JP2001515952A - Bleaching composition - Google Patents

Abstract

  (57) [Summary] The present invention relates to a granular detergent composition comprising a special bleach system comprising a hydrophobic and a hydrophilic peracid bleach and a peroxide source, in particular a low density, phosphate containing detergent composition. Wherein the available oxygen from the hydrophobic and hydrophilic peracid bleach is at a specific low level, the available oxygen from the hydrophobic peracid bleach and the available oxygen from the hydrophilic peracid bleach Are in a specific ratio and the available oxygen of the peroxide source and the available oxygen of the peracid are in a specific ratio. The invention also relates to the use of a special mixed bleach system for disinfecting or reducing bacterial activity.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001] The present invention relates to suitable bleach-containing composition for use in the laundering process.

BACKGROUND OF THE INVENTION In the past few decades, research efforts have been directed at developing organic peracid-based bleaching systems that can effectively remove dyes and / or stains from fabrics at low wash temperatures. . Organic peracids are the in situ perhydrolysis of organic peracid bleach precursor compounds (bleach activators)
(perhydrolysis).

A commonly used precursor compound is tetraacetylethylenediamine (TAED), which provides an effective hydrophilic wash, especially for beverage dyeing. To achieve effective bleaching of detergents, it is necessary to bleach both hydrophobic and hydrophilic stains in a bleaching system. Therefore, other organic peracid precursor compounds have been developed that address hydrophobic dyeing and staining. Various publications disclose the use of mixtures of hydrophobic and hydrophilic bleaches in detergents (for example JP 7-238298, DE 196,16,782, International (Patent No. WO94 / 28103)
. However, the inventor has found that prior art bleaching compositions may require, for example, low wash temperatures, low agitation, low use of detergent actives, severely soiled fabrics, high levels of metal ions, or It has been found that when used under severe conditions, such as after storage at high humidity or high temperature, it is not always possible to achieve satisfactory results. These problems are especially encountered in low density detergents, especially when the overall level of bleach system in the detergent composition is low, and in detergents that are high in phosphate builders that can introduce metal ions into the wash liquor. Also happens.

In addition, to achieve an efficient bleach system, the system should provide good bleaching at low levels, thereby minimizing the chance of damaging the fabric.

[0005] Therefore, there is a need to provide a detergent composition comprising a low level of bleaching system and having very effective bleaching performance against both hydrophilic and hydrophobic stains under severe conditions. .

Here we have surprisingly found that available oxygen (Av) containing low levels of bleach activator and peroxide source, ie, derived from hydrophobic and hydrophilic bleach activators.
O) is less than 5000 ppm, the ratio of hydrophobic activator AvO to hydrophilic AvO is 3: 1 to 1:50, and the ratio of total AvO to activator AvO exceeds 2: 1 It has been found that by using the composition, excellent bleaching can be achieved under severe conditions. This bleach system has been found to be particularly useful in low-density detergents, in hand-wash detergents, in phosphate-containing compositions, and also in washing methods using low concentrations of detergents.

[0007] In general, bleaching agents, especially hypochlorite bleaching agents, are known to be bactericidal. High levels of bleach are generally required to reduce or eliminate bacteria sufficiently. Thus, most detergents comprising bleach systems known in the art contain only low levels of bleach and are not effective as sanitizing fungicides.

The present inventors have discovered that mixed bleach systems comprising specific levels and ratios of hydrophobic, hydrophilic bleach additives and peroxide sources are very effective as fungicides. .

[0009] Even when low levels of special bleaching compositions are used in washing solutions or detergents or detergents, the use of the bleaching components in the specific ratios described above effectively kills the washed fabric or surface. , Or bacteria were found to be effectively reduced.

[0010] All references cited in this description are relevant and are hereby incorporated by reference.

SUMMARY OF THE INVENTION The present invention has a density of from 330 g / liter to 700 g / liter comprising a bleaching system comprising a hydrophilic and a hydrophobic peracid bleach or a precursor thereof and a peroxide source. A detergent composition, wherein the total amount of available oxygen (AvO-a) from the hydrophilic and hydrophobic peracid bleach is less than 5000 ppm by weight of the composition, wherein the hydrophobic peracid or its precursor The ratio of available oxygen (AvO-hb) to the available oxygen (AvO-hp) of the hydrophilic peracid or its precursor is 3: 1 to 1:50, and the available oxygen (AvO-h -O) and the ratio of AvO-a is at least 2
: 1.

[0012] DETAILED DESCRIPTION detergent composition of the present invention, the total amount is less than 5000 ppm of available oxygen (AvO-a) derived from the hydrophilic and hydrophobic peracid bleaching agents or their precursors, or 40
Less than 00 ppm, or less than 3000 ppm, or less than 2500 ppm.

The ratio between the available oxygen (AvO-hb) of the hydrophobic peracid or its precursor and the available oxygen (AvO-hp) of the hydrophilic peracid or its precursor is preferably 3: 1 to 1:50, more preferably. Is 2.5: 1 to 1:30, furthermore 2: 1 to 1:20.

The ratio of available oxygen (AvO-o) and AvO-a of the peroxide source is at least 2
: 1, preferably at least 3: 1, even 4: 1.

The density of the composition is preferably between 370 g / l and 700 g / l, and more preferably
It is 650 g / l, and further 〜600 g / l.

The composition is preferably a low-density granular composition, especially a phosphate-containing composition, especially a highly effervescent composition, a dipping or pre-treatment composition, a manual cleaning composition.

Thus, the present invention also relates to a method of manually washing laundry, or pretreating or immersing laundry, using the detergent composition of the present invention.

The present invention comprises a hydrophobic and hydrophilic peracid bleach or precursor thereof, and a peroxide source, wherein the ratio of AvO-hb to AvO-hp is 3: 1 to 1: 1.
: 50, preferably 2.5: 1 to 1:10, more preferably 2: 1 to 1:20,
The ratio of AvO-o to AvO-a is at least 2: 1, preferably at least 3:
1, or even a 4: 1 bleaching composition, for use in reducing bacterial activity.

As used herein, “reducing the activity of a bacterium” includes killing the bacterium or a part thereof, and inhibiting further growth or proliferation of the bacterium.

Preferably, the bleaching composition is used to sanitize the fabric or surface to be washed with the bleaching composition. In the sanitizing method, the fabric or surface containing the bacteria, especially those where the bacteria are present in a dye on the fabric or surface, is contacted with the composition. Thus, the present invention sanitizes fabrics by contacting the fabrics with a composition or a solution of the composition comprising a hydrophilic and hydrophobic peracid bleach or their precursors and a peroxide source. A method of producing a hydrophobic peracid or a precursor available oxygen (
The ratio of AvO-hb) to the available oxygen (AvO-hp) of the hydrophilic peracid or its precursor is 3: 1 to 1:50, and the available oxygen (AvO-o) of the peroxide source and the hydrophilic Also included is a process characterized in that the ratio of the acidic and hydrophobic peracid bleach to the total amount of available oxygen (AvO-a) is at least 2: 1.

The bleaching composition is preferably present in a cleaning composition for fabric or surface cleaning, preferably a laundry or dishwashing detergent or hard surface cleaner. Laundry detergent compositions comprising the components described below are preferred.

The level of AvO-a in a cleaning or detergent composition, or a solution thereof, including a bleaching composition and used to reduce bacterial activity, is preferably 10,
Up to 000 ppm, more preferably up to 5,000 ppm, and even 4,000 ppm
Or even up to 3,000 ppm or 2,500 ppm.

Preferred hydrophilic and hydrophobic peracid bleaches or their precursors and preferred peroxide sources are described below.

Hydrophobic and hydrophilic peracid bleaches or precursors thereof An essential component of the detergent composition of the present invention is a hydrophobic peracid or a precursor thereof. The bleaching system preferably has the formula R ¹ -CO ₃ M (wherein R ¹ has at least 6 carbon atoms and M is a counter ion) or the following formula R ¹ -COL (where L is Is a leaving group bonded to the R ¹ —CO— group by an oxygen atom, and R ¹ has at least 6 carbon atoms) and / or a precursor thereof. Preferred leaving groups are benzoic acid and its derivatives, especially benzenesulfonate.

A percarboxylic acid bleach precursor is a compound that reacts with hydrogen peroxide in a perhydrolysis reaction to form a percarboxylic acid.

The counter ion M of the percarboxylic acid is preferably sodium, potassium or hydrogen.

Preferably, such a hydrophobic peracid or precursor thereof has a critical micelle concentration of its parent carboxylic acid of less than 0.5 mol / l, measured at 20-50 ° C. in an aqueous solution. A certain compound.

The percarboxylic acid, preferably a percarboxylic acid formed from the precursor, has at least 7 or at least 8 or 9 carbon atoms and has 7 to 12 carbon atoms.
Is more preferably 8 to 11, and most preferably 9 or 10. In a preferred embodiment, the percarboxylic acid or peracid formed from the precursor has at least 7, more preferably at least 8, and most preferably 9 carbon atoms.
Having an alkyl chain of

The percarboxylic acid precursors include all esters described as bleach activators for use in laundry detergents, such as the alkyl percarboxylic acid precursors described herein,
Sugar esters such as pentaacetylglucose, esters of imidic acid such as ethylbenzimidate triacyl cyanurate such as triacetyl cyanurate and tribenzoyl cyanurate, and relatively surface-active oxidizing substances such as GB-A-864798, GB-A
Such as described in EP A-1147871 herein _{C 8-18} alkanoic acid (alkan
oic acid) or -aralkanoic acid, and the esters described in EP-A-98129 and EP-A-106634.

Preferred materials are C _14-22 alkanoic or alkenoic acid
) Phenyl ester, hydroxylamine ester, lower alkanoic acid and gem-
Gem-diesters of idols, such as the substances disclosed in EP-A-0125781, especially 1,1,5-triacetoxypent-4-ene and 1,1,5,5-tetraacetoxy Pentane and the corresponding butene and butane compounds, ethylidene benzoate acetate and bis (ethylidene acetate) adipate and enol esters, for example European Patent EP-
They may be the substances described in A-01406648 and EP-A-092932.

Other highly preferred hydrophobic alkyl percarboxylic acid precursors include decanoyloxybenzoic acid or a salt thereof, dodecanoyloxy-benzenesulfonate sodium or potassium salt, decanoyloxy-benzenesulfonate sodium or potassium salt ( DOBS), sodium or potassium benzoyloxy-benzenesulfonate (BOBS), more preferably sodium or potassium 3,5,5-tri-methylhexanoyloxybenzenesulfonate (iso-
NOBS) and more preferred sodium or potassium nonanoyloxybenzenesulfonate (NOBS).

Amide-substituted bleach activator compounds, such as EP-A-01
The materials described in 70386 are also useful herein. Suitable examples of this group of materials include precursors or acids such as (6-hexylamino) -6-oxo-caproic acid, (6-octylamino) -6-oxo-caproic acid, (6-nonylamino) -6-oxo-caproic acid, (6-decylamino) -6-oxo-
Caproic acid, magnesium monoperoxyphthalate hexahydrate, salts of meta-chloroperbenzoic acid, 4-nonylamino-4-oxoperoxybutyric acid and diperoxide decandionic acid, or precursors thereof, especially benzenesulfonate leaving groups Substances. Such bleach is disclosed in U.S. Pat. No. 4,483,78.
No. 1, US Pat. No. 4,634,551, European Patent No. 0,1
No. 33,354, U.S. Pat. No. 4,412,934 and EP 0,170,386.

Other suitable organic peracids include diperoxyalkandioic acids having more than 7 carbon atoms, such as diperoxidedecandionic acid (DPDA), diperoxytetradecandionic acid and diperoxyhexadecandionic acid. Mono- and di-perazelaic acid, mono- and di-perbrachialic acid and N-phthaloylaminoperoxycaproic acid (PAP), nonanoylamide peroxo-adipic acid (
NAPAA) and hexanesulfenoylperoxypropionic acid are also suitable here.

The composition preferably has the following formula R ¹ —CO ₃ M (where R ¹ has less than 6 carbon atoms and M is a counter ion) or the following formula R ¹ —COL ( Wherein L is a leaving group bonded to the R ¹ —CO— group with oxygen, and R ¹ has less than 6 carbon atoms), or a precursor thereof. A preferred hydrophilic precursor is TAED.

Peroxide Source Inorganic perhydrate salts are a preferred source of peroxide. These salts are preferably present in an amount of 0.01 to 30% by weight, more preferably 0.5 to 10% by weight. 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 perhydrate salts, a preferred embodiment of such a granular composition uses a coated form of the material to improve the storage stability of the perhydrate salt in the granular product. are doing. 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.

[0036] Sodium perborate is a preferred perhydrate salt may be in the form of a tetrahydrate of the monohydrate or _{NaBO 2 H 2 O 2 · 3H} 2 O nominal formula NaBO ₂ H ₂ O ₂ .

[0037] Alkali metal percarbonates, especially sodium percarbonate, are the preferred perhydrates here. Sodium percarbonate is an adduct having the formula corresponding to 2Na ₂ CO ₃ .3H ₂ O ₂ and is commercially available as a crystalline solid.

[0038] Potassium peroxymonopersulfate is another inorganic perhydrate salt used in the present detergent compositions.

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.

The composition of the present invention comprises other surfactants, other bleaching agents, bleach catalysts, alkalinity systems, builders, phosphate-containing builders, organic polymer compounds, enzymes, foam inhibitors, lime soaps It preferably comprises one or more additional detergent components selected from dispersants, soil dispersants and anti-redeposition agents, soil release agents, fragrances, brighteners, photobleaches, and additional corrosion inhibitors.

Bleach Catalyst Bleach systems can include a transition metal containing bleach catalyst. Suitable types of bleach catalysts include transition metal cations having defined bleach catalytic activity, such as copper, iron or manganese cations, and auxiliary metal cations having little or no bleach catalytic activity, such as zinc or aluminum. Catalytic system comprising a cation and a sequestering agent having a defined stability constant for the catalyst and auxiliary metal cations, especially ethylenediaminetetraacetic acid, ethylenediaminetetra (methylenephosphonic acid) and their water-soluble salts It is. Such catalysts are described in U.S. Pat. No. 4,430,243.

Another type of bleach catalyst is disclosed in US Pat. No. 5,246,621 and US Pat.
Includes manganese-based complexes described in Japanese Patent No. 5,244,594.
. Preferred examples of these catalysts include Mn^IV ₂(uO)₃(1,4,7-trim
Tyl-1,4,7-triazacyclononane)₂-(PF₆)₂ , Mn^III ₂(u-
O)₁(u-OAc)₂(1,4,7-trimethyl-1,4,7-triazacyclononane)₂− (ClO₄)₂ , Mn^IV ₄(uO)₆(1,4,7-triazasi chrononane)₄− (ClO₄)₂ , Mn^IIIMn^IV ₄(uO)₁(u-OAc
)₂(1,4,7-trimethyl-1,4,7-triazacyclononane)₂-(ClO ₄ )₃ , And mixtures thereof. Other catalysts have published European patents
No. 549,272. Other suitable ligands here include:
1,5,9-trimethyl-1,5,9-triazacyclododecane, 2-methyl-
1,4,7-triazacyclononane, 2-methyl-1,4,7-triazacyclo
Nonane, 1,2,4,7-tetramethyl-1,4,7-triazacyclononane,
And mixtures thereof.

For examples of suitable bleach catalysts, see US Pat. No. 4,246,612 and US Pat. No. 5,227,084. Mononuclear manganese (IV) complexes, for example Mn (1,4,7-trimethyl-1,4,7-triazacyclononane)-(OC
Referring (PF _6), U.S. Patent No. 5,194,416 which discloses a - H _{3) 3.} Yet another type of bleach catalyst described in U.S. Pat. No. 5,114,606 comprises a ligand that is a non-carboxylate polyhydroxy compound having at least three consecutive C-OH groups. Manganese (III) and / or (I
V) is a water-soluble complex. Preferred ligands include sorbitol, iditol, dulcitol, mannitol, xylitol, arabitol, adonitol, meso-
There are erythritol, meso-inositol, lactose, and mixtures thereof.

US Pat. No. 5,114,611 discloses a bleaching catalyst comprising a complex of a transition metal, including Mn, Co, Fe or Cu, with a non- (large) cyclic ligand. The ligand has the following formula: R ² R ³ || R ¹ -N = C-B-C = N-R ^{4 wherein} R ¹ , R ² , R ³ and R ⁴ are each R ¹ -N = C-R ² And R ³ -C = N-R ⁴ form a 5- or 6-membered ring, respectively.
, Substituted alkyl and aryl groups. The ring may be further substituted. B is a bridge group selected from O, S, CR ⁵ R ⁶ , NR ⁷ and C ＝ O, wherein R ⁵ , R ⁶ , and R ⁷ are each H
, Or an alkyl or aryl group, including substituted or unsubstituted groups. Preferred ligands include pyridine, pyridazine, pyrimidine, pyrazine, imidazole, pyrazole, and triazole rings. If desired, the ring may be substituted with substituents such as alkyl, aryl, alkoxy, halide and nitro. Particularly preferred is the ligand 2,2'-bispyridylamine. Preferred catalysts include Co, Cu, Mn, Fe, -bispyridylmethane and bispyridylamine complexes. Highly preferred catalysts include Co (2,2 '
-Bispyridylamine) Cl ₂ , di (isothiocyanato) bispyridylamine-cobalt (II), trisdipyridylamine-cobalt (II) perchlorate, Co (2
, _{2-bispyridylamine)} 2 _O 2 ClO _4, perchloric acid bis (2,2'
Bispyridylamine) copper (II), tris (di-2-pyridylamine) iron perchlorate (I)
I), and mixtures thereof. Highly preferred materials are manganese bridged cyclams, such as Mn dichlorocyclam or Mn1,4,8,11-
And tetraazacyclotetradecane.

Other examples include N ₄ Mn ^III (u—O) ₂ Mn ^IV N ₄ ) ⁺ and [Bipy ₂ Mn ^{II I} (u—O) ₂ Mn ^IV Bipy ₂ ] — (ClO ₄ ) ₃ . And dinuclear Mn complexes with 4-N- and 2-N-dentate ligands.

Other bleaching catalysts are described, for example, in published European patent application 408,131 (
Cobalt complex catalysts), published European patent applications 384,503 and 306,089 (metallo-porphyrin catalysts), U.S. Pat.
8,455 (manganese / polydentate catalyst), U.S. Pat. No. 4,711,7
No. 48 and published European patent application 224,952 (manganese absorbed on aluminosilicate catalyst), U.S. Pat. No. 4,601,845 (aluminosilicate support with manganese and zinc or Magnesium salt), U.S. Pat. No. 4,626,373 (manganese / ligand catalyst), U.S. Pat.
, 119,557 (ferric complex catalyst), German Patent 2,054,019
US Pat. No. 4,430,243 (with manganese cations and non-catalytic metal cations). Chelating substances), and US Pat.
No. 28,455 (manganese gluconate catalyst). A highly preferred catalyst is pentaamine cobalt (III) acetate dichloride.

[0047] The bleach catalyst is typically used in the compositions and methods of the present invention in a catalytically effective amount.
By "catalytically effective amount" is meant an amount sufficient to bleach and remove the soil of interest from the target substrate using any of the comparative test conditions. The test conditions vary depending on the type of washing device used and the habits of the user. Some users use very hot water for the washing operation, while others use hot or cold water. Of course, the catalytic performance of the bleaching catalyst is affected by such conditions, and the amount of bleaching catalyst used in a well-formulated detergent composition and bleaching composition can be adjusted as appropriate. In practice, but not by way of limitation, the compositions and methods of the present invention may comprise at least one
It is possible to provide on the order of 10 parts per million active bleaching catalyst material to the wash water, preferably from about 0.2 ppm to about 200 ppm, preferably from 0.4 ppm to 100 ppm of the catalyst material in the washing liquor. Can be adjusted. To further explain this point,
Micromolar manganese catalysts are effective at 40 ° C., pH 10, under European conditions using perborates and peracids. Under US conditions, concentrations would need to be increased 3-5 fold to achieve the same result.

Surfactants The detergent compositions of the present invention preferably comprise anionic, nonionic, cationic, amphoteric, amphoteric and zwitterionic surfactants and mixtures thereof. Including.

For a typical listing of anionic, nonionic, amphoteric, and zwitterionic classes and their surfactant varieties, see US Pat. No. 3,929,678, 197.
Promulgated in Laughlin and Heuring on December 30, 5th. Other examples include Surface Active Agents and Detergents (Vol.I and II, Schwartz,
Perry and Berch). A list of suitable cationic surfactants is described in U.S. Pat. No. 4,259,217, issued Mar. 31, 1981 to Murphy.

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

Anionic Surfactants The detergents of the present invention preferably comprise an additional anionic surfactant. Virtually all anionic surfactants useful for cleaning purposes can be incorporated into the present detergent compositions. These surfactants include salts of anionic sulfate, sulfonate, carboxylate and sarcosinate surfactants (eg, sodium,
Potassium, ammonium and substituted ammonium salts such as the mono-, di- and triethanolamine salts). Anionic sulphate surfactants are preferred.

A sulfonate and sulfate surfactant, preferably a linear or branched alkyl benzene sulfonate and alkyl ethoxy sulfate as described herein, preferably in combination with a cationic surfactant as described herein, Surfactant systems comprising are highly preferred.

Other anionic surfactants include isethionates such as acyl isethionates, N-acyl taurates, fatty acid amides of methyl tauride, alkyl succinates and sulfosuccinates, monoesters of sulfosuccinates ( in particular saturated and unsaturated _C 12 _{-C 18} monoesters), diesters of sulfosuccinate (especially saturated and unsaturated _C 6 _{-C 14} diesters), include N- acyl sarcosinates. Resin acids and hydrogenated resin acids such as rosin, hydrogenated rosin,
Also suitable are resin acids and hydrogenated resin acids which are present in or derived from tallow oil.

[0054] Suitable anionic sulphate surfactants for use herein anionic sulfate surfactant, linear,
And branched primary and secondary alkyl sulfates, alkyl ethoxy sulfates, fatty oleoyl glycerol sulfates, alkyl phenol ethylene oxide ether _sulfates, C 5 _{-C 17 acyl-N-(C} 1 ~
C ₄ alkyl) and -N- (C ₁ ~C ₂ hydroxyalkyl) glucamine sulfates, and alkyl polysaccharides sulfates, for example sulfates of alkylpolyglucoside (the nonionic nonsulfated compounds described herein), include .

The alkyl sulphate surfactant is preferably a linear and branched primary C ₁₀ -C ₁₈ alkyl sulphate, more preferably a C ₁₁ -C ₁₅ branched chain alkyl sulphate and a C ₁₂ -C ₁₄ sulphate. Selected from chain alkyl sulfates. The alkyl ethoxy sulfate surfactant is preferably a molecule 1
Selected from the group consisting of _C 10 _{-C 1 8} alkyl sulfates ethoxylated with pieces per 0.5 to 20 moles of ethylene oxide. More preferably, the alkyl ethoxysulfate surfactant is 0.5 to 7 moles per one molecule, preferably _C 11 _{-C 18} ethoxylated with 1-5 moles of ethylene oxide, most preferably _C 11 _{-C 15} alkyl It is a sulfate.

In a particularly preferred embodiment of the invention, a mixture of the preferred alkyl sulphates and / or sulphonates and alkyl ethoxy sulphate surfactants is used. Such mixtures are described in PCT Patent Application No. WO 93/18124.

Anionic Sulfonate Surfactants Suitable anionic sulfonate surfactants for use herein include C _5-
C ₂₀ linear alkylbenzene sulfonates, alkyl ester sulfonates,
C ₆ -C ₂₂ primary or secondary alkane sulfonates, C ₆ -C ₂₄ olefin sulfonates, sulfonated polycarboxylic acids, alkyl glycerol sulfonates, fatty acyl glycerol sulfonates, and fatty oleyl glycerol sulfonates, and mixtures thereof .

Anionic Carboxylate Surfactants Suitable anionic carboxylate surfactants include alkyl ethoxy carboxylate, alkyl polyethoxy polycarboxylate surfactants and soaps ("alkyl carboxyls"), especially The particular secondary soaps mentioned are mentioned.

Suitable alkylethoxycarboxylates include those having the formula: _{RO (CH 2 CH 2 O)} x CH 2 COO - M + wherein, R is _C 6 _{-C 18} alkyl group, x is 0-10, the amount of ethoxylate, x is from 0 substance Is less than 20% by weight, and M is a cation. Suitable alkyl polyethoxy polycarboxylate surfactants include those having the formula: RO- (CHR ₁ -CHR ₂ -O) _x -R _{3 In the} formula, R is a C ₆ -C ₁₈ alkyl group, x is 1-25, R ₁ and R ₂ are hydrogen, methyl acid group Wherein R ₃ is hydrogen, a substituted or unsubstituted hydrocarbon having 1 to 8 carbon atoms, and succinic acid, hydroxysuccinic acid, and mixtures thereof. Selected from the group consisting of mixtures.

Suitable soap surfactants include secondary soap surfactants that contain a carboxyl unit attached to a secondary carbon. 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-octane. A water-soluble substance selected from the group consisting of acids and water-soluble salts of 2-pentyl-1-heptanoic acid. Certain soaps can also be included as foam inhibitors.

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

Alkoxylated nonionic surfactants Virtually all alkoxylated nonionic surfactants are preferred here.
Ethoxylated and propoxylated nonionic surfactants are preferred.

Preferred alkoxylated surfactants are alkylphenols, nonionic ethoxylated alcohols, nonionic condensates of nonionic ethoxylated / propoxylated fatty alcohols, nonionic ethoxylates / propoxylates with propylene glycol It can be selected from the group of condensates and non-ionic ethoxylate condensation products with propylene oxide / ethylenediamine adducts.

Nonionic alkoxylated alcohol surfactants Condensation products of aliphatic alcohols with 1 to 25 moles of alkylene oxides, especially ethylene oxide and / or propylene oxide, are preferred for use herein. The alkyl chain of the aliphatic alcohol may be linear or branched, primary or secondary, and generally has from 6 to 22 carbon atoms. A condensation product of an alcohol having an alkyl group having 8 to 20 carbon atoms and 2 to 10 moles of ethylene oxide per mole of alcohol is particularly preferred.

[0065]Nonionic polyhydroxy fatty acid amide surfactant Polyhydroxy fatty acid amides suitable for use herein have the following structural formula:
Substance. R²CONR¹In the formula, R1 is H, C₁~ C₄Hydrocarbyl, 2-hydroxyethyl, 2-
Hydroxypropyl, ethoxy, propoxy, or mixtures thereof, preferably
Is C1 -C4 alkyl, more preferably C1 -C4 alkyl₁Or C₂Alkyl, most preferred
Or C₁Alkyl (ie, methyl);₂Is C₅~ C₃₁Hid
Locarbyl, preferably linear C₅~ C₁₉Alkyl or alkenyl, more preferred
Preferably straight chain C₉~ C₁₇Alkyl or alkenyl, most preferably straight chain C ₁₁ ~ C₁₇Alkyl or alkenyl, or a mixture thereof, wherein Z is
Has a hydrocarbyl straight chain with at least three hydroxyls directly attached to the chain
Polyhydroxyhydrocarbyls or their alkoxylation (preferably
Toxylated or propoxylated) derivatives. Z is preferably aminated
And is derived from a reducing sugar, more preferably Z is glycityl.

Nonionic Fatty Acid Amide Surfactants Suitable fatty acid amide surfactants include those having the formula: R ⁶ CON (R ⁷ ) _{2 In the} formula, R ⁶ is an alkyl group having ^{7 to} 21, preferably 9 to 17 carbon atoms, and each R ⁷ is hydrogen, C _{1 to} C ₄ alkyl, C ₁ to C _4. Selected from the group consisting of C ₄ hydroxyalkyl, and — (C ₂ H ₄ O) _x H, wherein x is 1-3
Is an integer.

Nonionic Alkyl Polysaccharide Surfactants Alkyl polysaccharides suitable for use herein are described in US Pat. No. 4,565,647, Llenado, issued Jan. 21, 1986. Has 6 carbon atoms
And a hydrophilic group of a polysaccharide having 1.3 to 10 saccharide units, for example, a polyglycoside.

Preferred alkyl polyglycosides have the formula: R ² O (C _n H _2n O) _t (glycosyl) _{x In the} formula, R ² represents alkyl, alkylphenyl, hydroxyalkyl, hydroxyalkylphenyl having 10 to 18 carbon atoms in the alkyl group, and a mixture thereof. Wherein n is 2 or 3, t is 0-10, x
Is from 1.3 to 8. Glycosyl is preferably derived from glucose.

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

Suitable amine oxides include compounds having the formula: R³(OR⁴)_xN⁰(R⁵)₂ Where R³Is an alkyl, hydroxyalkyl, a having 8 to 26 carbon atoms
Choose from silamidopropyl and alkylphenyl groups or mixtures thereof
And R⁴Is an alkylene or hydroxyalkylene group having 2 to 3 carbon atoms
Or a mixture thereof, wherein x is 0-5, preferably 0-3, and each R⁵  Is an alkyl or hydroxyalkyl group containing 1 to 3, or
It is a polyethylene oxide group having 1 to 3 lenoxide groups. C₁₀~ C ₁₈ Alkyldimethylamine oxide, and C_10-18Acyl amido al
Killed dimethylamine oxide is preferred.

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

Zwitterionic Surfactants Zwitterionic surfactants can also be incorporated into the detergent compositions of the present invention.
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.

Suitable betaines are compounds having the formula: R (R ')₂N⁺R²COO⁻ Where R is C₆~ C₁₈A hydrocarbyl group, each R¹Is typically C ₁ ~ C₃Alkyl, R²Is C₁~ C₅Is a hydrocarbyl group
. Preferred betaines are C_12-18Dimethyl-ammoniohexanoate and
And C_10-18Acylamidopropane (or ethane) dimethyl (or die
Chill) Betaine. Complex betaine surfactants are also suitable for use herein.
is there.

Cationic Surfactants Suitable cationic surfactants for use in the detergents of the present invention include quaternary ammonium surfactants. Preferably, the quaternary ammonium surfactant is mono C ₆ -C _16, preferably _C 6 _-C 10 N-alkyl or alkenyl ammonium surfactants, the remaining N positions are substituted methyl, the hydroxyethyl or hydroxypropyl groups. Monoalkoxylated and bis-alkoxylated amine surfactants are also preferred.

Another suitable group of cationic surfactants that can be used in the detergent compositions or components thereof are cationic ester surfactants. The cationic ester surfactant is preferably dispersed in water having surfactant properties, comprising at least one ester (i.e., -COO-) linkage and at least one cationically charged group. It is a compound that can be used.

Suitable cationic ester surfactants, including choline ester surfactants, are described, for example, in US Pat. Nos. 4,228,042, 4,239,660 and 4,260,529.

In a preferred embodiment, the ester linkage and the cationically charged group are at least 3 atoms (ie 3 chain length), preferably 3 to 8 atoms, more preferably 3 to 5 atoms within the surfactant molecule. Are separated from each other by spacer groups consisting of a chain comprising atoms, most preferably 3 atoms. The atoms forming the chain of the spacer group are selected from the group consisting of carbon, nitrogen and oxygen atoms and mixtures thereof, provided that any nitrogen or oxygen in the chain is only associated with carbon in the chain. Are combined. Thus, for example, -OO- (i.e., peroxide), -NN-, and-
Although spacer group having a N-O-bonds are excluded, for example, _-CH 2 -O-C
H ₂ - and _{-CH 2} -NH-CH 2 - spacer group having a bond are included. In a preferred embodiment, the chain of the spacer group comprises only carbon atoms, most preferably the chain is a hydrocarbyl chain.

[0078] Cationic mono - alkoxylated amine surfactants Highly preferred surfactants herein are cationic mono having the general formula I below - is an alkoxylated amine surfactant. ^{R 1 ApR 4 \ / N +} X - (I) / \ R in 2 ^{R 3} Formula, ^{R 1} is from about 6 to about 18 carbon atoms, preferably from 6 to about 16, and most preferably from about 6 to about 14 Certain alkyl or alkenyl moieties wherein R ² and R ³ are each independently an alkyl group having from 1 to about 3 carbon atoms, preferably methyl, most preferably both R ² and R ³ are methyl And R ⁴ is selected from hydrogen (preferred), methyl and ethyl, and X ⁻ is an anion to provide electrical neutrality, such as chloride, bromide, methyl sulfate, sulfate, and the like. And A is an alkoxy group, especially an ethoxy, propoxy or butoxy group, and p is 0 to about 30, preferably 2 to about 15, most preferably 2 to about 8.

Preferably, ApR ⁴ is a hydroxyalkyl group having 6 or less carbon atoms, wherein the —OH group is separated from the quaternary ammonium nitrogen atom by 3 or less carbon atoms. Particularly preferred ApR ⁴ groups are —CH ₂ CH ₂ OH, —C
_{H 2 CH 2 CH 2 OH,} -CH 2 CH (CH 3) OH and -CH (
CH ₃₎ a _{CH 2 OH, -CH 2 CH 2} OH is particularly preferred. Preferred R ¹ groups are linear alkyl groups. Linear R ¹ having 8 to 14 carbon atoms Groups are preferred.

Another highly preferred cationic mono-alkoxylated amine surfactant is a material having the formula: ^{_{R 1 (CH 2 CH 2 O}} ) 2-5 H \ / N + X - / in \ _CH 3 CH ₃ Formula, ^{R 1} is _C 10 _{-C 18} hydrocarbyl and mixtures thereof, especially _C 10 _{-C 14} Alkyl, preferably C ₁₀ and C ₁₂ alkyl, X
Is a convenient anion to balance the charge, preferably chloride or bromide.

As mentioned above, compounds of the above type include ethoxy (CH ₂ CH ₂ O) units (EO) with butoxy, isopropoxy [CH (CH ₃ ) CH ₂ O] and [CH ₂ CH ( CH ₃ ) O] unit (i-Pr) or n-propoxy unit (
Pr), or EO and / or Pr and / or i-Pr units.

The amount of the cationic mono-alkoxylated amine surfactant used in the detergent composition of the present invention is preferably 0.1 to 20% by weight of the composition, more preferably 0.2 to 20%.
7% by weight, most preferably 0.3-3.0% by weight.

Cationic bis-alkoxylated amine surfactants Cationic bis-alkoxylated amine surfactants preferably have the following general formula II: ^{R 1 ApR 3 \ / N +} X - (II) / in \ ^R 2 A'qR ⁴ formula, ^{R 1} is from about 8 to about 18 carbon atoms, about preferably 10 to about 16, and most preferably from about 10 14, an alkyl or alkenyl moiety wherein R ² is an alkyl group having 1 to 3 carbon atoms, preferably methyl; R ³ and R ⁴ can be independently varied; ), Methyl and ethyl, wherein X ⁻ is an anion sufficient to provide electrical neutrality, such as chloride,
Bromide, methyl sulphate, sulphate, etc., wherein A and A ′ can vary independently and each is a C ₁ -C ₄ alkoxy, especially ethoxy (ie, —C
H ₂ CH ₂ O-), propoxy, selected from butoxy and mixtures thereof, p is from 1 to about 30, preferably from 1 to about 4, q is from 1 to about 30, preferably in from 1 to about 4 , Most preferably, both p and q are 1.

Highly preferred cationic bis-alkoxylated amine surfactants for use herein are those having the formula: R ¹ CH ₂ CH ₂ OH＼ / N ⁺ X ⁻ / ＼ CH ₃ CH ₂ CH ₂ OH wherein R ¹ is C ₁₀ -C ₁₈ hydrocarbyl and mixtures thereof, preferably C ₁₀ , C ₁₂ , C _{12 14} alkyl and mixtures thereof, wherein X is
An anion, preferably chloride, which is convenient for charge balancing. Respect general cationic bis alkoxylated amine structure noted above, since in a preferred compound R ¹ is derived from (coconut) C ₁₂ -C ₁₄ alkyl fraction fatty acids,
R ² is methyl, ApR ³ and A'qR ⁴ are each monoethoxy.

[0085] Other cationic bisalkoxylated amine surfactants suitable for use herein include compounds having the formula: R ¹ (CH ₂ CH ₂ O) pH＼ / N ⁺ X ⁻ / R ² (CH ₂ CH ₂ O) qH wherein R ¹ is C ₁₀ -C ₁₈ hydrocarbyl, preferably C ₁₀ -C ₁₄ alkyl. And independently p is 1 to about 3, q is 1 to about 3, and R ² is C ₁ -C ₃ alkyl, preferably methyl, X is an anion, especially chloride or bromide.

Other compounds of the above type include ethoxy (CH ₂ CH ₂ O) units (EO)
But butoxy (Bu), isopropoxy _{[CH (CH 3) CH 2} O] and _{[CH 2 CH (CH 3)} O] units (i-Pr) or n- propoxy units (
Pr), or EO and / or Pr and / or i-Pr units.

Water-soluble builder compounds The detergent compositions of the present invention typically contain from 1 to 80% by weight of the composition in the detergent composition.
It is preferred to include a water-soluble builder compound, preferably present in an amount of 10-60% by weight, most preferably 15-40% by weight.

The detergent composition of the present invention is preferably 0.5 to 60% by weight, more preferably 5 to 60% by weight.
Comprising a phosphate-containing builder material present in an amount of 50% by weight, more preferably 8-40% by weight.

[0089] The phosphate-containing builder material preferably comprises tetrasodium pyrophosphate, more preferably anhydrous sodium tripolyphosphate.

Suitable water-soluble builder compounds include water-soluble monomeric polycarboxylic acid salts, or their acid forms, homo- or copolymeric polycarboxylic acids or their salts, wherein the polycarboxylic acid is , Containing at least two carboxyl groups separated from each other by no more than 2 carbon atoms), borates, and mixtures of any of the above.

The carboxylate or polycarboxylate builder can be monomeric or oligomeric, but monomeric polycarboxylates are generally preferred for cost and performance reasons.

Suitable carboxylates containing one carboxyl group include the water-soluble salts of lactic acid, glycolic acid and their ether derivatives. Polycarboxylates containing two carboxyl groups include water-soluble salts of succinic, malonic, (ethylenedioxy) diacetate, maleic, diglycolic, tartaric, tartronic and fumaric acids, and ether carboxylic acids. And sulfinylcarboxylates. Polycarboxylates or their acids containing three carboxyl groups include, in particular, water-soluble citrates, aconitates and citraconic acid salts, and succinate derivatives, such as GB 1,379,241. The carboxymethyloxysuccinate described in the specification, the lactoxysuccinate described in GB 1,389,732, and the Dutch application 72058073 are described. Aminosuccinate and oxypolycarboxylate materials,
For example, 2-oxa-1 described in British Patent 1,387,447.
, 1,3-propanetricarboxylate. The most preferred polycarboxylic acid containing three carboxyl groups is citric acid, preferably 0.1% of the composition.
-15% by weight, more preferably 0.5-8% by weight.

[0093] Polycarboxylates containing four carboxyl groups include GB 1,261,
No. 829, 1,1,2,2-ethanetetracarboxylate, 1,1,3,3-propanetetracarboxylate and 1,
1,2,3-propanetetracarboxylate. Polycarboxylates containing sulfo substituents include those described in GB 1,398,421 and 1,39.
8,422 and US Pat. No. 3,936,448, and the sulfonated pyrolysis described in British Patent 1,439,000. Citrate. Preferred polycarboxylates are hydroxycarboxylates containing up to 3 carboxy groups per molecule, especially citrates.

Also useful builder components are the parent acids of the monomeric or oligomeric polycarboxylate chelators or mixtures of these acids and their salts, such as citric acid and / or citrate / citric acid mixtures. It is considered as.

[0095] Borate builders, as well as builders that include borate-forming materials capable of forming borate under detergent storage or washing conditions, are useful as water-soluble builders.

Good examples of water-soluble phosphate builders are alkali metal tripolyphosphates, pyrophosphates of sodium, potassium and ammonium, pyrophosphates of sodium and potassium and ammonium, orthophosphates of sodium and potassium, Polymeta / sodium phosphate, which is about 6-21, and salts of phytic acid.

Partially soluble or insoluble builder compounds The detergent compositions of the present invention may comprise from 0.5 to 60%, preferably from 5 to 50%, most preferably from 8 to 40% by weight of the composition. May be included in the partially soluble or insoluble builder compound.

Examples of builders that are almost insoluble in water include sodium aluminosilicate.

A suitable aluminosilicate zeolite has the following unit cell formula: _{Na z [(AlO 2) z} (SiO 2) y]. xH in ₂ O formula, z and y are at least 6, the molar ratio of z and y is 1.0-0.5, x is at least 5, preferably from 7.5 to 276, more preferably 10 ~ 2
64. The aluminosilicate material is in a hydrated form, preferably crystalline, and contains 10% to 28%, more preferably 18% to 22%, of water in bound form. The aluminosilicate zeolite may be a naturally occurring material, but a synthetic product is preferred. Synthetic crystalline aluminosilicate ion exchange materials are commercially available under the names Zeolite A, Zeolite B, Zeolite P, Zeolite X, Zeolite HS, and mixtures thereof. Zeolite A has the following formula: Na ₁₂ [AlO ₂ ) ₁₂ (SiO ₂ ) ₁₂ ]. xH ₂ O In the formula, x is from 20 to 30, especially 27. Zeolite X has the formula Na ₈₆ [AlO ₂ ) ₈₆ (SiO ₂ ) ₁₀₆ ]. That having a 276H ₂ O.

Another preferred aluminosilicate zeolite is a zeolite MAP builder. Zeolite MAP can be present in an amount of 1 to 80%, more preferably 15 to 40% by weight of the composition.

Zeolite MAP is described in EP 384070A (Unilever). This material is defined as a zeolite P-type alkali metal aluminosilicate having a ratio of silicon to aluminum of 1.33 or less, preferably 0.9 to 1.33, more preferably 0.9 to 1.2. ing.

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

[0103] In a preferred embodiment, builders zeolite MAP _detergent particle size, expressed as _{the d 50} value is 1.0 to 10.0 micrometers, more preferably 2.0 to 7.0 micrometers, and most preferably 2 0.5-5.0 micrometers.

The d ₅₀ value indicates that 50% by weight of the particles have a smaller diameter than that value. The particle size can in particular be measured using conventional analytical techniques, for example microscopy using a scanning electron microscope, or using a laser granulometer. Other methods of determining the d ₅₀ value is described in EP 384070A.

Heavy Metal Ion Sequestering Agent The detergent composition of the present invention preferably contains a heavy metal ion sequestering agent as an optional component. 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, but have the selectivity to preferentially bind heavy metal ions such as iron, manganese and copper.

Heavy sequestrants generally comprise from 0.005 to 10%, preferably from 0.1 to 5%, more preferably from 0.25 to 7.5%, most preferably from 0,5% to 10% by weight of the composition.
. It is present in an amount of 3 to 2% by weight.

Suitable heavy metal ion sequestering agents for use herein include organic phosphonates, such as aminoalkylene poly (alkylene phosphonates), alkali metal ethane 1-
Hydroxydiphosphonate, and nitrilotrimethylenephosphonate.

Preferred among the above substances are diethylenetriaminepenta (methylenephosphonate), ethylenediaminetri (methylenephosphonate), hexamethylenediaminetetra (methylenephosphonate) and hydroxy-ethylene 1,1 diphosphonate, 1,1 hydroxyethane. Diphosphonic acid and 1,1 hydroxyethane dimethylene phosphonic acid.

Other heavy metal sequestering agents suitable for use herein include nitrilotriacetic acid and polyaminocarboxylic acids such as ethylenediaminotetraacetic acid, ethylenediaminedisuccinic acid, ethylenediaminediglutaric acid, 2-hydroxypropylenediaminedisuccinate. An acid or any salt thereof is included.

Other suitable heavy sequestering agents for use herein are iminodiacetic acid derivatives, such as EP-A-317,542 and EP-A-39.
2-hydroxyethyldiacetic acid or glyceryl iminodiacetic acid as described in US Pat. No. 9,133. Sequestration of iminodiacetic acid-N-2-hydroxypropyl sulfonic acid and aspartic acid N-carboxymethyl N-2-hydroxypropyl-3-sulfonic acid described in EP-A-516,102. Agents are also suitable here. European Patent EP-A-5
Also preferred are the β-alanine-N, N′-diacetic acid, aspartic acid-N, N′-diacetic acid, aspartic acid-N-monoacetic acid and iminodisuccinate sequestering agents described in JP-A-09,382. It is.

European Patent EP-A-476,257 describes suitable amino sequestering agents. European Patent EP-A-510,331 describes suitable sequestering agents derived from collagen, keratin or casein. European Patent EP-A-528,859 describes suitable alkyliminodiacetic acid sequestering agents. Dipicolinic acid and 2
-Phosphonobtan-1,2,4-tricarboxylic acid are also suitable. Glycinamide-N, N′-disuccinic acid (GADS), ethylenediamine-NN′-diglutaric acid (EDDG) and 2-hydroxypropylenediamine-NN′-disuccinic acid (HPDDS) are also suitable.

Diethylenetriaminepentaacetic acid, ethylenediamine-N, N′-disuccinic acid (EDDS), 1,1hydroxyethanediphosphonic acid and 1,1hydroxyethanedimethylenephosphonic acid or their alkali metals, alkaline earth metals, ammonium Or substituted ammonium salts, or mixtures thereof, are particularly preferred.

Another preferred ingredient useful in an enzyme detergent composition is one or more additional enzymes.

Preferred additional enzyme materials include commercially available lipases, cutinases, amylases, neutral and alkaline proteases, cellulases, endases, esterases, pectinases, lactases and peroxidases conventionally formulated in detergent compositions. Suitable enzymes are described in U.S. Pat. Nos. 3,519,570 and
, 533, 139.

Preferred commercially available protease enzymes include Alcalase, Savinase, Primase, Dura
enzymes sold by Novo Industries A / S (Denmark) under the trade names zym and Esperase, enzymes sold by Gist-Brocades under the trade names Maxatase, Maxacal and Maxapem, enzymes sold by Genencor International, And enzymes sold by Solvay Enzymes under the trade names Opticlean and Optimase. The protease enzyme is present in the composition of the present invention in an amount of 0.000% of the composition.
It can be incorporated in an amount of 1 to 4% by weight active enzyme.

Preferred amylases are described, for example, in GB 1,269,839 (Nov
o) include α-amylases from a special strain of B. licheniformis, described in more detail. Preferred commercially available amylase is, for example, by Gist-Brocades
Enzyme sold under the trade name Rapidase and trade name by Novo Industries A / S
Includes enzymes sold under Termamyl and BAN. Highly preferred amylase enzymes are described in PCT / US 9703635 and in International Patent WO 95
/ 26397 and WO96 / 23873.

The amylase enzyme is incorporated into the compositions of the present invention in an amount of 0.0001 to 2% active enzyme by weight of the composition.

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

The lipase may be of fungal or bacterial origin, for exampleHumicola sp., Thermomyces sp. orPseudomonas pseudoalcaligenes OrPseudomas fl uorescens EncompassesPseudomonas Obtained from lipase-producing varieties of sp. this
Lipases from chemically or genetically modified mutants of these varieties
Useful here. Described in European Patent EP-B-0218272
Have beenPseudomonas pseudoalcaligenes A lipase derived from is preferred. Another lipase preferred here is European Patent Application No. EP-A-02580.
As described in the specification of No. 68,Humicola lanuginosa The gene obtained from
Loan and hostAspergillus oryza By expressing the gene in
Lipolase trade name from Novo Industri A / S, Bagsvaerd, Denmark,
It is commercially available at This lipase is disclosed in U.S. Pat. No. 4,810,414,
It is also described in Huge-Jensen et al., Promulgated March 7, 1989.

Organic Polymeric Compound The organic polymeric compound is a preferred additional component of the detergent composition of the present invention, and is preferably present as a constituent of all particulate components, wherein the particulate component is one It can act to join together. Organic polymeric compounds are commonly used as dispersants and anti-redeposition and soil dispersants in detergent compositions, meaning substantially all polymeric organic compounds, wherein as a clay flocculant It includes all of the high molecular weight organic polymeric compounds described and includes the quaternized ethoxylated (poly) amine clay soil removal / redeposition inhibitor of the present invention.

The organic polymeric compound is generally present in the detergent composition of the present invention in an amount of from 0.1 to 3% of the composition.
0% by weight, preferably 0.1-15% by weight, most preferably 0.5-10% by weight
The amount is mixed.

Examples of organic polymeric compounds include water-soluble organic homopolymers or copolymers wherein the polycarboxylic acid comprises at least two carboxyl groups separated from each other by no more than two carbon atoms. Includes polycarboxylic acids or their salts. Polymers of the latter type are described in GB-A-1,596,756. Examples of such salts are polyacrylates of molecular weight 1000-5000 and their copolymers with maleic anhydride, such copolymers having a molecular weight of 20.
000 to 100,000, especially 40,000 to 80,000.

EP-A-305282, EP-A-30528
Useful herein are polyamino compounds, including compounds derived from aspartic acid, as described in EP-A-3,351 and EP-A-351629.

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

[0125] Other organic polymeric compounds suitable for incorporation in the detergent compositions of the present invention include cellulose derivatives such as methylcellulose, carboxymethylcellulose, hydroxypropylmethylcellulose and hydroxyethylcellulose. Other useful organic polymeric compounds are polyethylene glycols, especially those having a molecular weight of from 1,000 to 10,000, especially from 2,000 to 8,000, most preferably about 4,000.

Highly preferred components here are described in US Pat. No. 4,968,451, Sche
ibel et al. and US Pat. No. 5,415,807; Goseelink et al.
And especially according to U.S. Patent Application No. 60/051517, a cotton and non-cotton soil release polymer.

Another organic compound which is a preferred clay dispersant / anti-redeposition agent for use herein is ethoxylated cationic monoamines and diamines having the formula:

Embedded image In the formula, X, H, a C ₁ -C ₄ alkyl or hydroxyalkyl ester or ether groups, and non-ionic group selected from the group consisting of mixtures thereof, a is 0 to 20, preferably 0 4 (eg, ethylene, propylene, hexamethylene), b is 1 or 0, and a cationic monoamine (b = 0)
N is at least 16, typically 20-35, and for cationic diamines (b = 1), n is at least 12, typically about 12 to about 42. .

Other dispersants / anti-redeposition agents used herein are described in European Patent EP-B-0.
No. 11,965, U.S. Pat. No. 4,659,802 and U.S. Pat. No. 4,664,848.

Foaming Inhibition System The detergent composition of the present invention, when formulated for a machine cleaning composition, has a composition content of 0.01%.
-15% by weight, preferably 0.02-10% by weight, most preferably 0.05-3%
Comprising a foam control system present in an amount of weight percent.

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

By defoaming compound is meant here all compounds or mixtures of compounds which act by means of a solution of the detergent composition, in particular the foaming or foaming which occurs when the solution is stirred.

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

Other suitable defoaming compounds include monocarboxylic fatty acids and their soluble salts. These materials are described in U.S. Pat. No. 2,954,347, issued Sep. 27, 1960 to Wayne St. John. Monocarboxylic fatty acids and their salts used as foam inhibitors generally have 10 to 24 carbon atoms,
It preferably has a hydrocarbyl chain of 12-18. Suitable salts include the alkali metal salts such as sodium, potassium, and lithium salts, and ammonium and alkanolammonium salts.

Other suitable defoaming compounds include, for example, high molecular weight fatty esters (eg, fatty acid triglycerides), fatty acid esters of monohydric alcohols, aliphatic C ₁₈ -C ₄₀ ketones (eg, stearone), N-alkylated aminotriazines. E.g. tri- to hexa-alkylmelamine or di-tetra-alkyldiamine formed as a reaction product of cyanuric chloride with 2 or 3 moles of a primary or secondary amine having 1 to 24 carbon atoms having 1 to 24 carbon atoms Chlorotriazine, propylene oxide, bisstearic acid amide and monostearyl dialkali metal (eg, sodium, potassium, lithium) phosphates and phosphates are mentioned.

Preferred foam control systems include (a) an antifoam compound, preferably a silicone antifoam compound, most preferably (i) an amount of 50-99%, preferably 75-95%, by weight of the silicone antifoam compound. A silicone antifoam compound comprising (ii) a silica / silica antifoam compound in an amount of from 1 to 50% by weight, preferably from 5 to 25% by weight of the silicone / silica antifoam compound. Is incorporated in an amount of 5 to 50% by weight, preferably 10 to 40% by weight), (b) a dispersant compound in an amount of 0.5 to 10% by weight, preferably 1 to 10% by weight, most preferably A silicone glycol rake copolymer having a polyoxyalkylene content of 72 to 78% and a ratio of ethylene oxide to propylene oxide of 1: 0.9 to 1: 1.1 A particularly preferred silicone glycol rake copolymer of this type is commercially available from DOW Corning under the trade name DCO 544), (c) an inert carrier fluid in an amount of from 5 to 80% by weight, preferably from 10 to 70% by weight. compound (most preferably a degree of ethoxylation from 5 to 50, preferably a _C 16 _{-C 18} ethoxylated alcohol is 8-15) comprising.

[0136] Highly preferred particulate foam control systems are described in EP-A-02107.
No. 31, the silicone antifoaming compound and a melting point of 50 ° C. to 8
An organic carrier material at 0 ° C., wherein the organic carrier material comprises a monoester of glycerol and a fatty acid having a carbon chain of 12 to 20 carbon atoms. EP-A-0210721 discloses another preferred particulate foam control system wherein the organic carrier material comprises a fatty acid or alcohol having a carbon chain of 12 to 20 carbon atoms, or a mixture thereof. A melting point of 4
5 ° C to 80 ° C.

Other highly preferred foam control systems comprise mixtures of polydimethylsiloxane or silicone, such as polydimethylsiloxane, aluminosilicate and polycarboxylic acid polymers, such as copolymers of laic and acrylic acid. .

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.
% By weight of a polymeric dye transfer inhibitor may also be included.

The polymeric dye transfer inhibitor is preferably a polyamine N-oxide polymer, N-
It is selected from copolymers of vinylpyrrolidone and N-vinylimidazole, polyvinylpyrrolidone polymers or combinations thereof, wherein these polymers may be cross-linked polymers.

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

[0141] Hydrophilic optical brighteners useful in the present invention include those having the following structural formula.

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

In the above formula, when R ₁ is anilino, R ₂ is N-2-bis-hydroxyethyl, and M is a cation, for example, sodium, the brightener is 4,4 ′ -Bis [(4-anilino-6- (N-2-bis-hydroxyethyl) -s-triazin-2-yl) amino] -2,2'-stilbenedisulfonic acid and disodium salt. This special brightener is available from Ciba-Geigy Corpora
is sold under the trade name Tinopal-UNPA-GX. Tinopal-CBS-X and Ti
nopal-UNPA-GX is a preferred hydrophilic optical brightener useful in the detergent compositions of the present invention.

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

In the above formula, when R ₁ is anilino, R ₂ is morpholino, and M is a cation, for example, 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 commercially available from Ciba-Geigy Corporation under the trade names Tinopal-DMS-X and Tinopal AMS-GX.

Polymer Soil Release Agent The detergent composition of the present invention may optionally contain a known polymer soil release agent (hereinafter referred to as “SRA”).
When used, the SRA generally represents from 0.01 to 10.0%, especially from 0.1 to 5%, preferably from 0.2 to 3% by weight of the composition. .
Accounts for 0% by weight.

Preferred SRAs are hydrophilic moieties for imparting hydrophilicity to the surface of hydrophobic fibers, such as polyester and nylon, and are deposited on the hydrophobic fibers and adhere thereto through washing and rinsing cycles. It generally has a hydrophobic part that acts as an anchor for the sexual part. As a result, dirt generated after the treatment with SRA is more easily washed in a later washing step.

Preferred SRAs are oligomeric terephthalic acids typically prepared by processes involving at least one transesterification / oligomerization (often using metal catalysts such as titanium (IV) alkoxides) And esters. Such esters are of course made using additional monomers that can be incorporated into the ester structure through one, two, three, four or more positions, without forming a tightly crosslinked overall structure. be able to.

Suitable SRAs are described, for example, in terephthaloyl and oxyalkyleneoxy repeats, as described in US Pat. No. 4,968,451, issued Nov. 6, 1990 to JJ Scheibel and EP Gosselink. Includes a substantially linear ester oligomer sulfonation product comprising an oligomeric ester backbone of the unit and a sulfonated end moiety derived from allyl covalently attached to the backbone. Such ester oligomers include (a) ethoxylating allyl alcohol and (b) converting the product of (a) to a two-stage ester with dimethyl terephthalate ("DMT") and 1,2-propylene glycol ("PG"). It can be produced by reacting in an exchange reaction / oligomerization step and reacting the products (c) and (b) with sodium metabisulfite in water. Another SRA is disclosed in U.S. Pat.
Non-ionic end-capped 1,2-propylene / polyoxyethylene terephthalate polyesters from Gosselink et al., Dec. 8, 1987, December 8, 1987, such as poly (ethylene glycol) methyl ether, DMT,
Includes materials made by transesterification / oligomerization of PG and poly (ethylene glycol) ("PEG"). Other examples of SRA include partially and fully anionic end-capped oligomeric esters of US Pat. No. 4,721,580, Jan. 26, 1988, Gosselink, such as ethylene glycol (" EG "), PG, DMT and oligomers obtained from Na-3,6-dioxa-8-hydroxyoctanesulfonate, U.S. Pat. No. 4,702.
No. 857, Oct. 27, 1987, Gosselink, nonionic capped block polyester oligomeric compounds such as DMT, methyl (Me
) Materials made from capped PEG and EG and / or PG, or DMT, EG and / or PG, a combination of Me-capped PEG and Na-dimethyl-5-sulfoisophthalate, and US Pat. No. 4,877. No. 896, Oct. 31, 1989, Maldonado, Gosselink et al., Anionic systems, especially sulfoalloyl end-capped terephthalates, the latter being useful in both laundry and fabric conditioning products. Is a typical material of SRA
An example is an ester composition made from m-sulfobenzoic acid monosodium salt, PG and DMT, but optionally, but optionally, preferably further comprising an added PEG, such as PEG 3400.

SRA includes simple copolymer blocks of ethylene terephthalate or propylene terephthalate and polyethylene oxide or polypropylene oxide terephthalate (US Pat. No. 3,959,230, Hays, May 2, 1976).
5th, and U.S. Pat. No. 3,893,929, Basadur, July 1975
Month 08, reference), cellulosic derivatives, such as the commercially available hydroxy ether cellulosic polymer as METHOCEL from _Dow, C 1 -C ₄ alkylcelluloses and _{C 4} hydroxyalkyl celluloses (US Pat. No. 4,000,093 , Dec. 28, 1976, Nicol, et al.) And the average degree of substitution (methyl) per anhydroglucose unit is about 1.6 to about 2.3, measured as a 2% aqueous solution at 20 ° C. Methyl cellulose ethers having a solution viscosity of about 80 to about 120 centipoise. Such materials are available as METOLOSE SM100 and METOLOSE SM200, trade names of methylcellulose ether manufactured by Shin-Etsu Chemical Co., Ltd.

Another group of SRAs includes (I) nonionic terephthalates which use a diisocyanate coupling agent to attach the polymer ester structure (US Pat. No. 4,201,82
No. 4, Violland et al. And U.S. Pat. No. 4,240,918,
Lagasse et al.), And (II) trimellitic anhydride to a known SRA,
Includes SRA containing carboxylate end groups prepared by converting terminal hydroxyl groups to trimellitate. By selecting an appropriate catalyst, trimellitic anhydride forms a bond at the end of the polymer through an isolated carboxylic acid ester of trimellitic anhydride, rather than opening an anhydride bond. Either nonionic or anionic SRAs can be used as starting materials, as long as they have an esterifiable hydroxyl end group. U.S. Pat. No. 4,525,524, Tung
See et al. Other types include (III) SRA based on anionic terephthalate having various urethane bonds (US Pat. No. 4,201,824, Viol.
land et al.).

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. is there.

It is highly preferred to incorporate speckle particles. The following speckle particles are preferred speckle particles. Sodium carbonate particles in which 75% of the particles have a particle size of 600-850 microns and 25% of the particles have a particle size of 425-600 microns are obtained by aggregating and sieving the sodium carbonate powder. It is formed. The particles thus obtained are sprayed with a Monastral blue BV paste solution and subsequently dried to obtain speckle particles comprising about 1000 ppm of dye.

Highly preferred compositions comprise about 2 to about 10% by weight of an organic acid, preferably citric acid. Also, preferably in combination with carbonates, small amounts (less than about 20% by weight)
Neutralizers, buffers, phase modifiers, hydrotropes, enzyme stabilizers, polyacids, foam regulators, opacifiers, antioxidants, bactericides and dyes, such as U.S. Pat.
No. 841, Barrat et al., Issued Aug. 25, 1981, incorporated herein by reference.

Composition Forms The detergent compositions of the present invention can be prepared by various methods, including dry mixing and coagulation and / or spray drying of the various compounds contained in the detergent components.

The compositions of the present invention can take a variety of physical forms, including liquid and solid forms, such as tablets, flakes, pastels and bars, with granular forms being preferred.

The compositions of the present invention can also be used in combination with a bleach additive composition, for example, a composition comprising a chlorine bleach.

The chlorine-based bleach detergent composition may include, as an additional component, a chlorine-based bleach. However, since the preferred detergent compositions of the present invention are solids, most liquid chlorine-based bleaching are not suitable for these detergent compositions, and only granular or powdered chlorine-based bleaching agents are preferred.

Alternatively, the detergent composition is compatible with the chlorine bleach and should be formulated so that the user can add the chlorine bleach to the detergent composition at or during the start of washing. Can also.

A chlorine bleach is a material from which hypochlorite is formed in an aqueous solution. Hypochlorite ions are represented chemically by the formula OCT.

Bleaches that form hypochlorite in aqueous solution include hypochlorites of alkali metals or alkaline earth metals, hypochlorite addition products, chloramine, chlorimine,
Chloramide, and chlorimide. Specific examples of such compounds include sodium hypochlorite, potassium hypochlorite, monobasic calcium hypochlorite, magnesium dibasic hypochlorite, sodium chlorinated phosphate dodecahydrate, Potassium dichloroisocyanurate, sodium dichloroisocyanurate, sodium dichloroisocyanurate dihydrate, trichlorocyanuric acid, 1,3-dichloro-5,5
-Dimethylhydantoin, N-chlorosulfamide, Chloramine T, Dichlorami
ne T, chloramine B and Dichloramine B. Preferred bleaches for the compositions of the present invention are sodium hypochlorite, potassium hypochlorite, or mixtures thereof. A preferred chlorine bleach is Triclosan®.

Most of the above-described hypochlorite-forming bleaches are available in solid or concentrated form and dissolve in water in making the compositions of the present invention. Some of the above materials are commercially available as aqueous solutions.

The average particle size of the components of the granular composition of the present invention is preferably such that particles having a diameter of more than 1.8 mm are 25% or less and particles having a diameter of less than 0.25 mm are 25% or less. Should. An average particle size such that 10% to 50% of the particles have a particle size of 0.2 mm to 0.7 mm in diameter is preferred.

As defined herein, the term “average particle size” refers to a sample of the composition which is taken through a series of sieves, preferably
It is calculated by dividing into multiple fractions (typically 5 fractions) through a Tyler sieve. The weight fraction obtained is plotted against the sieve mesh size. The average particle size is defined as the size of an eye through which 50% by weight of the sample passes.

Washing Methods Machine washing methods typically involve cleaning soiled laundry with an effective amount of a washing aqueous solution in which an effective amount of a machine laundry detergent composition of the present invention has been dissolved or dispensed in a washing machine. Processing. An effective amount of the detergent composition is 10 g to 300 g dissolved or dispersed in a washing solution having a volume of 5 to 65 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 a preferred mode of use, the detergent composition is formulated to be suitable for manual laundry. In another preferred use, the detergent composition is a pre-treatment or dip composition used to pre-treat or soak soiled, stained fabrics.

[0166]

【Example】

Abbreviations used in examples In the detergent composition, the abbreviated components have the following meanings. LAS: Sodium linear C_11-13Alkylbenzenesulfonate TAS: Sodium tallow alkyl sulfate CxyAS: Sodium C_1x~ C_1yAlkyl sulfate C46SAS: Sodium C₁₄~ C₁₆Secondary (2,3) alkyl sulphate
CxyEzS: Sodium C condensed with zmol of ethylene oxide_1x~ C_1y Alkyl sulfate CxyEz: C condensed with an average of z moles of ethylene oxide_1x~ C_1yWith the Lord
And linear primary alcohol QAS: R₂N⁺(CH₃)₂(C₂H₄OH), R₂= C_{1 2} ~ C₁₄ QS1: R₂N⁺(CH₃)₂(C₂H₄OH), R₂= C ₈ ~ C₁₁ SADS: Formula 2- (R). C₄H₇-1,4- (SO₄-)₂Sodium C₁₄~ C₂₂Alkyl disulfate (where R = C₁₀~ C₁₈) SADE2S: Formula 2- (R) .Fused with z moles of ethylene oxide. C₄ H₇-1,4- (SO₄-)₂Sodium C₁₄~ C₂₂Alkyl disulfate (where R = C₁₀~ C₁₈) MES: C₁₈X-sulfomethyl ester of fatty acid APA: C₈~ C₁₀Amidopropyldimethylamine soap: nato derived from an 80/20 mixture of tallow and coconut fatty acids
Lithium linear alkyl carboxylate STS: Sodium toluene sulfonate CFAA: C₁₂~ C₁₄(Coco) alkyl N-methylglucamide TFAA: C₁₆~ C₁₈Alkyl N-methylglucamide TPKFA: C₁₆~ C₁₈topped whole cut fatty acid STPP: anhydrous sodium tripolyphosphate TSPP: tetrasodium pyrophosphate zeolite A: formula Na₁₂(AlO₂SiO₂)₁₂. 27H₂O hydration
Sodium aluminosilicate, primary particle size 0.1-10 micrometers (weight is
NaSKS-6: Formula δ-Na₂Si₂O₅Crystalline layered silicate of citric acid: anhydrous citric acid borate: sodium borate carbonate: anhydrous sodium carbonate, particle size 200 μm to 900 μm bicarbonate: anhydrous sodium bicarbonate, particle size distribution 400 μm to 1200 μm silicate : Amorphous sodium silicate (SiO₂: Na₂O = 2.0: 1) Sulfate: anhydrous sodium sulfate Mg: anhydrous magnesium sulfate Citrate: trisodium citrate dihydrate, activity 86.4%, particle size distribution 4
25 μm to 850 μm MA / AA: maleic acid / acrylic acid 1: 4 copolymer, average molecular weight about 70,
000 MA / AA (1): maleic acid / acrylic acid 4: 6 copolymer, average molecular weight about
10,000 AA: sodium polyacrylate polymer, average molecular weight 4,500 CMC: sodium carboxymethyl cellulose Cellulose ether: methylcellulose ether, degree of polymerization 650, manufactured by Shin-Etsu Chemical Protease: proteolytic enzyme, active enzyme 3.3% by weight, Savinase Product
Produced by NOVO Industries A / S under the name Protease I: Proteolytic enzyme, 4% by weight of active enzyme
Alcalase: Proteolytic enzyme, 5.3% by weight of active enzyme, NOVO Industries A / S described in 5/10591 and sold by Genencor Int. Inc.
Cellulase: Cellulolytic enzyme, 0.23% by weight of active enzyme, NOVO Industrie
Amylase: amylolytic enzyme, 1.6% by weight of active enzyme, NOVO Industries A / S
Amylase II: amylolytic enzyme, sold under the trade name Termamyl 120T from S
Listed Lipase: Lipolytic enzyme, active enzyme 2.0% by weight, from NOVO Industries A / S
Lipase (1): Lipolytic enzyme, active enzyme 2.0% by weight, NOVO Industries A /
Endolase: Endoglucanase enzyme, active enzyme 1.5% by weight, NOVO Industrie
s Sold from A / S PB4: Nominal NaBO₂. 3H₂O. H₂O₂Of sodium perborate
Tetrahydrate PB1: Nominal formula NaBO₂. H₂O₂Anhydrous sodium perborate bleach percarbonate: nominal formula 2Na₂CO₃. 3H₂O₂DOBS: decanoyloxybenzenesulfonate in the form of sodium salt DPDA: diperoxidedecandionic acid NOBS: nonanoyloxybenzenesulfonate in the form of sodium salt NACA-OBS: (6-nonamidocaproyl) oxybenzenesulfonate LOBS : Dodecanoyloxybenzenesulfonate in the form of sodium salt DOBS: decanoyloxybenzenesulfonate in the form of sodium salt DOBA: decanoyloxybenzoic acid TAED: tetraacetylethylenediamine DTPA: diethylenetriaminepentaacetic acid DTPMP: diethylenetriaminepenta (methylenephosphonate) , Monsan
EDDS: ethylenediamine-N, N-disuccinic acid, (S, S) isomer, its
Sodium salt form Photoactivated bleach (1): sulfo encapsulated in dextrin soluble polymer
Zinc phthalocyanine photoactivated bleach (2): sulfo encapsulated in dextrin-soluble polymer
Aluminozinc phthalocyanine brightener 1: disodium 4,4'-bis (2-sulfostyryl) biphe
Nyl Brightener 2: Disodium 4,4'-bis (4-anilino-6-morpholine
No-1,3,5-triazin-2-yl) amino) stilbene-2: 2'-dis
Ruphonate HEDP: 1,1-hydroxyethanediphosphonic acid HEDMP: 1,1-hydroxyethanedimethylenephosphonic acid PEGx: polyethylene glycol, molecular weight x (typically 4,000) PEO: polyethylene oxide, average molecular weight 50,000 TEMPAE: tetraethylene pentaamine ethoxylate PVI: polyvinyl imidazole, average molecular weight 20,000 PVP: polyvinyl pyrrolidone polymer, average molecular weight 60,000 PVNO: polyvinyl pyridine N-oxide polymer, average molecular weight 50,000 PVP VI: polyvinyl pyrrolidone Copolymer of vinylimidazole, average content
20,000 QEA: Screw ((C₂H₅O) (C₂H₄O_n) (CH₃) -N⁺-C₆H₁₂-N⁺-(
CH₃) Screw ((C₂H₅O)-(C₂H₄O)_n), N = 20-30 SRP1: Anionically end-capped polyester SRP2: Diethoxylated poly (1,2 propylene terephthalate) short block
Copolymer PEI: polyethyleneimine, average molecular weight 1800, average degree of ethoxylation nitrogen
7 ethyleneoxy residues per unit Silicone defoamer: Contains siloxane-oxyalkylene copolymer as dispersant
Polydimethylsiloxane foam control agent, a ratio of the foam control agent to the dispersant 1
0: 1-100: 1 opacifier: aqueous monostyrene latex mixture, from BASF Aktiengesellschaft
Sold under the trade name Lytron 621 Wax: paraffin wax Speckle particles: Speckle particles described here on page 40

In the examples below, all amounts are given as% by weight of the composition.

Example 1 The following detergent composition is in accordance with the invention.

[0169] ABCD Blown powder MES 2.0 0.5 1.0- SADS---2.0 LAS 6.0 5.0 11.0 6.0 TAS 2.0--2.0 Zeolite A 24.0--20.0 STPP-27.0 24.0- Sulfate 4.0 6.0 13.0- MA / AA 1.0 4.0 6.0 2.0 Silicate 1.0 7.0 3.0 3.0 CMC 1.0 1.0 0.5 0.6 Brightener 1 0.2 0.2 0.2 0.2 Silicone defoamer 1.0 1.0 1.0 0.3 DTPMP 0.4 0.4 0.2 0.4 spray Brightener 0.02--0.02 C45E7---5.0 C45E2 2.5 2.5 2.0- C45E3 2.6 2.5 2.0- Fragrance 0.3 0.3 0.5 0.2 Silicone defoamer 0.3 0.3 0.3- Dry additives QEA---1.0 EDDS 0.3--- Sulfate 2.0 3.0 5.0 10.0 Carbonate 6.0 13.0 15.0 14.0 Citric acid 2.5--2.0 QASII 0.5--0.5 SKS-6 10.0--- Percarbonate 4.0 3.0-1.9 PB4--5.0 NOBS 0.5--0.3 TAED 0.75 0.5 0.2 0.5 DOBS-0.5 0.6- Protease 1.0 1.0 1.0 1.0 Lipase-0.4-0.2 Lipase (1) 0.4-0.4- Amylase 0.2 0.2 0.2 0.4 Brightener 1 0.05--0.05 Other / small components100% in total

Example 2 The following granular detergent composition is in accordance with the invention EFGHI J Blown powder LAS 23.0 8.0 7.0 9.0 7.0 7.0 QAS ---- 1.0- C45AS 6.0 6.0 5.0 8.0-- C45E11S-1.0 1.0 1.0-- MES 2.0 --- 2.0 4.0 Zeolite A 10.0 18.0 14.0 12.0 10.0 10.0 MA / AA-0.5 --- 2.0 MA / AA (1) 7.0----- AA-3.0 3.0 2.0 3.0 3.0 Sulfate 5.0 6.3 11.1 11.0 11.0 18.1 Silicate 10.0 1.0 1.0 1.0 1.0 1.0 1.0 Carbonate 15.0 20.0 10.0 20.7 8.0 6.0 PEG 4000 0.4 1.5 1.5 1.0 1.0 1.0 DTPA-0.9 0.5--0.5 Brightener 2 0.3 0.2 0.3-0.1 0.3 Spray C45E7-2.0--2.0 2.0 C25E9 3.0 -----C23E9--1.5 2.0-2.0 Fragrance 0.3 0.3 0.3 2.0 0.3 0.3 agglomerates C45AS - 5.0 5.0 2.0 - 5.0 LAS - 2.0 2.0 - - 2.0 zeolite A - 7.5 7.5 8.0 - 7.5 carbonate - 4.0 4.0 5.0 - 4.0 PEG4000 - 0.5 0.5 - - 0.5 Others (water, etc. ) - 2.0 2.0 2.0 - 2.0 dry additives QAS (I) - - - - 1.0 - click Enoic acid - - - - 2.0 - PB4 - 3.0 - - 5 - PB1 - - 4 1.0 - - percarbonate 2.0 - - 1.0 - 2.0 Carbonate - 5.3 1.8 - 4.0 4.0 NOBS 0.5 - 0.4 0.3 - 0.6 DOBS - 0.9 - - 0.3 - TAED 0.6 0.4 0.6 0.3 0.9 0.5 methylcellulose 0.2 - - - - 0.5 DTPA 0.7 0.5 1.0 0.5 0.5 1.2 SKS-6 8.0----- STS-- 2.0-1.0-Cumenesulfonic acid-1.0---2.0 Lipase 0.2-0.2-0.2 0.4 Cellulase 0.2 0.2 0.2 0.3 0.2 0.2 Amylase II 0.2-0.1-0.2- Protease 0.5 0.5 0.5 0.3 0.5 0.5 PVPVI----0.5 0.1 PVP ---- 0.5- PVNO--0.5 0.3-- QEA----1.0- SRP1 0.2 0.5 0.3-0.2- Silicone defoamer 0.2 0.4 0.2 0.4 0.1- Sulfuric acid Mg--0.2-0.2- Speckle-2.0 1.0 0.5 2.0 6.0 Other / small component total 100%

Example 3 The following granular detergent composition is in accordance with the present invention. KLNM N basic granule STPP-22.0-15.0 Zeolite A 30.0-24.0 5.0 Sulfate 5.5 5.0 7.0 7.0 MA / AA 3.0 ---AA-1.6 2.0- MA / AA (1)-12.0-6.0 LAS 14.0 10.0 9.0 20.0 C45AS 8.0 7.0 9.0 7.0 C45AE11S-1.0-1.0 MES 0.5 4.0 6.0- SADS 2.5--1.0 Silicate-1.0 0.5 10.0 Soap-2.0-- Brightener 1 0.2 0.2 0.2 0.2 Carbonate 6.0 9.0 8.0 10.0 PEG4000-1.0 1.5- DTPA-0.4-- Spray C25E9---5.0 C45E7 1.0 1.0-- C23E9-1.0 2.5- Fragrance 0.2 0.3 0.3- Dry additive carbonate 5.0 10.0 13.0 8.0 PVPVI / PVNO 0.5-0.3- Protease 1.0 1.0 1.0 0.5 Lipase 0.4- - 0.4 amylase 0.1 - - 0.1 cellulase 0.1 0.2 0.2 0.1 DTPA / HEDP 0.5 0.3 0.5 1.0 LOBS - 0.8 - 0.3 PB1 5 3.0 10 4.0 DOBA 1.0 - 0.4 - TAED 0.5 0.3 0.5 0.6 sulfate 4.0 5.0 - 5.0 S PI - 0.4 - - suds suppressor - 0.5 - - Speckle 1.0 0.5 - - Other / minor 100% the sum of component

Example 4 The following composition is a pretreatment composition according to the present invention. O P Q R S T U MES 1.0 2.0 0.8 4.0 - - - C45E7 6.5 7.5 - - - - - C23E3 - 2.0 5.0 5.0 7.0 9.0 3.0 C25E2.5S 10.0 14.0 17.0 8.0 5.0 15.0 20.0 SADS - - 3.0 - 1.0 1.0 2.0 Citric Acetic acid 3.5 4.0 2.5--3.0 3.5 Tyl triethyl percarbonate--3.0 2.0 3.0-- Perborate 2.0 3.0 ---1.0 5.0 NACA-OBS 0.3 --- 0.6 0.4 NOBS / LOBS / DOBS 1.0-1.0 0.2 0.4 - - TAED 0.5 0.6 0.3 0.8 0.9 0.4 0.7 chelating agent 0.3 0.5 - - 0.2 - 0.8 to pH4 by addition of water and minor ingredients H ₂ SO ₄

[0173] Example 5 V W X Y Z AA BB sodium _{C 11 ~C 13 12.0 16.0 23.0 19} 18.0 20.0 16.0 alkylbenzene sulfonate sodium _{C 14 ~C 15 4.5 - - -} 4.0 alcohol sulfate C ₁₄ -C ₁₅ alcohol - - - - - ethoxylate (0.5) sulfate C ₁₄ -C ₁₅ alcohol - - 2.0 - 1.0 1.0 1.0 ethoxylate (3) sulfate sodium _{C 14 ~C 15 2.0 2.0 - 1.3} - - 0.6 alcohol ethoxylate (3.0) _C 9 _{-C 14} Alkyl--1.0 0.5 2.0 Dimethylhydroxyethyl quaternary ammonium salt tallow fatty acid----1.0 Tallow alcohol ------- Ethoxylate (50) sodium tripolyphosphate 23.0 25.0 24.0 22.0 20.0 15.0 20.0 Sodium carbonate 15.0 12.0 15.0 10.0 13.0 11.0 10.0 Sodium poly 0.5 0.5 0.5 0.5--- Acrylate (45%) Sodium polyacryl--1.0 1.0 1.0 2.0 0.5 rate / Maleate polymer sodium silicate (1: 6 ratio 3.0 6.0 9.0 8.0 9.0 6.0 8.0 NaO / SiO ₂ ) (46%) Sodium sulfate 25.0 18.0 20.0 18.0 20.0 22.0 13.0 Sodium perborate 5.0 5.0 10.0 8.0 3.0 1.0 2.0 poly (ethylene glycol 1.5 1.5 1.0 1.0 - - 0.5 Le), about 4000 (50%) molecular weight sodium carboxymethyl 1.0 1.0 1.0 - 0.5 0.5 0.5 methylcellulose citrate - - - - - - - NOBS / DOBS 0.5 1.0 0.5 0.5 1.0 0.7 0.3 TAED 1.5 1.0 2.5 3.0 0.3 0.2 0.5 Soil release polymer ¹ 1.5 1.5 1.0 1.0 - 1.0 - Soil release polymer 2 ^- - - - 1.0 - 1.0 moisture 7.5 7.5 6.0 7.0 5.0 3.0 5.0 magnesium sulphate - - - - 1.0 0.5 1.5 Speckle 0.5 3.0-5.0 2.0-0.2 Chelating agent----0.8 0.6 1.0 Enzymes, amylase, amy-----2.0 1.5 2.0 Minor components including enzyme II, cellulase, protease and lipase , e.g. perfume, 1.0 1.0 1.0 1.0 0.5 1.5 1.0 Brightener, Photo bleach, dye 1. Non-cotton soil release polymer according to U.S. Pat. No. 5,415,807 issued to Gosselink, Pan, Kellett and Hall, May 16, 1995. 2. Non-cotton soil release polymer according to US Patent Application No. 60/051517.

Example 6 CC DD EE FF Sodium C ₁₁ -C ₁₃ 13.3 13.7 10.4 8.0 Sodium alkylbenzenesulfonate C ₁₄ -C ₁₅ 3.9 4.0 4.5 -alcohol sulfate C ₁₄ -C ₁₅ alcohol 2.0 2.0-- ethoxylate (0.5) sulfate C ₁₄ -C ₁₅ alcohol - - - - ethoxylate (3) sulfate sodium _C 14 _{-C 15} alcohol 0.5 0.5 0.5 5.0 ethoxylate (6.5) _C 9 _{-C 14} alkyl dimethyl 1.0 - - 0.5 hydroxyethyl quaternary ammonium salt Taro Fatty acid 0.5 ---Tallow alcohol ethoxylate (50)--1.0 0.3 Sodium tripolyphosphate-41.0-20.0 Zeolite A, hydrate 26.3-21.3 1.0 (0.1-10 micron size) Sodium carbonate 23.9 12.4 25.2 17.0 Sodium polyacrylate ( 45%) 3.4 0.0 2.7 -Sodium polyacrylate /- -1.0 1.5 Maleate polymer sodium silicate (1: 6 ratio NaO / SiO ₂ ) (46%) 2.4 6.4 2.1 6.0 Sodium sulfate 10.5 10.9 8.2 15.0 Sodium perborate 1.0 1.0 1.0 2.0 Poly (ethylene glycol), 1.7 0.4 1.0 - about 4000 (50%) molecular weight sodium carboxymethyl cellulose 1.0 - - 0.3 citric acid - - 3.0 - NOBS / DOBS 0.2 0.5 0.5 0.1 TAED 0.6 0.5 0.4 0.3 Soil release polymer ¹ 1.5 - - - Soil release polymer ² - 1.5 1.0 1.0 Moisture 7.5 3.1 6.1 7.3 Magnesium sulfate---1.0 Chelating agent --- 0.5 Enzymes, amylase, amylase II, -1.0-1.5 Minor components including cellulases, proteases and lipases , e.g. perfume, brightener, 1.0 1.0 1.0 1.0 Light bleach, dye U.S. Pat. No. 4,968,451, Scheibel et al., 1990.
Non-cotton stain free polymer according to the promulgation on January 6th. 2. Non-cotton soil release polymer according to US Patent Application No. 60/051517.

──────────────────────────────────────────────────続 き Continuation of front page (81) Designated country EP (AT, BE, CH, CY, DE, DK, ES, FI, FR, GB, GR, IE, IT, LU, MC, NL, PT, SE ), OA (BF, BJ, CF, CG, CI, CM, GA, GN, ML, MR, NE, SN, TD, TG), AP (GH, GM, KE, LS, MW, SD, SZ, UG, ZW), EA (AM, AZ, BY, KG, KZ, MD, RU, TJ, TM), AL, AM, AT, AU, AZ, BA, BB, BG, BR, BY, CA, CH, CN, CU, CZ, DE, DK, EE, ES, FI, GB, GE, GH, GM, GW, HU, ID, IL, IS, JP, KE, KG, KP, KR , KZ, LC, LK, LR, LS, LT, LU, LV, MD, MG, MK, MN, MW, MX, NO, NZ, PL, PT, RO, RU, SD, SE, SG, SI, SK, SL, TJ, TM, TR, TT, UA, UG, US, UZ, VN, YU, ZW (71) Applicant ONE PROCTER & GANBLE PLAZA, CINCINNATI, OHIO, UNITED STATES OF AMERICA (72) Invention Rudevin, Pascal, Marie, Gripe Newcastle, UK, Appon, Tyne, Grosvenor, Road, 2 (72) Inventor Null-Edine, Guedilla Newcastle, UK, Appon, Tyne, Jesmond, Osborne, Road, 115th (72) Inventor Donald, Ray, Brown Middleta, Ohio, USA , Maple, Creek, Drive, 7045 (72) Inventor Michael, Frances, Melea, Ohio, USA, Hamilton, Eaton, Road, 4061 F-term (reference) 4H003 AB19 AB21 AB27 AB35 AC08 AE06 DA01 EA08 EA09 EA12 EA15 EA16 EA28 EB08 EB12 EB13 EB19 EB22 EB32 EB37 EB42 EC01 EC02 EC03 EE05 FA34 FA42 4H011 AA02 BB09 BB18 DA02 DA13 DD01

Claims (11)

[Claims] 1. A detergent composition having a density of 330 g / l to 700 g / l comprising a bleaching system comprising a hydrophilic and a hydrophobic peracid bleach or a precursor thereof and a peroxide source. The total amount of available oxygen (AvO-a) from the hydrophilic and hydrophobic peracid bleach is less than 5000 ppm by weight of the composition, and the available oxygen (AvO-a) of the hydrophobic peracid or its precursor -Hb) to the available oxygen (AvO-hp) of the hydrophilic peracid or its precursor is from 3: 1 to 1:50, and the available oxygen (AvO-o) of the peroxide source and AvO -A is at least 2
1: a detergent composition. 2. The detergent composition of claim 1, wherein the hydrophilic bleach precursor comprises TAED. 3. The hydrophobic peracid or precursor thereof comprises a hydrophobic group derived from a fatty acid and having at least 8 carbon atoms, preferably the peracid precursor has an oxybenzenesulfonate leaving group. The detergent composition according to claim 2. 4. The detergent composition according to claim 1, wherein the ratio of AvO-o to AvO-a is at least 3: 1, more preferably 4: 1. 5. The detergent composition according to claim 1, comprising a phosphate builder. 6. A method according to claim 1, wherein the peroxide source bleach comprises one or more inorganic perhydrate salts, preferably perborate or percarbonate. A detergent composition according to claim 1. 7. The detergent composition according to claim 1, which comprises one or more enzymes, preferably at least an amylase enzyme. 8. A method for manually washing laundry using the detergent composition according to claim 1. 9. A method for pretreating or immersing laundry with the detergent composition according to claim 1. 10. Use of a bleaching agent to reduce bacterial activity, wherein the bleaching composition comprises a hydrophilic and a hydrophobic peracid bleach or a precursor thereof and a peroxide source. Wherein the ratio of the available oxygen of the hydrophobic peracid or its precursor (AvO-hb) to the available oxygen of the hydrophilic peracid or its precursor (AvO-hp) is 3: 1 to 1:50. The ratio of available oxygen from the peroxide source (AvO-o) to the total amount of available oxygen from the hydrophilic and hydrophobic peracid bleach (AvO-a) is at least 2: 1; Is preferably present in the detergent composition in an amount such that the AvO-a is less than 10,000 ppm, alternatively less than 5000 ppm. 11. Contacting the fabric with a composition or a solution of a composition comprising a hydrophilic and hydrophobic peracid bleach or precursor thereof and a peroxide source,
A method for sanitizing a fabric, wherein the ratio of the available oxygen of a hydrophobic peracid or its precursor (AvO-hb) to the available oxygen of a hydrophilic peracid or its precursor (AvO-hp) is 3: A ratio of available oxygen from the peroxide source (AvO-o) to the total amount of available oxygen from the hydrophilic and hydrophobic peracid bleach (AvO-a) is at least 2: 1. Method.