CN107474982A

CN107474982A - Synergy capsule

Info

Publication number: CN107474982A
Application number: CN201710671408.5A
Authority: CN
Inventors: 周玉成; 蔡悦
Original assignee: Novo Nordisk AS
Current assignee: Novo Nordisk AS
Priority date: 2017-08-08
Filing date: 2017-08-08
Publication date: 2017-12-15
Anticipated expiration: 2037-08-08
Also published as: WO2019029530A1; CN107474982B

Abstract

A kind of synergy capsule for being used to strengthen the clean result in short distance washing, it includes capsule shell, and the washing enzyme included in capsule.A kind of synergy capsule for being used to strengthen clean result, it includes capsule shell made of pulullan polysaccharide material, and the washing enzyme in above-mentioned capsule shell.Pulullan polysaccharide is preparing the application in being used to strengthen the synergy capsule of clean result.A kind of kit, it includes described synergy capsule, has corresponding visual identity key element on capsule.

Description

Synergy capsule

Invention neck city

The present invention relates to the synergy capsule for strengthening clean result, and the method for preparing the synergy capsule.

Background of invention

The one or more for removing different spot components would generally be included in detergent applications, the detergent of high-quality performance Enzyme.The formula design of Betengent product will be considered to mix the stability of enzyme therein.Generally, enzyme is average in the form of granules It is dispersed in whole cleaning product.Keep enzyme stability be a technical challenge because enzyme is protein, its activity by The influence of composition such as anion surfactant or bleaching agent in detergent etc., while protease can also pass through its albumen water Solution acts on to be had an impact to the activity of other enzymes."Laundry detergent compatibility of the Alkaline protease from Bacillus cereus ", Banika, Rathindra Mohan and Prakash, Monika, Microbiological Research, Volume 159, Issue 2, pp 135-140 (2004), which are discussed, to be made to wash The various factors that clothing is inactivated with enzyme, including bleaching agent and surfactant.

It is in the art to have there are a variety of methods to be attempted the activity for stablizing the expensive enzyme in detergent such as logical Cross：1) stabilizer or protease inhibitors of enzyme, such as " Formulation of Detergent Enzymes " are added, Becker et al., Enzymes in Detergency, Jan H van Ee and Onno Misset, by Erik J Baas, NY Marcel Dekker (1997) are published, the method for describing the enzyme in stable detergent；2) attempt that there is multi-compartment Unit dose package detergent, enzyme and bleaching agent are separated.EP0481547A1 is disclosed including surfactant, enzyme With the dishwasher detergent agent piece of chlorine bleach, there are at least three layers to be isolated " incompatible composition such as enzyme and chlorine bleach " for it. United States Patent (USP) 6,413,928 describes the method for preparing the multi-phase detergent piece with gel section.Described makes enzyme and bleaching Agent and surfactant are physically separate.The described commercially available product with enzyme and bleaching agent can be obtained in the form of tablet Arrive, be known as Reckitt Benckiser Vanish Action Ball (magical effect washing ball).So further increase The cost of detergent containing enzyme.

For the detergent of economic level, its cost structure frequently results in can not be wherein using enzyme or high dose Enzyme, or the extra composition of control enzymatic activity can not be added in formula, or can not configure and will influence the composition of enzymatic activity With in the labyrinth of enzyme physical isolation.

In the industry, it is necessary to which effective single dose solid enzyme product, consumer can select as required in terms of cost Enzyme product and enzyme product is added in washing process, the washing process applies existing cleaning formulation, particularly without The cheap cleaning formulation and cleaning liquid formulation of enzyme.

CN101218334A (Genencor International Co., Ltd.) discloses the enzyme fabric care tablet for consumer, the enzyme Tablet can add in single dose in the washing cycle of automatic washing machine or dish-washing machine.The tablet of the single dose is by streaming bed Technique by enzyme and excipient such as microcrystalline cellulose, stearic acid enzymes etc. together.The technique of tabletting is relative complex, and in order to prevent Dust caused by tablet causes enzyme allergy during the direct catalase synergist of consumer or use, it is also necessary to which spraying is for example poly- The water miscible filmogen such as ethylene glycol is in the surface of tabletting.In order to prevent the tabletting moisture absorption from causing enzymatic activity impacted, it is also necessary to A housing material is chemically treated or provided to tabletting to carry out protection against the tide.All these steps add into again This.In addition, when referring to gelatine capsule comprising enzyme synergist, CN101218334A only discloses washs journey in European long-range Application in sequence.

The invention provides the effective method in terms of cost, by the form of capsule by enzyme be directly delivered to consumer and Not the problem of not meeting with enzyme stability, and can be in the washing cycle of relative short distance, such as relatively European long-range washing procedure For in the Asia washing procedure that significantly shortens, promptly play the washing synergistic effect of enzyme.Averagely it is scattered in enzyme therein Detergent is compared, and when the enzyme being included in capsule separately provided is used in conjunction with the detergent without enzyme, consumer can be more Enzyme is easily recognized for removing the increased clean result of specific spot, and tends to more receiving and accreditation enzymes washed The use of journey.The use of enzyme can save the energy largely used needed for detergent application process of the tradition without enzyme, including The usage amount of electricity and water resource, while reach same or increased clean result, it can additionally reduce washes discharge pair Pressure caused by environment.

Summary of the invention

In one aspect, the present invention relates to a kind of synergy capsule for being used to strengthen the clean result in short distance washing, it is wrapped Include capsule shell, and the washing enzyme inside capsule shell.

In another aspect, the present invention relates to a kind of synergy capsule for being used to strengthen clean result, it is more that it includes Propiram Capsule shell made of sugared material, and the washing enzyme in above-mentioned capsule shell.

In another aspect, the present invention relates to pulullan polysaccharide to prepare for strengthening in the synergy capsule of clean result Using.

In another aspect, the present invention relates to a kind of kit, it includes one or more previously described synergy capsules, There is corresponding visual identity key element on the synergy capsule.

In another aspect, the present invention relates to the method for preparing previously described synergy capsule, including：Screening is at 25 DEG C Washing process in residual rate be no more than 18% capsule shell, and washing is filled into inside capsule shell with enzyme synergist.

Definition

δ enzyme performance values：Term " δ enzymes reflected value " or " δ Enz " or " Δ Enz " is defined herein as the reflectivity at 460nm Or the result of reflectance measurement.With a kind of swatch with similar color, preferably a kind of napkin from repeated washing Sample measures the swatch as background.Before washing, measurement represents the swatch of every kind of swatch type.δ enzymes Energy value is to be subtracted to be washed with the detergent in the absence of enzyme with the reflected value that the swatch that a kind of detergent of enzyme washs be present The reflected value of similar swatch.

δ reflected values (Δ Rem)：Term " δ reflections " or " δ reflected values " are defined as the reflectivity at a certain wavelength herein Or the result of reflectance measurement, the wavelength are typically 460nm.With a kind of cloth specimen with similar color, preferably one kind comes from The cloth specimen of repeated washing measures the cloth specimen as background.Before washing, measurement represents the cloth specimen of every kind of cloth specimen type.δ reflects It is that the reflected value of the cloth specimen of washing subtracts the reflected value of unwashed cloth specimen.

Detergent composition：Term " detergent composition " refer to for from have article to be cleaned (such as textile, meal Tool and crust) remove the composition of undesirable compound.The detergent composition can be used for such as cleaning fabric, meal Tool and crust, for both household cleaners and industry cleaning.These terms cover selection and are used for desired particular type Cleasing compositions and product form (for example, liquid, gel, powder, particle, pasty state or spray composite) any material Material/compound, and including but not limited to detergent composition is (for example, liquid and/or solid laundry detergent and high-count fabric Detergent；Hard-surface cleaning preparation, such as glass, timber, ceramics and metal table top and window；Carpet cleaner； Oven cleaners；Fabric refreshers；Fabric softener；And textile and the pre- detergent of clothing (pre-spotter), together with meal Has detergent).In addition to the dual-function compound comprising the present invention, the detergent preparation can also include one or more Other enzyme (such as protease, amylase, lipase, cutinase, cellulase, endoglucanase, xyloglucanase enzymes, fruit Glue enzyme, pectin lyase, xanthase, peroxidase, halo peroxygenases, catalase and mannase, or Its any mixture), and/or component, such as surfactant, builder, chelating agent (chelator) or chelating reagent (chelating agent), bleaching system or bleaching component, polymer, fabric conditioner, foam improver, foam inhibitor, dyestuff, perfume (or spice) Material, tarnish inhibitor, optical brightener, bactericide, fungicide, soil suspender, corrosion inhibitor, enzyme inhibitor or stably Agent, zymoexciter, one or more transferases, hydrolase, oxidoreducing enzyme, blueing agent and fluorescent dye, antioxidant and Solubilizer.

Dishwashing detergent：Term " dishwashing detergent " refers to the washing tableware of form of ownership, such as manually or automatically dishwashing detergent (ADW).Washing tableware includes but is not limited to, and cleans the pottery of form of ownership, such as plate, cup, glass, bowl, and institute is tangible The dining instrument of formula, such as spoon, knife, fork, and apparatus of serving is together with ceramics, plastics, metal, porcelain, glass and acrylate.

Short distance is washed：Term " short distance washing " refers to compared to for the common washing habits in Europe and washing duration, whole Individual washing process is the Asia washing process significantly shortened.Generally, the master that includes of European wash program washes cycle and Rinse Cycle Long-range order is 3 hours when whole, wherein master, which washes the cycle, is 50-110 minutes；The short distance washing that the present invention describes is washed Washing the cycle is typically not greater than 110 minutes, preferably more than 100 minutes, no more than 90 minutes, no more than 80 minutes, no more than 60 Minute, no more than 50 minutes, no more than 30 minutes.

Master washes the cycle：Term " master washes the cycle " refers to include textile or other articles to be washed being immersed in cleaning solution, Certain mechanism is applied to the textile, to discharge dirt, and assist cleaning solution flow in and out the textile or its His article to be washed, and finally remove the process of unnecessary cleaning solution.The master of the short distance washing of the present invention washes the cycle and not surpassed typically 90 minutes are spent, preferably more than 70 minutes, preferably more than 50 minutes, preferably more than 30 minutes, preferably more than 20 minutes, Preferably more than 15 minutes, preferably more than 12 minutes.

Rinse Cycle：Term " Rinse Cycle " refers to use the clear water without cleaning solution to textile after the completion of master washes the cycle Or the process that other articles to be washed are eluted and are dehydrated.

Cleaning solution：Herein term " cleaning solution " is defined as optionally including and is used to wash textile or other articles to be washed Water and detergent solution or mixture.

Hard-surface cleaning：Term " hard-surface cleaning " is defined as cleaning of hard surfaces herein, wherein crust can include Floor, desk, wall, roof etc., together with the surface of hard object, such as automobile (car cleaning) and tableware (dishwashing detergent).Meal Tool washing includes but is not limited to, cleaning plate, cup, glass, bowl, dining instrument (such as spoon, knife, fork), apparatus of serving, pottery Porcelain, plastics, metal, porcelain, glass and acrylate.

The clean result of enhancing：Term " clean result of enhancing " is defined herein as adding synergy capsule in washing process Increased clean result is shown relative to the clean result of the detergent composition of no synergy capsule, for example, removal spot, Maintain whiteness, reduce balling-up, fabric color nursing, remove smell, remove biomembrane, prevent, reduce and/or go dirt attached .Term " enhancing clean result " is included in clothes washing and for example such as automates dishwashing detergent (ADW) in hard-surface cleaning In clean result.The synergy capsule of the present invention can be used for strengthening above-mentioned one or more clean results.

Laundry：Term " laundry " be related to both household laundry and industrial washing clothes and mean with comprising the present invention cleaning or The process of the solution processing textile of detergent composition.Laundry processes for example can be entered using such as household or industrial washing machine Row can be carried out manually.

Textile：Term " textile " means to include yarn, yarn intermediate, fiber, non-woven material, natural material Any textile material of material, synthetic material and any other textile material, the fabric of these material manufactures and by these Product made of fabric (such as apparel and other objects).The textile or fabric may be at knitwear, woven fabric, cowboy Cloth, non-woven, felt, the form of yarn and towelling.These textiles can be cellulose base, such as native cellulose, Including cotton, flax/linen, jute, ramie, sisal hemp or coir fibre or artificial cellulose's (for example, deriving from wood pulp), Including viscose/artificial silk, cellulose acetate fibre (three categories of overseas Chinese), Lyocell fibers (lyocell) or its blend.Textile or Fabric can also be not based on cellulose, such as natural polyamide, including wool, camel hair, cashmere, mohair yarn, the rabbit hair and silk or conjunction Into polymer such as nylon, aromatic polyamides, polyester, acrylic acid, polypropylene and spandex/elastomer (spandex/ ) or its blend itself and blend based on cellulose and the fiber for being not based on cellulose elastane.The example of blend It is cotton and/or artificial silk/viscose and one or more of blends with material, this is, for example, wool, synthesis with material Fiber (such as Fypro, acrylic fiber, polyester fiber, polyvinyl chloride fibre, polyurethane fiber, polyurea fibre, aromatics Fypro) and/or the fiber of containing cellulose (such as artificial silk/viscose, ramie, flax/linen, jute, acetic acid are fine Cellulose fiber, Lyocell fibers).Fabric can be conventional washable clothing, such as stained household clothing.When using term When fabric or clothes, it is intended to also including broad terms textile.

Whiteness：Term " whiteness " is defined as to have the wide of different implications in different field and for different customers herein Adopted term.The loss of whiteness can for example be attributed to ashing, yellow or the removal of optical brightener/toner.Ashing and yellow It is attributable to soil redeposition, body soil, the coloring shifted from such as iron and copper ion or dyestuff.Whiteness can include coming From the one or several problems of list below：Colouring agent or dyestuff effect；Incomplete dirt removes (such as body soil, sebum Deng)；Redeposited (ashing, yellow or other discolorations of object) (other parts of the dirt of removal and textile are (making dirty or not Make dirty) associate again)；The chemical change of textile in application process；And clarification or the light color of color.

Disintegrating property：The term " disintegrating property " used in the present invention refers to be limited by disintegration time under given conditions Capsule shell cracking release content velocity correlation property.

Disintegration time：The term " disintegration time " used in the present invention refers to the capsule shell rupture exposure in washing process The time gone out required for washing enzyme, it specifically determines retouching in detail for analysis method part " disintegration time measure " part that sees below State.

Residual rate：The term " residual rate " used in the present invention refers to that capsule shell is without completely molten in washing process Solution, and the ratio of washing articles or the part on washing machine surface is remained in, it specifically determines the analysis method part that sees below The detailed description of " residual rate ".

Detailed description of the invention

In one aspect, the present invention relates to it is a kind of be used for strengthen in short distance washing procedure clean result synergy capsule, It includes capsule shell, and the washing enzyme inside capsule shell.Generally Europe and the common washing procedure in the U.S. Total duration is long the washing cycle common than in the washing procedure in Asia with the main duration for washing the cycle.The present inventor makes People is surprised to find that synergy capsule prepared by the capsule shell of some certain materials can be in relatively short washing cycle and/or phase Washing synergistic effect to realizing washing enzyme under relatively low wash temperature, is growed without going through what is usually required in Europe More wash times and general of a relatively high wash temperature.

It is not only restricted to the limitation of theory, the physics of the capsule shell of the synergy capsule suitable for short distance washing procedure of the invention Chemical constitution and property, such as water-soluble, disintegrating property, and its may with the interaction of the washing enzyme of capsule intension, It contribute to the clean result significantly increased of the synergy capsule of the present invention.In washing procedure with the present invention synergy capsule with Detergent is used in conjunction with, and can be obtained under relatively short wash time and relatively low wash temperature and without using synergy capsule Compared to more excellent clean result, so as to the energy resource consumption being effectively saved needed for washing, the consumption of water, and sewage is reduced Discharge, is advantageous to the protection of environment and the saving of resource, is advantageous to the development of green ecological society.

In one embodiment, the capsule shell of synergy capsule of the invention has contains 2% surface-active at 20 DEG C Disintegration time was no more than 30 minutes, preferably more than 20 minutes in the cleaning solution of agent, no more than 15 minutes, no more than 10 minutes, No more than 8 minutes, no more than 6 minutes, no more than 5 minutes.Because Asia washing process is generally the washing cycle of relative short distance, If expecting that washing can be played a role with enzyme in short distance washing cycle, need synergy capsule capsule shell have it is shorter Disintegration time so that washing can be discharged so as to there is the catalytic action that longer time carries out enzyme as early as possible with enzyme in cleaning solution, Realize the washing synergistic function of washing enzyme.

Because Asia washing process is generally the washing cycle of relative short distance, this requires the capsule shell of synergy capsule not Only to be disintegrated as early as possible to discharge content, also to ensure that its residual after terminating in washing cycle is as few as possible, it is impossible to consumption Person causes the puzzlement for the residual being observed that.In another embodiment, the capsule shell tool of synergy capsule of the invention Have and be no more than 18% in the washing process at 15 DEG C -30 DEG C, no more than 12%, preferably more than 10%, preferably more than 8%, preferably more than 6%, preferably more than 4%, preferably more than 3%, preferably more than 1% residual rate.

In another embodiment, synergy capsule of the invention can realize significant washing in short distance washing procedure The effect of synergy, wherein short distance washing includes the washing cycle no more than 110 minutes, preferably more than 100 minutes, do not surpass 80 minutes are spent, no more than 60 minutes, no more than 50 minutes, no more than 30 minutes.In another embodiment, short distance washing Main in program to wash the cycle no more than 90 minutes, no more than 70 minutes, preferably more than 50 minutes, preferably more than 30 minutes were excellent Choosing is no more than 20 minutes, preferably more than 15 minutes, preferably more than 12 minutes.

The synergy capsule of the present invention is preferably able to realize the synergistic effect of washing enzyme in relatively low wash temperature, and There is no significant residue problem.In another embodiment, there is the wash temperature no more than 60 DEG C in short distance washing procedure, Preferably more than 40 DEG C, no more than 35 DEG C, no more than 30 DEG C, no more than 20 DEG C, no more than 10 DEG C.

In another embodiment, the capsule shell of synergy capsule of the invention is derived by cellulose derivative, starch Thing or pulullan polysaccharide material are made, and preferably pulullan polysaccharide material is made.

In another embodiment, the washing included in synergy capsule of the invention is selected from following group with enzyme：Albumen Enzyme, amylase, cellulase, lipase, phosphatidase, cutinase, oxidizing ferment, oxygenase, transferase, reductase, hemicellulose Enzyme, mannonase esterase, isomerase, pectase, lactase, peroxidase, lyase, laccase, DNA Enzyme, lichenase, and combinations thereof.In another embodiment, the washing is selected from following group with enzyme：Protease, shallow lake Powder enzyme, mannase, cellulase and combinations thereof.

In one embodiment, included in the synergy capsule of the present invention washing with containing substantially no surface-active in enzyme Agent, bleaching agent or bleach activator.

Detergent of the synergy capsule of the present invention preferably with low cost is applied in washing process jointly, described inexpensive Detergent does not include washing enzyme generally, or only comprising a small amount of and/or cheap a certain or several enzyme.Due to this hair Bright synergy capsule is adhered to the clothing and utensil that can be washed independently of the offer of the single dose form of washing, consumer with optic zone The situation of specific spot and select specific one or more synergy capsules to be used in conjunction with detergent, can effectively go to decontaminate Stain.

In another embodiment, the washing enzyme included in synergy capsule of the invention is without without enzyme stabilizers The inexpensive enzyme granulate form of composition.The synergy capsule of the present invention can be provided in effective method in terms of cost, and enzyme is direct Consign to consumer and be not a concern enzyme stability and with detergent the problem of the compatibility of other compositions.

In one embodiment, its size of synergy capsule of the invention is about 5mm, about 10mm, about 20mm, about 30mm, About 40mm, to about 100mm.The capsule shape of the present invention is similar to the administration of general visible capsule for medicine, is oval or length Circle, when describing its size, the indication of its size is used as generally using the major axis of capsule.

In another embodiment, the clean result for the enhancing that synergy capsule of the invention provides is selected from：Removal spot, Maintain whiteness, reduce balling-up, fabric color nursing, remove smell, and combinations thereof.

In another aspect, the present invention relates to a kind of kit, it includes one or more previously described synergy capsules, There is corresponding visual identity key element on the synergy capsule.It is specific that described visual identity key element can help consumer to understand The one or more washing synergistic effects that can provide of each synergy capsule.In one embodiment, described synergy capsule It is individually wrapped in blister package material, above-mentioned synergy capsule can be with the combination of individual packaging or multiple packagings, such as forms A continuous row, or the form that continuous several row form square formation provide.

In another aspect, the present invention relates to the method for preparing synergy capsule as previously described, including：A) screening is 15 Residual rate is no more than 18% in washing process at DEG C -30 DEG C, no more than 12%, preferably more than 10%, preferably more than 8%, preferably more than 6%, preferably more than 4%, preferably more than 3%, preferably more than 1% capsule shell, and b) will Washing is filled into inside capsule shell with enzyme synergist.In one embodiment, the following step before being additionally included in step b Suddenly：C) screening is no more than the capsule shell of 30 minutes with disintegration rate in the cleaning solution containing 2% surfactant at 20 DEG C, Wherein step c) is carried out afterwards or simultaneously before step a).

Capsule shell/synergy capsule

The capsule shell of the synergy capsule of the present invention can be chosen such that the synergy capsule is hard shell capsules or soft capsule. Usual hard shell capsules are used to filling powder or the content of particle form, and soft capsule is more suitable for liquid, semiliquid or oil base Content.The difference of the capsule of the present invention and content of the medicament capsule because expecting to realize delivering, approach and side in delivering There is also significant difference in formula.

In one embodiment of the invention, synergy capsule is hard shell capsules.The hard shell capsules are made up of two parts shell, point Active material Bao Kuo not inserted " capsule body " therein, and " cap " being snugly fit inside on " capsule body ".Capsule body and cap Can be with previously prepared, or can be bought from capsule manufacturer.As its name implies, hard shell capsules are hard and non-flexible.Washing With enzyme, whether particle or powder type, though also its whether with carrier material or suitable diluent and excipient such as lactose, Magnesium stearate, or the mixing such as starch, can be loaded into the capsule body of sky.Then cap is placed on capsule body, both closely match somebody with somebody Close with complete encapsulating washing enzyme.The method can be carried out by hand, but more usually by using a variety of commercially available glue Capsule filling machine is completed.

In one embodiment of the invention, hard shell capsules shell is made up of polysaccharide material, includes but is not limited to：

Using water-soluble cellulose derivative as capsule made of primary raw material：Such as hydroxypropyl methylcellulose (HPMC) capsule, such as Chinese patent prospectus CN1418081A, CN1329478A disclose water-soluble by gelatin or such as hydroxypropyl methyl cellulose Capsule made of property cellulose derivative, plasticizer etc..CN1202102A discloses calcium carboxymethylcellulose or cross-linked carboxymethyl is fine Tie up plain sodium, capsule made of gelatinized starch and crospovidone etc..CN1292261A is disclosed by hydrophilic gel, water Plant hard capsule made of cellulose of solubleness, flocculation aid.CN1646369A discloses to be spread out by gelatin or water-soluble cellulose Biology capsule as made of hydroxypropyl methyl cellulose, plasticizer etc..CN1745745A discloses to be spread out by K- carragheens, cellulose Biology such as hydroxypropyl methylcellulose, ethyl cellulose, hydroxypropyl cellulose, carboxymethyl cellulose, Capsules made of alcohols；

Vegetable starch capsule：It is primary raw material by plant amylum and starch derivatives, for example, farina, para arrowroot Powder, certain plasticizer etc. is coordinated to be made.As disclosed in Chinese patent prospectus CN1483393A starch hollow capsule and Its production technology, it is made up of the component such as plant amylum or starch derivatives, plasticizer, water.Capsule disclosed in CN1623529A by Potato starch, carragheen, surfactant, plasticizer composition.CN1739488A is disclosed with konjac glucomannan through acid hydrolysis oxidative It is modified, with modified or unmodified vegetable protein (including soybean protein, zeins, wheat gluten, zein), animal One or both of gelatin or isinglass are complex as main component, and the auxiliary element system such as glycerine, dodecane sulfonate Into Capsules.Capsules disclosed in CN1895234A is made with amylose, glycerine for primary raw material.CN1903157A is public Open and manufacture Capsules soluble in the stomach by raw material of algal polysaccharides glue.CN1931145A is disclosed by amylose or soluble starch such as jade Plant hollow capsule is made in rice, potato, cassava, sweet potato, the extract of sweet potato and glycerine etc., and CN1687203A is disclosed by starch Hard shell capsules or soft capsule made of plasticizer, gel, surfactant, opacifier, food coloring etc. are proportionally added into after gelatinization.

Using other polysaccharide polymers as capsule made of primary raw material, pulullan polysaccharide capsule in this way.Pulullan polysaccharide English Literary fame claims pullulan, and Chinese is also translated into pulullan, pullulan, pullulan, pullulan, can be by Starch Hydrolysis Thing, sucrose or other carbohydrate direct fermentations produce, and are the mould caused exocellular polysaccharides of budding falx, mainly with α -1,6- glycosidic bonds Homotype polysaccharide is formed with reference to maltose, i.e. glucose is combined into maltotriose by α-Isosorbide-5-Nitrae-glycosidic bond, and both ends are again with α -1,6- sugar Glycosidic bond combines with other maltotriose, is so connected to become macromolecule polysaccharide, α-Isosorbide-5-Nitrae-glycosidic bond and α -1,6- glucosides repeatedly The ratio of key is 2: 1, the degree of polymerization 10~30000, the dalton of molecular weight 2.0 × 103~5.0 × 106.Pulullan polysaccharide can be by general The blue sugared zymotic fluid in Shandong obtains through sterilizing, decolourize, being dehydrated after desalination with modes such as spraying, fluid beds, can also use organic The dried object that extract by solvents forms, such as the method that Chinese patent prospectus CN1651467A is introduced, pulullan is sent out After zymotic fluid sterilization, obtained with the drying precipitate after the decolouring of the organic solvents such as ethanol, isopropanol, desalination and dehydration.Other are suitable Pulullan polysaccharide capsule for the present invention is included as disclosed in European patent EP 2663294B1.

In a preferred embodiment of the invention, the capsule shell of synergy capsule is cellulose derivative capsule or general Shandong orchid polyoses capsule.

In a preferred embodiment of the invention, the capsule shell of synergy capsule is pulullan polysaccharide capsule.Pu Lu Blue polyoses capsule has the transparency suitable with gelatine capsule so that filling content is clearly visible, in wide temperature humidity range Storage is stable, the low oxidation for avoiding filling content of oxygen transmission rate, while avoids in gelatine capsule preparation process and handle Animal Skin Pollution problem and gelatin disintegration rate in washing process are not rapid enough caused by hair etc., and produce glue after washing process terminates The residue of capsule material is adhered to washing clothing and other crusts, so as to have a strong impact on evaluation of the consumer to clean result Problem.

Commercially available hard shell capsules include：Plant capsule(Suzhou capsule company Capsugel), this is one Kind HPMC (hydroxypropyl methylcellulose) capsule, natural capsule Plantcaps^TM(Suzhou capsule company Capsugel), this is a kind of general Shandong orchid polyoses capsule,(pulullan polysaccharide) capsule (Suzhou Li Fan capsules company), this is another HPMC (hydroxypropyls Methylcellulose) capsule.Other capsules of available hard shell capsules for example described in EP2663294B1, CN101480447A etc..

In one embodiment of the invention, the capsule shell is made up of non-gelatin materials.

In one embodiment of the invention, hard shell capsules are preferably a kind of capsule shell, and the capsule shell has No more than 30 minutes, preferably more than 20 minutes in the cleaning solution containing 2% surfactant at 20 DEG C, no more than 15 minutes, no More than 10 minutes, no more than 8 minutes, no more than 6 minutes, the disintegration time no more than 5 minutes.

In another embodiment of the present invention, the selection of the material of hard shell capsules of the invention preferably has in 15-30 It is no more than 18% in DEG C washing process, no more than 12%, preferably more than 10%, preferably more than 8%, preferably more than 6%, Preferably more than 4%, preferably more than 3%, preferably more than 1% residual rate.

In another embodiment of the present invention, the capsule shell of synergy capsule is soft gel capsule.Soft gel capsule It is the soft shell of a piece of sealing, its interior liquid, suspension or semisolid of containing is used as filler.Soft gel capsule shell is by filmogen It is made with water-dispersible or water-soluble plasticizer, so as to assign flexibility.Soft capsule can be made up of polymer, such as hydroxypropyl first Base cellulose.Suitable liquid filling material is vegetable oil, wax or polyethylene glycol or the other liquid compatible with capsule composition Body.Soft gel capsule can convey liquid enzymes, or the enzyme granulate that conveying is dry, such as suspending agent.Prepare soft gel capsule, by enzyme or Active component mixes with packing material.Meanwhile by mixing filmogen and plastification material, prepare capsule substrate.The shape of capsule Carried out simultaneously into filling.Capsule substrate is formed as two films by packing machine, and it is supplied between two rotating moulds.Mould Depression containing capsule shape and size.The pump conveying liquid filling material synchronous with mould enters depression, then, is filling Afterwards, capsule is sealed by pressure immediately.After packing, soft gel capsule undergoes two step drying processes, in drumdrier Or completed in fluid bed dryer, it is followed by carrying out tray drying, or solidification a couple of days.

Washing enzyme

The synergy capsule of the present invention includes being included in the washing enzyme inside capsule shell.

The enzyme that the application context uses can be the combination of any enzyme or different enzymes that can be obtained by fermenting.Accordingly Ground, when mentioning " enzyme ", it is generally understood that being the combination for the enzyme for including single enzyme and more than one.

It should be understood that：The variant (such as being prepared with recombinant technique) of term " enzyme " including enzyme.The variant of these enzymes Example is recorded in documents below：Such as EP 251,446 (Genencor), WO 91/00345 (Novo Nordisk), EP 525,610 (Solvay) and WO 94/02618 (Gist-Brocades NV).The enzyme used in the specification and claims Classification and Academic Press Inc publish within 1992《Biochemistry and molecular biology international federation naming committee It is recommended that (1992)》Unanimously (Recommendations (1992) of the Nomenclature Committee of the International Union of Biochemistry and Molecular Biology, Academic Press, Inc., 1992).

The washing being suitable in the synergy capsule of the present invention includes protease, cellulase, lipase, phosphatide with enzyme Enzyme, cutinase, oxidizing ferment, oxygenase, transferase, reductase, hemicellulase, mannonase amylase, esterase, isomery Enzyme, pectase, lactase, peroxidase, pectate lyase, laccase, deoxyribonuclease, lichenase, and it Mixture.Preferable enzyme includes those enzymes that can hydrolyze substrate (for example, stain).These enzymes are known as hydrolase, bag Include but be not limited to protease (bacterium, fungi, acidity, neutrality or basic protein), amylase (a or p), lipase, cellulase, With their mixture.

Protease

Suitable protease can be animal, plant or microbe-derived.In one embodiment of the invention, albumen Enzyme is chemical modification or protein engineering.In one embodiment, protease is serine protease or metalloproteinases, excellent Select alkaline microbial protease or trypsin like proteases.The example of alkali protease such as subtilopeptidase A, such as Those come from Bacillus, for example, subtilopeptidase A promise and (Novo), subtilopeptidase A Carlsberg, withered grass bar Mycoproteinase 309, subtilopeptidase A 147, the protease of subtilopeptidase A 168 (being described in WO89/06279).Pancreas The example of protease sample protease includes ox source trypsase, the trypsase and Fusarium protease in pig source, is described in WO 89/06270 and WO 94/25583.

The example of useful protease is those WO 92/19729, WO 98/20115, WO 98/20116, and WO 98/ The variant of protease described in 34946, especially those protease in following site with one or more substitutions：27, 36,57,76,87,97,101,104,120,123,167,170,194,206,218,222,2 24,235, and 274.

Preferable commercially available protease includesDuralase^TM,Durazym^TM,Ultra,Ultra, Ultra, Ultra,Blaze100T,Blaze125T,Blaze150T,With(Novozymes A/S), PurafectPurafect Excellenz P1000^TM,Excellenz P1250^TM,Preferenz P100^TM, PurafectPreferenz P110^TM,Effectenz P1000^TM, ^TM, Effectenz P1050^TM,Purafect ^TM,Effectenz P2000^TM,With(Danisco/DuPont),Axapem^TM(Gist-Brocases N.V.), BLAP is (in US5352604 Figure 29 Shown sequence) and its variant (Henkel Corp.), and KAP (Bacillus alkalophilus subtilisin) (flower princes and dukes Department).

Cellulase

Suitable cellulase can be animal, plant or microbe-derived.In one embodiment of the invention, egg White enzyme is chemical modification or protein engineering.The cellulase can be derived from Bacillus, pseudomonas, humicola lanuginosa, Fusarium, fusarium globosum shuttle category or Acremonium.In one embodiment of the invention, the cellulase is derived from special detritus Mould, thermophilic fungus destroyed wire, Sporotrichum pulverulentum, Fusarium oxysporum, trichoderma reesei, Thielavia terrestris, Acremonium species, Acremonium species CBS 478.94, Kidney bean shell ball spore bacterium CBS 281.96, Crinipellis Scabella CBS 280.96, Volutella colletotrichoides or excrement life excrement shell bacterium ATCC 52644 or brood cell's bar Pseudomonas SP-KSMS237.The example of suitable cellulase is included in US 4,435,307, US 5,648,263, US 5,691, 178, US 5,776,757, WO 89/09259, EP 0 495 257, EP 0 531 372, WO 96/11262, WO 96/ 29397,WO 98/08940.WO 94/07998,EP 0 531 315,US 5,457,046,US 5,686,593,US 5, Those disclosed in 763,254, WO 95/24471, WO 98/12307 and WO99/001544.

Other cellulases are with the SEQ ID NO with WO 2002/099091:2 amino acid of the 1 to 773rd Inscribe-Isosorbide-5-Nitrae -1,4 beta-glucanase with least 97% sequence identity, or with the SEQ ID with WO 2001/062903 NO:2 amino acid of the 40 to 559th has 44 family's xyloglucanase enzymes of at least 60% sequence identity.

Preferable commercially available cellulase includes Celluzyme^TM,and Carezyme^TM(Novozymes A/ S)Carezyme PRemium^TM(Novozymes A/S),Celluclean^TM(Novozymes A/S),Celluclean Classic^TM(Novozymes A/S),Cellusoft^TM(Novozymes A/S),Whitezyme^TM(Novozymes A/S), Clazinase^TM,and Puradax HA^TM(Genencor International Inc.), and KAC-500 (B)^TM(Kao Corporation)。

Amylase

Amylase is alpha-amylase or glucoamylase, preferably microbe-derived or chemical modification or protein engineering 's.It is bacterium or originated from fungus.For example, the amylase can be obtained from Bacillus, such as bacillus licheniformis Alpha-amylase.Such as the alpha-amylase of from bacillus licheniformis a specific bacterial strain being described in detail in GB1,296,839.

The example of useful amylase, especially there is the variant of substitution in one or more following positions：15、23、 105、106、124、128、133、154、156、181、188、190、197、202、208、209、243、264、304、305、391、 408 and 444, WO 94/02597, WO 94/18314, WO 1995/010603, WO 1995/026397, WO 96/23873, WO 97/43424 and WO 00/60060, WO 2001/066712, described in WO 2006/002643.

In specific embodiments, alpha-amylase is derived from Bacillus sp bacterial strain NCIB 12289, NCIB 12512nd, NCIB 12513 and DSM 9375.In the especially preferred SEQ ID NOS 1 and 2 for being displayed at WO 95/26397 Alpha-amylase.

Preferable commercially available amylase includes Duramyl^TM,Termamyl^TM,Fungamyl^TM,Stainzyme^TM, Stainzyme Plus^TM,Natalase^TM,Liquozyme X and BAN^TM(from Novozymes A/S),and Rapidase^TM,Purastar^TM/Effectenz^TM,Powerase,Preferenz S1000,Preferenz S100and Preferenz S110(from Genencor International Inc./DuPont)。

Lipase and cutinase

Lipase is bacterium or fungal source.Including chemical modification or protein engineered mutant enzyme.Example includes Lipase from thermophilic fungal category, such as be such as described in coming from EP 258068 and EP 305216 and dredge lanuginosus spore Bacterium (is named as thin cotton like humicola lanuginosa) previously；Cutinase from Humicola, such as Humicola insolens (WO 96/13580)； The lipase (some in these are renamed as primary gram of Hall Bordetella now) of bacterial strain from pseudomonas, such as production alkali are false Monad or pseudomonas pseudoalcaligenes (EP 218272), Pseudomonas cepacia (EP 331376), pseudomonas strain SD705 (WO 95/06720＆WO 96/27002), Wisconsin pseudomonad (P.wisconsinensis) (WO 96/12012)； GDSL- type streptomyces lipase (WO 10/065455)；Cutinase (WO 10/107560) from Pyricularia oryzae；From door The cutinase (US 5,389,536) of more Sa pseudomonads；Fat from brown thermophilic to split spore bacterium (Thermobifida fusca) Fat enzyme (WO 11/084412)；Geobacillus stearothermophilus lipase (WO 11/084417)；From bacillus subtilis Lipase (WO 11/084599)；And from streptomyces griseus (WO 11/150157) and rotation streptomycete (S.pristinaespiralis) lipase (WO 12/137147).

Other examples are lipase Variants, such as are described in EP 407225, WO 92/05249, WO 94/01541, WO 94/25578、WO 95/14783、WO 95/30744、WO 95/35381、WO 95/22615、WO 96/00292、WO 97/ 04079th, WO 97/07202, WO 00/34450, WO 00/60063, WO 01/92502, WO 07/87508 and WO 09/ Those in 109500.

Preferable commercialization lipase product includes Lipolase^TM、Lipex^TM、Lipolex^TMAnd Lipoclean^TM(Novi Letter company), Lumafast (coming from Genencor Company (Genencor)) and Lipomax are (public from Ji Site Buro Cadizs Take charge of (Gist-Brocades)).

Other examples are the lipase of sometimes referred to as acyltransferase or Perhydrolase, for example, with antarctic candida (Candida antarctica) lipase A has the acyltransferase (WO 10/111143) of homology, from shame dirt branch Acyltransferase (WO 05/56782), the Perhydrolase from the families of CE 7 of bacillus (Mycobacterium smegmatis) The variant of (WO 09/67279) and M. smegmatis perhydrolase (steps the limited public affairs of textile dyeization especially from Hensel Take charge of S54V used in the commercial product Gentle Power Bleach of (Huntsman Textile Effects Pte Ltd) Variant) (WO 10/100028).

Pectate lyase

Pectate lyase can be derived from bacillus particularly bacillus licheniformis or B.agaradhaerens Wild-type enzyme, or for example such as US 6,124,127 (NZ 5543), WO 1999/027083 (NZ 5377), WO 1999/ 027084 (NZ 5378), WO 2002/006442 (NZ10044), WO 2002/092741 (NZ 10171) or WO 2003/ These derivative variants described in 095638 (NZ 10190).

Mannase

Mannase is the enzyme of hydrolyzing mannan.Suitable mannase includes coming from bacterium or originated from fungus , also including chemical modification or protein engineered mutant enzyme.Mannase can be the alkaline sweet dew of family 5 or 26 Dextranase.It can be from bacillus or Humicola, particularly B.agaradhaerens, bacillus licheniformis, resistance to The wild type of salt bacillus (B.halodurans), Bacillus clausii (B.clausii) or Humicola insolens.

Suitable mannase is described in WO 1999/064619.Commercially available mannase is for example(Novozymes A/S), and EFFECTENZ^TM M1000(Dupont)。

Peroxidase/oxidizing ferment

Suitable peroxidase/oxidizing ferment includes peroxidase/oxidizing ferment of plant, bacterium or originated from fungus.Change In modification mutant or protein engineering mutant are also included within.The example of useful peroxidase includes coming from ghost agaric Belong to the peroxidase of (Coprinus), such as the peroxidase from Coprinus cinereus (C.Cinereus).Such as EP 179, It is described in detail in 486, and its variant described in WO 93/24618, WO 95/10602 and WO 98/15257.

Commercially available peroxidase includes Guardzyme^TM(Novo Nordisk A/S)。

Deoxyribonuclease

Polypeptide or deoxyribonuclease (DNA enzymatic) with deoxyribonuclease (DNA enzymatic) activity are catalytic dna bones The hydrolysis cutting of phosphodiester bond in frame is so as to any enzyme of degradation of dna.Two terms are interchangeably used, there is DNA enzymatic The polypeptide and DNA enzymatic of activity.

Preferable DNA enzymatic is available from bacterium or fungi.Chemical modification mutant or protein engineering mutant also include Inside.

Preferable DNA enzymatic may be selected from any following enzyme family：E.C.3.1.21.x, wherein x=l, 2,3,4,5,6,7,8 Or 9, E.C.3.1.22.y wherein y=l, 2,4 or 5, E.C.3.1.30.Z wherein z=1 or 2, E.C.3.1.31.1 and its mixed Compound.

Other preferable DNA enzymatics are those DNA enzymatics and its derivative variant disclosed in EP 17165320.7.

The washing enzyme being suitable in the synergy capsule of the present invention can be with single pure enzyme or the mixture of variety classes enzyme Form provide.The content of single enzyme or enzymatic mixture in synergy capsule can change, and commercial contain enzyme with common one spoonful Detergent is compared, and it typically provides higher enzyme dosage in washing cycle.Pure enzyme dosage in selective advance capsule is to strengthen The cleaning capacity of conventional cleaning product.For example, the final concentration of pure enzyme or active enzyme can be chosen, to be each laundry Or wash the dish cycle and about 0.0001ppm, about about 0.001ppm, about 0.01ppm, 0.1ppm are provided, to about 1ppm, about 2.5ppm, about 5ppm, about 10ppm, about 25ppm, about 50ppm enzyme.It will be appreciated by those skilled in the art that can in the present invention in some cases With application more than 50ppm enzyme concentration.

Particle form can be used as to provide for the enzyme component in synergy capsule.In preferred embodiments, the enzyme Particle is inexpensive particle, without the composition costly needed for the stable upon storage enzyme in detergent, such as shielding material, Enzyme stabilizers and bleaching nertralizer etc..Certainly, if desired and effective in cost, some in these compositions can be total to enzyme With exist with the present invention washing synergy capsule in.

A kind of for example Chinese granted patent ZL00814580.6 (Novi of the method for the drying enzyme granulate of inexpensive good properties Letter) described in, it is integrally incorporated herein.This method, which includes spraying the fermentation broth raw material containing enzyme and biomass, to be done Dry, wherein the biomass forms at least the 10% of the biomass obtained from fermentation.

A kind of such particle has the salt coated layer of the enzyme and relative thin that are coated in salt kind (salt seed).Enzyme into It point can also be dry powder enzyme or be dispersed on carrier or enzyme of the bed board on carrier, the carrier such as sugar, starch or wheat Bud dextrin.Enzyme can also add during wet granulation, and such as United States Patent (USP) 6, described in 852,336, it is integrally incorporated herein.

Following non-limiting patent disclosure enumerate illustrate can in the present invention using oneself enzyme formulation for knowing, and Preferably, it is modified to reduce or eliminate enzyme stabilizers, including reduces or eliminate shielding material and protectiveness coating：US4,689, 297；US5,254,283；US5,324,649；EP 656058B1；EP804532B1；US6,120,811；US6,248,706； US6,20,236；US6,423,517；US6,432,902；EP1124945B1；US6,413,749；US6,602,841；US6, 534,466；EP1220887B1；US6,310,027；US7,018,821；US4,106,991；US6,924,133；US6,933, 141；EP1324651B1；EP170360；EP458849；EP2787464；W097/29116；WO93/07260；WO02/0746； And W096/38527.

The washing synergy capsule of the present invention can also include and washing enzyme in addition to the particle comprising washing enzyme The other compositions of grain mixing.In one embodiment of the invention, the enzyme granulate in washing capsule accounts for capsules weight at least About 1%, 2.5%, 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 60%, 70%, 80%, 90%, 95%, 99%.

Polymer

The washing synergy capsule of the present invention can also include as known in the art in addition to the particle comprising washing enzyme For any polymer used in detergent.Polymer can work as co-builder as mentioned above, or can To provide antiredeposition, fiber protection, dirt release, the cleaning of dyestuff metastasis suppressor, greasy dirt and/or anti-foam characteristic.Some polymerizations Thing can have more than one above-mentioned characteristic and/or more than one motif (motif) mentioned below.It is exemplary Polymer includes (carboxymethyl) cellulose (CMC), poly- (vinyl alcohol) (PVA), PVP (PVP), poly- (second two Alcohol) or poly- (oxirane) (PEG), poly- (ethylenimine) of ethoxylation, Carboxymethylinulin (CMI) and poly- carboxylate, example Such as PAA, PAA/PMA, poly- aspartic acid and lauryl methacrylate/acrylic copolymer, hydrophobically modified CMC (HM-CMC) Copolymer, poly- (PETP) and poly- (oxygen ethene terephthaldehyde with silicone, terephthalic acid (TPA) and oligoethylene glycol Sour second diester) copolymer (PET-POET), PVP, poly- (vinyl imidazole) (PVI), poly- (vinylpyridine-N-oxide) (PVPO or PVPNO) and polyvinyl pyrrolidone/vinyl base imidazoles (PVPVI).Other illustrative polymers include sulfonation Polycarboxylate, PEO and PPOX (PEO-PPO) and ethyoxyl sulfuric acid di-quaternary ammonium salt.Other are exemplary poly- Compound is disclosed in such as WO 2006/130575.It has also contemplated that the salt of above-mentioned polymer.

Fabric hueing agent

The washing synergy capsule of the present invention can also include as known in the art in addition to the particle comprising washing enzyme For the fabric hueing agent in detergent, such as dyestuff or pigment, when preparing in detergent compositions, when the fabric Fabric hueing agent can be deposited on fabric when being contacted with a kind of cleaning solution, and the cleaning solution includes the detergent composition, and And the color of the fabric is therefore changed by the absorption/reflection of visible ray.Fluorescent whitening agent launches at least some visible rays.Phase Than under, because they absorb at least a portion visible light, fabric hueing agent changes the color on surface.Suitable knits Thing toner includes dyestuff and dye clay conjugates, and can also include pigment.Suitable dyestuff includes small molecule dyes And polymeric dye.Suitable small molecule dyes include the small molecule dyes being selected from the group, and the group is by falling into color index The following dyestuff composition of (Colour Index) (C.I.) classification：Directly blue, direct red, direct purple, acid blue, acid red, acid Property purple, alkali blue, alkalescence purple and alkalescence is red or its mixture, for example, be described in WO 2005/03274, WO 2005/03275, (it is combined hereby by reference) in WO 2005/03276 and EP 1876226.Detergent composition is preferably included from about 0.00003wt% to about 0.2wt%, from about 0.00008wt% to about 0.05wt% or even from about 0.0001wt% to about 0.04wt% fabric hueing agent.Said composition can include the fabric hueing agent from 0.0001wt% to 0.2wt%, when the group When compound is in the form of unit dose bag, this can be particularly preferred.Suitable toner is also disclosed in such as WO In 2007/087257 and WO 2007/087243.In one embodiment of the invention, the fabric hueing agent in washing capsule accounts for About the 0.002% of capsules weight, about 0.02%, about 0.2%, about 0.5%, about 1%, more.

Dye transfer inhibitor

The washing synergy capsule of the present invention can also include one or more dye transfer inhibitors.Suitable polymeric dye Transfer inhibitor includes but is not limited to polyvinyl pyrrolidone polymers, polyamines N- oxide polymers, N- vinylpyrrolidones Copolymer, Ju Yi Xi oxazolidones and polyvinyl imidazole or its mixture with N- vinyl imidazoles.Increase when being present in washing When imitating in capsule, dye transfer inhibitor can account for about the 0.1% of capsules weight, and 0.2%, 0.5% or more.

Fluorescent whitening agent

The washing synergy capsule of the present invention can also include other component, and these components can give the article cleaned Coloring, such as fluorescent whitening agent or optical brightener.In the present compositions can use be suitable in clothes washing Any fluorescent whitening agent used in agent composition.The most frequently used fluorescent whitening agent is those for belonging to following classification：Diaminourea Stilbene-sulfonic acid, diaryl pyrazole quinoline derivant and diphenyl-distyrene radical derivative.Diamino-stilbene-sulfonic acid The example of the fluorescent whitening agent of type includes following sodium salt：4,4'- pairs-(2- diethanolaminos -4- anilino--sym-triazines - 6- bases amino) stilbene -2,2'- disulfonates, 4,4'- be double-sulphurs of (2,4- hexichol amido-sym-triazine -6- bases amino) stilbene -2.2'- two Hydrochlorate, 4,4'- pairs-(2- anilino-s -4- (N- methyl-N-2- hydroxy-ethyls amino)-sym-triazine -6- bases amino) stilbene -2,2'- Disulfonate, 4,4'- pairs-(4- phenyl -1,2,3- triazole -2- bases) stilbene -2,2'- disulfonates and 5- (2H- naphtho-s [1,2- D] [1,2,3] triazole -2- bases) -2- [(E) -2- phenyl vinyls] benzene sulfonic acid sodium salt.Preferable fluorescent whitening agent be can from vapour bar- Tinopal (Tinopal) DMS and Tinopal that Jia Ji limited companies (Ciba-Geigy AG) (Basel, Switzerland) obtain CBS.Tinopal DMS is 4,4'- pairs-(2- morpholino -4- anilino--s- triazine -6- bases amino) stilbene -2,2'- disulfonates Disodium salt.Tinopal CBS is the disodium salt of 2,2'- pairs-(phenyl-styryl)-disulfonate.Further preferably fluorescent whitening agent, It is commercially available Parawhite KX, by Paramount mineral and chemical (Paramount Minerals and Chemicals), Bombay, India's supply.Other fluorescers for being suitable for using in the present invention include 1-3- diaryl pyrazole oxazolines and 7- alkane ammonia Butylcoumariii.Suitable brightener or fluorescent whitening agent can account for about the 0.1% of the washing synergy capsules weight of the present invention, about 0.5%, about 1%, about 5%, 10%, 20%, 50% or more.

Dirt release polymer

The washing synergy capsule of the present invention can also include one or more dirt release polymers, and these polymer help Dirt is removed from fabric (such as cotton and fabric based on polyester), particularly removes hydrophobic soil from the fabric based on polyester. Dirt release polymer may, for example, be non-ionic or anionic terephthalic acid (TPA) based polyalcohol, Vinylcaprolactam homopolymer With related copolymers, vinyl graft copolymer, polyester-polyamide, see, for example, detergent powder, surfactant science system Arrange the 7th chapter of volume 71, Marcel moral Kerr Corp (Marcel Dekker, Inc.).Another type of dirt release polymerization Thing is the amphipathic alkoxylate greasy dirt cleaning for the multiple Alkoxylated groups for including a cored structure and being connected to the cored structure Polymer.Core texture can include poly- alkyl imino structure or poly- alkanol amine structure, as retouched in detail in WO 2009/087523 (it is combined hereby by reference) stated.In addition, random graft copolymer is suitable dirt release polymer.Suitable Graft copolymer is described in greater detail in WO 2007/138054, WO 2006/108856 and WO 2006/113314 (by it Combined hereby by reference).Other dirt release polymers be substitution polysaccharide structures, the cellulose knot especially substituted Structure, such as modified cellulose derivative, such as those described in EP 1867808 or WO 2003/040279 are (all logical by the two Cross reference and combine hereby).Suitable cellulosic polymer include cellulose, cellulose ether, cellulose esters, cellulose amides and Its mixture.Suitable cellulosic polymer includes anion-modified cellulose, nonionic modified cellulose, cation and changed Cellulose, the cellulose and its mixture of zwitterionic modification of property.Suitable cellulosic polymer includes methylcellulose, carboxylic Methylcellulose, ethyl cellulose, hydroxyethyl cellulose, hydroxypropyl methyl cellulose, ester carboxymethyl cellulose and its mixture. In one embodiment of the invention, the dirt release polymer washed in synergy capsule accounts for about the 0.1%, 1% of capsules weight, 5%, 10%, 50%, 60% or more.

Anti-redeposition agents

The washing synergy capsule of the present invention can also include one or more anti redeposition agents, such as carboxymethyl cellulose (CMC), polyvinyl alcohol (PVA), polyvinylpyrrolidone (PVP), polyoxyethylene and/or polyethylene glycol (PEG), acrylic acid it is equal Polymers, the copolymer of acrylic acid and maleic acid and the poly- ethyleneimine of ethoxylation.Described above under dirt release polymer Cellulose-based polymer is also used as anti redeposition agent.In one embodiment of the invention, wash anti-in synergy capsule Reprecipitation agent accounts for about the 0.1% of capsules weight, and 1%, 5%, 10%, 50%, 60% or more.

In one embodiment of the invention, the content that synergy capsule includes is in addition to washing enzyme, substantially Material of some being common in detergent to enzyme causticity, such as surfactant, bleaching agent, bleach activator etc. are not contained.

The common detergent bleaching system components that are used for as is generally known in the art include bleaching catalyst, optical white, bleaching Activator, hydrogen peroxide source such as SODIUM PERCARBONATE, sodium perborate and hydrogen peroxide-urea (1:1), preforming peracid and its mixing Thing.Suitable preforming peracid includes but is not limited to peroxycarboxylic acid and salt, diperoxy dicarboxylic acids, crosses imidic acid (perimidic ) and salt, permonosulphuric acid and salt (such as potassium hydrogen persulfate (Oxone (R)) and its mixture acid.Bleach system it is unrestricted Property example include forming the bleach system based on peroxide that combines of bleach-activating with peracid, it can include for example inorganic Salt, include sodium salt (being usually list or tetrahydrate), percarbonate, excessively persulfate, the phosphorus of alkali metal salt such as perborate Hydrochlorate, persilicate.Term bleach-activating means a kind of and hydroperoxidation to be formed via hydrolysis excessively herein The compound of acid.The peracid formed in this way forms the bleaching agent of activation.Need suitable bleach-activating bag as used herein Include belong to ester, acid amides, acid imide or anhydrides it is other those.Suitable example be tetra acetyl ethylene diamine (TAED), 4- [(3, 5,5- trimethyl acetyls base) epoxide] benzene -1- sodium sulfonates (ISONOBS), 4- (dodecanoyl epoxide) benzene -1- sulfonate (LOBS), 4- (capryl epoxide) benzene -1- sulfonate, 4- (capryl epoxide) benzoate (DOBS or DOBA), 4- (pelargonyl group epoxide) Benzene -1- sulfonate (NOBS) and/or those being disclosed in WO 98/17767.The specific family of bleach-activating interested It is disclosed in EP 624154 and ATEC (ATC) is particularly preferably in that family.ATC or short chain Triglyceride (as triacetin) has advantages below, and it is environment-friendly.In addition, ATEC and triacetin There is good hydrolytic stability in the product in storage, and be a kind of effective bleach-activating.Finally, ATC is more Function, because the citrate discharged in hydrolysis is crossed can work as builder.Alternately, bleaching system Such as peroxy acid of acid amides, acid imide or sulfone type can be included.Bleaching system can also include peracid, such as 6- (O-phthalics Imide) peroxy caproic acid (PAP).Bleaching system can also include bleaching catalyst.In certain embodiments, bleaching component can To be the organic catalyst being selected from the group, the group is made up of the following：Organic catalyst with following formula：

（i)

(ii)

And its mixture (iii)；

Wherein each R1 is independently comprising the branched alkyl of a carbon from 9 to 24 or includes the straight chain alkane of a carbon from 11 to 24 Base, preferably each R1 be independently comprising the branched alkyl of a carbon from 9 to 18 or include the straight chained alkyl of a carbon from 11 to 18, More preferably each R1 is made up of independently selected from the following group, the group the following：2- propylheptyls, 2- butyl octyls, 2- amyl groups Nonyl, 2- hexyls decyl, dodecyl, myristyl, cetyl, octadecyl, isononyl, isodecyl, isotridecyl And different pentadecyl.Other exemplary bleaching systems are described in such as WO 2007/087258, WO 2007/087244, WO 2007/087259th, in EP 1867708 (vitamin K) and WO 2007/087242.Suitable optical white may, for example, be The Phthalocyanine Zinc or aluminum phthalocyanine of sulfonation.

Preferably, in addition to bleaching catalyst, particularly organic bleaching catalyst, bleaching component also includes source of peracid. Source of peracid can be selected from (a) pre-formed peracid；(b) percarbonate, perborate or persulfate (hydrogen peroxide source), preferably Combined with a kind of bleach-activating；Perhydrolase and ester, in textile processing step in presence of water former (c) Position forms peracid.

In another aspect, the present invention relates to a kind of synergy capsule for being used to strengthen clean result, it is more that it includes Propiram Capsule shell made of sugared material, and the washing enzyme in above-mentioned capsule shell.Pulullan polysaccharide capsule have with it is bright The suitable transparency of glue capsule so that filling content is clearly visible, stabilization is stored in wide temperature humidity range, oxygen transmission rate is low to be kept away Exempt to fill the oxidation of content, at the same avoid handled in gelatine capsule preparation process pollution problem caused by animal skin etc. and Gelatin disintegration rate in washing process is not rapid enough, and the residue of generation capsule material is adhered to after washing process terminates Clothing and other crusts are washed, the problem of so as to have a strong impact on evaluation of the consumer to clean result.

In another aspect, the present invention relates to a kind of kit, it includes one or more previously described synergy capsules, There is corresponding consumer's identifying feature on the synergy capsule.Described consumer's identifying feature can help consumer to understand One or more washing synergistic effects that specific each synergy capsule can provide.The identifying feature can be wanted including vision Element, olfactory component or other sensation key elements.The visible elements can be such as word, pattern, color or its combination, described to smell Feel that key element can be specific fragrance.The purpose of design of these consumer's identifying features is to help consumer to understand corresponding increase Imitate the specific washing synergistic effect of capsule.

In an embodiment of foregoing invention, in the kit, synergy capsule is individually wrapped in blister package In material, above-mentioned synergy capsule can be with the combination of individual packaging or multiple packagings, such as forms a continuous row, or continuous several row The form for forming square formation provides.Common, blister package during the blister package material is medicament capsule preparation and provided Material can be made of aluminium foil and plastic material, the molded plastics piece usually with back lining materials such as layers of foil material so that disappear Expense person can be discharged it from the package by pressing capsule.

The synergy capsule of the present invention can also provide in seal box, bottle, tank.Any container or packaging can match somebody with somebody There is distributor.The distinguishing mark that uses of capsule, including above-mentioned vision recognition mark can be included in outer packing.

In another aspect, the present invention relates to the method for preparing synergy capsule as previously described, including：A) screening is 15 Residual rate is no more than 18% in washing process at DEG C -30 DEG C, no more than 12%, preferably more than 10%, preferably more than 8%, preferably more than 6%, preferably more than 4%, preferably more than 3%, preferably more than 1% capsule shell, and b) will Washing is filled into inside capsule shell with enzyme synergist.

In one embodiment, the following steps being additionally included in before step b：C) screening has contains 2% at 20 DEG C Disintegration rate is no more than the capsule shell of 30 minutes in the cleaning solution of surfactant, wherein step c) before step a), it Carry out afterwards or simultaneously.

Suitable capsule shell material is screened by the residual rate and disintegration rate of the capsule of the invention defined, can be effective Ground prepares the washing synergy capsule for meeting consumer demand of the present invention.

Analysis method

1. difference (Δ REM) analysis between light intensity value

After the completion of washing procedure, all samples after washing are dried overnight under conditions of aeration-drying.Then to dry Dry sample carries out light reflectivity assessment, uses the reflection spectrophotometrics of Macbeth Color Eye 7000 for being equipped with minimum aperture Meter.Do not have to measure under conditions of UV in incident light, and extract 460nm reflectivity.Scrubbed sample is surveyed Amount.The test sample that will be measured is placed on another sample of same type and color (sisters' sample).When textile table During difference DELTA REM between the light intensity value in face >=3, it is considered as visible difference.

2. disintegration time determines

The preparation of model washing powder solution：Deionized water, it is 2%w/w to add foregoing model washing powder to concentration.

By blue dyes (Remazol Br Blue R spec 160%, DyStar Kimya San.ve Tic.Ltd.Sti) and national standard washing powder (GB/T2013174-2008, being purchased from China Daily Chemical Industry Research Institute) is with 1:6 After weight is than being well mixed, weighing 0.3g said mixtures is filled in capsule to be measured, is discharged as counterweight content and disintegration Indicator.The capsule to be measured of above-mentioned preparation is put into the glass for the 200mL models washing powder solution (2w/w%) for filling 20 DEG C respectively In glass beaker (beaker volume is 250ml), start to stir, magneton (C200, hundred prosperous sensible Science and Technology Ltd.s, long 20mm, diameter 7mm) stir speed (S.S.) is 400rpm.Because washing with enzyme has stronger water solubility, dissolution time is short, and T50 is 30s at 20 DEG C, Therefore above-mentioned capsule to be measured rises brokenly, the time that blue dyes disengages can be considered the washing synergy glue being equal in practical application containing enzyme At the time of capsule disintegration starts, i.e., at the time of initial visual observations to blueness are leaked in solution out of capsule.

3. residual rate determines

Capsule shell allows for being completely dissolved after washing procedure terminates, and will not just be formed and remain and adhere to clothing On cause the puzzlement of consumer.Therefore, residual rate of the capsule material after washing is to judge it if appropriate for applying in wash environment In one of major criterion.

The weight remnants percentages of residual rate (R%), i.e. Capsules are determined as follows：Accurately weigh at ambient temperature The weight W (0) (being accurate to 0.01g) of Capsules, then the Capsules after weighing is put into non-woven fabrics tea bag (being purchased from supermarket) And measure sack and total capsule weight amount W (1).Capsules to be measured is put into washing machine with bag.Because tea bag is being washed During washing it is possible that because absorption detergent residual (such as zeolite 4A) or friction breakage cause weight change, therefore entering Tea bag need to have been added as calibration samples during row often wheel experiment, change the error delta brought to correct tea bag own wt, The value of wherein Δ is derived from the average value obtained by five measurement parallel samples.The gross weight of rear tea bag and Capsules, note are washed in measurement Make W (2).R% is calculated according to following formula, wherein W (1)-W (0)+Δ is the weight for washing rear tea bag.The meter of the residual rate of every kind of capsule Calculate the average value for being derived from three groups of parallel samples.

R%=(W (2)-(W (1)-W (0)+Δ)) ÷ W (0) × 100%

Following non-limiting examples are further discussed below the preferred embodiment in the scope of the invention.Providing embodiment is only For illustrative purposes, and should not be understood as limitation of the present invention because without departing from the spirit with scope Under the conditions of can carry out many changes to it.

4. difference (Δ L) analysis between brightness value

After the completion of washing procedure, all samples after washing are dried overnight under conditions of aeration-drying.Then to dry Dry sample carries out light reflectivity assessment, uses the reflection spectrophotometrics of Macbeth Color Eye 7000 for being equipped with minimum aperture Meter.Do not have to measure under conditions of UV in incident light, and extract Lab measured values, scrubbed sample is measured.Will The test sample to be measured is placed on another sample of same type and color (sisters' sample).For for the black of test Color cotton fabric, L values are lower, and surface fabric surface is more smooth, as the difference DELTA L between the brightness value of textile surface >=0.5, depending on For visible difference.

Embodiment

Material：

1. washing pollution fabric sample

The following commercially available 12 pollutions fabric sample of rotary drum washing machine method washing.

2. solid enzyme granulate mixture

Accurately weigh solid enzyme granulate (being accurate to 0.005g), 0.45g protease (Novozymes A/S, Savinase 24T), 0.15g amylase (Novozymes A/S, Stainzyme 12T) and 0.01g mannases (Novozymes A/S, Mannaway 4T).Uniformly mixing.

3. detergent compositions

Model liquid detergent：

Model washing powder：

LAS(C10-C13)	15%
		AEO	2%
Sodium carbonate	20%
		Sodium disilicate	12%
Zeolite 4A	15%
		Polymer	1%
Sodium sulphate	35%

The preparation of above-mentioned model washing powder and model liquid detergent is referred to the configuration of chinese national standard washing powder.

Washing facility and condition

1. rotary drum washing machine washs

2. roller washing machine is tested

The parameter of different washing procedures in roller washing machine is as follows：

3. Terg-O-Tometer is tested

The disintegration time of 1. different capsule materials of embodiment

Capsule a '-d ' to be measured are prepared according to the description of analysis method 2 with 4 kinds of commercially available Capsuleses, and determine different capsules The disintegration time of material.Capsules is respectively：

A. gelatine capsule(#0, purchased from Suzhou capsule company Capsugel),

B. plant capsule(#0, purchased from Suzhou capsule company Capsugel), this is that (hydroxypropyl first is fine by a kind of HPMC Dimension element) capsule

C. natural capsule Plantcaps^TM(#0, purchased from Suzhou capsule company Capsugel), this is a kind of pulullan polysaccharide Capsule

d.(pulullan polysaccharide) capsule (#0, purchased from Suzhou Li Fan capsules company), this is another HPMC (hydroxypropyl methylcellulose) capsule

Each experiment takes three capsules to test under the same conditions three times, and measured value takes arithmetic mean of instantaneous value.Test result is such as Shown in table 7.

Table 7：The disintegration time (20 DEG C) of different capsules

Capsule to be measured	Disintegration time
		a’	34′34″
b’	5′31″
		c'	4′5″
d'	4′31″

In addition, for influence of the research different temperatures to capsule disintegration time, by above-mentioned experiment respectively at 30 DEG C, 40 DEG C are respectively entered Row is corresponding to be repeated, and test takes arithmetic mean of instantaneous value three times.Test result is as shown in table 8 and table 9.

Table 8：The disintegration time (30 DEG C) of different capsules

Capsule species	Disintegration time
		a’	11′25″
b’	5′31″
		c'	4′5″
d'	3′39″

Table 9：The disintegration time (40 DEG C) of different capsules

Capsule species	Disintegration time
		a’	1′59″
b’	5′31″
		c'	4′5″
d'	6′49″

The disintegration time of the gelatine capsule phase in low temperature (20 DEG C, 30 DEG C) washing process is can be seen that from table 7-9 result Capsule to other materials is most long, and disintegration time just starts to show compared with other capsules in high temperature (40 DEG C) washing process Shorten.This shows that the disintegration time of gelatine capsule has significant wash temperature dependence；And the disintegration time of HPMC capsules exists It is influenced by temperature in common wash temperature section not notable.

Influence of the ionic strength of embodiment 2. to the disintegration time of capsule material

The purpose of this experiment is the increase of cleaning solution ionic strength caused by verifying the auxiliary agent included in detergent to capsule The influence of material disintegration time.The preparation of capsule to be measured in experimental group, the configuration of model washing powder solution and the survey of rate of release Amount method is tested and carried out at 20 DEG C with described in analysis method 2.

Contain the 0.4%Na as auxiliary agent in the model washing powder that experimental group uses₂CO₃And 0.7%Na₂SO₄；

Other conditions are consistent in auxiliary agent enhancing group, but additionally addition auxiliary agent, auxiliary agent contain on the basis of original detergent Measure as the 3.4%Na of washing powder ratio₂CO₃+ 2.7%Na₂SO₄；

Pure water control group, without using model washing powder, the same experimental group of other conditions.

This experiment test two kinds of capsule b ' and c ' to be measured disintegration time.As a result as shown in the table, each data take phase The arithmetic mean of instantaneous value repeated twice with the conditions of.

The plant capsule of table 10.The disintegration time of (HPMC capsules, i.e. b ' capsules) is washed

The natural capsule Plantcaps of table 11.^TMThe disintegration time of (pulullan polysaccharide capsule, i.e. c ' capsules)

Disintegration time ionic strength and/or the pH caused by by auxiliary agent of HPMC capsules are can be seen that from table 10-11 result It is worth increased influence and significantly extends, and the disintegration time of pulullan polysaccharide capsule is by ionic strength and/or the increased shadow of pH value Sound is not notable.

The clean result of washing synergist is assessed made of 3. different capsule materials of embodiment.

1. wash the preparation of synergy capsule

The laundry booster to be measured of 4 kinds of enzyme granulates containing solid is prepared with 4 kinds of commercially available Capsuleses respectively.Capsules a-d Described in embodiment 1, solid enzyme granulate mixture is as described in " material " 2 " solid enzyme granulate mixture " part above.Will be hard Capsule both ends are opened and the solid enzyme granulate mixture weighed are respectively charged into Capsules a-d, then capsule both ends are buckled Tightly, so as to preparing each washing synergy capsules A-D of the enzyme granulate containing solid.

2. wash synergy capsule synergy test

Experimental group 1-4 is separately added into a washing synergy capsules A-D when washing and originating.

Positive controls are then directly added into the solid enzyme granulate with contained equivalent in washing synergy capsule when washing and originating Mixture.

It is that product are 12 kinds as described in the Materials section above " fabric sample is polluted in washing " to wash targeted spot In 11 kinds of samples characterized in spot.Set using the rotary drum washing machine of embodiment above " washing facility and condition " part Put and washed, wash temperature is 25 DEG C.After the completion of washing, measure and calculate the light intensity value of each experimental group 1-4 fabric faces With the difference of the light intensity value of the fabric face of positive controls, i.e. Δ Rem.

Δ Rem=Rem (T)-Rem (0)

Washed textile surface when solid enzymatic mixture (positive control) being put into washing machine when Rem (0) is 0min Light intensity value；

Rem (T) is the light intensity value with the textile surface after washing synergy capsule washing；

Experimental result is shown in table 3 and 4.

Table 12：12 kinds of spots are washed using what model liquid detergent and washing synergy capsules A-D were presented in rotary drum washing machine Wash effect (Δ Rem)

It is can be seen that from the result of table 12 in the environment washed using model liquid detergent：

When the washing synergy capsule of addition is the washing enzyme of gelatine capsule parcel, it is being washed relative to positive controls Effect after washing, have in 11 kinds of spots and occur significantly reducing for clean result, i.e. Δ REM in the test spot of 6 kinds (55%) Absolute value be more than 3；

And when the washing synergy capsule added is other materials, during such as HPMC capsules or pulullan polysaccharide capsule, at 11 kinds The clean result compared with positive control occur without one kind (0%) in spot significantly reduces.

Table 13：12 kinds of spots are washed using what model washing powder and washing synergy capsules A-D were presented in rotary drum washing machine Wash effect (Δ REM)

It is can be seen that from the result of table 13 in the environment washed using model washing powder：

When the washing synergy capsule of addition is the washing enzyme of gelatine capsule parcel, it is being washed relative to positive controls Effect after washing, have in 11 kinds of spots and occur significantly reducing for clean result, i.e. Δ REM in the test spot of 7 kinds (64%) Absolute value be more than 3；

And it is other materials to work as the washing synergy capsule added, such as HPMC capsules, almost do not occur in 11 kinds of spots Clean result significantly reduces compared with positive control, or during pulullan polysaccharide capsule, in the clean result of 11 kinds of spots only Have 1 or the clean result of 2 kind of spot occur significant reduction compared with positive control.

It was found from the result of table 12 and 13, gelatine capsule can influence the operating efficiency of the content containing enzyme, especially when it makes It is the impeller of the washing cycle more popular in Asia shorter (main wash the time be 15min, a length of 40min when always washing) with environment When in washing procedure of washing machine.And washing synergy capsule made of other materials, such as HPMC capsules and pulullan polysaccharide capsule not The reduction of the significant clean result compared with positive control can be significantly affected.

The capsule material residual rate of embodiment 4.

Evaluated and tested by the description of analysis method part " measure of residual rate " capsule a-d commercially available to 4 kinds, 4 kinds of cities Sell consistent described in capsule a-d and embodiment 1.Drum wash is respectively adopted and impeller washing carries out the survey of capsule material residual rate Fixed, the condition of washing is as described in " washing facility and condition " above.

First, the corrected value of tea bag is shown in Table 14.

Table 14：Tea bag weight (gram) changes delta before and after washing test

Table 15 below -18 carries out the test analysis of residual rate at different conditions to various capsules respectively.

Table 15：The residual rate of the different washing durations of 30 DEG C of capsule a (gelatine capsule) roller washing machine

	Washing cycle	Master washes the cycle	Residual rate
				Express and (subtract drift) express 20short	11	20	78%
Express express 20	11	30	97%
				Shirt shirt short	23	44	72%
Dark clothing dark garments	22	62	79%
				Exempt to press minimum ion	83	87	84%
Cotton short are washed and (subtracted drift) to pure cotton	51	119	0%
				Pure cotton washes cotton	51	149	38%
Intensive is washed in reinforcement	108	167	- 7%

Table 16：The residual rate of the different washing durations of 30 DEG C of capsule b (HPMC capsules) roller washing machine

Table 17：Residual rates of the capsule c (pulullan polysaccharide capsule) in 30 DEG C of different washing durations of roller washing machine

	Washing cycle	Master washes the cycle	Residual rate
				Express and (subtract drift) express 20short	11	20	3%
Express express 20	11	30	3%
				Shirt shirt short	23	44	0%
Dark clothing dark garments	22	62	6%
				Exempt to press minimum ion	83	87	- 4%
Cotton short are washed and (subtracted drift) to pure cotton	51	119	0%
				Pure cotton washes cotton	51	149	0%
Intensive is washed in reinforcement	108	167	3%

Table 18：Residual rates of the capsule d (pulullan polysaccharide capsule) in 30 DEG C of different washing durations of roller washing machine

	Washing cycle	Master washes the cycle	Residual rate
				Express and (subtract drift) express 20short	11	20	3%
Express express 20	11	30	- 10%
				Shirt shirt short	23	44	3%
Dark clothing dark garments	22	62	- 6%
				Exempt to press minimum ion	83	87	10%
Cotton short are washed and (subtracted drift) to pure cotton	51	119	- 15%
				Pure cotton washes cotton	51	149	- 4%
Intensive is washed in reinforcement	108	167	6%

The error that balance weighs is ± 0.01g, and capsule a-d is #0 capsules, its weight range between 0.08-0.12g, Therefore the systematic error that residual rate calculates is 8%-12%.To ensure the accuracy judged, to capsule while test is weighed Residual condition carried out sense organ evaluation and test, it is found that residual rate does not find to remain in the range of ± 18%, but residual rate exceeds the mistake Poor scope is shown has significant residual after washing.

Gelatine capsule is can be seen that from above-mentioned table 15-18 result under 30 DEG C of roller washing machine wash environments respectively to exist There is obvious residual in wash time 20min, 30min, 44min, 62min, 87min, 149min each program.And other materials The capsule of material, including HPMC capsules, pulullan polysaccharide capsule under 30 DEG C of roller washing machine wash environments various durations it is above-mentioned Do not find significantly to remain in washing procedure.

Table 19：Residual rates of the capsule a (gelatine capsule) in the different washing durations of rotary drum washing machine

	Washing cycle	Master washes the cycle	Residual rate
				15℃	40 minutes	15 minutes	102%
25℃	40 minutes	15 minutes	92%

Table 20：Residual rates of the capsule b (HPMC capsules) in the different washing durations of rotary drum washing machine

	Washing cycle	Master washes the cycle	Residual rate
				15℃	40 minutes	15 minutes	3%
25℃	40 minutes	15 minutes	1%

Table 21：Residual rates of the capsule c (pulullan polysaccharide capsule) in the different washing durations of rotary drum washing machine

	Washing cycle	Master washes the cycle	Residual rate
				15℃	40 minutes	15 minutes	- 1%
25℃	40 minutes	15 minutes	- 5%

Table 22：Residual rates of the capsule d (pulullan polysaccharide capsule) in the different washing durations of rotary drum washing machine

	Washing cycle	Master washes the cycle	Residual rate
				15℃	40 minutes	15 minutes	- 2%
25℃	40 minutes	15 minutes	- 2%

Gelatine capsule is can be seen that under 15 DEG C and 25 DEG C of rotary drum washing machine wash environments from above-mentioned table 15-18 result There is obvious residual.And the capsule of other materials, including HPMC capsules, pulullan polysaccharide capsule are equal under identical wash environment Do not find significantly to remain.

The capsule of embodiment 5. washs assessment of the synergist to fabric nursing effect

1. prepared by material

(the Novozymes A/ of enzyme granulate containing solid cellulose are prepared using commercially available Capsules c (pulullan polysaccharide capsule) S, Carezyme Premium 5000T) laundry booster C to be measured, cellulase content is 0.6g, and enzyme granulate is filled into glue The method in intracapsular portion is as described in example 3 above.

Fabric nursing material used in assessing is EMPA252 (color fringe cloth, the spandex of 94% cotton 6%, purchased from Center For Testmaterials B.V, Netherlands), it is standby after following methods carry out material aging.The side of material aging Method is：EMPA252 after prewashing is placed in Wascator automatic washing machines continuous washing 12 hours, treatment temperature 40 ℃.EMPA252 surfaces after processing it is easy to nursing efficacy to evaluate and test obvious balling-up.

Wash conditions are 25 with reference to embodiment " washing facility and condition " above, the wherein wash temperature of rotary drum washing machine DEG C, detergent surpasses effect enzymatic laundry powder for commercially available Ace of receiving, and the wash temperature of roller washing machine is 40 DEG C, and detergent is commercially available indigo plant Moon deep layer cleaning liquid detergent.For the lasting fabric nursing effect of synergy capsule of withdrawing deposit, the same fabric of continuous monitoring in experiment Clean result of the EMPA252 samples after three-wheel washing is successively gone through.

2. wash synergy capsule synergy test

● experimental group：2,4,6,8 such as the previously described synergy capsule C of the present embodiment are separately added into when washing and originating.

● negative control group：It is added without synergy capsule.

The appraisal procedure of fabric nursing effect is to measure the brightness value (L values) of blackstreak on aging EMPA252, due to mill Sun Qi clubs decline the bright-coloured degree of clothing, i.e., it is graying to be reflected as black on EMPA252 blackstreaks, brightness value rise.Therefore After the completion of washing, measure and calculate the brightness value (L) of each experimental group 1-5 fabric faces and the aging without carrying out washing treatment The difference of the brightness value of EMPA252 fabric face, i.e. Δ L.

Δ L is bigger to prove that fabric nursing effect is more excellent, and it is visible difference to remind during Δ L >=0.5.

Using receiving that the super effect enzymatic laundry powder of Ace and washing is presented after synergy capsule C is washed in rotary drum washing machine to old Nursing efficacy (Δ L) experimental result for changing EMPA252 surfaces is as shown in table 23 below.

Table 23.

Wash round	Negative control group	Experimental group 1	Experimental group 2	Experimental group 3	Experimental group 4
						1	0.42	0.44	0.48	0.36	0.32
2	0.20	0.62	0.61	0.86	1.11
						3	0.08	0.80	1.30	1.78	1.75

As can be seen from Table 23, in the wash environment of rotary drum washing machine：Adding washing synergy capsule C can wash The effect of significantly visible fabric nursing is provided after 2nd wheel, its effect is with the increase of synergy capsule dosage and carrying for washing wheel number Rise and strengthen.The Δ L of negative control group then reduces as washing wheel number increases, and prompts further breaking for fabric face performance It is bad.This shows that the washing synergy capsule comprising cellulase of the present invention provides the significant laundry care effect for removing ball top.

Presented after being washed using blue moon deep layer cleaning and nursing liquid detergent and washing synergy capsule C in roller washing machine It is as shown in table 24 below to nursing efficacy (Δ L) experimental result on aging EMPA252 surfaces.

Table 24.

Wash round	Negative control group	Experimental group 5	Experimental group 6	Experimental group 7	Experimental group 9
						1	-0.42	0.50	0.85	1.23	1.49
2	-0.17	1.69	2.49	3.05	3.16
						3	0.16	3.71	3.98	4.39	4.72

It can be drawn from the experimental result of table 24, in the wash environment of roller washing machine, compared to negative control, sheet The washing synergy capsule C of invention can bring the effect of going the textile finishing of ball top of highly significant after the 1st wheel washing, imitate Fruit is significantly improved with the increase of washing synergy capsule C supply volumes and the increase of washing wheel number.

The capsule of embodiment 6. washs assessment of the synergist to fabric whiteness maintenance effects

1. prepared by material

(the Novozymes A/ of enzyme granulate containing solid cellulose are prepared using commercially available Capsules c (pulullan polysaccharide capsule) S, Carezyme Premium 5000T) and water soluble fluorescers (BASF, CBS-X) laundry booster capsule 1- to be measured 2, capsule 's content content is as described in table 25.Enzyme granulate and fluorescent whitening agent are filled into the method such as embodiment 3 of capsule Described in.

Table 25

Capsule 1	0.018g Celluclean 5000T
		Capsule 2	0.005g FWA+0.018g Celluclean 5000T

Fabric nursing material used in assessing is white knitting cotton (CN42, purchased from Center for Testmaterials B.V, Netherlands) and white towel cloth (WFK12AW, purchased from Testfabrics, Inc.).Using The setting of the Terg-O-Tometer of embodiment " washing facility and condition " part is washed above, and detergent is done washing for above-mentioned model Powder.For speeding-up simulation white fabrics, whiteness caused by grime declines situation in washing repeatedly, is added in wash environment 0.8g/L liquid carbon blacks simulate spot.

For the test condition of each experimental group as described in table 26, positive control is unprocessed, negative control and other each realities It is to be washed using 2g/L models washing powder (as described in embodiment material part above) to test group, and wherein fluorescent whitening agent group is (real Test group and 0.005g fluorescent whitening agents, capsule 1 group (experimental group 2) and capsule 2 groups (experimental groups 3) 1) are additionally added in washing process Then additionally add 1-2 grains and wash synergy capsule accordingly.

After the completion of washing, the decline that surface luminous intensity after each experimental group fabric washing corresponds to positive controls is measured and calculated Value, i.e. Δ Rem.Δ Rem is smaller to represent that fabric face light intensity value reduces fewer, i.e. whiteness maintenance effect is better.

Table 26

It is can be seen that from the result of table 26 compared to undressed negative control group, fluorescent whitening agent group (experimental group 1) The reduction of the whiteness of fabric can effectively be slowed down with the experimental group 2 for adding the laundry booster capsule 1 containing cellulase.And The experimental group 3 of laundry booster capsule 2 of the addition containing both compositions then embodies the synergy between both components, i.e., Significantly more whiteness maintenance effect, and the effect strengthens with the increase of the usage amount of capsule 2.

Dimension disclosed herein and value, which are not intended to, to be understood to be limited strictly to described exact value.It is on the contrary, unless another Indicate outside, each such dimension refer to cited numerical value and around the numerical value work(40mm " dimension be intended to indicate that " about 40mm"。

The All Files quoted in detailed description of the invention is hereby incorporated herein by relevant portion.For any file Reference be not construed as recognizing that it is prior art for the present invention.When any implication of term or definition in the present invention During with being introduced into any implication of term in file for reference or define contradiction, it should obey and assign the term in the present invention Implication or definition.

Although specific embodiments of the present invention have had been illustrated and described, come for those skilled in the art Say it is readily apparent that multiple other changes and modification can be made in the case of without departing substantially from spirit and scope of the present invention.Cause This, claims are intended to cover in all such changes and modification in the scope of the invention.

Claims

1. a kind of synergy capsule for being used to strengthen the clean result in short distance washing, it includes capsule shell, and included in capsule Internal washing enzyme.

2. the synergy capsule described in claim 1, wherein the capsule shell has the washing containing 2% surfactant at 20 DEG C Wash in liquid disintegration time and be no more than 30 minutes, preferably more than 20 minutes, no more than 15 minutes, no more than 10 minutes, no more than 8 Minute, no more than 6 minutes, the disintegrating property no more than 5 minutes.

Do not surpass in 15 DEG C -30 DEG C of washing process 3. the synergy capsule described in claim 1 or 2, wherein capsule shell have 18% is crossed, no more than 12%, preferably more than 10%, preferably more than 8%, preferably more than 6%, preferably more than 4% are excellent Choosing is no more than 3%, preferably more than 1% residual rate.

4. the synergy capsule described in claim any one of 1-3, wherein short distance washing includes the washing no more than 110 minutes Cycle, preferably more than 100 minutes, no more than 90 minutes, no more than 80 minutes, no more than 60 minutes, no more than 50 minutes, no More than 30 minutes.

5. the synergy capsule described in claim 4, wherein the master in the washing cycle washed the cycle no more than 90 minutes, it is no more than 70 minutes, preferably more than 50 minutes, preferably more than 30 minutes, preferably more than 20 minutes, preferably more than 15 minutes, it is excellent Choosing is no more than 12 minutes.

6. the synergy capsule described in any one of the claims, wherein short distance washing, which has, is no more than 90 DEG C, preferably not More than 60 DEG C, preferably more than 40 DEG C, preferably more than 35 DEG C, preferably more than 30 DEG C, preferably more than 20 DEG C, preferably do not surpass 10 DEG C are crossed, preferably more than 4 DEG C of master washes temperature.

7. the synergy capsule described in any one of the claims, wherein the capsule shell is by selected from the material system of the following group Into：Cellulose derivative, starch derivatives, pulullan polysaccharide, and combinations thereof.

8. the synergy capsule described in claim 7, the capsule shell are made up of pulullan polysaccharide material.

9. the synergy capsule described in any one of the claims, wherein the washing is selected from following group with enzyme：Protease, form sediment Powder enzyme, it is cellulase, lipase, phosphatidase, cutinase, oxidizing ferment, oxygenase, transferase, reductase, hemicellulase, sweet Reveal dextranase, esterase, isomerase, pectase, lactase, peroxidase, lyase, laccase, deoxyribonuclease, lichens Polysaccharase, and combinations thereof.

10. the synergy capsule described in claim 9, the washing is selected from following group with enzyme：Protease, amylase, sweet dew gather Carbohydrase, cellulase and combinations thereof.

11. the synergy capsule described in any one of the claims, the washing is with containing substantially no surfactant, drift in enzyme White agent or bleach activator.

12. the synergy capsule described in any one of the claims, the washing enzyme for without enzyme stabilizers composition it is low into This enzyme granulate form.

13. the synergy capsule described in any one of the claims, its size is 5mm-100mm.

14. the synergy capsule described in claim 1, the clean result of the enhancing are selected from：Spot is removed, whiteness is maintained, reduces Balling-up, fabric color nursing, remove smell, remove biomembrane, prevent, reduce and/or go dirt to adhere to, and combinations thereof.

15. a kind of synergy capsule for being used to strengthen clean result, it includes capsule shell made of pulullan polysaccharide material, and bag The washing enzyme being contained in above-mentioned capsule shell.

16. pulullan polysaccharide is preparing the application in being used to strengthen the synergy capsule of clean result.

17. a kind of kit, it includes the synergy capsule described in one or more any one of claim 1-13, the synergy glue There is corresponding visual identity key element on capsule.

18. the kit described in claim 14, the synergy capsule is individually wrapped in blister package material.

19. the method for the synergy capsule as described in claim any one of 1-12 is prepared, including：

A. screen in the washing process at 25 DEG C residual rate and be no more than 18%, preferably more than 12%, preferably more than 10%, Preferably more than 8%, preferably more than 6%, preferably more than 4%, preferably more than 3%, outside preferably more than 1% capsule Shell,

B. washing is filled into inside capsule shell with enzyme synergist.

20. the method described in claim 16, the following steps being additionally included in before step b：

C. screening is no more than 30 minutes with disintegration rate in the cleaning solution containing 2% surfactant at 20 DEG C, does not preferably surpass 20 minutes are spent, no more than 15 minutes, no more than 10 minutes, no more than 8 minutes, no more than 6 minutes, the capsule no more than 5 minutes Shell,

Wherein step c is carried out afterwards or simultaneously before step a.