CN1330706A - Detergent compositions or components - Google Patents

Abstract

The present invention relates to detergent compositions or components comprising certain cyclic amine based polymers and certain anionic cellulose materials. This combination imparts improved appearance and integrity benefits to fabrics and textiles laundered in washing solutions formed from such compositions, while also providing improved whiteness and/or brightness maintenance.

Description

Detergent composition or component

Technical field

The present invention relates to compositions or components comprising certain cyclic amine-based polymers and certain anionic cellulosic materials.

Background of the Invention

Fabrics and textiles are known to wear out with time and use. Also, laundering of fabrics and textiles (over many cycles) can exacerbate and contribute to the loss of integrity and appearance of fabrics and textiles. Loss of fabric integrity and appearance can manifest in several ways. For example, short fibers are released from woven and knitted fabric/textile structures by the mechanical action of laundering. These dislodged fibers can form lint, fuzz, or "pompons" that are visible on the surface of the fabric, diminishing the appearance of newness to the fabric. In addition, repeated washing of fabrics and textiles, especially with laundry products containing bleach, removes dyes from fabrics and weaves, weakens shades, and in many cases changes the tint or shade of color, imparting fading wear Appearance.

In view of this, there is clearly an ongoing need to find materials which can be incorporated into laundry detergent products, which themselves bind to the fibers of the fabrics and textiles washed with the detergent products, thereby reducing or reducing the tendency of the washed fabric/textile to lose its appearance. Of course, such detergent product additives should benefit fabric appearance and integrity without unduly interfering with the laundry detergent's ability to perform its fabric cleaning function. Co-pending patent application PCT/US98/19143 describes the use of certain cyclic amine based polymers which were found to impart excellent integrity to fabrics.

The present inventors have now discovered that these amine-based polymers, when used in combination with specific anionic cellulosic materials, further improve fabric care and fabric integrity. It is believed that these benefits are obtained due to the interaction of the anionic cellulosic material and the amine-based polymer having positively charged groups in such a way that both polymer materials have improved surface activity, resulting in an improved surface activity with the fabric surface. Better interaction or better deposition on the fabric surface. It is believed that when the polymeric materials are present in an intimate admixture, the interaction between the polymeric materials is even more likely or even stronger, resulting in the polymeric materials being in an intimate admixture or in the same component or particle form Works better when present in the product.

These compounds, when used together, not only provide improved fabric integrity, but also improved stain removal and whiteness or brightness retention. The inventors have also found that these benefits are even more pronounced when the anionic cellulosic material and the amine-based polymer are present in an intimate mixture such as agglomerates, pressed granules or spray-dried granules.

Invention Summary

The present invention relates to a detergent composition or component or additive comprising:

a) 0.01 to 90% by weight, preferably 0.05 to 50% by weight, of anionic cellulose materials containing anionic substituents R-X-Z, wherein R is a saturated, unsaturated or aromatic spacer, X is oxygen, nitrogen or sulfur, and Z is a carboxylate, sulfonate, sulfate or phosphonate groups; and

b) 0.01 to 90% by weight, preferably about 0.05 to about 20% by weight cyclic amine-based polymer.

The present invention also relates to washing or treating fabrics and textiles in an aqueous wash or treatment solution formed from an effective amount of the detergent compositions or components described herein, or from the individual polymeric materials of said compositions or components . Washing fabrics and textiles in such wash solutions imparts fabric appearance benefits to the fabrics and textiles so treated. Such benefits may include improved overall appearance, pill/lint reduction, fade resistance, improved abrasion resistance, and/or enhanced softness, also improved whiteness and/or brightness retention, and even improved cleaning performance.

The cyclic amine-based polymer and cellulosic material are preferably an intimately mixed mixture with each other. In a preferred embodiment, the compounds are intimately mixed prior to incorporation into the compositions or components of the present invention.

Preferably, when the composition or component is a solid, the mixture is in the form of agglomerated, compacted or spray-dried particles.

The compound is preferably mixed with an anionic surfactant, preferably LAS, as described hereinafter. It is also preferred to incorporate a hydrotrope, preferably STS, into the mixture. It is also preferred that inorganic and/or organic salts and acids and/or silicates or aluminosilicates are present in the mixture, including zeolites, amorphous silicates, layered crystalline silicates, carbonates, bicarbonates salt, phosphate, citric acid, malic acid, maleic acid, tartaric acid or their salts, or mixtures of these ingredients.

                    Invention Details

Cyclic amine based polymer material

Essential components of the compositions or components of the present invention include one or more cyclic amine-based polymers.

The term "polymer" as used herein includes not only polymers, but also oligomers, copolymers, low copolymers, which exist in any structural arrangement including crosslinked arrangements. As is known to those skilled in the art, oligomers are molecules made up of only a few monomeric units, whereas polymers contain a considerable number of monomeric units. For purposes of this invention, oligomers are defined as molecules having an average molecular weight of less than about 1000, polymers are molecules having an average molecular weight of greater than about 1000; copolymers or oligomers are materials in which two or more different monomers are polymerized simultaneously or sequentially. The copolymer or oligomer of the present invention includes, for example, a polymer or oligomer polymerized from a mixture of a primary cyclic amine-based monomer such as piperadine and a secondary cyclic amine monomer such as morpholine.

Depending on the application of the composition or component of the invention, the amount of cyclic amine-based polymer may vary. The cyclic amine-based polymers described herein generally comprise from about 0.01 to about 90%, more preferably from 0.05 to 20%, even from 0.05 to 15%, by weight of the detergent compositions or components. For example, in the detergent composition of the present invention, it is preferred that the polymer is present in an amount of 0.05 to 10% by weight, preferably 0.05 to 5% by weight, more preferably 0.05 to 3% by weight, or even 0.1 to 2% by weight of the detergent composition. content exists. In detergent components or additives, said polymers are preferably present at levels of 0.05 to 40% by weight, more preferably 0.05 to 20% by weight, even more preferably 0.1 to 15% by weight, even 1 to 10% by weight.

The cyclic amine-based polymer is preferably present in the composition or component in such an amount that the concentration of cyclic amine in the wash solution is from 100 to 10000 ppm, preferably from 500 to 7000 ppm, even from 1000 to about 3000 ppm.

其中：The preferred cyclic amine-based polymers of the present invention can be characterized by the general formula:

in:

Each T is independently selected from H, C ₁ -C ₁₂ alkyl, substituted alkyl, C ₇ -C ₁₂ alkaryl, -(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 comprises at least one cyclic moiety selected from the group consisting of:

In addition to the at least one cyclic moiety, W may also comprise aliphatic or substituted aliphatic moieties of the general formula:

-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 dialkylarylenediyl (dialkylylarylenediy1), 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 groups;

- 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 dihydroxyalkylene, 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 moiety;

Provided that when R _is a C ₃ -C ₁₂ hydrocarbyl moiety, said hydrocarbyl moiety may contain from about 2 to about 4 branched moieties of the following general structure:

- each R ₃ is independently selected from H, O, R ₂ , C ₁ -C ₂₀ hydroxyalkyl, C ₁ -C ₂₀ alkyl, substituted alkyl, C ₆ -C ₁₁ aryl, substituted aryl , C ₇ -C ₁₁ alkaryl, C ₁ -C ₂₀ 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 alkaryl;

- each R ₅ is independently selected from C ₂ -C ₈ alkylene, C ₂ -C ₈ alkyl substituted alkylene; and

A is a compatible monovalent, divalent or polyvalent anion;

M is a compatible cation;

b = the number needed to balance the charge;

each x is independently from 3 to about 1000;

each c is independently 0 or 1;

each h is independently from about 1 to about 8;

each q is independently 0 to about 6;

each n is independently from 1 to about 20;

each r is independently 0 to about 20; and

Each t is independently 0 to 1.

The cyclic amine-based polymer may comprise a combination of these cyclic amine-based materials. For example, a mixture of piperadine and epihalohydrin condensates can be combined with a mixture of morpholine and epihalohydrin condensates to achieve the desired fabric treatment results. Additionally, the molecular weight of the cyclic polymers can be varied within the mixtures described herein.

最优选的化合物是以下的化合物：-其中每个R₁为H；和-至少一个W选自：

Preferred compounds falling within this general structural formula include compounds: - wherein each _R is H; and - at least one W is selected from: Even more preferred compounds are those: - wherein _each R is H; and - at least one W is selected from:

The most preferred compounds are those: - wherein _each R is H; and - at least one W is selected from:

Compounds preferably used as linker _R include, but are not limited to: polyepoxides, ethylene carbonate, propylene carbonate, urea, α,β-unsaturated carboxylic acids, esters of α,β-unsaturated carboxylic acids , amides of α, β-unsaturated carboxylic acids, anhydrides of α, β-unsaturated carboxylic acids, di- or polycarboxylic acids, esters of di- or polycarboxylic acids, amides of di- or polycarboxylic acids, di- or polycarboxylic acids Anhydrides of glycidyl halides, chloroformates, chloroacetates, derivatives of chloroformates, derivatives of chloroacetates, epihalohydrins, dichloroglycerin, dihalohydrins, polyethers Dihalides, carbonyl chlorides, polyhalogens, functionalized glycidyl ethers and mixtures thereof. In addition, _R can also contain one or more polyether diamines, alkylene diamines, polyalkylene polyamines, alcohols, alkylene glycols and polyalkylene glycols with α, β-unsaturated carboxylic Reaction products of 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 the reaction product contains at least two Double bond, two carboxyl groups, two amide groups or two ester groups.

Also preferred cyclic amine-based polymers for use in the present invention include those selected from the group consisting of piperazine, piperadine, epichlorohydrin, benzyl quaternized (quat) epichlorohydrin, methyl quaternized epichlorohydrin, Adducts of two or more combinations of phenolines and mixtures thereof.

A highly preferred cyclic amine based polymer is known as imidazole-epichlorohydrin copolymer.

These cyclic amine-based polymers can be linear or branched. A specific class of branching can be introduced with multifunctional crosslinkers. Examples of such polymers are listed below. anionic cellulose material

Compositions or components of the present invention include anionic cellulose materials containing anionic substituents R-X-Z, wherein R is a saturated, unsaturated or aromatic hydrocarbon spacer, X is oxygen, nitrogen or sulfur, and Z is carboxylate, sulfonate, sulfate or Phosphonate group.

The hydrocarbon spacer is preferably a C ₁ -C ₁₈ , more preferably a C ₁ -C ₁₄ , even more preferably a C ₁ -C ₄ saturated, unsaturated, or aromatic group, preferably an alkylene group. The spacer may also be substituted with one or more hydroxyl groups.

The group X is preferably nitrogen, or even more preferably an oxygen atom.

The group Z is preferably a carboxylate group.

Very preferred are the salts of so-called carboxyalkylcelluloses, wherein preferably the alkylene (or so-called alkyl) group contains 1 to 4 carbon atoms. Most preferred are the salts of carboxymethylcellulose.

The cation of the salt is preferably potassium or more preferably sodium.

The amount of cellulosic material may vary according to the application of the composition or components of the invention. The anionic cellulosic material generally comprises from about 0.01 to about 90%, more preferably from 0.05 to 50%, or even from 0.05 to 20% by weight of the detergent composition or component. For example, in detergent compositions, the material is preferably present in an amount of 0.05 to 10%, more preferably 0.05 to 7%, or even 0.05 to 5%, or even 0.5 to 3% by weight of the detergent composition weight. In components of the present invention such as detergent additives, said materials are preferably present in an amount of from 0.05 to 40% by weight of said component, or even from 0.05 to 20% by weight, or even from 0.1 to 15% by weight, or even from 1 to 10% by weight.

The anionic cellulosic material of the present invention is preferably present in the composition or component in such an amount that the concentration of cyclic amine in the wash liquor is from 100 to 10000 ppm, preferably from 500 to 7000 ppm, or even from 1000 to about 3000 ppm.

Detergent composition or component

The compositions or components of the invention are preferably laundry compositions, preferably in the form of granules, extrudates, flakes or tablets, liquids or pastes.

The compositions or components of the present invention may also contain other detergent ingredients. The nature of these other components and the amounts incorporated therein will depend on the physical form of the composition or component and the exact nature of the laundering operation employed.

They preferably comprise one or more other detergent ingredients selected from surfactants, bleaches, bleach catalysts, alkaline systems, builders, phosphate-containing builders, other organic polymeric compounds including dispersants, Soil-suspending and anti-redeposition agents, soil releasing agents, enzymes, suds suppressors, calcium soaps, perfumes, brighteners, fluorescent bleaches and other corrosion inhibitors.

Preferred additional ingredients are hydrophobicity-improving cellulose ether and ester polymers as described in co-pending patent applications PCT/US98/19139 and PCT/US98/19142. These polymers may be present in an amount of 0.01 to 10%, more preferably 0.05 to 5%, or even 0.1 to 2% by weight of the composition, or 0.05 to 30% by weight of the component, more preferably 0.1 to 20% by weight, or even 0.3 to 10% by weight.

Also highly preferred are enzymes, cationic softeners, clays, and optionally polymeric flocculants, dye transfer inhibiting agents, or preferably mixtures thereof, as hereinafter described.

Surfactant

The components or compositions of the present invention preferably comprise one or more surfactants selected from anionic, nonionic, cationic, amphiphilic, amphoteric and zwitterionic surfactants and mixtures thereof.

Typical anionic, nonionic, amphoteric and zwitterionic surfactants and classes of such surfactants are listed in US Patent 3,929,678, Laughlin and Heuring, issued December 30, 1975. Examples are given in "Surface Active Agents and Detergents" (Volumes I, II, Schwartz, Perry and Berch). Suitable cationic surfactants are listed in US Patent 4,259,217, Murphy, issued March 31,1981.

When present, amphiphilic, amphoteric and zwitterionic surfactants are generally used in combination with one or more anionic and/or nonionic surfactants.

anionic surfactant

The components or compositions of the present invention preferably comprise other anionic surfactants. Any anionic surfactant suitable for detersive use may optionally be included in the detergent component or composition. These may include salts of sulfate, sulfonate, carboxylate and sarcosinate anionic surfactants (including, for example, sodium, potassium, ammonium and substituted ammonium salts such as mono-, di- and tri-ethanolamine salts). Sulfate and sulphonate anionic surfactants are preferred.

Surfactant systems comprising sulfonate and sulfate surfactants are very preferred, preferably linear or branched alkylbenzenesulfonates and alkylhydroxyethylsulfates (as described herein), preferably as described herein. The cationic surfactant combination.

Other anionic surfactants include isethionates such as acyl isethionates, N-acyl taurates, fatty acid amides of methyl taurine, alkyl succinates and sulfosuccinates, sulfo Succinic acid monoester (especially saturated and unsaturated C ₁₂ -C ₁₈ monoester), sulfosuccinic acid diester (especially saturated and unsaturated C ₆ -C ₁₄ diester), N-acyl sarcosine Salt. Resin acids and hydrogenated resin acids are also suitable, such as rosin, hydrogenated rosin, and resin acids and hydrogenated resin acids present in or derived from tallow oil.

Anionic Sulfate Surfactant

Anionic sulfate surfactants suitable for use herein include linear and branched primary and secondary alkyl sulfates, alkyl ethoxy sulfates, aliphatic oleoyl glycerol sulfates, alkylphenol oxirane ether sulfates salt, C ₅ -C ₁₇ acyl-N-(C ₁ -C ₄ alkyl) and -N-(C ₁ -C ₂ hydroxyalkyl) glucosamine sulfates, sulfates of alkyl polysaccharides such as alkyl polysaccharides Sulfate of glucose (non-ionic, non-sulfate-type compound described herein).

Alkyl sulfate surfactants are preferably selected from linear and branched primary C ₁₀ -C ₁₈ alkyl sulfates, more preferably C ₁₁ -C ₁₅ branched chain alkyl sulfates and C ₁₂ -C ₁₄ linear alkyl sulfates Salt.

The alkyl ethoxy sulfate surfactants are preferably selected from C ₁₀ -C ₁₈ alkyl sulfates ethoxylated with 0.5 to 20 moles of ethylene oxide per mole. More preferably, the alkyl ethoxy sulfate surfactant is a C ₁₁ -C ₁₈ most preferably a C ₁₁ -C 15 ethoxylated with 0.5 to 7, preferably 1 to 5 moles of ethylene oxide per mole _. Alkyl sulfates.

Particularly preferred aspects of the invention employ mixtures of the preferred alkyl sulfate and/or sulfonate and alkyl ethoxy sulfate surfactants. Such mixtures are disclosed in WO93/18124.

Anionic Sulfonate Surfactant

Anionic sulfonate surfactants suitable for use in the present invention include C ₅ -C ₂₀ linear alkylbenzene sulfonates, alkyl ester sulfonates, C ₆ -C ₂₂ primary or secondary alkane sulfonates, C ₆ -C ₂₄ Olefin sulfonates, sulfonated polycarboxylic acids, alkyl glycerol sulfonates, fatty acyl glycerol sulfonates, fatty oleoyl glycerol sulfonates, and any mixtures thereof.

Anionic Carboxylate Surfactants

Suitable anionic carboxylate surfactants include alkyl ethoxy carboxylates, alkyl polyethoxy polycarboxylate surfactants and soaps (alkyl carboxyl), especially some of the secondary soaps described herein .

Suitable alkyl ethoxy carboxylates include those of the formula: RO(CH ₂ CH ₂ O) _x CH ₂ COO ^- M ⁺ , where R is C ₆ -C ₁₈ alkyl and x ranges from 0 to 10 Within, the distribution of the ethoxylates is such that the amount of material where x is 0 is less than 20%, and M is a cation. Suitable alkyl polyethoxy polycarboxylate surfactants include those of the formula: RO-(CHR ₁ -CHR ₂ -O)-R ₃ , wherein R is C ₆ -C ₁₈ alkyl and x is 1 to 25, R ₁ and R ₂ are selected from hydrogen, methyl acid, succinic acid, hydroxysuccinic acid and mixtures thereof, R ₃ is selected from hydrogen, substituted or unsubstituted hydrocarbons with 1 to 8 carbon atoms, and mixtures thereof.

Suitable soap surfactants include secondary soap surfactants comprising a carboxyl unit attached to a secondary carbon. Preferred secondary soap surfactants for use herein are water soluble secondary soaps selected from the group consisting of 2-methyl-1-undecanoic acid, 2-ethyl-1-decanoic acid, 2-propyl-nonanoic acid , 2-butyl-1-octanoic acid and 2-pentyl-1-heptanoic acid water-soluble salts.

Certain soaps may also be included as suds suppressors.

Alkali metal sarcosinate surfactant

Other suitable anionic surfactants are alkali metal sarcosinates of the formula: R-CON(R ¹ )CH ₂ COOM, wherein R is C ₅ -C ₁₇ linear or branched alkyl or alkenyl, and R ¹ is C ₁ -C ₄ alkyl, M is an alkali metal ion. Preferred examples are myristyl and oleoyl methyl sarcosinates in the sodium salt form.

Alkoxylated Nonionic Surfactants

Essentially any alkoxylated nonionic surfactant is suitable for use in the present invention. Ethoxylated and propoxylated nonionic surfactants are preferred.

Preferred alkoxylated surfactants may be selected from nonionic condensates of alkylphenols, nonionic ethoxylated alcohols, nonionic ethoxylated/propoxylated fatty alcohols, nonionic ethoxylated Condensation products of / propoxylates with propylene glycol, and condensation products of nonionic ethoxylates with propylene oxide / ethylenediamine adducts.

Nonionic Alkoxylated Alcohol Surfactants

Condensation products of aliphatic alcohols with 1 to 25 moles of alkylene oxides, especially ethylene oxide and/or propylene oxide, are suitable for use in the present invention. The alkyl chain of the aliphatic alcohol may be straight or branched (primary or secondary), generally containing 6 to 22 carbon atoms. Particularly preferred are the condensation products of alcohols having an alkyl group of 8 to 20 carbon atoms with 2 to 10 moles of ethylene oxide per mole of alcohol.

Nonionic Polyhydroxy Fatty Acid Amide Surfactant

^Polyhydroxy fatty acid amides suitable for use in the present invention are those having the formula: ^R2CONR1Z , wherein ^R1 is H, _C1 - _C4 hydrocarbyl, 2-hydroxyethyl, 2-hydroxypropyl, ethoxy , propoxy, or a mixture thereof, preferably C ₁ -C ₄ alkyl, more preferably C ₁ or C ₂ alkyl, most preferably C ₁ alkyl (ie methyl); R ² is C ₅ -C ₃₁ hydrocarbon group, Preferably straight chain C ₅ -C ₁₉ alkyl or alkenyl, more preferably straight chain C ₉ -C ₁₇ alkyl or alkenyl, most preferably straight chain C ₁₁ -C ₁₇ alkyl or alkenyl, or a mixture thereof; Z is Polyhydroxyl hydrocarbyl (linear hydrocarbyl chain having at least 3 hydroxyl groups directly attached thereto), or alkoxylated derivatives thereof (preferably ethoxylated or propoxylated). Z is preferably derived from a reducing sugar in a reductive amination reaction; more preferably Z is glycityl.

Nonionic Fatty Acid Amide Surfactant

Suitable fatty acid amide surfactants include those of the formula: R ⁶ CON(R ⁷ ) ₂ , wherein R ⁶ is an alkyl group containing 7 to 21, preferably 9 to 17 carbon atoms, each R ⁷ being selected from hydrogen, C ₁ -C ₄ alkyl, C ₁ -C ₄ hydroxyalkyl, and -(C ₂ H ₄ O) _x H, where x is in the range of 1 to 3.

Nonionic Alkyl Polysaccharide Surfactant

Alkylpolysaccharides suitable for use in the present invention are disclosed in US4565647 (Llenado, January 21, 1986), polysaccharides having a hydrophobic group of 6 to 30 carbon atoms and 1.3 to 10 sugar units (such as polydextrose ) hydrophilic group.

Preferred alkyl polydextrose has the formula:

R ² O(C _n H _2n O) _t (glycosyl) _x

Wherein ^R is selected from alkyl, alkylphenyl, hydroxyalkyl, hydroxyalkylphenyl, and mixtures thereof, wherein the alkyl contains 10 to 18 carbon atoms; n is 2 or 3; t is 0 to 10; and x is from 1.3 to 8. The glycosyl is preferably derived from glucose.

amphoteric surfactant

Amphoteric surfactants suitable for use herein include amine oxide surfactants and alkyl amphocarboxylic acids.

Suitable amine oxides include those compounds of the formula: R ³ (OR ⁴ ) _x N ⁰ (R ⁵ ) ₂ , wherein R ³ is selected from the group consisting of alkyl, hydroxyalkyl, amidopropyl, containing 8 to 26 carbon atoms and alkylphenyl or a mixture thereof; R ⁴ is an alkylene or hydroxyalkylene group containing 2 to 3 carbon atoms or a mixture thereof; x is 0 to 5, preferably 0 to 3; each R ⁵ is 1 Alkyl or hydroxyalkyl groups of up to 3 carbon atoms, or polyoxyethylene groups containing 1 to 3 oxyethylene groups. Preferred are C ₁₀ -C ₁₈ alkyldimethylamine oxides, and C ₁₀ -C ₁₈ amidoalkyldimethylamine oxides.

An example of a suitable alkyl aphodicarboxylic acid is Miranol(TM) C2M Conc. manufactured by Miranol, Inc., Dayton, NJ.

zwitterionic surfactant

Zwitterionic surfactants can also be incorporated into the detergent ingredients or compositions of the present invention. These surfactants can be broadly described as derivatives of secondary and tertiary amines, derivatives of heterocyclic secondary and tertiary amines, or derivatives of quaternary ammonium, quaternary phosphonium or tertiary sulfonium compounds. Betaine and sultaine surfactants are examples of amphoteric surfactants useful in the present invention.

Suitable betaines are those compounds of the formula: R(R') ₂ N ⁺ R ² COO ⁻ , wherein R is C ₆ -C ₁₈ hydrocarbyl, each R ¹ is typically C ₁ -C ₃ alkyl, R ² is a C ₁ -C ₅ hydrocarbon group. Preferred betaines are C _12-18 dimethylcarbamate and C _10-18 amidopropane (or ethane) dimethyl (or diethyl) betaine. Complex betaine surfactants are also suitable for use in the present invention.

cationic surfactant

Cationic surfactants suitable for use in the detergents of the present invention include quaternary ammonium surfactants. Preferred quaternary ammonium surfactants are mono C ₆ -C ₁₆ , preferably C ₆ -C ₁₀ N-alkyl or alkenyl ammonium surfactants in which the remaining N positions are substituted by methyl, hydroxyethyl or hydroxypropyl groups . The mono-alkoxylated and bis-alkoxylated amine surfactants are also preferred.

Another class of cationic surfactants which may be used in the detergent compositions or components of the present invention are cationic ester surfactants. Cationic ester surfactants are preferably water-dispersible compounds having surfactant properties comprising at least one ester (ie -COO-) linkage and at least one positively charged group.

Suitable cationic ester surfactants include the choline ester surfactants disclosed, for example, in US4228042, 4239660 and 4260529.

In a preferred aspect, the ester bond and the positively charged group are separated by a spacer in the surfactant molecule, and the spacer consists of at least three atoms (ie, a three-atom chain length), preferably 3 to 8 atoms, more preferably 3 to 5 atoms, most preferably 3 atoms. The atoms making up the spacer are selected from carbon, nitrogen and oxygen atoms and any mixtures thereof, provided that any nitrogen or oxygen atom in the chain is bonded only to a carbon atom in the chain. Spacers such as -OO- (i.e. peroxide), -NN-, and -NO- linkages are thus excluded, but spacers such as _-CH2 -O- _CH2- and _-CH2- NH- _CH2 - a spacer for the bond. Preferably the spacer chain comprises only carbon atoms, most preferably the chain is a hydrocarbyl chain.

Cationic Monoalkoxylated Amine Surfactants

其中R¹为含约6至约18个碳原子、优选6至约16个碳原子、最优选约6至约14个碳原子的烷基或烯基部分；R²和R³独立地为含1至约3碳原子的烷基、优选甲基、最优选R²和R³均为甲基；R⁴选自氢(优选)、甲基和乙基；X^-为提供电中性的阴离子如氯、溴、甲基硫酸根、硫酸根等阴离子；A为烷氧基，特别是乙氧基、丙氧基或丁氧基；p为0至约30、优选2至约15、最优选2至约8。Very preferred herein are cationic monoalkoxylated amine surfactants of the general formula I:

wherein ^R is an alkyl or alkenyl moiety containing from about 6 to about 18 carbon atoms, preferably from 6 to about 16 carbon atoms, most preferably from about 6 to about 14 carbon atoms; R ^{and R} are independently Alkyl of 1 to about 3 carbon atoms, preferably methyl, most preferably ^R2 and ^R3 are both methyl; ^R4 is selected from hydrogen (preferred), methyl and ethyl; X ^- is an anion that provides electrical neutrality Such as chlorine, bromine, methylsulfate, sulfate and other anions; A is alkoxy, especially ethoxy, propoxy or butoxy; p is 0 to about 30, preferably 2 to about 15, most preferably 2 to about 8.

Preferably ^the ApR group in formula I has p=1, is a hydroxyalkyl group, and has no more than 6 carbon atoms, so that the -OH group is separated from the quaternary ammonium nitrogen atom by no more than 3 carbon atoms. open. Particularly preferred ^ApR4 radicals _{are -CH2CH2OH} , _{-CH2CH2CH2OH , -CH2CH} ( _CH3 )OH and -CH _{( CH3 ) CH2OH} , particularly preferably _-CH2CH2OH . Preferably the R ^group is a straight chain alkyl group. Straight-chain ^R groups having 8 to 14 carbon atoms are preferred.

其中R¹为C₁₀-C₁₈烃基及其混合物、特别是C₁₀-C₁₄烷基、优选C₁₀和C₁₂烷基，X为使电荷平衡的任何方便的阴离子，优选氯或溴离子。Another very preferred cationic monoalkoxylated amine surfactant for use herein is a compound of the formula:

wherein R ¹ is C ₁₀ -C ₁₈ hydrocarbyl and mixtures thereof, especially C ₁₀ -C ₁₄ alkyl, preferably C ₁₀ and C ₁₂ alkyl, and X is any convenient anion for charge balancing, preferably chloride or bromide.

Compounds of the above type include those in which ethoxy (CH ₂ CH ₂ O) units (EO) are replaced by butoxy, isopropoxy [CH(CH ₃ )CH ₂ O] and [CH ₂ CH(CH ₃ O] units Those replaced by (i-Pr) or n-propoxy units (Pr), or mixtures of EO and/or Pr and/or i-Pr units.

The cationic monoalkoxylated amine surfactants are preferably used in the detergent compositions herein at a level of from 0.1 to 20%, more preferably from 0.2 to 7%, most preferably from 0.3 to 3.0% by weight of the composition.

Cationic bis-alkoxylated amine surfactants

其中R¹为含约8至约18个碳原子、优选10至约16个碳原子、最优选约10至约14个碳原子的烷基或烯基；R²为含1至3个碳原子的烷基、优选甲基；R³和R⁴独立地选自氢(优选)、甲基和乙基；X^-为足以提供电中性的阴离子如氯、溴、甲基硫酸根、硫酸根等阴离子。A和A’独立地选自C₁-C₄烷氧基，特别是乙氧基(即-CH₂CH₂O-)、丙氧基、丁氧基及其混合物；p为1至约30、优选1至约4，q为1至约30、优选1至约4，最优选p和q均为1。Cationic bis-alkoxylated amine surfactants preferably have the following general formula II:

wherein R ¹ is an alkyl or alkenyl group containing about 8 to about 18 carbon atoms, preferably 10 to about 16 carbon atoms, most preferably about 10 to about 14 carbon atoms; R ² is an alkyl or alkenyl group containing 1 to 3 carbon atoms Alkyl, preferably methyl; R ³ and R ⁴ are independently selected from hydrogen (preferred), methyl and ethyl; X ^- is an anion sufficient to provide electrical neutrality such as chlorine, bromine, methylsulfate, sulfate and other anions. A and A' are independently selected from C ₁ -C ₄ alkoxy, especially ethoxy (ie -CH ₂ CH ₂ O-), propoxy, butoxy and mixtures thereof; p is from 1 to about 30 , preferably 1 to about 4, q is 1 to about 30, preferably 1 to about 4, most preferably both p and q are 1.

其中R¹为C₁₀-C₁₈烃基及其混合物，优选C₁₀、C₁₂、C₁₄烷基及其混合物。X为使电荷平衡的任何方便的阴离子，优选氯离子。关于上述阳离子双烷氧基化胺结构通式，在优选的化合物中R¹由(椰子)C₁₂-C₁₄烷基脂肪酸衍生，R²为甲基，ApR³和A’qR⁴均为单乙氧基。Very preferred cationic bisalkoxylated amine surfactants for use herein are those of the formula:

Wherein R ¹ is C ₁₀ -C ₁₈ hydrocarbon groups and mixtures thereof, preferably C ₁₀ , C ₁₂ , C ₁₄ alkyl groups and mixtures thereof. X is any convenient charge balancing anion, preferably chloride. With regard to the general formula of cationic bis-alkoxylated amines described above, in preferred compounds ^R1 is derived from (coconut) _C12 - _C14 alkyl fatty acid, ^R2 is methyl, ^ApR3 and ^A'qR4 are both mono Ethoxy.

Other cationic bisalkoxylated amine surfactants suitable for use herein include compounds of the formula: wherein R ¹ is C ₁₀ -C ₁₈ hydrocarbyl, preferably C ₁₀ -C ₁₄ alkyl, p is 1 to about 3, q is 1 to about 3, R ² is C ₁ -C ₃ alkyl, preferably methyl, X is an anion, especially chloride or bromide.

Other compounds of the above type include those in which ethoxy (CH ₂ CH ₂ O) units (EO) are replaced by butoxy (Bu), isopropoxy [CH(CH ₃ )CH ₂ O] and [CH ₂ CH(CH ₃ O] units (i-Pr) or n-propoxy units (Pr), or mixtures of EO and/or Pr and/or i-Pr units are substituted.

Perhydrate Bleach

A preferred further component of the component or composition is a perhydrate bleach, such as metal perborates, metal percarbonates, especially the sodium salts. Perborates can be mono- or tetrahydrated. Sodium percarbonate has the formula: _{2Na2CO3-3H2O2 and is} commercially available as _a crystalline solid. Potassium, sodium peroxymonopersulfate are another class of optional inorganic peroxide salts useful in the detergent components or compositions of the present invention.

Organic peroxyacid bleaching system

A preferred feature of said component or composition is an organic peroxyacid bleaching system. In a preferred embodiment, the bleach system comprises a source of hydrogen peroxide and an organic peroxyacid bleach precursor compound. Organic peroxyacids are produced by in situ reaction of said precursors with a source of hydrogen peroxide. Preferred sources of hydrogen peroxide include inorganic perhydrate bleaches such as the perborate bleaches claimed herein. In another preferred embodiment, a preformed organic peroxyacid is incorporated directly into the component or composition. Components or compositions comprising a source of hydrogen peroxide and a mixture of organic peroxyacid precursors and preformed organic peroxyacids are also contemplated.

Peroxyacid Bleach Precursors

其中L为离去基团，X为任何必要的官能团，以致强双氧水解时产生的过氧酸结构为：

Peroxyacid bleach precursors are compounds which react with hydrogen peroxide in a strong perhydrolysis reaction to produce peroxyacids. Peroxyacid bleach precursors can generally be expressed as:

Wherein L is a leaving group, and X is any necessary functional group, so that the peroxyacid structure produced during strong hydrogen peroxide hydrolysis is:

Peroxyacid bleach precursor compounds are preferably incorporated at levels of from 0.5 to 20%, more preferably from 1 to 15%, most preferably from 1.5 to 10% by weight of the detergent composition.

Suitable peroxyacid bleach precursor compounds typically contain one or more N- or O-acyl groups and may be selected from a wide range of types. Suitable classes include anhydrides, esters, imides, lactams, and acylated derivatives of imidazoles and oximes. Examples of suitable materials of these classes are disclosed in GB-A-1586789. Suitable esters are disclosed in GB-A-836988, 864798, 1147871, 2143231 and EP-A-0170386.

leaving group

The leaving group (hereinafter referred to as L group) must be sufficiently reactive to the strong hydrogen peroxide hydrolysis reaction to react within an optimal time frame (eg, wash cycle). But if the activity of L is too high, the activator is difficult to use stably in bleaching components or compositions.

及其混合物，其中R¹为含1至14个碳原子的烷基、芳基、或烷芳基，R³为含1至8个碳原子的烷基链，R⁴为H或R³，Y为H或加溶基。R¹、R³和R⁴均可被任何必要的官能基取代，所述官能基包括例如烷基、羟基、烷氧基、卤素、胺、亚硝酰、酰胺和铵或烷基铵基。Preferred L groups are selected from:

and mixtures thereof, wherein R ¹ is an alkyl, aryl, or alkaryl group containing 1 to 14 carbon atoms, R ³ is an alkyl chain containing 1 to 8 carbon atoms, R ⁴ is H or R ³ , Y is H or a solubilizing group. R ¹ , R ³ and R ⁴ may be substituted with any desired functional groups including, for example, alkyl, hydroxyl, alkoxy, halogen, amine, nitrosyl, amide, and ammonium or alkylammonium groups.

Preferred solubilizing groups are -SO ₃ ^- M ⁺ , -CO ₂ ^- M ⁺ , -SO ₄ ^- M ⁺ , -N ⁺ (R ³ ) ₄ X ^- and O<--N(R ³ ) ₃ , most Preferred are -SO ₃ ^{-M +} and -CO ₂ ^{-M +} , wherein R ³ is an alkyl chain containing 1 to 4 carbon atoms, M is a cation that provides solubility for the bleach activator, and X is a cation for the bleach activator. The activator provides a soluble anion. Preferably, M is an alkali metal, ammonium or substituted ammonium cation, most preferably sodium and potassium, and X is a halide, hydroxide, methylsulfate or acetate anion.

Alkyl percarboxylic acid bleach precursor

Alkyl percarboxylic acid bleach precursors form percarboxylic acids on strong hydrogen peroxide hydrolysis. Preferred precursors of this type yield peracetic acid upon strong hydrogen peroxide hydrolysis.

Preferred imide-type alkyl percarboxylic acid precursor compounds include N,N,N ¹ ,N ¹ -tetraacetylated alkylenediamines, wherein the alkylene group contains 1 to 6 carbon atoms, especially Those compounds wherein said alkylene group contains 1, 2 and 6 carbon atoms. Particular preference is given to tetraacetylethylenediamine (TAED).

Other preferred alkyl percarboxylic acid precursors include sodium 3,5,5-trimethylhexanoyloxybenzenesulfonate (iso-NOBS), sodium nonanoyloxybenzenesulfonate (NOBS), acetoxybenzene Sodium Sulfonate (ABS) and Pentaacetyl Glucose.

Amide Substituted Alkyl Peroxyacid Precursors

其中R¹为有1至14个碳原子的烷基，R²为含1至14个碳原子的亚烷基，R⁵为H或含1至10个碳原子的烷基，L可为必要的任何离去基团。此类酰胺取代的漂白活化剂化合物描述在EP-A-0170386中。Amide substituted alkyl peroxyacid precursor compounds are suitable for use in the present invention and include those of the general formula:

Wherein R ¹ is an alkyl group with 1 to 14 carbon atoms, R ² is an alkylene group with 1 to 14 carbon atoms, R ⁵ is H or an alkyl group with 1 to 10 carbon atoms, and L can be necessary any leaving group. Amide substituted bleach activator compounds of this type are described in EP-A-0170386.

preformed organic peroxyacids

In addition to or as an alternative to organic peroxyacid bleach precursor compounds, the detergent composition may comprise preformed organic peroxyacids, typically from 1 to 15% by weight of the composition, more preferably 1 to 10% by weight.

A preferred class of organic peroxyacid compounds are amide substituted compounds of the general formula: Wherein R ¹ is an alkyl group, aryl group or alkaryl group with 1 to 14 carbon atoms, R ² is an alkylene group, arylene group, and alkarylene group with 1 to 14 carbon atoms, and R ⁵ is H or an alkyl, aryl, or alkaryl group containing 1 to 10 carbon atoms. Amide substituted organic peroxyacid compounds of this type are described in EP-A-0170386.

Other organic peroxyacids include diacyl and tetraacyl peroxides, especially diperoxydodecanedioic acid, diperoxytetradecanedioic acid and diperoxycetadedioic acid. Mono- and diperazelaic acid, mono- and dipertridecanedioic acid, and N-phthalamidopercaproic acid are also suitable for use in the present invention.

water soluble builder compound

The components or compositions of the present invention preferably comprise a water soluble builder compound, typically present in the detergent composition in an amount of from 1 to 80% by weight of the composition, preferably from 10 to 60% by weight, most preferably from 15 to 40% weight.

The detergent ingredients or compositions of the present invention preferably include phosphate-containing builder materials. It is preferably present in an amount of 0.5 to 60%, more preferably 5 to 50%, more preferably 8 to 40%.

Phosphate-containing builder materials preferably include tetrasodium pyrophosphate, even more preferably anhydrous sodium tripolyphosphate.

Suitable water-soluble builder compounds include water-soluble monomeric polycarboxylates or acid forms thereof, homo- or co-polymeric polycarboxylic acids or salts thereof (wherein said polycarboxylic acid contains at least two and not more than two carbon atoms separated carboxyl), borates, and mixtures of any of the foregoing.

The carboxylate or polycarboxylate builders can be of the monomeric or oligomeric type, but the monomeric form of the polycarboxylate is generally preferred for reasons of cost and performance.

Suitable carboxylate salts containing one carboxy group include the water-soluble salts of lactic acid, glycolic acid and ether derivatives thereof. Polycarboxylates containing two carboxy groups include water-soluble salts of succinic acid, malonic acid, (ethylenedioxy) diacetic acid, maleic acid, diglycolic acid, tartaric acid, tartronic acid, and fumaric acid , and ether carboxylates and sulfinyl carboxylates. Polycarboxylates containing three carboxyl groups or their acids include water-soluble citrate, aconitate and citraconic acid salts, and succinate derivatives such as carboxymethoxysuccinate as described in GB1379241, GB1389732 The lactoxy (lactoxy) succinate, and the amino succinate described in NL7205873, and the oxygen-containing polycarboxylate material such as 2-oxa-1,1,3-propanetricarboxylate as described in GB1387447 salt. The most preferred polycarboxylic acid containing three carboxy groups is citric acid, preferably present in an amount of from 0.1 to 15%, more preferably from 0.5 to 8% by weight of the composition.

Polycarboxylates containing four carboxyl groups include oxydisuccinates, 1,1,2,2-ethane tetracarboxylates, 1,1,3,3-propane tetracarboxylates disclosed in GB1261829 and 1,1,2,3-propane tetracarboxylate. Polycarboxylates containing sulfo substituents include sulfosuccinic acid derivatives disclosed in GB1398421, 1398422 and US3936448, sulfonated pyrolyzed citrates described in GB1439000. Preferred polycarboxylates are hydroxycarboxylates containing up to three carboxy groups per molecule, especially citrates.

Parent acids of monomeric or oligomeric polycarboxylate chelating agents or mixtures thereof, such as citric acid or citrate/citric acid mixtures, are also suitable builder ingredients.

Borate builders and builders comprising borate-forming materials which generate borate under detergent storage or wash conditions are also suitable water-soluble builders for use herein.

Examples of suitable water-soluble phosphate builders are alkali metal tripolyphosphates, sodium, potassium and ammonium pyrophosphates, sodium and potassium orthophosphates, sodium polymeta/phosphates having a degree of polymerization in the range of about 6 to 21, and salts of phytic acid.

Partially soluble or insoluble builder compounds

The components or compositions of the present invention may comprise partially soluble or insoluble builder compounds, typically present in detergent compositions at levels of from 0.5 to 60% by weight of the composition, preferably from 5 to 50% by weight, most preferably 8 to 40% by weight.

Examples of water insoluble builders include sodium aluminosilicates.

Suitable aluminosilicate zeolites have the following unit cell formula: Na _z [(AlO ₂ ) _z (SiO ₂ ) _y ].xH ₂ O, where z and y are at least 6; the molar ratio of z to y is from 1.0 to 0.5 , x is at least 5, preferably 7.5 to 276, more preferably 10 to 264. The aluminosilicate material is in hydrated form, preferably crystalline, containing 10 to 28%, more preferably 18 to 22% water in bound form.

The aluminosilicate zeolites may be naturally occurring materials, but are preferably synthetic. Synthetic crystalline aluminosilicate ion exchange materials are available under the designations A-type zeolites, B-type zeolites, P-type zeolites, X-type zeolites, HS-type zeolites, and mixtures thereof. Type A zeolite has the following formula:

Na ₁₂ [AlO ₂ ) ₁₂ (SiO ₂ ) ₁₂ ].xH ₂ O where x is 20 to 30, especially 27. Type X zeolite has the following formula: Na ₈₆ [(AlO ₂ ) ₈₆ (SiO ₂ ) ₁₀₆ ]·276H ₂ O.

Another preferred class of aluminosilicate zeolites are zeolite builders of the MAP type. The MAP type zeolite may be present in an amount of 1 to 80% by weight of the composition, more preferably 15 to 40% by weight.

Zeolites of the MAP type are described in EP384070A (Unilever). Alkali metal aluminosilicates defined as zeolites of type P having a silicon to aluminum ratio not greater than 1.33, preferably in the range of 0.9 to 1.33, more preferably in the range of 0.9 to 1.2.

Of particular interest are MAP-type zeolites having a silica-to-alumina ratio of not greater than 1.15, especially not greater than 1.07.

Preferably, the MAP-type zeolite builder has a particle size expressed as a _d50 value of 1.0 to 10.0 microns, more preferably 2.0 to 7.0 microns, most preferably 2.5 to 5.0 microns.

A _d50 value means that 50% by weight of the particles have a diameter smaller than this number. In particular the particle size can be determined by conventional analytical techniques such as microscopic measurement with a scanning electron microscope or by laser granulometers. Other methods of determining _d50 values are disclosed in EP384070A.

Heavy metal ion (polyvalent) chelating agent

The components or compositions of the present invention preferably comprise a heavy metal ion (sequestering) agent as an optional component. Herein heavy metal ion (multivalent) chelating agent means a component that acts to chelate heavy metal ions. These components may also have calcium and magnesium chelating capacity, but are preferably selective for binding heavy metal ions such as iron, manganese and copper.

The heavy metal ion (sequestering) chelating agent is generally present in an amount of 0.005 to 10%, preferably 0.1 to 5%, more preferably 0.25 to 7.5%, most preferably 0.3 to 2% by weight of the composition or component.

Heavy metal ion (multivalent) sequestrants suitable for use in the present invention include organic phosphonates such as aminoalkylene poly(alkylene phosphonates), alkali metal ethane 1-hydroxydiphosphonates, and nitrilotriethylene Methylphosphonate.

Among the above substances, diethylenetriaminepenta(methylenephosphonate), ethylenediaminetris(methylenephosphonate), hexamethylenediaminetetrakis(methylenephosphonate), hydroxyl - Ethylene-1,1-diphosphonate, 1,1-hydroxyethanediphosphonic acid and 1,1-hydroxyethane dimethylenephosphonic acid.

Other heavy metal ion (multivalent) sequestrants suitable for use in the present invention include nitrilotriacetic acid and polyaminocarboxylic acids such as ethylenediaminotetraacetic acid, ethylenediaminedisuccinic acid, ethylenediaminediglutaric acid, 2-hydroxy Propylenediamine disuccinic acid or any salt thereof.

Other suitable heavy metal sequestrants for use herein are iminodiacetic acid derivatives such as 2-hydroxyethyldiacetic acid or glyceryl iminodiacetic acid, as described in EP-A-317542 and EP-A-399133. Also suitable are the iminodiacetic acid-N-2-hydroxypropylsulfonic acid and aspartic acid N-carboxymethyl N-2-hydroxypropyl-3-sulfonic acid sequestrants described in EP-A-516102 in the present invention. β-alanine-N,N'-diacetic acid, aspartic acid-N,N'-diacetic acid, aspartic acid-N-monoacetic acid and iminodisuccinic acid described in EP-A-509382 (Polyvalent) chelating agents are also suitable.

EP-A-476257 describes suitable amino (sequestering) chelating agents. EP-A-510331 describes suitable (sequestering) sequestrants derived from collagen, keratin or casein. EP-A-528859 describes suitable alkyliminodiacetic acid (multivalent) sequestrants. Also suitable are dipicolinic acid and 2-phosphonobutane-1,2,4-tricarboxylic acid. Glycinamide-N,N'-disuccinic acid (GADS), ethylenediamine-N,N'-diglutaric acid (EDDG) and 2-hydroxypropylenediamine-N,N'-disuccinic acid (HPDDS ) also applies.

Particularly preferred are diethylenetriaminepentaacetic acid, ethylenediamine-N,N'-di-succinic acid (EDDS) and 1,1-hydroxyethanediphosphonic acid or their alkali metals, alkaline earth metals, ammonium or Substitution of ammonium salts, or mixtures thereof.

enzyme

Another preferred ingredient suitable for use in the components or compositions of the present invention is one or more additional enzymes.

Preferred additional enzyme materials include lipases, cutinases, amylases, neutral and alkaline proteases, cellulases, endolases, esterases, which are commonly incorporated into detergent ingredients or compositions. Pectinase, lactase and peroxidase. Suitable enzymes are disclosed in US3519570 and US3533139.

Preferred commercially available proteases include those sold under the tradenames Alcalase, Savinase, Primase, Durazym, and Esperase by Novo Industries A/S (Denmark), those sold under the tradenames Maxatase, Maxacal, and Maxapem by GistBrocades, those sold by Genencor International, and those sold by Solvay Enzymes under the trade names Opticlean and Optimase. Proteases may be incorporated in the compositions of the present invention in amounts ranging from 0.0001 to 4% active enzyme by weight of the composition.

Preferred amylases include, for example, alpha-amylases obtained from strains of B. licheniformis, described in GB1269839 (Novo). Preferred commercially available amylases include, for example, those sold under the tradename Rapidase by GistBrocades, and those sold under the tradename Termamyl, Duramyl and BAN by Novo Industries A/S. Highly preferred amylases are those described in PCT/US97/03635, WO95/26397 and WO96/23873.

Amylases may be incorporated in the compositions of the present invention in amounts ranging from 0.0001 to 2% active enzyme by weight of the composition.

The lipolytic enzyme may be present in an amount of 0.0001 to 2%, preferably 0.001 to 1%, most preferably 0.001 to 0.5% active lipase by weight of the composition.

The lipase may be of fungal or bacterial origin, for example from lipase-producing strains of Humicola spp., Thermomyces spp. or Pseudomonas spp., including Pseudomonas pseudoal caligenes or fluorescent Pseudomonas fluorescens. Lipases from chemically modified or genetically modified mutants of these strains are also suitable for use in the present invention. A preferred lipase is derived from Pseudomonas pseudoalcaligenes, described in granted EP-B-0218272.

Another preferred lipase of the present invention is obtained by cloning a gene from Humicola lanuginosa and expressing it using Aspergillus oryzae as a host, as described in EP-A-0258068, commercially available under the tradename Lipolase from Novo Industri A/S, Bagsvaerd, Denmark. This lipase is also described in US4810414, issued March 7, 1989 (Huge-Jensen et al.).

organic polymer compound

Organic polymeric compounds are preferred additional components of the components or compositions of the present invention, preferably present as components of any particulate components, which bind said particulate components together. Organic polymeric compound herein means any necessary polymeric organic compound useful as a dispersant, anti-redeposition agent and soil-suspension agent in detergent ingredients or compositions, including any high molecular weight compounds referred to herein as clay flocculants Organic polymeric compounds, including the quaternized ethoxylated (poly)amine clay-soil release/anti-redeposition agents of the present invention.

The organic polymeric compound is typically incorporated in the detergent compositions of the present invention at a level of from 0.01 to 30%, preferably from 0.1 to 15%, most preferably from 0.5 to 10% by weight of the composition.

Examples of organic polymeric compounds include water-soluble organic homo- or co-polymeric polycarboxylic acids or salts thereof, wherein the polycarboxylic acids include at least two carboxyl groups separated by not more than 2 carbon atoms. Polymers of the latter type are disclosed in GB-A-1596756. Examples of such salts are polyacrylates of MWt 1000-5000 and their copolymers with maleic anhydride, said copolymers having a molecular weight of from 2,000 to 100,000, especially from 40,000 to 80,000.

Polyamino compounds are also suitable for use in the present invention, including those derived from aspartic acid, such as those disclosed in EP-A-305282, EP-A-305283 and EP-A-351629.

Terpolymers comprising monomer units selected from maleic acid, acrylic acid, polyaspartic acid and vinyl alcohol, especially those having an average molecular weight of 5,000 to 10,000, are also suitable for use in the present invention.

Other organic polymeric compounds suitable for incorporation in the detergent components or compositions of the present invention include cellulose derivatives such as methylcellulose, carboxymethylcellulose, hydroxypropylmethylcellulose and hydroxyethylcellulose.

Other suitable organic polymeric compounds are polyvinyl alcohols, especially those having a molecular weight of 1,000-10,000, more preferably 2,000 to 8,000, most preferably about 4,000.

Highly preferred polymeric components of the present invention are the cotton and non-cotton soil release polymers of US4968451 (Scheiber et al.), and US5415807 (Gosselink et al.), especially US Application No. 60/051517.

Another organic compound suitable for use in the present invention, which is the preferred clay dispersant/anti-redeposition agent, may be the ethoxylated cationic monoamines and diamines of the formula: wherein X is a nonionic group selected from H, C ₁ -C ₄ alkyl or hydroxyalkyl esters or ether groups, and mixtures thereof, a is 0 to 20, preferably 0 to 4 (e.g. ethylene, propylene , hexylene), b is 1 or 0; for cationic monoamines (b=0), n is at least 16, typically in the range of 20 to 35; for cationic diamines (b=1), n is at least about 12. Typically in the range of about 12 to about 42.

Other dispersants/anti-redeposition agents suitable for use in the present invention are described in EP-B-011965, US4659802 and US4664848.

Antifoam system

When formulated for use in machine wash compositions, the detergent compositions of the present invention may contain a suds suppressing system which may be present in an amount from 0.01 to 15%, preferably from 0.02 to 10%, most preferably from 0.05 to 3% by weight of the composition.

Suds suppressing systems suitable for use in the present invention may comprise any necessary known antifoam compounds including, for example, silicone antifoam compounds and 2-alkyl alcanol antifoam compounds.

By antifoam compound is meant herein any compound or mixture of compounds which acts to inhibit foam or foaming of a solution of a detergent composition, especially in the presence of agitation of the solution.

Particularly preferred antifoam compounds for use in the present invention are silicone antifoam compounds, defined herein as any antifoam compound that includes a silicone component. Such silicone antifoam compounds typically also contain a silica component. As used herein, the term "polysiloxane" (commonly used in the industry) includes all types of higher molecular weight polymers containing siloxane units and various types of hydrocarbyl groups. Preferred silicone antifoam compounds are silicones, especially polydimethylsiloxanes having trimethylsilyl endblocking units.

Other suitable antifoam compounds include monocarboxylic fatty acids and soluble salts thereof. These materials are described in US2954347, published September 27, 1960 (Wayne St. John). The monocarboxylic fatty acids and salts thereof useful as suds suppressors typically have hydrocarbyl chains of 10 to 24 carbon atoms, preferably 12 to 18 carbon atoms. Suitable salts include alkali metal salts such as sodium, potassium, and lithium salts, ammonium and alkanolammonium salts.

Other suitable antifoam compounds include, for example, high molecular weight fatty esters (such as fatty acid triglycerides), fatty acid esters of monovalent alcohols, aliphatic C ₁₈ -C ₄₀ ketones (such as stearyl ketone), N-alkylated amino triglycerides, Azines such as tri- or hexa-alkylmelamines or di- to tetraalkyldiamine chlorotriazines formed as reaction products of cyanuric chloride with 2 or 3 moles of primary or secondary amines containing 1 to 24 carbon atoms, cyclic Propylene oxide, distearamide and monostearyl dialkali metal (eg sodium, potassium, lithium) phosphates and esters.

Preferred suds suppressor systems include:

(a) An antifoam compound, preferably a silicone antifoam compound, most preferably a silicone antifoam compound comprising a combination of:

(i) polydimethylsiloxane, comprising 50 to 99%, preferably 75 to 95%, by weight of the polysiloxane antifoam compound; and

(ii) silicon dioxide from 1 to 50%, preferably from 5 to 25%, by weight of the polysiloxane/silica antifoam compound;

Wherein the silicon dioxide/polysiloxane antifoaming compound is incorporated in an amount of 5 to 50%, preferably 10 to 40% by weight;

(b) A dispersant compound, most preferably comprising 0.5 to 10%, preferably 1 to 10%, by weight of a silicone glycol rake copolymer with a polyoxyalkylene content of 72-78%, epoxy The ratio of ethane to propylene oxide is from 1:0.9 to 1:1.1; a particularly preferred silicone glycol rake copolymer of this type is DCO544, available from DOW Corning under the tradename DCO544;

(c) An inert carrier fluid compound, most preferably comprising from 5 to 80%, preferably from 10 to 70%, by weight of a _C16 - _C18 ethoxylated alcohol having a degree of ethoxylation of from 5 to 50, preferably from 8 to 15.

A highly preferred granular antifoam system is described in EP-A-0210731, comprising a polysiloxane antifoam compound and an organic carrier material having a melting point in the range of 50 to 85° C., wherein the organic carrier material comprises glycerol and has a concentration of 12 to A monoester of a fatty acid with a carbon chain of 20 carbon atoms. EP-A-0210721 discloses other preferred granular suds suppressor systems in which the organic carrier material is a fatty acid or alcohol or a mixture thereof having a melting point of 45 to 80° C. with a carbon chain of 12 to 20 carbon atoms.

Other highly preferred suds suppressing systems comprise dimethicone or mixtures of polysiloxanes such as dimethicone, aluminosilicates and polycarboxylic acid polymers such as copolymers of laic and acrylic acid .

Polymeric Dye Transfer Inhibitors

The compositions according to the invention may further comprise from 0.01 to 10%, preferably from 0.05 to 0.5%, by weight of polymeric dye transfer inhibiting agents.

The polymeric dye transfer inhibiting agent is preferably selected from polyamine N-oxide (polyamineN-oxide) polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, polyvinylpyrrolidone or combinations thereof, whereby these polymerized The substance can be a cross-linked polymer.

Fluorescent whitening agent

The compositions of the present invention also optionally contain from about 0.005 to 5% by weight of certain types of hydrophilic optical brighteners.

Hydrophilic fluorescent whitening agents suitable for use in the present invention include those of the following structural formula: Wherein R ₁ is selected from anilino, N-2-two-hydroxyethyl and NH-2-hydroxyethyl; R ₂ is selected from N-2-two-hydroxyethyl, N-2-hydroxyethyl-N- Methylamino, morpholino, chloro and amino; M is a salt-forming cation such as sodium or potassium.

In the above formula, when R ₁ is anilino, R ₂ is N-2-di-hydroxyethyl and M is a cation such as sodium, the whitening agent is 4,4'-bis[(4-anilino-6- (N-2-Di-hydroxyethyl)-s-triazin-2-yl)amino]-2,2'-stilbene disulphonic acid and disodium salt. Such brighteners are sold under the trade name Tinopal-UNPA-GX by the company Ciba-Geigy. Tinopal-CBS-X and Tinopal-UNPA-GX are preferred hydrophilic optical brighteners for use in the detergent compositions of the present invention.

In the above formula, when R ₁ is anilino, R ₂ is N-2-hydroxyethyl-N-2-methylamino and M is a cation such as sodium, the brightener is 4,4'-bis[(4- Anilino-6-(N-2-hydroxyethyl-N-methylamino)-s-triazin-2-yl)amino]-2,2'-stilbene disulphonic acid disodium salt. Such brighteners are sold under the tradename Tinopal 5BM-GX by the company Ciba-Geigy.

In the above formula, when R ₁ is an anilino group, R ₂ is a morpholino group and M is a cation such as sodium, the whitening agent is 4,4'-bis[(4-anilino-6-morpholino-s- Triazin-2-yl)amino]-2,2'-stilbene disulfonic acid, sodium salt. Such brighteners are sold under the tradenames Tinopal-DMS-X and Tinopal AMS-GX by the company Ciba Geigy.

Polymeric Soil Release Agent

Supplementary polymeric soil release agents (hereinafter "SRA") may optionally be used in the compositions of the present invention. If used, SRA's will generally comprise from 0.01 to 10.0%, typically from 0.1 to 5%, preferably from 0.2 to 3.0%, by weight of the composition.

The additional SRP's include hydrophilicity-improving cellulose derivatives such as ester derivatives of CMC. Also included are nonionic cellulose ethers and derivatives.

Preferred SRA's typically have a hydrophilic segment that makes the surface of hydrophobic fibers such as polyester and nylon hydrophilic, and a hydrophobic segment that deposits on the hydrophobic fiber and remains attached to it through the completion of the wash and rinse cycle, thereby serving as The anchor (fixer) of the above-mentioned hydrophilic segment. This makes stains that appear after treatment with the SRA easier to remove in subsequent wash steps.

Preferred SRA's include oligomeric terephthalates, typically prepared by a process involving at least one transesterification/oligomerization, by using a metal catalyst such as titanium(IV) alkoxide. Such esters can be prepared with additional monomers which can be incorporated into the ester structure through one, two, three, four or more positions, without, of course, producing a densely crosslinked overall structure.

Suitable SRA's include substantially linear esters composed of an oligoester backbone of terephthaloyl and oxyalkyleneoxy repeat units and an allyl-derived sulfonated end group moiety covalently attached to said backbone Sulfonated products of oligomers as described, for example, in US4968451, issued November 6, 1990 to J.J. Scheibel and E.P. Gosselink. Such ester oligomers can be prepared by: (a) ethoxylating allyl alcohol; (b) reacting the product of (a) with dimethyl terephthalate ("DMT") and 1,2-propanediol ("PG") is reacted in two transesterification/oligomerization steps; and (c) reacting the product of (b) with sodium metabisulfite in water. Other SRP's include the non-ionically terminated 1,2-propylene/polyoxyethylene terephthalate polyesters of US4711730 issued December 8, 1987 to Gosselink et al., e.g. by poly(ethylene glycol) methyl ether, Those produced by transesterification/oligomerization of DMT, PG and polyethylene glycol ("PEG"). Other examples of SRA's include: US4721580, issued January 26, 1988 to Gosselink, partially and fully anionically terminated oligoesters such as those derived from ethylene glycol ("EG"), PG, DMT and Na-3,6-dioxo Oligomers of hetero-8-hydroxyoctane sulfate; non-ionically terminated polyester oligomers such as DMT, methyl (Me)-terminated PEG and EG of US4702857 issued 27 October 1987 to Gosselink and/or PG, or DMT, EG and/or PG, Me-terminated PEG and Na-dimethyl-5-sulfoisophthalate mixture production; and granted to Maldonado on October 31, 1989, Anionically (especially sulfoaroyl) terminated terephthalates of US4877896 to Grosselink et al., the latter being typical SRA's suitable for laundry and fabric conditioning products, examples are derived from m-sulfobenzoic acid monosodium salt, PG and The DMT prepared ester composition optionally but preferably further comprises an additional PEG, eg PEG3400.

SRA's also include: pure copolymeric blocks of ethylene terephthalate or propylene terephthalate with polyoxyethylene or polyoxypropylene terephthalic acid, see US3959230 and 1975 issued May 25, 1976 to Hays _US3893929 issued July 8 _, 1976 to Basadur; cellulose derivatives such as _hydroxyether cellulose polymers obtained from Dow as METHOCEL; US4000093, Nicol et al., issued January 28; and having an average degree of substitution (methyl) of about 1.6 to about 2.3 per anhydroglucose unit and a solution viscosity of about 80 to about 120 centipoise as measured in 2% aqueous solution at 20°C of methyl cellulose ether. These materials are commercially available as METOLOSE SM100 and METOLOSE SM200, which are trade names of methyl cellulose ethers manufactured by Shin-etsu Kagaku Kogyo KK.

Other types of SRA's include: (I) nonionic terephthalates linked to polymeric ester structures with diisocyanate coupling agents, see US4201824 (Violland et al.) and US4240918 (Lagasse et al.); SRA's with carboxylate end groups are prepared by adding trimellitic anhydride to SRA's to convert the terminal hydroxyl groups into trimellitate esters. By proper choice of catalyst, the trimellitic anhydride bonds to the end of the polymer through the ester of the isolated carboxylic acid of trimellitic anhydride rather than by opening the anhydride bond. Both nonionic and anionic SRA's can be used as starting materials as long as they have terminal hydroxyl groups that can be esterified. See US4525524 (Tung et al.). Other classes include: (III) urethane-linked various anionic terephthalate SRA's, see US4201824 (Violland et al);

other optional ingredients

Other optional ingredients suitable for inclusion in the components or compositions of the present invention include fragrances, pigments and filler salts, the preferred filler salt being sodium sulfate.

Very preferred compositions contain from about 2 to about 10% by weight of an organic acid, preferably citric acid. Also, preferably in combination with carbonates, small amounts (e.g., less than about 20% by weight) of neutralizing agents, buffers, phase regulators, hydrotropes, enzyme stabilizers, polyacids, foam regulators, opacifiers, Antioxidants, fungicides and dyes, such as those described in US 4,285,841, Barrat et al., issued August 25, 1981 (incorporated herein by reference).

The form of the component or composition

The components or compositions of the invention may take a variety of physical forms, including liquid and solid forms such as tablets, flakes, lozenges and bars, preferably granular forms. The components or compositions can be prepared by various methods, depending on their product form. Solid compositions or components can be prepared by methods such as dry mixing, agglomeration, compression molding, or spray drying of the various compounds contained in the detergent component, or a combination of these techniques.

It is very preferred that the cyclic amine-based polymer described herein and the anionic cellulosic material are present in an intimate admixture. In the solid compositions or components of the present invention, this mixture may be obtained by any mixing method including agglomeration. The intimate mixture is preferably in the form of compacted, agglomerated or spray-dried granules.

The detergent compositions and components of the invention preferably have a bulk density of from 300 g/l, even 350 g/l or 450 g/l to 1500 g/l, or 1000 g/l, or even 850 g/l.

fabric washing method

The invention also provides a washing method. The method involves contacting the fabrics with an aqueous wash liquor formed from an effective amount of the detergent component or composition of the present invention as hereinbefore described or from components of said component or composition. Contacting of the fabrics with the lotion typically occurs under agitation, but the components or compositions of the present invention may also be used to form non-agitated aqueous fabric cleaning and treatment immersion solutions. As noted above, it is preferred that the wash solution has a pH of less than about 11.0, preferably less than 10.5, most preferably less than 9.5.

Effective amounts of dense liquid or granular detergent components or compositions in washing machine wash liquors are preferably from about 500 to about 10,000 ppm or even 7,000 ppm, more preferably from about 1,000 to about 3,000 ppm.

Fabric Conditioning and Softening

The detergent components or compositions of the present invention can also be used to treat and condition fabrics and textiles. For example, a fabric conditioning component or composition comprising a cyclic amine-based polymer and anionic cellulosic polymer described herein can be added during the rinse cycle of a conventional household laundry operation to impart the aforementioned fabric appearance and integrity benefits. Preferably at least about 1%, preferably about 10%, more preferably about 20% to about 80%, more preferably up to about 60%, of the composition or component is one or more fabric softening actives, such as positively charged Hydrocarbons, such as C12-C22 dialkyl substituted quaternary ammonium salts and/or clays, optionally with flocculating polymers.

Alternatively, the compositions or components of the present invention may be present in or in the form of softening and cleaning compositions, as described in EP-B1-313146 and WO93/01267, preferably containing other softening ingredients such as clay and optionally flocculated polymer.

The following are chemical structures of some cyclic amine-based polymers of the present invention, prepared as described in co-pending patent applications PCT/US98/19143 and PCT/US98/19142. Side reactions expected to occur during the condensation are not shown.

Table 1

Abbreviations used in the examples of foaming components and detergent compositions LAS : sodium linear C11-13 alkylbenzene sulfonate LAS(I): potassium linear or branched C11-13 alkylbenzene sulfonate TAS : tallow Sodium Alkyl Sulfate CxyAS : C1x-C1y Sodium Alkyl Sulfate C46SAS : C14-C16 Secondary (2,3) Sodium Alkyl Sulfate CxyEzS : C1x-C1y Sodium Alkyl Sulfate CxyEz condensed with z moles of ethylene oxide CxyEz : with the average C1x-C1y major linear primary of z molar ethylene oxide condensation

Alcohol QAS : R2.N+(CH3)2(C2H40H), R2=C12-C14QAS1 : R2.N+(CH3)2(C2H4OH), R2=C8-C11APA : C8-C10 aminopropyl dimethylamine soap : made of cattle Linear alkanes derived from an 80/20 blend of oil and coconut fatty acids

Sodium carboxylate adduct x: adduct with number x according to table I STS: sodium toluenesulfonate CFAA: C12-C14 (coco) alkyl N-methylglucamide TFAA: C16-C18 alkane Base N-methylglucamide TPKFA : C12-C14 topped whole fraction fatty acid STPP : Anhydrous sodium tripolyphosphate TSPP : Tetrasodium pyrophosphate A-type zeolite : Formula with primary particle size in the range of 0.1 to 10 μm

  Na12(AlO2SiO2)12·27H2O hydrated sodium aluminosilicate (by dry basis

Weight representation) NaSKS-6: layered crystalline silicate of formula d-Na2Si2O5 Citric acid I: anhydrous citric acid Citric acid II: monohydrate citric acid Malic acid: anhydrous malic acid, 80% particle size 50 to 100 μm, volume average particle size

  75 μm maleic acid : Anhydrous maleic acid, 80% particle size is 5 to 30 μm, volume average particle size is

  15 μm tartaric acid : anhydrous tartaric acid, 80% particle size is 25 to 75 μm, volume average particle size is

50 μm Carbonate: Anhydrous sodium carbonate Bicarbonate: Anhydrous sodium bicarbonate Silicate: Amorphous sodium silicate (SiO ₂ : Na ₂ O = 2.0:1) Sulfate: Anhydrous sodium sulfate Mg Sulfate: Magnesium Sulfate Citrate Anhydrous: 86.4% active trisodium citrate dihydrate, particle size distribution at 425

and 850μm MA/AA : 1:4 maleic acid/acrylic acid copolymer, average molecular weight about 70000MA/AA : 4:6 maleic acid/acrylic acid copolymer, average molecular weight about 10000 (1)AA : polyacrylic acid Sodium polymer, average molecular weight 4500CMC: Sodium carboxymethylcellulose Cellulose ether: Methylcellulose with a degree of polymerization of 650 purchased from Shin Etsu Chemicals

  Vitamin Ether Protease : Proteolytic enzyme, 3.3% by weight active enzyme, supplied by NOVO

Industries A/S sells Protease I under the tradename Savinase: proteolytic enzyme with 4% by weight active enzyme as in WO95/10591

As described, sold by Genencor Int. Inc. Alcalase: proteolytic enzyme, 5.3% by weight active enzyme, sold by NOVO

Industries A/S sells Cellulase: Cellulolytic enzymes, 0.23% by weight active enzyme, sold by NOVO

Industries A/S sells amylase under the tradename Carezyme: amylolytic enzyme, 1.6% by weight active enzyme, supplied by NOVO

Industries A/S sells lipase under the tradename Termamyl 120T: lipolytic enzyme, 2.0% by weight active enzyme, supplied by NOVO

Industries A/S sells lipase (1) under the tradename Lipolase: lipolytic enzyme, 2.0% by weight active enzyme, supplied by NOVO

Industries A/S sells Endolase under the tradename Lipolase Ultra: Endoglucanase with 1.5% by weight active enzyme, supplied by NOVO

Industries A/S sells PB4: Granules of sodium perborate tetrahydrate containing the formula NaBO ₂ 3H ₂ O, weight average

950 μm, 85% of the particles have a particle size of 850 to 950 μm PB1: Granules of anhydrous sodium perborate bleach containing formula NaBO ₂ ·H ₂ O ₂ , weight

The average particle _size is 800 μm, 85% of the particles have _a particle size of 750 to 950 μm Percarbonate: particles of sodium percarbonate containing the formula _{2Na2CO3 3H2O2} , the weight average particle size is

  850μm, 5% or less particle size is smaller than 600μ.m, 2% or less particle size is larger than

      1180μmNOBS  : Contains particles of nonanoyloxybenzenesulfonate in the form of sodium salt, with a weight average particle size of

  750 to 900 μmNAC-OBS : particles containing (6-nonylaminocaproyl)oxybenzenesulfonate, weight average particle size

  for 825 to 875 μm TAED : Granular Tetraacetylethylenediamine DTPA : Diethylenetriaminepentaacetic acid DTPMP : Diethylenetriaminepenta(methylene phosphonate), commercialized by Monsanto

Sold under the name Dequest 2060 Photosensitization: Sulfonated Zinc Phthalocyanine Encapsulated in Bleach (1) Dextrin Soluble Polymer Photosensitization: Sulfonated Aluminum Phthalocyanine Encapsulated in Bleach (2) Dextrin Soluble Polymer Brightener 1: 4,4'-bis(2-sulfostyreneyl)biphenyl disodium Brightener 2: 4,4'-bis(4-anilino-6-morpholino-1,3 , 5-triazin-2-yl) ammonia

Disodium stilbene-2,2'-disulphonate EDDS : Ethylenediamine-N,N'-disuccinic acid, (S,S) isomer in the form of sodium salt HEDP : 1,1-hydroxyethane Diphosphonic acid PEGx : Polyethylene glycol, molecular weight x (typically 4000) PEO : Polyethylene oxide, average molecular weight 50,000 TEPAE : Tetraethylenepentamine ethoxylate PVI : Polyvinyl imidosole, average molecular weight 20,000PVP : Polyvinylpyrrolidone polymer, average molecular weight 60,000PVNO : Polyvinylpyridine N-oxide polymer, average molecular weight 50,000PVPVI : Copolymer of polyvinylpyrrolidone and vinylimidazole, average molecular weight

Quantity 20000QEA : double ((C2H5O)(C2H4O)n)(CH3)-N+-C6H12-N+-(CH3) double

  ((C2H5O)-(C2H4O))n, where n=20-30SRP1 : Anion-terminated polyester SRP2 : Diethoxylated poly(1,2-propylene terephthalate) short-block polymerization

 Physical PEI  : Polyethyleneimine, with an average molecular weight of 1800 and an average degree of ethoxylation of

7 ethoxyl residues per nitrogen polysiloxane: polydimethylsiloxane defoamer with siloxane-oxyalkylene copolymer as dispersant The ratio of the dispersant is

10:1 to 100:1 sunscreens: Water-based monostyrene latex blends, manufactured by BASF

Aktiengesellschaft sells wax under the trade name Lytron 621: Paraffin Wax Bubbles: Any of Bubbles I to XII

In the following examples, all contents are % by weight of the composition:

The following compositions in Table II are compositions of the present invention. A B C D. E. f G h I spray dried granules LAS 10.0 10.0 15.0 5.0 5.0 10.0 - - - STS - 1.0 - - - - MBAS - - 5.0 5.0 - - - C ₄₅ AS - - 1.0 2.0 2.0 - - - C ₄₅ AE ₃ S - - 1.0 - - - Adduct 1 or 2 2.0 0.5 1.0 1.0 3.0 5.0 1.0 1.5 0.2 DTPA, HEDP and/or EDDS 0.3 0.3 0.5 0.3 - - - _MgSO4 0.5 0.5 0.1 - - - - Sodium citrate - - - 3.0 5.0 - - - Sodium carbonate 10.0 7.0 15.0 10.0 - - - sodium sulfate 5.0 5.0 - - 5.0 3.0 - - - Sodium silicate 1.6R - - - - 2.0 - - - Type A zeolite 16.0 18.0 20.0 20.0 - - - - - SKS-6 - - - 3.0 5.0 - - - - MA/AA or AA 1.0 2.0 11.0 - - 2.0 - - - PEG4000 - 2.0 - 11.0 - 11.0 - - - QEA 1.0 - - - 1.0 - - - - brightener 0.05 0.05 0.05 - 0.05 - - - - silicone oil 0.01 0.01 0.01 - - 0.01 - - - CMC 1.0 2.0 2.5 1.5 0.5 4.0 1.0 2.0 0.5 Agglomerates LAS - - - - 2.0 2.0 - MBAS - - - - - - 1.0 C ₄₅ AS - - - - 2.0 - - AE ₃ - - - - - 1.0 0.5 carbonate - - 4.0 1.0 1.0 1.0 - Sodium citrate - - - - - - 5.0 CFAA - - - - - citric acid - - - 4.0 - 1.0 1.0 QEA - - - 2.0 2.0 1.0 - SRP - - - 1.0 1.0 0.2 - Type A zeolite - - - 15.0 26.0 15.0 16.0 Sodium silicate - - - - - - - PEG - - - - - - 4.0 - - builder agglomerates SKS-6 6.0 - - - 6.0 3.0 - 7.0 10.0 LAS 4.0 5.0 - - 5.0 3.0 - 10.0 12.0 Dry Add Granular Components foaming particles - 4.0 10.0 4.0 25 8.0 12.0 2.0 4.0 QEA - - - 0.2 0.5 - - - - NACAOBS 3.0 - - 4.5 - - - 2.5 - NOBS 1.0 3.0 3.0 - - - - - 5.0 TAEDI 2.5 - - 1.5 2.5 6.5 - 1.5 - MBAS - - - 8.0 - - 8.0 - 4.0 LAS (thin slice) 10.0 10.0 - - - - - 8.0 - Citric acid II - - - spray on brightener 0.2 0.2 0.3 0.1 0.2 0.1 - 0.6 0.3 dye - - - 0.3 0.05 0.1 - - - AE7 - - - - - 0.5 - 0.7 - spices 1.0 0.5 1.1 0.8 0.3 0.5 0.3 0.5 - dry plus Citrate - - 20.0 4.0 - 5.0 15.0 - 5.0 Percarbonate 15.0 3.0 6.0 10.0 - - 24.0 18.0 5.0 Perborate - - - - 6.0 18.0 - - - photobleach 0.02 0.02 0.02 0.1 0.05 - 0.3 - 0.03 Enzymes (cellulase, amylase, protease, lipase) 1.3 0.3 0.5 0.5 0.8 2.0 0.5 0.16 0.2 carbonate 0.0 10.0 - - - 5.0 8.0 10.0 5.0 Spices (encapsulated) - 0.5 0.5 - 0.3 - 0.2 - - Foam suppressor 1.0 0.6 0.3 - 0.10 0.5 1.0 0.3 1.2 Soap 0.5 0.2 0.3 3.0 0.5 - - 0.3 - citric acid (I or crude) - - - 6.0 6.0 - - - 5.0 Dyed carbonate (blue, green) 0.5 0.5 1.0 2.0 - 0.5 0.5 0.5 1.0 SKS-6 - - - 4.0 - - - 6.0 - fill to 100%

Table III The following compositions are compositions of the present invention. A B C D. E. f G h I spray dried granules LAS or LAS(I) 10.0 10.0 16.0 5.0 5.0 10.0 - - - TAS - 1.0 - - - - MBAS - - - 5.0 5.0 - - - C ₄₅ AS - - 1.0 2.0 2.0 - - - C ₄₅ AE ₃ S - - - 1.0 - - - QAS - - 1.0 1.0 - - - DTPA, HEDP and/or EDDS 0.3 0.3 0.3 0.3 - - - MgSO4 0.5 0.4 0.1 - - - - Sodium citrate 10.0 12.0 17.0 3.0 5.0 - - - Sodium carbonate 15.0 8.0 15.0 10.0 - - - sodium sulfate 5.0 5.0 - - 5.0 3.0 - - - Sodium silicate 1.6R - - - - 2.0 - - - Type A zeolite - - - 2.0 - - - - - SKS-6 - - - 3.0 5.0 - - - - MA/AA or AA 1.0 2.0 0.0 - - 2.0 - - - PEG4000 - 2.0 - 1.0 - 1.0 - - - QEA 1.0 - - - 1.0 - - - - brightener 0.05 0.05 0.05 - 0.05 - - - - silicone oil 0.01 0.01 0.01 - - 0.01 - - - Blister Granules I, III, IV, VII or VIII 5 12 - - - - - - - Agglomerates LAS 4.0 3.0 4.0 5.0 - - 2.0 2.0 - STS 1.0 1.0 - - - - - 1.0 C ₄₅ AS - - - - - - 2.0 - - AE ₃ - - - - - - - 1.0 0.5 carbonate - - - - 4.0 1.0 1.0 1.0 - Sodium citrate - - - - - - - - 5.0 CMC 1.0 1.5 0.8 2.0 1.0 0.5 0.3 2.8 1.5 citric acid - - - - - 4.0 - 1.0 1.0 QEA 1.0 - - - - - 2.0 1.0 2.0 Adduct 1, 2 or 3 2.0 0.3 1.5 2.0 0.5 1.0 1.0 0.2 0.5 Type A zeolite - - - - - 15.0 26.0 15.0 16.0 Sodium silicate - - - - - - - - - PEG - - - - - - 4.0 - - TAEDII 3.0 1.5 builder agglomerates SKS-6 6.0 5.0 - - 6.0 3.0 - 7.0 10.0 LAS 4.0 5.0 - - 5.0 3.0 - 10.0 12.0 Dry Add Granular Components foaming particles - 10.0 4.0 5 15 8.0 2.0 20 4.0 NACAOBS 3.0 - - 1.5 - - - 5.5 - NOBS/LOBS/DOBS - 3.0 3.0 - - - - - 5.0 TAED1 2.5 - - 1.5 2.5 6.5 - 1.5 - MBAS - - - 8.0 - - 8.0 - 4.0 LAS (thin slice) - - - - - - - 8.0 - spray on brightener 0.2 0.2 0.3 0.1 0.2 0.1 - 0.6 - dye - - - 0.3 0.05 0.1 - - - AE7 - - - - - 0.5 - 0.7 - spices - - - 0.8 - 0.5 0.8 0.5 1.0 dry plus QEA - - - 0.2 0.5 - - - - Citrate 4.0 - 3.0 4.0 - 5.0 15.0 - 5.0 Percarbonate 15.0 3.0 6.0 10.0 - - 12.0 18.0 5.0 Perborate - - - - 6.0 18.0 - - - photobleach 0.02 0.02 0.02 0.1 0.05 - 0.3 - 0.03 Enzymes (cellulase, amylase, protease, lipase) 1.5 0.3 0.5 0.5 0.8 2.0 0.5 0.16 0.2 Carbonate II - - - - - 5.0 8.0 10.0 5.0 Spices (encapsulated) 0.6 0.5 0.5 - 0.3 0.5 0.2 0.1 0.6 Foam suppressor 1.0 0.6 0.3 - 0.10 0.5 1.0 0.3 1.2 Soap 0.5 0.2 0.3 3.0 0.5 - - 0.3 - Citric acid II - - - - - - - 5.0 5.0 Dyed carbonate (blue, green) 0.5 0.5 ? 2.0 - 0.5 0.5 0.5 1.0 SKS-6 - - - 4.0 - - - 6.0 - fill to 100%

Table IV The following is a high-density detergent formulation containing bleach according to the present invention: A B C blown powder Type A zeolite - - 15.0 sodium sulfate 0.0 5.0 0.0 LAS 3.0 - 3.0 C45AS 3.0 2.0 4.0 QAS - - 1.5 DTPMP 0.4 0.4 0.4 CMC 0.4 0.4 0.4 MA/AA 4.0 2.0 2.0 Blister Granules I or VIII 7.0 - - TAED - - 3.0 Agglomerates CMC - 1.0 1.5 Adduct 1 or 2 - 0.5 0.8 LAS - 11.0 7.0 TAS or STS 2.0 2.0 1.0 Silicate 3.0 - 4.0 Type A zeolite 8.0 8.0 8.0 carbonate 8.0 8.0 4.0 Agglomerates Adduct 1 or 2 1.0 - - CMC 3.0 - - spray on - spices 0.3 0.3 0.3 C25E3 2.0 - 2.0 brightener 0.1 0.4 photobleach 0.03 0.05 - dry additive QEA 1.0 0.5 0.5 Citric acid I 5.0 - 2.0 Bicarbonate I - 3.0 - Carbonate II 8.0 15.0 10.0 NACOBS 6.0 - 5.0 manganese catalyst - - 0.3 TAEDI 3.0 - NOBS - 2.0 - Percarbonate 14.0 7.0 10.0 Polyethylene oxide of MW5000000 - - 0.2 bentonite clay - - 10.0 foaming particles - 5.5 7.5 protease 1.0 1.0 1.0 Lipase 0.4 0.4 0.4 Amylase 0.6 0.6 0.6 cellulase 0.6 0.6 0.6 Silicone defoamer 5.0 5.0 5.0 Balance (moisture and others) 100.0 100.0 100.0 Density (g/l) 850 850 850

The following table V is the liquid composition of the present invention: Component Wt% Wt% Wt.% C _12-15 alkyl ether (2.5) sulfate 38 38 38 C ₁₂ Glucamide 6.86 6.86 6.86 Citric acid 4.75 4.75 4.75 C _12-14 fatty acids 2.00 2.00 2.00 Enzyme 1.02 1.02 1.02 MEA 1.0 1.0 1.0 Propylene glycol 0.36 0.36 0.36 Borax 6.58 6.58 6.58 Dispersant 1.48 1.48 1.48 Sodium tosylate 6.25 6.25 6.25 Adduct 1, 2, 4 or 5 1.0 0.5 2.0 CMC 1.0 2.5 0.5 Dyes, fragrances, brighteners, preservatives, balance balance balance suppressors, other minor components, water 100% 100% 100%

The following liquid detergent formulations of Table VI are prepared according to the present invention:

A      B      C      D      ELAS           11.5    9.0     -     4.0     -C25E2.5S       -      3.0   18.0     -    16.0C45E2.25S     11.5    3.0     -    16.0     -C23E9          -      3.0    2.0    2.0    1.0C23E7          3.2     -      -      -      -CFAA           -       -     5.0     -     3.0TPKFA          2.0     -     2.0    0.5    2.0 Citric acid (50 %) 6.5 1.0 2.5 4.0 2.5 Calcium methampuel 0.1 0.06 0.1-0.5 0.06 0.1 0.05 0.05sts 4.0 1.0 1.2-Boron 0.6-3.0 3.0 Sodium hydroxide 6.0.0 3.0 3.0 Etanol 2.0 1.0 4.0 4.0 4.0 4.0 4.0 4.0 3.01, 2-propylene glycol 3.0 2.0 8.0 8.0 5.0 single ethanlamine 3.0 1.0 2.5 1.0cmc 2.0 1.0 1.0 3.0 0.4 Integration 1, 2 or 6 0.3 1.0 2.0 0.8 1.0 protease 0.03 0.03 0.02 0.02 lipase-0.002-- Amylase - - - - - 0.00 -

                                                                                                                      

2 05SRP 0.2 — 0.1 -DTPA-0.3 -PVNO-0.3-0.2 White agent 1 0.2 0.07 0.1-Siliconxane Antimary 0.04 0.02 0.1 0.1 0.1 Others and Water Water

The following liquid detergent formulations of Table VII are prepared according to the present invention:

A B C D E F g Hlas 10.0 13.0 9.0-25.0--C25AS 4.0 1.0 2.0 10.0-13.0 15.0c25E3S 1.0-3.0-2.0 2.0c25E7 6.0 13.0 2.5-4.0-4.5-6.0 8.0 8.0APA-1.4-3.0 1.0 2.0 -TPKFA 2.0-13.0 7.0-15.0 11.0 Citric acid 2.0 3.0 1.5 1.0 1.0 1.0 1.0 Twelve Plately/12.0-15.0---Tithyne Bid Ambol Amber Caucifon Fatty acid 4.0 2.0 1.0-1.0-3.5-ethanol 4.0 4.0 7.0 2.0 7.0 2.0 2.01, 2-propane 4.0 4.0 7.0 6.0 8.0 10.0 single ethanlamine--5.0-9.0 9.0-8.0-0.4 0.3 CMC 0.2 2.0 0.5 0.7 2.0 1.2 1.0 4.0 Integration 1 or 2 0.3 0.5 1.0 1.0 1.0 0.5 1.0detpmp 1.0 1.0 0.5 1.0 Agly enzyme 0.02 0.01 0.02 protease 0.02 0.01.008-.003.003 lipase-. 002-.002.004 0.01 0.01 0.01 amylase .004.004 0.01.008 -.004 .003 cellulose enzyme-.002-0.2 0.1SRP2 0.3-0.3 0.1 1.0 1.5 2.5 boric acid 0.1 0.2 1.0 2.0 4.0 4.0--0.02-0.01 0.1 0.2 0.3-White agent 1 ～ 0.4-0.4--泡 0.3-0.1 0.8 0.7--0.4-0.3 8.0 8.0 8.2NAOH to pH 8.0 8.0 7.6 7.7

Others and water

Claims (11)

1. detergent composition or component comprise:

A) 0.01 to 90% weight, preferred 0.05 to 50% weight contain the anion fiber cellulosic material of anion substituent R-X-Z, and wherein R is saturated, unsaturated or the aromatic hydrocarbons spacer, and X is oxygen, nitrogen or sulphur, and Z is carboxylate radical, sulfonate radical, sulfate radical or phosphonate groups; With

B) 0.01 to 90% weight, preferred about 0.05 is to about 20% weight ring amine based polymer.

2. the detergent composition of claim 1 or component, R is C in the wherein said cellulose materials ₁-C ₄Alkylidene group, X are oxygen.

3. the detergent composition of claim 2 or component, wherein said anion fiber cellulosic material comprises carboxymethyl cellulose, preferably its sodium-salt form.

4. the detergent composition of above-mentioned arbitrary claim or component, wherein said cyclic amine based polymer, oligopolymer or multipolymer have following general formula: Wherein: each T is independently selected from H, C ₁-C ₁₂The alkyl of alkyl, replacement, C ₇-C ₁₂Alkaryl ,-(CH ₂) _hCOOM ,-(CH ₂) _hSO ₃M, CH ₂CH (OH) SO ₃M ,-(CH ₂) _hOSO ₃M,

With-R ₂Q;-wherein W comprises the ring-type component part that at least one is selected from following group:

Except that described at least one ring-type component part, W can also comprise the aliphatic series of following general structure or the aliphatic part that replaces:

-each B is C independently ₁-C ₁₂Alkylidene group, C ₁-C ₁₂The alkylidene group, the C that replace ₃-C ₁₂Alkenylene, C ₈-C ₁₂Dialkyl group arylidene, C ₈-C ₁₂Dialkyl group arylidene two bases and-(R ₅O) _nR ₅-;

-each D is C independently ₂-C ₆Alkylidene group;

-each Q is independently selected from hydroxyl, C ₁-C ₁₈Alkoxyl group, C ₂-C ₁₈Hydroxyl alkoxyl group, amino, C ₁-C ₁₈Alkylamino, dialkyl amido, trialkyl amino, heterocycle one amino and diamino;

-each R ₁Be independently selected from H, C ₁-C ₈Alkyl and C ₁-C ₈Hydroxyalkyl;

-each R ₂Be independently selected from C ₁-C ₁₂Alkylidene group, C ₁-C ₁₂Alkenylene ,-CH ₂-CH (OR ₁)-CH ₂, C ₈-C ₁₂Alkarylene, C ₄-C ₁₂Alkyl sub-dihydroxy, poly-(C ₂-C ₄Alkylene oxide group) alkylidene group, H ₂CH (OH) CH ₂OR ₂OCH ₂CH (OH) CH ₂-and C ₃-C ₁₂Hydrocarbyl portion;

Condition is to work as R ₂Be C ₃-C ₁₂During hydrocarbyl portion, described hydrocarbyl portion can comprise about 2 components to about 4 following general structures:

-each R ₃Be independently selected from H, O, R ₂, C ₁-C ₂₀Hydroxyalkyl, C ₁-C ₂₀The alkyl of alkyl, replacement, C ₆-C ₁₁The aryl of aryl, replacement, C ₇-C ₁₁Alkaryl, C ₁-C ₂₀Aminoalkyl,

-(CH ₂) _hCOOM，-(CH ₂) _hSO ₃M，CH ₂CH(OH)SO ₃M，-(CH ₂) _hOSO ₃M，

-each R ₄Be independently selected from H, C ₁-C ₂₂Alkyl, C ₁-C ₂₂Hydroxyalkyl, aryl and C ₇-C ₂₂Alkaryl;

-each R ₅Be independently selected from C ₂-C ₈Alkylidene group, C ₂-C ₈The alkylidene group that alkyl replaces; With

A is compatible monovalence, divalence or multivalent anions;

M is compatible positively charged ion;

The number that the b=balancing charge is required;

Each x is 3 to about 1000 independently;

Each c is 0 or 1 independently;

Each h is about 1 to about 8 independently;

Each q is 0 to about 6 independently;

Each n is 1 to about 20 independently;

Each r is 0 to about 20 independently; With

Each t is 0 to 1 independently.

5. the detergent composition of above-mentioned arbitrary claim, wherein said cyclic amine based polymer is the adducts that comprises the group that is selected from piperazine, piperidines, Epicholorohydrin, benzyl quaternary ammonium Epicholorohydrin, the quaternized Epicholorohydrin of methyl, morpholine and composition thereof, preferred imidazoles-epichlorohydrin copolymer.

6. the detergent composition of claim 4 or component, wherein each R ₁Be H, and at least one W is selected from:

7. the detergent composition of claim 4 or component, wherein each R ₁Be H, and at least one W is selected from:

8. the detergent composition of claim 4 or component, wherein each R ₁Be H, and at least one W is selected from:

9. the detergent composition of above-mentioned arbitrary claim or component, wherein said cyclic amine based polymer and described anion fiber cellulosic material are intimate mixture.

10. the component of claim 9 or composition, wherein said intimate mixture exists with agglomerated particle, die mould particle or spray-dried granules form.

11. the laundry detergent composition of above-mentioned arbitrary claim, wherein said composition comprise one or more fabric softening components and/or dye transfer constituents for suppressing.