CN1238798A - Detergent compositions - Google Patents

Abstract

This invention relates to granular detergent compositions or components thereof for use in laundry and dishwashing, including oxygen-releasing bleaching systems containing a peroxygen source, and one or more cationic compounds, namely cationic (partial) quaternized ethoxylated polyamine compounds having sludge removal/anti-redeposition properties.

Description

detergent composition

technical field

The present invention relates to granular detergent compositions or components thereof for laundry and dishwashing comprising cationic compounds having particulate/soil removal/anti-redeposition properties and an oxygen releasing bleach system.

Background of the Invention

A particularly important property of detergent compositions is their ability to remove particulate soils from a variety of fabrics during the wash cycle. Probably the most common form of granular dirt is the mud-type dirt. Sludge particles typically comprise a negative layer of aluminosilicate, and positively charged cations (such as calcium) located between the layers and associated with the negative layer.

Various modes can be proposed for compounds with particulate/sludge removal properties. A pattern requires the compound to have two different properties. One is the ability of the compound to adsorb to the negatively charged layer of the soil particle and the other is the ability of the compound, once adsorbed, to pull apart (swell) the negatively charged layer so that the soil particle loses its cohesion and can then be removed in the wash water.

In addition to particle/soil removal, there is a need to keep the removed soil in suspension during the laundry (or dishwashing) cycle. Soil removed from the fabric and suspended in the wash water can redeposit onto the fabric surface. This redeposited soil can produce a particularly noticeable matting or "greying" effect on white fabrics. To reduce this problem, anti-redeposition agents can be included in detergent compositions.

For example, EP-B-111965 discloses the use in detergents of cationic compounds having both soil removal and antiredeposition properties.

US4659802 and US4664848 describe quaternized amines having soil removal and anti-redeposition properties which can be used in combination with anionic surfactants.

Regarding the anti-redeposition effect of positively reactive anti-redeposition compounds, a model is proposed below. Adsorption of positively charged molecules on the surface of soil particles in wash water imparts molecular dispersibility to these particles. As more and more of the compound is adsorbed onto the suspended sludge particles, the latter become encapsulated in the hydrophilic layer created by the attached ethoxy units. In this way, redeposition of hydrophilic coated soils on fabrics, especially hydrophobic fabrics such as polyester, is inhibited during the laundry or dishwashing cycle.

Another ingredient traditionally used in detergents is bleach to remove bleachable stains or soils from fabrics, such as bleach that releases oxygen.

A disadvantage in the use of most bleaches is that, since many other detergent ingredients are bleach sensitive they can be oxidized by the bleach and thus lose their original properties. Therefore, not all detergent ingredients are compatible with bleach.

The applicants have found that cationic, (partially) quaternized ethoxylated (poly)amines having soil removal/anti-redeposition properties are fully compatible with formulated oxygen-releasing bleaches. Thus, the overall cleaning and/or whiteness maintenance of detergent compositions or components thereof containing both cationic quaternary ethoxylated (poly)amines and bleaches can be improved because bleachable sludge stains are more Effectively removes from fabrics.

It has also been found that in detergent compositions (or components thereof), the use of (releasing-oxygen) bleaches in combination with partially quaternized ethoxylated (poly)amines makes (oxygen-releasing) bleaches Combined with fully quaternized ethoxylated (poly)amines, it can better improve the cleaning or whiteness maintenance effect. But even partially quaternized ethoxylated (poly)amines can be combined with bleach to improve cleaning or whiteness retention.

Without being bound by theory, the bleach compatibility of cationic quaternary ethoxylated (poly)amines can be explained as follows. In these molecules, the quaternization of the nitrogen group is believed to have a dual effect. For soil particles on the surface of the fabric or dispersed in the wash water, the adsorption on it can be improved by creating a positive charge in the molecule; Electron pair, which stabilizes the molecule in laundry detergents containing bleach.

All cited documents in this specification and their relevant parts are incorporated herein as a reference.

Summary of the invention

The present invention relates to granular detergent compositions or components thereof comprising an oxygen-releasing bleaching system comprising a peroxide source and one or more cationic compounds having particulate/sludge removal/anti-redeposition properties, i.e. cationic (Partially) quaternized ethoxylated (poly)amine compounds.

In more detail, the present invention relates to granular detergent compositions or components thereof comprising:

(a) oxygen-releasing bleaching systems containing a source of peroxygen; and

(b) Water-soluble cationic compounds having soil removal/anti-redeposition properties selected from the group consisting of:

1) Ethoxylated cationic monoamines having the following structural formula:

或 或

2) Ethoxylated cationic diamines having the formula:

or or

Wherein ^M1 is N+ or N group; each ^M2 is N+ or N group; and at least one ^M2 is N+ group;

3) Ethoxylated cationic polyamines having the following structural formula:

或-O-，4) and mixtures thereof; wherein A ¹ is

or -O-,

R is H or C ₁ -C ₄ alkyl or hydroxyalkyl, R ¹ is C ₂ -C ₁₂ alkylene, hydroxyalkylene, alkenylene, arylene or alkarylene, or has 2- A C ₂ -C ₃ oxyalkylene moiety of about 20 oxyalkylene units, but not capable of forming any ON bonds; each R ² is a C ₁ -C ₄ alkyl or hydroxyalkyl group, a -LX moiety, or two R ² together Forms the -(CH ₂ ) _r -A ² -(CH ₂ ) _s - moiety, where A ² is -O- or -CH ₂ -, r is 1 or 2, s is 1 or 2, and r+s is 3 or 4; each R ³ is C ₁ -C ₈ alkyl or hydroxyalkyl, benzyl, -LX moiety, or, two R ³ or one R ² together with one R ³ form -(CH ₂ ) _r - A ² -(CH ₂ ) _s - moiety; R ⁴ is substituted C ₃ -C ₁₂ alkyl, hydroxyalkyl, alkenyl, aryl or alkaryl with para-substitution; R ⁵ is C ₁ - C ₁₂ alkenyl, hydroxyalkylene, alkenylene, arylene or alkarylene, or C ₂ -C ₃ oxyalkylene moieties having 2 to about 20 oxyalkylene units, but not forming any OO or ON bond; X is a nonionic group selected from H, C ₁ -C ₄ alkyl or hydroxyalkyl ester or ether group, and a mixed group thereof; L is a polyoxyalkylene moiety-[(R ⁶ O ) _m (CH ₂ CH ₂ O) _n ]- the hydrophilic chain; wherein R ⁶ is C ₃ -C ₄ alkylene or hydroxyalkylene, and the number of m and n should be such that -(CH ₂ CH ₂ O ) _{the n-} moiety comprises at least about 50% by weight of said polyoxyalkylene moiety; when ^M is N+, d is 1, and when M is ^N , d is 0; for said cationic monoamine, n is at least about 16, At least about 6 for the cationic diamine, at least about 3 for the cationic polyamine; p is 3-8; q is 1 or 0; t is 1 or 0, but when q is 1, t is 1.

Wherein the ratio of (a) to (b) is 80:1 to 1:5.

Detailed description of the invention

An essential feature of the present invention is a water-soluble cationic compound having particulate/soil removal/anti-redeposition properties selected from the group consisting of cationic monoamines, diamines and polyamines.

The ratio of oxygen releasing bleaching system to water-soluble cationic compound is from 80:1 to 1:5, preferably from 40:1 to 1:2, most preferably from 20:1 to 1:1.

In detergent compositions, the water-soluble cationic compound is preferably present at 0.01-30%, more preferably 0.1-15%, most preferably 0.2-3.0% by weight of the detergent composition.

cationic amine

Water-soluble cationic compounds of the invention which may be used in granular detergent compositions or components thereof according to the invention include ethoxylated cationic monoamines, ethoxylated cationic diamines and ethoxylated cationic polyamines as defined above. amine.

环状的(如，或最优选直链的(如In the preceding formulas for cationic amines, ^R can be branched (e.g.,

circular (eg, or most preferably linear (eg

-CH ₂ CH ₂ -, -CH ₂ CH ₂ CH ₂ -)

) alkylene, hydroxyalkylene, alkenylene, alkarylene or alkylene oxide. For ethoxylated cationic diamines, R ¹ is preferably C ₂ -C ₆ alkylene. Each R ² is preferably a methyl group or a -LX moiety; each R ³ is preferably a C ₁ -C ₄ alkyl or hydroxyalkyl group, most preferably a methyl group.

The positive charge of the N+ group is offset by an appropriate number of counter anions. Suitable counter anions include Cl ⁻ , Br ⁻ , SO ₃ ⁻² , PO ₄ ⁻² , MeOSO ₃ ⁻ and the like. Particularly preferred counteranions are Cl ⁻ and Br ⁻ .

X may be a nonionic group selected from hydrogen (H), C ₁ -C ₄ alkyl or hydroxyalkyl ester or ether groups, and mixtures thereof. Preferred esters or ethers are acetate and methyl ether, respectively. Particularly preferred nonionic groups are H and methyl ether.

In the aforementioned structural formula, the hydrophilic chain L generally consists entirely of the polyoxyalkylene moiety [(R ⁶ O) _m (CH ₂ CH ₂ O) _n ]-. -(R ⁶ O) _m - and -(CH ₂ CH ₂ O) _n - in the polyoxyalkylene moiety may be mixed together, or preferably form a -(R ⁶ O) _m - moiety with -(CH ₂ CH ₂ O ) _n - a block of sections. R ⁶ is preferably C ₃ H ₆ (propylene); m is preferably 0 to about 5, most preferably 0, ie the polyoxyalkylene moiety consists entirely of -(CH ₂ CH ₂ O) _n -. The -( _CH2CH2O ) _n- moiety preferably comprises at least about 85% by weight of _the polyoxyalkylene moiety, most preferably 100% by weight (m is 0).

In the preceding formulas, M ¹ and each M ² are preferably N+ groups for cationic diamines and polyamines.

Preferred ethoxylated cationic monoamines and diamines have the formula:

Wherein X and n are as defined above, a is 0-20, preferably 0-4 (eg, ethylene, propylene, hexylene), b is 1 or 0. For the preferred cationic monoamines (b=0), n is preferably at least about 16, with typical values in the range of about 20-35. For the preferred cationic diamines (b=1), n is at least about 12, with typical values in the range of about 12-42.

In the aforementioned structural formula of ethoxylated cationic polyamine, R ⁴ (linear, branched, or cyclic) is preferably substituted with C ₃ -C ₆ alkyl, hydroxyalkyl or aryl; A ¹ is preferably

n is preferably at least about 12, with typical values in the range of about 12-42; p is preferably 3-6. When R ⁴ is a substituted aryl or alkaryl group, q is preferably 1 and R ⁵ is preferably a C ₂ -C ₃ alkylene group. When R ⁴ is a substituted alkyl, hydroxyalkyl or alkenyl, and q is 0, R ⁵ is preferably a C ₂ -C ₃ alkylene oxide moiety; when q is 1, R ⁵ is preferably a C ₂ -C ₃ alkylene base.

These ethoxylated cationic polyamines can be derived from polyaminoamides such as: or

These ethoxylated cationic polyamines can also be derived from polyaminopropylene oxide derivatives such as:

-(OC ₃ H ₆ ) _c -NH ₂

CH ₃ -(OC ₃ H ₆ ) _c -NH ₂

-(OC ₃ H ₆ ) _c -NH ₂

wherein each c is from 2 to about 20.

Oxygen Release Bleach System

Another essential feature of the present invention is an oxygen-releasing bleaching system comprising essentially a peroxygen source, preferably present at from 1% to 40% by weight of the detergent composition, for example comprising inorganic perhydrate bleaches and organic peroxyacids.

The ratio of oxygen releasing bleach system to water soluble cationic compound is from 80:1 to 1:5, preferably from 40:1 to 1:2, most preferably from 20:1 to 1:1.

A preferred bleaching system comprises a source of hydrogen peroxide and a peroxyacid bleach precursor compound. Peroxyacids are produced by in situ reaction of the precursors with a source of hydrogen peroxide. Preferred sources of hydrogen peroxide include inorganic perhydrate bleaches.

Silicate materials can be used as stabilizers in granular detergent compositions (containing oxygen releasing bleaches) of the present invention. Especially alkali metal silicates having a SiO ₂ :Na ₂ O ratio (R) of about 1.6:1 to 3.2:1 are suitable for use herein, although silicates outside this preferred range can also be used, although less worse. The sodium salt form of the silicate is generally employed, but the overall stability of the composition can be further increased if magnesium is included, as described more fully below. In situ formation of magnesium silicate is also suitable by adding sodium silicate and a magnesium salt (eg magnesium sulfate or magnesium chloride) in the same granule (eg in the same slurry when preparing spray-dried granules). Suitable silicates for the present invention include sodium silicate 1.6R solution, sodium silicate 2.0R solid or sodium silicate 3.2R solid available from Hoechst or Akzo. The ratio of silicate to the oxidation-sensitive component to be stabilized is preferably 1:1.

Inorganic perhydrate bleach

Inorganic perhydrate salts are the preferred source of hydrogen peroxide. These salts are usually sodium salts and are added in an amount of 1-40% by weight of the composition, more preferably 2-30% by weight, most preferably 5-20% by weight.

Inorganic perhydrate salts include perborates, percarbonates, perphosphates, persulfates and persilicates. These inorganic perhydrate salts are usually alkali metal salts. Inorganic perhydrate salts may be added as crystalline solids without other protection. For certain perhydrate salts, however, preferred embodiments of such granular compositions employ a coating of material which provides better storage stability for the perhydrate salt in the granular product.

Sodium perborate may be a monohydrate having the nominal structural formula NaBO ₂ H ₂ O ₂ , or a tetrahydrate NaBO ₂ H ₂ O ₂ .3H ₂ O.

Sodium percarbonate is the preferred perhydrate of the present invention. Sodium percarbonate is an adduct compound whose structural formula corresponds to 2Na ₂ BO ₂ .3H ₂ O ₂ and is available as a crystalline solid. Percarbonate is most preferably added to the composition as a coating to provide product stability.

Suitable coating materials to provide product stability include water soluble mixed salts of alkali metals, sulfates and carbonates. GB1,466,799 has already introduced this kind of coating and coating method. The weight ratio of the mixed salt coating material to the inorganic perhydrate is in the range of 1:200 to 1:4, more preferably 1:99 to 1:9, most preferably 1:49 to 1:19. Preferred mixed salts of sodium sulfate and sodium _carbonate have the general formula _{Na2SO4.nNa2CO3} , where n _is 0.1 to 3, preferably _0.3 to 1.0, most preferably 0.2 to 0.5.

Other coatings containing silicates (alone or mixed with borates, or boric acid, or other inorganics), waxes, oils, fatty soaps are also suitable for use in the present invention.

Potassium peroxymonopersulfate is another inorganic perhydrate salt useful in the detergent compositions of the present invention.

Peroxyacid Bleach Precursors

Peroxyacid bleach precursors 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 composition.

Suitable hydrophobic organic peroxyacid bleach precursor compounds generally contain one or more N- or O-acyl groups and such precursors can be selected from a wide range. Suitable species include anhydrides, esters, imides, lactams, or acylated derivatives of imidazoles and oximes. Among these classes, examples of useful substances are disclosed in GB-A-1586789. Suitable esters are disclosed in GB-A-836988, 864798, 1147871, 2143231 and EP-A-0170386.

N-acylated lactam precursors

N-acylated precursor compounds of lactams are generally disclosed in GB-A-955735. While the broadest scope of the present invention includes any lactam as a precursor of peroxyacids, preferred such materials include caprolactam and valerolactam.

Suitable N-acylated lactam precursors have the formula:

wherein n is 0 to about 8, preferably ⁰ to about 2, and R is alkyl, aryl, alkoxyaryl or alkaryl containing 1 to 12 carbons, or a substitution containing 6 to 18 carbons phenyl.

A suitable caprolactam bleach precursor is of the formula:

wherein ^R is hydrogen or alkyl, aryl, alkoxyaryl or alkaryl of 1-12 carbons, preferably 6-12 carbon atoms, most preferably ^R is phenyl.

Suitable valerolactams have the formula:

Wherein R ¹ is hydrogen or an alkyl group, aryl group, alkoxyaryl group, or alkaryl group containing 1-12 carbon atoms, preferably 6-12 carbon atoms. R ¹ is more preferably selected from phenyl, heptyl, octyl, nonyl, 2,4,4-trimethylpentyl, decenyl and mixed groups thereof.

The most preferred substances are generally solid substances below 30°C, especially phenyl derivatives, i.e. benzoyl valerolactam, benzoyl caprolactam and their substituted benzoyl analogs, such as chloro, aminoalkyl, Alkyl, aryl and alkoxy derivatives.

R ¹ contains at least 6 carbons, preferably 6-12 carbons caprolactam and valerolactam precursors that provide peroxyacids, impart nucleophilicity and body soil cleansing action upon perhydrolysis of hydrophobes. Precursor compounds containing 1 to 6 carbons in ^R1 provide hydrophilic bleaches which are particularly effective in bleaching beverage stains. Mixtures of hydrophobic and hydrophilic caprolactams and valerolactams, generally in a weight ratio of 1:5 to 5:1, preferably 1:1, are used in the present invention for mixture stain removal.

Most preferred caprolactam and valerolactam precursors include benzoyl caprolactam, nonanoyl caprolactam, benzoyl valerolactam, nonanoyl valerolactam, 3,5,5-trimethylacetylcaprolactam, 3,5,5 -Trimethylcaproyl valerolactam, octanoyl caprolactam, capryloyl valerolactam, decanoyl caprolactam, decanoyl valerolactam, undecyl caprolactam, undecyl valerolactam, (6-octanoyl amide Hexanoyl)oxybenzenesulfonate, (6-nonanoylaminocaproyl)oxybenzenesulfonate, (6-decanoylaminocaproyl)oxybenzenesulfonate and mixtures thereof. Most preferred substituted benzoyl lactams include toluamide caprolactam, toluyl valerolactam, ethyl benzoyl caprolactam, ethyl benzoyl valerolactam, propyl benzoyl caprolactam, Propylbenzoyl valerolactam, Isopropyl benzoyl caprolactam, Isopropyl benzoyl valerolactam, Butyl benzoyl caprolactam, Butyl benzoyl valerolactam, Tert-butyl benzoyl caprolactam , tert-butylbenzoyl valerolactam, amyl benzoyl caprolactam, pentyl benzoyl valerolactam, hexyl benzoyl valerolactam, hexyl benzoyl valerolactam, ethoxybenzoyl caprolactam, ethyl benzoyl valerolactam Oxybenzoyl valerolactam, propoxybenzoyl caprolactam, propoxybenzoyl valerolactam, isopropoxybenzoyl caprolactam, isopropoxybenzoyl caprolactam, butoxybenzoyl Acyl caprolactam, butoxybenzoyl valerolactam, tert-butoxybenzoyl valerolactam, tert-butoxybenzoyl valerolactam, pentoxybenzoyl caprolactam, pentoxybenzoyl valerolactam , hexyloxybenzoyl caprolactam, hexyloxybenzoyl valerolactam, 2,4,6-trichlorobenzoyl caprolactam, 2,4,6-trichlorobenzoyl valerolactam, pentafluorobenzene Formyl caprolactam, pentafluorobenzoyl valerolactam, dichlorobenzoyl caprolactam, dimethoxybenzoyl caprolactam, 4-chlorobenzoyl caprolactam, 2,4-dichlorobenzoyl caprolactam, p-phenylene Diacyl dicaprolactam, dichlorobenzoyl valerolactam, dimethoxybenzoyl valerolactam, 4-chlorobenzoyl valerolactam, 2,4-dichlorobenzoyl valerolactam, p-phenylene Diacyl dipalerolactam, 4-nitrobenzoylcaprolactam, 4-nitrobenzoylvalerolactam, and mixtures thereof.

Precursor of perbenzoic acid

Essentially all perbenzoic acid precursors are suitable for the present invention, including the preferred N-acylated lactam type precursors.

Suitable O-acylated perbenzoic acid precursor compounds include substituted and unsubstituted benzoyloxybenzenesulfonates, such as compounds of the formula:

The benzoylated products formed by sorbitol, glucose and all sugars and benzoylating reagents are also suitable for the present invention, such as compounds of the following formula:

A _c = COCH ₃ ; B _g = benzoyl

Preferred imide perbenzoic acid precursor compounds include N-benzoyl succinimide, tetrabenzoyl ethylene diamine and N-benzoyl substituted ureas. Suitable imidazole-type perbenzoic acid precursors include N-benzoyl imidazole and N-benzoylbenzimidazole, and other N-acyl-containing perbenzoic acid precursors, including N-benzoylpyrrolidone, diphenyl Formyl taurine and benzoyl pyroglutamate.

Preferred perbenzoic acid precursors include benzoyl diacyl peroxide, benzoyl tetrayl peroxide, and compounds of the formula:

Phthalic anhydride is another suitable perbenzoic acid precursor compound for the present invention:

Perbenzoic acid derivative precursor

Suitable perbenzoic acid derivative precursors include the perbenzoic acid precursors described herein in which the perbenzoic acid group is substituted by any functional group including an alkyl group.

cationic peroxyacid precursor

Cationic peroxyacid precursor compounds are also suitable in the present invention. The cationic peroxyacid precursors are generally formed by substituting the peroxyacid moieties with ammonium or alkylammonium groups, preferably ethylammonium or methylammonium.

阳离子过氧酸前体在下述专利中介绍过：U.S.4,904,406、4,751,015、4,988,451、4,397,757、5,269,962、5,127,852、5,093,022、5,106,528、U.K.1,382,594、EP475,512、458,396和284,292以及JP87-318,332。 Preferred such precursors are disclosed in UK Patent Application No. 9407944.9 and US Application Nos. 08/298903, 08/298650, 08/298904 and 08/298906.

Suitable cationic peroxyacid precursors include ammonium or alkylammonium salts of all substituted alkyl or benzoyloxybenzenesulfonic acids, N-acylated caprolactams, and monobenzoyltetraacetylglucose benzoylperoxy compounds .

A preferred cationic substituted benzoyloxybenzenesulfonic acid is the 4-(trimethylammonium)methyl derivative of benzoyloxybenzenesulfonic acid of the formula:

A preferred cationic substituted alkyloxybenzenesulfonic acid is the methylammonium derivative of 2,3,3-trimethylhexanoyloxybenzenesulfonic acid.

Preferred cationic N-acylated caprolactam peroxyacid precursors include trialkylammonium methylenebenzoyl caprolactam:

Another class of preferred cationic peroxyacid precursors is sodium 2-(N,N,N-trimethylammonium chloride)ethyl 4-sulfophenyl carbonate.

Alkyl fatty peroxyacid bleach precursor

Alkyl fatty peroxyacid bleach precursors form alkyl fatty peroxyacids on perhydrolysis. Preferably such precursors give peracetic acid upon perhydrolysis.

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

organic peroxyacid

Detergent compositions may contain an organic peroxyacid as an additional component of the oxygen-releasing bleaching system, typically at a level of from 1% to 15%, preferably from 1% to 10%, by weight of the composition.

cationic polymer

The detergent composition and components thereof may comprise other cationic ethoxylated amine polymers having particulate/soil removal/anti-redeposition properties selected from water-soluble cationic polymers. These polymers comprise a polymer backbone, at least 2 M groups and at least one LX group, wherein M is a cationic group attached to or integral with the backbone; as a nonionic group, X is selected from H, C ₁ -C ₄ alkyl or hydroxyalkyl ester or ether groups, and mixed groups thereof; and L is a hydrophilic group that connects the M group and the X group, or connects X to the polymer backbone chain.

In detergent compositions, the cationic ethoxylated amine polymers are used in an amount of from 0.01 to 30%, more preferably from 0.1 to 15%, most preferably from 0.2 to 3%, by weight of the detergent composition.

As used herein, the term "polymer backbone" refers to the polymeric moiety to which the groups M and L-X are connected or combined as one. The term includes oligomeric backbones (2-4 units), and true polymeric backbones (5 or more units).

As used herein, the term "attached to" means that the group is a side group coming out of the polymer backbone. Examples of this attachment can be represented by the following general formulas A and B:

M M L

L L X

X

A B

In this context, the term "integrated" means that the group becomes part of the polymer backbone, examples of which can be represented by the following general formulas C and D:

-M- -M-

L L L

X X X

C D

Any polymer backbone can be used as long as the cationic polymer formed is water soluble and has soil removal/anti-redeposition properties. Suitable polymer backbones may be derived from polyurethanes, polyesters, polyethers, polyamides, polyimides, etc.; polyacrylates, polyacrylamides, polyvinyl ethers, polyethylene, polypropylene and similar polyalkenes , polystyrene and similar poly(alkarylene), polyalkyleneamines, polyalkyleneimines, polyvinylamines, polyalkylamines, polydiallylamines, polyvinylpyridines, Polyaminotriazoles, polyvinyl alcohols, aminopoly(1,3-ureidenes), and mixtures thereof.

M can be any compatible cationic group containing a positive N ⁺ (quaternary salt) center. The positive centers of quaternary salts can be represented by the following structures E and F:

- ⁺ N-

E F

Particularly preferred M groups contain a quaternary salt center represented by Formula E. The cationic groups are preferably close to or integrated with the polymer backbone.

The positive charge of the N ⁺ center is offset by a suitable number of counter anions. Suitable counter anions include Cl ⁻ , Br, SO ₃ ²⁻ , SO ₄ ²⁻ , PO ₄ ² , MeOSO ₃ ⁻ , or similar anions. Particularly preferred counteranions are Cl- ^and Br.

X may be a nonionic group selected from hydrogen (H), C ₁ -C ₄ alkyl or hydroxyalkyl ester or ether groups, and mixtures thereof. Preferred esters or ethers are acetate and methyl ether, respectively. Particularly preferred nonionic groups are H and methyl ether.

In cationic polymers suitable for use in detergent compositions and components thereof according to the present invention, the ratio of cationic groups M to nonionic groups X will generally be from about 1:1 to 1:2. However, the ratio of cationic groups M to nonionic groups X can be varied, for example, by appropriately copolymerizing cationic monomers, nonionic monomers (ie, containing L-X groups), and mixed cationic/nonionic monomers. The ratio of groups M to groups X can generally be from about 2:1 to 1:10. In preferred cationic polymers, the ratio is about 1:1 to 1:5. The polymers formed by such copolymerization are generally random, that is, the cationic monomers, nonionic monomers, and mixed cationic/nonionic monomers are copolymerized in a non-repeating order.

Units containing groups M and groups LX can represent 100% of the cationic polymers of the invention. However, it is also possible to contain other units (preferably nonionic) in the polymer. Examples of other units include acrylamides, vinyl ethers, and those containing non-quaternized tertiary amine groups (M ¹ ) (with an N center). These other units may comprise from 0 to about 90% of the polymer (about 10-100% of the polymer is units containing M and LX groups (including Mi ^- LX groups)). Typically, these other units may comprise from 0 to about 50% of the polymer (about 50-100% of the polymer is units containing M and LX groups).

The number of groups of M and L-X is about 2-200, respectively. Typically, the number of M and L-X groups is about 3-100, respectively. The preferred number of M and L-X groups is about 3-40, respectively.

Except for the part used to connect the M group and the X group, or to connect to the polymer backbone, the hydrophilic chain L is usually composed entirely of polyoxyalkylene moieties - [(R'O) _m (CH ₂ CH ₂ O ) _n ] - composition. The -(R'O) _m - and -(CH ₂ CH ₂ O) _n - moieties in the polyoxyalkylene moiety may be mixed together, or preferably form -(R'O) _m - with -(CH ₂ CH ₂ O ) _n - a block of sections. R' is preferably _C3H6 ( _propylene ); m is preferably 0 to about 5, most preferably 0, ie _the polyoxyalkylene moiety consists entirely of -( _CH2CH2O ) _n- . The -( _CH2CH2O ) _n- moiety preferably comprises at least about 85% by weight of _the polyoxyalkylene moiety, most preferably 100% by weight (m is 0). For the -(CH ₂ CH ₂ O) _n - moiety, n is typically about 3-100. n is preferably about 12-42.

Multiple (2 or more) -L-X moieties can also be linked together and then attached to the M group or polymer backbone, examples of which can be represented by the following general formulas G and H:

M

L L L L L

                                       , 

G H H

Structures such as G and H can be obtained, for example, by reacting glycidol with M groups or with the polymer backbone, followed by ethoxylation of the resulting hydroxyl groups.

Representative examples of cationic polymers of the present invention are as follows:

A． Polyurethane, polyester, polyether, polyamide or similar polymers.

One class of suitable cationic polymers is derived from polyurethanes, polyesters, polyethers, polyamides or the like. These polymers comprise units selected from those having the formulas I, II and III:

(R ⁵ ) _k -[(C ₃ H ₆ O) _m (CH ₂ CH ₂ O) _n ]-X

或 (R ⁵ ) _k -[(C ₃ H ₆ O) _m (CH ₂ CH ₂ O) _n ]-X where A ¹ is

or

X is 0 or 1; R is H or C ₁ -C ₄ alkyl or hydroxyalkyl; R ¹ is C ₂ -C ₁₂ alkylene, hydroxyalkylene, alkenylene, cycloalkylene, arylene or alkarylene, or a C ₂ -C ₃ oxyalkylene moiety with 2 to about 20 oxyalkylene units, but cannot form any OO or ON bonds with A ¹ ; when x is 1, R ² is -R ⁵ - unless A ¹ is

or -(OR ⁸ ) _y - or -OR ⁵ -, but cannot form any OO or ON bond with A ¹ , and R ³ is -R ⁵ -, unless A ¹ is

或 or -(OR ⁸ ) _y - or -OR ⁵ -, but cannot form any OO or ON bond with A ¹ ; when x is 0, R ² is:

or

And R ³ is -R ⁵ -; R ⁴ is C ₁ -C ₄ alkyl or hydroxyalkyl, or (R ⁵ ) _k -[(C ₃ H ₆ O) _m (CH ₂ CH ₂ O) _n ]- Moiety X; R ⁵ is C ₁ -C ₂ alkylene, hydroxyalkylene, alkenylene, arylene, or alkarylene; each R ⁶ is C ₁ -C ₄ alkyl or hydroxyalkyl , or -(CH ₂ ) _r -A ² -(CH ₂ ) _s -, wherein A ² is -O- or -CH ₂ -; R ⁷ is H or R ⁴ ; R ⁸ is C ₂ -C ₃ alkylene or hydroxyalkylene; X is H,

-R ⁹ , or a mixed group thereof, wherein R ⁹ is C ₁ -C ₄ alkyl or hydroxyalkyl; k is 0 or 1; m and n should be such that -(CH ₂ CH ₂ O) _n -partially accounts for- [( _C3H6O ) _m ( _CH2CH2O ) _n ] - at least about 85% by weight of the moiety _; m _is 0 to about 5; n is at least about 3; r is 1 or 2; s is 1 or 2 , and r+s is 3 or 4; y is 2 to about 20; the values of u, v and w are such that there are at least 2 N ⁺ centers and at least 2 X groups.

或

A²优选-O-；x优选1；且R优选H。R¹可以是直链的(如，In the above structural formula, A ¹ is preferably

or

^A2 is preferably -O-; x is preferably 1; and R is preferably H. R ¹ can be linear (eg,

或支链的(如 -CH ₂ -CH ₂ -CH ₂ -,

or branched (such as

Alkylene, hydroxyalkylene, alkenylene, cycloalkylene, alkarylene or oxyalkylene; when R ^is a _C2 - _C3 oxyalkylene moiety, the number of oxyalkylene units is preferably about 2-12 R ¹ is preferably C ₂ -C ₆ alkylene or phenylene, most preferably C ₂ -C ₆ alkylene (eg, ethylene, propylene, hexylene). R ² is preferably -OR ⁵ - or -(OR ⁸ ) _y -; R ³ is preferably -R ⁵ O- or -(OR ⁸ ) _y -; R ⁴ and R ⁶ are preferably methyl. Like R ¹ , R ⁵ can be linear or branched, preferably C ₂ -C ₃ alkylene; R ⁷ is preferably H or C ₁ -C ₃ alkyl; R ⁸ is preferably ethylene; R ⁹ is preferably Methyl; X is preferably H or methyl; k is preferably 0; m is preferably 0; r and s are each preferably 2;

In the above formula, n is preferably at least about 6, where the number of N ⁺ centers and X groups is 2 or 3; n is most preferably at least about 12, with typical values in the range of about 12-42. For homopolymers (v and w are 0), u is preferably about 3-20. For random copolymers (u is at least 1 or preferably 0), v and w are preferably about 3-40, respectively.

B． Polyacrylate, polyacrylamide, polyvinyl ether, or similar polymers.

Another suitable cationic polymer is derived from polyacrylates, polyacrylamides, polyvinyl ethers, or similar polymers. These polymers comprise units selected from those having the formulas IV, V and VI:

where ^A1 is

R is H or C ₁ -C ₄ alkyl or hydroxyalkyl; R ¹ is substituted C ₂ -C ₁₂ alkylene, hydroxyalkylene, alkenylene, arylene or alkarylene, or C ₂ -C ₃ alkylene oxide moiety; each R ² is C ₁ -C ₁₂ alkylene, hydroxyalkylene, alkenylene, arylene, or alkarylene; each R ³ is C ₁ -C ₄ alkane or hydroxyalkyl, -(R ² ) _k -[(C ₃ H ₆ O) _m (CH ₂ CH ₂ O) _n ]-X moiety, or together form -(CH ₂ ) _r -A ² -(CH ₂ ) _s -moiety, wherein A ² is -O- or -CH ₂ -; each R ⁴ is C ₁ -C ₄ alkyl or hydroxyalkyl, or two R ⁴ together form -(CH ₂ ) _r - A ² -(CH ₂ ) _s -moiety; X is H,

-R ⁵ , or a mixed group thereof, wherein R ⁵ is C ₁ -C ₄ alkyl or hydroxyalkyl; j is 1 or 0; k is 1 or 0; the values of m and n should be such that -(CH ₂ CH _{The 2} O) _n -moiety is at least about 85% by weight of the -[(C ₃ H ₆ O) _m (CH ₂ CH ₂ O) _n ]- moiety; m is 0 to about 5; n is at least about 3; r is 1 or 2; s is 1 or 2, and r+s is 3 or 4; the values of u, v and w are such that there are at least 2 N ⁺ centers and at least 2 X groups.

或-O-，A²优选-O-；R优选H。R¹可以是直链的(如，或支链的(如

In the above structural formula, A ¹ is preferably

Or -O-, ^A2 is preferably -O-; R is preferably H. R ¹ can be linear (eg, or branched (such as

Substituted alkylene, hydroxyalkylene, alkenylene, alkarylene or alkylene oxide; R ^is preferably substituted C ₂ -C ₆ alkylene or substituted C ₂ -C ₃ alkylene oxide, most preferably

-CH ₂ CH- or

Each R ² is preferably C ₂ -C ₃ alkylene; R ³ and R ⁴ are each preferably methyl; R ⁵ is preferably methyl; X is preferably H or methyl; j is preferably 1; k is preferably 0; m is preferably 0; r and s are preferably 2, respectively.

In the above formula, n, u, v and w can be varied according to n, u, v and w of polyurethane and similar polymers.

C． Polyalkyleneamines, polyalkyleneimines, or similar polymers.

Another suitable cationic polymer is derived from polyalkyleneamines, polyalkyleneimines, or similar polymers. These polymers comprise units selected from those having the formulas VII, VIII and IX:

(R ³ ) _k -[(C ₃ H ₆ O) _m (CH ₂ CH ₂ O) _n )-X

(R ³ ) _k -[(C ₃ H ₆ O) _m (CH ₂ CH ₂ O) _n ]-X

wherein R ¹ is C ₂ -C ₁₂ alkylene, hydroxyalkylene, alkenylene, cycloalkylene, arylene or alkarylene, or C ₂ - C ₃ alkylene oxide moiety, but cannot form any ON bond; each R ² is C ₁ -C ₄ alkyl or hydroxyalkyl, or -(R ³ ) _k -[(C ₃ H ₆ O) _m (CH ₂ CH ₂ O) _n ]-X moiety; R ³ is C ₁ -C ₁₂ alkylene, hydroxyalkylene, alkenylene, arylene or alkarylene; M' is N ⁺ or N center; X for H,

-R ⁴ , or a mixed group thereof, wherein R ⁴ is C ₁ -C ₄ alkyl or hydroxyalkyl; when M' is N ⁺ , d is 1, and when M' is N, d is 0; M' is When N ¹ , e is 2, and when M' is N, e is 1; k is 1 or 0; the values of m and n should make -(CH ₂ CH ₂ O) _n -partially account for -[(C ₃ H ₆ O) _m (CH ₂ CH ₂ O) _n ]- moiety at least about 85% by weight; m is 0 to about 5; n is at least about 3; x, y and z are such that there are at least 2 M' groups group, at least 2 N ⁺ centers and at least 2 X groups.

In the above formula, R ¹ can vary as in polyurethanes and similar polymers; each ^{R 2 is} preferably methyl or -(R ³ ) _k -[(C ₃ H ₆ O) _m (CH ₂ CH ₂ O) _n ]-X moiety; R ³ is C ₂ -C ₃ alkylene; R ⁴ is preferably methyl; X is preferably H; k is preferably 0;

In the above formula, n is preferably at least about 6, where the number of M' and X groups is 2 or 3; n is most preferably at least about 12, with typical values in the range of about 12 for all ranges of x+y+z -42. Typically, x+y+z is 2 to about 40, preferably 2 to about 20. For short-chain polymers, x+y+z is 2-9, while 2-9 N ⁺ centers and 2-11 X groups are present. For long chain polymers, x+y+z is at least 10, preferably 10 to about 42. M' is typically a mixture of about 50-100% N ⁺ centers and 0-about 50% N centers for short and long chain polymers.

Preferred cationic polymers of this type are derived from C ₂ -C ₃ polyalkyleneamines (x+y+z is 2-9) and polyalkyleneimines (x+y+z is at least 10, preferably 10- about 42). Particularly preferred cationic polyalkyleneamines and polyalkyleneimines are cationic polyethyleneamines (PEA's) and polyethyleneimines (PEI's). These preferred cationic polymers comprise units of the general formula:

wherein R ² (preferably methyl), M′, X, d, x, y, z and n are as defined above; a is 1 or 0.

Prior to ethoxylation, the PEA used to prepare the cationic polymers of the present invention has the general formula:

wherein x+y+z is 2-9, and a is 0 or 1 (molecular weight of about 100-400). Each hydrogen atom attached to each nitrogen atom represents an active site for subsequent ethoxylation reactions. For the preferred PEA, x+y+z is about 3-7 (molecular weight of about 140-310). These PEAs are obtainable by reactions involving ammonia and ethylene dichloride, followed by fractional distillation. Commonly obtained PEAs are triethylenetetramine (TETA) and tetraethylenepentamine (TEPA). For more than pentamines, namely hexamines, heptamines, octaamines and possibly nonamines, other substances, such as cyclic amines and especially piperazine, may be contained in the derivative mixture which is not easy to be separated by distillation. Cyclic amines with side chains containing nitrogen atoms may also be present. See, US Patent No. 2,792,372, issued April 14, 1957 to Dickson, which describes the preparation of PEA.

Depending on the number of units in the PEA, the minimum degree of ethoxylation required for preferred soil removal/anti-redeposition performance can vary. When y+z is 2 or 3, n is preferably at least about 6. If y+z is 4-9, n of at least about 3 produces suitable results. For preferred cationic PEAs, n is at least about 12, with typical values in the range of about 12-42.

The PEI used to make the polymers of this invention has a molecular weight of at least about 440 prior to ethoxylation, which represents at least about 10 units. The preferred PEI used to prepare these polymers has a molecular weight of about 600-1800. The polymer backbone of these PEIs can be represented by the general formula:

where the sum of x, y and z represents a number of sufficient size to obtain a polymer having the aforementioned molecular weight. Although a linear polymer backbone is possible, branched chains are also possible. Depending on the mode of preparation, the relative proportions of primary, secondary and tertiary amine groups in the polymer can vary. The distribution of amine groups is usually as follows:

_{-CH2CH2 - NH2} 30%

_{-CH2CH2 -} NH- 40%

-CH ₂ CH ₂ -N- 30%

Each hydrogen atom attached to each nitrogen atom in PEI represents an active site for subsequent ethoxylation reactions. These PEIs can be obtained by polymerizing ethyleneimine in the presence of catalysts such as carbon dioxide, sodium bisulfite, sulfuric acid, hydrogen peroxide, hydrochloric acid, acetic acid and the like. The specific method for preparing PEI is disclosed in U.S. Patent No. 2182306 issued to Ulrich et al. on December 5, 1939; U.S. Patent No. 3033746 issued to Mayle et al. on March 8, 1962; and Esselmann et al. issued on July 16, 1940. US Patent No. 2,208,095 issued to Crowther on September 17, 1957, and US Patent No. 2,533,696 issued to Wilson on March 21, 1951 (all incorporated herein by reference).

As defined in the preceding formula, n is at least about 3 for cationic PEI. It should be noted, however, that the minimum degree of ethoxylation required for adequate soil removal/anti-redeposition performance can increase with increasing PEI molecular weight, especially when the PEI molecular weight goes well beyond about 1800. In addition, it is preferred that the degree of ethoxylation of the polymer also increases as the molecular weight of PEI increases. For PEI having a molecular weight of at least about 600, n is preferably at least about 12, with typical values in the range of about 12-42. For PEI having a molecular weight of at least 1800, n is preferably at least about 24, with typical values in the range of about 24-42.

D． Diallylamine polymer.

Another suitable cationic polymer is derived from diallylamine. These polymers comprise units selected from those having the formulas X and XI:

Wherein R ¹ is C ₁ -C ₄ alkyl or hydroxyalkyl, or -(R ² ) _k -[(C ₃ H ₆ O) _m (CH ₂ CH ₂ O) _n ]-X moiety; R ² is C ₁ -C ₁₂ alkylene, hydroxyalkylene, alkylene, arylene or alkarylene; each R ³ is C ₁ -C ₄ alkyl or hydroxyalkyl, or together form -(CH ₂ ) _r -A-(CH ₂ ) _s -moiety, wherein A is -O- or -CH ₂ -; X is H,

-R ⁴ , or a mixed group thereof, wherein R ⁴ is C ₁ -C ₄ alkyl or hydroxyalkyl; k is 1 or 0; the values of m and n should make -(CH ₂ CH ₂ O) _n -part At least about 85% by weight of the moiety -[(C ₃ H ₆ O) _m (CH ₂ CH ₂ O) _n ]-; m is 0 to about 5; n is at least about 3; r is 1 or 2; s is 1 or 2, and r+s is 3 or 4; x is 1 or 2; when x is 0, y is 1, and when x is 1, y is 0; the values of u and v should be such that there are at least 2 N ⁺ center and at least 2 X groups.

In the above formula, A is preferably -O-; ^R1 is preferably methyl; each ^R2 is preferably _C2 - _C3 alkylene; each ^R3 is preferably methyl; ^R4 is preferably methyl; X is preferably H; k 0 is preferred; m is preferably 0; r and s are each preferably 2.

In the above formula, n is preferably at least about 6, where the number of N ⁺ centers and X groups is 2 or 3; n is most preferably at least about 12, with typical values ranging from about 12 to all ranges of u+v 42. Typically, v is 0 and u is 2 to about 40, preferably 2 to about 20.

other detergent ingredients

According to the present invention, the detergent compositions and components thereof may also comprise other detergent components. The exact nature of these other ingredients, and the amounts added, will depend upon the physical form of the composition or component and the exact nature of the laundering operation in which it is employed.

The compositions and components thereof according to the present invention preferably comprise one or more other detergent ingredients selected from the group consisting of additional surfactants, additional bleaches, bleach catalysts, alkaline systems, builders, organic polymers , enzymes, foam suppressors, calcium soap dispersants, additional soil-suspending and anti-redeposition agents, detergents, fragrances and corrosion inhibitors.

Additional surfactant

According to the present invention, the detergent compositions and components thereof preferably comprise an additional surfactant selected from the group consisting of anionic, nonionic, cationic, amphoteric, and zwitterionic surfactants and mixtures thereof.

Typical anionic, nonionic, amphoteric and zwitterionic surfactants are listed in US Patent 3,929,678, issued December 30, 1975 to Laughlin and Heuring. Further examples are given in "Surfactants and Detergents" (Volumes I and II, Schwartz, Perry and Berch). Suitable cationic surfactants are listed in US Patent 4,259,217, Murphy, issued March 31,1981.

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

anionic surfactant

According to the present invention, the detergent compositions and components thereof preferably comprise additional anionic surfactants. Essentially any anionic surfactant useful for cleaning can be included in the detergent composition. These include anionic sulfuric, sulfonic, carboxylic, and sarcosine salts (eg, including sodium, potassium, ammonium, and substituted ammonium salts such as mono-, di, and triethanolamine salts) as surfactants. Sulfate anionic surfactants are preferred.

Other anionic surfactants include isethionates such as acyl isethionates, N-acyl taurates, fatty amides of methyl taurates, alkyl succinates and sulfosuccinates salts, monoesters of sulfosuccinates (especially saturated and unsaturated C ₁₂ -C ₁₈ monoesters), diesters of sulfosuccinates (especially saturated and unsaturated C ₆ -C ₁₄ diesters) , N-acyl sarcosinate. 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.

Sulfate Anionic Surfactant

Sulfate anionic surfactants suitable for use in the present invention include linear or branched primary and secondary alkyl sulfates, alkyl ethoxy sulfates, fatty oleoyl glycerol sulfates, alkylphenol ethylene oxide Ether sulfates, C ₅ -C ₁₇ acyl-N-(C ₁ -C ₄ alkyl) and -N-(C ₁ -C ₂ hydroxyalkyl)glucosamine and sulfates, and sulfates of alkyl polyglycosides Salts such as alkyl polyglucoside sulfates (nonionic sulfate compounds are described in this article).

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

The alkyl ethoxy sulphate surfactants are preferably selected from ethoxylated C ₁₀ -C ₁₈ alkyl sulphates having from 0.5 to 20 moles of ethylene oxide per molecule, more preferably C ₁₁ -C ₁₈ alkyl, Most preferred are C ₁₁ -C ₁₅ alkyl, such surfactants ethoxylated with 0.5 to 7, preferably 1 to 5 moles of ethylene oxide per molecule.

A particularly preferred aspect of the invention employs mixtures of the preferred alkyl sulfate and alkyl ethoxy sulfate surfactants. Such mixtures are disclosed in PCT Patent Application No. WO 93/18124.

Anionic Sulfonate Surfactant

Anionic sulfonate surfactants suitable for use herein include C ₅ -C ₂₀ linear alkylbenzene sulfonates, alkyl ester sulfonates, C ₆ -C ₂₂ primary or secondary alkyl sulfonates, C ₆ - _C24 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 ethoxy polycarboxylate surfactants and soaps ('alkyl carboxyl'), especially some of those described herein. Second soap.

Suitable alkyl ethoxy carboxylates include those _having the formula RO( _CH2CH2O ) _xCH2COO ^- M ⁺ , wherein R is _C6 - _C18 alkyl, x _is 0-10, E The oxide distribution is such that, on a weight basis, the amount of this 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- 25, R ₁ and R ₂ are selected from hydrogen atoms, methyl acid groups, succinic acid groups, hydroxysuccinic acid groups, and mixed groups thereof, and R ₃ is selected from hydrogen atoms with 1-8 carbon atoms substituted or unsubstituted hydrocarbons, and mixtures thereof,

Suitable soap surfactants include secondary soap surfactants containing carboxyl units attached to secondary carbon atoms. Preferred secondary soap surfactants for use in the present invention are water soluble selected from 2-methyl-1-undecanoic acid, 2-ethyl-1-decanoic acid, 2-propyl-1-nonanoic acid, 2 - Water-soluble salts of butyl-1-octanoic acid and 2-pentyl-1-heptanoic acid. Certain soaps may also be included as suds suppressors.

Alkali metal sarcosinate surfactant

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

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.

Alkoxylated Alcohol Nonionic Surfactant

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 can be straight or branched, primary or secondary, and generally contains 6 to 22 carbon atoms. Particular preference is given to condensation products of alcohols whose alkyl groups contain 8 to 20 carbon atoms with 2 to 10 moles of ethylene oxide per mole of alcohol.

Polyhydroxy fatty acid amide nonionic surfactant

Polyhydroxy fatty acid amides suitable for use in the present invention have the formula R ² CONR ¹ Z, wherein R ¹ is H, C ₁ -C ₄ hydrocarbyl, 2-hydroxyethyl, 2-hydroxypropyl, ethoxy, propoxy, or a mixed group 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 and Z is a polyhydroxyl hydrocarbon radical having at least 3 hydroxyl groups directly attached to its linear hydrocarbon chain, or an alkoxylated derivative thereof (preferably ethoxylated and propoxylated). Z is preferably derived from a reducing sugar in a reductive amination reaction; Z is more preferably glycidyl.

Fatty Amide Nonionic Surfactant

Suitable fatty amide surfactants have the formula R ⁶ CON(R ⁷ ) ₂ , wherein R ⁶ is an alkyl group containing 7-21 carbon atoms, preferably 9-17 carbon atoms, and each R ⁷ is selected from a hydrogen atom , C ₁ -C ₄ alkyl, C ₁ -C ₄ hydroxyalkyl, and -(C ₂ H ₄ O) _x H, wherein x is 1-3.

Alkyl polysaccharide nonionic surfactant

Alkyl polysaccharides suitable for use in the present invention are disclosed in U.S. Patent 4,565,647 issued to Llenado on January 21, 1986, which contain hydrophobic groups with 6-30 carbon atoms, and polysaccharides, such as polyglycosides, with 1.3-10 The hydrophilic group of the sugar unit.

Preferred alkyl polyglycosides have the formula:

R ² O(C _n H _2n O)t(glycosyl) _x

Wherein: ^R is selected from alkyl, alkylphenyl, hydroxyalkyl, hydroxyalkylphenyl, and mixed groups thereof, wherein the alkyl group contains 10-18 carbon atoms; n is 2 or 3; t is 0-10; and x is 1.3-8. 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 having 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 and Alkylphenyl, or a mixed group thereof; R ⁴ is an alkylene or hydroxyalkylene group containing 2-3 carbon atoms, or a mixed group thereof; x is 0-5, preferably 0-3; and each R ⁵ is an alkyl or hydroxyalkyl group containing 1-3 carbon atoms, or a polyoxyethylene group containing 1-3 ethylene oxide groups. Preference is given to C ₁₀ -C ₁₈ alkyl dimethyl amine oxides, and C _10-18 amido alkyl dimethyl amine oxides.

A suitable example of an alkyl amphodicarboxylic acid is Miranol (TM) C2M Conc., manufactured by Miranol, Inc., Dayton, NJ.

zwitterionic surfactant

Zwitterionic surfactants can also be incorporated into detergent compositions and components thereof according to 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 zwitterionic surfactants useful herein.

Suitable betaines have 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, and R ² is C ₁ - C ₅ hydrocarbyl. Preferred betaines are C _12-18 dimethylammonium hexanoate and C _10-18 amidopropane (or ethane) dimethyl (or diethyl) betaine. Mixed betaine surfactants are also suitable for use in the present invention.

cationic surfactant

Cationic surfactants suitable for use in the detergent compositions and components thereof of the present invention include quaternary ammonium surfactants selected from C ₆ -C ₁₆ , preferably C ₆ -C ₁₀ N-alkyl or alkenyl ammonium surfactants , wherein the remaining N sites are substituted by methyl, hydroxyethyl or hydroxypropyl.

Another type of cationic surfactant suitable for use in the detergent compositions and components thereof of the present invention are cationic ester surfactants.

A cationic ester surfactant is a preferably water-dispersible compound having surfactant properties which contains at least one ester (ie, -COO-) linkage and at least one positively charged group.

For example, US Patent Nos. 4,228,042, 4,239,660 and 4,260,529 disclose suitable cationic ester surfactants, including choline ester surfactants.

The ester bond and the positively charged group in the preferred surfactant molecule are separated from each other by a spacer group whose chain comprises at least 3 atoms (i.e. a chain length of 3 atoms), preferably 3-8 atoms, more preferably 3-5 atoms, most preferably 3 atoms. The atoms forming the spacer chain may be selected from carbon, nitrogen and oxygen atoms, and any mixtures thereof, provided that any nitrogen or oxygen atoms in the chain are bonded only to carbon atoms in the chain. Thus, spacer groups such as -OO- (i.e., peroxide), -NN-, and -NO- linkages are excluded, but are included, for example, _-CH2 -O- _CH2- and _-CH2- NH- _CH2 - a spacer for a bond or the like. The spacer chain preferably comprises only carbon atoms, most preferably a hydrocarbon chain.

water soluble builder compound

According to the present invention, the detergent composition and its components preferably comprise a water-soluble builder compound, which is usually used in the detergent composition in an amount of 1-80% by weight of the composition, preferably 10-70% by weight, most preferably 20-60% by weight.

Water-soluble builder compounds include water-soluble monomeric polycarboxylates, or acid forms thereof, homo- and co-polymeric polycarboxylates or salts thereof, borates, phosphates, and mixtures of any of the foregoing, wherein the polycarboxylates Carboxylic acids contain at least two carboxyl groups separated from each other by no more than two carbon atoms.

Carboxylate and polycarboxylate builders can be in monomeric or oligomeric form, although monomeric polycarboxylates are generally preferred for reasons of cost and performance.

Suitable carboxylates containing one carboxy group include the water-soluble salts of lactic acid, glycolic acid and ether derivatives thereof. Polycarboxylates containing 2 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 3 carboxyl groups specifically include water-soluble citrate, aconitate and citraconic acid salt and succinate derivatives, such as carboxymethyloxysuccinate described in British Patent No. 1379241, Lactyloxysuccinates described in British Patent No. 1389732, aminosuccinates described in Dutch Patent Application 7205873, and oxypolycarboxylates such as 2-oxa-1, as described in British Patent No. 1387447, 1,3-Propane tricarboxylate.

Polycarboxylates containing 4 carboxyl groups include oxydisuccinates disclosed in British Patent No. 1261829, 1,1,2,2-ethane tetracarboxylates, 1,1,3,3-propane tetracarboxylates, and 1,1,2,3-propane tetracarboxylates. Polycarboxylates containing sulfo substituents include the sulfosuccinate derivatives disclosed in British Patent Nos. 1398421 and 1398422 and U.S. Patent No. 3936448, and the sulfonated pyrolyzed citric acid disclosed in British Patent No. 1439000 Salt. Preferred polycarboxylates are hydroxycarboxylates, especially citrates, containing up to 3 carboxy groups per molecule.

Also contemplated as useful builder ingredients are the parent acids of monomeric or oligomeric polycarboxylate chelating agents, or mixtures thereof with salts, such as citric acid or citrate/citric acid mixtures.

Borate builders, and builders containing borate-forming species that generate boron under detergent storage or wash conditions, are useful water-soluble builders herein. salt.

Suitable examples of water soluble phosphate builders are alkali metal tripolyphosphates, sodium, potassium and ammonium pyrophosphates, sodium, potassium and ammonium orthophosphates, sodium and potassium metaphosphates, polymetaphosphoric acid with a degree of polymerization of about 6-21 Sodium, and salts of phytic acid.

Partially soluble or insoluble builder compounds

According to the present invention, the detergent composition and its components may contain partially dissolved or insoluble builder compounds, which are generally used in the detergent composition in an amount of 1-80% by weight of the composition, preferably 10-70% by weight , most preferably 20-60% by weight.

Examples of most water insoluble builders include sodium aluminosilicates.

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

Aluminosilicate zeolites may be natural substances, but are preferably synthetically derived. Synthetic crystalline aluminosilicate ion exchange materials are commercially available under the tradenames Zeolite A, Zeolite B, Zeolite P, Zeolite X, Zeolite HS and mixtures thereof. Zeolite A has the structural formula

Na ₁₂ [(AlO ₂ ) ₁₂ (SiO ₂ ) ₁₂ ].xH ₂ O

Wherein x is 20-30, especially 27. Zeolite X has the structural formula

Na ₈₆ [(AlO ₂ ) ₈₆ (SiO ₂ ) ₁₀₆ ].276H ₂ O.

Another preferred aluminosilicate zeolite is the zeolite MAP builder. The amount of zeolite MAP is 1-80% by weight of the composition, more preferably 15-40%.

EP384070A (Unilever) describes zeolite MAP builders. It is defined as an alkali metal aluminosilicate of zeolite P in which the ratio of silicon to aluminum does not exceed 1.33, preferably 0.9-1.33, more preferably 0.9-1.2.

Of particular value are zeolites MAP in which the silicon to aluminum ratio does not exceed 1.15, more particularly does not exceed 1.07.

Zeolite MAP detergent builders preferably have a particle size, expressed as a _d50 value, of 1.0-10.0 microns, more preferably 2.0-7.0 microns, most preferably 2.5-5.0 microns.

The d ₅₀ value indicates that 50% by weight of the particles have a diameter smaller than this value. Particle size can be determined inter alia by conventional analytical methods, such as using a scanning electron microscope or using a laser particle size analyzer. Other methods of determining _d50 values are disclosed in EP384070A.

Heavy metal ion chelating agent

The detergent compositions of the present invention preferably comprise, as an optional ingredient, heavy metal ion sequestrants. Herein, "heavy metal ion chelating agent" refers to a component capable of chelating heavy metal ions. These components may also have calcium and magnesium chelating capacity, but they preferably have selectivity for binding heavy metals such as iron, manganese and copper.

The amount of heavy metal chelating agent is generally 0.005-20% by weight of the composition, preferably 0.1-10%, more preferably 0.25-7.5%, most preferably 0.5-5%.

Heavy metal ion sequestrants suitable for use herein include organic phosphonates such as aminoalkylene poly(alkylene phosphonates), alkali metal salts of ethane 1-hydroxydiphosphonic acid, and nitrilotrimethylenephosphine salt.

Among the above substances, diethylenetriaminepenta(methylenephosphonate), ethylenediaminetri(methylenephosphonate), hexamethylenediaminetetrakis(methylenephosphonate), and hydroxyl- Ethylene-1,1-diphosphonate.

Other heavy metal chelating agents suitable for use in the present invention include nitrilotriacetic acid and polyaminocarboxylic acids such as ethylenediaminotetraacetic acid, ethylenetriaminepentaacetic acid, ethylenediamine disuccinic acid, ethylenediamine dipentamyl acid, 2-hydroxypropylenediamine disuccinic acid, or all salts thereof. Particularly preferred is ethylenediamine-N,N'-disuccinic acid (EDDS), or its alkali metal, alkaline earth metal, ammonium or substituted ammonium salts, or mixtures thereof.

Other heavy metal sequestrants suitable 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. The iminodiacetic acid-N-2-hydroxypropylsulfonic acid and aspartic acid N-carboxymethyl N-2-hydroxypropyl-3-sulfonic acid chelating agents described in EP-A-516102 are also suitable for this invention. β-alanine-N,N'-diacetic acid, aspartic acid-N,N'-diacetic acid, aspartic acid-N-monoacetic acid and iminodisuccinate described in EP-A-509382 Acid sequestrants are also suitable.

EP-A-476257 describes suitable amino-based chelating agents. EP-A-510331 describes suitable chelating agents derived from collagen, keratin and casein. EP-A-528859 describes suitable alkyliminodiacetic acid 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) is also applicable.

bleach catalyst

The oxygen-releasing bleach system may comprise a transition metal-containing bleach catalyst.

A suitable bleach catalyst is a catalyst system comprising transition metal cations, such as copper, iron or manganese cations, with determinant bleach catalytic activity; auxiliary metal cations, such as zinc or aluminum cations, with little or no bleach catalytic activity and chelating agents with determining stability constants for catalytic and auxiliary metal cations, in particular ethylenediaminetetraacetic acid, ethylenediaminetetrakis(methylenephosphonic acid) and water-soluble salts thereof. These catalysts are disclosed in US Patent No. 4,430,243.

Other bleach catalysts include the manganese-based complexes disclosed in US 5,246,621 and US 5,244,594. Preferred examples of these catalysts include: Mn ^Ⅳ ₂ (uO) ₃ (1,4,7-trimethyl-1,4,7-triazacyclononane) ₂ (PF ₆ ) ₂ , Mn ^Ⅲ ₂ (uO ) ₁ (u-OAc) ₂ (1,4,7-trimethyl-1,4,7-triazacyclononane) ₂ (ClO ₄ ) ₂ 、Mn ^Ⅳ ₄ (uO) ₆ (1,4 ,7-triazacyclononane) ₄ (ClO ₄ ) ₄ , Mn ^Ⅲ Mn ^Ⅳ ₄ (uO) ₁ (u-OAc) ₂ (1,4,7-trimethyl-1,4,7-tri Azacyclononane) ₂ (ClO ₄ ) ₃ and mixtures thereof. European Patent Publication No. 549272 describes other catalysts. Other ligands suitable for use in the present invention include 1,5,9-trimethyl-1,5,9-triazacyclononane, 2-methyl-1,4,7-triazacyclononane, 2-methyl-1,4,7-triazacyclononane, 1,2,4,7-tetramethyl-1,4,7-triazacyclononane, and mixtures thereof.

Bleach catalysts suitable for use in the present invention can also be selected. Suitable examples of bleach catalysts can be found in US4246612 and US5227084. See also US5194416, which describes mononuclear manganese (IV) complexes, such as Mn (1,4,7-trimethyl-1,4,7-triazacyclononane) (OCH ₃ ) ₃ (PF ₆ ).

Another bleach catalyst disclosed in U.S. Patent No. 5,114,606 is the combination of manganese (III) and/or (IV) with a non-carboxylate polyol ligand having at least 3 consecutive C-OH groups. Water soluble complex. Preferred ligands include sorbitol, iditol, erythritol, (dulsitol), mannitol, xylitol, arabitol, fusitol, mesoerythritol, meso-inositol, Lactose, and mixtures thereof.

US Patent No. 5114611 describes a bleach catalyst comprising a complex of a transition metal such as Mn, Co, Fe or Cu with a non-(large)-cyclic ligand. The ligand has the structural formula:

Wherein R ¹ , R ² , R ³ , and R ⁴ are respectively selected from H, substituted alkyl, and aryl, so that each of R ¹ -N=CR ² and R ³ -C=NR ⁴ forms a 5- or 6-membered ring. The rings can be further substituted. B is a bridging group selected from O, S, CR ⁵ R ⁶ , NR ⁷ and C=O, wherein R ⁵ , R ⁶ , and R ⁷ are each H, alkyl or aryl, including substituted or unsubstituted groups group. Preferred ligands include pyridine, pyridazine, pyrimidine, piperazine, imidazole, pyrazole and triazole rings. The rings may bear substituents such as alkyl, aryl, alkoxy, halogen, and nitro. Preferred bleach catalysts include Co, Cu, Mn, Fe-bispyridylmethane and -bispyridylamine complexes. Highly preferred catalysts include Co(2,2'-dipyridylamine) _Cl2 , bis(isothiocyanato)bispyridylamine-cobalt(II), tris(dipyridylamine)-cobalt perchlorate ( Ⅱ), Co(2,2'-dipyridylamine) ₂ O ₂ ClO ₄ , bis(2,2'-bipyridylamine)-copper(II) perchlorate, tris(di-2-pyridyl Amine) - iron (II) perchlorate, and mixtures thereof.

Other examples include dinuclear Mn complexes with tetra-N-dentate and di-N-dentate ligands such as N ₄ Mn ^III (uO) ₂ Mn ^IV N ₄ ) ⁺ and [ Dipyridyl ₂ Mn ^III (uO) ₂ Mn ^IV Dipyridyl ₂ ]-(ClO ₄ ) ₃ .

Other bleach catalysts are described, for example, in European Patent Application Publication No. 408131 (cobalt complex catalysts), European Patent Application Publication Nos. 384503 and 306089 (metalloporphyrin catalysts), US4728455 (manganese/multidentate ligand catalysts), US4711748 and European Patent Application Publication No. 224952 (adsorption of manganese on aluminosilicate catalyst), US4601845 (aluminosilicate matrix with manganese and zinc or magnesium salt), US4119557 (iron complex catalyst), German patent specification 2054019 ( cobalt chelation catalysts), Canada 866191 (transition metal containing salts), US4430243 (chelating agents with manganese cations and non-catalytic metal cations), and US4728455 (manganese gluconate catalysts).

In the compositions and methods of the present invention, the bleach catalyst is generally used in a catalytically effective amount. By "catalytically effective amount" is meant an amount sufficient, under any comparative test conditions, to enhance bleach removal of soils from the target substrate. The test conditions may vary, depending on the type of washing utensils used and the habits of the users. In laundry operations, some users prefer to use hot water, while others use warm or even cold water. Of course, the catalytic performance of the bleach catalyst is influenced by these factors, so the level of the bleach catalyst can be adjusted appropriately in fully formulated detergent and bleach compositions. In practice (and not limitation), the compositions and processes of the present invention can be adjusted to produce a catalytic concentration of active bleach in the aqueous wash solution of at least 0.1 ppm, preferably from about 1 ppm to about 200 ppm. To illustrate this further, at 40°C, pH = 10, and European washing machine conditions, manganese catalyst concentrations on the order of 3 millimolar are effective if perborate and bleach precursors are used. To achieve the same result, the concentration is required to be increased by 3-5 times under the condition of American washing machine.

enzyme

Another preferred ingredient for use in detergent compositions and components thereof is one or more additional enzymes.

Preferred additional enzymes include commercially available lipases, cutinases, amylases, neutral and alkaline proteases, cellulases, endoenzymes, esterases, pectinases, lactases and peroxidases commonly added to detergent compositions. enzymes. Suitable enzymes are described in US Patent Nos. 3,519,570 and 3,533,139.

Preferred commercially available proteases include those sold under the trade names Alcalase, Savinase, Primase, Durazym and Esperase by Novo Industries A/S of Denmark, those sold under the trade names Maxatase, Maxacal and Maxapem by Gist-Brocades, and those sold by Genencor International and those sold by Solvay Enzyme under the trade names Opticlean and Optimase. According to the present invention, the protease may be used in the composition in an amount of 0.0001-4% active enzyme by weight of the composition.

Preferred amylases include alpha-amylases obtained from special strains of Bacillus licheniformis described in detail in GB 1,296,839 (NoVo). Preferred commercially available amylases include those sold under the tradename Rapidase by Gist-Brocades, those sold under the tradename Termamyl and BAN by Novo Industries A/S. According to the present invention, amylase may be used in the composition in an amount of 0.0001-2% active enzyme by weight of the composition.

Lipase may be used in an amount of 0.0001-2% by weight of the composition, preferably 0.001-1% by weight, most preferably 0.001-0.5% by weight of active lipase.

Lipases can be obtained from fungi and bacteria, eg, strains of Humicola that produce lipases. , Thermomyces, or Pseudomonas including Pseudomonas pseudoalcaligenes or Pseudomonas fluorescens. Lipases obtained from chemically or genetically modified variants of these genera are also useful in the present invention. A preferred lipase is derived from Pseudomonas pseudoalcaligenes as disclosed in granted European patent EP-B-0218272.

Another preferred lipase of the present invention can be obtained by cloning the gene of Humicola lanuginosa and then expressing the gene in the host Aspergillus oryzae, which is described in European patent application EP-A-0258068, Novo Industries, Bagsvaerd, Denmark A/S sells it under the trade name Lipolase. This lipase is also described in US Patent 4,810,414, issued March 7,1989 to Huge-Jensen et al.

organic polymer

According to the present invention, organic polymers are preferred additional components of detergent compositions and components thereof, and are therefore preferred components of any particulate components where they bind the particulate components together. As used herein, "organic polymer" means essentially any organic polymer conventionally used as a dispersant, as well as an anti-redeposition and soil-suspension agent in detergent compositions, according to the present invention, including herein as clay Any high molecular weight organic polymer of a flocculant other than a quaternary ethoxylated (poly)amine soil removal/anti-redeposition agent.

The amount of organic polymer used in the detergent composition of the present invention is generally 0.1-30%, preferably 0.5-15%, most preferably 1-10% by weight of the composition.

Examples of organic polymers include water-soluble organic homo- or co-polycarboxylic acids or salts thereof, wherein the polycarboxylic acids contain at least two carboxyl groups separated from each other by no more than two carbon atoms. The latter polymers are disclosed in GB-A-1596756.

Examples of these salts are their polycarboxylates of MWt 1800-5000 and their copolymers with maleic anhydride, these copolymers having a molecular weight of 2000-100000, especially 40000-80000.

Polyamino compounds are useful herein, including those derived from aspartic acid, as disclosed in EP-A-3052282, EP-A-305283 and EP-A-351629.

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

Other organic polymers suitable for use in the detergent compositions of the present invention include cellulose derivatives such as methylcellulose, carboxymethylcellulose, hydroxypropylmethylcellulose and hydroxyethylcellulose.

Other useful organic polymers are polyethylene glycols, especially polyethylene glycols having a molecular weight of 1000-10000, more preferably 2000-8000, most preferably about 4000.

Antifoam system

When the detergent composition of the present invention is formulated for use in machine washing compositions, it preferably contains an antifoam system in an amount of 0.01-15%, preferably 0.05-10%, most preferably 0.1-5%, by weight of the composition.

Suitable suds suppressing systems for use herein may comprise essentially any known antifoam compound including, for example, silicone antifoam compounds and 2-alkyl alcohol antifoam compounds.

As used herein, "antifoam compound" means any compound or mixture thereof which reduces the degree of foaming or foaming produced by a solution of a detergent composition, especially when the solution is agitated.

Particularly preferred antifoam compounds for use in the present invention are silicone antifoam compounds, which are defined herein as any antifoam compound comprising a silicone component. These silicone antifoam compounds typically also contain a silica component. As used herein, and in the general field of industry, the term "siloxane" includes various higher molecular weight polymers containing siloxane units and various hydrocarbyl groups. Preferred silicone antifoam compounds are silicones, especially polydimethylsiloxanes having trimethylsilyl endblock units.

Other suitable antifoam compounds include fatty monocarboxylic acids and their water soluble salts. These materials are described in US Patent 2,954,347, issued December 27, 1960 to Wayne St. John. The hydrocarbyl chains of the aliphatic monocarboxylic acids and their water-soluble salts useful as suds suppressors generally have from 10 to 24 carbon atoms, preferably from 12 to 18 carbon atoms. Suitable salts thereof include alkali metal salts, such as sodium, potassium and lithium, and ammonium and alkanolammonium salts.

Other suitable antifoam compounds include, for example, high molecular weight fatty esters (e.g., fatty acid triglycerides), fatty acid esters of monohydric alcohols, aliphatic _C18 - _C40 ketones (e.g., stearyl ketone), N-alkylated Aminotriazines, such as tri- to hexa-alkylmelamines, or di- to tetra-alkyldiamine chlorotriazines (reaction of cyanuric chloride with two or three moles of primary or secondary amines having 1 to 24 carbon atoms product, propylene oxide), distearylamide and monostearyl di-alkali metal (eg, sodium, potassium and lithium) phosphates and esters.

A preferred suds suppressor system comprises:

(a) an antifoam compound, preferably a silicone antifoam compound, most preferably a silicone antifoam compound comprising

(i) polydimethylsiloxane in an amount of 50-99%, preferably 75-95%, by weight of the silicone antifoam compound; and

(ii) silica in an amount of 1-50%, preferably 5-25%, by weight of the silicone/silica antifoam compound;

Wherein said silicon dioxide/siloxane antifoam compound is added in an amount of 5-50% by weight, preferably 10-40% by weight;

(b) a dispersant compound in an amount of 0.5-10% by weight, preferably 1-10% by weight, most preferably comprising a silicone diol rake copolymer, wherein the polyoxyalkylene content is 72-78%, and the ratio of ethylene oxide to propylene oxide is 1:0.9-1:1.1; a particularly preferred siloxane diol rake copolymer of this type is DC0544, commercially available from DOW Corning under the trade name DC0544;

(c) an inert carrier compound in an amount of 5-80% by weight, preferably 10-70% by weight, most preferably comprising a C ₁₆ -C ₁₈ ethoxylated alcohol, wherein the degree of ethoxylation is 5-50, preferably 8 -15.

EP-A-0210731 describes a highly preferred particulate suds suppressor system comprising a silicone antifoam compound and an organic vehicle having a melting point of 50-85°C, wherein the organic vehicle comprises glycerol with 12-20 carbon atoms Monoesters of fatty acids. EP-A-0210721 discloses other preferred particulate suds suppressor systems in which the organic carrier is a fatty acid or an alcohol, or a mixture thereof, with a melting point of 45-80° C. and a carbon chain having 12-20 carbon atoms.

dye transfer inhibiting polymer

The detergent compositions herein may also comprise from 0.01 to 10% by weight, preferably from 0.05 to 0.5% by weight, of a dye transfer inhibiting polymer.

Dye transfer inhibiting agents are preferably selected from polyamine N-oxides, copolymers of N-vinylpyrrolidone and N-vinylimidazole, polyvinylpyrrolidone or mixtures thereof, wherein these polymers may be crosslinked polymers.

a) Polyamine N-oxide

Polyamine N-oxides suitable for use in the present invention comprise units having the formula:

P

(1) Ax

R

where P is a polymerizable unit,

O O O

A is NC.CO.C.-O-.-S-.-N-.x is O or 1

R is an aliphatic, ethoxylated aliphatic, aromatic, heterocyclic or alicyclic group or any mixed group thereof, and the nitrogen atom in the N-O group can be attached to it or become a part of it.

或

The NO group can be represented by the following general formula:

or

Wherein R ₁ , R ₂ , R ₃ are aliphatic, aromatic, heterocyclic or alicyclic groups or their mixed groups, x or/and y or/and z are 0 or 1, and the NO group Nitrogen atoms can be attached to or be part of it. The NO group can be part of the polymerizable unit (P), or can be attached to the polymer backbone, or 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, cycloaliphatic or heterocyclic groups. One such polyamine N-oxide includes those polyamine N-oxides wherein the nitrogen of the N-O group becomes part of the R group. Preferred polyamine N-oxides are those wherein R is a heterocyclic group such as pyridine, pyrrole, imidazole, pyrrolidine, piperidine, quinoline, acridine and derivatives thereof.

Other suitable polyamine N-oxides are polyamine oxides in which the N—O groups are attached to polymerisable units. Preferred of these polyamine N-oxides include polyamine N-oxides of the general formula (I) wherein the nitrogen atom in the N-O functional group is part of said R group, wherein R is aromatic, heterocyclic or alicyclic family group. Examples thereof are those polyamine N-oxides wherein R is a heterocyclic compound such as pyridine, pyrrole, imidazole, and derivatives thereof.

Polyamine N-oxides are available with 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 properties. Its average molecular weight is usually 500-1,000,000.

b) Copolymer of N-vinylpyrrolidone and N-vinylimidazole

Copolymers of N-vinylpyrrolidone and N-vinylimidazole with a molecular weight of 5000-50000 are also suitable for the present invention. In preferred copolymers, the molar ratio of N-vinylimidazole to N-vinylpyrrolidone is 1-0.2.

c) Polyvinylpyrrolidone

Polyvinylpyrrolidone ("PVP") having an average molecular weight of from 2,500 to 400,000 may also be used in the detergent compositions herein. Suitable polyvinylpyrrolidones are available from ISPCorporation, New York, NY and Montrel, Canada under the product names PVP K-15 (viscosity average molecular weight 10000), PVP K-30 (average molecular weight 40000), PVP K- 60 (average molecular weight 160000) and PVP K-90 (average molecular weight 360000). PVP K-15 is also commercially available from ISP Corporation. Other suitable polyvinylpyrrolidones available from BASF Corporation include Sokalan HP165 and Sokalan HP12.

d) Polyvinyloxazolidinone

The detergent compositions herein may also employ polyvinyloxazolidinones as dye transfer inhibiting polymers. The average molecular weight of the polyvinyl oxazolidone is 2500-400000.

e) Polyvinylimidazole

The detergent compositions herein may also employ polyvinylimidazole as the dye transfer inhibiting polymer. The average molecular weight of the polyvinylimidazole is preferably 2500-400000.

Fluorescent whitening agent

Certain hydrophilic optical brighteners can also optionally be included in the detergent compositions of the present invention at about 0.005% to about 5% by weight.

The hydrophilic fluorescent whitening agent that can be used in the present invention has the following structural formula:

Wherein R ₁ is selected from anilino, N-2-bis-hydroxyethyl and NH-2-hydroxyethyl; R ₂ is selected from N-2-bis-hydroxyethyl, N-2-hydroxyethyl-N- methylamino, morpholino, chlorine and amino; and 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-bis-hydroxyethyl, and M is a cation, such as sodium, the whitening agent is 4,4'-bis[(4-anilino -6-(N-2-bis-hydroxyethyl)-s-triazin-2-yl)amino]-2,2'-stilbene disulfonic acid and its disodium salt. This particular brightener is commercially available from Ciba-geigy Corporation under the tradename Tinopal-UNPA-GX. Tinopal-UNPA-GX is the preferred hydrophilic optical brightener for use in the detergent compositions herein.

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 whitening agent is 4,4′-bis[ (4-anilino-6-(N-2-hydroxyethyl-N-methylamino)-s-triazin-2-yl)amino]-2,2'-stilbene disulfonic acid disodium salt. This particular brightener is commercially available from Ciba-geigy Corporation under the tradename Tinopal 5BM-GX.

In the above formula, when R ₁ is anilino, R ₂ is morpholino, 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 disodium salt. This particular brightener is commercially available from Ciba-geigy Corporation under the tradename Tinopal AMS-GX.

polymer detergent

In the detergent compositions of the present invention, known polymeric soil release agents, hereinafter referred to as "SRA", are optionally employed. If used, SRA will generally comprise from 0.01 to 10.0%, usually from 0.1 to 5%, preferably from 0.2 to 3.0%, by weight of the composition.

In general, preferred SRAs contain a hydrophilic portion and a hydrophobic portion, wherein: the hydrophilic portion hydrophilizes the surface of hydrophobic fibers such as polyester and nylon; and the hydrophobic portion deposits onto the hydrophobic fiber , then becomes the anchor for the hydrophilic portion by adhering to the hydrophobic fibers through the completion of the wash and rinse cycle. This ensures that stains created after SRA treatment are more easily removed in subsequent washing steps.

Preferred SRAs include oligomeric terephthalates, which are synthesized by a process involving at least one transesterification/oligomerization reaction, usually in the presence of a metal catalyst, such as a titanium(IV) alkoxide. preparation. These esters can be made with other monomers that can be incorporated into the ester structure via one, two, three, four, or more sites, and of course do not form a highly crosslinked overall structure.

Suitable SRAs include the sulfonation products of substantially linear ester oligomers comprising an oligoester backbone of terephthaloyl and oxyalkyleneoxy repeat units, and covalently attached to the backbone Allyl-derived sulfonated terminal moieties are described, for example, in US Patent 4,968,451, November 6, 1990, by JJ. Scheibei and E.P. Gosselink. Such ester oligomers can be prepared by (a) ethoxylating allyl alcohol, (b) converting the product of (a) in a two-step transesterification/oligomerization Reaction with dimethyl terephthalate ("DMT") and 1,2-propanediol ("PG"), and (c) reacting the product of (b) with sodium metabisulfite in water. Other SRAs include, Gosselink et al., US 4,711,730, December 8, 1987, Non-ionically blocked 1,2-propylene terephthalate/poly(oxyethylene) terephthalate , as can be produced by transesterification/oligomerization of poly(ethylene glycol) methyl ether, DMT, PG, and poly(ethylene glycol) ("PEG"). Other examples of SRAs include; partially and fully anionically terminated oligoesters such as ethylene glycol ("EG"), PG, DMT and 3,6-di Oligomers of sodium oxa-8-hydroxyoctanesulfonate; Gosselink in US4,702,857, October 27, 1987, nonionic end-block polyester oligomers, e.g., composed of DMT, methyl (Me )-blocked PEG and EG and/or PG, or produced from a mixture of DMT, EG and/or PG, Me-blocked PEG, and sodium dimethyl-5-sulfoisophthalate; and Granted October 31, 1989 Anionically (especially sulfoaroyl) terminated terephthalates in US 4,877,896 to Maldonado, Gosselink et al., the latter is a typical SRA useful in laundry and fabric finishing products, exemplified by the meta-sulfo An ester composition made from monosodium benzoate, PG and DMT, optionally but preferably comprising added PEG (eg, PEG3400).

SRA also includes: simple block copolymers of ethylene terephthalate or propylene terephthalate with polyethylene oxide terephthalate or polypropylene oxide terephthalate, see May 1976 US _{Pat . C4} hydroxyalkyl cellulose, see US 4,000,093, Nico et al., issued December 28, 1976; and methyl cellulose ethers having an average degree of substitution (methyl) of about 1.6-2.3 per glucoside unit. It has a viscosity (2% aqueous solution) of about 80-120 centipoise at 20°C. These materials are commercially available as METOLOSE SM100 and METOLOSE SM200, which are manufactured by Shinetsu Kagaku Kogyo KK. Trade name for manufactured methyl cellulose ethers.

Another class of SRAs includes: (I) nonionic terephthalate esters linked to polymeric ester structures using diisocyanate coupling agents, see US 4,201,824 to Violland et al. and US 4,240,918 to Lagasse et al; and (II) SRA with carboxylate end groups obtained by adding trimellitic anhydride to known SRA to convert the terminal hydroxyl groups to trimellitate. By proper selection of the catalyst, trimellitic anhydride can be bonded to the end group of the polymer through the ester of an isolated carboxylic acid of trimellitic anhydride without opening the anhydride bond. Both nonionic and anionic SRAs can be used as starting materials as long as they contain esterifiable hydroxyl end groups. See US 4,525,524 to Tung et al. Also included: (III) Urethane-linked SRAs based on terephthalate anion salts, see Violland et al. US Patent 4,201,824.

other optional ingredients

Other optional ingredients suitable for use in the compositions of the present invention include fragrances, coloring agents and filler salts, with sodium sulfate being the preferred filler salt.

Detergent formulations with near-neutral pH of the lotion

Although the detergent composition of the present invention is used in a wide wash pH range (such as about 5-12), it is formulated to a near-neutral wash pH value, that is, in 20°C water, at about 0.1-2% by weight. Concentrations are particularly useful when the initial pH is about 7.0-10.5. The near-neutral pH formula of the lotion is good for stabilizing enzymes and preventing dirt from settling. In these formulations, the pH of the lotion is preferably about 7.0-10.5, more preferably about 8.0-10.5, most preferably about 8.0-9.0.

European Patent Application 83.200688.6 filed May 16, 1983 by J.H.M. Wertz and P.C.E. Goffinet discloses detergent formulations for preferred wash liquors at near neutral pH.

Highly preferred compositions of this type also preferably comprise about 2-10% by weight citric acid and minor amounts (e.g., less than about 20% by weight) of neutralizing agents, buffers, phase regulators, hydrotropes, enzymes, enzyme stabilizers Agents, polybasic acids, foam regulators, opacifiers, antioxidants, bactericides, dyes, fragrances and brighteners, as described in US Patent 4,285,841 issued August 25, 1981 to Barrat et al.

composition formation

The detergent compositions of the present invention can be prepared by various methods which include dry mixing and agglomerating the various compounds contained in the detergent components.

The detergent components preferably form part of the detergent composition.

Compositions according to the present invention may be in a variety of physical forms including granules, tablets, flakes, lozenges and bars. Compositions that are added to washing machines with soiled fabrics using a dispensing device located in the washing machine drum are so-called concentrated granular detergent compositions.

The compositions according to the invention may also be used, for example, in bleach additive compositions containing chlorine bleaches, or in combination therewith.

In general, granular detergent compositions according to the present invention can be prepared by a variety of methods including dry mixing, spray drying, agglomeration and granulation. The quaternizing sludge removal/anti-redeposition agents according to the invention can be added to other detergent components by dry mixing, agglomeration (preferably in combination with a carrier material) or as a spray-dried component.

In granular compositions comprising water-soluble cationic soil removal/anti-redeposition compounds, the average particle size of the components should preferably be no more than 15% of the particles are larger than 1.8mm in diameter and no more than 15% of the particles are smaller than 0.25mm in diameter. The average particle size should preferably be such that 10-50% of the particles have a diameter of 0.2-0.7 mm.

The term "average particle size" as defined herein is calculated by sieving a sample of the composition into a number of fractions (usually 5 fractions) on a series of sieves, preferably Tyler sieves. The fraction weight thus obtained is plotted against the sieve aperture. The pore size through which 50% by weight of the sample passes is considered the average particle size.

Granular detergent compositions according to the present invention will generally have a bulk density of at least 600 g/l, more preferably 650 g/l to 1200 g/l. Bulk density is measured using a simple funnel and a measuring cup with a flap valve at its lower end, wherein the contents of the funnel can be poured entirely through the flap valve into an axially aligned cylindrical measuring cup located below the funnel. The funnel is 130 mm high and has an inner diameter of 130 mm and 40 mm at its upper and lower ends, respectively. When installed, its lower end is located 140 mm above the base surface. The measuring cup has an overall height of 90mm, an inner height of 87mm and an inner diameter of 84mm. Its nominal volume is 500 ml.

To measure, manually pour powder into the funnel, open the flap valve, and allow the powder to fill the measuring cup. Remove the filled measuring cup from the stand, and use a straight-edged tool, such as a knife, over its top rim to remove excess powder. The filled measuring cup is then weighed and the resulting powder weight value is multiplied to give the bulk density (grams per liter). Repeat measurements can be made as needed.

A compacted solid may be produced using any suitable compaction process, such as tabletting, briquetting or extrusion, preferably tabletting. Tablets for dishwashing can preferably be manufactured using a standard rotary tablet press using a pressure of 5-13 KN/ ^cm2 , more preferably 5-11 KN/ ^cm2 such that the compacted solid has a minimum hardness of 176- 275N, preferably 195-245N, as measured by a C100 hardness tester supplied by I. Hollandinstrument. This method can be used to prepare uniform or layered tablets of any size and shape. The tablet is preferably symmetrical to ensure uniform dissolution of the tablet in the wash solution.

laundry method

The machine washing methods herein generally involve treating soiled laundry with an aqueous wash solution in a washing machine in which an effective amount of the machine wash detergent composition of the present invention is dissolved or formulated. "Effective amount of detergent composition" means that 10-300 g of the product is dissolved or formulated in 5-65 liters of lotion, which is the usual dosage of the product and the usual volume of lotion in conventional machine washing methods.

In the washing process, preferably a dispensing device is used. The dispensing device holds the detergent product, which then introduces the product directly into the drum of the washing machine before the wash begins. Its volume should be such that it can contain enough detergent products normally used in washing methods.

Before, during or after the washing machine is loaded with laundry, the dispensing device containing the detergent product is placed in the drum before the wash begins. To start the wash cycle, the drum is filled with machine water and the drum rotates periodically. Dispensing equipment should be designed to contain dry detergent product, which is then released during the wash cycle due to the agitation action of the drum rotation and through contact with the wash water.

In order to release the detergent product during washing, the device has a number of openings through which the product can pass. In addition, the device is made of a material that is permeable to liquids but not solid products, thus allowing the release of dissolved products. Preferably the detergent product is released quickly at the start of the wash cycle, whereby a brief localized high concentration of product is produced in the drum of the washing machine during this wash phase.

Preferred dispensing devices are reusable and designed to maintain the integrity of the container in the dry state and through the wash cycle. The following patents describe particularly preferred dispensing devices for use with compositions of the invention: GB-B-2157717, GB-B-2157718, EP-A-0201376, EP-A-0288345 and EP-A-0288346. The article by J. Bland, Manufacturing Chemist, November 1989, pages 41-46 also describes a particularly preferred dispensing device for use with granular laundry products commonly referred to as "granules". Another preferred dispensing device for use with the compositions of the present invention is disclosed in PCT Patent Application No. WO 94/11562.

Particularly preferred dispensing devices are disclosed in European Patent Application Nos. 0343069 & 0343070. The latter patent application discloses a bag-like flexible sheath device extending from a support ring enclosing an aperture, the opening of which is adapted to fill the bag with sufficient product for one wash cycle in the washing step. A portion of the wash medium flows through the opening into the bag, dissolves the product, and the solution then flows out through the opening into the wash medium. The support ring has a shielded structure to prevent ingress of wetted, undissolved product, usually comprising radially extending walls extending from a central shell in a spoke configuration, or similar structure having helical walls.

Alternatively, the dispensing device may be a flexible container, such as a bag. The bag may be a fibrous structure coated with a water-impermeable protective material to retain the contents, as disclosed in European Patent Application Publication No. 0018678. It can also be made of a water insoluble synthetic polymer with a rupturable edge seal design in aqueous media, as disclosed in European Patent Application Publication Nos. 0011501, 0011502 and 0011968. A simple water breakable seal comprising a water soluble adhesive sealed along the edges of a bag made of a water impermeable polymer film such as polyethylene or polypropylene.

Machine washing dishes

Any method suitable for machine dishwashing or cleaning soiled tableware, in particular soiled silverware, is conceivable.

A preferred method of machine dishwashing comprises treating a variety of soils selected from the group consisting of crockery, glassware, dishware, silverware, and cutlery, and combinations thereof, with an aqueous liquid in which an effective amount of the machine dishwashing composition of the present invention is dissolved or formulated. utensils. "An effective amount of a machine dishwashing composition" means 8-60 grams of the product dissolved or formulated in 3-10 liters of wash liquor, which is the typical dosage and volume of wash liquor used in conventional machine dishwashing methods.

Composition packaging

Actual commercial bleaching compositions may be packaged in any suitable container including containers constructed of paper, paperboard, plastic and any suitable laminate. European Patent Application No. 94921505.7 describes preferred packaging examples.

Abbreviation used for example

In detergent compositions, the symbols for component abbreviations have the following meanings: LAS: Sodium linear C ₁₂ alkylbenzene sulfonate TAS: Sodium tallow alkyl sulphate CxyAS: C _1x -C _1y sodium alkyl sulphate C46SAS: C ₁₄ -C ₁₆ secondary (2,3) alkyl sodium sulfate CxyEzS: C _1x -C _1y alkyl sodium CxyEz condensed with z moles of ethylene oxide CxyEz: C _1x-1y condensed with an average of z moles of ethylene oxide (mostly

number) linear primary alcohol QAS R ₂ N ¹ (CH ₃ ) ₂ (C ₂ H ₄ OH), R ₂ =C ₁₂ -C ₁₄ soap: linear sodium alkyl carboxylate derived from tallow and coconut oil

80/20 Blend CFAA: C ₁₂ -C ₁₄ (Coconut) Alkyl N-Methyl Glucamide TFAA: C ₁₆ -C ₁₈ Alkyl N-Methyl Glucamide TPKFA: C ₁₂ -C ₁₄ Topped Whole Fatty Acid STPP : Anhydrous sodium tripolyphosphate TSPP: Tetrasodium pyrophosphate zeolite A: Hydrated silicon with the formula Na ₁₂ (AlO ₂ SiO ₂ ) _12.27 H ₂ O

Sodium aluminate with a primary particle size of 0.1-10 microns Boiling MAP: Hydrated sodium aluminosilicate zeolite with a silicon to aluminum ratio of 1.07

_MAPNaSKS -6: crystalline layered silicate with structural formula δ- _Na2Si2O5 Citric acid _: Anhydrous citrate borate Sodium borate carbonate: Anhydrous sodium carbonate, particle size 200-900 μm Bicarbonate Salt: Anhydrous sodium bicarbonate, particle size distribution 400-1200 μm Silicate: Amorphous sodium silicate (SiO ₂ :Na ₂ O=2.0:1) Sodium sulfate: Anhydrous sodium sulfate Citrate: Lemon dihydrate Trisodium acid, 86.4% active, particle size

The distribution is 425-850μm MA/AA: 1:4 copolymer of maleic acid/acrylic acid, the average molecular weight is about

70000AA: Sodium polyacrylate, average molecular weight 4500 CMC: Sodium carboxymethyl cellulose cellulose ether: Methyl cellulose ether with a degree of polymerization of 650, obtained from Shin

Etsu Chemicals Protease: Proteolytic enzyme with an activity of 4KNP U/g, supplied by NOVO

Sold by Industries A/S, the trade name is SavinaseAlcalase: a proteolytic enzyme with an activity of 3 AU/g, produced by NOVO

Industries A/S sells cellulase: Cellulolytic enzyme with an activity of 1000 CEVU/g, supplied by NOVO

          Sold by Industries A/S, trade name Carezyme amylase: amylolytic enzyme with an activity of 120KNU/g, produced by NOVO

Sold by Industries A/S, trade name Termamyl 120T lipase: lipolytic enzyme with an activity of 100KLU/g, trade name

Lipolase, sold by NOVO Industries A/S Endoenzyme: Endoglucanase, activity 3000 CEVU/g, sold by NOVO

Industries A/S sells PB4: Sodium perborate tetrahydrate, nominal structural formula

NaBO ₂ 3H ₂ O H ₂ O ₂ PB1: Anhydrous sodium perborate bleach, nominal formula NaBO ₂ H ₂ O ₂ Percarbonate: Sodium percarbonate, nominal formula 2Na ₂ CO ₃ .3H ₂ O ₂ NOBS: Sodium salt of nonanoyloxybenzenesulfonic acid TAED: Tetraacetylethylenediamine Mn Catalyst: Mn ^Ⅳ ₂ (mO) ₃ (1,4,7-trimethyl-1,4,7-triazacyclic

nonane) ₂ (PF ₆ ) ₂ , such as US Patent No. 5246621 and

    DTPA as described in 5244594: Diethylenetriaminepentaacetic acid DTPMP: Diethylenetriaminepenta(methylene phosphonate), composed of

Supplied by Monsanto under the trade name DEQUEST 2060 Photoactivator: Sulfonated zinc phthalocyanine coated with bleached dextrin Water-soluble polymer Brightener 1: 4,4′-Bis(2-sulfostyreneyl)biphenyl Disodium brightener 2: 4,4′-bis(4-anilino-6-morpholino-1,3,5-triazine-

2-yl)amino)stilbene-2,2′-disodium sulfonate HEDP: 1,1-hydroxyethylenediphosphonic acid EDDS: ethylenediamine-N,N’-disuccinic acid QEA1: bis((C ₂ H ₅ O)(C ₂ H ₄ O) _n (CH ₃ )-N ⁺ -C ₆ H ₁₂ -N ⁺ -(CH ₃ )

Bis((C ₂ H ₅ O)-(C ₂ H ₄ O) _n ), where n=20-30QEA2: Bis((C ₂ H ₅ O)(C ₂ H ₄ O) _n (CH ₃ )-N ⁺ R ₁ , where R ₁ is

C ₄ -C ₁₂ alkyl, and n=20-30QEA3: Tri{bis((C ₂ H ₅ O)-(C ₂ H ₄ O) _n (CH ₃ )-N ⁺ )-

(CONC ₃ H ₆ )}-C ₃ H ₆ O, where n=20-26 PEGX: Polyethylene glycol with a molecular weight of xPEO: Polyethylene oxide with a molecular weight of 50000 TEPAE: Tetraethylenepentamine ethoxylate PVP : polyvinylpyrrolidone polymer PVNO: polyvinylpyridine N-oxide PVPVI: copolymer of polyvinylpyrrolidone and vinylimidazole SRP1: sulfonyl-terminated ester with oxyethyleneoxy and p-

    Phthaloyl backbone SRP2: Diethoxylated poly(1,2-propylene terephthalate) short

      Block Polymer Silicone Antifoam Agents: Polydimethylsiloxane foam control agents in which silicone

     - oxyalkylene copolymer as a dispersant, the foam control

The ratio of the formulation to the dispersant is 10:1-100:1

Wax: paraffin paraffin

In the following examples, all contents refer to the weight percentage (%) of the composition.

Example 1

In accordance with the present invention, the following high density granular laundry detergent compositions AF are prepared which are particularly suitable for European machine washing conditions. A B C D. E. f LAS 8.0 8.0 8.0 8.0 8.0 8.0 C25E3 3.4 3.4 3.4 3.4 3.4 3.4 C46AS 1.0 2.0 2.5 - 3.0 4.0 C68AS 3.0 2.0 5.0 7.0 1.0 0.5 QAS - - 0.8 - - 0.8 Zeolite A 18.1 18.1 16.1 18.1 18.1 18.1 Zeolite MAP - 4.0 3.5 - - - carbonate 13.0 13.0 13.0 27.0 27.0 27.0 Silicate 1.4 1.4 1.4 3.0 3.0 3.0 sodium sulfate 26.1 26.1 26.1 26.1 26.1 26.1 MA/AA 0.3 0.3 0.3 0.3 0.3 0.3 CMC 0.2 0.2 0.2 0.2 0.2 0.2 PB4 9.0 9.0 9.0 9.0 9.0 9.0 TAED 1.5 1.5 1.0 1.5 - 1.5 Mn catalyst - 0.03 0.07 - - - DTPMP 0.25 0.25 0.25 0.25 0.25 0.25 HEDP 0.3 0.3 0.2 0.2 0.3 0.3 EDDS - - 0.4 0.2 - - QEA1 1.0 0.8 0.7 1.2 - 0.5 QEA2 - - - - 1.0 0.5 protease 0.26 0.26 0.26 0.26 0.26 0.26 Amylase 0.1 0.1 0.4 0.3 0.1 0.1 Photoactivated Bleach (ppm) 15ppm 15ppm 15ppm 15ppm 15ppm 15ppm Brightener 1 0.09 0.09 0.09 0.09 0.09 0.09 spices 0.3 0.3 0.3 0.3 0.3 0.3 Silicone Antifoam 0.5 0.5 0.5 0.5 0.5 0.5 Miscellaneous/small matter, to 100% Density (g/L) 850 850 850 850 850 850

Example 2

In accordance with the present invention, the following granular laundry detergent compositions GI, particularly suitable for European machine washing conditions, were prepared. G h I LAS 5.25 5.61 4.76 TAS 1.25 1.86 1.57 C45AS - 2.24 3.89 C25E3S - 0.76 1.18 C45E7 3.25 - 5.0 C25E3 - 5.5 - QAS 0.8 2.0 2.0 STPP 19.7 - - Zeolite A - 19.5 19.5 Zeolite MAP 2.0 - - NaSKS-6/citric acid (79:21) - 10.6 10.6 carbonate 6.1 21.4 21.4 Bicarbonates - 2.0 2.0 Silicate 6.8 - - sodium sulfate 39.8 - 14.3 MA/AA 0.8 1.6 1.6 CMC 0.2 0.4 0.4 PB4 5.0 12.7 - Percarbonate 5.0 - 12.7 TAED 0.5 3.1 - Mn catalyst 0.04 - - DTPMP 0.25 0.2 0.2 HEDP - 0.3 0.3 QEA1 0.9 1.2 - QEA2 - - 1.0 protease 0.26 0.85 0.85 Lipase 0.15 0.15 0.15 cellulase 0.28 0.28 0.28 Amylase 0.4 0.1 0.1 pvp 0.9 1.3 0.8 Photoactivated Bleach (ppm) 15ppm 27ppm 27ppm Brightener 1 0.08 0.19 0.19 Brightener 2 - 0.04 0.04 spices 0.3 0.3 0.3 Silicone Antifoam 0.5 2.4 2.4 Miscellaneous/small matter, to 100%

Example 3

According to the present invention, the following detergent formulations, particularly suitable for European machine wash conditions, were prepared. J K L m Blown powder: LAS 6.0 5.0 11.0 6.0 TAS 2.0 - - 2.0 Zeolite A - 27.0 - 20.0 STPP 24.0 - 24.0 - Sulfate 9.0 6.0 13.0 - MA/AA 2.0 4.0 6.0 4.0 Silicate 7.0 3.0 3.0 3.0 CMC 1.0 1.0 0.5 0.6 OEA1 0.8 1.0 1.4 0.5 OEA2 - - - 0.5 brightener 0.2 0.2 0.2 0.2 Silicone Antifoam 1.0 1.0 1.0 0.3 DTPMP 0.4 0.4 0.2 0.4 Spray onto: C45E7 - - - 5.0 C45E2 2.5 2.5 2.0 - C45E3 2.6 2.5 2.0 - spices 0.3 0.3 0.3 0.2 Silicone Antifoam 0.3 0.3 0.3 - Dry additives: Sulfate 3.0 3.0 5.0 10.0 carbonate 6.0 13.0 15.0 14.0 PB1 - - - 1.5 PB4 18.0 18.0 10.0 18.5 TAED 3.0 2.0 - 2.0 EDDS - 2.0 2.4 - protease 1.0 1.0 1.0 1.0 Lipase 0.4 0.4 0.4 0.2 Amylase 0.2 0.2 0.2 0.4 photoactivated bleach - - - 0.15 total 100.0 100.0 100.0 100.0

Example 4

According to the present invention, the following granular detergent formulations were prepared. Formulation N is especially suitable for use under Japanese machine wash conditions. Formula OS is especially suitable for use under US machine wash conditions. N o P o R S Blown powder: LAS 22.0 5.0 4.0 9.0 8.0 7.0 C45AS 7.0 7.0 6.0 - - - C46AS - 4.0 3.0 - - - C45E35 - 3.0 2.0 8.0 5.0 4.0 Zeolite A 6.0 16.0 14.0 19.0 16.0 14.0 MA/AA 6.0 3.0 3.0 - - - AAA - 3.0 3.0 2.0 3.0 3.0 sodium sulfate 7.0 18.3 11.3 24.0 19.3 19.3 Silicate 5.0 1.0 1.0 2.0 1.0 1.0 carbonate 28.3 9.0 7.0 25.7 8.0 6.0 OEA1 0.9 0.9 - - 0.5 1.1 OEA2 - - 0.8 1.0 - - OEA3 - - 0.4 - - - PEG4000 0.5 1.5 1.5 1.0 1.5 1.0 sodium oleate 2.0 - - - - - DTPA 0.4 - 0.5 - - 0.5 brightener 0.2 0.3 0.3 0.3 0.3 0.3 Spray onto: C25E9 1.0 - - - - - C45E7 - 2.0 2.0 0.5 2.0 2.0 spices 1.0 0.3 0.3 1.0 0.3 0.3 Gathering: C45AS - 5.0 5.0 - 5.0 5.0 LAS - 2.0 2.0 - 2.0 2.0 Zeolite A - 7.5 7.5 - 7.5 7.5 HEDP - 1.0 - - 2.0 - carbonate - 4.0 4.0 - 4.0 4.0 PEG4000 - 0.5 0.5 - 0.5 0.5 debris (water, etc.) - 2.0 2.0 - 2.0 2.0 Dry additives: TEAD 1.0 2.0 3.0 1.0 3.0 2.0 PB4 - 1.0 4.0 - 5.0 0.5 PB1 6.0 - - - - - Percarbonate - 5.0 12.5 - - - carbonate - 5.3 1.8 - 4.0 4.0 NOBS 4.5 - 6.0 - - 0.6 Cumene Sulfonic Acid - 2.0 2.0 - 2.0 2.0 Lipase 0.4 0.4 0.4 - 0.4 0.4 cellulase 0.1 0.2 0.2 0.2 0.2 0.2 Amylase 0.1 0.3 0.3 - - - protease 1.0 0.5 0.5 0.5 0.5 0.5 PVPVI - 0.5 0.5 - - - pvp 0.5 0.5 0.5 - - - PVNO - 0.5 0.5 - - - SRP1 - 0.5 0.5 - - - Silicone Antifoam - 0.2 0.2 - 0.2 0.2 total 100.0 100.0 100.0 100.0 100.0 100.0

Example 5

According to the present invention, the following granular detergent formulations were prepared. Formulations W and X are particularly suitable for use under US machine wash conditions. Y is especially suitable for use under Japanese machine wash conditions. T u V Blown powder: Zeolite A 30.0 22.0 6.0 sodium sulfate 19.0 5.0 7.0 MA/AA 3.0 3.0 6.0 LAS 14.0 12.0 22.0 C45AS 8.0 7.0 7.0 Silicate - 1.0 5.0 soap - - 2.0 Brightener 1 0.2 0.2 0.2 OEA1 0.6 2.0 1.0 carbonate 0.8 16.0 20.0 DTPMP - 0.4 0.4 Spray onto: - 1.0 5.0 C45E7 1.0 1.0 1.0 Dry additives: HEDP 1.0 - - PVPVI/PVNO 0.5 0.5 0.5 protease 1.0 1.0 1.0 Lipase 0.4 0.4 0.4 Amylase 0.1 0.1 0.1 cellulase 0.1 0.1 0.1 TEAD - 6.1 4.5 PB 11.0 5.0 6.0 sodium sulfate - 6.0 - Balance (moisture and sundries)

Example 6

According to the present invention, the following granular detergent combinations are prepared which are particularly suitable for use under European machine washing conditions. W x Blown powder: Zeolite A 20.0 - STPP - 20.0 LAS 6.0 6.0 C68AS 2.0 2.0 Silicate 3.0 8.0 MA/AA 4.0 2.0 CMC 0.6 0.6 OEA1 0.9 0.6 OEA3 0.1 - Brightener 1 0.2 0.2 DTPMP 0.4 0.4 Spray onto: C45E7 5.0 5.0 Silicone Antifoam 0.3 0.3 spices 0.2 0.2 Dry additives: carbonate 14.0 9.0 PB1 1.5 2.0 PB4 18.5 13.0 TAED 2.0 2.0 photoactivated bleach 15ppm 15ppm protease 1.0 1.0 Lipase 0.2 0.2 Amylase 0.4 0.4 cellulase 0.1 0.1 Sulfate 10.0 20.0 Balance (moisture and sundries) Density (g/L) 700 700

Example 7

According to the present invention, the following detergent compositions were prepared. Y Z AAA Blown powder: Zeolite A 15.0 15.0 15.0 sodium sulfate 0.0 5.0 0.0 LAS 3.0 3.0 3.0 OAS - 1.5 1.5 DTPMP 0.4 0.2 0.4 CMC 0.4 0.4 0.4 MA/AA 4.0 2.0 2.0 Gathering: LAS 5.0 5.0 5.0 TAS 2.0 2.0 1.0 Silicate 3.0 3.0 4.0 OEA1 1.0 2.5 0.6 Mn catalyst 0.03 - - Zeolite A 8.0 8.0 8.0 carbonate 8.0 8.0 4.0 Spray onto: spices 0.3 0.3 0.3 C45E7 2.0 2.0 2.0 C25E3 2.0 - - Dry additives: Citrate 5.0 - 2.0 Bicarbonates - 3.0 - carbonate 8.0 15.0 10.0 Percarbonate - 7.0 10.0 TAED 6.0 2.0 5.0 PB1 14.0 7.0 10.0 EDDS - 2.0 - Polyethylene oxide with a MW of 5,000,000 - - 0.2 Bentonite - - 10.0 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 Antifoam 5.0 5.0 5.0 Dry additives: sodium sulfate 0.0 3.0 0.0 Balance (moisture and sundries) 100.0 100.0 100.0 Density (g/L) 850 850 850

Example 8

According to the present invention, the following detergent compositions were prepared. BB CC DD EE LAS 20.0 14.0 24.0 22.0 OAS 0.7 1.0 - 0.7 TFAA - 1.0 - - C25E5/C45E7 - 2.0 - 0.5 C45E3S - 2.5 - - STPP 30.0 18.0 30.0 22.0 Silicate 9.0 5.0 10.0 8.0 carbonate 13.0 7.5 - 5.0 Oxycarbonate - 7.5 - - Percarbonate - 5.0 9.0 15.0 DTPMP 0.7 1.0 - - OEA1 0.4 1.2 0.5 2.0 OEA2 0.4 - - - SRP1 0.3 0.2 - 0.1 MA/AA 2.0 1.5 2.0 1.0 CMC 0.8 0.4 0.4 0.2 protease 0.8 1.0 0.5 0.5 Amylase 0.8 0.4 - 0.25 Lipase 0.2 0.1 0.2 0.1 cellulase 0.15 0.05 - - Photoactivated Bleach (ppm) 70ppm 45ppm - 10ppm Brightener 1 0.2 0.2 0.08 0.2 PB1 6.0 2.0 - - HEDP - - 2.3 - TEAD 2.0 1.0 - - Balance (moisture and sundries)

Example 9

The following compacted high density (0.96 kg/l) dishwashing detergent compositions FF to KK were prepared according to the invention, and the abbreviations of the ingredients used in the detergents have the following meanings: Metasilicate: Sodium metasilicate (SiO ₂ :Na ₂ O=1.0) nonionic: sold under the trade name Plurafac LF404 by BASF GmbH,

The average degree of ethoxylation is 3.8, while the average degree of propoxylation is 4.5

C ₁₃ -C ₁₅ mixed ethoxylated/propoxylated fatty alcohols (low foam) PAAC: cobalt(III) pentaamine acetate B _z P: benzoyl peroxide paraffin: sold under the tradename Winog 70 by Wintershall Paraffin oil BTA: benzotriazole bismuth nitrate: bismuth nitrate salt terpolymer: containing acrylic acid: maleic acid: ethacrylic acid monomer unit, its weight

The ratio is 60:20:20, the terpolymer 480N with an average molecular weight of about 7000: 3:7 acrylic acid/methacrylic acid, the average molecular weight is about 3500

random copolymer of FF GG HH II JJ KK STPP 24.80 24.80 25.00 28.39 28.50 20.00 Citrate - - - - 10.00 10.00 carbonate - - 17.50 17.50 - - OEA1 0.5 1.5 2.0 1.0 0.3 0.8 Silicate 20.36 20.36 14.81 14.81 14.81 - Metasilicate 2.50 2.50 2.50 - - - PB1 7.79 7.79 9.74 14.28 9.74 - PB4 - - - - 10.4 Percarbonate - - - - - 6.70 Non-ionic 1.50 1.50 2.00 1.50 2.00 2.60 TAED 2.39 2.00 2.70 2.00 3.60 4.00 HEDP 0.46 0.46 1.00 - 0.83 - DETPMP - - 0.65 - - - PAAC - - - 0.20 - - B ₂ P - - - 4.44 - - paraffin 0.50 0.50 0.50 0.50 - 0.20 protease 2.20 2.20 2.20 2.20 2.00 0.50 Amylase 1.50 1.50 1.20 1.50 1.00 1.10 BTA 0.30 0.30 0.30 0.30 - - bismuth nitrate - - 0.30 - - - trimer - - - 4.00 - - 480N 2.77 2.77 6.00 - 6.67 - Sulfate 8.44 8.44 20.77 - 23.24 1.00 Debris and Water Balance PH(1% solution) 10.90 10.90 11.00 10.80 10.90 9.60

Claims (24)

1. A granular detergent composition or component thereof comprising: (a) oxygen-releasing bleaching systems containing a peroxygen source; and (b) Water-soluble cationic compounds having soil removal/anti-redeposition properties selected from the group consisting of: 1) Ethoxylated cationic monoamines having the following structural formula:

2) Ethoxylated cationic diamines having the formula:

or

or

Wherein ^M1 is N+ or N group; each ^M2 is N+ or N group; and at least one ^M2 is N+ group; 3) Ethoxylated cationic polyamines having the following structural formula: 1) and mixtures thereof; wherein: A ¹ is

or -O-, R is H or C ₁ -C ₄ alkyl or hydroxyalkyl, R ¹ is C ₂ -C ₁₂ alkylene, hydroxyalkylene, alkenylene, arylene or alkarylene, or has 2- A C ₂ -C ₃ oxyalkylene moiety of about 20 oxyalkylene units, but not capable of forming any ON bonds; each R ² is a C ₁ -C ₄ alkyl or hydroxyalkyl group, a -LX moiety, or two R ² together Forms the -(CH ₂ ) _r -A ² -(CH ₂ ) _s - moiety, where A ² is -O- or -CH ₂ -, r is 1 or 2, s is 1 or 2, and r+s is 3 or 4; each R ³ is C ₁ -C ₈ alkyl or hydroxyalkyl, benzyl, -LX moiety, or, two R ³ or one R ² together with one R ³ form -(CH ₂ ) _r - A ² -(CH ₂ ) _s - moiety; R ⁴ is substituted C ₃ -C ₁₂ alkyl, hydroxyalkyl, alkenyl, aryl or alkaryl with para-substitution; R ⁵ is C ₁ - C ₁₂ alkenyl, hydroxyalkylene, alkenylene, arylene or alkarylene, or C ₂ -C ₃ oxyalkylene moieties having 2 to about 20 oxyalkylene units, but not forming any OO or ON bond; X is a nonionic group selected from H, C ₁ -C ₄ alkyl or hydroxyalkyl ester or ether group, and a mixed group thereof; L is a polyoxyalkylene moiety-[(R ⁶ O ) _m (CH ₂ CH ₂ O) _n ]- the hydrophilic chain; wherein R ⁶ is C ₃ -C ₄ alkylene or hydroxyalkylene, and the number of m and n should be such that -(CH ₂ CH ₂ O ) _{the n-} moiety comprises at least about 50% by weight of said polyoxyalkylene moiety; when ^M is N+, d is 1, and when M is ^N , d is 0; for said cationic monoamine, n is at least about 16, At least about 6 for said cationic diamine, at least about 3 for said cationic polyamine; p is 3-8; q is 1 or 0; t is 1 or 0, but when q is 1, t is 1, wherein ( The ratio of a) to (b) is 80:1 to 1:5. 2. A detergent composition or component thereof according to claim 1, wherein said ratio is from 20:1 to 1:1. 3. A granular detergent composition according to claim 1 or 2, wherein said cationic compound is used in an amount of 0.01-30% by weight of the detergent composition. 4. A granular detergent composition according to any one of claims 1 to 3, wherein said cationic compound is present in an amount of from 0.2% to 3% by weight of the detergent composition. 5. A granular detergent composition or component thereof according to any one of claims 1-4, wherein said cationic compound is an ethoxylated cationic monoamine, characterized in that one R is ^methyl and ^two R are In the LX moiety, m is 0 and n is at least about 20. 6. A granular detergent composition or component thereof according to any one of claims 1-4, wherein said cationic compound is an ethoxylated cationic diamine, characterized in that R ¹ is C ₂ -C ₆ alkylene. 7. A granular detergent composition or component thereof according to claim 6, wherein said ethoxylated cationic diamine is characterized in that ^R1 is hexylene. 8. A granular detergent composition or component thereof according to any one of claims 6 or 7, wherein said cationic compound is characterized in that ^R is a methyl or LX moiety, each ^R is a methyl, and ^M and each ^M2 is an N ⁺ group. 9. A granular detergent composition or component thereof according to any one of claims 6-8, wherein m is 0 and n is at least 12. 10. A detergent composition or component thereof according to any one of claims ^1-4 , wherein said cationic compound is an ethoxylated cationic polyamine, characterized in that R is a substituted _C3 - _C6 alkyl, hydroxyl Alkyl or aryl; Al is

And p is 3-6. 11. A granular detergent composition or component thereof according to any one of claims 6-8, wherein m is 0 and n is at least 20. 12. A granular detergent composition or component thereof according to any one of claims 1-11, wherein the cationic polymer having soil removal/anti-redeposition properties is characterized by having a main chain, at least 2 M groups and at least 1 LX group, where M is a cationic group connected to the main chain, or integrated with the main chain, and contains an N ⁺ positive charge center; L connects the M group and the X group, or connects X to the On the polymer main chain; X is a nonionic group selected from H, C ₁ -C ₄ alkyl or hydroxyalkyl ester or ether group, and a mixed group thereof; and L is a polyoxyalkylene moiety-[ (R ⁶ O) _m (CH ₂ CH ₂ O) _n ]- the hydrophilic chain. 13. A granular detergent composition or component thereof according to claim 12, wherein said cationic polymer is a backbone selected from the group consisting of polyurethanes, polyesters, polyethers, polyimides, polyalkyleneimides and mixtures thereof ethoxylated cationic polymers. 14. A granular detergent composition according to any one of claims 1-13, wherein said oxygen-releasing bleach system comprising a peroxygen source is used in an amount of 1% to 40% by weight of the composition. 15. A granular detergent composition according to any one of claims 1-14, wherein said peroxygen source is an inorganic perhydrate salt in an amount of from 2% to 30% by weight of the composition. 16. A granular detergent composition according to claim 15, wherein said inorganic perhydrate salt is sodium percarbonate or sodium perborate. 17. A granular detergent composition or component thereof according to any one of claims 1 to 14, wherein the oxygen releasing bleach system comprises a source of hydrogen peroxide and a peroxyacid bleach precursor compound. 18. A granular detergent composition according to claim 17 wherein said peroxyacid bleach precursor compound is present in an amount of from 1.0% to 15% by weight of the detergent composition. 19. A granular detergent composition according to any one of claims 1-18, comprising a bleach catalyst selected from the group consisting of Mn ^IV ₂ (uo) ₃ (1,4,7-trimethyl-1,4,7-triaza cyclononane) ₂ -(PF ₆ ) ₂ , Mn ^Ⅲ ₂ (uo) ₁ (u-OA _c ) ₂ (1,4,7-trimethyl-1,4,7-triazacyclononane) ₂ -(ClO ₄ ) ₂ , Mn ^Ⅳ ₄ (uo) ₆ (1,4,7-triazacyclononane) ₄ -(ClO ₄ ) ₂ , Mn ^Ⅲ Mn ^Ⅳ ₄ (uo) ₁ (u-OA _c ) ₂ (1,4,7-trimethyl-1,4,7-triazacyclononane) ₂ -(ClO ₄ ) ³ , Mn(1,4,7-trimethyl-1,4 ,7-triazacyclononane (OCH ₃ ) ₃ -(PF ₆ ), Co(2,2'-dipyridylamine)Cl ₂ , bis-(isothiocyanato)dipyridylamine cobalt ( Ⅱ), tris(dipyridylamine)-cobalt(II) perchlorate, Co(2,2-dipyridylamine) ₂ -O ₂ ClO ₄ , bis(2,2'-dipyridylamine) perchlorate Cu(II) acid, tris(di-2-pyridylamine) iron(II) perchlorate, Mn gluconate, Mn(CF ₃ SO ₃ ) ₂ , Co(NH ₃ ) ₅ Cl, binuclear Mn and Complexes of tetra-N-dentate ligands and di-N-dentate ligands, including N ⁴ Mn ^Ⅲ (uo) ₂ Mn ^Ⅳ N ₄ ) ⁺ and [diPy ₂ Mn ^Ⅲ (uo) ₂ Mn ^Ⅳ diPy ₂ ] (ClO ₄ ) ₃ and mixtures thereof. 20. A granular detergent composition according to any one of claims 1-19, formulated in such a way that the wash liquor has a pH of 8.0-10.5 twenty one. According to any one detergent composition in the claim 1-20, wherein the consumption of heavy metal ion chelating agent is the 0.1-10% of described detergent composition weight twenty two. A granular detergent composition or component thereof according to any one of claims 1-21, comprising an anionic surfactant, a nonionic surfactant, a cationic surfactant, an amphoteric surfactant, and a zwitterionic surfactant Active agents and surfactants for mixtures thereof. twenty three. A method of washing clothes in a domestic washing machine, wherein an effective amount of a granular detergent composition according to any one of claims 1-22 is introduced into the drum of the washing machine before commencing washing, preferably using a dispensing device, said The dispensing device enables the gradual release of the granular detergent composition into the wash liquor during washing. twenty four. Use of a granular detergent composition according to claims 1-22 or components thereof in a dishwashing process.