JPH07506137A - Capsules containing easily degradable components and composite polymers - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] Background of the invention field of invention The present invention relates to polymeric capsules suitable for use in heavy duty liquid detergent compositions. , this capsule contains detergent-sensitive active ingredients, and hydrophobic and hydrophilic polymers. and a novel composite polymer comprising

Conventional technology Heavy liquid detergents may be incompatible with desirable ingredients such as bleach, enzymes and fragrances. It is well known to those skilled in the art that it presents a favorable environment. Therefore, the sensitivity of enzymes etc. Protect the ingredients from the composition during storage, but when the liquid is used by the consumer. It is often desirable to ensure release in a controlled and reproducible manner. this components that are sensitive to other components found in the composition (e.g., detergents). Enzymes in compositions, particularly concentrated detergent compositions, are denatured by surfactants in the detergent composition. You can protect it by enclosing it until it is time to release it, or you can simply add a washing solution (th Examples of other ingredients (e.g. fragrances and antifoaming agents) that are desirable to release during For example, the release may be controlled by diluting the concentrate.

In particular, it is desirable to encapsulate one or more enzymes, since the enzymes are contaminated during the cleaning process. A highly effective laundry cleaning ingredient used to accelerate the removal of dirt and stains. This is because that.

European Patent Application Publication Box 266, 796 (Shova Denko) Preferably, the enzyme can be harvested by dissolving or dispersing it in water containing a polyhydroxy compound. The authors teach water-soluble microcapsules containing water-soluble microcapsules, which can be water-soluble polyvinyl alcohol (PVA) or partially hydrolyzed polyvinyl as coated with alcohol. chemically or physically combined with a hydrophilic polymer The system contains enzymes or other detergent-sensitive active ingredients composed of hydrophobic particles. Or, there is no teaching or suggestion of composite polymers containing network structures trapped in the structure. stomach. In addition, the PVA used in this Showa Denko reference is The average of 200-3.000 is different from pv^ which can be used as a hydrophilic component of light. It has a degree of polymerization and a hydrolysis rate of 90% or more, preferably 95% or more. of P.V.A. When the hydrolysis rate is less than 90%, the microcapsules are not stable and contain water. It is said to dissolve in liquid detergents during storage. Perhaps not surprisingly, Kap. Nothing other than a crosslinking agent is mentioned as something that stabilizes the cell; Ethylene polymers can be chemically or physically linked to form a capture network. Hydrophobic core particles with sexually unsaturated groups are neither taught nor suggested. That is, this pull The example encapsulation polymer uses only water-soluble polymers (i.e., PVA); A soluble portion or region (i.e., the bound hydrophilic polymer) and a water-insoluble portion or region A complex emulsion containing a hydrophilic polymer (i.e. hydrophobic particles bound to a hydrophilic polymer) A capture polymer that is a copolymer was not used. Pores that are generally water soluble Optimal water resistance is not achieved using reamers.

Such polymers are also more difficult to process than the composite polymers of the present invention. lastly, The level of hydrolysis of PVA taught in this reference (i.e., greater than 90%, preferably 90%) 5%), the capsule or polymer will be protected from dissolution at ambient temperature. The added components are only partially released upon dilution. Moreover, the above cited example has a lower rate We do not accept the option of using PVA hydrolyzed at Decomposed PVA dissolves more easily when diluted; This is because it is sensitive and cannot protect the open needle in storage.

U.S. Pat. No. 4,906,396 (Falholt et al.) He teaches enzymes that have been developed. In this reference as well, both the water-soluble part and the water-insoluble part Polymers that are complex emulsion copolymers containing .

British Patent No. 1.390.503 (Unileverl: Assigned) discloses that when diluted It teaches polymers that dissolve when the ionic strength of the body is reduced. Once again, sparse chemically and/or physically bonded to the aqueous core (i.e. hydrophobic particles); The hydrophilic moieties that make up the capture emulsion polymer capture enzyme components by (i.e., one or more hydrophilic polymers) Mar system is not taught.

U.S. Patent No. 4.777,089 and U.S. Patent No. 4.908.233 (Takiza wa, etc.) is a single water-soluble polymer (which undergoes phase separation due to the action of electrolytes in the composition). Microphones that include a “core” material (i.e. the material to be protected forms the core) coated with teaches the use of rocapsules. This reference also shows that the hydrophobic core particle is chemically or physically bound hydrophilic moieties, and are used to capture sensitive substances that are easily degraded. Composite emulsion polymers that may be used are neither taught nor suggested. hydrophilic part and Composite polymers such as those described above, which have both hydrophobic moieties, can trap sensitive components. This prevents the harsh ingredients from approaching the sensitive ingredients from outside the capsule. , and to delay the approach of sensitive components to water and strong-acting components outside the capsule. This is a significant advantage over the cited encapsulating polymers, which are merely water-soluble.

U.S. Patent No. 4,842°761 (Rutherford) This paper teaches compositions and methods for the controlled release of fragrances. The cited compositions include water-soluble and water-insoluble polymers (both usually solid) and fragrances. composition, where part of the fragrance composition is a water-soluble polymer and a part is a water-insoluble polymer. Contained in polymers. The two polymers are discontinuous, one in the matrix of the other. mutually physical in the form of discrete entities have a relationship. The particles of this reference have a particle size of less than 100 μm. Unlike capsules, they have a particle size of 100 to 3,000 μm. In addition, capsules The formation of a polymer homogeneously mixes water-soluble and water-insoluble polymers under high shear stress. The emulsion polymer capsules of the present invention are A capsule system is formed.

No. 07/766,477, filed by the assignee of the present application, discloses the use of fragrances and waxes. teaches a water-soluble polymer used to encapsulate particles consisting of an emulsifying mixture with are doing. The waxes used are hydrocarbons, including paraffin wax and microcrystalline wax. wax, etc. These waxes are different from the hydrophobic core particles of the present invention. That's right Well, the core is not just a waxy substance surrounding the fragrance, but a homogeneous mixture of wax and fragrance. This point is completely different from the core particle of the present invention, which can exist alone.

In fact, the enzyme of the invention is not present inside the hydrophobic core particle at all. lastly In this reference, the release of the encapsulated substance is triggered by heat, but in the present invention, the release of the encapsulated substance is caused by heat. Quality release is induced by dilution.

U.S. Pat. No. 4,115,474 (Vassiliades) describes hydroxyl The graft polymerization of a polymeric shell containing silane onto a water-insoluble core has been disclosed. There is. The hydroxyl shell is crosslinked with formaldehyde condensate and diluted with water. does not release chloroform. Moreover, this reference shows that captured It doesn't even mention sensitive substances. In fact, the capsule even releases pressure It is intended as a load-bearing capsule.

None of the above-mentioned patents are designed to release captured sensitive substances upon dilution. does not teach capsules containing the particular composite emulsion polymers of the present invention, much less There is no teaching of such capsules for use in heavy liquids.

Thus, there is a need in the art for capsules suitable for use in heavy liquid compositions. In this case, the capsule contains components that are susceptible to decomposition (hereinafter referred to as "detergent-like"). can stabilize sensitive active ingredients (“active ingredients”), while at the time of use, e.g., especially at ambient temperature. Contains a novel composite polymer that can easily decompose and release components in diluted aqueous media. nothing.

Thus, the present invention allows sensitive components to be stabilized and sequestered in heavy liquid compositions, while at the same time When the composition is diluted with water, the ingredients are released in a controlled and reproducible manner. It is an object of the present invention to provide a novel composite polymer as described above.

Summary of the invention The present invention provides polymeric capsules suitable for use in detergent compositions, and Psel is (a) a detergent-sensitive active ingredient, and (b) (i) formed by emulsion polymerizable monomers having ethylenically unsaturated groups; (ii) a nonionic and water-soluble synthetic polymer; Polysaccharides, modified polysaccharides; proteins, modified proteins, polymers with carboxyl groups and a hydrophilic polymer selected from these copolymers; The ratio of hydrophobic core particles to hydrophilic water-soluble polymer is about 2:8 to about 7:3. Contains composite polymers.

Second, the present invention includes from about 5 to about 85% by weight surfactant and a polymer capsule. A heavy-duty liquid detergent composition is provided, wherein the polymer capsule is (a) a detergent-sensitive active ingredient, and (b) (i) formed by an emulsion-polymerizable heptamer having an ethylenically unsaturated group; (ti) a hydrophobic polymeric core particle that is insoluble in the detergent composition; a hydrophilic polymer that dissolves or disperses when the composition is diluted with water; wherein the ratio of hydrophobic core particles to hydrophilic water-soluble polymer is from about 228 to about The composite emulsion copolymer of the present invention has a hydrophilic portion of 7=3. (i.e., the hydrophilic polymer attached to the hydrophobic particle) and the hydrophobic polymer core (i.e., and a part of the particle to which the hydrophilic polymer is bonded.

The hydrophilic moiety is one or more types that physically or chemically bind to the hydrophobic polymer particles. A hydrophilic (preferably crosslinkable) water-soluble polymer. few percent hydrophilic The polymer can remain free and not bound. The hydrophobic part is emulsion poly It constitutes the core of Mar.

The emulsion copolymer of the present invention has a network structure consisting of hydrophobic particles and Entrapment of enzymes or other sensitive components between preferably cross-linked water-soluble polymers Ru. The emulsion copolymers of the present invention function as gels and are sensitive to sensitive ingredients. and degradable components move from outside the capsule to the outside of the capsule. It is believed that this slows down the flow to susceptible components trapped within the molecule.

Composition Regarding the various components of heavy liquid (IIDL) compositions that may contain the capsules of the present invention: The details will be explained later.

detergent active ingredients The composition may contain anionic, nonionic, cationic, amphoteric and zwitterionic surfactants, or or a mixture thereof. Like New surfactant detergents are mixtures of anionic and nonionic surfactants. but any surfactant alone or one or more other optional surfactants It should be understood that it can be used in combination with

Anionic surfactant detergent Anionic surfactants that can be used have long-chain hydrocarbon hydrophobic groups in their molecular structure. However, a field containing hydrophilic groups such as gas sulfonic acid groups and sulfuric acid groups, that is, groups that dissolve in water, It is a surface active compound. Anionic surfactants include water-soluble higher alkyl benzenes. higher alkyl sulfonic acid, higher alkyl sulfonic acid, higher alkyl sulfuric acid and higher alkyl polymer Contains alkali gold II (e.g. sodium and potassium) salts of riether sulfates. Ru. Fatty acids and fatty acid soaps may also be included in anionic surfactants.

Preferred anionic surfactants are alkali of higher alkylbenzene sulfonic acids. Metal, ammonium or alkanolamide salts, and higher alkyl sulfonic acids alkali metal, ammonium or alkanolamide salts. preferred high The class alkyl sulfonic acid has 8 to 26 alkyl groups, preferably 12 to 22 alkyl groups. , more preferably 14 to 18 carbon atoms. Alkylben The number of alkyl groups in zenesulfonic acid is preferably 8 to 16, more preferably 10 to 1. It has 5 carbon atoms. A particularly preferred alkylbenzene sulfonate is dodecylbenzene sulfonate. Sodium or potassium salts of rubenzenesulfonic acid, e.g. sodium zenesulfonate. Primary and secondary alkyl sulfonates are , long chain α-olefins as sulfites or bisulfites, e.g. sodium bisulfite. It can be produced by reacting with Alkyl sulfonates are surfactant detergents. Obtain normal or secondary higher alkyl sulfonates suitable for use as agents U.S. Pat. Nos. 2.503.280, 2.507.088, and 3. 372.188 and 3.260.741, the long chain nor Also produced by reacting marparaffinic hydrocarbons with sulfur dioxide and oxygen. It is possible to build Alkyl substituents are preferably straight-chain alkyls, i.e. normal alkyls. However, branched alkyl sulfonates may also be used.

Alkanes or alkyl substituents may be terminally sulfonated, or e.g. can be bonded to the carbon atom at the 2-position, ie, can be a secondary sulfonic acid. Substituent It will be understood by those skilled in the art that it may be attached to any carbon on the kill chain.

Higher alkyl sulfonic acids are salts of alkali metals such as sodium and potassium. It can be used as The preferred salt is the sodium salt. Preferred alkyl sulfonates is Cl11""C1a primary normal alkyl sulfonate sodium and potassium C1°~cps primary normal alkyl sulfonate is more preferable. Delicious.

A mixture of a higher alkylbenzene sulfonate and a higher alkyl sulfonate may also be used. Mixture of higher alkylbenzene sulfonate and higher alkyl polyether sulfate objects can also be used. The alkali metal salt of alkylbenzenesulfonic acid is 0 to 70% by weight. , preferably in an amount of 10 to 50% by weight, more preferably 10 to 20% by weight. Ru. Alkali metal salts of sulfonic acids, mixtures with alkylbenzene sulfonates It can be used in an amount of 0 to 70% by weight, preferably 10 to 50% by weight.

Also normal alkyl and branched alkyl sulfates (e.g. primary alkyl sulfates) Can be used as an anionic component.

The higher alkyl polyether sulfates used contain normal or branched chain alkyls. and may contain lower alkoxyl groups which may have 2 or 3 carbon atoms.

Higher alkyl polyether sulfates containing normal alkyls contain branched chain alkyls. It is preferable because it is more highly biodegradable than those containing lower polyalkoxyl. The group is preferably an ethoxyl group.

Preferred higher alkyl polyethoxy sulfates for use in accordance with the present invention have the formula %formula% [In the formula, R1 is C8-C2° alkyl, preferably C1°-C18, more preferably is CI2-cps alkyl, p is 2-8, preferably 2-6, more preferably or 2 to 4, and M11 alkali metals such as sodium and potassium or ammonium cation]. sodium and potassium salts is preferred.

Preferred higher alkyl polyethoxyfluorinated sulfates have the formula % formula % It is a sodium salt of C+Z~CI6 alkyltriethoxysulfate having the following formula.

Examples of suitable alkyl ethoxy sulfates that may be used include chi to CI5 normal or is the sodium salt of primary alkyltriethoxysulfate; n-decyljethoxysulfate Sodium salt of CI! Ammonium salt of primary alkyl jetoxysulfate; C1 Sodium salt of primary alkyl triethoxysulfate; Sodium salt of toxysulfate; CI4~C+slf! Combined normal primary alkyl Sodium salt of ethoxy and tetraethquin mixed sulfuric acid; stearyl pentaeth Sodium salt of quinsulfuric acid; and Cl11-C11 mixed normal primary alkyl salt There is a potassium salt of ethoxysulfate.

Normal alkyl ethoxy sulfates are easily biodegradable and are preferred. Poly - Alkyl sulfates having lower alkoxyl groups are and/or the higher alkylbenzenes mentioned above, It can be used in combination with a kill sulfonate or a higher alkyl sulfate.

Alkali metal salt of higher alkyl polyethoxy sulfuric acid to alkylbenzenesulfonic acid salt and/or alkyl sulfonate or sulfate of the total composition. 70% by weight, preferably 10-50% by weight, more preferably 10-20% by weight Can be used in amounts.

Nonionic synthetic organic detergent that can be used alone or in combination with other surfactants will be explained below.

As is well known, nonionic detergents are characterized by the presence of organic hydrophobic groups and organic hydrophilic groups. attached, typically organic aliphatic or alkyl aromatic hydrophobic compounds (hydrophilic is produced by condensation with ethylene oxide. A suitable nonio Typical examples of surfactants include U.S. Pat. 0.929.

Normally, nonionic detergents are polyalkoxylated lipophilic substances, and the lipophilic part By adding hydrophilic poly lower alkoxyl groups, desired hydrophilic-lipophilic properties can be obtained. Lance is obtained. Preferred nonionic detergents are alkoxylated alkanols. The alkanol has 9 to 18 carbon atoms, and (the carbon atom The number of moles of the alkylene oxide (two or three children) is from 3 to 12. like this Among substances, alkanols are fats with 9 to 11 carbon atoms or 12 to 15 carbon atoms. It is an alcohol, and the number of alkoxyl groups per mole is 5 to 8 or 5 to 9. It is preferable to use a substance that is

Examples of such compounds include alkanols with 2 to 15 carbon atoms per mole; Compounds containing about 7 ethylene oxide groups per cell, such as 5hell Che Neodol 25-, a product of mical Coa+pany, Inc. 7 and Neodol 23-6.5. Neodo125-7 has an average A mixture of higher fatty alcohols having about 12 to 15 carbon atoms and about 7 mol Neodol 23-6.5 is a condensation product with ethylene oxide, and Neodol 23-6.5 is a high-grade fat The number of carbon atoms in the fatty alcohol is 12 to 13, and the number of ethylene oxide groups present is average. The corresponding mixture is approximately 6.5 in average. Higher alcohols are primary alkano It is le.

Other useful nonionic surfactants are sold under the trademark "Plurafac" represented by a group of commercially well-known nonionic surfactants that . Plurafac is a higher linear alcohol with a hydroxyl group at the end. Ethylene oxide and propylene oxide containing mixed chains of ethylene oxide and propylene oxide It is a reaction product obtained by reacting with a mixture with lopylene oxide. For example is CI condensed with 6 moles of ethylene oxide and 3 moles of propylene oxide 3-CI5 fatty alcohol, 7 moles propylene oxide and 4 moles ethylene CI3-C eye fat condensed with oxide - propylene oxide of alcohol and a CI3 to CI5 fatty alcohol condensed with 10 moles of ethylene oxide, or or any mixture of these fatty alcohols.

Another liquid nonionic surfactant is 5hell Chemical Comp Any, Inc. under the trademark "DobanoL" and Banol 91-5 has an average of 5 moles of ethylene oxide per mole of fatty alcohol. Dobanol 25-7, C.~C0 fatty alcohol ethoxylated with cid is ethoxylated with an average of 7 moles of ethylene oxide per mole of fatty alcohol. These are C111-CI8 fatty alcohols.

C+Z to CI5 with an ethylene oxide content within a relatively narrow range of about 7 to 9 moles Ethoxylated with a primary fatty alcohol and about 5 to 6 moles of ethylene oxide. Among the preferred nonionic surfactants are 09-CI+fatty alcohols.

Glycoside surfactants are also nonionic surfactants that can be used. suitable for use The glycoside surfactant has the formula %formula%() [In the formula, R is a carbon atom having about 6 to about 30 (preferably about 8 to about 18) carbon atoms] a valent organic radical, and R1 is a divalent hydrocarbon having about 2 to 4 carbon atoms. is an elementary radical, where 0 is an oxygen atom, and y can have an average value of 0 to about 12; most preferably a number that is 0 and Z has 5 or 6 carbon atoms. is a moiety derived from a polysaccharide, and X is 1 to about 10 (preferably about IV2 to about 10) number with an average value of ].

Particularly preferred groups of glycoside surfactants include glycoside surfactants of the above formula: R in the formula is a monovalent compound having about 6 to about 18 (particularly about 8 to about 181 [1) carbon atoms] is an organic radical (straight or branched), where y is 0 and 2 is glucose or a moiety derived from glucose, and X is from 1 to about 4 (preferably about 1 % to 4).

It is also possible to use a mixture of two or more of the above-mentioned nonionic surfactants. Ru.

Cationic surfactant Many cationic surfactants are known to those skilled in the art and contain about 10 to 24 carbon atoms. Almost any cationic surfactant containing at least one long-chain alkyl group Also suitable for the present invention. Such compounds are referred to herein as "Ca tionic 5 urfactants”, Jungermann, 197 0.

Certain cationic surfactants that may be used are described in US Pat. No. 4.497.718.

Like nonionic and anionic surfactants, cationic surfactants can also be used in the composition. Can be used alone or in combination with any other surfactants known to those skilled in the art. Ru. Naturally, the composition must contain all (or no) cationic surfactants or amphoteric synthetic detergents. Agents are broadly defined as aliphatic derivatives or heterocyclic secondary and tertiary amines. It can be explained that it is an aliphatic derivative of may be branched (and one aliphatic substituent has about 8 to 18 carbon atoms) , and at least one aliphatic substituent is a water-soluble anionic group, e.g. Contains xyl group, sulfonic acid group, and sulfate group. Examples of compounds that fit this definition include: Sodium 3-(dodecylamino)propionate, sodium 3-(dodecyl Amino)propane-1-sulfonate, sodium 2-(dodecylamino)-e Tylsulfate, sodium 2-(dimethylamino)octadecanoate, di Sodium 3-(N-carboxymethyldodecylamino)propane-1-sulfo ate, disodium octadecyl-iminodiacetate, sodium l-cal Boxymethyl-2-undecylimidazole and sodium N,N-bis(2 -hydroxy-ethyl)-2-sulfato-3-dodecoxypropylamine. Ru. Sodium 3-(dodecylamino)propane-1-sulfonate is preferred .

Twin surfactants broadly refer to secondary and tertiary amine derivatives, heterocyclic secondary and and derivatives of tertiary amines, or quaternary ammonium compounds, It can be explained as a derivative of a tertiary sulfonium compound or a tertiary sulfonium compound. Fourth class A cation atom of a compound can be part of a heterocycle. In any of the above compounds Also, at least a straight or branched aliphatic group having about 3 to 18 carbon atoms one aliphatic substituent and one aliphatic substituent present in a small number (one aliphatic substituent is an anionic group that is soluble in water, e.g. For example, it contains a carboxyl group, a sulfonic acid group, a sulfuric acid group, a phosphoric acid group or a phosphonic acid group. nothing.

Specific examples of twinning surfactants that may be used are provided in U.S. Pat. No. 4.062.647.

The amount of active substance used is from 1% to 85% by weight, preferably from 10% by weight. It can vary up to 50% by weight.

The composition containing the capsules of the present invention may or may not have a specific structure. This point should be kept in mind.

A liquid composition with a specific structure means that at least one of the detergent actives is a solid It means a composition that constitutes a specific structural phase in which particulate matter can be suspended.

In particular, when a liquid with a specific structure is contemplated, the composition may be a soap/surfactant. inducing the formation of a lamellar phase, thereby providing the ability to suspend solids. Requires large amounts of electrolytes. Selecting the type and amount of electrolyte(s) Matching the electrolyte to the pre-selected soap/surfactant by can be achieved using very well known methods. This method allows for very different Special techniques described in references are used. One such technology is conductivity Including measurements. Detection of the presence of lamellar phases etc. is also very good (known, e.g. conductive This can be done by optical and electron microscopy measurements assisted by rate measurements and by X-ray diffraction.

When using a liquid with a specific structure, a combination of surfactants with a specific structure For example, LAS/ethoxylated alcohol alcohol S/lauryl ether sulfate Phate (LES), LAS/LES/ethoxylated alcohol, amine oxy de/SDS, coconut oil ethanolamitolu^S1 and its Other combinations may be included.

As previously pointed out, aqueous surfactant liquids with specific structures require other thickening agents. The solid particles can be suspended without the presence of a single surfactant or interfacial Can be obtained by using a mixture of activators in combination with an electrolyte . The liquid of specific structure thus obtained has lamellar droplets in a continuous aqueous phase. Ru.

The preparation of suspensions based on surfactants is known to those skilled in the art and is usually nonionic. and/or require anionic surfactants and electrolytes; Other types of surfactants and surfactant mixtures such as surfactants and twin surfactants It is also possible to use

Builder/Electrolyte Builders that may be used include ordinary alkaline detergent builders, inorganic or organic. The builder comprises about 0.5% to about 50% by weight of the composition, preferably 3% to about 35% by weight of the composition. It can be used at the level of %. In particular, preferred buildings when using compositions with specific structures. The amount of goo is 5 to 35% by weight.

As pointed out earlier, a liquid with a specific structure is a soap/surfactant lame liquid. A sufficient amount of electrical current to cause the formation of a phase and thereby the ability to suspend solids. It is a liquid that requires solutes.

As used herein, the term "electrolyte" refers to any water-soluble salt.

The amount of electrolyte used when a composition with a specific structure is desired depends on the soap/surfactant. It has the ability to induce the formation of a lamellar phase by a sex agent, thereby suspending solids. should be sufficient to Preferably, the composition contains at least 1.0 wt. % electrolyte, more preferably at least 5.0% by weight, most preferably contains at least 10.0% by weight electrolyte. The electrolyte is added to the inorganic builder. It is also possible to use detergents such as sodium lipolyphosphate, or Alternatively, electrolytes are non-functional electrolytes such as sodium sulfate and sodium chloride. obtain. Preferably, all or part of the electrolyte is an inorganic builder.

Even if the composition does not have the specific structure achieved by the electrolyte, A sufficient amount of electrolyte should be present to stabilize the cells (described below). The following points should be kept in mind. That is, whether or not the composition has a specific structure, A small amount (both about 1% by weight, preferably a small amount (both about 3% by weight, preferably 3% by weight) % up to about 50% by weight electrolyte.

With a composition having a specific structure, the composition can suspend particulate solids; Preferred are systems in which the solids are actually suspended as described above. solid electrolyzed An undissolved electrolyte that is the same as or different from the electrolyte in a saturated solution. could be. In addition, or in other cases, the solid is not substantially soluble in water alone It can be a substance. Examples of such substantially insoluble substances include aluminosilicates Contains builder and calcite abrasive particles.

Suitable inorganic alkali that can be used (in compositions with or without a specific structure) Examples of water-soluble detergent building blocks include water-soluble alkali metal phosphates, polyphosphates, There are borates, silicates and carbonates. Specific examples of these salts are triphosphate, birophosphate, Phosphoric acid, orthophosphoric acid, hexametaphosphoric acid, tetraboric acid, silicic acid and sodium carbonate and potassium.

Examples of suitable organic alkaline detergent bilgoux salts include (1) water-soluble aminopolycarboxylic salts; carbonates such as ethylenediaminetetraacetic acid, nitrilotriacetic acid and N-(2-hydroacetic acid). (2) phytic acid Water-soluble salts such as sodium and potassium phytate (U.S. Pat. No. 2.379. 942), (3) ethane-1-hydroxy-1,1-diphosphonic acid Lithium, potassium and lithium salts: sodium, potassium and methylene diphosphonic acid Sodium, potassium and lithium salts of ethylene diphosphonic acid salts; and sodium, potassium and lithium salts of ethane-1,1,2-triphosphonic acid. In addition, ethane-2-carboxy-1,1-niphosphonic acid, hydroxide Roxymethane diphosphonic acid, carpoxyl diphosphonic acid, ethane-1-hydroxy C-1,1,2-triphosphonic acid, ethane-2-hydroxy-1,1,2-triphosphonic acid Phonic acid, propane-1,1,3,3-tetraphosphonic acid, propane-1,1,2,3 -alkali metal salts of tetraphosphonic acid and propane-1,2,2,3-tetraphosphonic acid (4) U.S. Patent No. 3.308.067 Water-soluble salts of disclosed polycarboxylate polymers and copolymers, etc. be.

In addition, water-soluble salts of mellitic acid, citric acid and carboxymethyloxysuccinic acid , salts of polymers of itaconic and maleic acids, tartrate-succinates, tartrates Polycarboxylate salts including disuccinates and mixtures thereof (TMS/TDS) Bilgoo is fully usable.

Some zeolites or aluminosilicates may also be used. The composition of the present invention has One of those aluminosilicates for use is the formula Na, (yAlO,.5iOx)C In the formula, X is 1.0 to 1.2, and y is l. Amorphous water-insoluble hydrated compound This amorphous material also contains approximately 5011 g of CaC03 per μ. characterized by a particle size of about 0.01 to about 5 μm . This ion exchange builder is detailed in British Patent No. 1.470.250. .

The second water-insoluble synthetic aluminosilicate ion exchange material useful in the present invention is in crystalline form. Yes, formula Na, [(^102), ・(SiOri]・xll□0 [in the formula, 2 and y are an integer greater than or equal to 6, the molar ratio of z:y is from 1.0 to about 0.5, and X is from about 15 to about 264 integers].

The particle size of the aluminosilicate ion exchange material is about 0.1 to about 100 μm; Calcium ion exchange capacity on anhydrous basis is low at 0.1 hardness of CaC per 1μ The calcium exchange rate on an anhydrous basis is at least about 200 mg equivalent. It is also about 2gr/gal/5hin, /g. Such synthetic aluminosilicate Salts are detailed in British Patent No. 1.429.143.

capsule polymer The present invention comprises a decomposable sensitive component and a composite polymer, as detailed below. Provides capsules of more than seeds.

The composite polymer of the capsule consists of a free-radically polymerizable monomer or monomer mixture ( In other words, 7 polymers constituting hydrophobic core particles to which one or more types of hydrophilic polymers are bonded. can be prepared by emulsion polymerization in the presence of one or more water-soluble polymers. . Preferably more than 20%, more preferably more than 40% of one or more water-soluble polymers. The remer binds to the polymer particles.

The remaining polymer remains free, but of course cross-links to further shape the capsule. It can be stabilized.

The particle size of the hydrophobic particles is usually less than 10 μm, preferably less than 1 μm, more preferably less than 1 μm. or less than 0.5μ.

Various polar polymers can be used as hydrophilic polymers constituting the composite emulsion polymer of the present invention. polar and semipolar polymers may be used.

Preferred hydrophilic polymers are suitable for use in compositions containing capsules, preferably concentrated liquids. in the preparation of composite polymers. can interact with and stabilize the core derived from the hydrophobic monomer particles. It is something that Useful hydrophilic polymers fall into two broad categories.

The first type consists of relatively high condensation temperatures. ure) or a nonionic water-soluble polymer that exhibits a cloud point. Publicly available to those skilled in the art As you know (P, Molyneaux.

1fater 5olable Po1)vers, CRCPress, B oca Raton, 1984), polymers such as those mentioned above have their solubility or The cloud point is electrolyte sensitive and can be improved by the appropriate type and level of electrolyte. Such polymers usually have a practical level (<10%) of electrical charge. Capable of effectively salting out with solute, and also enables formation of highly graft-polymerized composite particles. It has a sufficient amount of hydrophobic groups to interact with hydrophobic monomers such as styrene. . Suitable polymers of this type include polyvinyl alcohol and polyvinyl alcohol. Copolymer of coal and vinyl acetate (salt); polyvinylpyrrolidone and polyvinylpyrrolidone Various copolymers of nylpyrrolidone with styrene and vinyl acetate (salts); Molyneaux (supra) and M of acrylamide and polyacrylamide cCormick (Encyclopedia of PolymerScie nce Vol, 17. Considered by John Wiley, New York various modifications such as: and cobolimers and modifications of these polymers. Synthetic nonionic water-soluble polymers including Partial addition to another group of useful polymers Hydrolyzed cellulose acetate, hydroxyalkyl (e.g. ethyl, propyl and butyl) (modified) polysaccharides such as cellulose, alkyl (e.g. methyl) cellulose, etc. There is. Proteins and modified proteins such as gelatin are also used, especially those containing polymers. When selecting one with an isoelectric point pH close to the isoelectric point of the liquid composition to be , constitutes one of the group of polymers useful in the present invention.

The compound of the present invention is bound to (and/or to each other) the hydrophobic polymer core particles. A second type of polymer useful as a hydrophilic polymer for making emulsion polymers is The remer is a chemical cross-linker or an ionic bond that is reactive with the cross-linking agent added in some cases. It is a polymer with functional groups that can form crosslinking bonds. “Reactive cross-linking” is a reversible cross-linking bond that decomposes under the conditions imposed on the composite polymer upon dilution. That is.

Polymers with hydroxyl groups are particularly suitable in this respect because Such polymers form complexes with boron-containing salts such as borax in alkaline media. This is because it will happen. This complex decomposes upon dilution, i.e., a convenient reversible crosslinking means. provide. Examples of polymers containing hydroxyl groups include polyvinyl alcohol and copolymers of polyvinyl alcohol and vinyl acetate, any polysaccharides, and There are modified polysaccharides such as droxyethylcellulose and methylcellulose.

Various proteins also contain tannic acid, trichloroacetic acid and sulfuric acid as another group of polymers. It is known to form reversible cross-linking bonds with suitable cross-linking agents such as ammonium chloride. . Indeed, such reactions are well known to those skilled in the art and widely used in protein purification. I'm tired.

Some polymers that can be reversibly crosslinked have charged groups, especially carboxyl groups. Ru. This polymer can be crosslinked with metal ions such as zinc and calcium. this species Examples of polymers include polyacrylic acid, polymethacrylic acid, and a variety of these. There are acrylic polymers such as copolymers with esters. maleic acid and methyl or maleic acid-containing polymers such as copolymers with ethyl vinyl ether, These are examples of polymers as described above.

From the above studies, various hydrophilic polymers can be used as composite polymers disclosed herein. It is clear that it has potential usefulness as a water-soluble ingredient.

Essentially, it is substantially insoluble in the composition (preferably a concentrated liquid system) under normal electrolyte concentrations. suitable for dissolving or dispersing when the composition is diluted under the conditions of use. The key is to select a suitable hydrophilic polymer. Such polar polymers can be It is sufficient that the general requirements are known and the principle is presented. is possible to a person skilled in the art.

Dissolution or dispersion at the above dilutions is sufficient to ensure that the captured sensitive components have the required potency. This means that it is released in a certain amount. The required potency is usually the captured effectively exert at least 60% of the efficacy it would exert if the quality was not captured. It is defined as the act of performing.

Particularly preferred water-soluble polymers for use in the composite polymer are partially hydrolyzed (i.e. less than 100% hydrolyzed) polyvinyl alcohol (PV A) whose hydrolysis rate is less than 95%, preferably less than 90%; The molecular weight is less than 50,000, preferably less than 30,000.

It is understood that the hydrophilic component of the composite polymer can be formed from one or more hydrophilic groups in the aqueous phase. It should be.

of the composite polymer used in the polymer system (optionally one or more hydrophilic polymers) (chemically bonded) monomers or molecules used to construct the hydrophobic core particle. mixture of styrene, α-methylstyrene, divinylbenzene, and vinyl acetate. acrylamide or methacrylamide and its derivatives, acrylic acid or methacrylamide Tacrylic acid and its ester derivatives, such as butyl acrylate or methyl methacrylate Can be any emulsion polymerizable monomer containing ethylenically unsaturated groups such as acrylates. Ru. As already indicated, mixtures of such monomers are also useful. child It is important to note that these compounds are emulsion polymerizable monomers and not hydrophobic polymers. should be taken into account.

The ratio of hydrophobic polymer core to hydrophilic water-soluble polymer is from 2:8 based on the critical condition. 7=3, preferably 4:6 to 6:4. derived from this emulsion Film properties are determined by the ratio of hydrophobic core to water-soluble polymer, emulsion polymer composition, It can be adjusted by the composition of the water-soluble polymer or by the composition of the water-soluble polymer.

Composite polymers useful in the present invention can be prepared using a variety of techniques well known to those skilled in the art. I can. Among these techniques are batch polymerization, semi-continuous polymerization and seeded polymerization. clopedia of Polymer 5science and Eng ineering; V5). Particularly useful manufacturing methods include, for example, This is a semi-continuous batch polymerization method disclosed in Japanese Patent No. 3.431.226.

Macro and microcapsules using the novel composite polymer of the present invention can be prepared by those skilled in the art. It can be manufactured by a variety of well-known methods. Those methods include U.S. Pat. 247.014 and 2.648.609M. Spray coating using a coater or fluidized bed coater: U.S. Pat. No. 3,202.3 71 and 4.276,312; or Based on coacervation (includes various techniques Hi, especially convenient and easy) The method is spray drying. In this method, the inclusion material (e.g., one or more enzymes), Combine the polymer and additional optional agents such as initial crosslinkers and enzyme stabilizers with water. , mix well. Pump the mixture through the spray dryer nozzle with the desired opening spray into a heated drying chamber. Fine powder obtained Microcapsules can be applied as is or further conditioned if necessary. It is also possible to pass through a noyoning process.

The particle size of the capsules is less than 250μm, preferably less than 10μm, more preferably should be between 0.1 and 60 μm.

As mentioned above, one or more hydrophilic water-soluble polymers are chemically bonded to the hydrophobic core particles. and/or physically combine.

Chemical bonding occurs when a portion of the hydrophobic polymer chemically bonds to the hydrophilic core particle during polymerization. It is caused by The hydrophilic part and the hydrophobic part are, for example, They can also be bonded by interaction of Lus forces. Alternatively, a hydrophilic molecule can be In some cases, they form a web that loosely surrounds the core particle and become physically entangled.

Without intending to be bound by theory, one or more hydrophilic polymers may be hydrophobic. While chemically reacting with the core particle, other hydrophilic polymers cross-link to each other and this together they form a seed web or gel-like sieve into which enzymes or It is believed that other sensitive components are trapped.

In addition, the above-mentioned "sieve" is composed of enzyme capsules, that is, hydrophilic groups bonded to core particles. While delaying the movement of the composition components to the outside of the formed capsule, It is thought that the function is to delay the intrusion into the capsule.

That is, the emulsion polymer capsule protects sensitive ingredients that “float” inside the sieve. do. − This polymer capsule contains detergent agents such as one or more enzymes, fragrances, optical brighteners, etc. It is particularly useful for encapsulating sensitive active ingredients. One or more enzymes are simply enzymes and the above. by spray drying the mixture with an emulsion polymer such as It can be contained. Various enzymes are included in liquid laundry detergents. It is possible. These enzymes include lipase, cellulase, amylase, and oxidase. etc., and combinations of these enzymes. The enzyme suitable for the application at hand is -Ropper Patent No. 0.286.773^2 and U.S. Patent No. 4.908.150 is being considered.

The amount of one or more enzymes within the capsule is about 0.5-50% by weight, more preferably 0.5-50% by weight. It may be 75 to 30% by weight, preferably 1 to 25% by weight.

The capsules are free from small amounts of water, alkalis, and alkalis that enter the microcapsules during storage. may contain composition components that assist in stabilizing the enzyme against other destabilizing components. is often useful. (In addition to any stabilizers that may be desirably added to the composition itself) Additionally, a variety of suitable enzyme stabilizers can be used inside the capsule. those enzyme stabilizers Calcium salts such as CaC12; formic acid, propionic acid, calcium acetate or or short-chain carboxylic acids or their salts such as calcium propionate: Polyethylene large molecules such as glycols; various polyols; and certain hydrolyzed proteins. Includes children. Examples of suitable enzyme stabilizers are all included herein by reference. U.S. Pat. No. 4.518.694, U.S. Pat. No. 4.908.150 and U.S. Pat. No. 11.169. Typically, enzyme stabilizers are present in detergent compositions ranging from 0.01 to 0.01%. 5%. Stabilizers are usually used inside the capsule and when used outside the capsule. Less volume is needed.

An interesting aspect of the invention is that the polymer of the invention is a composite polymer; - has a hydrophilic molecule attached to a hydrophobic core to effectively capture the captured substance (e.g. Since it constitutes a web or mesh of seeds covering (more than one enzyme) (e.g. Relatively small molecules (e.g., enzyme stabilizers such as calcium acetate) can “diffuse out of the web.” Large particles (e.g. cationic protein stabilizers) that cannot be easily diffused Although it may be considered to be much less effective as a stabilizer than Yes. However, surprisingly, both large and small stabilizer molecules Equal stabilization (depending, at least in part, on the choice of enzyme) when used within molecules It has been found that it can exhibit auxiliary properties.

“Large molecules” are molecules with a molecular weight larger than the normal fO, 000g/■o1. ``Small molecules'' are molecules with a molecular weight smaller than the typical 500g/■ol. It is a molecule that I don't want to get too hung up on theory, but this also applies to diffusion effects. However, the capsule preferably retains the desired ingredients inside until the time of release or dilution. It is thought that this explains the

Another feature of the invention is that by using an enzyme stabilizer inside the capsule, Uses far less stabilizer (by an order of magnitude) than if used outside the cell It means you'll be better off without them. Moreover, lowering the stabilizer dose sacrifices cleaning power. It is realized without That is, by simply transferring the stabilizer material into the capsule of the present invention. Obviously, a significant and surprising enhancement of stabilization can be achieved by Stabilizer is inside the capsule It can be used on the inside of the capsule, on the outside of the capsule, or even between the inside and outside of the capsule. It should be understood by those skilled in the art that it may be used for both.

If the capsule is present in a concentrate, the ingredients protected within the capsule will Released when diluted with water from washing solution.

Concentrate refers to water in addition to other ingredients of up to 60% by weight, preferably up to 50% by weight. A composition containing the following amounts:

The water content of detergent compositions is important when used in diluted compositions (e.g. detergent compositions). (can range from about 10% to about 80%, but preferably the composition is such that the capsule is heavy). quality in detergent compositions, i.e., water-soluble polymers are insoluble. The drug should be formulated to contain appropriate levels of agents that can cause sex. The above drugs are Can be an electrolyte or a crosslinking agent, thereby making the capsule stable in liquid detergent compositions. structure, but the concentration of the detergent in the cleaning solution (typically 0.5 detergent per liter of water) Disintegrates when diluted to ~6g).

Electrolytes are monovalent, divalent, trivalent or tetravalent compounds that salt out water-soluble polymers from solution. Can be a water-soluble electrolyte. Preferably the electrolyte is IA and a group metal halogen, Group IA metal sulfates, Group I^ metal citrates, Group IA metal carbonates, and Group I^ metal li selected from salts of phosphates, as well as salts of low molecular weight carboxylates. For example, sodium chloride calcium and potassium, calcium and magnesium chloride, sodium and potassium sulfate um, sodium citrate, sodium carbonate, sodium phosphate, and Nicosuccinate, tartrate- and/or nicosuccinate, carboxymethyloxy These include low molecular weight polycarboxylic acid salts such as succinates and the like.

Crosslinking agents that are highly suitable for the present invention are metal borates, i.e. sodium borates, Various borates such as potassium borate and complex borates such as borax (coa+ plex borates). These substances include PVA, dextrin, etc. It is well known to those skilled in the art to form reversible complexes with polyhydric alcohols such as There is. Of course, crosslinks other than those mentioned above that form reversible polyvalent complexes with polyhydric alcohols Agents can also be used provided the complex has sufficient stability.

The level of electrolyte and/or crosslinker required in the composition will depend on the composition of the capsule and the It depends on the conditioning or finishing that can be applied to the pussel. For example, a place where In some cases, it may be advantageous to add the drug directly to the capsule composition before spray drying. can be obtained. In other cases, agents may be used to harden the capsule prior to addition to the HDL. The capsules may be immersed in the conditioning liquid contained therein. Furthermore, top the capsule. It is also possible to spray with a "curing" liquid as described below. Level of drug in composition Bell is sufficient to ensure that the capsules are not compromised in any way in heavy liquid detergent compositions. It should be something. Typically, the amount of the above agent is between 0.1 and 0.1 based on the weight of the composition. It is about 20% by weight, preferably 1-20% by weight. “Unimpaired” means The composite porous found in the polymer system of the present invention ensures that the cells do not dissolve in the composition. Rimmer is used to protect components that may be destroyed in the solution outside the capsule. Designed. List one or more enzymes as one of the ingredients listed above. You can do it.

Lipases, such as Lipolase® (Novc), are used in liquid detergents. The composition contains about 0.1-log/l, more preferably 0.5-7 g/l of the final composition. , most preferably at a level of 1-2g// when the composition is used in a cleaning cycle. 100 to 0.005 LU/ml, preferably 25 to 0.05 LIJ/ml It can be contained in an amount such that it exhibits lipolytic enzyme activity.

Lipase units (LU) are measured at 1/μ/min at pl+stat under the following conditions: The amount of lipase that produces mol of titratable fatty acids. Temperature 30℃; pH = 9.0; substrate is 3.3% by weight olive oil and 3.3% by weight gum arabic in the presence of 13a + mol # of Ca” and 20 mmol/l NaCl Emulsion dispersed in l# Tris buffer.

Of course, it is also possible to use mixtures of lipases. Lipase is in unpurified form It can also be used in well-known adsorption systems, e.g. It may be used in a purified form purified using a harvesting method.

When using a protease, this proteolytic enzyme may be of plant origin or an animal. It may be of biological origin or of microbial origin. Preferably, the protease is Particularly preferred are microorganisms, including microorganisms, fungi, molds and microorganisms, such as From specific strains of B. 5ubtilis and B. licheniformis The resulting bacterial stearic acid protease.

Examples of suitable commercially available proteases include both Novo Indust-ri /S ^1calase, 5avinaseSEsperase; G15t -Brocades Maxatase and Maxacal; Showa K Enko's Kazusase; BPN and BPN' protease, etc. set The amount of proteolytic enzyme to be included in the composition is 0.05 to 5, based on the final composition. 0.0OOGU/11g, preferably 0.1-50GU/+*g. Naturally However, mixtures of various proteolytic enzymes may also be used.

Although various specific enzymes are mentioned above, it is important to note that the desired proteolytic activity can be imparted to the composition. Any protease that can be used can be used, and the above embodiments of the invention include What should be construed exclusively as a specific selection of proteolytic enzymes should be understood.

In addition to lipases and proteases, well known cellulases and oxidases are well known to those skilled in the art. It is understood that other enzymes such as enzymes, amylases, peroxidases, etc. may also be used. Should. Enzymes may be used with cofactors necessary to facilitate enzymatic activity, i.e. If so, it can be used by being present in the enzyme system. Enzymes with mutations at various sites (e.g. Enzymes that have been genetically engineered to improve potency and/or stability) are also contemplated by the present invention. It should also be understood that it is a more intended enzyme.

An example of a commercially available genetically engineered enzyme is Novo's Durazys (registered trademark). There is.

Optional ingredients In addition to the enzymes mentioned above, several other optional ingredients may also be used.

Alkalinity buffers that may be added to the compositions of the invention include monoethanolamine, Contains triethanolamine, borax, etc.

Hydrotropes that can be added include ethanol, sodium xylene sulfonate, Contains sodium cumene sulfonate, etc.

Other substances, particularly those that are water-insoluble, such as clay, may contain capsules of the invention. can be a useful addition to compositions that contain Particularly useful is bentonite.

This material is primarily montmorillonite, which is an aluminium-based Hydrated aluminum silicate in which about 176 of the umium atoms can be replaced by magnesium atoms It weakly binds with various amounts of hydrogen, sodium, potassium, calcium, etc. obtain.

Bases in a relatively refined form (i.e. free from coarse grains, sand, etc.) suitable for detergents. montonite contains at least 50% montmorillonite, i.e. its cations The exchange capacity is small (approximately 50 to 75 meq) per 100 g of bentonite. . A particularly preferred bentonite is by Georgfa KaoLin Co. fyowing sold as Th1xo-jets 1.2.3 and 4 Or festern U, S, bentonite. These bentonites Marriott British Patent No. 401.413 and Marriott and woven fabrics as described in Guam British Patent No. 461.221. It is known to soften.

Detergent products may also include other features that add to the product's desired properties, whether functional or aesthetic. Various detergent additives or auxiliaries may be present that impart additional properties.

The composition contains a small amount of aluminum salts of higher fatty acids, such as aluminum stearate. Improves the physical stability and anti-settling properties of the composition by adding it in active form It is possible. The aluminum stearate stabilizer is 0-3%, preferably 0.1-2. It may be added in an amount of 0%, more preferably 0.5-1.5%.

The composition may contain small amounts of soil anti-settling or anti-redeposition agents, such as polyvinyl alcohol. alcohol, fatty acid amide, carboxymethyl cellulose sodium, hydroxy Propyl methylcellulose may also be included. A preferred anti-redeposition agent has the trade name “ C1l/IIC ratio 2 sold under “Re1atin DM 4050” :1 carboxymethylcellulose sodium.

Optical brighteners for cotton, polyamide and polyester textiles may also be used. appropriate fireflies The optical brightener is Tinopal LMS-X.

Stilbene, triazole and benzidine sulfone compositions, especially sulfonated substitutions triazinyl stilbene, sulfonated naphthotriazole stilbene, pendide The most preferred combination is a combination of a stilbene and a triazole. It's a lie. A preferred brightener is dimorpholinedianilinostilbene sulfone. This is the 5tiLbene Bright-ner N4.

Antifoaming agents, such as silicon compounds such as 5ilicane L 7604, also contain small amounts. Can be added in effective amounts.

Bactericides, such as tetrachlorosalicylanilide and hexachlorophene, bactericides Bacterial agents, dyes, pigments (water dispersible), preservatives such as formalin, ultraviolet absorbers, Fluorescent blue tinting agents such as sodium ruboxymethylcellulose (anti-yello w-ing agents), pH adjusters and PL (buffers, non-fading ( color 5afe)fi whitening agent, fragrance, and Iragor+ Blue L 2D.

Dyes and blue tints such as Detergent Blue 4721572 and ultramarine can also be used.

Soil release polymers and cationic softeners may also be used.

Additionally, when using liquids with specific structures, high activity levels of such liquids may It tends to become viscous due to the large amount of lamellar phase produced by solute (>6 ．． 000cP). This liquid is diluted to be acceptable for normal consumer use. (<3.0OOcP), so an excess amount of electrolyte and polyacrylate and polyester The water content of the lamellar phase is reduced using both ethylene glycol and other substances. This reduces the phase volume and lowers the total viscosity (osmotic compaction). Normally, the above port The rimer is sufficiently hydrophilic (less than 5% hydrophobic groups) to not interact with the lamellar droplets. and have sufficient molecular weight (>2.0 00).

Another optional component that may be used in liquids, particularly those having a specific structure, is a peptizing polymer. child No. 5,147,576 (which is incorporated by reference in this application). Montague et al.). Typically, peptized polymers are hydrophobic The need for low viscosity products that contain a main chain and one or more hydrophobic side chains and are, if desired, stable. allows for the inclusion of surfactants and/or electrolytes in larger amounts than are compatible with Also, if desired, lamellar dispersions have a high degree of stability sensitivity. It also allows for the inclusion of larger amounts of other components that exert their effects.

Hydrophilic backbones are usually straight, branched, with one or more relatively hydrophobic monomer units. chain, or a highly crosslinked molecular composition, wherein the monomers are preferably , has sufficient solubility when dissolved in water to yield a solution of 1% by weight or more. parent The structure of the aqueous backbone includes a hydrophilic backbone that is included in an active aqueous liquid composition having a specific structure. form from monomers that are constituents of the hydrophilic backbone. The polymer corresponding to the main chain made of The only constraint is that the object rotates.

Further, the hydrophilic main chain is preferably mainly linear, for example, the main part of the main chain (th e main chain of backbone) is small (both 50% by weight) preferably greater than 75% by weight, most preferably greater than 90% by weight form a large part.

The hydrophilic backbone is selected from a variety of monomer units that are effective in polymer production, and H composed of monomer units joined by any chemical bond, including

Preferably, the hydrophobic side chain is composed of a hydrophobic monomer and a hydrophilic monomer constituting the main chain. It is a part of the seven units contained in the polymer by copolymerization. hydrophobic side chain preferably includes those that are relatively water-insoluble when separated from their bond, i.e. Hydrophobic polymers that are soluble in water at ambient temperature and a pH of 3.0 to 12.5 are preferred. Preferably less than 1 g/1, more preferably less than 0.5 g/1, most preferably 0.5 g/1. It is less than 1 g/J.

Preferably, the hydrophobic moiety is a siloxane, and for example 5 to 24, preferably 6 Saturated and unsaturated alkyls having ~18, most preferably 8 to 16 carbon atoms from 1 to 50 alkoxyl chains, and optionally in the hydrophilic backbone. Alkoxylene or polyalkoxylene linkages with linking via polypropoxy, polypropoxy or butyroxy linkages (or mixtures thereof). Match. Alternatively, in other cases, the hydrophobic side chain is an alkyl or alkenyl group. In the absence of relatively hydrophobic alkoxyl groups, such as butylene oxide and/or It can consist of propylene oxide.

The monomer units that make up the hydrophilic main chain include acrylic acid, methacrylic acid, and maleic acid. by hydrolysis of acids, vinyl methyl ether, vinyl sulfonate or vinyl acetate. unsaturated, preferred vinyl alcohol such as acrolein monomer, Preferably mono-unsaturated auto-s acids, ethers, Alcohol, aldehyde, ketone or ester: unsaturated or mono Other groups that can form intermer bonds (carbohydrates and glucosides, alkoxyl units and hydromaleic acid, etc.); and glycerol or other saturated polyalcohols. Contains calls.

Monomer units containing both a hydrophilic backbone and a hydrophobic side chain include amino, amine, amino de, sulfonic acid, sulfuric acid, phosphonic acid, phosphoric acid, hydroxyl, carboxyl and It may be substituted with groups such as oxide groups.

The hydrophilic backbone preferably consists of one or two types of monomer units, but three or more types It is also possible to have various monomer units. The main chain also If the solubility meets the requirements discussed earlier, then the solubility in water is Ig/md1. It is also possible to have small amounts of relatively hydrophilic units such as those derived from polymers that are be. Examples include polyvinyl acetate and polymethyl methacrylate.

When a peptizing polymer is used, the amount is usually from about 0.1% to about 5% of the composition, and is preferably preferably from 0.1% to about 2%, most preferably from about 0.5% to about 1.5%.

The above list of optional ingredients is not considered exhaustive and may not be listed here. However, other optional ingredients well known to those skilled in the art may also be included in the composition. Ru.

The viscosity of the aqueous liquid detergent composition of the present invention is 50 to 20,000 cP, preferably 10 0 to 1.000 cP, but compositions with other suitable viscosities are also useful. obtain. At the above viscosities, liquid detergents are stable dispersions/emulsions and easily Injectable. The pi of the liquid detergent dispersion/emulsion is between 5 and 12.5, preferably 6 ~IO.

In particular, the ideal liquid detergent composition composition for liquids without a specific structure is as follows. It can be.

Cleaning solutions (i.e., e.g. Li-berati et al., included by reference in this application) pI bijump solution) as taught in National Patent No. 5.073.285). In compositions where it is desirable to keep the initial pH value low, Monoethanolamine/triethanolamine buffer systems are Usually replaced by sorbitol and glycerol.

An example of a composition having a specific structure is as shown below. The following examples are intended to explain the invention in further detail and do not limit the invention. There is nothing to do.

Example 1 According to the compounding method shown in Table I below, eight types of composite polymers were mixed at Ml 2,000: Hydrolysis rate 75% 50-----50-'-1fl 13.00 0 to 23.000; Hydrolysis rate 78% -50---50-Mf 13.0 00~23.000; Hydrolysis rate 89% --50---MW 13.0 00-23.000: Hydrolysis rate 98%---50---n 13.000~23.000; Hydrolysis rate 78%---30---Styrene 50 50 50 50 6 0 30 - 15 Butyl acrylate - - - - 20 - Vinyl acetate - ------50- The amount of woody polymer bound to the hydrophobic polymer particles was 49.1%.

Zero; the amount of hydrophilic polymer bound to hydrophobic polymer particles was 50.1% .

The general method for synthesizing Polymers 1-7 of Table I is as follows. polymerization reaction A half-simmer equipped with a stirrer, a condenser, a nitrogen inlet and a temperature controller was used for the generation. A four-neck, round-bottom flask with a torr capacity was used. Polyvinyl alcohol (PVA) and deionization ion water into the reaction vessel and the vessel was heated and maintained at 75°C, thereby causing slow nitrification. All Pv^ was dissolved under a plain flow. Add 6 g of monomer or monomer mixture to the reaction volume. and emulsified for 2 minutes. 20g of 1% potassium persulfate (initiator) solution was added to the reaction vessel to start the emulsion polymerization reaction. remaining monomer or monomer Weigh the mixture into the reaction vessel for 30-35 minutes, then react and mix for an additional 30 minutes. The reaction was completed by maintaining the temperature at 75°C. After the reaction is complete, the emulsion is cooled to room temperature and Particles were determined by photon correlation spectroscopy using a Brookhaven B190 light scattering instrument. The diameter was measured. The results are shown in Table I above.

Polymer 8 containing methylcellulose and polystyrene was prepared as follows. . 15g methylcellulose (15cP in 2% solution) and 0.1g bisulfur Sodium chloride and 250 g of deionized water were added to a stirrer, condenser, nitrogen inlet and It was placed in a half liter four neck round bottom flask equipped with a temperature controller.

The solution was stirred at room temperature under a slow flow of nitrogen to dissolve all the methylcellulose. Methi After all cellulose was dissolved, the reaction vessel was heated and maintained at 35°C. 5g of Add styrene to the reaction vessel and add 20g of 1% potassium persulfate solution to polymerize. The reaction was started. After 5 minutes of addition of the potassium persulfate solution, the remaining styrene monomer was metered into the reaction vessel over a period of 20-25 minutes, then the reaction vessel was incubated for an additional 40 minutes. It was maintained at 5°C. After the reaction was completed, the emulsion was cooled to room temperature.

Example 2 The eight composite polymer compositions of Example 1 (shown in Table 1) were prepared (at various levels of hydration). polymer film compared to four compositions containing only r'VA (degraded) The sensitivity to salt was determined.

Weighed 2 g of various polymer solutions to measure the properties of various films. It was placed in an aluminum dish and air-dried for 4 days.

The polymer film was incubated at room temperature for 24 hours with various sodium sulfate concentrations ranging from 0 to 8% by weight. Solubility of polymer film in sodium sulfate solution by placing it in solution was measured. The solubility and film appearance were recorded and summarized as shown in Table H below. Ta.

NalSO4 concentration PVA 100%; Ml 2,000: Hydrolysis rate 75% 1 l 2 4 Comparative example 2 PVA 100%: MY 13,000-23,000; Hydrolysis rate 78% 1 2 2 3 Comparative example 3 PVA100%, MY 13,000-23,000; Hydrolysis rate 89% 1 124 Comparative example 4 PVA100%; Ml 13,000-23,000; Hydrolysis rate 98% 3 4 4 4 Comparative example 5 Methylcellulose 100% 1 2 3 4 Polymer 1 PS50% PVA50% l 2 4 4 Polymer 2 PVA50! J6PS50% 1 1 4 4 Polymer 5 PVA 33.3% PS 66.7% 2 3 4 4 Polymer 3 PVA5096PS50% 1 2 4 4 Polymer 4 PVA50%PS50%4 4 4 4 Polymer 8 Methyl cellulose 50% PS 50% 2 3 3 4 points 1-The film completely dissolves or disintegrates into submicroscopic particles.

2-The film disintegrates into small pieces.

3-The film swells but remains intact.

4-The appearance of the film did not change.

The results shown in Table ■ above indicate that most of the PVA was hydrolyzed (i.e., with a hydrolysis rate of 98%). Comparative Example 4) does not decompose in water at room temperature (i.e., the score at electrolyte concentration θ% is 3). ), it is clearly stated that it is not suitable for the purpose of inclusion. partially hydrolyzed PVA is completely soluble in water at room temperature, but polymers consisting of partially hydrolyzed Pv^ - (Comparative Examples 1 to 3) collapsed into small pieces. In addition, (as shown in Example 3 below) ) Partially hydrolyzed PVA has a tendency to swell excessively in concentrated liquid detergents. (i.e. 78% swelling compared to 230% for 98% hydrolyzed PVA) The swelling rate of % hydrolyzed PVA is 708%).

The drawbacks of these polymers can be overcome by using composite polymers produced by the method disclosed in the present invention. You can overcome it by being there. Polymerizing styrene in the presence of partially hydrolyzed PVA Films derived from emulsions prepared by As shown in Example 3, this film is used for composite polymers. salt sensitivity and complete solubility in water at room temperature or to the submicron level. Excellent compatibility with the ability to disperse is realized.

This means that, for example, it is clearly salt tolerant at a salt concentration of 4% and odorless at a salt concentration of 0%. Polymer 1 shows excellent salt resistance at a concentration of 2%, but at a concentration of 0. %, it can be seen that polymer 5 easily disintegrates.

Example 3 Water resistance was measured by comparing the polymer of the present invention with a polymer containing only PVA. Ta. As in Example 2, 2 g of the polymer solution was weighed to measure film properties. It was weighed out and placed in an aluminum dish, which was then dried for 4 days.

By measuring the swelling rate of the film in concentrated liquid detergent with the following composition: We investigated water resistance.

Water 60.7% The film was placed in the concentrated liquid for 24 hours at room temperature. Rinse the film with deionized water; Remove excess water that is not absorbed with a vapor towel, and then remove the swollen film. The weight of the sample was measured. Swelling is calculated by dividing the weight of swollen film by the weight of unswollen film. calculated the rate. The results are shown in the following table ■.

Table■ Swelling rate (%) in concentrated liquid detergent (Ml 13.000-23.000; Hydrolysis rate 78%) Poly? -5: P VA 33.3% PS 66, 7% 203 (Iff 13.000~23. 000: Hydrolysis rate 78%) Polymer 4: PVA 50% PS 50% 158 (MW 13,000-23,000; hydrolysis rate 98%) The above results are partially This shows that PVA that has been hydrolyzed (with a hydrolysis rate of 78%) swells significantly. ing. As seen in Example 2, in this regard, 98% hydrolyzed PVA Appropriately, this polymer is readily soluble upon dilution (i.e. at salt levels θ%). I don't like it because I don't understand it.

Both of the composite polymers of the present invention (Polymers 2.4 and 5) are partially added. Hydrolyzed (i.e. 78% hydrolyzed) PVA is significantly more effective than 100% polymer Shows only slight swelling.

Tables ■ and ■ of Examples 2 and 3 also show that even if the ratio of polystyrene to PV^ is changed, This shows that film properties can be adjusted by That is, Comparative Example 2 (PVA50 %), polymer 2 (pv^50%, styrene 50%), and poly? -5 (PVA 33.3%, styrene 66.7%) differs only in the Pv^ to styrene ratio. No (i.e. both pv^(7) MWha 13.000-23.000, water added Polymer 5 has a lower decomposition rate than Polymer 2 (Haf 8%), but Polymer 5 has a lower (i.e. already salt tolerant at a salt level of 2%) and polymer 2 Both Polymer 5 and Polymer 5 have lower electrolyte levels than Comparative Example 2 (which disintegrates at salt levels higher than 4%). becomes much more effectively insoluble (ie, forms an insoluble capsule) in the cell.

Furthermore, both Polymer 2 and Polymer 5 swelled much less than Comparative Example 2. (i.e., the swelling ratios of Polymer 2 and Polymer 5 are 455% and 20%, respectively) 3%, whereas the swelling ratio of Comparative Example 2 was 708%).

Example 4 Production of enzyme microcapsules Using the composite emulsion polymer shown in Table I The lipase enzyme was then encapsulated to be included in the concentrated liquid detergent composition. 69g of Emma solution polymer (pH 6~g) and 37.5g of Lipolase 100L ( Yamato Pulvis Min Spray drying using i5pray under the following conditions to obtain exposed particles with a particle size of l~30 μm. Free flowing enzyme microcapsule spray nozzle 1650 S type The composition of the enzyme microcapsule is shown in the table below.

Polymer (%) Lipolase 100L (%) Capsule 1 64.8* 35.2 Capsule 2 64.80 pieces 35.2 Capsule 3 64.8 Kimoto * 35.2 Zero: The polymer used is Polymer 1 in Table ■ (i.e. PVA Ml is 2.000, hydrolysis rate is 75%, 50:50) PV^/styrene).

**: The polymer used was Table 1 (7) Polymer 2 (i.e. PVA (7) MW7!J< 13.000-23.000, PV of 50:50 with a hydrolysis rate of 78% ^/Styrene).

Hayashi: The polymers used are Table 1 (7) Polymer 3 (i.e. PVAI7) MY is 13. 000-23.000, 50:50 PV^/s with a hydrolysis rate of 89% tyrene).

Example 5 Enzyme stability in concentrated liquid detergent The enzyme microcapsules of Example 4 were Concentrated liquid detergents were prepared according to the compositions shown in the table below.

Enzyme-containing concentrated liquid detergent Enzyme capsule 2 - 0.6 - - Enzyme capsule 3 - - 0.6 - *; 11N approx. 5.000 acrylic acid-lauryl methacrylate which is a peptizing polymer Copolymer〇 As a comparative example, a concentrated liquid detergent with the same composition was also used as a non-encapsulated Lipolase 1. Manufactured using 00L. The concentrated liquid detergent thus prepared was stored at 37°C. . The stability of the enzyme at 37°C was investigated by measuring enzyme activity. The table below shows the enzymes. Indicates half-life.

Enzyme stability in concentrated liquid detergents Capsule half-life at 37℃ (days) Comparative Example (Lipolase 100L) 2 Capsules of Example 4 3***64 Ne: The capsule polymer is PVA with 1lIW of 2.000. Hydrolysis rate is 75% 50:50 was Lipolase.

This example clearly demonstrates that the polymers of the invention confer high stability to lipases. It shows. Moreover, capsule 1 and capsule 2 are MIF 2,000, Polyvinyl alcohol with a hydrolysis rate of 75% and MY 13,000-23.00 0, it is interesting to synthesize it from polyvinyl alcohol with a hydrolysis rate of 78% (pointed out) be done. The prior art (European Patent Application Publication Box 0.266, No. 796) is Partially hydrolyzed substances such as It states that only substances with a water decomposition rate of 90% or higher should be used. However, the present invention By grafting the above polymer onto a hydrophobic core particle as disclosed in , the resulting material becomes perfectly suitable for the encapsulation of enzymes.

Example 6 Release of enzyme under washing conditions Release of encapsulated enzyme under washing conditions at 25°C and 40°C. 1 g of the sample of Example 4 was added to 1 t of water and various Enzyme activity was measured at different time points. The results are shown in the table below. As seen from the table, The enzyme was completely released within 1 minute at 40°C and within 3 minutes at 25°C.

1 0.47 0.55 2 0.47 0.51 3 0.52 0.54 4 0.52 0.53 5 0.53 0.54 10 0.53 0.52 15 0.47 0.53 Example 7: Production of microcapsules Protease enzyme contained in a concentrated liquid detergent composition using Polymer 2 in Table ■ was enclosed. 163 g of Polymer 2 and 18.3 g of protease solution (Max aca1) and a solution containing Yamato Pu1vis Mini 5 Using pray, the inlet temperature was 130°C, the outlet temperature was 65°C, and the atomizing air pressure was 1,5 Capsules 4 were prepared by spray drying at 14 kgf/cs+”. 9g of polymer 2, 0.2g of calcium acetate, and 3.9g of glycerol. , and 18.3 g of protease solution (llaxaca1). Capsule 5 was prepared by spray drying under the same spray drying conditions as for capsule 4. Manufactured.

Example 8: Enzyme Stability in Concentrated Liquid Detergent Containing Enzyme Capsules of Example 7 A concentrated liquid detergent was prepared according to the composition shown in the table below.

Ethoxylated alcohol C+z-+s 9EO12,012,012,0 citric acid Acid? , 1 7.1 7.1 Sodium borate 2.7 2.7 2.7 PPE 1067 (33%) bottles 3.0 3.0 3.0Na0+1 (50%) 14.4 14.4 14. 4 Ethanolamine 2.0 2.0 2.0 Triethanolamine 2.0 2.0 2.0 Water 27.7 27.7 28.3 Protease solution 0.6 Capsule 4 1.2 - - Capsule 5 1.2 - Acrylic acid-lauryl methacrylate with a MW of about 5.000, which is a peptizing polymer copolymer.

As a comparative example, a concentrated liquid detergent with the same composition was also prepared using an unencapsulated protease solution (M axaca1). The liquid detergent thus prepared was stored at 37°C. I stored it. The stability of the enzyme at 37°C was investigated by measuring enzyme activity. In the next table The half-life of the enzyme (the point at which 50% of the enzyme activity still remains) is shown.

Enzyme stability in concentrated liquid detergents Capsule 528 of Example 7 Example 9: Production of enzyme capsules Mix 145g of Polymer 3 from Table 1 with 75g of Lipolase 100L. The solution prepared using Yamato Pu1vis Mini 5play Inlet temperature: 120℃, exhaust port temperature: 65℃, and spray air pressure: 1.5kgf/e11 32 g (72% yield) of free-flowing capsules were obtained. .

145g of polyvinyl alcohol solution (solids 23%; hydrolysis rate 89%; MY 13.000/23.000) and 71.5g of Lipolase. A comparative solution prepared in the same manner was spray dried under the same conditions. Capsules with fiber-like structure Only 10 g (yield 22.7%) was obtained.

Example 10: Production of enzyme capsules 58.5g of Polymer 4 from Table 1 and 37.5g of Lipolase 100L. The mixed and manufactured solution was mixed into a Yamato Pu1vis Mini 5play The intake port temperature was 120°C, the exhaust port temperature was 65°C, and 1.　Okgf/cm” It was then spray dried. 18.2 g (72%) of free-flowing capsules were obtained.

145g polyvinyl alcohol solution (23% solids; Iris? 13.000/23 , 000; hydrolysis rate 98%) and 71.5g of Lipolase ID0L. A comparative solution prepared by mixing the following was spray dried under the same conditions.

No free-flowing capsules were obtained. The spray-dried polymer has a fiber-like structure. formed large aggregates with

Example 11 Manufactured by mixing 100g of Polymer 8 and 21g of Lipolase 100L The solution was absorbed using Yaa+ato Pu1vis Mint 5play. Spray drying was carried out at an inlet temperature of 130°C and an outlet temperature of 70°C. 3.6g of Sara Exposed enzyme capsules were obtained. 100g of 7% methylcellulose solution and 15g of A comparison solution prepared by mixing with Lipolase 100L was sprayed under the same conditions. Although it was dried, only 0.4 g of capsules were obtained.

Examples 9.10 and 11 demonstrate that the polymers of the present invention significantly improved the yield of spray-dried capsules. It has been shown that the polymers can be further enhanced to produce more useful capsules than water-soluble polymers. It shows clearly.

Polymer 2 (50% polystyrene, 50% Pv^) and different enzyme bases Various capsules were manufactured using the fixing agent.

various polymers (as shown in the following table), 11.25 g of protease solution (M axaca1) and various amounts of stabilizers (also shown in Table ■) , using Yamato Pu1vis Mini 5play, inlet temperature 1 Spray drying at 30℃, exhaust port temperature 65℃, and spray air pressure 1.5kgf/cm2. Capsules were prepared by drying. The capsules were used in Composition A below.

Table■ detergent composition Control composition B contains the protease directly in the composition rather than in capsule form. The composition was the same except that

The theoretical composition of the rotiase capsule is shown in Table ■.

Table V Composition of the feed material to the spray dryer QuatProE --9,0--- ^1-55 - - - 4.0 + - Sodium propionate - - - 2,25- n, o---5,06,757,5 Capsule yield (g) 24.8 21.9 23.6 23.9 22.3 2 3.6 Table ■ Theoretical composition of protease capsule Polymer 85 76.6 77.5 77.5 77.5 80 Glycerol -8---1 Ca acetate -0,4--5 QuatProE --7,5-- ＾1-55 - - - 7.5 - - Sodium propionate --- 7,5- The experimental results are shown in the table below.

Table■ At room temperature At 37℃ Sample Stabilizer Half-life (days) Half-life (days) Control 808 a Not contained 144 17 b Glycerol + Ca acetate 200 30c Quat Pro E 210 30d ^1-55 250 30 e Sodium propionate 190 40 f Ca acetate 178 40 Both QuBj Pro E and At-55 are incorporated herein by reference. No. 5,073,292.

As can be easily seen, when using a stabilizer with a small molecule, it is difficult to use a stabilizer with a large molecule. There was no difference in stability regardless of which agent was used (i.e. equally good stability was obtained). Ta). Such results are similar to those of calcium acetate and sodium propionate (such as calcium acetate and sodium propionate). Contrary to what one might expect (based on the prediction that small molecules diffuse), small Stabilizers for type molecules can provide just as effective stabilization as stabilizers for large molecules. This shows that.

Example 13 Stabilization of enzymes in detergent compositions where encapsulation requires much less stabilizer Various enzyme stabilizers are required in the amounts shown in the following table. these needs The amounts used in the compositions taught in U.S. Pat. No. 5,073,292 are as follows: It is also the amount of the agent.

The above required amount was added to the composition using 1.2% capsules (capsules of Example 12). compared to the level of stabilizer required inside the capsule if the The results are shown in the table below. vinegar.

In the composition, in the capsule Quat Pro E 1 7.5 0.09AI-5527,50,09 Sodium propionate 5 7.5 0.09 Ca acetate O, 150,06 Glycerol/borax 5.0/3.5 - Glycerol/Ca 810.4 0.1010.005 In addition, the effect of encapsulation on protease efficacy is shown in the following table. It is shown.

Table■ Maxacal (liquid) 10.2 Maxacal (capsule) io.

5avinase (liquid) 10.9 Savinase (Capsule) As can be seen from Table 10.3, Capsule The amount of enzyme stabilizer used in the cell is less than the amount of enzyme stabilizer used in the composition itself. One digit less. Furthermore, even if a capsule is used, it cannot be explained in terms of delta-delta reflectance units. The Terg-o-toleter measured cleanliness of AS-10 monitor cloth and It can also be seen that the cleaning power was not adversely affected. This test Delta reflectance is defined as the difference in reflectance between unwashed fabric and washed fabric, and delta The delta reflectance is improved by the enzyme with respect to the enzyme-free composition. It is used to measure detergency whenever it is defined as

Example 14: Effect of glycerol Glycerol (present both inside and outside the capsule) stabilizes the encapsulated enzyme. The table below shows the effects on

Half-life at 37℃ (days) +1 Glycerol in DL Absence of glycerol in IIDL Role presence protease liquid (Composition C of Example 8) 10 37 Protease inclusion (Composition of Example 8^) 24 59 Protease and glycerol Encapsulation (composition B of Example 8) 43 This example shows that the stabilizer increases stability from inside the capsule (43 days vs. 24 days). It has been shown that it can also be used to boost the capsule from outside the capsule (59 days vs. 24 days). are doing. It is also possible to add stabilizers both inside and outside the capsule. It should be understood that

Example 15 The novel capsules of the present invention used in compositions containing non-proteolytic enzymes Demonstrates successful protection of proteolytic enzymes from degradation by proteases Be(, the applicant of the present application) (proteolytic enzymes) Proteolytic enzymes seal the half-results of lipolytic enzymes (protected from lipolytic enzymes). The same lipolytic enzyme was halved (containing an enzyme stabilizer and Comparisons were made in both the liquid and slurry containing no liquid.

The experiments specified above were carried out on the following composition C.

Ingredients Weight% Anionic surfactant (LAS): approx. 25 Nonionic surfactant: approx. 12 Borax approx. 3 Sodium citrate approximately 1O Alkaline hydroxide approx. 3 Peptized polymer approx. 1 Triethanolamine approx. 2 Methanolamine approx. 2 Lipolase approximately 0.5 Water remaining amount Enzyme stability is expressed as the half-life, ie, the time required for the initial activity to be reduced by half.

Lipase in the absence of proteases was tested for 30-35 days in composition A as defined above. Has a half-life.

This is the best achievable solution in which lipases are completely protected from proteases. Stability.

In this example, 6 g of enzyme liquid (both wild-type protein available from Novo) was used. Rotease 5avinase 16L or genetically engineered Durazym 1 6L) was added under stirring to 50g of controlled release polymer, and this was added to Yamato M Spray drying was performed using an int Pu1vis 5 play Drier. This fruit The polymers used in the examples had low molecular weights (3,400 to 23,000) and relatively Low hydrolysis rate (78%) (7) 50150 PVA/polis using PVA It was chirene. In the obtained capsules, the specific activity is increased by passing through a spray dryer. Showing activity recovery, 1.8 in each of 5avinase and Durazyi 00.000 GO/g and 500.000 GLI/g. Composition C Capsules were prepared at 24,000 GO/g using IIDL composition shown in DL's 5avina-se or 17,000 GU/g IIDL's Dura zym was added in an amount to release it. Novo's Lipolase 100L is 1 , 350 GU/g IIDL.

The test results are shown in the table below.

Capsule 20 Durazym As can be clearly seen, without capsules 5avinase and Du The stability of lipase in the presence of either was also extremely low. Lipase Stability Protease Nonionic Slurry , for example, Novo's 5avinase 16SL or Durazym 16 In contrast, when protease is encapsulated, it is stable (stable). The stability of Lipolase (in the absence of agents) is 20 days for 5avinase; In the case of Durazy-, it was 30 days.

Example 16 The capsule of the present invention also protects the protease itself from being degraded by other components in the composition. Protection was also shown in the absence of stabilizers.

5avinase Liquid 352 Capsule 40 Durazya+ Liquid　＞　90　10 Capsule 100 1 (DL is a heavy liquid composition (composition C).

As pointed out earlier, the stability of proteases in liquids in the absence of stabilizers is , will be very low if no capsule is used. using capsules (in the absence of stabilizers) If the protease is used in a liquid containing a stabilizer, the stability is equivalent to or better than that of using a protease in a liquid containing a stabilizer. is provided by the capsule.

This example demonstrates that the protease-containing polymer capsules of the present invention are (1) in the composition; (2) protects non-proteolytic enzymes from proteases, and (2) assembles proteases; protection against ring-acting components in formulations, e.g. having high pli values, preferably safe The protease-containing composition of the present invention has been shown to provide high stability even in the absence of a fixing agent. The novel capsules of the present invention used in compositions convert non-proteolytic enzymes into proteolytic enzymes. In order to demonstrate that the present invention was successfully protected from degradation by Half reduction in lipolytic enzymes (protected from protease-containing compositions by capsules) The results were compared to the same lipolysis in protease-containing compositions without stabilizing capsules. The results were compared with the half-reduction results of the enzyme. As a control, in a composition containing no protease. The presence of unencapsulated lipase was also tested. The three experiments specified above are This was also carried out using the following composition.

Zero nibrothiase was not present in the control without use, and the experimental results are shown in the following table.

Enzyme capsule application: 30-40 Zero: Novo lipase As can be seen from the above results, the capsules of the present invention contain encapsulated non-protein It clearly prolongs the half-life of degrading enzymes. The capsule used in this experiment was Example 4. Capsule 2 (PVA (D Ml is 13.000-23.000, hydrolysis rate is It was heated at 50150 Pv^/styrene) which is 78%.

Example 18 The capsules of the present invention may contain non-proteolytic enzymes by other stabilization methods known to those skilled in the art. In order to show that the protection is as good as the protection of the as shown in Example 10 above (containing protease) in the capsule of the invention. The half-reduction result of the enzyme when used in the composition, i.e. 30-40 days, is also compared with the composition. The results were compared with the half-reduction results of the enzyme slurry used in A (the slurry was Nova's 3 avinase 16SL).

Applicant also discloses that the enzyme may be present in related compositions B below (e.g. U.S. Patent No. 4.9S9.179 to Aronson et al. 5.089.163)). We also compared the halving results when protected.

The enzyme stability results are shown in the table below (the capsules used in this experiment were the capsules from Example 4). cell 2).

NeHNova's Lipolase From this table, it can be seen that the capsules of the present invention contain proteases and non-proteolytic enzymes. known to be at least as good as other methods of stabilizing the composition. can be seen.

Example 19 It has been shown that the capsules of the present invention are effective in various protease-containing base compositions. In order to reduce the number of non-proteolytic enzymes by half in various basic compositions, The results were compared both with and without the enzyme encapsulated. .

The compositions used were the following compositions C and D.

Sorbitol approx. 3 Electrolytic reality: approx. 20 Peptized polymer approx. 1 Protease approximately 0.5 bottles Anionic surfactant approximately 15 Nonionic surfactant approximately 10 Fatty acid approx. 5 Glycerol approx. 2 Borax about 10 Bilgoo approx. 15 Electrolyte approximately 20 Peptized polymer approx. 1 Protease approximately 0.5 bottles Water remaining amount The enzyme stability results are shown in the table below.

Half-life of lipase (Lipolase of Novo composition) when stored at 37°C (Japanese) Composition C14 without capsule application Composition C47 with capsule application Composition D 30 without capsule application Composition 0 to which capsules were applied 100% active after 35 days (all other examples 50% after the number of days of landing active) The capsule used in this example was Capsule 2 of Example 4.

Example 20 In order to show that protection of other non-proteolytic enzymes is also possible, the applicant has Pseudomonas glumae from ASF, using capsules, and It was present in the above composition without being used. The results are shown in the table below.

Composition Enzyme stability, i.e. half-life (days) Composition without capsule application o<1 Composition 0 to which capsules were applied 64% active after 12 days The capsules used were 1 6g of water, 0.12g of calcium acetate, and 1.9g of Pseudomonas s glumae lipase and 27.6 g of polymer 2 from Example 1 for 10 minutes. Mix and mix the resulting mixture with Yaa+ato Pu1vis Mint 5pr Spray dry using ay at an inlet temperature of 130°C and atomizing air pressure of 1.5 kgf/cm. Manufactured by drying.

This example shows that the capsules of the invention are extremely sensitive to the lipase used here. This indicates that the activity of the enzyme is also preserved.

The scope of the claims 1. In a copolymer with a polymer capsule suitable for use in detergent compositions. The modified polysaccharides are selected from cellulose acetate, alkyl cellulose and hydroxyl cellulose. The acrylic polymer is selected from polyacrylic cellulose, polyacrylic acid, poly selected from methacrylic acid, and esters or salts of these acids. Capsule according to claim 1, characterized in that:

3. II aqueous polymer has a hydrolysis rate of less than 95% and a molecular weight of less than 50,000 The cap according to claim 2, characterized in that it is made of polyvinyl alcohol having Psel.

international search report Continuation of front page (31) Priority claim number 037,068 (32) Priority port March 25, 1993 Japan (33) Priority claim country United States (US) (81) Designated countries EP (AT, BE, CH, DE.

DK, ES, FR, GB, GR, IE, IT, LU, MC, NL, PT, SE) , 0A (BF, BJ, CF, CG, CI, CM, GA, GN, ML, MR, NE , S.N.

TD, TG), AT, AU, BB, BG, BR, CA.

CH, CZ, DE, DK, ES, FI, GB, HU, JP, KP, KR, LK, LU, MG, MN, MW, NL, No, NZ, PL, PT, RO, RU, SD, S.E.

SK, U.A. (72) Inventor Tourle, Liang Jian New Chassis, USA - 07648, Knollwood, Garnet Brace 12 (72) Inventor: Morgan, Leslie Joe New York, USA Duncan Avenue Number, Chassis City, Sea 07304 55.53

Claims (12)

[Claims] 1. A polymeric capsule suitable for use in detergent compositions comprising: (a) a detergent-sensitive active ingredient, and (b) (i) formed by emulsion polymerizable monomers having ethylenically unsaturated groups; (ii) a nonionic and water-soluble synthetic polymer; Polysaccharides, modified polysaccharides; proteins, modified proteins, polymers with hydroxyl groups -, polymers having carboxyl groups, and copolymers thereof. hydrophilic polymer and wherein the ratio of hydrophobic core particles to hydrophilic water-soluble polymer is from about 2:8 to about Capsules containing a composite polymer that is 7:3. 2. Nonionic and water-soluble synthetic polymers are polyvinyl alcohol and polyvinyl alcohol. Copolymers of alcohol and vinyl ester salts, polyvinylpyrrolidone, pyro Copolymers of lydone and styrene and copolymers of pyrrolidone and vinyl ester salts The modified polysaccharide is selected from among remers, cellulose acetate, alkyl cellulose and Selected among hydroxyalkylcelluloses, ataryl polymers are polyacrylic selected from lyric acid, polymethacrylic acid, and esters or salts of these acids. Capsule according to claim 1, characterized in that: 3. The hydrophilic polymer has a hydrolysis rate of less than 95% and a molecular weight of less than 50,000. The cap according to claim 2, characterized in that it is made of polyvinyl alcohol having cell. 4. Emulsion polymerizable monomers with ethylenically unsaturated groups are styrene and methylstyrene. divinylbenzene, vinyl acetate, acrylamide, methacrylamide, acrylic Esters of lylic acid and acrylic acid, methacrylic acid and esters of methacrylic acid, and monomers selected from mixtures of any of these monomers. Capsule according to any one of claims 1 to 3, characterized in that it consists of a polymer. Le. 5. The ratio of hydrophobic core to hydrophilic water-soluble polymer is about 4:6 to about 6:4. Capsule according to any one of claims 1 to 4, characterized in that: 6. Heavy liquid containing from about 5 to about 85% by weight surfactant and polymer capsules A detergent composition comprising: a polymer capsule; (a) a detergent-sensitive active ingredient, and (b) (i) formed by emulsion polymerizable monomers having ethylenically unsaturated groups; (ii) a hydrophobic polymeric core particle that is insoluble in the detergent composition; a hydrophilic polymer that dissolves or disperses when the composition is diluted with water; wherein the ratio of hydrophobic core particles to hydrophilic water-soluble polymer is from about 2:8 to about A composition comprising a composite polymer having a ratio of 7:3. 7. A claim characterized in that it contains from 0.1 to 10% by weight of polymer capsules. 6. The composition according to 6. 8. Sufficient amount of electrolyte to ensure that the capsule remains intact in the heavy detergent composition The composition according to claim 6 or 7, characterized in that it contains and/or a crosslinking agent. thing. 9. The electrolyte may be selected from monovalent, divalent, trivalent or tetravalent water-soluble electrolytes. The composition according to claim 8, characterized in that: 10. 9. A set according to claim 8, characterized in that the crosslinking agent is a Group IA metal borate. A product. 11. Any one of claims 6 to 10, characterized in that an enzyme stabilizer is added. The composition described in Section. 12. Claims 1 to 11 characterized in that an oxygen stabilizer is housed inside the capsule. The polymer capsule according to any one of the above.