WO2019029530A1 - 增效胶囊 - Google Patents

增效胶囊 Download PDF

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Publication number
WO2019029530A1
WO2019029530A1 PCT/CN2018/099196 CN2018099196W WO2019029530A1 WO 2019029530 A1 WO2019029530 A1 WO 2019029530A1 CN 2018099196 W CN2018099196 W CN 2018099196W WO 2019029530 A1 WO2019029530 A1 WO 2019029530A1
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Prior art keywords
capsule
washing
synergistic
minutes
enzyme
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PCT/CN2018/099196
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English (en)
French (fr)
Inventor
周玉成
蔡悦
Original Assignee
诺维信公司
周玉成
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Application filed by 诺维信公司, 周玉成 filed Critical 诺维信公司
Publication of WO2019029530A1 publication Critical patent/WO2019029530A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/38—Products with no well-defined composition, e.g. natural products
    • C11D3/386—Preparations containing enzymes, e.g. protease or amylase
    • C11D3/38672—Granulated or coated enzymes

Definitions

  • the present invention relates to a synergistic capsule for enhancing the washing effect, and a method of preparing the synergistic capsule.
  • high quality performance detergents typically contain one or more enzymes that remove different soil components.
  • the formulation of the detergent product is designed to take into account the storage stability of the enzyme incorporated therein and the stability of application during the washing process.
  • the enzyme is dispersed evenly throughout the wash product in the form of granules. Maintaining the stability of the enzyme is a technical challenge because the enzyme is a protein whose activity is affected by components in the detergent such as anionic surfactants or bleaches, and the protease also acts on other enzymes by its proteolysis. The activity has an effect.
  • 6,413,928 describes the preparation of a multiphase detergent tablet having a gel fraction.
  • the sheet physically separates the enzyme from the bleach and surfactant.
  • the commercially available product with enzymes and bleaches can be obtained in the form of tablets and is known as Recinitt Benckiser's Vanish Action Ball. Such technical solutions further increase the cost of enzyme-containing detergents.
  • the cost structure often results in the inability to use enzymes or high doses of enzymes in them, or the addition of additional ingredients that control enzyme activity to the formulation, or the inability to configure the ingredients that will affect enzyme activity.
  • the complex structure of the enzyme is physically isolated.
  • CN101218334A discloses fabric care enzyme tablets for consumers that can be added in a single dose during the wash cycle of an automatic washing machine or dishwasher.
  • the single dose tablet is an enzyme together with an excipient such as microcrystalline cellulose, stearic acid enzyme or the like by a flow bed process.
  • the process of tableting is relatively complicated, and in order to prevent the consumer from directly contacting the enzyme synergist or the dust generated by the tablet during use, the enzyme is allergic, and it is also required to spray a water-soluble film-forming material such as polyethylene glycol for tableting. surface.
  • CN101218334A only discloses the use in European long-range washing procedures.
  • the present invention provides a cost effective method for delivering an enzyme directly to a consumer in the form of a capsule without encountering problems with enzyme stability, and can be significant in relatively short-range wash cycles, such as relatively long-range washing procedures in Europe.
  • the enzyme washing synergy is rapidly exerted.
  • the consumer can more easily recognize the increased washing of the enzyme for removing specific stains than the detergent in which the enzyme is dispersed evenly. The effect and tend to be more acceptable and recognized for the use of the enzyme in the washing process.
  • the use of enzymes can save a lot of energy used in traditional enzyme-free detergent applications, including electricity and water use, while achieving the same or increased washing effect, in addition to reducing the impact of washing wastewater discharge Environmental pressure.
  • the present invention is directed to a synergistic capsule comprising a capsule outer shell, and a washing enzyme contained within the outer shell of the capsule, which is capable of enhancing the washing effect in short-range washing.
  • the present invention is directed to a synergistic capsule comprising a capsule shell made of a pullulan material, and a washing enzyme contained in the capsule shell described above, which is capable of enhancing the washing effect in short-range washing.
  • the present invention relates to the use of a cellulose derivative, a starch and a starch derivative, pullulan, and combinations thereof for the preparation of a synergistic capsule for enhancing the washing effect.
  • the invention in another aspect, relates to a kit comprising one or more of the synergistic capsules described above having visual recognition elements corresponding to the function of the enzymes contained within the wash enzyme.
  • the present invention relates to a method of preparing a synergistic capsule as hereinbefore described, comprising: screening a capsule shell having a residual rate of no more than 18% during washing at 25 ° C, and filling the washing enzyme synergist with Inside the capsule housing.
  • delta Enzyme Performance Value The term "deltaase reflectance value" or “ ⁇ Enz” or “ ⁇ Enz” is defined herein as the result of a reflectance or reflectance measurement at 460 nm.
  • the patch swatch is measured as a background using a small swatch of similar color, preferably a small swatch from repeated washing. Prior to washing, a small swatch representing each swatch type was measured.
  • the delta enzyme performance value is the reflection value of the small swatch washed with the detergent in the presence of an enzyme minus the similar swatch-like reflection value washed with the detergent-free detergent.
  • Delta Reflection Value ([Delta]Rem):
  • the term "delta reflection” or “delta reflection value” is defined herein as the result of a reflectance or reflection measurement at a wavelength, typically 460 nm.
  • the swatch is measured with a swatch of similar color, preferably a swatch from repeated washing as a background. A swatch representing each swatch type is measured before washing.
  • the delta reflection is the reflection value of the washed swatch minus the reflection value of the unwashed swatch.
  • Detergent Composition refers to a composition for removing undesirable compounds from articles to be cleaned, such as textiles, tableware, and hard surfaces.
  • the detergent compositions can be used, for example, for cleaning textiles, tableware, and hard surfaces for both household cleaners and industrial cleaning.
  • washing Compositions for example, liquid and/or solid laundry detergents and fine fabric detergents; hard surface cleaning formulations, for example for glass, wood, ceramics and metal countertops and windows; carpet cleaners; stove cleaners; fabric fresheners a fabric softener; and a pre-spotter for textiles and clothing, together with dishwashing detergents.
  • the detergent formulation may also comprise one or more additional enzymes (eg protease, amylase, lipase, cutinase, cellulase, endoglucanase) , xyloglucanase, pectinase, pectin lyase, xanthan gumase, peroxidase, halogen peroxygenase, catalase, and mannanase, or any mixture thereof), and / or components, such as surfactants, builders, chelators or chelating agents, bleaching systems or bleaching components, polymers, fabric conditioners, foam boosters, suds suppressors, Dyes, perfumes, tarnish inhibitors, optical brighteners, bactericides, fungicides, soil suspending agents, corrosion inhibitors, enzyme inhibitors or stabilizers, enzyme activators, one or more transferases, hydrolases , oxidoreductases, bluing
  • additional enzymes eg protease,
  • Dishwashing refers to all forms of dishwashing, such as manual or automatic dishwashing (ADW). Washing dishes include, but are not limited to, cleaning all forms of pottery, such as plates, cups, glasses, bowls, all forms of dining tools such as spoons, knives, forks, and serving utensils along with ceramics, plastics, metals, porcelain, glass. And acrylate.
  • Short-range washing refers to the Asian washing process and the American washing process which are significantly shortened throughout the washing process compared to the usual washing habits and washing time in Europe.
  • the European wash program includes a main wash cycle and a rinse cycle for a total length of up to 3 hours, wherein the main wash cycle can be as long as 50-110 minutes; the short wash wash described in the present invention typically does not exceed 110 minutes. Preferably, it does not exceed 100 minutes, does not exceed 90 minutes, does not exceed 80 minutes, does not exceed 60 minutes, does not exceed 50 minutes, and does not exceed 30 minutes.
  • Main wash cycle is meant to include soaking a textile or other item to be washed in a wash liquor, applying a mechanical action to the textile to release the dirt, and assisting the flow of the wash liquid into and out of the wash. The process of textiles or other items to be washed, and eventually removing excess washing liquid.
  • the main wash cycle of the short-range wash of the present invention generally does not exceed 90 minutes, preferably does not exceed 70 minutes, preferably does not exceed 50 minutes, preferably does not exceed 30 minutes, preferably does not exceed 20 minutes, preferably does not exceed 15 minutes, preferably does not exceed 15 minutes, preferably does not exceed 12 minutes. .
  • Leaching cycle refers to the process of rinsing and dehydrating textiles or other items to be washed with clean water without washing liquid after the main washing cycle is completed.
  • Washing liquid is defined herein as a solution or mixture optionally comprising water and detergent for washing textiles or other items to be washed.
  • Hard surface cleaning is defined herein as a clean hard surface, wherein the hard surface may include a floor, table, wall, roof, etc., along with the surface of a hard object, such as a car (car wash) and tableware (dishwashing) ).
  • Dishwashing includes, but is not limited to, cleaning dishes, cups, glasses, bowls, dining utensils (eg spoons, knives, forks), serving utensils, ceramics, plastics, metals, porcelain, glass, and acrylates.
  • Enhanced Washing Effect is defined herein to mean that the addition of a synergistic capsule during the washing process exhibits an increased washing effect relative to the washing effect of a detergent composition without a synergistic capsule, for example, removal of stains, Maintain whiteness, reduce pilling, fabric color care, remove odors, remove biofilms, prevent, reduce and/or remove dirt adhesion.
  • the term “enhanced washing effect” includes washing effects in laundry washing and, for example, in hard surface cleaning such as automated dishwashing (ADW).
  • the synergistic capsules of the present invention can be used to enhance one or more of the above washing effects.
  • Laundry relates to both domestic laundry and industrial laundry and refers to the process of treating textiles with a solution comprising the cleaning or detergent composition of the present invention.
  • the laundry process can be performed, for example, using, for example, a domestic or industrial washing machine or can be performed manually.
  • Textile means any textile material comprising yarns, yarn intermediates, fibers, non-woven materials, natural materials, synthetic materials, and any other textile material, fabrics made from these materials and made from these fabrics. Products (such as clothing and other items).
  • the textile or fabric may be in the form of knitwear, woven fabric, denim, non-woven fabric, felt, yarn, and terry cloth.
  • These textiles may be cellulose based, such as natural cellulose, including cotton, linen/linen, jute, ramie, sisal or coir or man-made cellulose (eg, derived from wood pulp), including viscose/artificial Silk, cellulose acetate fibers (tricone), lyocell or blends thereof.
  • Textiles or fabrics may also be based on cellulose, such as natural polyamides, including wool, camel hair, cashmere, mohair, rabbit hair and silk or synthetic polymers such as nylon, aramid, polyester, acrylic, polypropylene and spandex. / spandex/elastane, or blends thereof, and blends based on cellulose and non-cellulose based fibers.
  • cellulose such as natural polyamides, including wool, camel hair, cashmere, mohair, rabbit hair and silk or synthetic polymers such as nylon, aramid, polyester, acrylic, polypropylene and spandex. / spandex/elastane, or blends thereof, and blends based on cellulose and non-cellulose based fibers.
  • a blend is a blend of cotton and/or rayon/fibrous glue with one or more accompanying materials such as wool, synthetic fibers (eg polyamide fibers, acrylic fibers, polyester fibers, Polyvinyl chloride fiber, polyurethane fiber, polyurea fiber, aramid fiber) and/or cellulose-containing fiber (such as rayon/fiber glue, ramie, linen/linen, jute, cellulose acetate fiber, Lacey Fiber).
  • the fabric can be a conventional washable garment, such as a stained household garment. When the term fabric or garment is used, it is intended to also include the broad term textile.
  • Whiteness is defined herein as a broad term that has different meanings in different fields and for different customers.
  • the loss of whiteness can be attributed, for example, to ashing, yellowing, or removal of optical brightener/toner. Ashing and yellowing can be attributed to soil redeposition, body soiling, coloration from, for example, iron and copper ions or dye transfer.
  • Whiteness may include one or several problems from the following list: colorant or dye action; incomplete soil removal (eg body dirt, sebum, etc.); redeposition (ashing, yellowing or other discoloration of the object) (removed The soil is re-associated with other parts of the textile (stained or unsoiled); chemical changes in the textile during application; and clarification or lightening of the color.
  • Disintegration performance refers to the speed-related property of the capsule shell cleavage release content defined by the disintegration time under specific conditions.
  • Disintegration time refers to the time required for the capsule shell to rupture to expose the enzyme for washing during the washing process, and the specific measurement is as described in the section “Measurement of Disintegration Time” in the section of the analysis method below. Detailed Description.
  • Residual rate means the proportion of the portion of the capsule casing which is not completely dissolved during the washing process and remains on the surface of the washing article or the washing machine, and the specific measurement is described in the section “Analysis Method” below. A detailed description of the rate.
  • the present invention is directed to a synergistic capsule comprising a capsule outer shell, and a washing enzyme contained within the outer shell of the capsule, which is capable of enhancing the washing effect in a short-range washing procedure.
  • a synergistic capsule comprising a capsule outer shell, and a washing enzyme contained within the outer shell of the capsule, which is capable of enhancing the washing effect in a short-range washing procedure.
  • the total duration of common washing procedures in Europe and the duration of the main wash cycle are longer than those common in washing procedures in Asia and the United States.
  • the inventors of the present invention have surprisingly discovered that synergistic capsules prepared from capsule shells of certain materials can achieve a washing synergistic effect of the washing enzyme at a relatively short wash cycle and/or a relatively low wash temperature without It experiences much longer wash times and generally higher wash temperatures that are typically required in Europe, while not producing unwanted capsule residues.
  • the physicochemical structure and properties of the capsule shell of the synergistic capsules of the present invention suitable for short-term washing procedures, such as water solubility, disintegration properties, and enzymes which may be involved in the encapsulation of the capsules
  • the interaction contributes to the significantly enhanced washing effect of the synergistic capsules of the present invention.
  • the use of the synergistic capsule of the present invention in combination with a detergent in a washing procedure can achieve a superior washing effect compared to the use of a synergistic capsule at a relatively short washing time and a relatively low washing temperature, thereby being effective in effectively It can save energy consumption, water consumption, and reduce sewage discharge, which is conducive to environmental protection and resource conservation, and is conducive to the development of green ecological society.
  • the capsule shell of the synergistic capsule of the present invention has a disintegration time of no more than 30 minutes, preferably no more than 20 minutes, no more than 15 minutes, in a wash solution containing 2% surfactant at 20 ° C. More than 10 minutes, no more than 8 minutes, no more than 6 minutes, no more than 5 minutes. Since the Asian washing process is generally a relatively short-term washing cycle, if the washing enzyme is expected to function in the short-term washing cycle, the capsule shell of the synergistic capsule is required to have a shorter disintegration time, so that the washing enzyme can be The washing liquid is released as soon as possible to allow a longer period of time for the catalysis of the enzyme to achieve the washing and synergistic function of the enzyme for washing.
  • the capsule shell of the synergistic capsule of the present invention has no more than 18%, no more than 12%, preferably no more than 10%, preferably no more than 8% during the washing process at 15 ° C to 30 ° C.
  • a residual ratio of not more than 6%, preferably not more than 4%, preferably not more than 3%, preferably not more than 1% is preferred.
  • the synergistic capsules of the present invention are capable of achieving significant synergistic effects in a short-range wash procedure, wherein the short-range wash comprises a wash cycle of no more than 110 minutes, preferably no more than 100 minutes, no more than 80 minutes, no more than 60 minutes, no more than 50 minutes, no more than 30 minutes.
  • the main wash cycle in the short-range wash procedure is no more than 90 minutes, no more than 70 minutes, preferably no more than 50 minutes, preferably no more than 30 minutes, preferably no more than 20 minutes, preferably no more than 15 minutes, preferably No more than 12 minutes.
  • the synergistic capsule of the present invention is preferably capable of achieving a synergistic effect of the enzyme for washing at a relatively low washing temperature without significant residual problems.
  • the short-range washing procedure has a washing temperature of no more than 60 ° C, preferably no more than 40 ° C, no more than 35 ° C, no more than 30 ° C, no more than 20 ° C, no more than 10 ° C, no more than 4 ° C .
  • the capsule shell of the synergistic capsule of the present invention is made of a material comprising a cellulose derivative, a starch derivative or pullulan, preferably a material comprising pullulan.
  • the enzyme for washing contained in the synergistic capsule of the present invention is selected from the group consisting of proteases, amylases, cellulases, lipases, phospholipases, cutinases, oxidases, oxygenases, Transferase, reductase, hemicellulase, mannanase, esterase, isomerase, pectinase, lactase, peroxidase, lyase, laccase, deoxyribonuclease, lichenase And its combination.
  • the washing enzyme is selected from the group consisting of a protease, an amylase, a mannanase, a cellulase, and combinations thereof.
  • the enzyme for washing contained in the synergistic capsule of the present invention contains substantially no surfactant, bleach or bleach activator.
  • the synergistic capsules of the present invention are preferably used in conjunction with low cost detergents in the washing process, which typically do not contain detergent enzymes, or contain only a small amount and/or a low price of one or more Kind of enzyme. Since the synergistic capsule of the present invention is provided in a single dose form independent of washing, the consumer can select a particular one or more synergistic capsules to be used in conjunction with the detergent depending on the particular stain to which the laundry and appliance are to be attached. Can effectively remove stains.
  • the enzyme for washing contained in the synergistic capsule of the present invention is in the form of a low cost enzyme granule containing no enzyme stabilizer component.
  • the synergistic capsules of the present invention can provide a cost effective method of delivering the enzyme directly to the consumer without concern for enzyme stability and compatibility with other ingredients in the detergent.
  • the synergistic capsules of the present invention have a size of about 5 mm, about 10 mm, about 20 mm, about 30 mm, about 40 mm, to about 100 mm.
  • the capsule shape of the present invention is similar to that of a generally visible pharmaceutical capsule, which is oval or oblong, and when describing its size, the long axis of the capsule is usually used as an indication of its size.
  • the synergistic capsules of the present invention provide enhanced cleaning effects selected from the group consisting of: removing stains, maintaining whiteness, reducing pilling, fabric color care, removing odors, and combinations thereof.
  • the present invention is directed to a synergistic capsule for enhancing a washing effect comprising a capsule shell made of a material comprising pullulan, and a washing enzyme contained in the capsule shell.
  • the invention relates to the use of pullulan in the preparation of a synergistic capsule for enhancing the washing effect.
  • the invention in another aspect, relates to a kit comprising one or more of the synergistic capsules described above, the synergistic capsule having corresponding visual recognition elements thereon.
  • the visual identification element can help the consumer to understand one or more of the washing synergies that a particular booster capsule can provide.
  • the synergistic capsules are individually wrapped in a blister packaging material, and the synergistic capsules may be in a single package or a combination of multiple packages, for example, forming a continuous row, or forming a square matrix in successive rows. The form is provided.
  • the invention in another aspect, relates to a method of preparing a synergistic capsule as hereinbefore described, comprising: a) screening a residual rate of no more than 18%, no more than 12 during the washing process at 15 ° C to 30 ° C, preferably 25 ° C. %, preferably no more than 10%, preferably no more than 8%, preferably no more than 6%, preferably no more than 4%, preferably no more than 3%, preferably no more than 1% of the capsule shell, and b) synergistic for washing enzymes The agent is filled into the interior of the capsule casing.
  • step c) screening has a disintegration rate in the wash liquor containing 2% surfactant at 20 ° C of no more than 30 minutes, preferably no more than 20 minutes, 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 of the capsule casing, wherein step c) is carried out before, after or simultaneously with step a).
  • the capsule shell of the synergistic capsule of the present invention may be selected such that the synergistic capsule is a hard capsule or a soft capsule.
  • Hard capsules are typically used to fill the contents of the powder or granules, while soft capsules are more suitable for liquid, semi-liquid or oil-based contents.
  • the capsules and drug capsules of the present invention also differ in the manner and manner of delivery due to the differences in the content that is expected to be delivered.
  • the synergistic capsule is a hard capsule.
  • the hard capsule consists of a two-part shell comprising a "capsule body" in which the active substance is filled, and a "cap” closely fitted to the "capsule body".
  • the capsule body and cap can be prepared in advance or can be purchased from a capsule manufacturer. As the name suggests, hard capsules are hard and non-flexible.
  • the washing enzyme whether in granules or powder form, and whether or not it is mixed with a carrier material or a suitable diluent and excipient such as lactose, magnesium stearate, or starch, can be incorporated into the empty capsule body.
  • the cap is then placed on the capsule body and the two are closely fitted to completely encapsulate the enzyme for washing. This method can be done manually, but more typically by applying a variety of commercially available capsule filling machines.
  • the hard capsule shell is made of a material comprising a polysaccharide, including but not limited to:
  • CN1202102A discloses capsules made of carboxymethylcellulose calcium or croscarmellose sodium, gelatinized starch and polyvinylpolypyrrolidone.
  • CN1292261A discloses a plant hard capsule made of a hydrophilic gel, a water-soluble cellulose, a coagulant.
  • CN1646369A discloses capsules made of a water-soluble cellulose derivative such as hydroxyprolylmethylcellulose, a plasticizer or the like.
  • CN1745745A discloses hollow capsules made of K-carrageenan, cellulose derivatives such as hypromellose, ethylcellulose, hydroxypropylcellulose, carboxymethylcellulose, alcohols.
  • Plant starch capsule made of plant starch (such as potato starch, tapioca starch) and starch derivatives (such as hydroxypropyl starch, hydroxypropyl carboxymethyl starch) as the main raw material, with a certain plasticizer.
  • Hydroxypropyl starch especially hydroxypropyl starch with a hydroxypropyl group content within a certain range, after being gelatinized by heating at a certain temperature, and stable for a certain time under different temperature conditions, can be added or not Under conditions of little addition of plasticizers, binders and gelling agents, hydroxypropyl starch hollow capsules which are fully compatible in performance and quality for use in the present invention are obtained.
  • CN1483393A and the production process thereof are made of plant starch or starch derivative, plasticizer, water and the like.
  • the capsule disclosed in CN1623529A consists of potato starch, carrageenan, a surfactant, and a plasticizer.
  • CN1739488A discloses a modification of konjac glucomannan by acid hydrolysis, with modified or unmodified vegetable protein (including soy protein, zein, wheat protein, zein), animal gelatin or fish gelatin. Or two kinds of complexes as main components, and auxiliary components such as glycerin and dodecylsulfonate are made into hollow capsules.
  • the hollow capsule disclosed in CN1895234A is prepared by using amylose and glycerin as main raw materials.
  • CN1931145A discloses plant hollow capsules made of amylose or soluble starch such as corn, potato, cassava, sweet potato, hawthorn extract and glycerin
  • CN1687203A discloses gelatinization of starch and proportional addition of plasticizer, gel and surface activity.
  • CN103893772B discloses a hydroxypropyl starch hollow capsule composed of hydroxypropyl starch, water, a binder, an opacifier, a colorant, a fragrance, and/or a flavoring agent.
  • CN104800189B discloses a starch plant hollow capsule, which is mainly prepared by a process of preparing a hollow capsule by 50-80 parts of natural starch, 30-50 parts of vegetable fiber and 50-90 parts of deionized water, and then characterized by
  • the plant fiber is mainly selected from the group consisting of pomelo cellulose
  • the natural starch is selected from tapioca starch
  • the hollow capsule further comprises carrageenan, konjac gum, gellan gum, xanthan gum and flax gum in vegetable gum.
  • One or a combination of phthalocyanine One or a combination of phthalocyanine.
  • CN104586813B discloses a whole starch plant capsule comprising 75% to 90% of whole starch vegetable gum, 5% to 20% water, 0 to 5% binder, 0 to 2% sunscreen agent, and 0 to 3% coloring agent.
  • the flavoring agent is 0 to 5%.
  • starch capsules are disclosed, for example, in CN105395513B, CN105030723B, CN105017567B, CN104800188B, CN104800189B, CN104586813B CN103893772B, CN104800186B.
  • polysaccharide capsules include, for example, a hollow capsule made of a seaweed polysaccharide gum as disclosed in CN1903157A.
  • a capsule made of other polysaccharide polymers as a main raw material such as a pullulan capsule.
  • Pullulan the English name of Pullulan, is also translated as pullulan, pullulan, scutellaria, and polysaccharide. It can be directly fermented by starch hydrolysate, sucrose, or other sugars. It is a spore stalk.
  • the extracellular polysaccharide produced by mildew mainly combines maltose with ⁇ -1,6-glycosidic bond to form homopolysaccharide, that is, glucose is combined into ⁇ -1,4-glycosidic bond to form maltotriose, and both ends are ⁇ -1,6-
  • the glycosidic bond is combined with another maltotriose, and thus repeatedly connected to form a polymer polysaccharide, the ratio of the ⁇ -1,4-glycosidic bond to the ⁇ -1,6-glycosidic bond is 2:1, the degree of polymerization is 10 to 30000, and the molecular weight is 2.0. ⁇ 103 to 5.0 ⁇ 106 Daltons.
  • Pullulan polysaccharide can be obtained by sterilizing, decolorizing, desalting, and then dehydrating and drying the pullulan fermentation broth by spraying, fluidized bed, etc., or by using organic solvent method, such as dried product, such as Chinese patent publication CN1651467A
  • the pullulan fermentation broth is sterilized, and then obtained by decolorizing, desalting, and dehydrating the precipitate with an organic solvent such as ethanol or isopropyl alcohol.
  • Other pullulan capsules suitable for use in the present invention include those disclosed in European Patent No. EP 2 663 294 B1, CN 107951858 A, CN 106236730 A, CN 105055365 B.
  • the capsule shell of the synergistic capsule is a cellulose derivative capsule or a pullulan capsule.
  • the capsule shell of the synergistic capsule is a pullulan capsule.
  • Pullulan capsules have the same transparency as gelatin capsules, making the filling contents clearly visible, stable in wide temperature and humidity range, low oxygen permeability and avoiding oxidation of the filling contents, while avoiding the treatment of animals during gelatin capsule preparation.
  • the pollution problem caused by fur and the like and the disintegration speed of gelatin in the washing process are not fast enough, and the residue of the capsule material adheres to the washing clothes and other hard surfaces after the washing process, thereby seriously affecting the evaluation of the washing effect by the consumer. The problem.
  • hard capsules include: plant capsules (Suzhou Capsule Capsugel), this is a kind of HPMC (hypromellose) capsule, natural capsule Plantcaps TM (Suzhou Capsule Capsugel), which is a pullulan capsule.
  • HPMC high-methylcellulose
  • Plantcaps TM Stezhou Capsule Capsugel
  • seaweed polysaccharide capsule #0, respectively, can be purchased from Jiangsu Chenxing Pharmaceutical Co., Ltd. and Shanghai Hongxing Plant Rubber Pill Co., Ltd., Xiangerkang Starch Capsule (#0, purchased from Hunan Erkang Pharmaceutical Co., Ltd.).
  • the capsule shell is made of a non-gelatin material.
  • the hard capsule is preferably a capsule shell having no more than 30 minutes, preferably no more than 20 minutes, in a wash solution containing 2% surfactant at 20 ° C. 15 minutes, no more than 10 minutes, no more than 8 minutes, no more than 6 minutes, no more than 5 minutes of disintegration time.
  • the material of the hard capsule of the invention is preferably selected to have no more than 18%, no more than 12%, preferably no more than 10%, preferably no more than 8% during the washing at 15-30 °C.
  • the residual ratio is not more than 6%, preferably not more than 4%, preferably not more than 3%, preferably not more than 1%.
  • the capsule shell of the synergistic capsule is a soft gel capsule.
  • a soft gel capsule is a sealed, soft shell containing a liquid, suspension or semi-solid as a filler.
  • the soft gel capsule shell is made of a film-forming material and a water-dispersible or water-soluble plasticizer to impart flexibility.
  • Soft capsules can be made from polymers such as hydroxypropyl methylcellulose. Suitable liquid filling materials are vegetable oils, waxes, or polyethylene glycols or other liquids that are compatible with the capsule composition.
  • Soft gel capsules can deliver liquid enzymes or deliver dried enzyme granules such as suspending agents.
  • a soft gel capsule is prepared and the enzyme or active ingredient is mixed with the filling material.
  • a capsule substrate is prepared by mixing a film forming material and a plasticizing material. The formation and filling of the capsules are carried out simultaneously.
  • the encapsulation machine forms the capsule substrate into two films that are fed between two rotating dies.
  • the mold contains depressions of capsule shape and size.
  • the pump in synchronism with the mold transports the liquid filling material into the depression, and then, after filling, the capsule is immediately sealed by pressure.
  • the soft gel capsules are subjected to a two-step drying process, which is done in a tumble dryer or a fluid bed dryer, followed by tray drying or curing for several days.
  • the synergistic capsule of the present invention comprises a washing enzyme contained inside the capsule casing.
  • the enzyme used in the context of the present application may be any enzyme or a combination of different enzymes that can be obtained by fermentation.
  • enzyme it is generally understood to include a single enzyme and a combination of more than one enzyme.
  • enzyme includes variants of the enzyme (eg, prepared by recombinant techniques). Examples of variants of these enzymes are described in, for example, EP 251,446 (Genencor), WO 91/00345 (Novo Nordisk), EP 525,610 (Solvay) and WO 94/02618 (Gist-Brocades NV).
  • Genencor Gene Chemas X-100
  • WO 91/00345 Novo Nordisk
  • EP 525,610 Solvay
  • WO 94/02618 Gist-Brocades NV.
  • the classification of enzymes used in the present specification and claims is consistent with the recommendations of the International Federation of Biochemistry and Molecular Biology Committee Nomenclature (1992) published by the Academic Publishing Company in 1992 (Recommendations (1992) of the Nomenclature Committee of The International Union of Biochemistry and Molecular Biology, Academic Press, Inc., 1992).
  • Washing enzymes suitable for use in the synergistic capsules of the present invention include proteases, cellulases, lipases, phospholipases, cutinases, oxidases, oxygenases, transferases, reductases, hemicellulases, mannose Carbohydrase, amylase, esterase, isomerase, pectinase, lactase, peroxidase, pectate lyase, laccase, deoxyribonuclease, lichenase, and mixtures thereof.
  • Preferred enzymes include those capable of hydrolyzing substrates (e.g., stains). These enzymes are known as hydrolases including, but not limited to, proteases (bacterial, fungal, acidic, neutral or basic proteins), amylases (a or p), lipases, cellulases, and mixtures thereof.
  • Suitable proteases may be of animal, plant or microbial origin.
  • the protease is chemically modified or protein engineered.
  • the protease is a serine protease or a metalloprotease, preferably an alkaline microbial protease or a trypsin-like protease.
  • alkaline proteases are, for example, subtilisins, such as those from the genus Bacillus, for example, subtilisin and (Novo), subtilisin Carlsberg, subtilisin 309, subtilisin 147, subtilisin 168 (described in Protease of WO89/06279).
  • trypsin-like proteases include bovine trypsin, porcine trypsin and Fusarium protease, as described in WO 89/06270 and WO 94/25583.
  • useful proteases are those described in WO 92/19729, WO 98/20115, WO 98/20116, and WO 98/34946, especially those having one or more substituted proteases at the following positions : 27, 36, 57, 76, 87, 97, 101, 104, 120, 123, 167, 170, 194, 206, 218, 222, 224, 235, and 274.
  • Preferred commercially available proteases include, but are not limited to, Duralase TM , Durazym TM , Ultra, Ultra, Uno, Excel, Ultra, Ultra, Blaze 100T, Blaze 125T, Blaze 150T, with (Novozymes A/S),, Purafect Purafect Excellenz P1000 TM , Excellenz P1250 TM , Preferenz P100 TM , Purafect Preferenz P110 TM , Effectenz P1000 TM , Effectenz P1050 TM , Purafect Effectenz P2000 TM , with (Danisco / DuPont), Axapem TM (Gist-Brocases NV), BLAP ( US5352604 sequence shown in FIG. 29) and variants (Henkel), and KAP (Bacillus alkalophilus subtilisin) (Kao Corporation).
  • Suitable cellulases may be of animal, vegetable or microbial origin.
  • the protease is chemically modified or protein engineered.
  • the cellulase may be derived from Bacillus, Pseudomonas, Humicola, Fusarium, Thielavia or Acremonium.
  • the cellulase is derived from Humicola insolens, Myceliophthora thermophilum, Sporotrichum pulverulentum, Fusarium oxysporum, Trichoderma reesei, Thielavia trematosus, Acremonium Species, Acremonium species CBS 478.94, Coccidioides CBS 281.96, Crinipellis scabella CBS 280.96, Volutella colletotrichoides or Pseudomonas faecalis ATCC 52644 or Bacillus sp. KSMS237.
  • Suitable cellulases include those 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 5,763,254, WO 95/24471, WO 98/12307 and WO 99/001544.
  • cellulases are endo-1,4-beta-glucanases having at least 97% sequence identity to amino acids 1 to 773 of SEQ ID NO: 2 of WO 2002/099091, or A 44 family xyloglucanase having at least 60% sequence identity to amino acids 40 to 559 of SEQ ID NO: 2 of WO 2001/062903.
  • Preferred commercially available cellulases include, but are not limited to, 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).
  • the amylase is an alpha-amylase or a glucoamylase, preferably of microbial origin or chemically modified or protein engineered. It is of bacterial or fungal origin.
  • the amylase may be an alpha-amylase obtained from a genus of Bacillus, such as Bacillus licheniformis. An alpha-amylase from a particular strain of Bacillus licheniformis as described in detail in GB 1,296,839.
  • Examples of useful amylases especially variants having substitutions in one or more of the 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, in WO 94/02597, WO 94/18314, WO 1995/010603, WO 1995/026397, WO 96/23873, WO 97/43424 And described in WO 00/60060, WO 2001/066712, WO 2006/002643.
  • the alpha-amylase is derived from Bacillus sp. strains NCIB 12289, NCIB 12512, NCIB 12513, and DSM 9375. Particularly preferred are the alpha-amylases shown in SEQ ID NOS 1 and 2 of WO 95/26397.
  • Preferred commercially available amylases include, but are not limited to 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 S100 and Preferenz S110 (from Genencor International Inc./DuPont).
  • Lipases are of bacterial or fungal origin. Chemically modified or protein engineered mutant enzymes are included. Examples include lipases from the genus Thermophilus, such as from Thermomyces glabrata (formerly known as Humicola insolens) as described in EP 258068 and EP 305216; keratin from Humicola Enzymes, such as Humicola insolens (WO 96/13580); lipases from strains of the genus Pseudomonas (some of which are now renamed Burkholderia), such as Pseudomonas aeruginosa or Pseudomonas aeruginosa (EP 218272), Pseudomonas cepacia (EP 331376), Pseudomonas strain SD705 (WO 95/06720 & WO 96/27002), P.
  • Thermophilus such as from Thermomyces glabrata (formerly known as Humi
  • wisconsinensis P. wisconsinensis
  • GDSL-type Streptomyces lipase WO 10/065455
  • cutinase from Magnaporthe oryzae WO 10/107560
  • cutinase from Pseudomonas Mendocs US 5,389,536
  • Lipase from Thermobifida fusca WO 11/084412
  • Bacillus stearothermophilus lipase WO 11/084417
  • lipase from Bacillus subtilis WO 11/084599
  • And lipases from Streptomyces griseus WO 11/150157
  • S. pristinaspiralis WO 12/137147
  • lipase variants as described, for example, in EP 407 225, 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 97/04079, WO 97/07202, WO 00/34450, WO 00/60063, WO 01/92502, WO 07/87508, and WO 09/109500.
  • Preferred commercial lipases include but are not limited to products Lipolase TM, Lipex TM, Lipolex TM and Lipoclean TM (Novozymes), Lumafast (from Genencor (Genencor)) and Lipomax (Gist Broken card from Gist-Brocades).
  • lipases sometimes referred to as acyltransferases or perhydrolases
  • acyltransferases having homology to Candida antarctica lipase A (WO 10/111143), from smear-splitting branches
  • An acyltransferase of Mycobacterium smegmatis (WO 05/56782), a perhydrolase from the CE 7 family (WO 09/67279) and a variant of M. smegmatis perhydrolase (especially from Huntsman Textiles) S54V variant used in Gentle Power Bleach, a commercial product of Huntsman Textile Effects Pte Ltd. (WO 10/100028).
  • the pectate lyase may be a wild-type enzyme derived from Bacillus, in particular Bacillus licheniformis or B. agaradhaerens, or for example as US 6,124,127 (NZ 5543), WO 1999/027083 (NZ 5377), WO 1999/027084 These derived variants are described in (NZ 5378), WO 2002/006442 (NZ 10044), WO 2002/092741 (NZ 10171) or WO 2003/095638 (NZ 10190).
  • Mannanase is an enzyme that hydrolyzes mannan. Suitable mannanases include those derived from bacterial or fungal sources, as well as chemically modified or protein engineered mutant enzymes.
  • the mannanase may be a family 5 or 26 alkaline mannanase. It may be in the wild from Bacillus or Humicola, in particular B.agaradhaerens, Bacillus licheniformis, B. halodurans, B. clausii or Humicola insolens. type.
  • Suitable mannanases are described in WO 1999/064619. Commercially available mannanases such as (Novozymes A / S), and EFFECTENZ TM M1000 (Dupont).
  • Suitable peroxidases/oxidases include peroxidases/oxidases of plant, bacterial or fungal origin. Chemically modified mutants or protein engineered mutants are also included. Examples of useful peroxidases include peroxidases from the genus Coprinus, such as peroxidase from C. Cinereus. It is described in detail in EP 179,486 and its variants as described in WO 93/24618, WO 95/10602 and WO 98/15257.
  • peroxidases include, but are not limited to Guardzyme TM (Novo Nordisk A / S ).
  • a polypeptide having deoxyribonuclease (DNase) activity or a deoxyribonuclease (DNase) is any enzyme that catalyzes the hydrolysis cleavage of a phosphodiester bond in a DNA backbone to degrade DNA.
  • DNase deoxyribonuclease
  • DNase deoxyribonuclease
  • Two terms, polypeptides having DNase activity and DNase are used interchangeably.
  • DNases are obtainable from bacteria or fungi. Chemically modified mutants or protein engineered mutants are also included.
  • DNases are those disclosed in EP 17165320.7 and variants derived therefrom.
  • the washing enzyme used in the synergistic capsule of the present invention can be provided as a single pure enzyme or a mixture of different kinds of enzymes.
  • the amount of a single enzyme or mixture of enzymes in a synergistic capsule can vary, generally providing a higher enzyme dosage during the wash cycle than a typical scoop of commercially available enzyme-containing detergent.
  • the pure enzyme dosage in the synergistic capsule is chosen to enhance the cleaning power of traditional cleaning products.
  • the final concentration of pure enzyme or active enzyme can be selected to provide about 0.0001 ppm, about 0.001 ppm, about 0.01 ppm, about 0.1 ppm, to about 1 ppm, about 2.5 ppm, for each laundry or dishwashing cycle. About 5 ppm, about 10 ppm, about 25 ppm, about 50 ppm of enzyme.
  • an enzyme concentration of 50 ppm or more can be applied in the present invention.
  • the enzyme component used in the synergistic capsule can be provided in the form of granules.
  • the enzyme granules are low cost granules without the more expensive ingredients required to stabilize the enzyme when stored in a detergent, such as barrier materials, enzyme stabilizers, bleach neutralizers, and the like.
  • a detergent such as barrier materials, enzyme stabilizers, bleach neutralizers, and the like.
  • some of these ingredients may be co-present with the enzyme in the wash booster capsules of the present invention, if desired and cost effective.
  • a low-cost, high-quality method for drying enzyme granules is described in Chinese Patent No. ZL00814580.6 (Novozymes), which is incorporated herein in its entirety.
  • the method comprises spray drying a fermentation broth containing enzyme and biomass, wherein the biomass constitutes at least 10% of the biomass obtained from the fermentation.
  • One such particle has an enzyme coated on a salt seed and a relatively thin salt coating layer.
  • the enzyme component may also be a dry powder enzyme or an enzyme dispersed on a carrier or plated on a carrier such as sugar, starch or maltodextrin. Enzymes can also be added during the wet granulation process, as described in U.S. Patent No. 6,852,336, which is incorporated herein in its entirety.
  • the detergent-enhancing capsule of the present invention may contain, in addition to the particles of the enzyme for washing, other components to be mixed with the enzyme particles for washing.
  • the enzyme granules in the wash capsule comprise at least about 1%, preferably at least 2.5%, at least 5%, at least 10%, at least 15%, at least 20%, at least 25%, at least at least 25% by weight of the capsule. 30%, at least 35%, at least 40%, at least 45%, at least 50%, at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, or at least 99%.
  • the detergent booster capsules of the present invention may comprise, in addition to the particles of the enzyme for washing, any polymer known in the art for use in detergents.
  • the polymer can function as a co-builder as mentioned above, or can provide anti-redeposition, fiber protection, soil release, dye transfer inhibition, oil stain cleaning and/or anti-foaming properties.
  • Some polymers may have more than one of the above mentioned characteristics and/or more than one of the following mentioned motifs.
  • Exemplary polymers include (carboxymethyl)cellulose (CMC), poly(vinyl alcohol) (PVA), poly(vinylpyrrolidone) (PVP), poly(ethylene glycol) or poly(ethylene oxide) (PEG) Ethoxylated poly(ethyleneimine), carboxymethyl inulin (CMI), and polycarboxylates such as PAA, PAA/PMA, poly-aspartic acid, and lauryl methacrylate /Acrylic copolymer, hydrophobically modified CMC (HM-CMC) and copolymer of silicone, terephthalic acid and oligoethylene glycol, poly(ethylene terephthalate) and poly(oxyethylene terephthalate) Copolymer of ethylene glycol formate (PET-POET), PVP, poly(vinylimidazole) (PVI), poly(vinylpyridine-N-oxide) (PVPO or PVPNO), and polyvinylpyrrolidone-vinylimidazole
  • Additional exemplary polymers include sulfonated polycarboxylates, polyethylene oxide and polypropylene oxide (PEO-PPO), and diquaternary ammonium ethoxysulfate.
  • PEO-PPO polyethylene oxide and polypropylene oxide
  • diquaternary ammonium ethoxysulfate diquaternary ammonium ethoxysulfate.
  • Other exemplary polymers are disclosed, for example, in WO 2006/130575. Salts of the above-mentioned polymers are also contemplated.
  • the detergent synergistic capsule of the present invention may comprise, in addition to the particles of the enzyme for washing, a fabric toner known in the art for use in detergents, such as dyes or pigments, when formulated in a detergent composition.
  • a fabric toner known in the art for use in detergents, such as dyes or pigments, when formulated in a detergent composition.
  • the fabric toner may be deposited on the fabric when the fabric is in contact with a washing liquid, the washing liquid including the detergent composition, and thus the color of the fabric is changed by absorption/reflection of visible light.
  • the fluorescent whitening agent emits at least some visible light.
  • fabric toners change the color of the surface because they absorb at least a portion of the visible light spectrum.
  • Suitable fabric toners include dyes and dye-clay conjugates, and may also include pigments.
  • Suitable dyes include small molecule dyes and polymeric dyes.
  • Suitable small molecule dyes include small molecule dyes selected from the group consisting of the following dyes classified by the Colour Index (CI): direct blue, direct red, direct violet, acid blue, acid red, Acidic violet, basic blue, basic violet and basic red, or mixtures thereof, are described, for example, in WO 2005/03274, WO 2005/03275, WO 2005/03276 and EP 1 876 226, which are hereby incorporated by reference.
  • the detergent composition preferably comprises from about 0.00003 wt% to about 0.2 wt%, from about 0.00008 wt% to about 0.05 wt%, or even from about 0.0001 wt% to about 0.04 wt% of a fabric toner.
  • the composition may comprise from 0.0001% to 0.2% by weight of fabric toner, which may be particularly preferred when the composition is in the form of a unit dose bag. Suitable toners are also disclosed, for example, in WO 2007/087257 and WO 2007/087243.
  • the fabric toner in the wash capsule comprises about 0.002%, about 0.02%, about 0.2%, about 0.5%, about 1%, more by weight of the capsule.
  • the wash synergistic capsules of the present invention may also include one or more dye transfer inhibiting agents.
  • Suitable polymeric dye transfer inhibiting agents include, but are not limited to, polyvinylpyrrolidone polymers, polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, polyvinyloxazolidones, and polyethylenes. Imidazole or a mixture thereof.
  • the dye transfer inhibiting agent can comprise from about 0.1%, 0.2%, 0.5% or more by weight of the capsule.
  • the detergent booster capsules of the present invention may also comprise additional components which can color the article being cleaned, such as an optical brightener or an optical brightener.
  • an optical brightener suitable for use in laundry detergent compositions can be used in the compositions of the present invention.
  • the most commonly used fluorescent whitening agents are those belonging to the following classes: diaminoanthracene-sulfonic acid derivatives, diarylpyrazoline derivatives and diphenyl-distyryl derivatives.
  • fluorescent whitening agents of the diaminopurine-sulfonic acid derivative type include the following sodium salts: 4,4'-bis-(2-diethanolamino-4-anilino---triazin-6-ylamino ⁇ -2,2'-disulfonate, 4,4'-bis-(2,4-diphenylamino---triazin-6-ylamino)indole-2.2'-disulfonate, 4 , 4'-bis-(2-anilino-4-(N-methyl-N-2-hydroxy-ethylamino)-ho-triazin-6-ylamino)indole-2,2'-disulfonate Acid salt, 4,4'-bis-(4-phenyl-1,2,3-triazol-2-yl)indole-2,2'-disulfonate and 5-(2H-naphtho[1] , 2-d][1,2,3]triazol-2-yl)-2-[
  • a preferred fluorescent whitening agent is Tinopal DMS and Tianlaibao CBS available from Ciba-Geigy AG (Basel, Switzerland).
  • Tianlaibao DMS is the disodium salt of 4,4'-bis-(2-morpholino-4-anilino-s-triazin-6-ylamino)indole-2,2'-disulfonate.
  • Tianlaibao CBS is the disodium salt of 2,2'-bis-(phenyl-styryl)-disulfonate.
  • fluorescent whitening agents commercially available Parawhite KX, supplied by Paramount Minerals and Chemicals, Mumbai, India.
  • fluorescers suitable for use in the present invention include 1-3-diarylpyrazoline and 7-alkylaminocoumarin.
  • Suitable brightening or fluorescent whitening agents can comprise from about 0.1%, about 0.5%, about 1%, about 5%, 10%, 20%, 50% or more by weight of the cleansing capsules of the present invention.
  • the wash synergistic capsules of the present invention may also include one or more soil release polymers which aid in the removal of soils from fabrics, such as cotton and polyester based fabrics, particularly from polyester based fabrics. Remove hydrophobic dirt.
  • the soil release polymer may, for example, be a nonionic or anionic terephthalic acid based polymer, polyvinyl caprolactam and related copolymers, a vinyl graft copolymer, a polyester polyamide, see for example a powdered detergent, surface Active Agent Science Series, Volume 71, Chapter 7, Marcel Dekker, Inc.
  • Another type of soil release polymer is an amphiphilic alkoxylated oil cleaning polymer comprising a core structure and a plurality of alkoxylated groups attached to the core structure.
  • the core structure may comprise a polyalkylenimine structure or a polyalkanolamine structure as described in detail in WO 2009/087523 (which is hereby incorporated by reference).
  • random graft copolymers are suitable soil release polymers. Suitable graft copolymers are described in more detail in WO 2007/138054, WO 2006/108856 and WO 2006/113314, which are hereby incorporated by reference.
  • Other soil release polymers are substituted polysaccharide structures, especially substituted cellulose structures, such as modified cellulose derivatives, such as those described in EP 1 867 808 or WO 2003/040279 (both of which are hereby incorporated by reference) ).
  • Suitable cellulosic polymers include cellulose, cellulose ethers, cellulose esters, cellulose amides, and mixtures thereof. Suitable cellulosic polymers include anionically modified cellulose, nonionic modified cellulose, cationically modified cellulose, zwitterionic modified cellulose, and mixtures thereof. Suitable cellulosic polymers include methylcellulose, carboxymethylcellulose, ethylcellulose, hydroxyethylcellulose, hydroxypropylmethylcellulose, ester carboxymethylcellulose, and mixtures thereof. In one embodiment of the invention, the soil release polymer in the wash booster capsule comprises about 0.1%, 1%, 5%, 10%, 50%, 60% or more by weight of the capsule.
  • the wash synergistic capsules of the present invention may also include one or more antiredeposition agents such as carboxymethyl cellulose (CMC), polyvinyl alcohol (PVA), polyvinylpyrrolidone (PVP), polyoxyethylene and/or Polyethylene glycol (PEG), a homopolymer of acrylic acid, a copolymer of acrylic acid and maleic acid, and an ethoxylated polyethyleneimine.
  • CMC carboxymethyl cellulose
  • PVA polyvinyl alcohol
  • PVP polyvinylpyrrolidone
  • PEG Polyethylene glycol
  • the cellulose-based polymers described above under the soil release polymer can also be used as antiredeposition agents.
  • the anti-redeposition agent in the wash booster capsule comprises about 0.1%, 1%, 5%, 10%, 50%, 60% or more by weight of the capsule.
  • the synergistic capsule comprises a content which, besides the enzyme for washing, is substantially free of some of the enzyme caustic substances commonly found in detergents, such as surfactants, bleaches, bleaching activation Agents, etc.
  • Suitable preformed peracids include, but are not limited to, peroxycarboxylic acids and salts, diperoxydicarboxylic acids, perimidic acids and salts, peroxymonosulfuric acid and salts (eg, potassium persulfate (Oxone ( R)) and mixtures thereof.
  • Non-limiting examples of bleaching systems include peroxide-based bleaching systems in combination with peracid forming bleach activators, which may comprise, for example, inorganic salts, including alkali metal salts such as sodium perborate a salt (usually mono or tetrahydrate), percarbonate, persulphate, perphosphate, persilicate.
  • the term bleach activator herein means a reaction with hydrogen peroxide to form via a perhydrolysis reaction.
  • Peracid compounds. The peracid formed in this manner constitutes an activated bleach.
  • Suitable bleach activators to be used herein include those belonging to the class of esters, amides, imides or anhydrides. A suitable example is tetraacetyl B.
  • TAED Diamine
  • ISONOBS 4-[(3,5,5-trimethylhexanoyl)oxy]benzene-1-sulfonate
  • LOBS 4-(dodecanoyloxy)benzene-1-sulfonate Acid salt
  • DOBS 4-(decanoyloxy)benzene-1-sulfonate
  • DOBS 4-(nonanoyloxy)benzoate
  • NOBS 4-(decanoyl) Oxy)benzene-1-sulfonate
  • ATC acetyl Triethyl citrate
  • ATC or short-chain triglycerides have the following advantages, which are environmentally friendly.
  • acetyl triethyl citrate and triacetin are stored in the product. It has good hydrolytic stability and is an effective bleach activator.
  • ATC is multifunctional because the citrate released in the perhydrolysis reaction can act as a builder.
  • bleaching The system may include a peroxyacid such as an amide, imide or sulfone type.
  • the bleaching system may also include a peracid such as 6-(phthalimido) peroxyhexanoic acid (PAP).
  • PAP 6-(phthalimido) peroxyhexanoic acid
  • the bleaching system may also A bleach catalyst is included.
  • the bleach component can be an organic catalyst selected from the group consisting of: an organic catalyst having the formula:
  • each R1 is independently a branched alkyl group comprising from 9 to 24 carbons or a linear alkyl group comprising from 11 to 24 carbons, preferably each R1 independently comprises from 9 to 18 carbons.
  • Suitable bleaching systems are described in, for example, WO 2007/087258, WO 2007/087244, WO 2007/087259, EP 1867708 (vitamin K), and WO 2007/087242.
  • Suitable photobleaches can be, for example, sulfonated zinc phthalocyanine or aluminum phthalocyanine.
  • the bleaching component in addition to the bleach catalyst, particularly the organic bleach catalyst, also includes a source of peracid.
  • the peracid source may be selected from (a) a preformed peracid; (b) a percarbonate, perborate or persulphate (a source of hydrogen peroxide), preferably in combination with a bleach activator; and (c Perhydrolase and ester for the in situ formation of peracid in the presence of water in the textile processing step.
  • the present invention is directed to a synergistic capsule for enhancing a washing effect
  • a synergistic capsule for enhancing a washing effect comprising a capsule shell made of a pullulan material, and a washing enzyme contained in the capsule shell.
  • Pullulan capsules have the same transparency as gelatin capsules, making the filling contents clearly visible, stable in wide temperature and humidity range, low oxygen permeability and avoiding oxidation of the filling contents, while avoiding the treatment of animals during gelatin capsule preparation.
  • the pollution problem caused by fur and the like and the disintegration speed of gelatin in the washing process are not fast enough, and the residue of the capsule material adheres to the washing clothes and other hard surfaces after the washing process, thereby seriously affecting the evaluation of the washing effect by the consumer. The problem.
  • the present invention relates to the use of a cellulose derivative, a starch and a starch derivative, and pullulan in the preparation of a synergistic capsule for enhancing the washing effect.
  • the present invention is directed to a kit comprising one or more of the synergistic capsules described above having a consumer identification element corresponding to the function of the enzyme enzyme contained within the interior.
  • the consumer identification element can help the consumer to understand one or more of the washing synergies that a particular booster capsule can provide.
  • the identification element may include a visual element, an olfactory element, or other sensory element.
  • the visual element may be, for example, a text, a pattern, a color, or a combination thereof, and the olfactory element may be a specific fragrance.
  • the synergistic capsules are individually wrapped in a blister packaging material, and the synergistic capsules may be in a single package or a combination of a plurality of packages, for example, forming a continuous row, or continuously. Several columns are provided in the form of a square matrix.
  • the blister packaging material is common in pharmaceutical capsule preparations and delivery processes, and the blister packaging material may be made of aluminum foil and plastic material, usually a molded plastic sheet with a backing material such as a foil layer material, so that the consumer It can be released from the package by pressing the capsule.
  • the synergistic capsules of the present invention can also be provided in sealed boxes, bottles, cans. Any type of container or package can be equipped with a dispensing device. A use identification mark of the capsule may be included on the outer package, including the visual identification mark described above.
  • the present invention relates to a method of preparing a synergistic capsule as hereinbefore described, comprising: a) screening a residual rate in a washing process at 15 ° C to 30 ° C of no more than 18%, no more than 12%, preferably no More than 10%, preferably no more than 8%, preferably no more than 6%, preferably no more than 4%, preferably no more than 3%, preferably no more than 1% of the capsule shell, and b) a washing enzyme filled into the interior of the capsule shell.
  • the method further comprises the steps of: c) screening a capsule shell having a disintegration rate of no more than 30 minutes in a wash solution containing 2% surfactant at 20 ° C, wherein step c) Step a) before, after or at the same time.
  • the detergent synergistic capsule of the present invention which meets the needs of the consumer can be efficiently prepared.
  • a synergistic capsule comprising a capsule outer shell, and a washing enzyme contained inside the capsule, the synergistic capsule capable of enhancing the washing effect in the short-course washing.
  • the short-range wash comprises a wash cycle of no more than 110 minutes, preferably no 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.
  • the short-range washing has a temperature of not more than 90 ° C, preferably not more than 60 ° C, preferably not more than 40 ° C, preferably not more than 35 ° C, preferably not more than 30 ° C, preferably
  • the main wash temperature does not exceed 20 ° C, preferably does not exceed 10 ° C, preferably does not exceed 4 ° C.
  • the capsule shell is made of a material comprising a group consisting of a cellulose derivative, a starch and a starch derivative, a pullulan, and combinations thereof.
  • washing enzyme is selected from the group consisting of a protease, an amylase, a cellulase, a lipase, a phospholipase, a cutinase, an oxidase, and an oxygenase. , transferase, reductase, hemicellulase, mannanase, esterase, isomerase, pectinase, lactase, peroxidase, lyase, laccase, deoxyribonuclease, lichen Enzymes, and combinations thereof.
  • the synergistic capsule of embodiment 11, wherein the enzyme for washing is selected from the group consisting of a protease, an amylase, a mannanase, a cellulase, and combinations thereof.
  • the synergistic capsule according to any one of the above aspects which has a size of 5 mm to 100 mm.
  • a synergistic capsule comprising a capsule shell made of a material comprising pullulan, and a washing enzyme contained in the capsule shell, the synergistic capsule capable of enhancing a washing effect.
  • a kit comprising one or more synergistic capsules according to any one of aspects 1-17, wherein the synergistic capsule has a visual recognition element corresponding to a function of an enzyme contained in the interior.
  • Screening has a disintegration rate in a wash solution containing 2% surfactant at 20 ° C of no more than 30 minutes, preferably no more than 20 minutes, 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 in the capsule casing,
  • step c is performed before, after or simultaneously with step a.
  • model washing powder solution deionized water, the aforementioned model washing powder was added to a concentration of 2% w/w.
  • the magnets (C200, Baiwang Tongda Technology Co., Ltd.) The length is 20 mm and the diameter is 7 mm. The stirring rate is 400 rpm. Since the enzyme for washing has strong water solubility and the dissolution time is short, the T50 is 30 s at 20 ° C. Therefore, the time when the capsule to be tested is broken and the blue dye is released can be regarded as equivalent to the washing increase of the enzyme in the practical application. The moment when the disintegration of the capsule begins, that is, the moment when blue is leaked from the capsule into the solution is initially visually observed.
  • the capsule shell must be able to completely dissolve after the end of the washing process so as not to form a residue and stick to the clothing causing consumer trouble. Therefore, the residual rate of the capsule material after washing is one of the important criteria for determining whether it is suitable for use in a washing environment.
  • the residual rate (R%) that is, the weight percentage of the hollow capsule is determined as follows: the weight W(0) of the hollow capsule is accurately weighed at room temperature (accurate to 0.01 g), and the weighed hollow capsule is placed.
  • Non-woven tea bags purchased in supermarkets
  • the hollow capsule to be tested is put into the washing machine along with the bag. Since the tea bag may undergo weight change due to adsorption of detergent residue (such as zeolite 4A) or frictional damage during the washing process, an empty tea bag should be added as a calibration sample for each round of experiments to correct the tea bag's own weight change zone.
  • the resulting error ⁇ where the value of ⁇ is taken from the average of five measured parallel samples.
  • the total weight of the washed tea bags and hollow capsules was measured and recorded as W (2).
  • R% is calculated according to the following formula, where W(1) - W(0) + ⁇ is the weight of the washed tea bag.
  • the residual rate of each capsule was calculated from the average of three sets of parallel samples.
  • the pulsator washing machine method washes the following commercially available 12 contaminated fabric samples.
  • the preparation of the above model washing powder and model laundry liquid can refer to the configuration of the Chinese national standard washing powder.
  • Capsules a'-d' to be tested were prepared according to the description of Analytical Method 2 using four commercially available hollow capsules, and the disintegration time of the different capsule materials was determined.
  • the hollow capsules are:
  • gelatin capsules #0, purchased from Suzhou Capsule Capsugel
  • the disintegration time of gelatin capsules is the longest in the low temperature (20 ° C, 30 ° C) washing process compared to the capsules of other materials, and disintegrates during the high temperature (40 ° C) washing process. Time begins to show shorter than other capsules. This indicates that the disintegration time of the gelatin capsule has a significant washing temperature dependency; while the disintegration time of the HPMC capsule is not significantly affected by the temperature in the common washing temperature range.
  • the dissolution rate of seaweed extract capsules and starch capsules is also affected by temperature. When the temperature is low (20 ° C), the dissolution rate is better than gelatin, and the dissolution rate is significantly improved in the solution at higher temperature (30 ° C, 40 ° C), but The increase is weaker than gelatin capsules.
  • the purpose of this experiment was to verify the effect of the increase in the ionic strength of the wash liquor caused by the auxiliaries contained in the detergent on the disintegration time of the capsule material.
  • the preparation of the capsule to be tested in the experimental group, the configuration of the model washing powder solution and the measurement method of the release rate were the same as those described in the analytical method 2, and the experiment was carried out at 20 °C.
  • the model washing powder used in the experimental group contained 0.4% Na 2 CO 3 and 0.7% Na 2 SO 4 as auxiliary agents;
  • This experiment tested the disintegration time of the two capsules to be tested b' and c'. The results are shown in the table below, and each data takes the arithmetic mean of two repetitions under the same conditions.
  • Example 3 Evaluation of the washing effect of washing synergists made of different capsule materials.
  • Experimental groups 1-4 were each added with one wash boosting capsule A-D at the start of washing.
  • the positive control group was added directly to the same amount of solid enzyme granule mixture contained in the wash booster capsule at the start of washing.
  • the stains targeted for washing are stains characterized in 11 of the 12 samples as described in the "Materials" section "Washing Contaminated Fabric Samples" above.
  • the washing was carried out using the setting of the pulsator washing machine of the "washing equipment and conditions” section of the previous example, and the washing temperature was 25 °C.
  • the difference between the light intensity value of the surface of each of the experimental groups 1 to 4 and the light intensity value of the fabric surface of the positive control group, that is, ⁇ Rem was measured and calculated.
  • Rem(0) is the light intensity value of the surface of the textile washed when the solid enzyme mixture (positive control) is put into the washing machine at 0 min;
  • Rem(T) is the light intensity value of the surface of the textile after washing with the synergistic capsule
  • Table 12 Washing effect ( ⁇ Rem) on 12 stains using model laundry detergent and washing synergistic capsule A-D in pulsator washing machine
  • the added detergent synergistic capsule is a washing enzyme encapsulated by gelatin capsules
  • the effect of washing after washing with respect to the positive control group, 6 (55%) of the 11 stains showed significant washing effect on the stain.
  • Table 13 Washing effect on 12 stains using model washing powder and washing synergistic capsule A-D in pulsator washing machine ( ⁇ REM)
  • the added detergent synergistic capsules are other materials, such as HPMC capsules, there is almost no significant reduction in the washing effect compared to the positive control in the 11 stains, or the washing effect on the 11 stains in the pullulan capsules. There was only a significant reduction in the washing effect of only 1 or 2 stains compared to the positive control.
  • gelatin capsules can affect the working efficiency of enzyme-containing contents, especially when the environment is relatively popular in Asia, the washing cycle is shorter (main wash time is 15 min, total wash time is 40 min).
  • the pulsator washing machine is used in the washing process. Washing synergistic capsules made of other materials, such as HPMC capsules and pullulan capsules, did not significantly affect the significant reduction in washing performance compared to the positive control.
  • Table 15-18 below shows the test analysis of the residual ratio of various capsules under different conditions.
  • Table 15 Residual rate of different washing time of capsule a (gelatin capsule) drum washing machine at 30 ° C
  • Table 16 Residual rate of different washing time of capsule b (HPMC capsule) drum washing machine at 30 ° C
  • Wash cycle Main wash cycle Residual rate Quick wash (reduction drift) express 20 short 11 20 2% Quick wash express 20 11 30 10% Shirt short twenty three 44 0% Dark clothing dark garments twenty two 62 7% Iron free 83 87 0% Cotton wash (reduce) cotton short 51 119 -7% Cotton washed cotton 51 149 7% Enhanced wash intensive 108 167 -4%
  • Wash cycle Main wash cycle Residual rate Quick wash (reduction drift) express 20 short 11 20 3% Quick wash express 20 11 30 3% Shirt short twenty three 44 0% Dark clothing dark garments twenty two 62 6% Iron free 83 87 -4% Cotton wash (reduce) cotton short 51 119 0% Cotton washed cotton 51 149 0% Enhanced wash intensive 108 167 3%
  • Wash cycle Main wash cycle Residual rate Quick wash (reduction drift) express 20 short 11 20 3% Quick wash express 20 11 30 -10% Shirt short twenty three 44 3% Dark clothing dark garments twenty two 62 -6% Iron free 83 87 10% Cotton wash (reduce) cotton short 51 119 -15% Cotton washed cotton 51 149 -4% Enhanced wash intensive 108 167 6%
  • Table 27 Residual rate of capsule e (Chenxing seaweed capsule) in different washing time of drum washing machine at 30 °C
  • Wash cycle Main wash cycle Residual rate Quick wash (reduction drift) express 20 short 11 20 0% Quick wash express 20 11 30 6% Shirt short twenty three 44 1% Dark clothing dark garments twenty two 62 1% Iron free 83 87 2%
  • Table 28 Residual rate of capsule f (red star seaweed capsule) in different washing time of drum washing machine at 30 ° C
  • Wash cycle Main wash cycle Residual rate Quick wash (reduction drift) express 20 short 11 20 6% Quick wash express 20 11 30 9% Shirt short twenty three 44 2% Dark clothing dark garments twenty two 62 2% Iron free 83 87 5% Cotton wash (reduce) cotton short 51 119 4% Cotton washed cotton 51 149 1% Enhanced wash intensive 108 167 2%
  • Wash cycle Main wash cycle Residual rate Quick wash (reduction drift) express 20 short 11 20 1% Quick wash express 20 11 30 1% Shirt short twenty three 44 1% Dark clothing dark garments twenty two 62 1% Iron free 83 87 7% Cotton wash (reduce) cotton short 51 119 1% Cotton washed cotton 51 149 -1% Enhanced wash intensive 108 167 1%
  • the balance weighing error is ⁇ 0.01g
  • the capsule a-g is #0 capsule
  • the weight range is between 0.08-0.12g, so the systematic error of the residual rate calculation is 8%-12%.
  • the sensory evaluation of the residual state of the capsule was carried out at the same time as the weighing test, and it was found that no residue was found in the residual rate within the range of ⁇ 18%, but the residual rate exceeded the error range, indicating that there was significant after washing. Residue.
  • the laundry detergent synergist C containing solid cellulase particles (Novozymes A/S, Carezyme Premium 5000T) was prepared using commercially available hollow capsule c (Pullen polysaccharide capsule), and the cellulase content was 0.6 g, and the enzyme particles were filled.
  • the method to the inside of the capsule is as described in Example 3.
  • the material used in the fabric care evaluation was EMPA 252 (color stripe cloth, 94% cotton 6% spandex, available from Center for Testmaterials B.V, Netherlands), and the material was aged after use as described below.
  • the aging of the material was carried out by placing the prewashed EMPA 252 in a Wascator automatic washing machine for 12 hours with a treatment temperature of 40 °C.
  • the surface of the treated EMPA252 will be clearly pilling for easy evaluation of the care effect.
  • the washing conditions are as follows: "washing equipment and conditions", wherein the washing temperature of the pulsator washing machine is 25 ° C, the detergent is commercially available, and the washing temperature of the drum washing machine is 40 ° C, the detergent For the commercial blue moon deep cleansing laundry detergent.
  • the washing effect of the same fabric EMPA252 sample after three consecutive washings was continuously monitored in the experiment.
  • Negative control group no synergistic capsules were added.
  • the evaluation method of the fabric care effect is to measure the brightness value (L value) of the black stripe on the aging EMPA 252.
  • the wear pilling will reduce the brightness of the clothes, that is, the black ash on the EMPA 252 black stripe is reflected as black and the brightness value is increased. Therefore, after the washing was completed, the difference between the brightness value (L) of the surface of each of the experimental groups 1-5 and the brightness value of the surface of the fabric of the aging EMPA 252 which was not washed was measured and calculated, that is, ⁇ L.
  • the addition of the washing synergistic capsule C can provide the remarkable visible fabric care effect after the second round of washing, the effect of which increases with the dose of the synergistic capsule and The number of washing wheels is increased and enhanced.
  • the ⁇ L of the negative control group decreased as the number of wash cycles increased, suggesting further damage to the surface properties of the fabric. This indicates that the cellulase-containing wash synergy capsule of the present invention provides a significant depilatory ball laundry care effect.
  • Solid cellulase-containing granules Novozymes A/S, Carezyme Premium 5000T
  • water-soluble fluorescent whitening agent FWA, available from BASF, product name
  • the laundry synergist capsule 1-2 to be tested of CBS-X the contents of the capsule contents are as described in Table 25.
  • the method of filling the inside of the capsule with the enzyme granules and the fluorescent whitening agent is as described in Example 3.
  • the materials used in the fabric care evaluation were white knitted cotton (CN42, available from Center for Testmaterials B.V, Netherlands) and white terry cloth (WFK12AW, available from Testfabrics, Inc.).
  • the washing was carried out using the setting of the vertical decontamination machine of the "washing equipment and conditions" section of the previous example, and the detergent was the above model washing powder.
  • 0.8 g/L of liquid carbon black was added to simulate the stain in the washing environment.
  • test conditions of each experimental group are as described in Table 26, the positive control is untreated, the negative control and the other experimental groups are all washed with 2g/L model washing powder (as described in the material section of the previous example), wherein the fluorescence In the whitening agent group (experiment group 1), an additional 0.55 g of fluorescent whitening agent was added during the washing process, and the capsule 1 group (experiment group 2) and the capsule 2 group (experiment group 3) were additionally added with 1-2 corresponding washing additions. Capsules.
  • the decrease in the surface light intensity after washing of each experimental tissue corresponding to the positive control group that is, ⁇ Rem
  • the fluorescent whitening agent group (experimental group 1) and the experimental group 2 containing the cellulase synergist capsule 1 were effective compared to the untreated negative control group. Slowing down the whiteness of the fabric.

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Abstract

一种增效胶囊，其包括胶囊外壳，和包含在胶囊内部的洗涤用酶，所述增效胶囊能够增强在短程洗涤中的洗涤效果。一种用于增强洗涤效果的增效胶囊，其包括普鲁兰多糖材料制成的胶囊外壳，和包含在上述胶囊外壳内的洗涤用酶。普鲁兰多糖在制备用于增强洗涤效果的增效胶囊中的应用。一种试剂盒，其包含所述的增效胶囊，胶囊上具有相应的视觉识别要素。

Description

增效胶囊
发明领城
本发明涉及用于增强洗涤效果的增效胶囊，和制备该增效胶囊的方法。
发明背景
在洗涤剂领域，优质性能的洗涤剂中通常会包含去除不同污渍组分的一种或多种酶。洗涤剂产品的配方设计要考虑到掺入其中的酶的储存稳定性和洗涤过程中的应用稳定性。通常，酶是以颗粒的形式平均分散在整个洗涤产品中。保持酶的稳定性是一个技术上的挑战，因为酶是蛋白质，其活性受洗涤剂中的成分比如阴离子表面活性剂或漂白剂等的影响，同时蛋白酶也会通过其蛋白水解作用对其他的酶的活性产生影响。"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)论述了使洗衣用酶失活的各种因素，包括漂白剂和表面活性剂。
本领域内已经有多种方法被尝试用来稳定洗涤剂中的昂贵的酶的活性，比如通过：1)添加酶的稳定剂或蛋白酶抑制剂，例如"Formulation of Detergent Enzymes",Becker et al.，Enzymes in Detergency,Jan H van Ee and Onno Misset,由Erik J Baas,NY Marcel Dekker(1997)出版，描述了稳定洗涤剂中的酶的方法；2)尝试具有多隔室的单剂量包装的洗涤剂，将酶和漂白剂分隔开来。EP0481547A1公开了包括表面活性剂、酶和氯漂白剂的洗碟机洗涤剂片，其具有至少三层来隔离"不相容的成分，如酶和氯漂白剂"。美国专利6,413,928描述了制备具有凝胶部分的多相洗涤剂片的方法。所述片使酶与漂白剂和表面活性剂物理分开。所述的具有酶和漂白剂的商业可得的产品可以以片剂的形式得到，并且已知为Reckitt Benckiser的Vanish Action Ball(神效洗衣球)。这样的技术方案进一步增加了含酶洗涤剂的成本。
对于经济级的洗涤剂而言，其成本结构常常导致无法在其中使用酶或高剂量的酶，或者无法在配方中加入控制酶活性的额外的成分，或无法配置在将影响酶活性的成分与酶物理隔绝的复杂结构中。
在工业中，需要在成本方面有效的单剂量固体酶产品，消费者可以按照需要选择酶产品和在洗涤过程中加入酶产品，所述洗涤过程应用现有的清洁 配制物，特别是有可能允许使用不带有酶的便宜的清洁配制物和液体清洁配制物。
CN101218334A(金克克国际有限公司)公开了用于消费者的织物护理酶片剂，该酶片剂可以在自动洗衣机或洗碗机的洗涤周期中单剂量添加。该单剂量的片剂是通过流式床工艺将酶与赋形剂例如微晶纤维素，硬脂酸酶等一起。压片的工艺相对复杂，并且为了防止消费者直接接触酶增效剂或者使用过程中片剂产生的粉尘造成酶过敏，还需要喷涂例如聚乙二醇等水溶性的成膜材料于压片的表面。为了防止压片吸潮导致酶活性受影响，还需要对压片进行化学处理或者提供一个外包装材料以进行防潮。所有这些步骤又重新增加了成本。此外，当提及包含酶增效剂的明胶胶囊时，CN101218334A仅公开了在欧洲长程洗涤程序中的应用。
本发明提供了在成本方面有效的方法，通过胶囊的形式将酶直接交付给消费者而不遭遇酶稳定性的问题，并且可以在相对短程的洗涤周期，比如相对欧洲的长程洗涤程序而言显著缩短的亚洲和美国洗涤程序中，迅速地发挥酶的洗涤增效作用。与酶平均分散于其中的洗涤剂相比，独立提供的内含于胶囊中的酶与不含酶的洗涤剂共同使用时，消费者能够更容易地认知酶对于去除特定污渍的增加的洗涤效果，并倾向于更多接受和认可酶在洗涤过程的使用。酶的使用可以节省传统不含酶的洗涤剂应用过程中所需大量使用的能源，包括电和水资源的使用量，同时达到同样或增加的洗涤效果，此外还可以减少洗涤废水排放产生的对环境的压力。
发明概述
在一个方面，本发明涉及一种增效胶囊，其包括胶囊外壳，和包含在胶囊外壳内部的洗涤用酶，其能够增强在短程洗涤中的洗涤效果。
在另一个方面，本发明涉及一种增效胶囊，其包括普鲁兰多糖材料制成的胶囊外壳，和包含在上述胶囊外壳内的洗涤用酶，其能够增强在短程洗涤中的洗涤效果。
在另一个方面，本发明涉及纤维素衍生物、淀粉及淀粉衍生物、普鲁兰多糖及其组合在制备用于增强洗涤效果的增效胶囊中的应用。
在另一个方面，本发明涉及一种试剂盒，其包含一个或多个前文所述的 增效胶囊，所述增效胶囊上具有与内部包含的洗涤用酶的功能相应的视觉识别要素。
在另一个方面，本发明涉及制备前文所述的增效胶囊的方法，包括：筛选在25℃下的洗涤过程中残留率不超过18％的胶囊外壳，和将洗涤用酶增效剂填充到胶囊外壳内部。
定义
δ酶性能值：术语“δ酶反射值”或“δEnz”或“ΔEnz”在此定义为在460nm处的反射比或反射测量值的结果。用一种具有类似颜色的小块布样，优选一种来自重复洗涤的小块布样作为背景测量该小块布样。在洗涤之前，测量代表每种小块布样类型的小块布样。δ酶性能值是用存在一种酶的洗涤剂洗涤的小块布样的反射值减去用不存在酶的洗涤剂洗涤的类似小块布样的反射值。
δ反射值(ΔRem)：在此将术语“δ反射”或“δ反射值”定义为在某一波长处的反射比或反射测量值的结果，该波长典型地是460nm。用一种具有类似颜色的布样，优选一种来自重复洗涤的布样作为背景测量该布样。在洗涤之前，测量代表每种布样类型的布样。δ反射是洗涤的布样的反射值减去未洗涤的布样的反射值。
洗涤剂组合物：术语“洗涤剂组合物”是指用于从有待清洁的物品(例如纺织品、餐具和硬表面)去除不希望的化合物的组合物。该洗涤剂组合物可以用于例如清洁纺织品、餐具以及硬表面，用于家用清洁剂和工业清洁二者。这些术语涵盖选择用于希望的具体类型的清洁组合物和产品的形式(例如，液体、凝胶、粉末、颗粒、糊状、或喷雾组合物)的任何材料/化合物，并且包括但不限于洗涤剂组合物(例如，液体和/或固体衣物洗涤剂和精细织物洗涤剂；硬表面清洁配制品，例如用于玻璃、木材、陶瓷以及金属台面和窗户；地毯清洁剂；炉灶清洁剂；织物清新剂；织物柔软剂；以及纺织品和衣物预去污剂(pre-spotter)，连同餐具洗涤剂)。除了包含本发明的双功能化合物之外，该洗涤剂配制品还可以包含一种或多种另外的酶(例如蛋白酶、淀粉酶、脂肪酶、角质酶、纤维素酶、内切葡聚糖酶、木葡聚糖酶、果胶酶、果胶裂解酶、黄原胶酶、过氧化物酶、卤代过氧合酶、过氧化氢酶以及甘露 聚糖酶，或其任何混合物)，和/或组分，例如表面活性剂、助洗剂、螯合剂(chelator)或螯合试剂(chelating agent)、漂白系统或漂白组分、聚合物、织物调理剂、增泡剂、抑泡剂、染料、香料、晦暗抑制剂、光学增亮剂、杀细菌剂、杀真菌剂、污垢悬浮剂、防蚀剂、酶抑制剂或稳定剂、酶激活剂、一种或多种转移酶、水解酶、氧化还原酶、上蓝剂和荧光染料、抗氧化剂以及增溶剂。
餐具洗涤：术语“餐具洗涤”是指所有形式的洗涤餐具，例如手动或自动餐具洗涤(ADW)。洗涤餐具包括但不限于，清洁所有形式的陶器，例如盘子、杯子、玻璃杯、碗，所有形式的用餐工具，例如匙、刀、叉，以及上菜用具连同陶瓷，塑料，金属，瓷器，玻璃及丙烯酸酯。
短程洗涤：术语“短程洗涤”是指相较于欧洲通常的洗涤习惯和洗涤时长而言，整个洗涤过程为显著缩短的亚洲洗涤过程和美国洗涤过程。通常，欧洲洗涤程序的包括主洗周期和淋洗周期整个时长程序可长达3小时，其中主洗周期可长达50-110分钟；本发明描述的短程洗涤的洗涤周期通常不超过110分钟，优选不超过100分钟，不超过90分钟，不超过80分钟，不超过60分钟，不超过50分钟，不超过30分钟。
主洗周期：术语“主洗周期”是指包括将纺织品或其他待洗物品浸泡在洗涤液中，将某种机械作用施加至该纺织品，以释放污物，并且协助洗涤液流进和流出该纺织品或其他待洗物品，并且最终去除多余的洗涤液的过程。本发明的短程洗涤的主洗周期一般不超过90分钟，优选不超过70分钟，优选不超过50分钟，优选不超过30分钟，优选不超过20分钟，优选不超过15分钟，优选不超过12分钟。
淋洗周期：术语“淋洗周期”是指在主洗周期完成后用不含洗涤液的清水对纺织品或其他待洗物品进行淋洗和脱水的过程。
洗涤液：在此将术语“洗涤液”定义为任选地包含用于洗涤纺织品或其他待洗物品的水和洗涤剂的溶液或混合物。
硬表面清洁：在此将术语“硬表面清洁”定义为清洁硬表面，其中硬表面可以包括地板、桌子、墙壁、屋顶等，连同硬物体的表面，例如汽车(汽车洗涤)和餐具(餐具洗涤)。餐具洗涤包括但不限于，清洁盘子、杯子、玻璃杯、碗、用餐工具(例如匙、刀、叉)、上菜用具、陶瓷、塑料、金属、 瓷器、玻璃及丙烯酸酯。
增强的洗涤效果：术语“增强的洗涤效果”在此定义为在洗涤过程中添加增效胶囊相对于没有增效胶囊的洗涤剂组合物的洗涤效果展示出增加的洗涤效果，例如，去除污渍、维持白度、减少起球、织物颜色护理，去除气味，去除生物膜，防止、减少和/或去除污垢附着。术语“增强的洗涤效果”包括在衣物洗涤并且例如在硬表面清洁如自动化餐具洗涤(ADW)中的洗涤效果。本发明的增效胶囊可以用于增强上述的一种或多种洗涤效果。
洗衣：术语“洗衣”涉及家用洗衣和工业洗衣两者并且意指用包含本发明的清洁或洗涤剂组合物的溶液处理纺织品的过程。洗衣过程可以例如使用例如家用或工业洗衣机进行或可以手动进行。
纺织品：术语“纺织品”意指包括纱线、纱线中间体、纤维、非机织物材料、天然材料、合成材料、以及任何其他纺织品材料的任何纺织品材料，这些材料制造的织物和由这些织物制成的产品(例如服装和其他物品)。该纺织品或织物可以处于针织品、机织物、牛仔布、非机织物、毡、纱线、以及毛巾布的形式。这些纺织品可以是纤维素基的，如天然纤维素，包括棉布、亚麻/亚麻布、黄麻、苎麻、剑麻或椰壳纤维或者人造纤维素(例如，来源于木浆)，包括纤维胶/人造丝、醋酸纤维素纤维(三胞)、莱赛尔纤维(lyocell)或其共混物。纺织品或织物也可以不基于纤维素，如天然聚酰胺，包括羊毛、驼毛、羊绒、马海毛、兔毛和蚕丝或合成聚合物如尼龙、芳族聚酰胺、聚酯、丙烯酸、聚丙烯和氨纶/弹性纤维(spandex/elastane)、或其共混物其以及基于纤维素和不基于纤维素的纤维的共混物。共混物的实例是棉和/或人造丝/纤维胶与一种或几种伴随材料的共混物，该伴随材料例如是羊毛、合成纤维(例如聚酰胺纤维、丙烯酸纤维、聚酯纤维、聚氯乙烯纤维、聚氨酯纤维、聚脲纤维、芳族聚酰胺纤维)和/或含纤维素的纤维(例如人造丝/纤维胶、苎麻、亚麻/亚麻布、黄麻、醋酸纤维素纤维、莱赛尔纤维)。织物可以是常规的可洗涤衣物，例如玷污的家居衣物。当使用术语织物或服装时，旨在也包括广义术语纺织品。
白度：在此将术语“白度”定义为在不同领域并且针对不同顾客具有不同含义的广义术语。白度的损失可以例如归因于灰化、黄化、或光学增亮剂/调色剂的去除。灰化和黄化可归因于污垢再沉积、身体污垢、来自例如铁和 铜离子或染料转移的着色。白度可以包括来自以下列表的一个或若干问题：着色剂或染料作用；不完全污物去除(例如身体污垢、皮脂等)；再沉积(物体的灰化、黄化或其他变色)(去除的污垢与纺织品的其他部分(弄脏的或未弄脏的)再关联)；在应用过程中纺织品的化学变化；以及颜色的澄清或淡色化。
崩解性能：本发明中使用的术语“崩解性能”是指在特定条件下由崩解时间所限定的胶囊外壳裂解释放内容物的速度相关的性质。
崩解时间：本发明中使用的术语“崩解时间”是指在洗涤过程中胶囊外壳破裂暴露出洗涤用酶所需要的时间，其具体测定见下文分析方法部分“崩解时间测定”部分的详细描述。
残留率：本发明中使用的术语“残留率”是指在洗涤过程中胶囊外壳没有完全溶解，而残留在洗涤物品或洗涤机器表面上的部分的比例，其具体测定见下文分析方法部分“残留率”的详细描述。
发明详细说明
在一个方面，本发明涉及一种增效胶囊，其包括胶囊外壳，和包含在胶囊外壳内部的洗涤用酶，其能够增强在短程洗涤程序中的洗涤效果。通常欧洲常见洗涤程序的总时长和主洗周期的时长均比亚洲和美国的洗涤程序中常见的洗涤周期要长。本发明的发明人令人惊奇地发现一些特定材料的胶囊外壳制备的增效胶囊可以在相对短的洗涤周期和/或相对较低的洗涤温度下实现洗涤用酶的洗涤增效效果，而不必经历欧洲中所通常需要的长得多的洗涤时间和一般相对较高的洗涤温度，同时不会产生不需要的胶囊残留物。
不受限于理论的限制，本发明的适于短程洗涤程序的增效胶囊的胶囊外壳的物理化学结构和性质，比如水溶解性，崩解性能，及其可能与胶囊内包涵的洗涤用酶的相互作用，贡献了本发明的增效胶囊的显著增强的洗涤效果。在洗涤程序中运用本发明的增效胶囊与洗涤剂共同使用，可以在相对短的洗涤时间和相对低的洗涤温度下取得与不使用增效胶囊相比更优的洗涤效果，从而可以有效地节省洗涤所需的能源消耗，水的消耗，并减少污水的排放，有利于环境的保护和资源的节省，有利于绿色生态社会的发展。
在一个实施方案中，本发明的增效胶囊的胶囊外壳具有在20℃下含2％ 表面活性剂的洗涤液中崩解时间不超过30分钟，优选不超过20分钟，不超过15分钟，不超过10分钟，不超过8分钟，不超过6分钟，不超过5分钟。由于亚洲洗涤过程一般为相对短程的洗涤周期，如果期待洗涤用酶能够在该短程洗涤周期中起到作用，则需要增效胶囊的胶囊外壳有较短的崩解时间，使得洗涤用酶能在洗涤液中尽早释放从而有较长的时间进行酶的催化作用，实现洗涤用酶的洗涤增效功能。
由于亚洲和美国洗涤过程一般为相对短程的洗涤周期，这就要求增效胶囊的胶囊外壳不仅要尽快崩解以释放内容物，还要保证其在洗涤周期结束后的残留尽可能少，不能对消费者造成可以观察到的残留的困扰。在另一个实施方案中，本发明的增效胶囊的胶囊外壳具有在15℃-30℃下的洗涤过程中不超过18％，不超过12％，优选不超过10％，优选不超过8％，优选不超过6％，优选不超过4％，优选不超过3％，优选不超过1％的残留率。
在另一个实施方案中，本发明的增效胶囊能够在短程洗涤程序中实现显著的洗涤增效的效果，其中所述短程洗涤包含不超过110分钟的洗涤周期，优选不超过100分钟，不超过80分钟，不超过60分钟，不超过50分钟，不超过30分钟。在在另一个实施方案中，短程洗涤程序中主洗周期不超过90分钟，不超过70分钟，优选不超过50分钟，优选不超过30分钟，优选不超过20分钟，优选不超过15分钟，优选不超过12分钟。
本发明的增效胶囊优选能够在相对低的洗涤温度内实现洗涤用酶的增效效果，而没有显著的残留问题。在另一个实施方案中，短程洗涤程序中具有不超过60℃的洗涤温度，优选不超过40℃，不超过35℃，不超过30℃，不超过20℃，不超过10℃，不超过4℃。
在另一个实施方案中，本发明的增效胶囊的胶囊外壳由包含纤维素衍生物、淀粉衍生物或普鲁兰多糖的材料制成，优选由包含普鲁兰多糖的材料制成。
在另一个实施方案中，本发明的增效胶囊中包含的洗涤用酶选自以下的组：蛋白酶，淀粉酶，纤维素酶、脂肪酶、磷脂酶、角质酶、氧化酶、加氧酶、转移酶、还原酶、半纤维素酶、甘露聚糖酶、酯酶、异构酶、果胶酶、乳糖酶、过氧化物酶、裂合酶、漆酶、脱氧核糖核酸酶,地衣多糖酶，及其组合。在另一个实施方案中，所述洗涤用酶选自以下的组：蛋白酶、淀粉酶、 甘露聚糖酶，纤维素酶及其组合。
在一个实施方案中，包含在本发明的增效胶囊中洗涤用酶中基本不包含表面活性剂、漂白剂或漂白激活剂。
本发明的增效胶囊优选与低成本的洗涤剂共同应用在洗涤过程中，所述低成本的洗涤剂通常不包含洗涤用酶，或只包含少量的和/或价格便宜的某一种或几种酶。由于本发明的增效胶囊以独立于洗涤的单剂量形式提供，消费者可以视待洗涤的衣物和器具附着的具体污渍的情形而选择特定的一种或多种增效胶囊与洗涤剂共同使用，可以有效地去除污渍。
在另一个实施方案中，本发明的增效胶囊中包含的洗涤用酶为不含酶稳定剂成分的低成本酶颗粒形式。本发明的增效胶囊可以提供在成本方面有效的方法，将酶直接交付给消费者而不用顾虑酶稳定性和与洗涤剂中其他成分的兼容性的问题。
在一个实施方案中，本发明的增效胶囊其大小为约5mm，约10mm，约20mm，约30mm，约40mm，到约100mm。本发明的胶囊形状类似于一般可见的药用胶囊的行政，为卵圆形或长圆形，当描述其大小时，通常以胶囊的长轴作为其大小的指征。
在另一个实施方案中，本发明的增效胶囊提供的增强的洗涤效果选自：去除污渍、维持白度、减少起球、织物颜色护理，去除气味，及其组合。
在另一个方面，本发明涉及一种用于增强洗涤效果的增效胶囊，其包括由包含普鲁兰多糖的材料制成的胶囊外壳，和包含在上述胶囊外壳内的洗涤用酶。
在另一个方面，本发明涉及普鲁兰多糖在制备用于增强洗涤效果的增效胶囊中的应用。
在另一个方面，本发明涉及一种试剂盒，其包含一个或多个前文所述的增效胶囊，所述增效胶囊上具有相应的视觉识别要素。所述的视觉识别要素可以帮助消费者了解具体的各个增效胶囊能提供的一种或多种洗涤增效效果。在一个实施方案中，所述的增效胶囊被单独包裹在泡状包装材料中，上述增效胶囊可以单个包装或多个包装的组合，例如组成连续的一列，或连续几列形成方阵的形式提供。
在另一个方面，本发明涉及制备如前文所述的增效胶囊的方法，包括： a)筛选在15℃-30℃，优选25℃下的洗涤过程中残留率不超过18％，不超过12％，优选不超过10％，优选不超过8％，优选不超过6％，优选不超过4％，优选不超过3％，优选不超过1％的胶囊外壳，和b)将洗涤用酶增效剂填充到胶囊外壳内部。在一个实施方案中，还包括在步骤b之前的如下步骤：c)筛选具有在20℃下含2％表面活性剂的洗涤液中崩解速率不超过30分钟，优选不超过20分钟，不超过15分钟，不超过10分钟，不超过8分钟，不超过6分钟，不超过5分钟的胶囊外壳，其中步骤c)在步骤a)之前，之后或同时进行。
胶囊外壳/增效胶囊
本发明的增效胶囊的胶囊外壳可以被选择使得所述增效胶囊为硬胶囊或软胶囊。通常硬胶囊被用来灌装粉末或颗粒形式的内容物，而软胶囊更适用于液体，半液体或油基的内容物。本发明的胶囊与药物胶囊因期待实现递送的内容物的不同，在递送的途径和方式上也存在着差异。
在本发明的一个实施方案中，增效胶囊是硬胶囊。所述硬胶囊由两部分壳组成，分别包括将活性物质填入其中的"胶囊体"，和紧密地配合在“胶囊体”上的"帽"。胶囊体和帽可以预先制备，或可以从胶囊制造商购得。如其名称所示，硬胶囊是硬的和非柔性的。洗涤用酶，不论是颗粒或粉末形式，也不论其是否与载体材料或合适的稀释剂和赋形剂如乳糖，硬脂酸镁，或淀粉等混合，可以被装入空的胶囊体中。随后将帽放在胶囊体上，两者紧密配合以完全包封洗涤用酶。此方法可以手工进行，但是更通常地通过应用多种商业可得的胶囊填充机器来完成。
在本发明的一个实施方案中，硬胶囊外壳由包含多糖的材料制成，包括但不限于：
以水溶性纤维素衍生物为主要原料制成的胶囊：如羟丙基甲基纤维素(HPMC)胶囊，如中国专利公开说明书CN1418081A、CN1329478A公开由羟丙基甲基纤维素的水溶性纤维素衍生物、增塑剂等制成的胶囊。CN1202102A公开羧甲基纤维素钙或交联羧甲基纤维素钠，明胶化淀粉和聚乙烯聚吡咯烷酮等制成的胶囊。CN1292261A公开由亲水性凝胶、水溶性纤维素、助凝剂制成的植物硬胶囊。CN1646369A公开由可溶于水的纤维素衍生物如羟脯氨酰甲基纤维素、增塑剂等制成的胶囊。CN1745745A公开由K- 卡拉胶，纤维素衍生物如羟丙甲纤维素、乙基纤维素、羟丙基纤维素、羧甲基纤维素，醇类制成的空心胶囊。
植物淀粉胶囊：由植物淀粉(比如马铃薯淀粉，木薯淀粉)及淀粉衍生物(例如羟丙基淀粉，羟丙基羧甲基淀粉)为主要原料，配合一定的增塑剂等制成。羟丙基淀粉，尤其是羟丙基含量在一定范围内的羟丙基淀粉，经过在一定温度下加热糊化得到的胶液，并在不同温度条件下分别稳定一定时间，可以在不添加或很少添加增塑剂、粘合剂以及凝胶剂的条件下，制得性能和质量完全能够适合本发明使用的羟丙基淀粉空心胶囊。如中国专利公开说明书CN1483393A公开的淀粉空心胶囊及其生产工艺，由植物淀粉或淀粉衍生物、增塑剂、水等组分制成。CN1623529A公开的胶囊由薯类淀粉、卡拉胶、表面活性剂、增塑剂组成。CN1739488A公开以魔芋葡苷聚糖经酸解氧化改性，与改性或未改性植物蛋白(包括大豆蛋白、玉米醇溶蛋白、小麦蛋白、玉米蛋白)，动物明胶或鱼明胶中的一种或两种复合为主要成分，以及甘油、十二烷基磺酸盐等辅助成分制成空心胶囊。CN1895234A公开的空心胶囊以直链淀粉，甘油为主要原料制得。CN1931145A公开由直链淀粉或可溶性淀粉如玉米、马铃薯、木薯、番薯、山芋的提取物和甘油等制成植物空心胶囊，CN1687203A公开由淀粉糊化后按比例加入增塑剂、凝胶、表面活性剂、遮光剂、食用色素等制成的硬胶囊或软胶囊。CN103893772B公开的一种羟丙基淀粉空心胶囊，其由羟丙基淀粉、水、粘合剂、遮光剂、着色剂、芳香剂和(或)矫味剂构成。CN104800189B公开的一种淀粉植物空心胶囊，主要由天然淀粉50-80份、植物纤维30-50份和去离子水50-90份，然后采用常规制备空心胶囊的工艺制备而得，其特征在于，所述的植物纤维主要选自柚皮纤维素，所述的天然淀粉选自木薯淀粉，所述的空心胶囊还包括植物胶中的卡拉胶、魔芋胶、结冷胶、黄原胶、胡麻胶、田菁胶中的一种或组合。CN104586813B公开的全淀粉植物胶囊，其中包含全淀粉植物胶75％～90％，水5％～20％，粘合剂0～5％，遮光剂0～2％，着色剂0～3％，矫味剂0～5％。
其他的淀粉胶囊公开于例如CN105395513B,CN105030723B，CN105017567B,CN104800188B,CN104800189B,CN104586813B CN103893772B,CN104800186B。
此外其他的多糖胶囊还包括例如CN1903157A公开的以海藻多糖胶为原 料制造空心胶囊。
以其他多糖高分子为主要原料制成的胶囊，例如普鲁兰多糖胶囊。普鲁兰多糖英文名称pullulan，中文也译为普鲁兰糖、茁霉多糖、出芽短梗孢糖、普聚多糖，可由淀粉水解物、蔗糖、或其它糖类直接发酵产生，是出芽孢梗霉产生的胞外多糖，主要以α-1，6-糖苷键结合麦芽糖构成同型多糖，即葡萄糖按α-1，4-糖苷键结合成麦芽三糖，两端再以α-1，6-糖苷键同另外的麦芽三糖结合，如此反复连接成为高分子多糖，α-1，4-糖苷键和α-1，6-糖苷键的比例为2∶1，聚合度10～30000，分子量2.0×103～5.0×106道尔顿。普鲁兰多糖可由普鲁兰糖发酵液经杀菌、脱色、脱盐后用喷雾、流化床等方式脱水干燥而得，也可以采用有机溶剂法提取而成的干燥物，如中国专利公开说明书CN1651467A介绍的方法，将普鲁兰糖发酵液杀菌后，用乙醇、异丙醇等有机溶剂脱色、脱盐和脱水后的沉淀物干燥而获得。其他适用于本发明的普鲁兰多糖胶囊包括如欧洲专利EP2663294B1,CN107951858A,CN106236730A,CN105055365B中公开的。
在本发明的一个优选实施方案中，增效胶囊的胶囊外壳是纤维素衍生物胶囊或普鲁兰多糖胶囊。
在本发明的一个优选实施方案中，增效胶囊的胶囊外壳是普鲁兰多糖胶囊。普鲁兰多糖胶囊具有与明胶胶囊相当的透明度，使得充填内容物清楚可见，在宽温湿度范围内贮存稳定，透氧率低避免充填内容物的氧化，同时避免了明胶胶囊制备过程中处理动物皮毛等产生的污染问题和明胶在洗涤过程中崩解速度不够迅速，并在洗涤过程结束后产生胶囊材料的残留物粘附在洗涤衣物和其他硬表面，从而严重影响消费者对洗涤效果的评价的问题。
商业可获得的硬胶囊包括：植物胶囊
Figure PCTCN2018099196-appb-000001
(苏州胶囊公司Capsugel)，这是一种HPMC(羟丙甲纤维素)胶囊，天然胶囊Plantcaps TM(苏州胶囊公司Capsugel)，这是一种普鲁兰多糖胶囊，
Figure PCTCN2018099196-appb-000002
(普鲁兰多糖)胶囊(苏州力凡胶囊公司)，这是另一种HPMC(羟丙甲纤维素)胶囊；海藻多糖胶囊(#0，分别可购自江苏辰星药业股份有限公司和上海红星植物胶丸有限公司，湘尔康淀粉胶囊(#0，购于湖南尔康制药有限公司)。
其他可用的硬胶囊例如在EP2663294B1,CN101480447A等中描述的胶囊。
在本发明的一个实施方案中，所述胶囊外壳为非明胶材料制成。
在本发明的一个实施方案中，硬胶囊优选是一种胶囊外壳，所述胶囊外壳具有在20℃下含2％表面活性剂的洗涤液中不超过30分钟，优选不超过20分钟，不超过15分钟，不超过10分钟，不超过8分钟，不超过6分钟，不超过5分钟的崩解时间。
在本发明的另一个实施方案中，本发明的硬胶囊的材料的选择优选具有在15-30℃洗涤过程中不超过18％，不超过12％，优选不超过10％，优选不超过8％，优选不超过6％，优选不超过4％，优选不超过3％，优选不超过1％的残留率。
在本发明的另一个实施方案中，增效胶囊的胶囊外壳是软凝胶胶囊。软凝胶胶囊是一片密封的软壳，其内含有液体、悬浮液或半固体作为填充物。软凝胶胶囊壳由成膜材料和水可分散性或水溶性增塑剂制成，从而赋予柔性。软胶囊可以由聚合物制成，如羟丙基甲基纤维素。合适的液体填充材料是植物油、蜡、或聚乙二醇或与胶囊组合物相容的其它液体。软凝胶胶囊可以输送液体酶，或输送干燥的酶颗粒，如悬浮剂。制备软凝胶胶囊，将酶或活性成分与填充材料混合。同时，通过混合成膜材料和增塑材料，制备胶囊基底。胶囊的形成和填充同时进行。包囊机将胶囊基底形成为两个薄膜，其供给在两个旋转模具之间。模具含有胶囊形状和大小的凹陷。与模具同步的泵输送液体填充材料进入凹陷，随后，在填充后，胶囊立即通过压力被密封。包囊之后，软凝胶胶囊经历两步干燥过程，在转筒式干燥机或流化床干燥机中完成，随后是进行盘式干燥，或固化数天。
洗涤用酶
本发明的增效胶囊包括包含在胶囊外壳内部的洗涤用酶。
本申请上下文使用的酶可以是能够通过发酵得到的任何酶或不同酶的组合。相应地，当提到“酶”时，通常应理解为包括单一的酶和一种以上的酶的组合。
应理解的是：术语“酶”包括酶的变体(例如用重组技术制备的)。这些酶的变体的例子记载于以下文献中：例如EP 251,446(Genencor)，WO 91/00345(Novo Nordisk)，EP 525,610(Solvay)和WO 94/02618(Gist-Brocades NV)。本说明书和权利要求书中使用的酶的分类法与学术出版公司1992年出 版的《生物化学和分子生物学国际联合会命名委员会的建议(1992)》一致(Recommendations(1992)of the Nomenclature Committee of the International Union of Biochemistry and Molecular Biology，Academic Press，Inc.，1992)。
适合用于本发明的增效胶囊中的洗涤用酶包括蛋白酶、纤维素酶、脂肪酶、磷脂酶、角质酶、氧化酶、加氧酶、转移酶、还原酶、半纤维素酶、甘露聚糖酶、淀粉酶、酯酶、异构酶、果胶酶、乳糖酶、过氧化物酶、果胶酸裂合酶、漆酶、脱氧核糖核酸酶,地衣多糖酶，和它们的混合物。优选的酶包括能够水解底物(例如，污迹)的那些酶。这些酶已知为水解酶，包括但不限于蛋白酶(细菌、真菌、酸性、中性或碱性蛋白)、淀粉酶(a或p)、脂肪酶、纤维素酶、和它们的混合物。
蛋白酶
合适的蛋白酶可以是动物、植物或微生物来源的。在本发明的一个实施例中，蛋白酶是化学修饰或蛋白质工程的。在一个实施例中，蛋白酶是丝氨酸蛋白酶或金属蛋白酶，优选碱性微生物蛋白酶或胰蛋白酶样蛋白酶。碱性蛋白酶的例子例如枯草杆菌蛋白酶，例如那些来自芽胞杆菌属，例如，枯草杆菌蛋白酶诺和(Novo)、枯草杆菌蛋白酶嘉士伯、枯草杆菌蛋白酶309、枯草杆菌蛋白酶147、枯草杆菌蛋白酶168(描述于WO89/06279)的蛋白酶。胰蛋白酶样蛋白酶的例子包括牛源胰蛋白酶、猪源的胰蛋白酶和镰刀菌属蛋白酶，描述于WO 89/06270和WO 94/25583。
有用的蛋白酶的例子是那些WO 92/19729,WO 98/20115,WO 98/20116,和WO 98/34946中描述的蛋白酶，尤其是那些在以下位点具有一个或多个取代的蛋白酶的变体：27,36,57,76,87,97,101,104,120,123,167,170,194,206,218,222,224,235,和274。
优选的商业可获得的蛋白酶包括但不限于
Figure PCTCN2018099196-appb-000003
Duralase TM，Durazym TM，
Figure PCTCN2018099196-appb-000004
Ultra,
Figure PCTCN2018099196-appb-000005
Ultra,
Figure PCTCN2018099196-appb-000006
Uno,
Figure PCTCN2018099196-appb-000007
Excel,
Figure PCTCN2018099196-appb-000008
Figure PCTCN2018099196-appb-000009
Ultra,
Figure PCTCN2018099196-appb-000010
Ultra,
Figure PCTCN2018099196-appb-000011
Blaze
Figure PCTCN2018099196-appb-000012
100T,Blaze
Figure PCTCN2018099196-appb-000013
125T,Blaze
Figure PCTCN2018099196-appb-000014
150T,
Figure PCTCN2018099196-appb-000015
和
Figure PCTCN2018099196-appb-000016
(Novozymes A/S),,
Figure PCTCN2018099196-appb-000017
Purafect
Figure PCTCN2018099196-appb-000018
Purafect
Figure PCTCN2018099196-appb-000019
Excellenz P1000 TM,Excellenz P1250 TM,
Figure PCTCN2018099196-appb-000020
Preferenz P100 TM,Purafect
Figure PCTCN2018099196-appb-000021
Preferenz P110 TM,Effectenz P1000 TM,
Figure PCTCN2018099196-appb-000022
Effectenz P1050 TM,Purafect
Figure PCTCN2018099196-appb-000023
Effectenz P2000 TM,
Figure PCTCN2018099196-appb-000024
和
Figure PCTCN2018099196-appb-000025
(Danisco/DuPont),Axapem TM(Gist-Brocases N.V.),BLAP(US5352604图29中所示序列)及其变体(汉高公司)，和KAP(Bacillus alkalophilus subtilisin)(花王公司)。
纤维素酶
合适的纤维素酶可以是动物、植物或微生物来源的。在本发明的一个实施例中，蛋白酶是化学修饰或蛋白质工程的。该纤维素酶可以源自芽胞杆菌属、假单胞菌属、腐质霉、镰孢霉属、梭孢壳菌属或支顶孢属。在本发明的一个实施例中，该纤维素酶源自特异腐质霉、嗜热毁丝霉、Sporotrichum pulverulentum、尖孢镰刀菌、里氏木霉、太瑞斯梭孢壳霉、支顶孢属物种、支顶孢属物种CBS 478.94、菜豆壳球孢菌CBS 281.96、Crinipellis scabella CBS 280.96、Volutella colletotrichoides或粪生粪壳菌ATCC 52644或芽胞杆菌属SP-KSMS237。合适的纤维素酶的例包括在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 5,763,254,WO 95/24471,WO 98/12307和WO99/001544中公开的那些。
其他的纤维素酶是具有与WO 2002/099091的SEQ ID NO:2的第1到773位的氨基酸具有至少97％序列一致性的内切-1,4-β-葡聚糖酶，或具有与WO 2001/062903的SEQ ID NO:2的第40到559位的氨基酸具有至少60％序列一致性的44家族木葡聚糖酶。
优选的商业可获得的纤维素酶包括但不限于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.),和KAC-500(B) TM(Kao Corporation)。
淀粉酶
淀粉酶是α-淀粉酶或葡糖淀粉酶，优选是微生物来源的或化学修饰或蛋 白质工程的。其是细菌或真菌来源的。例如，该淀粉酶可以是从芽胞杆菌属，例如地衣芽孢杆菌获得的α-淀粉酶。如GB1,296,839中详细描述的来自地衣芽孢杆菌的一个特定菌株的α-淀粉酶。
有用的淀粉酶的例子，尤其是在一个或多个下述位置中具有取代的变体：15、23、105、106、124、128、133、154、156、181、188、190、197、202、208、209、243、264、304、305、391、408和444，在WO 94/02597、WO 94/18314、WO 1995/010603、WO 1995/026397、WO 96/23873、WO 97/43424和WO 00/60060、WO 2001/066712、WO 2006/002643中描述。
在特定实施方案中，α-淀粉酶衍生自芽孢杆菌属菌种菌株NCIB 12289、NCIB 12512、NCIB 12513和DSM 9375。尤其优选的是显示于WO 95/26397的SEQ ID NOS 1和2中的α-淀粉酶。
优选的商业可获得的淀粉酶包括但不限于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 S100 and Preferenz S110(from Genencor International Inc./DuPont)。
脂肪酶和角质酶
脂肪酶是细菌或真菌源的。包括化学修饰的或蛋白质工程化的突变酶。实例包括来自嗜热真菌属的脂肪酶，例如如描述于EP 258068和EP 305216中的来自疏绵状嗜热丝孢菌(早先命名为疏棉状腐质霉)；来自腐质霉属的角质酶，例如特异腐质霉(WO 96/13580)；来自假单胞菌属的菌株的脂肪酶(这些中的一些现在改名为伯克霍尔氏菌属)，例如产碱假单胞菌或类产碱假单胞菌(EP 218272)、洋葱假单胞菌(EP 331376)、假单胞菌属菌株SD705(WO 95/06720&WO 96/27002)、威斯康星假单胞菌(P.wisconsinensis)(WO 96/12012)；GDSL-型链霉菌属脂肪酶(WO 10/065455)；来自稻瘟病菌的角质酶(WO 10/107560)；来自门多萨假单胞菌的角质酶(US 5,389,536)；来自褐色嗜热裂孢菌(Thermobifida fusca)的脂肪酶(WO 11/084412)；嗜热脂肪土芽孢杆菌脂肪酶(WO 11/084417)；来自枯草芽孢杆菌的脂肪酶(WO 11/084599)；以及来自灰色链霉菌(WO 11/150157)和始旋链霉菌(S.pristinaespiralis)的脂肪酶(WO 12/137147)。
其他实例是脂肪酶变体，例如描述于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 97/04079、WO 97/07202、WO 00/34450、WO 00/60063、WO 01/92502、WO 07/87508以及WO 09/109500中的那些。
优选的商业化脂肪酶产品包括但不限于Lipolase TM、Lipex TM、Lipolex TM和Lipoclean TM(诺维信公司)，Lumafast(来自杰能科公司(Genencor))以及Lipomax(来自吉斯特布罗卡德斯公司(Gist-Brocades))。
其他实例是有时称为酰基转移酶或过水解酶的脂肪酶，例如与南极假丝酵母(Candida antarctica)脂肪酶A具有同源性的酰基转移酶(WO 10/111143)、来自耻垢分枝杆菌(Mycobacterium smegmatis)的酰基转移酶(WO 05/56782)、来自CE 7家族的过水解酶(WO 09/67279)以及耻垢分枝杆菌过水解酶的变体(特别是来自亨斯迈纺织品染化有限公司(Huntsman Textile Effects Pte Ltd)的商业产品Gentle Power Bleach中所用的S54V变体)(WO 10/100028)。
果胶酸裂合酶
果胶酸裂合酶可以是衍生自芽孢杆菌属特别是地衣芽孢杆菌或B.agaradhaerens的野生型酶，或例如如US 6,124,127(NZ 5543)、WO 1999/027083(NZ 5377)、WO 1999/027084(NZ 5378)、WO 2002/006442(NZ 10044)、WO 2002/092741(NZ 10171)或WO 2003/095638(NZ 10190)中所述的这些衍生的变体。
甘露聚糖酶
甘露聚糖酶是水解甘露聚糖的酶。合适的甘露聚糖酶包括来自于细菌或真菌来源的，也包括化学修饰的或蛋白质工程化的突变酶。甘露聚糖酶可以是家族5或26的碱性甘露聚糖酶。它可以是来自芽孢杆菌属或腐质霉属，特别是B.agaradhaerens、地衣芽孢杆菌、耐盐芽孢杆菌(B.halodurans)、克劳氏芽孢杆菌(B.clausii)或特异腐质霉的野生型。
合适的甘露聚糖酶在WO 1999/064619中描述。商业可获得的甘露聚糖酶例如
Figure PCTCN2018099196-appb-000026
(Novozymes A/S),和EFFECTENZ TMM1000(Dupont)。
过氧化物酶/氧化酶
适合的过氧化物酶/氧化酶包括植物、细菌或真菌来源的过氧化物酶/氧化酶。化学修饰突变体或蛋白质工程突变体也包括在内。有用的过氧化物酶的例子包括来自鬼伞菌属(Coprinus)的过氧化物酶，例如来自灰盖鬼伞(C.Cinereus)的过氧化物酶。如EP 179,486中所详细描述，和WO 93/24618、WO 95/10602和WO 98/15257中所描述的它的变体。
商业上可获得的过氧化物酶包括但不限于Guardzyme TM(Novo Nordisk A/S)。
脱氧核糖核酸酶
具有脱氧核糖核酸酶(DNA酶)活性的多肽或脱氧核糖核酸酶(DNA酶)是催化DNA骨架中的磷酸二酯键的水解切割从而降解DNA的任何酶。可互换地使用两个术语，具有DNA酶活性的多肽和DNA酶。
优选的DNA酶可获得自细菌或真菌。化学修饰突变体或蛋白质工程突变体也包括在内。
优选的DNA酶可选自任何下述的酶家族：E.C.3.1.21.x,其中x＝l,2,3,4,5,6,7,8或9,E.C.3.1.22.y其中y＝l,2,4或5,E.C.3.1.30.Z其中z＝1or2,E.C.3.1.31.1及其混合物。
其他优选的DNA酶是EP 17165320.7中公开的那些DNA酶及其衍生的变体。
合用于本发明的增效胶囊中的洗涤用酶可以单一纯酶或不同种类酶的混合物的形式提供。增效胶囊中的单一酶或酶混合物的含量可以变化，与普通一勺商业上的含酶洗涤剂相比，其一般在洗涤周期中提供更高的酶剂量。选择增效胶囊中的纯酶剂量以增强传统清洁产品的清洁能力。例如，纯酶或有活性的酶的终浓度可以被选择，以便为每个洗衣或洗碟周期提供约0.0001ppm，约0.001ppm，约0.01ppm，约0.1ppm，至约1ppm，约2.5ppm，约5ppm，约10ppm，约25ppm，约50ppm的酶。本领域技术人员将知道，在有些情况下本发明中可以应用50ppm以上的酶浓度。
用于增效胶囊中的酶成分可以作为颗粒形式提供。在优选的实施方案中，所述酶颗粒是低成本颗粒，不带有在洗涤剂中贮存时稳定酶所需的较昂贵的成分，例如屏蔽材料，酶稳定剂和漂白中和剂等。当然，如果需要并且成本上有效，这些成分中的一些可以与酶共同存在与本发明的洗涤增效胶囊中。
一种低成本的性质优良的干燥酶颗粒的方法如中国授权专利ZL00814580.6(诺维信)中所描述的，其整体并入本文。该方法包括将含有酶和生物质的发酵肉汤原料喷雾干燥，其中该生物质构成从发酵得到的生物质的至少10％。
一种这样的颗粒具有包被在盐种(salt seed)上的酶和相对薄的盐包被层。酶成分也可以是干燥的粉末酶或分散在载体上或铺板在载体上的酶，所述载体如糖、淀粉或麦芽糊精。酶也可以在湿颗粒化过程中加入，如美国专利6,852,336所述，其整体并入本文。
下列非限制性专利公布列举说明了可以在本发明中应用的己知的酶配制物，并且优选地，被修改以降低或消除酶稳定剂，包括降低或消除屏蔽物质和保护性包被：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；和W096/38527。
本发明的洗涤增效胶囊除了包含洗涤用酶的颗粒之外，还可以包含与洗涤用酶颗粒混合的其他成分。在本发明的一个实施方案中，洗涤胶囊中的酶颗粒占胶囊重量的至少约1％,优选至少2.5％,至少5％,至少10％,至少15％,至少20％,至少25％，至少30％，至少35％，至少40％，至少45％，至少50％，至少60％，至少70％，至少80％，至少90％，至少95％，或至少99％。
聚合物
本发明的洗涤增效胶囊除了包含洗涤用酶的颗粒外，还可以包含本领域中已知的用于在洗涤剂中使用的任何聚合物。聚合物可以作为如以上提到的共助洗剂起作用，或可以提供抗再沉积、纤维保护、污垢释放、染料转移抑制、油污清洁和/或防沫特性。一些聚合物可以具有多于一种的以上提到的特性和/或多于一种的以下提到的基序(motif)。示例性聚合物包括(羧甲基)纤维素(CMC)、聚(乙烯醇)(PVA)、聚(乙烯吡咯烷酮)(PVP)、聚(乙二醇) 或聚(环氧乙烷)(PEG)、乙氧基化的聚(亚乙基亚胺)、羧甲基菊粉(CMI)、和聚羧化物，例如PAA、PAA/PMA、聚-天冬氨酸、和甲基丙烯酸月桂酯/丙烯酸共聚物、疏水改性CMC(HM-CMC)和硅酮、对苯二甲酸和低聚乙二醇的共聚物、聚(对苯二甲酸乙二酯)和聚(氧乙烯对苯二甲酸乙二酯)的共聚物(PET-POET)、PVP、聚(乙烯基咪唑)(PVI)、聚(乙烯吡啶-N-氧化物)(PVPO或PVPNO)以及聚乙烯吡咯烷酮-乙烯基咪唑(PVPVI)。另外的示例性聚合物包括磺化的聚羧酸盐、聚环氧乙烷和聚环氧丙烷(PEO-PPO)以及乙氧基硫酸二季铵盐。其他示例性聚合物披露于例如WO 2006/130575中。也考虑了以上提到的聚合物的盐。
织物调色剂
本发明的洗涤增效胶囊除了包含洗涤用酶的颗粒外，还可以包含本领域中已知的用于在洗涤剂中的织物调色剂，例如染料或色素，当配制在洗涤剂组合物中时，当所述织物与一种洗涤液接触时织物调色剂可以沉积在织物上，该洗涤液包括所述洗涤剂组合物，并且因此通过可见光的吸收/反射改变所述织物的色彩。荧光增白剂发射至少一些可见光。相比之下，因为它们吸收至少一部分可见光光谱，所以织物调色剂改变表面的色彩。适合的织物调色剂包括染料和染料-粘土轭合物，并且还可以包括色素。适合的染料包括小分子染料和聚合物染料。适合的小分子染料包括选自下组的小分子染料，该组由落入颜色索引(Colour Index)(C.I.)分类的以下染料组成：直接蓝、直接红、直接紫、酸性蓝、酸性红、酸性紫、碱性蓝、碱性紫和碱性红、或其混合物，例如描述于WO 2005/03274、WO 2005/03275、WO 2005/03276和EP 1876226中(将其通过引用而特此结合)。洗涤剂组合物优选包括从约0.00003wt％至约0.2wt％、从约0.00008wt％至约0.05wt％、或甚至从约0.0001wt％至约0.04wt％的织物调色剂。该组合物可以包括从0.0001wt％至0.2wt％的织物调色剂，当该组合物处于单位剂量袋的形式时，这可以是特别优选的。适合的调色剂还披露于例如WO 2007/087257和WO 2007/087243中。本发明的一个实施方案中，洗涤胶囊中的织物调色剂占胶囊重量的约0.002％，约0.02％，约0.2％，约0.5％，约1％，更多。
染料转移抑制剂
本发明的洗涤增效胶囊还可以包括一种或多种染料转移抑制剂。适的聚合物染料转移抑制剂包括但不限于聚乙烯吡咯烷酮聚合物、多胺N-氧化物聚合物、N-乙烯吡咯烷酮与N-乙烯基咪唑的共聚物、聚乙烯噁唑烷酮以及聚乙烯咪唑或其混合物。当存在于洗涤增效胶囊中时，染料转移抑制剂可以占胶囊重量的约0.1％，0.2％，0.5％或更多。
荧光增白剂
本发明的洗涤增效胶囊还可以包含另外的组分，这些组分可以给正在清洁的物品着色，例如荧光增白剂或光学增亮剂。在本发明的组合物中可以使用适合用于在衣物洗涤剂组合物中使用的任何荧光增白剂。最常用的荧光增白剂是属于以下类别的那些：二氨基芪-磺酸衍生物、二芳基吡唑啉衍生物和二苯基-联苯乙烯基衍生物。二氨基芪-磺酸衍生物类型的荧光增白剂的实例包括以下的钠盐：4,4'-双-(2-二乙醇氨基-4-苯胺基-均-三嗪-6-基氨基)芪-2,2'-二磺酸盐、4,4'-双-(2,4-二苯胺基-均-三嗪-6-基氨基)芪-2.2'-二磺酸盐、4,4'-双-(2-苯胺基-4-(N-甲基-N-2-羟基-乙基氨基)-均-三嗪-6-基氨基)芪-2,2'-二磺酸盐、4,4'-双-(4-苯基-1,2,3-三唑-2-基)芪-2,2'-二磺酸盐以及5-(2H-萘并[1,2-d][1,2,3]三唑-2-基)-2-[(E)-2-苯基乙烯基]苯磺酸钠。优选的荧光增白剂是可从汽巴–嘉基股份有限公司(Ciba-Geigy AG)(巴塞尔，瑞士)获得的天来宝(Tinopal)DMS和天来宝CBS。天来宝DMS是4,4'-双-(2-吗啉代-4-苯胺基-s-三嗪-6-基氨基)芪-2,2'-二磺酸盐的二钠盐。天来宝CBS是2,2'-双-(苯基-苯乙烯基)-二磺酸盐的二钠盐。还优选荧光增白剂，是可商购的Parawhite KX，由派拉蒙矿物与化学(Paramount Minerals and Chemicals)，孟买，印度供应。适合用于在本发明中使用的其他荧光剂包括1-3-二芳基吡唑啉和7-烷氨基香豆素。适合的增亮剂或荧光增白剂可占本发明的洗涤增效胶囊重量的约0.1％,约0.5％,约1％，约5％，10％，20％，50％或更多。
污物释放聚合物
本发明的洗涤增效胶囊还可以包括一种或多种污物释放聚合物，这些聚合物帮助从织物(如棉布和基于聚酯的织物)移除污物，特别是从基于聚酯 的织物移除疏水性污物。污物释放聚合物可以例如是非离子型或阴离子型对苯二甲酸基聚合物、聚乙烯基己内酰胺和相关共聚物、乙烯基接枝共聚物、聚酯聚酰胺，参见例如粉状洗涤剂，表面活性剂科学系列第71卷第7章，马塞尔·德克尔公司(Marcel Dekker，Inc.)。另一种类型的污物释放聚合物是包括一个芯结构和连接至该芯结构的多个烷氧基化基团的两亲性烷氧基化油污清洁聚合物。核心结构可以包括聚烷基亚胺结构或聚烷醇胺结构，如WO 2009/087523中详细描述的(将其通过引用而特此结合)。此外，随机接枝共聚物是适合的污物释放聚合物。适合的接枝共聚物更详细地描述于WO 2007/138054、WO 2006/108856和WO 2006/113314中(将其通过引用而特此结合)。其他污物释放聚合物是取代的多糖结构，尤其是取代的纤维素结构，例如改性纤维素衍生物，例如EP 1867808或WO 2003/040279中描述的那些(将二者都通过引用而特此结合)。适合的纤维素聚合物包括纤维素、纤维素醚、纤维素酯、纤维素酰胺及其混合物。适合的纤维素聚合物包括阴离子改性的纤维素、非离子改性的纤维素、阳离子改性的纤维素、兼性离子改性的纤维素及其混合物。适合的纤维素聚合物包括甲基纤维素、羧甲基纤维素、乙基纤维素、羟乙基纤维素、羟丙基甲基纤维素、酯羧甲基纤维素及其混合物。本发明的一个实施方案中，洗涤增效胶囊中的污物释放聚合物占胶囊重量的约0.1％，1％，5％，10％，50％，60％或更多。
抗再沉淀剂
本发明的洗涤增效胶囊还可以包括一种或多种抗再沉积剂，例如羧甲基纤维素(CMC)、聚乙烯醇(PVA)、聚乙烯吡咯烷酮(PVP)、聚氧乙烯和/或聚乙二醇(PEG)、丙烯酸的均聚物、丙烯酸和马来酸的共聚物、和乙氧基化的聚乙亚胺。以上在污物释放聚合物下描述的纤维素基聚合物还可以用作抗再沉积剂。本发明的一个实施方案中，洗涤增效胶囊中的抗再沉淀剂占胶囊重量的约0.1％，1％，5％，10％，50％，60％或更多。
在本发明的一个实施方案中，增效胶囊包含的内容物除了洗涤用酶之外，基本上不含有常见于洗涤剂中的一些对酶苛性的物质，比如表面活性剂，漂白剂，漂白激活剂等。
常见的本领域中已知用于洗涤剂漂白系统组分包括漂白催化剂、光漂白剂、漂白活化剂、过氧化氢源如过碳酸钠、过硼酸钠和过氧化氢-尿素(1:1)、预成型过酸及其混合物。适合的预成型过酸包括但不限于过氧羧酸及盐、二过氧二羧酸、过亚氨酸(perimidic acid)及盐、过氧单硫酸及盐(例如过硫酸氢钾(Oxone(R))及其混合物。漂白体系的非限制性例子包括与过酸形成漂白活化剂组合的基于过氧化物的漂白体系，其可以包含例如无机盐，包括碱金属盐例如过硼酸盐的钠盐(通常为单或四水合物)、过碳酸盐、过硫酸盐、过磷酸盐、过硅酸盐。术语漂白活化剂在此意指一种与过氧化氢反应以经由过水解反应形成过酸的化合物。以此方式形成的过酸构成活化的漂白剂。有待在此使用的适合漂白活化剂包括属于酯、酰胺、酰亚胺或酸酐类别的那些。适合的实例是四乙酰基乙二胺(TAED)、4-[(3,5,5-三甲基己酰基)氧基]苯-1-磺酸钠(ISONOBS)、4-(十二酰基氧基)苯-1-磺酸盐(LOBS)、4-(癸酰基氧基)苯-1-磺酸盐、4-(癸酰基氧基)苯甲酸盐(DOBS或DOBA)、4-(壬酰基氧基)苯-1-磺酸盐(NOBS)和/或披露于WO 98/17767中的那些。感兴趣的漂白活化剂的具体家族披露于EP 624154中并且在那个家族中特别优选的是乙酰柠檬酸三乙酯(ATC)。ATC或短链甘油三酸酯(像三醋汀)具有以下优点，它是环境友好的。此外，乙酰柠檬酸三乙酯和三醋汀在存储时在产品中具有良好的水解稳定性，并且是一种有效的漂白活化剂。最后，ATC是多功能的，因为在过水解反应中释放的柠檬酸盐可以作为助洗剂起作用。可替代地，漂白系统可以包括例如酰胺、酰亚胺或砜型的过氧酸。漂白系统还可以包括过酸，例如6-(邻苯二甲酰亚胺基)过氧己酸(PAP)。漂白系统还可以包括漂白催化剂。在一些实施例中，漂白组分可以是选自下组的有机催化剂，该组由以下各项组成：具有下式的有机催化剂：
Figure PCTCN2018099196-appb-000027
(iii)及其混合物；
其中每个R1独立地是包含从9到24个碳的支链烷基或包含从11到24个碳的直链烷基，优选地每个R1独立地是包含从9到18个碳的支链烷基或 包含从11到18个碳的直链烷基，更优选地每个R1独立地选自下组，该组由以下各项组成：2-丙基庚基、2-丁基辛基、2-戊基壬基、2-己基癸基、十二烷基、十四烷基、十六烷基、十八烷基、异壬基、异癸基、异十三烷基以及异十五烷基。其他示例性漂白系统描述于例如WO 2007/087258、WO 2007/087244、WO 2007/087259、EP 1867708(维生素K)以及WO 2007/087242中。适合的光漂白剂可以例如是磺化的酞菁锌或酞菁铝。
优选地，除了漂白催化剂、特别是有机漂白催化剂以外，漂白组分还包括过酸源。过酸源可以选自(a)预形成的过酸；(b)过碳酸盐、过硼酸盐或过硫酸盐(过氧化氢源)，优选与一种漂白活化剂组合；和(c)过水解酶以及酯，用于在纺织品处理步骤中在水的存在下原位形成过酸。
在另一个方面，本发明涉及一种用于增强洗涤效果的增效胶囊，其包括普鲁兰多糖材料制成的胶囊外壳，和包含在上述胶囊外壳内的洗涤用酶。普鲁兰多糖胶囊具有与明胶胶囊相当的透明度，使得充填内容物清楚可见，在宽温湿度范围内贮存稳定，透氧率低避免充填内容物的氧化，同时避免了明胶胶囊制备过程中处理动物皮毛等产生的污染问题和明胶在洗涤过程中崩解速度不够迅速，并在洗涤过程结束后产生胶囊材料的残留物粘附在洗涤衣物和其他硬表面，从而严重影响消费者对洗涤效果的评价的问题。
在另一个方面，本发明涉及纤维素衍生物、淀粉及淀粉衍生物、普鲁兰多糖在制备用于增强洗涤效果的增效胶囊中的应用。
在另一个方面，本发明涉及一种试剂盒，其包含一个或多个前文所述的增效胶囊，所述增效胶囊上具有与内部包含的洗涤用酶的功能相应的消费者识别要素。所述的消费者识别要素可以帮助消费者了解具体的各个增效胶囊能提供的一种或多种洗涤增效效果。所述识别要素可以包括视觉要素、嗅觉要素或其他感觉要素。所述视觉要素可以是例如文字、图案，色彩或其组合，所述嗅觉要素可以是特定的香味。这些消费者识别要素的设计目的在于帮助消费者理解对应的增效胶囊的特定洗涤增效效果。
在上述发明的一个实施方案中，所述试剂盒中，增效胶囊被单独包裹在泡状包装材料中，上述增效胶囊可以单个包装或多个包装的组合，例如组成连续的一列，或连续几列形成方阵的形式提供。所述泡状包装材料是药物胶囊制剂和提供过程中常见的，泡状包装材料可以是铝箔和塑料材料制成，通 常为带有背衬材料如箔层材料的模制塑料片，使得消费者可以通过按压胶囊将其从包装中释放。
本发明的增效胶囊也可以在密封盒、瓶、罐中提供。任何一种容器或包装都可以配有分配装置。在外包装上可以包括胶囊的使用识别标志，包括上述的视觉识别标志。
在另一个方面，本发明涉及制备如前文所述的增效胶囊的方法，包括：a)筛选在15℃-30℃下的洗涤过程中残留率不超过18％，不超过12％，优选不超过10％，优选不超过8％，优选不超过6％，优选不超过4％，优选不超过3％，优选不超过1％的胶囊外壳，和b)将洗涤用酶填充到胶囊外壳内部。
在一个实施方案中，还包括在步骤b之前的如下步骤：c)筛选具有在20℃下含2％表面活性剂的洗涤液中崩解速率不超过30分钟的胶囊外壳，其中步骤c)在步骤a)之前，之后或同时进行。
通过本发明定义的胶囊的残留率和崩解率来筛选合适的胶囊外壳材料，可以有效地制备本发明的符合消费者需求的洗涤增效胶囊。
本发明的技术方案还包括如下：
1.一种增效胶囊，其包括胶囊外壳，和包含在胶囊内部的洗涤用酶，所述增效胶囊能够增强在短程洗涤中的洗涤效果。
2.方案1所述的增效胶囊，其中所述胶囊外壳具有在20℃下含2％表面活性剂的洗涤液中崩解时间不超过30分钟，优选不超过20分钟，不超过15分钟，不超过10分钟，不超过8分钟，不超过6分钟，不超过5分钟的崩解性能。
3.方案1或2所述的增效胶囊，其中胶囊外壳具有在15℃-30℃的洗涤过程中不超过18％，不超过12％，优选不超过10％，优选不超过8％，优选不超过6％，优选不超过4％，优选不超过3％，优选不超过1％的残留率。
4.方案1-3任一项所述的增效胶囊，其中所述短程洗涤包含不超过110分钟的洗涤周期，优选不超过100分钟，不超过90分钟，不超过80分钟，不超过60分钟，不超过50分钟，不超过30分钟。
5.方案4所述的增效胶囊，其中所述洗涤周期中的主洗周期不超过90分钟，不超过70分钟，优选不超过50分钟，优选不超过30分钟，优选不超过 20分钟，优选不超过15分钟，优选不超过12分钟。
6.上述方案任一项所述的增效胶囊，其中所述短程洗涤具有不超过90℃，优选不超过60℃，优选不超过40℃，优选不超过35℃，优选不超过30℃，优选不超过20℃，优选不超过10℃，优选不超过4℃的主洗温度。
7.上述方案任一项所述的增效胶囊，其中所述胶囊外壳由包含选自以下组的材料制成：纤维素衍生物、淀粉及淀粉衍生物、普鲁兰多糖，及其组合。
8.方案7所述的增效胶囊，所述胶囊外壳由包含普鲁兰多糖的材料制成。
9.方案7所述的增效胶囊，所述的胶囊外壳由包含羟丙基淀粉的材料制成。
10.方案7所述的增效胶囊，所述的胶囊外壳由包含羟丙基甲基纤维素的材料制成。
11.上述方案任一项所述的增效胶囊，其中所述洗涤用酶选自以下的组：蛋白酶，淀粉酶，纤维素酶、脂肪酶、磷脂酶、角质酶、氧化酶、加氧酶、转移酶、还原酶、半纤维素酶、甘露聚糖酶、酯酶、异构酶、果胶酶、乳糖酶、过氧化物酶、裂合酶、漆酶、脱氧核糖核酸酶,地衣多糖酶，及其组合。
12.方案11所述的增效胶囊，所述洗涤用酶选自以下的组：蛋白酶、淀粉酶、甘露聚糖酶，纤维素酶及其组合。
13.上述方案任一项所述的增效胶囊，所述洗涤用酶中基本不包含表面活性剂、漂白剂或漂白激活剂。
14.上述方案任一项所述的增效胶囊，所述洗涤用酶为不含酶稳定剂成分的低成本酶颗粒形式。
15.上述方案任一项所述的增效胶囊，其大小为5mm-100mm。
16.上述方案任一项所述的增效胶囊，所述增强的洗涤效果选自：去除污渍、维持白度、减少起球、织物颜色护理，去除气味，去除生物膜，防止、减少和/或去除污垢附着，及其组合。
17.一种增效胶囊，其包括由包含普鲁兰多糖的材料制成的胶囊外壳，和包含在上述胶囊外壳内的洗涤用酶，所述增效胶囊能够增强洗涤效果。
18.纤维素衍生物、淀粉及淀粉衍生物、普鲁兰多糖，及其组合在制备方案1-17中任一项所述的增效胶囊中的应用。
19.一种试剂盒，其包含一个或多个方案1-17任一项所述的增效胶囊，所述增 效胶囊上具有与内部包含的洗涤用酶的功能相应的视觉识别要素。
20.方案19所述的试剂盒，所述增效胶囊被单独包裹在泡状包装材料中。
21.制备如方案1-17任一项所述的增效胶囊的方法，包括：
a.筛选在25℃下的洗涤过程中残留率不超过18％，优选不超过12％，优选不超过10％，优选不超过8％，优选不超过6％，优选不超过4％，优选不超过3％，优选不超过1％的胶囊外壳，
b.将洗涤用酶填充到胶囊外壳内部。
22.方案21所述的方法，还包括在步骤b之前的如下步骤：
c.筛选具有在20℃下含2％表面活性剂的洗涤液中崩解速率不超过30分钟，优选不超过20分钟，不超过15分钟，不超过10分钟，不超过8分钟，不超过6分钟，不超过5分钟的胶囊外壳，
其中步骤c在步骤a之前，之后或同时进行。
分析方法
1.光强度值间的差值(ΔREM)分析
洗涤程序完成后，在通风干燥的条件下将洗涤后的所有样品过夜干燥。然后对干燥的样品进行光反射率评估，使用配备极小光圈的Macbeth Color Eye 7000反射分光光度计。在入射光中没有UV的条件下进行测量，并提取460nm的反射率。对经洗涤的样本进行测量。将要测量的测试样本放置在相同类型和颜色的另一样本之上(姊妹样本)。当纺织品表面的光强度值间的差值ΔREM≥3时，视为可见区别。
2.崩解时间测定
模型洗衣粉溶液的配制：去离子水，加入前述模型洗衣粉至浓度为2％w/w。
将蓝色染料(Remazol Br Blue R spec 160％，DyStar Kimya San.ve Tic.Ltd.Sti)和国标洗衣粉(GB/T2013174-2008，购于中国日用化学工业研究院)以1:6的重量比混合均匀后，称取0.3g上述混合物填充在待测胶囊内，作为配重内容物和崩解释放指示剂。将上述制备的待测胶囊分别投入盛有20℃的200mL模型洗衣粉溶液(2w/w％)的玻璃烧杯内(烧杯容积为250ml)，开 始搅拌，磁子(C200，百旺通达科技有限公司，长20mm，直径7mm)搅拌速率为400rpm。由于洗涤用酶具有较强的水溶性，溶解时间短，20℃时T50为30s，因此上述待测胶囊涨破、蓝色染料释出的时间可视为等同于实际应用中含酶的洗涤增效胶囊崩解开始的时刻，即最初目测观察到蓝色从胶囊内泄露到溶液中的时刻。
3.残留率测定
胶囊外壳必须能够在洗涤程序结束之后完全溶解，才不会形成残留并粘着在衣物上造成消费者的困扰。因此，胶囊材料在洗后的残留率是判定其是否适合应用在洗涤环境中的重要标准之一。
残留率(R％)，即空心胶囊的重量残余百分比的测定如下：在室温条件下精确称取空心胶囊的重量W(0)(精确到0.01g)，再将称重后的空心胶囊放入无纺布茶袋(购于超市)并测量袋子和胶囊总重量W(1)。将待测的空心胶囊随袋一起投入洗衣机中。由于茶袋在洗涤过程中可能会出现由于吸附洗涤剂残留(如沸石4A)或摩擦破损等造成重量变化，故在进行每轮实验时需加入一空茶袋作为校正样本，用以校正茶袋自身重量变化带来的误差Δ，其中Δ的值取自五个测量平行样品所得的平均值。测量洗后茶袋和空心胶囊的总重量，记作W(2)。根据下式计算R％，其中W(1)-W(0)+Δ是洗后茶袋的重量。每种胶囊的残留率的计算取自三组平行样品的平均值。
R％＝(W(2)－(W(1)－W(0)+Δ))÷W(0)×100％
4.亮度值间的差值(ΔL)分析
洗涤程序完成后，在通风干燥的条件下将洗涤后的所有样品过夜干燥。然后对干燥的样品进行光反射率评估，使用配备极小光圈的Macbeth Color Eye 7000反射分光光度计。在入射光中没有UV的条件下进行测量，并提取Lab测量值，对经洗涤的样本进行测量。将要测量的测试样本放置在相同类型和颜色的另一样本之上(姊妹样本)。对于用于测试的黑色棉织物，L值越低表面织物表面越平整，当纺织品表面的亮度值间的差值ΔL≥0.5时，视为可见区别。
下列非限制性实施例进一步叙述本发明范围内的优选实施方案。给出实施例仅是为了举例说明的目的，并且不应理解为是对本发明的限制，因为在 不背离其实质和范围的条件下可对其进行许多改变。
实施例
材料：
1.洗涤用污染织物样品
波轮洗衣机方法洗涤下列商业可得的12个污染织物样品。
Figure PCTCN2018099196-appb-000028
2.固体酶颗粒混合物
精确称取固体酶颗粒(精确到0.005g)，0.45g蛋白酶(Novozymes  A/S，Savinase 24T)，0.15g淀粉酶(Novozymes A/S，Stainzyme 12T)和0.01g甘露聚糖酶(Novozymes A/S，Mannaway 4T)。均匀混合。
3.洗涤剂配方
模型洗衣液：
LAS(C10-C13) 3.8％
AES 8％
AEO 4％
月桂酸钠 1.0％
柠檬酸钠(Na3citrate) 2％
氢氧化钠 0.6％
CaCl 2,2H 2O 0.02％
卡松(防腐剂) 0.1％
三乙醇胺(TEA) 0.4％
模型洗衣粉：
LAS(C10-C13) 15％
AEO 2％
碳酸钠 20％
二硅酸钠 12％
沸石4A 15％
聚合物 1％
硫酸钠 35％
上述模型洗衣粉和模型洗衣液的配制可以参照中国国家标准洗衣粉的配置。
洗涤设备和条件
1.波轮洗衣机洗涤
Figure PCTCN2018099196-appb-000029
2.滚筒洗衣机测试
Figure PCTCN2018099196-appb-000030
滚筒洗衣机中的不同洗涤程序的参数如下：
Figure PCTCN2018099196-appb-000031
3.立式去污机测试
Figure PCTCN2018099196-appb-000032
实施例1.不同胶囊材料的崩解时间
用4种市售空心胶囊根据分析方法2的描述制备待测胶囊a’-d’，并测定不同胶囊材料的崩解时间。空心胶囊分别为：
a.明胶胶囊
Figure PCTCN2018099196-appb-000033
(#0，购自苏州胶囊公司Capsugel)，
b.植物胶囊
Figure PCTCN2018099196-appb-000034
(#0，购自苏州胶囊公司Capsugel)，这是一种HPMC(羟丙甲纤维素)胶囊
c.天然胶囊Plantcaps TM(#0，购自苏州胶囊公司Capsugel)，这是一种普鲁兰多糖胶囊
d.
Figure PCTCN2018099196-appb-000035
(普鲁兰多糖)胶囊(#0，购自苏州力凡胶囊公司)，这是另一种HPMC(羟丙甲纤维素)胶囊
e.辰星植物胶囊(海藻多糖)(#0，颜色，购自江苏辰星药业股份有限公司)，这是一种海藻多糖胶囊
f.红星植物胶囊(海藻提取物和植物纤维)(#0，上海红星植物胶丸有限公司)，这是另一种植物胶囊
g.湘尔康淀粉胶囊(#0，购于湖南尔康制药有限公司)，这是一种淀粉胶囊
每个实验取三个胶囊在相同条件下测试三次，测量值取算术平均值。测试结果如表7所示。
表7：不同胶囊的崩解时间(20℃)
待测胶囊 崩解时间
a’ 34′34″
b’ 5′31″
c' 4′5″
d' 4′31″
e’ 13′15″
f’ 12′49″
g 16′52″
此外，为研究不同温度对胶囊崩解时间的影响，将上述实验分别在30℃，40℃各进行相应的重复，测试取三次的算术平均值。测试结果如表8和表9所示。
表8：不同胶囊的崩解时间(30℃)
胶囊种类 崩解时间
a’ 11′25″
b’ 5′31″
c' 4′5″
d' 3′39″
e’ 8′01″
f’ 7′56″
g 10′41″
表9：不同胶囊的崩解时间(40℃)
胶囊种类 崩解时间
a’ 1′59″
b’ 5′31″
c' 4′5″
d' 6′49″
e’ 5′35″
f’ 10′00″
g 5′11″
从表7-9的结果可以看出，明胶胶囊的崩解时间在低温(20℃，30℃)洗涤过程中相对其他材料的胶囊为最长，而在高温(40℃)洗涤过程中崩解时间才开始显示出较其他胶囊变短。这表明明胶胶囊的崩解时间具有显著的洗涤温度依赖性；而HPMC胶囊的崩解时间在常见洗涤温度区间内受温度的影响不显著。海藻提取物胶囊和淀粉胶囊的溶解速率也受温度影响，温度较低时(20℃)溶解速度优于明胶，在较高温度(30℃，40℃)的溶液中溶解速度有显著提升，但上升幅度弱于明胶胶囊。
实施例2.离子强度对胶囊材料的崩解时间的影响
本实验的目的是验证洗涤剂中包含的助剂造成的洗涤液离子强度的增加对胶囊材料崩解时间的影响。实验组中待测胶囊的制备，模型洗衣粉溶液的配置和释放速率的测量方法同分析方法2中所述，实验在20℃下进行。
实验组使用的模型洗衣粉中含有作为助剂的0.4％Na 2CO 3和0.7％Na 2SO 4；
助剂增强组中其他条件一致，但在原有洗涤剂的基础之上额外添加助剂，助剂含量为洗衣粉比例的3.4％Na 2CO 3+2.7％Na 2SO 4；
纯水对照组，不使用模型洗衣粉，其他条件同实验组。
本实验测试了两种待测胶囊b’和c’的崩解时间。结果如下表所示，每个数据取相同条件下两次重复的算术平均值。
表10.植物胶囊
Figure PCTCN2018099196-appb-000036
(HPMC胶囊，即b’胶囊)的崩解时间受洗涤
Figure PCTCN2018099196-appb-000037
表11.天然胶囊Plantcaps TM(普鲁兰多糖胶囊，即c’胶囊)的崩解时间
Figure PCTCN2018099196-appb-000038
从表10-11的结果可以看出，在该测试体系下，HPMC胶囊的崩解时间受助剂造成的离子强度和/或pH值增加的影响而显著延长，而普鲁兰多糖胶囊的崩解时间受离子强度和/或pH值增加的影响不显著。
实施例3.不同胶囊材料制成的洗涤增效剂的洗涤效果评估。
1.洗涤增效胶囊的制备
分别用4种市售空心胶囊制备4种含固体酶颗粒的待测洗衣增效剂。空心胶囊a-d同实施例1中所述，固体酶颗粒混合物如前文“材料”2“固体酶颗粒混合物”部分所述。将硬胶囊两端打开并将称取好的固体酶颗粒混合物分别装入空心胶囊a-d内，再将胶囊两端扣紧，从而制备含固体酶颗粒的各洗涤增效胶囊A-D。
2.洗涤增效胶囊增效测试
实验组1-4在洗涤起始时分别加入一粒洗涤增效胶囊A-D。
阳性对照组则在洗涤起始时直接加入与洗涤增效胶囊中所含等量的固体酶颗粒混合物。
洗涤所针对的污渍是品是如前文“材料”部分“洗涤用污染织物样品”所述的12种中的11种样品中所表征的污渍。采用前文实施例“洗涤设备和条件”部分的波轮洗衣机的设置进行洗涤，洗涤温度为25℃。洗涤完成后，测量并计算各实验组1-4织物表面的光强度值与阳性对照组的织物表面的光强度值的差值，即ΔRem。
ΔRem＝Rem(T)–Rem(0)
Rem(0)是0min时将固体酶混合物(阳性对照)投入洗衣机时洗涤过的纺织品表面的光强度值；
Rem(T)是用洗涤增效胶囊洗涤后的纺织品表面的光强度值；
实验结果显示在表3和4中。
表12：波轮洗衣机中使用模型洗衣液和洗涤增效胶囊A-D呈现的对12种污渍的洗涤效果(ΔRem)
Figure PCTCN2018099196-appb-000039
Figure PCTCN2018099196-appb-000040
从表12的结果可以看出，在使用模型洗衣液洗涤的环境中：
当加入的洗涤增效胶囊是明胶胶囊包裹的洗涤用酶时，其相对于阳性对照组在洗涤后的效果，在11种污渍中有6种(55％)的测试污渍上出现洗涤效果的显著降低，即ΔREM的绝对值大于3；
而当加入的洗涤增效胶囊是其他材料，如HPMC胶囊或普鲁兰多糖胶囊时，在11种污渍中没有一种(0％)出现与阳性对照相比洗涤效果的显著降低。
表13：波轮洗衣机中使用模型洗衣粉和洗涤增效胶囊A-D呈现的对12种污渍的洗涤效果(ΔREM)
Figure PCTCN2018099196-appb-000041
Figure PCTCN2018099196-appb-000042
从表13的结果可以看出，在使用模型洗衣粉洗涤的环境中：
当加入的洗涤增效胶囊是明胶胶囊包裹的洗涤用酶时，其相对于阳性对照组在洗涤后的效果，在11种污渍中有7种(64％)的测试污渍上出现洗涤效果的显著降低，即ΔREM的绝对值大于3；
而当加入的洗涤增效胶囊是其他材料，如HPMC胶囊，在11种污渍中几乎没有出现与阳性对照相比洗涤效果的显著降低，或普鲁兰多糖胶囊时，在11种污渍的洗涤效果上只有1或2种污渍的洗涤效果与阳性对照相比出现显著的降低。
从表12和13的结果可知，明胶胶囊会影响含酶内容物的工作效率，尤其是当其使用环境是在亚洲较为流行的洗涤周期较短(主洗时间为15min，总洗涤时长为40min)的波轮洗衣机洗涤程序中时。而其他材料制成的洗涤增效胶囊，如HPMC胶囊和普鲁兰多糖胶囊不会显著影响与阳性对照相比显著的洗涤效果的降低。
实施例4.胶囊材料残留率
按分析方法部分“残留率的测定”的描述对4种市售胶囊a-d进行评测，所述4种市售胶囊a-d与实施例1中所述一致。分别采用滚筒洗涤和波轮洗涤 进行胶囊材料残留率的测定，洗涤的条件如前文“洗涤设备和条件”中所述。
首先，茶袋的校正值见表14。
表14：洗涤测试前后茶袋重量(克)变化Δ
Figure PCTCN2018099196-appb-000043
下表15-18分别对各种胶囊在不同条件下进行残留率的测试分析。
表15：胶囊a(明胶胶囊)滚筒洗衣机30℃不同洗涤时长的残留率
  洗涤周期 主洗周期 残留率
快洗(减漂)express 20 short 11 20 78％
快洗express 20 11 30 97％
衬衣shirt short 23 44 72％
深色衣物dark garments 22 62 79％
免熨minimum ion 83 87 84％
纯棉洗(减漂)cotton short 51 119 0％
纯棉洗cotton 51 149 38％
加强洗intensive 108 167 -7％
表16：胶囊b(HPMC胶囊)滚筒洗衣机30℃不同洗涤时长的残留率
  洗涤周期 主洗周期 残留率
快洗(减漂)express 20 short 11 20 2％
快洗express 20 11 30 10％
衬衣shirt short 23 44 0％
深色衣物dark garments 22 62 7％
免熨minimum ion 83 87 0％
纯棉洗(减漂)cotton short 51 119 -7％
纯棉洗cotton 51 149 7％
加强洗intensive 108 167 -4％
表17：胶囊c(普鲁兰多糖胶囊)在滚筒洗衣机30℃不同洗涤时长的残留率
  洗涤周期 主洗周期 残留率
快洗(减漂)express 20 short 11 20 3％
快洗express 20 11 30 3％
衬衣shirt short 23 44 0％
深色衣物dark garments 22 62 6％
免熨minimum ion 83 87 -4％
纯棉洗(减漂)cotton short 51 119 0％
纯棉洗cotton 51 149 0％
加强洗intensive 108 167 3％
表18：胶囊d(普鲁兰多糖胶囊)在滚筒洗衣机30℃不同洗涤时长的残留率
  洗涤周期 主洗周期 残留率
快洗(减漂)express 20 short 11 20 3％
快洗express 20 11 30 -10％
衬衣shirt short 23 44 3％
深色衣物dark garments 22 62 -6％
免熨minimum ion 83 87 10％
纯棉洗(减漂)cotton short 51 119 -15％
纯棉洗cotton 51 149 -4％
加强洗intensive 108 167 6％
表27：胶囊e(辰星海藻胶囊)在滚筒洗衣机30℃不同洗涤时长的残留率
  洗涤周期 主洗周期 残留率
快洗(减漂)express 20 short 11 20 0％
快洗express 20 11 30 6％
衬衣shirt short 23 44 1％
深色衣物dark garments 22 62 1％
免熨minimum ion 83 87 2％
纯棉洗(减漂)cotton short 51 119 3％
纯棉洗cotton 51 149 4％
加强洗intensive 108 167 1％
表28：胶囊f(红星海藻胶囊)在滚筒洗衣机30℃不同洗涤时长的残留率
  洗涤周期 主洗周期 残留率
快洗(减漂)express 20 short 11 20 6％
快洗express 20 11 30 9％
衬衣shirt short 23 44 2％
深色衣物dark garments 22 62 2％
免熨minimum ion 83 87 5％
纯棉洗(减漂)cotton short 51 119 4％
纯棉洗cotton 51 149 1％
加强洗intensive 108 167 2％
表29：胶囊g(尔康淀粉胶囊)在滚筒洗衣机30℃不同洗涤时长的残留率
  洗涤周期 主洗周期 残留率
快洗(减漂)express 20 short 11 20 1％
快洗express 20 11 30 1％
衬衣shirt short 23 44 1％
深色衣物dark garments 22 62 1％
免熨minimum ion 83 87 7％
纯棉洗(减漂)cotton short 51 119 1％
纯棉洗cotton 51 149 -1％
加强洗intensive 108 167 1％
天平称量的误差为±0.01g，而胶囊a-g为#0号胶囊，其重量范围在0.08-0.12g间，因此残留率计算的系统误差为8％-12％。为保证判断的准确性，在称重测试的同时对胶囊的残留情况进行了感官评测，发现残留率在±18％范围内未发现残留，但残留率超出该误差范围即显示在洗涤后存在显著的残留。
从上述表15-18和表27-29的结果可以看出，明胶胶囊在30℃滚筒洗衣机洗涤环境下分别在洗涤时间20min，30min，44min，62min，87min， 149min的各程序中都有明显的残留。而其他材料的胶囊，包括HPMC胶囊，普鲁兰多糖胶囊，海藻胶囊和淀粉胶囊在30℃滚筒洗衣机洗涤环境下各种时长的上述洗涤程序中均未发现显著残留。
表19：胶囊a(明胶胶囊)在波轮洗衣机不同洗涤时长的残留率
  洗涤周期 主洗周期 残留率
15℃ 40分钟 15分钟 102％
25℃ 40分钟 15分钟 92％
表20：胶囊b(HPMC胶囊)在波轮洗衣机不同洗涤时长的残留率
  洗涤周期 主洗周期 残留率
15℃ 40分钟 15分钟 3％
25℃ 40分钟 15分钟 1％
表21：胶囊c(普鲁兰多糖胶囊)在波轮洗衣机不同洗涤时长的残留率
  洗涤周期 主洗周期 残留率
15℃ 40分钟 15分钟 -1％
25℃ 40分钟 15分钟 -5％
表22：胶囊d(普鲁兰多糖胶囊)在波轮洗衣机不同洗涤时长的残留率
  洗涤周期 主洗周期 残留率
15℃ 40分钟 15分钟 -2％
25℃ 40分钟 15分钟 -2％
从上述表19-22的结果可以看出，明胶胶囊在15℃和25℃波轮洗衣机洗涤环境下都有明显的残留。而其他材料的胶囊，包括HPMC胶囊，普鲁兰多糖胶囊在相同洗涤环境下均未发现显著残留。
实施例5.胶囊洗涤增效剂对织物护理效果的评估
1.材料制备
使用市售空心胶囊c(普鲁兰多糖胶囊)制备含固体纤维素酶颗粒 (Novozymes A/S，Carezyme Premium 5000T)的待测洗衣增效剂C，纤维素酶含量为0.6g，酶颗粒填充到胶囊内部的方法如实施例3中所述。
织物护理评估中所用的材料为EMPA252(彩色条纹布，94％棉6％氨纶，购自Center for Testmaterials B.V,Netherlands)，经下述方法进行材料老化后备用。材料老化的方法为：将预洗后的EMPA252放置在Wascator自动洗衣机中连续洗涤12小时，处理温度为40℃。处理后的EMPA252表面将明显起球，便于护理效果评测。
洗涤条件参照前文实施例“洗涤设备和条件”，其中波轮洗衣机的洗涤温度为25℃，洗涤剂为市售纳爱斯超效加酶洗衣粉，滚筒洗衣机的洗涤温度为40℃，洗涤剂为市售蓝月亮深层洁净洗衣液。为提现增效胶囊持续的织物护理效果，实验中连续监测了同一织物EMPA252样品在连续经历三轮洗涤后的洗涤效果。
2.洗涤增效胶囊增效测试
·实验组：在洗涤起始时分别加入2，4，6，8粒如本实施例前文所述的增效胶囊C。
·阴性对照组：不加入增效胶囊。
织物护理效果的评估方法是测量老化EMPA252上黑色条纹的亮度值(L值)，由于磨损起球会使衣物鲜艳程度下降，即在EMPA252黑色条纹上反映为黑色变灰，亮度值升高。故在洗涤完成后，测量并计算各实验组1-5织物表面的亮度值(L)与未经洗涤处理的老化EMPA252的织物表面的亮度值的差值，即ΔL。
ΔL越大证明织物护理效果越优，ΔL≥0.5时提醒为可见区别。
使用纳爱斯超效加酶洗衣粉和洗涤增效胶囊C在波轮洗衣机中洗涤后呈现的对老化EMPA252表面的护理效果(ΔL)实验结果如下表23所示。
表23.
洗涤轮次 阴性对照组 实验组1 实验组2 实验组3 实验组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
从上表23可以看出，在波轮洗衣机的洗涤环境中：加入洗涤增效胶囊C 能够在洗涤第2轮后提供显著可见的织物护理的功效，其效果随增效胶囊剂量的增大及洗涤轮数的提升而增强。阴性对照组的ΔL则随着洗涤轮数增加而降低，提示出织物表面性能的进一步破坏。这表明本发明的包含纤维素酶的洗涤增效胶囊提供显著的去毛球的衣物护理效果。
使用蓝月亮深层洁净护理洗衣液和洗涤增效胶囊C在滚筒洗衣机中洗涤后呈现的对老化EMPA252表面的护理效果(ΔL)实验结果如下表24所示。
表24.
洗涤轮次 阴性对照组 实验组5 实验组6 实验组7 实验组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
从表24的实验结果中可以得出，在滚筒洗衣机的洗涤环境中，相较于阴性对照，本发明的洗涤增效胶囊C能够在第1轮洗涤后即带来非常显著的去毛球的织物整理的功效，效果随着洗涤增效胶囊C投放数量的增大及洗涤轮数的增加而有明显的提高。
实施例6.胶囊洗涤增效剂对织物白度维护效果的评估
1.材料制备
使用市售空心胶囊c(普鲁兰多糖胶囊)制备含固体纤维素酶颗粒(Novozymes A/S，Carezyme Premium 5000T)和水溶性荧光增白剂(Fluroscent Whitening Agent,FWA,购自BASF，产品名CBS-X)的待测洗衣增效剂胶囊1-2，胶囊内容物含量如表25中所述。酶颗粒和荧光增白剂填充到胶囊内部的方法如实施例3中所述。
表25
胶囊1 0.018g Celluclean 5000T
胶囊2 0.005g FWA+0.018g Celluclean 5000T
织物护理评估中所用的材料为白色针织棉布(CN42，购自Center for Testmaterials B.V,Netherlands)和白色毛巾布(WFK12AW，购自Testfabrics,Inc.)。采用前文实施例“洗涤设备和条件”部分的立式去污机的设置进行洗涤，洗涤剂为上述模型洗衣粉。为加速模拟白色织物在反复洗涤中污渍沉积 导致的白度下降情况，在洗涤环境中加入0.8g/L液体炭黑模拟污渍。
各实验组的测试条件如表26中所述，阳性对照为未经处理，阴性对照和其他各实验组均为使用2g/L模型洗衣粉(如前文实施例材料部分所述)洗涤，其中荧光增白剂组(实验组1)在洗涤过程中额外加入0.005g荧光增白剂，胶囊1组(实验组2)和胶囊2组(实验组3)则额外加入1-2粒相应的洗涤增效胶囊。
洗涤完成后，测量并计算各实验组织物洗后表面光强度对应于阳性对照组的下降值，即ΔRem。ΔRem越小表示织物表面光强度值降低的越少，即白度维护效果越佳。
表26
Figure PCTCN2018099196-appb-000044
从表26的结果可以看出，相较于未经处理的阴性对照组，荧光增白剂组(实验组1)和加入含有纤维素酶的洗衣增效剂胶囊1的实验组2都能有效的减缓织物的白度的降低。而加入含有这两种成分的洗衣增效剂胶囊2的实验组3则体现出这两种组分间的协同作用，即更为显著的白度维护效果，并且 该效果随胶囊2的使用量的增加而增强。
本文所公开的量纲和值不旨在被理解为严格地限于所述的精确值。相反，除非另外指明，每个这样的量纲是指所引用的数值和围绕该数值的功40mm"的量纲旨在表示"约40mm"。
发明详述中引用的所有文件在相关部分中以引用的方式并入本文。对于任何文件的引用不应当解释为承认其是有关本发明的现有技术。当本发明中术语的任何含义或定义与引入以供参考的文件中术语的任何含义或定义矛盾时，应当服从在本发明中赋予该术语的含义或定义。
虽然已经举例说明和描述了本发明的具体实施方案，但是对于本领域技术人员来说显而易见的是，在不背离本发明实质和范围的情况下可以做出多个其他改变和变型。因此，权利要求书意欲包括在本发明范围内的所有这样的改变和变型。

Claims (22)

  1. 一种增效胶囊，其包括胶囊外壳，和包含在胶囊内部的洗涤用酶，所述增效胶囊能够增强在短程洗涤中的洗涤效果。
  2. 权利要求1所述的增效胶囊，其中所述胶囊外壳具有在20℃下含2％表面活性剂的洗涤液中崩解时间不超过30分钟，优选不超过20分钟，不超过15分钟，不超过10分钟，不超过8分钟，不超过6分钟，不超过5分钟的崩解性能。
  3. 权利要求1或2所述的增效胶囊，其中胶囊外壳具有在15℃-30℃的洗涤过程中不超过18％，不超过12％，优选不超过10％，优选不超过8％，优选不超过6％，优选不超过4％，优选不超过3％，优选不超过1％的残留率。
  4. 权利要求1-3任一项所述的增效胶囊，其中所述短程洗涤包含不超过110分钟的洗涤周期，优选不超过100分钟，不超过90分钟，不超过80分钟，不超过60分钟，不超过50分钟，不超过30分钟。
  5. 权利要求4所述的增效胶囊，其中所述洗涤周期中的主洗周期不超过90分钟，不超过70分钟，优选不超过50分钟，优选不超过30分钟，优选不超过20分钟，优选不超过15分钟，优选不超过12分钟。
  6. 上述权利要求任一项所述的增效胶囊，其中所述短程洗涤具有不超过90℃，优选不超过60℃，优选不超过40℃，优选不超过35℃，优选不超过30℃，优选不超过20℃，优选不超过10℃，优选不超过4℃的主洗温度。
  7. 上述权利要求任一项所述的增效胶囊，其中所述胶囊外壳由包含选自以下组的材料制成：纤维素衍生物、淀粉及淀粉衍生物、普鲁兰多糖，及其组合。
  8. 权利要求7所述的增效胶囊，所述胶囊外壳由包含普鲁兰多糖的材料制成。
  9. 权利要求7所述的增效胶囊，所述的胶囊外壳由包含羟丙基淀粉的材料制成。
  10. 权利要求7所述的增效胶囊，所述的胶囊外壳由包含羟丙基甲基纤维素的材料制成。
  11. 上述权利要求任一项所述的增效胶囊，其中所述洗涤用酶选自以下的组：蛋白酶，淀粉酶，纤维素酶、脂肪酶、磷脂酶、角质酶、氧化酶、加氧酶、 转移酶、还原酶、半纤维素酶、甘露聚糖酶、酯酶、异构酶、果胶酶、乳糖酶、过氧化物酶、裂合酶、漆酶、脱氧核糖核酸酶,地衣多糖酶，及其组合。
  12. 权利要求11所述的增效胶囊，所述洗涤用酶选自以下的组：蛋白酶、淀粉酶、甘露聚糖酶，纤维素酶及其组合。
  13. 上述权利要求任一项所述的增效胶囊，所述洗涤用酶中基本不包含表面活性剂、漂白剂或漂白激活剂。
  14. 上述权利要求任一项所述的增效胶囊，所述洗涤用酶为不含酶稳定剂成分的低成本酶颗粒形式。
  15. 上述权利要求任一项所述的增效胶囊，其大小为5mm-100mm。
  16. 上述权利要求任一项所述的增效胶囊，所述增强的洗涤效果选自：去除污渍、维持白度、减少起球、织物颜色护理，去除气味，去除生物膜，防止、减少和/或去除污垢附着，及其组合。
  17. 一种增效胶囊，其包括由包含普鲁兰多糖的材料制成的胶囊外壳，和包含在上述胶囊外壳内的洗涤用酶，所述增效胶囊能够增强洗涤效果。
  18. 纤维素衍生物、淀粉及淀粉衍生物、普鲁兰多糖，及其组合在制备权利要求1-17中任一项所述的增效胶囊中的应用。
  19. 一种试剂盒，其包含一个或多个权利要求1-17任一项所述的增效胶囊，所述增效胶囊上具有与内部包含的洗涤用酶的功能相应的视觉识别要素。
  20. 权利要求19所述的试剂盒，所述增效胶囊被单独包裹在泡状包装材料中。
  21. 制备如权利要求1-17任一项所述的增效胶囊的方法，包括：
    a.筛选在25℃下的洗涤过程中残留率不超过18％，优选不超过12％，优选不超过10％，优选不超过8％，优选不超过6％，优选不超过4％，优选不超过3％，优选不超过1％的胶囊外壳，
    b.将洗涤用酶填充到胶囊外壳内部。
  22. 权利要求21所述的方法，还包括在步骤b之前的如下步骤：
    c.筛选具有在20℃下含2％表面活性剂的洗涤液中崩解速率不超过30分钟，优选不超过20分钟，不超过15分钟，不超过10分钟，不超过8分钟，不超过6分钟，不超过5分钟的胶囊外壳，
    其中步骤c在步骤a之前，之后或同时进行。
PCT/CN2018/099196 2017-08-08 2018-08-07 增效胶囊 WO2019029530A1 (zh)

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