CN1200998C - Detergent composition - Google Patents

Abstract

The present invention relates to a detergent composition which comprises an anionic mid-chain branched surfactant, a builder system with low content and an alkaline system comprising carbonate. The detergent composition is especially suited to serve as a solid detergent composition for washing clothes.

Description

detergent composition

field of invention

The present invention relates to detergent compositions comprising anionic mid-chain branched surfactants, low levels of builder systems and alkaline systems comprising carbonates. The compositions are particularly suitable for use as solid laundry detergent compositions.

Background of the invention

Recently, certain novel anionic mid-chain branched surfactants have been developed. Hard water conditions due to the presence of Ca and Mg ions in the wash water and on fabrics can cause degradation of various components in the detergent, especially charged surfactants such as anionic surfactants. Therefore, builders are traditionally used in detergent compositions to bind Ca and Mg ions, thereby softening the water. However, a disadvantage of high levels of builders is that many of these builders are water insoluble or only partially water soluble. This can lead to poor solubility of the detergent in the wash water and can lead to deposits of builder material on the washed fabrics and/or on the (dish) machine, causing eg graying of the fabrics. Additionally, the use of high levels of builder materials can be very expensive.

It has now surprisingly been found that these particular mid-chain branched surfactants have excellent surface activity and cleaning performance under (severe) hard water conditions. Furthermore, it has surprisingly been found that detergent compositions comprising these mid-chain branched surfactants and only very low amounts of builders have excellent cleaning performance. It has also been found that mid-chain branched surfactants work better in (slightly) alkaline environments. However, reducing the level of builder materials in detergent compositions containing these mid-chain branched surfactants, which are known sources of alkalinity in detergent compositions, results in a weakly alkaline environment . To compensate for this aspect, the inventors have found that the addition of small amounts of alkalinity sources, preferably carbonates, to detergent compositions can provide the alkalinity required for optimum performance of mid-chain branched surfactants, while at the same time allowing builder materials to content decreased.

An additional advantage is that reducing the level of builder materials in detergent compositions can lead to reduced formulation costs.

All documents cited are hereby incorporated by reference.

Summary of the invention

The present invention relates to a solid detergent composition having a density of 330-1400 g/l, comprising:

a) at least 0.5%, preferably at least 5%, more preferably 10%, by weight of the composition, of a surfactant system comprising a long alkyl chain mid-chain branched surfactant compound of the formula:

A ^b -XB

in:

(I) A ^b is a hydrophobic mid-chain branched alkyl moiety of 9 to 22 carbon atoms in total, preferably 12 to about 18 carbon atoms, having: - the longest linear carbon chain in the range of 21 carbon atoms; (2) one or more C ₁ -C ₃ alkyl moieties branched from the longest linear carbon chain; (3) at least one branched chain alkyl moiety Directly to the 2-carbon position on the longest linear carbon chain counting from the 1-carbon position (#1) to which the -XB moiety is attached to the terminal carbon atom minus 2 carbons ((ω-2) carbons) and (4) when there are more than one of these compounds, the average total number of carbon atoms of the A ^b -X moiety in the above formula is greater than 14.5 to about 18, preferably about 15 to about 17;

(II) B is a hydrophilic moiety selected from sulfates, sulfonates, amine oxides, polyoxyalkylenes, preferably polyoxyethylenes and polyoxypropylenes, alkoxylated sulfates, polyhydroxy moieties, phosphates, Glyceryl Sulfonate, Polygluconate, Polyphosphate, Phosphonate, Sulfosuccinate, Sulfosuccinamate, Polyalkoxylated Carboxylate, Glucamide, Taurate, Sarcosinate, Glycinate, Isethionate, Dialkanolamide, Monoalkanolamide, Monoalkanolamide Sulfate, Diglycolamide, Diglycolamide Sulfate, Glycerides, Glycerides Sulfates, glyceryl ethers, glyceryl ether sulfates, polyglyceryl ethers, polyglyceryl ether sulfates, sorbitan esters, polyalkoxylated sorbitan esters, ammonioalkanesulfonate, amidopropyl betaine, alkylated quaternary ammonium salt, alkylated/polyhydroxyalkylated quaternary ammonium salt, alkylated quaternary ammonium salt, alkylated/polyhydroxylated oxypropyl quaternary ammonium salt, imidazoline, 2- Alkyl-succinates, sulfonated alkyl esters, and sulfonated fatty acids; and

(III) X is selected from _-CH2- and -C(O)-; and

b) 0.5% to 25% builder system by weight of the composition; and

c) 0.0% to 50% of an alkaline system comprising carbonate, by weight of the composition;

The prerequisite is that when the content of system a) is 3% by weight and the content of system b) is 19% by weight, the alkaline system c) does not include 8% by weight of sodium carbonate.

Preferably the surfactant system a) comprises mid-chain branched primary alkyl sulfate or sulfonate surfactants.

Detailed description of the invention

Surfactant systems containing mid-chain branched surfactant compounds

The detergent compositions of the present invention comprise at least 0.5%, preferably at least 5%, more preferably at least 10% by weight of a surfactant system comprising surfactant compounds of formula as defined above Long alkyl chain mid-chain branched surfactant compound.

Preferred surfactant systems of the present invention comprise long alkyl chain mid-chain branched surfactant compounds of the above formula wherein the A ^b moiety is a branched primary alkyl moiety having the formula:

wherein the total number of carbon atoms in the branched primary alkyl portion of the formula (including R, ^R and ^R branches) is 13-19; R, ^R and R ^{are each} independently selected from hydrogen and _{C -C} Alkyl (preferably methyl), with the proviso that R, ^R and ^R are not all hydrogen, and when z is 0, at least R or ^R is not hydrogen; w is an integer from 0 to 13; x is an integer of 0-13; y is an integer of 0-13; z is an integer of 0-13; and w+x+y+z is 7-13.

Typically, for mid-chain branched surfactant compounds of surfactant systems, certain branch points (e.g., chain positions along the R, R ^, and/or ^R moieties in the above formula) are more active than along the surface active Other branching points of the agent backbone are preferred. The following formulas illustrate the range of mid ^- chain branching (i.e., at which points branching occurs), the preferred range of mid-chain branching, and the more preferred range of chain branching.

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

The following formulas illustrate the range of mid-chain branching, preferred ranges of mid-chain branching, and more preferred ranges of mid-chain branching for dimethyl-substituted alkyl A ^b moieties suitable according to the present invention.

Preferred are surfactant compounds wherein the A ^b moiety in the above formula does not have any tetrasubstituted carbon atoms (ie 4 carbon atoms directly bonded to one carbon atom).

The most preferred mid-chain branched surfactant compounds for use in the detergent compositions herein are mid-chain branched primary alkyl sulphonates and even more preferably sulphate surfactants.

Preferred mid-chain branched primary alkyl sulfate surfactants have the formula:

These surfactants have a backbone of linear primary alkyl sulfate chains (i.e. the longest linear carbon chain including the sulfated carbon atoms) which preferably contain 12-19 carbon atoms and their branched primary alkyl moieties preferably contain A total of at least 14 carbon atoms, preferably no more than 20 carbon atoms. In surfactant systems comprising more than one of these sulfate surfactants, the average total number of carbon atoms in the branched primary alkyl moieties is preferably from greater than 14.5 to about 17.5. Accordingly, the surfactant system preferably comprises at least one branched primary alkyl sulfate surfactant compound having the longest linear carbon chain of not less than 12 carbon atoms or not more than 19 carbon atoms, and The total number of carbon atoms including branching must be at least 14, additionally, for branched primary alkyl moieties, the average total number of carbon atoms is from greater than 14.5 to about 17.5.

R, ^R and ^R are each independently selected from hydrogen and C ₁ -C ₃ alkyl (preferably hydrogen or C ₁ -C ₂ alkyl, more preferably hydrogen or methyl, and most preferably methyl), with the proviso that R , R ¹ and R ² are not both hydrogen. Additionally, when z is 1, at least R or ^R1 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, tetraalkylammonium having the formula:

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 ( ^R3 , ^R4 , ^R5 and ^R6 are all hydrogen), sodium, potassium, mono-, di- and trialkanolammonium, and mixtures thereof. R ³ of the monoalkanol ammonium compound of the present invention is C ₁ -C ₆ alkanol, R ⁴ , R ⁵ and R ⁶ are hydrogen; R ³ and R ⁴ of the dialkanol ammonium compound of the present invention are C ₁ -C ₆ alkanol Alcohol, R ⁵ and R ⁶ are hydrogen; R ³ , R ⁴ and R ⁵ of the trialkanol ammonium compound of the present invention are C ₁ -C ₆ alkanol, R ⁶ is hydrogen. Preferred alkanolammonium salts of the present invention are mono-, di- and triquaternary ammonium compounds having the formula:

H ₃ N ⁺ CH ₂ CH ₂ OH, H ₂ N ⁺ (CH ₂ CH ₂ OH) ₂ , HN ⁺ (CH ₂ CH ₂ OH) ₃ . Preferably M is sodium, potassium and the above mentioned _C2 alkanolammonium salts; most preferably sodium.

Also regarding the above formula, w is an integer of 0-13; x is an integer of 0-13; y is an integer of 0-13; z is an integer of at least 1; and w+x+y+z is an integer of 8-14 .

Another preferred surfactant system of the present invention has one or more branched primary alkyl sulfates of the formula:

wherein the total number of carbon atoms including branching is from 15 to 18, and when more than one of these sulfates are present, the average total number of carbon atoms in the branched primary alkyl portion having the above formula is greater than 14.5 to about 17.5 ; R ¹ and R ² are each independently hydrogen or C ₁ -C ₃ alkyl; M is a water-soluble cation; x is 0-11; y is 0-11; z is at least 2; and x+y+z is 9-13; with the proviso that ^R1 and ^R2 are not both hydrogen.

Preferably the surfactant system comprises at least 20%, more preferably at least 60%, even more preferably at least 90% mid-chain branched primary alkyl sulfate by weight of the system, preferably R ^{and R} are independently hydrogen or formazan group, provided that R ^and R are not ^both hydrogen; x+y is equal to 8, 9 or 10, and z is at least 2, whereby the average total number of carbon atoms in these sulfate surfactants is preferably 14-18, More preferably 15-17, even more preferably 16-17.

Additionally, preferred surfactant systems comprise at least about 20%, more preferably at least 60%, and even more preferably at least 90%, by weight of the system, of one or more mid-chain branched alkyl sulfates having the formula or Its mixture:

or

Wherein M represents one or more cations; a, b, d and e are integers, a+b is 10-16, d+e is 8-14, and wherein:

When a+b=10, a is an integer of 2-9 and b is an integer of 1-8;

When a+b=11, a is an integer of 2-10 and b is an integer of 1-9;

When a+b=12, a is an integer of 2-11 and b is an integer of 1-10;

When a+b=13, a is an integer of 2-12 and b is an integer of 1-11;

When a+b=14, a is an integer of 2-13 and b is an integer of 1-12;

When a+b=15, a is an integer of 2-14 and b is an integer of 1-13;

When a+b=16, a is an integer of 2-15 and b is an integer of 1-14;

When d+e=8, d is an integer of 2-7 and e is an integer of 1-6;

When d+e=9, d is an integer of 2-8 and e is an integer of 1-7;

When d+e=10, d is an integer of 2-9 and e is an integer of 1-8;

When d+e=11, d is an integer of 2-10 and e is an integer of 1-9;

When d+e=12, d is an integer of 2-11 and e is an integer of 1-10;

When d+e=13, d is an integer of 2-12 and e is an integer of 1-11;

When d+e=14, d is an integer of 2-13 and e is an integer of 1-12.

Thus, when more than one of these sulfate surfactants is present in the surfactant system, the average total number of carbon atoms of the branched primary alkyl moiety having the above formula is from greater than 14.5 to about 17.5.

Preferred monomethyl branched primary alkyl sulfates are selected from the group consisting of: 3-methylpentadecanol sulfate, 4-methylpentadecanol sulfate, 5-methylpentadecanol sulfate, 6 -Methylpentadecanol Sulfate, 7-Methylpentadecanol Sulfate, 8-Methylpentadecanol Sulfate, 9-Methylpentadecanol Sulfate, 10-Methylpentadecane Alcohol Sulfate, 11-Methylpentadecanol Sulfate, 12-Methylpentadecanol Sulfate, 13-Methylpentadecanol Sulfate, 3-Methylhexadecanol Sulfate, 4- Methyl Cetyl Sulfate, 5-Methyl Cetyl Sulfate, 6-Methyl Cetyl Sulfate, 7-Methyl Cetyl Sulfate, 8-Methyl Cetyl Sulfate Sulfate, 9-methyl cetyl sulfate, 10-methyl cetyl sulfate, 11-methyl cetyl sulfate, 12-methyl cetyl sulfate, 13-methyl cetyl sulfate Cetyl Cetyl Sulfate, 14-Methyl Cetyl Sulfate, and mixtures thereof.

Preferred dimethyl branched primary alkyl sulfates are selected from the group consisting of: 2,3-methyltetradecyl sulfate, 2,4-methyltetradecyl sulfate, 2,5-methyltetradecane Alcohol Sulfate, 2,6-Methyltetradecyl Sulfate, 2,7-Methyltetradecyl Sulfate, 2,8-Methyltetradecyl Sulfate, 2,9-Methyltetradecyl Sulfate Tetradecyl Sulfate, 2,10-Methyltetradecyl Sulfate, 2,11-Methyltetradecyl Sulfate, 2,12-Methyltetradecyl Sulfate, 2,3-Methyltetradecyl Sulfate Pentadecyl alcohol sulfate, 2,4-methyl pentadecyl alcohol sulfate, 2,5-methyl pentadecyl alcohol sulfate, 2,6-methyl pentadecyl alcohol 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, 2,13-methylpentadecanol sulfate, and mixtures thereof.

The following branched primary alkyl sulfates comprising 16 carbon atoms and having one branching unit are examples of preferred branched surfactants suitable for use in the compositions of the present invention:

5-Methylpentadecyl sulfate having the formula:

6-methylpentadecyl sulfate having the formula:

7-Methylpentadecyl sulfate having the formula:

8-Methylpentadecyl sulfate having the formula:

9-methylpentadecyl sulfate having the formula:

10-methylpentadecyl sulfate having the formula:

wherein M is preferably sodium.

The following branched primary alkyl sulfates comprising 17 carbon atoms and having two branch units are examples of branched surfactants which are preferred according to the invention:

2,5-Dimethylpentadecyl sulfate having the formula:

2,7-Dimethylpentadecyl sulfate having the formula:

2,8-Dimethylpentadecyl sulfate having the formula:

2,9-Dimethylpentadecyl sulfate having the formula:

2,10-Dimethylpentadecyl sulfate having the formula:

wherein M is preferably sodium.

Builder system

The detergent compositions of the present invention comprise from 0.5% to 25% by weight of the detergent composition of a builder system, preferably from 1.0% to 20%, more preferably from 5% to 18%, even more preferably from 8% to 18%.

Water-soluble and partially water-soluble or water-insoluble builder compounds can be included in the builder systems of the present invention.

Suitable water-soluble builder compounds include water-soluble monomeric polycarboxylates or their acid forms, homo- or co-polymeric polycarboxylic acids or salts thereof. Preferably the polycarboxylic acid or salt thereof comprises at least two carboxyl groups separated from each other by not more than two carbon atoms. The builder compounds also include borates and mixtures of any of the foregoing.

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

Suitable carboxylate salts or acids thereof containing one carboxyl group include the water soluble salts of lactic acid, glycolic acid and ether derivatives thereof. Polycarboxylates containing two carboxy groups or their acids including succinic acid, malonic acid, (ethylenedioxy) diacetic acid, maleic acid, glyoxylic acid, tartaric acid, tartronic acid and fumaric acid Water-soluble salts, as well as ether carboxylates and thionyl carboxylates. Polycarboxylates containing three carboxy groups or their acids including, inter alia, the water-soluble citrates, aconitates and citraconates, and succinate derivatives such as carboxymethoxysuccinate as described in British Patent 1,379,241 salts, lactyloxysuccinates described in British Patent 1389732, aminosuccinates described in Dutch Patent 7205873, and oxygen polycarboxylate substances such as 2-oxa-1 , 1,3-propane tricarboxylate. The most preferred polycarboxylic acid containing three carboxyl groups is citric acid, monohydrate in anhydrous form or optionally in liquid form, preferably at a level of from 0.1% to 15%, more preferably at 0.5% by weight of the composition %-8%.

Polycarboxylates containing four carboxyl groups or their acids include oxydisuccinates described in British Patent 1,261,829, and 1,1,2,2-ethane tetracarboxylates, 1,1,3,3-propane Tetracarboxylates and 1,1,2,3-propane tetracarboxylates. Polycarboxylates containing sulfo substituents or acids thereof include sulfosuccinate derivatives described in British Patents 1,398,421 and 1,398,422 and U.S. Patent No. 3,936,448, and sulfonated pyrolyzed citric acids described in British Patent 1,439,000 Salt. Preferred polycarboxylates or acids thereof are hydroxycarboxylates or acids thereof containing up to 3 carboxy groups per molecule, more particularly citrates or citric acids as described above.

It should be understood that mixtures of monomeric or oligomeric polycarboxylate parent acids or salts thereof such as citric acid or citrate/citric acid mixtures are also contemplated as useful builder compounds for the builder systems of the present invention.

Organic polymers are preferred builder compounds for the builder system of the detergent compositions of the present invention and are preferably present as a component of any particulate components which may serve, for example, to bind the particulate components together. By organic polymeric builder compounds, it is meant here any polymeric or oligomeric (poly)carboxylate compounds other than the aforementioned polymeric or oligomeric (poly)carboxylate compounds commonly used in detergents as builders, dispersants, anti-redeposition agents and soil suspension agents Essentially any organic polymer.

Organic polymers are typically incorporated in the builder systems of the present invention at levels of from 0.1 to 50%, preferably from 0.5 to 35%, more preferably from 1 to 20%, by weight of the builder system.

Such materials include the water-soluble salts of copolymers of acrylic acid and maleic acid/maleic anhydride. The average molecular weight of such acid form copolymers may range from 1,000 to 100,000, more preferably from 2,000 to 75,000, even more preferably up to 70,000, but most preferably are copolymers having an average molecular weight of from 2,500 to 20,000 or in another preferred example is 60000-75000 or even 70000 copolymers. The ratio of acrylate to maleate moieties in such copolymers is generally from 30:1 to 1:30, more preferably from 10:1 to 1:1, most preferably from 4:1 to 7:3. Water-soluble salts of such acrylic acid/maleic acid copolymers can include, for example, alkali metal, ammonium and substituted ammonium salts. Soluble acrylate/maleate copolymers of this type are known materials and are described in European Patent Application 66915, published December 15, 1982, and in EP193360, published September 3, 1986.

Other suitable polymeric carboxylate-containing builder compounds are available from acrylic acid. Such acrylic acid-based polymers that can be used in the present invention are, for example, water-soluble salts of polyacrylic acid. The average molecular weight of the homopolymer in the acid form is preferably 1800-100000, more preferably 2000-10000, most preferably 3000-5000. Water-soluble salts of such acrylic acid polymers may include, for example, alkali metal, ammonium and substituted ammonium salts. Such soluble polymers are known materials. For example, Diehl's US Patent No. 3,308,067 issued on March 7, 1967 discloses the use of such polyacrylates in detergent compositions.

Additional polyamino based compounds are also useful herein, including those derived from aspartic acid, for example those described in EP-A-305282, EP-A-305283 and EP-A-351629.

Another example of a polymeric carboxylate-containing builder compound suitable for the purposes of the present invention includes maleic/acrylic acid/vinyl alcohol terpolymers. Such materials are also disclosed in EP193160 and include, for example, a 45/45/10 acrylic acid/maleic acid/vinyl alcohol terpolymer.

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

Other useful polymeric carboxylate-containing builder compounds are polyelectrolyte-containing glycols, especially those having a molecular weight of 1,000-10,000, more preferably 2,000-8,000, most preferably about 4,000.

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

Such polymeric carboxylate-containing builder compounds preferably have a molecular weight of 500-100,000, more preferably 1,000-70,000, particularly preferably 1,500-10,000, or in another preferred embodiment, 2,800-6,000. The polymeric carboxylate-containing builder compounds useful in the present invention can be prepared, for example, by using conventional aqueous polymerization methods, suitable methods being described, for example, in GB8924477, GB8924478 and GB8924479.

Usually the hydrophilic backbone of the polymer is predominantly linear (the main chain of the backbone constitutes at least 50%, preferably more than 75%, and most preferably more than 90% by weight of the backbone), suitable monomer groups for the hydrophilic backbone Components are, for example, unsaturated C ₁ -C ₆ acids, ethers, alcohols, aldehydes, ketones or esters, sugar units, alkoxy units, maleic anhydride and saturated polyols such as glycerol. Preferably the hydrophobic side chains consist of alkoxy groups, for example oxybutylene and/or oxypropylene and/or alkyl or alkenyl chains having 5 to 24 carbon atoms. Hydrophobic groups can be attached to the hydrophilic backbone through oppositely hydrophilic linkages, such as polyethoxy linkages.

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

Preferred counterions for polymeric organic (carboxylate-containing) builder compounds are, for example, sodium, magnesium or calcium ions.

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

The builder systems of the present invention may comprise phosphate-containing builder materials. Preferably, however, the builder system is substantially free of phosphate-containing builders. Suitable examples of water-soluble phosphate builders are alkali metal tripolyphosphates, sodium, potassium and ammonium pyrophosphates, sodium and potassium orthophosphates, sodium polymeta/phosphates, wherein the degree of polymerization is about 6-21, and phytic acid Salt.

The builder system may also comprise silicate-containing builder compounds. Preference is given to sodium silicate, preferably with SiO ₂ :Na ₂ O=2:1. Preferred may be amorphous sodium silicate.

Other preferred silicate-containing builder compounds are crystalline layered silicates, preferably sodium silicates. Preference may be given to the crystalline layered silicate _{of the} formula δ- _Na2Si2O5 , known as NaSKS-6 (Hoechst).

Other highly preferred builders for inclusion in the builder systems of the present invention are aluminosilicate zeolites, preferably having the unit cell formula Na _z [(AlO ₂ ) _z (SiO ₂ ) _y ]-xH ₂ O, Wherein z and y are at least 6, the molar ratio of z to y is 1.0-0.5, x is at least 5, preferably 7.5-276, more preferably 10-264. The aluminosilicate material is in hydrated form, preferably in crystalline form, containing 10-28%, more preferably 18-22%, by weight of the material, of bound water.

Aluminosilicate zeolites may be naturally occurring materials, but are preferably synthetically derived. Synthetic crystalline aluminosilicate ion exchange materials are commercially available as 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 ) ₁₂ ]-xH ₂ O

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

Zeolite MAP builder is another preferred aluminosilicate zeolite.

Zeolite MAP is described in EP 384070A (Unilever) and is defined as a zeolite P-type alkali metal aluminosilicate having a silicon to aluminum ratio not greater than 1.33, preferably 0.9-1.33, more preferably 0.9-1.2.

Of particular interest are zeolites MAP having a silicon to aluminum ratio not greater than 1.15, more specifically not greater than 1.07.

In a preferred aspect, the particle size of the zeolite MAP detergent builder, expressed as d ₅₀ , is 1.0-10.0 μm, more preferably 2.0-7.0 μm, most preferably 2.5-5.0 μm.

The d ₅₀ value means that 50% by weight of the particles have a diameter smaller than this value. Specifically, the particle size can be determined by conventional analytical techniques, such as microscopic measurement using a scanning electron microscope or measurement with a laser particle size analyzer. Other methods of determining _d50 values are described in EP 384070A.

alkaline system

The detergent compositions of the present invention preferably comprise up to 50%, more preferably from 5% to 30%, more preferably from 8% to 20%, even more preferably from 10% to 15%, by weight of the composition, of carbonate-comprising alkaline system.

Examples of preferred carbonates are alkaline earth metal and alkali metal carbonates, including sodium carbonate, sodium bicarbonate and sodium sesquicarbonate and any mixtures thereof with ultrafine calcium carbonate, such as disclosed in Nov. 15, 1973 German patent application 2321001. Alkali metal percarbonates may also be included in the alkaline system of detergent compositions and are also suitable carbonates, which are described in more detail below.

A highly suitable carbonate may be anhydrous sodium carbonate. Preferably the carbonates are included in particles with a particle size of 200 μm to 900 μm, the anhydrous sodium bicarbonate having a particle size distribution between 400 μm and 1200 μm.

other detergent components

The detergent compositions of the present invention may also contain other detergent ingredients. The exact nature of these other components and the amount incorporated therein will depend upon the physical form of the composition or component and the exact nature of the laundering operation in which it is used.

The compositions or components thereof according to the invention preferably comprise one or more other detergent components selected from other surfactants, bleaches, bleach catalysts, other organic polymers, enzymes, suds suppressors, lime soap dispersants , Soil Suspending and Anti-redeposition Agents, Soil Release Agents, Fragrances, Brighteners, Photo-Bleaches and Other Corrosion Inhibitors.

Other Detergent Surfactants

Optionally, other surfactants may be present, selected from anionic, zwitterionic and amphoteric surfactants.

Based on the weight of the detergent composition, the total amount of surfactant is preferably 1%-95%, preferably 3%-70%, more preferably 5%-40%, even more preferably 10%-30%, most preferably 12%-25%.

A preferred aspect of the invention is a granular detergent composition. One or more surfactants may be included in the base composition, optionally with a hydrophobic peroxyacid bleach component and/or a hydrophilic nonionic surface active component. The base composition may be prepared by spray drying and/or dry mixing/agglomeration as described herein.

anionic surfactant

The detergent compositions of the present invention may contain one or more other anionic surfactants. Any anionic surfactant used for detersive purposes is suitable. Examples include anionic sulfate, sulfonate, carboxylate and sarcosinate surfactants (including, for example, sodium, potassium, ammonium and substituted ammonium salts such as mono-, di- and triethanolamine salts). Anionic sulfate surfactants are preferred.

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

The anionic surfactant is preferably present in an amount of 0.5%-60%, preferably 3%-50%, more preferably 5%-35%, most preferably 6%-20%, by weight of the composition.

Anionic Sulfate Surfactant

Other anionic sulfate surfactants suitable for use herein include linear and branched primary and secondary alkyl sulfates, alkyl ethoxy sulfates, fatty oleoyl glycerol sulfates, alkylphenol oxirane ether sulfates salt, C ₅ -C ₁₇ acyl-N-(C ₁ -C ₄ alkyl) and -N-(C ₁ -C ₂ hydroxyalkyl) glucosamine sulfates, and sulfates of alkyl polysaccharides such as alkane Sulfate salts of polyglucosides (non-ionic, non-sulfated compounds are described below).

Alkyl sulfate surfactants are preferably selected from linear and branched primary C ₉ -C ₂₂ alkyl sulfates, more preferably C ₁₁ -C ₁₅ branched chain alkyl sulfates and C ₁₂ -C ₁₄ linear alkyl sulfates Salt.

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

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

Anionic Sulfonate Surfactant

Other anionic sulfonate surfactants suitable for use herein include C ₅ -C ₂₀ linear alkylbenzene sulfonates, alkyl ester sulfonates, C ₆ -C ₂₂ primary or secondary alkane sulfonates, C ₆ - _C24 olefin sulfonates, sulfonated polycarboxylic acids, alkyl glycerol sulfonates, fatty acyl glycerol sulfonates, fatty oleoyl glycerol sulfonates, and any mixtures thereof.

Anionic Carboxylate Surfactants

Suitable anionic carboxylate surfactants include alkyl ethoxy carboxylates, alkyl polyethoxy polycarboxylate surfactants and soaps ("alkyl carboxy" soaps), especially as described herein. Certain secondary soaps.

Suitable alkyl ethoxy carboxylates include those having the formula RO(CH ₂ CH ₂ O) _x CH ₂ COO ^- M ⁺ , wherein R is C ₆ -C ₁₈ alkyl, x is 0-10, E The oxide distribution should be such that the amount of species where x is 0 is less than 20% by weight and M is a cation. Suitable alkyl polyethoxy polycarboxylate surfactants include those having the formula RO-(CHR ₁ -CHR ₂ -O) _x -R ₃ wherein R is a C ₆ -C ₁₈ alkyl group and x is 1-25, R ₁ and R ₂ are selected from hydrogen, methyl acid, succinic acid, hydroxysuccinic acid and mixtures thereof, R ₃ is selected from hydrogen, substituted or unsubstituted hydrocarbon groups with 1-8 carbon atoms , and mixtures thereof.

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

Alkali metal sarcosinate surfactant

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

nonionic surfactant

When present in the detergent compositions herein, nonionic surfactants are preferably present at low levels, preferably 0.5% to 20%, more preferably 1% to 15%, even more preferably 1.5% to 8% by weight. Nonionic surfactants, when present, are preferably present in a ratio of 5:1 to 1:20, more preferably 5:1 to 1:10, even more preferably 1:1 to 1:10 to the surfactant system.

Alkoxylated Nonionic Surfactants

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

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

Nonionic Alkoxylated Alcohol Surfactants

Condensation products of fatty alcohols with 1 to 25 moles of alkylene oxides, especially ethylene oxide and/or propylene oxide, are suitable for use in the present invention. The alkyl chain of the fatty alcohol may be straight or branched, primary or secondary, and generally contains 6 to 22 carbon atoms. Particular preference is given to alcohols having alkyl groups of 8 to 20 carbon atoms, or more preferably 9 to 15 carbon atoms, condensation products with 3 to 12 moles of ethylene oxide per mole.

Nonionic Polyhydroxy Fatty Acid Amide Surfactant

Polyhydroxy fatty acid amides suitable for use in the present invention are those having the formula: R ² CONR ¹ Z, where R ¹ is H, C ₁ -C ₄ hydrocarbyl, 2-hydroxyethyl, 2-hydroxypropyl, ethoxy , propoxy or a mixture thereof, preferably C ₁ -C ₄ alkyl, more preferably C ₁ or C ₂ alkyl, most preferably C ₁ alkyl (ie methyl); R ² is C ₅ -C ₃₁ hydrocarbon, preferably Straight chain C ₅ -C ₁₉ alkyl or alkenyl, more preferably straight chain C ₉ -C ₁₇ alkyl or alkenyl, most preferably straight chain C ₁₁ -C ₁₇ alkyl or alkenyl, or a mixture thereof; Z is a polyhydroxyhydrocarbyl group having a linear hydrocarbyl chain directly attached to at least 3 hydroxyl groups, or an alkoxylated derivative (preferably ethoxylated or propoxylated) thereof. Z is preferably obtained from a reducing sugar in a reductive amination reaction. More preferably Z is a sugar group.

Nonionic Fatty Acid Amide Surfactant

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

Nonionic Alkyl Polysaccharide Surfactant

Alkyl polysaccharides suitable for use in the present invention are described in US 4,565,647, Llenado, issued January 21, 1986, they have hydrophobic groups containing 6-30 carbon atoms, and polysaccharides containing 1.3-10 sugar units are hydrophilic groups, such as polyglycosides.

Preferred alkyl polyglycosides have the formula:

R ² O(C _n H _2n O) _t (glycosyl) _X

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

amphoteric surfactant

Suitable amphoteric surfactants for use herein include amine oxide surfactants and alkyl amphocarboxylic acids.

Suitable amine oxides include those compounds of the formula R ³ (OR ⁴ ) _x N ⁰ (R ⁵ ) ₂ wherein R ³ is selected from the group consisting of alkyl, hydroxyalkyl, acylamidopropyl and Alkylphenyl, or a mixture thereof; R ⁴ is an alkylene or hydroxyalkylene group containing 2-3 carbon atoms, or a mixture thereof; x is 0-5, preferably 0-3; each R ⁵ is a Alkyl or hydroxyalkyl groups of 1-3 carbon atoms, or polyethylene oxide groups containing 1-3 oxirane groups. Preference is given to C ₁₀ -C ₁₈ alkyldimethylamine oxides and C ₁₀ -C ₁₈ acylamidoalkyldimethylamine oxides.

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

zwitterionic surfactant

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

Suitable betaines are those compounds having the formula: R(R') ₂ N ⁺ R ² COO ^- , wherein R is C ₆ -C ₁₈ hydrocarbyl, each R ₁ is typically C ₁ -C ₃ alkyl, R ² is a C ₁ -C ₅ hydrocarbon group. Preferred betaines are C ₁₂ -C ₁₈ dimethylammonium hexanoate and C ₁₀ -C ₁₈ acylamidopropane (or ethane) dimethyl (or diethyl) betaine. Complex betaine surfactants are also suitable for use in the present invention.

cationic surfactant

Suitable cationic surfactants for use in the detergents of the present invention include quaternary ammonium surfactants. Quaternary ammonium surfactants are preferably mono C ₆ -C ₁₆ , preferably C ₆ -C ₁₀ N-alkyl or alkenyl ammonium surfactants in which the remaining positions of N are substituted by methyl, hydroxyethyl or hydroxypropyl groups . Also preferred are monoalkoxylated and bisalkoxylated amine surfactants.

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

Suitable cationic ester surfactants include choline ester surfactants such as those disclosed in US4228042, 4239660 and 4260529.

In a preferred aspect, the ester bond and the cationic charged group are separated from each other in the surfactant molecule by a spacer consisting of a chain comprising at least three atoms (i.e. three atoms long). ), preferably 3-8 atoms, more preferably 3-5 atoms, most preferably 3 atoms. The atoms forming the spacer chain are selected from carbon, nitrogen and oxygen atoms and any mixtures thereof, provided that any nitrogen or oxygen atom in said chain is bonded only to a carbon atom in the chain. Thus, spacers having linkages such as -OO- (ie peroxide), -NN- and -NO- are excluded and spacers having linkages such as _-CH2 -O- _CH2- and _-CH2 -NH- _CH2 - a spacer for the bond. In a preferred aspect, the spacer chain contains only carbon atoms, most preferably the chain is a hydrocarbyl chain.

Cationic Monoalkoxylated Amine Surfactants

Cationic monoalkoxylated amine surfactants preferably have the general formula I:

wherein ^R is an alkyl or alkenyl moiety containing from about 6 to 18 carbon atoms, preferably from 6 to about 16 carbon atoms, most preferably from about 6 to 14 carbon atoms; R ^{and R} are each independently 1-Alkyl of about 3 carbon atoms, preferably methyl, most preferably ^R2 and ^R3 are both methyl; ^R4 is selected from hydrogen (preferred), methyl and ethyl, X ^- is to provide electrical neutrality Anions such as chlorine, bromine, methylsulfate, sulfate, etc. A is alkoxy, especially ethoxy, propoxy or butoxy; p is 0 to about 30, preferably 2 to about 15, most preferably 2 to about 8, provided that if A is ethoxy, R ⁴ is hydrogen and p is 1, then R ₁ is not C ₁₂ -C ₁₄ alkyl.

In formula I, it is preferred that the ApR ⁴ group has p=1 and is a hydroxyalkyl group having not more than 6 carbon atoms, whereby the -OH group is separated from the quaternary ammonium nitrogen atom by not more than 3 carbon atoms. Particularly _{preferred ApR4 groups are -CH2CH2OH, -CH2CH2CH2OH, -CH2CH} ⁽ _{CH3 ) OH and -CH ( CH3 ) CH2OH} , _-CH2CH2OH is particularly preferred. Preferably the ^R1 group has no more than 10 carbon atoms, or even no more than 8 or 9 carbon atoms. Preferably the ^R1 group is a straight chain alkyl group. Straight chain R ¹ groups having 8-11 carbon atoms or having 8-10 carbon atoms are preferred. Highly preferred such cationic surfactants are of the formula wherein R ¹ is C ₈ -C ₁₀ alkyl, p is 1, A is ethoxy, R ² and R ³ are methyl.

Another highly preferred cationic monoalkoxylated amine surfactant for use herein has the formula:

wherein R ¹ is C ₁₀ -C ₁₈ hydrocarbyl and mixtures thereof, especially C ₁₀ -C ₁₄ alkyl, preferably C ₁₀ and C ₁₂ alkyl, and X is any suitable anion providing charge balance, preferably chlorine or bromine.

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

The level of cationic monoalkoxylated amine surfactants used in the detergent compositions of the present invention is preferably from 0.1% to 20%, more preferably from 0.4% to 7%, most preferably from 0.5% by weight of the composition -3.0%.

Cationic dialkoxylated amine surfactants

Cationic dialkoxylated amine surfactants preferably have the general formula II:

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

Highly preferred cationic dialkoxylated amine surfactants for use herein have the formula:

wherein R ¹ is C ₁₀ -C ₁₈ hydrocarbyl and mixtures thereof, preferably C ₁₀ , C ₁₂ , C ₁₄ alkyl and mixtures thereof, and X is any suitable anion providing charge balance, preferably chlorine. With regard to the general structure of the above cationic dialkoxylated amines, in preferred compounds ^R1 is derived from (coco) _C12 - _C14 alkyl moiety fatty acid, ^R2 is methyl, ^ApR3 and A'qR ⁴ are all monoethoxy groups.

Other cationic dialkoxylated amine surfactants suitable for use herein include compounds of the formula:

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

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

The level of cationic dialkoxylated amine surfactants used in the detergent compositions of the present invention is preferably from 0.1% to 20%, more preferably from 0.4% to 7%, most preferably from 0.5% by weight of the composition -3.0%.

optional surfactant

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

Other optional additional anionic surfactants are carboxylate-based anionic surfactants and alkali metal sarcosinates of formula R—CON(R ¹ )CH ₂ COOM, where R is C ₅ -C ₁₇ Straight chain or branched alkyl or alkenyl, R ¹ is C ₁ -C ₄ alkyl, M is an alkali metal ion. Preferred examples are endomyristyl and oleoyl methyl sarcosinates in the sodium salt form.

perhydrate bleach

Preferred further ingredients of the detergents according to the invention are perhydrate bleaches, such as metal perborate, metal percarbonate, especially sodium salts. Perborate may be monohydrate or tetrahydrate. Sodium percarbonate _has a chemical formula corresponding to _{2Na2CO3-3H2O2} and is commercially available as _a crystalline _solid .

Potassium peroxymonopersulfate, sodium is another optional inorganic perhydrate salt for use in the detergent compositions herein.

Organic peroxyacid bleaching system

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

Peroxyacid Bleach Precursors

Peroxyacid bleach precursors are compounds which react with hydrogen peroxide in a perhydrolysis reaction to produce a peroxyacid. Typically, peroxyacid bleach precursors are represented by the formula:

Wherein, L is a leaving group, and X is basically any functional group, so that the peroxyacid structure produced during perhydrolysis is

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

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

leaving group

The leaving group, hereinafter referred to as the L group, must be sufficiently reactive for the perhydrolysis reaction to occur during an optimal period of time, such as a wash cycle. However, if L is too reactive, the activator will be difficult to use stably in bleaching compositions.

Preferred L groups are selected from the following groups or mixtures thereof:

and

and

Wherein, R ¹ is an alkyl, aryl or alkaryl group containing 1-14 carbon atoms, R ³ is an alkyl chain containing 1-8 carbon atoms, R ⁴ is H or R ³ , Y is H or Solubilizing group. Any of ^R1 , ^R3 , and ^R4 may be substituted with essentially any functional group, including, for example, alkyl, hydroxyl, alkoxy, halogen, amino, nitrosyl, amido, and ammonium or alkylammonium groups .

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

Alkyl percarboxylic acid bleach precursor

Alkyl percarboxylic acid bleach precursors form percarboxylic acids on perhydrolysis. Preferred precursors of this type provide peracetic acid upon perhydrolysis.

Preferred imide-type alkyl percarboxylic acid precursor compounds include N,N,N',N'-tetraacetylated alkylenediamines, wherein the alkylene group contains 1-6 carbon atoms, Especially those compounds in which the alkylene group contains 1, 2 and 6 carbon atoms. Particular preference is given to tetraacetylethylenediamine (TAED). TAED is preferably absent from the agglomerated granules of the present invention, but is preferably present in detergent compositions comprising the granules according to the present invention.

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

Amide Substituted Alkyl Peroxyacid Precursors

Amide substituted alkyl peroxyacid precursor compounds are suitable for use in the present invention and include compounds of the general formula:

or

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

Precursor of perbenzoic acid

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

cationic peroxyacid precursor

Cationic peroxyacid precursor compounds produce cationic peroxyacids upon perhydrolysis.

Typically, cationic peroxyacid precursors are formed by substituting a positively charged functional group such as an ammonium or alkylammonium group, preferably an ethyl or methylammonium group, for the peroxyacid moiety of a suitable peroxyacid precursor compound. Forming. The cationic peroxyacid precursor is usually present in solid detergent compositions as a salt with a suitable anion such as a halide.

Such cationic substituted peroxyacid precursor compounds may be perbenzoic acid or substituted derivatives thereof, such as the aforementioned precursor compounds. Alternatively, the peroxyacid precursor compound may be an alkyl percarboxylic acid precursor compound or an amide substituted alkyl peroxyacid precursor as described below.

阳离子过氧酸前体在下述文献中有述：US 4,904,406；4,751,015；4,988,451；4,397,757；5,269,962；5,127,852；5,093,022；5,106,528；U.K.1,382,594；EP 475,512；458,396和284,292；JP87-318,332。

Examples of preferred cationic peroxyacid precursors are described in UK Patent Application No. 9407944.9 and US Patent Application Nos. 08/298903, 08/298650, 08/298904 and 08/298906.

Suitable cationic peroxyacid precursors include ammonium or alkylammonium substituted alkyl or benzoyloxybenzenesulfonates, N-acylated caprolactam and monobenzoyltetraacetylglucose benzoyl peroxide of any kind. Preferred N-acylated caprolactam cationic peroxyacid precursors include trialkylammoniummethylenebenzoylcaprolactam and trialkylammoniummethylenealkylcaprolactam.

Benzoxazine Organic Peroxyacid Precursor

Also suitable are precursor compounds of the benzoxazine type, such as those described in EP-A-332,294 and EP-A-482,807, especially compounds of the formula:

Wherein, R ₁ is H, alkyl, alkaryl, aryl or aralkyl.

preformed organic peroxyacids

The detergent compositions of the present invention may comprise, in addition to or as an alternative to organic peroxyacid bleach precursor compounds, preformed organic peroxyacids, typically at a level of from 1 to 15% by weight of the compositions of the present invention , more preferably 1-10%.

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

或

or

Wherein, R ¹ is an alkyl group, aryl group or alkaryl group with 1-14 carbon atoms, R ² is an alkylene group, arylene group and alkarylene group with 1-14 carbon atoms, 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 disclosed in EP-A-0179386.

Other organic peroxyacids include diacyl and tetraacyl peroxides, especially diperoxydodecanedioic acid, diperoxytetradecanedioic acid and diperoxyhexadecandioic acid. Mono- and diperazelaic acid, mono- or dipertridecanedioic acid and N-naphthoylaminoperoxycaproic acid are also suitable for the present invention.

bleach catalyst

The detergent compositions herein may contain a transition metal-containing bleach catalyst.

A suitable type of bleach catalyst is one comprising transition metal cations such as copper, iron or manganese cations having defined bleach catalytic activity, auxiliary metal cations such as zinc or aluminum cations having little or no bleach catalytic activity, and catalytic and Catalyst systems assisting chelating agents with stability constants defined by metal cations, in particular ethylenediaminetetraacetic acid, ethylenediaminetetrakis(methylenephosphonic acid) and water-soluble salts thereof. Such catalysts are disclosed in US 4,430,243.

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

Bleach catalysts can also be selected for use in the present invention as appropriate for the present invention. See, for example, US 4,246,612 and 5,227,084 for suitable bleach catalysts. See also US 5,194,416 which teaches mononuclear manganese(IV) complexes such as Mn(1,4,7-trimethyl-1,4,7-triazacyclononane)-(OCH ₃ ) ₃ ( _PF6 ).

Another class of bleach catalysts as disclosed in US 5114606 are water-soluble complexes of manganese (III) and/or (IV) with polyol ligands of non-carboxylic acids having at least three consecutive C-OH groups . Preferred ligands include sorbitol, iditol, dulcitol, mannitol, xylitol, arabitol, adonitol, meso-erythritol, meso-inositol , lactose and mixtures thereof.

US Patent No. 5,114,611 teaches bleach catalysts comprising complexes of transition metals including Mn, Co, Fe or Cu with non-(macro)cyclic ligands. The ligand has the formula:

wherein each of R ¹ , R ² , R ³ and R ⁴ can be selected from H, substituted alkyl and aryl such that each of R ¹ -N=CR ² and R ³ -C=NR ⁴ forms a five- or six-membered ring . The rings can also be substituted. B is a bridging group selected from O, S, CR ⁵ R ⁶ , NR ⁷ and C═O, wherein each of R ⁵ , R ⁶ and R ⁷ can be H, alkyl or aryl, including substituted or unsubstituted groups group. Preferred ligands include pyridine, pyridazine, pyrimidine, pyrazine, imidazole, pyrazole and triazole rings. Optionally, the rings may be substituted with substituents such as alkyl, aryl, alkoxy, halogen and nitro. Particular preference is given to 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) _Cl2 , bis(isothiocyanato)bispyridylamine cobalt(II), tripyridylamine cobalt(II) perchlorate, Co( 2,2'-bispyridylamine) ₂ O ₂ ClO ₄ , bis(2,2'-bispyridylamine)copper(II) perchlorate, tris(bis-2-pyridylamine)iron(II) perchlorate salts and mixtures thereof.

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

Other bleach catalysts are disclosed in, for example, European Patent Application Publication No. 408,131 (cobalt complex catalysts), European Patent Application Publication Nos. 384,503 and 306,089 (metal-porphyrin catalysts), US 4,728,455 (manganese/polydentate ligand catalysts), US 4,711,748 and European Patent Application Publication No. 224,952 (manganese catalysts adsorbed on aluminosilicates), US 4,601,845 (manganese and zinc or magnesium salts supported on aluminosilicates), US 4,626,373 (manganese /ligand catalyst), US 4,119,557 (iron complex catalyst), DE 2,054,019 (cobalt chelate catalyst), CA 866,191 (transition metal-containing salt), US4,430,243 (chelate with manganese cation and non-catalytic metal cation) Mixture) and US4,728,455 (manganese gluconate catalyst).

Bleach catalysts are generally used in the compositions and methods of the present invention in catalytically effective amounts. By "catalytically effective amount" is meant an amount sufficient to enhance the bleaching and removal of the stain or some stain of concern on the target substrate, whatever the comparative experimental conditions used. The experimental conditions will vary according to the type of washing equipment used and the habits of the user. Some users choose to use very hot water; others use warm or even cold water in their washing operations. Of course, the catalytic performance of the bleach catalyst will be influenced by these considerations and the amount of bleach catalyst employed in fully formulated detergent and bleach compositions can be appropriately adjusted. In practice, without limitation, the compositions and methods of the present invention can be adjusted to provide at least about one part per million active bleach catalyst in the wash solution, preferably about 1 ppm to about 200 ppm catalyst in the wash solution. To further illustrate this point, about 3 micromolar manganese catalyst was effective under European conditions at 40°C, pH 10 using perborate and bleach precursors. Under US conditions, a 3-5 fold increase in concentration may be required to obtain the same results.

enzyme

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

Preferred additional enzymatic materials include the commercially available lipases, cutinases, amylases, neutral and alkaline proteases, cellulases, endolases, esterases, fruit enzymes conventionally added to detergent compositions. Gelase, Lactase and Peroxidase. Suitable enzymes are discussed in US3519570 and US3533139.

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

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

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

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

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

Antifoam system

When the detergent composition of the present invention is formulated as a composition for machine washing, it preferably comprises a suds suppressing system in an amount of 0.01-15%, preferably 0.05-10%, more preferably by weight of the composition 0.1-5%.

Suitable suds suppressing systems for use in the present invention may comprise essentially any known antifoam compound, including, for example, silicone antifoam compounds and 2-alkyl alkanol antifoam compounds.

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

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

Other suitable antifoam compounds include monobasic fatty carboxylic acids and soluble salts thereof. These substances are described in US 2954347, issued September 27, 1960 to Wayne St. John. The monohydric fatty carboxylic acids and salts thereof useful as suds suppressors generally have hydrocarbyl chains of 10-24 carbon atoms, preferably 12-18 carbon atoms. Suitable salts include alkali metal salts, such as sodium, potassium, and lithium salts, and ammonium and alkanolammonium salts.

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

A preferred suds suppressor system comprises:

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

(i) polydimethylsiloxane, its content accounts for 50-99%, preferably 75-95% of polysiloxane defoamer compound; And

(ii) silicon dioxide in an amount of 1-50%, preferably 5-25%, of the polysiloxane/silica defoamer compound;

Wherein the blending amount of the silicon dioxide/polysiloxane antifoaming agent compound is 5%-50%, preferably 10%-40% by weight;

(b) a dispersant compound, most preferably comprising polysiloxane diol comb copolymer (rake copolymer), its polyoxyalkylene content is 72-78%, the ratio of oxyethylene to oxypropylene is 1:0.9- 1:1.1 in an amount of 0.5-10%, preferably 1-10% by weight; a particularly preferred polysiloxane diol comb copolymer of this type is DC0544, commercially available under the trade name DC0544 from the company DOW Corning;

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

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

polymeric dye transfer inhibitor

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

The polymeric dye transfer inhibiting agents are preferably selected from polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, polyvinylpyrrolidone polymers or mixtures thereof, whereby these polymers may be cross-linked polymer.

a) Polyamine N-oxide polymers

Polyamine N-oxide polymers suitable for use in the present invention contain units having the following formula:

where P is a polymerizable unit, and

A is: X is 0 or 1;

R is an aliphatic group, ethoxylated aliphatic group, aromatic group, heterocyclic group or alicyclic group or any combination thereof, wherein the nitrogen atom of the N-O group can be attached to the above group or the nitrogen of the N-O group is part of these groups.

The N-O group can be represented by the following general structure:

或

or

Wherein R ₁ , R ₂ and R ₃ are aliphatic, aromatic, heterocyclic or alicyclic or combinations thereof; x or/and y or/and z are 0 or 1; and wherein the nitrogen of the NO group The nitrogen of the NO group may be attached to or form part of these groups. The NO group may form part of the polymerisable unit (P) or may be attached to the polymeric backbone, or may be a combination of both.

Suitable polyamine N-oxides wherein the N-O group forms part of the polymerizable unit include polyamine N-oxides wherein R is selected from the group consisting of: aliphatic, aromatic, cycloaliphatic or heterocyclic group. One class of said polyamine N-oxides comprises the polyamine N-oxides in which the nitrogen of the N-O group forms part of the R-group. R of preferred polyamine N-oxides is a heterocyclic group, such as pyridine, pyrrole, imidazole, pyrrolidine, piperidine, quinoline, acridine and derivatives thereof.

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

Polyamine N-oxides are available in almost any degree of polymerization. The degree of polymerisation is not critical so long as the material has the desired water solubility and dye-suspending abilities. Typically, the average molecular weight is in the range of 500-1000,000.

b) Copolymers of N-vinylpyrrolidone and N-vinylimidazole

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

c) Polyvinylpyrrolidone

The detergent compositions of the present invention may also employ polyvinylpyrrolidone ("PVP") having an average molecular weight of 2,500-400,000. Suitable polyvinylpyrrolidones are available from ISP Corporation (New York, NY) and Montreal (Canada) under the product names PVP K-15 (viscosity molecular weight 10,000), PVP K-30 (average molecular weight 40,000), PVP K-60 ( Average molecular weight 160,000) and PVP K-90 (average molecular weight 360,000) are commercially available. PVP K-15 is also commercially available from ISP Corporation. Other suitable are polyvinylpyrrolidones commercially available from BASF Corporation, including Sokalan HP 165 and Sokalan HP 12.

d) Polyvinyloxazolidinone

The detergent compositions herein can also employ polyvinyloxazolidinones as polymeric dye transfer inhibiting agents. The average molecular weight of the polyvinyl oxazolidinone is 2,500-400,000.

e) Polyvinylimidazole

The detergent compositions herein can also employ polyvinylimidazoles as polymeric dye transfer inhibiting agents. The average molecular weight of the polyvinylimidazole is preferably 2,500-400,000.

Fluorescent whitening agent

The detergent compositions herein can also optionally contain from about 0.005% to 5% by weight of certain types of hydrophilic optical brighteners.

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

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

In the above formula, when R ₁ is anilino, R ₂ is N-2-bis-hydroxyethyl and M is a cation such as sodium, the brightener is 4,4'-bis[(4-anilino-6- (N-2-Bis-hydroxyethyl)-s-triazin-2-yl)amino]-2,2'-stilbene disulphonic acid and disodium salt. This particular brightener is commercially available from Ciba-Geigy under the trade designation Tinopal-UNPA-GX. Tinopal-UNPA-GX is the preferred hydrophilic optical brightener for use in the detergent compositions herein.

In the above formula, when R ₁ is anilino, R ₂ is N-2-hydroxyethyl-N-2-methylamino and M is a cation such as sodium, the whitening agent is 4,4'-bis[(4- Anilino-6-(N-2-hydroxyethyl-N-methylamino)-s-triazin-2-yl)amino]-2,2'-stilbene disulphonic acid disodium salt. This particular brightener is commercially available from Ciba-Geigy under the tradename Tinopal 5BM-GX.

In the above formula, when _R1 is anilino, _R2 is morpholino and M is a cation such as sodium, the brightener is 4,4'-bis[(4-anilino-6-morpholino-s-tri Azin-2-yl)amino]-2,2'-stilbene disulfonic acid sodium salt. This particular brightener is commercially available from Ciba-Geigy under the tradename Tinopal AMS-GX.

polymeric soil release agent

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

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

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

Suitable SRA's include sulfonation products of substantially linear ester oligomers containing a terephthaloyl oligoester backbone with oxyalkylene oxygen repeat units and allyl derivatives covalently attached to the backbone. Sulfonated terminal moieties are described, for example, in US Patent No. 4,968,451, issued November 6, 1990 to J.J. Scheibel and E.P. The ester oligomer can be prepared by (a) ethoxylating allyl alcohol; (b) combining the product of (a) with dimethyl terephthalate in a two-step transesterification/oligomerization process ("DMT") and 1,2-propanediol ("PG"); and (c) reacting the product of (b) with sodium metabisulfite in water. Other SRA's include the non-ionically terminated 1,2-propylene/polyoxyethylene terephthalate polyesters in U.S. Patent No. 4,711,730 issued December 8, 1987 to Gosselink et al. Alcohol) methyl ether, DMT, PG and poly(ethylene glycol) ("PEG") transesterification/oligomerization products. Other examples of SRA's include partially and fully anionically terminated oligoesters such as those derived from ethylene glycol ("EG"), PG, DMT and 3,6- Oligomers of sodium dioxa-8-hydroxyoctane sulfonate; non-ionic end-capped block polyester oligomers in U.S. Patent No. 4,702,857, Gosselink, issued October 27, 1987, such as DMT, methyl (Me)-capped PEG and EG and/or PG, or products prepared from a mixture of DMT, EG and/or PG, Me-capped PEG and sodium dimethyl 5-sulfoisophthalate; and anions in U.S. Patent No. 4,877,896, Maldonado, Gosselink et al., issued October 31, 1989, especially sulfoaroyl-terminated terephthalates, which are typically useful in both laundry and fabric conditioning products An example of the SRA's is an ester composition prepared from m-sulfobenzoic acid monosodium salt, PG and DMT, optionally but preferably also containing added PEG, eg, PEG3400.

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

Another class of SRA's includes: (I) nonionic terephthalate esters linked to polyester structures using diisocyanate coupling agents, see U.S. Pat. Nos. 4,201,824 to Violland et al. and U.S. Pat. SRA's having carboxylate end groups prepared by adding trimellitic anhydride to known SRA's to convert the terminal hydroxyl groups to trimellitate esters. With proper choice of catalyst, trimellitic anhydride forms linkages to the terminal groups of the polymer through the isolated carboxylate of trimellitic anhydride rather than by opening the anhydride linkage. Both nonionic and anionic SRA's can be used as starting materials as long as they have hydroxyl end groups that can be esterified, see U.S. Patent 4,525,524 to Tung et al. Other types include: (III) Anionic terephthalate-based SRA's linked to urethanes, see U.S. Patent 4,201,824 to Violland et al.

other optional ingredients

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

Highly preferred compositions preferably contain from about 2% to about 10% by weight of organic citric acid, preferably citric acid. Carbonates, minor amounts (e.g., less than about 20% by weight) of neutralizing agents, buffers, phase regulators, hydrotropes, enzyme stabilizers, polyacids, foam regulators, Sunscreens, antioxidants, bactericides, dyes, fragrances such as those described in US Patent No. 4,285,841, Barrat et al., issued August 25, 1981 (herein incorporated by reference).

form of composition

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

Compositions according to the invention may take various physical forms such as tablets, cakes, lozenges and bars, preferably in granular form.

In addition, the detergent compositions of the present invention can be formulated such that they are compatible with chlorine-based bleaches, thereby ensuring that the user can incorporate chlorine-based bleaches into the detergent compositions at the beginning or during the wash cycle.

Generally, the granular detergent compositions of the present invention can be prepared by a variety of methods including dry blending, spray drying, agglomeration and granulation.

The mid-chain branched surfactant system of the present invention, preferably in combination with other surfactants, is present in a granular composition, preferably in the form of surfactant agglomerate particles, which preferably do not contain pre-bleach Bodies, which may take the form of tablets, spheres, pellets, needles and ribbons, but are preferably in the form of granules. The most preferred way of processing the granules is to agglomerate the powder with a highly active surfactant paste (eg aluminosilicates, carbonates) and control the particle size of the resulting agglomerates within specified limits. The method comprises mixing an effective amount of powder with a high active surfactant paste in one or more agglomerators, such as a disc agglomerator, a Z-blade mixer or more preferably an in-line mixer, For example those devices manufactured by Schugi (Netherlands) BV, 29 Chroomstraat 8211 AS, Lelystad, The Netherlands, and Gebruder Lodige Maschinenbau GmbH, D-4790 Paderborn 1, Elsenerstasse 7-9, Postfach 2050 Germany. Most preferably a high shear mixer such as Lodige CB (trade name) is used.

High active surfactant pastes containing 50% to 95% by weight, preferably 70% to 85% by weight of surfactants including mid-chain branched surfactants are typically used. The paste can be pumped into the agglomerator at a temperature high enough to maintain a pumpable viscosity but low enough to avoid degradation of the anionic surfactant used, typically the paste operates at a temperature of 50°C-80 ℃.

The components of the granular composition of the invention should preferably have an average particle size such that no more than 25% are particles with a diameter greater than 1.8 mm; no more than 25% are particles with a diameter less than 0.25 mm. Preferably the average particle size is such that 10%-50% of the particles have a diameter of 0.2mm-0.7mm.

The term mean particle size as defined herein is calculated by sieving a sample of the composition over a set of sieves, preferably Tyler sieves, into fractions (usually 5 fractions). The fractional weights thus obtained are plotted against the aperture of the sieve, with the average particle size being the aperture size through which 50% by weight of the sample passes.

The bulk density of the solid detergent composition of the present invention is from 330 g/l to 1240 g/l, more preferably from 380 g/l to 1200 g/l, most preferably from 420 g/l to 850 g/l. Bulk density is determined by a simple funnel and cup arrangement consisting of a conical funnel rigidly molded on a base with a flap valve at its lower end to allow the contents of the funnel to drain into a shaft placed under the funnel into the aligned cylindrical cups. The funnel is 130 mm high, and the inner diameters at the upper and lower ends are 130 mm and 40 mm, respectively. The funnel was installed such that its lower end was 140 mm above the upper surface of the base. The cup has an overall height of 90mm, an internal height of 87mm, an inner diameter of 84mm and a nominal volume of 500ml.

To measure, fill the funnel with powder by hand, open the flap valve, and allow the powder to overflow the cup. The filled cup is removed from the frame and excess powder is removed by scraping the top rim of the cup with a straight-edged implement, such as a knife. The filled cup is then weighed and the value obtained for the powder weight is doubled to obtain a bulk density value in g/l. Repeat measurements as needed.

laundry method

The machine laundry methods of the present invention generally comprise treating soiled garments with an aqueous wash solution comprising dissolved or dispersed in a washing machine an effective amount of the machine laundry detergent composition of the present invention. An effective amount of the detergent composition means dissolving or dispersing 10 g to 300 g of product in a wash solution volume of 5 to 65 liters, which is a typical amount of product and wash solution volume commonly used in conventional machine washing methods.

In a preferred use aspect, the detergent composition is formulated such that it is suitable for hand washing.

In another preferred aspect, the detergent composition is a pretreatment or soaking composition for pretreating or soaking soiled and soiled fabrics.

Abbreviations used in the examples

In detergent compositions, the abbreviated component symbols have the following meanings:

LAS: Sodium linear _C12 alkylbenzene sulfonate

TAS : Sodium Tallow Alkyl Sulfate

C45AS: Sodium C ₁₄ -C ₁₅ Linear Alkyl Sulfate

MES: Sulfomethyl esters of _C18 fatty acids

C _xy E _z S : C _1X -C _1y branched alkyl sodium sulfate condensed with z moles of ethylene oxide

MBAS _x,y : mid-chain branched sodium alkyl sulfate with an average of x carbon atoms, where

On average y carbon atoms are contained in a branch unit

C ₄₈ SAS : C ₁₄ -C ₁₈ secondary alcohol sodium sulfate

SADE2S: sodium C ₁₄ -C ₂₂ alkyl disulfate _of the formula 2-(R)C ₄ H ₇ -1,4-(SO ₄ -) 2,

Wherein R＝C ₁₀ -C ₁₈ , condensation of z moles of ethylene oxide

C45E7: mainly linear C _14-15 primary alcohols condensed with an average of 7 moles of ethylene oxide

C _xy E _z : C _1x -C _1y branched primary alcohol condensed with an average z moles of ethylene oxide

QASII: R ₂ N ⁺ (CH ₃ ) ₂ (C ₂ H ₄ OH), R ₂ =50%-60% C ₉ ; 40%-50

%C ₁₁

QAS1V: R ₁ N ⁺ (CH ₃ )(C ₂ H ₄ OH) ₂ , R ₁ =C ₁₂ -C ₁₄

QAS V : R ² O(C ₂ H ₄ O) _x (glycosyl) ₂ , wherein R ² is C ₈ -C ₁₀ alkyl; t is 2-

8

Soap: Sodium Linear Alkyl Carboxylate, derived from an 80/20 blend of tallow and coconut oil

arrive

TFAA: C ₁₆ -C ₁₈ Alkyl N-methyl Glucamide

TPKFA: C ₁₂ -C ₁₄ Topped Full Fraction Fatty Acids

STPP : Anhydrous sodium tripolyphosphate

Zeolite A: hydrated sodium aluminosilicate of formula Na ₁₂ (AlO ₂ SiO ₂ ) ₁₂ .27H ₂ O, primary particle

The degree is 0.1-10 microns

NaSKS-6: crystalline layered silicate _{of the} formula δ- _Na2Si2O5

Carbonate: anhydrous sodium carbonate with a particle size of 200-900 microns

Bicarbonate: anhydrous sodium bicarbonate with a particle size distribution of 400-1200 microns

Silicate: Amorphous sodium silicate (SiO ₂ :Na ₂ O; 2.0 ratio)

Sodium Sulfate : Anhydrous Sodium Sulfate

Citric acid: anhydrous citric acid

Citrate: trisodium citrate dihydrate, active 86.4%, particle size distribution in

                                               

MA/AA: 1:4 maleic acid/acrylic acid copolymer, average molecular weight about 70000

MA/AA2 : 4:6 maleic acid/acrylic acid copolymer, average molecular weight about 3000

MA/AA3: 4:6 maleic acid/acrylic acid copolymer, average molecular weight about 12000

AA : Sodium polyacrylate polymer with an average molecular weight of 4500

CMC : Sodium Carboxymethyl Cellulose

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

    Proteolytic enzyme, activity 4KNPU/g

Alcalase: proteolytic enzyme sold by Novo Industries A/S, activity 3AU/g

Cellulase: sold under the tradename Carezyme by Novo Industries A/S

     Cellulolytic enzyme, activity 1000CEVU/g

Amylase: marketed under the tradename Termamyl 60T by Novo Industries A/S

Amylolytic enzyme sold, activity 60KNU/g

Lipase: sold under the tradename Lipolase by Novo Industries A/S

       Lipolytic enzyme, activity 100kLU/g

Endonuclease: Endoglunase enzyme, sold by Novo Industries A/S, (Endolase) activity 3000CEVU/g

PB4: Sodium perborate tetrahydrate of nominal formula NaBO ₂ .3H ₂ OH ₂ O ₂

PB1: Anhydrous sodium _perborate bleach _of nominal formula _NaBO2.H2O2

Percarbonate: sodium percarbonate of nominal formula 2Na ₂ CO ₃ 3H ₂ O ₂

NAC-OBS : (Nonanoylaminocaproyl)oxybenzenesulfonate, sodium salt form

NOBS : Nonanoyloxybenzenesulfonate, sodium salt form

DPDA : Diperoxydodecanedioic acid

PAP : N-phthaloylaminoperoxycaproic acid

NAPAA : Nonanoylamidoperoxyadipate

NACA : 6-Nonylamino-6-oxo-caproic acid

TAED Tetraacetylethylenediamine

DTPMP: Diethylenetriaminepenta(methylene phosphonate), sold by Monsanto under the trade name

Dequest 2060 Sales

Photoactivated: encapsulated sulfonated zinc or aluminum phthalocyanine

Brightener 1: 4,4'-bis(2-sulfostyrene)biphenyl disodium

Brightener 2: 4,4'-bis(4-anilino-6-morpholino-1,3,5-triazin-2-yl)amino)

     Stilbene-2:2’-disodium disulfonate

HEDP ：Hydroxyethane 1,1-diphosphonic acid

PVNO : Polyvinylpyridine N-oxide

PVPVI : Copolymer of polyvinylpyrrolidone and vinylimidazole

QEA: Di((C ₂ H ₅ O)-(C ₂ H ₄ O) _n )(CH ₃ )-N ⁺ -C ₆ H ₁₂ -N ⁺ -(CH ₃ ) di

((C ₂ H ₅ O)-(C ₂ H ₄ O) _n ), where n=20-30

SRP1: Sulfobenzoyl with oxyethyleneoxy and terephthaloyl backbone

Group-terminated esters

SRP2 : Diethoxylated poly(1,2-propylene terephthalate) short block copolymer

Polysiloxane Disinfection: Polydimethylsiloxane Foam Control Agent and Polysiloxane-Oxygen as Dispersant

Foaming agent polyolefin copolymer, the weight ratio of described foam control agent and described dispersing agent is

10:1-100:1

In the following examples, all amounts are expressed in parts by weight of the composition or in % by weight of the composition, as indicated:

Example 1

The following high density granular laundry detergent compositions AF especially suitable for use in European washing machine conditions were prepared according to the present invention: A B C D. E. f LAS 12.0 12.0 10 8.0 18.0 8.0 TAS 1.0 0 2.0 0 0 2.0 C25E9 3.4 - - 3.4 5.4 2.4 C25E7 - 3.0 4.5 - - - C46AS 2.0 2.0 - - - 4.0 C24AS - - 5.0 5.0 4.0 0.5 SADS - - - - 1.0 - MBAS 16.5, 1.7 6.0 3.0 8.0 10.5 4.0 2.0 QASII - - 0.8 - - 0.8 Zeolite A 10.1 5.7 8.0 12.0 16.0 18.1 carbonate 13.0 13.0 13.0 20.0 20.0 20.0 citric acid 2.0 1.0 2.0 - - - Silicate 1.4 1.4 1.4 3.0 3.0 1.0 Sulfate 26.1 26.1 26.1 26.1 26.1 26.1 MA/AA 0.3 2.0 - - - - AAA - - - 0.5 2.0 - CMC 0.2 0.2 0.2 0.2 0.2 0.2 PB4 9.0 9.0 9.0 - - - Percarbonate - - - 18.0 15.0 20.0 TAED - - 1.0 1.5 - - NAC-OBS 4.0 2.5 0.5 1.0 2.0 5.0 DTPMP 0.25 0.25 0.25 0.25 0.25 0.25 EDDS - - 0.25 0.4 - - HEDP 0.3 0.3 0.3 0.3 0.3 0.3 QEA 0.5 1.0 - - 0.5 - protease 0.26 0.26 0.26 0.26 0.26 0.26 Amylase 0.1 0.1 0.1 0.1 0.1 0.1 Photoactivated Bleach (ppm) 15ppm 15ppm 15ppm 15ppm 15ppm 15ppm Brightener 1 0.09 0.09 0.09 0.09 0.09 0.09 spices 0.3 0.3 0.3 0.3 0.3 0.3 Polysiloxane defoamer 0.5 0.5 0.5 0.5 0.5 0.5 Density g/l 850 850 850 850 850 850

Example 2

The following granular laundry detergent compositions GI having a bulk density of 750 g/l are compositions according to the invention: G h I LAS 18.0 8.0 11.5 TAS 1.25 2.86 1.57 C45AS 3.5 3.24 2.0 C25AE3S - 3.0 1.0 C45E7 3.25 - - C25E3 - 3.5 3.5 QASI 0.8 2.0 - MBAS 17, 1.5 7.0 10.0 5.0 STPP 10.5 Zeolite A - 12.0 5.0 NaSKS-6/silicate (79:21) - 5.5 10.6 Citric Acid/Citrate 2.0 2.0 1.0 carbonate 6.1 21.4 21.4 Bicarbonates - 2.0 2.0 Silicate 2.0 - - sodium sulfate 10.0 - 7.0 PB4 5.0 12.7 - TAED 0.5 0.2 - NAC OBS 1.0 2.2 - DTPMP 0.25 0.2 0.2 HEDP - 0.3 0.3 protease 0.26 0.85 0.85 Lipase 0.15 0.15 0.15 cellulase 0.28 0.28 0.28 Amylase 0.1 0.1 0.1 MA/AA 0.8 1.6 1.6 CMC 0.2 0.4 0.4 pvp - - 0.8 Photoactivated Bleach (ppm) 15ppm 27ppm 27ppm Brightener 1 0.08 0.19 0.19 Brightener 2 - 0.04 0.04 spices 0.3 0.3 0.3 Polysiloxane defoamer 0.5 2.4 2.4 Minor/Minor Components to 100% na na

Example 3

The following is a detergent formulation according to the present invention, wherein J is a phosphorus-containing detergent composition, K is a zeolite-containing detergent composition, and L is a compact detergent composition: J K L m blown powder STPP 8.0 - 12.0 - Zeolite A - 14.0 - 7.0 C45AS 4.0 - 4.0 5.0 QASI - 1.0 - - MBAS 17, 1.5 4.0 11.0 10.0 6.0 SASDE2S 2.0 - - - C ₂₅ AE ₃ S - 1.0 - 1.0 MA/AA - 1.0 - 1.0 MA/AA2 2.0 - 1.0 - LAS 14.0 2.0 3.0 1.6 TAS - 4.0 2.0 - Silicate 1.0 3.0 3.0 - CMC 1.0 1.0 0.5 1.0 Brightener 2 0.2 0.2 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 - 4.0 1.5 Polysiloxane defoamer 0.3 0.3 0.3 0.3 spices 0.3 0.3 0.3 0.3 dry additive QEA - 0.5 1.0 - carbonate 6.0 13.0 15.0 13.0 PB4 18.0 18.0 10.0 - PB1 4.0 4.0 - - NOBS 3.0 4.2 1.0 - photoactivated bleach 0.02 0.02 0.02 0.02 manganese catalyst - - 0.5 - protease 1.0 1.0 1.0 1.0 Lipase 0.4 0.4 0.4 0.4 Amylase 0.25 0.30 0.15 0.3 dry mix sodium sulfate 3.0 3.0 5.0 3.0. Balance (moisture and trace components) 100.0 100.0 100.0 100.0 Density (g/l) 630 670 670 670

Example 4

Following is the detergent formula according to the present invention: N o P Q LAS - 14.0 8.0 12.0 TAS - 1.0 4.0 - MBAS 16.5, 1.8 15.0 10.0 6.0 8.0 C45AS 4.0 4.0 6.0 6.0 MES 3.0 - - - QASII 0.4 - 1.0 - TFAA - 1.0 - - C25E5/C45E7/C _{2 5} E ₃ - 2.0 - 1.0 STPP 16.0 18.0 8.0 12.0 Silicate 2.0 1.0 5.0 6.0 carbonate 13.0 7.5 4.0 5.0 Bicarbonates - 7.5 - - DTPMP 0.7 1.0 - - SRP1 0.3 0.2 - 0.1 MA/AA 2.0 1.0 - 1.0 AAA - - 2.0 - CMC 0.8 0.4 0.4 0.2 protease 0.8 1.0 0.5 0.5 Amylase 0.8 0.4 - 0.25 Lipase 0.2 0.1 0.2 0.1 cellulase 0.15 0.05 - - Photoactivated Bleach (ppm) 70ppm 45ppm - 10ppm Brightener 1 0.2 0.2 0.08 0.2 PB1 6.0 2.0 - - NACA - - - 3.0 NAC OBS 2.0 1.0 0.9 3.1 Balance (moisture and trace components) 100 100 100 100

Example 5

Following is the detergent formula according to the present invention: R S T blown powder MBAS 16.5, 1.8 - 10.0 3.0 MBAS 17, 2.6 6.0 - 4.0 Zeolite A 8.0 12.0 6.0 sodium sulfate 19.0 5.0 7.0 MA/AA 1.0 3.0 1.0 MES - 5.0 - LAS 10.0 9.0 13.5 C45AS 3.0 4.0 7.0 Silicate - 1.0 1.0 soap - - 2.0 Brightener 1 0.2 0.2 0.2 carbonate 8.0 16.0 20.0 spray on C45E5 1.0 1.0 - dry additive PVPVI/PVNO 0.5 0.5 0.5 protease 1.0 1.0 1.0 Lipase 0.4 0.4 0.4 Amylase 0.1 0.1 0.1 cellulase 0.1 0.1 0.1 NOBS - 6.1 - NAC OBS - - 4.5 sodium sulfate - 6.0 - Balance (moisture and trace components) 100 100 100

Example 6

The following are high density and bleach-containing detergent formulations according to the invention: u V W blown powder Zeolite A - 7.0 10.0 sodium sulfate 0.0 5.0 0.0 LAS 10.0 - 10.0 C45AS 3.0 2.0 4.0 QAS - - 1.5 DTPMP 0.4 0.4 0.4 CMC 0.4 0.4 0.4 MA/AA 4.0 2.0 2.0 MBAS 6.5, 1.8 5.0 8.0 4.0 Agglomerates LAS 3.0 1.0 1.0 TAS 2.0 2.0 1.0 Silicate 3.0 3.0 4.0 Zeolite A 8.0 5.0 5.0 carbonate 8.0 8.0 4.0 spray on encapsulated spices 0.3 0.3 0.3 C25E3 2.0 - 2.0 dry additive QEA - - 0.5 Citrate 5.0 - 2.0 Bicarbonates - 3.0 - carbonate 8.0 15.0 10.0 NAC OBS 6.0 - 5.0 manganese catalyst - - 0.3 NOBS - 2.0 - PBI 14.0 7.0 10.0 Polyethylene oxide of MW5000 000 - - 0.2 Bentonite - - 10.0 citric acid - 1.0 0.5 protease 1.0 1.0 1.0 Lipase 0.4 0.4 0.4 Amylase 0.6 0.6 0.6 cellulase 0.6 0.6 0.6 Polysiloxane defoamer 5.0 5.0 5.0 dry additive sodium sulfate 0.0 3.0 0.0 Balance (moisture and trace components) 100.0 100.0 100.0 Density (g/l) 850 850 850

Example 7

Following is the formula of high-density detergent according to the present invention: x Y Agglomerates MES - 12.0 LAS 12.0 - TAS - 2.0 C45AS 6.0 4.0 MBAS16.5, 1.6 - 9.0 MBAS16.5, 2.8 10.0 - Zeolite A 10.0 6.0 carbonate 4.0 8.0 MA/AA 1.0 2.0 CMC 0.5 0.5 DTPMP 0.4 0.4 spray on C25E3 1.0 1.0 spices 0.5 0.5 dry additive HEDP 0.5 0.3 SKS 6 5.0 6.0 Citrate - 1.0 citric acid 2.0 - NAC OBS 4.1 - TAED 0.8 2.0 Percarbonate 20.0 20.0 SRP1 0.3 0.3 protease 1.4 1.4 Lipase 0.4 0.4 cellulase 0.6 0.6 Amylase 0.6 0.6 QEA 1.0 - Polysiloxane defoamer 5.0 5.0 Brightener 1 0.2 0.2 Brightener 2 0.2 - Density (g/l) 850 850

Example 8

The following granular detergent formulations are examples of the invention: AH AI AJ blown powder MES - 2.0 - LAS 2.0 - 3.0 C45AS - 1.0 - C46AS 4.0 - - C45AE35 7.0 5.0 3.0 MBAS14.5, 1.7 8.0 - - Zeolite A 6.0 4.0 6.0 MA/AA2 1.0 - - AAA 1.0 2.0 1.0 sodium sulfate 3.3 24.0 13.3 Silicate 1.0 2.0 1.0 carbonate 9.0 15.0 8.0 QEA 0.4 - 0.5 PEG4000 - 1.0 1.5 brightener 0.3 0.3 0.3 spray on C25E5 0.5 1.0 - spices 0.3 1.0 0.3 Agglomerates C45AS 5.0 2.0 5.0 LAS 4.0 11.0 2.0 MBAS17, 2.0 15.0 6.0 - Zeolite A 7.5 - 7.5 HEDP 1.0 - 2.0 carbonate 4.0 - 4.0 PEG4000 0.5 - 0.5 Minor components (water, etc.) 2.0 - 2.0 dry additive NOBS 4.0 - - TAED - - 2.0 PB4 1.0 - 2.0 carbonate 5.3 - 2.5 cumenesulfonic acid 2.0 - 2.0 Lipase 0.4 0.1 0.05 cellulase 0.2 - 0.2 Amylase 0.3 - - protease 1.6 - 1.6 PVPVI 0.5 - - PVNO 0.5 - - SRP1 0.5 - - Polysiloxane defoamer 0.2 - 0.2

Example 9 AK AL AM AN AO AP C45AS 11.0 5.1 4.0 8.5 4.1 9.8 C25AES 1.3 1.0 - 1.3 1.0 - LAS 9.4 6.6 23.5 3.7 1.7 4.3 C25E3/C25E5 1.5 4.7 3.3 1.5 4.7 3.3 MBAS16.5, 1.7 9.0 5.0 10.0 12.2 5.9 14.1 QAS - 1.15 0.7 - 1.7 - Zeolite A 16.0 10.7 8.0 7.7 16.7 10.0 SKS-6 - 9.0 6.0 - 3.0 5.0 citric acid - 1.5 - - 1.5 - MA/AA - 0.6 - - 0.6 - MA/AA3 - - 3.0 - - 2.0 AAA 2.2 - - 2.6 - - EDDS - 0.3 - - 0.3 - HEDP - 0.5 - - 0.5 - Carbonate 26.0 12.5 14.9 26.0 12.5 14.9 Silicate 0.8 0.8 3.0 0.8 0.8 3.0 PB1 1.0 - 3.9 1.0 - 3.9 NACA-OBS - 2.75 - - 2.7 - PC - 17.3 - - 17.3 - NOBS - 2.7 4.0 - - 4.0 TAED - 3.5 - - 3.5 - protease 0.26 0.3 0.2 0.6 0.3 0.2 Lipase - - - - - - cellulase 0.3 0.2 - 0.3 0.3 - Amylase - 0.3 - - 0.3 - whitening agent 0.17 0.06 0.30 0.17 0.06 0.3 SRP1 0.41 0.2 0.5 0.41 0.2 0.5 PEG 1.6 - 0.19 1.6 - 0.19 Sulfate 5.8 6.4 3.0 5.5 6.0 3.8 CMC - 0.5 - - 0.5 - MgSO4 - 0.13 - - 0.13 - photobleach - 0.0026 - - 0.0026 - Polysiloxane defoamer 0.02 0.21 0.17 0.02 0.21 0.17 Spices 0.42 0.55 0.25 0.42 0.55 0.25

Example 10

The following laundry detergent compositions AQ-AT were prepared according to the invention: AQ AR AS AT MBAS 16.5, 1.7 twenty two 16.5 11 5.5 C45AS 8 10 11 4 C45E1S 4 3 - 1 LAS 8 14 - 4 C16 SAS - - 3 - MES - - 12 - C23E6.5 1.5 1.5 1.5 1.5 Zeolite A 7.0 10.0 12.0 14.0 AAA 2.3 2.3 2.3 2.3 carbonate 7.0 15.0 27.0 25.0 Silicate 0.6 0.6 0.6 0.6 Perborate 1.0 1.0 1.0 1.0 protease 0.3 0.3 0.3 0.3 cellulase 0.3 0.3 0.3 0.3 SRP1 0.4 0.4 0.4 0.4 brightener 0.2 0.2 0.2 0.2 PEG 1.6 1.6 1.6 1.6 Sulfate 5.5 5.5 5.5 5.5 Polysiloxane defoamer 0.42 0.42 0.42 0.42 Moisture and Minor Components ---Balance amount--- Density (g/l) 660 660 660 660

Example 11

The following laundry detergent compositions AU-AY were prepared according to the invention: AU AV AW AX AY MBAS 16.5, 1.7 14.8 16.4 12.3 8.2 4.1 C45 AS 5 7 6 4 12 C45E3S 2 - 4 - 5 LAS 14 8 - 18 5 C16 SAS - - 1 - 1 MES - - 10 - - TFAA 1.6 0 0 0 0 C24E3 4.9 4.9 4.9 4.9 4.9 Zeolite A 10 5 7 11 15 NaSKS-6 6 9 5 2.0 4.6 Citrate/citric acid 1.0 1.0 2.0 - 0.5 MA/AA 4.8 2.8 - 1.0 1.0 HEDP 0.5 0.5 0.5 0.5 0.5 carbonate 8.5 8.5 8.5 8.5 8.5 PB1 13.0 - 15.0 - - Percarbonate - 20.7 - 20.7 20.7 NACAOBS 4.0 3.0 1.0 - - TAED - - 4.8 4.8 4.8 QEA 1.0 1.0 - - - QAS 1.0 - - - 1.0 protease 0.9 0.9 0.9 0.9 0.9 Lipase 0.15 0.15 0.15 0.15 0.15 cellulase 0.26 0.26 0.26 0.26 0.26 Amylase 0.36 0.36 0.36 0.36 0.36 SRP 0.2 0.2 0.2 0.2 0.2 brightener 0.2 0.2 0.2 0.2 0.2 Sulfate 2.3 2.3 2.3 2.3 2.3 Polysiloxane defoamer 0.4 0.4 0.4 0.4 0.4 Moisture and Minor Components ---Balance amount--- Density (g/l) 850 850 850 850 850

Example 12

The following laundry detergent compositions AZ-Ee were prepared according to the present invention: AZ A Bb Cc Dd Ee MBAS 16.5, 7.1 32 twenty four 12 16 16 8 C45AS 5 8 6.5 5.0 12.0 - C45E1S - - - - 2.5 7.2 LAS - 2.0 8 twenty three 12 16 C16 SAS 1.0 - - - - - MES 14 - - - - - C23E6.5 3.6 3.6 3.6 3.6 3.6 3.6 QAS - 0.5 - - 0.5 - Zeolite A 9.0 5.0 12.0 3.0 9.0 8.0 polycarboxylate 2.0 5.0 3.0 7.0 6.0 5.0 carbonate 18.4 18.4 18.4 18.4 18.4 18.4 Silicate 1.0 10 5.0 10 4.5 3.0 Perborate 3.9 3.9 3.9 3.9 3.9 3.9 NOBS 4.1 4.1 4.1 4.1 4.1 4.1 protease 0.9 0.9 0.9 0.9 0.9 0.9 SRP1 0.5 0.5 0.5 0.5 0.5 0.5 brightener 0.3 0.3 0.3 0.3 0.3 0.3 PEG 0.2 0.2 0.2 0.2 0.2 0.2 Sulfate 5.1 5.1 5.1 5.1 5.1 5.1 Polysiloxane defoamer 0.2 0.2 0.2 0.2 0.2 0.2 Moisture and Minor Components ---Balance amount--- Density (g/l) 810 810 810 810 810 810

Claims (18)

1. A density of 550-900 g/L solid detergent composition comprising: a) From 0.5 to 32% by weight of the composition of a surfactant system comprising a long alkyl chain mid-chain branched surfactant compound of the formula: A ^b -XB in: (I) A ^b is a hydrophobic mid-chain branched alkyl moiety totaling 9-22 carbon atoms having: (1) the longest chain in the range of 8-21 carbon atoms attached to the -XB moiety Linear carbon chain; (2) one or more C ₁ -C ₃ alkyl moieties branched from the longest linear carbon chain; (3) at least one branched chain alkyl moiety is directly connected to the longest linear carbon chain The carbon atom linkage between the 2-carbon position counting from the 1-carbon position attached to the -XB moiety to the terminal carbon atom minus 2 carbons; and (4) when more than one of these compounds is present, the above The average total number of carbon atoms of the A ^b -X part in the formula is greater than 14.5-18; (II) B is a hydrophilic moiety selected from sulfates, sulfonates, amine oxides, polyoxyalkylenes, alkoxylated sulfates, polyhydroxy moieties, phosphates, glycerol sulfonates, polygluconic acid salt, polyphosphate, phosphonate, sulfosuccinate, sulfosuccinamate, polyalkoxylated carboxylate, glucosamide, taurate, sarcosinate, glycinate, hydroxy Ethylsulfonate, Dialkanolamide, Monoalkanolamide, Monoalkanolamide Sulfate, Diethylene Glycolamide, Diethylene Glycolamide Sulfate, Glycerides, Glyceryl Ester Sulfate, Glyceryl Ether, Glyceryl Ether Sulfate salt, polyglyceryl ethers, polyglyceryl ether sulfates, sorbitan esters, polyalkoxylated sorbitan esters, aminoalkane sulfonates, amidopropyl betaines, alkylated quaternary ammonium salts, alkanes alkylated/polyhydroxyalkylated quaternary ammonium salts, alkylated/polyhydroxylated oxypropyl quaternary ammonium salts, imidazolines, 2-yl-succinates, sulfonated alkyl esters, and sulfonated fatty acids; and (III) X is _-CH2- ; and b) 0.5-25% by weight of a builder system by weight of the composition; and c) 0.0-50% by weight of the composition of an alkaline system including carbonate, provided that when the content of system a) is 3% by weight and the content of system b) is 19% by weight, the alkaline System c) does not include 8% by weight of sodium carbonate. 2. A detergent composition according to claim 1, wherein the surfactant system a) is present in an amount of 5 to 32% by weight. 3. A detergent composition according to claim 2, wherein the surfactant system a) is present in an amount from 10 to 32% by weight. 4. A detergent composition according to claim 1 wherein ^Ab is a hydrophobic mid-chain branched alkyl moiety having a total of 12 to 18 carbon atoms. 5. A detergent composition according to claim 1 wherein when more than one of said compounds is present the moieties Ab ^-X have an average total number of carbon atoms of 15-17. 6. The detergent composition according to claim 1, wherein said polyoxyalkylene in (II) is selected from polyoxyethylene and polyoxypropylene. 7. A detergent composition according to claim 1, wherein the surfactant compound of the surfactant system a) has the above formula wherein the A ^b moiety is a branched primary alkyl moiety of the formula:

Wherein the branched primary alkyl moiety of the formula includes R, R ¹ and R ² branches with a total carbon number of 13-19; R, R ¹ and R ² are each independently selected from hydrogen and C ₁ -C ₃ alkane base, provided that R, ^R1 and ^R2 are not all hydrogen, and when z is 0, at least R or ^R1 is not hydrogen; w is an integer from 0-13; x is an integer from 0-13; y is 0 an integer of -13; z is an integer of 0-13; and w+x+y+z is 7-13. 8. A detergent composition according to claim 7, wherein R, ^R1 and ^R2 are each independently selected from methyl. 9. A detergent composition according to any one of claims 1 to 8, wherein the surfactant system a) comprises at least 20% by weight of one or more mid-chain branched alkyl sulfates of the formula or Its mixture: or Wherein M represents one or more cations; a, b, d and e are integers, a+b is 10-16, d+e is 8-14, and wherein: When a+b=10, a is an integer of 2-9 and b is an integer of 1-8; When a+b=11, a is an integer of 2-10 and b is an integer of 1-9; When a+b=12, a is an integer of 2-11 and b is an integer of 1-10; When a+b=13, a is an integer of 2-12 and b is an integer of 1-11; When a+b=14, a is an integer of 2-13 and b is an integer of 1-12; When a+b=15, a is an integer of 2-14 and b is an integer of 1-13; When a+b=16, a is an integer of 2-15 and b is an integer of 1-14; When d+e=8, d is an integer of 2-7 and e is an integer of 1-6; When d+e=9, d is an integer of 2-8 and e is an integer of 1-7; When d+e=10, d is an integer of 2-9 and e is an integer of 1-8; When d+e=11, d is an integer of 2-10 and e is an integer of 1-9; When d+e=12, d is an integer of 2-11 and e is an integer of 1-10; When d+e=13, d is an integer of 2-12 and e is an integer of 1-11; When d+e=14, d is an integer of 2-13 and e is an integer of 1-12; Thus, the average total number of carbon atoms in the branched primary alkyl moiety is from 14.5 to 17.5. 10. A detergent composition according to claim 9, wherein the surfactant system a) comprises at least 90% by weight of one or more of said mid-chain branched alkyl sulfates or mixtures thereof. 11. A detergent composition according to any one of claims 1 to 8, wherein the surfactant compound of the surfactant system a) has an A ^b -X moiety comprising 16 to 18 carbon atoms and B is a sulfate group . 12. A detergent composition according to any one of claims 1 to 8, wherein the builder system comprises one or more builder materials selected from the group consisting of amorphous silicates, crystalline layered silicates, Aluminum silicates, polymeric or monomeric polycarboxylates and their acids, and optionally phosphates. 13. A detergent composition according to any one of claims 1 to 8, wherein the builder system is substantially free of phosphate builder materials. 14. A detergent composition according to any one of claims 1 to 8 wherein the builder material is present in an amount of from 5 to 18% by weight of the composition. 15. A detergent composition according to any one of claims 1-8, wherein the alkaline system comprises sodium carbonate in an amount of 4-20% by weight. 16. A detergent composition according to any one of claims 1-8, wherein the ratio of nonionic surfactant to anionic surfactant is from 10:1 to 1:10. 17. A detergent composition according to claim 16, wherein the nonionic surfactant is a _C9-15 primary alcohol ethoxylate containing 3-12 moles of ethylene oxide per mole of alcohol. 18. A detergent composition according to claim 16, wherein the ratio of nonionic surfactant to anionic surfactant is from 1:1 to 1:10.