CN109312267A - Dumpable detergent suspension comprising bleach catalyst particles - Google Patents
Dumpable detergent suspension comprising bleach catalyst particles Download PDFInfo
- Publication number
- CN109312267A CN109312267A CN201780016161.1A CN201780016161A CN109312267A CN 109312267 A CN109312267 A CN 109312267A CN 201780016161 A CN201780016161 A CN 201780016161A CN 109312267 A CN109312267 A CN 109312267A
- Authority
- CN
- China
- Prior art keywords
- weight
- water
- detergent
- suspension
- coating
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
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
- C11D3/39—Organic or inorganic per-compounds
- C11D3/3947—Liquid compositions
-
- 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
- C11D3/2003—Alcohols; Phenols
- C11D3/2065—Polyhydric alcohols
-
- 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
- C11D3/26—Organic compounds containing nitrogen
- C11D3/33—Amino carboxylic acids
-
- 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
- C11D3/3902—Organic or inorganic per-compounds combined with specific additives
- C11D3/3905—Bleach activators or bleach catalysts
- C11D3/3935—Bleach activators or bleach catalysts granulated, coated or protected
Abstract
The present invention relates to a kind of dumpable detergent suspension, it includes: the hygroscopic component of 30-80 weight % is selected from aminocarboxylate chelators, glycerol and combinations thereof；The water of 8-25 weight %；The bleaching agent of 1-30 weight %；The bleach catalyst particles that the diameter of 0.1-5 weight % is 20-2000 μm, the bleach catalyst particles include: one or more nuclear particles of 30-90 weight %；The coating of cladding one or more nuclear particles of 10-70 weight %, the coating are formed and are contained by one or more dope layers: the coating containing at least catalyst granules of the manganese bleaching catalyst of 30 weight % of 1-30 weight %；With the coating of the water-soluble alkali sulfate of 50-99 weight %；The bleach catalyst particles are free of enzyme, the catalyst granules containing 0.3-20 weight % and the water-soluble alkali sulfate containing 30-99 weight %.The dumpable detergent suspension is easily fabricated and shows good storage stability, although it contains bleaching agent, bleaching catalyst and a large amount of water.
Description
Technical field
The present invention relates to the dumpable detergent suspension comprising bleaching agent and bleaching catalyst.More specifically, of the invention
It is related to dumpable detergent suspension, it includes:
● hygroscopic component is selected from aminocarboxylate chelators, glycerol and combinations thereof；
● water；
● bleaching agent；With
● bleach catalyst particles.
Despite the presence of bleaching catalyst, bleaching agent and a large amount of water, but detergent suspension of the invention combines and can incline
Property and high stability.
Background technique
Detergent formulations usually contain many different active components, including surfactant, builder, enzyme and bleaching
Agent.
Spot and dirt are discharged using surfactant and the component of release is distributed in cleaning solution.Enzyme passes through hydrolysis
The stain of protein, starch and lipid and help to remove these ingredients.Bleaching agent is used in detergent composition to pass through
Oxidation constitute can bleach spot (such as with tea, coffee, red wine and the related spot of various fruits and vegetables products) component and
Remove these spots.Typical bleaching agent for detergent formulations is the compound based on chlorine and peroxide, is such as hypochlorous acid respectively
Salt and percarbonate bleach.Use bleaching catalyst to activate bleaching agent in detergent composition, especially in lower temperature
Under.
Builder is mixed in detergent formulations so that magnesium and calcium ion and maintenance alkaline pH is complexed.Helping based on phosphorus
Lotion, such as phosphate, using for many years in a variety of detergent compositions.However, as environmentally friendly wash is intended to
The a part for washing the increase trend of agent composition has developed alternative builder, and these alternative builders are
Them are found into the mode in commercial laundering agent product.Aminocarboxylate chelators' Pidolidone-N, N- diacetate esters are to use
In the example of the environmentally friendly builder of commercial laundering agent product.In general, aminocarboxylate chelators are with its (complete deprotonation
Change) form of sodium salt is present in detergent formulations.The aqueous solution of aminocarboxylate is alkaline.
Liquid detergent preparation is developed, because of the advantages of these products are provided better than powder formulation, i.e., they are easy
In application, the active constituent containing higher concentration is less subject to moisture damage during storage and/or is easier to be distributed to water
In property cleaning solution.It is washed to provide the liquid of cleaning, point sample (spotting) and filming performance that delivering is similar to powder formulation
Wash agent composition, it is necessary to comprising keeping undissolved component in liquid product matrix.These undissolved components are needed whole
Even suspension in a product, to guarantee constant, optimal cleaning effect.Although this can be by instructing user to shake before use
Movable property product are realized, it is apparent that preferably providing the liquid for keeping stable suspension form during the life cycle of product
Detergent formulations.However, since sedimentation and emulsification/hydro-planing occur for suspended particulate, so that suspension is layered at any time, therefore
This target is very difficult.
Bleaching agent is to lose its active water sensitivity at any time if the water activity of detergent composition is too high
Detergent ingredients.Combined detergent composition containing bleaching agent and bleaching catalyst is especially sensitive to moisture.
EP-A1129160 is described containing water, glycerol, builder, the liquid waterborne cleaning compositions of enzyme and thickener.
WO2013/092276 is described containing GLDA, water, citric acid, nonionic surfactant, the spray drying of coating
Percarbonate, the detergent formulations of Mn catalyst granules and other compositions.
WO2014/107578 is described containing water, glycerol, polyaminocarboxylic acid (chelating agent), nonionic surfactant
Detergent composition.
WO2008/064935 describes a kind of method for preparing bleach catalyst particles, the bleach catalyst particles packet
Containing the total weight relative to the particle,
A) bleaching catalyst of 0.1 to 30 weight %,
B) carrier material of 40 to 95 weight %,
C) adhesive of the group from organic polymer of 0.1 to 5 weight %,
The adhesive of wherein bleaching catalyst, carrier material and the group from organic polymer is in contact with each other in a mixer
And it is granulated, it is characterised in that
A) carrier material is introduced into mixer first, wherein carrier material contains the carbonate and silicon greater than 70 weight %
Hydrochlorate, and the weight ratio of carbonate and silicate is in the range of 10:1 to 1:10, and
B) spraying includes the solution or suspension of bleaching catalyst and adhesive.
WO2016/005392 describes particle, it includes
● the core comprising enzyme, the core is by following encirclement:
● the first dope layer, it includes the bleaching catalyst containing manganese and ligand, the ligand is two or trimethyl azepine
Cyclononane or derivatives thereof, first dope layer is by following encirclement:
● the second dope layer, it is described it includes at least 60 weight % with the water soluble salt of constant humidity at 20 DEG C
Constant humidity is higher than 85%.
Summary of the invention
It is easily fabricated and to show good storage steady inventor developed a kind of dumpable detergent suspension
It is qualitative, although it contains bleaching agent, bleaching catalyst and a large amount of water.
Dumpable detergent suspension of the invention includes:
● the hygroscopic component of 30-80 weight % is selected from aminocarboxylate chelators, glycerol and combinations thereof；
● the water of 8-25 weight %；
● the bleaching agent of 1-30 weight %；
● the bleach catalyst particles that the diameter of 0.1-5 weight % is 20-2000 μm, the bleach catalyst particles packet
Contain:
One or more nuclear particles of zero 30-90 weight %；
The coating of cladding one or more nuclear particles of zero 10-70 weight %, the coating are applied by one or more
The bed of material forms and contains:
The coating containing at least catalyst granules of the manganese bleaching catalyst of 30 weight % of -1-30 weight %；With
The coating of the water-soluble alkali sulfate of -50-99 weight %；
The bleach catalyst particles are without enzyme, the catalyst granules containing 0.3-20 weight % and contain 30-99
The water-soluble alkali sulfate of weight %.
Although the present inventor is not wishing to be bound by theory, it is believed that hygroscopic component can be living by the moisture of detergent suspension
Degree is reduced to extremely low level, despite the presence of at least water of 8 weight %.Therefore, although to contain moisture quick for detergent suspension
Perceptual bleach system (bleaching agent and bleaching catalyst), but suspension is highly stable.To this stability it is further contribution be
Special bleach catalyst particles containing manganese bleach catalyst particles, by water-soluble alkali sulfuric acid base status with can incline
The other components for the suspension of falling detergent separate.
Detergent composition of the invention also provides extensive detergent ingredients and can mix in the form dispersed or dissolved
Wherein the advantages of.Bleach catalyst particles are evenly dispersed in entire detergent suspension.
Specific embodiment
The present invention provides a kind of dumpable detergent suspension, it includes:
● the hygroscopic component of 30-80 weight % is selected from aminocarboxylate chelators, glycerol and combinations thereof；
● the water of 8-25 weight %；
● the bleaching agent of 1-30 weight %；
● the bleach catalyst particles that the diameter of 0.1-5 weight % is 20-2000 μm, the bleach catalyst particles packet
Contain:
One or more nuclear particles of zero 30-90 weight %；
The coating of cladding one or more nuclear particles of zero 10-70 weight %, the coating are applied by one or more
The bed of material forms and contains:
The coating containing at least catalyst granules of the manganese bleaching catalyst of 30 weight % of -1-30 weight %；With
The coating of the water-soluble alkali sulfate of -50-99 weight %；
The bleach catalyst particles are without enzyme, the catalyst granules containing 0.3-20 weight % and contain 30-99
The water-soluble alkali sulfate of weight %.
Term " drumped " as used herein is the composition for referring to flow at ambient conditions.Shearing can be passed through
It is drumped that desaturation is also considered as its drumped thixotropic composition.
Term " thixotropic " as used herein refers to that composition (such as gel or fluid) is viscous in a stationary situation
Property and shaking, agitation or otherwise by stress when become less sticky.It is this so-called in thixotropic composition
" shear-thinning effect " be reversible, once that is, composition is no longer influenced by shear stress, will return to more viscous state.
The term as used herein " aminocarboxylate chelators " refers to containing by carbon atom and one or more carboxyl companies
The compound of the one or more nitrogen-atoms connect, by providing electronics to multiple to be formed from nitrogen and oxygen atom to metal ion
Chelate ring and with metal ion formed strong complex.
Term " water-soluble alkali sulfate " refers to that the solubility at 20 DEG C in distilled water is at least 10g/l, excellent
The choosing at least alkali metal sulfates of 50g/l.
Unless otherwise stated, referring to that use meets whenever referring to " granularity " or " particle diameter " herein
The system of requirement described in ISO13320:2009 (such as can be obtained from Malvern Instruments Ltd
MastersizerTM2000) pass through the particle diameter of determination of laser diffraction.
Unless otherwise stated, the water content includes unbonded (dissociates herein whenever referring to water content
) and combine water.
When the parameter of such as concentration or ratio, which is referred to as, is less than some upper limit, it should be understood that do not specifying
In the case where lower limit, the lower limit of the parameter is 0.
Whenever quantifying the amount or concentration of component herein, unless otherwise stated, the amount of quantization or the concentration of quantization relate to
And described component itself, even if common practice is by such component and one or more other compositions with solution or mixture
Form addition.
Detergent suspension of the invention is uniform products.Therefore, undissolved component, such as bleach catalyst particles are equal
It is dispersed in entire detergent suspension evenly.
Detergent suspension preferably comprises one or more aminocarboxylate chelators.It is highly preferred that detergent suspension
Containing water and no more than one or more aminocarboxylate chelators of 2:1 weight ratio, preferably more than 1.5:1, most preferably not
More than 1.2:1.Water and one or more aminocarboxylate chelators are usually at least 1:3, more preferably at least 1:2, most preferably extremely
The weight ratio of few 1:1.8 is included in detergent suspension.
Detergent suspension preferably comprises glycerol.Glycerol and water preferably are contained in dumpable detergent suspension, heavy
Ratio is measured in the range of 2:3 to 1:6, more preferably in the range of 1:2 to 1:5, most preferably in the range of 1:2.2 to 1:4.
Dumpable detergent suspension preferably comprises 20-75 weight %, more preferable 30-60 weight %, most preferably 35-55 weight
Measure the glycerol of %.
The water content of detergent suspension is preferably 10-22 weight %, more preferably 11-20 weight %, most preferably 12-
18 weight %.
Water activity of the detergent suspension at 20 DEG C is usually 0.2 to 0.6.It is highly preferred that detergent suspension exists
Water activity at 20 DEG C is in the range of 0.3 to 0.5, and most preferably 0.35 to 0.45.
Dumpable detergent suspension preferably comprises at least 8 weight %, more preferable 10-40 weight %, most preferably 12-30 weights
Measure one or more aminocarboxylate chelators of %.
Preferably, one or more aminocarboxylate chelators are selected from glutamic acid N, N- oxalic acid (GLDA), the sweet ammonia of methyl
Sour oxalic acid (MGDA), iminodisuccinic acid (IDS), ethylenediamine tetra-acetic acid (EDTA), diethylene triamine pentacetic acid (DTPA) (DTPA),
Hydroxyethyliminodiacetic acid (HEIDA), nitrilotriacetic acid (NTA), aspartic acid diethyl oxydisuccinic acid (AES), asparagus fern ammonia
Acid-N ,-oxalic acid (ASDA), hydroxyethylenediamine tetracetic acid (HEDTA), hydroxyethylethylene diamine tri-acetic acid (HEEDTA), imino group
Two fumaric acid (IDF), imino-diacetic tartaric acid (IDT), imino-diacetic maleic acid (IDMAL), imino-diacetic malic acid (IDM),
Two fumaric acid of ethylenediamine (EDDF), two malic acid of ethylenediamine (EDDM), two tartaric acid of ethylenediamine (EDDT), ethylenediamine disuccinic acid
(EDDS), two maleic acid of ethylenediamine (EDDMAL) and two pyridine carboxylic acids (dipicolinic acid) and its salt.
It is highly preferred that one or more aminocarboxylate chelators are selected from GLDA, MGDA, IDS, HEIDA, EDDS and NTA
And its salt.In even more preferably embodiment, one or more aminocarboxylate chelators be selected from GLDA, MGDA, IDS and
Its salt.Most preferably, one or more aminocarboxylate chelators are selected from GLDA and its salt.
GLDA used in this suspension is preferably glutamic acid-N, the alkali metal salt of N- oxalic acid.It is highly preferred that used
GLDA is glutamic acid-N, the sodium salt of N- oxalic acid.Most preferably, GLDA used is glutamic acid-N, the tetrasodium salt of N- oxalic acid.
The combination of glycerol, water and one or more aminocarboxylate chelators usually account at least 45 weights of detergent suspension
Measure %, preferably at least 55 weight %, most preferably at least 60 weight %.
Bleaching agent
Detergent suspension of the invention preferably comprises at least 1.5 weight %, more preferable 1.8-15 weight %, most preferably 2-
The bleaching agent of 12 weight %.
Bleaching agent is preferably selected from per-compound bleaching agent, and hydrogen peroxide discharges compound, and hydrogen peroxide generates system, mistake
Oxygen acid and its salt, peroxyacid bleach precursor system and combinations thereof.Even further preferably, bleaching agent is selected from alkali-metal peroxide
The hydrogen peroxide source of object, organic peroxide bleaching compounds and inorganic persalt bleaching compounds and combinations thereof.Even preferably
Ground, bleaching agent are peroxide.
The example of peroxide is single persulfate, perborate monohydrate, perborate tetrahydrate and percarbonic acid
The acid of salt and corresponding salt.Organic peracid for use in the present invention include alkyl peroxy acids and aryl peroxy acids such as benzoyl hydroperoxide and
Cyclosubstituted benzoyl hydroperoxide (such as peroxide-α-naphthoicacid), aliphatic series and the single peroxy acid of the aliphatic series replaced (such as peroxide lauric acid
And peroxystearic acid) and phthalyl amide groups peroxy caproic acid (PAP).
Typical case's diperoxy acid for use in the present invention includes alkyl diperoxy acid and aryl diperoxy acid, such as 1,12-, bis- mistake
Oxygen dodecanedioic acid (DPDA), 1,9- diperoxyazelaic acid, diperoxy brazilic acid, diperoxy decanedioic acid and diperoxy isophthalic diformazan
Acid and 2- decyl diperoxy butyl- Isosorbide-5-Nitrae-diacid.
Most preferably, bleaching agent is percarbonate.
Detergent suspension of the invention preferably comprises the bleaching agent of particle form.It is highly preferred that suspension contains 1-15
Weight %, the particle comprising bleaching agent of more preferable 2-12 weight %.Preferably, these particles contain at least 10 weight %, more
Preferably at least 30 weight %, the most preferably at least bleaching agent of 50 weight %.
According to a preferred embodiment, the particle of bleaching agent (such as percarbonate) be comprising it is one or more containing
The particle of the coating of the nuclear particle of bleaching agent, one or more nuclear particles are surrounded by water-soluble coating.Water-soluble coating is advantageous
Ground includes to be selected from alkali metal sulfates, the coating agent of alkali carbonate or alkali metal chloride and combinations thereof.
The diameter of bleach particle is usually 10-3000 μm, more preferable 20-2000 μm, most preferably 30-1500 μm.
The volume weighting average grain diameter of bleach particle is preferably 10 to 3000 μm, and more preferable 100 to 1500 μm, most preferably
200 to 1000 μm.
Bleach catalyst particles
Dumpable detergent suspension of the invention usually contains 0.2-4 weight %, more preferable 0.2-3 weight %, optimal
Select the bleach catalyst particles of 0.4-2.5 weight %.
Bleach catalyst particles usually contain at least 0.5 weight %, more preferable 0.8-10 weight %, most preferably 1-8 weight
Measure the manganese bleaching catalyst of %.
Bleach catalyst particles usually contain at least 40 weight %, more preferably at least 50 weight %, most preferably at least 60 weights
Measure the water soluble salt of %.
Bleach catalyst particles usually have at least 50 μm, more preferable 100-1500 μm, even more preferably 250-1200 μm,
Most preferably 350-1000 μm of diameter.Bleach catalyst particles are preferably spheric granules.
Catalyst granules in bleach catalyst particles usually contains at least 50 weight %, more preferably at least 80 weight %'s
Manganese bleaching catalyst.
Present inventors have unexpectedly discovered if the diameter of catalyst granules is very small, can prepare has especially
The particle of good stability.Therefore, according to another preferred embodiment, the diameter of at least catalyst granules of 90 weight % exists
In the range of 0.2 to 25 μm, more preferably in the range of 0.4 to 20 μm, even more preferably in the range of 0.5 to 18 μm, most
It is preferred that in the range of 0.6 to 15 μm.
In general, the volume weighted average diameter of catalyst granules is 1-12 μm, most preferably 1.5-10 μm.
Water-soluble alkali sulfate in bleach catalyst particles has preferably at 2 DEG C higher than 85%, especially high
In 90% constant humidity.The specific example of suitable salt is Na2SO4(CH20℃=93%), K2SO4(CH20℃=98%),
KHSO4(CH20℃=86%).Water-soluble alkali sulfate can be anhydrous form or it can be hydrated salt, that is, have
The crystallization salt hydrate of the combination water of crystallization.Specific example is anhydrous sodium sulfate (Na2SO4)。
Bleach catalyst particles preferably comprise at least 35 weight %, more preferable 40-80 weight %, most preferably at least 45-75
One or more nuclear particles of weight %.
According to particularly preferred embodiment, bleach catalyst particles contain a kind of single nuclear particle.
The diameter of one of bleach catalyst particles or a variety of nuclear particles is preferably 40-1500 μm, more preferably 80-
1200 μm, even more preferably 200-1000 μm, most preferably 300-900 μm.
Nuclear particle can be made of inert support material.Core can suitably contain functional detergent ingredient, such as help and wash
Agent, bleach-activating, dispersed polymeres, silicate, scale preventative, glass corrosion inhibitors, antirust agent, surfactant and its group
It closes.Preferably, nuclear particle contains at least 50 weight %, more preferably at least 80 weight %, the most preferably at least inertia of 90 weight %
Carrier material is selected from water soluble salt (such as sulfate and/or carbonate), cellulose fibre, dextrin, disaccharides and combinations thereof.
The thickness of the coating of bleach catalyst particles is preferably 5 to 150 μm, and more preferably 10 to 120 μm, even more preferably
It is 12 to 80 μm, most preferably 15 to 50 μm.
Coating usually account for bleach catalyst particles be no more than 65 weight %, more preferable 20-60 weight %, most preferably 25-
55 weight %.
Coating preferably comprises 2-25%, more preferable 3-20%, and most preferably 3.5-15 weight %'s includes manganese bleaching catalyst
Catalyst granules coating.
According to a particularly preferred embodiment, bleach catalyst particles contain single nuclear particle, and have been selected
The size of the size of nuclear particle, the thickness of coating and catalyst granules suspension stability and was used with providing storage stability
The optimal combination of the active delivering of bleaching catalyst in journey.Therefore, under bleach catalyst particles preferably comprise and have and meet
A kind of nuclear particle of column specification:
● nuclear particle diameter: 200-1000 μm；
● catalyst particle diameter: 0.4-20 μm；
● coating layer thickness: 10-150 μm.
Even further preferably, bleach catalyst particles meet following specification:
● nuclear particle diameter: 300-900 μm；
● catalyst particle diameter: 0.5-18 μm；
● coating layer thickness: 15-50 μm.
Preferably, the thickness of coating is more than the volume weighted average diameter at least 50% of catalyst granules, more preferably at least
100%, most preferably at least 200%.
The coating of bleach catalyst particles preferably comprises 55-90 weight %, the water soluble salt of more preferable 60-85 weight %.
The coating of particularly preferred embodiment according to the present invention, bleach catalyst particles contains at least two dope layer,
Including (i) the first dope layer, it includes the water-soluble binders of the catalyst granules of 30-90 weight % and 10-70 weight %, and
(ii) second layer of first dope layer is surrounded, second dope layer includes at least 60 weight %, more preferably at least 70 weights
Measure %, even more desirably at least 80 weight %, the most preferably at least water soluble salt of 90 weight %.
Water-soluble binder is preferably selected from monosaccharide, disaccharides, trisaccharide, dextrin and combinations thereof.Most preferably, water-soluble binder
Selected from sucrose, lactose, dextrin and combinations thereof.Most preferably, water-soluble binder is dextrin, such as maltodextrin.
The combination of catalyst granules, water soluble salt and water-soluble binder usually accounts for the coating of bleach catalyst particles extremely
Few 60 weight %, more preferably at least 70 weight %, most preferably at least 75 weight %.
The average thickness of above-mentioned first dope layer is preferably 2-50 μm, more preferably 3-30 μm, even more preferably 4-25 μ
M, most preferably 5-20 μm.
First dope layer generally comprises the 2-15% based on the weight of core, the catalyst granules of the amount of more preferable 3-10%.The
One dope layer preferably comprises the 1-20% based on the weight of core, the water-soluble binder of the amount of more preferable 2-10%.
Second dope layer of bleach catalyst particles usually accounts at least 5%, more preferably at least 10% based on the weight of core, most
Preferably at least 20%.Second dope layer preferably accounts at most 100 weight %, more preferably up to 80 weight % based on the weight of core, most
Preferably up to 75 weight %.
The average thickness of second dope layer is preferably at least 3-100 μm, more preferably 5-80 μm, even more preferably 8-60
μm, most preferably 10-40 μm.
Optionally, bleach catalyst particles may include the other third dope layer around the second dope layer.The third applies
The bed of material preferably comprises at least 20 weight %, more preferably at least 25 weight %, and most preferably at least 30 weight %'s is selected from polyethylene glycol
(PEG), hydroxypropyl methyl cellulose (HPMC), the film-forming components of polyvinyl alcohol (PVA) and combinations thereof.Preferably, third coating
Layer with a thickness of 1-50 μm, most preferably 2-30 μm.
According to particularly preferred embodiment, the manganese bleaching catalyst in the coating of bleach catalyst particles is by formula (I) table
Show:
[LnMnmXp]zYq(I)
Wherein:
- Mn is manganese, and each Mn independently has the oxidation state selected from II, III, IV and V；
- n and m is 1 to 4 independent integer；
- X represents coordination or bridge joint type；
- p is 0 to 12 integer；
- Y is counter ion counterionsl gegenions, and type depends on the charge z of complex compound；
- q is charge of the charge z divided by Y；With
- L is the ligand of the big ring organic molecule as logical formula (II)
Wherein:
■R1And R2It each is selected from H, alkyl and aryl；
■ t and t' are respectively 2 to 3 independent integer；
The each D of ■ is independently selected from N, NR, PR, O or S, and wherein R is H, alkyl or aryl；With
■ s is 2 to 5 integer；
The weight % of manganese bleaching catalyst is expressed as the weight % of the molar equivalent concentrations of complex compound, and wherein L is Isosorbide-5-Nitrae, 7-
Trimethyl-Isosorbide-5-Nitrae, 7- 7-triazacyclononane, m are that 2, X is O2-, p 3, z 2+, Y PF6 -And q is 2.
Manganese bleaching catalyst is preferably indicated that wherein both n and m are preferably 1 or 2, more preferably wherein n=m=2 by formula (I).
Coefficient p is preferably 3 to 6 integer.
According to another preferred embodiment, each Mn independently has the oxidation state selected from III and IV.
X in formula (I) is preferably represented selected from H2O, OH-, O2-, S2 -, HOO-, O2 2-, O2 1-, R-COO-Coordination or bridge joint kind
Class, wherein R is H, the alkyl optionally replaced, the aryl optionally replaced, NR3, wherein R is H, and the alkyl optionally replaced optionally takes
The aryl in generation, Cl-, SCN-, N3 -, etc., or combinations thereof.It is preferred that X represents O2-Or (OAc)-, more preferable O2-.Herein, Ac is indicated
Acyl group.
Y is counter ion counterionsl gegenions, and type depends on the charge z of complex compound, can be it is positive, zero or negative.If z is just
, then Y is anion, such as Cl-, Br-, I-, NO3 -, ClO4 -, NCS-, PF6 -, RSO4 -, OAc-, BPh4 -, CF3SO3 -, RSO3 -,
RSO4 -, etc., wherein R represents alkyl or aryl.Preferably, Y is PF6 -Or ClO4 -.If z be it is negative, Y be cation,
Such as alkali metal, alkaline-earth metal or (alkyl) ammonium cation etc..
L in formula (I) is the ligand of big ring organic molecule form shown in logical formula (II)
Wherein R1And R2It respectively can be zero, H, alkyl or aryl；T and t' is respectively 2 to 3 independent integer；Each D can
It independently is N, NR, PR, O or S, wherein R is H, alkyl or aryl.
D in formula (II) is preferably NR.If D is N, one of miscellaneous carbon key connected to it can be unsaturated, example
Such as generation-N=CR1Segment, R2It is 0.
Coefficient s in formula (II) is preferably 2,3 or 4, and even more preferably s is 2.
Preferred ligand L is that wherein each D independently selected from NH or NR, t and t' is 2 or 3, s=2 and R1=R2=H that
A bit, more preferable wherein at least one D is NCH3And t=t'=2.Other preferred ligand Ls are that wherein each D is NCH3；T=t'
=2；S=2 and R1And R2It respectively can be those of H or alkyl.The example of such preferred ligand mentions in EP-A-0458397
For.
Particularly preferred ligand is Isosorbide-5-Nitrae, 7- trimethyl-Isosorbide-5-Nitrae, and 7- 7-triazacyclononane is encoded to Me-TACN, Isosorbide-5-Nitrae, 7-
7-triazacyclononane, is encoded to TACN, 1,5,9- trimethyl -1,5, and 9- triazododecane is encoded to Me-TACD；2- first
Base-Isosorbide-5-Nitrae, 7- trimethyl-Isosorbide-5-Nitrae, 7- 7-triazacyclononane are encoded to Me/Me-TACN and 2- methyl-1,4,7- tri- azacyclo- nonyls
Alkane is encoded to Me/TACN.In these ligands, Me-TACN and Me/Me-TACN are most preferred.
The example of suitable manganese bleaching catalyst provides in EP-A-0458397.
Preferably manganese bleaching catalyst includes one of following or a variety of
[MnIII 2(μ-O)1(μ-OAc)2(Me-TACN)2](ClO4)2,
[MnIIIMnIV(μ-O)1(μ-OAc)2(Me-TACN)2](ClO4)3,
[MnIII 2(μ-O)1(μ-OAc)2(Me-TACN)2](PF6)2,
[MnIII 2(μ-O)1(μ-OAc)2(Me/Me-TACN)2](PF6)2,
[MnIV 2(μ-O)3(Me-TACN)2](PF6)2, and
[MnIV 2(μ-O)3(Me/Me-TACN)2](PF6)2。
It is even furthermore preferable that manganese bleaching catalyst includes one of following or a variety of: [MnIV 2(μ-O)3(Me-TACN)2]
(PF6)2[MnIV 2(μ-O)3(Me/Me-TACN)2](PF6)2.It is even more preferred that manganese bleaching catalyst is [MnIV 2(μ-O)3
(Me-TACN)2](PF6)2。
Bleach catalyst particles of the invention can be prepared suitably by fluidized bed coating process.According to a particularly preferred reality
Mode is applied, by the way that the aqueous suspension of the catalyst granules for the adhesive for containing dissolution to be sprayed on the fluidized bed of nuclear particle
Apply the first dope layer.Next, passing through fluidized bed coating process and saline solution is sprayed on the fluidized bed of coated particle
Second dope layer is coated to the coated particle so obtained.
Bleach-activating
Detergent composition can contain one or more bleach-activatings, such as peroxyacid bleach precursor.Peroxy acid drift
White dose of precursor is well known in the art.As non-limiting examples, N, N, N', the tetra-acetylated second of N'- can be mentioned
Diamines (TAED), nonanoyloxybenzene sulfonate (SNOBS), before benzoyloxy benzene sulphonate (SBOBS) and Cationic Peroxyacid
Body (SPCC), such as US-A-4, described in 751,015.
Surfactant
This detergent suspension preferably comprises one or more surfactants.Surfactant in the present invention be as
" Surfactant Science Series ", Vol.82, Handbook of detergents, Part A:Properties,
Chapter 2 (Surfactants, classification), the component in classification described in G.Broze (editor).In general,
Detergent composition contains 0.5-30 weight %, preferably 1-20 weight %, one or more tables of more preferable 1.3-10 weight %
Face activating agent.In a preferred embodiment, surfactant is selected from one or more nonionic surfactants.
According to particularly preferred embodiment, composition contains 0.1-15 weight %, more preferable 0.5-10 weight %, optimal
Select the nonionic surfactant of 1-5 weight % or the mixture of two or more nonionic surfactants.It can be used for this
The example of nonionic surfactant in inventive composition includes the hydrophobic alkyl with functional group, alkenyl or alkyl aromatic
The condensation product of object is closed, the functional group, which has, can be used for being condensed with hydrophilic epoxy alkane to form nonionic surfactant
Free reactive hydrogen, the hydrophilic epoxy alkane are such as ethylene oxide, propylene oxide, epoxy butane, polyethylene oxide or poly-
Ethylene glycol.The example of such functional group includes hydroxyl, carboxyl, sulfydryl, amino or amide groups.
The example of the useful hydrophobe of commercial nonionic surfactant includes C8-C18 alkyl alcohol, C8-C14 alkyl
Phenol, C8-C18 alkyl fatty acid, C8-C18 alkyl hydrosulfide, C8-C18 alkyl fatty amine, C8-C18 alkylamide and C8-C18 alkane
Base fatty alkanolamides.Therefore, suitable ethoxylized fatty alcohol can be selected from ethoxylation cetanol, and ethoxylation ketone is stearic
Alcohol, the different tridecanol of ethoxylation, ethoxylated lauryl, ethoxylated oleyl and its mixture.For of the invention suitable
Nonionic surfactant example be found in by BASF provide PlurafacTMLF is serial and by Croda offer
SynperonicTMNCA series down to non-foamed ethoxylated/propoxylated straight chain alcohol.Also of interest that can make from BASF
For the sealing end ethoxylated alcohol that SLF18 series obtains, and from the Lutensol provided by BASFTMThe linear saturation C16- of AT series
The alkyl polyglycol ether of C18 fatty alcohol preparation.Other non-ion reagents suitable for the present composition are can be from BASF/
Cognis is as DehyponTM3697GRA or DehyponTMThe modified fatty alcohol polyglycol ether that Wet is obtained.Suitable for this hair
The bright Lutensol also from BASFTMThe non-ion reagent of TO series is from the poly- second of alkyl for being saturated different C13 alcohol preparation
Glycol ethers.Amine oxide surfactant can also be used as antiredeposition surfactant in the present invention.Suitable amine oxide table
The example of face activating agent is C10-C15 alkyl dimethyl amine oxide and C10-C15 amido alkyl dimethyl amine.The present invention
People discovery, if the nonionic surfactant used is solid at ambient temperature, can produce not only in chemistry and
And physically highly stable detergent composition.Therefore, advantageously, composition of the invention contains 0.1-30 weight %,
More preferable 0.5-20 weight %, further preferred 1-10 weight %, most preferably 1-5 weight % be at 25 DEG C solid it is non-from
Sub- surfactant.
If existing total amount is preferably smaller than 5 weight %, more preferably no more than 2 weights using anionic surfactant
Measure %.In addition, if then preferably there is the defoaming agent for inhibiting foaming there are anionic surfactant.Suitable anion table
The example of face activating agent is methyl ester sulfonate (methylester sulphonate) or NaLS.It is preferred that in the present invention
Composition in be not present anionic surfactant.
Silicate
Silicate can be added in preparation.Silicate can be used as builder, buffer or article care agent.Preferably
Silicate is sodium metasilicate, such as sodium disilicate, sodium metasilicate and crystallization phyllosilicate and its mixture.Silicate is preferably to suspend
The concentration of 0.5 to 8 weight %, more preferable 0.8 to 6 weight % of liquid is in detergent suspension.
Enzyme
The example of enzyme suitable for present invention cleaning suspension includes lipase, cellulase, peroxidase, protease
(proteolytic enzyme), amylase (amylolytic enzyme) and other, degradation changes or promotes the biochemistry met in cleaning situation dirty
The degradation or change of dirt and spot, to more easily get on dirt or spot from substrate body, so that dirt or spot exist
It is easier to remove in subsequent cleaning.Both degradation and change can improve dirt removal.
Preferably, the one or more organized enzymes for including in suspension of the present invention are selected from protease, amylase, cellulose
Enzyme, peroxidase, mannase, transelminase and lipase.Most preferably, organized enzyme is selected from protease, starch
Enzyme and combinations thereof.
Suspension of the invention usually contains at least 10mg/kg, more preferably at least 20mg/kg, even more desirably at least
50mg/kg, most preferably at least 100mg/kg organized enzyme.The concentration of organized enzyme is preferably more than 50g/kg, more preferably no more than
40g/kg, most preferably not more than 30g/kg.
According to particularly preferred embodiment, suspension contains at least 10mg/kg, more preferably at least 20mg/kg, most preferably
At least active amylase of 50mg/kg.
According to another particularly preferred embodiment, suspension contains at least 100mg/kg, more preferably at least 200mg/
Kg, the most preferably at least active protease of 400mg/kg.
Enzyme can be added with liquid or encapsulated form.Encapsulating enzyme example be Genencor D, E and HS type enzyme granulate and
T, GT, TXT and the Evity of NovozymesTMType particle.
Proteolytic enzyme in the present invention includes metalloproteinases and serine protease, including neutral or alkaline microbial
Serine protease, such as subtilopeptidase A (EC 3.4.21.62).It can be and be originated from for proteolytic enzyme of the invention
Those of bacterium or fungi.Mutant (variant) including chemistry or genetic modification.Preferred proteolytic enzyme is derived from following
Those of: bacillus, such as bacillus lentus, bacillus gibsonii, bacillus subtilis, bacillus licheniformis, basophilic
Bacillus, bacillus amyloliquefaciens and bacillus pumilus, wherein bacillus lentus and bacillus gibsonii are most preferably
's.The example of such proteolytic enzyme is the Excellase of GenencorTM, ProperaseTM, PurafectTM,
PurafectTMPrime, PurafectTMOx；And Novozymes is with trade name BlazeTM, OvozymeTM, SavinaseTM,
AlcalaseTM, EverlaseTM, EsperaseTM, RelaseTM, PolarzymeTM, LiquinaseTMAnd CoronaseTMSale
Those of.
It can be for amylolytic enzyme of the invention from those of bacterium or fungi.Including chemical or genetic modification
Mutant (variant).Preferred amylolytic enzyme is derived from Bacillus strain such as bacillus subtilis, bacillus licheniformis, solution
The alpha-amylase of bacillus amyloliquefaciens or bacillus stearothermophilus.The example of such amylolytic enzyme by Novozymes with
Trade name StainzymeTM, StainzymeTMPlus, TermamylTM, NatalaseTMAnd DuramylTMProduction and distribution；With
And the Powerase of GenencorTM, PurastarTM, PurastarTMOxam。StainzymeTM, StainzymeTMPlus and
PoweraseTMIt is preferred amylase.
Particularly preferred embodiment according to the present invention, suspension contain active protease, and freshly prepd suspension
When storing 8 weeks in closed container at 20 DEG C, proteinase activity, which reduces, is no more than 70%, more preferably no more than 50%,
Most preferably not more than 20%.Well-known enzyme stabilizers such as polyalcohol/borax, calcium, formates or protease inhibitors such as 4-
Formyl phenylboronic acid also is present in suspension.
Dispersed polymeres
Detergent suspension can suitably contain one or more dispersed polymeres.The dispersed polymeres referred in the present invention
Selected from antispot agent and/or scale preventative.
The example of suitable antiplaque polymeric reagent includes the polybasic carboxylic acid of hydrophobically modified, such as AcusolTM460ND (comes
From the Alcosperse of Dow) and AkzoNobelTM747, and synthesis of clay, preferably have the synthesis of those of high surface area viscous
Soil, highly useful for preventing spot, the residue of especially dirt and dispersion is present in water at the place gathered on glass
Those of formed, and the spot formed when water then evaporates.
The example of suitable scale preventative includes organic phosphonate, aminocarboxylate, multifunctional substituted compound, and its mixed
Close object.
Particularly preferred scale preventative is organic phosphonate, such as alpha-hydroxy-2 phenyl ethyl diphosphonic acid salt, ethylidene diphosphine
Hydrochlorate, hydroxyl 1,1- hexylidene (hydroxy 1,1-hexylidene), ethenylidene -1,1- diphosphonate, 1,2- dihydroxy
Ethane 1,1- diphosphonate and hydroxy-ethylene 1,1- diphosphonate.Most preferably hydroxy-ethylene 1,1- diphosphonate
(EDHP) and 2- phosphinylidyne butane, 1,2,4- tricarboxylic acids (Bayhibit comes from Bayer).Suitable scale preventative is water-soluble point
Polymer is dissipated, from allyloxy benzene sulfonic acid monomer, methallylsulfonic acid monomer, copolymerizable non-ionic monomer and copolymerizable alkene
Belong to unsaturated carboxylic acid monomer preparation, as described in US 5 547612, or is acrylic acid sulfonated polymer, such as EP 851 022
Described in.Such polymer includes polyacrylate and methyl methacrylate, methallylsulfonic acid sodium and sulfo group
Phenolmethyl allyl ether, such as the Alcosperse of supplyTM240(AkzoNobel).It also suitable is containing polyacrylate
With the terpolymer of 2- acrylamido -2- methyl propane sulfonic acid, such as the Acumer 3100 that Dow is provided.As alternative
The polymer and copolymer of acrylic acid of the molecular weight between 500 and 20,000 also can be used in case, such as with as monomer
The homopolymerization multi-carboxylic acid compounds of the acrylic acid of unit.The average weight of such homopolymer of sour form be preferably 1,000 to
100,000, especially 3,000 to 10,000, such as the Sokolan from BASFTMPA 25 or from Dow's
AcusolTM425。
Equally suitable is multi-carboxylate's copolymer of the monomer of derived from propylene acid and maleic acid, such as from BASF's
CP5.The average molecular weight of these polymer of sour form is preferably 4,000 to 70,000.Also modified polycarboxylic acid's salt can be used
Such as from the Sokalan of BASFTMCP42, SokalanTMCP50, or the Alcoguard from AkzoNobelTM4160。
Also the mixture of scale preventative can be used.It is especially useful that the mixing of organic phosphonate and acrylate copolymer
Object.Preferably, the content of dispersed polymeres is 0.2 to 10 weight %, preferably 0.5 to the 8 weight % of total suspension, further
It is preferred that 1 to 6 weight %.
Glass corrosion inhibitors can prevent irreversible corrosion and iris of the glass surface in Dishwashing detergent for machine washing.
Claimed suspension can suitably contain glass corrosion inhibitors.Suitable glass corrosion agent can be selected from zinc, bismuth, aluminium, tin,
Magnesium, calcium, strontium, titanium, zirconium, manganese, the salt of lanthanum, mixture and its precursor.The salt or combinations thereof of most preferably bismuth, magnesium or zinc.This
The preferred content of glass corrosion inhibitors is 0.01-2 weight %, more preferable 0.01-0.5 weight % in suspension.
The rust that antirust agent can prevent or reduce metal (such as silver, copper, aluminium and stainless steel) is dirty, corrosion or oxidation.Antirust
Agent is as described in benzotriazole or double-benzotriazole and its substitution or substituted derivative and EP 723 577 (Unilever)
Those can also reside in suspension.It refers to may include in detergent suspension in WO 94/26860 and WO 94/26859
Other antirust agent.Suitable redox active agent is such as selected from cerium, cobalt, hafnium, gallium, manganese, titanium, vanadium, the complexing of zinc or zirconium
Object, wherein metal is in the oxidation state of II, II, IV, V or VI.
It is optionally possible to other components are added in preparation, such as fragrance, colorant or preservative.Detergent suspends
The desired viscosity property (profile) of liquid depends on the final use of product.Depending on application, it can be liquid, gel or
Paste.Another aspect of the present invention relates to a kind of water-soluble pouch (sachet), filled with suspension as defined hereinabove.
Rheology
Particularly preferred embodiment according to the present invention, detergent suspension are thixotropic liquid suspensions.
Term " thixotropic " be product be in a stationary situation viscosity and shaking, agitation or otherwise by
Become less sticky when stress.In thixotropic composition, this so-called " shear-thinning effect " is reversible, once i.e. group
It closes object and is no longer influenced by shear stress, more viscous state will be returned to.This thixotropic behavior of detergent suspension can lead to
It crosses and measures storage modulus (G ') and loss modulus of the product as the function of angular frequency (ω) on the rheometer of oscillation mode
(G ") is shown.Both G ' and G " of fluid product as angular frequency (ω) function and increase because G " is with faster than G '
Rate increases.At low-down angular frequency (ω), the G " of fluid product is lower than G ', but the ω within the scope of 0.05-50rad/s
Under, G " is more than G '.
Using board-to-board geometry, main shaft PP50/S (sandblasting) and 3mm gap size use AntonMCR
302 rheometers measure both storage modulus (G ') and loss modulus (G ") of fluid product at 20 DEG C.The program of application is arranged
It is as follows:
● selection strain γ in linear viscous-elastic range of product (LVER is determined by amplitude scan).Strain is maintained at
0.1% is constant.
● since 0.01rad/s, from low frequency to high-frequency, the cumulative slope pair of angular frequency is set on sample
Number.Except non-sample is very rigid, otherwise terminating ω is 100rad/s.
● the setting for collecting measurement point is " no time setting ".In this mode, equipment is before it obtains its measurement point
Wait lower state.
● every ten take six measurement points.
Using oscillatory rheological, both sticky sample and elasticity sample characteristic of material can be quantified on different time scales.
The basic principle of oscillatory rheometer is to cause sinusoidal shear-deformable in the sample and measure combined stress response；The time ruler of detection
Degree is determined by shear-deformable frequency of oscillation ω.Sample is placed between two plates.When top plate is remain stationary, motor makes bottom
Plate rotation, thus application time dependence strain γ (t)=γ sin (ω t) on sample.Meanwhile it being applied by measuring sample
The torque being added on top plate carrys out quantization time dependence stress σ (t).
This time dependence stress response is measured under single-frequency discloses key difference between material immediately.If
Material is ideal elastic solid (Hookean body), then the deformation of sample stress and strain is proportional, and proportionality constant is the modulus of shearing of material.
Stress deforms with the sinusoidal strain of application completely in phase always.
On the contrary, case of materials that pure viscous fluid, then the stress and strain deformation rate in sample is proportional, and wherein ratio is normal
Number is the viscosity of fluid.The strain of application and the stress of measurement are out-phase, phase angle δ=pi/2.
Viscoelastic material is shown containing with the response mutually with both out-phase contributions.These contributions disclose solid-like and liquid
The degree of sample behavior.As a result, phase shift delta of the total stress response display relative to the strain deformation of application, is located at solid and liquid
Between, 0 < δ < pi/2.Viscoelastic sexual behaviour of the system at ω is characterized in that storage modulus G ' (ω) and loss modulus G "
(ω) characterizes solid-like and the fluid-like contribution to the stress response measured respectively.γ (t)=γ is deformed for sinusoidal strain
0sin (ω t), the stress response of viscoelastic material is by σ (t)=G ' (ω) γ 0sin (ω t)+G " (ω) γ 0cos (ω T) gives
Out.
Product behaves much like solid or depends on the time scale when it is deformed more like liquid.It is minimum can
Up under frequency, detergent suspension of the invention has the loss modulus lower than storage modulus, indicates solid-like behavior, and most
It is high to be responded up under frequency, loss modulus is leading, indicate sticky sample behavior.
A particularly advantageous embodiment according to the present invention, detergent suspension is thixotropic composition, is had
In the storage modulus (G ' (ω)) at 20 DEG C and the loss modulus (G " (ω)) at 20 DEG C, two kinds of modulus are under 0.1% strain
Function measurement on the rheometer of the oscillation mode of operation as angular frequency (ω), in which:
● under the angular frequency (ω) in the range of 50 to 100rad/s, G " (ω) > G ' (ω), and
● under the angular frequency (ω) in the range of 0.01 to 0.05rad/s, G " (ω) < G ' (ω).
Particularly preferably there is the storage modulus (G ') and loss modulus (G ") for meeting at least one of the following conditions
Detergent suspension:
● in the range of 30 to 100rad/s, under the angular frequency (ω) more preferably in the range of 10 to 100rad/s,
G " (ω) > G ' (ω), and
● the angular frequency (ω) in the range of 0.01 to 0.2rad/s, more preferably in the range of 0.01 to 0.5rad/s
Under, G " (ω) < G ' (ω).
Dumpable detergent suspension has 1 to 100Pa, more preferable 8 to 30Pa, most preferably 10 usually at 0.2rad/s
To the storage modulus (G ') of 20Pa.
Loss modulus (G ") of the dumpable detergent suspension at 0.2rad/s be preferably 1 to 100Pa, more preferable 3 to
60Pa, most preferably 8 to 30Pa.
It is further illustrated by the following non-limitative examples the present invention.
Embodiment
Embodiment 1
Dumpable thixotropy machine washing tableware product is prepared based on formula shown in table 1.
Table 1
| Ingredient | Weight % |
| Glycerol | 48.67 |
| Citric acid (50%) | 1.43 |
| DissolvineTMGL 47-S1 | 9.40 |
| DissolvineTMPD-S 22 | 18.40 |
| Process water | 7.99 |
| Xanthan gum | 0.21 |
| Light carbonate ash (carbonate ash light) | 12.05 |
| Percarbonate3 | 1.10 |
| Bleach catalyst particles | 1.2 |
| LutensolTMAT80 (nonionic surfactant) | 1.87 |
1The water of GLDA containing about 48 weight % and 45 weight %
2The water of GLDA containing about 85 weight % and 9 weight %
3The percarbonate of coating, 98 weight %, 0.2 millimeter to 1.4 millimeters
Bleach catalyst particles are prepared as follows:
● the nuclear particle that volume weighted average diameter is about 600 μm is prepared by high shear granulation
● three dope layers are coated to these nuclear particles by fluidized bed coating process.In addition nuclear particle is successively coated containing bonding
The aqueous suspension of the catalyst granules of agent (dextrin), the aqueous suspension and PEG 4000 of sodium sulphate and titanium oxide, dioxy
Change titanium and kaolinic aqueous suspension.The volume weighted average diameter of the bleach catalyst particles so obtained is about 700 μ
m。
The composition of bleach catalyst particles is summarised in table 2.
Table 2
1Bleaching catalyst (manganese trimethyl -1,4,7- 7-triazacyclononane (triazacyclononanone)；CAS
No.116633-52.4 particle)；D99< 25 μm, D10≥1μm；D50In the range of 5-10 μm.
Machine washing tableware product is prepared as follows.It is pre- to prepare liquid by the way that glycerol and xanthan gum are mixed into uniform suspension
Mixed object.Then, water is added under constant stirring.Later, Dissolvine is given at ambient temperatureTMGL 47-S and citric acid.
Next, by DissolvineTMPD-S is mixed into.Finally, residual components are added in mixture under stiring.All the components are existed
Mixing is so that the formation of bubble minimizes under vacuum.
The detergent product so obtained is stable suspension, and when storing at ambient conditions, which is not sent out
It is raw mutually to separate or settle.During normal storage, the bleaching activity of product is not significantly reduced.The product is very sticky, but can
Unquestionably to be poured out from bottle.
Embodiment 2
By dumpable detergent suspension according to the present invention and identical but inclining using different bleach catalyst particles
Detergent composition is compared.Bleach catalyst particles A is based on the preparation of preparation shown in table 3.
Table 3
| Weight % | |
| ManCat (MN-TACN crystal) Mncat 1033 | 4 |
| Sodium carbonate (lightweight monohydrate ash) | 46.5 |
| Sodium metasilicate (Britesil H20) | 46.5 |
| Polyacrylate (adhesive) (25 pH > 8 CL 50% solution Pa) | 3 |
Bleach catalyst particles A is prepared as follows:
Carbonate and silicate and ManCat crystal are put into togerther in ploughshare mixer (ploughshare mixer).
While mixing, 3% adhesive is sprayed in powder bed with single-phase nozzle in 3 minutes.Continue to mix after the completion of spraying
It closes 10 minutes.Next, particle is discharged and is sieved on 710-255 μm of sieve plate.>255 μm and<710 μm of part is used for
Experiment.
Preparing dumpable detergent suspension based on formula shown in table 4, (bleach catalyst particles 1 are in embodiment 1
The bleach catalyst particles).Detergent suspension 1 is detergent suspension according to the present invention, and detergent suspending liquid A is not
It is.
Table 4
Detergent suspension is prepared with the batch of 3kg in Unimix (coming from Haagen&Rinau) mixer,
It is operated under the vacuum of 70rpm, while keeping the temperature of mixer content at 20 DEG C.The combination process used is as follows:
Glycerol and xanthan gum are introduced, is mixed 20 minutes；
Process water is added, continues stirring 20 minutes；
Citric acid solution and Dissolvine is addedTMGL 47-S is continuesd to mix 5 minutes；
Dissolvine is addedTMPD-S 2 is continuesd to mix 40 minutes；
Lutensol is addedTMAT80 and carbonate continue stirring 30 minutes；
Percarbonate and bleach catalyst particles are added, continues to mix 35 minutes.
The feature of two kinds of detergent suspension is summarized in table 5.
Table 5
1Using ATAM III system (coming from TA Instruments) measurement suspension sample when being kept for 40 hours for 50 DEG C
The standardization heat (J/g) of generation
The above results show the catalyst granules that suspending liquid A contains oxidation, and the percarbonate in suspending liquid A divides too early
Solution, it may be possible to due to the interaction with Mn catalyst.
Claims (14)
1. a kind of dumpable detergent suspension, it includes:
● the hygroscopic component of 30-80 weight % is selected from aminocarboxylate chelators, glycerol and combinations thereof；
● the water of 8-25 weight %；
● the bleaching agent of 0.5-30 weight %；
● the bleach catalyst particles that the diameter of 0.1-5 weight % is 20-2000 μm, the bleach catalyst particles include:
One or more nuclear particles of zero 30-90 weight %；
The coating of cladding one or more nuclear particles of zero 10-70 weight %, the coating is by one or more dope layers
It forms and contains:
The coating containing at least catalyst granules of the manganese bleaching catalyst of 30 weight % of -1-30 weight %；With
The coating of the water-soluble alkali sulfate of -50-99 weight %；
The bleach catalyst particles are without enzyme, the catalyst granules containing 0.3-20 weight % and contain 30-99 weight
Measure the water-soluble alkali sulfate of %.
2. detergent suspension according to claim 1, the wherein at least diameter of the catalyst granules of 90 weight %
It is 0.2-25 μm.
3. detergent suspension according to claim 1 or 2, wherein the bleach catalyst particles contain a kind of nuclear particle
And meet following specification:
● the diameter of the nuclear particle: 200-1000 μm；
● the volume weighted average diameter of the catalyst granules: 1-12 μm；
● the thickness of the coating: 10-150 μm.
4. detergent suspension according to claim 3, wherein the coating of the bleach catalyst particles includes at least two
A dope layer comprising (i) includes the catalyst granules of 30-90 weight % and the water-soluble binder of 10-70 weight %
The first dope layer, and (ii) surround the second layer of first dope layer, and second dope layer includes at least 60 weight %
Water soluble salt.
5. detergent suspension according to claim 4, wherein the water-soluble binder is selected from monosaccharide, disaccharides, trisaccharide,
Dextrin and combinations thereof.
6. detergent suspension according to any one of the preceding claims, wherein the water-soluble alkali sulfate is
Sodium sulphate.
7. detergent suspension according to any one of the preceding claims, wherein the suspension includes 8-40 weight %
Aminocarboxylate chelators.
8. detergent suspension according to any one of the preceding claims, wherein the suspension includes 20-75 weight
Measure the glycerol of %.
9. detergent suspension according to any one of the preceding claims, wherein glycerol, water and aminocarboxylate chelate
The combination of agent accounts for at least 45 weight % of the suspension.
10. detergent suspension according to any one of the preceding claims, wherein the suspension contains 10-22 weight
Measure the water of %.
11. detergent suspension according to any one of the preceding claims, wherein the suspension has at 20 DEG C
0.2 to 0.6 water activity.
12. detergent suspension according to any one of the preceding claims, wherein the suspension contains the weight by water
The structuring biological polymer of meter at least 0.1%.
13. detergent suspension according to claim 12, wherein the structuring biological polymer is selected from xanthan gum, thorn
Locust bean gum, guar gum, gum arabic, gellan gum, carrageenan, carboxymethyl cellulose, microcrystalline cellulose, microfibrous cellulose
And combinations thereof.
14. detergent suspension according to any one of the preceding claims, wherein the suspension is that thixotropy suspends
Liquid has in the storage modulus (G ' (ω)) at 20 DEG C and the loss modulus (G " (ω)) at 20 DEG C, and two kinds of modulus exist
Function measurement on the rheometer of the lower oscillation mode operated of 0.1% strain as angular frequency (ω), in which:
● under the angular frequency (ω) in the range of 50 to 100rad/s, G " (ω) > G ' (ω), and
● under the angular frequency (ω) in the range of 0.01 to 0.05rad/s, G " (ω) < G ' (ω).
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP16159923.8 | 2016-03-11 | ||
| EP16159923 | 2016-03-11 | ||
| PCT/EP2017/055553 WO2017153528A1 (en) | 2016-03-11 | 2017-03-09 | Pourable detergent suspension comprising bleach catalyst granules |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109312267A true CN109312267A (en) | 2019-02-05 |
| CN109312267B CN109312267B (en) | 2021-02-05 |
Family
ID=55527420
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201780016161.1A Active CN109312267B (en) | 2016-03-11 | 2017-03-09 | Pourable detergent suspensions comprising bleach catalyst particles |
Country Status (8)
| Country | Link |
|---|---|
| EP (1) | EP3426756B1 (en) |
| JP (1) | JP2019507808A (en) |
| CN (1) | CN109312267B (en) |
| AR (1) | AR107853A1 (en) |
| PL (1) | PL3426756T3 (en) |
| PT (1) | PT3426756T (en) |
| TR (1) | TR201911286T4 (en) |
| WO (1) | WO2017153528A1 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2568867A (en) * | 2017-10-31 | 2019-06-05 | Mcbride Sa | Dishwashing detergent gel comprising bleach |
| GB201814981D0 (en) | 2018-09-14 | 2018-10-31 | Reckitt Benckiser Finish Bv | Granulate |
| EP3967742A1 (en) | 2020-09-15 | 2022-03-16 | WeylChem Performance Products GmbH | Compositions comprising bleaching catalyst, manufacturing process thereof, and bleaching and cleaning agent comprising same |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000029533A1 (en) * | 1998-11-12 | 2000-05-25 | Henkel Kommanditgesellschaft Auf Aktien | Aqueous detergents for dishwasher |
| WO2008064935A1 (en) * | 2006-11-27 | 2008-06-05 | Henkel Ag & Co. Kgaa | Granulated bleached catalysts |
| US20090256113A1 (en) * | 2005-07-28 | 2009-10-15 | Georg Borchers | Method for the Production of Bleaching Catalyst Granules |
| WO2013092276A1 (en) * | 2011-12-22 | 2013-06-27 | Unilever N.V. | Detergent composition comprising glutamic-n,n-diacetate, water and bleaching agent |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4751015A (en) | 1987-03-17 | 1988-06-14 | Lever Brothers Company | Quaternary ammonium or phosphonium substituted peroxy carbonic acid precursors and their use in detergent bleach compositions |
| ES2100925T3 (en) | 1990-05-21 | 1997-07-01 | Unilever Nv | WHITENING ACTIVATION. |
| EP0697036B1 (en) | 1993-05-08 | 1999-07-28 | Henkel Kommanditgesellschaft auf Aktien | Silver-corrosion protection agent (ii) |
| CZ286401B6 (en) | 1993-05-08 | 2000-04-12 | Henkel Kgaa | Use of inorganic redox-active substances |
| CA2171312A1 (en) | 1993-10-14 | 1995-04-20 | Petrus Adrianus J. M. Angevaare | Detergent compositions containing silver anti-tarnishing agents |
| US5547612A (en) | 1995-02-17 | 1996-08-20 | National Starch And Chemical Investment Holding Corporation | Compositions of water soluble polymers containing allyloxybenzenesulfonic acid monomer and methallyl sulfonic acid monomer and methods for use in aqueous systems |
| US6210600B1 (en) | 1996-12-23 | 2001-04-03 | Lever Brothers Company, Division Of Conopco, Inc. | Rinse aid compositions containing scale inhibiting polymers |
| KR20150103370A (en) | 2013-01-03 | 2015-09-10 | 바스프 에스이 | Homogeneous detergent composition |
| US20170145353A1 (en) | 2014-07-08 | 2017-05-25 | Novozymes A/S | Co-Granulate of Enzyme and Bleach Catalyst |
-
2017
- 2017-03-09 WO PCT/EP2017/055553 patent/WO2017153528A1/en active Application Filing
- 2017-03-09 CN CN201780016161.1A patent/CN109312267B/en active Active
- 2017-03-09 JP JP2018540153A patent/JP2019507808A/en not_active Withdrawn
- 2017-03-09 PL PL17709682T patent/PL3426756T3/en unknown
- 2017-03-09 PT PT177096823T patent/PT3426756T/en unknown
- 2017-03-09 TR TR2019/11286T patent/TR201911286T4/en unknown
- 2017-03-09 EP EP17709682.3A patent/EP3426756B1/en active Active
- 2017-03-10 AR ARP170100602A patent/AR107853A1/en active IP Right Grant
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000029533A1 (en) * | 1998-11-12 | 2000-05-25 | Henkel Kommanditgesellschaft Auf Aktien | Aqueous detergents for dishwasher |
| US20090256113A1 (en) * | 2005-07-28 | 2009-10-15 | Georg Borchers | Method for the Production of Bleaching Catalyst Granules |
| WO2008064935A1 (en) * | 2006-11-27 | 2008-06-05 | Henkel Ag & Co. Kgaa | Granulated bleached catalysts |
| WO2013092276A1 (en) * | 2011-12-22 | 2013-06-27 | Unilever N.V. | Detergent composition comprising glutamic-n,n-diacetate, water and bleaching agent |
Also Published As
| Publication number | Publication date |
|---|---|
| PL3426756T3 (en) | 2020-01-31 |
| AR107853A1 (en) | 2018-06-13 |
| JP2019507808A (en) | 2019-03-22 |
| EP3426756B1 (en) | 2019-07-03 |
| EP3426756A1 (en) | 2019-01-16 |
| CN109312267B (en) | 2021-02-05 |
| TR201911286T4 (en) | 2019-08-21 |
| WO2017153528A1 (en) | 2017-09-14 |
| PT3426756T (en) | 2019-10-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5571203B2 (en) | Liquid detergent composition comprising pH-adjustable amide gelling agent and production method | |
| JP2018104720A (en) | Itaconic acid polymers | |
| JP4318759B2 (en) | Non-aqueous speckle-containing liquid detergent composition | |
| TWI637053B (en) | Polymers, process for preparing polymer solution thereof, and process of chelating metal ions from solution | |
| JPH11514029A (en) | Non-aqueous liquid detergent composition | |
| JP2001512177A (en) | Tablet detergent | |
| JPH11501357A (en) | Bleach catalyst plus enzyme particles | |
| JP2001526307A (en) | Non-aqueous liquid detergent compositions containing ethoxylated quaternized amine clay compounds | |
| CN109312267A (en) | Dumpable detergent suspension comprising bleach catalyst particles | |
| JP2002508440A (en) | Cleaning tablets | |
| CN105324475A (en) | Composition comprising glutamic-N,N-diacetate (GLDA), water and enzyme | |
| JP4663825B2 (en) | Cleaning enzyme composite particles having a water-soluble carboxylate barrier layer and an automatic dishwashing composition comprising the same | |
| JP2002507230A (en) | Non-aqueous liquid detergent composition containing enzyme particles | |
| JP2002535449A (en) | Detergent tablet | |
| CN105492589A (en) | Pourable detergent composition comprising suspended particles | |
| CN105308165A (en) | Hygroscopic detergent formulation comprising water, aminocarboxylate chelant and moisture-sensitive ingredients | |
| CN109790486A (en) | Low PH laundry detergent composition | |
| JPH11514030A (en) | Preparation of Non-Aqueous Particle-Containing Liquid Detergent Composition Containing Pretreated and Dry Components | |
| CN108713056B (en) | Detergent composition in the form of a suspension | |
| TWI409328B (en) | Bleach activator granules | |
| JPH11514027A (en) | Non-aqueous liquid cleaning compositions containing coated particles | |
| CN104508107A (en) | Solid detergent composition | |
| CN105473700A (en) | Bleach and oxidation catalyst | |
| WO2017148985A1 (en) | Pourable detergent composition | |
| JP2008001736A (en) | Powdered bleaching agent composition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20210817 Address after: Rotterdam Patentee after: Unilever Intellectual Property Holdings Ltd. Address before: Rotterdam Patentee before: Netherlands Unilever Co.,Ltd. |
|
| TR01 | Transfer of patent right |