CN1361815A

CN1361815A - Dishwashing detergent composition containing mixtures of crystallinity-disrupted surfactants

Info

Publication number: CN1361815A
Application number: CN 99816501
Authority: CN
Inventors: J·J·谢贝尔; K·L·科特; D·S·康诺; T·A·克里佩; P·K·温森; W·M·谢赫珀; C·卡斯图里; J·C·T·R·布尔凯特-圣劳伦特
Original assignee: Procter and Gamble Ltd
Current assignee: Procter and Gamble Ltd; Procter and Gamble Co
Priority date: 1999-01-20
Filing date: 1999-12-15
Publication date: 2002-07-31
Also published as: EP1144573A2; JP2002535441A; CZ20012575A3; WO2000043476A2; BR9916941A; WO2000043476A3

Abstract

A hand dishwashing compositions comprising; a) about 0.1% to about 99.9% by weight of said composition of an alkylarylsulfonate surfactant system comprising from about 10% to about 100% by weight of said surfactant system of two or more crystallinity-disrupted alkylarylsulfonate surfactants of formula (B-Ar-D)a(M<q+>)b wherein D is SO3<->, M is a cation or cation mixture, q is the valence of said cation, a and b are numbers selected such that said composition is electroneutral; Ar is selected from benzene, toluene, and combinations thereof; and B comprises the sum of at least one primary hydrocarbyl moiety containing from 5 to 20 carbon atoms and one or more crystallinity-disrupting moieties, wherein said crystallinity-disrupting moieties interrupt or branch from said hydrocarbyl moiety; and wherein said alkylarylsulfonate surfactant system has crystallinity disruption to the extent that its sodium critical solubility temperature, as measured by the CST Test, is no more than about 40 DEG C; and wherein further said alkylarylsulfonate surfactant system has at least one of the following properties: percentage biodegradation, as measured by the modified SCAS test, that exceeds tetrapropylene benzene sulfonate; and weight ratio of nonquaternary to quaternary carbon atoms in B of at least about 5:1; and b) from about 0.00001% to about 99.9% by weight of said composition of a conventional hand dishwashing adjunct; c) from about 0.01% to about 7% by weight of composition of a divalent ion selected from the group consisting of magnesium, calcium and mixtures thereof.

Description

The dish washing compositions that contains crystallinity-disrupted surfactant mixtures

Invention field

The present invention relates to comprise the dish washing compositions of alkylaryl sulfonate surfactants system, this system contains crystallinity-disrupted, preferred branched, the mixture of isomers of alkylaryl sulfonate surfactants and choosing any one kind of them or the unbroken alkylaryl sulfonate surfactants of multiple crystallinity.

Background of invention

Typical commercial manual dishwashing composition adds divalent ion, and (Mg Ca), thereby has guaranteed suitable grease performance in soft water.Yet bivalent ions existence makes that product and water blended speed reduce (therefore make moment foam poor), rinsing is poor and low-temperature stability is poor in the goods that contain negatively charged ion, nonionic or other tensio-active agent (for example amine oxide, alkylethoxylate, LAS, alkyloyl glucamide, alkyl betaine).And, reduce with pH, because of the sedimentation problem relevant, so be difficult to the stable dish washing detergent that preparation contains Ca/Mg with Ca and Mg.Therefore, the detergent composition that needs a kind of suitable manual dishwashing, it is stable at low temperatures, in addition it in hard water and pH typically be 9 or the lower advantage that can have degrease and clean hard food, and conventional Ca/Mg system is with advantage unstable and that do not have degrease and clean hard food.

Background technology

US5,026,933; US4,990,718; US4,301,316; US4,301,317; US4,855,527; US4,870,038; US2,477,382; EP466,558,1/15/92; EP469,940,2/5/92; FR2,697,246,4/29/94; SU793,972,1/7/81; US2,564,072; US3,196,174; US3,238,249; US3,355,484; US3,442,964; US3,492,364; US4,959,491; WO88/07030,9/25/90; US4,962,256; US5,196,624; US5,196,625; EP364,012B, 2/15/90; US3,312,745; US3,341,614; US3,442,965; US3,674,885; US4,447,664; US4,533,651; US4,587,374; US4,996,386; US5,210,060; US5,510,306; WO95/17961,7/6/95; WO95/18084; US5,510,306; US5,087,788; 4,301,316; 4,301,317; 4,855,527; 4,870,038; 5,026,933; 5,625,105 and 4,973,788.Observed the production of alkyl benzene sulfonate surfactant recently.Referring to " tensio-active agent science (SurfactantScience) " book series the 56th volume, Marcel Dekker, New York, 1996, especially comprise that the 39-108 page or leaf is entitled as the 2nd chapter of " alkylaryl sulfonate: history, manufacturing, analysis and environmental characteristics (Alkylarylsulfonates:History; Manufacture, Analysis andEnvironmental Properties) ", comprising 297 pieces of reference.The full content of these reference is incorporated herein.

The invention summary

Now unexpectedly find, the isomer that comprises the alkylaryl sulfonate surfactants that two or more are crystallinity-disrupted when the alkylaryl sulfonate surfactants system, also optional when containing the unbroken alkylaryl sulfonate surfactants of one or more crystallinity, increase surprisingly than the performance of the alkylaryl sulfonate surfactants that does not contain crystallinity-disrupted alkylaryl sulfonate surfactants isomer.

The present invention mentioned above one or more aspect in many advantages are arranged, include but not limited to: good cold water-soluble, when for example cold water cleans; Good hardness patience; With good washing.And the present invention's expection has the grease greasiness removal of raising.This exploitation makes the production easness of high relatively 2-phenylbenzimidazole sulfonic acid salt composition obtain the raising of quite expection, also improve the preparation easness and the quality of resulting product; And attracting economic advantages have been given.

The present invention is with the unforeseeable basis that is found to be, in old highly branched non-biodegradation alkylbenzene sulfonate and the intermediate range between the novel linear type, there is some alkylbenzene sulfonate, they are better than the latter's performance, and are more biodegradable than the former.

These novel alkylbenzene sulfonates can be by several acquisitions easily in many known alkylbenzene sulfonate production methods.For example, use some dealuminzation mordenite to make their convenient productions.

According to the present invention, provide a kind of novel manual dishwashing composition.This novel manual dishwashing composition comprises:

A) the alkylaryl sulfonate surfactants system of the about 0.1%-of described composition weight meter about 99.9%, this system comprise two or more crystallinity-disrupted following formula alkylaryl sulfonate surfactants of the about 10%-of described surfactant system weight meter about 100%:

(B-Ar-D) a (Mq+) b wherein D be SO ₃ ^-, M is positively charged ion or cation mixt, and q is described cationic valency, and the number of a and b is through selecting, so that described composition is an electric neutrality; Ar is selected from benzene, toluene and combination thereof; B comprises that at least one contains 5-20 carbon atom, preferred 7-16 carbon atom, more preferably 9-15 carbon atom, most preferably the uncle's hydrocarbyl portion of 10-14 carbon atom and the summation of one or more crystallinity-disrupted parts, wherein said crystallinity-disrupted part is interrupted or branch from described hydrocarbyl portion; And the crystallinity-disrupted degree of wherein said alkylaryl sulfonate surfactants system is not higher than about 40 ℃ for its sodium critical solubility temperature by the CST test determination, and wherein said alkylaryl sulfonate surfactants system also has at least one following performance:

Biological degradation percentage ratio by improved SCAS test determination surpasses tetrapropyl benzene sulfonate; With

The weight ratio of non-quaternary carbon atom and quaternary carbon atom is at least about 5: 1 (preferably at least about 10: 1 among the B; More preferably at least about 100: 1); With

B) the conventional manual dishwashing auxiliary agent of the about 99.9wt% of the about 0.00001%-of described composition weight meter;

C) divalent ion that is selected from magnesium, calcium and composition thereof of the about 7wt% of the about 0.01%-of composition weight meter.

Composition preferably contain described composition weight at least about 0.1%, more preferably at least about 0.5%, even more preferably at least about 1% surfactant system.Cleaning combination also preferably contains and is not higher than the about 80% of described composition weight, more preferably no higher than about 60%, even more preferably no higher than about 40% surfactant system.

Surfactant system preferably contain described surfactant system weight at least about 15%, more preferably at least about 30%, even more preferably at least about two or more crystallinity-disrupted alkylaryl sulfonate surfactants of 40%.This surfactant system also preferably contains and is not higher than the about 100% of described surfactant system weight, more preferably no higher than about 90%, even more preferably no higher than two or more crystallinity-disrupted alkylaryl sulfonate surfactants of about 80%.

Therefore, one aspect of the present invention provides novel cleaning combination.By following detailed and additional claims, these and other aspect, feature and advantage will become apparent.

Except as otherwise noted, all per-cents, ratio and the ratio of this paper all are the weight in the component of preparation final composition.Except as otherwise noted, all temperature all be degree centigrade (℃).All documents of quoting as proof in this paper relevant portion are added herein by reference.

Detailed Description Of The Invention

The present invention relates to novel manual dishwashing composition.Component (a) contains the alkylaryl sulfonate surfactants system of the described composition of the about 99.9wt% of the 0.1%-that has an appointment, and this system comprises two or more crystallinity-disrupted following formula alkylaryl sulfonate surfactants of the described surfactant system of the about 100wt% of about 10%-:

(B-Ar-D) a (Mq+) b wherein D be S0 ₃ ^-, M is a positively charged ion or cation mixt.Preferably, M is basic metal, alkaline-earth metal, ammonium, replacement ammonium or its mixture, more preferably sodium, potassium, magnesium, calcium or its mixture.Described cationic valency q is preferably 1 or 2.So that being electroneutral several a and b, described composition is preferably 1 or 2 and 1 respectively.

Ar is preferably selected from benzene, toluene and combination thereof, most preferably benzene.

B comprises uncle's hydrocarbyl portion and the one or more disconnected or branch that at least one contains 5-20 carbon atom; Preferred B had not only comprised the odd number chain length but also had comprised the hydrocarbyl portion of even number chain length.It is the hydrocarbyl portion that preferred B is not limited to all odd numbers or even number chain length.Uncle's hydrocarbyl portion of B has 5-20, preferred 7-16 carbon atom.1-3 crystallinity-disrupted part can be arranged.These crystallinity-disrupted parts are interrupted or branch from described hydrocarbyl portion.When crystallinity-disrupted part was side chain, they were preferably C1-C3 alkyl, C1-C3 alkoxyl group, hydroxyl and composition thereof, more preferably C1-C3 alkyl, C1-C2 alkyl most preferably, even more preferably methyl.When crystallinity-disrupted part was interrupted hydrocarbyl portion, they were preferably ether, sulfone, silicone and composition thereof, more preferably ether.Preferred crystallinity-disrupted alkylaryl sulfonate surfactants comprises two or more homologues." homologue " contained carbonatoms difference in B.This paper back described in detail " isomer " has those compounds of different attachment positions on B particularly including crystallinity-disrupted part.

Also preferred crystallinity-disrupted alkylaryl sulfonate surfactants comprises and is selected from following at least two kinds " isomer ":

I) based on substituting group at the ortho position of the attachment position of Ar-, a position-and contraposition-isomer, when Ar for replacing or during unsubstituted benzene.This means B can and ortho position, a position and the contraposition of D, B can and the Ar except that D on substituting group ortho position, a position and contraposition, D can and the Ar except that B on substituting group ortho position, a position and contraposition, perhaps other possible selection arbitrarily;

Ii) based on the positional isomers of described crystallinity-disrupted part at the attachment position of described uncle's hydrocarbyl portion of B; With

Iii) based on the steric isomer of chiral carbon atom among the B.

More preferably, crystallinity-disrupted alkylaryl sulfonate surfactants will comprise at least two types of isomer ii), most preferably at least four types of isomer ii).

Preferred described surfactant system weight at least about 60%, more preferably from about 70% or above or most preferably from about 80% or above described crystallinity-disrupted alkylaryl sulfonate surfactants be isomeric forms, wherein Ar attached to the described uncle hydrocarbyl portion of B first, on second or the 3rd carbon atom.

The optional components of the present composition is the unbroken following formula alkylaryl sulfonate surfactants of one or more crystallinity of about 0%-about 85% of surfactant system weight:

(L-Ar-D) a (Mq+) b wherein D, M, q, a, b, Ar definition as above.L is the linear primary hydrocarbyl portion that contains 5-20 carbon atom.Preferred L is the straight-chain alkyl part of 7-16 carbon atom.

The crystallinity-disrupted degree of alkylaryl sulfonate surfactants system preferably is not higher than about 20 ℃ for its sodium critical solubility temperature (there is definition this paper back) by the CST test determination is not higher than about 40 ℃, most preferably is not higher than about 5 ℃.Also preferred its calcium critical solubility temperature by the CST test determination is lower than about 80 ℃, preferably is not higher than about 40 ℃, more preferably no higher than about 20 ℃.

The alkylaryl sulfonate surfactants system also has at least one following performance:

A) the biological degradation percentage ratio of measuring by improved SCAS test (explanation is arranged below this paper) surpasses tetrapropyl benzene sulfonate; Or

B) weight ratio of non-quaternary carbon atom and quaternary carbon atom is at least about 5: 1 among the B.The weight ratio of non-quaternary carbon atom and quaternary carbon atom is at least about 10: 1 among the preferred B; More preferably at least about 20: 1, most preferably at least about 100: 1.

More preferably, the absolute value of the biological degradation percentage ratio by improved SCAS test determination is preferably at least about 60%, and more preferably at least 70%, even more preferably at least 80%, most preferably at least 90%.

Manual dishwashing composition of the present invention also comprises b) the conventional manual dishwashing auxiliary agent of the described composition of the about 99.9wt% of about 0.00001%-; And c) divalent ion that is selected from magnesium, calcium and composition thereof of the about 7wt% composition of about 0.01%-.Describe these materials and optional other material useful below in detail to this paper.

As for the using method of composition of the present invention, for example have dirty tableware that needs are cleaned with or the method that contacts of the aqueous solution of pure composition or composition.These methods can randomly comprise the step of water with the composition dilution.And, can be pure or the aqueous solution directly said composition is applied on the tableware or surface to be cleaned, perhaps be coated directly onto on cleaning means such as sponge or the scrubbing cloth.These methods are a part of the present invention.Crystallinity-disrupted

Term " crystallinity-disrupted " meaning of this paper definition is that the indication tensio-active agent is the tensio-active agent that contains a kind of hydrophobic part: this hydrophobic part is through selecting to form following tensio-active agent, and it is the formula CH that length or chain length scope can be compared with described tensio-active agent with hydrophobic part ₃(CH ₂) _n-the reference table surface-active agent of pure linear alkyl chain compare, the former tensio-active agent wraps in the lattice with poor efficiency.

In general, crystallinity-disrupted can flowing from any several modifications of tensio-active agent by molecular level.Especially linear hydrophobic part for example

Be CH ₃(CH ₂) ₁₁-, itself be " crystallinity is unbroken ",, as follows according to the present invention by different piece such as ether moiety, silicone or sulfone are inserted in the chain, its modification can be formed crystallinity-disrupted structure:

More preferably, the crystallinity-disrupted, as follows of this paper taken place in the time will adding the structure from one or more branches of B:

Just have formula (B-Ar-D) a (Mq+) b and (L-Ar-D) with regard to this paper tensio-active agent of a (Mq+) b, it should be noted that the crystallinity-disrupted hydrophobic part of B representative representative, and L represents the unbroken hydrophobic part of crystallinity.Equally, in two kinds of terms, crystallinity-disrupted hydrophobic part B comprises the major portion of being made up of following: (i) all parts among the B except that crystallinity is destroyed part; (ii) crystallinity-disrupted part.

In a preferred embodiment, the part that B has (i) 7-16 carbon atom with (ii) be selected from following crystallinity-disrupted part: (a) side chain that links to each other with B (or " side chain "), it can change in general, but is preferably selected from C ₁-C ₃Alkyl, hydroxyl and composition thereof, more preferably C ₁-C ₃Alkyl, most preferably C ₁-C ₂Alkyl, even more preferably methyl; (b) part of interruption B structure is selected from ether, sulfone, silicone; (c) its mixture.This paper is not that preferred other crystallinity-disrupted part comprises alkene.The alkylaryl sulfonate surfactants system

The main ingredient of manual dishwashing composition of the present invention is the alkylaryl sulfonate surfactants system.This alkylaryl sulfonate surfactants system comprises main crystallinity-disrupted component.

The present invention relates to contain at least two or more these crystallinity-disrupted alkylaryl sulfonate surfactants and optional cleaning combination that contains the unbroken alkylaryl sulfonate surfactants of one or more crystallinity.These two kinds of components are described below: the alkylaryl sulfonate surfactants that (1) is crystallinity-disrupted:

Manual dishwashing composition of the present invention comprises an alkylaryl sulfonate surfactants system, and it contains at least that two or more have the crystallinity-disrupted alkylaryl sulfonate surfactants of following formula:

(B-Ar-D) a (Mq+) b definition and this paper front identical of D, B, M, q, a, b, Ar wherein.Possible crystallinity-disrupted alkylaryl sulfonate surfactants comprises:

Structure (a)-(o) has only been described some possible crystallinity-disrupted alkylaryl sulfonate surfactants, does not plan its restriction scope of the invention.

Also preferred crystallinity-disrupted alkylaryl sulfonate surfactants comprises that at least two kinds are selected from following isomer:

I) based on substituting group at the ortho position of the attachment position of Ar-, a position-and contraposition-isomer, when Ar for replacing or during unsubstituted benzene.This means B can and D ortho position, a position and contraposition, B can and the Ar except that D on substituting group ortho position, a position and contraposition, D can and the Ar except that B on substituting group ortho position, a position and contraposition, perhaps arbitrarily other possible selection;

Iii) based on the steric isomer of chiral carbon atom among the B.

Type (ii) 2 examples of isomer is a structure (a) and (c).Its difference is methyl in (a) attached to the 5th position, and (c) methyl attached to the 7th position.

2 examples of type (i) isomer are structure (1) and (n).Its difference is the sulfonic acid position between group and hydrocarbyl portion very in (1), but in (n) sulfonate radical and hydrocarbyl portion ortho position.

Type (iii) 2 examples of isomer is a structure (c) and (d).Its difference is that these isomer are steric isomer.Chiral carbon is the 7th carbon atom of hydrocarbyl portion.(2) the unbroken alkylaryl sulfonate surfactants of crystallinity:

Manual dishwashing composition of the present invention can also be chosen wantonly and comprise an alkylaryl sulfonate surfactants system, and it can contain the unbroken alkylaryl sulfonate surfactants of one or more crystallinity with following formula:

(L-Ar-D) a (Mq+) b definition and this paper front identical of D, M, L, q, a, b, Ar wherein.The unbroken alkylaryl sulfonate surfactants of possible crystallinity comprises the normal linearity alkylbenzene sulfonate, and for example those of commercially available acquisition as so-called high 2-phenyl linear alkyl benzene sulfonate, are known as DETAL or conventional LAS.Can obtain from Huntsman or Vista.These linear alkyl arylsulphonates can be added in these crystallinity-disrupted alkylaryl sulfonate surfactants, thereby the alkylaryl sulfonate surfactants that uses in the cleaning combination of the present invention system is provided.Perhaps, may since before the reaction, during or therefore isomerization afterwards, unbroken alkylaryl sulfonate surfactants of production crystallinity and crystallinity-disrupted alkylaryl sulfonate surfactants in same reaction.The unbroken alkylaryl sulphonate of crystallinity depends on used catalyzer with the ratio of crystallinity-disrupted alkylaryl sulphonate.No matter use which kind of catalyzer, this surfactant system must have be no more than about 40 ℃ sodium critical solubility temperature and or the biological degradation percentage ratio by improved SCAS test determination surpass tetrapropyl benzene sulfonate, be preferably greater than 60%, more preferably greater than 80%, perhaps the weight ratio of non-quaternary carbon atom and quaternary carbon atom was at least about 5: 1 among the B.

Embodiment 1

Prepare through the skeletal isomerization linear alpha-olefin

Crystallinity-disrupted surfactant system step (a): the linearity (by being pre-formed) that reduces alkene to small part to the olefin skeletal isomerization of the chain length that is applicable to the cleaning products decontamination

With the mixture (for example can obtain) of 1-decene, 1-undecylene, 1-dodecylene and 1-tridecylene from Chevron with weight ratio 1: 2: 2: 1 at 220 ℃ and any suitable LHSV as 1.0 times by a Pt-SAPO catalyzer.With US5, the mode of 082,956 embodiment prepares this catalyzer.Referring to WO95/21225, for example embodiment 1 and specification sheets.This product is fit to the slight branched olefin that the preparation human consumer mixes the skeletal isomerization of the alkyl benzene sulfonate surfactant that cleaning combination uses for the chain length scope.The more conventional temperature of this step can be about 200 ℃-Yue 400 ℃, preferred about 230 ℃-Yue 320 ℃.Pressure typically is the about 2000psig of about 15 psig-, the about 1000psig of preferably about 15psig-, the more preferably from about about 600psig of 15psig-.Hydrogen is useful supercharging gas.Space velocity (LHSV or WHSV) is suitably about 0.05-about 20.Low and the space velocity hourly of pressure is low will to improve selectivity, isomerization is more and cracking still less.To remove the boiling volatile matter up to 40 ℃/10mmHg distillation.Step (b): use the product alkylation of aromatic hydrocarbon with step (a)

In a glass pressure kettle sleeve pipe, add the slight branching of producing in the step (a) of 1 molar equivalent alkene mixture, 20 molar equivalents benzene and in shape selective zeolite catalyst (the acidic mordenite catalyst Zeocat of alkene mixture 20wt% ^TMFM-8/25H).This glass bushing is enclosed in stainless steel to be shaken in the pressure kettle.Use 250psig N ₂This pressure kettle is purged twice, add 1000psig N then ₂While stirring with this mixture heating up to 170-190 ℃, continue 14-15 hour, then with its cooling and from pressure kettle, take out.Reaction mixture is removed by filter catalyzer and concentrated by unreacted raw material and/or impurity (for example benzene, alkene, paraffin, trace material reclaim useful material if necessary) are evaporated, thereby obtain the approximate colourless product liquid of clarification.Then this product is formed required crystallinity-disrupted surfactant system,, the shipment of this system can be transported to remote processing units, can finish sulfonation therein and join other step in human consumer's cleaning combination as a kind of selection.Step (c): with the product sulfonation of step (b)

Use methylene dichloride as the solvent product sulfonation of equivalent chlorsulfonic acid with step (b).Methylene dichloride is distilled.Step (d): the product of neutralization procedure (c)

Product with the sodium methylate neutralization procedure (c) in the methyl alcohol evaporates methyl alcohol, obtains a crystallinity-disrupted surfactant system.

Embodiment 2

The linear alpha-olefin preparation of process skeletal isomerization

Crystallinity-disrupted surfactant system

Repeat the step of embodiment 1, just sulfonation procedure (c) uses sulphur trioxide (not having dichloromethane solvent) as sulphonating agent.At the US3 of Chemithon, provide in 427,342 and used suitable air/sulfur trioxide mixture sulfonated details.And step (d) uses sodium hydroxide to replace the sodium methylate neutralization.

Embodiment 3

Prepare through the skeletal isomerization linear alpha-olefin

Crystallinity-disrupted surfactant system step (a): the linearity that reduces alkene to small part

Mixture with C11, C12 and C13 monoolefine under 430 ℃ passes through the H-ferrierite catalyzer with weight ratio at 1: 3: 1.Can be with US5, method and catalyzer in 510,306 are used for this step.To remove the boiling volatile matter up to 40 ℃/10mmHg distillation.Step (b): use the product alkylation of aromatic hydrocarbon with step (a)

In a glass pressure kettle sleeve pipe, add 1 molar equivalent step (a) slight branching alkene mixture, 20 molar equivalents benzene and in shape selective zeolite catalyst (the acidic mordenite catalyst Zeocat of alkene mixture 20wt% ^TMFM-8/25H).This glass bushing is enclosed in stainless steel to be shaken in the pressure kettle.Use 250psig N ₂This pressure kettle is purged twice, add 1000psig N then ₂A whole night while stirring with this mixture heating up to 170-190 ℃, continue 14-15 hour, then with its cooling and from pressure kettle, take out.Reaction mixture is removed by filter catalyzer.Benzene distillation is reclaimed, also remove volatile impunty.Obtain the colourless or approximate colourless product liquid of a clarification.Step (c): with the product sulfonation of step (b)

Embodiment 4

Prepare through the skeletal isomerization fossil waxes

Crystallinity-disrupted surfactant system step (ai)

At the hydrogen of about 300-340 ℃ temperature, 1000psig, per hour weight-space velocity and the 30mol H of 2-3 ₂Under/mol the hydrocarbon on Pt-SAPO-11 with n-undecane, n-dodecane, n-tridecane 1: 3: the mixture isomerization of 1wt, transformation efficiency surpasses 90%.This isomerization is given at Microporous Materials in detail by S.J.Miller, the 2nd volume, and (1994) are among the 439-449.In other embodiment, linear starting paraffin mixture can be with used identical during conventional LAB produces.To remove the boiling volatile matter up to 40 ℃/10mmHg distillation.(a ii) for step

Use the paraffin dehydrogenation of ordinary method with step (ai).For example referring to US5,012,021,4/30/91 or US3,562,797,2/9/71.Suitable dehydrogenation catalyst is US3, disclosed any catalyzer in 274,287,3,315,007,3,315,008,3,745,112,4,430,517 and 3,562,797.For the purpose of present embodiment,, carry out dehydrogenation in 562,797 according to US3.Catalyzer is zeolite A.At aerobic (paraffin: dioxygen 1: in vapor phase, carry out dehydrogenation under situation 1mol).Temperature is 450 ℃-550 ℃.The gram number of catalyzer hourly is 3.9 with the ratio of total mole number that feeds in raw material.Step (b): use the product alkylation of aromatic hydrocarbon with step (a)

In a glass pressure kettle sleeve pipe, add the step (a) of 1 molar equivalent mixture, 5 molar equivalents benzene and in shape selective zeolite catalyst (the acidic mordenite catalyst Zeocat of alkene mixture 20wt% ^TMFM-8/25H).This glass bushing is enclosed in stainless steel shakes the pressure kettle still.Use 250psig N ₂This autoclave is purged twice, add 1000psig N then ₂A whole night while stirring with this mixture heating up to 170-190 ℃, continue 14-15 hour, then with its cooling and from pressure kettle, take out.Reaction mixture is removed by filter catalyzer.Benzene and any unreacted paraffin distillation are reclaimed.Obtain the colourless or approximate colourless product liquid of a clarification.Step (c): with the product sulfonation of step (b)

Use sulphur trioxide/air and do not use the product sulfonation of solvent step (b).Referring to US3,427,342.The mol ratio of sulphur trioxide and alkylbenzene is about 1.05: about 1.15: 1 of 1-.Separate with the reaction stream cooling and with the residue sulphur trioxide.Step (d): the product of neutralization procedure (c)

With of the product neutralization of excessive a little sodium hydroxide, obtain a crystallinity-disrupted surfactant system with step (c).

Embodiment 5

Through what react from Ge Liya (Grignard)

The crystallinity-disrupted surfactant system of specific tertiary alcohol preparation

The mixture for preparing 5-methyl-5-undecyl alcohol, 6-methyl-6-lauryl alcohol and 7-methyl-7-tridecanol through following Grignard reaction.The mixture that adds 28g methyl-n-butyl ketone, 28g2-heptanone, 14g methyln-hexyl ketone and 100g diethyl ether to a feed hopper.In 1.75 hours, this alcohol/ketone mixtures is added drop-wise in the stirring three neck round-bottomed flasks of nitrogen covering then, is equipped with reflux exchanger and contains bromination hexyl magnesium and the other 100mL diethyl ether of 350mL 2.0M in diethyl ether.Add after the end, under 20 ℃, reaction mixture was stirred other 1 hour.While stirring this reaction mixture is added in the mixture of ice and water of 600g then.30% sulphuric acid soln that in this mixture, adds 228.6g.Two liquid phases of gained are added in the separating funnel.Bleed off the waterbearing stratum, remaining ether layer washes 2 times with 600mL water.Under vacuum, this ether layer is evaporated then, obtain the required alcohol mixture of 115.45g.With this faint yellow alcohol mixture sample of 100g and 300mL benzene and 20g shape selective zeolite catalyst (acidic mordenite catalyst Zeocat ^TMFM-8/25H) join together in the glass pressure kettle sleeve pipe.This glass bushing is enclosed in stainless steel to be shaken in the pressure kettle.Use 250psig N ₂This autoclave is purged twice, add 1000psig N then ₂Continue 14-15 hour while stirring with this mixture heating up to 170 ℃ a whole night, then with its cooling and take out from autoclave.Reaction mixture is removed by filter catalyzer.By distilling benzene it is concentrated, the benzene drying also reclaims.Obtain the colourless or approximate colourless slight branched olefin mixture of a clarification.

With slight branched olefin mixture and 150mL benzene and 10g shape selective zeolite catalyst (the acidic mordenite catalyst Zeocat of 50g by top Ge Liya alcohol mixture dehydration is provided ^TMFM-8/25H) join together in the glass pressure kettle sleeve pipe.This glass bushing is enclosed in stainless steel to be shaken in the autoclave.Use 250psig N ₂This autoclave is purged twice, add 1000psig N then ₂Continue 14-15 hour while stirring with this mixture heating up to 195 ℃ a whole night, then with its cooling and take out from pressure kettle.Reaction mixture is removed by filter catalyzer.By distilling benzene it is concentrated, the benzene drying also reclaims.Obtain the colourless or approximate colourless slight branched olefin mixture of a clarification.Down with this product distillation, keep 95 ℃-135 ℃ fraction in vacuum (1-5mm Hg).

The fraction that keeps is promptly clarified colourless or approximate colourless product liquid, uses the SO 3 sulfonated of 1 molar equivalent then, and products therefrom evaporates methyl alcohol with the neutralization of the sodium methylate in the methyl alcohol, obtains a crystallinity-disrupted surfactant system.Critical solubility temperature test, or CST test

This critical solubility temperature test is a critical solubility temperature of measuring surfactant system.When briefly, this critical solubility temperature increases suddenly or remarkably for measuring solubleness the temperature of surfactant system.Along with wash temperature nowadays trends towards more and more lowlyer, this temperature becomes more and more important.Find that unexpectedly the critical solubility temperature of alkylaryl sulfonate surfactants system of the present invention can reduce by the quantity and the type of the crystallinity-disrupted alkylaryl sulfonate surfactants that exists in the alkylaryl sulfonate surfactants system.

Measure this critical solubility temperature in the following manner:

All used glasswares are cleaned and thorough drying.Use the stdn mercurythermometer to measure all temperature.Specimen in use weight is based on the anhydrous form of solid surfactant or tensio-active agent.

A) the sodium critical solubility temperature-99g deionized water is weighed into be equipped with in the clean dry beaker of magnetic stirring apparatus.Then this beaker is put into an ice-water bath, up to deionized water being cooled to 0 ℃.Add the tensio-active agent of 1.0g sodium critical solubility temperature to be determined or the solid sodium salt sample of surfactant mixture then.With the inhomogeneous solution stirring of gained 1 hour.If surfactant samples was dissolved in 1 hour under without any the situation of heating, obtain the uniform solution of a clarification, so its sodium critical solubility temperature is recorded as≤0 ℃.Do not become clarifying homogeneous solution if surfactant samples was not dissolved in 1 hour, so under agitation should slowly heat by inhomogeneous solution with 0.1 ℃/minute speed.The thermograph that the surfactant samples dissolving obtains a clarifying homogeneous solution is its sodium critical solubility temperature.

B) the calcium critical solubility temperature-99g deionized water is weighed into be equipped with in the clean dry beaker of magnetic stirring apparatus.Then this beaker is put into an ice-water bath, up to deionized water being cooled to 0 ℃.Add the tensio-active agent of 1.0g calcium critical solubility temperature to be determined or the solid calcium salt sample of surfactant mixture then.With the inhomogeneous solution stirring of gained 1 hour.If surfactant samples was dissolved in 1 hour under without any the situation of heating, obtain the uniform solution of a clarification, so its calcium critical solubility temperature is recorded as≤0 ℃.Do not become clarifying homogeneous solution if surfactant samples was not dissolved in 1 hour, so under agitation should slowly heat by inhomogeneous solution with 0.1 ℃/minute speed.The thermograph that the surfactant samples dissolving obtains a clarifying homogeneous solution is its calcium critical solubility temperature.

The surfactant mixture sodium salt of this paper is the most common form that tensio-active agent uses.Known to the simple substitute effect, for example in dilute solution or the help by suitable organic solvent change into calcium salt.Improved SCAS test

This method is suitable for estimating initial biodegradable SDA Soap and Detergent Association (Soap and Detergent Association) semicontinuous activated mud (SCAS) step of alkylbenzene sulfonate.The microorganism long-time (possible some months) that this method relates to chemical substance and relative high density contacts.During this period microorganism is maintained vigour by adding the dirty feed of fixed every day.This improved test also is to be used for the standard OECD of intrinsic biodegradability test or 302A.This is tested on April 12nd, 1981 and is adopted by OECD.The details of " not improved " SCAS can be at " the biodegradability method for measuring and the standard that are used for alkylbenzene sulfonate and linear alkylate sulfonate " (A procedure and Standards forthe Determination of the Biodegradability of Alkyl BenzeneSulphonate and Linear Alkylate Sulphonate), Journal ofthe Ametican Oil Chemists ' Society, 42 volumes find in 986 pages (1965).

With the presentation of results that this testing surface promoting agent or surfactant system obtain, it has high biological degradation potential, and it can be used as intrinsic biodegradability mensuration most for this reason.

Disclosed identical in used ventilation plant and " not improved " SCAS test.That is, 30 ° of a plexi-glass tubular 83mm (31/4 inch) I.D. (internal diameter) steeple lower ends from vertical line to bottom 13mm (1/2 inch) hemisphere.25.4mm on the junction of vertical line and conical wall (1 inch) is positioned at the bottom of 25.4mm (1 inch) diameter opening, is used to insert air delivery pipe.Ventilating chamber's length overall should be 600mm (24 inches) at least.Optional discharge orifice can be positioned at the 500ml level, is convenient to sampling.Holding device is to atmosphere opening.Supply air to ventilation plant from small scale experiments chamber air compressor.Air passes through glass wool or other appropriate medium filtration arbitrarily, thereby removes crude removal, wet goods.Air is also used the water presaturation, to reduce the vaporization losses from this device.Air is with 500ml/min (1ft ³/ hour) speed is carried.Air is carried through a 8mm O.D. (external diameter), 2mm I.D. kapillary.Capillary end is positioned at from bottom, ventilating chamber 7mm (1/4 inch).

Improved SCAS test-ventilation plant is cleaned and is fixed in the suitable support.This step is carried out under 25 ℃+3 ℃.The stock liquid of formation determination tensio-active agent or surfactant system: required concentration is 400mg/l usually, and organic carbon is not taking place to have mensuration tensio-active agent or the surfactant system concentration of 20mg/l when biodegradable each biological degradation circulation begins usually.

Acquisition is from the mixed solution sample of the activated sludge factory of main processing domestic sewage.Each ventilation plant is equipped with the 150ml mixed solution and begins and ventilates.After 23 hours, stop to ventilate, this rubbish was staticly settled 45 minutes.Extract the 100ml supernatant liquor.At any time obtain through sedimentary domestic sewage sample before use, and 100ml is added in the sewage that is retained in each ventilation plant.Restart to ventilate.Do not adding this period of measuring material, only add domestic sewage every day in this device, obtains clarifying supernatant liquor up to precipitation.This is 2 weeks of cost usually, so far when each ventilation loop ends in the supernatant liquor dissolved organic carbon should be lower than 12mg/l.

When this stage finishes, each sedimentary mud is mixed, and 50ml gained combination mud is added in each device.

The sewage that 100ml was precipitated is added in the ventilation plant of comparison device.The mensuration tensio-active agent that sewage that 95ml was precipitated and 5ml are suitable or the stock liquid (400mg/l) of surfactant system are added in the ventilation plant of comparison device.Begin again to ventilate and continue 23 hours.Made sludge settling then 45 minutes, and extracted supernatant liquor out and analyze the dissolved organic carbon content.Use SHIMADZU Model TOC-5000 TOC analyser to analyze this carbon content (D.O.C.).Repeat this filling and extraction step every day in whole mensuration.Before precipitation, may need the wall of washing unit, to prevent that solids accumulation is on liquid level.Each device uses independent scraper or brush, to prevent crossed contamination.

Although allow more not frequent analysis, measure dissolved organic carbon in the supernatant liquor ideally every day.Before the analysis, filter also centrifugal by the 0.45 micron film filter that cleaned supernatant liquor.Sample temperature scarcely will be above 40 ℃ when it is centrifugal.

Draw the dissolved organic carbon result graph of a relation in time of measuring supernatant liquor in ventilation plant and the contrast ventilation plant.That finds in level of finding in measuring ventilation plant when biological degradation finishes and the contrast ventilation plant is approaching.In case when finding that the difference of two levels in 3 METHOD FOR CONTINUOUS DETERMINATION is constant, measure again 3 times, calculate the biological degradation percentage ratio of measuring tensio-active agent or surfactant system by equation: Wherein

O _T=when beginning to ventilate as adding the Method for Measuring Organic Carbon tensio-active agent in the sewage that precipitated or the concentration of surfactant system to

O ₁=when aeration structure, measure the concentration of the dissolved organic carbon of finding in the supernatant liquor of ventilation plant

O _c=the concentration of the dissolved organic carbon found in the supernatant liquor of contrast ventilation plant

Therefore its biological degradation level is to remove the percentage ratio of organic carbon.

This improvement test provides tetrapropyl benzene sulfonate (" TPBS "; Referring to " Surfactant Science Series ", 56 volumes, Marcel Dekker, N.Y., 1996,43 pages) following data (as be used for the 7th page of report of the standard OECD test of intrinsic biodegradability, perhaps 302A): measure tensio-active agent or O _TO ₁-O _cBiological degradation percentage table surfactant system (mg/l) (mg/l)

TPBS?????????????17.3???????8.4?????????????51.4

Many variations of this manual dishwashing composition are useful.These variations comprise:

● contain the manual dishwashing composition of industrial highly branched alkyl benzene sulfonate surfactant (for example TPBS or tetrapropyl benzene sulfonate), its amount is at least about 0.1%, preferably be no more than about 10%, more preferably no more than about 5%, even more preferably no more than about 1%;

● contain the manual dishwashing composition of nonionogenic tenside, its amount is about 25% for about 0.5%-of described detergent composition weight, and wherein said nonionogenic tenside is the poly-alkoxyl alcohol with following end-blocking or non-end-blocking form :-be selected from following hydrophobic grouping: straight chain C ₁₀-C ₁₆Alkyl, medium chain C ₁-C ₃Branching C ₁₀-C ₁₆Alkyl, Guerbet branching C ₁₀-C ₁₆Alkyl and composition thereof; With-being selected from following hydrophilic radical: 1-15 ethoxylate, 1-15 propoxylated glycerine, 1-15 butoxy thing and composition thereof are end-blocking or non-end-blocking form.(when being non-end-blocking form, also have a terminal primary hydroxylic moiety, when be the end-blocking form, the terminal portions of the same form-OR in addition, wherein R is C ₁-C ₆Hydrocarbyl portion, the optional uncle's alkyl that comprises preferably is secondary alcohol when existing);

● contain the manual dishwashing composition of alkyl sulfate surfactant; Its amount is about 25% for about 0.5%-of described detergent composition weight, and wherein said alkyl sulfate surfactant has one and is selected from following hydrophobic grouping: C ₁₀-C ₁₈Alkyl, medium chain C ₁-C ₃Branching C ₁₀-C ₁₈Alkyl, Guerbet branching C ₁₀-C ₁₈Alkyl and composition thereof and be selected from the positively charged ion of Na, K and composition thereof;

● contain the manual dishwashing composition of alkyl (poly-alkoxyl group) sulfate surfactant, its amount is about 25% for about 0.5%-of described detergent composition weight, and wherein said alkyl (gathering alkoxyl group) sulfate surfactant has :-be selected from following hydrophobic grouping: straight chain C ₁₀-C ₁₆Alkyl, medium chain C ₁-C ₃Branching C ₁₀-C ₁₆Alkyl, Guerbet branching C ₁₀-C ₁₆Alkyl and composition thereof; With-being selected from following (poly-alkoxyl group) sulfate radical hydrophilic radical: 1-15 polyethoxye sulfate radical, the poly-propoxy-sulfate radical of 1-15, the poly-butoxy sulfate radical of 1-15,1-15 mix poly-(oxyethyl group/propoxy-/butoxy) sulfate radical and composition thereof, are end-blocking or non-end-blocking form; With the positively charged ion that is selected from Na, K and composition thereof;

Preferably when the manual dishwashing composition contained alkyl (poly-alkoxyl group) sulfate surfactant, this tensio-active agent had one and is selected from following hydrophobic grouping: straight chain C ₁₀-C ₁₆Alkyl, medium chain C ₁-C ₃Branching C ₁₀-C ₁₆Alkyl, Guerbet branching C ₁₀-C ₁₆Alkyl and composition thereof; With one be selected from following (poly-alkoxyl group) sulfate radical hydrophilic radical: 1-15 polyethoxye sulfate radical, the poly-propoxy-sulfate radical of 1-15, the poly-butoxy sulfate radical of 1-15,1-15 mix poly-(oxyethyl group/propoxy-/butoxy) sulfate radical and composition thereof, are end-blocking or non-end-blocking form; With the positively charged ion that is selected from Na, K and composition thereof.

Preferably when the manual dishwashing composition contained nonionogenic tenside, this promoting agent was the poly-alkoxyl alcohol of an end-blocking or non-end-blocking form, and it has one and is selected from following hydrophobic grouping: straight chain C ₁₀-C ₁₆Alkyl, medium chain C ₁-C ₃Branching C ₁₀-C ₁₆Alkyl, Guerbet branching C ₁₀-C ₁₆Alkyl and composition thereof; With one be selected from following hydrophilic radical: 1-15 ethoxylate, 1-15 propoxylated glycerine, 1-15 butoxy thing and composition thereof are end-blocking or non-end-blocking form.When being non-end-blocking form, also have a terminal primary hydroxylic moiety, when be the end-blocking form, the terminal portions of the same form-OR in addition, wherein R is C ₁-C ₆Hydrocarbyl portion, the optional uncle's alkyl that comprises is secondary alcohol when existing preferably perhaps.

Preferably when the manual dishwashing composition contained an alkyl sulfate surfactant, this alkyl sulfate surfactant had one to be selected from following hydrophobic grouping: C ₁₀-C ₁₈Alkyl, medium chain C ₁-C ₃Branching C ₁₀-C ₁₈Alkyl, Guerbet branching C ₁₀-C ₁₈Alkyl and composition thereof and be selected from the positively charged ion of Na, K and composition thereof.

Manual dishwashing composition of the present invention can use or coating and/or use with unit or the dosage that freely changes with hand, and perhaps by the use of autofeed device, they can use in the cleaning system of moisture or non-water.Although pH is a preferred implementation for the alkaline detergent composition of about 8-about 11, they can have pH widely, for example about 2-about 12 or higher, and they can have basicity deposit widely.High foam and low foam type are all included, and these types all can be used in all known moisture and non-water consumer's goods purging methods.

The manual dishwashing composition can be any conventional form, i.e. liquid, powder, aggregate, paste, tablet, rod, gel, liquid gel, microemulsion, liquid crystals or particle.Conventional manual dishwashing auxiliary agent and method:

The precise nature of these annexing ingredients and add-on thereof will depend on the physical form of composition and the character of cleaning operation to be used.

The amount of conventional manual dishwashing auxiliary agent is about 0.00001%-about 99.9% of composition weight.The consumption of whole composition can have very big variation according to the purposes of wanting, and for example scope directly is applied to pure cleaning combination on the clean surface to so-called for the several ppm from solution.

Preferred conventional manual dishwashing auxiliary agent is selected from: washing assistant, detersive enzyme, except that crystallinity destructive alkylaryl sulfonate surfactants, typically be selected from negatively charged ion, positively charged ion, both sexes, zwitter-ion, the tensio-active agent of nonionic and composition thereof, at least be partially soluble in water or be scattered in the polymkeric substance of water, abrasive, sterilant, tarnish inhibitor, dyestuff, solvent, hydrotropic agent, spices, thickening material, antioxidant, processing aid, suds booster, suds suppressor, buffer reagent, anti-mycotic agent, mould control agent, insect repellent, the protection against corrosion auxiliary agent, sequestrant and composition thereof.Most preferably conventional cleaning additive comprise following one or more:

Consumer's goods cleaning combination is described in " Surfactant Science Series ", Marcel Dekker, and New York is in 1-67 volume and the higher volume.Liquid composition especially is described in the 67th volume, liquid washing agent (Liquid Detergents), and Kuo-Yann Lai edits, and 1997, ISBN 0-8247-9391-9 is added herein by reference it.More typical prescription, particularly particle form are described in " Detergent Manufactureincluding Zeolite Builders and Other New Materials ", M.Sittig edits, Noyes Data Corporation in 1979, is added herein by reference it.Also referring to Kirk Othmer ' s Encyclopedia of Chemical Technology.

Have lasting fragrance washing composition (for example referring to US5,500,154; WO96/02490) become more and more popular, can expect being used in combination with this surfactant mixture.

In general, conventional manual dishwashing auxiliary agent changes into any material of the composition that is used for manual dishwashing for the composition that need will only contain minimum neccessary composition (this paper is necessary crystallinity-disrupted alkylaryl sulfonate surfactants).In a preferred embodiment, those skilled in the art can easily recognize the conventional manual dishwashing auxiliary agent as the absolute specificity of cleaning products.

Conventional manual dishwashing auxiliary agent comprises washing assistant, tensio-active agent, enzyme and polymkeric substance etc.Other auxiliary agent of this paper can comprise that suds booster, suds suppressor (defoamer) etc., various activeconstituents or specific material such as polymer dispersant are (for example from BASF AG or Rohm; Haas), colored spot, protect silver, antirust and/or anticorrosive agent, dyestuff, filler, sterilant, source of alkalinity, hydrotropic solvent, antioxidant, enzyme stabilizers, fragrance precursor, spices, solubilizing agent, carrier, processing aid, pigment and be used for the solvent of liquid preparation, have a detailed description below this paper.

Quite typically, the composition of this paper may need several auxiliary agents, although some simple formulated product may only need a kind of auxiliary agent.Suitable laundry or cleaning additive material and rot-resistant comprehensive list can be in applications on July 21st, 1997 and to transfer Procter; Find in the U.S. Provisional Patent Application 60/053,318 of Gamble.

Crystallinity-disrupted alkylaryl sulfonate surfactants of the present invention can be used for manual dishwashing goods widely.This novel surfactant system can be used for the conventional LAS of the existing manual dishwashing composition of all or part of replacement.Crystallinity-disrupted alkylaryl sulfonate surfactants of the present invention can replenishing or including, but are not limited to as the goods of all or part of substitute of LAS in this surfactant system as existing surfactant system:

WO98/12290; US5728668; WO98/05745; US5756441; US5714454; US5712241; US5707955; US4,133,779; WO97/47717; US5688754; US5665689; WO9738073; US5696073; WO97/38071; WO97/00930 A; GB2,292,562 A; US5,376,310; US5,269,974; US5,230,823; US4,923,635; US4,681,704; US4,316,824; US4,133,779; US5700773; WO9735947; WO97/34976; US5629279; WO9715650; US5616548; US5610127; US5565421; WO96/31586; US5561106; US5552089; WO96/22347; US5503779; US 5480586; EP 573329; US5382386; EP487169; US5096622; EP431050; US5102573; US4772425; US4725337; EP228797; US4556509; US4454060; US4554098; US4430237; US4877546; US4064076; US4101456; US3944663; US4040989; US4102826; US5767051; US5780417; WO97/26315; US5290482; US3954679; US5700331; US5679877; US5565419; WO98/22569; US5736496; US5733560; US574169; US5733860; US5741770; US5719114; US5604195; EP848749; EP839177; US5646104; US5580848; EP781324US5415812; US5435936; US5082584; US5393468; Detergent surfactant-this composition comprises the employed detergent surfactant of cosurfactant as main surfactant mixture ideally.Because the present invention is relevant with tensio-active agent, when describing the preferred implementation of detergent composition of the present invention, the described separately and explanation of tensio-active agent material and on-surface-active auxiliary agent.Detergent surfactant has carried out broad description in following document: authorized people's such as Laughlin US3929678 on December 30th, 1975 and authorized the US4259217 of Murphy on March 31st, 1981; " SurfactantScience " book series, Marcel Dekker, Inc., New York and Basel; " Handbook of Surfactants ", M.R.Porter, Chapman and Hall, 2nd Ed., 1994; " Surfactants in Consumer Products ", Ed.J.Falbe, Springer-Verlag, 1987; With authorize Procter ﹠amp; The patent that the many and washing composition of Gamble is relevant and other washing composition and consumer's goods manufacturer.

The detergent surfactant of this paper comprises the known tensio-active agent that is used as negatively charged ion, nonionic, positively charged ion, zwitter-ion or the amphoteric type of clean-out system, but does not comprise complete non-foam or complete insoluble tensio-active agent (but they can be used as optional adjuvants).

In more detail, the useful detergent surfactant of this paper comprises aptly: (1) conventional alkylbenzene sulfonate, comprise hard (ABS, TPBS) or straight chain type and through currently known methods such as various HF or solid HF, for example DETAL ^(UOP) method production is perhaps by using other lewis acid catalyst such as AlCl ₃Preparation is perhaps used the preparation of acid silica/alumina or is prepared by chlorinated hydrocarbon; (2) ethylenic sulfonate comprises alpha-alefinically sulfonate and the sulfonate that is obtained by lipid acid or fatty acid ester; (3) the alkyl or alkenyl sulfosuccinic ester comprises its diester and half ester type and sulphosuccinamate and the sulfosuccinic ester of other sulfonate/carboxylate surface active agent type as being obtained by ethoxy alcohol and alkylolamide; (4) paraffin or sulfonated alkane type and alkyl or alkenyl carboxyl sulfonate type comprise the product that bisulfite is added to alhpa olefin; (5) sulfonated alkyl naphathalene; (6) alkyl isethionate and alkoxypropan sulfonate, and the ester of hydroxyethylsulfonic acid fatty ester, ethoxylation hydroxyethylsulfonic acid fatty ester and other sulfonated ester such as 3-hydroxy-propanesulfonic acid or AVANEL S type; (7) benzene, cumene, toluene, dimethylbenzene and naphthalenesulfonate, particularly useful to its hydrotrophy; (8) alkylether sulfonate; (9) alkane amidosulfonic acid salt; (10) alpha-sulfo-fatty acid salt or ester and interior sulfo fatty acid ester; (11) alkyl glycerol sulfonate; (12) sulfonated lignin; (13) sulfonated petro-leum, the known sometimes alkylate sulfonate of attaching most importance to; (14) phenyl ether stilbene-4,4'-bis-(1-azo-3, 4-dihydroxy-benzene)-2,2'-disulfonate; (15) straight or branched alkyl-sulphate or alkenyl sulfate; (16) alkyl or alkyl phenolic alkoxy vitriol and corresponding poly-alkoxylation thing are referred to as sulfated alkyl ether sometimes, and thiazolinyl alkoxy sulfate or the poly-alkoxy sulfate of thiazolinyl; (17) alkylamide vitriol or alkenyl amide vitriol comprise sulfated alkylolamide and alcoxylates thereof and poly-alkoxylation thing; (18) sulfated oil, sulfation alkyl glycerol ester, sulfation alkyl polyglycerol ester or sulfated sugar deriving surface promoting agent; (19) the poly-alkoxyl group carboxylate salt of alkyl alkoxy carboxylate salt and alkyl comprises the galacturonic hydrochlorate; (20) alkyl ester carboxylate salt and alkenyl esters carboxylate salt; (21) alkyl or alkenyl carboxylate salt, particularly conventional soap and alpha, omega-dicarboxylic acid salt also comprise alkyl and alkenyl succinate; (22) alkyl or alkenyl acid amides alkoxyl group and poly-alkoxyl group carboxylate salt; (23) alkyl and thiazolinyl amido carboxylic acids salt surfactant type comprise sarcosinate, taurate, glycinate, L-Ala salt and imido propionic salt; (24) acid amides soap is referred to as the lipid acid cyanamide sometimes; (25) alkyl polyaminocarboxylate; (26) phosphorus based surfactants comprises the alkyl or alkenyl phosphoric acid ester, comprises alkyl ether phosphate, phosphotidats, alkyl phosphonate, alkyl two (polyoxyalkylene alkanol) phosphoric acid salt, amphoteric phosphate such as the Yelkin TTS of its alkoxy derivative; And phosphoric acid salt/carboxylate salt, phosphoric acid salt/vitriol and phosphoric acid salt/sulfonate type; (27) Pluronic-and Tetronic-type nonionogenic tenside; (28) so-called EO/PO block polymer comprises diblock and three block EPE and PEP type; (29) polyol esters of fatty acids; (30) end-blocking and non-end-blocking alkyl or alkyl phenol ethoxylate, propoxylated glycerine and butoxy thing comprise fatty alcohol polyglycol ether; (31) Fatty Alcohol(C12-C14 and C12-C18) is in particular as the tensio-active agent that improves viscosity or exist as the unreacted components of other tensio-active agent; (32) N-alkyl polyhydroxy fatty acid amide, particularly alkyl N-alkyl glucose amide; (33) nonionogenic tenside, particularly APG that obtains by monose or polysaccharide or sorbitanic, and sucrose fatty ester; (34) ethylene glycol-, propylene glycol-, glycerine-and Polyglycerine-ester and alcoxylates thereof, particularly glyceryl ether and fatty acid one ester and diester; (35) two alditol acidamide surfactants; (36) alkyl succinimide nonionic surfactants; (37) alkynol tensio-active agent, for example SURFYNOLS; (38) alkylolamide tensio-active agent and alkoxy derivative thereof comprise fatty acid alkyl amide and fatty acid alkyl amide polyol ethers; (39) alkyl pyrrolidone; (40) alkyl amine oxide comprises alkoxylate or poly-alkoxylation amine oxide and the amine oxide that is obtained by sugar; (41) alkyl phosphine oxide; (42) sulfoxide tensio-active agent; (43) both sexes sulfonate, particularly sultaine; (44) betaine type amphoteric surfac-tant comprises amino carboxylate derived type; (45) both sexes vitriol, for example alkyl polyethoxye ammonium sulfate; (46) alkylamine and the amine salt of fat and petroleum derivation; (47) alkyl imidazoline; (48) alkyl amido amine and alcoxylates thereof and poly-alkoxylation thing derivative; (49) conventional cats product comprises water-soluble alkyl trimethyl ammonium salt.And, comprise more uncommon tensio-active agent, for example: (50) alkyl amido amine oxide, carboxylate and quaternary salt; (51) the sugared deutero-tensio-active agent that after any above-cited more common non-sugared type, imitates; (52) fluorine surfactant; (53) bio-surfactant; (54) organosilicon or fluorocarbon tensio-active agent; (55) geminal surfactant is not above-cited phenyl ether stilbene-4,4'-bis-(1-azo-3, 4-dihydroxy-benzene)-2,2'-disulfonate, comprises those that are obtained by glucose; (56) polymeric surfactant comprises many carboxyls of both sexes glycinate; (57) meteor capitate tensio-active agent; Become known for the arbitrary surfaces promoting agent that moisture or non-water cleans in brief.

In the detergent surfactant, hydrophobic chain length typically is common scope C on arbitrarily ₈-C ₂₀, often preferred chain length C ₈-C ₁₈, particularly when in cold water, doing washing.For conventional purpose has instruction to being chosen in of chain length and degree of alkoxylation in the national textbook.When detergent surfactant is salt, can there be compatible positively charged ion arbitrarily, comprise H (promptly can use the acid or the sour form of part of potential acid surface active agent), Na, K, Mg, ammonium or alkanol ammonium or cationic combination.Usually the mixture, particularly negatively charged ion/positively charged ion, cationic/nonionic, anionic/nonionic/positively charged ion, anionic/nonionic/both sexes, nonionic/positively charged ion and the nonionic/amphoteric admixture that preferably have the detergent surfactant of different electric charges.And; can with any single detergent surfactant with have different chain length, degree of unsaturation or the degree of branching, degree of alkoxylation (particularly ethoxylation), substituent insertion replaces as the mixture of other similar detergent surfactant of the ether oxygen atom in hydrophobic grouping or its arbitrary combination, often obtains the desired result of cold water washing.

Preferred in the above-mentioned detergent surfactant: C ₉-C ₂₀Linear alkyl benzene sulphonic acid, its sodium salt and ammonium salt, particularly linear secondary alkyl C ₁₀-C ₁₅Benzene sulfonic acid sodium salt, although can use ABS in some place, (1); Ethylenic sulfonate, (2) are promptly passed through alkene, particularly C ₁₀-C ₂₀Alpha-olefin is with the material that the sulphur trioxide reaction neutralizes then and the hydrolysis reaction product prepares; C ₇-C ₁₂Dialkyl sodium sulfosuccinate and ammonium, (3); The alkane monosulfonate, (4) are for example passed through C ₈-C ₂₀Those that the reaction of alpha-olefin and Sodium Metabisulphate 65 obtains and with paraffin and SO ₂And Cl ₂Reaction is then with in the alkali and form those of random sulfonate; Alpha-sulfo-fatty acid salt or ester, (10); The alkyl glycerol sodium sulfonate, those ethers of (11), the particularly higher alcohols that obtains by butter or Oleum Cocois and the synthol that obtains by oil; Alkyl or alkenyl vitriol, (15), what it can be for uncle or secondary, saturated or unsaturated, branching or non-branching.These compounds can be for random or regular when branching.When being secondary, they preferably have formula CH ₃(CH ₂) _x(CHOSO ₃ ^-M ⁺) CH ₃Or CH ₃(CH ₂) _y(CHOSO ₃ ^-M ⁺) CH ₂CH ₃, x and (y+1) be at least 7 integer wherein, preferably at least 9, M is a water-soluble cationic, preferably sodium.When being unsaturated, the vitriol of preferred oil acyl sulfate salt, sodium alkyl sulfate and ammonium particularly pass through C simultaneously ₈-C ₁₈Those that the alcohol sulfation is produced also are useful by those of butter or Oleum Cocois production for example; Also preferred alkyl or alkene ether vitriol, (16) particularly have 0.5mol or higher ethoxylation, the ethoxy sulfate of preferred 0.5-8; The alkyl ether carboxy acid salt, (19), particularly EO1-5 ethoxy carboxylate; Soap or lipid acid, (21), type preferably more soluble in water; Amino acid surfactant, (23), for example sarcosinate, particularly oleoyl sarcosinates; Phosphoric acid ester, (26); Alkyl or moieties ethoxylate, propoxylated glycerine and butoxy thing, (30), particularly ethoxylate " AE " comprises so-called narrow peak alkylethoxylate and C ₆-C ₁₂Moieties alcoxylates and aliphatic series uncle or secondary straight or branched C ₈-C ₁₈The product of alcohol and ethylene oxide, 2-30 EO usually; N-alkyl polyhydroxy fatty acid amide, particularly C ₁₂-C ₁₈The N-methyl glucose amide, (32) are referring to WO9206154 and N-alkoxyl group polyhydroxy fatty acid amide, for example C ₁₀-C ₁₈N-(3-methoxy-propyl) glucamide, the N-propyl group is to N-hexyl C simultaneously ₁₂-C ₁₈Glucamide can be used for reducing foaming; APG, (33); Amine oxide, (40), preferred N-oxidation of alkyl dimethyl amine and dihydrate thereof; Sultaine or " sultaine ", (43); Trimethyl-glycine (44); And geminal surfactant.

Be applicable to that cats product of the present invention comprises those with long chain hydrocarbon groups.The example of these positively charged ion cosurfactants for example comprises the ammonium cosurfactant of halogenated alkyl Dimethyl Ammonium and those cosurfactants with following formula:

[R ²(OR ³) _y] [R ⁴(OR ³) _y] ₂R ⁵N ⁺X ^-R wherein ²Be alkyl or the alkylbenzene methyl that in alkyl chain, has 8-18 carbon atom, each R ³Be selected from-CH ₂CH ₂-,-CH ₂CH (CH ₃)-,-CH ₂CH (CH ₂OH)-,-CH ₂CH ₂CH ₂-, and composition thereof; Each R ⁴Be selected from C ₁-C ₄Alkyl, C ₁-C ₄Hydroxyalkyl, by connecting two R ⁴The phenmethyl ring structure that group forms ,-CH ₂CHOH-CHOHCOR ⁶CHOHCH ₂OH, R wherein ⁶For molecular weight is lower than about 1000 any hexose or hexose polymkeric substance and is H (when y is not 0), R ⁵With R ⁴Identical or be alkyl chain, wherein R ²With R ⁵In the carbonatoms summation be no more than about 18; Each y is that 0-is about 10, and y value sum is 0-about 15; And X is any compatible negatively charged ion.

The example of the cats product that other is suitable is described in the following document, their full content all is added herein by reference: M.C.Publishing Co., McCutcheon ' s, washing composition and emulsifying agent (Detergents ﹠amp; Emulsifiers), (North American edition 1997); People such as Schwartz, tensio-active agent, its chemistry and technology (Surface Active Agents, Their Chemistry andTechnology), New York: Interscience Publishers, 1949; US3155591; US3929678; US3959461; US4387090 and US4228044.

The example of suitable cats product is corresponding to those of following general formula:

R wherein ₁, R ₂, R ₃And R ₄Be independently selected from the aliphatic group of about 22 carbon atoms of 1-or have aryl, alkoxyl group, polyalkylene oxide, alkyl amido, hydroxyalkyl, aryl or alkylaryl up to about 22 carbon atoms; And X for example is selected from those of halogen (for example Cl, Br), acetate moiety, citrate, lactate, glycol acid radical, phosphate radical, nitrate radical, sulfate radical and alkyl sulfate for becoming salt anionic.Except carbon and hydrogen atom, this aliphatic group can contain ehter bond and other for example amino group.This long-chain aliphatic group, for example about 12 carbon atoms or higher those can be for saturated or unsaturated.Preferably work as R ₁, R ₂, R ₃And R ₄Be independently selected from C ₁-Yue C ₂₂During alkyl.Especially preferably contain the cationic materials of two long alkyl chains and two short alkyl chains or contain 1 long alkyl chain and those of 3 short alkyl chains.Long alkyl chain described in the previous sentence in the compound has about 22 carbon atoms of about 12-, about 22 carbon atoms of preferably about 16-, and the short alkyl chain in the compound described in the previous sentence has about 3 carbon atoms of 1-, preferred about 2 carbon atoms of 1-.

The sufficient quantity of cationic detersive tensio-active agent is about 20% for about 0.1%-herein, and preferably about 1%-is about 15%, although high-content more, for example up to about 30% or more, may be at nonionic: particularly useful in positively charged ion (be restricted or the do not have negatively charged ion) goods.A kind of possible purposes of cats product is as the grease release agent.Cats product can be independently or with solvent/or solubilizing agent combination.Referring to US5552089.

Another kind of useful tensio-active agent is so-called dianionic surfactant.These are the tensio-active agents that have at least 2 anionic groups on surfactant molecule.Some suitable dianionic surfactants also are described in pending trial United States serial 60/020503 (case 6160P), 60/020772 (case 6161P), 60/020928 (case 6158P), 60/020832 (case 6159P) and 60/020773 (the case 6162P) of application on June 28th, 1996; And pending trial United States serial 60/023539 (case 6192P), 60/023493 (case 6194P), 60/023540 (case 6193P) and 60/023527 (the case 6195P) of application on August 8th, 1996, its disclosed content is added herein by reference.

Also preferred in addition, this tensio-active agent can be mid-chain branched alkyl-sulphate, mid-chain branched alkyl alkoxylates or mid-chain branched alkyl alkoxylates vitriol.These tensio-active agents also are described in: lawyer's case on October 14th, 1997 number is 60/061 of 6881P, 971, lawyer's case on October 14th, 1997 number is 60/061 of 6882P, 975, lawyer's case on October 14th, 1997 number is 60/062 of 6883P, 086, lawyer's case on October 14th, 1997 number is 60/061 of 6884P, 916, lawyer's case on October 14th, 1997 number is 60/061 of 6885P, 970, lawyer's case on October 14th, 1997 number is 60/062,407 of 6886P.Other suitable mid-chain branched tensio-active agent can find in following U.S. Patent Application Serial Number: 60/032,035 (case 6401P), 60/031,845 (case 6402P), 60/031,916 (case 6403P), 60/031,917 (case 6404P), 60/031,761 (case 6405P), 60/031,762 (case 6406P) and 60/031,844 (case 6409P).These branched surfactants and conventional straight chain surfactant mixtures also are applicable in this composition.

Also should expect the combination of tensio-active agent.A kind of like this combination should be the alkylbenzenesulfonatsurfactants surfactants of the present invention that forms electronegative mixture with alkylene carbonate (alkylene carbonate) tensio-active agent.Referring to US5736496.Perhaps these alkylene carbonate tensio-active agents can make up with the alkyl benzene sulfonate surfactant of modification of the present invention, but do not form electronegative mixture.The composition among the US5733860 for example.Any one all comprises following formula in these two kinds of combinations that alkylene carbonate is fit to:

R wherein ¹Be C _nAlkyl, R ²Be H or C _mAlkyl, and n+m is number 11-14;

May be combined as and the monoalkyl Succinamate with another of the alkyl benzene sulfonate surfactant of modification, more preferably with the C of the about 6wt% of about 0.5- ₁₀-C ₁₈The monoalkyl Succinamate, wherein this alkyl can be used the ethoxylated up to 8 moles, and the monoalkyl Succinamate has following structure:

Wherein R is the aliphatic group of 10-18 carbon atom, and M is positively charged ion, is selected from sodium, potassium, ammonium and alkanolamine.Referring to US5480586.

The sufficient quantity of the anionic detergent tensio-active agent of this paper is about 1%-about 50% of detergent composition weight or higher, and preferably about 2%-is about 30%, even 5%-about 20% more preferably from about.

The sufficient quantity of the nonionic detergent surfactant of this paper is about 40% for about 1%-, and preferably about 2%-is about 30%, and more preferably from about 5%-about 20%.

Anion surfactant comprises 1.0 with the ideal weight ratio of nonionogenic tenside in the combination: 9.0-1.0: 0.25, preferred 1.0: 1.5-1.0: 0.4.

Anion surfactant comprises 50 with the ideal weight ratio of cats product in the combination: 1-5: 1, more preferably 35: 1-15: 1.

The optimal level of cationic detersive tensio-active agent is about 0.1%-about 20% herein, preferred about 1%-about 15%, but can be higher level, for example up to about 30% or more, particularly at nonionic: in positively charged ion (be conditional or the do not have negatively charged ion) goods may be useful.

Both sexes or zwitierionic detergent surfactant are when existing, and it has consumption often to be the 0.1%-about 20% of detergent composition weight.Often its horizontal constraints is about 5% or lower, particularly when amphoterics is expensive.Tensio-active agent

Composition preferably contain described composition weight at least about 0.01%, more preferably at least about 0.1%, even more preferably at least about 0.2%, even more preferably at least about 0.5% tensio-active agent.Composition also will preferably contain be no more than about 90%, more preferably no more than about 70%, even more preferably no more than about 60%, even more preferably no more than about 35% tensio-active agent of described composition weight.

Anion surfactant useful among the present invention is preferably selected from: linear alkylbenzene sulfonate, α ethylenic sulfonate, paraffin sulfonate class, alkyl ester sulfonate class, alkylsurfuric acid salt, alkyl alkoxy sulfate, alkyl sulfonates, alkyl alkoxy carboxylate salt, alkyl alkoxylated suifate class, sarkosine salt, taurine salt, and composition thereof.

When existing, anion surfactant typically exists with significant quantity.More preferably composition can contain at least about 0.5%, more preferably at least about 5%, even more preferably at least about the anion surfactant of 10% described composition weight.Composition also preferably contain be no more than about 90%, more preferably no more than about 50%, even more preferably no more than the anion surfactant of about 30% described composition weight.

Alkyl sulfate surfactant is an another kind of important anion surfactant used herein.As formula ROSO ₃The water-soluble salt of M or acid with polyhydroxy fatty acid amide class (referring to following) when using except good whole cleansing power is provided, can also obtain to be included in widely in temperature, wash concentration and the washing time the good cleaning of fat/oil, the solvability of alkyl-sulphate and the preparation of the raising in the liquid washing agent goods, formula ROSO ₃R is preferably C among the M ₁₀-C ₂₄Alkyl preferably has C ₁₀-C ₂₀The alkyl of alkyl component or hydroxyalkyl, more preferably C ₁₂-C ₁₈Alkyl or hydroxyalkyl, and M is H or positively charged ion, for example alkali metal cation (IA family) (for example sodium, potassium, lithium), replacement or unsubstituted ammonium cation for example methyl-, dimethyl-and trimethyl ammonium and quaternary ammonium cation, for example tetramethyl-ammonium and lupetidine, and the positively charged ion that obtains by the alkanolamine of for example thanomin, diethanolamine, trolamine, and composition thereof etc.Typically, C _12-16Alkyl chain is preferred for low wash temperature (for example about below 50 ℃) and C _16-18Alkyl chain is preferred for higher wash temperature (for example about more than 50 ℃).

Alkyl alkoxylated sulfate surfactant is another kind of useful anion surfactant.These tensio-active agents typically are formula RO (A) _mSO ₃The water-soluble salt of M or acid, wherein R is unsubstituted C ₁₀-C ₂₄Alkyl or have C ₁₀-C ₂₄The hydroxyalkyl of alkyl component, preferred C ₁₂-C ₂₀Alkyl or hydroxyalkyl, more preferably C ₁₂-C ₁₈Alkyl or hydroxyalkyl, A are oxyethyl group or propoxy-unit, and m is greater than 0, and be typically about 6 at about 0.5-, and more preferably from about 0.5-is about 3, and M is H or positively charged ion, for example can be metallic cation (for example sodium, potassium, lithium etc.), ammonium or replace ammonium cation.This paper comprises alkyl ethoxylated sulfate class and alkyl propoxylated sulphates class.The object lesson that replaces ammonium cation comprise methyl-, dimethyl-, trimethylammonium-ammonium and quaternary ammonium cation, for example tetramethyl-ammonium and lupetidine, and the positively charged ion that obtains by the alkanolamine of for example Monoethanolamine MEA BASF, diethanolamine and trolamine, and composition thereof.The tensio-active agent of illustration is C ₁₂-C ₁₈Alkyl polyethoxylated (1.0) vitriol, C ₁₂-C ₁₈Alkyl polyethoxylated (2.25) vitriol, C ₁₂-C ₁₈Alkyl polyethoxylated (3.0) vitriol and C ₁₂-C ₁₈Alkyl polyethoxylated (4.0) vitriol, wherein M often is selected from sodium and potassium.Tensio-active agent used herein can be made by natural or synthol raw material.On behalf of average hydrocarbon, chain length distribute, and comprises branching.This anion surfactant component can contain alkyl-sulphate and the sulfated alkyl ether that is obtained by the pure source of routine, and these alcohol for example have natural alcohols, synthetic alcohols as with trade(brand)name NEODOL ^TM, ALFOL ^TM, LIAL ^TM, LUTENSOL ^TMDeng sell those.Sulfated alkyl ether also is referred to as alkyl polyethoxylated vitriol.

In " tensio-active agent and washing composition (Surface Active Agents andDetergents) " (I and II volume, Schwartz, Perry and Berch), provided suitable examples of anionic surfactants.The 23rd hurdle the 58th that many these tensio-active agents also are disclosed in the US3929678 that authorized people such as Laughlin on December 30th, 1975 usually walks to the 29th hurdle the 23rd row.

A utilizable analog anion surfactants comprises alkylether sulfonate.Because they can prepare with reproducible non-petroleum source, so they are comparatively ideal.Can carry out the preparation of alkylether sulfonate tensio-active agent according to disclosed currently known methods in this technical literature.For example, straight chain C 8-C20 carboxylicesters can be according to " U.S. oiling association will " (The Journal ofthe American Oil Chemists Society), 52 (1975), 323-329 page or leaf gaseous state SO ₃Sulfonation.Suitable raw material comprises the natural fat material that obtains from butter, palm and coconut wet goods.

Preferred alkylether sulfonate tensio-active agent especially for what do washing, comprises the alkyl sulfonate surfactants of following structural formula:

R wherein ³Be C ₈-C ₂₀Alkyl, preferred alkyl, or its combination, R ⁴Be C ₁-C ₆Alkyl, preferred alkyl, or its combination, and M is the solubility salt-forming cation.Suitable salt comprises for example metal-salt of sodium, potassium and lithium salts, and replacement or unsubstituted ammonium salt, for example monomethyl-, dimethyl, trimethylammonium and quaternary ammonium salt, for example tetramethyl ammonium and lupetidine, and the positively charged ion that obtains by the alkanolamine of for example Monoethanolamine MEA BASF, diethanolamine, trolamine.Preferred R ³Be C ₁₀-C ₁₆Alkyl, R ⁴Be methyl, ethyl or sec.-propyl.Preferred especially R ³Be C ₁₄-C ₁₆The methyl ether sulfonate of alkyl.

In the present composition, can also comprise other useful anion surfactant of washing purpose.These can comprise soap salt (for example comprise sodium, potassium, ammonium and substituted ammonium salt as one, two and triethanolamine salt), C ₉-C ₂₀Linear alkylbenzene sulfonate class, C ₈-C ₂₂Uncle or secondary alkansulfonic acid salt, C ₈-C ₂₄The ethylenic sulfonate class; the sulfonated poly carboxylic acid of pyrolysis product preparation by sulfonation alkali earth salt described in English Patent 1082179; the alkyl glycerol sulfonate class; fatty oil base glycerol Sulfonates; the fat acidyl glycerine sulphate class; alkylphenol ethylene oxide ether sulfate class; the paraffin sulfonate class; the alkylphosphonic acid carboxylic acid salt; the different thiosulfates of different thiosulfates such as acyl group; N-acyl taurine salt class; the fatty acid acyl amine of N-methyltaurine; amber alkyl amide salts class and sulfo-succinic acid salt; sulfo-succinic acid one ester class (particularly saturated and unsaturated C ₁₂-C ₁₈One ester class), sulfosuccinic acid diesters class (particularly saturated and unsaturated C ₆-C ₁₄The diester class), the Sulfates of N-acyl sarcosinate class, alkyl polysaccharide Sulfates such as APG (nonionic non-sulfuric acid compound described below), branched primary alkyl sulphates class, alkyl polyethoxye metal carboxylate are suc as formula RO (CH ₂CH ₂O) _kCH ₂COO ^-M ⁺Those, wherein R is C ₈-C ₂₂Alkyl, k are the integer of 0-10, and M is the solubility salt-forming cation, and also use sodium hydroxide neutral lipid acid with the isethionic acid esterification.Resinous acid and hydrogenated resin acid also are fit to, for example rosin, staybelite and be present in Yatall MA or by the resinous acid and the hydrogenated resin acid of its acquisition.Further example is given among " tensio-active agent and washing composition " (Surface Active Agents and Detergents) (volume I and II, Schwartz, Perry and Berch).These a large amount of tensio-active agents also are disclosed in the US3 that authorized people such as Laughlin on December 30th, 1975 usually, and 929,678 the 23rd hurdle the 58th walks to the 29th hurdle the 23rd row.

Nonionic detergent tensio-active agent-suitable nonionic detergent tensio-active agent is disclosed in the US3 that authorized people such as Laughlin on December 30th, 1975 usually, and 929,678 the 13rd hurdle the 14th walks to the 16th hurdle the 6th row, and it is added herein by reference.The useful ionic surfactant pack of illustrative, non-limiting type is drawn together: alkylethoxylate, alkyloyl glucamide, C ₁₂-C ₁₈Alkylethoxylate (" AE ") comprises so-called narrow peak alkylethoxylate and C ₆-C ₁₂Alkylphenol alcoxylates (particularly ethoxylate and mixing oxyethyl group/propoxy-), and composition thereof.

When existing, nonionogenic tenside typically exists with significant quantity.More preferably composition can contain at least about 0.1%, more preferably at least about 0.5%, even more preferably at least about the nonionogenic tenside of 0.5% described composition weight.Composition also preferably contain be no more than about 20%, more preferably no more than about 15%, even more preferably no more than the nonionogenic tenside of about 10% described composition weight.

The polyoxyethylene of alkylphenol, polyoxytrimethylene and polyoxybutylene condenses.In general, preferred its polyoxyethylene condenses.These compounds are included as the straight or branched configuration and have the alkylphenol of alkyl of about 12 carbon atoms of about 6-and the condensation product of alkylene oxide.In a preferred embodiment, ethylene oxide exists with the amount of every mole of about 25 mole ethylene oxides of the about 5-of alkylphenol.This class ionic surfactant pack of commercially available acquisition is drawn together the Igepal that is sold by GAF company ^CO-630; And Rohm ﹠amp; The Triton that Haas company sells ^X-45, X-114, X-100 and X-102.These compounds are referred to as alkylphenol alcoxylates (for example alkyl phenol ethoxylate) usually.

The condensation product of fatty alcohol and about 25 mole ethylene oxides of about 1-.The alkyl chain of fatty alcohol can be straight or branched, uncle or the second month in a season, and contains about 22 carbon atoms of the 8-that has an appointment usually.The alcohol of preferred especially every mole of alkyl with about 20 carbon atoms of about 10-and the condensation product of about 18 mole ethylene oxides of about 2-.The example of this class nonionogenic tenside of commercially available acquisition comprises Tergitol ^15-S-9 (C ₁₁-C ₁₅The condensation product of linear secondary and 9 mole ethylene oxides), Tergitol ^24-L-6 NMW (C ₁₂-C ₁₄The condensation product of primary alconol and 6 mole ethylene oxides has narrow molecular weight distribution), they are all sold by Union Carbide company; Neodol ^45-9 (C ₁₄-C ₁₅The condensation product of straight chain alcohol and 9 mole ethylene oxides), Neodol ^23-6.5 (C ₁₂-C ₁₃The condensation product of straight chain alcohol and 6.5 mole ethylene oxides), Neodol ^45-7 (C ₁₄-C ₁₅The condensation product of straight chain alcohol and 7 mole ethylene oxides), Neodol ^45-4 (C ₁₄-C ₁₅The condensation product of straight chain alcohol and 4 mole ethylene oxides), sell by Shell Chemical Company, and Kyro ^EOB (C ₁₃-C ₁₅The condensation product of alcohol and 9 mole ethylene oxides), by Procter ﹠amp; Gamble Company sells.The ionic surfactant pack of other commercially available acquisition is drawn together the Dobanol 91-8 that is produced by Shell Chemical company ^With the Genapol UD-080 that produces by Hoechst ^This class nonionogenic tenside is referred to as " alkylethoxylate " usually.

The condensation product of the hydrophobic alkali that ethylene oxide and propylene oxide and propylene glycol condensation form.The hydrophobic part of these compounds preferably has the molecular weight of about 1500-about 1800, and presents water-insoluble.In this hydrophobic part, add the polyoxyethylene part and be tending towards increasing the water-soluble of this molecule on the whole, when polyoxyethylene content up to about 50% of condensation product gross weight, corresponding to up to about 40 mole ethylene oxide condensations the time, product still keeps the characteristics of liquids of product.The example of this compounds comprises the Pluronic of some commercially available acquisition ^Tensio-active agent is sold by BASF.

The condensation product of the product that ethylene oxide and propylene oxide and reacting ethylenediamine obtain.The hydrophobic part of these products is made up of the reaction product of quadrol and excessive oxidation propylene, has the molecular weight of about 2500-about 3000 usually.This hydrophobic part and ethylene oxide be condensed to condensation product contain the polyoxyethylene of the about 80wt% of 40%-that has an appointment and have about 5, the molecular weight of 000-about 11,000.The example of this class nonionogenic tenside comprises the Tetronic of some commercially available acquisition ^Compound is sold by BASF.

The example that is applicable to ethylene oxide-oxypropylene block copolymer of this paper is described in detail in to be authorized among the US 5,167,872 of Pancheri/Mao on December 2nd, 1992.This patent is added herein by reference.

Preferred APG has following formula:

R ²O (C _nH _2nO) _t(glycosyl) _xR wherein ²Be selected from alkyl, alkyl-phenyl, hydroxyalkyl, hydroxyalkyl phenyl, and composition thereof, wherein to contain the 10-that has an appointment about 18 for alkyl, about 14 carbon atoms of preferably about 12-; N is 2 or 3, preferred 2; T is 0-about 10, preferred 0; And x is about 10 for about 1.3-, and preferably about 1.3-is about 3, and most preferably from about 1.3-about 2.7.Glycosyl is preferably obtained by glucose.In order to prepare these compounds, at first form alcohol or alkyl polyethoxye alcohol, then with glucose or source of glucose reaction, thereby form glucosides (on the 1-position, linking to each other).Other glycosyl units can be connected in then between 2-, 3-, 4-and/or the 6-position of its 1-position and front glycosyl units, preferably mainly in the 2-position.

Authorize the US4 of Llenado on January 21st, 1986,565, disclosed APG in 647, have one to contain about 30 carbon atoms of about 6-, the hydrophobic group and a polysaccharide of preferred about 16 carbon atoms of about 10-, for example poly glucoside, to contain about 1.3-about 10, preferably about 1.3-is about 3, most preferably from about the hydrophilic radical of about 2.7 sugar units of 1.3-.Can use any reducing sugar that contains 5 or 6 carbon atoms, for example glucose, semi-lactosi, and the galactosyl part can partly be substituted by glucosyl.(optional this hydrophobic grouping is connected in 2-, 3-, 4-position etc., therefore makes glucose or semi-lactosi relative with glucoside or galactoside.) key can be between position and 2-, 3-, 4-and/or 6-position on the sugar unit of front of for example other sugar unit between sugar.

Optional, not very not ideally, the polyalkylene oxide chain can connect hydrophobic part and polysaccharide part.Preferred alkylene oxide is an ethylene oxide.Typical hydrophobic grouping comprises or saturated or unsaturated, branching or non-branching and to contain the 8-that has an appointment about 18, the alkyl of about 16 carbon atoms of preferably about 10-.Preferred alkyl is the straight chain saturated alkyl.This alkyl can contain up to about 3 hydroxyls and/or polyalkylene oxide chain and can contain up to about 10, preferably is lower than 5 alkylene oxide parts.Suitable alkyl polysaccharide be octyl group, nonyl, decyl, 11 carbon backs, ten dicarbonyls, 13 carbon backs, 14 carbon backs, 15 carbon backs, 16 carbon backs, 17 carbon backs and 18 carbon backs, two-, three-, four-, five-and six glucosides, galactoside, lactoside, glucose, fructoside, fructose and/or semi-lactosi.Suitable mixture comprise coconut alkyl, two-, three-, four-and pentasaccharides glycosides and tallow alkyl four-, five-and six-glucosides.

Another kind of ionic surfactant pack is drawn together a mixture (this paper back is referred to as ethoxylated glycerol type compound), it is the ethoxylation polyvalent alcohol of whole esterifications, the ethoxylation polyvalent alcohol of partial esterification and the mixture of nonesterified polyvalent alcohol, wherein preferred polyhydric alcohols is a glycerine, and this compound is:

Formula (I) and

Formula (II) wherein w equals 1-4, and most preferably 1.B is selected from the group of hydrogen or following formula representative:

Wherein R is selected from: have 6-22 carbon atom, the alkyl of 11-15 carbon atom and have a 6-22 carbon atom most preferably, the thiazolinyl of 11-15 carbon atom most preferably, wherein most preferably hydrogenated tallow alkyl chain or cocoa alkyl chain, wherein at least one B group is by shown in the following formula:

And R ' is selected from: hydrogen and methyl; The value of x, y and z is 0-60, more preferably 0-40, as long as (x+y+z) equal 2-100, preferred 4-24, most preferably 4-19, the weight ratio of one ester/diester in its Chinese style (I)/three esters is 45-90/5-40/1-20, more preferably 50-90/9-32/1-12, its Chinese style (I) is 3-0.02 with the weight ratio of formula (II), preferred 3-0.1,1.5-0.2 most preferably, the mixture Chinese style (II) that wherein most preferably forms compound is more than (I).

The ethoxylated glycerol type compound that can be used in this composition is produced by Kao company and is sold with trade(brand)name Levenol, for example average EO be 6 and the mol ratio of coconut fatty acid and glycerine be 0.55 Levenol F-200 or on average EO be 17 and the mol ratio of tallow fatty acid and glycerine be 1.0 Levenol V501/2.The mol ratio of preferred fatty acid and glycerine is lower than 1.7, more preferably less than 1.5, and most preferably is lower than 1.0.The molecular weight of ethoxylated glycerol type compound is 400-1600, and pH (50g/l water) is 5-7.The Levenol compound does not almost stimulate people's skin and has by what Wickbold methodBias-7d measured and is higher than 90% initial biodegradability.Two examples of this Levenol compound are to have 17 ethoxylation groups and are that molecular weight that 1.0 tallow fatty acid obtains is 1465 Levenol V-501/2 and has 6 ethoxylation groups and be the Levenol F-200 that 0.55 coconut fatty acid obtains by the ratio of lipid acid and glycerine by the ratio of lipid acid and glycerine.Levenol F-200 and Levenol V-501/2 are made up of the mixture of formula (I) and formula (II).The Levenol compound has＞ecological oxicity (ecoxicity) that the algal grown of 100mg/l suppresses; The Daphnia acute toxicity of＞100mg/l and＞the fish acute toxicity of 100mg/l.Measure according to the biodegradable OECD 301B of acceptable, these Levenol compounds have 60% the rapid biodegradability that is higher than for minimum desirable value.Also can be used for polyester non-ionic compound in this composition Crovol PK-40 and the Crovol PK-70 that the Croda GMBH of Holland produces that serve as reasons.Crovol PK-40 is polyoxyethylene (12) the palm nuclear glyceryl ester with 12 EO groups.For preferred CrovolPK-70 is polyoxyethylene (45) the palm nuclear glyceryl ester with 45 EO groups.The more information of these nonionogenic tensides can find in US5719114,

Another kind of suitable ionic surfactant pack is drawn together the polyhydroxy fatty acid amide class.These materials more detailed are described in the US5 that authorized Pan/Gosselink on July 26th, 1994, and 332,528, it is added herein by reference.These polyhydroxy fatty acid amides have following general formula:

Wherein: R ¹Be H, C ₁-C ₄Alkyl, 2-hydroxyethyl, 2-hydroxypropyl or its mixture, preferred C ₁-C ₄Alkyl, more preferably C ₁Or C ₂Alkyl, most preferably C ₁Alkyl (being methyl); And R ²Be C ₅-C ₃₁Alkyl, preferred straight chain C ₇-C ₁₉Alkyl or alkenyl, more preferably straight chain C ₉-C ₁₇Alkyl or alkenyl, most preferably straight chain C ₁₁-C ₁₅Alkyl or alkenyl, or its mixture; And Z is polyhydroxy alkyl or the alkoxy derivative (preferred ethoxylation or propoxylation) with straight-chain alkyl chain of at least 3 hydroxyls that directly link to each other with the straight-chain alkyl chain.Z is preferably obtained by reducing sugar in reductive amination process; More preferably Z is glycosyl (glycityl).Suitable reducing sugar comprises glucose, fructose, maltose, lactose, semi-lactosi, seminose and wood sugar.As raw material, can use high-sucrose maize treacle, high-fructose corn syrup and high malt sugar maize treacle and top listed various sugar.These maize treacle can obtain to be used for the sugar component mixture of Z.Be interpreted as, never plan to get rid of other suitable raw material.Z is preferably selected from :-CH ₂-(CHOH) _n-CH ₂OH ,-CH (CH ₂OH)-(CHOH) _N-1-CH ₂OH ,-CH ₂-(CHOH) ₂(CHOR ') (CHOH)-CH ₂OH and alkoxy derivative thereof, wherein n is the integer of 3-5, R ' is H or ring-type or aliphatic monose.Most preferably n is 4 glycosyl, particularly-and CH ₂-(CHOH) ₄-CH ₂OH.

R ' can be for example N-methyl, N-ethyl, N-propyl group, N-sec.-propyl, N-butyl, N-2-hydroxyethyl or N-2-hydroxypropyl.

R ²-CO-N＜can be is cocoamide, stearylamide, oleylamide, laurylamide, myristic amide, decyl amide, palmitic amide, tallow acid amides etc. for example.

Z can be 1-deoxy-glucose base, 2-deoxidation fructosyl, 1-deoxidation malt-base, 1-deoxidation lactose base, 1-deoxy-galactose base, 1-deoxymannose base, 1-deoxidation maltotriose glycosyl etc.

The method for preparing polyhydroxy fatty acid amide is in the art for known.In general, they can be by following preparation: in the reductive amination reaction alkylamine and reducing sugar reaction are formed the many azanols of corresponding N-alkyl, in condensation/amination step the many azanols of this N-alkyl and fatty aliphatic ester or tri-glyceride are reacted formation N-alkyl, N-polyhydroxy fatty acid amide product then.The method for compositions that preparation contains polyhydroxy fatty acid amide is disclosed in for example following document: February 18 nineteen fifty-nine by the disclosed GB809060 of Thomas Hedley company limited, the US2965576 that authorizes E.R.Wilson December 20 nineteen sixty, authorize the US2703798 of Anthony M.Schwartz March 8 nineteen fifty-five and authorized the US1985424 of Piggott on December 25th, 1934, they all are added herein by reference.

The example of these tensio-active agents comprises C ₁₀-C ₁₈N-methyl or N-hydroxypropyl, glucamide class.This N-propyl group is to N-hexyl C ₁₂-C ₁₆Glucamide can be used for reducing lathering property.

Preferred acid amides is C ₈-C ₂₀Aminoacyl amine, a glycolyl amine, diglycollic amide class and isopropanol amide class.

Another kind of suitable tensio-active agent is the alkylolamide tensio-active agent, comprises glutamine, a glycollic amide and the diglycollic amide of the lipid acid with the acyl moiety that contains about 18 carbon atoms of about 8-.These materials are expressed from the next:

R wherein ₁For having about 7-21, saturated or unsaturated, the no hydroxyl aliphatic hydrocarbyl of preferred 11-17 carbon atom; R ₂Represent methylene radical or ethylidene; And m is 1,2 or 3, preferred 1.The specific examples of these acid amides is Monoethanolamine MEA BASF coconut fatty acid acid amides and diethanolamine lauroyl fatty acid amide.These acyl moieties can be obtained by naturally occurring glyceryl ester such as Oleum Cocois plam oil, soybean oil and butter, but can obtain through synthetic, for example by petroleum oxidate or by Fischer-Tropsch method hydrogenation carbon monoxide.Preferred C _12-14One glycollic amide and the diglycollic amide of lipid acid.

Amphoterics-can choose wantonly adds amphoterics in this detergent composition.These tensio-active agents can broadly be described as the aliphatic derivatives of the second month in a season or tertiary amine or the aliphatic derivatives of the heterocycle second month in a season and tertiary amine, and wherein aliphatic group can be straight or branched.Aliphatic series one of substituting group contains at least about 8 carbon atoms, about 18 carbon atoms of typically about 8-, and at least one contains anionic water and add the dissolubility group, for example carboxyl, sulfonate radical, sulfate radical.Authorize people's such as Laughlin US3 referring on December 30th, 1975, the example of the amphoterics that the 19th hurdle 18-35 is capable in 929,678.Preferred amphoterics comprises C ₁₂-C ₁₈Trimethyl-glycine and sultaine (" sultaines "), C ₁₀-C ₁₈Amine oxide, and composition thereof.

When existing, amphoterics typically exists with significant quantity.More preferably composition can contain at least about 0.1%, more preferably at least about 0.2%, even more preferably at least about the amphoterics of 0.5% described composition weight.Composition also preferably contain be no more than about 20%, more preferably no more than about 15%, even more preferably no more than the amphoterics of about 10% described composition weight.

Amine oxide is an amphoterics, comprising: water-soluble amine oxides, and it contains the moieties of about 18 carbon atoms of about 10-and two and is selected from the alkyl that contains about 3 carbon atoms of the 1-that has an appointment and the part of hydroxyalkyl; The water soluble oxidized phosphine, it contains the moieties of about 18 carbon atoms of about 10-and two and is selected from the alkyl that contains about 3 carbon atoms of the 1-that has an appointment and the part of hydroxyalkyl; With water-soluble sulfoxide, it contains the moieties of about 18 carbon atoms of about 10-and one and is selected from the alkyl that contains about 3 carbon atoms of the 1-that has an appointment and the part of hydroxyalkyl.

Preferred amine oxide surfactant has following formula:

R wherein ³Be alkyl, hydroxyalkyl or alkyl phenyl or its mixture that contains about 22 carbon atoms of the 8-that has an appointment; R ⁴Be alkylidene group or hydroxy alkylidene or its mixture that contains about 3 carbon atoms of the 2-that has an appointment; X is 0-about 3; And each R ⁵Be alkyl or hydroxyalkyl that contains about 3 carbon atoms of the 1-that has an appointment or the polyoxyethylene group that contains about 3 the ethylene oxide groups of the 1-that has an appointment.R ⁵Group can be connected with each other, and for example by Sauerstoffatom or nitrogen-atoms, forms a ring texture.

These amine oxide surfactants especially comprise oxidation C ₁₀-C ₁₈Alkyl dimethyl amine and oxidation C ₈-C ₁₂Alkoxyethyl dihydroxy ethyl amine.

When existing, amine oxide surfactant typically exists with significant quantity.More preferably composition can contain at least about 0.1%, more preferably at least about 0.2%, even more preferably at least about the amine oxide surfactant of 0.5% described composition weight.Composition also preferably contain be no more than about 20%, more preferably no more than about 15%, even more preferably no more than the amine oxide surfactant of about 10% described composition weight.

The example of suitable amine oxide surfactant is given in " tensio-active agent and washing composition " (Surface Active Agents and Detergents) (volume I and II, Schwartz, Perry and Berch).

Suitable beet alkali surface activator comprises those of following general formula:

Wherein R is a hydrophobic grouping, is selected from: contain about 22 carbon atoms of the 10-that has an appointment, the alkyl of about 18 carbon atoms of preferably about 12-; Alkylaryl and arylalkyl, it contains similar carbonatoms, and wherein phenyl ring is taken as and about 2 carbon atom equivalences, and contains by the analog structure of amino or ehter bond interruption; Each R ¹For containing the alkyl of about 3 carbon atoms of 1-; R ²For containing the alkylidene group of about 6 carbon atoms of 1-.

The example of preferred trimethyl-glycine is lauryl dimethyl trimethyl-glycine, hexadecyl dimethyl betaine, lauryl amido propyl-dimethyl trimethyl-glycine, tetradecyl dimethyl betaine, tetradecyl amido propyl-dimethyl trimethyl-glycine and lauryl dimethyl ammonium trimethyl-glycine.Other suitable amidoalkyl trimethyl-glycine is disclosed in US3,950,417,4,137,191 and 4,375,421; And GB2, in 103,236, they all are added herein by reference.

Zwitterionics-zwitterionics can also be added in this detergent composition.These tensio-active agents can broadly be described as the derivative of the second month in a season or tertiary amine or the derivative of the heterocycle second month in a season and tertiary amine, the perhaps derivative of quaternary ammonium, quaternary phosphine or uncle's sulfonium compound.Authorize people's such as Laughlin US3 referring on December 30th, 1975, the 19th hurdle the 38th walks to the example of the zwitterionics of the 22nd hurdle the 48th row in 929,678.Both sexes and zwitterionics common and one or more negatively charged ion and/or nonionic surfactant combinations use.Detersive enzyme-for various purposes comprises and remove protein-based, carbohydrate-based or tri-glyceride base spot from substrate, preferably includes enzyme in the detergent composition of the present invention.Recent findings comprises chondroitinase (EP747 to the useful enzyme of washing composition of the present invention, 469A), ease variants (WO96/28566A, WO96/28557A, WO96/28556A, WO96/25489A), zytase (EP709,452A), M-Zyme (EP747,470A), lipase (GB2,297,979A, WO96/16153A, WO96/12004A, EP698,659A, WO96/16154A), cellulase (GB2,294,269A, WO96/27649A, GB2,303,147A), aluminothermy enzyme (WO96/28558A).More routinely, Shi Yi enzyme comprises: the mixture in cellulase, hemicellulase, proteolytic enzyme, glucoamylase, amylase, lipase, at, polygalacturonase, zytase, M-Zyme, reductase enzyme, oxydase, oxidation of phenol enzyme, lipoxygenase, lignoenzyme, Starch debranching enzyme, tannase, chondroitinase, aluminothermy enzyme, pentosanase, mannase (malanase), beta-glucanase, arabinofuranosidase/xylosidase or its any suitable source such as plant, animal, bacterium, fungi and yeast source.The preferred stability of selecting to be subjected to following factor affecting: pH-active and/or stable optimum condition, thermostability and activated detergent, washing assistant etc.Preferred bacterium or fungal enzyme, for example bacterial amylase and proteolytic enzyme and fungal cellulase in this respect.Preferably combination is that detergent composition contains the mixture just like the enzyme commonly used of proteolytic enzyme, amylase, lipase, at and/or cellulase.Suitable enzyme also is described in US5, in 677,272,5,679,630,5,703,027,5,703,034,5,705,464,5,707,950,5,707,951,5,710,115,5,710,116,5,710,118,5,710,119 and 5,721,202.

Composition preferably contains at least about 0.0001%, more preferably at least about 0.0005%, even more preferably at least about the enzyme of 0.001% described composition weight.Cleaning combination also preferably contain be no more than about 5%, more preferably no more than about 2%, even more preferably no more than the enzyme of about 1% described composition weight.

" detersive enzyme " used herein meaning is any enzyme that has cleaning, decontamination or other beneficial effect in cleaning combination.Preferred detersive enzyme is lytic enzyme such as proteolytic enzyme, amylase and lipase.Height preferred starch enzyme and/or proteolytic enzyme not only comprise the type of present commercially available acquisition but also comprise the improvement type.

Usually with the level that " cleaning significant quantity " enough is provided enzyme is added in washing composition or the detergent builder composition.Term " cleaning significant quantity " is meant produces for the substrate of fabric, tableware etc. for example to clean, remove dirty, decontamination, brighten, deodorization or increase any amount of new effect.In the actual terms of present article of commerce, the typical weight of organized enzyme is up to about 5mg weight, more typically 0.01mg-3mg in every gram detergent composition.In other words, the composition of this paper typically contains 0.001%-5%, the commercial enzyme goods of preferred 0.01%-1wt%.Proteolytic enzyme often enough provides the active amount of 0.005-0.1 Anson unit (AU) to be present in these article of commerce with every gram composition.With regard to some washing composition, can increase the organized enzyme content in the article of commerce ideally, so that the total amount of on-catalytic active substance is minimized, improve thus and remove spot/film forming or other net result.Higher live vol also can be gratifying in highly spissated detergent body.Proteolytic ferment-proteolytic ferment can be from animal, plant or microorganism (preferably) source.Used proteolytic enzyme includes, but is not limited to trypsinase, subtilysin, Quimotrase and elastoser proteinoid enzyme in this paper detergent composition.This paper preferably uses subtilysin proteinoid lytic enzyme.Preferred especially bacillary serine proteinase enzyme from Bacillus subtilus and/or bacillus licheniformis acquisition.

Suitable proteolytic ferment comprises commercially available Novo Industri A/SAlcalase ^(preferably), Esperase ^, Savinase ^(Copenhagen, Denmark), Gist-brocades ' Maxatase ^, Maxacal ^With Maxapem 15 ^(the Maxacal of protein design ^) (Delves spy, Holland) and subtilysin BPN and BPN ' (preferably).Preferred proteolytic enzymes also has the bacillary serine protease through modifying, for example by Genencor International, Inc. (San Francisco, markon's welfare Asia) those of Zhi Zaoing, it is described in the EP251 that authorized on December 28th, 1994, among the 446B (particularly the 17th, 24 and 98 page), also be called " proteolytic enzyme B " in this article.Authorized the US5 of Venegas on July 9th, 1991,030, the 378 bacillary serine proteinase enzyme (Genencor International) that is referred to as to modify, this paper is called it " protease A " (identical with BPN ').Particularly referring to US5, whole descriptions on 030,378 the 2nd and 3 hurdles comprise the amino sequence of protease A and variant thereof.Other proteolytic enzyme is sold with following trade(brand)name: Primase, Durazym, Opticlean and Optimase.Then, preferred proteolytic enzymes is selected from: A ' lcalase ^(Novo Industri A/S), BPN ', protease A and proteolytic enzyme B (Genencor) and composition thereof.Proteolytic enzyme B most preferably.

Special protein of interest enzyme used herein is described in US5,470,733.

At our co-pending application USSN08/136, the proteolytic enzyme described in 797 also can be included in the detergent composition of the present invention.

Another preferred protease that is referred to as " proteolytic enzyme D " is that its aminoacid sequence is at the also undiscovered carbonylic hydrolase variant of occurring in nature, it by the precursor carbonylic hydrolase by be equivalent at described carbonylic hydrolase+76 positions substitute different aminoacids with many amino-acid residues and obtain, preferably should substitute also be selected from according to April 20 nineteen ninety-five by described in the disclosed WO95/10615 of GenencorInternational people such as (in the U. S. application sequence number 08/322,676 that is entitled as " cleaning combination (Protease-ContainingCleaning Compositions) that contains proteolytic enzyme " of application on October 13rd, 1994) A.Baeck according to being equivalent to of bacillus amyloliquefaciens subtilysin counting+99, + 101, + 103, + 104, + 107, + 123, + 27, + 105, + 109, + 126, + 128, + 135, + 156, + 166, + 195, + 197, + 204, + 206, + 210, + 216, + 217, + 218, + 222, + 260, + 265 and/or+one or more amino acid residue positions in 274 substitute different aminoacids with many amino-acid residues and combine.

Useful proteolytic enzyme also is described in during following PCT openly applies for: November 9 nineteen ninety-five is by Procter; The disclosed WO95/30010 of Gambe company; November 9 nineteen ninety-five is by Procter; The disclosed WO95/30011 of Gambe company; November 9 nineteen ninety-five is by Porcter; The disclosed WO95/29979 of Gambe company.

Can be that the level of the 0.0001%-2% of composition weight adds proteolytic enzyme in the composition of the present invention by organized enzyme.

Composition preferably contains at least about 0.0001%, more preferably at least about 0.0002%, and more preferably at least about 0.0005%, even more preferably at least about the active protease of 0.001% described composition weight.Composition also preferably contain be no more than about 2%, more preferably no more than about 0.5%, more preferably no more than about 0.1%, even more preferably no more than the active protease of about 0.05% described composition weight.Amylase-can contain is useful on the amylase of removing based on the carbohydrate dirt (α and/or β).Suitable amylase has Termamyl ^(Novo Nordisk), Fungamyl ^And BAN ^(Novo Nordisk).These enzymes can be from any suitable source, for example plant, animal, bacterium, fungi and yeast source.

Composition preferably contains at least about 0.0001%, more preferably at least about 0.0002%, and more preferably at least about 0.005%, even more preferably at least about the active amylase of 0.001% described composition weight.Composition also preferably contain be no more than about 2%, more preferably no more than about 0.5%, more preferably no more than about 0.1%, even more preferably no more than the active amylase of about 0.05% described composition weight.

Amylase also comprises those described in the co-pending application PCT/DK96/00056 of WO95/26397 and Novo Nordisk.Other the specific amylase that is used for detergent composition of the present invention comprises:

(a) under the pH of 25 ℃-55 ℃ and 8-10, pass through Phadebas ^The specific activity of α-Dian Fenmei activity test determination compares Termamyl ^High at least 25% α-Dian Fenmei.This Phadebas ^The test of α-Dian Fenmei activity is described in the 9-10 page or leaf of WO95/26397.

(b) contain the αDian Fenmei of (a) of the amino sequence shown in the sequence table in the top cited literature 2 (SEQ ID), perhaps at least 80% homologous α-Dian Fenmei is arranged with the aminoacid sequence shown in this sequence table.

(c) α-Dian Fenmei of (a) that obtains from the alkalophilic bacillus kind contains following amino sequence at the N-end: His-His-Asn-Gly-Thr-Asn-Gly-Thr-Met-Met-Gln-Tyr-Phe-Glu-Trp-Tyr-Leu-Pro-Asn-Asp.

Confirm that identity is X% if compare each aminoacid sequence by algorithm (for example Lipman and Pearson are described " Science " the 227,1985,1435th page), polypeptide is considered to its parental generation amylase the X% homology is arranged so.

(d) α-Dian Fenmei (a-c), wherein this α-Dian Fenmei can obtain from the alkalophilic bacillus kind; And especially any one acquisition from bacterial strain NCIB 12289, NCIB 12512, NCIB 12513 and DSM 935.

In the context of the invention, term " can from ... acquisition " not only refer to the amylase produced by bacillus strain, and refer to by separated DNA sequence encoding from this bacillus strain and the amylase in described dna sequence dna host transformed organism, produced.

(e) has the α-Dian Fenmei that shows positive immune cross-reactivity respectively corresponding to the antibody of the α-Dian Fenmei of the aminoacid sequence of these α-Dian Fenmei in (a-d) with resisting.

(f) variant of following parental generation α-Dian Fenmei: (i) have respectively corresponding to one of aminoacid sequence shown in these α-Dian Fenmei in (a-e), perhaps (ii) has at least 80% homology with one or more described aminoacid sequences, and/or have immune cross-reactivity, and/or by having the dna sequence encoding of the identical probe hybridization of the DAN sequence of α-Dian Fenmei of one of described aminoacid sequence with coding with anti-antibody with α-Dian Fenmei of one of described aminoacid sequence; Variant wherein:

1, at least one amino-acid residue of described parental generation α-Dian Fenmei lacks; And/or

2, at least one amino-acid residue of described parental generation α-Dian Fenmei is replaced by the different aminoacids residue; And/or

3, at least one relevant with described parental generation α-Dian Fenmei amino-acid residue is inserted into;

Described variant has alpha-amylase activity and presents the relevant following performance of at least a and described parental generation α-Dian Fenmei: thermostability increase, oxidative stability increase, the reduction of Ca ionic dependent, increase at neutrality to stability and/or Alpha-starch hydrolytic activity under the high relatively pH value, under high relatively temperature the Alpha-starch hydrolytic activity increase and iso-electric point (pI) increases or reduction so that (the pI value of amylase variant and the pH of substratum mate better.

Described variant is described among patent application PCT/DK96/00056.

Other amylase of suitable this paper for example comprises that Novo is at the α-Dian Fenmei described in the GB1296839, International Bio-Synthetics, the RAPIDASE of Inc. ^TERMAMYL with Novo ^The FUNGAMYL of Novo ^Particularly useful.Improve stability, for example the enzyme engineering of oxidative stability is known.For example referring to " journal of biological chemistry (J.BiologicalChem.) " the 260th volume o. 11th, in June, 1985,6518-6521 page or leaf.Some of the preferred embodiment of the invention can be used in the washing composition of for example automatic dishwashing class has stability-enhanced amylase, particularly with the industrial TERMAMYL that uses in 1993 ^The reference point of measuring is compared the amylase that oxidative stability improves.These preferred amylase have " stability-enhanced " diastatic characteristic herein, at least characterize by the following raising that one or more can be measured: oxidative stability is to the oxidative stability of hydrogen peroxide/tetraacetyl ethylene diamine in the damping fluid of 9-10 at pH for example; Thermostability is for example in conventional wash temperature according to appointment under 60 ℃; Or alkaline stability, for example under the pH of about 8-about 11, be reference point determination of amylase defined above relatively.Can use the disclosed any engineering test in this area to measure stability.For example referring to disclosed parameter among the WO9402597.Can obtain stability-enhanced amylase from Novo or GenencorInternational.The highly preferred amylase of a class has the site-directed mutagenesis of use by one or more amylase bacillus herein, and particularly (denominator that the amylase bacillus obtains, and do not consider whether a kind of, two or more amylase strains are its direct precursor.The preferred amylase of oxidative stability raising and the reference amylase of identifying above of using is especially for the bleaching of this paper, more preferably in the detergent composition of oxygen bleaching (different with chlorine bleaching).These preferred amylase comprise: (a) WO9402597 (Novo that quotes previously of this paper, on February 3rd, 1994) a kind of amylase in, it also is described as using L-Ala or Threonine, preferred Threonine, replacement is positioned at the mutant of the methionine residues of bacillus licheniformis α-Dian Fenmei the 197th position, is known as TERMAMYL ^, or the mutant of the homology change in location of similar parental generation amylase such as bacillus amyloliquefaciens, Bacillus subtilus or stearic acid thermophilic bacteria; (b) stability-enhanced amylase is described in C.Mitchinson in the article of being entitled as in the 207th the national meeting of the whole America Chemical Society 13-17 day in March, 1994 " oxidation resistant α-Dian Fenmei (OxidativelyResistant alpha-Amylases) " by Genencor International.Here it should be noted that the SYNTHETIC OPTICAL WHITNER in the automatic dishwashing detergent makes the α-Dian Fenmei inactivation, but Genencor has prepared the amylase that oxidative stability improves by bacillus licheniformis NCIB8061.Methionine(Met) (Met) is confirmed as most possible adorned residue.Met once replaces one in position 8,15,197,256,304,366 and 438, obtain the specific mutant body, particularly importantly M197L and M197T, and the M197T variant is the most stable expression variant.Measure CASCADE ^And SUNLIGHT ^In stability; (c) the particularly preferred amylase of this paper is included in and has the additional amylase variant of modifying and can be from transferee Novo with DURAMYL in the direct parental generation described in the WO9510603A ^Obtain.The amylase that other particularly preferred oxidative stability improves comprise Genencor International at WO9418314 and Novo at described in the WO9402597 those.The amylase that can use arbitrarily other oxidative stability to improve is for example obtained by site-directed mutagenesis by obtainable diastatic known chimeric, the hybridization or the parental generation form of simply suddenling change.Can utilize other preferred enzyme modification.WO9509909A referring to Novo.

The cellulase that can be used for this paper had both comprised that bacteria type also comprised the fungi type, and preferred pH optimum condition is 5-9.5.Authorized people's such as Barbesgoard US4 on March 6th, 1984,435,307 disclose from unusual humicola lanuginosa (Humicola insolens) or Humicola strain DSM 1800 or have belonged to the suitable fungal cellulase of fungi of cellulase-producing 212 of Aeromonas and the cellulase that extracts from the liver pancreas of sea mollusk Dolabella Auricula Solander.Suitable cellulase also is disclosed in GB-A-2075028; Among GB-A-2095275 and the DE-OS-2247832.CAREZYME ^And CELLUZYME ^(Novo) particularly useful.Also referring to the WO9117243 of Novo.

Composition preferably contains at least about 0.0001%, more preferably at least about 0.0002%, and more preferably at least about 0.0005%, even more preferably at least about the active cellulase and/or the peroxidase of 0.001% described composition weight.Composition also preferably contain be no more than about 2%, more preferably no more than about 0.5%, more preferably no more than about 0.1%, even more preferably no more than the active cellulase and/or the peroxidase of about 0.05% described composition weight.

Can think the at [EC 3.1.1.50] of certain kinds lipase, promptly not need the lipase of interface activation, also be fit to.Adding in detergent composition for example is described among the WO-A-88/09367 (Genencor).Lipase-suitable lipase comprises by the pseudomonas microorganism belonging to genus, as Situ Ci Shi aeruginosa atcc 19.154, and those of production, as GB1, disclosed in 372,034.Suitable lipase comprises by microorganism Pseudomonas fluorescens IAM 1057 and produces and show those of positive immunological cross-reaction with this lipase antibody.This lipase can be from Amono Pharmacevtical Co., Ltd. (AmanoPharmaceutical Co.Ltd.), and Japan Nagoya obtains with trade(brand)name Lipase P " Amano, ", and this paper back is referred to as " Amano-P ".Other suitable lipase has for example M1 Lipase ^And Lipomax ^(Gist-Brocades) lipase.Other suitable commercial lipase comprises Amano-CES, lipase by the acquisition of thickness look bacillus, for example from Toyo Jozo Co., Tagata, Japan thickness look bacillus steatolysis variant (var.Lipolyticum) NRRLB 3673, from U.S.'s biochemical corp (U.S.BiochemicalCorp.), the U.S. and Disoynth company, the thickness look bacillus lipase of Holland and the lipase that obtains by the gladiolus pseudomonas.Obtain and can be purchased also referring to EP341 947 LIPOLASE from Novo by the fine hair humicola lanuginosa ^Enzyme is the preferred fat enzyme that is used for this paper.Lipase that antioxidase is stable and amylase variant are described among the WO9414951 of Novo.Also referring to WO9205249 and RD94359044.

Highly preferred lipase is the D96L lipolytic enzyme variants of the native lipase that obtained by the fine hair humicola lanuginosa described in U. S. application sequence number 08/341,826.(also referring to patent application WO92/05249, promptly aspartic acid (D) residue at 96 places replaces with leucine (L) in the position in the native lipase that is obtained by the fine hair humicola lanuginosa.According to this nomenclature, the described aspartic acid at 96 places is shown as with leucic replacement in the position: D96L.) preferably use fine hair humicola lanuginosa strain DSM 4106.

Although a large amount of applications are arranged, only obtain and found to be widely used as so far the auxiliary agent of cleaning product with the lipase that aspergillus oryzae is produced as the host by the fine hair humicola lanuginosa about lipase.It can be from Novo Nordisk with trade(brand)name Lipolase ^With Lipolase Ultra ^Obtain, as mentioned above.In order to make the detergency ability optimizing of Lipolase, Novo Nordisk has made many variants.Described in WO92/05249, the lard spot efficient of going of the D96L variant of natural fine hair humicola lanuginosa lipase is that (amount of enzyme relatively is that the 35944th phase of Research Disclosure that 4.4 times of .1994 of 0.075-2.5mg albumen/l) were published by Novo Nordisk at March 10 to disclose lipase Variant (D96L) can be that 0.001-100mg (5-500000 LU/l) adds by the respective amount of lipase Variant in every liter of washing lotion to wild-type lipase.

Composition preferably contains at least about 0.0001%, more preferably at least about 0.0002%, and more preferably at least about 0.0005%, even more preferably at least about the active lipase of 0.001% described composition weight.Composition also preferably contain be no more than about 2%, more preferably no more than about 0.5%, more preferably no more than about 0.1%, even more preferably no more than the active lipase of about 0.05% described composition weight.

Can also contain the various carbohydrases of giving anti-microbial activity in the present invention.These enzymes comprise endoglycosidase, II type endoglycosidase and the glucuroide that is disclosed among the US5041236,5395541,5238843 and 5356803, and disclosed content in these documents is added herein by reference.Certainly, also can use other enzyme, comprise peroxidase, oxygenase and various other enzyme with anti-microbial activity.

Many enzyme materials and its mode in synthetic detergent composition of adding also is described in the WO8908694A of the WO9307263A of Genencor International and WO9307260A, Novo and authorized people's such as McCarty US3 on January 5th, 1971, in 553,139.Enzyme also is disclosed in the US4 that authorized people such as Place on July 18th, 1978, authorizes the US4 of Hughes on March 26th, 101,457 and 1985, in 507,219.The method that is used for the enzyme material of liquid washing agent goods and adds in these goods is disclosed in the US4 that authorized people such as Hora on April 14th, 1981, in 261,868.The enzyme that is used for washing composition can be by various consistent.Authorize people US3 such as Gedge on August 17th, 1971, authorized the EP199 of Venegas on October 29th, 600,319,1986, open and illustrated the enzyme stabilization technique in 405 and EP200,586.For example at US3, the enzyme stabilising system has also been described in 519,570.The useful bacillus species AC13 that gives proteolytic enzyme, zytase and cellulase is described among the WO9401532A of Novo.

When any enzyme is present in the composition, can also contain the enzyme stabilising system in the composition of the present invention.It is about 10% that the preferred composition of enzyme stabilising system-this paper can contain the 0.001%-that has an appointment in addition, and preferably about 0.005%-is about 8%, most preferably from about the enzyme stabilising system of about 6% weight of 0.01%-.This enzyme stabilising system can for can with used proteolytic enzyme or the compatible any stabilising system of other enzyme in the composition of this paper.These stabilising systems can comprise calcium ion, boric acid, propylene glycol, the short chain carboxy acid, boronic acid containing (boronic acid), polyol and composition thereof, for example authorized people's such as Hora US4 on April 4th, 1981,261,868, authorize 4 of Tai September 13 nineteen eighty-three, 404,115, people's such as Letton 4,318,818, authorized people's such as Guildert 4 on January 6th, 1981,243,543, authorized 4,462 of Boskamp on July 31st, 1984,922, authorized 4 of Boskamp on July 30th, 1985, authorized 4,537 of Severson Jr. on August 27th, 532,064 and 1985,707, they all are added herein by reference.

Composition preferably contains at least about 0.001%, more preferably at least about 0.005%, even at least about the enzyme stabilising system of 0.01% described composition weight.Composition also preferably contain be no more than about 10%, more preferably no more than about 8%, more preferably no more than the enzyme stabilising system of about 6% described composition weight.

A kind of stable scheme is that the water-soluble sources with calcium and/or magnesium ion is used for providing in these ionic final compositions to these enzymes.Calcium ion is more effective than magnesium ion usually, if only use a kind of ionic to talk about preferred calcium ion.Typical detergent composition, particularly liquid, it is about 30 to contain the 1-that has an appointment, and preferably about 2-is about 20, and the final detergent composition of the about 12mmol calcium ion/l of 8-more preferably from about is although can change according to multiplicity, type and the content of the enzyme that comprises adding.Preferred water-soluble calcium or the magnesium ion of using for example comprises calcium chloride, calcium hydroxide, calcium formiate, calcium malate, calcium maleate, calcium hydroxide and lime acetate; More conventionally can use calcium sulfate or corresponding to the magnesium salts of illustration calcium salt.And the calcium of increasing amount and/or magnesium can be used for for example promoting the grease cutting action of the tensio-active agent of certain type naturally.Yet special preferred composition does not contain the calcium ion of adding, even more preferably composition does not have calcium ion.

In addition-stable scheme is to use borate family.Referring to the US4 of Severson, 537,706.The borate stablizer, when using, its content can up to composition 10% or higher, although more typically its content is applicable to liquid washing agent up to the boric acid of about 3wt% or other borate mixture such as borax or borate.Can use substituted boracic acid such as phenyl-boron dihydroxide, fourth boric acid, bromophenyl boric acid etc. be replaced propionic acid, although use these to replace the total content that boron derivatives can reduce boron in the detergent composition.

In addition, attack enzyme or make it inactivation for the chlorine bleach that prevents to be present in many waterworkss, it is about 10% to add 0%-in composition of the present invention, the chlorine bleach of about 6% weight of preferably about 0.01%-or the scavenging agent of oxygen bleaching agent.Although the cl content in the water may be little, typically be the about 1.75ppm of about 0.5ppm-, the obtainable chlorine in the whole volume water that contacts with enzyme in the wash up process is often big; Enzyme stability may be a problem when therefore using.

Suitable chlorine scavenger negatively charged ion is the salt that contains ammonium cation.These can be selected from: reducing substances such as sulphite, bisulfite, thiosulfite, iodide etc.; Antioxidant such as carbonate, ascorbate salt etc.; Organic amine such as ethylenediamine tetraacetic acid (EDTA) (EDTA) or its an alkali metal salt and Monoethanolamine MEA BASF (MEA), and composition thereof.Also can use the removing negatively charged ion of other routine such as sulfate radical, bisulfate ion, carbonate, bicarbonate radical, percarbonic acid root, nitrate radical, chlorion, borate, sodium perborate tetrahydrate, Sodium peroxoborate monohydrate, percarbonic acid root, phosphate radical, condensed phosphoric acid root, acetate, benzoate anion, citrate, formate, lactate, malate, tartrate anion, salicylate etc., and composition thereof.The optional detergent builder compound that contains in washing assistant-composition of the present invention.In solid articles, washing assistant uses as the absorption agent of tensio-active agent sometimes.Perhaps, according to its required purposes, some composition can with or organic or inorganic complete water-soluble washing assistant preparation.

Suitable silicate-like builder comprise water-soluble and aqueous solid type and comprise have chain type, those and amorphous solid silicate or other type of stratiform or three-dimensional structure, for example particularly be applicable to the non-structure liquid washing agent.Preferred as alkali silicate, particularly SiO ₂: Na ₂O comprises that than those liquid and solid at 1.6-1 to 3.2-1 Pq Corp. is with trade(brand)name BRITESIL ^The moisture 2-ratio of the solid silicate of selling, for example BRITESIL H ₂O; And layered silicate, for example authorized described in the US4664839 of H.P.Rieck those on May 12nd, 1987.NaSKS-6 is abbreviated as " SKS-6 " sometimes, is the crystalline layered no aluminium (Na that is sold by Hoechst ₂SiO ₅Morphology silicate, and particularly preferably in the particulate composition.Referring to the preparation method among DE-A-3417649 and the DE-A-3742043.This paper also can selectively use other laminar silicic acid salt, for example has general formula NaMSi _xO _2z+1.yH ₂Those of O, wherein M is Na or H, x is for number 1.9-4, and is preferred 2, and y is number 0-20, preferred 0.Also comprise NaSKS-5, NaSKS-7 and NaSKS-11 from the laminar silicic acid salt of Hoechst with α, β and γ layer silicate form.Other silicates also can use, Magnesium Silicate q-agent for example, and it can be used as the labilizer (crispeningagent) in the particle, and as the component of foam control system.

Also suitable synthetic crystallization ion-exchange material or its hydrate: the xM that uses the composition of following general formula representative of this paper with chain structure and anhydrous form ₂O.ySiO ₂.zM ' and O, wherein M is Na and/or K, M ' is Ca and/or Mg; Y/x is that 0.5-2.0 and z/x are 0.005-1.0, authorizes people's such as Sakaguchi US5 as June 27 nineteen ninety-five, instruction in 427,711.

The silico-aluminate washing assistant, particularly useful in granulated detergent as zeolites, but also can add in liquid, paste or the gel.Suitable this purpose be to have those of following empirical formula: [M _z(AlO ₂) _z(SiO ₂) _v] .xH ₂O, wherein z and v are at least 6 integer, M is a basic metal, preferred Na and/or K, the mol ratio of z and v is that 1.0-is about 0.5, x is the integer of 15-264.Silico-aluminate can be crystallization or armorphous and can be for naturally occurring or obtain through synthetic.A kind of silico-aluminate production method is authorized on October 12nd, 1976 among people's such as Krummel the US3985669.Preferred synthetic crystal aluminosilicate ion-exchange material can zeolite A, zeolite P (B), X zeolite and what and zeolite P are different is called zeolite MAP and obtains.Can use natural type, comprise clinoptilolite.Zeolite A has following formula: Na ₁₂[(AlO ₂) ₁₂(SiO ₂) ₁₂] .xH ₂O, wherein x is 20-30, particularly 27.Also can use dehydration zeolite (x=0-10).The particle diameter of preferably aluminosilicate salt is about 0.1-10 micron (diameter).

Replacement or the detergent builder compound except this paper silicate recited above and silico-aluminate can be chosen wantonly and be included in this paper composition, for example help to control mineral substance, particularly Ca and/or Mg, hardness of washing water or help to remove lip-deep particulate fouling.Washing assistant can be operated through various mechanism, thereby comprises by ion-exchange and by providing surface and hardness ions than the easier precipitation hardness ions in the surface of article to be cleaned to form solubility or insoluble mixture.The content of washing assistant can great changes have taken place according to the physical form of end-use and composition.Built detergent typically contains the washing assistant at least about 1%.It is about 50% that flowing product typically contains the 5%-that has an appointment, more typically the washing assistant of 5%-35%.Particle product comprises that typically about 10%-is about 80%, more typically the washing assistant of 15%-50% detergent composition weight.Do not get rid of low or high-load washing assistant yet.For example, some goods can be without composite, and promptly composition does not contain washing assistant, for example in some manual dishwashing composition.

The washing assistant that this paper suits can be selected from: phosphoric acid salt and polyphosphate, particularly sodium salt; Carbonate, supercarbonate, sesquicarbonate and carbonate inorganics except that yellow soda ash and concentrated crystal soda; Organic one-, two-, three-and four-carboxylate salt, particularly with the water-soluble nonsurfactant carboxylate salt and the oligomeric or water-soluble low molecular weight polymeric carboxylates of acid, sodium, potassium or alkanol ammonium salt form, comprise aliphatic series and aromatics type; And phytic acid.These can replenish with borate, for example are used for pH-buffering purpose, perhaps replenish with vitriol, and sodium sulfate particularly, and other may and/or contain the very important filler or the carrier of design of the detergent composition of washing assistant to stabilized surfactant arbitrarily.

Can use the washing assistant mixture, be sometimes referred to as " builder system ", typically contain two or more conventional washing assistants, optional additional with sequestrant, pH-buffer reagent or filler, although these materials of back are considered respectively usually when describing amount of substance.In the relative quantity of tensio-active agent in this washing composition and washing assistant, preferred builder system is about 60 with the weight ratio of tensio-active agent and washing assistant typically: 1-preparation in about 1: 80.Ratio described in some preferred detergent for washing clothes is 0.90: 1.0-4.0: 1.0, more preferably 0.95: 1.0-3.0: 1.0.

Often preferred phosphorus-containing detergent washing assistant includes, but not limited to basic metal, ammonium and the alkanol ammonium salt of Tripyrophosphoric acid such as tripolyphosphate, tetra-sodium, glassiness polymerization metaphosphoric acid in allowed by law place; And phosphonate.

Suitable carbonate builders comprises alkaline-earth metal and alkaline carbonate, as disclosed German patent application 2 on November 15th, 1973,321, disclosed in 001, although for example can use as required sodium bicarbonate, yellow soda ash, concentrated crystal soda and other carbonate inorganics such as urao or arbitrarily easily the composite salt of yellow soda ash and lime carbonate as when anhydrous, having composition 2Na ₂CO ₃.CaCO ₃Those, and even comprise the lime carbonate class of calcite, aragonite and vaterite particularly having the form of high surface area with respect to fine and close calcite.

Suitable " the organic detergent builder compound " that is used for cleaning combination just as described herein comprises the polycarboxylic acid salt compound, comprises the dicarboxylate and the tricarboxylate of water-soluble nonsurfactant.More typical washing assistant polycarboxylate has many carboxylate groups, preferably at least 3 carboxylate salts.The carboxylate salt washing assistant can sour, partly neutral, neutral or excessively alkalization form preparation.When using with salt form, preferred as alkali such as sodium, potassium and lithium or alkanol ammonium salt.The polycarboxylate washing assistant comprises the ether polycarboxylate, and oxo disuccinate for example is referring to the US3128287 that authorized Berg in April 7 in 1964 with authorized people's such as Lamberti US3635830 on January 18th, 1972; Authorized " TMS/TDS " washing assistant of people's such as Bush US4663071 on May 5th, 1987; With other ether carboxylate that comprises ring-type and alicyclic compound, those described in the US3923679,3835163,4158635,4120874 and 4102903 for example.

Other suitable organic detergent builder compound is the multipolymer, 1 of ether hydroxy-polycarboxylate, maleic anhydride and ethene or vinyl methyl ether, 3,5-trihydroxybenzene-2,4,6-trisulfonic acid and carboxy methoxy-succinic acid, as Different Alkali metal, ammonium and the substituted ammonium salt of the poly-acetate of ethylenediamine tetraacetic acid (EDTA) and nitrilotriacetic acid(NTA) and benzene hexacarboxylic acid, succsinic acid, polymaleic acid, benzene 1,3,5-tricarboxylic acid, carboxy methoxy-succinic acid and soluble salt thereof.

The Citrate trianion washing assistant, for example citric acid and soluble salt thereof owing to the operability and the biological degradability of renewable origin, are the important carboxylate salt washing assistants of for example light-duty liquid washing agent therefore.Citrate trianion also can be used in the granulated detergent, particularly with the combination of zeolite and/or layered silicate in.Oxo disuccinic acid salt also is useful especially in this composition and combination.

When allowing, particularly in the strip goods, can use alkali metal phosphate such as tripoly phosphate sodium STPP, trisodium phosphate and sodium orthophosphate.Also can use as ethane-1-hydroxyl-1 the phosphonate washing assistant of 1-diphosphonate and other known phosphonate, US3 for example, 159,581,3,213,030,3,422,021,3,400, in 148 and 3,422,137 those, and can have the ideal anti-scaling property.

Some detergent surfactant or its short chain homologue also have the effect of washing that helps.For clear and definite formula computation purpose, when they had the surfactivity ability, these materials were summarized as the detergency tensio-active agent.Authorize among the US4566984 of Bush disclosedly 3 by January 28 in 1986, it is functional that 3-dicarboxyl-4-oxa--1,6-hexanodioic acid salt and related compound thereof are described the washing assistant of preferred type.The succsinic acid washing assistant comprises C ₅-C ₂₀Alkyl and alkenyl succinic and salt thereof.The succinate washing assistant also comprises: dodecyl succinate salt, tetradecyl succinate, hexadecyl succinate, 2-dodecenyl succinic succinate (preferably), 2-15 carbene base succinates etc.The dodecyl succinate salt is described in the disclosed european patent application 86200690.5/0200263 on November 5th, 1986.Lipid acid, for example C ₁₂-C ₁₈Monocarboxylic acid can also add in the composition together separately or with aforementioned washing assistant, particularly Citrate trianion and/or succinate washing assistant, thereby additional washing assistant activity is provided.Other suitable polycarboxylate is disclosed in US4144226 that authorized people such as Crutchfield on March 13rd, 1979 and the US3308067 that authorized Diehl on March 7th, 1967.Also referring to the US3723322 of Diehl.

The inorganic builders material of operable other type has formula (M _x) _iCa _y(CO ₃) _z, wherein x and i are the integer of 1-15, and y is the integer of 1-10, and z is the integer of 2-25, M _iBe positively charged ion, wherein at least one is water miscible, and satisfies the equation ∑ _I=1-15(x _i* M _i)+2y=2z is so that these goods have neutrality or " balance " electric charge.These washing assistants are referred to as " mineral substance washing assistant " in this article, and the example of these washing assistants, its Use and preparation method can be at US 5,707, find in 959.Another kind of suitable inorganic builders is a Magnesiosilicates, referring to WO97/0179.

The suitable polycarboxylate washing assistant that is used for this paper comprises toxilic acid, citric acid, preferably water dissolubility salt form, formula R-CH (COOH) CH ₂(COOH) succinic acid derivative, R is C in this formula _10-20Alkyl or alkenyl, preferred C _12-16, perhaps wherein R can use hydroxyl, sulfo-time sulfonyl, sulfo group substituting group to replace.Also can contemplate the mixture of these suitable polycarboxylate washing assistants, comprise the mixture of toxilic acid and citric acid.Specific examples comprises dodecyl succinate salt, tetradecyl succinate, hexadecyl succinate, 2-dodecenyl succinic succinate, 2-tetradecene base succinate.The succinate washing assistant preferably uses with its water-soluble salt form, comprises sodium, potassium, ammonium and alkanol ammonium salt.

Other suitable polycarboxylate is the mixture of oxo disuccinate and one succsinic acid of the tartrate described in US4663071 and tartrate disuccinic acid.

Particularly with regard to the liquid of this paper was implemented, the lipid acid washing assistant that is applicable to this paper was saturated or unsaturated C _10-18Lipid acid and corresponding soap.Preferred saturated kind has 12-16 carbon atom in alkyl chain.Preferred unsaturated fatty acids is an oleic acid.Other the preferred builder system that is used for liquid composition is based on dodecenyl succinic succsinic acid and citric acid.

Composition preferably contains at least about 0.2%, more preferably at least about 0.5%, and more preferably at least about 3%, even more preferably at least about the washing assistant of 5% described composition weight.Cleaning combination also preferably contain be no more than about 50%, more preferably no more than about 40%, more preferably no more than about 30%, even more preferably no more than the washing assistant of about 25% described composition weight.The existence of magnesium ion-magnesium (divalence) ionic has improved various compositions, promptly contains the smeary cleaning performance of the composition of alkyl ethoxy sulfate and/or polyhydroxy fatty acid amide.When these compositions were used for containing considerably less bivalent ions soft water, this particularly protruded.Although it is believed that and do not want to be limited by theory, magnesium ion has increased parcel to tensio-active agent in oil/water termination, has therefore reduced interfacial tension and has improved the grease cleaning performance.The present composition that contains magnesium ion has good degreasing, proves the skin gentleness, and has good storage stability.

Composition preferably contains at least about 0.01%, more preferably at least about 0.015%, and more preferably at least about 0.02%, even at least about the magnesium ion of 0.025% described composition weight.Cleaning combination also preferably contain be no more than about 5%, more preferably no more than about 2.5%, more preferably no more than about 1%, even more preferably no more than the magnesium ion of about 0.05% described composition weight.In any case, the amount of magnesium ion always with composition in mole or lower such as the diamines that exists than it.

The preferably magnesium ion joins in the composition of the present invention with oxyhydroxide, muriate, acetate, formate, oxide compound or nitrate.

Because the uncompatibility of divalent ion, particularly magnesium ion and hydroxide ion, therefore may be difficult to prepare these in alkaline pH matrix contains bivalent ions composition.When divalent ion and alkaline pH during all with surfactant mixture combination of the present invention, obtain than only by alkaline pH or divalent ion obtain separately will be good the grease cleaning performance.Yet, in storage, owing to form precipitation of hydroxide, so the poor stability of these compositions.Therefore, also may need to add the sequestrant that this paper discusses later.Diamines-preferred used diamines of the present invention does not have impurity basically.That is, " not having basically " meaning is that the purity of diamines surpasses 95%, and is promptly preferred 97%, more preferably 99%, even more preferably 99.5%, there is not impurity.The example of the impurity that may exist in the diamines of commercial offers comprises the 2-methyl isophthalic acid, 3-diaminobutane and alkyl hydrogenation pyrimidine.And, for fear of two amine degradations with form ammonia, it is believed that these diamines answer the oxygen-free reagent.In addition, if amine oxide and/or other tensio-active agent exist, amine oxide or tensio-active agent should not contain hydrogen peroxide.The preferred content of hydrogen peroxide in the surfactant pastes of amine oxide or amine oxide is 0-40ppm, more preferably 0-15ppm.Amine impurity in amine oxide and the trimethyl-glycine, if present, the level that relates to regard to hydrogen peroxide above should being minimized to.

When composition contained enzyme, the composition that preparation does not contain hydrogen peroxide was very important.Hydrogen peroxide can add any impact of performance in the composition with enzyme reaction and destructive enzyme.Even a spot of hydrogen peroxide also can bring problem to containing enzyme preparation.Yet diamines can and play enzyme stabilizers with any peroxide reactions that exists, and prevents hydrogen peroxide and enzyme reaction.Unique defective by the diamines stabilized enzyme is that the nitride produced it is believed that and brings stench, and it may reside in the composition that contains diamines.Diamines plays enzyme stabilizers also have been prevented to give the advantage that composition has at first to composition, i.e. grease cleaning, whipability, solvability and low-temperature stability.Therefore, preferably contain the component of hydrogen peroxide hardly and/or use non-diamines antioxidant (even diamines can play enzyme stabilizers by using, owing to may produce malodorous compound) and reduce the amount of the diamines that can obtain of carrying out its primary action, the amount of the hydrogen peroxide that exists as impurity in the present composition is minimized.

Also preferred composition of the present invention does not have " stench ".That is, the smell of headspace does not bring negative olfaction reaction to the user.This can realize by many modes, comprises using spices to cover any undesirable smell, use the stablizer of for example antioxidant, sequestrant etc. and/or using pure basically diamines.It is believed that and do not want to be limited by theory that the impurity that is present in the diamines is malodorous main source in the composition of the present invention.These impurity can form when preparation and storage diamines.They can also form when the preparation and the storage present composition.For example use the stablizer of antioxidant and sequestrant to suppress and/or prevented these impurity from preparation when the user finally uses and composition, form later on.Therefore, most preferably by adding spices, stablizer and/or using the diamines that does not have impurity basically to remove, suppress and/or prevent that these stenches from forming.

It is about 11.5 at about 8.0-that the preferred organic diamine of one class is pK1 and pK2, and preferably about 8.4-is about 11, even those of 8.6-about 10.75 more preferably from about.Consider that preferable material is 1,3-two (methylamine)-hexanaphthene, 1,3-propylene diamine (pK1=10.5 from performance and supply side; PK2=8.8), 1,6-hexanediamine (pK1=11; PK2=10), 1,3-pentamethylene diamine (Dytek EP) (pK1=10.5; PK2=8.9), 2-methyl 1,5-pentamethylene diamine (Dytek A) (pK1=11.2; PK2=10.0).Other preferred material is primary/primary diamines that alkylidene group is spaced apart C4-C8.In general, it is believed that primary diamines is more preferred than the second month in a season and tertiary diamine.

The definition of pK1 and pK2-used herein " pKa1 " and " pKa2 " are the amounts of those skilled in the art with " pKa " known type, with pKa to be used for this paper with the known same way as of chemical field technician.The value that this paper quotes can from for example Smith and Martel " the neutrality constant: the 2nd the volume, amine (Critical Stability Constants:Volume2, Amines) " Plenum Press, NY and London obtains in 1975 the document.Can be about the out of Memory of pKa from the associated companies document, for example obtain in the information that provides by Dupont (diamines supplier).

Operate definition as this paper, the pKa of diamines is defined in all aqueous solution under 25 ℃, and ionic strength is 0.1-0.5M.PKa is can be with the equilibrium constant of temperature and ionic strength variation; Therefore, the value of reporting in the document is inequality sometimes, and this depends on measuring method and condition.In order to eliminate polysemy, correlated condition that pKa of the present invention is used and/or parameter such as this paper or " the neutrality constant: the 2nd volume, amine (Critical Stability Constants:Volume 2, Amines) " in defined.A kind of typical measuring method with sodium hydroxide potentiometric titration acid and by as Shugar and Dean " the standby reference hand of chemist is (The Chemist ' s Ready Reference Handbook) then " New York McGraw Hill, described in 1990 and the proper method of reference mensuration pKa.

Measure, make pK1 and pK2 be reduced to about below 8.0 replacement and structurally-modifiedly be unwelcome and can cause loses in performance.This can comprise the diamines that causes ethoxylation diamines, hydroxyethyl to replace, in the replacement of the diamines (for example Jeffamine EDR 148) of β (and being low to moderate γ) the position aerobic of the nitrogen of spacer groups.In addition, the material based on quadrol is not suitable for.

Diamines more used herein can be by following organization definition:

R wherein _2-5Be independently selected from H, methyl ,-CH ₃CH ₂And ethylene oxide; C _xAnd C _vBe independently selected from methylene radical or branched-chain alkyl, wherein x+y is about 3-about 6; And A is optional to be existed and is selected from through selecting to give electronics or electrophilic part with what diamines pKa was adjusted to required scope.If A exists, x and y must be 1 or bigger so.

Perhaps, diamines can be those organic diamines that molecular weight is less than or equal to 400g/mol.Preferred these diamines have following formula:

Each R wherein ⁶Be independently selected from H, C ₁-C ₄The straight or branched alkyl, have the alkylene oxide group of following formula:

-(R ⁷O) _mR ⁸R wherein ⁷Be C ₂-C ₄Straight or branched alkylidene group and composition thereof; R ⁸Be H, C ₁-C ₄Alkyl and composition thereof; M is 1-about 10; X is selected from following unit:

I) C ₃-C ₁₀Straight-chain alkyl-sub-, C ₃-C ₁₀Branched alkylidene, C ₃-C ₁₀Ring alkylidene group, C ₃-C ₁₀Prop up the chain link alkylidene group, have the alkyleneoxyalkylene group of following formula:

-(R ⁷O) _mR ⁷-R wherein ⁷As defined above identical with m and this paper;

Ii) C ₃-C ₁₀Straight chain, C ₃-C ₁₀Branching straight chain, C ₃-C ₁₀Ring-type, C ₃-C ₁₀Branching ring alkylidene group, C ₆-C ₁₀Arylidene, wherein said unit comprise one or more pKa that make described diamines greater than about 8 give electronic section or electrophilic part; With

Iii) (i) and mixture (ii),

As long as the pKa of described diamines is at least about 8.

The example of preferred diamines comprises following: dimethylamino-propyl amine, 1,6-hexanediamine, 1,3-propylene diamine, 2-methyl isophthalic acid, 5-pentamethylene diamine, 1,3-pentamethylene diamine (can trade(brand)name Dytek EP obtain), 1,3-diaminobutane, 1,2-two (2-amino ethoxy) ethane (can trade(brand)name Jeffamine EDR 148 obtain), isophorone diamine, 1,3-two (aminomethyl)-hexanaphthene, and composition thereof.Polymeric foam stablizer-composition of the present invention can be chosen wantonly and contain the polymeric foam stablizer.These polymeric foam stablizers prolong lather volume and foam duration, and the grease cutting power of liquid detergent composition is not damaged.These polymeric foam stablizers are preferably selected from:

I) has the homopolymer of (N, N-dialkyl amido) alkyl acrylate of following formula

Respectively do for oneself H, C of each R wherein ₁-C ₈Alkyl, and composition thereof, R ¹Be H, C ₁-C ₆Alkyl, and composition thereof, n is 2-about 6; With

The ii) multipolymer of (i) and following formula

R wherein ¹Be H, C ₁-C ₆Alkyl, and composition thereof, condition is to be about 2 with the ratio of (i) (ii): about 1: 2 of 1-; The molecular weight of this polymeric foam stablizer by conventional gel permeation chromatography is about 1, and 000-is about 2,000,000, and is preferred about 5, and 000-about 1,000,000, more preferably from about 10,000-is about 750,000, and more preferably from about 20,000-is about 500,000, even more preferably from about 35,000-about 200,000.This polymeric foam stablizer can be chosen wantonly with salt form and exist, and perhaps is inorganic salt or for organic salt, for example Citrate trianion, vitriol or the nitrate of (N, N-dimethylamino) alkyl acrylate.

A kind of preferred polymeric foam stablizer is (N, N-dimethylamino) alkyl acrylate, promptly

Composition preferably contains at least about 0.01%, more preferably at least about 0.05%, even more preferably at least about the polymerization suds booster of 0.1% described composition weight.Cleaning combination also preferably contain be no more than about 15%, more preferably no more than about 10%, even more preferably no more than the polymerization suds booster of about 5% described composition weight.

The polymeric foam stablizer of other use, comprise protenacious suds-stabilizing agent and zwitter-ion suds-stabilizing agent, can in the PCT/US98/24699 of the PCT/US98/24707 of the PCT/US98/24853 of on November 20th, 1998 application (case number 6938), application on November 20th, 1998 (case number 6939), application on November 20th, 1998 (case number 6943) and the PCT/US98/24852 that applied on November 20th, 1998 (case number 6944), find.

Another kind of suitable suds-stabilizing agent is the cationic copolymer stablizer, and it contains the unit by acrylamide, Methacrylamide or the acquisition of its mixture of having an appointment greater than 50%, the side chain C of 0.5-2% side chain quaternary nitrogen and 0.1-10% by weight _8-24Hydrophobic grouping, preferred copolymer contains the unit by acrylamide, Methacrylamide or the acquisition of its mixture of the 55-95% that has an appointment by weight, the hydrophile function unit with the unitary molecular configuration that is obtained by at least a monomer that contains the unsaturated quaternary ammonium group of thiazolinyl of 4-30% and 1-15% are by at least a unsaturated C of thiazolinyl that contains _8-24Hydrophobic grouping and the unit that does not have the monomer of quaternary nitrogen to obtain.The monomer that more preferably contains quaternary ammonium group has following formula:

R wherein ₁Be H or CH ₃, R ₂And R ₃Be C independently _1-4Alkyl, R ₄Be C _1-4Alkyl, C _2-3Hydroxyalkyl or phenmethyl, R ₂, R ₃And R ₄Contain altogether and be lower than 9 carbon atoms, Z is a water-soluble one-tenth salt anionic, and M can be--CO--X--, and X is so--O--or--NR ₅--, R ₅Be H or C _1-4Alkyl, and x is 1-6, perhaps M can be phenylene, x is 1 so, and the monomer that contains hydrophobic grouping has following formula:

R wherein ₁Be H or CH ₃, X is--O--or--NR ₇--, Y is--C ₂H ₄O--or--C ₃H ₇O--, y are 0-60, when X is--during O--, R ₆Be C _8-24Alkyl, and as X be--during NR7--, R ₆Be C _1-24Alkyl and R ₇Be H or C _1-24Alkyl, R ₆And R ₇In at least one is C _8-24Alkyl.About the detailed description of these cationic copolymer stablizers referring to US4454060.The dish washing detergent compositions of thickening material-this paper can also contain the thickening material of the 0.2%-5% that has an appointment.More preferably this thickening material accounts for about 0.5%-2.5% of this paper composition.Thickening material typically is selected from the derivatived cellulose class.Suitable thickening material comprises Natvosol, Walocel MT 20.000PV, carboxymethyl cellulose, Quatrisoft LM200 etc.Preferred thickening is a Vltra tears.

Composition can preferably contain at least about 0.1%, more preferably at least about 0.2%, even more preferably at least about the thickening material of 5% described composition weight.Said composition also preferably contain be no more than about 5%, more preferably no more than about 3%, even more preferably no more than the thickening material of about 2.5% described composition weight.

The number-average molecular weight of hydroxypropyl methyl cellulose polymers is about 50,000-125, and 000, and be about 50 in 25 ℃ of following 2wt% viscosity in aqueous solution (ADTMD2363), 000-is about 100,000cps.Particularly preferred hydroxypropyl cellulose polymer is Methocel ^J75MS-N is about 75 25 ℃ of following 2.0wt% viscosity in aqueous solution wherein, 000cps.Particularly preferred hydroxypropyl cellulose polymer is through surface treatment, is at least about in 8.5 the aqueous solution so that hydroxypropyl cellulose polymer is easy to be distributed to pH under 25 ℃.

When being mixed with the detergent composition of wash up of the present invention, hydroxypropyl methyl cellulose polymers should be given the Brookfield viscosity of this detergent composition about 500-3500cps under 25 ℃.More preferably, this Vltra tears is the 25 ℃ of viscosity that will give about 1000-3000cps down.For the purposes of the present invention, use the Brookfield LVTDV-11 viscometer measuring apparatus viscosity of under 12rpm, using the RV#2 rotating shaft.

The clay thickening material is also suitable to be used as thickening material.A kind of suitable clay thickening material is Laponite.With the about 2.0wt% of about 0.25%-, more preferably from about the concentration of the about 1.75wt% of 0.5-is present in this composition this Laponite clay when using, and it is the optional synthetic colored clay that has at least about 5.0wt% tetrapotassium pyrophosphate peptizing agent of LaponiteRDS.Among the Laponite RDS that produces by Britain Laponite inorganics＜2% be particle diameter greater than 250 microns, tap density is about 1000Kg/m ³, surface-area is about 330m ³/ g.Laponite RD does not have peptizing agent, and wherein＜the 2%th, particle diameter is greater than 250 microns, and surface-area is about 370m ²/ g, tap density is about 1000Kg/m ³

When composition contained abrasive, this dish washing detergent compositions can also contain formation colloidal swellable clay, and it had both played the thickening material of goods, played the suspension agent of abrasive again.These expandable clays are to be categorized as those of terre verte and attapulgite on the geology.Suitable smectic clays is the hectorite that is initially the montmorillonitic clay of hydrated aluminosilicate and is initially hydrated magnesium silicate.Be interpreted as, the water ratio of hydration in smectic clays changes with the processing mode of clay.Yet because the inflatable characteristic of hydration smectic clays is by the lattice silicate structures shape, so the amount of water is inessential.In addition, in the montmorillonite electric charge of shortage by as the positively charged ion of sodium, calcium, potassium etc. compensate, like this they by sorption in three layers of (two-layer tetrahedron and one deck octahedron) clay mineral interlayer.Be used for the smectic clays of liquid composition can trade(brand)name such as Thixogel No.1 and Gelwhite GP obtain from R.T.Vanderbilt (two kinds of montmorillonites all are) from GeorgiaKaolin Company (two kinds of montmorillonites all are) and trade(brand)name Veegum Pro and Veegum F.The high viscosity colloid montmorillonitic clay that preferred clay is sold for GeorgiaKaolin company.This clay contains the water of the 6%-10wt% that has an appointment and is following hopcalite: 59%SiO ₂, 21%Al ₂O ₃, 1%Fe ₂O ₃, 2.4%CaO, 3.8%MgO, 4.1%Na ₂O and 0.4%K ₂O.This clay of 100wt% is by 200 mesh sieves.Be easy to be scattered in the water, but need in water, expand before use the biglyyest.This expansion of clay is very important to eliminating the liquid layering.In this expansion process, clay/water mixture constitutes sizable viscosity.It also is thixotropic, therefore also presents a yield-point, has identified 350dynes/cm ²Be the preferred yield-point of clay/water mixture of Gelwhite GP, this be because this time final composition other physical properties be acceptable as cast property, dispersiveness, suspending power and liquid layering.(term " layering " is meant the amount (in millimeter) of the clarified liq that end article can be seen in its surface after 49 ℃ of aging down 1 weeks and 10 weeks.) yield-point is 350dynes/cm ²Clay/water mixture be acceptable, and no matter Gelwhite GP concentration.Usually use HAAKE rvl2, MVIP, E=0.3, R=100 O=113min continued in 18 minutes, and groove rotor and cup are measured yield-point.Another the expandable clay material that is applicable to liquid composition classifies as attapulgite, the magniferous clay of a kind of richness on geology.Typical attapulgite analysis has 55.02%SiO ₂, 10.24%Al ₂O ₃, 3.53%Fe ₂O ₃, 10.49%MgO, 0.47%K ₂O; Under 150 ℃, remove 9.73%H ₂O and under higher temperature, remove 10.13%H ₂O.These clays have little particle diameter, and 100% clay all passes through 200 mesh sieves.Attapulgite clay can trade(brand)name such as Attagel 40, Attagel 50 and Attagel 150 from EngelhardMinerals ﹠amp; Chemicals Corporation is commercially available.Certainly, the mixture of smectic clays and attapulgite clay is also suitable gives the composite behaviour that top any class clay all can not obtain.Material reaches required expansion, and slurry in water is through enough high shear mixing for a long time, abundant basically hydration before in the organic moiety that adds goods at this clay.For example, required expansion can be by realizing 8% moisture clay dispersion high speed shear in 25 minutes.When clay basically fully during hydration, the viscosity of aq suspension remarkably increases, so expanding method allows to use the clay of lower concentration.For example, clay concentration is low to moderate 1%-1.55% and high to maximum 3%, and preferred 1.2%-2wt% can stablize abrasive composition of the present invention effectively, and can side effect do not arranged to its dispersiveness in water.As mentioned above, the clay/water mixture that is used for described composition preferably has about 350dyne/cm ²Yield-point, but be low to moderate 300dyne/cm with yield-point ²And it is high to 450dyne/cm ²Moisture clay dispersion can prepare gratifying abrasive composition.Water-insoluble, the low density abrasive of front are suspended in the dish washing detergent liquid composition, its concentration range is 3%-15%, preferred 5%-15wt%, if desired, can be with a small amount of, for example the crystallization abrasive of the Mohs hardness with 2-7 of 1%-25wt% (in the gross weight of abrasive in the composition) such as silicon-dioxide or lime carbonate partly replace the low density abrasive, as long as the gained dish washing detergent compositions is stable basically.Abrasive-this cleaning combination can be chosen wantonly and contain the about 20wt% of the 0-that has an appointment, the more preferably from about abrasive of the about 10wt% of 0.5-.Abrasive is preferably selected from: the amorphous hydrated SiO 2, be the calcite of Wingdale lime carbonate and polyethylene powders particle and composition thereof.The suitable amorphous silicas (oral level) that improves the friction, capability of composition is provided by Zeoffin.The median size of Zeoffin silicon-dioxide is 8 to up to 10mm.Its apparent density is 0.32-0.37g/ml.Another kind of silicon-dioxide is the Tixosil 103 that Rhone-Poulenc makes.Also can use the amorphous hydrated SiO 2 of the different-grain diameter from Crosfield (9,15 and 300mm) of identical apparent density.The particle diameter that is applicable to a kind of polyethylene powders of the present invention is about 500 microns of about 200-, and density is the about 0.99g/l of about 0.91-, and more preferably from about 0.94-about 0.96.Another preferred abrasive is for being about 0%-20wt% with concentration, and more preferably 1wt%-10wt% uses and by the calcite of J.M.Huber Corporation of Illinois production.Calcite is the calcite of mainly being made up of lime carbonate and 1%-5% magnesiumcarbonate, and its median size is 5 microns, oil absorbency (wiping) be about 10 and hardness be about 3.0Mohs.Various water-miscible liquid of solvent-can use such as low-grade alkane alcohol, glycol, other polyvalent alcohol, ether, amine etc.Preferred especially C ₁-C ₄Alkanol.These solvents can be present in the composition of this paper by about 1%-8%.

When existing, composition preferably contains at least about 0.01%, more preferably at least about 0.5%, even more preferably at least about the solvent of 1% described composition weight.Said composition also preferably contain be no more than about 20%, more preferably no more than about 10%, even more preferably no more than the solvent of about 8% described composition weight.

These solvents can be used in combination with aqueous liquid carriers such as water, and perhaps they can use without any under the aqueous liquid carriers.It is liquid and the compound of not thinking tensio-active agent that solvent is defined as widely under 20 ℃-25 ℃ temperature.One of its distinguishing characteristics is that solvent is tending towards as discrete global existence, rather than as the generalized mixed thing of compound.The example of suitable solvent of the present invention comprises methyl alcohol, ethanol, propyl alcohol, Virahol, 2-methyl-2-pyrrolidone, phenylcarbinol and morpholine n-oxide compound.Particular methanol and Virahol in these solvents.

Suitable solvent used herein comprises 4-14 carbon atom, preferred 6-12 carbon atom, the more preferably ether of 8-10 carbon atom and diether.Other The suitable solvent also has glycol or alkoxylated diols, alkoxylate aromatic alcohol, aromatic alcohol, aliphatic branching alcohol, alkoxylate aliphatic series branching alcohol, alkoxylate straight chain C 1-C5 alcohol, straight chain C 1-C5 alcohol, C8-C14 alkyl and cycloalkyl hydrocarbon and halohydrocarbon, C6-C16 glycol ethers and composition thereof.

The suitable glycol that can be used for this paper is formula HO-CR1R2-OH, and wherein R1 and R2 are the saturated of H or C2-C10 or unsaturated aliphatic hydrocarbon chain and/or ring independently.Suitable glycol used herein is 12 carbon glycol and/or propylene glycol.Suitable polypropylene glycol in addition, for example molecular weight is those of about 100-1000.A kind of suitable polypropylene glycol has about 2700 molecular weight.

The suitable alkoxylated diols that can be used for this paper is formula R-(A) n-R1-OH, wherein R is H, OH, a 1-20 carbon atom, preferred 2-15 carbon atom be the more preferably saturated or unsaturated alkyl of straight chain of 2-10 carbon atom also, wherein R1 is H or 1-20 carbon atom, preferred 2-15 the carbon atom and the more preferably saturated or unsaturated alkyl of straight chain of 2-10 carbon atom, and A is alkoxyl group, preferably oxyethyl group, methoxyl group and/or propoxy-, n is 1-5, preferred 1-2.Suitable alkoxylated diols used herein is methoxyl group octadecanol and/or ethoxy ethoxy ethanol.

The suitable alkoxylate aromatic alcohol that can be used for this paper is formula R (A) _n-OH, wherein R is a 1-20 carbon atom, also more preferably the replacement of the alkyl of 2-10 carbon atom or that non-alkyl the replaces aryl of preferred 2-15 carbon atom, wherein A is an alkoxyl group, preferred butoxy, propoxy-and/or oxyethyl group, and n is the integer of 1-5, preferred 1-2.Suitable alkoxylate aromatic alcohol is benzoyloxy ethanol and/or benzoyloxy propyl alcohol.

The suitable aromatic alcohol that can be used for this paper is formula R-OH, and wherein R is a 1-20 carbon atom, preferred 1-15 the carbon atom aryl that also more preferably the alkyl of 1-10 carbon atom replaces or non-alkyl replaces.Suitable aromatic alcohol for example used herein is a phenylcarbinol.

The suitable aliphatic branching alcohol that can be used for this paper is formula R-OH, and wherein R is a 1-20 carbon atom, and preferred 2-15 carbon atom be the more preferably saturated or unsaturated alkyl of branching of 5-12 carbon atom also.Suitable especially aliphatic branching alcohol used herein comprises 2-ethyl butanol and/or 2-methyl butanol.

The suitable alkoxylate aliphatic series branching alcohol that can be used for this paper is formula R (A) _n-OH, wherein R is a 1-20 carbon atom, preferred 2-15 the carbon atom and the more preferably saturated or undersaturated alkyl of branching of 5-12 carbon atom, wherein A is an alkoxyl group, preferably butoxy, propoxy-and/or oxyethyl group, and n is the integer of 1-5, preferably 1-2.Suitable alkoxylate aliphatic series branching alcohol comprises 1-methyl-prop ethoxy-ethanol and/or 2-methyl butyl cellosolve.

The suitable alkoxylate straight chain C 1-C5 alcohol that can be used for this paper is formula R (A) _n-OH, wherein R is a 1-5 carbon atom, the saturated or undersaturated alkyl of straight chain of preferred 2-4 carbon atom, wherein A is an alkoxyl group, preferred butoxy, propoxy-and/or oxyethyl group, and n is the integer of 1-5, preferably 1-2.Suitable alkoxylate aliphatic straight chain C1-C5 alcohol has butoxy propoxy-propyl alcohol (n-BPP), butyl cellosolve, butoxy propyl alcohol, ethoxy ethanol or its mixture.Butoxy propoxy-propyl alcohol can trade(brand)name n-BPP ^Commercially available from Dow Chemical Company (Dow chemical).

The suitable straight chain C 1-C5 alcohol that can be used for this paper is formula R-OH, and wherein R is a 1-5 carbon atom, the saturated or undersaturated alkyl of straight chain of preferred 2-4 carbon atom.Suitable straight chain C 1-C5 alcohol has methyl alcohol, ethanol, propyl alcohol or its mixture.

Other The suitable solvent includes, but not limited to butyldiglycol ether (BDGE), Butyl Triglycol Ether 99, ter amilic alcohol etc.The particularly preferred solvent that can be used for this paper has butoxy propoxy-propyl alcohol, butyldiglycol ether, phenylcarbinol, butoxy propyl alcohol, ethanol, methyl alcohol, Virahol and composition thereof.

Other The suitable solvent that is used for this paper comprises propanediol derivative, for example n-butoxy propyl alcohol or n-butoxy propoxy-propyl alcohol, water-soluble CARBITOL ^RSolvent or water-soluble CELLOSOLVE ^RSolvent; Water-soluble CARBITOL ^RSolvent is the compound of 2-(2-alkoxyl group oxyethyl group) ethanol class, and wherein alkoxyl group derives from ethyl, propyl group or butyl; Preferred water-soluble Trivalin SF is 2-(2-butoxy oxyethyl group) ethanol, and it is also known as diethylene glycol monobutyl ether.Water-soluble CELLOSOLVE ^RSolvent is the compound of 2-alkoxyl group ethoxy ethanol class, preferred 2-bu-toxyethoxy.Other The suitable solvent comprises phenylcarbinol and 2-ethyl-1 for example, 3-hexylene glycol and 2,2,4-trimethylammonium-1, glycols of 3-pentanediol and composition thereof.Preferred solvents more used herein have n-butoxy propoxy-propyl alcohol, BUTYL CARBITOL ^And composition thereof.

These solvents also can be selected from: comprise one-, two-and compound of the ether derivant of three-ethylene glycol, propylene glycol, butanediol ethere and composition thereof.The molecular weight of these solvents preferably is lower than 350,100-300 more preferably, even more preferably 115-250.The example of preferred solvent comprises for example monoethylene glycol n-hexyl ether, a propylene glycol n-butyl ether and tripropylene glycol methyl ether.Gylcol ether and propylene glycol ethers can be from Dow Chemical Company with trade(brand)names " Dowanol " and commercially available with trade(brand)name " Arcosolv " from Arco chemical company.Other the preferred solvent that comprises monoethylene glycol n-hexyl ether and Diethylene Glycol n-hexyl ether can obtain from associating carbide company (UnionCarbide).Solubilizing agent-this composition can be chosen wantonly and contain the about 12wt% of the 0wt%-that has an appointment, at least a solubilizing agent of the about 10wt% of 1wt%-more preferably from about, and it can be hydrotropic solvent such as sodium xylene sulfonate or cumene sodium sulfonate; C _2-3One or dihydroxyl alkanols such as ethanol, Virahol and propylene glycol and composition thereof.Contain solubilizing agent in order to control low temperature muddy clarification performance.Can choose wantonly in this composition and use urea solubilizing agent as a supplement, its concentration is the about 10wt% of 0-, more preferably from about the about 8wt% of 0.5wt%-.Other solubilizing agent that is suitable for has glycerine; Molecular weight is water-soluble polyethylene glycol class, the formula HO (CH of 300-600 ₃CHCH ₂O) _nThe polypropylene glycol of H, wherein n is number 2-18; Mixture of polyoxyethylene glycol and polypropylene glycol (Synalox) and structural formula are R (X) _nOH and R ₁(X) _nOne C of the ethylene glycol of OH and propylene glycol ₁-C ₆Alkyl ether and ester class, wherein R is C ₁-C ₆Alkyl, R ₁Be C ₂-C ₄Acyl group, X are (OCH ₂CH ₂) or (OCH ₂(CH ₃) CH), n comprises that for the representative member of number 1-4, polypropylene glycol dipropylene glycol and molecular weight are the polypropylene glycol of 200-1000, for example polypropylene glycol 400.Other gratifying glycol ethers has ethylene glycol monobutyl ether (ethylene glycol butyl ether), Diethylene Glycol monobutyl ether (diethylene glycol monobutyl ether), the triethylene glycol monobutyl ether, one, two, the tripropylene glycol monobutyl ether, the TEG monobutyl ether, one, two, the tripropylene glycol monomethyl ether, the propylene glycol monomethyl ether, ethylene glycol one hexyl ether, Diethylene Glycol one hexyl ether, the glycol tertiary butyl ether, glycol monoethyl ether, methyl glycol, propyl cellosolve, ethylene glycol one amyl ether, methyl carbitol, Diethylene Glycol one ether, Diethylene Glycol one propyl ether, Diethylene Glycol one amyl ether, the triethylene glycol monomethyl ether, triethylene glycol one ether, triethylene glycol one propyl ether, triethylene glycol one amyl ether, triethylene glycol one hexyl ether, one, two, tripropylene glycol one ether, one, two, tripropylene glycol one propyl ether, one, two, tripropylene glycol one amyl ether, one, two, tripropylene glycol one hexyl ether, one, two, three butyleneglycol monomethyl ethers, one, two, three butyleneglycols, one ether, one, two, three butyleneglycols, one propyl ether, one, two, three butyleneglycol monobutyl ethers, one, two, three butyleneglycols, one amyl ether and one, two, three butyleneglycols, one hexyl ether, ethylene glycol monoacetate and dipropylene glycol propionic ester.Polymerization dirt release agent-composition of the present invention can randomly contain one or more dirt release agents.The polymerization dirt release agent is characterised in that both have the hydrophilic segment that makes the hydrophobic fiber surface hydrophilic, for example polyester and nylon have again and are deposited on the hydrophobic fiber and adhere on it in the whole process of wash cycle and therefore as the hydrophobic fragment of the anchor of hydrophilic segment.This make the spot of existence can be enough dirt release agent handle, thereby easy cleaning more in the washing step in the back.

If you are using, it is about 10% that dirt release agent accounts for about 0.01%-of composition weight usually, and preferably about 0.1%-is about 5%, and more preferably from about 0.2%-about 3%.

Following document description be applicable to soil release polymers of the present invention, they all are added herein by reference.Authorized people's such as Gosselink US5 on November 25th, 1997,691,298; Authorized people's such as Pan US5 on February 4th, 1997,599,782; Authorize people's such as Gosselink US5 May 16 nineteen ninety-five, 415,807; Authorized people's such as Morrall US5 on January 26th, 1993,182,043; Authorize people's such as Gosselink US4 September 11 nineteen ninety, 956,447; Authorize people's such as Maldonado US4 September 11 nineteen ninety, 976,879; Authorize people's such as Scheibel US4 November 6 nineteen ninety, 968,451; Authorize Borcher, people's such as Sr. US4,925,577 May 15 nineteen ninety; Authorized the US4 of Gosselink, 861,512 on August 29th, 1989; Authorized people's such as Maldonado US4 on October 31st, 1989,877,896; Authorized people's such as Gosselink US4 on October 27th, 1987,702,857; Authorized people's such as Gosselink US4 on December 8th, 1987,711,730; Authorized the US4 of Gosselink, 721,580 on January 26th, 1988; Authorized people's such as Nicol US4 on December 28th, 1976,000,093; Authorized the US3 of Hayes, 959,230 on May 25th, 1976; Authorized the US3 of Basadur, 893,929 on July 8th, 1975; And on April 22nd, 1987 is by the disclosed EP0219048A of people such as Kud.

Other suitable dirt release agent is described in people's such as Voilland US4,201,824; People's such as Lagasse US4,240,918; People's such as Tung US4,525,524; People's such as Ruppert US4,579,681; US4,220,918; US4,787,989; Rhone-Poulencchemie is in disclosed EP279 in 1988,134A; The EP457 of BASF (1991), 205A; And the DE2 of Unilever N.V. (1974), 335,044; They all are added herein by reference.Stand oil fat release agent-composition of the present invention can also be chosen wantonly and contain stand oil fat release agent.Suitable polymer blend grease release agent comprises those of following formula: Wherein x is H and alkali metal cation, and n is number 2-16, and R1 is selected from: methyl or H, R ₂Be C ₁-C ₁₂The straight or branched alkyl, R ₃Be C ₂-C ₁₆The straight or branched alkyl, y is for making that molecular weight is about 5, the value of 000-about 15,000.Referring to US5573702.Clay soil removal/anti deposition agent-composition of the present invention more also can be chosen wantonly to contain and has that clay soil is removed and the water-soluble ethoxylated amine of antiredeposition performance.The granular detergent composition that contains these compounds typically contains the water-soluble ethoxylated amine of the about 10.0wt% of 0.01%-that has an appointment; Liquid detergent composition typically contains the 0.01%-that has an appointment about 5%.

Preferred soil release and anti redeposition agent are the ethoxylation tetraethylene-pentamine.The ethoxylated amine of illustration also is described in the US4 that authorized VanderMeer on July 1st, 1986, in 597,898.Another kind of preferred clay soil removal-anti redeposition agent is the 0h that announced on June 27th, 1984 and the EP111 of Gosselink, disclosed cation compound in 965.Operable other clay soil removal-anti redeposition agent is the EP111 of the Gosselink that announced on June 27th, 1984, disclosed ethoxylated amine polymer in 984; The EP112 of the Gosselink that announced on July 4th, 1984, disclosed amphoteric ion polymer in 592; With the US4 that authorized Connor on October 22nd, 1985, disclosed amine oxide in 548,744.Other clay soil known in the art removes and/or anti redeposition agent also can be used in the composition of this paper.Referring to the US4 that authorizes VanderMeer January 2 nineteen ninety, 891,160 and November 30 nineteen ninety-five disclosed WO95/32272.Another kind of preferred anti redeposition agent comprises carboxymethyl cellulose (CMC) material.These materials are known in the art.Polymeric dispersant-polymeric dispersant can advantageously be used for the composition of this paper with the amount of the about 7wt% of about 0.1%-, particularly under the situation that zeolite and/or layered silicate washing assistant are arranged.Suitable polymeric dispersant comprises polymer poly-carboxylate and polyoxyethylene glycol, although also can use other dispersion agent known in the art.Though do not plan bound by theory, it is believed that when with other washing assistant (comprising the lower molecular weight polycarboxylate) when being used in combination, polymeric dispersant improves whole detergent builders performance by suppressing crystal growth, freeing particulate fouling, peptization and antiredeposition.

By polymerization or the suitable unsaturated monomer of copolymerization, preferably, can make polymer poly-carboxylate's material with its sour form.The unsaturated monomer acid that can polymerization forms suitable polymer poly-carboxylate comprises vinylformic acid, toxilic acid (or maleic anhydride), fumaric acid, methylene-succinic acid, equisetic acid, methylfumaric acid, citraconic acid and methylene radical propanedioic acid.Contain non-carboxylate group such as vinyl methyl ether, vinylbenzene, ethene etc. aptly in the polymer poly-carboxylate of this paper or the monomer fragment, as long as these fragments are no more than about 40wt%.

Shi Yi polymer poly-carboxylate can obtain from vinylformic acid especially.These acrylic acid based polymers that are used for this paper are the water-soluble salt of polymeric acrylic acid.Preferably about 2 with the molecular-weight average of these polymkeric substance of sour form, 000-10,000, more preferably from about 4,000-7,000, most preferably from about 4,000-5,000.The water-soluble salt of these acrylate copolymer for example can comprise, its basic metal, ammonium and substituted ammonium salt.This class soluble polymer is a known materials.The purposes of this class polyacrylate in detergent composition has been disclosed in the US3 that for example authorized Diehl on March 7th, 1967, in 308,067.

Also can use the preferred ingredient of vinylformic acid/toxilic acid-base co-polymer as this dispersion/anti redeposition agent.These materials comprise the water-soluble salt of the multipolymer of vinylformic acid and toxilic acid.Be preferably with the molecular-weight average of these multipolymers of sour form about 2,000-100,000, more preferably from about 5,000-75,000, most preferably from about 7,000-65,000.The segmental ratio of propylene acid group and maleate is generally about 30 in these multipolymers: about 1: 1 of 1-, more preferably from about 10: 1-2: 1.The water-soluble salt of these vinylformic acid/maleic acids can comprise for example its basic metal, ammonium and substituted ammonium salt.This class solubility acrylate/maleate copolymer is a known materials, they are described among the disclosed EP66915 on November 15 nineteen eighty-two, and on September 3rd, 1986 disclosed EP193, in 360, it has also described these multipolymers that contain the hydroxypropyl acrylate.Other useful dispersion agent comprises toxilic acid/vinylformic acid/vinyl alcohol trimer.These materials also are disclosed in EP193, in 360, for example comprise 45/45/10 trimer of vinylformic acid/toxilic acid/vinyl alcohol.

Another polymeric material that can comprise is polyoxyethylene glycol (PEG).PEG can have dispersing agent performance and can be used as clay soil removal-anti redeposition agent.About 100,000 for about 500-, preferably about 1 for the typical molecular weight of these purposes, 000-is about 50,000, and more preferably from about 1,500-about 10,000.

Also can use polyaspartic acid salts and polyglutamic acid dipersant, particularly combine with zeolite builders.For example the dispersion agent of polyaspartic acid salts preferably has about 10,000 molecular weight (on average).

At the bleach stability of biodegradability, raising or clean and to comprise various trimers and hydrophobically modified multipolymer by comparatively ideal other polymer type aspect the purpose, comprise ﹠amp by Rohm; Haas, BASF Corp., those that Nippon Shokubai sells and other material that is used for all modes of water treatment, textile treatment or washing composition application.The composition of sequestrant-this paper can also be chosen wantonly and contain one or more sequestrants, is used in particular for the sequestrant of external transition metal.Be common in the washing water those and comprise the iron and/or the manganese of water-soluble colloid or particle form, and can be attended by oxide compound or oxyhydroxide, perhaps find together with dirt such as Humus.Preferred sequestrant is effectively to control these transition metal, particularly comprise these transition metal of control or its compound be deposited on fabric and/or control control washing medium in and/or at those of the undesirable redox reaction of fabric or crust interface.These sequestrants comprise that molecular weight is low and be those of aggretion type, and at least one is typically arranged, preferred two or single body heteroatoms such as O or the N of giving, they can with transition-metal coordination.Common sequestrant can be selected from: aromatic chelating agent of aminocarboxylate, amino phosphonates do, multifunctional replacement and composition thereof.

Optional aminocarboxylate as sequestrant comprises edetate, N-hydroxyethyl-ethylenediamine triacetate, nitrilotriacetic acid(NTA) salt, ethylenediamine tetrapropionic acid(EDTP) salt, teiethylene tetramine-hexacetic acid salt, diethylenetriamine pentaacetic acid salt and ethanol Diglycocol, its basic metal, ammonium and substituted ammonium salt and composition thereof.

When allowing a small amount of at least total phosphorus in detergent composition, amino phosphonates do also is suitable for as the sequestrant in the present composition, and comprises ethylenediamine tetraacetic (methylene phosphonic acid salt), as DEQUEST.Preferred these amino phosphonates do do not contain alkyl or the alkenyl that surpasses about 6 carbon atoms.

The aromatic chelating agent of multifunctional replacement also can be used in the composition of this paper.Authorize people's such as Connor US3 referring on May 21st, 1974,812,044.With this class preferred compound of sour form be dihydroxyl disulfobenzene class as 1,2-dihydroxyl-3,5-disulfobenzene.

A kind of preferred biodegradable cheating agent that is used for this paper is ethylenediamine disuccinate (" EDDS "), particularly authorizes the US4 of Hartman and Perkins, [S, the S] isomer described in 704,233 on November 3rd, 1987.

The composition of this paper can also contain water-soluble methylglycine oxalic acid (MGDA) salt (or sour form) as sequestrant or auxiliary washing assistant.Similarly, so-called " weak " washing assistant such as Citrate trianion also can be used as the sequestrant use.

If you are using, sequestrant accounts for about 0.001%-about 15% of detergent composition weight usually.More preferably, if you are using, sequestrant accounts for about 0.01%-about 3.0% of these composition weights.Suds suppressor-when according to required purposes needs when particularly doing washing in washing is used, can add in the composition of the present invention reducing or suppress the compound that foam forms.Other composition for example is designed for those of hand washing, may be desirably high the foaming, and can not want these components.Suppressing foam may be at US4, and 489,455 and 4,489, particularly important in the positive reinforced European shape washing machine of the what is called described in 574 " high density purging method " neutralization.

Can use various materials as suds suppressor and be known in the art.For example, the 3rd edition, roll up 7, the 430-447 pages or leaves (Wiley, 1979) referring to Kirk Othmer Encyclopedia of Chemical Technology.

The composition of this paper contains the suds suppressor of 0%-about 10% usually.When using monocarboxylic acid lipid acid and salt thereof as suds suppressor, it is about 5% with up to detergent composition weight typically, and the amount of preferred 0.5%-3% exists.But can use high level.Preferred use about 0.01%-about 1%, more preferably from about the polysiloxane suds suppressor of 0.25%-about 0.5%.These weight percentage comprise any silicon-dioxide that can be used in combination with organopolysiloxane, and utilizable any suds suppressor subsidiary material.Usually use a stearyl phosphoric acid salt suds suppressor with the amount of the about 2wt% composition of 0.1%-.Typically use the hydrocarbon suds suppressor, but can use high level with the amount of about 0.01%-about 5.0%.Typically use pure suds suppressor with the amount of 0.2%-3% final composition weight.Alkoxylate polycarboxylate-this paper can use the alkoxylate polycarboxylate as by those of polyacrylate preparation, thereby provides additional grease to remove performance.These materials are described in the page 4 of WO91/08281 and PCT90/01815 and page or leaf afterwards, and it is added herein by reference.Chemically these materials comprise that there is the polyacrylate of an oxyethyl group side chain every 7-8 acrylate unit.These side chains are formula-(CH ₂CH ₂O) _m(CH ₂) _nCH ₃, wherein m is 2-3, n is 6-12.These side chains are connected through ester bond with polyacrylate " main chain ", thereby one " pectination " polymer-type structure is provided.Its molecular weight can change, but typically is about 2000-about 50,000.These alkoxylate polycarboxylates can account for about 0.05%-about 10% of this paper composition total weight.Spices-spices and fragrance component useful in the present composition and method comprises various natural and synthetic chemistry compositions, includes, but not limited to aldehydes, ketone, ester class etc.The various natural extracts and the essence that also comprise the complex mixture that can contain following composition: for example sweet orange oil, lemon oil, rose extract, lavender, Moschus, patchouli, face cream essence, santal oil, pine tar, cdear etc.Final spices can contain the utmost point complex mixture of these compositions.It is about 2% that final spices typically accounts for about 0.01%-of this paper detergent composition weight, and single fragrance component can account for about 0.0001%-about 90% of final flavor compositions.

The non-limitative example of fragrance component used herein comprises: 7-ethanoyl-1,2,3,4,5,6,7,8-eight H-1,1,6,7-tetramethyl-naphthalene; The methyl ionone; γ methyl ionone; The methyl deodarone; Methyl dihydrojasmonate; Methyl 1,6,10-trimethylammonium-2,5,9-cyclododecatriene-1-base ketone; 7-ethanoyl-1,1,3,4,4,6-hexamethyl naphthane; 4-ethanoyl-6-the tertiary butyl-1,1-dimethyl indane; The p-hydroxybenzene butanone; Benzophenone; Methyl betanaphthyl ketone; 6-ethanoyl-1,1,2,3,3,5-hexamethyl indane; 5-ethanoyl-3-sec.-propyl-1,1,2,6-tetramethyl-indane; 1-12 carbon aldehyde, 4-(4-hydroxy-4-methyl amyl group)-3-tetrahydrobenzene-1-carboxylic aldehyde (carboxaldehyde); 7-hydroxyl-3,7-dimethyl octanal; 10-undecene-1-aldehyde; Dissident's thiazolinyl hexahydrobenzaldehyde; The formyl radical tristane; The condensation product of the condensation product of the condensation product of laurine and methyl o-aminobenzoate, laurine and indoles, phenylacetic aldehyde and indoles; 2-methyl-3-(to tert-butyl-phenyl)-propionic aldehyde; Vanirone; Piperonylaldehyde; Hexyl cinnamic aldehyde; Amyl cinnamic aldehyde; 2-methyl-2-(p-isopropyl phenyl)-propionic aldehyde; Tonka bean camphor; The γ decalactone; The cyclopentyl decyl amide; 16-hydroxyl-palmitoleic acid lactone; 1,3,4,6,7,8-six H-4,6,6,7,8,8-hexamethyl-cyclopentyl-γ-2-chromene; The 2-Naphthol methyl ether; Hogweed alkane; 12 H-3a, 6,6,9a-tetramethyl-naphthalene [2,1b] furans; Cypress camphor, 5-(2,2,3-front three basic ring penta-3-thiazolinyl)-3-methylpent-2-alcohol; 2-ethyl-4-(2,2,3-trimethylammonium-3-cyclopentenes-1-yl) 2-fourth-1-alcohol; Caryophyllenol; The tricyclic decenyl propionic ester; The tricyclo decene yl acetate; Benzyl salicylate; Cedryl acetate and to (tertiary butyl) cyclohexyl acetic acid ester.

Particularly preferred spices material is that those that maximum smell improves are provided in the finished product composition of cellulase.These spices include but not limited to: hexyl cinnamic aldehyde; 2-methyl-3-(to tert-butyl-phenyl)-propionic aldehyde; 7-ethanoyl-1,2,3,4,5,6,7,8-eight H-1,1,6,7-tetramethyl-naphthalene; Benzyl salicylate; 7-ethanoyl-1,1,3,4,4,6-hexamethyl naphthane; To (tertiary butyl) cyclohexyl acetic acid ester; Methyl dihydrojasmonate; The 2-Naphthol methyl ether; Methyl betanaphthyl ketone; 2-methyl-2-(p-isopropyl phenyl)-propionic aldehyde; 1,3,4,6,7,8-six H-4,6,6,7,8,8-hexamethyl-cyclopentyl-γ-2-chromene; 12 H-3a, 6,6,9a-tetramethyl-naphthalene [2,1b] furans; Aubepine; Tonka bean camphor; Cypress camphor; Vanillin food grade,1000.000000ine mesh; The cyclopentyl decyl amide; Tricyclo decene yl acetate and tricyclic decenyl propionic ester.

Other spices material comprises essential oil, resinoid and from the resin that includes, but is not limited to following each provenance: Surinam balsam, frankincense resinoid, Styrox, labdanum resin, Semen Myristicae, Oleum Cinnamomi, styrax resinoid, coriander and lavender element.Other flavor chemistry material comprises phenylethyl alcohol, Terpineol 350, coriandrol, phanteine, geraniol, vernol, 2-(1, the 1-dimethyl ethyl)-adnoral acetate, phenylmethyl acetate and Eugenol.In final flavor compositions, can use for example carrier of diethyl phthalate.

Particularly in microemulsion, composition can use essential oil or water-fast organic compound to replace this spices, and this organic compound is for example for having water-fast hydrocarbon such as paraffin or isoparaffin such as isoparH, isodecane, α-Pai Xi, beta-pinene, decyl alcohol and the terpinol of 6-18 carbon atom.Suitable essential oil is selected from: natural methyl allylphenol 20/21, the anise oil Chinese star, anise oil ball board, face cream (Peru), basil oil (India), Fructus piperis nigrum oil, black pepper oleoresin 40/20, Bois de Rose (Brazil) FOB, borneol (China), white oil of camphor, White camphor powder synthetic technology, cananga oil (Java), cardamom oil, Oleum Cinnamomi (China), oleum Cunninghamiae lanceolatae (China) BP, cinnamon bark oil, Cortex Cinnamomi leaf oil, pamorusa oil, clove bud oil, Dingxiangye FOLIUM SYRINGAE, coriander (Russia), 9 ℃ of coumarin 6s (China), Xian Kelaiquan, benzophenone, vanirone, eucalyptol, volatile oil extracted from eucalyptus' leaves or twigs, Eucalyptus citriodora, olium anisi, Herba Erodii oil, ginger oil, oleoresin ginger (India), the white grapes shaddock, guaiac wood oil, gurjun balsam, piperonylaldehyde, the isobornyl acetic ester, Isolongifolene, needle juniper berry oil, acetate L-methyl esters, oleum lavendulae, lemon oil, West Indian lemon grass oil, distilled limette oil, litsea cubeba oil, longifolene, the mentha camphor crystal, methyl cdear base ketone, the methyl chavicol, wintergreen oil, musk ambrette, muskone, musk xylene, ucuhuba oil, orange oil, patchouli oil, oleum menthae piperitae, phenylethyl alcohol, sweet green pepper berry oil, sweet green pepper leaf oil, Rosalin, santal wood oil, Sandenol, sage oil, Salvia Sclare L., sassafras wood oil, Oleum Menthae Rotundifoliae, lavender, Flower of Aztec Marigold, tea tree oil, vanillin food grade,1000.000000ine mesh, Vetyver oil (Java), wintergreen oil.Composition pH-dish washing detergent compositions of the present invention will stand the acid stress that the food dirt produces when using, promptly through diluting and being applied on the dirty tableware.If greater than the more effective words of 7 composition, can choosing wantonly to contain so, pH can in composition and diluent, provide common buffer reagent, i.e. about 0.1%-0.4% aqueous solution of composition weight than alkaline pH in composition and diluent.The pKa value of this buffer reagent should be and is lower than the following about 0.5-1.0pH unit of the required pH value of composition (measuring as mentioned above).The pKa of preferred this buffer reagent should be about 7-about 10.Under these conditions, when using its minimum, buffer reagent can be controlled its pH most effectively.

The pH of preferred composition of the present invention (with 10% determination of aqueous solution) serves as that about 2.0-is about 12.5, more preferably from about-and Yue.

Buffer reagent itself can be activated detergent, perhaps can be for being used for lower molecular weight, the organic or inorganic material that this composition only keeps alkaline pH.The preferred reducing that is used for the present composition is a nitrogenous material.Some examples for the acid of lysine amino for example or rudimentary hydramine as one-, two-and three-thanomin.Other preferred nitogen-contained buffer agent is three (methylol) aminomethane (HOCH ₂) ₃CNH ₃(TRIS), 2-amino-2-ethyl-1, ammediol, 2-amino-2-methyl-propyl alcohol, 2-amino-2-methyl-1, ammediol, disodium glutamate, N-methyl diglycollic amide, 1,3-diamino-propyl alcohol, N, N '-tetramethyl--1,3-diamino-2-propyl alcohol, N, N-two (2-hydroxyethyl) glycine (bicine) and N-three (methylol) methylglycine (N-triglycine).Above-mentioned mixture also is an acceptable arbitrarily.Useful inorganic buffer agent/source of alkalinity comprises alkaline carbonate and alkali metal phosphate, for example yellow soda ash, sodium polyphosphate.Other buffer reagent is referring to McCutcheon ' s EMULSIFIERS AND DETERGENTS, the North America version, and 1997, McCutcheon Division, MC Publishing Company Kirk and WO95/07971 are added herein by reference them.

Composition preferably contains at least about 0.1%, more preferably at least about 1%, even more preferably at least about the buffer reagent of 2% described composition weight.Said composition also preferably contain be no more than about 15%, more preferably no more than about 10%, even more preferably no more than the buffer reagent of about 8% described composition weight.Hydrotropic agent-aqueous liquid carriers can contain one or more and be hydrotropic material.Be applicable to that the hydrotropic agent in this paper composition comprises C ₁-C ₃Alkylaryl sulphonate, C ₆-C ₁₂Alkanol, C ₁-C ₆Carboxyl vitriol and sulfonate, urea, C ₁-C ₆Hydrocarbon carboxylic acids salt, C ₁-C ₄Carboxylate salt, C ₂-C ₄Organic diacid and these hydrotropic mixtures.Liquid detergent composition of the present invention preferably contain liquid detergent composition weight about 0.5%-8% be selected from following hydrotropic agent: the xylenesulfonate of basic metal and calcium and tosylate.

Suitable C ₁-C ₃Alkylaryl sulphonate comprises sodium xylene sulfonate, potassium, calcium and ammonium; Toluenesulfonic acid sodium salt, potassium, calcium and ammonium; Cumene sodium sulfonate, potassium, calcium and ammonium; And replacement or unsubstituted sodium naphthalene sulfonate, potassium, calcium and ammonium and composition thereof.

Suitable C ₁-C ₈Carboxyl vitriol or sulfonate for contain 1-8 carbon atom (not comprising substituting group), with the replacement of sulfate radical or sulfonate radical and have any water-soluble salt or the organic compound of at least one carboxyl.The organic compound of this replacement can be ring-type, acyl family or aromatics, i.e. benzene derivative.The preferred alkyl compound has 1-4 the carbon atom that replaces with sulfate radical or sulfonate radical and has 1-2 carboxyl.The hydrotropic example of this class comprises sulfosuccinate, sulfosalicylic phthalate salt, sulfosalicylic acetate, a sulfosalicylic acid salt and diester sulfosuccinate, disclosed sodium or sylvite among the preferred US3915903.

Suitable C used herein ₁-C ₄Hydrocarbon carboxylic acids salt and C ₁-C ₄Carboxylate salt comprises acetate and propionic salt and Citrate trianion.Suitable C used herein ₂-C ₄Diacid comprises succsinic acid, pentanedioic acid and hexanodioic acid.

Discharge water-soluble growth encourage effect and be applicable to that this paper comprises C as other compound that hydrotropic solvent uses ₆-C ₁₂Alkanol and urea.

The preferred hydrotropic agent that is used for this paper is cumene sodium sulfonate, potassium, calcium and ammonium; Sodium xylene sulfonate, potassium, calcium and ammonium; Toluenesulfonic acid sodium salt, potassium, calcium and ammonium; And composition thereof.Most preferably cumene sodium sulfonate and calcium xylene sulfonate and composition thereof.These preferred hydrotropic agents can be present in the composition by about 0.5%-8wt%.

Composition preferably contains at least about 0.1%, more preferably at least about 0.2%, even more preferably at least about the hydrotropic agent of 0.5% described composition weight.Said composition also preferably contain be no more than about 15%, more preferably no more than about 10%, even more preferably no more than the hydrotropic agent of about 8% described composition weight.Other component-this detergent composition can also preferably contain one or more and be selected from following washing auxiliary detergent: soil release polymers, polymeric dispersant, polysaccharide, abrasive, sterilant, tarnish inhibitor, color stable agent, dyestuff, ionogen (for example NaCl etc.), anti-mycotic agent or mould inhibitor, wormer, miticide, hydrotropic agent, processing aid, suds booster, whitening agent, resistant to tarnishing auxiliary agent, stablizer and antioxidant.Various other compositions that can be used in the detergent composition can comprise in the composition of this paper, comprise the used solvent of other activeconstituents, carrier, antioxidant, processing aid, dyestuff or pigment, flowing product, solid packing of bar compositions etc.If wish high whipability, can be with for example C ₁₀-C ₁₆The suds booster of alkylolamide adds in this composition with 1%-10% level typically.C ₁₀-C ₁₄One ethanol and diglycollic amide are the typical types of these suds boosters.It also is useful that these suds boosters use as amine oxide, trimethyl-glycine and sultaine with high foaming auxiliary agent tensio-active agent above-mentioned.

Can randomly antioxidant be added in the detergent composition of the present invention.They can be any conventional antioxidants used in the detergent composition, for example 2,6 di tert butyl 4 methyl phenol (BHT), carbamate, ascorbate salt, thiosulphate, Monoethanolamine MEA BASF (MEA), diethanolamine, trolamine etc.When antioxidant, preferably its amount in composition is the about 5wt% of about 0.001%-.

Various cleaning ingredients used in this composition can also be coated with described substrate with hydrophobic coating and be stablized then randomly by described composition is adsorbed on the porous hydrophobic substrate.Preferably cleaning ingredients is mixed with tensio-active agent, then it is sucked in the porous substrate.During use, cleaning ingredients is discharged into the aqueous cleaning solution from substrate, and it exercises its washing function of wanting therein.

In order to describe this technology in detail, (trade name SIPERNATD10 DeGussa) mixes with the proteolysis enzyme solution that contains 3%-5% ethoxy alcohol (EO7) nonionogenic tenside with porous hydrophobic silicon-dioxide.Typically, the weight of this enzyme/surfactant soln is 2.5 times of silicon-dioxide.Under agitation the gained powder is scattered in the silicone oil (can use the various silicone oil of range of viscosities) at 500-12500.With the emulsification of gained silicone oil dispersion liquid, perhaps it is added in the final washing composition matrix in addition.In this way, the composition that for example is used for aforementioned enzyme, SYNTHETIC OPTICAL WHITNER, bleach-activating agent, bleaching catalyst, light activating agent, dyestuff, fluorescent agent, fabric conditioner and the hydrolyzable tensio-active agent of washing composition (comprising liquid laundry detergent compositions) can obtain " protection ".The form of composition

Composition of the present invention can be any conventional form of manual dishwashing composition, for example paste, liquid, particle, powder, gel, liquid gel, microemulsion crystallization or its composition.Highly preferred embodiment is liquid or gel form.Liquid composition can contain water or not moisture.When composition when being liquid, aqueous, composition other aqueous liquid carriers main and optional moiety that preferably also contains dissolving, disperses or suspend.

When composition when being liquid, aqueous, composition preferably contains at least about 5%, more preferably at least about 10%, even more preferably at least about the aqueous liquid carriers of 30% described composition weight.Said composition also preferably contain be no more than about 95%, more preferably no more than about 60%, even more preferably no more than the aqueous liquid carriers of about 50% described composition weight.

Certainly, a kind of main component of aqueous liquid carriers is a water.Yet aqueous liquid carriers can contain promising liquid or at room temperature be dissolved in the liquid vehicle and can be used as except that the function of simple filler other material that some other functions are used.These materials can comprise for example hydrotropic agent and solvent.For example the lower molecular weight of methyl alcohol, ethanol, propyl alcohol and Virahol and so on uncle or secondary alcohol suit.With regard to making surface active agent solubilization, preferred monohydroxy-alcohol, but also can use polyvalent alcohol for example contains about 6 carbon atoms of 2-and about 6 hydroxyls of 2-those (for example 1, ammediol, ethylene glycol, glycerine and 1,2-propylene glycol).

The example of the detergent composition particulate preparation process of this paper is as follows :-alkylbenzene sulfonate, citric acid, water glass, sodium sulfate spices, diamines and the water of modification is added in the crutcher, heats and mixes.The gained slurries are spray dried to particle form.

The example of the step of preparation this paper liquid detergent composition is as follows :-adding Citrate trianion in free-water also dissolves.In this solution, add amine oxide, trimethyl-glycine, ethanol, hydrotropic agent and nonionogenic tenside.If can not obtain free-water, in the mixture, stir up to dissolving then above so Citrate trianion being added.Add these goods of acid neutralization this moment.Preferred acid is selected from for example organic acid of toxilic acid and citric acid, yet, also can use mineral acid.In a preferred embodiment, before adding diamines, in goods, add these acid.Add AExS at last.

The anhydrous liq washing composition

The liquid detergent composition that can contain the anhydrous carrier medium: US4,753,570 according to disclosed content preparation in the following document, 4,767,558,4,772,413,4,889,652,4,892,673, GB-A-2,158,838, GB-A-2,195,125, GB-A2,195,649, US4,988,462, US5,266,233, EP-A-225,654 (6/16/87), EP-A-510,762 (10/28/92), EP-A-540,089 (5/5/93), EP-A-540,090 (5/5/93), US4,615,820, EP-A-565,017 (10/13/93), EP-A-030,096 (6/10/81); They are added herein by reference.These compositions can contain the various particle cleaning ingredients that stably suspend wherein.Therefore these anhydrous compositions contain a liquid phase, an optional but preferred solid phase, and all these have detailed explanation in this paper back and the document quoted as proof.

These compositions of the present invention can be used for being formed for the aqueous cleaning solution of manual dishwashing.In general, these compositions of significant quantity are added in the entry, form moisture cleaning or soak solution.The aqueous solution that will so form contacts with tableware, mess kit and mess kit then.

Add the significant quantity that forms this paper detergent composition that contains aqueous cleaning in the entry and can comprise the about 500-20 of enough formation, the amount of the aqueous solution of 000ppm composition.More preferably in moisture cleaning liquid, provide about 800-5, this paper detergent composition of 000ppm.

Embodiments of the invention are described below, but and do not mean that restriction or otherwise limit its scope.All umbers used herein, percentage ratio and ratio all represent with weight percent, except as otherwise noted.

In following examples, all content all are that the weight % with composition quotes.Detergent composition embodiment

In these embodiments, use following abbreviation: MLAS according to crystallinity-disrupted alkyl benzene sulphonate (ABS), sodium-salt form or the potassium salt form of any previous methods embodiment preparation

Below abbreviation is used for the cleaning products promoter material: Cxy amine oxide: alkyl dimethyl amine n-oxide RN (O) Me with chain length Cxy ₂,

Wherein the average total carbon of the moieties R of non-methyl be 10+x extremely

10+yCxyAPG: formula R with chain length Cxy ₂O (C _nH _2nO) _t(glycosyl) _xAlkyl many

Glycosides, wherein R ₂Be C _10-18Alkyl; N is 2 or 3, and t is that 0-is about 10,

Preferred 0; And x is about 1.3-about 2.7.Glycosyl preferably derives from the Portugal

Grape sugar.Amylase: activity is the amylolytic enzyme of 60KNU/g, by NOVO Industries

A/S sells with trade(brand)name Termamyl 60T.Perhaps, amylase choosing

From: Fungamyl ^, Duramyl ^, BAN ^, and WO95/26397

With institute among the co-pending application PCT/DK96/00056 of Novo Nordisk

The αDian Fenmei APA:C that states ₈-C ₁₀Amido propyl group dimethylamine Cxy trimethyl-glycine: average total carbon number of moieties is the alkyl-dimethyl of 10+x to 10+y

Base trimethyl-glycine calcium salt calcium chloride, calcium sulfate, calcium hydroxide and composition thereof carbonate: anhydrous sodium carbonate, 200 microns-900 microns Citrate trianions: citrate trisodium dihydrate, 86.4%, 425 microns-850 microns citric acids: Citric Acid, usp, Anhydrous Powder CMC: Xylo-Mucine CxyAS: alkylsurfuric acid, sodium salt or specified other salt, moieties average

Total carbon number is 10+x to 10+yCxyEz: industrial straight or branched alcohol ethoxylate (does not have the medium chain methyl to prop up

Chain), average total carbon number of moieties is 10+x to 10+y, has

The ethylene oxide CxyEzS of average z mole: alkyl ethoxylated sulfate, sodium salt (perhaps specified other salt),

Average total carbon number of moieties is 10+x to 10+y, has average

The ethylene oxide DEA diethanolamine diamines alkyl diamine of z mole, for example 1,3-propylene diamine, Dytek EP, Dytek

A (Dupont) or be selected from: dimethylaminopropyl amine, 1,6-oneself two

Amine, 1,3-propylene diamine, 2-methyl isophthalic acid, 5-penta dioxane, 1,3-penta 2

Amine, 1-methyl-diaminopropanes, 1,3-cyclohexanediamine, 1,2-ring

Hexanediamine, 1,3-two (aminomethyl)-hexanaphthene DTPA: diethylenetriamine pentaacetic acid DTPMP: Diethylenetriamine five (phosphonic acids methylene ester), Monsanto (Dequest

2060) Et0H: the ethanol hydrotropic solvent is selected from: the sodium of toluenesulphonic acids, naphthene sulfonic acid, cumene sulfonic acid, xylene monosulfonic acid,

Potassium, magnesium, calcium, ammonium or water-soluble substituted ammonium salt LAS: linear alkylbenzene sulfonate (for example C11.8, sodium or sylvite) lipase: fat hydrolase, 100kLU/g, NOVO, Lipolase ^Perhaps

Lipase is selected from: Amano-P, M1 Lipase ^, Lipomax ^,

Described in US patent application serial numbers 08/341,826 by the fine hair humicola lanuginosa

The D96L-fat splitting enzyme variants of the native lipase that obtains; And suede

Hair humicola lanuginosa strain DSM 4106LMFAA:C _12-14Alkyl N-methyl glucose amide MA/AA:1: 4 toxilic acids/acrylic acid multipolymer, sodium salt, molecular-weight average

70000MBAxEy: mid-chain branched primary alkyl ethoxylate (average total carbon number=x; On average

EO=y) MBAxEyS: the primary alkyl ethoxylated sulfate of mid-chain branched or modification, sodium salt

(average total carbon number=x; Average EO=y)

According to the present invention (referring to embodiment 9) MBAyS: the mid-chain branched primary alkyl sulphates, sodium salt (the MEA:-thanomin CxyMES of average total carbon number=y): alkyl methyl sulfonated ester, sodium salt, average total carbon number of moieties

Be 10+x to 10+y magnesium salts: magnesium chloride, sal epsom, magnesium hydroxide and composition thereof NaOH: sodium hydroxide CxyNaPS: paraffin sulfonate, the average total carbon number of moieties be 10+x extremely

The sodium salt NaTS toluenesulfonic acid sodium salt PAA of 10+y: polyacrylic acid (molecular weight=4500) PAE: ethoxylation tetraethylene-pentamine PEG: polyoxyethylene glycol (molecular weight=4600) PG: propylene glycol proteolytic enzyme: proteolytic ferment, 4KNPU/g, NOVO, Savinase ^Perhaps egg

White enzyme is selected from: Maxatase ^, Maxacal ^, Maxapem 15 ^,

Subtilysin BPN and BPN ', proteolytic enzyme B, protease A, egg

White enzyme D, Primase ^, Durazym ^, Opticlean ^With

Optimase ^And Alcalase ^CxySAS secondary alkyl sulfate, the average total carbon number of moieties be 10+x extremely

The sodium salt silicate amorphous silicic acid sodium (SiO of 10+y ₂: Na ₂O=2.0) solvent hexylene glycol, ethanol or propylene glycol STPP tripoly phosphate sodium STPP, anhydrous foam enhancing polymkeric substance vinylformic acid (N, N-dimethylamino) alkyl ester; Methacrylic acid (N, N-

Dimethylamino) ethyl ester homopolymer; The amino second of dimethylaminoethyl acrylate methyl base

Ester/DMAA multipolymer; Poly-(DMAM) homopolymer; Poly-

(DMAM-is common-AA) (2: 1) multipolymer; Contain Lys, Ala, Glu,

Tyr (5: 6: 2: 1) and molecular weight be about 52,000 daltonian polypeptide vitriol sulfuric acid sodium, anhydrous TFA C _16-18Alkyl N-methyl glucose amide

Be often referred to as " accessory " general composition and can comprise spices, dyestuff, pH trims etc.

By following examples explanation the present invention, but and do not mean that restriction or otherwise limit its scope.Used all umbers, percentage ratio and ratio all represent with weight percent, except as otherwise noted.

Embodiment 6

Composition	???wt％ ???A	???wt％ ???B	????wt％ ????C	???Wt％ ???D
Composition	???wt％ ???A	???wt％ ???B	????wt％ ????C	???Wt％ ???D	MLAS	???5	???10	????20	???30
The C of middle branching _12-13Alkylethoxylate (9 moles of EO)	???1	???1	????1	???1	MLAS	???5	???10	????20	???30
	???1	???1	????1	???1	C _12-13Alkyl ethoxy (1-3) sodium sulfate	???25	???20	????10	???0
C _12-14Glucamide	???4	???4	????4	???4	C _12-13Alkyl ethoxy (1-3) sodium sulfate	???25	???20	????10	???0
C _12-14Glucamide	???4	???4	????4	???4	The coconut amine oxide	???4	???4	????4	???4
EO/PO segmented copolymer Tetronic ^704	???0.5	???0.5	????0.5	???0.5	The coconut amine oxide	???4	???4	????4	???4
EO/PO segmented copolymer Tetronic ^704	???0.5	???0.5	????0.5	???0.5	Ethanol	???6	???6	????6	???6
Hydrotropic agent	???5	???5	????5	???5	Ethanol	???6	???6	????6	???6
Hydrotropic agent	???5	???5	????5	???5	Magnesium ⁺⁺Salt	???3.0	???3.0	????3.0	???3.0
Water, thickening material and submember	To 100%	To 100%	To 100%	To 100%	Magnesium ⁺⁺Salt	???3.0	???3.0	????3.0	???3.0
Water, thickening material and submember	To 100%	To 100%	To 100%	To 100%	PH@10% (preparation)	???7.5	???7.5	???7.5	???7.5

Embodiment 7

	????A	????B	????C
	????A	????B	????C
pH10％	????9	????10	????10
pH10％	????9	????10	????10
MLAS	????30	????28	????25
MLAS	????30	????28	????25	Amine oxide (C12-14)	????5	????3	????7
Trimethyl-glycine	????3	????0	????1	Amine oxide (C12-14)	????5	????3	????7
Trimethyl-glycine	????3	????0	????1	Polyhydroxy fatty acid amide (C14)	????0	????1.5	????0
The AE nonionogenic tenside	????2	????0	????4	Polyhydroxy fatty acid amide (C14)	????0	????1.5	????0
The AE nonionogenic tenside	????2	????0	????4	Diamines	????1	????5	????7
Magnesium salts	????0.25	????0.2	????0.5	Diamines	????1	????5	????7
Magnesium salts	????0.25	????0.2	????0.5	Citrate trianion (cit2K3)	????0.25	????0	????0
				Citrate trianion (cit2K3)	????0.25	????0	????0
				Add up to by (spices, dyestuff, water, ethanol etc.)	(to 100%)

	????D	????E	????F
	????D	????E	????F
pH10％	????9.3	????8.5	????11
pH10％	????9.3	????8.5	????11
MLAS	????10	????15	????10
MLAS	????10	????15	????10	Paraffin sulfonate	????10	????0	????0
Linear alkylbenzene sulfonate	????5	????15	????12	Paraffin sulfonate	????10	????0	????0
Linear alkylbenzene sulfonate	????5	????15	????12	Trimethyl-glycine	????3	????1	????0
Polyhydroxy fatty acid amide (C12)	????3	????0	????1	Trimethyl-glycine	????3	????1	????0
Polyhydroxy fatty acid amide (C12)	????3	????0	????1	The AE nonionogenic tenside	????0	????0	????20
DTPA	????0	????0.2	????0	The AE nonionogenic tenside	????0	????0	????20
DTPA	????0	????0.2	????0	Citrate trianion (cit2K3)	????0.7	????0	????0
Diamines	????1	????5	????7	Citrate trianion (cit2K3)	????0.7	????0	????0
Diamines	????1	????5	????7	Magnesium salts	????1	????0	????0
Calcium salt	????0	????0.5	????0.2	Magnesium salts	????1	????0	????0
Calcium salt	????0	????0.5	????0.2	Proteolytic enzyme	????0.01	????0	????0.05
Amylase	????0	????0.05	????0.05	Proteolytic enzyme	????0.01	????0	????0.05
Amylase	????0	????0.05	????0.05	Hydrotropic agent	????2	????1.5	????3
Add up to by (spices, dyestuff, water, ethanol etc.)	(to 100%)			Hydrotropic agent	????2	????1.5	????3

Embodiment 8

	????A	????B	????C	????D	????E	????F
	????A	????B	????C	????D	????E	????F
pH10％	????8.5	????9	????9.0	????9.0	????8.5	????8.0
pH10％	????8.5	????9	????9.0	????9.0	????8.5	????8.0	MLAS	????10	????5	????5	????15	????10	????5
Middle branching alcohol oxyethyl group (0.6) vitriol	????0	????0	????0	????10	????0	????0	MLAS	????10	????5	????5	????15	????10	????5
Middle branching alcohol oxyethyl group (0.6) vitriol	????0	????0	????0	????10	????0	????0	Middle branching alcohol oxyethyl group (1) vitriol	????0	????25	????0	????0	????0	????25
Middle branching alcohol oxyethyl group (1.4) vitriol	????20	????0	????27	????0	????20	????0	Middle branching alcohol oxyethyl group (1) vitriol	????0	????25	????0	????0	????0	????25
Middle branching alcohol oxyethyl group (1.4) vitriol	????20	????0	????27	????0	????20	????0	Middle branching alcohol oxyethyl group (2.2) vitriol	????0	????0	????0	????10	????0	????0
Amine oxide	????5	????5	????5	????3	????5	????5	Middle branching alcohol oxyethyl group (2.2) vitriol	????0	????0	????0	????10	????0	????0
Amine oxide	????5	????5	????5	????3	????5	????5	Trimethyl-glycine	????3	????3	????0	????0	????3	????3
The AE nonionogenic tenside	????2	????2	????2	????2	????2	????2	Trimethyl-glycine	????3	????3	????0	????0	????3	????3
The AE nonionogenic tenside	????2	????2	????2	????2	????2	????2	Diamines	????1	????2	????0	????0	????0	????0
Magnesium salts	????0.25	????0.25	????0.01	????0.3	????0.25	????0.2	Diamines	????1	????2	????0	????0	????0	????0
Magnesium salts	????0.25	????0.25	????0.01	????0.3	????0.25	????0.2	Hydrotropic agent	????0	????0.4	????0	????0	????0	????0
Add up to by (spices, dyestuff, water, ethanol etc.)	(to 100%)						Hydrotropic agent	????0	????0.4	????0	????0	????0	????0

	????G	????H	????I	????J	????K	????L
	????G	????H	????I	????J	????K	????L	pH10％	????9.3	????8.5	????11	????10	????9	????9.2
							pH10％	????9.3	????8.5	????11	????10	????9	????9.2
							Middle branching alcohol oxyethyl group (0.6) vitriol	????10	????15	????10	????25	????2	????10
Paraffin sulfonate	????10	????0	????0	????0	????0	????0	Middle branching alcohol oxyethyl group (0.6) vitriol	????10	????15	????10	????25	????2	????10
Paraffin sulfonate	????10	????0	????0	????0	????0	????0	LAS	????0	????0	????0	????0	????7	????10
MLAS	????5	????15	????12	????2	????7	????10	LAS	????0	????0	????0	????0	????7	????10
MLAS	????5	????15	????12	????2	????7	????10	Trimethyl-glycine	????3	????1	????0	????2	????2	????0
Amine oxide	????0	????0	????0	????2	????5	????7	Trimethyl-glycine	????3	????1	????0	????2	????2	????0
Amine oxide	????0	????0	????0	????2	????5	????7	Polyhydroxy fatty acid amide (C12)	????3	????0	????1	????2	????0	????0
The AE nonionogenic tenside	????0	????0	????20	????1	????0	????2	Polyhydroxy fatty acid amide (C12)	????3	????0	????1	????2	????0	????0
The AE nonionogenic tenside	????0	????0	????20	????1	????0	????2	Hydrotropic agent	????0	????0	????0	????0	????0	????5
Diamines	????1	????5	????7	????2	????2	????5	Hydrotropic agent	????0	????0	????0	????0	????0	????5
Diamines	????1	????5	????7	????2	????2	????5	Magnesium salts	????1	????0	????0.2	????0.3	????0	????0
Calcium salt	????0	????0.5	????0	????0	????0.1	????0.1	Magnesium salts	????1	????0	????0.2	????0.3	????0	????0
Calcium salt	????0	????0.5	????0	????0	????0.1	????0.1	Proteolytic enzyme	????0.1	????0	????0	????0.05	????0.06	????0.1
Amylase	????0	????0.07	????0	????0.1	????0	????0.05	Proteolytic enzyme	????0.1	????0	????0	????0.05	????0.06	????0.1
Amylase	????0	????0.07	????0	????0.1	????0	????0.05	Lipase	????0	????0	????0.025	????0	????0.05	????0.05
DTPA	????0	????0.3	????0	????0	????0.1	????0.1	Lipase	????0	????0	????0.025	????0	????0.05	????0.05
DTPA	????0	????0.3	????0	????0	????0.1	????0.1	Citrate trianion (Cit2K3)	????0.65	????0	????0	????0.3	????0	????0
Add up to by (spices, dyestuff, water, ethanol etc.)	(to 100%)						Citrate trianion (Cit2K3)	????0.65	????0	????0	????0.3	????0	????0

Embodiment 9

	????A	????B	????C	????D	????E
	????A	????B	????C	????D	????E
pH10％	????8.5	????9	????10	????10	????10
pH10％	????8.5	????9	????10	????10	????10
LAS	????0	????0	????0	????15	????0
LAS	????0	????0	????0	????15	????0	MLAS	????30	????30	????27	????15	????33
Amine oxide	????5	????5	????5	????3	????6	MLAS	????30	????30	????27	????15	????33
Amine oxide	????5	????5	????5	????3	????6	Trimethyl-glycine	????3	????3	????0	????0	????0
The AE nonionogenic tenside	????2	????2	????2	????2	????4	Trimethyl-glycine	????3	????3	????0	????0	????0
The AE nonionogenic tenside	????2	????2	????2	????2	????4	Diamines	????1	????2	????4	????4	????5
Tripotassium Citrate	????0.25	????0.5	????0	????3.5	????2	Diamines	????1	????2	????4	????4	????5
Tripotassium Citrate	????0.25	????0.5	????0	????3.5	????2	Toxilic acid	????0.5	????1	????3	????0	????2
Magnesium salts	????0.25	????0.25	????0.01	????0.02	????0.2	Toxilic acid	????0.5	????1	????3	????0	????2
Magnesium salts	????0.25	????0.25	????0.01	????0.02	????0.2	Hydrotropic agent	????0	????0.4	????0	????0	????0
Add up to by (spices, dyestuff, water, ethanol etc.)	(to 100%)					Hydrotropic agent	????0	????0.4	????0	????0	????0

Embodiment 10

C ₁₂E _1.5S MLAS non-ionic surface active agent magnesium salts hydrotropic agent MEA/DEA antiseptic aqueous solvent and submember 10%pH	????A	????B	????C	????D	????E
	????A	????B	????C	????D	????E	-11.2 0.158 0.4 0.1-in right amount to 100% 6.67	9.66 13.71-0.19-1.07 0.14-in right amount to 100% 7.3	9.3 20.4-0.17-2.3-2.6 in right amount to 100% 7.3	22.4 13.4 0.14 2.31 1.4 4.5 in right amount to 100% 7.47	2.0 12.8 0.2 0.4----in right amount to 100% 5.23

Embodiment 11

C ₁₂E _1.5S C ₁₂E _2.9S C ₁₂E _3.7S MLAS non-ionic surface active agent amine oxide citrate APG betaine magnesium salts NaCl soap hydrotropic agent MEA/DEA antiseptic sodium carbonate silicate sodium sulphate aqueous solvent and submember (spices etc.) composition form	????A	????B	????C	????D	????E
	????A	????B	????C	????D	????E	4--7--0.1-1-0.1--4.0-in right amount to 100% liquid	---25 0.2 11.0 2.0 26.0-in right amount to 100% paste	2.2-17.8 2.3 0.01 1.4 1.6 in right amount to 100% gel	6.7--0.6 0.8 0.1 0.06 in right amount to 100% liquid	14.3 6.0 7.1 0.8 16.6 0.3 4.3 3.7 0.3 5.2 in right amount to 100% liquid

Embodiment 12

C ₁₂E _2.9S C ₁₂E _1.5S MLAS C ₁₂E _2.9The pH of MEA hydrotropic agent APG polymeric viscosifier betaine NaCl solvent magnesium salts spice water and submember 10% solution	????A	????B	????C	????D
	????A	????B	????C	????D	4.0 4.0 2.0 20.6 1.4 1.1--5.4 1.1-0.11 0.2 in right amount to 100% 4.9	2.0 2.0 4.0 20.6 1.4 1.1--5.4 1.1-0.11 0.2 in right amount to 100% 4.9	-9.0 26.7 2.0 3.0 1.5 0.5 0.2 0.3 in right amount to 100% 7.5	22.0 1.35 1.5 2.5 11 4.5 0.75 0.25 in right amount to 100% 7.5

Embodiment 13

A B C D EAE0.6S 6 10 13 15 20 amine oxides 6.5 6.5 7.5 7.5 7.5C10E8 33 4.5 4.5 4.5MLAS 20 16 13 11 6 diamines 0.5 0.5 1.25 10 magnesium salts 0.2 0.4 1.0 0.1 0.2 foam enhancing polymer 0 0.2 0.5 0.2 0.5 hydrotropic agents 1.5 1.5 111 ethanol 88888 sodium chloride 0.5 0.5 00 0.2pH 9998 10

F G H IAE0.6S 6 10 13 20 amine oxides 6.50 6.50 6.50 7.20MLAS 20 16 13 11 foam enhancing polymer 0.20 0.20 0.20 0.22 hydrotropic agent 1.50 1.50 3.50 2.0 polypropylene glycols, (MW2700) 111 1C10E8,3.00 3.00 3.00 3.30 diamines 0.50 00 0.55 magnesium salts, 0.22 0.3 0.5 0.25 sodium chloride 0.5-0.5-water and submember surplus surplus surplus surplus viscosity, (cps@70F) 150 330 650 330 pH@10% 8.3 9.0 9.0 9.0

J KAE0.6S 14.8 20MLAS 14 8 amine oxides 7.20 7.20 citric acids 3.00---maleic acid---2.50 magnesium salts, 0.22 0.1 sodium chloride 0.5-foam enhancing polymer, 0.22 0.22 cumene sodium sulfonate 3.30 3.30 ethanol, 6.50 6.50C10E8-------C11E9,3.33 3.33 diamines 0.55 0.55 spices, 0.31 0.31 water surplus surplus viscosity (cps@70F), 330 330pH@10% 9.0 9.0

Embodiment 14

A?????????B?????????C????????D????????E

14.2 14.3 6.5 13.1 10MLAS---21.3 14AE1S-16.8 20.5AE0.8S 9.6--AS 11.4AE3S---10 7APG 4.0 3.8 3.8 acid amides MEA 2.9 2MEA/DEA--1.5 betaine-4.0 4.0C10E8 0.3 0.29 0.35 0.2 0.3 magnesium salts water and submember an amount of to an amount of to an amount of to an amount of in right amount extremely

100％?????100％?????100％???100％????100％

Claims

1. manual dishwashing composition comprises:

A) the alkylaryl sulfonate surfactants system of described composition weight meter 0.1%-99.9%, this system comprise two or more crystallinity-disrupted following formula alkylaryl sulfonate surfactants of described surfactant system weight meter 10%-100%:

(B-Ar-D) _a(M ^Q+) _bWherein D is SO ₃ ^-, M is positively charged ion or cation mixt, and q is described cationic valency, and the number of a and b is through selecting, so that described composition is an electric neutrality; Ar is selected from benzene, toluene and combination thereof; B comprises that at least one contains the summation of uncle hydrocarbyl portion and one or more crystallinity-disrupted parts of 5-20 carbon atom, and wherein said crystallinity-disrupted part is interrupted or branch from described hydrocarbyl portion; And the crystallinity-disrupted degree of wherein said alkylaryl sulfonate surfactants system is not higher than 40 ℃ for its sodium critical solubility temperature by the CST test determination, and wherein said alkylaryl sulfonate surfactants system also has at least one following performance:

The weight ratio of non-quaternary carbon atom and quaternary carbon atom is at least 5: 1 among the B; With

B) the conventional manual dishwashing auxiliary agent of described composition weight meter 0.00001%-99.9%;

C) divalent ion that is selected from magnesium, calcium and composition thereof of composition weight meter 0.01%-7%.

2. manual dishwashing composition as claimed in claim 1 also contains the detersive enzyme of described composition weight meter 0.0001%-10%, and wherein said detersive enzyme is selected from proteolytic enzyme, cellulase, lipase, amylase, peroxidase and composition thereof.

3. as each manual dishwashing composition of claim 1-2, wherein Ar is a benzene.

4. as each manual dishwashing composition of claim 1-3, wherein said crystallinity-disrupted alkylaryl sulfonate surfactants comprises and is selected from least two kinds of following isomer:

I) based on substituting group at the ortho position of the attachment position of Ar-, a position-and contraposition-isomer, when Ar for replacing or during unsubstituted benzene;

Ii) based on the positional isomers of substituting group at the attachment position of B; With

Iii) based on the steric isomer of chiral carbon atom among the B.

5. as each manual dishwashing composition of claim 1-4, wherein the alkylaryl sulfonate surfactants system also comprises the unbroken following formula alkylaryl sulfonate surfactants of one or more crystallinity of the described surfactant system weight of 0%-85%:

(L-Ar-D) _a(M ^Q+) _bWherein the definition of D, M, q, a, b, Ar and described crystallinity-disrupted alkylaryl sulfonate surfactants is identical; And L is the straight-chain alkyl part that contains 5-20 carbon atom.

6. as each manual dishwashing composition of claim 1-5, wherein said crystallinity-disrupted alkylaryl sulfonate surfactants comprises two or more homologues, and two or more isomer of at least a homologue.

7. as each manual dishwashing composition of claim 1-6, wherein B not only comprises the odd number carbon chain length but also comprise the even carbon chain length.

8. as each manual dishwashing composition of claim 1-7, wherein uncle's hydrocarbyl portion of B accurately is one to have the straight-chain alkyl part of 7-16 carbon atom, and wherein said crystallinity-disrupted part is selected from:

I) side chain that links to each other with B is selected from: C1-C3 alkyl, C1-C3 alkoxyl group, hydroxyl and composition thereof;

Ii) interrupt the part of B structure, be selected from: ether, sulfone, silicone; With

Iii) and composition thereof.

9. as each manual dishwashing composition of claim 1-8, at least 60% described crystallinity-disrupted alkylaryl sulfonate surfactants of wherein said surfactant system weight is an isomeric forms, and wherein Ar is attached on second of the described straight-chain alkyl part of B or the 3rd carbon atom.

10. as each manual dishwashing composition of claim 1-9, wherein said cleaning combination is liquid, paste, liquid gel, gel, microemulsion, liquid crystals, particle, aggregate or powder.

11. as each manual dishwashing composition of claim 1-10, wherein said cleaning combination auxiliary agent also comprises and is selected from following tensio-active agent: alkylene carbonate, an alkyl Succinamate class, alkyl polysaccharide class, ethoxylated glycerol compounds and composition thereof.

12. as each manual dishwashing composition of claim 1-11, the crystallinity-disrupted degree of wherein said alkylaryl sulfonate surfactants system is not higher than 20 ℃ for its sodium critical solubility temperature by the CST test determination.

13. as each manual dishwashing composition of claim 1-12, the crystallinity-disrupted degree of wherein said alkylaryl sulfonate surfactants system is not higher than 80 ℃ for its calcium critical solubility temperature by the CST test determination.

14. as each manual dishwashing composition of claim 1-13, wherein the described biological degradation percentage ratio by improved SCAS test determination is at least 60%.

15. as each manual dishwashing composition of claim 1-14, wherein said conventional manual dishwashing auxiliary agent is selected from: the tensio-active agent except that (a), washing assistant, detersive enzyme, at least be partially soluble in water or be scattered in the polymkeric substance of water, abrasive, sterilant, tarnish inhibitor, dyestuff, solvent, hydrotropic agent, spices, thickening material, antioxidant, processing aid, suds booster, suds suppressor, suds-stabilizing agent, diamines, carrier, enzyme stabilizers, antioxidant, polysaccharide, buffer reagent, anti-mycotic agent, mould control agent, insect repellent, the protection against corrosion auxiliary agent, sequestrant and composition thereof.

16. as each manual dishwashing composition of claim 1-15, also contain nonionogenic tenside, its amount is that the 0.5%-25% of described detergent composition weight, wherein said nonionogenic tenside are the poly-alkoxyl alcohol with following end-blocking or non-end-blocking form:

-be selected from following hydrophobic grouping: straight chain C ₁₀-C ₁₆Alkyl, medium chain C ₁-C ₃Branching C ₁₀-C ₁₆Alkyl, Guerbet branching C ₁₀-C ₁₆Alkyl and composition thereof; With

-being selected from following hydrophilic radical: 1-15 ethoxylate, 1-15 propoxylated glycerine, 1-15 butoxy thing and composition thereof are end-blocking or non-end-blocking form.

17. as each manual dishwashing composition of claim 1-16, also contain alkyl sulfate surfactant, its amount is the 0.5%-25% of described detergent composition weight, and wherein said alkyl sulfate surfactant has one to be selected from following hydrophobic grouping: straight chain C ₁₀-C ₁₈Alkyl, medium chain C ₁-C ₃Branching C ₁₀-C ₁₈Alkyl, Guerbet branching C ₁₀-C ₁₈Alkyl and composition thereof and be selected from the positively charged ion of Na, K and composition thereof.

18. as each manual dishwashing composition of claim 1-17, also contain alkyl (poly-alkoxyl group) sulfate surfactant, its amount is the 0.5%-25% of described detergent composition weight, and wherein said alkyl (poly-alkoxyl group) sulfate surfactant has:

-being selected from following (poly-alkoxyl group) sulfate radical hydrophilic radical: 1-15 polyethoxye sulfate radical, the poly-propoxy-sulfate radical of 1-15, the poly-butoxy sulfate radical of 1-15,1-15 mix poly-(oxyethyl group/propoxy-/butoxy) sulfate radical and composition thereof, are end-blocking or non-end-blocking form; With

-be selected from the positively charged ion of Na, K and composition thereof.

19. as each manual dishwashing composition of claim 1-18, also contain tensio-active agent, wherein said tensio-active agent is selected from: anion surfactant, nonionogenic tenside, amphoterics, zwitterionics and composition thereof.

20. as each manual dishwashing composition of claim 1-19, also contain organic diamine, wherein said diamines is selected from following formula:

R wherein _2-5Be independently selected from H, methyl, ethyl and ethylene oxide; C _xAnd C _vBe independently selected from methylene radical or branched-chain alkyl, wherein x+v is 3-6; And A is optional to be existed and is selected from through selecting to give electronics or electrophilic part with what diamines pKa was adjusted to required scope.If A exists, x and y must be 2 or bigger so.

21. as each manual dishwashing composition of claim 1-20, also contain organic diamine, wherein said diamines has following formula: Each R wherein ⁶Be independently selected from H, C ₁-C ₄The straight or branched alkyl, have the alkylene oxide group of following formula:

-(R ⁷O) _mR ⁸R wherein ⁷Be C ₂-C ₄Straight or branched alkylidene group and composition thereof; R ⁸Be H, C ₁-C ₄Alkyl and composition thereof; M is 1-10; X is selected from following unit:

Ii) C ₃-C ₁₀Straight chain, C ₃-C ₁₀Branching straight chain, C ₃-C ₁₀Ring-type, C ₃-C ₁₀Branching ring alkylidene group, C ₆-C ₁₀Arylidene, wherein said unit comprise one or more pKa that make described diamines greater than 8 give electronic section or electrophilic part; With

Iii) (i) and mixture (ii),

As long as the pKa of described diamines is at least 8.

22. as each manual dishwashing composition of claim 20-21, wherein said diamines is selected from: dimethyl aminopropyl amine, 1,6-hexanediamine, 1,3-propylene diamine, 2-methyl isophthalic acid, 5-pentamethylene diamine, 1,3-pentamethylene diamine, 1,3-diaminobutane, 1,2-two (2-amino ethoxy) ethane, isophorone diamine, 1,3-two (methylamine)-hexanaphthene and composition thereof.

23. as each manual dishwashing composition of claim 1-22; also contain anion surfactant, wherein said anion surfactant is selected from: alkyl-sulphate, alkyl alkoxy sulfate, linear alkylbenzene sulfonate, α ethylenic sulfonate, paraffin sulfonate, methyl ester sulfonate, alkylsulfonate, alkyl alkoxylated suifate, sarcosinate, taurate, alkyl alkoxy carboxylate salt and composition thereof.

24. as each manual dishwashing composition of claim 1-23, also contain nonionogenic tenside, wherein said nonionogenic tenside is selected from: alkylethoxylate, polyhydroxy fatty acid amide, alkyl poly glucoside, alkylethoxylate and composition thereof.

25. as each manual dishwashing composition of claim 1-24, also contain amphoterics, wherein said amphoterics is selected from: trimethyl-glycine, sultaine, amine oxide and composition thereof.

26. as each manual dishwashing composition of claim 1-25, also contain the polymeric suds-stabilizing agent, it is selected from:

I) have the homopolymer of (N, N-dialkyl amido) alkyl acrylate of following formula:

Respectively do for oneself H, C of each R wherein ₁-C ₈Alkyl, and composition thereof, R ¹Be H, C ₁-C ₆Alkyl, and composition thereof, n is 2-6; With

The ii) multipolymer of (i) and following formula

R wherein ¹Be H, C ₁-C ₆Alkyl, and composition thereof, condition is to be 2 with the ratio of (i) (ii): 1-1: 2; And the molecular weight of wherein said foam of polymers stablizer is 1,000-2,000,000 dalton.

27. the method for a wash dining set, described method comprise that each the aqueous solution of composition of dirty tableware and claim 1-26 that needs are cleaned contacts.

28., also comprise the step of water with described composition dilution as the method for claim 27.

29., also comprise described composition is coated directly onto step on sponge or the towel as the method for claim 27.