CN1408004A - Water unstable foam - Google Patents

Abstract

An elastic article is provided which comprises a foam matrix formed from a polymeric material and a plasticiser, a stabilising agent and an active ingredient, such as a detergent active ingredient, typically to be delivered to an aqueous environment. Said elastic article provides a means to deliver an active ingredient to an aqueous environment, preferably the active ingredients being a detergent active ingredient, preferably enzymes, and the aqueous environment being the wash water.

Description

The foam of water unstable

Invention field

The present invention relates to be generally the particulate foam formation, it comprises the matrix that is formed by a kind of polymer materials and softening agent, and solubilising reagent and as the activeconstituents of sanitising agent activeconstituents generally is discharged into this component in the aqueous environment.

Background of invention

For example cleaning product and personal care product, the composition of makeup and medicine usually comprises the activeconstituents that will be released in the water, perhaps requires to have active activeconstituents under aqueous environment.The great majority of these activeconstituentss when storage to humidity, temperature variation, light and/or air-sensitive.

Also there are another problem in the great majority of these activeconstituentss, especially enzyme, promptly in operating process, because the physical force that acts directly on these activeconstituentss makes them tend to form dust.Not only produce waste material thus, and these dust also can cause health and health problem.

For addressing these problems, carried out research with coating-forming agent or sealing agent protection activeconstituents.The problem that most of this coating particless have is: in operating process, these particles always do not demonstrate enough shock-resistance, and under the effect of the common physical force that runs in operating process, these particles form the dust that can produce health and health problem.And these coating particless are always easily not molten in aqueous environment, show the solubility property of going on business when contacting with water.

The inventor has found a kind ofly to protect activeconstituents and these activeconstituentss are discharged into improving one's methods in the aqueous environment.The specific foam formation that they have found to comprise the matrix that is formed by polymer materials and softening agent is impact resistance very, and the activeconstituents that is incorporated into wherein is protected to avoid acting on the physical force on the described foam formation.In addition, the inventor found when also adding dissolution aids in foam formation, and this foam formation is easy to dissolving or decomposes when contacting with water, goes thereby activeconstituents is discharged in the aqueous environment.

Therefore foam formation of the present invention has good shock-resistance, has reduced fracture or the abrasion in the operating process, has reduced the formation of dust, dissolves easily when contacting with water.For example, can obtain safer and more valid function and use contain the enzyme foam formation, as particle or bead.And can so prepare these components, and make that it can be with the activeconstituents that is incorporated into wherein, be discharged in the aqueous environment effectively as enzyme and go.To air-stable, but instability when contacting with water discharges activeconstituents to component of the present invention thus under common humidity storage condition.This foam formation can be used in any product, especially for cleaning product, and medicine, the personal care product is in makeup and the fabric care product.

Summary of the invention

The invention provides a kind of foam formation, it comprises polymer materials, dissolution aids and the preferred mixture that in aqueous environment, has active activeconstituents, and this foam formation is stable when contacting with air, is unsettled when contacting with water.

Described dissolution aids has improved the water-soluble of this foam formation or water decomposition performance.

The dissolution aids of preferred described foam formation comprises the foaming system, hydrotropic agent or the combination of the two.

The invention still further relates to the method for this foam formation of preparation.

Preferably obtain this foam formation by the method that may further comprise the steps;

A) obtain a kind of polymer materials;

B) in described polymer materials, introduce a kind of gas with chemistry or physics mode;

C) before the step b) and/or, described polymer materials is contacted with a kind of activeconstituents with the step b) while and/or after step b);

D) before the step b) and/or, described polymer materials is contacted with a kind of dissolution aids with the step b) while and/or after step b); With

E) the resulting polymers material component is shaped;

If there is water, preferably a) to e) one or more steps after or remove portion water simultaneously.

In another embodiment of the present invention, the application of foam formation is provided, be about to activeconstituents and be discharged in the aqueous environment, wherein preferred activeconstituents is the sanitising agent activeconstituents, be preferably enzyme, and aqueous environment is preferably bath water.

Detailed Description Of The Invention

Foam formation

Foam formation of the present invention is also referred to as " component " in the present invention, comprises a kind of activeconstituents, a kind of matrix and a kind of dissolution aids.Described activeconstituents, matrix and dissolution aids will be described in detail hereinafter.

Component of the present invention is preferably water dispersible, water decomposition or water dissolution.Preferred water dispersible component has at least 50% among the present invention, preferably at least 75%, or even at least 95% dispersiveness, be to be that 50 microns glass filter is measured with the maximum diameter of hole, this method will be set forth hereinafter; Preferred component can water-soluble or water decomposition among the present invention, and has at least 50%, and preferably at least 75%, or even at least 95% water-soluble or decomposability, be to be that 20 microns glass filter is measured with the maximum diameter of hole, this method will be set forth hereinafter, that is:

It is water-soluble to measure component among the present invention, the gravimetric analysis method of water decomposition or water dispersible:

Component among the present invention 50 grams ± 0.1 gram is joined in fixed 400 ml beakers of weight, and add the distilled water of 245ml ± 1ml.Stirred 30 minutes with the magnetic stirrer that is set in 600rpm is powerful.Using as defined above then, the folding qualitative fritted glass filter of pore size (maximum 20 or 50 microns) filters this component mixture.The water drying in the filtrate of having collected, measure the weight (be dissolved, decompose or the dispersive part) of residual component with traditional way.Can calculate dissolving then, decompose or dispersive percentage ratio.

Component among the present invention generally is used for active substance is discharged into aqueous environment.So the component among the present invention, preferably its matrix is unsettled when contacting with water.When this situation took place, a kind of (or multiple) activeconstituents that exists in the component or the part of activeconstituents were released in the liquid, preferably for example in the aqueous environment of water.Preferred this composition or a part of composition sex change are decomposed, and preferably are dispersed or dissolved in the liquid, preferably in aqueous environment, more preferably in water.Can be preferably with the activeconstituents snap-out release in water, this composition disperses or dissolves fast thus; Preferred described composition is with after water contacts, in 30 minutes at least 10% of this composition weight, perhaps more preferably at least 30% or even at least 50%, or even at least 70%, or even at least 90% dissolving or disperse (concentration with 1 weight % is incorporated in the water).Even but preferred ingredient contacts with water in back 20 minutes, or even 10 minutes in, or even 5 minutes in above-mentioned situation takes place.The method that can above introduce is measured solvability or dispersiveness, to measure the dissolving of composition among the present invention, decomposes or dispersiveness.

Preferred ingredients is that the component cumulative volume is compared with initial cumulative volume and changed, and preferably reduces at least 10%, for example under 25 ℃ temperature, works as 1cm ³Said components be added in the 100ml softening water, measured when simultaneously under the speed of 200rpm, stirring 5 minutes like that.The variation of preferred this cumulative volume perhaps is reduced at least 20%, or even at least 40%, or even at least 60%, or even at least 90%, or even about 100%, for example because can be preferably basically all components be decomposed fast, disperse or be preferably dissolved in the water.

Available any method known in the art is measured this, especially uses following method of the present invention (secondary immersion method):

With the 1cm that obtains ³Component is incorporated in the long-pending test cylinder of microbody that 100ml is filled with the organic inert solvent of 50ml ± 0.1ml.Can not make the polymer materials sex change of component matrix of the present invention at acetone, and/or can not react, for example when polymer materials is PVA, for example can use acetone with it.Discover according to the performance of material and can use other neutral organic medium; This inert solvent can make this component substantially not by this dissolution with solvents, disperses, and decomposes or sex change.

Right cylinder is bubble-tight, and it was left standstill 1 minute, and solvent is penetrated in the whole component thus.The variation of measurement volumes, and note is made the initial volume V of foam sample _iFrom solvent, remove component then, and this component is stayed air drying, make solvent evaporates.

Then component is placed in the 250ml beaker that the 100ml softening water is housed, remains under 25 ℃, the speed with 200rpm under the help of magnetic stirrer stirred 5 minutes.If have residually, leach the component sample residue with the copper strainer of 60mm sieve mesh, and be placed in the baking oven of certain temperature, keep for some time, remove residual moisture thus.With drying residual component be reintroduced in the measuring right cylinder, wherein the volume of acetone is transferred to 50ml again.

Detect the increasing amount of cumulative volume, note is made the final volume V of this component _fThen the reduction Δ V of component sample cumulative volume is: $\%\mathrm{\ΔV}=\frac{\mathrm{Vf}}{\mathrm{Vi}}*100$

This component preferably has 0.01 to 0.95, more preferably 0.05 to 0.9, or even 0.1 to 0.8, or even 0.3 to 0.7 relative density ρ ^*This relative density is the density (ρ of component ^*) be used to form the summation (ρ of all loose material partial densities of component _s) the ratio.

Among the present invention the preferred foam formation that uses be air-stable or be stable when contacting with air, when this just meaned in being exposed to air, the stacking volume of this component or its matrix remained unchanged substantially.Particularly this just means (humidity=RH60% under the envrionment conditions of control; temperature=25 ℃); opening beaker (9 centimetre the diameter of component in thermostat container; do not have any protection baffle plate) in when storing 24 hours; component preferably keeps 75% to 125%; even 90% to 110%, perhaps even its stacking volume of 95% to 100%.Preferred this component humidity be 80% and above-mentioned storage condition under, component preferably remains 75% to 125% of its stacking volume, even 90% to 110%, perhaps even 95% to 100%.

Available any traditional method is measured the variation of stacking volume.What be particularly useful is the digitized video register system of band digital camera, and digital camera links to each other with the PC that itself is equipped with the measurement image analysis software.With gained 1cm ³Component sample be incorporated in the opening beaker that diameter is 9cm, and stored under these conditions 24 hours.After 24 hours, measure the size of all three-dimensional dimensions with the image analysing computer register system.To the measurement triplicate of each sample, and the variation of calculating the average bulk of representing with %.

Preferred ingredients is such, and when to be in median size be 2000 microns or littler particle form, these particles still kept 75% to 125% of its stacking volume, even 90% to 110%, perhaps even 95% to 100%.This available for example following method is measured: the particle that 20g is such, or comprise more than the particle of 500 particle weight and put into the capacity beaker that diameter is 9cm.The bottom of this beaker of tapping redistributes stable position until particle itself a little, and has horizontal upper surface.Measure this volume.To have these particulate opening beakers then carefully and be placed in the thermostat container, and under required %RH that sets and temperature, keep 24 hours.After 24 hours, measure stacking volume, and calculate the variation of the stacking volume of representing with %.

This component preferably includes (representing with weight) and accounts for composition weight at least 1%, and more preferably 5% to 70%, more preferably at least 10%, more preferably from 15% or even 20% or even a kind of (or multiple) activeconstituents of 25% to 50%.

This component preferably includes (representing with weight) 10% to 99%, more preferably at least 20% or even 30% to 99%, more preferably from 20% or 30% to 90% to 80% matrix.

This component comprises (representing with weight) at least 1%, more preferably from 5% or from 10%, or from 15%, or from 20% to 50%, or to 40%, or to 30%, or to 25% dissolution aids.

Matrix

The matrix of component of the present invention is referred to herein as " matrix ", is formed by polymer materials and softening agent.Described polymer materials and described softening agent be more detailed description hereinafter.

The ratio of softening agent and polymer materials is preferably 1 to 100 in the matrix, more preferably 1 to 70 or 1 to 50, more preferably 1 to 30 or even 1 to 20, this depends on the type of used softening agent and polymer materials.For example comprise PVA when polymer materials, and softening agent is when comprising glycerine or glycerol derivative and optional water, then this ratio preferably 1: 15 near 1: 8, preferred ratio is about 10: 1.

Matrix of the present invention can further contain the activeconstituents of component of the present invention and/or the dissolution aids of component of the present invention.Described activeconstituents and described dissolution aids will be described in more detail below.Also can add linking agent to change the performance of matrix or final component suitably.Borate comes in handy to matrix of the present invention.

Matrix optimization of the present invention has and is lower than 50 ℃, preferably is lower than 40 ℃, preferably less than 20 ℃ or even less than 10 ℃ or even less than 0 ℃ second-order transition temperature (Tg).The Tg of preferred matrix of the present invention is at-20 ℃ or even more than-10 ℃.

When using matrix Tg herein, refer to the Tg that is present in the matrix in the component, therefore this matrix may be the independent polymer materials and the mixture of softening agent, or polymer materials, softening agent, the mixture of activeconstituents and/or dissolution aids, and under any circumstance can choose wantonly and have annexing ingredient (stablizer for example as mentioned below, the thickening auxiliary agent, filler, lubricant etc.).

Tg such as the definition in the textbook " Dynamic Mechanical Analysis " (the 53rd page, the 57th page of Fig. 3 .11c) that the present invention uses are materials (matrix) during from glassy transition to rubbery state, and promptly segment obtains enough transport propertys each other and carries out the mobile temperature.

The Tg of the matrix of composition of the present invention can use Perkin-Elmer DMA 7e device measuring, according to the explanation of the operational manual of this equipment, produces a kind of as the described curve among the 57th page of Fig. 3-11 in Dynamic MechanicalAnalysis book.With the Tg of this device measuring is to be in the temperature between glass and " like the leather zone (leathery region) " or the logarithm of frequency, as defined in this article.

Described matrix, and preferred ingredient has special elasticity and flexibility because of its special second-order transition temperature on the whole.Specifically, but the matrix of this means and component reversible deformation, and the energy of absorption surging force or reactive force makes that component or matrix keep its original stacking volume substantially after the physical force invasion and attack and being applied on the described component.

Available matrix, or even the Young's modulus of component definition elasticity, and Young's modulus can use Young (Young ' s) modulus to define.The mechanical test method of available tension force known in the art or stress is calculated this modulus, for example uses Perkin-Elmer DMA 7e equipment, at the static tension range of special %, promptly measures according to producer's experimental procedure under the static tension force of 10-40%.This has represented applicable maximum tension in common production or operating process.Therefore, the Young's modulus of the present invention definition is with the maximum modulus of this device measuring in the static tension range of 10-40%.For example with this testing equipment the time, can use a 1cm ³The matrix (or component) of size.

With Perkin-Elmer DMA 7e device measuring matrix of the present invention the time, described matrix typically has less than 4GNm ^-2, or typically less than 2GNm ^-2, even be more preferably less than 1GNm ^-2, but typical even less than 0.5GNm ^-2, or even less than 0.1GNm ^-2, or even less than 0.01GNm ^-2Young's modulus or Young's modulus.When matrix especially of the present invention for example contained by the formed bubble of the method for introducing gas in matrix, its Young's modulus was lower than 0.1GNm ^-2, or even 0.01GNm ^-2, or even be lower than 0.005GNm ^-2, or even be lower than 0.0001GNm ^-2

Preferred this matrix is flexible, and with Perkin-Elmer DMA 7e device measuring the time, it has greater than 2%, is preferably greater than 15% or even greater than 50% relative yield strain.(this yield strain is the ultimate deformation when a matrix is in irreversible deformation in this test).

Specifically, this just means to have length-specific, for example (this static action power is variable to the matrix sample in the cross section of 1cm by along static action force compresses that this cross-sectional axis applies the time, but equal the twice of barometric point at least), after removing this reactive force, this length variations is at least 90% to 110% of original length.Available for example Perkin-ElmerDMA 7e equipment is measured.

Similarly, this matrix optimization has the flexibility of following degree, when using when the axle in this cross section applies a static action power and elongates the matrix sample in the cross section with length-specific (as 1cm), this static action power is variable, but equal the twice of barometric point at least, after removing this reactive force, this length variations is at least 90% to 110% of original length.Available for example Perkin-Elmer DMA 7e equipment is measured.

Particularly when this equipment of use, along 1cm ³The static action power that applies of axle of matrix sample in cross section increases gradually, is deformed into 70% until this component along above-mentioned cross-wise direction.Then, remove this reactive force and measure of the final deformation of matrix sample along cross-wise direction.Preferably after this test, cross-sectional length is preferably 90% to 110% of original cross-sectional length, and preferably from 95% to 105%, or even 98% to 100%.

Young's modulus or Young's modulus are relevant with relative density, promptly $\frac{E^{*}}{E_s}\≈{\left(\frac{{\mathrm{\ρ}}^{*}}{{\mathrm{\ρ}}_s}\right)}^2,$

ρ wherein ^*Be the relative density of matrix even component, ρ _sBe the relative density of matrix components or component as described in the present invention, E ^*Be matrix or even the Young's modulus of component itself, Es is matrix components or even the Young's modulus of component.This just means by regulating the amount and/or the type of softening agent, it is (perhaps as described below randomly to change density, for example by introducing air in making the process of foam formation), can with or even hard polymer materials with high Es become flexible and flexible matrix.

Matrix, or or even whole component be form of foam, preferably the interconnected reticulated structure of chamber and/or closed chamber is opened in its formation, especially forms the edge open chamber and/or closed chamber or the solid-state support or the dull and stereotyped reticulated structure of face.Space in the cell can contain part activeconstituents and/or gas, as air.

Preferably in component matrix, or closed chamber and the ratio of opening the chamber were preferably greater than 3: 2 greater than 1: 1 in the component integral body, even greater than 2: 1 or even greater than 3: 1.Can be by calculating the cumulative volume V of matrix or component sample _T, (being assumed to be sphere) opens chamber volume (V with the measurement of Mercury PorosimetryTest method then ₀), deduct this from cumulative volume and open the chamber volume and can obtain closed chamber volume (V _C: V _T=V ₀+ V _C), thereby determine this ratio.

Polymer materials

Available any polymer materials forms matrix of the present invention, and the preferred polymers material itself has aforesaid Tg, and perhaps more typically, available an amount of softening agent makes this polymer materials formation have the matrix of Tg as mentioned above.

Preferred this polymer materials comprises or is made up of a kind of (or multiple) amorphous polymer.

This polymer materials can be made up of the homopolymer of single type, or is the mixture of multiple polymers.The mixture of multiple polymers is particularly advantageous in the machinery and/or the solubility property of control component, and this depends on application and its requirement of component.

Preferred this polymer materials comprises that a kind of water can disperse or more preferably water-soluble polymers.According to the method for the water-soluble and water dispersible of measuring component of the present invention, water can disperse or water-solublely typically define according to mentioned above.With the maximum diameter of hole is 50 microns glass filter, and when measuring by method mentioned above, preferred water dispersible polymers of the present invention has at least 50%, preferably at least 75%, or even at least 95% dispersiveness; Polymkeric substance more preferably of the present invention is a water-soluble polymers, is 20 microns glass filter with the maximum diameter of hole, and when measuring by method mentioned above, it has at least 50%, preferably at least 75%, or even at least 95% water-soluble.

This polymkeric substance can have any molecular-weight average, be preferably about 1000 to 1000000, or even from 4000 to 250000, or even from 10000 to 200000, or even from 20000 to 75000.Preferred polymer materials has 30000 to 70000 weight-average molecular weight.

According to the performance of required component of the present invention, can regulate polymer materials.For example, be to reduce solubility property, be included in polymkeric substance in the material can have general 50000 or even 100000 above high molecular, vice versa.For example solubility property for a change can use the polymkeric substance with different degree of hydrolysis.For example, can increase the degree of crosslinking of polymkeric substance and/or can increase molecular weight for improving (reduction) Young's modulus.

The polymkeric substance that is preferred for component of the present invention has second kind of function, for example as a function in the composition that will mix this component.Therefore, for example, the polymkeric substance in polymer materials is the polymkeric substance that suppresses dye transfer, during dispersion agent etc., is useful for cleaning product.

Preferred polymkeric substance is selected from polyvinyl alcohol and derivative thereof, polyoxyethylene glycol and derivative thereof, polyvinylpyrrolidone and derivative thereof, ether of cellulose and derivative thereof, and these polymkeric substance mutually between or with the multipolymer of other monomer or oligopolymer.Most preferably PVP (and derivative) and/or PEG (and derivative), the most preferably mixture of PVA (and derivative) or PVA and PEG and/or PVP (and derivative).Most preferred polymer materials also can only comprise PVA.Preferred these polymkeric substance hydrolysis degree are at least 50%, more preferably at least 70%, or even 85% to 95%.

Softening agent

Can use any auxiliary softening agent that forms matrix of the present invention that is suitable for.Also can use the mixture of softening agent.

Preferred this softening agent, or at least a softening agent has and be higher than 40 ℃, preferably is higher than 60 ℃, or even be higher than 95 ℃, or even be higher than 120 ℃, or even be higher than 150 ℃ boiling point.

Preferred plasticizer comprises trivalent alcohol or glycerine, comprises the alkylene glycol deriv of ethylene glycol, and glycol oligomer is Diethylene Glycol for example, triethylene glycol, TEG and weight-average molecular weight are lower than 1000 polyoxyethylene glycol, paraffin and chloroflo, ethanol ethanamide, the ethanol methane amide, trolamine or its acetate and ethanolamine salt, Sodium Thiocyanate 99, ammonium thiocyanate, polyvalent alcohol for example 1, the 3-butyleneglycol, sugar, sugar alcohol, urea, dibutyl phthalate or dimethyl ester, oxa-monoprotic acid, oxa-diprotic acid, diglycollic acid and other have at least one linear carboxylic acid along the ether of its segment distribution, the mixture of water or these materials.

When making water, preferably there is a kind of additional softening agent.If used water, the water yield that then exists in foam formation typically is at least 3 weight %, more preferably more than 3 weight %, preferably even at least 5 weight %, or even at least 10 weight %.

The amount that softening agent exists be preferably article, preferably matrix weight at least 0.5%, as long as when water is unique softening agent, its amount be component or preferably matrix weight at least 3%.

The amount of preferred plasticizer is 1% to 3 5% of article or a matrix weight, is more preferably 2% to 25% of article or matrix weight, or even to 15%, or even to 10% or even to 8%.Definite amount depends on used polymer materials and softening agent, but must make the matrix of article have ideal Tg.For example when using urea, its amount is preferably 1% to 10% of matrix weight, and when using glycerine or ethylene glycol or other glycol derivative, preferred higher amount for example is 2% to 15% of component or a matrix weight.

Activeconstituents

This activeconstituents can be anyly will be released to liquid environment, or the material in the preferred aqueous environment, and preferably has active composition in aqueous environment.For example, when using in cleaning composition, this component can contain any active cleansing.This component also can comprise composition, for example cleaning compositions or personal care composition.

Especially advantageously in this component, mix to moisture-sensitive or with moisture and contact the activeconstituents that reacts, perhaps have limited impact resistance intensity, and in operating process, be easy to form the solids component of dust.

Activeconstituents generally is the composition to moisture-sensitive, thermally sensitive composition, oxidable composition, the combination of volatilizable composition or these materials.This activeconstituents can be a biological active materials, dangerous or deleterious material, for example the agricultural composition of agrochemical, for example medicinal ingredients of medicine or medicament, perhaps cleansing.

Especially preferred activeconstituents is an enzyme for example in this component, spices, SYNTHETIC OPTICAL WHITNER, bleach boosters, fabric positively charged ion and/or silicone softener and/or adjust agent, antiseptic-germicide, brightener, the mixture of optical white and these materials.

Other activeconstituents is the perhydrate SYNTHETIC OPTICAL WHITNER, metal perborate for example, metal percarbonate, especially sodium salt.Other preferred activeconstituents also has organic peroxy acid blanching precursor or promoter compound, and preferably the alkyl peroxy acids precursor compound of imide type comprises N-, N, N ¹N ¹Tetrem acidylate Alkylenediamine; wherein alkylidene group contains 1 to 6 carbon atom; the alkylidene group of these concrete compounds contains 1,2 and 6 carbon atom, for example tetrem acyl ethylene diamine (TAED); 3; 5,5-trimethyl acetyl oxygen base benzene sulfonic acid sodium salt (different-NOBS), acyloxy benzene sulfonic acid sodium salt in the ninth of the ten Heavenly Stems (NOBS); acetoxyl group benzene sulfonic acid sodium salt (ABS) and penta-acetyl glucose, and the alkyl peroxy acids precursor compound of acid amides replacement.

The activeconstituents that more preferably uses in component of the present invention is one or more enzymes.Preferred enzyme comprises the commercially available lipase that is incorporated into usually in the cleanser compositions, at, amylase, neutral and alkaline proteolytic enzyme, cellulase, restriction endonuclease (endolases), esterase, polygalacturonase, Sumylact L and peroxidase.Suitable enzyme has argumentation in US3519570 and 3533139.Preferred commercially available proteolytic enzyme comprises that the trade(brand)name that Novo Industries A/S (Denmark) sells is Alcalase, Savinase, Primase, those materials of Durazym and Esperase, the trade(brand)name that Gist-Brocades sells is Maxatase, those materials of Maxacal and Maxapem, the trade(brand)name that material that Genencor International sells and Solvay Enzymes sell is those materials of Opticlean and Optimase.Preferred amylase for example comprises the α-Dian Fenmei that obtains from the special bacterial strain of Bacillus licheniformis, and this has more detailed description in GB-1269839 (Novo).Preferred commercially available amylase comprises that the trade(brand)name that Gist-Brocades for example sells is those materials of Rapidase, and the trade(brand)name that Novo Industries A/S sells is Termamyl, those materials of Duramyl and BAN.Preferred amylase may be to be described in PCT/US9703635, the amylase among WO95/26397 and the WO96/23873.The starting raw material of described lipase can be fungi or bacterium, for example from the mould genus of humic, ThermomycesSp. or comprise the lipase that the bacterial strain of the Rhodopseudomonas of pseudomonas pseudoalcaligenes or Pseudomonas fluorescens obtains.The present invention also can use the lipase that is obtained by the chemistry of these bacterial strains or genetic modification variant.Preferred lipase obtains from pseudomonas pseudoalcaligenes, and this has description in the European patent EP-B-0218272 that authorizes.

Other preferred lipase of the present invention is the clone Humicola LanuginosaGene, and be expressed on the gene of aspergillus oryzae and obtain, described at European patent application EP-A-0258068, can be from Novo Industri A/S, Bagsvaerd, Denmark buys, trade(brand)name is Lipolase.This lipase also has description in the U.S. Pat 4810414 that people such as Huge-Jensen proposed on March 7th, 1989.

Dissolution aids

Component of the present invention comprises a kind of dissolution aids.

This dissolution aids is the replenishing of activeconstituents of component of the present invention.If component of the present invention comprises more than a kind of activeconstituents, then preferred one of them activeconstituents is chosen from dissolution aids or is served as dissolution aids.In order to reach purpose of the present invention, the supplementary component of dissolution aids composition activity composition always of the present invention.

Therefore, in order to reach purpose of the present invention, for using the component that comprises dissolution aids and activeconstituents qualification, wherein said component comprises a kind of composition with dual-use function, and can play defined activeconstituents of the present invention or dissolution aids, and except this has the composition of dual-use function, in article of the present invention, also must there be other dissolution aids or activeconstituents, to obtain the component that comprises activeconstituents and dissolution aids of the present invention.

When considering other embodiment of the present invention, above-mentioned narration about composition with dual-use function also is correct.For component of the present invention, comprise activeconstituents, polymer materials and softening agent (formation matrix) and dissolution aids are necessary.Therefore in order to obtain component of the present invention, in described component, must there be at least four kinds of different compositions.Can preferably select to have the neccessary composition of dual-use function.

When considering the preferred embodiment of the present invention, above-mentioned narration about composition with dual-use function also is correct, and for example preferred ingredient comprises the supplementary component as stabilization aid.

This dissolution aids can preferably include sulfonated compound, for example C ₁-C ₄Alkyl (thiazolinyl) sulfonate, C ₁-C ₄Arylsulphonate, the diisobutyl benzene sulfonate, tosylate, cumene sulfonate, xylenesulfonate, and the salt such as the sodium salt of these materials, and derivative or its composition, diisobutyl benzene sulfonate preferably, toluenesulfonic acid sodium salt, the isopropyl benzene sodium sulfonate, the combination of sodium xylene sulfonate and these materials.

This dissolution aids can comprise C ₁-C ₄Alcohols, methyl alcohol for example, ethanol, propyl alcohol, the combination as derivative and these materials of Virahol and these materials is preferably ethanol and/or Virahol.

This dissolution aids can comprise C ₄-C ₁₀Glycol, for example hexylene glycol and/or cyclohexanediol, preferred 1,6-hexylene glycol and/or 1,4 cyclohexane dimethanol.

This dissolution aids can comprise can be as the compound of thickening material, as based on cellulosic compound, particularly modification Mierocrystalline cellulose.

This dissolution aids can comprise the swelling agent as clay.Preferred clay is a montmorillonitic clay, particularly dioctahedron or trioctahedral montmorillonitic clay.Preferred clay is montmorillonite clay and HECTABRITE DP, perhaps other clay that finds in the bentonite structure.

This dissolution aids preferably includes the foaming system.Preferred foaming system comprises when having water, can with the acid source of alkali source reaction, be used for producing gas.The gas that produces by this reaction comprises nitrogen, oxygen and carbon dioxide.Acid source can be any organic acid, mineral acid or mineral acid, or these sour derivative or mixtures.Preferred acid source comprises organic acid.Suitable acid source comprises citric acid, oxysuccinic acid, toxilic acid, fumaric acid, aspartic acid, pentanedioic acid, tartrate, succsinic acid or hexanodioic acid, mono phosphoric acid ester sodium, the derivative of boric acid or these materials.Particularly preferably be citric acid, toxilic acid or oxysuccinic acid.

As previously mentioned, the foaming system preference comprises alkali source, but to achieve the object of the present invention, is to be understood that alkali source can be used as the part of this component, or comprise the part of the composition of this component, maybe can be present in and join this component or comprise in the washing lotion in the composition of this component.Can all can be used for the present invention with any alkali source of acid source generated reactive gas.Preferred alkali source is the perhydrate SYNTHETIC OPTICAL WHITNER, comprises perborate and silicate material.

Preferred gas is carbonic acid gas, and therefore preferred alkali source is a carbonate source, and it can be the carbonate of any kind of known in the art.In a preferred embodiment, carbonate source is a kind of carbonate.The example of preferred carbonate is alkaline-earth metal and alkaline carbonate, comprise yellow soda ash or salt of wormwood, supercarbonate and sesquicarbonate, and the mixture of these salt and calcium carbonate superfine powder are as disclosed in the German patent application of announcing on November 15th, 1,973 2321001.Alkali metal percarbonate also can be used as the source of suitable carbonate, and it can exist with one or more other carbonate source combinations.

The described acid source that exists in component and the mol ratio of alkali source are preferably 50: 1 to 1: 50, and more preferably 20: 1 to 1: 20, more preferably 10: 1 to 1: 10, more preferably 5: 1 to 1: 3, more preferably 3: 1 to 1: 2, more preferably 2: 1 to 1: 2.

Supplementary component

Component of the present invention preferably includes the supplementary component that can improve article activeconstituents stability of the present invention.

These supplementary components generally can be stablized the activeconstituents of component of the present invention, and work as this (or multiple) activeconstituents comprise oxidation or to the activeconstituents of moisture-sensitive, for example especially preferred during one or more enzymes.These supplementary components can also be stablized the matrix in the component of the present invention, have therefore stablized activeconstituents indirectly.These are stable to be defined as " stablizer " in the present invention with composition.

This stablizer is stabilizing active component or matrix preferably, when preventing to store by oxidation and/or moisture and the compound of degrading.This stablizer can be or comprise the foam matrix stablizer.This stablizer can be or comprise activeconstituents stablizer, particularly enzyme stabilizers.Keep stable by the foam matrix that makes article, thereby the stablizer of stabilizing active ingredient is called " suds-stabilizing agent " in the present invention indirectly.

Suds-stabilizing agent preferably includes tensio-active agent, for example Fatty Alcohol(C12-C14 and C12-C18), lipid acid, alkanolamide, the derivative of amine oxide or these materials or its composition.Suds-stabilizing agent can comprise trimethyl-glycine, sultaine, phosphine oxide, the derivative of alkyl sulfoxide or these materials or its composition.

Other preferred foam stablizer comprises one or more negatively charged ion or positively charged ion, for example single-, two-, trivalent or other polyvalent metal ion, preferred sodium, calcium, magnesium, potassium, aluminium, zinc, copper, nickel, cobalt, iron, the salt of manganese and silver, preferably having the anion balance ion is sulfate radical, carbonate, oxide compound, muriate, bromide, iodide, phosphate radical, borate, acetate moiety, citrate and nitrate radical, or the combination of these materials.

Suds-stabilizing agent can comprise finely divided particulate, and the median size that preferred finely divided particulate has is more preferably less than 1 micron, even is more preferably less than 0.5 micron less than 10 microns, or less than 0.1 micron.Preferred finely divided particulate is an aluminosilicate as indicated above, zeolite for example, and silica or ionogen, and be the finely divided particulate form.

Suds-stabilizing agent can comprise agar, sodiun alginate, sodium lauryl sulphate, polyethylene oxide, guar gum, the derivative of polyacrylic ester or these materials or its composition.

Suds-stabilizing agent can be with article in the isolating coating of matrix.Suds-stabilizing agent is partially enclosed with article or its activeconstituents typically, and preferred complete closed therein.

Typically, contact, and before preferably being incorporated in the article, coating contacts with described activeconstituents, preferably form coating thus thereon at the softening agent of activeconstituents with polymer materials or matrix.

Typically, after polymer materials and softening agent form matrix, preferably activeconstituents with among described matrix contacts or is incorporated into article after, coating contacts with these article, preferably forms coating thus thereon.

Preferred coating comprises polymkeric substance, typically be selected from polyvinyl alcohol and derivative thereof, polyoxyethylene glycol and derivative thereof, polyvinylpyrrolidone and derivative thereof, ether of cellulose and derivative thereof, and the multipolymer between these polymkeric substance or with the multipolymer of other monomer or oligopolymer.Most preferably PVP (and derivative) and/or PEG (and derivative), the most preferably mixture of PVA (and derivative) or PVA and PEG and/or PVP (and derivative).These polymkeric substance do not form the matrix of article of the present invention, so these polymkeric substance are different from the polymer materials of foam matrix.

Preferred coating comprises compound such as trivalent alcohol or glycerine, comprises the alkylene glycol deriv of ethylene glycol, the oligopolymer of polyoxyethylene glycol (digomeric), Diethylene Glycol for example, triethylene glycol, TEG and weight-average molecular weight M.W. are lower than 1000 polyoxyethylene glycol, wax and polyoxyethylene glycol, ethanol ethanamide, ethanol methane amide, trolamine or its acetate, ethanolamine salt, Sodium Thiocyanate 99, ammonium thiocyanate, polyvalent alcohol for example 1, the 3-butyleneglycol, sugar, sugar alcohol, urea, dibutyl phthalate or dimethyl ester, oxa-monoprotic acid, oxa-diprotic acid, diglycollic acid and other have at least one linear carboxylic acid along the ether of its segment distribution, the mixture of water or these materials.These compounds do not form the foam matrix of thing of the present invention.Therefore these compounds are different from the softening agent of foam matrix.

If particularly described activeconstituents comprises one or more enzymes, preferred stablizer is directly those reagent of stabilizing active ingredient of energy, is defined as " active stabilizer " or " enzyme stabilizers " in the present invention.Typical active stabilizer directly and activeconstituents have an effect and make it stable.

Be used for typical activity stablizer of the present invention and preferably include tensio-active agent.Being used for suitable tensio-active agent of the present invention is that this paper is at previously described those suitable tensio-active agents as the matrix stablizer.Except these tensio-active agents, be applicable to that other tensio-active agent of the present invention can comprise alkyl (alkenyl) sodium sulfonate, the alkoxyl group sodium sulfonate, preferred alkoxyl group sodium sulfonate is those of 10 to 18 carbon atoms that comprise any configuration, preferably linear, and average ethoxyquin degree is 1 to 7, is preferably 2 to 5.

Other preferred active stabilizer comprises boric acid, formic acid, acetate and salt thereof.These sour salt preferably comprise the gegenion of calcium for example and/or sodium.

Preferred active stabilizer comprises the positively charged ion as calcium and/or sodium.Be preferably calcium chloride and/or sodium-chlor.

Other preferred active stabilizer comprises average out to 3 to 20, preferred 3 to 10 amino acid whose little peptide chains, and itself and activeconstituents, particularly a kind of (or multiple) enzyme interacting also makes it stable.

Other active stabilizer comprises little nucleic acid molecule, and typically comprises 3 to 300, preferred 10 to 100 nucleosides.Typical nucleic acid molecule is thymus nucleic acid and Yeast Nucleic Acid.This nucleic acid molecule can be and other molecule, exist as the form of protein with complexing, perhaps can with the activeconstituents in the goods of the present invention, particularly form complex compound with a kind of (or multiple) enzyme.

Be suitable for the active stabilizer that the present invention uses, when particularly in article of the present invention, comprising a kind of SYNTHETIC OPTICAL WHITNER, it comprises antioxidant and/or reductive agent, as thiosulphate, methionine(Met), urea, thiourea peroxide, Guanidinium hydrochloride, Guanidinium carbonate, Guanidine Sulfamate 99, monoethanolamine, diethanolamine, trolamine, amino acid such as glycine, Sodium Glutamate, protein such as bovine serum albumin and casein, tertiary butyl hydroxytoluene, 4,4-butylidene two (the 6-tertiary butyl-3-methylphenol), 2,2 '-butylidene two (the 6-tertiary butyl-4-methylphenol), (single vinylbenzene cresols, toluylene cresols, single styrenated phenol, toluylene phenol, 1,1-two (4-hydroxyl-phenyl) hexanaphthene and derivative thereof, or the combination of these materials.

Other active stabilizer can comprise reversible activeconstituents inhibitor.Under the situation of not wishing to be bound by theory, if the researchist believes when particularly activeconstituents comprises one or more enzymes, reversible activeconstituents inhibitor can form complex compound with described activeconstituents, and improve the stability of described activeconstituents, make this activeconstituents stable when storage thus.When this activeconstituents discharges, when typically being discharged in the liquid environment, the reversible inhibitor dissociates with activeconstituents, and this activeconstituents can carry out that it is appointed or want the reaction carried out then.

Be applicable to that active stabilizer of the present invention can comprise sugar, be used for typical steamed bun stuffed with sugar of the present invention and draw together those that are selected from sucrose, glucose, fructose, raffinose, trehalose, lactose, maltose and derivative thereof and its combination.

This active stabilizer also can comprise sugar alcohol, as Sorbitol Powder, mannitol, nucite and derivative thereof and its composition.

Preferably this active stabilizer is coating or sealing coat form, partially enclosed at least article of the present invention or its activeconstituents, the activeconstituents of preferred complete closed article of the present invention or particularly enzyme. The method for preparing foam formation

Component of the present invention can prepare with following any method: preparation has the polymeric matrix that limits Tg, and this polymeric matrix is formed by polymer materials and softening agent, and with this matrix and activeconstituents and stablizer chemical combination.Preferable methods comprises with chemistry or physics mode gas is incorporated into polymer materials and softening agent, and in the optional activeconstituents.The preferred method of preparation component of the present invention may further comprise the steps:

A) obtain the mixture of a kind of polymer materials and softening agent, this preferred plasticizer is water and additional softening agent;

B) in the mixture of described polymer materials and water, introduce gas with chemistry or physics mode;

C) before the step b) and/or, add activeconstituents to described mixture with the step b) while and/or after step b);

D) before the step c) and/or, described mixture is contacted with dissolution aids with the step c) while and/or after step c);

E) the gained mix product is shaped;

If there is water, then a) to e) one or more steps after or remove portion water simultaneously.

Mixture is preferably aqueous mixture or slurry in step a), at b), c) and/or d) after the step or among remove portion water, make obtained component comprise 3% weight or more freedom moisture.

Step c) preferably includes the body that obtains comprising activeconstituents or a part of activeconstituents, and seals the step of this body with the mixture in the step b).

Step d) is preferably included in stablizer, preferred activeconstituents and before described mixture contacted, described activeconstituents mixed with described stablizer, more preferably mixing fully, or the step of sealing described activeconstituents with described stablizer.

Preferred this component comprises out chamber and/or closed chamber, and this method may further comprise the steps:

A) form polymer materials, active material, dissolution aids, softening agent and mixtures of liquids, wherein liquid can be identical compound with softening agent;

B) make claim b) mixture forming be body, and

C) vaporised liquid or a part of liquid, to form the space in mixture, this space forms the interior region of cell in the said components,

Wherein step c) is preferably undertaken by lyophilize or is undertaken by heater body, makes liquid or a part of liquid evaporation thus.

Step b) can also be carried out in that a) mixture is added to depress, and preferably under mixing and/or increase under the temperature and carry out, removes pressure or a part of pressure subsequently, makes liquid evaporation thus.For example, can use extrusion method.Wherein preferably with polymer materials, preferably include the softening agent of water, the optional activeconstituents and/or the mixture of dissolution aids are incorporated in the forcing machine, therein owing to mixing with because the heat that is applied, the further mixed and heating of mixture, preferred mixture wherein forms melts, (it can be formed required shape at extrusioning mixture then, for example granular) exit of leaving forcing machine reduces pressure, liquid or a part of liquid evaporation thus, or preferably water is evaporated from extrusioning mixture with the form of steam.This just produces the aforesaid spatial cell that has, and this cell can contain a kind of gas, is preferably air and optional activeconstituents.These spaces form the interior region of cell in the component matrix of the present invention.

Step b) in this method also can be undertaken by heated mixt, makes liquid or a part of liquid evaporation to form aforesaid space.Preferably mixture is transported in the spray-drying tower this step of operation, preferably mixture is sent from the nozzle that forms mixture droplets, and under conventional temperature this drop of spraying drying, obtain described component thus.

Available above-mentioned any currently known methods is introduced gas or foam by physics or chemical mode, preferably

-to choose wantonly and pass through in mixing, high shear force stirs (doing or wet approach), comprises injecting gas (doing or wet approach) under the critical gas gas dissolving of spreading and (doing or the wet approach) condition that relaxes and physical blowing;

-form gas with original position and (, comprise with effervescent system forming CO by the chemical reaction of one or more compositions ₂) the mode chemical foaming;

The foaming of-steam, uv radiation curing.

Preferably carry out drying step or additional excess liq or a part of liquid, for example drying step of water removed after these foaming step.Especially this drying step carries out after forming polymeric matrix at least, and chooses wantonly after adding activeconstituents and carry out, preferably as last step in this method.This drying step is preferred to be implemented like this, makes that the final component volume after the drying step is roughly the same with the volume before dry.In addition, preferably carry out this drying step, under the temperature of vacuum and reduction, remove for example water that desolvates thus by lyophilize.Fluidised bed drying slowly equally usefully, perhaps under the temperature that appropriateness increases, for example 40-80 ℃, or even 40-60 ℃ under use oven drying.

Preferred method comprises formation polymer materials and mixtures of liquids at least, preferred polymers material and a kind of solvent (preferably including water), and to the step that wherein adds softening agent (perhaps may be to add additional softening agent).If when requiring to have activeconstituents and/or dissolution aids in matrix, these materials can also join in the mixture of polymer materials solvent and softening agent.Perhaps, or can preferably matrix be formed on around the active material in addition, preferably around the core of active material and solid support material.

The preferred method that dissolution aids is incorporated in the component of the present invention comprises:

A) dissolution aids is contacted with the dry foam component, preferably dissolution aids is added in the dry foam component, to obtain foam formation of the present invention, for example by injection, or sealing component matrix is implemented; And/or

B) the cooling foam formation makes its temperature near the freezing point of described foam formation, has preferably just surpassed freezing point, dissolution aids is contacted with described foam formation, or dissolution aids is joined in the described foam formation, obtains foam formation of the present invention; And/or

C) as b), freezing afterwards described foam formation is for example before lyophilize; And/or

D) use a kind of material,, preferably be coated with this dissolution aids as the coating of hexadecyl alcohol moiety.

Further handling is for example to make final component be shaped to body as particle or bead, generally is dried to obtain component.Preferably before forming step, add gas.Forming step comprises granulation step, and for example atomizing or spraying drying are extruded, and make little ingot.Lyophilize is with the dry preferred method that forms component of body.

Below be preferable methods, measured with as described below prestress Heubach method of testing, described preferred method can obtain less dust or or even non-dusting particle, and the Tg of its matrix is lower than 10 ℃, Young's modulus is lower than 0.5GNm ^-2, this will further describe in following specific examples. First preferred method is as follows:

Obtain the polymer material solution (or polymkeric substance and mixtures of liquids) of aequum, and for example (introducing) in mixing tank.The active material (solution) that adds aequum then, for example enzyme solution, and dissolution aids, and add softening agent and other optional supplementary component of aequum, filler for example, thickening material etc.Stirring these materials makes it become the mixture of homogeneous.Preferably use above-mentioned any method, preferably for example gas of air is incorporated in this solution with the hybrid mode of physical method by high shear force.

Make this mixture forming particle with atomising method then, preferably use positive-displacement pump that mixture solution is transferred in (a plurality of) nozzle, preferably produce drop with single or many liquid jets.Preferably these drops are freezed then by refrigerant (can comprise liquid nitrogen, fluorine Lyons, refrigeration oil).Then these frozen granuless are transferred in the vacuum chamber, and preferred temperature (as what measure at particle surface) is lower than 0 ℃.

Preferably collect frozen granules, and do not improving under the temperature its transfer from spray tower.The sidewall of Freeze Dryers and contact disc temperature preferably remain on below 0 ℃, so that particle keeps frozen state.Vacuumize, the ice crystal that then freezes will rise the formation gas form, form cell in the particle thereby make.By vacuum tightness, cell sidewall and dish contact the whole degree of drying of temperature control.

After particle had been dried to the ideal water content, they were with unrestricted flow.Preferably particle is classified then by various sieves and/or treatment facility.

Have been found that the optional above-mentioned steps that gas (bubble) is incorporated in the polymkeric substance appearance liquid mixture can make particle have better shock-resistant ability, and reflect by its electric mould.Can introduce bubble in various manners.

In atomization steps, atomizing nozzle should be preferably placed in the spray column, and has enough height so that particle freezes when descending with gravity.Nozzle can have various designs-single hydraulic efficiency pressure nozzle, and rotation is inserted, sound wave or many liquid jets.Important aspect is that the blocking-up liquid air stream is to form independently drop.When these drops descend with gravity, must it be freezed these drop coolings.Refrigerant preferably is non-aqueous vapor body or liquid, and it can make the drop quick freezing.These drop coolings are formed the particulate actual temperature preferably be lower than 0 ℃, preferably be lower than-20 ℃.

Also preferably change aforesaid method in such a way:

With gas, preferred CO ₂Gas is incorporated in the mixture, and as mentioned above this mixture is incorporated in the spray-drying tower, forms spray-dired effervescent granules thus, can classify to it if desired.The temperature in of preferred this tower is about 130 ℃, and temperature out is about 75 ℃, and spray velocity is 12.5g/min.For example can use the Niro Mobil Minor that has two liquid jets thus.The gained particle may be a desired form, or can carry out further lyophilize under vacuum condition. Another kind of preferred method is as follows:

Obtain the polymer material solution (if or added liquid alternately, can use polymer powder) of aequum, and for example be incorporated in the mixing tank.Softening agent and optional other supplementary component of adding aequum then, filler for example, thickening material etc.Stirring these materials makes it become the mixture of homogeneous.Preferably by above-described any means, preferably the high shear force blending means by physics is incorporated into for example gas of air in the solution.

Preparation comprises activeconstituents such as enzyme in addition, and dissolution aids, with other composition chosen wantonly such as the particle of filler or carrier, for example be coated with by first ' core ' (is typically when these active substances are enzyme by fluidized-bed, these core particles are sugar or starch granules) be loaded on the fluidized-bed, and with the spray solution of active material or this active material to these core materials, then with the fluidization air of heat for example solvent drying from this living solution of water remove.

Then above polymeric blends is incorporated on these actives/cores, for example it is imported on the atomizing nozzle in the aforesaid fluidized-bed by positive-displacement pump.Can use nozzle, can preferably heterogeneity be joined in the core by different spray nozzles more than one.

Required fluidizing agent preferably is lower than 0 ℃, preferred about-20 ℃.Then fluidizing agent is with the freezing outside to activity core of polymeric blends/solution.This is the key parameter of a needs control, and generally this air themperature must be lower than 0 ℃, so that polymeric blends/solution quick freezing is to core particle.

Preferably thus obtained frozen granules is transferred in the aforesaid vacuum chamber then, perhaps classified.

The particle of the present invention that obtains with this technology comprises by the cingens matrix of activeconstituents.

Have been found that the optional above-mentioned steps that gas (bubble) is incorporated in the polymers soln mixture can make particle have better shock-resistant ability, and reflect by its Young's modulus. Another kind of preferred method is as follows:

Obtain the polymer material solution (or solid polymer and an amount of liquid) of aequum, and for example be incorporated in the mixing tank.(to this mixing tank) adds the active material (solution) of aequum then, for example enzyme solution and dissolution aids (solution), and add for example filler of the softening agent of aequum and optional other supplementary component, thickening material.Stirring these materials makes it become the mixture of homogeneous.Preferably by above-described any means, preferably the high shear force blending means by physics is incorporated into for example gas of air in the solution.

From mixing tank, this polymers soln is extracted in the forcing machine with pump then, or is extracted into end and has in the cavity of profiled sheeting.Before in entering forcing machine or cavity, can gas be injected in the mixture by mechanical shearing agitator or static mixer, for example with its dispersion.

When extrudate left profiled sheeting, pressure change caused the brilliant a little bloated or expansion of extrudate.Use die end milling cutter or some miscellaneous equipments (for example warmed-up wire, the slotting tool that is rotating etc.) that extrudate is switched to correct length then.This extrudate can be chosen wantonly by additional rounding step and make it become round.The treatment facility of realizing this function can comprise (rotating disk, accumulation dish, pelletizer, rotary drum, mixing drum etc.).

For example, by mixing 75g PVOH, 15g citric acid, 2g PEO and 22.5g glycerine with high shear force, promptly are set to continue for 40 seconds under the speed at full speed and prepare creme: add 80g H then in the Braum mixing tank ₂O and 80g enzyme and with high shear force promptly mix until forming slick and sly foam, greatly within 2 minutes under the speed at full speed being set to.From the 10ml injector, foam is expressed on the plastic plate.It is left standstill made its drying in 24 hours.In case dry, foam strips is cut into the long part of about 1-2mm, be 63.2% polyvinyl alcohol to form prescription, 19% glycerine, 12.7% citric acid, 1.6%PEO, 4% water, (drying) particle of 3.2% enzyme.

Gained particulate Young's modulus is 0.00016GNm ^-2

When with the test of prestress Heubach measuring method, the gained particle produces 0% dust, and this shows that particle has extraordinary impact resistance.(prestress Heutach measuring method is well known in the art, the equipment that uses German Heubach Engineering GMbH to provide, the stress deformation of the speed of rotation of its rotor (stressed modification) is 75 ± 1rpm, and bead is a wolfram varbide, and each bead weighs 82 grams). Preferably molded/system lozenge method

Most preferred method comprises uses mould that above-described compound particles is shaped; Thus mixture of the present invention is incorporated in the mould, carries out drying (lyophilize) subsequently.Preferred in addition a kind of method of using system ingot equipment with the aforesaid drum that preferably also comprises the mixture pressure of the gas of introducing to some extent by a perforation of rotating, is fallen on the mobile charge releasing belt, and it is configured as lozenge (drop or particle).After dry or sclerosis, the particle or the bead that will form thus with scraper plate remove down from charge releasing belt.

Preferred first step prepares polymer materials and softening agent, liquid ingredient and the activeconstituents of choosing wantonly and the mixture of dissolution aids.Preferably gas is incorporated in the mixture of the present invention.Preferred this mixture must not have big not dissolved particles, and this particle can block the perforation in the drum.Mixture preferably is in 0-50 ℃ temperature range.This mixture is extracted in the splitter, this splitter enter into rotation perforated drums and with the drum major axis parallel.It is inner that mixture is extracted into drum, and when the drum rotation, mixture is contacted with inner scraper plate, and this blade is installed on the bulging internal surface and contact with it along the length direction of perforated drums, and parallel with the charging splitter.The distance of perforated drums outside surface is (it is less than the diameter of perforation) in the scope of required particle height, but do not contact with the drum of the surface smoothing of charge releasing belt that moves or rotation, put inner scraper plate at this and contact, the tangential velocity coupling of the speed of perforated drums tangential velocity and charge releasing belt or the drum of surface smoothing with the internal surface of perforated drums.When order about this mixture by aperture size generally between the 300-2000 micron during perforation of (but also can be littler or bigger), this mixture is deposited on following surface.The rotational shear power of perforated drums makes raw material leave material on the smooth-flat-surface, stays thus required particulate drop of formation or lozenge.Can fix these lozenge by condensation or the mode that some or all of solvent liquids are evaporated.Condensation if desired, the temperature of the drum of charge releasing belt or surface smoothing can be in envrionment temperature in-20 ℃ scope.Evaporating solvent if desired then can be realized in the charge releasing belt thermal conduction between the envrionment temperature to 70 ℃ by temperature range, dry air (can be heated to 200 ℃ to reduce time of drying) is realized by the lozenge surface, perhaps by these two realization.With scraper plate the gained particle is removed down from drum or charge releasing belt then.This method of removing can be by using for example silicone oil improvement of a kind of examples of suitable lubricants (releasing agent) on drum.This lubricant or releasing agent bring extra advantage to particle, if the lozenge height is a kind of feature of wanting, can increase the lozenge height by the adhesive property that reduces between polyblend and the band/drum.

Embodiment

Embodiment 1

The method for preparing foam formation of the present invention

Polyvinyl alcohol solution (weight-average molecular weight M.W. is between 30000 to 70000) and 3360g enzyme solution (containing the organized enzyme of 5 weight % and the water of 85 weight %) with 4700g33%w/w, 159.3g glycerine and 155g cyclohexanedimethanol in the high speed shear mixing tank, mix, until forming level and smooth foam.This mixture is transferred in the charging stock tank, and its pump for example is extracted in the little ingot device of system that the Sandvik ProcessSystem by Totowa New York provides with toothed gear pump, and with having the 1mm diameter, being spaced apart the perforated drums of the perforation of 2.5mm.This device is deposited on lozenge and scribbles silicon layer and be heated on the drum of about 30 ℃ surface smoothing.When the drum when 1/4 was covered by lozenge, drum stopped the rotation.With these lozenge dryings, touching until the lozenge surface is exsiccant with hot air heater.Scrape and collect these gained particles then.

Embodiment 2

The method for preparing foam formation of the present invention is tablet, bead or particle form Device: microbalance, graduated 100ml flask is provided with Kenwood " Chef " food processor of agitator and mixing tank, glass or plastics grinding tool, scraper.

Chemical: poly-(vinyl alcohol) (Aldrich Chemicals, molecular weight Mw=30-70k), glycerine (99%, Aldrich Chemicals), citric acid (Aldrich, citric acid, anhydrous USP), distilled water, dry ice (or solid phase CO ₂), adiabatic box.

Step

1 PVA that weighs 50 ± 0.2g, the glycerine of 30 ± 0.2g, the cyclohexanedimethanol of 50 ± 0.2g.

2 (are designated as 2, low-shearing power) with mixing tank mixing PVA, glycerine and citric acid under the lower velocity that sets.

3 progressively join the water of 50 ± 1ml in the dry blending device, and keep this mechanically mixing 2 minutes.Obtain slick and sly colloid.

4 increase mixing velocity, improve shearing force until maximum set value (being designated as 8).The water that adds 10-20ml is until forming the PVA foam.Keeping this high shear force mixed 3 minutes.

5 under the condition that keeps mechanically mixing, and with activeconstituents, for example the enzyme of 2-10g progressively joins in the foam, obtains the active foam of homogeneous thus.

6 stop to mix.In mould, and avoid any structure to subside the PVA foam dispersion.

7 are placed on the mould that is filled with in the adiabatic box that is filled with 1/3 dry ice.Left standstill freezing 5 hours.

8 are placed on (Edward XX) in the vacuum freeze drying with freezing sample fast, keep 24 hours.

9 samples that from mould, remove dry down.

Any activeconstituents that can in step 5, add any amount, general high to about 50g, fabric softening agent for example, SYNTHETIC OPTICAL WHITNER, nonionogenic tenside.

Any dissolution aids that can add any amount in step 5 is general high to about 50g, for example cyclohexanedimethanol or toluenesulfonic acid sodium salt.

Embodiment 3

The method for preparing foam formation of the present invention is tablet, bead or particle form

Device: as above an embodiment is described

Chemical: poly-(vinyl alcohol) (Aldrich Chemicals, molecular weight Mw=30-70k), glycerine (99%, Aldrich Chemicals), yellow soda ash (Aldrich, anhydrous), dodecyl sulfate tensio-active agent (Aldrich), distilled water, training Ti Shi culture dish (diameter 90mm), baking oven (being set in 45 ℃ ± 2 ℃).

Step

1 PVA that weighs 50 ± 0.2g, the glycerine of 30 ± 0.2g, the cyclohexanedimethanol of 20 ± 0.2g, the yellow soda ash of 20 ± 0.2g and the dodecyl sulfate of 2 ± 0.2g.

2 (are designated as 2) with mixing tank mixing PVA, glycerine, citric acid and dodecyl sulfate under the lower velocity that sets.

3 progressively join the water of 50 ± 1ml in the dry blending device, and keep this mechanically mixing 2 minutes.Obtain slick and sly colloid.

4 add for example activeconstituents of 5g enzyme, and yellow soda ash, and brute force stirs 30 seconds until obtaining adequately expanded foam.

5 with foam dispersion in training Ti Shi culture dish, become the thick-layer of uniform 1cm.

6 will train in the baking oven that the Ti Shi culture dish is placed on 40 ℃ 24 hours.

7 foam films that from mould, remove dry down.

Any activeconstituents that can in step 4, add any amount, general high to about 50g, fabric softening agent for example, SYNTHETIC OPTICAL WHITNER, nonionogenic tenside.

Any dissolution aids that can in step 1, add any amount, general high to about 50g, SDS for example, STS, SXS, SCS, CHDM.

Available 55wt% polycarboxylic acid polymer, the enzyme of 20wt% anhydrous sodium carbonate and 25wt%, softening clays etc. repeat above-mentioned steps; And use the 45wt% polycarboxylic acid polymer, and the 15wt% polyoxyethylene glycol, the enzyme of 20wt% anhydrous sodium carbonate and 20wt%, softening clays etc. repeat above-mentioned steps.

Claims (14)

1. foam formation, it comprises the matrix that is formed by polymer materials and softening agent, dissolution aids and preferred activated activeconstituents in aqueous environment, this foam formation is stable when contacting with air, is unsettled when contacting with water.

2. foam formation as claimed in claim 1, it is release of active ingredients or part activeconstituents when contacting with water, partly or entirely decomposes when preferably this component contacts with water, disperses sex change and/or dissolving.

3. the foam formation of arbitrary claim as previously mentioned, its Young's modulus that has is less than 10GNm ^-2, preferably less than 1GNm ^-2

4. the foam formation of arbitrary claim as previously mentioned, wherein said activeconstituents is the cleaning product composition, the fabric nursing composition, drug ingredient or cosmetic composition, preferably from enzyme, tensio-active agent, brightener, dyestuff, froth suppressor, SYNTHETIC OPTICAL WHITNER, bleach boosters, fabric softening agent, fabric is adjusted agent, the mixture of antiseptic-germicide and these materials.

5. the foam formation of arbitrary claim as previously mentioned, wherein said dissolution aids comprises the foaming system, hydrotropic agent, cellulose materials, the combination of water-soluble salt or these materials.

6. the foam formation of arbitrary claim as previously mentioned, the second-order transition temperature of wherein said polymer materials is less than 50 ℃, preferably less than 40 ℃.

7. the foam formation of arbitrary claim as previously mentioned, wherein said polymer materials comprises water-soluble polymers, is preferably water-soluble poval.

8. the foam formation of arbitrary claim as previously mentioned, it is a particle form, and median size is 50 to 4000 microns, is preferably 100 to 150 microns.

9. the foam formation of arbitrary claim as previously mentioned, it has 0.05 to 0.9, preferred 0.3 to 0.7 relative density.

10. the foam formation of arbitrary claim as previously mentioned, wherein said component comprises a series of chamber and closed chambers opened, and the number of wherein opening chamber and closed chamber is than preferably being at least 1: 1.

11. the foam formation of arbitrary claim as previously mentioned, its available method that may further comprise the steps obtains:

A) obtain the mixture of polymer materials;

B) in described mixture, introduce gas with chemistry or physics mode;

C) before the step b) and/or, described mixture is contacted with activeconstituents with the step b) while and/or after step b);

D) before the step b) and/or, described mixture is contacted with dissolution aids with the step b) while and/or after step b); With

E) the gained mixture is configured as goods;

If wherein there is water, preferably a) to e) one or more steps after or remove portion water simultaneously.

12., described dissolution aids is contacted with the mixture of described polymer materials and softening agent as the foam formation of claim 11.

13. each the purposes of foam formation of claim 1 to 12 is that activeconstituents is discharged in the aqueous environment, preferred activeconstituents is the sanitising agent activeconstituents, is preferably enzyme, and aqueous environment is a bath water.

14. each the purposes of foam formation in cleaning compositions, Fabrid care composition, personal care composition, make-up composition or composite medicine of claim 1 to 12 preferably mixed the activeconstituents of the mixture that is selected from enzyme, spices, tensio-active agent, brightener, dyestuff, froth suppressor, SYNTHETIC OPTICAL WHITNER, bleach boosters, fabric softening agent, antiseptic-germicide, foaming system and these materials in these compositions.