CN1225669A - Detergent composition - Google Patents

Abstract

The present invention provides a detergent composition suitable for use in laundry or dish washing methods, which comprises (a) a hard acid cationic component; and (b) a hard base polymeric component, wherein the ratio of cationic component to hard base polymeric component being from 10:1 to 1:3.

Description

Detergent composition

Technical field

The present invention relates to contain the detergent composition of cationic components and hard base polymeric constituent, it is applicable to laundry and dishware washing method.

Background of invention

Be used to do washing and the makers-up of the detergent composition of dishware washing method faces and removes unctuousness dirt/spot satisfactorily, promptly have the challenge of the dirt/spot of tri-glyceride at high proportion or lipid acid.In Betengent product, adopt surface active agent composition to help to remove these unctuousness dirt/spots traditionally.Particularly, to be used to remove unctuousness dirt/spot be well-known to the surfactant system that contains cats product.

For example, EP-B-21491 has described the detergent composition that contains nonionic/cats product mixture and contain silico-aluminate and multi-carboxy acid salt washing agent's washing assistant mixture.Cats product can be a cationic ester.The particle of improvement and the removal of greasy/oily soil have been described.

U-A-4228042 discloses the biodegradable cats product that comprises the cationic ester tensio-active agent, and it is used for detergent composition so that the removal of greasy/oily soil to be provided.These cats products and the combination of nonionogenic tenside in composition have also been described to be used to remove particulate fouling.

Polymkeric substance also is the known component of detergent composition, and they are mixed in detergent composition as soil-suspending agent usually.

Spot and greasy dirt removal character that the detergent composition of cationic components and polymeric constituent is mixed in our discovery simultaneously obtain beat all enhancing when two kinds of components are used with specific proportions.The combination of the component of use in the particular ratio scope also makes the total amount of one or both components reduce and obtains scourability identical or that improve simultaneously.

The relevant portion of all documents of quoting in this manual is incorporated herein by reference.

Summary of the invention

Detergent composition of the present invention contains the hard acid cationic components and by total detergent composition weight hard base polymeric constituent of 1.7% nearly, wherein the ratio of hard acid cationic components and hard base polymeric constituent is 10: 1-1: 3, and composition contains and is less than 20% phosphate component by weight.

Of the present invention preferred aspect, the ratio of hard acid cationic components and hard base polymeric constituent is 5: 1-1: 2.Ratio can be 5: 1-1: 1.Aspect preferred, described hard acid cationic components comprises the cats product of following formula:

R ¹R ² _mR ³ _3-mN ⁺A is R wherein ¹Expression C _6-24Alkyl or alkenyl or C _6-12Alkaryl, each R2 represents (C independently _nH _2nO) _xR ₄Group, wherein n is 1-4, x is 1-14, and R ⁴Expression hydrogen (preferably), methyl or ethyl are at R ² _mMiddle C _nH _2nThe sum of O group is 1-14, each R ³Represent C independently _1-12Alkyl or alkenyl, aryl or C _1-6Alkaryl, m be 1,2 or 3 and A provide electroneutral counter ion.

The detailed description hard acid cationic components of invention

The necessary component of detergent composition of the present invention is a cationic components.Usually the hard acid cationic components comprises quaternary ammonium compound, preferred surfactant.Cationic components is preferably in by detergent composition weight 0.5%-20.0%, more preferably 0.1%-10%, most preferably 1.0%-5.0% or even be lower than 1.5% content and exist.

Can use any quaternary ammonium cation tensio-active agent, yet according to a preferred aspect of the present invention, cationic components comprises the tensio-active agent that is selected from following formula: compound:

R ¹R ² _mR ³ _3-mN ⁺A ^-R wherein ¹Expression C _6-24Alkyl or alkenyl or C _6-12Alkaryl, each R ²Represent (C independently _nH _2nO) _xR ⁴Group, wherein n is 1-4, x is 1-14, and R ⁴Expression hydrogen (preferably), methyl or ethyl are at R ² _mMiddle C _nH _2nThe sum of O group is 1-14, each R ³Represent C independently _1-12Alkyl or alkenyl, aryl or C _1-6Alkaryl, m be 1,2 or 3 and A provide electroneutral counter ion.

R in the especially preferred tensio-active agent ²Equal-CH ₂CH ₂OH, each R ³Be independently selected from C _1-4Alkyl, preferable methyl, m is 1 or 2.R ¹Straight chain C preferably _6-14Alkyl, C _8-10Alkyl is found to be especially suitable, C _12-14Alkyl also is found to be especially suitable.

Cationic components is the single cropping ammonium compound preferably.

The dispersible compound of water that cationic components tensio-active agent of the present invention preferably has surfactant properties.

Cationic components can comprise the cationic ester tensio-active agent.Suitable cationic ester tensio-active agent comprises the cholinesterase tensio-active agent, for example is being disclosed among the US4228042,42396600 and 4260529.

In the preferred cationic ester surfactant, the ester bond of cationic ester (promptly-COO-) and the group of band cationic charge in surfactant molecule by by containing at least three atoms (i.e. three atom chain lengths), preferred 3-8 atom, more preferably 3-5 atom, most preferably the spacer groups formed of the chain of 3 atoms separately.The atom that forms the spacer groups chain is selected from carbon, nitrogen and Sauerstoffatom and its mixture arbitrarily, and its prerequisite is that any nitrogen in described chain or Sauerstoffatom only are connected with carbon atom in the chain.Therefore, got rid of and for example contained-O-O-(being superoxide) ,-N-N-and-spacer groups of N-O-key, and comprise and for example containing-CH ₂-O-CH ₂-and-CH ₂-NH-CH ₂The spacer groups of-key.Aspect preferred, the spacer groups chain only contains carbon atom, and optimum select chain is an alkyl.

The cationic ester tensio-active agent preferably has the compound of 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) _sX and Y are independently selected from COO, OCO, O, CO, OCOO, CONH, NHCO, OCONH and NHCOO; Be COO, OCO, OCOO, OCONH or NHCOO group one of at least among X or the Y wherein; R ₂, R ₃, R ₄, R ₆, R ₇And R ₈Be independently selected from alkyl, alkenyl, hydroxyalkyl and hydroxyl alkenyl with 1-4 carbon atom, and alkaryl; And R ₅Be H or C independently ₁-C ₃Alkyl; Wherein the value of m, n, s and t is 0-8 independently, and the value of b is 0-20, and the value of a, u and v is 0 or 1 independently, and its prerequisite is that at least one must be 1 among u or the v; Wherein M is counter ion.

M is preferably selected from halide-ions, methylsulfate, sulfate radical and nitrate radical, more preferably methylsulfate, chlorion, bromide anion or iodide ion.

The cationic ester tensio-active agent can be selected from the compound with following formula:

R wherein ₁Be C ₅-C ₃₁Straight or branched alkyl, alkenyl or alkaryl chain; X is selected from COO, OCO, OCOO, OCONH and NHCOO; R ₂, R ₃And R ₄Be independently selected from alkyl and hydroxyalkyl with 1-4 carbon atom; And R ₅Be H or C independently ₁-C ₃Alkyl; Wherein the value of n is 0-8, and the value of b is 0-20, and the value of a is 0 or 1, and the value of m is 3-8.

More preferably, R ₂, R ₃And R ₄Be independently selected from C ₁-C ₄Alkyl and C ₁-C ₄Hydroxyalkyl.One preferred aspect, R ₂, R ₃And R ₄In at least one, preferably only one be hydroxyalkyl.Hydroxyalkyl preferably contains 1-4 carbon atom, more preferably 2 or 3 carbon atoms, most preferably 2 carbon atoms.Another preferred aspect, R ₂, R ₃And R ₄In at least one is C ₂-C ₃More preferably there are two C in alkyl ₂-C ₃Alkyl.

The ester that the dispersible cationic ester tensio-active agent of very preferred water is a following formula: Wherein m is 1-4, preferred 2 or 3, and R ₁Be C ₁₁-C ₁₉The straight or branched alkyl chain.

The especially preferred cholinesterase of this class comprises stearyl-cholinesterase tetramethyl-ammonium halogenide (R ¹=C ₁₇Alkyl), palmitoyl cholinesterase tetramethyl-ammonium halogenide (R ¹=C ₁₅Alkyl), myristoyl cholinesterase tetramethyl-ammonium halogenide (R ¹=C ₁₃Alkyl), lauroyl cholinesterase tetramethyl-ammonium halogenide (R ¹=C ₁₁Alkyl), coconut acyl group cholinesterase tetramethyl-ammonium halogenide (R ¹=C ₁₁-C ₁₃Alkyl), Tallow, beef acyl group cholinesterase tetramethyl-ammonium halogenide (R ¹=C ₁₅-C ₁₇Alkyl) and their any mixture.

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

Aspect preferred, the cationic ester tensio-active agent is hydrolyzable under the condition of clothes washing method.

Preferred cationic surfactants comprises alkoxy quaternary ammonium (AQA) tensio-active agent of following general formula:

Wherein R1 contains about 18 carbon atoms of the 8-that has an appointment, preferred about 16 carbon atoms of 10-, the most preferably from about alkyl of about 14 carbon atoms of 10-or alkenyl part; R ²And R ³Be the alkyl that contains about 3 carbon atoms of 1-independently of one another, preferable methyl; R ⁴Be selected from hydrogen (preferably), methyl and ethyl, X-provides electroneutral negatively charged ion, for example chlorion, bromide anion, methylsulfate, sulfate radical etc.; A is selected from C ₁-C ₄Alkoxyl group, especially oxyethyl group (promptly-CH ₂CH ₂O-), propoxy-, butoxy and their mixture; P is that 2-is about 30, and preferred 2-is about 15, and most preferably 2-about 8.Other preferred cationic surfactants comprises the tensio-active agent of following formula:

One or more washings (comprising fabric nursing) auxiliary substance of Miao Shuing hereinafter is wherein for AQA tensio-active agent, R ¹Be to contain about 18 carbon atoms of the 8-that has an appointment, preferred about 16 carbon atoms of 10-, the most preferably from about alkyl of about 14 carbon atoms of 10-or alkenyl part; R ²Be the alkyl that contains 1-3 carbon atom, preferable methyl; R ²And R ⁴Can change independently, and be selected from hydrogen (preferably), methyl and ethyl, X-provides electroneutral negatively charged ion, for example chlorion, bromide anion, methylsulfate, sulfate radical etc.; A and A ' can change independently, and are selected from C respectively ₁-C ₄Alkoxyl group, especially oxyethyl group (promptly-CH ₂CH ₂O-), propoxy-, butoxy and their mixture; P is that 1-is about 30, and preferred 1-is about 4, and q is that 1-is about 30, and preferred 1-is about 4,, most preferably p and q are 1.

The hard base polymeric constituent

The hard base polymeric constituent preferably includes the polymkeric substance that has side group (promptly be not the group of polymkeric substance chain link group, so it not forming the part of polymer backbone), and it is the alkali harder than the benzene sulfonate group of following formula according to the Pearson of hard and soft matter classification:

Polymeric constituent preferably includes and contains than sulfonate groups, for example CH ₃CH ₂CH ₂-SO ₃ ^-The polymkeric substance of the side group of hard alkali.Polymeric constituent is usually by by weight at least 5%, preferably at least 25% or even at least 50%, more preferably at least 60%, most preferably at least 90% monomer that forms this side group forms.Polymeric constituent preferably has 1500-150000, most preferably the molecular weight of 2000-100000, especially 5000-80000.The mensuration of molecular weight uses vinylbenzene to carry out as standard by GPC.

Especially preferred side group is carboxyl (acidic group that this paper relates to also comprises their salt).Polymeric poly carboxylic acid material can be preferably their acid preparation by polymerization or the suitable unsaturated monomer of copolymerization.The unsaturated monomer acid that polymerizable 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.Exist in polymkeric substance of the present invention and do not contain hard base group (for example carboxylate groups), for example the monomer segment of vinyl methyl ether, vinylbenzene, ethene etc. is suitable, as long as this segment preferably is no more than about by weight 40%.The homopolymer of vinylformic acid and toxilic acid or multipolymer are especially preferred.

Vinylformic acid/maleic copolymer comprises the water-soluble salt of the multipolymer of vinylformic acid and toxilic acid.The molecular-weight average of the multipolymer of this acid is preferably about 2000-100000, more preferably from about 5000-75000, most preferably from about 7000-65000 or even 10000-50000.The pulsating ratio of vinylformic acid and toxilic acid is generally about 30 in this preferred copolymer: about 1: 1 of 1-, more preferably from about 10: 1-2: 1.The water-soluble salt of this vinylformic acid/maleic acid can comprise for example ammonium salt of basic metal, ammonium and replacement.Acrylate/the maleate copolymer of such solubility is known, they were described among the disclosed EP193360 in December 15 nineteen eighty-two disclosed EP66915 and on September 3rd, 1986, and the latter has also described this polymkeric substance that contains the hydroxypropyl acrylate.

Can also use poly aspartic acid and polyglutamic acid dispersion agent, especially be used in combination with zeolite builders.Dispersion agent, for example poly aspartic acid 10000 the molecular weight (on average) of preferably having an appointment.

The hard base polymkeric substance can be to contain any organic polymer material that is used as the hard base group of dispersion agent, anti redeposition agent and soil-suspending agent usually in detergent composition.

The example of organic polyhydroxyl compound also comprises poly carboxylic acid or its salt of water-soluble all organic or copolymerization, and wherein poly carboxylic acid comprises that at least two quilts are no more than the carboxyl that two carbon atoms separate.The polymkeric substance of back one type is disclosed in GB-A-1596756.The example of this salt comprises the polyacrylate of MWt1500-5000.

Being used for polyamino compounds of the present invention comprises as EP-A-305282, EP-A-305283 and the disclosed compound that obtains from aspartic acid of EP-A-351629.

The terpolymer that contains the monomeric unit that is selected from toxilic acid, vinylformic acid, poly aspartic acid and vinyl alcohol, the terpolymer that especially has the molecular weight of 5000-10000 also is suitable for.They comprise toxilic acid/vinylformic acid/vinyl alcohol terpolymer.These materials are disclosed in EP193360, comprise for example 45/45/10 terpolymer of vinylformic acid/toxilic acid/vinyl alcohol.

The hard base polymeric constituent preferably exists as any grain fraction, and wherein they are useful as tackiness agent.

Detergent composition of the present invention preferably contains and is no more than 5% sodium sulfate.

Additional detergent components

Detergent composition of the present invention also can contain additional detergent components.The definite character of these annexing ingredients and their add-on will depend on the physical form of composition and the definite character of its washing operation that is used for.

Composition of the present invention preferably contains one or more additional detergent components, and it is selected from additional surfactant, additional SYNTHETIC OPTICAL WHITNER, bleaching catalyst, alkaline system, washing assistant, organic polymer, additional enzyme, suds suppressor, lime soap dispersing agent, soil-suspending agent and anti redeposition agent and corrosion inhibitor.

Peroxyacid bleaching system

The preferred characteristics of detergent composition of the present invention is organic bleach system.Bleach system preferably contains hydrogen peroxide cource and organic peroxide acid bleach precursor compound.Situ reaction by precursor and hydrogen peroxide cource produces organic peroxide acid.Preferred hydrogen peroxide cource comprises inorganic perhydrate SYNTHETIC OPTICAL WHITNER.In alternative preferred embodiment, the organic peroxide acid bleach system contains preformed organic peroxide acid, and it directly adds in the composition.Also can imagine the composition that contains with the mixture of preformed organic peroxide acid bonded hydrogen peroxide cource and organic peroxy acid precursor.

Inorganic perhydrate SYNTHETIC OPTICAL WHITNER

Inorganic perhydrate salt is preferred hydrogen peroxide cource.These salt are usually with basic metal, and the form of particular certain cancers adds, and its add-on is counted 1%-40% by composition weight, more preferably 2%-30%, most preferably 5%-25%.

The example of inorganic perhydrate salt is perborate, percarbonate, superphosphate, persulphate and persilicate.Inorganic perhydrate salt is an alkali metal salt normally.It is involved that inorganic perhydrate salt can not have the form of crystalline solid of supplementary protection.Yet for some perhydrate salt, the preferred embodiment of this particulate composition is used the material that is provided at the preferable package stability of perhydrate salt in the particulate product of coated form.Suitable coating compounds comprises inorganic salt, for example alkalimetal silicate, carbonate or borate or their mixture, or organic materials, for example paraffin, oil or fatty soap.

Sodium peroxoborate is preferred perhydrate salt, can be nominal formula NaBO ₂H ₂O ₂Monohydrate or tetrahydrate NaBO ₂H ₂O ₂3H ₂The form of O.

Alkali metal percarbonate, especially SPC-D are preferred perhydrate of the present invention.SPC-D is to have corresponding to 2Na ₂CO ₃3H ₂The addition compound of the chemical formula of O obtains with crystalline solid commercial.

The peroxide Potassium peroxysulfate is another the inorganic perhydrate salt that is used for this detergent composition.

Peroxyacid bleach precursor

Peroxyacid bleach precursor is the compound that generates peroxy acid in crossing hydrolysis reaction with hydroperoxidation.Peroxyacid bleach precursor is expressed from the next usually:

Wherein L is a leavings group, and X is any functional group basically, and the structure of the peroxy acid that was generated when making hydrolysis is:

The peroxyacid bleach precursor compound is preferably in by detergent composition weight 0.05%-20%, more preferably 0.1%-15% by weight, and most preferably the content of 0.2%-10% adds by weight.

Suitable peroxyacid bleach precursor compound contains one or more N-or O-carboxyl groups usually, the optional kind from wide region of this precursor.Suitable kind comprises the acyl derivative of acid anhydride, ester, imide, lactan and imidazoles and oxime.The example of useful material is disclosed in GB-A-1586789 in these classes.Suitable ester GB-A-836988,864798,1147871,2143231 and EP-A-0170386 in be disclosed.Leavings group

Leavings group, L group hereinafter referred to as, for cross hydrolysis reaction must be enough reactive with in the time of the best (for example wash(ing)cycle) react.Yet if L is too active, this activator is used for bleaching composition and will be difficult to stablize.

Preferred L, group is selected from:

With

With

With their mixture, wherein R ¹Be alkyl, aryl or the alkaryl that contains 1-14 carbon atom, R ³Be the alkyl chain that contains 1-8 carbon atom, R ⁴Be H or R ³And Y is H or solubilizing group.Any R ¹, R ³And R ⁴Can be by any functional group basically, for example comprise that alkyl, hydroxyl, alkoxyl group, halogen, amine, nitrosyl radical, acid amides and ammonium or alkylammonium replace.

Preferred solubilizing group is-SO ₃ ^-M ⁺,-CO ₂ ^-M ⁺,-SO ₄ ^-M ⁺,-N ⁺(R ³) ₄X ^-And O ← N (R ³) ₃, most preferably-SO ₃ ^-M ⁺With-CO ₂ ^-M ⁺, R wherein ³Be the alkyl chain that contains 1-4 carbon atom, M provides water miscible positively charged ion to bleach-activating agent, and X provides water-soluble anionic to bleach-activating agent.M is the ammonium cation of basic metal, ammonium or replacement preferably, most preferably sodium and potassium, and X is halogenide, oxyhydroxide, methylsulfate or acetic acid anion.Alkyl percarboxylic acids bleach precursor

Alkyl percarboxylic acids bleach precursor forms percarboxylic acids when crossing hydrolysis, the preferred precursor of this class forms peracetic acid when crossing hydrolysis.

The alkyl peroxycarboxylic acid precursors compound of preferred imide-type comprises N-; tetra-acetylatedization of N ＇ N ＇ Alkylenediamine, wherein alkylidene group contains 1-6 carbon atom, and especially wherein alkylidene group contains 1; the compound of 2 and 6 carbon atoms, tetra acetyl ethylene diamine (TAED) is especially preferred.

Other preferred alkyl peroxycarboxylic acid precursors comprises 3,5,5-trimethyl acetyl oxygen base benzene sulfonic acid sodium salt (iso-NOBS), acyloxy benzene sulfonic acid sodium salt in the ninth of the ten Heavenly Stems (NOBS), acetoxyl group benzene sulfonic acid sodium salt (ABS) and penta-acetyl glucose.Hydrophilic when bleach precursor, more particularly, when it contained TAED and is, it was preferably in by total detergent composition weight at least 1.5%, or even by weight at least 3.5%, most preferably at least 5% or above content exist.The alkyl peroxy acids precursor that acid amides replaces

Preferred peroxyacid precursor is the alkyl peroxy acids precursor compound that acid amides replaces, and it comprises the compound of following general formula:

Or

R wherein ¹For comprising the alkyl or the alkaryl of about 14 carbon atoms of about 1-, R ²Be alkylidene group, arylidene and the alkarylene group that comprises about 1-14 carbon atom, R ⁵For H or contain alkyl, aryl or the alkylaryl group of 1-10 carbon atom, and L is essentially any leavings group.R ¹Preferably contain 6-12 the carbon atom of having an appointment.R ²Preferably contain 4-8 the carbon atom of having an appointment.R ¹Can be the aryl or the alkaryl of straight or branched alkyl, replacement, it contains side chain, substituting group or both, and can comprise that for example animal tallow obtains by synthetic source or natural origin.To R ²Also can allow similar structural changes.R ²Can comprise alkyl, aryl, wherein said R ²Also can contain halogen, nitrogen, sulphur and other typical substituting group or organic compound.R ⁵Preferred hydrogen or methyl.R ¹And R ⁵The carbonatoms that contains amounts to should be no more than 18.The bleach activating immunomodulator compounds that this class acid amides replaces is described in EP-A-0170386.

The preferred embodiment of such bleach precursor comprises the peroxyacid precursor compound that acid amides replaces; it is selected from as (the amino caproyl of 6-decoyl) oxygen base benzene sulfonate of describing among the EP-A-0170386, (the amino caproyl of 6-caprinoyl) oxygen base benzene sulfonate; highly preferred (the amino caproyl of 6-nonanoyl) oxygen base benzene sulfonate and their mixture.Peroxybenzoic acid precursors

The peroxybenzoic acid precursors compound provides peroxybenzoic acid when crossing hydrolysis.Suitable O-acylations peroxybenzoic acid precursors compound comprises the benzoyl product of replacement and unsubstituted benzoyl oxygen base benzene sulfonate and Sorbitol Powder, glucose and all carbohydrates and benzoyl reagent, and this class imide-type compound comprises the urea that N-benzoyl succinimide, four benzoyl quadrols and N-benzoyl replace.Suitable imidazole type peroxybenzoic acid precursors comprises N-benzoyl imidazoles and N-benzoyl benzo imidazoles.The peroxybenzoic acid precursors that contains the N-acyl group that other is useful comprises N-benzoyl pyrrolidone, dibenzoyl taurine and benzoyl Pyrrolidonecarboxylic acid.The positively charged ion peroxyacid precursor

Positively charged ion peroxyacid precursor compound produces the positively charged ion peroxy acid when crossing hydrolysis.

The positively charged ion peroxyacid precursor is usually by with positively charged functional group, for example ammonium or alkyl ammonium group, and the peroxy acid of the peroxyacid precursor compound that preferred ethyl or the replacement of methyl ammonium are suitable partly forms.The positively charged ion peroxyacid precursor usually with suitable negatively charged ion, for example the form of halogen ionic salt is present in the solid detergent composition.

So the peroxyacid precursor compound that is replaced by positively charged ion can be the precursor compound of the derivative of aforesaid peroxybenzoic acid or its replacement.In addition, the peroxyacid precursor compound can be the alkyl peroxy acids precursor that alkyl peroxycarboxylic acid precursors compound or acid amides hereinafter described replace.

The positively charged ion peroxyacid precursor US4904406,4751015,4988451,43977757,5269962,5127852,5093022,5106528, UK1382594, EP475512,458396 and 284292 and JP87-318332 in be described.

The example of preferred cation peroxyacid precursor is described in patent application 9407944.9 and US patent application 08.298903,08/298650,08/298904 and 08/298906.

Suitable positively charged ion peroxyacid precursor comprises alkyl or benzoyl oxygen base sulfonate, N-acylations hexanolactam and the tetra-acetylated glucose benzoyl peroxide of single benzoyl that any ammonium or alkylammonium replace.Preferred N-acylations hexanolactam cationoid peroxyacid precursor comprises trialkyl ammonium methylene radical benzoyl caprolactam and trialkyl ammonium methylene radical alkyl hexanolactam.

Benzoxazine organic peroxy acid precursor

Also suitable is disclosed benzo oxazinyl precursor compound in for example EP-A-332294 and EP-A-482807, especially has those of following formula:

(the 17th page of square frame 1 of original text, empty 5 row)

R wherein ₁Be alkyl, alkaryl, aryl or aralkyl.N-acylations lactan precursor

Another kind of hydrophobic bleach activator is a general disclosed lactams N-acylations precursor compound in GB-A-955735.Preferred such material comprises hexanolactam.

Suitable caprolactam bleach agent precursor has following formula:

R wherein ¹Be alkyl, aryl, alkoxy aryl or the alkaryl that contains 6-12 carbon atom.Preferred hydrophobic N-acyl caprolactam bleach precursor material is selected from benzoyl caprolactam, capryloyl hexanolactam, nonanoyl hexanolactam, decanoyl hexanolactam, undecylene acyl caprolactam, 3; 5,5-trimethyl acetyl base hexanolactam and their mixture.Nonanoyl hexanolactam most preferably.

Suitable Valerolactim has following formula:

R wherein ¹Be alkyl, aryl, alkoxy aryl or the alkaryl that contains 6-12 carbon atom.R ¹More preferably be selected from phenyl, heptyl, octyl group, nonyl, 2,4,4-tri-methyl-amyl, decene base and their mixture.

Can also use the mixture of any above-mentioned peroxyacid bleach precursor.Preformed organic peroxide acid

Except that organic peroxide acid bleach precursor compound or alternatively, the organic peroxide acid bleach system can contain preformed organic peroxide acid, common content is for pressing composition weight meter 0.05%-20%, more preferably 1%-10% by weight.

The compound that the acid amides that preferred hydrophobic organic peroxy acid compound is following general formula replaces:

Or

R wherein ¹For containing the alkyl or the alkaryl of about 14 carbon atoms of the 1-that has an appointment, R ²For containing alkylidene group, arylidene and the alkarylene of 1-14 the carbon atom of having an appointment, R ⁵For H or contain alkyl, aryl or the alkaryl of 1-10 carbon atom.R ¹Preferably contain 6-12 the carbon atom of having an appointment.R ²Preferably contain 4-8 the carbon atom of having an appointment.R ¹Can be the aryl or the alkaryl of straight or branched alkyl, replacement, it contains side chain, substituting group or both, and can comprise that for example animal tallow obtains by synthetic source or natural origin.To R ²Also can allow similar structural changes.R ²Can comprise alkyl, aryl, wherein said R ²Also can contain halogen, nitrogen, sulphur and other typical substituting group or organic compound.R ⁵Preferably hydrogen or methyl.R ¹And R ⁵Should not contain and surpass 18 carbon atoms altogether.The bleach activating immunomodulator compounds that this class acid amides replaces is described in EP-A-0170386.The suitable example of such reagent comprises magnesium salts, 4-amino in the ninth of the ten Heavenly Stems-4-oxo Perbutyric Acid and the diperoxy dodecanedioic acid of (6-is hot amino)-6-oxo caproic acid, (6-amino in the ninth of the ten Heavenly Stems)-6-oxo caproic acid, (6-amino in the last of the ten Heavenly stems)-6-oxo caproic acid, monoperphthalic acid magnesium hexahydrate, inclined to one side chlorine peroxybenzoic acid.These SYNTHETIC OPTICAL WHITNER are described in US4483781, US4634551, EP0133354, US4412934 and EP0170386.Hydrophobic preformed peroxy acid bleach immunomodulator compounds preferred for the present invention is single nonanoyl amidoperoxycarboxylic acid.

Other suitable organic peroxide acid comprises diperoxy chain docosandioic acid, as diperoxy dodecanedioic acid, diperoxy tetradecane diacid and diperoxy Thapsic acid.

Other suitable organic peroxide acid comprises the diamino peroxy acid, and it is described in WO95/03275, has following general formula:

Wherein: R is selected from C ₁-C ₁₂Alkylidene group, C ₅-C ₁₂Cycloalkylidene, C ₆-C ₁₂Arylidene and their moiety combinations; R ¹And R ²Be independently selected from H, C ₁-C ₁₆Alkyl and C ₆-C ₁₂Aryl and and R ³Can form C together with two nitrogen ₃-C ₁₂The group of ring; R ³Be selected from C ₁-C ₁₂Alkylidene group, C ₅-C ₁₂Cycloalkylidene and C ₆-C ₁₂Arylidene; Each integer of selecting naturally of n and n ' make they and be 1; Each integer of selecting naturally of m and m ' make they and be 1; With

M is selected from H, basic metal, alkaline-earth metal, ammonium, alkanol ammonium cation and their moiety combinations.

Other suitable organic peroxide acid comprises the amido peroxy acid, and it is described in WO95/16673, and has following by general formula:

X-Ar-CO-NY-R (Z)-CO-OOH wherein X represents hydrogen or compatible substituting group, and Ar is an aryl, and R represents (CH ₂) _n, wherein n is 2 or 3 and Y and Z represent to be selected from hydrogen or alkyl or aryl or alkaryl independently of one another or the substituting group of the aryl that replaced by compatible substituting group, and its condition is if n=3, and at least one is not a hydrogen among Y and the Z.Substituent X on benzene nucleus preferably hydrogen or to substituting group, it is selected from halogen, be generally the chlorine atom, or some do not discharge not interferential group, alkyl for example, nearly C6, for example methyl, ethyl or propyl group usually.X can represent second amido percarboxylic acids substituting group of following formula in addition:

-CO-NY-R (Z)-CO-OOH wherein R, Y, Z and n is as defined above.

MOOC-R ¹CO-NR ²-R ³-NR ⁴-CO-R ⁵COOOM is R wherein ¹Be selected from C ₁-C ₁₂Alkylidene group, C ₅-C ₁₂Cycloalkylidene, C ₆-C ₁₂Arylidene and their moiety combinations; The R additional surfactant

Detergent composition of the present invention preferably contains additional surfactant, and it is preferably selected from negatively charged ion, nonionic, both sexes (ampholytic), both sexes (amphoteric) and zwitterionics and its mixture.

The classification and the kind of typical negatively charged ion, nonionic, both sexes and the zwitterionics of these tensio-active agents in authorizing the US3929678 of Laughlin and Heuring on December 30th, 1975, have been listed.Other example is listed in " tensio-active agent and washing composition) " (volume I and II, Schwartz, Perry and Berch).

If exist, both sexes (ampholytic), both sexes (amphoteric) and zwitterionics are used in combination with one or more negatively charged ion and/or nonionogenic tenside usually.

Anion surfactant

Detergent composition of the present invention preferably contains additional anion surfactant.Basically any anion surfactant that is used for washing purposes all can be used for detergent composition.They can comprise anion sulfate, sulfonate, carboxylate salt and sarcosinate surfactant salt (comprise for example ammonium salt of sodium, potassium, ammonium and replacement, for example single, two and triethanolamine salt).The anion sulfate acid salt surfactant is preferred.

Other anion surfactant comprises isethionate, for example fatty acid amide, alkyl succinate and the sulfosuccinate of acyl isethinate, N-acyl taurine salt, N-methyltaurine, sulfosuccinic acid monoesters (especially saturated and undersaturated C ₁₂-C ₁₈Monoesters), sulfosuccinic acid diesters (especially saturated and unsaturated C ₆-C ₁₄Diester), N-acyl sarcosinate.Resinous acid and hydrogenated resin acid also are suitable, for example rosin, staybelite and the resinous acid and the hydrogenated resin acid that are present in or obtain from tallow oil.

The anion sulfate acid salt surfactant

Be applicable to that anion sulfate tensio-active agent of the present invention comprises straight chain and side chain primary and secondary alkyl-sulphate, alkyl ethoxy sulfate, fatty oil acylglycerol vitriol, alkylphenol oxyethane ether sulfate, C ₅-C ₁₇Acyl group-N-(C ₁-C ₄Alkyl) and-N-(C ₁-C ₂Hydroxyalkyl) vitriol of glucosamine sulfate and alkyl polysaccharide, for example vitriol of alkyl polyglucoside (the not Sulfated compound of the nonionic of Miao Shuing herein).

Alkyl sulfate surfactant is preferably selected from straight chain and side chain uncle C ₁₀-C ₁₈Alkyl-sulphate, more preferably C ₁₁-C ₁₅Branched-chain alkyl vitriol and C ₁₂-C ₁₄Straight-chain alkyl sulfate.

Alkyl ethoxy sulfate surfactant is preferably selected from C ₁₀-C ₁₈Alkyl-sulphate, every mole of this alkyl-sulphate is by O.5 to 20 moles of ethylene oxide ethoxylations.Alkyl ethoxy sulfate surfactant is more preferably C ₈-C ₁₈, C most preferably ₁₁-C ₁₅Alkyl-sulphate, every mole of this alkyl-sulphate be by 0.5-7, preferred 1-5 moles of ethylene oxide ethoxylation.

The especially preferred aspect of the present invention is to adopt the mixture of preferred alkyl-sulphate and alkyl ethoxy sulfate surfactant.These mixtures are disclosed in PCT patent application WO93/18124.Work as C ₁₂When alkylbenzene sulfonate was added in the detergent composition of the present invention, it can be lower than 8% amount existence by composition weight meter.The anion sulfoacid salt surfactant

Be applicable to that anionic sulphonate tensio-active agent of the present invention comprises C ₅-C ₂₀Linear alkylbenzene sulfonate, alkyl ester sulfonate, C ₆-C ₂₂Uncle or secondary paraffin sulfonate, C ₆-C ₂₄Alkene sulfonate, sulfonation poly carboxylic acid, alkyl glycerol sulfonate, fatty acyl group glycerol sulfonate, fatty oil acylglycerol sulfonate and their any mixture.Work as C ₁₂When alkylbenzene sulfonate was added in the detergent composition of the present invention, it can be lower than 8% amount existence by composition weight meter.The anionic carboxylic acid salt surfactant

The anionic carboxylate tensio-active agent that is suitable for comprises alkyl ethoxy carboxylate, alkyl polyethoxye multi-carboxylate's tensio-active agent and soap (' alkyl carboxyl '), especially some secondary soap of describing herein.

Suitable alkyl ethoxy carboxylate comprises formula RO (CH ₂CH ₂O) _xCH ₂COO ^-M ⁺Compound, wherein R is C ₆-C ₁₈Alkyl, x are 0 to 10, based on weight basis, ethoxylate distribute to make x wherein be 0 amount of substance be less than about 20% and M be positively charged ion.Suitable alkyl polyethoxye multi-carboxylate tensio-active agent comprises formula RO-(CHR ₁-CHR ₂-O)-R ₃Compound, wherein R is C ₆-C ₁₈Alkyl, x are 1 to 25, R ₁And R ₂Be selected from hydrogen, methyl acidic group, amber acidic group, hydroxy succinic acid base and their mixture, and R ₃Be selected from hydrogen, contain replacement or the unsubstituted hydrocarbon and their mixture of 1 to 8 carbon atom.

Suitable soap surfactant comprises secondary soap surfactant, and it contains the carboxyl unit that is connected in secondary carbon(atom).The preferred secondary soap surfactant that uses is water miscible material, and it is selected from 2-methyl isophthalic acid-undeeanoic acid, 2-ethyl-1-capric acid, 2-propyl group-1-n-nonanoic acid, 2-butyl-1-is sad and the water-soluble salt of 2-amyl group-1-enanthic acid.Can comprise that also some soap is as suds suppressor.The basic metal sarcosinate surfactant

Other suitable anion surfactant is formula R-CON (R ¹) CH ₂The basic metal sarcosinate of COOM, wherein R is C ₅-C ₁₇Straight or branched alkyl or alkenyl, R ¹Be C ₁-C ₄Alkyl, M are alkalimetal ions.Preferred examples is the tetradecyl and the oleoyl methyl sarcosinate of sodium-salt form.Alkoxy-based non-ionic surface active agent

Basically any alkoxy-based non-ionic surface active agent is applicable to the present invention, preferred ethoxylation and propoxylation nonionogenic tenside.

The preferred alkoxylated tensio-active agent can be selected from alkylphenol nonionic condenses, nonionic ethoxylated alcohol, nonionic ethoxylated/propoxylated fatty alcohol, propylene glycol nonionic ethoxylate/propoxylated glycerine condenses and propylene oxide/ethylenediamine adduct nonionic ethoxylate condensation product.Nonionic alcohol alcoxylates tensio-active agent

The condensation product of the alkylene oxide of fatty alcohol and 1-25 mole, especially oxyethane and/or propylene oxide is applicable to the present invention.The alkyl chain of fatty alcohol can be a straight or branched, and uncle or secondary is contained 6-22 carbon atom usually.Especially preferred is to have the alcohol of the alkyl that contains 8-20 carbon atom and the condensation product of every mol of alcohol 2-10 moles of ethylene oxide.The nonionic polyhydroxy fatty acid amide surfactant

Be applicable to that polyhydroxy fatty acid amide of the present invention is a formula R ²CONR ¹Those materials of Z, wherein R ¹Be hydrogen, C ₁-C ₄Alkyl, 2-hydroxyethyl, 2-hydroxypropyl, oxyethyl group, propoxy-or their mixture, preferred C ₁-C ₄Alkyl, more preferably C ₁Or C ₂Alkyl, most preferably C ₁Alkyl (being methyl); R ₂Be C ₅-C ₃₁Alkyl, preferred straight chain C ₅-C ₁₉Alkyl or alkenyl, more preferably straight chain C ₉-C ₁₇Alkyl or alkenyl, most preferably straight chain C ₁₁-C ₁₇Alkyl or alkenyl or its mixture; Z has at least three polyhydroxy alkyl or its alkoxy derivatives (preferred ethoxylation or propoxylation) that directly are connected the hydroxyl on the linear hydrocarbyl chain.Z is preferably obtained by reducing sugar in reductive amination process, and more preferably Z is a glycosyl.The nonionic fatty acid amide surfactant

The suitable fatty acids acidamide surfactant comprises having formula: R ⁶CON (R ⁷) ₂Those materials, R wherein ⁶Be to contain 7-21, the alkyl of preferred 9-17 carbon atom, each R ⁷Be selected from hydrogen, C ₁-C ₄Alkyl, C ₁-C ₄Hydroxyalkyl and-(C ₂H ₄O) _xH, wherein x is 1-3.The nonionic alkyl polysaccharide surfactant

Be used for the US4565647 that suitable alkyl polysaccharide of the present invention authorizes Llenado on January 22nd, 1986 and be disclosed, polysaccharide such as many glycosides hydrophilic radical that it contains the hydrophobic grouping of 6-30 carbon atom and contains 1.3-10 sugar unit.

Preferred alkyl polyglycoside has following formula:

R ²O (C _nH _2nO) _t(glycosyl) _x

R wherein ²Be selected from alkyl, alkyl phenyl, hydroxyalkyl, hydroxyalkyl phenyl and their mixture, wherein alkyl contains 10-18 carbon atom; N is 2 or 3; T is 0-10, and x is 1.3-8.Glycosyl is preferably obtained by glucose.Amphoterics

Be applicable to that amphoterics of the present invention comprises amine oxide surfactant and alkyl both sexes carboxylic acid.

Suitable amine oxide comprises having formula R ³(OR ⁴) _xN ⁰(R ⁵) ₂Compound, R wherein ³Be selected from alkyl, hydroxyalkyl, amido propyl group and the alkyl phenyl or their mixture that contain 8-26 carbon atom; R ⁴Be alkylidene group or hydroxy alkylidene or their mixture that contains 2-3 carbon atom; X is 0-5, preferred 0-3; With each R ⁵Be alkyl or the hydroxyalkyl that contains 1-3 carbon atom, or contain the polyethylene oxide group of 1-3 ethylene oxide group.Preferred C ₁₀-C ₁₈Alkyl dimethyl amine oxide and C ₁₀-C _18xAmidoalkyl dimethyl oxidation amine.

The suitable example of alkyl both sexes dicarboxylic ester is by Miranol, Inc., Dayton, Miranol (TM) the C2M Conc. of NJ preparation.Zwitterionics

Zwitterionics also can add in the detergent composition of the present invention.These tensio-active agents can broadly be described as the derivative of derivative, the heterocycle second month in a season and tertiary amine of secondary and tertiary amine or the derivative of quaternary ammonium, quaternary phosphonium or uncle's sulfonium compound.Trimethyl-glycine and sultaine tensio-active agent are the exemplary zwitterionicss of the present invention that is used for.

Suitable trimethyl-glycine is to have formula R (R ¹) ₂N+R ²COO ^-Compound, wherein R is C ₆-C ₁₈Alkyl, each R ¹C normally ₁-C ₃Alkyl and R ²Be C ₁-C ₅Alkyl.Preferred trimethyl-glycine is C _12-18Dimethyl Ammonium hexanoate and C _10-18Amido propane (or ethane) dimethyl (or diethyl) trimethyl-glycine.The beet alkali surface activator of complexing also is applicable among the present invention.Alkaline system

In detergent composition of the present invention, preferably exist alkaline system to obtain best cationic ester surfactant properties.Alkaline system contains the component that alkaline matter can be provided in solution herein.Alkaline matter is meant herein: carbonate, supercarbonate, oxyhydroxide, various silicate anion, percarbonate, perborate, superphosphate, persulphate and persilicate.

When for example being selected from basic metal or alkaline earth metal carbonate, supercarbonate, oxyhydroxide or silicate, comprise crystalline layered silicate, when being dissolved in water, can form this alkaline matter with the basic salt of percarbonate, perborate, superphosphate, persulphate and persilicate and their any mixture.

The example of carbonate is alkaline-earth metal and alkaline carbonate, comprises any mixture of yellow soda ash and concentrated crystal soda and they and calcium carbonate superfine powder, described on November 15th, 1973 disclosed German patent application 2321001.

Suitable silicate comprises SiO ₂: Na ₂The O ratio is 1.0-2.8, preferred 1.6-2.0, most preferably 2.0 water-soluble metasilicate.Silicate can be anhydrous salt or salt hydrate form.SiO ₂: Na ₂The O ratio is that 2.0 water glass is most preferred silicate.

Be used for preferred crystalline layered silicate of the present invention and have following general formula:

NaMSi _xO _2x+1YH ₂O wherein M is sodium or hydrogen, and x is the number of 1.9-4 and the number that y is 0-20.This class crystalline layered sodium silicate is described in EP-A-0164514, and their preparation method is described in DE-A-3417649 and DE-A-3742043.Here, x preferably 2,3 or 4, preferred 2 in the above-mentioned general formula.Most preferred material is δ-Na ₂Si ₂O ₅, obtain with NaSKS-6 by Hoechst AG.The water soluble detergency promoter compound

Detergent composition of the present invention preferably contains the water soluble detergency promoter compound, and its content is generally by composition weight meter 1%-80%, preferred 10%-70%, most preferably 20%-60%.

Suitable water soluble detergency promoter compound comprises water-soluble monomer multi-carboxylate or their sour form, all or the poly carboxylic acid of copolymerization or their salt, and wherein poly carboxylic acid contains any mixture that at least two quilts are no more than carboxylic acid group, borate, phosphoric acid salt or aforementioned substances that two carbon atoms separate.

Carboxylate salt or multi-carboxy acid salt washing agent can be monomer or oligopolymer type, because cost and performance, monomeric multi-carboxylate is normally preferred.

The suitable carboxylate salt that contains a carboxyl comprises the water-soluble salt of lactic acid, glycolic acid and their ether derivant.The multi-carboxylate of containing two carboxyls comprises water-soluble salt and the ether carboxylate and the sulfinyl carboxylate salt of succsinic acid, propanedioic acid, (ethylenedioxy) oxalic acid, toxilic acid, diglycollic acid, tartrate, tartronic acid and fumaric acid.The multi-carboxylate of containing three carboxyls especially comprises water-soluble citrate, itaconate and citraconate and succinate derivative, for example the carboxy methoxy-succinic acid salt of in English Patent 1379241, describing, the newborn acyloxy succinate of in English Patent 1389732, describing and the aminosuccinic acid salt of in Holland's application 7205873, describing and oxygen Quito carboxylate salt material of in English Patent 1387447, describing, 2-oxa--1 for example, 1,3-tricarballylic acid salt.

The multi-carboxylate of containing four carboxyls is included in disclosed oxygen di-succinate, 1,1,2 in the English Patent 1261829,2-ethane tetracarboxylic acid hydrochlorate, 1,1,3,3-propane tetracarboxylic acid salt and 1,1,2,3-propane tetracarboxylic acid salt.Contain the substituent multi-carboxylate of sulfo group be included in English Patent 1398421 and 1398422 and US3936448 in disclosed sulfosuccinate and in English Patent 1439000 disclosed sulfonation pyrolysis Citrate trianion.Preferred multi-carboxylate is that each molecule contains the nearly hydroxycarboxylate of three carboxyls, more preferably Citrate trianion.

The mixture of the parent acid of monomer or oligomerisation multi-carboxylate sequestrant or they and salt, for example citric acid or Citrate trianion/citric acid mixture also can be used as builder component.

The borate washing assistant and contain washing composition store or wash conditions under can to produce the washing assistant that boratory borate forms material be the useful water soluble detergency promoter of the present invention.

The suitable example of water-soluble phosphate washing assistant is tripolyphosphate an alkali metal salt, trisodium phosphate, potassium and ammonium, trisodium phosphate, potassium and ammonium, sodium orthophosphate and potassium, partially poly-/sodium phosphate, and wherein the polymerization degree is the salt of about 6-21 and phytinic acid.

Composition of the present invention contains and is less than 20% phosphate component by weight, preferably is less than 15%, or even less than 10% or 5% phosphate component by weight.Therefore, if phosphate builders exists as phosphate component, preferably lower amount.Be partly dissolved or undissolved washing-aid compound

Detergent composition of the present invention can contain and is partly dissolved or undissolved washing-aid compound, and its content is generally 1%-80% by composition weight meter, preferred 10%-70% by weight, most preferably 20%-60% by weight.

The example that major part is not dissolved in the washing assistant of water comprises sodium silicoaluminate.

Suitable aluminosilicate zeolite has formula N _aZ[(AlO ₂) _z(SiO ₂) _y] .xH ₂The structure cell of O, wherein z and y are at least 6; The mol ratio of z and y is 1.0-0.5, and x is at least 5, preferred 7.5-276, more preferably 10-264.Alumino-silicate materials is a hydrated form, preferably contains 10%-28%, more preferably the crystal of the water of the bonding scheme of 18%-22%.

Aluminosilicate zeolite can be naturally occurring material, but preferably synthetic obtaining.Synthetic crystal aluminosilicate ion exchange material obtains with title zeolite A, zeolite B, zeolite P, X zeolite, zeolite HS, zeolite MAP and their mixture, and zeolite A has following formula:

Na ₁₂[(AlO ₂) ₁₂(SiO ₂) ₁₂] xH ₂O wherein x is 20-30, especially 27.X zeolite has formula: Na ₈₆[(AlO ₂) ₈₆(SiO ₂) ₁₀₆] .276H ₂O.Bleaching catalyst

Composition randomly contains the bleaching catalyst of transition metal.A kind of bleaching catalyst of adequate types is to contain the active heavy metal cation of definite bleaching catalyst, for example copper, iron or manganese positively charged ion, contain less or do not have the active assistant metal positively charged ion of bleaching catalyst, the catalyst system of zinc or aluminium cations and sequestrant, especially ethylenediamine tetraacetic acid (EDTA), ethylenediamine tetraacetic (methylene phosphonic acid) and their water-soluble salt that catalysis and assistant metal positively charged ion are had definite stability constant for example.This catalyzer is disclosed in US4430243.

The bleaching catalyst of other type is included in disclosed manganese basigamy compound among US5246621 and the US5244594.The preferred embodiment 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) ₂, Mn ^IIIMn ^IV ₄(u-O) ₁(u-OAc) ₂-(1,4,7-trimethylammonium-1,4,7-7-triazacyclononane) ₂-(ClO ₄) ₃With their mixture.Other bleaching catalyst is disclosed in the open № .549272 of european patent application.Be applicable to that other ligand of the present invention comprises 1,5,9-trimethylammonium-1,5,9-triazododecane, 2-methyl isophthalic acid, 4,7-7-triazacyclononane, 2-methyl isophthalic acid, 4,7-7-triazacyclononane, 1,2,4,7-tetramethyl--1,4,7-7-triazacyclononane and their mixture.

The example of suitable bleaching catalyst is referring to US4246612 and US5227084.Also referring to US5194416, it discloses monokaryon manganese (IV) title complex, for example Mn (1,4,7-trimethylammonium-1,4,7-7-triazacyclononane) (OCH ₃) ₃-(PF ₆).As disclosed among the US5114606, the bleaching catalyst of another type is the water-soluble complexes of manganese (III) and/or (IV) and ligand, and described ligand is the non-carboxylate salt polyol that contains at least three continuous C-OH groups.The double-core Mn that other example comprises with four-N-dentate and two-N-dentate ligand cooperates comprises N ₄Mn ^III(u-O) ₂Mn ^IVN ₄) ⁺[(2,2 ＇-dipyridyl) ₂Mn ^III(u-O) ₂Mn ^IV(2,2 ＇-dipyridyl) ₂]-(ClO ₄) ₃

Other suitable bleaching catalyst is described in following document, for example EP patent application 408131 (cobalt complex catalyzer), the EP patent application discloses 384503 and 306089 (catalysis of metalloporphyrin agent), US4728455 (manganese/multiple ligand polymerization of olefin using catalyst body catalyst), US4711748 and EP patent application disclose 224952 (being adsorbed on the manganese on the aluminosilicate catalyst), US4601845 (being loaded with the aluminosilicate carrier of manganese and zinc or magnesium salts), US4626373 (manganese/ligand catalyzer), US4119557 (iron complex catalyzer), German patent specification 2054019 (cobalt sequestrant catalyzer), CA866191 (salt that contains transition metal), US4430243 (sequestrant that contains manganese positively charged ion and non-catalytic metallic cation) and US4728455 (managanese gluconate catalyzer).Heavy metal ion chelating agent

Detergent composition of the present invention preferably contains the heavy metal ion chelating agent as optional components.Heavy metal ion chelating agent has been meant the component of sequester (chelating) heavy metal ion effect.These components can also have calcium and magnesium sequestering power, but preferably show in conjunction with heavy metal ion, for example the selectivity of iron, manganese and copper.

Press the composition weight meter heavy metal ion chelating agent usually with 0.005%-20%, preferred 0.1%-10%, more preferably 0.25%-7.5%, most preferably the content of 0.5%-5% exists.

Be used for suitable heavy metal ion chelating agent of the present invention and include organic phosphonates, for example poly-(alkylene phosphonic acids salt), basic metal ethane 1-hydroxyl diphosphonate and nitrilo trimethylene phosphonic salt of amino alkylidenyl.

Preferred above-mentioned substance is diethylenetriamine five (methylene phosphonic acid salt), quadrol three (methylene phosphonic acid salt), hexamethylene-diamine four (methylene phosphonic acid salt) and hydroxy ethylene 1,1 diphosphonate.

Be used for other suitable heavy metal ion chelating agent of the present invention and comprise nitrilotriacetic acid(NTA) and polyaminocarboxylic acid, for example ethylenediamine tetraacetic acid (EDTA), ethylidene pentaacetic acid, ethylenediamine disuccinic acid, quadrol two pentanedioic acids, 2-hydroxyl propylene diamine disuccinic acid or its any salt.Especially preferred quadrol-N, the ammonium salt of N '-disuccinic acid (EDDS) or its basic metal, alkaline-earth metal, ammonium or replacement or their mixture.

Being used for other suitable heavy metal ion chelating agent of the present invention is iminodiacetic acid derivatives, 2-hydroxyethyl oxalic acid of for example describing in EP-A-317542 and EP-A-399133 or glyceryl iminodiethanoic acid.Also can use iminodiethanoic acid-N-2-hydroxypropyl sulfonic acid and the aspartic acid N-carboxyl methyl N-2-hydroxypropyl-3-sulfonic acid sequestrant in EP-A-516102, described.Beta-alanine-the N that in EP-A-509382, describes, N '-oxalic acid, aspartic acid-N, single acetate of N '-oxalic acid, aspartic acid-N-and imino-diacetic succsinic acid sequestrant also are suitable for.

EP-A-476257 has described suitable amino based sequestrant.EP-A-510331 has described and has derived from collagen protein, Keratin sulfate or caseic suitable sequestrant.EP-A-528859 has described suitable alkyl imino oxalic acid sequestrant.Pyridine dicarboxylic acid and 2-phosphono-containing butane-1,2,4-tricarboxylic acid also are suitable.G-NH2-N, N '-disuccinic acid (GADS), quadrol-N-N '-two pentanedioic acid (EDDG) and 2-hydroxyl propylene diamine-N-N '-disuccinic acid (HPDDS) also is suitable.

Enzyme

Another preferred ingredient that is used for detergent composition of the present invention is one or more additional enzymes.

Preferred additional enzyme material comprises commercial available lipase, at, amylase, neutrality and Sumizyme MP, cellulase, endolase, esterase, polygalacturonase, laccase and the peroxidase that is routinely added in the detergent composition.Suitable enzyme comes into question in US3519570 and 3533139.

The proteolytic enzyme that preferred commercially available proteolytic enzyme comprises the proteolytic enzyme sold with trade(brand)name Alcalase, Savinase, Primase, Durazym and Esperase by Novo IndustriesA/S (Denmark), sold with trade(brand)name Maxatase, Maxacal and Maxapem by Gist-Brocades, the proteolytic enzyme of selling by Genencor International and the proteolytic enzyme of selling with trade(brand)name Opticlean and Optimase by Solvay Enzymes.Proteolytic enzyme can be that the content of 0.0001%-4% adds in the composition of the present invention by composition weight meter organized enzyme amount.

Preferably amylase comprises, for example the α-Dian Fenmei that obtains as the special bacterial strain of describing in detail among the GB-1269839 (Novo) from Bacillus licheniformis.Preferred commercial available amylase comprises the amylase of for example being sold with trade(brand)name Termamyl and BAN with trade(brand)name Rapidase sale and NovoIndustries A/S by Gist-Brocades.Amylase can be that the content of 0.0001%-2% adds in the composition of the present invention by composition weight meter organized enzyme amount.

Lipolytic enzyme can be by composition weight meter 0.0001%-2%, preferably 0.001%-1%, the most preferably active lipolytic enzyme content existence of 0.001%-0.5% by weight by weight.

Lipase can be fungi or bacterial origin, for example from detritus enzyme genus, Thermomicrobium or Rhodopseudomonas, comprises that the bacterial strain of the generation lipase of pseudomonas pseudoalcaligenes or Pseudomonas fluorescens obtains.Lipase chemical or that genetically altered mutant obtains by these bacterial strains also can be used among the present invention.Preferred lipase obtains from pseudomonas pseudoalcaligenes, and it is described in the EP-B-0218272 that authorizes.

The gene that obtains from the fetal hair humicola lanuginosa by the clone described in another preferred lipase of the present invention such as the European patent application EP-A-0258068 is also expressed the lipase that this gene obtains as host's aspergillus oryzae, it commercial by Novo Industri A/S, Bagsvaerd, Denmark obtains with trade(brand)name Lipolase.This lipase also is described in authorizing the US4810414 of Huge-Jensen etc. on March 7th, 1989.Organic polymer

Organic polymer is the preferred annexing ingredient in the detergent composition of the present invention, the organic polymer that is suitable for adding in the detergent composition of the present invention comprises derivatived cellulose, for example methylcellulose gum, carboxymethyl cellulose, Vltra tears and hydroxy ethyl cellulose.

In addition, useful organic polymer is a polyoxyethylene glycol, molecular weight 1000-10000 especially, more preferably 2000-8000 and most preferably from about 4000 compound.Press down foam system

Detergent composition of the present invention is when preparation when being used for the machine-washing composition, preferably contains by composition weight meter with 0.01%-15%, and preferred 0.05%-10%, most preferably the content of 0.1%-5% exists presses down foam system.

Being used for the suitable foam that presses down of the present invention is mainly to contain any known defoaming compounds, comprises for example polysiloxane defoaming compounds and 2-alkyl chain triacontanol defoaming compounds.

Defoaming compounds is meant and plays the solution that for example suppresses by detergent composition herein, especially has the mixture that foams under the situation of solution stirring or produce any compound of foamy or compound.

Be used for especially preferred defoaming compounds of the present invention and be the polysiloxane defoaming compounds of any defoaming compounds that comprises the polysiloxane component that defines herein.These polysiloxane defoamers also contain silica component usually.Reach herein at industrial normally used term " polysiloxane " and comprise the various relative high molecular weight polymers that contains siloxane unit and various types of alkyl.Preferred polysiloxane defoamers compound is a siloxanes, especially contains the unitary polydimethylsiloxane of trimethyl silyl end-blocking.

Other suitable defoaming compounds comprises mono carboxylic lipid acid and its soluble salt.These materials are authorized among the US2954347 of Wayne St.John in September 27 nineteen sixty and are described.Mono carboxylic lipid acid and salt thereof as suds suppressor contain 10-24 carbon atom usually, 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.

Other suitable defoaming compounds comprises, for example high molecular fatty ester (for example fatty acid triglyceride), the fatty acid ester of monovalent alcohol, aliphatic C ₁₈-C ₄₀Ketone (for example stearone) N-alkylation aminotriazine, for example as cyanuric chloride and two or three moles contain that the product of the uncle of 1-24 carbon atom or secondary amine forms three-to six-alkyl melamine or two-to the tetraalkyl diammonium chloride for triazine, propylene oxide, distearyl acid acid amides and single stearyl two basic metal (for example sodium, potassium, lithium) phosphoric acid salt and phosphoric acid ester.

The preferred foam system that presses down is contained

(a) defoaming compounds, preferred polysiloxane defoaming compounds, most preferably in conjunction with the polysiloxane defoaming compounds that contains following component:

(ⅰ) by polysiloxane defoaming compounds weight, content is 50%-99%, the polydimethylsiloxane of preferred 75%-95%; With

(ⅱ) by polysiloxane/silicon-dioxide defoaming compounds weight, content is 1%-50%, the silicon-dioxide of preferred 5%-25%;

Wherein said silicon-dioxide/polysiloxane defoaming compounds is with 5%-50% by weight, and the content of preferred 10%-40% adds;

(b) compound dispersing agent, most preferably contain the rake formula multipolymer of silicone glycol, wherein the content of polyoxyalkylene is 72-78%, and the ratio of oxyethane and propylene oxide is 1: 0.9-1: 1.1, its content is 0.5%-10% by weight, preferred 1%-10%; Especially preferred this class silicone glycol rake formula multipolymer is the commercial DC0544 that can obtain with trade(brand)name DC0544 from DOW Corning;

(c) inert support fluid compound, most preferably containing ethoxylation degree is 5-50, the C of preferred 8-15 ₁₆-C ₁₈Ethoxylated alcohol; Its content is 5%-80% by weight, preferred 10%-70%.

Highly preferred granular suds suppressing system is described in EP-A-0210731, it contains polysiloxane defoaming compounds and fusing point is 50 ℃-85 ℃ organic carrier material, and wherein the organic carrier material contains monoglyceride and contains the lipid acid of the carbochain of 12-20 carbon atom.EP-A-0210721 discloses other preferred granular suds suppressing system, and wherein the organic carrier material is that fusing point is 45 ℃-80 ℃ the lipid acid with the carbochain that contains 12-20 carbon atom or alcohol or their mixture.The soft system of clay

Detergent composition can contain the soft system of clay, and it contains clay mineral compound and randomly clay flocculating agent.

The clay mineral compound is the terre verte compound preferably.Terre verte is disclosed in US3862058,3948790,3954632 and 4062647.P ﹠amp; The EP-A-299575 of G company and EP-A-313146 have described suitable organic polymer clay flocculating agent.The polymeric dye transfer inhibitor

Detergent composition of the present invention also contains 0.01%-10% by weight, preferred 0.05%-0.5% polymeric dye transfer inhibitor.

The polymeric dye transfer inhibitor is preferably selected from multipolymer, polyvinylpyrrolidonepolymers polymers or their combination of polyamine N-oxide pllymers, N-vinyl pyrrolidone and N-vinyl imidazole.A) polyamine N-oxide pllymers

Be applicable to that polyamine N-oxide pllymers of the present invention contains the unit with following structural formula:

p(1)?????Ax

R wherein P be polymerisable unit and

A is -S-,-N-; X is 0 or 1; R is aliphatic series, aliphatic, the aromatics of ethoxylation, heterocycle or alicyclic group or its any combination, the part that the nitrogen of N-O group can nitrogen coupled or wherein N-O group is these groups.

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

Wherein R1, R2 and R3 are aliphatic group, aromatics, heterocycle or alicyclic group or their combination, x or/and y or/and z is 0 or 1, the part that the nitrogen of N-O group can be connected with it or wherein the nitrogen of N-O group constitutes these groups wherein.The N-O group can be the part of polymerizable unit (P) or can link to each other or both with polymeric skeleton.

Wherein the suitable polyamine N-oxide of the part of N-O group formation polymerizable unit comprises polyamine N-oxide, and wherein R is selected from aliphatic series, aromatics, alicyclic ring or heterocyclic group.The described polyamine N-oxide of one class comprises one group of polyamine N-oxide, and wherein the nitrogen of N-O group constitutes the part of R-group.Preferred polyamine N-oxide compound is that wherein R is a heterocyclic group, for example those of pyridine, pyrroles, imidazoles, tetramethyleneimine, piperidines, quinoline, acridine and their derivative.

Other suitable polyamine N-oxide is the polyamine oxide compound that is connected with polymerizable unit of N-O group wherein.These polyamine N-oxide of preferred class comprise the polyamine N-oxide with logical formula I, and wherein R is aromatics, heterocycle or alicyclic group, and wherein the nitrogen of N-O functional group is the part of described R group.The example of this compounds is the polyamine oxide compound, and wherein R is a heterogeneous ring compound, for example pyridine, pyrroles, imidazoles and their derivative.

Polyamine N-oxide of the present invention can almost obtain with any polymerization degree.The polymerization degree is not crucial, as long as material has required water-soluble and dye suspension ability.Molecular-weight average is generally 500-1000000.B) its polymers of N-vinyl pyrrolidone and N-vinyl imidazole

Be applicable to that N-vinyl imidazole of the present invention and N-vinyl pyrrolidone polymer have the molecular-weight average of 5000-50000.The N-vinyl imidazole of preferred multipolymer and the mol ratio of N-vinyl pyrrolidone are 1: 0.2.C) Polyvinylpyrolidone (PVP)

Detergent composition of the present invention can also use the Polyvinylpyrolidone (PVP) (" PVP ") of molecular-weight average as 2500-400000.Suitable Polyvinylpyrolidone (PVP) commercial from ISPCorporation, New York, NY and Montreal, Canada is with ProductName PVP K-15 (viscosity molecular weight is 10000), PVP K-30 (molecular-weight average 40000), and PVP K-60 (molecular-weight average 160000) and PVP K-90 (molecular-weight average 360000) obtain.PVP K-15 also can be obtained by ISP Corporation commercial.What other was suitable comprises Sokalan HP 165 and SokalanHP 12 at the commercial Polyvinylpyrolidone (PVP) that obtains from BASFCooperation.D) Ju Yi Xi oxazolidinone

Detergent composition of the present invention also can use Ju Yi Xi oxazolidinone as the polymeric dye transfer inhibitor.Said Ju Yi Xi oxazolidinone has the molecular-weight average of 2500-400000.E) polyvinyl imidazol

Detergent composition of the present invention also can use polyvinyl imidazol as the polymeric dye transfer inhibitor.Described polyvinyl imidazol has the molecular-weight average of 2500-400000.White dyes

Detergent composition of the present invention also can randomly contain the hydrophilic white dyes of about by weight some type of 0.005% to 5%.The hydrophilic white dyes of Shi Yonging has following structural formula in the present invention: R wherein ₁Be selected from anilino, the two hydroxyethyls of N-2-and NH-2-hydroxyethyl; R ₂Be selected from N-2-pair-hydroxyethyl, N-2-hydroxyethyl-N-methylamino, morpholino, chlorine and amino; M is a salt-forming cation, for example sodium or potassium.

When in above-mentioned formula, R ₁Be anilino, R ₂Be N-2-two-hydroxyethyl and M are positively charged ions, for example during sodium, whitening agent is 4,4 '-two [(4-anilino-6-(N-2-two-hydroxyethyl)-s-triazine-2-yl) amino]-2,2 '-stilbene disulfonic acid disodium salt.This special whitening agent material is sold with trade(brand)name Tinopal-UNPA-GX by Ciba-Geigy company commercial.Tinopal-UNPA-GX is the preferred hydrophilic white dyes that is used for detergent composition of the present invention.

When in above-mentioned formula, R ₁Be anilino, R ₂Be that N-2-hydroxyethyl-N-2-methylamino and M are positively charged ions, for example during sodium, 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 special whitening agent material is sold with trade(brand)name Tinopal 5BM-GX by Ciba-Geigy company commercial.

When in above-mentioned formula, R ₁Be anilino, R ₂Be that morpholino and M are positively charged ions, for example during sodium, whitening agent is 4,4 '-two [(4-anilino-6-morpholino-s-triazine-2-yl) amino] 2,2 '-stilbene disulfonic acid sodium salt.This special whitening agent is sold with trade(brand)name Tinopal AMS-GX by Ciba-Geigy company commercial.Cationic fabric softener

Cationic fabric softener also can add in the detergent composition of the present invention.Suitable cationic fabric softener is included in disclosed water-insoluble tertiary amine or two long-chain acid amides materials among GB-A-1514276 and the EP-B-0011340.

Cationic fabric softener is usually with 0.5%-15%, the total content of 1%-5% adding by weight usually by weight.Other optional components

Other optional components that is included in the present composition comprises colorant and filling salt, and sodium sulfate is preferred filling salt.The pH of composition

Measure composition of the present invention in 1% distilled water solution, its pH is preferably at least 8.5, more preferably 9.0-12.5, most preferably 9.5-11.0.The form of composition

Composition of the present invention can adopt various physical form, comprises particle, tablet, bar and liquid form.The especially so-called concentrated granular detergent composition of composition, it is adapted to pass through the distribution device that is placed in the machine roll that dirt fabric load is housed and adds in the washing machine.

Usually, granular detergent composition of the present invention can pass through the whole bag of tricks, comprise do to mix, spraying drying, agglomeration and granulation preparation.

The average particle size particle size of particulate composition component of the present invention should preferably make and be no more than 5% particulate diameter greater than 1.7mm, is no more than 5% particulate diameter less than 0.15mm.

Ding Yi term average particle size particle size is by composition sample is divided into mass part (common 5 parts) at one group of Tyler sieve top sieve herein.The wt part that so obtains is with respect to the aperture curve that draws of sieve, and average particle size particle size is by weight the pore size that 50% sample passes through.

The bulk density of granular detergent composition of the present invention is generally 600g/l at least, more preferably 650g/l-1200g/l.Bulk density is measured by simple funnel and cup device, and described device is made up of the conical funnel that is embossed in rigidly on the pedestal, and vacuum breaker is equipped with in the funnel lower end makes the material in the funnel enter in the cylinder cup of axially aiming at placement under funnel.Funnel is 130 millimeters high, and the internal diameter at two ends is respectively 130 millimeters and 40 millimeters up and down.Funnel is installed like this so that 140 millimeters places on pedestal upper surface, its lower end, the height overall of cup is 90 millimeters, and internal height is 87 millimeters, and internal diameter is 84 millimeters.Its nominal volume is 500 milliliters.

For measuring, in funnel, fill powder with hand, open vacuum breaker, make powder overflow cup.The cup of filling is taken out from framework, and by the instrument with straight flange, for example pocket knife was scraped the cup upper limb and was removed excessive powder.The cup of weighing then and filling obtains bulk density value g/l with 2 with the powder weight that obtains is on duty.Carry out replicate measurement on demand.The surfactant agglomerates particle

Cationic ester tensio-active agent of the present invention preferably with additional surfactant, preferably is present in the particulate composition with the surfactant agglomerates particle form, and agglomerate can adopt sheet, ball, ball, pin and band shape, but preferably takes particle form.The most preferably mode of processing granular is that particle size with high active surfactant slurry agglomerating powder (for example silico-aluminate, carbonate) and the agglomerate that obtains of control is in specified limit.This method is included in the powder that mixes significant quantity in one or more cyclone agglomerators with highly active surfactant paste, cyclone agglomerator comprises for example plate-like cyclone agglomerator, Z-shaped blade stirrer or preferred on-line mixing device, for example by Schugi (Holland) BV, 29 Chroomstraat, 8211 AS, Lelystad, those equipment that Holland makes, with Gebruder Lodige Maschinenbau GmbH, D-4790 Paderborn1, Elsenerstrasse 7-9, Postfach 2050, Germany.Most preferably use high-shear mixer, for example Lodige CB (trade(brand)name).

Usually use and contain 50%-95% by weight, the preferred high active surfactant slurry of the tensio-active agent of 70%-85% by weight.Slurry is can be enough high keeping pumpable viscosity, but enough low with in the temperature pump suction cyclone agglomerator of avoiding used anion surfactant decomposition.Usually the service temperature of slurry is 50 ℃-80 ℃.Clothes washing method

The machine clothes washing method is usually included in the washing machine with containing dissolving or disperseing the machine-wash wash water solution of detergent composition of the present invention of significant quantity wherein to handle dirty fabric among the present invention.The detergent composition of significant quantity is meant under the general product consumption and washing soln volume in being generally used for conventional machine washing method, dissolves or is dispersed in the product that 5-65 rises the 40g-300g in the volume washing soln.

Aspect preferred use, in washing methods, use distribution device.Distribution device is equipped with the washing composition product, is used for directly adding product at the washing machine rotating cylinder before beginning wash(ing)cycle.Its volume capacity can contain enough washing composition products in the time of should making it in being generally used for washing methods.

In case after washing machine is equipped with clothing, the distribution device that the washing composition product is housed is put into rotating cylinder.When begin the wash(ing)cycle of washing machine, in rotating cylinder, add entry, rotating cylinder periodically rotates.The design distribution device make it that dry detergent product is housed but in wash(ing)cycle in response to the stirring action of the rotation of rotating cylinder with owing to discharge these products with contacting of washing water.

Can discharge the washing composition product for making in washing process, device should have the opening that many products can pass through.In addition, device should be by liquid permeable but the material of impermeable solid product make, this can allow to discharge the dissolved product.The washing composition product preferably discharges rapidly when begin wash(ing)cycle, thereby the product of temporary transient high local concentrations was provided in the washing machine rotating cylinder in this stage wash(ing)cycle.

Preferred distribution device is reusable, and design made at dried state and keep the globality of container in wash(ing)cycle.The especially preferred distribution device that is used for the present composition is described in following patent: GB-B-2157717, GB-B-2157718, EP-A-0201376, EP-A-0288345 and EP-A-0288346.At Manufacturing Chemist, in November, 1989, the especially preferred distribution device that is used for the granular laundry product also described in the article of delivering in the 41-46 page or leaf by J.Bland, and it is the type that is commonly referred to " granulette ".Another distribution device that preferably is used for detergent composition of the present invention is disclosed at PCT patent application WO94/11562.

Especially preferred distribution device is disclosed in the open EP0343069 and 0343070 of european patent application.Back one application discloses the device of the rubbing property shell that comprises the bag shape form of extending along sustained ring, and described ring defines a hole, enough products that this hole is suitable for packing in bag a wash(ing)cycle being used for washing methods.Part washing medium is gone in the bag by orifice flow, lysate, and solution outwards flows in the washing medium by the hole subsequently.Sustained ring is equipped with safety guard and runs off to avoid product that wet, undissolved, and this device generally includes with spoke wheel structure formation by the wall of the radially extension of centre strut expansion or the similar structures that its mesospore has spiral form.

Alternatively, distribution device can be rubbing a property container, for example bag or box.Bag can be to apply the fibrous texture of water impervious protecting materials to keep content, and is for example disclosed such in European publication application EP0018678.Alternatively, as disclosed among the European publication application EP0011500,0011501,0011502 and 0011968, it can be made by the synthetic polymeric material that is not dissolved in water, has edge sealing or closure designs with isolated water-bearing media.The enclosed construction that the yew of conventionally form looses contains the edge by water impervious polymeric film, and for example the water-soluble binder of its sealing is placed and made at an edge of the box of polyethylene or polypropylene formation.The packing of composition

The bleaching composition of commercial distribution can be packaged in any suitable containers, comprises the container that is formed by paper, presspaper, plastic material and any suitable veneer sheet.Preferred packing embodiment is described in European application No.94921505.7.

The abbreviation of using among the embodiment

In detergent composition, the component of abbreviation has following implication: LAS: straight chain C ₁₂Sodium alkyl benzene sulfonate TAS: Tallow, beef sodium alkyl sulfate C45AS: C ₁₄-C ₁₅Straight-chain alkyl sulfate C _XYE _ZS: with the C of z moles of ethylene oxide condensation _1X-C _1YBranched-chain alkyl sodium sulfate C45E7: with the C that is mainly of average 7 moles of ethylene oxide condensations _14-15Linear primary

Alcohol C25E3: with the C1 of average 3 moles of ethylene oxide condensations _2-15Branched-chain primary alcohol C25E5: with the C of average 5 moles of ethylene oxide condensations _12-15Branched-chain primary alcohol CEQ I: R ₁COOCH ₂CH ₂N ⁺(CH ₃) ₃, R ₁=C ₁₁-C ₁₃CEQ II: R ₁COOCH ₂CH ₂CH ₂N ⁺(CH ₃) ₃, R ₁=C ₁₁-C ₁₃CEQ III: R ₁COOCH ₂CH ₂N ⁺(CH ₃) ₃(CH ₂CH ₂OH), R ₁=C ₁₁-C ₁₃CEQ IV: R ₁COOCH ₂CH ₂N ⁺(CH ₃CH ₂) ₂(CH ₃), R ₁=C ₁₁-C ₁₃QAS I: R ₂N ⁺(CH ₃) ₂(C ₂H ₄OH), R ₂=C ₁₂-C ₁₄QAS II: R ₂N ⁺(CH ₃) ₂(C ₂H ₄OH), R ₂=C ₈-C ₁₀Soap: the straight chained alkyl that obtains from 80/20 mixture of Tallow, beef and Oleum Cocois

Carboxylic acid sodium TFAA: C ₁₆-C ₁₈Alkyl N-methyl glucose amide TPKFA: C ₁₂-C ₁₄Dial the full cut lipid acid STPP on top: anhydrous sodium tripolyphosphate zeolite A: formula Na ₁₂(AlO ₂SiO ₂) ₁₂.27H ₂The hydrated sodium aluminosilicate of O, elementary

Particle size is 0.1-10 micron NaSKS-6: formula δ-Na ₂Si ₂O ₅The crystalline layered silicate citric acid: Citric Acid, usp, Anhydrous Powder carbonate: particle size is a 200-900 micron anhydrous sodium carbonate supercarbonate: particle size distribution is the anhydrous sodium bicarbonate silicate of 400-1200 micron: amorphous sodium silicate (SiO ₂: Na ₂O ratio=2.0) sodium sulfate: anhydrous slufuric acid na citrate: citrate trisodium dihydrate, activity 86.4%, particle size distribution

Be 425-850 micron MA/AA: 1: 4 toxilic acid/acrylic copolymer, the about 70000CMC of molecular-weight average: Xylo-Mucine proteolytic enzyme: sell with trade(brand)name Savinase by Novo Industries A/S

Proteolytic enzyme, active 4KNPU/gAlcalase: by the proteolytic ferment that Novo Industries A/S sells, activity

3AU/g cellulase: sell with trade(brand)name Carezyme by Novo Industries A/S

Cellulase, active 1000CEVU/g amylase: by Novo Industries A/S with trade(brand)name Termamyl 60T

The amylase of selling, active 60KNU/g lipase: sell with trade(brand)name Lipolase by Novo Industries A/S

Lipase, active 100KLU/gEndolase: endoglucanase (Endoglunase), by Novo Industries

A/S sells, active 3000CEVU/gPB4: formula NaBO ₂.3H ₂O.H ₂O ₂Sodium perborate tetrahydrate PB1: nominal formula NaBO ₂.H ₂O ₂Anhydrous sodium perborate SYNTHETIC OPTICAL WHITNER percarbonate: nominal formula 2Na ₂CO ₃3H ₂O ₂SPC-D NOBS: nonanoly acyloxy benzene sulfonate; sodium-salt form NAC-OBS: (the amino caproyl of nonanoyl) oxygen base benzene sulfonate; sodium-salt form NACA: 6-nonyl amino-6-oxo-caproic acid TAED: tetra acetyl ethylene diamine DTPMP: diethylenetriamine five (methylene phosphonic acid salt), by Meng Shan all with commodity

Name Dequest 2060 sells the photoactivation SYNTHETIC OPTICAL WHITNER: the sulfonation zinc phthalocyanine phthalocyanine whitening agent of usefulness dextrin polymer soluble encapsulate 1: 4,4 '-two (2-sulfo group styryl) biphenyl disodium whitening agent 2: 4,4 '-two (4-phenylamino-6-morpholino-1,3,5-triazines-2-yl) ammonia

Base) stilbene-2:2 '-disulfonic acid disodium HEDP: 1,1-hydroxyl-ethane di 2 ethylhexyl phosphonic acid PVNO: polyvinylpyridine N-oxide compound PVPVI: the multipolymer SRP1 of Polyvinylpyrolidone (PVP) and vinyl imidazole: sulfo group benzene first with ethylene oxide oxygen base and terephthaloyl skeleton

The end capped ester SRP2 of acyl group end group: the short block of diethoxyization poly-(phthalic acid 1,2 propylidene ester)

Multipolymer polysiloxane froth breaking: the polydimethylsiloxane Foam Control with as the siloxanes agent-oxyalkylene copolymers of dispersion agent, described Foam Control and described dispersion agent

Weight ratio is 10: 1-100: 1

In following embodiment, all content are represented with the % by composition weight meter: embodiment 1

Following laundry detergent composition A-F is embodiments of the invention:

	A	B	C	D	E	F
							LAS	8.0	8.0	8.0	8.0	8.0	8.0
C25E3	3.4	3.4	3.4	3.4	3.4	3.4
							CEQⅠ	0.2	0.8	1.0	2.0	1.0	0.7
CEQⅡ	-	0.5	0.5	0.7	2.0	0.8
							QASⅠ	-	-	0.8	-	-	0.8
QASⅡ	0.8	-	-	-	-	-
							Zeolite A	18.1	18.1	18.1	18.1	18.1	18.1
Carbonate	13.0	l3.0	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	9.0	9.0	9.0
NAC?OBS	2.5	1.5	3.0	4.0	3.2	2.2
							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
							Photoactivation SYNTHETIC OPTICAL WHITNER (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
Polysiloxane defoamers	0.5	0.5	0.5	0.5	0.5	0.5
							Moisture/minor component to 100%
							Density, g/l	850	850	850	850	850	850

Embodiment 2

Bulk density is that the following granular laundry detergent compositions G-I of 750g/l is embodiments of the invention.

	G	H	I
				LAS	5.25	5.61	4.76
TAS	1.25	1.86	1.57
				C45AS	-	2.24	3.89
C25AE3S	-	0.76	1.18
				C45E7	3.25	-	5.0
C25E3	-	5.5	-
				CEQ?Ⅱ	0.8	2.0	2.0
CEQ?Ⅲ	0.4	1.0	0.5
				STPP	19.7	-	-
Zeolite A	-	19.5	19.5
				NaSKS-6/ citric acid (79: 21)	-	10.6	10.6
Carbonate	16.1	21.4	21.4
				Supercarbonate	-	2.0	2.0
Silicate	6.8	-	-
				Sodium sulfate	39.8	-	14.3
PB4	5.0	12.7	-
				TAED	0.5	1.6	-
NAC?OBS	1.0	1.2	1.3
				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
				Photoactivation SYNTHETIC OPTICAL WHITNER (ppm)	15ppm	27ppm	27ppm
Whitening agent 1	0.08	0.19	0.19

Whitening agent 2	-	0.04	0.04
				Spices	0.3	0.3	0.3
Polysiloxane defoamers	0.5	2.4	2.4
				A small amount of component/minor component to 100%

Embodiment 3

Following detergent formulation is embodiments of the invention, and wherein J is the phosphorus-containing detergent composition, and K contains the zeolite detergent composition and L is a compact detergent compositions.

	????J	????K	????L
				The blowing powder
????????????????STPP	????19.0	????-	????19.0
				Zeolite A	????-	????24.0	????-
???????????????C45AS	????9.0	????6.0	????13.0
				??????????????CEQ?Ⅰ	????-	????2.0	?????-
??????????????CEQ?Ⅱ	????-	????-	????2.0
				??????????????CEQ?Ⅲ	????2.0	????-	?????-
???????????????MA/AA	????1.5	????1.2	????1.2
				?????????????????LAS	????6.0	????7.8	????11.0
?????????????????TAS	????2.0	?????-	?????-
				Silicate	????7.0	????3.0	????3.0
?????????????????CMC	????1.0	????1.0	????0.5
				Whitening agent 2	????0.2	????0.2	????0.2
Soap	????1.0	????1.0	????1.0
				???????????????DTPMP	????0.4	????0.4	????0.2
Spray
				???????????????C45E7	????2.5	????2.5	????2.0
???????????????C25E3	????2.5	????2.5	????2.0
				Polysiloxane defoamers	????0.3	????0.3	????0.3
Spices	????0.3	????0.3	????0.3
				Dried additive

Carbonate	????6.0	????13.0	????15.0
				?????????????????PB4	????18.0	????18.0	????10
?????????????????PB1	????4.0	????4.0	????0
				?????????????NAC?OBS	????3.0	????4.2	????1.0
The photoactivation SYNTHETIC OPTICAL WHITNER	????0.02	????0.02	????0.02
				Proteolytic enzyme	????1.0	????1.0	????1.0
Lipase	????0.4	????0.4	????0.4
				Amylase	????0.25	????0.30	????0.15
Do and mix sodium sulfate	????3.0	????3.0	????5.0
				Equipoise (moisture and minor component)	????100	????100	????100
Density (g/l)	????630	????670	????670

Embodiment 4 following detergent formulation are embodiments of the invention:

	?????P	?????Q	?????R	?????S
					LAS	????20.0	????6.0	????24.0	???22.0
QASⅠ	????0.7	????1.0	?????-	????0.7
					CEQ?Ⅲ	????0.4	????0.4	????2.2	????1.5
CEQ?Ⅳ	????1.5	????0.4	????1.0	????1.5
					TFAA	?????-	????1.0	????-	?????-
C25E5/C45E7	?????-	????6.5	????-	????0.5
					C45E3S	?????-	????7.5	????-	?????-
STPP	????30.0	????9.0	????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	?????-	?????-
					SRP1	????0.3	????0.2	?????-	????0.1
MA/AA	????1.0	????1.5	????1.0	????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	????-	???-
Photoactivation SYNTHETIC OPTICAL WHITNER (ppm)	???70ppm	???45ppm	????-	??10ppm
					Whitening agent 1	????0.2	????0.2	????0.08	???0.2
PB1	????6.0	????2.0	????-	???-
					NAC?OBS	????2.0	????1.0	????0.9	???3.1
Equipoise (moisture and minor component)	????100	????100	????100	???100

Embodiment 5 following detergent formulation are embodiments of the invention:

	????T	????U	????V
				The blowing powder
??????????CEQ?Ⅱ	????-	????0.4	????1.5
				??????????CEQ?Ⅳ	????0.8	????0.8	????1.5
Zeolite A	????30.0	????22.0	????6.0
				Sodium sulfate	????19.0	????5.0	????7.0
???????????MA/AA	????1.5	????1.5	????1.2
				?????????????LAS	????14.0	????12.0	????22.0
???????????C45AS	????7.0	????7.0	????7.0
				Silicate	????-	????1.0	????5.0
Soap	????-	????-	????2.0
				Whitening agent 1	????0.2	????0.2	????0.2
Carbonate	????8.0	????16.0	????20.0
				Spray
???????????C45E7	????1.0	????1.0	????1.0
				Dried additive
??????PVPVI/PVNO	????0.5	????0.5	????0.5
				Proteolytic enzyme	????1.0	????1.0	????1.0

Lipase	????0.4	????0.4	????0.4
				Amylase	????0.1	????0.1	????0.1
Cellulase	????0.1	????0.1	????0.1
				????????????????????NACA	????3.4	????6.1	????4.5
Sodium sulfate	????-	????6.0	????-
				Equipoise (moisture and minor component)	????100	????100	????100

Embodiment 6 following high-density are embodiments of the invention with the detergent formulation that contains SYNTHETIC OPTICAL WHITNER:

	????W	????X	????Y
				The blowing powder
Zeolite A	????15.0	????15.0	????15.0
				Sodium sulfate	????0.0	????5.0	????0.0
?????????LAS	????3.0	????3.0	????3.0
				?????????QAS	????-	????1.5	????1.5
??????CEQ?Ⅱ	????0.2	????0.5	????2.4
				??????CEQ?Ⅲ	????0.3	????0.9	????-
???????DTPMP	????0.4	????0.4	????0.4
				?????????CMC	????0.4	????0.4	????0.4
???????MA/AA	????1.3	????1.7	????1.7
				Agglomerate
?????????LAS	????5.0	????5.0	????5.0
				?????????TAS	????2.0	????2.0	????1.0
Silicate	????3.0	????3.0	????4.0
				Zeolite A	????8.0	????8.0	????8.0
Carbonate	????8.0	????8.0	????4.0
				Spray
Spices	????0.3	????0.3	????0.3
				???????C45E7	????2.0	????2.0	????2.0
???????C25E3	????2.0	????-	????-

Dried additive
				Citrate trianion	????5.0	????-	????2.0
Supercarbonate	????-	????3.0	????-
				Carbonate	????8.0	????15.0	????10.0
?????????????????NAC?OBS	????6.0	????2.0	????5.0
				????????????????????NACA	????2.0	????1.8	????1.2
?????????????????????PB1	????14.0	????7.0	????10.0
				Polyethylene oxide, MW5000000	????-	????-	????0.2
Wilkinite	????-	????-	????10.0
				Proteolytic enzyme	????1.0	????1.0	????1.0
Lipase	????0.4	????0.4	????0.4
				Amylase	????0.6	????0.6	????0.6
Cellulase	????0.6	????0.6	????0.6
				Polysiloxane defoamers	????5.0	????5.0	????5.0
Dried additive
				Sodium sulfate	????0.0	????3.0	????0.0
Equipoise (moisture and minor component)	????100.0	????100.0	????100.0
				Density (g/l)	????850	????850	????850

Embodiment 7 following high density detergent agent formulations are embodiments of the invention:

	??Z	??AA
			Agglomerate
???????C45AS	??11.0	??14.0
			???????CEQⅢ	??0.6	??1.1
Zeolite A	??15.0	??6.0
			Carbonate	??4.0	??8.0
???????MA/AA	??1.3	??2.0
			?????????CMC	??0.5	??0.5
???????DTPMP	??0.4	??0.4

Spray
			???????????????C25E5	????5.0	????5.0
Spices	????0.5	????0.5
			Dried additive
????????????????HEDP	????0.5	????0.3
			????????????????SKS6	????13.0	????10.0
Citrate trianion	????3.0	????1.0
			?????????????NAC?OBS	????4.1	????6.2
????????????????TAED	????1.6	????1.7
			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
			Polysiloxane defoamers	????5.0	????5.0
Whitening agent 1	????0.2	????0.2
			Whitening agent 2	????0.2	????-
Equipoise (moisture and minor component)	????100	????100
			Density (g/l)	????850	????850

Embodiment 8 following liquid detergent formulas are embodiments of the invention:

	?AB	?AC	?AD	?AE	?AF	?AG	?AH	?AI
									?CEQⅠ	?0.4	?1.0	?0.8	?0.4	?2.0	?2.5	?-	?3.5
?CEQⅡ	?0.6	?1.2	?0.7	?0.4	?1.2	?-	?3.5	?-
									?LAS	?10.0	?13.0	?9.0	?-	?25.0	?-	?-	?-
?C25AS	?4.0	?1.0	?2.0	?10.0	?-	?13.0	?18.0	?15.0
									?C25E3S	?1.0	?-	?-	?3.0	?-	?2.0	?2.0	?4.0
?C25E7	?6.0	?8.0	13.0	?2.5	?-	?-	?4.0	?4.0

TFAA	-	-	-	4.5	?-	?6.0	?8.0	?8.0
									QAS	-	-	-	-	?3.0	?1.0	?-	?-
MA/AA	1.6	1.4	1.0	0.6	?1.2	?0.9	?0.4	?1.4
									TPKFA	2.0	-	13.0	2.0	?-	?15.0	?7.0	?7.0
Vegetable seed lipid acid	-	-	-	5.0	?-	??-	?4.0	?4.0
									Citric acid	2.0	3.0	1.0	1.5	?1.0	?1.0	?1.0	?1.0
Dodecenyl succinic/tetradecene base succsinic acid	12.0	10.0	-	-	?15.0	?-	?-	?-
									Oleic acid	4.0	2.0	1.0	-	?1.0	?-	?-	?-
Ethanol	4.0	4.0	7.0	2.0	?7.0	?2.0	?3.0	?2.0
									1,2 propylene glycol	4.0	4.0	2.0	7.0	?6.0	?8.0	?10.0	?13.0
Monoethanolamine	-	-	-	5.0	?-	?-	?9.0	?9.0
									Trolamine	-	-	8	-	?-	?-	?-	?-
Sodium hydroxide is to pH	8.0	8.0	7.6	?7.7	?8.0	?7.5	?8.0	?8.2
									The ethoxylation tetren	0.5	-	0.5	?0.2	?-	?-	?0.4	?0.3
NAC?OBS	1.0	1.0	0.5	?1.0	?2.0	?1.2	?1.0	?1.6
									NACA	0.7	1.1	1.8	?1.5	?1.9	?2.1	?1.4	?1.0
PB4	2.0	2.6	3.1	?3.0	?3.1	?3.5	?2.9	?2.5
									SRP2	0.3	-	0.3	?0.1	?-	?-	?0.2	?0.1
PVNO	-	-	-	?-	?-	?-	?-	?0.10
									Proteolytic enzyme	0.5	0.5	0.4	?0.25	?-	?0.5	?0.3	?0.6
Alcalase	-	-	-	?-	?1.5	?-	?-	?-
									Lipase	-	0.10	-	?0.01	?-	?-	?0.15	?0.15
Amylase	0.25	0.25	0.6	?0.5	?0.25	?0.9	?0.6	?0.6
									Cellulase	-	-	-	?0.05	?-	?-	?0.15	?0.15
Endolase	-	-	-	?0.10	?-	?-	?0.07	?-
									Boric acid	0.1	0.2	-	?2.0	?1.0	?1.5	?2.5	?2.5
Sodium formiate	-	-	1.0	?-	?-	?-	?-	?-
									Calcium chloride	-	0.015	-	?0.01	?-	?-	?-	?-

Wilkinite	-	?-	?-	?-	?4.0	?4.0	?-	?-
									Suspended clay SD3	-	?-	?-	?-	?0.6	?0.3	?-	?-
Balance material (moisture and minor component)	100	?100	?100	?100	?100	?100	?100	?100

Claims (17)

1. one kind contains the hard acid cationic components and by total detergent composition weight detergent composition of 1.7% hard base polymeric constituent nearly, wherein the ratio of hard acid cationic components and hard base polymeric constituent is 10: 1-1: 3, and composition contains and is less than 20% phosphate component by weight.

2. according to the detergent composition of claim 1, wherein the hard acid cationic components exists to be lower than 1.5% amount.

3. according to the detergent composition of claim 1 or 2, it contains and is no more than 25% sodium sulfate by weight.

4. the detergent composition that requires according to arbitrary aforesaid right, it also contains the bleach precursor compound, and when bleach precursor was hydrophilic bleach precursor, the amount of bleach precursor was by weight at least 1.5% in composition.

5. according to the detergent composition of claim 4, wherein hydrophilic bleach precursor is a tetra acetyl ethylene diamine.

7. according to the detergent composition of arbitrary aforesaid right requirement, it contains and is less than 8% straight chain C by weight ₁₂Sodium alkyl benzene sulfonate.

8. the detergent composition that requires according to arbitrary aforesaid right, wherein the hard base polymeric constituent exists with the content of 0.01%-1.4% by weight.

9. according to the detergent composition of arbitrary aforesaid right requirement, wherein said hard acid cationic components contains quaternary ammonium compound.

10. according to the detergent composition of arbitrary aforesaid right requirement, wherein the hard acid cationic components contains the cats product of following formula:

R ¹R ² _mR ³ _3-mN ⁺A ^-R wherein ¹Expression C _6-24Alkyl or alkenyl or C _6-12Alkaryl, each R ²Represent (C independently _nH _2nO) _xR ⁴Group, wherein n is 1-4, x is 1-14, and R ⁴Expression hydrogen (preferably), methyl or ethyl are at R ² _mMiddle C _nH _2nThe sum of O group is 1-14, each R ³Represent C independently _1-12Alkyl or alkenyl, aryl or C _1-6Alkaryl, m be 1,2 or 3 and A provide electroneutral counter ion.

11. according to the detergent composition of claim 10, wherein R ²Be-CH ₂CH ₂OH, R ³(independently) be C _1-4Alkyl, m are 1 or 2, R ¹It is straight chain C _6-14Alkyl.

12. according to the detergent composition of claim 10, wherein R ²Be-CH ₂CH ₂OH, R ³(independently) be C _1-4Alkyl, m are 1 or 2, R ¹Be C _8-10Alkyl.

13. according to the detergent composition of claim 10 or 11, wherein R ¹Be C _8-10Alkyl.

14. according to the detergent composition that arbitrary aforesaid right requires, wherein polymeric constituent contains side group, it is the alkali harder than the material of following formula:

15. according to the detergent composition that arbitrary aforesaid right requires, wherein the hard base polymeric constituent contains the polymkeric substance of band side group carboxylic acid functional.

16. according to the detergent composition of claim 15, wherein said hard base polymeric constituent contains vinylformic acid, toxilic acid or succsinic acid/salt polymkeric substance.

17. according to the detergent composition that arbitrary aforesaid right requires, the molecular weight of wherein said hard base polymeric constituent is 2000-150000.

18. method of washing clothes in the family expenses washing machine, wherein before washing beginning, will be equipped with significant quantity according to claim 1-17 in each the distribution device of solid detergent composition put into the washing machine rotating cylinder, wherein said distribution device can be released into described detergent composition in the washings in washing process gradually.