CN1309693A - Detergent tablet - Google Patents

Abstract

A multi-phase detergent tablet for use in a washing machine, the 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. 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 of invention

Detergent compositions in tablet form is that prior art is known.People know that detergent compositions in tablet form has several big advantages than granular detergent composition, for example measures easily, operates, transports and store.

The preparation of detergent tablet is the most normally with the component pre-mixing of detergent composition, and uses the equipment that is fit to, and for example tabletting machine is made sheet with premixed detergent components.Generally speaking, the component film-making of compacting detergent composition will make the sheet of making enough firm, can withstand operation and transportation, and can not suffer breakage.Except firm, sheet also must dissolve fully apace, so that detergent components just can be discharged in the washing water when begin wash(ing)cycle as far as possible.

Yet, if being applied power, compacting improves, just favourable also have a fraud, because of the dissolution rate of sheet can be slack-off.Therefore the present invention is devoted to seek the balance between the solvability of the soundness of sheet and sheet.

By prior art, the method for head it off comprises uses the low pressure compressed tablet.Yet, although comparatively faster dissolution rate is arranged, tend to easy fragmentation, become damaged and make the human consumer dissatisfied with the sheet of this method preparation.Additive method comprises that use relatively high pressure power prepares sheet, so that obtain the soundness of required degree, wherein adds dissolution aids, for example pore forming material.

Multi-phase detergent sheet described in the prior is by first kind of composition of compacting in tabletting machine, forms to be basically that the planar the first layer prepares.Then another kind of detergent composition is supplied with tabletting machine, on the top of the first layer.Then this second kind of composition is pressed into another kind is the planar second layer basically.Because in second kind of composition process of compacting, also suppressed, the first layer generally stands more than once compacting thus.Generally, for the first time and for the second time pressure is the same order of magnitude.The applicant has found that in this case because pressure must be bonded together first and second kinds of compositions fully, the pressure that uses must (cross section of supposition sheet be about 10cm at about 4000-20000kg in first and second pressing steps ²).The dissolution rate of sheet is slower as a result.Also prepared the multi-phase tablets of other performance different solubilities, its second layer is pressed with the pressure that is lower than the first layer.Yet although the dissolution rate of the second layer is enhanced, therefore the relative the first layer softness of the second layer is subject to operate and transport the destruction that causes.

EP-B-0055100 has described the washing block that a kind of slow dissolved formed body is combined with sheet and forms.This washing piece is designed to be put in the retention basin of washroom, and at several days, dissolving in preferred several weeks.As the method that reduces washing piece dissolution rate, introduced in the document and mixed one or more solubleness control agents.The example of described solubleness control agent is santochlor, paraffin, longer chain fatty acid and pure and mild its ester and fatty alkyl acid amides.Be used to do washing or the detergent tablet of automatic dishwashing must be at the one-period of washing machine or wash up machine, dissolving fully in promptly 15-120 minute.

Summary of the invention

According to a first aspect of the invention, provide a kind of multi-phase detergent sheet that is used for washing machine, this sheet comprises:

A) have formed body formula first phase of at least one mould; With

B) be compressed on interior granular solids formula second phase of described mould.

In preferred embodiments, first is to be about 40kg/cm at least by exerting pressure mutually ², preferably at least about 250kg/cm ², more preferably at least about 350kg/cm ²(3.43kN/cm ²), even 400-2000 more preferably from about, particularly about 600-1200kg/cm ²The formed body of the compacting of preparation (the pressure here is to apply power divided by the punch die cross-sectional area transverse to the cross-sectional area that applies power planar sheet-be actually rotation forming press).(this term meaning is possible comprise a plurality of " second " phase to the granular solids of also preferred second phase, this paper is sometimes referred to as ' optional its second phase ') impose on exerting pressure of first phase and be pressed in the described mould to be lower than, preferred pressure is lower than about 350kg/cm ², the about 300kg/cm of preferably about 40- ², the about 270kg/cm of 70-more preferably from about ², consider that from integrity that good movie is provided and intensity (for example press Child BiteStrength[CBS] measuring) and the angle of product dissolution characteristics this is that the present invention is preferred.Of the present invention preferred its CBS is at least about 6kg, is preferably greater than about 8kg, and more preferably greater than about 10kg, particularly greater than about 12kg, more especially greater than about 14kg, CBS measures by Consumer Product Safety Commission's test regulation.In addition, the general ratio of pressure that imposes on first and second phases was at least about 1.2: 1, preferably at least about 2: 1, more preferably at least about 4: 1.

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

A) have compression moulding body formula first phase of at least one mould, described formed body be

At least about 350kg/cm ²Pressure prepares down; With

B) be compressed on granular solids formula second phase in the described mould, this second is to be lower than mutually

About 350kg/cm ²The pressure compacting.

In another embodiment preferred, second is press type mutually or can for example is that physics or chemical adhesion effect adhere to the formed body at least one mould in the first phase body.Also preferred first and second phases weight ratio each other is quite high, for example at least about 6: 1, preferably at least about 10: 1, 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.) in addition, its mainly be concentrated in second mutually in, for example at least about 50%, preferably at least about 60%, particularly about 80% weight actives (in actives gross weight in the sheet) be sheet second mutually in.In addition, this composition is to sheet intensity, solvability, cleaning and pH regulator characteristic the best, for example enable to be dissolved in the wash water solution, so that washing process begin 10,5,4 or even 3 minutes in wash water solution, discharge at least 50%, preferably at least 60%, more preferably at least 80% weight detergent active.

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

A) have at least one mould formed body formula first phase and

B) be compressed on interior granular solids formula second phase of described mould, and wherein this sheet comprises at least a detergent active, and its preparation method will make at least 50%, preferably at least 60%, more preferably at least 80% weight detergent active was at 10 minutes at the beginning of washing process, preferably 5 minutes at the beginning, more preferably be discharged in the washings in 3 minutes at the beginning.

Other advantages of the present invention are to realize the dissolving respectively of phase, so that an obviously dissolving before another phase of sheet, even a dissolving fully basically before other phased solns.This is particularly conducive to provides detergent active respectively.

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

A) have formed body formula first phase of at least one mould; With

B) be contained in compression forming body second phase in the described mould with adhesion system, wherein this tablet composition comprises one or more and mainly is concentrated in second the detergent active in mutually, and wherein second also comprises cracked dose mutually.

According to a further aspect in the invention, provide a kind of multi-phase detergent sheet, it comprises:

A) have formed body formula first phase of at least one mould; With

B) adhesion system is contained in compression forming body second phase in the described mould, wherein sheet combination

Thing comprises one or more and mainly is concentrated in second the detergent active in mutually, and wherein

Two-phase also comprises tackiness agent.

Suitable enzyme, SYNTHETIC OPTICAL WHITNER, bleach-activating agent, bleaching catalyst, tensio-active agent, sequestrant, crystal growth inhibitor and its mixture of being selected from of one or more detergent active, in order to promote cold water washing or the cleaning performance of cleaning operation initial period, the enzymic activity thing is particularly preferred.Therefore the present invention it is highly preferred that the enzyme detergent actives, and particularly being included in has the enzyme of enhanced activity or optimum activity and the mixture of one or more enzymes (for example Natalase) under 25 ℃-55 ℃ of temperature and the pH8-10.

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

A) have formed body formula first phase of at least one mould; With

B) be contained in compression forming body second phase in the described mould with adhesion system, wherein second also comprises enzyme mutually.

Detailed Description Of The Invention

The purpose of this invention is to provide a kind of detergent tablet, it is not only enough firm, hold out against operation and transportation, and major part can be dissolved into fast in the washing water at least, the snap-out release detergent active.At least one 10 minutes of beginning in the wash(ing)cycle of automatic dishwashing machine or washing machine of preferred sheet preferred 5 minutes, more preferably are dissolved in the washing water in 4 minutes.Preferred washing machine is automatic dishwashing machine or washing machine.Measure multi-phase tablets or its phase, or the washing composition active constituent dissolved time carry out according to DIN44990, use the wash up machine of buying by Bosch, in normal 65 ℃ of washing procedures, the water hardness is 18 ° of H, and revision test minimum 6 times or enough number of times guarantee reproducibility.

Multi-phase detergent sheet of the present invention comprises first phase, second phase and its optional second phase.First is the formed body detergent composition mutually, and it comprises the detergent components that will introduce below one or more.Preferred detergent components comprises washing assistant, SYNTHETIC OPTICAL WHITNER, enzyme and tensio-active agent.The component of detergent composition mixes or is sprayed onto on the liquid components by dry basis for example and is mixed together.Use any suitable equipment then, but preferred by compacting, for example in tabletting machine, component is made first phase.In addition, first also can pass through preparations such as extruding, casting mutually.First mutually can take various geometrical shapies, for example spheroid, cubes etc., but embodiment preferred generally has axisymmetric shape, and circle, square or rectangular cross section are generally arranged.

Prepare its surface of first mutual-assistance and comprise at least one mould at formed body.The size of mould or relative first phase of a plurality of mould, shape and its position, orientation and layout also can change.For example, mould or a plurality of mould are generally circle, square or oval cross-section; They can form the hole of inner sealing or surperficial recessed at formed body, or they can extend (for example axially opposite face) between the non-linking zone on formed body surface, form ' hole ' of one or more layouts on formed body; But and their axial arrangings, in addition can relative first symmetrically arrange or can asymmetricly arrange.In preferred embodiments, use the tabletting machine of particular design to prepare this mould, the shape that wherein contacts the punch head surface of detergent composition is such: when its contact and compacting during detergent composition, mould or a plurality of mould can be pressed into the multi-phase detergent sheet first mutually in.Preferably, mould has the face that concaves into or total improvement and the second mutually adherent concave surface.In addition, the precast body of the detergent composition that mould can be arranged by ring-type around the compacting center dyestuff is made, and forms the formed body that has between the opposite face of formed body by axially extended hollow cavity shaped mould thus.

Of the present invention also comprises other one or more phases, by the preparation of compositions that comprises following one or more detergent components.At least one phase (being called second phase here) is preferably taked the granular solids shape, and (this term comprises powder, particle, agglomerate and other granular solids, the mixture that comprises itself and liquid adhesive, fusible solid, spray etc.), they are pressed in one or more moulds of detergent tablet first phase, so that second itself takes the formed body shape mutually.Optional other are included as independent layer or one or more compositions of multiwalled mutually.Preferred detergent components comprises washing assistant, tinting material, tackiness agent, tensio-active agent, cracked dose and enzyme, particularly amylase and proteolytic enzyme.Another preferred aspect of the present invention, second comprises cracked dose with its optional second phase mutually, and it can be selected from disintegrating agent or pore forming material.The disintegrating agent that is fit to comprises swelling when contact with water, or forms path promote water inflow and/or effusive reagent in detergent tablet.Being applicable to that any known disintegrating agent that laundry or wash up are used or pore forming material all can be imagined is used for the present invention.The disintegrating agent that is fit to comprises that starch is (for example natural, the starch of modification and pre-gelledization, for example by corn, rice and yam starch obtain), starch derivative, U-Sperse (trade(brand)name) for example, Primojel (trade(brand)name) and Explotab (trade(brand)name), Mierocrystalline cellulose, Microcrystalline Cellulose, and derivatived cellulose, for example Arbocel (trade(brand)name) and Vivapur (trade(brand)name), the both is buied by Rettenmaier, the Nymcel (trade(brand)name) that buys by Metsa-serla, Avicel (trade(brand)name), Lattice NT (trade(brand)name) and Hanfloc (trade(brand)name), alginate, the acetate trihydrate, the carbonic acid alum, formula Na ₂CO ₃H ₂The hydrated carbonate of O, phase I content is at least about 40% hydration STPP, carboxymethyl cellulose (CMC), based on the polymkeric substance of CMC, sodium acetate, aluminum oxide.The pore forming material that is fit to is to contact those that produce gas with water.The pore forming material that is fit to can be the material that discharges oxygen, nitrogen peroxide or carbonic acid gas.The example of preferred pore forming material can be selected from perborate, percarbonate, carbonate, supercarbonate, with carboxylic acid or for example citric acid, thionamic acid, oxysuccinic acid or toxilic acid combination of other acid.

The component of the present composition is to mix by dry component, and mixes or spray and go up liquid components and be mixed together.Be packed into second phase and its optional second phase component then, and make it to remain on by in first mould that provides mutually.

The preferred embodiment of the invention comprises two-phase: first and second phases.First generally comprises a mould mutually, and second generally is made up of single washing composition active constituent mutually.Yet imagination first can comprise more than a mould that mutually second mutually can be by preparing more than a kind of washing composition active constituent.In addition, also estimate second can comprise mutually be contained in the mould more than a kind of washing composition active constituent.Also estimate in each mould that separates, to contain several washing composition active constituents.Use this method, can be separately with chemosensitive detergent components, because any loss of the performance that causes of reacting to each other of component, and may make it become inactive composition or depleted to avoid.

The present invention preferred aspect, first, second mutually and/or its optional second phase can comprise tackiness agent.When existing, tackiness agent is selected from organic polymer, for example polyoxyethylene glycol and/or polypropylene glycol, particularly molecular weight is those of 4000,6000 and 9000, paraffin, polyvinylpyrrolidone (PVP), the particularly PVP of molecular weight 90000, polyacrylic ester, sugar and sugar derivatives, starch and starch derivative, for example Vltra tears (HPMC) and carboxymethyl cellulose (CMC); And inorganic polymer, for example hexametaphosphate.As described below, the integrity that tackiness agent helps sheet with help to realize first and second mutually the dissolvings respectively.

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

In another embodiment of the present invention, the blocking layer that comprises barrier layer composition is first and second mutually and/or between its optional second phase or even second mutually and between its optional second phase.Barrier layer composition comprises at least a tackiness agent, and it is selected from aforesaid all kinds of.The advantage that has the blocking layer is to suppress or reduce component from moving of another phase in opposite directions, for example from first second the moving of its second phase mutually and/or randomly in opposite directions, on the contrary easily right.

For the normally used pressure of preparation sheet, the component of second phase and its second phase of choosing wantonly preferably is pressed with low-down pressure.Advantage of the present invention thus is owing to used low pressure, makes heat, and pressure or chemosensitive detergent components can be mixed in the detergent tablet, the performance loss thereupon that runs in the time of can not suffering to mix this component in the sheet usually.In addition, second phase (or other phase) available with the compacting of the first mutually identical or higher pressure so that be achieved as follows the dissolving respectively of described phase.

Another advantage of the present invention is the protection that has improved second phase, avoids the damage that causes by for example operating and transporting.As mentioned above, prior art has been prepared the multi-phase detergent sheet, and wherein the second layer is suppressed with the pressure that is lower than the first layer.Yet, although improved dissolution rate, the second layer of these sheets sensitive for damages that becomes, trend is broken or break when contact.Yet what the quilt of detergent tablet of the present invention was slightly suppressed is protected in the mould that is provided mutually by first of detergent tablet mutually.

Another advantage of the present invention is to prepare the multi-phase detergent sheet, wherein one can be designed to dissolving before another phase mutually, preferred obviously dissolving.In the present invention, preferred second mutually and its optional second phase dissolve before mutually first.According to above-mentioned preferred weight range, preferred first at 5-20 minute, more preferably dissolves in 10-15 minute, and second phase and/or its optional second phase are being shorter than 5 minutes, more preferably are shorter than 4.5 minutes, most preferably are shorter than dissolving in 4 minutes.In addition, second can dissolve mutually or after other phases first mutually, for example is preferably in the ending of washing operation, provides and cleans and the rinse effect.First, second mutually and/or the dissolution time of its optional second phase irrelevant each other.The present invention particularly preferred aspect, realized the dissolving respectively of phase.Can realize the multi-phase detergent sheet respectively the dissolved special benefits be can cause that by another kind of component the component of chemical inactivation can separately mix not in the homophase.In this case, the component of inactivation is preferably placed at second mutually and in its optional second phase.

Another advantage of the present invention is the adhesivity of having improved between the phase of multi-phase tablets.Compare with the known multi-phase tablets of prior art, the adhesivity of believing this improvement is to realize by the exposure that reduces by second phase, and is in the sheet of the present invention as a result, just not too easy along breaking of osculatory between phase and phase.Technology

The multi-phase detergent sheet can use any suitable production facility to prepare, for example CourtoyR253.Preferably, in the tabletting machine that can prepare the sheet that comprises mould, prepare.In the particularly preferred embodiment of the present invention, first is to use the tabletting machine of particular design to prepare by following step mutually.The drift of this tabletting machine is modified, so that the surface of punch head surface for protruding of contact detergent composition.

First kind of detergent composition delivered in the mould of tabletting machine, fallen drift contact detergent composition, and it is pressed into first phase.It is about 250kg/cm at least that general use is exerted pressure ², preferably about 350-2000kg/cm ², 500-1500kg/cm more preferably from about ², 600-1200kg/cm most preferably from about ²Suppress first kind of detergent composition.Rise drift then, expose first phase that contains mould.Second kind and optional secondly detergent composition are sent in the mould then.Fall the tabletting machine drift of particular design the second time then, slightly suppress second kind and optional secondly detergent composition, form second phase and its optional second phase.In another embodiment of the present invention, under the situation that has its optional second phase, its optional second phase is to prepare basically with in similarly optional next pressing step of the above-mentioned second step pressing.Second kind and optional secondly detergent composition are preferably to be lower than about 350kg/cm ², the about 300kg/cm of 40-more preferably from about ², the about 270kg/cm of 70-most preferably from about ²Pressure compacting.After having suppressed second kind of detergent composition, rise drift for the second time, from tabletting machine, release this multi-phase detergent sheet.Detergent components

Multi-phase detergent sheet as herein described first and second mutually and/or its optional second phase be to prepare by one or more compositions that compacting contains the washing composition active constituent.These middle mutually compositions that use should comprise various detergent components, as comprise washing-aid compound, tensio-active agent, enzyme, SYNTHETIC OPTICAL WHITNER, alkali source, tinting material, spices, lime soap dispersing agent, organic polymer, comprise 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 first mutually highly preferred detergent components comprises washing-aid compound, tensio-active agent, enzyme and SYNTHETIC OPTICAL WHITNER.The second mutually highly preferred detergent components comprises washing assistant, enzyme, crystal growth inhibitor and cracked dose and/or tackiness agent.Washing-aid compound

Of the present invention preferably contains washing-aid compound, and by the weight of composition, generally its content is 1%-80%, preferred 10%-70%, most preferably 20%-60% activated detergent component.The water soluble detergency promoter compound

Suitable water soluble detergency promoter compound comprises water-soluble monomer multi-carboxylate or its sour form, homopolymerization or copolymerization poly carboxylic acid or its salt, wherein poly carboxylic acid comprises each other by being no more than two carboxyls that two carbon atoms separate are opened at least, comprise carbonate, supercarbonate, borate, the mixture of phosphoric acid salt and aforementioned any compound.

Carboxylate salt or multi-carboxy acid salt washing agent can be monomer type or oligomer types, but because Cost And Performance, the multi-carboxylate of preferred monomers type usually.

The suitable carboxylate salt that contains a carboxyl comprises the water-soluble salt and the ether derivant thereof of lactic acid, oxyacetic acid.The multi-carboxylate of containing two carboxyls comprises the water-soluble salt of succsinic acid, propanedioic acid, (ethylidene dioxy base) oxalic acid, toxilic acid, Glyoxylic acid hydrate, tartrate, tartronic acid and fumaric acid and ether carboxylate and sulfinyl carboxylate salt.The multi-carboxylate of containing three carboxyls specifically comprises water-soluble citrate, aconitate and citraconate, and the succinate derivative, as English Patent 1,379,241 described carboxy methoxy-succinic acid salt, the newborn acyloxy succinate described in the English Patent 1389732, HOII P 7205873 described aminosuccinic acid salt, and English Patent 1,387,447 described oxygen multi-carboxylate material, for example 2-oxa-s-1,1,3-tricarballylic acid salt.

The multi-carboxylate of containing four carboxyls comprises English Patent 1,261,829 described oxygen di-succinates, 1,1,2,2-ethane tetracarboxylic acid hydrochlorate, 1,1,3,3-propane tetracarboxylic acid salt and 1,1,2,3-propane tetracarboxylic acid salt.Comprise the substituent multi-carboxylate of sulfo group and comprise English Patent 1,398,421 and 1,398,422 and U.S. Pat 3,936,448 described sulfo-succinic acid salt derivatives, and English Patent 1,439,000 described sulfonation pyrolytic Citrate trianion.

Alicyclic ring and heterocyclic multi-carboxylate comprise pentamethylene-suitable, suitable, suitable-tetracarboxylic acid hydrochlorate, cyclopentadiene 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, 1,2,3,4,5,6-hexane hexacarboxylic acid salt and polyvalent alcohol, for example carboxymethyl derivant of sorbyl alcohol, N.F,USP MANNITOL and Xylitol.Aromatic multi-carboxy acid's salt comprises English Patent No.1, disclosed mellitic acid, 1,2,4 in 425,343, the derivative of 5-pyromellitic acid and phthalic acid.

More than in these compounds, preferred multi-carboxylate is the hydroxycarboxylate of containing three carboxyls of as many as in each molecule, Citrate trianion more specifically.

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

The borate washing assistant and washing composition store or wash conditions under can produce boratory, as to contain formation borate composition washing assistant material and also can be used, 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 yellow soda ash and sesquicarbonate and its mixture and the calcium carbonate superfine powder on November 15th, 1973 disclosed German patent application 2321001.

Being used for highly preferred washing-aid compound of the present invention is the water-soluble phosphate washing assistant.The specific examples of water-soluble phosphate washing assistant is an alkali metal tripolyphosphates, trisodium phosphate, potassium and ammonium, and sodium orthophosphate and potassium, Sodium polymetaphosphate/sodium phosphate, wherein, the polymerization degree is 6-21, and phytate.

The specific examples of water-soluble phosphate washing assistant is an alkali metal tripolyphosphates, trisodium phosphate, potassium and ammonium, and sodium orthophosphate and potassium, Sodium polymetaphosphate/sodium phosphate, wherein, the polymerization degree is 6-21, and phytate.Part solubility or insoluble washing-aid compound

Sheet of the present invention can contain part solubility or insoluble washing-aid compound.Part solubility and insoluble washing-aid compound are particularly useful for making the sheet that is used to the method for doing washing.The example of part water soluble detergency promoter comprises for example EP-A-0164514, disclosed crystal type layered silicate among DE-A-3417649 and the DE-A-3742043.The crystal type lamina sodium silicate that preferred formula is following:

NaMSi _xO ₂₊₁YH ₂O wherein, M is sodium or hydrogen, x is 1.9-4, y is 0-20.This class crystal type lamina sodium silicate has ' sheet ' structure of bidimensional, and for example so-called δ-laminate structure is described in EP0164514 and EP0293640.The preparation method of this class crystal type layered silicate is disclosed among DE-A-3417649 and the DE-A-3742043.For the object of the invention, x is 2,3 or 4 in the above general formula, preferred 2.

Most preferred crystal type laminar silicic acid sodium compound is formula δ-Na ₂Si ₂O ₅, be called NaSKS-6 (trade(brand)name), be to be purchased from Hoechst AG.

Crystal type lamina sodium silicate material preferably is present in the granular detergent composition as the intimate mixture particle with the ionizable material of solid, water soluble, described in PCT patent application WO92/18594.The ionogenic material of this solid, water soluble is selected from organic acid, organic and inorganic acid salt and its mixture, optimization citric acid.

Basically the example of water-insoluble washing assistant comprises sodium silicoaluminate.

The silico-aluminate that is fit to comprises aluminosilicate zeolite, and its unit structure cell is suc as formula Na _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 at least 5, preferred 7.5-276, more preferably 10-264.Alumino-silicate materials can be hydrated form, and preferably xln contains 10-28%, preferred 18-22% combination water.

Aluminosilicate zeolite can be natural product, but preferably synthetic obtaining.Synthetic crystallization type aluminosilicate ion exchange material can be by zeolite A, zeolite B, zeolite P, the X zeolite of registration, and zeolite HS and composition thereof buys.

The preferred method of synthesizing Si-Al hydrochlorate zeolite is by descriptions such as Schoeman (being disclosed in " zeolite " (1994) 14 (2), among the 110-116), and wherein the author has described the method for preparing the colloidal state aluminosilicate zeolite.Colloidal state aluminosilicate zeolite particle should be preferably such, and no more than 5% grain graininess is greater than 1 μ m, and no more than 5% grain graininess is less than 0.05 μ m.The median size of preferably aluminosilicate salt zeolite granular is 0.01 μ m-1 μ m, more preferably 0.05 μ m-0.9 μ m, most preferably 0.1 μ m-0.6 μ m.

Zeolite A is a following formula:

Na ₁₂[(AlO ₂) ₁₂(SiO ₂) ₁₂] xH ₂O wherein x is 20-30, particularly 27.X zeolite is formula: Na ₈₆[(AlO ₂) ₈₆(SiO ₂) ₁₀₆] 276H ₂O.As disclosed zeolite MAP among the EP-B-384070 is the preferred zeolite builders of the present invention.

Preferred aluminosilicate zeolite is the colloidal aluminosilicate zeolite.When the colloidal state aluminosilicate zeolite was used as the component of detergent composition, particularly colloidal state zeolite A with regard to improving detersive power, can strengthen washing aid performance.Strengthening washing aid performance also shows reduction fabric incrustation and improves on the fabric whiteness retentivity; Believe that these problems are to help to wash poor detergent composition and often run into.

Find surprisingly, comprise the mixed type aluminosilicate zeolite detergent composition of colloidal state zeolite A and colloidal state zeolite Y and the calcium ion chelating ability that zeolite A compares provides identical that is purchased of equivalent.The zeolite A that is purchased that finds above-mentioned blended aluminosilicate zeolite detergent composition and equivalent in addition surprisingly compares the magnesium ion chelating ability that improves is provided.Tensio-active agent

Tensio-active agent is the preferred washing composition active constituent of composition described herein.The tensio-active agent that is fit to 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 have low foaming matter, the foaming that is used for the surfactant system of wash up method thus must be inhibited, or is more preferably low foaming, generally is nonionic.Be used for the foaming that the surfactant system of clothes washing method causes and do not need to be suppressed to the same degree required with wash up.The content of tensio-active agent is generally the 0.2%-30% weight of activated detergent composition, more preferably 0.5%-10% weight, most preferably 1%-5% weight.

Be issued to the US3 of Laughlin and Heuring on December 30th, 1975, listed the general content and the kind thereof of negatively charged ion, nonionic, both sexes and zwitterionics in 929,678.The catalogue of suitable cats product is given the US4 that is issued to Murphy on March 31st, 1981, in 259,217.The catalogue of the general tensio-active agent that comprises in the automatic dishwashing detergent composition is given in for example EP-A-0414549 and PCT application WO93/08876 and WO93/08874.Nonionogenic tenside

Basically any nonionogenic tenside that can be used for the decontamination purpose all can be included in the detergent tablet.The unrestricted type column of preferred useful nonionogenic tenside hereinafter.The non-ionic type ethoxylated alcohol surfactant

The alkyl ethoxylated condensation product of Fatty Alcohol(C12-C14 and C12-C18) and 1-25 moles of ethylene oxide is applicable to the present invention.The alkyl chain of Fatty Alcohol(C12-C14 and C12-C18) can be a straight or branched, can be primary alconol or secondary alcohol, and generally contains 6-22 carbon atom.Particularly preferably be the alcohol of the alkyl that contains 8-20 carbon atom, by every mol of alcohol, with the condensation product of 2-10 moles of ethylene oxide.The alkyl alkoxylates tensio-active agent of end envelope

The alkyl alkoxylates tensio-active agent of the end envelope that is fit to 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] (1) R wherein ₁It is the aliphatic hydrocarbyl of the straight or branched of 4-18 carbon atom; R ₂It is the aliphatic hydrocarbyl of the straight or branched of 2-26 carbon atom; X is that mean value is 0.5-1.5, more preferably 1 integer; Y is at least 15, more preferably at least 20 integer.

In the tensio-active agent of preferred formula I, the epoxide unit [CH of end ₂CH (OH) R ₂] at least 10 carbon atoms are arranged.According to the present invention, suitable formula I tensio-active agent is the POLY-TERGENT that the Olin company described among the WO94/22800 of the Olin Corporation that for example announced on October 13rd, 1994 produces ^The SLF-18B nonionogenic tenside.Ether capped poly-(o-alkylation) alcohol

Be used for ether capped poly-(o-alkylation) alcohol that preferred surfactants of the present invention comprises 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 aliphatic series or aromatic hydrocarbyl; R ³Be H or linear aliphatic alkyl with 1-4 carbon atom; X is that mean value is the integer of 1-30, wherein when x be 2 or greater than 2 the time, R ³Can be identical or different, k and j are that mean value is 1-12, more preferably the integer of 1-5.

R ¹And R ²Preferably have 6-22 carbon atom, most preferably the straight or branched of 8-18 carbon atom, saturated or unsaturated aliphatic or aromatic hydrocarbyl.R ³H or have the linear aliphatic alkyl of 1-2 carbon atom most preferably.Preferred x is that mean value is the integer of 1-20, more preferably 6-15.

As mentioned above, in preferred embodiments, when x greater than 2 the time, R ³Can be identical or different.Be R ³Can in above-mentioned any alkylidene group oxygen unit scope, change.For example, if x is 3, can select R ³Be inferior ethoxyl (EO) or inferior propoxy-(PO) and (EO) (PO) (EO) in order, (EO) (EO) (PO), (EO) (EO) (EO), (PO) (EO) (PO), (PO) (PO) (EO) and (PO) (PO) (PO) change.Certainly, selecting integer 3 only is as an example, if x is bigger integer, then changing can be bigger, for example comprises (PO) unit of a plurality of (EO) unit and much less.

Above-mentioned particularly preferred tensio-active agent comprises those of the low cloud point that is lower than 20 ℃.As detailed below, these low cloud point tensio-active agents can be used in combination with the tensio-active agent of high cloud point, obtain excellent cleaning grease effect.

Most preferred ether capped poly-(o-alkylation) pure tensio-active agent is that wherein k is 1, and j is those of 1, like this this tensio-active agent as shown in the 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 1-30, preferred 1-20, even the more preferably integer of 6-18.R wherein most preferably ¹And R ²Contain 9-14 carbon atom, R ³For H (formation inferior ethoxyl) and x are those tensio-active agents of 6-15.

Ether capped poly-(o-alkylation) pure tensio-active agent comprises three kinds of general compositions, i.e. straight or branched alcohol, oxyalkylene and end capped alkyl oxide.End capped alkyl oxide and alcohol are as hydrophobic, oil-soluble part of this molecule, and oxyalkylene group then constitutes hydrophilic, water-soluble part of this molecule.

These tensio-active agents are when being used in combination with high cloud point tensio-active agent, and Chang Gui tensio-active agent shows the improved action that significantly removes spot, film-forming properties and removal grease relatively.

In general, the preparation of poly-(oxyalkylene) pure tensio-active agent that the present invention is ether capped can with the base-material reaction, generate second kind of epoxide then by fatty alcohol and epoxide reaction are generated ether.With this second kind of epoxide and alcohol alcoxylates reaction, generate the new compound of the present invention then.The example of the method for preparing ether capped poly-(o-alkylation) pure tensio-active agent: C has below been described _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 buy from Aldrich) be blended in the 500ml three neck round-bottomed flasks that condenser, hydrogen inlet pipe, feed hopper, magnetic stirring bar and interior hygrosensor are housed.With mixture heating up to 60 ℃.Be added dropwise to Epicholorohydrin (47.70g, 0.515mol buy from Aldrich), maintain the temperature at 60-65 ℃.After the stirring, 60 ℃ of following reheat 1 hour, cooling mixture was to room temperature.Handle this mixture with 50% sodium hydroxide solution (61.80g, 0.773mol, 50%), simultaneously mechanical stirring.After adding, mixture is 90 ℃ of down heating 1.5 hours, and cooling is also filtered by ethanol.Separating filtrate, water (100ml) washing organic phase, through MgSO ₄Drying is filtered and is concentrated.Distill this oily matter down at 100-120 ℃ (0.1mmHg), obtain being the buttery glycidyl ether.C _12/14Alkyl-C _9/11The preparation of ether capped pure tensio-active agent

With Neodol ^91-8 (buys 20.60g by Shell chemical company, 0.0393mol ethoxylated alcohol) and tin chloride (IV) (0.58g, 2.23mmol) be blended in the 250ml three neck round-bottomed flasks that condenser, hydrogen inlet pipe, feed hopper, magnetic stirring bar and interior hygrosensor are housed. with mixture heating up to 60 ℃, be added dropwise to C this moment in 15 minutes _12/14Alkyl glycidyl ether (11.00g, 0.0393mol).60 ℃ down stir 18 hours after, mixture be cooled to room temperature and be dissolved in a methylene dichloride that equates with it.Make this solution by 1 inch silicagel pad, use the methylene dichloride wash-out simultaneously.Concentrate this filtrate by rotary evaporation, (100 ℃, 0.5mmHg) middle stripping obtains the buttery tensio-active agent at the kugelrohr thermostatted then.The non-ionic type ethoxylated/propoxylated fatty alcohol surfactant

Ethoxylation C6-C18 Fatty Alcohol(C12-C14 and C12-C18) and C6-C18 blended ethoxylated/propoxylated fatty alcohol are to be applicable to tensio-active agent of the present invention, particularly under water miscible situation.Preferred ethoxylized fatty alcohol is that ethoxylation degree is the C10-C18 ethoxylized fatty alcohol of 3-50, most preferably is that ethoxylation degree is the C12-C18 ethoxylized fatty alcohol of 3-40.The alkyl chain length of preferred blended ethoxylated/propoxylated fatty alcohol is 10-18 carbon atom, and ethoxylation degree is 3-30, and the propoxylation degree is 1-10.Non-ionic type EO/PO condenses with the propylene glycol condensation

Oxyethane and hydrophobic group by propylene oxide and propylene glycol condensation the formation product of condensation again are applicable to the present invention.The hydrophobic part preferred molecular weight 1500 to 1800 of these compounds, and performance water outlet insoluble.The example of this type compound comprises some commercially available Pluronic ^TMTensio-active agent, it is sold by BASF.Non-ionic type EO condensation product with propylene oxide/quadrol affixture condensation

Oxyethane is applicable to the present invention with the product that the product that is obtained by propylene oxide and reacting ethylenediamine carries out condensation.The hydrophobic part of these products is made of the reaction product of quadrol and excessive propylene oxide, and generally has 2500 to 3000 molecular weight.The example of this type nonionogenic tenside comprises some commercial Tetronic by the BASF sale that buy ^TMCompound.The blended nonionic surfactant system

In the preferred embodiment of the invention, detergent tablet comprises the blended nonionic surfactant system, and this system comprises the nonionogenic tenside of at least a low cloud point and the nonionogenic tenside of at least a high cloud point.

" cloud point " described here is the known property of nonionogenic tenside, be the result of tensio-active agent along with temperature rising solvability variation, observe second the temperature when occurring mutually and be called as " cloud point " (referring to " chemical technology encyclopaedia " of Kirk Othmer, the 3rd edition, the 22nd volume, 360-379).

" low cloud point " nonionogenic tenside described here is defined as cloud point and is lower than 30 ℃, preferably is lower than 20 ℃, most preferably is lower than 10 ℃ nonionic surfactant system component.General low cloud point non-ionic surfactants comprises the nonionic alkoxy-based surface-active agent, particularly by primary alconol deutero-ethoxylate, and the anti-block polymer of polyoxypropylene/polyoxyethylene/polyoxypropylene (PO/EO/PO).In addition, this low cloud point non-ionic surfactants comprises, for example ethoxylated/propylated alcohol (for example, the Poly-Tergent of Olin company ^SLF18), epoxide end capped poly-(o-alkylation) alcohol (for example, the Poly-Tergent of Olin company ^The SLF18B series non-ionic surfactants, for example on October 13rd, 1994 disclosed Olin company WO94/22800 described in) and ether capped poly-(o-alkylation) pure tensio-active agent.

Nonionogenic tenside can randomly contain the propylene oxide up to 15% weight.Other preferred nonionic can be by the method preparation described in the United States Patent (USP) 4223163 of the Builloty that authorized on September 16th, 1980, and the document is quoted for referencial use at this paper.

The nonionogenic tenside of low cloud point also comprises polyoxyethylene, polyoxypropylene block polymerization compound.Block polyoxyethylene-polyoxypropylene polymer comprises based on ethylene glycol, propylene glycol, glycerine, TriMethylolPropane(TMP) and quadrol as those of active dydrogen compounds initiator.By BASF-Wyandotte company, Wyandotte, Michigan is registered as PLURONIC ^, REVERSED PLURONIC ^And TETRONIC ^Some block polymer surfactant compounds be suitable for ADD composition of the present invention.Preferred examples comprises REVERSED PLURONIC ^25R2 and TETRONIC ^702.This tensio-active agent generally is used as low cloud point non-ionic surfactants in the present invention.

" high cloud point " nonionogenic tenside described here is defined as cloud point greater than 40 ℃, is preferably greater than 50 ℃, more preferably greater than 60 ℃ nonionic surfactant system component.The preferred nonionic surfactants system comprises ethoxylated surfactant, and it, is obtained with the reaction of 6-15 moles of ethylene oxide with average every mol of alcohol or alkylphenol by monohydroxy-alcohol that contains 8-20 carbon atom or alkylphenol.This high cloud point non-ionic surfactants comprises for example Tergitol 15S9 (by Union Carbide supply), Rhodasurf TMD8.5 (by Rhone Poulenc supply) and Neodol 91-8 (by the Shell supply).

For the object of the invention, also preferred high cloud point non-ionic surfactants further has hydrophilic-hydrophobic balance (" HLB "; Referring to Kirk Othmer above) value is for 9-15, preferred 11-15.This material comprises, for example Tergitol 15S9 (by Union Carbide supply), Rhodasurf TMD8.5 (by Rhone Poulenc supply) and Neodol 91-8 (being supplied by Shell).

Another kind of preferred high cloud point non-ionic surfactants derives 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.Preferably, high cloud point non-ionic surfactants is side chain or secondary alcohol ethoxyl compound, more preferably blended C9/11 or C11/15 branched-chain alcoho ethoxylate, the average condensation 6-15 of its every mol of alcohol mole, preferred 6-12 mole, most preferably 6-9 moles of ethylene oxide.The preferred relative mean value of deutero-ethoxylated non-ionic surface active agent like this has narrow ethoxylation distribution.Anion surfactant

Any basically anion surfactant that is used for the decontamination purpose all is suitable for.These can comprise anion sulfate, sulfonate, carboxylate salt and sarcosinate surfactant (for example, comprise the ammonium salt of sodium, potassium, ammonium and replacement, as one, two and triethanolamine salt etc.).The preferred anionic sulfate surfactant.

Other anion surfactants comprise isethionate, as fatty acid amide, alkyl succinate and the alkyl sulfo succinate of acyl isethinate, N-acyl taurine salt, methylamino esilate, the monoesters of sulfosuccinate (particularly saturated and unsaturated C ₁₂-C ₁₈Monoesters), the diester of sulfosuccinate (particularly saturated and unsaturated C ₆-C ₁₄Diester), N-acyl sarcosinate.Resinous acid and hydrogenated resin acid also suit, as rosin, staybelite, and the resinous acid and the hydrogenated resin acid that are present in the butter or obtain by butter.The anion sulfate acid salt surfactant

Be applicable to that anion sulfate tensio-active agent of the present invention comprises straight chain and side chain primary and secondary alkyl-sulphate, alkyl ethoxy sulfate, fatty oil acylglycerol vitriol, alkylphenol oxygen Vinyl Ether vitriol, C ₅-C ₁₇Acyl group-N-(C ₁-C ₄Alkyl) and-N-(C ₁-C ₂Hydroxyalkyl) vitriol of glucosamine sulfate and alkyl polysaccharide is as the vitriol (compound of nonionic non-sulfuric acid salinization is described hereinafter) of alkyl polyglucoside.

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

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

The particularly preferred aspect of the present invention is to adopt the mixture of preferred alkyl-sulphate and alkyl ethoxy sulfate surfactant.This mixture is disclosed among the PCT number of patent application WO93/18124.The anion sulfoacid salt surfactant

Be applicable to that anionic sulphonate tensio-active agent of the present invention comprises C ₅-C ₂₀Linear alkylbenzene sulfonate, alkyl ester sulfonate, C ₆-C ₂₂Uncle or secondary paraffin sulfonate, C ₆-C ₂₄Alkene sulfonate, sulfonated poly carboxylic acid, alkyl glycerol sulfonate, fatty acyl group glycerol sulfonate, fatty oil base glycerol 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 "), the secondary soap class of particularly as described herein some.

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

Suitable soap class tensio-active agent comprises secondary soap surfactant, and it comprises the carboxyl unit that links to each other with secondary carbon(atom).Being preferred for secondary soap surfactant of the present invention is to be selected from following water-soluble salt: the water-soluble salt that the water-soluble salt of the water-soluble salt of 2-methyl isophthalic acid-undecanoic acid, 2-ethyl-1-capric acid, the water-soluble salt of 2-propyl group-1-n-nonanoic acid, 2-butyl-1-are sad and the water-soluble salt of 2-amyl group-1-enanthic acid.Some soap class also can be used as suds suppressor and adds.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 ₁₇-straight or branched alkyl or alkenyl, R ¹Be C ₁-C ₄Alkyl, M are alkalimetal ion.Preferred examples is the myristyl and the oleoyl methyl sarcosinate of sodium-salt form.Amphoterics

Be used for the amphoterics that the present invention is fit to and comprise amine oxide surfactant and alkyl both sexes carboxylic acid.

Suitable amine oxide comprises 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 ⁵Be alkyl or the hydroxyalkyl that contains 1-3 carbon atom, perhaps contain the polyoxyethylene group of 1-3 oxyethylene group group.Preferred C ₁₀-C ₁₈Alkyl dimethyl amine oxide and C ₁₀-C ₁₈Acyl group amidoalkyl dimethyl oxidation amine.

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

Zwitterionics also can add in the detergent composition of the present invention.These tensio-active agents can be described as the derivative of derivative, heterocyclic secondary and the tertiary amine of secondary amine and tertiary amine widely, or the derivative of quaternary ammonium, quaternary phosphine or uncle's sulfonium compound.Trimethyl-glycine and sultaine tensio-active agent are the examples that is used for zwitterionics of the present invention.

Suitable trimethyl-glycine is the compound of following formula: R (R ') ₂N ⁺R ²COO ^-, wherein R is C ₆-C ₁₈Alkyl, each R ¹Be generally C ₁-C ₃Alkyl, R ²Be C ₁-C ₅Alkyl.Preferred trimethyl-glycine is C ₁₂-C ₁₈Dimethyl Ammonium hexanoate and C ₁₀-C ₁₈Acyl group amido propane (or ethane) dimethyl (or diethyl) trimethyl-glycine.The compound betaine tensio-active agent also is applicable to the present invention.Cats product

Be used for the water dispersible compound that cationic ester tensio-active agent of the present invention preferably has surfactant properties, it comprises at least one ester bond (promptly-COO-) with at least one positively charged ion charged group.Other suitable cationic ester tensio-active agents comprise the cholinesterase tensio-active agent, for example are disclosed in US 4228042,4239660 and 4260529.

The cats product that is fit to comprises quaternary surfactant, and it is selected from single C ₆-C ₁₆, preferred C ₆-C ₁₀N-alkyl or alkenyl ammonium surfactant, wherein all the other positions of N are replaced by methyl, hydroxyethyl or hydroxypropyl.Enzyme

Enzyme is first phase, and especially second mutually and/or the preferred detergent components of other optional phases.Described enzyme is selected from cellulase, hemicellulase, peroxidase, proteolytic enzyme, glucose-amylase, amylase, zytase, lipase, Phospholipid hydrolase, esterase, at, polygalacturonase, M-Zyme, reductase enzyme, oxydase, phenol oxidase, lipoxygenase, lignoenzyme, Starch debranching enzyme, tannase, pentosanase, malic enzyme (malanase), beta-glucanase, arabinofuranosidase/xylosidase, hyaluronic enzyme, chondroitinase, laccase or their mixture.

Preferred enzyme comprises the combination of proteolytic enzyme, amylase, lipase, peroxidase, at and/or cellulase and one or more plant cell-wall degrading enzymes.

The cellulase that can be used among the present invention comprises bacterium or mould cellulase.Preferably their best pH is that 5-12 and activity are higher than 50CEVU (Mierocrystalline cellulose viscosity unit).Suitable cellulase is disclosed in people's such as Barbesgoard U.S. Pat 4,435,307, among J61078384 and the WO96/02653, it discloses the mould cellulase that is produced by Humicola insolens, Trichoderma, careless Rhizopus and Sporothrix respectively.EP739982 has described from the isolated cellulase of new bacillus specie.Suitable cellulase also is disclosed in GB-A-2075028; GB-A-2095275; Among DE-OS-2247832 and the WO95/26398.

The example of this cellulase is by insolens Humicola (mutation of grey humicola lanuginosa thermophilic) bacterial strain, particularly the cellulase of Humicola strain DSM 1800 generations.Other cellulase that is fit to is that to come from insolens Humicola, molecular weight 50KDa, iso-electric point be 5.5 and contains 415 amino acid whose cellulases, with by Humicola insolens, the DSM1800 deutero-have cellulase activity～endoglucanase of 43kD; Preferred endoglucanase component has disclosed aminoacid sequence among the PCT application WO91/17243.Also the cellulase of Shi Heing is the EG III cellulase that is obtained by long-armed Trichoderma, and it is described among the WO94/21801 of disclosed Genencor on the 29th September in 1994.Particularly suitable cellulase is the cellulase with the effect of protection color.The example of this cellulase is those cellulases of describing in the european patent application No.91202879.2 (Novo) that submitted on November 6th, 1991.Trade(brand)name Carezyme and Celluzyme (Novo Nordisk A/S) are particularly suitables.Also referring to WO91/17244 and WO91/21801.Other cellulases that are fit to nursing fabric and/or cleaning character are described among WO96/34092, WO96/17994 and the WO95/24471.

The described cellulase generally incorporation in detergent composition is the 0.0001%-2% organized enzyme of detergent composition weight.

For example percarbonate, perborate, persulphate, hydrogen peroxide etc. are used in combination peroxidase with oxygen source.They are used for " liquid lime chloride ", promptly suppress in the washing process on the dyestuff that comes off from substrate or pigment migration other substrates to the washing soln.Peroxidase is being known in the art, for example comprises, horseradish peroxidase, lignoenzyme and halo peroxidase are as chloro or bromoperoxidase.The detergent composition that contains peroxidase is disclosed among for example PCT International Application No. WO 89/099813, the WO89/09813 and among the european patent application No.91202882.6 that submitted on November 6th, 1991 and among the EP96870013.8 that submitted on February 20th, 1996.What also be fit to is laccase.

The thiodiphenylamine that preferred synergistic agent is replacement is with phenoxazine, 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 cloves ester (the alkyl cloves ester that C3-C5 replaces) and the phenol that replace.SPC-D or Sodium peroxoborate are preferred hydrogen peroxide cources.

Described cellulase and/or the peroxidase generally incorporation in detergent composition are the 0.0001%-2% organized enzyme of detergent composition weight.

Other preferred enzymes that detergent composition of the present invention can comprise comprise lipase.The spendable suitable lipase of washing composition comprises by the microorganism in the Rhodopseudomonas family, as those lipase of Situ Ci Shi (stutzeri) aeruginosa atcc 19.154 generations, as is disclosed in the English Patent 1372034.The lipase that is fit to comprises that the antibody with lipase that is produced by microorganism Pseudomonas fluorescens IAM 1057 shows those lipase of positive immunological cross-reaction.This lipase can be by Amano Pharmacetical company limited, Nagoya, and Japan has bought, and commodity are called lipase P " Amano ", hereinafter are referred to as " Amano-P ".Other commercial lipase that are fit to comprise Amano-CES, the lipase that obtains by thickness look bacillus (Chromobacterviscosum), and for example by Toyo Jozo company, Tagata, the thickness look bacillus steatolysis mutation NRRLB 3673 that Japan obtains; By U.S.Biochemical company, thickness look bacillus lipase that the Disoynth company of U.S.A. and Holland obtains and the lipase that obtains by gladiolus pseudomonas (Pseudomonas gladioli).Particularly suitable lipase is such as M1 Lipase ^RAnd Lipomax ^R(Gist-Brocades) and Lipolase ^RWith Lipolase Ultra ^RLipase such as (Novo) has found that be very effective when they and the present composition are used in combination.What also be fit to is to be described in EP258068, WO92/05249 and WO95/22615 and to be described in lipolytic enzyme among WO94/03578, WO95/35381 and the WO96/00292 by Unilever by Novo Nordisk.

Also the enzyme of Shi Heing is at [EC 3.1.1.50], thinks that it is a kind of lipase of particular variety, is called the lipase that does not need interface activation.In detergent composition, add at and be described in for example WO-A-88/09367 (Genencor); Among WO90/09446 (PlantGenetic System) and WO94/14963 and the WO94/14964 (Unilever).

Lipase and/or the at generally incorporation in detergent composition are the 0.0001%-2% organized enzyme of this detergent composition weight.

Suitable proteolytic enzyme is subtilisin, and it is that special bacterial strain by Bacillus subtillis and bacillus licheniformis obtains (subtilisin BPN and BPN ').A kind of suitable proteolytic enzyme is to be obtained by bacillus strain, and it has maximum activity in the pH8-12 scope, and it is by the Novo Industries A/S company exploitation of Denmark and with ESPERASE ^Trade(brand)name is sold, and hereinafter is called " Novo ".The preparation of this kind of enzyme and similar enzyme is described among the GB1243784 of Novo company.Other proteolytic enzyme that are fit to comprise the KANNASE from Novo ^, ALCALASE ^, DURAZYM ^And SAVINASE ^With from the MAXATASE of Gist-Brocades ^, MAXACAL ^, PROPERASE ^And MAXAPEM ^(Maxacal of protein engineering).Proteolytic ferment also comprises the bacterial serine proteolytic enzyme of modification, those that (particularly the 17th, 24 and 98 page) described in the European Patent Application No. of submitting on April 28th, 1,987 87303761.8 for example, it is called as " proteolytic enzyme B " at this paper, with describe in the european patent application 199404 of disclosed Venegas on the 29th October in 1986 those, they are bacterial serine proteolytic ferments of modification, are called as at this paper " protease A ".What be fit to is that this paper is called the proteolytic enzyme of " proteolytic enzyme C ", they are variants of the alkaline serine protease that obtained by bacillus, wherein Methionin replaces 27 arginine, tyrosine replaces 104 Xie Ansuan, l-asparagine and the L-Ala that Serine replaces 123 replaces 274 Threonine.Proteolytic enzyme C is described among the EP90915958:4, and it is corresponding to disclosed WO91/06637 on May 16th, 1991.Particularly the variant of the genetic modification of proteolytic enzyme C is also included among the present invention.

The preferred protease that is called as " proteolytic enzyme D " is to have the carbonylic hydrolase variant that occurring in nature does not have the aminoacid sequence of discovery, and it obtains from carbonylic hydrolase is precursor-derived, and this derivative is the numbering according to the bacillus amyloliquefaciens subtilysin, in described carbonylic hydrolase, be equivalent to+76 position, also preferred combination be equivalent to be selected from+99 ,+101, + 103 ,+104 ,+107, + 123 ,+27 ,+105, + 109 ,+126 ,+128, + 135, + 156 ,+166 ,+195, + 197, + 204 ,+206 ,+210, + 216, + 217 ,+218 ,+222, + 260, + 265, and/or+one or more amino-acid residue places of 274, get with a plurality of amino-acid residues of different said these positions of aminoacid replacement, as the people's such as C.Ghosh that submit in WO95/10591 and on October 13rd, 1994 U.S. Patent Application Serial 08/322677, exercise question is for describing in the patent application of " bleaching composition that contains proteolytic enzyme ".

Also being suitable for of the present invention is to be described in proteolytic enzyme among patent application EP251446 and the WO91/06637, to be described in the proteolytic enzyme BLAP among the WO91/02792 ^With their variant that is described among the WO95/23221.

Also referring to the high pH proteolytic enzyme that derives from bacillus NCIMB40338 among the WO93/18140A that is described in Novo.Contain proteolytic enzyme, the enzyme-containing detergent of one or more other enzymes and reversible protease inhibitors is described among the WO92/03529A of Novo.When needs, as at Procter ﹠amp; Describe among the WO95/07791 of Gamble, can obtain adsorbing the proteolytic enzyme of reduction and hydrolysis raising.The recombination classes trypsinase that is suitable for washing composition of the present invention is described among the WO94/25583 of Novo.Other proteolytic enzyme that are fit to are described among the EP516200 of Unilever.

Other preferred proteolytic enzyme are included as the proteolytic enzyme of carbonylic hydrolase variant, and it has the aminoacid sequence that occurring in nature does not have discovery, and its a plurality of amino-acid residues by different aminoacid replacement carbonylic hydrolase precursors obtain, substituted a plurality of amino-acid residues are corresponding to+210 residues in the pre-enzyme described here, and in conjunction with the one or more residues that replace following site :+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, Bian Hao site is equivalent to the numbering position of the subtilysin of the natural generation that obtained by bacillus amyloliquefaciens here, or is equivalent to the amino-acid residue that is equal in other carbonylic hydrolases or the subtilysin (for example slowly genus bacillus subtilysin).The preferred enzyme of this class be included in site+210 ,+76 ,+103 ,+104 ,+156 and+166 places vicissitudinous those.

The incorporation of proteolytic ferment in detergent composition of the present invention by the weight of said composition, is 0.0001%-2%, preferred 0.001%-0.2%, the more preferably pure enzyme of 0.005%-0.1%.

Can comprise that amylase (α and/or β) is used to remove the spot based on carbohydrate.On February 3rd, 1994, the WO/94/02597 of disclosed Novo Nordisk A/S described the cleaning combination that mixes mutant amylase.Also referring to the WO95/10603 of disclosed NovoNordisk A/S on the 20th in April nineteen ninety-five.Other known amylase that are used for cleaning combination comprise α-and beta-amylase.α-Dian Fenmei is that prior art is known, comprises US5003257; EP252666; WO91/00353; FR 2676456; EP285123; EP525610; Those disclosed amylase in EP368341 and the british patent specification 1296839 (Novo).Other amylase that is fit to is stable enhanced amylase, and it is described on the August 18th, 1994 of disclosed WO94/18314 and in the WO96/05295 of disclosed Genencor on the 22nd February in 1996; And among in April, the 95 disclosed WO95/10603, modify the amylase variants that obtains from buy direct parent is added of Novo NordiskA/S.What also be fit to is the amylase that is described among EP277216, WO95/26397 and the WO96/23873 (all being applied for by Novo Nordisk).

The example of commercial α-Dian Fenmei product is the Purafect OxAm that buys from Genencor ^And Termamyl ^, Ban ^, Fungamyl ^And Duramyl ^, Natalase ^, they all can be buied from Novo Nordisk A/S Denmark.WO95/26397 has described other amylase that are fit to: α-Dian Fenmei is characterized in that passing through Phadebas ^The alpha-amylase activity measuring has specific activity greater than Termamyl in 25 ℃ of-55 ℃ of temperature and pH value under the 8-10 scope ^Specific activity at least 25%.Be advisable with the variant that is described in the above enzyme among the WO96/23873 (Novo Nordisk).Its activity level, and thermostability other amylolytic enzymes of improved performance such as combine with the greater activity level are described among the WO95/35382.

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

The incorporation of amylolytic enzyme in detergent composition of the present invention by the weight of said composition, 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 comprises amylase, particularly is described in application those amylase that make up with complementary amylase among the PCT/DK96/00056 of not winding up the case of WO95/26397 and Novo Nordisk.

" complementation " meaning is to add to be suitable for washing one or more amylase of purpose.The case description of complementary amylase (α and/or β) hereinafter.The WO94/02597 of Novo Nordisk A/S and WO95/10603 have described and have mixed the diastatic cleaning combination of mutant.Other known amylase that are used for cleaning combination comprise α-and beta-amylase.α-Dian Fenmei is that prior art is known, comprises US5003257; EP252666; WO91/00353; FR 2676456; EP285123; EP525610; Those disclosed amylase in EP368341 and the british patent specification 1296839 (Novo).Other amylase that are fit to are stable enhanced amylase, and it is described among the WO96/05295 of WO94/18314 and Genencor; And disclosedly among the WO95/10603 modify the amylase variants obtain from buy direct parent is added of Novo Nordisk A/S.What also be fit to is the amylase that is described among the EP277216 (Novo Nordisk).

The example of commercial α-Dian Fenmei product is the Purafect OxAm that buys from Genencor ^And Termamyl ^, Ban ^, Fungamyl ^And Duramyl ^, they all can be buied from NovoNordisk A/S Denmark.WO95/26397 has described other amylase that are fit to: α-Dian Fenmei is characterized in that passing through Phadebas ^The alpha-amylase activity measuring has specific activity greater than Termamyl in 25 ℃ of-55 ℃ of temperature and pH value under the 8-10 scope ^Specific activity at least 25%.Be advisable with the variant that is described in the above enzyme among the WO96/23873 (Novo Nordisk).Its activity level and thermostability other amylolytic enzymes of improved performance such as combine with the greater activity level are described among the WO95/35382.The preferred complementary amylase of the present invention be in WO94/18314, WO96/05295, describe by Genencor by trade(brand)name Purafect Ox Am ^RThe amylase of selling; Termamyl ^, Fungamyl ^, Ban ^, Natalase ^And Duramyl ^Maxamyl commercially available and that sell by Gist-Brocades all by Novo Nordisk A/S ^

Described complementary amylase is the incorporation in detergent composition of the present invention generally, by the weight of said composition, is 0.0001%-2%, preferred 0.00018%-0.06%, the more preferably pure enzyme of 0.00024%-0.048%.Preferred specific amylase is 9 with complementary diastatic pure enzyme weight ratio: 1-1: 9, more preferably 4: 1-1: 4, most preferably 2: 1-1: 2.

Above-mentioned enzyme can have any suitable source, as plant, animal, bacterium, mould and yeast source.This source can also be have a liking for temperature or have a liking for special conditions (psychrophilic, suitable cold, thermophilic, have a liking for pressure, that have a liking for alkali, have a liking for acid, have a liking for salt etc.).Can use the purifying or the non-purified form of these enzymes.The mutant that also comprises natural enzyme by definition.Mutant can obtain by protein engineering and/or genetic engineering, chemistry and/or the physically modified to natural enzyme.Common way is to express enzyme by host's organism, wherein the genetic material that produces enzyme is cloned.

The described enzyme generally incorporation in detergent composition is 0.0001% to 2% organized enzyme of detergent composition weight.Enzyme can be used as one-component independently and adds and (contain a kind of ball, grain of enzyme, stable liquid etc..) or add (for example composite particles) as the mixture of two or more enzymes.

The detergent component that other that can add are fit to is the oxydasis scavenging agent, and it is described in the existing autre action pendante european patent application of submitting on January 31st, 1,992 92870018.6.The example of this kind of enzyme oxidation scavengers is four alkylidene group polyamine of ethoxylation.

Various enzyme materials and their methods in the synthetic detergent composition of mixing also are disclosed in WO9307263A and the WO9307260A of Genencor International, in the people's such as McCarty that the WO8908694A of Novo and on January 5th, 1971 authorize the U.S. Pat 3553139.Some enzymes also be disclosed in the people's such as Place that authorized on July 18th, 1978 U.S. Pat 4101457 and the U.S. Pat 4507219 of the Hughes that authorized on March 26th, 1985 in.The enzyme material that is used for liquid detergent formula is disclosed in the people's such as Hora that authorized on April 14th, 1981 the U.S. Pat 4261868 with methods that they are incorporated into these prescriptions.The enzyme that is used for washing composition can make its stabilization with various technology.The enzyme stabilization technology discloses and illustrates the people's such as Gedge that authorize on August 17th, 1971 U.S. Pat 3600319, among the EP200586 of the EP199405 and the Venegas on October 29th, 1986.The enzyme stabilising system for example also is described in the U.S. Pat 3519570.The useful bacillus AC13 that produces proteolytic enzyme, zytase and cellulase is described among the WO9401532A of Novo.SYNTHETIC OPTICAL WHITNER

Highly preferred component in the composition of detergent components is a SYNTHETIC OPTICAL WHITNER.The SYNTHETIC OPTICAL WHITNER that is fit to comprises the SYNTHETIC OPTICAL WHITNER that discharges chlorine and oxygen.

A kind of preferred situation, the SYNTHETIC OPTICAL WHITNER that discharges oxygen contains hydrogen peroxide cource and organic peroxide acid bleach precursor compound.Situ reaction by precursor and hydrogen peroxide cource produces organic peroxide acid.Preferred hydrogen peroxide cource comprises inorganic perhydrate SYNTHETIC OPTICAL WHITNER.In in addition preferred situation, the ready-formed organic peroxide acid is directly added in the composition.Also consider to use the composition that contains with ready-formed organic peroxide acid blended hydrogen peroxide cource and organic peroxide acid precursor mixture.Inorganic perhydrate SYNTHETIC OPTICAL WHITNER

The composition of detergent components preferably includes hydrogen peroxide cource as the SYNTHETIC OPTICAL WHITNER that discharges oxygen.The hydrogen peroxide cource that is fit to comprises inorganic perhydrate salt.

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

The example of inorganic perhydrate salt is perborate, percarbonate, superphosphate, persulphate and persilicate.Inorganic perhydrate salt is an alkali metal salt normally.In the crystalline solid forms that inorganic perhydrate salt can be used as no supplementary protection is included in.Yet for some perhydrate salt, the preferred embodiment of this particulate composition is used the material of coated form, and this provides better package stability for the perhydrate salt in the granular product.

Sodium peroxoborate is standard type NaBO ₂H ₂O ₂The monohydrate form, or formula NaBO ₂H ₂O ₂3H ₂The tetrahydrate form of O.

Alkali metal percarbonate, especially SPC-D are the preferred perhydrate that comprises in the present composition.SPC-D is corresponding to 2Na ₂CO ₃3H ₂O ₂The addition compound of formula, commercially available form are crystalline solid.SPC-D is because of being hydrogen peroxide adduct, and its trend very discharges hydrogen peroxide apace when dissolving, and this has increases the trend that produces local high SYNTHETIC OPTICAL WHITNER concentration.Percarbonate most preferably mixes in this composition with coated form, is provided at the stability in the product.

Provide the coating material that is fit to of stability to comprise blended water-soluble alkali vitriol and carbonate to product.This coating material and coating method before be described in to be authorized among the GB-1466799 of Interox on March 9th, 1977.The weight ratio of mixing salt coating and percarbonate is 1: 200-1: 4, more preferably 1: 99-1: 9, most preferably 1: 49-1: 19.Preferably, sodium sulfate and yellow soda ash mixing salt general formula: Na ₂SO ₄NNa 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.

The coating that provides the another kind of stability to be fit to product comprises water glass, SiO ₂: Na ₂The O ratio is 1.8: 1-3.0: 1, preferred 1.8: 1-2.4: 1, and/or Starso, preferably its coated weight is 2%-10% (3%-5% usually) SiO ₂The inorganic perhydrate salt of weight.In coating, also can comprise Magnesium Silicate q-agent.The coating that contains silicate and borate or boric acid or other inorganicss also is fit to.

It also is favourable that other coatings that contain paraffin, oil, fatty soap are used for the present invention.

Peroxide one Potassium Persulphate is the another kind of inorganic perhydrate salt that can be used in the present composition.Peroxyacid bleach precursor

Peroxyacid bleach precursor was the compound that produces peroxy acid in the hydrolysis reaction with hydroperoxidation.Usually, peroxyacid bleach precursor can be expressed from the next:

Wherein, L is a leavings group, and X is any functional group substantially, as long as the peroxy acid structure that produces when making hydrolysis is a following formula,

With composition weight meter, the content of peroxyacid bleach precursor compound is preferably 0.5%-20%, more preferably 1%-10%, most preferably 1.5%-5%.

Suitable peroxyacid bleach precursor compound comprises one or more N-or O-acyl group usually, and its precursor can be selected from type widely.Suitable type comprises the acylated derivatives of acid anhydrides, ester, imide, lactan and imidazoles and oxime.The example of useful matter is disclosed among the GB-A-1586789 in these classes.Suitable ester be disclosed in GB-A-836988,864798,1147871,2143231 and EP-A-0170386 in.Leavings group

Leavings group hereinafter referred to as the L group must have enough activity to the hydrolysis reaction of crossing that occurs in the Best Times section (for example wash(ing)cycle).But if L is too active, this activator will be difficult to stably be used for bleaching composition.

Preferred L group is selected from following radicals or its mixture:

Wherein, R ¹Be alkyl, aryl or the alkaryl that comprises 1-14 carbon atom, R ³For comprising the alkyl chain of 1-8 carbon atom, R ⁴Be H or R ³, R ⁵For the alkenyl and the Y that contain 1-8 carbon atom is H or solubilization radical.R ¹, R ³And R ⁴In any can be replaced by any functional group basically, comprise for example alkyl, hydroxyl, alkoxyl group, halogen, amino, nitrosyl radical, acid amides and ammonium or alkyl ammonium group.

Preferred solubilization radical is-SO ₃ ^-M ⁺,-CO ₂ ^-M ⁺,-SO ₄ ^-M ⁺,-N ⁺(R ³) ₄X ^-And O＜--N (R ³) ₃, most preferably-SO ₃ ^-M ⁺With-CO ₂ ^-M ⁺, wherein, R ³For containing the alkyl of 1-4 carbon atom, M is for providing deliquescent positively charged ion to bleach-activating agent, and X is for providing deliquescent negatively charged ion to bleach-activating agent.Preferred M is the ammonium cation of basic metal, ammonium or replacement, most preferably sodium and potassium, and X is halogen, hydroxide radical, methylsulfate or acetic acid anion.Peroxybenzoic acid precursors

The peroxybenzoic acid precursors compound provides peroxybenzoic acid when having served as hydrolysis.

The peroxybenzoic acid precursors compound of the O-acylations that is fit to comprises and replacing and unsubstituted benzoyl oxygen benzene sulfonate, comprises for example benzoyl oxygen benzene sulfonate:

What also be fit to is the benzoylation product of Sorbitol Powder, glucose and all carbohydrates and benzoylation reagent, for example comprises: Ac=COCH ₃The Bz=benzoyl.

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

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

Tetra hydro Phthalic anhydride is the another kind of peroxybenzoic acid precursors compound that is fit to of the present invention:

The N-acylated lactams peroxybenzoic acid precursors that is fit to is a following formula:

Wherein n is 0-8, preferred 0-2, and R ⁶It is benzoyl.Peroxybenzoic acid derivative precursor

The peroxybenzoic acid that peroxybenzoic acid derivative precursor obtains replacing through hydrolysis.

The peroxybenzoic acid derivative precursor of the replacement that is fit to comprises any peroxybenzoic acid precursors disclosed herein; wherein benzoyl is comprised for example alkyl, hydroxyl, alkoxyl group, halogen, amine, nitrosyl radical and amide group by any non-positive charge (being non-cationic) functional group replacement basically.

The replacement peroxybenzoic acid precursors compound of preferred type is the compound that the acid amides of following general formula replaces: R wherein ¹Be aryl or alkaryl with 1-14 carbon atom, R ²Be arylidene and the alkarylene 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 the aryl of aryl, replacement or contain side chain, substituting group or the two alkaryl that it can be obtained by synthetic source or natural source, comprises for example butter fat.The variant of similar structures is to R ²Also allow.Substituting group can comprise alkyl, aryl, halogen, nitrogen, sulphur and other typical substituting group or organic compound.R ⁵Preferably H or methyl.R ¹And R ⁵Should not contain altogether and surpass 18 carbon atoms.The bleach activating immunomodulator compounds that this class acid amides replaces is described among the EP-A-0179386.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, as ammonium or alkyl ammonium group, and preferred ethyl or ammonium methyl group, the peroxy acid of the peroxyacid precursor compound that replacement is suitable partly forms.The positively charged ion peroxyacid precursor has a suitable negatively charged ion as a kind of usually, is present in the composition as halogen ion or methylsulfate ionic salt.

The peroxyacid precursor compound that this positively charged ion replaces can be the derivative of peroxybenzoic acid or its replacement, precursor compound as the aforementioned.Perhaps, the peroxyacid precursor compound can be the alkyl peroxy acids precursor that alkyl peroxycarboxylic acid precursors compound or acid amides as described below replace.

The positively charged ion peroxyacid precursor is stated in following document: US4,904,406; 4,751,015; 4,988,451; 4,397,757; 5,269,962; 5,127,852; 5,093,022; 5,106,528; U.K.1,382,594; EP475,512; 458,396 and 284,292; JP87-318,332.

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

The benzoyloxy benzene sulfonate that preferred cationic replaces is 4-(trimethyl ammonium) methyl-derivatives of benzoyloxy benzene sulfonate: The alkyl oxygen benzene sulfonate that preferred cation replaces as shown in the formula:

The preferred cationic peroxyacid precursor of N-acidylate hexanolactam class comprises trialkyl ammonium methylene radical benzoyl caprolactam, particularly trimethyl ammonium methylene radical benzoyl caprolactam:

Other preferred cation peroxyacid precursors of the hexanolactam class of N-acidylate comprise trialkyl ammonium methylene radical alkyl hexanolactam: Wherein n is 0-12, particularly 1-5.

Another kind of preferred cation peroxyacid precursor is chlorination 2-(N, N, a N-trimethyl ammonium) ethyl 4-sulfo group phenyl-carbonic acid sodium.Alkyl percarboxylic acids bleach precursor

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

Preferred imide-type alkyl peroxycarboxylic acid precursors compound comprises N, N, and N ', N '-tetra-acetylatedization Alkylenediamine, wherein, alkylidene group comprises 1-6 carbon atom, and particularly wherein alkylidene group comprises those compounds of 1,2 and 6 carbon atom.Preferred especially tetraacetyl ethylene diamine (TAED).

Other preferred alkyl peroxycarboxylic acid precursors comprise 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 penta-acetyl glucose.The alkyl peroxy acids precursor that acid amides replaces

The alkyl peroxy acids precursor compound that acid amides replaces also is fit to, and comprises the compound of following general formula: Wherein, R ¹For having the alkyl of 1-14 carbon atom, R ²For having the alkylidene group of 1-14 carbon atom, R ⁵For H or comprise the alkyl of 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 to contain side chain, substituting group or the two straight or branched alkyl, and can obtain, comprise for example butter fat by synthetic source or natural source.The variant of similar structures is for R ²Also allow.Substituting group can comprise alkyl, halogen, nitrogen, sulphur and other typical substituting group or organic compound.R ⁵Preferably H or methyl.R ¹And R ⁵Should not contain altogether and surpass 18 carbon atoms.The bleach activating immunomodulator compounds that such acid amides replaces is described among the EP-A-0179386.Benzoxazine organic peroxy acid precursor

What also be fit to is benzoxazine type precursor compound, EP-A-332 for example, and 294 and EP-A-482, the compound of those described in 807, particularly following formula:

The benzoxazine that comprises the replacement of following type:

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

The particularly preferred precursor of benzoxazine type is: The ready-formed organic peroxide acid

The organic peroxide acid bleach system also can contain prefabricated organic peroxide acid except containing organic peroxide acid bleach precursor compound, by the weight of said composition, generally its content is 0.5%-25% weight, 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 and the alkarylene 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, contain the aryl or the alkaryl of side chain, substituting group or the two replacement, it can be obtained by synthetic source or natural source, comprises for example butter fat.The variant of similar structures is to R ²Also allow.Substituting group can comprise alkyl, aryl, halogen, nitrogen, sulphur and other typical substituting group or organic compound.R ⁵Preferably H or methyl.R ¹And R ⁵Should not contain altogether and surpass 18 carbon atoms.The organic peroxy acid compound that this class acid amides replaces is described among the EP-A-0179386.

Other organic peroxide acids comprise diacyl and four acyl peroxides, particularly diperoxy dodecanedioic acid, diperoxy tetradecane diacid and diperoxy Thapsic acid.Dibenzoyl peroxide is the preferred organic peroxide acid of the present invention.Single-as and two to cross nonane diacid, single-or two cross undecane dicarboxylic acid and the amino oxy hexanoic acid of crossing of N-naphthoyl also is suitable for the present invention.The method of sustained release speed

Can provide sustained release SYNTHETIC OPTICAL WHITNER speed to washing soln, particularly discharge the method for oxygen bleaching agent speed.

The method of sustained release SYNTHETIC OPTICAL WHITNER speed can provide the superoxide of sustained release to washing soln.This method can comprise for example any inorganic perhydrate salt of sustained release in washing soln, as hydrogen peroxide cource.

The another kind of mechanism of sustained release SYNTHETIC OPTICAL WHITNER speed is the SYNTHETIC OPTICAL WHITNER by applying with coating, and it is designed to the delivery mode that provides controlled.Therefore coating can comprise the material of poorly water-soluble etc., or coating is enough thick, and the dissolution kinetics of thick coating provides controlled release rate.

Can make the coating composition that ins all sorts of ways.Coating generally is with coating: the SYNTHETIC OPTICAL WHITNER weight ratio is 1: 99-1: 2, and preferred 1: 49-1: 9 apply.

The coating that is fit to comprises triglyceride level (for example partially hydrogenated vegetables oil, soybean oil, oleum gossypii seminis), one or two glyceryl ester, micro-crystallization paraffin, gelatin, Mierocrystalline cellulose, lipid acid and its any mixture.

Other coating that are fit to can comprise basic metal and alkaline earth metal sulphate, silicate and carbonate, comprise lime carbonate and silicon-dioxide.

Preferred coating particularly for inorganic perhydrate salt bleach source, comprises 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 the weight of inorganic perhydrate salt, preferred glue spread is 2%-10% (3%-5% usually) SiO ₂Magnesium Silicate q-agent also can be included in the coating.

Any inorganic salt coating can combine with the organic binder bond material, obtains compound inorganic salt/organic binder bond coating.The tackiness agent that is fit to 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 comprise some polymeric material.Molecular-weight average is that Polyvinylpyrolidone (PVP) and the molecular-weight average of 12000-700000 is 600-5 * 10 ⁶, preferred 1000-400000, most preferably the polyoxyethylene glycol of 1000-10000 (PEG) is the example of this polymeric material.The multipolymer of maleic anhydride and ethene, methylvinylether or methacrylic acid also is the example that can be used as the polymeric material of tackiness agent, and wherein maleic anhydride constitutes at least 20 moles of % of this polymkeric substance.These polymeric materials can use separately or and solvent, for example water, propylene glycol and above-mentioned every mol of alcohol contain the C of 5-100 moles of ethylene oxide ₁₀-C ₂₀Alcohol ethoxylate is used in combination.Other examples of tackiness agent comprise C ₁₀-C ₂₀List and two glyceryl ethers also have C ₁₀-C ₂₀Lipid acid.

Derivatived cellulose for example poly carboxylic acid or its salt of methylcellulose gum, carboxymethyl cellulose and Natvosol and homopolymerization or copolymerization is to be applicable to other examples of adhesives of the present invention.

A kind of method of coating composition comprises agglomeration.Preferred agglomeration technique comprises the above-mentioned any organic binder bond material of use.Any conventional cyclone agglomerator/mixing tank be can use, still formula, drum-type and vertical agitator type included, but is not limited to.Also can be with the fused coating composition by toppling over or atomize spraying is applied on the moving-bed of SYNTHETIC OPTICAL WHITNER.

The additive method that provides desired control to discharge comprises the physical property that changes SYNTHETIC OPTICAL WHITNER, thereby controls the mechanical means of its dissolving and release rate.The scheme that is fit to can comprise compacting, mechanical injection, manual injection and pass through to select the solvability of the granularity of particle component with the adjusting bleaching compounds.

Although the selection of granularity depends on the composition of particle component and satisfy the dynamic (dynamical) requirement of required sustained release, preferably granularity should be greater than 500 microns, and preferred average particulate diameter is the 800-1200 micron.

Any other component that provides other schemes of sustained release method to comprise suitable selection detergent composition matrix is so that when composition was added in the washing soln, the ionic strength environment that wherein provides can reach the desired control release dynamics.Metallic bleaching catalyst

The SYNTHETIC OPTICAL WHITNER that contains as herein described also can contain metallic bleaching catalyst as preferred component as the composition of detergent components.Metallic bleaching catalyst preferably contains the bleaching catalyst of transition metal, more preferably contains the bleaching catalyst of manganese or cobalt.

A kind of bleaching catalyst of suitable type comprises the active heavy metal cation of the bleach catalyst with definition, as copper, iron positively charged ion, have very little or do not have the active assistant metal positively charged ion of bleach catalyst, as zinc or aluminium cations, with sequestrant, particularly ethylenediamine tetraacetic acid (EDTA) with catalysis and the defined stability constant of assistant metal positively charged ion, ethylenediamine tetraacetic (methylene phosphonic acid) and its water-soluble salt.This catalyzer is disclosed in US4, in 430,243.

Preferred bleaching catalyst type comprises and is disclosed in US5, the manganese basigamy compound in 246,621 and US5,244,594.The preferred embodiment of these catalyzer comprises: Mn ^IV ₂(u-O) ₃(1,4,7-trimethylammonium-1,4,7-7-triazacyclononane) ₂(PF ₆) ₂, Mn ^III ₂(u-O) ₁(u-OAc) ₂(1,4,7-trimethylammonium-1,4,7-7-triazacyclononane) ₂(ClO ₄) ₂, Mn ^IV ₄(u-O) ₆(1,4, the 7-7-triazacyclononane) ₄(ClO ₄) ₂, Mn ^IIIMn ^IV ₄(u-O) ₁(u-OAc) ₂(1,4,7-trimethylammonium-l, 4,7-7-triazacyclononane) ₂(ClO ₄) ₃And their mixture.Other are described in the European patent application publication No. 549272.Other are applicable to that ligand of the present invention comprises 1,5,9-trimethylammonium-1,5,9-triazododecane, 2-methyl isophthalic acid, 4,7-7-triazacyclononane, 2-methyl isophthalic acid, 4,7-7-triazacyclononane, 1,2,4,7-tetramethyl--1,4,7-7-triazacyclononane and its mixture.

The bleaching catalyst that can be used for the present composition can suitably be selected to be used for the present invention.For example, the bleaching catalyst that is fit to is referring to United States Patent (USP) 4,246, and 612 and 5,227,084.Also referring to United States Patent (USP) 5,194,416, it has introduced for example Mn (1,4,7-trimethylammonium-1,4,7-7-triazacyclononane)-(OCH of monokaryon manganese (IV) title complex ₃) ₃(PF ₆).

Be disclosed in another kind of bleaching catalyst in the United States Patent (USP) 5114606 and be the water-soluble complexes of manganese (III) and/or (IV) and the polyol ligand of the non-carboxylate salt that has three continuous C-OH groups at least.Preferred ligand comprises Sorbitol Powder, iditol, galactitol, mannitol, Xylitol, arabitol, adonitol, meso-tetrahydroxybutane, meso-inositol, lactose and its mixture.

U.S. Pat 5114611 has been introduced bleaching catalyst, comprises the title complex of transition metal and non-(greatly) ring ligand, and described transition metal comprises Mn, Co, Fe or Cu.Described ligand as shown in the formula: R wherein ¹, R ², R ³And R ⁴Each can be selected from the alkyl and the aryl of H, replacement, makes each R ¹-N=C-R ²And R ³-C=N-R ⁴Formation five or six-ring.Described ring also can be substituted.B is an abutment, is selected from O, S, CR ⁵R ⁶, NR ⁷And C=O, wherein R ⁵, R ⁶And R ⁷Can be H, alkyl or aryl separately, comprise replacing or unsubstituted group.Preferred ligand comprises pyridine, pyridazine, pyrimidine, pyrazine, imidazoles, pyrazoles and triazole ring.Optionally described ring can be substituted base, and for example alkyl, aryl, alkoxyl group, halogen and nitro replace.Particularly preferably be ligand 2,2 '-two pyridine amine.Preferred bleaching catalyst comprises Co, Cu, the two pyridine methane of Mn, Fe and two pyridine amine complex.Highly preferred catalyzer comprises Co (2,2 '-two pyridine amine) Cl ₂, two (different sulfo-cyanato-) two pyridine amine cobalts (II), three pairs of pyridine amine cobalts (II) perchlorate, Co (2,2 '-two pyridine amine) ₂O ₂ClO ₄, two (2,2 '-two pyridine amine) copper (II) perchlorate, three (two-2-pyridine amine) iron (II) perchlorate and its mixture.

Preferred examples comprises the double-core Mn title complex that has 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 the structure of the manganese complex of catalytically bleaching agent of the present invention is not illustrated, can infer that they comprise by the carboxyl of ligand and nitrogen-atoms and manganese positively charged ion the interact inner complex that obtains or the coordinate complex of other hydrations.The cationic, oxidized attitude of manganese is imprecise in this catalytic process equally knows, can be (+II), (+III), (+IV) or (+V) valence state.Because ligand has six points and contacts with the manganese positively charged ion, therefore can infer in the aqueous bleaching medium, to have multinuclear material and/or " cage shape " structure with having reason.No matter active Mn-ligand material reality with what form exists, it all has obvious catalysis, provides stain, for example improved bleachabilities such as tea stain, strained tomatoes, coffee, wine, fruit juice.

Other bleaching catalysts are described in for example European patent application publication No. 408131 (cobalt complex catalyzer), European patent application publication No. 384503 and 306089 (catalysis of metalloporphyrin agent), United States Patent (USP) 4728455 (manganese/polygamy position polymerization of olefin using catalyst body catalyst), United States Patent (USP) 4711748 and European patent application publication No. 224952 (catalyzer of absorption manganese on silico-aluminate), United States Patent (USP) 4601845 (being loaded with the silico-aluminate of manganese and zinc or magnesium salts), United States Patent (USP) 4626373 (manganese/ligand catalyzer), United States Patent (USP) 4119557 (ferric iron composition catalyst), German patent specification 2054019 (cobalt sequestrant catalyzer), Canadian Patent 866191 (salt that contains transition metal), United States Patent (USP) 4430243 (sequestrant that has manganese positively charged ion and on-catalytic metallic cation) and United States Patent (USP) 4728455 (manganese gluconate catalyzer).

Other preferred examples comprise cobalt (III) catalyzer of following formula:

Co[(NH ₃) _nM ' _mB ' _bT ' _tQ _qP _p] Y _yWherein cobalt is+3 valency oxidation state, and n is 0 to 5 integer (preferred 4 or 5; Most preferably 5), M ' represents single coordinate ligand; M is 0 to 5 integer (preferred 1 or 2, most preferably 1); The two coordinate ligands of B ' expression; B is 0 to 2 integer; The ligand of T ' expression three-fold coordination; T is 0 or 1; Q is the ligand of four-coordination; Q is 0 or 1; P is the ligand of pentacoordinate; P is 0 or 1; N+m+2b+3t+4q+5p=6; Y is that number is one or more counter anion of suitably selecting of y, and wherein y is an integer 1 to 3 (preferred 2 to 3; When Y was a-1 charged negatively charged ion, most preferably y was 2) so that obtain the salt of charge balance, preferred Y is selected from chlorine, nitrate radical, nitrite anions, sulfate radical, citrate, acetate moiety, carbonate and their mixture; Under the automatic dishwashing working conditions, be active wherein with at least one coordination site of cobalt bonded, cobalt is stablized in remaining coordination site under the automatic dishwashing condition, the relative ordinary hydrogen electrode of reduction potential that makes cobalt under alkaline condition (III) be reduced to cobalt (II) is lower than 0.4 volt (preferably being lower than 0.2 volt).

The preferred cobalt catalyst of this type as shown in the formula:

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

The preferred cobalt catalyst of this class that the present invention is suitable for is formula [Co (NH ₃) ₅Cl] Y _yCobalt five amine chloride salts, particularly [Co (NH ₃) ₅Cl] Cl ₂

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

[Co (NH ₃) _n(M) _m(B) _b] T _yWherein cobalt is+3 valency oxidation state; N is 4 or 5 (preferred 5); M passes through the one or more ligands of site coordinate with cobalt; M is 0,1 or 2 (preferred 1); B passes through two site coordinate ligands with cobalt; B is 0 or 1 (preferred 0), when b=0, and m+n=6 then, when b=1, then m=0 and n=4; And T to be number be suitable selecteed one or more counter anion of y, wherein y is an integer, (preferably y is 1 to 3 so that obtain the salt of balancing charge; When T was the negatively charged ion of a-1 electric charge of band, most preferably y was 2); Its basic hydrolysis rate constant of wherein said catalyzer is lower than 0.23M ^-1s ^-1(25 ℃).

Preferred T is selected from chlorine, iodine, I ₃ ^-, formate, nitrate radical, nitrite anions, sulfate radical, inferior sulfate radical, citrate, acetate moiety, carbonate, bromine, PF ₆ ^-, BF ^{4 -}, B (Ph) ₄ ^-, phosphate radical, orthophosphite, silicate, tosylate, methanesulfonate and their mixture.If in T, exist more than anionic group, for example a HPO ₄ ^2-, HCO ₃ ^-, H ₂PO ₄ ^-Deng, then T is optional can be by protonated.In addition, T can be selected from the inorganic anion thing of non-transition, for example anion surfactant (as linear alkylbenzene sulfonate (LAS), alkyl-sulphate (AS), alkyl ethoxy sulfonate (AES) etc.) and/or anionic polymer (for example polyacrylate, polyisobutene hydrochlorate etc.).

M partly includes, but is not limited to for example F ^-, SO ₄ ^-2, NCS ^-, SCN ^-, S ₂O ₃ ^-2, NH ₃, PO ₄ ^3-And carboxylate radical (it is the monocarboxylic acid root preferably, but this part can exist more than a carboxylate radical, as long as combine with cobalt is that each M part is only passed through a carboxylate radical, and in this case, M other carboxylate radicals partly can be by protonated or exist with the form of its salt).If in M, exist more than an anionic group (HPO for example ₄ ^2-, HCO ₃ ^-, H ₂PO ₄ ^-, HOC (O) CH ₂C (O) O-etc.), M is optional can be by protonated.Preferred M partly is the replacement and the unsubstituted C of following formula ₁-C ₃₀Carboxylate radical:

RC (O) O-wherein R is preferably selected from hydrogen, 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, R ' is selected from hydrogen and C here ₁-C ₆Part.Therefore the R of this replacement comprises-(CH ₂) _nOH and-(CH ₂) _nNR ' ₄ ⁺Part, wherein n is 1 to 16 integer, and is preferred 2 to 10, most preferably 2 to 5.

Most preferably M is the carboxylate radical with following formula, and wherein R is selected from hydrogen, methyl, ethyl, propyl group, straight or branched C ₄-C ₁₂Alkyl and benzyl.Most preferably R is a methyl.Optimization acid's root M comprises formate, benzoate anion, sad, n-nonanoic acid root, decanoate, dodecane acid group, malonate, maleate, amber acid radical, hexanodioic acid root, phthalic acid root, 2 ethyl hexanoic acid root, cycloalkanes acid group, oleic acid root, palm acid group, trifluoromethanesulfonic acid root, tartrate anion, stearate radical, butyric acid root, citrate, propylene acid group, aspartate, fumaric acid radical, laurate, linoleate, lactate, malate and particularly acetate moiety.

B partly comprises carbonate, binary or high carboxylic acid's root (for example oxalate, malonate, malate, amber acid radical, maleate), pyridine carboxylic acid root and α-and beta-amino acid group (for example glycine root, L-Ala root, Beta-alanine root, phenylalanine root).

It is known being used for cobalt bleaching catalyst of the present invention, relevant its details, for example their basic hydrolysis speed etc. is described in M.L.Tobe, " basic hydrolysis of transition metal complex ", " the inorganic mechanism of high lithotroph " (Adv.Inorg.Bioinorg.Mech.), (1983), 2, in the 1-94 page or leaf. for example in 17 page tables 1, provide and 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 ℃)) the basic hydrolysis speed of coordinate cobalt five amine catalysts (is expressed as k in this article _OH).Being used for the most preferred cobalt catalyst of the present invention is formula [Co (NH ₃) ₅OAc] T _yCobalt five amine acetates, wherein OAc represents the acetate moiety part, particularly cobalt chloride five amine acetate [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(this paper " PAC ").

These cobalt catalyst are easily with known method preparation, for example in the reference that above Tobe article neutralization is wherein quoted, authorize introduction in the United States Patent (USP) 4,810,410 of Diakun etc. on March 7th, 1989; J.Chem.Ed. (1989), 66 (12), 1043-1045; " the synthetic and sign of mineral compound ", W.L.Jolly (Prentice-Hall; 1970), 461-463 page or leaf; Inorganic chemistry, 18,1497-1502 (1979); Inorganic chemistry, 21,2881-2885 (1982); Inorganic chemistry, 18,2023-2025 (1979); Inorganic synthetic, 173-176 (1960); With the physical chemistry magazine, 56,22-25 (1952); And tell about in the synthetic example provided below.

The suitable cobalt catalyst that mixes in the detergent tablet of the present invention can be according to disclosed synthetic route preparation in United States Patent (USP) 5559261,5581005 and 5597936, and its disclosure is quoted for referencial use at this paper.

If according to the product aesthetic requirement, these catalyzer can be processed jointly with subsidiary material, so that reduce the influence of color, or be included in the hereinafter illustrational enzyme containing granule, or composition can be made into to contain catalyzer " look grain ".Organic polyhydroxyl compound

The preferred component that organic polyhydroxyl compound can be used as detergent tablet of the present invention adds.The organic polyhydroxyl compound meaning is meant any organic polyhydroxyl compound that is present in usually in the detergent composition basically, and it has dispersion agent, anti redeposition agent, dirt release agent or other washing character.

Press composition weight meter, the organic polyhydroxyl compound generally incorporation in 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 poly carboxylic acid or its salt of water-soluble organic homopolymerization or copolymerization poly carboxylic acid, modification, and wherein poly carboxylic acid comprises at least two and is no more than the carboxyl that two carbon atoms separate are opened each other.The polymkeric substance of back one type is disclosed in GB-A-1, in 596,756.The example of this salt be molecular weight 2000-10000 polyacrylate and with the multipolymer of any other monomeric unit that is fit to, described other monomeric units comprise vinylformic acid, 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 any mixture of modification.Preferably molecular weight is the vinylformic acid of 20000-100000 and the multipolymer of maleic anhydride.

Preferred commercially available molecular weight be lower than 15000 contain the polymerizing acrylic acid thing comprise sell with trade(brand)name Sokalan PA30, PA20, PA15, PA10 and Sokalan CP10 by BASF GmbH those and sell with trade(brand)name Acusol 45N, 480N, 460N by Rohm and Haas those.

Preferably contain acrylic acid multipolymer and comprise those that contain following monomeric unit: a) 90%-10%, preferred 80%-20% weight percent acrylic acid or its salt and b) 10%-90%, Acrylic Acid Monomer or its salt that preferred 20%-80% weight replaces, its general formula is-[CR ₂-CR ₁(CO-O-R ₃)]-, R wherein ₁, R ₂Or R ₃At least one substituting group, 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.The most preferably Acrylic Acid Monomer of Qu Daiing, wherein R ₁Be methyl, R ₂Be hydrogen (being methacrylic acid monomer).The most preferred molecular weight of copolymer 3500 of this class also contains the 60%-80% weight percent acrylic acid and the 40%-20% weight methacrylic acid.

The polyamino compound of polyamine and modification can be used for the present invention, comprises those materials that obtained by aspartate-derived, and for example EP-A-305282, EP-A-305283 and EP-A-351629 are described.

Other optional polymer can be Mierocrystalline cellulose, polyoxyethylene, polyoxypropylene and its multipolymers of modification and unmodified polyvinyl alcohol and acetate, Mierocrystalline cellulose and modification, the both can be modification and unmodified, ethylene glycol or propylene glycol or its mixture and the unitary terephthalate of polyoxy alkylidene.

The example that is fit to is disclosed in United States Patent (USP) 5591703,5597789 and 4490271.Dirt release agent

The polymkeric substance dirt release agent that is fit to comprises those dirt release agents with following composition: (a) mainly by (ⅰ) or (ⅱ) or one or more nonionic hydrophilic components of (ⅲ) forming, wherein (ⅰ) is that the polymerization degree is at least 2 polyoxyethylene part, (ⅱ) be the polyoxypropylene part that the propylene oxide or the polymerization degree are at least 2-10, wherein said hydrophilic segment does not comprise any propylene oxide unit, unless this unit is attached at the adjacent segment two ends by ehter bond, (ⅲ) contain the mixture of the oxygen alkylidene unit of an ethylene oxide and 1-30 propylene oxide unit, described hydrophilic segment preferably contains at least 25% ethylene oxide unit, more preferably, particularly, has 50% ethylene oxide unit at least for this component that contains 20-30 propylene oxide unit; Or (b) by (ⅰ), (ⅱ), (ⅲ) or (ⅳ) one or more hydrophobic ingredients of forming, wherein (ⅰ) is C3 alkylidene oxide terephthalic acid ester moiety, if wherein described hydrophobic ingredient also comprises the ethylene oxide terephthalate, then the ratio of ethylene oxide terephthalate and C3 alkylidene oxide terephthalate units is 2: 1 or lower, (ⅱ) be C4-C6 alkylidene group or oxidation C4-C6 alkylene moiety, or their mixture, (ⅲ) be poly-(vinyl ester) part, preferred degree of polymerization is at least 2 poly-(vinyl-acetic ester), (ⅳ) be C1-4 alkyl oxide or C4 hydroxyalkyl ether substituting group, or their mixture, wherein said substituting group exists with C1-4 alkyl oxide or C4 hydroxyalkyl ether derivatived cellulose or its form of mixtures, or (a) and combination (b).

Generally speaking, (a) polymerization degree of the part of the polyoxyethylene in (ⅰ) is 200, although also can use the higher polymerization degree, and preferred 3-150; 6-100 more preferably.The oxidation C4-6 alkylidene group hydrophobic part that is fit to includes, but is not limited to polymerization dirt release agent end-blocking part, as MO ₃S (CH ₂) _nOCH ₂CH ₂O-, M is a sodium in the formula, n is the integer of 4-6, as in the United States Patent (USP) 4721580 of authorizing in 26 days January in 1988 of Gosselink disclosed those.

The polymerization dirt release agent that uses among the present invention also comprises derivatived cellulose, hydroxy ethers cellulose polymer compound for example, the copolymerization block thing of glycol terephthalate or propylene glycol terephthalate and polyoxyethylene terephthalate or polyoxypropylene terephthalate etc.These reagent all have commercially available, comprising the Mierocrystalline cellulose hydroxy ethers as METHOCEL (Dow).The Mierocrystalline cellulose dirt release agent that the present invention uses also comprises C1-4 alkyl and C4 hydroxy alkyl cellulose; United States Patent (USP) 4000093 referring to the people such as Nicol that authorized on December 28th, 1976.

The dirt release agent that is characterised in that poly-(vinyl ester) hydrophobic part comprises poly-(vinyl ester), as the graft copolymer of C1-6 vinyl ester, preferably grafts on the polyoxyalkylene skeleton, as poly-(vinyl-acetic ester) on the polyoxyethylene skeleton.European patent application 0219048 referring to people such as disclosed Kud on the 22nd April in 1987.

Other dirt release agents that are fit to are to have glycol terephthalate and polyoxyethylene (PEO) terephthalate statistic copolymer.The molecular weight of this polymerization dirt release agent is 25000-55000.United States Patent (USP) 3893929 referring to the United States Patent (USP) 3959230 of the Hays that authorized on May 25th, 1976 and the Basadur that authorized on July 8th, 1975.

The another kind of polymerization dirt release agent that is fit to is the polyester that has the glycol terephthalate repeating unit, wherein contain the glycol terephthalate unit of 10%-15% (weight) and the polyoxyethylene terephthalate unit of 90%-80% (weight), it is that the polyoxy glycol of 300-5000 obtains by molecular-weight average.

The another kind of polymerization dirt release agent that is fit to is the sulfonated products that is essentially the linear ester oligopolymer, and this oligopolymer is by terephthaloyl and the multiple unitary oligomer ester skeleton of oxyalkylene oxygen basic weight, and the terminal portions that links to each other with this skeleton covalency constitutes.In J.J.Scheibel that authorize November 6 nineteen ninety and the United States Patent (USP) 4968451 of E.P.Gosselink these dirt release agents there is complete description.Other polymerization dirt release agents that are suitable for comprise the terephthalate polyester in the people's such as Gosselink that on December 8th, 1987 authorized the United States Patent (USP) 4711730, the block polyester oligopolymer in the United States Patent (USP) 4702857 of the Gosselink that the end capped oligomer ester of negatively charged ion and on October 27th, 1987 authorize in the United States Patent (USP) 4721580 of the Gosselink that on January 26th, 1988 authorized.Other polymerization dirt release agents also comprise the dirt release agent in the people's such as Maldonado that authorized on October 31st, 1989 the United States Patent (USP) 4877896, this patent disclosure negatively charged ion, the particularly end capped terephthalate of sulfo group aroyl.

Another kind of dirt release agent is the oligopolymer with following repeating unit: terephthaloyl unit, sulfo group isophthaloyl unit, oxygen ethylidene oxygen and oxygen-1,2-propylidene unit, these repeating units have constituted the skeleton of oligopolymer, and preferably use the isethionate end-blocking of modification.The oxygen ethylidene oxygen that it is 1.7-1.8 that particularly preferred this type of dirt release agent comprises a sulfo group isophthaloyl unit, 5 terephthaloyl unit, ratios and the end-blocking unit of oxygen-propylene oxygen unit and 2 2-(2-hydroxy ethoxy) ethane sulfonic acid sodium.Heavy metal ion chelating agent

Sheet of the present invention preferably contains heavy metal ion chelating agent as optional component.Heavy metal ion chelating agent has been meant the component of chelating heavy metal ion effect in this paper meaning.These components also can have calcium and magnesium sequestering power, but preferably they demonstrate the selectivity in conjunction with heavy metal ion such as iron, manganese and copper.

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

Heavy metal ion chelating agent, it is acid, for example have phosphonic acids or carboxylic functionality, can its sour form exist or conduct and proper equilibrium positively charged ion, for example the title complex of the ammonium ion of basic metal or alkaline-earth metal ions, ammonium or replacement or its any mixture/salt form exists.Preferred any salt/title complex is water miscible.The mol ratio of described balance cation and heavy metal ion chelating agent preferably was at least 1: 1.

Be suitable for heavy metal ion chelating agent of the present invention and include organic phosphonates, as amino alkylidenyl poly-(alkylene phosphonic acids salt), basic metal ethane 1-hydroxyl diphosphonate and WSI 3310 salt.Preferably diethylenetriamine five (methylene phosphonic acid salt), quadrol three (methylene phosphonic acid salt), hexamethylene-diamine four (methylene phosphonic acid salt) and hydroxyl-ethylidene 1 in the above-mentioned substance, the 1-diphosphonate.

Other are applicable to that heavy metal ion chelating agent of the present invention comprises nitrilotriacetic acid(NTA) and polyamino carboxylic acid, as ethylenediamine tetraacetic acid (EDTA), ethylidene pentaacetic acid, ethylenediamine disuccinic acid, quadrol two pentanedioic acids, 2-hydroxyl propylene diamine disuccinic acid or its any salt.

Particularly preferably be quadrol-N, the ammonium salt of N '-disuccinic acid (EDDS) or its basic metal, alkaline-earth metal, ammonium or replacement, or its mixture.Preferred EDDS compound is free acid form and sodium or magnesium salts or its title complex.The crystal growth inhibitor component

Detergent tablet preferably contains the crystal growth inhibitor component, preferred organic diphosphonic acid component, and by the weight of said composition, preferably its content is 0.01%-5%, more preferably 0.1%-2%.

Organic diphosphonic acid, the meaning is the organic diphosphonic acid that does not contain as the nitrogen of its chemical structure part here.Therefore, organic amino phosphonates do has been got rid of in this definition, yet it can be included in the present composition as the heavy metal ion chelating agent component.

Organic diphosphonic acid is C preferably ₁-C ₄Di 2 ethylhexyl phosphonic acid, more preferably C ₂Di 2 ethylhexyl phosphonic acid, for example ethylidene diphosphonic acid or most preferably ethane 1-hydroxyl-1,1-di 2 ethylhexyl phosphonic acid (HEDP), it can partially or completely Ionized form exist, and particularly exists as salt or title complex.Water soluble sulfate

The optional water soluble sulfate that contains of detergent tablet.When existing, by the weight of composition, the content of water soluble sulfate is 0.1%-40%, more preferably 1%-30%, most preferably 5%-25%.

Water soluble sulfate can be any vitriol with any balance cation basically.Preferred salt is selected from basic metal and alkaline earth metal sulphate, particularly sodium sulfate.Alkalimetal silicate

Alkalimetal silicate is the preferred component 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.The water glass preferred content is lower than 20%, preferred 1%-1 5%, most preferably 3%-12% weight SiO ₂Alkalimetal silicate can anhydrous salt or the existence of salt hydrate form.

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

Alkaline system also preferably contains Starso, and its content is 0.4%SiO at least ₂(weight).The SiO of Starso ₂: Na ₂O nominal ratio is 1.0.The weight ratio of described water glass and described Starso is pressed SiO ₂Measure, be preferably 50: 1-5: 4, more preferably 15: 1-2: 1, most preferably 10: 1-5: 2.Tinting material

Term as herein described ' tinting material ' meaning is any material that can absorb the special wavelength light in the visible spectrum.This tinting material has the effect that changes visual color when time in the adding detergent composition, has therefore changed the outward appearance of detergent composition.Tinting material can for example be dyestuff or pigment.Preferred tinting material is stable in the composition that they mix.Therefore in the composition of high pH, tinting material is alkaline stability preferably, and in the composition of low pH, tinting material is acid acceptance preferably.

First and/or second other can contain the mixture of mixture, colored particles or the colored particles of tinting material, tinting material mutually mutually and/or randomly, so that each has different visual appearances mutually.One of preferred first or second phase comprises tinting material.When first and second mutually and/or its second phase when comprising tinting material, preferred tinting material has different visual appearances.

The dyestuff example that is fit to comprises reactive dyestuffs, substantive dyestuff, azoic dyestuff.Preferred dyestuff comprises phthalocyanine pigment, anthraquinone dye, quinoline dye, a nitrogen, phenodiazine and many nitrogen dyestuff.Preferred dyestuff comprises anthraquinone, quinoline and a nitrogen dyestuff.Preferred dyestuff comprises SANDOLANE-HRL 180% (trade(brand)name), SANDOLAN MILLING BLUE (trade(brand)name), TURQUOISEACID BLUE (trade(brand)name) and SANDOLAN BRILLIANT GREEN (trade(brand)name), they all can be purchased from Clariant UK, HEXACOL QUINOLINE YELLOW (trade(brand)name) and HEXACOL BRILLIANT BLUE (trade(brand)name), the both is from Pointings, UK buys, the ULTRA MARINE BLUE (trade(brand)name) that can buy from Holliday or from Bayer, the LEVAFIX TURQUISE BLUE EBA (trade(brand)name) that USA buys all can.

During tinting material can mix mutually with any suitable method.The method that is fit to is included in the cylinder mixes all or selected detergent components with tinting material, or in cylinder tinting material is sprayed onto on all or the detergent components selected.

When tinting material existed when the component as first phase, its content was 0.001%-1.5%, preferred 0.01%-1.0%, most preferably 0.1%-0.3%.Tinting material is when as second and/or when randomly the component of other phases exists, and the content of tinting material is generally 0.001%-0.1%, more preferably 0.005%-0.05%, most preferably 0.007%-0.02%.Corrosion inhibition immunomodulator compounds

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

The organic silver liniment is described among PCT publication number WO94/16047 and the autre action pendante European application EP-A-690122.Nitrogenous corrosion inhibition immunomodulator compounds is disclosed among the autre action pendante European application EP-A-634478.Be used for suppressing corrosive Mn (II) compound and be described in autre action pendante European application EP-A-672749.

Apply the organic reagent of silver, by the weight of total composition, its content is 0.05%-10%, preferred 0.1%-5%.

The reagent effect that applies silver is that all silverwares partly form the supercoat of ' in the use ' on using the washes of the present composition.Apply argentum reagent and therefore should have the high-affinity that contacts the solid silver surface, particularly when the component as the wash water solution of handling the solid silver surface and liquid lime chloride exists.

The organic reagent of the coating silver that the present invention is fit to is included in the monobasic that has 1-40 carbon atom in the hydrocarbon chain or the fatty acid ester of polyvalent alcohol.

The fatty acid part of fatty acid ester can be obtained by monobasic that has 1-40 carbon atom in the hydrocarbon chain or polycarboxylic acid.The example that the monobasic aliphatic carboxylic acid is fit to 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.The polycarboxylic example that is fit to comprises n-butylmalonic acid, isocitric acid, citric acid, toxilic acid, oxysuccinic acid and succsinic acid.

The typical example of the Fatty Alcohol(C12-C14 and C12-C18) part of fatty acid ester is one or the polyvalent alcohol that has 1-40 carbon atom in the hydrocarbon chain.The example of the Fatty Alcohol(C12-C14 and C12-C18) that is fit to comprises behenyl alcohol, n-Eicosanol, lauric alcohol, oleyl alcohol and lauryl alcohol, ethylene glycol, glycerine, ethanol, Virahol, vinyl alcohol, two glycerine, Xylitol, sucrose, erythritol, tetramethylolmethane, Sorbitol Powder or sorbitan.

Preferably, the alkyl chain of the lipid acid of fatty acid ester subsidiary material and/or Fatty Alcohol(C12-C14 and C12-C18) has 1-24 carbon atom.

The preferred fatty acid ester of the present invention is ethylene glycol, glycerine and sorbitan ester, and wherein the fatty acid part of this ester generally comprises the material that is selected from mountain Yu acid, stearic acid, oleic acid, palmitinic acid or tetradecanoic acid.

Glyceryl ester also is highly preferred.These are one, two or three esters as above-mentioned glycerine and lipid acid.

The specific examples that is used for aliphatic alcohol ester of the present invention comprises the stearic alcohol ester of acetate, lactyl-lactic acid palm alcohol ester, isopropylformic acid cocounut oil alcohol ester, toxilic acid oleyl alcohol ester, two toxilic acid oleyl alcohol esters and propionic acid butter ester.The useful fatty acid ester of the present invention comprises a palmitinic acid xylitol ester, the monostearate pentaerythritol ester, the monostearate sucrose ester, glyceryl monostearate, the monostearate glycol ester, sorbitan ester, the sorbitan ester that is fit to comprises the monostearate sorbitan ester, the palmitinic acid sorbitan ester, one lauric acid sorbitan ester, one tetradecanoic acid sorbitan ester, one mountain Yu acid sorbitan ester, the monooleate sorbitan ester, two lauric acid sorbitan esters, distearyl acid sorbitan ester, two mountain Yu acid sorbitan ester, two oleic acid sorbitan esters, and blended tallow alkyl sorbitan one and diester.

Glyceryl monostearate, monooleate glyceryl ester, a palmitin, a Glyceryl Behenate and distearin are the preferred glyceryl ester of the present invention.

The organic reagent of the coating silver that is fit to comprises triglyceride level, one or two glyceryl ester, its all or part of hydrogenant derivative and its any mixture.The fatty acid ester source that is fit to comprises plant and fish oil and animal tallow.The vegetables oil that is fit to comprises soybean oil, oleum gossypii seminis, Viscotrol C, sweet oil, peanut oil, Thistle oil, sunflower oil, rapeseed oil, wine stone oil, plam oil and Semen Maydis oil.

Paraffin comprises that micro-crystallization paraffin is the organic reagent of the coating silver that is fit to of the present invention.Preferred paraffin has 35 ℃-110 ℃ of fusing points ,-as comprise 12-70 carbon atom.The petroleum wax of paraffin and micro-crystallization type preferably, it is made of the long-chain saturated hydrocarbon compound.

Alginates and gel are the organic reagents of the coating silver that is fit to of the present invention.

Dialkyl group amine oxide, for example C ₁₂-C ₂₀Methyl oxidation amine, dialkyl quats compound and its salt for example, C ₁₂-C ₂₀The methyl ammonium halide also is fit to.

The organic reagent of the coating silver that other are fit to comprises some polymeric material.Molecular-weight average is the Polyvinylpyrolidone (PVP) of 12000-700000, the polyoxyethylene glycol (PEG) that molecular-weight average is 600-10000, the multipolymer and the derivatived cellulose of polyamine N-oxide pllymers, N-vinyl pyrrolidone and N-vinyl imidazole, for example methylcellulose gum, carboxymethyl cellulose and Natvosol are the examples of this polymeric material.

Some spices, particularly confirming has those of high-affinity to the metallic surface, also is suitable as the organic reagent that the present invention applies silver.

The polymerization dirt release agent also can be used as the organic reagent that applies silver.

The preferred organic reagent that applies silver is a paraffin oil, and generally it mainly is that carbonatoms is the branched aliphatic hydrocarbons of 20-50; It mainly is the C of side chain that preferred paraffin oil is selected from _25-45Material, the ratio of its ring-type and non-cyclic hydrocarbon are 1: 10-2: 1, preferred 1: 5-1: 1.Satisfy the paraffin oil of these features, wherein the ratio of ring-type and non-cyclic hydrocarbon is 32: 68, is German Wintershall, and Salzbergen sells by trade(brand)name WINOG70.Nitrogenous corrosion inhibition immunomodulator compounds

The nitrogenous corrosion inhibition immunomodulator compounds that is fit to comprises imidazoles and its derivative, those imdazole derivatives of describing among benzoglyoxaline, 2-heptadecyl imidazoles and Czech patents 139279 and the English Patent GB-A-1137741 for example, it also discloses the method for preparing this imidazolium compounds.

What also be suitable as nitrogenous corrosion inhibition immunomodulator compounds is that pyrazole compound and its derivative, particularly pyrazoles 1,3,4 or 5 is substituted basic R ₁, R ₃, R ₄And R ₅Those that replace, wherein R ₁Be H, CH ₂OH, CONH ₃Or COCH ₃In any, R ₃And R ₅Be any C ₁-C ₂₀Alkyl or hydroxyl, R ₄Be H, NH ₂Or NO ₂In any.

Other nitrogenous corrosion inhibition immunomodulator compounds that are fit to comprise benzotriazole, 2-sulfydryl benzotriazole, 1-phenyl-5-sulfydryl-1; 2; 3,4-tetrazolium, thionalid, morpholine, trimeric cyanamide, distearyl amine, stearyl-stearylamide, cyanuric acid, aminotriazole, amino tetrazole and indazole.

Nitrogenous compound for example amine, particularly distearyl amine and ammonium compound for example ammonium chloride, brometo de amonio, ammonium sulfate or two ammonium hydrogenation Citrate trianions also are fit to.The corrosion inhibition immunomodulator compounds of Mn (II)

This detergent tablet can contain the corrosion inhibition immunomodulator compounds of Mn (II).By the weight of composition, Mn (II) compound preferred content is a 0.005%-5% weight, more preferably 0.01%-1%, most preferably 0.02%-0.4%.The incorporation of preferred Mn (II) compound is can provide 0.1ppm-250ppm in any liquid lime chloride, more preferably 0.5ppm-50ppm, the most preferably amount of 1ppm-20ppm weight Mn (II) ion.

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

Mn (II) compound can be organic ligand salt or title complex.In a kind of preferred situation, organic ligand is a heavy metal ion chelating agent.In another preferred situation, organic ligand is a crystal growth inhibitor.Other corrosion inhibition immunomodulator compounds

Other additional corrosion inhibition immunomodulator compounds that are fit to comprise mercaptan and glycol, particularly have the mercaptan of 4-20 carbon atom, comprise lauryl mercaptan, thiophenol, thionaphthol, thionalid and sulfo-anthrol.That also be fit to is saturated or unsaturated C ₁₀-C ₂₀Lipid acid or their salt, particularly Aluminium Tristearate Micronized sterile.C ₁₂-C ₂₀Hydroxy fatty acid or their salt also are fit to.Phosphine acidifying octadecane and other antioxidants, for example β hydroxytoluene (BHT) also is fit to.

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

Being used for the preferred detergent components of another kind of the present invention is hydrocarbon ils, and generally it mainly is that carbonatoms is the long chain aliphatic hydrocarbon of 20-50, and preferred hydrocarbon is saturated and/or side chain, and it mainly is the C of side chain that preferred hydrocarbon ils is selected from _25-45Material, wherein the ratio of ring-type and non-cyclic hydrocarbon is 1: 10-2: 1, preferred 1: 5-1: 1.Preferred hydrocarbon ils is a paraffin.Satisfy the paraffin oil of above-mentioned feature, wherein the ratio of ring-type and non-cyclic hydrocarbon is 32: 68, and by German Wintershall, Salzbergen 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, and by the weight of composition, preferably its content is 0.005%-20%, more preferably 0.01%-5%, most preferably 0.1%-1%.

Water-soluble bismuth compound can be to have any inorganic or organic balanced anionic any bismuth salt or title complex basically.Preferred inorganic bismuth salt is selected from three halogenation bismuths, Bismuth trinitrate and bismuth phosphate.Bismuth acetate and bismuth citrate are to have organic balanced anionic preferably salt.The enzyme stabilising system

The present invention preferably contains enzyme composition can contain 0.001% to 10%, preferred 0.005% to 8%, most preferably the enzyme stabilising system of 0.01% to 6% (weight).The enzyme stabilising system can be any stabilising system compatible with detersive enzyme.This stabilising system can comprise calcium ion, boric acid, propylene glycol, short chain carboxy acid, boric acid, chlorine bleach scavenging agent and their mixture.This stabilising system also can comprise the reversible enzyme inhibitors, for example the reversible proteinase inhibitor.The lime soap dispersing agent compound

Sheet of the present invention can contain the lime soap dispersing agent compound, and by the weight of composition, preferably its content is 0.1%-40%, more preferably 1%-20%, most preferably 2%-10%.

Lime soap dispersing agent is to suppress basic metal, ammonium or the amine salt of lipid acid by calcium or the sedimentary material of magnesium ion.Preferred lime soap dispersing agent compound is disclosed among the PCT application WO93/08877.Press down foam system

Detergent tablet of the present invention preferably comprises a kind of foam system that presses down when being mixed with the composition that is used to machine-wash, by the weight of composition, its content is 0.01-15%, preferred 0.05-10%, more preferably 0.1-5%.

What be used for that the present invention is fit to presses down foam system and can comprise any basically known defoaming compounds, comprises for example polysiloxane defoaming compounds, 2-alkyl and alkanol defoaming compounds.But preferred foam system and defoaming compounds are disclosed among PCT application WO93/08876 and the EP-A-705324.The polymeric dye transfer inhibitor

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

The polymeric dye transfer inhibitor is preferably selected from multipolymer, polyvinylpyrrolidonepolymers polymers or its mixture of polyamine N-oxide pllymers, N-vinyl pyrrolidone and N-vinyl imidazole.White dyes

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

Can be used for hydrophilic white dyes of the present invention and have the following formula structure: R wherein ₁Be selected from anilino, N-2-pair-hydroxyethyl and NH-2-hydroxyethyl; R ₂Be selected from N-2-pair-hydroxyethyl, N-2-hydroxyethyl-N-methylamino-, morpholino, chlorine and amino; With M be salt-forming cation, as sodium or potassium.

In following formula, work as R ₁Be anilino, R ₂Be N-2-two-hydroxyethyl and M are positively charged ions, during as sodium, this whitening agent is 4,4 '-two [(4-anilino-6-(N-2-two-hydroxyethyl)-guanamine-yl) amino]-2,2 '-stilbene disulfonic acid and disodium salt.Such special whitening agent is to be sold by trade(brand)name Tinopal-UNPA-GX merchant by Ciba-Geigy company.Tinopal-UNPA-GX is the preferred hydrophilic white dyes that can be used in the detergent composition of the present invention.

In following formula, work as R ₁Be anilino, R ₂Be that N-2-hydroxyethyl-N-2-methylamino-and M are positively charged ions, during as sodium, this whitening agent is 4,4 '-two [(4-anilino-6-(N-2-hydroxyethyl-N-methylamino-)-guanamine-yl) amino]-2,2 '-stilbene disulfonic acid disodium salt.Such special whitening agent is to be sold by trade(brand)name Tinopal 5BM-GX merchant by Ciba-Geigy company.

In following formula, work as R ₁Be anilino, R ₂Be that morpholino and M are positively charged ions, during as sodium, this whitening agent is 4,4 '-two [(4-anilino-6-morpholino-guanamine-yl) amino]-2,2 '-stilbene disulfonic acid sodium salt.Such special whitening agent is sold by trade(brand)name Tinopal AMS-GX merchant by Ciba-Geigy company.The soft system of clay

The detergent tablet that is applicable to the laundry purging method can contain the soft system of clay, and it contains clay mineral compound and optional clay flocculating agent.

The clay mineral compound is the smectic clays compound preferably.Smectic clays is disclosed among US3862058, US3948790, US3954632 and the US4062647.Procter ﹠amp; European patent EP-the A-299575 of Gamble Company and EP-A-313146 have described suitable organic polymer clay flocculating agent.Cationic fabric softener

Also cationic fabric softener can be incorporated in the present composition that is applicable to clothes washing method.Suitable cationic fabric softener comprises water-insoluble tertiary amine or two long-chain acid amides material, as disclosed among GB-A-1514276 and the EP-B-0011340.

The general total add-on of cationic fabric softener is a 0.5%-15% weight, usually 1%-5% weight.The component that other are optional

Other optional components that are fit to be included in the present composition comprise 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, presses 1% measured in solution in the distilled water, and preferably its pH is 8.0-12.5, more preferably 9.0-11.8, most preferably 9.5-11.5.Machine washing tableware method

Can imagine the method for using any suitable machine washing or cleaning dirty tableware.

Preferred machine washing tableware method comprises that it is selected from pottery, glass wares, silverware, metal products, cutlery and their mixture with the dirty goods of liquid, aqueous processing that dissolve or disperseed significant quantity detergent tablet of the present invention.The detergent tablet meaning of so-called significant quantity refers to the 8-60g product is dissolved or dispersed in the washing soln that volume is 3-10L, and this is to be generally used for the common product dosage in the conventional machine washing method and the volume of washing soln.The weight of preferred detergent tablet is 15g-40g, more preferably 20g-35g.Clothes washing method

Machine washing clothing method of the present invention is usually included in the washing machine with dissolving or has disperseed the machine-wash wash water solution of clothing detergent tablet composition of the present invention of significant quantity to handle dirty clothing.The detergent tablet composition of so-called significant quantity is meant that the product with 40-300g is dissolved or dispersed in the washing soln that volume is 5-65L, and they are common product dosage and the washing soln volumes that are generally used in the conventional machine washing clothing method.

In a kind of preferred application, in washing methods, use distribution device.Distribution device is equipped with Betengent product, is used for before beginning wash(ing)cycle, and product is directly injected the cylinder of washing machine, and its capacity should enable to be equipped with the Betengent product that is generally used for the q.s in the washing method.

In case washing machine is equipped with clothes, the distribution device that contains Betengent product just is placed into cylinder inside.When washing machine begins wash(ing)cycle, in rotating cylinder, add entry, make rotating cylinder carry out Periodic Rotating.The design of distribution device should make and allow to comprise the dry detergent product, discharges this product corresponding to stirring with the cylinder rotation then in cycles of washing, and this also is its result who contacts with washing water.

In order to discharge Betengent product in washing process, device should have the perforate that a plurality of products can pass through.Perhaps, but this device by the sepage body but the material that does not ooze solid phase prod make, allow to discharge the dissolved product.Preferred Betengent product will discharge rapidly when begin wash(ing)cycle, thereby in this cycles of washing stage, provide of short duration high local concentrations product in washing machine drum.

Preferred distribution device is reusable, should be designed so that container all keeps globality in drying regime with in wash(ing)cycle.

Perhaps, distribution device is a deformable container, as bag or pouch.This bag is the fibre object structure, scribbles the protecting materials that do not seep water, thereby can keep content, described in the number of patent application 0018678 of European publication.Perhaps, it can be made by the water-insoluble synthetic polymeric material, provide can be in water-bearing media disruptive sealed edge or seal, described in the patent application publication number 0011500,0011501,0011502 and 0011968 of European publication.The suitable form that seals that chance water easily splits comprises the water-soluble binder that is provided with and seals along sack on one side, and described pouch is by water pressuretightness polymeric membrane, makes as polyethylene or polypropylene.

Embodiment

The abbreviation of using among the embodiment

In detergent composition, below the component symbol definition of abbreviation: STPP: the tripoly phosphate sodium STPP supercarbonate: the sodium bicarbonate citric acid: Citric Acid, usp, Anhydrous Powder carbonate: the Carbon Dioxide sodium silicate: amorphous sodium silicate (SiO ₂: Na ₂O ratio=2.0) SKS-6: formula δ-Na ₂Si ₂O ₅Crystalline layered silicate PB1: anhydrous sodium perborate monohydrate non-ionic type: average degree of ethoxylation be 3.8 and average propoxylation degree be

4.5 C ₁₃-C ₁₅Mixed ethoxylated/propoxylation fat

Alcohol is sold TAED by BASF with trade(brand)name Plurafac merchant: tetra acetyl ethylene diamine HEDP: 1-hydroxyl ethane 1,1-di 2 ethylhexyl phosphonic acid PAAC: five amine cobaltous acetate (III) salt paraffin: by the stone of Wintershall with trade(brand)name Winog70 sale

Wax oil proteolytic enzyme: proteolytic ferment amylase: amylolytic enzyme BTA: benzotriazole vitriol: anhydrous sodium sulphate PEG3000: the polyoxyethylene glycol PEG6000 of the molecular weight of buying by Hoechst about 3000: the polyoxyethylene glycol pH of the molecular weight of buying by Hoechst about 6000: measure by 20 ℃ 1% distilled water solutions

In following examples, all content are to represent by weight:

Embodiment I-IV

Below explanation is applicable to the detergent tablet embodiment of the present invention of wash up.

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 2.40 SKS-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 1.20PEG 6,000 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 0.07PEG 3,000 0.06 0.06 0.06 0.06 0.06 0.06

Amount to 2.0g 2.0g 2.0g 2.0g 2.0g 2.0g

Prepare the multi-phase tablets composition by following program.The washing composition active composition of phase I is by granular and liquid components is mixed, and sends into then to prepare in the mould of conventional rotation forming press.This forming press includes the drift of the formation mould of suitable shape.About 30 * the 38mm of the cross section of this mould.Composition stands 940kg/cm then ²Pressure then rises drift, and its upper surface just exposes first phase of band mould in the detergent tablet.With the washing composition active composition of similar approach preparation phase 2, and send in the mould.Make granular active composition withstanding pressure 170kg/cm then ², rise drift, from tabletting machine, discharge this multi-phase tablets.Dissolving or decomposition are in washing machine in 12 minutes as mentioned above for the sheet that obtains, and second of sheet dissolved in 5 minutes.This sheet has excellent dissolving and cleaning characteristics, has good sheet integrity and intensity.

Claims (18)

1. the heterogeneous detergent tablet of the usefulness of machine-washing, this tablet comprises:

A) have formed body formula first phase of at least one mould; With

B) be compressed on solid granular second phase in the described mould.

2. according to the heterogeneous detergent tablet of claim 1, wherein second with less than about 350kg/cm ²The pressure compacting.

3. the heterogeneous detergent tablet of the usefulness of machine-washing, this tablet comprises:

A) have compression moulding body formula first phase of at least one mould, this formed body is with at least about 350kg/cm ²Pressing force is pressed into; With

B) be compressed on solid granular second phase in the described mould, this is second with less than about 350kg/cm ²Pressure is pressed into.

4. according to each heterogeneous detergent tablet of aforementioned claim, wherein second to compare first phased soln faster.

5. according to each heterogeneous detergent tablet of aforementioned claim, wherein second after 5 minutes, be dissolved in the dishwasher.

6. the heterogeneous detergent tablet of the usefulness of machine-washing, this tablet comprises:

A) have formed body formula first phase of at least one mould; With

B) be compressed on second phase of the solid granular in the described mould.

Wherein this tablet contains at least a detergent active thing, and its manner of formulation will make at least 50%, and preferably at least 60%, more preferably at least 80% (weight) actives in 10 minutes, in preferred 5 minutes, more preferably is transported on the washes in 3 minutes.

7. the heterogeneous detergent tablet of the usefulness of machine-washing, this tablet comprises:

A) have formed body formula first phase of at least one mould; With

B) be compressed on solid granular second phase in the described mould.

Wherein this sheet-like composition contains one or more detergent active things, is selected from enzyme, SYNTHETIC OPTICAL WHITNER, bleach-activating agent, bleaching catalyst, tensio-active agent, sequestrant, crystal growth inhibitor and their mixture, and described actives mainly concentrates in second phase.

8. according to each heterogeneous detergent tablet of aforementioned claim, wherein second also contains cracked dose mutually.

9. according to each heterogeneous detergent tablet of aforementioned claim, wherein second contains enzyme mutually.

10. the heterogeneous detergent tablet of the usefulness of machine-washing, this tablet comprises:

A) have formed body formula first phase of at least one mould; With

B) be compressed on second phase of the solid granular in the described mould, and wherein this second contains enzyme mutually.

11. according to each heterogeneous detergent tablet of aforementioned claim, wherein first and/or second contains tackiness agent mutually.

12. according to the heterogeneous detergent tablet of claim 11, wherein said tackiness agent is selected from sugar and sugar derivatives, starch and starch derivative, inorganic and organic polymer.

13. according to each heterogeneous detergent tablet of aforementioned claim, wherein first and second also contain the obstruct phase between mutually.

14. according to the heterogeneous detergent tablet of claim 13, wherein barrier layer contains the tackiness agent with the liquid form coating.

15. prepare the method for heterogeneous detergent tablet, comprise the following steps:

A) the compacting first washing composition active composition forms first phase that contains mould:

B) with particle form the second washing composition active composition is delivered in the mould; With

C) this granular detergent composition of compacting in mould.

16. according to the method for claim 15, wherein second detergent composition is with less than 350kg/cm ²Pressure be pressed into.

17. the machine washing washing methods comprises that one or more multi-phase detergents with aforementioned arbitrary claim add in the washing machine.

18. according to the method for claim 17, wherein according to the dissolution test method of this paper, this heterogeneous detergent tablet with less than 15 minutes time dissolving or disintegration in dishwasher.