CN1337997A - Detergent tablet - Google Patents

Abstract

A multi-phase detergent tablet comprising: a) a first phase in the form of a shaped body having at least one mould therein; and b) a second phase in the form of a compressed body adhesively contained within said mould, and wherein the second phase comprises an enzyme. The multi-phase tablets provide improved dissolution and cleaning characteristics together with excellent tablet integrity and strength.

Description

Detergent tablet

Technical field

The present invention relates to the multi-phase detergent sheet.

Background technology

The detergent composition of sheet form is known in the prior art.Much less, the detergent composition of sheet form has several advantages than the detergent composition of particle form, for example is easy to dosage, loading and unloading, transportation and storage.

Detergent tablet is the most normally by pre-mixing detergent composition component, and uses the preferred tabletting machine of any suitable device will this premixed detergent component to make that sheet prepares.These sheets generally are to make by the component that compresses detergent composition, cause the sheet of formation to have enough soundnesses and can stand loading and unloading and transportation and do not suffer damage.Except firm, thereby these sheets also must dissolve fast enough and make detergent component be discharged in the washing water as quickly as possible when the beginning of cycles of washing.

, contradiction is the increase along with pressure, and sheet dissolved speed is slack-off.Therefore, the present invention attempts to seek a kind of balance between sheet soundness and sheet solvability.

As seeing in the prior art, the terms of settlement of this problem comprises with low pressure suppresses these sheets.Yet Zhi Bei sheet though have fast relatively dissolution rate, is understood fragmentation in this way, and become damage and human consumer can not accept.Other terms of settlement comprises that the high relatively pressure of use prepares sheet, so that reach needed firm level and contain for example pore forming material of dissolution aids.

The multi-phase detergent sheet of Miao Shuing is preparation so in the prior art, thereby first kind of composition of compacting forms planar the first layer basically in tabletting machine.In this tabletting machine, another kind of detergent composition is fed to the upper end of the first layer then.Thereby suppress this second kind of composition then and form another planar second layer basically.Therefore, because it also has been pressed during the compacting of second kind of composition, so the first layer has stood the compacting more than once usually.General for the first time and the second time pressure be the identical order of magnitude.The applicant has been found that in this case, because pressure must be enough to first and second kinds of compositions are bonded together, thus in pressing step for the first time and for the second time used power (cross section of supposing sheet is about 10cm in must the scope at about 4000-20000kg ²).This result is that the dissolution rate of sheet is slower.Other demonstrates different deliquescent multi-phase tablets is preparations like this, and the second layer is pressed under the pressure lower than the first layer.Yet, although the dissolution rate of the second layer has been enhanced,, the second layer is softer than the first layer, therefore causes damage by loading and unloading and transportation easily.

EP-B-0055100 has described the toilet cleaning block that is combined together to form by with slow dissolved formed body and sheet.This toilet cleaning block is designed to be placed in the toilet water receiver and a couple of days, and the time of preferred several weeks just dissolves.As the method for this toilet cleaning block dissolution rate that slows down, the document has been instructed and has been mixed one or more solubleness control agents.The example of such solubleness control agent is a santochlor, wax, longer chain fatty acid and alcohol with and ester and fatty alkyl acid amides.Be used for doing washing and the detergent tablet of automatic dishwashing must be dissolving basically in 15-120 minute in the once circulation of washing machine or wash up machine.

Summary of the invention

According to a first aspect of the invention, provide the multi-phase detergent that is used to machine-wash sheet, this sheet contains:

A) first phase of formed body form wherein has at least one mold; With

B) be compressed on second phase of described mold endoparticle solid form.

In preferred embodiments, first is the formed body of compacting mutually, and it is to be in application to few about 40kg/cm ², preferably at least about 250kg/cm ², more preferably at least about 350kg/cm ²(3.43kN/cm ²), 400-2000kg/cm more preferably from about ², particularly about 600-1200kg/cm ²Pressure down preparation (pressure herein be apply power divided by with vertical cross-sectional area in exerting pressure plane-be actually cross-sectional area of rotational pressure machine punch die).Further preferably second phase (this term meaning is the possibility that comprises a plurality of " second " phase, is sometimes referred to as " its optional second phase " herein) granular solids is being lower than about 350kg/cm under the condition that applied pressure is exerted pressure less than first phase and preferably ²Condition under, preferably at about 40-300kg/cm ², 70-270kg/cm more preferably from about ²Condition be pushed down in the described mold, from best sheet integrity and intensity (for example by Child Bite Strength[CBS] test determination) and the deliquescent angle of product are provided, such sheet is preferred in this article.Preferably, of the present invention CBS is at least about 6kg, be preferably greater than about 8kg, more preferably greater than about 10kg, particularly greater than about 12kg, more especially greater than about 14kg, CBS measures according to U.S. consumer safety council test procedure (US Consumer Product SaftyCommission Test Specification).In addition, the ratio that puts on the pressure of first and second phases generally is at least about 1.2: 1, preferably at least about 2: 1, more preferably at least about 4: 1.Therefore, according to another aspect of the present invention, provide the multi-phase detergent that is used to machine-wash sheet, this sheet contains:

A) compacting is first phase of formed body form, wherein has at least one mold, and this formed body is at least about 350kg/cm ²Down preparation of pressure; With

B) be compressed on second phase of described mold endoparticle solid form, this second is to be lower than about 350kg/cm mutually ²Down compacting of pressure.

In other embodiment preferred, second is press body or formed body form mutually, and its bonding (for example by physics and chemical adhesion) is included at least one mold of first formed body.Further preferably this first and second mutually mutual weight ratio is high relatively, for example at least about 6: 1, preferably at least about 10: 1; In addition, this tablet composition contains one or more detergent active (for example enzyme, SYNTHETIC OPTICAL WHITNER, bleach-activating agent, bleaching catalyst, tensio-active agent, sequestrant etc.), its mainly be concentrated in second mutually in, for example this sheet second mutually in, by weight, at least about 50%, preferably at least about 60%, particularly about 80% actives (by actives gross weight in the sheet).Have again, such composition is best providing aspect sheet intensity, solvability, cleaning and the pH regulator, for example thereby this tablet composition can be dissolved in 10 minutes that begin at washing process in the washings, 5 minutes, will be by weight in 4 minutes or 3 minutes at least 50%, preferably at least 60%, more preferably at least 80% detergent active is discharged in the washings.

Therefore, according to a further aspect of the invention, provide the multi-phase detergent that is used for washing machine sheet, this sheet contains:

A) first phase of formed body form wherein has at least one mold; With

B) be compressed on second phase of described mold endoparticle solid form, wherein to contain at least a detergent active and its be preparation like this to this sheet, cause by weight at least 50%, preferably at least 60%, more preferably at least 80% detergent active is in preceding 10 minutes of washing process, in preferred preceding 5 minutes, be released in the washings in more preferably preceding 3 minutes.

Other benefit of the present invention is to have the difference dissolved ability that realizes these phases, causes a mainly dissolving before another phase mutually of this sheet, even can dissolving fully basically before other phased soln.This release respectively for detergent active is particularly useful.

Therefore, according to a further aspect of the invention, provide the multi-phase detergent sheet, it contains:

A) first phase of formed body form wherein has at least one mold; With

B) second phase of press body form, it adhesively is included in the described mold, and this tablet composition contains one or more and mainly be concentrated in second the detergent active in mutually, and wherein this second also contains cracking agent (disrupting agent) mutually.

According to another aspect of the present invention, provide the multi-phase detergent sheet, it contains:

A) first phase of formed body form wherein has at least one mold; With

B) second phase of press body form, it adhesively is included in the described mold, and this tablet composition contains one or more and mainly be concentrated in second the detergent active in mutually, and wherein this second also contains tackiness agent mutually.

These one or more detergent active suitably are selected from: enzyme, SYNTHETIC OPTICAL WHITNER, bleach-activating agent, bleaching catalyst, tensio-active agent, sequestrant, crystal growth inhibitor, with its mixture, this enzymic activity thing is particularly preferred for strengthening cleaning performance in the cold water stage of washing or cleaning operation begins.Therefore, what very preferably use herein is the enzyme detergent actives, particularly various enzymes and the enzyme mixture that contains one or more enzymes, it is 25-55 ℃ temperature range and have enhanced or best activity (for example Natalase) under the pH of 8-10 scope value.

Therefore, according to a further aspect of the invention, provide the multi-phase detergent sheet, it contains:

A) first phase of formed body form wherein has at least one mold; With

B) second phase of press body form, it adhesively is included in the described mold, and wherein this second also contains enzyme mutually.

Detailed Description Of The Invention

An object of the present invention is to provide a kind of detergent tablet, it not only have enough soundnesses can stand loading and unloading and the transportation, thereby and at least its sizable part can be dissolved in the snap-out release that detergent active is provided in the washing water apace.Preferably, at least one of this sheet be at preceding 10 minutes of automatic dishwashing machine or washing machine wash(ing)cycle, preferred preceding 5 minutes, is dissolved in the washing water in more preferably preceding 4 minutes.This washing machine is automatic dishwashing machine or washing machine preferably.This multi-phase tablets or its phase or detergent active ingredients dissolved time are measured according to DIN44990, the wash up machine that use obtains from Bosch, under 65 ℃ of common washing procedures, with the water of 18 ° of H hardness, least repeated 6 times or enough number of times are to guarantee reproducibility.

Multi-phase detergent sheet of the present invention contains first phase, second phase and its optional second phase.First is the detergent composition of formed body form mutually, and it contains one or more detergent components described below.Preferred detergent component comprises: washing assistant, SYNTHETIC OPTICAL WHITNER, enzyme and tensio-active agent.The component of this detergent composition is that liquid ingredient mixes by for example mixing the component of doing or spraying upward.Then, use any suitable device, but preferred by compacting for example in tabletting machine, these components are formed first phase.In addition, first mutually also can be by extruding, and casting waits and prepares.This first can be various geometrical shapies mutually, and is for example spherical, cubes etc., but embodiment preferred to have generally be the axisymmetric shape of circle, four directions or rectangular cross section.

First is to prepare so mutually, and it makes it comprise at least one mold on the surface of formed body.This mold or these molds can change aspect this first mutually position, orientation and layout aspect size and dimension with at it.For example, the cross section of this mold or these molds can be general circle, square or ellipse; They can form the hole of inner sealing or at the lip-deep groove of formed body, perhaps they can be in the surface (for example the surface of axle) relatively thus fill " hole " that in formed body, forms one or more layouts between the connecting zone; They can be with respect to first axial mutually or other symmetric offset spread, and perhaps they can be asymmetric geometries.In preferred embodiments; this mold is to use specially designed tabletting machine to form; wherein the punch head surface that contacts with detergent composition is such shape; it makes when its contact and compacting detergent composition, its pressure with a mold or a plurality of mold be pressed onto the multi-phase detergent sheet first mutually in.Preferably, this mold have inside concave surface or common concave surface in case improvement is provided with second mutually the binding property.In addition, this mold can form like this, suppresses a ready-formed detergent composition around the arrangement of center dyestuff, forms a formed body thus, and it has the mold of axially extended hollow cavity shaped between this formed body apparent surface.

Of the present invention also comprises one or more additional phases, and it is by the preparation of compositions that contains one or more detergent components as described below.At least one phase (being referred to as second phase herein) preferably granular solids (this term comprises powder, particle, agglomerate, comprise the mixture of itself and liquid adhesive, melting solid, spraying object etc. with other granular solids) form, it is pressed into/goes in one or more molds of first phase of detergent tablet, makes second itself to be the form of formed body mutually.Optional other comprises one or more compositions mutually, they be separately layer or a plurality of layers form.Preferred detergent component comprises: washing assistant, tinting material, tackiness agent, tensio-active agent, cracking agent and enzyme, particularly amylase and proteolytic enzyme.Of the present invention another preferred aspect, second mutually and its optional second phase contain cracking agent, it can be selected from disintegrating agent or pore forming material.Suitable disintegrants comprises and expands when contacting with water or be convenient to water and flow into and/or effusive reagent by form passage in detergent tablet.Any known disintegrating agents or the pore forming material that are applicable to the application of laundry or wash up can be considered to be used in this article.Suitable disintegrants comprises: starch is (for example natural, modification, starch with pre-gelledization, for example from corn, rice and yam starch deutero-those), starch derivative is U-Sperse (trade(brand)name) for example, Primojel (trade(brand)name) and Explotab (trade(brand)name), Mierocrystalline cellulose, Arbocel (trade(brand)name) and Vivapur (trade(brand)name) that Microcrystalline Cellulose and derivatived cellulose for example can obtain from Rettenmaier, the Nymcel (trade(brand)name) that can obtain from Metsa-serla, Avicel (trade(brand)name), Lattice NT (trade(brand)name) and Hanfloc (trade(brand)name), alginate, acetate trihydrate, burkeite, the carbonate of the hydration of formula Na2CO3.H2O, have the STPP at least about the hydration of 40% phase I content, carboxymethyl cellulose (CMC) is based on the polymkeric substance of CMC, sodium acetate, aluminum oxide.Suitable pore forming material is those materials that produce gas when contacting with water.Suitable pore forming material can be to emit oxygen, the material of nitrogen peroxide or carbonic acid gas.The example of preferred pore forming material can be selected from: with carboxylic acid or other acid citric acid for example, thionamic acid, the perborate that oxysuccinic acid or toxilic acid are combined, percarbonate, carbonate, supercarbonate.

Mix by the component of liquid ingredient in the dried component of for example mixing and mixing or the spraying detergent composition.Then with second mutually and the component feeding of its second phase of choosing wantonly advance and be retained in by in first mold that provides mutually.

The preferred embodiment of the invention comprises two phases: first mutually with second mutually.First generally includes a mold mutually, and second is made up of single washing composition active composition mutually usually., can consider that first can comprise mutually more than a mold, second mutually also can be from preparing more than a kind of detergent active composition.In addition, also can consider second comprise mutually be included in the mold more than a kind of washing composition active composition.It is also conceivable that several washing composition active compositions are included in the different molds.In this method, thereby possible chemosensitive detergent component can be separated to avoid to react any performance loss that causes and the inactivation or be consumed of may becoming by these components together.

The present invention preferred aspect, first, second and/or its optional second phase can contain tackiness agent.When it exists, this tackiness agent is selected from: organic polymer, and for example polyoxyethylene glycol and/or polypropylene glycol, particularly molecular weight are 4000, those of 6000 and 9000, paraffin, polyvinylpyrrolidone (PVP), especially molecular weight are 90000 PVP, polyacrylate, sucrose and sucrose derivative, starch and starch derivative, for example HYDROXY PROPYL METHYLCELLULOSE (HPMC) and carboxymethyl cellulose (CMC); And inorganic polymer, for example hexametaphosphate.As described below, tackiness agent is useful for the integrity of sheet with helping realization first and second dissolving respectively mutually.

Of the present invention preferred aspect, the weight of first phase is preferably greater than about 4g greater than about 3g, more preferably greater than about 5g.Preferably, the weight of first phase is about 10-30g, more preferably from about 15-25g, most preferably from about 18-24g.The weight of second phase and its second phase of choosing wantonly is less than 4g.More preferably second mutually and/or the weight of its optional second phase between about 0.1-3.5g, preferably at about 1-3.5g, most preferably from about 1.3-2.5g.

Mutually and/or between its optional second phase or in fact in another embodiment of the invention, a blocking layer of containing barrier layer composition is placed on first mutually with second second mutually and between its optional second phase.This barrier layer composition comprises at least a aforesaid tackiness agent that is selected from.The advantage that has the blocking layer is to prevent or reduce the migration of component from one to another phase, for example first enters second mutually mutually and/or its optional second phase and vice versa.

With respect to the pressure that is generally used for preparing sheet, preferably under low-down pressure, suppress the component of second phase and optional its second phase.Therefore, advantage of the present invention is: owing to use low pressure, and the performance loss of the corresponding generation that does not suffer when being incorporated into such component in the sheet, to run into usually so can will be incorporated into heat, power or chemosensitive detergent component in the detergent tablet.In addition, can identical or than the first mutually higher pressure under compacting second mutually or these are mutually so that reach the dissolving respectively of phase as described below.

Other advantage of the present invention is to improve to have prevented by for example loading and unloading and transporting second mutually the infringement that causes.As mentioned above, the multi-phase detergent sheet is to prepare under the situation of the compacting second layer under the pressure lower than the first layer., although improved dissolution rate, the second layer of these sheets becomes and is easy to damage, and understands fragmentation or become fragment when contact.Yet, being protected in mutually in the mold that provides mutually by first of detergent tablet of the light compacting of detergent tablet of the present invention.

Another advantage of the present invention is to prepare such multi-phase detergent sheet, and one of them can be designed to preferably dissolving significantly before another phase mutually.In the present invention, preferably second mutually and its optional second phase dissolve before mutually first.According to preferred weight range recited above, preferably first at 5-20 minute, more preferably dissolving in 10-15 minute, with second mutually and/or its optional second phase less than 5 minutes, be more preferably less than 4.5 minutes, most preferably dissolved less than 4 minutes.In addition, second can dissolve mutually or after other phase first mutually, for example, need provide when finishing near washing operation under the situation of cleaning or rinse action.First phase, second mutually and/or the dissolution time of its optional second phase be separately independently.Therefore, the present invention particularly preferred aspect, realized the dissolving respectively of these phases.Can realize the multi-phase detergent sheet respectively the special benefit of dissolved be by exist other component cause the component of chemical inactivation can be separated different mutually in.In this case, this inactivation component preferably is placed on second mutually and in its optional second phase.

Another advantage of the present invention is the binding property of having improved between the multi-phase tablets phase.It is believed that this improved binding property is achieved in that with the known multi-phase tablets of prior art compares, and has reduced the exposure of second phase, thereby has caused of the present invention osculatory that is not easy between mutually to split.

Method

Use any suitable pelletizer for example Courtoy R253 prepare the multi-phase detergent sheet.These sheets preferably prepare by compacting in the tabletting machine that can prepare the sheet that comprises mold.In particularly preferred embodiment of the present invention, first tabletting machine that is to use particular design mutually is by following step preparation.The drift of this tabletting machine is modified, so that the punch head surface of contact detergent composition has the surface of protrusion.

First kind of detergent composition delivered in the mould of tabletting machine, and the decline drift contacts detergent composition and it is pressed into first phase.Use usually at least about 250kg/cm ², preferably at about 350-2000kg/cm ²Between, 500-1500kg/cm more preferably from about ², 600-1200kg/cm most preferably from about ²Pressure suppress first detergent composition.The drift that raises then exposes first phase that contains mold.Be provided in this mold with optional secondly detergent composition second then.For the second time reduce specially designed tabletting machine drift then, gentlier suppress second and optional secondly detergent composition form second mutually with its second phase of choosing wantonly.In another embodiment of the invention, when having optional secondly phase time, its optional second phase of preparation in being similar to the optional follow-up pressing step of above-mentioned second pressing step substantially.Preferably be lower than about 350kg/cm ², 40-300kg/cm more preferably from about ², 70-270kg/cm most preferably from about ²Pressure down compacting second and optional secondly detergent composition.Suppress after second detergent composition, drift and the multi-phase detergent sheet discharged from tabletting machine raises for the second time.

Detergent component

By suppress the described herein multi-phase detergent sheet of one or more preparation of compositions that contain detergent active ingredients first mutually and second mutually or its second phase of choosing wantonly.Be used for any of these composition mutually and can suit to comprise various detergent component, comprising: washing-aid compound, tensio-active agent, enzyme, SYNTHETIC OPTICAL WHITNER, alkali source, tinting material, spices, lime soap dispersing agent, organic polyhydroxyl compound comprise the polymeric dye transfer inhibitor, crystal growth inhibitor, heavy metal ion chelating agent, metal cation salt, enzyme stabilizers, corrosion inhibitor, suds suppressor, solvent, fabric softener, white dyes and hydrotropic agent.

The detergent component very preferably of first phase comprises: washing-aid compound, tensio-active agent, enzyme and SYNTHETIC OPTICAL WHITNER.The detergent component very preferably of second phase comprises: washing assistant, enzyme, crystal growth inhibitor and cracking agent and/or tackiness agent.

Washing-aid compound

Of the present invention preferably contains washing-aid compound, and by the weight of composition, its general amount that exists is 1-80%, preferred 10-70%, most preferably the activated detergent component of 20-60%.

The water soluble detergency promoter compound

Suitable water soluble detergency promoter compound comprises the water-soluble monomer multi-carboxylate, or its sour form, the poly carboxylic acid of homopolymerization or copolymerization or its salt, wherein this poly carboxylic acid comprises at least 2 by no more than 2 carboxyls that carbon atom separates, carbonate, supercarbonate, borate, the mixture of phosphoric acid salt and above-mentioned arbitrary material.

Carboxylate salt or multi-carboxy acid salt washing agent can be monomeric or oligomer on type, but owing to the reason monomer multi-carboxylate of cost and performance is normally preferred.

The suitable carboxylate salt that contains 1 carboxyl comprises: the water-soluble salt of lactic acid, oxyacetic acid and its ether derivant.The multi-carboxylate of containing 2 carboxyls comprises: the water-soluble salt of succsinic acid, propanedioic acid, (ethylenedioxy) oxalic acid, toxilic acid, diethyl alkyd, tartrate, tartronic acid and fumaric acid, and ether multi-carboxylate and sulfinyl carboxylate salt.The multi-carboxylate of containing 3 carboxyls comprises: particularly, water-soluble citrate, aconitate and citraconate and succinate derivative, for example, the carboxyl methoxy succinate described in the British Patent No. 1379241, the newborn oxidation succinate described in the British Patent No. 1389732 and at the aminosuccinic acid salt described in the Holland application 7205873 and oxidation multi-carboxylate material for example at the 2-oxa--1 described in the British Patent No. 1387447,1,3-tricarballylic acid salt.

The multi-carboxylate of containing 4 carboxyls comprises: disclosed oxygen di-succinate, 1,1,2 in British Patent No. 1261829,2-ethane tetracarboxylic acid hydrochlorate, 1,1,3,3-propane tetracarboxylic acid salt and 1,1,2,3-propane tetracarboxylic acid salt.Containing the substituent multi-carboxylate of sulfo group comprises: British Patent No. 1398421 and 1398422 and US3936448 in disclosed sulfo-succinic acid salt derivative and at the sulfonated pyrolytic Citrate trianion described in the British Patent No. 1439000.

Alicyclic ring and heterocycle multi-carboxylate comprise: pentamethylene-suitable, suitable, suitable-the tetracarboxylic acid hydrochlorate, cyclopentadiene acid anhydride pentacarboxylic acid salt, 2,3,4,5-tetrahydrofuran (THF)-suitable, suitable, suitable-tetracarboxylic acid hydrochlorate, 2,5-tetrahydrofuran (THF)-suitable-dicarboxylate, 2,2,5,5-tetrahydrofuran (THF)-tetracarboxylic acid hydrochlorate, 1,2,3,4,5, the carboxymethyl derivant of 6-hexane-hexacarboxylic acid salt and polyvalent alcohol (for example sorbyl alcohol, mannitol and Xylitol).Aromatic polycarboxylic acids salt comprises: disclosed mellitic acid, 1,2,4,5 in British Patent No. 1425343 ,-pyromellitic acid and phthalic acid derivative.

Among the superincumbent multi-carboxylate, preferred multi-carboxylate is that per molecule contains the most nearly hydroxycarboxylate of 3 carboxyls, Citrate trianion more specifically.

The parent acid of monomer or oligomeric multi-carboxylate's sequestrant or with the mixture of its salt, for example citric acid or Citrate trianion/citric acid mixture also are considered to useful builder component.

The borate washing assistant and contain washing composition store or wash conditions under can to produce the washing assistant that boratory borate forms material also be useful, but be lower than 50 ℃, it is not preferred particularly being lower than under 40 ℃ the wash conditions.

The example of carbonate builders is alkaline-earth metal and alkaline carbonate, comprises the mixture of yellow soda ash and sesquicarbonate and itself and calcium carbonate superfine powder, as disclosed on November 15th, 1973 disclosed German patent application numbers 2321001.

Being used for the present invention's washing assistant very preferably is the water-soluble phosphate washing assistant.The object lesson of water-soluble phosphate washing assistant is an alkali metal tripolyphosphates, trisodium phosphate, potassium and ammonium, and trisodium phosphate, potassium and ammonium, sodium orthophosphate and potassium, wherein the polymerization degree is partially poly-/sodium phosphate of 6-21, and phytate.

The specific examples of water-soluble phosphate washing assistant is alkali metal tripolyphosphates, trisodium phosphate, potassium and ammonium, sodium orthophosphate and potassium, and the polymerization degree is partially poly-/sodium phosphate of 6-21, and phytate.

Partly soluble or insoluble washing-aid compound

Of the present invention can contain partly soluble or insoluble washing-aid compound.Partly soluble and insoluble washing-aid compound is specially adapted to being used for the prepared sheet of purging method of doing washing.The example of the water miscible washing assistant of part for example comprises at EP-A-0164514, disclosed crystalline layered silicate among DE-A-3417649 and the DE-A-3742043.The crystalline layered sodium silicate of following formula preferably:

NaMSi _xO ₂₊₁YH ₂O wherein M is sodium or hydrogen, and x is that 1.9-4 and y are 0-20.Such crystalline layered sodium silicate preferably has bidimensional " sheet " structure, and for example so-called δ-laminate structure is as described in EP0164514 and the EP0293640.The method for preparing this class crystalline layered silicate is disclosed among DE-A-3417649 and the DE-A-3742043.For purpose of the present invention, above x value in the general formula be 2,3 or 4, preferably 2.

Most preferred crystalline layered sodium silicate compound has formula δ-Na ₂Si ₂O ₅, being referred to as NaSKS-6 (trade(brand)name), can obtain from Hoechst AG.

Crystalline layered sodium silicate preferably as with the intimate mixture of solid, water soluble ionizable material in particulate material be present in the granular detergent composition, as described in the PCT application WO92/18594.This solid, water soluble ionizable material is selected from organic acid, organic and inorganic acid salt and its mixture, and citric acid is preferred.

Basically the example of water-insoluble washing assistant comprises sodium silicoaluminate.Suitable silico-aluminate washing assistant comprises aluminosilicate zeolite, and it has unit cell formula M _z[(AlO ₂) _z(SiO ₂) _y] xH ₂O, wherein z and y are at least 6, and the mol ratio of z and y is 1.0-0.5, and x is 5 at least, preferred 7.5-276, more preferably 10-264.This alumino-silicate materials be hydrated form and preferably crystallization, contain 10-28%, more preferably the water of 18-22% combining form.

Aluminosilicate zeolite can be naturally occurring material, but preferably synthetic deutero-.Synthetic crystal aluminosilicate ion-exchange material can title zeolite A, zeolite B, and zeolite P, X zeolite, zeolite HS and its mixture obtain.

The preferred method of synthesizing Si-Al hydrochlorate zeolite be by people such as Schoeman (be published in zeolite (Zeolite) (1994) 14 (2), the 110-116) method of Miao Shuing, in the method, the author has described the method for preparing the colloid aluminosilicate zeolite.This colloid aluminosilicate zeolite particle should be preferably such: no more than 5% particle grain size greater than the particle grain size of 1 μ m and no more than 5% less than 0.05 μ m.This aluminosilicate zeolite particulate median size is preferably between 0.01-1 μ m, more preferably between 0.05-0.9 μ m, most preferably between 0.1-0.6 μ m.

Zeolite A has following formula:

Na ₁₂[AlO ₂) ₁₂(SiO ₂) ₁₂] xH ₂O wherein x is 20-30, particularly 27.X zeolite has formula Na ₈₆[(AlO ₂) ₈₆(SiO ₂) ₁₀₆] .76H ₂O.As at the zeolite MAP described in the EP-B-384070 being preferred zeolite builders herein.

Preferred aluminosilicate zeolite is the colloid aluminosilicate zeolite.When using as the component of detergent composition, colloid aluminosilicate zeolite, especially colloidal zeolite A provide enhanced washing assistant performance aspect the improved greasiness removal providing.Harden and improve and also seen enhanced washing assistant performance aspect the fabric whiteness maintenance reducing fabric; It is relevant with the detergent composition of composite difference that these problems it is believed that.

Unexpected discovery be comprise the mixing aluminosilicate zeolite detergent composition of colloidal zeolite A and colloidal zeolite Y with etc. the commercially available zeolite A of weight compare the calcium ion that equates sequestering action be provided.

Another beyond thought discovery be above-mentioned mixing aluminosilicate zeolite detergent composition with etc. the commercially available zeolite A of weight compare improved magnesium ion sequestering action be provided.

Tensio-active agent

Tensio-active agent is the preferred detergent active ingredients of described composition herein.Suitable tensio-active agent is selected from negatively charged ion, positively charged ion, nonionic, both sexes and zwitterionics and its mixture.The product that the automatic dishwashing machine is used should be low bubble property, and the whipability or be more preferably that therefore must suppress to be used for the surfactant system of wash up method is hanged down and foamed, and generally is nonionic.The foaming that is caused by the surfactant system that uses in the clothes washing method does not need to be suppressed to the same degree with the wash up needs.Press composition weight meter, the amount that tensio-active agent exists generally is 0.2-30%, more preferably 0.5-10%, most preferably the activated detergent component of 1-5%.

In the US3929678 of the Laughlin of 30 promulgations December in 1975 and Heuring, provided the generality tabulation of negatively charged ion, nonionic, both sexes and the zwitter-ion type and the material of these tensio-active agents.In the US4259217 of the Murphy of on March 31st, 1981 promulgation, provided the tabulation of suitable cationic surfactants.For example, in EP-A-0414549 and PCT application WO93/08876 and WO93/08874, provided the tabulation that generally is included in the tensio-active agent in the automatic dishwashing detergent composition.

Nonionogenic tenside

Basically anyly can be included in the detergent tablet washing purpose useful nonionogenic tenside.Below the type of preferred nonrestrictive useful nonionogenic tenside is listed in.

Nonionic alcohol alcoxylates tensio-active agent

The alkylethoxylate condensation product of fatty alcohol and 1-25 moles of ethylene oxide is applicable to herein.The alkyl chain of this fatty alcohol can be straight or branched, uncle or secondary, and contain 6-22 carbon atom usually.Particularly preferably be and have the alcohol that contains 8-20 carbon atom alkyl and the condensation product of every mol of alcohol 2-10 moles of ethylene oxide.

End capped alkyl alkoxylates tensio-active agent

Suitable end capped alkyl alkoxylates tensio-active agent is end capped poly-(o-alkylation) alcohol of epoxide that is expressed from the next:

R ₁O[CH ₂CH (CH ₃) O] _x[CH ₂CH ₂O] _y[CH ₂CH (OH) R ₂] (I) R wherein ₁It is straight or branched aliphatic hydrocarbyl with 4-18 carbon atom; R wherein ₂It is straight or branched aliphatic hydrocarbyl with 2-26 carbon atom; X is that mean value is the integer of 0.5-1.5, more preferably 1; Y is at least 15 integer, more preferably at least 20.

Preferably, the tensio-active agent of formula I is at end group epoxide unit [CH ₂CH (OH) R ₂] in have 10 carbon atoms at least.According to the present invention, the tensio-active agent of suitable formula I is as the POLY-TERGEN by the Olin company described in the disclosed WO94/22800 of Olin company on October 13rd, 1994 ^RThe SLF-18B nonionogenic tenside.

Ether capped poly-(o-alkylation) alcohol

Preferred surfactants used herein comprises ether capped poly-(o-alkylation) alcohol with following formula:

R ¹O[CH ₂CH (R ³) O] _x[CH ₂] _kCH (OH) [CH ₂] _jOR ²R wherein ¹And R ²Be have 1-30 carbon atom straight or branched, saturated or undersaturated, aliphatics or aromatic alkyl; R ³Be H, or have the linear aliphatic alkyl of 1-4 carbon atom; X is the integer of mean value 1-30, wherein when x be 2 or when bigger, R ³Can be identical or different, k and j are that mean value is the integer of 1-12, more preferably 1-5.

R ¹And R ²Be have 6-22 carbon atom (8-18 carbon atom is preferred) straight or branched, saturated or undersaturated, aliphatics or aromatic alkyl; To R ³H or have the linear aliphatic alkyl of 1-2 carbon atom most preferably; Preferably, x is the integer of mean value 1-20, most preferably 6-15.

As mentioned above, when in preferred embodiments, and x is greater than 2 o'clock, R ³Can be identical or different.Be R ³Can between aforesaid any alkene oxygen unit, change.For example, if x is 3, R so ³Can be selected from vinyloxy group (EO) or propenyloxy group (PO) and can be with (EO) (PO) (EO), (EO) (EO) (PO), (EO) (EO) (EO), (PO) (EO) (PO), (PO) (PO) (EO) and (PO) (PO) order (PO) change.Certainly, select integer 3 only as an example, for the x of higher value, variation can be much bigger, for example comprises a plurality of (EO) unit and much smaller (PO) unit of amount.

Above-mentioned particularly preferred tensio-active agent comprises that cloud point is lower than those tensio-active agents of 20 ℃.These low cloud point tensio-active agents can use with the high cloud point tensio-active agent of describing in detail below so, to reach excellent grease cleaning performance.

Most preferred ether capped poly-(o-alkylation) pure tensio-active agent be wherein k be 1 and j be 1 those, thereby this tensio-active agent has following formula:

R ¹O[CH ₂CH (R ³) O] _xCH ₂CH (OH) CH ₂OR ²R wherein ¹, R ²And R ³Definition as above, x is that mean value is the integer of 1-30, preferred 1-20, more preferably 6-18.Most preferably such tensio-active agent, wherein R ¹And R ²At the scope of 9-14, R ³Be the H that forms vinyloxy group, x is in the scope of 6-15.

This ether capped poly-(o-alkylation) pure tensio-active agent comprises 3 kinds of common components, i.e. straight or branched alcohol, alkylene oxide and alkyl oxide end-blocking.The hydrophobic oil dissolubility part that alkyl oxide end-blocking and alcohol serve as molecule, and alkylene oxide group forms the hydrophilic, water soluble part of molecule.

When using with high cloud point tensio-active agent, with respect to conventional surfactants, these tensio-active agents are becoming aspect spot and the film-forming properties and are demonstrating tangible improvement aspect the grease dirt removing.

In general, ether capped poly-(o-alkylation) pure tensio-active agent of the present invention can prepare like this: fatty alcohol and epoxide reaction are formed ether, then itself and second kind of epoxide of alkali reaction formation.Second kind of epoxide and oxyalkylated alcohol reaction form new compound of the present invention then.The example of ether capped poly-(o-alkylation) the pure surfactivity agent method of preparation is described below:

C _12/14The preparation of alkyl glycidyl ether

With C _12/14Fatty Alcohol(C12-C14 and C12-C18) (100.00g, 0.515mol) and tin chloride (IV) (0.58g, 2.23mmol obtain from Aldrich) be blended in the condenser that is equipped with of 500mL, the argon gas import, feed hopper is in the 3 neck round bottom beakers of magnetic stirring apparatus and internal temperature detector.With this mixture heating up to 60 ℃.Drip Epicholorohydrin (47.70g, 0.515mol can obtain from Aldrich) so that temperature is remained between 60-65 ℃.At 60 ℃ of restir after 1 hour, with this mixture cool to room temperature.Sodium hydroxide solution with 50% (61.80g, 0.773mol, 50%) is handled this mixture mechanical stirring simultaneously.After adding, through 1.5 hours, cooling was filtered by ethanol with this mixture heating up to 90 ℃.Separating filtrate and water (100mL) washing organic phase is through MgSO ₄Drying is filtered and is concentrated.This oil distills under 100-120 ℃ of (0.1mmHg) condition and obtains the Racemic glycidol ether oil.

C _12/14Alkyl-C _9/11The preparation of ether capped pure tensio-active agent

With Neodol ^R91-8 (20.60g, the alcohol of 0.0393mol ethoxylation obtain from ShellChemical Co.) and tin chloride (IV) (0.58g, 2.23mmol) be blended in the condenser that is equipped with of 250mL, the argon gas import, feed hopper is at the bottom of the 3 neck gardens of magnetic stirring apparatus and internal temperature detector in the beaker.With this mixture heating up to 60 ℃, under this temperature, with dripping C in 15 minutes _12/14Alkyl glycidyl ether (11.00g, 0.0393mol).60 ℃ stir 18 hours after, with this mixture cool to room temperature and be dissolved in the methylene dichloride of equivalent.This solution is used the methylene dichloride wash-out simultaneously by 1 inch silica-gel plate.Concentrate this filtrate by rotary evaporation, then the Tim Koogle if (kugelrohr) baking oven (100 ℃, 0.5mmHg) in stripping obtain tensio-active agent oil.

The fatty alcohol surfactant of nonionic ethoxylated/propoxylated

Ethoxylation C ₆-C ₁₈Fatty Alcohol(C12-C14 and C12-C18) and C ₆-C ₁₈The Fatty Alcohol(C12-C14 and C12-C18) of blended ethoxylated/propoxylated is the suitable tensio-active agent that is used for herein, when particularly it is water-soluble.

The Fatty Alcohol(C12-C14 and C12-C18) of ethoxylation preferably ethoxylation degree is the C of 3-50 ₁₀-C ₁₈The Fatty Alcohol(C12-C14 and C12-C18) of ethoxylation most preferably is that ethoxylation degree is the C of 3-40 ₁₂-C ₁₈The Fatty Alcohol(C12-C14 and C12-C18) of ethoxylation.Preferably, this blended ethoxylation, propenoxylated Fatty Alcohol(C12-C14 and C12-C18) have the chain length alkyl of 10-18 carbon atom, and ethoxylation degree is 3-30, and the propoxylation degree is 1-10.

Nonionic EO/PO condenses with the propylene glycol condensation

Oxyethane is applicable to herein with the condensation product of the hydrophobic group that forms from propylene oxide and ethylene glycol condensation.The hydrophobic part of these compounds has the molecular weight of 1500-1800 and shows water-insoluble.The example of this class nonionogenic tenside comprises some Pluronic that is commercially available that is sold by BASF ^TM

Nonionic EO condensation product with propylene oxide/quadrol affixture

Oxyethane is applicable to the present invention with the condensation product of the product that is formed by propylene oxide and reacting ethylenediamine.The hydrophobic part of these products is made of the reaction product of quadrol and excessive propylene oxide, and general molecular weight is 2500-3000.The example of this class nonionogenic tenside comprises some the commercially available Tetronic that is sold by BASF ^TMCompound.

The blended nonionic surfactant system

In the preferred embodiment of the invention, detergent tablet contains the blended nonionic surfactant system, and it contains at least a low cloud point non-ionic surfactants and at least a high cloud point non-ionic surfactants.

As using in this article, " cloud point " is the known properties of nonionogenic tenside, it is a tensio-active agent along with the temperature more insoluble result that becomes that raises, observe the temperature that second phase occur and be referred to as " cloud point " (seeing the chemical technology encyclopaedia the 3rd edition of Kirk Othmer, 22 volume 360-379 pages or leaves).

As using in this article, " low cloud point " nonionogenic tenside is defined as to have and is lower than 30 ℃, preferably is lower than 20 ℃, more preferably less than the nonionic surfactant system component of 10 ℃ of cloud points.General low cloud point non-ionic surfactants comprises the oxyalkylated tensio-active agent of nonionic, especially from primary alconol and the anti-block polymer deutero-of polyoxypropylene/polyoxyethylene/polyoxypropylene (PO/EO/PO) ethoxylate.In addition, so low cloud point non-ionic surfactants also comprises: for example, and the ethoxylation-propenoxylated alcohol (Poly-Tergent of Olin company for example ^RSLF18), epoxide end capped poly-(o-alkylation) alcohol (Poly-Tergent of Olin company for example ^RThe nonionogenic tenside of SLF18B series is as described in the WO94/22800 of disclosed Olin company on October 13rd, 1994) and ether capped poly-(o-alkylation) pure tensio-active agent.

Nonionogenic tenside can randomly contain the propylene oxide that its amount is up to 15% (weight).Other preferred nonionic can prepare with the method described in the US4223163 of promulgation on September 16th, 1980, and the document is incorporated herein by reference.

Low cloud point non-ionic surfactants also comprises polyoxyethylene, the compound of polyoxypropylene block polymerization.Block polyoxyethylene-polyoxypropylene polymeric compounds comprises based on ethylene glycol, propylene glycol, glycerine, TriMethylolPropane(TMP) and quadrol those compounds as the active dydrogen compounds initiator.By BASF-Wyanotte Corp., Wyandotte, the PLURONIC of Michigan registration ^, REVERSED PLURONIC ^, and TETRONIC ^Some block polymer surfactant compounds in ADD composition of the present invention, be suitable.Preferred example comprises REVERSED PLURONIC ^R25R2 and TETRONIC ^R702, such tensio-active agent is general to be useful as low cloud point non-ionic surfactants in this article.

As using in this article, " high cloud point " nonionogenic tenside is defined as to have and is higher than 40 ℃, preferably is higher than 50 ℃, more preferably is higher than the nonionic surfactant system component of 60 ℃ of cloud points.Preferably, this nonionic surfactant system comprises the tensio-active agent of the ethoxylation that is obtained by the single hydroxyl alcohol that contains 8-20 carbon atom or alkylphenol and every mol of alcohol or the average 6-15 moles of ethylene oxide reaction of alkylphenol.High cloud point non-ionic surfactants like this comprises: for example, and Tergitol 15S9 (providing), RhodasurfTMD8.5 (providing) and Neodol 91-8 (providing) by Shell Co. Ltd (Shell) by Rhone Poulenc by Union Carbide.

For purpose of the present invention, further preferably this high cloud point non-ionic surfactants also has the hydrophile-lipophile balance value (" HLB " in the 9-15 scope; The document of Kirk Othmer in seeing above), preferred 11-15.Such material comprises: for example, and Tergitol 15S9 (providing), Rhodasurf TMD8.5 (providing), and Neodol91-8 (providing) by Shell by Rhone Poulenc by Union Carbide.

Another preferred high cloud point non-ionic surfactants is from the straight chain that contains 6-20 carbon atom or preferred side chain or secondary Fatty Alcohol(C12-C14 and C12-C18) (C ₆-C ₂₀Alcohol) comprise secondary alcohol and branched-chain primary alcohol deutero-.High cloud point non-ionic surfactants is side chain or secondary alcohol and the average 6-15 mole of every mol of alcohol preferably, preferred 6-12 mole, the most preferably ethoxylate of 6-9 moles of ethylene oxide condensation, more preferably blended C9/11 or C11/15 branched-chain alcoho ethoxylate.Preferably, the nonionogenic tenside of deutero-ethoxylation has narrow ethoxylate distribution with respect to mean value like this.

Anion surfactant

Basically any anion surfactant that is used to wash purpose all is suitable.These tensio-active agents can comprise anion sulfate, sulfonate, carboxylate salt and sarcosinate surfactant salt (comprise, for example, sodium, potassium, ammonium and substituted ammonium salt be for example single, two and triethanolamine salt).The anion sulfate acid salt surfactant is preferred.

Other anion surfactant comprises: isethionate is acyl isethinate for example, N-acyl taurine salt, the fatty acid amide of N-methyltaurine acid anhydride, alkyl succinate and sulfosuccinate, the monoesters of sulfo-succinic acid (particularly saturated and unsaturated C ₁₂-C ₁₈Monoesters), the diester of sulfo-succinic acid (particularly saturated and unsaturated C ₆-C ₁₄Diester), N-acyl sarcosinate.Resinous acid and hydrogenant resinous acid also are suitable, for example rosin, staybelite and resinous acid and the hydrogenated resin acid that is present in or is derived from tallol.

The anion sulfate acid salt surfactant

Be applicable to that anion sulfate tensio-active agent herein comprises: the uncle of straight or branched or secondary alkyl sulfate, alkyl ethoxy sulfate, fatty oil acylglycerol vitriol, alkyl phenol epoxy ethane ether salt, C ₅-C ₁₇Acyl group-N-(C ₁-C ₄Alkyl) and-N-(C ₁-C ₂Hydroxyalkyl) vitriol of glucosamine sulfate and the alkyl polysaccharide vitriol of alkyl polyglucoside (compound of described herein nonionic non-sulfuric acidization) for example.

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

Alkyl ethoxy sulfate surfactant is preferably selected from the C of every mole of molecule with the ethoxylation of 0.5-20 moles of ethylene oxide ₁₀-C ₁₈Alkyl-sulphate.More preferably, this alkyl ethoxy sulfate surfactant is every mole of molecule 0.5-7 mole, the C of preferred 1-5 moles of ethylene oxide ethoxylation ₁₁-C ₁₈, C most preferably ₁₁-C ₁₅Alkyl-sulphate.

The present invention uses particularly preferred aspect the mixture of preferred alkyl-sulphate and alkyl ethoxy sulfate surfactant.Such mixture is disclosed among the PCT patent application WO93/18124.

The anion sulfoacid salt surfactant

Be applicable to that anionic sulphonate tensio-active agent herein comprises: C ₅-C ₂₀Linear alkylbenzene sulfonate, alkyl ester sulfonate, C ₆-C ₂₂Uncle or secondary paraffin sulfonate, C ₆-C ₂₄Alkene sulfonate, sulfonated poly carboxylic acid, alkyl glycerol sulfonate, fatty acyl group glycerol sulfonate, fatty oil acylglycerol sulfonate and its any mixture.

The anionic carboxylic acid salt surfactant

Suitable anionic carboxylate tensio-active agent comprises: alkyl ethoxy carboxylate, alkyl polyethoxye multi-carboxylate's tensio-active agent and soap (" alkyl carboxylate "), particularly some secondary soap as described herein.

Suitable alkyl ethoxy carboxylate comprises formula RO (CH ₂CH ₂O) _xCH ₂COO ^-M ⁺Those, wherein R is C ₆-C ₁₈Alkyl, x be in the scope of 0-10, and this oxyethyl group is to distribute like this, causes by weight when x is 0, and it is measured less than 20%, and M is a positively charged ion.Suitable alkyl polyethoxye multi-carboxylate tensio-active agent comprises formula RO-(CHR ₁CHR ₂-O)-R ₃Those, wherein R is C ₆-C ₁₈Alkyl, x are 1-25, R ₁And R ₂Be selected from hydrogen, formyloxy, amber acidic group, hydroxy succinic acid base and its mixture, R ₃Be selected from alkyl and its mixture of hydrogen, replacement or the unsubstituted 1-8 of a having carbon atom.

Suitable soap surfactant comprises and contains the unitary secondary soap surfactant of the carboxyl that is connected on the secondary carbon(atom).The preferred secondary soap surfactant that is used for herein is water miscible, and it is selected from 2-methyl isophthalic acid-undecanoic 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 surfactant is formula R-CON (R ¹) CH ₂The basic metal sarcosinate of COOM, wherein R is C ₅-C ₁₇Straight or branched alkyl or alkenyl, R ¹Be C ₁-C ₄Alkyl, M are alkalimetal ions.Preferred example is the myristyl and the oleoyl methyl sarcosinate of its sodium-salt form.

Amphoterics

The suitable amphoterics that is used for herein 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 the alkyl, hydroxyalkyl, acyl group amido propyl group and the alkyl phenyl that contain 8-26 carbon atom, or its mixture; R ⁴Be alkylidene group or the hydroxy alkylidene that contains 2-3 carbon atom, or its mixture; X is 0-5, preferred 0-3; Each R ⁵It is the polyethylene oxide base that contains the alkyl or the hydroxyalkyl of 1-3 carbon atom or contain 1-3 ethylene oxide group.C preferably ₁₀-C ₁₈Alkyl dimethyl amine oxide and C ₁₀-C ₁₈Acyl group amidoalkyl dimethyl oxidation amine.

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

Zwitterionics

Also zwitterionics can be incorporated in its detergent composition.These tensio-active agents can briefly be described as the derivative of the second month in a season or tertiary amine, the derivative of the heterocyclic second month in a season or tertiary amine, or the derivative of quaternary ammonium, quaternary phosphine or uncle's sulfonium compound.Trimethyl-glycine and sultaine are the examples that is used for zwitterionics herein.

Suitable trimethyl-glycine is to have formula R (R ¹) ₂N ⁺R ²COO ^-Those compounds, wherein R is C ₆-C ₁₈Alkyl, each R ¹Generally be C ₁-C ₃Alkyl, R ²Be C ₁-C ₅Alkyl.Preferred trimethyl-glycine is C _12-18Dimethyl caproic acid ammonium and C _10-18Acyl group amido propane (or ethane) dimethyl (or diethyl) trimethyl-glycine.The compound beet alkali surface activator also is applicable to herein.

Cats product

What the cationic ester tensio-active agent that is used for the present invention preferably had a surfactant properties comprises at least one ester (dispersible compound of water of key and at least one band cationic charge promptly-COO-).The cationic ester tensio-active agent that other is suitable comprises the cholinesterase tensio-active agent, is for example disclosing among US4228024, US4239660 and the US4260529.

Suitable cationic surfactants comprises quaternary surfactant, and it is selected from single 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.

Enzyme

Enzyme is first mutually and more particularly second mutually and/or the preferred detergent component of other phase of choosing wantonly.When it existed, described enzyme was selected from cellulase, hemicellulase, peroxidase, proteolytic enzyme, glucoamylase, amylase, zytase, lipase, Phospholipid hydrolase, esterase, keratanase, polygalacturonase, M-Zyme, reductase enzyme, oxydase, oxidation of phenol enzyme, lipoxygenase, lignoenzyme, Starch debranching enzyme, tannase, pentosanase, malic enzyme (malanases), beta-glucanase, alglucerase, Unidasa, chondroitinase, laccase or its mixture.

Preferred enzyme comprises proteolytic enzyme, amylase, and lipase, peroxidase, keratanase and/or cellulase are together with one or more plant cell-wall degrading enzymes.

The cellulase that is used for the present invention comprises bacterium and the plain enzyme of mould fiber type.Preferably, their best pH is between the 5-12 and active on 50CEVU (Mierocrystalline cellulose viscosity unit).Suitable cellulase is disclosed in people's such as Barbesgoard US4435307, among J61078384 and the WO96/02653, it discloses the mould cellulase of producing from unusual humicola lanuginosa (Humicolainsolens), Trichoderma, careless Rhizopus and Sporothrix respectively.EP739982 has described from the new isolated cellulase of genus bacillus kind.Suitable cellulase also is disclosed in GB-A-2075028; GB-A-2095275; Among DE-OS-2247832 and the WO95/26398.

The example of such cellulase is unusual humicola lanuginosa (grey Humicola mutation thermoidea) bacterial strain, particularly the cellulase of Humicola strain DSM 1800 productions.Other suitable cellulase is that to come from molecular weight be that 50KDa, iso-electric point are 5.5 and contain the cellulase of 415 amino acid whose unusual humicola lanuginosas; With from unusual humicola lanuginosa, the DSM1800 deutero-, demonstrate cellulase activity～the 43kD endoglucanase; Preferred endoglucanase component has the disclosed aminoacid sequence at PCT patent application WO91/17243.Also suitable cellulase is the EGIII cellulase that obtains from the Trichoderma longibrachiatum described in the WO94/21801 of disclosed Genencor on the 29th September in 1994.Specially suitable cellulase is to have the cellulase that color is safeguarded benefit.The example of such cellulase is at the cellulase described in the European Patent Application No. 91202879.2 (Novo) of application on November 6th, 1991.Carezyme and Celluzyme (Novo Nordisk A/S) are useful especially.Referring to WO91/17244 and WO91/21801.The cellulase of fabric nursing that other is suitable and/or cleaning character is described in WO96/34092, among WO96/17994 and the WO95/24471.

By detergent composition weight, the add-on of described cellulase in detergent composition is generally the organized enzyme of 0.0001-2%.

Peroxidase can use with oxygen source such as percarbonate, perborate, persulphate, hydrogen peroxide etc.They generally are used for " solution bleaching " and prevent that promptly the dyestuff or the pigment that break away from from transferring to another substrate at washing soln from a substrate during washing operations.Peroxidase is known in this area, and comprises, for example, horseradish peroxidase, lignoenzyme and halo peroxidase be chloro or bromoperoxidase for example.The detergent composition that contains peroxidase is disclosed in, for example the PCT International Application No. WO 89/099813, and laccase also is suitable enzyme among WO89/09813 and European patent application EP 91202882.6 (application on November 6th, 1991) and the EP96870013.8 (application on February 20th, 1996).

The thiodiphenylamine that preferred toughener is replacement is with Fen Evil arsenic lysivane propionic acid (PPT), 10-ethyl thiodiphenylamine-4-carboxylic acid (EPC), 10-phenoxazine propionic acid (POP) and 10-Jia Ji phenoxazine (being described among the WO94/12621) and the syringic acid (the alkyl syringic acid that C3-C5 replaces) and the phenols that replace.SPC-D or Sodium peroxoborate are preferred hydrogen peroxide cources.

By detergent composition weight, described cellulase and/or the peroxidase add-on in detergent composition is generally the organized enzyme of 0.0001-2%.

Other preferred enzyme that can be included in the detergent composition of the present invention comprises lipase.The suitable lipase that is used for the washing composition purposes comprises as disclosed in English Patent 1372034, by the microorganism of pseudomonas, for example Situ Ci Shi aeruginosa atcc 19.154 produce those.Suitable lipase comprises that the antibody with the lipase of being produced by the false unit cell IAM1057 of microorganism fluorescence demonstrates those lipase of positive immunological cross-reaction.This lipase can be from Amono Pharmacevtical Co., Ltd. (Amano Pharmaceutical Co.Ltd.), and Japan Nagoya obtains with trade(brand)name Lipase P " Amano " (hereinafter referred to as " Amano-P ").Other suitable commercially available lipase comprises Amano-CES, from the lipase of thickness look bacillus (Chromobacter viscosum), as thickness look bacillus variant lipolyticum NRRLB3673 (from Toyo Jozo Co., Tagata, Japan); With from other thickness look bacillus lipase of U.S.'s biochemical corp (US Biochemical Corp.) (U.S.) and Disoynth Co. (Holland) with from the lipase of gladiolus pseudomonas.Specially suitable lipase is M1Lipase ^RAnd Lipomax ^R(Gist-Brocades) and Lipolase ^RWith Lipolase Ultra ^R(Novo), find that it is very effective when using with composition of the present invention.That suitable is the EP258068 that is described in Novo Nordisk, the WO94/03578 of WO92/05249 and WO95/22615 and Unilever N.V (Unilever), the lipolytic enzyme among WO95/35381 and the WO96/00292.

That also suitable is keratanase [EC3.1.1.50], and this enzyme can be considered to a kind of special lipase, does not promptly need the lipase of interfacial activity.Keratanase joined in the detergent composition be described in: WO-A-88/09367 (Genencor) for example, among WO90/09446 (Plant Genetic System) and WO94/14963 and the WO94/14964 (Unilever).

By detergent composition weight, lipase and/or the keratanase add-on in detergent composition is generally the organized enzyme of 0.0001-2%.

Suitable proteolytic enzyme is the subtilysin (subtilysin BPN and BPN ') that the specific bacterial strain from bacillus subtilis Pseudomonas and Bacillus licheniformis obtains.Suitable proteolytic enzyme is that the bacterial strain from bacillus obtains, and it has maximum activity in the pH of whole 8-12 scope, is to sell by Novo Industries A/S (hereinafter " the Novo ") exploitation of Denmark and with ESPERSER.The preparation of this enzyme and similar enzyme is described among the GB1243784 of Novo.Other suitable proteolytic enzyme comprises the KANNASE that derives from Novo ^R, ALCALASE ^R, DURAZYM ^RAnd SAVINASE ^RAnd derive from the MAXATASE of Gist-Brocades ^R, MAXACAL ^R, PROPERASE ^RAnd MAXAPEM ^R(through the Maxacal of protein engineering).Proteolytic enzyme also comprises the bacterial serine proteolytic enzyme of modification, for example in the European Patent Application No. 87303761.8 of on April 28th, 1987 application (particularly 17,24 and 98 pages) middle those that describe, it is referred to herein as " proteolytic enzyme B ", with in the European Patent Application No. 199404 of disclosed Venegas on the 29th October in 1986, describe those, it relates to the bacterial serine proteolytic enzyme of modification, and it is referred to herein as " protease A ".Suitable is the enzyme that is called " proteolytic enzyme C " herein, it is the mutation that derives from the alkaline serine protease of bacillus, wherein replace arginine at 27 Methionins, replace Xie Ansuan at 104 tyrosine, replace l-asparagine and replace Threonine at 123 Serines at 274 L-Ala.Proteolytic enzyme C is described among the EP9015958.4, and it is equivalent to WO91/06637, and is open on May 16th, 1991.The modification mutation of the mutation of gene modification, particularly proteolytic enzyme C is also included within herein.

Preferred proteolytic enzyme is referred to as " proteolytic enzyme D ", be to have a carbonylic hydrolase variant that not have aminoacid sequence of discovery at occurring in nature, it be by following mode from precursor carbonylic hydrolase deutero-: according to the numbering of bacillus amyloliquefaciens subtilysin, being equivalent to+76 positions of described carbonylic hydrolase, preferably also be selected from conjunction with being equivalent to+99 ,+101, + 103 ,+104 ,+107, + 123 ,+27 ,+105, + 109, + 126 ,+128 ,+135, + 156, + 166 ,+195 ,+197, + 204, + 206 ,+210 ,+216, + 217, + 218 ,+222 ,+260, + 265, and/or+one or more amino acid residue positions of 274, replace the multiple amino acids residue of described position with different amino acid, as at the WO95/10591 of application on October 13rd, 1994 be called in name people such as C.Ghosh described in the U.S. Patent Application Serial 08/322677 of " BleachingCompositions Comprising Protease Enzymes ".

Also being suitable for of the present invention is the proteolytic enzyme of describing in patent application EP251446 and WO91/06637, at the proteolytic enzyme BLAP described in the WO91/02792 ^RAnd its mutation in WO95/23221.

The high pH proteolytic enzyme of in WO93/18140A, describing referring to Novo that obtains from genus bacillus NCIMB40338 also.Contain proteolytic enzyme, the enzyme detergent of one or more other enzymes and reversible protease inhibitors is described among the WO92/03529 of Novo.When needs, it is available having the adsorptivity of reduction and improving water-disintegrable proteolytic enzyme, as (the Procter﹠amp of P﹠G; Gamble) described in the WO95/07791.Be suitable for being described among the WO94/25583 of Novo of washing composition herein like tryptic recombinant protein enzyme.Other suitable proteolytic enzyme is described among the EP516200 by Unilever.

Other preferred proteolytic enzyme comprises it being the proteolytic enzyme of carbonylic hydrolase variant, and it has the aminoacid sequence that does not have discovery at occurring in nature, and it is to obtain by a plurality of amino-acid residues with different aminoacid replacement precursor carbonylic hydrolases, wherein in pre-enzyme, be equivalent to+210 positions, replace described a plurality of amino-acid residue, and in conjunction with the residues of one or more down column positions :+33, + 62, + 67 ,+76 ,+100, + 101, + 103 ,+104 ,+107, + 128, + 129 ,+130 ,+132, + 135, + 156 ,+158 ,+164, + 166, + 167 ,+170 ,+209, + 215, + 217 ,+218 and+222, wherein the position of label is corresponding to the amino-acid residue that is present in natural subtilysin or the equivalence other carbonylic hydrolase or subtilysin (for example slow genus bacillus (Bacillus lentus) subtilysin) that obtains from bacillus amyloliquefaciens (Bacillus amyloliquefaciens).Such preferred enzyme is included in+and 210 ,+76 ,+103 ,+104 ,+156 and+166 have those of change in location.

Press composition weight meter, the amount that is incorporated into the proteolytic enzyme in the detergent composition of the present invention is 0.0001-2%, preferred 0.001-0.2%, the more preferably pure enzyme of 0.005-0.1%.

In order to remove spot, can comprise amylase (α and/or β) based on carbohydrate.The WO94/02597 of disclosed Novo Nordisk A/S described and mixed the diastatic cleaning combination of mutant on February 3rd, 1994.WO95/10603 referring to disclosed NovoNordisk A/S on the 20th in April nineteen ninety-five.Other become known for amylase in the cleaning combination comprise α-and-βDian Fenmei.α-Dian Fenmei is known in the art and is included in those disclosed in the following document: US5003257; EP252666; WO91/00353; FR2676456; EP285123; EP525610; EP368341 and GB1296839 (Novo).Other suitable amylase be described on August 18th, 1994 disclosed WO94/18314 and February in 1996 disclosed Genencor on the 22nd WO96/05295 in the amylase and the amylase mutation from Novo Nordisk A/S WO95/10603 that obtain, that be disclosed in April, 95, that in direct parent, have other modification of enhanced stability.Also suitable is to be described in EP277216, the amylase among WO95/26397 and the WO96/23873 (they are all by Novo Nordisk application).

The example of commercially available α-Dian Fenmei product is the Purafect OxAm that derives from Genencor ^, the Termamyl that obtains from Denmark Novo Nordisk A/S ^, Ban ^, Fungamyl ^And Duramyl ^WO95/26397 has described other suitable amylase: be characterized as in 25-55 ℃ of temperature range and the 8-10 scope in pH under, compare Termamyl ^The α-Dian Fenmei of specific activity high at least 25%, specific activity is to use Phadebas ^Alpha-amylase activity is tested and is measured.Suitable is the above-mentioned diastatic mutation that is described among the WO96/23873 (Novo Nordisk).Aspect active and have other amylase that improves character in thermostability and more highly active combined aspects and be described among the WO95/35382.

Preferred amylase comprises among the application PCT/DK96/00056 that do not wind up the case jointly that is described in WO95/26397 and Novo Nordisk.

Press composition weight meter, the diastatic amount that is incorporated in the detergent composition of the present invention is 0.0001-2%, preferred 0.00018-0.06%, the more preferably pure enzyme of 0.00024-0.048%.

In particularly preferred embodiments, detergent tablet of the present invention contains amylase, particularly is described in those enzymes and auxiliary amylase among the common application PCT/DK96/00056 that do not wind up the case of WO95/26397 and Novo Nordisk.

About " assisting ", it refers to and adds the amylase that one or more are suitable for cleaning purpose.The example of auxiliary amylase (α and/or β) is described below.The WO94/02597 of Novo Nordisk A/S and WO95/10603 have described and have mixed the diastatic cleaning combination of mutant.Other become known for amylase in the cleaning combination comprise α-and-βDian Fenmei.α-Dian Fenmei is known in the art and is included in those disclosed in the following document: US5003257; EP252666; WO91/00353; FR2676456; EP285123; EP525610; EP368341 and GB1296839 (Novo).Other suitable amylase be described in the amylase of the enhanced stability among the WO96/05295 of WO94/18314 and Genencor and obtain from Novo Nordisk A/S, be disclosed in amylase mutation the WO95/10603, that in direct parent, have other modification.Also suitable is the amylase that is described among the EP277216 (Novo Nordisk).The example of commercially available α-Dian Fenmei product is the Purafect Ox Am that derives from Genencor ^, the Termamyl that obtains from Denmark Novo Nordisk A/S ^, Ban ^, Fungamyl ^And Duramyl ^WO95/26397 has described other suitable amylase: be characterized as in 25-55 ℃ of temperature range and the 8-10 scope in pH under, compare Termamyl ^The α-Dian Fenmei of specific activity high at least 25%, specific activity is to use Phadebas ^Alpha-amylase activity is tested and is measured.Suitable is the above-mentioned diastatic mutation that is described among the WO96/23873 (Novo Nordisk).Aspect active and have other amylase that improves character in thermostability and more highly active combined aspects and be described among the WO95/35382.The preferably auxiliary amylase of the present invention is to be described in WO94/18314, among the WO96/05295, by Genencor with trade(brand)name Purafect Ox Am ^The amylase of selling; The Termamyl that obtains from Novo NordiskA/S ^, Fungamyl ^, Ban ^, Natalase ^And Duramyl ^, Natalase ^Maxamyl with Gist-Brocades ^

Press composition weight meter, the described auxiliary diastatic amount that is incorporated in the detergent composition of the present invention is 0.0001-2%, preferred 0.00018-0.06%, the more preferably pure enzyme of 0.00024-0.048%.Specific amylase and auxiliary diastatic pure enzyme part by weight are preferably 9: 1-1: between 9, more preferably 4: 1-1: between 4, most preferably 2: 1-1: between 2.

Above-mentioned enzyme can be from any suitable source, for example plant, animal, bacterium, mould and yeast source.The source can also be close mesomeric state or have a liking for special conditions (extremophilic) (have a liking for cold, suitable cold, thermophilic, have a liking for pressure, have a liking for alkali, have a liking for acid, have a liking for salt, or the like).Can use the purifying or the non-purified form of these enzymes.What also comprise in the definition is the mutant of natural enzyme.For example can be by the albumen and/or the genetic engineering of natural enzyme, chemistry and/or physically modified obtain mutant.The common practice is to express enzyme by host's organism, has wherein cloned the genetic material of responsible generation enzyme.

Press composition weight meter, the amount that is incorporated into the described enzyme in the detergent composition of the present invention generally is the 0.0001-2% organized enzyme.This enzyme can be used as independent one-component (ball that contains a kind of enzyme, particle, stable liquid etc.) or adds as the mixture (for example composite particles) of two or more enzymes.

Other suitable detergent component that can add is to be described in oxydasis scavenging agent on January 31st, 1992 application, in the autre action pendante european patent application 92870018.6.The example of such oxydasis scavenging agent is four ethylidene polyamine of ethoxylation.

Various enzymes and their methods in the synthetic detergent composition of joining also are disclosed in WO9307263A and the WO9307260A of Genencor International are among the WO8908694 of Novo and the US3553139 (being presented to people such as McCarty on January 5th, 1971).Enzyme also is disclosed among the US4101457 (people such as Place, on July 18th, 1978) and among the US4507219 (people such as Hughes, on March 26th, 1985).Be used for the enzyme material of liquid detergent formula and it is joined in such prescription, be disclosed among the US4261868 (people such as Hora, on April 14th, 1981).The enzyme that is used for washing composition can be with various consistent.The enzyme stabilization technique is open and be illustrated among US3600319 people such as (, on August 17th, 1971) Gedge and among European patent application EP 0199405 and the EP200586 (Venegas, on October 29th, 1986).The enzyme stabilising system also is disclosed in, for example among the US3519570.The useful bacillus AC13 that obtains proteolytic enzyme, zytase and cellulase is described among the WO9401532A (Novo).

SYNTHETIC OPTICAL WHITNER

Component very preferably in the detergent composition component is a SYNTHETIC OPTICAL WHITNER.Suitable SYNTHETIC OPTICAL WHITNER comprises the SYNTHETIC OPTICAL WHITNER that discharges chlorine and oxygen.

One preferred aspect, the SYNTHETIC OPTICAL WHITNER that discharges oxygen contains hydrogen peroxide cource and organic peroxide acid bleach precursor compound.Reaction in by this precursor and hydrogen peroxide cource forms organic peroxide acid.Preferred hydrogen peroxide cource comprises inorganic perhydrate SYNTHETIC OPTICAL WHITNER.Another preferred aspect, the ready-formed organic peroxide acid is directly joined in the composition.Contain the row that the composition of hydrogen peroxide cource and organic peroxy acid precursor and ready-formed organic peroxy acid mixture also is being considered.

Inorganic hydrogen peroxide compound SYNTHETIC OPTICAL WHITNER

The composition of detergent component preferably includes hydrogen peroxide cource as the SYNTHETIC OPTICAL WHITNER that discharges oxygen.Suitable hydrogen peroxide cource comprises inorganic perhydrate salts.

Inorganic perhydrate salts normally adds with the form of sodium salt, and by composition total weight, its amount is 1-40%, more preferably 2-30%, most preferably 5-25%.

The example of inorganic perhydrate salts comprises: perborate, percarbonate, superphosphate, persulphate and persilicate.Inorganic perhydrate salts is an alkali metal salt normally.Inorganic perhydrate salts can be used as crystalline solid and need not other protection and be included in the composition.Yet for some perhydrate salt, the preferred implementation of these particulate compositions is to use the coated form of this material, and it provides better stability in storage for the perhydrate salt in the granulated product.

Sodium peroxoborate can be standard type NaBO ₂H ₂O ₂Monohydrate or tetrahydrate NaBO ₂H ₂O ₂3H ₂O.

Alkali metal percarbonate, particularly SPC-D are the preferred perhydrates that is included in the present composition.SPC-D is corresponding to formula 2Na ₂CO ₃.3H ₂O ₂Addition compound, and can be used as crystalline solid and buy.Discharge hydrogen peroxide thereby can at a good pace dissolve for the SPC-D of hydrogen peroxide addition compound, this can increase the tendency that causes local high SYNTHETIC OPTICAL WHITNER concentration.Percarbonate most preferably joins in the above-mentioned composition with the form (it provides the stability in product) that applies.

In product, provide the coating material of stability to comprise blended water-soluble alkali vitriol and carbonate.Such coating and coating method have been described in licensing to the GB-1466799 of Interox on March 9th, 1977.The weight ratio of mixing salt coating material and percarbonate is 1: 200-1: in 4 the scope, and more preferably 1: 99-1: 9, most preferably 1: 49-1: 19.This mixing salt is sodium sulfate and yellow soda ash preferably, and it has general formula Na ₂SO ₄.n.Na ₂CO ₃, wherein n is 0.1-3, and preferred n is 0.3-1.0, and most preferably n is 0.2-0.5.

Another is suitable, and to provide the coating material of stability to product be SiO ₂: Na ₂The O ratio is 1.8: 1-3.0: 1, preferred 1.8: 1-2.4: 1 water glass, and/or Starso, by inorganic perhydrate salts weight, preferred coated weight is the SiO of 2-10% (3-5% usually) ₂Magnesium Silicate q-agent also can be included in this coating.The coating that contains silicate and borate or boric acid or other inorganics also is suitable.

Other contains wax, oil, and the coating of fatty soap also can be advantageously used among the present invention.

The peroxide Potassium peroxysulfate is another inorganic perhydrate salts that is used for this paper detergent composition.

Cross the hydracid bleach precursor

Peroxyacid bleach precursor is the compound that forms peroxy acid in crossing hydrolysis reaction with hydroperoxidation.Usually peroxyacid bleach precursor can be expressed as

Wherein L is a leavings group, and X is any functional group basically, causes the structure of the peroxy acid that produces when crossing hydrolysis to be

By detergent composition weight, the peroxyacid bleach precursor compound is preferably with 0.5-20%, more preferably 1-10%, and most preferably the amount of 1.5-5% adds.

Suitable peroxyacid bleach precursor compound generally contains one or more N-or O-acyl group, and this precursor can be selected from all kinds.Suitable type comprises: the acyl derivative of acid anhydrides, ester, imide, lactan and imidazoles and oxime.Example of useful materials is disclosed among the GB-A-158789 in such.Suitable ester is disclosed among English Patent 836988,864798,1147871,2143231 and the EP-A-0170386.

Leavings group

Leavings group, L group hereinafter must have enough reactivities to the hydrolysis reaction of crossing that takes place in Best Times section (for example cycles of washing)., if the L reactivity is too strong, for being used for bleaching composition, this activator will be difficult to stablize so.

Preferred L group is selected from following these groups and its mixture: With

With

R wherein ¹Be alkyl, aryl or the alkaryl that contains 1-14 carbon atom, R ³Be the alkyl chain that contains 1-8 carbon atom, R ⁴Be H or R ³, R ⁵Be the alkenyl that contains 1-8 carbon atom, Y is H or solubilizing group.Any R ¹, R ³And R ⁴Basically can be replaced by any functional group, these functional groups comprise: for example alkyl, hydroxyl, alkoxyl group, halogen, amine, nitrosyl radical, acid amides and ammonium or alkyl ammonium group.

Preferred solubilizing group is-SO ₃ ^-M ⁺,-CO ₂ ^-M ⁺,-SO ₄ ^-M ⁺,-N ⁺(R ³) ₄X ^-And O＜-(R ³) ₃, most preferably-SO ₃ ^-M ⁺With-CO ₂ ^-M ⁺, R wherein ³Be the alkyl chain that contains 1-4 carbon atom, M provides deliquescent positively charged ion to this bleach-activating agent, and X provides deliquescent negatively charged ion to this bleach-activating agent.Preferably, M is basic metal, ammonium or replacement ammonium cation, and sodium and potassium are most preferred, and X is halogen, hydroxide radical, methylsulfate or acetate anion.

Peroxybenzoic acid precursors

The peroxybenzoic acid precursors compound provides peroxybenzoic acid when crossing hydrolysis.

The phenylformic acid precursor compound of suitable neighbour-acylations comprises and replacing or unsubstituted benzoyloxy benzene sulfonate, comprises for example benzoyloxy sulfonate:

Also suitable is with the product of the methylated sorbyl alcohol of benzoyl reagent benzene, glucose and all many saccharidess, for example comprises:

Ac=COCH ₃The Bz=benzoyl

The peroxybenzoic acid precursors compound of acid imide comprises the urea that N-benzoyl succinimide, four benzoyl quadrols and N-benzoyl replace.Suitable imidazoles peroxybenzoic acid precursors comprises N-benzoyl imidazoles and N-benzoyl benzo imidazoles.The peroxybenzoic acid precursors that contains the N-acyl group that other is useful comprises N-benzoyl pyrrolidone, dibenzoyl taurine and benzoyl Pyrrolidonecarboxylic acid.

Other peroxybenzoic acid precursors comprises the benzoyl diacyl peroxide, benzoyl four acyl peroxides and have the compound of following formula: Tetra hydro Phthalic anhydride is another suitable peroxybenzoic acid precursors compound herein:

The lactan peroxybenzoic acid precursors of suitable N-acylations has following formula:

Wherein n is 0-8, preferred 0-2, R ⁶It is benzoyl.

Peroxybenzoic acid derivative precursor

Peroxybenzoic acid derivative precursor provides the peroxybenzoic acid that replaces when crossing hydrolysis.

The peroxybenzoic acid derivative precursor of suitable replacement comprises any peroxybenzoic acid precursors disclosed herein; wherein this benzoyl is replaced by any not positively charged (being non-cationic) functional group basically; these functional groups comprise: for example; alkyl; hydroxyl, alkoxyl group, halogen; amine, nitrosyl radical and amide group.

The preferred type of the peroxybenzoic acid precursors compound that replaces is the compound that the acid amides of following general formula replaces: Or

R wherein ¹Be aryl or alkaryl with 1-14 carbon atom, R ²Be arylidene or the alkyl arylene that contains 1-14 carbon atom, R ⁵Be H or alkyl, aryl or the alkaryl that contains 1-10 carbon atom, L can be any leavings group basically.R ¹Preferably contain 6-12 carbon atom.R ²Preferably contain 4-8 carbon atom.R ¹Can be aryl, the aryl of replacement or alkaryl, it contains side chain, substituting group or both, and can come from synthetic source or natural origin comprises for example tallow.For R ², similarly structural changes allows.Substituting group can comprise alkyl, aryl, halogen, nitrogen, sulphur and other general substituting group or organic compound.R ⁵Preferably H or methyl.R ¹And R ⁵Sum should be not more than 18 carbon atoms.The bleach activating immunomodulator compounds that this class acid amides replaces is described among the EP-A-0170386.

The positively charged ion peroxyacid precursor

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

Usually, the positively charged ion peroxyacid precursor is by with positively charged functional group for example ammonium or alkylammonium, and preferred ethyl or ammonium methyl replace that the peroxy acid of suitable peroxyacid precursor compound partly forms.The positively charged ion peroxyacid precursor is general as for example halide ions or methylsulfate ionic salt are present in the composition with suitable negatively charged ion.

The peroxyacid precursor compound of positively charged ion replacement can be the derivative of peroxybenzoic acid or its replacement, precursor compound as previously described like this.In addition, this peroxyacid precursor compound can be the alkyl peroxy acids precursor that alkyl peroxycarboxylic acid precursors compound or acid amides replace, and is as mentioned below.

The positively charged ion peroxyacid precursor is described in United States Patent (USP) 4904406,4751015,4988451,4397757,5269962,5127852,5093022,5106528; English Patent 1382594; European patent 475512,458396 and 284292; And among the Japanese Patent 87-318332.

Suitable positively charged ion peroxyacid precursor comprises the hexanolactam and the tetra-acetylated glucose benzoyl peroxide of single benzoyl of alkyl that ammonium or alkylammonium replace or benzoyloxy benzene sulfonate, N-acylations.

The benzoyl oxygen base benzene sulfonate that preferred cation replaces is 4-(trimethyl ammonium) methyl-derivatives of benzoyl oxygen base Phenylsulfonic acid:

The alkyl oxy benzene sulfonate that preferred institute positively charged ion replaces has following formula:

The positively charged ion peroxyacid precursor of the hexanolactam class of preferred N-acylations comprises the trialkyl ammonium methylene radical benzoyl caprolactam of trialkyl ammonium methylene radical benzoyl caprolactam, particularly following formula:

The positively charged ion peroxyacid precursor of the hexanolactam class of other preferred N-acylations comprises trialkyl ammonium methylene radical alkyl hexanolactam:

Wherein n is 0-12, particularly 1-5.

Another preferred cation peroxyacid precursor is 2-(N, N, a N-trimethyl ammonium) sodium ethyl 4-sulfo group phenyl carbons hydrochlorate muriate.

Alkyl percarboxylic acids bleach precursor

Alkyl percarboxylic acids bleach precursor forms percarboxylic acids when crossing hydrolysis.Preferred this class precursor provides peracetic acid when hydrolysis.

The alkyl peroxycarboxylic acid precursors compound of preferred imide type comprises N, N, N ¹N ¹The Alkylenediamine of tetra-acetylatedization, wherein this alkylidene group contains 1-6 carbon atom, and especially wherein this alkylidene group contains those compounds of 1,2 or 6 carbon atom.Tetra acetyl ethylene diamine (TAED) is particularly preferred.

Other preferred alkyl peroxycarboxylic acid precursors comprises: 3,5,5-trimethyl acetyl oxygen base benzene sulfonic acid sodium salt (different-NOBS), acyloxy benzene sulfonic acid sodium salt in the ninth of the ten Heavenly Stems (NOBS), acetoxyl group benzene sulfonic acid sodium salt (ABS) and five acetyl glucose.

The alkyl peroxy acids precursor that acid amides replaces

The alkyl peroxy acids precursor compound that acid amides replaces also is suitable, comprises those compounds with following general formula:

Or

R wherein ¹Be alkyl with 1-14 carbon atom, R ²Be the alkylidene group that contains 1-14 carbon atom, R ⁵Be H or the alkyl that contains 1-10 carbon atom, L can be any leavings group basically.R ¹Preferably contain 6-12 carbon atom.R ²Preferably contain 4-8 carbon atom.R ¹Can the straight or branched alkyl, it contains side chain, substituting group or the two, and can come from synthetic source or natural source comprises for example tallow.For R ², similarly structural changes allows.Substituting group can comprise alkyl, halogen, nitrogen, sulphur and other general substituting group or organic compound.R ⁵Preferably H or methyl.R ¹And R ⁵Sum should be not more than 18 carbon atoms.The bleach activating immunomodulator compounds that this class acid amides replaces is described among the EP-A-0170386.

The benzoxazine peroxyacid precursor

Also suitable is the benzo oxazinyl precursor compound, as disclosed in EP-A-332294 and EP-A-482807, particularly has those compounds of following formula:

The benzoxazine that comprises such replacement:

R wherein ₁Be H, alkyl, alkaryl, aryl or aralkyl, wherein R ₂, R ₃, R ₄And R ₅Can be to be selected from H, halogen, alkyl, alkenyl, aryl, hydroxyl, alkoxyl group, amino, alkylamino, COOR ₆(R wherein ₆Be H or alkyl) and carbonyl functional group's identical or different substituting group.

Particularly preferred benzo oxazinyl precursor is:

The ready-formed organic peroxide acid

Except organic peroxide acid bleach precursor compound, perhaps as the quid pro quo of organic peroxide acid bleach precursor, this organic peroxide acid bleach system can contain the ready-formed organic peroxide acid, with composition weight meter, its amount is generally 0.5%-25%, more preferably 1-10%.

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

R wherein ¹Be alkyl, aryl or alkaryl with 1-14 carbon atom, R ²Be alkylidene group, arylidene or the alkyl arylene that contains 1-14 carbon atom, R ⁵Be H or alkyl, aryl or the alkaryl that contains 1-10 carbon atom.R ¹Preferably contain 6-12 carbon atom.R ²Preferably contain 4-8 carbon atom.R ¹Can be the straight or branched alkyl, the aryl of replacement or alkaryl, it contains side chain, substituting group or the two, and can come from synthetic source or natural source comprises for example tallow.For R ², similarly structural changes allows.Substituting group can comprise alkyl, aryl, halogen, nitrogen, sulphur and other general substituting group or organic compound.R ⁵Preferably H or methyl.R ¹And R ⁵Sum should be not more than 18 carbon atoms.The organic peroxy acid compound that this class acid amides replaces is described among the EP-A-0170386.

Other organic peroxide acid comprises diacyl and four acyl peroxides, especially diperoxy dodecanedioic acid, diperoxy tetradecane diacid and diperoxy Thapsic acid.The dibenzoyl superoxide is the preferred organic peroxide acid of this paper.List and two is crossed nonane diacid, undecane dicarboxylic acid crossed by list and two and the amino peroxide hexanodioic acid of N-phthaloyl also is suitable for herein.

Release rate-the method for control

Can provide a kind of method with the control SYNTHETIC OPTICAL WHITNER particularly oxygen bleaching agent be discharged into speed in the washing soln.

The method of sustained release SYNTHETIC OPTICAL WHITNER can with peroxide Quality Control system be discharged in the washing soln.For example, such method comprises that control is discharged in the washing soln as any inorganic perhydrate salt of hydrogen peroxide cource.

The mechanism of another control SYNTHETIC OPTICAL WHITNER release rate is the coating coating SYNTHETIC OPTICAL WHITNER with a design, to reach sustained release.Therefore, this coating can comprise the material of poorly water-soluble, or enough thick coating, and this thick coating dissolved kinetics provides the release rate of control.

Can make ins all sorts of ways applies this coated material.Coated material is 1 with the ratio of coated material and SYNTHETIC OPTICAL WHITNER generally: 99-1: 2, preferred 1: 49-1: 9 amount exists.

The suitable coating compounds material comprises: triglyceride level (for example the vegetables oil of partial hydrogenation, soya-bean oil, Oleum Gossypii semen), single or two glyceryl ester, Microcrystalline Wax, gelatin, Mierocrystalline cellulose, lipid acid and its mixture.

Other suitable coating compounds material can comprise basic metal and alkaline earth metal sulphate, silicate and carbonate, comprises lime carbonate and silica.

Preferred coating materials comprises SiO especially for the coated material of inorganic perhydrate salt bleach source ₂: Na ₂The O ratio is 1.8: 1-3.0: 1, preferred 1.8: 1-1: 2.4 water glass, and/or Starso, preferred coated weight are counted the SiO of 2-10% (3-5% usually) with this inorganic perhydrate weight ₂Magnesium Silicate q-agent also can be included in this coating.

The inorganic salt coated material can with the organic binder bond combination of materials so that compound inorganic salt and/or organic binder bond coating to be provided.Suitable binder comprises that every mol of alcohol contains the C of 5-100 moles of ethylene oxide ₁₀-C ₂₀Alcohol ethoxylate, more preferably every mol of alcohol contains the C of 20-100 moles of ethylene oxide ₁₅-C ₂₀Primary alcohol ethoxylate.

Other preferred adhesive comprises some polymeric material.Molecular-weight average is that polyvinylpyrrolidone and the molecular-weight average of 12000-700000 is 600 to 5 * 10 ⁵, preferred 1000-400000, most preferably the polyoxyethylene glycol of 1000-10000 (PEG) is the example of such polymeric material.The multipolymer of maleic anhydride and ethene, ethylene methacrylic ether or methacrylic acid (maleic anhydride constitutes at least 20 moles of % of this multipolymer) is other example as the useful polymeric material of tackiness agent.These polymeric materials can use like this, and perhaps with solvent water for example, propylene glycol and above-mentioned every mol of alcohol contain the C of 5-100 moles of ethylene oxide ₁₀-C ₂₀Alcohol ethoxylate uses together.Other example of tackiness agent comprises C ₁₀-C ₂₀List and two glyceryl ethers also have C ₁₀-C ₂₀Lipid acid.

Derivatived cellulose is methylcellulose gum for example, and the poly carboxylic acid of carboxymethyl cellulose and Natvosol and homopolymerization and copolymerization or its salt are other examples that is applicable to tackiness agent herein.

A kind of method that applies this coated material comprises agglomeration.Preferred agglomeration method comprises any above-mentioned organic binder bond material of use.Can use the agglomeration machine/mixing machine of any routine, include, but are not limited to disc type, rotary drum and vertical mixer type.Also can be by being poured into or atomize is sprayed on the moving-bed of SYNTHETIC OPTICAL WHITNER the fused coating composition is applied.

Provide other method of needed sustained release to comprise that change SYNTHETIC OPTICAL WHITNER physical properties is so that control the mechanical means of its solvability and release rate.Suitable scheme comprises compacting, machinery injection, manual injection and select the solvability of the particle size adjustment SYNTHETIC OPTICAL WHITNER compound of grain fractions by some.

Satisfied the dynamic (dynamical) needs of required sustained release although the selection of particle diameter has not only been depended on the composition of grain fraction but also depended on, it is desirable to this particle diameter should be greater than 500 micron, and preferred median size is the 800-1200 micron.

Provide other scheme of sustained release method to comprise that other component of suitably selecting detergent composition matrix makes that the ionic strength environment that wherein provides can reach the dynamic (dynamical) needs of required sustained release when joining said composition in the washing soln.

Metallic bleaching catalyst

The described herein SYNTHETIC OPTICAL WHITNER that contains can contain metallic bleaching catalyst as preferred ingredients in addition as the composition of detergent component.This metallic bleaching catalyst preferably contains the bleaching catalyst of transition metal, is more preferably the bleaching catalyst that contains manganese or cobalt.

The bleaching catalyst of adequate types is to contain the active heavy metal cation of definite bleach catalyst for example copper, iron positively charged ion, have very little or do not have the active assistant metal positively charged ion of bleach catalyst for example zinc or aluminium cations, with the sequestrant that this catalysis and assistant metal positively charged ion is had definite stability constant, specifically be the catalyzer of ethylenediamine tetraacetic acid (EDTA), ethylenediamine tetraacetic (methylene phosphonic acid) and its water-soluble salt.Such catalyzer is disclosed among the US4430243.

The bleaching catalyst of preferred type is included in the manganese basigamy compound among US5246621 and the US5244594.The preferred example of these catalyzer comprises: Mn ^IV ₂(u-O) ₃(1,4,7-trimethylammonium-1,4,7-7-triazacyclononane) ₂-(PF ₆) ₂, Mn ^III ₂(u-O) ₁(u-OAc) ₂(1,4,7-trimethylammonium-1,4,7-7-triazacyclononane) ₂-(ClO ₄) ₂, Mn ^IV ₄(u-O) ₆(1,4, the 7-7-triazacyclononane) ₄-(ClO ₄) ₂, Mn ^IIIMn ^IV ₄(u-O) ₁(u-OAc) ₂-(1,4,7-trimethylammonium-1,4,7-7-triazacyclononane) ₂-(ClO ₄) ₃With its mixture.Other is described in the European Patent Application No. 549272.Be applicable to that other ligand herein comprises 1,5,9-trimethylammonium-1,5,9-triazododecane, 2-methyl isophthalic acid, 4,7-7-triazacyclononane, 2-methyl isophthalic acid, 4,7-7-triazacyclononane, 1,2,4,7-tetramethyl--1,4,7-7-triazacyclononane and its mixture.

Useful bleaching catalyst also can be selected from and be suitable among the present invention those in this paper composition.The example of suitable bleaching catalyst is seen US4246612 and US5227084.Also referring to US5194416, it discloses for example Mn (1,4,7 ,-trimethylammonium-1,4,7-7-triazacyclononane) (OCH of monokaryon manganese (IV) title complex ₃) ₃-(PF ₆).

Another kind of as bleaching catalyst that be disclosed among the US5114606 is manganese (III) and/or the water-soluble complexes (IV) with ligand, and this ligand is the non-carboxylate radical polyol with at least 3 continuous C-OH groups.Preferred ligand comprises: sorbyl alcohol, iditol, galactitol, mannitol, Xylitol, arabitol, adonitol, in-tetrahydroxybutane, in-inositol, lactose and its mixture.

US5114611 discloses a kind of bleaching catalyst, and it contains the title complex that transition metal comprises Mn, Co, Fe or Cu and non--(greatly)-ring ligand.Described ligand is the following formula material:

R1 wherein, R2, R3 and R4 can be selected from H separately, and the alkyl of replacement and aryl make each R ¹-N=C-R ²And R ³-C=N-R ⁴Form 5 or 6 yuan of rings.Described ring can further be substituted.B is the abutment that is selected from O, S.CR ⁵R ⁶, NR ⁷And C=O, wherein R ⁵, R ⁶And R ⁷Can each H naturally, alkyl or aryl comprises replacement or unsubstituted group.Preferred ligand comprises: pyridine, pyridazine, pyrimidine, pyrazine, imidazoles, pyrazoles and triazole ring.Randomly, described ring can be with substituting group alkyl for example, aryl, and alkoxyl group, halogen and nitro replace.Particularly preferably be ligand 2,2 '-two pyridyl amine.Preferred bleaching catalyst comprises Co, Cu, Mn, Fe ,-two pyridyl methane and-two pyridyl amine complexes.Catalyzer very preferably comprises Co (2,2 '-two pyridyl amine) Cl ₂, two (isocyanide sulfenyl) two pyridyl amine-cobalts (II), three (bipyridyl amine)-cobalt (II) supersalt hydrochlorates, Co (2,2 '-two pyridyl) ₂O ₂ClO ₄, two (2,2 '-two pyridyl) copper (II) perchlorate, three (2-bipyridyl amine-) iron (II) perchlorate) and its mixture.

Preferred example comprises the double-core Mn title complex with four-N-dentate and two-N-dentate ligand, comprises N ₄Mn ^III(u-O) ₂Mn ^IVN ₄) ⁺[Bipy ₂Mn ^III(u-O) ₂Mn ^IVBiPy ₂]-(ClO ₄) ₃

Although do not illustrate the structure of manganese bleach catalyst title complex of the present invention, can infer that they comprise inner complex or other hydration coordinate complex, it is by the carboxyl of ligand and nitrogen-atoms and the cationic interaction of manganese and produce.Similarly, the cationic, oxidized attitude of manganese neither be known for certain in catalytic process, can be (+II), (+III), (+IV) or (+V) valence state.Because ligand has 6 points and is connected on the manganese positively charged ion, therefore have reason to infer in the aqueous bleaching medium, to have multinuclear material and/or " cage " structure.Regardless of the form of in esse active Mn ligand material, for example tealeaves, strained tomatoes, coffee, wine, orange juice etc. provide improved bleachability to stain thereby it works with a kind of tangible catalytic way.

Other bleaching catalyst is described in: european patent application 408131 (cobalt complex catalyzer) for example, European patent application publication No. 384503 and 306089 (catalysis of metalloporphyrin agent), US4728455 (manganese/polygamy position polymerization of olefin using catalyst body catalyst), US4711748 and European patent application publication No. 224952 (manganese is adsorbed on catalyzer on the silico-aluminate), US4601845 (aluminosilicate carrier) with manganese and zinc or magnesium salts, US4626373 (manganese/ligand catalyzer) US4119557 (iron complex catalyzer), German patent specification 2054019 (cobalt sequestrant catalyzer), Canadian patent application 866191 (salt that contains transition metal), among US4430243 (sequestrant) and the US4728455 (manganese gluconate catalyzer) with manganese positively charged ion and on-catalytic metallic cation.

Other preferred example comprises cobalt (III) catalyzer with following formula:

Co[(NH ₃) _nM ' _mB ' _bT ' _tQ _qP _p] Y _yWherein cobalt is+oxidation state of 3 valencys; N is the integer (preferred 4 or 5, most preferably 5) of 0-5; M ' represents unidentate ligand; M is the integer (preferred 1 or 2, most preferably 1) of 0-5; B ' represents bidentate ligand; B is the integer of 0-2; T ' represents tridentate ligand; T is 0 or 1; Q ' four closes ligand; Q is 0 or 1; P ' is the pentahapto ligand; P is 0 or 1; And n+m+2b+3t+4q+5p=6; Y is one or more to count the counter ion of the suitable selection that y exists, wherein y is integer (the preferred 2-3 of 1-3, when Y is-1 valency negatively charged ion, most preferably 2), so that obtain the salt of charge balance, preferred Y is selected from: muriate, nitrate radical, nitrite anions, sulfate radical, citrate, acetate moiety, carbonate and its mixture; And wherein also at least one coordination position that is connected on the cobalt is unsettled under the automatic dishwashing working conditions, and cobalt is stablized in remaining coordination position under the automatic dishwashing condition, causes cobalt under alkaline condition (III) to arrive the reduction potential relative standard hydrogen electrode of cobalt (II) less than 0.4 volt (preferably less than 0.2 volt).

Preferred this class cobalt catalyst has following formula:

[Co (NH ₃) _n(M ') _m] Y _yWherein n is the integer (preferred 4 or 5, most preferably 5) of 3-5; M ' is unstable coordination part, be preferably selected from chlorine, bromine, hydroxide radical, water and its mixture (when m greater than 1 the time); M is the integer (preferred 1 or 2, most preferably 1) of 1-3; M+n=6; Y is the counter ion of the suitable selection that exists with number y, and this number is the integer (preferred 2-3, when Y is-1 valency negatively charged ion most preferably 2) of 1-3, so that obtain the salt of charge balance.

Being used for the preferred cobalt catalyst of this class of the present invention is to have formula [Co (NH ₃) ₅Cl] Y _y, [Co (NH particularly ₃) ₅Cl] Cl ₂Cobalt chloride five amine salt.

The preferred present composition that is to use with following formula cobalt (III) bleaching catalyst:

[Co (NH ₃) _n(M) _m(B) _b] T _yWherein cobalt is+oxidation state of 3 valencys; N is 4 or 5 (preferred 5); M one or morely passes through 1 coordination sites in the ligand of this cobalt; M is 0,1 or 2 (preferred 1); B is by the ligand of 2 coordination sites in this cobalt; B is 0 or 1 (preferred 0); And when b=0, m+n=6 so, and when b=1, m=0 and=4 so; T is the counter ion of one or more suitable selections that exist with number y, and wherein y is integer (preferred y is 1-3 so that obtain the salt of charge balance; When T is-1 valency negatively charged ion most preferably 2); And wherein said catalyzer also has the 0.23M of being lower than ^-1s ^-1The alkaline hydrolysis velocity constant of (25 ℃).

Preferred T is selected from: muriate, iodide, I ₃ ^-, formate, nitrate radical, nitrite anions, sulfate radical, inferior sulfate radical, citrate, acetate moiety, carbonate, bromide, PF ₆ ^-, BF ₄ ^-, B (Ph) ₄ ^-, phosphate radical, orthophosphite, silicate, tosylate, methylsulphonic acid root, and mixture.Randomly, if exist in T more than 1 anionic word, T can be by protonated, for example HPO ₄ ^2-, HCO ₃ ^-, H ₂PO ₄ ^-Deng.In addition, T can be selected from: unconventional inorganic anion, for example anion surfactant (for example linear alkylbenzene sulfonate (LAS), alkyl-sulphate (AS), alkyl ethoxy sulfonate (AES) etc.) and/or anionic polymer (for example polyacrylate, poly-methyl acrylate etc.).

M partly includes, but are not limited to: F for example ^-, SO ₄ ^-2, NCS ^-, SCN, S ₂O ₃ ^-, NH ₃, PO ₄ ^-And carboxylate radical (monovalence carboxylate radical preferably, but can exist to need only every part more than 1 carboxylate radical and only be bonded on this cobalt by 1 carboxylate radical in this part, other carboxylate radical of M part can be by protonated or be its salt form in this case).Randomly, if exist in M more than 1 anionic group, M can be by protonated (HPO for example ₄ ^-, HCO ₃ ^-, H ₂PO ₄ ^-, HOC (C) CH ₂C (C) O ^-Deng).Preferred L partly is to have the replacement of following formula or do not replace C ₁-C ₃₀Carboxylic acid:

RC (O) O ^-Wherein R is preferably selected from: hydrogen and C ₁-C ₃₀(preferred C ₁-C ₁₈) alkyl, the C that do not replace and replace ₆-C ₃₀(preferred C ₆-C ₁₈) aryl and the C that do not replace and replace ₃-C ₃₀(preferred C ₅-C ₁₈) heteroaryl that do not replace and replace, wherein substituting group is selected from :-NR ' ₃,-NR ' ₄ ⁺,-C (O) OR ' ,-OR ', C (O) NR ' ₂, wherein R ' is selected from hydrogen and C ₁-C ₆Part.Therefore the R of such replacement comprises-(CH ₂) _nOH and-(CH ₂) _nNR ' ₄ ⁺, wherein n is the integer of 1-16, preferred 2-10, most preferably 2-5.

Most preferred M is the carboxylic acid with following formula, and wherein R is selected from: the C of hydrogen, methyl, ethyl, propyl group, straight or branched ₄-C ₁₂Alkyl and benzyl.Most preferred R is a methyl.Preferred carboxylic acid M partly comprises: formic acid, phenylformic acid, sad, n-nonanoic acid, capric acid, dodecylic acid, propanedioic acid, toxilic acid, succsinic acid, hexanodioic acid, phthalic acid, 2 ethyl hexanoic acid, naphthenic acid, oleic acid, palmitinic acid, triflate, tartrate, stearic acid, butyric acid, citric acid, vinylformic acid, aspartic acid, fumaric acid, lauric acid, linolic acid, lactic acid, oxysuccinic acid and especially acetate.

B partly comprises: carbonate, two and higher carboxylate radical (for example oxalate, malonate, malate, amber acid radical, maleate), pyridine carboxylic acid root and α and beta amino acids (for example glycine, alanine, β-An Jibingsuan, phenyl amino propionic acid).

Useful herein cobalt bleaching catalyst is known, for example, it is described in M.L.Tobe with its alkaline hydrolysis speed, the alkaline hydrolysis of transition metal complex (" Base Hydrolysisof Transition-Metal Complexes ") the inorganic mechanism of high lithotroph (Adv.Inorg.Bioinorg Mech.), (1983), in 2, the 1-94 pages or leaves.For example, provide the alkaline hydrolysis speed with cobalt five amine catalysts of following acid group complexing (wherein to be expressed as k at 17 pages table 1 _OH): oxalate (k _OH=2.5 * 10 ^-4M ^-1s ^-1(25 ℃)), NCS ^-(k _OH=5.0 * 10 ^-4M ^-1s ^-1(25 ℃)), formate (k _OH=5.8 * 10 ^-4M ^-1s ^-1(25 ℃)) and acetate moiety (k _OH=9.6 * 10 ^-4M ^-1s ^-1(25 ℃)).Useful herein most preferred cobalt catalyst is to have formula [Co (NH ₃) ₅OAc] T _yCobalt five amine acetates, " OAc " expression acetate moiety part, especially cobalt five amine acetate muriates wherein, [Co (NH ₃) ₅OAc] Cl ₂And [Co (NH ₃) ₅OAc] (OAc) ₂[Co (NH ₃) ₅OAc] (PF ₆) ₂[Co (NH ₃) ₅OAc] (SO ₄); [Co (NH ₃) ₅OAc] (BF ₄) ₂[Co (NH ₃) ₅OAc] (NO ₃) ₂(herein " PAC ").

These cobalt catalyst prepare with known method easily, are for example instructed in the document below: Tobe article and the reference of wherein quoting, US4810410 (people such as Diakun, promulgation on March 7th, 1989), J.Chem.Ed. (1989), 66 (12), 1043-45; Synthetic and the sign (The Synthesis and Characterization ofInorganic Compounds) of mineral compound, W.L.Jolly (Prentice-Hall; 1970), 461-3 page or leaf; Inorganic chemistry (Inorg.Chem.) .18.1497-1502 (1979); Inorganic chemistry (Inorg.Chem.) .21,2881-2885 (1982); Inorganic chemistry (Inorg.Chem.), 18,2023-2025 (1979); Inorganic synthetic (Inorg.Sythesis), 173-176 (1960); With physical chemistry magazine (Journal of Physical Chemistry), 56,22-25 (1952); And among the synthetic embodiment that provides hereinafter.

The cobalt catalyst that is suitable for being incorporated in the detergent tablet of the present invention can be according to being disclosed in US5559261, and the synthetic route among US5581005 and the US5597936 prepares, and these documents are incorporated by reference in this article.

These catalyzer can be with the common processing of additive material so that reduce color influence (aesthetic effect as fruit product needs), perhaps be included in the particle that contains enzyme, as hereinafter illustrated, perhaps said composition can manufacture " the look grain " that contains catalyzer.

The compound of organic polymer

The preferred ingredient that organic polyhydroxyl compound can be used as detergent tablet of the present invention adds.About organic polyhydroxyl compound, it refer to usually in detergent composition, find have dispersion agent, anti redeposition agent, an any basically organic polyhydroxyl compound of dirt release agent or other clean character.

Press composition weight meter, the general quantity that organic polyhydroxyl compound joins in the detergent composition of the present invention is 0.1-30%, preferred 0.5-15%, most preferably 1-10%.

The example of organic polyhydroxyl compound comprises the poly carboxylic acid of water miscible organic homopolymerization and copolymerization, the poly carboxylic acid of modification or its salt, and wherein this poly carboxylic acid comprises at least 2 carboxyls, it is each other by no more than 2 carbon atoms separately.The polymkeric substance of latter's type is disclosed among the GB-A-1596756.The example of salt is that molecular weight is the multipolymer of the polyacrylate of 2000-10000 and itself and any suitable other monomeric unit like this, and this monomeric unit comprises the vinylformic acid of modification, fumaric acid, toxilic acid, methylene-succinic acid, equisetic acid, methylfumaric acid, citraconic acid and methylene radical propanedioic acid or their salt, maleic anhydride, acrylamide, alkylidene group, vinyl methyl ether, vinylbenzene and its be mixture arbitrarily.Preferably molecular weight is the vinylformic acid of 20000-100000 and the multipolymer of maleic anhydride.

Preferably containing the commercially available vinylformic acid that molecular weight is lower than 15000 polymkeric substance comprises by BASFGmbH with trade(brand)name Sokalan PA30, PA20, PA15, those materials that PA10 and Sokalan CP10 sell, with by Rohm and Haas with trade(brand)name Acusol 45N, 48N, 480N, those materials that 460N sells.

Preferably containing acrylic acid multipolymer comprises and contains following as monomeric unit those: a) 90-10% by weight, and preferred 80-20% vinylformic acid and its salt, b) 10-90%, preferred 20-80% has general formula-[CR ₂-CR ₁(CO-O-R ₃)]-Acrylic Acid Monomer or its salt of replacement, at least one substituent R wherein ₁, R ₂Or R ₃, preferred R ₁Or R ₂Be the alkyl or the hydroxyalkyl of 1-4 carbon atom, R ₁Or R ₂Can be hydrogen, R ₃Can be hydrogen or an alkali metal salt.R wherein most preferably ₁Be methyl, R ₂It is the Acrylic Acid Monomer (being methacrylic acid monomer) of the replacement of hydrogen.Most preferred this analog copolymer has 3500 molecular weight and contains the vinylformic acid of 60-80% (weight) and the methacrylic acid of 40-20% (weight).

The polyamino compound of polyamine and modification is useful in this article, comprises from aspartate-derived those, for example is disclosed in EP-A-305282, those among EP-A-305283 and the EP-A-351629.

Other optional polymer can be modification and unmodified polyvinyl alcohol and acetic ester, the Mierocrystalline cellulose of Mierocrystalline cellulose and modification, polyoxyethylene, polyoxypropylene, with its modification and unmodified multipolymer, the terephthalate of ethylene glycol or propylene glycol or itself and the unitary mixture of polyoxyalkylene.

Suitable example is disclosed in United States Patent (USP) 5591703,5597789 and 4490271.

Dirt release agent

Suitable polymeric dirt release agent comprises these dirt release agents, it contains: (a) one or more nonionic hydrophilic components, it is made up of following these parts basically: (i) polymerization degree is 2 polyoxyethylene part at least, or (ii) the polymerization degree is propylene oxide or the polyoxytrimethylene part of 2-10, wherein said hydrophilic segment does not comprise any propylene oxide unit, unless it is bonded on the adjacent part at every end by ehter bond, or (iii) contain the mixture of the oxyalkylene units of ethylene oxide and 1-30 propylene oxide unit, described hydrophilic segment preferably contains at least 25% ethylene oxide unit, more preferably, particularly for the such component with 20-30 propylene oxide unit, at least 50% ethylene oxide unit; Or (b) one or more hydrophobic components, it contains: (i) C ₃Oxyalkylene terephthalic acid ester moiety, wherein, if described hydrophobic components also contains the ethylene oxide terephthalate, ethylene oxide terephthalate: C so ₃The ratio of oxyalkylene terephthalate unit is 2: 1 or lower, (ii) C ₄-C ₆Alkylidene group or oxidation C ₄-C ₆Alkylene moiety, or its mixture, (iii) poly-(vinyl acetate) part, preferably polyethylene base acetic ester, its polymerization degree is 2 at least, or (iv) C ₁-C ₄Alkyl oxide or C ₄Hydroxyalkyl ether substituting group, or its mixture, wherein said substituting group is with C ₁-C ₄Alkyl oxide or C ₄Hydroxyalkyl ether derivatived cellulose, or the existence of the form of its mixture; Perhaps (a) and combination (b).

Although can use the higher polymerization degree, the polymerization degree of general (a) polyoxyethylene part (i) is 200, preferred 3-150, more preferably 6-100.Suitable oxidation C ₄-C ₆The alkylidene group hydrophobic part includes, but are not limited to: the end-blocking of polymerization dirt release agent is MO for example ₃S (CH ₂) _nOCH ₂CH ₂O-, wherein M is a sodium, n is the integer of 4-6, as disclosed in US4721580 (Gosselink, promulgation on January 26th, 1988).

Useful polymerization dirt release agent also comprises for example copolymerization block etc. of hydroxy ethers cellulose polymer compound, ethylene terephthalate or terephthalic acid propylene glycol ester and polyethylene oxide or poly(propylene oxide) terephthalate of derivatived cellulose among the present invention.Such reagent be commercially available and comprise for example METHOCEL (Dow) of cellulosic hydroxy ethers.Being used for herein Mierocrystalline cellulose dirt release agent also comprises and is selected from C ₁-C ₄Alkyl and C ₄Those of hydroxy alkyl cellulose; See US4000093 (people such as Nicol, promulgation on December 28th, 1976).

Dirt release agent is characterised in that: poly-(vinyl ester) hydrophobic part comprises poly-(vinyl ester) for example C ₁-C ₆The graft copolymer of vinyl ester preferably will gather (vinyl acetate) and be grafted to the polyalkylene oxide skeleton for example on the polyethylene oxide skeleton.See european patent application 0219048 (people such as Kud, on April 22nd, 1987 is open).

Another kind of suitable dirt release agent is the multipolymer with terephthalic acid ethanol ester and polyethylene oxide (PEO) terephthalate random block.The molecular weight of this polymerization dirt release agent is in the scope of 25000-55000.See US3959230 (Hays, promulgation on May 25th, 1976) and US3893929 (Basadur, promulgation on July 8th, 1975).

Another polymerization dirt release agent that is fit to is the polyester with ethylene terephthalate repeating unit, and it contains 10-15% weight ethylene terephthalate unit and 90-80% weight is the polyoxyethylene glycol deutero-polyoxyethylene terephthalate unit of 300-5000 from molecular-weight average.

The polymerization dirt release agent that another is fit to is the sulfonated products of linear ester oligopolymer basically, and it partly is made up of the oligomer ester skeleton of terephthaloyl and oxyalkylene oxygen repeating unit and covalently bound end group to skeleton.These dirt release agents have complete description in US4968451 (J.J.Scheibel and E.P.Gosselink, promulgation on November 6 nineteen ninety).Other suitable polymerization dirt release agent comprises US4711730 (people such as Gosselink, promulgation on December 8th, 1987) terephthalic acid polyester, US4721580 (Gosselink, promulgation on January 26th, 1988) the end capped oligomer ester of negatively charged ion, and the block polyester oligomeric compound of US4702857 (Gosselink, promulgation on October 27th, 1987).Other polymeric dirt release agent also comprises the dirt release agent of US4877896 (people such as Maldonado, promulgation on October 31st, 1989), and it discloses negatively charged ion, particularly the end capped terephthalate of sulfo group aroyl (sulfoarolyl).

Another kind of dirt release agent is to have repeating unit terephthaloyl unit, the different terephthaloyl of sulfo group unit, the unitary oligopolymer of oxygen ethylidene oxygen and oxygen-propylene.This repeating unit has constituted the skeleton of this oligopolymer, and preferably uses the isethionate end-blocking of modification.The particularly preferred dirt release agent of this class comprises a sulfo group isophthaloyl base unit, 5 terephthaloyl unit, and ratio is oxygen ethylidene oxygen and oxygen-propylene oxygen unit and two 2-(2-hydroxy ethoxy) the ethyl sulfonic acid sodium end-blocking unit of 1.7-1.8.

Heavy metal ion chelating agent

Of the present invention preferably contains heavy metal chelant as optional components.Referred to the component of sequester (chelating) heavy metal ion effect herein about " heavy metal ion chelating agent ".These components also can have calcium and magnesium sequestering power, but preferably they demonstrate for example selectivity of iron, manganese and copper of bonding heavy metal ion.

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

The tart heavy metal ion chelating agent, it has for example phosphonic acids or carboxylic functionality, can with its sour form or as with suitable counter cation (for example basic metal or alkaline-earth metal ions, ammonium, or substituted ammonium ion, perhaps its mixture) title complex/salt exist.Any salt/title complex is preferably water miscible.The mol ratio of described counter cation and heavy metal ion chelating agent preferably at least 1: 1.

The suitable heavy metal ion chelating agent that is used for herein comprises: organic phosphonate is poly-(alkylene phosphonic acids salt), basic metal ethane 1-hydroxyl diphosphonate of amino alkylidenyl, nitrilo trimethylene phosphonic salt for example.Preferably diethylenetriamine five (methylene phosphonic acid salt), quadrol three (methylene phosphonic acid), hexamethylene-diamine four (methylene phosphonic acid salt) and hydroxy ethylene 1,1 diphosphonate in the above-mentioned substance.

Other the suitable heavy metal ion chelating agent that is used for herein comprises: nitrilotriacetic acid(NTA) and polyaminocarboxylic acid be the amino tetraacethyl of ethylene, ethylidene pentaacetic acid, ethylenediamine disuccinic acid, quadrol two pentanedioic acids, 2-hydroxyl propylene diamine disuccinic acid or its any salt for example.

Particularly preferably be quadrol-N, N '-disuccinic acid (EDDS) or its basic metal, alkaline-earth metal, ammonium or substituted ammonium salt, or its mixture.Preferred EDDS compound is free acid and its sodium or magnesium salts or complex form.

The crystal growth inhibitor component

Detergent tablet of the present invention preferably contains the crystal growth inhibitor component, organic diphosphonic acid component preferably, and its add-on is the 0.01-5% of composition weight preferably, more preferably 0.1-2%.

About organic diphosphonic acid, refer to herein and do not contain the organic diphosphonic acid of nitrogen as its chemical structure part.Therefore, organic amino phosphonates do has been got rid of in this definition, yet it can be used as the heavy metal ion chelating agent component and is included in the composition of the present invention.

This organic diphosphonic acid is C preferably ₁-C ₄Di 2 ethylhexyl phosphonic acid, more preferably C ₂Di 2 ethylhexyl phosphonic acid, ethylidene diphosphonic acid for example, ethane 1-hydroxyl-1 most preferably, 1-di 2 ethylhexyl phosphonic acid (HEDP) and can particularly existing with partially or completely Ionized form as salt or title complex.

Water soluble sulfate

This detergent tablet randomly contains water soluble sulfate.When it exists, press composition weight meter, the amount of this water soluble sulfate is 0.1-40%, more preferably 1-30%, most preferably 5-25%.

This water soluble sulfate can be the vitriol with any counter cation basically.Preferred salt is selected from basic metal and alkaline earth metal sulphate, particularly sodium sulfate.

Alkalimetal silicate

Alkalimetal silicate is the preferred ingredients of sheet of the present invention.Preferred alkalimetal silicate is SiO ₂: Na ₂O is than being 1.8-3.0, preferred 1.8-2.4, most preferably 2.0 water glass.By weight, the amount that water glass exists preferably is lower than 20%, preferred 1-15%, the most preferably SiO of 3-12% ₂This alkalimetal silicate can be the form of anhydrous salt or salt hydrate.

The component that alkalimetal silicate also can be used as alkaline system exists.

This alkaline system also preferably contains Starso, and by weight, the amount of its existence is 0.4% SiO at least ₂Starso has 1.0 nominal SiO ₂: Na ₂The O ratio.The weight ratio of described water glass and described Starso (is pressed SiO ₂Measure) preferably 50: 1-5: 4, more preferably 15: 1-2: 1, most preferably 10: 1-5: 2.

Tinting material

As using in this article, term " tinting material " refers to any material that absorbs special wavelength light from visible spectrum.When joining such tinting material in the detergent composition, it has the effect that changes visible light colors, and changes the outward appearance of detergent composition thus.Tinting material can be for example dyestuff or pigment.This tinting material is preferably stable in the composition that they add.Therefore in the composition of high pH, this tinting material preferably alkali is stable, and in low pH composition, this tinting material is preferably sour stable.

First and/or second and/or optional other can contain tinting material mutually, the mixture of tinting material, the painted particle or the mixture of colored particles make the various different visual appearances that have mutually.One of preferred first or second phase contains a kind of tinting material.When first and second mutually and/or its second phase when containing a kind of tinting material, preferably this tinting material has different visual appearances.

The example of suitable dyestuff comprises reactive dyestuffs, substantive dyestuff, azoic dyestuff.Preferred dyestuff comprises: phthalocyanine pigment, anthraquinone dye, quinoline dye, monoazo, tetrazo and polyazo.Preferred dyestuff comprises anthraquinone, quinoline and monoazo-dyes.Preferred dyestuff comprises SANDOLAN E-HRL180% (trade(brand)name), SANDOLANMILLING BLUE (trade(brand)name), TURQUOISE ACID BLUE (trade(brand)name) and the SANDOLANBRILLIANT GREEN (trade(brand)name) that obtains from Clariant UK, from Pointings, HEXACOLQUINOLINE YELLOW (trade(brand)name) that UK obtains and HEXACOL BRILIANT BLUE (trade(brand)name), the ULTRA MARINE BLUE (trade(brand)name) that obtains from Holliday or from Bayer, the LEVAFIX TURQUISE BLUE EBA (trade(brand)name) that USA obtains.

Can with any suitable method with tinting material join these mutually in.Suitable method comprises mixes maybe all or the detergent component selected and tinting material with all or the component selected tinting material in the sprinkling in the drum that rotates in a drum.

When the component as first phase existed, the amount that tinting material exists was 0.001-1.5%, preferred 0.01-1.0%, most preferably 0.1-0.3%.When as second mutually and/or the component of its optional second phase when existing, the amount that tinting material exists is 0.001-0.1%, more preferably 0.005-0.05%, most preferably 0.007-0.02% normally.

Corrosion inhibition immunomodulator compounds

Of the present invention that is applicable to the wash up method can contain corrosion inhibitor, and it is preferably selected from the coating agent, particularly paraffin of organic silver, Mn (II) salt of nitrogenous corrosion inhibition immunomodulator compounds and Mn (II) compound, particularly organic ligand.

Organic silver applies agent and is described among PCT publication number WO94/16047 and the autre action pendante European patent application EP-A-690122.Nitrogenous corrosion inhibition immunomodulator compounds is disclosed among autre action pendante European patent application EP-A-634478.Mn (II) compound that is used for corrosion inhibitor is described among autre action pendante European patent application EP-A-672749.

Can be with the 0.05-10% of composition total weight, the amount of preferred 0.1-5% adds organic silver and applies agent.

The function that this silver applies agent is to form " in the use " supercoat on any silverware parts of loading of the present composition on using.Therefore should silver apply agent and should have the high avidity that is attached on the solid silver surface, when particularly existing as the component of aqueous cleaning that is used for handling this solid silver surface and liquid lime chloride.

Suitable organic silver herein applies agent and is included in the list that has 1-40 carbon atom in the hydrocarbon chain or the fatty acid ester of polyvalent alcohol.

The fatty acid part that can obtain this fatty ester from the list that carbochain, has 1-40 carbon atom or polyprotonic acid.The suitable example of mono carboxylic lipid acid comprises: mountain Yu acid, stearic acid, oleic acid, palmitinic acid, tetradecanoic acid, lauric acid, acetate, propionic acid, butyric acid, isopropylformic acid, valeric acid, lactic acid, oxyacetic acid and β, β '-dihydroxyl isopropylformic acid.Suitable polycarboxylic example comprises: n-butylmalonic acid, isocitric acid, citric acid, toxilic acid, oxysuccinic acid and succsinic acid.

Can be used in the list that has 1-40 carbon atom in the hydrocarbon chain or polyvalent alcohol and represent Fatty Alcohol(C12-C14 and C12-C18) residue in this fatty acid ester.The example of suitable Fatty Alcohol(C12-C14 and C12-C18) comprises: behenyl alcohol, n-Eicosanol, lauric alcohol and lauryl alcohol, ethylene glycol, glycerine, ethanol, Virahol, vinyl alcohol, Glycerol dimer, Xylitol, sucrose, tetrahydroxybutane, tetramethylolmethane, Sorbitol Powder or sorbitan.

The lipid acid of these fatty acid ester subsidiary material and/or Fatty Alcohol(C12-C14 and C12-C18) group preferably have 1-24 carbon atom in alkyl chain.

Preferred herein fatty acid ester is an ethylene glycol, glycerine and sorbitan ester, and wherein the fatty acid part of this ester generally includes and is selected from mountain Yu acid, stearic acid, oleic acid, the material of palmitinic acid or tetradecanoic acid.

Glyceryl ester also is very preferred.These esters are single, two or three esters of the lipid acid of glycerine and above-mentioned definition.

The object lesson that is used for aliphatic alcohol ester herein comprises: stearyl acetic ester, palmityl lactyl-lactic acid ester, coco group isobutyrate, oil base maleic acid ester, oil base dimaleate and tallow base propionic ester.Useful herein fatty acid ester comprises: Xylitol monopalmitate, pentaerythritol monostearate, sucrose monostearate, Zerol, ethylene glycol monostearate, sorbitan ester.Suitable sorbitan ester comprises: sorbitan monostearate, dehydrated sorbitol palmitate, sorbitan monolaurate, sorbitan list myristinate, sorbitan list behenate, dehydrated sorbitol mono-fatty acid ester, the sorbitan dilaurate, dehydrated sorbitol distearate, sorbitan two behenates, sorbitan dioleate and blended tallow alkyl sorbitan list and diester.

Zerol, glyceryl monooleate, glycerine monopalmitate, Glyceryl monobehenate and Stearic diglyceride are preferred herein glyceryl ester.

Suitable organic silver applies agent and comprises: triglyceride level, monoglyceride or triglyceride and its be derivative and its mixture of hydrogenation wholly or in part.Suitable fatty acids ester source comprises: vegetables oil and fish oil and animal tallow.Suitable vegetables oil comprises soya-bean oil, Oleum Gossypii semen, Viscotrol C, sweet oil, peanut oil, Thistle oil, Trisun Oil R 80, rape seed oil, raisin seed oil, plam oil and Semen Maydis oil.

Wax comprises that Microcrystalline Wax is that suitable organic silver applies agent herein.The fusing point of preferred wax is 35-110 ℃ scope and generally include 12-70 carbon atom.The petroleum wax of paraffin and crystallite wax pattern preferably, it is made up of the long-chain saturated hydrocarbon compound.

Alginate and gelatin are that suitable herein organic silver applies agent.

The dialkyl group amine oxide is C for example ₁₂-C ₂₀Methyl oxidation amine and dialkyl quats compound and salt is C for example ₁₂-C ₂₀The methyl ammonium halide also is suitable.

Other suitable organic silver applies agent and comprises some polymeric material.The polyvinylpyrrolidone of molecular-weight average 12000-700000, the polyoxyethylene glycol of molecular-weight average 600-10000 (PEG), polyamine N-oxide pllymers, the multipolymer of N-vinyl pyrrolidone and N-vinyl imidazole, with derivatived cellulose methylcellulose gum for example, carboxymethyl cellulose and Natvosol are the examples of such polymeric material.

The organic silver that some spices material, particularly those materials that the metallic surface is demonstrated high-affinity also can be used as herein applies agent.

The polymerization dirt release agent also can be used as organic silver and applies agent.

It is paraffin oil that preferred organic silver applies agent, and general main is the branched aliphatic hydrocarbons with 20-50 carbonatoms; It mainly is the C of side chain that preferred paraffin oil is selected from _25-45Material, its cyclic hydrocarbon is 1 with the ratio of non-cyclic hydrocarbon: 10-2: 1, preferred 1: 5-1: 1.A kind ofly satisfy these characteristics to have cyclic hydrocarbon and non-cyclic hydrocarbon ratio be that 32: 68 paraffin oil is by Wintershall, Salzbergen, Germany sells with trade(brand)name WINOG70.

Nitrogenous corrosion inhibition immunomodulator compounds

The nitrogenous corrosion inhibition immunomodulator compounds that is fit to comprises: imidazoles and its derivative be benzoglyoxaline for example, 2-heptadecyl imidazoles and be described in those imdazole derivatives among Czech patents numbers 139279 and the GB-A-1137741 (it also discloses the method for preparing imidazolium compounds).

Also suitable as nitrogenous corrosion inhibition immunomodulator compounds be pyrazole compound and its derivative, particularly those are 1,3,4 or 5 optional position is by R ₁, R ₃, R ₄And R ₅The pyrazoles that replaces, wherein R ₁Be H, CH ₂OH, CONH ₃Or COCH ₃In any, R ₃And R ₅Be C ₁-C ₂₀Any of alkyl or hydroxyl, R ₄Be H, NH ₂Or NO ₂Any.

Other suitable nitrogenous corrosion inhibition immunomodulator compounds comprises: benzotriazole, 2-sulfydryl benzotriazole, 1-phenyl-5-sulfydryl-1,2,3; the 4-tetrazolium, thionalid, morpholine, melamine, distearyl amine; stearyl-stearylamide, cyanuric acid, aminotriazole, amino tetrazole and indazole.

Nitrogenous compound is amine for example, distearyl amine and ammonium compound ammonium chloride for example especially, and brometo de amonio, ammonium sulfate and diammonium hydrogen citrate also are suitable.

The corrosion inhibition immunomodulator compounds of Mn (II)

Detergent tablet can contain the corrosion inhibition immunomodulator compounds of Mn (II).Press composition weight meter, this Mn (II) compound is preferably with 0.005-5%, more preferably 0.01-1%, and most preferably the amount of 0.02-0.4% adds.This Mn (II) compound is preferably to provide 0.1-250ppm in liquid lime chloride, more preferably 0.5-50ppm, and most preferably 1-20ppm weight Mn (II) ionic amount adds.

This Mn (II) compound can be the inorganic salt of anhydrous or hydrated form.Suitable salt comprises: manganous sulfate, manganous carbonate, manganous phosphate, manganous nitrate, manganous acetate and Manganous chloride tetrahydrate.This Mn (II) compound can be the salt of organic aliphatic acid or title complex for example manganous acetate or manganese stearate.

This Mn (II) compound can be the salt or the title complex of organic ligand.In a preferred scheme, this organic ligand is a heavy metal ion chelating agent.In another preferred scheme, this organic ligand is a crystal growth inhibitor.

Other corrosion inhibition immunomodulator compounds

Other suitable corrosion inhibition immunomodulator compounds comprises: mercaptan and glycol, particularly have the mercaptan of 4-20 carbon atom, and comprise lauryl mercaptan, thiophenol, thionaphthol, thionalid and anthracene thiophenol.That also suitable is saturated or undersaturated C ₁₀-C ₂₀Lipid acid or its salt, particularly Aluminium Tristearate Micronized sterile.C ₁₂-C ₂₀Hydroxy fatty acid or its salt also are suitable.The octadecane of phosphorylation and other antioxidant for example beta-hydroxy toluene (BHT) also are suitable.

Found the multipolymer of divinyl and toxilic acid, particularly be especially suitable for use as corrosion inhibition immunomodulator compounds with those of trade mark reference number 07787 supply by Polysciences Inc.

Hydrocarbon ils

Another preferred detergent component that is used for the present invention is a hydrocarbon ils, generally is the aliphatic hydrocrbon that is mainly long-chain with 20-50 scope carbonatoms; Preferred hydrocarbon is saturated and/or side chain; It mainly is the C of side chain that preferred hydrocarbon ils is selected from _25-45Material, its cyclic hydrocarbon is 1 with the ratio of non-cyclic hydrocarbon: 10-2: 1, preferred 1: 5-1: 1.Preferred hydrocarbon ils is a paraffin.Satisfying above-mentioned characteristic, to have cyclic hydrocarbon and non-cyclic hydrocarbon ratio be that 32: 68 paraffin oil is by Wintershall, Salzbergen, and Germany sells with trade(brand)name WINOG70.

Water-soluble bismuth compound

The detergent tablet of the present invention that is applicable to the wash up method can contain water-soluble bismuth compound, presses composition weight meter, and the amount of its existence is preferably 0.005-20%, more preferably 0.01-5%, most preferably 0.1-1%.

This water-soluble bismuth compound can be any salt or the title complex of bismuth and any inorganic or organic counter anion basically.Preferred inorganic bismuth salt is selected from three halogenation bismuth, Bismuth trinitrate and bismuth phosphates.Bismuth acetate and bismuth citrate are the salt that preferably has organic counter anion.

The enzyme stabilising system

Preferably contain enzyme composition herein and can contain 0.001-10% by weight, preferred 0.005-8%, most preferably the enzyme stabilising system of 0.01-6%.This enzyme stabilising system can be any stabilising system compatible with detersive enzyme.Such stabilising system can comprise: calcium ion, boric acid, propylene glycol, short chain carboxy acid, boric acid (boronic acid), chlorine bleach scavenging agent and its mixture.Such stabilising system also can contain the reversible enzyme inhibitors, for example the reversible proteinase inhibitor.

The lime soap dispersing agent compound

Of the present invention can contain the lime soap dispersing agent compound, presses composition weight meter, and the amount of its existence is 0.1-40% preferably, more preferably 1-20%, most preferably 2-10%.

Lime soap dispersing agent is that the basic metal, ammonium or the amine salt that prevent lipid acid pass through calcium or the sedimentary material of magnesium ion.Preferred lime soap dispersing agent compound is disclosed among the PCT application WO93/08877.

Foam inhibition system

When detergent tablet of the present invention was mixed with the composition that is used to machine-wash, it preferably included foam inhibition system, and the amount of its existence is counted 0.01-15% by composition weight, preferred 0.05-10%, most preferably 0.1-5%.

The suitable foam inhibition system that is used for herein consists essentially of any known anti-foam compound, comprising: for example, siloxanes is prevented the foam compound, and 2-alkyl and alkanol are prevented the foam compound.Preferred foam inhibition system and anti-foam compound are disclosed among PCT application WO93/008876 and the EP-A-705324.

The polymeric dye transfer inhibitor

By weight, detergent tablet herein also can contain 0.01-10%, the polymeric dye transfer inhibitor of preferred 0.05-0.5%.

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

White dyes

Be applicable to that the detergent tablet of the washing methods of doing washing as described herein also can randomly contain the hydrophilic white dyes of some type of 0.005-5% (weight).

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

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

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

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

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

The soft system of clay

Be applicable to that the detergent tablet in the laundry purging method can contain the soft system of clay of the clay flocculating agent that comprises the clay mineral compound and choose wantonly.

This clay mineral compound is the smectic clays compound preferably.Smectic clays is disclosed in United States Patent (USP) 3862058,3948790 and 4062647.The clay flocculating agent that the European patent EP-A-299575 of Procter and Gamble Company and EP-A-313146 have described suitable organic polymer.

Cationic fabric softener

Also cationic fabric softener can be joined in the composition of the present invention, it is suitable for the washing methods of doing washing.Suitable cationic fabric softener comprises water-insoluble tertiary amine or two long-chain acid amides materials, as disclosed in GB-A-1514276 and EP-B-0011340.

By weight, cationic fabric softener is generally with 0.5-15% weight, and the total amount of 1-5% weight adds usually.

The component that other is optional

Other optional components that is suitable for being included in the present composition comprises spices and filling salt, and sodium sulfate is preferred filling salt.

The pH of composition

Detergent tablet of the present invention preferably is not formulated into has too high pH, is preferably 8.0-12.5 as the pH of 1% measured in solution in distilled water, more preferably 9.0-11.8, most preferably 9.5-11.5.

Machine washing tableware method

Anyly be suitable for machine-washing or clean the row that the method for stolen goods tableware all is being considered.

The method of preferred machine washing tableware comprises with dissolving or is dispersed in wherein that the liquid, aqueous processing of the detergent tablet of the present invention of significant quantity is selected from pottery, glassware, silver-colored tool, metal, the booty product of cutter and its mixture.About the detergent tablet of significant quantity, it refers at volume is dissolving or disperse the product of 8-60g, normally used common product dosage and washing soln volume in the conventional machine washing tableware method that coexists in the washing soln that rises of 3-10.Preferred detergent tablet heavily is the 15-40 gram, more preferably the 20-35 gram.

The laundry washing methods

Machine washing of clothes method herein generally comprises with dissolving or is dispersed in the wherein aqueous cleaning liquid processing stolen goods clothing of the laundry detergent sheet of the present invention of significant quantity.About the detergent tablet of significant quantity, it refers at volume is dissolving or disperse the product of 40-300g, normally used common product dosage and washing soln volume in the conventional machine washing of clothes method that coexists in the washing soln that rises of 5-65.

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

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

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

Preferred distribution device can re-use, and is the integrity that promptly all keeps container in dried state and during the cycles of washing that designs by this way.

In addition, this distribution device can be flexible container, for example bag or box.This bag can be so that maintenance thing wherein is for example disclosed in european patent application 0018678 with the filamentary structure of water impervious protecting materials coating.In addition, it can be formed by the water-insoluble synthetic polymeric material, is provided with disruptive edge sealer or closure in water-bearing media, as disclosed in European patent application publication No. 0011500,0011501,0011502 and 0011968.Make things convenient for the frangible closure of water of form to comprise water-soluble binder, it is for example placed and with its sealing on a limit of the bag that forms of polyethylene or polypropylene along water impervious polymeric membrane.

Embodiment

The abbreviation of Shi Yonging in an embodiment.

In detergent composition, abbreviation component symbol has following meaning:

STPP: tripoly phosphate sodium STPP

Supercarbonate: sodium bicarbonate

Citric acid: Citric Acid, usp, Anhydrous Powder

Carbonate: anhydrous sodium carbonate

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

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

PB1: anhydrous sodium perborate monohydrate

Non-ionic type: by the average degree of ethoxylation of BASF with trade(brand)name Plurafac sale

Be 3.8 and average propoxylation degree be 4.5 C ₁₃-C ₁₅Mix ethoxy

Baseization/propoxylated fatty alcohol

TAED: tetra acetyl ethylene diamine

HEDP:ethane 1-hydroxyl-1; 1-di 2 ethylhexyl phosphonic acid PAAC: five amine cobalt acetate (III) salt paraffin: the paraffin oil protease of being sold with trade name Winog70 by Wintershall: albumen (hydrolysis) enzyme amylase: starch (decomposition) enzyme BTA: BTA sulfate: anhydrous sodium sulfate PEG3000: the polyethylene glycol PEG6000 of the molecular weight about 3000 that obtains from Hoechst: the polyethylene glycol pH of the molecular weight about 6000 that obtains from Hoechst: among the below embodiment as 1% measured in solution the distilled water in the time of 20 ℃, all amounts all mark with parts by weight:

Example I-IV the following describes the example that the present invention is applicable to the detergent tablet of machine washing tableware.

I II III IV V VI phase 1STPP 9.62 9.62 10.45 9.57 9.57 11.47 silicate 0.50 0.67 1.60 1.00 1.00 2.40SKS-6 1.5 1.50 2.30 2.25 carbonate 2.33 2.74 3.5 3.59 4.10 5.25HEDP 0.18 0.18 0.18 0.28 0.28 0.28PB1 2.45 2.45 2.45 3.68 3.68 3.68PAAC 0.002 0.002 0.002 0.003 0.004 0.004 amylase 0.148 0.110 0.110 0.252 0.163 0.163 proteinase-10 .06 0.06 0.06 0.09 0.09 0.09 nonionic 0.40 0.80 0.80 1.20 1.20 1.20PEG6000 0.4 0.26 0.26 0.38 0.39 0.39BTA 0.04 0.04 0.04 0.06 0.06 paraffin 0.10 0.10 0.10 0.15 0.15 0.15 spices 0.02 0.02 0.02 0.013 0.013 0.013 sulfate 0.502 0.05 2.843

Amount to mutually 2 amylase, 0.30 0.35 0.25 0.30 0.35 0.25 proteinase-10 .25,0.22 0.30 0.25 0.22 0.30 citric acid, 0.3 0.30 0.3 0.30 sulfamic acids, 0.3 0.3 bicarbonates, 1.09 0.45 0.45 1.09 0.45 0.45 carbonate, 0.55 0.55 silicate, 0.64 0.64CaCl of 17.75g 18.55g 19.57g 23.0g 23.0g 23.0g₂0.07 0.07PEG3000 0.06 0.06 0.06 0.06 0.06 0.06 amounts to 2.0g 2.0g 2.0g 2.0g 2.0g 2.0g

The multi-phase tablets preparation of compositions is as follows.By particle and liquid ingredient are mixed, feed the washing composition active composition of the mould preparation phase 1 of conventional rotational pressure machine then.This pressing machine comprises that the drift of suitable shape is used for forming mold.The cross section of this mould is about 30 * 38mm.Said composition stands 940kg/cm then ²The pressure and the drift that raises expose first phase that contains the sheet of this mold on the surface thereon.Prepare the washing composition active composition of phase 2 and make it feed this mould with similar method.This seed activity composition stands 170kg/cm then ²Pressure, the rising drift is extruded multi-phase tablets from tabletting machine.The sheet that obtains is dissolving or disintegration in 12 minutes in aforesaid washing machine, and the phase 2 of sheet was dissolved in 5 minutes.These sheets provide fabulous solvability and cleaning and good sheet globality and intensity.

Claims (8)

1. multi-phase detergent sheet that is used for washing machine, this sheet contains:

A) first phase of formed body form wherein has at least one mold; With

B) second phase of press body form, it adhesively is included in the described mold; Wherein this tablet composition contain one or more main spissated second mutually in detergent active, and wherein this second also contains tackiness agent mutually in addition.

2. multi-phase detergent sheet that is used for washing machine, this sheet contains:

A) first phase of formed body form wherein has at least one mold, and this formed body is at least about 350kg/cm ²Down preparation of pressure; With

B) second phase of press body form, it adhesively is included in the described mold, and this tablet composition contains one or more and mainly be concentrated in second the detergent active in mutually, and wherein this second also contains tackiness agent mutually.

3. according to the multi-phase detergent sheet of above-mentioned arbitrary claim, wherein one or more detergent active are selected from: enzyme, SYNTHETIC OPTICAL WHITNER, bleach-activating agent, bleaching catalyst, tensio-active agent, sequestrant, crystal growth inhibitor and its mixture.

4. according to the multi-phase detergent sheet of above-mentioned arbitrary claim, wherein this tackiness agent is selected from sugar and sugar derivatives, starch and starch derivative, inorganic and organic polymkeric substance.

5. according to the multi-phase detergent sheet of above-mentioned arbitrary claim, it also contains between first phase and second phase and stops phase.

6. according to the multi-phase detergent sheet of claim 5, wherein this blocking layer comprises the tackiness agent of using with liquid form.

7. method of washing in washing machine, it comprises packs one or more multi-phase detergent sheets of above-mentioned arbitrary claim in the washing machine into.

8. according to the method for claim 7, wherein according to described dissolution test method herein, this multi-phase detergent sheet is being less than in 15 minutes dissolving or disintegration in dish-washing machine.