JP2002524575A - Distribution method - Google Patents

Abstract

  (57) [Summary] The present invention provides a detergent composition comprising a surfactant component or a part thereof and a complete mixture of a crystal-laminated silicate, thereby providing a detergent composition comprising a surfactant and other detergent components or a component thereof. A method is provided for improving dispensability.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

【Technical field】

The present invention relates to the use of certain detergent components in detergent compositions to improve the distribution of the product or its components.

[0002]

BACKGROUND OF THE INVENTION

Over the past decades, research efforts have been directed to developing detergents with improved cleaning performance. In addition, the focus was on the development of high-density detergent products.

[0003] It has recently been found that one of the main complaints of detergent users is that products are not always distributed or dissolved satisfactorily. This causes the product to remain on the dispensing drawer, in the washing machine and even on the fabric after washing, for example in the form of a gel or in the form of a powder residue. This is the case when cold water washing conditions or when a limited amount of water is used in the washing process, for example when a small amount of water comes into contact with the product inside the dispensing drawer or washing machine early in the washing process. This can be particularly problematic for high density products.

[0004] The inventors have found that various detergent components can cause these problems. They have found that, in particular, certain surfactants can form a gel upon initial contact with water. We have also found that dense granules containing high levels of surfactant, dense granules containing high levels of aluminosilicate and granules containing high levels of water can cause gelation and dissolution problems. . For example, aggregates of crystal-laminated silicates containing high levels of water are described in
le), however, wherein aluminosilicate is described as a preferred builder component over crystal-laminated silicate. EP 425804
Disclose particles containing high levels of aluminosilicates, surfactants and crystal-laminated silicates. These agglomerates known in the art are exactly the components that have been found to cause distribution problems with detergents.

[0005] The formation of these gels not only limits the delivery of the gelling ingredients to the laundry, but also the delivery of other detergent ingredients entrapped in the gel. This causes inefficient delivery of the detergent composition, in whole or in part, thereby reducing cleaning performance. Yet another problem with certain components that tend to gel is that they have a tendency to solidify, reducing the fluidity of the product. In addition, residues that occur in washing machines and possibly even fabrics are undesirable,
The reason is that they give the washing machine and clothing a dirty appearance, and even damage the fabric. Another problem with detergent products is that certain ingredients are not water soluble and have a tendency to adhere to fabrics or washing machines, forming undesirable residues.

[0006] The present inventors ameliorate these problems when the surfactant is thoroughly mixed with the specified amount of crystal-laminated silicate builder material, preferably by aggregation, before addition to the detergent formulation. I discovered that. The level of completely mixed crystal-laminated silicate and surfactant has been found to be important in remedying these problems, for example, a complete mixture containing about 60% or more surfactant is distributed perfectly. Do not mean.

[0007] The use of a fully mixed anionic surfactant and a crystal-laminated silicate, particularly an aggregate thereof, in a solid detergent composition improves the partitionability of the detergent composition, improves the solubility of the detergent composition, or It has been found that contact with water reduces gelling of the detergent composition.

[0008]

[Summary of the Invention]

The present invention provides a detergent composition comprising a complete mixture of a surfactant component and a crystal-laminated silicate, thereby improving the distribution of a detergent composition comprising a surfactant and other detergent components or the components thereof. Provide a way to The present invention provides a complete mixture obtained by thoroughly mixing a surfactant and a crystal-laminated silicate in a detergent composition containing a surfactant and other detergent components in order to improve the distribution of the detergent components. Also relates to the use of.

The complete mixture is preferably less than 10% by weight, or even less than 5%, or 3%.
% Free water. The surfactant preferably comprises an anionic surfactant, especially a sulfonate surfactant. The detergent composition is preferably a solid dishwashing detergent composition or a laundry detergent composition.

In the use or method of the present invention, by providing the surfactant or a part thereof in intimate admixture with the crystal-laminated silicate, an improved distribution of the detergent composition is obtained. The dispensability of the detergent composition or its components from the dispensing drawer or dispenser of the washing machine to the wash water is improved as compared to detergent compositions where the anionic surfactant is not completely mixed with the crystal-laminated silicate. That is what is meant here.

[0011] Improvements in dispensability include washing water during dispensing and washing water inside the washing machine compared to detergent compositions where the anionic surfactant is not completely mixed with the crystal-laminated silicate. It may also include improving the solubility of the detergent composition or its components in the wash water.

[0012] To improve the distribution of detergent compositions or components thereof, anionic surfactants are compared to detergent compositions that are not completely mixed with the crystal-laminated silicate, in that the detergent in the wash liquor is applied to the fabric or washing machine. It may also include reducing the adherence of residues of the detergent composition or its components.

[0013] The distribution of the detergent composition or its components can be improved by contact with water, especially at the beginning of the cleaning process, as compared to compositions in which the anionic surfactant is not completely mixed with the crystal-laminated silicate. It may also include a reduction in gelling of the detergent composition or its components, especially due to the dispensing drawer of the washing machine or the initial contact of the detergent composition with water inside the washing machine.

[0014]

DETAILED DESCRIPTION OF THE INVENTION Complete Mix As used herein, a "complete mixture" is a mixture of the components of the mixture, substantially uniformly, in a mixture, preferably in the form of particles. This is meant for the purpose of the present invention. Complete mixing or mixing should be interpreted accordingly. A complete mixture is obtained by any process involving mixing of the components, which can be part of a tableting process, an extrusion process, and granulation, such as spray drying and agglomeration processes. 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.

The complete mixture is preferably 90-35% by weight of the mixture, more preferably 80-35%
At 40%, or even 70-45% or 50% level, contains the crystalline stacked silicate material. Preferably, the weight ratio of crystal-laminated silicate to surfactant in the complete mixture is 4: 5 to 7: 3, more preferably 1: 1 to 2: 1, most preferably 5: 4 to 3.
: 2. Preferably, the complete mixture comprises 10 to 55% by weight of the mixture, more preferably 20%.
Contains surfactant at levels of ~ 55%, or even 30-45%.

Preferably, the complete mixture, especially the agglomerated particles, contains less than 10% by weight of the complete mixture, or even less than 5%, most preferably less than 3%. The free moisture used here is determined by placing 5 g of the complete mixture 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.

The complete mixture may also contain additional components, for example in an amount of from 0 to 25% by weight of the complete mixture, usually within 20% or even 15%. The very nature of these additional ingredients,
And the level of formulation depends on the use of the component or composition, and on the physical form of the component and composition. The complete mixture preferably contains less than 15% by weight of the mixture, or even less than 10%, or even less than 5%, or even 0% aluminosilicate.
If the complete mixture takes the form of an agglomerate, it is preferred that any aluminosilicate present is in the form of a powder in the agglomerate. The complete mixture also preferably contains less than 15% by weight, or even less than 10%, or even less than 5%, or even 0% nonionic surfactant. 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 complete mixture is mixed with the other components of the detergent composition. The complete mixture may then be present in the form of individual particles, or the complete mixture may be agglomerated with other components or sprayed or dusted with other components.

When in the form of individual particles, the particles preferably have a weight average particle size similar to the weight average particle size of the other components of the detergent composition. The particles are preferably 150
Particles having a weight average particle size of １1500 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 particles having less than 10% by weight are 1180 It has a particle size of microns or even 710 microns or more (with Tyler mesh sieve 24).

Preferably, the density of the complete mixture, when present as individual particles, is between 380 and 1
500 g / L, more preferably 500 to 1200 g / L, more preferably 550
９００900 g / L.

Surfactants The compositions of the present invention contain one or more surfactants, at least some of which are intimately mixed with the crystal-laminated silicate material. The surfactant includes any surfactant known in the art selected from anionic, nonionic, cationic, 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.

Preferably, at least 50% by weight of the surfactant in the complete mixture is an anionic surfactant, preferably an anionic sulfonate surfactant, preferably an alkyl sulfonate surfactant as described herein It is. More preferably, the anionic surfactant is 50-100% by weight of the surfactant in the complete mixture,
Alternatively, it is 60 to 100%, or even 75 to 100%. The complete mixture may be preferred even if it contains only an anionic surfactant as a surfactant, or even only an anionic sulfonate surfactant. When a nonionic surfactant is present, its level is preferably within 15% by weight of the mixture, more preferably less than 10% or even less than 5%, or preferably no nonionic surfactant is present.

Anionic Surfactants The compositions and intact mixtures according to the 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 surfactants comprising a sulfonate as described herein, preferably a linear or branched alkyl benzene sulfonate, preferably together with a cationic surfactant as described herein. System.

Other anionic surfactants include isethionates such as acyl isethionates, fatty acid amides of N-acyl taurates, methyl taurides, 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 Here, especially highly preferred, especially in the complete mixture containing the crystal-laminated silicate, are anionic sulfonate surfactants. Here, C _5-
There are salt to 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 sulfonates, sulfonated polycarboxylic acids, alkyl glycerol sulfonates, fatty acyl Glycerol sulfonate, fatty oleyl glycerol sulfonate and mixtures thereof may also be used. 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 present invention, a mixture of the preferred alkyl sulphate and / or sulphonate 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 surfactants and soaps ('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.

[0031] 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 Other suitable anionic surfactants are alkali metal sarcosinates 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.

[0033] In terms of exerting a medium 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 (that is, 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 formula below shows the range of intermediate chain branching, the preferred range of intermediate chain branching, and the more preferred range of intermediate chain branching for the dimethyl-substituted alkyl ^Ab moiety 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 sulfate 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 surfactant 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 Polyhydroxy fatty acid amides suitable 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 ).

Nonionic alkyl polysaccharide surfactant: a polysaccharide having 6 to 30 carbon atoms and a hydrophobic group 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 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.

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 with 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.

[0060] 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.

[0061] 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% by weight.
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.

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.

[0066] crystalline layered silicates 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 1.9 to 4 Where 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, especially 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 crystal-laminated silicate is a coarse substance having a weight average particle diameter of 150 μm or more as measured by sieving with a Tyler sieve, or a fine substance having a weight average particle diameter of 20 μm or less with a Malvern Instruments SB.OC light scattering device. Preferably, there is. At least 95% by weight, or even 98% or even 100%, of the crystal-laminated silicate, as measured on a Malvern Instruments SB.
It has a particle size of less than 8 microns, more preferably less than 88.2 microns, or even less than 65.6 microns, while at the same time greater than 15.0 microns, preferably 16.0-6.0.
It is also preferred to have a weight average particle size of 48.8 microns or even 17.3-42.1 microns. Preferably, according to the Malvern Instrument user manual, at least 90% by weight of the particles are 17% when the weight average particles are 16.0-48.8 microns, as measured on a Malvern Instruments SB.OC light scattering device.
. When the particles have a particle size of 3-88.2 microns and the weight average particles are 17.3-42.1 microns, at least 90% by weight of the particles have a particle size of 23.3-76.0 microns. are doing.

The crystal-laminated silicate material is preferably a powdered material, and is preferably obtained by pulverizing a coarse crystal-laminated silicate material with an air jet mill or a ceramic ball mill.

Detergent Composition Additional Detergent Ingredients The compositions and intact mixtures according to the invention may contain additional detergent components. The exact nature of these additional components, and their level of incorporation, depend on the exact physical form of the composition or complete mixture, and the exact nature of the washing operation in which it is used. The composition of the present invention preferably comprises a bleach, a bleach catalyst, an alkaline system, an additional builder, an organic polymer compound, an enzyme, a foam inhibitor, a lime soap, a dispersant, a stain suspending and anti-redeposition agent, and a soil release agent. And one or more additional detergent components selected from fragrances, brighteners, photobleaches and additional corrosion inhibitors.

[0071] Preferred additional components pel hydrate bleach composition or intimate mixture is pel hydrate bleach, such as metal perborates, metal percarbonates, particularly 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 composition or complete mixture 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:
There is an 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 composition may 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 Substances Water-soluble builder The present composition or intimate mixture may preferably 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 it is present in the detergent composition at a level of 15-40% by weight. 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 present compositions or intact mixtures may contain insoluble builder compounds, 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 formula: Na ₁₂ [(AlO ₂ ) ₁₂ (SiO ₂ ) ₂₁ ] .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.

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.

[0110] Heavy metal ion sequestrants 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 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.

[0113] 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 are 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 at 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., for example Psuedomonas psuedoalca
Obtained from lipase producing strains of 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 present compositions or the present complete mixtures, which act to bind the components of the complete mixture 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 polymeric 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 dispersion / 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.

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) an antifoam compound, preferably a silicone antifoam compound, most preferably a silicone antifoam compound in combination with (i) 50-99% by weight of the silicone antifoam 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 and 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 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", can 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 include hydrophilic segments that hydrophilize the surface of hydrophobic fibers, such as polyester and nylon, and a hydrophilic segment that adheres to the hydrophobic fibers and remains attached to them until the end of the wash and rinse cycle. 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, which are typically prepared by a process involving at least one transesterification / oligomerization with a metal catalyst, often 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.

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.

The 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 [0145] 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 alkyl benzene 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 of z moles of ethylene oxide QAS: R ₂ N ⁺ (CH ₃ ) ₂ (C ₂ H ₄ OH) (R ₂ = C ₁₂ -C ₁₄ ) QS1: R ₂ N ⁺ (C H ₃ ) ₂ (C ₂ H ₄ OH) (R ₂ ＣC 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 -C) condensed with z moles of ethylene oxide ₁₈ ) Sodium C ₁₄ -C ₂₂ alkyl disulfate APA: C ₈ -C ₁₀ amidopropyldimethylamine Soap: Sodium linear alkyl carboxylate derived from an 80/20 mixture of tallow and coconut fatty acids STS: Sodium toluenesulfonate CFAA: C ₁₂ -C ₁₄ (coco) alkyl N- methyl glucamide TFAA: _C 16 _{-C 18} alkyl N- methyl glucamide T KFA: _C 16 _{-C 18} Top de-hole cut (topped whole cut) fatty STPP: Anhydrous sodium tripolyphosphate TSPP: Tetrasodium pyrophosphate Zeolite A: formula _Na 12 (AlO ₂ having a main particle size of 0.1~10μm range SiO _{2) 12} · 27H ₂ O of hydration of sodium aluminosilicate (wt displayed on a dry basis) NaSKS-6 (I): crystalline layered silicate NaSKS-6 of formula _{δ-Na 2 Si 2 O 5} (II): the weight average Crystalline laminated silicate of formula δ-Na ₂ Si ₂ O _{5 with} a particle size of 18 microns; at least 90% by weight has a particle size of less than or equal to 65.6 microns Citric acid: anhydrous citric acid borate: sodium borate carbonate: 200 Anhydrous sodium carbonate bicarbonate having a particle size of ９００900 μm: having a particle size distribution of 400 to 1200 μm Anhydrous sodium bicarbonate silicate: amorphous sodium silicate (SiO ₂ : Na ₂ O = 2.0: 1) Sulfate: anhydrous sodium sulfate Mg sulfate: anhydrous magnesium sulfate citrate: having a particle size distribution of 425 to 850 μm 86.4% trisodium citrate dihydrate MA / AA: copolymer of 1: 4 maleic / acrylic acid, average molecular weight about 70,000 MA / AA (1): copolymer of 4: 6 maleic / acrylic acid, Average molecular weight of about 10,000 AA: sodium polyacrylate polymer having an average molecular weight of 4500 CMC: sodium carboxymethylcellulose cellulose ether: methylcellulose ether protease having a polymerization degree of 650 commercially available from Shin-Etsu Chemical: sold by NOVO Industries A / S under the trade name Savinase Has been Proteolytic enzyme with 3.3% by weight of active enzyme Protease I: Proteolytic enzyme with 4% by weight of active enzyme, Alcalase, sold by Genencor Int. Inc. as described in WO 95/10591: Cellulase, a proteolytic enzyme with 5.3% by weight active enzyme sold by NOVO Industries A / S: 0.23% by weight active enzyme sold by NOVO Industries A / S under the trade name Carezyme Cellulolytic enzyme amylase having: amylolytic enzyme amylase II having 1.6% by weight of active enzyme, sold by NOVO Industries A / S under the trade name Termamyl 120T: starch as disclosed in PCT / US9703635 Degradative enzyme lipase: Lipoase with 2.0% by weight of active enzyme sold by NOVO Industries A / S under the trade name Lipolase ( ): A lipolytic enzyme with 2.0% by weight active enzyme sold by NOVO Industries A / S under the trade name Lipolase Ultra Endolase: 1.5% by weight sold by NOVO Industries A / S endoglucanase enzyme having an active enzyme PB4: wherein _{NaBO 2 · 3H 2 O · H} 2 sodium perborate of _{O 2} four hydrated compound PB1: formula NaBO ₂ · _H 2 _{O 2} in anhydrous sodium perborate bleach percarbonate : formula _2Na 2 _CO 3 · _3H 2 sodium percarbonate _{O 2} DOBS: sodium salt form of decanoyl oxybenzene sulphonate DPDA: diperoxydodecanedioic acid NOBS: nonanoyl sodium salt form oxybenzene sulphonate NACA-OBS: (6 -Nonamidocaproyl) oxybenzenesulfonate LOBS: Dodecano in sodium salt form Luoxybenzenesulfonate DOBS: decanoyloxybenzenesulfonate in sodium salt form DOBA: decanoyloxybenzoic acid TAED: tetraacetylethylenediamine DTPA: diethylenetriaminepentaacetic acid DTPMP: diethylenetriaminepenta (methylenephosphonate sold under the trade name Dequest 2060 by Monsanto ) EDDS: Sodium salt form of ethylenediamine-N, N'-disuccinic acid, (S, S) isomer Photoactivated bleach (1): Sulfonated zinc phthalocyanine encapsulated in dextrin-soluble polymer Photoactivated bleach (2 ): Sulfonated aluminophthalocyanine encapsulated in dextrin-soluble polymer Brightener 1: 4,4′-bis (2-sulfostyryl) biphenyl disodium Brightener 2: 4, '-Bis [(4-anilino-6-morpholino-1,3,5-triazin-2-yl) amino] stilbene-2,2'-disulfonate disodium HEDP: 1,1-hydroxyethanediphosphonic acid PEGx : Polyethylene glycol having a molecular weight x (typically 4000) PEO: polyethylene oxide having an average molecular weight of 50,000 TEMPAE: tetraethylenepentamine ethoxylate PVI: polyvinylimidazole having an average molecular weight of 20,000 PVP: polyvinyl having an average molecular weight of 60,000 pyrrolidone polymers PVNO: polyvinyl pyridine N- oxide polymers PVPVI average molecular weight of 50,000: average molecular weight of 20,000, a copolymer of polyvinyl pyrrolidone and vinyl imidazole QEA: bis _[(C 2 _{H 5 ) (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-chain block polymer PEI: average molecular weight of 1800 and average ethoxylation degree of 7 ethyleneoxy residues per nitrogen Polyethyleneimine having a silicone antifoam agent: having a ratio of foam control agent to dispersant of 10: 1 to 100: 1, polydimethylsiloxane foam control agent containing siloxaneoxyalkylene copolymer as dispersant Opaque agent: from BASF Aktiengesellschaft Water-based monostyrene latex mixture wax sold under the trade name Lytron 621: Ruffin 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 AE 3 S - 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 6.0 9.0 5.9 5.0 Dry Additives: 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 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 mixes sodium sulfate 3.0 3.0 5.0 3.0 balance (water & other) 100.0 100.0 100.0 100.0 Density (g / L) 630 670 670 670

Example 2 The following formulation is an example of a composition according to the invention and may be in the form of granules or in the form of a tablet. EFGH I 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 Aggregate C25AE5 / AE3 2.0-5.0 2.0 2.0 QAS---1.01 2.0 Zeolite A 20.0 10.0 10.0-10.0 NaSKS-6 (I) (dry additive)--2.0--MA / AA 2.0 2.0 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 Other (whitening agent / 0.5 0.5 0.5 0. 5 0.5 SRP1 / CMC / photobleach / MgSO ₄ / PVPVI / suds suppressor / PEG) perfume 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) Inventors Silvestre, Canseille Newcastle, England, Tyne, Killingworth, Oakfield, Drive, 12F term (reference) 4H003 AB03 AB19 AB27 AB31 AC08 AE06 BA10 CA15 EA09 EA12 EA15 EA16 EA20 EA25 EA28 EB19 EB22 EB24 EB26 EB32 EB34 EB37 EB42 EC01 EC02 EE05 FA32

Claims (10)

[Claims] 1. A detergent composition comprising a surfactant and other detergent components by providing a detergent composition comprising a complete mixture of a surfactant component or a part thereof and a crystal-laminated silicate, or a component thereof. How to improve the distribution of 2. The method according to claim 1, wherein the surfactant or a part thereof comprises an anionic surfactant, preferably a sulfonate surfactant, and the crystal-laminated silicate comprises a crystal-laminated silicate of the formula Na ₂ Si ₂ O _5. The described method. 3. The method according to claim 1, wherein the complete mixture is an agglomerate and comprises the crystal-laminated silicate and the agglomerated surfactant component or a part thereof. 4. The agglomerate comprises crystal-laminated silicate at a level of 80 to 40%, or even 70 to 50% by weight of the complete mixture, and 20 to 55%, or even 30 to 45% by weight of the complete mixture. The method according to any one of claims 1 to 3, wherein the method comprises a surfactant at a level of% by weight. 5. The method according to claim 1, wherein the complete mixture has a free moisture level of less than 10% by weight of the complete mixture, or even less than 3%. 6. The process as claimed in claim 1, wherein the complete mixture contains less than 15% by weight of the complete mixture, preferably less than 10%. 7. The process according to claim 1, wherein the complete mixture contains less than 15% by weight of the complete mixture, preferably less than 5% by weight of nonionic surfactant. 8. The process as claimed in claim 1, wherein the complete mixture contains less than 25% by weight, preferably less than 10%, of an ethylene oxide polymer. 9. The method according to claim 1, wherein the detergent composition is a solid composition having a bulk density of at least 500 g / L. 10. A detergent composition containing a surfactant and another detergent component to improve the distribution of the detergent component, wherein the surfactant and the crystal-laminated silicate are completely mixed. Use of mixtures.