JP3202246B2 - Detergent compositions comprising modified polyamines as dye transfer inhibitors - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to a bleach-stable modified polyamine additive which can be used to wash colored fabrics containing dyes and which prevents dye transfer between the fabrics during the washing operation. And a laundry detergent composition comprising: The present invention also relates to a method of washing a colored fabric containing a dye in an aqueous solution formed from a laundry composition comprising a fabric surface modifying polyamine of the present invention.

BACKGROUND OF THE INVENTION One of the most persistent and troublesome events that occur in modern fabric washing operations is that certain colored fabrics tend to release dye in the washing solution. Such dyes often migrate to other fabrics being washed in the same wash solution.

One way to address the problem of dye transfer in laundry operations is to complex or adsorb floating dyes washed from dyed fabrics before attaching them to other clothes in the washing solution. For example, certain polymeric dyes have been proposed as effective laundry detergent additives that can complex or adsorb floating dyes in aqueous laundry solutions. For example, Abel U.S. Pat. No. 4,545,919, issued Oct. 8, 1985,
Describes the use of a carboxyl-containing polymer in a fabric washing operation. German Patent DE-A-28 by Waldhoff et al.
No. 14329, published October 11, 1979, is N-vinyl-
Disclosed is the use of oxazolidone polymers in British Patent GB 1,348,212 to Cracco et al., Published March 13, 1974, which discloses 15-35% polyvinylpyrrolidone and nitrile acrylate or maleic anhydride in a powder detergent. It describes the use of acid copolymers. Clements et al., European Patent No.
EP-A-265257, published April 27, 1988, discloses a detergent composition comprising an alkali metal carboxy-metal carboxymethylcellulose, a vinylpyrrolidone polymer and a polycarboxylate polymer.

Despite prior art attempts to solve the problem of dye transfer when washing fabrics, there remains a development of detergent compositions, detergent composition additives and fabric washing methods that are particularly effective against dye transfer. is needed. Therefore,
SUMMARY OF THE INVENTION It is an object of the present invention to provide a detergent composition comprising certain components that eliminates or at least minimizes dye transfer between fabrics during use in the laundry operation of the fabrics.

It has now surprisingly been found that the combination of certain dye transfer inhibitors and certain modified polyamines enhances dye transfer prevention properties. From this unexpected result, a wide variety of fabrics, mainly cotton, synthetic,
And a composition which provides this advantage for synthetic-cotton blend fabrics was obtained.

The methods and compositions of the present invention prevent dye transfer of textile products even in the presence of conventional bleaches because the modified polyamines described herein are stable to bleaches.

The procedures or methods of the present invention are equally effective whether the laundry detergent compositions disclosed herein are solid or liquid. The solid laundry detergent may be in the form of granules, flakes or laundry bars. Liquid detergents can have a wide range of viscosities and can include heavy concentrates, flowable "ready-to-use" detergents, or light duty fabric pretreatment agents.

The modified polyamines disclosed in this method have particularly good compatibility with other laundry detergent additives and auxiliary ingredients.

Another object of the present invention is to provide a detergent composition in granular or liquid form that is particularly effective in preventing such dye transfer.

It is yet another object of the present invention to provide a method for fabricating a colored fabric in an aqueous wash solution that contains a substance that has been washed from the laundry composition of the present invention and that therefore eliminates or at least minimizes dye transfer between the fabrics during the wash. The purpose is to provide a method for washing.

BACKGROUND ART In addition to the above techniques, the following documents disclose modified polyamines. U.S. Pat.No. 4,548,744, Conno
r, promulgated on October 22, 1985, U.S. Pat.No. 4,597,898, Vander Meer, promulgated July 1, 1986, U.S. Pat.
No. 91,160, Vander Meer, promulgated on January 2, 1990, U.S. Pat.No. 4,235,735, Marco, et al., 1980 1
Promulgated on January 25, International Patent No.WO 95/32272, 1995
Published November 30, 2000, UK Patent No. 1,537,288, 1978
Published December 29, 1980, UK Patent No. 1,498,520, 1978
Published January 18, 1998, German Patent No. DE2329022, 1980
Promulgated on January 10, 2000, Japanese Patent Publication No. JP06313271, 19
Published 27 April 1994, and European Patent EP 634,486
Issue specification, published on January 18, 1995.

SUMMARY OF THE INVENTION The laundry detergent composition of the present invention particularly effectively prevents dye transfer between fabrics being washed in an aqueous wash solution formed from the composition.

The laundry detergent composition of the present invention comprises the following a) to d).

a) at least about 5% by weight of a detersive surfactant; b) at least about 0.01% by weight of a dye transfer inhibitor; c) at least about 0.01% by weight of a modified polyamine fabric surface modifier which is soluble or dispersible in c. The agent has the formula Having the formula V _{(n + 1)} W _m Y _n Z of a modified polyamine, Comprises a polyamine backbone for the formula V _{(n-k + 1)} of the modified polyamine has a _{W m Y n Y 'k Z} , wherein, k is less than or equal to n, said polyamine backbone modified before Has a molecular weight of greater than about 200 daltons, i) V units are terminal units having the formula: ii) W units are skeletal units having the formula: iii) Y units are branch units having the formula: iv) Z units are terminal units having the formula: Wherein the skeleton-bonded R units are C ₂ -C ₁₂ alkylene, C ₄ -C
₁₂ alkenylene, C ₃ -C ₁₂ hydroxy - alkylene, C ₄
-C ₁₂ dihydroxy - alkylene, C ₈ -C ₁₂ dialkyl _{^{arylene, - (R 1 O) x}} R 1 -, - (R 1 O) x R 5 (OR 1)
_x −, − (CH ₂ CH (OR ² ) CH ₂ O) _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 is selected from the group consisting of a mixture thereof, R ¹ is C ₂ -C ₆ alkylene and mixtures thereof, R ² is hydrogen, - (R ¹ O) _x B, and mixtures thereof, wherein 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, wherein 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 hydroxy alkylene, C ₄ -C ₁₂ dihydroxy - alkylene, C
₈ -C ₁₂ dialkyl arylene, -C (O) -, - C
(O) NHR ⁶ NHC (O)-, -R ¹ (OR ¹ )-, -C (O)
(R ⁴ ) _r C (O)-, -CH ₂ CH (OH) CH _2- , -CH ₂ CH (O
^{_{H) CH 2 O (R 1}} O) y R 1 -OCH 2 CH (OH) CH 2 -, and mixtures thereof, R ⁶ is C ₂ -C ₁₂ alkylene or C ₆ -C ₁₂
Arylene, and the E unit is 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, -
When (R ¹ O) _x B, is -C (O) R ^3, and is selected from the group consisting of a mixture thereof (provided that either E unit of a nitrogen is a hydrogen, said nitrogen is not a N- oxide ),
B is hydrogen, C ₁ -C _{6 alkyl, - (CH 2) q -SO} 3 M, - (C
_{H 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) a _{p PO 3 M, -PO 3 M} , and mixtures thereof, M is a sufficient amount of hydrogen to satisfy charge balance Or a water-soluble cation,
X is a water-soluble anion, m has a value of 4 to about 400, n has a value of 0 to about 200, p has a value of 1 to 6, and q has a value of 0 to 6 Has a value, r has a value of 0 or 1, w has a value of 0 or 1, x has a value of 1-100, y has a value of 0-100, z Has a value of 0 or 1 and d) the carrier and auxiliary components that make up the remainder.

It is another object of the present invention to provide a modified polyamine dye transfer inhibitor that is stable to bleach and a method of preventing dye transfer from laundry to the fabric being washed.

All percentages, ratios, and proportions are by weight unless otherwise indicated. Unless otherwise indicated, all temperatures are given in degrees Celsius (° C). All cited documents are relevant and are hereby incorporated by reference.

DETAILED DESCRIPTION OF THE INVENTION The laundry detergent composition of the present invention comprises the following a) to d).

a) at least about 5% by weight of a detersive surfactant; b) at least about 0.01% by weight of a dye transfer inhibitor; c) at least about 0.1% by weight of a modified polyamine fabric surface of the present invention that is soluble or dispersible in water. Modifiers, and d) carriers and auxiliary ingredients which make up the remainder.

Preferred laundry detergent compositions of the present invention include the following a) to
e).

a) at least about 5% by weight anionic detersive surfactant; b) at least about 1% by weight nonionic detersive surfactant; c) at least about 0.01% by weight dye transfer inhibitor; d) at least about 0.5% % By weight of the modified polyamine fabric surface modifier of the present invention, which can be dissolved or dispersed in water, and e) the carrier and auxiliary ingredients that make up the balance.

Another preferred laundry detergent composition according to the invention comprises the following a)
~ F).

a) at least about 5% by weight anionic detersive surfactant; b) at least about 1% by weight nonionic detersive surfactant; c) at least about 0.01% by weight dye transfer inhibitor; d) optionally at least About 1% by weight of bleach, e) at least about 0.5% by weight of the modified polyamine fabric surface modifier of the present invention, which can be dissolved or dispersed in water, and f) the carrier and auxiliary ingredients which make up the balance.

More preferred laundry detergent compositions of the present invention include the following a)
~ G).

a) at least about 5% by weight anionic detersive surfactant; b) at least about 1% by weight nonionic detersive surfactant; c) at least about 0.01% by weight dye transfer inhibitor; d) optionally at least About 1% by weight of a bleaching agent, e) at least about 0.1% by weight of a soil-free polymer, f) at least about 0.5% by weight of a water-soluble or dispersible modified polyamine fabric surface modifier of the present invention, and g ) The carrier and auxiliary ingredients that make up the rest.

Another more preferred laundry detergent composition of the present invention comprises the following a) to f).

a) at least about 5% by weight of an anionic detersive surfactant selected from the group consisting of alkyl sulfates, alkyl alkoxy sulfates, and mixtures thereof; b) at least about 5% by weight of a polyhydroxy fatty acid amide A nonionic detersive surfactant selected from the group consisting of: alcohol ethoxylates, and mixtures thereof; c) at least about 0.01% by weight of a dye transfer inhibitor; d) optionally at least about 1% by weight of a bleaching agent; e) at least about 0.5% by weight of the modified polyamine fabric surface modifier of the present invention, which can be dissolved or dispersed in water, and f) the carrier and auxiliary ingredients that make up the balance.

Preferred laundry detergent compositions of the present invention comprise the following preferred materials.

Polymeric Dye Transfer Inhibitor The detergent compositions of the present invention must contain from about 0.01 to 10% by weight of a particular type of polymeric dye transfer inhibitor. Preferably, the detergent composition of the present invention comprises from about 0.05 to 0.5.
% By weight of these polymeric dye transfer inhibitors.

The dye transfer inhibiting polymeric materials selected include certain polyamine N-oxide polymers, certain copolymers of N-vinyl pyrrolidone and N-vinyl imidazole, polyethoxylated urethanes, acrylamide containing polymers, Amino acids and combinations of these materials may be used. These types of polymers / copolymers are described in detail below.

Polyamine N-oxide Suitable polyamine N-oxide polymers for use herein have the following structural formula Wherein P is a polymerizable unit to which an N—O group can be added, or N—O
The group may form part of a polymerizable unit, or
An O group can be added to both units and A has the following structure Wherein x is 0 or 1 and R is an aliphatic, ethoxylated aliphatic, aromatic, heterocyclic or alicyclic group or a combination thereof; Can be added, or the NO group is part of these groups.

The NO group is represented by the following general formula Wherein R ₁ , R ₂ , R ₃ are an aliphatic, aromatic, heterocyclic or alicyclic group or a combination thereof, and x, y
And z are 0 or 1 and the nitrogen of the NO group can be added or form part of any of the groups described above. Further, the NO group can be part of the polymerizable unit (P) or can be added to the polymer backbone,
Or a combination of both may be used.

Suitable polyamine N-oxides wherein the N-O group forms part of a polymerizable unit include those wherein R is aliphatic, aromatic,
Polyamine N- selected from alicyclic or heterocyclic groups
There are oxides. One such polyamine N-oxide
Species include the group of polyamine N-oxides where the nitrogen of the NO group forms part of the R group. Preferred polyamine N-oxides are those in which R is a heterocyclic group such as pyridine, pyrrole, imidazole, pyrrolidine, piperidine and derivatives thereof.

Another class of polyamine N-oxides is the group of polyamine N-oxides in which the nitrogen of the NO group has been added to the R group. Other suitable polyamine N-oxides are N-O
A polyamine oxide in which a group is attached to a polymerizable unit. A preferred group of these polyamine N-oxides has the general formula above, wherein R is an aromatic, heterocyclic or alicyclic group and the nitrogen of the NO functional group is part of the R group Polyamine N-oxide. Examples of these groups are
Polyamine oxide wherein R is a heterocyclic compound such as pyridine, pyrrole, imidazole and derivatives thereof.

Another preferred group of polyamine N-oxides has the general formula above, where R is an aromatic, heterocyclic or alicyclic group and the nitrogen of the NO functional group is attached to the R group. Polyamine N-oxide. Examples of these groups are polyamine oxides in which the R groups can be aromatic, such as phenyl.
Any polymer backbone can be used so long as the amine oxide polymer formed is water soluble and has dye transfer inhibiting properties. Examples of suitable polymer backbones are polyvinyl, polyalkylene, polyester, polyether, polyamide, polyimide, polyacrylate and mixtures thereof.

Amine N-oxide polymers useful in the detergent compositions of the present invention generally have a ratio of amine to amine N-oxide.
10: 1 to 1: 1,000,000. However, the number of amine oxide groups present in the polyamine oxide polymer can be varied by a suitable copolymerization or by a suitable degree of N-oxidation. Preferably, the ratio of amine to amine N-oxide is from 3: 1 to 1: 1000000. Polymers useful in the detergent compositions of the present invention include, in fact, random or block copolymers where one of the monomers is an amine N-oxide and the other monomer is an N-oxide.

The amine oxide unit of the polyamine N-oxide is pK
It has a10, preferably pKa7, more preferably pKa6.
Polyamine oxides can be obtained at almost all degrees of polymerization. The degree of polymerization is not critical as long as the material has the desired water solubility and dye dispersing power. Generally, the average molecular weight is between 500 and 1,000,000, more preferably between 1,000 and
It is between 0 and 500,000, most preferably between 5,000 and 100,000.

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

Polyamine N-oxides useful in the present invention can be synthesized by polymerizing an amine monomer and oxidizing the resulting polymer with a suitable oxidizing agent, or by polymerizing the amine oxide monomer itself to form the desired polyamine N-
An oxide can be obtained. Such a reaction mechanism is well known to those skilled in the art.

N-vinylpyrrolidone and N-vinylimidazole copolymer The detergent composition of the present invention comprises a copolymer of N-vinylpyrrolidone and N-vinylimidazole (here, "PVPV
I "). Copolymers of N-vinylpyrrolidone and N-vinylimidazole have been found to provide excellent dye transfer inhibiting properties when used in the compositions of the present invention.

In a preferred embodiment, the copolymer of N-vinylpyrrolidone and N-vinylimidazole polymer has an average molecular weight of 5,000 to 1,000,000, more preferably 5,000 to 200,000.
It is. A highly preferred copolymer for the detergent composition of the present invention has an average molecular weight of 5,000 to 50,000, more preferably 8,000.
~ 30,000, most preferably 10,000-20,000. The average molecular weight range is set forth in Bart, the disclosure of which is incorporated herein by reference.
h Chemical Analysis of JHG and Mays JW, Vol 11
3, Measured by light scattering described in “Modern Methods of Polymer Characterization”.

The copolymer of N-vinylpyrrolidone and N-vinylimidazole useful in the present invention has a molar ratio of N-vinylimidazole to N-vinylpyrrolidone of 1: 1 to 0.2: 1,
More preferably 0.8: 1 to 0.3: 1, most preferably 0.6: 1 to
0.4: 1. The copolymer of N-vinylpyrrolidone and N-vinylimidazole may be linear or branched.

Polyethoxylated Urethanes Polyethoxylated urethanes known for use as associative thickeners in latex compositions are condensation polymers of polyether polyols and isocyanates. U.S. Pat.No. 4,079, both of which are incorporated herein by reference.
No. 028 and 4,155,892 describe these polyurethane thickeners in detail, but these materials, when formulated in the present invention in combination with the modified polyamines described below, It has been found to be effective as a dye transfer agent.

The polyethoxylated urethane is produced in a non-aqueous medium and is a reaction product of at least reactants (a) and (c) described below, wherein the polymer optionally comprises reactants (b) and (d) You can also.

(A) at least one water-soluble polyether alcohol containing one or more hydroxyl groups; (b) at least one water-insoluble organic polyisocyanate; (c) a monofunctional active hydrogen compound and an organic monoisocyanate. At least one monofunctional hydrophobic organic compound selected, and (d) at least one polyhydric alcohol or polyhydric alcohol ether.

Reactant (a), which is a polyether alcohol containing one or more functional hydroxyl groups, is generally an adduct of an aliphatic, cycloaliphatic, or aromatic polyhydroxy compound, such as an alkylene oxide and a polyhydric alcohol or polyhydric alcohol. Adducts of polyhydric alcohol ethers, hydroxyl-terminated prepolymers of such adducts and organic polyisocyanates, or mixtures of such adducts and such prepolymers. If desired, the polyether alcohol can contain only one hydroxyl group, such as an alkyl polyethylene glycol, an alkyl aryl polyethylene glycol, or a polycyclic alkyl polyethylene glycol, wherein the alkyl group has 1 to about 20 carbon atoms.

A convenient source of the hydrophilic polyether polyol adduct is a polyalkylene glycol (also referred to as a polyoxyalkylene diol) such as polyethylene glycol, polypropylene glycol, or polybutylene glycol having a molecular weight of about 200 to about 20,000. However, adducts of alkylene oxides and monofunctional reactants, such as fatty alcohols, phenols or amines,
Alternatively, adducts of an alkylene oxide and a bifunctional reactant such as an alkanolamine (eg, ethanolamine) are also useful. Such adducts are also called diol ethers and alkanolamine ethers.

Suitable compounds that provide a polyether moiety also include amino-terminated polyoxyethylenes having the formula:

NH in _{2 (CH 2 CH 2 O)} x H formula, x is a value of from about 10 to about 200.

Reactant (c), a monofunctional hydrophobic organic compound,
Reacts with one or both terminal functional groups of the reaction product of reactants (a) and (b). Monofunctional hydrophobic organic compounds include both monofunctional active hydrogen compounds and organic monoisocyanates.

For the purposes of the present invention, a “monofunctional active hydrogen compound” is
It has only one group that can react with isocyanate, such group contains an active hydrogen atom, and all other functional groups
It is defined as an organic compound that, when present, does not substantially react with the isocyanate. Such compounds include monohydroxy compounds such as alcohols, alcohol ethers, and monoamines, and polyfunctional compounds that are only monofunctional with respect to isocyanates. Representative examples of monofunctional active hydrogen compounds include, for example, fats (C ₁ to
C ₂₄₎ alcohols, such as methanol, ethanol, octanol, decanol, dodecanol, tetradecanol, hexadecanol and cyclohexanol,
Phenolic compounds, such as phenol, cresol,
Octylphenol, nonyl and dodecylphenol, alcohol ethers such as monomethyl, monoethyl and monobutyl ethers of ethylene glycol, and similar ethers of diethylene glycol, alkyl and alkaryl polyether alcohols such as linear or branched (C ₁ -C ₂₂ ) alkanols / There are ethylene oxide and alkylphenol / ethylene oxide adducts.

The amino compound can be used as a hydrophobic monofunctional active hydrogen compound instead of all or a part of the monohydroxy compound. Amino compounds include primary or secondary aliphatic, cycloaliphatic, or aromatic amines, such as straight or branched chain alkylamines having about 1 to about 20 carbon atoms in the alkyl group, or mixtures thereof. There is.
Suitable amine, n- and t-octylamine, n- dodecylamine, C ₁₂ -C ₁₄ or C ₁₈ -C ₂₀ t-
Alkylamine mixtures, and secondary amines such as N,
There are N-dibenzylamine, N, N-dicyclohexylamine and N, N-diphenylamine. Amino compounds are
It can contain more than one active hydrogen atom only under normal reaction conditions if it is only monofunctional to the isocyanate group. Primary amines are examples of such compounds.

In addition to the monofunctional active hydrogen compound, reactant (c) may be a monoisocyanate. The monoisocyanate is C ₆
-C ₁₈ linear, branched, and cyclic isocyanates such as butyl isocyanate, octyl isocyanate, dodecyl isocyanate, octadecyl isocyanate,
And cyclohexyl isocyanate. These isocyanates can be used alone or as a mixture of two or more.

As the organic polyisocyanate reactant (b), di-
And triisocyanates, such polyhydric alcohols and organic di- or triisocyanate-terminated compounds, and polyalkylene ether glycols and organic di- or triisocyanate-terminated prepolymers. The reactant (b) is preferably an organic polyisocyanate, but a reactant containing one or more functional groups other than isocyanate is also suitable. Examples of monomers that can be used as the reactant (b) are shown below. These monomers can be used alone or in combination with one or more of the reactant (b) monomers.

1,6-hexamethylene diisocyanate (HDI) 1,6- and 2,4-tolylene diisocyanate (TDI) 4,4'-methylenediphenyl isocyanate (MDI) Hydrolytic trimolecular polymerization of 1,6-hexamethylene diisocyanate Aliphatic triisocyanate product, DESMODUR
Commercially available under the trade name N, polyisocyanates are all obtained from the reaction of any of the above isocyanates with an active hydrogen compound having at least two functional groups, such that at least one isocyanate group remains unreacted. Of polyfunctional isocyanates. Such isocyanates are equivalent to chain extending an isocyanate-terminated isocyanate / diol reaction product with a reactant containing at least two active hydrogen atoms in a manner well known in polyurethane synthesis.

The isocyanate can contain any number of carbon atoms effective to provide the required degree of hydrophobicity.
Generally, about 4 to about 30 carbon atoms will suffice, but the choice will depend on the proportion of other hydrophobic groups and hydrophilic polyethers in the product.

Reactant (d), a polyhydric alcohol or polyhydric alcohol ether, can be used to terminate the isocyanate functionality or to bind a reaction intermediate having an isocyanate end. The polyhydric alcohol or polyhydric alcohol ether can be aliphatic, cycloaliphatic or aromatic and can be used alone or in either type of mixture or in two types of mixtures.

By appropriate choice of the reaction conditions, including the reactants and the proportions and molecular weights of the reactants, the structure can be linear or
Alternatively, complex, various polymer compositions are obtained. In summary, the reaction products formed include:

i) a reactant (a) that is at least one water-soluble polyether alcohol containing at least one functional hydroxyl group, a water-insoluble organic polyisocyanate reactant (b) and an organic monoisocyanate reactant, (c) )
Ii) the reaction product of a reactant (a) in which the water-soluble polyether alcohol contains at least one functional hydroxyl group, and the organic monoisocyanate reactant (c); iii) the reaction product (a ), A reaction product of reactant (b), an organic monoisocyanate reactant (c), and a reactant (d) selected from at least one polyhydric alcohol and a polyhydric alcohol ether; iv) a reactant ( a) a reaction product of a water-insoluble organic polyisocyanate reactant (b) containing two isocyanate groups and a monofunctional active hydrogen-containing compound, and v) at least three reactants (a) The reaction product of a water-insoluble organic polyisocyanate reactant (b) containing an isocyanate group of (b) and a monofunctional active hydrogen-containing compound.

Polyethoxylated urethanes which are effective as dye transfer inhibitors include: i) the polyether moiety has a molecular weight of at least 200; ii) the polyethoxylated urethane has at least one hydrophobic group and at least one water-soluble polyether. Iii) generally prevents dye transfer during washing when the total number of carbon atoms in the hydrophobic group is at least 4 and iv) the total molecular weight is at least 300 to about 600,000.

The polymer is preferably prepared by techniques generally known in urethane synthesis such that the isocyanate does not remain unreacted. Since water consumes the functional groups of the isocyanate, water should be excluded from the reaction.

If desired, the reaction can be performed in a solvent medium to reduce the viscosity in those reactions that produce high molecular weight products. Generally, when the molecular weight is 30,000 or more, a solvent is useful. The solvent should be inert to the isocyanate and be capable of dissolving the polyoxyalkylene reactant and urethane product at the reaction temperature.

The order of addition, the proportions of reactants, and other reaction conditions, such as the choice of catalyst, can be adjusted to adjust the geometric production, molecular weight and other properties of the product according to well-known principles of urethane synthesis. Can be changed.

Acrylamide-Containing Polymers Water-soluble or water-dispersible acrylamide-containing polymers that are effective in preventing dye deposition are known as thickeners, rheology modifiers, and dispersants.

Generally, acrylamide-containing polymers are prepared by a polymerization process that initiates free radicals in the presence of a chain transfer agent. The acrylamide-containing polymer may be (i) at least one acrylamide or N
-Formed from substituted acrylamide monomers and, if desired, (ii) one or more vinyl monomers.
(I) Acrylamide having the following structure or N-substituted acrylamide.

Wherein R ¹ is hydrogen or C ₁ -C ₆ alkyl, preferably hydrogen and methyl, and R ² and R ³ are independently hydrogen,
Methyl, ethyl, propyl, isopropyl, butyl, t
Or R ² and R ³ , together with the nitrogen to which R ² and R ³ are attached, form a 3-6 membered monoaromatic nitrogen heterocyclic compound Form.

ii) vinyl monomers such as (meth) acrylic acid C ₁ -C ₆
Alkyl, hydroxyalkyl (meth) acrylate,
Hydroxyaryl (meth) acrylate, alkoxyalkyl (meth) acrylate, alkoxyalkyl (meth) acrylate, styrene, vinyltoluene, alkyl vinyl ether such as butyl vinyl ether, amino monomer such as amino-substituted (meth) acrylic acid Alkylamino-alkyl vinyl ethers, and maleic anhydride. Further, a vinyl monomer substituted with a carboxylic acid, for example, maleic acid, fumaric acid, itaconic acid,
(Meth) acrylic acid or salts thereof can also be used.

For the purposes of the present invention, the term "(meth) acrylate" means acrylic acid or methacrylic acid or ester. Salts of carboxylic acid-substituted vinyl monomers are obtained by partially carboxyl-substituting vinyl monomers with one or more common alkali or alkaline earth metals, ammonia, low molecular weight amines, or lower quaternary salt hydroxides. It can be formed by neutralization or complete neutralization.

Acrylamide polymers useful in the present invention can be made by a number of techniques well known to those skilled in the art. A preferred method is radical-initiated solution polymerization in water or a mixture of water and a co-solvent. The co-solvent may be, for example, tert-butanol, monobutyl ether of ethylene glycol, or diethylene glycol. Next preferred methods are polar organic solvents such as methanol, ethanol, n-propanol, isopropanol, n-
Butanol, sec-butanol, isobutanol, tert
Precipitation polymerization in butanol, ethylene glycol monoalkyl ether, diethylene glycol ether, acetone, methyl ethyl ketone, ethyl acetate, acetonitrile, dimethylsulfoxide or tetrahydrofuran, and mixtures of these solvents, with or without water. Some of the above solvents act as effective chain transfer agents and reduce the molecular weight of the resulting polymer.

The chain transfer agent is present at about 0.5 to the total weight of reactants added.
In amounts of up to about 12% by weight, the molecular weight of the polymer can be reduced or a hydrophobic group can be added to the polymer to produce an associative thickener in addition to the polymerization step. Examples of chain transfer agents effective for reducing the molecular weight include mercaptans such as ethyl mercaptan, n-propyl mercaptan, n-amyl mercaptan, hydroxyethyl mercaptan, mercaptopropionic acid, and mercaptoacetic acid; carbon tetrachloride;
There are halogen compounds such as tetrachlorethylene, certain primary alkanols such as benzyl alcohol, ethylene glycol, and diethylene glycol, certain secondary alcohols such as isopropanol, and bisulfites such as sodium bisulfite. . Chain transfer agents useful for making the associative thickener are water-insoluble, preferably long-chain alkyl mercaptans, such as n-dodecyl mercaptan, t-dodecyl mercaptan, octyl mercaptan, tetradecyl mercaptan, and hexadecyl mercaptan. is there. The total amount of chain transfer agent added to the polymerization step depends on the efficiency of the chain transfer agent. For example, when using a less efficient chain transfer agent such as sodium bisulfite, about 5 to about 12% by weight of the chain transfer agent must be used, while an efficient chain transfer agent such as mercaptan is used. In some cases, only about 0.5 to about 5% by weight of the chain transfer agent may be required.

The molecular weight range of these polymers is from about 2,000 to about 300,000. Preferably, the molecular weight is between about 20,000 and 60,000.
The acrylamide-containing polymer comprises about 50-100% by weight of acrylamide or N-acrylamide monomer (i),
And from 0 to about 50% by weight of vinyl monomer (ii). An acrylamide-containing polymer that is particularly effective in preventing dye transfer is where the acrylamide or N-acrylamide monomer is dimethylacrylamide, methylacrylamide, and acrylamide, and mixtures thereof, and the vinyl monomer is a nonionic material, such as (meth).
Polymers that are hydroxyalkyl acrylates or alkyl (meth) acrylates.

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

Modified polyamine: a surface modifier having enhanced dye transfer prevention properties The modified polyamine of the present invention is a substance having surface modification properties. As a result of this surprising property, these substances can work in concert with dye transfer inhibitors to surprisingly increase dye transfer resistance. The surface modifier which enhances the dye transfer-preventing property of the present invention is a modified polyamine comprising a water-soluble or water-dispersible bleach-stable, linear or cyclic polyamine skeleton. The polyamine backbone can also include more or less polyamine branches. Generally, the polyamine backbone described herein has
Each nitrogen of the polyamine chain has been modified as described below with respect to units that are substituted, quaternized, oxidized, or combinations thereof.

For the purposes of the present invention, the term "modified" refers to replacing the backbone -NH hydrogen atom with an E unit (substitution), quaternizing the backbone nitrogen (quaternization), or replacing the backbone nitrogen with N-.
It is defined as oxidizing to an oxide (oxidation). The terms "denaturation" and "substitution" are used interchangeably with respect to the step of replacing a hydrogen atom attached to the backbone nitrogen with an E unit. The quaternization or oxidation may optionally occur without substitution, but preferably the substitution involves oxidation or quaternization of at least one skeletal nitrogen.

The linear or non-cyclic polyamine skeleton constituting the cotton soil release agent of the present invention has the following general formula: Wherein the backbone comprises, prior to subsequent modification, primary, secondary and tertiary amine nitrogens connected by R "attachment" units. The cyclic polyamine skeleton constituting the cotton soil release agent of the present invention has the following general formula Wherein the backbone comprises, prior to subsequent modification, primary, secondary and tertiary amine nitrogens connected by R "attachment" units.

For the purpose of the present invention, the first
A tertiary amine nitrogen is defined as a V or Z "terminal" unit after modification. For example, if a primary amine moiety having the structure H ₂ N—R] —, located at the end of the main polyamine skeleton or branch, is modified according to the present invention, then as a V “terminal” unit or simply as a V unit Defined. However, for the purposes of the present invention, some or all of the primary amine moiety may remain unmodified, subject to the limitations described below. These unmodified primary amine moieties remain "terminal" units due to their position in the backbone. Similarly, located at the end of the main polyamine backbone, primary amine moiety having the structure -NH ₂ is subject to modification by the present invention, then is defined as Z "terminal" unit, or simply Z units. This unit may be left unmodified, subject to the restrictions described below.

Similarly, the secondary amine nitrogens that make up the backbone or branch are defined as W "backbone" units after organization.
For example, the structure which is a main component of the skeleton and the branched chain of the present invention When a secondary amine moiety having the formula (I) is modified according to the present invention, it is subsequently defined as a W "skeleton" unit or simply a W unit. However, for the purposes of the present invention, some or all of the secondary amine moiety may remain unmodified. These unmodified secondary amine moieties remain "backbone" units because of their position in the backbone.

Further similarly, the tertiary amine nitrogens that make up the backbone or branch are defined as Y "branched" units after modification. For example, a structure that is a branch point of a polyamine backbone or other branch or ring chain. When a tertiary amine moiety having the formula is modified according to the present invention, it is subsequently defined as a Y "branched" unit or simply a Y unit. However, for the purposes of the present invention, some or all of the tertiary amine moiety may remain unmodified. These unmodified tertiary amine moieties remain "branched" units because of their position in the backbone.
R, which serves to connect the nitrogen of the polyamine, associated with the nitrogen of the V, W and Y units is described below.

Therefore, the final modified structure of the polyamine of the present invention is
For the linear polyamine cotton soil free polymer, represented by the general formula V _{(n + 1)} W _m Y _n Z, for the cyclic polyamine cotton soil free polymer,
Formula V _{(n-k + 1)} can be represented by _{W m Y n Y 'k Z} . In the case of a polyamine comprising a ring, the formula Y 'unit serves as a skeleton or a branch point of a branched ring. For each Y 'unit, the formula There are Y units having the formula: which forms the point connecting the ring to the polymer backbone or branch. In the special case where the backbone is a complete ring, the polyamine backbone has the formula And therefore does not include the Z-terminal unit and has the formula V _nk W _m Y _n Y ′ _k , where k is the number of branched units forming a ring. Preferably, the polyamine backbone of the present invention does not contain a ring.

In the case of acyclic polyamines, the ratio of the index n to the index m is related to the relative degree of branching. The completely acyclic, linearly modified polyamines of the present invention have the formula VW _m z, ie, n is 0. The greater the number of n (the smaller the ratio of m to n), the greater the degree of branching in the molecule.
Generally, the value of m has a minimum value of 4 to about 400, but large values of m are also preferred, especially if the value of the index n is very small or close to zero.

Each polyamine nitrogen, whether primary, secondary or tertiary, after being modified according to the present invention, has three general classes: simple substituted, quaternized or oxidized. Was further defined as one of Unmodified polyamine nitrogen units are those which are primary, secondary,
Classified as V, W, Y or Z depending on whether it is a primary or tertiary nitrogen. That is, for purposes of the present invention, unmodified primary amine nitrogen is V or Z units, unmodified secondary amine nitrogen is W units, and unmodified tertiary amine nitrogen is Y units. It is.

A modified primary amine moiety is defined as a V "terminal" unit having one of three forms:

a) Structure A simply substituted unit having the formula: b) structure A quaternized unit having the formula: where X is a suitable counter ion to provide charge balance; and c) the structure An oxidized unit having the formula:

A modified secondary amine moiety is defined as a W "skeleton" unit having one of three forms:

a) Structure A simple substituted unit having the formula: b) the structure A quaternized unit having the formula: where X is a suitable counter ion to provide charge balance; and c) the structure An oxidized unit having the formula:

A modified tertiary amine moiety is defined as a Y "branched" unit having one of three forms:

a) Structure A) a native unit having A quaternized unit having the formula: where X is a suitable counter ion to provide charge balance; and c) the structure An oxidized unit having the formula:

Certain modified primary amine moieties are defined as Z "terminal" units having one of three forms:

a) Structure A simple substituted unit having the formula: b) the structure A quaternized unit having the formula: where X is a suitable counter ion to provide charge balance; and c) the structure An oxidized unit having the formula:

If any position on the nitrogen is unsubstituted or unmodified, hydrogen will of course replace E. For example, primary amine unit comprising one E unit in the form of a hydroxyethyl moiety is a V terminal unit having the formula (HOCH ₂ CH ₂₎ HN-.

For the purposes of the present invention, there are two types of linkage termination units, V and Z units. Z "terminal" units have the structure -NH
Derived from ₂ terminal primary amino moieties. While the acyclic polyamine backbone of the present invention has only one Z unit,
Cyclic polyamines do not contain Z units. Unless the Z unit has been modified to form an N-oxide, the Z "terminal" unit can be replaced by any of the E units described below. If the Z unit nitrogen has been oxidized to the N-oxide, the nitrogen must be modified, so E cannot be hydrogen.

The polyamines of the present invention contain a backbone R "attachment" unit that serves to connect the nitrogen atoms of the backbone. R units are referred to as "hydrocarbyl R" units and "oxy R" for the purposes of the present invention.
Includes units called units. "Hydrocarbyl R" units are C ₂ -C ₁₂ alkylene, C ₄ -C ₁₂ alkenylene, C ₃ -C ₁₂
Hydroxyalkylene (the hydroxy moiety can be taken at any position on the R unit chain except for the carbon atom directly attached to the polyamine backbone nitrogen), C ₄ -C ₁₂ dihydroxy-alkylene (the hydroxy moiety is a polyamine backbone nitrogen except a carbon atom directly attached to the can occupy any two of the carbon atoms of R unit chain), C ₈ -C ₁₂
Dialkylarylene, which is, for the purposes of the present invention, an arylene moiety having two alkyl substituents as part of the linking chain. For example, a dialkylarylene unit is represented by the following formula: Has a, the unit is not 1,4-substituted only, may be a 1,2 or 1,3 substituted C ₂ -C ₁₂ alkylene, preferably ethylene, 1,2-propylene, and mixtures thereof And more preferably ethylene. “Oxy” R units are — (R ¹ O) _x R ⁵ (OR ¹ ) _x —, — (CH ₂ CH (OR ² ) CH
^{_{2 O) z - (R 1}} O) y R 1 (OCH 2 CH (OR 2) CH 2) w -, - (CH
^{_{2 CH (OR 2) CH 2}} -, - (R 1 O) x R 1 -, and comprises a mixture thereof. Preferred R units are C ₂ -C ₁₂ alkylene, C ₃ -C ₁₂ hydroxyalkylene, C ₄ -C ₁₂ dihydroxy alkylene, C ₈ -C ₁₂ dialkyl arylene, - (R
¹ O) _x R ¹ -,-(CH ₂ CH (OR ² ) CH ₂ -,-(CH ₂ CH (OH) C
H ₂ O) _z (R ¹ O) _y R ¹ (OCH ₂ CH- (OH) CH ₂ ) _w -,-(R ¹
O) _x R ⁵ (OR ¹ ) _x —, more preferably the R unit is C ₂
-C ₁₂ alkylene, C ₃ -C ₁₂ hydroxyalkylene, C ₄ ~
C ₁₂ dihydroxyalkylene,-(R ¹ O) _x R ¹ -,-(R
¹ O) _x R ⁵ (OR ¹ ) _x -,-(CH ₂ CH (OH) CH ₂ O) _z (R ¹ O)
^{_{y R 1 (OCH 2 CH- (}} OH) CH 2) w -, and mixtures thereof, more preferably R units are C ₂ -C ₁₂ alkylene, C ₃ hydroxyalkylene, and mixtures thereof, most preferably a C ₂ -C ₆ alkylene. The most preferred scaffold of the present invention comprises at least 50% of R units that are ethylene.

R ¹ unit is a C ₂ -C ₆ alkylene, and mixtures thereof,
Preferably it is ethylene.

R ² is hydrogen, and _{^{- (R 1 O) 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 ₂ -C ₁₂
Alkyl, C ₇ -C ₁₂ arylalkylene, more preferably C ₁ -C ₁₂ alkyl, most preferred methyl. R ³ units serve as part of E units described below.

R ⁴ is R ₁ -C ₁₂ alkylene, C ₄ -C ₁₂ alkenylene, C ₈ ~
C ₁₂ arylalkylene, C ₆ -C ₁₀ arylene, preferably C ₁ -C ₁₀ alkylene, C ₈ -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 hydroxy-alkylene, 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 ¹ (OR ¹ )
_{-, - CH 2 CH (OH} ) CH 2 O (R 1 O) y R 1 OCH 2 CH (OH) CH 2 -,
^{-C (O) (R 4)} r C (O) -, - CH 2 CH (OH) CH 2 - and is, R ⁵ is preferably ethylene, -C (O) -, - C
(O) NHR ⁶ NHC (O)-, -R ¹ (OR ¹ )-, -CH ₂ CH (O
_{H) CH 2 -, - CH} 2 CH (OH) CH 2 O (R 1 O) y R 1 OCH 2 CH- (O
H) CH ₂ -, more preferably _{-CH 2 CH (OH) CH 2} - is.

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

Preferred "oxy" R units are further limited as to R ^1, R ^2, and R ⁵ units. Preferred "oxy" R units comprise the preferred R ^1, R ^2, and R ⁵ units. A preferred cotton soil releaser of the present invention comprises at least 50% of R ¹ units which are ethylene. Preferred R ¹ , R ² , and R ⁵ units are combined with “oxy” R units to form preferred “oxy” R units in the manner described below.

i) More preferably, R ⁵ is-(CH ₂ CH ₂ O) _x R ⁵ (OCH ₂ CH ₂ ) _x
-(CH ₂ CH ₂ O) _x CH ₂ CHOHCH ₂ (OCH ₂ C
H ₂ ) _x − is obtained.

ii) Preferred R ¹ and R ² a ^{_{- (CH 2 CH (OR 2}} ) CH 2 O) z -
(R ¹ O) _y R ¹ O (CH ₂ CH (OR ² ) CH ₂ ) _w
(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} - obtained.

substituting _{in, -CH 2 CH (OH) CH} 2 - - iii) the preferred ^{_{R 2 -CH 2 CH (OR 2}} ) CH 2 obtained.

E units are selected from 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, - (R 1 O) m B, -C (O) R
^3, the preferred hydrogen, C ₂ -C ₂₂ hydroxyalkylene, benzyl, C ₁ -C _{22 ^{alkylene, - (R 1 O) m}} B, -C (O)
_{^{R 3, - (CH 2)}} P CO 2 M, - (CH 2) q SO 3 M, -CH (CH 2 CO
₂ M) CO ₂ M, more preferably C ₁ -C ₂₂ alkylene, - (R
_{^{1 O) x B, -C (}} O) R 3 -, - (CH 2) p CO 2 M, - (CH 2) q
SO ₃ M, the _{-CH (CH 2 CO 2 M)} CO 2 M, most preferably C ₁ -C ₂₂ alkylene, - selected from the group consisting of (R ¹ O) _x B, and -C (O) R ^3. If no modification or substitution is made on the nitrogen, the hydrogen atom remains as a representative of E.

If the V, W or Z unit is oxidized, ie the nitrogen is an N-oxide, the E unit does not contain a hydrogen atom. For example, it does not include a unit having the following structure of a skeletal chain or a branch.

Further, when a V, W or Z unit is oxidized, ie, the nitrogen is an N-oxide, the E unit does not include a carbonyl moiety directly attached to the nitrogen. In the present invention, E
Unit -C (O) R ³ moiety is not bonded to the nitrogen which is N- oxide-modified, i.e. structure Or N-oxide amides having a combination thereof are not present.

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) C
_{H 2 SO 3 M, - (} CH 2) q - is _{(CH 2) q SO 3 M} - (CHSO 2 M) CH 2 SO 3 M, more preferably hydrogen or.

M is hydrogen or a water-soluble cation in an amount sufficient to satisfy the charge balance. For example, sodium cations _{- (CH 2) p CO 2} M, and _{- (CH 2) q SO 3} M equal to satisfy, whereby _{- (CH 2) p CO 2} Na , and, - (C
H ₂ ) _q Form a SO ₃ Na moiety. Two or more monovalent cations (sodium, potassium, etc.) can be combined to satisfy the required chemical charge balance. However, two or more anionic groups can be balanced in charge by a divalent cation, or two or more monovalent cations are required to meet the charge requirements of a polyanionic group. Would. For example,-(C substituted with a sodium atom
H _{2) p} PO ₃ M moiety of the formula - with a _{(CH 2) p PO 3 Na} 3. A divalent cation such as calcium (Ca ²⁺ ) or magnesium (Mg ²⁺ ) can be replaced by or combined with other suitable monovalent water-soluble cations. Preferred cations are sodium and calcium, with sodium being more preferred.

X represents chlorine (Cl ⁻ ), bromine (Br ⁻ ) and iodine (I ⁻ )
X is a water-soluble anion such as
₄ ^2-) and methosulfate _{(methosulfate) (CH 3 SO 3} -) , such as may be all the negatively charged groups.

The exponent of the formula has the following values: p has a value of 1 to 6, q has a value of 0 to 6, r has a value of 0 or 1, and w has a value of 0 or 1. Has a value, x has a value of 1 to 100, y has a value of 0 to 100, z has a value of 0 or 1, k has a value of less than n, and The value of k is less than 20, m has a value of 4 to about 400, n has a value of 0 to about 200, and m + n has a value of at least 5.

Preferred dye transfer inhibiting enhancers of the present invention have an R group of about
Less than 50%, preferably less than about 20%, more preferably 5%
Less than contains "oxy" R units, most preferably the R units comprise a polyamine backbone that does not contain "oxy" R units.

The most preferred dye transfer inhibitor containing no "oxy" R units contains a polyamine backbone in which less than 50% of the R groups contain 4 or more carbon atoms. For example, those having 3 or less carbon atoms, ethylene, 1,2-propylene, and 1,3-propylene, are preferred "hydrocarbyl" R units. That is, when the R unit of the skeleton is C ₂ -C ₁₂ alkylene, preferred is C ₂ -C ₃ alkylene, and ethylene is most preferred.

The dye transfer retardant of the present invention comprises a modified homogeneous and heterogeneous polyamine backbone, wherein -NH
Less than 100% of the units are denatured. For the purposes of the present invention, the term "homogeneous polyamine backbone" is defined as a polyamine backbone having the same R units (ie all ethylene). However, this definition of identity does not exclude other polyamines that contain extraneous units that make up the polyamine backbone that are present because they are artifacts of the chosen chemical synthesis method. For example, as will be apparent to those skilled in the art, ethanolamine can be used as an "initiator" in the synthesis of polyethyleneimine, and thus, a polyethyleneimine comprising a hydroxyethyl moiety resulting from the polymerization "initiator" Are considered to comprise a homogeneous polyamine backbone for the purposes of the present invention.
A polyamine skeleton comprising all ethylene R units and no branch Y units is a homogeneous skeleton. The polyamine skeleton comprising all ethylene R units is a homogeneous skeleton, regardless of the degree of branching or the number of cyclic branches present.

For the purposes of the present invention, the term “heterogeneous polymer backbone” means a polyamine backbone that is a composite material consisting of various lengths of R units and types of R units. For example, a heterogeneous backbone comprises R units that are a mixture of ethylene and 1,2-propylene units. For purposes of the present invention, "hydrocarbyl" and "oxy" R
No unit mixture is required. These "R unit chain lengths"
By properly manipulating the fabric, the prescriber can determine the solubility and fabric substability of the cotton soil release agent of the present invention.
antivity).

Preferred dye transfer inhibiting enhancers of the present invention are homogeneous polyamine backbones completely or partially substituted by polyethyleneoxy moieties, fully or partially quaternary.
Graded amines, nitrogen completely or partially oxidized to N-oxides, and mixtures thereof. However, not all backbone amine nitrogens need to be modified in the same manner, and the choice of modification is left to the specific needs of the formulator. The degree of ethoxylation is also determined by the conditions specifically required by the prescriber.

Preferred polyamines containing the skeleton of the compounds of the invention are
Generally, polyalkyleneamine (PAA), polyalkyleneimine (PAI), preferably polyethyleneamine (PE
A), polyethylene imine (PEI) or parent PAA, PA
PEA or PEI connected by moieties with R units longer than I, PEA or PEI. A common polyalkyleneamine (PAA) is tetrabutylenepentamine. P
EA is obtained by fractional distillation following a reaction involving ammonia and ethylene dichloride. Typical PEAs obtained are triethylenetetramine (TETA) and tetraethylenepentamine (TEPA). Similarly derived mixtures above pentamine, ie, hexamine, heptamine, octamine and optionally nonamine, are not expected to separate by distillation and may contain other substances such as cyclic amines, especially piperazine. Cyclic amines containing side chains where a nitrogen atom appears may also be present. U.S. Pat.No. 2,792,372, describing the production of PEA, Dicki
See nson, promulgated May 14, 1957.

Preferred amine polymer backbones comprise R units which are C ₂ alkylene (ethylene) units and are also called polyethylene imines (PEI). Preferred PEI have at least moderate branching, i.e., the ratio of m to n is less than 4: 1, but PEI having an m: n ratio of about 2: 1 is most preferred. The drinkable skeleton has the following formula before denaturation And m and n are as defined above. Preferred PEIs have a molecular weight before denaturation of greater than about 200 daltons.

The relative proportions of primary, secondary and tertiary amine units in the polyamine backbone depend on the mode of production, especially in the case of PEI. Each hydrogen atom added to each nitrogen atom of the polyamine backbone represents a point where subsequent substitution, quaternization or oxidation is possible.

These polyamines can be produced, for example, by polymerizing ethyleneimine in the presence of a catalyst such as carbon dioxide, sodium bisulfite, sulfuric acid, hydrogen peroxide, hydrochloric acid, and acetic acid. Specific methods for preparing these polyamine backbones are described in U.S. Pat. No. 2,182,306, Ulrich et al., Issued Dec. 5, 1939, U.S. Pat. No. 3,033,746, Mayle et al., All of which are incorporated herein by reference. U.S. Pat. No. 2,208,095, issued May 8, 1962, Esselma
nn et al., promulgated July 16, 1940, U.S. Pat.No. 2,806,839, Crowther, promulgated September 17, 1957, and U.S. Pat.
It is described in.

The dye transfer inhibiting enhancers of the present invention comprising PEI are shown in Formulas I-IV.

Formula I represents that hydrogen is a polyoxyalkyleneoxy unit-
By replacing _{(CH 2 CH 2 O) 7} H, showing all substitutable nitrogen is modified, the dye transfer anti-enhancing agent comprising a PEI backbone.

This is an example of a cotton soil release polymer that is completely modified in one part.

Formula II represents that hydrogen is a polyoxyalkyleneoxy unit-
By replacing _{(CH 2 CH 2 O) 7} H, denature all substitutable primary amine nitrogen, followed by oxidizing all primary capable of oxidizing and secondary nitrogen in N- oxide Shows a dye transfer preventing enhancer comprising a PEI skeleton, the molecule of which is modified by the following formula. The dye transfer inhibitor has the following formula:

Formula III shows a dye transfer inhibiting enhancer comprising a PEI backbone, wherein all backbone hydrogen atoms are replaced and some backbone amine units are quaternized. The substituent is a polyoxyalkyleneoxy unit — (CH ₂ CH ₂ O) ₇ H or a methyl group. The modified PEI dye transfer inhibitor has the formula:

Formula IV is replaced skeletal nitrogen (i.e. _{- (CH 2 CH 2 O)} 7 H
Or with methyl), quaternized, oxidized to N-oxide, or a combination thereof, showing a dye transfer inhibiting enhancer comprising a PEI backbone. The resulting dye transfer inhibitor has the following formula:

In the above example, not all nitrogens in one unit section contain the same modification. The present invention allows the formulator to ethoxylate some of the secondary amine nitrogens and oxidize other secondary amine nitrogens to N-oxides. This is because the formulator can choose to modify all or part of the primary amine nitrogen before oxidation or quaternization with one or more substituents. This is also true. With the exception of the above restrictions, any possible combination of E groups can be substituted on the primary and secondary amine nitrogen.

Method of Use The present invention relates to a method of imparting the advantage of preventing dye transfer to dyed or colored fabrics. The method comprises contacting the dyed or colored fabric with a water soluble or dispersible bleach stable, modified polyamine fabric surface modifier. The agent has the following formula Having the formula V _{(n + 1)} W _m Y _n Z of the modified polyamine, or comprising the following formula: Comprises a corresponding polyamine backbone, modified formula V _{(n-k + 1)} of the polyamine having a _{W m Y n Y 'k Z} , wherein, k is less than or equal to n, said polyamine backbone, modified Before, the molecular weight was about 200
I) V units are terminal units having the formula: ii) W units are skeletal units having the formula: iii) Y units are branch units having the formula: iv) Z units are terminal units having the formula: Wherein the skeleton-bonded R units are C ₂ -C ₁₂ alkylene, C ₄ -C ₁₂
Alkenylene, C ₃ -C ₁₂ hydroxyalkylene, C ₄ -C ₁₂
Dihydroxy - alkylene, C ₈ -C ₁₂ dialkyl _{^{arylene, - (R 1 O) x}} R 1 -, - (R 1 O) x R 5 (OR 1) x -, -
(CH ₂ CH (OR ² ) CH ₂ O) _z- (R ¹ O) _y R ¹ (OCH ₂ CH (OR ² ) C
H ₂ ) _w- , -C (O) (R ⁴ ) _r C (O)-,-(CH ₂ CH (O
R ² ) is selected from the group consisting of CH ₂ —, and mixtures thereof, wherein R ¹ is C ₂ -C ₆ alkylene and mixtures thereof, R ² is hydrogen, — (R ¹ O) _x B, and a mixture of, 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 hydroxy - alkylene, C ₄ -C ₁₂ dihydroxy - alkylene, C ₈ -C ₁₂ dialkyl arylene, -C (O) -, - C (O) NHR 6 NH
C (O) -, - R 1 (OR 1) -, - 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) CH}} 2 -, and mixtures thereof, R ⁶
Is C ₂ -C ₁₂ alkylene or C ₆ -C ₁₂ arylene,
E units are selected from 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, - (R 1 O) x B, -C (O)
Selected from the group consisting of R ³ , and mixtures thereof, provided that when any E unit of nitrogen is hydrogen, the nitrogen is 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) q
(CHSO ₃ M) CH ₂ SO ₃ M, − (CH ₂ ) _q (CHSO ₂ M) CH ₂ SO ₃ M,
- (CH ₂₎ a _{p PO 3 M, -PO 3 M} , and mixtures thereof, M is a sufficient amount of hydrogen or water soluble cation to satisfy charge balance, X is a water soluble anion M, having a value of 4 to about 400, n having a value of 0 to about 200, p having a value of 1 to 6, q having 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, and z has a value of 0 or 1. These methods also use aqueous solutions of the laundry compositions of the present invention.

The method of the present invention is suitable for use when the fabric being treated for soil removal also requires bleaching. The fabric surface modifier of the present invention is compatible with compositions comprising bleaching agents commonly used to wash white fabrics.

The present invention also provides a method for washing colored fabrics with little or no dye transfer. In such methods, the fabrics are contacted with an effective amount of an aqueous wash solution formed from the above detergent composition. Contact of the fabric with the cleaning solution generally occurs under agitation conditions.

Detergent Surfactants Suitable detergent surfactants for use in the present invention are cationic, anionic, nonionic, amphoteric, zwitterionic, and mixtures thereof, as described in detail below. The laundry detergent composition may be in any suitable form, such as a granular or laundry bar, as well as a thick liquid, a light liquid or other flowable form. The cotton soil release polymer of the present invention can be incorporated into any detergent matrix selected by the formulator.

The laundry detergent composition of the present invention may further comprise at least about 0.01% by weight, preferably at least about 0.1% by weight, more preferably at least about 1% by weight of the following detersive surfactants. Generally about 1 to 55% by weight in the present invention
Examples of amounts surfactants which can be used in the conventional C ₁₁
-C ₁₈ alkyl benzene sulfonates ( "LAS") and primary branched chain and random C ₁₀ -C ₂₀ alkyl sulfates ( "AS"), the formula _{CH 3 (CH 2) x (} CHOSO 3 - M +) CH 3 and CH _{3 (CH 2) y (CHOSO} 3 - M +) C 10 ~C 18 second class CH ₂ CH ₃ (2,3) in the alkyl sulfates [wherein, x and (y +
1) at least about 7, preferably at least about 9 integer, M is a cation, especially sodium, which solubilized in water, unsaturated sulfates such as oleyl sulfate, C ₁₀ -C ₁₈ alkyl alkoxy sulfates ("AE _X S", especially O 1-7 ethoxy sulfate),
C ₁₀ -C ₁₈ alkylalkoxycarboxylates (especially EO
1-5 ethoxy carboxylates), C ₁₀ -C ₁₈ glycerol ethers, C ₁₀ -C ₁₈ alkyl polyglycosides and their corresponding sulfated polyglycosides, and C ₁₂
There are ~ _C18 alpha-sulfonated fatty acid esters,
It is not limited to these. If desired, conventional nonionic and amphoteric surfactants such C ₁₂ -C ₁₈ alkyl ethoxylates including the alkyl ethoxylates of the so-called narrow peak ( "AE") and C ₆ -C ₁₂ alkyl phenol alkoxylates (especially ethoxylates and mixed ethoxy / propoxy), C ₁₂ -C ₁₈ betaines and sulfobetaines ( "sultaines"), C ₁₀ -C ₁₈ amine oxides, and the like can also be included in the overall compositions. C _{10 to} C ₁₈ N
-Alkyl polyhydroxy fatty acid amides can also be used.
Representative examples have C ₁₂ -C ₁₈ N-methyl glucamides.
See International Patent No. WO 9,206,154. The surfactant derived from other sugars, N- alkoxy polyhydroxy fatty acid amides, for example, a C ₁₀ ~C ₁₈ N- (3- methoxypropyl) glucamide. N-propyl to N-hexyl
C ₁₂ -C ₁₈ glucamides can be used for low foaming. Conventional C
_{10 ~C 20} soaps can also be used. If high foaming is desired, the branched C ₁₀ -C ₁₆ soaps may be used. Mixtures of anionic and nonionic surfactants are particularly useful. Other commonly useful surfactants are described in standard textbooks.

Anionic Surfactant Component The detergent composition of the present invention preferably comprises at least about 5% by weight of an anionic surfactant component, preferably about 5-60% by weight. . More preferably, such compositions comprise about 10-40% by weight of the anionic surfactant component.

A significant portion of the anionic surfactant component, ie, at least 50%, more preferably at least 75%, is an ethoxylated alkyl sulfate surfactant. Such ethoxylated alkyl sulfates are materials corresponding to the formula:

During ^{_{R 2 -O- (C 2 H 4}} O) n -SO 3 M type, R ² is C ₁₀ -C ₂₂ alkyl radical, n is from about 1 to 20
And M is a salt-forming cation. Preferably R ² is C
₁₂ to _C18 alkyl, n is about 1 to 15, and M is sodium, potassium, ammonium, alkyl ammonium or alkanol ammonium. Most preferably R ² is C ₁₂ ~C _16, n is from about 1 to 6, M is sodium. These materials, also referred to as alkyl ether sulfates, provide particularly desirable dye transfer inhibiting properties when used in combination with the specific polymeric dye transfer inhibitors described below.

Alkyl ether sulfates are typically used in the form of a variety of R ² chain lengths and mixtures comprising various degree of ethoxylation. Such mixtures have the formula of certain non-ethoxylated alkyl sulfate materials, i.e., the ethoxylated alkyl sulfates described above,
A surfactant in which n is 0 is often inevitably included. Such non-ethoxylated alkyl sulfate anionic surfactants tend to be less effective than ethoxylated alkyl sulfates in preventing dye transfer in the compositions of the present invention. It is therefore important that the anionic surfactant component of the present invention does not exceed about 50% of such non-ethoxylated alkyl sulfate material components. Preferably, the content of non-ethoxylated alkyl sulfate is less than about 25% of the anionic surfactant component.

In addition to the ethoxylated alkyl sulphate surfactant used as an essential component, the anionic surfactant component of the composition of the present invention can also optionally include an additional anionic surfactant. Such additional, optionally used, materials are compatible with the other components of the composition and do not significantly affect the performance of the composition, e.g., dye transfer inhibition or composition stability. is necessary. As the anionic surfactant to be used if desired, there is generally a carboxylate type anionic substance. The carboxylate-type anionic substances such C ₁₀ -C ₁₈ soaps, C ₁₀ -C ₁₈ alkyl alkoxy carboxylates (especially ethoxy carboxylates EO1～5) and C ₁₀ -C ₁₈ sarcosinates, especially oleyl sarcosinate There is.

One common type of anionic surfactant that should not be used in the anionic surfactant component of the composition of the present invention is a sulfonated anionic material that is an alkylbenzene sulfonate. Non-bleach-activated sulfonated anionic surfactants, such as linear alkyl benzene sulfonates (LAS), include the polymer dye transfer used here to reduce dye transfer between fabrics when washing the fabric They tend to interfere with the efficacy of the inhibitor. Accordingly, the anionic surfactant of the detergent composition of the present invention should be substantially free of such an alkylbenzene sulfonate anionic surfactant.

Nonionic Surfactant Component The detergent composition of the present invention preferably comprises from about 5% by weight,
Preferably, it also contains about 1 to 20% by weight of a nonionic surfactant component. More preferably, such compositions comprise from about 2 to 10
% By weight of the nonionic surfactant component.

The non-ionic surfactant component comprises one, and preferably both, of two special types of non-ionic surfactant materials as essential components. These materials are polyhydroxy fatty acid amides and alcohol ethoxylates.

1) Polyhydroxy fatty acid amide Another preferred nonionic surfactant is a polyhydroxy fatty acid amide having the formula:

Wherein R ⁷ is C ₅ -C ₃₁ alkyl, preferably linear C ₇ -C
₁₉ alkyl or alkenyl, more preferably C ₉ -C ₁₇
Alkyl or alkenyl, most preferably linear C ₁₁ -C
₁₅ alkyl or alkenyl, or a mixture thereof, wherein R ⁸ is selected from the group consisting of hydrogen, C ₁ -C ₄ alkyl, C ₁ -C ₄ hydroxyalkyl, preferably methyl or ethyl, more preferably methyl. is there. Q is a polyhydroxyalkyl moiety having a straight chain alkyl chain containing at least three hydroxyls directly attached to the chain, or an alkoxylated derivative thereof, with preferred alkoxy being ethoxy or propoxy, and mixtures thereof. Preferred Q is derived from a reducing sugar in a reductive amination reaction. More preferably, Q is a glycityl moiety. Suitable reducing sugars include glucose, fructose,
Maltose, lactose, galactose, mannose,
And xylose. Raw materials include high dextrose corn syrup, high fructose corn syrup,
High maltose corn syrup, as well as the individual sugars described above, can be used. These corn syrups
A mixture of sugar components for Q can be provided. Of course, this does not exclude other suitable raw materials. Q is more preferably _{-CH 2 - (CHOH) n CH} 2 OH-, -CH (CH 2 OH) (CHOH) n-1 CH 2 OH-, -CH 2 - (CHOH) 2 (CHOR ') ( CHOH) -CH ₂ OH-, and is selected from the group consisting of alkoxylated derivatives, where n is an integer from 3 to 5, R 'is a monosaccharide hydrogen or a cyclic or aliphatic. The most preferred substituents on the Q moiety is n is 4 glycityls, particularly -CH ₂ (CHOH) ₄
CH ₂ OH.

R ⁷ -CO-N <is, for example, cocamide, stearamide, oleamide, lauramide, myristamide, capricamide,
Palmitamide, tallowamide and the like may be used.

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

Q is 1-deoxyglucityl, 2-deoxyfrucchityl, 1-deoxymultityl, 1-deoxylactytyl, 1-deoxygalacticyl, 1-deoxymannicyl, 1-deoxymaliltotriotyl, etc. Is fine.

Particularly preferred surfactants of this type for use in the compositions of the present invention have the formula above, wherein R ⁷ is alkyl (preferably C ₁₁ -C ₁₃ ), R ₈ is methyl, Q is 1-
Deoxyglucityl, alkyl-N-methylglucamide.

Methods for producing polyhydroxy fatty acid amides are known, for example, Wils, the disclosure of which is incorporated herein by reference.
on in U.S. Pat. No. 2,965,576 and Schwartz in U.S. Pat. No. 2,703,789. The materials themselves and their method of manufacture are described in Honsa U.S. Pat.
No. 4,937, promulgated on December 26, 1992, this patent is also incorporated herein by reference.

When a non-ionic polyhydroxy fatty acid amide is used as the non-ionic surfactant component of the detergent composition of the present invention, it is generally used in an amount of about 1 to 20% by weight of the composition.
More preferably, the non-ionic polyhydroxyfatty acid amide can make up about 2 to 10% by weight of the composition of the present invention.

Alcohol Ethoxylate Another suitable component of the nonionic surfactant used in the composition of the present invention is an ethoxylated fatty alcohol nonionic surfactant. Such materials are those corresponding to the following general formula:

R ¹ in _{(C 2 H 4 O) n} OH formula, R ¹ is C ₈ -C ₁₆ alkyl or C ₆ -C ₁₂ alkyl phenol radical, n is about 1-80. Preferably
R ¹ is a primary or secondary alkyl group having about 9 to 15 carbon atoms, more preferably about 10 to 14 carbon atoms. Preferably, the ethoxylated fatty alcohol has about 2 per molecule.
~ 12 ethylene oxide moieties, more preferably one molecule
It contains about 3 to 10 ethylene oxide moieties per piece.

Ethoxylated fatty alcohols and nonionic surfactants often have a hydrophilic-lipophilic balance (HLB) of about 3-17. More preferably, the HLB of this material is about 6-1
5, most preferably about 10-15.

Examples of fatty alcohol ethoxylates useful as liquid nonionic surfactants essential to the compositions of the present invention include materials made from alcohols having 12 to 15 carbon atoms and containing about 7 moles of ethylene oxide. is there. One such material is Neodol 25 from Shell Chemical Company.
-7 and Neodol 23-6.5.
Other useful Neodols include Neodol 1-5, an ethoxylated fatty alcohol having an average of 11 carbon atoms in the alkyl chain, containing about 5 moles of ethylene oxide, ethoxylated primary alcohols having about 9 moles of ethylene oxide. grade C ₁₂ -C ₁₃ alcohols Neodol 23-9, having the ethylene oxide about 10 mol, there are ethoxylated C ₉ ~C ₁₁ Neodol 91-10 is a primary alcohol. This type of alcohol ethoxylate is also commercially available from Shell Chemical Company under the trade name Dobanol. Dobanol 91-5 is an ethoxylated C ₉ -C ₁₁ fatty alcohol with an average of 5 moles of ethylene Oki tides, Dobanol 25-7 is an ethoxylated C ₁₂ -C having ethylene oxide average 7 moles per fatty alcohol 1 mole ₁₅ fatty alcohols.

Other examples of suitable ethoxylated alcohol nonionic surfactants include both Union Carbide Corporatio
Tergitol 15-S-7 and Tergitol 15-S, linear secondary alcohol ethoxylates commercially available from
-9. The former contains 7 moles of ethylene oxide
C ₁₁ -C ₁₅ is a mixed ethoxylation product of linear secondary alcohol, the latter is a similar product obtained by reacting 9 moles of ethylene oxide.

Another type of alcohol ethoxylate non-ionic material useful in the composition is a high molecular weight non-ionic material such as Neodol 45-11, which is an ethylene oxide condensation product similar to higher fatty alcohols, Higher fatty alcohols have 14 to 15 carbon atoms and about 11 ethylene oxide groups per mole. Shell Ch for such products
Commercially available from emical Company.

When an alcohol ethoxylate nonionic material is used for the nonionic surfactant component of the detergent composition of the present invention, that material is generally present in an amount of about 0.5 to 10% by weight of the composition. More preferably, the alcohol ethoxylate nonionic material generally comprises from about 1 to 5 of the composition of the present invention.
Accounts for% by weight.

Non-Liner Soil Release Agent A known polymer soil release agent (hereinafter referred to as “SRA”) can be used in the detergent composition of the present invention, if desired. When used, the SRA generally ranges from 0.01 to 10.
It accounts for 0% by weight, in particular 0.1 to 5% by weight, preferably 0.2 to 3.0% by weight.

Preferred SRAs are hydrophilic moieties for imparting hydrophilicity to the surface of hydrophobic fibers, such as polyester and nylon, and are deposited on the hydrophobic fibers and adhere to them until the wash and rinse cycle is complete. It generally has a hydrophobic part that acts as an anchor for the sexual part. This makes it easier to clean dirt that has been applied after the SRA treatment in a later washing step.

SRA can be any of a variety of charged, eg, anionic or cationic, materials (US Pat. No. 4,956,447, 1990).
Published by Gosselink et al., Sep. 11, 2011), as well as uncharged monomer units, whose structure may be linear, branched or star-shaped. The SRA can include a cap moiety that is particularly effective in adjusting molecular weight or improving physical properties or surface activity. The structure and charge distribution can be adapted for use on different fiber or textile types, and for different detergents or detergent additive products.

Preferred SRAs include oligomeric terephthalates produced by processes involving at least one transesterification / oligomerization (often using a metal catalyst such as a titanium (IV) alkoxide). Such esters are of course made using additional monomers that can be incorporated into the ester structure through one, two, three, four or more positions, without forming a tightly crosslinked overall structure. be able to.

Other SRAs include U.S. Pat.No. 4,711,730, 1987
December 8, Gosselink et al., Nonionic end-capped 1,2-propylene / polyoxyethylene terephthalate polyesters such as poly (ethylene glycol) methyl ether, DMT, PG and poly (ethylene glycol) ("PEG"). There are materials produced by the transesterification / oligomerization of Other examples of SRA include U.S. Pat. No. 4,721,580, Jan. 26, 1988, Gosseli
nk, partially and completely anionic end-capped oligomeric esters such as ethylene glycol (“E
G "), PG, DMT and oligomers such as those obtained from Na-3,6-dioxa-8-hydroxyoctanesulfonate, and U.S. Pat. No. 4,877,896, Oct. 3, 1989.
One day, there is an anionic system from Maldonado, especially sulfoaroyl end-capped terephthalates, the latter being a typical SRA useful for both laundry and fabric conditioning products, one example of which is m-sulfobenzo. Acid monosodium salt, ester composition made from PG and DMT, but optionally but preferably further added
Comprising PEG, for example PEG3400.

SRA includes simple copolymer blocks of ethylene terephthalate or propylene terephthalate and polyethylene oxide or polypropylene oxide terephthalate (US Pat. No. 3,959,230, Hays, May 2, 1976).
5, and U.S. Pat.No. 3,893,929, Basadur, 1
Jul. 8, 975), cellulose derivatives such as Dow
Commercially available hydroxy ether cellulosic polymers, C ₁ -C ₄ alkylcelluloses and C ₄ hydroxyalkyl cellulose as MECHOCEL from (U.S. Pat. No. 4,000,093, Dec. 28, 1976, Nicol, see etc.), and anhydro Average degree of substitution (methyl) per glucose unit is about 1.
Some methyl cellulose ethers have a solution viscosity of about 80 to about 120 centipoise, measured at 20 ° C. as a 2% aqueous solution, from 6 to about 2.3. Such materials are available as METOLOSE SM100 and METOLOSE SM200, trade names of methylcellulose ether manufactured by Shin-Etsu Chemical Co., Ltd.

Poly Suitable SRA characterized by (vinyl ester) hydrophobic moiety, polyalkylene oxide backbone grafted onto poly (vinyl ester), e.g., C ₁ -C ₆ vinyl esters, preferably poly (vinyl acetate) Is a graft copolymer. See European Patent Application No. 0219048, Kud et al., Published April 22, 1987. Commercially available examples include SOKA, commercially available from BASF, Germany.
There is a LAN SRA, such as SOKALAN HP-22. Other SRA is 10
~ 15 wt% ethylene terephthalate, 80-90 wt%
Is a polyester having a repeating unit containing polyoxyethylene terephthalate derived from polyoxyethylene glycol having an average molecular weight of 300 to 5,000. Commercially available examples include Dupont's ZELCON 5126 and ICI
There is MILEASE T made by.

Another preferred SRA is empirical formula (CAP) ₂ (EG / P
G) An oligomer having ₅ (T) ₅ (SIP) ₁ ,
It comprises terephthaloyl (T), sulfoisophthaloyl (SIP), oxyethyleneoxy and oxy-1,2-propylene (EG / PG) units, preferably end caps (CAP), preferably modified isethionate ends Having, for example, one sulfoisophthaloyl unit, five terephthaloyl units, in a limited ratio, preferably about
0.5: 1 to about 10: 1 oxyethyleneoxy and oxy-
There are oligomers comprising 1,2-propylene units and two end caps derived from sodium 2- (2-hydroxyethoxy) -ethanesulfonate. The SRA
Is preferably 0.5 to 20% by weight of the oligomer, a substance selected from crystallinity-reducing stabilizers such as sodium linear dodecylbenzenesulfonate or xylene-, cumene-, and toluene-sulfonates or mixtures thereof. Further comprising an anionic surfactant such as, for example, US Pat.
No. 5,807, Gosselink, Pan, Kellett and Hall,
Introduced into synthetic containers as disclosed on May 16, 1995. Suitable monomers for the above SRA include Na-2- (2-hydroxyethoxy) -ethanesulfonate, DMT, Na-dimethyl-5-sulfoisophthalate, EG and PG.

Another group of SRAs include (I) nonionic terephthalates which use a diisocyanate coupling agent to link the polymer ester structure (U.S. Pat. No. 4,201,824;
iolland et al. and U.S. Pat.No. 4,240,918, Lagass
e) and (II) trimellitic anhydride with known SRA
And SRAs containing carboxylate salts and groups prepared by converting the terminal hydroxyl groups to trimellitate esters. By selecting an appropriate catalyst, trimellitic anhydride forms a bond at the end of the polymer through an isolated carboxylic acid ester of trimellitic anhydride, rather than opening an anhydride bond. Nonionic or anionic SRs as long as they have an esterifiable hydroxyl end group
You can use either of A. See U.S. Pat. No. 4,525,524, Tung et al. Other types include (III) SRA based on anionic terephthalate having various urethane bonds (see U.S. Pat. No. 4,201,824, Violland et al.), (IV) nonionic and cationic heavy Poly (vinylcaprolactam) and related copolymers with monomers such as vinylpyrrolidone and / or dimethylaminoethyl methacrylate (US Pat.
No. 4,579,681, Ruppert et al.), And (V) In addition to SOKALAN type commercially available from BASF, there is a graft copolymer produced by grafting an acrylic monomer onto a sulfonated polyester. These SRAs are claimed to have soil release and anti-redeposition activity similar to known cellulose ethers (see EP 279,134A to Rhone-Poulenc Chemie). Yet another class includes (VI) the grafting of vinyl monomers such as acrylic acid and vinyl acetate onto proteins such as casein (EP 457,205 to BASF, EP 457,205 (199).
1)) and (VII) polyesters prepared by condensation of adipic acid, caprolactam and polyethylene glycol, especially for treating polyamide fabrics.
There is a polyamide SRA (Bevan et al., DE 2,335,044 to Unilever NV, 1974). Other useful SRAs are described in U.S. Pat.Nos. 4,240,918, 4,787,98
No. 9 and 4,525,524.

Preferred Non-Cotton Soil Release Agents Laundry detergent compositions of the present invention include: a) i) at least one portion having the formula: ii) at least one moiety having the formula: Wherein R ⁹ is C ₂ -C ₆ straight chain alkylene, C ₃ -C ₆ branched chain alkylene, C ₅ -C ₇ cyclic alkylene, and mixtures thereof, and R ¹⁰ is independently hydrogen or -L-SO ₃ is selected from -M ^+, L is an alkylene, oxyalkylene, alkyleneoxyalkylene, arylene, oxyarylene, alkylene-oxy arylene, poly (oxyalkylene), oxy-alkylene-oxy arylene, poly (oxyalkylene) oxy A side chain moiety selected from the group consisting of arylene, alkylene poly (oxyalkylene), and mixtures thereof, wherein M is hydrogen or a salt-forming cation and i has a value of 0 or 1), iii) At least one trifunctional, ester-forming branching moiety; and iv) at least one 1,2-oxyalkyleneoxy moiety And b) i) an ethoxylated or propoxylated hydroxyethanesulfonate or ethoxylated or propoxylated formula (MO ₃ S) (CH ₂ ) _m (R ¹¹ O) _n − A hydroxypropanesulfonate unit (where M is
A salt-forming cation such as sodium or tetraalkylammonium, R ¹¹ is ethylene or propylene or a mixture thereof, m is 0 or 1,
n is 0 to 20), ii) formula _{- (O) C (C 6} H 4) (SO 3 - M +) Suruhoaroiru units (in the formula, M is a salt forming cation), iii) formula R ¹² O (CH ₂ CH ₂ O) _k -modified poly (oxyethylene) oxymonoalkyl ether unit (wherein R ¹² has 1 to 4 carbon atoms and k has about 3 to about 100) , and iv) formula _{MO 3 S (C 6 H 4} ) (oR 13) n O- ethoxylated or propoxylated phenols sulfonate end-capping units (wherein, n is 1 to 20, M is a salt Preferred are soil release polymers comprising one or more cap units comprising the forming cation and R ¹³ is ethylene, propylene and mixtures thereof.

A preferred soil release polymer of this type according to the invention can be described as a substance having the formula:

[(Cap) (R ⁴ ) _t ] [(AR ¹ -AR ² ) _u (AR ¹ -AR ³ ) _v (AR ¹ -AR ⁵ ) _w -A- R ¹ -A-] [(R ⁴ ) _t (Cap)] wherein A is a carboxy-binding moiety having the formula: R ¹ is arylene, preferably a 1,4-phenylene moiety having the formula: When the A unit and R ¹ together form the formula AR ¹ -A,
Forming a terephthalate unit having the formula: The R ² unit is ethyleneoxy or 1,2-propyleneoxy. R ² units are combined with the terephthalate moiety,
Forming (A-R ¹ -A-R ² ) units having the formula: Here, R 'and R "are hydrogen or methyl, provided that both R' and R" are not methyl at the same time.

The R ³ unit is a trifunctional, ester-forming branching moiety having the formula: Preferably R ³ units comprises a glycerol moiety which is placed into the soil release polymer backbone give a branch point. When R ³ units are combined with a terephthalate moiety to form units of the polymer skeleton, for example, (AR ¹ -AR ³ ) -AR ¹ -A units, these units have the formula: Or the following formula Wherein ^one terephthalate residue is (A-R ^1-
A-R ³⁾ becomes part of the unit, the second phthalates another backbone unit, e.g., ^{(A-R 1 -A-R} 2) units, (A-R ¹ -A
-R ⁵ ) units, -AR ¹ -A-[(R ⁴ ) _t (Cap)] units or part of the second (AR ¹ -AR ³ ) units. The third functional group at the head of the branched chain is also (A-
R ¹ -AR ² ) units, (AR ¹ -AR ⁵ ) units, -AR ¹
-A-[(R ⁴ ) _t (Cap)] units or another (A-R ^1-
Generally binds to terephthalate residues, which is part of the A-R ³⁾ unit.

Examples of moieties which contain a soil release polymer comprises glycerol units "trifunctional, branched moiety forms an ester" R ³ units, Wherein R ₄ units are R ² , R ³ or R ⁵ units, wherein R ⁵ units have the following formula: Wherein R ⁹ is C ₂ -C ₆ linear alkylene, C ₃ -C ₆ branched alkylene, and mixtures thereof, preferably R 9
¹⁰ are independently selected from hydrogen or -L-SO ₃ -M ^+, L is an alkylene, oxyalkylene, alkyleneoxyalkylene, arylene, oxyarylene, alkylene-oxy arylene, poly (oxyalkylene), oxyalkylene A side chain unit selected from the group consisting of oxyarylene, poly (oxyalkylene) oxyarylene, alkylenepoly (oxyalkylene), and mixtures thereof, wherein M is hydrogen or a salt-forming cation, and i is 0 or It has a value of 1.

Each carbon atom of the R ⁹ units is substituted by R ¹⁰ units, but R ¹⁰ units are independently selected from hydrogen or -L-SO ₃ -M ^+, provided that at least two to R ⁹ units -L-SO ₃ -M
^{No +} unit is added, L is alkylene, oxyalkylene, alkyleneoxyalkylene, arylene, oxyarylene, alkyleneoxyarylene, poly (oxyalkylene), oxyalkyleneoxyarylene,
A side chain connecting moiety selected from the group consisting of poly (oxyalkylene) oxyarylene, alkylene poly (oxyalkylene), and mixtures thereof.

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

Preferred R ⁵ units are substantially C ₂ -C ₆ alkylene chain R ¹⁰ substituted. R ⁵ units, or containing one C ₂ -C ₆ alkylene chain substituted by one or more independently selected R ¹⁰ moieties (preferred), or two connected by an ether oxygen bond includes C ₂ -C ₆ alkylene chain, each alkylene chain are replaced by the selected R ¹⁰ moieties one or more independently, i.e. R ⁵ comprises two separate R ⁹ units, R ⁹ it can be substituted by R ¹⁰ moiety each unit is one or more independently selected. Preferably, only one carbon atom of the R ⁹ moiety is -L-SO ₃ -M
⁺ Unit, the remaining R ¹⁰ substituents contain hydrogen atoms. If the value of the index i is equal to 1 (two R ⁹ units make up R ⁵ units), the preferred formula is Wherein each R ⁹ comprises a C ₂ alkylene moiety. Preferably one R ¹⁰ moiety is -L-SO ₃ ^- M a ^+, preferably C
₂ carbon -L-SO ₃ ^- M ⁺ moiety is substituted with, the remainder is a hydrogen atom, thus the formula Wherein L is a polyethyleneoxymethyl substituent and x is 0 to about 20.

The expression used here, "R ⁵ part is practically a unit Made, the index i is equal to 0, R ¹⁰ units are hydrogen, one is the R ¹⁰ units -L-SO ₃ ^- equal to M ^+, L is alkylene, alkenylene, alkoxyalkylene, oxyalkylene, arylene , alkylarylene, alkoxy and arylene and is selected side chains connecting portion from mixtures thereof ", R ¹⁰ moiety is one -L-SO ₃ ^- consists M ⁺ moiety and the remaining R ¹⁰ Preferred compounds of the invention wherein the moiety is a hydrogen atom, for example It refers to, the compounds may be incorporated as an -A-R ⁵ -A- backbone moiety in the polymer backbone of the soil release polymers of the present invention. These units have the general formula (Where x is 0 to 20 for the purpose of the L moiety of the present invention) can be easily incorporated into the oligomer or polymer backbone.

Other suitable monomers which may be incorporated preferably of type A in the non-cotton soil release polymer backbone as R ⁵ parts of the present invention, the alkylene poly (oxyalkylene) oxyarylene containing monomer having the general formula is there.

In the formula, x is 0-20. i is equal to 0, preferred
Other examples of preferred monomers to produce R ⁵ units are sodium sulfo poly (ethyleneoxy) methyl-1,2-propanediol having the formula.

Wherein x is 0 to about 20. More preferred are monomers It is.

Preferred soil release agents of the present invention are R ¹ , R ² , R ³ ,
In addition to R ⁴ and R ⁵ , one or more cap groups (Cap)
Also comprises. These capping group is independently of the formula _{(MO 3 S) (CH 2} ) m (R 11 O) n - of the ethoxylated or propoxylated hydroxyethanesulfonate and propane sulfonate units (in the formula, M A salt-forming cation such as sodium or tetraalkylammonium, as described above, R ¹¹ is ethylene or propylene or a mixture thereof, m is 0 or 1, and n is 1 to
20; preferably n is 1 to about 4);
_{(O) C (C 6 H} 4) - Suruhoaroiru units (SO ₃ M ⁺⁾ (wherein, M is such salt forming cation of the above), wherein R ¹² O
_{(CH 2 CH 2 O) k} - modified poly (oxyethylene) oxy monoalkyl ether units (in the formula, R ¹² is 1 to carbon atoms
4, preferably R ¹² is methyl and k is about 3 to
About 100, preferably about 3 to about 50, more preferably 3 to about 3
0), and an ethoxylated or propoxylated phenolsulfonate end-cap unit of the formula MO ₃ S (C ₆ H ₄ ) (OR ¹³ ) _n O—, wherein n is 2020 and M is a salt forming cation, R ¹³ is selected from ethylene, propylene and mixtures thereof).

The most preferred endcap unit is an isethionate-type endcap unit, which comprises a hydroxyethane moiety,
(MO ₃ S) (CH ₂ ) _m (R ¹¹ O) _n −, and preferably R
¹¹ is ethyl, m is 0, and n is 2-4.

The value of t is 0 or 1, the value of u is about 0 to about 60, the value of v is about 0 to about 35, and the value of w is 0 to 35.

The following formula [(Cap) (R ⁴ ) _t ] [(AR ¹ -AR ² ) ^u (AR ¹ -AR ³ ) _v (AR ¹ -AR ⁵ ) _w A preferred soil release polymer of the present invention having -AR ¹ -A-] [(R ⁴ ) _t (Cap)] can be represented by the following general structural formula.

The following structure is an example of a preferred soil release polymer of the present invention.

The preferred soil release agents described above are described in U.S. Patent Application Serial No. 08 / 355,938, 1994, both of which are incorporated herein by reference.
U.S. patent application Ser.
No. 45,351, filed Nov. 22, 1995. Other non-cotton soil release polymers useful in the compositions of the present invention are described further below.

Other preferred SRAs are (1) (a) dihydroxysulfonate, polyhydroxysulfonate, at least 3
Functional, whereby an ester bond is formed,
At least one unit selected from the group consisting of units that result in a branched oligomer backbone, and combinations thereof; (b) at least one unit that is a terephthaloyl moiety; and (c) a 1,2-oxyalkyleneoxy moiety. And (2) a nonionic cap unit, an anionic cap unit, such as an alkoxylated, preferably ethoxylated isethionate, an alkoxylated unit. Ester oligomers comprising one or more cap units selected from propane sulfonate, alkoxylated propane disulfonate, alkoxylated phenol sulfonate, sulfoalloyl derivatives, and mixtures thereof. Preferred materials are esters having the following empirical formula:

{(CAP) x (EG / PG) y '(DEG) y "(PEG) y (T) z (SIP) z' (SEG) q (B) m where CAP, EG / PG, PEG, T and SIP are terephthaloyl (T), sulfoisophthaloyl (SIP), oxyethyleneoxy and oxy-1,2-propylene (EG / PG)
Defined as units, endcap (CAP), poly (ethylene glycol) (PEG), (DEG) stands for di (oxyethylene) oxy unit, and (SEG) is a unit derived from the sulfoethyl ether of glycerin and related (B) represents a branch unit that is at least trifunctional, thereby forming an ester bond and resulting in a branched oligomer backbone; x is from about 1 to about 12;
y 'is about 0.5 to about 25; y "is 0 to about 12;
Is 0 to about 10, and the sum of y '+ y "+ y is about 0.5
To about 25, z is about 1.5 to about 25, and z 'is 0 to about 1
2, the sum of z + z 'is about 1.5 to about 25, and q is about
0.05 to about 12, m is about 0.01 to about 10, x,
y ′, y ″, y, z, z ′, q and m represent the average of the number of moles of the corresponding unit per one ester,
The ester has a molecular weight of about 500 to about 5,000.

Preferred SEG and CAP monomers for the above esters include Na-2- (2-, 3-dihydroxypropoxy) ethanesulfonic acid salt ("SEG"), Na-2- {2- (2-
There are ethoxylated and sulfonated products of (hydroxyethoxy) ethoxydiethanesulfonate ("SE3"), and homologs and mixtures thereof and allyl alcohol. Preferred SRA esters of this type include:
Sodium 2- {2- (2-hydroxyethoxy) ethoxy} ethanesulfonate and / or 2- [2- {2- (2-hydroxyethoxy) ethoxy} ethoxy] ethane using a suitable Ti (IV) catalyst There are products obtained by transesterification and oligomerization of sodium sulfonate, DMT, sodium 2- (2,3-dihydroxypropoxy) ethane sulfonate, EG, and PG, (CA
P) is represented by 2 (T) 5 (EG / PG) 1.4 (SEG) 2.5 (B) 0.13, CAP is _{(Na + O 3 S [CH} 2 CH 2 O] 3.5) - and is, B is derived from glycerin In units, the EG / PG molar ratio is about 1.7: 1 as determined by conventional gas chromatography after completion of the hydrolysis.

Bleaching Compounds-Bleaching Agents and Bleaching Activators The detergent compositions of the present invention can optionally include a bleaching agent or a bleaching composition comprising a bleaching agent and one or more bleaching activators. Bleaching agents, when present, especially for fabric laundering, are present in amounts from about 0.05% to about 30%, more preferably from about 1% to about 30%, most preferably from about 5% to about 20% of the detergent composition. It is. When present, the amount of bleach activator will generally range from about 0.1% to about 60%, more usually from about 0.5% to about 40%, of the bleaching composition comprising the bleach activator in addition to the bleach. %.

The bleach used herein may be any of the currently known bleaches useful for detergent compositions in fabric washing. These bleaches include oxygen bleaches as well as other bleaches. Here, perborate bleaches, such as sodium perborate (eg mono- or tetrahydrate), can be used.

Other types of bleaches that can be used successfully include percarboxylic acid bleaches and their salts. Preferred examples of this type of bleach include magnesium monoperoxyphthalate hexahydrate, magnesium salt of metachloroperbenzoic acid,
There are 4-nonylamino-4-oxoperoxybutyric acid and diperoxidedecanedioic acid. Such bleach is described in U.S. Pat.No. 4,483,781, Hartman, November 1984.
Promulgated on May 20, U.S. Patent Application No. 740,446, Burns
Et al., Filed June 3, 1985, European Patent Application 0,133,
No. 354, Banks et al., Published Feb. 20, 1985, and U.S. Pat. No. 4,412,935, Chung et al., Promulgated November 1, 1983. 6-nonylamino-6-oxoperoxycaproic acid, described in U.S. Pat. No. 4,634,551, issued Jan. 6, 1987 to Burns et al., Is also a highly preferred bleaching agent.

Peroxygen bleaches can also be used. Suitable peroxygen bleaching compounds include sodium hydrogen carbonate peroxide and equivalent "percarbonate" bleaches, sodium pyrophosphate hydrogen peroxide, urea hydrogen peroxide, and sodium peroxide. Persulfate bleach (eg, OXONE, manufactured and sold by DuPont) can also be used.

Preferred percarbonate bleaches have an average particle size of from about 500 micrometers to about 1,000 micrometers, with a mean particle size of about 200 micrometers.
Less than about 10% by weight of particles less than micrometers,
Less than about 10% by weight of particles greater than about 1,250 micrometers. If desired, the percarbonate can be coated with a silicate, borate or water-soluble surfactant. Percarbonates can be obtained from various commercial sources, such as FMC, Solvay and T
Available from okai Denka.

 Mixtures of bleach can also be used.

The peroxygen bleaches, perborates, percarbonates, etc., are preferably used in combination with the respective aqueous solutions of peracids with bleach activators which are formed in situ (ie during the washing step). Various non-limiting examples of activators are described in U.S. Pat.
No. 4,915,854, issued Apr. 10, 1990 to Mao et al., And in U.S. Pat. No. 4,412,934. Nonanoyloxybenzenesulfonate (NOBS) and tetraacetylethylenediamine (TAED) activators are representative, and mixtures thereof can also be used. For other representative bleaches and activators useful herein, see U.S. Pat.
See also 4,634,551.

Highly preferred amide-derived bleach activators are those having the formula:

R ¹ N (R ⁵ ) C (O) R ² C (O) L or R ¹ C (O) N (R ⁵ ) R ² C (O) L wherein R ¹ has about 6 to about 12 carbon atoms. R ² is alkylene having 1 to about 6 carbons, R ⁵ is H or alkyl, aryl, or alkaryl having 1 to about 10 carbons, and L is a suitable leaving group Group. By leaving group is meant a group that is excluded from the bleach activator as a result of a nucleophilic attack on the bleach activator by a perhydrolysis anion. A preferred leaving group is phenylsulfonate.

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

Another type of bleach activator is U.S. Pat.No. 4,966,723, Hodge et al., Oct. 30, 1990, incorporated herein by reference.
There are benzoxazine-type active agents described on the date. A highly preferred activator of the benzoxazine type is of the formula

Yet another preferred class of bleach activators are acyllactam activators, especially acylcaprolactam and acylvalerolactam having the formula:

Wherein R ⁶ is H or an alkyl, aryl, alkoxyaryl, or alkaryl group having 1 to about 12 carbon atoms. Highly preferred lactam activators include benzoylcaprolactam, octanoylcaprolactam, 3,5,5-
Trimethylhexanoylcaprolactam, nonylcaprolactam, decanoylcaprolactam, undecenoylcaprolactam, benzoylvalerolactam, octanoylvalerolactam, decanoylvalerolactam, undecenoylvalerolactam, nonanoylvalerolactam, 3,5,5-trimethyl Hexanoyl valerolactam and mixtures thereof. Include here for reference,
See U.S. Pat. No. 4,545,784, Sanderson, issued Oct. 8, 1985, which discloses acylcaprolactams containing benzoylcaprolactam adsorbed in sodium perborate.

Bleaches other than oxygen bleaches are also known in the art,
Can be used here. One class of particularly important non-oxygen bleaches is light activated bleaches, such as zinc sulfonates and / or
Or there is aluminum phthalocyanine. U.S. Patent No.
See 4,033,718, Holcombe et al., Promulgated July 5, 1977. When used, detergent compositions generally range from about 0.025 to about
It contains 1.25% by weight of such bleaches, especially sulfonated zinc phthalocyanines.

If desired, the bleaching compound can be catalyzed using a manganese compound. Such compounds are well known in the art and are described, for example, in U.S. Patent No. 5,246,621.
No., U.S. Pat.No. 5,244,594, U.S. Pat.
No. 5,194,416, U.S. Pat.No. 5,114,606, and published European Patent Application 549,271 A1,
49,272A1, 544,440A2, and 54
There is a manganese-based catalyst described in 4,490A1. Preferred examples of these catalysts include Mn ^IV ₂ (u
—O) ₃ (1,4,7-trimethyl-1,4,7-triazacyclononane) ₂ (PF ₆ ) ₂ , Mn ^III ₂ (uO) ₁ (u-OAc)
₂ (1,4,7-trimethyl-1,4,7-triazacyclononane) ₂ (ClO ₄ ) ₂ , Mn ^IV ₄ (uO) ₆ (1,4,7-triazacyclononane) ₄ (ClO ₄ ) ₄ , Mn ^III Mn ^IV ₄ (uO)
₁ (u-OAc) 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 (} P
F ₆ ), and mixtures thereof. Other metal-based bleach catalysts include those described in U.S. Pat. No. 4,430,243 and U.S. Pat. No. 5,114,611. The use of manganese with various complexing ligands to enhance bleachability is also described in U.S. Pat.Nos. 4,728,455 and 5,284,9.
No. 44, No. 5,246,612, No. 5,256,779, No. 5,280,117, No. 5,274,147, No. 5,
Nos. 153,161 and 5,227,084.

As a practical matter, but not by way of limitation, the cleaning compositions and cleaning methods of the present invention preferably provide about 0.1 parts per million active bleach catalyst in an aqueous cleaning liquor, preferably about 0.1 parts per million. It can be adjusted to provide from about ppm to about 700 ppm, more preferably from about 1 ppm to about 500 ppm, of the catalytic material in the wash liquor.

The compositions of the present invention include detergent compositions that include other active ingredients, carriers, hydrotropic agents, processing aids, dyes or pigments, solvents like liquid formulations, solid fillers for bar compositions, and the like. It can include a wide variety of other useful components. High If foaming is desired, C ₁₀ -C ₁₆ generally from 1% to such foam promoting material in the compositions of the alkanolamide to 10%
Can be blended. C ₁₀ -C ₁₄ monoethanol and diethanol amides are representative examples of such blowing promoter. It is also advantageous to use such foaming accelerators in combination with the high foaming auxiliary surfactants such as the amine oxides, betaines and sultaines described above. If desired, MgCl
₂ , soluble magnesium salt such as MgSO ₄ is generally 0.1%
It can be added in an amount of up to 2% and further foamed to enhance the degreasing performance.

The various detergent components used in the composition may optionally include
The components can be further stabilized by absorbing them onto a porous hydrophobic substrate and then applying a hydrophobic coating to the substrate. Preferably, the detergent components are mixed with the surfactant before being absorbed into the porous substrate. During use, the detergent components are released from the substrate into the wash water to perform its intended detergent function.

In order to explain this technique in more detail, a porous hydrophobic silica (trade name: SIPERNAT D10, DeGussa) was added at 3% to
Mix with proteolytic enzyme solution containing 5% _C13-15 ethoxylated alcohol (EO7) nonionic surfactant. Generally, the enzyme / detergent solution is based on the weight of the silica.
2.5 times. The resulting powder is dispersed in the silicone oil with stirring (various silicone oil viscosities from 500 to 12,500 can be used). The resulting silicone oil dispersion is emulsified or otherwise added to the final detergent matrix. That is, components such as the above enzymes, bleaches, bleach activators, bleach catalysts, photoactivators, dyes, fluorescers, fabric conditioners, and water-degradable surfactants can be added to detergents including liquid laundry detergent compositions. "Protect" for use
be able to.

Liquid detergent compositions can include water and other solvents as carriers. Preferred are low molecular weight primary or secondary alcohols represented by methanol, ethanol, propanol, and isopropanol. Monohydric alcohols are preferred for solubilizing surfactants, but polyols such as polyols having 2 to about 6 carbon atoms and 2 to about 6 hydroxyl groups (e.g., 1,3-propanediol, ethylene Glycol, glycerin, and 1,2-propanediol) can also be used. Composition 5
% To 90%, generally 10% to 50%, of such carriers.

The detergent composition has a pH of the wash water when washing with water.
Is preferably about 6.5 to about 11, preferably about 7.5 to 10.5. Laundry products have a pH of 9-11. Techniques for adjusting the pH to the recommended use level include buffer, alkali,
It involves the use of acids, etc., and is well known to those skilled in the art.

Enzymes The detergent compositions include, for example, removing protein-based, carbohydrate-based, or triglyceride-based stains from textile-like surfaces, such as preventing floating dye transfer during washing,
Enzymes can be included for a variety of purposes, including and for fabric recovery. Suitable enzymes include proteases, amylases, lipases, cellulases, peroxidases, and mixtures thereof, from any time period, for example, from plants, animals, bacteria, fungi and yeast. The preferred choice depends on factors such as pH activity and / or optimal stability, thermal stability, stability to active detergents, builders, and the like. In this connection, bacterial or fungal enzymes such as bacterial amylase and protease, and fungal cellulase are preferred.

As used herein, "detergent enzyme" means any enzyme that has a detergent, stain removal, or other beneficial effect in a laundry, hard surface cleaning or cosmetic detergent composition. Preferred detergent enzymes are hydrolases for proteases, amylases and lipases. Preferred enzymes for laundry purposes include, but are not limited to, proteases, cellulases, lipases, and peroxidases.

The enzyme is generally incorporated in the detergent or detergent additive in an amount sufficient to provide a "cleaning effective amount". By "cleaning effective amount" is meant any amount that can achieve a cleaning, stain removal, stain removal, whitening, deodorizing, or freshness improving effect on a substrate such as fabric. Typical amounts for practical use of current commercial formulations are up to about 5 mg, more usually 0.01 mg to 3 mg, of active enzyme per gram of detergent composition. That is, the composition generally comprises about 0.001-5% by weight, preferably 0.01-1% by weight, of a commercially available enzyme preparation. Protease enzymes are usually present in such commercial preparations in 0.005 to 0.1 Anson units (A) per gram of composition.
It is present in an amount sufficient to provide the activity of U). For certain detergents, it is desirable to increase the active enzyme content of the commercial formulation to minimize the total amount of non-catalytically active material, thereby improving spotting / filming or other end results In some cases. For highly concentrated detergent compositions, higher levels of activity may be desirable.

Suitable examples of proteases are B. Subtilis and B.lich
It is a subtilisin obtained from a specific variety of eniformis. One suitable protease is obtained from Bacillus varieties, has maximum activity in the pH range 8-12,
ESP, developed by Industries A / S, [Novo]
Sold as ERASE (product name). The production of this and similar enzymes is described in Novo UK Patent 1,243,784. Other suitable proteases include ALCALASE® from Novo and SAVINASE
(Trade name) and International Bio-Synthetics, In
c. MAXATASE (trade name) commercially available from the Netherlands, and European Patent Application No. 130,756A, January 9, 1985.
Protease A and European Patent Application 30
There is protease B described in 3,761A, Apr. 28, 1987 and European Patent Application No. 130,756A, Jan. 9, 1985. See also high pH protease obtained from Bacillus sp. NCIMB 40338 described in International Patent No. WO 9318140A to Novo. An enzyme detergent comprising a protease, one or more other enzymes, and a reversible protease inhibitor is described in International Patent No. WO 9203529A to Novo. Other preferred proteases include
There is a protease of International Patent No. WO 95105914A to Procter & Gamble. Procter & Gam if desired
Some proteases have reduced adsorptivity and increased hydrolyzability, as described in WO 9507791 to ble. Suitable recombinant trypsin-like proteases for detergents here are described in WO 9425583 to Novo.

More particularly, a particularly preferred protease, termed "Protease D", is a carbonyl hydrolase variant having an amino acid sequence not found in nature, which is derived from the precursor carbonyl hydrolase by Genencor I
The numbering of Bacillus amyloliquefaciens subtilisin to multiple amino acid residues at a position equal to position +76 in the carbonyl hydrolase is preferred, as described in International Patent WO 95/10615 by nternational. Is +99, +101, +103, +104, +107, +
123, +27, +105, +109, +126, +128, +135, +15
6, +166, +195, +197, +204, +206, +210, +21
6, +217, +218, +222, +260, +265 and / or +274 in combination with one or more amino acid residue positions equal to a position selected from the group consisting of and replaced by a different amino acid.

Useful proteases are described in the PCT literature, ie, WO95 / 3001.
0, November 9, 1995, The Procter & Gamble Company,
WO95 / 30011, November 9, 1995, The Procter & Gamble
Company, WO95 / 29979, November 9, 1995, The Procter
& Gamble Company, also listed.

Amylases suitable for the present invention include, for example, α-amylase, RAPIDASE (trade name), International Bio-Synth described in GB 1,296,839 to Novo.
etics, Inc. and TERMAMYL (trade name) Novo. Novo
Particularly useful is FUNGAMYL (trade name) commercially available from. Studies of enzymes to improve stability, eg, oxidative stability, are known. For example, J. Biological Chem., Vol. 260, No.
See 11, 1985, pages 6518-6521. In certain preferred embodiments of the composition, an amylase having improved stability in detergents, especially improved oxidative stability, as measured against the reference point of TERMAMYL (trade name) commercially available in 1993, is used. can do. These preferred amylases have in common the feature of "enhanced stability" amylase, such as oxidative stability to hydrogen peroxide / tetraacetylethylenediamine in a buffer solution at pH 9-10, e.g. It is characterized by at least a considerable improvement in thermal stability at normal wash temperatures, or alkaline stability, for example at a pH of about 8 to about 11, as measured against the standard amylase described above. Stability can be measured using any of the technical tests disclosed in the art. See, for example, the literature described in International Patent No. WO 9402597. Amylases with enhanced stability are available from Novo or Genencor International. A very preferred group of amylases here is 1,
Whether or not two or more amylase species are direct precursors, one or more Bacillus amylase, especially Baci
There is a commonality that is obtained from llus α-amylase using site-specific displacement induction. Amylases with enhanced oxidative stability relative to the standard amylases described above are particularly preferred for use in oxygen bleaching detergent compositions different from bleaching, more preferably chlorine bleaching. Such preferred amylases include (a) WO9402597, supra, Novo, 1994.
Amylase, [TERMAMYL (trade name)
197 positions of B. Licheniformis alpha-amylase, also known as B. amyloliquefaciens, B. subtil
methionine residues at similar positions in similar parent amylase, such as is or B. stearothermophilus, are further indicated by mutants that have been replaced with alanine or threonine, preferably threonine.
(B) the 207th American Chemical Society National
Meeting, March 13-17 Genencor International at 1994
al, a stability-enhancing amylase researched and published by C. Mitchinson entitled "Oxidation-resistant alpha-amylase". In that research presentation, bleach in automatic dishwashing detergents inactivates alpha-amylase, but an amylase with improved oxidative stability was reported by Genencor to B. Licheniformis NCIB.
8061. Methionine (Met) has been identified as the most easily modified residue. Replacing Met with positions 8, 15, 197, 256, 304, 366 and 438 respectively to form a special mutant,
Of particular interest are M197L and M197T, with the M197T mutant being the most stable expression mutant. CASCADE stability
(Product name) and SUNLIGHT (product name).
(C) Particularly preferred amylases here include WO 951060
Amylase variant further modified in the immediate parent as described in 3A, DURA from assignee Novo
It is commercially available as MYL (trade name). Other particularly preferred amylases with enhanced oxidative stability include Genencor
Amylases described in WO 9418314 to international and WO 9402597 to Novo. Any other oxidatively-stable amylase may be used, such as obtained by swabbing-specific mutagenesis from known chimeric, hybrid, or parent forms of simple mutants of available amylase. Other preferred enzyme modifications can also be used. See WO 9509909A to Novo.

As the cellulase that can be used here, the optimum pH is 5
9.5, including both bacterial and fungal types. U.S. Patent No. 4,435,307, Barbesgoard et al., March 6, 1984, discloses Humicola insolens or Humicola variety DSM1800.
Also disclosed are suitable fungal cellulases produced from cellulase 212-producing fungi belonging to the genus Aeromonas, and cellulases extracted from the hepatopancreas of the marine mollusc, Dolabella Auricula Solander. Suitable cellulases are
GB-A-2,075,028, GB-A-2,0
It is also described in DE 95,275 and DE-OS-2,247,832. CAREZYZE (product name) (Nov
o) is particularly useful. See also WO 9117243 to Novo.

Lipase enzymes suitable for detergents include those produced by microorganisms of the Pseudomas family, such as the Pseudomas stutzeri ATCC 19.154 described in GB 1,372,034. See also Japanese Patent Application No. 53,20487, published Feb. 24, 1978, this lipase is disclosed in Aman
o Lipas from Pharmaceutical Co. Ltd., Nagoya, Japan
It is commercially available under the trade name of eP “Amano” or “Amano-P”. Other suitable commercially available lipases include:
Amano-CES, commercially available from Toyo Jozo Co., Tagata, Japan, Chromobacter viscosum, e.g., Chromobac
lipase from ter viscosum var.lipolyticum NRRLB 3673, USBiochemical Corp., USA and Disoyn
Chromobacter viscosum commercially available from th Co., The Netherlands
There are lipases and lipases from Pseudomonas gladioli. The LIPOLASE® enzyme, derived from Humicola lanuginosa and commercially available from Novo (see also EP 341,947), is a preferred lipase for use herein. Lipase and amylase variants stabilized against peroxidase enzyme
It is described in WO 9414951. WO 9205249A
See also the specification and RD 94359044.

A suitable cutinase enzyme for use herein is Genencor
In WO 8809367A.

Peroxidase enzymes are combined with an enzyme source such as percarbonate, perborate, hydrogen peroxide, etc. to "solution bleach", i.e., the removal of dyes or pigments from a substrate during washing by the washing solution. It can be used to prevent migration to other substrates present therein. Known peroxidases include horseradish peroxidase, ligninase, and haloperoxidases, such as chloro- or bromoperoxidase. Detergent compositions containing peroxidase are described in WO89099813 to Novo
A specification, October 19, 1989, and WO8909813 to Novo
It is described in the specification of A.

Various enzyme materials and means for incorporating them into synthetic detergent compositions are also described in WO 9308263A and WO 9307260A to Genencor International and WO 8908 to Novo.
694A and U.S. Patent No. 3,553,139 to McCarty et al.
No., January 5, 1971. Enzymes are further described in U.S. Patent No. 4,101,457, Place et al., July 18, 1978, and U.S. Patent No. 4,507,219, Hughe.
s, promulgated on March 26, 1985. Enzymatic materials useful in liquid detergent compositions and their incorporation into compositions are described in U.S. Pat. No. 4,261,868 Hora et al., April 1, 1981.
It is listed on the 4th. The enzymes used in detergents can be stabilized by various techniques. Enzyme stabilization techniques are described, for example, in US Pat. No. 3,600,319, Aug. 1, 1971.
7, Gedge et al., EP 199,405 and EP 200,586, Oct. 29, 1986.
Sun, Venegas, has been disclosed. Enzyme stabilization systems are also described in US Pat. No. 3,519,570. Useful Bacillus, sp. AC13, which produces proteases, xylanases and cellulases, is described in WO 9401532A to Novo.

Enzyme Stabilizing System Liquid compositions containing (but not limited to) enzymes may comprise from about 0.001% to about 10%, preferably about 0.005%, by weight.
% To about 8%, most preferably about 0.01% to about 6% of the enzyme stable system. The enzyme stable system may be any stable system that is compatible with the detergent enzyme. Such systems may be provided by the other active ingredients of the composition, or added separately, for example, by the formulator or by the manufacturer of the ready-to-use enzyme in detergents. Such a stable system is
For example, it can comprise calcium ions, boric acid, propylene glycol, short chain carboxylic acids, boronic acids, and mixtures thereof, addressing various stabilization issues depending on the type and physical form of the detergent composition. It is designed to do.

One method of stabilization is to use an aqueous source of calcium and / or magnesium ions in the finished composition injection and to provide such ions to the enzyme. Calcium is generally more effective than magnesium ion, where calcium ion is preferred if only one cation is used. Typical detergents, especially liquids, are about 1 to 1 liter per finished detergent composition.
About 30, preferably about 2 to about 20, more preferably about 8 to about
It comprises 12 mmol of calcium ions, but can be varied depending on the variety, type and amount of enzyme to be incorporated. Preferably, use is made of water-soluble calcium or magnesium salts, including, for example, calcium chloride, calcium hydroxide, calcium formate, calcium malate, calcium maleate, calcium hydroxide and calcium acetate, more usually sulfuric acid. Calcium or the magnesium salt corresponding to the calcium salt described above can be used. Furthermore, more calcium and / or magnesium ions are, of course, also effective, for example, to enhance the grease removal effect of certain surfactants.

Another stabilization method is to use a borate material. See U.S. Pat. No. 4,537,706 to Severson. The borate stabilizer, if used, may be up to 10% or more of the composition, but more usually up to about 3% by weight of boric acid or other additives such as borax or orthoborate. The borate compounds are also suitable for liquid detergents. Substituted boric acids such as phenylboronic acid, butaneboronic acid, and p-bromophenylboronic acid can also be used in place of boric acid, and the use of such substituted boron derivatives reduces the total amount of boron in the detergent composition. Can be lowered.

Certain cleaning composition stabilizing systems include 0 to about 10% by weight;
Preferably, comprising about 0.01 to about 6% by weight of a chlorine bleach scavenger, the chlorine bleaching substance present in many tap waters comprises:
Particularly under alkaline conditions, the enzyme can be prevented from attacking and inactivating the enzyme. The amount of chlorine in the water is small, generally from about 0.5 ppm to about 1.75 ppm, but the chlorine in the water used to contact the enzyme during washing of the fabric, for example, is relatively large, so the chlorine in use is relatively large. The problem is the stability of the enzyme against In some compositions of the present invention, perborate or percarbonate that can react with chlorine bleach may be present in an amount that is considered separately from the stable system. Use is not necessary in most cases,
Their use may improve the results. Suitable chlorine scavenger anions are widely known and readily available and, when used, include ammonium cations, sulfites, bisulfites, thiosulfites, thiosulfates, iodine. And the like. Antioxidants such as carbamates, ascorbates, etc., organic amines such as ethylenediaminetetraacetic acid (EDTA) or its alkali metal salts, monoethanolamine (MEA), and mixtures thereof can be used as well. Similarly, special enzyme suppression systems can be included to ensure that other enzymes have maximum compatibility. Sources of other common scavengers such as bisulfate, nitrate, hydrochloride, hydrogen peroxide, such as sodium perborate tetrahydrate, sodium perborate monohydrate and sodium percarbonate, and phosphorus Acid salts, condensed phosphates, acetates, benzoates, citrates, formates,
Lactate, malate, tartrate, salicylate, and the like, and mixtures thereof, can also be used if desired. In general, the function of the chlorine scavenger can be fulfilled by components whose function is more well-recognized (e.g., a hydrogen peroxide source), so that the compound that fulfills that function to the desired extent is an enzyme of the present invention. There is no absolute reason to add a separate chlorine scavenger unless the inclusion embodiment is lacking, but nonetheless, the scavenger is only added for optimal results. In addition, the formulator exercises his or her usual skills to avoid the use of enzyme scavengers or stabilizers that, when formulated, are largely incompatible with the other reactive ingredients used. Will do. With respect to the use of ammonium salts, such salts can be simply mixed with the detergent composition, but tend to adsorb water and / or release ammonia gas during storage. Accordingly, such materials, if present, are disclosed in U.S. Patent No. 4,652,392, Baginski et al.
It is desirable to protect in the particles as described in

The compositions of the present invention may optionally contain one or more other detergent adjuncts, or other additives to assist or enhance cleaning performance, treat the substrate to be cleaned, or improve the aesthetics of the detergent composition. Materials (eg, fragrances, colorants, dyes, etc.) can be included. Examples of such auxiliary materials are given below.

Builder In the detergent composition of the present invention, a detergent builder can be blended if desired, so that the mineral hardness can be easily adjusted. Inorganic and organic builders can be used. Builders are commonly used in fabric detergent compositions to help remove particulate soil.

The amount of builder will vary greatly depending on the end use of the composition and its desired physical form. When present, the composition will generally comprise at least about 1% builder. Liquid formulations generally comprise from about 5 to about 50%, more usually from about 5 to about 30%, by weight of the detergent builder.
Granular formulations generally comprise from about 10% to about 80%, more usually from about 15% to about 50%, by weight, of detergent builder. However, higher or lower amounts of builders can also be used.

Inorganic or P-containing detergent builders include alkali metals,
Ammonium and alkanolammonium polyphosphates (eg, tripolyphosphate, pyrophosphate, and glassy polymer metaphosphate), phosphonates, phytic acid, silicates, carbonates (bicarbonate and sesquicarbonate) ), Sulfates and aluminosilicates,
It is not limited to these. However, in some areas non-phosphate builders are needed. Importantly, even in the presence of so-called "weak" builders such as citric acid (as compared to phosphates) or in so-called "low builders" situations, which occur with zeolites or layered silicate builders. The compositions of the invention are surprisingly effective.

Examples of silicate builders are the alkali metal silicates, particularly SiO _2: Na ₂ O ratio of 1.6: 1 to 3.2: alkali metal silicate having a 1 and layered silicates, e.g., U.S. Patent No. 4,664,
No. 839, issued May 12, 1987 to HP Rieck, a layered sodium silicate. NaSK-
6 is the trade name of a crystalline layered silicate commercially available from Hoechst (generally abbreviated "SKS-6"). Unlike zeolite builders, NaSKS-6 silicate builders do not contain aluminum. NaSKS-6 has the delta -Na ₂ SiO ₅ form of layered silicate. This product is described in DE-A-3,417,649 and DE-A-
It is produced by a method as described in the specification of 3,742,043. SKS-6 is a highly preferred layered silicate for use herein, but other such layered silicates such as the general formula NaMSi _x O _{2x + 1} .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 commercially available from Hoechst include NaSKS-5, NaSKS-7 and NaSKS-11 in alpha, beta and gamma forms.
There is. As mentioned above, to use here, Delta-Na
₂ SiO ₅ (NaSKS-6 form) is most preferred. Other silicates, such as magnesium silicate, are also useful and serve as crispening agents in granular formulations, as stabilizers for enzyme bleaches, and as components of foam control systems.

Examples of carbonate builders are described in German Patent Application No. 2,321,001, published Nov. 15, 1973,
Alkaline earth and alkali metal carbonate.

Aluminosilicate builders are useful in the present invention. Aluminoate is very important in most heavy duty granular detergent compositions currently on the market,
It is also an important builder component in liquid detergent formulations. The aluminosilicate builders, there is a substance having the empirical formula _{M z (zAlO 2) y]} · xH 2 O, wherein z and y are integers of at least 6, the molar ratio of z to y is 1.0 About 0.5,
x is an integer from about 15 to about 264.

Useful aluminosilicate ion exchange materials are commercially available. These aluminosilicate structures can be crystalline or amorphous and can be natural aluminosilicates or synthetic. The method for producing an aluminosilicate ion exchange material is as follows:
U.S. Pat.No. 3,985,669, Krummel et al., October 1976
Promulgated on the 12th. Synthetic crystalline aluminosilicate ion exchange materials useful herein include zeolite A, zeolite P (B), zeolite MAP and zeolite X.
It is commercially available under the name. In a particularly preferred embodiment,
Crystalline aluminosilicate ion exchange material has the formula _{Na 12 [(AlO 2) 12} (SiO 2) 12] · xH 2 O, wherein, x is from about 20 to about 30, especially about 27. This material is called zeolite A. Here, dehydrated zeolite (x = 0 to 10) can also be used. Preferably, the aluminosilicate has a particle diameter of about 0.1 to 10 microns.

Organic detergent builders useful for the purposes of the present invention include, but are not limited to, a wide variety of polycarboxylate compounds. As used herein, "polycarboxylate" refers to a compound having a plurality of carboxylate groups, preferably at least three carboxylate groups. The polycarboxylate builder is generally added to the composition in the form of an acid, but can also be added in the form of a neutralized salt. When used in the form of a salt, the salts of the alkali metals, such as sodium, potassium and lithium, or alkanolammonium are preferred.

There are various types of useful materials for polycarboxylate builders. An important class of polycarboxylate builders is Berg, U.S. Patent No. 3,128,287, 1
Issued April 7, 964, and U.S. Pat.
There is an oxydisuccinate as described in 3,635,830, issued Jan. 18, 1972. US Patent 4,66
No. 3,071, issued on May 5, 1987 to Bush et al.
See also / TDS builder. Suitable ether polycarboxylates include cyclic compounds, especially alicyclic compounds, such as U.S. Pat.Nos. 3,923,679, 3,835,163
No. 4,158,635, No. 4,120,874, and No. 4,
There are compounds described in 102,903.

Other useful detergent builders include ether hydroxy polycarboxylates, copolymers of maleic anhydride and ethylene or vinyl methyl ether, 1,3,5-trihydroxybenzene-2,4,6-trisulfonic acid, and Various alkali metal, ammonium and substituted ammonium salts of carboxymethyloxysuccinic acid, polyacetic acids such as ethylenediaminetetraacetic acid and nitrilotriacetic acid,
And polycarboxylates such as melitic acid, succinic acid, oxydisuccinic acid, polymaleic acid, benzene 1,3,5-tricarboxylic acid, carboxymethyloxysuccinic acid, and soluble salts thereof.

Citrate builders, such as citric acid and its soluble salts, especially the sodium salt, are polycarboxylate builders that are particularly important in heavy-duty liquid detergent formulations because of their availability from renewable sources and their biodegradability. is there. Citrates can also be used in granular compositions, especially in combination with zeolites and / or layered silicate builders. Oxydisuccinates are also particularly useful in such compositions and combinations.

The detergent compositions of the present invention include those described in U.S. Patent No. 4,566,984, Bush, promulgated
Also suitable are 3-dicarboxy-4-oxa-1,6-hexanedioate and related compounds. Useful succinic acid builders, there is a C ₅ -C ₂₀ alkyl and alkenyl succinic acids and salts thereof. A particularly preferred compound of this type is dodecenyl succinic acid. Specific examples of the succinate builder include lauryl succinate, myristyl succinate, palmityl succinate, 2-dodecenyl succinate (preferred), and 2-pentadecenyl succinate. Lauryl succinate is a preferred builder of this type and is described in European Patent Application No. 86200690.5 / 0,200263.
Issue, published November 5, 1986.

Other suitable polycarboxylates are described in U.S. Pat.
No. 4,226, Crutchfield et al., Promulgated on March 13, 1979,
And U.S. Pat. No. 3,308,067, Diehl, March 1967
Promulgated on March 7th. Diehl US Patent 3,7
See also specification 23,322.

Fatty acids such as C ₁₂ -C ₁₈ monocarboxylic acids, even alone composition or the builders, formulated in combination especially citrate and / or the succinate builders, and,
Builder activity can be added. The use of such fatty acids generally results in reduced effervescence and the formulator should take this into account.

Where phosphorus-based builders are available, especially in bars used for manual washing, various alkali metal phosphates, such as the well-known sodium tripolyphosphate, sodium pyrophosphate and sodium orthophosphate, are used. can do. Phosphonate builder,
For example, ethane-1-hydroxy-1,1-diphosphonate and other known phosphonates (eg, U.S. Pat.
9,581, 3,213,030, 3,422,021, 3,400,148, and 3,422,137) can also be used.

Chelating Agents The detergent compositions of the present invention can also optionally include one or more iron and / or manganese chelating agents.
Such chelators can all be selected from the group consisting of aminocarboxylates, aminophosphonates, polyfunctionally substituted aromatic chelators and mixtures thereof, described below. Without wishing to be bound by theory, it is believed that the advantages of these materials are due, in part, to their exceptional ability to remove iron and manganese from the wash solution by forming soluble chelates.

Aminocarboxylates useful as the optional chelating agent include ethylenediaminetetraacetate, N-hydroxyethylethylenediaminetriacetate, nitrilotriacetate, ethylenediaminetetrapropionate, triethylenetetraaminehexaacetate, diethylenetriaminepentaacetate,
And ethanol diglycine, their alkali metals,
There are ammonium, and substituted ammonium salts, and mixtures thereof. Methylglycine di-acetic acid (MGDA) is also suitable for use as a chelating agent.

Aminophosphonates are also useful as chelating agents when at least a small amount of total phosphorus content is acceptable in the detergent composition, and include ethylene diamine tetrakis (methylene phosphonate) such as DEQUEST. These aminophosphonates preferably do not contain alkyl and alkenyl groups having 7 or more carbon atoms.

Polyfunctionally substituted aromatic chelators are also useful in the compositions of the present invention. U.S. Pat.No. 3,812,044, 1974
Promulgated and referred to Connor et al. A preferred compound of this type in the acid form is dihydroxydisulfobenzene, for example 1,2-dihydroxy-3,5-disulfobenzene.

A preferred biodegradable chelating agent for use herein is ethylenediamine disuccinate ("EDDS"), particularly US Pat. No. 4,704,233, Hartman Nov. 3, 1987.
And the [S, S] isomer described in Perkins.

When used, these chelating agents generally comprise from about 0.1 to about 10% by weight of the detergent compositions of the present invention. More preferably, when used, these chelating agents
It comprises about 0.1 to about 3.0% by weight of such compositions.

Clay Soil Removal / Anti-Redeposition Agent The compositions of the present invention can optionally include a water-soluble ethoxylated amine having clay soil removal and anti-redeposition properties. Granular detergent compositions containing these compounds generally contain from about 0.01 to about 10.0% by weight, and liquid detergent compositions generally contain from about 0.01 to about 5% by weight of a water-soluble ethoxylated amine.

The most preferred antifouling and anti-redeposition agent is ethoxylated tetraethylenepentamine. Representative ethoxylated amines are further described in U.S. Pat. No. 4,597,898, VanderMeer, issued Jul. 1, 1986. Another group of preferred clay soil removal-redeposition agents are
European Patent Application No. 111,965, Oh and Gosse
link, published on June 27, 1984. Other clay soil removal / anti-redeposition agents that can be used include ethoxylated amine polymers described in European Patent Application No. 111,984, Gosselink, published June 27, 1984, and European Patent Application No. 11
Zwitterionic polymers described in US Pat. No. 2,592, Gosselink, published June 4, 1984, and U.S. Pat.
There are amine oxides described in US Pat. No. 548,744, Connor, promulgated October 22, 1985. Other clay soil removal and / or anti-redeposition agents known in the art can also be used in the compositions of the present invention. Another type of preferred anti-redeposition agent is a carboxymethyl cellulose (CMC) based material. These materials are well known in the art.

Polymeric Dispersants Polymeric dispersants are present in the compositions of the present invention, especially in the presence of zeolites and / or layered silicate builders, in an amount of about 0.1%.
It can be used effectively in amounts from 1 to about 7% by weight.
Suitable polymeric dispersants include polymeric polycarboxylates and polyethylene glycols, although other dispersants known in the art can be used. While not wishing to be bound by theory, polymeric dispersants prevent crystal growth, free particulate peptization, and redeposition when used in combination with other builders, including low molecular weight polycarboxylates. Prevention is believed to enhance overall builder performance.

Polymeric polycarboxylate materials can be prepared by polymerizing or copolymerizing suitable unsaturated monomers, preferably in their acid form. Unsaturated monomeric acids that can form suitable polymeric polycarboxylates upon polymerization include acrylic acid, maleic acid (or maleic anhydride), fumaric acid, itaconic acid, aconitic acid, mesaconic acid, citraconic acid and methylene malonic acid. There is. The presence of monomeric moieties, such as vinyl methyl ether, styrene, ethylene, etc., containing no carboxylate groups in the polymeric polycarboxylate is preferred, unless such moieties account for about 40% by weight. is there.

Particularly suitable polymeric carboxylate can be derived from acrylic acid. Such acrylic polymers useful herein are polymerized water-soluble salts of acrylic acid. The average molecular weight of such acid form polymers is preferably from about 2,000 to 10,000, more preferably from about 4,000 to 7,000,
Most preferably it is about 4,000-5,000. Such water soluble salts of acrylic acid polymers include, for example, alkali metal, ammonium and substituted ammonium salts. This type of chemically soluble polymer is a known material. The use of such polyacrylates in detergent compositions is described, for example, in Dieh.
l, U.S. Patent No. 3,308,067, issued March 7, 1967.

Acrylic / maleic acid copolymers can also be used as a preferred component of the dispersing / anti-redeposition agent. Such materials include the water-soluble salts of copolymers of acrylic acid and maleic acid. The average molecular weight of such acid form copolymer is preferably from about 2,000 to 100,000, more preferably from about 5,
000 to 75,000, most preferably about 7,000 to 65,000.
The ratio of acrylate to maleate moieties in such copolymers is generally from about 30: 1 to about 1: 1, more preferably from about 10: 1 to 2: 1. Such water-soluble salts of acrylic acid / maleic acid copolymer include, for example, salts of alkali metals, ammonium and substituted ammonium. This type of soluble acrylate / maleate copolymer is a known material and is described in European Patent Application No. 66 915,1.
Published December 15, 982, and European Patent No. 193,360
No. 6,078,028, issued Sep. 3, 1986, which patent also discloses such polymers including hydroxypropyl acrylate. Still other useful dispersants include maleic / acrylic / vinyl alcohol terpolymers. Such materials are described in European Patent No. 19
3,360. For example, maleic acid /
Includes 45/45/10 terpolymer of acrylic acid / vinyl alcohol.

Another polymeric material that can be incorporated is polyethylene glycol (PEG). PEG exhibits dispersant performance and also acts as a viscous soil removal-redeposition inhibitor. Typical molecular weight ranges for these purposes are from about 500 to about 100,000,
Preferably about 1,000 to about 50,000, more preferably about 1,500
~ About 10,000.

Polyaspartate and polyglutamate dispersants can also be used, especially in combination with zeolite builders. Dispersants such as polyaspartate preferably have an (average) molecular weight of about 10,000.

Brighteners All optical brighteners or other glossing or whitening agents known in the art can be incorporated into the detergent compositions of the present invention, generally in an amount of about 0.05 to about 1.2% by weight. . Commercially available optical brighteners that can be effectively used in the present invention include stilbene derivatives, pyrazolines, coumarins, carboxylic acids, methine cyanines, dibenzothiophene-5,5-dioxides, azoles, 5- and 6-membered heterocyclic compounds, and other (Including, but not limited to) various agents. Examples of such brighteners are described in "Production and Use of Fluorescent Brighteners", M. Zahradnik, John Wiley & Sons, New York (19
82) Publications.

Examples of optical brighteners useful in the compositions of the present invention are described in U.S. Pat.No. 4,790,856, Wixon, December 1988.
It is listed on the 13th. These brighteners include Ve
Includes PHORWHITE series available from rona. Other brighteners described in this document include Ciba-Geig
Commercially available Tinopal UNPA, Tinopal CBS and Tinopal from y
Artic White CC commercially available from 5BM, Hilton-Davis, Italy
And Artic White CWD, 2- (4-styryl-phenyl) -2H-naphthol [1,2-d] triazole, 4,4 '
-Bis- (1,2,3-triazol-2-yl) -stilbene, 4,4'-bis (styryl) bisphenyl, and aminocoumarin. Specific examples of these brighteners include 4-methyl-7-diethylaminocoumarin,
1,2-bis (-benzimidazol-2-yl) -ethylene, 1,3-diphenylpyrazolin, 2,5-bis (benzoxazol-2-yl) -thiophene, 2-styryl-naphtho- [1, 2-d] -oxazole, and 2-
There is (stilben-4-yl) -2H-naphtho [1,2-d] triazole. U.S. Pat.No. 3,646,015, 197
See also promulgation to Hamilton on February 29, 2 years. Here, an anionic brightener is preferred.

Foaming Inhibitor The composition of the present invention may contain a compound for reducing or suppressing foam formation. Foam control is particularly important for so-called "high-concentration cleaning methods" and pre-loaded washing machines of the European type, as described in U.S. Pat. Nos. 4,489,455 and 4,489,574.

A wide variety of materials are used as foam inhibitors, which are well known to those skilled in the art. For example, Kirk O
thmer Encyclopedia of Chemical Technology, 3rd
Edition, Volume 7, pp. 430-447 (John Wiley & Sons, Inc., 197
See 9). One group of particularly important foam inhibitors is the monocarboxylic fatty acids and their soluble salts. U.S. Pat. No. 2,954,347, Wayne St. Jo, Sep. 27, 1960
Promulgated to hn, see. Monocarboxylic fatty acids and their salts used as foam inhibitors generally have a carbon number of
It has from 10 to about 24, preferably 12 to 18, hydrocarbyl chains. Suitable salts include the alkali metal salts such as sodium, potassium, and lithium salts, and ammonium and alkanolammonium salts.

The detergent composition of the present invention may also include a non-surfactant based foam inhibitor. These materials include, for example, high molecular weight hydrocarbons such as paraffin, fatty acid esters (eg, fatty acid triglycerides), fatty acid esters of monohydric alcohols, and aliphatic C ₁₈ -C ₄₀ ketones (eg, stearone). Other foam inhibitors include N-alkylated aminotriazines such as cyanuric chloride and 2 or 3 moles of triamine formed as the reaction product of a primary or secondary amine having 1 to 24 carbon atoms. -Hexa-alkylmelamine or di-tetra-alkyldiaminechlorotriazine, propylene oxide, and monostearyl phosphates, such as monostearyl alcohol phosphate and monostearyl dialkali metal (e.g., K, Na and Li) phosphates And phosphate esters. Hydrocarbons such as paraffins and haloparaffins can be used in liquid form. Liquid hydrocarbons become liquid at room temperature and atmospheric pressure, have a pour point of −40 ° C. to about 50 ° C., and have a minimum boiling point of about 11 ° C.
0 ° C (atmospheric pressure) or higher. It is also known to use waxy hydrocarbons, preferably having a melting point below about 100 ° C. Hydrocarbons are a preferred class of foam inhibitors for detergent compositions. Hydrocarbon foam inhibitors are described, for example, in U.S. Pat. No. 4,265,779, Gandolfo et al., Issued May 5, 1981. Hydrocarbons include, for example, aliphatic, cycloaliphatic, aromatic, and heterocyclic saturated or unsaturated hydrocarbons having from about 12 to about 70 carbon atoms. The term "paraffin" as used in this discussion of foam control agents is intended to include a mixture of native paraffins and cyclic hydrocarbons.

Another preferred class of non-surfactant based foam inhibitors include:
There are silicone foam inhibitors. This group uses polyorganosiloxane oils, such as polydimethylsiloxanes, dispersions or emulsions of polyorganosiloxane oils or resins, and combinations of polyorganosiloxanes and silica particles in which the polyorganosiloxanes are chemisorbed or fused onto silica. Is done. Silicone foam inhibitors are well known in the art and are described, for example, in U.S. Pat.
4,265,779, Gandolfo et al., Issued May 5, 1981, and European Patent Application No. 89307851.9,
Starch, MS, published February 7, 1990.

Other silicone suds suppressors are disclosed in U.S. Pat.
No. 839.

Mixtures of silicone and silanized silica are described, for example, in German Patent Application DOS 2,124,526. Silicone defoamers and foam control agents in granular detergent compositions are described in U.S. Pat. No. 3,933,672, Bartolotta
Et al., And U.S. Pat.No. 4,652,392, Baginski
Et al., Promulgated March 24, 1987.

Typical silicone foaming inhibitors used here are:
(I) a polydimethylsiloxane liquid having a viscosity of about 20 cs. To about 1,500 cs. At 25 ° C., (ii) (i) about 5 to about 50 parts per 100 parts by weight, CH ₃ )
Consists of ₃ SiO _1/2 units and SiO ₂ units, (CH ₃ ) ₃ SiO _1/2
(Iii) (i) about 1 to about 20 parts per 100 parts by weight of solid silica gel of a siloxane resin having a ratio of units to SiO ₂ units of about 0.6: 1 to about 1.2: 1, is there.

In the preferred silicone foam inhibitor used herein,
The solvent for the continuous phase consists of certain polyethylene glycols or polyethylene-polypropylene glycol copolymers or mixtures thereof (preferred), or polypropylene glycol. Primary silicone foam inhibitors are branched / crosslinked and are preferably not linear.

To further illustrate this point, a typical foamed liquid laundry detergent composition may optionally comprise from about 0.001 to about 1, preferably from about 0.01 to about 0.7, and most preferably from about 0.05 to about 0.7.
From about 0.5% by weight of the silicone suds suppressor, comprising (1) (a) a polyorganosiloxane, (b) a silicone compound that produces a resinous siloxane or silicone resin, and (c) a finely divided filler. , And (d)
A non-aqueous emulsion of a primary antifoaming agent which is a mixture of the mixture components (a), (b) and (c), a catalyst which promotes the reaction to form a silanolate; (2) at least one nonionic silicone interface An activator and (3) polyethylene glycol or a copolymer of polyethylene-polypropylene glycol (excluding polypropylene glycol) having a water solubility at room temperature of greater than about 2% by weight. Similar amounts can be used for granular compositions, gels, and the like. U.S. Pat.No. 4,978,471, Starch, 199
Promulgated on December 18, 0, and 4,983,316, Starc
h, promulgated January 8, 1991, specification No. 5,288,431, Huber
Et al., Promulgated February 22, 1994, and U.S. Patent No. 4,639,489.
See also U.S. Pat. No. 4,749,740, Aizawa et al., Paragraphs 1, line 46 to paragraph 4, line 35.

The silicone foam control agents are preferably polyethylene glycol and polyethylene glycol / polyethylene glycol / polyethylene glycol /
It comprises a copolymer of polypropylene glycol. Here, the polyethylene glycol and the polyethylene / polypropylene glycol copolymer have a water solubility at room temperature of more than about 2% by weight, preferably more than about 5% by weight.

Preferred solvents here have an average molecular weight of less than about 1,000,
More preferably about 100-800, most preferably 200-400 polyethylene glycol, and polyethylene glycol / polypropylene glycol, preferably PPG200 / PEG
300 copolymers. The weight ratio of polyethylene glycol: polyethylene-polypropylene glycol copolymer is preferably about 1: 1 to 1:10, most preferably 1: 3 to 1: 6.
It is.

The preferred silicone suds suppressors used herein do not include polypropylene glycol, especially of molecular weight 4,000. These foam inhibitors preferably also do not comprise a block copolymer of ethylene oxide and propylene oxide, such as PLURONIC L101.

Other foam control agents useful herein are secondary alcohols (e.g., 2-alkyl alkanols) and such alcohols, as well as U.S. Pat. No. 4,798,679, 4,075,1.
No. 18 and EP-A-150,872 comprising mixtures of silicone oils such as the silicones described. Secondary alcohols include C ₆ -C ₁₆ alkyl alcohols having a C ₁ -C ₁₆ chain. A preferred alcohol is 2-butyloctanol, commercially available from Condea under the trade name ISOFOL 12. A mixture of secondary alcohols is commercially available from Enichem under the trade name ISALCHEM 123. Mixed foam inhibitors generally comprise a mixture of alcohol and silicone in a weight ratio of 1: 5 to 5: 1.

For detergent compositions used in automatic washing machines, lather should not be generated to the extent that the washing machine overflows. When used, the foam inhibitor is preferably present in a "foam inhibiting amount". By "foam control amount" is meant that the formulator of the composition can select an amount of the foam control agent that is sufficient to control foaming and form a low foaming laundry detergent for use in automatic washing machines.

The compositions of the present invention generally comprise from 0% to about 5% of a foam control agent. When used as a foam suppressant, monocarboxylic fatty acids and salts thereof may be present in the detergent composition at about 5%.
It is present in amounts up to% by weight. Preferably, about 0.5% to about 3% of a fatty monocarboxylate foam inhibitor is used. Silicone foam inhibitors are generally used in amounts up to about 2.0% by weight of the detergent composition, but can be used in larger amounts. This upper limit is realistic in nature, and is set in order to minimize the cost first and to effectively suppress foaming with a small amount. Preferably about 0.01% to about 1%, more preferably about 0.25% to about 0.5%, of a silicone suds suppressor is used. As used herein, these weight percentage values include all silica used in combination with the polyorganosiloxane, as well as any accompanying materials that can be used.
Monostearyl phosphate foam suppressants are commonly used in compositions.
It is used in an amount of 0.1 to about 2% by weight. Hydrocarbon foam inhibitors are generally used in amounts from about 0.01% to about 5.0%, but can be used in larger amounts. Alcohol foam inhibitors are generally used in amounts of 0.2 to 3% by weight of the final composition.

Fabric softener, if desired, added during various launderings (through-the
-Wash) fabric softeners, particularly the fine smectite clays of U.S. Patent No. 4,062,647, Storm and Nirschl, promulgated December 13, 1977, and other softener clays known in the art, Generally from about 0.5 to about 0.5 in the composition
Used in an amount of about 10% by weight, it can provide the softening properties of the fabric while washing the fabric. Clay softeners are described, for example, in US Pat. No. 4,375,416, Crisp et al., March 1, 1983.
And US Patent No. 4,291,071, Harris
Et al., Published September 22, 1981, can be used in combination with amines and like ionic softeners.

Optical Brighteners The detergent compositions of the present invention can also optionally contain from about 0.005 to 5% by weight of certain hydrophilic optical brighteners which also exhibit dye transfer inhibition. If used,
The compositions of the present invention preferably comprise from about 0.01 to 1% by weight of such an optical brightener.

Useful hydrophilic optical brighteners of the invention are materials having the following structural formula:

Wherein R ₁ is selected from anilino, N-2-bis-hydroxyethyl and NH-2-hydroxyethyl, and R ₂ is N-2-bis-hydroxyethyl, N-2-hydroxyethyl-N-methylamino , Morpholino, chloro and amino, wherein M is a salt-forming cation, such as sodium or potassium.

Where R ₁ is anilino, R ₂ is N-2-bis-hydroxyethyl and M is a cation such as sodium, the brightener is 4,4′-bis [ (4-anilino-6- (N-2-bis-hydroxyethyl) -s-triazin-2-yl) amino] -2,2 '
-Stilbene disulfonic acid and disodium salt. This special brightener is commercially available from Ciba-Geigy Corporation under the trade name Tinopal-UNPA-GX. Tinopal-UNPA-GX is a preferred hydrophilic optical brightener useful in the detergent compositions of the present invention.

In the above formula, when R ₁ is anilino, R ₂ is N-2-hydroxyethyl-N-2-methylamino, and M is a cation such as sodium, the brightener is 4,4 Disodium salt of 4'-bis [(4-anilino-6- (N-2-hydroxyethyl-N-methylamino) -s-triazin-2-yl) amino] -2,2'-stilbene disulfonic acid is there. This special brightener is sold under the trade name Tinopal 5BM-GX by Ciba-Geigy Corporati
It is commercially available from on.

In the above formula, where R ₁ is anilino, R ₂ is morpholino, and M is a cation such as sodium, the brightener is 4,4′-bis [(4-anilino-6).
-Morpholino-s-triazin-2-yl) amino]
-2,2'-Styrbenzylsulfonic acid, sodium salt. This special brightener is commercially available from Ciba-Geigy Corporation under the trade name Tinopal AMS-GX.

Production ethoxylation of Example 1 PEI 1800 E _7, the temperature measurement and control, pressure measurement, vacuum and inert gas purging, sampling, and 2 gallons made stirring stainless steel subjected to equipment for introducing the ethylene oxide as a liquid Perform in an autoclave. Ethylene oxide (ARC) k A cylinder of about 20 lb. net is placed on a balance and ethylene oxide is pumped as a liquid into the autoclave so that changes in the weight of the cylinder can be monitored.

750 g of polyethylene imine (PEI) (Nippon Shokubai, Epomi
n SP-018, nominal average molecular weight 1800, corresponding to about 0.417 mol of polymer and 17.4 mol of nitrogen functional groups) in an autoclave. The autoclave is then sealed and (vacuum is -2
Exclude the air (by operating at 8 "Hg, followed by pressurizing to 250 psia with nitrogen and then venting to atmospheric pressure). Heat the contents of the autoclave to 130 ° C. while applying vacuum. Thereafter, the autoclave is filled with nitrogen to about 250 psia while cooling the autoclave to about 105 ° C. Ethylene oxide is then slowly added to the autoclave over time, while carefully monitoring the autoclave pressure, temperature, and ethylene oxide flow. Stop the ethylene oxide pump and cool to prevent temperature increase due to exothermic reaction.Gradually increase the total pressure during the reaction while maintaining the temperature at 100-110 ° C. Total 750 g ethylene oxide (nitrogen functional group of PEI) (Equivalent to about 1 mole of ethylene oxide per piece) into an autoclave, and then increase the temperature to 110 ° C. The blanking further 1
Stir for hours. At this point, vacuum is applied to remove any remaining unreacted ethylene oxide.

Then, vacuum was continuously applied while cooling the autoclave to about 50 ° C., and 376 g of a methanol solution of 25% sodium methoxide (1.74 mol, 10% based on the PEI nitrogen functional group).
To achieve a catalytic amount). The methoxide solution is aspirated under vacuum into the autoclave, then the set point of the autoclave temperature controller is increased to 130 ° C. Use equipment to monitor the power consumed by the stirrer. Monitor stirrer power along with temperature and pressure. Stirrer power and temperature values indicate that methanol was removed from the autoclave and gradually increased as the viscosity of the mixture increased, stabilized in about 1 hour, and that most of the methanol was removed. The mixture is further vacuumed for another 30
Heat and stir for minutes.

Remove the vacuum and place the autoclave at 250 psia with cooling to 105 ° C. and then vent to atmospheric pressure.
Fill the autoclave with 200 psia of nitrogen. The pressure, temperature, and ethylene oxide flow rate of the autoclave are carefully monitored, and ethylene oxide is gradually added to the autoclave again as before, maintaining the temperature at 100 to 110 ° C. and limiting the temperature increase due to the exothermic reaction. 4500g
Of ethylene oxide (total of 7 moles of ethylene oxide per mole of PEI nitrogen function) is added over several hours, then the temperature is increased to 110 ° C. and the mixture is stirred for another hour.

The reaction mixture is then collected in a nitrogen purged vessel and finally transferred into a 22 three-necked round bottom flask equipped with heating and stirring. 167 g of methanesulfonic acid (1.74 mol) are added to neutralize the strong alkali catalyst. The mixture is then stirred and heated to 130 ° C. while passing through a gas dispersion frit,
The reaction mixture is deodorized by passing about 100 cubic feet of an inert gas (argon or nitrogen) through the reaction mixture.

The final reaction product is cooled slightly and collected in a glass vessel purged with nitrogen.

In another production, neutralization and deodorization are performed in a reactor before discharging the product.

Erlenmeyer flask 500ml equipped with a quaternized porcelain stir bar Example 2 PEI 1800 E _7, nitrogen 1
Polyethyleneimine having a molecular weight of 1800 and ethoxylated to about 7 ethyleneoxy residues (PEI 180
0 E ₇ ) (207.3 g, 0.590 mol nitrogen, prepared in Example 1) and acetonitrile (120 g). Dimethyl sulfate (28.3 g, 0.224 mol) is added in one portion to the rapidly stirring solution, stoppered and stirred overnight at room temperature. Acetonitrile is removed by rotary evaporation at about 60 ° C., followed by further removal of solvent at about 80 ° C. using a Kugelrohr apparatus to give 220 g of the desired partially quaternized material as a dark brown viscous liquid. Can be The ¹³ C-NMR (D ₂ O) spectrum obtained from the reaction product sample shows that the carbon resonance at about 58 ppm corresponding to dimethyl sulfate has disappeared. ^{The 1} H-NMR (D ₂ O) spectrum shows that the resonance at about 2.5 ppm for the methylene adjacent to the non-quaternized nitrogen is partially shifted to about 3.0 ppm. This is consistent with the desired quaternization of nitrogen of about 38%.

Example 3 PEI 1800 Erlenmeyer flask 500ml equipped with a formed magnetic stir bar amine oxides E _7, nitrogen 1
Polyethyleneimine having a molecular weight of 1800 and ethoxylated to about 7 ethyleneoxy residues (PEI 180
0 E ₇ ) (209 g, 0.595 mol nitrogen, prepared in Example 1) and hydrogen peroxide (120 g of a 30% by weight aqueous solution, 1.06 mol).
Plug and after initial exotherm, stir solution at room temperature overnight. The ¹ H-NMR (D ₂ O) spectrum obtained on the reaction mixture sample indicates complete conversion. This shows that the resonance due to the methylene protons adjacent to the unoxidized nitrogen is shifted from the original position by about 2.5 ppm to 3.5 ppm. 0.5% P on about 5g alumina pellet
d is added and the solution is left at room temperature for about 3 days. This solution was tested with indicator paper and found to be negative for peroxide. This material is suitably stored as is in a 51.5% active aqueous solution.

Example 4 Erlenmeyer flask 500ml equipped with a oxide magnetic stir bar of the quaternized PEI 1800 E _7, nitrogen 1
Polyethyleneimine with a molecular weight of 1800 (PEI 1800 E ₇ ) which was ethoxylated to about 7 ethyleneoxy residues per piece and subsequently quaternized to about 4.7% with dimethyl sulfate
(121.7 g, about 0.32 mol of oxidizable nitrogen), hydrogen peroxide (40 g of a 50% by weight aqueous solution, 0.588 mol), and water (109.4 mol)
g). Plug the flask and after the initial fever,
The solution is stirred overnight at room temperature. Obtained in the reaction mixture Sample ¹ H-
NMR (D ₂ O) spectrum shows that the methylene peak at 2.5~3.0ppm is shifted to approximately 3.5 ppm. 0.5% Pd on about 5g alumina pellet
Is added and the solution is left at room temperature for about 3 days. This solution was tested with indicator paper and found to be negative for peroxide. About 4.7% of nitrogen is quaternized and about 95.3%
This gives the desired material in which the nitrogen has been oxidized to the amine oxide, which is suitably stored as a 46.5% aqueous solution.

Production ethoxylation example 4A PEI 1200 E _7, the temperature measurement and control, pressure measurement, vacuum and inert gas purging, sampling, and 2 gallons made stirring stainless steel subjected to equipment for introducing the ethylene oxide as a liquid Perform in an autoclave. A cylinder of about 20 lb. net of ethylene oxide (ARC) is placed on a scale and ethylene oxide is pumped as a liquid into the autoclave so that changes in the weight of the cylinder can be monitored. 750 g of polyethyleneimine (PEI) (nominal molecular weight 1200, corresponding to about 0.625 mol of polymer and 17.4 mol of nitrogen functional unit) are placed in an autoclave. The autoclave is then sealed and the air is purged (by applying a vacuum to -28 "Hg, followed by pressurizing to 250 psia with nitrogen and then venting to atmospheric pressure). While heating to about 130 ° C. After about one hour, while cooling the autoclave to about 105 ° C.
The autoclave is charged to about 250 psia with nitrogen. The ethylene oxide is then slowly added to the autoclave over time, while carefully monitoring the autoclave pressure, temperature, and ethylene oxide flow. The ethylene oxide pump is stopped and cooled to prevent an increase in temperature due to the exothermic reaction. The total pressure is gradually increased during the reaction while maintaining the temperature at 100-110 ° C. After charging a total of 750 g of ethylene oxide (corresponding to about 1 mole of ethylene oxide per nitrogen function of PEI) into the autoclave, the temperature was increased to 11
Increase to 0 ° C. and stir autoclave for another hour. At this point, vacuum is applied to remove any remaining unreacted ethylene oxide.

Then, vacuum was continuously applied while cooling the autoclave to about 50 ° C., and 376 g of a methanol solution of 25% sodium methoxide (1.74 mol, 10% based on the PEI nitrogen functional group).
To achieve a catalytic amount). The methoxide solution is aspirated under vacuum into the autoclave, then the set point of the autoclave temperature controller is increased to 130 ° C. Use equipment to monitor the power consumed by the stirrer. Monitor stirrer power along with temperature and pressure. Stirrer power and temperature values indicate that methanol was removed from the autoclave and gradually increased as the viscosity of the mixture increased, stabilized in about 1 hour, and that most of the methanol was removed. The mixture is further vacuumed for another 30
Heat and stir for minutes.

Remove the vacuum and place the autoclave at 250 psia with cooling to 105 ° C. and then vent to atmospheric pressure.
Fill the autoclave with 200 psia of nitrogen. The pressure, temperature, and ethylene oxide flow rate of the autoclave are carefully monitored, and ethylene oxide is gradually added to the autoclave again as before, maintaining the temperature at 100 to 110 ° C. and limiting the temperature increase due to the exothermic reaction. 4500g
Of ethylene oxide (to a total of 7 moles of ethylene oxide per mole of PEI nitrogen functionality) is added over several hours, then the temperature is increased to 110 ° C. and the mixture is stirred for a further hour.

The reaction mixture is then collected in a nitrogen purged vessel and finally transferred into a 22 three-necked round bottom flask equipped with heating and stirring. 167 g of methanesulfonic acid (1.74 mol) are added to neutralize the strong alkali catalyst. The mixture is then stirred and heated to 130 ° C. while passing through a gas dispersion frit,
The reaction mixture is deodorized by passing about 100 cubic feet of an inert gas (argon or nitrogen) through the reaction mixture.

The final reaction product is cooled slightly and collected in a glass vessel purged with nitrogen.

In another production, neutralization and deodorization are performed in a reactor before discharging the product.

Other preferred examples, such as PEI 1200 E15 and PEI 1
200 E20 can be produced by the above-mentioned method by adjusting the reaction time and the amount of ethylene oxide used during the reaction.

Example 4B 9.7% Quaternization of PEI 1200 E _{7 In} a 500 ml Erlenmeyer flask equipped with a magnetic stir bar, a polyethylene imine having a molecular weight of 1200 ethoxylated to a degree of 7 (248.4 g, 0.707 mol nitrogen, prepared in Example 5) And acetonitrile (Baker, 200 ml). Dimethyl sulfate (Aldrich, 8.48 g, 0.067 mol) is added in one portion to the rapidly stirring solution, stoppered and stirred at room temperature overnight. Acetonitrile was removed at about 60 ° C. on a rotary evaporator, followed by Ku.
Further removal of the solvent using a gelrohr apparatus (Aldrich) at about 80 ° C. gives 220 g of the desired material as a dark brown viscous liquid. ^{The 13} C-NMR (D ₂ O) spectrum shows that the peak at about 58 ppm corresponding to dimethyl sulfate has disappeared. ^{The 1} H-NMR (D ₂ O) spectrum shows that the peak at 2.5 ppm (methylene added to the non-quaternized nitrogen) is partially shifted to about 3.0 ppm.

Example 5 Preparation of non-cotton soil free polymer Synthesis of sodium 2- (2,3-dihydroxypropoxy) ethanesulfonate monomer Magnetic stir bar, modified Claisen head, condenser (installed for distillation), thermometer, and temperature controller (Ther
In a 500 ml three-necked round-bottom flask equipped with mO-Watch (trade name, I ² R), isethionic acid, sodium salt (Al
drich, 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 is heated at 190 ° C. under argon overnight to distill water from the reaction mixture. ¹³ C-NMR
(DMSO-d _6), the isethionate peaks at about 53.5ppm and medicine 57.4ppm disappeared and about 51.4ppm (-CH ₂ SO ₃ N
Product peaks appear at a) and at about 67.5 ppm (CH ₂ CH ₂ SO ₃ Na), indicating that the reaction is complete. The solution was cooled to about 100 ° C and methanesulfonic acid (Aldri
Ch) to neutralize to pH7. Add 0.8 mol% potassium phosphate, monobasic as buffer, Kugelrohr apparatus (Aldrich)
Above, heating to 200 ° C. for about 3 hours at about 1 mm Hg gives 77 g of the desired pure substance as a yellow waxy solid. Alternatively, not all of the glycerin is removed before use in producing the oligomer. The use of a glycerin solution of SEG facilitates handling of this sulfonated monomer.

Example 6 Synthesis of sodium 2- [2- (2-hydroxyethoxy) ethoxy] ethanesulfonate monomer Magnetic stir bar, modified Claisenhead, condenser (installed for distillation), thermometer, and temperature controller (Ther
In a 1-liter three-necked round-bottomed flask equipped with m-O-Watch (trade name, I ² R), isethionic acid, sodium salt (Aldrich, 100.0 g, 0.675 mol) and distilled water (about 90
ml). After dissolution, a drop of hydrogen peroxide (Aldrich,
(30% by weight in water) to oxidize traces of bisulfite. The solution is stirred for one hour. The peroxide indicator strip shows a very weak solubility test. Add sodium hydroxide pellets (MCB, 2.5 g, 0.0625 mol), followed by diethylene glycol (Fisher, 303.3 g, 2.86 mol). The solution is heated at 190 ° C. under argon overnight to distill water from the reaction mixture. ¹³ C-NMR (DMSO-d ₆ ) indicates that the reaction is complete, as the isethionate peaks at about 53.5 ppm and about 57.4 ppm have disappeared. The solution is cooled to room temperature and neutralized to pH 7 with 57.4 g of a 16.4% solution of p-toluenesulfonic acid monohydrate in diethylene glycol (alternatively, methanesulfonic acid can be used). The ¹³ C-NMR (DMSO-d ₆ ) spectrum of the product is approximately 51 ppm (—CH ₂
SO ₃ Na), about 60 ppm (CH ₂ OH), and about 69 ppm, about 72 pp
m and the remaining four methylenes at about 77 ppm. There is also a small resonance for the sodium p-toluenesulfonate formed during neutralization. This reaction gives 451 g of a 35.3% solution of sodium 2- [2- (2-hydroxyethoxy) ethoxy] ethanesulfonate in diethylene glycol. 0.
Add 8 mol% monobasic potassium phosphate (Aldrich),
Excess diethylene glycol is removed on a Kugelrohr apparatus (Aldrich) at about 1 mm Hg at 150 ° C. for about 3 hours to obtain the desired “SE ₃ ” (defined above) as a very viscous oil or glass. Can be

Example 7 Synthesis of sodium 2- {2- [2- (2-hydroxyethoxy) ethoxy] ethoxy} ethanesulfonate monomer Magnetic stir bar, modified Claisenhead, condenser (installed for distillation), thermometer, and temperature controller (Ther
In a 1 liter three-necked round bottom flask equipped with m-O-Watch (trade name, I ² R), isethionic acid, sodium salt (Aldrich, 205.0 g, 1.38 mol) and distilled water (about 200
ml). After dissolution, a drop of hydrogen peroxide (Aldrich,
(30% by weight in water) to oxidize traces of bisulfite. The solution is stirred for one hour. The peroxide indicator strip shows a very weak positive test. Add sodium hydroxide pellets (MCB, 5.5 g, 0.138 mol), followed by triethylene glycol (Aldrich, 448.7 g, 3.0 mol). If desired, the triethylene glycol can be purified by heating with a strong base such as NaOH until color is stable, and then the purified glycol can be distilled off and used in the synthesis. The solution is heated at 190 ° C. under argon overnight to distill water from the reaction mixture. ¹³ C-NMR (DMSO-d ₆ )
And isethionate peaks disappeared at 53.5ppm and about 57.4 ppm, about _{51ppm (-CH 2 SO 3 Na)} , about 60 ppm (CH ₂ O
H), and the remaining methylene at about 67 ppm, about 69 ppm, and about 72 ppm,
This indicates that the reaction is complete. The solution is cooled to room temperature and neutralized to pH 7 with methanesulfonic acid. The reaction yields 650 g of a 59.5% solution of sodium 2- {2- [2- (2-hydroxyethoxy) ethoxy] ethoxy) ethanesulfonate in triethylene glycol. 0.8 mol% monobasic potassium phosphate as buffer (Aldrich)
At 180 ° C on a Kugelrohr apparatus (Aldrich) at about 1 mmHg.
Heat for about 5.5 hours to remove excess triethylene glycol and obtain the desired material as a brown solid. In removing excess triethylene glycol, a more soluble buffer was found to be more effective at adjusting the pH. An example of a more soluble buffer for such use is the salt of N-methylmorpholine with methanesulfonic acid. Alternatively, the pH can be adjusted by the frequent or continuous addition of an acid, such as methanesulfonic acid, to maintain the pH near neutral while removing excess glycol.

This material is believed to contain a small amount of disulfonate resulting from the reaction of isethionate with both ends of triethylene glycol. However, the crude is used without further purification as an anionic capping group for polymer production.

Other preparations use a larger excess of triethylene glycol, such as 5 to 10 moles per mole of isethionate.

Example 8 Sodium 2- [2- (2-hydroxyethoxy) ethoxy] ethanesulfonate, dimethyl terephthalate, 2
-Synthesis of oligomers of sodium (2,3-dihydroxypropoxy) ethanesulfonate, glycerin, ethylene glycol and propylene glycol Magnetic stir bar, modified Claisen head, condenser (installed for distillation), thermometer and temperature controller ( Ther
In a 250 ml three-necked round bottom flask equipped with m-O-Watch (trade name, 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 (Ba
ker, 14.0 g, 0.225 mol), propylene glycol (Fis
her, 17.5 g, 0.230 mol), and titanium (IV) propoxide (0.01 g, 0.02% of the total weight of the reaction mixture). The mixture is heated to 180 ° C. in argon, kept at that temperature overnight, and methanol and water are distilled from the reaction vessel. This material was transferred into a 500 ml one-necked round bottom flask and brought to 240 ° C. at about 2 mm Hg in a Kugelrohr apparatus (Aldrich).
Heat slowly over 20 minutes and maintain at that temperature for 1.5 hours. The reaction flask is then air-cooled in a vacuum very quickly (approximately 30 minutes) to near room temperature. With this reaction,
21.3 g of the desired oligomer are obtained as a brown glass. ¹³ C-NMR (DMSO-d ₆ ) indicates that at about 63.2 ppm
Shows the resonance of (O) OCH2CH2O (O) C- (diester) and the resonance of -C (O) OCH2CH2OH (monoester) at about 59.4 ppm. The ratio of diester peak height to monoester peak height is about 10. There are also resonances at about 51.5 ppm and about 51.6 ppm representative of the sulfoethoxy group (-CH2SO3Na). ¹ H-NMR (DMSO-d ₆ ) shows a resonance at about 7.9 ppm representing terephthalate aromatic hydrogen. Analysis by hydrolysis-gas chromatography shows a molar ratio of incorporated ethylene glycol to incorporated propylene glycol of 1.7: 1. This analysis shows that the final polymer weight is approximately 0.9%.
It also shows that% is glycerin. If all glycerin monomers are incorporated as esters of glycerin, the glycerin monomers will be about 4% of the final oligomer weight. The solubility is tested by weighing a small amount of material into a glass bottle, adding sufficient distilled water to make a 35% by weight solution, and stirring the glass bottle vigorously. This material can easily dissolve under these conditions.

Example 9 Sodium 2- [2- (2-hydroxyethoxy) ethoxy] ethanesulfonate, dimethyl terephthalate, 2-
Synthesis of oligomers of sodium (2,3-dihydroxypropoxy) ethanesulfonate, ethylene glycol and propylene glycol Magnetic stir bar, modified Claisen head, condenser (installed for distillation), thermometer and temperature controller (Ther
In a 250 ml three-necked round bottom flask equipped with m-O-Watch (trade name, 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 g of the total weight of the reaction mixture)
%). The mixture is heated to 180 ° C. in argon, kept at that temperature overnight, and methanol is distilled from the reaction vessel. The material is transferred into a 500 ml single-necked round bottom flask and gradually heated to about 0.1 mm Hg at 240 ° C. over about 20 minutes in a Kugelrohr apparatus (Aldrich) and maintained at that temperature for 110 minutes. The reaction flask is then air-cooled in a vacuum very quickly (approximately 30 minutes) to near room temperature. This reaction gives 24.4 g of the desired oligomer as a brown glass. ¹³ C-NMR (DMSO-d ₆ ) indicates that at about 63.2 ppm
Shows the resonance of (O) OCH2CH2O (O) C- (diester) and the resonance of -C (O) OCH2CH2OH (monoester) at about 59.4 ppm. The ratio of diester peak to monoester peak is measured as 8. Sulfoethoxy group (-CH2S
There are also resonances at about 51.5 ppm and about 51.6 ppm representing O3Na). ¹ H-NMR (DMSO-d ₆ ) shows a resonance at about 7.9 ppm representing terephthalate aromatic hydrogen. Analysis by hydrolysis-gas chromatography shows a molar ratio of incorporated ethylene glycol to incorporated propylene glycol of 1.6: 1. For solubility, weigh a small amount of material into a glass bottle,
Test by adding enough distilled water to a 35% by weight solution and stirring the glass bottle vigorously. This material can easily dissolve under these conditions.

Example 10 Sodium 2- [2- (2-hydroxyethoxy) ethoxy] ethanesulfonate, dimethyl terephthalate, 2-
Synthesis of oligomers of sodium (2,3-dihydroxypropoxy) ethanesulfonate, glycerin, ethylene glycol and propylene glycol Magnetic stir bar, modified Claisen head, condenser (installed for distillation), thermometer and temperature controller (Ther
Sodium 2- [2- (2-hydroxyethoxy) ethoxy] ethanesulfonate (7.0 g, 0.1 g) was placed in a 250 ml three-necked round bottom flask equipped with m-O-Watch (trade name, I ² R).
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 (Ba
ker, 6.1 g, 0.100 mol), propylene glycol (Fish
er, 7.5 g, 0.100 mol), and titanium (IV) propoxide (0.01 g, 0.02% of the total weight of the reaction mixture).
The mixture is heated to 180 ° C. in argon, kept at that temperature overnight, and methanol is distilled from the reaction vessel. This material is transferred into a 250 ml single neck round bottom flask and gradually heated to 240 ° C. over about 20 minutes at about 3 mm Hg in a Kugelrohr apparatus (Aldrich) and maintained at that temperature for 1.5 hours. The reaction flask is then air-cooled in a vacuum very quickly (approximately 30 minutes) to near room temperature. This reaction gives 18.1 g of the desired oligomer as a brown glass. ¹³ C-NMR
(DMSO-d ₆₎ has, -C about 63.2ppm (O) OCH2CH2O
(O) shows resonance of C- (diester). No resonance of -C (O) OCH2CH2OH (monoester) at about 59.4 ppm was detected, at most one-twelfth the size of the diester peak. There are also resonances at about 51.5 ppm and about 51.6 ppm representative of the sulfoethoxy group (-CH2SO3Na). ¹ H-NMR (DMSO-d ₆ ) shows a resonance at about 7.9 ppm representing terephthalate aromatic hydrogen. Analysis by hydrolysis-GC showed a molar ratio of incorporated ethylene glycol to incorporated propylene glycol of 1.6:
1 is shown. The glycerin incorporated was found to be 0.45% by weight of the final polymer. Solubility is tested by weighing a small amount of material into a glass bottle, adding sufficient distilled water to a 35% by weight solution, and stirring the glass bottle vigorously. This material can easily dissolve under these conditions.

Example 11 Sodium 2- [2- (2-hydroxyethoxy) ethoxy] ethanesulfonate, dimethyl terephthalate, 2-
Synthesis of oligomers of sodium (2,3-dihydroxypropoxy) ethanesulfonate, glycerol, ethylene glycol and propylene glycol Magnetic stir bar, modified Claisen head, condenser (installed for distillation), thermometer and temperature controller (Ther
In a 250 ml three-necked round bottom flask equipped with mO-Watch (trade name, I ² R), sodium 2- [2- (2-hydroxyethoxy) ethoxy] ethanesulfonate (similar to Example 2) 2.7 g, 0.011 mol), dimethyl terephthalate (12.
0 g, 0.062 mol, Aldrich), sodium 2- (2,3-dihydroxypropoxy) ethanesulfonate (5.0 g, 0.022 mol as in Example 1), glycerol (Baker, 0.50 g,
0.0055 mol), ethylene glycol (Baker, 6.8 g, 0.1
10 mol), propylene glycol (Baker, 8.5, 0.112 mol), and titanium (IV) propoxide (0.01 g, 0.02% of the total weight of the reaction mixture) are added. The mixture is heated to 180 ° C. in argon, kept at that temperature overnight, and methanol and water are distilled from the reaction vessel. 500m of this material
l into a single-necked round-bottom flask and transfer to Kugelrohr apparatus (Aldric
During h), gradually heat to 240 ° C. over about 20 minutes at about 0.5 mmHg and maintain at that temperature for 150 minutes. The reaction flask is then air-cooled in a vacuum very quickly (approximately 30 minutes) to near room temperature. By this reaction, the desired oligomer 16.7 g
Is obtained as a brown glass. ¹³ C-NMR (DMSO-
d ₆₎ has, -C at about 63.2ppm (O) OCH2CH2O (O)
C- (diester) resonance and at about 59.4 ppm
The resonance of C (O) OCH2CH2OH (monoester) is shown. The ratio of the peak height of the diester resonance to the peak height of the monoester resonance is measured as 6.1. About 51.5 ppm and about 51.6 ppm representing a sulfoethoxy group (-CH2SO3Na)
There is also a resonance at ¹ H-NMR (DMSO-d ₆ ) shows a resonance at about 7.9 ppm representing terephthalate aromatic hydrogen. Analysis by hydrolysis-gas chromatography shows a molar ratio of incorporated ethylene glycol to incorporated propylene glycol of 1.42: 1. The solubility is tested by weighing a small amount of material into a glass bottle, adding sufficient distilled water to make a 35% by weight solution, and stirring the glass bottle vigorously. This material can easily dissolve under these conditions. A further 9 g sample of this material is further heated in a Kugelrohr apparatus at about 0.5 mm Hg at 240 ° C. and maintained at that temperature for 80 minutes. ¹³ C-NMR (DMSO-
d ₆ ) shows no detectable monoester peak at about 59.4 ppm. The diester peak at about 63.2 ppm is at least 11 times greater than the monoester peak.
The solubility of this material was tested as described above and found to be readily soluble under these conditions.

The modified polyamine of the present invention useful as a cotton soil release agent is effectively produced by the following method.

Detergent Composition Formulations The detergent compositions of the present invention may be in liquid, paste or granular form. Such compositions can be prepared by combining the essential and optional ingredients in the required concentration and in any suitable order and by conventional means.

A liquid detergent composition can be prepared by combining the essential components and optional ingredients, in any suitable order, to obtain a composition containing the required concentration of the components. The liquid composition of the present invention may be in "compressed form", in which case the liquid detergent composition of the present invention contains a small amount of water compared to a normal liquid detergent.

The compositions described in Table I are suitable for selecting colored fabrics in aqueous washing solutions and exhibit excellent dye transfer inhibiting properties. PVNO or PVPI and selected polyamines (PEI 1
The dye transfer inhibition performance provided by the combination of 800E7) is much better than using the dye transfer inhibiting polymer or polyamine alone.

For example, in the manufacture of a granular composition, generally the basic granule components (eg, surfactant, builder, water, etc.) are combined as a slurry, and the resulting slurry is spray dried,
Reduce the amount of residual moisture (5-12%). The remaining dry ingredients, in the form of a granular powder, are mixed with the spray-dried granules in a rotary mixing drum, and the resulting granules are sprayed with liquid ingredients (eg enzymes, binders and fragrances) and the final detergent composition Things can be formed. The granular composition of the present invention,
It may be in "compressed form", ie have a relatively higher density than conventional granular detergents, i.e. 550-950 g /. In such a case, the granular composition of the present invention contains a lower amount of "inorganic filler salt" as compared to a conventional granular detergent, but a representative filler salt is an alkaline earth metal. Sulfates and hydrochlorides, especially sodium sulfate,
The filler salt content of "compressed" detergents is generally less than 10%.

The compositions described in Table IV are suitable for washing colored fabrics in aqueous washing solutions and exhibit excellent dye transfer inhibiting properties. PVNO or PVPI and selected polyamines (PEI
The dye transfer inhibition performance provided by the combination of 1800E7) is much better than when the dye transfer inhibiting polymer or polyamine is used alone.

Method of Use The present invention also provides a method for washing colored fabrics with little or no dye transfer. In such a method, the fabrics are contacted with an effective amount of an aqueous wash formed from the above detergents. Contact between the fabric and the cleaning solution generally occurs under agitation conditions.

For good washing, stirring is performed in a washing machine.
After washing, the wet fabric is preferably dried in a conventional clothes dryer. The effective amount of the liquid or granular detergent composition in the aqueous washing solution in the washing machine is preferably from about 500 to
It is about 7000 ppm, more preferably about 1000 to about 3000 ppm.

────────────────────────────────────────────────── 72 Continuation of the front page (72) Inventor Chanchal, Kumar, Gauche Ohio, USA, West, Chester, Pinemill, Drive, 7005 (56) References JP-A-7-316590 (JP, A) JP-A Sho 62-34996 (JP, A) WO 95/32272 (WO, A1) WO 94/2579 (WO, A1) (58) Fields investigated (Int. Cl. ⁷ , DB name) C11D 3/37

Claims (7)

(57) [Claims] 1. A laundry composition, comprising: a) at least 0.01% by weight of a dye transfer inhibitor; b) at least 0.1% by weight of a water-soluble or dispersible modified polyamine fabric surface modifier; modifier has the formula _{V (n + 1) W m} Y n Z of the modified polyamine, comprise polyamine backbone corresponding to the formula, or A modified polyamine having the formula V _{(n-k + 1)} W _m Y _n Y ′ _k Z, comprising a polyamine skeleton corresponding to the following formula, In the above formula, k is n or less, the polyamine skeleton has a molecular weight of more than 200 daltons before modification, and the modification is performed by converting at least one nitrogen skeleton in the polyamine skeleton with N-oxide. I) V units are terminal units having the formula: ii) W units are skeletal units having the formula: iii) Y units are branch units having the formula: iv) Z units are terminal units having the formula: In the above formula, backbone linkages R units, C ₂ -C ₁₂ alkylene, C ₄ -C ₁₂ alkenylene, C ₃ -C ₁₂ hydroxyalkylene, C ₄ -C ₁₂ dihydroxy - alkylene, C ₈ -C ₁₂ dialkyl arylene,
− (R ¹ O) _x R ¹ −, − (R ¹ O) _x R ⁵ (OR ¹ ) _x −, − (CH ₂ CH
(OR ² ) CH ₂ O) _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 R ¹ is C ₂ -C ₆ alkylene, or a mixture thereof, R ² is hydrogen, — (R ¹ O) _x B, Or a mixture thereof, wherein 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,
Or a mixture thereof, R ⁴ is, C ₁ -C ₁₂ alkylene, C ₄ -C ₁₂ alkenylene, C ₈ ~
C ₁₂ arylalkylene, a C ₆ -C ₁₀ arylene, or mixtures thereof,, R ⁵ is, C ₁ -C ₁₂ alkylene, C ₃ -C ₁₂ hydroxyalkylene, C ₄ -C ₁₂ dihydroxy - alkylene, C ₈ ~ C ₁₂ dialkylarylene, -C (O)-, -C (O) NHR ⁶ NHC
(O)-, -R ¹ (OR ¹ )-, -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) CH ₂ —, or a mixture thereof, wherein R ⁶ is C ₂ -C ₁₂ alkylene or C ₆ -C ₁₂ arylene, and the E unit is 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, - (R 1 O) x B, -C (O)
R ^3, and is one selected from the group consisting of mixtures thereof, 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, - (C
_{H 2) q (CHSO 2 M} ) CH 2 -SO 3 M, - (CH 2) p PO 3 M, -PO
₃ M, or a mixture thereof, M is hydrogen or a water-soluble cation in an amount sufficient to satisfy the charge balance, X is a water-soluble anion, and m has a value of 4 to 400. N has a value of 0 to 200; p has a value of 1 to 6; q has a value of 0 to 6; r has a value of 0 or 1; Has a value of 1, x has a value of 1 to 100, y has a value of 0 to 100, z has a value of 0 or 1, and c) constitutes the remaining part, A carrier and an auxiliary component, wherein the auxiliary component is a builder, an optical brightener, a bleach, a bleach accelerator, a bleach activator, an enzyme, an enzyme stabilizer, a foam inhibitor, a dye, a fragrance, and coloring. A composition selected from the group consisting of an agent, a filler salt, a hydrotrope, and mixtures thereof. 2. A laundry detergent composition which provides dye transfer inhibiting properties, comprising: a) at least 3% by weight of an anionic cleaning surfactant, wherein the cleaning surfactant is an alkyl alkoxy sulfate, an alkyl sulfate, And b) at least 2% by weight of a nonionic detersive surfactant, wherein the detersive surfactant is an alkyl alkoxylate, A nonionic surfactant selected from the group consisting of a fatty acid amide having, and a mixture of the surfactants, In the above formula, R ⁷ is C ₇ -C ₂₂ alkyl, and R ⁸ is independently hydrogen, C ₁ -C ₄ alkyl, C ₁ -C ₄ hydroxyalkyl, — (C ₂ H ₄ O) _{jH wherein} j is 1-3, and mixtures thereof; Q is a linear alkyl chain comprising at least three hydroxyl moieties directly attached to the chain C) at least 0.01% by weight of a dye transfer inhibitor, and d) at least 0.05% by weight of a water-soluble or dispersible modified polyamine fabric surface modifier. When, and said modifier has the formula V _{(n + 1)} of the modified polyamine having a W _m Y _n Z, comprises a polyamine backbone corresponding to the formula, or A modified polyamine having the formula V _{(n-k + 1)} W _m Y _n Y ′ _k Z, comprising a polyamine skeleton corresponding to the following formula: In the above formula, k is n or less, and the polyamine skeleton has a molecular weight of more than 200 daltons before modification, and the modification comprises oxidizing at least one nitrogen skeleton in the polyamine skeleton with N-oxide. I) the V unit is a terminal unit having the formula: ii) W units are skeletal units having the formula: iii) Y units are branch units having the formula: iv) Z units are terminal units having the formula: In the above formula, backbone linkages R units, C ₂ -C ₁₂ alkylene, C ₄ -C ₁₂ alkenylene, C ₃ -C ₁₂ hydroxyalkylene, C ₄ -C ₁₂ dihydroxy - alkylene, C ₈ -C ₁₂ dialkyl arylene,
− (R ¹ O) _x R ¹ −, − (R ¹ O) _x R ⁵ (OR ¹ ) _x −, − (CH ₂ CH
(OR ² ) CH ₂ O) _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 R ¹ is C ₂ -C ₆ alkylene, or a mixture thereof, R ² is hydrogen, — (R ¹ O) _x B, Or a mixture thereof, wherein 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,
Or a mixture thereof, R ⁴ is, C ₁ -C ₁₂ alkylene, C ₄ -C ₁₂ alkenylene, C ₈ ~
C ₁₂ arylalkylene, a C ₆ -C ₁₀ arylene, or mixtures thereof,, R ⁵ is, C ₁ -C ₁₂ alkylene, C ₃ -C ₁₂ hydroxyalkylene, C ₄ -C ₁₂ dihydroxy - alkylene, C ₈ ~ C ₁₂ dialkylarylene, -C (O)-, -C (O) NHR ⁶ NHC
(O)-, -R ¹ (OR ¹ )-, -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) CH ₂ —, or a mixture thereof, wherein R ⁶ is C ₂ -C ₁₂ alkylene or C ₆ -C ₁₂ arylene, and the E unit is 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, - (R 1 O) x B, -C (O)
R ³ , and mixtures thereof; 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, - (C
_{H 2) q (CHSO 2 M} ) CH 2 -SO 3 M, - (CH 2) p PO 3 M, -PO
₃ M, or a mixture thereof, M is hydrogen or a water-soluble cation in an amount sufficient to satisfy the charge balance, X is a water-soluble anion, and m has a value of 4 to 400. N has a value of 0 to 200; p has a value of 1 to 6; q has a value of 0 to 6; r has a value of 0 or 1; Has a value of 1, x has a value of 1 to 100, y has a value of 0 to 100, z has a value of 0 or 1, and e) constitutes the rest, A carrier and an auxiliary component, wherein the auxiliary component is a builder, an optical brightener, a bleach, a bleach accelerator, a bleach activator, an enzyme, an enzyme stabilizer, a foam inhibitor, a dye, a fragrance, a colorant, and a filler. A composition selected from the group consisting of wood salts, hydrotropes, and mixtures thereof. 3. A laundry detergent composition providing dye transfer inhibiting properties, comprising: a) at least 10% by weight of an anionic detergent selected from the group consisting of alkyl sulfates, alkyl alkoxy sulfates, and mixtures thereof. A surfactant; b) at least 3% by weight of a non-ionic 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 An antimigration 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 modified polyamine fabric surface modifier; having the formula _{V (n + 1) W m} Y n Z, comprises a polyamine backbone corresponding to the formula, or A modified polyamine having the formula V _{(n-k + 1)} W _m Y _n Y ′ _k Z, comprising a polyamine skeleton corresponding to the following formula: In the above formula, k is n or less, and the polyamine skeleton has a molecular weight of more than 200 daltons before modification, and the modification comprises oxidizing at least one nitrogen skeleton in the polyamine skeleton with N-oxide. I) the V unit is a terminal unit having the formula: ii) W units are skeletal units having the formula: iii) Y units are branch units having the formula: iv) Z units are terminal units having the formula: In the above formula, backbone linkages R units, C ₂ -C ₁₂ alkylene, C ₄ -C ₁₂ alkenylene, C ₃ -C ₁₂ hydroxyalkylene, C ₄ -C ₁₂ dihydroxy - alkylene, C ₈ -C ₁₂ dialkyl arylene,
− (R ¹ O) _x R ¹ −, − (R ¹ O) _x R ⁵ (OR ¹ ) _x −, − (CH ₂ CH
(OR ² ) CH ₂ O) _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 R ¹ is C ₂ -C ₆ alkylene, or a mixture thereof, R ² is hydrogen, — (R ¹ O) _x B, Or a mixture thereof, wherein 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,
Or a mixture thereof, R ⁴ is, C ₁ -C ₁₂ alkylene, C ₄ -C ₁₂ alkenylene, C ₈ ~
C ₁₂ arylalkylene, a C ₆ -C ₁₀ arylene, or mixtures thereof,, R ⁵ is, C ₁ -C ₁₂ alkylene, C ₃ -C ₁₂ hydroxyalkylene, C ₄ -C ₁₂ dihydroxy - alkylene, C ₈ ~ C ₁₂ dialkylarylene, -C (O)-, -C (O) NHR ⁶ NHC
(O)-, -R ¹ (OR ¹ )-, -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) CH ₂ —, or a mixture thereof, wherein R ⁶ is C ₂ -C ₁₂ alkylene or C ₆ -C ₁₂ arylene, and the E unit is 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, - (R 1 O) x B, -C (O)
R ^3, and is one selected from the group consisting of mixtures thereof, 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, a -PO ₃ M, or mixtures thereof,, M is hydrogen in an amount sufficient to satisfy charge balance, or X is a water-soluble anion, X is a water-soluble anion, m has a value of 4 to 400, n has a value of 0 to 200, p has a value of 1 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, and y has a value of 0 to 100. Wherein z has a value of 0 or 1 and f) comprises a carrier and auxiliary components, which make up the remainder, said auxiliary components comprising a builder, an optical brightener, a bleaching accelerator, It is selected from the group consisting of bleach activators, enzymes, enzyme stabilizers, foam inhibitors, dyes, fragrances, colorants, filler salts, hydrotropes, and mixtures thereof. Composition. 4. A laundry detergent composition which provides dye transfer inhibiting properties, comprising: a) at least 10% by weight of an anionic detergent selected from the group consisting of alkyl sulfates, alkyl alkoxy sulfates, and mixtures thereof. A surfactant; b) at least 3% by weight of a non-ionic 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 An antimigration 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 modified polyamine fabric surface modifier; having the formula _{V (n + 1) W m} Y n Z, comprises a polyamine backbone corresponding to the formula, or A modified polyamine having the formula V _{(n-k + 1)} W _m Y _n Y ′ _k Z, comprising a polyamine skeleton corresponding to the following formula: In the above formula, k is n or less, and the polyamine skeleton has a molecular weight of more than 200 daltons before modification, and the modification comprises oxidizing at least one nitrogen skeleton in the polyamine skeleton with N-oxide. I) the V unit is a terminal unit having the formula: ii) W units are skeletal units having the formula: iii) Y units are branch units having the formula: iv) Z units are terminal units having the formula: In the above formula, backbone linkages R units, C ₂ -C ₁₂ alkylene, C ₄ -C ₁₂ alkenylene, C ₃ -C ₁₂ hydroxyalkylene, C ₄ -C ₁₂ dihydroxy - alkylene, C ₈ -C ₁₂ dialkyl arylene,
− (R ¹ O) _x R ¹ −, − (R ¹ O) _x R ⁵ (OR ¹ ) _x −, − (CH ₂ CH
(OR ² ) CH ₂ O) _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 R ¹ is C ₂ -C ₆ alkylene, or a mixture thereof, R ² is hydrogen, — (R ¹ O) _x B, Or a mixture thereof, wherein 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,
Or a mixture thereof, R ⁴ is, C ₁ -C ₁₂ alkylene, C ₄ -C ₁₂ alkenylene, C ₈ ~
C ₁₂ arylalkylene, a C ₆ -C ₁₀ arylene, or mixtures thereof,, R ⁵ is, C ₁ -C ₁₂ alkylene, C ₃ -C ₁₂ hydroxyalkylene, C ₄ -C ₁₂ dihydroxy - alkylene, C ₈ ~ C ₁₂ dialkylarylene, -C (O)-, -C (O) NHR ⁶ NHC
(O)-, -R ¹ (OR ¹ )-, -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 O
CH ₂ CH (OH) CH ₂ — or a mixture thereof, wherein R ⁶ is C ₂ -C ₁₂ alkylene or C ₆ -C ₁₂ arylene, and the E unit is hydrogen, C ₁ -C ₂₂ alkyl, 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, - (R 1 O) x B, -C (O)
R ^3, or is one selected from the group consisting of mixtures thereof, 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, - (C
_{H 2) q (CHSO 2 M} ) CH 2 -SO 3 M, - (CH 2) p PO 3 M, -PO
₃ M, or a mixture thereof, M is hydrogen or a water-soluble cation in an amount sufficient to satisfy the charge balance, X is a water-soluble anion, and m has a value of 4 to 400. N has a value of 0 to 200; p has a value of 1 to 6; q has a value of 0 to 6; r has a value of 0 or 1; X has a value of 1 to 100, y has a value of 0 to 100, z has a value of 0 or 1, and f) constitutes the remainder, A composition comprising a carrier and auxiliary ingredients. 5. The method of claim 1, wherein the dye transfer inhibitor comprises: a) a polyamine N-oxide polymer having the formula: In the above formula, P is a polymerizable unit, i) an NO group added to the polymerizable unit, and ii) an NO group is a part of the polymerizable unit. And iii) a mixture thereof, wherein A is selected from the following groups or mixtures thereof: x is 0 or 1, R is aliphatic, ethoxylated aliphatic, aromatic, heterocyclic, alicyclic, or a mixture thereof, wherein i) the nitrogen of the NO group is R Or ii) the N—O group is part of R; and the N—O group has the following formula: Wherein R ₁ , R ₂ , and R ₃ are an aliphatic, aromatic, heterocyclic, alicyclic group, or a mixture thereof, x, y, and z are 0 or 1, and N- nitrogen atom of the O group, i) and R _1, R ₂ or added nitrogen atom in R _3,, and a nitrogen atom which is a unit of ii) in R _1, R ₂ or R _3,, iii) polymerizing Selected from the group consisting of: a nitrogen atom which is one unit constituting part of the possible unit P; iv) a nitrogen atom added to the polymer skeleton comprising the P unit; and v) a combination thereof. B) a polyethoxylated urethane compound, wherein the polyethoxylated urethane compound comprises: i) at least one compound comprising at least one functional hydroxyl group;
Reaction products of at least one water-soluble polyether alcohol, a water-insoluble organic polyisocyanate, and an organic monoisocyanate; ii) at least one containing at least one functional hydroxyl group;
A reaction product of at least one water-soluble polyether alcohol with an organic monoisocyanate; iii) at least one water-soluble polyether alcohol containing at least one functional hydroxyl group; a water-insoluble organic polyisocyanate; An organic monoisocyanate,
A reaction product of at least one polyhydric alcohol and at least one polyhydric alcohol ether; iv) at least one containing at least one functional hydroxyl group;
A water-soluble polyether alcohol, a water-insoluble organic polyisocyanate reactant containing two isocyanate groups, and a reaction product of a monofunctional active hydrogen-containing compound, and v) at least one functional group. At least one containing a hydroxyl group
A water-soluble polyether alcohol, a water-insoluble organic polyisocyanate reactant containing at least three isocyanate groups, and a reaction product of a monofunctional active hydrogen-containing compound; And the polyether moiety has a molecular weight of at least 200; the polyethoxylated urethane comprises at least one hydrophobic group and at least one water-soluble polyether moiety; and the total number of carbon atoms in the hydrophobic group. Is at least 4 and the total molecular weight is between 300 and 60,000. c) an acrylamide polymer, wherein the acrylamide polymer comprises: (i) an N-substituted acrylamide having the following formula: Wherein R ¹ is hydrogen, C ₁ -C ₆ alkyl, or a mixture thereof, and R ² and R ³ are independently hydrogen, methyl, ethyl, propyl, isopropyl, butyl, t-butyl, Or R ² and R ³ together with the nitrogen to which R ² and R ³ are attached form a 3-7 membered monoaromatic nitrogen heterocyclic compound, selected from the group consisting of isobutyl, and mixtures thereof. To form. (Ii) C ₁ -C ₆ alkyl (meth) acrylate, hydroxyalkyl (meth) acrylate, hydroxyaryl (meth) acrylate, alkoxyalkyl (meth) acrylate, alkoxyalkyl (meth) acrylate, styrene, Vinyltoluene, alkyl vinyl ether, amino-substituted alkyl (meth) acrylate, amino-alkyl vinyl ether, maleic anhydride, maleic acid,
A vinyl monomer selected from the group consisting of fumaric acid, itaconic acid, (meth) acrylic acid, and mixtures thereof, and wherein the acrylamide dye transfer inhibitor comprises at least one N
5. The composition of claim 1, which is formed from the substituted acrylamide monomer acrylamide and, optionally, one or more vinyl monomers, and d) a polyamino acid. A composition according to any one of the preceding claims. 6. The method according to claim 1, wherein the dye transfer inhibitor is poly (4-vinylpyridine N-oxide), poly (2-vinylpyridine N-oxide).
The composition according to any one of claims 1 to 4, wherein the composition is selected from the group consisting of -oxide), polyvinylpyrrolidone, a copolymer of polyvinylpyrrolidone and vinylimidazole, and a mixture thereof. 7. A method for preventing dye transfer between dyed or colored fabrics during washing, wherein the dyed or colored fabrics are washed according to any one of claims 1 to 6. Contacting with an aqueous solution of the composition for use.