JP2002524574A - Builder ingredients - Google Patents

Abstract

  (57) [Summary] The present invention relates to at least a crystalline laminated silicate having a particle size of less than 150 microns or even less than 102 microns and at the same time a weight average particle size of 15.0 microns or more, preferably 16.0 to 48.8 microns. A builder component is provided which comprises a powdered crystal-laminated silicate at 95% by weight, or even 98% or even 100%. The builder component can be used in particular in solid detergent compositions.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

【Technical field】

The present invention relates to builder components that have excellent building performance, improved dispensability and solubility, and are particularly useful in detergent compositions.

[0002]

BACKGROUND OF THE INVENTION

Over the past decades, detergent manufacturers have focused on developing improved builders as alternatives to phosphate builders. On the one hand new builder substances have been developed and on the other hand existing builders or builder combinations have been improved, for example by optimizing the level or ratio of the builder substances. In general, most detergents still use polycarboxylate and silicate builders, such as aluminosilicates, amorphous and crystalline sodium silicates.

[0003] One of the major complaints of detergent product users has been found to be that products are not always distributed satisfactorily. This causes the product to remain on the dispensing drawer, for example in the form of a gel, in the washing machine and even on the fabric after washing. This is because under cold water wash conditions or when a limited amount of water is used in the wash process.
Certain components or high density products can be particularly problematic, for example, when small amounts of water come into contact with the product inside the distribution drawer or machine early in the cleaning process.

[0004] A problem associated with gelling of products is that the products are not efficiently delivered to the laundry because not only does the gelling component not distribute well, Without good distribution, these components cannot contribute to the cleaning performance. In addition, the incorporation of certain ingredients that have a tendency to gel or solidify into detergents has a negative effect on the flowability of the product.

Another problem with certain detergent components, such as aluminosilicates, amorphous silicates, coarse silicate materials, is that they do not always dissolve well. This can result in reduced cleaning performance or adhesion of the product in the fabric or washing machine.

The present inventors have discovered that even well-dispersed ingredients often have a tendency to adhere to fabrics and form residues upon washing without being thoroughly dissolved. On the other hand, components that dissolve well have a tendency to gel on initial contact with water. The present inventors have found that the builder component containing the powder crystal-laminated silicate in which the particles have a particle size of less than about 100 microns and a weight average particle size of about 15 microns or more easily dissolves and exhibits excellent building properties. That's what we found here. Preferably, the builder component comprises 90% by weight of the particles, 17.3-88.2.
It has a micron particle size.

They compare detergent compositions containing this builder component with other silicate materials, such as larger and smaller particle size materials, aluminosilicates, amorphous materials or non-laminated materials. It has been found that in washing machines and fabrics it has improved flowability, improved dispensability, reduced gelling properties and less product retention in dispensers. It is believed that the laminated structure is essential in reducing gel formation, while particle size is essential in providing a product that can be distributed and dissolved while having good flowability. In addition, it is believed that the powdered material has an altered surface structure, resulting in improved building and distribution. In addition, complete mixing of the crystal-laminated silicate material with other detergent ingredients that have a tendency to form residues or gel, such as surfactants, especially anionic surfactants, results in residue formation and various It has been found that the gelling of the components is reduced, improving the distribution of the components and the efficient cleaning performance.

[0008]

[Summary of the Invention]

The present invention relates to at least one crystalline laminated silicate having a particle size of less than 150 microns or even less than 102 microns, and at the same time having a weight average particle size of 15.0 microns or more, preferably 16.0-48.8 microns. A builder component is provided that includes a powdered crystal-laminated silicate at 95% by weight, or even at 98% or 100%. The builder component is particularly useful in solid detergent compositions, especially solid laundry and dishwashing detergent compositions.

[0009] The present invention provides a detergent composition containing surfactants and other detergent components that has a particle size of less than 150 microns or even less than 102 microns, while simultaneously improving the dispensability of the detergent. Powdered crystalline silicate comprising at least 95% by weight, or even 98% or 100%, crystalline laminated silicate having a weight average particle size of greater than or equal to 0.0 microns, preferably 16.0-48.8 microns The invention also relates to the use of builder systems containing.

[0010]

DETAILED DESCRIPTION OF THE INVENTION Builder Component Crystalline Silicate The builder component powder crystal laminate silicate of the present invention, as described in the Malvern Instrument user manual, has a crystallized layered silicate as measured by a Malvern Instruments SB.OC light scattering device. At least 95% by weight of silicate or even 98%
% Or even 100% has a particle size of less than 150 microns or even less than 102 microns, or even less than 88.2 microns, or even less than 65.6 microns, while at the same time being 15.0 microns or more, preferably It has a weight average particle size of 16.0-48.8 microns or even 17.3-42.1 microns. Preferably, when the weight average particle size is 16.0 to 48.8 microns, at least 90% by weight of the particles is 17.3 to 88.2 microns, as measured by a Malvern Instruments SB.OC light scattering device. Having a diameter of 17.3 to 42.
At 1 micron, at least 90% by weight of the particles have a particle size of 23.3 to 76.0 microns.

The pulverulent material is obtained by pulverizing a crystal-laminated silicate material having a larger particle size than the material of the present invention by any pulverizing method, preferably in a ceramic ball mill or air jet mill.

The preferred crystalline layered silicate herein have the following general _{formula: NaMSi x O 2x + 1 ·} yH 2 O above wherein M is sodium or hydrogen, x is the number of 1.9 to 4 Yes, y is 0
-20. This type of crystal-laminated sodium silicate is EP-A-0
164514 and their method of preparation is described in DE-A-3417649.
And DE-A-3740243. For the purposes of the present invention, x in the above general formula has a value of 2, 3 or 4, and is preferably 2. M is preferably H, K, Na or a mixture thereof, preferably Na. The most preferred material is α-N, commercially available, for example, as NaSKS-6 from Clariant.
a ₂ Si ₂ O ₅ , β-Na ₂ Si ₂ O ₅ , δ-Na ₂ Si ₂ O ₅ or mixtures thereof, preferably at least 75% -Na ₂ Si ₂ O ₅ .

Crystal-stacked silicate materials, in particular of the formula Na ₂ Si ₂ O ₅ , are for example EP 5789
It may optionally have other elements, such as B, P, S, obtained by a process as described in 86-B.

The components of the present invention may also contain other detergent builders or other detergent components, as described herein. Typically, the builder component contains up to 85%, preferably 75 or 50%, of other components. Therefore, the builder component of the present invention preferably comprises a complete mixture of the crystal-laminated silicate and other components. As used herein, "perfect mixing / mixing" or "perfect mixture"
For the purposes of the present invention, it is meant that the components of the particles are substantially uniformly distributed throughout the particles.

A complete mixture is obtained by any process that mixes the components, which can be part of a spray drying process, a tableting process, an extrusion process, and a granulation process, such as an agglomeration process. . Thus, preferably, the first step comprises forming a mixture of the crystal-laminated silicate and another component, preferably a surfactant, and granulating the mixture to form particles. The complete mixing step is preferably performed by aggregating the surfactant and the crystal-laminated silicate. This may be done in any conventional agglomeration process. Thus, the builder component preferably takes the form of an agglomerate.

Preferred materials are organic acids or salts, including (poly) carboxylic acids and salts thereof, including polymeric compounds such as acrylic acid and / or maleic acid polymers, carbonates and sulfates, as described herein. And inorganic acids or salts including other silicate materials, such as amorphous silicates, metasilicates, other crystalline silicates and aluminosilicates.

The builder component of the present invention preferably contains at least a surfactant, preferably including at least an anionic surfactant, as described below. Particles are 10-60% by weight, preferably 20-50% or even 35-45%
35-90%, preferably 40-80% or even 45-65%
% Of the crystal-laminated silicate. It is preferable to contain a surfactant as another component. Preferably, the weight ratio of crystal-laminated silicate to surfactant in the builder component is from 4: 5 to 7: 3, more preferably from 1: 1 to 2: 1, and most preferably from 5: 4 to 3: 2.

Preferably, the builder component contains less than 10% by weight of free water, preferably less than 5% by weight. The free moisture used here is determined by placing 5 g of the builder component in a Petri dish, placing the Petri dish in a convection oven at 50 ° C. for 2 hours, and then measuring the weight loss due to water evaporation.

Preferably, the complete mixture contains a polymeric binder material. then,
It is preferred to use as little binder material as possible. Preferably, the complete mixture contains less than 25%, preferably less than 10%, more preferably less than 5%, most preferably 0% by weight of the ethylene oxide polymer.

The builder component is preferably present in the detergent composition. The builder composition is then preferably present in the form of individual particles, preferably agglomerates, having a weight average particle size of 150 to 1700 microns, more preferably 80% by weight of the particles are 300 microns Particles having the above particle size (80% by weight with Tyler sieve mesh 48) and less than 10% by weight (with Tyler mesh sieve 14)
It has a particle size greater than 1180 microns or even 710 microns (with Tyler mesh sieve 24).

The detergent composition may have any form, including aqueous and non-aqueous liquids,
Preferably, the composition is a solid composition in the form of bars, flakes, extrudates, and the composition is in the form of granules or tablets. When the composition consists of granules, the granules preferably have a particle size of 150 to 2500 microns or even 1500 microns, or more preferably 80% by weight
Have a particle size of 300 microns or more (80% by weight with Tyler sieve mesh 48) and less than 10% by weight granules have a particle size of 1180 microns or even 710 microns (with Tyler mesh sieve 24). Have.

Preferably, the detergent composition comprises 300 g / L to 1500 g / L, more preferably 4 g / L
00 g / L or even 580 g / L to 1200 g / L or even 850 g / L
L density. The detergent composition and the builder composition as described above may contain additional components,
Preferred components are described below.

[0023] Detergent compositions containing the builder component of the present invention, as a builder system or as part thereof, preferably intimately mixed with any of the components described herein, have been found to have improved distribution. Was. Therefore, the present invention provides at least 90% by weight,
Preferably, at least 95% have a particle size of 20.2 microns or more, and at least 90%
Detergent compositions containing a builder system by providing a builder system or a detergent composition containing, by weight, preferably 95%, of a powdered crystal laminated silicate having a particle size of less than 100.2 microns, Also provided are methods for improving the partitionability of an article or a component thereof.

It has been found that the dispensability of the detergent composition or its components from the dispensing drawer or dispensing device of the washing machine to the wash water is improved compared to the detergent composition without the builder component of the present invention. Is meant. As used herein, "improve partitionability" includes improved solubility, reduced gelation and reduced residue formation.

Additional Components The builder component or composition may include an additional detergent component. The exact nature of these additional components, and their level of incorporation, depends on the exact physical form of the builder component and the composition containing the builder component, and the exact nature of the washing operation in which it is used. The builder components and compositions are preferably surfactants, bleach, bleach catalysts, alkaline, additional builders, organic polymer compounds, enzymes, foam inhibitors,
It contains one or more additional detergent ingredients selected from lime soaps, dispersants, soil suspending and anti-redeposition agents, soil release agents, fragrances, brighteners, photobleaches and additional corrosion inhibitors.

Surfactant The builder component or detergent composition of the present invention preferably contains one or more surfactants. The surfactants include anionic, nonionic, cationic,
There are any surfactants known in the art, selected from amphoteric, amphoteric and zwitterionic surfactants, and mixtures thereof. It is to be understood that, for the purposes of the present invention, the detergent composition may contain a surfactant that is not present as a complete mixture with the crystal-laminated silicate, but is present as another detergent component.

Anionic Surfactants The compositions and builder components according to the present invention preferably contain an anionic surfactant. Essentially, any anionic surfactant useful for cleaning purposes may be included in the detergent composition. These include salts of anionic sulfate, sulfonate, carboxylate and sarcosinate surfactants, including, for example, sodium, potassium, ammonium and substituted ammonium salts such as the mono, di and triethanolamine salts. Anionic sulfate and sulfonate surfactants are preferred.

Highly preferred are the sulfonate and sulfate surfactants as described herein, preferably together with the cationic surfactants described herein, preferably linear or branched alkyl benzene sulfonates and It is a surfactant system containing alkyl ethoxyl sulfate.

Other anionic surfactants include isethionates such as acyl isethionates, N-acyl taurates, fatty acid amides of methyl tauride, alkyl succinates and sulfosuccinates, monoesters of sulfosuccinates (especially saturated And unsaturated C ₁₂ -C ₁₈ monoesters), diesters of sulfosuccinates (especially saturated and unsaturated C ₆ -C ₁₄ diesters), N-acyl sarcosinates. Resin acids and hydrogenated resin acids, such as rosins, hydrogenated rosins, resin acids and hydrogenated resin acids present or derived from tallow oil are also suitable.

Anionic sulfonate surfactants Highly preferred here are anionic sulfonate surfactants. Here, the those used on particularly suitable _not only salts of C 5 _{-C 20} linear or branched alkyl benzene sulfonates, alkyl ester _sulfonates, C 6 _{-C 22} primary or secondary alkane _sulfonates, C 6 _{-C 24} olefin There are also sulfonates, sulfonated polycarboxylic acids, alkyl glycerol sulfonates, fatty acyl glycerol sulfonates, fatty oleyl glycerol sulfonates and mixtures thereof. Most preferred are C ₉ -C ₁₄ straight chain alkyl benzene sulfonates.

Anionic sulphate surfactants suitable for use herein include linear and branched primary and secondary alkyl sulphates, alkyl ethoxy sulphates, fatty oleoyl glycerol sulphates, alkyl phenol ethylene oxide ether sulphates , C ₅ -C ₁₇ acyl-N- (C ₁ -C ₄ alkyl) and —N- (C ₁ -C ₂ hydroxyalkyl) glucamine sulfate, and sulfates of alkyl polysaccharides, such as sulfates of alkyl polyglucosides ( Nonionic non-sulfate compounds are also described herein).

The alkyl sulfate surfactants are preferably straight-chain and branched primary _{C 1} 0 _{-C 18} alkyl sulfates, more preferably _C 11 _{-C 15} branched chain alkyl sulfates and _C 12 _{-C 14} linear alkyl sulfate Is selected from Preferably, the alkyl ethoxy sulphate surfactant is selected from the group consisting of C ₁₀ -C ₁₈ alkyl sulphates ethoxylated with 0.5 to 20 moles of ethylene oxide per molecule. More preferably, the alkyl ethoxy sulfate surfactant is a C ₁₁ -C ₁₈ , most preferably a C ₁₁ -C ₁₅ alkyl sulfate ethoxylated with 0.5 to 7, preferably 1 to 5 moles of ethylene oxide per molecule. It is.

In a particularly preferred aspect of the invention, a mixture of the preferred alkyl sulphates and / or sulphonates and alkyl ethoxy sulphate surfactants is used. Such a mixture is disclosed in PCT patent application WO 93/18124.

Anionic Carboxylate Surfactants Suitable anionic carboxylate surfactants include alkyl ethoxy carboxylate, alkyl polyethoxy polycarboxylate surfactant and soap ('alkyl carboxyl'), particularly as described herein. There are some second-class soaps that look like.

Suitable alkylethoxycarboxylates have the formula RO (CH ₂ CH ₂ O) _x C
Some have H ₂ COO ⁻ M ⁺ , where R is a C ₆ -C ₁₈ alkyl group, x is 0 to 10, and the ethoxylate distribution is based on the weight of the material where x is 0. M is a cation, such that the amount is less than 20%. Suitable alkyl polyethoxy polycarboxylate surfactants include those of the formula RO- (CHR _1-
CHR ₂ -O) -R ₃ , where R is a C ₆ -C ₁₈ alkyl group, x is 1 to 25, and R ₁ and R ₂ are hydrogen, methyl acid group, succinic acid group is selected from the group consisting of hydroxy succinic acid and mixtures thereof, R ₃ is hydrogen, a substituted or unsubstituted hydrocarbon having from 1 to 8 carbon atoms, and is selected from the group consisting of a mixture thereof.

[0036] Suitable soap surfactants include secondary soap surfactants having a carboxyl unit attached to a secondary carbon. The secondary soap surfactant preferred here for use is 2-
From the group consisting of water-soluble salts of methyl-1-undecanoic acid, 2-ethyl-1-decanoic acid, 2-propyl-1-nonanoic acid, 2-butyl-1-octanoic acid and 2-pentyl-1-heptanoic acid The water-soluble member of choice. Certain soaps may also be included as suds suppressors.

Alkali Metal Sarcosinate Surfactants Another suitable anionic surfactant is an alkali metal sarcosinate of the formula R-CON (R ¹ ) CH ₂ COOM, where R is a C ₅ -C ₁₇ linear or branched. An alkyl or alkenyl group, R ¹ is a C ₁ -C ₄ alkyl group, and M is an alkali metal ion. Preferred examples are myristyl and oleoyl methyl sarcosinate in the form of the sodium salt.

[0038] on to exhibit the intermediate chain branched anionic surfactants particularly improved detergent performance, where a highly preferred are, A ^b moiety is a branched primary alkyl moiety having the formula, the formula An alkyl chain intermediate chain branched surfactant compound of the formula:

Embedded image In the above, the total number of carbon atoms in the branched primary alkyl moiety of this formula (including the R, R ¹ and R ² branches) is 13-19; R, R ¹ and R ² are each independently hydrogen and C ₁ -C ₃ alkyl (preferably methyl), provided that R, R ¹ and R ² are not all hydrogen and when z is 0, at least R or R ¹ is not hydrogen; w is an integer from 0 to 13; x is an integer from 0 to 13; y is an integer from 0 to 13; z is an integer from 0 to 13;
y + z is 7-13.

In general, in a surfactant-based intermediate-chain branched surfactant compound, a certain branch (ie, a position along the chain of the R, R ¹ and / or R ² portion in the above formula) is an interface. Preferred along the main chain of the activator over other branches. The formula below shows the range of mid-chain branching (ie, where the branch point is present), the preferred mid-chain branching range, and the more preferred mid-chain branching range for the monomethyl branched alkyl ^Ab portion useful in the present invention.

Embedded image It should be noted that for monomethyl substituted surfactants, these ranges exclude the two terminal carbon atoms of the chain and the carbon atom immediately adjacent to the -XB group.

The following formula illustrates the range of mid-chain branching, the preferred range of mid-chain branching, and the more preferred range of mid-chain branching for dimethyl-substituted alkyl ^Ab moieties useful in the present invention.

Embedded image In the above formula, A ^b moiety is any quaternary substituted carbon atoms (i.e., coupled directly to the four one carbon atom is a carbon atom) also surfactant compounds are preferably non have.

The most preferred mid-chain branched surfactant compound for use in the present detergent compositions is a mid-chain branched primary alkyl sulfonate, even more preferably a sulfate surfactant. For the purposes of the present invention, the surfactant system preferably comprises a mixture of two or more intermediate-chain branched primary alkyl sulphate or sulphonate surfactants.

Preferred medium chain branched primary alkyl sulphate surfactants have the formula:

Embedded image These surfactants have a linear primary alkyl sulfate backbone, preferably containing 12 to 19 carbon atoms (ie, the longest carbon linear chain containing sulfated carbon atoms), and their branches Such primary alkyl moieties preferably have a total of at least 14, and preferably no more than 20, carbon atoms. In surfactant systems containing two or more of these sulfate surfactants, the average total number of carbon atoms in the branched primary alkyl moiety is preferably in the range of greater than 14.5 and up to about 17.5. Thus, the surfactant system preferably comprises at least one branched primary alkyl sulphate surfactant compound having a longest carbon straight chain of 12 or more carbon atoms or 19 or less carbon atoms, and contains branched. The total number of carbon atoms must be at least 14, and for branched primary alkyl moieties the average total number of carbon atoms is greater than 14.5 and up to about 17.5.

R, R ¹ and R ² are each independently selected from hydrogen and a C ₁ -C ₃ alkyl group (preferably hydrogen or C ₁ -C ₂ alkyl, more preferably hydrogen or methyl, most preferably methyl). Provided that R, R ¹ and R ² are not all hydrogen. Further, when z is 1, at least R or R ¹ is not hydrogen.

M is hydrogen or a salt-forming cation, depending on the method of synthesis. Examples of salt-forming cations are lithium, sodium, potassium, calcium, magnesium, quaternary alkylamines having the formula:

Embedded image (Wherein R ³ , R ⁴ , R ⁵ and R ⁶ are independently hydrogen, C ₁ -C ₂₂ alkylene, C ₄ -C ₂₂ branched alkylene, C ₁ -C ₆ alkanol, C ₁ -C ₂₂ alkenylene, C ₄ -C ₂₂ branched alkenylene) and mixtures thereof. Preferred cations are ammonium (R ³ , R ⁴ , R ⁵ and R ⁶ are hydrogen), sodium, potassium, mono, di and trialkanol ammonium,
And mixtures thereof. The monoalkanol ammonium compounds of the invention are those wherein R ³ is a C ₁ -C ₆ alkanol and R ⁴ , R ⁵ and R ⁶ are hydrogen; the dialkanol ammonium compounds of the invention are those wherein R ³ and R ⁴ are C ₁ -C ₆ alkanols, wherein R ⁵ and R ⁶ are hydrogen; trialkanol ammonium compounds of the present invention are those wherein R ³ , R ⁴ and R ⁵ are C ₁ -C ₆ alkanols and R ⁶ is hydrogen. Preferred alkanol ammonium salts of the present invention are those having the following formula:
Di and tri quaternary ammonium _{^{compounds: H 3 N + CH 2 CH}} 2 OH, H 2 N + (CH 2 CH 2 OH) 2, HN + (CH 2 CH 2 OH) 3 preferred M is sodium, potassium and a said C ₂ alkanol ammonium salts, and most preferred is sodium. Further with respect to the above formula, w is an integer from 0 to 13; x is an integer from 0 to 13; y is an integer from 0 to 13; z is an integer at least 1; w + x + y + z is from 8 to 14; Is an integer.

Preferred medium chain branched primary alkyl sulphate surfactants have 13 carbon atoms in the backbone and 1, 2 or 3 branching units of a total of 3 carbon atoms (ie, R
, R ¹ and / or R ² ) with a total carbon primary alkyl sulfate surfactant (so that the total number of carbon atoms is at least 16). Preferred branching units are one propyl branching unit or three methyl branching units.

Other preferred surfactant systems of the present invention have one or more branched primary alkyl sulfates having the formula:

Embedded image In the above, the total number of carbon atoms including the branch is 15 to 18, and when two or more of these sulfates are present, the average total number of carbon atoms in the branched primary alkyl moiety having the above formula is greater than 14.5. R ¹ and R ² are each independently hydrogen or C ₁ -C ₃ alkyl; x is from 0 to 1
1 is; y is 0-11; z is at least 2; x + y + z is 9-13
Provided that R ¹ and R ² are not both hydrogen.

Preferably, the surfactant system is such that R ¹ and R ² are independently hydrogen or methyl, provided that R ¹ and R ² are not both hydrogen and x +
The intermediate-chain branched primary alkyl sulfate wherein y is 8, 9 or 10 and z is at least 2 is at least 20% by weight of the system, more preferably at least 60% by weight of the system, even more Preferably at least 90% by weight, the average total number of these sulfate surfactants is preferably 15-17, more preferably 16-17.

Further, a preferred surfactant system comprises one or more mid-chain branched alkyl sulfates having the formula: at least about 20% by weight of the system, more preferably at least 6%.
0% by weight, even more preferably at least 90% by weight:

Embedded image Or a mixture thereof; wherein M represents one or more cations; a, b, d, and e
Is an integer, a + b is 10-16, d + e is 8-14, and when a + b = 10, a is an integer of 2-9, b is an integer of 1-8; a + b = 11 When a is an integer of 2 to 10, b is an integer of 1 to 9; When a + b = 12, a is an integer of 2 to 11; b is an integer of 1 to 10; When a + b = 13, a is an integer of 2 to 12, b is an integer of 1 to 11; when a + b = 14, a is an integer of 2 to 13; b is an integer of 1 to 12; when a + b = 15, a is An integer of 2 to 14, b is an integer of 1 to 13; when a + b = 16, a is an integer of 2 to 15; b is an integer of 1 to 14; when d + e = 8, d is 2 An integer of 7 and e is an integer of 1 to 6; when d + e = 9, d is an integer of 2 to 8 and e is an integer of 1 to 7; And d is an integer of 2 to 9 and e is an integer of 1 to 8; when d + e = 11, d is an integer of 2 to 10; e is an integer of 1 to 9; d is an integer of 2 to 11, e is an integer of 1 to 10; When d + e = 13, d is an integer of 2 to 12; e is an integer of 1 to 11; When d + e = 14, d is An integer from 2 to 13 and e is an integer from 1 to 12; when two or more of these sulfate surfactants are present in the surfactant system, the average of the carbon atoms in the branched primary alkyl moiety having the above formula The total number is in the range of greater than 14.5 and up to about 17.5.

Preferred monomethyl branched primary alkyl sulfates are 3-methylpentadecanol sulfate, 4-methylpentadecanol sulfate, 5-methylpentadecanol sulfate, 6-methylpentadecanol sulfate, 7-methylpentadecanol sulfate,
Methylpentadecanol sulfate, 8-methylpentadecanol sulfate, 9-methylpentadecanol sulfate, 10-methylpentadecanol sulfate, 11-methylpentadecanol sulfate, 12-methylpentadecanol sulfate, 13-methylpentane Decanol sulfate, 3-
Methylhexadecanol sulfate, 4-methylhexadecanol sulfate, 5-methylhexadecanol sulfate, 6-methylhexadecanol sulfate, 7-methylhexadecanol sulfate, 8-methylhexadecanol sulfate, 9-methylhexa Decanol sulfate, 10-methylhexadecanol sulfate, 11-methylhexadecanol sulfate,
It is selected from the group consisting of 12-methylhexadecanol sulfate, 13-methylhexadecanol sulfate, 14-methylhexadecanol sulfate and mixtures thereof.

Preferred dimethyl branched primary alkyl sulfates are 2,3-methyltetradecanol sulfate, 2,4-methyltetradecanol sulfate, 2,5
-Methyltetradecanol sulfate, 2,6-methyltetradecanol sulfate, 2,7-methyltetradecanol sulfate, 2,8-methyltetradecanol sulfate, 2,9-methyltetradecanol sulfate, 2
, 10-methyltetradecanol sulfate, 2,11-methyltetradecanol sulfate, 2,12-methyltetradecanol sulfate, 2,3-
Methylpentadecanol sulfate, 2,4-methylpentadecanol sulfate, 2,5-methylpentadecanol sulfate, 2,6-methylpentadecanol sulfate, 2,7-methylpentadecanol sulfate, 2,
8-methylpentadecanol sulfate, 2,9-methylpentadecanol sulfate, 2,10-methylpentadecanol sulfate, 2,11-methylpentadecanol sulfate, 2,12-methylpentadecanol sulfate, 2, It is selected from the group consisting of 13-methylpentadecanol sulfate and mixtures thereof.

The following branched primary alkyl sulfates containing 16 carbon atoms and having one branching unit are examples of preferred branched surfactants useful in the compositions of the present invention: 5-methyl having the formula: Pentadecyl sulfate

Embedded image 6-methylpentadecyl sulfate having the formula

Embedded image 7-methylpentadecyl sulfate having the formula:

Embedded image 8-methylpentadecyl sulfate having the formula

Embedded image 9-methylpentadecyl sulfate having the formula:

Embedded image 10-methylpentadecyl sulfate having the formula:

Embedded image In the above formula, M is preferably sodium.

The following branched primary alkyl sulphates containing 17 carbon atoms and having two branching units are examples of preferred branched surfactants according to the invention: 2,5-dimethylpentadecyl having the formula: Sulphate

Embedded image 2,6-dimethylpentadecyl sulfate having the formula:

Embedded image 2,7-dimethylpentadecyl sulfate having the formula

Embedded image 2,8-dimethylpentadecyl sulfate having the formula

Embedded image 2,9-dimethylpentadecyl sulfate having the formula

Embedded image 2,10-dimethylpentadecyl sulfate having the formula

Embedded image In the above formula, M is preferably sodium.

Alkoxylated nonionic surfactants Essentially any alkoxylated nonionic surfactant is suitable here.
Ethoxylated and propoxylated nonionic surfactants are preferred. Preferred alkoxylated surfactants are nonionic condensates of alkylphenols, nonionic ethoxylated alcohols, nonionic ethoxylated / propoxylated fatty alcohols, nonionic ethoxylate / propoxylate condensates with propylene glycol, and propylene oxide / It can be selected from the class of nonionic ethoxylate condensation products with ethylenediamine adducts.

Nonionic Alkoxylated Alcohol Surfactants Nonionic surfactants can also be present in the detergent composition. Preferably, the level of ethoxylated nonionic surfactant in the complete mixture is no more than 10% by weight of the mixture, preferably no more than 5%. The condensation products of aliphatic alcohols with 1 to 25 mol of alkylene oxides, in particular ethylene oxide and / or propylene oxide, are suitable for use here. The alkyl chain of the aliphatic alcohol may be straight or branched, primary or secondary and usually has from 6 to 22 carbon atoms. Condensation products of alcohols having alkyl groups of 8 to 20 carbon atoms with 2 to 10 moles of ethylene oxide per mole of alcohol are particularly preferred.

Nonionic polyhydroxy fatty acid amide surfactants Suitable polyhydroxy fatty acid amides for use herein are those having the structural formula R ² CONR ¹ Z: R ¹ is H, C ₁ -C ₄ hydrocarbyl, 2- Hydroxyethyl, 2-hydroxypropyl, ethoxy, propoxy or mixtures thereof, preferably C ₁ -C ₄ alkyl, more preferably C ₁ or C ₂ alkyl, most preferably C ₁ alkyl (ie methyl); R ² _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 1 7} alkyl or alkenyl Or a mixture thereof; Z is a linear hydrocarbyl chain and Or an alkoxylated (preferably ethoxylated or propoxylated) derivative thereof having at least three hydroxyls directly attached to the chain of Z is preferably derived from a reducing sugar in a reductive amination reaction, more preferably Z is glycityl.

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

A nonionic alkyl polysaccharide surfactant: a polysaccharide having 6 to 30 carbon atoms and a polysaccharide having 1.3 to 10 saccharide units,
Alkyl polysaccharides suitable for use herein, for example, having the hydrophilic groups of a polyglycoside are described in Llenado US Pat. No. 4,565,647 issued Jan. 21, 1986.
Are disclosed. Preferred alkylpolyglycosides have the ^{_{formula: R 2 O (C n H}} 2n O) t ( _{glycosyl) x} above wherein ^{R 2} is an alkyl, alkylphenyl, hydroxyalkyl, hydroxy alkylphenyl, and mixtures thereof Selected from the group consisting of alkyl groups having 10 to 18 carbon atoms; n is 2 or 3; t is 0-10; x is 1.3-8. Glycosyl is preferably derived from glucose.

Amphoteric surfactants Suitable amphoteric surfactants for use herein include amine oxide surfactants and alkyl amphocarboxylic acids. Suitable amine oxides, there is a compound having the formula _{^{R 3 (OR 4) x NO}} (R 5) 2, wherein alkyl ^{R 3} is having carbon atoms of 8 to 26, hydroxyalkyl, acyl amidopropyl and alkyl is selected from phenyl groups, or mixtures thereof, R ⁴ is an alkylene or hydroxyalkylene group or mixtures thereof having 2 to 3 carbon atoms, x is 0-5, preferably 0-3, each R ⁵ Is an alkyl or hydroxyalkyl group having 1 to 3 carbon atoms,
Or a polyethylene oxide group having 1 to 3 ethylene oxide groups. Preferred are C ₁₀ -C ₁₈ alkyldimethylamine oxide and C ₁₀ -C ₁₈ acylamidoalkyldimethylamine oxide. Suitable examples of alkyl amphodicarboxylic acids are available from Miranol, Inc., Dayton, NJ.
iranol (TM) C2M Conc.

Zwitterionic Surfactants Zwitterionic surfactants can also be incorporated into the detergent compositions or builder components according to the present invention. These surfactants can be broadly described as derivatives of secondary and tertiary amines, derivatives of heterocyclic secondary and tertiary amines, or derivatives of quaternary ammonium, quaternary phosphonium or tertiary sulfonium compounds. . Betaine and sultaine surfactants are zwitterionic surfactants exemplified for use herein. Suitable betaines are compounds having the formula R (R ¹ ) ₂ N ⁺ R ² COO ⁻ , where R is a C ₆ -C ₁₈ hydrocarbyl group, and each R ¹ is typically C ₁ -C _3. Alkyl and R ² is a C ₁ -C ₅ hydrocarbyl group. Preferred betaines are C _12-18 dimethyl ammonio hexanoate and C _10-18 acylamido propane (or ethane) dimethyl (or diethyl) betaines. Complex betaine surfactants are also suitable for use herein.

Cationic surfactants Suitable cationic surfactants for use herein include quaternary ammonium surfactants. Preferably, quaternary ammonium surfactants are the mono C ₆ -C _16, preferably C ₆ -C 10 _N-alkyl or alkenyl ammonium surfactants, the remaining N positions are methyl, hydroxyethyl or hydroxypropyl groups Has been replaced. Monoalkoxylated and bisalkoxylated amine surfactants are also preferred.

[0061] Another suitable group of cationic surfactants that can be used in the present detergent compositions or components are cationic ester surfactants. Cationic ester surfactants are preferably water-dispersible, surface-active compounds having at least one ester (ie, -COO-) linkage and at least one positively charged group. Suitable cationic ester surfactants, including choline ester surfactants, include
For example, it is disclosed in U.S. Patent Nos. 4228042, 4239660 and 4260529.

In one preferred aspect, the ester linking chain and the positively charged group are at least 3 atoms (ie, 3 atom chain length), preferably 3-8 atoms, more preferably 3-5 atoms, most preferably It is separated from each other in the surfactant molecule by a spacer group consisting of a chain with three atoms. The atoms forming the spacer group are selected from the group consisting of carbon, nitrogen, oxygen and mixtures thereof, with the proviso that any nitrogen or oxygen in the chain is bonded to only carbon in the chain. Therefore, for example, -O-O-(i.e., peroxide), - a spacer group having a N-N-and -N-O-linked chains are excluded, on the other hand, for example, _-CH 2 -O-CH ₂ - and -CH ₂ -NH-CH ₂ - spacer group having a binding chain contained. In a preferred aspect, the spacer group contains only carbon atoms, and most preferably the chain is a hydrocarbyl chain.

Cationic monoalkoxylated amine surfactants, preferably cationic monoalkoxylated amine surfactants of the following general formula I, are highly preferred here:

Embedded image The formula R ¹ is from about 6 to about 18 carbon atoms, is preferably 6 to about 16 carbon atoms, most preferably an alkyl or alkenyl moiety having from about 6 to about 14 carbon atoms; R ² and R ³ are each independently an alkyl group having from 1 to about 3 carbon atoms, preferably methyl; most preferably, R ² and R ³ are both methyl groups; R ⁴ is hydrogen (preferred); Selected from methyl and ethyl; X ⁻ is an anion which provides electroneutrality, such as chloride, bromide, methylsulfate, sulfate, etc .; A is an alkoxy group, especially ethoxy, propoxy or butoxy group; To about 30, preferably 2 to about 15, and most preferably 2 to about 8.

Preferably, the ApR ⁴ group in Formula I has p = 1 and is a hydroxyalkyl group having 6 or less carbon atoms, and the —OH group is a quaternary group having 3 or less carbon atoms. Separated from ammonium nitrogen atoms. Particularly preferred ApR ⁴ groups are —CH ₂ CH ₂ OH, —CH ₂ CH ₂ CH ₂ OH, —CH ₂ CH (CH ₃ ) OH and —CH (CH ₃ ) CH ₂ OH, and —CH ₂ CH ₂ OH Is particularly preferred. Preferred R ¹ groups are straight-chain alkyl groups. Linear ^{R 1} groups having from 8 to 14 carbon atoms are preferred.

[0065] Another highly preferred cationic monoalkoxylated amine surfactant for use herein is of the formula:

Embedded image In the above formula, R ¹ represents C ₁₀ -C ₁₈ hydrocarbyl and mixtures thereof, especially C _10-
C ₁₄ alkyl, preferably C ₁₀ and C ₁₂ alkyl, and X is an anion convenient for charge balancing, preferably chloride or bromide. Thus, compounds of the type described above include ethoxy (CH ₂ CH ₂ O) units (E
O) is butoxy, isopropoxy [CH (CH ₃ ) CH ₂ O] and [CH ₂ C
H (CH ₃ ) O] units (i-Pr) or n-propoxy units (Pr), or those replaced with a mixture of EO and / or Pr and / or i-Pr units.

The level of cationic monoalkoxylated amine surfactant used in the detergent composition of the present invention is preferably 0.1-20% by weight of the composition, more preferably 0.1%.
It is 2 to 7%, most preferably 0.3 to 3.0%.

Cationic bisalkoxylated amine surfactant The cationic bisalkoxylated amine surfactant preferably has the following general formula II
have:

Embedded image Wherein R ¹ is from about 8 to about 18 carbon atoms, preferably from 10 to about 16 carbon atoms;
Most preferably, it is an alkyl or alkenyl moiety having about 10 to about 14 carbon atoms; R ² is an alkyl group having 1 to 3 carbon atoms, preferably methyl; R ³ and R ⁴ are independently And X is selected from hydrogen (preferred), methyl and ethyl; X ⁻ is an anion sufficient to provide electroneutrality, such as chloride, bromide, methyl sulfate, sulfate, etc .; A and A ′ are independent And
Each is 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, and most preferably p and q are both 1.

A highly preferred cationic bisalkoxylated amine surfactant for use herein is of the formula:

Embedded image Wherein R ¹ is C ₁₀ -C ₁₈ hydrocarbyl and mixtures thereof, especially C ₁₀ ,
C ₁₂ , C ₁₄ alkyl and mixtures thereof. X is an anion convenient for charge balancing, preferably chloride. With respect to the general cationic bisalkoxylated amine structure described above, R ¹ in the preferred compound is derived from a (coconut) C ₁₂ -C ₁₄ alkyl fraction fatty acid,
R ² is methyl, ApR ³ and A'qR ⁴ are each monoethoxy.

[0069] Other cationic bisalkoxylated amine surfactants useful herein include compounds of the formula:

Embedded image Wherein R ¹ is C ₁₀ -C ₁₈ hydrocarbyl, preferably C ₁₀ -C ₁₄ alkyl, independently p is 1 to about 3, q is 1 to about 3, and R ² is C ₁ -C ₃ alkyl, preferably methyl, X is an anion, in particular chloride or bromide.

Other compounds of the above type include ethoxy (CH ₂ CH ₂ O) units (EO) with butoxy (Bu), isopropoxy [CH (CH ₃ ) CH ₂ O] and [CH ₂ C
H (CH ₃ ) O] units (i-Pr) or n-propoxy units (Pr), or those replaced by a mixture of EO and / or Pr and / or i-Pr units.

The perhydrate bleach builder component, preferably a preferred additional component of the composition, is a perhydrate bleach, such as metal perborates, metal percarbonates, especially the sodium salt. Perborate may be mono- or tetra-hydrated. Sodium percarbonate has a formula corresponding to 2Na ₂ CO ₃ .3H ₂ O ₂ and is commercially available as a crystalline solid. Potassium peroxy monopersulfate is another optional inorganic perhydrate salt useful in the present detergent compositions.

Organic Peroxy Acid Bleaching System A preferred feature of the present composition or agglomerate is an organic peroxy acid bleaching system. In one preferred embodiment, the bleaching system contains a source of hydrogen peroxide and an organic peroxyacid bleach precursor compound. Generation of the organic peroxyacid occurs by an in situ reaction of its precursor with a source of hydrogen peroxide. Preferred sources of hydrogen peroxide include inorganic perhydrate bleach, such as the perborate bleach of the present invention. In another preferred embodiment, the preformed organic peroxyacid is directly incorporated into the composition. Compositions containing a mixture of a hydrogen peroxide source and an organic peroxyacid precursor together with the preformed organic peroxyacid are also contemplated.

Peroxyacid bleach precursor The peroxyacid bleach precursor is a compound that reacts with hydrogen peroxide in a perhydrolysis reaction to generate peroxyacid. Typically, the peroxyacid bleach precursor is represented as follows:

Embedded image In the above formula, L is a leaving group, X can be essentially any functional group, and the structure of the peroxyacid resulting from perhydrolysis is:

Embedded image The peroxyacid bleach precursor compound is preferably present in the detergent composition in an amount of from 0.5 to 2%.
0% by weight, more preferably 1 to 15% by weight, most preferably 1.5 to 10% by weight
At the level of

Suitable peroxyacid bleach precursor compounds typically have one or more N- or O-acyl groups, the precursors of which can be selected from a wide range of classes. Suitable classes include anhydrides, esters, imides, lactams, and acylated derivatives of imidazoles and oximes. Examples of useful substances belonging to these classes are disclosed in GB-A-1586789. Suitable esters are G
BA-836988, 864798, 1147871, 2143231 and EP-A-0170386.

The leaving group, hereinafter the L group, must be sufficiently reactive that the perhydrolysis reaction occurs within an optimal time frame (eg, a wash cycle). However,
If L is too reactive, the activator will have difficulty stabilizing the bleaching composition for use.

[0076] Preferred L groups are selected from the group consisting of: and mixtures thereof:

Embedded image In the above formula, R ¹ is an alkyl, aryl or alkaryl group having ¹ to 14 carbon atoms, R ³ is an alkyl chain having 1 to 8 carbon atoms, R ⁴ is H or R ³ , Y is H or a solubilizing group. R ¹ , R ³ and R ⁴ are each, for example, alkyl, hydroxy, alkoxy, halogen, amine, nitrosyl,
It may be substituted with essentially any functional group, including amides and ammonium or alkyl ammonium groups.

[0077] Preferred dissolution groups _{^{-SO 3 - M +, -CO 2}} - M +, -SO 4 - M +, -N + (R 3) 4 X - and _{^{O ← N (R 3) 3}} , most preferably is _-SO ³ - ^{M +} and _-CO ² - a ^{M +,} where ^{R 3} is an alkyl chain having 1 to 4 carbon atoms, M is a cation which provides solubility to the bleach activator, X is an anion that imparts solubility to the bleach activator. Preferably, M is an alkali metal, ammonium or substituted ammonium cation, most preferably sodium and potassium, and X is a halide, hydroxide, methyl sulfate or acetate anion.

Alkyl percarboxylate bleach precursor The alkyl percarboxylic bleach precursor forms percarboxylic acid on perhydrolysis. Preferred precursors of this type yield peracetic acid on perhydrolysis.

Preferred alkyl percarboxylic acid precursor compounds of the imide type include N, N, N ′, N′-tetraacetylated alkylenediamines in which the alkylene group has 1 to 6 carbon atoms, in particular, the alkylene group having 1 to 6 carbon atoms. There are compounds with 2, 2 and 6 carbon atoms. Tetraacetylethylenediamine (TAED) is particularly preferred. TAED
Is preferably not present in the agglomerated particles of the present invention, but is preferably present in the detergent composition containing the particles.

Other preferred alkyl percarboxylic acid precursors include sodium 3,5,5-trimethylhexanoyloxybenzenesulfonate (isoNOBS), sodium nonanoyloxybenzenesulfonate (NOBS), sodium acetoxybenzenesulfonate (ABS) and pentaacetylglucose.

Amide-Substituted Alkyl Peroxy Acid Precursors Amide-substituted alkyl peroxy acid precursor compounds, including those of the following general formula:
Here is suitable:

Embedded image In the above formula, R ¹ is an alkyl group having ¹ to 14 carbon atoms, and R ² is 1 to 14
R ⁵ is H or an alkyl group having 1 to 10 carbon atoms, and L may be essentially any leaving group. Amide-substituted bleach activator compounds of this type are described in EP-A-0170386.
It is described in.

Perbenzoic acid precursor The perbenzoic acid precursor compound produces perbenzoic acid by perhydrolysis. Suitable O-acylated perbenzoic acid precursor compounds include substituted and unsubstituted benzoyloxybenzenesulfonates; benzoylated products of sorbitol, glucose and all saccharides with benzoylating agents; N-benzoylsuccinimide, tetrabenzoylethylenediamine and N -There are imide types including benzoyl-substituted ureas. Suitable imidazole-type perbenzoic acid precursors include N-benzoylimidazole and N-benzoylbenzimidazole. Other useful N-acyl group-containing perbenzoic acid precursors include N-benzoylpyrrolidone, dibenzoyltaurine and benzoylpyroglutamic acid.

Cationic Peroxyacid Precursor The cationic peroxyacid precursor compound produces a cationic peroxyacid on perhydrolysis. Typically, the cationic peroxyacid precursor is replaced with a positively charged functional group such as an ammonium or alkylammonium group, preferably an ethyl or methylammonium group, to replace the peroxyacid moiety of the appropriate peroxyacid precursor compound. Formed by The cationic peroxyacid precursor is typically present in the solid detergent composition as a salt with a suitable anion, such as a halide ion.

The peroxyacid precursor compound substituted in such a cationic manner includes perbenzoic acid or a substituted derivative thereof, and the above-described precursor compounds. On the other hand, the peroxyacid precursor compound may be an alkylpercarboxylic acid precursor compound or an amide-substituted alkylperoxyacid precursor as described above.

The cationic peroxyacid precursors are disclosed in US Pat. Nos. 4,904,406, 4,751
, 015,4,988,451,4,397,757,5,269,962,5
, 127,852, 5,093,022, 5,106,528, UK1,382
, 594, EP 475, 512, 458, 396 and 284, 292, and JP 87-318, 332. Examples of preferred cationic peroxyacid precursors are described in UK patent application 9407944.
. 9 and US patent applications 08 / 298,903, 08 / 298,650, 08/29.
8904 and 08/298906.

Suitable cationic peroxyacid precursors include ammonium or alkyl ammonium substituted alkyl or benzoyloxybenzene sulfonates, N-acylated caprolactam, and monobenzoyl tetraacetylglucose benzoyl peroxide. Preferred cationic peroxyacid precursors of the N-acylated caprolactam class include trialkyl ammonium methylene benzoyl caprolactam and trialkyl ammonium methylene alkyl caprolactam.

Benzoxazine organic peroxyacid precursors are also suitable, for example precursor compounds of the benzoxazine type as disclosed in EP-A-332,294 and EP-A-482,807, especially those having the formula :

Embedded image In the above formula, R ₁ is H, alkyl, alkaryl, aryl or arylalkyl.

The preformed organic peroxyacid detergent composition is typically present in an amount of from 1 to 15%, more preferably from 1 to 10%, by weight of the composition, in addition to or instead of the organic peroxyacid bleach precursor compound. At the level of%, it may contain preformed organic peroxy acids.

A preferred class of organic peroxyacid compounds are the amide substituted compounds of the general formula:

Embedded image In the above formula, R ¹ is an alkyl, aryl or alkaryl group having ¹ to 14 carbon atoms, R ² is an alkylene, arylene or alkarylene group having 1 to 14 carbon atoms, and R ⁵ is H or an alkyl, aryl or alkaryl group having 1 to 10 carbon atoms. Amide-substituted organic peroxyacid compounds of this type are described in EP-A-0170386.

Other organic peroxy acids include diacyl and tetraacyl peroxides, especially diperoxide decandioic acid, diperoxytetradecandioic acid and diperoxyhexadecandioic acid. Also suitable here are mono- and diperazellaic acid, mono- and diperbracylic acid, and N-phthaloylaminoperoxycaproic acid.

Bleach Catalyst The builder component or composition can contain a transition metal containing bleach catalyst. Other suitable types of bleach catalysts are heavy metal cations of predetermined bleach catalytic activity such as copper, iron or manganese cations, auxiliary metal cations having little or no bleach catalytic activity such as zinc or aluminum cations, and A catalyst system comprising a sequestering agent having a predetermined stability constant for the catalyst and the auxiliary metal cation, particularly ethylenediaminetetraacetic acid, ethylenediaminetetra (methylenephosphonic acid) and a water-soluble salt thereof. Such catalysts are US
It is disclosed in Patent 4,430,243.

Other types of bleach catalysts include the manganese-based complexes disclosed in US Pat. No. 5,246,621 and US Pat. No. 5,244,594. Preferred examples of these catalysts include Mn ^IV ₂ (uO) ₃ (1,4,7-trimethyl-1,4,7-triazacyclononane) ₂ (PF ₆ ) ₂ and Mn ^III ₂ (u- O) ₁ (u-OAc)
₂ (1,4,7-trimethyl-1,4,7-triazacyclononane) ₂ (ClO ₄ ) ₂ , Mn ^IV ₄ (uO) ₆ (1,4,7-triazacyclononane) ₄ (Cl
O ₄ ) ₂ , Mn ^III Mn ^IV ₄ (uO) ₁ (u-OAc) ₂ (1,4,7-trimethyl-1,4,7-triazacyclononane) ₂ (ClO ₄ ) ₃ and the like There is a mixture of Others are described in EP-A-549,272. Other ligands suitable for use herein include 1,5,9-trimethyl-1,5
, 9-Triazacyclododecane, 2-methyl-1,4,7-triazacyclononane, 2-methyl-1,4,7-triazacyclononane, 1,2,4,7-tetramethyl-1 , 4,7-Triazacyclononane and mixtures thereof.

[0093] The bleach catalyst useful herein may be appropriately selected in the present invention. For examples of suitable bleach catalysts, see US Pat. No. 4,246,612 and US Pat.
See 84. US Pat. No. 5,194,416 which discloses a mononuclear manganese (IV) complex such as Mn (1,4,7-trimethyl-1,4,7-triazacyclononane) (OCH ₃ ) ₃ (PF ₆ ) See also.

Yet another type of bleach catalyst, as disclosed in US Pat. No. 5,114,606, is a ligand that is a non-carboxylate polyhydroxy compound having at least three consecutive C—OH groups. And manganese (III) and / or (IV). Preferred ligands include sorbitol, iditol, daritol, mannitol, xylitol, arabitol, adonitol, mesoerythritol, meso-inositol, lactose or mixtures thereof.

US Pat. No. 5,114,611 discloses a bleach catalyst consisting of a complex of a transition metal, including Mn, Co, Fe or Cu, with a non- (macro) cyclic ligand. The ligand is of the formula:

Embedded image In the above formula, R ¹ , R ² , R ³ and R ⁴ are each R ¹ -N = CR ² and R ³ -C
= As N-R ⁴ form a 5- or 6-membered ring, each H, may be selected from substituted alkyl and aryl groups. The ring may be further substituted. B is O, S
, CR ⁵ R ⁶ , NR ⁷ and C ＝ O, wherein R ⁵ , R ⁶ and R ⁷ are each H, alkyl or aryl groups, including substituted or unsubstituted groups . Preferred ligands include pyridine, pyridazine, pyrimidine, pyrazine, imidazole, pyrazole and triazole rings. Optionally, said ring is substituted with substituents such as alkyl, aryl, alkoxy, halide and nitro. Particularly preferred is the ligand 2,2'-bispyridylamine. Preferred bleach catalysts include Co, Cu, Mn, Fe-bispyridylmethane and -bispyridylamine complexes. Highly preferred catalysts include Co (
2,2′-bispyridylamine) Cl ₂ , di (isothiocyanato) bispyridylamine-cobalt (II), trisdipyridylamine-cobalt (II) perchlorate, Co (2,2-bispyridylamine) ₂ O ₂ ClO ₄ 、 Bis (2,2'-
There are bis (pyridylamine) copper (II) perchlorate, tris (di-2-pyridylamine) iron (II) perchlorate and mixtures thereof.

[0096] Other examples, four -N- seat and secondary -N- tetradentate ligand complexed with a binuclear Mn, for example, ^{_{N 4 Mn III (u-O}} ) 2 Mn IV N 4 + and [Bipy ₂ Mn ^III (uO) ₂ Mn ^IV bipy ₂ ]-(ClO ₄ ) ₃ .

Other bleach catalysts are, for example, EP 408,131 (cobalt complex catalysts), EP 384,503 and 306,089 (metallo-porphyrin catalysts), US Pat. No. 4,728,455 (manganese / Multidentate ligand catalyst), U
S4,711,748 and EP-A-224,952 (manganese absorbed on aluminosilicate catalyst), US 4,601,845 (aluminosilicate carrier carrying manganese and zinc or magnesium salts), US 4,626
, 373 (manganese / ligand catalyst), US 4,119,557 (ferric complex catalyst), German Patent Specification 2,054,019 (cobalt chelating catalyst), Canada 8
66,191 (transition metal containing salts), US Pat. No. 4,430,243 (chelants with manganese cations and non-catalytic metal cations) and US Pat.
Manganese gluconate catalyst).

[0098] Bleach catalysts are typically used in the compositions and processes in a catalytically effective amount. By "catalytically effective amount" is meant an amount sufficient to enhance the bleaching and removal of the target soil or stain from the target substrate, regardless of any of the comparative test conditions. The test conditions vary depending on the type of cleaning utensil used and the habits of the user. Some users choose to use very hot water, others use hot or even cold water in the washing operation. Of course, the catalytic performance of the bleach catalyst is affected by such considerations and the level of bleach catalyst used in a fully formulated detergent, and the bleach composition may be adjusted accordingly. In practice, and without limitation, the compositions and processes can be adjusted to provide at least about 0.1 ppm of active bleach catalyst species in the aqueous cleaning liquor, and preferably from about 1 to about 200 ppm of catalyst species in the cleaning liquor. To serve. To explain this point in more detail, a manganese catalyst of about 3 μM is effective at 40 ° C. and pH 10 under European conditions using perborate and bleach precursors. A 3-5 fold increase in concentration may be required under U.S.A. conditions to achieve similar results.

Additional Builder Material Water-Soluble Builder The builder component or, preferably, the composition may contain a water-soluble builder compound, which typically comprises from 1 to 80%, preferably from 10 to 60%, by weight of the composition. %, Most preferably from 15 to 40% by weight, in the detergent composition. The detergent composition of the present invention may contain a phosphate-containing builder substance, preferably tetrasodium pyrophosphate or, more preferably, anhydrous sodium tripolyphosphate, from 0.5 to 60%, preferably from 5 to 50%, more preferably from 5 to 50%. Preferably it is present at a level of 8-40%. It is also preferred that the composition does not contain a phosphate-containing builder substance.

Suitable water-soluble builder compounds include water-soluble monomeric polycarboxylates or their acid forms, homo- or copolymeric polycarboxylic acids or their salts (polycarboxylic acids being separated from each other by no more than 2 carbon atoms). (Having at least two carboxylic acid groups), borates, phosphates, and mixtures of any of the foregoing. Carboxylate or polycarboxylate builders are monomeric or oligomeric in type, but monomeric polycarboxylates are usually preferred for cost and performance reasons.

Suitable carboxylates having one carboxy group include the water-soluble salts of lactic acid, glycolic acid and their ether derivatives. Polycarboxylates having two carboxy groups include water-soluble salts of succinic acid, malonic acid, (ethylenedioxy) diacetate, maleic acid, diglycolic acid, tartaric acid, tartronic acid and fumaric acid, and ether carboxylate. And sulfinyl carboxylate. Polycarboxylates with three carboxy groups or their acids include, in particular, water-soluble citrates, aconitrates and citraconates, and succinate derivatives, such as carboxymethyloxysuccinates described in GB 1,379,241, UK Lactoxysuccinate described in patent 1,389,732, aminosuccinate described in Dutch application 72052073,
And oxypolycarboxylate materials such as 2-oxa-1,1,3-propanetricarboxylate described in British Patent 1,387,447. 3
The most preferred polycarboxylic acid with two carboxy groups is citric acid, preferably present at a level of 0.1 to 15%, more preferably 0.5 to 8% by weight of the composition.

[0102] Polycarboxylates having four carboxy groups are described in British Patent 1,261.
Oxydisuccinate, 1,1,2,2-ethanetetracarboxylate, 1,1,3,3-propanetetracarboxylate and 1,1
There is 1,2,3-propanetetracarboxylate. Polycarboxylates with sulfo substituents include the sulfosuccinate derivatives disclosed in British Patents 1,398,421, 1,398,422 and US Pat. No. 3,936,448, as well as British Patent 1,439,000. There is a sulfonated pyrolytic citrate described in. Preferred polycarboxylates are hydroxycarboxylates having up to 3 carboxy groups per molecule, more particularly citrates.

Mixtures of the monomeric or oligomeric polycarboxylate chelators with the parent acid, or salts thereof, such as citric acid or citrate / citric acid mixtures,
Considered as a useful builder component. The polymer or oligomeric polycarboxylate comprises less than 5% by weight of the composition;
It is preferably present at a level of less than 3%, or even less than 2% or even 0%.

[0104] Borate builders, as well as builders containing borate-forming substances capable of borate under detergent storage or washing conditions, are also useful water-soluble builders herein.

Insoluble Builder Compounds The builder component or composition may contain an insoluble builder compound, preferably at a level of only 0 to 25%, most preferably 0 to 15% by weight of the composition, or It is also present at 0-10% by weight of the product. An example of a fairly water-insoluble builder is sodium aluminosilicate. Suitable aluminosilicate zeolites have the unit cell formula Na _z [(AlO ₂ ) _z (
SiO ₂ ) _y ] xH ₂ O, where z and y are at least 6, the molar ratio of z to y is 1.0-0.5, x is at least 5, Preferably 7.5
To 276, more preferably 10 to 264. The aluminosilicate material is a hydrated form, preferably a crystal containing 10 to 28%, more preferably 18 to 22%, of water in bound form.

The aluminosilicate zeolite may be a natural substance, but is preferably derived synthetically. Synthetic crystalline aluminosilicate ion exchange materials are commercially available under the names zeolite A, zeolite B, zeolite P, zeolite X, zeolite HS and mixtures thereof. Zeolite A has the following formula: Na ₁₂ [(AlO ₂ ) ₁₂ (SiO ₂ ) ₁₂ ] xH ₂ O where x is 20-30, especially 27. Zeolite X has the formula Na ₈₆ [(Al
O ₂ ) ₈₆ (SiO ₂ ) ₁₀₆ ] · 276H ₂ O.

[0107] Another preferred aluminosilicate zeolite is a zeolite MAP builder. Zeolite MAP is described in EP 384070A (Unilever). It is a zeolite P-type alkali metal alumino having a silicon: aluminum ratio of 1.33 or less, preferably in the range of 0.9 to 1.33, more preferably in the range of 0.9 to 1.2. -Defined as silicate. Of particular interest are zeolite MAPs having a silicon: aluminum ratio of 1.15 or less, more specifically 1.07 or less.

In a preferred aspect, the zeolite MAP detergent builder comprises 1.0 to 10.0 μm
m, more preferably 2.0～7.0Myuemu, and most preferably has a particle size that is displayed as _{the d 50} value of 2.5～5.0Myuemu. the d ₅₀ value indicates that 50 wt% of the particles have a smaller diameter than that number. The particle size is measured in particular by conventional analytical techniques, such as by microscopy using a scanning electron microscope or by a laser granulometer. Other methods of measuring the d ₅₀ value is disclosed in EP384070A.

The builder component or composition may also include additional silicate materials, including amorphous silicate materials, metasilicates, and additional coarse crystalline laminated silicate materials having a particle size of 150 microns or more. The additional silicate material is preferably present at a level of less than 20%, preferably less than 15%, or even less than 10% by weight of the composition.

Heavy Sequestering Agents Heavy sequestering agents are also useful additional components herein. The heavy metal ion sequestering agent means here a component that acts to sequester (chelate) heavy metal ions. These components also have calcium and magnesium chelation abilities, but over them, they exhibit selectivity for binding heavy metal ions such as iron, manganese and copper. The heavy metal ion sequestering agent is used usually in an amount of 0.005 to 10% by weight of the composition, preferably
. 1-5%, more preferably 0.25-7.5%, most preferably 0.3-2%
Exist at the level of.

[0111] Heavy sequestering agents suitable for use herein include organic phosphonates, such as aminoalkylene poly (alkylene phosphonates), alkali metal ethane 1-hydroxydiphosphonates and nitrilotrimethylene phosphonates. Preferred among the above species are diethylenetriaminepenta (methylenephosphonate), ethylenediaminetri (methylenephosphonate), hexamethylenediaminetetra (methylenephosphonate) and hydroxyethylene 1,1-diphosphonate, 1,1-hydroxyethanediphosphonic acid And 1,1-hydroxyethanedimethylenephosphonic acid.

Other suitable heavy sequestering agents for use herein include nitrilotriacetic acid and polyaminocarboxylic acids such as ethylenediaminotetraacetic acid, ethylenediaminedisuccinic acid, ethylenediaminediglutaric acid, 2-hydroxypropylenediaminedisuccinic acid. Or have their salts.

Other suitable heavy sequestering agents for use herein are such as 2-hydroxyethyl diacetate or glyceryl iminodiacetic acid as described in EP-A-317,542 and EP-A-399,133. It is an iminodiacetic acid derivative. EP-A-516
The iminodiacetic acid-N-2-hydroxypropyl sulfonic acid and aspartic acid N-carboxymethyl N-2-hydroxypropyl-3-sulfonic acid sequestrants described in U.S. Pat. Β-alanine-N, N'-diacetate, aspartic acid-N, N'-diacetic acid, aspartic acid-N-monoacetic acid and iminodisuccinic acid sequestrants described in EP-A-509,382 are also suitable ing.

EP-A-476,257 describes suitable amino-based sequestrants. EP-A-510,331 describes suitable sequestering agents derived from collagen, keratin or casein. EP-A-528,859 describes suitable alkyliminodiacetic acid sequestering agents. Dipicolinic acid and 2-phosphonobutane-1,2,4-tricarboxylic acid are also suitable. Glycinamide-N, N
'-Disuccinic acid (GADS), ethylenediamine-N, N'-diglutaric acid (E
DDG) and 2-hydroxypropylenediamine-N, N'-disuccinic acid (H
PDDS) are also suitable.

Particularly preferred are diethylenetriaminepentaacetic acid, ethylenediamine-N,
N'-disuccinic acid (EDDS) and 1,1-hydroxyethanediphosphonic acid,
Or their alkali metal, alkaline earth metal, ammonium or substituted ammonium salts, or mixtures thereof.

Enzymes Other preferred components useful herein are one or more additional enzymes. Preferred additional enzymatic materials include commercially available lipases, cutinases, amylases, neutral and alkaline proteases, cellulases, endolases, esterases, pectinases, lactases and peroxidases conventionally formulated in detergent compositions. Suitable enzymes are described in US Patents 3,519,570 and 3,533,
139.

Preferred commercially available protease enzymes include those sold by Novo Industries A / S (Denmark) under the trade names Alcalase, Savinase, Primase, Durazym and Esperase, and those sold by Gist-Brocades under the trade names Maxatase, Maxacal and Maxapem Is sold, sold by Genencor International, and Solvay Enzym
Some are sold by es under the trade names Opticlean and Optimase. The protease enzyme may be incorporated into the composition according to the present invention at an active enzyme level of 0.0001-4% by weight of the composition.

Preferred amylases include, for example, α-amylases obtained from certain strains of B. licheniformis, described in more detail in GB-1,296,839 (Novo). Preferred commercially available amylase, for example, Gist-Brocades trade name Rapidase
Some are sold by Novo Industri A / S under the tradenames Termamyl, Duramyl and BAN. A highly preferred amylase enzyme is PCT
/ US9703635, WO95 / 26397 and WO96 / 23873. The amylase enzyme may be incorporated into the composition according to the present invention at an active enzyme level of 0.0001 to 2% by weight of the composition.

The lipolytic enzyme is also present at 0.0001 to 2% by weight of the composition, preferably 0.001 to 2%.
It may be present at an active lipolytic enzyme level of 1% by weight, most preferably 0.001 to 0.5% by weight. Lipases may be fungal or bacterial in origin, for example, Humicola
sp., Thermomyces sp. or Psuedomonas sp., such as a lipase-producing strain of Psuedomonas psuedoalca ligenes or Psuedomonas fluorescens . Lipases from chemically or genetically modified variants of these strains are also useful herein. Preferred lipases are derived from Psuedomonas psuedoalcaligenes and are described in licensed European patent EP-B-0218272. Another preferred lipase here is obtained by cloning the gene from Humicola lanuginosa and expressing the gene in Aspergilus oryza as host, as described in European patent application EP-A-0258068, trade name
Commercially available from Novo Industri A / S, Bagsvaerd, Denmark in Lipolase. This lipase is also disclosed in US Patent No. 4,8,878, issued to Huge-Jensen et al.
10,414.

Organic Polymer Compounds Organic polymer compounds are preferred additional components of the composition or the present aggregates, which act to bind the components of the aggregate together. By organic polymeric compound is meant essentially a polymeric organic compound commonly used as a binder, dispersant, anti-redeposition and soil suspending agent in detergent compositions, which is described herein as a soil flocculant. There are also any high molecular weight organic polymer compounds, such as quaternized ethoxylated (poly) amine soil removal / anti-redeposition agents according to the present invention. The organic polymer compound is present in an amount of 0.01 to 30% by weight, preferably 0.1 to 30% by weight of the composition.
Typically at a level of 15%, most preferably 0.5 to 10%, in the detergent compositions of the present invention.

Examples of organic polymeric compounds include water-soluble organic homo- or copolymeric polycarboxylic acids, or salts thereof, wherein the polycarboxylic acid has at least two carboxyl groups separated from each other by no more than two carbon atoms. are doing. The latter type of polymer is G
BA-1,596,756. Examples of such salts are MWt1
000-5000 polyacrylates, and their copolymers with maleic anhydride, such copolymers being 2000-100,000, in particular 40,000
It has a molecular weight of 000-80,000.

Those derived from aspartic acid, such as EP-A-305282, EP-
Polyamino compounds, including those disclosed in A-305283 and EP-A-351629, are also useful herein. Terpolymers comprising monomer units selected from maleic acid, acrylic acid, polyaspartic acid and vinyl alcohol, especially those having an average molecular weight of 5000 to 10,000, are also suitable here.

Other organic polymer compounds suitable for incorporation into the present detergent compositions include cellulose derivatives such as methylcellulose, carboxymethylcellulose, hydroxypropylmethylcellulose and hydroxyethylcellulose. Another useful organic polymer compound is polyethylene glycol, especially with a molecular weight of 10
00 to 10000, more specifically 2000 to 8000, most preferably about 40
00. Highly preferred polymer compounds here are described in US Pat. No. 4,968, Scheibel et al.
No. 451 and Gosselink et al., US Pat.
No. 051517 is a cotton and non-cotton soil release polymer.

Another organic compound, which is a preferred soil dispersion / anti-redeposition agent for use herein, is an ethoxylated cationic monoamine and diamine of the formula:

Embedded image Wherein 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; a is 0-20, preferably 0-4 (eg, , Ethylene, propylene, hexamethylene) and b is 1 or 0; for cationic monoamines (b = 0), n is at least 16 and a typical range is 20-35; For the diamines of nature (b = 1), n is at least about 12, and a typical range is from about 12 to
It is about 42.

Other dispersing / anti-redeposition agents useful herein are disclosed in EP-B-011965, US Pat.
659,802 and US Pat. No. 4,664,848.

Antifoaming System The detergent composition of the present invention, when formulated for a machine cleaning composition, contains 0.1% of the composition.
01-15% by weight, preferably 0.02-10%, most preferably 0.05-3%
May contain a foam suppression system. Foam control systems suitable for use herein may include essentially any known antifoam compound, including, for example, silicone antifoam compounds and 2-alkylalkanol antifoam compounds. By defoaming compound is meant a compound or a mixture of compounds that acts to suppress foaming or foaming caused by the solution of the detergent composition, especially under stirring of the solution.

[0127] Particularly preferred defoaming compounds for use herein are the silicone defoaming compounds defined herein as defoaming compounds including a silicone component. Such silicone antifoam compounds typically also include a silica component. The term "silicone", as used herein and generally throughout the industry, encompasses various relatively high molecular weight polymers having various types of siloxane units and hydrocarbyl groups. Preferred silicone antifoam compounds are siloxanes, especially polydimethylsiloxanes having trimethylsilyl endblock units.

Other suitable antifoam compounds include monocarboxylic fatty acids and their soluble salts. These materials are described in Wayne St. John, US Pat. No. 2,954,347, issued Sep. 27, 1960. Monocarboxylic fatty acids and salts thereof useful as suds suppressors typically contain 10 to 24 carbon atoms, preferably 12 to 18 carbon atoms.
Has the following carbon atoms. Suitable salts include alkali metal salts such as sodium, potassium and lithium salts, and ammonium and alkanolammonium salts.

Other suitable defoaming compounds include, for example, high molecular weight fatty esters (eg, fatty acid triglycerides), fatty acid esters of monohydric alcohols, aliphatic C ₁₈ -C ₄₀ ketones (eg, stearone) N-alkylation Aminotriazines, such as tri-hexaalkylmelamine or di-tetraalkyldiaminechlorotriazine, propylene oxide, formed as the product of cyanuric chloride and 2 or 3 moles of a primary or secondary amine having 1 to 24 carbon atoms There are bisstearic acid amide and monostearyl dialkali metal (eg, sodium, potassium, lithium) phosphates and phosphate esters.

Preferred foam control systems include: (a) a defoaming compound, preferably a silicone defoaming compound, most preferably a silicone defoaming compound in combination with (i) 50-99% by weight of the silicone defoaming compound, preferably Is 75 to 95% level of polydimethylsiloxane, and (ii) 1 to 50% by weight of the silicone / silica defoaming compound, preferably 5 to 25% level of silica (the silica / silicone defoaming compound is 5 to 50% by weight. (B) formulated at a level of 0.5-10% by weight, preferably 1-10%, most preferably 72-78% polyoxyalkylene. Rate and 1: 0.9 to 1: 1
. A dispersant compound consisting of a silicone glycol lake copolymer having an ethylene oxide to propylene oxide ratio of 1 (a particularly preferred silicone glycol lake copolymer of this type is DCO 544, commercially available from DOW Corning under the trade name DCO 544); (c) 5-80% by weight, consists preferably is at the level of 10% to 70%, and most preferably, ethoxylation 5-50, preferably inert carrier fluid compound consisting of 8 to 15 _C 16 _{-C 18} ethoxylated alcohols Have been.

A highly preferred particulate foam control system is described in EP-A-0210731, which comprises a silicone antifoam compound and an organic carrier material having a melting point in the range of 50-85 ° C. Is a monoester of a fatty acid and glycerol having a carbon chain of 12 to 20 carbon atoms. EP-A-0210721
Describes another preferred particulate foam control system wherein the organic carrier material is a fatty acid or alcohol having a carbon chain of 12 to 20 carbon atoms, or a mixture thereof, having a melting point of 45 to 80 ° C. Has been disclosed.

Other highly preferred foam control systems contain mixtures of polydimethylsiloxanes or silicones, such as polydimethylsiloxane, aluminosilicate and polycarboxylic acid polymers, such as copolymers of lactic acid and acrylic acid.

Polymer Discoloration Inhibitors The present compositions may also contain from 0.01 to 10% by weight, preferably from 0.05 to 0.5%, of polymer discoloration inhibitors. The polymer transfer inhibitor is preferably a polyamine N-oxide polymer, N-
Selected from copolymers of vinylpyrrolidone and N-vinylimidazole, polyvinylpyrrolidone polymers or combinations thereof, these polymers may be cross-linked polymers.

Fluorescent Whitening Agent The present composition optionally also contains about 0.005 to 5% by weight of a type of hydrophilic fluorescent whitening agent. Useful hydrophilic optical brighteners herein include those having the following structural formula:

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

Wherein R ₁ is anilino, R ₂ is N-2-bis-hydroxyethyl, and M
Is a cation such as sodium, the brightener is 4,4'-bis [[4-anilino-6- (N-2-bis-hydroxyethyl) -s-triazin-2-yl] amino]- 2,2'-stilbene disulfonic acid and disodium salt.
This particular brightener species is commercially available from Ciba-Geigy Corporation under the trade name Tinopal-UNPA-GX. Tinopal-CBS-X and Tinopal-UNPA-GX are preferred hydrophilic optical brighteners useful in the present detergent compositions.

Where R ₁ is anilino, R ₂ is N-2-hydroxyethyl-N-2-methylamino, and M is a cation such as sodium, the brightener is 4,4 ′
-Bis [[4-anilino-6- (N-2-hydroxyethyl-N-methylamino) -s-triazin-2-yl] amino] -2,2'-stilbene disulfonic acid disodium salt. This particular brightener species is commercially available from Ciba-Geigy Corporation under the trade name Tinopal 5BM-GX.

Where R ₁ is an anilino, R ₂ is a 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 sodium salt. This particular brightener species is commercially available from Ciba-Geigy Corporation under the trade names Tinopal-DMS-X and Tinopal AMS-GX.

Polymeric Soil Release Agents Polymeric soil release agents, hereinafter referred to as "SRA", may also optionally be used in the present compositions. If utilized, the SRA is typically 0.01-10.
0% by weight, typically 0.1-5%, preferably 0.2-3.0%.

Preferred SRAs are hydrophilic segments that hydrophilize the surface of hydrophobic fibers, such as polyester and nylon, and remain on the hydrophobic fibers and remain attached to them until the end of the wash and rinse cycle, and And a hydrophobic segment that serves as an anchor for the segment. This makes it possible to more easily wash dirt generated after the SRA processing by a subsequent cleaning operation.

Preferred SRAs include oligomeric terephthalate esters, typically prepared by a process involving at least one transesterification / oligomerization with a metal catalyst such as a titanium (IV) alkoxide. Such esters are of course made with additional monomers that can be incorporated into the ester structure at 1, 2, 3, 4 or more positions without forming a tightly crosslinked overall structure.

[0141] Suitable SRAs include, for example, JJ Scheibel and EPGo dated November 6, 1990.
Substantially composed of an oligomeric ester backbone of terephthaloyl and oxyalkyleneoxy repeating units and an allyl-derived sulfonated terminal moiety covalently linked to the backbone, as described in US Pat. No. 4,968,451 to sselink. There are sulfonated products of linear ester oligomers. Such ester oligomers can be obtained by (a) ethoxylating allyl alcohol and (b) converting the product of (a) to dimethyl terephthalate ("DMT") in a two-stage transesterification / oligomerization operation.
And 1,2-propylene glycol ("PG") and (c) (
It can be prepared by reacting the product of b) with sodium metabisulfite in water. Other SRAs include Gosselink et al., US Pat. No. 4,711, December 8, 1987.
730 nonionic end-capped 1,2-propylene / polyoxyethylene terephthalate polyesters, such as prepared by transesterification / oligomerization of poly (ethylene glycol) methyl ether, DMT, PG and poly (ethylene glycol) ("PEG") There are things to be done. Other examples of SRA include 1988
Partial and fully anionic end-capped oligomeric esters of US 4,721,580 from Gosselink, January 26, 2006, such as ethylene glycol ("EG")
, PG, DMT and 3,6-dioxa-8-hydroxyoctanesulfonic acid N
Oligomers from a; US 4,702, Gosselink, Oct. 27, 1987.
857 nonionic capped block polyester oligomer compounds, such as DMT, methyl (Me) capped PEG and EG and / or PG, or DMT, EG and / or PG, Me capped PEG and dimethyl-5
Made from a combination of -sulfoisophthalate Na; October 31, 1989
There are US 4,877,896 anionic, especially sulfoaroyl end-capped terephthalate esters of Maldonado, Gosselink et al. Dated, the latter being a representative example of an SRA useful in both laundry and fabric conditioning products, examples of which are m.
-An ester composition made from monosodium sulfobenzoate, PG and DMT, optionally but preferably with the addition of PEG, for example PEG3400.

SRA includes simple copolymer blocks of ethylene terephthalate or propylene terephthalate and polyethylene oxide or polypropylene oxide terephthalate (Hays US Pat. No. 3,959,230 and May 25, 1976.
See US 3,893,929, Basadur, July 8, 975); Dow to METHOD
Cellulose derivatives such as hydroxyethercellulose polymers commercially available as: C ₁ -C ₄ alkylcellulose and C ₄ hydroxyalkylcellulose (see US Pat. No. 4,000,093 to Nicol et al., Dec. 28, 1976); anhydroglucose units Some methylcellulose ethers have an average degree of substitution (methyl) of about 1.6 to about 2.3 per solution and a solution viscosity of about 80 to about 120 centipoise when measured at 2O <0> C as a 2% aqueous solution. Such a substance is METOLOSE SM1
It is commercially available as 00 and METROLOSE SM200, which is the trade name for methylcellulose ether manufactured by Shin-Etsu Chemical KK.

Additional classes of SRAs include (I) nonionic terephthalates using diisocyanate coupling agents to link the polymer ester structure (see Violland et al., US Pat. No. 4,201,824 and Lagasse et al., US Pat. No. 4,240,918). And (II) SRA with carboxylate end groups made by adding trimellitic anhydride to known SRA to convert terminal hydroxyl groups to trimellitate esters. With the proper choice of catalyst, trimellitic anhydride forms a linking chain at the end of the polymer via a carboxylic acid ester of the trimellitic anhydride rather than ring opening of the linking anhydride. Nonionic or anionic SR
A may be used as a starting material as long as they have a hydroxyl end group that is esterified. See U.S. Pat. No. 4,525,524 to Tung et al. For other classes
(III) There is an anionic terephthalate-based SRA of a urethane binding type. Viollan
See US Pat. No. 4,201,824 to d et al.

Other Optional Ingredients Other optional ingredients suitable for inclusion in the compositions of the present invention include flavors, speckles, colorants or pigments, filler salts, with sodium sulfate being the preferred filler salt. Small amounts (eg, less than about 20% by weight) of neutralizing agents, buffers, phase modifiers, hydrotropes, enzyme stabilizers, polyacids, foam regulators, opacifiers, antioxidants, bactericides and pigments; For example, US Pat. No. 4,2,2, Barrat et al. Issued on Aug. 25, 1981.
There may also be those described at 85,841 (incorporated herein by reference).

Composition Forms The compositions of the present invention can be made by various methods, including dry mixing, agglomeration, compression or spray drying of various compounds contained in the detergent ingredients, or a combination of these techniques. The composition may take various physical forms, including liquids, preferably solid forms such as tablets, flakes, pastels and bars, preferably granules or tablet forms. The composition according to the invention may be used in combination with a bleaching composition comprising, for example, chlorine bleach. The detergent composition, especially a laundry detergent, is preferably 280 g / L to 200 g / L,
It preferably has a bulk density of 300 or 350 or 420 g / L to 2000 g / L, more preferably 1500 g / L, or 100 g / L, or 700 g / L.

In [0146] laundry washing method Machine laundry methods, typically by washing aqueous solution of the washing machine in which is dissolved or dispensed an effective amount of a machine laundry detergent composition according to the present invention, it processes the dirty laundry. The effective amount of the detergent composition refers to the typical product usage and washing solution volume commonly used in conventional machine washing methods, and the amount of product 10 dissolved or distributed in a 5-65 L wash solution.
Means ~ 300 g. The composition may be formulated to be suitable for hard surface cleaning or hand washing, or for pre-treatment or dipping of soiled and stained fabrics.

In the abbreviated detergent compositions used in the examples , the abbreviated component designations have the following meanings: LAS: sodium linear C _11-13 alkylbenzene sulfonate MES: α-sulfomethyl ester of C ₁₈ fatty acid TAS: sodium Tallow alkyl sulfate CxyAS: Sodium C _1x -C _1y alkyl sulfate C46SAS: Sodium C ₁₄ -C ₁₆ secondary (2,3) alkyl sulfate CxyEzS: Sodium C _1x -C _1y alkyl sulfate CxyEz condensed with z moles of ethylene oxide C _1x -C _1y predominantly linear primary alcohol condensed with an average z mole of ethylene oxide 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) SADS: formula _{2- (R) C 4 H 7} -1,4- (SO 4) 2 (R = C 10 - C ₁₈ ) Sodium C ₁₄ -C ₂₂ alkyl disulphate SADE2S: Formula 2- (R) C ₄ H ₇ -1,4- (SO ₄ ) ₂ (R = C ₁₀ −) condensed with z moles of ethylene oxide sodium _C 14 _{-C 22} alkyl disulfate APA of _{C 18):} C 8 _{-C 10} amidopropyl dimethylamine soap: tallow and coconut sodium linear alkyl carboxylate derived from a 80/20 mixture of fatty acid STS: sodium toluene sulfonate CFAA: _C 12 _{-C 14} (coco) alkyl N- methyl glucamide TFAA: _C 16 _{-C 18} alkyl N- main Rugurukamido TPKFA: _C 16 _{-C 18} Top de-hole cut (topped whole cut) fatty STPP: Anhydrous sodium tripolyphosphate TSPP: Tetrasodium pyrophosphate Zeolite A: Formula _Na 12 having a main particle size of 0.1~10μm range (AlO _{2 SiO 2) 12 · 27H 2} O of hydration of sodium aluminosilicate (wt displayed on a dry basis) NaSKS-6 (I): crystalline layered silicate with a weight average particle diameter of 18 microns of formula _{δ-Na 2 Si 2 O 5} ; NaSKS-6 (II): a crystalline laminated silicate of the formula δ-Na ₂ Si ₂ O _{5 with} a weight average particle size of 18 microns; at least 90% by weight is at least 90% by weight Citric acid: anhydrous citric acid borate: sodium borate carbonic acid with a particle size of 42.1 micron or less : Anhydrous sodium bicarbonate carbonate having a particle size of 200～900Myuemu: particle size distribution of anhydrous sodium bicarbonate silicates having the 400～1200Myuemu: Amorphous sodium silicate _{(SiO 2: Na 2 O =} 2.0: 1 ) Sulfate: anhydrous sodium sulfate Mg: anhydrous magnesium sulfate citrate: 86.4% active trisodium citrate dihydrate with a particle size distribution of 425 to 850 μm MA / AA: 1: 4 maleic / acrylic acid Copolymer, average molecular weight of about 70,000 MA / AA (1): copolymer of 4: 6 maleic / acrylic acid, average molecular weight of about 10,000 AA: sodium polyacrylate polymer of average molecular weight of 4500 CMC: sodium carboxymethyl cellulose cellulose ether: Shin-Etsu Commercially available from Chemistry Methyl cellulose ether protease with a degree of 650: Proteolytic enzyme with 3.3% by weight of active enzyme, sold by NOVO Industries A / S under the trade name Savinase Protease I: described in WO 95/10591, Genencor Int. Inc., a proteolytic enzyme with 4% by weight of active enzyme Alcalase: a proteolytic enzyme with 5.3% by weight of active enzyme, cellulase, sold by NOVO Industries A / S: Cellulase degrading enzyme with 0.23% by weight of active enzyme sold by NOVO Industries A / S under the trade name Carezyme Amylase: 1.6 weight sold by NOVO Industries A / S under the trade name Termamyl 120T Amylolytic enzyme with% active enzyme Amylase II: amylolytic enzyme lipase as disclosed in PCT / US9703635: quotient 1. Lipase (1), sold by NOVO Industries A / S under the name Lipolase, having 2.0% by weight of active enzyme: Sold by NOVO Industries A / S under the name Lipolase Ultra; 0 wt% of a lipolytic enzyme Endolase had active enzyme: NOVO Industries a / endoglucanase having 1.5% by weight of active enzyme, sold by S deaminase enzyme PB4: wherein NaBO ₂ · _{3H 2} O · H ₂ O ₂ of sodium perborate sum thereof PB1: formula NaBO ₂ · _H 2 _{O 2} in anhydrous sodium perborate bleach percarbonate: sodium percarbonate of the formula _{2Na 2 CO 3 · 3H 2 O} 2 DOBS: sodium salt Form decanoyloxybenzenesulfonate DPDA: diperoxide decane diacid NOBS: sodium salt form nonanoyloxybenzenesulfonate NACA- BS: (6-nonamidocaproyl) oxybenzenesulfonate LOBS: sodium salt form dodecanoyloxybenzenesulfonate DOBS: sodium salt form decanoyloxybenzenesulfonate DOBA: decanoyloxybenzoic acid TAED: tetraacetylethylenediamine DTPA: diethylenetriamine Acetate DTPMP: Diethylenetriaminepenta (methylenephosphonate) EDDS sold by Monsanto under the trade name Dequest 2060: Ethylenediamine-N, N'-succinic acid, sodium salt form, (S, S) isomer Photoactivated bleach (1) ): Sulfonated zinc phthalocyanine encapsulated in dextrin-soluble polymer Photo-activated bleach (2): Sulfonated aluminofta encapsulated in dextrin-soluble polymer Cyanine Brightener 1: 4,4'-bis (2-sulfostyryl) biphenyl disodium Brightener 2: 4,4'-bis [(4-anilino-6-morpholino-1,3,5-triazine- 2-yl) amino] stilbene-2,2'-disulfonate disodium HEDP: 1,1-hydroxyethanediphosphonic acid PEGx: polyethylene glycol of molecular weight x (typically 4000) PEO: average molecular weight 50,000 Polyethylene oxide TEMPAE: Tetraethylene pentaamine ethoxylate PVI: Polyvinylimidazole with an average molecular weight of 20,000 PVP: Polyvinylpyrrolidone polymer with an average molecular weight of 60,000 PVNO: Polyvinylpyridine N-oxide polymer with an average molecular weight of 50,000 PVPVI: Average molecular weight 20, 000, a copolymer of polyvinyl pyrrolidone and vinyl imidazole QEA: bis _{[(C 2 H 5 O) (} C 2 H 4 O) n ] ^{_{(CH 3) -N + - C}} 6 H 12 -N + - (CH 3) bis _{[(C 2 H 5 O) -} (C 2 H 4 O) ] _{n (n} = _20~30) SRP1: anionic end-capped polyester SRP2: diethoxylated poly (1,2-propylene terephthalate) short block Polymers PEI: Polyethyleneimine having an average molecular weight of 1800 and an average degree of ethoxylation of 7 ethyleneoxy residues per nitrogen Silicone defoamer: Dispersant having a foam control agent to dispersant ratio of 10: 1 to 100: 1 Polydimethylsiloxane foam control agent containing siloxane oxyalkylene copolymer as opaque agent: BASF A Water based monostyrene latex mixture, sold by ktiengesellschaft under the trade name Lytron 621 Wax: paraffin wax

Example 1 The following is a detergent formulation according to the invention: ABCD base powder: STPP--10.0-Zeolite A 16.0--16.0 C45AS 4.0-4.0 5.0 QASI-1.0--MBAS 17, 2.1 2.0 4.0- _{- C 25 AE3S - 1.0 - 1.0} MA / AA 2.0 1.0 2.0 1.0 LAS 4.0 2.0 3.0 1.6 TAS - 4.0 - - silicate - 3.0 - 3.0 CMC 1.0 1.0 0.5 1.0 brightener 2 0.2 0.2 - - soap 1.0 - - 1.0 DTPMP 0.4 0.4 0.2 0.4 Spray-on: C45E7-2.5--C25E3 2.5----Silicone defoamer 0.3 0.3 0.3 0.3 Fragrance 0.3 0.3 0.3 0.3 Aggregate: NaSKS-6 (II) 9.0 16.0 10.0 6.8 LAS 8.0 9.0 4.0 5.0 Dry additive : QEA-0.5 1.0-Carbonate 6.0 13.0 15.0 13.0 PB4 18.0 18.0 10.0-PB1 4.0 4.0--NOBS 3.0 4.2 1.0-Light activated bleach 0.02 0.02 0.02 0.02 Manganese contact Medium--0.5-Protease 1.0 1.0 1.0 1.0 Lipase 0.4 0.4 0.4 0.4 Amylase 0.25 0.30 0.15 0.3 Dry mix sodium sulfate 3.0 3.0 5.0 3.0 Rest (moisture & other) 100.0 100.0 100.0 100.0 Density (g / L) 630 670 670 670

Example 2 The following is a detergent formulation according to the invention: EFGH base product: TAS-1.0 4.0-LAS 5.0-11.0 8.0 C45AS 4.0 4.0. 6.0 6.0 MES 3.0 - - - QASII 0.4 - 1.0 - TFAA - 1.0 - - C 25 E 5 / C 45 E 7 / C 25 E 3 - 2.0 - 1. 0-18.0--Zeolite 9.0 5.0-8.0 Carbonate 13.0 7.5-5.0 Bicarbonate-7.5--DTPMP 0.7 1.0--SRP10 0.3 0.2-0.1 MA / AA 2.0 1.5 2.0 1.0 1.0 CMC 0.8 0.4 0.4 0.2 Protease 0.8 1.0 0.5 0.5 Amylase 0.8 0.4-0.25 Lipase 0.2 0.1 0.2 0.1 0.1 Cellulase 0.15 0.05 -Light activated bleach (ppm) 70 ppm 45 ppm-10 ppm Brightener 1 0.2 0.2 0.08 0.2 PB1 6.0 2.0---NACA----3.0 NAC-OBS 2.0 1.0 0.9 3.1 Aggregate: NaSKS-6 (I) 6.6 6.0 20.0 10.0 LAS 3.0-15.0 7.0 C45AS 3.0 6.0-- Balance (moisture & other) 100 100 100 100

Example 3 The following is a detergent formulation according to the invention: IJK base powder: MBAS 17.5,1.8-2.0 Zeolite A-22.0 6.0 Sodium sulfate 1.0 5.0- MA / AA 3.0 3.0 3.0 MES-5.0-LAS--3.5 C45AS 3.0 4.0 7.0 7.0 Silicate-1.0 5.0 Soap--2.0 Brightening Agent 1 0.2 0.2 0.2 Carbonate 8.0 16.0 5.0 Citric acid 3.0 2.0 1.5 Spray-on: C45E5 1.0 1.0-Aggregate: NaSKS-6 (I) or (II) 17.0 6.0 7.0 LAS / MES 10.0 6.0 5.0 Moisture 0.5 0.1 0.5 Powdered zeolite-0.8 0.5 Dry additive : PVPVI / PVNO 0.5 0.5 0.5 Protease 1.0 1.0 1.0 Pase 0.4 0.4 0.4 Amylase 0.1 0.1 0.1 Cellulase 0.1 0.1 0.1 NOBS-6.1-NAC-OBS--4.5 Sodium sulfate-6.0 -Balance (moisture & other) 100 100 100

Example 4 The following is a high-density and bleach-containing detergent formulation according to the present invention: LM N blown powder: zeolite A--15.0 sodium sulphate 0.0 5.0 0.0 LAS 3.0-3.0 C45AS 3.0 2.0 4.0 QAS --1.5 DTPMP 0.4 0.4 0.4 CMC 0.4 0.4 0.4 MA / AA 4.0 2.0 2.0 Aggregate: QAS 1.0--LAS-11.0 7.0 TAS 2.0 2.0 1.0 Silicate 3.0-4.0 Zeolite A 8.0 8.0 8.0 Carbonate 8.0 8.0 4.0 Aggregate: NaSKS -6 (I) or (II) 15.0 12.0 5.0 LAS 8.0 7.0 4.0 AS 5.0--Spray-on: encapsulated fragrance 0.3 0.3 0.3 C25E3 2.0-2.0 Dry additive: QEA 1.0 0.5 0.5 citric acid / citrate 5.0-2.0 bicarbonate -3.0-Carbonate 8.0 15.0 10.0 NAC-OBS 6.0-5.0 Manganese catalyst--0.3 NOBS-2.0-PB1 14.0 7.0 10.0 MW 5,000,000--0. 2 Polyethylene oxide Bentonite clay--10.0 Citric acid--0.5 Protease 1.0 1.0 1.0 Lipase 0.4 0.4 0.4 Amylase 0.6 0.6 0.6 Cellulase 0.6 0.6 0.6 Silicone defoamer 5.0 5.0 5.0 Dry additive: Sodium sulfate 0.0 3.0 0.0 Balance (moisture & other) ) 100.0 100.0 100.0 Density (g / L) 850 850 850

Example 5 The following is a high-density detergent formulation according to the present invention: OPQR agglomerate: QAS 2.0-2.0-MES-2.0- LAS 6.0- TAS-2.0- C45AS 6.0 4.0 2.0- MBAS 16.5,1.9 4.0---Zeolite A 15.0 6.0--Carbonate 4.0 8.0 4.0 8.0 MA / AA 4.0 2.0-2.0 CMC 0.5 0.5-0.5 DTPMP 0.4 0.4-0.5 Spray-on: C25E3 1.0 1.0--Fragrance 0.5 0.5 0.5 0.5 Aggregate: SKS-6 7.0 15.0 20.0 10.0 LAS 5.8 9.0 15.0 10.0 Zeolite-0.9--C45AS-3.0--Water 0.08 0.1-0.2 Dry additive: EDDS / HEDP 0.5 0.3 0.5 0.8 NaSKS-6 (I) 5.0 6.0 4.0 11.0 Citrate-1.0--Citric acid 2.0-2.0 4.0 NAC-OBS 4.1-5.0 4.0 TAED 0.8 2.0-2.0 Percarbonate 20.0 20.0 15.0 17.0 SRP1 0.3 0.3-0.3 Protea X 1.4 1.4 1.0 0.5 Lipase 0.4 0.4 0.3-Cellulase 0.6 0.6 0.5 0.5 Amylase 0.6 0.6-0.3 QEA 1.0-1.0 1.0 Silicone defoamer 1.0 0.5 0.5 1.5 Brightener 1 0.2 0.2-6.2 Brightener 2 0.2-0.2-Density (G / L) 850 850 800 775

Example 6 STUVWX C45AS 11.0 5.0 4.6 6.5 4.1 9.0 C25AES 1.3 1.0-1.3 1.0-LAS-3.0 2.7-2.0-C25E3 / C25E5 1.5 4.7 3.3-4.7 3.3 MBAS 16.5, 1.7 15.0 12.0 10.0 10.2 7.0 14.1 QAS-1.15 0.6-1.7-Zeolite A 5.0 16.7-7.0 16.7 11.2 SKS-6 / LAS aggregate 5: 4 20.0-17.5 20.0 9.0 17.5 Citric acid-1.5 2.5-1.5-MA / AA-0.6--0.6- MA / AA3--7.03--7.03 AA 2.3--2.8--EDDS-0.3--0.3-HEDP-0.5--0.5-Carbonate 6.0 12.5 14.5 6.0 12.5 14.0 Silicate 0.58 0.8 12 0.58 0.8 12 PB1 11.0-14.0- -4.0 NACA-OBS-4.7--2.7-PC-17.3-20.0 17.3-NOBS--4.0--4.0 TAED-2.5--3.5 2.0 Protease 0.25 0.36 0.2 0.26 0.36 0.2 Lipase---- ----Cellulase 0.3 0.26-0.3 0.26-Amylase-0.36--0.36-Brightener 0.17 0.06 0.30 0.17 0.06 0.30 SRP1 0.4 0.2 0.5 0.4 0.2 0.5 PEG 1.6-0.19 1.6-0.19 Sulfate 5.5 6.4 3.5 5.5 6.4 3.5 CMC-0.5 - - 0.5 - MgSO ₄ - 0.13 - - 0.13 - photobleach - 0.0026 - - 0.0026 - silicone antifoam 0.02 0.21 0.17 0.02 0.21 0.17 perfume 0.42 0.55 0.25 0.42 0.55 0.25

Example 7 The following laundry detergent compositions Y-AB are prepared in accordance with the present invention: YZAAAB MBAS16.5,1.7--5.5 C45AS 9.0 8.0 4.14 C45E1S 0---LAS--3.7-C16SAS-2.0--MES---4 C23E6.5-1.5-1.5 SKS-6 / LAS aggregate 5: 4 18.0 10.0 35.0 12.0 Zeolite A 7.8 17.0-20.0 AA 2.3 2.3 2.3 2.3 Carbonate 7.0 7.0 12.5 2.5 Silicate 0.60 0.6 0.6-perborate / PC 11.0 2.0--protease 0.3 0.3 0.3 0.3 cellulase 0.3 0.3 0.3 0.3 SRP1 0.4 0.4 0.4 0.4 Brightener 0.2 0.2 0.2 0.2 PEG 1.6 1.6 1.6 1.6 1.6 Sulfate 5.5 5.5 5.5 5.5 Silicone defoamer 0.42 0.42 0.42 0.42 Moisture & other balance Density (g / L) 663 663 663 663

Example 8 The following laundry detergent compositions AC-AG are prepared according to the present invention: AC AD AE AF AG MBAS 16.5, 1.7 14.8 16.4 12.3 8.2 4.1 C45AS 6.0 8.0 4.3 4.0 5.0 C45E1S 2.0--1.0-LAS- --3.0 5.0 C16SAS-1.0----MES-5.0----TFAA 1.6 00 0 0 C24E3 4.9 4.9 4.9 4.9 4.9 Zeolite A 5.0 15----NaSKS-6 / LAS3: 2 spray dry particles 21 7 22 17 20 Citrate / citric acid 1.0 3 3 2.0-MA / AA 4.8 4.8 4.8 4.8 4.8 4.8 HEDP 0.5 0.5 0.5 0.5 0.5 Carbonate 8.5 8.5 8.5 8.5 8.5 Percarbonate 20.7 20.7 20.7 20.7 20.7 TAED 4.8 4.8--4.8 NACA-OBS--5.0 6.0 2.0 Protease 0.9 0.9 0.9 0.9 0.9 Lipase 0.15 0.15 0.15 0.15 0.15 Cellulase 0.26 0.26 0.26 0.26 0.26 Amylase 0.36 0.36 0.36 0.36 0.36 SRP1 0.2 0.2 0.2 0.2 0.2 Brightener 0.2 0.2 0.2 0.2 0.2 Sulf Over preparative 2.3 2.3 2.3 2.3 2.3 QEA 1.0 1.0 - - - QAS 1.0 - - - 1.0 Silicone antifoam 0.4 0.4 0.4 0.4 0.4 water & other remaining portion Density (g / L) 850 850 850 850 850

Example 9 The following formulation is an example of a composition according to the present invention, which may be in the form of granules or tablets. AH AI AJ AK AL Base product C45AS / TAS 8.0 5.0 3.0 3.0 3.0 LAS 8.0-8.0-7.0 C25AE3S 0.5 2.0 1.0--3 : 2 ratio LAS / NaSKS-6 5.0 17.0 9.0 20.0 15.0 (I) or (II) aggregate C25AE5 / AE3 2.0-5.0 2.0 2.0 QAS ---1.0 1.0 Zeolite A 20.0 10.0 10.0-10.0 SKS-6 (I) (dry additive)--2.0--MA / AA 2.0 0 2.0--AA----4.0 Citrate-2.0----Citric acid 2.0-1.5 2.0-DTPA 0.2 0.2---EDDS---0. 5 0.1-HEDP--0.2 0.1-PB1 3.0 5.0 10.0-4.0 PC---18.0-NOBS 3.0 4 0--4.0 NACA-OBS--2.0--TAED--2.0 5.0-Carbonate 15.0 18.0 8.0 15.0 15.0 Sulfate 5.0 12.0 2.0 17.0 3.0 Silicate -1.0--8.0 Enzyme 0.3 0.3 1.0 1.0 0.2 Others (whitening agent / 0.5 0.5 0.5 0.5 0.5 SRP1 / CMC / photobleach / MgSO ₄ / PVPVI / foaming inhibitor / PEG) Fragrance 0.2 0.3 0.5 0.2 0.1

──────────────────────────────────────────────────続 き Continued on the front page (71) Applicant ONE PROCTER & GANBLE PLAZA, CINCINNATI, OHIO, UNITED STATES OF AMERICA (72) Inventor Francisco, Ramon, Figueroa, Tyne, England, Wear, Nose, Shields, Preston, Wood, 35 (72) Inventor Michael, Keith, Fenny Newcastle, UK, Upon, Tyne, Forest, Hall, Studley, Villas, 27F term (reference) 4H003 AB03 AB19 AB27 AB31 AC08 AE06 BA01 BA10 DA01 EA09 EA15 EA16 EA20 EA25 EA28 EB19 EB22 EB24 EB26 EB32 EB34 EB37 EB42 EC01 EC02 ED02 EE05 FA04 FA32

Claims (10)

[Claims] 1. It has a particle size of less than 150 microns or even less than 102 microns,
A powder comprising at least 95% by weight, or even 98% or even 100% by weight, of a crystal-laminated silicate having a weight average particle size of 5.0 microns or more, preferably 16.0-48.8 microns. A builder component containing a crystal-laminated silicate. 2. A formula _{NaMSi 2 O 5 · yH 2 O} (M is H, K, preferably Na or mixtures thereof,, y is 0 to 20, preferably 20) a crystalline powder layered silicate The builder component according to claim 1, comprising a builder component. 3. The builder component according to claim 1, wherein at least 90% by weight of the crystal-laminated silicate has a particle size of 17.3 to 88.2. 4. Surfactants 20-5, preferably comprising at least anionic surfactants.
The builder component according to any one of claims 1 to 3, which is in the form of particles consisting of 40 to 80% by weight of the crystal-laminated silicate completely mixed with 0% by weight. 5. The builder component according to claim 4, wherein the surfactant is an anionic sulfonate surfactant, preferably an alkyl benzene sulfonate salt, or a medium chain branched alkyl sulfate or sulfonate surfactant. 6. The builder component according to claim 1, wherein the builder component is in the form of an agglomerate, preferably having a weight average particle size of 300 to 1100 microns. 7. The builder component according to claim 1, which contains less than 10% by weight, preferably less than 5% by weight, of free water. 8. Preferably at a level of 1 to 60% or even 5 to 45% by weight of the composition,
A detergent composition comprising the builder component according to any one of claims 1 to 7. 9. Forming a mixture of a crystal-laminated silicate and a surfactant and granulating the mixture to form particles, preferably by forming agglomerates by agglomeration;
A method for producing the builder component according to claim 4. 10. To improve the distribution of detergent components, the detergent composition containing surfactants and other detergent components has a particle size of less than 150 microns or even less than 102 microns and at the same time 15 particles. A powder comprising at least 95% by weight, or even 98% or even 100% by weight, of a crystal-laminated silicate having a weight-average particle size of at least 0.0 microns, preferably 16.0 to 48.8 microns. Use of a builder system comprising a crystal-laminated silicate.