CN1239986A - Detergent compositions containing isopeptidase - Google Patents

Abstract

Cleaning compositions, preferably laundry detergent compositions, comprising an isopeptidase enzyme having the ability to catalytically cleave the isopeptide bond between the glutamine gama-carboxamide and lysine epsilon-amino group.

Description

The detergent composition that contains isopeptidase

The cross reference document

The application requires the right of priority of the provisional application series number 60/028496 of application on October 15th, 1996 according to the 35th of United States Code 119 (e).

Invention field

The present invention relates to contain the cleaning combination of isopeptidase, preferred laundry detergent composition.Preferred laundry composition is a granular form.More specifically, the present invention relates to contain isopeptidase, detergent surfactant and washing assistant (for example silico-aluminate, silicate) are preferably with the detergent composition of detersive enzyme (for example proteolytic enzyme, lipase, amylase, cellulase) combination.

Background of invention

The most conventional detergent composition contains the mixture of various components, generally comprises to have the enzyme that cleans character.Usually the detersive enzyme that industry is used in laundry composition that runs into comprises: proteolytic enzyme, amylase, cellulase and lipase.In addition, also have in the document much in cleaning combination, using a large amount of combinations of other type enzyme of studying.Yet they seldom exceed the initial evaluation stage that is used for commercial composition.The tangible technical problem of using any enzyme to run in cleaning combination comprises: with other conventional component (tensio-active agent for example that cleans, washing assistant, other enzyme) consistency, stability and validity and operability under the pH condition of general storage and use have only been enumerated more here.

One class was not also studied the enzyme of using before in cleaning combination and was called isopeptidase.Identified first this fermentoid recently, this is the new enzymic activity in the salivary gland secretion of having found medicinal leech, utilize it [to see after having decomposed isopeptide bond between glutamine γ-methane amide and the Methionin epsilon-amino, for example, Fradkov etc., " in decomposing particularly-ε-(enzyme from medicinal leech (Hirudo medicinalis) of γ-Glu-)-Lys isopeptide bond: cDNA clone and protein primary structure " (" Enzyme from the medicinalleech (Hirudo medicinalis) that specifically splits endo-ε (γ-Glu-)-Lys isopeptide bonds:cDNA cloning and protem primary structure "), FEBS Letters, 390 (1996) 145-148].The isopeptidase that this enzyme (being referred to as " going stabilized enzyme (destabilase) ") especially decomposes in the stabilised blood fibrin chain is crosslinked, but stays complete polypeptide chain, thus at the stable fibrinogen of external liquefaction.Based on this enzymic activity (it reverses the final step in the blood clotting), isopeptidase is studied at present and may be used as thrombus dissolving reagent.

Now definite: it is useful that such activity is removed in the cleaning process of certain human body dirt at needs.It comprises attempts to remove the general difficult human body dirt of removing and the laundry processes of stain.A kind of such human body dirt attempting to remove or stain material be because in chemically stable-(γ-Glu-)-Lys isopeptide bond closes crosslinked and dirt fragment that anti-washing composition of part and proteolytic enzyme are removed ε, it is found in the angling shell of stratum corneum (skin) cell, derives part or all of human body dirt and stain on the fabric that is cleaned thus.(it can part generally be found in (γ-Glu-)-crosslinked protein of Lys is formed) on the collar of clothes and the cuff and on the underwear by interior-ε for dirt that such difficulty is removed and stain.Therefore, the purpose of this invention is to provide cleaning combination and the method for using isopeptidase.

Background technology

Finot.P.-A., Mottu.F., Bujard, E. and Mauron, J. (1978) Adv.Exp.Med.Bio.105,549-570, the document has illustrated the hydrolytic activity of γ-Gu Anxianji-ε-Methionin in the mouse kidney extract.Baskova, I.P., and Nikonov; G.I. (1985) Biokhimya50 (3); 424-431, the document has reported that the leech of liquefaction fibrinogen goes stabilized enzyme mechanism (hydrolysis of γ-Gu Anxianji-ε-Methionin), comprises the kinetics on artificial substrate γ-Gu Anxianji-pNA.[also referring to, Baskova, I.P. and Nikonov, G.I. (1991) Blood Coagulation and Fibrinolysis2,167-172, the document contains the kinetics of additional substrate.] Fradkov, A., Berezhnoy, S., Barsova, E., Zavalova, L, Lukyanov, S., Baskova, I. and Sverdlov, E.D. (1996) FEBS Letters390,145-148, the document has been described clone and the sequencing that goes stabilized enzyme.Also referring to Baskova, I.P., Nikonov, G.I. " goes stabilized enzyme, a kind of enzyme in the salivary gland secretion of medicinal leech, isopeptide bond in the hydrolysis-stable fibrinogen " (" Destabilase:An Enzyme in the Salivary GlandSecretion of Medicinal Leech-Hydrolyzes Isopetide Bonds in StabilizedFibrin "), Biokhimiya, Vol50 (3), 1985, pp.424-431; Baskova, I.P., Nikonov, G.I., Zavalova, L.L., and Larionova, " going stabilized enzyme, a kind of enzyme, the kinetics of hydrolysis L-γ-Glu-pNA " (" Kineticsof the Hydrolysis of L-γ-Glu-pNA by Destabilase; an Enzyme fromthe Leech Hirudo medicinalis ") from leech Hirudo medicinalis, Biochimiya, Vol 55 (4), pp674-479 (1990).

Hoshino, E., Maruta, K., Wada, Y. and Kazuo, M. (1995) JAOCS72 (7), 785-791, the document has been described the highly purified Sumizyme MP and the interaction that is contained in the human body skin keratinocyte of skin dirt that derive from bacillus KSM-K16 (it is said that K16 proteolytic enzyme has been separated and has been used for detergent for washing clothes) by electron microscope observation.It is said that this proteolytic enzyme penetrates into earlier in the keratinocyte, the initial period in hydrolysis mainly is adsorbed on the internal structure of this cell then, and the direct hydrolysis keratin fiber.

Summary of the invention

According to the present invention, provide a kind of cleaning combination that contains the isopeptidase of isopeptidase live vol (preferred laundry detergent composition for example is used for the composition of washing machine washing or pre-soaking).

Laundry detergent composition preferably, it comprises:

A) isopeptidase of about 0.0001-5% (preferably about 0.001-2%) weight; With

B) the detergent composition binder component of about 95-99.9999% weight.

The invention still further relates to laundry detergent composition, it comprises:

A) detergent surfactant of about 0.1-80% (preferably about 1-50%) weight;

B) isopeptidase of about 0.0001-5% (preferably about 0.001-2%) weight; With

C) the detergent composition binder component of about 0.1-99.8% weight preferably includes the washing assistant (for example, silico-aluminate, silicate, phosphoric acid salt, phosphonate etc.) of about 0.1-80%.Preferred compositions is a granular form.

The invention still further relates to detergent composition, it comprises:

A) the active detersive enzyme of about 0.0001-2% weight (being preferably selected from proteolytic enzyme, cellulase, lipase, amylase, peroxidase and its mixture);

B) isopeptidase of about 0.0001-5% (preferably about 0.001-2%) weight; With

C) the detergent composition binder component of about 0.1-99.8% weight (being preferably selected from detergent surfactant and/or washing assistant).

Preferably, these detergent composition comprise that one or more are selected from following detergent surfactant: anion surfactant is preferably selected from alkyl alkoxylated vitriol, alkyl-sulphate and/or linear alkyl sulfonate surfactant; Cats product is preferably selected from quaternary ammonium surfactant; Nonionogenic tenside is preferably selected from alkylethoxylate, alkyl polyglucoside and/or amine oxide surfactant; Amphoterics is preferably selected from trimethyl-glycine and/or multi-carboxylate (for example polyglycine salt); And zwitterionics.

Preferred detergent composition also comprises oxygen bleaching agent; it is selected from perborate, percarbonate; with its mixture, more preferably with the bleach-activating agent for example combination of nonanoly acyloxy benzene sulfonate (NOBS) and tetra acetyl ethylene diamine (TAED) activator and its mixture.Also can use ready-formed percarboxylic acids SYNTHETIC OPTICAL WHITNER.

Preferred composition of the present invention relates to granular detergent composition, and it comprises:

A) SYNTHETIC OPTICAL WHITNER of about 0.1-50% weight;

B) washing assistant that is selected from silico-aluminate, silicate and its mixture of about 1-80% weight;

C) the active detersive enzyme of about 0.0001-2% weight, it is selected from proteolytic enzyme, amylase, lipase, cellulase and its mixture;

D) isopeptidase of about 0.0001-5% (preferably about 0.001-2%) weight; With

E) the detergent composition binder component of about 0.1-99.8% weight.

The invention still further relates to the method for laundering of textile fabrics.The machine washing method that its aqueous solution that is included in fabric that makes the needs cleaning in the washing machine and the isopeptidase that contains the isopeptidase live vol (with preferred detergent surfactant in addition) contacts.Another washing methods is the hand washing method, and it comprises that the fabric that needs are cleaned soaks (preferably at least about 5 minutes, more preferably at least about 15 minutes) in the aqueous solution of the isopeptidase that contains the isopeptidase live vol.

Except as otherwise noted, all percentage ratios, ratio and ratio herein is all to prepare the weight of final composition component.All documents of quoting herein are all incorporated by reference in this article at relevant portion.

Detailed Description Of The Invention

The invention provides detergent composition, said composition is by using isopeptidase as described herein, preferably with one or more SYNTHETIC OPTICAL WHITNER, silico-aluminate, silicate, the combination of detergent surfactant and/or detersive enzyme provides effective dirt and stain to clean, and it is granular form preferably.

Preferred compositions and the preparation of one or more detergent surfactants are so that assist to use the cleaning process of isopeptidase.General and preferred detergent surfactant is selected from: anion surfactant is preferably selected from alkyl alkoxylated vitriol, alkyl-sulphate and/or linear alkyl sulfonate surfactant; Cats product is preferably selected from quaternary ammonium surfactant; And nonionogenic tenside, preferred alkyl ethoxylate, the many polyglycosides of alkyl and/or amine oxide surfactant.

Percarbonate and perborate that peroxide bleaching agent is discharged in the washings are the basic technologies of modern super compact grained laundry detergent formulations.Peroxide bleaching agent is very hydrophilic; although it can not be compared with the bleaching action that is provided by peracid (for example interacted by superoxide and TAED and forms), aspect pigment (for example in particle or beverage stain) decolouring be effectively and help from the organic residue relevant, remove color with the human body dirt.

The present invention also provides detergent composition, and said composition is by being used in combination bleach-activating agent (comprising the ready-formed peracid) with isopeptidase in the present composition and method, and preferred hydrophobic bleach activator provides effective cleaning of dirt and stain.

The present invention also provides such composition, and said composition provides effective cleaning of dirt and stain by use bleaching catalyst in the present composition and method.Bleaching catalyst (it is characterized by and have at least a transition metal atoms) thus interact to form very powerful hydrophilic SYNTHETIC OPTICAL WHITNER with superoxide.These SYNTHETIC OPTICAL WHITNER provide very strong effect to coloured hydrophilic stain and hydrophilic daily dirt (being socks).Catalyzer generally is used for cleaning products with extremely low content.As disclosed herein, the product that contains isopeptidase and SYNTHETIC OPTICAL WHITNER and catalyzer provides excellent cleaning and/or whiteness performance.Yet should be realized that: using bleaching catalyst in the past is inconvenient because relate to fabric infringement (known two Mn catalysts can cause the fabric infringement), therefore must consider this problem when preparation contains the present composition of bleaching catalyst.

The present invention also provides such composition, said composition is by in the present composition, preferably use the washing assistant that is selected from silico-aluminate, silicate, phosphoric acid salt, carbonate and its mixture that effective cleaning of dirt and stain is provided in the composition of granular form.

In addition, the invention provides such composition, said composition provides effective cleaning of dirt and stain by use additional detersive enzyme in the compositions and methods of the invention.

Isopeptidase:

A basal component of cleaning combination of the present invention is an isopeptidase.Term used herein " isopeptidase " refers to the enzyme with isopeptide bond ability between catalytic decomposition glutamine γ-methane amide and the Methionin epsilon-amino.For purpose of the present invention, term used herein " isopeptidase live vol " refers to the amount that has the isopeptidase that the catalytic activity necessary amounts of cleaning benefit effectively is provided under normal service condition.Preferably, with about 0.0001-5%, preferably the amount of about 0.01-2% joins isopeptidase in the composition of the present invention.

The catalytic activity of isopeptidase generally can change, and this depends on used concrete enzyme variant.Use Baskova, I.P. and Nikonov, G.I. (1991), Blood Coagulation and Fibrinolysis2, the method of 167-172 can be measured the catalytic activity of each isopeptidase, this method is as follows: " according to described methods such as Svendsen [Svendsen L.; Blomback B; Blomback M. etc.; Synthetic chromogenic substrate for determmation of trypsin, thrombin andthrombin-like enzymes.Thromb Res 1972; 1:267-278], (Behringwerke is Austria) at the amide decomposition activity of 405nm place determination test preparation to use chromogenic substrate L-γ-Glu-pNA.With the slow middle solution (pH8.0) of Tris (Tutofusin tris)-HCl of (0.9-x) ml 0.05M, 0.2ml substrate solution (0.45mg/ml, 1.58 * 10 ^-3M contains 0.01M CaCl at 0.05M ₂, during the Tris-HCl of pH8.0 is slow in the solution) and the stabilized enzyme solution that goes of xml be put in the spectrophotometric cuvette.Measure dynamics data with Lineweaver and Burk method.”

" containing the different peptide of 32nmol, 11.9nmol enzyme, the H of 2.5 μ l ₂During the 0.05M boric acid of O and 80 μ l is slow in the system of solution, pH7.4 measures down at 36 ℃ and to go stabilized enzyme to different peptide ε-(hydrolytic action of γ-Glu)-Lys.With the citric acid of the 0.2M of the 0.1N HCl of 10 μ l and 100 μ l slow in solution (pH2.2) be divided into the aliquots containig of 20 μ l.Control sample brackish water rather than go stabilized enzyme.The sample of 50 μ l is placed on the only resin B iotronic BTC2710 of Biotronic LC500l of amino acid analysis, and the analytical column of 7-8mmk is (on 400 * 32mm)." [at the 168th page]

Use these methods, it is reported (waiting 169 pages) that this isopeptidase " goes stabilized enzyme " and has following surface properties: " specific activity is 0.15 * 10 ^-9Mol/s.mg, K _m=2.2 * 10 ^-4M, k _Kat=3.53 * 10 ^-3s ^-1(pH9.0,37 ℃).”

Isopeptidase herein comprises that natural deutero-isopeptidase is as " going stabilized enzyme ", its aminoacid sequence is from document [Fradkov etc. " Enzyme from the medicinal leech (Hirudomedicinalis) that specifically splits endo-ε-(γ-Glu)-Lys isopeptidebonds:cDNA cloning and protein primary structure ", FEBS Letters, 390 (1996) 145-148; See SEQ ID Nos.2 and 7] in be known and any mutation (for example SEQID Nos.4 and 6) of isopeptidase live vol of the purpose of cleaning combination of the present invention and method can be provided.Such mutation can be naturally occurring or genetic engineering obtains.Preferred mutation shows positive immunological cross-reaction to the antibody of naturally occurring isopeptidase.

Because preparation is used for the isopeptidase of the present composition and method should be cheap as much as possible, so this enzyme must be able to be produced therefore preferably its expression of design in the transgene expression system in large quantities economically.These systems are known in field of protein expression, and can comprise, but be not limited to: express in the system below: gram-negative bacteria is intestinal bacteria for example, gram-positive bacteria is Bacillus subtilus for example, yeast is Saccharomyces cerevisiae or Pichia pastoris for example, mould is aspergillus for example, mammalian or insect cell substratum, or crop for example tobacco, cereal, soybean or other can change gene so that express and put aside proteinic plant.Isolate cDNA Nucleotide and measured the sequence of going stabilized enzyme and two mutation (SEQ ID Nos1,3 and 5).

Render a service about the optimum performance in detergent composition of the present invention and method, can design any such mutation particularly.For example, can design mutation like this makes this enzyme and the consistency of the cleaning combination component that runs into usually improve.Also can design mutation like this makes the best pH, bleach stability, catalytic activity etc. of this enzyme be suitable for granulated detergent to use.

Additional detergent component

Detergent composition of the present invention also can contain additional detergent component.The definite character of these annexing ingredients and the content of its adding depend on the physical form of composition and the definite character of the washing operation that the use composition carries out.

Composition of the present invention preferably contains one or more additional detergent components, and it is selected from: tensio-active agent, and SYNTHETIC OPTICAL WHITNER, other enzyme, washing assistant, alkaline system, organic polymer, suds suppressor, dirt suspends and anti redeposition agent, and corrosion inhibitor.

Detergent surfactant:

Detergent composition of the present invention preferably also comprises tensio-active agent, also be referred to as cosurfactant herein, it is preferably selected from: anion surfactant is preferably selected from alkyl alkoxylated vitriol, alkyl-sulphate and/or linear alkyl sulfonate surfactant; Cats product is preferably selected from quaternary ammonium surfactant; Nonionogenic tenside, preferred alkyl ethoxylate, alkyl polyglucoside and/or amine oxide surfactant; Amphoterics is preferably selected from trimethyl-glycine and/or multi-carboxylate (for example polyglycine salt); And zwitterionics.In detergent composition of the present invention, can use the cosurfactant of wide region.The tabulation and the kind of negatively charged ion, nonionic, both sexes and the zwitterionic classes of these cosurfactants in the US3664961 of the Norris of on May 23rd, 1972 promulgation, have been provided.In " amphoterics (the 2nd edition) " (Marcel Dekker, Inc. published in 1996) that E.G.Lomax compiles, also described amphoterics in detail.

Laundry detergent composition of the present invention generally contains the 0.1-35% weight of having an appointment, the cosurfactant of preferably about 0.5-15% weight.The tensio-active agent of selecting further specifies as follows:

(1) negatively charged ion cosurfactant:

The nonrestrictive example that content is generally the useful negatively charged ion cosurfactant of about 0.1-50% weight herein comprises: conventional C ₁₁-C ₁₈Alkylbenzene sulfonate (" LAS ") and primary, side chain and random C ₁₀-C ₂₀Alkyl-sulphate (" AS "), formula CH ₃(CH ₂) _x(CHOSO ₃ ^-M ⁺) CH ₃And CH ₃(CH ₂) _y(CHOSO ₃ ^-M ⁺) CH ₂CH ₃C ₁₀-C ₁₈Secondary (2,3) alkyl-sulphate, x and (y+1) be to be at least approximately 7 wherein, preferably being at least about 9 integer and M is water-soluble cationic, sodium especially, unsaturated vitriol is oleyl sulfate for example, C ₁₀-C ₁₈α-sulfonated fatty acid ester, C ₁₀-C ₁₈APG, C ₁₀-C ₁₈Alkyl alkoxy sulfate (" AE _xS ", EO1-7 ethoxy sulfate especially), C ₁₀-C ₁₈Alkyl alkoxy carboxylate salt (especially EO1-5 ethoxy carboxylate).C ₁₂-C ₁₈Trimethyl-glycine and sultaine (" sultaine "), C ₁₀-C ₁₈Amine oxides etc. also can be included in the whole composition.Also can use C ₁₀-C ₂₀Conventional soap class.High if desired whipability can be used the C of side chain ₁₀-C ₁₆Soap.Other conventional useful negatively charged ion cosurfactant is listed in the standard textbook.

Useful herein alkyl alkoxylated sulfate surfactant is formula RO (A) preferably _mSO ₃The water-soluble salt of M or acid, wherein R is unsubstituted C ₁₀-C ₂₄Alkyl or have C ₁₀-C ₂₄The hydroxyalkyl of moieties, preferred C ₁₂-C ₁₈Alkyl or hydroxyalkyl, more preferably C ₁₂-C ₁₅Alkyl or hydroxyalkyl, A are oxyethyl group or propoxy-unit, and m is greater than 0, be generally about 0.5-6, more preferably from about 0.5-3 and M are H or positively charged ion, and this positively charged ion can be: for example metallic cation (as sodium, potassium, lithium, calcium, magnesium etc.), ammonium or replace ammonium cation.Estimate to use alkyl ethoxylated sulfate and alkyl propoxylated sulphates herein.The object lesson that replaces ammonium cation comprises: ethanol, three ethanol, methyl, dimethyl, trimethyl ammonium positively charged ion and quaternary ammonium cation tetramethyl-ammonium and lupetidine positively charged ion and from alkylamine such as ethamine, diethylamine, triethylamine, its those positively charged ions of mixture deutero-etc.Illustrational tensio-active agent is: C ₁₂-C ₁₅Alkyl polyethoxylated (1.0) vitriol (C ₁₂-C ₁₅E (1.0) M), C ₁₂-C ₁₅Alkyl polyethoxylated (2.25) vitriol (C ₁₂-C ₁₅E (2.25) M), C ₁₂-C ₁₅Alkyl polyethoxylated (3.0) vitriol (C ₁₂-C ₁₅E (3.0) M) and C ₁₂-C ₁₅Alkyl polyethoxylated (4.0) vitriol (C ₁₂-C ₁₅E (4.0) M), wherein M is selected from sodium and potassium easily.

Useful herein alkyl sulfate surfactant is formula ROSO preferably ₃The water-soluble salt of M or acid, wherein R C preferably ₁₀-C ₂₄Alkyl preferably has C ₁₀-C ₁₈The alkyl of moieties or hydroxyalkyl, more preferably C ₁₂-C ₁₅Alkyl or hydroxyalkyl, with M be H or positively charged ion, for example alkali metal cation (as sodium, potassium, lithium), or ammonium or replace ammonium (as methyl, dimethyl and trimethyl ammonium positively charged ion and quaternary ammonium cation for example tetramethyl-ammonium and lupetidine positively charged ion and from alkylamine for example ethamine, diethylamine, triethylamine and its mixture deutero-quaternary ammonium cation etc.).

Other operable suitable anion surfactant is an alkyl sulfonate surfactants, comprises according to " The Journal of the American Oil Chemists Society ", 52 (1975), pp.323-329 gaseous state SO ₃Sulfonated C ₈-C ₂₀The linear ester of carboxylic acid (being lipid acid).Proper raw material comprises from tallow, palm wet goods deutero-natural fat material.

Preferred alkyl sulfonate surfactants (in particular for the laundry purposes) comprises the alkyl sulfonate surfactants of following structural formula:

R ³-CH (SO ₃M)-C (O)-OR ⁴R wherein ³Be C ₈-C ₂₀Alkyl, preferred alkyl, or its mixture, R ⁴Be C ₁-C ₆Alkyl, preferred alkyl, or its mixture and M are the positively charged ions that forms water-soluble salt with the alkyl ester sulfonate radical.The salifiable positively charged ion of suitable shape comprises metallic cation such as sodium, potassium and lithium and replacement or unsubstituted ammonium cation such as monoethanolamine, diethanolamine and trolamine.Preferably, R ³Be C ₁₀-C ₁₆Alkyl, and R ⁴Be methyl, ethyl or sec.-propyl.Particularly preferably be methyl ester sulfonate, wherein R ⁵Be C ₁₀-C ₁₆Alkyl.

Other also can be included in the laundry detergent composition of the present invention the useful negatively charged ion cosurfactant of washing purpose.They can comprise: the salt of soap (comprise, for example sodium, potassium, ammonium and the ammonium that replaces such as list, two and triethanolamine salt), C ₈-C ₂₂Uncle or secondary paraffin sulfonate, C ₈-C ₂₄The sulfonated poly carboxylic acid of alkene sulfonate, the preparation of the sulfonation by the alkaline earth metal citrate pyrolysis product (for example, as described in the British Patent No. 1082179), C ₈-C ₂₄Alkyl polyglycol ether sulfate (containing the most nearly 10 moles oxyethane); Monoesters (the particularly saturated and unsaturated C of alkyl glycerol sulfonate, fatty acyl group glycerol sulfonate, fatty oil base glycerol vitriol, alkyl phenol epoxy ethane ether salt, paraffin sulfonate, alkylphosphonic, isethionate such as acyl isethinate, N-acyl taurine salt, amber alkyl amide salts and sulfosuccinate, sulfo-succinic acid ₁₂-C ₁₈Monoesters) and the diester of sulfo-succinic acid (particularly saturated and unsaturated C ₆-C ₁₂Diester), the vitriol of the alkyl polysaccharide vitriol of the many polyglycosides of alkyl (compound of nonionic non-sulfuric acidization described below) and alkyl polyethoxye carboxylate salt those formulas RO (CH for example for example ₂CH ₂O) _k-CH ₂COO ^-M ⁺Salt, wherein R is C ₈-C ₂₂Alkyl, k are that integer and the M of 0-10 is the positively charged ion that forms soluble salt.Resinous acid and hydrogenant resinous acid also are suitable, for example rosin, staybelite and the resinous acid and the hydrogenated resin acid that are present in or are derived from tallol.Other example is described among " Surface Active Agents andDetergents " (volume I and II, Schwartz, Perry and Berch).Various such tensio-active agents also usually are disclosed in 58 row-29 hurdles, 23 hurdles, 23 row of US3929678 (people such as Laughlin, promulgation on December 30th, 1975) (document is incorporated herein by reference).

Preferred dithionate has following formula:

Wherein R is that chain length is C ₁-C ₂₈, preferred C ₃-C ₂₄, C most preferably ₈-C ₂₀Alkyl, alkyl, alkenyl, aryl, alkaryl, ether, ester, amine or the amide group of replacement, perhaps hydrogen; It is C that A and B are selected from chain length independently of one another ₁-C ₂₈, preferred C ₁-C ₅, C most preferably ₁Or C ₂Alkyl, the alkyl and the alkenyl of replacement, or covalent linkage, and A and B contain at least 2 atoms altogether; A, B and R contain about 31 carbon atoms of 4-altogether; X and Y are the anionic groups that is selected from sulfate radical and sulfonate radical, and condition is that at least one is a sulfate radical among X or the Y; M is a cationic moiety, preferably replaces or unsubstituted ammonium ion, perhaps basic metal or alkaline-earth metal ions.

Most preferred dithionate tensio-active agent has following formula, and wherein R is that chain length is C ₁₀-C ₁₈Alkyl, A and B are C independently of one another ₁Or C ₂, X and Y are sulfate radicals, M is potassium, ammonium or sodium ion.

By detergent composition weight, the amount that this dithionate tensio-active agent exists generally is about 0.1-50%, preferably about 0.1-35%, most preferably from about 0.5-15%.

Preferred herein dithionate tensio-active agent comprises:

(a) 1,3 dithionate compound, preferred 1,3 C7-C23 (being carbon sum in the molecule) straight or branched alkyl or alkenyl dithionate more preferably have following formula:

Wherein R is that chain length is about C ₄-C ₁₈Straight or branched alkyl or alkenyl;

(b) 1,4 dithionate compound, preferred 1,4 C8-C22 straight or branched alkyl or alkenyl dithionate more preferably have following formula:

Wherein R is that chain length is about C ₄-C ₁₈Straight or branched alkyl or alkenyl; Preferred R is selected from: octyl group, nonyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl and its mixture; With

(c) 1,5 dithionate compound, preferred 1,5 C9-C23 straight or branched alkyl or alkenyl dithionate more preferably have following formula:

Wherein R is that chain length is about C ₄-C ₁₈Straight or branched alkyl or alkenyl.

The known synthetic alkyl or the alkenyl succinic anhydrides used usually of some dithionate tensio-active agent is as main raw material.It begins to stand reduction step, obtains glycol by this step.Then, thus this glycol stands the sulfation step obtains two sulfating products.As an example, US-A-3634269 has described 2-alkyl or alkenyl-1,4-butyleneglycol dithionate, and it is preparation like this: thus prepare alkenyl or alkyl diol by alkenyl succinic anhydrides with lithium aluminium hydride reduction, then with this glycol sulfation.In addition, US-A-3959334 and US-A-4000081 have described 2-alkyl-1,4-butyleneglycol dithionate, thus it also is to use and comprises with lithium aluminium hydride reduction alkenyl succinic anhydrides preparation alkenyl or alkyl diol, then its Sulfated method is prepared.

Also referring to US-A-3832408 and US-A-3860625, it has described 2-alkyl or alkenyl-1,4-butyleneglycol ethoxylate dithionate, it is to prepare alkenyl or alkyl diol with the lithium aluminium hydride reduction alkenyl succinic anhydrides, what ethoxylation prepared before sulfation then.

These compounds also can be by such method preparation, and this method comprises that this cyclic anhydride has the carbochain substituting group that one or more sums are at least 5 carbon atoms from the synthetic dithionate tensio-active agent of the cyclic anhydride that replaces, and it comprises following step:

(i) cyclic anhydride with described replacement reduces to form glycol; With

(ii) thereby described glycol sulfation is formed dithionate

Wherein said reduction step is included in the pressurization hydrogenation step that contains under the existence of transition metal hydrogenation catalyst.

When it comprised, laundry detergent composition of the present invention generally contained the 0.1-50% that has an appointment, the anion surfactant of preferably about 1-40% weight.

(2) nonionic cosurfactant:

The non-limitative example that its amount is generally the useful in this article nonionic cosurfactant of about 0.1-50% weight comprises: oxyalkylated alcohol (AE) and alkylphenol, polyhydroxy fatty acid amide (PFAA), APG (APG), C ₁₀-C ₁₈Glyceryl ether etc.

More specifically, the primary and secondary fatty alcohol is suitable as nonionogenic tenside of the present invention with the ethylene oxide condensate (AE) of about 1-25 mole.The alkyl chain of this fatty alcohol can be straight or branched, uncle or secondary, and contain 8-22 the carbon atom of having an appointment usually.Preferably have and contain about 8-20 carbon atom, the about 1-10 mole of the alcohol of 10-18 carbon atom alkyl and every mol of alcohol more preferably from about, preferred 2-7 mole, the most preferably condensation product of 2-5 moles of ethylene oxide.Particularly preferred this class nonionogenic tenside is the C that every mol of alcohol contains the 3-12 moles of ethylene oxide ₉-C ₁₅Primary alcohol ethoxylate, particularly every mol of alcohol contains the C of 5-10 moles of ethylene oxide ₁₂-C ₁₅Primary alconol.

The example of this class nonionogenic tenside that is commercially available comprises: by the Tergitol of UnionCarbide Corporation sale ^TM15-S-9 (C ₁₁-C ₁₅The condensation product of straight chain alcohol and 9 moles of ethylene oxide) and Tergitol ^TM24-L-6 NMW (the C of narrow molecular weight distributions ₁₂-C ₁₄The condensation product of primary alconol and 6 moles of ethylene oxide); With the Neodol that sells by Shell ChemicalCompany ^TM45-9 (C ₁₄-C ₁₅The condensation product of straight chain alcohol and 9 moles of ethylene oxide), Neodol ^TM23-3 (C ₁₂-C ₁₃The condensation product of straight chain alcohol and 3.0 moles of ethylene oxide), Neodol ^TM45-7 (C ₁₄-C ₁₅The condensation product of straight chain alcohol and 7 moles of ethylene oxide), Neodol ^TM45-5 (C ₁₄-C ₁₅The condensation product of straight chain alcohol and 5 moles of ethylene oxide); By Procter﹠amp; The Kyro that Gamble Company sells ^TMEOB (C ₁₃-C ₁₅The condensation product of alcohol and 9 moles of ethylene oxide); With the Genapol LA030 or the 050 (C that sell by Hoechst ₁₂-C ₁₄The condensation product of alcohol and 3 or 5 moles of ethylene oxide).The preferable range of the HLB of these AE nonionogenic tensides is 8-17, most preferably 8-14.Also can use and the condenses of propylene oxide and butylene oxide ring.

The polyhydroxy fatty acid amide surfactant that to be used for another kind of preferred nonionic cosurfactant herein be following formula:

R wherein ¹Be H, or R ¹Be C _1-4Alkyl, 2-hydroxyethyl, 2-hydroxypropyl or its mixture, R ²Be C _5-31Alkyl and Z be have the straight-chain alkyl chain, at least 3 hydroxyls are directly connected to the polyhydroxy alkyl on this chain, or its oxyalkylated derivative.Preferably, R ¹Be methyl, R ²It is straight chain C _11-15Alkyl or C _15-17Alkyl or alkenyl chain, for example coconut alkyl or its mixture and Z in reductive amination process from reducing sugar such as glucose, fructose, maltose, lactose-derived.General example comprises C ₁₂-C ₁₈And C ₁₂-C ₁₄The N-methyl glucose amide.See US5194639 and US5298636.Also can use N-alkoxyl group polyhydroxy fatty acid amide; See US5489393.

As nonionic cosurfactant of the present invention also alkyl polysaccharide usefully, for example at US4565647 (Llenado, promulgation on January 21st, 1986) disclosed alkyl polysaccharide in, this polysaccharide has and contains about 6-30, the hydrophobic grouping of preferred about 10-16 carbon atom with contain about 1.3-10, preferred about 1.3-3, the most preferably from about polysaccharide of 1.3-2.7 sugar unit such as polysaccharide glycosides hydrophilic radical.Can use any reducing sugar that contains 5 or 6 carbon atoms, for example, can partly replace the glucosyl part (randomly, at 2-with glucose, semi-lactosi and galactosyl, 3-, thereby 4-equipotential connection hydrophobic grouping obtains glucose or semi-lactosi corresponding to glucoside or galactoside).Between this sugar key can, for example, a position of additional sugar unit and the 2-of above-mentioned sugar unit, 3-, 4-, and/or between the 6-position.

Preferred APG has following formula:

R ²O (C _nH _2nO) _t(glycosyl) _x

R wherein ²Be selected from: alkyl, alkyl phenyl, hydroxyalkyl, hydroxyalkyl phenyl and its mixture, wherein alkyl contains the 10-18 that has an appointment, preferably about 12-14 carbon atom; N is 2 or 3, preferred 2; T is 0-10, preferred 0; X is about 1.3-10, preferably about 1.3-3, most preferably from about 1.3-2.7.This glycosyl is preferably from the glucose deutero-.In order to prepare these compounds, form alcohol or alkyl polyethoxye alcohol earlier, then with glucose, or the source of glucose reaction, form glucoside (connecting) in the 1-position.Then at the 2-of its 1-position and above-mentioned glycosyl units, 3-, 4-, and/or 6-position are preferably mainly connecting other glycosyl units between the 2-position.This compounds and be used for washing composition and be disclosed among the EP-B-0070077,0075996 and 0094118.

The polyethylene oxide of alkylphenol, poly(propylene oxide) and polybutylene oxide condenses are applicable to the nonionogenic tenside as surfactant system of the present invention, and the condenses of polyethylene oxide is preferred.These compounds comprise: have and contain about 6-14 carbon atom, the alkylphenol of the straight or branched alkyl of preferably about 8-14 carbon atom and the condensation product of alkylene oxide.In preferred embodiments, the amount of oxyethane equals every mole of about 2-25 mole of alkylphenol, the more preferably from about oxyethane of 3-15 mole.This class ionic surfactant pack that is commercially available is drawn together: by the Igepal of GAF Corporation sale ^TMCO-630; With by Rohm﹠amp; The Triton that HaasCompany sells ^TMX-45, X-114, X-100 and X-102.These tensio-active agents are referred to as alkyl phenolic alkoxy thing (for example, alkylphenol ethoxylate) usually.

Oxyethane also is suitable as additional nonionogenic tenside of the present invention with the condensation product of the hydrophobic group that forms by propylene oxide and propylene glycol condensation.The molecular weight of the hydrophobic part of these compounds is preferably about 1500-1800 and demonstrates water-insoluble.Polyoxyethylene is partly added to this hydrophobic portion branch increase the water-soluble of whole molecule, and it is the about 50% of this condensation product gross weight that the liquid property that keeps this product is up to polyoxyethylene content, it corresponding to about 40 moles ethylene oxide condensation at most.The example of this compounds comprises the Pluronic by the BASF sale that some is commercially available ^TMTensio-active agent.

The nonionogenic tenside that also is suitable as nonionic surfactant system of the present invention is an oxyethane and the condensation product of the product that obtains from propylene oxide and reacting ethylenediamine.The hydrophobic part of these products is made up of the reaction product of quadrol and excessive propylene oxide, and molecular weight generally is about 2500-3000.This hydrophobic part and ethylene oxide condensation, its degree is about 5000-11000 for polyoxyethylene and the molecular weight that this condensation product contains the 40-80% that has an appointment (weight).The example of this class nonionogenic tenside comprises the Tetronic by the BASF sale that some is commercially available ^TMCompound.

Also preferred nonionic is an amine oxide surfactant.Composition of the present invention can comprise the amine oxide of following general formula I:

R ¹(EO) _x(PO) _y(BO) _zN(O)(CH ₂R') ₂·qH ₂O????(I)

Usually can see that structural formula (I) provides 1 long-chain part R ¹(EO) _x(PO) _y(BO) _zWith 2 short chain portion C H ₂R '.R ' be preferably selected from hydrogen, methyl and-CH ₂OH.Common R ¹Be the alkyl of uncle or side chain, it can be saturated or undersaturated, preferred R ¹It is primary alkyl.When x+y+z=0, R ¹It is alkyl with about 8-18 chain length.When x+y+z is not equal to 0, R ¹Can be longer a little, have C ₁₂-C ₂₄Chain length.This general formula also can comprise wherein x+y+z=0, R ¹=C ₈-C ₁₈, R '=H and q=0-2, preferred 2 amine oxide.These amine oxides are described as follows: C _12-14Alkyl dimethyl amine oxide, cetyl dimethyl amine oxide, octadecyl amine oxide and its hydrate, especially dihydrate, as disclosed in US5075501 and US5071594, these 2 pieces of documents are incorporated by reference in this article.

The present invention also comprises such amine oxide, and wherein x+y+z is not equal to 0, and especially x+y+z equals about 1-10, R ¹Be to contain about 24 carbon atoms of 8-, the primary alkyl of preferably about 12-16 carbon atom; In these embodiments, y+z preferably 0, the preferably about 1-6 of x, more preferably from about 2-4; EO represents vinyloxy group; PO represents propenyloxy group; BO represents butenyloxy.By the synthetic method of routine, for example then the amine oxidation of ethoxylation can be prepared such amine oxide with hydrogen peroxide by the reaction of alkyl ethoxy sulfate and dimethyl amine.

Amine oxide very preferably at room temperature is a solution herein.Be applicable to that amine oxide herein made by the industry of a lot of manufacturerss, they comprise Akzo Chemie, Ethyl Corp. and Procter﹠amp; Gamble.See the compilation of McCutcheon and the survey article of Kirk-Othmer for other amine oxide manufacturers.

Although R ' is H in some preferred embodiment, for some latitudes being arranged than longer slightly the R ' of H.Particularly, the present invention comprises that also wherein R ' is CH ₂The embodiment of OH, for example two (2-hydroxyethyl) amine oxides of hexadecyl, two (2-hydroxyethyl) amine oxides of butter, two (2-hydroxyethyl) amine oxides of stearyl and two (2-hydroxyethyl) amine oxides of oil base, dimethyl dodecyl amine oxide dihydrate.

(3) cats product:

The non-limitative example that its amount is generally the positively charged ion cosurfactant of about 0.1-50% weight comprises: cholinesterase type quaternary ammonium and oxyalkylated quaternary ammonium (AQA) surfactant compounds etc.

As the useful positively charged ion cosurfactant of surfactant system component is cholinesterase type quaternary ammonium surfactant, and it preferably has surfactant properties and comprises at least one ester (compound of the water dispersible of key and at least one positively charged ion charged group promptly-COO-).For example, suitable cationic ester tensio-active agent comprises the cholinesterase tensio-active agent, discloses in US4228024, US4239660 and US4260529.

The preferred cation ester surfactant is those compounds with following formula:

R wherein ₁Be C ₅-C ₃₁Straight or branched alkyl, alkenyl or alkaryl chain or M ^-N ⁺(R ₆R ₇R ₈) (CH ₂) s; X and Y are selected from COO, OCO, O, CO, OCOO, CONH, NHCO, OCONH and NHCOO independently of one another, and wherein at least one is COO, OCO, OCOO, OCONH or NHCOO group among X or the Y; R ₂, R ₃, R ₄, R ₆, R ₇And R ₈Be selected from alkyl, alkenyl, hydroxyalkyl, hydroxyl alkenyl and alkaryl independently of one another with 1-4 carbon atom; And R ₅Be H or C independently ₁-C ₃Alkyl; Wherein in the scope of 0-8, the value of b is in the scope of 0-20 independently of one another for the value of m, n, s and t, and the value of a, u and v is 0 or 1 independently of one another, and condition is that among u or the v at least one must be 1; M is a counter anion.

R ₂, R ₃And R ₄Preferably be selected from CH independently of one another ₃With-CH ₂CH ₂OH.

M is preferably selected from halogenide, methylsulfate, sulfate radical and nitrate radical, more preferably methylsulfate, muriate, bromide or iodide.

The cationic ester tensio-active agent of preferred water dispersible is the cholinesterase with following formula:

R wherein ₁Be C ₁₁-C ₁₉The straight or branched alkyl chain.

Particularly preferred this cholinomimetic ester comprises: stearyl-cholinesterase season ammonium methyl halogenide (R ¹=C ₁₇Alkyl), palmitoyl cholinesterase season ammonium methyl halogenide (R ¹=C ₁₅Alkyl), myristoyl cholinesterase season ammonium methyl halogenide (R ¹=C ₁₃Alkyl), lauroyl cholinesterase season ammonium methyl halogenide (R ¹=C ₁₁Alkyl), coconut acyl group cholinesterase season ammonium methyl halogenide (R ¹=C ₁₁-C ₁₃Alkyl), butter acyl group cholinesterase season ammonium methyl halogenide (R ¹=C ₁₅-C ₁₇Alkyl) and its any mixture.

Lipid acid and the dimethylaminoethanol particularly preferred cholinesterase that direct esterification provides above can preparing in the presence of acid catalyst by required chain length.This reaction product is the C of every mole of 3-50 oxyethyl group at solvent such as ethanol, propylene glycol or preferred fat alcohol ethoxylate such as ethoxylation degree preferably with methyl halide then ₁₀-C ₁₈Thereby there is the quaternized down needed cationic materials that forms in fatty alcohol ethoxylate.They also can prepare with the direct esterification in the presence of the acid catalyst material of 2-ethylene halohydrin by the lipid acid with required chain length.Then thereby reaction product is formed needed cationic materials with Trimethylamine is quaternized.

Other suitable cationic ester tensio-active agent has following structural formula, and wherein d can be 0-20:

Aspect preferred, these cationic ester tensio-active agents are hydrolyzable under laundry washing methods condition.

Useful herein positively charged ion cosurfactant comprises oxyalkylated quaternary ammonium (AQA) surfactant compounds (hereinafter being referred to as " AQA compound ") with following formula:

R wherein ¹Be to contain 8-18 the carbon atom of having an appointment, preferred about 16 carbon atoms of 10-, the most preferably from about alkyl of 10-14 carbon atom or alkenyl; R ²Be the alkyl that contains 1-3 carbon atom, preferable methyl; R ³And R ⁴Can change and be selected from hydrogen (preferably), methyl and ethyl independently of one another; X ^-Be to be enough to provide electroneutral negatively charged ion, for example muriate, bromide, methylsulfate, sulfate radical or analogue.A and A ' can change and be selected from respectively C independently of one another ₁-C ₄Alkoxyl group, especially oxyethyl group (promptly-CH ₂CH ₂O-), propoxy-, butoxy and blended oxyethyl group/propoxy-; P is that 1-is about 30, preferred 1-about 4; Q is that 1-is about 30, and preferred 1-is about 4, most preferably-Yue 4; Preferred p and q are 1.Also referring to: on May 30th, 1979 disclosed Procter﹠amp; The EP2084 of Gamble Company, it has described this useful in this article cationoid cosurfactant.

Hydrocarbyl substituent R wherein ¹Be C ₈-C ₁₁, C especially ₁₀The AQA compound compare with higher chain length material and strengthened laundry particulate dissolution rate, especially under the cold water condition.Therefore, some preferably C of teacher that fills a prescription ₈-C ₁₁The AQA tensio-active agent.The content that is used to prepare the AQA tensio-active agent of finished product laundry detergent composition can be in the scope of about 0.1-5% weight, generally about 0.45-2.5% weight.

According to top described, be that the nonrestrictive of AQA tensio-active agent used herein specifies below.Should understand: according to the common convention of the nonionogenic tenside of conventional ethoxylation, the degree of alkoxylation of Shuo Ming AQA tensio-active agent is a mean value herein.Therefore, for example " EO2.5 ", " EO3.5 " etc. are normal to non-integral total EO value.Symbol R ¹R ²ApR ³A ' qR ⁴AQA-1 C ₁₂-C ₁₄CH ₃EO EO (being also referred to as coconut methyl EO2) AQA-2 C ₁₂-C ₁₆CH ₃(EO) ₂EOAQA-3 C ₁₂-C ₁₄CH ₃(EO) ₂(EO) ₂(coconut methyl EO4) AQA-4 C ₁₂CH ₃EO EOAQA-5 C ₁₂-C ₁₄CH ₃(EO) ₂(EO) ₃AQA-6 C ₁₂-C ₁₄CH ₃(EO) ₂(EO) ₃AQA-7 C ₈-C ₁₈CH ₃(EO) ₃(EO) ₂AQA-8 C ₁₂-C ₁₄CH ₃(EO) ₄(EO) ₄AQA-9 C ₁₂-C ₁₄C ₂H ₅(EO) ₃(EO) ₃AQA-10 C ₁₂-C ₁₈C ₃H ₇(EO) ₃(EO) ₄AQA-11 C ₁₂-C ₁₈CH ₃(propoxy-) (EO) ₃AQA-12 C ₁₀-C ₁₈C ₂H ₅(isopropoxy) ₂(EO) ₃AQA-13 C ₁₀-C ₁₈CH ₃(EO/PO) ₂(EO) ₃AQA-14 C ₈-C ₁₈CH ₃(EO) ₁₅ ^*(EO) ₁₅ ^*AQA-15 C ₁₀CH ₃EO EOAQA-16 C ₈-C ₁₂CH ₃EO EOAQA-17 C ₉-C ₁₁CH ₃-EO 3.5 mean values-AQA-18 C ₁₂CH ₃-EO 3.5 mean values-AQA-19 C ₈-C ₁₄CH ₃(EO) ₁₀(EO) ₁₀AQA-20 C ₁₀C ₂H ₅(EO) ₂(EO) ₃AQA-21 C ₁₂-C ₁₄C ₂H ₅(EO) ₅(EO) ₃AQA-22 C ₁₂-C ₁₈C ₃H ₇Bu (EO) ₂

* oxyethyl group is randomly with methyl or ethyl capping.

The cats product of preferred two ethoxylations herein can be buied with trade(brand)name ETHOQUAD from Akzo NobelChemicals Company.

Two-AQA the compound very preferably that is used for herein has following formula:

R wherein ¹Be C ₁₀-C ₁₈Alkyl and its mixture, preferred C ₁₀, C ₁₂, C ₁₄Alkyl and its mixture, X is any suitable negatively charged ion that electrobalance is provided, preferred muriate.With reference to above-mentioned general AQA structural formula because in preferred compound R ¹Be from coconut (C ₁₂-C ₁₄Alkyl) fraction fatty acid derived, R ²Be methyl and ApR ³And A ' qR ⁴Be respectively monosubstituted ethoxy, so the compound of this preferred type is referred to as " coconut methyl EO2 " or " AQA-1 " in last table in this article.

The preferred AQA compound of herein other comprises the compound of following formula:

R wherein ¹Be C ₁₀-C ₁₈Alkyl, preferred C ₁₀-C ₁₄Alkyl, independently, p is that 1-is about 3, and q is that 1-is about 3, and R is C ₁-C ₃Alkyl, preferable methyl, X is a negatively charged ion, especially muriate.

The compound of other the above-mentioned type comprises wherein oxyethyl group (CH ₂CH ₂O) unit (EO) is by butoxy (Bu), isopropoxy [CH (CH ₃) CH ₂O] and [CH ₂CH (CH ₃O)] unit (i-Pr) or positive propoxy unit (Pr), or EO and/or Pr and/or displaced those compounds of the unitary mixture of i-Pr.

The following describes other binder component that can be used for the present composition, but do not plan to be limited to these components.Although the combination of isopeptidase and these compositions of additives components can use routine techniques to provide as finished product with the form of liquid, gel, bar or analogue, the manufacturing of granular laundry detergent herein needs some special processing technologies so that reach best performance.Therefore, be prescription teacher's convenience, narrate the particulate manufacturing of doing washing separately in granule manufacture part (face as follows) in following.

The detergent composition of bleaching compounds-SYNTHETIC OPTICAL WHITNER and bleach-activating agent-herein preferably also contains SYNTHETIC OPTICAL WHITNER or contains SYNTHETIC OPTICAL WHITNER or the bleaching composition of one or more bleach-activating agents.The amount of SYNTHETIC OPTICAL WHITNER generally is about 1-30% of detergent composition, is more typically about 5-20%, in particular for fabric washing.If present, the amount of bleach-activating agent generally is to comprise that SYNTHETIC OPTICAL WHITNER adds about 0.1-60% of the bleaching composition of bleach-activating agent, is more typically about 0.5-40% so.

Be used for herein SYNTHETIC OPTICAL WHITNER and can be any in fabric washing, hard surface cleaning, perhaps other useful SYNTHETIC OPTICAL WHITNER of detergent composition in the known washing purpose that maybe will know now.These comprise oxygen bleaching agent and other SYNTHETIC OPTICAL WHITNER.Can use perborate bleach herein, for example, Sodium peroxoborate (as monohydrate or tetrahydrate).

Another kind of SYNTHETIC OPTICAL WHITNER that can unrestricted use comprises percarboxylic acids salt SYNTHETIC OPTICAL WHITNER and its salt.The suitable example of this class reagent comprises: the magnesium salts of monoperphthalic acid magnesium hexahydrate, metachloroperbenzoic acid, 4-amino in the ninth of the ten Heavenly Stems-4-oxo Perbutyric Acid and diperoxy dodecanedioic acid.Such SYNTHETIC OPTICAL WHITNER is disclosed in US4483781 (Hartman, on November 20th, 1984 promulgation), U.S. Patent application 740446 (people such as Burns, on June 3rd, 1985 application), EP0133354 (people such as Banks, on February 20th, 1985 is open) and US4412934 people such as (, issue November 1 nineteen eighty-three) Chung in.SYNTHETIC OPTICAL WHITNER very preferably also comprises as crossing oxy hexanoic acid in 6-amino in the ninth of the ten Heavenly Stems-6-oxo described in the US4634551 (people such as Burns, promulgation on January 6th, 1987).

Also can use peroxygen bleach.Suitable peroxy bleaching agent compound comprises: yellow soda ash peroxyhydrate and " percarbonate " SYNTHETIC OPTICAL WHITNER, trisodium phosphate peroxyhydrate, urea peroxyhydrate and sodium peroxide of equal value.Also can use persulphate SYNTHETIC OPTICAL WHITNER (for example, OXONE, DuPont industrial production) herein.

Preferred percarbonate bleach comprises that median size is the dried particle of about 500-1000 micron, the described particle of no more than about 10% (weight) less than about 200 microns described particles with no more than about 10% (weight) greater than about 1250 microns.Randomly, percarbonate can use silicate, borate or water soluble surfactant active to apply.Percarbonate can be buied from various commercial source such as FMC, Solvay and Tokai Denka.

Also can use the mixture of SYNTHETIC OPTICAL WHITNER.

Preferred and bleach-activating agent such as peroxygen bleach, perborate, percarbonate is combined, and this causes producing on the spot the peroxy acid corresponding to bleach-activating agent in aqueous solution (promptly in washing process).The various non-limitative examples of activator are disclosed among US4915854 (people such as Mao, promulgation on April 10 nineteen ninety) and the US4412934.Nonanoly acyloxy benzene sulfonate (NOBS) and tetra acetyl ethylene diamine (TAED) activator are typical, also can use its mixture.For the general SYNTHETIC OPTICAL WHITNER of useful other herein and activator referring to US4634551.

Amido deutero-bleach-activating agent very preferably is those of following formula:

R ¹N (R ⁵) C (O) R ²C (O) L or R ¹C (O) N (R ⁵) R ²C (O) L

R wherein ¹Be the alkyl that contains 6-12 the carbon atom of having an appointment, R ²Be the alkylidene group that contains 1-6 carbon atom, R ⁵Be hydrogen or alkyl, aryl or the alkaryl that contains 1-10 the carbon atom of having an appointment, L is any suitable leavings group.Leavings group is any group that is replaced from bleach-activating agent owing to cross hydrolysis negatively charged ion nucleophilic attack bleach-activating agent.Preferred leavings group is a phenylbenzimidazole sulfonic acid salt.

The preferred example of the bleach-activating agent of following formula comprises: as (the amino caproyl of 6-decoyl) Oxybenzene sulfonate, (the amino caproyl of 6-nonanoyl) Oxybenzene sulfonate, (the amino caproyl of 6-caprinoyl) Oxybenzene sulfonate and its mixture of describing in this paper US4634551 incorporated by reference.

Another kind of bleach-activating agent comprises the disclosed benzoxazine type activator in US4966723 (promulgation on October 30 nineteen ninety) by people such as Hodge, and the document is incorporated herein by reference.Benzoxazine type activator very preferably is:

The preferred bleach-activating agent of another class comprises the acyl lactam activator, especially as shown in the formula acyl caprolactam and acyl group Valerolactim:

R wherein ⁶Be H or alkyl, aryl, alkoxy aromatic yl or the alkaryl that contains about 12 carbon atoms of 1-.Lactan activator very preferably comprises: benzoyl caprolactam, capryloyl hexanolactam, 3; 5; 5-trimethyl acetyl base hexanolactam, nonanoyl hexanolactam, decanoyl hexanolactam, undecylene acyl caprolactam, benzoyl Valerolactim, capryloyl Valerolactim, decanoyl Valerolactim, undecylene acyl group Valerolactim, nonanoyl Valerolactim, 3; 5,5-trimethyl acetyl base Valerolactim and its mixture.Also referring to United States Patent (USP) 4545784 (Sanderson, promulgation on October 8th, 1985) (document is incorporated herein by reference), it discloses acyl caprolactam, comprises the benzoyl caprolactam that is adsorbed on the Sodium peroxoborate.

SYNTHETIC OPTICAL WHITNER except oxygen bleaching agent also is known in the art and can uses in this article.A special class non-oxygen bleaching agent of being concerned about comprises the photoactivation SYNTHETIC OPTICAL WHITNER, for example sulfonated zinc and/or aluminium phthalocyanine.License to people's such as Holcombe US4033718 referring on July 5th, 1977.If you are using, detergent composition generally contains such SYNTHETIC OPTICAL WHITNER of the 0.025-1.25% that has an appointment (weight), especially sulfonated zinc phthalocyanine.

If desired, bleaching compounds can be used manganic compound catalysis.Such compound is known in the art and comprises: for example, be disclosed in United States Patent (USP) 5246621; 5244594; 5194416; 5114606; With the manganese-based catalyst among European patent application publication No. 549271A1,549272A1,544440A2 and the 544490A1.The preferred example of these catalyzer comprises: Mn ^IV ₂(u-O) ₃(1,4,7-trimethylammonium-1,4,7-7-triazacyclononane) ₂-(PF ₆) ₂, Mn ^III ₂(u-O) ₁(u-OAc) ₂(1,4,7-trimethylammonium-1,4,7-7-triazacyclononane) ₂-(ClO ₄) ₂, Mn ^IV ₄(u-O) ₆(1,4, the 7-7-triazacyclononane) ₄-(ClO ₄) ₄, Mn ^IIIMn ^IV ₄(u-O) ₁(u-OAc) ₂(1,4,7-trimethylammonium-1,4,7-7-triazacyclononane) ₂-(ClO ₄) ₃, Mn ^IV(1,4,7 ,-trimethylammonium-1,4,7-7-triazacyclononane)-(OCH ₃) ₃(PF ₆) and its mixture.Other metal matrix bleach-activating agent is included in those disclosed in United States Patent (USP) 4430243 and 5114611.The manganese that use has the complex compound ligand of various enhancing bleaching actions has report below in the United States Patent (USP): 4728455; 5284944; 5246612; 5256779; 5280117; 5274147; 5153161; With 5227084.

As practical situation, and non-limited way can be regulated the composition of this paper and method so that provide at least about 1,000 ten thousand/a active bleaching catalyst material in wash water solution, in washings, preferably provide about 0.1ppm-700ppm, more preferably from about the catalyst substance of 1-50ppm.

Useful herein cobalt bleaching catalyst is known and is described in, for example, and M.L.Tobe, " Base Hydrolysis of Transition-Metal Complexes ", Adv.Inorg.BioinorgMech., (1983) are in 2, the 1-94 pages or leaves.Useful herein most preferred cobalt catalyst is to have formula [Co (NH ₃) ₅OAc] T _yCobalt five amine acetates, " OAc " expression acetate moiety part wherein, " Ty " is negatively charged ion, cobalt five amine acetate muriates especially, [Co (NH ₃) ₅OAc] Cl ₂And [Co (NH ₃) ₅OAc] (OAc) ₂[Co (NH ₃) ₅OAc] (PF ₆) ₂[Co (NH ₃) ₅OAc] (SO ₄); [Co (NH ₃) ₅OAc] (BF ₄) ₂[Co (NH ₃) ₅OAc] (NO ₃) ₂(herein " PAC ").

These cobalt catalyst are easily with known method preparation, are for example instructed in the document below: the embodiment of Tobe article neutralizes in the reference of wherein quoting, US4810410 (people such as Diakun, promulgation on March 7th, 1989), J.Chem2Ed. (1989), 66 (12), 1043-45; Synthetic and the sign (The Synthesis and Characterizationof Inorganic Compounds) of mineral compound, W.L.Jolly (Prentice-Hall; 1970), pp.461-3; Inorg.Chem., 18,1497-1502 (1979); Inorg.Chem., 21,2881-2885 (1982); Inorg.Chem., 18,2023-2025 (1979); Inorg.Sythesis, 173-176 (1960); With Journal of Physical Chemistry, 54,22-25 (1952).

As practical situation, and non-limited way, can regulate the composition of this paper and method so that in wash water solution, provide at least about 1,000 ten thousand/a active bleaching catalyst material, about 0.01-25ppm preferably is provided in washings, more preferably from about 0.05-10ppm, most preferably from about the bleaching catalyst material of 0.1-5ppm.In order to obtain such content in the washings of automatic washing methods, by cleaning combination weight, general composition herein contains the 0.0005-0.2% that has an appointment, more preferably from about the bleaching catalyst of 0.004-0.08%, especially manganese or cobalt catalyst.

Enzyme-for various purposes comprises from substrate and removes protein-based, carbohydrate-based or triglyceride level base stain, in order to prevent that fugitive dye from shifting and for the fabric renewing, detergent composition of the present invention preferably includes enzyme in fabric washing.Suitable enzyme comprises any suitable source for example proteolytic enzyme, amylase, lipase, cellulase, peroxidase and its mixture in plant, animal, bacterium, mould and yeast source.The preferred influence of selecting to be subjected to these factors: for example best pH is active and/or stable, thermostability and to the stability of activated detergent, washing assistant etc.In this respect, bacterium and fungous enzyme are preferred, for example bacterial amylase and proteolytic enzyme and mould cellulase.

As used herein, " detersive enzyme " is meant anyly have cleaning in laundry, hard surface cleaning or personal care detergent composition, removes the enzyme of stain or other beneficial effect.Preferred detersive enzyme is a lytic enzyme, for example proteolytic enzyme, amylase and lipase.The purpose preferred enzyme that is used to do washing includes, but not limited to proteolytic enzyme, cellulase, lipase and peroxidase.Be used for washing automatically it is most preferred that amylase and/or proteolytic enzyme, comprise to obtain type in the market and improving type, but still SYNTHETIC OPTICAL WHITNER deactivation susceptibility is to a certain degree arranged although this improvement type is more compatible with SYNTHETIC OPTICAL WHITNER by continuous improvement.

Generally to be enough to the providing amount of " cleaning significant quantity " that enzyme is joined in washing composition or the detergent additives composition.Term " cleaning significant quantity " expression can for example generation such as fabric, tableware be cleaned, stain is removed, dirt is removed, brightens, gone to distinguish the flavor of or newly spend the amount of improved action to substrate.In fact in the market preparation, general amount is that every gram detergent composition is up to about 5mg (weight), more general about 0.01-3mg organized enzyme.In other words, composition herein generally contains 0.001-5% (weight), the commercial enzyme preparation of preferred 0.01-1% (weight).The amount that proteolytic enzyme exists usually in above-mentioned commodity preparation is for being enough to provide the activity of every gram composition 0.005-0.1Anson unit (AU).To some washing composition, for example therefore the washing composition of automatic dishwashing also is modified into spot/film forming or other net result for the total amount that the on-catalytic active material that provides is provided is minimum, it is desirable to improve the organized enzyme content of commodity preparation.Higher active content also is an ideal in highly enriched detergent formulation.

The suitable example of proteolytic enzyme is the subtilysin that obtains from specific subtilis and Bacillus licheniformis bacterial strain.A suitable proteolytic enzyme obtains from Bacillus strain, and it has maximum activity in the scope of pH8-12, sells by Novo Industries A/S (hereinafter being " the Novo ") development of Denmark and with registered trademark ESPERASE.The preparation of this enzyme and similar enzyme has been described in the british patent specification 1,243,784 of Novo.Other suitable proteolytic enzyme comprises the ALCALASE of Novo ^RAnd SAVINASE ^R, International Bio-Synthetics, the MAXATASE of Inc. (Holland) ^RAnd the disclosed protease A and the EP303 on April 28th, 1987 among the european patent application 130756A on January 9th, 1985, the proteolytic enzyme B among the 761A and the EP130756A on January 9th, 1985.Also referring to the high pH proteolytic enzyme that obtains from bacillus NCIMB40338 among the WO9318140A that is described in Novo.Comprise proteolytic enzyme, the enzyme detergent of one or more other enzymes and reversible protease inhibitors is described among the WO9203529A of Novo.Other preferred proteolytic enzyme comprises Procter﹠amp; Among the WO9510591A of Gamble those.When needs, the adsorptivity that can be reduced and the water-disintegrable proteolytic enzyme of increase are as Procter﹠amp; The WO9507791 of Gamble is described.The proteolytic enzyme that is suitable for the recombinant chou trypsinase shape in this paper washing composition is described among the WO9425583 of Novo.

In more detail, the proteolytic enzyme of a kind of particularly preferred being called " proteolytic enzyme D " is to have a carbonylic hydrolase variant that does not have the aminoacid sequence found at occurring in nature, it be by following mode from precursor carbonylic hydrolase deutero-: by being equivalent at described carbonylic hydrolase+76 positions, preferred also be equivalent in numbering according to the bacillus amyloliquefaciens subtilysin be selected from+99 ,+101 ,+103, + 104 ,+107 ,+123, + 27, + 105 ,+109 ,+126, + 128, + 135 ,+156 ,+166, + 195, + 197 ,+204 ,+206, + 210, + 216 ,+217 ,+218, + 222, + 260 ,+265, and/or+one or more amino acid residue positions of 274, replace the multiple amino acids residue with different amino acid, as described at the WO95/10615 of Genencor Intemational (April 20 nineteen ninety-five is open).

Useful proteolytic enzyme also be described in following PCT open in: November 9 nineteen ninety-five disclosed Procter﹠amp; The WO95/30010 of Gamble Company, November 9 nineteen ninety-five disclosed Procter﹠amp; The WO95/30011 of Gamble Company, November 9 nineteen ninety-five disclosed Procter﹠amp; The WO95/29979 of Gamble Company.

The amylase that is suitable for herein especially but is not limited to the automatic dishwashing purpose comprises, for example, and the α-Dian Fenmei of in GB1296839 (Novo), describing, RAPIDASE ^R(International Bio-Synthetics, Inc.) and TERMAMYL ^R(Novo).The FUNGAMYL of Novo ^RBe useful especially.Improve stability, for example the enzyme engineering of oxidative stability is known.See, for example, J.Biological Chem., Vol.260, No.11, in June, 1985, pp6518-6521.Some preferred embodiment of the present invention can be utilized has the stability of improvement in washing composition such as automatic dishwashing type washing composition, especially improve the amylase of oxidative stability, and it is the commercial TERMAMYL that uses with respect to 1993 ^RReference point is measured.These preferred amylase have the diastatic characteristic of " stability strengthen " herein, and its feature is at least measurable improvement of following one or more stability: for example at pH being the oxidative stability of the hydrogen peroxide/tetra acetyl ethylene diamine in the buffered soln of 9-10; For example in the common washing Wen Ding thermostability under 60 ℃ according to appointment; Or for example pH is the alkalescence stability of about 8-11; All measurements all are with the reference amylase comparative measurement of pointing out above.Can use any prior art test determination stability.See, for example be disclosed in the reference among the WO9402597.Stability enhanced amylase can obtain from Novo or Genencor International.

One class very preferably amylase herein has from one or more bacillus amylases, and especially the genus bacillus α-Dian Fenmei is used site-directed mutagenesis deutero-general character, and whether in the middle of with a kind of, two or more amylase strains being precursor is irrelevant.Be preferred for especially bleaching with reference to amylase oxidative stability enhanced amylase with respect to above-mentioned, more preferably in this paper detergent composition of oxygen bleaching (different) with chlorine bleaching.Preferred amylase like this comprises: (a) according to the amylase of the WO94/02597 of the Novo in the 3 days February in 1994 of above introducing, as being further specified by mutant, wherein use L-Ala or Threonine, preferred Threonine replacement is positioned at and is referred to as TERMAMYL ^The methionine residue of Bacillus licheniformis α-Dian Fenmei 197 positions, or similar parent's amylase, for example the same source position mutation of bacillus amyloliquefaciens, subtilis or bacstearothermophilus constitutes; (b) as Genencor International by the stable enhanced amylase of C.Mitchinson described in the article of being entitled as of on 207th American Chemical SocietyNational Meeting, submitting to 13-17 day in March, 1994 " oxidation resistant α-Dian Fenmei (OxidativelyResistant α-Amylases) ".The SYNTHETIC OPTICAL WHITNER of wherein mentioning in the automatic dishwashing washing composition makes the α-Dian Fenmei deactivation, but the amylase of improvement oxidative stability is made from Bacillus licheniformis NCIB8061 by Genencor.Methionine(Met) (Met) is considered to the residue that most probable is modified.8,15,197,256,304,366 and 438 replace Met one at a time and have caused specific mutant, and particularly important is M197L and M197T, and the M197T variant is the variant of stably express.At CASCADE ^RAnd SUNLIGHT ^RThe middle stability of measuring; (c) particularly preferred herein amylase be included in WO9510603A have among the parent in the middle of described other modification the amylase mutation and can be from transferee Novo with DURAMYL ^Obtain.Other particularly preferred oxidative stability enhanced amylase is included in those described in the WO9402597 of the WO9418314 of Genencor International and Novo.Can use any other oxidative stability enhanced amylase, for example diastatic known chimeric from obtaining, hybrid or simple mutant parent form are by the site-directed mutagenesis deutero-.Other preferred amylase modification can reach.See the WO9509909A of Novo.

Other amylase comprises those enzymes described in the application PCT/DK96/00056 of not winding up the case that are described in WO95/26397 and Novo Nordisk.The concrete amylase that is used for detergent composition of the present invention comprises and it is characterized by 25-55 ℃ temperature range and have the Termamyl of ratio under the pH of 8-10 scope ^RThe α-Dian Fenmei of specific activity of specific activity height at least 25%, it is to use Phadebas ^RThe alpha-amylase activity test determination.(above-mentioned Phadebas ^RThe alpha-amylase activity test is described in the 9-10 page or leaf of WO95/26397.) also be included in herein be with the SEQ ID tabulation that is shown in reference in aminoacid sequence at least 80% homologous α-Dian Fenmei.Press general composition weight meter, preferably with these enzymes with the pure enzyme of 0.00018-0.060%, more preferably the amount of the pure enzyme of 0.00024-0.048% joins in the laundry detergent composition.

The cellulase that can be used among the present invention comprises bacterium and the plain enzyme of mould fiber type, and preferred best pH is between 5-9.5.US4435307 (people such as Barbesgoard, on March 6th, 1984 promulgation) cellulase that discloses from Humicola insolens or humicola lanuginosa strain DSM 1800 or belonged to mould cellulase that the mould of the production of cellulose enzyme 212 of Aeromonas produces and extract from the hepatopancreas of sea mollusk (Dolabella Auricula Solander).Suitable cellulase also is disclosed in GB-A-2075028; Among GB-A-2095275 and the DE-OS-2247832.CAREZYME ^And CELLUZYME ^(Novo) be useful especially.Referring to WO9117243 (Novo).

The suitable lipase that is used for the washing composition purposes comprises as disclosed at English Patent GB 1372034, by the microorganism of pseudomonas, for example Situ Ci Shi aeruginosa atcc 19.154 produce those.Also referring to the lipase in Japanese patent application 53,20487 (on February 24th, 1987, special permission was open).This lipase can be from Amano Pharmaceutical Co.Ltd., Nagoya, and Japan buys with trade(brand)name Lipase P " Amano " or " Amano-P ".Other suitable merchant sells lipase and comprises Amano-CES, from the lipase of Chromobacter viscosum, as Chromobacter viscosum var.lipolyticum NRRLB3673 (from Toyo Jozo Co., Tagata, Japan); With from other Chromobacter viscosum lipase of US Biochemical Corp. (U.S.) and Disoynth Co. (Holland) with from the lipase of gladiolus pseudomonas.LIPOLASE that obtain from Humicola lanuginosa and that buy from Novo ^Enzyme (also referring to EP341947) is to be used for preferred fat enzyme of the present invention.Lipase and the amylase mutation stable to peroxidase are described among the WO9414951A (Novo).Also referring to WO9205249 and RD94359044.

Although disclose a lot of lipase, only find till now to obtain and the lipase produced as the host aspergillus oryzae is widely used as the fabric washing product additive from Humicolalanuginosa.As mentioned above, it is with trade(brand)name Lipolase from Novo Nordisk ^TMBuy.In order to make decontamination dirt performance the best of lipase, Novo Nordisk has made a lot of mutation.As described in the WO92/05249, compare (comparing these enzymes) every liter of proteinic scope of 0.075-2.5mg with the lipase of wild-type, the D96L mutation of natural Humicolalanuginosa lipase is removed the effectiveness of lard stain and has been improved 4.4 times.NovoNordisk disclosed in the disclosed research publication number 35944 and can add this lipase mutation (D96L) with the amount that is equivalent to every liter of washings 0.001-100mg (5-500000LU/ liter) lipase mutation on March 10th, 1994.In containing the detergent composition of isopeptidase, the present invention uses the D96L mutation of low levels in mode disclosed herein, and especially the content with every liter of about 50-8500LU of washings uses D96L that the benefit of improving the fabric whiteness maintenance is provided.

Be applicable to that keratanase herein is described among the WO8809367A of Genencor.

Peroxidase can for example percarbonate, perborate, persulphate, hydrogen peroxide etc. use with oxygen source.They generally are used for " solution bleaching " or the dyestuff or the pigment that prevent to break away from during washing operation are transferred to another substrate at washing soln from a substrate.Known peroxidase comprises horseradish peroxidase, lignoenzyme and halo peroxidase for example chloro or bromoperoxidase.The detergent composition that contains peroxidase is disclosed in WO89099813A, and (on October 19th, 1989 is Novo) and among the WO8909813A (Novo).

Various enzymes and their methods in the synthetic detergent composition of joining also being disclosed among the WO8908694A and US3553139 (being presented to people such as McCarty on January 5th, 1971) of the WO9307263A of Genencor International and WO9307260A, Novo.Enzyme also is disclosed among the US4101457 (people such as Place, promulgation on July 18th, 1978) and US4507219 people such as (, issued on March 26th, 1985) Hughes in.Be used for the enzyme material of liquid detergent formula and it joined being disclosed in such prescription among the US4261868 (people such as Hora, on April 14th, 1981).The enzyme that is used for washing composition can be with various consistent.The enzyme stabilization technique is open and be illustrated among US3600319 people such as (, promulgation on August 17th, 1971) Gedge and among European patent application EP 199405 and the EP200586 (Venegas, on October 29th, 1986).The enzyme stabilising system also is described in, for example among the US3519570.The useful bacillus AC13 that obtains proteolytic enzyme, zytase and cellulase is described among the WO9401532A (Novo).

The containing enzyme composition and can randomly contain the 0.001-10% that has an appointment (weight), preferably about 0.005-8% (weight), most preferably from about the enzyme stabilising system of 0.01-6% (weight) of enzyme stabilising system-herein.This enzyme stabilising system can be any enzyme stabilising system compatible with detersive enzyme.Such system can provide inherently with other actives of filling a prescription, and is perhaps for example added respectively by the manufacturers of prescription teacher or washing composition alternation enzyme.Such stabilising system can comprise: calcium ion, boric acid, propylene glycol, short chain carboxy acid, boronic acid and its mixture, and be designed to solve different stabilization problem with physical form according to the type of detergent composition.

A kind of stabilising method are to use water miscible calcium and/or magnesium ion source (it offers enzyme with above-mentioned ion) in final composition.If only use one type of cationic word, calcium ion is more effective a little and be preferred in this article than magnesium ion usually so.General detergent composition, especially every liter of final detergent composition of liquid composition comprises about 1-30, preferably about 2-20, the more preferably from about calcium ion of 8-12mmol, although have variation, this depends on these factors: comprise the diversity, type and the content that add enzyme.Preferred water miscible calcium or the magnesium salts of using comprises, for example: and calcium chloride, calcium hydroxide, calcium formiate, calcium malate, calcium maleate, calcium hydroxide and lime acetate, more generally, can use calcium sulfate or corresponding to the magnesium salts of the calcium salt that exemplifies.The content that further increases calcium and/or magnesium also is useful certainly, for example promotes the removal grease effect of some type list surface-active agent.

Another stabilising method are to use borate.See the US4537706 of Severson.When using, the content of borate stablizer be up to composition 10% or higher, but be more typically boric acid or other borate compound that is up to about 3% (weight), for example borax or orthoboric acid salt are applicable to that liquid washing agent uses.Can be with the boric acid that replaces phenyl-boron dihydroxide for example, butane boric acid replaces boric acid to bromophenylboronic acid or analogue, although and use the boron derivative of such replacement, can reduce the total boron content in the detergent composition.

Some cleaning combination for example stabilising system of automatic dishwashing composition can also contain about 10% (weight) of 0-, the chlorine bleach scavenging agent of preferred about 0.01-6% (weight), add this scavenging agent so that prevent to be present in the chlorine bleach material damage in a lot of water sources and make enzyme deactivation, particularly under alkaline condition.Although the cl content in water is very little, generally in the scope of about 0.5ppm-1.75ppm, during tableware or fabric washing with Total Water that enzyme contacts in available chlorine can be relatively large, so enzyme stability in use has problem sometimes.Because perborate or percarbonate (it has the ability with the chlorine bleach reaction) may reside in some composition of the present invention, its amount is the branch meter that comes with the enzyme stabilising system, so do not need to use other chlorine stablizer usually, but result who uses the chlorine stablizer to be improved.Suitable chlorine scavenger negatively charged ion is extensively known and can be easy to obtain, and if you are using, it can be the salt of ammonium cation and sulphite, hydrosulphite, thiosulfite, thiosulphate, iodide etc.Also can use antioxidant for example carbamate, xitix etc., organic amine is ethylenediamine tetraacetic acid (EDTA) (EDTA) or its an alkali metal salt, monoethanolamine (MEA) and its mixture for example.Equally, can mix special enzyme inhibition system makes different enzymes have maximum consistency.If desired, can use for example for example sodium perborate tetrahydrate, Sodium peroxoborate monohydrate and SPC-D and phosphoric acid salt, condensed phosphate, acetate, benzoate, Citrate trianion, formate, lactic acid salt, malate, tartrate, salicylate etc. and its mixture of hydrosulfate, nitrate, muriate, peroxide source of other conventional scavenging agent.Usually because can be by to recognize that better component (for example hydrogen peroxide cource) that its function is listed respectively carries out the function of chlorine scavenger, so add chlorine scavenger in addition is not absolute demand, unless at the compound that does not have this function of the carrying out of desired content in the enzyme embodiment that contains of the present invention; Even in this case, also only be to add this scavenging agent for optimum.In addition, the prescription teacher conventional technical ability that can use the chemist is when avoiding using preparation and inconsistent substantially enzyme scavenging agent of other reactive component or stablizer.About using ammonium salt, can mix this salt with detergent composition simply but this salt is easy to suction and/or discharges ammonia when storing.Therefore, if present, so such material better preserved is in particle as described in the US4652392 of Baginski etc.

Washing assistant-the be used for present composition especially preferred washing assistant of the composition of granular form is the detergent builders that is selected from silico-aluminate and silicate, it preferably includes in this article the composition, so that for example help to control mineral especially Ca and/or Mg hardness or help from the surface removal particulate fouling in the washing water.

That suitable silicate-like builder comprises water-soluble and aqueous solid type and comprise chain, stratiform or three-dimensional structure and unformed solid or non-structured kind of liquid.Preferably alkalimetal silicate, especially SiO ₂: Na ₂O is than 1.6: 1-3.2: those liquid and the solid of 1 scope, comprise, particularly for the automatic dishwashing purpose, by PQ Corp. with trade(brand)name BRITESIL ^RThe silicate of the BRITESIL H2O aqueous 2-ratio of solid of selling for example; With layered silicate for example at the lamina sodium silicate described in the US4664839 (H.P.Rieck, on May 12nd, 1987 promulgation).NaSKS-6 is abbreviated as " SKS-6 " sometimes, is crystalline layered, no aluminium, the δ-Na that is sold by Hoechst ₂SiO ₅The silicate of form and being particularly preferred in the granular laundry compositions.In DE-A-3417649 and DE-A-3742043, can see its preparation method.Other layered silicate for example has general formula NaMSi _xO _2x+1YH ₂Those of O, wherein M is sodium or hydrogen, x is 1.9-4, preferred 2 and y be 0-20, preferred 0, also can or be used for herein in addition.The layered silicate that derives from Hoechst comprises: as NaSKS-5, NaSKS-7 and the NaSKS-11 of α, β and γ form.Other silicate also is useful, Magnesium Silicate q-agent for example, and it can be as crisp (crispening) agent in granular recipe, as the stablizer of SYNTHETIC OPTICAL WHITNER with as the component of foam control system.

Also be applicable to herein be to have chain structure and have by acid anhydride formula general formula xM as disclosed in US5427711 (Sakaguchi etc., June 27 nineteen ninety-five) ₂OySiO ₂ZM ' O, wherein M is Na and/or K, M ' is Ca and/or Mg; Y/x is that 0.5-2.0 and z/x are 0.005-1.0, the synthetic crystallization ion-exchange material of the composition of expression or its hydrate.

The silico-aluminate washing assistant is useful especially in granulated detergent, but also can join liquid, in lotion or the gelatinous composition.Be suitable for the present invention seeks to the formula of seeing service [M _z(AlO ₂) _z(SiO ₂) _v] xH ₂Those of O, wherein z and v are at least 6 integer, and the mol ratio of z and v is 1.0-0.5, and x is the integer of 15-264.Silico-aluminate can be crystalline or unbodied, can naturally occurringly or synthetic obtain.A kind of method of producing silico-aluminate is disclosed in US3985669 (people such as Krummel, promulgation on October 12nd, 1976).Preferred synthetic crystallization aluminosilicate ion exchange material can zeolite A, and the title of zeolite P (B), X zeolite and the so-called zeolite MAP different with zeolite P obtains.Can use natural type, comprise clinoptilolite.Also can use and have formula Na ₁₂[(AlO ₂) ₁₂(SiO ₂) ₁₂] xH ₂The zeolite A of O, wherein x is 20-30, particularly 27.The zeolite (x=0-10) of dehydration also can use.Preferably, the particle diameter of silico-aluminate is the 0.1-10 micron.

Replace or also can randomly be included in the composition of this paper so that for example help to control mineral substance, especially Ca and/or the Mg hardness in the washing water or help except silicate mentioned above and the detergent builders the silico-aluminate from the surface removal particulate fouling.Washing assistant can work by various mechanism, comprises by ion-exchange and hardness ions forming soluble or insoluble complex compound and providing than being cleaned the surface that article surface is more conducive to precipitate hardness ions.Washing assistant content can have the variation on ground very on a large scale, and this depends on the end-use and the physical form of composition.The washing composition of adding assistant generally contains the washing assistant at least about 1%.Liquid formulations generally contains the 5-50% that has an appointment (weight), the washing assistant of more general 5-30% (weight).By detergent composition weight, granular recipe generally contains the 10-80% that has an appointment (weight), the washing assistant of more general 15-50% (weight).Yet, do not get rid of the washing assistant of lower or high level.For example some detergent additives or high surface agent prescription can be that adding assistant is insufficient.

Suitable herein washing assistant is selected from: phosphoric acid salt and poly-phosphate, especially sodium salt; Carbonate; Supercarbonate; The carbonate mine material of sesquicarbonate and non-yellow soda ash or concentrated crystal soda; Acid, sodium, potassium or alkanol ammonium salts form organic single, two, three and the tetracarboxylic acid hydrochlorate, especially water miscible nonsurfactant carboxylate salt; And oligomeric or water-soluble low molecular weight polymeric carboxylates, comprise aliphatic series and aromatic series type; And phytinic acid.It can use borate, for example is used for the slow purpose of pH, or uses vitriol, especially sodium sulfate and be that important other filler or carrier replenishes to the engineering of the detergent composition that contains stabilized surfactant and/or washing assistant.

Can use the washing assistant mixture, sometimes be referred to as " builder system ", it generally comprises the washing assistant that two or more are conventional, randomly is supplemented with sequestrant, the slow middle agent of pH or filler, and these materials of back are normally described the quantity of material time-division of the present invention and do not mentionleted alone bright.With respect to the amount of tensio-active agent in the washing composition of the present invention and washing assistant, preferred builder system is generally with about 60: 1-1: 80 tensio-active agent and the preparation of the weight ratio of washing assistant.This ratio of some preferred detergent for washing clothes is 0.90: 1.0-4.0: 1.0 scope, more preferably 0.95: 1.0-3.0: 1.0.

In allowed by law place, often preferred phosphorus-containing detergent washing assistant includes, but are not limited to: the basic metal of poly-phosphate, ammonium and alkanol ammonium salts, for example tri-polyphosphate, pyrophosphate salt, glass polymetaphosphate and phosphonate.

Suitable carbonate builders is included in disclosed alkaline-earth metal and alkaline carbonate in the German patent application numbers 2321001 (on November 15th, 1973 is open), but sodium bicarbonate, yellow soda ash, concentrated crystal soda and other carbonate mine material for example trona or the yellow soda ash of any routine and the double salt of lime carbonate for example consist of 2Na when it is anhydrous ₂CO ₃CaCO ₃And or even lime carbonate, comprise calcite, aragonite and vaterite, especially the form that has a high surface area with respect to the calcite of densification can be useful, for example as crystal seed or be used for the synthetic detergent soap bar.

Suitable organic washing-assisting detergent comprises multi-carboxylate's compound, comprises water miscible nonsurfactant dicarboxylate and tricarboxylate.More generally, the washing assistant multi-carboxylate has a plurality of carboxylate group, preferably at least 3 carboxylate radicals.Can be with acid, part neutral, neutrality or peralkaline form preparation carboxylate salt washing assistant.When being salt form, basic metal for example sodium, potassium and lithium or alkanol ammonium salts is preferred.The multi-carboxy acid salt washing agent comprises for example oxygen di-succinate of ether multi-carboxylate, sees US3128287 (Berg, on April 7th, 1964) and US3635830 (Lamberti etc., on January 18th, 1972); " TMS/TDS " washing assistant of US4663071 (Bush etc., on May 5th, 1987); Ether carboxylate washing assistant with other comprises ring-type and alicyclic compound, for example those that describe in the United States Patent (USP) below: US3923679, US3835163, US4158635, US4120874 and US4102903.

Other suitable washing assistant is an ether hydroxypolycarboxylic acid salt, the multipolymer of maleic anhydride and ethene or vinyl methyl ether, 1,3,5-trihydroxybenzene-2,4,6-trisulfonic acid, and carboxy methoxy-succinic acid, the ammonium salt of various basic metal, ammonium and the replacement of polyacetic acid is ethylenediamine tetraacetic acid (EDTA) and nitrilotriacetic acid(NTA) for example, and mellitic acid, succsinic acid, polymaleic acid, benzene 1,3,5-tricarboxylic acid, carboxy methoxy-succinic acid and its soluble salt.

The Citrate trianion washing assistant, for example citric acid and its soluble salt are because it is from available and its biodegradability of renewable source, so for example be the carboxylate salt washing assistant of particularly important for heavy duty liquid laundry detergent.Citrate trianion also can be used for particulate composition, particularly is used in combination with zeolite and/or layered silicate.Oxygen di-succinate also is useful especially in such composition and combination.

When allowing, in the soap bar prescription especially for the hand washing operation, can use alkali metal phosphate for example tripoly phosphate sodium STPP, trisodium phosphate and sodium orthophosphate.Also can use for example ethane-1-hydroxyl-1 of phosphonate washing assistant, 1-diphosphonate and other known phosphonate, for example US3159581; US3213030; US3422021; Among US3400148 and the US3422137 those, it has ideal antiscale character.

Some detergent surfactant or its short chain homologue also have the washing assistant effect.For the purpose of clear and definite formula calculation, when they have the tensio-active agent ability, these materials are summed up as detergent surfactant.The preferred type that is used for the washing assistant function is described as follows: be disclosed in 3 among the US4566984 (Bush, on January 28th, 1986), 3-dicarboxyl-4-oxa--1,6-adipate and relevant compound.The succsinic acid washing assistant comprises C ₅-C ₂₀Alkyl and alkenyl succinic and its salt.The succinate washing assistant also comprises: lauryl succinate, myristyl succinate, palmityl succinate, 2-laurylene base succinate (preferably), 2-ten pentaene base succinates etc.The lauryl succinate is described in the disclosed european patent application 8600690.5/0200263 on November 5th, 1986.Also can be with lipid acid C for example ₁₂-C ₁₈Monocarboxylic acid is incorporated into separately in the composition or with above-mentioned washing assistant especially Citrate trianion and/or succinate washing assistant as tensio-active agent/washing assistant material and makes up, so that additional washing assistant activity is provided.Other suitable multi-carboxylate is disclosed among US4144226 (Crutchfield etc., on March 13rd, 1979) and the US3308067 (Diehl etc., on March 7th, 1967).Also referring to the US3723322 of Diehl.

The inorganic builders material of operable other type has formula (M _x) _iCa _y(CO ₃) _z, wherein x and i are the integers of 1-15, and y is the integer of 1-10, and z is the integer of 2-25, M _iBe positively charged ion, its at least one be water miscible, and satisfy the formula ∑ _i=1-15 (x _iTake advantage of M _iValence state)+2y=2z, causing prescription to have neutrality or " equilibrated " electric charge.These washing assistants are referred to as " mineral washing assistant " herein.Can add the water of hydration or the negatively charged ion of non-carbonate, condition is that total charge is balance or neutral.These anionic electric charges or valence state effect should be added to the right of following formula.The preferred water-soluble cationic that is selected from hydrogen, water-soluble metal, hydrogen, boron, ammonium, silicon and its mixture that exists, more preferably sodium, potassium, hydrogen, reason, ammonium and its mixture, sodium and potassium are very preferred.The non-limitative example of non-carbonate anion comprises and is selected from following those: muriate, sulfate radical, fluorochemical, oxygen, oxyhydroxide, silicon-dioxide, chromate, nitrate radical, borate and its mixture.The preferred washing assistant of this class of its simple form is selected from: Na ₂Ca (CO ₃) ₂, K ₂Ca (CO ₃) ₂, Na ₂Ca ₂(CO ₃) ₃, NaKCa (CO ₃) ₂, NaKCa ₂(CO ₃) ₃, K ₂Ca ₂(CO ₃) ₃With its mixture.The Na that described herein particularly preferred washing assistant material is its crystalline modified form ₂Ca (CO ₃) ₂The suitable washing assistant of the above-mentioned type also illustrates with following material, it comprise natural or synthetic below any or its array configuration of mineral substance: Ah's cancrinite, andersonite, Y type ashcroftine, beyerite, the carbon kurchatovite, yellow water chestnut strontium cerium ore deposit, aqueous carbonate potassium calcium stone, cancrinite, stone cerium sodium stone, the carbon canasite, davyne, Y type carbon yttrium strontium stone, carbon potassium calcium stone, Ferrisurite, franzinite, carbon boron manganese calcium stone, gaylussite, Girvasite, Gregoryite, sulphur carbon calcium manganese stone, Kamphaugite Y, Kettnerite, Khanneshite, LepersonniteGd, liottite, Y type carbon barium yttrium ore deposit, microsommite, the carbon carlfriesite, Buddhist nun's shortite, Buddhist nun's shortite, RemonditeCe, the Sa davyne, the plate carburane, shortite, the plumbous stone of carbon sial, carbon sodium mayenite, sulphur silico-calcium potassium stone, tyrolite, vishnevite, Zemkorite.The preferable material form comprises Buddhist nun's shortite, carbon potassium calcium stone and shortite.

Polymeric dirt release agent-can randomly use known polymeric dirt release agent in detergent composition of the present invention hereinafter is referred to as " SRA ".If you are using, SRA accounts for the 0.01-10.0% of composition weight usually, general 0.1-5%, preferred 0.2-3.0%.

Preferred SRA generally have make hydrophobic fiber for example polyester and nylon surface hydrophilic hydrophilic segment and be deposited on the hydrophobic fiber and keep adhering to it and go up up to finishing and wash and rinse cycle, thus hydrophilic segment is played the hydrophobic part of an anchor effect.This can make handles dirt more easily cleaning in the washing process of back that the back exists with dirt release agent.

SRA can comprise various electric charges for example negatively charged ion or even cationic substance (seeing US4956447), and uncharged monomeric unit, and its structure can be straight chain, side chain or or even star.They can be included in the control molecular weight or change physics or the effective especially end-blocking part in surface-active property aspect.In order to be applied to different fibers or fabric type and, can to adjust structure and charge distribution in order to make the variation of washing composition or detergent additives product.Preferred SRA comprises oligomeric terephthalate, and it generally is by comprising that at least one is usually with for example method preparation of titanium (IV) alcoxylates transesterification/oligomerization of carrying out of metal catalyst.Use by 1,2,3,4 or more multi-position can join the other monomer that (does not form dense crosslinked one-piece construction certainly) in the ester structure and can prepare such ester.

Suitable SRA comprises the sulfonated products of linear ester oligopolymer basically; it partly is made up of the oligomer ester skeleton of terephthaloyl and the multiple unit of oxyalkylene oxygen basic weight and covalently bound allyl group deutero-sulfonation end group to skeleton; for example described in the US4968451 (J.J.Scheibel and E.P.Gosselink, November 6 nineteen ninety promulgation).Such ester oligomer can prepare by following step: (a) with the vinyl carbinol ethoxylation; (b) product and dimethyl terephthalate (DMT) (" DMT ") and 1 that will (a) in 2 step transesterification/oligomerization process, 2-propylene glycol (" PG ") reacts; (c) product with (b) reacts with sodium metabisulfite in water.Other SRA comprises US4711730 (people such as Gosselink, promulgation on December 8th, 1987) nonionic end capped 1,2-propylene/polyoxyethylene terephthalate polyester, those that transesterification/oligomerisation of for example passing through to gather (ethylene glycol) methyl ether, DMT, PG and gather (ethylene glycol) (" PEG ") prepares.Other example of SRA comprises: US4721580 (Gosselink, promulgation on January 26th, 1988) part and whole negatively charged ion end-blocking oligopolymer ester, for example derive from ethylene glycol (" EG "), PG, DMT and 3, the oligopolymer of 6-two oxa-s-8-hydroxyl perfluorooctane sulfonate; US4702857 (Gosselink, on October 27th, 1987 promulgation) the end capped block polyester oligomeric compound of nonionic is for example from those compounds of DMT, the end capped PEG of methyl (Me) and EG and/or PG or DMT, EG and/or end capped PEG of PG, Me and the preparation of 5-sodium sulfonate dimethyl isophthalate; And US4877896 (Maldonado; Gosselink etc.; promulgation on October 31st, 1989) negatively charged ion; the end capped terephthalate of sulfo group aroyl particularly; the latter generally is used for doing washing and the SRA of fabric-conditioning product; example is from a sulfosalicylic acid list sodium salt, PG and DMT, chooses wantonly but the preferred ester composition that also comprises PEG (for example PEG3400) preparation of adding.

SRA also comprises: the simple copolymerization block of ethylene terephthalate or terephthalic acid propylene glycol ester and terephthalic acid polyethylene oxide or poly(propylene oxide) ester, see US3959230 (Hays, issued on May 25th, 1976) and US3893929 (Basadur, promulgation on July 8th, 1975); The hydroxy ethers cellulosic polymer that derivatived cellulose for example obtains with METHOCEL from Dow; C ₁-C ₄Alkylcellulose and C ₄Hydroxy alkyl cellulose is seen US4000093 (Nicol etc., promulgation on December 28th, 1976).The suitable SRA that is characterized as poly-(vinyl ester) hydrophobic part comprises poly-(vinyl ester) that be grafted on the polyalkylene oxide skeleton for example C ₁-C ₆Vinyl ester, the graft copolymer of preferred poly-(vinyl-acetic ester).See disclosed european patent application 0219048 on April 22nd, 1987 such as Kud.The example that commerce is buied comprises the SOKALAN HP-22 that SOKALAN SRA for example obtains from German BASF.Other SRA has to contain 10-15% (weight) ethylene terephthalate and 80-90% (weight) is the polyester of the polyoxyethylene glycol deutero-polyoxyethylene terephthalate repeating unit of 300-5000 from molecular-weight average.Commercial example comprises the ZELCON5126 of Dupont and the MILEASE T of ICI.

Another preferred SRA is the formula of seeing service (CAP) ₂(EG/PG) ₅(T) ₅(SIP) ₁Oligopolymer; it contains terephthaloyl (T); sulfo group isophthaloyl base (SIP); ethylene oxide oxygen base and oxidation-1; 2-propylidene (EG/PG) unit and its are preferably used END CAPPED GROUP (CAP); the isethionate terminated of preferred modification; it comprises 1 sulfo group isophthaloyl base unit as oligopolymer; 5 terephthaloyl unit; the qualification ratio; preferred about 0.5: 1-10: 1 ethylene oxide oxygen base and oxidation-1,2-propenyloxy group unit and 2 are from 2-(2-hydroxyl-oxethyl)-ethane sulfonic acid sodium deutero-end-blocking unit.By oligopolymer weight, described SRA preferably also contains the stablizer of the reduction degree of crystallinity of 0.5-20%, for example anion surfactant such as linear alkyl benzene sulphonate or be selected from the material of dimethylbenzene, cumene and tosylate or its mixture, these stablizers or properties-correcting agent are joined in the synthesising container, as at US5415807 (Gosselink, Pan, Kellet and Hall, promulgation on May 16 nineteen ninety-five) instructed.The suitable monomers that is used for following formula SRA comprises 2-(2-hydroxyl-oxethyl)-ethane sulfonic acid sodium, DMT, 5-sodium sulfonate dimethyl isophthalate, EG and PG.

The preferred SRA of a class is an oligomer ester again, it comprises: (1) skeleton, this skeleton comprises: (a) at least one is selected from following unit: dihydroxyl sulfonate, polyhydroxy sulfonate, be that therefore trifunctional forms unit and its mixture that ester bond causes the branched oligomer skeleton at least; (b) at least one terephthaloyl unit; (c) unit of at least one unsulfonated, this unit is 1,2-oxidation alkylene oxide group; (2) one or morely be selected from following end-blocking unit: nonionic end-blocking unit; negatively charged ion end-blocking unit is for example oxyalkylated; isethionate, oxyalkylated propane sulfonate, oxyalkylated propane stilbene-4,4'-bis-(1-azo-3, 4-dihydroxy-benzene)-2,2'-disulfonate, the oxyalkylated phenolsulfonate of preferred ethoxylation, sulfo group aromatic acyl derivative and its mixture.The ester that preferably has following empirical formula:

{(CAP)x(EG/PG)y’(DEG)y”(PEG)y”’(T)z(SIP)z’(SEG)q(B)m}

CAP wherein, EG/PG, PEG, T is identical with top definition with SIP, (DEG) expression two (ethylene oxide) oxygen base unit, (SEG) expression is from the sulfo group ethyl ether and the deutero-unit, relevant portion unit of glycerine, and (B) expression is that therefore trifunctional forms the collateralization unit that ester bond causes the branched oligomer skeleton at least, and x is about 1-12, y ' is about 0.5-25; y " be that 0-is about 12, y " ' be that 0-is about 10, y '+y "+y " ' summation is about 0.5-25; z is about 1.5-25; z ' is that 0-is about 12, and z+z ' summation is about 1.5-25, and q is about 0.05-12; M is about 0.01-10; And x, y ', y ", y " ', z, z ', q and m represent the average mol of every mole of described ester corresponding units, and the molecular weight of described ester is in the scope of about 500-5000.

The preferred SEG and the CAP monomer of above-mentioned ester comprise: 2-(2-, 3-dihydroxyl propoxy-) ethane sulfonic acid sodium (" SEG "), 2-{2-(2-dihydroxyl oxyethyl group) oxyethyl group } product of ethane sulfonic acid sodium (" SE3 ") and its homologue and its mixture and ethoxylation and sulfonation vinyl carbinol.Preferred SRA ester in this class comprises with suitable Ti (IV) catalyzer following material transesterification and oligomeric product: 2-{2-(2-dihydroxyl oxyethyl group) oxyethyl group } ethane sulfonic acid sodium and/or 2-[2-{2-(2-dihydroxyl oxyethyl group) oxyethyl group } oxyethyl group] ethane sulfonic acid sodium, DMT, 2-(2-, 3-dihydroxyl propoxy-) ethane sulfonic acid sodium, EG and PG; It can be referred to as (CAP) 2 (T) 5 (EG/PG) 1.4 (SEG) 2.5 (B) 0.13, and wherein CAP is (Na ^+-O ₃S[CH ₂CH ₂O] 3.5)-and B be the unit that derives from glycerine, and the EG/PG mol ratio is about 1.7: 1, it is with conventional gas Chromatographic Determination after complete hydrolysis.

Also have a class SRA to comprise: (I) to connect the nonionic terephthalate of polymeric ester structure, see US4201824 (Violland etc.) and US4240918 (Lagasse etc.) with the vulcabond coupling agent; Thereby (II) by trimellitic acid 1,2-anhydride being joined the SRA that among the known SRA terminal hydroxy group is transformed into the trimellitate preparation with carboxylicesters end group.Selecting catalyst suitably, this trimellitic acid 1,2-anhydride forms the key that connects polymer terminal group by the ester of the isolating carboxylic acid of trimellitic acid 1,2-anhydride rather than by opening anhydride bond.Can use nonionic or negatively charged ion SRA as raw material, as long as they have can esterification hydroxyl end groups.See US4525524 (people such as Tung); (III) urethane bond connects the SRA of the negatively charged ion terephthalic acid ester group of variant, sees US4201824 (Violland etc.); (IV) poly-(caprolactam) and relevant and monomeric multipolymer such as vinyl pyrrolidone and/or dimethylaminoethyl acrylate methyl base amino-ethyl ester comprise nonionic and cationic polymers, see 4579681 (Ruppert etc.); (V) graft copolymer, except the SOKALAN type that derives from BASF, it prepares by Acrylic Acid Monomer is grafted on the sulfonated polyester.These SRA have soil release and the antiredeposition activity that is similar to known ether of cellulose certainly: see EP279134A (Rhone-Poulenc Chemie, 1988); (VI) for example vinylformic acid and vinyl-acetic ester are seen the EP457205 (1991) of BASF at the protein grafts on the casein for example to vinyl monomer; (VII) the polyester-polyamide SRA by condensation hexanodioic acid, hexanolactam and polyoxyethylene glycol preparation in particular for handling polyamide fabric, sees the DE2335044 (Unilever N.V., 1974) of Bevan etc.Other useful SRA is described in United States Patent (USP) 4240918,4787989,4525524 and 4877896.

Clay soil removal/anti deposition agent-composition of the present invention more also can randomly contain and has that clay soil is removed and the amine of the water-soluble ethoxylation of antiredeposition character.The granular detergent composition that contains these compounds generally contains the amine of the water-soluble ethoxylation of the 0.01-10.0% that has an appointment (weight); Liquid detergent composition generally contains the 0.01-5% that has an appointment (weight).

Most preferred soil release and anti redeposition agent are the tetrens of ethoxylation.Illustrative ethoxylated amine has further description in US4597898 (VanderMeer, promulgation on July 1st, 1986).Another kind of preferred clay soil removal-anti redeposition agent is the cation compound that is disclosed in the european patent application 111965 (Oh and Gosselink, on June 27th, 1984 is open).Operable other clay soil removal/anti deposition agent again comprises the amine polymer that is disclosed in the ethoxylation in the european patent application 111984 (Gosselink, on June 27th, 1984 is open); Be disclosed in the amphoteric ion polymer in the european patent application 112592 (Gosselink, on July 4th, 1984 is open); With the amine oxide that is disclosed among the US4548744 (Connor, promulgation on October 22nd, 1985).Other clay soil removal known in the art and/or anti redeposition agent also can be used for the composition of this paper.Referring to the US4891160 of the VanderMeer that authorizes January 2 nineteen ninety and November 30 nineteen ninety-five disclosed WO95/32272.Another kind of preferred anti redeposition agent comprises carboxymethyl cellulose (CMC) material.These materials are known in this area.

Polymeric dispersion agent-polymeric dispersion agent can be advantageously used in the amount of about 0.1-7% (weight) in herein the composition, when especially having zeolite and/or layered silicate washing assistant.Suitable polymeric dispersion agent comprises polymeric multi-carboxylate and polyoxyethylene glycol, although also can use other dispersion agent known in the art.Although do not plan bound by theory, but it is believed that: when with other washing assistant (comprising the lower molecular weight multi-carboxylate) when being used in combination, free peptization and antiredeposition by crystal growth inhibition, particulate fouling, the polymeric dispersion agent has strengthened total detergent builders performance.

By suitable unsaturated monomer preferably can be prepared polymeric multi-carboxylate material with its sour form polymerization or copolymerization.The monomer that can polymerization forms suitable multi-carboxylate polymer comprises: vinylformic acid, toxilic acid (or maleic anhydride), fumaric acid, methylene-succinic acid, equisetic acid, methylfumaric acid, citraconic acid and methylene radical propanedioic acid.The monomer fragment that has carboxylate-containing group not among the polymeric multi-carboxylate in this article for example vinyl methyl ether, vinylbenzene, ethene etc. is suitable, and condition is that such fragment does not constitute greater than about 40% (weight).

Specially suitable polymeric multi-carboxylate can obtain from vinylformic acid.The polymkeric substance of useful in this article acrylic like this is the acrylic acid water-soluble salt of polymeric.The molecular-weight average of such polymkeric substance of acid form is preferably in the scope of about 2000-10000, more preferably from about 4000-7000, most preferably from about 4000-5000.The water-soluble salt of such acrylate copolymer can comprise: the salt of basic metal, ammonium and replacement ammonium for example.This class soluble polymer is known material.The purposes of this class polyacrylate in detergent composition has been disclosed among the US3308067 (Diehl, promulgation on March 7th, 1967).

The multipolymer of vinylformic acid/maleic also can be as the preferred ingredient of dispersion agent/anti redeposition agent.Such material comprises the water-soluble salt of vinylformic acid and maleic acid.The molecular-weight average of such multipolymer of acid form is preferably in the scope of about 2000-100000, more preferably from about 5000-75000, most preferably from about 7000-65000.Acrylate in such multipolymer and the ratio of maleate fragment are usually about 30: 1-1: 1 scope, preferred about 10: 1-2: 1.The water-soluble salt of such vinylformic acid/maleic acid comprises: for example, and the salt of basic metal, ammonium and replacement ammonium.This class solubility acrylate/maleate copolymer is known material, it is described in european patent application 66915 (December 15 nineteen eighty-two is open) and EP193360 (on September 3rd, 1986 is open), and it has also described this polymkeric substance that contains the hydroxypropyl acrylate.Other also useful dispersion agent comprises toxilic acid/vinylformic acid/vinyl alcohol terpolymer.Such material also is disclosed among the EP193360, comprises for example 45/45/10 terpolymer of vinylformic acid/toxilic acid/vinyl alcohol.

The polymeric material that another can comprise is polyoxyethylene glycol (PEG).PEG can demonstrate the performance of dispersion agent and play clay soil removal-anti redeposition agent.Be used for the scope of the general molecular weight ranges of this purpose, preferably about 1000-50000, more preferably from about 1500-10000 at about 500-100000.

Also can use polyaspartic acid salts and polyglutamate, especially use with zeolite builders.Dispersion agent such as aspartate preferably have about 10000 molecular weight (on average).

Whitening agent-can with any white dyes known in the art or other increases gorgeous or whitening agent joins in the detergent composition of this paper, its amount generally is about 0.01-1.2% (weight).Commercially available white dyes of the present invention can be useful on and subgroup can be divided into, it comprises, but be not necessarily limited to stilbene, pyrazoline, tonka bean camphor, carboxylic acid, methyne cyanine, dibenzothiophene-5,5-dioxide, pyrroles, 5-and 6-unit's heterocyclic derivative and other all ingredients.The example of such whitening agent is disclosed in " production of white dyes and application (The Production andApplication of Fluorescent Brightening Agents) ", M.Zahradnik, Jone Wiley﹠amp; Sons, New York publishes (1982).

The object lesson of useful white dyes is those that point out in US4790856 (Wixon, promulgation on December 1st 3,1988) in the present composition.These whitening agent comprise the PHORWHITE series whitening agent of Verona.Other whitening agent that is disclosed in this reference comprises: can be from the Tinopal UNPA of Ciba-Geigy acquisition, Tinopal CBS and Tinopal5BM; Artic White CC and Artic White CWD; 2-(4-styryl-phenyl)-2H-naphtho-[1,2-d] triazole; 4,4 '-two-(1,2,3-triazoles-2-yl)-stilbene; 4,4 '-two (styryl) biphenyl; And aminocoumarin.The specific examples of these whitening agent comprises 4-methyl-7-diethyl amino coumarin; 1, the two (ethene of benzimidazolyl-2 radicals-yl) of 2-; 1,3-phenylbenzene-pyrazoline; 2, the two (benzoxazoles of 5--2-yl) thiophene; 2-styryl-naphtho--[1,2-d] oxazole; And 2-(stilbene-4-yl)-2H-naphtho-[1,2-d] triazole.Referring to US3646015 (being presented to Hamilton on February 29th, 1972).

Dye transfer inhibitor-composition of the present invention can comprise that also one or more transfer to the effective material of another fabric to suppressing dyestuff from a fabric in washing process.Usually such dye transfer inhibitor comprises multipolymer, manganese phthalocyanine, peroxidase and its mixture of polyvinyl pyrrolidone polymers, polyamine N-oxide pllymers, N-vinyl pyrrolidone and N-vinyl imidazole.If you are using, the content of these reagent generally is about 0.01-10% of composition weight, preferably about 0.01-5% and 0.05-2% more preferably from about.

More specifically, preferably be used for the unit that herein polyamine N-oxide pllymers contains following structural formula: R-A _x-P; Wherein P is a polymerizable unit, and the N-O group can be connected on the polymerizable unit or the N-O group can form polymerizable unit a part or N-O group can be connected on these two unit; A is one of following structure :-NC (O)-,-C (O) O-,-S-,-O-,-N=; X is 0 or 1; R is aliphatic series, aromatic series, heterocycle or alicyclic group or its mixture of aliphatic series, ethoxylation, and the nitrogen-atoms of N-O group can be connected thereto or the N-O group is the part of these groups.Preferred polyamine N-oxide compound is that wherein R is for example those of pyridine, pyrroles, imidazoles, tetramethyleneimine, piperidines and its derivative of heterocyclic group.

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

R wherein ₁, R ₂, R ₃Be aliphatic series, aromatic series, heterocycle or alicyclic group or its mixture, x, y and z are 0 or 1; The nitrogen-atoms of N-O group can be connected or form the part of arbitrary above-mentioned group.The unitary pKa of the amine oxide of polyamine N-oxide＜10, preferred pKa＜7, more preferably pKa＜6.

Can use any polymer backbone, as long as the amine oxide polymers that forms is water miscible and has the dye transfer inhibition activity.The example of suitable polymeric skeleton is polyvinyl, polyalkylene, polyester, polyethers, polymeric amide, polyimide, polyacrylate and its mixture.These polymkeric substance comprise that wherein a kind of monomer type is that amine n-oxide and other monomer type are the random or segmented copolymers of N-oxide compound.The amine of amine n-oxide polymkeric substance generally is 10 with the ratio of amine n-oxide: 1-1: 1000000.Yet the quantity that is present in the amine oxide group in the polyamine oxide polymer can change by suitable copolymerization or by suitable N-oxidisability.Can obtain polyoxygenated amine with almost any polymerization degree.Usually, molecular-weight average is in the scope of 500-1000000; More preferably 1000-500000; 5000-100000 most preferably.Preferred this class material can be referred to as " PVNO ".

Useful most preferred polyamine N-oxide is poly-(4-vinylpridine-N-oxide compound) in this paper detergent composition, its molecular-weight average be about 50000 and the ratio of amine and amine n-oxide be about 1: 4.

The multipolymer of N-vinyl pyrrolidone and N-vinyl imidazole polymkeric substance (being referred to as " PVPVI " class) also is preferred for herein.The average molecular weight range of PVPVI is 5000-1000000 preferably, more preferably 5000-200000 and most preferably 10000-20000.(average molecular weight range is by as people such as Barth, at " chemical analysis " Chemical Analysis, scattering of light described in the Vol113 " modernism of polymer characterization (Modern Methods of PolymerCharacterization) " determines that the disclosed content of the document is incorporated herein by reference.) the N-vinyl imidazole of PVPVI multipolymer and the mol ratio of N-vinyl pyrrolidone generally be 1: 1-0.2: 1, more preferably 0.8: 1-0.3: 1, most preferably 0.6: 1-0.4: 1.These multipolymers can be straight chain also can be side chain.

The present composition also can use molecular-weight average to be about 5000-400000, preferably about 5000-200000, the more preferably from about Polyvinylpyrolidone (PVP) of 5000-50000 (" PVP ").PVP is known for the technician of detergent applications; See, for example, EP-A-262897 and EP-A-256696, they are incorporated herein by reference.It is about 500-100000 that the composition that contains PVP also can contain molecular-weight average, preferably the polyoxyethylene glycol of about 1000-10000 (" PEG ").The ratio of PEG and PVP is to be released in the ppm preferably about 2 in the washings: 1-50: 1, more preferably from about 3: 1-10: 1.

Detergent composition herein also can randomly contain the 0.005-5% that has an appointment (weight) particular type also provide dye transfer inhibiting hydrophilic white dyes.If you are using, composition herein preferably includes such white dyes of about 0.01-1% (weight).

Useful hydrophilic white dyes is those compounds with following structural formula among the present invention:

R wherein ₁Be selected from anilino, N-2-two-hydroxyethyl and NH-2-hydroxyethyl; R ₂Be selected from N-2-pair-hydroxyethyl, N-2-hydroxyethyl-N-methylamino, morpholino, chloro and amino; With M be for example sodium or potassium of the salifiable positively charged ion of shape.

As the R in following formula ₁Be anilino, R ₂Be N-2-two-hydroxyethyl and M are positively charged ions for example during sodium, this whitening agent is 4,4 ' ,-two [(4-anilino-6-(N-2-two-hydroxyethyl)-s-triazine-2-yl) amino]-2,2 '-stilbene disulfonic acid and disodium salt.This specific whitening agent is sold by Ciba-Geigy Corporation with trade(brand)name Tinopal-UNPA-GX.Tinopal-UNPA-GX is a preferred hydrophilic white dyes useful in this paper detergent composition.

As the R in following formula ₁Be anilino, R ₂Be that N-2-hydroxyethyl-N-2-methylamino and M are positively charged ions for example during sodium, this whitening agent is 4,4 '-two [(4-anilino-6-(N-2-hydroxyethyl-N-methylamino)-s-triazine-2-yl) amino]-2,2 '-stilbene disulfonic acid disodium salt.This specific whitening agent is sold by Ciba-Geigy Corporation with trade(brand)name Tinopal-5BM-GX.

As the R in following formula ₁Be anilino, R ₂Be that morpholino and M are positively charged ions for example during sodium, this whitening agent is 4,4 '-two [(4-anilino-6-morpholino-s-triazine-2-yl) amino] 2,2 '-stilbene disulfonic acid, sodium salt.This specific whitening agent is sold by Ciba-Geigy Corporation with trade(brand)name Tinopal-AMS-GX.

Specific for selecting to be used for white dyes of the present invention when being used in combination with previously described polymeric dye transfer inhibitor through selecting, effective especially dye transfer rejection benefit is provided.Compare with these the two kinds of detergent composition components when using separately, the polymeric material of above-mentioned selection (for example, PVNO and/or PVPVI) in aqueous cleaning solution, provide obviously better dye transfer restraining effect with the mixture of the white dyes (for example, Tinopal UNPA-GX, Tinopal 5BM-GX and/or Tinopal AMS-GX) of above-mentioned selection.Bound by theory not, we believe that above-mentioned whitening agent works by this way, promptly because they have high affinity to fabric in washings, so they are deposited on these fabrics relatively soon.The degree that whitening agent is deposited on the fabric in washing soln can be with the parameter-definition that is referred to as " consumption coefficient ".In general consumption coefficient is whitening agent material and the b that a) is deposited on the fabric) ratio of initial whitening agent concentration in washings.Whitening agent with high relatively consumption coefficient is suitable for suppressing dye transfer in the present invention most.

Certainly, be appreciated that other conventional fluorescent brightening formulation compound randomly to be used for composition of the present invention so that provide conventional fabric " to brighten " benefit, rather than real dye transfer restraining effect.Such use is conventional to the detergent formulation teacher and is known.

The detergent composition of sequestrant-herein also can randomly contain one or more iron and/or manganese sequestrant.Such sequestrant can be selected from: as fragrant chelating agent and its mixture of hereinafter defined aminocarboxylate, amino phosphonates do, polyfunctional group replacement.Do not plan bound by theory, the benefit that it is believed that these materials partly is because it removes the special ability of iron and mn ion by forming solvable inner complex from washing soln.

Comprise edetate, N-Oxyethylethylenediaminetriacetic acid salt, nitrilotriacetic acid(NTA) salt, ethylenediamine tetrapropionic acid(EDTP) salt as the optional useful aminocarboxylate of sequestrant.Triethylenetetraaminehexaacetic acid salt, diethylentriamine pentacetate and hydroxyethyl Diglycocol and its basic metal, ammonium and substituted ammonium salt and its mixture.

When allowing low total phosphorus content at least in detergent composition, amino phosphonates do also is suitable for the sequestrant of doing in the present composition, and it is included as the ethylenediamine tetraacetic (methylene phosphonic acid salt) of DEQUEST.Preferably, these amino phosphonates do do not contain alkyl or the alkenyl more than about 6 carbon atoms.

Also be useful in the fragrant chelating agent of the multifunctional replacement composition in this article.See the US3812044 that people such as Connor issued on May 21st, 1974.The preferred compound of this class of acid form is a dihydroxyl disulfobenzene for example 1,2-dihydroxyl-3,5-disulfobenzene.

Be used for herein preferred biodegradable cheating agent and be as at ethylenediamine disuccinate (" EDDS "), especially [S, the S] isomer described in the US4704233 (Hartman and Perkins, promulgation on November 3rd, 1987).

Composition herein also can contain water miscible methylglycine oxalic acid (MGDA) salt (or sour form) as sequestrant or with the common washing assistant that uses such as zeolite, layered silicate for example of insoluble washing assistant for example.

If you are using, these sequestrants account for about 0.1-15% of detergent composition weight herein usually.More preferably, if you are using, this sequestrant accounts for about 0.1-3.0% of above-mentioned composition weight.

Suds suppressor-the compound that reduces or the inhibition foam forms can be joined in the composition of the present invention.Foam inhibition as so-called " the high density cleaning process " in United States Patent (USP) 4489455 and 4489574, described in and in preceding year Europe class washing machine, be particularly important.

Can use various materials as suds suppressor, and suds suppressor is known for those skilled in the art.For example, see " chemical technology encyclopaedia " (Encyclopediaof Chemical Technology) the 3rd edition of Kirk Othmer, the 7th volume, 430-447 page or leaf (Jone Wiley﹠amp; Sons, Inc.1979).The suds suppressor of one class particularly important comprises monocarboxylic acid lipid acid and its soluble salt.See US2954347 (Wayne St.John, promulgation on September 27 nineteen sixty).Monocarboxylic acid lipid acid and its salt as suds suppressor generally have about 24 carbon atoms of 10-, the hydrocarbyl chain of preferred 12-18 carbon atom.Suitable salt comprises an alkali metal salt, for example sodium, potassium and lithium salts and ammonium and alkanol ammonium salts.

Detergent composition herein also can contain the nonsurfactant suds suppressor.They comprise: for example, and high-molecular-weight hydrocarbons such as paraffin, fatty acid ester (for example, fatty acid triglyceride), the fatty acid ester of monovalent alcohol, aliphatic C ₁₈-C ₄₀Ketone (as stearone) or the like.Other suds suppressor comprises: the alkylating aminotriazine of N-for example three-to six-alkyl melamine or as the product of the uncle of containing 1-24 carbon atom of cyanuric chloride and 2 or 3 moles or secondary amine form two-to four-alkyl diamine chlorination triazine, propylene oxide and mono phosphoric acid ester the stearyl for example stearic alcohol ester of mono phosphoric acid ester and single stearyl di(2-ethylhexyl)phosphate an alkali metal salt (for example K, Na and Li) and phosphoric acid ester.Can use hydrocarbon with liquid form, for example paraffin and halo paraffin.Liquid hydrocarbon is a liquid under room temperature and normal atmosphere, and pour point is-40 ℃ to about 50 ℃ approximately, and minimum boiling point is not less than about 110 ℃ (under normal atmosphere).It also is known using wax shape hydrocarbon, and preferably its fusing point is lower than about 100 ℃.Hydrocarbon has constituted the suds suppressor that a class preferably is used for detergent composition.The hydrocarbon suds suppressor exists, and for example, among the US4265779 (people such as Gandolfo, promulgation on May 5th, 1981) description is arranged.Therefore, hydrocarbon comprises saturated or unsaturated aliphatics with about 12-70 carbon atom, alicyclic, aromatic series and heterocyclic hydrocarbon.As using in this suds suppressor is discussed, term " paraffin " is intended to comprise the real paraffin and the mixture of cyclic hydrocarbon.

Another kind of preferred nonsurfactant suds suppressor comprises silicone suds suppressor.Such comprises that use organopolysiloxane oil is as polydimethylsiloxane, the dispersion liquid of organopolysiloxane oil or resin or emulsion, with the composition of organopolysiloxane and silica dioxide granule, organopolysiloxane chemisorption or be melted on the silicon-dioxide wherein.Silicone suds suppressor in this area be know and be disclosed in, for example in US4265779 (people such as Gandolfo, promulgation on May 5th, 1981) and the european patent application 89307851.9 (disclose February 7 nineteen ninety for Starch, M.S.).

Other silicone suds suppressor is disclosed among the US3455839, and it relates to by toward wherein adding composition and the method that a spot of polydimethylsiloxane fluid is used for aqueous solution froth breaking.

The mixture of siloxanes and silanized silica is disclosed in, for example among the German patent application DOS2124526.Silicone antifoam agent in granular detergent composition and Foam Control are disclosed among US3933672 people such as () Bartolotta and the US4652392 people such as (, promulgation on March 24th, 1987) Baginski.

The suds suppressor that is used for illustrative siloxanes herein is the Foam Control of foam inhibition amount, and it is made up of following material substantially:

(i) viscosity is the polydimethylsiloxane fluid of about 20-1500cs (25 ℃);

The silicone resin of (i) about 5-50 weight part of (ii) per 100 weight parts, this resin is by (CH ₃) ₃SiO _1/2Unit and SiO ₂The unit is formed, (CH ₃) ₃SiO _1/2Unit and SiO ₂Unitary ratio is about 0.6: 1-1.2: 1; With

The solid silicone of (i) about 1-20 weight part of (iii) per 100 weight parts.

At the preferred silicone suds suppressor that is used for herein, the solvent that is used for external phase is by specific polyoxyethylene glycol or polyethylene glycol-propylene glycol copolymers or its mixture (preferably), and perhaps polypropylene glycol constitutes.Main silicone suds suppressor is side chain/crosslinked and preferably is non-straight chain.

In order to further specify this point, the general liquid laundry detergent compositions with control foam randomly comprises about 0.001-1% (weight), preferred about 0.01-0.7% (weight), the described silicone suds suppressor of 0.05-0.5% (weight) more preferably from about, this silicone suds suppressor comprises: the nonaqueous emulsion of (1) main foam reducing composition, it is (a) organopolysiloxane, (b) silicone compounds of arborescens siloxanes or generation silicone resin, (c) finely divided packing material, (d) promote component of mixture (a), (b) with the mixture of catalysts of (c) reacting formation silane alkoxide; (2) at least a nonionic siloxane tensio-active agent; (3) polyoxyethylene glycol or at room temperature the solubleness in water greater than about 2% (weight) and polyethylene glycol-propylene glycol copolymers that do not have polypropylene glycol.At particulate composition, can use similar amount in the gel etc.Also referring to US4978471 (Starch, and US4983316 (Starch, promulgation on January 8th, 1991), US5288431 (people such as Huber December 18 nineteen ninety promulgation),, on February 22nd, 1994 promulgation) and US4639489 and US4749740 people such as (, 46 row-4 hurdles, 1 hurdle, 35 row) Aizawa.

Silicone suds suppressor herein preferably includes the multipolymer of polyoxyethylene glycol and polyethylene/polypropylene glycol, its molecular-weight average all be lower than about 1000, preferably between about 100-800.The polyoxyethylene glycol herein and the multipolymer of the polyethylene/polypropylene glycol at room temperature solubleness in water are greater than about 2%, are preferably greater than about 5% (weight).

Preferred solvent herein is a molecular-weight average less than about 1000, more preferably between about 100-800, and the multipolymer of polyoxyethylene glycol between about 200-400 and polyethylene/polypropylene glycol most preferably, preferred PPG200/PEG300.Polyoxyethylene glycol preferably: the weight ratio of the multipolymer of polyethylene glycol-propylene glycol is 1: 1-1: between 10, most preferably 1: 3-1: between 6.

The preferred silicone suds suppressor that is used for does not herein contain polypropylene glycol, and especially molecular weight is 4000 polypropylene glycol.They preferably do not contain the segmented copolymer of oxyethane and propylene oxide yet, as PLURONIC L101.

Other useful herein suds suppressor comprise secondary alcohol (for example 2-alkyl chain triacontanol) and above-mentioned alcohol and silicone oil for example be disclosed in US4798679,4075118 and EP150872 in the mixture of siloxanes.This secondary alcohol comprises having C ₁-C ₁₆The C of chain ₆-C ₁₆Alkyl alcohol.Preferred alcohol is 2-butyl octanol, and it can obtain with trade(brand)name ISOFOL12 from Condea.The mixture of secondary alcohol can obtain with trade(brand)name ISALCHEM123 from Enichem.It is 1 that the blended suds suppressor generally comprises weight ratio: 5-5: the mixture of alcohol+siloxanes of 1.

For the detergent composition that is used for automatic washing machine, should not form and make it overflow the foam of washing machine degree.When it used, suds suppressor preferably existed with " foam inhibition amount ".Be meant that about " foam inhibition amount " formulator of composition can select the amount of Foam Control to make and be enough to control foam, the result is formed for the low foam laundry washing composition of automatic washing machine.

Composition herein generally includes the suds suppressor of 0-about 10%.When monocarboxylic acid lipid acid and salt thereof use as suds suppressor, about 5% (weight) of the general as many as detergent composition of the amount of its existence.The preferred fatty monocarboxylate suds suppressor that uses about 0.5-3%.About 2.0% (weight) of the generally as many as composition of the usage quantity of silicone suds suppressor is although also can use higher amount.This upper limit is actual, mainly is because relevant with the efficient that keeps minimum cost and low amount to control whipability effectively.The preferably about 0.01-1% of amount of the silicone suds suppressor that uses, more preferably from about 0.25-0.5%.As employed in this article, these weight percent numerical value comprise any silicon-dioxide that can be used in combination with organopolysiloxane, and operable any additional materials.The amount of normally used single stearyl phosphoric acid ester suds suppressor is about 0.1-2% (weight) of composition.The amount of the hydrocarbon suds suppressor that uses generally is about 0.01-5.0%, although can use higher amount.The amount of the pure suds suppressor that uses generally is the 0.2-3% (weight) of the finished product composition.

Oxyalkylated multi-carboxylate-oxyalkylated multi-carboxylate is useful so that additional removal grease performance is provided from those of polyacrylate preparation in this article for example.Such material is described in the page 4 and nextpage of WO91/08281 and PCT90/01815, and these 2 pieces of documents are incorporated herein by reference.Every 7-8 acrylate unit contains the polyacrylate with 1 oxyethyl group side chain on these materials chemistries.This side chain has formula-(CH ₂CH ₂O) _m(CH ₂) _nCH ₃, wherein m is 2-3, n is 6-12.This side chain is that ester is connected to polyacrylate " skeleton " upward so that " comb " polymkeric substance shape structure is provided.Its molecular weight can change, but generally at about 2000-50000.Oxyalkylated multi-carboxylate like this can account for about 0.05-10% of composition weight herein.

Fabric softener-in composition of the present invention, can randomly use various fabric softeners by washing, especially US4062647 (Storm and Nirschl, promulgation on December 13rd, 1977) the particulate terre verte in, and other softening agent clay known in the art, its consumption generally is about 0.5-10% (weight), so that laundering of textile fabrics provides the fabric softener benefit simultaneously.The clay softening agent can be used in combination with amine and cationic softener, as, for example US4375416 (people such as Crisp, promulgation on March 1 nineteen eighty-three) and US4291071 people such as (, issued on September 22nd, 1981) Harris are disclosed.

Spices-spices and perfume composition useful in the present composition and method comprises various natural and synthetic chemical compositions, includes, but are not limited to: aldehyde, ketone, ester etc.What also comprise is various natural extracts and volatile oil, and it comprises for example complex mixture of orange oil, lemon oil, rose extract, lavender, Moschus, patchouli, balsamic tone essential oil, santal oil, pine tar, cdear etc. of each component.Final spices can comprise the extremely complicated mixture of such component.Final spices generally accounts for about 0.01-2% of detergent composition weight herein, and each perfume composition can account for about 0.0001-90% of final flavor compositions.

Several fragrance formulations are described among hereinafter the embodiment XXI.The non-limitative example of useful herein perfume composition comprises: 7-ethanoyl-1; 2; 3; 4; 5; 6; 7; 8-octahydro-1; 1; 6; 7-tetramethyl-naphthalene; the methyl ionone; γ methyl ionone; vertofix coeur; the dihydro methyl jasmonate; methyl 1; 6; 10-trimethylammonium-2; 5; 9-CDT-1-base ketone; 7-ethanoyl-1; 1; 3; 4; 4; the 6-vegolysen; 2; 3; the 4-tetraline; 4-ethanoyl-6-the tertiary butyl-1; 1-dimethyl-1; the 2-indane; the p-hydroxybenzene butanone; benzophenone; methyl β naphthyl ketone; 6-ethanoyl-1; 1; 2; 3; 3; the 5-vegolysen; the 2-indane; 5-ethanoyl-3-sec.-propyl-1; 12; 6-tetramethyl--1; the 2-indane; the 1-lauric aldehyde; 4-(4-hydroxy-4-methyl amyl group)-3-tetrahydrobenzene-1-formaldehyde; 7-hydroxyl-3; 7-dimethyl octanal; 10-undecene-1-aldehyde; dissident's thiazolinyl hexahydrobenzaldehyde; the formyl radical tristane; the condensation product of laurine and methyl oaminobenzoate; the condensation product of laurine and indoles; the condensation product of phenyl acetaldehyde and indoles; 2-methyl-3-(to tert-butyl-phenyl)-propionic aldehyde; vanillal; heliotropine; basic phenylacrolein; amyl cinnamic aldehyde; 2-methyl-2-(p-isopropyl phenyl)-propionic aldehyde; tonka bean camphor; the γ decalactone; the Cyclopentadecanol acid anhydride; 16-hydroxyl-palmitoleic acid lactone; 1,3,4; 6; 7,8-six hydrogen-4,6; 6; 7,8,8-pregnancy basic ring five-γ-2-chromene; the 2-Naphthol methyl ether; ambroxane; ten dihydros-3a; 6; 6,9a-tetramethyl-naphtho-[2,1b] furans; cypress camphor; 5-(2; 2; 3-front three basic ring penta-3-thiazolinyl)-3-methylpent-2-alcohol; 2-ethyl-4-(2,2,3-trimethylammonium-3-cyclopentenes-1-yl)-2-butylene-1-alcohol; caryophyllenol; the propionic acid tricyclodecenyl ester; tricyclodecenyl acetate; benzyl salicylate; cedryl acetate and acetate is right-(tertiary butyl) cyclohexyl ester.

Particularly preferred spices material is to provide maximum smell improved those spices in containing the finished product composition of cellulase.These spices include, but are not limited to: hexyl cinnamic aldehyde; 2-methyl-3-(to tert-butyl-phenyl)-propionic aldehyde; 7-ethanoyl-1,2; 3,4,5; 6,7,8-octahydro-1; 1,6,7-tetramethyl-naphthalene; benzyl salicylate; 7-ethanoyl-1; 1,3,4; 4,6-vegolysen, 2; 3, the 4-tetraline; acetate is to the tert-butylcyclohexyl ester; the dihydro methyl jasmonate; the 2-Naphthol methyl ether; methyl betanaphthyl ketone; 2-methyl-2-(p-isopropyl phenyl)-propionic aldehyde; 1,3; 4,6,7; 8-six hydrogen-4,6,6; 7,8,8-pregnancy basic ring five-γ-2-chromene; ten dihydros-3a; 6; 6,9a-tetramethyl-naphtho-[2,1b] furans; aubepine; tonka bean camphor; cypress camphor; Vanillin; the Cyclopentadecanol acid anhydride; tricyclodecenyl acetate and propionic acid tricyclodecenyl ester.

Other perfume material package is drawn together: volatile oil, resinoid and from the resin in various sources, these sources include, but are not limited to: Surinam balsam, frankincense resinoid, Styrax, ladanum resin, Semen Myristicae, Oleum Cinnamomi, styrax resinoid, coriander and lavender element.Other flavor chemistry product also comprise: phenylethyl alcohol, terpinol, linalool, linalyl acetic ester, Geraniol, vernol, acetate 2-(1, the 1-dimethyl ethyl)-hexamethylene alcohol ester, jasmal and oxymethoxyallylbenzene.In final flavor compositions, can use for example diethyl phthalate of carrier.

Other component-various other components useful in detergent composition can be included in the composition of this paper, and it comprises other active ingredient, carrier, hydrotropic agent, processing aid, dyestuff or pigment, is used for the solvent of liquid formulations, is used for the solid packing of bar compositions etc.High if desired whipability so can be with suds booster C for example ₁₀-C ₁₆Alkanolamide joins in the composition, and its amount generally is 1-10% (weight).C ₁₀-C ₁₄Monoethanolamine and diglycollic amide illustrate such suds booster of general type.With the cosurfactant of above-mentioned high whipability for example amine oxide, trimethyl-glycine and sultaine to use such suds booster also be favourable.If necessary, can add for example MgCl of water soluble magnesium and/or calcium salt ₂, MgSO ₄, CaCl ₂, CaSO ₄Deng, its amount is generally 0.1-2%, so that additional foam is provided and removes performance so that strengthen grease.

The various scrubbed component of using in the present composition randomly can also apply described matrix with hydrophobic coating and further stablize then by described component is adsorbed on the porous hydrophobic matrix.Preferably, in being adsorbed into porous matrix before, scrubbed component is mixed with tensio-active agent.In use, scrubbed component discharges from matrix and enters aqueous cleaning solution, and it plays its predetermined washing function in aqueous cleaning solution.

In order to illustrate in greater detail this technology, with porous hydrophobic silicon-dioxide (trade(brand)name SIPERNAT D10, DeGussa) with contain 3-5%C _13-15The protein enzyme solution of ethoxylated alcohol (EO7) nonionogenic tenside mixes.Usually, enzyme/surfactant soln is 2.5 times of silica weight.Under agitation the powder that obtains is dispersed in the silicone oil (can use the various silicone oil of viscosity) in the 500-12500 scope.With the silicone oil dispersion emulsification of gained or with other method it is joined in the final detergent base.In this way, can protect and be used for for example above-mentioned enzyme, SYNTHETIC OPTICAL WHITNER, bleach-activating agent, bleaching catalyst, light activating agent, dyestuff, fluorescent agent, fabric conditioner and the hydrolyzable tensio-active agent of component that washing composition comprises liquid laundry detergent compositions.

Liquid detergent composition can contain water and other solvent as carrier.Low-molecular-weight uncle or secondary alcohol for example methyl alcohol, ethanol, propyl alcohol and butanols are suitable.For the solubilizing surfactant monohydroxy-alcohol is preferred, but also can use polyvalent alcohol for example to contain those alcohol (for example 1, ammediol, ethylene glycol, glycerine and 1,2-propylene glycol) of about 6 carbon atoms of 2-and about 6 hydroxyls of 2-.Composition can contain 5-90%, the general such carrier of 10-50%.

Detergent composition herein is preparation so preferably, makes the pH of washing water when being used for moisture cleaning operation between about 6.5-11, preferably about 7.5-10.5.The pH of liquid wash up formula for a product is preferably between about 6.8-9.0.The pH of laundry product is generally 9-11.With pH be controlled at recommend to use the technology of content to comprise to use slow in agent, alkali, acid etc. and those skilled in the art know.

The form of composition-composition of the present invention can adopt various physical form, comprises granular, sheet, strip and liquid form.Especially, said composition is so-called spissated granular detergent composition, and it is adapted to pass through distribution device and joins in the washing machine, and this distribution device is placed in the washing machine rotating cylinder with dirty fabric.

Median size according to the component of granular composition of the present invention should be preferably such, and it makes no more than 5% particle diameter greater than 1.7mm, and no more than 5% particle diameter is less than 0.15mm.

Defined herein term median size is calculated by composition sample is divided into a lot of particle size fractions (generally being 5 particle size fractions) at a series of Tyler sieve top sieves.The weight particle size fraction that obtains thus is to the aperture mapping of sieve.Median size is that sample passes through the aperture of 50% (weight).

The bulk density of granular detergent composition of the present invention generally is 600g/l, more preferably 650-1200g/l at least.Bulk density is by being measured by simple funnel and measuring cup device, and it is installed in by rigidity that coniform funnel on the base is formed and a plate valve is housed so that allow object in the funnel be emptied to be placed in the axially aligned coniform measuring cup below the funnel in its lower end.This funnel 130mm height, the upper and lower ends internal diameter is respectively 130mm and 40mm.It is to install like this, makes 140mm place on base, lower end.The height overall of measuring cup is 90mm, and interior height is 87mm, and internal diameter is 84mm.It demarcates volume is 500ml.

In order to measure, topple over hand this funnel is filled up powder, open plate valve and allow the powder measuring cup that overfills.From base, take out this measuring cup that fills up and with a straight flange instrument for example cutter remove excessive powder by its upper limb.This measuring cup that fills up of weighing then multiply by 2 values that obtain by powder weight bulk density (g/l) is provided.If desired, repeat to measure.

The cleaning system of agglomerate granule-herein preferably is present in the granular composition with the form of agglomerate granule, this agglomerate granule can be sheet, bead, ball, bar, belt-like form, but particle form preferably.This particulate method of most preferred processing is by being controlled in the specific limit with powder (for example silico-aluminate, carbonate) and the agglomeration of high level of surfactant cream and with the particle diameter of the agglomerate that obtains.Such method comprises the active lotion of the powder of significant quantity and high surfactant at one or more agglomeration machines for example in disc type agglomeration machine, the Z type blade mixing machine, perhaps more preferably at placed in-line mixing machine for example by Schugi (Holland) BV, 29 Chroomstraat8211AS, Lelystad, Netherlands and Gebruder Lodige Maschinenbau GmbH, D-4790Paderbron 1, Elsenerstrasse7-9, Postfach2050, those that Germany produces.Most preferably use high shear mixer, for example Lodige CB (trade(brand)name).

The general use contained 50-95% (weight), the active lotion of the high surfactant of preferred 70-85% (weight) tensio-active agent.Can be high enough to keep pumpable viscosity but low to the temperature that is enough to avoid used tensio-active agent degraded with this ointment pumping in the agglomeration machine.The service temperature of this lotion generally is 50-80 ℃.

The machine washing clothes washing method of laundry washing methods-herein generally comprises in washing machine with dissolving therein or having disperseed the machine-wash aqueous cleaning solution of laundry detergent composition of the present invention of significant quantity to handle the dirt clothes.About the detergent composition of significant quantity, it refers to the product dissolving of 40-300g or is dispersed in the washing soln of 5-65 liter, and this is normally used common product dosage and a washing soln volume in the machine washing clothes washing method of routine.

As mentioned above, isopeptidase is used for cleaning combination herein, its preferably with detergent surfactant combination, its amount is that the direct improvement of cleaning performance aspect is effective to reaching at least.In the fabric laundry composition, above-mentioned " usage quantity " can change, and this not only depends on the type and the severity of dirt and stain, but also depends on the type of temperature of washing water, washing water volume and washing machine.

For example, in washing bath, use about 45-83 premium on currency, in the American version automatic washing machine of uploading Z-axis of the about 10-14 of cycles of washing minute and the about 10-50 of temperature of washing water ℃, preferably in washings, comprise about 2-625ppm, preferred about 2-550ppm, the more preferably from about tensio-active agent of 10-235ppm.According to the usage ratio of the about 50-150ml of every wash load, for the heavy-filth liquid detergent for washing clothes, it changes into, and concentration (weight) is about 0.1-40%, preferably about 0.1-35%, more preferably from about 0.5-15% in the product of tensio-active agent.Usage ratio according to the about 30-950g of every wash load, for dense (" densification ") granular laundry detergent (density is greater than about 650g/l), it changes into, and concentration (weight) is about 0.1-50%, preferably about 0.1-35%, more preferably from about 0.5-15% in the product of tensio-active agent.According to the usage ratio of the about 80-100g of every load, for spray-dired particle (i.e. " fluffy "; Density is lower than about 650g/l) washing composition, it changes into, and concentration (weight) is about 0.07-35%, preferably about 0.07-25%, more preferably from about 0.35-11% in the product of tensio-active agent.

For example, in washing bath, use about 8-15 premium on currency, in the Europe class automatic washing machine of preceding year transverse axis of the about 10-60 of cycles of washing minute and the about 30-95 of temperature of washing water ℃, preferably in washings, comprise about 3-14000ppm, preferred about 3-10000ppm, the more preferably from about tensio-active agent of 15-4200ppm.According to the usage ratio of the about 45-270ml of every wash load, for the heavy-filth liquid detergent for washing clothes, it changes into, and concentration (weight) is about 0.1-50%, preferably about 0.1-35%, more preferably from about 0.5-15% in the product of tensio-active agent.Usage ratio according to the about 40-210g of every wash load, for dense (" densification ") granular laundry detergent (density is greater than about 650g/l), it changes into, and concentration (weight) is about 0.12-53%, preferably about 0.12-46%, more preferably from about 0.6-20% in the product of tensio-active agent.According to the usage ratio of the about 140-400g of every load, for spray-dired particle (i.e. " fluffy "; Density is lower than about 650g/l) washing composition, it changes into, and concentration (weight) is about 0.03-34%, preferably about 0.03-24%, more preferably from about 0.15-10% in the product of tensio-active agent.

For example, in washing bath, use about 26-52 premium on currency, in the Japanese type automatic washing machine of uploading Z-axis of the about 8-15 of cycles of washing minute and the about 5-25 of temperature of washing water ℃, preferably in washings, comprise about 0.67-270ppm, preferred about 0.67-236ppm, the more preferably from about tensio-active agent of 3.4-100ppm.According to the usage ratio of the about 20-30ml of every wash load, for the heavy-filth liquid detergent for washing clothes, it changes into, and concentration (weight) is about 0.1-40%, preferably about 0.1-35%, more preferably from about 0.5-15% in the product of tensio-active agent.Usage ratio according to the about 18-35g of every wash load, for dense (" densification ") granular laundry detergent (density is greater than about 650g/l), it changes into, and concentration (weight) is about 0.1-50%, preferably about 0.1-35%, more preferably from about 0.5-15% in the product of tensio-active agent.According to the usage ratio of the about 30-40g of every load, for spray-dired particle (i.e. " fluffy "; Density is lower than about 650g/l) washing composition, it changes into, and concentration (weight) is about 0.06-44%, preferably about 0.06-30%, more preferably from about 0.3-13% in the product of tensio-active agent.

As can be seen from the above: the amount of the isopeptidase of the laundry aspect that is used to machine-wash can change, and this depends on type of user's custom and practice situation, washing machine etc.Yet in this respect, one of isopeptidase unknown up to now advantage is: it provides direct at least improved ability to various dirts and stain on performance, even also is like this during the amount use of low levels relatively in final composition.

Aspect preferred use, in washing methods, use distribution device.This distribution device has been full of Betengent product, and with it product is introduced directly into before cycles of washing begins in the rotating cylinder of washing machine.Its volume capacity should be such so that can contain enough conducts normally used Betengent product in this washing methods.

In case the washing machine load has clothes, the distribution device that contains Betengent product just is put in the rotating cylinder.When the cycles of washing of washing machine began, water was introduced in this rotating cylinder and rotating cylinder rotates periodically.The design of this distribution device should be such, causes it can contain dried Betengent product, then during cycles of washing along with its stirring (owing to rotating cylinder rotation) with also make this product release as the result who contacts with washing water.

For the ease of discharge Betengent product during washing, this device can have a lot of perforates, and Betengent product can pass through these holes.In addition, this device can be by liquid permeable but not the material of porous solid phase prod make, this can discharge the dissolved product.Preferably, thus this Betengent product just rapidly discharges the product of the high local concentrations that provides temporary transient in this cycles of washing stage rotating cylinder at washing machine when cycles of washing begins.

Preferred distribution device can re-use, and is the integrity that promptly all keeps container in dried state and during the cycles of washing that designs by this way.Narrated the particularly preferred distribution device that is used for the present composition below in the patent: GB-B-2157717, GB-B-2157718, EP-A-0201376, EP-A-0288345 and EP-A-0288346.Also described the particularly preferred distribution device that is used for the granular laundry product by J.Bland at the disclosed article of 41-46 page or leaf of the Manufacturing Chemist in November, 1989, it is to be referred to as " granulette " type usually.Another is disclosed among the PCT patent application WO94/11562 with the preferred distribution device that detergent composition herein uses.

Particularly preferred distribution device is disclosed in European patent application publication No. 0343069 and 0343070.Back one application discloses the device of the flexible cover that comprises the bag form that extends from the support ring that limits the aperture, makes this aperture lead to sack, and this bag is useful on once washing round-robin adequate prod in the washing process.The part washing medium flows in this bag by this aperture, dissolves this product, and solution outwards flows out by this aperture and enters in the washing medium then.This support ring is equipped with shielding unit and flows out outward with the not dissolved product that prevents to wet, and this device generally comprises from radial extension wall that extends in the center hub of spoke wheel configuration or similar structure, and wherein this wall has the helical form.

In addition, this distribution device can be flexual container, for example bag or box.This bag can be so that maintenance thing wherein is for example disclosed in european patent application 0018678 with the filamentary structure of water impervious protecting materials coating.In addition, it can be formed by the water-insoluble synthetic polymeric material, this material is designed to disruptive edge sealer or closure in water-bearing media, as disclosed in European publication application number 0011500,0011501,0011502 and 0011968.Make things convenient for the frangible closure of water of form to comprise water-soluble binder, it is for example placed and with its sealing on a limit of the bag that forms of polyethylene or polypropylene along water impervious polymeric membrane.

Liquid composition of the present invention is " conc forms " preferably; In this case, compare with the liquid washing agent of routine, liquid detergent composition of the present invention contains the water of low amount.By detergent composition weight, this water-content is lower than 50%, preferably is lower than 30%.

Described concentrated product has offered advantage and has given the human consumer, and it has obtained and can measure the product that uses with low, and the producer, and it has obtained lower transportation cost.

When directly being applied to dirt and stain in the pre-treatment step before laundering of textile fabrics, liquid composition is effective especially.

Detergent composition of the present invention also can be used as the detergent additives product.Such additive product is the performance that is used for replenishing or promotes conventional detergent composition.

Detergent composition of the present invention comprises and is used to clean the substrate for example composition of fabric, fiber, crust etc., for example hard-surface cleaning composition that (has or do not have friction agent), laundry detergent composition, automatic and non-automatic dishwashing compositions.

The packing of composition

The commercial embodiments of this bleaching composition may be packaged in any suitable containers, comprises those containers that constitute from paper, cardboard, plastic material and any proper lamination thing.Preferred packing embodiment is described in the european patent application 94921505.7.

Among the embodiment, the dummy suffix notation that is used for the various components of composition has following meaning below:

LAS: straight chain C ₁₂Sodium alkyl benzene sulfonate

Isopeptidase: be called " going stabilized enzyme (destabilase) " (SEQ ID No.7)

Isopeptidase

C45AS: C ₁₄-C ₁₅Straight-chain alkyl sulfate

CxyEzS: with the C of z moles of ethylene oxide condensation _1x-C _1yBranched-chain alkyl sulphur

Acid sodium

CxyEz: with the C of average Z moles of ethylene oxide condensation _1x-1yBranched-chain primary alcohol

QAS???????：R ₂·N ⁺(CH ₃) ₂(C ₂H ₄OH)，R ₂＝C ₁₂-C ₁₄

TFAA: C ₁₆-C ₁₈Alkyl N-methyl grape sugar acid amides

STPP: anhydrous sodium tripolyphosphate

Zeolite A: formula Na ₁₂(AlO ₂SiO) ₁₂.27H ₂The primary particle diameter of O is 0.1-10

The hydrated sodium aluminosilicate of micron

NaSKS-6: formula δ-Na ₂Si ₂O ₅Crystalline layered silicate

Carbonate: the anhydrous sodium carbonate of particle diameter between 200-900 μ m

Sodium bicarbonate: the anhydrous sodium bicarbonate of particle diameter between 400-1200 μ m

Silicate: amorphous silicic sodium (SiO ₂: Na ₂O is than=2.0)

Sodium sulfate: anhydrous sodium sulphate

MA/AA: toxilic acid/acrylic copolymer of 1: 4, molecular-weight average are approximately

70000

CMC: Xylo-Mucine

Proteolytic enzyme: sell with trade(brand)name Savinase by NOVO Industries A/S

Activity be the proteolytic enzyme of 4KNPU/g

Cellulase: sell with trade(brand)name Carezyme by NOVO Industries A/S

Activity be the cellulase of 1000CEVU/g

Amylase: by NOVO Industries A/S with trade(brand)name Termamyl 60T

The activity of selling is the amylolytic enzyme of 60KNU/g

Lipase: sell with trade(brand)name Lipolase by NOVO Industries A/S

Activity is the lipolytic enzyme of 100kLU/g

PB4: the nominal formula is NaBO ₂3H ₂OH ₂O ₂Sodium peroxoborate four

Hydrate

PB1: the nominal formula is NaBO ₂H ₂O ₂The anhydrous sodium perborate SYNTHETIC OPTICAL WHITNER

Percarbonate: the nominal formula is 2Na ₂CO ₃.3H ₂O ₂SPC-D

NaDCC: dichloroisocyanuric acid sodium

NOBS: the nonanoly acyloxy benzene sulfonate of sodium-salt form

TAED: tetra acetyl ethylene diamine

DTPMP: by two Asias of Monsanto with trade(brand)name Dequest2060 sale

Ethyl triamine five (methylene phosphonic acid salt)

The SYNTHETIC OPTICAL WHITNER of photoactivation: the sulfonated zinc phthalocyanine of encapsulate in the dextrin polymer soluble

Whitening agent 1: 4,4 '-two (2-sulfo group styryl) biphenyl disodium

Whitening agent 2: 4,4 '-it is two that [(4-anilino-6-morpholino-1,3,5-three

Piperazine-2-yl) amino] 2,2 '-stilbene disulfonic acid disodium

HEDP: 1,1-hydroxyl ethane di 2 ethylhexyl phosphonic acid

SRP1: sulfo group benzene with ethylene oxide oxygen base and terephthaloyl skeleton

The end capped ester of formyl radical

Polysiloxane kilfoam: contain siloxanes-oxyalkylene copolymers as poly-two of dispersion agent

The methylsiloxane Foam Control, described Foam Control and described

The ratio of dispersion agent is 10: 1-100: 1

DTPA: diethylene triaminepentaacetic acid(DTPA)

Among the embodiment, all content all are the percentage ratio by composition weight meter below.Following embodiment illustrates the present invention, rather than limits or limit in addition its scope.Except as otherwise noted, all umbers used herein, percentage ratio and ratio are all represented with weight percentage.

Embodiment 1

Laundry detergent composition A-F below produced according to the present invention.These compositions can be used for machine washing or hand washing method, comprise as the pre-soaking before the machine washing clothes washing method.

	????A	????B	????C	????D	????E	????F
							Isopeptidase	????0.26	????0.26	????0.26	????0.26	????0.26	????0.26
?C25E3	????3.4	????3.4	????3.4	????3.4	????3.4	????3.4
							?LAS	????20	????20	????15	????17	????22	????14
?QAS	?????-	????-	????0.8	????-	????-	????0.8
							Zeolite A	????18.1	???18.1	????18.1	????18.1	????18.1	????18.1
Carbonate	????13.0	???13.0	????13.0	????27.0	????27.0	????27.0
							Silicate	????1.4	????1.4	????1.4	????3.0	????3.0	????3.0
Sodium sulfate	????26.1	????26.1	????26.1	????26.1	????26.1	????26.1
							?PB4	?????-	?????-	????-	????9.0	????9.0	????9.0
?TAED	?????-	?????-	????-	????1.5	????1.5	????1.5
							?DETPMP	????0.25	????0.25	????0.25	????0.25	????0.25	????0.25
?HEDP	????0.3	????0.3	????0.3	????0.3	????0.3	????0.3

Proteolytic enzyme	????0.26	????0.26	????0.26	????0.26	????0.26	????0.26
							Amylase	????0.1	????0.1	????0.1	????0.1	????0.1	????0.1
?MA/AA	????0.3	????0.3	????0.3	????0.3	????0.3	????0.3
							?CMC	????0.2	????0.2	????0.2	????0.2	????0.2	????0.2
The SYNTHETIC OPTICAL WHITNER of photoactivation (ppm)	???15ppm	???15ppm	???15ppm	???15ppm	???15ppm	???15ppm
							Whitening agent 1	????0.09	????0.09	????0.09	????0.09	????0.09	????0.09
Spices	????0.3	????0.3	????0.3	????0.3	????0.3	????0.3
							The polysiloxane kilfoam	????0.5	????0.5	????0.5	????0.5	????0.5	????0.5
Other/small number of groups assigns to 100%
Density, g/l	????850	????850	????850	????850	????850	????850

Embodiment 2

Bulk density is the granular laundry detergent compositions of 750g/l below produced according to the present invention:

	????G	????H	????I
				Isopeptidase	???0.26	????0.85	????0.85
?C45AS	????-	????2.24	????3.89
				?C25AE3S	????-	????0.76	????1.18
?C45E7	????325	?????-	????5.0
				?C25E3	????-	????5.5	?????-
?QAS	????0.8	????2.0	????2.0
				?STPP	???10.7	?????-	?????-
Zeolite A	???10.7	????19.5	????19.5
				?SKS-6	????-	????10.6	????10.6
Carbonate	????6.1	????21.4	????21.4
				Supercarbonate	????-	????2.0	????2.0
Silicate	????6.8	?????-	?????-
				Sodium sulfate	???39.8	?????-	???14.3
?PB4	????5.0	????12.7	????8.0
				?TAED	????0.5	????3.1	????-

DETPMP	????0.25	????0.2	????0.2
				?HEDP	??????-	????0.3	????0.3
Proteolytic enzyme	????0.26	????0.85	????0.85
				Lipase	????0.15	????0.15	????0.15
Cellulase	????0.28	????0.28	????0.28
				Amylase	????0.1	????0.1	????0.1
?MA/AA	????0.8	????1.6	????1.6
				?CMC	????0.2	????0.4	????0.4
The SYNTHETIC OPTICAL WHITNER of photoactivation (Ppm)	???15ppm	???27ppm	???27ppm
				Whitening agent 1	????0.08	????0.19	????0.19
SYNTHETIC OPTICAL WHITNER 2	?????-	????0.04	????0.04
				Spices	????0.3	????0.3	????0.3
The polysiloxane kilfoam	????0.5	????2.4	????2.4
				A small amount of component/other component to 100%

Embodiment 3

Detergent formulations of the present invention below the preparation:

	????J	????K	????L	????M
					LAS	????15.0	????14.0	????14.0	????18.0
Isopeptidase	????0.8	????1.0	????0.5	????0.5
					TFAA	?????-	????1.0	?????-	?????-
C25E5/C45E7	?????-	????2.0	????-	????0.5
					C45E3S	?????-	????2.5	????-	?????-
Zeolite A	????30.0	????18.0	????30.0	????22.0
					Silicate	????9.0	????5.0	????10.0	????8.0
Carbonate	????13.0	????7.5	?????-	????5.0
					Supercarbonate	?????-	????7.5	?????-	?????-
DTPMP	????0.7	????1.0	?????-	?????-
					SRP?1	????0.3	????0.2	?????-	????0.1
MA/AA	????2.0	????1.5	????2.0	????1.0
					CMC	????0.8	????0.4	????0.4	????0.2
Proteolytic enzyme	????0.8	????1.0	????0.5	????0?5
					Amylase	????0.8	????0.4	?????-	????0.25
Lipase	????0.2	????0.1	????0.2	????0.1
					Cellulase	????0.15	????0.05	????-	?????-
The SYNTHETIC OPTICAL WHITNER of photoactivation (ppm)	??70ppm	???45ppm	????-	???10ppm
					Whitening agent 1	????0.2	????0.2	????0.08	????0.2
PB1	????6.0	????2.0	????5.0	????3.0
					NOBS	????2.0	????1.0	?????-	?????-
Polyethylene oxide, MW5,000,000	?????-	????0.2	?????-	????0.2
					Wilkinite	?????-	?????-	??????-	????10.0
Equipoise (moisture and other component)	????100	????100	????100	????100

Embodiment 4

High density detergent agent formulation of the present invention below the preparation:

	????N	????O
			Agglomerate
???????????????????C45AS	????11.0	????14.0
			Isopeptidase	????1.4	????1.4
Zeolite A	????15.0	????10.0
			Carbonate	????4.0	????8.0
???????????????????MA/AA	????4.0	????2.0
			?????????????????????CMC	????0.5	????0.5
???????????????????DTPMP	????0.4	????0.4
			In the spraying
???????????????????C25E5	????5.0	????5.0
			Spices	????0.5	????0.5
The admixture of doing
			?????????????????C 20SADS	????6.0	????3.0
????????????????????HEDP	????0.5	????0.3
			???????????????????SKS-6	????13.0	????6.0
Citrate trianion	????3.0	????1.0
			????????????????????TAED	????5.0	????7.0
Percarbonate	????20.0	????20.0
			????????????????????SRP1	????0.3	????0.3
Proteolytic enzyme	????1.4	????1.4
			Lipase	????0.4	????0.4
Cellulase	????0.6	????0.6
			Amylase	????0.6	????0.6
The polysiloxane kilfoam	????5.0	????5.0
			Whitening agent 1	????0.2	????0.2
Whitening agent 2	????0.2	?????-
			Equipoise (moisture and other component)	????100	????100
Density (g/l)	????850	????850

Embodiment 5

According to following formulation liquid detergent composition:

The percentage ratio of detergent composition weight

	A	B	C	D
					C 25AE3S	2	8	7	5
Isopeptidase	0.5	0.5	0.5	0.5
					C 12-C 14Alkyl dimethyl amine oxide	-	-	-	2
C 25AS	15	12	8	8
					C 24N-methyl grape sugar acid amides	5	4	3	3
C 24AE5	6	1	1	1
					C 12-C 18Lipid acid	11	4	4	3
Citric acid	1	3	3	2
					DTPMP	1	1	1	0.5
MEA	8	5	5	2
					NaOH	1	2.5	1	1.5
PG	14.5	13.1	10.0	8
					EtOH	1.8	4.7	5.4	1
Amylase (300KNU/g)	0.1	0.1	0.1	0.1
					Lipase D96/L (100KNU/g)	0.15	0.15	0.15	0.15
Proteolytic enzyme (35g/l)	0.5	0.5	0.5	0.5)
					Endoenzyme	0.05	0.05	0.05	0.5
Cellulase	0.09	0.09	0.09	0.9
					The terephthalate based polyalcohol	0.5	-	0.3	0.3
Boric acid	2.4	2.8	2.8	2.4
					Sodium xylene sulfonate	-	3	-	-
2-butyl octanol	1	1	1	1
					The polysiloxane of branching	0.3	0.3	0.3	0.3
Water and accessory constituent	To 100%

^*SEASA is α-sulfonated C ₁₆/ C ₁₈The ester of the isethionate ethoxylation of lipid acid.

Liquid detergent composition (A-D) above finding is removed various stains and dirt is very effective from fabric under various working conditionss.

Embodiment 6-11

Be according to heavy-filth liquid laundry detergent composition of the present invention below.： 6 7 8 9 10 11 0.6 0.6 0.9 0.9 1.2 1.2C25 AS 10 8.0--5.0 5.0C35AE3S/C25AE3S 2.0 9.0--7.0 7.0C24 N- 6.0 5 0 4.5 3.7 4.0 4.0C35 E7 6.0 1.0----C25 AE2.5S--12.0 12.0--C23 E9--2.0 1.0 5.0 5.0C10 APA-1.5-2.0-2.5C24 7.5 1.1 2.0 4.0 5.0 5.0C48 3.0 3.5---- 1.0 3.5 3.0 3.0 3.0 3.0 ( 34g/# ) 0.6 0.6 0.9 0.9 1.2 1.2 0.1 0.1 0.1 0.1 0.2 0.2 ( 300KMU/g ) 0.1 0.1 0.1 0.1-0.1 0.03 0.03 0.05 0.05 0.2 0.2 0.1 0.1----2 0.1 0.1---- 3.0 3.0 3.5 3.5 4.0 4.0MEA 8.0 4.0 1.0 1.5 7.0 7.0NaOH 1.0 4.0 3.0 2.5 1.0 1.0PG 12.0 12 0 7.5 7.5 7.0 7.0EtOH 1.0 1.0 3.5 3.5 6.0 6.0Na TS--2.5 2.5-- ………………………………………

The heavy duty liquid laundry detergent composition that contains the nonaqueous carrier medium especially is designed for the production of those compositions of fabric washing can carry out with more detailed disclosed method hereinafter.In another method, can prepare such non-aqueous composition: US4753570 according to the disclosure of following patent documentation, US4767558, US4772413, US4889652, US4892673, GB-A-2158838, GB-A-2195125, GB-A-2195649, US4988462, US5266233, EP-A-225654 (6/16/87), EP-A-510762 (10/28/92), EP-A-540089 (5/5/93,) EP-A-540090 (5/5/93), US4615820, EP-A-565017 (10/13/93), EP-A-030096 (6/10/81), these documents are incorporated by reference in this article.Such composition can contain and stably is suspended in wherein each kind of particle scrubbed component (comprise SYNTHETIC OPTICAL WHITNER, as mentioned in disclosed).Therefore such non-aqueous composition comprises liquid phase, with optional but preferred solid mutually, as hereinafter and in the document of quoting in greater detail.With method and the content above isopeptidase is joined in the composition so that prepare other laundry detergent composition.

Liquid phase

Liquid phase accounts for about 35-99% of detergent composition weight herein usually.More preferably this liquid phase accounts for about 50-95% of composition weight.Most preferably this liquid phase accounts for about 45-75% of composition weight herein.The liquid phase of detergent composition contains the anion surfactant of the particular type of relative high density basically herein, and is combined with the liquid diluent of the non-water of particular type.

(A) basic anion surfactant

The anion surfactant of main basal component as the on-aqueous liquid phase is selected from: wherein alkyl contains an alkali metal salt of alkyl benzene sulphonate (ABS) of the straight or branched configuration of 10-16 the carbon atom of having an appointment.(see US2220099 and US2477383, these 2 pieces of documents are incorporated by reference in this article.) average carbon atom number that particularly preferably is in the alkyl wherein is linear alkylbenzene sulphonic acid and the potassium (LAS) of about 11-14.C ₁₁-C ₁₄LAS sodium is particularly preferred.

The alkyl benzene sulphonate (ABS) salt anionic surfactant is dissolved in the on-aqueous liquid thinner that constitutes the 2nd basal component of this nonaqueous phase.In order to form the suitable stable mutually and needed structurized liquid phase of acceptable rheological property, the amount that the alkyl benzene sulphonate (ABS) salt anionic surfactant exists usually is about 30-65% of this liquid phase.More preferably this alkyl benzene sulphonate (ABS) salt anionic surfactant accounts for about 35-50% of this paper composition on-aqueous liquid phase weight.The anionic surfactant concentration that uses this anion surfactant to be equivalent in total composition with these concentration is about 15-60% of composition weight, more preferably from about 20-40%.

(B) on-aqueous liquid thinner

In order to form the liquid phase of detergent composition, with above described alkyl benzene sulphonate (ABS) salt anionic surfactant and the on-aqueous liquid mixing diluents that contains 2 kinds of basal components.These 2 kinds of components are the low polar organic solvents of liquid alcohol alcoxylates material and non-water.

I) pure alkane hydrogen base thing

A kind ofly be used to form herein that the basal component of the liquid diluent of composition comprises oxyalkylated Fatty Alcohol(C12-C14 and C12-C18) material.Such material itself also is a nonionogenic tenside.Such material is corresponding to following general formula:

R ¹(C _mH _2mO) _nOH

R wherein ¹Be C ₈-C ₁₆Alkyl, m are 2-4, and n is in the scope of about 2-12.Preferred R ¹Be alkyl, it can be uncle or secondary, contains have an appointment 9-15 carbon atom, the more preferably from about alkyl of 10-14 carbon atom.Also preferred this oxyalkylated Fatty Alcohol(C12-C14 and C12-C18) is the material that per molecule contains the ethoxylation of 2-12 the ethylene oxide moiety of having an appointment.

The hydrophile-lipophile balance value (HLB) of the oxyalkylated Fatty Alcohol(C12-C14 and C12-C18) component of liquid diluent is through the scope of about 3-17 that is everlasting.More preferably the HLB of this material is at the scope of about 6-15, most preferably from about 8-15.

As the example of the fatty alcohol alkoxy compound of one of on-aqueous liquid thinner basal component in this paper composition comprise by 12-15 carbon atom that prepare and that contain 7 moles of ethylene oxide of having an appointment those.Such material is sold with trade name Neodol25-7 and Neodol23-6.5 by Shell Chemical Company.Other useful Neodol comprises: Neodol1-5 on average has the Fatty Alcohol(C12-C14 and C12-C18) of the ethoxylation of about 5 moles of ethylene oxide of having of 11 carbon atoms in its alkyl chain; Neodol23-9 has the C of the ethoxylation of about 9 moles of ethylene oxide ₁₂-C ₁₃Primary alconol and Neodol91-10, the C with about 10 moles of ethylene oxide ₉-C ₁₁Primary alconol.This class alcohol ethoxylate is also sold with trade(brand)name Donanol by Shell Chemical Company.Dobanol91-5 is the C with ethoxylation of average 5 moles of ethylene oxide ₉-C ₁₁Fatty Alcohol(C12-C14 and C12-C18), Donoal25-7 are the C that every mole of Fatty Alcohol(C12-C14 and C12-C18) has the ethoxylation of average 7 moles of ethylene oxide ₁₂-C ₁₅Fatty Alcohol(C12-C14 and C12-C18).

Other example of suitable ethoxylated alcohol comprises straight chain primary alcohol ethoxylate Tergitol15-S-7 and the Tergitol15-S-9 that sells by Union Carbide Corporation.The former is C ₁₁-C ₁₅The mixed ethoxylated product of linear primary alkanol and 7 moles of ethylene oxide, the latter is C ₁₁-C ₁₅The mixed ethoxylated product of linear primary alkanol and 9 moles of ethylene oxide.

The alcohol ethoxylate of other useful type is for example Neodol45-11 of high-molecular weight nonionogenic tenside in the present composition, it is the oxirane condensation product of similar high fatty alcohol, high fatty alcohol has 14-15 carbon atom, and every mole ethylene oxide group number is about 11.Such product is sold by Shell Chemical Company.

The main amount that exists as this alcohol alkoxylate component of partially liq thinner in this paper non-aqueous composition is about 1-60% of this liquid phase composition normally.More preferably about 5-40% of this alcohol alkoxylate ingredients constitute liquid phase.Most preferably, about 5-30% of this alcohol alkoxylate ingredients constitute detergent composition liquid phase that mainly uses.Using alcohol alkoxylate to be equivalent to by the alcohol alkoxylates substrate concentration of composition weight meter in total composition with such concentration in liquid phase is about 1-60%, more preferably from about 2-40%, most preferably from about 5-25%.

The ii) low polar organic solvent of non-water

The 2nd basal component that forms this liquid diluent of this paper detergent composition partially liq phase comprises the low polar organic solvent of non-water.Term used herein " solvent " refers to the on-surface-active carrier or the thinner part of composition liquid phase.Although some herein basic the and/or optional components of composition in fact can be dissolved in the liquid phase that contains this " solvent ", other component will exist as being dispersed in the particle in the liquid phase that contains this " solvent ".Therefore term " solvent " and do not mean that all detergent composition components that need this solvent material to dissolve veritably to join wherein.

Non-water organic materials as solvent is low polar liquid herein.For the purposes of the present invention, " low polarity " liquid is to have very low (if any) dissolving to be used for one of this paper composition preferred type particulate material be the tendency of peroxygen bleach, Sodium peroxoborate or SPC-D.The solvent that therefore should not use relative polarity is ethanol for example.The suitable type of useful low polar solvent comprises in the non-aqueous liquid detergent compositions of this paper: the C of non-vicinal ₄-C ₈Alkylene dihydric alcohol, alkylene dihydric alcohol list lower alkyl ether, low molecular poly, lower molecular weight methyl ester and acid amides etc.

The preferred non-water low polar solvent of a class that is used for this paper composition comprises: the C of non-vicinal ₄-C ₈Side chain or straight-chain alkyl-sub-dibasic alcohol.This class material comprises: hexylene glycol (4-methyl-2,4-pentanediol), 1,6-hexylene glycol, 1,3 butylene glycol and 1,4-butyleneglycol.Hexylene glycol is most preferred.

The another kind of preferred non-water low polar solvent that is used for herein comprises: single, two, three or four C ₂-C ₃Alkylene dihydric alcohol list C ₂-C ₆Alkyl oxide.The object lesson of compound comprises like this: diglycol monotertiary butyl ether, Tetraglycol 99 single-butyl ether, dihydroxypropane single-ethyl ether and dipropylene glycol single-butyl ether.Diglycol monotertiary butyl ether and dipropylene glycol single-butyl ether are particularly preferred.This compounds is sold with trade(brand)name Dowanol, Carbitol and Cellosolve.

The low polar organic solvent of another kind of useful herein preferred non-water comprises low molecular poly (PEG).Such material is that molecular weight is at least about those of 150.Molecular weight is most preferred at the PEG of about 200-600 scope.

Also the preferred nonpolar non-aqueous solvent of a class comprises the lower molecular weight methyl ester.Such material is that general formula is: R ¹-C (O)-OCH ₃Those materials, R wherein ¹Scope at 1-about 18.The example of suitable lower molecular weight methyl ester comprises methyl acetate, methyl propionate, methyl caprylate and methyl laurate.

Certainly, the low polar organic solvent of the non-water of use should be that for example SYNTHETIC OPTICAL WHITNER and/or activator are compatible and do not have reactive with other composition component that is used for this paper liquid detergent composition.By liquid phase weight, use such solvent composition with the amount of about 1-70% usually.More preferably, the low polar organic solvent of this non-water accounts for about 10-60% of composition liquid phase weight, most preferably from about 20-50%.Using this organic solvent to be equivalent to by the solvent strength of composition weight meter in total composition with such concentration in liquid phase is about 1-50%, more preferably from about 5-40%, most preferably from about 10-30%.

The iii) ratio of alcohol alkoxylate and solvent

The ratio that can be used in alcohol alkoxylate in the liquid diluent and organic solvent changes the rheological property of the detergent composition of final formation.Usually the weight ratio of alcohol alkoxylate and organic solvent is about 50: 1-1: 50 scope.More preferably, this ratio is about 3: 1-1: 3 scope.

The iv) concentration of liquid diluent

As for the concentration of alkyl benzene sulphonate (ABS) salt anionic surfactant, the total amount of the liquid diluent of this paper on-aqueous liquid in mutually is to determine by the type of other composition component and amount and by the character of needed composition.This liquid diluent accounts for about 35-70% of this paper composition on-aqueous liquid phase usually.More preferably this liquid diluent accounts for about 50-65% of on-aqueous liquid phase.This is equivalent to by the on-aqueous liquid diluent concentration of composition weight meter in total composition is about 15-70%, more preferably from about 20-50%.

The solid phase

Nonaqueous detergent composition herein mainly also comprises about 1-65% weight, more preferably from about 5-50% weight be dispersed in be suspended in liquid phase in particulate material solid mutually.The particle diameter of usually such particulate material is in the scope of about 0.1-1500 micron.More preferably the particle diameter of such material is in the scope of about 5-200 micron.

Be used for the detergent composition component that herein particulate material can comprise one or more types, it with particle form be insoluble to basically the composition on-aqueous liquid mutually in.Operable this class particulate material is described in detail as follows:

Preparation of compositions and use

Can be by fundamental sum optional components with any blend compositions of order easily, thus with for example stir the component mixture that obtains and form herein stable composition mutually and prepare herein non-aqueous liquid detergent compositions by mixing.In the general method of preparation said composition, with specific order with mix basic and some preferred optional component under given conditions.

In above-mentioned general preparation method's the 1st step, the mixture of 2 kinds of basal components by these mixtures of material being heated to about 30-100 ℃ temperature formation alkyl benzene sulphonate (ABS) salt anionic surfactant and non-diluent water.

In the 2nd processing step, the mixture of the heating of above-mentioned formation was kept shear agitation about 2 minutes-20 hours under about 40-100 ℃ temperature.Randomly, at this moment vacuum can be put on this mixture.The 2nd processing step play a part with anion surfactant be dissolved in fully on-aqueous liquid mutually in.

In the 3rd processing step, the liquid phase mixture of material is cooled to about 0-35 ℃ temperature.This cooling step plays a part to form the structurized liquid base material that contains tensio-active agent, the particulate material of this paper detergent composition can be joined and be dispersed in this liquid base material.

In the 4th processing step,, particulate material adds particulate material by being mixed with liquid base material under maintaining the shear agitation condition.In the time will adding, preferably observe specific adding order more than a kind of particulate material.For example, when keeping shear agitation, can add the optional tensio-active agent of particle diameter in the particle form of all solids basically of the particle form of about 0.2-1000 micrometer range.After adding any optional surfactant granules, can add for example Citrate trianion and/or lipid acid and/or the alkali source particle of yellow soda ash for example of all basically organic washing-assisting detergents, continue simultaneously the mixture of said composition component is maintained under the shear agitation condition.Then at this moment, the optional components of other solid form can be joined in the composition.Continue to stir this mixture, and if necessary, form the uniform dispersion liquid of insoluble solid phase particle in liquid phase thereby can at this moment improve to stir.

After joining some or all of above-mentioned solid materials in this stirred mixture, the particle of SYNTHETIC OPTICAL WHITNER can be joined in the composition, again mixture be maintained under the shear agitation condition simultaneously.By last or after all or most of other component, and particularly after the alkaline source particle is added into, add the SYNTHETIC OPTICAL WHITNER material, can obtain ideal bleach-stable benefit.If add the enzyme bead, so preferably at last they joined in the on-aqueous liquid matrix.

As last processing step, after all particulate materials add, continue to stir this mixture for some time, it is enough to form and has the required viscosity and the composition of stabilising characteristic mutually.Usually this comprises stir about 1-30 minute.

As above-mentioned composition preparation method's a variation, one or more solid ingredients can be joined as with the mixture that is stirring of the premixed particulate slurry of one or more liquid ingredients of small part in.Therefore, can form the particulate premixture of the particle in the particle of small part alcohol alkoxylate and/or non-water low polar solvent and organic washing-assisting detergent material and/or inorganic alkaline source and/or bleach-activating agent and it is joined in the mixture of the composition component that is stirring respectively as slurries.The adding of above-mentioned slurries premixture should be prior to itself forming partly-premixed the close SYNTHETIC OPTICAL WHITNER of slurries and/or the adding of enzyme granulate in a similar manner.

Zhi Bei the present composition can be used for being formed for the aqueous cleaning solution of fabric washing and bleaching as mentioned above.Thereby usually preferred in the fabric washing automatic washing machine of routine the above-mentioned composition of significant quantity being added to the water forms such aqueous cleaning/liquid lime chloride.Then aqueous cleaning/the liquid lime chloride that will so form preferably under agitation with to contact with the fabric of its washing and bleaching.

This paper liquid detergent composition of the formation aqueous cleaning/liquid lime chloride that is added to the water of significant quantity can comprise the amount that presents in an amount at least sufficient to form about 500-7000ppm composition in the aqueous solution.The detergent composition of the present invention of about 800-3000ppm more preferably, is provided in aqueous cleaning/liquid lime chloride.

Embodiment 12

Preparation has the non-limitative example of the on-aqueous liquid detergent for washing clothes of forming described in the Table I that contains SYNTHETIC OPTICAL WHITNER.

Table I

Component Wt.% scope (%wt.) liquid phase C ₁₂Linear alkylbenzene sulphonic acid (LAS) 25.3 18-35 isopeptidases 0.4 0.01-1C _12-14, EO5 alcohol ethoxylate 13.6 10-20 hexylene glycols 27.3 20-30 spices 0.4 0-1.0 solid protein enzyme 0.4 0-1.0 anhydrous sodium citrate 4.3 3-6 sodium perborate 3.4 2-7 acyloxy in ninth of the ten Heavenly Stems benzene sulfonic acid sodium salts (NOBS) 8.0 2-12 sodium carbonate 13.9 5-20 diethyl pentetic acids (DTPA) 0.9 0-1.5 brightening agent 0.4 0-0.6 foam inhibitor 0.1 0-0.3 accessory constituent aequum

The composition that obtains is stable anhydrous heavy-filth liquid detergent for washing clothes, and when it was used for common fabric washing operation, it provided fabulous stain and dirt to remove performance.About manual dishwashing liquid, the following examples further illustrate the present invention.

Embodiment 13 component % (wt.) scope (%wt.) isopeptidases 0.5 0.01-1C _12-13Alkylsurfuric acid ammonium 7.0 2-35C ₁₂-C ₁₄Oxyethyl group (1) vitriol 20.5 5-35 coconut amine oxides 2.6 2-5 trimethyl-glycine/Tetronic704 ^{ * *}0.87-0.10 0-2 (mixture) alcohol ethoxylate C ₈E ₁₁5.0 2-10 ammonium xylene sulfonate 4.0 1-6 ethanol 4.0 0-7 ammonium citrates 0.06 0-1.0 magnesium chloride 3.3 0-4.0 calcium chloride 2.5 0-4.0 ammonium sulfate 0.08 0-4.0 hydrogen peroxide 200ppm 10-300ppm spices 0.18 0-0.5Maxatase^Proteinase-10 .50 0-1.0 water and accessory constituent ... equal amount ^*The coconut alkyl betaine

The information of sequence table (1) SEQ ID NO:1:

(i) sequence signature:

(A) length: 557 base pairs

(B) type: nucleic acid

(C) chain: strand

(D) topology configuration: line style

(ii) molecule type: DNA (genomic)

(iii) sequence description: SEQ ID NO:1GAACTGGCAA TCTTAATATC TCACTA ATG AAT TAC GTT ATC TTT GTG GTC TTA 53

Met?Asn?Tyr?Val?Ile?Phe?Val?Val?Leu

1???????????????5GTG?GCA?CTT?TAC?GTC?ATC?GAG?GTA?GCG?AAG?TGC?ACC?GTC?CCA?TCC?GAT?????????101Val?Ala?Leu?Tyr?Val?Ile?Glu?Val?Ala?Lys?Cys?Thr?Val?Pro?Ser?Asp?10?????????????????15???????????????????20??????????????????25TGC?TTG?AGG?TGC?ATT?TGC?CAG?GTA?GAG?GGA?TGT?AAC?AAT?GAG?ATT?GGA?????????149Cys?Leu?Arg?Cys?Ile?Cys?Gln?Val?Glu?Gly?Cys?Asn?Asn?Glu?Ile?Gly

30??????????????????35??????????????????40AGG?TGC?GGC?ATG?GAC?GCA?GGA?AGT?CTG?AGC?TGT?GGT?CCT?TAC?CAG?ATC?????????197Arg?Cys?Gly?Met?Asp?Ala?Gly?Ser?Leu?Ser?Cys?Gly?Pro?Tyr?Gln?Ile

45??????????????????50??????????????????55AAG?GAG?CCC?TAC?AGG?ATT?GAC?TGT?GGA?AGG?CCA?GGA?GGA?GGA?TAC?CAG?????????245Lys?Glu?Pro?Tyr?Arg?Ile?Asp?Cys?Gly?Arg?Pro?Gly?Gly?Gly?Tyr?Gln

60??????????????????65??????????????????70CAG?TGC?ACG?AAG?GAG?AAG?GCA?TGT?TCT?GAA?AGG?TGT?GTC?CAC?GCT?TAC?????????293Gln?Cys?Thr?Lys?Glu?Lys?Ala?Cys?Ser?Glu?Arg?Cys?Val?His?Ala?Tyr

75??????????????????80??????????????????85ATG?GAC?AGG?TAT?GCC?AGA?AGG?TGT?ACT?GGA?GGA?CGC?CAA?CCG?ACC?TGC?????????341Met?Asp?Arg?Tyr?Ala?Arg?Arg?Cys?Thr?Gly?Gly?Arg?Gln?Pro?Thr?Cys?90??????????????????95?????????????????100?????????????????105CAA?GAC?TAC?GCC?AAA?ATT?CAC?AAC?ATG?GGA?CCG?AAC?GGA?TGC?CAA?TCT?????????389Gln?Asp?Tyr?Ala?Lys?Ile?His?Asn?Met?Gly?Pro?Asn?Gly?Cys?Gln?Ser

110?????????????????115?????????????????120TCA?AAC?AAC?CAC?TAC?TGG?GAT?AAT?GTC?AGG?AGA?TGT?TTG?GGC?TGA?????????????434Ser?Asn?Asn?His?Tyr?Trp?Asp?Asn?Val?Arg?Arg?Cys?Leu?Gly??*

The information of 125 130 135AGGAAGAAGG AGGAACAACA TTGCCTCAAG GTGGGCCATT TTAAAGATGG CTGCTGTTGA 494TGTATCAAAT TCTAAATTAA AGAAAAGNCA TTTTTAAATT GAATAAATAC CAAATGATAA 554ATG, 557 (2) SEQ ID NO:2:

(i) sequence signature:

(A) length: 136 amino acid

(B) type: amino acid

(D) topology configuration: line style

(ii) molecule type: protein

(iii) sequence description: SEQ ID NO:2Met Asn Tyr Val Ile Phe Val Val Leu Val Ala Leu Tyr Val Ile Glu 15 10 15Val Ala Lys Cys Thr Val Pro Ser Asp Cys Leu Arg Cys Ile Cys Gln

20??????????????????25??????????????????30Val?Glu?Gly?Cys?Asn?Asn?Glu?Ile?Gly?Arg?Cys?Gly?Met?Asp?Ala?Gly

35??????????????????40??????????????????45Sar?Leu?Ser?Cys?Gly?Pro?Tyr?Gln?Ile?Lys?Glu?Pro?Tyr?Arg?Ile?Asp

50??????????????????55??????????????????60Cys?Gly?Arg?Pro?Gly?Gly?Gly?Tyr?Gln?Gln?Cys?Thr?Lys?Glu?Lys?Ala?65??????????????????70??????????????????75??????????????????80Cys?Ser?Glu?Arg?Cys?Val?His?Ala?Tyr?Met?Asp?Arg?Tyr?Ala?Arg?Arg

85??????????????????90??????????????????95Cys?Thr?Gly?Gly?Arg?Gln?Pro?Thr?Cys?Gln?Asp?Tyr?Ala?Lys?Ile?His

100?????????????????105?????????????????110Asn?Met?Gly?Pro?Asn?Gly?Cys?Gln?Ser?Ser?Asn?Asn?His?Tyr?Trp?Asp

115?????????????????120?????????????????125Asn?Val?Arg?Arg?Cys?Leu?Gly??*

The information of 130 135 (3) SEQ ID NO:3:

(i) sequence signature:

(A) length: 571 base pairs

(B) type: nucleic acid

(C) chain: strand

(D) topology configuration: line style

(ii) molecule type: DNA (genomic)

(iii) sequence description: SEQ ID NO:3CTTGAGCTGA ACTGACAATC TTAATATCTC ACTG ATG AAT TAC GTT ATC TTT 52

Met?Asn?Tyr?Val?Ile?Phe

1????????????????5GTG?GTC?TTA?GTG?GCA?CTT?TAC?GTC?ATC?GAG?GTA?GCG?AAG?TGC?ACC?GTT????????100Val?Val?Leu?Val?Ala?Leu?Tyr?Val?Ile?Glu?Val?Ala?Lys?Cys?Thr?Val

10??????????????????15??????????????????20CCA?TCC?GAC?TGC?TTG?AGT?TGC?ATT?TGC?GAG?GTA?GAG?GGA?TGT?GAC?AAA????????148Pro?Ser?Asp?Cys?Leu?Ser?Cys?Ile?Cys?Glu?Val?Glu?Gly?Cys?Asp?Lys

25??????????????????30??????????????????35GAG?ATT?GGA?AGG?TGC?GGC?GAT?GAC?GCA?GGA?AGT?CTG?AGC?TGT?GGT?CCT????????196Glu?Ile?Gly?Arg?Cys?Gly?Asp?Asp?Ala?Gly?Ser?Leu?Ser?Cys?Gly?Pro

40??????????????????45??????????????????50TAC?CAG?ATC?AAG?GAG?CCC?TAC?TGG?ATT?GAC?TGT?GGA?AGT?CCA?GGA?GCA????????244Tyr?Gln?Ile?Lys?Glu?Pro?Tyr?Trp?Ile?Asp?Cys?Gly?Ser?Pro?Gly?Ala?55??????????????????60??????????????????65??????????????????70GGA?TAC?CAG?GAG?TGC?ACT?AAG?GAG?AAG?GCA?TGT?TCC?GAA?ACG?TGT?GTC????????292Gly?Tyr?Gln?Glu?Cys?Thr?Lys?Glu?Lys?Ala?Cys?Ser?Glu?Thr?Cys?Val

75??????????????????80??????????????????85NAC?NCT?TAC?ATG?GAC?AGG?TAT?NCC?ACA?AGG?TGT?ACT?CGA?GGN?NNN?NAA????????340Xaa?Xaa?Tyr?Met?Asp?Arg?Tyr?Xaa?Thr?Arg?Cys?Thr?Arg?Gly?Xaa?Xaa

90??????????????????95?????????????????100CCG?ACC?TGC?CAA?GAC?TAC?GCC?AAA?ATT?CAC?AAC?ATG?GGA?CCG?AAC?GGG????????388Pro?Thr?Cys?Gln?Asp?Tyr?Ala?Lys?Ile?Nis?Asn?Met?Gly?Pro?Asn?Gly

105?????????????????110?????????????????115TGC?AGA?CGT?ACG?AGC?AAC?ACC?TAC?TGG?AAC?AAA?GCC?AAT?GCG?TGT?CTG????????436Cys?Arg?Arg?Thr?Ser?Asn?Thr?Tyr?Trp?Asn?Lys?Ala?Asn?Ala?Cys?Leu

The information of 120 125 130AAC TGAACAAGAC ATTATCGTCA GCTTCAGTCT GCCATCGTCT TTAAAGATGG 489Asn135NNGCTCTCAA ATTCTAAATT GTAAAGAGAT TTCTACAGAC AGAATTATTA GTTGAATTTT 549TAATAAATTA TATTAAAATT GT, 571 (4) SEQ ID NO:4:

(i) sequence signature:

(A) length: 135 amino acid

(B) type: amino acid

(D) topology configuration: line style

(ii) molecule type: protein

(iii) sequence description: SEQ ID NO:4Met Asn Tyr Val Ile Phe Val Val Leu Val Ala Leu Tyr Val Ile Glu 15 10 15Val Ala Lys Cys Thr Val Pro Ser Asp Cys Leu Ser Cys Ile Cys Glu

20??????????????????25??????????????????30Val?Glu?Gly?Cys?Asp?Lys?Glu?Ile?Gly?Arg?Cys?Gly?Asp?Asp?Ala?Gly

35??????????????????40??????????????????45Ser?Leu?Ser?Cys?Gly?Pro?Tyr?Gln?Ile?Lys?Glu?Pro?Tyr?Trp?Ile?Asp

50?????????????????55??????????????????60Cys?Gly?Ser?Pro?Gly?Ala?Gly?Tyr?Gln?Glu?Cys?Thr?Lys?Glu?Lys?Ala?65??????????????????70??????????????????75??????????????????80Cys?Ser?Glu?Thr?Cys?Val?Xaa?Xaa?Tyr?Met?Asp?Arg?Tyr?Xaa?Thr?Arg

85??????????????????90??????????????????95Cys?Thr?Arg?Gly?Xaa?Xaa?Pro?Thr?Cys?Gln?Asp?Tyr?Ala?Lys?Ile?His

100?????????????????105?????????????????110Asn?Met?Gly?Pro?Asn?Gly?Cys?Arg?Arg?Thr?Ser?Asn?Thr?Tyr?Trp?Asn

115?????????????????120?????????????????125Lys?Ala?Asn?Ala?Cys?Leu?Asn

The information of 130 135 (5) SEQ ID NO:5:

(i) sequence signature:

(A) length: 630 base pairs

(B) type: nucleic acid

(C) chain: strand

(D) topology configuration: line style

(ii) molecule type: DNA (genomic)

(iii) sequence description: SEQ ID NO:5AGTAATGAAA ATTCACCTTT CGGACAAGG ATG ATC ATT GCA ATT TAT GTT TCC 53

Met?Ile?Ile?Ala?Ile?Tyr?Val?Ser

1???????????????5CTA?GCT?CTT?CTA?ATC?GCC?TCT?GTG?GAG?GTG?AAT?AGC?CAA?TTC?ACT?GAT???????101Leu?Ala?Leu?Leu?Ile?Ala?Ser?Val?Glu?Val?Asn?Ser?Gln?Phe?Thr?Asp

10??????????????????15??????????????????20TCT?TGC?CTT?CGG?TGT?ATT?TGC?AAG?GTG?GAA?GGA?TGT?GAC?AGT?CAA?ATT???????149Ser?Cys?Leu?Arg?Cys?Ile?Cys?Lys?Val?Glu?Gly?Cys?Asp?Ser?Gln?Ile?25??????????????????30??????????????????35??????????????????40GGA?AAA?TGT?GGA?ATG?GAT?GTT?GGA?AGC?TTG?AGT?TGC?GGA?CCA?TAC?CAG????????197Gly?Lys?Cys?Gly?Met?Asp?Val?Gly?Ser?Leu?Ser?Cys?Gly?Pro?Tyr?Gln

45??????????????????50??????????????????55ATT?AAG?AAA?CCG?TAC?TGG?ATT?GAT?TGT?GGA?AAA?CCA?GGG?GGA?GGT?TAC????????245Ile?Lys?Lys?Pro?Tyr?Trp?Ile?Asp?Cys?Gly?Lys?Pro?Gly?Gly?Gly?Tyr

60??????????????????65??????????????????70GAA?TCA?TGC?ACA?AAA?AAT?AAA?GCC?TGT?TCA?GAG?ACT?TGT?GTG?AGA?GCT????????293Glu?Ser?Cys?Thr?Lys?Asn?Lys?Ala?Cys?Ser?Glu?Thr?Cys?Val?Arg?Ala

75??????????????????80??????????????????85TAC?ATG?AAG?AGG?TAT?GGA?ACC?TTC?TGC?ACA?GGT?GGA?CGA?ACC?CCA?ACC????????341Tyr?Met?Lys?Arg?Tyr?Gly?Thr?Phe?Cys?Thr?Gly?Gly?Arg?Thr?Pro?Thr

90?????????????????95????????????????100TGC?CAG?GAT?TAT?GCT?AGG?ATT?CAT?AAC?GGT?GGA?CCA?CGC?GGT?TGC?AAG????????389Cys?Gln?Asp?Tyr?Ala?Arg?Ile?His?Asn?Gly?Gly?Pro?Arg?Gly?Cys?Lys

105?????????????110?????????????????115?????????????120AGT?TCT?GCT?ACT?GTT?GGT?TAC?TGG?AAC?AAG?GTA?CAG?AAA?TGT?TTG?AGA????????437?Ser?Ser?Ala?Thr?Val?Gly?Tyr?Trp?Asn?Lys?Val?Gln?Lys?Cys?Leu?Arg

The information of 125 130 135TGAATTCGAA ATCTTTGAGT AGCNCCTGTC TTACATTTGA AAGGCCTTTT AATTCAAAAT 497TATTTTGGGA ATCNAATGAT TTTAAACATT TATTTGAAAT TATTCNGAAA TAGAAACAAC 557TATAAATTGC TCCAAGAATT GTATAATCAT GAAGTGTTTG AAAGCTGTTT TCTGAAATAA 617ACTTCCCATA AAT, 630 (6) SEQ ID NO:6:

(i) sequence signature:

(A) length: 136 amino acid

(B) type: amino acid

(D) topology configuration: line style

(ii) molecule type: protein

(iii) sequence description: SEQ ID NO:6Met Ila Ile Ala Ile Tyr Val Ser Leu Ala Leu Leu Ile Ala Ser Val 15 10 15Glu Val Asn Ser Gln Phe Thr Asp Ser Cys Leu Arg Cys Ile Cys Lys

20??????????????????25??????????????????30Val?Glu?Gly?Cys?Asp?Ser?Gln?Ile?Gly?Lys?Cys?Gly?Met?Asp?Val?Gly

35??????????????????40??????????????????45Ser?Leu?Ser?Cys?Gly?Pro?Tyr?Gln?Ile?Lys?Lys?Pro?Tyr?Trp?Ile?Asp

50??????????????????55??????????????????60Cys?Gly?Lys?Pro?Gly?Gly?Gly?Tyr?Glu?Ser?Cys?Thr?Lys?Asn?Lys?Ala?65??????????????????70??????????????????75??????????????????80Cys?Ser?Glu?Thr?Cys?Val?Arg?Ala?Tyr?Met?Lys?Arg?Tyr?Gly?Thr?Phe

85??????????????????90??????????????????95Cys?Thr?Gly?Gly?Arg?Thr?Pro?Thr?Cys?Gln?Asp?Tyr?Ala?Arg?Ile?His

100?????????????????105?????????????????110Asn?Gly?Gly?Pro?Arg?Gly?Cys?Lys?Ser?Ser?Ala?Thr?Val?Gly?Tyr?Trp

115?????????????????120?????????????????125Asn?Lys?Val?Gln?Lys?Cys?Leu?Arg

The information of 130 135 (7) SEQ ID NO:7:

(i) sequence signature:

(A) length: 115 amino acid

(B) type: amino acid

(D) topology configuration: line style

(ii) molecule type: protein

(iii) sequence description: SEQ ID NO:7Thr Val Pro Ser Asp Cys Leu Arg Cys Ile Cys Gln 15 10Val Glu Gly Cys Ase Asn Glu Ile Gly Arg Cys Gly Met Asp Ala Gly

15??????????????????20??????????????????25Ser?Leu?Ser?Cys?Gly?Pro?Tyr?Gln?Ile?Lys?Glu?Pro?Tyr?Trp?Ile?Asp

30??????????????????35??????????????????40Cys?Gly?Arg?Pro?Gly?Gly?Gly?Tyr?Gln?Gln?Cys?Thr?Lys?Glu?Lys?Ala?45??????????????????50??????????????????55??????????????????60Cys?Ser?Glu?Tnr?Cys?Val?His?Ala?Tyr?Met?Asp?Arg?Tyr?Ala?Arg?Arg

65??????????????????70??????????????????75Cys?Thr?Gly?Gly?Arg?Gln?Pro?Thr?Cys?Gln?Asp?Tyr?Ala?Lys?Ile?His

80??????????????????85??????????????????90Asn?Met?Gly?Pro?Asn?Gly?Cys?Gln?Ser?Ser?Asn?Asn?His?Tyr?Trp?Asp

95?????????????????100?????????????????105Asn?Val?Arg?Arg?Cys?Leu?Gly

110?????????????????115

Claims (10)

1. cleaning combination, it contains the isopeptidase of isopeptidase live vol.

2. laundry detergent composition, it comprises:

A) 0.0001-5% weight, the isopeptidase of preferred 0.001-2% weight; With

B) the detergent composition binder component of 95-99.9999% weight.

3. laundry detergent composition, it comprises:

A) 0.1-80% weight, the detergent surfactant of preferred 1-50% weight;

B) 0.0001-5% weight, the isopeptidase of preferred 0.001-2% weight; With

C) the detergent composition binder component of 0.1-99.8% weight.

4. laundry detergent composition, it comprises:

A) the active detersive enzyme of 0.0001-2% weight, it is preferably selected from proteolytic enzyme, cellulase, lipase, amylase, peroxidase and its mixture;

B) 0.0001-5% weight, the isopeptidase of preferred 0.001-2% weight; With

C) the detergent composition binder component of 0.1-99.8% weight, it is preferably selected from detergent surfactant, washing assistant and its mixture.

5. granular detergent composition, it comprises:

A) SYNTHETIC OPTICAL WHITNER of 0.1-50% weight;

B) washing assistant that is selected from silico-aluminate, silicate and its mixture of 1-80% weight;

C) the active detersive enzyme of 0.0001-2% weight, it is selected from proteolytic enzyme, amylase, lipase, cellulase and its mixture;

D) 0.0001-5% weight, the isopeptidase of preferred 0.001-2% weight; With

E) the detergent composition binder component of 0.1-99.8% weight.

6. according to each laundry detergent composition of claim 1-5, it contains washing assistant, detergent surfactant or its mixture, and wherein washing assistant is selected from silico-aluminate, silicate, phosphoric acid salt, phosphonate and its mixture; And wherein tensio-active agent is selected from alkyl alkoxylated vitriol, alkyl-sulphate, linear alkyl sulfonate surfactant, cats product, nonionogenic tenside, amphoterics, zwitterionics and its mixture.

7. according to each laundry detergent composition of claim 1-6, said composition is a granulous.

8. the method for a laundering of textile fabrics, this method is included in will need the aqueous solution of fabric that cleans and the isopeptidase that contains the isopeptidase live vol to contact in the washing machine.

9. the method for a laundering of textile fabrics, this method are included in and will need the fabric that cleans in the washing machine and contain each the aqueous solution of the composition that contains isopeptidase of with good grounds claim 1-7 and contact.

10. method of hand-washing fabric, this method comprise that the fabric that needs are cleaned is immersed in the aqueous solution of the isopeptidase that contains the isopeptidase live vol.