CN1218029C - Detergent tablet - Google Patents

Detergent tablet Download PDF

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Publication number
CN1218029C
CN1218029C CN98809752.4A CN98809752A CN1218029C CN 1218029 C CN1218029 C CN 1218029C CN 98809752 A CN98809752 A CN 98809752A CN 1218029 C CN1218029 C CN 1218029C
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CN
China
Prior art keywords
acid
press portion
preferred
detergent
composition
Prior art date
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Expired - Fee Related
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CN98809752.4A
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Chinese (zh)
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CN1272875A (en
Inventor
B·罗兰德
A·D·麦克格雷戈尔
M·C·阿迪森
L·A·斯佩德
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Procter and Gamble Co
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Procter and Gamble Co
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Application filed by Procter and Gamble Co filed Critical Procter and Gamble Co
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0047—Detergents in the form of bars or tablets
    • C11D17/0065—Solid detergents containing builders
    • C11D17/0073—Tablets
    • C11D17/0078—Multilayered tablets
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0047—Detergents in the form of bars or tablets
    • C11D17/0065—Solid detergents containing builders
    • C11D17/0073—Tablets
    • C11D17/0091—Dishwashing tablets
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/08—Silicates
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/22—Carbohydrates or derivatives thereof
    • C11D3/222—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/38—Products with no well-defined composition, e.g. natural products
    • C11D3/384—Animal products
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/38—Products with no well-defined composition, e.g. natural products
    • C11D3/386—Preparations containing enzymes, e.g. protease or amylase
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39—Organic or inorganic per-compounds

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Zoology (AREA)
  • Inorganic Chemistry (AREA)
  • Molecular Biology (AREA)
  • Emergency Medicine (AREA)
  • Detergent Compositions (AREA)
  • Cosmetics (AREA)
  • Washing And Drying Of Tableware (AREA)
  • Medicinal Preparation (AREA)
  • External Artificial Organs (AREA)

Abstract

The present invention provides a detergent tablet comprising: a) a compressed portion comprising active detergent components; b) a non compressed, non-encapsulating portion comprising active detergent components. Detergent components which are sensitive to compression can be incorporated into tablets and greater control of washing processes can be achieved.

Description

Detergent tablet
Technical field
The invention provides a kind of press portion and detergent tablet not downtrodden, non-encapsulated part of comprising.
Background
Detergent compositions in tablet form is known in the prior art.Can think that detergent compositions in tablet form has several advantages that are better than granular detergent composition, for example handles easily, transports and store.
Detergent tablet is the component by the premix detergent composition and adopt tabletting machine to make sheet the detergent component of premix to prepare the most normally.Sheet normally prepares in flakes by the component compacting with detergent composition.But the applicant has been found that some components of detergent composition can be subjected to being used to making the disadvantageous effect of the pressing pressure of sheet.These components can not be included in advance in the detergent tablet composition and not lose performance.In some cases, this component may be influenced by compacting even to become unstable or loses activity.
In addition, because the component of detergent composition is pressed, this component is closer proximity to each other.The approaching result of component is some component and other component reaction, becomes unstable, loses activity or is consumed.As what seen in the prior art, ways of addressing this issue is to be separated in the component of detergent composition being suppressed the detergent composition that may react each other when in blocks.The separation of component can followingly be finished, for example, the preparation multilayer tablet, wherein the component that may react each other is comprised in the different layers of sheet.Multilayer tablet normally adopts a plurality of pressing steps to prepare.The layer of the sheet that carried out an above pressing step accumulation and whole pressing pressure that may be bigger have been applied.Pressing pressure during known raising compressing tablet can reduce the dissolution rate of sheet, the result, and this multilayer may can not dissolved in use satisfactorily.
The method of other separating, washing agent component is on the books.For example, EP-A-0224135 has put down in writing the dishwashing washing composition that contains warm water dissolved melt form, has suppressed a kind of sheet of cold-water solution therein.The document provides and has comprised two-part detergent composition, and first part dissolves when pre-rinsing, and second section is washed middle dissolving the master of dishwashing.
EP-B-0055100 has described by slow dissolved molding and sheet are merged the washing piece for preparing.This washing piece be intended to be placed in the groove of washroom and in a few days, preferred a few week dissolvings.As control washing piece dissolved method, the document points out to mix one or several dissolving control agents.The example of these dissolving control agents is santochlor, wax, longer chain fatty acid and alcohol and their ester and fatty alkyl acid amides.Be used to do washing or the detergent tablet of dishwashers must dissolving basically in a circulation of washing or dishwashers automatically, as at 30 to 120 minutes.
The applicant have been found that by provide a kind of contain press portion and do not seal, the detergent tablet of press portion not, think that unacceptable detergent component can be incorporated in the detergent tablet concerning detergent tablet before making.In addition, the possible reactive component of detergent composition can effectively be separated.
Another advantage that adopts the detergent tablet of the present invention's record be can obtained performance advantage because when preparing washing agent sheet, if desired, press portion and the speed that press portion can be not different are dissolved.This feature performance benefit can obtain by the activated detergent component is released into detergent solution in the different time selectivity.
Summary of the invention
The invention provides a kind of detergent tablet, this sheet contains:
(a) contain the press portion of activated detergent component; With
(b) contain the activated detergent component not compacting, do not seal part, wherein this detergent tablet contains a kind of enzyme.
In a selectivity embodiment, a kind of detergent tablet also is provided, it contains:
(a) contain the press portion of activated detergent component; With
(b) contain the activated detergent component not compacting, do not seal part, wherein press portion and the weight ratio of press portion not be greater than 0.5: 1, and this detergent tablet contains a kind of silicate.
In another selectivity embodiment, a kind of detergent tablet also is provided, it contains:
(a) contain the press portion of activated detergent component; With
(b) contain the activated detergent component not compacting, do not seal part, wherein press portion and the weight ratio of press portion not be greater than 0.5: 1, and this detergent tablet adopts dissolution rate that the said SOTAX dissolution test method of the present invention measures greater than 0.33 gram/minute.
In another selectivity embodiment, a kind of detergent tablet also is provided, it contains:
(a) contain the press portion of activated detergent component; With
(b) contain the activated detergent component not compacting, do not seal part, wherein the weight of detergent tablet is less than 40 grams, the dissolution rate of detergent tablet adopts dissolution rate that the said SOTAX dissolution test method of the present invention measures greater than 0.33 gram/minute.
In another selectivity embodiment, a kind of detergent tablet also is provided, it contains:
(a) contain the press portion of activated detergent component; With
(b) contain the activated detergent component not compacting, do not seal part, wherein press portion provides and holds the not mould of press portion.
In addition, also provide the method for preparing the said detergent tablet of the present invention.
The present invention relates to the preparation method of detergent tablet, this detergent tablet comprise press portion and not the compacting, non-encapsulated part, this method comprises following step:
A) compacting contains activated detergent component and the composition that is selected from the cracking agent of the agent of bursting apart, pore forming material and their mixture, forms at least one mould in described press portion; With
B) composition that will contain the activated detergent component of solid form is put at least one mould of described press portion, forms at least a compacting, non-encapsulated part,
Wherein said detergent tablet comprises more than a kind of not press portion, and first and second contain with optional follow-up not press portion and to have different average grain particle diameters, make first and second and/or the difference of the average grain particle diameter of follow-up not press portion greater than 5%; And described first and second and optional follow-up not press portion have different density, make first and second and/or the density difference of follow-up not press portion greater than 5%.
The invention still further relates to the preparation method of another kind of detergent tablet, this detergent tablet comprise press portion and not the compacting, non-encapsulated part, this method comprises following step:
A) compacting contains activated detergent component and the composition that is selected from the cracking agent of the agent of bursting apart, pore forming material and their mixture, forms at least one mould in described press portion; With
B) fill at least one mould in the described press portion with the composition of activated detergent component that contains liquid or gel form, forms at least aly suppress, non-encapsulated part.
The method according to this invention, wherein said not press portion comprise that median size is 800 to 1200 microns a particle.
The method according to this invention, wherein press portion and the weight ratio of press portion not be greater than 0.5: 1, and described detergent tablet contains alkalimetal silicate.
The method according to this invention, wherein press portion and the weight ratio of press portion not be greater than 0.5: 1, and described detergent tablet adopts bath temperature to be adjusted at 50 ℃ and agitator to set dissolution rate that the SOTAX dissolution test method that rotates with 250rpm measures greater than 0.33 gram/minute.
The method according to this invention, wherein the weight of detergent tablet is less than 40 grams, and described detergent tablet adopts temperature to be adjusted at 50 ℃ and agitator to set the SOTAX that rotates with 250rpm
The dissolution rate that dissolution test method is measured is greater than 0.33 gram/minute.
The method according to this invention, wherein said detergent tablet further contains enzyme, and wherein said enzyme is selected from amylase, proteolytic enzyme, cellulase, hemicellulase, peroxidase, lipase, Phospholipid hydrolase and their mixture.
The method according to this invention, wherein cracking agent is selected from starch, starch derivative, alginate, carboxymethyl cellulose-based polymkeric substance, sodium-acetate, aluminum oxide, carbonate, supercarbonate, carboxylic acid and their mixture.
The method according to this invention, wherein said detergent tablet further comprises more than a kind of not press portion, first and second contain with optional follow-up not press portion and to have different average grain particle diameters, make first and second and/or the difference of the average grain particle diameter of follow-up not press portion greater than 5%.
The method according to this invention, wherein said first and second and optional follow-up not press portion have different density, make first and second and/or the density difference of follow-up not press portion greater than 5%.
The method according to this invention, wherein said press portion provides a plurality of moulds, and fills each mould with at least a not press portion.
The method according to this invention, wherein at least two in first, second and the optional follow-up not press portion are contained the activated detergent component, have at least in the component one inequality.
The method according to this invention, this method further comprises the subsequent coated step, the wherein not coated coating of at least a portion of press portion is not so that press portion sticks at least one mould of described press portion.
The method according to this invention, wherein said coating contain the component that is selected from lipid acid, alcohol, ester and ether, carboxylic acid, Polyvinylpyrolidone (PVP), poly-acetate, polyoxyethylene glycol and their mixture.
The method according to this invention, wherein said coating contain the component that is selected from glycol, hexanodioic acid, dicarboxylic acid, polyvinyl acetate base ester and their mixture.
The method according to this invention, wherein said coating contain and are selected from: the component of hexanodioic acid, lauric acid, suberic acid, nonane diacid, sebacic acid, undecane diacid, dodecanedioic acid, undecane dicarboxylic acid and their mixture.
The method according to this invention, this method further comprises follow-up set-up procedure, wherein not press portion and/or coating sclerosis.
Detailed Description Of The Invention
According to the present invention, the activated detergent component of detergent tablet of disadvantageous effect that is subjected to being used for the pressing pressure of film-making before having been found that can be included in detergent tablet now.The example of these components comprises SYNTHETIC OPTICAL WHITNER and enzyme.In addition, according to the present invention, have been found that the activated detergent component of detergent tablet can be come separated from one another by containing one or several compatible components and contain one or several compatible components in the not press portion of sheet in the press portion of sheet.Therefore may interact and need the example of isolating component to comprise SYNTHETIC OPTICAL WHITNER, bleach activator or catalyzer and enzyme; SYNTHETIC OPTICAL WHITNER and bleaching catalyst or promoting agent; SYNTHETIC OPTICAL WHITNER and tensio-active agent; Alkali source and enzyme.
In addition, provide compacting with press portion not so that they are dissolved in the washing water with different dissolution raties is favourable.By controlling each part, can control them and be discharged into order in the washing water, and improve the cleaning effect of detergent tablet with respect to the dissolution rate of other parts with by being chosen in the separately activated detergent component of each several part.For example, preferred enzyme is discharged in the washing water prior to SYNTHETIC OPTICAL WHITNER and/or bleach activator usually.Also preferably alkali source is discharged in the washing water quickly than other component of detergent tablet.Can also estimate that the detergent tablet that the release of wherein some component prepared in accordance with the present invention is delayed with respect to other component may be favourable.
It is also envisioned that the part that this sheet can contain a plurality of compactings or not suppress.For example, in multilayer, can arrange a plurality of press portion and/or a plurality of not press portion and can be used as the independent sector existence that is pressed the sheet that partly separates.Therefore, first and second and optional follow-up compacting and/or press portion not can be arranged, each part comprises the activated detergent part, and wherein first can contain the different activated detergent components or the mixture of component with second part at least.The a plurality of compactings of this class or not press portion have to be beneficial to and make the sheet of being produced for example have first and second and optional further part so that they have different dissolution raties.The effect of this performance can obtain by the activated detergent component is discharged in the washing water in the different time selectivity.
The detergent tablet preferred weight of the present invention's record is between 15 grams and 100 grams, more preferably between 18 grams and 80 grams, most preferably between 20 grams and 60 grams.The detergent tablet that the present invention put down in writing that is applicable to automatic dishwashing method most preferably weight between 20 grams and 40 grams.Be applicable to that the detergent tablet in the fabric cleaning process most preferably restrains at 40 grams and 100, more preferably at 40 grams and 80 grams, most preferably between 40 grams and 65 grams.The weight ratio of press portion and press portion not is preferably greater than 1: 1 usually greater than 0.5: 1, more preferably greater than 2: 1, more preferably greater than 3: 1 or even 4: 1, the most preferably at least 5: 1.
The children of detergent tablet of the present invention bite intensity (Child Bite Srrength) into pieces (CBS) generally greater than 10 kilograms, are preferably greater than 12 kilograms, most preferably greater than 14 kilograms.CBS measures according to U.S. Consumer Product Safety Commission's testing standard (U.S.Consumer ProductSafety Commission Test Specification).
Children bite the strength test method into pieces: according to this method, sheet is lain in a horizontal plane between two tinsel/plates.Top plate and following plate make the jaw of this template die apery in a side twisting.On upper plate, apply the downward power of increase, the closed action of imitation jaw, cracked until sheet.The CBS of sheet is the power in the flinders of kilogram.
The dissolution rate of detergent tablet of the present invention is preferably greater than 0.5 gram/minute usually greater than 0.33 gram/minute, more preferably greater than 1.00 gram/minute, most preferably greater than 2.00 gram/minute, the most is preferably greater than 2.73 gram/minute.Dissolution rate adopts SOTAX dissolution rate test determines.Based on purpose of the present invention, the dissolving of detergent tablet adopts SOTAX (trade(brand)name) equipment to obtain, and this equipment is the AT7 type that provided by SOTAX.
The SOTAX dissolution test method: SOTAX equipment comprises temperature controlled water bath with cover.7 jars are suspending in this water-bath.7 electric stirring rod are got off from the inside suspension of lid, in corresponding to water-bath on the position of potentiometer position.The lid of water-bath also can be used as the lid of jar.
The SOTAX water-bath is filled water and temperature is adjusted at 50 ℃.Each jar is put into 1 liter of deionized water and the agitator setting is rotated with 250rpm.Cover the lid of water-bath, with temperature that made deionized water in jar in 1 hour and the water balance in the water-bath.
Sheet is weighed, and in each jar, place a sheet, close the lid.The range estimation sheet dissolves fully until it.Time when documentary film is dissolved fully.The dissolution rate of sheet is calculated with the weight in average (gram) that per minute is dissolved in the sheet in the deionized water.
Press portion
The downtrodden press portion of detergent tablet comprises at least a activated detergent component, but also can comprise the mixture of more than one activated detergent component.Usually all detergent tablet components that can be used in the known detergent tablet all are applicable to the press portion that joins detergent tablet of the present invention.Suitable activated detergent component is described below.Preferred activated detergent component comprises auxiliary compound, tensio-active agent, SYNTHETIC OPTICAL WHITNER, bleach activator, bleaching catalyst, enzyme and alkali source.
Be present in activated detergent component in the neutralizing layer can be randomly with carrier and/or tackiness agent, for example water, polymkeric substance (as PEG), the preparation of silicate solutions bonded form.The activated detergent component preferably prepares with particle (being powder or particle) form, and can be by any known method preparation, for example conventional jet drying, granulation or agglomeration.Then adopt any suitable equipment compressed granulate activated detergent component that is applicable to preparation compressed tablet, bulk, fritter or briquet; Detailed content is documented in hereinafter.
Do not suppress, do not seal part
The compacting do not seal the part (following title is press portion not) contain at least a activated detergent component, also can contain the mixture of more than one activated detergent components.Be applicable to that joining the activated detergent component of press portion not comprises and the interactional component of one or several detergent components that is present in press portion.Particularly, the preferred ingredient of press portion is not that those can be subjected to for example part of the disadvantageous effect of tabletting machine pressing pressure.The example of this class activated detergent component includes, but are not limited to tensio-active agent, SYNTHETIC OPTICAL WHITNER, bleach activator, bleaching catalyst, enzyme, corrosion inhibitor, spices and alkali source.These component write ups hereinafter.These activated detergent components can be any forms, for example particle (being powder or particle), gel or liquid form.Except containing the activated detergent component, press portion also can randomly not contain carrier component.The activated detergent component with can exist with the form of solid, gel or liquid before carrier component combines.
The not press portion of detergent tablet can be solid, gel or liquid form.
Detergent tablet of the present invention needs not press portion to put into press portion, then press portion and not press portion be in contact with one another.Press portion can not put in the press portion with solid or fluid form.When press portion was not solid, it can be prefabricated, and randomly be shaped, and then puts into press portion again.Then press portion is not fixed on the preformed press portion, and is for example bonding or be inserted on the common operating surface of press portion by press portion not.
Preferred press portion contains prefabricated concave portion or mould, wherein can put into not press portion.
Press portion preferably is not placed into press portion with flowable form.Then press portion is not fixed on the press portion, for example by bonding, by not forming coating on the neutralizing layer, to guarantee it and the combining of press portion, perhaps by sclerosis, for example (i) by being cooled to below the fusing point, but flow composition becomes solid-state melt under this fusing point; (ii) pass through evaporating solvent; (iii) by crystallization; (iv) by making the polymeric constituent polymerization that to flow and not suppress component; (v) when flowable not press portion contains polymkeric substance and shear-stress is used for not press portion, by pseudo-plasticity matter; (vi) caking agent is combined with flowable not press portion.In an optional embodiments, flowable not press portion can be the extrudate that is fixed on the press portion, is to fix by for example any above-mentioned mechanism or the parameter by mould that extrudate swelling is provided to press portion.
Preferred this press portion comprises the ready-formed recess or wherein puts into the not mould of press portion (hereinafter being meant ' mould ').In an optional embodiments, the surface of press portion comprises wherein puts into the not mould of press portion more than one.The preferred at least a portion of this mould is held one or several not press portion.Again will be not press portion put into mould and by said fixing in press portion.
Press portion can not contain particle.This particle can be by any known method preparation, for example conventional jet drying, granulation, seals or agglomeration.Particle can be by adding tackiness agent or being fixed on the press portion by form coating on press portion not.
When detergent tablet contained more than one not press portion, first and second can contain with optional follow-up not press portion and to have the particle of different median sizes basically.Basically different median sizes be meant first and second and/or the difference of the average grain particle diameter of subsequent group compound greater than 5% of less median size, be preferably greater than 10%, more preferably greater than 15%, perhaps even 20%.
The average grain granularity that is used for granulated detergent active ingredient of the present invention adopts serial Tyler sieve to calculate.This series comprises a plurality of sieves, and each sieve has different apertures.The sample of the composition of activated detergent component is sieved by sieve series (generally being 5 sieves).Be retained in of the aperture tracing of the weight of the sample composition on the sieve with respect to sieve.The average grain granularity of composition in the aperture of the sieve that the sample composition of 50% weight passes through is.
In another embodiment, first and second and the composition of optional follow-up activated detergent component have different basically density, make first and second and/or the density difference of subsequent group compound greater than 5% of less density, be preferably greater than 10%, more preferably greater than 15% or even 20%.The density of the particulate composition of activated detergent component can be measured by any currently known methods that is suitable for measuring particulate matter density.
The density of the composition of preferred activated detergent component is to adopt a simple funnel and cup device to measure, and cup device is pressed on the base and in its bottom by rigid mould and provides a vacuum breaker so that the conical funnel that the material in the funnel can be emptied in the coaxial cup of placing under the funnel constitutes.This funnel is high 130 millimeters, and its high-end and low side internal diameter is respectively 130 millimeters and 40 millimeters.It is installed and must make low side be higher than 140 millimeters of upper base surface.The height overall of cup is 90 millimeters, and interior height is 87 millimeters, and internal diameter is 84 millimeters.Its nominal volume is 500 milliliters.
Density measurement is by with hand composition impouring funnel being carried out.Funnel one is full, and vacuum breaker is opened, and makes powder pass through funnel, makes a glass overfill.Take off from shelf and to take advantage of full cup, streak its edge, too much powder is removed from cup with straight flange instrument (as cutter).Then will take advantage of full cup to weigh, the powder weight that is obtained on duty 2 obtains the tap density in grams per liter.But replication as required.
One of them or several not press portion comprise particle and first and second and the average grain granularity of optional follow-up not press portion and/or density significantly different sheets be preferred, wherein first and second and optional follow-up not press portion need have different dissolution raties.
When press portion did not comprise solid-state melt, this melt can prepare to form flowable melt to the temperature that is higher than its fusing point by the composition that heating contains detergent active ingredients and optional carrier component.Then, make its cooling with in the flowable melt impouring mould.Along with the melt cooling, it becomes solid, at ambient temperature the shape of delivery.When said composition contained one or several carrier component, this carrier component can be heated to above the temperature of its fusing point, added the activated detergent component again.The carrier component that is suitable for preparing solid-state melt generally is inactive component, and this component can be heated to the above liquid that forms of fusing point, and cooling forms intermolecular matrix, and this matrix can be caught the activated detergent component effectively.Preferred non-active carrier component is to be the solid organic polymer at normal temperatures.Preferred nonactive detergent component is polyoxyethylene glycol (PEG).The press portion of detergent tablet preferably provides the mould that holds this melt.
Flowable not press portion can be the form that comprises the activated detergent component of dissolved or suspension.Can flowing not, press portion can form not press portion of solid, semisolid or highly viscous liquid by above-mentioned any method through sclerosis after a while.Particularly, the press portion that can flow not can be hardened by evaporating solvent.Be applicable to that solvent of the present invention comprises any known solvent of solubilized tackiness agent.Preferred solvent can be a polar or nonpolar, comprises water, alcohol (for example ethanol, acetone) and alcohol derivate.In a selectivity embodiment, can adopt more than one solvent.
Flowable not press portion can comprise one or several tackiness agents.Estimate anyly to have the tackiness agent that makes composition become solid, semisolid or high viscosity effect and all can be used for the present invention through the time.Although be not intended to be limited by theory, can think that still the mechanism that tackiness agent makes non-solid composition become solid, semisolid or high viscosity comprises: but the chemical reaction (for example chemically crosslinked) between in the flow composition two kinds or several component or interact; The chemistry of tackiness agent and composition component or physical action.Preferred adhesive comprises sugar/gel combination, starch, glycerine and organic polymer.Sugar can be any monose (as glucose), disaccharides (as sucrose or maltose) or polysaccharide.Most preferred sugar is common available sucrose.Based on purpose of the present invention, can adopt A type or Type B gel, for example provide by Sigma.A type gel is preferred, and this is because it has higher stability with comparing of Type B under alkaline condition.The frosting intensity of preferred gel is 65 to 300, most preferably 75 to 100.Preferred organic polymer comprises that molecular weight is 500 to 10000, and is preferred 750 to 8000, and most preferably 1000 to 6000 polyoxyethylene glycol (PEG) is provided by Hoechst.
When press portion was not extrudate, this extrudate can be made viscous pastes by premix activated detergent component and optional carrier component and prepare.Then adopt any suitable normally used extrusion device that this viscous pastes is extruded, install for example by APV BakerPeterborough simple helix that U.K. provides or duplex forcing machine.Then extrudate is cut off granulating after delivering to the press portion of detergent tablet or before delivering to press portion.The press portion of this sheet preferably includes the mould that the not press portion of extruding can be delivered to wherein.
In a preferred embodiment, press portion does not apply with coating.This coating can be used for press portion not is fixed on the press portion.When but press portion did not comprise flow particles, gel or liquid, this was particularly advantageous.
This coating is preferably included in and preferably is less than 15 minutes, more preferably less than 10 minutes, further preferably is less than 5 minutes, most preferably be less than in time of 60 seconds kinds by the contact compacting and/or not press portion become the solid material.Preferred this coating is water miscible.Preferred coatings comprises the material that is selected from lipid acid, alcohol, glycol, ester and ether, hexanodioic acid, carboxylic acid, dicarboxylic acid, polyvinyl acetate base ester (PVA), Polyvinylpyrolidone (PVP) (PVP), poly-acetate (PLA), polyoxyethylene glycol (PEG) and their mixture.Preferred carboxylic acid or dicarboxylic acid preferably contain the even carbon atom.Preferred carboxylic acid or dicarboxylic acid contain at least 4, and more preferably at least 6, further preferably at least 8,8 to 13 carbon atoms most preferably.Preferred dicarboxylic acid comprises hexanodioic acid, suberic acid, nonane diacid, sebacic acid, undecane diacid, dodecanedioic acid, undecane dicarboxylic acid and their mixture.Preferred lipid acid is that carbon chain lengths is C12-C22, and most preferably C18 is to the lipid acid of C22.Coating also preferably contains cracking agent.When having coating, its amount is generally at least 0.05% of detergent tablet, and preferably at least 0.1%, more preferably at least 1%, most preferably at least 2%, perhaps even at least 5%.
As a selectivity embodiment, coating can be sealed detergent tablet.In this embodiment, the amount of coating is at least 4% of a detergent tablet, more preferably at least 5%, most preferably at least 10%.
In a preferred embodiment, press portion and/or press portion and/or coating also do not contain cracking agent.This cracking agent can be disintegrating agent or pore forming material.Suitable disintegrants comprises contacting with water and expands or by in press portion and/or do not form passage in the press portion and the water capacity is easily flow to and/or effusive reagent.Any be applicable to the laundry or the dishwashing purposes in known disintegrating agent or pore forming material all can be used for the present invention.Suitable disintegrants comprises starch, starch derivative, alginate, carboxymethyl cellulose (CMC), the polymkeric substance of CMC base, sodium-acetate, aluminum oxide.Suitable pore forming material is to contact those that produce bubble with water.Suitable pore forming material can be the material of emitting oxygen, nitrogen peroxide or carbonic acid gas.The example of preferred pore forming material can be selected from perborate, percarbonate, carbonate, supercarbonate and carboxylic acid, for example citric acid and toxilic acid.
The advantage that comprises cracking agent in detergent tablet of the present invention is the advantage aspect transportation, storage and the processing, and this can pass through to improve the hardness of detergent tablet, and does not have the disadvantageous effect cleaning effect to obtain.
Method
The invention provides a kind of method of preparing washing agent sheet, comprise following step:
A) compacting activated detergent component is made press portion; With
B) the not compacting that will comprise the activated detergent component is not sealed part and is put into press portion.
As mentioned above, detergent tablet of the present invention is to form the corresponding press portion and the composition of the activated detergent component of press portion not by preparation respectively, again the general not the composition of press portion put into or stick to and prepare on the press portion.
Press portion is by obtaining at least a activated detergent component and randomly preparing with the carrier component premix.All premixs can carry out in suitable mixing machine, for example pan type mixer, rotary drum, vertical mixer or high shear mixer.Preferably will do grain fraction and in aforesaid mixing machine, mix, and liquid ingredient will be used for doing grain fraction, for example do on the grain fraction by liquid ingredient is directly injected to.Then adopt any known suitable equipment to be configured as press portion at pressing step the composition that generates.The preferred tabletting machine that adopts is configured as press portion with said composition, and wherein sheet is by composition is prepared between upper punch and lower punch.In a preferred embodiment of the invention, said composition is placed in the punch press chamber of tabletting machine, adopts to be preferably greater than 6.3KN/cm 2, more preferably greater than 9KN/cm 2, most preferably greater than 14.4KN/cm 2Pressure be pressed into press portion.
In order to prepare preferred sheet of the present invention, wherein press portion provides and receives the not mould of press portion, and press portion adopts improved tabletting machine to prepare, and this improved tabletting machine comprises improved upper punch and/or lower punch.The upper punch and the lower punch of this improved tabletting machine are modified, so that press portion provides one or several to form toward wherein putting into the not indent of the mould of press portion.
Press portion does not comprise at least a activated detergent component.When press portion does not contain more than one activated detergent components, adopt any known suitable these components of mixing equipment premix.In addition, press portion can randomly not contain a kind of and activated detergent component blended carrier.Press portion can not be made into solid or the part that can flow.Composition one prepares, and just puts into press portion.Press portion can or not adopt nozzle charging machine or forcing machine to put into press portion by artificial conveyance.When press portion has mould, preferably adopt accurate handling equipment not press portion put into mould, nozzle charging machine for example, the weightless self-conveyor feed or the forcing machine that provide as Optima by Germany.
When flowable not when press portion is particle form, this method comprises puts into press portion with flowable not press portion at supplying step, then apply not at least one part of press portion, press portion is not sticked to effect on the press portion basically so that coating has with coating.
When flowable not press portion was fixed on the press portion by sclerosis, this method comprised a supplying step, and in this step, flowable not press portion is placed into press portion, and a follow-up regulating step, wherein not press portion sclerosis.This regulating step can comprise the drying, cooling of press portion not, bonding, polymerization etc., and in this process, press portion does not become solid-state, semi-solid state or high viscosity.Can heat at drying step.Can heat or be exposed to radiation and in polymerization procedure, finish polymerization.
Can also estimate that press portion can be prepared into has a plurality of moulds.Then a plurality of moulds are filled up not press portion.Can also estimate that each mould can be filled up by different not press portion, perhaps optionally each mould is filled up by a plurality of different not press portion.
The activated detergent component
The press portion of detergent tablet of the present invention can prepare by the composition of compacting activated detergent component.Suitable composition can comprise various detergent active ingredients, comprises auxiliary compound, tensio-active agent, enzyme, SYNTHETIC OPTICAL WHITNER, alkali source, tinting material, spices, lime soap dispersion agent, organic polymer (comprising the polymeric dye transfer inhibitor), crystal growth inhibitor, heavy metal ion chelating agent, metal cation salt, enzyme stabilizers, corrosion inhibitor, fouling inhibitor, solvent, fabric softener, white dyes and hydrotropic agent.
Activated detergent component very preferably comprises auxiliary compound, tensio-active agent, enzyme and SYNTHETIC OPTICAL WHITNER.
Auxiliary compound
Detergent tablet of the present invention preferably contains auxiliary compound, and content is generally 1% to 80% weight of the composition of activated detergent component, and is preferred 10% to 70%, most preferably 20% to 60% weight.
The water-soluble additive compound
Suitable water-soluble additive compound comprises water-soluble monomer polycarboxylate or the poly carboxylic acid of their sour form, homopolymerization or copolymerization or their salt, wherein poly carboxylic acid comprises two hydroxy-acid groups that separated by no more than two carbon atom at least, and carbonate, supercarbonate, borate, phosphoric acid salt and above-mentioned any mixture of ingredients.
Carboxylate salt or polycarboxylate auxiliary agent can be haplotype or the oligomerization type, although monomeric polycarboxylates is owing to the reason of price and performance is normally preferred.
The suitable carboxylate salt that contains a carboxyl comprises the water-soluble salt of lactic acid, oxyacetic acid and its ether derivant.The polycarboxylate that contains two carboxyls comprises the water-soluble salt of Succinic Acid, propanedioic acid, (ethylenedioxy) oxalic acid, toxilic acid, diethyl alkyd, tartrate, tartronic acid and fumaric acid and ether carboxylate and sulfinyl carboxylate salt.The polycarboxylate that contains three carboxyls is particularly including water miscible Citrate trianion, aconitate and citraconate, and succinate derivative, for example be documented in carboxymethyl oxygen succinate in the English Patent 1379241, be documented in lactoyl oxygen succinate in the English Patent 1389732, be documented in amino-succinic acid salt and oxygen polycarboxylate material in the HOII P 7205873,2-oxo-1 for example, 1,3-tricarballylic acid salt, as be documented in the English Patent 1387447.
The polycarboxylate that contains four carboxyls comprises oxygen two succinates, 1,1,2 that are disclosed in the English Patent 1261829,2-ethane tetracarboxylic acid hydrochlorate, 1,1,3,3-propane tetracarboxylic acid salt and 1,1,2,3-propane tetracarboxylic acid salt.Contain the substituent polycarboxylate of sulfo group comprise be disclosed in English Patent 1398421 and 1398422 and US3936448 in sulfosuccinate derivant, and be documented in sulfonated pyrolytic Citrate trianion in the English Patent 1439000.
Alicyclic ring and heterocyclic polycarboxylate comprise pentamethylene-suitable, suitable, suitable-tetracarboxylic acid hydrochlorate, cyclopentadiene penta carboxylate 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 polyhydroxy-alcohol is as the carboxyl methyl-derivatives of sorbyl alcohol, mannitol and Xylitol.The fragrance polycarboxylate comprises mellitic acid, petroleum benzene pregnancy acid and phthalic acid derivatives, is disclosed in the English Patent 1425343.
Wherein preferred polycarboxylate is the hydroxycarboxylate, and its per molecule contains maximum three carboxyls, more especially Citrate trianions.
Female acid of monomer or oligomeric polycarboxylate sequestrant or with the mixture of their salt, also can be used as effective adjuvant component as citric acid or Citrate trianion/citric acid mixture.
Also can adopt the borate auxiliary agent and contain washing composition store or wash conditions under can produce the boratory auxiliary agent that forms boratory material, but be lower than 50 ℃, it is not preferred particularly being lower than under 40 ℃ the wash conditions.
The example of carbonate auxiliary agent is alkaline-earth metal and alkaline carbonate, comprises the mixture of yellow soda ash and concentrated crystal soda and they and calcium carbonate superfine powder, as is disclosed in German patent application in 15,2321001,1973 on November.
Very preferably being used for auxiliary compound of the present invention is the water-soluble phosphoric acid salt assitant.The object lesson of water-soluble phosphoric acid salt assitant is an alkali metal tripolyphosphates, the sodium of tetra-sodium, potassium and ammonium salt, and the sodium of tetra-sodium, potassium and ammonium salt, the sodium of former phosphoric acid and sylvite, wherein extent of polymerization is 6 to 21 the salt that gathers inclined to one side/sodium phosphate and phytinic acid.
The object lesson of water-soluble phosphoric acid salt assitant is an alkali metal tripolyphosphates, the sodium of tetra-sodium, potassium and ammonium salt, and the sodium of tetra-sodium, potassium and ammonium salt, the sodium of former phosphoric acid and sylvite, wherein extent of polymerization is 6 to 21 the salt that gathers inclined to one side/sodium phosphate and phytinic acid.
Solvable or the insoluble auxiliary compound of part
Detergent tablet of the present invention can contain the solvable or insoluble auxiliary compound of part.Solvable and the insoluble auxiliary compound of part is specially adapted to be the prepared sheet of laundry cleaning method.The example that is partially soluble in the auxiliary agent of water comprises crystalline layered silicate, as for example is disclosed among EP-A-0164514, the DE-A-3417649 and DE-A-3742043.The crystalline layered sodium silicate that preferred formula is following:
NaMSixO 2+1·yH2O
Wherein M is sodium or hydrogen, and x is from 1.9 to 4 number, and y is 0 to 20 number.This class crystalline layered sodium silicate preferably has two dimension " sheet " structure, as so-called δ-laminate structure, puts down in writing as EP0164514 and EP0293640.
The method for preparing this class crystalline layered silicate is disclosed among DE-A-3417649 and the DE-A-3742043.Based on purpose of the present invention, x has 2,3 or 4 value in above-mentioned general formula, and preferred 2.
The general formula of most preferred crystalline layered sodium silicate compound is δ-Na 2Si 2O 5, known is NaSKS-6 (trade name), is provided by Hoechst AG.
In granular detergent composition, the crystalline layered sodium silicate material preferably with the intimate mixture of solid, water-soluble ionizable material in particle, as be documented among the PCT patent application WO92/18594.The ionizable material of solid, water soluble is selected from organic acid, organic and inorganic acid salt and their mixture, optimization citric acid.
Basically the example of water-fast auxiliary agent comprises sodium aluminium silicate.Suitable aluminosilicate comprises the manosil AS zeolite, and its elementary cell general formula is Na z[(AlO 2) z(SiO 2) y] .xH 2O, wherein z and y are at least 6; The mol ratio of z and y is 1.0 to 0.5, and x is at least 5, is preferably 7.5 to 276, more preferably 10 to 264.Aluminosilicate be hydrated form and crystal preferably, contain 10% to 28%, more preferably 18% to 22% combination water.
Aluminosilicate zeolites can be spontaneous material, also synthetic preferably.Synthetic crystalline aluminosilicate ion exchange material is that the title with zeolite A, zeolite B, zeolite P, X zeolite, zeolite HS and their mixture provides.
The preferred method of preparation aluminosilicate zeolites is described by (being disclosed in Zeolite (1994), 14 (2), 110～116) such as Schoeman, and wherein the author has described a kind of method for preparing the colloidal aluminum silicate zeolite.This colloidal aluminum silicate zeolite particle preferably is no more than 5% particle grain size greater than 1 micron, is no more than 5% particle grain size less than 0.05 micron.Preferred aluminosilicate zeolites particulate average grain particle diameter is at 0.01 micron to 1 micron, and more preferably 0.05 micron to 0.9 micron, most preferably 0.1 micron to 0.6 micron.
Zeolite A has general formula:
Na 12[(AlO 2) 12(SiO 2) 12].xH 2O
Wherein X is 20 to 30, particularly 27.The general formula of X zeolite is Na 86[(AlO 2) 86(SiO 2) 106] .276H 2O.The zeolite MAP that is disclosed in EP-B-384070 is the preferred zeolite builder of the present invention.
Preferred aluminosilicate zeolites is the colloidal aluminum silicate zeolite.When adopting the colloidal aluminum silicate zeolite, particularly during colloidal zeolite A, providing improved additive performance aspect the clean effect improving as the component of detergent composition.Improved additive performance also can be from reducing the fabric crust and improving fabric whiteness persistence aspect and see; It is relevant with composite relatively poor detergent composition that these problems all are considered to.
Wonderful discovery be contain the aluminum mixture silicate zeolite detergent composition of colloidal zeolite A and colloidal zeolite Y can provide with etc. the calcium ion chelating effect of the zeolite A equivalence used of weight industry.Another wonderful discovery be above-mentioned blended aluminosilicate zeolites detergent composition provide with etc. the industrial zeolite A that provides of weight compare the magnesium ion chelating effect of having improved.
Tensio-active agent
Tensio-active agent is the preferred detergent active ingredients of the present composition.Suitable tensio-active agent is selected from negatively charged ion, positively charged ion, nonionic, both sexes and zwitterionics and their mixture.Automatically the dishwashers product should have low foamy character, so, must suppress to be used for the surfactant system foaming of dishwashing method, perhaps be more preferably low foamy, normally the nonionic feature.The foaming that will be caused by the surfactant system of the cleaning method that is used for doing washing is not suppressed to the required degree of dishwashing.The content of tensio-active agent is 0.2% to 30% weight of the composition of activated detergent component normally, more preferably 0.5% to 10% weight, most preferably 1% to 5% weight.
The kind of the negatively charged ion of listing usually, nonionic, both sexes and zwitterionic classes and these tensio-active agents is documented in USP3929678, Laughlin and Heuring, on December 30th, 1975.The catalogue of suitable cationic surfactants is documented in USP4259217, Murphy, on March 31st, 1981.The catalogue that is usually included in the tensio-active agent in the automatic dishwashing detergent composition is documented in EP-A-0414549 and PCT application WO9 3/08876 and WO93/08874.
Nonionogenic tenside
Basically all nonionogenic tensides that can be used for washing purposes all can be included in the detergent tablet.Effective nonionogenic tenside of the indefiniteness kind of preferably listing below.
The nonionic ethoxylated alcohol tensio-active agent
The alkyl ethoxylated condensation product of Fatty Alcohol(C12-C14 and C12-C18) and 1 to 25 moles of ethylene oxide is applicable to the present invention.The alkyl chain of Fatty Alcohol(C12-C14 and C12-C18) can be linearity or collateralization, uncle or secondary chain, and contain 6 to 22 carbon atoms usually.Particularly preferably be that alcohol and the every mol of alcohol that contains the alkyl of 8 to 20 carbon atoms is the condensation product of 2 to 10 moles oxyethane.
The end-blocking alkyl alkoxylated surfactants
The alkyl alkoxylated tensio-active agent of suitable end-blocking is end capped poly-(o-alkylation) alcohol of epoxy group(ing), and its general formula is as follows:
R 1O[CH 2CH(CH 3)O] x[CH 2CH 2O] y[CH 2CH(OH)R 2] (I)
Wherein R1 has the linearity of 4 to 18 carbon atoms or the aliphatic group of collateralization; R2 has the linearity of 2 to 26 carbon atoms or the aliphatic group of collateralization; X is that mean value is 0.5 to 1.5 integer, more preferably 1; Y is at least 15 integer, and more preferably at least 20.
Preferably in the tensio-active agent of general formula I, epoxide unit [CH endways 2CH (OH) R 2] at least 10 carbon atoms are arranged.According to the present invention, the tensio-active agent that general formula I is suitable is an Olin Corporation ' s POLY-TERGENT  SLF-18B nonionogenic tenside, as is documented in for example WO94/22800, is disclosed on October 13rd, 1994 by Olin Corporation.
Ether capped poly-(o-alkylation) alcohol
Be used for preferred surfactant of the present invention and comprise ether capped poly-(o-alkylation) alcohol, its general formula is:
R 1O[CH 2CH(R) 3O] x[CH 2] kCH(OH)[CH 2] jOR 2
R wherein 1And R 2Be have the linearity of 1 to 30 carbon atom or collateralization, saturated or undersaturated, fat or aromatic hydrocarbon group; R 3Be H, the perhaps linear aliphatic hydrocarbyl group of 1 to 4 carbon atom; X is that mean value is 1 to 30 integer, and wherein x is 2 or when bigger, R3 can be identical or different, and k and j are that mean value is 1 to 12 integer, more preferably 1 to 5.
R 1And R 2Preferably the linearity of 6 to 22 carbon atoms, preferred 8 to 18 carbon atoms or collateralization, saturated or undersaturated, aliphatic hydrocarbon or aromatic hydrocarbon group.The linear aliphatic hydrocarbyl group of H or 1 to 2 carbon atom is to R 3Be most preferred.X is the integer of average out to 1 to 20 preferably, and more preferably 6 to 15.
As mentioned above, in preferred embodiments, when x greater than 2 the time, R 3Can be identical or different.That is R, 3Can between above-mentioned all alkylene oxide group unit, change.For example, if x is 3, R 3Can be selected from inferior ethoxyl (EO) or inferior propoxy-(PO), and order can be (EO) (PO) (EO) (EO) (EO) (PO), (PO) (PO) (EO) and (PO) (PO) (PO) of (EO), (PO) of (PO), (EO) of (EO), (EO).Certainly, select 3 just for example, have bigger round values for x, changing can be more, for example, and a plurality of (EO) unit and still less (PO).
Above-mentioned particularly preferred tensio-active agent comprises that cloud point is less than those of 20 ℃.The tensio-active agent of these low cloud points can be used in combination with the high cloud point tensio-active agent of describing in detail below, be used for high fat cleaning effect.
Preferred ether capped poly-(o-alkylation) pure tensio-active agent be wherein k be 1 and j be 1 those, so this tensio-active agent has following general formula:
R 1O[CH 2CH(R 3)O] xCH 2CH(OH)CH 2OR 2
R wherein 1, R 2And R 3Identical with above-mentioned qualification, x is the integer of average out to 1 to 30, and is preferred 1 to 20, more preferably 6 to 18.Most preferably be wherein R1 and R2 9 to 14, R 3Be that H formation inferior ethoxyl, x are 6 to 15 tensio-active agents.
Ether capped poly-(o-alkylation) pure tensio-active agent contains three kinds of conventional components, i.e. the alcohol of linearity or collateralization, alkylene oxide and alkyl oxide end-blocking.Alkyl oxide end-blocking and alcohol play the effect of the molten part of hydrophobic oil of molecule, and alkylene oxide group forms the hydrophilic water-soluble part of molecule.
These tensio-active agents are compared with conventional surfactants, when being used in combination with high cloud point tensio-active agent, can improve point sample and film forming characteristics greatly and the performance that removes grease.
In general, ether capped poly-(oxyalkylene) pure tensio-active agent of the present invention can be prepared as follows: Fatty Alcohol(C12-C14 and C12-C18) and epoxide reaction are generated ether, then, itself and alkali reaction are generated second kind of epoxide.With second kind of epoxide and oxyalkylated alcohol reaction, generate new compound of the present invention again.The example for preparing the method for ether capped poly-(o-alkylation) pure tensio-active agent is described below.
Preparation C 12 / 14 Alkyl glycidyl ether
Mixed C in 500 milliliters of three mouthfuls of round-bottomed flasks that are equipped with prolong, argon gas import, feed hopper, magnetic stirring apparatus and internal temperature probe 12/ 14Fatty Alcohol(C12-C14 and C12-C18) (100.00 grams, 0.515 mole) and tin chloride (IV) (0.58 gram, 2.23 mmoles are provided by Aldrich).With this mixture heating up to 60 ℃.Drip Epicholorohydrin (47.70 grams, are provided by Aldrich by 0.515 mole), to maintain the temperature at 60～65 ℃.After 60 ℃ of restir 1 hour, with the mixture cool to room temperature.Handle this mixture with 50% sodium hydroxide solution (61.80 grams, 0.773 mole, 50%), carry out mechanical stirring simultaneously.After adding, this mixture 90 ℃ of heating 1.5 hours, is cooled off, and filter by means of ethanol.Separating filtrate, water (100 milliliters) washing organic phase is used MgSO 4Drying is filtered and is concentrated.At 100～120 ℃ of distillation this oil (0.1 mmhg), obtain the oily glycidyl ether.
Preparation C 12 / 14 Alkyl-C 9 / 11 Ether capped pure tensio-active agent
Neodol  91-8 (20.60 grams, 0.0393 mole of ethoxylated alcohol that provides by Shell chemical Co.) and tin chloride (IV) (0.58 restrain, 2.23 mmoles) are provided in 250 milliliters of three mouthfuls of round-bottomed flasks that are equipped with prolong, argon gas import, feed hopper, magnetic stirring apparatus and internal temperature probe.With this mixture heating up to 60 ℃, under this temperature with dripping C12/14 alkyl glycidyl ether (11.00 grams, 0.0393 mole) in 15 minutes.After 60 ℃ of restir 18 hours, with the mixture cool to room temperature and be dissolved in the methylene dichloride of equivalent.With the silicon-dioxide silica gel backing plate of this solution, use eluent methylene chloride simultaneously by 1 inch.Adopt the rotary evaporator concentrated filtrate, stripping in stove (100 ℃, 0.5 mmhg) generates the oily surface promoting agent again.
The nonionic ethoxylated/propoxylated fatty alcohol surfactant
The C of ethoxylation 6-C 18Fatty Alcohol(C12-C14 and C12-C18) and C 6-C 18Mixed ethoxylated/propoxylated fatty alcohol is to be applicable to tensio-active agent of the present invention, and is particularly water miscible.The Fatty Alcohol(C12-C14 and C12-C18) of preferred ethoxylation is that degree of ethoxylation is 3 to 50 C 10-C 18Ethoxylized fatty alcohol, most preferably those degree of ethoxylation are 3 to 40 C 12-C 18Ethoxylized fatty alcohol.The alkyl chain of preferred mixed ethoxylated/propoxylated fatty alcohol is 10 to 18 carbon atoms, and degree of ethoxylation is 3 to 30, and degree of propoxylation is 1 to 10.
Nonionic EO/PO condenses with propylene glycol
Oxyethane is applicable to the present invention with the condensation product of the hydrophobic alkali that generates by condensation propylene oxide and propylene glycol.The hydrophobic part preferred molecular weight of these compounds is 1500 to 1800, and water insoluble.Some industrial Pluronic that provides is provided the example of this compounds TMTensio-active agent is provided by BASF.
Nonionic EO condensation product with propylene oxide/ethylenediamine adduct
Oxyethane is applicable to the present invention with the condensation product of the product that is generated by propylene oxide and reacting ethylenediamine.The hydrophobic part of these products has constituted the reaction product of quadrol and excessive oxidation propylene, and molecular weight is generally 2500 to 3000.The example of this class nonionogenic tenside comprises some industrial available Tetronic TMCompound is provided by BASF.
The blended nonionic surfactant system
In a preferred embodiment of the invention, detergent tablet contains the blended nonionic surfactant system, and this system contains at least a low cloud point non-ionic surfactants and at least a high cloud point non-ionic surfactants.
" cloud point " is meant the known properties of nonionogenic tenside in the present invention, it is a tensio-active agent along with the result that the rising solvability of temperature diminishes, can be observed the temperature that second phase occurs and be meant that " cloud point " is (referring to Kirk Othmer ' s Encyclopedia of ChemicalTechnology, 3rd Ed.vol.22, pp.360～379).
As of the present invention, " low cloud point " nonionogenic tenside be meant cloud point less than 30 ℃, preferably less than 20 ℃, be more preferably less than 10 ℃ nonionic surfactant system component.Typical low cloud point non-ionic surfactants comprises the oxyalkylated tensio-active agent of nonionic, the contrary block polymer of the particularly b-oxide that is produced by primary alconol, and polyoxypropylene/polyoxyethylene/polyoxypropylene (PO/EO/PO).The low cloud point non-ionic surfactants of this class for example comprises also that ethoxylation-propenoxylated alcohol (as Olin Corporation ' s Poly-Tergent  SLF18), oxyethyl group end capped poly-(o-alkylation) alcohol are (as the nonionogenic tenside of OlinCorporation ' s Poly-Tergent  SLF18B series, for example be documented in WO94/22800, be disclosed on October 13rd, 1994 by Olin Corporation) and ether capped poly-(o-alkylation) pure tensio-active agent.
Nonionogenic tenside can randomly contain the propylene oxide of 15% weight at the most.Other preferred nonionic can be by being documented in the method preparation among the US4223163, and this patent is obtained power on September 16th, 1980 by Buiiloty, and the document in this combination as a reference.
Low cloud point non-ionic surfactants contains polyoxyethylene, polyoxypropylene block polymer in addition.Block polyoxyethylene-polyoxypropylene polymer comprises based on ethylene glycol, propylene glycol, glycerine, three hydroxyl methoxy-propanes and quadrol as those of initiator activity hydrogen compound.The block polymer surfactant compounds that some commodity that provided by BASF-Wyandotte Corp. are called PLURONIC , REVERSEDPLURONIC  and TETRONIC  is applicable to ADD composition of the present invention.Preferred example comprises REVERSED PLURONIC  25R2 and TETRONIC  702, and this class tensio-active agent is usually in the present invention as low cloud point non-ionic surfactants.
As of the present invention, " high cloud point " nonionogenic tenside be meant cloud point be higher than 40 ℃, preferably be higher than 50 ℃, most preferably be higher than 60 ℃ nonionic surfactant system component.Preferred this nonionic surfactant system contains the tensio-active agent by the ethoxylation of the MHA that contains 8 to 20 carbon atoms or alkylphenol and average every mol of alcohol or alkylphenol 6 to 15 moles of ethylene oxide reaction generation.The high cloud point non-ionic surfactants of this class comprises, for example Tergitol 15S9 (being provided by Union Carbide), RhodasurfTMD8.5 (being provided by Rhone Poulenc) and Neodol 91-8 (being provided by Shell).
Based on purpose of the present invention, the hydrophile-lyophile balance of preferred high cloud point non-ionic surfactants (" HLB " also; Referring to Kirk Othmer above) value is 9 to 15, in preferred 11 to 15 scopes.For example Tergitol 15S9 (being provided by Union Carbide), Rhodasurf TMD8.5 (being provided by Rhone Poulenc) and Neodol 91-8 (being provided by Shell) are provided this class material.
Another kind of preferred high cloud point non-ionic surfactants is by containing 6 to 20 carbon atoms linear or preferred collateralization chain or secondary Fatty Alcohol(C12-C14 and C12-C18) (C 6-C 20Alcohol) produce, comprise secondary alcohol and collateralization chain primary alconol.Preferred high cloud point non-ionic surfactants is and average 6 to 15 moles of every mol of alcohol, preferred 6 to 12 moles, the collateralization or the secondary alcohol b-oxide of most preferably 6 to 9 moles of ethylene oxide condensations, more preferably blended C9/11 or C11/15 collateralization alcohol b-oxide.The nonionogenic tenside of preferred ethoxylation of making like this distributes with respect to having narrow b-oxide on average.
In preferred embodiments, the detergent tablet that contains such mixed surfactant system also contains a certain amount of water-soluble salt, measure greater than 3 Siemens/ centimetre of milli to be provided in 25 ℃ of deionized waters, be preferably greater than 4 Siemens/ centimetre of milli, more preferably greater than the electric conductivity of Siemens/ centimetre of 4.5 milli, as (attorney's number of documents is CM1573F) put down in writing in the pending application GB patent application.
In a further preferred embodiment, the blended surfactant system be dissolved in hardness in all cold year automatic washing machines that are suitable for be 1.246 mmoles/liter water in, generate surface tension below 45 ℃, preferred below 40 ℃, more preferably under the temperature below 35 ℃ less than 4 dyne/cm 2Solution, as be documented in (attorney's number of documents 6252) in the U.S. Patent application.
In a further preferred embodiment, separate high cloud point and low cloud point tensio-active agent in the mixed surfactant system, so that a kind of being present in first matrix in high cloud point or the low cloud point tensio-active agent, another is present in second matrix, as being put down in writing in the US patent application (attorney's number of documents is 6252).Based on purpose of the present invention, first kind of matrix can be first kind of particle, and second kind of matrix can be second kind of particle.Tensio-active agent can be used for particle by any suitable method, preferably tensio-active agent is sprayed onto on the particle.One preferred aspect, first kind of matrix is the press portion of detergent tablet of the present invention, second kind of matrix is press portion not.Preferred low cloud point tensio-active agent is present in the press portion of detergent tablet of the present invention, and high cloud point tensio-active agent is present in the not press portion of detergent tablet of the present invention.
Anion surfactant
All anion surfactants basically that can be used for washing purpose all are suitable for.They comprise the salt of anion sulfate, sulfonate, carboxylate salt and musculamine acid salt surfactant (ammonium salt that for example comprises sodium, potassium, ammonium and replacement, for example one, two and triethanolamine salt).The anion sulfate acid salt surfactant is preferred.
Other anion surfactant comprises isethionate (isothionates), as fatty acid amide, alkyl succinate and sulfosuccinate, sulfosuccinic acid monoesters (the particularly saturated and undersaturated C of acyl isethinate, N-acyl taurine salt, methyl tauryl amine (tauride) 12-C 18One ester), the diester of sulfo-succinic acid (particularly saturated and undersaturated C 6-C 14Diester), N-acyl group musculamine hydrochlorate.Resinous acid and hydrogenant resinous acid also are suitable, for example sylvic acid, hydrogenant sylvic acid, and the resinous acid and the hydrogenant resinous acid that are present in or result from tallow oil.
The anion sulfate acid salt surfactant
Be applicable to primary and secondary alkyl-sulphate, alkyl ethoxy sulfate, fatty oil acylglycerol vitriol, alkylphenol oxyethane ether sulfate, the C of anion sulfate surfactant package vinculum of the present invention and collateralization 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 record nonionic non-sulfuric acidization in the present invention) of alkylpolyglycosides.
Alkyl sulfate surfactant is preferably selected from the uncle C of linear and collateralization 10-C 18Alkyl-sulphate, more preferably C 11-C 15Collateralization alkyl group vitriol and C 12-C 14The linear chain alkyl-sulphate.
Alkyl ethoxy sulfate surfactant is preferably selected from C 10-C 18Alkyl-sulphate, it is by (every mole) 0.5 to 20 moles of ethylene oxide ethoxylation.More preferably, alkyl ethoxy sulfate surfactant is C 11-C 18, more preferably C 11-C 15Alkyl-sulphate, it is 0.5 to 7 by (every mole), preferred 1 to 5 mole oxyethane ethoxylation.
The particularly preferred aspect of the present invention is to adopt the mixture of preferred alkyl-sulphate and alkyl ethoxy sulfate surfactant.This mixture has been disclosed among the PCT patent application WO93/18124.
The anion sulfoacid salt surfactant
Be applicable to that anionic sulphonate tensio-active agent of the present invention comprises C5-C20 linear alkyl benzene sulfonate, alkyl ester sulfonate, C 6-C 22Uncle or secondary alkyl sulfonate, C 6-C 24Sulfonated alkene, sulfonated poly carboxylic acid, alkyl glycerol sulfonate, fatty acyl group glycerol sulfonate, the salt of fatty oil base glycerol sulfonate and their mixture.
The anionic carboxylic acid salt surfactant
Suitable anionic carboxylate tensio-active agent comprises alkyl ethoxy carboxylate, alkyl polyethoxye polycarboxylate tensio-active agent and soap class (alkyl carboxyl), particularly uncle's soap of some the present invention's records.
Suitable alkyl ethoxy carboxylate comprises that general formula is RO (CH 2CH 2O) xCH 2COO -M +Carboxylate salt, wherein R is C 6To C 18Alkyl, x are 0 to 10, the distribution of b-oxide based on weight to make x be 0 amount of substance less than 20%, and M is a positively charged ion.Suitable alkyl polyethoxye polycarboxylate tensio-active agent comprises that general formula is RO-(CHR 1-CHR 2-O-)-R 3Carboxylate salt, wherein R is C 6-C 18Alkyl, x are 1 to 25, R 1And R 2Be selected from hydrogen, methyl acid group, Succinic Acid group, hydroxy-butanedioic acid group and their mixture, R 3Be selected from the replacement of hydrogen, 1 to 8 carbon atom or do not replace hydrocarbon and their mixture.
Suitable soap surfactant comprises secondary soap surfactant, and it contains the carboxyl unit that links to each other with secondary carbon.Be used for preferred secondary soap surfactant of the present invention and be to be selected from 2-methyl isophthalic acid-undecanoic acid, 2-ethyl-1-capric acid, 2-propyl group-1-n-nonanoic acid, 2-butyl-1-is sad and the water-soluble salt of 2-amyl group-1-enanthic acid.Some soaps also can be used as froth suppressor and exist.
Basic metal musculamine acid salt surfactant
Other suitable anion surfactant is that general formula is R-CON (R 1) CH 2The basic metal musculamine hydrochlorate of COOM, wherein R is C 5-C 17Linearity or collateralization alkyl or alkenyl, R 1Be C 1-C 4Alkyl, M are alkalimetal ions.Preferred example is the tetradecyl and the oil base methyl musculamine hydrochlorate of sodium-salt form.
Amphoterics
Be used for suitable amphoterics of the present invention and comprise amine oxide surfactant and alkyl both sexes carboxylic acid.
Suitable amine oxide comprises that general formula is R 3(OR 4) xNO (R 5) 2Compound, wherein R3 is selected from alkyl, hydroxyalkyl, acyl group amido propyl and the alkyl phenyl of 8 to 26 carbon atoms, perhaps their mixture; R 4Be the alkylidene group or the hydroxy alkylidene of 2 to 3 carbon atoms, perhaps their mixture; X is 0 to 5, preferred 0 to 3; Each R 5Be alkyl or the hydroxyalkyl that contains 1 to 3 ethylene oxide group, perhaps contain the polyethylene oxide group of 1 to 3 oxyethane.C preferably 10-C 18Alkyl dimethyl amine oxide, and C 10- 18Acyl group acid amides alkyl dimethyl amine oxide.
The suitable example of alkyl both sexes dicarboxylic acid is Miranol (TM) C2M Conc., by Miranol, and Inc., Dayton, NJ produces.
Zwitterionics
Zwitterionics also can join in the detergent composition.These tensio-active agents can be described as the derivative of derivative, heterocyclic secondary and tertiary amine of secondary amine and tertiary amine or the derivative of quaternary ammonium, quaternary phosphonium or uncle's sulfonium compound widely.Trimethyl-glycine and sultaine (sultaine) tensio-active agent is to can be used for typical zwitterionics of the present invention.
Suitable trimethyl-glycine is that general formula is R (R ') 2N +R 2COO -Compound, wherein R is C 6-C 18Alkyl, each R 1C normally 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 acid amides propane (perhaps ethane) dimethyl (perhaps diethyl) trimethyl-glycine.The compound betaine tensio-active agent also is applicable to the present invention.
Cats product
Can be used for the dispersible compound of water that cationic ester tensio-active agent of the present invention preferably has surfactant properties, it contains at least one ester bond (promptly-COO-) and the group of at least one positively charged.Other the suitable cationic ester tensio-active agent that comprises the cholinesterase tensio-active agent for example has been disclosed in US4228042,4239660 and 4260529.
Suitable cationic surfactants comprises quaternary ammonium surfactant, and it is selected from single C 6-C 16, preferred C 6-C 10N-alkyl or alkenyl ammonium surfactant, wherein remaining N position can be replaced by methyl, hydroxyethyl or hydroxypropyl.
Enzyme
In one embodiment of the invention, enzyme is the principal character of detergent tablet.In other embodiments of the present invention, enzyme is the detergent active ingredients of choosing wantonly.When having enzyme, said enzyme is selected from cellulase, hemicellulase, peroxidase, proteolytic enzyme, glucoamylase, amylase, zytase, lipase, Phospholipid hydrolase, esterase, at (cutinase), polygalacturonase, M-Zyme, oxydo-reductase, oxydase, phenol oxidase, lipoxygenase, lignoenzyme, Starch debranching enzyme, tannase, pentosanase (pentosanase), malanases, beta-glucanase, arabinosidases, Unidasa, chondroitinase, laccase or their mixture.
Preferred enzyme comprises and one or several plant cell-wall degrading enzymes bonded proteolytic enzyme, amylase, lipase, peroxidase, at and/or cellulase.
Can be used for cellulase of the present invention and comprise fungi or bacteria cellulose enzyme.Preferably their pH optimum value is 5 to 12, and activity is greater than 50CEVU (Mierocrystalline cellulose viscosity unit).Suitable cellulase is disclosed in US4435307, and among the J61078384 and WO96/02653 of Barbegoard etc., they disclose the fungal cellulase by Humicola insolens, Trichoderma, Thielavia and Sporotrichum preparation.EP739982 has put down in writing from the isolating cellulase of new Bacillus.Suitable cellulase also is disclosed in GB-A-2075028, GB-A-2095275, DE-OS-2247832 and WO95/26398.
The example of the plain enzyme of this fibrid is to be belonged to by Humicolainsolens (Humicola griseavar.thermoidea), particularly belongs to the cellulase that DSM 1800 produces by Humicola.Other suitable cellulase is to be that 50KDa, iso-electric point are 5.5 and contain the cellulase of 415 amino acid whose Humicola insolens preparations by molecular weight; With by DSM1800, have that the Humicola insolens of cellulase activity produces～43kDendoglucanase; The aminoacid sequence of preferred endoglucanase component is disclosed among the PCT patent application WO91/17243.Also having suitable cellulase is the EGIII cellulase that is produced by Trichodermalongibrachiatum, and it is documented in WO94/21801, and Genencor is disclosed on September 29th, 1994.Specially suitable cellulase is the cellulase with color provide protection.The example of these cellulases is the cellulases that are documented in the european patent application 91202879.2, and the document is on November 5th, 1991 open (Novo).Carezyme and Celluzyme (Novo Nordisk A/S) are effective especially.Also can be referring to WO91/17244 and WO91/21801.Other the suitable cellulase that is used for fabric nursing and/or has a cleaning effect is recorded in WO96/34092/WO96/17994 and WO95/24471.
Said cellulase adds organized enzyme in detergent composition with the amount of 0.0001% to 2% weight of detergent composition usually.
Peroxidase can with oxygen source, as combinations such as percarbonate, perborate, persulphate, hydrogen peroxide.They can be used for " solution bleaching ", prevent that promptly the dyestuff or the pigment that fall down from matrix in washing process from transferring on other matrix that exists washing soln.Peroxidase is known in this area, and comprises for example horseradish peroxidase, ligninase and halo peroxidase, as chloro or bromoperoxidase.The detergent composition that contains peroxidase is disclosed in PCT patent application WO89/099813, WO89/09813 and European patent application EP submission on November 6th, 91202882.6,1991 and EP96870013.8, and on February 20th, 1996 submitted to.Laccase also is suitable.
The thiodiphenylamine that preferred toughener is replacement is with syringates of Fen Evil arsenic lysivane propionic acid (PPT), 10-ethyl thiodiphenylamine-4-carboxylic acid (EPC), 10-phenoxazine propionic acid (POP) and 10-Jia Ji phenoxazine (being documented in WO94/12621) and replacement (the alkyl syringates that C3-C5 replaces) and phenol.SPC-D or Sodium peroxoborate are preferred hydrogen peroxide cources.
Said cellulase and/or peroxidase add organized enzyme in detergent composition with the amount of 0.0001% to 2% weight of detergent composition usually.
Other preferred enzyme that is included in the detergent composition of the present invention comprises lipase.The suitable lipase that is used to wash purposes comprises those by Rhodopseudomonas, for example executes the microorganism preparation of stilbene aeruginosa atcc 19.154, and is disclosed as GB1372034.Suitable lipase comprises having with lipase antibody and carries out those of positive immunological cross-reaction, is to be prepared by microorganism Pseudomonas fluroescent IAM1057.This lipase is by AmanoPharmaceutical Co.Lth., Nagoya, and Japan provides with trade name Lipase P " Amano " (this paper is called " Amano-P " later on).Other suitable industrial lipase comprises Amano-CES, the lipase that is produced by Chromobacter viscosum, the Chromobacter viscosumvar.lipolyticum NRRLB 3673 that provides as the Toyo Jozo Co.Tagata by Japan; The Chromobacter viscosum lipase that provides by the Disoynth Co. of the U.S.Biochemical Corp. of the U.S. and Holland, and by the lipase of gladiolus pseudomonas preparation.Specially suitable lipase is the lipase of M1LipaseR and LipomaxR (Gist-Brocades) and LipolaseR and LipolaseUltraR (Novo) for example, and is effective especially when they are found in and are used in combination with composition of the present invention.What also be suitable for is lipolytic enzyme, and it is documented in EP258068, the WO92/05249 of Novo Nordisk and WO94/03578, WO95/35381 and the WO96/00292 of WO95/22615 and Unilever.
That also be suitable for is at [EC3.1.1.50], and it can be counted as a kind of special lipase, the promptly so-called lipase that does not need interface activation.In detergent composition, add at and be documented in for example WO-A-88/09367 (Genencor), WO90/09446 (PlantGenetic System) and WO94/14963 and WO94/14964 (Unilever).
Lipase and/or at generally join in the detergent composition with the amount of 0.0001% to 2% weight organized enzyme of detergent composition.
Suitable proteolytic enzyme is subtilysin, and it is the specified genus preparation by Bacillus subtillis and lichenoid form bacillus (subtilysin BPN and BPN ').A kind of useful proteases is by Bacillaceae preparation, and the pH scope of maximum activity is 8～12, this enzyme by the NovoIndustries A/S (this paper is " Novo ") of Denmark with ESPERASE Exploitation is also sold.The preparation of this kind of enzyme and similar enzyme is documented among the GB1243784 of Novo.The ALCALASE that is provided by Novo is provided other useful proteases , DURAZYM And SAVINASE With the MAXATASE that provides by Gist-Brocades , MAXACAL , PROPERASE And MAXAPEM (protein engineering Maxacal).Proteolytic ferment also comprises the bacterial serine proteolytic enzyme of modification, as be documented in european patent application 87303761.8, in on April 28th, 1987 (particularly the 17th, 24 and 98 page), it is called as " proteolytic enzyme B " in the present invention, with at european patent application 199404, Venegas is disclosed on October 29th, 1986, and it is meant the bacterial serine proteolytic enzyme of the modification that is called as " protease A " at this paper.Most preferably alleged in the present invention " proteolytic enzyme C ", it be from BacillusThe variant of alkaline serine protease, wherein 27 replace arginine in the position at Methionin, tyrosine 104 replaces Xie Ansuans in the position, Serine 123 replaces aspartic acids in the position, L-Ala 274 replaces Threonines in the position.Proteolytic enzyme C is documented among the EP90915958.4, is WO91/06637 accordingly, is disclosed on May 16th, 1991.The variant of gene modification, particularly the variant of proteolytic enzyme C is also contained among the present invention.
The preferred protease of a kind of being called as " proteolytic enzyme D " is the variant with carbonylic hydrolase of the undiscovered aminoacid sequence of nature, it is by being equal at said carbonylic hydrolase+position of 76 positions by the precursor carbonylic hydrolase, also preferred combination one or several be equal to be selected from according to the layout of bacillus amyloliquefaciens subtilysin sequence+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+274 amino acid residue position, sequence according to the bacillus amylolyticus subtilysin, replace a plurality of amino-acid residues to prepare with different amino acid, as WO95/10591 and at C.Ghosh etc. described in the US08/322677 of " BleachingCompasitions Comprising Protease Enzymes ", submit in October 13 nineteen forty-four.
Be applicable to that also of the present invention is to be documented in the proteolytic enzyme among EP251446 and the WO91/06637 and to be documented in proteolytic enzyme BLAP among the WO91/02792 And be documented in its variant of putting down in writing among the WO95/23221.
Also can be referring to the high pH proteolytic enzyme of the WO93/18140A that is documented in Novo from bacillus NCIMB40338.The enzyme washing composition that contains proteolytic enzyme, one or more other enzymes and reversible proteinase inhibitor is documented among the WO92/03529A of Novo.When needing, can adopt Procter ﹠amp; The reduction of putting down in writing among the WO95/07791 of Gamble absorbs and improves the proteolytic enzyme of hydrolysis.The proteolytic enzyme that is used for the recombinant chou Trypsin enzyme of washing composition of the present invention is documented in the WO94/25583 of Novo.Other useful proteases is documented in the EP516200 of Unilever.
Other preferred proteolytic enzyme comprises the proteolytic enzyme of the carbonylic hydrolase variant with the undiscovered aminoacid sequence of nature, it prepares by a plurality of amino-acid residues that adopt different aminoacid replacement precursor carbonylic hydrolases, wherein in pre-enzyme substituted said a plurality of amino-acid residues be equivalent to combine at+210 residues below one or several+33, + 62, + 67, + 76, + 100, + 101, + 103, + 104, + 107, + 128, + 129, + 130, + 132, + 135, + 156, + 158, + 164, + 166, + 167, + 170, + 209, + 215, + 217, + 218 and+222, wherein Bian Hao position with by Bacillus AmyloliquefaciensThe molten rhzomorph of the withered grass of natural generation is identical, perhaps with at other carbonylic hydrolase or withered grass (for example melts rhzomorph Bacillus lentusWithered grass is melted rhzomorph) in the amino-acid residue that equates identical.The preferred enzyme of this class comprise the position change into+210 ,+76 ,+103 ,+104 ,+156 and+166 those.
Proteolytic ferment can be being 0.0001% to 2% of composition weight, and is preferred 0.001% to 0.2%, and more preferably the amount of 0.005% to 0.1% pure enzyme joins in the detergent composition of the present invention.
Can comprise amylase (α and/or β) to remove the spot of carbohydrate-based.WO94/02597, Novo Nordisk A/S is disclosed in and put down in writing the detergent composition that adds mutant amylase on February 3rd, 1994.Also can be referring to WO95/10603, NovoNordisk A/S is disclosed in April 20 nineteen ninety-five.Other becomes known for amylase in the detergent composition and comprises α-and beta-amylase.α-Dian Fenmei is known in the art, and comprises and be disclosed in US5003257, EP252666, WO/91/00353, FR2676456, EP285123, EP525610, EP368341 and the English Patent 1296839 (Novo) those.Other suitable amylase is to have improved stable amylase, comprise and being documented among the WO94/18314, it is disclosed on August 18th, 1994 and WO96/05295, Genencor, it is disclosed on February 22nd, 1996, and directly has other improved amylase variant in the parent in the patent of the WO95/10603 that is disclosed in August, 95 of Novo Nordisk A/S.What also be suitable for is the amylase that is documented among EP277216, WO95/26397 and the WO96/23873 (all being Novo Nordisk).
The example of industry α-Dian Fenmei product is the Purafect OxAm that is provided by Genencor And Termamyl , Ban , Fungamyl And Duramyl , they all are to be provided by NovoNordisk A/S Denmark.WO95/26397 has put down in writing other suitable amylase: be characterised in that specific activity is at least than Termamyl Specific activity in 25 to 55 ℃ scope and pH α-Dian Fenmei of big at least 25% in 8 to 10 scope, specific activity is to pass through Phadebas α-Dian Fenmei activity analysis method is measured.The suitable variant of above-mentioned enzyme is documented in WO96/23873 (Novo Nordisk).Other has has the starch fermentoid that improves character and linkage heat stability and greater activity to be documented in WO95/35382 aspect activity.
Preferred amylase comprises those among the pending application PCT/DK96/00056 that is documented in WO95/26397 and Novo Nordisk.
The starch fermentoid can be being 0.0001% to 2% of composition weight, and is preferred 0.00018% to 0.06%, and more preferably the amount of 0.00024% to 0.048% pure enzyme joins in the detergent composition of the present invention.
In particularly preferred embodiments, detergent tablet of the present invention contains amylase, particularly be documented among the pending application PCT/DK96/00056 of WO95/26397 and Novo Nordisk, with auxiliary amylase bonded those.
" assist " be meant based on the washing purpose add one or several amylase.The example of auxiliary amylase (α and/or β) is described below.WO94/02597 and WO95/10603, NovoNordisk A/S have put down in writing the detergent composition that adds mutant amylase.Other amylase that becomes known in the cleaning compositions comprises α and beta-amylase.α-Dian Fenmei is known in the art, and comprises and be disclosed in US5003257, EP252666, WO/91/00353, FR2676456, EP285123, EP525610, EP368341 and the English Patent 1296839 (Novo) those.Other suitable amylase is to have improved stable amylase, comprise and being documented among the WO94/18314, it is disclosed on August 18th, 1994 and WO96/05295, Genencor, it is disclosed on February 22nd, 1996, and has other improved amylase variant in the patent of the WO95/10603 that is disclosed in August, 95 of NovoNordisk A/S.What also be suitable for is the amylase that is documented among the EP277216 (Novo Nordisk).The example of industry α-Dian Fenmei product is the Purafect Ox Am that is provided by Genencor And Termamyl , Ban , Fungamyl And Duramyl , they all are to be provided by Novo Nordisk A/S Denmark.WO95/26397 has put down in writing other suitable amylase: be characterised in that specific activity is at least than Termamyl Specific activity in 25 to 55 ℃ scope and pH α-Dian Fenmei of big at least 25% in 8 to 10 scope, specific activity is to pass through Phadebas α-Dian Fenmei activity analysis method is measured.The variant that is documented in the above-mentioned enzyme among the WO96/23873 (Novo Nordisk) is suitable.Other has aspect activity and improves character and combine thermostability and the starch fermentoid of greater activity is documented in WO95/35382.Being used for preferred auxiliary amylase of the present invention is the amylase that is documented in WO94/18314, WO96/05295 that is provided by Genencor; Purafect Ox Am And Termamyl , Ban , Fungamyl And Duramyl , they all are to be provided by NovoNordisk A/S, and the Maxamyl that is provided by Gist-Brocades
Said auxiliary amylase can be being 0.0001% to 2% of composition weight, and is preferred 0.00018% to 0.06%, and more preferably the amount of 0.00024% to 0.048% pure enzyme joins in the detergent composition of the present invention.Preferred concrete diastatic pure enzyme is 9: 1 to 1: 9 with auxiliary diastatic weight ratio, more preferably 4: 1 to 1: 4, most preferably is 2: 1 to 1: 2.
Above-mentioned enzyme can be from any suitable source, for example by plant, animal, bacterium, fungi and fermentative preparation.Raw material can further be mesophilic or extremophilic (have a liking for cold, psychrotrophic, thermophilic, have a liking for pressure, have a liking for alkali, have a liking for acid, have a liking for halogen etc.).Can adopt the purification body or the non-purification body of these enzymes.What also can comprise is the mutant of natural enzyme.Mutant can be for example albumen and/or genetically engineered, chemistry and/or physical modification by natural enzyme obtain.Generalized case is to represent enzyme by the host microorganism that has wherein cloned the genetic stew relevant with producing this kind of enzyme.
Said enzyme joins in the detergent composition with the amount of the organized enzyme of 0.0001% to 2% weight of detergent composition usually.This enzyme can add with the form of independent component (containing a kind of ball, particle, stabilising liq of enzyme etc.) or two kinds or several enzyme (as agglomerate).
Other suitable detergent components that add are oxydasis scavenging agents, record and narrate in common EPA92870018.6, and on January 31st, 1992 submitted to.This kind of enzyme oxidation scavengers is four ethylidene polyamines of ethoxylation.
The scope of enzyme material and their methods in the synthetic detergent composition of joining are disclosed in the US3553139 of the WO8908694 A of the WO9307263A of Genencor International and WO9307260A, Novo and McCarty etc., on January 5th, 1971.Enzyme also further is disclosed in US4101457, Place etc., on July 18th, 1978 and at US4507219, Hughes, on March 26th, 1985.Can be used for the enzyme material in the liquid detergent preparation and they joined in this class preparation being disclosed in US4261868, Hora etc., on April 14th, 1981.The enzyme that is used for washing composition can be by various consistent.The enzyme stabilization technique is open and illustrate at US3600319 on August 17th, 1971, Gedge etc., EP199405 and EP200586, on October 29th, 1986, Venegas.The enzyme stabilising system for example also is documented among the US3519570.The effective Bacillus sp.AC13 that produces proteolytic enzyme, zytase and cellulase also is documented among the WO9401532A of Novo.
SYNTHETIC OPTICAL WHITNER
The component very preferably of the composition of activated detergent component is a SYNTHETIC OPTICAL WHITNER.Suitable SYNTHETIC OPTICAL WHITNER comprises the SYNTHETIC OPTICAL WHITNER that can discharge chlorine and oxygen.
One preferred aspect, the SYNTHETIC OPTICAL WHITNER that can discharge oxygen contains hydrogen peroxide cource and organic peracid bleach precursor compound.Organic peroxide acid generates by the situ reaction of precursor hydrogen peroxide cource.Preferred hydrogen peroxide cource comprises inorganic perhydrate SYNTHETIC OPTICAL WHITNER.Another preferred aspect, directly the organic peroxide acid that is prefabricated into is joined in the composition.Contain hydrogen peroxide cource and also can expect with the composition of the mixture of the organic peroxide acid bonded organic peracid precursor that is prefabricated into.
Inorganic perhydrate SYNTHETIC OPTICAL WHITNER
The composition of activated detergent component preferably contains hydrogen peroxide cource as the SYNTHETIC OPTICAL WHITNER that discharges oxygen.Suitable peroxide source comprises inorganic perhydrate salt.
Inorganic perhydrate salt is generally with 1～40% weight of composition, more preferably 2%～30% weight and the most preferably form adding of the sodium salt of 5%～25% weight.
The example of inorganic perhydrate salt comprises perborate, percarbonate, superphosphate, persulphate and persilicate.Inorganic perhydrate salt generally is an alkali metal salt.Inorganic perhydrate salt can add with the form of the crystalline solid that do not have Additional Protection.But for some perhydrate salt, the preferred version of this class particulate composition is to adopt the material that applies, and provides stability in storage preferably to the perhydrate salt in the particulate product like this.
Sodium peroxoborate can be monohydrate NaBO 2H 2O 2Perhaps tetrahydrate NaBO 2H 2O 2.3H 2O.
Alkali metal percarbonate, particularly SPC-D are to be included in preferred perhydrate in the composition of the present invention.SPC-D is that general formula is 2Na 2CO 3.3H 2O 2Addition compound, and industrially be suitable for as crystalline solid.SPC-D also is the addition compound of hydrogen peroxide, and it can dissolve the release hydrogen peroxide very fast, can locally improve SYNTHETIC OPTICAL WHITNER concentration.Percarbonate most preferably joins in this based composition with coating form, so that the stability of product to be provided.
Provide the suitable coating substance of product stability to contain the mixing salt of water-soluble alkali vitriol and carbonate.This coating was disclosed among the GB1466799 together with coating method, and the document obtains power by Interox on March 9th, 1977.The weight ratio of mixing salt coated substance and percarbonate is at 1: 200 to 1: 4, and more preferably 1: 99 to 1: 9, most preferably in 1: 49 to 1: 19 scope.Preferred mixing salt is sodium sulfate and yellow soda ash, has general formula Na 2SO 4.n.Na 2CO 3, wherein n is 0.1 to 3, and preferred n is 0.3 to 1.0, and most preferably n is 0.2 to 0.5.
Another kind provides the suitable coating compounds material of product stability to contain water glass, wherein SiO 2: Na 2The ratio of O is 1.8: 1 to 3.0: 1, and preferred 1.8: 1 to 2.4: 1 and/or Starso preferably use (being generally 3% to 5%) with the concentration of 2% to 10% weight SIO2 of inorganic perhydrate salt.Coating also can comprise manganous silicate.The coating that contains silicate and borate or boric acid or other inorganics also is suitable for.
Other coating that contains wax, oil ﹠ fat soap also can be advantageously utilised among the present invention.
Peroxide one Potassium Persulphate is the inorganic perhydrate salt that another kind is used for the present composition.
Peroxyacid bleach precursor
Peroxyacid bleach precursor is the compound that generates peroxy acid in crossing hydrolysis reaction with hydroperoxidation.Usually peroxyacid bleach precursor can be represented with following formula:
Figure C9880975200341
Wherein L is a leavings group, and X can be any group basically, and like this, by crossing hydrolysis, the structure of the peroxy acid of generation is:
The peroxyacid bleach precursor compound is preferably with 0.5% to 20% weight of composition, preferred 1% to 10% weight, the most preferably amount adding of 1.5% to 5% weight.
Suitable peroxyacid bleach precursor compound generally contains one or several N-or O-carboxyl groups, and this precursor can be selected from the type of wide region.Suitable type comprises the acylated derivatives of acid anhydrides, ester, imide, lactan and imidazoles and oxime.The example of active substance is disclosed in GB-A-1586789 in these kinds.Suitable ester is disclosed in GB-A-836988,864798,1147871,2143231 and EP-A-0170386.
Leavings group
Leavings group, promptly L group hereinafter must have enough reactivities, and hydrolysis reaction was taken place in Best Times (as cycles of washing).But if the L reactivity is too strong, this promoting agent will be difficult to the stable bleaching composition that is used for.
Preferred L group is selected from following group:
With
With
Figure C9880975200355
With their mixture, wherein R 1Be alkyl, aryl or the alkaryl that contains 1 to 14 carbon atom, R 3Be the alkyl chain that contains 1 to 8 carbon atom, R 4Be H or R 3, R 5Be the alkenyl that contains 1 to 8 carbon atom, Y is H or solubilizing group.All R 1, R 3And R 4Can be replaced by all groups basically, for example alkyl, hydroxyl, alkoxyl group, halogen, amine, nitrosyl, acid amides and ammonium or alkyl ammonium group.
Preferred solubilizing group is-SO 3 -M +,-CO 2 -M +,-SO 4 -M +,-N +(R 3) 4X and O＜... N (R 3) 3, and preferred-SO 3 -M +With-CO 2 -M +, R wherein 3Be the alkyl chain that contains 1 to 4 carbon atom, M is the positively charged ion that makes the bleach activator solubilising, and X is the negatively charged ion that makes the bleach activator solubilising.Preferably, M is the ammonium cation of basic metal, ammonium or replacement, most preferably sodium and potassium, and X is halogenide, oxyhydroxide, Methylsulfate or acetic acid anion.
Peroxybenzoic acid precursors
The peroxybenzoic acid precursors compound passed through hydrolysis and produced peroxybenzoic acid.
The peroxybenzoic acid precursors compound of suitable O-acidylate comprises and replacing and unsubstituted benzoyl oxygen benzene sulfonate, comprises for example benzoyl oxygen benzene sulfonate:
Suitable also have sorbyl alcohol, glucose and all carbohydrates adopt benzoyl reagent to carry out the product of benzoylization, for example comprise:
Figure C9880975200362
Ac=COCH3; The Bz=benzoyl
The peroxybenzoic acid precursors compound of acid imide comprises the urea that N-benzoyl succinimide, four benzoyl quadrols and N-benzoyl replace.Suitable imidazoles peroxybenzoic acid precursors comprises N-benzoyl imidazoles and N-Benzoylbenzene imidazoles, and other effectively contains N-acyl group peroxybenzoic acid precursors, comprises N-benzoyl pyrrolidone, dibenzoyl taurine and benzoyl pyroglutamic acid.
Other peroxybenzoic acid precursors comprises benzoyl diacyl peroxide, benzoyl four acyl peroxides and has the compound of following general formula:
Phthalate anhydride is the another kind of suitable peroxybenzoic acid precursors compound of the present invention.
The lactan peroxybenzoic acid precursors of suitable N-acidylate has general formula:
Wherein n is 0 to 8, and is preferred 0 to 2, and R6 is a benzoyl.
Peroxybenzoic acid derivative precursor
Peroxybenzoic acid derivative precursor is by crossing the peroxybenzoic acid that hydrolysis provides replacement.
The peroxybenzoic acid derivative precursor of suitable replacement comprises all peroxybenzoic acid precursors disclosed by the invention; wherein benzoyl is that all non-positive charges (that is: non-cationic) functional group replaces basically, and these functional groups comprise for example alkyl, hydroxyl, alkoxyl group, halogen, amine, nitrosyl radical and amide group.
The preferred kind of the peroxybenzoic acid precursors compound that replaces is the compound with acid amides replacement of following general formula:
Figure C9880975200373
Or
Figure C9880975200374
R wherein 1Be the aryl or the alkaryl of 1 to 14 carbon atom, R 2Be the alkarylene of arylidene or 1 to 14 carbon atom, R 5Be alkyl, aryl or the alkaryl of H or 1 to 10 carbon atom, L can be any leavings group basically.R 1Preferably contain 6 to 12 carbon atoms.R 2Preferably contain 4 to 8 carbon atoms.R 1Can be to contain collateralization, aryl, substituted aryl or alkylaryl that replace or that the two all has, and can be derived from synthesis material or natural matter, comprise for example tallow.To R 2Can allow the variant of similar structures.Substituting group comprises alkyl, aryl, halogen, nitrogen, sulphur and other typical substituting group or organic compound.R 5Preferably H or methyl.R 1And R 5Sum should be more than 18 carbon atoms.The bleaching activity immunomodulator compounds that this class acid amides replaces is documented in EP-A-0170386.
The positively charged ion peroxyacid precursor
Positively charged ion peroxyacid precursor compound passed through hydrolysis and produced the positively charged ion peroxy acid.
Usually, the positively charged ion peroxyacid precursor is partly to prepare by the peroxy acid that replaces suitable peroxyacid precursor compound with positive charge functional group, and positive charge functional group for example is ammonium or alkyl ammonium group, preferably ethyl or ammonium methyl group.The positively charged ion peroxyacid precursor is present in the composition with the form with the salt of suitable anion usually, for example halogen ion or methylsulfuric acid radical ion.
The peroxyacid precursor compound that is replaced by positively charged ion can be a peroxybenzoic acid, perhaps the derivative of its replacement, previously described precursor compound.Randomly, this peroxyacid precursor compound can be the alkyl peroxy acids precursor that alkyl peroxycarboxylic acid precursors compound or acid amides described below replace.
The positively charged ion peroxyacid precursor is documented in US4904406,4751015,4988451,4397757,5269962,5127852,5093022,5106528, UK1382594, EP475512,458396 and 284292, and in JP87-318332.
Suitable positively charged ion peroxyacid precursor comprises the hexanolactam and the tetra-acetylated glucose benzoyl peroxide of a benzoyl of alkyl that all ammoniums or alkylammonium replace or benzoyl oxygen benzene sulfonate, N-acidylate.
The benzoyl oxygen benzene sulfonate that preferred cation replaces is 4-(trimethyl ammonium) methyl-derivatives of benzoyl oxygen benzene sulfonate:
The alkyl oxygen benzene sulfonate that preferred cation replaces has general formula:
Figure C9880975200391
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 precursor of N-acidylate hexanolactam class comprises trialkyl ammonium methylene radical alkyl hexanolactam:
Figure C9880975200393
Wherein n is 0 to 12, particularly 1 to 5.
Another kind of preferred cation peroxyacid precursor is 2-(N, N, a N-trimethyl ammonium) sodium ethyl 4-sulfo group benzol carbonate muriate.
Alkyl percarboxylic acids bleaching precursor
Alkyl percarboxylic acids bleaching precursor passed through hydrolysis and generated percarboxylic acids.The preferred precursor of this class provides peracetic acid by crossing hydrolysis.
The preferred alkyl peroxycarboxylic acid precursors compound of acid imide comprises N, N, N 1, N 1Tetrem acidylate Alkylenediamine, wherein alkylidene group has 1 to 6 carbon atom, and particularly wherein alkylidene group has the compound of 1,2 and 6 carbon atom.Tetra-acetylated ethylene diamine (TAED) is particularly preferred.
Other preferred alkyl peroxycarboxylic acid precursors comprises 3,5,5-trimethyl acetyl base oxygen benzene sulfonic acid sodium salt (different-NOBS), nonanoyl oxygen benzene sulfonic acid sodium salt (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 suitable for, and comprises those compounds with following general formula:
Or
R wherein 1Be the alkyl of 1 to 14 carbon atom, R 2Be the alkylidene group that contains 1 to 14 carbon atom, R 5Be alkyl, aryl or the alkaryl of H or 1 to 10 carbon atom, L can be any leavings group basically.R 1Preferably contain 6 to 12 carbon atoms.R 2Preferably contain 4 to 8 carbon atoms.R 1Can be to contain collateralization, straight or branched alkyl that replace or that the two all has, and can be derived from synthesis material or natural matter, comprise for example tallow.Concerning R2, can allow the variant of similar structures.Replace and comprise alkyl, halogen, nitrogen, sulphur and other typical substituting group or organic compound.R 5Preferably H or methyl.R 1And R 5Sum should be more than 18 carbon atoms.The bleaching activity immunomodulator compounds that this class acid amides replaces is documented in EP-A-0170386.
Benzoxazine organic peroxy acid precursor
The precursor compound that makes benzo oxazinyl of Shi Yonging also, as for example be disclosed among the EP-A-332294 and EP-A-482807, particularly have the compound of following general formula:
Figure C9880975200403
Comprise following replacement benzoxazine:
Figure C9880975200411
R wherein 1Be H, alkyl, alkaryl, aryl, aralkyl, wherein R 2, R 3, R 4And R 5Can be identical or different substituting groups, 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 benzo oxazinyl is:
Figure C9880975200412
The ready-formed organic peroxide acid
Except organic peroxy acid blanching precursor compound, perhaps replace, the organic peroxide acid bleach system can comprise a kind of preformed organic peroxide acid, its content is generally 0.5% to 25% weight of composition, more preferably 1% to 10% weight.
The organic peroxy acid compound of preferred kind is the compound with acid amides replacement of following general formula:
Figure C9880975200413
Or
Figure C9880975200414
R wherein 1Be alkyl, aryl or the alkaryl of 1 to 14 carbon atom, R 2Be alkylidene group, arylidene or the alkarylene of 1 to 14 carbon atom, R 5Be alkyl, aryl or the alkaryl of H or 1 to 10 carbon atom.R 1Preferably contain 6 to 12 carbon atoms.R 2Preferably contain 4 to 8 carbon atoms.R 1Can be the aryl of straight or branched alkyl, replacement or contain alkylaryl collateralization, that replace or that the two all has, and can be derived from synthesis material or natural matter, comprise for example tallow.To R 2Can allow the variant of similar structures.Substituting group comprises alkyl, aryl, halogen, nitrogen, sulphur and other typical substituting group or organic compound.R 5Preferably H or methyl.R 1And R 5Sum should be more than 18 carbon atoms.The organic peroxy acid compound that this class acid amides replaces is documented in EP-A-0170386.
Other organic peroxide acid comprises diacyl and four acyl peroxides, particularly diperoxy dodecanedioic acid, diperoxy tetradecane diacid and diperoxy Thapsic acid.The dibenzoyl superoxide is the preferred organic peroxide acid of the present invention.One and two cross the amino oxy hexanoic acid of crossing of nonane diacid, one and two state's brassylic acids and N-phthaloyl also is applicable to the present invention.
The method of sustained release speed
A kind of method that sustained release SYNTHETIC OPTICAL WHITNER, particularly oxygen bleaching agent are discharged into the speed in the washing soln that is used for can be provided.
The method that can be provided for controlling the SYNTHETIC OPTICAL WHITNER release rate is controlled the release of superoxide in washing soln.This method for example comprises control, and all play the release of inorganic perhydrate salt in washing soln of hydrogen peroxide cource effect.
Suitable sustained release method comprises SYNTHETIC OPTICAL WHITNER is limited in press portion or press portion not.When having more than one not press portion, SYNTHETIC OPTICAL WHITNER can be limited in first and/or second and/or optional after not press portion.
The method of another kind of control SYNTHETIC OPTICAL WHITNER release rate can be by adopting coating to apply SYNTHETIC OPTICAL WHITNER, sustained release being provided.Coating can comprise for example material of poorly water-soluble, or the coating of adequate thickness, the dissolution kinetics may command release rate of thick coating.
Coated substance can adopt the whole bag of tricks to use.The weight ratio that the content of any coated substance is generally coated substance and SYNTHETIC OPTICAL WHITNER is 1: 99 to 1: 2, preferred 1: 49 to 1: 9.
The suitable coating compounds material comprises triglyceride level (as partially hydrogenated vegetables oil, soya-bean oil, Oleum Gossypii semen), monoglyceride or diester, Microcrystalline Wax, gelatin, Mierocrystalline cellulose, lipid acid and their any mixture.
Other suitable coating compounds material can comprise basic metal and alkaline earth metal sulphate, silicate and carbonate, comprises lime carbonate and silicon-dioxide.
Preferred coatings material especially for inorganic perhydrate salt bleach source contains water glass, wherein SiO 2: Na 2The O ratio is 1.8: 1 to 3.0: 1, preferred 1.8: 1 to 2.4: 1, and/or Starso, preferable amount is the SiO of 2% to 10% (being generally 3% to 5%) of inorganic perhydrate salt 2
All inorganic salt coated substances all can mix with the organic binder bond material, so that complex inorganic salt catalyst/organic binder bond coating to be provided.Suitable binder comprises C 10-C 20The alcohol b-oxide, its every mol of alcohol contains the 5-100 moles of ethylene oxide, and preferred every mol of alcohol contains the C of 20-100 moles of ethylene oxide 15-C 20Primary alconol.
Other preferred adhesive contains some polymeric material.Molecular-weight average is that 12000 to 700000 Polyvinylpyrolidone (PVP) and molecular-weight average are 600 to 5 * 10 6, preferred 1000 to 400000, most preferably 1000 to 10000 polyoxyethylene glycol (PEG) is the example of this base polymer matter.The multipolymer of maleic anhydride and ethene, methylvinylether or methacrylic acid (wherein maleic anhydride constitutes at least 20 moles of % of polymkeric substance) is another example that can be used as the polymerizable material of tackiness agent.These polymerizable materials can directly use, and perhaps are used in combination with solvent, and solvent is water, propylene glycol and above-mentioned every mole of C that contains 5～100 moles of ethylene oxide for example 10-C 20The alcohol b-oxide.Another example of tackiness agent comprises C 10-C 20One and two glyceryl ether and C 10-C 20Lipid acid.
Derivatived cellulose, for example methylcellulose gum, carboxymethyl cellulose and Natvosol, and poly carboxylic acid homopolymerization or copolymerization or their salt are the examples that can be used for other tackiness agent of the present invention.
A method of using these coated substances comprises agglomeration.Preferred agglomeration method comprises any above-mentioned organic binder bond material of employing.All conventional cyclone agglomerator and/or mixing machines be can adopt, disc type, rotary drum and vertical mixer included, but are not limited to.The fusion coating composition also can be used by toppling over or being ejected on the moving-bed of SYNTHETIC OPTICAL WHITNER.
Other provides the method for required sustained release to comprise that mechanical means changes the physical properties of SYNTHETIC OPTICAL WHITNER, controls its solvability and release rate.Suitable scheme comprises the solubleness that compacting, machinery inject, manually inject and regulate the bleaching mixture by the granularity of selecting all grain fractions.
Though granularity selects to depend on the composition of grain fraction and need satisfy required sustained release kinetics, but wish granularity greater than 500 microns, preferred median size is 800 to 1200 microns.
All other components that other provides the method for sustained release to comprise suitable selection detergent composition matrix are so that when joining said composition in the washing soln, the ionic strength environment that wherein provides satisfies the required sustained release kinetics that will obtain.
The bleaching catalyst that contains metal
Contain SYNTHETIC OPTICAL WHITNER and can contain metallic bleaching catalyst in addition as preferred ingredient as the present composition of activated detergent component.Preferred this metallic bleaching catalyst is the bleaching catalyst that contains transition metal, is more preferably the bleaching catalyst that contains manganese or cobalt.
The bleaching catalyst of adequate types is such catalyzer: it contains the active heavy metal cation of qualification bleach catalyst, for example copper, iron positively charged ion, a kind of conduct have seldom or do not have the active assistant metal positively charged ion of bleach catalyst (as zinc or aluminium cations) and catalytic and auxiliary metallic cation is had qualification stable sequestrant, particularly ethylene diaminetetraacetic acid, ethylene diamine four (methylene phosphonic acid) and its water-soluble salt.This class catalyzer is disclosed among the US4430243.
The bleaching catalyst of preferred type comprises manganese basigamy compound, is disclosed among US5246621 and the US5244594.These catalyzer preferred example comprise Mn IV 2(u-O) 3(1,4,7-trimethylammonium-1,4,7-three azo-cycle nonanes) 2(PF 6) 2, Mn III 2(u-O) 1(u-OAc) 2(1,4,7-trimethylammonium-1,4,7-three azo-cycle nonanes) 2-(ClO 4) 2, Mn IV 4(u-O) 6(1,4,7-three azo-cycle nonanes) 4(ClO 4) 2, Mn IIIMn IV 4(u-O) 1(u-OAc) 2-(1,4,7-trimethylammonium-1,4,7-three azo-cycle nonanes) 2(ClO 4) 3With their mixture.Other catalyzer is documented in the european patent application 549272.Other is applicable to that title complex of the present invention comprises 1,5,9-trimethylammonium-1,5,9-triazododecane, 2-methyl isophthalic acid, 4,7-7-triazacyclononane, 2-methyl isophthalic acid, 4,7-7-triazacyclononane, 1,2,4,7-tetramethyl--1,4,7-7-triazacyclononane and their mixture.
If suitably, also can select to be used for the bleaching catalyst of the present composition.For example, suitable bleaching catalyst is referring to US4246612 and US5227084.Also can be referring to US5194416, this patent disclosure monokaryon manganese (IV) title complex, Mn (1,4,7-trimethylammonium-1,4,7-7-triazacyclononane) (OCH for example 3) 3-(PF 6).
Also having another kind of bleaching catalyst, as be disclosed among the US5114606, is a kind of manganese (III) and/or (IV) and the water-soluble complexes of ligand, and said ligand is the non-carboxylic acid polyol with at least three continuous C-OH groups.Preferred ligand comprises sorbyl alcohol, iditol, galactitol, mannitol, Xylitol, arabitol, adonitol, meso tetrahydroxybutane, meso hexanol, lactose and their mixture.
US5114611 has put down in writing bleaching catalyst, and it contains the title complex of the transition metal that comprises Mn, Co, Fe or Cu and non--(greatly) ring ligand.Said ligand has general formula:
R wherein 1, R 2, R 3And R 4Can be selected from the alkyl and the aryl of H, replacement, so that each R 1-N=C-R 2And R 3-C=N-R 4Form five yuan or six-ring.Said ring can further be replaced.B is selected from O, S, CR 5R 6, NR 7With the bridged bond of C=O, wherein R 5, R 6And R 7Can be H, alkyl or aryl, comprise replacing or unsubstituted group.Preferred ligand comprises pyridine, pyridazine, pyrimidine, pyrazine, imidazoles, pyrazoles and triazole ring.Randomly, said ring can be replaced by substituting groups such as for example alkyl, aryl, alkoxyl group, halogen and nitros.Particularly preferably be ligand 2,2 '-bipyridyl amine.
Preferred bleaching catalyst comprises Co, Cu, Mn, Fe's-bipyridyl methane and-the bipyridyl amine complex.Catalyzer very preferably comprises Co (2,2 '-bipyridyl amine) C 12, two (lsothiocyanates) bipyridyl amine-cobalt (II), three bipyridyl amine-cobalt (II) perchlorates, Co (2,2 '-bipyridyl amine) 2O 2ClO 4, two-(2,2 ') bipyridyl amine copper (II) perchlorates, three (two-2-pyridyl amine) iron (II) perchlorate and their mixture.
Preferred example comprises and the double-core Mn title complex of the ligand of four-N-dentate and two-N-dentate, comprises N 4Mn III(u-O) 2Mn IVN 4) +[Bip y2Mn III(u-O) 2Mn IVBipy 2]-(ClO 4) 3
Though the structure of the manganese complex of bleach catalyst of the present invention can't determine, can predict that they contain sequestrant or other hydration coordination compound, they are to be interacted by the carboxyl of ligand and nitrogen-atoms and manganese positively charged ion to produce.Equally, the cationic, oxidized attitude of manganese is not definitely known in catalytic process, can be in (+II), (+III), (+IV) or (+V) valence state.Because ligand has six positions that are connected with the manganese positively charged ion, so can reasonably infer and in the Javelle water medium, may have multinuclear and/or " cage " structure.No matter active Mn ligand reality with which kind of form exists, it provides improved bleaching effect to stain with tangible catalytic way, and stain for example is tea, ketchup, coffee, wine, fruit juice etc.
Other bleaching catalyst is documented in for example EP408131 (cobalt complex catalyzer), EP384503 and 306089 (catalysis of metalloporphyrin agent), US4728455 (manganese/polygamy position polymerization of olefin using catalyst body catalyst), US4711748 and EP224952 (on aluminosilicate, absorbing the catalyzer of manganese), US4601845 (the aluminosilicate carrier that contains manganese and zinc or manganese salt), US4626373 (manganese/ligand catalyzer), US4119557 (iron coordinate catalyzer), Germany's 2054019 (catalyzer of cobalt chelating), CA866191 (salt that contains transition metal), US4430243 (sequestrant that contains manganese positively charged ion and non-catalytic metal ion) and US4728455 (managanese gluconate catalyzer).
Other preferred example comprises cobalt (III) catalyzer with following general formula
Co[(NH 3) nM′ mB′ bT′ tQ qP p]Y y
Wherein cobalt is+3 oxidation state; N is 0 to 5 integer (preferred 4 or 5, more preferably 5); The ligand of M ' expression monodentate; M is 0 to 5 integer (preferred 1 or 2, more preferably 1); The ligand of B ' expression bidentate; B is 0 to 2 integer; The ligand of T ' expression tri-dentate; T is 0 or 1; Q is the tetradentate ligand; Q is 0 or 1; P is the ligand of pentacoordinate base; P is 0 or 1; And n+m+2b+3t+4q+5p=6; Y is counting one or several antagonism negatively charged ion of suitably selecting that y exists, and wherein y is 1 to 3 (preferred 2 to 3; When Y is-1 valency negatively charged ion, most preferably 2), to obtain the salt of charge balance, preferred Y is selected from muriate, nitrate, nitrite, vitriol, Citrate trianion, acetate, carbonate and their combination; And wherein at least one and cobalt bonded point are unstable under the automatic dishwashing situation, and remaining coordination electricity can be stablized cobalt under automatic dishwashing condition, the reduction potential that is reduced into cobalt (II) with cobalt (III) under alkaline condition with respect to standard hydrogen electrode less than 0.4 volt (preferably less than 0.2 volt).
Preferred this class cobalt catalyst has general formula:
[Co(NH 3) n(M′) m]Y y
Wherein n is 3 to 5 integer (preferred 4 or 5; Most preferably 5); M ' is unstable coordinate part, be preferably selected from chlorine, bromine, hydroxide radical, water and (when m greater than 1 the time) their combination; M is 1 to 3 integer (preferred 1 or 2, most preferably 1); M+n=6; Y is counting the antagonism negatively charged ion of the suitable selection that y exists, and wherein y is 1 to 3 integer (preferred 2 to 3, when Y is-1 valency negatively charged ion, most preferably 2), to obtain the salt of charge balance.
It is cobalt five amine chloride salts that preferred this class can be used for cobalt catalyst of the present invention, and it has general formula [Co (NH 3) 5Cl] Y y, [Co (NH particularly 3) 5Cl] Cl 2
More preferably be the present composition that adopts cobalt (III) bleaching catalyst with following general formula:
[Co(NH 3) n(M) m(B) b]T y
Wherein cobalt is+3 oxidation state; N is 4 or 5 (preferred 5); M is that one or several are in a position and cobalt coordinate ligand; M is 0,1 or 2 (preferred 1); B is in two positions and cobalt coordinate ligand; B is 0 or 1 (preferred 0), when b=0, and m+n=6, when b=1, m=0 and n=4; T is counting one or several antagonism negatively charged ion of suitably selecting that y exists, and wherein y is integer (preferred y is 1 to 3 with the salt that obtains charge balance; When T is-1 valency negatively charged ion, most preferably 2); And wherein the alkaline hydrolysis velocity constant of said catalyzer is less than 0.23M -1s -1(25 ℃).
Preferred T is selected from; Chlorion, iodide ion, I 3 -, formate, nitrate radical, nitrite anions, sulfate radical, inferior sulfate radical, citrate, acetate, carbonate, bromide anion, PF 6-, BF 4-, B (Ph) 4-, phosphate radical, orthophosphite, silicate, tosylate, methanesulfonate and their combination.Randomly, if there is more than one anionic group in T, T can be protonated, for example HPO 4 2-, HCO 3 -, H 2PO 4 -Deng.In addition, T can be selected from unconventional inorganic anion, and for example anion surfactant is (as LINER ALKYL BENZENE SULPHONIC ACID SOFT 96 root (LAS), alkyl sulfate (AS), alkyl ethoxy sulfonate radical (AES etc.) and/or anionic polymer (as polyacrylate, poly-methyl acrylate etc.).
M partly includes, but are not limited to for example F -, SO 4 -2, NCS -, SCN -, S 2O 3 -2, NH 3, PO 4 3-, carboxylate radical (monocarboxylic acid root preferably, but as long as every part only is connected by a carboxylate radical with cobalt, also can have more than one carboxylate radical wherein partly can be by the form of protonated or its salt at M).Randomly, if having more than one other carboxylate anion group at M, M can be by protonated (as HPO 4 2-, HCO 3 -, H 2PO 4 -, HOC (O) CH 2C (O) O -Deng).Preferred M replaces and unsubstituted C 1-C 30Carboxylic acid, it has following general formula:
RC(O)O-
Wherein R is preferably selected from H and C 1-C 30(preferred C 1-C 18) not replacement and substituted alkyl, C 6-C 30(preferred C 6-C 18) not replacement and substituted aryl and C 3-C 30(preferred C 5-C 18) do not replace and substituted heteroaryl, wherein substituting group is selected from-NR ' 3,-NR ' 4 +,-C (O) OR ' ,-OR ' ,-C (O) NR ' 2, wherein R ' is selected from H and C 1-C 6Part.This class substituent R comprises-(CH 2) nOH and-(CH 2) nNR ' 4 +, wherein n is 1 to 16 integer, and is preferred 2 to 10, most preferably 2 to 5.
Most preferably M is the carboxylic acid of above-mentioned general formula, and wherein R is selected from H, methyl, ethyl, propyl group, linearity or collateralization C 4-C 12The group of alkyl and benzyl.Most preferred R is a methyl.Preferred carboxylic acid M partly comprises formic acid, phenylformic acid, sad, n-nonanoic acid, capric acid, dodecylic acid, propanedioic acid, toxilic acid, Succinic Acid, hexanodioic acid, phthalic acid, 2 ethyl hexanoic acid, naphthenic acid, oleic acid, palmitinic acid, triflate, tartrate, stearic acid, butyric acid, citric acid, vinylformic acid, aspartic acid, fumaric acid, lauric acid, linolic acid, lactic acid, oxysuccinic acid, particularly acetic acid.
B partly comprises carbonate, two and high carboxylic acid's root (as oxalate, malonate, malate, succinic, maleate), pyridine carboxylic acid and α and beta amino acids (as glycine, L-Ala, Beta-alanine, phenylalanine).
It is known being used for cobalt bleaching catalyst of the present invention and their alkaline hydrolysis speed is disclosed in for example M.L.Tobe together, " Base Hydrolysis of Transition-MetalComplexes ", Adv.Inorg.Bioinorg.Mech., (1983), 2, the 1-94 page or leaf.For example, the 17th page table 1 provides 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 alkaline hydrolysis speed of coordinate cobalt five amine catalysts (is expressed as k here OH).Can be used for most preferably cobalt catalyst of the present invention is cobalt five amine acetates, and its general formula is [Co (NH 3) 5OAc] T y, wherein OAc represents the acetate moiety part, and cobalt five amine acetate muriate [Co (NH particularly 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(being called " PAC " in the present invention).
These cobalt catalyst are easy to adopt known method to prepare, for example be documented in the article of Tobe above, its at this as a reference, US4810410, Diakun etc., on March 7th, 1989, J.Chem.Ed.(1989), 66(12) .1043-45; The Synthesis andCharacterization of InorganicCompounds, W.L.Jolly (Prentice-Hall; 1970), pp.461-3; Inorg.Chem., 18, 1497-1502 (1979); Inorg.Chem., 21, 2881-2885 (1982); Inorg.Chem., 18, 2023-2025 (1979); InorgSynthesis, 173-176 (1960); And J Ournal of Physical Chemistry, 56, 22-25 (1952); And the synthetic embodiment that provides below.
Be applicable to that the cobalt catalyst that joins in the detergent tablet of the present invention can produce according to disclosed route of synthesis among the US5559261,5581005 and 5597936, these are disclosed in this in conjunction with as a reference.
Consider the attractive in appearance of product if desired, these catalyzer can prepare with additive materials, with the influence of minimizing color, and perhaps as mentioned below joining in the enzyme containing granule, perhaps composition is made into to contain catalyzer " speckle ".
Organic polymer
Organic polymer can be used as preferred ingredient and joins in the detergent tablet of the present invention.Organic polymer is meant all basically polymerizable organic compounds of generally finding in the detergent composition with dispersion, anti-redeposition, stain remover or other washing character.
Organic polymer generally with composition 0.1% to 30%, the amount of preferred 0.5% to 15%, most preferably 1% to 10% weight adds.
The example of organic polymer comprises polycarboxylate or its salt of poly carboxylic acid water miscible organic homopolymerization or copolymerization, modification, and wherein poly carboxylic acid contains the carboxyl that carbon atom that at least two quilts are no more than two is separated from each other.The polymkeric substance that the back is one type is disclosed in GB-A-1596756.The example of this class salt is that molecular weight is the multipolymer of the polyacrylate of 2000-10000 and they and suitable other monomeric unit, and these unit 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, acryl acid amides, alkylidene group, vinyl methyl ether, vinylbenzene and their any mixture of modification.Preferably vinylformic acid and molecular weight are the multipolymer of 20000 to 100000 maleic anhydride.
Preferred industry provides contains acrylic acid molecular weight and is lower than 15000 polymkeric substance and comprises those that sold with trade(brand)name Sokalan PA30, PA20, PA15, PA10 and Sokalan CP10 by BASF GmbH, and sell with trade(brand)name Acusol 45N, 480N, 460N by Rohm and Haas those.
Contain acrylic acid preferred copolymer and comprise those that contain following monomeric unit: a) 90% to 10%, the vinylformic acid of preferred 80% to 20% weight or its salt, and b) 10% to 90%, the Acrylic Acid Monomer of the replacement of preferred 20% to 80% weight or its salt, general formula is-[CR 2-CR 1(CO-O-R 3)]-, substituent R wherein 1, R 2Or R 3At least one, preferred R 1Or R 2Be the alkyl or the hydroxyalkyl of 1 to 4 carbon atom, R 1Perhaps R 2Can be hydrogen, R 3Can be hydrogen or an alkali metal salt.Most preferably be the Acrylic Acid Monomer that replaces, wherein R 1Be methyl, R 2Be hydrogen (being methacrylic acid monomer).The molecular weight of most preferred this analog copolymer is 3500, and contains the vinylformic acid of 60% to 80% weight and the methacrylic acid of 40% to 20% weight.
The polyamine of polyamine and modification can be used for the present invention, comprises those that are produced by aspartic acid, as is disclosed among EP-A-305282, EP-A-305283 and the EP-A-351629 those.
Other optional polymer can be Mierocrystalline cellulose, polyoxyethylene, polyoxypropylene and their multipolymer (they can be modification with unmodified), ethylene glycol or the propylene glycol or their the unitary terephthalate of mixture band polyoxy alkylidene of the polyvinyl alcohol that is modified or be not modified and acetic ester, Mierocrystalline cellulose and modification.
Suitable example is disclosed among the US5591703,5597789 and 4490271.
Stain remover
The suitable polymers stain remover comprises the stain remover that contains following component: (a) one or several nonionic hydrophilic components, its main ingredient following (i) polymerization degree is at least 2 polyoxyethylene segment, perhaps (ii) the polymerization degree is 2 to 10 propylene oxide or polyoxytrimethylene segment, wherein said hydrophilic segment does not comprise any propylene oxide unit, unless this unit is connected with adjacent part with ehter bond at each end, or the (iii) mixture of oxyalkylene units, it contains ethylene oxide and 1 to 30 propylene oxide unit, described hydrophilic segment preferably contains at least 25% oxygen alkylidene unit and more preferably, particularly, contain at least 50% ethylene oxide unit for having 20-30 the unitary component of oxygen propylidene; Perhaps (b) one or several hydrophobic components comprise: (i) C 3Oxyalkylene terephthalate segment, wherein, if said hydrophobic components also comprises the ethylene oxide terephthalate, ethylene oxide terephthalate: C so 3The oxyalkylene terephthalate unit is 2: 1 or lower, (ii) C 4-C 6Alkylidene group or oxygen C 4-C 6The alkylidene group segment, perhaps their mixture, (iii) poly-(vinyl ester) segment, preferred polyvinyl acetate base ester, its polymerization degree is at least 2, perhaps (iv) C 1-C 4Alkyl oxide or C 4The hydroxyalkyl ether substituting group, perhaps their mixture, wherein said substituting group is with C 1-C 4Alkyl oxide or C 4The form of hydroxyalkyl ether derivatived cellulose or their mixture exists, perhaps (a) and (b) combination.
In general, (a) polymerization degree of the polyoxyethylene segments of (i) is 200, and is preferred 3 to 150 although can adopt high-polymerization degree more, more preferably 6 to 100.Suitable oxygen C 4-C 6The alkylidene group hydrophobic segment includes, but are not limited to the end-blocking of polymkeric substance stain remover, for example MO 3S (CH 2) nOCH 2CH 2O-, wherein M is a sodium, n is 4 to 6 integer, as is disclosed in US4721580, on January 26th, 1988, Gosselink.
Be used for polymkeric substance stain remover of the present invention and also comprise derivatived cellulose, for example copolymerization block of hydroxy ethers cellulose polymer compound, ethylene terephthalate or terephthalic acid propylene glycol ester and polyethylene oxide or polyoxytrimethylene terephthalate etc.This reagent can provide industrial, and comprises cellulosic hydroxy ethers, for example METHOCEL (Dow).Be used for Mierocrystalline cellulose stain remover of the present invention and also be selected from C 1-C 4Alkyl and C 4Hydroxy alkyl cellulose ' referring to USP4000093, on December 28th, 1976, Nicol etc.
The stain remover that is characterised in that poly-(vinyl ester) hydrophobic segment comprises poly-(vinyl ester), as C 1-C 6The graft copolymer of vinyl ester, preferred poly-(vinyl-acetic ester) is grafted on the polyoxyalkylene main chain, on the polyethylene oxide main chain.Referring to EPA0219048, be disclosed on April 22nd, 1987, Kud etc.
Another kind of suitable stain remover is the multipolymer that contains the random block of ethylene terephthalate and polyethylene oxide (PEO) terephthalate.The molecular weight of this polymkeric substance stain remover is 25000 to 55000.Referring to US3959230, Hays, on May 25th, 1976 and US3893929, Basadur, on July 8th, 1975.
Another kind of suitable polymers stain remover is the polyester that contains the ethylene terephthalate repeating unit, this unit contains the ethylene terephthalate unit and 90～80% weight polyoxyethylene terephthalate unit of 10～15% weight, is to be that 300 to 5000 polyoxyethylene glycol produces by molecular-weight average.
Another kind of suitable polymers stain remover is to be the sulfonated product of ol ester oligomer basically, and this oligomer comprises the oligomer main chain and the covalently bound terminal portions on main chain of terephthaloyl and oxyalkylene oxygen repeating unit.These stain removers all are documented in US4968451, November 6 nineteen ninety, J.J.Scheibel and E.P.Gosselink.Other suitable polymers stain remover comprises US4711730, on December 8th, 1987, the terephthalate polyester of Gosselink etc., US4721580, on January 26th, 1988, the end capped oligomerization ester of the negatively charged ion of Gosselink, and US4702857, on October 27th, 1987, the block polyester oligomeric compounds of Gosselink.Other polymkeric substance stain remover also comprises US4877896, on October 31st, 1989, and the stain remover of Maldonado etc., the document discloses anionic, particularly sulfoarolyl, end capped terephthalate.
Another kind of stain remover is the oligomer that has terephthaloyl unit, sulfo group isophthaloyl base unit, ethylene oxide oxygen and the unitary repeating unit of oxygen-propylene.Repeating unit forms the main chain of oligomer, and is end with the lsothiocyanates end-blocking of modification preferably.It is 1.7 to 1.8 the oxygen ethylidene oxygen and the end-blocking unit of oxygen-propylene oxygen unit and two 2-(2-hydroxyl-oxethyl)-ethyl sulfonic acid sodium that particularly preferred this class stain remover contains a sulfo group isophthaloyl base unit, 5 terephthaloyl unit, ratios.
Heavy metal ion chelating agent
Detergent tablet of the present invention preferably contains heavy metal ion chelating agent as an optional component.Heavy metal ion chelating agent is meant the component with the effect of chelating (complexing) heavy metal ion in the present invention.These components also can have calcium and magnesium sequestering power, but preferably they are optionally in conjunction with heavy metal ion, for example iron, manganese and copper.
The content of heavy metal ion chelating agent is generally 0.005% to 20% of composition, and is preferred 0.1% to 10%, and more preferably 0.25% to 7.5%, 0.5% to 5% weight most preferably.
Heavy metal ion chelating agent with phosphonic acids for example or carboxylic acid functional, come down to acid, they can or be to exist with suitable relative cationic title complex/salt with its sour form, positively charged ion for example is the ammonium ion of basic metal or alkaline-earth metal ions, ammonium or replacement, perhaps their any mixture.Preferred all salt/title complexs are water miscible.The molar ratio of said counter cation and heavy metal ion chelating agent preferably was at least 1: 1.
Be used for suitable heavy metal ion chelating agent of the present invention and comprise Organophosphonate, for example poly-(alkylene phosphonic acids ester), ethane 1-hydroxyl di 2 ethylhexyl phosphonic acid an alkali metal salt and nitrilo trimethylene phosphonic ester of amino alkylidenyl.Wherein preferably diethylenetriamine five (methene phosphonate ester), ethylene diamine three (methene phosphonate ester) hexamethylene-diamine four (methene phosphonate esters) and hydroxyl-ethylidene 1, the 1-bisphosphonates.
Be used for other suitable heavy metal ion chelating agent of the present invention and comprise nitrilotriacetic acid(NTA) and polyaminocarboxylic acid, for example the amino tetraacethyl of ethylene, ethylidene pentaacetic acid, ethylene diamine two Succinic Acid, ethylene diamine two pentanedioic acids, 2-hydroxy propylidene diamines two Succinic Acid or their any salt.
Particularly preferably be ethylene diamine-N, the ammonium salt of N '-two Succinic Acid (EDDS) or their basic metal, alkaline-earth metal, ammonium or replacement, perhaps their mixture.Preferred EDDS compound is free acid and its sodium salt or magnesium salts or title complex.
The crystal growth inhibitor component
Detergent tablet preferably contains a kind of crystal growth inhibitor component, preferably a kind of organic diphosphonic acid component, and its content is 0.01% to 5% of composition, more preferably 0.1% to 2% weight.
Organic diphosphonic acid is meant in the present invention and does not contain the organic diphosphonic acid of nitrogen as the part of its chemical structure.This notion does not comprise organic amino phosphonates do, and still, it also can be included in the composition of the present invention as the heavy metal chelant component.
Organic diphosphonic acid is C preferably 1-C 4Di 2 ethylhexyl phosphonic acid, more preferably C 2Di 2 ethylhexyl phosphonic acid, ethylidene diphosphonic acid for example, ethane 1-hydroxyl-1 most preferably, 1-di 2 ethylhexyl phosphonic acid (HEDP), and can exist with some or all of Ionized form, preferably as a kind of salt or title complex.
Water soluble sulfate
Detergent tablet randomly contains a kind of water soluble sulfate.When having water soluble sulfate, its content is 0.1% to 40% of composition, more preferably 1% to 30%, and 5% to 25% weight most preferably.
Water soluble sulfate can contain nearly all salt of the vitriol of counter cation.Preferred salt is selected from the vitriol, particularly sodium sulfate of basic metal and alkaline-earth metal.
Alkalimetal silicate
According to embodiment of the present invention, alkalimetal silicate is the main ingredient of detergent tablet.In another embodiment of the invention, can choose wantonly and have alkalimetal silicate.Preferred alkalimetal silicate is a water glass, SiO wherein 2: Na 2O is 1.8～3.0, and is preferred 1.8～2.4, most preferably 2.0.Water glass is preferably with less than 20%, and is preferred 1%～15%, more preferably 3%～12%SiO 2The amount of weight exists.Alkalimetal silicate can be anhydrous salt or salt hydrate.
Alkalimetal silicate also can be used as the component of alkaline system.
Alkaline system also preferably contains Starso, with 0.4%SiO at least 2The amount of weight exists.SiO in the Starso 2: Na 2The ratio of O is 1.0.The weight ratio of said water glass and said Starso is with SiO 2Meter is preferably 50: 1 to 5: 4, and more preferably 15: 1 to 2: 1, most preferably 10: 1 to 5: 2.
Staining agent
Term " staining agent " is meant all substances of the light of specific wavelength in the visible light absorbing spectrum in the present invention.When joining this staining agent in the detergent composition, its change visible light colors and therefore change the effect of detergent composition outward appearance.Staining agent can be for example dyestuff or pigment.Preferred staining agent is stable in the composition that it is added into.In the high composition of PH, staining agent preferably alkali is stable, and in the composition of low PH, staining agent is preferably sour stable.
Press portion and/or not press portion can contain the mixture of mixture, coloured particle or the coloured particle of staining agent, staining agent so that press portion and not press portion have distinct colors.Preferred press portion or not any one of press portion contain staining agent.
When press portion not contains the composition of two kinds or several activated detergent components, preferred first and second and/or other composition at least one contain staining agent.When first and second and/or other composition all contain staining agent, preferred staining agent has distinct colors.
When coating, preferred coatings contains staining agent.When press portion and coating contained staining agent, preferred staining agent had different visual effects.
The example of suitable dyestuff comprises chemically-reactive dyes, substantive dyestuff, azoic dyestuff.Preferred dyestuff comprises phthalein mountain valley with clumps of trees and bamboo dyestuff, anthraquinone dye, quinoline dye, monoazo, two azos and polyazo.Most preferred dyestuff comprises anthraquinone, quinoline and monoazo-dyes.Preferred dyestuff comprises SANDOLAN E-HRL 180% (trade(brand)name), SANDOLAN MILLING BLUE (trade(brand)name), TURQUOISE ACID BLUE (trade(brand)name) and SANDOLAN BRILLIANT GREEN (trade(brand)name), they provide by UK, with HEXACOL QUINOLINE YELLOW (trade(brand)name) and HEXACOL BRILLIANT BLUE (trade(brand)name), they are by Pointings, UK provides, ULTRA MARINE BLUE (trade(brand)name), provide by Holliday, perhaps LEVAFIX TURQUISE BLUE EBA (trade(brand)name), by Bayer, USA provides.
Staining agent can join press portion and/or not in the press portion by any suitable method.Suitable method comprises mixes with staining agent whole or selected activated detergent component in rotary drum, the whole or selected activated detergent component that perhaps will contain staining agent is ejected in the rotary drum.
When staining agent existed as a component of press portion, its content was 0.001% to 1.5%, and is preferred 0.01% to 1.0%, most preferably 0.1% to 0.3%.When staining agent when a component of press portion does not exist, its content is 0.001% to 0.1%, and is preferred 0.005% to 0.05%, most preferably 0.007% to 0.02%.When staining agent existed as a component of coating, its content was 0.01% to 0.5%, and is preferred 0.02% to 0.1%, most preferably 0.03% to 0.06%.
Corrosion inhibition compound
The detergent tablet of the present invention that is applicable to wash dining set can contain corrosion inhibitor, is preferably selected from Mn (II) salt of organic silver coating-forming agent, particularly paraffin, nitrogenous corrosion inhibition immunomodulator compounds and Mn (II) compound, particularly organic ligand.
The organic silver coating-forming agent is documented among PCT application WO94/16047 and the unsettled European application EP-A-690122.Nitrogenous corrosion inhibition immunomodulator compounds is disclosed among the unsettled European application EP-A-634478.Be used for corrosion inhibition Mn (II) compound and be documented in unsettled European application EP-A-672749.
The organic silver coating-forming agent can be with 0.05% to 10% of total composition, and preferred 0.1% to 5% amount adds.
To be " in use " form protective layer on all present compositions will be with silverware thereon in the effect of silver coating agent.The silver coating agent should have very high affinity to the solid silver surface, and in the time of particularly in be present in washing and aqueous bleaching solution as a component, the solid silver surface adopts this solution to handle.
The suitable organic silver coating-forming agent of the present invention is included in the list that 1 to 40 carbon atom is arranged on the hydrocarbon chain or the fatty ester of polyhydroxy-alcohol.
The fatty acid part of fatty ester can obtain from list or the poly carboxylic acid that 1 to 40 carbon atom is arranged at hydrocarbon chain.The suitable example of monocarboxylic acid lipid acid comprises mountain Yu's acid, stearic acid, oleic acid, palmitinic acid, tetradecanoic acid, lauric acid, acetic acid, propionic acid, butyric acid, isopropylformic acid, valeric acid, lactic acid, oxyacetic acid and β, β '-dihydroxyl isopropylformic acid.The example of suitable poly carboxylic acid comprises n-butyl malonic acid, isocitric acid, citric acid, toxilic acid, oxysuccinic acid and Succinic Acid.
Fatty Alcohol(C12-C14 and C12-C18) group in fatty ester can be used in the list or the polyhydroxy-alcohol that contain 1 to 40 carbon atom on the hydrocarbon chain and represent.The example of suitable Fatty Alcohol(C12-C14 and C12-C18) comprises behenyl alcohol, n-Eicosanol, coconut alcohol (cocoyl), oleyl alcohol and lauryl alcohol, ethylene glycol, glycerine, ethanol, Virahol, vinyl alcohol, Glycerol dimer, Xylitol, sucrose, tetrahydroxybutane, five tetrahydroxybutanes, sorbyl alcohol or anhydro sorbitol.
The lipid acid of fatty ester additive materials and/or Fatty Alcohol(C12-C14 and C12-C18) group preferably have 1 to 24 carbon atom on alkyl chain.
The preferred fatty ester of the present invention is ethylene glycol, glycerine and Isosorbide Dinitrate, and wherein the fatty acid part of these esters generally is selected from mountain Yu's acid, stearic acid, oleic acid, palmitinic acid or tetradecanoic acid.
Glyceryl ester also is very preferred.These be glycerine and above-mentioned lipid acid list-, two-or three-ester.
The suitable example that can be used for aliphatic alcohol ester of the present invention comprises: acetate stearate, lactyl-lactic acid palm ester, isopropylformic acid coconut ester, toxilic acid grease, two toxilic acid greases and propionic acid butter ester.Be used for fatty acid ester of the present invention and comprise single palmitinic acid wood sugar ester, monostearate five red moss esters, Stearinsaeure sucrose ester, glyceryl monostearate, Tego-stearate, Isosorbide Dinitrate.Suitable Isosorbide Dinitrate comprises Arlacel-60, Span 40, Arlacel-20, anhydro sorbitol list myristinate, anhydro sorbitol list mountain Yu's acid esters, polyoxyethylene-sorbitan mono-oleate, anhydro sorbitol dilaurate, anhydro sorbitol SUNSOFT Q-182S, anhydro sorbitol two mountain Yu's acid esters, anhydro sorbitol dioleate, and blended tallow alkyl anhydro sorbitol list and diester.
Zerol, glyceryl monooleate, glycerine monopalmitate, glycerine list mountain Yu's acid esters and Stearic diglyceride are the preferred glyceryl ester of the present invention.
Suitable organic silver coating-forming agent comprises Witepsol W-S 55, list or two glyceryl ester and their all or part of hydrogenant derivatives, and their any mixture.The suitable source of fatty acid ester comprises vegetables oil and fish oil and Tallow, beef.Suitable vegetables oil comprises soya-bean oil, Oleum Gossypii semen, Viscotrol C, sweet oil, peanut oil, Thistle oil, sunflower oil, rapeseed oil, glucose seed oil, plam oil and Semen Maydis oil.
Wax comprises Microcrystalline Wax, also is to be applicable to organic silver coating-forming agent of the present invention.The fusing point of preferred wax is at 35 ℃ to 110 ℃ and contain 12 to 70 carbon atoms usually.The preferably petroleum wax of paraffin and the Microcrystalline Wax formed by the long-chain stable hydrocarbon.
Alginate and gelatin are the organic silver coating-forming agents that the present invention is suitable for.
Dialkylamine oxide compound, for example C 12-C 20Methylamine oxide compound and dialkyl quats compound and salt, for example C 12-C 20The methyl ammonium halide also is suitable for.
Other suitable organic silver coating-forming agent comprises some polymkeric substance.Molecular-weight average is that 12000 to 700000 Polyvinylpyrolidone (PVP), molecular-weight average are the multipolymer of 600 to 10000 polyoxyethylene glycol (PEG), polyamine N-oxide pllymers, N-vinyl pyrrolidone and N-vinyl imidazole, and derivatived cellulose, for example methylcellulose gum, carboxymethyl cellulose and Natvosol are the examples of this base polymer.
Some fragrance materials prove that particularly the metallic surface is had highly direct those, also can be used for the present invention as the organic silver coating-forming agent.
The polymkeric substance stain remover also can be used for the organic silver coating-forming agent.
Preferred organic silver coating-forming agent is a paraffin oil, the aliphatic hydrocarbon of main collateralization normally, and carbonatoms is 20 to 50; Preferred paraffinic oils is selected from the C of main collateralization 25-45, cyclic hydrocarbon and non-cyclic hydrocarbon ratio be 1: 10 to 2: 1, preferred 1: 5 to 1: 1 paraffin oil.The ratio of cyclic hydrocarbon and non-cyclic hydrocarbon be 32: 68 the paraffin oil that satisfies these features by Wintershall, Salzbergen, Germany sells with the trade(brand)name of Winog 70.
Nitrogenous corrosion inhibition immunomodulator compounds
Suitable nitrogenous corrosion inhibition immunomodulator compounds comprises imidazoles and its derivative, for example benzoglyoxaline, 2-heptadecyl imidazoles and be documented in those imdazole derivatives of Czech patent 139279 and GB-A-1137741, they also disclose the method for preparing imidazolium compounds.
Be applicable to that the compound as nitrogenous corrosion inhibitor also has pyrazole compound and their derivative, particularly is substituted basic R at 1,3,4 or 5 1, R 3, R 4And R 5The pyrazoles that replaces, wherein R 1Be H, CH 2OH, CONH 3Perhaps COCH 3, R 3And R 5Be C arbitrarily 1-C 20Alkyl or hydroxyl, R 4Be H, NH 2Or NO 2
Other nitrogenous corrosion inhibition immunomodulator compounds that is suitable for comprises benzotriazole, 2-mercaptobenzothiazole, 1-phenyl-5-sulfydryl-1; 2; 3,4-tetrazolium, thionalid, morpholine, melamine, 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 diammonium hydrogen citrate also are suitable for.
Mn (II) corrosion inhibition immunomodulator compounds
Detergent tablet can contain the corrosion inhibition immunomodulator compounds of Mn (II).This Mn (II) compound is preferably with 0.005% to 5% weight of composition, and is preferred 0.01% to 1%, and most preferably the amount of 0.02% to 0.4% weight adds.Preferably, it is to provide 0.1ppm to 250ppm in liquid lime chloride that Mn (II) compound adds concentration, and more preferably 0.5ppm is to 50ppm, and most preferably 1ppm is to the Mn ion (II) of 20ppm weight.
Mn (II) compound can be the inorganic salt of anhydrous or any hydrated form.Suitable salt comprises manganous sulfate, manganous carbonate, manganous phosphate, manganous nitrate, manganese acetate and Manganous chloride tetrahydrate.Mn (II) compound can be the salt or the title complex of organic acid acetic, for example manganese acetate or manganese stearate.
Mn (II) compound can be the title complex of salt or organic ligand.One preferred aspect, organic ligand is a heavy metal ion chelating agent.Another preferred aspect, organic ligand is a crystal growth inhibitor.
Other corrosion inhibition immunomodulator compounds
Other suitable additional corrosion inhibition immunomodulator compounds comprises mercaptan and glycol, particularly contains the mercaptan of 4 to 20 carbon atoms, comprises lauryl mercaptan, thiophenol, thionaphthol, thionalid and thioanthranol.That also be suitable for is saturated or unsaturated C 12-C 20Lipid acid or their salt, particularly Aluminium Tristearate Micronized sterile.C 12-C 20Hydroxy fatty acid or their salt also are suitable for.Phosphine acidifying octadecane and other antioxidant, for example β hydroxytoluene (BHT) also is suitable for.
The multipolymer of divinyl and toxilic acid, particularly Polysciences Inc provide with commodity label 07787 those to be found as corrosion inhibition immunomodulator compounds be effective especially.
Hydrocarbon ils
It is hydrocarbon ils that another kind is used for preferred activated detergent component of the present invention, and normally advantage long-chain, carbonatoms are 20 to 50 aliphatic hydrocarbon; Preferred hydrocarbons is saturated and/or collateralization; Preferred hydrocarbon ils is selected from the C of advantage collateralization 25-45Material, wherein the ratio of cyclic hydrocarbon and non-cyclic hydrocarbon is 1: 10 to 2: 1, preferred 1: 5 to 1: 1.Preferred hydrocarbon ils is a paraffin.The ratio of cyclic hydrocarbon and non-cyclic hydrocarbon be 32: 68 the paraffin oil that satisfies above-mentioned these features by Wintershall, Salzbergen, Germany sells with the trade(brand)name of Winog 70.
Water-soluble bismuth compound
The detergent tablet of the present invention that is applicable to the wash dining set method can contain water-soluble bismuth compound, preferably with 0.005% to 20% of composition, and more preferably 0.01% to 5%, most preferably the amount of 0.1% to 1% weight exists.
Water-soluble bismuth compound can be a bismuth and all salt or title complexs basically inorganic or the organic phase pair anion basically.Preferred inorganic bismuth salt is selected from three halogenation bismuths, Bismuth trinitrate and bismuth phosphate.Bismuth acetate and bismuth citrate are the preferably salt that contains an organic phase pair anion.
The enzyme stabilizers system
The present invention preferably contains enzyme composition and contains 0.001% to 10%, and is preferred 0.005% to 8%, most preferably the enzyme stabilising system of 0.01% to 6% weight.This enzyme stabilising system can be any stabilising system compatible with detersive enzyme.This stabilising system can contain calcium ion, boric acid, propylene glycol, short chain carboxy acid, boronic acid, chlorine bleaching scavenging agent and their mixture.This stabilising system can also contain the reversible enzyme inhibitors, for example the reversible proteinase inhibitor.
The lime soap dispersing agent compound
The activated detergent components composition can contain the lime soap dispersing agent compound, preferably with 0.1% to 40% weight of composition, and more preferably 1% to 20% weight, most preferably the amount of 2% to 10% weight exists.
Lime soap dispersing agent be prevent lipid acid basic metal, ammonium or amine salt by calcium ion or the sedimentary material of magnesium ion.Preferred lime soap dispersing agent compound is disclosed among the PCT application WO93/08877.
Foam inhibition system
Detergent tablet of the present invention preferably contains foam inhibition system when preparation is used for machine-washing agent composition, and its content is 0.01% to 15% weight of composition, more preferably 0.05% to 10% weight, most preferably 0.1% to 5% weight.
Be used for suitable foam inhibition system of the present invention and can contain any basically known antifoams compound, comprise for example siloxanes antifoams compound, 2-alkyl and alcanol antifoams compound.Preferred foam inhibition system and antifoams compound 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 contain 0.01% to 10%, the polymeric dye transfer inhibitor of preferred 0.05% to 0.5% weight.
The polymeric dye transfer inhibitor is preferably selected from multipolymer, polyvinylpyrrolidonepolymers polymers or their combination of polyamine N-oxide pllymers, N-vinyl pyrrolidone and N-vinyl imidazole.
White dyes
Be applicable to that the detergent tablet in the laundry washing methods of the present invention can randomly contain the hydrophilic white dyes of some types of 0.005% to 5% weight.
Be used for the optional white dyes of wetting ability of the present invention and comprise those with following general structure:
R wherein 1Be selected from anilino, N-2-two-hydroxyethyl and NH-2-hydroxyethyl; R 2Be selected from N-2-two-hydroxyethyl, N-2-hydroxyethyl-N-methylamino, morpholine, chlorine and amino; M is a salt-forming cation, for example sodium or potassium.
In above-mentioned general formula, work as R 1Be anilino, R 2Be N-two-hydroxyethyl, M is during as the positively charged ion of sodium, and whitening agent is 4,4 '-two [(4-anilino-6 (N-2-two-hydroxyethyl) s-triazine-2-yl) amino]-2,2 '-Stilbene disulfonic acid and disodium salt.This special whitening agent material is to be sold on market by Ciba-Geigy Corporation with the trade(brand)name of Tinopal-UNPA-GX.Tinopal-UNPA-GX is the preferred hydrophilic white dyes that can be used for detergent composition of the present invention.
In above-mentioned general formula, work as R 1Be anilino, R 2Be N-2-hydroxyethyl-N-2-methylamino, M is during such as the positively charged ion of sodium, and whitening agent is 4,4 '-two [(4-anilino-6-(N-2-hydroxyethyl-N-methylamino)-s-triazine-2-yl) amino]-2,2 '-Stilbene disulfonic acid disodium salt.This special whitening agent material is to be sold on market by Ciba-Geigy Corporation with the trade(brand)name of Tinopal 5BM-GX.
In above-mentioned general formula, work as R 1Be anilino, R 2Be morpholino, M is the positively charged ion such as sodium, and this whitening agent is 4,4 '-two [(4-anilino-6-morpholino-s-triazine-2-yl) amino]-2,2 '-Stilbene disulfonic acid, sodium salt.This special whitening agent material is to be sold on market by Ciba-Geigy Corporation with the trade(brand)name of TinopalAMS-GX.
The clay softening system
The detergent tablet that is applicable to the laundry cleaning method can contain the clay softening system, contains clay mineral compound and randomly clay flocculating agent.
The preferably green clay compound of clay mineral compound.Green clay is disclosed among the US3862058,3948790,3954632 and 4062647.European patent EP-the A-299575 of Procter and GambleCompany and EP-A-313146 have described suitable organic polymer clay flocculating agent.
Cationic fabric softener
Cationic fabric softener also can join in the present composition that is applicable to the laundry washing methods.Suitable cationic fabric softener comprises water miscible quaternary amine or two long-chain acid amides material, as is disclosed in GB-A-1514276 and EP-B-0011340.
Cationic fabric softener is 0.5% to 15% with total amount usually, and the amount that is generally 1% to 5% weight is mixed.
The component that other is optional
Be applicable to that other optional components that adds in the present composition comprises spices and filling salt, sodium sulfate is a kind of preferred filling salt.
The PH of composition
Detergent tablet of the present invention preferably is not mixed with has very high PH, and to be 1% measured in solution in distilled water, PH is preferably 8.0 to 12.5, and more preferably 9.0 to 11.8, most preferably 9.5 to 11.5.
In another aspect of this invention, compacting can be configured to different PH with press portion not.
Machine wash up method
All suitable methods that are used to machine-wash or clean dirty plate all are suitable for.
A kind of preferred machine dishwashing method comprises adopting to contain and is dissolved in or is scattered in the article that the solution-treated of the detergent tablet of the present invention of significant quantity is wherein made dirty, comprises pottery, vierics, silverware, metal device, cutter and their composite product.The detergent tablet of significant quantity is meant that restraining 60 gram products dissolvings or be dispersed in volume 8 is that this is usual production dosage and the washing soln volume that is used for conventional machine dishwashing method in 3 to 10 liters the washing soln.The weight of preferred detergent tablet is 15 to restrain 40 grams, more preferably 20 restrains 35 grams.
The laundry washing methods
Machine of the present invention laundry washing methods generally comprises the wash water solution that employing wherein was dissolved with or was dispersed with the machine detergent for washing clothes tablet composition of the present invention of significant quantity and handle the fabric of making dirty in washing machine.The detergent tablet composition of significant quantity is meant that restraining 300 gram products dissolvings or be dispersed in volume 40 is that this is usual production dosage and the washing soln volume that is used for conventional machine clothes washing method in 5 to 65 liters the washing soln.
Aspect preferred use, in washing methods, adopt diverting device.Loaded onto Betengent product in this diverting device, and be used to before cycles of washing begins, this product directly be joined in the rotating cylinder of washing machine.Its volume capacity should want to contain enough Betengent products that is generally used in the washing methods.
In case washing machine has been put into clothing, the diverting device that just will contain Betengent product is put into rotating cylinder.When the cycles of washing of washing machine begins, water is added rotating cylinder and the rotating cylinder cycle is rotated.The design of diverting device should make it can comprise the dry detergent product, then with this product in the cycles of washing process when rotating cylinder rotates, discharge along with its stirring, and also be its result who contacts with washing water.
For Betengent product is discharged in washing process, this device can comprise several perforates, and product can pass through these perforates.Randomly, this device can adopt and allow liquid to see through, but the material that does not allow solid phase prod to see through makes, and so just can discharge the dissolved product.Preferably, Betengent product is snap-out release when cycles of washing begins, thereby in this cycles of washing stage, the product instantaneous in the rotating cylinder of washing composition, that the part provides high density.
Preferred diverting device is reusable, and is designed under drying regime and container maintenance globality in the cycles of washing process.
Randomly, this diverting device can be the softish container, for example sack or box.Sack can be the woven fabric structure that waterproof protecting materials coating is arranged, and to keep content, for example is disclosed among the EP0018678.Randomly, it can be made with the water-fast synthesizing polymeric material of isolating aqueous medium by edge sealing or locking design, as is disclosed among the EP0011500,0011501,0011502 and 0011968.The form that makes things convenient for of water fragility locking comprises water-soluble tackiness agent, and it is placed and seal along an edge of the box of being made by fluid-tight polymeric film, and the said polymer for example is polyethylene or polypropylene.
Embodiment
The abbreviation of being adopted among the embodiment
In detergent composition, the component sign of abbreviation has following implication:
STPP: tripoly phosphate sodium STPP
The Citrate trianion citrate trisodium dihydrate
The supercarbonate sodium bicarbonate
The anhydrous citric acid citric acid
The carbonate anhydrous sodium carbonate
Silicate amorphous sodium silicate (SiO 2: Na 2O ratio=1.6～3.2)
Metasilicate Starso (SiO 2: Na 2O ratio=1.0)
PB1 anhydrous sodium perborate monohydrate
PB4 sodium perborate tetrahydrate, general formula are NaBO 2.3H 2O.H 2O 2
Plurafac C 13-C 15The Fatty Alcohol(C12-C14 and C12-C18) of blended ethoxylated/propoxylated, it is flat
All degree of ethoxylation is 3.8, and average degree of propoxylation is
4.5, sell with trade(brand)name Plurafac by BASF
The Tergitol nonionogenic tenside, by Union Carbid with trade(brand)name
Tergitol 15S9 provides
End capped poly-(the oxygen of the epoxy group(ing) of the EXAMPLE III of SLF18 WO94/22800
Alkylidene groupization) alcohol, wherein 1,2-epoxy group(ing) dodecane has replaced 1,
2-epoxy group(ing) decane, by OLIN with trade(brand)name Polytergent
SLE18D provides
The tetra-acetylated ethylene diamine of TAED
HEDP ethane 1-hydroxyl-1, the 1-di 2 ethylhexyl phosphonic acid
DETPMP diethyl triamine five (methylene radical) phosphonate, by monsanto with
Trade(brand)name Dequest 2060 provides
PAAC five amine Cobaltous diacetate (III) salt
The BzP benzoyl peroxide
The paraffin oil that paraffin is sold with trade(brand)name Winog70 by Wintershall
The protease protein lytic enzyme
The amylase amylolytic enzyme
The BTA benzotriazole
The PA30 molecular-weight average moon is about 4500 polyacrylic acid
480N vinylformic acid/methacrylic acid is 7: 3 a random copolymers, average mark
The son amount is 3500
The vitriol anhydrous sodium sulphate
The molecular weight that PEG3000 is provided by Heschst is about 3000 polyoxyethylene glycol
The molecular weight that PEG6000 is provided by Heschst is about 6000 polyoxyethylene glycol
The sugar table sugar
Gelatin category-A gelatin is provided by Sigma, 65bloom intensity
The CMC carboxymethyl cellulose
Dodecanedioic acid C12 dicarboxylic acid
Hexanodioic acid C6 dicarboxylic acid
Lauric acid C12 monocarboxylic acid
It is 1% solution that PH is determined in the distilled water at 20 ℃
In the following embodiments, all content is meant by compacting part, the % weight of press portion or coating not.
Embodiment 1
The following describes the detergent tablet of the present invention that is applicable to dishwashers.
Press portion is by putting into the composition of activated detergent component in the punching press chamber of improved 12 rotary tablet machines, and with the pressure compacting said composition of 13KN/cm2.This improved tabletting machine can provide press portion to have the sheet of mould.Based on the purpose of embodiment A to F, press portion is not a particle.Employing nozzle charging machine not press portion is placed in the mould of press portion exactly.Adopt the coating that contacts with press portion to apply not press portion, press portion does not stick on the press portion.
A B C D E F
Press portion
STPP - 55.10 52.0 52.80 50.00 38.20
Citrate trianion 26.40 - - - - -
Carbonate - 14.0 16.0 15.40 18.40 15.00
Silicate 26.40 14.80 15.0 12.60 10.00 10.10
Proteolytic enzyme - - - 1.0 - -
Amylase 0.6 0.75 0.75 0.95 2.0 0.85
PB1 1.56 12.50 12.20 12.60 15.70 11.00
PB4 6.92 - - - - -
Nonionogenic tenside 1.50 1.5 1.50 1.65 0.80 1.65
PAAC - 0.016 0.016 0.012 - 0.008
TAED 4.33 - - - 1.30 -
HEDP 0.67 - - - - 0.92
DETPMP 0.65 - - - - -
Paraffin 0.42 0.50 0.5 0.55 0.50 -
BTA 0.24 0.30 0.3 0.33 0.33 -
PA30 3.2 - - - - -
Spices - - - 0.05 0.20 0.2
Vitriol 24.05 - 2.00 - 10.68 22.07
Micro substance/water is to balance
Weight (gram) 20.0 20.0 20.0 20.0 30.0
Press portion not
Proteolytic enzyme 12.80 8.12 9.92 8.00 8.00 8.00
Amylase 7.20 13.00 6.00 10.00 - 13.00
Metasilicate - 50.02 - 45.10 40.00 50.00
Supercarbonate - 13.00 20.02 13.00 6.00 13.00
Citric acid - 13.00 14.98 14.00 6.00 13.00
BzP - - - 9.00 - -
Citrate trianion 35.00 - - - 40 -
Silicate 42.00 - 48.03 - - -
Weight (gram) 5.0 3.0 3.0 3.0 5.0
Coating
Dodecanedioic acid - 90.00 82.00 - - 90.00
Hexanodioic acid - - - 92.00 - -
Lauric acid - - 8.00 - - -
Starch 15.00 10.00 10.00 8.0 - 10.00
PEG - - - - 100 -
Weight (gram) 1.00 1.00 1.20 0.80 0.50 1.00
The gross weight of sheet (gram) 25g 23g 23g 23g 18g 35g
Embodiment 2
Press portion sees through the punching press chamber of the composition of activated detergent component being put into improved 12 rotary tablet machines, and with 13KN/cm 2Pressure compacting said composition.This improved tabletting machine can provide press portion to have the sheet of mould.Based on the purpose of embodiment G to K, press portion does not contain activated detergent component and tackiness agent.Then not in the mould of press portion impouring press portion.Below, detergent tablet is carried out set-up procedure, in this stage, not press portion sclerosis.
G H I J K L
Press portion
STPP - 55.10 52.0 52.80 50.00 38.20
Citrate trianion 26.40 - - - - -
Carbonate - 14.0 16.0 15.40 18.40 15.00
Silicate 26.40 14.80 15.0 12.60 10.00 10.10
Proteolytic enzyme - - - 1.0 - -
Amylase 0.6 0.75 0.75 0.95 2.0 0.85
PB1 1.56 12.50 12.20 12.60 15.70 11.00
PB4 6.92 - - - - -
Nonionogenic tenside 1.50 1.5 1.50 1.65 0.80 1.65
PAAC - 0.016 0.016 0.012 - 0.008
TAED 4.33 - - - 1.30 -
HEDP 0.67 - - - - 0.92
DETPMP 0.65 - - - - -
Paraffin 0.42 0.50 0.5 0.55 0.50 -
BTA 0.24 0.30 0.3 0.33 0.33 -
PA30 3.2 - - - - -
Spices - - - 0.05 0.20 0.2
Vitriol 24.05 - 2.00 - 10.68 22.07
Micro substance/water is to balance
Weight (gram) 20.0g 20.0g 20.0g 20.0g 22g 30.0g
Press portion not
Tergitol - - 21.5 18.92 - -
PEG3000 89.40 - - - - -
PEG6000 86.9 - - - -
BzP 10.60 11.00 - - 20.00 20.00
Sugar - - 53.4 29.04 65.00 65.00
Gelatin - - 15.01 30.00 5.00 5.00
Starch - - - 10.00 - -
Water - - 10.00 10.00 10.00 10.00
Minor component/balance
Weight (gram) 2.5g 5.0g 2.5g 2.5g 3g 3g
The gross weight of sheet (gram) 22.5g 25g 22.5g 22.5g 25g 33g

Claims (9)

1. the preparation method of detergent tablet, this detergent tablet comprises press portion and not compacting, non-encapsulated part, this method comprises following step:
A) compacting contains activated detergent component and the composition that is selected from the cracking agent of the agent of bursting apart, pore forming material and their mixture, forms at least one mould in described press portion; With
B) fill at least one mould in the described press portion with the composition of activated detergent component that contains liquid or gel form, forms at least aly suppress, non-encapsulated part.
2. according to the process of claim 1 wherein the weight ratio of press portion and press portion not greater than 0.5: 1, and described detergent tablet contains alkalimetal silicate.
3. according to the method for claim 1, wherein press portion and the weight ratio of press portion not be greater than 0.5: 1, and described detergent tablet adopts bath temperature to be adjusted at 50 ℃ and agitator to set dissolution rate that the SOTAX dissolution test method that rotates with 250rpm measures greater than 0.33 gram/minute.
4. according to the process of claim 1 wherein the weight of detergent tablet less than 40 grams, and described detergent tablet adopts temperature to be adjusted at 50 ℃ and agitator to set dissolution rate that the SOTAX dissolution test method that rotates with 250rpm measures greater than 0.33 gram/minute.
5. according to the process of claim 1 wherein that described press portion provides a plurality of moulds, and fill each mould with at least a not press portion.
6. according to the method for claim 5, wherein at least two in first, second and the optional follow-up not press portion are contained the activated detergent component, have at least in the component one inequality.
7. according to the method for claim 1, this method further comprises the subsequent coated step, and the wherein not coated coating of at least a portion of press portion is not so that press portion sticks at least one mould of described press portion.
8. according to the method for claim 7, wherein said coating contains and is selected from: the component of hexanodioic acid, lauric acid, suberic acid, nonane diacid, sebacic acid, undecane diacid, dodecanedioic acid, undecane dicarboxylic acid and their mixture.
9. according to the method for claim 1, this method further comprises follow-up set-up procedure, wherein not press portion and/or coating sclerosis.
CN98809752.4A 1997-08-02 1998-08-03 Detergent tablet Expired - Fee Related CN1218029C (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB9716351.3 1997-08-02
GB9716351A GB2327949A (en) 1997-08-02 1997-08-02 Detergent tablet

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Publication Number Publication Date
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CN1218029C true CN1218029C (en) 2005-09-07

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JP (1) JP2001512177A (en)
CN (1) CN1218029C (en)
AT (3) ATE350456T1 (en)
BR (1) BR9815605A (en)
CA (1) CA2298510C (en)
DE (3) DE69836835T2 (en)
DK (1) DK0960187T3 (en)
ES (3) ES2142782T3 (en)
GB (1) GB2327949A (en)
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DE69818871T2 (en) 2004-07-22
ATE226626T1 (en) 2002-11-15
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GB2327949A (en) 1999-02-10
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ATE251665T1 (en) 2003-10-15
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ATE350456T1 (en) 2007-01-15
DE69836835T2 (en) 2007-10-11
DE69808885T2 (en) 2003-06-18
EP1134281B1 (en) 2003-10-08
ES2280302T3 (en) 2007-09-16
DE69836835D1 (en) 2007-02-15
EP1162258A3 (en) 2004-01-14
CA2298510A1 (en) 1999-02-11
WO1999006522A1 (en) 1999-02-11
JP2001512177A (en) 2001-08-21
ES2142782T3 (en) 2003-05-01
DE69818871D1 (en) 2003-11-13
ES2142782T1 (en) 2000-05-01
CA2298510C (en) 2004-05-11
EP1134281A1 (en) 2001-09-19
BR9815605A (en) 2001-11-20

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