CN1387559A - Laundry detergent compositions with fabric care - Google Patents

Abstract

This invention relates to laundry detergent compositions comprising a semi-polar nonionic surfactant and a polymer, oligomer, or copolymer of cyclic amine groups. The compositions provide good cleaning performance and desired benefits for fabric appearance and integrity.

Description

Laundry detergent composition having fabric care properties

field of invention

The present invention relates to laundry detergent compositions comprising a semi-polar nonionic surfactant and certain cyclic amine based polymeric, oligomeric or copolymeric materials.

Background of the invention

It is well known that alternating cycles of wearing and washing fabrics and textiles, such as used clothes and clothing items, has an unavoidable negative effect on the appearance and integrity of the fabrics and textiles so worn and laundered. Fabrics and textiles wear out over time. Fabrics and textiles must be washed to remove stains and soils that have accumulated in and on them during normal wear. However, the laundering operation itself weakens over many cycles and can itself damage the integrity and appearance of these fabrics and textiles.

Damage to fabric integrity and appearance can manifest in several ways. The mechanical action of washing will dislodge short fibers from woven and knitted fabric/textile structures. These displaced fibers can form lint, fuzz, or "pills" that are visible on the surface of the fabric, which will cause the fabric to lose its pristine appearance. In addition, repeated washing of fabrics and textiles, especially with laundry products containing bleach, will strip dyes from fabrics and textiles, and the result of this reduced color intensity will be a faded, worn-out appearance, and in In many cases, this is the result of changes in the hue and shade of the color.

In light of this, the art has discovered several materials that can be incorporated into laundry detergent products, which themselves can bind to the fibers of fabrics and textiles washed with the detergent product, with a tendency to spoil the appearance of the washed fabric/textile diminished or minimized. Examples of such materials are cationic emollient surfactants, cyclic amine based polymers, dye transfer inhibiting agents, chelating agents, crystal growth inhibitors.

It has been found, however, that fabric care cationic cyclic amine based polymers are not highly compatible with the large number of anionic surfactants commonly formulated in conventional laundry detergent compositions. It was also found that those anionic surfactants would greatly impair the effectiveness of the cyclic amine-based compounds. Good cleaning performance is generally produced with such high amounts of the anionic surfactant. Therefore, to formulate compositions with the cationic cyclic amine-based polymers, the detergent compositions are formulated with nonionic surfactants instead of anionic surfactants. However, it has been found that detergent compositions formulated with high amounts of nonionic surfactants do not provide the same cleaning performance and are more difficult to formulate than high amounts of anionic surfactants, especially at high electrolyte levels.

In view of the above, it is an object of the present invention to formulate a laundry detergent composition which provides both superior cleaning performance and superior fabric care benefits. It has surprisingly been found that the combination of a semi-polar nonionic surfactant and a cationic cyclic amine-based polymer as described above can produce excellent cleaning performance and excellent fabric care benefits.

We have also found that the combination of the semi-polar nonionic surfactant of the present invention and a cyclic amine-based polymer has good dye transfer inhibition and fade resistance.

We have also found that the compositions of the present invention possess a high degree of physical stability when formulated in liquid form.

Summary of the invention

The present invention relates to laundry detergent compositions comprising a semi-polar nonionic surfactant and a cyclic amine based polymer, oligomer or copolymer. The compositions are capable of delivering good cleaning performance and desirable fabric appearance and integrity benefits. The cyclic amine-based polymer, oligomer or copolymer is characterized in that it has the following formula as defined below:

In its method aspect, the present invention relates to a method for laundering fabrics and textiles in an aqueous washing and treatment solution formed with an effective amount of the detergent composition of the present invention, or with the individual components of the composition of. Fabrics and textiles are washed in the wash solution, then rinsed and dried, to impart fabric cleaning and fabric appearance benefits to the fabrics and textiles so treated. These fabric care benefits include improved overall appearance, reduced pill/lint, fade resistance, improved dye transfer inhibition, improved abrasion resistance and/or enhanced softness. Detailed description of the invention

The laundry detergent compositions of the present invention comprise a cyclic amine based polymer and an amine oxide surfactant and provide excellent cleaning performance and excellent fabric care benefits.

Without wishing to be bound by theory, it is believed that semi-polar nonionic surfactants introduce some "hidden" anionic character through their chemical structure. Thus, those semi-polar nonionic surfactants thus provide good cleaning performance while not reacting with the cationic polymer, thus providing excellent fabric cleaning performance and excellent fabric care performance.

In addition, it has also surprisingly been found that the semi-polar nonionic surfactant acts as a hydrotrope in the compositions of the present invention when formulated in liquid form. In fact, without wishing to be bound by theory, it is known to those skilled in the art that large amounts of nonionic surfactants in liquid compositions can cause phase separation. It has been found that the semi-polar nonionic surfactants of the present invention act as hydrotropes and greatly reduce phase separation. Thus, it has been found that these semi-polar nonionic surfactants facilitate the formulation of highly nonionic detergent compositions and increase the physical stability of the liquid product. This allows the formulation of laundry detergent compositions containing high levels of nonionic surfactant which are fully isotropic liquids.

The first essential ingredient of the laundry detergent composition of the present invention is the following cyclic amine-based polymer, oligomer or copolymer: A) cyclic amine-based polymer, oligomer or copolymer Material

The first essential ingredient of the compositions of the present invention is one or more polymers, oligomers or copolymers of cyclic amine groups. These materials have been found to impart appearance benefits to fabrics and textiles washed in aqueous wash solutions formed with detergent compositions containing the cyclic amine-based fabric treatment materials. These fabric appearance benefits may include, for example, improved overall laundered fabric appearance, reduced pill and fuzz formation, improved dye transfer inhibition, resistance to fading, improved abrasion resistance, and the like.

As noted above, the combination of semi-polar nonionic surfactants and cyclic amine-based fabric treatment materials used in the compositions and methods of the present invention provide these fabric appearance benefits while maintaining good cleaning performance.

The cyclic amine-based polymer, oligomer or copolymer component of the compositions of the present invention may comprise combinations of such cyclic amine-based materials. For example, a mixture of piperadine and epihalohydrin condensation products can be combined with a mixture of morpholine and epihalohydrin condensation products to achieve the desired fabric treatment benefit. Additionally, the molecular weight of these cyclic amine-based fabric treatment materials in the mixture can vary, as will be illustrated in the Examples below.

It will be apparent to those of ordinary skill in the art that an oligomer is a molecule consisting of only a few monomer units, whereas a polymer contains a considerable number of monomer units. The present invention defines oligomers as molecules having an average molecular weight of less than about 1000 and polymers as molecules having an average molecular weight of greater than about 1000. A copolymer is a polymer or oligomer formed by the simultaneous or sequential polymerization of two or more different monomers. The copolymer of the present invention may include a polymer such as a mixture of primary cyclic amine based monomers, such as piperadine, and secondary cyclic amine monomers, such as morpholine, or Oligomer.

The cyclic amine based fabric treatment components in the detergent compositions of the present invention will generally constitute from 0.01% to 5%, preferably from 0.1% to 4%, more preferably from 0.75% to 3%, by weight of the detergent compositions.

除了至少一个环状部分外，W还可以包括通式结构的脂肪族或取代脂肪族部分；-每一个B都独立地是C₁-C₁₂亚烷基，C₁-C₁₂取代的亚烷基，C₃-C₁₂亚烯基，C₈-C₁₂二烷基亚芳基(dialkylarylene)，C₈-C₁₂二烷基亚芳基二基(dialkylarylenediyl)，和-(R₅O)_nR₅-；-每一个D都独立地是C₂-C₆亚烷基；-每一个Q都独立地选自于羟基，C₁-C₁₈烷氧基，C₂-C₁₈羟基烷氧基，氨基，C₁-C₁₈烷基氨基，二烷基氨基，三烷基氨基，杂环单氨基和二氨基；-每一个R₁都独立地选自于H，C₁-C₈烷基和C₁-C₈羟基烷基；-每一个R₂都独立地选自于C₁-C₁₂亚烷基，C₁-C₁₂亚烯基，-CH₂-CH(OR₁)-CH₂，C₈-C₁₂亚烷芳基(alkarylene)，C₄-C₁₂二羟基亚烷基，聚(C₂-C₄亚烷氧基)亚烷基(poly(C₂-C₄ alkyleneoxy)alkylene)，H₂CH(OH)CH₂OR₂OCH₂CH(OH)CH₂-和C₃-C₁₂烃基部分；Cyclic amine-based polymers, oligomers or copolymers suitable for the purposes of the present invention are characterized by the general formula: Where: each T is independently selected from H, C ₁ -C ₁₂ alkyl, substituted alkyl, C ₇ -C ₁₂ alkylaryl, -(CH ₂ ) _h COOM, -(CH ₂ ) _h SO ₃ M, CH ₂ CH(OH)SO ₃ M, -(CH ₂ ) _h OSO ₃ M, and -R ₂ Q; -wherein W includes at least one cyclic component selected from:

In addition to at least one cyclic moiety, W may also include aliphatic or substituted aliphatic moieties of the general structure; -Each B is independently C ₁ -C ₁₂ alkylene, C ₁ -C ₁₂ substituted alkylene, C ₃ -C ₁₂ alkenylene, C ₈ -C ₁₂ dialkylarylene ), C ₈ -C ₁₂ dialkylarylene diyl (dialkylylarylenediyl), and -(R ₅ O) _n R ₅ -; - each D is independently C ₂ -C ₆ alkylene; - each Each Q is independently selected from hydroxyl, C ₁ -C ₁₈ alkoxy, C ₂ -C ₁₈ hydroxyalkoxy, amino, C ₁ -C ₁₈ alkylamino, dialkylamino, trialkylamino, Heterocyclic monoamino and diamino; - each R ₁ is independently selected from H, C ₁ -C ₈ alkyl and C ₁ -C ₈ hydroxyalkyl; - each R ₂ is independently selected from C ₁ -C ₁₂ alkylene, C ₁ -C ₁₂ alkenylene, -CH ₂ -CH(OR ₁ )-CH ₂ , C ₈ -C ₁₂ alkarylene, C ₄ -C ₁₂ dihydroxy Alkylene _, poly(C ₂ -C ₄ alkyleneoxy _{)alkylene, H 2 CH} (OH)CH ₂ OR ₂ OCH ₂ CH(OH)CH ₂ - and C ₃ -C ₁₂ hydrocarbyl moieties;

-每一个R₃都独立地选自于H，R₂，O，C₁-C₂₀羟基烷基，C₁-C₂₀烷基，取代的烷基，C₆-C₁₁芳基，取代芳基，C₇-C₁₁烷基芳基，C₁-C₁₂氨基烷基，-(CH₂)_hCOOM，-(CH₂)_hSO₃M，CH₂CH(OH)SO₃M，-(CH₂)_hOSO₃M，

Provided that when R _is a _C3 - _C12 hydrocarbyl moiety, the hydrocarbyl moiety comprises from about 2 to about 4 branched moieties of the general formula:

- each R ₃ is independently selected from H, R ₂ , O, C ₁ -C ₂₀ hydroxyalkyl, C ₁ -C ₂₀ alkyl, substituted alkyl, C ₆ -C ₁₁ aryl, substituted aryl radical, C ₇ -C ₁₁ alkylaryl, C ₁ -C ₁₂ aminoalkyl, -(CH ₂ ) _h COOM, -(CH ₂ ) _h SO ₃ M, CH ₂ CH(OH)SO ₃ M, - (CH ₂ ) _h OSO ₃ M,

Among the cyclic amine-based compounds suitable for use in the present invention are those wherein at least about 10 mole %, preferably at least about 20 mole %, more preferably at least about 30 mole %, most preferably at least about 50 mole % of the _R groups are O, Provided that O is only present on the tertiary nitrogen.

及其混合物。-每一个R₄都独立地选自于H，C₁-C₂₂烷基，C₁-C₂₂羟基烷基，芳基和C₇-C₂₂烷基芳基；-每一个R₅都独立地选自于C₂-C₈亚烷基，C₂-C₈烷基取代的亚烷基；和A是相容的单价或二价或多价阴离子；M是相容的阳离子；b＝平衡电荷必需的数；每一个x都独立地是3至约1000，优选3-25，更优选4-20；每一个c都独立地是0或1；每一个h都独立地是约1至约8；每一个q都独立地是0至约6；每一个n都独立地是1至约20；每一个r都独立地是0至约20；和每一个t都独立地是0-1。Among them, the compounds suitable for the cyclic amine groups of the present invention are those compounds that meet the following conditions: - T and _R3 in the total number of groups, at least about 1.0%, preferably at least about 5.0%, more preferably at least about 10% %, most preferably at least about 20% is an anionic moiety selected from: -(CH ₂ ) _h COOM, -(CH ₂ ) _h SO ₃ M, CH ₂ CH(OH)SO ₃ M, -(CH ₂ ) _h OSO ₃ M,

and mixtures thereof. -each R ₄ is independently selected from H, C ₁ -C ₂₂ alkyl, C ₁ -C ₂₂ hydroxyalkyl, aryl and C ₇ -C ₂₂ alkylaryl; -each R ₅ is independently is selected from C ₂ -C ₈ alkylene, C ₂ -C ₈ alkyl substituted alkylene; and A is a compatible monovalent or divalent or multivalent anion; M is a compatible cation; b= The number necessary to balance the charge; each x is independently 3 to about 1000, preferably 3-25, more preferably 4-20; each c is independently 0 or 1; each h is independently about 1 to about 8; each q is independently 0 to about 6; each n is independently 1 to about 20; each r is independently 0 to about 20; and each t is independently 0-1 .

These cyclic amine-based polymers may be linear or branched. A specific kind of branching can be introduced with a multifunctional cross-linking agent. An example of such a polymer is illustrated below.

The Examples section below includes various non-limiting examples of cyclic amine polymers of the present invention.

1) Cyclic amines such as imidazole, alkylimidazole, aminoalkylimidazole, benzimidazole, piperazine, aminoalkylpiperazine, bis(N-aminoalkyl)piperazine, aminoalkylmorpholine, aminoalkyl Piperidine, and optionally acyclic amines and mixtures thereof;

2) crosslinking agent, which is selected from 1,2-dichloroethane, 1,2-dichloropropane, 1,3-dichloropropane, 1,3-dichloropropane-2-alcohol (1,3 dichloropronae-2-ol), 1,4-dichlorobutane, 1,6-dichlorohexane, epichlorohydrin, butylene oxide, 4,4′-dihydroxydiphenyl-dimethyl Bisglycidyl ethers of methane, dihalohydrins of _C2 - _C8 diols, bisglycidyl ethers of _C2 - _C8 diols (bisglycidyl ethers C2-C8 diols), polyalkylenes Bisglycidyl ethers of diols, and mixtures thereof.

为了织物外观和完整性益处的最优选的化合物是那些满足下述条件的化合物：-其中，每一个R₁都是H；和-至少一个W选自于： Preferred cyclic amino compounds falling within the above general formula include compounds satisfying the following conditions: - wherein each _R is H; and - at least one W is selected from: More preferred compounds for fabric appearance and integrity benefits are those wherein: - wherein each _R is H; and - at least one W is selected from:

Most preferred compounds for fabric appearance and integrity benefits are those wherein: - wherein each _R is H; and - at least one W is selected from:

Compounds preferably used as linking group _R include but are not limited to: polyepoxides, ethylene carbonate, propylene carbonate, urea, α,β-unsaturated carboxylic acids, α,β-unsaturated carboxylic acids Esters, amides of α,β-unsaturated carboxylic acids, α,β-unsaturated carboxylic anhydrides, di- or polycarboxylic acids, di- or polycarboxylates, amides of di- or polycarboxylic acids, di- or polycarboxylic anhydrides, shrinkage Glyceryl halides, chloroformates, chloroacetates, chloroformate derivatives, chloroacetate derivatives, epihalohydrins, α-dichloroglycerols, bis-(halohydrins), polyethers Dihalogenated compounds, phosgene, polyhalides, functionalized glycidyl ethers, and mixtures thereof.

In addition, R can _also include one or more polyether diamines, alkylene diamines, polyalkylene polyamines, alcohols, alkylene glycols and polyalkylene glycols with α, β- Reaction products of saturated carboxylic acids, esters of α,β-unsaturated carboxylic acids, amides of α,β-unsaturated carboxylic acids and anhydrides of α,β-unsaturated carboxylic acids, provided that these reaction products contain at least two bis bond, two carboxyl groups, two amide groups or two ester groups.

Other preferred cyclic amine-based polymers, oligomers or copolymers suitable for use in the present invention comprise adducts of two or more components selected from piperazine, piperadine, Imidazole, epichlorohydrin benzylquat (quat), epichlorohydrin methylquat, morpholine, and mixtures thereof. B) Semi-polar nonionic surfactant

A second essential ingredient of the laundry detergent compositions of the present invention is a semi-polar nonionic surfactant, preferably an amine oxide surfactant.

Semi-polar nonionic surfactants are a special class of nonionic surfactants comprising an alkyl moiety having from about 8 to about 18 carbon atoms and two alkyl moieties selected from the group consisting of about 1 to about 3 Water-soluble amine oxides of alkyl and hydroxyalkyl moieties of carbon atoms; containing 1 alkyl moiety having from about 8 to about 18 carbon atoms and 2 alkyl moieties selected from the group consisting of alkyl moieties having from about 1 to about 3 carbon atoms and hydroxyalkyl moieties; and containing an alkyl moiety having from about 8 to about 18 carbon atoms and being selected from the group consisting of alkyl and hydroxyalkyl moieties having from about 1 to about 3 carbon atoms Part of the water-soluble sulfoxide.

Preferred semi-polar nonionic detergent surfactants suitable for the purposes of the present invention are amine oxide surfactants having the formula: wherein: ^R3 is an alkyl group having from about 8 to about 22 carbon atoms, a hydroxyalkyl group, or an alkylphenyl group, or a mixture thereof; ^R4 is an alkylene group having from about 2 to about 3 carbon atoms, hydroxy Alkylene or a mixture thereof; x is 0 to about 3; and each ^R is an alkyl or hydroxyalkyl group having about 1 to about 3 carbon atoms or having about 1 to about 3 oxiranyl groups group of polyethylene oxide groups. These R ⁵ may be connected to each other, for example, via an oxygen or nitrogen atom to form a ring structure.

These amine oxide surfactants especially include C ₁₀ -C ₁₈ alkyl dimethyl amine oxide and C ₈ -C ₁₂ alkoxyethyl dihydroxyethyl oxide, more preferably C ₁₂ -C ₁₄ alkyl dimethyl Amine oxide.

The laundry detergent compositions of the present invention generally contain from 0.1% to 20%, preferably from about 1% to about 10%, more preferably from 2% to 7% by weight of such semi-polar nonionic surfactants. detergent components

The laundry detergent compositions of the present invention may contain other additional detergent ingredients. The exact nature of these additional components and the amount added will depend upon the physical form of the composition and the nature of the cleaning operation with which it is to be used.

The laundry detergent compositions of the present invention preferably further comprise nonionic and/or cationic surfactants, cellulose-based polymers or oligomers, dye transfer inhibiting polymers, mannanase and/or mixtures thereof.

When formulated for use in washing machine washing methods, the compositions of the present invention preferably contain a surfactant and a builder compound, and one or more additional compounds, preferably selected from the group consisting of organic polymeric compounds, bleaching agents, additional Detergent component of enzymes, suds suppressors, dispersants, lime soap dispersants, soil suspending agents, antiredeposition agents and corrosion inhibitors. Laundry compositions can also contain softening agents as additional detergent ingredients.

The compositions of the present invention can also be used as detergent additive products. Such additive products are used to supplement or enhance the performance of conventional detergent compositions.

The laundry detergent compositions of the present invention may be in the form of liquids, pastes, gels, bars, tablets, sprays, foams, powders or granules. Granular compositions can also be in "compressed" form, and liquid compositions can also be in "concentrated" form.

If desired, the laundry detergent compositions according to the invention have a density of 400-1200 g/l, preferably 500-950 g/l, measured at 20°C.

Compositions in "compressed" form according to the invention are best reflected by density and for the composition, by the amount of inorganic filler salt; inorganic filler salt is a traditional ingredient in detergent compositions in powder form; in traditional detergent compositions , the filler salt is present in large amounts, typically 17-35% of the total weight of the composition. In the compressed composition, the filler salt is present in an amount not exceeding 15%, preferably not exceeding 10%, most preferably not exceeding 5% by weight of the total composition. Inorganic filler salts such as those meant in the compositions of the present invention are selected from alkali and alkaline earth metal sulphates and chlorides. A preferred filler salt is sodium sulfate.

The liquid detergent compositions of the present invention may also be in "concentrated" form, in which case the liquid detergent compositions of the present invention contain a lower amount of water than conventional liquid detergents. The water content of the concentrated liquid detergents is generally preferably less than 40%, more preferably less than 30%, most preferably less than 20% by weight of the detergent composition.

Detergent compounds suitable for use in the present invention are selected from the compounds set forth below. Surfactant

The laundry detergent compositions of the present invention may also contain other detersive surfactants selected from anionic, nonionic, zwitterionic, amphoteric or cationic surfactants, or may contain these types of surfactants compatible mixture.

Preferably, the laundry detergent compositions of the present invention contain high levels of one or more nonionic surfactants and low levels of one or more anionic surfactants. More preferably, the laundry detergent compositions of the present invention contain nonionic surfactants in an amount of from 1% to 50% by weight of the total composition, most preferably from 5% to 30%, even most preferably from 15% -25%. More preferably, the laundry detergent compositions of the present invention comprise anionic surfactants in an amount of from 0% to 10%, most preferably from 0% to 5%. Even most preferably, the laundry detergent compositions of the present invention are free of anionic surfactants.

Preferred nonionic surfactants suitable for use in the laundry detergent compositions herein are the condensation products of primary and secondary fatty alcohols with from about 1 to about 25 moles of ethylene oxide, and/or mixtures thereof. The alkyl chain of the fatty alcohol may be straight or branched, primary or secondary, and generally contains from about 8 to about 22 carbon atoms. Preferred are the condensation products of alcohols having alkyl groups containing from about 8 to about 20 carbon atoms, more preferably from about 10 to about 18 carbon atoms, with about 2 to about 10 moles of ethylene oxide per mole of alcohol. There are about 3 to about 9 moles of ethylene oxide, and most preferably 5-7 moles of ethylene oxide, per mole of alcohol in the condensation product. Examples of commercially available nonionic surfactants of this type include Tergitol ^™ 15-S-9 (a condensation product of C ₁₁ -C ₁₅ linear alcohols with 9 moles of ethylene oxide), Tergitol ^™ 24-L-6NMW ( Condensation product of C ₁₂ -C ₁₄ primary alcohol with 6 moles of ethylene oxide, with narrow molecular weight distribution), both commercially sold by Union Carbide Corporation; Neodol ^TM 45-9 (C ₁₄ -C ₁₅ straight chain alcohol Condensation product with 9 moles of ethylene oxide), Neodol ^TM 23-3 (condensation product of C ₁₂ -C ₁₃ linear alcohols with 3.0 moles of ethylene oxide), Neodol ^TM 45-7 (C ₁₄ -C ₁₅ straight Condensation product of chain alcohol with 7 moles of ethylene oxide), Neodol ^TM 45-5 (condensation product of C ₁₄ -C ₁₅ linear alcohol with 5 moles of ethylene oxide), all sold by Shell Chemical Company; Kyro ^TM EOB (condensation product of C ₁₃ -C ₁₅ alcohols with 9 moles of ethylene oxide), commercially sold by the Procter & Gamble Company; and Genapol LA O3O or O5O (C ₁₂ -C ₁₄ alcohols with 3 or 5 moles of ethylene oxide Condensation products of alkanes), sold commercially by Hoechst. The preferred range of HLB in these products is 8-11, and 8-10 is most preferred.

Also useful as the nonionic surfactants of the present invention are the alkylpolysaccharides disclosed in U.S. Patent No. 4,565,647 issued to Llenado on January 21, 1986, which have from about 6 to about 30 carbon atoms, preferably from about 10 to Hydrophobic groups of about 16 carbon atoms and polysaccharides having from about 1.3 to about 10, preferably about 1.3 to about 3, most preferably about 1.3 to about 2.7 saccharide units, such as polyglucosides, hydrophilic groups. Any reducing sugar containing 5 or 6 carbon atoms can be used, such as glucose, galactose, and galactosyl moieties can be substituted for glucosyl moieties (optionally, the hydrophobic group attached at 2-, 3-, 4- Equivalently, glucose or galactose is opposed to glucoside or galactoside). The intersaccharide linkage may be, for example, between one position of the additional sugar unit and the 2-, 3-, 4- and/or 6-position of the preceding sugar unit.

Preferred alkyl polyglucosides have the formula:

R ² O(C _n H _2n O) _t (glycosyl) _x wherein, R ² is selected from alkyl, alkylphenyl, hydroxyalkyl, hydroxyalkylphenyl, and mixtures thereof, wherein the alkyl contains From about 10 to about 18, preferably from about 12 to about 14 carbon atoms; n is 2 or 3, preferably 2; t is from 0 to about 10, preferably 0; and x is from about 1.3 to about 10, preferably from about 1.3 to about 3, most preferably from about 1.3 to about 2.7. The glycosyl is preferably derived from glucose. To prepare these compounds, the alcohol or alkylpolyethoxylated alcohol is first formed and then reacted with glucose or a source of glucose to form the glucoside (attached at the 1-position). Additional glycosyl units may then be attached between their 1-position and the 2-, 3-, 4- and/or 6-position, preferably predominantly the 2-position, of the aforementioned glycosyl units.

Also useful as nonionic surfactants are the condensation products of ethylene oxide and a hydrophobic base formed by the condensation of propylene oxide with propylene glycol. The hydrophobic portion of these compounds preferably has a molecular weight of from about 1500 to about 1800 and exhibits water insolubility. The addition of a polyoxyethylene moiety to the hydrophobic moiety will generally increase the water solubility of the molecule, and the condensation product will retain its liquid properties up to a polyoxyethylene content of about 50% of the total weight of the condensation product, which is relative to Condensed with up to about 40 moles of ethylene oxide. Examples of such compounds include certain commercially available Plurafac ^™ LF404 and Pluronic ^™ surfactants, both sold by BASF.

Also suitable as nonionic surfactants are the condensation products of ethylene oxide and the product formed by the reaction of propylene oxide with ethylenediamine. The hydrophobic portion of these products consists of the reaction product of ethylenediamine with an excess of propylene oxide and generally has a molecular weight of from about 2500 to about 3000. The hydrophobic moiety is condensed with ethylene oxide to the extent that the condensation product contains from about 40 wt% to about 80 wt% polyoxyethylene and has a molecular weight of about 5,000 to about 11,000. Examples of such nonionic surfactants include certain of the commercially available Tetronic( ^TM) compounds, all sold by BASF.

Useful nonionic surfactants are also polyhydroxy fatty acid amide surfactants having the formula

其中，R¹是H，或者R¹是C_1-4烃基，2-羟基乙基，2-羟基丙基或其混合物，R²是C_5-31烃基，Z是具有至少有3个羟基直接连在该链上的直链烃基链的多羟基烃基或其烷氧基化衍生物。优选地是，R¹是甲基，R²是直链C_11-15烷基或C_16-18烷基或烯基如椰子油烷基或其混合物，Z是在还原氨化反应中衍生自还原糖如葡萄糖，果糖，麦芽糖，乳糖。:

Wherein, R ¹ is H, or R ¹ is a C _1-4 hydrocarbon group, 2-hydroxyethyl, 2-hydroxypropyl or a mixture thereof, R ² is a C _5-31 hydrocarbon group, and Z has at least 3 hydroxyl groups directly A polyhydroxyhydrocarbyl group or an alkoxylated derivative thereof of a linear hydrocarbyl chain attached to the chain. Preferably, R ¹ is methyl, R ² is straight chain C _11-15 alkyl or C _16-18 alkyl or alkenyl such as coconut oil alkyl or a mixture thereof, and Z is derived in a reductive amination reaction from Reducing sugars such as glucose, fructose, maltose, lactose.

Nonionic surfactants are also polyethylene oxide, polypropylene oxide and polybutylene oxide condensation products of alkylphenols, preferably polyethylene oxide condensation products. These compounds include the condensation products of alkylphenols and alkylene oxides having alkyl groups having from about 6 to about 14 carbon atoms, preferably from about 8 to about 14 carbon atoms, in straight and branched chain configurations. In a preferred embodiment, the ethylene oxide is present in an amount of about 2 to about 25 moles, more preferably about 3 to about 15 moles of ethylene oxide per mole of alkylphenol. Commercially available nonionic surfactants of this type include Igepal ^™ CO-630 sold by GAF Corporation; and Triton ^™ X-45, X-114, X-100 and X-102 all sold by Rohm & Haas Company. These surfactants are generally referred to as alkylphenol alkoxylates (eg, alkylphenol ethoxylates).

Cationic detersive surfactants suitable for use in the laundry detergent compositions of the present invention are those having a long chain hydrocarbyl group. Examples of such cationic surfactants include ammonium surfactants such as alkyltrimethylammonium halides, and those of the formula: [R ² (OR ³ ) _y ][R ⁴ (OR ³ ) _y ] ₂ R ⁵ N ^{+ X} -wherein, R ² is an alkyl or alkylbenzyl group with about 8 to about 18 carbon atoms in the alkyl chain, each R ³ is selected from -CH ₂ CH ₂ -, -CH ₂ CH(CH ₃ )-, -CH ₂ CH(CH ₂ OH)-, -CH ₂ CH ₂ CH ₂ -, and mixtures thereof; each R ⁴ is selected from C ₁ -C ₄ alkyl, C ₁ -C ₄ hydroxyalkyl, a benzyl ring structure formed by the combination of two R ⁴ groups, -CH ₂ CHOH-CHOHCOR ⁶ CHOHCH ₂ OH (where R ⁶ is any hexose sugar or a hexose sugar with a molecular weight less than about 1000 substance), and hydrogen (when y is not 0); R is the ^same as ^R , or is an alkyl chain in which R plus ^R has a total carbon number not greater than about ¹⁸ ; each y is from 0 to about 10 and the sum of the y values is from 0 to about 15; X is any compatible anion.

式I其中，R₁是短链长的烷基(C₆-C₁₀)或具有式(II)的烷基酰氨基烷基：式IIy是2-4，优选3。其中，R₂是H或C₁-C₃烷基，其中，x是0-4，优选0-2，最优选0，其中，R₃，R₄和R₅可以相同或不同，可以是短链烷基(C₁-C₃)或是具有式III的烷氧基化的烷基，其中，X^-是相反离子，优选是卤素离子，如氯离子或甲基硫酸根(methylsulfate)。式IIIR₆是C₁-C₄，z是1或2。Quaternary ammonium surfactants suitable for use in the present invention have the formula (I):

Formula I wherein R ₁ is short chain length alkyl (C ₆ -C ₁₀ ) or alkylamidoalkyl having formula (II): Formula IIy is 2-4, preferably 3. Wherein, R ₂ is H or C ₁ -C ₃ alkyl, wherein, x is 0-4, preferably 0-2, most preferably 0, wherein, R ₃ , R ₄ and R ₅ can be the same or different, and can be short Alkyl (C ₁ -C ₃ ) or alkoxylated alkyl having formula III, wherein X ⁻ is a counter ion, preferably a halide ion, such as chloride or methylsulfate. Formula IIIR ₆ is C ₁ -C ₄ , z is 1 or 2.

Preferred quaternary ammonium surfactants are those defined by formula I, wherein R ₁ is C ₈ , C ₁₀ or mixtures thereof, x=0, R ₃ , R ₄ =CH ₃ , and R ₅ =CH ₂ CH ₂ OH.

Highly preferred cationic surfactants are water-soluble quaternary ammonium compounds suitable for use herein having the formula: R ₁ R ₂ R ₃ R ₄ N ⁺ X ^- (i) wherein R ₁ is C ₈ -C ₁₆ alkyl , each of R ₂ , R ₃ and R ₄ is independently C ₁ -C ₄ alkyl, C ₁ -C ₄ hydroxyalkyl, benzyl, and -(C ₂ H ₄₀ ) _x H (where x is 2-5), X is an anion. There should be no more than one of _R2 , _R3 or _R4 be benzyl.

Preferred R ₁ alkyl chain lengths are C ₁₂ -C ₁₅ , especially when the alkyl group is a mixture of chain lengths derived from coconut or palm kernel oil or derived from olefin synthesis or OXO alcohol synthesis. Preferred _R2 , _R3 and _R4 groups are methyl or hydroxyethyl and the anion X may be selected from the group consisting of halogen, methylsulfate, acetate and phosphate ions.

并且R₂R₃R₄是甲基)。二烷基咪唑啉类化合物[式(i)的化合物]。Examples of quaternary ammonium compounds represented by formula (i) suitable for use in the present invention are: Coco trimethyl ammonium chloride or bromide; Coco methyl dihydroxyethyl ammonium chloride or bromide; Decyl triethyl ammonium chloride or bromide; Ammonium Chloride; Decyl Dimethyl Hydroxyethyl Ammonium Chloride or Bromide; C _12-15 Dimethyl Hydroxyethyl Ammonium Chloride or Bromide; Coco Dimethyl Hydroxyethyl Ammonium Chloride or Bromide ; myristyltrimethylammonium methylsulfate; lauryldimethylbenzylammonium chloride or bromide; lauryldimethyl(oxyethylene) ₄ ammonium chloride or bromide; choline esters ( A compound of formula (i), wherein R ₁ is

and R ₂ R ₃ R ₄ is methyl). Dialkylimidazolines [compounds of formula (i)].

Other cationic surfactants suitable for use in the present invention are also described in U.S. Patent 4,228,044, Cambre, issued October 14, 1980, and European Patent Application EP000224.

Other cationic materials are fabric softening components which include water insoluble quaternary ammonium fabric softening actives or their corresponding amine precursors, most commonly two long alkyl chain ammonium chlorides or methylsulfates.

Among these materials, preferred cationic softeners include: 1) dihydrogenated tallow dimethyl ammonium chloride (DTDMAC); 2) dihydrogenated tallow dimethyl ammonium chloride; 3) dihydrogenated tallow dimethyl ammonium Methylsulfate; 4) Distearyldimethylammonium chloride; 5) Dioleyldimethylammonium chloride; 6) Dipalmitylhydroxyethylmethylammonium chloride; 7) Stearylbenzene Methyl dimethyl ammonium chloride; 8) tallow trimethyl ammonium chloride; 9) hydrogenated tallow trimethyl ammonium chloride; 10) C _12-14 alkyl hydroxyethyl dimethyl ammonium chloride; 11) C _12-18 alkyl dihydroxyethyl methyl ammonium chloride; 12) bis(stearyloxyethyl) dimethyl ammonium chloride (DSOEDMAC); 13) bis(tallow-oxy-ethyl ) dimethylammonium chloride; 14) ditallow imidazoline methyl sulfate; 15) 1-(2-tallowamidoethyl)-2-tallow imidazoline methyl sulfate.

Biodegradable quaternary ammonium compounds as an alternative to the traditionally used two long alkyl chain ammonium chlorides or methyl sulfates. Such quaternary ammonium compounds contain long chain alkyl (alkenyl) groups interrupted by functional groups such as carboxyl groups. These materials and fabric softening compositions containing these materials are disclosed in publications such as EP-A-0040562 and EP-A-0239910.

The quaternary ammonium compounds and amine precursors of the present invention have the following formula (I) or (II): Wherein, Q is selected from -OC(O)-, -C(O)-O-, -OC(O)-O-, -NR ⁴ -C(O)-, -C(O)NR ⁴ -; R ¹ is (CH ₂ ) _n -QT ² or T ³ ; R ² is (CH ₂ ) _m -QT ⁴ or T ⁵ or R ³ ; R ³ is C ₁ -C ₄ alkyl or C ₁ -C ₄ hydroxyl Alkyl or H; R ⁴ is H or C ₁ -C ₄ alkyl or C ₁ -C ₄ hydroxyalkyl; T ¹ , T ² , T ³ , T ⁴ , T ⁵ are independently C ₁₁ -C ₂₂ alkane group or alkenyl; n and m are integers from 1 to 4; and X ^- is a softener compatible anion. Non-limiting examples of softener compatible anions include chloride and methylsulfate.

The alkyl, or alkenyl, chains ^T1 , ^T2 , ^T3 , ^T4 , ^T5 must contain at least 11 carbon atoms, preferably at least 16 carbon atoms. Chains can be straight or branched. Tallow is an inexpensive and readily available source of long chain alkyl and alkenyl materials. Particular preference is given to compounds wherein ^T1 , ^T2 , ^T3 , ^T4 , ^T5 represent a mixture of long chain materials, typically tallow.

Specific examples of quaternary ammonium compounds suitable for use in the aqueous fabric softening compositions of the present invention include:

N,N-di(tallow-oxygen-ethyl)-N,N-dimethylammonium chloride;

N,N-di(canolyl-oxygen-ethyl)-N,N-dimethylammonium chloride;

N, N-bis(tallow-oxygen-ethyl)-N-methyl, N-(2-hydroxyethyl)ammonium chloride;

N,N-di(canolyl-oxy-ethyl)-N-methyl,N-(2-hydroxyethyl)ammonium chloride;

N,N-bis(2-tallowyloxy-2-oxo-ethyl)-N,N-dimethylammonium chloride;

N,N-di(2-canolyl oxygen-2-oxo-ethyl)-N,N-dimethylammonium chloride;

N,N-bis(2-tallowyloxyethylcarbonyloxyethyl)-N,N-dimethylammonium chloride;

N,N-bis(2-canolyloxyethylcarbonyloxyethyl)-N,N-dimethylammonium chloride;

N-(2-tallowyloxy-2-ethyl)-N-(2-tallowyloxy-2-oxo-ethyl)-N,N-dimethylammonium chloride;

N-(2-canolyl oxygen-2-ethyl)-N-(2-canolyl oxygen-2-oxo-ethyl)-N,N-two Methyl ammonium chloride;

N,N,N-tris(tallowyl-oxygen-ethyl)-N-methylammonium chloride;

N,N,N-tris(canolyl-oxy-ethyl)-N-methylammonium chloride;

N-(2-tallowyloxy-2-oxoethyl)-N-(tallowyl)-N,N-dimethylammonium chloride;

N-(2-canolyl oxygen-2-oxoethyl)-N-(canolyl)-N,N-dimethylammonium chloride;

1,2-Ditallowyloxy-3-N,N,N-trimethylammoniumpropane chloride; and

1,2-Dicanolyloxy-3-N,N,N-trimethylammoniumpropane chloride; and

and mixtures of the above active substances.

When present, the laundry detergent compositions of the present invention generally contain from about 0.2% to about 25%, preferably from about 1% to about 8%, by weight of such cationic surfactants.

Traditionally used anionic surfactants themselves come in several different types. For example, water-soluble salts of higher fatty acids, ie "soaps", are suitable anionic surfactants for use in the compositions of the present invention. These include alkali metal soaps such as the sodium, potassium, ammonium and alkanolammonium salts of higher fatty acids containing from about 8 to about 24 carbon atoms, preferably from about 12 to about 18 carbon atoms. Soaps can be made by directly saponifying fats and oils, or by neutralizing them with free fatty acids. Particularly useful are the sodium and potassium salts of fatty acid mixtures derived from coconut oil and tallow, ie sodium or potassium tallow and coconut soap.

Other non-soap anionic surfactants suitable for use herein include alkyl groups having from about 10 to about 20 carbon atoms in their molecular structure (the alkyl portion of an acyl group is also included in the term "alkyl") and sulfonic acids or the water-soluble salts of organosulfur reaction products of sulfate groups, preferably alkali metal and ammonium salts. Examples of this combination of synthetic surfactants are a) sodium, potassium and ammonium alkyl sulfates, especially those obtained by sulfating higher alcohols (C ₈ -C ₁₈ carbon atoms) (such as those reducing tallow or coconut oil those obtained from glycerides of glycerides); b) sodium, potassium and ammonium alkyl polyethoxylate sulfates, especially those wherein the alkyl group contains 10-22, preferably 12-18 carbon atoms, and Salts with polyethoxylate chains containing 1-15, preferably 1-6 ethoxylate moieties; and c) sodium and potassium alkylbenzene sulfonates wherein the alkyl group contains from about 9 to about 15 carbons Atoms, the configuration of which is linear or branched, such as those kinds of salts described in US Pat. Particularly useful are linear alkylbenzene sulfonates wherein the average number of carbon atoms in the alkyl group is about 11-13, abbreviated _C11-13 LAS.

其中，R₁是C₆-C₁₂烷基，R₅是H或CH₃。适用于上述定义的表面活性剂中的特别优选的胺包括那些选自于辛基胺，己基胺，癸基胺，十二烷基胺，C₈-C₁₂双(羟基乙基)胺，C₈-C₁₂双(羟基异丙基)胺，C₈-C₁₂酰氨基丙基二甲基胺或其混合物的胺。在一个高度优选的实施方案中，用式R₁-C(O)-NH-(CH₂)₃-N(CH₃)₂表示胺基的表面活性剂，其中R₁是C₈-C₁₂烷基。纤维素基的聚合物或低聚物Surfactants suitable for use in the laundry detergent compositions of the present invention are also amine-based surfactants having the general formula: Wherein, R ₁ is C ₆ -C ₁₂ alkyl; n is about 2 to about 4, X is a bridging group selected from NH, CONH, COO or O, and there is no X; R ₃ and R ₄ are each independently selected from H, C ₁ -C ₄ alkyl, or (CH ₂ -CH ₂ -O(R ₅ )), wherein R ₅ is H or methyl. Particularly preferred amine-based surfactants include: R ₁ -(CH ₂ ) ₂ -NH ₂ R ₁ -O-(CH ₂ ) ₃ -NH ₂ R ₁ -C(O)-NH-(CH ₂ ) ₃ -N(CH ₃ ) ₂

Wherein, R ₁ is C ₆ -C ₁₂ alkyl, R ₅ is H or CH ₃ . Particularly preferred amines suitable for use in the surfactants defined above include those selected from the group consisting of octylamine, hexylamine, decylamine, dodecylamine, C ₈ -C ₁₂ bis(hydroxyethyl)amine, C Amines of ₈ -C ₁₂ bis(hydroxyisopropyl)amine, C ₈ -C ₁₂ amidopropyldimethylamine or mixtures thereof. In a highly preferred embodiment, amine-based surfactants are represented by the formula R ₁ -C(O)-NH-(CH ₂ ) ₃ -N(CH ₃ ) ₂ wherein R ₁ is C ₈ -C ₁₂ alkyl. Cellulose based polymers or oligomers

The laundry detergent compositions of the present invention may also contain one or more cellulose based polymers or oligomers. These materials have been found to impart appearance benefits to fabrics and textiles washed in aqueous wash solutions formed with detergent compositions comprising the cellulose-based fabric treatment materials. These fabric appearance benefits may include, for example, improved overall appearance of laundered fabrics, reduced pill and fuzz formation, resistance to fading, improved abrasion resistance, and the like.

One class of cellulosic based polymeric or oligomeric fabric treatment materials suitable for use herein has an average molecular weight of from about 5,000 to about 2,000,000, preferably from about 50,000 to about 1,000,000.

These cellulose-based compounds generally constitute from 0.1% to 5%, preferably from 0.5% to 4%, more preferably from 0.75% to 3%, by weight of the detergent compositions.

其中，每一个R选自于R₂，R_c和其中：-每一个R₂独立地选自于H和C1-C4烷基；-每一个R_c是其中，每一个Z独立地选自于M，R₂，R_c和R_H；-每一个R_H独立地选自于C₅-C₂₀烷基，C₅-C₇环烷基，C₇-C₂₀烷基芳基，C₇-C₂₀芳基烷基，取代的烷基，羟基烷基，C₁-C₂₀烷氧基-2-羟基烷基，C₇-C₂₀烷基芳氧基-2-羟基烷基，(R₄)₂N-烷基，(R₄)₂N-2-羟基烷基，(R₄)₃N-烷基，(R₄)₃N-2-羟基烷基，C₆-C₁₂芳氧基-2-羟基烷基，

-每一个R₄独立地选自于H，C₁-C₂₀烷基，C₅-C₇环烷基，C₇-C₂₀烷基芳基，C₇-C₂₀芳基烷基，氨基烷基，烷基氨基烷基，二烷基氨基烷基，哌啶子基烷基，吗啉代烷基，环烷基氨基烷基和羟基烷基；-每一个R₅独立地选自于H，C₁-C₂₀烷基，C₅-C₇环烷基，C₇-C₂₀烷基芳基，C₇-C₂₀芳基烷基，取代的烷基，羟基烷基，(R₄)₂N-烷基和(R₄)₃N-烷基；其中：M是合适的阳离子，其选自于Na，K，1/2Ca和1/2Mg；每一个x是0至约5；每一个y是约1至约5；且条件是：-R_H的取代度是约0.001-0.1，更优选约0.005-0.05，最优选约0.01-0.05；-其中Z是H或M的R_C的取代度是约0.2-2.0，更优选约0.3-1.0，最优选约0.4-0.7；-如果任一R_H带有正电荷，则有合适的阴离子进行电荷平衡；和-同一个氮原子上的两R₄′能够一起形成选自于哌啶和吗啉的环结构。A group of cellulose-based polymeric or oligomeric materials suitable for use in the present invention are characterized in that they have the formula:

wherein each R is selected from R ₂ , R _c and Wherein: - each R ₂ is independently selected from H and C1-C4 alkyl; - each R _c is Wherein, each Z is independently selected from M, R ₂ , R _c and R _H ; - each R _H is independently selected from C ₅ -C ₂₀ alkyl, C ₅ -C ₇ cycloalkyl, C ₇ -C ₂₀ alkylaryl, C ₇ -C ₂₀ arylalkyl, substituted alkyl, hydroxyalkyl, C ₁ -C ₂₀ alkoxy-2-hydroxyalkyl, C ₇ -C ₂₀ alkylaryl Oxygen-2-hydroxyalkyl, (R ₄ ) ₂ N-alkyl, (R ₄ ) ₂ N-2-hydroxyalkyl, (R ₄ ) ₃ N-alkyl, (R ₄ ) ₃ N-2 -Hydroxyalkyl, C ₆ -C ₁₂ aryloxy-2-hydroxyalkyl,

- each R ₄ is independently selected from H, C ₁ -C ₂₀ alkyl, C ₅ -C ₇ cycloalkyl, C ₇ -C ₂₀ alkylaryl, C ₇ -C ₂₀ arylalkyl, amino Alkyl, alkylaminoalkyl, dialkylaminoalkyl, piperidinoalkyl, morpholinoalkyl, cycloalkylaminoalkyl and hydroxyalkyl; each _R is independently selected from H, C ₁ -C ₂₀ alkyl, C ₅ -C ₇ cycloalkyl, C ₇ -C ₂₀ alkylaryl, C ₇ -C ₂₀ arylalkyl, substituted alkyl, hydroxyalkyl, (R ₄ ) ₂ N-alkyl and (R ₄ ) ₃ N-alkyl; wherein: M is a suitable cation selected from Na, K, 1/2Ca and 1/2Mg; each x is 0 to about 5 ; each y is from about 1 to about 5; and with the proviso that: -R _H has a degree of substitution of about 0.001-0.1, more preferably about 0.005-0.05, most preferably about 0.01-0.05; -R where Z is H or M The degree of substitution of _C is about 0.2-2.0, more preferably about 0.3-1.0, most preferably about 0.4-0.7; - if either R _H is positively charged, there is a suitable anion for charge balancing; and - the same nitrogen atom The two R ₄ ' on can together form a ring structure selected from piperidine and morpholine.

The "degree of substitution" of the R _H group, sometimes abbreviated as "DS _RH ", refers to the number of moles of R _H groups substituted per anhydroglucose unit, where the anhydroglucose unit is in the above general structure The six-membered ring shown in the repeating unit of .

The "degree of substitution" of the R _C group, sometimes abbreviated "DS _RC ", refers to the number of moles of R _C groups where Z is H or M that is substituted per anhydroglucose unit, where, anhydroglucose The unit is a six-membered ring as shown in the repeating unit of the general structure above. It is necessary to require Z to be H or M in order to ensure that there are enough carboxymethyl groups so that the resulting polymer is soluble. It should be understood that in addition to the desired number of _RC groups where Z is H or M, there may be, and most preferably are, other _RC groups where Z is other than H or M. detergent builder

The laundry detergent compositions of the present invention may also contain from 0.1% to 80% by weight of a detergent builder. The liquid form compositions preferably contain from about 1% to about 10% by weight of the builder component. The compositions in granular form preferably contain from about 1% to about 50% by weight of builder component. Detergent builders are well known in the art and can include, for example, phosphates and various organic and inorganic phosphate-free builders.

Water-soluble, phosphorus-free organic builders suitable for use herein include the various alkali metal, ammonium and substituted ammonium polyacetates, carboxylates, polycarboxylates and polyhydroxy sulfonates. Examples of polyacetate and polycarboxylate builders are sodium, potassium, lithium, ammonium and substituted ammonium ethylenediaminetetraacetate, nitrilotriacetate, oxydisuccinate, mellitidine salts, benzene polycarboxylates and citrates. Other polycarboxylates suitable for use in the present invention are the polyacetal carboxylates described in U.S. Patent 4,144,226, issued March 13, 1979 to Crutchfield et al. In U.S. Patent No. 4,246,495, these two patents are incorporated herein by reference. Particularly preferred polycarboxylate builders are oxydisuccinate and ether carboxylate builder compositions containing a combination of tartrate monosuccinate and tartrate disuccinate, described in May 1987. U.S. Patent No. 4,663,071, issued May 5 to Bush et al., which is incorporated herein by reference.

Examples of suitable phosphorus-free inorganic builders include silicates, aluminosilicates, borates and carbonates. Particularly preferred are sodium and potassium carbonates, bicarbonates, sesquicarbonates, tetraborate decahydrates and _SiO2 to alkali metal oxides in a weight ratio of from about 0.5 to about 4.0, preferably from about 1.0 to about 2.4 Silicates. Also preferred are aluminosilicates including zeolites. These materials and their use as detergent builders are fully described in US Patent No. 4,605,509 to Corkill et al., which patent is incorporated herein by reference. Crystalline layered silicates suitable for use in the detergent compositions of the present invention are also discussed in US Patent No. 4,605,509. optional detergent ingredients

The laundry detergent compositions of the present invention may also comprise any number of additional optional ingredients. These optional ingredients include conventional detergent composition components such as enzymes and enzyme stabilizers, suds boosters or suppressors, antitarnish and preservatives, bleaching agents, soil suspending agents, soil release agents, bactericides, pH Conditioners, sources of alkalinity for non-builders, chelating agents, organic and inorganic fillers, solvents, hydrotropes, optical brighteners, dye transfer inhibitors, dyes and fragrances.

In some applications where the pH of the wash solution is greater than about 10.0, a pH adjuster is necessary because the fabric integrity benefits of this defined composition begin to diminish at higher pHs. Therefore, if the pH of the wash solution is greater than about 10.0 after adding the cyclic amine-based polymer of the present invention, the pH of the wash solution should be lowered to below about 10.0, preferably about 10.0, with a pH regulator. 9.5 or less, most preferably about 7.5 or less. Suitable pH adjusting agents are well known to those of ordinary skill in the art.

Preferred optional ingredients for incorporation into the detergent compositions of the present invention include bleaching agents, such as peroxygen bleaches. The peroxygen bleach can be organic or inorganic in nature. Inorganic peroxygen bleaches are often used in combination with bleach activators.

Useful organic peroxygen bleaches include percarboxylic acid bleaches and their salts. Suitable examples of agents of this type include magnesium monoperoxyphthalate hexahydrate, magnesium m-chloroperbenzoate, 4-nonylamino-4-oxoperoxybutyrate and Diperoxydodecyl dioate. Such bleaching agents are disclosed in U.S. Patent 4,483,781 issued to Hartman on November 20, 1984; European Patent Application EP-A-133354 of Banks et al. published on February 20, 1985; U.S. 4,412,934 issued to Chung et al. on the 1st. Highly preferred bleaching agents also include 6-nonylamino-6-oxoperoxycaproic acid (NAPAA) described in U.S. Patent 4,634,551, Burns et al., issued January 6,1987.

Inorganic peroxygen bleaches can also be used, typically in granular form in the detergent compositions herein. In fact, the use of inorganic bleaching agents is preferred. Such inorganic peroxygen compounds include alkali metal perborate and percarbonate materials. For example, sodium perborate (eg, monohydrate or tetrahydrate) may be used. Suitable inorganic bleaches also include sodium or potassium carbonate peroxyhydrate and equivalent "percarbonate" bleaches, sodium pyrophosphate peroxyhydrate, urea peroxyhydrate and sodium peroxide. Persulfate bleaches (eg, OXONE commercially available from DuPont) can also be used. Inorganic peroxygen bleaches are usually coated with silicates, borates, sulfates or water soluble surfactants. For example, coated percarbonate particles are available from several commercial sources such as FMC, Solvay Interox, Tokai Denka and Degussa.

Inorganic peroxygen bleaches, such as perborates, percarbonates, etc., are preferably used in combination with bleach activators for in situ (i.e., after washing/bleaching with the compositions of the present invention) an aqueous solution corresponding to the bleach activator. Fabric process) generates peroxyacids. Various non-limiting examples of activators are disclosed in U.S. Patent No. 4,915,854, issued April 10, 1990 to Mao et al. and U.S. Patent No. 4,412,934 issued November 1, 1983 to Chung et al. Typically and preferably nonanoyloxybenzenesulfonate (NOBS) and tetraacetylethylenediamine (TAED) activators are used. Mixtures thereof can also be used. See also U.S. Patent 4,634,551, referenced above, for other typical bleaches and activators suitable for use herein.

Other useful amido-derived bleach activators are those of 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 is an alkyl group having about 6 to about 12 carbon atoms, R ² is an alkylene group having about 1 to about 6 carbon atoms, R ⁵ is H or has about 1 An alkyl, aryl or alkaryl group of up to about 10 carbon atoms, L being any suitable leaving group. A leaving group is any group which is removed from the bleach activator as a result of nucleophilic attack on the bleach activator with the perhydrolyzed anion. The leaving group is preferably phenolsulfonate.

Preferred examples of bleach activators of the above formula include: (6-octanoylamino-caproyl)oxybenzenesulfonate, (6-nonanoylaminocaproyl)oxybenzenesulfonate, (6-decanoylamino-hexanoyl) Acyl)oxybenzenesulfonates and mixtures thereof, these materials are described in the above-referenced US Patent No. 4,634,551. Another class of useful bleach activators includes the benzoxazine-type activators disclosed in US Patent 4,966,723, Hodge et al., issued October 30, 1990, which is incorporated herein by reference. Highly preferred benzoxazine-type activators are

Another class of useful bleach activators includes acyl lactam activators, especially acyl caprolactams and acyl valerolactams having the formula: wherein ^R6 is H or an alkyl, aryl, alkoxyaryl, or alkaryl group having 1 to about 12 carbon atoms. Highly preferred lactam activators include benzoyl caprolactam, octanoyl caprolactam, 3,5,5-trimethylhexanoyl caprolactam, nonanoyl caprolactam, decanoyl caprolactam, undecylenoyl caprolactam, benzoyl valerolactam Amides, octanoyl valerolactam, nonanoyl valerolactam, decanoyl valerolactam, undecylenoyl valerolactam, 3,5,5-trimethylhexanoyl valerolactam and mixtures thereof. See also US Patent No. 4,545,784, Sanderson, issued October 8, 1985, which is incorporated herein by reference, which discloses acyl caprolactams, including benzoyl caprolactam, absorbed in sodium perborate.

Peroxygen bleach, if employed, will comprise from about 2% to about 30% by weight of the detergent compositions herein. More preferably, the peroxygen bleach comprises from about 2% to about 20% by weight of the composition. Most preferably, the peroxygen bleach comprises from about 3% to about 15% by weight of the composition. Bleach activators, if employed, comprise from about 2% to about 10% by weight of the detergent compositions herein. Generally, the amount of activator is such that the molar ratio of bleach to activator is from about 1:1 to 10:1, more preferably from about 1.5:1 to 5:1.

Another highly preferred optional ingredient in the detergent compositions of the present invention is a detersive enzyme component. The enzymes contained in the compositions of the present invention serve a variety of purposes including removing protein-based, sugar-based or triglyceride-based soils from substrates, preventing release dye transfer from fabric washes, and restoring fabrics to their original condition. Suitable enzymes include proteases, amylases, lipases, cellulases, peroxidases, mannanases and mixtures thereof, which may be of any suitable origin, such as vegetable, animal, bacterial, fungal and yeast origin. The preferred choice is influenced by various factors such as pH activity and/or stability, optimum thermostability and stability to active detergents, builders, and the like. In this respect bacterial or fungal enzymes are preferred, such as bacterial amylases and proteases and fungal cellulases.

"Detergent enzyme" is used herein to mean any enzyme that provides cleaning, stain removal and other benefits in laundry detergent compositions. Preferred enzymes for washing purposes include, but are not limited to, proteases, cellulases, lipases, amylases and peroxidases.

Generally, enzymes are incorporated into detergent compositions in an amount sufficient to provide a "cleaning effective amount". The term "cleaning effective amount" refers to all amounts capable of producing cleaning, stain removal, soil removal, whitening, deodorizing or refreshment improving benefits on substrates, such as fabrics. In presently practical commercial preparations, the amount of active enzyme is generally up to about 5 mg per gram of detergent composition, more typically from 0.01 mg to 3 mg by weight. Unless otherwise specified, the composition of the present invention generally contains 0.001wt%-5wt%, preferably 0.01wt%-1wt% of commercial enzyme preparation. Generally, the amount of protease in such commercial preparations should be sufficient to produce an activity of 0.005-0.1 Anson Units (AU) per gram of composition. Higher active levels may be required in highly concentrated detergent formulations.

Examples of suitable proteases are subtilisins, which are obtained from special strains of Bacillus subtilis and Bacillus licheniformis. A suitable protease is the protease obtained from a Bacillus strain having maximal activity throughout the pH range 8-12 developed by Novo Industries A/S, Denmark, hereinafter referred to as "Novo" and marketed as ESPERASE(R). The preparation of this enzyme and analogous enzymes is described in British Patent GB 1,243,784 to Novo. Other suitable proteases include ALCALASE® and SAVINASE® marketed by Novo and MAXATASE® marketed by International Bio-Synthetics, Inc., The Netherlands; and Protease A disclosed in EP 130756A, Jan. Protease B in EP 303761A of April 28 and EP 130756A of January 9, 1985. See also a description of the high pH protease produced by Bacillus sp. NCIMB 40338 described in WO 9318140 A to Novo. Enzymatic detergents comprising a protease, one or more other enzymes and a reversible protease inhibitor are described in WO 9203529 A to Novo. Other preferred proteases include those in WO 9510591 A to Procter & Gamble. When desired, proteases with reduced adsorption and increased hydrolysis are commercially available as described in WO 9507791 to Procter & Gamble. Recombinant trypsin-like proteases suitable for use in the detergents of the present invention are described in WO 9425583 to Novo.

Cellulases suitable for use in the present invention include bacterial and fungal types of cellulases, preferably, these cellulases have an optimum pH range of 5-10. U.S. 4435307, Barbesgaard et al., March 6, 1984, discloses suitable fungal cellulases produced by Humicola insolens or Humicola strain DSM1800 or cellulase 212-producing fungi belonging to the genus Aeromonas, and from marine Cellulase extracted from the hepatopancreas of molluscs, DolabellaAuricula Solander. Suitable cellulases are also disclosed in GB-A-2075028; GB-A-2095275 and DE-OS-2247832. CAREZYME(R) and CELLUZYME(R) (Novo) are particularly useful. See also WO 9117243 issued to Novo.

Compositions of the invention may include amylases (alpha and/or beta) for removal of sugar-based soils. Cleaning compositions incorporating mutant amylases are described in WO 94/02597, Novo Nordisk A/S, published February 3, 1994. See also WO 95/10603, NovoNordisk A/S, published April 20, 1995. Other known amylases for use in cleaning compositions include alpha- and beta-amylases. Alpha-amylases are well known in the art, including those disclosed in U.S. Patents U.S. 5,003,257; EP 252,666; WO/91/00353; FR 2,676,456; EP 285,123; EP 525,610; of amylase. Other suitable amylases are the stability-enhanced amylases (described in WO 94/18314, published August 18, 1994, and WO 96/05295, published February 22, 1996, by Genencor) and available in Novo Nordisk There are additional modified amylase variants in the immediate parent of the A/S commercially available as disclosed in WO 95/10603 published April 1995. Other suitable amylases are described in EP 277 216, WO 95/26397 and WO 96/23873 (both Novo Nordisk applications). Examples of commercial alpha-amylase products are Purafect Ox Am® commercially available from Genencor and Termamyl®, Ban®, Fungamyl® and Duramyl® all commercially available from Novo Nordisk A/S Denmark. Other suitable amylases are described in WO 95/26397: α-amylase, characterized by a Phadebas® α-amylase activity assay at a temperature of 25-55°C and a pH in the range of 8-10 Provides a specific activity at least 25% higher than that of Termamyl(R). Suitable are variants of the above mentioned enzymes as described in WO 96/23873 (Novo Nordisk). Other amylolytic enzymes with improved properties with respect to activity level and thermostability in combination with higher activity levels are described in WO 95/35382.

Lipases suitable for detergent use include those produced by microorganisms of the Pseudomonas group, such as Pseudomonas stutzeri ATCC 19.154 disclosed in British Patent GB 1,372,034. See also lipases described in Japanese Patent Application No. 5320487, published February 24, 1978. This lipase is commercially available from Amano Pharmaceutical Co. Ltd., Nagoya, Japan under the trade name Lipase P "Amano" or "Amano-P". Other suitable commercially available lipases include Amano-CES, a lipase obtained from Chromobacter viscosum, e.g. Chromobacter viscosum var. lipolyticum NRRLB 3673 from Toyo Jozo Co., Tagata, Japan lipase from U.S. Biochemical Corp., U.S.A and Disoynth Co. The Netherlands obtained from Chromobacterium viscosus lipase and from Pseudomonas gladioli. A preferred lipase for use in the present invention is the LIPOLASE(R) enzyme derived from Humicola lanuginosa and commercially available from Novo (see also EP 341947).

A preferred enzyme for use in the compositions of the invention is mannanase. It includes the following three mannan-decomposing enzymes: EC 3.2.1.25: β-mannosidase, EC 3.2.1.78: endo-1,4-β-mannosidase, hereinafter referred to as "mannosidase )" and EC 3.2.1.100: 1,4-β-mannobiosidase (mannobiosidase) (IUPAC Classification - Enzyme Nomenclature, 1992 ISBN 0-12-227165-3 Academic Press). Preferably, the detergent compositions of the present invention contain beta-1,4-mannosidase (EC 3.2.1.78) known as "mannanase". In fact, it has been found that compositions of the invention further comprising mannanase provide excellent color care while maintaining super clean performance.

Preferably, the mannanase is an alkaline mannanase as defined below, more preferably a mannanase obtained from bacterial origin. The composition of the invention comprises in particular an alkaline mannanase selected from the group consisting of: mannanase obtained from strain Bacillus agaradhaerens NICMB 40482; mannanase obtained from Bacillus subtilis strain 168, gene yght Glycanase; mannanase from Bacillus sp. 1633; mannanase from Bacillus sp. AAI12 and/or mannanase from strain Bacillus halodurans. The most preferred mannanase for inclusion in the detergent compositions of the present invention is the mannanase produced by Bacillus sp. 1633, which is described in WO 99/64619. The term "alkaline mannanase" refers to an enzyme comprising at least 10%, preferably at least 25%, more preferably at least 40% of the maximum activity in a given pH range of 7-12, preferably 7.5-10.5 .

A first more preferred mannanase for use in the present invention is the alkaline mannanase obtained from Bacillus agaradhaerens NICMB 40482 described in WO 99/64619. More specifically, the mannanase is:

i) polypeptides produced by Bacillus agaradhaerens, NCIMB 40482;

or

ii) a polypeptide comprising the amino acid sequence shown in positions 32-344 of SEQ ID NO: 6 as shown in WO 99/64619; or

iii) an analogue of the polypeptide as defined in i) or ii), which is at least 70% homologous to said polypeptide, or which is derived from said polypeptide by substitution, deletion or addition of one or more amino acids, or which is purified from Polyclonal antibodies produced by forms of the polypeptide present an immunological response.

The invention also includes a corresponding isolated polypeptide having mannanase activity selected from the group consisting of:

(a) a polynucleotide molecule encoding a mannanase active polypeptide, which contains the nucleotide sequence shown in nucleotide 94-nucleotide 1032 in SEQ ID NO: 5 as shown in WO99/64619;

(b) species homologs of (a);

(c) a polynucleotide molecule encoding a polypeptide having mannanase activity at least 70% identical to the amino acid sequence from amino acid residue 32 to amino acid residue 344 of SEQ ID NO: 6 shown in WO 99/64619 ;

(d) a molecule complementary to (a), (b) or (c); and

(e) The degenerate nucleotide sequence of (a), (b), (c) or (d).

The plasmid pSJ1678 containing the polynucleotide molecule (DNA sequence) encoding the mannanase was transformed into an Escherichia coli strain, which was deposited by the inventor at the internationally recognized depository of microorganisms for patent procedures, the German Deposit of Microorganisms under the Budapest Treaty Center (the Deutsche Sammlung von Mikroorganismen und Zellkulturen GmbH, Mascheroder Weglb, D-38124 Braunschweig, Federal Republic of Germany) deposited on May 18, 1998 under the accession number DSM 12180.

A second more preferred enzyme is the mannanase obtained from Bacillus subtilis strain 168 described in U.S. Patent No. 6,060,299. More specifically, the mannanase is:

i) coded by the coding portion of the DNA sequence shown in SED ID No.5 as shown in U.S. Patent No.6060299 or an analog of said sequence; and/or

ii) a polypeptide containing the amino acid sequence shown in SEQ ID No. 6 as shown in U.S. Patent No. 6060299; or

iii) An analogue of the polypeptide as defined in ii), which is at least 70% homologous to said polypeptide, or which is derived from said polypeptide by substitution, deletion or addition of one or several amino acids, or which is identical to said polypeptide in purified form The polyclonal antibody produced by the polypeptide showed an immunological reaction.

The invention also includes a corresponding isolated polypeptide having mannanase activity selected from the group consisting of:

(a) a polynucleotide molecule encoding a polypeptide with mannanase activity and containing the nucleotide sequence shown in SEQ ID NO: 5 as shown in U.S. Patent No. 6060299;

(b) homologues of (a);

(c) a polynucleotide molecule encoding a polypeptide having mannanase activity at least 70% identical to the amino acid sequence of SEQ ID NO: 6 as shown in U.S. Patent No. 6060299;

(d) a molecule complementary to (a), (b) or (c); and

(e) The degenerate nucleotide sequence of (a), (b), (c) or (d).

A third more preferred enzyme is described in WO 99/64619. More specifically, the mannanase is:

i) a polypeptide produced by Bacillus sp. I633;

ii) a polypeptide comprising the amino acid sequence shown in positions 31-330 of SEQ ID NO: 2 as shown in WO 99/64619; or

iii) An analogue of the polypeptide as defined in i) or ii), which is at least 65% homologous to said polypeptide, obtained from said polypeptide by substitution, deletion or addition of one or several amino acids, or with anti-purification The polyclonal antibody produced by the polypeptide in the form of the polypeptide is immunologically reactive.

The invention also includes corresponding isolated polynucleotide molecules selected from the group consisting of:

(a) coding has mannanase active polypeptide, and contains the polynucleotide of the nucleotide sequence shown in nucleotide 94-nucleotide 990 in SEQ ID NO:1 as shown in WO 99/64619 molecular;

Homologues of (b) and (a);

(c) a polynucleotide molecule encoding a polypeptide having mannanase activity at least 65% identical to the amino acid sequence from amino acid residue 31 to amino acid residue 330 of SEQ ID NO: 2 as shown in WO 99/64619 ;

(d) a molecule complementary to (a), (b) or (c); and

(e) The degenerate nucleotide sequence of (a), (b), (c) or (d).

The plasmid pBXM3 containing the polynucleotide molecule (DNA sequence) encoding the mannanase of the present invention was transformed into an Escherichia coli strain, which was deposited by the inventor at the internationally recognized depository of microorganisms for patent procedures under the Budapest Treaty, Germany The Deutsche Sammlung von Mikroorganismen und Zellkulturen GmbH, Mascheroder Weg lb, D-38124 Braunschweig, Federal Republic of Germany was deposited on May 29, 1998 under the accession number DSM 12197.

A fourth more preferred enzyme is described in WO 99/64619. More specifically, the mannanase is:

i) a polypeptide produced by Bacillus sp. AAI 12;

ii) a polypeptide comprising the amino acid sequence shown in positions 32-362 of SEQ ID NO: 10 as shown in WO 99/64619; or

iii) an analogue of the polypeptide defined in i) or ii), which is at least 65% homologous to said polypeptide, or which is derived from said polypeptide by substitution, deletion or addition of one or several amino acids, or which is Polyclonal antibodies produced by the polypeptide in purified form are immunologically reactive.

The invention also includes corresponding isolated polynucleotide molecules selected from the group consisting of:

(a) a polynucleotide molecule encoding a polypeptide having mannanase activity and containing the nucleotide sequence shown in nucleotide 94-nucleotide 1086 in SEQ ID NO: 9 as shown in WO 99/64619 ;

(b) homologues of (a);

(c) a polynucleotide molecule encoding a polypeptide having mannanase activity at least 65% identical to the amino acid sequence from amino acid residue 32 to amino acid residue 362 in SEQ ID NO: 10 shown in WO 99/64619 ;

(d) a molecule complementary to (a), (b) or (c); and

(e) The degenerate nucleotide sequence of (a), (b), (c) or (d).

The plasmid pBXM1 containing the polynucleotide molecule (DNA sequence) encoding the mannanase of the present invention was transformed into an Escherichia coli strain which was deposited by the inventor at the internationally recognized depository of microorganisms for patent procedures under the Budapest Treaty, Germany The Microorganism Collection (the Deutsche Sammlung von Mikroorganismen und Zellkulturen GmbH, Mascheroder Weg lb, D-38124 Braunschweig, Federal Republic of Germany) was deposited on October 7, 1998 under the accession number DSM 12433.

A fifth more preferred enzyme is described in WO 99/64619. More specifically, the mannanase is:

i) polypeptides produced by Bacillus halodurans;

ii) a polypeptide comprising the amino acid sequence shown in positions 33-331 of SEQ ID NO: 12 as shown in WO 99/64619; or

iii) An analogue of the polypeptide as defined in i) or ii), which is at least 65% homologous to said polypeptide, or which is derived from said polypeptide by substitution, deletion or addition of one or several amino acids, or which is purified by The polyclonal antibody produced by the polypeptide in the form of the polypeptide is immunologically reactive.

The invention also includes corresponding isolated polynucleotide molecules selected from the group consisting of:

(a) a polynucleotide molecule encoding a polypeptide having mannanase activity and containing the nucleotide sequence shown in nucleotide 97-nucleotide 993 in SEQ ID NO: 11 as shown in WO 99/64619 ;

(b) homologues of (a);

(c) a polynucleotide molecule encoding a polypeptide providing mannanase activity that is at least 65% identical to the amino acid sequence from amino acid residue 33 to amino acid residue 331 of SEQ ID NO: 12 shown in WO 99/64619 ;

(d) a molecule complementary to (a), (b) or (c); and

(e) The degenerate nucleotide sequence of (a), (b), (c) or (d).

The plasmid pBXM5 containing the polynucleotide molecule (DNA sequence) encoding the mannanase of the present invention was transformed into an Escherichia coli strain obtained by the inventor at the internationally recognized depository of microorganisms for patent procedures under the Budapest Treaty, Germany The Microorganism Collection (the Deutsche Sammlung von Mikroorganismen und Zellkulturen GmbH, Mascheroder Weg lb, D-38124 Braunschweig, Federal Republic of Germany) was deposited on October 9, 1998 under the accession number DSM 12441.

The enzyme-containing compositions of the present invention may also optionally contain from about 0.001 wt% to about 10 wt%, preferably from about 0.005 wt% to about 8 wt%, most preferably from about 0.01 wt% to about 6 wt% of an enzyme stabilizing system. The enzyme stabilization system can be any stabilization system compatible with the detergent enzyme. This system can be provided by the other formulation actives themselves, or can be added separately, for example, by the formulator or the manufacturer of detergent-ready enzymes. The stabilizing system can include, for example, calcium ions, boric acid, propylene glycol, short chain carboxylic acids, boronic acids, and mixtures thereof, and is designed to address different stabilizing conditions depending on the type and physical form of the detergent composition. question.

The laundry detergent compositions of the present invention may also include dye transfer inhibiting compounds for inhibiting the transfer of dissolved and suspended dyes from one fabric to another during fabric laundering operations involving colored fabrics will meet. These compounds are generally contained in the laundry detergent compositions of the present invention in an amount of 0.001 wt% to 10 wt%, preferably 0.01 wt% to 2 wt%, more preferably 0.05 wt% to 1 wt%. Inhibit dye transfer from colored fabrics to co-washed fabrics with polymeric dye transfer inhibiting agents. These polymers are capable of complexing or absorbing fugitive dyes eluted from dyed fabrics before they have a chance to attach to other items in the wash. Particularly suitable polymeric dye transfer inhibiting agents are polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, polyvinylpyrrolidone polymers, polyvinyloxazolidone and polyvinyl imidazole or mixtures thereof. a) Polyamine N-oxide polymers

其中，P是可聚合单元，R-N-O基团可连接其上或R-N-O基团形成该可聚合单元的一部分，或二者的结合。A是

-O-，-S-，-N-；x是0或1；R是脂族乙氧基化脂族、芳族、杂环或脂环基团，或其任意组合，N-O基团上的氮可连接其上或N-O基团上的氮是这些基团的一部分。Polyamine N-oxide polymers suitable for use in the present invention contain units having the formula:

Where P is a polymerizable unit to which the RNO group may be attached or form part of the polymerizable unit, or a combination of both. A is

-O-, -S-, -N-; x is 0 or 1; R is an aliphatic ethoxylated aliphatic, aromatic, heterocyclic or alicyclic group, or any combination thereof, on the NO group The nitrogen to which the nitrogen may be attached or to the NO group is part of these groups.

其中，R1，R2和R3是脂族基，芳族、杂环或脂环基团，或其任意组合，x或/和y或/和z是0或1且其中N-O基团上的氮可连接或其中N-O基团上的氮形成这些基团的一部分。The NO group can be represented by the following general structure:

Wherein, R1, R2 and R3 are aliphatic groups, aromatic, heterocyclic or alicyclic groups, or any combination thereof, x or/and y or/and z are 0 or 1 and wherein the nitrogen on the NO group can be The nitrogen on the linkage or where the NO group forms part of these groups.

The N-O group can be part of the polymerizable unit (P) or attached to the polymeric backbone, or a combination of both.

Suitable polyamine N-oxides wherein the N-O group forms part of the polymerizable unit include polyamine N-oxides wherein R is selected from aliphatic, aromatic, alicyclic or heterocyclic groups.

One class of said polyamine N-oxides includes the group of polyamine N-oxides in which the nitrogen on the N-O group forms part of the R group. Preferred polyamine N-oxides are those wherein R is a heterocyclic group such as pyrimidine, pyrrole, imidazole, pyrrolidine, piperidine, quinoline, acridine and derivatives thereof.

Another class of said polyamine N-oxides includes a group of polyamine N-oxides in which the nitrogen on the N-O group is attached to the R group.

Other suitable polyamine N-oxides are polyamine oxides in which N—O groups are attached to polymerisable units.

A preferred class of these polyamine N-oxides are polyamine N-oxides of general formula (I) wherein R is an aromatic, heterocyclic or alicyclic group and wherein the nitrogen on the N-O functional group is part of said R group. oxide.

Examples of these classes are polyamine oxides where R is a heterocyclic compound such as pyrimidine, pyrrole, imidazole and their derivatives.

Another preferred class of polyamine N-oxides are polyamines providing general formula (I) wherein R is an aromatic, heterocyclic or alicyclic group and wherein the nitrogen on the N-O functional group is attached to said R group oxide.

Examples of these classes are polyamine oxides wherein R is an aromatic group such as phenyl.

Any polymer backbone can be used as long as the amine oxide polymer formed is water soluble and has dye transfer inhibiting properties. Examples of suitable polymeric backbones are polyvinyls, polyalkylenes, polyesters, polyethers, polyamides, polyimides, polyacrylates and mixtures thereof.

The ratio of amine to the amine N-oxide in the amine N-oxide polymers of the present invention is generally from 10:1 to 1:1,000,000. However, the amount of amine oxide groups present in the polyamine oxide polymer can be varied by suitable copolymerization or by a suitable degree of N-oxidation. The ratio of amine to amine N-oxide is preferably from 2:3 to 1:1000000. More preferably 1:4-1:1000000, most preferably 1:7-1:1000000. The polymers of the present invention actually include random or block copolymers in which one monomer type is an amine N-oxide and the other monomer type may or may not be an amine N-oxide . The amine oxide units of the polyamine N-oxides have a PKa<10, preferably a PKa<7, more preferably a PKa<6.

Polyamine oxides can be obtained in almost any degree of polymerization. The degree of polymerisation is not critical so long as the material has the desired water solubility and dye suspending capabilities.

Its average molecular weight is generally 500-1,000,000; preferably 1,000-50,000, more preferably 2,000-30,000, most preferably 3,000-20,000. b) Copolymers of N-vinylpyrrolidone and N-vinylimidazole

The average molecular weight of the N-vinylimidazole N-vinylpyrrolidone polymer used in the present invention is 5,000-1,000,000, preferably 5,000-200,000.

Highly preferred polymers for use in the laundry detergent compositions of the present invention include polymers selected from the group consisting of N-vinylimidazole N-vinylpyrrolidone copolymers, wherein said polymer has an average molecular weight of from 5,000 to 50,000 , more preferably 8000-30000, most preferably 10000-20000.

The average molecular weight range was determined by light scattering as described in Barth H.G. and Mays J.W. Chemical Analysis Vol 113, "Modern Methods of Polymer Characterization".

Highly preferred N-vinylimidazole N-vinylpyrrolidone copolymers have an average molecular weight of 5,000-50,000; more preferably 8,000-30,000; most preferably 10,000-20,000.

The N-vinylimidazole N-vinylpyrrolidone copolymers characterized by said average molecular weight range provide excellent dye transfer inhibiting properties without negatively affecting the cleaning performance of detergent compositions formulated therefrom.

In the N-vinylimidazole N-vinylpyrrolidone copolymer of the present invention, the molar ratio of N-vinylimidazole to N-vinylpyrrolidone is 1-0.2, more preferably 0.8-0.3, most preferably 0.6-0.4. c) Polyvinylpyrrolidone

Polyvinylpyrrolidone ("PVP") also useful in the laundry detergent compositions of the present invention has an average molecular weight of from about 2,500 to about 400,000, preferably from about 5,000 to about 200,000, more preferably from about 5,000 to About 50,000, most preferably, about 5,000 to about 15,000. Suitable polyvinylpyrrolidones are commercially available from ISP Corporation, New York, NY and Montreal, Canada under the product names PVP K-15 (viscosity molecular weight 10000), PVP K-30 (average molecular weight 40000), PVP K- 60 (average molecular weight is 160000) and PVP K-90 (average molecular weight is 360000). Other suitable commercially available polyvinylpyrrolidones from BASF Cooperation include Sokalan HP 165 and Sokalan HP 12; polyvinylpyrrolidones are well known to those of ordinary skill in the detergent art (for example: see EP-A-262897 and EP-A256696). d) Polyvinyloxazolidinone

Polyvinyloxazolidinones may also be used as polymeric dye transfer inhibiting agents in the laundry detergent compositions of the present invention. The average molecular weight of the polyvinyloxazolidinone is from about 2,500 to about 400,000, preferably from about 5,000 to about 200,000, more preferably from about 5,000 to about 50,000, most preferably from about 5,000 to about 15,000. e) Polyvinylimidazole

Polyvinylimidazoles can also be used as polymeric dye transfer inhibiting agents in the laundry detergent compositions of the present invention. The average molecular weight of the polyvinylimidazole is from about 2,500 to about 400,000, preferably from about 5,000 to about 200,000, more preferably from about 5,000 to about 50,000, most preferably from about 5,000 to about 15,000. f) Cross-linked polymers

Cross-linked polymers are polymers whose backbones are connected to each other to a certain extent; these connections can be chemical or physical, and can be connected to active groups on the backbone or branch chains; cross-linked polymers Described in Journal of Polymer Science, Vol. 22, pp. 1035-1039. In one embodiment, the cross-linked polymer is made in such a way as to form a three-dimensional rigid structure, the cross-linked polymer traps the dye in the pores formed by the three-dimensional structure. In another embodiment, the crosslinked polymer entraps the dye by swelling. Such crosslinked polymers are described in US5912221.

Additionally, pearlescent agents may optionally be included in the laundry detergent compositions of the present invention to improve product aesthetics. Suitable pearlescent agents are those known in the art to enable pearlescent effects in surfactant compositions. For example, pearlescent mica pigments such as Iriodin from Merck or equivalents such as Mearlin Magnapearl from Meare Corp., or organic compounds having the property of crystallizing into pearlescent needles in the product. Typical compounds with this property are polyol esters such as ethylene glycol mono- (EGMS) or di-stearate (EGDS), or polyethylene glycol mono- (PGMS) or distearate (PGDS ). There are several commercial sources for these materials. By way of example, but not exhaustively, PEG6000MS ex, available from Stepan, and Empilan EGDS/A, available from Albright & Wilson, are suitable pearlescent agents. Other suitable pearlescent agents can be found in WO 99/09944. It is well known to those skilled in the art that liquid products containing pearlescent agents and pearlescent crystal enhancers can also be added. Suitable enhancers are acids, salts, alcohols and esters with a hydrophobic moiety of at least 16C, preferably at least 18C; as described in EP520551B. It has been surprisingly found that the semi-polar nonionic surfactants and preferably the amine oxide compounds of the present invention can act as crystallization enhancers for organic pearlescent agents. Liquid detergent compositions comprising an organic pearlescent agent and a semi-polar nonionic surfactant, preferably an amine oxide, provide a very attractive pearlescent appearance. It has also been found that liquid laundry detergent compositions comprising the surfactant system of the present invention provide a particularly attractive pearlescent effect.

Preparation of detergent compositions

The laundry detergent compositions of the present invention can be prepared by combining the essential and optional ingredients in any suitable order and in any conventional manner at the necessary concentrations.

For example, granular compositions are typically prepared by mixing basic granular ingredients such as surfactants, builders, water, etc. into a slurry and spray drying the resulting slurry to low residual moisture (5-12%). The remaining dry ingredients, such as the requisite cyclic amine-based fabric treatment material in granular powder form, are mixed with the spray-dried granules in a rotating mixing drum. Solutions of liquid ingredients such as requisite cyclic amine-based fabric treatment materials, enzymes, binders and perfumes are sprayed onto the resulting granules to make the final detergent composition.

Liquid detergent compositions can be prepared by admixing the essential and optional ingredients in any desired order to produce a composition containing the components in the necessary concentrations. The liquid compositions of the invention may also be in "compressed form". In this case, the liquid detergent composition of the present invention contains a small amount of water compared to conventional liquid detergents. Cyclic amine based polymers, oligomers and copolymers can be successfully incorporated into liquid detergents and other aqueous compositions of the present invention by simply mixing the desired cyclic amine based fabric treatment material into the liquid solution Material.

fabric washing method

The present invention also provides a method of washing fabrics to impart to the fabrics produced by combining the semi-polar nonionic surfactant used in the present invention and a cyclic amine-based polymer, oligomer and copolymer material Benefits in cleaning and fabric appearance. The method involves contacting these fabrics with an aqueous wash solution formed with an effective amount of the above-described detergent composition, or with the individual components of the composition. Although aqueous non-agitated soaking solutions for fabric cleaning and treatment can be prepared using the compositions of the present invention, contacting of the fabrics with the wash solution will generally be carried out under agitation. As noted above, it is preferred that the pH of the wash solution is below about 10.0, preferably, the pH is about 9.5, most preferably about 7.5.

For good cleaning results, agitation is preferably carried out in a washing machine. After washing, the wet fabrics are preferably dried in a conventional laundry dryer. Concentrations of effective amounts of dense liquid or granular detergent compositions in aqueous wash solutions in washing machines are preferably from about 500 ppm to about 7000 ppm, more preferably from about 1000 ppm to about 3000 ppm.

Example

The following examples are intended to illustrate the compositions and methods of the invention and are not intended to limit or otherwise define the scope of the invention. Example 1

Synthesis of adducts of imidazole and epichlorohydrin (imidazole: epichlorohydrin = 1:1)

The polycation condensation product is prepared by reacting imidazole and epichlorohydrin. In a round bottom flask equipped with a magnetic stirrer, condenser and thermometer was charged imidazole (0.68 mol) and 95 mL of water. The solution was heated to 50°C, and then epichlorohydrin (0.68 mol) was added dropwise. After all the epichlorohydrin had been added, the temperature was raised to 80°C until all the alkylating agent was consumed. The resulting condensation product has a molecular weight of about 12,500. Example 2

Synthesis of adducts of imidazole and epichlorohydrin (imidazole: epichlorohydrin = 1.4:1)

In a round bottom flask equipped with a magnetic stirrer, condenser and thermometer was charged imidazole (0.68 mol) and 95 mL of water. The solution was heated to 50°C, and then epichlorohydrin (0.50 mol) was added dropwise. After all the epichlorohydrin had been added, the temperature was raised to 80°C until all the alkylating agent was consumed. The resulting condensation product has a molecular weight of about 2000. Example 3

Synthesis of adducts of piperazine, morpholine and epichlorohydrin (the ratio is 1.8/0.8/2.0)

Add 154.8 g (1.8 mol) of piperazine and 69.6 g (0.8 mol) of morpholine and 220 mL of water into a round bottom flask equipped with a stirrer, thermometer, dropping funnel and reflux condenser. After obtaining a transparent solution at 40°C, the solution was heated to 55-65°C, and 185 g (2 mol) of epichlorohydrin was added under vigorous stirring at a rate such that the temperature did not exceed 80°C. After all the epichlorohydrin had been added, the reaction mixture was heated to 85° C. until all the alkylating agent was consumed (negative Preussmann test after 4 hours). 108.8 g (0.68 mol) of 25% NaOH and 40 g of water were added and the reaction mixture was stirred at 85° C. for a further 1 hour. Then 47 g of water were added and the mixture was allowed to cool to room temperature. Example 4

Synthesis of adducts of piperazine and epichlorohydrin (piperazine (imidazole): epichlorohydrin = 1:1)

Piperazine (0.68 mol) and 95 mL of water were added to a round bottom flask equipped with a magnetic stirrer, condenser and thermometer. The solution was heated to 50°C, and then epichlorohydrin (0.68 mol) was added dropwise. After all the epichlorohydrin had been added, the temperature was raised to 80°C until all the alkylating agent was consumed. Example 5

1.4 molar equivalents of piperazine-based methyl chloride were added to the condensate from Example 4 and stirred until all the methyl chloride was consumed. Example 6

Synthesis of adducts of imidazole, piperazine and epichlorohydrin (imidazole: piperazine: epichlorohydrin=1:3:4)

68.8 g (1.0 mol) of imidazole and 260.6 g (3.0 mol) of piperazine were dissolved in 700.2 g of water, and 370 g (4.0 mol) of epichlorohydrin were added dropwise at 50-60°C. After the addition was complete, the reaction mixture was stirred at 80°C for an additional 5 hours. Embodiment 7 (a) the reaction that two (aminopropyl) piperazine and epichlorohydrin carry out with the molar ratio of 2:1

600 g (3 mol) of bis(aminopropyl)piperazine were dissolved in 750 g of water. The solution was heated to 90°C. As soon as this temperature was reached, 140.1 g (1.5 mol) of epichlorohydrin were added at 90° C. within 60 minutes. The reaction mixture was then stirred at 90°C for 150 minutes. Epichlorohydrin was subsequently undetectable. The condensation product contains NH groups. (b) Permethylation of the condensation product obtained in (a)

99.7 g (the amount of NH groups is 0.87 mol) of the condensation product obtained in (a) was mixed with 100.3 g (2.18 mol) of formic acid (99%) under stirring and then cooled in an ice bath. 104.5 g (1.045 mol) of a 30% strength by weight aqueous formaldehyde solution were added at room temperature over a period of 20 minutes. The reaction mixture was then carefully heated to 60°C. The evolution of carbon dioxide from the reaction mixture started at about 50°C and evolved substantially at 60°C. Therefore, heating can be stopped at this time. After the evolution of carbon dioxide had slowed, the reaction mixture was refluxed for 12 hours. After cooling, 100 ml of concentrated hydrochloric acid was added, and the reaction mixture was dehydrated. After 153.6 g of solid was obtained, it was dissolved in water to form a 50% by weight polymer solution of cyclic amine groups substantially free of primary and secondary amino groups. More than 90% of the NH groups were converted to tertiary nitrogen atoms as determined by 13C-NMR spectroscopy. The amount of quaternary ammonium groups in the polymer is less than 5%. The pH of the aqueous polymer solution was 9.58. The k value of the polymer was 8.6. Example 8

A solution of 92.6 g (1.36 mol) of imidazole in 140.5 g of water was heated to 50° C. and combined within 10 minutes with a solution of 8.2 g (0.07 mol) of the sodium salt of 2-chloroacetic acid in 50 g of water. The solution is then heated to 65°C until all the sodium salt of 2-chloroacetic acid has reacted, which can be determined by analytically measuring the chloride ion content in the solution. While stirring, 5.6 g (0.07 mol) of 50 wt % aqueous sodium hydroxide solution and 89.7 g (0.97 mol) of epichlorohydrin were added within 30 minutes to keep the temperature of the reaction mixture at 55-65°C. After the addition of epichlorohydrin the reaction mixture was heated to 80° C. and stirred at this temperature for 4 hours. After 4 hours, no alkylating agent was detected. A yellow aqueous solution of 377.7 g of an amphoteric amine-based polymer having a net cationic charge of 4.2 mequiv per gram of polymer was obtained. The solution had a pH of 6.97 and contained 50.3% water, 0.06% glycolic acid and less than 0.05% 2-chloroacetic acid. The molecular weight of the polymer is Mn=700, Mw=1460 and Mw/Mn=2.1. Example 9

According to the step of embodiment 8, make the imidazole of 92.6g (1.36mol), the sodium salt of the 2-chloroacetic acid of 16.3g (0.14mol), the concentration of 11.2g (0.14mol) is the aqueous solution of the sodium hydroxide of 50wt%. React with 86.1 g (0.93 mol) of epichlorohydrin. A yellow aqueous solution of 386.3 g of an amphoteric amine-based polymer having a net cationic charge of 3.4 mequiv per gram of polymer was obtained. The solution has a pH of 7.10 and contains 49.6% water, 0.1% glycolic acid and less than 0.05% 2-chloroacetic acid. The molecular weight of the polymer is Mn=650, Mw=1320 and Mw/Mn=2.0. Example 10

According to the step of embodiment 8, make the imidazole of 92.6g (1.36mol) being dissolved in 122.6g water, the sodium salt of the 2-chloroacetic acid of 39.6g (0.34mol) being dissolved in 100g water, 27.2g (0.34mol) The concentration is 50wt% sodium hydroxide aqueous solution and 76.8g (0.83mol) epichlorohydrin reaction. A yellow aqueous solution of 386.3 g of an amphoteric amine-based polymer having a net cationic charge of 2.8 mequiv per gram of polymer was obtained. The solution had a pH of 7.82 and contained 53.4% water, 0.2% glycolic acid and less than 0.05% 2-chloroacetic acid. The molecular weight of the polymer is Mn=540, Mw=1060 and Mw/Mn=2.0. Example 11

Repeat embodiment 7, difference is: make the imidazole of 68.1g (1.0mol) be dissolved in 54.9g water, be dissolved in the sodium salt of the 2-chloroacetic acid of 72.0g (0.6mol) in 150g water, 48.0g ( 0.6mol) of 50wt% sodium hydroxide aqueous solution and 64.8g (0.mol) of epichlorohydrin were reacted. A deep yellow aqueous solution of 446.4 g of an amphoteric amine-based polymer having a net cationic charge of 3.2 mequiv per gram of polymer was obtained. The solution had a pH of 12.29 and contained 48.2% water, 0.5% glycolic acid and less than 0.05% 2-chloroacetic acid. The molecular weight of the polymer is Mn=740, Mw=1690 and Mw/Mn=2.3. Example 12

Repeat embodiment 8, difference is: make the imidazole of 71.5g (1.05mol) be dissolved in 116.3g water, be dissolved in the sodium salt of the 2-chloroacetic acid of 40.8g (0.34mol) in 100g water, 27.2g ( 0.24 mol) of 50 wt% sodium hydroxide aqueous solution and 76.8 g (0.83 mol) of epichlorohydrin were reacted. A yellow aqueous solution of 427.6 g of an amphoteric amine-based polymer having a net cationic charge of 3.7 mequiv per gram of polymer was obtained. The solution had a pH of 11.62 and contained 54.2% water, 0.3% glycolic acid and less than 0.05% 2-chloroacetic acid. The molecular weight of the polymer is Mn=1050, Mw=2380 and Mw/Mn=2.3. Example 13

Dissolve 68.1g (1mol) of imidazole in 73.6g of water and heat to 50°C. Once the temperature is reached, 73.5g (0.34mol) of 3-chloro-2- A solution of the sodium salt of hydroxypropanesulfonic acid in 150 g of water and 27.2 g (0.34 mol) of a 50% by weight aqueous solution of sodium hydroxide. The reaction mixture is then stirred at 65-90°C until all of the sodium salt of 3-chloro-2-hydroxypropanesulfonic acid has reacted, which can be determined analytically by measuring the chloride ion content of the solution. After cooling the solution to 55°C, 76.8 g (0.83 mol) of epichlorohydrin were added over 30 minutes at such a rate that the temperature of the reaction mixture was maintained at 55°C. After the addition of epichlorohydrin was complete, the reaction mixture was heated to 80°C and stirred at this temperature for 4 hours. After this time, no alkylating agent was detected in the reaction mixture. A clear yellow aqueous solution of 461.3 g of an amphoteric amine-based polymer having a net cationic charge of 2.9 mequiv per gram of polymer and a K value of 10.0 was obtained. The solution had a pH of 11.55 and contained 52.4% water. The molecular weight of the polymer is Mn=1800, Mw=3490 and Mw/Mn=1.95. Example 14

Repeat Example 13, difference is: make the imidazole of 34.1g (0.5mol) be dissolved in 31.3g water, be dissolved in the 2-chloroacetic acid sodium salt of 64.8g (0.35mol) in 100g water, 24.0g (0.3 mol) concentration of 50 wt% sodium hydroxide aqueous solution and 32.4g (0.35mol) of epichlorohydrin reaction. A clear yellow aqueous solution of 284.1 g of an amphoteric amine-based polymer having a net cationic charge of 3.3 mequiv per gram of polymer and a K value of 7.6 was obtained. The solution had a pH of 11.92 and contained 51.7% water. The molecular weight of the polymer is Mn=1100, Mw=1990 and Mw/Mn=1.80. Example 15

Synthesis of adducts of imidazole/piperazine/epichlorohydrin (epi) in a ratio of 1.0/3.0/4.0

100% oxidized

68.8 g (1.0 mol) of imidazole and 260.6 g (3.0 mol) of piperazine were dissolved in 700.2 g of water and 370 g (4.0 mol) of epichlorohydrin were added dropwise at 50-60°C. After the addition was complete, the reaction mixture was stirred at 80°C for an additional 5 hours. To 237 g of _this product (corresponding to 1022 mol of oxidizable nitrogen atoms) were added 80.7 g (1.12 mol) of 47.2% _H2O2 in water at 40° C. within 5 hours. Then, the mixture was heated to 50-60° C. until the theoretical amount of H ₂ O ₂ was consumed. Unreacted _H2O2 was destroyed with Pt/C, and _the solution was filtered.

The characteristics of the reaction product are as follows: Water content: 58.6% pH: 2.86 Chloride content: 3.694 mmol/g Mn (GPC): 340 Mw (GPC): 940 Mn/Mw: 2.8+/-0.1 Example 16

The following 2 groups of liquid laundry detergent compositions were prepared according to the present invention: I II III IV C _12-18 fatty acids 8.0 8.0 8.0 8.0 citric acid 2.0 2.0 2.0 2.0 C _12-14 Alcohol Ethoxylate 7EO 20.0 20.0 - 10.0 C _12-13 Alcohol Ethoxylate 9EO - - 20.0 - C _13-15 Alcohol Ethoxylate 5EO - - - 10.0 C _12-14 Dimethylamine Oxide 5.0 5.0 5.0 5.0 ethanol 2.0 2.0 - - Propylene Glycol 7.0 7.0 9.0 7.0 Monoethanolamine 5.0 5.0 5.0 5.0 Dispersant polymer 3.0 3.0 2.5 2.5 Phosphonate 1.0 1.0 - 1.0 Chelating agent - - 1.0 1.0 Cyclic amine-based polymers - The compounds and their amounts are shown in the table below enzyme 1.0 1.0 1.5 2.0 Ethylene Glycol Distearyl 0.5 1.0 - - borate 2.0 2.0 3.0 2.0 other and water reach 100% V VI VII VIII IX C _12-18 fatty acids - 8.0 8.0 8.0 - citric acid 7.0 2.0 2.0 2.0 6.0 C _12-14 Alcohol Ethoxylate 7EO 22.0 20.0 - 15.0 - C _12-13 Alcohol Ethoxylate 9EO - - 17.0 - - C _13-15 Alcohol Ethoxylate 5EO - - - - 23.0 C _12-14 Dimethylamine Oxide 3.0 3.0 5.0 4.0 2.5 C _8-10 amidopropyl dimethylamine - 1.5 - - - C _12-15 Alkyl Sulfate - 2.0 - 2.0 - C _12-15 Alkyl Ether 2.5EO Sulfate - - 3.0 - - C _14-15 Alkyl Ether 0.35EO Sulfate - - - 1.0 - linear alkylbenzene sulfonate - - - 2.0 - ethanol 1.0 - - - 1.0 Propylene Glycol 7.0 9.0 9.0 9.0 12.0 Monoethanolamine 7.0 6.5 5.0 5.0 7.5 Dispersant polymer 2.5 2.0 2.5 2.5 3.0 Phosphonate 1.0 0.5 - - 1.0 Chelating agent - - 1.0 1.0 - Cyclic amine-based polymers The compounds and their amounts are shown in the table below enzyme 0.8 2.0 1.5 1.5 1.0 Mannanase - - - - 0.3 Ethylene glycol distearyl ester - 1.0 - 1.0 - borate 2.0 2.0 2.5 2.0 2.0 other and water reach 100% Wherein, the definition of component is as follows: 1) the polymer of cyclic amine group is selected from one or more compounds listed in the following table 2) chelating agent is selected from ethylenediamine-N, N'-disuccinic acid , (S, S) isomer, use its sodium salt form and/or diethylenetriaminepentaacetic acid. 3) The enzyme is selected from the above-mentioned traditional protease, amylase, lipase and/or cellulase. Mannanase is a mannanase sold under the tradename Mannaway by Novo Nordisk A/S. 4) The dispersant polymer is a poly(ethyleneimine) ethoxylated polymer with a molecular weight of 200-3000 and an EO of 7-30. Example 17

The following are granular laundry detergent compositions prepared according to the present invention: I II III Sodium C ₁₂ linear alkylbenzene sulfonate 3.0 3.0 5.0 Sodium C _14-15 Alkyl Sulfonate 2.0 2.0 - Zeolite Builder 27.8 27.8 27.8 Sodium carbonate 27.3 27.3 27.3 PEG4000 1.6 1.6 1.6 Dispersant, sodium polyacrylate 2.3 2.3 2.3 C _12-13 Alkyl Ethoxylates (E9) 15.0 15.0 10.0 C _12-14 Dimethylamine Oxide 2.0 2.5 5.0 Polyvinylpyridine-N-oxide, the average molecular weight is 50000 0.5 - - cellulosic polymer 1.0 1.0 - sodium perborate 1.03 1.03 1.03 Cyclic amine-based polymers/oligomers Its dosage is shown in the table below other additives reach 100%

Wherein, cellulose polymer is carboxymethyl cellulose, it is characterized in that: Degree of carboxymethylation DS _RC =0.3-2.0; preferred DS _RC =0.5-0.70 Distribution of carboxymethyl groups Carboxymethyl groups are evenly and randomly distributed along the backbone molecular weight Mw: 5000-2000000. Preferred: intermediate values (about 250000 g/mol) Modified type Ether modification (except carboxymethylation). mixed cellulose ethers degree of modification DS _RH = about 0.001 to about 0.1

Wherein, the cyclic amine-based polymer/oligomer is selected from one or more compounds listed in the following table. The chemical structures shown in the examples below are idealized structures. Side reactions that may occur during the condensation are not shown in the table.

Claims (18)

1. A laundry detergent composition comprising a semi-polar nonionic surfactant and a cyclic amine-based polymer, oligomer or copolymer, wherein the cyclic amine-based polymer, oligomer or Copolymers provide the following general formula: Where: each T is independently selected from H, C ₁ -C ₁₂ alkyl, substituted alkyl, C ₇ -C ₁₂ alkylaryl, -(CH ₂ ) _h COOM, -(CH ₂ ) _h SO ₃ M, CH ₂ CH(OH)SO ₃ M, -(CH ₂ ) _h OSO ₃ M,

and -R ₂ Q; -wherein W includes at least one cyclic moiety selected from:

In addition to at least one cyclic moiety, W may also include aliphatic or substituted aliphatic moieties providing the general formula: -Each B is independently C ₁ -C ₁₂ alkenyl, C ₁ -C ₁₂ substituted alkenyl, C ₃ -C ₁₂ alkenylene, C ₈ -C ₁₂ dialkylarylene, C ₈ -C ₁₂ dialkylarylene diradicals and -(R ₅ O) _n R ₅ -; - each D is independently C ₂ -C ₆ alkylene; - each Q is independently selected from hydroxyl, C ₁ -C ₁₈ alkoxy, C ₂ -C ₁₈ hydroxyalkoxy, amino, C ₁ -C ₁₈ alkylamino, dialkylamino, trialkylamino, heterocyclic monoamino and diamino; - each R ₁ is independently selected from H, C ₁ -C ₈ alkyl and C ₁ -C ₈ hydroxyalkyl; -each R ₂ is independently selected from C ₁ -C ₁₂ alkylene, C ₁ -C ₁₂ alkylene alkenyl, -CH ₂ -CH(OR ₁ )-CH ₂ , C ₈ -C ₁₂ alkarylene, C ₄ -C ₁₂ dihydroxyalkylene, poly(C ₂ -C ₄ alkyleneoxy)alkylene Alkyl, H ₂ CH(OH)CH ₂ OR ₂ OCH ₂ CH(OH)CH ₂ - and a C ₃ -C ₁₂ hydrocarbyl moiety; provided that when R ₂ is a C ₃ -C ₁₂ hydrocarbyl moiety, the hydrocarbyl moiety can Including about 2 to about 4 branched moieties having the general formula:

- each R ₃ is independently selected from H, R ₂ , O, C ₁ -C ₂₀ hydroxyalkyl, C ₁ -C ₂₀ alkyl, substituted alkyl, C ₆ -C ₁₁ aryl, substituted aryl radical, C ₇ -C ₁₁ alkylaryl, C ₁ -C ₁₂ aminoalkyl, -(CH ₂ ) _h COOM, -(CH ₂ ) _h SO ₃ M, CH ₂ CH(OH)SO ₃ M, - (CH ₂ ) _h OSO ₃ M, -each R ₄ is independently selected from H, C ₁ -C ₂₂ alkyl, C ₁ -C ₂₂ hydroxyalkyl, aryl and C ₇ -C ₂₂ alkylaryl; -each R ₅ is independently selected from From C ₂ -C ₈ alkylene, C ₂ -C ₈ alkyl substituted alkylene; and A is a compatible monovalent or divalent or multivalent anion; M is a compatible cation; b = balance the The number necessary for the charge; each x is independently 3 to about 1000; each c is independently 0 or 1; each h is independently about 1 to about 8; each q is independently about 0 to about 6; Each n is independently about 1 to about 20; each r is independently about 0 to about 20; and each t is independently about 0 to about 1. 2. The laundry detergent composition according to claim 1, wherein said cyclic amine-based polymer, oligomer or copolymer is selected from piperazine, piperadine, epichlorohydrin, epichlorohydrin Benzylquat, Epichlorohydrin Methylquaternium, Morpholine, and mixtures thereof. 3. A laundry detergent composition according to claims 1-2, wherein each _R is H and at least one W is selected from:

4. A laundry detergent composition according to claims 1-3, wherein each _R is H and at least one W is selected from:

5. A laundry detergent composition according to claims 1-4, wherein each _R is H and at least one W is selected from:

6. A laundry detergent composition according to any preceding claim wherein x is 3-25, preferably 4-20. 7. A laundry detergent composition according to any preceding claim, wherein said cyclic amine-based polymer, oligomer or copolymer constitutes from 0.01% to 5%, preferably 0.1% by weight of the total composition. %-4%, more preferably 0.75%-3%. 8. A laundry detergent composition according to any preceding claim, wherein said semi-polar nonionic surfactant constitutes from 0.1% to 20%, preferably from 1% to 10%, more preferably by weight of the total composition Preferably 2%-7%. 9. A laundry detergent composition according to any preceding claim, wherein the semi-polar nonionic surfactant is an amine oxide surfactant, preferably selected from the group consisting of C ₁₀ -C ₁₈ alkyl dimethyl amine oxide and C ₈ -C ₁₂ alkoxyethyl dihydroxyethyl oxide, C ₁₂ -C ₁₄ alkyl dimethylamine oxide and/or mixtures thereof, more preferably C ₁₂ -C ₁₄ alkyl Dimethylamine Oxide. 10. A laundry detergent composition according to any preceding claim, further comprising from 1% to 50%, preferably from 5% to 30%, more preferably from 15% to 25%, by weight of the total composition, of non- ionic surfactant. 11. A laundry detergent composition according to any preceding claim which additionally contains less than 10%, preferably less than 5%, of anionic surfactant. 12. A laundry detergent composition according to any preceding claim, which is free of anionic surfactant. 13. A laundry detergent composition according to any preceding claim which additionally comprises cellulose-based polymers or oligomers, cationic surfactants, dye transfer inhibiting polymers, mannan Constituents of enzymes, pearlescent agents, and/or mixtures thereof. 14. A laundry detergent composition comprising a semi-polar nonionic surfactant, preferably an amine oxide surfactant, and an organic pearlescent agent. 15. A laundry detergent composition according to any preceding claim wherein the pearlizing agent is selected from ethylene glycol distearate, ethylene glycol monostearate and/or mixtures thereof. 16. Use of semi-polar nonionic surfactants, preferably amine oxide surfactants, as crystallization enhancers for organic pearlescent agents. 17. Use of a laundry detergent composition according to claims 1-13 and 15 to provide cleaning and fabric care performance. 18. A laundry detergent composition as claimed in claim 17 for providing fabric color maintenance.