JP3174068B2 - Detergent composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a detergent composition comprising an amylase enzyme in combination with a rudder system, which is particularly suitable for laundering.

Builder systems are commonly used in detergent compositions because of their ability to remove soil and soften water.
Often a composite builder system comprising two or more builder compounds is used, including a system comprising an aluminosilicate zeolite, a crystalline layered silicate and an optional organic polymeric compound. .

Thorough removal of special stains / stains from soiled / stained substrates, such as blood, spinach, ink, chocolate and tomato sauce, is used in washing methods such as washing or mechanical dishwashing. This is a challenging and rewarding task for the formulator of detergent compositions. The enzyme is used to facilitate removal of such stains / stains from the substrate during washing.
Commonly used in detergent compositions.

One of the problems encountered when using enzymes as a component of detergents is that the activity of the enzyme during washing is sensitive to the presence of other chemical components in the washing solution. In particular, it has been found that a certain level of hardness ions, especially calcium on, is required to ensure effective enzymatic action. Without wishing to be bound by theory, it is believed that the formation of a hardness ion-enzyme association is necessary to ensure this enzymatic action. Starch degrading enzymes have been found to be particularly sensitive to hardness ion levels.

When certain builder systems, particularly systems comprising an aluminosilicate zeolite, a crystalline layered silicate and optionally an organic polymeric compound, are present in the amylase-containing detergent composition, the detergent composition is washed. It has been found that certain problems arise because both the amylase and the builder system are usually present together in the laundry solution when introduced into the solution. The builder system is believed to prevent or disrupt the formation of hardness ion-enzyme associations required for effective enzyme activity. This has been observed to reduce the ability to remove dirt / stain.

However, the inventor now relates to a detergent composition comprising both an amylase enzyme and a builder system comprising an aluminosilicate zeolite, a crystalline sheet silicate and preferably an organic polymeric compound. The weight ratio of layered silicate to amylase (basic activity 120KNU / g)
It has been found that when the ratio is 7: 1 to 20: 1, the stain / soil removal performance for stains / soils particularly sensitive to enzymes is mad.

Although the problem of enzymatic degradation is only partially recognized in the art, the importance of the enzyme-calcium association for effective enzyme performance does not appear to be particularly recognized. For example, U.S. Pat.No. 4,176,079A states that "enzymes tend to degrade and become inactive in a highly alkaline detergent composition environment" and that enzymes are "non-phase like phosphates in laundry solutions. May be attacked by dissolution). Thus, the problem of enzymatic degradation is related to high pH and / or phosphate, but not particularly to the type of builder systems provided herein.

European Patent No. EP-A-552,287 is an amount of the zeolite 60 to 96 wt%, wherein _{NaMSi x O 2x + 1 · yH} 2 O
Wherein M is sodium or hydrogen, and x is 0-20
In a quantity of from 2 to 25% by weight and the polymeric polycarboxylate in 2% by weight.
A phosphate-free builder combination in an amount of 1616% by weight, and optionally containing a phosphonate, wherein the weight ratio of crystalline layered silicate to polymeric polycarboxylate is from 3: 1 to 1: 3 Is described. Enzymes are generally described as optional components.

According to the present invention, there is provided a detergent composition containing the following (a) and (b).

(A) an amylase enzyme; and (b) a builder system comprising the following (i) and (ii): (i) an aluminosilicate zeolite; and (ii) a crystalline layered silicate.

(The amylase enzyme of the crystalline layered silicate (120 KNU /
Most preferably, the builder system also comprises an organic polymeric compound.

Amylase One of the essential components of the composition is an amylase enzyme, ie an enzyme having amylolytic activity.

The amount of amylase enzyme present in the detergent composition is proportional to the amount of crystalline sheet silicate builder present in the detergent composition. Amylase enzyme of crystalline layered silicate (120K
The weight ratio to NU / g (kilo Novo units / gram activity basis) is 7: 1 to 20: 1, preferably 8: 1 to 18: 1, most preferably
10: 1 to 16: 1.

In general, the amylase enzyme is present in detergent compositions at a concentration of 120 KNU / g (kilo Novo units / gram) activity in 0.1% of the composition.
-5% by weight, preferably 0.2-3% by weight, more preferably 0.3-2% by weight, most preferably 0.4-1.5% by weight.

Kilo Novo units / gram (KNU / g) is a well-known measure of the activity of amylolytic enzymes and is disclosed in GB 1,269,839A (Novo).
More specifically, 1KNU is prepared from 5.25 grams of starch per hour (Merck, Amylum Solubile Erg.) In a method having the following standard conditions described in GB 1,269,839A:
B.6, batch 9947275).

Substrate Soluble starch Calcium content in solvent 0.0043M Reaction time 7-20 minutes Temperature 37 ° C pH 5.6 Amylase enzyme may be derived from fungi or bacteria. Amylases obtained by chemical or genetic manipulation of varieties derived from fungi or bacteria are also useful herein. The amylase enzyme is preferably α-amylase.

Preferred amylases include, for example, GB 1,269,83
B. lichenifor, described in more detail in specification 9A
There is α-amylase obtained from ms special varieties. α-
Deposit numbers reported for B. licheniforms varieties capable of producing amylase include NCIB8061, NCIB8059, ATCC
6634, ATCC6598, ATCC11945, ATCC8480 and ATCC9945a
There is.

Preferred commercially available α-amylases include, for example, amylase sold by Gist-Brocades under the trade names Rapidase and Maxamyl, Miles Laboratories, E
Amylase sold by Lkhart, Indiana under the trade name Taka-Therm L-340, Rohm and Hass, West Philadelp
Amylase sold under the trade name Rohalase AT from hia, PA, and Termamyl 60T from Novo Industries A / S
And amylase sold under the trade names 120T, Fungamyl and BAN.

In a preferred embodiment, the amylase has improved stability,
In particular, it is designed to improve the stability to oxidation and the thermal stability, for example in a bleaching environment. Stability can be measured using any of the technical tests known in the art, including those described in WO 94 / 02597A. Amylase with enhanced stability is available from Novo Industries A / S or Genencor International
Commercially available from l.

Highly preferred amylase with enhanced oxidative stability is
Regardless of whether one, two or more amylase species are direct precursors, they are obtained from one or more Bacillus amylase, in particular Bacillus α-amylase, using site-directed mutagenesis. Preferred amylases of this type are described in WO / 94 / 02597A and are described in B. Lichen
position 197 of iformis α-amylase (sold under the trade name Termamyl), or B. amyloliquefaciens, B. sub.
comprising a mutant in which a methionate group at a similar position in a similar parent amylase, such as tilis or B. stearothermophilus, has been replaced using alanine or threonine, preferably threonine.

Other preferred amylases with enhanced oxidative stability are B.
Derived from Licheniformis NCIB806, the 207th American
Chemical Society Natinal Meeting, March 13-17 1994
At Genencor International, C. Mitchinson, in a research presentation entitled "Oxidation-Resistant α-Amylase". Methionine (Met) has been identified as the most easily modified residue. Met at positions 8, 15, 197, 256, 30
4,366 and 438, respectively, forming special mutants, of particular importance are M197L and M197T, with the M197T mutant being the most stable expression mutant.

Other preferred amylases having oxidized stability have been described in WO 94 / 18314A (Genencor International)
l) and amylases described in WO 94 / 02597A (Novo). It is possible to use any of the other oxidatively stable amylases, such as those obtained by site-directed mutagenesis from the known chimeric, hybrid, or simple mutant forms of the available amylase. it can. Other enzyme variants can be used, including those described in WO 95 / 09909A (Novo).

Enzymes for incorporation into solid detergent compositions are commonly marketed as enzyme prills containing active enzyme supported on various inert carriers including, for example, alkali metal sulfates, carbonates and silicates. ing.

If desired, an organic binder can also be included. In a preferred embodiment, the calcium content of these enzyme prills is minimized, thereby ensuring good storage stability of the enzyme in the product.

Builder system The present detergent composition contains, as essential components, a builder system containing an aluminosilicate zeolite and a crystalline layered silicate. If desired, other builders, especially organic polymeric compounds, can also be present.

Here, the builder means a component capable of suppressing the amount of hardness ions, that is, Ca ²⁺ and Mg ²⁺ , in the washing solution. The suppression can be performed by chelation or sequestration of hardness ions or by an ion exchange mechanism.

The builder system is typically present in an amount of 1-80%, preferably 10-70%, most preferably 20-60% by weight of the detergent composition.

Aluminosilicate zeolite builder Virtually all known aluminosilicate zeolites can be used here. Aluminosilicate zeolite is
Naturally occurring materials may be used, but synthetic products are preferred. Synthetic crystalline aluminosilicate ion exchange materials include zeolite A,
It is commercially available as zeolite B, zeolite P, zeolite X, zeolite MAP, zeolite HS, and mixtures thereof.

Suitable aluminosilicate zeolite builders are those having the unit cell formula Na _z [(AlO ₂ ) _z (SiO ₂ ) _y ] .XH ₂ O. Wherein z and y are at least 6, the molar ratio of z to y is 1.0 to 0.5, and x is at least 5, preferably 7.5 to 276, more preferably 10 to 264. The aluminosilicate material is in a hydrated form, preferably crystalline, and in bound form 10% to 28%, more preferably 18%
% To 22% water.

 Zeolite A has the following formula:

_{Na 12 [AlO 2) 12 (} SiO 2) 12] .xH in ₂ O formula, x is 20 to 30, in particular 27. Zeolite X has the formula Na ₈₆ [(AlO ₂ ) ₈₆ (SiO ₂ ) ₁₀₆ ] .276H ₂ O.

Zeolite MAP is described in European patent specification 384070A (Unilever). This material is defined as an alkali metal aluminosilicate of the zeolite P type and has a silicon to aluminum ratio of 1.33 or less, preferably
0.9 to 1.33, more preferably 0.9 to 1.2.

Of particular interest are zeolite MAPs having a silicon to aluminum ratio of 1.15 or less, especially 1.07 or less.

The aluminosilicate zeolite builder is preferably 40-98%, more preferably 50-95% of the builder system, by weight of active aluminosilicate zeolite in the builder system,
Most preferably it is present in an amount of 60-90%. Here, "by weight of activated aluminosilicate zeolite" means that the weight of aluminosilicate zeolite is expressed on an active basis, i.e. without any water of crystallization.

Crystalline layered silicate builders Virtually all crystalline layered silicate builders are suitable here. The preferred crystalline layered sodium silicate here has the following general formula:

NaMSi _x O _{2x + 1} .yH ₂ O wherein M is sodium or hydrogen and x is 1.9 to
And y is a number from 0 to 20. Such crystalline layered sodium silicates are disclosed in EP-A-0164.
No. 514, their production process is described in DE-A-3417649 and DE-A-374.
No. 2043. For the purposes of the present invention, the value of x in the above general formula is 2, 3 or 4, preferably 2. Most preferred material from Hoechst AG
Δ-Na ₂ Si ₂ O ₅ commercially available as NaSKS-6.

The crystalline layered silicate material, in the granular detergent composition,
Preferably, it is present as finely divided particles which are intimately mixed with a solid, water-soluble ionizable material. The solid, water-soluble, ionizable material is selected from organic acids, organic and inorganic acid salts and mixtures thereof.

The crystalline layered silicate builder is present in the builder system, preferably from 1 to 35% by weight of the builder system, more preferably from 3 to
It is present in an amount of 30% by weight, most preferably 5 to 25% by weight.

Builder optionally used Suitable builder compounds optionally used include:
An organic polymeric compound, a water-soluble monomeric polycarboxylate, or an acid form thereof, a homopolymer or copolymer polycarboxylate or a salt thereof (wherein the polycarboxylic acid has no more than 2 carbon atoms) (Comprising at least two carboxyl groups separated from each other by atoms), carbonates, bicarbonates, borates, phosphates, silicates, and mixtures thereof.

Suitable carboxylate or polycarboxylate builders are in monomeric or oligomeric form, but monomeric polycarboxylates are generally preferred for cost and performance reasons.

Suitable carboxylate containing one carboxyl group include water-soluble salts of lactic acid, glycolic acid and their ether derivatives. Examples of polycarboxylates containing two carboxyl groups include succinic acid (pK (Ca) at pH 10.5 = 1.20), malonic acid (pK at pH 10.5)
(Ca) = 1.51), water-soluble salts of (ethylenedioxy) diacetate, maleic acid, diglycolic acid, tartaric acid, tartronic acid and fumaric acid, as well as ether carboxylate and sulfinylcaroxylate. Polycarboxylates containing three carboxyl groups include, in particular, water-soluble citrates, aconitrates and citraconates, and succinate derivatives such as carboxymethyloxysuccinate, described in GB 1,379,241, Lactoxysuccinate described in 1,389,732, and aminosuccinate and oxypolycarboxylate materials described in Netherlands Application No. 7205873, such as those described in GB 1,387,447. 2-oxa-1,1,3-propanetricarboxylate.

Polycarboxylates containing four carboxyl groups include oxydisuccinates described in GB 1,261,829, 1,1,2,2-ethanetetracarboxylate, 1,1,3, There are 3-propanetetracarboxylate and 1,1,2,3-propanetetracarboxylate. Polycarboxylates containing sulfo substituents include GB 1,398,421 and 1,398,422.
And the sulfosuccinate derivatives described in US Pat. No. 3,936,448, and the sulfonated pyrolytic citrates described in British Patent 1,439,000.

Alicyclic and heterocyclic polycarboxylates include cyclopentane-cis, cis, cis-tetracarboxylate, cyclopentadienide 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 sorbitol Carboxymethyl derivatives of polyhydric alcohols such as mannitol and xylitol. Aromatic polycarboxylates include melitic acid, pyromellitic acid and phthalic acid derivatives described in GB 1,425,343.

Among the above, the preferred polycarboxylate is molecule 1
Hydroxycarboxylates containing up to three carboxyl groups per unit, more preferably citrates. The citrate has a pK (Ca) of 3.50 at pH 10.5.

Mixtures of the monomeric or oligomeric polycarboxylate chelators with the parent acid or salts thereof, such as citric acid or citrate / citric acid mixtures, are also useful as builder components.

Borate builders, as well as borate-forming materials capable of forming borate under detergent storage or washing conditions, can also be used as builders if desired,
It is not preferred under washing conditions below about 50 ° C, especially below about 40 ° C.

Carbonate builders are also suitable as builders to be used if desired, for example, sodium carbonate and sodium sesquicarbonate and those as described in German Patent Application No. 2,321,001, published Nov. 15, 1973. Alkaline earth and alkali metal carbonates, including mixtures of the same carbonates with ultrafine calcium carbonate.

Specific examples of the water-soluble phosphate builder suitable as a builder optionally used herein include alkali metal salts of tripolyphosphate, pyrophosphate salts of sodium, potassium and ammonium, orthophosphates of sodium and potassium, and a polymerization degree of about 6 to about 6. Polymeta / sodium phosphate which is 21 and a salt of phytic acid.

Preferred optional builders include SiO ₂ : N
The ratio of a ₂ O is 1.0 to 2.8, preferably 1.6 to 2.4, most preferably silicates including water-soluble sodium silicate is 2.0. Silicates may be in the form of anhydrous or hydrated salts. Sodium silicate with a SiO ₂ : Na ₂ O ratio of 2.0 is the most preferred silicate.

Other optional builders suitable for the present invention include:
Organic phosphonates such as aminoalkylene poly (alkylene phosphonate), alkali metal ethane 1-hydroxydiphosphonate and nitrilotrimethylene phosphonate. In the above substances, pK at pH 10.5
Diethylenetriaminepenta (methylene phosphonate) having a (Ca) of about 9.95, and a pK (Ca) of 6.84 at pH 10.5
Is ethylenediaminetri (methylenephosphonate)
Hexamethylene diamine tetra (methylene phosphonate) and hydroxy-ethylene 1,1 diphosphonate are preferred.

Ethylenediaminetetraacetic acid (EDTA) is also a suitable optional builder here.

For clarity, naturally acidic builders having, for example, phosphonic or carboxylic acid functionalities may be used in their acid form or in suitable counterparts such as alkali or alkali metal ions, ammonium or substituted ammonium ions. It can be present as a complex / salt with the ion, or a mixture of any of them. Preferably, all salts / complexes are water-soluble.

Organic polymeric compounds All organic polymeric compounds that can act as builders are suitable as preferred optional components of the builder system in the present invention. The organic polymeric compound can also function as a dispersant, anti-redeposition or soil dispersant when incorporated into the detergent composition.

Preferred organic polymeric compounds include water-soluble organic homopolymers or copolymer polycarboxylic acids, wherein the polycarboxylic acid comprises at least two carboxyl groups separated from each other by no more than two carbon atoms. There are those salts. The latter type of polymer is disclosed in GB-A
No. 1,596,756. An example of such a salt is a polymer containing acrylic acid monomer units. Preferred examples are polyacrylates having a molecular weight of 2000-5000 and their copolymers with maleic anhydride,
Such copolymers have molecular weights between 20,000 and 1,000,000, especially 4
It is between 0,000 and 80,000.

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

European Patent EP-A-305282, EP-A
Useful herein are polyamino compounds, including substances derived from aspartic acid, as described in -305283 and EP-A-351629.

Also suitable here are terpolymers comprising monomer units selected from maleic acid, acrylic acid, polyaspartic acid and vinyl alcohol, in particular terpolymers having an average molecular weight of 5,000 to 10,000.

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

Other useful organic polymeric compounds are polyethylene glycols, especially those having a molecular weight of 1000 to 10,000, more preferably 200
0-8000, most preferably about 4000 polyethylene glycol.

The organic polymeric compound is generally incorporated into the builder system in an amount of 0.1 to 20%, preferably 1 to 16%, and most preferably 2 to 12% by weight of the builder system.

Other Detergent Components The detergent composition of the present invention can also include other detergent components. The exact nature of these other components and their loading will depend upon the physical form of the composition and the nature of the cleaning operation using the composition.

For example, the compositions of the present invention may be formulated as detergent compositions for manual and machine laundering, and machine dishwashing compositions, including laundry additive compositions and compositions suitable for the pre-treatment of soiled fabrics. Can be.

When formulated as a composition suitable for machine washing methods, such as machine washing and machine dishwashing methods, the compositions of the present invention include:
One or more selected from additional enzymes, enzyme stabilizing systems, surfactants, bleaching agents, heavy metal ion sequestrants, foam inhibitors, lime soap dispersants, soil dispersants and anti-redeposition and corrosion inhibitors. Preferably, an additional detergent component is included.

Additional enzymes Preferred additional enzymes include commercially available lipases, neutral and alkaline proteases, cellulases, pectinases, lactases and peroxidases conventionally incorporated into detergent compositions, i.e., lipolysis, proteolysis, cellulose degradation, pectin degradation, respectively. There are enzymes that have lactic acid and peroxide decomposing activities. Suitable enzymes are described in U.S. Patent Nos. 3,519,570 and 3,533,139.
It is described in the specification.

Protease enzymes are particularly preferred as enzyme components.
Preferred commercially available protease enzymes include Alcalase, Savi
Novo under the trade name nase, Primase, Durazym and Esperase
Gist- under the trade names of enzymes Maxatase, Maxacal and Maxapem sold by Industries A / S (Denmark)
Genencor Internati, an enzyme sold by Brocades
Enzymes sold by onal, and Opticlean and O
There is an enzyme sold by Solvay Enzymes under the trade name ptimase. Protease enzymes are present in the compositions of the present invention.
It may be present in an amount of 0.0001 to 4% active enzyme by weight of the composition.

Also preferred lipolytic enzymes (lipases) can be present in an amount of active lipolytic enzyme from 0.0001 to 4%, preferably from 0.001 to 1%, most preferably from 0.001 to 0.5% by weight of the composition.

The lipase can be of fungal or bacterial origin, such as Humicola sp., Thermomyces sp., Or Ps
eudomonas pseudoalcaligenes or Pseudomas fluor
Obtained from lipase producing varieties of Pseudomonas sp. including escens. Also useful herein are lipases obtained from mutants of these varieties that have been chemically or genetically modified.

Lipases from Pseudomonas pseudoalcaligenes, described in EP-B-0218272, are preferred.

Another preferred lipase is described in European Patent Application EP-EP-
As described in A-0258068, Humicola
It is obtained by cloning the gene obtained from lanuginosa and expressing the gene in Aspergillus oryza as a host and is commercially available from Novo Industri A / S, Bagsvaerd, Denmark, under the trade name Lipolase. This lipase is disclosed in U.S. Patent No. 4,810,414, Huge-Jensen.
et al., promulgated March 7, 1989.

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

The compositions of the present invention may contain from 0 to about 10% by weight, preferably from about 0.01% by weight, to prevent the chlorine substances present in many tap waters from attacking and inactivating enzymes, especially under alkaline conditions. From about 6% by weight of a chlorine bleach scavenger. The amount of chlorine in water is low, generally about 0.5 ppm to about
Although within the 1.75 ppm range, the amount of chlorine in the total volume of water that comes into contact with the enzyme during washing is generally high, so enzyme stability during use can be problematic.

Suitable chlorine scavenger anions are widely present and are represented by, for example, ammonium cations or salts containing sulfate, bisulfite, thiosulfite, thiosulfate, iodide, and the like. Antioxidants such as carbamates, ascorbates, etc., ethylenediaminetetraacetic acid (EDTA) or their alkali metal salts, organic amines such as monoethanolamine (MEA), and mixtures thereof can be used as well. Other usual scavengers,
Sources of hydrogen peroxide such as, for example, bisulfite, nitrate, chloride, sodium perborate tetrahydrate, sodium perborate monohydrate, sodium percarbonate, and phosphates, condensed phosphates, acetates, benzoic acid Salts, citrates, formates, lactates, malates, tartrates, satyrylates, and the like, and mixtures thereof, can also be used if desired.

Surfactant The detergent composition of the present invention comprises anionic, cationic, nonionic, amphoteric, amphoteric and zwitterionic surfactants as optional detergent components. Can be included.

The surfactant is generally present in an amount from 0.1 to 60% by weight. More preferably, the amount of the surfactant is 1 to 35% by weight, most preferably 1 to 20% by weight. The surfactant is preferably formulated so as to be compatible with the oxygen component present in the composition. For liquid or gel compositions, the surfactants are most preferably formulated so as to enhance or at least not reduce the stability of all oxygen in these compositions.

Anionic, nonionic, amphoteric, and zwitterionic classes and varieties of these surfactants are described in U.S. Pat.
929,678, Dec. 30, 1975, Laughlin and Heuri
ng promulgated. Another example is “Surfac
e Active Agents and Detergents "(Vol.I and II, Sc
hwartz, Perry and Berch). A list of suitable cationic surfactants can be found in U.S. Pat.
No. 7, issued March 31, 19181 to Murphy.

If present, ampholytic, amphoter
ic) and zwitterionic surfactants are generally used in combination with one or more anionic and / or nonionic surfactants.

Anionic Surfactants Virtually all detergent anionic surfactants can be incorporated into the present compositions. These surfactants are
Includes salts of anionic sulfates, sulfonates, carboxylate and sarcosinate surfactants (e.g., sodium, karimou, ammonium and substituted ammonium salts such as mono-, di- and triethanolamine salts). it can.

Other anionic surfactants include isethionates such as acyl isethionates, fatty acid amides of N-acyl taurates, tiltaurides, 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), there are N- acyl sarcosinates.
Also suitable are resin acids and hydrogenated resin acids such as rosin, hydrogenated rosin, and resin acids present in or derived from tallow oil.

Anionic Sulfate Surfactants Suitable anionic sulfate surfactants for use herein include linear and branched primary alkyl sulfates, alkyl ethoxy sulfates, fatty oleoyl glycerol sulfates, alkyl phenol ethylene oxide ether sulfates. , C ₅ ~C ₁₇ acyl -
N- of (C ₁ -C ₄ alkyl) and -N- (C ₁ ~C ₂ hydroxyalkyl) glucamine sulfates, and alkyl sulfates of polysaccharides, such as alkyl polyglucosides (nonionic non sulfate compounds described herein) There is sulfate.

The alkyl ethoxy sulfate surfactant is preferably selected from the group consisting of C ₆ -C ₁₈ alkyl sulfate ethoxylated with about 0.5 to about 20 moles of ethylene oxide per molecule. More preferably, the alkyl ethoxy sulfate surfactant comprises about 0.5 to about 0.5 molecules per molecule.
To about 20 mol, preferably C ₆ -C ₁₈ alkyl sulfates ethoxylated with from about 0.5 to about 5 moles of ethylene oxide.

Anionic Sulfonate Surfactants Suitable anionic sulfonate surfactants for use herein include C ₅ -C ₂₀ linear alkyl benzene sulfonates, alkyl ester sulfonates, C ₆ -C ₂₂ primary or secondary. grade alkane sulfonates, C ₆ -C ₂₄ olefin sulfonates, sulfonate polycarboxylic acids, alkyl glycerol sulfonates, fatty acyl glyceraldehyde roll sulfonates, fatty oleyl glycerol sulfonates, and mixtures thereof.

Anionic Carboxylate Surfactants Suitable anionic carboxylate surfactants for use herein include alkyl ethoxy carboxylate, alkyl polyethoxy polycarboxylate surfactants and soaps ("alkyl carboxyl"),
In particular, there are certain secondary soaps described herein.

Preferred alkyl ethoxy carboxylates for use herein, the formula _{RO (CH 2 CH 2 O)} x CH 2 COO - there is a material having a M ^+, wherein, R is a C ₆ -C ₁₈ alkyl group Yes,
x is from 0 to 10, and the ethoxylate is such that the amount of material where x is 0 is less than about 20% by weight, the amount of material where x is greater than 7 is less than about 25% by weight, and the average R is C If ₁₃ or less, the average x is from about 2 to 4 when the average R is greater than C _13, average x is distributed as with about 3 to 10, M is a cation, preferably It is selected from alkali metals, alkaline earth metals, ammonium, mono-, di-, tri-ethanol-ammonium, most preferably from sodium, potassium, ammonium and mixtures thereof with magnesium. Preferred alkyl ethoxy carboxylates are substances R is C ₁₂ -C ₁₈ alkyl group.

Alkyl polyethoxy polycarboxylate surfactants suitable for use herein include those of the formula RO- (CHR _1-
A surfactant having CHR ₂ —O) —R ₃ , wherein x is 1 to 25, and R ₁ and R ₂ are hydrogen, a methyl acid group, a succinic acid group, a hydroxysuccinic acid group, and At least one R ₁ and R ₂ selected from the group consisting of mixtures thereof;
Is a succinic or hydroxysuccinic group, R ₃ is hydrogen, substituted or unsubstituted,
-8 hydrocarbons, and mixtures thereof.

Anionic Secondary Soap Surfactants Preferred soap surfactants are secondary soaps containing carboxyl units connected to secondary carbon. Second
Grade carbon is, for example, as in p-octylbenzoic acid,
Or it may be in a ring structure, as in an alkyl-substituted cyclohexylcarboxylate. The secondary soap surfactant preferably does not contain an ether bond, an ester bond and a hydroxyl group. Preferably, the head portion (amphiphilic portion) is free of nitrogen. Secondary soap surfactants typically have 11 to 15 carbon atoms, but may be slightly more (e.g., up to 16) like p-octylbenzoic acid.

The structure below shows some of the preferred secondary soap surfactants.

A. Highly preferred secondary soap surfactants have the formula R ³ CH
(R ⁴ ) is a secondary carboxyl-based material having COOM, where R ³ is CH ₃ (CH ₂ ) _x and R ⁴ is CH ₃ (CH ₂ ) _y
And y may be 0 or an integer of 1 to 4, and x may be 4 to 10
And the sum of (x + y) is 6 to 10, preferably 7 to 9, and most preferably 8.

B. Another preferred secondary soap, carboxyl compounds wherein the carboxyl group substituent is on a ring hydrocarbyl unit, i.e., secondary soaps of the formula R ⁵ -R ⁶ COOM, wherein, R ⁵ is C ⁷ ~ C ^10, preferably C ⁸ -C ⁹ alkyl or alkenyl, R ⁶ is benzene, ring structures such as cyclopentane and cyclohexane. (Note: R ⁵ is ortho to the carboxyl on the ring, or a meta or para position) C. Still another class of preferred secondary soap surfactants formula _{CH 3 (CHR) k - (} CH 2 _{) m - (CHR) n -} CH (COOM) (CHR) o - (CH2) p - (CHR) a secondary carboxyl compounds with q -CH _3, wherein each R is C ₁ ~
It is a C ₄ alkyl, k, n, o, q is an integer from 0 to 8, provided that (including carboxylate) the total number of carbon atoms is 10 to 18.

In each of the above formulas A, B and C, M may be any suitable counterion, especially one which confers water solubility.

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

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

Nonionic Surfactants Virtually all nonionic surfactants useful for detergents can be included in the composition. Representative, useful nonionic surfactants include, but are not limited to, the following.

Nonionic polyhydroxy fatty acid amide surfactants Polyhydroxy fatty acid amides suitable for use herein are materials having the structural formula R ² CONR ¹ Z, wherein R ¹ is H, C ₁ -C ₄ Hydrocarbyl, 2-hydroxyethyl, 2
-Hydroxypropyl, or a mixture thereof, preferably C ₁ -C ₄ alkyl, more preferably C ₁ or C ₂ alkyl, most preferably C ₁ alkyl (ie methyl), and R ² is C ₅ -C ₃₁ hydrocarbyl , preferably straight-chain C ₅ ~C
₁₉ alkyl or alkenyl, more preferably linear C ₉ to
C ₁₇ alkyl or alkenyl, most preferably straight chain C ₁₁
CC ₁₇ alkyl or alkenyl, or a mixture thereof, wherein Z is a polyhydroxyhydrocarbyl having a hydrocarbyl straight chain having at least three hydroxyls directly attached to the chain, or an alkoxylated derivative thereof (preferably ethoxylated or propoxylated). ). Z is preferably obtained from a reducing sugar in a reductive amination reaction, more preferably Z is glycityl.

Nonionic Condensates of Alkyl Phenols Polyethylene, polypropylene, and polybutylene oxide condensates of alkyl phenols are suitable for use herein. Generally, polyethylene oxide condensates are preferred. These compounds include the condensation products of alkyl phenols and alkylene oxides having alkyl groups containing about 6 to about 18 carbon atoms in a linear or branched configuration.

Nonionic Ethoxylated Alcohol Surfactants Alkyl ethoxylate condensation products of aliphatic alcohols with about 1 to about 25 moles of ethylene oxide are suitable for use herein. The alkyl chain of the aliphatic alcohol is
It may be straight or branched, primary or secondary and generally has from 6 to 22 carbon atoms. An alcohol having an alkyl group having 8 to 20 carbon atoms;
Particular preference is given to condensation products of 10 mol of ethylene oxide.

Mixed ethoxylated / propoxylated fatty alcohols nonionic ethoxylated / propoxylated fatty alcohol surfactants, ethoxylated C ₆ -C ₁₈ fatty alcohols and C ₆ -C ₁₈ is,
Particularly when it is water-soluble, it is a surfactant suitable for use herein. Preferably, the ethoxylated fatty alcohols are ethoxylated degree is C ₁₀ -C ₁₈ ethoxylated fatty alcohols 3 to 50, and most preferably, C ₁₂ -C ₁₈ ethoxylated ethoxylation degree of 3 to 40 Fatty alcohol. Preferably, the mixed ethoxylated / propoxylated fatty alcohol has an alkyl chain length of 10 to 18 carbons, a degree of ethoxylation of 3 to 30, and a degree of propoxylation of 1 to 10.

Nonionic EO / PO Condensates with Propylene Glycol The hydrophobic-based condensation products of ethylene oxide formed by the condensation of propylene oxide with propylene glycol are suitable for use herein. The hydrophobic portion of these compounds preferably has a molecular weight of about 1500 to about 1800.
Which is insoluble in water. Examples of such compounds include Pluronic surfactants available from BASF.

Nonionic EO Condensation Product with Propylene Oxide / Ethylene Diamine Adduct The condensation product of ethylene oxide with the product obtained from the reaction of propylene oxide and ethylene diamine is suitable for use herein. The hydrophobic portion of these products consists of the reaction product of ethylenediamine and excess propylene oxide, typically having a molecular weight of about 2500 to about 30.
00. An example of this type of nonionic surfactant is the Tetronic compound available from BASF.

Nonionic Alkyl Polysaccharide Surfactants Alkyl polysaccharides suitable for use herein are described in U.S. Pat. No. 4,565,647, Llenado, issued Jan. 21, 1986.
And about 6 to about 30, preferably about 10 carbon atoms.
From about 16 hydrophobic groups, and from about 1.3 to about 10, preferably about
It has a hydrophilic group of a polysaccharide, such as a polyglycoside, containing 1.3 to about 3, most preferably about 1.3 to about 2.7 saccharide units. All reducing sugars having 5 or 6 carbon atoms,
For example, glucose, galactose, can be used, and the galactosyl moiety can be replaced with a glucosyl moiety (optionally, hydrophobic groups can be added at positions 2, 3, 4, etc. to provide glucose to glucoside or galactoside). Or give galactose). The intersugar linkage can be, for example, between one position of the additional saccharide unit and 2, 3, 4, and / or 6 positions on the preceding saccharide unit.

Preferred alkylpolyglycosides have the formula ^{_{R 2 O (C n H 2n}} O) t ( glycosyl) _x, wherein, R2 has a carbon number of alkyl group is 10 to 18, preferably 12 to 14 alkyl , Alkylphenyl, hydroxyalkyl, hydroxyalkylphenyl, and mixtures thereof, wherein n is 2 or 3, t is 0-10, preferably 0, and x is 1.
It is 3 to 8, preferably 1.3 to 3, and most preferably 1.3 to 2.7. Glycosyl is preferably derived from glucose.

Nonionic fatty acid amide surfactants Suitable fatty amide surfactants for use herein are those having the formula R ⁶ CON (R ⁷ ) ₂ , wherein R
⁶ is an alkyl group having ^{7 to} 21 carbon atoms, preferably 9 to 17 carbon atoms, and each R ⁷ is hydrogen, C ₁ -C ₄ alkyl, C ₁ -C ₄ hydroxyalkyl, and — (C ₂ H ₄ O) is selected from the group consisting of _x H, x is an integer of 1 to 3.

Amphoteric Surfactants Suitable amphoteric surfactants for use herein include amine oxide surfactants and alkyl amphoteric carboxylic acids.

A good example of an alkyl amphoteric dicarboxylic acid suitable for use herein is Miranol C2M Conc., Manufactured by Miranol, Inc., Dayton, NJ.

Amine oxide surfactants Suitable amine oxides for use herein include:
A compound having the formula R ³ (OR ⁴ ) _x N ⁰ (R ⁵ ) ₂ , wherein
R ³ is 8 to 26 carbon atoms, preferably selected from 8-18, alkyl, hydroxyalkyl, acylamidopropyl and alkyl phenyl group, or mixtures thereof from,, R ⁴
Is an alkylene or hydroxyalkylene group having 2 to 3 carbon atoms, preferably 2 carbon atoms, or a mixture thereof, and x
Is 0-5, preferably 0-3, and each R ⁵ has 1 carbon atom
1-3, preferably 1-2 alkyl or hydroxyalkyl groups, or 1-3, preferably polyethylene oxide groups containing one ethylene oxide group. R ⁵ groups, for example through an oxygen or nitrogen atom added together, may form a ring structure.

These amine oxide surfactants in particular include the C ₁₀ -C ₁₈ alkyl dimethyl amine oxides and C ₈ -C ₁₈ alkoxy ethyl dihydroxy ethyl amine oxides. Examples of such materials include dimethyloctylamine oxide, diethyldecylamine oxide, bis- (2-hydroxyethyl) dodecylamine oxide, dimethyldodecylamine oxide, dipropyltetradecylamine oxide, methylethylhexadecylamine oxide,
There are dodecylamidopropyl dimethylamine oxide, cetyl dimethylamine oxide, stearyl dimethylamine oxide, tallow dimethylamine oxide and dimethyl-2-hydroxyoctadecylamine oxide. C ₁₀ -C ₁₈ alkyl dimethyl amine oxides and C
_{10- C18} acylamidoalkyldimethylamine oxide is preferred.

Zwitterionic surfactant The detergent composition of the present invention can also include a zwitterionic surfactant. These surfactants include derivatives of secondary and tertiary amines, derivatives of heterocyclic secondary and tertiary amines, or derivatives of quaternary ammonium, quaternary phosphonium or tertiary sulfonium compounds. Can be roughly described as: Betaine and sultaine surfactants are representative of the zwitterionic surfactants used herein.

Betaine surfactants useful herein betaines of the formula ^{_{R (R ') 2 N +}} R 2 COO - is a compound having the formula, R represents C ₆ -C ₁₈ hydrocarbyl group, preferably a C ₁₀ -C ₁₆ an alkyl group or a C ₁₀ -C ₁₆ acylamido alkyl group, each R ¹ is typically C ₁ -C ₃
Alkyl, preferably methyl, and m and R ² are C _1-
C ₅ hydrocarbyl groups, preferably C ₁ -C ₃ alkylene group,
More preferably a C ₁ -C ₂ alkylene group. Examples of suitable betaines include coconut acylamidopropyl dimethyl betaine, hexadecyl dimethyl betaine, C
_12-14 acyl amidopropyl betaine, C _8-14 acyl amides hexyl diethyl betaines, 4 [C _14-16 acyl methylamide diethyl ammonio] -1-carboxymethyl-butane,
_{C16-18 acylamidodimethyl} betaine, _{C12-16 acylamidopentanediethyl-} betaine, [ _{C12-16 acylmethylamidodimethylbetaine} . Preferred betaines are
C _12-18 dimethylammoniohexanoate and _10-18
Acylamidopropane (or ethane) dimethyl (or diethyl) betaine. Complex betaine surfactants are also suitable for use herein.

Sultaine Surfactants Useful sultaines for use herein have the formula (R
A compound having (R ¹ ) ₂ N ⁺ R ² SO ₃ ^— , wherein R is C
_6-18 hydrosilation group, preferably a C ₁₀ -C ₁₆ alkyl group, more preferably a C ₁₂ -C ₁₃ alkyl group, each R ¹ is typically C ₁ -C ₃ alkyl, preferably methyl, R ² is C ₁ ~
C ₆ hydrocarbyl group, preferably a C ₁ -C ₃ alkylene or, preferably, hydroxyalkylene group.

Ampholytic Surfactants The compositions of the present invention can include an amphoteric surfactant. These surfactants are generally referred to as aliphatic derivatives of secondary or tertiary amines, or of aliphatic derivatives of heterocyclic secondary or tertiary amines, wherein the aliphatic group may be linear or branched. Can be explained.

Cationic surfactant A cationic surfactant can also be used in the detergent composition of the present invention. Suitable cationic surfactants, mono C ₆ -C _16, preferably has a quaternary ammonium surfactant selected from C ₆ -C ₁₀ N-alkyl or alkenyl ammonium surfactants, the remaining The N position is substituted by a methyl, hydroxyethyl or hydroxypropyl group.

Heavy Metal Ion Sequestering Agent The detergent composition of the present invention contains a heavy metal ion sequestering agent as a preferable component that is optionally used. The heavy metal ion sequestering agent means a component that sequesters (chelates) heavy metal ions. These components may have the ability to chelate calcium and magnesium,
It preferably has the selectivity of binding heavy metal ions such as iron, manganese and copper.

Heavy sequestrants generally comprise from 0.005% to 20%, preferably from 0.1% to 10%, more preferably from 0.25% by weight of the composition.
-7.5% by weight, most preferably 0.5-5% by weight.

Heavy sequestrants which are acidic in nature and have, for example, phosphonic or carboxylic acid functions can be used in the form of their acids or suitable counterparts such as alkali or alkali metal ions, ammonium or substituted ammonium ions or mixtures thereof. It can exist as a complex / salt with the ion. Preferably, all salts / complexes are water-soluble. The molar ratio of the counter ion to the heavy sequestering agent is preferably at least 1: 1.

Heavy metal ion sequestering agents suitable for use herein include nitrilotriacetic acid and polyaminocarboxylic acids such as ethylenediaminotetraacetic acid, ethylenetriaminepentaacetic acid, ethylenediaminedisuccinic acid, ethylenediaminediglutaric acid, 2-hydroxypropylenediaminedisuccinate. There are acids or salts of any of them.

A particularly preferred heavy sequestering agent is ethylenediamine-N, N'-disuccinic acid (EDDS) or an alkali metal, alkaline earth metal, ammonium, or substituted ammonium salt thereof, or a mixture thereof. preferable
The EDDS compound is in the form of the free acid, or a sodium or magnesium salt thereof, or a complex thereof.
Examples of such preferred sodium salts of EDDS include Na
₂ EDDS and Na ₃ EDDS are included. Examples of such preferred magnesium complexes of EDDS, MgEDDS or Mg ₂ EDD
There is S. EDDS is also a good calcium chelator and has a pK (Ca) of 4.96 at pH 10.5.

Other suitable heavy sequestering agents for use herein are iminodiacetic acid derivatives, such as EP-A-31.
2-hydroxyethyldiacetic acid or glyceilliminodiacetic acid as described in US Pat. No. 7,542 and EP-A-399,133.

Iminodiacetate-N-2-hydroxypropyl sulfonic acid and N-carboxymethyl N aspartate described in EP-A-516,102
-2-Hydroxypropyl-3-sulfonic acid sequestering agents are also suitable here. European Patent No. EP-A-
Β-alanine-N, N ′ described in US Pat.
Also preferred are diacetic acid, aspartic acid-N, N'-diacetic acid, aspartic acid-N-monoacetic acid and iminodiacetic acid sequestering agents.

EP-A-476,257 describes suitable amino sequestering agents. EP-A-510,331 describes suitable sequestering agents derived from collagen, keratin or casein. European Patent EP-A-528,859
The specification describes suitable alkyliminodiacetic acid sequestering agents. Dipicolinic acid and 2-phosphonobutane-1,2,4-tricarboxylic acid are also suitable. Glycinamide-N, N'-disuccinic acid (GADS) is also suitable.

Organic Peracid Bleaching System In one aspect of the present invention, the detergent composition comprises an organic peracid bleaching system. In a preferred embodiment, the bleaching system comprises a hydrogen peroxide source and an organic peracid bleach precursor compound. Organic peracids are formed by the in situ reaction of a precursor and a source of hydrogen peroxide. Preferred sources of hydrogen peroxide include inorganic perhydrate bleach. In another preferred embodiment, the preformed organic peracid is incorporated directly into the composition. Compositions comprising a mixture of a hydrogen peroxide source and an organic peracid precursor in combination with a preformed organic peracid are also contemplated.

Inorganic perhydrate bleach Inorganic perhydrate salts are a preferred source of hydrogen peroxide. These salts are generally present in the form of alkali metal, preferably sodium, salts in amounts of 1 to 40%, more preferably 2 to 30%, most preferably 5 to 25% by weight of the composition.

Examples of inorganic perhydrate salts include perborate, percarbonate, perphosphate, persulfate and persilicate. Inorganic perhydrate salts are generally alkali metal salts. The inorganic perhydrate salt can be formulated as a crystalline solid without further protection. However, for certain perhydrates, a preferred embodiment of such a granular composition is to provide a material in a coated form that provides superior storage stability to the perhydrate salt in the granular product. use. Suitable coatings comprise inorganic salts such as alkali metal silicates, carbonates or borates or mixtures thereof, or organic materials such as waxes, oils or fatty soaps.

Sodium perborate is a preferred water hydrate salt, nominal formula NaBO ₂ H ₂ monohydrate O ₂ or the tetrahydrate NaBO ₂ H ₂ O ₂ · 3H
It may be in the form of ₂ O.

Alkali metal percarbonates, especially sodium percarbonate, are the preferred perhydrates here. Sodium percarbonate is 2Na ₂
It is an addition compound having a formula corresponding to CO ₃ .3H ₂ O ₂ and is commercially available as a crystalline solid.

Potassium peroxymonopersulfate is another inorganic perhydrate salt used in the detergent compositions of the present invention.

Peracid Bleach Precursor Peracid bleach precursor is perhydrod
A compound that reacts with hydrogen peroxide in a rolysis reaction to form a peracid. Generally, the peracid bleach precursor is Where L is a leaving group and X is the structure of the peracid formed by perhydrolysis. Substantially all functional groups such that

The peracid bleach precursor compound is preferably present in the detergent composition at 0.5%.
-20% by weight, more preferably 1-15% by weight, most preferably 1.5-10% by weight. Suitable peracid bleach precursor compounds generally contain one or more N- or O acyl groups, and these precursors can be selected from a wide range of groups. Preferred types include acid anhydrides, esters, imides, lactams and acylated derivatives of imidazoles and oximes. Examples of useful materials falling into these categories are described in GB-A-1586789. Suitable esters are described in GB Patent GB-
A-836988, 864798, 1147871, 2143231 and EP EP
-A-0170386.

Leaving group The leaving group (hereinafter referred to as L group) must have sufficient reactivity so that the reaction takes place in an optimal time frame (eg, a wash cycle). However, if the reactivity of L is too high, the activator is difficult to stabilize for use in bleaching compositions.

Preferred L groups are And a mixture thereof, wherein R ¹ is an alkyl, aryl, or alkaryl group having 1 to 14 carbon atoms, and R ³ is an alkyl chain having 1 to 8 carbon atoms. And R ⁴ is H or R ³ , and Y is H or a group imparting solubility. Any of R ¹ , R ³ and R ⁴ may be substituted by substantially all functional groups including, for example, alkyl, hydroxy, alkoxy, halogen, amine, nitrosyl, amide and ammonium or alkyl ammonium groups.

Groups that impart desirable solubility, -SO ₃ ^- M ^+, -CO
^{_{2 - M +, -SO 4 -}} M +, -N + (R 3) 4 X - and O <- (R ³⁾
_3, and most preferably -SO ₃ ^- M ⁺ and -CO ₂ ^- a M ^+, R ³ is an alkyl chain from 1 to 4 carbon atoms, M confers solubility to the bleach activator X is a cation and X is an anion that confers solubility to the bleach activator. Preferably M is an alkali metal, ammonium or substituted ammonium cation, most preferably sodium and potassium, and X is a halide, hydroxide, methyl sulfate or acetate anion.

Alkyl percarbonate bleach precursor Alkyl percarbonate bleach precursor forms percarbonate by perhydrolysis. Preferred precursors of this type form peracetic acid by perhydrolysis.

Preferred imide-type alkyl percarbonate precursor compounds include N-, N, N ¹ and N ^{1 in} which the alkylene group has 1 to 6 carbon atoms.
There are tetraacetylated alkylenediamines, especially compounds in which the alkylene group has 1, 2 and 6 carbon atoms. Tetraacetylethylenediamine (TAED) is particularly preferred.

Other preferred alkyl percarbonate precursors include 3,5,
There are sodium 5-tri-methylhexanoyloxybenzenesulfonate (iso-NOBS), sodium nonanoyloxybenzenesulfonate (NOBS), sodium acetoxybenzenesulfonate (ABS) and pentaacetylglucose.

Amide-Substituted Alkyl Peracid Precursors Amide-substituted alkyl peracid precursors are preferred herein, including those having the general formula:

In the formula, R ¹ is an alkyl or aryl group having 1 to 14 carbon atoms, R ² is an alkylene group having 1 to 14 carbon atoms, and R ⁵ is H or 1 to 10 carbon atoms An alkyl group, L being substantially all leaving groups. Such amide-substituted bleach activator compounds are described in EP-A-0 170 386.

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

Cationic Peroxidation Precursor The cationic peracid precursor compound forms a cationic peracid by perhydrolysis.

Generally, the cationic peracid precursor replaces the peracid portion of a suitable peracid precursor compound with a positively charged functional group, such as an ammonium or alkyl ammonium group, preferably an ethyl or methyl ammonium group. It is formed by this. The cationic peracid precursor is generally present in the solid detergent composition as a salt with a suitable anion, such as a halide ion.

The peracid precursor compound so cationically substituted may be perbenzoic acid or a substituted derivative thereof, as described above. Alternatively, the peracid precursor compound may be an alkyl percarboxylic acid precursor compound or an amide substituted alkyl peracid precursor described above.

Cationic peracid precursors are described in U.S. Pat.Nos. 4,904,406, 4,751,015, 4,988,451.
No. 4,397,757, No. 5,269,962, No. 5,127,
852, 5,093,022, 5,106,528, British Patent 1,382,594, European Patent 475,512, 458,396 and 284,29
No. 2 and Japanese Patent No. 87-318,332.

Examples of preferred cationic peracid precursors are described in UK Patent Application No. 9407944.9 and U.S. Patent Application No. 08/298903.
No. 08/298650, 08/298904 and 08/298906.

Suitable cationic peracid precursors include all ammonium or alkyl ammonium substituted alkyl or benzoyloxybenzene sulfonates, N 2
-Acylated caprolactam, and monobenzoyltetraacetylglucosebenzoyl peroxide. N-
Preferred cationic peracid precursors of the acylated caprolactam group include trialkyl ammonium methylene benzoyl caprolactam and trialkyl ammonium methylene alkyl caprolactam.

Benzoxazine organic peracid precursors Precursor compounds of the benzoxazine type, for example as described in EP-A-332,294 and EP-A-482,807, in particular Is also preferred, wherein R ₁ is H, alkyl, alkaryl, aryl, or arylalkyl.

Preformed Organic Peracids The organic peracid bleaching system combines a preformed organic peracid in addition to or instead of an organic peracid bleach precursor compound.
Generally 1-15% by weight of the composition, more preferably 1-10%
% By weight.

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

In the formula, R ¹ is an alkyl, aryl or alkaryl group having 1 to 14 carbon atoms, R ² is an alkylene, arylene or alkarylene group having 1 to 14 carbon atoms, and R ⁵ is H Or an alkyl, aryl or alkaryl group having 1 to 10 carbon atoms. Such amide-substituted organic peracid compounds are described in EP-A-01.
No. 70386.

Other organic peracids include diacyl and tetraacyl peroxides, especially diperoxidedecandionic acid, diperoxytetradecandionic acid and diperoxyhexadecandionic acid. Mono- and diperazelaic acids, mono- and diperbracyl acids and N-phthaloylaminoperoxycaproic acid are also suitable for the present invention.

Organic Peracid Bleach Release Kinetics In a preferred embodiment, a means is provided to delay the release of the organic peracid bleach into the wash solution. This measure can delay the release of the organic peracid bleach source itself into the wash solution. Alternatively, where the organic peracid source is a peracid precursor compound, the release delaying means can include means for suppressing or preventing in situ perhydrolysis that releases the organic peracid in solution. Such means include delaying the release of the hydrogen peroxide source into the solution, for example, by delaying the release of the inorganic perhydrate salt acting as the hydrogen peroxide source into the wash solution. be able to.

Release delaying means involves coating the appropriate ingredient with a coating or coating mixture designed to delay release. Thus, the coating may, for example, comprise a substance with low water solubility or be of sufficient thickness such that the dissolution rate of the coating suppresses the release rate.

The coating material can be applied in various ways. Any material is generally present in a weight ratio of coating material to bleach of 1:99 to 1: 2, preferably 1:49 to 1: 9. Suitable coating materials include triglyceride (eg, partially) hydrogenated vegetable oils, soybean oil, cottonseed oil) mono or diglycerides, microcrystalline wax, gelatin, cellulose, fatty acids and mixtures thereof.
Other suitable coating materials include calcium carbonate,
There are inorganic salts including alkali and alkaline earth metal sulfates, silicates and carbonates.

Preferred coating materials, SiO _2: Na ₂ O ratio of 1.6: 1 to 3.4: 1,
Sodium silicate, preferably 2.8: 1, as an aqueous solution, 2-10% by weight of the percarbonate (usually 3-10% by weight).
(5% by weight) to give a silicate solid. Magnesium silicate can also be included in the coating.

Combine all inorganic salt coating materials with organic binders,
Inorganic salt / organic binder composite coatings can be formed. Suitable binders, alcohol C ₁₀ -C ₂₀ alcohol ethoxylates containing 1 5 to 100 mole per mole of ethylene oxide, C ₁₅ -C ₂₀ and more preferably containing 20 to 100 moles of ethylene oxide per mole of alcohol
There are primary alcohol ethoxylates.

Other preferred binders include certain polymeric materials. Polyvinyl pyrrolidone 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 are examples of such polymeric materials. Copolymers of maleic anhydride and ethylene, methyl vinyl ether or methacrylic acid, wherein maleic anhydride constitutes at least 20 mole percent of the polymer, are another example of a polymeric material useful as a binder.
These polymeric materials, per se, or water, to be used in combination with C ₁₀ -C ₂₀ such solvents alcohol ethoxylates containing propylene glycol and 5 to 100 moles of ethylene oxide per mole of the Can be. Other examples of binding agents are, C ₁₀ -C ₂₀ mono- - and diglycerol and C ₁₀ -C ₂₀ fatty acids are also included.

Cellulose derivatives such as methylcellulose, carboxymethylcellulose, ethylhydroxyethylcellulose ether and hydroxyethylcellulose, and homo- or copolymer polycarboxylic acids or their salts are other examples of suitable binders for the present invention.

One method of applying the coating material is aggregation. Preferred agglomeration methods use any of the organic binders described above. All conventional agglomerators / mixers including, but not limited to, pans, rotating drums and vertical mixing types can be used. The molten coating material can also be applied by pouring or spraying onto a fluidized bed of bleach.

Other means to achieve the required release delay include:
There are mechanical means to change the physical properties of the bleach and control its solubility and release rate. Suitable methods include compression, mechanical injection, manual injection, and adjusting the solubility of the bleach compound by selecting the particle size of the particulate component.

The choice of particle size will depend on the composition of the particulate component and the desired release rate delay, but it is desirable that the particle size be greater than 500 micrometers, preferably with an average particle size of 800-1200 micrometers.

Another method for providing a release delay means is to provide the required release rate delay when the composition is placed in a wash solution, due to the ionic strength environment provided therein.
All other components of the detergent composition matrix are appropriately selected.

Delayed Release-Rate Parameter The organic peracid bleach component has a time to achieve a concentration that is 50% of the ultimate concentration of the peracid bleach in the T50 test method described herein for more than 180 seconds, preferably Preferably, it is released for 180-480 seconds, more preferably 240-360 seconds.

In another preferred embodiment of the present invention, the T50 described herein
The test method takes more than 180 seconds to achieve 50% of the ultimate level of total enzyme (AvO) available,
The bleaching agent is released such that it is preferably 180-480 hours, more preferably 240-360 hours. A method for determining the AvO level is disclosed in European patent application no.

In another preferred embodiment of the present invention, wherein the peracid bleach source is a peracid bleach precursor used in combination with a hydrogen peroxide source, the rate of release of hydrogen peroxide into the cleaning solution is The time to achieve a concentration that is 50% of the ultimate concentration of the hydrogen peroxide and the peracid bleach precursor exceeds 180 seconds, preferably 180-480 hours, more preferably 240-3
It is a speed that will be 60 seconds.

The ultimate wash concentration of inorganic perhydrate bleach is generally
0.005 to 0.25% by weight, preferably more than 0.05%,
More preferably, it exceeds 0.075% by weight.

The ultimate wash concentration of the peracid precursor is typically 0.001
0.00.08% by weight, preferably 0.005% to 0.05% by weight, most preferably 0.015 to 0.05% by weight.

Delayed Release-Test Method The delayed release rate of the present invention is the time to achieve 50% of the ultimate concentration / level of the component when the composition containing the component is dissolved according to the standard conditions described herein. Is determined by the “T50 test method”.

Under standard conditions, a 1 liter glass beaker
Fill with 1000 ml of distilled water at 20 ° C. and add 10 g of the composition to this. Stir the contents of the beaker using a magnetic stirrer set at 100 rpm. The magnetic stirrer has a maximum dimension of 1.5 cm,
It has a bean / seed shape with a minimum dimension of 0.5 cm. The ultimate concentration / level is the concentration / level obtained 10 minutes after adding the composition to a water-filled beaker.

After adding the composition to the water in the beaker, the accompanying components of interest are associated. A suitable analysis method is selected so that the ultimate solution concentration can be determined reliably.

Such analytical methods include those that continuously monitor the concentration level of a component, including, for example, photometry and conductivity measurements.

Alternatively, the lyser process is stopped by appropriate means, such as taking the tyler from the solution at regular time intervals and rapidly reducing the temperature of the titer, and then stopping the titer by any means such as chemical titration. A method for measuring the component concentration can also be used.

If necessary, T50 values can be calculated from the results of the analysis by methods using suitable graphs, including curve fitting.

The particular analytical method selected for measuring the concentration of a component will depend on the nature of the component and the nature of the composition containing the component.

Bleach Catalyst The compositions of the present invention can optionally include a transition metal-containing bleach catalyst. A preferred type of bleach catalyst is copper,
Heavy metal cations with defined bleach catalytic activity, such as iron or manganese cations; auxiliary metal cations with little or no bleach catalytic activity, such as zinc or aluminum cations; and catalyst and auxiliary metal cations A catalyst system comprising a sequestering agent having a distinct stability constant against, especially ethylenediaminetetraacetic acid, ethylenediaminetetra (methylenephosphonic acid) and their water-soluble salts. Such catalysts are described in U.S. Pat. No. 4,430,243.

Other types of bleach catalysts include U.S. Pat.
There is a manganese-based complex described in No. 1 and US Pat. No. 5,244,594. Preferred examples of these catalysts include Mn ^IV ₂ (u-O) ₃ (1,4,7-trimethyl-1,4,7-triazacyclononane) _2- (PF ₆ ) ₂ , Mn
^III ₂ (u-O) ₁ (u-OAc) ₂ (1,4,7-trimethyl-
1,4,7-triazacyclononane) _2- (ClO ₄ ) ₂ , Mn ^IV _{4
(U-O) 6} (1,4,7- _{triazacyclononane) 4} - (C
lO ₄ ) ₂ , Mn ^III Mn ^IV I ₄ (uO) ₁ (u-OAc) ₂ (1,
4,7-trimethyl-1,4,7-triazacyclononane) _2-
(ClO ₄ ) ₃ , and mixtures thereof. Other catalysts are described in published European patent application 549,272. Other ligands suitable here include 1,5,9-trimethyl-1,5,9-triazacyclododecane, 2-methyl-
1,4,7-triazacyclononane, 2-methyl-1,4,7-triazacyclononane, 1,2,4,7-tetramethyl-1,4,7-
There are triazacyclononane, and mixtures thereof.

For examples of suitable bleaching catalysts, see U.S. Pat.
See No. 2 and U.S. Pat. No. 5,227,084. Mn
(1,4,7-trimethyl-1,4,7-triazacyclononane _{(OCH 3) 3 - (PF} 6) of such mononuclear manganese (IV) U.S. Patent No. 5,194,416 No. disclosing complex Yet another type of bleaching catalyst described in U.S. Patent No. 5,114,606 comprises at least three consecutive C-OH
Manganese (III) containing a ligand that is a non-carboxylate polyhydroxy compound having a group, and / or (I)
V) is a water-soluble complex. Another example is N ₄ Mn
4-N- and 2-N-locations, including ^III ₆ (u + O) ₂ Mn ^IV N ₄ ) ⁺ and [Bipy ₂ Mn ^III (u-O) ₂ Mn ^IV Bipy ₂ ]-(ClO ₄ ) ₃ There is a binuclear Mn complex with a ligand.

Other suitable bleaching catalysts are described, for example, in European Patent Application No.
408,131 (cobalt complex catalyst), published European patent applications 384,503 and 306,089 (metallo-porphyrin catalyst), U.S. Pat. No. 4,728,455
Specification (Manganese / multidentate ligand catalyst), U.S. Pat.
No. 711,748 and published European patent application No. 22
4,952 (manganese absorbed on aluminosilicate catalyst), U.S. Patent Application 4,601,845 (aluminosilicate support and manganese and zinc or magnesium salts), U.S. Patent 4,626,373 (manganese / coordination) US Pat. No. 4,119,557 (ferric complex catalyst), German Patent 2,054,019 (cobalt chelate catalyst), Canadian Patent No. 866,191 (transition metal-containing salt), US Pat. No. 4,430,243 (chelates with manganese cations and non-catalytic metal cations) and US Pat. No. 4,728,455 (manganese gluconate catalyst).

Bleaching catalysts, especially Mn-containing bleach catalysts, are particularly useful in detergent compositions where the ratio of anionic to nonionic surfactants is high (e.g., 3: 1 to 1: 1), and Provides a high level of ionic strength (eg, by incorporating a high level of citrate builder and / or sodium sulfate, for example, greater than 15% by weight of the detergent composition)
I know that.

Also, bleach catalysts, especially Mn-containing bleach catalysts, have high levels (eg, greater than 8% by weight of the detergent composition) of anionic surfactants and high levels (eg, 5% by weight of the detergent composition).
) Have also been found to be particularly useful in detergent compositions comprising anionic charged organic polymeric compounds, including, for example, polycarboxylates and polyamino compounds.

Furthermore, bleach catalysts, especially Mn-containing bleach catalysts, have also been found to be particularly useful in detergent compositions containing organic compounds having a cellulose skeleton, such as cellulose ethers, including carboxymethyl cellulose.

Lime Soap Dispersant Compound The compositions of the present invention may include a lime soap dispersant compound having a lime soap dispersing power (LSDP) as defined below of 8 or less, preferably 7 or less, and most preferably 6 or less. The lime soap dispersant compound is preferably present in an amount of 0.1 to 40%, more preferably 1 to 20%, most preferably 2 to 10% by weight of the composition.

Lime soap dispersants are substances that prevent the calcium or magnesium ions from precipitating the alkali metal, ammonium or amine salts of fatty acids. The effect of lime soap dispersant is HCBorghetty and CAB
ergman, J. Am. Oil. Chem. Soc., 27, pp. 88-90, (1950)
Is given numerically by the lime soap dispersing power (LSDP) measured by the lime soap dispersing test described in. The lime soap dispersion test method is widely used by experts in this field, for example, WNLinfield, Surfact
ant Science Series, Volume 7, page 3, WNLinfield, Tenside
Surf. Det., 27, 159-161 (1990), and MKN
agarajan, WFMasler, Cosmetics and Toiletries, 104
Vol., Pp. 71-73 (1989). LSDP is 333p
pm CaCO ₃ (Ca: Mg = 3: 2) equivalent weight hardness ratio of dispersant to sodium oleate required to disperse the lime soap precipitate formed by 0.025 g of sodium oleate in 30 ml of water It is.

Surfactants with good lime soap dispersing ability include certain amine oxides, betaines, sulfobetaines, alkyl ethoxy sulfates and ethoxylated alcohols.

Exemplary surfactants LSDP used is 8 or less by the present invention, C ₁₆ -C ₁₈ dimethyl amine oxide, C ₁₂ -C ₁₈ alkyl ethoxysulfate with an average ethoxylation degree of from 1 to 5, in particular ethoxylated C ₁₂ degrees is about 3
There are CC ₁₅ alkyl ethoxy sulfates (LSDP = 4) and C ₁₃ CC ₁₅ ethoxylated alcohols with an average degree of ethoxylation of 12 (LSDP = 6) or 30 (commercially available from BASFGmbH as Lutensol A012 and Lutensol A030, respectively). .

Polymeric lime soap dispersants suitable for use herein are described in an article by MK Nagarjan and WWF Masler, Cosme
tics and Toiletries, vol. 104, pp. 71-73, (1989). Examples of such polymeric lime soap dispersants include acrylic acid, methacrylic acid or mixtures thereof, and certain water-soluble salts of acrylamide or substituted acrylamide copolymers. The molecular weight is generally between 5,000 and 20,000.

Foam control system The detergent composition of the present invention, when formulated for a machine cleaning composition, preferably comprises from 0.01 to 15%, more preferably from 0.05 to 10%, most preferably from 0.1 to 5% by weight of the composition. Including foam suppression system.

Suitable foam control systems for use herein can include substantially all known antifoam compounds, including, for example, silicone antifoam compounds and 2-alkylalkanol antifoam compounds.

The defoaming compound is a solution of the detergent composition here,
In particular, it means a compound or a mixture of compounds that acts to suppress foaming or foaming that occurs when the solution is stirred.

Particularly preferred antifoam compounds for use herein are silicone antifoam compounds, defined herein as all antifoam compounds containing a silicone component. Such silicone antifoam compounds generally also include a silica component. The term "silicone", as generally used in the present invention and throughout this industry, encompasses a variety of relatively high molecular weight aggregates containing various types of siloxane units and hydrocarbyl groups. Preferred silicone antifoam compounds are siloxanes, especially polymethylsiloxanes having trimethylsilyl endblock units.

Other suitable antifoam compounds are monocarboxylic fatty acids and their soluble salts. These materials are disclosed in U.S. Pat. No. 2,954,347, Wayne St. John on September 27, 1960.
Promulgation, is described in. The monocarboxylic fatty acids and their salts used as foam inhibitors generally have a hydrocarbyl chain having 10 to about 24, preferably 12 to 18 carbon atoms. Suitable salts include the alkali metal salts such as sodium, potassium, and lithium salts, and ammonium and alkanolammonium salts.

Other suitable antifoam compounds include, for example high molecular weight fatty esters (e.g. fatty acid triglycerides), fatty acid esters of monohydric alcohols, aliphatic C ₁₈ -C ₄₀ ketones (e.g. stearone), N- alkylated amino triazines,
For example, cyanuric chloride and 2 or 3 moles of 1 to 3 carbon atoms
Tri- to hexa-alkyl melamine or di- to tetra-alkyl diamine chlorotriazine, propylene oxide, bisstearic acid amide and monostearyl dialkali metal formed as a reaction product of a primary or secondary amine which is 24 (Eg sodium, potassium, lithium) phosphates and phosphates.

Preferred foam control systems include: (a) an antifoam compound, preferably a silicone antifoam compound,
Most preferably, (i) 50-99%, preferably 75-95%, by weight of the silicone antifoam compound, of polydimethylsiloxane; and (ii) 1-50%, by weight of the silicone / silica antifoam compound,
Silicone antifoam compounds comprising preferably 5 to 25% by weight of a silica combination, wherein the silica / silicone antifoam compound comprises 5 to 50% by weight, preferably 10 to 10% by weight.
(B) 0.5 to 10%, preferably 1 to 10% by weight of a dispersant compound, most preferably 72 to 78% polyoxyalkylene content, propylene of ethylene oxide Silicone glycol rake with a ratio to oxide of 1: 0.9-1.1
Copolymers (particularly preferred silicone glycols of this type
rake copolymers are commercially available from DOW Corning under the trade name DCO544), (c) 5 to 80%, preferably 10 to 70%, by weight of an inert carrier fluid compound (most preferably having a degree of ethoxylation of 5-50, preferably comprise comprising C ₁₆ -C ₁₈ ethoxylated alcohols 8 to 15).

A highly preferred particulate foam control system is described in EP-A-0210731 and comprises a silicone defoaming compound and an organic carrier material having a melting point of 50 ° C. to 80 ° C., comprising an organic carrier. The material comprises a monoester of glycerol and a fatty acid having a carbon chain of 12 to 20 carbon atoms. European Patent No. EP-A-
No. 0210721 discloses another preferred particulate foam control system wherein the organic carrier has 12 carbon atoms.
Fatty acids or alcohols having a carbon chain of 2020, or mixtures thereof, melting at 45 ° C. to 80 ° C.

Polymeric dye transfer inhibitor The detergent composition of the present invention comprises 0.01 to 10% by weight, preferably
0.05 to 0.5% by weight of a polymeric dye transfer inhibitor may also be included.

The polymeric dye transfer inhibitor is preferably a polyamine N
-Selected from oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, polyvinylpyrrolidone polymers or combinations thereof.

a) Polyamine N-oxide polymers Polyamine N-oxide polymers suitable for use herein comprise units having the following structural formula:

In the formula, P is a polymerizable unit, and A is x is 0 or 1; R is an aliphatic, ethoxylated aliphatic, aromatic, heterocyclic or alicyclic group or a combination thereof, wherein N-
The nitrogen of the O group can be added or the nitrogen of the NO group is part of these groups.

 The NO group is represented by the following general structure.

Wherein R ₁ , R ₂ , and R ₃ are aliphatic groups, aromatic, heterocyclic or alicyclic groups or combinations thereof, and x and / or y and / or z are 0 or 1 , N
The nitrogen of the -O group can be added, or the nitrogen of the NO group forms part of these groups. The NO group may be part of the polymerizable unit (P) or may be added to the polymer backbone, or a combination of both.

Suitable polyamine N-oxides wherein the N-O group forms part of a polymerizable unit include those wherein R is aliphatic, aromatic,
Polyamine N- selected from alicyclic or heterocyclic groups
There are oxides. One category of the polyamine N-oxides is the polyamine N-oxides of the group where the nitrogen of the NO group forms part of the R group. Preferred polyamine N-oxides are those in which R is a heterocyclic group, for example pyridine,
Pyrrole, imidazole, pyrrolidine, piperidine, quinoline, acridine and their derivatives.

Other suitable polyamine N-oxides are polyamine oxides in which the N-O groups are attached to polymerizable units. A preferred class of these polyamine N-oxides has the general formula (I) wherein R is an aromatic, heterocyclic or alicyclic group and the nitrogen of the NO functional group is part of the R group. Is a polyamine N-oxide. Examples of these classes are polyamine oxides where R is a heterocyclic compound, such as pyridine, pyrrole, imidazole and derivatives thereof.

Polyamine oxides can be obtained with almost all polymers. The degree of polymerization is not critical as long as the material has the desired water solubility and dye dispersing power. Generally, the average molecular weight is between 500 and 1000,000.

b) Copolymers of N-vinylpyrrolidone and N-vinylimidazole Preferred here are N-vinylimidazole and N-vinylpyrrolidone copolymers having an average molecular weight of 5,000 to 50,000. Preferred polymers have a molar ratio of N-vinylimidazole to N-vinylpyrrolidone of 1 to 0.
2

c) Polyvinylpyrrolidone The detergent composition of the present invention has an average molecular weight of 2,500 to 400,000.
Polyvinylpyrrolidone ("PVP") can also be used. A suitable polyvinylpyrrolidone is ISP Corpor
product name PV from ation, New York, NY and Montreal, Canada
PK-15 (viscosity molecular weight 10,000), PVP K-30 (average molecular weight
40,000), PVP K-60 (average molecular weight 160,000), and
It is commercially available as PVP K-90 (average molecular weight 360,000). PV
PK-15 is also available from ISP Corporation. BASF Cor
Other suitable polyvinylpyrrolidones commercially available from poration include Sokalan HP 165 and Sokalan HP 12.

d) Polyvinyl oxazolidone In the detergent composition of the present invention, polyvinyl oxazolidone may be used as a polymer dye transfer inhibitor. The polyvinyl oxazolidone has an average molecular weight of 2,500 to 400,0
00.

e) Polyvinylimidazole In the detergent composition of the present invention, polyvinylimidazole may be used as a polymer dye transfer inhibitor. The polyvinyl imidazole preferably has an average molecular weight of 2,500
~ 400,000.

Optical Brightener The detergent compositions of the present invention can also optionally contain from about 0.005 to 5% by weight of certain hydrophilic optical brighteners.

As the hydrophilic optical brightener useful in the present invention, there is a substance having the following structural formula.

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

Where R ₁ is alinino, R ₂ is N-2-bis-hydroxyethyl and M is a proton ion such as sodium, the brightener is 4,4′-bis [ (4-anilino-6- (N-2-bis-hydroxyethyl) -s-triazin-2-yl) amino] -2,2 '
-Stilbene disulfonic acid and disodium salt. This special brightener is available from Ciba-Geigy Corporat
It is commercially available from Ion under the trade name Tinopal-UNPA-GX.
Tinopal-UNPA-GX is useful in the detergent compositions of the present invention.
Preferred hydrophilic optical brighteners.

In the above formula, when R ₁ is anilino, R ₂ is N-2-hydroxyethyl-N-2-methylamino, and M is a cation such as sodium, the ply toner is 4, Disodium salt of 4'-bis [(4-anilino-6- (N-2-hydroxyethyl-N-methylamino) -s-triazin-2-yl) amino] -2,2'-stilbenzenesulfonic acid It is. This special brightener is commercially available from Ciba-Geigy Corporation under the trade name Tinopal 5BM-GX.

In the above formula, where R ₁ is anilino, R ₂ is morpholino, and M is a cation such as sodium, the brightener is 4,4′-bis [(4-anilino-6).
-Morpholino-s-triazin-2-yl) amino]
-2,2'-Stilbene disulfonic acid, sodium salt. This special brightener is available from Ciba-Geigy Corporat
It is commercially available from Ion under the trade name Tinopal AMS-GX.

Softener The fabric detergent softener of the present invention may also contain a fabric softener. These softeners can be inorganic or organic. Inorganic softeners are represented by smectite clays described in GB-A-1400898. Organic fabric softeners include British Patent GB-A-
1514276 and EP-B-00113
There are water-soluble tertiary amines described in US Pat.

The amount of smectite clay is generally 5-15% by weight,
More preferably from 8 to 12% by weight, the material is added as a dry mix component to the rest of the composition. Organic fabric softeners such as water-insoluble tertiary amines or long-chain amide materials are
It is blended in an amount of 0.5 to 5% by weight, usually 1 to 3% by weight, but the high molecular weight polyethylene oxide material and the water-soluble cationic material are 0.1 to 2% by weight, usually 0.15 to 1.5% by weight.
The amount is mixed.

Other Optional Ingredients Other optional optional ingredients suitable for incorporation into the compositions of the present invention include flavors, colorants and filler salts, with sodium sulfate being the preferred filler salt.

Composition Forms The detergent compositions of the present invention can be formulated in any desired form, such as powders, granules, pastes, liquids and gels. Preferably, the composition is not in tablet form. Most preferably, the composition is in a granular form.

Liquid Composition The detergent composition of the present invention can be formulated as a liquid detergent composition. Such liquid detergent compositions generally contain 94
~ 35 wt%, preferably 90-40 wt%, most preferably
It comprises 80 to 50% by weight of a liquid carrier, for example water, preferably a mixture of water and an organic solvent.

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

Solid Composition The detergent composition of the present invention is preferably in the form of a solid, such as a powder and granules. Granular form is preferred.

The particle diameter of the component of the granular composition of the present invention is preferably such that 5% or less of particles having a diameter of more than 1.4 mm is 0.15 mm or less.
Less than 5% of the particles.

The bulk density of the granular detergent composition of the present invention is generally at least 450 g / liter, more usually at least 600 g / l.
g / liter, more preferably 650 g / liter to 1200 g / liter.

Bulk density is measured using a simple funnel and cup apparatus consisting of a conical funnel tightly molded on a foundation. The lower end of the funnel is equipped with a flap valve so that the contents of the funnel can be emptied into an axially aligned cylindrical cup located below the funnel. The upper and lower ends of the funnel are 130 mm and 40 mm, respectively. The funnel is mounted so that its lower end is 140 mm above the upper surface of the foundation. The total height of the cup is 90mm, the inside height is 87mm and the inside diameter is
84 mm. The nominal volume of the cup is 500 ml.

During the measurement, the funnel is filled with powder by hand, the flap valve is opened and the cup is overfilled with powder. Remove the filled cup from the frame and pass an instrument with a straight blade, such as a knife, across the top edge of the cup to remove excess powder. The filled cup is then weighed and the value obtained for the weight of the powder is doubled, indicating the bulk density in g / l. Repeat the measurement as needed.

Production Method-Granular Composition Generally, the granular detergent composition of the present invention is dry-mixed,
It can be manufactured in various ways, including spray drying, agglomeration and granulation.

Washing methods The compositions of the present invention can be used in virtually any washing or washing method, including machine washing and dishwashing methods.

Mechanical Dishwashing Method A preferred mechanical dishwashing method comprises dissolving an effective amount of a soiled product selected from pottery, glassware, silver basins and cutlery and mixtures thereof, or a dishwashing composition of the present invention, or Treat with the metered aqueous solution. An effective amount of a dishwashing composition generally means 8 g to 60 g of a product dissolved or dispersed in a 3 to 10 liter volume of a washing solution, which is commonly used in conventional mechanical dishwashing methods. Representative product usage and wash solution volume.

Machine Washing Method In a machine washing method, soiled laundry is treated with a washing solution in a washing machine in which an effective amount of a machine laundry detergent composition of the present invention has been dissolved or dispensed. The detergent can be added to the washing solution via the metering device aspirator of the washing machine or by the metering device. An effective amount of the detergent composition is 40 g to 300 g dissolved or dispersed in a washing solution having a volume of 5 to 6 liters, which is a typical product usage amount and a washing solution volume generally used in a normal machine washing method. Means the product.

In the preferred washing method here, the dosing device containing the effective amount of the detergent composition is placed in the drum of a previously loaded washing machine before the washing cycle is started.

The dosing device is a container for the detergent product, which is used to discharge the product directly into the drum of the washing machine. The volume should be such that it can hold enough detergent product commonly used in the washing method.

After placing the laundry in the washing machine, a dosing device containing the detergent product is placed inside the drum. When starting the washing cycle of the washing machine, water is put into the drum and the drum is rotated periodically. The dosing device is designed to accommodate the dry detergent product, but to be able to release the product during the wash cycle in response to agitation as the drum rotates and as a result of being immersed in the wash water. Should.

The device may have a number of openings through which the product can pass in order to release the detergent product during washing. Alternatively, the device can be made of a material that allows the passage of liquid but not the solid product, so that the dissolved product can pass. Preferably, the detergent product is released quickly at the beginning of the washing cycle, thereby providing a locally concentrated product in the washing machine drum at this stage of the washing cycle.

The dosing device is preferably designed to be reusable and to maintain the integrity of the container, both in the dry state and in the washing cycle. Particularly preferred dosing devices for use in accordance with the invention are GB-B-2,157,717, GB-B-2,157,718, EP-E.
It is described in the specifications of P-A-0201376, EP-A-0288345 and EP-A-0288346.
Article by J. Bland, Manufacturing Chemist 1989 11
Tsuki Shuppan, pp. 41-46, also describes particularly preferred dosing devices for use in granular laundry products of the type commonly referred to as "granules."

Particularly preferred dosing devices are disclosed in published European patent application 03
Nos. 43069 and 0343070. The latter application describes an apparatus comprising a flexible sheath in the form of a bag extending from a support ring defining an orifice, the orifice providing sufficient product to a bag for one washing cycle in a washing method. It is designed to fit. A portion of the selection medium flows through the orifice into the bag, dissolving the product, and then the solution flows out through the orifice and into the washing medium. The support ring is provided with a mask mechanism to block wet, undissolved product, which generally includes walls extending radially from a central boss in a spoked wheel structure. Or the wall has a similar structure with a helical shape.

Abbreviations used in the examples In the detergent composition, the components represented by the abbreviations have the following meanings.

LAS: linear C ₁₂ sodium alkylbenzene sulfonate TAS: sodium tallow alkyl sulfate C45AS: C _{14 to} C ₁₅ linear sodium alkyl sulfate CxyEzS: C _{1x to} C _1y condensed with z mole of ethylene oxide
Sodium branched alkyl sulfate CxyEz: C condensed with an average of z moles of ethylene oxide
Of _1x-1y, mainly straight-chain primary alcohols ^{_{QAS: R 2 .N + (CH}} 3) 2 (C 2 H 4 OH), wherein, R ₂ = C ₁₂ ~C ₁₄ soap: tallow and coconut oil Sodium linear alkyl carboxylate derived from 80/20 mixture TFAA: C ₁₆ -C ₁₈ alkyl N-methylglucamide TPKFA: C ₁₂ -C ₁₄ topped whole cut fatty acid STPP: anhydrous sodium tripolyphosphate zeolite A: formula Na ₁₂ ( AlO ₂ SiO _{2) 12} .27H ₂ hydrated sodium aluminosilicate of O, primary particle diameter of 0.1 to 10 micrometers NaSKS-6: crystalline layered silicate of citric acid of the formula _{δ-Na 2 Si 2 O 5} : anhydrous citric Acid Carbonate: anhydrous sodium carbonate, particle size 200 μm to 900 μm Bicarbonate: anhydrous sodium bicarbonate, particle size distribution 400 μm
12001200 μm silicate: amorphous sodium silicate (SiO ₂ : Na ₂ O ratio 2.0) sodium sulfate: anhydrous sodium sulfate citrate: trisodium citrate dihydrate, activity 86.4
%, Particle size distribution 425 μm to 850 μm MA / AA: copolymer of maleic acid / acrylic acid 1: 4, average molecular weight about 70,000 CMC: sodium carboxymethylcellulose Protease: protease, activity 4KNPU / g, Sav
Alcalase: Proteolytic enzyme, activity 3AU / g, NOVO Indus
tries Sell from A / S Cellulase: Cellulase degrading enzyme, activity 1000CEVU / g, NO
Amylase: amylolytic enzyme, active 120KNU / g, NOVO I from VO Industries A / S under the trade name Carezyme
Sold under the trade name Termamyl 120T from ndustries A / S Lipase: lipolytic enzyme, activity 100KLU / g, NOVO Industr
Endoase: Endoglucanase enzyme, active 3000CEVU, sold under the trade name of Lipolase from ies A / S
/ g, sold by NOVO Industries A / S PB4: nominal formula NaBO ₂ .3H ₂ OH ₂ O ₂ of sodium perborate tetrahydrate PB1: nominal formula NaB ₂ .H ₂ O ₂ in anhydrous sodium perborate bleach agent percarbonate: nominal formula 2Na ₂ CO ₃ .3H ₂ sodium percarbonate O ₂ NOBS: nonanoyl the form of the sodium salt oxybenzene sulfonate TAED: tetraacetylethylenediamine DTPMP: diethylene triamine penta (methylene phosphonate), from Monsanto Sold under the trade name Dequest 2060 Photoactivated bleach: sulfonated zinc phthalocyanine brightener encapsulated in dextrin-soluble polymer 1: disodium 4,4'-bis (2-sulfostyryl) biphenyl brightener 2: Disodium 4,4'-bis (4-anilino-6-morpholino-1,3,5-triazin-2-yl)
Amino) stilbene-2: 2'-disulfonate HEDP: 1,1-hydroxyethanediphosphonic acid PVNO: polyvinylpyridine N-oxide PVPVI: copolymer of polyvinylpyrrolidone and vinylimidazole SRP1: oxyethyleneoxy and terephthaloyl skeleton Sulfobenzoyl end-capped ester SRP2: short block polymer of diethoxylated poly (1,2 propylene terephthalate) Silicone defoamer: polydimethylsiloxane foam modifier containing siloxane-oxyalkylene copolymer as dispersant, foam control Ratio of the agent to the dispersant 10: 1-100:
1 In the examples below, all amounts are given as weight percent of the composition. The amount of aluminosilicate builder in these examples is given on an active basis.

Example 1 The following laundry detergent compositions A to F were produced according to the present invention. BF are according to the invention, A is a comparative composition. The T50 for peracid release into the cleaning solution, as measured by the T50 test method described herein, is greater than 180 seconds for each of the AF compositions.

Performance Comparison Test Test Method-Stain Removal Two white cotton sheets were prewashed with a non-biobleach free heavy duty detergent. Then, using a paint brush, dirt was uniformly applied to these cotton sheets in stripes of 2 cm width. The first sheet was stained with porridge stained with chocolate, and the second sheet was stained with chocolate pudding. Soil containing chocolate has been found to be sensitive to enzymes. A set of test cloth pieces having a size of 6 cm × 6 cm was cut out from each sheet. These sets of cloth pieces were subjected to a wash cycle using Composition A or Composition B as a detergent. This washing cycle was repeated for each of the eight sets of cloth pieces prepared as described above.

More specifically, use a Miele 820 automatic washing machine at 20 ° C
Selected the short cycle program. Water of 12 ゜ Clark hardness (= 1.8 mmol Ca ²⁺ / liter) was used. Detergent 140
g was metered through the suction device. Use a piece of cloth of each stain type 60/4 of a lightly stained synthetic and cotton fabric.
Washed with additional laundry comprising 2.0 kg of 0 mixture.
Additional laundry was placed prior to the start of the wash cycle and ensured distribution around the test cloth benzoyl.

Four well-known Scheffe by four judges
Using the scale, all pieces of cloth were assessed for removal of the two chocolate containing stains and the results for the eight comparisons were averaged.

Comparative Test-Results Following the soil removal test described above, the efficiencies of compositions A and B in the above soil removal were compared.

 The results obtained (PSU) are as follows.

Thus, it can be seen that the soil removal performance of the composition B of the present invention for chocolate stains is enhanced as compared with that of the composition A.

Example 2 According to the invention, the following granular detergent compositions GI having a bulk density of 750 g / l were prepared.

Example 3 The following inventive detergent composition was prepared.

Example 4 A bleach-free detergent composition was prepared according to the invention, particularly for use in washing colored garments, as described below.

Example 5 The following detergent composition of the present invention was prepared.

Example 6 The following high density bleach-containing detergent composition of the present invention was prepared.

Example 7 The following high-density detergent composition of the present invention was prepared.

Continuation of the front page (72) Inventor Allison, Leslie, Maine Tyne, And, Ware, Whitley, Bay, St., Pauls, Gardens, UK 12 (56) References JP-A-2-178398 (JP, A) Kaihei 2-178399 (JP, A) (58) Field surveyed (Int. Cl. ⁷ , DB name) C11D 7/42 C11D 3/386

Claims (12)

(57) [Claims] 1. An amylase enzyme, (b) a builder system comprising (i) and (ii) below, (i) an aluminosilicate zeolite, and (ii) a crystalline layered silicate; Here, the weight ratio of the crystalline layered silicate to the amylase enzyme (120 KNU / gram activity basis) is 8: 1 to 18: 1.
A detergent composition comprising: (c) a bleaching agent. 2. The detergent composition according to claim 1, wherein said amylase enzyme is α-amylase. 3. The detergent composition according to claim 1, wherein the amylase enzyme is present in an amount of 0.2 to 3% by weight of the composition (based on 120 KNU / g activity). 4. The method of claim 1, wherein said aluminosilicate zeolite is present in a builder system in an amount of 40% by weight of active aluminosilicate zeolite.
A detergent composition according to any of the preceding claims, being present in an amount of from% to 98%. 5. The detergent composition according to claim 1, wherein the crystalline phyllosilicate has the following general formula. NaMSi _x O _{2X + 1} .yH ₂ O (where M is sodium or hydrogen and x is 1.9 to
4 is a number and y is a number from 0 to 20) 6. The crystalline phyllosilicate according to claim 1, wherein the builder system contains 1
6. A method as claimed in claim 1, wherein the amount is from about 35% by weight.
The detergent composition according to Item. 7. The detergent composition according to claim 1, wherein the builder system further contains an organic polymer compound. 8. The detergent composition according to claim 7, wherein the organic polymer compound contains an acrylic acid monomer unit. 9. The detergent composition according to claim 7, wherein the organic polymeric compound is present in an amount of from 0.1% to 20% by weight of the organic polymeric compound of the builder type. 10. The organic peracid bleaching system according to claim 10, wherein said organic peracid is bleached such that the time required to achieve a concentration of 50% of the ultimate concentration of the organic peracid in the T50 test method exceeds 180 seconds. The detergent composition according to any of the preceding claims, comprising means for delaying the release of the acid into the cleaning solution. 11. The detergent composition according to claim 1, which is in the form of granules. 12. Use of the detergent composition according to claim 11 in a washing method, wherein the detergent composition is added to the washing solution using a metering device placed in the drum of the washing machine before the start of washing. Use characterized by adding.