CN1402778A - Elastic article - 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

Elastomeric article

Technical field

The present invention relates to elastomeric article, be generally particle, they comprise a kind of matrix that is formed by following material: polymer materials and softening agent, stablizer and activeconstituents as the sanitising agent activeconstituents, generally are released in the aqueous environments.

Background of invention

Composition such as cleaning product and personal care articles, makeup and medicine comprise activeconstituents usually, and this activeconstituents is released in the water or requires it to have activity in aqueous environments.Many these activeconstituentss when storing to humidity, temperature variation, light and/or air-sensitive.

Another problem of many these activeconstituentss, especially enzymes is: owing to the physical force that is applied in the treating processes above them, they tend to form dust.This not only produces waste product, and dust also can cause health and health problem.

The trial that overcomes these problems has caused protecting with coating or encapsulating drug the development of these activeconstituentss.The problem of many these coated particles is: they do not show enough shock resistances usually in treating processes, and do the time spent when the physical force that is subjected to generally can running in treating processes, can form dust, and this can cause health and health problem.

The inventor has been found that the protection activeconstituents and these activeconstituentss is discharged into improving one's methods in the aqueous medium.They have been found that the certain elasticity goods that comprise the foam base plate that is formed by polymer materials and softening agent are very shock-resistant, and can protect the activeconstituents that adds wherein to avoid acting on the influence of the physical force on this elastomeric article.Say that further the inventor has been found that when simultaneously stablizer being added elastomeric article, can further protect activeconstituents to avoid the influence of air, humidity and chemical reaction, they can cause the activeconstituents degraded.

Therefore; elastomeric article of the present invention is high-impact, therefore causes reducing fracture or wearing and tearing in the treating processes, and reduces the formation of dust; and protect the activeconstituents that adds wherein to avoid the influence of air, humidity or chemical reaction, and in storage process, in these goods, keep stable.For example, can obtain to comprise the elastomeric article of enzyme, as particle or bead, their safety and effectively more in handling and using.In addition, can make these goods that following effect is arranged: they will add wherein activeconstituents such as enzyme, very be discharged in the aqueous environments effectively.In general, the form of goods of the present invention is foam articles, and it is an air-stable when common humidity is stored, but is unsettled when contacting with water, therefore easy release of active ingredients.Elastomeric article all is useful in any product, is particularly useful in cleaning product, medicine, personal care articles, makeup and fabric nursing product.

The invention summary

Elastomeric article provided by the invention comprises:

A) activeconstituents; With

B) foam base plate that forms by polymer materials and softening agent; And

C) stablizer;

Wherein, described goods can be discharged into described activeconstituents in the liquid medium and go.

The elastomeric article here preferably comprises foam base plate, and its second-order transition temperature (Tg) is lower than 50 ℃, preferably is lower than 40 ℃.

Elastomeric article preferably exists with the foamy form, and stable when contacting with air, and instability when contacting with water, preferably the Young's modulus of these goods is less than 0.1GN.m ^-2, preferably less than 0.01GN.m ^-2

Stablizer can be stablized the activeconstituents in these goods.The stability of activeconstituents depends on the stability of foam base plate and/or depends on the stability of activeconstituents itself.

Therefore, stablizer can be, maybe can comprise the matrix stablizer, and it can stablize the foam base plate in the elastomeric article in the storage of elastomeric article or the course of processing.

Also can be with the direct stabilizing active ingredient of stablizer.For example, by increasing the structural stability of activeconstituents.Therefore, but also preferred stabilizer be or comprise the activeconstituents stablizer.

Also preferably the activeconstituents of this elastomeric article comprises at least a enzyme.If comprise enzyme in elastomeric article, then this enzyme can and have air, moisture or SYNTHETIC OPTICAL WHITNER existence to issue changing property or begin to take place sex change to moisture, air or SYNTHETIC OPTICAL WHITNER (if present) sensitivity.Therefore, preferred stabilizer is an enzyme stabilizers, and it can stablize the enzyme in the elastic granule, and also can stabilized enzyme in preparation elastic granule process.

The invention still further relates to the technology of preparation elastomeric article.Preferably obtain elastomeric article by the technology that comprises the following step:

A) mixture of acquisition polymer materials and softening agent, preferably water and other softening agent; With

B) in this mixture, introduce gas by chemistry or physical method; With

C) before step b) and/or simultaneously and/or afterwards this mixture is contacted with a kind of activeconstituents; With

D) before step c) and/or simultaneously and/or afterwards this mixture is contacted with a kind of stablizer; With

E) be goods with the gained mixture forming;

Wherein, preferably in step a) to e) in one or more steps after or remove portion water simultaneously, if there is water to exist.

In another specific examples of the present invention, provide and use elastomeric article that activeconstituents is discharged into purposes in the aqueous environments, preferably this activeconstituents is the cleaning action composition, preferred enzyme, and preferred aqueous environments is washing water.The detailed Description Of The Invention elastomeric article

Elastomeric article of the present invention is called " goods " here, comprises a kind of activeconstituents, a kind of matrix and a kind of stablizer.This activeconstituents, matrix and stablizer have more detailed explanation subsequently.

Preferred these goods are water dispersible, water decomposition or water miscible.The dispersity of preferred here water dispersible goods is at least 50%, preferably at least 75% or even be at least 95%, be that 50 microns glass filter is measured with method described below with the maximum diameter of hole; More preferably the goods here are water miscible or water decomposition, and solubleness or resolution be at least 50%, preferably at least 75% or even at least 95%, be 20 microns glass filter with the maximum diameter of hole, measure with method described below, that is:

Hydrometer method is measured water solubility, water decomposition degree or the moisture divergence of these goods:

These goods of 50g ± 0.1g are added in the 400ml beaker that weight claimed, and add the distilled water of 245ml ± 1ml.Being that 600 rev/mins magnetic stirring apparatus is powerful with rotating speed stirred material 30 minutes.Then, goods-mixture is filtered with a quantitative fritted glass filter of paper folding, the aperture of this strainer (is 20 or 50 microns to the maximum) as defined above.With water evaporate to dryness from the filtrate of collecting, and measure the weight of residue goods part (dissolved, decomposition or dispersive part) with any method commonly used.Then, can calculate the per-cent of solubleness, resolution or dispersity.

These goods generally are used for active substance is discharged in the aqueous medium.Preferred these goods, preferably its matrix is unsettled when contacting with water.It is to take place like this: an activeconstituents in these goods or its part are discharged in a kind of liquid, in preferred a kind of aqueous medium such as the water.Preferred these goods or its a part of sex change, decomposition preferably are dispersed or dissolved in the liquid, preferably in aqueous medium, more preferably in water.May be preferably with the activeconstituents snap-out release in water, and the preferred elastomeric goods disperse or dissolve fast; Preferably at these goods with after water contacts, at least 10 these goods of weight % dissolved in 30 minutes or disperse, or more preferably at least 30% or even at least 50% or even at least 70% or even at least 90%[add in the entry with the concentration of 1 weight %].Even can also preferred these goods with after water contact, 20 minutes or even 10 minutes or even 5 minutes in dissolving or dispersion take place.Can measure dissolving or dispersion with dissolving, decomposition and the dispersive method of these goods of measurement described below.

The preferred elastomeric goods are such: the cumulative volume of goods can change, and preferably compares with initial cumulative volume and is reduced by at least 10%, and this value can be pressed example and measure: with 1cm ³Goods put into the 100ml deionized water, and be to stir 5 minutes with 200 rev/mins rotating speed under 25 ℃ in temperature.The variation of preferred cumulative volume, or preferred cumulative volume be reduced by at least for for example 20% or even at least 40% or even at least 60% or even at least 90% or even about 100% because can decompose fast, disperse or be preferably dissolved in the water by preferably whole basically goods.

This can measure with any method known in the art, especially adopts following method (two method of soaking) here: get 1cm ³In elastomeric article and the long-pending graduated cylinder of microbody, filled the organic inert solvent of 50ml ± 0.1ml in the graduated cylinder with its adding 100ml.For example, when find acetone both unchangeability and/or not with this elastomeric article matrix in polymer materials when interacting, for example when polymer materials is PVA, just adopt acetone.Character according to research goods can adopt other neutral organic medium; Inert solvent is such: goods are not basically by dissolution with solvents, dispersion, decomposition or sex change.

Graduated cylinder is air impervious, and places 1 minute, so that make solvent permeate whole elastomeric article.Volumetric variation and with its original volume V as foam sample _iThen goods are taken out from solvent and make solvent evaporation at air drying.

Then goods are put into the 250ml beaker that comprises the 100ml deionized water, remained on 25 ℃, stirred 5 minutes with the speed of magnetic stirring apparatus with 200 rev/mins.Remaining product sample if any, filters with the copper mesh strainer of 60mm, and the baking oven that puts it into certain temperature keeps for some time to remove residual water.Put the residue goods that drying is crossed into graduated cylinder once more, wherein the volume of acetone is transferred to 50ml again.

The monitoring cumulative volume increase and with its final volume V as elastomeric article _fThen the long-pending minimizing Δ V of elastomeric article population of samples just is: $\%\mathrm{\ΔV}=\frac{V_f}{V_i}*100$

The relative density ρ of preferred elastomeric goods ^*Be 0.01-0.95, more preferably 0.05-0.9 or even be 0.1-0.8 or even for 0.3-0.7.Relative density is meant the density (ρ of goods ^*) with all material that is used for forming goods each minute density summation (ρ _s) the ratio.

Preferred foams goods used herein generally be air-stable or when contacting, be stable with air, this means that cumulative volume remained unchanged substantially when goods or its matrix were exposed to air.This especially shows: (diameter is 9cm to the uncovered beaker in being stored in thermostat container; without any protective layer) keep after 24 hours; preferred articles of manufacture keep cumulative volume 75%-125% or even 90%-110% or even 95%-100%; this thermostat container is controlled under the ambient environmental conditions (humidity=RH60%, temperature=25 ℃).Preferably under above-mentioned storage requirement elastomeric article keep its cumulative volume 75%-125% or even 90%-110% or even 95%-100%, wherein humidity is 80%.

The variation of cumulative volume can be measured with any ordinary method.What be particularly useful is the digital image register system, and it comprises a digital camera that is connected on the PC, and this computer is equipped with the reference image analysis software.Get a 1cm ³Product sample, and it is joined in the uncovered beaker that a diameter is 9cm, stored under these conditions 24 hours.After 24 hours, measure all three-dimensional dimensions with the image analysis register system.Each sample replicate measurement three times, the variation that average overall is amassed is with percentage calculation.

The preferred elastomeric goods are such: when with median size being 2000 microns or littler particulate state when existing, these particles also keep 75%-125% or even the 90%-110% or even the 95%-100% of cumulative volume.This can be by for example, adds this particle of 20g or comprise to surpass 500 particulate weight and measure in diameter is the volumetry beaker of 9cm.Knock gently at the bottom of the beaker, rearrange settling position up to elastic granule with horizontal surface.Measure volume.The uncovered beaker that will comprise elastic granule is then put thermostat container carefully into, keeps 24 hours, and is set under required %RH and temperature.Measure the cumulative volume after 24 hours, with the variation of percentage calculation cumulative volume.

Elastomeric article preferably comprises the activeconstituents of (weight percent) at least 1%, more preferably 5%-70%, more preferably at least 10 of goods weight %, more preferably 15% or even 20% or even 25%-50%.

Elastomeric article preferably comprises the matrix of (weight percent) 10%-99%, more preferably at least 20% or even 30%-99%, more preferably 20% or 30%-90%-80%.

Elastomeric article comprises (weight percent) at least 1% stablizer, more preferably from 5% or 10% or 15% or 20% to 50% or 40% or 30% or 25%.Matrix.

The matrix of elastomeric article of the present invention is called " matrix " here, is formed by polymer materials and softening agent.This polymer materials and this softening agent will be described in further detail hereinafter.

Softening agent is preferably 1: 100 with the ratio of polymer materials in the matrix, more preferably 1: 70 or 1: 50, more preferably 1: 30 or even 1: 20, this depends on the type of used softening agent and polymer materials.For example, when polymer materials comprises PVA, and softening agent is when comprising the derivative of glycerine or glycerine and optional water, and ratio preferably approximately 1: 15-1: 8, one preferred ratios are about 10: 1.

The matrix here can further comprise activeconstituents of these goods and/or the stablizer of these goods.This activeconstituents and this stablizer will be described in further detail hereinafter.Also can add the performance that linking agent is suitably adjusted matrix or end article.Perhaps useful at this paper matrix mesoboric acid salt.

The second-order transition temperature of this paper matrix (Tg) is lower than 50 ℃, preferably is lower than 40 ℃, preferably is lower than 20 ℃ or even be lower than 10 ℃ or even be lower than 0 ℃.The Tg of preferred this paper matrix is higher than-20 ℃ or even be higher than-10 ℃.

The Tg of the matrix of Shi Yonging is the Tg of the matrix that exists in goods herein, therefore it can only be the mixture of polymer materials and softening agent, it also can be the mixture of polymer materials, softening agent, activeconstituents and/or stablizer, and under any circumstance, can there be optional supplementary component (thickening material as mentioned below, filler, lubricant or the like).

(53 pages on Tg used herein and textbook " dynamic mechanical analysis ", Fig. 3 .11c in 57 pages) the lining definition is the same, promptly be when material (matrix) when glassy transition is rubbery state, the temperature of the material (matrix) when chain obtains enough reactivity and slides mutually just.

Can on Perkin-Elmer DMA 7e equipment, measure the Tg of matrix in the goods of the present invention,, produce a curve shown in 57 pages of Fig. 3-11c in the textbook " dynamic mechanical analysis " with reference to the guide of this operation of equipment handbook.Tg is with the temperature between the vitreous state as herein defined of this measuring apparatus and " the leather district ", or the logarithm of frequency.

Matrix, and preferably whole elastomeric article are because of its specific second-order transition temperature has specific elasticity and flexibility.Especially, this means the reversibly deformation of matrix and goods, absorb to impact or the energy of power that can to recover original overall basically long-pending thereby stop to apply after the physical pressure goods or matrix on parts.

Elasticity can with matrix or even the Young's modulus of goods define, also can define by Young's modulus.This can calculate from strain known in the art or stress mechanical test, for example, by producer's experimental procedure, with Perkin-Elmer DMA 7e equipment, in specific static strain percentage range, promptly tests in the static strain scope of 10-40%.This has represented the maximum strain that may apply in common production and treating processes.Therefore, the Young's modulus of definition is the maximum modulus of measuring in the static strain scope of 10%-40% with this equipment here.For example can be with a 1cm in the test of this equipment ³Matrix (or goods).

The Young's modulus or the Young's modulus of this matrix are generally less than 4GN.m ^-2, or be generally less than 2GN.m ^-2, even be more preferably less than 1GN.m ^-2, but general even less than 0.5GN.m ^-2, or even less than 0.1GN.m ^-2, or even less than 0.01GN.m ^-2, with Perkin-Elmer DMA 7e measuring apparatus.Especially, comprise this matrix of bubble, for example form bubble by the technology that relates to introducing air in matrix, its Young's modulus is less than 0.1GN.m ^-2, or even less than 0.01GN.m ^-2, or even less than 0.005GN.m ^-2Or even less than 0.0001GN.m ^-2

Preferred this matrix is flexible, thereby its relative yield strain is preferably greater than 15% or even greater than 50%, with Perkin-Elmer DMA 7e measuring apparatus greater than 2%.(in this test, yield strain is that a matrix produces the strain limit in the time of can not replying deformation.)

Especially, this means that matrix sample when the cross section with length-specific such as 1cm is subjected to along this sectional axis when the compression of static load, this static(al) is variable but equal 2 times of barometric point at least, and unloading back length variations is the 90%-110% at least of original length.This can measure with for example Perkin-Elmer DMA 7e equipment.

Equally, preferred substrate has certain snappiness, thereby when the matrix sample in the cross section with length-specific such as 1cm is being subjected to along this sectional axis when static(al) stretches, this static(al) is variable but be 2 times of barometric point at least, and unloading back length variations is the 90%-110% at least of original length.This for example can utilize Perkin-Elmer DMA 7e equipment to measure.

Especially, when using this equipment, this acts on 1cm ³The matrix sample sectional axis to static(al) increase gradually, be 70% up to the deformation of this test specimen on cross-wise direction.Unloading then, and measure the final deformation of matrix sample on cross-wise direction.Preferably, the length in cross section, current experiment back is preferably the 90%-110% of cross section original length, preferred 95%-105% or even be 98%-100%.

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

Wherein, ρ ^*For matrix or or even goods relative density, ρ _sBe the relative density of each component in matrix described here or the goods, E ^*Be matrix or even the Young's modulus of elastomeric article itself, E _sFor matrix or or even goods in the Young's modulus of each component.This means content by adjusting softening agent and/or type and randomly by adjusting density (or, for example, as mentioned below) by in preparation technology, introducing gas to form the elastic foam goods, can with or even high E arranged _sRigid polymer material make elasticity, softish matrix.

Preferred substrate, or even whole goods exist with form of foam, and preferably it forms the interconnection network of perforate and/or closed pore, especially by forming the network that perforate and/or closed pore edge and surperficial solid-state skeleton or plate are formed.Space in the hole can comprise part activeconstituents and/or gas, as air.

Preferably in the matrix or whole goods of goods, the ratio of closed pore and perforate is greater than 1: 1, is preferably greater than 3: 2 or even greater than 2: 1 or even greater than 3: 1.Can be by the cumulative volume V of compute matrix or product sample _TMeasure this ratio, (being assumed to be sphere) uses mercury voidage test method determination open volume (V then ₀), from cumulative volume, deduct open volume, then obtain closed pore volume (V _C: V _T=V ₀+ V _C).Polymer materials

Can form the matrix of this paper with any polymer materials, condition be it Tg as defined above, perhaps more typically, use an amount of softening agent can make it form the aforesaid matrix of Tg.

The preferred polymers material comprises or is made up of a kind of (or multiple) amorphous polymer.

Polymer materials can be formed or be made up of mixture of polymers by the homopolymer of single type.Polymeric blends is especially favourable to the mechanics and/or the solubility property of control elastomeric article, depends on their application and requirement.

The preferred polymers material comprises water dispersible or more preferably water miscible polymkeric substance.Water dispersible and water-soluble generally definition are as mentioned before determined according to the method for water solubility that is used for measuring these goods and moisture divergence.The dispersity of the preferred aqueous dispersion polymers here is at least 50%, preferably at least 75% or even at least 95%, be that 50 microns glass filter is measured by foregoing method with the maximum diameter of hole; More preferably the polymkeric substance here is a water-soluble polymers, and its solubleness is at least 50%, preferably at least 75% or even at least 95%, be that 20 microns glass filter is measured by foregoing method with the maximum diameter of hole.

Polymkeric substance can have any molecular-weight average, preferably approximately 1000-1,000,000, or even 4000-250,000 or even 10,000-200,000 or even 20,000-75,000.Very preferably the weight-average molecular weight of polymer materials is 30,000-70,000.

The performance required according to these goods can the telomerized polymer material.For example, in order to reduce solubleness, can comprise in the material have high score in the amount polymkeric substance, generally be higher than 50,000 or even be higher than 100,000, vice versa.For example, in order to change solubleness, can use polymkeric substance with different degree of hydrolysis.For example, in order to improve (minimizing) Young's modulus, can increase the degree of crosslinking of polymkeric substance and/or increase molecular weight.

Preferably the polymkeric substance that uses in this elastomeric article has a kind of subsidiary function, for example will be incorporated into the function in the composition of goods.Therefore, for example for cleaning product, when the polymkeric substance in the polymer materials is that a kind of dye migration is useful when suppressing polymkeric substance, dispersion agent etc.

Preferred polymkeric substance be selected from polyvinyl alcohol and derivative, polyoxyethylene glycol and derivative thereof, Polyvinylpyrolidone (PVP) and derivative thereof, ether of cellulose and derivative thereof and these polymkeric substance each other or with the multipolymer of other monomer or oligopolymer.Very preferably PVP (and derivative) and/or PEG (and derivative), the very preferably mixture of PVA (and derivative) or PVA and PEG and/or PVP (or derivatives thereof).The polymer materials that also can very preferably only comprise PVA.

The degree of hydrolysis of preferred these polymkeric substance is at least 50%, and more preferably at least 70% or even be 85%-95%.Softening agent

Can use any softening agent that defined matrix forms that is suitable for helping here.Also can use the mixture of softening agent.Preferably when making water, there is a kind of additional softening agent.

Preferably, softening agent or at least the boiling point of the softening agent of one of them be higher than 40 ℃, preferably be higher than 60 ℃, or even be higher than 95 ℃, or even be higher than 120 ℃, or even be higher than 150 ℃.

Preferred plasticizer comprises glycerine, glycol derivative, comprise ethylene glycol, oligomeric polyoxyethylene glycol such as glycol ether, triglycol and Tetraglycol 99, weight-average molecular weight M.W. is lower than 1000 polyoxyethylene glycol, wax and chloroflo, the ethanol ethanamide, the ethanol methane amide, trolamine or its acetic ester, and ethanolamine salt, Sodium Thiocyanate 99, ammonium thiocyanate, polyvalent alcohol is as 1, the 3-butyleneglycol, sugar, sugar alcohol, urea, dibutyl phthalate or dimethyl ester, contain the acid of oxygen list, contain the oxygen diacid, diglycollic acid, and along distributing other line style carboxylic acid of at least one ether of molecular chain, water or its mixture.

The consumption of preferred plasticizer accounts for product weight, preferably accounts at least 0.5% of matrix weight, and condition is that its consumption accounts for product weight, or preferably accounts at least 3% of matrix weight when water is unique softening agent.

The consumption of preferred plasticizer is the 1%-35% of goods or matrix weight, more preferably the 2%-25% of goods or matrix weight or even to 15% or even to 10% or even to 8%.Accurately consumption depends on used polymer materials and softening agent, but the matrix that should satisfy goods has required Tg.For example, when using urea, preferably its consumption is the 1%-10% of matrix weight, and when using glycerine or ethylene glycol or other glycol derivative, preferred higher consumption, as account for the 2%-15% of goods or matrix weight.Activeconstituents

Activeconstituents can be to be discharged into liquid environment, or any material of preferred aqueous environments, and preferably has active composition at aqueous environments.For example, when being used for cleaning compositions, goods can comprise any active cleansing.Goods also can comprise composition, as cleaning compositions or personal care composition.

Especially, it is useful adding activeconstituents or solids component in elastomeric article, and described activeconstituents reacts when contacting to moisture-sensitive or with moisture, and the resistance to impact shock of described solids component is limited and tend to form dust in treating processes.

Activeconstituents generally is the composition to moisture-sensitive, thermally sensitive composition, oxidable composition, volatilizable composition or their combination.Described activeconstituents can be biological active materials, harmful or toxic materials, agriculture composition such as agrochemicals, pharmaceutical cpd such as medicine for oral administration or narcotic or a kind of cleansing.

Especially preferred activeconstituents is in elastomeric article, for example enzyme, spices, SYNTHETIC OPTICAL WHITNER, bleach-activating agent, fabric positively charged ion and/or silicone tenderizer and/or conditioning agent, antiseptic-germicide, effervescent, whitening agent, optical white and their mixture.

A kind of preferred activeconstituents is the perhydrate SYNTHETIC OPTICAL WHITNER, as peroxyboric acid metal-salt, percarbonic acid metal-salt, especially sodium salt.Same preferred activeconstituents is organic peroxide acid bleach precursor or activator compound, and preferred imide-type alkyl peroxycarboxylic acid precursors compound comprises N, N, N ¹N ¹-tetrem acidylate Alkylenediamine; wherein alkylidene group comprises 1-6 carbon atom; especially those alkylidene groups comprise the compound of 1,2 and 6 carbon atom; as tetra acetyl 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, but also can be the alkyl peroxy acids precursor compound that acid amides replaces.

Be applicable to that the preferred activeconstituents of this elastomeric article camber is one or more enzymes.Preferred enzyme comprises commercially available lipase, at, amylase, neutrality and Sumizyme MP, cellulase, enolase, esterase, polygalacturonase, Sumylact L and peroxidase, and they are added in the cleaning compositions usually.

Suitable enzyme is at United States Patent (USP) 3,519, discusses in 570 and 3,533,139.Preferred commercially available proteolytic enzyme comprises: those of trade(brand)name Alcalase, Savinase, Primase, Durazym and Esperase, produce by Novo industrial (Denmark); Trade(brand)name Maxatase, those of Maxacal and Maxapem are produced by Gist-Brocades; Those that produce by Genencor international corporation; And sell with trade(brand)name Opticlean and Optimase by Solvay Enzymes company those.Preferred amylase comprises that for example, the α-Dian Fenmei by special bacterial strain Blicheniformis produces describes in greater detail at GB-1, among 269,839 (Novo).Preferred available commercial amylase comprises, for example, by Gist-Brocades by those of trade(brand)name Rapidase supply, and sell by trade(brand)name Termamyl, Duramyl and BAN by Novo industrial those.Highly preferred amylase may be those described in PCT/US 9703635 and WO9 5/26397 and the WO96/23873.Lipase can fungi or the form of bacterial origin obtain, for example can be by the bacterial strain that produces lipase: humicola lanuginosa bacterial classification, high temperature mould species or pseudomonas kind comprise that pseudomonas pseudoalcaligenes or Pseudomonas fluorescens produce.Here also can use by the lipase of this class bacterial strain through the mutant generation of chemical process or genetic method modification.A kind of preferred lipase is derived by pseudomonas pseudoalcaligenes, is described among the European patent EP-B-0218272 that authorizes.The preferred here lipase of another kind is to dredge wool detritus mould gene by cloning, and this genetic expression is obtained in the aspergillus oryzae host, be described among European patent application EP-A-0258 068, by (the Bagsvaerd of Novo industrial, Denmark) available commercial, commodity are called Lipolase.This lipase also is described in people such as Huge-Jensen, in the United States Patent (USP) 4,810,414 that 1989-03-07 delivers.Stablizer

These goods comprise a kind of stablizer, and it generally can stablize the activeconstituents in these goods, when activeconstituents comprises oxidisability or to the activeconstituents of moisture-sensitive, and during as one or more enzymes, especially preferred this class stablizer.Stablizer can be stablized the matrix in these goods equally, and thereby stabilizing active ingredient indirectly.

Stablizer is preferably a kind of at lay up period stabilizing active ingredient or matrix, makes it avoid the compound of oxidation and/or moisture degraded.

Stablizer joins in the activeconstituents of these goods.If comprise in these goods when surpassing a kind of activeconstituents, then can preferably select one of activeconstituents is a stablizer or a stabilizer function.For the purposes of the present invention, stablizer always is added in the activeconstituents of these goods as the supplementary component of these goods.

Therefore, for the purposes of the present invention, for the goods that will be defined as comprising stablizer and activeconstituents, wherein these goods comprise the component with dual-use function, and can play defined activeconstituents or function of stabilizer here, in order to obtain the goods that comprise activeconstituents and co-stabilizer according to the invention, except comprising compound, also must comprise a kind of additional stability agent or activeconstituents in the goods with dual-use function.

When considering other embodiment of the present invention, more than explanation about composition with dual-use function correct equally.For these goods, comprising a kind of activeconstituents, polymer materials and softening agent (they constitute matrix) and co-stabilizer is basic demand.Therefore, in order to obtain goods according to the invention, in these goods, comprise four kinds of different compositions at least.Can preferably select to have the basal component of dual-use function.

When considering highly preferred embodiment of the present invention, more than explanation about composition with dual-use function correct equally, for example preferred articles of manufacture comprises supplementary component such as solubility promoter.

Stablizer can be, or comprise a kind of foam base plate stablizer.Stablizer can be, or comprise a kind of activeconstituents stablizer, especially enzyme stabilizers.

Those can be by keeping in the goods the stable and stablizer of stabilizing active ingredient indirectly of foam base plate, be called " suds-stabilizing agent " here, preferably comprise tensio-active agent such as Fatty Alcohol(C12-C14 and C12-C18), lipid acid, alkanolamide, amine oxide or their derivative, or their combination.Suds-stabilizing agent can comprise trimethyl-glycine, sultaine, phosphine oxide, alkyl sulfoxide, their derivative or their combination.

Other preferred foam stablizer comprises one or more negatively charged ion or positively charged ion such as unit price, divalence, trivalent or other polyvalent metal ion, particular certain cancers, calcium salt, magnesium salts, sylvite, aluminium salt, zinc salt, mantoquita, nickel salt, cobalt salt, molysite, manganese salt and silver salt preferably have anionic gegenion sulfate radical, carbonate, oxide compound, muriate, bromide, iodide, phosphate radical, borate, acetate moiety, citrate and nitrate radical and their combination.

Suds-stabilizing agent can comprise the particle of fine dispersion, and preferred median size is more preferably less than 1 μ m, even is more preferably less than 0.5 μ m less than 10 μ m, or less than the fine dispersion particle of 0.1 μ m.Preferred fine dispersion particle is an aluminosilicate, for example the ionogen of zeolite, silicon-dioxide or fine dispersion particle form described above.

Suds-stabilizing agent can comprise agar-agar, sodium alginate, sodium lauryl sulphate, polyethylene oxide, guar gum, polyacrylic ester or their derivative, or their combination.

Suds-stabilizing agent can be the coating that the matrix with this paper goods separates.Suds-stabilizing agent generally partly preferably fully wraps up this paper goods or its activeconstituents.

This coating is contact activeconstituents earlier before the polymer materials of described activeconstituents contact matrix or softening agent generally, preferably contacts in the mode that forms coating on the activeconstituents surface, and preferred combination is advanced in this paper goods.

This coating generally can preferably after activeconstituents contacts described matrix or is attached in this paper goods, contact this paper goods in the mode that forms coating on goods after polymer materials and softening agent formation matrix.

Preferred coating comprises polymkeric substance, typically be selected from polyvinyl alcohol and derivative thereof, polyoxyethylene glycol and derivative thereof, Polyvinylpyrolidone (PVP) and derivative thereof, ether of cellulose and derivative thereof, and these polymkeric substance each other or with the multipolymer of other monomer or oligopolymer.Most preferably PVP (and derivative) and/or PEG (and derivative), the very preferably mixture of PVA (and derivative) or PVA and PEG and/or PVP (or derivatives thereof).These polymkeric substance do not form the matrix of this paper goods.Therefore, these polymkeric substance are different from the polymer materials of foam base plate.

Preferred coating comprises following compound, for example: glycerine, glycol derivative, comprise ethylene glycol, low polyoxyethylene glycol such as glycol ether, triglycol and Tetraglycol 99, weight-average molecular weight M.W. is lower than 1000 polyoxyethylene glycol, wax and chloroflo, the ethanol ethanamide, the ethanol methane amide, trolamine or its acetic ester, and ethanolamine salt, Sodium Thiocyanate 99, ammonium thiocyanate, polyvalent alcohol is as 1, the 3-butyleneglycol, sugar, sugar alcohol, urea, dibutyl phthalate or dimethyl ester, contain the acid of oxygen list, contain the oxygen diacid, diglycollic acid, and along distributing other line style carboxylic acid of at least one ether of molecular chain, water and composition thereof.These compounds do not form the foam base plate of this paper goods.Therefore, these compounds are different from the softening agent of foam base plate.

Directly the preferred stabilizer of stabilizing active ingredient especially when described activeconstituents comprises one or more enzymes, is defined as " active stabilizer " or " enzyme stabilizers " here.Typical active stabilizer and activeconstituents direct interaction also make it stable.

Typical activity stablizer used herein preferably comprises a kind of tensio-active agent.The tensio-active agent that is applicable to this is aforementioned those of matrix stablizer of being suitable as.Except these tensio-active agents, other is adapted at tensio-active agent used herein and can comprises such as following surfactant: the basic sodium sulfonate of alkane (alkene), alkoxyl group sodium sulfonate, preferred alkoxyl group sulfonate is to comprise 10～18 carbon atoms, no matter which kind of configuration, preferred line style also has 1～7, those of preferred 2～5 average degree of ethoxylation.

Other preferred active stabilizer comprises boric acid, formic acid, acetate and their salt.These sour salt preferably comprise the gegenion such as calcium and/or sodium.

Preferred active stabilizer comprises the positively charged ion of calcium and/or sodium and so on.Preferably calcium chloride and/or sodium-chlor.

Other preferred active stabilizer comprises average out to 3～20, preferred 3～10 amino acid whose little peptide chains, and these little peptide chain and activeconstituents, especially enzyme interactings also make it stable.

Other active stabilizer comprises the small nucleic acids molecule, generally comprises 3～300, preferred 10～100 Nucleotide.Typical nucleic acid molecule is thymus nucleic acid and Yeast Nucleic Acid.This nucleic acid molecule can be in and other molecule such as proteinic composite form, perhaps can form composite form with the activeconstituents of these goods, especially enzyme.

Be fit to active stabilizer used herein, especially when this paper goods comprise SYNTHETIC OPTICAL WHITNER, comprise antioxidant and/or reductive agent such as thiosulphate, methionine(Met), urea, thiourea peroxide, Guanidinium hydrochloride, Guanidinium carbonate, Guanidine Sulfamate 99, Monoethanolamine MEA BASF, diethanolamine, trolamine, amino acid such as glycine, Sodium Glutamate, protein such as bovine serum albumin and casein, tertiary butyl hydroxytoluene, 4-4 '-Ding fork two (the 6-tertiary butyl-3-methyl-phenol), 2,2 '-Ding fork two (the 6-tertiary butyl-4-methylphenol), one vinylbenzene cresols, toluylene cresols, one styrenated phenol, toluylene phenol, 1, two (4-hydroxyphenyl) hexanaphthenes of 1-, or their derivative, or their combination.

Other active stabilizer can comprise the reversible inhibitor of activeconstituents.Do not intend being limited to theory, but it is believed that the reversible inhibitor of activeconstituents, especially when activeconstituents comprises one or more enzymes, can form complex compound and improve its stability, thereby make activeconstituents keep stable at lay up period with described activeconstituents.When activeconstituents discharges, be discharged in typical case in the liquid environment, reversible inhibitor just dissociates from activeconstituents, so activeconstituents just can be realized the required effect that designs or intend realizing.

Be applicable to that the active stabilizer here comprises sugar.Sugar used herein generally comprises and is selected from sucrose, glucose, fructose, raffinose, trehalose, lactose, maltose, their derivative and those of their combination.

Active stabilizer also can comprise sugar alcohol such as Sorbitol Powder, mannitol, Inositol nf12 99 (inose), their derivative and their combination.

May be preferably, active stabilizer is taked coating or barrier layer form, wraps up this paper goods or its activeconstituents at least in part, preferably wraps up this paper goods or its activeconstituents, especially enzyme fully.

These goods can comprise (by weight) from 0.01% or from 0.1% or from 1% or from 2% or from 5% or from 7% or from 10% or from 15% or from 20% stablizer, and can comprise (by weight) to 70% or to 60% or to 50% or to 40% or to 30% or to 25% stablizer.The consumption of stablizer depends on the amount and the type of activeconstituents in these goods, also depends on the consumption and the type of this matrix.Supplementary component

Component of the present invention preferably comprises the supplementary component that can improve this paper goods dissolving properties.

Preferably improving this paper goods dissolved supplementary component preferably comprises: sulfonated compound, for example C ₁～C ₄The basic sulphonate of alkane (alkene), C ₁～C ₄Aromatic yl sulphonate, diisobutyl benzene sulfonate, tosylate, cumene sulphonate, xylene sulfonate, their salt such as sodium salt, their derivative or their combination, preferred diisobutyl benzene sulfonate, toluenesulfonic acid sodium salt, cumene sodium sulfonate, sodium xylene sulfonate and their combination; And/or C ₁～C ₄Alcohol is as methyl alcohol, ethanol, propyl alcohol such as Virahol, and their derivative, and their combination, preferred alcohol and/or Virahol; And/or C ₄～C ₁₀Glycol such as hexylene glycol and/or cyclohexane diol, preferred 1,6-hexylene glycol and/or 1,4 cyclohexane dimethanol; And/or can play the composition of wicking agent effect, as cellulose base composition, especially modified-cellulose; And/or swelling agent such as clay, preferred clay is a terre verte, especially dioctahedron or trioctahedron type terre verte, highly preferred clay are montmorillonitic clay and HECTABRITE DP or other clay of existing with the POLARGEL NF form; And/or effervescent system, preferred effervescent system comprise can with in the presence of water, the react acid source of generation gas of alkali source.The technology of preparation elastomeric article

Can use any technology that has the polymeric matrix of specific T g and in this matrix, add activeconstituents and stablizer by the preparation of polymer materials and softening agent to prepare elastomeric article of the present invention.Preferred technology relates to chemistry or physical method introduces a kind of gas in the mixture of the optional adding activeconstituents of polymer materials and softening agent.

A selection process for preparing these goods comprises the steps:

A) obtain a kind of polymer materials and softening agent, the mixture of preferably water and a kind of additional softening agent;

B) in the mixture of this polymer materials and water, introduce gas with chemistry or physical method;

C) before step b) or simultaneously or afterwards, in this mixture, add activeconstituents;

D) before step c) or simultaneously or afterwards, stablizer is contacted with this mixture;

E) be goods with the gained mixture forming;

Wherein one of in step a)-e) after step or the multistep or remove portion water simultaneously, if any.

In step a), preferably a kind of aqueous mixture of mixture or slurry, and at step b), c) and/or d) afterwards or among remove portion water, make end article comprise 3 weight % or more free-water.

Step c) preferably comprises a following step: obtain to comprise the core body of activeconstituents or part activeconstituents, and wrap up this core body with the mixture in the step b).

The step d) preferred package contains the mixing step, more preferably activeconstituents is closely mixed with stablizer or wraps up activeconstituents with stablizer.

Preferred articles of manufacture comprises perforate and/or closed pore, and this technology comprises following steps:

A) form polymer materials, active material, a kind of stablizer, a kind of softening agent and a kind of mixtures of liquids, wherein liquid and softening agent can be with a kind of compound;

B) by claim b) mixture shaping core body and

C) evaporate liquid or partially liq to form cavity in mixture, this cavity forms the interior region of goods mesopore,

Wherein preferably come performing step c by lyophilize or heating core body), thus make liquid or partially liq evaporation.

Also can on the mixture of step a), exert pressure performing step b), preferably under mixing and/or under the increase temperature, exert pressure, remove pressure or partial pressure then, thereby make liquid evaporation.For example, can use expressing technique.At this moment preferably that polymer materials, softening agent, preferred package is moisture, and the optional mixture that adds activeconstituents is introduced forcing machine, therein mixture is done further to mix and heating, owing to mixing or because heating, preferred mixture forms melt therein, (this mixture can form required shape at extrusioning mixture then, particulate state for example) exit of flowing out forcing machine reduces pressure, thereby make the evaporation of liquid or partially liq, or preferably water is evaporated from extrusioning mixture as steam.This causes the formation in hole, has cavity as mentioned above, and the hole can comprise a kind of gas then, and preferred air reaches randomly activeconstituents.These cavitys form the interior region of elastomeric article matrix mesopore of the present invention.

Also can as above cause the formation of cavity by heated mixt so that liquid or partially liq evaporate the step b) of carrying out in the technology.This can be preferably by spray-drying tower of mixture feeding is finished, preferably mixture is fed by nozzle, form the drop of mixture, and these drops of spraying drying routinely, form the particle of elastomeric article.

As mentioned above, the physics of gas or whipping agent and/or chemical introducing can be adopted any known method, preferably

-physical blowing, method is: gas (drying or water-based route) injects, and randomly injects under mixing, and high speed shear stirs (drying or water-based route), and gas dissolving and lax comprises critical gas diffusion (drying or water-based route);

-chemical foaming, method is: original position forms gas and (by the chemical reaction of one or more compositions, comprises by effervescent system forming CO ₂Interior);

The foaming of-steam, ultraviolet light irradiation solidifies.

A drying step or an additional drying step are preferably arranged to remove excessive liquid or partially liq, as water after these foaming step.Especially, this drying step forms the back at polymeric matrix at least and carries out, and randomly adds the back at activeconstituents and carry out, preferably as the final step of this technology.Preferred drying step will be accomplished drying step after finally before the volume of elastomeric article and drying step roughly the same.In addition, preferably carry out this drying step, therebetween under vacuum and reduce temperature and come to remove and to desolvate, as water by lyophilize.Be raised under the not too high temperature as 40-80 ℃, or or even 40-60 ℃ carry out slow fluidised bed drying or oven drying also is useful.

Preferred technology relates to the step that at least one forms polymer materials and mixtures of liquids, the solution of preferred a kind of polymer materials and a kind of solvent, and preferred package is moisture, and to wherein adding softening agent (or when the situation permission, adding softening agent).If require to exist in the matrix activeconstituents and/or stablizer, then these also will add in the mixture of polymer materials, solvent and softening agent.Perhaps, or in addition, can preferably around active material, form matrix, preferably around active material and solid support material core.

Further be processed into for example core body of end article shape then, as particle or bead, and general drying obtains goods.Preferably, before forming step, add a kind of gas.Forming step comprises granulation step, as atomizing or spraying drying, extrude, trace becomes ingot.Lyophilize is that dry core body is to form the selection process of goods.

Below be preferred technology, its form low dust or even zero dust granules, with following prestress Heubach method of testing mensuration, have Tg and be lower than 10 ℃ and Young's modulus and be lower than 0.5GNm ^-2Matrix, in following specific embodiment, will illustrate in greater detail.First selection process is as follows:

Obtain the solution (or polymkeric substance and a kind of mixtures of liquids) of aequum polymer materials, for example (adding) is in a mixing tank.The active substance (solution) that adds aequum then, for example enzyme solution, and stablizer, and add the softening agent of aequum, and randomly add other supplementary component, as filler, thickening material etc.Stir these materials and make it to become uniform mixture.Preferably, can introduce a kind of gas such as air in solution with any aforesaid method, preferred physical method mixes by high speed shear.

Then, form particle through atomizing, preferably mixture solution is transferred to nozzle, preferably use one or more fluid tips to form drop with positive-displacement pump by this mixture.

Freezing then drop is preferably by a kind of refrigerant (can comprise liquid nitrogen, freonll-11, refrigeration oil).Then, frozen granules is moved to vacuum chamber, preferred temperature is lower than 0 ℃ (measuring at particle surface).

Preferably collect frozen granules and under the situation of elevated temperature not, shift from spray column.The wall temperature of lyophilize tower and the temperature of pallet preferably maintain below 0 ℃, to keep particle freezing.Apply vacuum, the refrigerated ice crystal will make described gas be sublimate into gas form, thus in particle pore-forming.Can control total ridity with vacuum-chamber wall with the temperature that contacts of pallet with vacuum tightness.

After particle had been dried to required water-content, they just can unrestricted flow.Then preferably, can come particle is classified by different screen clothes and/or other processing unit.

Find that the above-mentioned optional step of introducing gas (bubble) in the polymers soln mixture has improved the particulate shock resistance well, this point reflects from electronic module.Can introduce bubble by different way.

In atomization steps, preferred fog nozzle is positioned at the enough height of spray column so that to finish drop during decline under action of gravity freezing.Bleed type can have different designs-single fluid pressure nozzle, rotation insertion, sound wave or multithread body nozzle.Important inventive point is that fracture liquid stream is to form isolating drop.Because these drops descend because of gravity, need they are cooled to freezing.Refrigerant preferably can make the non-aqueous gas or the liquid of drop quick freezing.Cool off these drops and preferably be lower than 0 ℃, and preferably be lower than-20 ℃ to form the particulate actual temperature.

Also can preferred above-mentioned process modification as follows:

In mixture, introduce a kind of gas, preferred CO ₂Gas, and mixture introduced aforesaid spray-drying tower, thus forming spray-dired expanded beads, if necessary can classify.Preferably going into the tower temperature is about 130 ℃, about 75 ℃ of tower exit temperature, and injection rate is 12.5g/ minute.For example herein can be with the Niro Mobil Minor that two fluid tips are arranged.The gained particle may be required shape, also can further carry out lyophilize under vacuum.

Another selection process is as follows:

Obtain the solution (maybe can and add liquid) of aequum polymer materials, for example be incorporated into a mixing tank with polymer powder.The softening agent that adds aequum then, and randomly add other supplementary component, as filler, thickening material etc.Stir material and make it to become uniform mixture.Preferably, introduce a kind of gas such as air by any aforesaid method in solution, preferred physical method mixes by high speed shear.

In addition, preparation comprises activeconstituents such as enzyme, stablizer and the particle of other composition such as filler or carrier randomly, for example be coated with by fluidized-bed, by with first kind " core " (generally when activeconstituents is enzyme, these core grains are sugar or starch granules) be fed to fluidized-bed, and with the solution spraying of active substance or active substance to these cores, go out any solvent such as water with warm fluidizing air drying from active substance solution then.

Then, above-mentioned polymeric blends is added on these active substance/cores, for example is directed to atomizing nozzle in the fluidized-bed as mentioned above by positive-displacement pump.Can use more than one nozzle, can be added on the core by different nozzles by preferably different compositions.

Required fluidization air preferably is lower than 0 ℃, preferred-20 ℃ approximately.Then, fluidization air is chilled in polymeric blends/solution the outside of active core.This is the critical parameter of a control, and generally air themperature must be lower than 0 ℃, and purpose is to make polymeric blends/solution quick freezing on the core grain.

Preferably thus obtained frozen granules is transferred to vacuum chamber then, as mentioned above, also can classify.

The particle of the present invention that this technology forms comprises a matrix around activeconstituents.

Found that the above-mentioned optional step of introducing gas (bubble) in the polymers soln mixture can improve the particulate shock resistance well, this point is reflected by Young's modulus.

Another selection process is as follows:

Obtain the solution (or solid polymer and an amount of liquid) of aequum polymer materials, for example be incorporated into a mixing tank.Then (in mixing tank) add aequum active substance (solution) as enzyme solution, and stablizer (solution), and add the softening agent of aequum, and randomly add other supplementary component is as filler, thickening material.Stir material and make it to become uniform mixture.Preferably, can add a kind of gas such as air in solution with above-mentioned any method, preferred physical method mixes by high speed shear.

Then, with polymers soln from mixing tank suction forcing machine or the die cavity of a template is arranged endways.Before entering forcing machine or die cavity, gas can be injected mixture, for example disperse by mechanical shearing mixing tank or static mixer.

When extrudate flowed out template, the variation of pressure produced slight bubbling or expansion in extrudate.Use mouthful die face cutting knife or miscellaneous equipment (as thermal wire, rotary plunger cutting knife etc.) that extrudate is cut into suitable length then.Can allow extrudate randomly by adding grinding steps to make it round.The processing unit that can finish this function comprises (spin finishing dish, coalescent dish, one-tenth ball machine, drum, mixing drum etc. roll).

For example,, promptly be arranged on 40 seconds full speed mixing 75gPVOH, 15g citric acid, 2gPEO and 22.5g glycerine, make a kind of thickener by in Braun mixing machine high speed shear agitation; Add 80g water and 80g enzyme and high speed shear then and mix, promptly be arranged at full speed, up in 2 minutes, forming uniform foam greatly.With 10 milliliters syringes foam is extruded on the plastic plate.Place and allowed its drying in 24 hours.In case dry foam strip soon is cut into the segment of about 1-2mm to form particle, its prescription is (dry state): 63.2% polyvinyl alcohol, 19% glycerine, 12.7% citric acid, 1.6% PEO, 4% water, 3.2% enzyme.

Gained particulate Young's modulus is 0.00016GM.m ^-2

When testing in prestress Heubach test, the gained particle has 0% dust, this means very good shock resistance.(prestress Heubach test is undertaken by the method known in the art, and the equipment that adopts German Herbach Engineering GMbH to provide is 75 ± 1 rev/mins by the angle of rake rotation rotating speed of stress changes, and ball is a wolfram varbide, and each grain is 82g).

Preferred molding/one-tenth ingot technology:

Highly preferred technology relates to the particle that comes the moulding said mixture with mould, wherein mixture described here is added in the mould and subsequent drying (lyophilize).Also preferred such technology is utilized system ingot equipment, therein with said mixture, preferably comprises the gas of adding, is pressed into mobile transport tape by rotation porous drum, is shaped to lozenge (drop or particle).When dry or sclerosis, formed particle or ball are scraped from transport tape with scraper.

The preferred the first step is preparation polymer materials and softening agent, liquid ingredient and the mixture of activeconstituents randomly.Preferably gas is added this mixture by method described here.This must preferably not have undissolved macrobead, and they can stop up the hole in the rotary drum.The temperature range of preferred mixture is 0-50 ℃.With arm of mixture suction, this arm is linked rotation porous drum and parallel with the longitudinal axis of drum.With in the mixture suction drum, when drum rotates, make mixture with blade-carrying in scraper contact, this scraper and porous are roused and contacted and along the internal surface length direction, and be parallel with the feeding arm.

The distance (less than diameter in hole) in the altitude range of required particle height of porous drum outside surface, but do not contact on the point that interior scraper and porous drum internal surface contacts with the rotary drum of mobile transport tape or smooth surface, the tangential velocity of the tangential velocity of porous drum and the speed of transport tape or smooth surface drum is mated.When mixture was compelled to be the hole of 300-2000 μ m (but can be littler or bigger) by typical size range, mixture was deposited on the lower surface.The rotation of porous drum cuts off the material of feeding get off from the material on the smooth surface, therefore stays drop or lozenge, and this will form required particle.These lozenge can be by freezing or evaporate some or all solvent liquids and solidify.Freezing if desired, then the temperature of transport tape or smooth surface drum can be at normal temperature in-20 ℃ scope.Evaporating solvent if desired, then can reach by thermal conduction from transport tape, the transport tape temperature can be in the scope of normal temperature to 70 ℃, or by allowing the surface of dry air (can be heated to 200 ℃ the to shorten time of drying) lozenge of flowing through realize, or the both uses.

Then, with scraper the particle of gained is removed from rotary drum or transport tape.Can on drum, adopt a kind of examples of suitable lubricants (releasing agent) to improve this technology as silicone oil.Lubricant or releasing agent can reduce the adhesivity between polymer materials and the band/drum, thereby particle performance is gone out another benefit, and therefore increase the height of lozenge, if this also is expectation.

Embodiment

The preparation method of embodiment 1 elastomeric article according to the present invention

(weight-average molecular weight is 30 with the polyvinyl alcohol of 4700g 33 weight %, 000-70,000) enzyme solution of solution and 3360g [water of 5 weight % organized enzymes and 85 weight %], 159.3g glycerine and 168g ammonium sulfate mix in the high speed shear mixing machine, up to forming uniform foam.This mixture is transferred to feed tank, and use toothed gear pump with the miniature system ingot of its suction equipment, for example provided by Sandvik Process Systems company (Totowa, New York), employings aperture is that 1mm, spacing are that the porous of 2.5mm is bulging.This equipment is deposited on lozenge and scribbles one deck silicone oil, and is heated on about 30 ℃ smooth surface drum.When 1/4th of drum is all covered by lozenge, stop operating.Feel dry up to the lozenge surface with dry this lozenge of hot air heater.Scrape and collect the gained particle then.

Embodiment 2 is with the method for tablet, ball or produced in particle form foam article of the present invention Equipment:Kenwood " chef " board food processor, glass or the mould of plastics of microbalance, 100ml measuring cup, belt stirrer and mixing cup, spatula.Pharmaceutical chemicals: polyvinyl alcohol (Aldrich chemical company, weight-average molecular weight Mw=30-70k), glycerine (99%, Aldrich chemical company), citric acid (USP is anhydrous for Aldrich, citric acid), distilled water, dry ice (or solid CO ₂), adiabatic box. Process:

1. the PVA of weighing 50 ± 0.2g, the glycerine of 30 ± 0.2g.

2. use mixing machine (2 grades of low speed; The low shearing) mix PVA and glycerine down.

3. the water that adds 50 ± 1ml in the dry state mixture gradually kept mechanically mixing 2 minutes.Obtain uniform colloid.

4. increase and mix velocity of shear to the most high-grade (8 grades).Add 10-20ml water, up to forming the PVA foam.Keep high speed shear to mix 3 minutes.

5. in foam, progressively add activeconstituents,, keep mechanically mixing to obtain uniform active foam as the enzyme of 2-10g.

6. stop to mix.The PVA foam is sprawled in mould, avoided the destruction of any structure.

7. the mould of filling is put into the 1/3 adiabatic box of having loaded dry ice.Allow its freezing 5 hours.

8. freezing sample is put into fast vacuum freeze drier (Edward XX), kept 24 hours.

9. from mould, take out dry sample.

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

Any stablizer that in step 5, can add any amount, general maximum about 50g, for example, bovine serum albumin, ammonium sulfate, sucrose and a vinylbenzene phenol.

Embodiment 3

Method with tablet, ball or produced in particle form elastomeric article of the present invention

Equipment: with identical in the last example.

Pharmaceutical chemicals: polyvinyl alcohol (Aldrich chemical company, weight-average molecular weight M _w=30-70k), glycerine (99%, Aldrich chemical company), citric acid (Aldrich, citric acid, USP is anhydrous), yellow soda ash (Aldrich, anhydrous), dodecyl sulfate tensio-active agent (Aldrich company), distilled water, petri dish (diameter 90mm), baking oven (being arranged on 45 ℃ ± 2 ℃).Technology:

1. the sodium lauryl sulphate of the yellow soda ash of the glycerine of the PVA of weighing 50 ± 0.2g, 30 ± 0.2g, 20 ± 0.2g and 2 ± 0.2g.

2. mix PVA, glycerine, sodium lauryl sulphate with mixing machine low speed (2 grades).

3. the water that adds 50 ± 1ml in drying composite was gradually kept mechanical stirring 2 minutes.Obtain uniform colloid.

4. adding activeconstituents, for example 5g enzyme and yellow soda ash, and powerfully stir the mixture 30 seconds up to the foam that obtains complete expansion.

5. foam is spread on the petri dish, form the inhomogeneous coating of thick 1cm.

6. the baking oven of petri dish being put into 40 ℃ kept 24 hours.

7. from mould, take out the exsiccant foam film.

Can in step 4, add any activeconstituents, general maximum about 50g, for example fabric softener, SYNTHETIC OPTICAL WHITNER, nonionogenic tenside with any amount.

Repeat this technology with the enzyme of the anhydrous sodium carbonate of the polycarboxylic acid polymer of 55 weight %, 20 weight % and 25 weight % and softening clay etc.; And repeat this technology with the enzyme of polycarboxylic acid polymer, 15 weight % polyoxyethylene glycol, 20 weight % anhydrous sodium carbonates and the 20 weight % of 45 weight % and softening clay etc.

Claims (15)

1. elastomeric article comprises:

A) a kind of activeconstituents; With

B) a kind of foam base plate that forms by at least a polymer materials and a kind of softening agent; With

C) a kind of stablizer;

Wherein said goods can be discharged into described activeconstituents in the liquid environment.

2. according to the elastomeric article of claim 1, wherein said activeconstituents is active in aqueous environments, and wherein said goods are water dispersible, water decomposition or water miscible, and is preferably water miscible.

3. according to the elastomeric article of arbitrary aforementioned claim, the second-order transition temperature of wherein said matrix (Tg) is lower than 50 ℃, preferably is lower than 40 ℃, and randomly between-20 ℃ to 20 ℃, preferably between-10 ℃ to 10 ℃.

4. according to the elastomeric article of arbitrary aforementioned claim, the Young's modulus of wherein said matrix is less than 1GN.m ^-2, preferably less than 0.1GN.m ^-2, or even less than 0.01GN.m ^-2

5. according to the elastomeric article of arbitrary aforementioned claim, wherein said stablizer comprises a kind of suds-stabilizing agent.

6. according to the elastomeric article of arbitrary aforementioned claim, wherein said activeconstituents is a kind of cleaning product composition, fabric nursing composition, medicine or cosmetic composition, is preferably selected from enzyme, tensio-active agent, whitening agent, dyestuff, froth suppressor, SYNTHETIC OPTICAL WHITNER, bleach-activating agent, fabric softener, fabric regulator, antiseptic-germicide, effervescent system and their mixture.

7. according to the elastomeric article of arbitrary aforementioned claim, wherein said activeconstituents comprises at least a enzyme, and wherein said stablizer comprises a kind of enzyme stabilizers, and preferred described stablizer is an enzyme stabilizers.

8. according to the elastomeric article of arbitrary aforementioned claim, wherein said polymer materials comprises a kind of water-soluble polymers, the preferably water soluble polyvinyl alcohol.

9. according to the elastomeric article of arbitrary aforementioned claim, it exists with the particulate form, and the equal particle diameter of body is the 50-4000 micron, preferred 100-1500 micron.

10. according to the elastomeric article of arbitrary aforementioned claim, its relative density is 0.05-0.9, preferred 0.3-0.7.

11. according to the elastomeric article of arbitrary aforementioned claim, wherein said matrix forms a series of closed pores and perforate, wherein closed pore is preferably at least 1: 1 with the ratio of the quantity of perforate.

12., can obtain by the technology that comprises the following step according to the elastomeric article of claim 7:

A) mixture of preparation polymer materials and softening agent, preferably water and another softening agent; With

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

C) before step b) and/or simultaneously and/or activeconstituents is contacted with described mixture; With

D) before step c) and/or simultaneously and/or stablizer is contacted with described mixture; With

E) be goods with the gained mixture forming;

Wherein preferably in step a) to e) in one the step or multistep after or remove portion water simultaneously, if any.

13. according to the elastomeric article of claim 12, wherein described activeconstituents with described activeconstituents is contacted before the mixture of described polymer materials and softening agent contacts with described stablizer.

14. according to the elastomeric article of any one among the claim 1-13 activeconstituents is discharged into application in the aqueous environments, preferred activeconstituents is the decontamination activeconstituents, preferred enzyme, and preferred aqueous environments is washing water.

15. according to the application of the elastomeric article of any one among the claim 1-13, be selected from following one group activeconstituents preferred the adding therein: enzyme, spices, tensio-active agent, whitening agent, dyestuff, suds suppressor, SYNTHETIC OPTICAL WHITNER, bleach-activating agent, fabric softener, antiseptic-germicide, effervescent system and their mixture in cleaning compositions, Fabrid care composition, personal care composition, make-up composition or composite medicine.