CN1238801A - Detergent composition or component - Google Patents

Abstract

The present invention relates to solid or ganular detergent composition or component or spray-dried particle containing one or more carboxylate-containing polyelectrolyte compounds, having builder or dispersant properties, and one or more cationic compounds, which are cationic, (partially) quaternized ethoxylated (poly)amine compounds with clay-soil removal/anti-redeposition properties, for use in laundry and dish washing processes.

Description

Detergent composition or component

Field of Invention

The present invention relates to detergent compositions or components for use in laundry and dishwashing processes which contain cationic compounds having clay soil/particulate soil/anti-redeposition properties and one or more Carboxylate-containing polyelectrolyte compounds with agent properties.

Background of the Invention

A particularly important property of detergent compositions is the ability to remove particulate soils from a variety of fabrics during laundering. An important class of particulate soil is earth soil. Earth soil particles generally comprise negatively charged aluminosilicate layers and positively charged cations (eg, calcium) positioned between and remaining attached to the negatively charged layers.

Various forms of compounds having earth soil removal properties can be proposed. A pattern requires the compound to have two different properties. The first property is the ability of the compound to adsorb to the negatively charged layer of the soil particle; and once adsorbed, the ability of the compound to repel (swell) the negatively charged layer such that the soil particle loses its adhesion and can be removed into the wash water .

In addition to removing soil soils, there is a need to keep the removed soils 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 cause a tarnish or "greying" effect, which is especially noticeable on white fabrics. To reduce such problems, antiredeposition agents are also often included in detergent compositions.

Other detergent compounds traditionally used in detergents are soil dispersants and anti-fouling agents, such as carboxylate-containing polyelectrolyte compounds.

EP-B-111965 discloses the use of cationic compounds in detergents having both clay soil removal and anti-redeposition properties.

US4659802 and US4664848 describe quaternary ammonium compounds having clay soil removal and anti-redeposition properties and which may be used in combination with anionic surfactants.

One proposed model for the anti-redeposition effects of these compounds is as follows. In wash water, the adsorption of positively charged molecules on the surface of soil particles imparts dispersive properties to the soil particle molecules. As more and more of these compounds adsorb to the suspended soil soil particles, the soil soil particles become trapped in the hydrophilic layer. This hydrophilic occluded soil is inhibited from redeposition onto hydrophobic fabrics such as polyester during the laundry or dishwashing cycle.

It has been found that known earth soil removal cationic compounds do not always remove earth particles from fabric surfaces quickly and efficiently into the wash water. This may be due to the fact that soil and granular soils are linked together by calcium bridges, which inhibit cationic compounds that remove soil-based soils from repelling the negatively charged layer of soil, thereby inhibiting soil particles from losing their adhesion.

It has also been found that during laundry or dishwashing, the anti-redeposition properties of these known earth soil removing cationic compounds are diminished under hard water conditions, i.e. when high levels of free calcium (and/or magnesium) are present in the wash water. hour.

The applicants have now found that these problems can be solved by, in detergent components or washes, (partially) quaternized ethoxylated (poly)amines containing specific amounts of cations having clay soil removal/anti-redeposition properties. Reagent compositions including specific amounts of carboxylate-containing polyelectrolyte compounds are improved. An example of such a component is spray dried granules. It has now been found that such detergent components or detergent compositions provide surprisingly superior soil/soil removal and cleaning performance over detergent compositions using either of these components alone. It has also been found that specific ratios of cationic quaternized ethoxylated (poly)amines to carboxylate-containing polyelectrolyte compounds are particularly preferred, enabling good performance to be obtained even when using very low amounts of each component .

It has been found that the cleaning performance of detergent compositions containing carboxylate-containing polyelectrolyte compounds and cationic, (partially) quaternized ethoxylated (poly)amines is dependent on the amount of carboxylate-containing polyelectrolyte compounds used and its properties (such as the molecular weight of the polymer and the monomer segments contained in the polymer). For example, under builder-containing conditions, it has been found that copolymeric polycarboxylic acid compounds such as maleic/acrylic acid copolymers have better (calcium) builder/dispersion properties than homopolymeric polycarboxylic acid compounds of the same molecular weight. agent performance. Thus, lower amounts of certain preferred polymeric compounds are as effective as higher amounts of other compounds.

Yet another advantage of the present invention is that soil/soil removal is even observable after only one wash cycle is completed.

All documents cited in this specification are, in relevant part, incorporated by reference.

Summary of Invention

According to the present invention there is provided a solid, preferably granular detergent composition or component thereof comprising: (a) a carboxylate-containing polyelectrolyte compound; and (b) having soil soil removal/anti-redeposition properties A water-soluble cationic compound selected from:

1) Ethoxylated cationic monoamines having the formula:

或

其中M¹是N+或N基团；每个M²是N+或N基团，至少一个M²是N+基团。2). Ethoxylated cationic diamines having the formula: or

or

wherein M ¹ is an N+ or N group; each M ² is an N+ or N group, and at least one M ² is an N+ group.

3) Ethoxylated cationic polyamines having the formula:

或 R是H或C₁-C₄烷基或羟烷基，R¹是C₂-C₁₂亚烷基、羟基亚烷基、亚链烯基、亚芳基或烷亚芳基，或具有2-约20个氧亚烷基单元的C₂-C₃氧亚烷基链段，条件是不形成O-N键；每个R²是C₁-C₄烷基或羟烷基，链段-L-X；或两个R²结合形成-(CH₂)_r-A²-(CH₂)_s-，其中A²是-O-或-CH₂-,r是1或2,s是1或2,r+s是3或4；每个R³是C₁-C₈烷基或羟烷基、苄基、链段L-X，或两个R³或一个R²和一个R³结合形成链段-(CH₂)_r-A²-(CH₂)_s-；R⁴是具有p个取代位置的取代的C₃-C₁₂烷基、羟烷基、链烯基、芳基或烷芳基；R⁵是C₁-C₁₂链烯基、羟基亚烷基、亚链烯基、亚芳基或烷亚芳基，或具有2-约20个氧亚烷基单元的C₂-C₃氧亚烷基链段，条件是不形成O-O或O-N键；X是选自H、C₁-C₄烷基或羟烷基酯或醚基团和它们的混合物的非离子基团；L是含有聚氧亚烷基链段：-[(R⁶O)_m(CH₂CH₂O)_n]-的亲水链；其中R⁶是C₃-C₄亚烷基或羟基亚烷基，m和n是使得链段-(CH₂CH₂O)_n-占所说的聚氧亚烷基链段至少约50％的数值；当M²是N+时，d是1，当M²是N时，d是0；对于所说的阳离子单胺，n是至少约16，对于所说的阳离子二胺，n是至少约6，和对于所说的阳离子聚胺，n是至少约3；p是3-8；q是1或0；t是1或0，条件是当q是1时，t是1；和其中(a)与(b)的比值是1∶95至95∶1。(a)与(b)的优选比值是1∶1至1∶6。4) their mixture; wherein A ¹ is

or 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 segment of about 20 oxyalkylene units, provided that no ON bond is formed; each R ² is a C ₁ -C ₄ alkyl or hydroxyalkyl, segment -LX ; or two R ² are combined to form -(CH ₂ ) _r -A ² -(CH ₂ ) _s -, wherein A ² is -O- or -CH ₂ -, r is 1 or 2, s is 1 or 2, r+s is 3 or 4; each R ³ is C ₁ -C ₈ alkyl or hydroxyalkyl, benzyl, segment LX, or two R ³ or one R ² and one R ³ combine to form a segment- (CH ₂ ) _r -A ² -(CH ₂ ) _s -; R ⁴ is a substituted C ₃ -C ₁₂ alkyl, hydroxyalkyl, alkenyl, aryl or alkaryl group with p substitution positions; R ⁵ is C ₁ -C ₁₂ alkenyl, hydroxyalkylene, alkenylene, arylene or alkarylene, or C ₂ -C ₃ oxygen having 2 to about 20 oxyalkylene units Alkylene segment, provided that no OO or ON bond is formed; X is a nonionic group selected from H, C ₁ -C ₄ alkyl or hydroxyalkyl ester or ether groups and mixtures thereof; L is a group containing Polyoxyalkylene segment: a hydrophilic chain of -[(R ⁶ O) _m (CH ₂ CH ₂ O) _n ]-; where R ⁶ is C ₃ -C ₄ alkylene or hydroxyalkylene, m and n is such that segment -(CH ₂ CH ₂ O) _n - comprises at least about 50% of said polyoxyalkylene segment; when M ² is N+, d is 1, when M ² is N When, d is 0; for said cationic monoamine, n is at least about 16, for said cationic diamine, n is at least about 6, and for said cationic polyamine, n is at least about 3; p is 3-8; q is 1 or 0; t is 1 or 0, with the proviso that when q is 1, t is 1; and wherein the ratio of (a) to (b) is 1:95 to 95:1. The preferred ratio of (a) to (b) is 1:1 to 1:6.

In addition, it has been found that detergent compositions, and especially detergent components and especially spray-dried The granules are friable and flowable, and have no tendency to stick, and they are capable of adsorbing other detergent compounds, if present, such as anionic, cationic and nonionic surfactants. This therefore reduces the cohesiveness of compositions comprising such components or spray-dried particles.

Thus, according to a preferred aspect of the present invention, it relates to spray-dried granules comprising the above-mentioned compounds (a) and (b) in a preferred ratio of (a) and (b) of 1:1 to 1:10.

Preferred anionic counterions for cationic water soluble compounds are halides such as Cl ⁻ or Br ⁻ , most preferably MeSO ₄ ⁻ .

Detailed description of the invention

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

In the composition or component of the present invention, the ratio of cationic compound to carboxylate-containing polyelectrolyte compound is 1:95-95:1, more preferably 1:25-25:1, most preferably 1:5-5:1 .

When the amount of cationic compound and carboxylate-containing polyelectrolyte is low, it may be preferred that the ratio of carboxylate-containing polyelectrolyte compound to water-soluble cationic compound in said composition is preferably 1:1 to 1:10, More preferably 1:1-1:4, most preferably 1:1-1:2.

When present in the detergent composition according to the present invention, the water-soluble cationic compound is preferably present in an amount of from 0.01% to 30%, more preferably from 0.1% to 15%, most preferably from 0.2% to 3.0% by weight of the detergent composition. %.

In spray-dried granules, it is particularly preferred that the ratio of carboxylate-containing polyelectrolyte compound to water-soluble cationic compound in said components is 1:1 to 1:10, more preferably 1:1 to 1:4, most preferably Preferably 1:1-1:2.

In the spray-dried granule or detergent component according to the present invention, the preferred content of water-soluble cationic compound is 0.1%-30%, more preferably 0.5%-15%, by weight of the spray-dried granule or detergent component, Even more preferably 0.5%-7%, most preferably 0.6%-2%.

Such spray-dried particles or components are preferably present in granular detergent compositions at 5% to 90%, more preferably 20% to 60%, most preferably 30% to 50%, by weight of the composition. cationic amine

Water-soluble cationic compounds of the invention suitable for use in the detergent compositions or components of the invention include ethoxylated cationic monoamines, ethoxylated cationic diamines and ethoxylated cationic polyamines as defined above.

环状(例如

或最优选直链(例如-CH₂CH₂-,-CH₂CH₂CH₂-)亚烷基、羟基亚烷基、亚链烯基、烷亚芳基或氧亚烷基。对于乙氧基化阳离子二胺，R¹优选是C₂-C₆亚烷基。每个R²优选是甲基或链段-L-X；每个R³优选是C₁-C₄烷基或羟烷基，最优选甲基。In the above formulas for cationic amines, ^R can be branched (for example:

circular (eg

Or most preferably straight chain (eg -CH ₂ CH ₂ -, -CH ₂ CH ₂ CH ₂ -) alkylene, hydroxyalkylene, alkenylene, alkarylene or oxyalkylene. For ethoxylated cationic diamines, R ¹ is preferably C ₂ -C ₆ alkylene. Each R ² is preferably methyl or segment -LX; each R ³ is preferably C ₁ -C ₄ alkyl or hydroxyalkyl, most preferably methyl.

The positive charge of the N+ group is offset by an appropriate number of counter anions. Suitable counteranions include Cl- ^, Br-, _SO3-2 , _PO4-2 , _MeSO4- ^, and ^the like. Particularly preferred counteranions are Cl- and Br-, but MeSO ₄ ^- is most preferred.

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

In the above formula, the hydrophilic chain L generally consists entirely of a polyoxyalkylene segment -[(R ⁶ O) _m (CH ₂ CH ₂ O) _n -]. The -(R ⁶ O) _m - and -(CH ₂ CH ₂ O) _n - segments of the polyoxyalkylene segment can be mixed together or preferably form -(R ⁶ O) _m - and -(CH ₂ Blocks of CH ₂ O) _n -segments. R ⁶ is preferably C ₃ H ₆ (propylene); m is preferably 0 to about 5, most preferably 0, ie the polyoxyalkylene segment consists entirely of the segment -(CH ₂ CH ₂ O) _n - composition. _The segment -( _CH2CH2O ) _n- preferably comprises at least about 85% by weight of the polyoxyalkylene segment, most preferably 100% by weight (m is 0).

In the above formulas, ^M1 and each ^M2 are preferably N+ groups for cationic diamines and polyamines.

其中X和n定义同上，a是0-20，优选0-4(例如亚乙基、亚丙基、六亚甲基)，b是1或0。对于优选的阳离子单胺(b=0)，n优选是至少约16，一般在约20-35范围。对于优选的阳离子二胺(b=1)，n至少约12，一般在约12-42范围。Preferred ethoxylated cationic monoamines and diamines have the formula:

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

In the ethoxylated cationic polyamines of the above formula, R ⁴ (linear, branched or cyclic) is preferably a substituted C ₃ -C ₆ alkyl, hydroxyalkyl or aryl group; A ¹ is preferably: n is preferably at least about 12, generally 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 substituted alkyl, hydroxyalkyl or alkenyl and when q is 0, R ⁵ is preferably C ₂ -C ₃ oxyalkylene; when q is 1, R ⁵ is preferably C ₂ - C ₃ alkylene.

或

这些乙氧基化阳离子聚胺还可衍生自聚氨基环氧丙烷衍生物，例如：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 the value of each c is from 2 to about 20. Carboxylate-containing polyelectrolyte compounds

An essential component of the present invention is one or more carboxylate-containing polyelectrolyte compounds which have builder or dispersant properties.

Preferably these compounds are homo or copolymeric polycarboxylic acid compounds, most preferably copolymeric polycarboxylic acid compounds wherein the acid monomers of said polycarboxylic acid compounds comprise at least two carboxyl. Salts of these polycarboxylic acid compounds are also contemplated in the present invention. In preferred aspects, the polycarboxylate compounds of the present invention comprise at least 12 carboxylate groups.

The carboxylate-containing polyelectrolyte compound, if present in the detergent composition according to the present invention, preferably comprises from 0.01% to 40% by weight of the detergent composition, more preferably from 0.1% to 10%, most preferably 0.2%-6%.

If the carboxylate-containing polyelectrolyte compound is present in the detergent component of the present invention, it is preferably present in an amount of 0.05% to 30%, more preferably 0.1% to 15%, more preferably 0.15% by weight of the detergent component. %-7%, most preferably 0.2%-2.0% or more preferably to 1.2%.

Where said component is a spray-dried granule, the carboxylate-containing polyelectrolyte compound is preferably present in an amount of from 0.2% to 2.0%, or more preferably to 1.2%, by weight of the spray-dried granule.

Such spray-dried particles or such components are preferably present in the granular detergent at a level of from 5% to 90%, more preferably from 20% to 60%, most preferably from 30% to 50%, by weight of the granular detergent composition. agent composition.

Carboxylate-containing polyelectrolyte materials can be prepared by polymerizing or copolymerizing suitable unsaturated monomers, preferably in their acid form. Unsaturated monomeric acids which can be polymerized to form suitable polymeric polycarboxylic acids are selected from the group consisting of acrylic acid, maleic acid (or maleic anhydride), fumaric acid, itaconic acid, aconitic acid, mesaconic acid, citraconic acid and Methylmalonic acid. Carboxylate-free monomeric moieties such as vinylmethyl ether, styrene, ethylene, etc. present in these carboxylate-containing polyelectrolyte compounds herein are also suitable provided that such moieties do not constitute more than 40% by weight. The carboxylate-containing material may also optionally include additional monomeric units such as nonionic spacer units. For example, suitable nonionic spacer units may include vinyl alcohol or vinyl acetate.

Particularly preferred carboxylate-containing polyelectrolyte compounds are based on acrylic acid/maleic acid copolymers. Such materials include the water-soluble salts of copolymers of acrylic acid and maleic acid/maleic anhydride. The average molecular weight of such copolymers in the acid form may preferably range from 1,000 to 100,000, more preferably from 2,000 to 75,000, or even more preferably to 70,000, but most preferably are copolymers having an average molecular weight of 2,500 to 20,000, or in another In preferred embodiments the average molecular weight is in the range of 60,000 to 75,000 or even to 70,000. In such copolymers, the ratio of acrylate to maleate moieties generally ranges from 30:1 to 1:30, more preferably from 10:1 to 1:1, most preferably from 4:1 to 7:3. Water-soluble salts of such acrylic acid/maleic acid copolymers can include, for example, alkali metal, ammonium and substituted ammonium salts. Suitable acrylic/maleic acid copolymers of this type are known materials and are described in European Patent Application No. 66915, published December 15, 1982, and in EP 193,360, published September 3, 1986.

Other suitable carboxylate-containing polyelectrolyte compounds can be derived from acrylic acid. Such acrylic acid-based polymers suitable for the present invention are, for example, the water-soluble salts of polyacrylic acid. The average molecular weight of the homopolymer in the acid form is preferably in the range 1800-100000, more preferably in the range 2000-10000, most preferably in the range 3000-5000. Water soluble salts of such acrylic acid polymers can include, for example, alkali metal, ammonium and substituted ammonium salts. Suitable polymers of this type are known substances. The use of polyacrylates of this type in detergent compositions is disclosed, for example, in US Patent 3,308,067, issued March 7, 1967 to Diehl.

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

Further examples of carboxylate-containing polyelectrolyte compounds suitable for the purposes of the present invention include maleic/acrylic acid/vinyl alcohol terpolymers. Such materials are also disclosed in EP193360 and include eg 45/45/10 acrylic acid/maleic acid/vinyl alcohol terpolymers.

Terpolymers containing monomeric units selected from maleic acid, acrylic acid and polyaspartic acid, especially those having an average molecular weight of 5,000-20,000, are also suitable for use in the present invention.

Further suitable carboxylate-containing polyelectrolyte compounds are ethylene glycol-containing polyelectrolytes, especially those having a molecular weight of 1,000-10,000, more preferably 2,000-8,000, most preferably about 4,000.

Other preferred carboxylate-containing polyelectrolyte compounds are those compounds generally having a hydrophilic backbone and at least one hydrophobic side chain.

Preferably, carboxylate-containing polyelectrolyte compounds of this type have a molecular weight between 500-100,000, more preferably between 1,000-70,000, especially 1,500-10,000, or in another preferred embodiment from 2,800-6,000. The carboxylate-containing polyelectrolyte compounds used in the present invention can be prepared, for example, by using conventional water-based polymerization methods, suitable methods are described in, for example, GB8924477, GB8924478 and GB8924479.

Generally, the hydrophilic backbone of polymers is mainly linear (the main chain of the backbone accounts for at least 50%, preferably more than 75%, and most preferably more than 90% of the weight of the backbone), suitable monomer components for the hydrophilic backbone These are, for example, unsaturated C ₁ -C ₆ acids, ethers, alcohols, aldehydes, ketones or esters, sugar units, alkoxy units, maleic anhydride and saturated polyols such as glycerol. Preferably the hydrophobic side chains consist of alkoxy groups such as butylene oxide and/or propylene oxide and/or alkyl or alkenyl chains having 5 to 24 carbon atoms. Hydrophobic groups can be attached to the hydrophilic backbone through relatively hydrophilic linkages such as polyethoxy linkages.

Preferred carboxylate-containing polyelectrolyte compounds of this type are the polymers described in WO 91/08281.

Preferred counterions for carboxylate-containing polyelectrolyte compounds are, for example, sodium, magnesium or calcium ions. spray dried granules

Preferred ingredients according to the invention include spray-dried granules useful in detergent compositions. The detergent composition may consist essentially of such granules, but preferably the detergent composition comprises the granules and other components of different chemical composition.

The spray-dried particles of the present invention are made by a process comprising a spray-drying step. This spray drying step produces spray dried granules generally having a free moisture content of less than 10% by weight, preferably less than 7%, or more preferably less than 6%.

The moisture content here is determined by placing a 2 g sample of detergent granules in, for example, a Petri dish, placing the sample in a heating chamber at a temperature of up to 160°C for 10 minutes, and then measuring the weight loss due to evaporation of water.

Generally, the granules of the present invention are formed by granulating a paste or slurry or blend comprising the cationic compound and carboxylate-containing polyelectrolyte by spray drying methods known in the art and drying.

The process for preparing spray-dried granules involves preparing an aqueous-dispersion, commonly referred to as a paste or slurry or blend, comprising the final granule components.

The cationic compound and carboxylate-containing polyelectrolyte may be mixed together before adding the other components of the blend which will be contained in the spray-dried granules. Additionally, the cationic compound and carboxylate-containing polyelectrolyte may be mixed with other organic compounds to be included in the final spray-dried granule prior to adding the other components of the blend (to be included in the final spray-dried granule). Alternatively, the cationic compound and carboxylate-containing polyelectrolyte can be added to the crutcher and blend at the same time as the other components to be contained in the final spray-dried granule.

In order to save energy and increase the production capacity of the drying equipment, the blend usually has a suitably high solids content, such as 40%-80%, and the balance substance is, for example, 10%-60% water. More water can be used, but energy requirements are increased, tower capacity is reduced, the resulting product may be stickier and less fluid, and often does not result in the desired low density base and final detergent Composition granules. The blend preferably has a temperature of 50°C to 100°C, typically 80°C prior to the drying step.

The blend is then sprayed at high pressure (usually 40-100 bar, preferably 70-90 bar, typically at about 80 bar) through one or more nozzles into a drying tower where the resulting dry air is passed through the drying tower. The droplets of the blend are dried into spherical particles. Equivalent atomizers of other designs may also be used in place of the nozzles. It is preferred that the spray drying tower is designed as countercurrent, the height of the tower is usually 5-25 meters, the hot gas flow entering is usually the gaseous product of oil or gas combustion, the temperature is in the range of 150°C-400°C, and the temperature of the outlet airflow is usually 50°C-160°C ℃. Parallel columns can also be used, where similar inlet and outlet gas stream temperatures are obtained.

The size of the nozzle for producing the admixture droplets is selected such that particles are formed with a preferred particle size, preferably 0.1 mm to 3.0 mm. Preferably, substantially all particles are within this size range when exiting the spray tower, but any out-of-size particles may be removed by sieving and may be reduced in size to the desired size range or may be recycled to the same or in subsequent blends.

Preferred additional components of the blend may be anionic surfactants, cationic softeners or cationic surfactants, nonionic surfactants, sulfates and carbonates, and hydrotropes.

Optionally, after drying is complete to obtain granules in the desired particle size range, additional detergent compounds or components may be added to the granules, preferably by melting the compounds or components and the melted compounds or components ( It may be a concentrated aqueous solution, but preferably contains no water) is sprayed onto the surface of the rolling substrate in an inclined drum through which the particles move from the high feed end to the discharge end.

The particles can be incorporated into detergent compositions by any means known in the art. Preferably the granules are dry blended into other detergent ingredients. additional detergent ingredients

The detergent compositions or components according to the invention may also contain further detergent components. The precise nature of these additional components and their incorporation levels will depend upon the physical form of the components and the precise nature of the laundering operation in which they are employed.

The components or detergent compositions according to the invention preferably contain one or more additional detergent components selected from the group consisting of surfactants, additional builders, chelating agents, bleaching agents, bleach precursors, bleaching agents agent catalysts, additional organic polymeric compounds, enzymes, suds suppressors, additional lime soap dispersants, additional soil suspending and anti-redeposition agents, soil release agents, perfumes and corrosion inhibitors. cationic polymer

A preferred additional component may be an additional cationic polymeric ethoxylated amine compound having particulate soil/clay soil/anti-redeposition action 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; X is a nonionic group selected from the group consisting of H, C ₁ - C ₄ alkyl or hydroxyalkyl ester or ether groups, and mixtures thereof; and L is the linking group M and X or a hydrophilic chain linking X to the polymer backbone.

The term "polymer backbone" as used herein refers to the polymeric segment to which the groups M and L-X are attached or integral. Included within this term are oligomeric backbones (2-4 units), as well as true polymeric backbones (5 or more units).

The term "connection" mentioned here means that the group is hung on the polymer backbone, examples of which are represented by the following general structural formulas A and B:

The term "hanging on" as used herein means that the group constitutes a part of the polymer backbone, examples of which are represented by the following general structural formulas C and D:

Any polymer backbone can be used as long as the cationic polymer formed is water soluble and has clay soil removal/anti-redeposition properties. Suitable polymer backbones are available from polyurethanes, polyesters, polyethers, polyamides, polyimides, etc., polyacrylates, polyacrylamides, polyvinyl ethers, polyethylene, polypropylene and similar polyalkylenes polystyrene and similar polyalkylarylenes, polyalkyleneamines, polyalkyleneimines, polyvinylamines, polyallylamines, polydiallylamines, polyvinylpyridines , polyaminotriazole, polyvinyl alcohol, aminopoly-1,3-urea and mixtures thereof.

M can be any compatible cationic group including N+ (quaternized) positively charged centers. The quaternized positively charged center can be represented by the following general structural formulas E and F:

Particularly preferred M groups are those containing a quaternization center represented by the general formula E. The cationic groups are preferably located close to or integral with the polymer backbone.

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

X can be a nonionic group selected from hydrogen (H), _C1 - _C4 alkyl or hydroxyalkyl ester or ether groups, and mixtures thereof. Preferred ester or ether groups are acetate and methyl ether, respectively. Particularly preferred nonionic groups are H and methyl ether.

Cationic polymers suitable for use in the granular detergent components of the present invention will generally have a ratio of cationic groups M to nonionic groups X of 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, nonionic (ie containing groups L-X) and mixed cationic/nonionic monomers. The ratio of M to X groups can generally range from about 2:1 to 1:10. In preferred cationic polymers, the ratio is about 1:1 to 1:5. The polymers resulting from such copolymerization are generally random, ie the cationic, nonionic and mixed cationic/nonionic monomers are copolymerized in a non-repeating sequence.

Units containing M and LX groups can constitute 100% of the cationic polymers of this invention. However, it is also permissible to include other units (preferably non-ionic) in the polymer. Examples of other units include acrylamide, vinyl ether and those units containing a non-quaternized tertiary amine group (M ¹ ) which contains an N center. These other units may comprise from 0% to about 90% of the polymer (units containing M and LX groups, including Mi ^- LX groups comprising about 10% to 100% of the polymer). Typically, these other units comprise from 0% to about 50% of the polymer (units containing M and LX groups comprise from about 50% to 100% of the polymer).

The number of each of the M and L-X groups typically ranges from about 2-200. Typically, the number of each of the M and L-X groups ranges from about 3-100. Preferably, the number of each of the M and L-X groups is about 3-40.

Other segments not used for linking groups M and X or linking polymer backbone, hydrophilic chain L are usually completely composed of polyoxyalkylene segments-[(R'O) _m (CH ₂ CH ₂ O) _n ] -composition. -(R'O) _m - and -(CH ₂ CH ₂ O) _n - of the polyoxyalkylene segment may be mixed together, or preferably -(R'O) _m - and -(CH ₂ CH ₂ O) _{The n} -segments form blocks. R' is preferably C ₃ H ₆ (propylene); m is preferably 0 to about 5, most preferably 0; that is, the polyoxyalkylene segment consists entirely of -(CH ₂ CH ₂ O) _n - segments composition. The segment -( _CH2CH2O ) _n- preferably comprises at least about 85%, most preferably 100% by weight of _the polyoxyalkylene segment (m is 0). For -(CH ₂ CH ₂ O) _n - segments, n is typically in the range of about 3-100. Preferably n is about 12-42.

A plurality (2 or more) of segments -LX can also be linked together and attached to the group M or to the polymer backbone, examples of which are represented by the following general structural formulas G and H:

For example, structures such as G and H can be obtained by reacting glycidol with the group M or with the polymer backbone and ethoxylating the subsequently formed hydroxyl groups.

Representative types of cationic polymers of the present invention are as follows: A. Polyurethane, polyester, polyether, polyamide or similar polymers.

其中A¹是： 或

X是0或1；R是H或C₁-C₄烷基或羟烷基；R¹是C₂-C₁₂亚烷基、羟基亚烷基、亚链烯基、环状亚烷基、亚芳基或烷亚芳基、或具有2-约20个氧亚烷基单元的C₂-C₃氧亚烷基链段，条件是不与A¹形成O-O或O-N键；当x是1时，R²是-R⁵-，除非当A¹是：或是-(OR⁸)_y-或-OR⁵-时，条件是不与A¹形成O-O或O-N键，和R³是-R⁵-，除非当A¹是：

或是-(R⁸O)_y-或-R⁵O-时，条件是不与A¹形成O-O或O-N键；当x是0时，R²是：

或

和R³是-R⁵-；R⁴是C₁-C₄烷基或羟烷基，或链段-(R⁵)_k-[(C₃H₆O)_m(CH₂CH₂O)_n]-X；R⁵是C₁-C₁₂亚烷基、羟基亚烷基、亚链烯基、亚芳基或烷亚芳基；各R⁶是C₁-C₄烷基或羟烷基，或链段-(CH₂)_r-A²-(CH₂)_s-，其中A²是-O-或-CH₂-；R⁷是H或R⁴；R⁸是C₂-C₃亚烷基或羟基亚烷基；X是H，

-R⁹或其混合物，其中R⁹是C₁-C₄烷基或羟烷基；k是0或1；m和n是使得-(CH₂CH₂O)_n-链段占-[(C₃H₆O)_m(CH₂CH₂O)_n]-链段至少约85％的数值；m是0-约5；n是至少约3；r是1或2,s是1或2，和r+s是3或4；y是2-约20；u、v和w数值是使得存在至少2个N+中心和至少2个X基团。One class of suitable cationic polymers is derived from polyurethanes, polyesters, polyethers, polyamides, and the like. These polymers comprise units selected from the group having formulas I, II and III:

where ^A1 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, cyclic alkylene, Arylene or alkarylene, or a _C2 - _C3 oxyalkylene segment having 2 to about 20 oxyalkylene units, provided that no OO or ON bond is formed with A; when x is ¹ , R ² is -R ⁵ -, except when A ¹ is: or -(OR ⁸ ) _y - or -OR ⁵ -, provided that no OO or ON bond is formed with A ¹ , and R ³ is -R ⁵ -, except when A ¹ is:

or -(R ⁸ O) _y - or -R ⁵ O-, provided that no OO or ON bond is formed 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 a segment -(R ⁵ ) _k -[(C ₃ H ₆ O) _m (CH ₂ CH ₂ O) _n ]-X; R ⁵ is C ₁ -C ₁₂ alkylene, hydroxyalkylene, alkenylene, arylene or alkarylene; each R ⁶ is C ₁ -C ₄ alkyl or hydroxyalkane Group, or segment -(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 mixture thereof, wherein R ⁹ is C ₁ -C ₄ alkyl or hydroxyalkyl; k is 0 or 1; m and n are such that -(CH ₂ CH ₂ O) _n -segments account for -[( C ₃ H ₆ O) _m (CH ₂ CH ₂ O) _n ] - value of at least about 85% of segments; 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; u, v and w are values such that there are at least 2 N+ centers and at least 2 X groups.

或

A²优选是-O-；x优选是1；R优选是H。R¹可以是直链(例如-CH₂-CH₂-CH₂-，

)或支(例如 亚烷基、羟基亚烷基、亚链烯基、环状亚烷基、烷亚芳基或氧亚烷基；当R¹是C₂-C₃氧亚烷基链段时，氧亚烷基单元的数目优选是约2-12；R¹优选是C₂-C₆亚烷基或亚苯基，最优选是C₂-C₆亚烷基(例如亚乙基、亚丙基、六亚甲基)。R²优选是-OR⁵-或-(OR⁸)_y-；R³优选是-R⁵O-或-(OR⁸)_y-；R⁴和R⁶优选是甲基。象R¹一样，R⁵可以是直链或支链，优选是C₂-C₃亚烷基；R⁷优选是H或C₁-C₃烷基；R⁸优选是亚乙基；R⁹优选是甲基；X优选是H或甲基；k优选是0；m优选是0,r和s各优选是2；y优选是2-约12。In the above formula, ^A is preferably:

or

^A2 is preferably -O-; x is preferably 1; R is preferably H. R ¹ can be a straight chain (eg -CH ₂ -CH ₂ -CH ₂ -,

) or branches (such as Alkylene, hydroxyalkylene, alkenylene, cyclic alkylene, alkarylene or oxyalkylene; when R ¹ is a C ₂ -C ₃ oxyalkylene segment, oxyalkylene The number of radical 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, hexa methylene). 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; y is preferably 2 to about 12.

In the above formula, when the number of N+ centers and X groups is 2 or 3, n is preferably at least about 6; n is most preferably at least about 12, generally in the range of 12-42 for u+v+w. 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 each preferably about 3-40.

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

其中A¹是

或

R是H或C₁-C₄烷基或羟烷基；R¹是取代的C₂-C₁₂亚烷基、羟基亚烷基、亚链烯基、亚芳基或烷亚芳基、或C₂-C₃氧亚烷基；各R²是C₁-C₁₂亚烷基、羟基亚烷基、亚链烯基、亚芳基或烷亚芳基；各R³是C₁-C₄烷基或羟烷基，或链段-(R²)_k-[(C₃H₆O)_m(CH₂CH₂O)_n]-X，或结合形成-(CH₂)_r-A²-(CH₂)_s-，其中A²是-O-或-CH₂-；各R⁴是C₁-C₄烷基或羟烷基，或两个R⁴结合形成-(CH₂)_r-A²-(CH₂)_s-链段；X是H,-R⁵或其混合物，其中R⁵是C₁-C₄烷基或羟烷基；j是1或0；k是1或0；m和n是使得-(CH₂CH₂O)_n-链段占-[(C₃H₆O)_m(CH₂CH₂O)_n]-链段至少约85％的数值；m是0-约5；n是至少约3；r是1或2,s是1或2，和r+s是3或4；u、v和w数值是使得存在至少2个N+中心和至少2个X基团。Another class of suitable cationic polymers is derived from polyacrylates, polyacrylamides, polyvinyl ethers, and the like. These polymers comprise units selected from the group having formulas IV, V and VI:

where ^A1 is

or

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 oxyalkylene; each R ² is C ₁ -C ₁₂ alkylene, hydroxyalkylene, alkenylene, arylene, or alkarylene; each R ³ is C ₁ -C ₄ Alkyl or hydroxyalkyl, or segment -(R ² ) _k -[(C ₃ H ₆ O) _m (CH ₂ CH ₂ O) _n ]-X, or combined to form -(CH ₂ ) _r -A ² -(CH ₂ ) _s -, wherein A ² is -O- or -CH ₂ -; each R ⁴ is C ₁ -C ₄ alkyl or hydroxyalkyl, or two R ⁴ are combined to form -(CH ₂ ) _r -A ² -(CH ₂ ) _s -segment; X is H, -R ⁵ or a mixture thereof, wherein R ⁵ is C ₁ -C ₄ alkyl or hydroxyalkyl; j is 1 or 0; k is 1 or 0; m and n are such that -(CH ₂ CH ₂ O) _n - Segments account for at least about 85% of -[(C ₃ H ₆ O) _m (CH ₂ CH ₂ O) _n ]- segments; 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.

A²优选是-O-；R优选是H。R¹可以是直链(例如-CH₂-CH-CH₂-，

)或支链(例如

取代的亚烷基、羟基亚烷基、亚链烯基、烷亚芳基或氧亚烷基；R¹优选是取代的C₂-C₆亚烷基或取代的C₂-C₃氧亚烷基，最优选：或

In the above formula, ^A is preferably: or

^A2 is preferably -O-; R is preferably H. R ¹ can be a straight chain (eg -CH ₂ -CH-CH ₂ -,

) or branched chains (e.g.

Substituted alkylene, hydroxyalkylene, alkenylene, alkarylene or oxyalkylene; R ¹ is preferably substituted C ₂ -C ₆ alkylene or substituted C ₂ -C ₃ oxyalkylene Alkyl, most preferably: or

Each R ² is preferably C ₂ -C ₃ alkylene, each R ³ and R ⁴ is 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 each preferably 2.

In the above formula, n, u, v and w can vary from n, u, v and w in polyurethane and similar polymers. C． Polyalkyleneamines, polyalkyleneimines, or similar polymers.

其中R¹是C₂-C₁₂亚烷基、羟基亚烷基、亚链烯基、环状亚烷基、亚芳基或烷亚芳基、或具有2-约20个氧亚烷基单元的C₂-C₃氧亚烷基链段，条件是不形成O-N键；各R²是C₁-C₄烷基或羟烷基，或链段-(R³)_k-[(C₃H₆O)_m(CH₂CH₂O)_n]-X；R³是C₁-C₁₂亚烷基、羟基亚烷基、亚链烯基、亚芳基或烷亚芳基；M’是N+或N中心；X是H、-R⁴或其混合物，其中R⁴是C₁-C₄烷基或羟烷基；当M’是N+时，d是1，当M’是N时，d是0；当M’是N+时，e是2，当M’是N时，e是1；k是1或0；m和n是使得-(CH₂CH₂O)_n-链段占-[(C₃H₆O)_m(CH₂CH₂O)_n]-链段至少约85％的数值；m是0-约5；n是至少约3；x、y和z数值是使得存在至少2个M’基团，至少2个N+中心和至少2个X基团。Another class of suitable cationic polymers is derived from polyalkyleneamines, polyalkyleneimines, and the like. These polymers comprise units selected from the group having the formulas VII, VIII and IX:

wherein ^R is C ₂ -C ₁₂ alkylene, hydroxyalkylene, alkenylene, cyclic alkylene, arylene or alkarylene, or has 2 to about 20 oxyalkylene units C ₂ -C ₃ oxyalkylene segment, provided that no ON bond is formed; each R ² is C ₁ -C ₄ alkyl or hydroxyalkyl, or segment -(R ³ ) _k -[(C ₃ H ₆ O) _m (CH ₂ CH ₂ O) _n ]-X; R ³ is C ₁ -C ₁₂ alkylene, hydroxyalkylene, alkenylene, arylene or alkarylene; M' is N+ or N center; X is H, -R ⁴ or a mixture thereof, wherein R ⁴ is C ₁ -C ₄ alkyl or hydroxyalkyl; when M' is N+, d is 1, when M' is N, d is 0; when M' is N+ When, e is 2, when M' is N, e is 1; k is 1 or 0; m and n are such that -(CH ₂ CH ₂ O) _n -segments account for -[(C ₃ H ₆ O) _m ( _CH2CH2O ) _n ] - a value of at least about 85% _of the segment; m is 0 to about 5; n is at least about 3; x, y and z values are such that there are at least 2 M' groups, 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 a segment -(R ³ ) _k -[(C ₃ H ₆ O) _m ( CH ₂ CH ₂ O) _n ]—X; R ³ is preferably C ₂ -C ₃ alkylene; R ⁴ is preferably methyl; X is preferably H; k is preferably 0;

In the above formula, when the number of M' and X groups is 2 or 3, n is preferably at least about 6; n is most preferably at least about 12, with a typical range of about 12-42 for x+y+z Inside. Generally, x+y+z is 2 to about 40, preferably 2 to about 20. For short chain polymers, x+y+z can range from 2-9 with 2-9 N+ centers and 2-11 X groups. For long chain polymers, x+y+z is at least 10, preferably in the range of 10 to about 42. For short and long chain polymers, the M' group is generally a mixture of about 50-100% N+ centers and 0 to about 50% N centers.

其中R²(优选甲基)、M’、X、d、x、y、z和n定义同上；a是1或0。Preferred cationic polymers of this class 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 polyethyleneamine (PEA) and polyethyleneimine (PEI). 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.

其中x+y+z是2-9,a是0或1(分子量约100-400)。与每个氮原子连接的每个氢原子代表后续乙氧基化的活性位置。对于优选的PEA,x+y+z是约3-7(分子量约140-310)。这些PEA可通过氨与二氯乙烷反应，然后经过分馏得到。所得到的一般PEA是三亚乙基四胺(TETA)和四亚乙基五胺(TEPA)。在五胺以上，即六胺、七胺、八胺和可能的九胺，它们是衍生的同类混合物，不能通过蒸馏分馏，并且可能包括其它的物质例如环胺和特别是哌嗪。还可能存在带侧链的环胺，其中存在氮原子。参见1957年5月14日授权的Dickson的美国专利2792372，其描述了PEA的制备。Prior to ethoxylation, the PEA used in the preparation of the cationic polymers of the present invention has the general formula:

Wherein x+y+z is 2-9, a is 0 or 1 (molecular weight is about 100-400). Each hydrogen atom attached to each nitrogen atom represents an active site for subsequent ethoxylation. For the preferred PEA, x+y+z is about 3-7 (molecular weight about 140-310). These PEAs are obtained by reacting ammonia with dichloroethane followed by fractional distillation. Common PEAs obtained are triethylenetetramine (TETA) and tetraethylenepentamine (TEPA). Above the pentamines, namely the hexamines, heptamines, octaamines and possibly nonamines, these are derived homogeneous mixtures which cannot be fractionated by distillation and may include other species such as cyclic amines and especially piperazines. There may also be cyclic amines with side chains in which nitrogen atoms are present. See US Patent 2,792,372, Dickson, issued May 14, 1957, which describes the preparation of PEA.

The minimum degree of ethoxylation required for preferred soil soil removal/anti-redeposition properties can vary depending on the number of units in the PEA. Where y+z is 2 or 3, n is preferably at least about 6. Desirable benefits are obtained when n is at least about 3 where y+z is 4-9. For preferred cationic PEAs, n is at least about 12, typically in the range of about 12-42.

The PEI used in making the polymers of this invention has a molecular weight of at least about 440, which means at least about 10 units, prior to ethoxylation. The preferred PEI used in the preparation of 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 value sufficiently large to obtain a polymer having the molecular weight specified above. Although a linear polymer backbone is possible, branched chains may also be present. The relative proportions of primary, secondary and tertiary amines present in the polymer can vary depending on the method of preparation. The distribution of amine groups is generally as follows:

_{-CH2CH2 - NH2} 30%

_{-CH2CH2 -} NH- 40%

_-CH2CH2 -N- 30% Each hydrogen atom attached to each nitrogen atom of PEI represents an _active site for subsequent ethoxylation. These PEIs can be prepared, for example, 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 the U.S. Patent 2,182,306 of Ulrich et al. authorized on December 5, 1939; the U.S. Patent 3,033,746 of Mayle et al. authorized on May 8, 1962; the U.S. Patent of Esselmann authorized on July 16, 1940 2,208,095; US Patent 2,806,839, Crowther, issued September 17, 1957; and US Patent 2,533,696, Wilson, issued May 21, 1951 (both incorporated herein by reference).

As defined in the above formula, n is at least about 3 for cationic PEI. It should be noted, however, that the minimum degree of ethoxylation required for suitable soil soil removal/anti-redeposition performance may increase with PEI molecular weight, particularly above about 1800. In addition, it is preferred that the degree of ethoxylation of the polymer increases with the molecular weight of PEI. For PEIs having a molecular weight of at least about 600, n is preferably at least about 12, generally in the range of about 12-42. For PEIs having a molecular weight of at least 1800, n is preferably at least about 24, generally in the range of about 24-42.

D． diallylamine polymer

其中R¹是C₁-C₄烷基或羟烷基，或链段-(R²)_k-[(C₃H₆O)_m(CH₂CH₂O)_n]-X；R²是C₁-C₁₂亚烷基、羟基亚烷基、亚链烯基、亚芳基或烷亚芳基；各R³是C₁-C₄烷基或羟烷基，或结合在一起形成链段-(CH₂)_r-A-(CH₂)_s-,其中A是-O-或-CH₂-；X是H，

-R⁴或其混合物，其中R⁴是C₁-C₄烷基或羟烷基；k是1或0；m和n是使得-(CH₂CH₂O)_n-链段占-[(C₃H₆O)_m(CH₂CH₂O)_n]-链段至少约85％的数值；m是0-约5；n是至少约3；r是1或2,s是1或2，和r+s是3或4；x是1或0；当x是0时，y是1，当x是1时，y是0；u和v的数值是使得存在至少2个N+中心和至少2个X基团。Another class of suitable cationic polymers are those derived from diallylamine. These polymers comprise units selected from the group having formulas X and XI:

Wherein R ¹ is C ₁ -C ₄ alkyl or hydroxyalkyl, or segment -(R ² ) _k -[(C ₃ H ₆ O) _m (CH ₂ CH ₂ O) _n ]-X; R ² is C ₁ -C ₁₂ alkylene, hydroxyalkylene, alkenylene, arylene, or alkarylene; each R ³ is C ₁ -C ₄ alkyl or hydroxyalkyl, or taken together to form a chain Paragraph -(CH ₂ ) _r -A-(CH ₂ ) _s -, where A is -O- or -CH ₂ -; X is H,

-R ⁴ or a mixture thereof, wherein R ⁴ is C ₁ -C ₄ alkyl or hydroxyalkyl; k is 1 or 0; m and n are such that -(CH ₂ CH ₂ O) _n -segments account for -[( C ₃ H ₆ O) _m (CH ₂ CH ₂ O) _n ] - value of at least about 85% of segments; 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 0; when x is 0, y is 1, when x is 1, y is 0; the values of u and v are such that there are at least 2 N+ centers 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 is H; k is preferably 0; m is preferably 0; r and s are each preferably 2.

In the above formula, when the number of N+ centers and X groups is 2 or 3, n is preferably at least about 6, n is preferably at least 12, and generally u+v is in the range of about 12-42. Generally, v is 0 and u is 2 to about 40, preferably 2 to about 20. additional surfactant

The detergent compositions or components of the present invention preferably contain 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 surfactant types and classes are listed in US Patent 3,929,678, Laughlin and Heuring, issued December 30,1975. Other examples are listed in "Surface Active Agents 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.

Amphoteric and zwitterionic surfactants, when present, are generally used in combination with one or more anionic and/or nonionic surfactants. anionic surfactant

The detergent compositions or components of the present invention preferably comprise additional anionic surfactants. Essentially any anionic surfactant useful in detersive applications can be included in the detergent compositions of the present invention. These may include anionic sulfate, sulfonate, carboxylate and sarcosinate surfactants (including, for example, sodium, potassium, ammonium and substituted ammonium salts such as mono-, di- and triethanolamine salts). Anionic sulfate surfactants are preferred.

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

Anionic sulfate surfactants suitable for the present invention include linear and branched primary and secondary alkyl sulfates, alkyl ethoxy sulfates, fatty oleoyl glycerol sulfates, alkylphenol oxirane ether sulfates , C ₅ -C ₁₇ acyl-N-(C ₁ -C ₄ alkyl) and -N-(C ₁ -C ₂ hydroxyalkyl) glucosamine sulfates and sulfates of alkyl polyglycosides such as alkyl Sulfate salts of polyglucosides (nonionic unsulfated compounds described herein).

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

The alkyl ethoxy sulfate surfactants are preferably selected from C ₁₀ -C ₁₈ alkyl sulfates ethoxylated with about 0.5 to about 20 moles of ethylene oxide per molecule. The alkyl ethoxy sulfate surfactant is more preferably a C ₁₁ -C ₁₈ , most preferably a C ₁₁ -C ₁₅ alkyl sulfate, ethoxylated with 0.5-7, preferably 1-5 moles of ethylene oxide per molecule Basicization.

In a particularly preferred aspect of the invention, mixtures of the preferred alkyl sulfate and alkyl ethoxy sulfate surfactants are employed. This mixture is disclosed in PCT patent application WO 93/18124. Anionic Sulfonate Surfactant

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

Suitable alkyl ethoxy carboxylates include compounds of the formula RO(CH ₂ CH ₂ O) _x CH ₂ COO ^- M ⁺ , where R is C ₆ -C ₁₈ alkyl, x is 0 to 10, ethoxy The compound distribution is such that, by weight, the amount of species where x is 0 is less than about 20%, and M is a cation. Suitable alkyl polyethoxy polycarboxylate surfactants include compounds of formula RO-(CHR ₁ -CHR ₂ -O)-R ₃ wherein R is C ₆ -C ₁₈ alkyl and x is 1 to 25 , _R1 and _R2 are selected from hydrogen, formyl, succinate, hydroxysuccinate and mixtures thereof, and _R3 is selected from hydrogen, substituted or unsubstituted hydrocarbon groups containing 1 to 8 carbon atoms and their mixture.

Suitable soap surfactants include secondary soap surfactants which contain carboxyl units attached to secondary carbon atoms. Preferred secondary soap surfactants for use in the present invention are water soluble members selected from 2-methyl-1-undecanoic acid, 2-ethyl-1-decanoic acid, 2-propyl-1- Water-soluble salts of nonanoic acid, 2-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 sarcosinates of the formula R-CON(R ¹ )CH ₂ COOM, wherein R is C ₅ -C ₁₇ linear or branched chain alkyl or alkenyl, and R ¹ is C ₁ -C ₄ alkyl, M is an alkali metal ion. Preferred examples are myristyl and oleoyl methyl sarcosinates in the sodium salt form. Alkoxylated Nonionic Surfactants

Essentially any alkoxylated nonionic surfactant is suitable for use herein, with ethoxylated and propoxylated nonionic surfactants being preferred.

Preferred alkoxylated surfactants may be selected from nonionic alkylphenol condensates, nonionic ethoxylated alcohols, nonionic ethoxylated/propoxylated fatty alcohols, nonionic Ethoxylate/propoxylate condensates of propylene glycol and condensation products of nonionic ethoxylates with propylene oxide/ethylenediamine adducts. Nonionic Alkoxylated Alcohol Surfactants

Condensation products of aliphatic alcohols with about 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 6-22 carbon atoms. Especially preferred are condensation products of alcohols having an alkyl group of 8 to 20 carbon atoms with 2 to 10 moles of ethylene oxide per mole of alcohol. Nonionic Polyhydroxy Fatty Acid Amide Surfactant

The polyhydroxy fatty acid amides suitable for use in the present invention are compounds of the structural formula R ² CONR ¹ Z, wherein R ¹ is hydrogen, C ₁ -C ₄ hydrocarbyl, 2-hydroxyethyl, 2-hydroxypropyl, ethoxy, propoxy or their mixtures, preferably C ₁ -C ₄ alkyl, more preferably C ₁ or C ₂ alkyl, most preferably C ₁ alkyl (i.e. methyl); R ₂ is C ₅ -C ₃₁ hydrocarbyl, preferably straight chain C ₅ -C ₁₉ alkyl or alkenyl, more preferably straight chain C ₉ -C ₁₇ alkyl or alkenyl, most preferably straight chain C ₁₁ -C ₁₇ alkyl or alkenyl or a mixture thereof; Z is A polyhydroxyhydrocarbyl group or an alkoxylated derivative thereof (preferably ethoxylated or propoxylated) having at least three hydroxyl groups attached directly to a linear hydrocarbyl chain. Z is preferably derived from a reducing sugar in a reductive amination reaction, more preferably Z is a glycityl. Nonionic Fatty Acid Amide Surfactant

Suitable fatty acid amide surfactants include compounds having the formula: R ⁶ CON(R ⁷ ) ₂ , wherein R ⁶ is an alkyl group containing 7-21, preferably 9-17 carbon atoms, each R ⁷ being selected from hydrogen, C ₁ -C ₄ alkyl, C ₁ -C ₄ hydroxyalkyl, and -(C ₂ H ₄ O) _x H, wherein x is 1-3. Nonionic Alkyl Polysaccharide Surfactant

Suitable alkylpolysaccharides for use in the present invention are disclosed in US4565647, Llenado, issued January 21, 1986, which contain hydrophobic groups of 6-30 carbon atoms and polysaccharides such as polyglycoside hydrophilic groups, which contain 1.3-10 sugar units.

Preferred alkyl polyglycosides have the formula:

R ² O(C _n H _2n O) _t (glycosyl) _x wherein R ² is selected from the group consisting of alkyl, alkylphenyl, hydroxyalkyl, hydroxyalkylphenyl and mixtures thereof, wherein the alkyl group contains 10-18 carbon atoms; n is 2 or 3; t is 0-10, 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 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 alkanes containing 8-26 carbon atoms phenyl or their mixtures; ^R4 is alkylene or hydroxyalkylene or their mixtures containing 2-3 carbon atoms; x is 0-5, preferably 0-3; and each ^R5 is containing Alkyl or hydroxyalkyl groups of 1-3 carbon atoms, or polyethylene oxide groups containing 1-3 oxirane groups. Preference is given to C ₁₀ -C ₁₈ alkyldimethylamine oxides and C ₁₀ -C ₁₈ amidoalkyldimethylamine oxides.

A suitable example of an alkyl amphocarboxylic acid is Miranol(TM) C2M Conc. made by Miranol, Inc., Dayton, NJ. zwitterionic surfactant

Zwitterionic surfactants can also be incorporated into the detergent compositions or components of the present invention. These surfactants are 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 typical zwitterionic surfactants for use in the present invention.

Suitable betaines are compounds of formula R(R ¹ ) 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. Betaine surfactant complexes are also suitable for use in the present invention. cationic surfactant

If present, cationic surfactants are preferably selected from cationic monoalkoxylated amine surfactants, cationic dialkoxylated amine surfactants and mixtures thereof.

The level of cationic surfactant is preferably from 0.1% to 20%, more preferably from 0.4% to 7%, most preferably from 0.5% to 3%, by weight of the detergent composition. Cationic Monoalkoxylated Amine Surfactants

The cationic surfactant may be a cationic monoalkoxylated amine surfactant having the general formula I Wherein R ¹ is an alkyl or alkenyl group containing about 6-18 carbon atoms, preferably 6-about 16 carbon atoms, most preferably about 6-14 carbon atoms; R ² and R ³ are each containing 1-about Alkyl of 3 carbon atoms, preferably methyl, most preferably ^R2 and ^R3 are both methyl; ^R4 is selected from hydrogen (preferred), methyl and ethyl, X- is an anion that provides electrical neutrality, For example chlorine, bromine, methylsulfate, sulfate, etc. A is alkoxy, especially ethoxy, propoxy or butoxy; p is 0 to about 30, preferably 2 to about 15, most preferably 2 to about 8, provided that if A is ethoxy , R ⁴ is hydrogen and p is 1, then R ₁ is not C ₁₂ -C ₁₄ alkyl.

In formula I, it is preferred that the ^ApR4 group has p=1 and is a hydroxyalkyl group having not more than 6 carbon atoms, whereby the -OH group is separated from the quaternary ammonium nitrogen atom by not more than 3 carbon atoms. Particularly _{preferred ApR4 groups are -CH2CH2OH, -CH2CH2CH2OH, -CH2CH} ⁽ _{CH3 ) OH and -CH ( CH3 ) CH2OH} , _-CH2CH2OH is particularly preferred. Preferably the ^R1 group has no more than 10 carbon atoms, or even no more than 8 or 9 carbon atoms. Preferably the ^R1 group is a straight chain alkyl group. Straight chain R ¹ groups having 8-11 carbon atoms or having 8-10 carbon atoms are preferred. Highly preferred such cationic surfactants are compounds of formula I wherein R ¹ is C ₈ -C ₁₀ alkyl, p is 1, A is ethoxy, R ² and R ³ are methyl.

其中R¹是C₁₀-C₁₈烃基和它们的混合物，特别是C₁₀-C₁₄烷基，优选C₁₀和C₁₂烷基，X是提供电荷平衡的任何便利的阴离子，优选氯或溴。阳离子二烷氧基化胺表面活性剂Another highly preferred cationic monoalkoxylated amine surfactant for use herein has the formula:

wherein R ¹ is C ₁₀ -C ₁₈ hydrocarbyl and mixtures thereof, especially C ₁₀ -C ₁₄ alkyl, preferably C ₁₀ and C ₁₂ alkyl, and X is any convenient anion that provides charge balance, preferably chlorine or bromine. Cationic dialkoxylated amine surfactants

其中R¹是含有约8-约18个碳原子，优选10-约16个碳原子，最优选约10-约14个碳原子的烷基或链烯基部分；R²是含有1-3个碳原子的烷基，优选甲基；R³和R⁴可独立地变化，它们选自氢(优选的)、甲基和乙基；X^-是足以提供电中性的阴离子，例如氯、溴、甲基硫酸根、硫酸根等。A和A’可独立地变化，各选自C₁-C₄烷氧基，特别是乙氧基(即-CH₂CH₂O-)、丙氧基、丁氧基和它们的混合物；p是1-约30，优选1-约4,q是1-约30，优选1-约4，最优选p和q都是1。The cationic surfactant may also be a cationic dialkoxylated amine surfactant having the general formula II:

wherein R ¹ is an alkyl or alkenyl moiety containing about 8 to about 18 carbon atoms, preferably 10 to about 16 carbon atoms, most preferably about 10 to about 14 carbon atoms; R ² is an alkyl or alkenyl moiety containing 1 to 3 Alkyl of carbon atoms, preferably methyl; ^R3 and ^R4 can vary independently, they are selected from hydrogen (preferred), methyl and ethyl; X ^- is an anion sufficient to provide electrical neutrality, such as chlorine, bromine , Methylsulfate, Sulfate, etc. A and A' can vary independently, each selected from C ₁ -C ₄ alkoxy, especially ethoxy (ie -CH ₂ CH ₂ O-), propoxy, butoxy and mixtures thereof; p is 1 to about 30, preferably 1 to about 4, q is 1 to about 30, preferably 1 to about 4, most preferably both p and q are 1.

Highly preferred cationic dialkoxylated amine surfactants for use herein have the formula: wherein R ¹ is C ₁₀ -C ₁₈ hydrocarbyl and mixtures thereof, preferably C ₁₀ , C ₁₂ , C ₁₄ alkyl and mixtures thereof, and X is any suitable anion providing charge balance, preferably chlorine. Regarding the general structure of the cationic dialkoxylated amines above, in preferred compounds, ^R1 is derived from (coconut) _C12 - _C14 alkyl partial fatty acid, ^R2 is methyl, ^ApR3 and ^A'pR4 Both are monoethoxy.

其中R¹是C₁₀-C₁₈烃基，优选C₁₀-C₁₄烷基，p独立地是1-约3,q是1-约3,R²是C₁-C₃烷基，优选甲基，X是阴离子，特别是氯或溴。Other cationic dialkoxylated amine surfactants suitable for use herein include compounds of the formula:

wherein R ¹ is C ₁₀ -C ₁₈ hydrocarbyl, preferably C ₁₀ -C ₁₄ alkyl, p is independently 1 to about 3, q is 1 to about 3, R ² is C ₁ -C ₃ alkyl, preferably methyl , X is an anion, especially chlorine or bromine.

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

The detergent ingredients or compositions may contain additional water-soluble builder compounds.

Suitable water-soluble builder compounds include carboxylate materials, borates, phosphates and mixtures of any of the foregoing.

Borate builders and builders containing borate-forming materials which produce borate under detergent storage or wash conditions are water-soluble builders useful herein.

Suitable examples of water-soluble phosphate builders are alkali metal tripolyphosphates, sodium, potassium and ammonium pyrophosphates, sodium and potassium orthophosphates, sodium polymeta/phosphates wherein the degree of polymerization is about 6-21, and inositol Salts of hexaphosphoric acid.

Carboxylate builders suitable for use in the detergent compositions or components of the present invention can be of the monomeric or oligomeric type (containing up to 4 carboxylate groups), but for cost and performance reasons, monomeric Carboxylate salts are generally preferred.

Suitable additional carboxylates containing one carboxyl group include the water-soluble salts of lactic acid, glycolic acid and their ether derivatives. Carboxylate salts containing two carboxyl groups include succinic, malonic, (ethylenedioxy) diacetic, maleic, diglycolic, tartaric, tartronic and fumaric acids as well as ether carboxylic and Water-soluble salt of sulfinyl carboxylic acid. Carboxylate salts containing three carboxy groups include especially water-soluble citrate, itaconate and citraconate and succinate derivatives such as carboxymethyloxysuccinate described in British Patent 1379241, in Lactyloxysuccinates described in UK Patent 1389732 and aminosuccinates described in Dutch Application 7205873 and oxypolycarboxylate substances described in UK Patent 1387447, such as 2-oxa-1,1 ,3-propane tricarboxylate.

Carboxylates containing four carboxyl groups include oxydisuccinates, 1,1,2,2-ethane tetracarboxylates, 1,1,3,3-propane tetracarboxylates described in British Patent 1261829 salt and 1,1,2,3-propane tetracarboxylate. Carboxylates containing sulfo substituents include the sulfosuccinate derivatives described in British Patents 1,398,421 and 1,398,422 and US 3,936,448, and the sulfonated pyrolytic citrates described in British Patent 1,439,000. Preferred additional carboxylates are hydroxycarboxylates containing up to three carboxy groups per molecule, more preferably citrates.

Mixtures of the parent acids of the monomeric or dimeric polycarboxylate chelating agents or their salts, for example citric acid or citrate/citric acid mixtures can also be used as builder components. partially soluble or insoluble builder compounds

The detergent components or compositions of the present invention may contain partially dissolved or insoluble builder compounds at a level of generally 1% to 80%, preferably 10% to 70%, most preferably 20%-60%.

Examples of substantially water-insoluble builders include sodium aluminosilicates.

Suitable aluminosilicate zeolites have a unit cell of the formula Na _Z [(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 , x is at least 5, preferably 7.5-276, more preferably 10-264. The aluminosilicates are in hydrated form, preferably crystalline containing 10% to 28%, more preferably 18% to 22%, of water in bound form.

Aluminosilicate zeolites may be naturally occurring materials, but are preferably synthetically derived. Synthetic crystalline aluminosilicate ion exchange materials are commercially available under the designations Zeolite A, Zeolite B, Zeolite P, Zeolite X, Zeolite HS, and mixtures thereof, Zeolite A having the formula:

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

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

Zeolite MAP is described in EP384070A (Unilever). It is defined as an alkali metal aluminosilicate of the zeolite P type having a silicon to aluminum ratio not greater than 1.33, preferably in the range 0.9-1.33, more preferably in the range 0.9-1.2.

Particularly advantageous is zeolite MAP having a silicon to aluminum ratio of not greater than 1.15, more preferably not greater than 1.07.

In a preferred aspect, the zeolite MAP builder builder has 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 data. The particle size can be determined, inter alia, by conventional analytical techniques such as microscopic determination techniques using scanning electron microscopy or by laser particle sizers. Other methods of determining _d50 values are disclosed in EP384070A. Heavy metal ion chelating agent

The detergent components or compositions of the present invention preferably contain, as an optional ingredient, heavy metal ion sequestrants. The heavy metal ion chelating agent refers to the components that play the role of chelating heavy metal ions. These components may also have calcium and magnesium chelating capacity, but preferably exhibit selectivity for binding heavy metal ions such as iron, manganese and copper.

The heavy metal ion chelating agent is usually present at a content of 0.005%-20%, preferably 0.1%-10%, more preferably 0.25%-7.5%, most preferably 0.5%-5%, by weight of the composition.

Suitable heavy metal ion sequestrants for use in the present invention include organic phosphonates such as aminoalkylene poly(alkylene phosphonates), alkali metal ethane 1-hydroxy diphosphonates, and nitrilotrimethylene Phosphonates.

Preferred of the aforementioned substances are diethylenetriaminepenta(methylenephosphonate), ethylenediaminetris(methylenephosphonate), hexamethylenediaminetetrakis(methylenephosphonate) and Hydroxyethylene 1,1 Diphosphonate.

Other suitable heavy metal ion sequestrants for use in the present invention include nitrilotriacetic acid and polyaminocarboxylic acids such as ethylenediaminetetraacetic acid, ethylenetriaminepentaacetic acid, ethylenediamine disuccinic acid, ethylenediamine diamine Glutaric acid, 2-hydroxypropylenediamine disuccinic acid, or any salt thereof. Especially preferred is ethylenediamine-N,N'-disuccinic acid (EDDS) or its alkali metal, alkaline earth metal, ammonium or substituted ammonium salts or mixtures thereof.

Other suitable heavy metal ion sequestrants for use in the present invention are iminodiacetic acid derivatives such as 2-hydroxyethyldiacetic acid or glyceryl iminodiacetic acid as described in EP-A-317542 and EP-A-399133 . Iminodiacetic acid-N-2-hydroxypropylsulfonic acid and aspartic acid N-carboxymethyl N-2-hydroxypropyl-3-sulfonic acid chelating agents described in EP-A-516102 can also be used . 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-functional chelating agents. EP-A-510331 describes suitable chelating agents derived from collagen, keratin or casein. EP-A-528859 describes suitable alkyliminodiacetic acid sequestrants. Also suitable are lutidine and 2-phosphinobutane-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 suitable. Organic Peroxyacid Bleach System

A preferred feature of the detergent compositions or components of the present invention is an organic peroxyacid bleach system. In a preferred embodiment, the bleach system comprises a source of hydrogen peroxide and an organic peroxyacid bleach precursor compound. Organic peroxyacids can be produced by in situ reaction of precursors with a source of hydrogen peroxide. Preferred sources of hydrogen peroxide include inorganic perhydrate bleaches. In another preferred embodiment, preformed organic peroxyacids are added directly to the composition. Compositions comprising a mixture of a hydrogen peroxide source and an organic peroxyacid precursor mixed with a preformed organic peroxyacid are also contemplated. Inorganic perhydrate bleach

Inorganic perhydrate salts are the preferred source of hydrogen peroxide and these salts are usually added in the form of alkali metal, preferably sodium, salts at a level of from 1% to 40%, more preferably from 2% to 30%, and most preferably from 2% to 30% by weight of the composition. Preferably 5%-25%.

Examples of inorganic perhydrate salts are perborates, percarbonates, perphosphates, persulfates and persilicates. Inorganic perhydrate salts are generally alkali metal salts. Inorganic perhydrate salts may be included in the form of crystalline solids without additional protection, however, for certain perhydrate salts, in preferred embodiments of such granular compositions, the perhydrate salts are used in coated form to provide Better storage stability of perhydrate salts in granular products. Suitable coatings include inorganic salts such as alkali metal silicates, carbonates or borates or mixtures thereof, or organic substances such as paraffins, oils or fatty soaps.

Sodium perborate is _the preferred perhydrate salt and can be in _the monohydrate form _{of the} standard formula _NaBO2H2O2 or the tetrahydrate form of _the formula _{NaBO2H2O2-3H2O} .

Alkali metal percarbonates, especially sodium percarbonate, are the preferred perhydrates of the present invention. Sodium percarbonate is _an adduct compound having the formula corresponding to _{2Na2CO3.3H2O2 and} is commercially available as a _crystalline solid.

Potassium peroxymonopersulfate is another inorganic perhydrate salt useful in the detergent compositions or components thereof herein. Peroxyacid Bleach Precursors

Peroxyacid bleach precursors are compounds which react with hydrogen peroxide in a perhydrolysis reaction to form peroxyacids. Peroxyacid bleach precursors are generally represented by the formula: Wherein L is a leaving group, and X is basically any functional group, so that the structure of the peroxyacid generated in the perhydrolysis reaction is:

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

Suitable peroxyacid bleach precursor compounds generally contain one or more N- or O-acyl groups and the precursors can be selected from a wide variety of classes. Suitable classes include anhydrides, esters, imides, lactams and acylated derivatives of imidazoles and oximes. Examples of useful materials of these classes are described in GB-A-1586789. Suitable esters are disclosed in GB-A-836988, 864798, 1147871, 2143231 and EP-A-0170386. leaving group

The leaving group, hereinafter referred to as the L group, must be sufficiently reactive for the perhydrolysis reaction to take place within an optimal time (eg one wash cycle). However, if L is too reactive, the active will be difficult to stabilize for use in bleach compositions.

和 和它们的混合物，其中R¹是含有1-14个碳原子的烷基、芳基或烷芳基，R³是含有1-8个碳原子的烷基链，R⁴是H或R³,R⁵是含有1-8个碳原子的链烯基链，和Y是H或增溶基团。任何R¹、R³和R⁴可基本上被任何官能团，包括例如烷基、羟基、烷氧基、卤素、胺、亚硝酰基、酰胺和铵或烷基铵基团取代。Preferred L groups are selected from: and

and and mixtures thereof, wherein R ¹ is an alkyl, aryl or alkaryl group containing 1-14 carbon atoms, R ³ is an alkyl chain containing 1-8 carbon atoms, R ⁴ is H or R ³ , ^R5 is an alkenyl chain containing 1-8 carbon atoms, and Y is H or a solubilizing group. Any of R ¹ , R ³ and R ⁴ may be substituted with essentially any functional group including, for example, alkyl, hydroxyl, alkoxy, halogen, amine, nitrosyl, amide, and ammonium or alkylammonium groups.

Preferred solubilizing groups are -SO ₃ ^- M ⁺ , -CO ₂ ^- M ⁺ , -SO ₄ ^- M ⁺ , -N ⁺ (R ³ ) ₄ X ^- and O←N(R ³ ) ₃ , most preferably -SO ₃ ^- M ⁺ and -CO ₂ ^- M ⁺ , wherein R ³ is an alkyl group containing 1-4 carbon atoms, M is a cation that provides solubility to bleach activators, and X is a cation that provides solubility to bleach activators of anions. Preferably M is an alkali metal, ammonium or substituted ammonium cation, most preferably sodium and potassium, and X is a halide, hydroxide, methylsulfate or acetate anion. Alkyl percarboxylic acid bleach precursor

Alkyl percarboxylic acid bleach precursors form percarboxylic acids in a perhydrolysis reaction, and such preferred precursors undergo hydrolysis to provide peracetic acid.

Preferred imido-type alkyl percarboxylic acid precursor compounds include N-, N, N ¹ N ¹ tetraacetylated alkylenediamines, wherein the alkylene group contains 1 to 6 carbon atoms, especially wherein the alkylene Compounds whose alkyl groups contain 1, 2 and 6 carbon atoms, tetraacetylethylenediamine (TAED) are especially preferred.

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

或

其中R¹为包含1-14个碳原子的烷基，R²为包含1-14个碳原子的亚烷基，R⁵为H或含有1-10个碳原子的烷基，且L基本上为任何离去基团。这类酰胺取代的漂白活性剂化合物在EP-A-0170386中描述。过苯甲酸前体Amylamino substituted alkyl peroxyacid precursor compounds are suitable for use in the present invention and include compounds of the general formula:

or

wherein ^R is an alkyl group containing 1-14 carbon atoms, R is ^an alkylene group containing 1-14 carbon atoms, R is ^H or an alkyl group containing 1-10 carbon atoms, and L is essentially for any leaving group. Amide substituted bleach activator compounds of this type are described in EP-A-0170386. perbenzoic acid precursor

Perbenzoic acid precursor compounds provide perbenzoic acid in the perhydrolysis reaction. Suitable O-acylated perbenzoic acid precursor compounds include substituted and unsubstituted benzoyloxybenzenesulfonates and benzoylation products of sorbitol, glucose and all sugars with benzoylating reagents, Such imide compounds include N-benzoyl succinimide, tetrabenzoyl ethylenediamine and N-benzoyl substituted ureas. Suitable imidazole-type perbenzoic acid precursors include N-benzoyl imidazole and N-benzoyl benzimidazole. Other useful N-acyl-containing perbenzoic acid precursors include N-benzoylpyrrolidone, dibenzoyltaurine and benzoylpyroglutamate. cationic peroxyacid precursor

Cationic peroxyacid precursor compounds undergo a hydrolysis reaction to form cationic peroxyacids.

Cationic peroxyacid precursors are generally formed by substituting the peroxyacid moiety of a suitable peroxyacid precursor compound with a positively charged functional group, such as ammonium or alkylammonium groups, preferably ethyl or methylammonium groups. Cationic peroxyacid precursors are usually present in solid detergent compositions as salts with suitable anions, eg halides.

The cationic substituted peroxyacid precursor compound may be a precursor compound of perbenzoic acid or a substituted derivative thereof as described above. In addition, the peroxyacid precursor compound may be an alkyl percarboxylic acid precursor compound or an amide-substituted alkyl peroxyacid precursor as described below.

Cationic peroxyacid precursors are described in US Pat.

Examples of preferred cationic peroxyacid precursors are described in UK patent application 9407944.9 and US patent applications 08/298903, 08/298650, 08/298904 and 08/298906.

Suitable cationic peroxyacid precursors include any ammonium or alkylammonium substituted alkyl or benzoyloxysulfonates, N-acylated caprolactams and monobenzoyltetraacetylglucose benzoyl peroxide. Preferred N-acylated caprolactam cationic peroxyacid precursors include trialkylammoniummethylenebenzoylcaprolactam and trialkylammoniummethylenealkylcaprolactam. Benzoxazine Organic Peroxyacid Precursor

其中R¹是H、烷基、烷芳基、芳基或芳烷基。预制的有机过氧酸Also suitable are benzoxazine precursor compounds disclosed in, for example, EP-A-332294 and EP-A-482807, especially of the formula:

wherein R ¹ is H, alkyl, alkaryl, aryl or aralkyl. preformed organic peroxyacids

In addition to or in addition to the organic peroxyacid bleach precursor compounds, organic peroxyacid bleach systems may contain preformed organic peroxyacids, typically at levels of from 1% to 15%, more preferably 1% by weight of the composition. %-10%.

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

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

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

Preferred additional enzyme materials include the commercially available cellulases, endolases, cutinases, lipases, amylases, neutral and alkaline proteases, esterases, pectinases, lactases conventionally incorporated into detergent compositions and peroxidase. Suitable enzymes are discussed in US3519570 and 3533139.

Preferred commercially available proteases include those sold under the tradenames Alcalase, Savinase, Primase, Durazym and Esperase by Novo Industries A/S (Denmark), the proteases sold under the tradenames Maxatase, Maxacal and Maxapem by Gist-Brocades, Proteases sold by Genencor International and under the tradenames Opticlean and Optimase by Solvay Enzymes. Proteases may be incorporated into the detergent compositions of the present invention at levels of 0.0001% to 4% active enzyme by weight of the composition.

Preferred amylases include, for example, the alpha-amylases obtained from a specific strain of Bacillus licheniformis as described in detail in GB-1269839 (Novo). Preferred commercially available amylases include, for example, those sold under the tradename Rapidase by Gist-Brocades and Termamyl and BAN by Novo Industries A/S. Amylases may be incorporated into the detergent compositions of the present invention at levels of 0.0001% to 2% active enzyme by weight of the composition.

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

The lipase may be of fungal or bacterial origin, for example from lipase-producing strains of Humicola, Thermomyces or Pseudomonas, including Pseudomonas paraalcaligenes or Pseudomonas fluorescens get. Lipases derived from chemically or genetically modified variants of these strains are also useful in the present invention. A preferred lipase is obtained from Pseudomonas pseudoalcaligenes, which is described in granted EP-B-0218272.

Another preferred lipase of the present invention is the lipase obtained by cloning the gene obtained from Humicola lanuginosa and expressing the gene in Aspergillus oryzae as described in EP-A-0258068, which is industrially produced by Novo Industri Available under the tradename Lipolase from A/S Bagsvaerd, Denmark. This lipase is also described in US4810414, Huge-Jinsen et al., issued March 7,1989. Foam suppressor system

The detergent compositions or components of the present invention, when formulated for use in washing machine compositions, preferably contain 0.01% to 15%, preferably 0.05% to 10%, most preferably 0.1% to 5% by weight of the composition. Antifoam system.

Suitable suds suppressor systems for use herein may consist essentially of any known antifoam compound including, for example, silicone antifoam compounds and 2-alkyl alkanol antifoam compounds.

By antifoam compound is meant herein any compound or mixture of compounds that acts, for example, to inhibit foaming or foaming of a detergent composition solution, especially when the solution is agitated.

Especially preferred antifoam compounds for use in the present invention are polysiloxane antifoam compounds as defined herein including any antifoam compound of a silicone component. The silicone defoamers also typically contain a silica component. The term "polysiloxane" as used herein and generally in the industry includes various relatively high molecular weight polymers containing siloxane units and various types of hydrocarbyl groups. Preferred silicone antifoam compounds are silicones, especially polydimethylsiloxanes containing trimethylsilyl endcapping units.

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

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

A preferred suds suppressor system comprises: (a) an antifoam compound, preferably a silicone antifoam compound, most preferably a silicone antifoam compound comprising: (i) a silicone antifoam compound Dimethicone present in an amount of 50%-99%, preferably 75%-95% by weight; and (ii) 1%- 50%, preferably 5%-25% of silicon dioxide; wherein said silicon dioxide/polysiloxane antifoam compound is added in a content of 5%-50% by weight, preferably 10%-40%; (b ) dispersant compound, most preferably comprising a crude copolymer of polysiloxane diol and polyoxyalkylene, wherein the content of polyoxyalkylene is 72-78%, the ratio of ethylene oxide to propylene oxide is 1:0.9- 1:1.1 in an amount of 0.5% to 10% by weight, preferably 1% to 10%; an especially preferred crude polysiloxane diol copolymer of this type is DOC544 commercially available from DOW Coming under the trade name DC0544 (c) an inert carrier liquid compound, most preferably containing a C ₁₆ -C ₁₈ ethoxylated alcohol with a degree of ethoxylation of 5-50, preferably 8-15; its content is 5%-80% by weight, Preferably 10%-70%.

A more preferred particulate suds suppressor system is described in EP-A-0210731, which comprises a silicone foam compound and an organic vehicle having a melting point of 50°C to 85°C, wherein the organic vehicle material comprises a monoglyceride and contains 12- A fatty acid with a carbon chain of 20 carbon atoms. EP-A-0210721 discloses other preferred particulate suds suppressor systems in which the organic carrier is a fatty acid or alcohol having a melting point of 45°C to 80°C or a mixture thereof having a carbon chain of 12 to 20 carbon atoms. polymeric dye transfer inhibitor

The detergent components or compositions of the present invention also contain from 0.01% to 10%, preferably from 0.05% to 0.5% by weight of polymeric dye transfer inhibiting agents.

其中P是可聚合的单元，和A是 x是0或1；R是脂族、乙氧基化脂族、芳香族、杂环或碳环基团或其任何组合，N-O基团的氮可与其相连或其中N-O基团的氮是这些基团的一部分。The polymeric dye transfer inhibiting agents are preferably selected from polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, polyvinylpyrrolidone polymers or mixtures thereof, wherein these polymers may be cross-linked Linked polymers. a) Polyamine N-oxide polymers Polyamine N-oxide polymers suitable for use in the present invention contain units having the formula:

where P is the polymerizable unit, and A is x is 0 or 1; R is an aliphatic, ethoxylated aliphatic, aromatic, heterocyclic or carbocyclic group or any combination thereof to which the nitrogen of the NO group may be attached or wherein the nitrogen of the NO group is part of the group.

The NO group can be represented by the following general structural formula: or wherein R1, R2 and R3 are aliphatic groups, aromatic, heterocyclic or carbocyclic groups or combinations thereof, and x and/or y and/or z are 0 or 1 to which the nitrogen of the NO group can be attached or wherein the nitrogen of the NO group forms part of these groups. The NO group can be part of the polymerizable unit (P) or can be attached to the polymeric backbone or a combination of both.

Suitable polyamine N-oxides wherein the N-O group forms part of the polymerizable unit include polyamine N-oxides wherein R is selected from aliphatic, aromatic, carbocyclic or heterocyclic groups. One class of the aforementioned polyamine N-oxides includes a group of polyamine N-oxides in which the nitrogen of the N-O group forms part of the R-group. Preferred polyamine N-oxides are those wherein R is a heterocyclic group such as pyridine, pyrrole, imidazole, pyrroline, piperidine, quinoline, acridine and derivatives thereof.

Other suitable polyamine N-oxides are polyamine oxides in which the N—O groups are attached to the polymerisable units. A preferred class of these polyamine N-oxides are polyamine N-oxides having the general formula (I), wherein R is an aromatic, heterocyclic or carbocyclic group, wherein the nitrogen of the N-O functional group is the R group a part of. Examples of such compounds are polyamine oxides wherein R is a heterocyclic compound such as pyridine, pyrrole, imidazole and their derivatives.

The polyamine N-oxides according to the invention can be obtained in almost any degree of polymerization. The degree of polymerisation is not critical so long as the material has the desired water solubility and dye suspending power. The average molecular weight is usually 500-1,000,000. b) Copolymers of N-vinylpyrrolidone and N-vinylimidazole

The N-vinylimidazole and N-vinylpyrrolidone copolymers suitable for the present invention have an average molecular weight of 5,000-50,000. The preferred copolymer has a molar ratio of N-vinylimidazole to N-vinylpyrrolidone of 1-0.2. c) Polyvinylpyrrolidone

Polyvinylpyrrolidone ("PVP") having an average molecular weight of from 2,500 to 400,000 may also be employed in the detergent components or compositions of the present invention. Suitable polyvinylpyrrolidones are commercially available from ISP Corporation, New York, NY and Montreal, under the Canadian product names PVPK-15 (viscosity average molecular weight 10,000), PVPK-30 (average molecular weight 40,000), PVPK-60 (average Molecular weight 160000) and PVPK-90 (average molecular weight 360000) obtained. PVPK-15 is also available from ISP Corporation. Other suitable polyvinylpyrrolidones commercially available from BASFCooperation include Sokalan HP165 and Sokalan HP12. d) Polyvinyloxazolidinone

The detergent components or compositions of the present invention may also employ polyvinyloxazolidinones having an average molecular weight of from 2,500 to 400,000 as polymeric dye transfer inhibiting agents. e) Polyvinylimidazole

The detergent components or compositions of the present invention may also employ polyvinylimidazoles having an average molecular weight of 2,500-400,000 as polymeric dye transfer inhibiting agents. Fluorescent whitening agent

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

Hydrophilic optical brighteners used in the present invention include those having 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-methyl ylamino, morpholino, chlorine and amino; M is a salt-forming cation such as sodium or potassium.

When in the above formula, R ₁ is anilino, R ₂ is N-2-bis-hydroxyethyl and M is a cation such as sodium, the brightener is 4,4'-bis[(4-anilino -6-(N-2-bis-hydroxyethyl)-s-triazin-2-yl)amino]-2,2'-stilbene disulphonic acid and its disodium salt. This particular brightener material is sold commercially by the 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.

When in the above formula _R1 is anilino, _R2 is N-2-hydroxyethyl-N-2-methylamino and M is a cation such as sodium, the brightener is 4,4'-bis [(4-anilino-6-(N-2-hydroxyethyl-N-methylamino)-s-triazin-2-yl)amino]-2,2'-stilbene disulphonic acid disodium salt. This particular brightener material is sold commercially by Ciba-Geigy under the trade name Tinopal 5BM-GX.

When in the above formula _R1 is anilino, _R2 is morpholino and M is a cation such as sodium, the brightener is 4,4'-bis[(4-anilino-6-morpholino -s-Triazin-2-yl)amino]2,2'-stilbene disulfonic acid, its sodium salt. This particular brightener is sold commercially by Ciba-Geigy under the tradename Tinopal AMS-GX. polymeric soil release agent

Known polymeric soil release agents, hereinafter abbreviated "SRAs", may optionally be used in the detergent ingredients or compositions of the present invention. If used, SRA's generally comprise from 0.01% to 10.0%, typically 0.1% to 5%, preferably 0.2% to 3.0%, by weight of the composition.

Preferred SRA's typically have a hydrophilic portion that hydrophilizes the surface of hydrophobic fibers such as polyester and nylon, and a hydrophobic portion that deposits on the hydrophobic fibers and remains attached to them throughout the wash and rinse cycle, thus acting as a hydrophilic part of the fixture. This can make subsequent stains treated with SRA easier to clean in subsequent washes.

Preferred SRA's include oligomeric terephthalates, which are generally prepared by a process involving at least one transesterification/oligomerization reaction, usually over a metal catalyst such as a titanium(IV) alkoxide. The esters can be prepared using other monomers that can incorporate ester structures through one, two, three, four or more positions, without, of course, forming a dense fully cross-linked structure.

Suitable SRA's include sulfonation products of substantially linear ester oligomers containing a terephthaloyl oligoester backbone with oxyalkylene oxygen repeat units and allyl derivatives covalently attached to the backbone. Sulfonated terminal moieties, such as those described in US Patent No. 4,968,451, issued November 6, 1990 to J.J. Scheibel and E.P. Gosselink. The ester oligomer can be prepared by (a) ethoxylating allyl alcohol; (b) combining the product of (a) with dimethyl terephthalate in a two-step transesterification/oligomerization process ester ("DMT") and 1,2-propanediol ("PG"); and (C) reacting the product of (b) with sodium metabisulfite in water; other SRA's include the December 8, 1987 authorization Non-ionic endcapped 1,2-propylene/polyoxyethylene terephthalate polyesters in US Pat. Products prepared by transesterification/oligomerization of diols) ("PEGs"); other examples of SRA's include partially and fully anionically terminated oligoesters in U.S. Patent 4,721,580, issued January 26, 1988 to Gosselink, Oligomers such as those derived from ethylene glycol ("EG"), PG, DMT and sodium 3,6-dioxa-8-hydroxyoctanesulfonate; US Patent 4,702,857 to Gosselink, issued Oct. 27, 1987 Nonionic end-block polyester oligomeric compounds in, for example prepared from DMT, methyl (Me)-terminated PEG and EG and/or PG, or DMT, EG and/or PG, Me-terminated The product prepared from the mixture of PEG and dimethyl-5-sodium sulfoisophthalate; and the anions, especially the sulfoaroyl-capped Terminated terephthalates, the latter are typically SRA's useful in both laundry and fabric conditioning products, an example being an ester composition prepared from m-sulfobenzoic acid monosodium salt, PG and DMT, optionally But preferably also contains added PEG, eg PEG3400.

SRA's also include: simple block copolymers of ethylene terephthalate or propylene terephthalate with polyethylene oxide or polypropylene oxide terephthalate, see May 25, 1976 U.S. Patent No. 3,959,230 to Hay and U.S. Patent No. 3,893,929 to Basadur of Jul. 8, 1975; cellulose derivatives such as hydroxyether cellulose polymers available as METHOCEL from Dow; C ₁ -C ₄ alkyl cellulose and C _4- Hydroxyalkylcelluloses, see US Patent 4,000,093, Nicol et al., December 28,1976. and methyl cellulose ethers having an average degree of substitution (methyl) of about 1.6-2.3 per anhydroglucose unit and a solution viscosity of about 80-120 centipoise as a 2% aqueous solution at 20°C. Such substances are commercially available as METOLOSE SM100 and METOLOSE SM200, which are trade names of methyl cellulose ethers produced by Shin-etsu Kagaku Kogyo KK.

Another class of SRA's includes: (I) nonionic terephthalate esters linked to polyester structures using diisocyanate coupling agents, see U.S. Pat. No. 4,201,824 to Violland et al. and U.S. Pat. SRA's having carboxylate end groups prepared by adding trimellitic anhydride to known SRA's to convert the terminal hydroxyl groups to trimellitate esters. With proper choice of catalyst, trimellitic anhydride forms linkages to the terminal groups of the polymer through the sequestered carboxylate of trimellitic anhydride rather than by opening the anhydride linkage. Both nonionic and anionic SRA's can be used as starting materials as long as they have hydroxyl end groups that can be esterified, see U.S. Patent No. 4,525,524 by Tung et al.; SRA's of diacid esters, see US Patent No. 4,201,824 to Violland et al.; other optional components

Other optional ingredients that may be included in the components or compositions of the present invention include fragrances, colors and filler salts, with sodium sulfate being the preferred filler salt. Detergent formulations near neutral wash pH

Although the detergent components of the present invention, particularly detergent compositions, comprise components that can operate over a wide range of wash pH (e.g. about 5-12), when they are formulated to have a near neutral wash pH (i.e. at An initial pH of about 7.0-10.5) at a concentration of about 0.1% to 2% by weight in water at 20°C is particularly suitable. Formulations near neutral wash pH are better for enzyme stability and for inhibiting soil fixation. In such formulations, the wash pH is preferably about 7.0-10.5, more preferably about 8.0-10.5, most preferably 8.0-9.0.

Preferred detergent formulations at near neutral wash pH are disclosed in European Patent Application 83200688.6, filed May 16, 1983, by J.H.M. Wertz and P.C.E. Goffinet.

Highly preferred components or compositions of this type also preferably contain from about 2% to 10% by weight citric acid and minor amounts (e.g., less than about 20% by weight) of neutralizing agents, buffers, phase regulators, hydrotropes such as Toluenesulfonates, xylenesulfonates or cumenesulfonates, enzyme stabilizers, foam regulators, opacifiers, antioxidants, bactericides, dyes, fragrances and brighteners, for example on 25.08.1981 Those described in issued US Patent 4,285,841 to Barrat et al. (which is incorporated herein by reference). Components and Forms of Composition

The detergent ingredients of the present invention may be prepared by various methods including agglomeration or extrusion of mixtures of various compounds contained in or contained in detergent ingredients, but preferably by spray drying containing water soluble A mixture or slurry of a cationic compound and a carboxylate-containing polyelectrolyte compound. This can be done by any spray drying method known in the art. Accordingly, the detergent components of the present invention are preferably spray-dried granules or granules or powders.

When the components of the invention are in the form of agglomerated particles, the cationic water-soluble compound is preferably associated with a carrier material.

The detergent components of the present invention preferably form part of detergent compositions. Compositions according to the invention may take a variety of physical forms including granules, tablets, cakes, lozenges and bars. The compositions according to the invention are in particular so-called concentrated granular detergent compositions which are suitable for addition to a washing machine by means of a dispensing device which is placed in the drum of the machine containing soiled linen.

The components or compositions of the present invention may also be used in or combined with bleach additive compositions such as compositions comprising chlorine bleach.

The average particle size of the component comprising the water-soluble cationic soil soil removal/anti-redeposition compound in the granular composition of the present invention should preferably be such that no more than 40%, more preferably no more than 15% of the particles have a diameter greater than 1.8mm; diameters are less than 0.25mm The particles do not exceed 40% or preferably do not exceed 15%. The average particle size is preferably such that 10% to 50% of the particles have a diameter of 0.2 mm to 0.7 mm.

The term mean particle size as defined herein is calculated by sieving a sample of the composition over a set of sieves, preferably Tyler sieves, into a number of fractions (usually 5 fractions). The resulting weight fraction is plotted against the pore size of the sieve, the average particle size being the size of the pores through which 50% by weight of the sample passes.

The bulk density of the granular detergent compositions of the present invention is usually at least 500 g/l, more preferably from 600 g/l to 1200 g/l. When the detergent component is a spray-dried granule, granule or powder, lower bulk density compositions containing the component are preferred. Bulk density is determined by a simple funnel and cup arrangement consisting of a conical funnel mounted perpendicular to the bottom, with a check valve at the bottom of the funnel allowing the contents of the funnel to drain into a cylindrical cup placed coaxially below the funnel. The funnel is 130mm high and has inner diameters of 130mm and 40mm at the upper and lower ends, respectively. The funnel is installed at its lower end 140 mm above the upper surface of the bottom. The cup has a total height of 90 mm, an internal height of 87 mm, an inner diameter of 84 mm, and a normal volume of 500 ml.

For measurement, the funnel is filled with powder by hand, the check valve is opened, and the powder is filled into the cup from above. The filled cup is removed from the frame and excess powder is removed by scraping the top edge of the cup with a straight-edged implement, such as a knife. The filled cup is then weighed and the resulting powder weight value multiplied by 2 to obtain a bulk density value in g/l. Repeat experiments are required.

The compacted solid may be produced using any suitable compacting method such as tableting, briquetting or extrusion, preferably tableting. Tablets for the dishwashing process are preferably produced using a standard rotary tablet press, using a pressure of 5-13 KN/cm ² , more preferably 5-11 KN/cm ² , so that the compact solid is provided by the I. Holland apparatus According to the C100 hardness test, it has a minimum hardness of 176N-275N, preferably 195N-245N. The method can be used to prepare uniform or layered tablets of any size or shape. Preferably the tablet is symmetrical to ensure uniform dissolution of the tablet in the wash solution. laundry method

The machine laundry methods of the present invention generally comprise treating soiled fabrics with an aqueous wash solution comprising dissolved or dispersed in a washing machine an effective amount of a machine washing detergent component of the present invention, but preferably a composition comprising the component. An effective amount of detergent composition means 10 g to 300 g of product dissolved or dispersed in a volume of 5 to 65 liters of wash solution, as typical product amounts and wash solution volumes are usually used in conventional machine washing methods.

In a preferred aspect of use, the dispersing device is used in a washing process. Dispensing units hold detergent product and are used to add product directly to the washing machine drum before the wash cycle begins. Its volume capacity should be such that it contains sufficient detergent product normally used in the washing process.

The dispensing device containing the detergent product is placed in the drum before the wash starts, or before, while or after the washing machine is loaded with clothes. After the washing cycle of the washing machine starts, water is added to the drum, and the drum rotates periodically. The dispenser is designed so that it holds dry detergent products, but then releases these products during the wash cycle in response to agitation as the drum rotates and due to contact with the wash water.

To enable release of detergent product during washing, the device should have a number of openings through which the product can pass. Additionally, the device should be fabricated from a material that is permeable to liquids but impermeable to solid products, thereby allowing release of dissolved product. The detergent product is preferably released rapidly at the start of the wash cycle, thereby providing a temporary localized high concentration of product in the drum of the washing machine during this wash cycle phase.

Preferred dispensing devices are reusable, designed so that the container maintains its integrity in the dry state and through the wash cycle. Particularly preferred dispersing devices for compositions of the invention are described in the following patents: GB-B-2157717, GB-B-2157718, EP-A-0201376, EP-A-0288345 and EP-A-0288346. A particularly preferred dispersing device for granular laundry products is also described by J. Bland in Manufacturing Chemist, November 1989, pp. 41-46, which is of the type commonly known as a "granulette". Another preferred dispensing device for the detergent compositions of the present invention is disclosed in PCT patent application WO 94/11562.

Particularly preferred dispersing devices are disclosed in EP0343069 and 0343070. The latter application discloses a device comprising a curved housing in the form of a bag extended by a support ring, said ring defining an aperture adapted to contain in the bag sufficient product for one wash cycle of the washing method . A portion of the wash medium flows into the bag through the holes, dissolves the product, and the solution then flows outward through the holes into the wash medium. The support ring is shielded to avoid loss of wet, undissolved product and the device usually comprises radially extending walls expanding from a central post in the form of a spoked wheel or similar structure in which the walls are in the form of a helix.

Additionally, the dispensing device may be a flexible container such as a bag or box. The bag may be a fibrous structure coated with a water impermeable protective material to hold the contents, such as disclosed in EP0018678. Alternatively, it may be made of a water insoluble synthetic polymeric material with edge seals or closed designs to keep out aqueous media as disclosed in EP0011500, 0011501, 0011502 and 0011968. A convenient form of water-loose closure includes a water-soluble adhesive for handling and sealing one edge of a box made of a water-impermeable polymer film, such as polyethylene or polypropylene. Machine washing dishes

Machine dishwashing or any suitable method of cleaning soiled tableware, especially soiled silverware, is conceivable.

A preferred machine dishwashing method comprises treating the soiled article with an aqueous solution comprising dissolved or dispersed an effective amount of a machine dishwashing component of the present invention, or a composition preferably comprising the same, selected from crockery, glassware, dishware Utensils, silverware and cutlery and mixtures thereof. An effective amount of a machine dishwashing composition means dissolving or dispersing 8g to 60g of product in a volume of wash solution of 3 to 10 liters, which is a typical amount of product and volume of wash solution commonly used in conventional machine dishwashing methods.

Abbreviations used in the examples

In detergent compositions, the abbreviated components have the following meanings: LAS: Sodium linear C _11-13 alkylbenzene sulfonate TAS: Sodium tallow alkyl sulfate C _xy AS: Sodium C _1X - _{C 1Y} alkyl sulfate C46SAS: Sodium C ₁₄ -C ₁₆ secondary (2,3) alkyl sulfate C _xy E _z S: Sodium C _1X -C _1Y alkyl sulfate condensed with Z moles of ethylene oxide C _XY E _Z : Ring with Z moles Oxyethane condensation is mainly linear C _1X -C _1Y

Primary alcohol QAS: R ₂ N ⁺ (CH ₃ ) ₂ (C ₂ H ₄ OH), R ₂ =C ₁₂ -C ₁₄ QAS1: R ₂ N ⁺ (CH ₃ ) ₂ (C ₂ H ₄ OH), R ₂ =C ₈ -C ₁₁ QAS2 :R ₂ N ⁺ (CH ₃ ) ₂ (C ₂ H ₄ OH),R ₂ =C ₈ APA :C ₈ -C ₁₀ amidopropyl dimethylamine soap: straight chain alkane Sodium carboxylate, 80/20 of tallow and coconut fatty acids

The mixture gives STS: sodium toluene sulfonate CFAA: C ₁₂ -C ₁₄ (coconut) alkyl N-methyl glucamide TFAA: C ₁₆ -C ₁₈ alkyl N-methyl glucamide TPKFA: C ₁₂ -C ₁₄ Top full cut fatty acid STPP: anhydrous sodium tripolyphosphate TSPP: tetrasodium pyrophosphate zeolite A: hydrated sodium aluminosilicate of formula Na ₁₂ (AlO ₂ SiO ₂ ) ₁₂ ·27H ₂ O, mainly

Particle size 0.1-10 microns ₍ weight expressed on anhydrous basis ₎ NaSKS-6: crystalline layered silicate of formula δ- _Na2Si2O5 Citric acid: Anhydrous citrate Borate: Sodium borate carbon Salt: anhydrous sodium bicarbonate with a particle size of 200-900 microns Bicarbonate: anhydrous sodium bicarbonate with a particle distribution of 400-1200 microns Silicate: amorphous sodium silicate (SiO ₂ : Na ₂ O ratio = 2.0:1) Sulfate: anhydrous sodium sulfate magnesium sulfate: anhydrous magnesium sulfate citrate: trisodium citrate dihydrate, activity 86.4%, particle size

The cloth is 425-850 microns MA/AA1: 3:7 maleic acid/acrylic acid copolymer, the average molecular weight is about 70000MA/AA2: 4:6 maleic acid/acrylic acid copolymer, the average molecular weight is about 3000MA/AA3: 4:6 Ma Lycic acid/acrylic acid copolymer with an average molecular weight of about 12000AA : sodium polyacrylate polymer with an average molecular weight of 4500 CM : sodium carboxymethyl cellulose cellulose ether: methyl cellulose ether with a polymerization degree of 650, by Shin Etsu

Protease available from Chemicals: sold under the tradename Savinase by Novo Industries A/S

Proteolytic enzyme with 3.3% by weight activity Enzyme Protease I: proteolytic enzyme described in WO95/10591 with 4%

Weight Active Enzyme, sold by Genencor Int. Inc. Alcalase: a proteolytic enzyme sold by Novo Industries A/S, having

5.3% by weight active enzyme cellulase: sold under the tradename Carezyme by Novo Industries A/S

Cellulase with 0.23% by weight active enzyme Amylase: trade name Termamyl 120T by Novo Industries A/S

Amylase sold with 1.6% by weight active enzyme lipase: sold by Novo Industries A/S under the tradename Lipolase

Lipolytic enzyme with 2.0% by weight active enzyme lipase (1): marketed under the tradename Lipolase Ultra by Novo Industries A/S

Lipolytic enzyme sold with 2.0% by weight active enzyme Endolase: Endoglucanase enzyme sold by Novo Industries A/S,

Enzyme PB4 with 1.5% by weight activity: sodium perborate tetrahydrate of formula NaBO ₂ 3H ₂ O H ₂ O ₂ : anhydrous sodium perborate bleach of formula NaBO ₂ .H ₂ O ₂ sodium percarbonate: formula Sodium percarbonate of 2Na ₂ CO ₃ 3H ₂ O ₂ NOBS: Nonanoyloxybenzenesulfonate, sodium salt form NAC-OBS: (6-nonanoylhexanoyl)oxybenzenesulfonate TAED: Tetraacetylethylenedi Amine DTPA: Diethylenetriaminepentaacetic acid DTPMP: Diethylenetriaminepenta(methylenephosphonic acid), commercially available from Monsanto

  Name Dequest 2060 Sales EDDS : Ethylenediamine-N,N’-disuccinic acid, (S,S) isomer, sodium

Photoactivated bleaching in salt form: sulfonated zinc phthalocyanine agent encapsulated with cyclodextrin-soluble polymer (1) Photoactivated bleaching: sulfonated aluminum phthalocyanine agent encapsulated with cyclodextrin-soluble polymer (2) Brightener 1: 4,4'-bis(2-sulfostyrene) disodium biphenyl Brightener 2: 4,4'-bis(4-phenylamino-6-morpholino-1,3 ,5-triazin-2-yl)amino)

Stilbene-2:2'-disodium disulfonate HEDP: hydroxyethane 1,1-diphosphonic acid PEG _x : polyethylene glycol, molecular weight x (generally 4000) PEO: polyoxyethylene, average molecular weight 50,000 TEPAE: B Oxylated Tetraethylenepentamine PVI: Polyvinylimidazole, average molecular weight 20,000PVP: Polyvinylpyrrolidone polymer, average molecular weight 60,000PVNO: Polyvinylpyridine N-oxide polymer, average molecular weight 50,000PVPVI: Polyvinylpyrrolidone Copolymers with vinylimidazole, average

Molecular weight 20000QEA1 : MeSO ₄ ^-di ((C ₂ H ₅ O)(C ₂ H ₄ O) _n (CH ₃ )-N ⁺ -C ₆ H ₁₂ -N ⁺ -

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

is C ₄ -C ₁₂ alkyl and n=20-30QEA3 : Tri{(two((C ₂ H ₅ O)-(C ₂ H ₄ O) _n )(CH ₃ )N ⁺ )-(CONC ₃ H ₆ )}-

Salt of C ₃ H ₆ O where n=20-26 SRP1: anion-terminated polyester SRP2: diethoxylated poly(1,2propylene phthalate) short-block co

     Polymer PEI    : Polyethyleneimine, with an average molecular weight of 1800, each nitrogen atom

The average degree of ethoxylation is 7 ethylene oxide residue polysiloxane defoaming: polydimethylsiloxane foam control agent and polysiloxane-agent as dispersant oxyalkylene copolymer, the Foam control agent and the weight of the dispersant

A 10:1-100:1 sunscreen: a water-based monostyrene latex blend, manufactured by BASF

Aktiengesellschaft sells wax under the trade name Lytron 621: Paraffin

In the following examples, all contents are expressed in % by weight of the composition: Example 1

The following high density granular laundry detergent compositions AF, especially for use in European washing machine conditions are examples according to the invention: 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 Sulfate 26.1 26.1 26.1 26.1 26.1 26.1 MA/AA1 0.6 0.8 0.3 1.0 0.5 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.O 0.8 0.7 1.2 - 0.5 QEA2 - - - - 1.O 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 Polysiloxane Antifoam Agent 0.5 0.5 0.5 0.5 0.5 0.5 Other/minor components to 100% Density g/L 850 850 850 850 850 850 Example 2

The following high density granular laundry detergent compositions GL for particular application in European washing machine conditions are examples according to the invention: G h I J K L 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 Sulfate 26.1 26.1 26.1 26.1 26.1 26.1 MA/AA1 0.5 0.8 0.3 1.0 0.5 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 Polysiloxane Antifoam Agent 0.5 0.5 0.5 0.5 0.5 0.5 Other/minor components to 100% Density g/L 850 850 850 850 850 850 Example 3

The following granular laundry detergent compositions MO with a bulk density of 750 g/l are compositions according to the invention: m N o LAS 5.25 5.61 4.76 TAS 1.25 1.86 1.57 C45AS - 2.24 3.89 C25AE3S - 0.76 1.18 C45E7 3.25 - 5.0 C25E3 - 5.5 - QAS 0.8 2.0 - QAS1 0.4 1.0 2.5 STPP 19.7 - - Zeolite A 19.5 19.5 NaSKS-6/citric acid (79:21) 10.6 10.6 carbonate 6.1 21.4 21.4 Bicarbonates - 2.0 2.0 citric acid 0.3 0.2 - Silicate 6.8 - - sodium sulfate 39.8 - 7.0 PB4 5.0 12.7 - TAED 0.5 0.2 - DPDA - - 0.3 NACOBS 1.0 2.2 - DTPMP 0.25 0.2 0.2 HEDP - 0.3 0.3 protease 0.26- 0.85 0.85 Lipase 0.15- 0.15 0.15 cellulase 0.28 0.28 0.28 Amylase 0.1- 0.1 0.1 MA/AA 0.5 0.8 0.4 QEA1 1.0 1.5 - QEA2 - - 0.8 CMC 0.2 0.4 0.4 pvp - - 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 Polysiloxane antifoam agent 1 0.5 2.4 2.4 Other/minor components to 100% na na Example 4

The following detergent formulations, particularly for use in European washing machine conditions, are examples according to the invention: P Q R S 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/AA2 2.0 - - 4.0 MA/AA1 - 1.0 0.5 - Silicate 7.0 3.0 3.0 3.0 CMC 1.0 1.0 0.5 0.6 QEA1 0.8 1.0 3.0 0.5 QEA2 - - - 0.5 brightener 0.2 0.2 0.2 0.2 Polysiloxane Antifoam Agent 1.0 1.0 1.0 0.3 DTPMP 0.4 0.4 0.2 0.4 spraying 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 Polysiloxane Antifoam Agent 0.3 0.3 0.3 - dry additive 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 5

The following detergent formulations, particularly for use in European washing machine conditions, are examples according to the invention: T u V W blown powder LAS 6.0 5.0 1.0 6.0 TAS 2.0 - - 2.0 Zeolite A 24.0 - - 20.0 STPP - 27.0 24.0 - Sulfate 9.0 6.0 13.0 5.0 QAS1 0.5 0.8 - 1.0 MA/AA1 0.4 0.9 - - MA/AA2 - - 0.4 0.5 QEA1 1.0 1.2 0.7 - QEA3 - - - 0.5 Silicate 1.0 7.0 3.0 3.0 CMC 1.0 1.0 0.5 0.6 Brightener 1 0.2 0.2 0.2 0.2 Polysiloxane Antifoam Agent 1.0 1.0 1.0 0.3 carbonate 5.0 3.0 - 4.0 STS 0.3 0.5 - 0.2 DTPMP 0.4 0.4 0.2 0.4 spraying brightener 0.02 - - 0.02 C45E7 - - - 5.0 C45E2 2.5 2.5 2.0 - C45E3 2.6 2.5 2.0 - spices 0.5 0.3 0.5 0.2 Polysiloxane Antifoam Agent 0.3 0.3 0.3 - dry additive QEA - - - 0.5 EDDS 0.3 - - - Sulfate 2.0 3.0 5.0 10.0 carbonate 6.0 10.0 12.0 9.0 citric acid 2.5 - - 2.0 QASⅡ 0.5 - - 0.5 SKS-6 10.0 - - - Percarbonate 18.5 - - - PB4 - 18.0 10.0 21.5 TAED 2.0 2.0 - 2.0 NAC-OBS 3.0 2.0 4.0 - protease 1.0 1.0 1.0 1.0 Lipase - 0.4 - 0.2 Lipase (1) 0.4 - 0.4 - Amylase 0.2 0.2 0.2 0.4 brightener 0.05 - - 0.05 Other/minor components to 100% Example 6

The following granular detergent formulations are examples according to the invention: x Y Z AAA BB CC blown powder LAS 23.0 8.0 7.0 9.0 7.0 7.0 TAS - - - - 1.0 - C45AS 6.0 6.0 5.0 8.0 - - C45AES - 1.0 1.0 1.0 - - C45E35 - - - - 2.0 4.0 Zeolite A 10.0 18.0 14.0 12.0 10.0 10.0 MA/AA - 0.5 0.4 - - 0.3 MA/AA(1) 0.9 - - - - - AAA - - 0.1 1.0 - 0.2 QAS1 0.5 0.6 - - 1.0 1.0 Sulfate 5.0 6.3 14.3 11.0 15.0 15.3 Silicate 10.0 1.0 1.0 1.0 1.0 1.0 QEA1 0.9 1.1 - - - 0.5 QEA2 - - 1.0 1.5 - - QEA3 - - - - - 0.5 carbonate 15.0 20.0 10.0 20.7 8.0 6.0 PEG4000 0.4 1.5 1.5 1.0 1.0 1.0 STS 0.2 - - 0.5 0.3 0.2 DTPA - 0.3 0.3 - - 0.4 Brightener 2 0.3 0.2 0.3 - 0.1 0.3 spraying - - - - - - C45E7 - 2.0 - - 2.0 2.0 C25E9 3.0 - - - - - C23E9 - - 1.5 2.0 - 2.0 spices 0.3 0.3 0.3 2.0 0.3 0.3 Agglomerates C45AS - 5.0 5.0 2.0 - 5.0 LAS - 2.0 2.0 - - 2.0 QEA1 - - - - 0.8 - MA/AA1 - - - - 0.8 - Zeolite - 7.5 7.5 8.0 - 7.5 carbonate - 4.0 4.0 5.0 - 4.0 PEG4000 - 0.5 0.5 - - 0.5 Other (water, etc.) - 2.0 2.0 2.0 - 2.0 dry additive QAS(Ⅰ) - - - - 1.0 - Citrate - 0.4 - - 2.0 0.5 PB4 - - - - 12.0 1.0 PB1 4.0 1.0 3.0 2.0 - - Percarbonate - - - - 2.0 10.0 carbonate - 5.3 1.8 - 4.0 4.0 NOBS 4.0 - 6.0 - - 0.6 Methylcellulose 0.2 - - - - - SKS-6 8.0 - - - - - STS - - 2.0 - 1.0 - cumenesulfonic acid - 1.0 - - - 2.0 Lipase 0.2 - 0.2 - 0.2 0.4 cellulase 0.2 0.2 0.2 0.3 0.2 0.2 Amylase 0.2 - 0.1 - 0.2 - protease 0.5 0.5 0.5 0.3 0.5 0.5 PVP VI - - - - 0.5 0.1 pvp - - - - 0.5 - PVNO - - 0.5 0.3 - - QEA - - - - 1.0 - SRP1 0.2 0.5 0.3 - 0.2 - Polysiloxane Antifoam Agent 0.2 0.4 0.2 0.4 0.1 - magnesium sulfate - - 0.2 - 0.2 - Other/minor components to 100% Example 7

The following bleach-free detergent formulations, especially for washing colored clothes, were prepared, which are examples according to the invention: DD EE FF blown powder Zeolite A 15.0 15.0 - Sulfate 0.0 10.0 - LAS 3.0 3.0 - DTPMP 0.4 0.5 - CMC 0.4 0.4 - QEA1 1.0 0.2 - QEA2 - 1.0 - MA/AA1 0.5 - - AAA - 0.6 - carbonate - 5.0 - STS - 0.2 - QAS1 - 1.0 - Agglomerates - C45AS - - 11.0 LAS 6.0 5.0 - TAS 3.0 2.0 - Silicate 4.0 4.0 - Zeolite A 10.0 15.0 13.0 QEA1 - - 1.0 CMC - - 0.5 MA/AA - - 0.8 carbonate 9.0 7.0 7.0 spraying spices 0.3 0.3 0.5 C45E7 4.0 4.0 4.0 C25E3 2.0 2.0 2.0 dry additive MA/AA - - 3.0 NaSKS-6 - - 12.0 citric acid 10.0 - 8.0 Bicarbonates 7.0 3.0 5.0 carbonate 8.0 5.0 7.0 PVPVI/PVNO 0.5 0.5 0.5 Alcalase 0.5 0.3 0.9 Lipase 0.4 0.4 0.4 Amylase 0.6 0.6 0.6 cellulase 0.6 0.6 0.6 Polysiloxane Antifoam Agent 5.0 5.0 5.0 Citrate - 1.0 - Sulfate 0.0 9.0 0.0 Other/minor components to 100% 100.0 100.0 100.0 Density (g/L) 700 700 700 Example 8

The following granular detergent compositions for particular application under European washing conditions are examples according to the invention: EE FF 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/AA1 4.0 2.0 MA/AA2 - 2.0 CMC 0.6 0.6 QEA1 0.9 0.6 QEA3 0.1 - Brightener 1 0.2 0.2 DTPMP 0.4 0.4 spraying C45E7 5.0 5.0 Polysiloxane Antifoam Agent 0.3 0.3 spices 0.2 0.2 dry additive 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 (water and others) Density (g/L) 700 700 Example 9

The following detergent compositions are examples according to the invention: GG HH II 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 QAS - 1.5 1.5 DTPMP 0.4 0.2 0.4 CMC 0.4 0.4 0.4 MA/AA1 - - 2.0 MA/AA2 2.0 - - AAA - 4.0 - Agglomerates LAS 5.0 5.0 5.0 TAS 2.0 2.0 1.0 Silicate 3.0 3.0 4.0 QEA1 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 spraying spices 0.3 0.3 0.3 C45E7 2.0 2.0 2.0 C25E3 2.0 - - dry additive - - - 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 - Polyoxyethylene MW5,000,000 - - 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 Polysiloxane Antifoam Agent 5.0 5.0 5.0 dry additive sodium sulfate 0.0 3.0 0.0 Balance (water and others) 100.0 100.0 100.0 Density (g/L) 850 850 850 Example 10

The following granular detergent formulations are examples according to the invention: JJ KK LL MM basic particles Zeolite A 30.0 22.0 24.0 10.0 Sulfate 10.0 5.0 10.0 7.0 MA/AA1 - 0.5 - - AAA 0.9 - 1.0 - MA/AA2 - - - 1.0 QEA1 - 1.2 1.2 - QEA3 1.5 - - 3.0 QAS2 - 1.0 0.5 - LAS 14.0 10.0 9.0 20.0 C45AS 8.0 7.0 9.0 7.0 C45AES - 1.0 1.0 - Silicate - 1.0 0.5 10.0 soap - 2.0 - - Brightener 1 0.2 0.2 0.2 0.2 carbonate 6.0 9.0 10.0 10.0 PEG4000 - 1.0 1.5 - DTPA - 0.4 - - spraying C25E9 - - - 5.0 C45E7 1.0 1.0 - - C23E9 - 1.0 2.5 - spices 0.2 0.3 0.3 - dry additive carbonate 5.0 10.0 18.0 8.0 PVPVI/PVNO 0.5 - 0.3 - protease 1.0 1.0 1.0 0.5 Lipase 0.4 - - 0.4 Amylase 0.1 - - 0.1 cellulase 0.1 0.2 0.2 0.1 NOBS - 4.0 - 4.5 PB1 1.0 5.0 1.5 6.0 Sulfate 4.0 5.0 - 5.0 SRPI - 0.4 - - Foam suppressor - 0.5 0.5 - Other/minor components to 100% Example 11

The following granular detergent compositions are examples according to the invention: NN OO PP QQ RR SS TT UU blown powder Zeolite A 20.0 - 15.0 15.0 15.0 15.0 15.0 15.0 STPP - 20.0 - - - - - - Sulfate - - 15.0 15.0 15.0 15.0 15.0 15.0 carbonate - - 5.0 5.0 5.0 5.0 5.0 5.0 TAS - - 1.0 1.0 1.0 1.0 1.0 1.0 LAS 6.0 6.0 6.0 6.0 6.0 6.0 6.0 6.0 Silicate 3.0 8.0 - - - - - - QEA1 1.2 1.5 0.9 0.9 0.9 0.9 0.9 0.9 QAS1 1.2 - 0.9 - 0.9 - - - QAS - 1.5 - 0.9 - 0.9 - - MA/AA1 1.7 1.7 0.5 0.5 0.5 0.5 0.5 0.5 CMC 0.4 0.4 0.2 0.2 0.2 0.2 0.2 0.2 Brightener 1 0.2 0.2 0.1 0.1 0.1 0.1 0.1 0.1 DTPMP 0.2 0.2 0.1 0.1 0.1 0.1 0.1 0.1 STS - 1.0 1.0 1.0 - - 1.0 - spraying C45E7 5.0 5.0 4.0 4.0 4.0 4.0 4.0 4.0 Polysiloxane Antifoam Agent 0.3 0.3 0.1 0.1 0.1 0.1 0.1 0.1 spices 0.2 0.2 0.3 0.3 0.3 0.3 0.3 0.3 dry additive QEA 1.0 1.0 - - - - - - carbonate 14.0 9.0 10.0 10.0 10.0 10.0 10.0 10.0 PB1 1.5 2.0 - - - - - - PB4 18.5 13.0 13.0 13.0 13.0 13.0 13.0 13.0 TAED 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 QAS1 1.0 1.0 - - - - 1.0 1.0 photoactivated bleach 15ppm 15ppm 15ppm 15ppm 15ppm 15ppm 15ppm 15ppm SKS-6 - - 3.0 3.0 3.0 3.0 3.0 3.0 protease 1.0 1.0 0.2 0.2 0.2 0.2 0.2 0.2 Lipase 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 Amylase 0.4 0.4 0.2 0.2 0.2 0.2 0.2 0.2 cellulase 0.1 0.1 0.2 0.2 0.2 0.2 0.2 0.2 Sulfate 10.0 20.0 5.0 5.0 5.0 5.0 5.0 5.0 Other/minor components to 100% Density (g/L) 690 690 690 690 690 690 690 690 Example 12

The following laundry bar detergent compositions are examples according to the invention: VV WW XX YY ZZ AB AC AD LAS - - 19.0 15.0 21.0 6.75 8.8 - C28AS 30.0 13.5 - - - 15.75 11.2 22.5 sodium laurate 2.5 9.0 - - - - - - Zeolite A 2.0 1.25 - - - 1.25 1.25 1.25 carbonate 20.0 3.0 13.0 8.0 10.0 15.0 15.0 10.0 calcium carbonate 21.5 - - - - - - - Sulfate 5.0 - - - - - - - TSPP 5.0 - 5.0 - 5.0 5.0 2.5 5.0 STPP 5.0 15.0 - - - 5.0 8.0 10.0 Bentonite - 10.0 - - 5.0 - - - DTPMP - 0.7 0.6 - 0.6 0.7 0.7 0.7 MA/AA1 0.4 1.0 - - 0.2 0.4 0.5 0.4 MA/AA2 - - 0.9 1.2 0.8 0.8 - - SRP1 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 protease - 0.12 - 0.08 0.08 - - 0.1 Lipase - 0.1 - 0.1 - - - - Amylase - - 0.8 - - - 0.1 - cellulase - 0.15 - - 0.15 - - - PEOs - 0.2 - 0.2 0.3 - - 0.3 spices 1.6 - - - - - - - Example 13

The following compact type high-density (0.96Kg/l) dishwashing detergent composition NN-SS is an embodiment according to the present invention, and the abbreviated component symbols used in this dishwashing detergent composition have the following definitions: metasilicate Salt: Sodium Metasilicate (SiO ₂ : Na ₂ O=1.0) Non-ionic: Has an average degree of ethoxylation of 3.8 and an average degree of propoxylation

4.5 C ₁₃ -C ₁₅ mixed ethoxylated/propoxylated fats

Alcohol, sold under the trade name PlurafacLF404 by BASF GmbH

Sold (Low Foam) PAAC : Cobalt(III) Pentaamine Acetate BzP : Benzoyl Peroxide Paraffin : Paraffin wax sold under the trade name Winog 70 by Wintershall

  Oil BTA   : Benzotriazole Bismuth Nitrate: Bismuth Nitrate Salt Terpolymer: Terpolymer with an average molecular weight of about 7000, which contains

 Acrylic acid:maleic acid:ethyl in a weight ratio of 60:20:20

Acrylic monomer 480N: 3:7 random copolymer of acrylic acid/methacrylic acid, average

Quantity about 3500 AE AF AG AH AI AJ STPP 24.80 24.80 25.00 28.39 28.50 20.00 Citrate - - - - 10.00 10.00 carbonate - - 17.50 17.50 - - QEA1 0.5 1.5 2.0 1.0 1.3 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 Nonionic 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 - - BzP - - - 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 - - - Terpolymer - - - 4.00 - - MA/AA2 0.5 1.0 1.00 0.50 0.7 0.8 Sulfate 8.44 8.44 20.77 - 23.24 1.00 Others and moisture to balance pH(1% solution) 10.90 10.90 11.00 10.80 10.90 9.60

Claims (27)

1. solid, preferred granular detergent composition or its component, it comprises: the polyelectrolyte compound that (a) contains carboxylate radical; (b) have the water-soluble cationic compound of removing native dirt/antiredeposition performance, it is selected from:

1) have the ethoxylation positively charged ion monoamine of following formula:

2). have the ethoxylation cationic diamine of following formula:

Or M wherein ¹Be N+ or N group; Each M ²Be N+ or N group, at least one M ²It is the N+ group.

3) have the ethoxylation cationic polyamine of following formula:

4) their mixture; A wherein ¹Be

Or

R is H or C ₁-C ₄Alkyl or hydroxyalkyl, R ¹Be C ₂-C ₁₂Alkylidene group, hydroxy alkylidene, alkylene group, arylidene or alkyl arylene, or have the C of about 20 oxygen alkylidene units of 2- ₂-C ₃Oxyalkylene segment, condition are not form the O-N key; Each R ²Be C ₁-C ₄Alkyl or hydroxyalkyl, segment-L-X; Or two R ²In conjunction with formation-(CH ₂) _r-A ²-(CH ₂) _s-, A wherein ²Be-O-or-CH ₂-, r is 1 or 2, and s is 1 or 2, and r+s is 3 or 4; Each R ³Be C ₁-C ₈Alkyl or hydroxyalkyl, benzyl, segment L-X, or two R ³Or R ²With a R ³In conjunction with forming segment-(CH ₂) _r-A ²-(CH ₂) _s-; R ⁴Be C with replacement of p the position of substitution ₃-C ₁₂Alkyl, hydroxyalkyl, alkenyl, aryl or alkaryl; R ⁵Be C ₁-C ₁₂Alkenyl, hydroxy alkylidene, alkylene group, arylidene or alkyl arylene, or have the C of about 20 oxygen alkylidene units of 2- ₂-C ₃Oxyalkylene segment, condition are not form O-O or O-N key; X is selected from H, C ₁-C ₄The non-ionic group of alkyl or hydroxy alkyl ester or ether group and their mixture; L contains the polyoxy alkylidene segment :-[(R ⁶O) _m(CH ₂CH ₂O) _n]-hydrophilic chain; R wherein ⁶Be C ₃-C ₄Alkylidene group or hydroxy alkylidene, m and n are to make segment-(CH ₂CH ₂O) _n-account for said polyoxy alkylidene segment at least about 50% numerical value; Work as M ²When being N+, d is 1, works as M ²When being N, d is 0; For said positively charged ion monoamine, n is at least about 16, and for said cationic diamine, n is that n is at least about 3 at least about 6 with for said cationic polyamine; P is 3-8; Q is 1 or 0; T is 1 or 0, and condition is when q is 1, and t is 1; Wherein (a) and ratio (b) are 1: 95 to 95: 1.

2. according to the detergent composition or the component of claim 1, wherein said ratio is 1: 25-25: 1.

3. according to the detergent component of claim 1, wherein said ratio is 1: 1-1: 10.

4. according to the detergent component of claim 1 or 3, wherein said ratio is 1: 1-1: 2.

5. the detergent component of a spray-dried granules, it comprises: the polyelectrolyte compound that (a) contains carboxylate radical; (b) have the water-soluble cationic compound of removing native dirt/antiredeposition performance, it is selected from:

1) have the ethoxylation positively charged ion monoamine of following formula:

2). have the ethoxylation cationic diamine of following formula:

Or

M wherein ¹Be N+ or N group; Each M ²Be N+ or N group, at least one M ²It is the N+ group.

3) have the ethoxylation cationic polyamine of following formula:

4) their mixture; A wherein ¹Be

R is H or C ₁-C ₄Alkyl or hydroxyalkyl, R ¹Be C ₂-C ₁₂Alkylidene group, hydroxy alkylidene, alkylene group, arylidene or alkyl arylene, or have the C of about 20 oxygen alkylidene units of 2- ₂-C ₃Oxyalkylene segment, condition are not form the O-N key; Each R ²Be C ₁-C ₄Alkyl or hydroxyalkyl, segment-L-X; Or two R ²In conjunction with formation-(CH ₂) _r-A ²-(CH ₂) _s-, A wherein ²Be-O-or-CH ₂-, r is 1 or 2, and s is 1 or 2, and r+s is 3 or 4; Each R ³Be C ₁-C ₈Alkyl or hydroxyalkyl, benzyl, segment L-X, or two R ³Or R ²With a R ³In conjunction with forming segment-(CH ₂) _r-A ²-(CH ₂) _s-; R ⁴Be C with replacement of p the position of substitution ₃-C ₁₂Alkyl, hydroxyalkyl, alkenyl, aryl or alkaryl; R ⁵Be C ₁-C ₁₂Alkenyl, hydroxy alkylidene, alkylene group, arylidene or alkyl arylene, or have the C of about 20 oxygen alkylidene units of 2- ₂-C ₃Oxyalkylene segment, condition are not form O-O or O-N key; X is selected from H, C ₁-C ₄The non-ionic group of alkyl or hydroxy alkyl ester or ether group and their mixture; L contains the polyoxy alkylidene segment :-[(R ⁶O) _m(CH ₂CH ₂O) _n]-hydrophilic chain; R wherein ⁶Be C ₃-C ₄Alkylidene group or hydroxy alkylidene, m and n are to make segment-(CH ₂CH ₂O) _n-account for said polyoxy alkylidene segment at least about 50% numerical value; Work as M ²When being N+, d is 1, works as M ²When being N, d is 0; For said positively charged ion monoamine, n is at least about 16, and for said cationic diamine, n is that n is at least about 3 at least about 6 with for said cationic polyamine; P is 3-8; Q is 1 or 0; T is 1 or 0, and condition is when q is 1, and t is 1; Wherein (a) is 1 with (b) ratio of compound: 1-1: 10.

6. according to the detergent composition or the component of any aforementioned claim, wherein the content of cation compound by detergent component or particulate weight, is 0.5%-15%.

7. according to the detergent composition or the component of any aforementioned claim, wherein the content of cation compound by the weight of said composition, is 0.01%-30%.

8. according to the detergent composition or the component of any aforementioned claim, wherein the content of cation compound by the weight of said composition, is 0.2%-3%.

9. according to the detergent composition or the component of any aforementioned claim, wherein said cation compound is an ethoxylation positively charged ion monoamine, is characterised in that a R ²Be methyl, two R ²Be segment L-X, m is 0, and n is at least about 20.

10. according to any detergent composition or the component of claim 1-8, wherein said cation compound is the ethoxylation cationic diamine, is characterised in that R ¹Be C ₂-C ₆Alkylidene group.

11. according to any detergent composition or the component of claim 1-8 or 10, wherein said ethoxylation cationic diamine is characterised in that R ¹It is hexa-methylene.

12. according to any detergent composition or the component of claim 1-8, wherein said cation compound is the ethoxylation cationic polyamine, is characterised in that R ⁴Be the C that replaces ₃-C ₆Alkyl, hydroxyalkyl or aryl; A1 is: With p be 3-6.

13. according to any detergent composition or the component of claim 10-12, wherein said cation compound is characterised in that each R ²Be methyl or segment-L-X, each R ³Be methyl, M ¹With each M ²Be N ⁺Group.

14. according to any detergent composition or the component of claim 10-13, wherein m is 0, n is at least 12.

15. according to the detergent composition or the component of claim 10 or 11, wherein m is 0, n is at least 20.

16. according to the detergent composition or the component of any aforementioned claim, wherein the cation water-soluble compound has one or more MeSO ₄ ^-The anionic counter-ion of form.

17. according to the detergent composition or the component of any aforementioned claim, wherein contain the content of the polyelectrolyte compound of carboxylate radical,, be 0.01%-40% by the weight of said composition.

18. according to the detergent component of claim 17, wherein contain the content of the polyelectrolyte compound of carboxylate radical,, be 0.1%-15% by the weight of this component.

19. according to the detergent component of claim 18, wherein contain the content of the polyelectrolyte compound of carboxylate radical, by this component or particulate weight, be 0.2%-2.0%, preferred 1.2%.

20. according to any detergent composition or the component of claim 1-19, the polyelectrolyte compound that wherein contains carboxylate radical is toxilic acid/acrylic copolymer or acrylate homopolymer.

21. according to the detergent composition or the component of claim 20, wherein the molecular-weight average of toxilic acid/acrylic copolymer is 2500-20000, or 60000-70000.

22., wherein have cation mono-or dialkoxy amine tensio-active agent according to the detergent composition or the component of any aforementioned claim.

23. detergent composition or component according to any aforementioned claim wherein exist carbonate and vitriol.

24. preparation is according to the method for the detergent component of the spray-dried granules of any aforementioned claim, this method may further comprise the steps: a) preparation cation compound and contain the polyelectrolyte of carboxylate radical and the mixture of additional detergent components randomly, wherein cation compound is 1 with the ratio that contains the polyelectrolyte of carboxylate radical: 95-95: 1, preferred 10: 1-1: 1; B) spraying drying mixture a).

25. preparation is according to the method for the detergent component of the spray-dried granules of any aforementioned claim, this method may further comprise the steps: a) preparation 1: 95-95: 1, preferred 10: 1-1: the cation compound of 1 ratio and the mixture that contains the polyelectrolyte of carboxylate radical; B) in the mixture of step a), add additional detergent component and form second kind of mixture; C) second kind of mixture b of spraying drying).

26. according to the method for claim 25, wherein additional detergent component is an organic constituent.

27. according to the method for claim 26, wherein second kind of mixture added in the other additional detergent components before the spraying drying step.