CN105814182B - The method for manufacturing the isotropism aqueous detergent liquid of external structurant - Google Patents
The method for manufacturing the isotropism aqueous detergent liquid of external structurant Download PDFInfo
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- CN105814182B CN105814182B CN201480070359.4A CN201480070359A CN105814182B CN 105814182 B CN105814182 B CN 105814182B CN 201480070359 A CN201480070359 A CN 201480070359A CN 105814182 B CN105814182 B CN 105814182B
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- 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
- C11D3/382—Vegetable products, e.g. soya meal, wood flour, sawdust
-
- 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
- C11D17/0008—Detergent materials or soaps characterised by their shape or physical properties aqueous liquid non soap compositions
- C11D17/0026—Structured liquid compositions, e.g. liquid crystalline phases or network containing non-Newtonian phase
-
- 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
- C11D3/12—Water-insoluble compounds
- C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
- C11D3/1246—Silicates, e.g. diatomaceous earth
- C11D3/1253—Layer silicates, e.g. talcum, kaolin, clay, bentonite, smectite, montmorillonite, hectorite or attapulgite
- C11D3/1266—Layer silicates, e.g. talcum, kaolin, clay, bentonite, smectite, montmorillonite, hectorite or attapulgite in liquid compositions
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- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Wood Science & Technology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Detergent Compositions (AREA)
Abstract
The present invention relates to the methods of the aqueous detergent liquid formulations of manufacture external structurant, the described method comprises the following steps:Form the pre-composition of citrus fruit fibres and water-swellable clay powders;Then so that citrus fruit fibres and the pre-composition of water-swellable clay powders is passed through high-pressure homogenizer to form homogenized addition of structurant, be then added to the surfactant of few 2 wt% and add at least non-clay solid particle of 0.001 wt% to form the liquid formulations of external structurant.
Description
Technical field
The present invention relates to manufacture external structurant aqueous detergent liquid method, for this method clay powders and
The structuring of citrus fruit fibres (citrus fibre), homogenized pre-composition and use the structuring, homogenized premix
The aqueous detergent liquid of the external structurant of gained prepared by object.
Background technology
Isotropic liquid detergent composition does not have suspended solid particles, such as indicant (cue) and encapsulant
(encapsulate) capability.Although can be suspended by suitably manipulating surfactant and electrolyte level
Medium, but such method imposes undesirable constraint to composition.This already leads to use so-called outside " structural agent
(structurant) ", it now is possible to by the suspension function (duty) needed for its acquisition without the level to component in composition
Impose restricted constraint.
The term " outside " used present document relates to structural agent refers to that can be added to preparation, while keeping detergent liquid
The reagent of the required fluid properties of body.This is contrasted with " inside " structural agent, and " inside " structural agent is using for example
Electrolyte or salt make detergent liquid structuring and its result in from inside can be with the lamellar phase of suspended solid particles or " solidifying
Glue ".Although the use of internal structure agent can be the method for the cost-efficient suspension property for generating particle in detergent,
But such preparation often has excessively high viscosity, results in the need for rheology modifier.In contrast, it is often preferable to use can be with
" outside " is added to preparation, while keeping the reagent of fluid properties.
In the presence of many structural agents applied for detergent.One example of external structurant is citrus fruit fibres.Packet
Composition containing citrus fruit fibres and its be used for the description of the purposes in food and personal care composition in US2004/0086626 and
In US2009/269376.
In addition, the citrus fruit fibres structural liquid detergent composition of activation exists with the compatibility description for cleaning and nursing enzyme
In WO2012/052306.Citrus fruit fibres are combined with Cationic Deposition Polvmer (Jaguar quaternized guars) is used for antidandruff
The purposes of shampoo is also disclosed in WO2012/019934.US 7981855 is disclosed comprising up to 15wt% surfactants
(comprising at least 1wt% anion surfactants), up to 2wt% bacteria celluloses (preferably MFC) and 0.001 are to 5wt% mandarin oranges
The detergent liquid surface activator composition of tangerine fiber.
Unfortunately, when using structural agent of the citrus fruit fibres as detergent preparation of activation, especially when with enough
There are disadvantages when high yield strength level use is with suspended solid particles, because ought liquid composition for example be poured out from container
When, this can lead to reservation of the residue on container.In addition, when citrus fruit fibres are used alone as external structurant, and do not have
When having citrus pulp (citrus pulp) fiber of overprocessing, level of stability needed for composition can not possibly be often obtained.
Such as EP1402877 (Rohm and Haas) and Research Disclosure, in June, 2000, the 434th phase,
Disclosed in 1032-1033 pages, another known architectures for suspended solid particles are clay and rheology modification of polymers
Combination.
Clay had previously been used as clay colloidal sol in detergent preparation in liquid form.Clay colloidal sol and clay powder
Difference lies in by clay is pre-dispersed and the stable components for belonging to supplier of logical usual additional at end.Although molten using clay
Glue than being easily processed colloidal sol using clay powders, is thus reduced by the intrinsic of the clay powders sucking generation during handling really
Some unique advantages are provided in terms of safety issue, but are led to the problem of using clay colloidal sol other, need to carry out it
It solves to allow efficient processing.This problem includes needing to use preservative, because clay is liquid form, Yi Jiyou
The increased processing cost caused by the high price of clay colloidal sol and collosol intermixture is processed into volume caused by detergent liquid
Outer expense.
In addition, the shortcomings that main thickener in using clay as detergent composition is that they are easy to and other ingredients
Interaction, the result is that the viscosity of composition changes over time and syneresis may occur.
Although there is also the preparations used with the citrus fruit fibres of clay aerosol composition as external structurant, also
It is found that such preparation shows stability problem.
In reducing preparation cost and overcoming the problems, such as the trial related to known detergent preparation, the present inventor is present
Thus gram it has been devised by improved novel method, allows coprocessing structural agent, especially clay powders and citrus fruit fibres,
Take intrinsic manufacturing issue and increased cost.
In addition, the present inventor has been designed that novel method now, through this can successfully coprocessing clay powders with
For citrus pulp fiber to obtain effective structurant system, which overcome previously undergone when structural agent is used alone or in combination
Prior art problem.
Therefore, it is an object of the present invention to provide for manufacturing the isotropism aqueous detergent for being used for external structurant
The improved method of the co-structured agent pre-composition of liquid, which overcome the problems related to existing method.
It is a further object to provide the detergent pre-composition preparations and packet of the structural agent comprising coprocessing
Isotropism aqueous detergent liquid containing its external structurant.
Invention content
According to the first aspect of the invention, the side of the aqueous detergent liquid formulations of manufacture external structurant is provided
Method comprising following steps:
I) pre-composition of citrus fruit fibres and water-swellable clay powders is formed;Then
Ii the pre-composition of external structurant) is made to pass through high-pressure homogenizer to form homogenized addition of structurant, so
Following substance is added to homogenized addition of structurant afterwards:
Iii) at least surfactant of 2wt%;With
Iv) the non-clay solid particle of at least 0.001wt%, and grind to form the detergent liquid of external aqueous structuring
Body preparation.
Preferably make pressure of the pre-composition of water-swellable clay powders and citrus pulp fiber 5000 to 80000kPa
Under pass through high-pressure homogenizer.It is highly preferred that make the pre-composition of water-swellable clay powders and citrus pulp fiber 700 to
Pass through high-pressure homogenizer under the pressure of 70000kPa.
Such pressure is absolute pressure.
So that citrus fruit fibres and the pre-composition of water-swellable clay powders is passed through high-pressure homogenizer leads to citrus fruit fibres and clay
The structure of powder is destroyed and hydration, forms homogenized addition of structurant.Then surfactant and non-clay solid are used
Grain disperses homogenized addition of structurant to form the detergent liquid preparation of external aqueous structuring.
In the present invention, therefore external structurant is citrus pulp fiber and water-swellable clay, and preferably Laponite is viscous
Soil has been subjected to mechanical treatment and therefore can absorb at least 15 times of water of its own dry weight.It is highly preferred that citrus pulp is fine
At least 20 times of water of its weight of peacekeeping water-swellable clay absorption.
Preferably pre-composition is preferably at least amount of 0.04wt% comprising clay powders and at least amount of 0.02wt%
Include the citrus pulp fiber of activation.It is highly preferred that amount of the citrus pulp fiber in pre-composition is 0.02 to 2.5wt%.Most preferably
Ground, amount of the citrus pulp fiber in pre-composition are 0.04 to 1.5wt%.
In addition, amount of the water-swellable clay in pre-composition is 0.04 to 5.0wt%.Most preferably, citrus pulp is premixing
Amount in object is 0.06 to 3.0wt%.
The yield stress of further preferably homogenized addition of structurant ranging from 10 to 200Pa.It is highly preferred that through equal
The yield stress of the addition of structurant of change ranging from 15 to 140Pa.
Method also about the present invention, the preparation of detergent preparation need to add surfactant, wherein surface-active
Agent accounts for the 2 to 70wt% of detergent preparation.It is highly preferred that amount of the surfactant in detergent preparation be 3 to
50wt%.The amount of anion surfactant existing for a part as the total amount of surfactant be 5 to 70wt%, and
The amount of amphoteric surfactant existing for a part as the total amount of surfactant is 1 to 20wt%.
In addition, the method also about the present invention, detergent preparation includes one or more non-stick soil particles of addition,
It is selected from:
Visual indicator (visual cues), fragrance encapsulant, nursing additive and cleansing.
Amount of the non-stick soil particle in detergent preparation is preferably 0.001 to 20wt%.It is highly preferred that non-stick soil particle
Amount in detergent preparation is preferably 0.01 to 10wt%.
In addition, the method for manufacturing detergent preparation according to the present invention include add one or more antifungal agents and/
Or antibacterial agent.Dyestuff can also be added in the preparation of the present invention.
Citrus fruit fibres are originated from citrus fruit and advantageously comprise the skin of lemon and/or bitter orange.Citrus fruit fibres can be inhaled
Receive and combine at least 15 times of water of its own weight, preferably at least 20 times and even up to 30 times of its own weight.
According to the second aspect of the invention, the water for providing the aqueous detergent liquid formulations for external structurant can
The homogenized addition of structurant of Swelling Clay and citrus fruit fibres slag, it includes:The water-swellable clay of at least 0.04wt%
At least citrus fruit fibres of 0.02wt%.
It is highly preferred that amount of the citrus fruit fibres slag in pre-composition is 0.02 to 2.5wt%.Most preferably, citrus fruit fibres slag
Amount in pre-composition is 0.04 to 1.5wt%.
In addition, amount of the water-swellable clay in pre-composition is 0.04 to 5.0wt%.Most preferably, water-swellable clay
Amount in pre-composition is 0.06 to 3.0wt%.
In addition, the yield stress of pre-composition ranging from 10 to 200Pa.It is highly preferred that the yield stress of pre-composition is ranging from
15 to 140Pa.Pre-composition pressure limit is preferably 5 000 to 80 000kPa.It is highly preferred that pre-composition pressure limit is 7000
To 70 000kPa.
The inventors have discovered that when preparing detergent liquid preparation, the citrus of water-swellable clay and activation is used
The pre-composition of slag fiber is compared to the citrus fruit fibres that activation is used alone or water-swellable clay is used alone, or is used alone and lives
The citrus fruit fibres of change then provide many benefits with water-swellable clay combination.
Therefore, according to the third aspect of the invention we, what the method for providing any one of usable claims 1 to 10 obtained
The aqueous detergent liquid formulations of external structurant, it includes the citrus fruit fibres and water-swellable of homogenized pre-composition form
Clay powders, wherein composition include:
I) at least clay powders of 0.04wt%;
Ii) the citrus pulp fiber of at least 0.02wt%;
Iii) at least surfactant of 2wt%;With
Iv) the non-clay solid particle of at least 0.001wt%.
It is viscous that external structurant aqueous detergent liquid composition according to a second aspect of the present invention preferably comprises water-swellable
The yield stress of the homogenized pre-composition of native powder and citrus fruit fibres, the pre-composition is most preferably 10 to 200Pa.More preferably
The yield stress of the homogenized pre-composition of ground, clay powders and citrus fruit fibres slag is 12 to 170Pa.Most preferably, clay powder
The yield stress of the homogenized pre-composition of end and citrus fruit fibres slag is 15 to 140Pa.
Level of the citrus fruit fibres slag in preparation is 0.02 to 2.5wt%.It is highly preferred that citrus pulp is in preparation
Level is 0.02 to 0.16.
Level of the water-swellable clay in preparation is 0.04 to 0.5wt%.It is highly preferred that water-swellable clay with
The clay that level in product is 0.04 to 0.45wt%.
The aqueous detergent liquid composition of external structurant preferably further include one or more antifungal agents and/or
Antibacterial agent and/or one or more dyestuffs.
In addition, the aqueous detergent liquid formulations of external structurant preferably comprise 0.02 to 2.5wt% ranges citrus
Fiber.It is highly preferred that the aqueous detergent liquid formulations of external structurant preferably comprise 0.02 to 0.16wt% ranges mandarin orange
Tangerine fibrous residue.
In addition, clay powders preferably exist with 0.04 to 0.5wt% range.It is highly preferred that clay powders preferably with
0.04 to 0.45wt% range is present in the aqueous detergent liquid formulations of external structurant.
Therefore, the present invention provides be used for being total in the isotropism aqueous detergent liquid of external structurant for manufacturing
The improved method of structuring agent premix;Including the detergent pre-composition preparation of the structural agent of coprocessing and comprising its
External structurant isotropism aqueous detergent liquid, whole overcome the problem related to existing method.
In addition, the present invention also provides following additional and unexpected benefits:Although the premix of preparation according to the present invention
The yield stress of object is relative to the pre-composition for example formed using clay colloidal sol and citrus pulp as the structural agent individually handled
It reduces, but total yield stress of final preparation improves.Therefore, detergent preparation can successfully suspend in preparation and exist
Solid particle without lose stability.
Specific implementation mode
Detergent composition
1. the citrus fruit fibres of activation
Can be by citrus fruit (mainly lemon and bitter orange) de- juice to leave insoluble plant cell wall material, some
Contain sugar and pectin in inside." the sponge micro-structure " for being referred to as white cortex (albedo) can be used for preparing acid powders shape mandarin orange
Tangerine fiber.The structure is dry, screening, is washed out to improve fiber content.Dried material is typically big (to have
100 microns of cell fragment is made of the fibrinogen of close adhesion/combination).Powdered citrus fruit fibres material is obtained after grinding
Material.The step keeps many natural fine cell walls complete and removes desaccharification.The swellable citrus fruit fibres material of gained is typically used as food additive
Add agent and is frequently used for such as low-fat mayonnaise.
Microexamination shows that powdered citrus fruit fibres are the heterogeneous mixtures of the particle with various sizes and shape.
The major part of material is made of the aggregation agglomerate of cell wall and cell wall fragments.However, it is possible to identify that many opening diameters are
About 10 microns of tubular structure, usual cluster arrangement.These so-called xylem vessels are predominantly located at citrus fruit
Water transport channel in skin.Xylem vessel is made of dead cell stacking, they are joined together to form 200 to 300 microns long
Relatively long pipe.The lignin enhancing that the outside of pipe is generally ring or spiral is laid with, to prevent pipe due in water delivery process
In act on the capillary force of tube wall and cave in.
For preferred type detergent composition and used according to the invention powdered citrus fruit fibres from
Herbafoods is with trade (brand) name HerbacelTMAQ+ type N citrus fruit fibres can obtain.The citrus fruit fibres have total more than 80wt%
(soluble and insoluble) fiber content and the soluble fibre content more than 20wt%.It is as the thin drying with light colour
Powder supplies and the water binding ability with about 20 kilograms of water of every Kg of powder.
In order to obtain structure appropriate, when forming the pre-composition of the present invention, via high shear dispersion method in water with viscous
The powdered citrus fruit fibres of native powder activation (be hydrated and opened in structure).Include in pre-composition by preservative advantageously,
This is because the citrus fruit fibres of the activation of dispersion are biodegradable.
Desirably being applied to the shearing of citrus fruit fibres should not up to cause fibril to detach (defibrillation).Cause
This, if using high-pressure homogenizer, preferably in 5 000 to 100 000kPa, more preferably between 7 000 to 70 000kPa
Operation.The shearing of application is bigger, and gained particle is got over not fine and close.Although changing form by high shear, appear not to change
The aggregate size of change method.But fiber is broken, is subsequently filled water phase.Cutting method also rubs the outside of loose fresh fruit cell wall,
And these can form the matrix of the water-bound outside the volume by pristine fibre.
Pulpous state citrus fruit fibres produce bacteria cellulose considerably cheaper.
2. water-swellable clay
Suitable water-swellable clay for laundry applications is aqueous layer aluminium silicate (aluminium
Phylosilicate), there is iron, magnesium, alkali metal, alkaline-earth metal and the other cations of variable sometimes.Clay forms class
It is similar to the flat hexagon piece of mica.Clay is ultrafine particulate (it has been generally acknowledged that being sorted in smaller in dimension than 2 based on standard particle size
Micron).
Clay is commonly known as 1:1 or 2:1 clay.Clay is substantially constructed by tetrahedron and/or octahedral sheet.1:1 clay
It is made of a tetrahedral sheet and an octahedral sheet, and example includes kaolinite and serpentine.2:1 clay is by being clipped in two
Octahedral sheet composition between tetrahedral sheet, and example is illite, smectite (smectite) and attapulgite.
Smectite class includes dioctahedron smectite, such as montmorillonite and nontronite and trioctahedron smectite, such as soap
Stone.And bentonite, pyrophyllite, hectorite, sauconite, talcum, beidellite.Other 2:1 clay type includes sepiolite
Or attapulgite, it is the clay that there is long aquaporin in its inside configuration.Phyllosilicate includes:Galapectite, kaolinite, she
Sharp stone, montmorillonite, vermiculite, talcum, palygorskite, pyrophyllite.Montmorillonite is smectite phyllosilicate (Na, Ca)0.33(Al,Mg)2
(Si4O10)(OH)2·nH2O.Montmorillonite is very soft laminar silicic acid salt mineral, and it typically is microcosmic crystal forms with shape
At clay.Montmorillonite is 2:1 clay, this indicates that it has 2 tetrahedral sheets for accompanying center octahedral sheet.The particle is sheet
, with about 1 micron of average diameter.Montmorillonite is the main component of bentonite (volcanic ash sedentary product).Hectorite
It is the natural smectite clay with high silicon dioxide content.Natural hectorite is very soft, oiliness white clay mineral.
Suitable water-swellable clay includes:Smectite, kaolin, illite, chlorite and attapulgite.It is such viscous
The specific example of soil includes bentonite, pyrophyllite, hectorite, saponite, sauconite, nontronite, talcum and beidellite conduct
Smectite type clay.Water-swellable clay is preferably smectite type clay.
Montmorillonitic clay is in the presence of a stabilizer to ionic strength sensitive.They are being typically found in many washings
Its liquid structure efficiency is lost under polyelectrolyte level in agent composition.Clay tends to be caved under these conditions certainly
With it or flocculate.If this occurs during storage to cave in, liquid will lose its physical stability, experience syneresis and/
Or solid sedimentation.
Preferred water-swellable clay used according to the invention is smectite type clay, selected from Laponite, silicic acid
Aluminium, bentonite and pyrogenic silica.Most preferably hectorite is commercially synthesized from BYK Additives (Altana
Corporate entity) Laponites.Particularly preferred synthetic li-montmorillonite is:Laponite S、Laponite ES、Laponite
RD, Laponite RDS, Laponite XLS, Laponite ESL and Laponite EL.Laponite RD、XLG、D、EL、
OG and LV is entirely lithium metasilicate magnesium sodium.Most preferably Laponite EL, Laponite ESL and Laponite ES.
Other synthetic li-montmorillonite type clays include:Velum Pro and Velum F from RT Vanderbilt, and come
From the Barasymacaloids and Proaloids of Baroid division of National Lead Company.
Smectite is synthesized by metal salt, such as the salt and silicate of sodium, magnesium and lithium, especially the combination of sodium metasilicate is controlled
Ratio is synthesized at a temperature of.This generates amorphous sediment object, then partially crystallizable.Then the product of gained is filtered, washed,
To generate the powder for including tablet (platelet), the tablet has the mean tabular less than 100nm for dry and grinding
Object size.Platelet size refers to the longest linear dimension of given tablet.Synthesis of clay avoids using to be existed in natural clay
Impurity.
By the ratio that carefully controls and at a temperature of combination sodium, magnesium and lithium salt synthesize Laponite with sodium metasilicate.This
Amorphous sediment object is generated, then passes through high-temperature process partially crystallizable.The product of gained is filtered, washed, dried and ground
To thin white powder.
The size of clay is important.Therefore, because the small grain size of synthetic li-montmorillonite, very thin synthetic li-montmorillonite
It is particularly preferred.Granularity is the discrete particle size for the clay got wet.Suitable granularity is 0.001 to 1 micron, more preferably
0.005 to 0.5 micron and most preferably 0.01 to 0.1 micron.It can be by clay abrasive or crushing so that average-size is in required model
In enclosing.
Laponite has the average platelet size full-size less than 100nm.Laponite has layer structure, point
It is the plate-shaped crystal form of respectively about 1nm thickness and about 25nm diameters when dissipating in water.Small platelet size provides good
Spraying property, rheological characteristic and transparency (clarity).Preferably, clay has the particle size range within the scope of colloid.In general, working as
When it is hydrated, such clay provides clear solution, this may be because when clay hydration and stripping (exfoliate), clay
Particle does not scatter light.Other larger clays will provide the low-shear viscosity built on demand, but composition will lack transparency.
It is by BYK Additives for the method for the present invention and the most preferred water-swellable clay of detergent preparation
With title Laponite EL, ES or ESL supply synthesis of clay because these clays combine very small granularity with to washing
Wash the tolerance of high ionic strength present in agent liquid.Laponite EL, ES or ESL form dispersion and have in water
High surface charge.In other words give its improved tolerance to electrolyte (including anion surfactant).
Laponite EL, ES or ESL can be obtained in the form of two kinds of powder and colloidal sol.Each is suitable in detergent liquid composition.
Laponite has layer structure, is plate-shaped crystal form when being dispersed in water.It can be envisioned for two-dimentional " nothing
Machine polymer ", wherein empirical formula form the structure cell in crystal, and the structure cell has two layers for being clipped in four tetrahedron silicon atoms
Between six octahedra magnesium ions.These groups are by 20 oxygen atoms and four hydroxyl counters.The height of structure cell represents
The thickness of Laponite crystal.Structure cell is repeated many times in both direction, brings the plate-like appearance of crystal.It has been expected typical case
Laponite crystal include up to 2000 these structure cells.The macromolecular of the granularity is referred to as colloid.Natural clay mineral increases
Thick dose, such as bentonite and hectorite are with similar plate-shaped crystal structure but dimensionally greatly higher than an order of magnitude.
The primary particle size of Laponite is more much smaller than natural hectorite or bentonite.Utopian structure will have neutral charge, six
A divalent magnesium ion generates 12 positive charges in octahedral layer.However in fact, some magnesium ions are by lithium ion (monovalence)
Substitution, and some positions are empty.The clay has 0.7 negative electrical charge per structure cell, is neutralized during manufacture, because of sodium
Ion is attracted on plane of crystal.Crystal arrangement is at stacking, by sharing the sodium in the interlayer region between adjacent crystal
Ion and electrostatical binding are together.At 25 DEG C in tap water and under fast stirring, this method is substantially after 10 minutes
It completes.High shear mixing, raised temperature or chemical dispersant are not needed.The dilution dispersions of Laponite in deionized water
The dispersions with low viscosity of non-interaction crystal can be kept for a long time.Plane of crystal has 50 to 55mmol.100g-1Negative electricity
Lotus.Crystal edge has small local positive charge, is generated by the Ions Absorption of crystal structure termination.The positive charge is usual
It is 4 to 5mmol.100g-1.Polar compound (such as simple salt, the surface of solution form are added to the dispersion of Laponite
The additive of the forms such as activating agent, agglomerated solvent, soluble impurity and pigment, filler or adhesive) osmotic pressure will be reduced, it keeps
Sodium ion is far from particle surface.This makes electric double layer shrink and makes the negativity table of positive charge weaker in crystal edge and adjacent crystal
Face interacts.
This method can continue with generation " playing cards room (house of cards) " structure, in Laponite, water and salt
Simple system in be considered as high thixotropic gel.The gel is by passing through the combined single coagulated particles group of weak electrostatic force
At.
The water-swellable Laponite clays for being used to form the pre-composition in the method for the present invention are powder types and can
To be used with the amount of at least 0.04wt%.
Preferably, water-swellable Laponite clays can be used with the amount of at least 0.05wt%.It is highly preferred that water soluble
Swollen Laponite clays can be used with the amount of at least 0.06wt%.
In addition, water-swellable clay preferably exists with the amount no more than 3.5wt%.It is highly preferred that water-swellable clay with
Amount no more than 3wt% exists.Most preferably, water-swellable clay exists with the amount no more than 2.5wt%.
Laponite EL, ES and ESL clays be also with such as the present invention in preparation containing citrus pulp be used together it is preferred
Structural agent because clay makes it possible to obtain the preparation of relatively low citrus pulp as co-structured agent by using clay.
According to the present invention it is possible to by using high-shear mixer, such as Silverson grindings prepare the citrus fibre of activation
Peacekeeping caly structure pre-composition.In the method for the invention, can make pre-composition by several successive high shear stages with
Ensure the abundant hydration of citrus fruit fibres and clay and disperses to form citrus fruit fibres/clay powders dispersion of activation.
Although pre-composition can be made further to be hydrated (or aging) after high shear dispersion, but it is preferred that in the pre- of activation
Mixed object uses when fresh.
In addition, the pre-composition through high pressure homogenization is more preferred than ground pre-composition, because the former for liquid to providing enough
Suspension function more weight it is effective.
It has been found that improving homogenization pressures provides the weight efficiency further increased for pre-composition.Suitable operating pressure
It is about 5000 to 80000kPa.It is highly preferred that the operating pressure for being about 10000 to 50000kPa can be used.
Because lacking the stability of the detergent preparation prepared under big plant layout sometimes (due in preparation
Entrapped air, macro (micronization) of this air usually during grinding by, deteriorate), mechanical degasser also may be used
For removing the air for suspending and capturing by process of lapping from the liquid of structuring.
It is used using (co-streamed) water-swellable Laponite clays according to the present invention flowed altogether and citrus pulp fiber
In reducing the aeration quantity in preparing, mechanical deaeration amount is thus reduced, the production cost of faster operating time and reduction is caused.
Level of the citrus fruit fibres of activation in pre-composition prepared in accordance with the present invention is preferably 0.2 to 3wt%.More preferably
Ground, the level of the citrus fruit fibres of activation in pre-composition prepared in accordance with the present invention is preferably 0.1 to 2wt%.Most preferably, living
Level of the citrus fruit fibres of change in pre-composition prepared in accordance with the present invention is preferably 0.04 to 1.5wt%.
However, to there is the reader of technology to will be apparent that concentration of the citrus fruit fibres of activation in pre-composition depends on equipment
Cope with the ability of viscosity higher (especially at higher concentrations).
Preferably, amount of the water in pre-composition is at least 20 times of the amount of citrus fruit fibres.It is highly preferred that water is in pre-composition
Amount be at least 25 times of amount of citrus fruit fibres.Even further preferably, amount of the water in pre-composition is up to the amount of citrus fruit fibres
50 times.It is also advantageous in that there are excessive water with the citrus fruit fibres of abundant Hydration Activation.Preferred pre-composition has at least 15Pa
Measurement yield stress, surveyed at 25 DEG C using Anton Paar zigzag cups and rotor (cup and bob) geometry
Measure yield stress.
When being added to liquid detergent composition, the citrus fruit fibres of activation promote composition yield stress and 21s-1Under
Topple over viscosity (pour viscosity), and composition is referred to as shear thinning liquid.Yield stress and 21s-1Under
Viscosity increases generally according to the horizontal of citrus fruit fibres of activation.
The citrus fruit fibres of activation have the advantages that further below:It is used with laundry and residential care detergent composition
Enzyme it is compatible.
It can add the water-swellable of preparation according to the present invention clay/citrus pulp pre-composition as rear dosing ingredient
It adds in detergent liquid preparation.Alternatively, can be by starting from water-swellable clay/citrus of preparation according to the present invention
Then slag pre-composition is added as needed on other ingredients and forms detergent liquid preparation.Some high shears are needed will premix
Object is well dispersed in detergent preparation, but high unlike the requirement prepared to pre-composition to the function.
The citrus fruit fibres of activation also have benefited from no air-treatment, because this improves the stability of gained liquid composition, especially
It is that " bottom clear layer " is detached.In other words, air, the air of macro cures experience especially in mill
(ripening), undesirable " rise " or floating for leading to the fibre structure agent in preparation, lead to detergent preparation
Non-uniform appearance.
It is expected that using the citrus fruit fibres of activation to ensure external structurant network not in its dead weight under sufficiently high level
Lower sedimentation.If network settles, the solid particle of any suspension settles together with network.In order to avoid in structured network
Air entrapment, the amounts of the citrus fruit fibres of activation is preferably decreased to (such as combine for household cleaning close to suspended solid particles
The aromatic of encapsulation in object or dento liva of milling (olive stone)) needed for minimum value.
It also have been discovered that the presence of the clay of a part as external structurant system also contributes to reduce detergent group
Close the level of the citrus fruit fibres of the activation needed in object.
The citrus fruit fibres of activation according to the present invention/caly structure pre-composition can be alternatively by using high shear mixed
Clutch, such as Silverson grind to prepare.Can make the pre-composition of clay and citrus fruit fibres by several high shear stages with
Ensure the abundant hydration of citrus fruit fibres and clay and disperses to form the citrus fruit fibres dispersion of activation.After high shear dispersion,
Pre-composition can be made further to be hydrated (also referred to as aging).However, it is preferred that being used when the pre-composition of activation is fresh, especially
When pre-composition is liquid form, if not using pre-composition within a few hours, lead to increased microbial activity at any time
The problem of.
However, the pre-composition through high pressure homogenization is more preferred than ground pre-composition, because the former more weight is effective and is
Liquid provides enough suspension functions.In addition, improving homogenization pressures provides the weight efficiency further increased for pre-composition.Properly
Operating pressure be about 50000kPa.
3. water
Detergent composition prepared in accordance with the present invention is aqueous, and water forms most of solvent in composition.
Can also include hydrotropic agent with degree more smaller than aqueous solvent, such as propylene glycol and glycerine/glycerine are as cosolvent.Group
It closes and needs water in object to protect other components of composition, such as surfactant, polymer, soluble builder, enzyme etc.
It holds in solution.The water referred in composition includes both free water and any combination water.The amount of water in the composition is preferably extremely
Few 20wt%.It is highly preferred that the amount of water in the composition is at least 30wt%.
4. mixed surfactant system
Citrus fruit fibres and clay using activation mean as external structurant to can be used for detergent composition
Mixed surfactant system type or amount exist almost without limitation.However, synthetic surfactant is preferably formed as table
The major part of surfactant system.Choosing according to formulator to the required cleaning function and required dosage of detergent composition
It selects, following whole can be used:The mixture or full anion blending surface of synthetic anionic and nonionic surfactant are lived
Property agent system or anion surfactant, nonionic surfactant and both sexes or the blending of zwitterionic surfactant
Object.
In addition, the surfactant for forming mixed surfactant system can be selected from description in ' Surface Active
Volume 1, Schwartz&Perry, Interscience 1949, volume 2, Schwartz, Perry&Berch of Agents ',
Interscience 1958, by the ' McCutcheon's published by Manufacturing Confectioners Company
Emulsifiers and Detergents ' or ' Tenside Taschenbuch ', H.Stache, second edition, Carl Hauser
Verlag, the surfactant in 1981.
The amount of surfactant in the composition can be 3 to 75wt%.It is highly preferred that surfactant is in the composition
Amount can be 4 to 60wt%.Most preferably, the amount of surfactant in the composition can be 6 to 50wt%.There is technology
Fiduciary (addressee) will additionally appreciate optimum surfactant concentration and will largely depend on product type and expection
Use pattern.
Anion surfactant can further include soap (i.e. the salt of aliphatic acid).For washing according to the present invention
Preferred soap in agent preparation is sour by hydrogenated coconut oil fatty, such asIt is prepared by the neutralization of 5908 (being purchased from Croda).
The mixture of saturation and unsaturated fatty acid can also be used.
Nonionic detergent surfactant is well known in the art.Preferred nonionic surfactant is C12-C18
Ethoxylated alcohol, per molecule include 3 to 9 ethylene oxide units.More preferably C12-C15Linear ethoxylated primary alconol,
With average 5 to 9 ethylene oxide groups.It is highly preferred that using having the linear ethoxylated of average 7 ethylene oxide groups
Alcohol.
The example of suitable synthetic anion surface active agent includes:NaLS, sodium laureth sulfate, bay
Base sulfosuccinate ammonium, Texapon Special, Zetesol AP, cocoyl hydroxyethyl sulfonate, lauroyl hydroxyl second sulphur
Sour sodium and N- sodium lauryl sarcosinates.Most preferably, synthetic anion surface active agent includes synthetic anion surface active agent
Linear alkylbenzene sulfonate (LAS) (LAS) or other synthetic anion surface active agent alcohol ethoxy ether sodium sulfates (SAES), most preferably
Including high-caliber C12Alcohol ethoxy ether sodium sulfate (SLES).Detergent composition according to the present invention preferably comprises LAS.
Preferred mixed surfactant system includes synthetic anionic and nonionic detergent active material and optional
Amphoteric surfactant, including amine oxide.
Another preferred mixed surfactant system includes two different anion surfactants, preferably straight chain alkane
Base benzene sulfonate and sulfate, such as LAS and SLES.
Synthetic anion surface active agent can be for example with the about 5wt% of mixed surfactant system to about 70wt%'s
Amount exists.
Detergent composition can further include amphoteric surfactant, wherein the amphoteric surfactant with 1 to
The concentration of 20wt% exists.Preferably, detergent composition includes with amophoteric surface active existing for 2 concentration to 15wt%
Agent.It is highly preferred that detergent composition includes with both sexes table existing for 3 concentration to 12wt% of mixed surfactant system
Face activating agent.The representative instance of suitable both sexes and zwitterionic surfactant includes:Alkyl betaines class (alkyl
Betaines), alkylamidoalkyl betaine class, amine oxide, aminopropionate, amino glycine salt, amphoteric imidazoline compound,
Two polyethoxy betaine class of alkyl dimethyl betaine class or alkyl.
5. the non-stick soil particle to suspend
Composition preferably comprises the non-stick soil particle of suspension.These particles are preferably solid;In other words they are not liquid
Body or gas.However, in the range of term solid comprising the particle with rigidity or deformable solid body shell, the solid
Shell can then accommodate fluid.For example, solid particle can be micro-capsule, such as the nursing of fragrance encapsulant or packing forms is added
Agent.Particle can take insoluble composition, such as polysiloxanes, quaternary material, insoluble polymer, insoluble fluorescent whitening agent
Such as the form of the other known beneficial agent described in EP1328616.The amount of suspended particulate can from 0.001 up to 10 or
Even 20wt%.A type of solid particle to be suspended is visual indicator, such as the flat membrane described in EP13119706
Type indicant.Indicant itself can include separation (segregated) component of detergent composition.Since indicant is necessary
It is water-soluble, but insoluble in the composition, is easily prepared by modified polyvinylalcohol, the modified polyvinylalcohol is mixed
It is insoluble in the presence of conjunction surfactant system.In this case, detergent composition preferably comprises at least the anion of 5wt%
Surfactant.
The non-stick soil particle to suspend can be any types.This include fragrance encapsulant, care agent (care) encapsulant and/
Or the pearlescent material and these materials of the visual indicator or cleansing of suspension, solid opacifying agent such as mica or other suspensions
The mixture of material.The density matching of suspended particulate and detergent liquid is closer, and adds detergent before external structurant
Liquid is thicker, and the amount that can be suspended in the particle in detergent preparation is bigger.In general, mixing external structurant can be used
The stable system suspension up to suspended particulate of 5wt%, but up to the amount of 20wt% is possible.
Suspension is realized by providing yield stress.Yield stress, which needs to be more than, to be applied to by micro-capsule or indicant on network
Stress, otherwise network is destroyed and particle may sink or float, and depends on whether they bigger than basal liquid density.It is fragrant
Expect that micro-capsule almost has neutral buoyancy (neutrally buoyant) and small therefore required yield stress is low.Bubble is larger simultaneously
It is and poor with maximal density, it is therefore desirable to which that high yield stress (is more than 0.5Pa, depend on bubble size).If yield stress is not
Too high, then bubble may be escaped by floating and being detached from surface.
Micro-capsule preferably includes solid shell.Answer the fully dispersed micro-capsule with anionic charge to avoid agglomeration problem.Also may be used
To use the micro-capsule with cationic charge.Micro-capsule can have melamino-formaldehyde shell, and can have the heavy of modification shell
Product auxiliary agent, such as polysaccharide or xyloglucan.Other suitable shell materials can be selected from (poly-) urea, carbamate or polyurethane
((poly) urethane), starch and hydroxypropyl cellulose.However, it is preferable that micro-capsule includes melamino-formaldehyde shell, polysaccharide
Or xyloglucan is deposited on the outside of the shell.
The average particle diameter of micro-capsule is in 1 to 100 micron range and the micro-capsule of at least 90wt% preferably has the model
Enclose interior diameter.It is highly preferred that the micro-capsule of 90wt% has 2 to 50 microns, it is straight in even more preferably 5 to 50 micron ranges
Diameter.Most preferably there is the micro-capsule less than 30 micron diameters.
Advantageously have very narrow size distribution, such as 90wt% micro-capsule in 8 to 11 micron ranges.Due to compared with
Short grained high surface area, the micro-capsule in 2 to 5 micron ranges so cannot effectively disperse.
Preferably, composition includes at least micro-capsule of 0.01wt%, preferably has anionic charge.Such micro-capsule can
To deliver various beneficial agents by being deposited on base material, such as laundry fabrics.In order to obtain maximum benefit, micro-capsule should be entire
Fully dispersed and most micro-capsules must cannot notable agglomeration in liquid detergent composition.Become during liquid manufactures
Any micro-capsule of agglomeration is so stayed in a reservoir and therefore will unevenly be distributed during using composition.This is height
It is undesirable.The content of micro-capsule is typically liquid.For example, aromatic, oil, fabric-softening additive and fabric care additive
It is possible content.Preferred micro-capsule is known as the particle of shell packet core (core-in-shell) micro-capsule.As used herein
, term shell packet core micro-capsule refers to that shell substantially or entirely not soluble in water wherein at 40 DEG C includes or by beneficial agent (its
In a liquid carrier for the liquid or dispersion) encapsulant of the core of composition.
Suitable micro-capsule is described those of in US-A-5 066 419, the covering that enbrittles (coating), preferably
Aminoplast polymers.Preferably, the covering be amine selected from or mixtures thereof urea and melamine with selected from formaldehyde, acetaldehyde,
The reaction product of the aldehyde of or mixtures thereof glutaraldehyde.Preferably, coating is the 1 to 30wt% of particle.
The shell packet core micro-capsule of other types can be also suitably used for the present invention.Prepare the other of such beneficial agent (such as fragrance)
The method of micro-capsule is included in interface (such as in aggregate) precipitation and deposited polymer (such as GB-A-751 600, US-A-3341
Disclosed in 466 and EP-A-385 534) and other polymerization approachs, such as interfacial condensation (such as US-A-3 577515, US-A-
2003/0125222, described in US-A-6 020 066 and WO-A-03/101606).Micro-capsule with polyurea wall is disclosed in US-
In A-6 797 670 and US-A-6 586 107.More particularly in waterborne liquid use melamine-formaldehyde shell packet core micro-capsule
Other patent applications be WO-A-98/28396, WO02/074430, EP-A-1 244 768, US-A-2004/0071746 and
US-A-2004/0142868。
Fragrance encapsulant is the micro-capsule suitable for the preferred type of the present invention.
The preferred kind of shell packet core perfume microcapsules includes those of being disclosed in WO 2006/066654A1.These include tool
There is the core of the fragrance for the about 5wt% to about 50wt% being dispersed in the carrier material of about 95wt% to about 50wt%.The carrier material
Material is preferably or mixtures thereof non polymerizing solid fatty alcohol or fatty ester carrier material.Preferably, ester or alcohol have about 100 to about
500 molecular weight and about 37 DEG C to about 80 DEG C of fusing point, and it is substantially insoluble in water.Including the core of fragrance and carrier material is at it
The covering for being substantially insoluble in water is coated on outer surface.Similar micro-capsule is disclosed in US 5,154,842 and these are also to close
Suitable.
Micro-capsule can be attached to suitable base material, such as to provide lasting fragrance, desirable after the completion of cleaning process
Ground discharges.
6. liquid detergent composition
Detergent composition has enough yield stresses of at least 0.08Pa, also referred to as limit stress.Preferably, it washs
Agent composition has at least yield stress of 0.09Pa.It is measured at least at 25 DEG C it is highly preferred that detergent composition has
0.1Pa, and the yield stress of even at least 0.15Pa.The yield stress of these Increased levels can be in fluid bulk (bulk
Liquid suspend the particle with incremental density variation in).The major part it has been found that yield stress of 0.09Pa suspends enough
The fragrance encapsulant of type.Pure clay is unstable and cannot provide effective knot of aqueous isotropism detergent liquid composition
Structure.Mixing external structurant system also keeps disperseing:Neither floating (generate bottom and clarify layer separation) nor (the generation top that sinks
Clarify layer separation in portion).This is from suspension by ensuring that structuring system will occupy whole volumes realization of detergent liquid.This depends on
In the amount of the citrus fruit fibres of the clay and activation that use.It has been found that only by the citrus fruit fibres that activate realize this point generate such as than
For high yield stress so that bubble suspends, these then make the structured network unstable.
Detergent liquid can be formulated as to concentrated cleaning liquid for being applied directly to base material, or for diluting
It is after-applied to be diluted to base material, such as by consumer before or during using liquid composition or in wash mill.
It can be by simply making the liquid medium that base material is constituted or prepared with by liquid cleansing composition contact enough
Period is cleaned.However, it is preferred that stirring on base material or accommodating the cleaning medium of base material.
Product form
Liquid detergent composition is preferably the liquid cleansing composition concentrated.Liquid composition or drumped liquid
Body.
Throughout this manual, unless otherwise indicated, the viscosity of all statements is in 21s-1Shear rate under and 25
The viscosity measured at a temperature of DEG C.The shear rate is that the shear rate of liquid is commonly applied to when being poured out from bottle.According to this
The liquid detergent composition of invention is shear thinning liquid.
Manufacturing method
Under the citrus fruit fibres of activation and the higher level of water-swellable clay for the heavier particle that needs to suspend, individually to mend
The amount of water that sufficient pre-composition can be removed from base-material (base) become too big, thus the rear dosing of addition of structurant be not can
Capable selection.On the contrary, can by activated fiber/water-swellable clay preparation structure detergent composition, with them
Normal adding order other ingredients are added to it.In addition to can fiber/clay of higher levels of activation be incorporated to detergent
Liquid China and foreign countries, with further advantage:The following component phase is added by being dispersed in for fiber/clay of the activation of high shear
Between continue, not as rear shearing step, thus reduce and divide the intermittent time.It also have been discovered that best practice is by liquid
Composition is deaerated before being packed into container.However, external structurant system allows the technological flexibility and the step of bigger
Suddenly it is not required.
Optional member
It has been found that the citrus fruit fibres and water-swellable clay of activation and the common composition phase that may be present in detergent liquid
Hold.Wherein it can be mentioned that by way of example:Polymer viscosifier, enzyme, especially:Lipase, cellulase, protease, sweet dew are poly-
Carbohydrase, amylase and pectin lyase;Clean polymer, including ethoxylated polyethylene imines (EPEI) and polyester soil release polymerization
Object;Chelating agent or sequestering agent (sequestrant), including HEDP (1- hydroxy ethylidene bases -1,1- di 2 ethylhexyl phosphonic acid), such as from
Thermphos conducts2010 can obtain;Detergent builder compound, hydrotropic agent, neutralizer and pH adjusting agent, brightener,
Antioxidant and other preservatives, such as antimicrobial, includingOther active constituents, processing aid, dyestuff or
Pigment, carrier, aromatic, foam inhibitor or foam improver, chelating agent, clay soil/anti redeposition agent, fabric softener, dyestuff
Transfer inhibitor and the transition-metal catalyst in the composition for being substantially free of peroxide substance.
Including these and other possible ingredient in the present invention further describes in WO 2009/153184.
Packaging
Composition can be packaged in any type of container.The typically plastics with detachable closing/pour spout
Bottle.The bottle can be rigid or deformable.Deformable bottle allows squeeze bottle to help to distribute.If using clear vial, it
Can be formed by PET.Polyethylene or transparent polypropylene can be used.Preferably, container is sufficiently transparent so that from it is external it is visible its
In with any visual indicator liquid.The bottle can have one or more labels, or have shrink wrapped sleeve, close
Meaning ground is at least partly transparent, such as the area of sleeve 50% is transparent.Adhesive for any clear label is not
Transparency should be negatively affected.
Embodiment
Description of the drawings
The present invention is further described referring now to following non-limiting embodiment and attached drawing, wherein:
Fig. 1 a are that the tradition for the isotropism aqueous detergent liquid for being used to prepare external structurant prepares the signal of route
Figure.
Fig. 1 b are the preparation roads for the isotropism aqueous detergent liquid for being used to prepare external structurant according to the present invention
The schematic diagram of line.
Fig. 2 a are the samples of the citrus pulp and water-swellable Laponite clays of the middle method processing illustrated according to fig. 1a
MIcrosope image.
Fig. 2 b are the microscopes according to the sample of the citrus pulp and clay of method processing that is of the invention and illustrating in Figure 1b
Image.
Fig. 3 a are to prepare according to the method for the present invention, the outside after then at room temperature balancing aqueous detergent 24 hours
The photographs of the isotropism aqueous detergent liquid of structuring.
Fig. 3 b are that according to fig. 1a prepared by the middle method illustrated, the external structurant after then balancing 24 hours at room temperature
The photographs of isotropism aqueous detergent liquid shows the deterioration of detergent liquid structure.
Abbreviation
The following abbreviated name used in these embodiments claims to have following meanings:
ACF is the citrus fruit fibres (2wt% pre-compositions) of high-pressure homogenizer (HPH) activation
Water is demineralised water
Glycerine is hydrotropic agent
MPG is monopropylene glycol (hydrotropic agent)
Neodol NI are nonionic surfactants, are purchased from Shell
NaOH is 50% sodium hydroxide alkali
LAS acid is linear alkyl benzene sulfonic acid anion surfactant
MEA is monoethanol amine base
TEA is triethanolamine alkali (not presenting)
Prifac 5908 is saturated fatty acid (soap), is purchased from Croda
SLES (3EO) is SLES 3EO anion surfactants
Dequest 2066 is diethylene triamine penta(methylene phosphonic acid) (or seven sodium of DTPMP) sequestering agent, is purchased from
Thermphos
Dequest 2010 is HEDP (1- hydroxy ethylidene bases -1,1- di 2 ethylhexyl phosphonic acid) sequestering agent, is purchased from Thermphos
EPEI is ethoxylated polyethylene imines PEI600EO20Sokalan HP20, is purchased from BASF
HPH is high-pressure homogenizer
Neolone MIT 950TMIt is anti-microbial preservative, is the methylisothiozoline -3- ketone in water, is purchased from Dow
Chemical fragrance encapsulants are the fragrance of encapsulation, and Oasis Cap Det B72 are fragrance purchased from Givaudan Polynesie
Oil
Preservative is Proxel GXLTMAnti-microbial preservative, 1,2-benzisothiazolin-3-one is in dipropylene glycol and water
In 20% solution, be purchased from Arch Chemicals
Fragrance is free oil flavors
Laponite EL are water-swellable synthetic li-montmorillonite clays, are purchased from BYK Additives
Laponite RD are water-swellable synthetic li-montmorillonite clays, are purchased from BYK Additives
Micro is ISP white microbeads (visual indicator)
Viscolam CK57 are crosslinked thickening polymers, are purchased from Lamberti
Tinopal 5BM-GX are fluorescent whitening agents
Kleen is the aromatic of encapsulation
1000L is pectin lyase, is purchased from Novozymes
Protease is Relase Ultra 16L EX, is purchased from Novozymes
L blends are the blends of 3 parts of Stainzyme (amylase) and 1 part of Mannaway (mannase), are purchased from
Novozymes
Savinase is the enzyme that Ultra 16L-are purchased from Novozymes
Liquitint is dyestuff.
Experiment
General procedure 1-tradition preparation method
The isotropism aqueous detergent liquid for being used to prepare external structurant as illustrated in Fig. 1 a is typically formulated road
Line is as follows.
First, this method includes preparing citrus powder/water pre-composition (100) to be used as external structurant, and it includes for example
The citrus fruit fibres powder (Herbacel AQ plus N Citrus Fibre (being purchased from Herbafoods)) of 2wt%.By citrus pulp
It is added slowly to the mixture of demineralised water and preservative (such as Proxel GXLTM), and uses the tool run at 200 rpm
There is the blender reaction stirred of top drive 15 minutes, it is ensured that be not aggregated, and make the abundant water of fiber before activation
It closes.Then using high-pressure homogenizer (HPH) (200) processing citrus pulp powder/water pre-composition to activate citrus pulp fiber.Use
Available from SPX APV2000 laboratory high pressures homogenizer at about 50000kPa, under 11kg/ hours flows be homogenized dissolving
Citrus pulp powder.
Dividually, clay preparation (300) is prepared, wherein by stirring at 300 rpm 15 minutes, it will such as 0.1wt%
Clay and encapsulant mixed with demineralised water (as needed).
Then before the citrus pulp pre-composition (210) of addition activation, the stir speed (S.S.) of clay preparation is reduced to
250rpm.Then citrus pulp and clay mixture are mixed 5 minutes.
Then the stir speed (S.S.) of reactant is further reduced to 200rpm and added and be selected from such as fluorescent whitening agent, alkali
Other components of (neutralizer), surfactant and sequestering agent simultaneously make preparation pass through 1.2 to 3.8kJ/Kg energy
All components are stirred 15 minutes before the mill of lower operation.
Finally, additional component, such as preservative, dyestuff, fragrance and enzyme are merged with ground preparation group
15 minutes are stirred under 200rpm to generate final detergent liquid preparation (400).
Program 2-is according to the present invention to flow method altogether
The isotropism aqueous detergent liquid according to the present invention for being used to prepare external structurant as illustrated in Fig. 1 b
Preparation route it is as follows.
Include demineralised water the method for the present invention includes initial prepare compared with the traditional route described in procedure above 1
(as needed) and preservative (such as Proxel GXLTM(0.02%)) pre-composition is added to citrus fruit fibres powder
(0.66wt%) (150) and clay powders (1.33wt%) (160), and reactant is stirred at 200 rpm 15 minutes.
Then using high-pressure homogenizer (HPH) processing citrus pulp powder/clay pre-composition to activate citrus pulp fiber
(250).The citrus pulp powder hydration that will be combined with clay powders, then using the APV2000 laboratory high pressures available from SPX
Homogenizer is homogenized under 50000kPa pressure under 11kg/ hours flows.
Then by the pre-composition of the citrus pulp fiber of activation and clay and such as encapsulant and batch of material water (batch water)
Combination, and reactant is stirred into 5 minutes (350) at 250rpm.
Then the stir speed (S.S.) of the citrus pulp of activation and the preparation of clay is reduced to 200rpm and added selected from for example
Fluorescent whitening agent, alkali (neutralizer), surfactant and sequestering agent other components and stir the mixture for 15 minutes.So
It is further processed preparation by by making it through the mill run under 1.2 to 3.8kJ/Kg energy rate.
Finally, additional component, such as preservative, dyestuff, fragrance and enzyme are merged with ground preparation group
Component is stirred 15 minutes to generate final detergent liquid preparation (450) under 200rpm.
The preparation of detergent liquid
That is summarized in program 2 more than use is directed to the citrus powder and clay system of different proportion according to the method for the present invention
A series of standby detergent liquids, for use more than general procedure 1 in the detergent for preparing of traditional preparation method for summarizing
Liquid is compared.The citrus fruit fibres of activation fresh enough/clay pre-composition can be added to mixer to grind as one sees fit
The citrus fruit fibres of the activation of required level in final product composition are generated before mill.The mill used includes two blade impeller.Using online
(in-line) industry high-shear mixer Silverson (L5T) realizes final detergent under ratio energy input as needed
The dispersion of preparation.
It is defined as energizing to generate the mixing condition of the uniform structure through liquid than energy (kJ/Kg).The energy
It can be by changing combined power and resonance time acquisition in mixer.1.2 to 3.8kJ/Kg ratio energy definition be for
Rational action pane for the dispersion of consistent structural agent.
Rheology flow curve measures
To the citrus pulp according to the present invention by activation and water-swellable clay powders, such as Laponite clay combinations
The pre-composition of preparation and both pre-compositions to using the citrus pulp pre-composition individually activated to prepare, and to using two kinds of premixs
Final detergent preparation prepared by object records rheology measurement.Then prepared for final detergent using following three steps regulation
Product generate rheology flow curve:
The instrument used is Paar Physica, MCR300, has automatic samplechanger (ASC)
Geometry is carried out with CC27, for special-shaped (profiled) DIN concentric cylinders.
Measurement carries out at 25 DEG C.
Step 1-0.01 to 400Pa controlled stress step;40 step stress log intervals, it is each point expend 40 seconds with
Measure shear rate (and therefore viscosity);Once reaching 0.1s-1Shear rate, then terminate step 1.
Step 2-0.1 to 1200s-1Controlled shear rate step;40 step shear rate log intervals, in each point consumption
Take 6 seconds to measure the stress kept needed for shear rate and therefore viscosity.
Step 3-1200 to 0.1s-1Controlled shear rate step;40 step shear rate log intervals, in each point consumption
Take 6 seconds to measure the stress kept needed for shear rate and therefore viscosity.
Then the result of first two steps is combined, carefully remove any overlapping and ensures to reach required shearing when step starts
Rate.
Then take yield stress using in terms of Pascal (Pa) as 0.1s-1Shear rate under stress value, i.e., shearing answer
Y intercept equivalent in the Herschel-Buckley curve graphs of power vs. shear rates.Then yield stress is taken to be considered as this
Data cut the point of (cut) viscosity=10Pa.s, and topple over viscosity and be recorded as 20s-1Under viscosity, at 25 DEG C.
The following table 1 be described in detail compared in general procedure outlined above only individually comprising activation citrus pulp with
The pre-composition of clay combination, to via according to the present invention and citrus pulp prepared by above total stream method summarized in program 2 and
The yield stress and viscosity number that the pre-composition of clay obtains.
As a result the citrus pre-composition that the yield-stress ratio of the pre-composition of the citrus pulp and clay that flow altogether individually activates is shown
Yield stress is low more than 60%.However in contrast, the surrender of the pre-composition of the citrus pulp and clay that flow altogether in the final product
The high yield stress for the clay pre-composition that stress ratio individually activates.This has the effect of that final detergent preparation is more stable.
Further, it can be seen that for the detergent liquid for using the total stream method of the present invention to prepare, detergent liquid was at 12 weeks
It keeps stablizing after Storage period, in contrast, when the detergent liquid prepared using conventional method is stored at room temperature, at only 1 week
Fail in stability test afterwards.It will be seen that improving the stabilization of final detergent preparation using the method for the present invention
Property, in the method detergent is prepared with the pre-composition of the citrus pulp and clay that flow altogether.
The comparison data of table 1-clay and citrus fruit fibres pre-composition that by standardization program 1 and altogether prepared by string routine 2
All methods have 2% solid in pre-composition, in addition to embodiment 14, have 3% solid in pre-composition.
In addition, using the embodiment of standardization program 1 compared with embodiment 11 and 12, citrus pulp and the water of 0.05/0.1 can
Fail under the ratio of Swelling Clay.
Detergent liquid preparation
Table 2:The detergent preparation prepared using citrus pulp/clay pre-composition of the embodiment 1 in table 1
Table 3:The detergent preparation prepared using citrus pulp/clay pre-composition of the embodiment 2 in table 1
Table 4:Use the detergent preparation that in table 1 prepared by the citrus pulp pre-composition of embodiment 3 individually activated
Table 5:Use the detergent preparation that in table 1 prepared by the citrus pulp pre-composition of embodiment 6 individually activated
Table 6:Use the detergent preparation that in table 1 prepared by the citrus pulp pre-composition of embodiment 13 individually activated
Table 7:Use the detergent preparation that in table 1 prepared by the citrus pulp pre-composition of embodiment 14 individually activated
It can be seen that in table 7, there are 3% more concentrated total stream pre-compositions.The concentration, which reduces, is manufactured into pre-composition
In water volume without influence stability.
It is following to carry out after preparing detergent liquid defined above using pre-composition prepared by the method for the present invention
Detergent liquid stability test.
Inflation test
Liquid detergent formulation is monitored for the appearance of bubble in liquid formulations.The presence of bubble can in preparation
To lead to the structural damage of the detergent preparation caused by the caving in of citrus fruit fibres.By bubble in detergent preparation
It is classified in the presence of from A0 to A3.The value of A0 indicates 0 or few bubble, and the value of A2 to A3 indicates that there are a large amount of bubbles.Such as under
As it can be seen that having the charged value of A0 using detergent preparation prepared by the pre-composition from embodiment 1 in table 5.
Photography stability test or " reducing (dip) " test
" reducing test "-visible inside detergent preparation " decline " or " rising " test
Also directed at the top of preparation or bottom formed non-uniform areas appearance monitor liquid detergent formulation.
Shoot the photo of the liquid detergent formulation in transparent vessel.As being respectively shown in Fig. 3 a and 3b, in room temperature
Lower balance uses the non-general procedure system flowed altogether after 24 hours, for the preparation comparison for using the total string routine of the present invention to prepare
Standby liquid detergent formulation visually compares detergent liquid preparation.
It may recognize that the example of the non-uniform areas at the top towards detergent liquid preparation illustrated in Fig. 3 b, wherein
Region " A " depicts clarification, non-uniform region, this show the destruction of the uniformity of detergent liquid and in appearance with wash
The remainder for washing agent liquid is different.Region " A " is referred to as " decline " or " reduction " in preparation.When liquid formulations are kept
When at room temperature or 5 DEG C, the decline or reduction of 1-2mm are acceptable.When liquid formulations are maintained at room temperature or 5 DEG C,
Decline more than 5mm is considered as product failure.In fig 3b, decline and be more than 5mm.
Table 8:Summary to the stability test of the detergent liquid preparation prepared in table 1
In table 9, the stabilization of detergent preparation for preparing according to embodiment 3 and being prepared as illustrated in table 2 is illustrated
Property test, citrus pulp and clay ratio is 0.05/0.1 and store under a set of conditions.
Table 9
It is contrasted with result shown in table 9, table 10, which is provided, to be prepared according to embodiment 2 and prepared as illustrated in table 4
Detergent preparation stability test, the preparation has in the citrus fruit fibres slag activated there is no clay,
Citrus pulp and clay ratio are 0.05 to 0.1 and store under a set of conditions.As it can be seen that all samples all lose such as in table 10
It loses.
Table 10
Therefore, from result above as it can be seen that compared to standard premixing method, for using by using total stream according to the present invention
The test that the liquid detergent composition that pre-composition prepared by program is prepared carries out uses a series of structural agent ratios
The detergent product that stream premix program is prepared altogether is same compared with the detergent product for using standard premix program to prepare
Sample is more stablized.
Also find out with upper table 9 and 10, for the pre-composition ratio of citrus fruit fibres and clay, program system is premixed using total stream
Standby detergent product sample is stablized in series of temperature and in several weeks.
In addition, for using coprocessing structuring agent premix, (it includes the water-swellables of 0.05% citrus fruit fibres/0.1%
The ratio of laponite EL clays) prepare preferred detergent preparation, to use the pre-composition preparation prepare detergent
Preparation carry out test as a result, it has been found that liquid detergent is more more stable than its standardization program counterpart.In addition, it was further observed that
The structure of the detergent preparation product prepared using the pre-composition of stream altogether according to the present invention is washed than what is prepared by standard method
Wash agent preparation product evenly.
MIcrosope image
To following sample record MIcrosope image:The pre-composition sample prepared using total string routine according to the present invention,
In activate citrus pulp in the presence of water-swellable Laponite clays, and the pre- of pre-composition sample is wherein prepared according to general procedure
Mixed object sample, wherein in the case that there is no other structures agents to activate citrus pulp.
The image generated to two kinds of samples is illustrated in Fig. 2 a and 2b respectively.
Using the dressing table equipped with Marzhauser motorizeds and equipped with the Zeiss controlled by Zeiss Axiovision softwares
The BX51Olympus microscopes of HRc Axiocam cameras obtain image.For each detergent liquid, sample is contained in
In depression slide, it is sealed with coverslip.Image is recorded under 10 enlargement ratios of x to transmit DIC patterns, the enlargement ratio
Make image with the visual field (field of view) of 1.29 μm of 669 μm of lateral resolution and 892x.
From Fig. 2 a and 2b as it can be seen that compared to the pre-composition for using general procedure to prepare, for passing through side according to the present invention
Method is existed using the sample that altogether prepared by string routine drops low-level visible structural agent materia, this shows that pre-composition has occurred and that
It significantly changes.
Conclusion
Have been observed that (it includes activation and water-swellable according to the method for the present invention from the above experiment and result
The citrus pulp of Laponite clay combinations) yield-stress ratio of pre-composition for preparing is related to preparing and only includes the pre-composition of citrus pulp
Method it is low.
In addition, it was further observed that for using the total stream method of citrus pulp and water-swellable Laponite clays according to the present invention
The pre-composition of preparation, yield stress is increase with time.This pre-composition with only citrus fruit fibres is on the contrary, observe only citrus fruit fibres
The yield stress of pre-composition reduces at any time.
Although being not intended to be bound to any particular theory, inventor believes that the surrender of pre-composition prepared in accordance with the present invention is answered
The increase of power be due to during citrus pulp activates in citrus pulp fiber include caly structure agent, altogether flow pre-composition with
Time gradually forms gel, thus increases the yield stress of pre-composition.
As by lacking bubble and the shortage " reduction " seen in preparation when balance in detergent, (Fig. 3 a are to figure
It 3b) proves, when pre-composition is in final detergent liquid preparation, the increased yield stress for flowing pre-composition altogether also carries
For static stabilization.
Therefore, because citrus pulp fibre is wherein activated in the presence of water-swellable Laponite clays according to the present invention to using
The increased stability that detergent preparation prepared by the pre-composition of dimension is observed, can use lower level structural agent group
It closes, such as citrus pulp/clay is 0.05%/0.1%.Due to the unstability of structural agent combination, lower level structuring
Agent combination can not achieve and used for detergent compositions designer before.
Therefore, the present invention provides the improved methods for producing stable co-structured agent pre-composition, wherein together
It processing structure agent and is handled under lower amount when than being prepared separately, and it can be used to detergent preparations to provide
The product for continuing 12 weeks stabilizations at all temperatures thereby conforms to current industrial standards test.
It is not previously possible to produce stable washing using the citrus pulp fiber of 0.05/0.1 and the ratio of water-swellable clay
Agent preparation.Therefore, citrus pulp fiber and water soluble are made by high-pressure homogenizer with such as 2% solids pre-mix according to the present invention
Thus gram method that swollen Laponite clay powders flow altogether together generates the product for keeping stabilization at 12 weeks at all temperatures, and
The clothes problem related to art methods.
Claims (15)
1. the method for manufacturing the aqueous detergent liquid formulations of external structurant comprising following steps:
I) pre-composition of citrus fruit fibres and water-swellable clay powders is formed;Then
Ii the citrus fruit fibres and the pre-composition of water-swellable clay powders) is made to pass through high-pressure homogenizer to form homogenized knot
Then following substance is added to homogenized addition of structurant by structure pre-composition:
Iii) at least surfactant of 2wt%;With
Iv) the non-clay solid particle of at least 0.001wt%, and grind and prepared with the detergent liquid for forming external structurant
Product.
2. the method according to claim 1, wherein make the pre-composition of water-swellable clay powders and citrus fruit fibres 5000 to
Pass through high-pressure homogenizer under the pressure of 80000kPa.
3. the method according to claim 1, wherein make the pre-composition of water-swellable clay powders and citrus fruit fibres 7000 to
Pass through high-pressure homogenizer under the pressure of 70000kPa.
4. according to the method for any one of claim 1-3, wherein the pre-composition includes clay powder at least amount of 0.04wt%
End and at least amount of 0.02wt% include citrus fruit fibres.
5. according to the method for any one of claim 1-3, wherein the pre-composition is viscous comprising water-swellable with the maximum value of 5wt%
Native powder.
6. according to the method for any one of claim 1-3, wherein the pre-composition includes that citrus is fine with the maximum value of 2.5wt%
Dimension.
7. according to the method for any one of claim 1-3, wherein at least the surfactant of 2wt% includes 5wt% to 70wt%
Anion surfactant and 1 to 20wt% amphoteric surfactant.
8. according to the method for any one of claim 1-3, wherein the non-clay particle is selected from:
Visual indicator, fragrance encapsulant, nursing additive and cleansing.
9. according to the method for any one of claim 1-3, the wherein homogenized knot of citrus fruit fibres and water-swellable clay powders
The yield stress of structure pre-composition is 10 to 200Pa.
10. according to the method for any one of claim 1-3, the wherein homogenized knot of citrus fruit fibres and water-swellable clay powders
The yield stress of structure pre-composition is 15 to 140Pa.
11. the homogenized addition of structurant of water-swellable clay powders and citrus fruit fibres, is used for the water of external structurant
Property detergent liquid preparation, it includes:The citrus of the water-swellable clay powders and at least 0.02wt% of at least 0.04wt%
Fiber.
12. the aqueous detergent liquid formulations of external structurant, the method that any one of claim 1-10 can be used obtains,
It includes:The citrus fruit fibres and water-swellable clay powders of homogenized pre-composition form, wherein the preparation includes:
I) at least clay powders of 0.04wt%;
Ii) at least citrus fruit fibres of 0.02wt%;
Iii) at least surfactant of 2wt%;With
Iv) the non-clay solid particle of at least 0.001wt%.
13. the aqueous detergent liquid composition of external structurant according to claim 12 further includes a kind of or more
Kind antifungal agent and/or antibacterial agent and/or one or more dyestuffs.
14. the aqueous detergent liquid composition of external structurant according to claim 12, wherein the citrus fruit fibres with
0.02 to 2.5wt% range exists.
15. the aqueous detergent liquid composition of external structurant according to claim 12, wherein the clay powders with
0.04 to 0.45wt% range exists.
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PCT/EP2014/072247 WO2015059031A1 (en) | 2013-10-22 | 2014-10-16 | Process to manufacture an externally structured isotropic aqueous detergent liquid |
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EP1402877A1 (en) * | 2002-09-30 | 2004-03-31 | Rohm And Haas Company | Thickener for high-surfactant aqueous systems |
WO2012052306A1 (en) * | 2010-10-22 | 2012-04-26 | Unilever Plc | Externally structured aqueous detergent liquid |
CN102858942A (en) * | 2010-03-31 | 2013-01-02 | 荷兰联合利华有限公司 | Microcapsule Incorporation In Structured Liquid Detergents |
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EP1402877A1 (en) * | 2002-09-30 | 2004-03-31 | Rohm And Haas Company | Thickener for high-surfactant aqueous systems |
CN102858942A (en) * | 2010-03-31 | 2013-01-02 | 荷兰联合利华有限公司 | Microcapsule Incorporation In Structured Liquid Detergents |
WO2012052306A1 (en) * | 2010-10-22 | 2012-04-26 | Unilever Plc | Externally structured aqueous detergent liquid |
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