CN1373180A - Washing method - Google Patents

Abstract

The invention relates to a washing method. There is a provided a detergent composition containing: (a) 0.005-1 wt.% a heavy metal ion sequestrant selected from ethylenediamine-N,N'-disuccinic acid, its salts or their mixture; and (b) a wash solution free of bleach is supplied to a base with dirt. The wash solution contacts with the base with dirt. The base with dirt then is cleaned by detergent composition containing bleach.

Description

cleaning method

This application is a divisional application of PCT/US95/04085 patent application for invention entitled "Detergent Containing Heavy Metal Sequestrant and Delayed Release Peroxyacid Bleach System" filed on April 3, 1995. The original application was filed in It entered the Chinese national phase on December 11, 1996, and obtained the Chinese patent application number 95193547.X.

Technical field

The present invention relates to a method of washing comprising supplying a bleach-free solution containing a heavy metal ion sequestrant to a soiled substrate, keeping the solution in contact with said soiled substrate, and then applying a bleach-containing solution to a soiled substrate. Detergent compositions clean said soiled substrates.

Background technique

Satisfactory removal of bleachable soils/stains such as tea, juice and pigmented vegetable soils from soiled/stained substrates For formulation of such detergent compositions for use in e.g. laundry or dishwashing machine washing processes The teacher is very challenging.

Traditional methods of removing such bleachable soils/stains may use bleach components such as oxygen bleaches, including hydrogen peroxide and organic peroxyacids. The organic peroxyacid is usually obtained in situ by the perhydrolysis reaction between hydrogen peroxide and an organic peroxyacid bleach precursor.

A problem encountered with the use of certain organic peroxyacid bleaches in laundry washing methods is that these peroxyacid bleaches tend to affect the color stability of fabrics in the wash. Types of damage to fabrics may include fading of colored dyes or localized irregular areas of colored bleaching on the fabric.

Detergent formulators are therefore faced with the dual challenge of formulating a product that maximizes the removal of bleachable soils/stains, but that minimizes any undesired contribution of the bleach to fabric color stability impact is minimized.

Applicants have found that the occurrence of any undesired effect on the color stability of fabrics caused by the use of peroxyacid bleaches in the wash process is related to the rate of release of the peroxyacid bleaches into the wash solution, and also to the rate of release of the peroxyacid bleach into the wash solution. related to the absolute amount of peroxyacid present in the

The rapid release rate of peroxyacid bleach into the wash solution tends to increase the likelihood that undesired effects on fabric color stability will be observed, as do high absolute levels of bleach in the wash solution.

Reducing the release rate of the peroxyacid bleach or reducing the absolute amount of bleach used in the wash tends to ameliorate this problem by a phased effect on bleachable stain/soil removal.

However, the applicants have now found that it is possible to use a composition comprising a heavy metal ion sequestrant and a source of peroxyacid bleach, and wherein the release of the peroxyacid bleach to the wash solution is delayed relative to the release of the heavy metal ion sequestrant. A method for enhancing the removal of bleachable stains/soils. In addition, use of the composition in a laundry washing method reduces the tendency to be observed to adversely affect the color stability of fabrics.

In addition, the applicants have discovered that when soiled substrates are pre-treated with a solution containing a heavy metal ion sequestrant and optionally a water-soluble builder prior to washing in a bleach-containing detergent product, improved Benefits of bleachable stain/soil removal.

Contents of the invention

It is therefore an object of the present invention to provide compositions suitable for use in laundry and dishwashing machine washing processes having enhanced bleachable stain removal.

Another object of the present invention is to provide compositions for use in laundry washing methods wherein said compositions exhibit a lower tendency to cause adverse effects on the color stability of fabrics.

A related object of the present invention is to provide a stain/soil pretreatment method comprising pretreating soiled substrates with a solution comprising a heavy metal ion sequestrant and optionally a water soluble builder prior to washing with a bleach-containing detergent product. thing.

Summary of the invention

According to one aspect of the present invention, there is provided a detergent composition comprising: (a) a heavy metal ion sequestrant; and (b) an organic peroxyacid bleach system, which provides release of the complex, a method of delaying the release of said organic peroxyacid into the wash solution such that in the T50 test method described herein the time to obtain a heavy metal ion sequestrant concentration of 50% of its final concentration is less than 120 seconds , the time to obtain an organic peroxyacid concentration of 50% of its final concentration is greater than 180 seconds.

According to another aspect of the present invention, there is provided a detergent composition comprising: (a) a heavy metal ion chelating agent; and (b) an organic peroxyacid bleaching system, which provides The release of the mixture, the method of delaying the release of said organic peroxyacid in the washing solution, so that in the T50 test method described herein, the concentration of said heavy metal ion chelating agent is 50% of its final concentration. The time required to obtain a concentration of said organic peroxyacid of 50% of its final concentration is at least 100 seconds shorter, preferably at least 120 seconds shorter, more preferably at least 150 seconds shorter.

Said organic peroxyacid bleaching system preferably comprises the combination of: (i) a source of hydrogen peroxide; and (ii) an organic peroxyacid bleach precursor compound.

According to a preferred aspect of the present invention, said composition also contains: (c) a water-soluble builder which provides release of said organic peroxyacid to the wash solution relative to said water-soluble builder method of delayed release, so that in the T50 test method described herein, the time to obtain a concentration of said water-soluble builder that is 50% of its final concentration is less than 120 seconds to obtain a concentration of said organic peroxyacid The time to 50% of its final concentration is greater than 180 seconds.

According to another aspect of the present invention, a washing method is provided, comprising the steps of:

(1) a bleach-free composition solution containing a heavy metal ion chelating agent is supplied to a soiled substrate;

(2) an effective time interval for maintaining said solution in contact with said soiled substrate;

(3) Washing said soiled substrate by a washing method comprising the use of a bleach-containing detergent composition. Heavy metal ion chelating agent

The detergent compositions of the present invention contain heavy metal ion sequestrants. By heavy metal ion sequestrant is meant herein a component that acts to sequester heavy metal ions. These components may also have calcium and magnesium chelating capacity, but preferably they exhibit selectivity for binding heavy metal ions such as iron, magnesium and copper.

The heavy metal ion sequestrant is generally present at 0.005% to 20%, preferably 0.1% to 10%, more preferably 0.25% to 7.5%, most preferably 0.5% to 5% by weight of the composition.

Heavy metal ion sequestrants, which are acidic in nature, having, for example, phosphonic acid or carboxylic acid functionality, which may be present in their acid form or as a combination with a suitable countercation such as an alkali metal or alkaline earth metal ion, ammonium, or Complex/salt form of substituted ammonium or any mixture thereof. Preferably any salt/complex is water soluble. The molar ratio of said counter cation to heavy metal ion sequestrant is preferably at least 1:1.

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

Preferred among the above substances are diethylene triamine penta(methylene phosphonate), ethylenediamine tri(methylene phosphonate), hexamethylene diamine tetra(methylene phosphonate) and hydroxyethylene 1,1 diphosphonate.

Other heavy metal ion sequestrants suitable for use in the present invention include nitrilotriacetic acid and polyaminocarboxylic acids such as ethylenediaminetetraacetic acid, ethylenetriaminepentaacetic acid, ethylenediamine disuccinic acid, ethylenediamine diglutamine acid, 2-hydroxypropylenediamine disuccinic acid, or any salt thereof.

Especially preferred is ethylenediamine-N,N'-disuccinic acid (EDDS) or its alkali metal, alkaline earth metal, ammonium or substituted ammonium salts, or mixtures thereof. Preferred EDDS compounds are in the free acid form, and their sodium or magnesium salts or complexes. Examples of such preferred sodium salts of EDDS include _Na2EDDS and _Na3EDDS . Examples of such preferred magnesium complexes of EDDS include MgEDDS and _Mg2EDDS .

Other suitable heavy metal ion sequestrants suitable for use in the present invention as described in EP-A-317,542 and EP-A-399,133 are iminodiacetic acid derivatives such as 2-hydroxyethyldiacetic acid or glycerylimino Diacetic acid.

The iminodiacetic acid-N-2-hydroxypropylsulfonic acid and aspartic acid N-carboxymethyl N-2-hydroxypropyl-3-sulfonic acid chelating agents described in EP-A-516,102 are also suitable for this invention. β-alanine-N,N'-diacetic acid, aspartic acid-N,N'-diacetic acid, aspartic acid-N-monoacetic acid and iminodisuccinate described in EP-A-509,382 Acid sequestrants are also suitable.

EP-A-476,257 describes suitable amino-based chelating agents. EP-A-510,331 describes chelating agents derived from collagen, keratin or casein. EP-A-528,859 describes suitable alkyliminodiacetic acid chelating agents, dipicolinic acid and 2-phosphonobutane-1,2,4-tricarboxylic acid are also suitable. Glycinamide-N,N'-disuccinic acid (GADS) is also suitable. Organic Peroxyacid Bleach System

An essential technical feature of the present invention is the organic peroxyacid bleach system. In a preferred implementation, the bleaching system comprises a hydrogen peroxide source and an organic peroxyacid bleach precursor compound. The preparation of organic peroxyacids is carried out by reacting their precursors with hydrogen peroxide sources in situ. Preferred sources of hydrogen peroxide include inorganic perhydrate bleaches. In another preferred practice, preformed organic peroxyacids are incorporated directly into the composition. Compositions comprising a source of hydrogen peroxide and a mixture of organic peroxyacid precursors and preformed organic peroxyacids are also proposed. Inorganic perhydrate bleach

Inorganic perhydrate salts are the preferred source of hydrogen peroxide. These salts are usually incorporated in the form of alkali metal, preferably sodium salts, in amounts of 1% to 40% by weight of the composition, more preferably 2% to 30% by weight, most preferably 5% to 25% by weight. %(Heavy).

Examples of suitable inorganic perhydrate salts include borates, percarbonates, perphosphates, persulfates and persilicates and any mixtures thereof. The inorganic hydrate salt is usually an alkali metal salt. Inorganic perhydrate salts may be included as crystalline solids without additional protection. For certain perhydrate salts, however, the preferred embodiment of this granular component is to use a coated form of the material, which provides better storage stability for the perhydrate salt in the granular product.

Sodium perborate can be in the monohydrate _form with _the standard formula _NaBO2H2O2 or _{the tetrahydrate form NaBO2H2O2-3H2O .}

Alkali metal percarbonates, especially sodium percarbonate, are preferred perhydrates for inclusion in the compositions of the present invention. Compositions containing percarbonate have been found to have a reduced tendency to form undesired gels in the presence of surfactant and water than similar compositions containing perborate. This is believed to be because percarbonates generally have less surface area and less porosity than perborate monohydrate. This low surface area and low porosity act to inhibit co-gelling with the fine particles of the surfactant agglomerates, so it is beneficial for dispersion.

Sodium percarbonate is _an addition compound corresponding to the formula _{2Na2CO3 3H2O2} , commercially available as a crystalline _solid , sodium percarbonate is most preferably incorporated into such compositions in coated form , which provides its stability in the product.

Suitable coating materials to provide stability in the product include mixed salts of water soluble alkali metal sulfates and carbonates. Such cladding materials and cladding methods are described in GB-1,466,799, issued March 9,1977 to Interox. The weight ratio of the mixed salt of the coating material to the percarbonate is in the range of 1:200 to 1:4, more preferably 1:99 to 1:9, most preferably 1:49 to 1:19. Preferably the mixed salt is a mixed salt of sodium sulfate and sodium carbonate, having the general formula: Na ₂ SO ₄ ·nNa ₂ CO ₃ , wherein n is 0.1 to 3, preferably n is 0.3 to 1.0, most preferably n is 0.2 to 0.5.

Other coating materials containing silicates (alone or with borates or boric acid or other inorganics), paraffins, oils, fatty soaps may also be advantageously used in the present invention.

Potassium peroxymonopersulfate is another class of inorganic perhydrate salts useful in the detergent compositions of the present invention. Peroxyacid Bleach Precursors

Peroxyacid bleach precursors are compounds which react with hydrogen peroxide in a perhydrolysis reaction to form peroxyacids. A general peroxyacid bleach precursor can be represented by the following formula: where L is a leaving group and X is any functionality necessary so that the structure of the peroxyacid produced after perhydrolysis is:

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

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

Applicants have found that "irregular" damage is especially associated with peroxyacid bleach precursor compounds which upon hydrolysis provide a peroxyacid which is: (i) perbenzoic acid, or its non-cationic a substituted derivative; or (ii) a cationic peroxyacid.

It has also been found that benzoxazine precursors are particularly sensitive to this problem. leaving group

The leaving group, hereinafter the L group, must be sufficiently reactive for the perhydrolysis reaction to occur within an optimal time frame (eg wash cycle). However, if L is too reactive the activator is difficult to stabilize for use in bleaching compositions.

和其混合物，其中R¹是含1至14个碳原子的烷基、芳基或烷芳基，R³是含1至8个碳原子的烷基链、R⁴是H或R³、和Y是H或加溶基团。任何R¹、R³和R⁴可被必要的任何官能基团取代，这些官能基团包括，例如烷基、羟基、烷氧基、卤素、胺、亚硝酰基、酰胺和铵或烷基铵基团。Preferred L groups are selected from:

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

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 cation that provides solubility to the bleach activator. Anion providing solubility, M is preferably an alkali metal, ammonium or substituted ammonium cation, sodium and potassium are most preferred, X is a halide, hydroxide, methylsulfate or acetate anion. Precursors of perbenzoic acid and its derivatives

Perbenzoic acid precursor compounds provide perbenzoic acid upon perhydrolysis.

Suitable O-acylated perbenzoic acid precursor compounds include substituted and unsubstituted benzoyloxybenzenesulfonates, including for example benzoyloxybenzenesulfonate:

Also suitable are benzoylation products of sorbitol, glucose and all saccharides with benzoylating agents, including for example: AC=COCH ₃ ; Bz=benzoyl

Imide-type perbenzoic acid precursor compounds include N-benzoylsuccinimide, tetrabenzoylethylenediamine, and N-benzoyl-substituted ureas. Suitable imidazole-type perbenzoic acid precursors include N-benzoyl imidazole and N-benzoylbenzimidazole, and useful N-acyl-containing perbenzoic acid precursors include N-benzoylpyrrolidone, diphenyl Formyl taurine and benzoyl pyroglutamate.

苯二甲酸酐是本文中另一适宜的过苯甲酸前体化合物：

适宜的N-酰化内酰胺过苯甲酸前体具有式：

其中n为0至8，优选0至2，R⁶为含有1至12个碳原子的芳基、烷氧芳基或烷芳基、或含有6至18个碳原子的取代的苯基，优选苯甲酰基。过苯甲酸衍生物前体Other perbenzoic acid precursors include benzoyl diacyl peroxide, benzoyl tetraacyl peroxide, and compounds having the following formulae.

Phthalic anhydride is another suitable perbenzoic acid precursor compound herein:

Suitable N-acylated lactam perbenzoic acid precursors have the formula:

Wherein n ^is 0 to 8, preferably 0 to 2, R for aryl, alkoxyaryl or alkaryl containing 1 to 12 carbon atoms, or substituted phenyl containing 6 to 18 carbon atoms, preferably Benzoyl. Perbenzoic acid derivative precursor

Hydrolysis of the perbenzoic acid derivative precursor provides the substituted perbenzoic acid.

Suitable substituted perbenzoic acid derivative precursors include any of the perbenzoic acid precursors disclosed herein in which the benzoyl group is substituted with any non-positively charged (i.e. non-cationic) functional groups as necessary, including, Examples include alkyl groups, hydroxyl groups, alkoxy groups, halogen atoms, amines, nitrosyl groups and amido groups.

其中R¹是具有1-14个碳原子的芳基或烷芳基，R²是含有1-14个碳原子的亚芳基或烷亚芳基，R⁵是H或含有1-10个碳原子的烷基、芳基、或烷芳基，L可是必要的任何离去基团。R¹优选含有6-12个碳原子。R²优选含有4-8个碳原子、R¹可以是芳基、含支链取代基的取代的芳基或烷芳基、或这两者，并且可以来源于合成物或天然物，包括例如牛油脂肪。类似结构的变种也适用于R²。取代物可包括烷基、芳基、卤原子、氮、硫和其它典型的取代基或有机化合物。R⁵优选为H或甲基。R¹和R⁵总共不应含多于18个碳原子。这类酰胺取代的漂白活化剂化合物描述在EP-A-0170386中。阳离子过氧酸前体A preferred class of substituted perbenzoic acid precursor compounds are amide substituted compounds of the general formula:

wherein ^R is an aryl or alkaryl group with 1-14 carbon atoms, ^R is an arylene or alkarylene group with 1-14 carbon atoms, ^R is H or has 1-10 carbon Atoms are alkyl, aryl, or alkaryl, and L may be any leaving group as necessary. R ¹ preferably contains 6-12 carbon atoms. ^R2 preferably contains 4-8 carbon atoms, ^R1 can be aryl, substituted aryl or alkaryl containing branched chain substituents, or both, and can be derived from synthetic or natural sources, including for example Butter fat. Variations of similar structures are also suitable for ^R2 . Substituents may include alkyl groups, aryl groups, halogen atoms, nitrogen, sulfur and other typical substituents or organic compounds. R ⁵ is preferably H or methyl. Together ^R1 and ^R5 should not contain more than 18 carbon atoms. Amide substituted bleach activator compounds of this type are described in EP-A-0170386. cationic peroxyacid precursor

Cationic peroxyacid precursor compounds undergo hydrolysis to produce cationic peroxyacids.

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

The cationic substituted peroxyacid precursor compound may be perbenzoic acid, or a substituted derivative thereof, the precursor compound described above. Additionally, the peroxyacid precursor compound may be an alkylpercarboxylic acid precursor compound or an amide-substituted alkylperoxyacid precursor described below.

Cationic peroxyacid precursors are described in U.S. Patents: 4,904,406; 4,751,015; 4,988,451; 4,397,757; 5,269,962; 5,127,852;

Examples of preferred cationic peroxyacid precursors are described in UK patent application 94 07944.9 and US patent applications 08/298903, 08/298650, 08/298904 and 08/298906.

Suitable cationic peroxyacid precursors include any amine or alkylamine substituted alkyl or benzoyloxybenzenesulfonate, N-acylated caprolactam and monobenzoyltetraacetylglucose benzoyl peroxide.

优选的阳离子取代的烷氧基苯磺酸盐具有式： A preferred cationic substituted benzoyloxybenzenesulfonate is the 4-(trimethylammonium)methyl derivative of benzoyloxybenzenesulfonate

Preferred cationic substituted alkoxybenzenesulfonates have the formula:

Preferred N-acylated caprolactam cationic peroxyacid precursors include trialkylammoniummethylenebenzoylcaprolactams, especially trimethylammoniummethylenebenzoylcaprolactams.

其中n为0至12。Other preferred N-acylated caprolactam cationic peroxyacid precursors include trialkylammoniummethylenealkylcaprolactams:

where n is 0 to 12.

Another preferred cationic peroxyacid precursor is 2-(N,N,N-trimethylammonium)ethyl 4-sulfophenyl sodium carbonate chloride. Alkyl percarboxylic acid bleach precursor

Alkyl percarboxylic acid bleach precursors are hydrolyzed to form percarboxylic acids. Preferred precursors of this type include peracetic acid provided upon hydrolysis.

Preferred imide-type alkyl percarboxylic acid precursor compounds include N, N, N', N' tetraacetylated alkylenediamines, wherein the alkylene group contains 1 to 6 carbon atoms, especially wherein the alkylene Those compounds whose radicals contain 1, 2 and 6 carbon atoms. Tetraacetylethylenediamine (TAED) is particularly preferred.

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

其中R¹是具有1-14个碳原子的烷基，R²是含有1-14个碳原子的亚烷基，R⁵是H或含有1-10个碳原子的烷基，L可是必要的任何离去基团。R¹优选含有6-12个碳原子。R²优选含有4-8个碳原子。R¹可以是直链烷基或含支链取代基的支链烷基、或这两者，并且可以来源于合成物或天然物，包括例如牛油脂肪。类似结构的变种也适用于R²。取代物可包括烷基、卤原子、氮、硫和其它典型的取代基或有机化合物。R⁵优选为H或甲基。R¹和R⁵总共不应含多于18个碳原子。这类酰胺取代的漂白活化剂化合物描述在EP-A-0170386中。苯并噁嗪有机过氧酸前体Amide substituted alkyl peroxyacid precursor compounds are also suitable, including those having the general formula:

Wherein R ¹ is an alkyl group having 1-14 carbon atoms, R ² is an alkylene group containing 1-14 carbon atoms, R ⁵ is H or an alkyl group containing 1-10 carbon atoms, L may be necessary any leaving group. R ¹ preferably contains 6-12 carbon atoms. ^R2 preferably contains 4-8 carbon atoms. ^R1 can be straight chain alkyl or branched chain alkyl with branched substituents, or both, and can be derived from synthetic or natural sources including, for example, tallow fat. Variations of similar structures are also suitable for ^R2 . Substituents may include alkyl groups, halogen atoms, nitrogen, sulfur and other typical substituents or organic compounds. R ⁵ is preferably H or methyl. Together ^R1 and ^R5 should not contain more than 18 carbon atoms. Amide substituted bleach activator compounds of this type are described in EP-A-0170386. Benzoxazine Organic Peroxyacid Precursor

其中R₁是H，烷基、烷芳基、芳基或芳烷基，其中R₂、R₃、R₄和R₅可以是相同或不同的取代基，选自H、卤原子、烷基、链烯基、芳基、羟基、烷氧基、氨基、烷氨基、COOR₆(其中R₆是氢或烷基)和羰基官能团。Also suitable are precursor compounds of the benzoxazine type, which are disclosed, for example, in EP-A-332,294 and EP-A-482,807, especially those compounds of the formula: Including such substituted benzoxazines:

Wherein R ₁ is H, alkyl, alkaryl, aryl or aralkyl, wherein R ₂ , R ₃ , R ₄ and R ₅ can be the same or different substituents selected from H, halogen atom, alkyl , alkenyl, aryl, hydroxy, alkoxy, amino, alkylamino, COOR ₆ (wherein R ₆ is hydrogen or alkyl) and carbonyl functional groups.

预制的有机过氧酸Particularly preferred benzoxazine-type precursors:

preformed organic peroxyacids

The organic peroxyacid bleaching system may contain, in addition to the organic peroxyacid bleach precursor compound, (or as a substitute for the compound) a preformed organic peroxyacid, generally in an amount of from 1% to 15% of the composition. % (weight), more preferably 1%-10% (weight).

其中R¹是具有1-14个碳原子的烷基、芳基或烷芳基，R²是含有1-14个碳原子的亚烷基、亚芳基或烷亚芳基，R⁵是H或含有1-10个碳原子的烷基、芳基、或烷芳基。R¹优选含有6-12个碳原子。R²优选含有4-8个碳原子。R¹可以是直链或支链烷基、含支链取代基的取代的芳基或烷芳基、或这两者，并且可以来源于合成物或天然物，包括例如牛油脂肪。类似结构的变种也适用于R²。取代物可包括烷基、芳基、卤原子、氮、硫和其它典型的取代基或有机化合物。R⁵优选为H或甲基。R¹和R⁵总共不应含多于18个碳原子。这类酰胺取代的有机过氧酸化合物描述在EP-A-0170386中。A preferred class of organic peroxyacid compounds are amide substituted compounds having the general formula:

Wherein ^R is an alkyl, ^aryl or alkaryl group with 1-14 carbon atoms, ^R is an alkylene, arylene or alkarylene group with 1-14 carbon atoms, R is H Or an alkyl, aryl, or alkaryl group containing 1-10 carbon atoms. R ¹ preferably contains 6-12 carbon atoms. ^R2 preferably contains 4-8 carbon atoms. ^R1 can be straight chain or branched chain alkyl, substituted aryl or alkaryl containing branched chain substituents, or both, and can be derived from synthetic or natural sources including, for example, tallow. Variations of similar structures are also suitable for ^R2 . Substituents may include alkyl groups, aryl groups, halogen atoms, nitrogen, sulfur and other typical substituents or organic compounds. R ⁵ is preferably H or methyl. Together ^R1 and ^R5 should not contain more than 18 carbon atoms. Amide substituted organic peroxyacid compounds of this type are described in EP-A-0170386.

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

Compositions of the present invention are preferably free of chlorine bleach. bleach catalyst

The present invention also includes compositions comprising a catalytically effective amount of a bleach catalyst, such as a water-soluble magnesium salt.

The bleach catalyst is used in the compositions of the present invention in a catalytically effective amount, by "catalytically effective amount" meaning that the amount is sufficient to enhance the beneficial bleaching and removal of stains or soils from the target substrate regardless of the comparative test conditions used. is enough. Whereas, in a fabric washing operation, the target substrate is generally a fabric with, for example, various food stains, and for automatic dishwashing, the target substrate may be, for example, a tea cup or saucer stained with tea, or a dish stained with tomato soup. Polyethylene dish. The test conditions will vary depending on the type of washing equipment used and the habits of the user. Front-load washers used in Europe typically use less water and higher detergent concentrations than top-load washers in the United States. Some washing machines have considerably longer wash cycles than others. Some users choose to use very hot water in their laundry operations; others use warm or even cold water. Naturally, the catalytic performance of the bleach catalyst will be influenced by these conditions and the level of bleach catalyst used in fully formulated detergent and bleach compositions can be adjusted appropriately. In practice, without being limited by theory, the compositions and methods of the present invention can be adjusted to provide about at least one part per million active bleach catalyst species in the wash water solution, preferably about 1 ppm to about 200 ppm catalyst material in the wash water solution . To further illustrate this point, specifically under European conditions using perborate and a bleach precursor such as benzoyl caprolactam, at 40°C and pH 10, about 3 micromolar magnesium catalyst is effective of. Under American conditions need to increase the concentration 3-5 times to get the same result. Conversely, the use of bleach precursors and magnesium catalysts with borates allows formulators to achieve equivalent bleaching power at lower perborate levels compared to products without magnesium catalysts.

The bleach catalyst materials herein may comprise the free acid or any suitable salt form.

One type of bleach catalyst is a catalytic system comprising heavy metal cations with defined bleach catalytic activity, where examples of heavy metal cations are copper, iron or magnesium cations, auxiliary metal cations with little or no bleach catalytic activity such as zinc or aluminum cations , and chelating agents with defined stability constants for catalytic and auxiliary metal cations, especially ethylenediaminetetraacetic acid, ethylenediaminetetrakis(methylenephosphonic acid) and water-soluble salts thereof. Such catalysts are disclosed in U.S. 4,430,243.

Other types of bleach catalysts include magnesium-based complexes disclosed in US 5,246,621 and US 5,244,594. Preferred examples of these catalysts include Mn ^IV ₂ (uO) ₃ (1,4,7-trimethyl-1,4,7-triazacyclononane) ₂ -(PF ₆ ) ₂ , Mn ^III ₂ (uO ) ₁ (u-OAc) ₂ (1,4,7-trimethyl-1,4,7-triazacyclononane) ₂ -(ClO ₄ ) ₂ , Mn ^IV ₄ (uO) ₆ (1, 4,7-triazacyclononane) ₄ -(ClO ₄ ) ₂ , Mn ^III Mn ^IV ₄ (uO) ₁ (u-OAc) ₂ -(1,4,7-trimethyl-1,4, 7-Triazacyclononane) ₂ -(ClO ₄ ) ₃ and mixtures thereof. Others are described in European Patent Application 549,272. 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.

For examples of suitable bleach catalysts see US 4,246,612 and US 5,227,084. See also US 5,194,416 which discloses mononuclear magnesium(IV) complexes such as Mn(1,4,7-trimethyl-1,4,7 -triazacyclononane)(OCH ₃ ) ₃ -(PF ₆ ).

Yet another class of bleach catalysts, disclosed in U.S. 5,114,606, is magnesium (II), (III) and/or (IV) in combination with a non-carboxylate polyamide having at least three adjacent C-OH groups. Water-soluble complexes of hydroxy compound ligands. Preferred ligands include sorbitol, iditol, dulsitol, mannitol, xylitol, arabitol, adonitol, meso erythritol, meso-inositol, lactose and mixtures thereof .

其中R¹、R²、R³和R⁴均选自H、取代的烷基和芳基，以致R¹-N＝C-R²和R³-C＝N-R⁴每个形成五或六员环。该环可进一步被取代。B是桥基，选自O、S、CR⁵R⁶、NR⁷和C＝O，其中R⁵、R⁶和R⁷均为H、烷基或芳基，包括取代的或未取代的基团。优选的配位体包括吡啶、哒嗪、嘧啶、吡嗪、咪唑、吡咯和三唑环。该环可任选地被取代基如烷基、芳基、烷氧基、卤化物和硝基取代。特别优选的是2，2’-联吡啶胺配位体。优选的漂白催化剂包括Co、Cu、Mn、Fe-联吡啶甲烷和联吡啶胺配合物。最优选的催化剂包括Co(2，2’-联吡啶胺)Cl₂，二(异硫氰酸根合)联吡啶胺-钴(II)、三联吡啶胺-钴(II)高氯酸盐、Co(2，2-联吡啶胺)₂O₂ClO₄、双(2，2’-联吡啶胺)铜(II)高氯酸盐、三(联-2-吡啶胺)铁(II)高氯酸盐和其混合物。US 5,114,611 discloses bleach catalysts comprising complexes of transition metals, including Mn, Co, Fe or Cu, with non-(macro)cyclic ligands. Said ligand has the formula:

wherein R ¹ , R ² , R ³ and R ⁴ are all selected from H, substituted alkyl and aryl such that R ¹ -N=CR ² and R ³ -C=NR ⁴ each form a five- or six-membered ring. This ring can be further substituted. B is a bridging group selected from O, S, CR ⁵ R ⁶ , NR ⁷ and C═O, wherein R ⁵ , R ⁶ and R ⁷ are all H, alkyl or aryl, including substituted or unsubstituted groups group. Preferred ligands include pyridine, pyridazine, pyrimidine, pyrazine, imidazole, pyrrole and triazole rings. The ring may be optionally substituted with substituents such as alkyl, aryl, alkoxy, halide and nitro. Particularly preferred are 2,2'-bipyridylamine ligands. Preferred bleach catalysts include Co, Cu, Mn, Fe-bipyridyl methane and bipyridylamine complexes. The most preferred catalysts include Co(2,2'-bipyridylamine) _Cl2 , bis(isothiocyanato)bipyridylamine-cobalt(II), terpyridylamine-cobalt(II) perchlorate, Co (2,2-bipyridylamine) ₂ O ₂ ClO ₄ , bis(2,2'-bipyridylamine)copper(II) perchlorate, tris(bi-2-pyridylamine)iron(II) perchlorate salts and mixtures thereof.

Other examples include manganese gluconate, Mn(CF ₃ SO ₃ ) ₂ , Co(NH ₃ ) ₅ Cl, and dinuclear Mn complexes with tetra-N-dentate and bi-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 .

The bleach catalyst of the present invention can be prepared by the following method: the water-soluble ligand and the water-soluble manganese salt are mixed in an aqueous medium, and the obtained mixture is evaporated and concentrated to prepare the bleach catalyst. Any convenient water-soluble salt of manganese can be used in the present invention. Manganese (II), (III), (IV) and/or (V) are readily available commercially. In some cases, sufficient manganese may be present in the wash solution, but usually the Mn cation is added to the composition to ensure that it is present in a catalytically effective amount. The sodium salt of the ligand and the manganese salt selected from MnSO ₄ , Mn(ClO ₄ ) ₂ or MnCl ₂ (rarely preferred) are dissolved in the ligand:Mn salt molar ratio of about 1:4 to 4:1 neutral or slightly alkaline pH water. The water is first deoxygenated by boiling, then cooled with a nitrogen purge. The resulting solution was evaporated (under _N2 , if necessary) and the resulting solid was used without further purification in the bleach and detergent compositions of the present invention.

In another embodiment, a water-soluble manganese source such as _MnSO4 is added to the ligand-containing bleach/cleaning composition or aqueous bleach/cleaning bath. Some types of complexes are apparently formed in situ, and the performance of the improved bleach is reliable. In this in situ generation method, it is appropriate to use a large molar excess of ligand to manganese, the molar ratio of ligand to Mn being generally 3:1 to 15:1. Other ligands also scavenge labile metal ions such as iron and copper, thereby inhibiting bleach decomposition. One possible class of such systems is described in European Patent Application 549,271.

The structures of some of the manganese complexes that catalyze bleaches described in this invention have been elucidated and may be speculated to include chelates or other hydrated coordination compounds resulting from the interaction of the ligand's carboxyl and nitrogen atoms with manganese cations of. In addition, the oxidation state of the manganese cation during the catalysis is indeed not known, it could be (+II), (+III), (+IV) or (+V) valence. Since the ligands may have six contact points with the manganese cation, it is reasonable to speculate that multinuclear species and/or cage structures may exist in the aqueous bleaching medium. Whatever form the active manganese ligand material is actually present, it is significantly catalytic to provide improved bleaching performance on tough stains such as tea, ketchup, coffee, blood and the like.

Other bleach catalysts are described, for example, in European Patent Application 408,131 (cobalt complex catalysts), European Patent Application 384,503 and 306,089 (metalloporphyrin catalysts), U.S. 4,728,455 (manganese/multidentate ligand catalysts), U.S. 4,711,748 and European Patent Applications 224,952 (manganese catalysts adsorbed on aluminosilicates), U.S. 4,601,845 (aluminosilicates loaded with manganese and zinc or manganese salts), U.S. 4,626,373 (manganese/ligand catalysts), U.S. 4,119,557 ( iron complex catalysts), German Patent Specification 2,054,019 (cobalt chelating agent catalysts), Canada 866,191 (transition metal-containing salts), U.S. 4,430,243 (chelating agents with manganese cations and non-catalytic metal cations) and U.S. manganese catalyst). relative release kinetics

It is an essential aspect of the present invention to provide a method for delaying the release of organic peroxyacid bleach into the wash solution relative to the release of heavy metal ion sequestrants.

Said method may comprise a method of delaying the release of the organic peroxyacid bleach into the wash solution.

Alternatively said methods may include methods of increasing the rate of release of the heavy metal ion sequestrant into solution. delayed release rate method

The method provides delayed release of the organic peroxyacid bleach source itself into the wash solution. Alternatively, when the source of peroxyacid is an organic peroxyacid precursor compound, the method of delaying release may include a method of inhibiting or preventing in situ perhydrolysis of the organic peroxyacid into solution. Such methods may include, for example, delaying the release of the source of hydrogen peroxide into the wash solution by, for example, delaying the release of any inorganic perhydrate salt that is the source of hydrogen peroxide into the wash solution.

The method of delayed release may comprise coating any suitable component with a coating material or mixture of coating materials designated to provide delayed release. Such coating materials may comprise, for example, poorly water soluble materials, or coating materials of sufficient thickness that the dissolution kinetics of such thick coating materials provide a controlled rate of release.

The cladding material can be provided using various methods. Typical amounts of any coating material are: coating material to bleach weight ratio of 1:99 to 1:2, preferably 1:49 to 1:9.

Suitable coating materials include triglycerides (eg, partially hydrogenated vegetable oils, soybean oil, cottonseed oil), mono- or diglycerides, microcrystalline waxes, gelatin, cellulose, fatty acids, and any mixtures thereof.

Other suitable cladding materials may include alkali and alkaline earth metal sulfates, silicates and carbonates, including calcium carbonate.

A preferred cladding material is sodium silicate having a SiO ₂ :Na ₂ O ratio of 1.6:1 to 3.4:1, preferably 2.8:1, provided as an aqueous solution to provide from 2% to 10% by weight of percarbonate. % (typically 3%-5%) silicate solids. Magnesium silicate may also be included in the cladding material.

Any inorganic salt coating material can be used in combination with an organic binder material to provide a composite inorganic salt/organic binder coating material. Suitable binders include C ₁₀ -C ₂₀ alcohol ethoxylates containing 5-100 moles of ethylene oxide per mole of alcohol; more preferably C ₁₅ -C ₂₀ primary alcohol ethoxylates containing 20-100 moles of ethylene oxide.

Other preferred binders include certain polymeric materials. Examples of such polymeric materials are polyvinylpyrrolidone having an average molecular weight of 12,000 to 700,000, and polyethylene glycol (PEG) having an average molecular weight of 600 to 10,000. Copolymers of maleic anhydride with ethylene, methyl vinyl ether or methacrylic acid, wherein maleic anhydride constitutes at least 20 mole percent of the polymer composition, are additional examples of polymeric materials useful as binders . These polymeric materials may be used by themselves or in combination with solvents such as water, propylene glycol and the above mentioned _C10 - _C20 alcohol ethoxylates containing 5-100 moles of ethylene oxide per mole of alcohol. Further examples of binders include _C10 - _C20 mono- and diglycerides, and also _C10 - _C20 fatty acids.

Cellulose derivatives such as methyl cellulose, carboxymethyl cellulose, ethyl hydroxyethyl cellulose, and hydroxyethyl cellulose, and homo- or co-polymerized polycarboxylic acids or their salts are suitable for use in the present invention Additional Examples of Adhesives.

One method of applying the cladding material involves agglomeration. A preferred method of agglomeration involves the use of any of the organic binder materials described herein above. Any conventional agglomerator/mixer can be used including, but not limited to, pan, drum and vertical blender types. The melt coat composition can also be applied by pouring or atomizing spraying it onto the moving bed bleach.

Other methods of providing the desired delayed release include mechanical methods in which the physical properties of the bleach are altered to control its solubility and rate of release. Suitable protocols include compaction, mechanical injection, manual injection and adjustment of the solubility of the bleaching compound through selection of the particle size of any particulate component of the bleaching compound.

The choice of particle size will depend on the composition of the particle components and the need to meet the desired delayed release kinetics. Ideally the particle size should be greater than 500 microns, preferably with an average particle diameter of 800 to 1200 microns.

Alternatives to providing a method of delayed release include suitable selection of any other components in the matrix of the detergent composition such that when the composition is added to a wash solution, the ionic strength environment provided therein enables the desired delayed release kinetics to be obtained. study. Increase release rate method

All suitable methods of increasing the rate of release of the heavy metal ion sequestrant into solution are contemplated.

Methods of enhancing release may include coating any suitable component with a coating material designed to enhance release. The wrapping material may comprise, for example, highly water-soluble or even foamable materials.

Other methods of providing the desired delayed release include mechanical methods in which the physical properties of the heavy metal ion sequestrant are altered to enhance their solubility and rate of release.

A suitable regimen may include judicious selection of the particle size of any component containing a heavy metal ion sequestrant. The choice of particle size will depend on both the composition of the particle components and the need to meet the desired enhanced release kinetics. Ideally the particle size should be less than 1200 microns, preferably with an average particle diameter of 1100 to 500 microns.

Alternatives to providing a method of delayed release include suitable selection of any other component in the matrix of the detergent composition, or suitable selection of any particulate component containing a heavy metal ion sequestrant, such that when the composition is added to the wash solution , where the ionic strength environment provided is such that the desired enhanced release kinetics are obtained. Relative Release Rate - Kinetic Parameters

The release of the organic peroxyacid bleach component from the peroxyacid bleaching system relative to the release of the heavy metal ion sequestrant component is such that, in the T50 test method described herein, the heavy metal ion sequestrant The time required for the concentration of its final concentration of 50% is less than 120 seconds, preferably less than 90 seconds, more preferably less than 60 seconds, and the time required to obtain the concentration of said organic peroxyacid bleaching agent for its final concentration of 50% is less than 120 seconds More than 180 seconds, preferably 180-480 seconds, more preferably 240-360 seconds, there are differences between them.

In the most preferred aspect of the invention, the release of the bleach is such that the time required to obtain the total amount of available oxygen (AVO) to 50% of its final amount in the T50 test method described herein is greater than 180 seconds, preferably 180-480 seconds, more preferably 240-360 seconds. A method for determining the AVO content is disclosed in European Patent Application 93870004.4.

In another preferred aspect of the invention wherein the source of peroxyacid bleach is a precursor of peroxyacid bleach which is used in combination with a source of hydrogen peroxide, the kinetics of the release of hydrogen peroxide into the wash solution The kinetics relative to the release of the heavy metal ion sequestrant component is such that, in the T50 test method described herein, the time required to obtain said heavy metal ion sequestrant at a concentration of 50% of its final concentration is less than 120 seconds, preferably Less than 90 seconds, more preferably less than 60 seconds, the time required to obtain said hydrogen peroxide concentration of 50% of its final concentration is greater than 180 seconds, preferably 180 to 480 seconds, more preferably 240 to 360 seconds.

The final washing concentration of the heavy metal ion chelating agent is generally 0.0001%-0.05%, preferably greater than 0.001%, more preferably greater than 0.002%.

The final wash level of any inorganic perhydrate bleach will generally be from 0.005% to 0.25% by weight, but preferably greater than 0.05%, more preferably greater than 0.075%.

The final wash level of any peroxyacid precursor is generally from 0.001% to 0.08% by weight, but preferably from 0.005% to 0.05%, most preferably from 0.015% to 0.05%. Delayed release test method

The "TA test method" is used herein to define the delayed release kinetics. The "TA test method" determines that when the composition containing the component to be tested is dissolved according to the standard conditions given herein, the amount of the component obtained is The time required for A% of its final concentration/content.

This standard condition involves adding 10 g of the composition to a 1 liter glass filled with 1000 ml of distilled water at 20°C. The contents of the glass were stirred at 100 rpm using a magnetic stirrer which was bean/pebble shaped with a maximum dimension of 1.5 cm and a minimum dimension of 0.5 cm. The concentration/amount reached 10 minutes after adding the composition to the beaker with water was taken as the final concentration/amount.

Appropriate analytical methods are chosen to enable accurate determination of the burst and final concentrations of the relevant components in solution after addition of the composition to the beaker of water.

Such analytical methods may include those that continuously monitor the concentration amount of a component, including, for example, photometric and conductimetric methods.

Alternatively, methods may be used which include removing titres from the solution at fixed time intervals, stopping their dissolution process by an appropriate method, such as by rapidly lowering the temperature of the titres, and then using any method such as The chemical titration method determines the concentration of the analyte component in the titration product.

Appropriate graphing methods, including curve fitting methods, where appropriate capable of calculating TA values from raw material analysis results, may be used.

The particular analytical method chosen to determine the concentration of a component will depend on the nature of the component and the nature of the composition containing the component. water soluble builder compound

The detergent compositions of the present invention can contain water-soluble builder compounds as a most preferred component, generally at a level of from 1% to 80%, preferably from 10% to 70%, most preferably from 20% to 60%, by weight of the composition.

The most preferred aspect of the present invention also provides a method of delaying the release of bleach into the wash solution relative to the release of the preferred water-soluble builder components. The method may comprise any of the delayed release methods described herein commensurate with achieving delayed release of the bleach component described herein above.

Preferably said delayed release method is selected such that, in the test method described herein, a concentration of said hydrobuilder is obtained which is 50% of its final concentration in less than 120 seconds, preferably less than 90 seconds, more preferably less than 60 seconds.

The final washing concentration of the water-soluble builder is generally 0.005%-0.4%, preferably 0.05%-0.35%, more preferably 0.1%-0.3%.

Suitable water-soluble builder compounds include water-soluble monopolymeric polycarboxylates or their acid forms, homo- or copolymeric polycarboxylic acids or their salts. Wherein the polycarboxylic acid comprises at least two carboxyl groups of not more than 2 carbon atoms separated from each other, carbonates, bicarbonates, borates, phosphates, silicates and mixtures of any of the foregoing.

Carboxylate or polycarboxylate builders can be of the monopolymeric or oligomeric type, but monopolymeric polycarboxylates are generally preferred for reasons of cost and performance.

Suitable carboxylate salts containing one carboxy group include the water-soluble salts of the following acids: lactic acid, glycolic acid and derivatives thereof. Polycarboxylates containing two carboxy groups include the water-soluble salts of the following acids: succinic acid, malonic acid, (ethylenedioxy)diacetic acid, maleic acid, diglycolic acid, tartaric acid, tartronic acid and fumaric acid, and ether carboxylates and thionyl carboxylates. Polycarboxylates containing three carboxy groups include, inter alia, the water-soluble citrate, aconitate and citraconate and succinate derivatives. Carboxymethoxysuccinates as described in British Patent 1,379.241, lactoxysuccinates as described in British Patent 1,389,732 and aminosuccinates as described in Dutch Application 7205873, and oxopolycarboxylates Acid acid materials such as 2-oxa-1,1,3-propane tricarboxylate are described in British Patent 1,387,447.

Polycarboxylates containing four carboxy groups include oxydisuccinates disclosed in British Patent 1,261,829, 1,1,2,2-ethane tetracarboxylate, 1,1,3,3-propane tetracarboxylate salt and 1,1,2,3-propane tetracarboxylate. Polycarboxylates containing sulfo substituents include the sulfosuccinate derivatives disclosed in British Patents 1,398,421 and 1,398,422 and U.S. 3,936,448, and the sulfonated pyrolyzed citrates described in British Patent 1,439,000.

Alicyclic and heterocyclic polycarboxylates include cyclopentane-cis, cis, cis-tetracarboxylate, cyclopentadiene pentacarboxylate, 2,3,4,5-tetrahydrofuran-cis, cis, cis- Tetracarboxylate, 2,5-tetrahydrofuran-cis-dicarboxylate, 2,2,5,5-tetrahydrofuran tetracarboxylate, 1,2,3,4,5,6-hexane hexacarboxylate and carboxymethyl derivatives of polyols such as sorbitol, mannitol and xylitol. Aromatic polycarboxylates include mellitic acid, pyromellitic acid and the phthalic acid derivatives disclosed in British Patent 1,425,343.

Among the above polycarboxylates, preferred are hydroxycarboxylates containing up to 3 carboxy groups per molecule, especially citrates.

The parent acids of monopolymeric or oligomeric polycarboxylate chelating agents or mixtures thereof and their salts, such as citric acid or citrate/citric acid mixtures, are also contemplated as useful builder ingredients.

Borate builders can also be used as well as builders containing borate-forming materials which can form borate under detergent storage or wash conditions, but at temperatures below about 50°C, especially low At about 40°C they are not preferred.

Examples of carbonate builders are alkaline earth and alkali metal carbonates including sodium carbonate and sodium sesquicarbonate and mixtures thereof and superfine calcium carbonate.

Specific 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 to 21, and inositol hexaphosphate salt of phosphoric acid.

Suitable silicates include water soluble sodium silicates having a _SiO2 : _Na2O ratio of 1.0 to 2.8, preferably 1.6 to 2.4, most preferably 2.0. The silicates may be in the form of anhydrous or hydrated salts. Sodium silicate with a _SiO2 : _Na2O ratio of 2.0 is the most preferred silicate.

Silicates are preferably present in the detergent compositions of the present invention in an amount of from 5% to 50% by weight of the composition, more preferably from 10% to 40% by weight. additional detergent ingredients

The detergent compositions of the present invention may also contain additional detergent ingredients. The precise identity of these additional components and their incorporation levels will depend upon the physical form of the composition and the nature of the laundering operation for which it is used.

The compositions of the present invention may, for example, be formulated as hand and washing machine detergent compositions, including laundry additive compositions and compositions suitable for pretreating stained fabrics, and machine dishwashing compositions.

When the compositions of the present invention are formulated as compositions suitable for use in machine washing methods, such as washing machine and dishwashing machine washing methods, the compositions of the present invention preferably contain one or more additional detergent components selected from surface Active agents, water insoluble builders, organic polymeric compounds, additional enzymes, suds suppressors, lime soap dispersants, soil suspending and anti-redeposition agents and corrosion inhibitors. Laundry compositions can also contain softening agents as additional detergent ingredients. Surfactant

The detergent compositions of the present invention may contain, as an additional detergent component, a surfactant selected from the group consisting of anionic, cationic, nonionic, amphoteric and zwitterionic surfactants and mixtures thereof.

Surfactants are generally present in an amount of 0.1% to 60% by weight. Surfactants are preferably incorporated in an amount of 1% to 35% by weight, most preferably 1% to 20% by weight.

Surfactants are preferably formulated to be compatible with any enzyme components present in the composition. In liquid or gel compositions, the surfactants are most preferably formulated to promote, or at least not degrade, the stability of any enzymes present in these compositions.

General illustrations of anionic, nonionic, amphoteric and zwitterionic surfactants and species of these surfactants are disclosed in U.S. Patent 3,929,678, issued December 30, 1975 to Laughlin and Heuring. ; Additional examples are disclosed in "Surface Active Agents and Detergents" (Volumes I and II, by Schwartz. Perry and Berch). Examples of suitable cationic surfactants are disclosed in U.S. Patent 4,259,217, Murphy, issued March 31,1981.

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

Essentially any anionic surfactant useful for detersive purposes can be included in the compositions of the present invention. These may include salts of anionic sulfate, sulfonate, carboxylate, and sarcosinate surfactants (including, for example, sodium, potassium, ammonium, and substituted ammonium salts such as mono-, di-, and triethanolamine salts).

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

Anionic sulfate surfactants suitable for use in the present invention include linear and branched primary alkyl sulfates, alkyl ethoxy sulfates, fatty oil-based glycerol sulfates, alkylphenol oxirane ether sulfates, C ₅ -C ₁₇ acyl-N-(C ₁ -C ₄ alkyl) glucosamine sulfate and C ₅ -C ₁₇ acyl-N-(C ₁ -C ₂ hydroxyalkyl) glucosamine sulfate, and Alkyl polysaccharide sulfates, such as sulfates of alkyl polyglucosides (non-sulfated nonionic compounds are also described herein).

The alkyl ethoxy sulfate surfactants are preferably selected from C ₆ -C ₁₈ alkyl sulfates which are ethoxylated with about 0.5 to about 20 moles of ethylene oxide per mole. More preferred alkyl ethoxy sulfate surfactants are C ₆ -C ₁₈ alkyl sulfates which are ethoxylated with about 0.5 to about 20 moles, preferably about 0.5 to about 5 moles, of ethylene oxide per mole. Anionic Sulfonate Surfactant

Anionic sulfonate surfactants suitable for use in the present invention include salts of C ₅ -C ₂₀ linear alkylbenzene sulfonates, alkyl ester sulfonates, C ₆ -C ₂₂ primary or secondary alkane sulfonates, C ₆ -C ₂₄ olefin sulfonates, sulfonated polycarboxylic acids, alkyl glycerol sulfonates, fatty acyl glycerol sulfonates, fatty oleyl glycerol sulfonates and any mixtures thereof. Anionic Carboxylate Surfactants

Anionic carboxylate surfactants suitable for use herein include alkyl ethoxy carboxylates, alkyl polyethoxy polycarboxylate surfactants and soaps (alkyl carboxylates), especially as described herein. Some secondary soaps.

Preferred alkyl ethoxy carboxylates for use in the present invention include those having _the formula RO( _CH2CH2O ) _xCH3COO ^- M ⁺ wherein R is _{a C6 to C18} alkyl group and x is 0 to 10, the ethoxylate distribution is such that, by weight, the amount of the material when x is 0 is less than about 20%; the amount of material when x is greater than 7 is less than about 25% when the average R is For C ₁₃ or lower, the average x is about 2 to 4; when the average R is greater than C ₁₃ , the average x is about 3 to 10, M is a cation, preferably selected from alkali metals, alkaline earth metals, ammonium, mono, di and Triethanolammonium, most preferably sodium, potassium, ammonium and mixtures thereof with magnesium ions. Preferred alkyl ethoxy carboxylates are those wherein R is C ₁₂ -C ₁₈ alkyl.

Alkyl polyethoxy polycarboxylate surfactants suitable for use herein include those having the formula RO-(CHR ₁ -CHR ₂ -O)-R ₃ wherein R is C ₆ -C ₁₈ alkyl, x is 1 to 25, R _{and R} are selected from hydrogen, methyl acid radical (methyl acid radical), succinic acid, hydroxysuccinic acid, and mixtures thereof, wherein at least one _R or _R is succinic or hydroxysuccinic Acid group, _R3 is selected from hydrogen, substituted or unsubstituted hydrocarbons with 1 to 8 carbon atoms, and mixtures thereof. Anionic secondary soap surfactant

Preferred soap surfactants are secondary soap surfactants containing carboxyl units attached to secondary carbons. The secondary carbon may be in a ring structure, for example in p-octylbenzoic acid or in alkyl substituted cyclohexyl carboxylates. The secondary soap surfactant should preferably be free of ether linkages, ester linkages and hydroxyl groups. Preferably there should be no nitrogen atoms in the head group (amphiphilic moiety). Secondary soap surfactants generally contain a total of 11-15 carbon atoms, although slightly more (eg, up to 16) carbon atoms are acceptable, eg p-octylbenzoic acid.

The following general structures further illustrate some preferred secondary soap surfactants:

A. The most preferred class of secondary soaps includes secondary carboxyl species of formula R ³ CH(R ⁴ )COOM, where R ³ is CH ₃ (CH ₂ ) _x and R ⁴ is CH ₃ (CH ₂ ) _y , where y can be is 0 or an integer from 1 to 4, x is an integer from 4 to 10, and the sum of (x+y) is 6-10, preferably 7-9, most preferably 8.

B. Other preferred classes of secondary soaps include those carboxyl compounds wherein the carboxyl substituent is on the cyclic hydrocarbyl unit, i.e. secondary soaps of formula ^R5 - ^R6 -COOM, wherein ^R5 is _C7 - _C10 , preferably _C8 -C ₉ alkyl or alkenyl, R ⁶ is a ring structure, such as benzene, cyclopentane and cyclohexane (note: R ⁵ can be in the ortho, meta or para position relative to the carboxyl group on the ring).

C. Yet another class of preferred secondary soaps includes the formula CH ₃ (CHR) _k -(CH ₂ ) _m -(CHR) _n -CH(COOM)(CHR) _o -(CH ₂ ) _p -(CHR) _q -Secondary carboxyl compounds of CH ₃ , wherein R are both C ₁ -C ₄ alkyl, wherein knoq is an integer from 0 to 8, provided that the total number of carbon atoms (including those of carboxylates) is 10 to 18.

In each of formulas A.B and C above, M can be any suitable, especially water solubilizing counterion.

Particularly preferred secondary soap surfactants for use herein are water-soluble salts of acids selected from the group consisting of 2-methyl-1-undecanoic acid, 2-ethyl-1-decanoic acid, 2-propyl- 1-nonanoic acid, 2-butyl-1-octanoic acid and 2-pentyl-1-heptanoic acid. Alkali metal sarcosinate

Other suitable anionic surfactants are alkali metal sarcosinates of the formula R-CON(R ¹ )CH ₂ COOM, wherein R is C ₅ -C ₁₇ linear or branched chain alkyl or alkenyl, and R ¹ is C ₁ -C ₄ alkyl, M is an alkali metal ion. Preferred examples are myristyl and oleyl methyl sarcosine sodium salts. nonionic surfactant

Essentially any nonionic surfactant useful for detersive purposes can be included in the composition. Representative of useful non-limiting classes of nonionic surfactants are listed below. Nonionic Polyhydroxy Fatty Acid Amide Surfactant

Polyhydroxy fatty acid amides suitable for use in the present invention are those compounds having the formula R ² CONR ¹ Z, wherein R ₁ is H, C ₁ -C ₄ hydrocarbyl, 2-hydroxyethyl, 2-hydroxypropyl or mixtures thereof, preferably C ₁ -C ₄ alkyl, more preferably C ₁ or C ₂ alkyl, most preferably C ₁ alkyl (i.e. methyl); R ₂ is C ₅ -C ₃₁ 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 poly A hydroxyhydrocarbyl group having at least 3 hydroxyl groups directly attached to the hydrocarbyl chain, or an alkoxylated (preferably ethoxylated or propoxylated) derivative thereof. Z is preferably derived from a reducing sugar in a reductive amination reaction; more preferably Z is a glycityl. Alkylphenol Condensate Nonionic Surfactant

Polyethylene oxide, polypropylene oxide and polybutylene oxide condensates of alkylphenols are suitable for use in the present invention. In general, polyethylene oxide condensates are preferred. These compounds include the condensation products of alkylphenols with alkylene oxides having alkyl groups having from about 6 to about 18 carbon atoms which are linear or branched chain structures. Ethoxylated Alcohol Nonionic Surfactant

Alkyl ethoxylated condensation products of fatty alcohols with from about 1 to about 25 moles of ethylene oxide are suitable for use in the present invention. The alkyl chain of the fatty alcohol can be straight or branched, primary or secondary, and generally contains 6 to 22 carbon atoms. Particularly preferred are condensation products of alcohols having alkyl groups having 8 to 20 carbon atoms with about 2 to about 10 moles of ethylene oxide per mole of alcohol. Ethoxylated/Propoxylated Fatty Alcohol Nonionic Surfactant

Ethoxylated _C6 - _C18 fatty alcohols and _C6 - _C18 mixed ethoxylated/propoxylated fatty alcohols, especially water soluble, are suitable surfactants for use in the present invention. Preferably the ethoxylated fatty alcohol is a C ₁₀ -C ₁₈ ethoxylated fatty alcohol with a degree of ethoxylation of 3-50, most preferably a C ₁₂ -C ethoxylated alcohol with a degree of ethoxylation of 3-40. ₁₈ Ethoxylated fatty alcohols. Preferred mixed ethoxylated/propoxylated fatty alcohols have an alkyl chain length of 10 to 18 carbon atoms, a degree of ethoxylation of 3 to 30, and a degree of propoxylation of 1 to 10. Non-ionic EO/PO condensate with propylene glycol

Condensation products of ethylene oxide with a hydrophobic base resulting from the condensation of propylene oxide with propylene glycol are suitable for use in the present invention. The hydrophobic portion of these compounds preferably has a molecular weight of from about 1500 to about 1800 and exhibits water insolubility. Examples of such compounds include certain of the commercially available Pluronic ^™ surfactants sold by BASF. Nonionic EO condensation products with propylene oxide/ethylenediamine adducts

Condensation products of ethylene oxide with the product obtained by reacting propylene oxide with ethylenediamine are suitable for use in the present invention. The hydrophobic portion of these products consists of the reaction product of ethylenediamine and excess propylene oxide, generally having a molecular weight of from about 2500 to about 3000. Examples of such nonionic surfactants include certain of the commercially available Tetronic( ^TM) compounds sold by BASF. Alkyl polysaccharide nonionic surfactant

Alkyl polysaccharides suitable for use in the present invention are disclosed in U.S. 4,565,647, Llenado, issued January 21, 1986, which have hydrophobic polysaccharides containing from about 6 to about 30 carbon atoms, preferably from about 10 to about 16 carbon atoms. moieties, and polysaccharide hydrophilic groups containing about 1.3 to about 10, preferably about 1.3 to about 3, most preferably about 1.3 to about 2.7 saccharide units, such as polyglycosides. Any reducing sugar containing 5 or 6 carbon atoms may be used, eg glucose, galactose and galactosyl moieties may be substituted for the glucosyl moiety. (Hydrophobic groups are selectively attached at 2-, 3-, 4-, etc. positions, thus giving glucose or galactose relative to glucoside or galactoside.) Bonds between glycosides can be located in additional glycoside units between a position on and the 2-, 3-, 4- and/or 6-position on the preceding saccharide unit.

Preferred alkyl polyglycosides have the formula

R ² O(C _n H _2n O) _t (glycosyl) _x wherein R ₂ is selected from alkyl, alkylphenyl, hydroxyalkyl, hydroxyalkylphenyl and mixtures thereof, wherein the alkyl group contains 10-18, Preferably 12-14 carbon atoms; n is 2 or 3; t is 0 to 10, preferably 0, x is 1.3 to 8, preferably 1.3 to 3, most preferably 1.3 to 2.7. The glycosyl is preferably derived from glucose. Fatty Acid Amide Nonionic Surfactant

Fatty acid amide surfactants suitable for use in the present invention are those having the formula ^R6CON ( ^R7 ) ₂ , wherein ^R6 is an alkyl group containing 7 to 21, preferably 9 to 17 carbon atoms, and ^R7 is each 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 to 3. amphoteric surfactant

Amphoteric surfactants suitable for use herein include amine oxide surfactants and alkyl amphocarboxylic acids.

An example of an alkylaphodicarboxylic acid suitable for use in the present invention is Miranol(TM) C2M Conc. amine oxide surfactant produced by Miranol, Inc., Dayton, NJ

Amine oxides useful in the present invention are those compounds having the formula R ³ (OR ⁴ ) _x NO(R ⁵ ) ₂ , wherein R ³ is selected from the group consisting of alkyl groups containing 8 to 26 carbon atoms, preferably 8 to 18 carbon atoms, Hydroxyalkyl, acylamidopropyl and alkylphenyl or mixtures thereof; ^R4 is alkylene or hydroxyalkylene or mixtures thereof containing 2 to 3 carbon atoms, preferably 2 carbon atoms; x is 0 to 5, preferably 0 to 3; R ⁵ are alkyl or hydroxyalkyl groups containing 1 to 3, preferably 1 to 2 carbon atoms, or polycyclic rings containing 1 to 3, preferably 1 oxirane group Oxygen group. The ^R5 groups may be attached to each other, for example via an oxygen or nitrogen atom, to form a ring structure.

Amine oxide surfactants include C ₁₀ -C ₁₈ alkyldimethylamine oxides and C ₈ -C ₁₈ alkoxyethyldihydroxyethylamine oxides, among others. Examples of such materials include dimethyloctylamine oxide, diethyldecylamine oxide, bis(2-hydroxyethyl)dodecylamine oxide, dimethyldodecylamine oxide, di Propyltetradecylamine oxide, methylethylhexadecylamine oxide, laurylamidopropyldimethylamine oxide, cetyldimethylamine oxide, stearyl Dimethylamine oxide, tallow dimethylamine oxide, and dimethyl-2-hydroxystearylamine oxide. Preferred are C ₁₀ -C ₁₈ alkyldimethylamine oxides and C ₁₀ -C ₁₈ acylamidoalkyldimethylamine oxides. zwitterionic surfactant

Zwitterionic surfactants can also be incorporated into the detergent compositions herein. 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. Betaines and sultaines are typical zwitterionic surfactants useful herein. Betaine Surfactant

Betaines useful in the present invention are those compounds having the formula R(R ¹ ) ₂ N ⁺ R ^{2 COO-} , wherein R is C ₆ -C ₁₈ hydrocarbyl, preferably C ₁₀ -C ₁₆ alkyl or C ₁₀ -C ₁₆ acylamidoalkyl, each R ¹ is generally C ₁ -C ₃ alkyl, preferably methyl, R ² is C ₁ -C ₅ hydrocarbon group, preferably C ₁ -C ₃ alkylene, more preferably C ₁ - C ₂ alkylene. Examples of suitable betaines include cocoyl amidopropyl dimethyl betaine; cetyl dimethyl betaine; C _12-14 acyl amidopropyl betaine; C _8-14 acyl amidohexyl diethyl 4[C _14-16 acyl amido diethylammonium (ammonio)]-1-carboxybutane; C _16-18 acyl amido dimethyl betaine; C _12-16 acyl amido Pentane diethyl betaine; [C _12-16 acylmethylamidodimethyl betaine. Preferred betaines are C _12-18 dimethylammonium (ammonio) hexanoate and C _10-18 acylamidopropane (or ethane) dimethyl (or diethyl) betaine. Complex betaine surfactants are also suitable for use in the present invention. Sultaine Surfactant

Sultaines useful in the present invention are those compounds having the formula R(R ¹ ) ₂ N ⁺ R ² SO ₃ ^- , wherein R is C ₆ -C ₁₈ hydrocarbyl, preferably C ₁₀ -C ₁₆ alkyl, more preferably C ₁₂ -C ₁₃ alkyl, each R ¹ is generally C ₁ -C ₃ alkyl, preferably methyl, R ² is C ₁ -C ₆ hydrocarbon, preferably C ₁ -C ₃ alkylene, preferably hydroxyalkylene . amphoteric surfactant

Amphoteric surfactants may be incorporated into the compositions of the present invention. These surfactants can be broadly described as aliphatic derivatives of secondary or tertiary amines or aliphatic derivatives of heterocyclic secondary and tertiary amines, where the aliphatic group may be straight or branched. cationic surfactant

Cationic surfactants may also be used in the detergent compositions herein. Suitable cationic surfactants include quaternary ammonium surfactants selected from mono C ₆ -C ₁₆ , preferably C ₆ -C ₁₀ N-alkyl or chain Alkenylammonium surfactants in which the remaining N positions are substituted with methyl, hydroxyethyl or hydroxypropyl groups. Partially soluble or insoluble builder compounds

The detergent compositions of the present invention may contain partially soluble or insoluble builder compounds, generally at a level of from 1% to 80% by weight of the composition, preferably from 10% to 70% by weight, most preferably from 20% to 60% by weight (Heavy).

Examples of some hydrobuilders include crystalline layered silicates. Examples of substantially water insoluble builders include sodium aluminosilicates.

Crystalline layered sodium silicate has the general formula:

NaMSi _x O _2x+1 .yH ₂ O wherein M is sodium or hydrogen, x is a number from 1.9 to 4, and y is a number from 0 to 20. Such crystalline layered sodium silicates are disclosed in EP-A-0164514 and processes for their preparation are disclosed in DE-A-3417649 and DE-A-3742043. For the purpose of the present invention. x in the above general formula is 2, 3 or 4, preferably 2. The most preferred species of this _type is delta- _Na2Si2O5 , commercially available from Hoechst as NaSK S-6 _.

The crystalline layered sodium silicate material is preferably present in granular detergent compositions as particles intimately mixed with solid water-soluble ionizable material. The solid water-soluble ionizable material is selected from organic acids, organic and inorganic acid salts and mixtures thereof.

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

Aluminosilicate ion exchange materials 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 MAP, 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 to 30, especially 27. Zeolite X has the formula Na ₈₆ [(AlO ₂ ) ₈₆ (SiO ₂ ) ₁₀₆ ]·276H ₂ O. enzyme

Another optional ingredient useful in detergent compositions is one or more additional enzymes.

Preferred additional enzyme materials include the commercially available lipases, amylases, neutral and alkaline proteases, esterases, cellulases, pectinases and peroxidases which are commonly incorporated into detergents composition. Suitable enzymes are disclosed in U.S. 3,519,570 and 3,533,139.

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

Preferred amylases include, for example, alpha-amylases obtained from a special strain of Bacillus licheniformis, described in more detail in GB-1,269,839 (Novo). Preferred commercially available amylases include, for example, those sold under the trademark Rapidase by Gist-Brocades, and those sold under the trademark Termamyl and BAN by Novo Industries A/S. Amylases may be incorporated into compositions according to the invention in amounts ranging from 0.0001% to 2% active enzyme by weight of the composition.

The lipolytic enzyme (lipase) is present in an amount of 0.0001% to 2% by weight of the composition, preferably 0.001% to 1% by weight, most preferably 0.001% to 0.5% by weight of active lipolytic enzyme.

Lipases may be of fungal or bacterial origin, for example lipases produced by Humicola species, Theophyllum species or Pseudomonas species, including strains of Pseudomonas pseudoalcaligenes or Pseudomonas fluorescens. Lipases derived from chemically or genetically modified variants of these strains are also useful in the present invention.

A preferred lipase is obtained from Pseudomonas genus Pseudoalcaligenes, which is described in granted European patent EP-B-0218272.

Other preferred lipases herein are obtained by cloning a gene from Humicola lanuginosa and expressing it using Aspergillus oryzae as a host, as described in European patent application EP-A-0258068, commercially available from Novo Industri A/S , Bagsvaerd, (Denmark) under the trademark Lipolase. This lipase is also described in U.S. 4,810,414, Huge-Jensen et al., issued March 7,1989. enzyme stabilization system

Preferred enzyme-containing compositions of the present invention may comprise from about 0.001% to 10%, preferably from about 0.005% to 8%, most preferably from about 0.01% to 6% by weight of an enzyme stabilizing system. The enzyme stabilization system can be any stabilization system compatible with the detergent enzyme. Such stabilizing systems may include calcium ions, boric acid, propylene glycol, short chain carboxylic acids, boric acid, and mixtures thereof. Such stabilizing systems may also include reversible enzyme inhibitors, such as reversible protease inhibitors.

The compositions of the present invention may also include from 0 to about 10%, preferably from about 0.01% to about 6% by weight, of a chlorine bleach scavenger added to inhibit the destruction of enzymes and Inactivates enzymes, especially under alkaline conditions. Chlorine levels in water may be small, typically in the range of about 0.5 ppm to about 1.75 ppm, but the chlorine available in the total volume of water in contact with the enzyme during washing is usually substantial, so enzyme stability in use is a problem.

Suitable chlorine scavenger anions come from a wide variety of sources, such as salts containing ammonium cations, sulfites, bisulfites, thiosulfites, thiosulfates, iodides, and the like. Antioxidants such as carbamates, ascorbic acid, etc., organic amines such as ethylenediaminetetraacetic acid (EDTA) or its alkali metal salts, monoethanolamine (MEA) and mixtures thereof may also be used. Other conventional scavengers such as bisulfate can be used if desired. Nitrates, chlorides, sources of hydrogen peroxide such as sodium perborate tetrahydrate, sodium perborate monohydrate and sodium percarbonate, as well as phosphates, condensed phosphates, acetates, benzoates, citrates , formate, lactate, malate, tartrate, salicylate, etc. and mixtures thereof. organic polymer compound

Organic polymeric compounds are particularly preferred ingredients of the detergent compositions of the present invention. By organic polymeric compound is meant any polymeric organic compound typically used as a powder, and anti-redeposition and soil-suspending agent essential in detergent compositions.

Typically, the detergent compositions of the present invention will incorporate organic polymeric compounds at a level of from 0.1% to 30%, preferably from 0.5% to 15%, most preferably from 1% to 10%, by weight of the composition.

Examples of organic polymeric compounds include water-soluble organic homo- or co-polymeric carboxylic acids or their salts, wherein the polycarboxylic acid comprises at least two carboxyl groups separated from each other by not more than two carbon atoms. Polymers of the latter type are disclosed in GB-A-1,596,756. Examples of such salts are polyacrylates having a molecular weight of 2000-5000 and their copolymers with maleic anhydride, such copolymers having a molecular weight of 20,000 to 100,000, especially 40,000 to 80,000.

Other suitable organic polymeric compounds include polymers of acrylamide and acrylate having a molecular weight of 3,000 to 100,000, and acrylate/fumarate copolymers having a molecular weight of 2,000 to 80,000.

Polyamino compounds useful in the present invention include those derived from aspartic acid, such as those disclosed in EP-A-305282, EP-A-305283 and EP-A-351629.

Also suitable according to the invention are terpolymers containing monomer units selected from the group consisting of maleic acid, acrylic acid, polyaspartic acid and vinyl alcohol, especially those having an average molecular weight of 5,000 to 10,000.

Other organic polymeric compounds suitable for incorporation in the detergent compositions of the present invention include cellulose derivatives such as methylcellulose, carboxymethylcellulose and hydroxyethylcellulose.

Further useful organic polymeric compounds are polyethylene glycols, especially those having a molecular weight of 1,000-10,000, more preferably 2,000 to 8,000, most preferably about 4,000. Calcium Soap Dispersant Compound

The compositions of the present invention may contain a lime soap dispersant compound having a lime soap dispersant power (LSDP) of no greater than 8, preferably no greater than 7, most preferably no greater than 6, as defined below. Lime soap dispersant compounds are preferably present at levels of 0.1% to 40% by weight of the composition, more preferably 1% to 20% by weight, most preferably 2% to 10% by weight.

Calcium soap dispersants are a class of substances that use calcium or magnesium ions to inhibit the precipitation of alkali metal, ammonium or amine salts of fatty acids. A numerical measure of the effectiveness of a lime soap dispersant is given by the lime soap dispersant power (LSDP) using the article Oil.Chem.Soc.27 by HC Borghetty and CABergman.J.Am. , determined by the calcium soap dispersion test described on pages 88-90 (1950). The calcium soap dispersion test method is widely used by those skilled in the art, this is referred to for example in the following review articles: WN Linfield, Surfactant Science Series, Vol. 7, p3; WN Linfield, Tenside Surf. Det., Vol. 27, p159-161 (1990); and MK Nagarajan, WF Masler, Cosmetics and Toiletries, Vol. 104, p71-73, (1989). LSDP is the ratio of the weight of the calcium soap deposit formed by 0.025g sodium oleate in 30ml 333ppm CaCO ₃ (Ca:Mg=3:2) equivalent hardness water to the weight of sodium oleate.

Surfactants with good lime soap dispersant capabilities include certain amine oxides, betaines, sultaines, alkyl ethoxy sulfates and ethoxylated alcohols.

Examples of surfactants having an LSDP of not more than 8 for use in the present invention include C ₁₆ -C ₁₈ dimethylamine oxide, C ₁₂ -C ₁₈ alkyl ethoxy groups having an average degree of ethoxylation of 1-5 Sulfates, especially C ₁₂ -C ₁₅ alkyl ethoxysulfate surfactants with a degree of ethoxylation of about 3 (LSDP=4), and with an average degree of ethoxylation of 12 (LSDP=6) or 30 C ₁₃ -C ₁₅ ethoxylated alcohols sold by BASF GmbH under the trademarks Lutensol A012 and Lutensol A030, respectively.

Polymeric calcium soap dispersants suitable for use in the present invention are described in Cosmetics and Toiletries, Vol. 104, p. 71-73, (1989) by M.K. Nagarajan and W.F. Masler. Examples of such polymeric lime soap dispersants include the water-soluble salts of certain copolymers of acrylic acid, methacrylic acid or mixtures thereof with acrylamide or substituted acrylamide, such polymers generally having a molecular weight of 5,000 to 20,000. Antifoam system

When the detergent composition of the present invention is formulated for use in washing machines, it preferably includes a suds suppressing system in an amount of 0.01% to 15%, preferably 0.05% to 10%, most preferably 0.1% to 5% ( Heavy).

Suds suppressing systems suitable for use herein may comprise essentially any known antifoam compound including, for example, silicone antifoam compounds, 2-alkyl and alcanol antifoam compounds.

By antifoam compound is meant herein any compound or mixture thereof which has the effect of inhibiting foaming or foaming from a solution of the detergent composition, especially under agitation of the solution.

Particularly preferred antifoam compounds for use in the present invention are silicone antifoam compounds as defined herein, such as any antifoam compound comprising a silicone component. Such silicone antifoam compounds generally also contain a silica component. The term "polysiloxane" as used herein is general in the industry and includes a variety of 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 block units.

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

Other suitable antifoam compounds include, for example, high molecular weight fatty acid esters (e.g. triglycerides), fatty acid esters of monohydric alcohols, aliphatic _C18 - _C40 ketones (e.g. stearyl ketone), N-alkylated amino Triazines, such as tri to hexaalkylmelamines or di to tetraalkyl diamine chlorotriazines, which are cyanuric chloride with 2 or 3 moles of primary or secondary amines containing 1 to 24 carbon atoms, propylene oxide The products of bisstearic acid amide and mono-stearyl phosphate dialkali metal (eg sodium, potassium, lithium) salts and monostearyl phosphate.

Copolymers of ethylene oxide and propylene oxide, especially mixed ethoxylates having an alkyl chain length of 10 to 16 carbon atoms, a degree of ethoxylation of 3 to 30, a degree of propoxylation of 1 to 10 Oxylated/propoxylated fatty alcohols are also suitable antifoam compounds for use herein.

2-Alkyl-alcanols antifoam compounds suitable for use in the present invention are described in DE4021265. 2-Alkyl-alcanols suitable for use in the present invention are composed of C ₆ -C ₁₆ alkyl chains with terminal hydroxyl groups substituted at two positions by C ₁ -C ₁₀ alkyl groups. Mixtures of 2-alkyl-alcanols may be used in the compositions of the present invention.

Preferred suds suppressor systems include

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

(i) from 50% to 90%, preferably from 75% to 95%, of polydimethylsiloxane by weight of the silicone antifoam compound; and

(ii) 1%-50%, preferably 5%-25% (weight) of silicon dioxide by weight of the polysiloxane/silica antifoam compound; wherein said silica/polysiloxane antifoam The compound is incorporated in an amount of 5%-50%, preferably 10%-40% (by weight);

(b) A dispersant compound, most preferably comprising a polysiloxane glycol rake copolymer having a polyoxyalkylene content of 72-78% and a ratio of ethylene oxide to propylene oxide of 1:0.9 To 1:1.1, the content of the dispersant compound is 0.5%-10%, preferably 1%-10% (weight), a particularly preferred polysiloxane rake copolymer of this type is DCO544, commercially available from DOW Corning Yes, the trademark is DCO544;

(c) 5%-80%, preferably 10%-70% by weight of an inert carrier fluid compound, most preferably comprising _C16 - _C18 ethoxy groups having a degree of ethoxylation of 5-50, preferably 8-15 Alcohol;

A preferred particulate suds suppressor system useful herein comprises a mixture of an alkylated polysiloxane of the type disclosed herein above and solid silica.

The solid silica may be fumed silica, precipitated silica, or silica prepared by gel-forming techniques. Suitable silica particles have an average particle size of 0.1 to 50 microns, preferably 1 to 20 microns, and a surface area of at least 50 m ² /g, which are obtained by using dialkylsilyl and/or trialkylmethyl Treatments in which silane groups are directly bonded to silica or with polysiloxane resins are made hydrophobic. Preference is given to using hydrophobic silica particles bearing dimethyl and/or trimethylsilyl groups. Preferred antifoam compound granules for inclusion in the detergent compositions of the present invention suitably contain silica in an amount such that the weight ratio of silica to polysiloxane is from 1:100 to 3:10, preferably 1:50 to 1:7.

Representative of other suitable particulate suds suppressing systems are hydrophobic silylated (most preferably trimethylsilylated) silicas having a particle size of 10 nm to 20 nm and a specific surface area above 50 ^m2 /g , is an intimate mixture with a dimethyl polysiloxane fluid having a molecular weight of from about 500 to about 200,000, wherein the weight ratio of polysiloxane to silanized silica is from about 1:1 to about 1:2.

The most preferred granular suds suppressing system is described in EP-A-0210731, comprising a polysiloxane antifoam compound and an organic carrier material having a melting point of 50°C to 85°C, wherein the organic carrier material comprises a monoglyceride and has a compound containing 12 Fatty acids with chains of up to 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, or a mixture thereof, with a carbon chain containing 12 to 20 carbon atoms, which has a melting point of 45°C to 80°C.

Other most preferred particulate suds suppressing systems are described in pending European patent application 91870007.1 of the company Procter and Gamble Company, which system comprises a polysiloxane antifoam compound, a carrier substance, an organic coating material and glycerin, wherein the glycerin is combined with The weight ratio of the silicone antifoam compound is from 1:2 to 3:1. Pending European application 91201342.0 also discloses the most preferred particulate suds suppressor system comprising polysiloxane antifoam compounds, carrier substances, organic coating materials and crystalline or amorphous aluminosilicates, wherein the aluminosilicates are combined with poly The silicone antifoam compound is present in a weight ratio of 1:3 to 3:1. The preferred carrier substance in the two most preferred granular foam control agents described above is starch.

An example of a particulate suds suppressing system useful in the present invention is a particulate agglomerate component prepared by an agglomeration process comprising the following combinations of (i), (ii), (iii) and (iv):

(i) 5%-30%, preferably 8%-15% (by weight) of a silicone antifoam compound component, preferably in admixture with polydimethylsiloxane and silicon dioxide;

(ii) 50%-90%, preferably 60%-80% (by weight) of the carrier component, preferably starch;

(iii) 5%-30%, preferably 10%-20% (weight) agglomerate binder compound component, this compound of the present invention can be any compound generally used as agglomerate binder or its a mixture, most preferably said agglomerate binder compound comprising a _C16 - _C18 ethoxylated alcohol having a degree of ethoxylation of 50 to 100; and

(iv) 2%-15%, preferably 3%-10% by weight of _C12 - _C22 hydrogenated fatty acids. dye transfer polymerization inhibitor

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

The dye transfer polymerization inhibitor is preferably selected from polyamine-N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, polyvinylpyrrolidone polymers or mixtures thereof. a) Polyamine N-oxide polymers

其中P是可聚合单元，R-N-O基团可与其连接，或者其中R-N-O基团是该可聚合单元的一部分，或这两者的组合。A是

-O-，-S-，-N-；x是0或1；R是脂族基、乙氧基化脂族基、芳族基、杂环或脂环基或其任何组合，N-O基团中的氮可以连结在R上或其中N-O基团中的氮是这些基团的一部分。Polyamine N-oxide polymers suitable for use in the present invention contain units having the formula:

Where P is a polymerizable unit to which the RNO group may be attached, or where the RNO group is part of the polymerizable unit, or a combination of both. A is

-O-, -S-, -N-; x is 0 or 1; R is aliphatic, ethoxylated aliphatic, aromatic, heterocyclic or alicyclic or any combination thereof, NO group The nitrogen in may be attached to R or where the nitrogen in the NO group is part of these groups.

The NO group can be represented by the following general structural formula: Wherein R ₁ , R ₂ and R ₃ are aliphatic groups, aromatic groups, heterocyclic or alicyclic groups, or a mixture thereof, x or/and y or/and z are 0 or 1, wherein the nitrogen in the NO group The nitrogen in the NO groups which may be attached thereto or therein forms part of these groups. The NO group can be part of the polymerizable unit (P) or attached to the polymeric backbone, or a combination of both.

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

Another class of the polyamine N-oxides includes a group of polyamine N-oxides in which the nitrogen of the N-O group is bonded to the R group.

Other suitable polyamine N-oxides are polyamine oxides, the N-O groups being attached to the polymerizable units thereof.

A preferred class of these polyamine N-oxides are polyamine N-oxides having the general formula (I), wherein R is an aromatic, heterocyclic or alicyclic group, wherein the nitrogen in the N-O functional group is the R part of the group. Examples of these types are polyamine oxides where R is a heterocyclic compound such as pyridine, pyrrole, imidazole and derivatives thereof.

Other preferred types of polyamine N-oxides are polyamine oxides of general formula (I), wherein R is an aromatic, heterocyclic or alicyclic group, wherein the nitrogen in the N-O functional group is attached to said On the R group. Examples of these types are polyamine oxides where the R group may be an aromatic group such as phenyl.

Any polymer backbone can be used so long as the amine oxide polymer formed is water soluble and has dye transfer inhibiting properties. Examples of suitable polymeric backbones are polyethylenes, polyalkylenes, polyesters, polyethers, polyamides, polyimides, polyacrylates and mixtures thereof.

The amine-N-oxide polymers of the present invention generally have a ratio of amine to amine N-oxide of from 10:1 to 1:1,000,000. However, the amount of amine oxide groups in the polyamine oxide polymer may vary according to suitable copolymerization or suitable degree of N-oxidation. Preferably the ratio of amine to amine N-oxide is from 2:3 to 1:1,000,000, more preferably from 1:4 to 1:1000000, most preferably from 1:7 to 1:1000000. The polymers of the present invention actually include random or block copolymers in which one monomer type is an amine N-oxide and the other monomer type is an amine N-oxide or not. The amine oxide units of the polyamine N-oxides have a pKa<10, preferably pKa<7, more preferably pKa<6.

Polyamine oxides can be obtained in virtually any degree of polymerization. The degree of polymerisation is not critical so long as the material has the requisite water solubility and dye-suspending capabilities. Generally, its average molecular weight is from 500 to 1,000,000, preferably from 1,000 to 50,000, more preferably from 2,000 to 30,000, most preferably from 3,000 to 20,000. b) Copolymers of N-vinylpyrrolidone and N-vinylimidazole

Preferred polymers for use in the present invention include polymers selected from N-vinylimidazole N-vinylpyrrolidone copolymers, wherein the polymer has an average molecular weight of 5,000 to 50,000, more preferably 8,000 to 30,000, most preferably 10,000 Preferred N-vinylimidazole N-vinylpyrrolidone copolymers have a molar ratio of N-vinylimidazole to N-vinylpyrrolidone of 1 to 0.2, more preferably 0.8 to 0.3, most preferably 0.6 to 0.4. c) Polyvinylpyrrolidone

The detergent compositions of the present invention may also employ polyvinylpyrrolidone ("PVP") having an average molecular weight of 2,500 to 400,000, preferably 5,000 to 200,000, more preferably 5,000 to 50,000, most preferably 5,000 to 15,000. Suitable polyvinylpyrrolidones are commercially available from ISP Corporation, New York, NY and Montreal, Canada under the product designations PVP K-15 (viscosity molecular weight 10,000), PVP K-30 (average molecular weight 40,000), PVP K-60 (average molecular weight 160,000), PVP K-90 (average molecular weight 360,000). PVP K-15 is also commercially available from ISP Corporation. Other suitable polyvinylpyrrolidones commercially available from BASF Cooperation include Sokalan HP 165 and Sokalan HP 12.

The amount of polyvinylpyrrolidone that can be incorporated in the detergent composition of the present invention is 0.01%-5% (weight), preferably 0.05%-3% (weight), more preferably 0.1% to 2% (weight) of the detergent composition Heavy). The amount of polyvinylpyrrolidone released in the wash solution is preferably from 0.5 ppm to 250 ppm, preferably from 2.5 ppm to 150 ppm, more preferably from 5 ppm to 100 ppm. d) Polyvinyloxazolidinone

The detergent compositions herein may also employ polyvinyloxazolidinones as dye transfer polymerization inhibitors. The polyvinyloxazolidinone has an average molecular weight of 2,500 to 400,000, preferably 5,000 to 200,000, more preferably 5,000 to 50,000, most preferably 5,000 to 15,000.

The amount of polyvinyloxazolidinone incorporated in the detergent composition may be from 0.01% to 5% by weight, preferably from 0.05% to 3% by weight, more preferably from 0.1% to 2% by weight. The amount of polyvinyloxazolidinone released in the wash solution is generally 0.5 ppm to 250 ppm, preferably 2.5 ppm to 150 ppm, more preferably 5 ppm to 100 ppm. e) Polyvinyl imidazole

The detergent compositions herein may also employ polyvinylimidazole as a dye transfer polymerization inhibitor. The polyvinylimidazole preferably has an average molecular weight of 2,500 to 400,000, more preferably 5,000 to 50,000, most preferably 5,000 to 15,000.

The amount of polyvinylimidazole incorporated in the detergent composition may be 0.01%-5% by weight, preferably 0.05%-3% by weight, more preferably 0.1%-2% by weight. The amount of polyvinylimidazole released in the washing solution is 0.5 ppm to 250 ppm, preferably 2.5 ppm to 150 ppm, more preferably 5 ppm to 100 ppm. Fluorescent whitening agent

The detergent compositions herein may also optionally contain from about 0.005% to 5% by weight of certain types of hydrophilic optical brighteners which also provide dye transfer inhibition. If used, the compositions of the present invention will preferably include from about 0.01% to about 1% by weight of such optical brighteners.

其中R₁选自苯胺基、N-2-双羟乙基和NH-2-羟乙基；  R₂选自N-2-双羟乙基、N-2-羟乙基-N-甲氨基、吗啉代(morphilino)、氯和氨基；M是成盐阳离子如钠或钾。Hydrophilic optical brighteners useful in the present invention are those having the following structural formula:

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

When in the above formula, R ₁ is anilino, R ₂ is N-2-bishydroxyethyl, and M is a cation such as sodium, the whitening agent is 4.4'-bis[(4-anilino-6-( N-2-bishydroxyethyl)-S-triazin-2-yl)amino]-2,2'-stilbene disulfonic acid and its disodium salt. This particular brightener is sold commercially by Ciba-Geigy Corporation under the trademark Tinopal-UNPA-GX. Tinopal-UNPA-GX is the preferred hydrophilic optical brightener useful in the detergent compositions of the present invention.

When in the above formula, 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 sold commercially by Ciba-Geigy Corporation under the trademark Tinopal 5BM-GX.

When in the above formula, R ₁ is anilino, R ₂ is morpholino (morphilino), and M is a cation such as sodium, the whitening agent is 4.4'-bis[(4-anilino-6-morpholino -S-triazin-2-yl)amino]2.2'-stilbene disulfonic acid sodium salt. This particular brightener is sold commercially by Ciba Geigy Corporation under the trademark Tinopal AMS-GX.

These particular optical brighteners selected for use in the present invention provide particularly effective dye transfer inhibiting performance benefits when used in combination with the selected polymeric dye transfer inhibiting agents described above. Combinations of the selected polymeric substances (such as PVNO and/or PVPVI) with the selected optical brighteners (such as Tinopal UNPA-GX, Tinopal 5BM-GX and/or Tinopal AMS-GX) are more effective than those used alone Either of these detergent composition components provides remarkably good dye transfer inhibition in the aqueous wash solution. Without being bound by theory, it is believed that the mode of action of such brighteners is that due to their high affinity for fabrics in the wash solution, they deposit relatively quickly on these fabrics. The extent to which brighteners deposit on fabrics in the wash solution is defined by a parameter known as the "waste factor". The depletion factor generally refers to the ratio of the brightener species a) deposited on the fabric to the initial brightener concentration b) in the wash water solution. Brighteners with relatively high consumption factors are most suitable for use in inhibiting dye transfer in this technical context of the present invention.

Of course, it will also be appreciated that these compounds and other types of conventional optical brighteners may optionally be used in the compositions of the present invention to provide conventional fabric "brightness" benefits without actually having a dye transfer inhibiting effect. Such use is conventional and well known for detergent formulation. softener

Fabric softeners can also be incorporated into the laundry detergent compositions of the present invention. These reagents can be of inorganic or organic type. Illustrative examples of inorganic softeners are the smectite clays disclosed in GB-A-1400898. Organic fabric softeners include the water insoluble tertiary amines disclosed in GB-A-1514276 and EP-B-0011340.

Smectite clay is generally present at levels of 5% to 15%, more preferably 8% to 12% by weight, which are added to the remainder of the formulation along with materials added as dry blend components. Organic fabric softeners such as water-insoluble tertiary amines or double long-chain amide materials are incorporated in an amount of 0.5%-5% (weight), generally 1%-3% (weight), and high molecular weight polyethylene oxide materials The addition amount of water-soluble cationic substances is 0.1%-2%, generally 0.15%-1.5% (weight). other optional components

Other optional ingredients suitable for inclusion in the compositions of the present invention include perfumes, pigments and filler salts, with sodium sulfate being the preferred filler salt. composition form

The detergent compositions of the present invention can be formulated in any desired form such as powders, granules, pastes, liquids, tablets and gels. liquid composition

The detergent compositions of the present invention may be formulated as liquid detergent compositions. This liquid detergent composition generally comprises 94% to 35% (weight), preferably 90% to 40% (weight), most preferably 80% to 50% (weight) liquid carrier, such as water, preferably water and organic solvent mixture. gel composition

The detergent compositions of the present invention may also be in the form of a gel. Such compositions are generally formulated with polyalkenyl polyethers having a molecular weight of from about 750,000 to about 4,000,000. solid composition

The detergent compositions of the present invention are preferably in solid form, such as powders and granules.

The particle size of the components of the granular composition of the invention should preferably be such that no more than 5% of the particles have a diameter greater than 1.4 mm and no more than 5% have a diameter of less than 0.15 mm.

Granular detergent compositions according to the invention will generally have a bulk density of at least 450 g/l, more usually at least 600 g/l, more preferably from 650 g/l to 1200 g/l.

Bulk density is determined using a simple funnel and cup apparatus consisting of a conical funnel molded securely on a base and a flap valve mounted at the lower end of the funnel to allow the funnel to The contents of the funnel flow into an axially aligned cylindrical cup placed under the funnel. The heights at the respective upper and lower ends of the funnel are 130mm and 40mm. Mount it on a base so that its lower end is 140 mm above the upper surface of the base. The cup has an overall height of 90mm, an inner height of 87mm and an inner diameter of 84mm. The nominal volume of the cup is 500ml.

For the determination, the powder is filled by hand into the funnel and the flap valve is opened to fill the cup with powder. The filler cup is removed from the base and excess powder is removed from the cup with a vertical edged implement, such as a knife, through the upper rim of the cup. The filler cup is then weighed and doubling the value to obtain the powder weight provides the bulk density in g/l. Repeat measurements were performed as needed. Preparation Process - Granular Composition

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. cleaning method

The compositions of the present invention may be used in essentially any washing or cleaning method, including washing machine and dishwashing methods. How to use a dishwasher

A preferred machine dishwashing method comprises treating a soiled item selected from the group consisting of china, glassware, sinkware and cutlery with an aqueous solution having dissolved or dispersed in the aqueous solution an effective amount of a machine dishwashing composition of the present invention , and mixtures thereof. An effective amount of a machine dishwashing composition generally means that 8 g to 60 g of product are dissolved or dispersed in a wash solution in a volume of 3 to 10 liters, which is the typical product dosage and wash solution normally used in conventional machine dishwashing methods volume. How to use a washing machine

The washing machine method herein comprises treating soiled laundry in a washing machine with an aqueous solution having dissolved or dispersed in the aqueous solution an effective amount of the washing machine detergent composition of the present invention. Detergent is added to the wash solution through the dispersion chamber of the washing machine or through a dispenser. An effective amount of a detergent composition generally means dissolving or dispersing 40 g to 300 g of product in a wash solution volume of 5 to 65 liters, which is typical product dosage and wash solution volume used in conventional washing machine methods.

In a preferred washing method of the present invention, a dispenser containing an effective amount of detergent product is placed in the tub of a preferably front loading washing machine prior to the start of the wash cycle.

A dispenser is a container of detergent product that is used to release product directly into the tub of a washing machine. Its volumetric capacity should be able to hold enough detergent product normally used in the washing process.

When the washing machine is loaded with laundry, the dispenser with the detergent product is placed into the tub. At the beginning of a washing machine wash cycle, water is poured into the tub and the tub rotates periodically. The design of the disperser should be such that it retains the dry detergent product but allows the product to be released during the wash cycle with agitation such as the rotation of the tub as a result of its immersion in the wash water.

In order to release the detergent product during washing, the dispenser may have a plurality of openings through which the product may pass. Alternatively, the dispenser may be made of a material that is permeable to liquids but impermeable to solid product, which allows release of the dissolved product. Preferably, the detergent product is released quickly at the start of the wash cycle, thereby providing a momentary localized high concentration of components such as hydrobuilder and heavy metal ion sequestrant components in the drum of the washing machine during this phase of the wash cycle.

Preferred dispensers are reusable and are designed to maintain the integrity of the container in the dry state and during wash cycles. Particularly preferred dispersers for use in the present invention are described in the following patents: GB-B-2,157,719, GB-B-2,157,718, EP-A-0201376, EP-A-0288345 and EP-A-0288346. An article by J. Bland in Manufacturing Chemist, November 1989, pages 41-46 also describes a particularly preferred disperser for use in granular detergent products, which are generally known granular types of products.

Particularly preferred dispersers are disclosed in European Patent Applications 0343069 & 0343070. The latter application discloses a dispenser comprising a flexible sleeve protruding from a support ring having a bag-like structure with defined apertures which allow the bag to contain A sufficient amount of product to circulate. Part of the wash medium flows into the bag through the pores, dissolves the product, and then the solution flows outward through the pores into the wash medium. The support ring is provided with a shield device to prevent the outflow of wet undissolved product, which device generally includes a radially extending wall projecting from a central boss of a spoke structure or similar structure, wherein the wall has a spiral shape structure. Pretreatment Washing Method

In the pretreatment wash method of the present invention, a soiled/stained substrate is treated with an effective amount of a pretreatment solution comprising a heavy metal ion chelating agent, but free of bleach components. The solution may optionally contain other non-bleach detergent ingredients such as surfactants, builders, enzymes and detergent polymers. Preferably the solution also contains a water-soluble builder.

The content of the heavy metal ion chelating agent in the pretreatment solution is generally 0.0005%-1%, preferably greater than 0.05%.

Keep the pretreatment solution in contact with the soil substrate for an effective interval of time. The time interval is generally 10 seconds to 1800 seconds, more preferably 60 seconds to 600 seconds.

The soiled substrate is then washed by a suitable washing method using a detergent composition containing bleach. The washing method may be, for example, any method described herein with a washing machine or with a dishwasher.

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

XYAS: Sodium C _1X -C _1Y Alkyl Sulfate

24EY: C ₁₂ -C ₁₄ condensed with an average of Y moles of ethylene oxide

Predominantly straight-chain primary alcohols

XYEZ: C _1X -C _1Y condensed with an average of Z moles of ethylene oxide

Predominantly straight-chain primary alcohols

XYEZS: C _1X with an average of Z moles of ethylene oxide condensed per mole

Sodium C _1Y Alkyl Sulfate

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

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

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

Carbonate : Anhydrous sodium carbonate Polycarboxylate : 1:4 maleic acid/acrylic acid copolymer, the average molecular weight is

                        About 80,000  Zeolite A     : Hydrated sodium aluminosilicate having the formula:

Na ₁₂ (AlO ₂ SiO ₂ ) ₁₂ ·27H ₂ O, the main particle size is

1 to 10 microns Citrate: Trisodium citrate dihydrate Percarbonate: Empirical formula (quick release particles) coated with a mixed salt of the formula Na ₂ SO ₄ n Na ₂ CO ₃ is 2Na ₂ CO ₃ 3H ₂ O anhydrous sodium percarbonate bleach, which

In n is 0.29, the weight ratio of percarbonate and mixed salt is

39:1Percarbonate: Anhydrous sodium percarbonate bleach coated with sodium silicate ( _Si2O :Na2O ratio of ₂ :1) coating (slow release particles), percarbonate and

Sodium silicate in a weight ratio of 39:1 TAED : Tetraacetylethylenediamine TAED : granules formed by agglomerating TAED with citric acid and polyethylene glycol (slow release granules) of molecular weight 4000 (PEG), TAED :

The weight ratio of citric acid:PEG is 75:10:15,

                                                                               , 

The weight ratio of the cladding layer is 95:5. Benzoyl Caprolactam: granules formed with citric acid and polyethylene glycol (PEG) with a molecular weight of 4000 (slow release granules) adhering polybenzoyl caprolactam (BzCl),

The weight ratio of BzCl: citric acid: PEG is 63:21:

                                                        ,

The weight ratio of the citric acid coating is 95:5 TAED : Partially neutralized polycarboxylate agglomerates TAED to form granules (quick release granules), the ratio of TAED to polycarboxylate is 93:7, Should

There is a polycarboxylate coating on the outside of the particle, and the agglomerate and the coating

96:4 weight ratio EDDS: granules formed by spray drying EDDS and MgSO ₄ , (quick release granules) EDDS to MgSO ₄ weight ratio 26:74 Protease: sold by Novo Industries A/S under the trademark

Protease from Savinase with an activity of 13 KNPU/gAmylase : sold by Novo Industries A/S under the trademark

Amylase from Termamyl 60T with an activity of 300KNU/gCellulase: sold by Novo Industries A/S with an activity of 1000

Cellulase Lipase at CEVU/g: sold by Novo Industries A/S under the trademark

Lipolase lipolytic enzyme with an activity of 165 KLU/gCMC : sodium carboxymethylcellulose HEDP : 1,1-hydroxyethanediphosphonic acid EDDS : ethylenediamine-N,N′-disuccinic acid in sodium salt form S, S]

Issia PVNO: Includes ethylene cepidazole (imidaxol) and ethylenecorropidone

Poly(4-vinylpyridine)-N-oxide copolymerization

Granular Suds with an average molecular weight of 10,000: 12% polysiloxane/silicon dioxide, 18% stearyl alcohol, Suppressor 70% starch, which is granular Nonionic: with an average degree of ethoxylation of 3.8 and an average Degree of Oxylation

4.5 C ₁₃ -C ₁₅ mixed ethoxylated/propoxylated esters

Fatty alcohol sold under the trademark Plurafac by BASF GmbH

LF404 (low foaming). Metasilicate: Sodium metasilicate (SiO ₂ : Na ₂ O ratio is 1.0) Phosphate: Sodium tripolyphosphate 480N: 3:7 random copolymer of acrylic acid/methacrylic acid, average

The molecular weight is about 3,500. PBI                                                                                      

Sodium borate monohydrate Catationic lactam : trialkylammonium methylene C ₅ -alkyl with tosylate

A cationic peroxyacid bleach precursor of caprolactam, DETPMP: Diethylenetriaminepenta(methylenephosphonic acid), by Monsanto

Sold under the trademark Dequest 2060 Bismuth nitrate : bismuth nitrate

Paraffin: Paraffin oil, sold by Wintershall under the trade name Winog 70

BSA: Amylase (decomposing) enzyme sold by Novo Industries A/S

Trademarked as LE17 (approximately 1% enzyme activity)

Sulphate : Anhydrous Sodium Sulfate

pH: Measured in 1% distilled water at 20°C.

Example 1

The following laundry detergent compositions were prepared, with values expressed as percentages by weight of the compositions: Composition A is a comparative composition and compositions B to E are compositions of the present invention: A B C D. E. 45AS/25AS (3:1) 9.1 9.1 9.1 9.1 7.0 35AE3S 2.3 2.3 2.3 2.3 2.0 24E5 4.5 4.5 4.5 4.5 6.0 TFAA 2.0 2.0 2.0 2.0 - Zeolite A 13.2 13.2 13.2 13.2 15.0 Na SKS-6/citric acid (79:21) 15.6 15.6 15.6 15.6 13.0 Carbonate 7.6 7.6 7.6 7.6 8.0 TAED (rapid release granules) 6.3 - - - - TAED (slow release granules) - 5.0 - 2.3 3.5 Benzoyl Caprolactam (slow-release granules) - - 5.0 2.7 - Percarbonate (quick release granules) 22.5 - - 22.5 - Percarbonate (slow release granules) - 22.5 22.5 - - PBL - - - - 16.0 DETPMP 0.5 - - - 0.3 EDDS (fast release granules) - 0.8 0.3 0.75 - Protease 0.55 1.27 0.55 1.27 1.5 Lipase 0.15 0.15 0.15 0.15 0.2 Cellulase 0.28 0.28 0.28 0.28 0.4 Amylase 0.27 0.27 0.27 0.27 0.4 Polycarboxylate 5.1 5.1 5.1 5.1 4.0 CMC 0.4 0.4 0.4 0.4 0.4 PVNO 0.03 0.03 0.03 0.03 - Granular suds suppressor 1.5 1.5 1.5 1.5 1.5 Minor components/miscellaneous to 100% The following are the T50 values (expressed in seconds) obtained for each of Products A to D: T50 A B C D. peroxy acid 130 190 205 240 AVO 95 225 230 115 Builder (citric acid) 90 60 60 60 Heavy metal ion chelating agent (DETPMP or EDDS) 150 30 30 60 Comparative Test Test Method - Stain Removal Swatch Preparation Three white cotton pieces were prewashed with a heavy duty detergent containing no non-biological bleach. Sets of test swatches measuring 6 cm x 6 cm were cut from each sheet, each set having six test swatches. Appropriately apply the stain to (eg paint on) each set of swatches.

Alternatively, pre-prepared swatches from the EMPA Institute can also be used.

In summary, use the following sets of swatches:

Enzyme-catalyzed stains:

Grass;

Bleachable stains:

empa blood;

EMPA blood, milk and ink;

Grease stains:

dirty oil;

shoe polish;

These multi-weave swatches were put through a wash cycle in an automatic washing machine. The swatches were then rated for stain removal by a panel of experts on a 4-point Scheffe scale. The average results for each group compared to the pairwise combination of prior art composition A used as a common reference are listed below.

In more detail, a Miele 698 WM automatic washing machine was used, and the 40°C short cycle program was selected. Water of 12° Geman hardness (Ca:Mg=3:1) was used. Use 75g of detergent dispensed from a granulette dispenser placed in the middle of the load. One swatch of each type was laundered with 2.7 kg of lightly soiled cloth pieces (1 week old household) ballast. Comparative Test - Stain Removal

Using the stain removal test method above, the effectiveness of Composition B in removing different types of stains was compared with Composition A of the prior art as a reference.

The results obtained are as follows: stain type Stain removal effect (PSU) EMPA blood +1.8 ^* EMPA BMI +0.6 Grass +0.7 dirty oil +0.6 shoe polish +0.7 ^* Validity is at 95% confidence level. Example 2

The following bleach-containing machine dishwashing compositions (parts by weight) were prepared according to the present invention. A B C D. E. f G Citrate 15.0 15.0 15.0 15.0 15.0 15.0 - 480N 6.0 6.0 6.0 6.0 6.0 6.0 - Carbonate 17.5 17.5 17.5 17.5 17.5 17.5 - Phosphates - - - - - - 38.0 Silicate (calculated as SiO ₂ ) 8.0 8.0 8.0 8.0 8.0 8.0 14.0 Metasilicate (calculated as SiO ₂ ) 1.2 1.2 1.2 1.2 1.2 1.2 2.5 PB1 - slow release particles (AvO) 1.2 1.2 1.5 1.5 1.5 2.2 1.2 TAED (slow release granules) 2.2 2.2 2.2 3.5 - 2.2 2.2 Cationic lactam - - - - 3.3 - - Pareffin 0.5 0.5 0.5 0.5 0.5 0.5 0.5 Bismuth nitrate - 0.2 0.2 0.2 0.3 0.4 0.2 Protease 2.0 2.0 2.0 2.0 2.0 2.0 2.0 Amylase 1.5 1.5 1.5 1.5 1.5 1.5 - BSA - - - - - - 1.5 DETPMP 0.13 0.13 0.13 0.13 0.13 0.13 - HEDP 1.0 1.0 1.0 1.0 1.0 1.0 - Nonionic 2.0 2.0 2.0 2.0 2.0 2.0 1.5 Sulphate 23.0 22.8 22.4 22.7 22.2 21.5 0.3 Miscellaneous including Moisture to Balance pH(1% solution) 10.7 10.7 10.7 10.7 10.7 10.7 11.0 Example 3:

The following representative beaker test procedure was performed to determine whether sequential exposure of a stained fabric to a heavy metal ion chelating agent and hydrogen peroxide bleach solution would cause a difference in the appearance of the stain being removed.

A pre-soiled cotton swatch was prepared by dipping the swatch in a strong tea solution. Tea stains contain high levels of magnesium and are considered difficult to remove from soiled/stained substrates.

Each 1000 ml beaker was individually charged with a solution containing EDDS at a concentration of 0.5% by weight, and a hydrogen peroxide solution corresponding to 2% AvO. Each heavy metal ion sequestrant, and bleach solution was buffered to a pH of 10.5, which is the "in-the-wash" pH typically encountered in laundry processes.

Groups of pre-soiled swatches were dipped in one, or sequentially, of the two solutions. The soaking time in each solution was 20 minutes. Each soak was then rinsed with a dilute NaOH solution.

In detail, use the following wash/soak protocol: Group plan A Soak in bleach solution only B Soak in EDDS solution only C Soak in bleach solution, then in EDDS solution D. Soak in EDDS solution followed by bleach solution

The stain removal results obtained for each wash/soak protocol were evaluated by comparison to a clean white cotton swatch using Macbeth Spectrophotometer to measure yellowness, whiteness and a, b and 1 values. The following is the result obtained Dirty swatches A B C D. yellow 55.1 35.7 36.7 29.4 19.3 White -141.2 -92.1 -94.1 -75.0 -50.1 1 -9.7 -5.8 -8.6 -4.5 -3.4 a 3.5 -.3 2.3 0.0 -0.7 b 23.8 16.1 15.5 13.4 8.9

Yellow positive values, lower a and b values are desired. White positive values and larger values of 1 are desired.

It can be seen that the stain removal results of the group of cloth swatches D are better than the results obtained for the cloth swatches A-C. It has thus been demonstrated that sequential exposure of soiled fabrics to a solution containing a heavy metal ion chelating agent prior to contacting a solution containing a bleach provides enhanced stain removal performance.

Example 4

The following representative test method demonstrates that when a stained cloth swatch is treated with a solution containing a heavy metal ion sequestrant prior to being laundered with a detergent product containing a fast (i.e., uncontrollable rate release) bleach, Outstanding removal performance on bleachable stains.

Pre-soiled cotton swatches were prepared by dipping the swatches in a strong tea solution. Tea stains are high in magnesium and are considered difficult to remove from soiled/stained substrates.

Each 1000 ml beaker was filled with a solution containing 0.005% by weight EDDS buffered to a pH of 10.5, which is the "in-the-wash" pH typically encountered in laundry processes.

Groups of pre-soiled swatches were rinsed with an EDDS solution and then laundered using a full laundry cycle using a bleach-containing detergent product. Rinse in EDDS solution was set for 2 or 5 minutes. The laundry method consisted of a main wash in a Miele washing machine using demineralized water at 40°C. The detergent product used in this wash method has fast release bleach, and has the composition of Example 1 Formulation A.

The effectiveness of pre-rinsing the pre-soiled swatches with a heavy metal ion sequestrant solution prior to laundering was evaluated using as a reference multiple sets of pre-soiled swatches that had only been subjected to the full laundry cycle.

Removal of bleachable stains was assessed visually using a 4-point Scheffe scale of known application panel scoring units (PSUs), and % stain removal values were calculated using a Macbeth spectrometer.

Here are the results obtained: Rinse/Wash Program % of stain removed PSU (Scheffe) relatively only washed only washed 87 - Rinse in EDDS solution for 2 minutes, then wash 92 +3 ^* Rinse in EDDS solution for 5 minutes, then wash 97 +3 ^{* *} Validity is at 95% confidence level.

Significant bleachable stain removal benefits were observed when swatches were exposed to heavy metal ion sequestrants prior to laundering with bleach-containing detergent products.

Example 5:

The wash/rinse protocol of Example 3 was repeated with the following differences:

1. The 0.005% EDDS solution was replaced by a solution containing 0.005% EDDS and 0.05% sodium citrate, which was also buffered to pH 10.5.

2. The rinse time was set to 3 minutes.

3. Use a cloth swatch (cotton) with the following stains one by one:

(a) Blood (EMPA)

(b) coffee

(c) red wine

(d) cocoa powder

(e) Blood, Milk and Ink (EMPA)

Swatches (a) and (e) were obtained from the EMPA organization. Swatches (b) to (d) were obtained by applying the stains to prewashed 15cm x 15cm white cotton swatches.

Using this modified test protocol, the effect of pre-rinsing soiled swatches with a solution containing a heavy metal ion sequestrant/builder prior to laundering was evaluated compared to the same soiled swatches being subjected to the laundry method only, without any Comparison of the results obtained in the pre-rinse step.

Stain removal results were evaluated using a Macbeth spectrophotometer and % stain removal values were calculated.

and get the following result: Rinse/Wash Program % remove stains blood coffee wine cocoa powder BMI only washed 78 76 100 36 70 Rinse in EDDS/builder solution for 3 minutes before washing 100 78 100 34 78

It can thus be seen that enhanced stain removal performance is obtained when a rinse step in a builder/heavy metal ion sequestrant solution is used prior to the wash step.

Claims (1)

1. A washing method, comprising the following steps: (1) supply the substrate with dirt with the solution without bleach containing 0.005-1% by weight of heavy metal ion chelating agent; (2) keeping the solution in contact with said soiled substrate; and (3) The said substrate with dirt is then washed with a detergent composition containing a bleaching agent; wherein, the heavy metal ion chelating agent is selected from the group consisting of ethylenediamine-N, N'-disuccinic acid, ethylenediamine- Salts of N,N'-disuccinic acid or mixtures thereof.