CN1113952C - Detergent compositions - Google Patents

Abstract

The present invention relates to granular detergent compositions or components thereof, which comprise an oxygen-releasing bleaching system, containing a peroxygen source and one or more cationic compounds, which are cationic, (partially) quaternized ethoxylated (poly)amine compounds with clay-soil removal/anti-redeposition properties, for use in laundry and dish washing processes.

Description

Detergent composition

Technical field

The present invention relates to be used to do washing and granular detergent composition or its component of wash up, wherein comprise and have particulate/cation compound and the oxygen release bleach system of dirt removal/antiredeposition performance.

Background of invention

The performance of a particularly important of detergent composition is its ability of removing granular dirt in washing process from various fabrics.Modal granular dirt may be an earth type dirt.The dirt particle generally comprises silico-aluminate negative electricity layer, and the positive electricity positively charged ion (as calcium) that is positioned at interlayer and combines with the negative electricity layer.

Remove the compound of performance for having particulate/dirt, can propose various patterns.A kind of pattern requires this compound to have two kinds of different characteristics.First compound is adsorbed onto the ability on the mud particles negative electricity layer, and it two is, in case absorption, this compound draws back the ability of (expansion) negative electricity layer, and mud particles just loses its bounding force like this, can remove in washing water then.

Except removing particle/dirt, also need make the dirt of being removed keep suspending in the cycle in laundry (or wash up).The dirt of removing and being suspended in the washing water from fabric can deposit on the fabric face again.This dirt that deposits again can produce particularly noticeable delustring or " burnt hair " effect on white fabrics.In order to reduce this problem, can contain anti redeposition agent in the detergent composition.

For example, EP-B-111965 disclose have simultaneously that dirt is removed and the cation compound of antiredeposition performance in detergent application.

US4659802 and US4664848 have described having of can being used in combination with anion surfactant, and dirt is removed and the season amine of antiredeposition performance.

About the positive reactive anti-redeposition of deposited compound again, a kind of pattern has been proposed below.In washing water, positively charged molecule can be given these granulin molecule dispersing propertys in the lip-deep adsorption of mud particles.Along with increasing this compound is adsorbed onto on the suspended state dirt particle, the latter just is enclosed in by connecting in the hydrophilic layer that ethoxy unit produced.Like this,, just can suppress hydrophilic coating dirt, especially deposit again on the hydrophobic fabric (as polyester) at fabric at laundry or wash up in the cycle.

It is but that SYNTHETIC OPTICAL WHITNER is used for removing bleach spot or dirt from fabric that tradition is used for another component of washing composition, for example discharges the SYNTHETIC OPTICAL WHITNER of oxygen.

Most of SYNTHETIC OPTICAL WHITNER shortcoming in use is, because of many other detergent component to SYNTHETIC OPTICAL WHITNER responsive they can so just have been lost its original performance by the oxidation of SYNTHETIC OPTICAL WHITNER institute.Therefore, not every detergent component all with bleach-compatible.

It is compatible fully that the applicant has been found that the oxygen release SYNTHETIC OPTICAL WHITNER is joined by positively charged ion with dirt removal/antiredeposition performance, (part) season ethoxylation (gathering) amine and institute.Therefore both cation season ethoxylation (gathering) amine contains the cleaning composition of SYNTHETIC OPTICAL WHITNER or the overall cleaning and/or the whiteness maintenance effect of its component again, can improve, and can more effectively remove from fabric because can bleach the mud spot.

Also find, in detergent composition (or its component), be used in combination with part season ethoxylation (gathering) amine compared with (oxygen-release) SYNTHETIC OPTICAL WHITNER, make (release-oxygen) SYNTHETIC OPTICAL WHITNER and complete being used in combination of season ethoxylation (gather) amine, can improve clean better or whiteness maintenance effect.Even if but part season ethoxylation (gathering) amine also can combine with SYNTHETIC OPTICAL WHITNER to improve clean or whiteness maintenance effect.

Under the prerequisite of bound by theory not, the bleach-compatible of positively charged ion season ethoxylation (gathering) amine is soluble as follows.In these molecules, the seasonization of nitrogen groups it is believed that and can produce dual function.For on the fabric face or be dispersed in mud particles in the washing water, can improve thereon adsorption by in molecule, producing positive charge; In addition, be subjected to the oxidable not share electron pair of SYNTHETIC OPTICAL WHITNER attack, molecule is stabilized in the cloth-washing detergent that contains SYNTHETIC OPTICAL WHITNER by the decapacitation of getting on from nitrogen groups.

Its relevant portion of the document that all are quoted in this specification sheets all in conjunction with this paper as reference.

Summary of the present invention

The present invention relates to granular detergent composition or its component, has the cation compound of particulate/dirt removal/antiredeposition performance comprising the bleaching system of the release oxygen that contains peroxide source and one or more, i.e. positively charged ion (part) season ethoxylation (gathering) amine compound.

In more detail, the present invention relates to granular detergent composition or its component, wherein comprise:

(a) contain the oxygen release bleach system of peroxygen source; With

(b) have the water-soluble cationic compound of dirt removal/antiredeposition performance, it is selected from:

1) have ethoxylation positively charged ion one amine of following structural formula:

2) have the ethoxylation cationic diamine of following structural formula: Or Or

M wherein ¹Be N+ or N group; Each M ²Be N+ or N group; And at least one M ²Be the N+ group;

3) have the ethoxylation cationic polyamine of following structural formula:

4) and composition thereof; A wherein ¹Be

Or-O-,

R is H or C ₁-C ₄Alkyl or hydroxyalkyl, R ¹Be C ₂-C ₁₂Alkylidene group, hydroxyl alkylidene group, alkenylene, arylidene or alkarylene or C with about 20 oxyalkylene units of 2- ₂-C ₃The oxyalkylene part, but can not form any O-N key; Each R ²Be C ₁-C ₄Alkyl or hydroxyalkyl ,-the L-X part, or two R ²Formation-(CH together ₂) _r-A ²-(CH ₂) _s-part, wherein A ²For-O-or-CH ₂-, r is 1 or 2, s is 1 or 2, and r+s is 3 or 4; Each R ³Be C ₁-C ₈Alkyl or hydroxyalkyl, benzyl ,-the L-X part, perhaps, two R ³Or R ²With a R ³Formation-(CH together ₂) _r-A ²-(CH ₂) _s-part; R ⁴For replacing C ₃-C ₁₂Alkyl, hydroxyalkyl, alkenyl, aryl or have the alkaryl of para-orientation position; R ⁵Be C ₁-C ₁₂Alkenyl, hydroxyl alkylidene group, alkenylene, arylidene or alkarylene or C with about 20 oxyalkylene units of 2- ₂-C ₃The oxyalkylene part, but can not form any O-O or O-N key; X is for being selected from H, C ₁-C ₄The non-ionic group of alkyl or hydroxy alkyl ester or ether group and mixed group thereof; L is for containing polyoxyalkylene part-[(R ⁶O) _m(CH ₂CH ₂O) _n]-hydrophilic chain; R wherein ⁶Be C ₃-C ₄Alkylidene group or hydroxyl alkylidene group, and the number of m and n should make-(CH ₂CH ₂O) _n-part account for described polyoxyalkylene part at least about 50% weight; M ²During for N+, d is 1, M ²During for N, d is 0; For described positively charged ion one amine, n is at least about 16, for described cationic diamine at least about 6, for described cationic polyamine at least about 3; P is 3-8; Q is 1 or 0; T is 1 or 0, but q is 1 o'clock, and t is 1.

And wherein (a) is 80: 1 to 1: 5 with (b) ratio.

Detailed description of the present invention

An essential characteristic of the present invention is the water-soluble cationic compound with particulate/dirt removal/antiredeposition performance, and it is selected from positively charged ion one amine, diamines and polyamine.

The oxygen release bleaching system is 80: 1 to 1: 5 with the ratio of water-soluble cationic compound, preferred 40: 1 to 1: 2, and most preferably 20: 1 to 1: 1.

In detergent composition, water-soluble cationic compound is preferably the 0.01-30% of detergent composition weight, more preferably 0.1-15%, most preferably 0.2-3.0%.

Cationic amine

According to the present invention, can be used for the water-soluble cationic compound of the present invention of granular detergent composition or its component, comprise ethoxylation positively charged ion one amine defined above, ethoxylation cationic diamine and ethoxylation cationic polyamine.

In the aforementioned structural formula of cationic amine, R ¹Can be side chain (as, Cyclic (as,

Or most preferably straight chain (as

-CH ₂CH ₂-，-CH ₂CH ₂CH ₂-)

) alkylidene group, hydroxyl alkylidene group, alkenylene, alkarylene or oxyalkylene.For ethoxylation cationic diamine, R ¹Preferred C ₂-C ₆Alkylidene group.Each R ²Preferable methyl or-the L-X part; Each R ³Preferred C ₁-C ₄Alkyl or hydroxyalkyl, most preferable.

The positive charge of N+ group is offset by the counter anion of suitable number.Suitable counter anion comprises Cl ^-, Br ^-, SO ₃ ^-2, PO ₄ ^-2, MeOSO ₃ ^-Deng.Particularly preferred counter anion is Cl ^-And Br ^-

X is selected from hydrogen (H), C ₁-C ₄The non-ionic group of alkyl or hydroxy alkyl ester or ether group and mixed group thereof.Preferred ester or ether are respectively acetic ester and methyl ether.Particularly preferred non-ionic group is H and methyl ether.

In aforementioned structural formula, hydrophilic chain L is usually fully by polyoxyalkylene part [(R ⁶O) _m(CH ₂CH ₂O) _n]-form.In the polyoxyalkylene part-(R ⁶O) _m-and-(CH ₂CH ₂O) _n-can mix, or be preferably formed-(R ⁶O) _m-part and-(CH ₂CH ₂O) _nThe block of-part.R ⁶Preferred C ₃H ₆(propylidene); The preferred 0-of m is about 5, and most preferably 0, promptly this polyoxyalkylene part is fully by-(CH ₂CH ₂O) _n-form.-(CH ₂CH ₂O) _n-part preferably account for polyoxyalkylene part at least about 85% weight, most preferably account for 100% weight (m is 0).

In aforementioned structural formula, for cationic diamine and polyamine, M ¹With each M ²Preferred N+ group.

Preferred ethoxylation positively charged ion one amine and diamines have following structural formula:

Wherein X and n define as above, and a is 0-20, preferred 0-4 (as, ethylidene, propylidene, hexylidene), b is 1 or 0.For preferred cation one amine (b=0), n is preferably at least about 16, and its representative value scope is about 20-35.For preferred cation diamines (b=1), n is at least about 12, and its representative value scope is about 12-42.

In the aforementioned structural formula of ethoxylation cationic polyamine, R ⁴(straight chain, side chain or cyclic) preferably replaces C ₃-C ₆Alkyl, hydroxyalkyl or aryl; A ¹Preferably

N is preferably at least about 12, and its representative value scope is about 12-42; The preferred 3-6 of p.Work as R ⁴During for substituted aryl or alkaryl, q preferred 1 and R ⁵Preferred C ₂-C ₃Alkylidene group.Work as R ⁴Be substituted alkyl, hydroxyalkyl or alkenyl, and q is at 0 o'clock, R ⁵Preferred C ₂-C ₃The oxyalkylene part; When q is 1, R ⁵Preferred C ₂-C ₃Alkylidene group.

These ethoxylation cationic polyamines can be derived from the polyamino acid amides, as:

Or

These ethoxylation cationic polyamines also can be derived from polyamino propylene oxide derivative, as:

Wherein each c is 2-about 20.

The oxygen release bleaching system

Another essential characteristic of the present invention is the bleaching system that mainly contains the release oxygen of peroxygen source, and this system preferably accounts for 1%-40% weight in detergent composition, for example comprises inorganic hydration SYNTHETIC OPTICAL WHITNER and the organic peroxide acid crossed.

The ratio of oxygen release bleaching system and water-soluble cationic compound is 80: 1 to 1: 5, preferred 40: 1 to 1: 2, and most preferably 20: 1 to 1: 1.

The preferred system that plays bleaching action comprises hydrogen peroxide cource and peroxy acid bleach precursor compound.Produce peroxy acid by described precursor and hydrogen peroxide cource situ reaction.Preferred hydrogen peroxide cource comprises the inorganic hydration SYNTHETIC OPTICAL WHITNER of crossing.

Silicate material can be used as the granular detergent composition of the present invention stablizer of (containing the oxygen release SYNTHETIC OPTICAL WHITNER).Especially SiO ₂: Na ₂The ratio (R) of O is that about 1.6: 1 to 3.2: 1 alkalimetal silicate is suitable in this article, and the silicate outside this preferable range also can use certainly, is more relatively poor.The general sodium-salt form that adopts silicate, if but comprise and can further increase the composition general stability by magnesium, more comprehensively introduce as following.By (when for example preparing spray-dried granules, in identical slurries) adding water glass and magnesium salts (for example sal epsom or magnesium chloride) in identical particle, it is also very suitable to form Magnesium Silicate q-agent in position.The silicate that the present invention suits comprises water glass 1.6R solution, water glass 2.OR solid or the water glass 3.2R solid available from Hoechst or Akzo.Silicate will become the ratio of branch to be preferably 1: 1 by stable in addition oxidation-sensitive with it.

Inorganic perhydrate SYNTHETIC OPTICAL WHITNER

Inorganic perhydrate salt is preferred hydrogen peroxide cource.These salt are generally sodium salt, and its add-on is the 1-40% weight of composition, more preferably 2-30% weight, most preferably 5-20% weight.

Inorganic perhydrate salt comprises perborate, percarbonate, superphosphate, persulphate and persilicate.These inorganic perhydrate salt are an alkali metal salt normally.Inorganic perhydrate salt can be used as the crystalline solid that does not have other protection and adds.But concerning some perhydrate salt, the preference of this particulate composition has adopted a kind of coating attitude material that perhydrate salt in the particulate product provides better stability in storage that can be.

Sodium peroxoborate can be to have nominal structural formula NaBO ₂H ₂O ₂Monohydrate or tetrahydrate NaBO ₂H ₂O ₂3H ₂O.

SPC-D is the preferred perhydrate of the present invention.SPC-D is a kind of its structural formula and 2Na ₂BO ₂3H ₂O ₂Corresponding addition compound, available its crystalline solid.Percarbonate most preferably adds in the said composition with coated form, and product stability is provided.

Provide the suitable coating material of product stability to comprise basic metal, the water-soluble mixing salt of vitriol and carbonate.GB1,466,799 introduced this kind coating and coating method already.Mixing salt coating material and inorganic perhydrate weight ratio are in 1: 200 to 1: 4 scope, more preferably 1: 99 to 1: 9, and most preferably 1: 49 to 1: 19.Preferably sulfuric acid sodium and yellow soda ash mixing salt general formula be Na ₂SO ₄NNa ₂CO ₃, wherein n is 0.1 to 3, and is preferred 0.3 to 1.0, most preferably 0.2 to 0.5.

Other coating that contains silicate (independent or mix with borate or boric acid or other inorganics), wax, oil, fat soap also is applicable to the present invention.

The peroxide Potassium peroxysulfate is another the inorganic perhydrate salt that uses in the cleaning composition of the present invention.

Peroxyacid bleach precursor

Peroxyacid bleach precursor is preferably with 0.5% to 20% of composition weight, and more preferably 1% to 15%, most preferably 1.5% to 10% amount adds.

Suitable hydrophobic organic peroxide acid bleach precursor compound comprises one or more N-or O-acyl group usually, and the selectable scope of this precursor is very wide.Suitable kind comprises the acylated derivatives of acid anhydrides, ester, imide, lactan or imidazoles and oxime.In these kinds, the example of useful matter is disclosed in GB-A-1586789.Suitable ester class is disclosed in GB-A-836988,864798,1147871,2143231 and EP-A-0170386.

N-acylated lactams precursor

The N-acidylate precursor compound of lactams, what GB-A-955735 was total discloses this.And wide region of the present invention comprises any lactan as peroxyacid precursor, and preferably this class material comprises hexanolactam and Valerolactim.

Suitable N-acylated lactams precursor has following structural formula:

Wherein n is 0 to about 8, preferred 0 to about 2, and R ⁶Be alkyl, aryl, alkoxy aromatic yl or the alkaryl that H contains 1-12 carbon, or contain the substituted-phenyl of 6-18 carbon.

Suitable caprolactam bleach agent precursor as shown in the formula:

R wherein ¹Be alkyl, aryl, alkoxy aromatic yl or the alkaryl of a hydrogen or 1-12 carbon, preferred 6-12 carbon atom, most preferably R ¹It is phenyl.

Suitable Valerolactim has following structural formula:

R wherein ¹For hydrogen or contain alkyl, aryl, alkoxy aryl or the alkaryl of 1-12 carbon atom, preferred 6-12 carbon.R ¹More preferably from phenyl, heptyl, octyl group, nonyl, 2,4,4-tri-methyl-amyl, decene base and mixed group thereof.

Most preferred material is to be generally solid material, especially phenyl derivatives, i.e. benzoyl Valerolactim, benzoyl caprolactam and substituted benzene formyl analogue thereof, for example chloro, aminoalkyl, alkyl, aryl and alkoxy derivative below 30 ℃.

R ¹Contain at least 6 carbon, the hexanolactam and the Valerolactim precursor substance of preferred 6-12 carbon provided peroxy acid, give nucleophilicity and body dirt cleaning action when hydrolysis took place hydrophobic materials.R ¹The precursor compound that contains 1-6 carbon provides hydrophilic bleaching thing, and is effective especially to bleaching beverage spot.The mixture of hydrophobic and hydrophilic hexanolactam and Valerolactim, generally its weight ratio is 1: 5 to 5: 1, uses mixture soil release effect at preferred 1: 1 o'clock in the present invention.

Most preferred hexanolactam and Valerolactim precursor comprise benzoyl caprolactam, the nonanoyl hexanolactam, the benzoyl Valerolactim, the nonanoyl Valerolactim, 3.5.5-pivalyl hexanolactam, 3.5.5-trimethyl acetyl Valerolactim, the decoyl hexanolactam, the decoyl Valerolactim, the caprinoyl hexanolactam, the caprinoyl Valerolactim, hendecene acyl hexanolactam, hendecene acyl Valerolactim, (6-caprylamide hexanoyl) oxygen benzene sulfonate, (6-nonanoyl ammonia hexanoyl) oxygen benzene sulfonate, (6-caprinoyl ammonia hexanoyl) oxygen benzene sulfonate and composition thereof.Most preferred substituted benzene formyl lactan comprises the methyl benzamide hexanolactam, acyl ammonia in the toluyl penta, the ethylbenzoyl hexanolactam, the ethylbenzoyl Valerolactim, the propyl group benzoyl caprolactam, propylbenzene carbamoyl pentyl lactan, the sec.-propyl benzoyl caprolactam, isopropyl benzene carbamoyl pentyl lactan, the butyl benzoyl caprolactam, butylbenzene carbamoyl pentyl lactan, tertiary butyl benzoyl caprolactam, tert.-butylbenzene carbamoyl pentyl lactan, the amyl group benzoyl caprolactam, amylbenzene carbamoyl pentyl lactan, the hexyl benzoyl caprolactam, hexyl benzene carbamoyl pentyl lactan, phenetole formyl hexanolactam, phenetole formyl Valerolactim, the propoxy-benzoyl caprolactam, propoxy-benzoyl Valerolactim, isopropoxy benzoyl hexanolactam, isopropoxy benzoyl hexanolactam, the butoxy benzoyl caprolactam, butyl phenyl ether carbamoyl pentyl lactan, the tert.-butoxy benzoyl caprolactam, tert.-butoxy benzoyl Valerolactim, the pentyloxy benzoyl caprolactam, amyl phenyl ether carbamoyl pentyl lactan, the hexyloxy benzoyl caprolactam, hexyloxy benzoyl Valerolactim, 2.4.6-trichlorine benzoyl caprolactam, 2.4.6-trichlorobenzene carbamoyl pentyl lactan, penta fluoro benzene formyl hexanolactam, penta fluoro benzene carbamoyl pentyl lactan, the dichloro-benzoyl hexanolactam, dimethoxy benzoyl hexanolactam, 4-chlorobenzoyl hexanolactam, 2.4-dichloro-benzoyl hexanolactam, the terephthaloyl dicaprolactam, the dichloro-benzoyl Valerolactim, dimethoxy benzene carbamoyl pentyl lactan, 4-chlorobenzoyl Valerolactim, 2.4-dichloro-benzoyl Valerolactim, terephthaloyl two Valerolactims, 4-oil of mirbane formyl hexanolactam, 4-oil of mirbane formyl Valerolactim and composition thereof.

Peroxybenzoic acid precursors

Basically all peroxybenzoic acid precursors all are suitable for the present invention, comprise preferred N-acylated lactams class precursor.

Suitable O-acidylate peroxybenzoic acid precursors compound comprise replacement with unsubstituted benzoyl oxygen benzene sulfonate, for example compound of following formula:

The benzoylation product that Sorbitol Powder, glucose and all carbohydrates and benzoylation reagent form also is suitable for the present invention, for example following formula: compound:

A _c=COCH ₃B _g=benzoyl

Preferred acid imide peroxybenzoic acid precursors compound comprises the ureas that N-benzoyl succinimide, four benzoyl ethylene diamines and N-benzoyl replace.Suitable imidazole type peroxybenzoic acid precursors comprises N-benzoyl imidazoles and N-benzoyl benzoglyoxaline and other the peroxybenzoic acid precursors that contains the N-acyl group, comprises N-benzoyl pyrrolidone, dibenzoyl taurine and benzoyl Pyrrolidonecarboxylic acid.

Preferred peroxybenzoic acid precursors comprises the compound of benzoyl diacyl peroxide, benzoyl four acyl peroxides and following formula:

Tetra hydro Phthalic anhydride is another suitable peroxybenzoic acid precursors compound of the present invention:

Peroxybenzoic acid derivative precursor

Suitable peroxybenzoic acid derivative precursor comprises that the peroxybenzoic acid group that this paper has introduced is comprised the peroxybenzoic acid precursors that any functional group of alkyl replaces.

The positively charged ion peroxyacid precursor

Positively charged ion peroxyacid precursor compound also is suitable for the present invention.Described positively charged ion peroxyacid precursor generally forms by replacing the peroxy acid part with ammonium or alkyl ammonium group (preferred ethyl ammonium or ammonium methyl).

The positively charged ion peroxyacid precursor was introduced in following patent: U.S.4,904,406,4,751,015,4,988,451,4,397,757,5,269,962,5,127,852,5,093,022,5,106,528, U.K.1,382,594, EP475,512,458,396 and 284,292 and JP87-318,332.Preferred this precursor is disclosed among UK patent application NO.9407944.9 and the US application NO.08/298903,08/298650,08/298904 and 08/298906.

Suitable positively charged ion peroxyacid precursor comprises ammonium salt or alkylammonium salt, N-acidylate hexanolactam and the tetra-acetylated glucose benzoyl of the benzoyl peralcohol of all substituted alkyls or benzoyl oxygen Phenylsulfonic acid.

Preferred cation substituted benzoyl acyl-oxygen Phenylsulfonic acid is 4-(trimethyl ammonium) methyl-derivatives of the benzoyl oxygen Phenylsulfonic acid of following formula:

Preferred cation substituted alkyl oxygen Phenylsulfonic acid is 2,3, the ammonium methyl derivative of 3-trimethyl acetyl oxygen Phenylsulfonic acid.

Preferred cation N-acidylate hexanolactam class peroxyacid precursor comprises trialkyl ammonium methylene radical benzoyl caprolactam:

Another kind of preferred cationic peroxyacid precursor is 2-(N, N, a N-trimethyl ammonium chloride) ethyl 4-sulfo group phenyl-carbonic acid sodium.

The alkyl fatty peroxyacid bleach precursor

The alkyl fatty peroxyacid bleach precursor forms the alkyl fatty peroxy acid when crossing hydrolysis.Preferred this type of precursor draws peracetic acid when crossing hydrolysis.

Preferred imide-type alkyl fatty peroxyacid precursor compound comprises N, N, N ¹, N ¹-tetrem acidylate Alkylenediamine, wherein alkylidene group contains the compound that 1 to 6 carbon atom, especially alkylidene group contain 1,2 and 6 carbon atom.Preferred especially tetrem acyl ethylene diamine (TAED)

Organic peroxide acid

Detergent composition can contain the supplementary component organic peroxide acid of oxygen release bleaching system, and general content is 1% to 15% of composition weight, and preferred 1% to 10%.

Cationic polymers

Detergent composition and component thereof can comprise other cationic ethoxy amine polymer with particulate/dirt removal/antiredeposition performance that is selected from water-soluble cationic polymer.These polymkeric substance comprise main polymer chain, at least 2 M groups and at least one L-X group, wherein M be connected on the main chain or with main chain be the cation group of one; As non-ionic group, X is selected from H, C ₁-C ₄Alkyl or hydroxy alkyl ester or ether group and mixed group thereof; And L is for connecting M group and X group or X being connected to hydrophilic chain on the main polymer chain.

In detergent composition, the consumption of cationic ethoxy amine polymer is the 0.01-30% of detergent composition weight, more preferably 0.1-15%, most preferably 0.2-3%.

Herein, term " polymer " main chain " be meant the polymeric part that group M and L-X are connected or are combined as a whole.This term comprises oligopolymer main chain (2-4 unit) and true polymers main chain (5 or more multiple-unit).

In this article, term " is connected to " and is meant, the side group of this group for coming out from main polymer chain, and the example of this mode of connection can be represented by following general formula A and B:

In this article, term " is combined as a whole " and is meant that this group becomes the part of main polymer chain, and its example can be represented by following general formula C and D:

As long as formed cationic polymers is water miscible and has earth removal/antiredeposition performance, just can use any main polymer chain.The suitable polymers main chain can be derived from urethane, polyester, polyethers, polymeric amide, polyimide etc.; Polyacrylic ester, polyacrylamide, polyvingl ether, polyethylene, polypropylene and similarly polyalkenes, polystyrene and similarly poly-(alkarylene), polyalkyleneamines, polyalkylene imines, polyvinylamine, poly-alkylamine, polydiene propyl group amine, polyvinylpyridine, polyamino triazole, polyvinyl alcohol, amino poly-(ureylene), and composition thereof.

M contains N ⁺Any compatible cation group of (quaternary salt) positive center.The positive center of quaternary salt can be represented by following structure E and F:

Particularly preferred M group contains the quaternary salt center of being represented by general formula E.Cation group preferably is combined as a whole near main polymer chain or with it.

N ⁺The positive charge at center is offset by the counter anion of suitable number.Suitable counter anion comprises Cl ^-, Br ^-, SO ₃ ^2-, SO ₄ ^2-, PO ₄ ^2-, MeOSO ₃ ^-, or similar negatively charged ion.Particularly preferred counter anion is Cl ^-And Br ^-

X is selected from hydrogen (H), C ₁-C ₄The non-ionic group of alkyl or hydroxy alkyl ester or ether group and mixed group thereof.Preferred ester or ether are respectively acetic ester and methyl ether.Particularly preferred non-ionic group is H and methyl ether.

According to the present invention, in the cationic polymers that is applicable to detergent composition and component thereof, the ratio of cation group M and non-ionic group X is generally about 1: 1-1: 2.But,, can change the ratio of cation group M and non-ionic group X for example by suitable copolymerizable cationic monomers, non-ionic monomer (promptly containing the L-X group) and cationic/nonionic mix monomer.The ratio of group M and radicals X generally can be about 2: 1-1: 10.In the preferred cation polymkeric substance, this ratio is about 1: 1-1: 5.Normally random by the polymkeric substance that this copolyreaction forms, that is, cationic monomer, non-ionic monomer and cationic/nonionic mix monomer carry out copolymerization according to non-repetitive order.

The unit that contains group M and group L-X can account for cationic polymers 100% of the present invention.But the unit (preferably non-ionic) that also can in polymkeric substance, comprise other.Other unitary example comprises acrylamide, vinyl ether and contains not season tertiary amine group (M ¹) those groups (having the N center).These other unit can comprise the polymkeric substance of 0-about 90%, and (polymkeric substance of about 10-100% is for containing M and the L-X group (comprises M ¹-L-X group) unit).Usually, these other unit can comprise the polymkeric substance (polymkeric substance of about 50-100% is the unit that contains M and L-X group) of 0-about 50%.

The group number of M and L-X is respectively about 2-200.Usually, the number of M and L-X group is respectively about 3-100.The number of preferred L and L-X group is respectively about 3-40.

Except being used to connect M group and X group or being used to be connected to part on the main polymer chain, hydrophilic chain L is usually fully by polyoxyalkylene part-[(R ' O) _m(CH ₂CH ₂O) _n]-form.In the polyoxyalkylene part-(R ' O) _m-and-(CH ₂CH ₂O) _n-part can mix, or be preferably formed-(R ' O) _m-with-(CH ₂CH ₂O) _nThe block of-part.The preferred C of R ' ₃H ₆(propylidene); The preferred 0-of m is about 5, and most preferably 0, promptly this polyoxyalkylene part is fully by-(CH ₂CH ₂O) _n-form.-(CH ₂CH ₂O) _n-part preferably accounts for the polyoxyalkylene part at least about 85% weight, most preferably 100% weight (m is 0).For-(CH ₂CH ₂O) _n-part, n is generally about 3-100.N is preferably about 12-42.

A plurality of (2 or more) but-L-X part also hook connect together, be connected to then on M group or the main polymer chain, its example can be represented by following general formula G and H:

The structure of G and H and so on can be for example reacted by Racemic glycidol and M group or with main polymer chain, then formed hydroxyl-oxethylization is obtained.

The typical example of cationic polymers of the present invention is as follows:

A. urethane, polyester, polyethers, polymeric amide or similarly polymkeric substance.

One class suitable cationic polymers is derived from urethane, polyester, polyethers, polymeric amide or analogue.These polymkeric substance comprise and are selected from those unit with structural formula I, II and III:

(R ⁵) _k-[(C ₃H ₆O) _m(CH ₂CH ₂O) _n]-X

(R ⁵) _k-[(C ₃H ₆O) _m(CH ₂CH ₂O) _n]-X is A wherein ¹For Or

X is 0 or 1; R is H or C ₁-C ₄Alkyl or hydroxyalkyl; R ¹Be C ₂-C ₁₂Alkylidene group, hydroxyl alkylidene group, alkenylene, cycloalkylidene, arylidene or alkarylene or C with about 20 oxyalkylene units of 2- ₂-C ₃The oxyalkylene part, but can not with A ¹Form any O-O or O-N key; When x is 1, R ²For-R ⁵-, unless A ¹For

Or be-(OR ⁸) _y-or-OR ⁵-, but can not with A ¹Form any O-O or O-N key, and R ³For-R ⁵-, unless A ¹For

Or be-(OR ⁸) _y-or-OR ⁵-, but can not with A ¹Form any O-O or O-N key; When x is 0, R ²For:

-(OR ⁸) _y-,-OR ⁵-,

Or

And R ³For-R ⁵-; R ⁴Be C ₁-C ₄Alkyl or hydroxyalkyl or (R ⁵) _k-[(C ₃H ₆O) _m(CH ₂CH ₂O) _n]-X part; R ⁵Be C ₁-C ₂Alkylidene group, hydroxyl alkylidene group, alkenylene, arylidene or alkarylene; Each R ⁶Be C ₁-C ₄Alkyl or hydroxyalkyl or-(CH ₂) _r-A ²-(CH ₂) _s-, A wherein ²For-O-or-CH ₂-; R ⁷Be H or R ⁴R ⁸Be C ₂-C ₃Alkylidene group or hydroxyl alkylidene group; X be H,

-R ⁹, or its mixed group, wherein R ⁹Be C ₁-C ₄Alkyl or hydroxyalkyl; K is 0 or 1; M and n should make-(CH ₂CH ₂O) _n-part accounts for-[(C ₃H ₆O) _m(CH ₂CH ₂O) _n]-part at least about 85% weight; M is 0-about 5; N is at least about 3; R is 1 or 2; S is 1 or 2, and r+s is 3 or 4; Y is 2-about 20; The numerical value of u, v and w should make it have at least 2 N ⁺Center and at least 2 X groups.

In above structural formula, A ¹Preferably Or A ²Preferably-O-; X preferred 1; And the preferred H of R.R ¹Can be straight chain (as,

-CH ₂-CH ₂-CH ₂-, Or side chain (as

Alkylidene group, hydroxyl alkylidene group, alkenylene, cycloalkylidene, alkarylene or oxyalkylene; Work as R ¹Be C ₂-C ₃During the oxyalkylene part, the preferably about 2-12 of the number of oxyalkylene units; R ¹Preferred C ₂-C ₆Alkylidene group or phenylene, most preferably C ₂-C ₆Alkylidene group (as, ethylidene, propylidene, hexylidene).R ²Preferably-OR ⁵-or-(OR ⁸) _y-; R ³Preferably-R ⁵O-or-(OR ⁸) _y-; R ⁴And R ⁶Preferable methyl.As R ¹The same, R ⁵Can be straight chain or side chain, preferred C ₂-C ₃Alkylidene group; R ⁷Preferred H or C ₁-C ₃Alkyl; R ⁸Preferred ethylidene; R ⁹Preferable methyl; Preferred H of X or methyl; K preferred 0; M preferred 0; R and s difference preferred 2; The preferably about 2-12 of y.

In above structural formula, n is preferably at least about 6, at this moment N ⁺The number of center and X group is 2 or 3; N is most preferably at least about 12, and for the u+v+w of all scopes, its representative value scope is about 12-42.For homopolymer (v and w are 0), the preferably about 3-20 of u.For random copolymers (u is at least 1 or preferred 0), v and w are preferably about 3-40 respectively.

B. polyacrylic ester, polyacrylamide, polyvingl ether or similarly polymkeric substance.

Another kind of suitable cationic polymers is derived from polyacrylic ester, polyacrylamide, polyvingl ether or similar polymkeric substance.These polymkeric substance comprise and are selected from those unit with structural formula IV, V and VI:

A wherein ¹For

R is H or C ₁-C ₄Alkyl or hydroxyalkyl; R ¹For replacing C ₂-C ₁₂Alkylidene group, hydroxyl alkylidene group, alkenylene, arylidene or alkarylene or C ₂-C ₃The oxyalkylene part; Each R ²Be C ₁-C ₁₂Alkylidene group, hydroxyl alkylidene group, alkenylene, arylidene or alkarylene; Each R ³Be C ₁-C ₄Alkyl or hydroxyalkyl ,-(R ²) _k-[(C ₃H ₆O) _m(CH ₂CH ₂O) _n]-X part or common formation-(CH ₂) _r-A ²-(CH ₂) _s-part, wherein A ²For-O-or-CH ₂-; Each R ⁴Be C ₁-C ₄Alkyl or hydroxyalkyl or two R ⁴Common formation-(CH ₂) _r-A ²-(CH ₂) _s-part; X be H,

-R ⁵, or its mixed group, wherein R ⁵Be C ₁-C ₄Alkyl or hydroxyalkyl; J is 1 or 0; K is 1 or 0; The numerical value of m and n should make-(CH ₂CH ₂O) _n-part accounts for-[(C ₃H ₆O) _m(CH ₂CH ₂O) _n]-part at least about 85% weight; M is 0-about 5; N is at least about 3; R is 1 or 2; S is 1 or 2, and r+s is 3 or 4; The numerical value of u, v and w should make it have at least 2 N ⁺Center and at least 2 X groups.

In above structural formula, A ¹Preferably Or-O-;

A ²Preferably-O-; The preferred H of R.R ¹Can be straight chain (as,

-CH ₂-CH-CH ₂-，

Or side chain (as

Substituted alkylene, hydroxyl alkylidene group, alkenylene, alkarylene or oxyalkylene; R ¹The preferred C that replaces ₂-C ₆Alkylidene group or replacement C ₂-C ₃Oxyalkylene, most preferably

-CH ₂CH-or

Each R ²Preferred C ₂-C ₃Alkylidene group; R ³And R ⁴The difference preferable methyl; R ⁵Preferable methyl; Preferred H of X or methyl; J preferred 1; K preferred 0; M preferred 0; R and s difference preferred 2.

In above structural formula, according to n, u, v and the w of urethane and similar polymkeric substance, can be with n, u, v and w change.

C. polyalkylene amine, polyalkyleneimine or similar polymkeric substance.

Another kind of suitable cationic polymers is derived from polyalkylene amine, polyalkyleneimine or similar polymkeric substance.These polymkeric substance comprise and are selected from those unit with structural formula VII, VIII and IX:

(R ³) _k-[(C ₃H ₆O) _m(CH ₂CH ₂O) _n)-X

(R ³) _k-[(C ₃H ₆O) _m(CH ₂CH ₂O) _n]-X

R wherein ¹Be C ₂-C ₁₂Alkylidene group, hydroxyl alkylidene group, alkenylene, cycloalkylidene, arylidene or alkarylene or C with about 20 oxyalkylene units of 2- ₂-C ₃The oxyalkylene part, but can not form any O-N key; Each R ²Be C ₁-C ₄Alkyl or hydroxyalkyl or-(R ³) _k-[(C ₃H ₆O) _m(CH ₂CH ₂O) _n]-X part; R ³Be C ₁-C ₁₂Alkylidene group, hydroxyl alkylidene group, alkenylene, arylidene or alkarylene; M ' is N ⁺Or N center; X be H,

-R ⁴, or its mixed group, wherein R ⁴Be C ₁-C ₄Alkyl or hydroxyalkyl; M ' is N ⁺The time, d is 1, when M ' was N, d was 0; M ' is N ⁺The time, e is 2, when M ' was N, e was 1; K is 1 or 0; The numerical value of m and n should make-(CH ₂CH ₂O) _n-part accounts for-[(C ₃H ₆O) _m(CH ₂CH ₂O) _n]-part at least about 85% weight; M is 0-about 5; N is at least about 3; The numerical value of x, y and z should make it have at least 2 M ' groups, at least 2 N ⁺Center and at least 2 X groups.

In above structural formula, R ¹Can resemble the R in urethane and the similar polymkeric substance ¹Change like that; Each R ²Preferable methyl or-(R ³) _k-[(C ₃H ₆O) _m(CH ₂CH ₂O) _n]-X part; R ³Be C ₂-C ₃Alkylidene group; R ⁴Preferable methyl; The preferred H of X; K preferred 0; M preferred 0.

In above structural formula, n is preferably at least about 6, and at this moment the number of M ' and X group is 2 or 3; N is most preferably at least about 12, and for the x+y+z of all scopes, its representative value scope is about 12-42.Usually, x+y+z is that 2-is about 40, preferred 2-about 20.For short chain polymer, x+y+z is 2-9, has 2-9 N simultaneously ⁺Center and 2-11 X group.For long chain polymer, x+y+z is at least 10, preferred 10-about 42.For short chain and long chain polymer, M ' is generally the N of about 50-100% ⁺The mixed form at the N center of center and 0-about 50%.

Preferred this cationoid polymer-derived is from C ₂-C ₃Polyalkylene amine (x+y+z is 2-9) and polyalkyleneimine (x+y+z is at least 10, preferred 10-about 42).Particularly preferred positively charged ion polyalkylene amine and polyalkyleneimine are the poly-ethyleneamines of positively charged ion (PEA ' s) and polyethylene imine based (PEI ' s).These preferred cation polymkeric substance comprise the unit with following general formula:

[(CH ₂CH ₂O '] _n-X] ₂

R wherein ²(preferable methyl), M ', X, d, x, y, z and n definition are as above; A is 1 or 0.

Before ethoxylation, the PEA that is used to prepare cationic polymers of the present invention has following general formula:

Wherein x+y+z is 2-9, and a is 0 or 1 (molecular weight of about 100-400).Each hydrogen atom that is connected on each nitrogen-atoms represents to be used for the reactive site of ethoxylation subsequently.For preferred PEA, x+y+z is about 3-7 (molecular weight of about 140-310).These PEA can obtain by fractionation then by comprising the reaction of ammonia and Ethylene Dichloride.Usually the PEA of gained is Triethylenetetramine (TETA) (TETA) and tetren (TEPA).More than five amine, promptly hexamine, seven amine, eight amine and may nine amine, be difficult for fractionation by distillation owing to belong to deriving mixture together, therefore wherein can comprise other material, as cyclammonium, piperazine particularly.Also can there be cyclammonium, wherein contains nitrogen-atoms with side chain.Referring to, authorize the United States Patent (USP) № 2792372 of Dickson April 14 nineteen fifty-seven, wherein described the preparation process of PEA.

According to the unit number among the PEA, can change the required minimum ethoxylation degree of preferred dirt removal/antiredeposition performance.When y+z was 2 or 3, n was preferably at least about 6.If y+z is 4-9, then n can produce suitable effect at least about 3 o'clock.For preferred cation PEA, n is at least about 12, and its representative value scope is about 12-42.

At least about 440, this represents at least about 10 unit the molecular weight of PEI that is used to prepare polymkeric substance of the present invention before ethoxylation.The molecular weight that is used to prepare the preferred PEI of these polymkeric substance is about 600-1800.The main polymer chain of these PEI can be represented by following general formula:

Wherein the summation of x, y and z represents to obtain to have the number of the required enough sizes of the polymkeric substance of aforementioned molecular weight.Although can be the simple linear polymer main chain, also side chain can be arranged.According to preparation method, can change in the polymkeric substance primary, the relative proportion of the second month in a season and tertiary amine group.The distribution of amine groups is as follows usually :-CH ₂CH ₂-NH ₂30%

-CH ₂CH ₂-NH- 40％

-CH ₂CH ₂-N- 30％

Be connected among the PEI each hydrogen atom on each nitrogen-atoms and represent to be used for the reactive site of ethoxylation subsequently.These PEI can exist down as carbonic acid gas, sodium bisulfite, sulfuric acid, hydrogen peroxide, spirit of salt, acetate etc. by at catalyzer, polymerization ethylenimine and obtaining.The concrete grammar of preparation PEI is disclosed in, and the United States Patent (USP) № that the United States Patent (USP) № that authorizes people such as Ulrich December 5 nineteen thirty-nine March 8 in 2182306,1962 authorized people such as Mayle authorized people's such as Esselmann United States Patent (USP) № 2208095, the United States Patent (USP) № 2806839 that authorizes Crowther September 17 nineteen fifty-seven and authorizes the United States Patent (USP) № 2533696 (incorporating the present invention as a reference at this) of Wilson March 21 nineteen fifty-one on July 16 in 3033746,1940.

As defined in aforementioned structural formula, for positively charged ion PEI, n is at least about 3.But should be noted that the required minimum ethoxylation degree of suitable dirt removal/antiredeposition performance can increase along with the raising of PEI molecular weight, particularly far surpass about 1800 the time when the PEI molecular weight.In addition, the ethoxylation degree of preferred polymers also increases along with the raising of PEI molecular weight.At least about 600 PEI, n is preferably at least about 12 for molecular weight, and its representative value scope is about 12-42.Be at least 1800 PEI for molecular weight, n is preferably at least about 24, and its representative value scope is about 24-42.

D. diallyl amine polymer.

Another kind of suitable cationic polymers is derived from diallyl amine.These polymkeric substance comprise and are selected from those unit with structural formula X and XI:

R wherein ¹Be C ₁-C ₄Alkyl or hydroxyalkyl or-(R ²) _k-[(C ₃H ₆O) _m(CH ₂CH ₂O) _n]-X part; R ²Be C ₁-C ₁₂Alkylidene group, hydroxyl alkylidene group, alkylidene group, arylidene or alkarylene; Each R ³Be C ₁-C ₄Alkyl or hydroxyalkyl or common formation-(CH ₂) _r-A-(CH ₂) _s-part, wherein A be-O-or-CH ₂-; X be H,

-R ⁴, or its mixed group, wherein R ⁴Be C ₁-C ₄Alkyl or hydroxyalkyl; K is 1 or 0; The numerical value of m and n should make-(CH ₂CH ₂O) _n-part accounts for-[(C ₃H ₆O) _m(CH ₂CH ₂O) _n]-part at least about 85% weight; M is 0-about 5; N is at least about 3; R is 1 or 2; S is 1 or 2, and r+s is 3 or 4; X is 1 or 2; X is 0 o'clock, and y is 1, and x is 1 o'clock, and y is 0; The numerical value of u and v should make it have at least 2 N ⁺Center and at least 2 X groups.

In above structural formula, A is preferred-O-; R ¹Preferable methyl; Each R ²Preferred C ₂-C ₃Alkylidene group; Each R ³Preferable methyl; R ⁴Preferable methyl; The preferred H of X; K preferred 0; M preferred 0; R and s difference preferred 2.

In above structural formula, n is preferably at least about 6, at this moment N ⁺The number of center and X group is 2 or 3; N is most preferably at least about 12, and for the u+v of all scopes, its representative value scope is about 12-42.Usually, v is 0, and u is that 2-is about 40, preferred 2-about 20.

Other detergent component

According to the present invention, detergent composition and component thereof also can comprise other detergent component.The exact nature of these other components and add-on thereof depend on the physical aspect of composition or component and the exact nature of used washing operation thereof.

Composition of the present invention and component thereof preferably comprise one or more other detergent component, and they are selected from additional surfactants, additional SYNTHETIC OPTICAL WHITNER, bleach catalysts, alkaline system, washing assistant, organic polymer, enzyme, suds suppressor, lime soap dispersing agent, additional dirt suspension and anti redeposition agent, stain remover, spices and stopping agent.

Additional surfactants

According to the present invention, detergent composition and component thereof preferably comprise the additional surfactants that is selected from negatively charged ion, nonionic, positively charged ion, both sexes and zwitterionics and composition thereof.

The United States Patent (USP) 3929678 that on December 30th, 1975 was authorized Laughlin and Heuring has been enumerated typical negatively charged ion, nonionic, both sexes and zwitterionic classes tensio-active agent.Other example provides in " tensio-active agent and washing composition " (volume I and II, Schwartz, Perry and Berch).The United States Patent (USP) 4259217 that on March 31st, 1981 was authorized Murphy has been enumerated suitable cationic surfactants.

As long as exist, both sexes and zwitterionics generally are used in combination with one or more negatively charged ion and/or nonionogenic tenside.

Anion surfactant

According to the present invention, detergent composition and component thereof preferably comprise additional anion surfactant.Basically can comprise any anion surfactant that is used to wash in this detergent composition.Comprising as the salt of anion sulfate acid, sulfonic acid, carboxylic acid and the sarkosine of tensio-active agent (for example, comprise sodium, potassium, ammonium and substituted ammonium salt, as single-, two and triethanolamine salt).Sulphate anion surface active agent is preferred.

Other anion surfactant comprises isethionate, as fatty amide, alkyl succinate and the sulfosuccinate of acyl-hydroxyethyl sulfonate, N-acyl taurine salt, methyl tauride, the monoesters of sulfosuccinate (especially saturated and unsaturated C ₁₂-C ₁₈Monoesters), the diester of sulfosuccinate (especially saturated and unsaturated C ₆-C ₁₄Diester), N-acyl sarcosinate.Resinous acid and hydrogenated resin acid also are suitable, as rosin, staybelite and be present in or derived from the resinous acid and the hydrogenated resin acid of butter.

Sulphate anion surface active agent

Be applicable to that sulphate anion surface active agent of the present invention comprises the uncle position and secondary position alkyl-sulphate, alkyl ethoxy sulfate, fatty oil acylglycerol vitriol, alkylphenol ethylidene oxygen ether sulfate, C of straight or branched ₅-C ₁₇Acyl group-N-(C ₁-C ₄Alkyl) and-N-(C ₁-C ₂Hydroxyalkyl) glycosamine and vitriol, and the vitriol of alkyl poly glucoside, for example alkyl polyglucoside vitriol (the nonionic sulphate is introduced in this article).

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

Alkyl ethoxy sulfate surfactant is preferably selected from the ethoxylation C that each molecule has 0.5 to 20 moles of ethylene oxide ₁₀-C ₁₈Alkyl-sulphate, more preferably C ₁₁-C ₁₈Alkyl, most preferably C ₁₁-C ₁₅Alkyl, per molecule be with 0.5 to 7, such tensio-active agent of preferred 1 to 5 moles of ethylene oxide ethoxylation.

The particularly preferred aspect of the present invention is to adopt the mixture of preferred alkyl vitriol and alkyl ethoxy sulfate surfactant.This type of mixture is disclosed in PCT patent application NO.WO93/18124.

The anion sulfoacid salt surfactant

Be suitable for anionic sulphonate tensio-active agent used herein and comprise C ₅-C ₂₀Linear alkylbenzene sulfonate, alkyl ester sulfonate, C ₆-C ₂₂Uncle or secondary alkyl sulfonate, C ₆-C ₂₄Alkene sulfonate, sulfonation poly carboxylic acid, alkyl glycerol sulfonate, fatty acyl group glycerol sulfonate, fatty oleoyl glycerol sulfonate and their any mixture.

The anionic carboxylic acid salt surfactant

Suitable anionic carboxylate tensio-active agent comprises alkyl ethoxy carboxylate, alkyl ethoxy multi-carboxylate tensio-active agent and soap (' alkyl carboxyl '), the secondary soap of especially described herein some.

Suitable alkyl ethoxy carboxylate comprises having formula R O (CH ₂CH ₂O) _xCH ₂COO ^-M ⁺Those, wherein R is C ₆-C ₁₈Alkyl, x are 0-10, and ethoxylate distributes and should make, based on weight, wherein x be this amount of substance of 0 o'clock less than 20%, and M is a positively charged ion.Suitable many oxyethyl groups of alkyl multi-carboxylate tensio-active agent comprises having formula R O-(CHR ₁-CHR ₂-O)-R ₃Those, wherein R is C ₆-C ₁₈Alkyl, x are 1-25, R ₁And R ₂Be selected from hydrogen atom, methyl acid group, succsinic acid group, hydroxy succinic acid group and mixed group thereof, and R ₃Be selected from hydrogen atom, have the replacement of 1-8 carbon atom or do not replace hydrocarbon, and composition thereof,

Suitable soap surfactant comprises and contains the unitary secondary soap surfactant of the carboxyl that is connected on the secondary carbon(atom).It is water miscible being used for preferred secondary soap surfactant of the present invention, is selected from 2-methyl isophthalic acid-undeeanoic acid, 2-ethyl-1-capric acid, 2-propyl group-1-n-nonanoic acid, 2-butyl-1-is sad and the water-soluble salt of 2-amyl group-1-enanthic acid.Also can comprise some soap as suds suppressor.

The basic metal sarcosinate surfactant

Other suitable anion tensio-active agent is for having formula R-CON (R ¹) CH ₂The basic metal sarcosinate surfactant of COOM, wherein R is C ₅-C ₁₇Straight or branched alkyl or alkenyl, R ¹Be C ₁-C ₄Alkyl, and M is an alkalimetal ion.Its preference is the sodium-salt form of myristyl and oleoyl methyl sarcosinate.

Alkoxy-based non-ionic surface active agent

Basically any alkoxy-based non-ionic surface active agent all is applicable to the present invention.Preferred ethoxylation and propoxylation nonionogenic tenside.The preferred alkoxylated tensio-active agent can be selected from alkylphenol nonionic condenses, nonionic ethoxylated alcohol, nonionic ethoxylated/propoxylated fatty alcohol, nonionic ethoxylate/propoxylated glycerine and propylene glycol condenses and the condensation product of nonionic ethoxylate and propylene oxide/ethylenediamine adduct.

The alcohol alcoxylates nonionogenic tenside

Fatty alcohol and 1-25 mole alkylene oxide, particularly ethylene oxide and/condensation product of propylene oxide is applicable to the present invention.The alkyl chain of fatty alcohol can be straight or branched, uncle position or secondary position, and generally comprises 6-22 carbon atom.Particularly preferably be, its alkyl contains the alcohol of 8-20 carbon atom and the condensation product of 2-10 mole ethylene oxide/every mol of alcohol.

The polyhydroxy fatty acid amide nonionogenic tenside

Be applicable to that polyhydroxy fatty acid amide of the present invention has formula R ²CONR ¹Z, wherein R ¹Be H, C ₁-C ₄Alkyl, 2-hydroxyethyl, 2-hydroxypropyl, oxyethyl group, propoxy-or its mixed group, preferred C ₁-C ₄Alkyl, more preferably C ₁Or C ₂Alkyl, most preferably C ₁Alkyl (that is methyl); R ²Be C ₅-C ₃₁Alkyl, preferred straight chain C ₅-C ₁₉Alkyl or alkenyl, more preferably straight chain C ₉-C ₁₇Alkyl or alkenyl, most preferably straight chain C ₁₁-C ₁₇Alkyl or alkenyl, or its mixed group; And Z is that at least 3 hydroxyls are directly connected to polyhydroxy alkyl or its alkoxylate deriveding group (preferred ethoxylation and propenoxylated) on its line style hydrocarbon chain.Z preferably in reduction amination derived from reducing sugar; Z is glycidyl more preferably.

The fatty amide nonionogenic tenside

Suitable fatty acid amide surfactants has formula R ⁶CON (R ⁷) ₂, R wherein ⁶For containing 7-21 carbon atom, the alkyl of preferred 9-17 carbon atom, and each R ⁷Be selected from hydrogen atom, C ₁-C ₄Alkyl, C ₁-C ₄Hydroxyalkyl and-(C ₂H ₄O) _xH, wherein x is 1-3.

The alkyl polysaccharide nonionogenic tenside

Be applicable to that alkyl polysaccharide of the present invention is disclosed in the United States Patent (USP) 4565647 of authorizing Llenado on January 21st, 1986, wherein comprise hydrophobic group and polysaccharide, as the glycan glycosides, have the hydrophilic radical of 1.3-10 sugar unit with 6-30 carbon atom.

Preferred alkyl poly glucoside has structural formula:

R ²O (C _nH _2nO) t (glycosyl) _x

Wherein: R ²Be selected from alkyl, alkane phenyl, hydroxyalkyl, hydroxyalkyl phenyl and mixed group thereof, wherein alkyl group contains 10-18 carbon atom; N is 2 or 3; T is 0-10; And x is 1.3-8.Glycosyl is preferably derived from glucose.

Amphoterics

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

Suitable amine oxide comprises having formula R ³(OR ⁴) _xN ⁰(R ⁵) ₂Those compounds, R wherein ³Be selected from alkyl, hydroxyalkyl, amido propyl group and the alkane phenyl or its mixed group that contain 8-26 carbon atom; R ⁴Be alkylidene group or hydroxyl alkylidene group or its mixed group that contains 2-3 carbon atom; X is 0-5, preferred 0-3; And each R ⁵Be alkyl or hydroxyalkyl that contains 1-3 carbon atom or the polyoxyethylene group that contains 1-3 ethylene oxide group.Preferred C ₁₀-C ₁₈Alkyl dimethyl amine oxide and C _10-18Amidoalkyl dimethyl oxidation amine.

The suitable example of alkyl both sexes dicarboxylic acid is Miranol (TM) C2M Conc., by Miranol, and Inc., Dayton, NJ makes.

Zwitterionics

According to the present invention, zwitterionics also can add in detergent composition and the component thereof.These tensio-active agents can briefly be described as the derivative of derivative, the heterocycle second month in a season and tertiary amine of secondary and tertiary amine or the derivative of quaternary ammonium, quaternary phosphonium or uncle's sulfonium compound.Trimethyl-glycine and sultaine tensio-active agent are the examples that can be used for zwitterionics of the present invention.

Suitable trimethyl-glycine has formula R (R ') ₂N ⁺R ²COO-, wherein R is C ₆-C ₁₈Alkyl, each R ¹Be generally C ₁-C ₃Alkyl, and R ²Be C ₁-C ₅Alkyl.Preferred trimethyl-glycine is C _12-18Dimethyl caproic acid ammonium and C _10-18Amido propane (or ethane) dimethyl (or diethyl) trimethyl-glycine.Mix beet alkali surface activator also applicable to the present invention.

Cats product

The cats product that is applicable to detergent composition of the present invention and component thereof comprises quaternary ammonium surfactant, is selected from C ₆-C ₁₆, preferred C ₆-C ₁₀N-alkyl or alkenyl ammonium surfactant, wherein remaining N position is replaced by methyl, hydroxyethyl or hydroxypropyl.

The another kind of cats product that is applicable to detergent composition of the present invention and component thereof is the cationic ester tensio-active agent.

The cationic ester tensio-active agent is a kind of compound with surfactant properties of preferably water dispersiveness, wherein contains at least one ester (that is ,-COO-) key and at least one positive charge group.

For example, United States Patent (USP) № 4228042,4239660 and 4260529 discloses suitable cationic ester tensio-active agent, comprising the cholinesterase tensio-active agent.

Ester bond in the preferred surfactants molecule and positive charge group are separated from each other by spacer groups, and the chain of described spacer groups comprises at least 3 atoms (i.e. the chain length of 3 atoms), preferred 3-8 atom, more preferably 3-5 atom, most preferably 3 atoms.The atom that forms the spacer groups chain can be selected from carbon, nitrogen and Sauerstoffatom and mixed form arbitrarily thereof, but any nitrogen on the described chain or Sauerstoffatom only are connected with carbon atom in the chain.Therefore, for example get rid of-O-O-(that is, superoxide) ,-N-N-and-N-O-key group uniformly-spaced, but for example comprise-CH ₂-O-CH ₂-and-CH ₂-NH-CH ₂The spacer groups of-key etc.The spacer groups chain preferably includes only carbon atom, most preferably hydrocarbon chain.

The water soluble detergency promoter compound

According to the present invention, detergent composition and component preferred package thereof contain water-soluble washing-aid compound, and its consumption in detergent composition is generally the 1-80% weight of composition, preferred 10-70% weight, most preferably 20-60% weight.

The water soluble detergency promoter compound comprises any mixture of water-soluble monomer multi-carboxylate or its sour form, homopolymerization and copolymerization poly carboxylic acid or its salt, borate, phosphoric acid salt and aforementioned substances, and wherein said poly carboxylic acid comprises and is separated from each other at least two carboxyls that are no more than two carbon atoms.

Carboxylate salt and multi-carboxy acid salt washing agent can be monomer or oligomeric form, although because cost and performance cause and preferred monomers multi-carboxylate usually.

The suitable carboxylic salt that contains a carboxyl comprises the water-soluble salt of lactic acid, oxyacetic acid and ether derivant thereof.The multi-carboxylate of containing 2 carboxyls comprises water-soluble salt and the ether carboxylate and the sulfinyl carboxylate salt of succsinic acid, propanedioic acid, (ethylidene dioxy) oxalic acid, toxilic acid, diglycollic acid, tartrate, tartronic acid and fumaric acid.The multi-carboxylate of containing 3 carboxyls specifically comprises, water-soluble citrate, aconitate and citraconate and succinate derivative, as English Patent № 1379241 described carboxymethyl oxydisuccinic acid salt, English Patent № 1389732 described lactoyl oxydisuccinic acid salt and Netherlands patent applications 7205873 described aminosuccinic acid salt, and oxygen connection multi-carboxylate, as English Patent № 1387447 described 2-oxa-s-1,1,3-tricarballylic acid salt.

The multi-carboxylate of containing 4 carboxyls comprises, disclosed oxygen di-succinate, 1,1,2 among the English Patent № 1261829,2-ethane tetracarboxylic acid hydrochlorate, 1,1,3,3-propane tetracarboxylic acid salt and 1,1,2,3-propane tetracarboxylic acid salt.Contain the substituent multi-carboxylate of sulfo group and comprise, English Patent № 1398421 and 1398422 and United States Patent (USP) № 3936448 in disclosed sulfonation pyrolysis Citrate trianion among disclosed sulfo-succinic acid salt derivative and the English Patent № 1439000.Preferred multi-carboxylate is for containing the hydroxycarboxylate, particularly Citrate trianion of maximum 3 carboxyls in each molecule.

As useful builder component, also can consider the mixture of the parent acid of monomer or oligomeric multi-carboxylate's sequestrant or itself and salt, as citric acid or Citrate trianion/citric acid mixture.

In the present invention, borate washing assistant and the washing assistant that contains into borate substance are useful water soluble detergency promoters, described one-tenth borate substance washing composition store or wash conditions under can produce borate.

The suitable example of water-soluble phosphate washing assistant is the Sodium polymetaphosphate of alkali metal tripolyphosphates, trisodium phosphate, potassium and ammonium, sodium orthophosphate, potassium and ammonium, sodium-metaphosphate and potassium, the about 6-21 of the polymerization degree and the salt of phytic acid.

Be partly dissolved or insoluble washing-aid compound

According to the present invention, detergent composition and component thereof can comprise and be partly dissolved or insoluble washing-aid compound, and its consumption in detergent composition is generally the 1-80% weight of composition, preferred 10-70% weight, most preferably 20-60% weight.

The example of the insoluble washing assistant of most of water comprises sodium silicoaluminate.

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

Aluminosilicate zeolite can be a crude substance, but preferred synthetic deriving.Synthetic crystallization silico-aluminate ion exchange material can be buied, and its commodity are called zeolite A, zeolite B, zeolite P, X zeolite, zeolite HS and composition thereof.Zeolite A has structural formula

Na ₁₂[(AlO ₂) ₁₂(SiO ₂) ₁₂].xH ₂O

Wherein x is 20-30, especially 27.X zeolite has structural formula

Na ₈₆[(AlO ₂) ₈₆(SiO ₂) ₁₀₆].276H ₂O。

Another preferred aluminosilicate zeolite is a zeolite MAP builder.The amount of zeolite MAP is the 1-80% of composition weight, more preferably 15-40%.

EP384070A (Unilever) has described zeolite MAP builder.It is defined the alkali metal aluminosilicate of making zeolite P, and wherein the ratio of silicon and aluminium is no more than 1.33, preferred 0.9-1.33, more preferably 0.9-1.2.

Valuable especially is that wherein the ratio of silicon and aluminium is no more than 1.15, more special 1.07 the zeolite MAP that is no more than.

With d ₅₀Value represents that the granularity of zeolite MAP detergent builders is preferably the 1.0-10.0 micron, more preferably 2.0-7.0 micron, most preferably 2.5-5.0 micron.

d ₅₀The particulate diameter of value representation 50% weight is worth less than this.Granularity especially can be by conventional method of analysis, as using scanning electronic microscope or utilizing laser particle size analyzer to measure.Determine d ₅₀Other method of value is disclosed among the EP384070A.

Heavy metal ion chelating agent

Detergent composition of the present invention preferably comprises the heavy metal ion chelating agent as selectable components.In this article, " heavy metal ion chelating agent " be meant can with the component of heavy metal ion chelating.These components also can have calcium and magnesium sequestering power, but they preferably have and heavy metal, as iron, manganese and copper bonded selectivity.

The consumption of heavy metal chelant is generally the 0.005-20% of composition weight, preferred 0.1-10%, more preferably 0.25-7.5%, most preferably 0.5-5%.

Be applicable to that heavy metal ion chelating agent of the present invention includes organic phosphonates, as an alkali metal salt and the nitrilo trimethylene phosphonic salt of amino alkylidenyl many (alkylene phosphonic acids salt), ethane 1-hydroxyl di 2 ethylhexyl phosphonic acid.

In the above material, preferred diethylenetriamine five (methylene phosphonic acid salt), quadrol three (methylene phosphonic acid salt), hexanediamine four (methylene phosphonic acid salt) and hydroxyl-ethylidene-1,1-diphosphonate.

Be applicable to that other heavy metal chelant of the present invention comprises nitrilotriacetic acid(NTA) and polyamino carboxylic acid, as the amino tetraacethyl of ethylene, ethylidene pentaacetic acid, ethylenediamine disuccinic acid, quadrol two valeric acids, 2-hydroxy propylidene diamines disuccinic acid or its all salt.Particularly preferably be ethylene diamine-N, N '-disuccinic acid (EDDS) or its basic metal, alkaline-earth metal, ammonium or substituted ammonium salt or its mixture.

Be applicable to that other heavy metal chelant of the present invention is an iminodiacetic acid derivatives, as 2-hydroxyethyl oxalic acid or the glyceryl iminodiethanoic acid described in EP-A-317542 and the EP-A-399133.Iminodiethanoic acid described in the EP-A-516102-N-2-hydroxypropyl sulfonic acid and aspartic acid N-carboxymethyl N-2-hydroxypropyl-3-sulfonic acid sequestrant also are applicable to the present invention.Beta-alanine-N described in the EP-A-509382, N '-oxalic acid, aspartic acid-N, single acetate of N '-oxalic acid, aspartic acid-N-and imino-diacetic succsinic acid sequestrant also are suitable for.

EP-A-476257 has described the suitable sequestrant based on amino.EP-A-510331 has described derived from collagen, Keratin sulfate and caseic suitable sequestrant.EP-A-528859 has described suitable alkyl imino oxalic acid sequestrant.Two pyridine carboxylic acids and 2-phosphinylidyne butane-1,2, the 4-tricarboxylic acid also is suitable for.G-NH2-N, N '-disuccinic acid (GADS), quadrol-N, N '-two pentanedioic acid (EDDG) and 2-hydroxy propylidene diamines-N, N '-disuccinic acid (HPDDS) also is suitable for.

Bleach catalysts

The bleach systems that discharges oxygen can comprise a kind of bleach catalysts that contains transition metal.

A kind of suitable bleach catalysts is a catalyst system, wherein comprises to have the active transition-metal cation of decision bleach catalyst, as copper, iron or manganese positively charged ion; Has seldom or do not have the assistant metal positively charged ion of SYNTHETIC OPTICAL WHITNER catalytic activity, as zinc or aluminium cations; And the sequestrant, particularly ethylenediamine tetraacetic acid (EDTA), ethylenediamine tetraacetic (methylene phosphonic acid) and the water-soluble salt thereof that catalysis and assistant metal positively charged ion are had the decision stability constant.These catalyzer are disclosed in United States Patent (USP) № 4430243.

Other bleach catalysts comprises US5, disclosed manganese base complex in 246,621 and US5,244,594.The preference of these catalyzer comprises: Mn ^IV ₂(u-O) ₃(1,4,7-trimethylammonium-1,4,7-7-triazacyclononane) ₂(PF ₆) ₂, Mn ^III ₂(u-O) ₁(u-OAc) ₂(1,4,7-trimethylammonium-1,4,7-7-triazacyclononane) ₂(ClO ₄) ₂, Mn ^IV ₄(u-O) ₆(1,4, the 7-7-triazacyclononane) ₄(ClO ₄) ₄, Mn ^IIIMn ^IV ₄(u-O) ₁(u-OAc) ₂(1,4,7-trimethylammonium-1,4,7-7-triazacyclononane) ₂(ClO ₄) ₃And composition thereof.The open № 549272 of European patent has described other catalyzer.Be applicable to that other part of the present invention comprises 1,5,9-trimethylammonium-1,5,9-7-triazacyclononane, 2-methyl isophthalic acid, 4,7-7-triazacyclononane, 2-methyl isophthalic acid, 4,7-7-triazacyclononane, 1,2,4,7-tetramethyl--1,4, the 7-7-triazacyclononane, and composition thereof.

Be applicable to that bleach catalysts of the present invention also can select.The suitable example of bleach catalysts can be referring to US4246612 and US5227084.Referring to US5194416, wherein introduce monokaryon manganese (IV) complex compound in addition, as Mn (1,4,7-trimethylammonium-1,4,7-7-triazacyclononane) (OCH ₃) ₃(PF ₆).

As disclosed another kind of bleach catalysts among the United States Patent (USP) № 5114606 be manganese (III) and/or (IV) and have a water soluble complex of the non-carboxylic acid type polyol part of at least 3 continuous C-OH groups.Preferred part comprise sorbyl alcohol, iditol, red algae alcohol, (dulsitol), mannitol, Xylitol, arabitol, adonit, meso tetrahydroxybutane, meso-inositol, lactose, and composition thereof.

The bleach catalysts of the complex compound of United States Patent (USP) № 5114611 has introduced transition metal such as a kind of Mn of comprising, Co, Fe or Cu non--(greatly)-ring-type part.Described part has structural formula:

R wherein ¹, R ², R ³, and R ⁴Be selected from H, substituted alkyl and aryl respectively, make each R ¹-N=C-R ²And R ³-C=N-R ⁴Form 5 or 6 yuan of rings.Described ring can further replace.B is for being selected from O, S, CR ⁵R ⁶, NR ⁷With the bridging group of C=O, wherein R ⁵, R ⁶, and R ⁷Be respectively H, alkyl or aryl, comprise replacing or substituted radical not.Preferred part comprises pyridine, pyridazine, pyrimidine, piperazine, imidazoles, pyrazoles and triazole ring.Described ring can have substituting groups such as alkyl, aryl, alkoxyl group, halogen and nitro.Preferred bleach catalysts comprise Co, Cu, the two pyridyl methane of Mn, Fe-and-two pyridyl amine complexes.Catalyzer very preferably comprises Co (2,2 '-bipyridyl amine) Cl ₂, two (different sulphur cyanato) two pyridyl amine-cobalts (II), three (bipyridyl amine)-cobaltous perchlorates (II), Co (2,2 '-bipyridyl amine) ₂O ₂ClO ₄, two (2,2 '-two pyridyl amine)-cupric perchlorates (II), three (two-2-pyridyl amine)-Iron triperchlorate (II), and composition thereof.

Other example comprises the double-core Mn complex compound of the dentate part of the dentate that has four-N-tooth and two-N-tooth, as N ₄Mn ^III(u-O) ₂Mn ^IVN ₄) ⁺[bipyridyl ₂Mn ^III(u-O) ₂Mn ^IVBipyridyl ₂]-(ClO ₄) ₃

Other bleach catalysts is described in, for example, the open № 408131 (cobalt complex catalyst) of european patent application, the open № 384503 and 306089 (catalysis of metalloporphyrin agent) of european patent application, US4728455 (manganese/tooth ligand catalyst), the open № 224952 (adsorbing manganese on the aluminosilicate catalyst) of US4711748 and european patent application, US4601845 (silico-aluminate matrix) with manganese and zinc or magnesium salts, US4119557 (iron complex catalyzer), German patent specification 2054019 (cobalt chelating catalyst), Canada's 866191 (salt that contain transition metal), US4430243 (sequestrant) with manganese positively charged ion and on-catalytic metallic cation, and US4728455 (gluconic acid Mn catalyst).

Other examples comprise Mn (CF ₃SO ₃) ₂, Co (NH ₃) ₅Cl.

In the compositions and methods of the invention, the consumption of bleach catalysts is generally catalytically effective amount." catalytically effective amount " is meant, this is measured under any simultaneous test condition, is enough to improve the effect of removing dirt from the target matrix bleaching.Test conditions can change, and this depends on the kind of used scrubber and user's custom.In laundry operations, the certain user likes using hot water, and other users then use warm water even cold water.Certainly, the catalytic performance of bleach catalysts is subjected to the influence of these factors, and therefore in allocating washing composition and whitener composition fully, the consumption of bleach catalysts can suitably be adjusted.In fact (infinite) can adjust composition of the present invention and method, in containing water lotion, to produce 0.1ppm at least, and the preferred active bleaching agent catalysis concentration of about 1-200ppm.In order further to be explained, at 40 ℃, under pH=10 and the European washing machine condition, if use perborate and bleach precursor, the Mn catalyst of 3 mmole order of magnitude concentration is exactly effective so.And to reach equifinality, under American washing machine condition, require concentration to improve 3-5 doubly.

Enzyme

Another preferred component that is used for detergent composition and component thereof is one or more additional enzymes.

Preferred additional enzymes comprises commercially available lipase, at, amylase, neutrality and Sumizyme MP, cellulase, endoenzyme, esterase, polygalacturonase, Sumylact L and the peroxidase in the common adding detergent composition.Suitable enzyme was introduced in United States Patent (USP) № 3519570 and 3533139.

Preferred commercially available proteolytic enzyme comprises, those that sell with trade(brand)name Alcalase, Savinase, Primase, Durazym and Esperase by the Novo Industries A/S of Denmark, those that sell with trade(brand)name Maxatase, Maxacal and Maxapem by Gist-Brocades, those that sell by Genencor International, and sell with trade(brand)name Opticlean and Optimase by Solvay Enzyme those.According to the present invention, the consumption of proteolytic enzyme in composition can be the 0.0001-4% organized enzyme of composition weight.

Preferred amylase comprises GB1, the α-Dian Fenmei of describing in detail among 296,839 (NoVo) that derives from the special bacterial strain of the dried bacterium of special lichens brood cell.Preferred commercially available amylase comprises, those that sold with trade(brand)name Rapidase by Gist-Brocades, those that sold with trade(brand)name Termamyl and BAN by Novo Industries A/S.According to the present invention, the consumption of amylase in composition can be the 0.0001-2% organized enzyme of composition weight.

The consumption of lipase can be the 0.0001-2% weight of composition weight, preferred 0.001-1% weight, the most preferably active lipase of 0.001-0.5% weight.

Lipase can derive from fungi and bacterium, for example, can produce the humic Pseudomonas bacterial strain of lipase., the mould Pseudomonas of high temperature or comprise pseudomonas pseudoalcaligenes or the Rhodopseudomonas of Pseudomonas fluorescens.Derive from the chemistry of these Pseudomonas or the lipase of gene modification mutation and also can be used for the present invention.Preferred lipase is derived from false pain alkali bacillus pseudomonas, and this is disclosed among mandate European patent EP-B-0218272.

Another preferred lipase of the present invention can be dredged cotton shape hair humic bacterium gene by the clone, in host's aspergillus oryzae, express this gene then and obtain, this has description at European patent application EP-A-0258068, and the Novo Industries A/S of Denmark Bagsvaerd sells with trade(brand)name Lipolase.This lipase is authorized on March 7th, 1989 in people's such as Huge-Jensen the United States Patent (USP) 4810414 also description.

Organic polymer

According to the present invention, organic polymer is the preferred annexing ingredient of detergent composition and component thereof, therefore is preferably the component in any granular component, and wherein they can bond together granular component.In this article, " organic polymer " is meant, in detergent composition, be commonly used for any basically organic polymer of dispersion agent and antiredeposition and soil-suspending agent, according to the present invention, as any high molecular organic polymer of earth flocculation agent, but is not season ethoxylation (gathering) amine dirt removal/anti redeposition agent comprising in this article.

The consumption of organic polymer in detergent composition of the present invention is generally the 0.1-30% of composition weight, preferred 0.5-15%, most preferably 1-10%.

The example of organic polymer comprises water-soluble organic homopolymerization-or copolymerization-poly carboxylic acid or its salt, and wherein said poly carboxylic acid comprises and is separated from each other at least two carboxyls that are no more than two carbon atoms.Back one polymkeric substance is disclosed in GB-A-1596756.

The example of these salt be its MWt1800-5000 the multi-carboxylate and with the multipolymer of maleic anhydride, the molecular weight of these multipolymers is 2000-100000, especially 40000-80000.

The polyamino compound can be used for the present invention, comprising those compounds derived from aspartic acid, as disclosed among EP-A-3052282, EP-A-305283 and the EP-A-351629.

The terpolymer that contains the monomeric unit that is selected from toxilic acid, vinylformic acid, poly aspartic acid and vinyl alcohol, especially molecular-weight average are that the terpolymer of 5000-10000 is also applicable to the present invention.

Other organic polymer that is applicable to detergent composition of the present invention comprises derivatived cellulose, as methylcellulose gum, carboxymethyl cellulose, Vltra tears and Natvosol.

Other useful organic polymer is that polyoxyethylene glycol, especially molecular weight are 1000-10000, more preferably 2000-8000, most preferably from about 4000 polyoxyethylene glycol.

Press down foam system

When detergent composition of the present invention is used to machine-wash composition in allotment, preferably comprise the 0.01-15% that its consumption is a composition weight, preferred 0.05-10%, most preferably the foam that presses down of 0.1-5% is.

Be used for the suitable foam system that presses down of the present invention and can comprise any basically known anti-foam compound, for example comprise anti-foam compound of siloxanes and the anti-foam compound of 2-alkyl alcohol.

In this article, " anti-foam compound " be meant and can reduce by detergent composition solution, particularly the foaming that is produced when stirring this solution or any compound or its mixture of the degree of foaming.

Being particularly preferred for anti-foam compound of the present invention is the anti-foam compound of siloxanes, and it is defined as any anti-foam compound that comprises silicone components in this article.The anti-foam compound of these siloxanes also comprises silica component usually.In this paper and general industry field, term " siloxanes " comprises the polymkeric substance of the various higher molecular weights that contain siloxane unit and various alkyl.The anti-foam compound of preferred siloxanes is a siloxanes, the polydimethylsiloxane that especially has trimethyl silyl end-blocking block unit.

Other suitable anti-foam compound comprises fatty monocarboxylic acid and water-soluble salt thereof.Authorize the United States Patent (USP) 2954347 of Wayne St.John and described these materials December 27 nineteen sixty.Generally have 10-24 carbon atom as the mono carboxylic acid of aliphatic series of froth suppressor and the hydrocarbyl chain of water-soluble salt thereof, be preferably 12-18 carbon atom.Its suitable salt comprises an alkali metal salt, as sodium, potassium and lithium salts, and ammonium and alkanol ammonium salt.

Other suitable anti-foam compound comprises, for example, and the fatty acid ester of high molecular fatty ester (as, fatty acid triglycercide), monohydroxy-alcohol, aliphatic C ₁₈-C ₄₀Ketone (as stearone), N-alkylation aminotriazine, as three-to six-alkyl melamine or two-to four-alkyl diamine chlorotriazine (cyanuryl chloride and two or three moles have the uncle of 1-24 carbon atom or reaction product, the propylene oxide of secondary amine), distearyl acid amides and single stearyl two-basic metal (as, sodium, potassium and lithium) phosphoric acid salt and phosphoric acid ester.

The preferred foam system that presses down comprises:

(a) anti-foam compound, the anti-foam compound of preferred siloxanes, the siloxanes that most preferably comprises following component is prevented the foam compound

(i) consumption is the 50-99% of the anti-foam compound weight of siloxanes, the polydimethylsiloxane of preferred 75-95%; With

(ii) consumption is the 1-50% of the anti-foam compound weight of siloxanes/silicon-dioxide, the silicon-dioxide of preferred 5-25%;

The add-on of the anti-foam compound of wherein said silica/silicon oxygen alkane is a 5-50% weight, preferred 10-40% weight;

(b) consumption is a 0.5-10% weight, the compound dispersing agent of preferred 1-10% weight, most preferably comprise siloxane glycol rake formula (rake) multipolymer, wherein the content of polyoxyalkylene is 72-78%, and the ratio of ethylene oxide and propylene oxide is 1: 0.9-1: 1.1; Particularly preferred this siloxane glycol rake formula multipolymer is DC0544, can be buied by DOW Corning, and commodity are called DC0544;

(c) consumption is a 5-80% weight, and the inertia carrier fluid compound of preferred 10-70% weight most preferably comprises C ₁₆-C ₁₈Ethoxylated alcohol, wherein ethoxylation degree is 5-50, preferred 8-15.

EP-A-0210731 has described a kind of particulate very preferably and has pressed down foam system, wherein comprises siloxanes and prevents that foam compound and fusing point are 50-85 ℃ organic carrier, and wherein organic carrier comprises glycerine and the monoesters with lipid acid of 12-20 carbon atom.The preferred particulate that EP-A-0210721 discloses other presses down foam system, and wherein organic carrier is fusing point 45-80 ℃, and its carbochain has lipid acid or alcohol or its mixture of 12-20 carbon atom.

The dye transfer inhibitor polymkeric substance

Detergent composition of the present invention also can comprise 0.01-10% weight, the dye transfer inhibitor polymkeric substance of preferred 0.05-0.5% weight.

Preferably from multipolymer, Polyvinylpyrolidone (PVP) or its mixture of polyamine N-oxide, N-vinyl pyrrolidone and N-vinyl imidazole, wherein these polymkeric substance can be cross-linked polymers to dye transfer inhibitor.

A) Polyamine N-oxide

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

Wherein P is a polymerizable unit,

A is

-O-,-S-,-N-; X is 0 or 1

R is aliphatic series, aliphatic, the aromatics of ethoxylation, heterocycle family or alicyclic group or its any mixed group, and nitrogen-atoms can connect on it or becomes its part in the N-O group.

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

Or

R wherein ₁, R ₂, R ₃Be aliphatic series, aromatics, heterocycle family or alicyclic group or its mixed group, x or/and y or/and z is 0 or 1, and the nitrogen-atoms of N-O group can connect on it or becomes its part.The N-O group can become the part of polymerizable unit (P), maybe can be connected on the main polymer chain, or either way have.

Wherein the N-O group suitable polyamine N-oxide that becomes a polymerizable unit part comprises, wherein R be selected from aliphatic series, aromatics, alicyclic or heterocyclic group group polyamine N-oxide.A kind of described polyamine N-oxide comprises that wherein the nitrogen in the N-O group becomes those polyamine N-oxide of a R group part.Preferred polyamine N-oxide compound is a heterocyclic group for R wherein, as those of pyridine, pyrroles, imidazoles, tetramethyleneimine, piperidines, quinoline, acridine and derivative thereof.

Other suitable polyamine N-oxide is connected to polyamine oxide compound on the polymerizable unit for N-O group wherein.Preferred these polyamine N-oxide comprise that wherein nitrogen-atoms is the polyamine N-oxide with general formula (I) of a described R group part in the N-O functional group, and wherein R is aromatics, heterocycle family or alicyclic group.Its example is that wherein R is a heterogeneous ring compound, as those polyamine N-oxide of pyridine, pyrroles, imidazoles and derivative thereof.

The polyamine N-oxide that can almost be had any polymerization degree.The polymerization degree is unimportant, as long as this material has required water-soluble and dye suspension performance.Its molecular-weight average is generally 500-1000000.

B) The multipolymer of N-vinyl pyrrolidone and N-vinyl imidazole

Molecular weight is that the N-vinyl pyrrolidone of 5000-50000 and the multipolymer of N-vinyl imidazole also are applicable to the present invention.In preferred copolymer, the mol ratio of N-vinyl imidazole and N-vinyl pyrrolidone is 1-0.2.

C) Polyvinylpyrolidone (PVP)

Detergent composition of the present invention also can use the Polyvinylpyrolidone (PVP) (" PVP ") of molecular-weight average as 2500-400000.Suitable Polyvinylpyrolidone (PVP) can be available from ISPCorporation, New York, NY and Montrel, Canada, its name of product are PVP K-15 (viscosity-average molecular weight is 10000), PVP K-30 (molecular-weight average is 40000), PVP K-60 (molecular-weight average is 160000) and PVP K-90 (molecular-weight average is 360000).PVP K-15 also can be available from ISP Corporation.Other suitable Polyvinylpyrolidone (PVP) available from BASF Corporation comprises Sokalan HP 165 and Sokalan HP 12.

D) Ju Yi Xi oxazolidinone

Detergent composition of the present invention also can use Ju Yi Xi oxazolidinone as the dye transfer inhibitor polymkeric substance.The molecular-weight average of described Ju Yi Xi oxazolidinone is 2500-400000.

E) Polyvinyl imidazol

Detergent composition of the present invention also can use polyvinyl imidazol as the dye transfer inhibitor polymkeric substance.The preferred 2500-400000 of the molecular-weight average of described polyvinyl imidazol.

White dyes

In detergent composition of the present invention, also optional certain hydrophilic white dyes that contains the 0.005-5% weight of having an appointment.

Can be used for hydrophilic white dyes of the present invention and have following structural formula:

R wherein ₁Be selected from anilino, N-2-two-hydroxyethyl and NH-2-hydroxyethyl; R ₂Be selected from N-2-pair-hydroxyethyl, N-2-hydroxyethyl-N-methylamino-, morpholino, chlorine and amino; And M is a salt-forming cation, as sodium or potassium.

In following formula, work as R ₁Be anilino, R ₂Be N-2-two-hydroxyethyl, and M is positively charged ion, during as sodium, whitening agent is 4,4 '-two [(4-anilino-6-(N-2-two-hydroxyethyl)-s-triazine-2-yl) amino]-2,2 '-stilbene disulfonic acid and disodium salt thereof.This specific whitening agent can have been bought from Ciba-geigy company, and its commodity are called Tinopal-UNPA-GX.In detergent composition of the present invention, Tinopal-UNPA-GX is the preferred hydrophilic white dyes that uses.

In following formula, work as R ₁Be anilino, R ₂Be N-2-hydroxyethyl-N-2-methylamino-, and M being positively charged ion, during as sodium, whitening agent is 4,4 '-two [(4-anilino-6-(N-2-hydroxyethyl-N-methylamino-)-s-triazine-2-yl) amino]-2,2 '-the Stilbene disulfonic acid disodium salt.This specific whitening agent can have been bought from Ciba-geigy company, and its commodity are called Tinopal 5BM-GX.

In following formula, work as R ₁Be anilino, R ₂Be morpholino, and M being positively charged ion, during as sodium, whitening agent is 4,4 '-two [(4-anilino-6-morpholino-s-triazine-2-yl) amino]-2,2 '-the Stilbene disulfonic acid disodium salt.This specific whitening agent can have been bought from Ciba-geigy company, and its commodity are called Tinopal AMS-GX.

The polymkeric substance stain remover

In detergent composition of the present invention, the known polymkeric substance stain remover of optional use below is called " SRA ".If use, SRA generally accounts for the 0.01-10.0% of composition weight, is generally 0.1-5%, is preferably 0.2-3.0%.

Usually, preferred SRA contains hydrophilic segment and hydrophobic part, wherein: but described hydrophilic segment hydrophilicity-imparting treatment hydrophobic fiber, as the surface of polyester and nylon; Described hydrophobic part then deposits on the hydrophobic fiber, then by finishing washing and rinse cycle adheres on the hydrophobic fiber, thereby becomes the sticking agent of hydrophilic segment.This can guarantee that the spot that is produced is easier to be cleaned in washing step afterwards after SRA handles.

Preferred SRA comprises low polyterephthalate, and it, prepares by the method that comprises at least a transesterification/oligomerization under the existence as titanium (IV) alkoxide normally at metal catalyst.These esters can be made with other monomer, these monomers can via one, two, three, four or more the multi-section position introduce in the ester structure, and surely not form highly cross-linked overall structure.

Suitable SRA comprises the sulfonated products of substantial linear ester oligomer; it comprises terephthaloyl and the multiple unitary oligomer ester main chain of oxygen base alkylidene group oxygen basic weight; with covalently bound allyl group to this main chain the sulfonation terminal portions of deriving; for example; JJ.Scheibei and E.P.Gosselink are at the US4 in November 6 nineteen ninety; 968,451 are described this.This ester oligomer can make by following steps: (a) allyl alcohol is handled in ethoxylation, (b) in two-step approach transesterification/oligomerization, product and dimethyl terephthalate (DMT) (" DMT ") and 1 with (a), 2-propylene glycol (" PG ") reacts, and (c) product and the sodium metabisulfite of (b) is reacted in water.Other SRA comprises, people such as Gosselink are at the US4 on December 8th, 1987,711, nonionic end-blocking terephthalic acid 1 in 730,2-propylidene ester/terephthalic acid gathers (oxygen ethylidene) ester, as generating by transesterification/oligomerization of poly-(ethylene glycol) methyl ether, DMT, PG and poly-(ethylene glycol) (" PEG ").Other example of SRA comprises; Gosselink is at the US4 on January 26th, 1988, disclosed part and the end capped oligomer ester of negatively charged ion fully in 721,580, and as ethylene glycol (" EG "), PG, DMT and 3, the oligopolymer of the hot sodium sulfonate of 6-two oxa-s-8-hydroxyl; Gosselink is at the US4 on October 27th, 1987, nonionic end-blocking block polyester oligopolymer in 702,857, as, by DMT, methyl (Me) end-blocking PEG and EG and/or PG, perhaps the mixture by DMT, EG and/or PG, Me end-blocking PEG and dimethyl-5-sulfoisophthalic acid sodium generates; And on October 31st, 1989 authorize Maldonado; people's such as Gosselink US4; 877; negatively charged ion in 896 (particularly sulphur aroyl) end-blocking terephthalate; the latter can be used for doing washing and the typical SRA of textile finishing product; between its example is served as reasons-and ester composition that sulfosalicylic acid list sodium salt, PG and DMT make, optional but preferably comprise institute and add PEG (for example, PEG 3400).

SRA also comprises: the simple segmented copolymer of ethylene glycol terephthalate or propylene glycol ester terephthalate and terephthalic acid polyethylene oxide or terephthalic acid poly(propylene oxide), authorize the US3 of Hays referring on May 25th, 1976,959, authorized the US3 of Basadur on July 8th, 230 and 1975,893,929; Derivatived cellulose, as derive from the hydroxy ethers cellulose polymer compound METHOCEL of Dow; C ₁-C ₄Alkylcellulose and C ₄Hydroxy alkyl cellulose is authorized people's such as Nico US4,000,093 referring on December 28th, 1976; And average (methyl) degree that replaces is the methyl cellulose ether of each about 1.6-2.3 in glucoside unit.Its viscosity (2% aqueous solution) under 20 ℃ is about 80-120 centipoise.These materials can METOLOSE SM100 and METOLOSE SM200 buy, they are trade(brand)names of the methyl cellulose ether made by Shinetsu Kagaku Kogyo KK..

Another kind of SRA comprises: (I) use the vulcabond coupler to connect the nonionic terephthalate of polymer esters structure, and referring to people's such as Violland US4,201,824 and people's such as Lagasse US4,240,918; (II) have the SRA of carboxylicesters end group, it is by trimellitic acid 1,2-anhydride being added on the known SRA, changing terminal hydroxyl group into trimellitate and obtain.By suitable selecting catalyst, trimellitic acid 1,2-anhydride can be received on the end group of polymkeric substance and not by opening anhydride bond by the ester bond of an isolated carboxylic acid of trimellitic acid 1,2-anhydride.Nonionic or negatively charged ion SRA can be used as starting raw material, but as long as they contain the terminal hydroxy group of esterification.Referring to people's such as Tung US4,525,524.In addition, also comprise: (III) urethanum-keyed jointing type is based on the SRA of terephthalic acid anion salt, referring to people's such as Violland US4, and 201,824.

Other optional component

Other optional component that is applicable to the present composition comprises spices, tinting material and filling salt, and wherein sodium sulfate is preferred filling salt.

The detergent formulation of the nearly pH neutral of washing lotion

Although detergent composition of the present invention uses in broad washing lotion pH scope (as, about 5-12), in allotment to nearly neutral wash solution pH value, promptly in 20 ℃ of water, under the concentration of about 0.1-2% weight, particularly suitable when initial pH is about 7.0-10.5.The nearly neutral pH prescription of washing lotion helps stabilized enzyme and prevents the dirt sedimentation.In these prescriptions, washing lotion pH value preferred about 7.0-10.5, more preferably from about 8.0-10.5, most preferably from about 8.0-9.0.

J.H.M.Wertz and P.C.E.Goffinet disclose the detergent formulation of the nearly pH neutral of preferred washing lotion in the european patent application 83.200688.6 of application on May 16 nineteen eighty-three.

This based composition very preferably also preferably comprise about 2-10% weight citric acid and a small amount of (as, less than about 20% weight) neutralizing agent, buffer reagent, phase modifier, hydrotropic solvent, enzyme, enzyme stabilizers, polyprotonic acid, foaming regulator, opacifying agent, antioxidant, sterilant, dyestuff, spices and whitening agent, authorize as on August 25th, 1981 described in people's such as Barrat the United States Patent (USP) 4285841.

The formation of composition

Detergent composition of the present invention can be made by the whole bag of tricks, comprising with all cpds dry mixed and gathering contained in the detergent component.

Detergent component is preferably formed the part of detergent composition.

According to composition of the present invention can be various physical forms, comprising particle, tablet, thin slice, lozenge and strip.It is so-called concentrated granular detergent composition that the partitioning device that utilization is arranged in washing machine drum adds the composition that the washing machine that pollutes fabric is housed.

Also can be used for according to composition of the present invention, for example in the bleaching compositions of additives of chlorine bleaching agent, or be used in combination with it.

In general, can make by the whole bag of tricks, comprising dry mixed, sprinkling drying, gathering and granulation according to granular detergent composition of the present invention.Can add in other the detergent component by dry mixed, gathering (preferably combining) or as spraying dried ingredients according to season removal mud/anti redeposition agent of the present invention with carrier substance.

In the particulate composition that comprises water-soluble cationic dirt removal/antiredeposition compound, the average particle size particle size of component should preferably be no more than 15% particle diameter greater than 1.8 millimeters and be no more than 15% particle diameter less than 0.25 millimeter.Average particle size particle size should make preferably that the particulate diameter of 10-50% is the 0.2-0.7 millimeter.

Defined herein term " average particle size " be by with composition sample at a series of sieves, be filtered into many fractions (being generally 5 fractions) on the preferred Tyler sieve and calculate.With the relative sieve of the fraction weight aperture mapping of gained thus.Average particle size is thought in the aperture that the sample of 50% weight can pass through.

According to the present invention, the volume density of granular detergent composition is generally at least 600 grams per liters, more preferably 650 grams per liter to 1200 grams per liters.The measuring cup that volume density is utilized simple funnel and had plate valve in its lower end is measured, and wherein, the content in the funnel can all be poured the axially aligned cylindric measuring cup that is arranged in the funnel below into by plate valve.130 millimeters in this funnel is high, and the internal diameter of its top and bottom is respectively 130 millimeters and 40 millimeters.During installation, its lower end is positioned at the above 140 millimeters places of base-plates surface.The total height of measuring cup is 90 millimeters, and inner height is 87 millimeters, and internal diameter is 84 millimeters.Its nominal volume is 500 milliliters.

In order to measure, powder is poured in the funnel by hand, open plate valve, make powder be full of measuring cup then.The measuring cup of filling is removed from support, used the straight flange instrument then,, cross its upper limb, remove excessive powder as cutter.This measuring cup of filling of weighing is then doubly taken advantage of the powder weight value of gained, obtains volume density (grams per liter).As required, can carry out replicate measurement.

The compacting solid can use any suitable compaction process, and as compressing tablet, briquetting or extrude, preferred pressed disc method is made.The tablet that is used for wash up can preferably use the standard Rotarytabletpress to make, and use therein pressure is 5-13KN/ centimetre ², more preferably 5-11KN/ centimetre ², compacting solid minimum hardness is 176-275N like this, preferred 195-245N, and this is by being measured by the C100 hardness-testing device of I.Hollandinstrument supply.This method can be used for preparing the even or stratiform tablet of virtually any size and shape.Tablet is preferably symmetric to guarantee the uniform dissolution of tablet in washing lotion.

Clothes washing method

The present invention that machine washing method herein is usually included in dissolving or allotment significant quantity machine-washes in the washing machine of detergent composition, uses the washings processing pollution clothes." detergent composition of significant quantity " is meant, dissolving or allotment rise 10-300 gram product in the washing lotion at 5-65, and this is the common dosage and the washing lotion volume commonly used of product in the conventional machine washing method.

In washing methods, preferably adopt partitioning device.Partitioning device is equipped with Betengent product, before beginning washing, by it product is directly introduced in the washing machine drum then.Its volume should make it possible to comprise enough Betengent products that is usually used in the washing methods.

Before washing machine is equipped with clothing, among or afterwards, begin the washing before, the partitioning device that will comprise Betengent product is put into cylinder.When beginning to carry out wash(ing)cycle, in cylinder, add the machine water, cylinder carries out Periodic Rotating then.The design of partitioning device should be able to comprise dry Betengent product, when wash(ing)cycle, owing to cylinder rotates the agitaion that produces, and by contacting with washing water, this product is discharged then.

In order to discharge Betengent product when washing, this equipment has many openings that this product can pass through.In addition, make the material liquid permeable of this equipment and impermeable solid phase prod, therefore can discharge dissolved product.Preferred Betengent product just discharges rapidly when begin wash(ing)cycle, in this washing stage, produces of short duration high local concentrations product in washing machine drum thus.

Preferred partitioning device is reusable, and through design, can keep the globality of container when drying regime and wash(ing)cycle.Following patent has been described the particularly preferred partitioning device that uses with the present composition: GB-B-2157717, GB-B-2157718, EP-A-0201376, EP-A-0288345 and EP-A-0288346.Be published in ManufacturingChemist by J.Bland, in November, 1989, the special preferred allocation equipment that the particle cleaning product with so-called " granula " uses also described in the article on the 41-46 page or leaf.Another preferred allocation equipment that uses with the present composition is disclosed in PCT patent application NoWO94/11562.

Special preferred allocation equipment is disclosed in european patent application № 0343069﹠amp; In 0343070.Back one patent application discloses a kind of bag shape flexible shroud equipment that is extended out by the support ring that surrounds a hole, its opening be suitable in bag, adding in the washing step one wash(ing)cycle required adequate prod.The part washing medium opening of flowing through enters in the bag, dissolved product, and solution outwards flows in the washing medium via this opening then.Support ring has a kind of screen type structure to prevent to enter wetting, undissolved product, and this structure generally includes the radial extension wall that is extended to form the spoked wheel configuration by the center shell, or has the similar structures of spirrillum wall.

In addition, partitioning device can be a flexible cell, as the bag shape.Bag can be to apply the impermeable protectiveness material of water to keep the fibrous texture of content here, as disclosed among the open № 0018678 of european patent application.As disclosed among the open № 0011500,0011501,0011502 and 0011968 of european patent application, it can also be made by the insoluble synthetic polymer of water, wherein has rupturable edge seal design in the water medium.A kind of easily broken simple seal of water of meeting comprises along the water-soluble binder of the edge sealing of bag, and described bag is made as polyethylene or polypropylene by water pressuretightness polymeric film.

Machine wash up method

It is contemplated that any machine wash up or cleaning pollution tableware of being suitable for, particularly clean the method for polluting silverware.

Preferred machine wash up method comprises, uses the liquid, aqueous processing of wherein dissolving or allotment significant quantity machine dishwashing compositions of the present invention to be selected from pottery, glassware, holloware, silverware and cutlery and the various pollution vessel of blended thereof." the machine dishwashing compositions of significant quantity " is meant, dissolving or allotment restrain product at the 8-60 that 3-10 rises in the washing lotion, and this is common dosage of product and the washing lotion volume that is usually used in the conventional machine wash up method.

The packing of composition

Actual commercially available bleaching composition can be packaged in any suitable containers, comprising the container that is made of paper, cardboard, plastics and any suitable laminate.European patent application № 94921505.7 has described preferred packing example.

The abbreviation that is used for embodiment

In detergent composition, the symbol that component is called for short has following connotation:

LAS: line style C ₁₂Sodium alkyl benzene sulfonate

TAS: tallow alkyl sodium sulfate

CxyAS:C _1x-C _1ySodium alkyl sulfate

C46SAS:C ₁₄-C ₁₆Secondary position (2,3) sodium alkyl sulfate

CxyEzS: with the C of z moles of ethylene oxide condensation _1x-C _1ySodium alkyl sulfate

CxyEz: with the C of average z moles of ethylene oxide condensation _1x-1y(account for mostly

Number) line style primary alconol

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

Soap: the linear alkyl carboxylic acid sodium, derived from tallow and Oleum Cocois

80/20 mixture

CFAA:C ₁₂-C ₁₄(coconut) alkyl N-methyl glucose amide

TFAA:C ₁₆-C ₁₈Alkyl N-methyl glucoside acid amides

TPKFA:C ₁₂-C ₁₄The topping TEFA

STPP: anhydrous sodium tripolyphosphate

TSPP: tetrasodium pyrophosphate zeolite A: have structural formula Na ₁₂(AlO ₂SiO ₂) ₁₂27H ₂The hydration silicon of O

Sodium aluminate, its main particle size are 0.1-10 micron zeolite MAP: the ratio of silicon and aluminium is 1.07 hydrated sodium aluminosilicate zeolite

MAPNaSKS-6: have structural formula δ-Na ₂Si ₂O ₅The crystalline layered silicate citric acid: Citric Acid, usp, Anhydrous Powder borate Sodium Tetraborate carbonate: anhydrous sodium carbonate, granularity is a 200-900 μ m supercarbonate: anhydrous sodium bicarbonate, distribution of particle sizes are 400-1200 μ m silicate: amorphous sodium silicate (SiO ₂: Na ₂O=2.0: 1) sodium sulfate: anhydrous slufuric acid na citrate: two hydration trisodium citrates, activity are 86.4%, granularity

Be distributed as 425-850 μ mMA/AA:1: 4 toxilic acids/acrylic acid multipolymer, molecular-weight average are approximately

70000AA: sodium polyacrylate, molecular-weight average are 4500CMC: the plain ether of sodium carboxyme-thylcellulose fibre: the polymerization degree is 650 methyl cellulose ether, derives from Shin

Etsu Chemicals company proteolytic enzyme: protease, active for 4KNP U/ gram, by NOVO

Trade(brand)name SavinaseAlcalase sells in Industries A/S company: protease, and active for the 3AU/ gram, by NOVO

Industries A/S sells cellulase: cellulolytic enzyme, and active for the 1000CEVU/ gram, by NOVO

Industries A/S sells, trade(brand)name Carezyme amylase: amylolytic enzyme, and active for the 120KNU/ gram, by NOVO

Industries A/S sells, trade(brand)name Termamyl 120T lipase: lipolytic enzyme, the active 100KLU/ of being restrains trade(brand)name

Lipolase, sell endoenzyme by NOVO Industries A/S: endo-dextranase, active for the 3000CEVU/ gram, by NOVO

Industries A/S sells PB4: four hydrated sodium perborates, nominal configuration formula

NaBO ₂3H ₂OH ₂O ₂PB1: anhydrous sodium perborate SYNTHETIC OPTICAL WHITNER, nominal configuration formula NaBO ₂H ₂O ₂Percarbonate: SPC-D, nominal configuration formula 2Na ₂CO ₃3H ₂O ₂NOBS: the sodium salt TAED of nonanoyl oxygen Phenylsulfonic acid: acetyl quadrol Mn catalyzer: Mn ^IV ₂(m-O) ₃(1,4,7-trimethylammonium-1,4,7-three nitrogen heterocyclics

Nonane) ₂(PF ₆) ₂, as US Patent No 5246621 Hes

DTPA described in 5244594: diethylene triaminepentaacetic acid(DTPA) DTPMP: diethylenetriamine five (methylene phosphonic acid salt), by

The Monsanto supply, commodity are called DEQUEST 2060 light activating agents: sulfonation zinc phthalocyanine phthalocyanine coats whitening agent 1:4 with bleaching dextrin water-soluble polymers, 4 '-two (2-sulfo group styryl) biphenyl disodium whitening agent 2:4,4 '-two (4-anilino-6-morpholino-1,3,5-triazines-

The 2-yl) amino) Stilbene-2,2 '-disulfonic acid disodium HEDP:1,1-hydroxyl second di 2 ethylhexyl phosphonic acid EDDS: quadrol-N, N '-disuccinic acid QEA1: two ((C ₂H ₅O) (C ₂H ₄O) _n(CH ₃)-N ⁺-C ₆H ₁₂-N ⁺-(CH ₃)

Two ((C ₂H ₅O)-(C ₂H ₄O) _n), n=20-30QEA2 wherein: two ((C ₂H ₅O) (C ₂H ₄O) _n(CH ₃)-N ⁺R ₁, R wherein ₁For

C ₄-C ₁₂Alkyl, and n=20-30QEA3: three { two ((C ₂H ₅O)-(C ₂H ₄O) _n(CH ₃)-N ⁺)-

(CONC ₃H ₆))-C ₃H ₆O; n=20-26PEGX wherein: polyoxyethylene glycol; molecular weight is xPEO: polyoxyethylene; molecular weight is 50000TEPAE: the ethoxylate PVP of tetren: polyvinylpyrrolidonepolymers polymers PVNO: polyvinylpyridine N-oxide compound PVPVI: the multipolymer SRP1 of Polyvinylpyrolidone (PVP) and vinyl imidazole: the end capped ester of sulphur benzoyl group has oxygen base ethyleneoxy group and right

Phenyl-diformyl base main chain SRP2: diethoxyization poly-(terephthalic acid 1,2-propylene glycol ester) is short

Block polymer siloxanes antifoams: the polydimethylsiloxane Foam Control, wherein use siloxanes

-oxygen base alkylidene group multipolymer is as dispersion agent, described foam control

The ratio of preparation and described dispersion agent is 10: 1-100: 1

Wax: paraffinic waxes

In following examples, all content all are meant the weight percentage (%) of composition.

Embodiment 1

According to the present invention, prepare the following high density granular laundry detergent composition A-F that is particularly suitable for European machine washing condition.

	A	B	C	D	E	F
							LAS	8.0	8.0	8.0	8.0	8.0	8.0
C25E3	3.4	3.4	3.4	3.4	3.4	3.4
							C46AS	1.0	2.0	2.5	-	3.0	4.0
C68AS	3.0	2.0	5.0	7.0	1.0	0.5
							QAS	-	-	0.8	-	-	0.8
Zeolite A	18.1	18.1	16.1	18.1	18.1	18.1
							Zeolite MAP	-	4.0	3.5	-	-	-
Carbonate	13.0	13.0	13.0	27.0	27.0	27.0
							Silicate	1.4	1.4	1.4	3.0	3.0	3.0
Sodium sulfate	26.1	26.1	26.1	26.1	26.1	26.1
							MA/AA	0.3	0.3	0.3	0.3	0.3	0.3
CMC	0.2	0.2	0.2	0.2	0.2	0.2
							PB4	9.0	9.0	9.0	9.0	9.0	9.0
TAED	1.5	1.5	1.0	1.5	-	1.5
							The Mn catalyzer	-	0.03	0.07	-	-	-

DTPMP	0.25	0.25	0.25	0.25	0.25	0.25
							HEDP	0.3	0.3	0.2	0.2	0.3	0.3
EDDS	-	-	0.4	0.2	-	-
							QEA1	1.0	0.8	0.7	1.2	-	0.5
QEA2	-	-	-	-	1.0	0.5
							Proteolytic enzyme	0.26	0.26	0.26	0.26	0.26	0.26
Amylase	0.1	0.1	0.4	0.3	0.1	0.1
							Photoactivation SYNTHETIC OPTICAL WHITNER (ppm)	15 ppm	15 ppm	15 ppm	15 ppm	15 ppm	15 ppm
Whitening agent 1	0.09	0.09	0.09	0.09	0.09	0.09
							Spices	0.3	0.3	0.3	0.3	0.3	0.3
The siloxanes antifoams	0.5	0.5	0.5	0.5	0.5	0.5
							Foreign material/a small amount of thing are to 100%
Density (grams per liter)	850	850	850	850	850	850

Embodiment 2

According to the present invention, prepare the following granular laundry detergent compositions G-I that is particularly suitable for European machine washing condition.

	G	H	I
				LAS	5.25	5.61	4.76
TAS	1.25	1.86	1.57
				C45AS	-	2.24	3.89
C25E3S	-	0.76	1.18
				C45E7	3.25	-	5.0

C25E3	-	5.5	-
				QAS	0.8	2.0	2.0
STPP	19.7	-	-
				Zeolite A	-	19.5	19.5
Zeolite MAP	2.0	-	-
				NaSKS-6/ citric acid (79: 21)	-	10.6	10.6
Carbonate	6.1	21.4	21.4
				Supercarbonate	-	2.0	2.0
Silicate	6.8	-	-
				Sodium sulfate	39.8	-	14.3
MA/AA	0.8	1.6	1.6
				CMC	0.2	0.4	0.4
PB4	5.0	12.7	-
				Percarbonate	5.0	-	12.7
TAED	0.5	3.1	-
				The Mn catalyzer	0.04	-	-
DTPMP	0.25	0.2	0.2
				HEDP	-	0.3	0.3
QEA1	0.9	1.2	-
				QEA2	-	-	1.0
Proteolytic enzyme	0.26	0.85	0.85
				Lipase	0.15	0.15	0.15

Cellulase	0.28	0.28	0.28
				Amylase	0.4	0.1	0.1
PVP	0.9	1.3	0.8
				Photoactivation SYNTHETIC OPTICAL WHITNER (ppm)	15 ppm	27 ppm	27 ppm
Whitening agent 1	0.08	0.19	0.19
				Whitening agent 2	-	0.04	0.04
Spices	0.3	0.3	0.3
				The siloxanes antifoams	0.5	2.4	2.4
Foreign material/a small amount of thing are to 100%

Embodiment 3

According to the present invention, prepare the following detergent formulation that is particularly suitable for European machine washing condition.

	J	K	L	M
					The blowing powder:
LAS	6.0	5.0	11.0	6.0
					TAS	2.0	-	-	2.0
Zeolite A	-	27.0	-	20.0
					STPP	24.0	-	24.0	-
Vitriol	9.0	6.0	13.0	-
					MA/AA	2.0	4.0	6.0	4.0
Silicate	7.0	3.0	3.0	3.0
					CMC	1.0	1.0	0.5	0.6
OEA1	0.8	1.0	1.4	0.5
					OEA2	-	-	-	0.5
Whitening agent	0.2	0.2	0.2	0.2
					The siloxanes antifoams	1.0	1.0	1.0	0.3
DTPMP	0.4	0.4	0.2	0.4
					Be sprayed onto:
C45E7	-	-	-	5.0

C45E2	2.5	2.5	2.0	-
					C45E3	2.6	2.5	2.0	-
Spices	0.3	0.3	0.3	0.2
					The siloxanes antifoams	0.3	0.3	0.3	-
Dried additive:
					Vitriol	3.0	3.0	5.0	10.0
Carbonate	6.0	13.0	15.0	14.0
					PB1	-	-	-	1.5
PB4	18.0	18.0	10.0	18.5
					TAED	3.0	2.0	-	2.0
EDDS	-	2.0	2.4	-
					Proteolytic enzyme	1.0	1.0	1.0	1.0
Lipase	0.4	0.4	0.4	0.2
					Amylase	0.2	0.2	0.2	0.4
The photoactivation SYNTHETIC OPTICAL WHITNER	-	-	-	0.15
					Amount to	100.0	100.0	100.0	100.0

Embodiment 4

According to the present invention, prepare following granulated detergent prescription.Prescription N is particularly suitable for using under Japan's machine washing condition.Prescription O-S is particularly suitable for using under U.S.'s machine washing condition.

	N	O	P	O	R	S
							The blowing powder:
LAS	22.0	5.0	4.0	9.0	8.0	7.0
							C45AS	7.0	7.0	6.0	-	-	-
C46AS	-	4.0	3.0	-	-	-
							C45E35	-	3.0	2.0	8.0	5.0	4.0
Zeolite A	6.0	16.0	14.0	19.0	16.0	14.0
							MA/AA	6.0	3.0	3.0	-	-	-
AA	-	3.0	3.0	2.0	3.0	3.0
							Sodium sulfate	7.0	18.3	11.3	24.0	19.3	19.3
Silicate	5.0	1.0	1.0	2.0	1.0	1.0
							Carbonate	28.3	9.0	7.0	25.7	8.0	6.0
OEA1	0.9	0.9	-	-	0.5	1.1
							OEA2	-	-	0.8	1.0	-	-
OEA3	-	-	0.4	-	-	-
							PEG 4000	0.5	1.5	1.5	1.0	1.5	1.0

Sodium oleate	2.0	-	-	-	-	-
							DTPA	0.4	-	0.5	-	-	0.5
Whitening agent	0.2	0.3	0.3	0.3	0.3	0.3
							Be sprayed onto:
C25E9	1.0	-	-	-	-	-
							C45E7	-	2.0	2.0	0.5	2.0	2.0
Spices	1.0	0.3	0.3	1.0	0.3	0.3
							Gather:
C45AS	-	5.0	5.0	-	5.0	5.0
							LAS	-	2.0	2.0	-	2.0	2.0
Zeolite A	-	7.5	7.5	-	7.5	7.5
							HEDP	-	1.0	-	-	2.0	-
Carbonate	-	4.0	4.0	-	4.0	4.0
							PEG 4000	-	0.5	0.5	-	0.5	0.5
Foreign material (water etc.)	-	2.0	2.0	-	2.0	2.0
							Dried additive:
TEAD	1.0	2.0	3.0	1.0	3.0	2.0
							PB4	-	1.0	4.0	-	5.0	0.5
PB1	6.0	-	-	-	-	-
							Percarbonate	-	5.0	12.5	-	-	-
Carbonate	-	5.3	1.8	-	4.0	4.0
							NOBS	4.5	-	6.0	-	-	0.6
Isopropyl benzene sulfonic acid	-	2.0	2.0	-	2.0	2.0
							Lipase	0.4	0.4	0.4	-	0.4	0.4
Cellulase	0.1	0.2	0.2	0.2	0.2	0.2
							Amylase	0.1	0.3	0.3	-	-	-
Proteolytic enzyme	1.0	0.5	0.5	0.5	0.5	0.5
							PVPVI	-	0.5	0.5	-	-	-
PVP	0.5	0.5	0.5	-	-	-
							PVNO	-	0.5	0.5	-	-	-
SRP1	-	0.5	0.5	-	-	-
							The siloxanes antifoams	-	0.2	0.2	-	0.2	0.2
							Amount to	100.0	100.0	100.0	100.0	100.0	100.0

Embodiment 5

According to the present invention, prepare following granulated detergent prescription.Prescription W and X are particularly suitable for using under U.S.'s machine washing condition.Y is particularly suitable for using under Japan's machine washing condition.

	T	U	V
				The blowing powder:
Zeolite A	30.0	22.0	6.0
				Sodium sulfate	19.0	5.0	7.0
MA/AA	3.0	3.0	6.0
				LAS	14.0	12.0	22.0
C45AS	8.0	7.0	7.0
				Silicate	-	1.0	5.0
Soap	-	-	2.0
				Whitening agent 1	0.2	0.2	0.2
OEA1	0.6	2.0	1.0
				Carbonate	0.8	16.0	20.0
DTPMP	-	0.4	0.4
				Be sprayed onto:	-	1.0	5.0
C45E7	1.0	1.0	1.0
				Dried additive:
HEDP	1.0	-	-
				PVPVI/PVNO	0.5	0.5	0.5
Proteolytic enzyme	1.0	1.0	1.0
				Lipase	0.4	0.4	0.4
Amylase	0.1	0.1	0.1
				Cellulase	0.1	0.1	0.1
TEAD	-	6.1	4.5
				PB1	11.0	5.0	6.0
Sodium sulfate	-	6.0	-
				Surplus (moisture and foreign material)

Embodiment 6

According to the present invention, prepare the following granulated detergent that is particularly suitable under the machine washing condition of Europe, using and make up.

	W	X
			The blowing powder:
Zeolite A	20.0	-
			STPP	-	20.0

LAS	6.0	6.0
			C68AS	2.0	2.0
Silicate	3.0	8.0
			MA/AA	4.0	2.0
CMC	0.6	0.6
			OEA1	0.9	0.6
OEA3	0.1	-
			Whitening agent 1	0.2	0.2
DTPMP	0.4	0.4
			Be sprayed onto:
C45E7	5.0	5.0
			The siloxanes antifoams	0.3	0.3
Spices	0.2	0.2
			Dried additive:
Carbonate	14.0	9.0
			PB1	1.5	2.0
PB4	18.5	13.0
			TAED	2.0	2.0
The photoactivation SYNTHETIC OPTICAL WHITNER	15ppm	15ppm
			Proteolytic enzyme	1.0	1.0
Lipase	0.2	0.2
			Amylase	0.4	0.4
Cellulase	0.1	0.1
			Vitriol	10.0	20.0
Surplus (moisture and foreign material)
			Density (grams per liter)	700	700

Embodiment 7

According to the present invention, prepare following detergent composition.

	Y	Z	AA
				The blowing powder:
Zeolite A	15.0	15.0	15.0
				Sodium sulfate	0.0	5.0	0.0
LAS	3.0	3.0	3.0
				OAS	-	1.5	1.5

DTPMP	0.4	0.2	0.4
				CMC	0.4	0.4	0.4
MA/AA	4.0	2.0	2.0
				Gather:
LAS	5.0	5.0	5.0
				TAS	2.0	2.0	1.0
Silicate	3.0	3.0	4.0
				OEA1	1.0	2.5	0.6
The Mn catalyzer	0.03	-	-
				Zeolite A	8.0	8.0	8.0
Carbonate	8.0	8.0	4.0
				Be sprayed onto:
Spices	0.3	0.3	0.3
				C45E7	2.0	2.0	2.0
C25E3	2.0	-	-
				Dried additive:
Citrate trianion	5.0	-	2.0
				Supercarbonate	-	3.0	-
Carbonate	8.0	15.0	10.0
				Percarbonate	-	7.0	10.0
TAED	6.0	2.0	5.0
				PB1	14.0	7.0	10.0
EDDS	-	2.0	-
				MW is 5000000 polyoxyethylene	-	-	0.2
Wilkinite	-	-	10.0
				Proteolytic enzyme	1.0	1.0	1.0
Lipase	0.4	0.4	0.4
				Amylase	0.6	0.6	0.6
Cellulase	0.6	0.6	0.6
				The siloxanes antifoams	5.0	5.0	5.0
Dried additive:
				Sodium sulfate	0.0	3.0	0.0
Surplus (moisture and foreign material)	100.0	100.0	100.0
				Density (grams per liter)	850	850	850

Embodiment 8

According to the present invention, prepare following detergent composition.

	BB	CC	DD	EE
					LAS	20.0	14.0	24.0	22.0
OAS	0.7	1.0	-	0.7
					TFAA	-	1.0	-	-
C25E5/C45E7	-	2.0	-	0.5
					C45E3S	-	2.5	-	-
STPP	30.0	18.0	30.0	22.0
					Silicate	9.0	5.0	10.0	8.0
Carbonate	13.0	7.5	-	5.0
					Supercarbonate	-	7.5	-	-
Percarbonate	-	5.0	9.0	15.0
					DTPMP	0.7	1.0	-	-
OEA1	0.4	1.2	0.5	2.0
					OEA2	0.4	-	-	-
SRP1	0.3	0.2	-	0.1
					MA/AA	2.0	1.5	2.0	1.0
CMC	0.8	0.4	0.4	0.2
					Proteolytic enzyme	0.8	1.0	0.5	0.5
Amylase	0.8	0.4	-	0.25
					Lipase	0.2	0.1	0.2	0.1
Cellulase	0.15	0.05	-	-
					Photoactivation SYNTHETIC OPTICAL WHITNER (ppm)	70 ppm	45 ppm	-	10 ppm
Whitening agent 1	0.2	0.2	0.08	0.2
					PB1	6.0	2.0	-	-
HEDP	-	-	2.3	-
					TEAD	2.0	1.0	-	-
Surplus (moisture and foreign material)

Embodiment 9

Following compacting high-density produced according to the present invention (0.96kg/1) dishwashing detergent composition F F to KK, and its meaning of the symbol of used composition is as follows in this washing composition: metasilicate: metasilicate sodium (SiO ₂: Na ₂O=1.0) non-ionic type: sell with trade(brand)name Plurafac LF404 by BASF GmbH,

Average degree of ethoxylation 3.8, and average propoxylation degree 4.5

C ₁₃-C ₁₅Mixed ethoxylated/propoxylated fatty alcohol (low bubble) PAAC: five amine cobaltous acetate (III) salt BzP: benzoyl peroxide paraffin: the paraffin oil BTA that sells with trade(brand)name Winog70 by Wintershall: benzotriazole Bismuth trinitrate: Bismuth trinitrate salt trimer: contain vinylformic acid: toxilic acid: ethylacrylic acid monomeric unit, its weight

Than being 60: 20: 20, the trimer 480N:3 of molecular-weight average about 7000: vinylformic acid/methacrylic acid of 7, molecular-weight average about 3500

Random copolymers

	FF	GG	HH	II	JJ	KK
							STPP	24.80	24.80	25.00	28.39	28.50	20.00
Citrate trianion	-	-	-	-	10.00	10.00
							Carbonate	-	-	17.50	17.50	-	-
OEA1	0.5	1.5	2.0	1.0	0.3	0.8
							Silicate	20.36	20.36	14.81	14.81	14.81	-
Metasilicate	2.50	2.50	2.50	-	-	-
							PB1	7.79	7.79	9.74	14.28	9.74	-
PB4		-	-	-	-	10.4
							Percarbonate	-	-	-	-	-	6.70
Non-ionic type	1.50	1.50	2.00	1.50	2.00	2.60
							TAED	2.39	2.00	2.70	2.00	3.60	4.00
HEDP	0.46	0.46	1.00	-	0.83	-
							DETPMP	-	-	0.65	-	-	-
PAAC	-	-	-	0.20	-	-
							BzP	-	-	-	4.44	-	-
Paraffin	0.50	0.50	0.50	0.50	-	0.20
							Proteolytic enzyme	2.20	2.20	2.20	2.20	2.00	0.50
Amylase	1.50	1.50	1.20	1.50	1.00	1.10

BTA	0.30	0.30	0.30	0.30	-	-
							Bismuth trinitrate	-	-	0.30	-	-	-
Trimer	-	-	-	4.00	-	-
							480N	2.77	2.77	6.00	-	6.67	-
Vitriol	8.44	8.44	20.77	-	23.24	1.00
							Foreign material and water surplus
PH (1% solution)	10.90	10.90	11.00	10.80	10.90	9.60

Claims (25)

1. granular detergent composition wherein comprises:

(a) contain the oxygen release bleach system of peroxygen source; With

(b) have the water-soluble cationic compound of dirt removal/antiredeposition performance, it is selected from:

1) have ethoxylation positively charged ion one amine of following structural formula:

2) have the ethoxylation cationic diamine of following structural formula: Or Or

M wherein ¹Be N+ or N group; Each M ²Be N+ or N group; And at least one M ²Be the N+ group;

3) have the ethoxylation cationic polyamine of following structural formula:

4) and composition thereof; Wherein: A ¹Be Or-O-,

R is H or C ₁-C ₄Alkyl or hydroxyalkyl, R ¹Be C ₂-C ₁₂Alkylidene group, hydroxyl alkylidene group, alkenylene, arylidene or alkarylene or C with about 20 oxyalkylene units of 2- ₂-C ₃The oxyalkylene part, but can not form any O-N key; Each R ²Be C ₁-C ₄Alkyl or hydroxyalkyl ,-the L-X part, or two R ²Formation-(CH together ₂) _r-A ²-(CH ₂) _s-part, wherein A ²For-O-or-CH ₂-, r is 1 or 2, s is 1 or 2, and r+s is 3 or 4; Each R ³Be C ₁-C ₈Alkyl or hydroxyalkyl, benzyl ,-the L-X part, perhaps, two R ³Or R ²With a R ³Formation-(CH together ₂) _r-A ²-(CH ₂) _s-part; R ⁴For replacing C ₃-C ₁₂Alkyl, hydroxyalkyl, alkenyl, aryl or have the alkaryl of para-orientation position; R ⁵Be C ₁-C ₁₂Alkenyl, hydroxyl alkylidene group, alkenylene, arylidene or alkarylene or C with about 20 oxyalkylene units of 2- ₂-C ₃The oxyalkylene part, but can not form any O-O or O-N key; X is for being selected from H, C ₁-C ₄The non-ionic group of alkyl or hydroxy alkyl ester or ether group and mixed group thereof; L is for containing polyoxyalkylene part-[(R ⁶O) _m(CH ₂CH ₂O) _n]-hydrophilic chain; R wherein ⁶Be C ₃-C ₄Alkylidene group or hydroxyl alkylidene group, and the number of m and n should make-(CH ₂CH ₂O) _n-part account for described polyoxyalkylene part at least about 50% weight; M ²During for N+, d is 1, M ²During for N, d is 0; For described positively charged ion one amine, n is at least about 16, for described cationic diamine at least about 6, for described cationic polyamine at least about 3; P is 3-8; Q is 1 or 0; T is 1 or 0, but q is 1 o'clock, and t is 1, and wherein (a) and ratio (b) are 80: 1 to 1: 5.

2. according to the detergent composition of claim 1, wherein said ratio is 20: 1 to 1: 1.

3. according to the detergent composition of claim 1 or 2, the consumption of wherein said cation compound is the 0.01-30% of detergent composition weight.。

4. according to the detergent composition of claim 1, the consumption of wherein said cation compound is the 0.2%-3% of detergent composition weight.

5. according to the detergent composition of claim 1, wherein said cation compound is ethoxylation positively charged ion one amine, it is characterized in that a R ²Be methyl, two R ²Be the L-X part, m be 0 and n be at least about 20.

6. according to the detergent composition of claim 1, wherein said cation compound is the ethoxylation cationic diamine, it is characterized in that R ¹Be C ₂-C ₆Alkylidene group.

7. according to the detergent composition of claim 6, wherein said ethoxylation cationic diamine is characterised in that R ¹Be hexylidene.

8. according to the detergent composition of claim 6, wherein said cation compound is characterised in that: R ²Be methyl or L-X part, each R ³Be methyl, and M ¹With each M ²Be N ⁺Group.

9. according to the detergent composition of claim 6, wherein m is 0, and n is at least 12.

10. according to the detergent composition of claim 1, wherein said cation compound is the oxyethyl group cationic polyamine, it is characterized in that R ⁴Be the C that replaces ₃-C ₆Alkyl, hydroxyalkyl or aryl; Al is

And p is 3-6.

11. according to the detergent composition of claim 6, wherein m is 0, and n is at least 20.

12. detergent composition according to claim 1, the cationic polymers that wherein has dirt removal/antiredeposition performance be characterised in that have main chain, at least 2 M groups and at least 1 L-X group, wherein M is for being connected on the main chain, or the cation group that is connected as a single entity with main chain, and comprises N ⁺Center of positive charge; L connects M group and X group or X is connected on the main polymer chain; X is for being selected from H, C ₁-C ₄The non-ionic group of alkyl or hydroxy alkyl ester or ether group and mixed group thereof; And L is for containing polyoxyalkylene part-[(R ⁶O) _m(CH ₂CH ₂O) _n]-hydrophilic chain.

13. according to the detergent composition of claim 12, wherein said cationic polymers is the ethoxylation cationic polymers that a kind of main chain is selected from urethane, polyester, polyethers, polyimide, polyalkyleneimine and composition thereof.

14. according to the detergent composition of claim 1, the wherein said oxygen release bleaching system consumption that contains peroxygen source is composition weight 1%-40%.

15. according to the detergent composition of claim 1, wherein said peroxygen source is the inorganic salt hydrate of crossing, consumption is the 2%-30% of composition weight.

16. according to the detergent composition of claim 15, wherein said inorganic salt hydrate excessively is SPC-D or Sodium peroxoborate.

17. according to the detergent composition of claim 1, wherein said oxygen release bleaching system contains hydrogen peroxide cource and peroxy acid bleach precursor compound.

18. according to the detergent composition of claim 17, wherein said peroxy acid bleach precursor compound consumption is the 1.0%-15% of detergent composition weight.

19. according to the detergent composition of claim 1, wherein contain bleach catalysts, be selected from Mn ^IV ₂(u-o) ₃(1,4,7-trimethylammonium-1,4,7-7-triazacyclononane) ₂-(PF ₆) ₂, Mn ^III ₂(u-o) ₁(u-OA _c) ₂(1,4,7-trimethylammonium-1,4,7-7-triazacyclononane) ₂-(ClO ₄) ₂, Mn ^IV ₄(u-o) ₆(1,4, the 7-7-triazacyclononane) ₄-(ClO ₄) ₂, Mn ^IIIMn ^IV ₄(u-o) ₁(u-OA _c) ₂(1,4,7-trimethylammonium-1,4,7-7-triazacyclononane) ₂-(ClO ₄) ₃, Mn (1,4,7-trimethylammonium-1,4,7-7-triazacyclononane (OCH ₃) ₃-(PF ₆), Co (2,2 '-bipyridyl amine) Cl ₂, two-(different sulfo-cyanato-) bipyridyl amine cobalt (II), three (bipyridyl amine)-cobaltous perchlorate (II), Co (2,2-bipyridyl amine) ₂-O ₂ClO ₄, two (2,2 '-two pyridine amine) cupric perchlorate (II), three (two-2-pyridyl amine) Iron triperchlorate (II), manganese gluconate, Mn (CF ₃SO ₃) ₂, Co (NH ₃) ₅The title complex of Cl, double-core Mn and four-N-tooth part and two-N-tooth part comprises N ₄Mn ^III(u-o) ₂Mn ^IVN ₄) ⁺(two Py ₂Mn ^III(u-o) ₂Mn ^IVTwo Py ₂) (ClO ₄) ₃And composition thereof.

20. according to the detergent composition of claim 1, the manner of formulation of said composition will make washing lotion pH value be 8.0-10.5.

21. according to the detergent composition of claim 1, wherein the consumption of heavy metal ion chelating agent is the 0.1-10% of described detergent composition weight.

22., wherein contain the tensio-active agent that is selected from anion surfactant, nonionogenic tenside, cats product, amphoterics and zwitterionics and composition thereof according to the detergent composition of claim 1.

23. a method of washing clothes in the family expenses washing machine is wherein introduced the detergent composition according to claim 1 of significant quantity in the washing machine drum.

24. according to the method for claim 23, wherein before beginning washing, use partitioning device that described detergent composition is introduced in the washing machine drum, described partitioning device can make described detergent composition be discharged in the washing lotion gradually during washing.

25. the application of detergent composition in the dishwashing detergent process according to claim 1.