit containing a fraction of the polymerizable unit P; O II (18) N-C 9 9 9 9 99 9 • 9 • 9 -95iv) by a unit which is attached to a polymer backbone containing P units; and (v) mixtures thereof; b) polyethoxylated urethane compounds formed i) the reaction product of at least one water-soluble polyether alcohol containing at least one hydroxyl functional group, a water-insoluble organic polyisocyanate and an organic monoisocyanate; ii) a reaction product of at least one water-soluble polyether alcohol, wherein the water-soluble polyether alcohol comprises at least one functional hydroxyl group and an organic monoisocyanate; iii) the reaction product of at least one water-soluble polyether alcohol comprising at least one hydroxyl functional group, a water-insoluble organic polyisocyanate, an organic monoisocyanate and at least one polyhydroxyl alcohol and at least one polyhydroxyl 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) the reaction product of at least one water-soluble polyether alcohol containing at least one functional hydroxyl group, a water-insoluble organic polyisocyanate containing at least three isocyanate groups, and monofunctional active hydrogen-containing compounds; provided that the polyether segment has a relative molecular weight of at least 200; the polyethoxylated urethane comprises at least one hydrophobic group and at least one water-soluble polyether segment; the sum of the carbon atoms in the hydrophobic groups is at least 4; and the total relative molecular weight is at least 300 to 60,000. (c) an acrylamide polymer containing: (i) N-substituted acrylamide of formula 26: OR ² CH ₂ = C-C-N (26) R ¹ R ³ wherein R ¹ is hydrogen or C 1 -C 6 alkyl and mixtures thereof; R ² and R ³ are independently selected from the group consisting of hydrogen, methyl, ethyl, propyl, butyl, t-butyl and isobutyl and mixtures thereof; or R ² and R ³ together with the nitrogen to ♦ Which R ² and R ^{3 are} attached to form three to seven membered monoaromatic nitrogen heterocycles; and ii) a vinyl monomer selected from the group consisting of C 1 -C 6 alkyl (meth) acrylate, hydroxyalkyl (meth) acrylate, hydroxyaryl (meth) acrylate, alkyoxyalkyl (meth) acrylate, polyalkoxyalkyl (meth) acrylate of styrene, vinyltoluene, alkyl vinyl ethers, amino -substituted alkyl (meth) acrylates, aminoalkyl 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 one of claims 1 to 4 wherein the dye transfer inhibiting agent is selected from the group consisting of poly (4-vinylpyridine-N-oxide), poly (2-vinylpyridine-N-oxide), polyvinylpyrrolidone, polyvinylpyrrolidone and vinylimidazole copolymers, and mixtures thereof. A method of inhibiting dye transfer between dyed or dyed fabrics during washing, comprising the step of contacting a dyed or dyed fabric with a water-soluble or dispersible, bleach-stable, modified polyamine fabric surface modifying agent, the agent comprising a polyamine backbone corresponding to a general spine formula 1: [H ₂ NR] _{n + 1} - [NR] _m - [NR] _n -NH ₂ having a modified polyamine of formula 2 V (n + 1) W _m Y _n Z or a polyamine backbone corresponding to formula 3: (1) (2) (3) [H ₂ NR] '. _{k + 1} - [NR] _m - [NR] 1 - | NR] ₁ -NH ₂ 0 0 0 Having a modified polyamine of formula 4 V _(n . K ₊ i) W _and Y _n Y ' _k Z, (4) wherein k is less than or equal to n, the polyamine backbone prior to modification has a relative molecular weight greater than 200 daltons, where (i) units V are terminal units having the general formula 5, 6, 7: x ~ ENR- (5) or E-N ⁺ -R- (6) or ENR- (7) E E E; (ii) units W are backbone units having the general formula8, 9,10: I ^x ' -NR- (8) or -N ⁺ -R- (9) or N-R- (10) (iii) Y units are branching units having the general formula 11,12, 13: -N-R- (11) or -N-R- (12) or -N-R- (13), and iv) Z units are terminal units having the general formula 14,15,16: N - E (14) or E; ΙΛ -N-E- (15) or -NE (16) wherein the backbone bond units R are selected from the group consisting of C 2 -C 12 alkylene, C 4 -C 12 alkenylene, C ₅ -C 12 hydroxyalkylene, C 4 -C 12 dihydroxyalkylene, C ₈ -C 12 dialkylarylene , - (R ¹ jxr -, - (R ^ xR ^ ^OR1 -, -C (O) (R ⁴⁾ r C (O) -, -CH2CH ^(OR2) CH2 -, - (CH 2 CH (OR ² ) CH2O) z (R ¹ O) y R ¹ (OCH 2 CH (OR ²⁾ CH 2) w and mixtures thereof, preferably C2-C12 alkylene, C3-Ci2hydroxyalkylenu, C4-C12 dihydroxyalkylene, C8-CI2 dialkylarylene, - (R jxr ¹ -, - (R ^ xR ^ OR ^ x-, - (CH2CH ^(OR2) CH2-, - (CH2CH (OH) CH2O) z (R ¹ O) y R ¹ (OCH 2 CH (OH) CH ₂₎ w a mixture of of these, more preferably C ₂ -C ₁₂ alkylene, C 3 -C ₁₂ hydroxyalkylene, C4-C12 dihydroxyalkylene, HdČOjxR ¹ -, - (R ¹⁰ ) xR ⁵ (OR ¹ ) _x -, - (CH ₂ CH (OH) CH ₂ O) z (R ¹⁰ O) y R ¹ (OCH ² CH (OH)) CH 2) w - and mixtures thereof, most preferably C ₂ -C ₁₂ alkylene and mixtures thereof; wherein R ¹ is C 2 -C 6 alkylene, preferably ethylene, and mixtures thereof; R ² is hydrogen, - (R ¹⁰ ) xB and mixtures thereof, preferably hydrogen; R ³ is C 1 -C 12 alkyl, C ₇ -C 12 arylalkyl, C ₇ -C 12 alkyl substituted aryl, C ₆ -C ₁₂ aryl and mixtures thereof; C 1 -C 6 alkyl and mixtures thereof, more preferably methyl; R ⁴ is C 1 -C 12 alkylene, C 4 -C 12 alkenylene, C 5 -C 12 arylalkylene, C 6 -C 10 arylene and mixtures thereof, preferably C 2 -C 12 alkylene, C 8 -C 12 arylalkylene and mixtures thereof, more preferably ethylene, butylene and mixtures thereof ; ^R5 is C1-C12 alkylene, C3-C12 hydroxyalkylene, C4-C12 dihydroxyalkylene, _C8-C12 dialkylarylene, -C (O) -, -QOjNHR HQO ^) -, -R ^ ^OR1) -, -C (O ) (R ⁴⁾ _r C (O) -, -CH ₂ CH (OH) CH ₂ -, -CH 2 CH (OH) CH ₂ O (R ¹ O) y R ¹ OCH 2 CH (OH) _CH2 -, and mixtures thereof ; preferably ethylene, -C (O) -, -C (O) NHR ⁶ NHC (O) -, -R ¹ OR ¹ ) 2, -CH ₂ CH (OH) CH ₂ O (R ¹⁰ ) y R ¹⁰ OCH ² CH (OH) CH 2) w -CH ₂ CH (OH) CH ₂ - and mixtures thereof, more preferably -CH ₂ CH (OH) CH ₂ -; R ⁶ is C 2 -C 12 alkylene or C 6 -C 12 arylene; the 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, - (CH 2) pPO 3 M, - (R ¹⁰ ) X B, -C (O) R ^3, and mixtures thereof; preferably hydrogen, C3-C22 hydroxy alkyl nominal, benzyl, C1-C22 alkyl, - (R'O) xB, -C (O) R ^3, - (CH 2) PCO2'M ^+, - (CH 2) q SO ₃ 'M ^+, -CH (CH2CO2M) CO2M and mixtures thereof, more preferably hydrogen, C1-C22 alkyl, - (R * O) xB, -C (O) ^R3, and mixtures thereof, most preferably - (R'O) xB; B is hydrogen, C 1 -C ₆ alkyl, - (CH ₂ ) qSO ₃ M, - (CH ₂ ) _p CO ₂ M, - (CH ₂ ) _p PO ₃ M - (CH ₂ ) _q (CHSO ₃ M) CH ₂ SO ₃ M, - (CH ₂ ) _q (CHSO ₂ M) CH ₂ SO ₃ M, -PO ₃ M, and mixtures thereof; preferably hydrogen, C 1 -C 6 alkyl, - (CH ₂ ) _q SO ₃ M, - (CH ₂ ) _q (CHSO ₃ M) CH ₂ SO ₃ M, - (CH ₂ ) _q (CHSO ₂ M) CH ₂ SO ₃ M and mixtures thereof, more preferably hydrogen, - (CH ₂ ) _q SO ₃ M, and mixtures thereof, most preferably hydrogen; M is hydrogen or a water-soluble cation in an amount sufficient to achieve a charge balance; X is a water-soluble anion; m has a value of from 4 to 400; n is from 0 to 200; p is from 1 to 6; q is from 0 to 6; r has a value of 0 or was not; w is 0 or 1; x is from 1 to 100; y is from 0 to 100; z is 0 or 1. A method of inhibiting dye transfer between dyed or colored fabrics during washing, comprising the step of contacting a dyed or colored fabric with an aqueous detergent solution according to any one of claims 1 to 6.