KR970001229B1 - Water insoluble encapsulated enzymes protected against deactivation by halogen bleaches - Google Patents

Abstract

A composition capable of releasing active enzyme into an aqueous, active chlorine containing media which in a first aspect comprises an enzyme core encapsulated with an initial coating of a time-release substance, a first coating of a bleach-neutralizing substance and a second coating of a time-release substance. In a second aspect, the composition comprises an enzyme encapsulated in a time-release substance designed to delay release of the enzyme in dissolution for a first-time delay, and a bleach-neutralizing substance, present as either a core material and/or a first coating on a diluent core, which is encapsulated in a time-release substance designed to delay release of the bleach-neutralizing substance into solution for a second-time delay; the first-time delay being longer than the second-time delay so that the bleach-neutralizing substance will be released and completely neutralize all active chlorine present in the solution before the enzyme is released. In a third aspect, the composition comprises an enzyme core encapsulated with a time-release substance, a diluent core encapsulated with a first coating of a bleachneutralizing substance and a second coating of a time-release substance, and a bleach-neutralizing substance core encapsulated with a time-release substance. The invention further includes a cleaning composition which is particularly effective in warewashing which comprises one of the encapsulated enzyme-containing compositions described above, chlorine bleach, and at least one additional detergent component.

Description

Encapsulated water soluble enzyme protected from inactivation by halogen bleach

The present invention relates broadly to encapsulated enzymes and in particular to encapsulated water soluble enzymes which can be mixed with halogen bleaches to form effective bleach / enzyme wash compositions.

Enzymes are capable of promoting certain biochemical reactions, such as converting starch to sugar (amylase), hydrolyzing fats to glycerol and fatty acids (lipases), and hydrolyzing proteins (proteases). Protein. It is known that enzymes can only catalyze a limited number of specific sites, commonly referred to as active sites.

Certain biological materials, such as proteins, lipids and polysaccharides, are substantially insoluble in conventional wash media and are difficult to remove from substrates such as dishes, dishes and fabrics. In order to remove these biological substances by increasing their solubility, methods are known to catalytically assist in the degradation of insoluble monomers and / or oligomeric molecules using enzymes in the wash medium. Enzymatic forms such as amylases, lipases, and proteases are known to be useful for this purpose because they can effectively remove these substances from the substrate without particularly damaging the substrate to be washed.

Halogen bleach is a well known class of chemicals that has the ability to remove stains caused by coffee and tea from the substrate. Halogen bleach removes these stains by breaking down the large colored organic molecules that form these stains into smaller colorless molecules.

The washing action of enzymes and halogen bleaches is complementary to one another by acting on different aspects of the stains typically found on plates, tableware fabrics. Therefore, the use of both enzyme and halogen bleach in a single wash composition can produce more powerful wash compositions. However, although theoretically simple, it has been found difficult to use such compositions because halogen bleach completely deactivates the enzyme even at low concentrations, such as 1 part active halogen per million parts of wash medium. Although it is not fully understood about the inactivation of such enzymes, it is believed that halogen bleach changes the structure or morphology of the active site of the enzyme, making the active site of the enzyme no longer available as a reaction site.

Initial studies of incorporating halogen bleach and enzyme into a stable wash composition include incorporating a stabilized amount of polysaccharide into the wash composition, incorporating a stabilized amount of nonionic polymer into the wash composition, and coupling the enzyme onto an insoluble support. Included. All of these early attempts faced limitations and sought other ways.

A somewhat successful method of mixing halogen bleach and enzyme into a stable wash composition is to encapsulate the bleach in a time-release coating. The release delay coating delays the release of the enzyme inactivating bleach for a time sufficient to perform its washing function before the enzyme is inactivated. However, this approach also faces limitations because it is economically impossible to block the release of the enzyme inactivation amount of bleach in advance.

A more successful method of mixing halogen bleach and enzyme into a stable detergent composition is described in US Pat. No. 4,421,664, where enzymatic activity encapsulates the bleach with a release delay coating and immediately reduces the previously released bleach. It has been described that a sufficient amount of reducing agent can be maintained in the presence of a halogen bleach incorporated into the composition. The method was more successful than the previous method, but to perform this process effectively with encapsulated bleach with very high encapsulation efficiency, it has been found that the process is a prohibitively expensive composition.

Therefore, there is a need for an inexpensive and stable cleaning composition that contains both enzymes and bleaches in which the enzymes and bleaches can accomplish their desired washing operations.

A first aspect of the present invention is capable of releasing an active enzyme into an aqueous, chlorine bleach-containing medium, comprising an encapsulant core encapsulated with an inner coat of bleach-neutralizing agent and an outer coat of release delaying material. To a composition. The encapsulated enzyme may further comprise a coating of release retardant between the enzyme and the bleach-neutralizing agent so that all of the chlorine bleach present in the solution is neutralized by the bleach-neutralizing agent before the enzyme is released. .

A second aspect of the invention is an enzyme core encapsulated with a release delay material designed to delay release of an enzyme into solution during a first delay period, and a release of bleach-neutralizer into solution during a second delay period. A bleach-neutralizing agent encapsulated with a release retardant designed to make the first delay longer than the second, so that the bleach-neutral is released before the enzyme is released, so that all chlorine bleach in the solution To a composition capable of releasing an active enzyme into an aqueous, chlorine bleach-containing medium that completely neutralizes it. The bleach-neutralizer may be present in the core state or in the form of an inner coating on the diluent center. It can also be encapsulated with an inner coating of bleach-neutralizing agent between the enzyme and the release retardant.

A third aspect of the invention is an enzymatic center encapsulated with a release retardant, a bleach-inner coating with a neutralizing material and a diluent center encapsulated with an outer coating with a release retardant, and a bleach encapsulated with a release retardant A composition capable of releasing an active enzyme comprising neutralizing centers into an aqueous, chlorine bleach-containing medium. Enzyme centers and bleach-neutral centers can be further encapsulated with an initial coat of bleach-neutralizer between the center and the release retardant. In addition, the enzyme core can be coated with a release retardant to delay the release of the enzyme into the solution during the first delay period, and the diluent and bleach-neutral centers coated with the release retardant are diluent and bleach-neutralizers. Delay release of the solution into the solution during the second delay period, and the first delay period is longer than the second delay period to release all of the bleach-neutralizing agents present in the core material or in the coating material on the diluent center to release the enzyme. Completely neutralize any chlorine bleach previously present in solution.

A fourth aspect of the invention relates to a cleaning composition which is particularly effective for dishwashing, comprising a composition comprising at least one of the above-mentioned encapsulated enzyme-containing compositions, chlorine bleach, and at least one additional detergent component.

Commercial enzymes usually contain significant amounts of inert fillers such as sodium sulfate, sodium chloride and the like.

By weight enzyme as used herein is meant both active enzyme and inert filler used in combination with the enzyme, unless stated otherwise. For example, when a mixture of 20 mg of enzyme and 60 mg of inert filler is encapsulated with an inner coating of 10 mg of bleach-neutralizing agent and an outer coating of 10 mg of release retardant, the encapsulated enzyme composition comprises 80% by weight enzyme center. Result.

As used herein, bleach means any chemical agent capable of removing color from the substrate through oxidation.

As used herein, active halogen or active chlorine means halogen or chlorine that is actually present in the compound at valence of at least -1.

1972, PP. 180-190]을 참조하고, 이것은 여기에서 참고문헌으로서 인용된다.More detailed meanings of bleach, active chlorine, and commercially available chlorine can be found in White, George,

1972, pp. 180-190, which is incorporated herein by reference.

Encapsulated Enzyme

A first aspect of the invention is capable of releasing an active enzyme into an aqueous, chlorine bleach-containing medium, comprising an encapsulant core encapsulated with an inner coat of bleach-neutralizing agent and an outer coat of release delaying material. It relates to a composition. The encapsulated enzyme may further contain an initial coating of release retardant between the enzyme and the bleach-neutralizing agent so that all of the chlorine bleach is neutralized by the bleach-neutralizing agent before the enzyme is released.

enzyme

Any enzyme capable of catalyzing the reaction of removing a biological stain from a substrate with little damage to the substrate can be usefully used in the present invention. Such enzymes include proteases, lipases, amylases and the like. Preferred enzymes or combinations of enzymes depend on the substrate to be washed and the stain to be removed. The enzyme is preferably in powder form for ease of handling and coating.

Commercially available enzymes contain significant amounts of inert fillers such as sodium sulfate, sodium chloride, and the like, but the presence of such fillers has no effect on the present invention.

Proteases (including peptidase) are enzymes that act on and degrade proteinaceous stains such as meat scraps, meat broth, and blood.

Proteases are classified under EC classification number 3, subclass number 3.4.

)로서 구입할 수 있다.EC class number 3.4.4 peptide faptido-hydrodrollase, such as subtylopeptidase A (EC 3.4 4.16), has been found to be particularly effective in the wash compositions of the invention. Suitable proteases are available from Novo Industries under the trade name Esperase (

Can be purchased as).

Lipase is an enzyme that acts on and breaks down fat stains such as cooking oil, grease, and ice cream. Lipases also belong to classification number 3, but subclass number 3.1. EC class number 3.1.1 enzymes such as glycerol ester hydrolase (EC 3.1.1.3) have been found to be particularly effective in the wash compositions of the invention. Suitable lipases are available from Enzyme Development under the trade name Lipase 30,000.

)로서 구입할 수 있다.Amylases are enzymes that act on and degrade starch, polysaccharides, and cellulosic stains such as potatoes, rice, oatmeal, and grass. Amyla Islands belongs to EC classification number 3 but belongs to subclass number 3.2. EC 3.2.1 glycose hydrolases such as alpha-1,4-glucan-4-glucano hydrolase (EC 3.2.1.1), and alpha 1,4-glucan maltohydrolase (EC 3.2.1.2) Has been found to be particularly effective in the cleaning compositions of the present invention. Suitable amylases are available from Novo Industries under the trade name tumamyl (

Can be purchased as).

A more in-depth and detailed discussion of suitable enzymes is described in US Pat. No. 4,421,664 (line 16 of column 4 to line 24 of column 6), which is incorporated herein by reference.

The encapsulated enzyme may contain up to about 95% by weight of enzyme center based on the total capsule. However, it is preferred that the capsules contain about 50 to 80% by weight of enzyme to sufficiently introduce the bleach-neutralizer into solution and to achieve an economic balance between the encapsulation efficiency and the amount of coating used.

Bleach-Neutralizing Materials

In a first aspect of the invention, encapsulating and protectively encapsulating the enzyme core is an inner coating of bleach-neutralizing substance, which, when released in solution, reduces all active chlorine present in the solution to inactivate the enzyme. prevent. The bleach-neutralizer, of course, must be a stable solid at room temperature and compatible with all other ingredients for mixing with enzymes and encapsulated enzymes. The bleach-neutralizer should also be one that does not damage the substrate to be washed.

It is possible to reduce the active chlorine so as not to inactivate the enzyme and all compositions belonging to the above-mentioned categories can be usefully used in the present invention. Suitable bleach-neutralizers include sulf-oxyacids and salts thereof, hydrogen peroxide production mixtures, sugars and the like.

)를 제조하는 알리드 코포레이션(Allied Corporation)을 포함하여 몇몇 제조업체로부터 구입할 수 있다.Sulph-oxyacids and salts thereof are known as groups of compounds that act as chlorine bleach neutralizing agents. Considering the low price, high performance and ease of purchase, ammonium sulfite ((NH ₄ ) ₂ SO ₃ ), sodium sulfite (Na ₂ SO ₃ ), sodium thiosulfite (Na ₂ S ₂ O ₃ ), sodium metabisulse Alkali metals of sulfo-oxy acids, such as pits (Na ₂ S ₂ O ₃ ), potassium metabisulfite (K ₂ S ₂ O ₅ ), lithium sulfide sulfide, lithium hydrosulfite (Li ₂ S ₂ O ₄ ), and the like And ammonium salts are preferred. Sulphoxy acid is brand name sulftech (

Can be purchased from several manufacturers, including Allied Corporation.

Due to their odorless and non-corrosive properties, preferred chlorine bleach-neutralizers are compounds which can produce hydrogen peroxide in solution. Such compounds include perborate, percarbonate, superphosphate, peranthate and the like. Such compounds are readily available from several manufacturers, including Interox Peroxid-Chemie GmbH and Dupont. Considering the price and ease of purchase, sodium perborate monohydrate, available from Interox Peroxid-Chemie GmbH, is a preferred hydrogen peroxide generating material.

The encapsulated enzyme may comprise from about 1 to 95 weight percent of a bleach-neutralizing agent, based on the total capsule. However, in order to achieve an economic balance between the efficiency of encapsulation and the amount of coating to be used and to obtain sufficient bleach-neutralizing substances to completely neutralize all active chlorine present in the solution, the capsules are based on total capsules. It is preferred to include about 10 to 60% by weight of the neutralizing material.

Delayed Release Material

In a first aspect of the invention, it is the outer coating of the release retardant that encapsulates and protectively encapsulates the primary coating of the enzyme core and the bleach-neutralizing substance. The release retardant delays the release of the bleach-neutralizer and the enzyme so that the bleach used as a combination with the capsule may perform its washing action before being inactivated by the bleach-neutralizer. The release retardant must, of course, be miscible with the enzyme, bleach-neutralizer, and all other ingredients to be mixed therewith. In addition, delayed release materials should not damage the substrate to be cleaned. Any material that can delay the release of the actual amount of bleach-neutralizing material for about 1 to 20 minutes, preferably 2 to 6 minutes while satisfying the above two conditions can be used in the present invention.

Generally, release delaying materials include high molecular weight semisolid or solid fats, inorganic solids, natural or synthetic polymers, and the like. Given the excellent film forming properties, preferred release delay materials are natural and synthetic polymers. Suitable release delay polymers are known in the art and include cellulose derivatives such as sodium carboxymethyl cellulose, sodium hydroxy ethyl cellulose, ethyl cellulose, hydroxy propyl cellulose, hydroxy propyl methyl cellulose, nitro cellulose, cellulose acetate phthalate, and Hydroxy propyl methyl cellulose phthalate), gelatin, starch, protein, fatty acid, wax (containing paraffin and microcrystalline wax), polyacrylamide, polyacrylic acid, polyvinyl alcohol, polyethylene glycol and the like. The use of these materials and other similar delayed release materials, including the selection of compounds suitable for a particular use, is known to those of ordinary skill in the art.

를 제조하는 허큘스 인코포레이티드(Hercules Inc.)를 포함한 몇몇 제조업체로부터 구입할 수 있다.Due to the nature of suspending solids in solution along with the nature of the release delay of these materials, preferred release delay materials are carboxymethyl cellulose and salts thereof. Suitable sodium carboxymethyl cellulose

It can be purchased from several manufacturers, including Hercules Inc., which manufactures.

The encapsulated enzyme may contain from about 1 to 50% by weight release delay based on the capsule as a whole. The preferred weight percent depends on the specific material used and the period of time that allows the action of the bleach before it is inactivated by the bleach-neutralizer. For dishware and fiber cleaning, about 1-20% by weight of release retardant based on the entire capsule is safe.

Initial release delay

To ensure that all active chlorine in the solution is neutralized by the bleach-neutralizer before the enzyme is released, the encapsulated enzyme may include an initial coating of release delay between the enzyme center and the bleach-neutralizer.

Although good results have been found to be obtained in the absence of initial coating, it is useful to use reactive reducing agents or small amounts of reducing agents in some cases, such as when using unstable enzymes. The initial coating of release retardant material may include all of the release retardant materials described above.

The amount of initial coating needed to inactivate all active chlorine before the enzyme is released depends on the amount and type of bleach-neutralizing agent and the initial coating to be used. However, about 0.5 to 5% by weight of the initial coating, based on the capsule as a whole, is usually sufficient to prevent release in advance.

Combination of Encapsulated Enzymes and Encapsulated Bleach-Neutralizers

A second aspect of the invention is an enzyme encapsulated with a release delay material designed to delay release of an enzyme into solution during a first delay period, to delay release of a bleach-neutralizer into solution during a second delay period. A composition comprising a bleach-neutralizing substance encapsulated with a designed release delaying substance, wherein the first delaying period is longer than the second delaying period, so that the bleaching-neutralizing substance is released before the enzyme is released, It is possible to completely neutralize all active chlorine. The bleach-neutralizer may be present as primary coating on the core or diluent center. In addition, the enzyme can be encapsulated with an inner coating of bleach-neutralizing agent between the enzyme and the release retardant. The enzyme can also be initially encapsulated with a release delaying material.

diluent

The diluent core is used as a carrier for the bleach-neutralizer coated on the diluent. This is particularly useful when the bleach-neutralizer does not readily form substantially homogeneous granules. The use of diluent centers simplifies the manufacturing process since the enzyme and diluent are simultaneously coated with bleach-neutralizer.

Suitable diluents include sodium sulfate, sodium chloride and the like.

The enzymes, chlorine bleach-neutralizers, release delays and chlorine bleaches described above in connection with the first aspect are all well studied for their purpose. The release retardant used to coat the enzyme and bleach-neutralizer may be the same or different. For ease of manufacture they are preferably the same.

The present composition is particularly useful in that the ratio of chlorine bleach-neutralizer to enzyme is so large that there is not enough enzyme present under attack by chlorine bleach-neutralizer.

Typically, the release retardation layer is designed to block the release of the bleach-neutralizer for at least 1 minute, preferably about 2 to 6 minutes, and the enzyme is protected for an additional 0.5 to 2 minutes after the release of the chlorine bleach-neutralizer. Is encapsulated.

In this respect, the encapsulated enzyme particles may be present in trace amounts of up to about 95% by weight, preferably from about 30 to 80% by weight of the enzyme from about 0 to 10% by weight, preferably from about 0 to 5% by weight. External coating of the prepared initial coating, about 0 to 95% by weight, preferably about 10 to 60% by weight of bleach-neutral, and about 1 to 50% by weight, preferably about 1 to 20% by weight The encapsulated chlorine bleach-neutral, comprising a coating, is preferably used in trace amounts of up to about 95 weight percent, preferably from about 50 to 80 weight percent diluent center, in trace amounts up to about 95 weight percent, as a center. When used as about 50 to 80% by weight or primary coating, about 15 to 40% by weight of chlorine bleach-neutralizer, and about 1 to 50% by weight, preferably about 1 to 20% by weight of release retardant It may include.

Combination of encapsulated enzyme, encapsulated bleach-neutral and encapsulated diluent with a coating of bleach-neutral

A third aspect of the invention is an enzymatic center encapsulated with a release retardant, an inner coat of bleach-neutralizing material and a diluent center encapsulated with an outer coating of release delaying material, and a bleach-neutralizing encapsulated with a release delaying material. A composition comprising a material center. The enzyme and bleach-neutral center can be encapsulated with an inner coating of bleach-neutralizer between the center and the release retardant. In addition, the release delay coating on the enzyme center may be designed to delay release of the enzyme into the solution during the first delay period, and the release delay coating on the diluent center and the bleach-neutralizing agent may be diluted and bleached during the second delay period. It can be designed to delay the release of the neutralizer into the solution, where the first delay period is longer than the second delay period so that the bleach-neutralization center and coating are released before the enzyme is released, present in the solution. Neutralize all active chlorine.

The enzymes, chlorine bleach-neutralizers, release delays, and chlorine bleaches already described in connection with the first aspect of the invention are also suitable for equal use in this respect. The release retardant and the bleach-neutralizer used to coat the enzymes, bleach-neutralizers and diluents may be the same or different. The same is preferable considering the ease of manufacture.

The present composition is particularly useful in that the ratio of chlorine bleach-neutralizer to enzyme is so large that there is not enough enzyme present under attack by chlorine bleach-neutralizer.

Typically, in the case of encapsulating enzymes, bleach-neutralizers and diluents to enable early release of bleach neutralizers, the release retardation layer provides for at least one minute, preferably about 2 to 6 minutes, release of the bleach-neutralizers. It is designed to block and the enzyme must be protectively encapsulated for an additional 0.5 to 2 minutes after all the bleach-neutralizer has been released into solution.

In this respect, the encapsulated enzyme particles may be present in trace amounts up to about 95% by weight, preferably from about 30 to 80% by weight of enzyme, from about 0 to 10% by weight, preferably from about 0 to 5% by weight Consisting of an initial coating of about 0 to 95% by weight, preferably about 10 to 60% by weight of bleach-neutralizing material, and about 1 to 50% by weight of release delay material The encapsulated chlorine bleach-neutral, comprising an outer coat, comprises about 50 to 80 weight percent chlorine bleach-neutral center, about 0 to 40 weight percent chlorine bleach-neutral coat, and about 1 to 50 weight percent Preferably, from about 1 to 20 weight percent release delay, the encapsulated diluent is from about 30 to 80 weight percent diluent center, from 10 to 60 weight percent chlorine bleach-neutral and from about 1 to 50 weight percent %, Preferably from about 1 to 20% by weight of release delay material Can be.

The present invention, in particular, obtains a diluent and bleach-neutralizing agent of approximately the same granule size as the enzyme granules, and simultaneously coats the enzyme, diluent and bleach-neutralizing granules with the bleach-neutralizing agent, and then releases the coated granules. An easy and effective method of encapsulating enzymes and bleach-neutralizers released in the desired order, characterized by coating with a substance.

Washing composition

A fourth aspect of the present invention is the mixing of the composition of the first, second and / or third aspect with at least one chlorine bleach and one or more additional detergent ingredients to form an effective cleaning composition. The chlorine bleach can dissolve quickly so that its cleaning function can be accomplished before the chlorine bleach-neutral is released. Most of the known chlorine bleach dissolves rapidly and is suitable for use in the present invention.

Chlorine bleach is a known group of compounds capable of releasing active chlorine (Cl ₂ ) or hypochlorite ions (OCL-) into solution. Suitable chlorine bleaches include alkali metal dichloro isocyanurate, chlorinated trisodium phosphate salts, alkali metal and alkaline earth metal hypochlorites, monochloramines, dichloramines, nitrogen trichloride, [(mono-tri-chloro) -tetra- (Mono-potassium dichloro)] penta-isocyanurate, 1,3-dichlor-5,5-dimethyl hydantoin, paratoluene sulfonedi-chloroamide, trichlormelamine, N-chloromelamine, N-chlorosuccinate Mead, N, N'-dichloroazodicarbonamide, N-dichloroacetylurea, N, N'-dichlorobiuret, chlorinated dicyandiamide, trichlorocyanuric acid, dichloroglycoluril and the like. Given excellent bleaching performance, preferred bleaches are hydrated and anhydrous sodium dichloroisocyanurate and chlorinated trisodium phosphate salts. Such bleaching agents include Olin Corporation, commercially available under the trade name Clearon CDB-56 (Sodium dichloroisocyanurate dihydrate), and Monsanto Industrial Chemical Co., commercially available under the trade name ACL-56. It can be purchased from some manufacturers.

The cleaning composition may comprise only chlorine bleach and encapsulated enzymes, but one or more additional detergent components such as surfactants, detergent fillers, detergent enhancers, metal ion sequestrants, chelating agents, etc. may be used to increase washing ability. It is preferable to contain.

Suitable organic surfactants include anionic, nonionic, amphoteric, cationic materials and mixtures thereof. Any miscible surfactant can be used, but the most widely used surfactant forms for detergent compositions include soaps of fatty acids, rosinic acid, and tall oil (ie, sodium or potassium salts); Alkyl laulene sulfonate; Alkyl sulfates, including primary and secondary sulphate groups as well as surfactants containing branched and straight chain hydrophobic substances; Sulfates and sulfonates containing intermediate linkages between hydrophobic and hydrophilic groups such as fatty acylated methyl taurate and sulfated fatty monoglycerides; Long-chain esters of polyethylene glycols, in particular tols esters; Polyethylene glycol ethers of alkyl phenols; Polyethylene glycol ethers of long chain alcohols and mercaptans; Fatty acyl diethanolamides; And block copolymers of ethylene oxide and propylene oxide.

Suitable detergent fillers, enhancers, metal ion sequestrants and chelating agents are all known ingredients having functions such as maintaining alkaline pH, suspending granulated material in solution, preventing re-degradation of the granulated material, and the like. Included. Typical examples of such detergent fillers, enhancers, metal ion sequestrants and chelating agents include condensed phosphates (e.g. sodium tripolyphosphate), alkalis (sodium carbonate, sodium metasilicate, and sodium hydroxide), fillers (e.g. sodium sulfate, sodium bicarbonate and Sodium chloride), stain suspending agents (such as carboxymethylcellulose), and chelating agents (such as ethylenediamine tetraacetic acid and polyacrylic acid).

The wash composition is about 0.1 to 1.5% by weight, preferably about 0.5 to 1% by weight of commercially available chlorine, about 0.3 to 20% by weight, preferably about 1.5 to 15% by weight of encapsulated enzyme, active chlorine In theory an excess of encapsulated bleach-neutral and about 0-99% by weight, preferably about 55-95% by weight of additional detergent components. It is preferred that the cleaning composition contain up to 10% by weight of surfactant as an additional detergent component.

The amount of chlorine bleach-neutralizer to be used should be sufficient to reduce all of the active chlorine in the solution. In order to immediately deactivate the active chlorine, it is preferred that the stoichiometric ratio of the bleach-neutralizing agent to the active chlorine is about 1: 1 to 1.5: 1.

Manufacturing method

Encapsulated enzymes and encapsulated bleach-neutralizers can be prepared by several known encapsulation methods such as pan coating, roller coating, spray freezing and the like. The preferred method is the fluidized bed encapsulation method.

Basically, the encapsulation process in a fluidized bed is characterized by comprising the following steps: i) liquefying the coating material by melting the material or dissolving the material in a suitable solvent (preferably water), and (ii) The particles to be encapsulated by flowing into the chamber and passing oil therethrough, i) spraying the liquefied coating material onto the fluidized particles to coat the particles with the coating material, and iii) the coated particles are cooled and Allow to dry.

Washing compositions can be prepared by simply mixing with other ingredients to minimize the potential for damage to the capsule.

Example I

Into a 32 liter container add 1.25 lbs of KLUCEL E (hydroxy propyl cellulose manufactured by Hercules, Inc.) and 39.4 lbs of soft water.

Mix KLUCEL E and soft water until KLUCEL E is dissolved. To the fluidized bed is added 23.75 lbs of TERMAMYL 60T (a powdered bacterial amylase manufactured by Novo Industri a / s). The TERMAMYL 60T is flowed in a bed of 40 psi air pressure and heated to 105 ° F. The total amount of KLUCEL E is sprayed onto the fluidized TERMAMYL 60T granules using a nebulizer (Gustav Schlick Nozzle, Model 941). The fluidized bed is heated to 125 ° F. and the encapsulated TERMAMYL 60T is dried at the same temperature for 1 minute. The capsules are cooled to 100 ° F. and separated in layers to give 24.5 lbs of encapsulated TERMAMYL 60T.

To the fluidized bed used is added 24.5 lbs of encapsulated TERMAMYL 60T and 27.86 lbs of granular sodium sulfate. To a 32 liter container add 5.68 lbs of sodium perborate monohydrate (manufactured by Interox Peroxid-Chemie GmbH) and 113 lbs of soft water. Stir the perborate monohydrate and water until the sodium perborate monohydrate is completely dissolved.

Encapsulated TERMAMYL 60T and sodium sulfate are flowed in a fluidized bed at 60 psi of air pressure and the bed is heated to a temperature between 140 and 168 ° F. The total amount of sodium perborate monohydrate solution is sprayed onto the molten TERMAMYL 60T and sodium sulfate granules. The temperature of the fluidized bed is adjusted between 142 and 150 ° F. and the encapsulated granules are left to dry. Add 2 lbs KLUCEL E and 60 lbs soft water to a 32 liter container. Stir KLUCEL E and soft water until KLUCEL E is completely dissolved. After drying the coating of sodium perborate monohydrate, the KLUCEL E solution is sprayed onto the primary coated granules to obtain a capsule firstly coated with sodium perborate monohydrate and secondly coated with KLUCEL E. The fluidized bed is heated to 170 ° F and the encapsulated granules are dried at this temperature for 2 minutes. The capsules are cooled to 100 ° F. and separated from the layers. A capsule having 90.4% activity of the original enzyme activity is obtained.

Example II

To a concentration of chlorine bleach solution is added an excess of the composition obtained in Example I than sodium perborate monohydrate sufficient to effect 2% stoichiometric bleach-neutralization. After dissolving the outer coating made of KLUCEL E, the coating made of sodium perborate monohydrate, and the initial coating made of KLUCEL E, the solution was analyzed and 27.0% of the initial enzyme activity was observed.

Example III

To a concentration of chlorine bleach solution is added an excess of the composition obtained in Example I than sodium perborate monohydrate sufficient to effect 20% stoichiometric bleach-neutralization. After dissolving the outer coating made of KLUCEL E, the coating made of sodium perborate monohydrate, and the initial coating made of KLUCEL E, the solution was analyzed and 54.6% of the initial enzyme activity was observed.

Example IV

To a 32 liter container add 1.5 lbs of sodium sulfate and 15 lbs of soft water. Mix sodium sulfate and soft water until the sodium sulfate is completely dissolved.

To the fluidized bed is added 18 lbs of ESPERASE 4.0T (a powdered bacterial protease manufactured by Novo Industri a / s). ESPERASE 4.0T is flowed in a fluidized bed with a spray pressure of 40 psi and the bed heated to 125 ° F. The entire amount of sodium sulfate solution is heated to 120 ° F and sprayed onto the fluidized ESPERASE 4.0T granules using a nebulizer (Gustav Schlick Nozzle, Model 941).

Into a 32 liter container add 4.6 lbs of sodium perborate monohydrate (Interox) and 93.48 lbs soft water. Sodium perborate and water are stirred until the sodium perborate monohydrate is completely dissolved. The fluidized bed is heated to 130 ° F., the sodium perborate monohydrate solution is maintained at 115 ° F. or lower, and then the entire amount of sodium perborate solution is sprayed onto the coated fluidized granules. To a 32 liter container add 1.51 lbs of CMC-CLT (sodium carboxymethyl cellulose; manufactured by Hercules Inc.) and 49.51 soft water. Mix CMC-CLT and soft water until CMC-CLT is completely dissolved. Finally the CMC-CLT solution is kept below 130 ° F. and the entire amount is sprayed onto the two coated fluidized granules.

The fluidized bed is heated to 130 ° F and the three encapsulated granules are dried at the same temperature for 1 minute, then cooled to 100 ° F and separated from the bed.

Example Ⅴ

To a beaker equipped with a stirring bar and plate is added 0.10 g of sodium dichloroisocyaturate dihydrate, 100.6 g of deionized water and 0.34 g of the encapsulated enzyme obtained in Example IV. The mixture is stirred vigorously and completely neutralized active chlorine for about 3 minutes. The resulting solution was found to have enzymatic activity of 2.28 kkn units per gram of encapsulated enzyme, indicating that it possesses 80% of theoretical activity.

Example VI

470.5 g of sodium sulfate and 1600 g of soft water are added to a 2-liter container. Mix sodium sulfate and soft water until the sodium sulfate is completely dissolved.

To a separate 1 liter container, 70.5 g of polyacrylic acid having a molecular weight of 3000 and 211.5 g of soft water are added. The polyacrylic acid and soft water are mixed until the polyacrylic acid is completely dissolved.

To the fluidized bed is added 352.9 g of ESPERASE 4.0M (Bacterial Protease from Powder; manufactured by Novi Industri a / s). ESPERASE 4.0M is flowed in the bed and the bed is heated to 80 ° F. The entire amount of sodium sulfate solution is heated to 84 ° F. and fluidized ESPERASE 4.0M is sprayed onto the granules.

The fluidized bed is heated to 110 ° F., and the entire polyacrylic acid solution is heated to 90 ° F. and then sprayed onto the coated granules once. The fluidized bed is heated to 120 ° F. and the twice coated granules are dried at the same temperature, then cooled to 100 ° F. and separated from the bed.

Example Ⅶ

To a beaker equipped with a stirring plate was added 0.4 g of sodium dichloro isocyanurate dihydrate (manufactured by EMC Corp.) and 150 g of soft water and heated to 140 ° F., followed by addition of 1.0 g of the encapsulated enzyme obtained in Example VI. do. The mixture is stirred vigorously and the active chlorine is completely neutralized. EMPA 116 test fabric is added to the solution and the enzyme activity is measured. The above description and examples are not intended to limit the invention. The invention is capable of many variations and aspects without departing from the spirit and scope thereof, and the invention is based on the claims hereinafter appended.

Claims (15)

(a) from 1 to 95% by weight of an enzyme core, based on the encapsulated enzyme; (b) a primary encapsulation coating of 1 to 95% by weight of chlorine bleach-neutralizing agent, based on the encapsulated enzyme; And (c) a secondary encapsulation coating of 1 to 50% by weight release delay material, based on the encapsulated enzyme, to deliver the active enzyme to a wash solution containing active chlorine. Encapsulated enzyme. The capsule of claim 1, further comprising 0.5-5% by weight, based on the encapsulated enzyme, of an initial encapsulating coating of release retardant between the enzyme center and the chlorine bleach-neutralizing primary coating. Oxidized enzyme. (a) 1 to 95 weight percent enzyme center based on the encapsulated enzyme; (Ii) a primary encapsulation coating with 1 to 95% by weight of chlorine bleach-neutralizing agent, based on the encapsulated enzyme; And (iv) a second encapsulated coating of 1 to 50% by weight of release retardant, based on the encapsulated enzyme, and (b) (v) encapsulated chlorine bleach 1 to 95% by weight of chlorine bleach-neutralizing substance core, based on neutralizing substance; And (ii) an encapsulated chlorine bleach-neutralizing agent, the encapsulating coating comprising 1-50% by weight of release retardant, based on the encapsulated chlorine bleach-neutralizing agent; Containing active chlorine, characterized in that the stoichiometric ratio of bleach-neutral to active chlorine is in the range of from 0.3 to 20% by weight in the resulting wash composition, wherein the enzymatic enzyme is from 1: 1 to 1.5: 1. A composition that delivers an active enzyme in solution to form a wash composition. (a) 1 to 95 weight percent enzyme center based on the encapsulated enzyme; (Ii) a primary encapsulation coating with 1 to 95% by weight of chlorine bleach-neutralizing agent, based on the encapsulated enzyme; And (iii) a second encapsulated coating of 1 to 50% by weight release delay based on the encapsulated enzyme, and (b) (iii) an encapsulated diluent. 30 to 80% by weight of a diluent core based on the standard; (Ii) a primary encapsulation coating of 10 to 60% by weight chlorine bleach-neutralizing agent, based on the encapsulated diluent; And (iii) a separately encapsulated diluent, comprising a second encapsulated coating of 1 to 50% by weight release delay material based on the encapsulated diluent, wherein the encapsulated enzyme is produced. Delivering the active enzyme to a wash solution containing active chlorine, which is present in the composition in an amount of 0.3 to 20% by weight and is characterized in that the stoichiometric ratio of bleach-neutralizer to active chlorine is from 1: 1 to 1.5: 1. To form a wash composition. The encapsulated enzyme of claim 1, wherein the enzyme is a protease, lipase, amylase or mixtures thereof. The encapsulated enzyme of claim 1, wherein the chlorine bleach-neutralizer is sulf-oxyacid or a salt thereof. The encapsulated enzyme of claim 6, wherein the sulf-oxy acid or salt thereof is thiosulfate, metabisulfite, bisulfite or salt thereof. The encapsulated enzyme of claim 1, wherein the chlorine bleach-neutralizer is perborate, persulfate, superphosphate or percarbonate. The encapsulated enzyme of claim 1, wherein the release retardant is a cellulose derivative. (a) 1 to 95 weight percent enzyme center based on the encapsulated enzyme; (Ii) a primary encapsulation coating with 1 to 95% by weight of chlorine bleach-neutralizing agent, based on the encapsulated enzyme; And (iii) a secondary encapsulation coating of 1-50% by weight of release retardant, based on the encapsulated enzyme, and 0.3-20% by weight of encapsulated enzyme, based on the wash composition. (b) 0.1 to 40 weight percent chlorine bleach, based on the wash composition, and (c) 55 to 95 weight percent detergent filler, formulation enhancer, surfactant, metal ion sequestrant based on the wash composition. And an additional detergent component selected from the group consisting of chelating agents. (a) 1 to 95 weight percent enzyme center based on the encapsulated enzyme; (Ii) a primary encapsulation coating with 1 to 95% by weight of chlorine bleach-neutralizing agent, based on the encapsulated enzyme; And (iii) 0.3-20% by weight of encapsulated, based on the wash composition, comprising a second encapsulated fibrate of 1-50% by weight of release retardant, based on the encapsulated enzyme. enzyme. (b) 1 to 95 weight percent diluent center based on the encapsulated diluent; (Ii) a primary encapsulating coating of 1 to 95% by weight of chlorine bleach-neutralizing agent, based on the encapsulated diluent; And (iii) a stoichiometric ratio of bleach-neutralizing agent to active chlorine of 1: 1 to 1.5, comprising a secondary encapsulating coating of 1 to 50% by weight of release retardant, based on the encapsulated diluent. : Bleach-neutralized encapsulated diluent to be 1, (c) 0.1 to 40% by weight of chlorine bleach, based on the wash composition, and (d) 55 to 95% by weight, based on the wash composition A detergent composition comprising a detergent component selected from the group consisting of detergent fillers, detergent enhancers, surfactants, metal ion sequestrants and chelating agents. The wash composition of claim 11 wherein the enzyme is a protease, lipase, amylase or mixtures thereof. The cleaning composition of claim 11, wherein the chlorine bleach-neutralizer is sulf-oxyacid or a salt thereof. The cleaning composition of claim 11, wherein the chlorine bleach-neutralizer is perborate, persulfate, superphosphate or percarbonate. 12. The cleaning composition of claim 11, wherein the release delay material is a cellulose derivative.