Liquid detergent compositions comprising encapsulated enzymes

Abstract

Disclosed is a liquid detergent composition comprising one or more shell-core capsule types. The core comprises one or more enzymes, wherein the material forming the shell is degradable by at least one of the enzymes. The capsule preserves the active properties of the enzymes during storage of the liquid detergent composition, and the capsule releases these components when shear forces are applied during use of the liquid detergent composition during washing. The method also enables the presence of incompatible benefit agents in the same product and reduces undesirable residues on the washed article.

Description

[0001] Related Applications

[0002] This application claims priority to U.S. Provisional Patent Application No. 62 / 844,924 filed on May 8, 2019, the entire contents of which are incorporated herein by reference. Field of the Invention

[0003] The present invention relates to a liquid detergent composition comprising one or more encapsulated enzymes via a shell-core capsule, wherein the encapsulation makes it possible to fix the enzyme in the liquid detergent composition and effectively release it during the washing process. More specifically, on the one hand, the present invention relates to a liquid detergent composition in which an enzyme is located in the capsule core, wherein the enzyme is a protease, a carbohydrase, a lipase or a mixture thereof. On the other hand, the present invention relates to a detergent composition having a shell-core capsule, wherein the shell of the capsule comprises a protein, a lipid, a wax, a polysaccharide or a mixture thereof. On the other hand, the present invention relates to a method for manufacturing a shell-core capsule comprising a protease, a carbohydrase, a lipase or a mixture thereof in the core. On the other hand, the present invention relates to a method for washing fabrics and other articles using a liquid detergent composition comprising encapsulated enzymes. Background of the Invention

[0005] Enzymes are common ingredients in liquid and powder detergent compositions for cleaning fabrics and other products. They are naturally occurring protein biocatalysts that show excellent performance in removing dirt and stains from fabrics and other products by degrading the structure of dirt and stain molecules. Degrading the structure of dirt and stain molecules means that at least one of the covalent bonds of the dirt and stain molecules is broken by enzyme action. This degradation converts dirt and stain molecules into smaller species, resulting in easier transfer of dirt and stains from fabrics or other products to wash water. These smaller species are then removed by discharging the wash water and then by discharging the rinse water. However, when exposed to certain harsh environments, enzymes tend to lose their activity. Known heavy-duty liquid detergents, which are medium alkaline aqueous solutions or dispersions, are hostile environments for enzymes, denaturing them, and as a result significantly reducing their activity. In addition, enzymes may be incompatible with other components of liquid detergent compositions. Such incompatible components may be decomposed by enzymes and / or they may irreversibly reduce enzyme performance. Therefore, it is often desired to protect the enzyme from the detergent composition during storage, and also to ensure that it is released in a controlled and reproducible manner when the consumer uses the liquid detergent composition. A method for protecting the enzyme is to include an enzyme stabilizer in the detergent composition, such as a boron compound (i.e., boric acid, borate) in combination with a polyol (i.e., propylene glycol, glycerol). However, the potential toxicity of this additive promotes new immobilization methods, such as the encapsulation of enzymes. Various capsules and various methods for triggering the release of enzymes from corresponding capsules during the washing process are disclosed in the art. They include release triggering mechanisms, such as changing (a) ionic strength, (b) dilution, (c) temperature, (d) pH, etc. However, existing encapsulation methods cause the capsule material to be virtually unaffected during the washing process, which means that some capsule materials are deposited on fabrics or other products to become undesirable residues, reducing the cleaning effectiveness of the liquid detergent composition. Therefore, it is necessary to develop a liquid detergent composition that makes it possible to (a) use capsules to preserve enzymes during storage of liquid detergent compositions, (b) efficiently and quickly release enzymes during the washing process, and (c) degrade capsule materials during the washing process.

[0006] The inventors of the present invention have surprisingly found that a liquid detergent composition comprising an enzyme selected from the group consisting of proteases, carbohydrases, lipases and mixtures thereof, wherein the enzyme is encapsulated in a shell comprising protein, lipid, wax and / or polysaccharide, meets these requirements. SUMMARY OF THE INVENTION

[0008] On the one hand, various embodiments of the present invention provide a liquid detergent composition. The liquid detergent composition comprises (a) about 90% to about 99.99% by weight of a continuous phase of the liquid detergent composition, (b) about 0.01% to about 10% by weight of a shell-core capsule of the liquid detergent composition. The continuous phase comprises (1) about 1% to about 50% by weight of one or more detersive surfactants of the liquid detergent composition, and (2) about 40% to about 99% by weight of water of the liquid detergent composition. Each of the shell-core capsules comprises a shell and a core. The shell is formed by a protein, a polysaccharide, a lipid, a wax, or a mixture thereof. The core comprises an effective amount of one or more enzymes selected from proteases, carbohydrases, lipases, or a mixture thereof. The shell of the capsule surrounds the core of the capsule. The shell of the capsule is insoluble in the continuous phase of the liquid detergent composition. The shell breaks in the presence of shear stress generated during the agitation step of the washing process, and the shell material is degradable by the action of one or more enzymes.

[0009] In another aspect, various embodiments of the present invention provide a method for making a liquid detergent composition comprising a shell-core capsule by: (a) making a shell-core capsule, and (b) mixing the shell-core capsule with water and a detersive surfactant. The shell-core capsule is made by: (1) mixing a water-insoluble material with an effective amount of one or more enzymes selected from proteases, lipases, carbohydrases, and mixtures thereof, wherein the water-insoluble material is solid, gel, or liquid at room temperature, (2) separating the mixture obtained from step (1) into particles or droplets; the average size of the largest dimension of the particles or droplets is from about 0.01 mm to about 5 mm, (3) coating the particles or droplets with a shell to form a shell-core capsule, wherein the shell is formed by a material selected from proteins, polysaccharides, lipids, waxes, and mixtures thereof, and (4) mixing the shell-core capsule prepared in step (3) with a continuous phase of the liquid detergent composition, the continuous phase of the liquid detergent composition comprising water and a detersive surfactant. The liquid detergent composition comprises (i) from about 90% to about 99.99% by weight of a continuous phase of the liquid detergent composition, wherein the continuous phase comprises from about 1% to about 50% by weight of the liquid detergent composition of one or more detersive surfactants, and from about 40% to about 90% by weight of the liquid detergent composition of water, and (ii) from about 0.01% to about 10% by weight of the liquid detergent composition of shell-core capsules, wherein each of the core-shell capsules comprises a shell and a core, wherein the shell is insoluble in the continuous phase of the liquid detergent composition, wherein the shell breaks down in the presence of shear stress generated during the agitation step of the washing process, and wherein the shell material is degradable by the action of one or more enzymes.

[0010] In another aspect, various embodiments of the present invention provide a method for washing fabrics or other articles, comprising the steps of: (a) providing a liquid detergent composition comprising a continuous phase and shell-core capsules, (b) combining the liquid detergent composition with water and with fabrics or other articles to be washed, (c) agitating the combination obtained from step (b), and (d) removing the wash water. The method for washing fabrics or other articles may further include step (e), wherein step (e) comprises (1) adding rinse water to a wash container, (2) agitating the contents of the wash container, and (3) removing the rinse water from the wash container, wherein step (e) is after step (d). The liquid detergent composition comprises about 90% to about 99.99% by weight of the continuous phase of the liquid detergent composition, and about 0.01% to about 10% by weight of the liquid detergent composition of shell-core capsules, wherein each of the shell-core capsules comprises a shell and a core. The continuous phase comprises one or more detersive surfactants of about 1 wt % to about 50 wt % of the liquid detergent composition, and about 40 wt % to about 99 wt % of the water of the liquid detergent composition. The core of the shell-core capsule comprises (i) an effective amount of one or more enzymes selected from proteases, lipases, carbohydrases and mixtures thereof, and (ii) a water-insoluble material, which is solid, liquid or gel at room temperature. The shell of the shell-core capsule surrounds the core of the capsule. The shell is formed by a material selected from proteins, polysaccharides, lipids, waxes and mixtures thereof. The shell is insoluble in the continuous phase of the liquid detergent composition. The shell breaks in the presence of shear stress generated during the stirring step of the washing process. The shell material is degradable by the action of one or more enzymes.

[0011] In another aspect of the present invention, the liquid detergent composition may contain only one type of shell-core capsule. One example is a capsule wherein the shell is formed of a protein or a cross-linked protein and the core comprises a protease; the core may further comprise a carbohydrase, a lipase, or a mixture thereof. Another example is a capsule wherein the shell comprises a polysaccharide and the core comprises a carbohydrase; the core may further comprise a protease, a lipase, or a mixture thereof. Another example is a capsule wherein the shell comprises a lipid or a wax, and the core comprises a lipase; the core may further comprise a carbohydrase, a protease, or a mixture thereof.

[0012] In another aspect of the present invention, the liquid detergent composition may comprise two or more types of shell-core capsules, a first capsule type and a second capsule type. The shell of the first capsule type may be formed from a polysaccharide, and the core of the second capsule type may comprise a carbohydrase.

[0013] In another aspect of the present invention, the liquid detergent composition may comprise two or more types of shell-core capsules, a first capsule type and a second capsule type. The shell of the first capsule type may be formed from a lipid, and the core of the second capsule type may comprise a lipase. The core of the first capsule type may further comprise a carbohydrase, and the shell of the second capsule type may be formed from a polysaccharide.

[0014] In another aspect of the present invention, the liquid detergent composition may comprise two or more types of shell-core capsules, a first capsule type and a second capsule type. The shell of the first capsule type may be formed of a protein or a cross-linked protein, and the core of the second capsule type may comprise a protease. The core of the first capsule type may further comprise a carbohydrase (or lipase), and the shell of the second capsule type may be formed of a polysaccharide (or lipid).

[0015] In another aspect of the present invention, the liquid detergent composition may comprise three or more types of shell-core capsules, a first capsule type, a second capsule type and a third capsule type, wherein the shell of the first capsule type may be formed of protein or cross-linked protein, the shell of the second capsule type may be formed of polysaccharide, and the shell of the third capsule type may be formed of lipid or wax. BRIEF DESCRIPTION OF THE DRAWINGS

[0017] Figure Figure 1 is a schematic diagram of one example of a shell-core capsule useful in the liquid detergent composition of the present invention, wherein the shell comprises an enzyme.

[0018] Figure 2 and 3 is a schematic representation of two different types of shell-core capsules; the core of each capsule contains a different type of enzyme, wherein both types of capsules are present in the same liquid detergent composition.

[0019] Figure 4 is a schematic diagram of an example of a shell-core capsule, wherein the core comprises an enzyme and an additional beneficial agent that is not an enzyme.

[0020] Figure 5 is a schematic diagram of two different types of shell-core capsules; the core of one type of capsule comprises an enzyme, while the core of the other type of capsule comprises a benefit agent that is not an enzyme. Both types of capsules are present in the same liquid detergent composition.

[0021] Fig. 6A , 6B and 6C are schematic diagrams of an example of a method for making a shell-core capsule. DETAILED DESCRIPTION OF THE INVENTION

[0023] Liquid detergent compositions comprising shell-core capsules are disclosed, the shell-core capsules comprising one or more enzymes in their cores, and comprising a material forming a shell, wherein the material forming the shell can be degraded by the one or more enzymes. The capsules preserve the active properties of the enzymes during storage of the liquid detergent composition, and they break in the presence of shear stresses generated during the agitation step of the washing process. The shells of the shell-core capsules can be degraded by one or more enzymes. The method enables stable product storage, rapid release and activation of enzymes during the washing process, and the presence of incompatible benefit agents in the liquid detergent composition.

[0024] The term "protein" as used herein includes polymers comprising at least 2 amino acid units linked by peptide bonds. That is, the term "protein" as used herein includes dipeptides and oligopeptides. The term also includes cross-linked proteins. Proteases are enzymes that degrade the peptide bonds of proteins to convert proteins into smaller molecules.

[0025] As used herein, the term "polysaccharide" includes polymers and oligomers comprising at least 2 monosaccharide units linked to each other. In this regard, the term also includes disaccharides, which contain two monosaccharide units; oligosaccharides, which contain 3 to 10 monosaccharide units; and polysaccharides, which contain more than 10 monosaccharide units. Carbohydrases are enzymes that degrade polysaccharides into smaller molecules.

[0026] The term "carbohydrase" as used herein includes any enzyme that catalyzes the decomposition of polysaccharides (as defined above) into smaller species. Carbohydrase, also known as glycosidase, can be any specialized enzyme that decomposes polysaccharides, such as amylase, invertase, glucoamylase and other enzymes that decompose carbohydrates.

[0027] The term "lipid" is defined as a material belonging to fat and fat-like material groups in this article, which is insoluble in water and can be extracted by non-polar solvents such as ether, chloroform, hydrocarbon solvents or benzene. Lipid comprises unsaturated and saturated fatty acids, saturated and unsaturated fatty esters, saturated and unsaturated fatty alcohols, saturated and unsaturated fatty amines and ammonium salts, non-volatile hydrocarbon liquids and waxes, steroids, phosphatide and other fatty materials. The typical molecular weight of lipid is approximately 100 to approximately 10000g / mol. Lipase is an enzyme that lipid degradation is become smaller molecules.

[0028] The term "solid" as used herein is a material with a definite volume and shape, and it resists forces that tend to change its volume and shape. The term "liquid" as used herein is a material that can flow and conform to the shape of a confining container, but it is quite incompressible. The term "liquid" as used herein also includes semi-solids, which are materials between solids and liquids. A typical example of a semi-solid is a liquid with high viscosity. The term "gel" as used herein is a two-phase system consisting of a solid network phase swollen by a liquid phase. A gel is a colloid in which the liquid medium becomes viscous enough to behave more or less as a solid. Therefore, a gel can be elastic and colloidal or solid and rigid. The particles of the solid network in the gel are generally too small to be seen with an ordinary optical microscope.

[0029] An "effective amount" refers to an amount of a compound or composition sufficient to significantly induce a positive benefit.

[0030] An "insoluble" compound or material in a solvent or composition is one in which less than 0.1 grams of the compound or material dissolves in 1 liter of solvent or composition at 25°C and 1 atmosphere of pressure. This means that a material is insoluble in a liquid detergent composition if its solubility in 1 liter of liquid detergent composition is less than 0.1 grams at 25°C and 1 atmosphere of pressure. Similarly, a material is insoluble in water if its solubility in 1 liter of distilled water is less than 0.1 grams at 25°C and 1 atmosphere of pressure.

[0031] The term "molecular weight" or "MW" as used herein refers to number average molecular weight, unless otherwise indicated. Number average molecular weight can be measured by gel permeation chromatography.

[0032] All percentages used herein represent weight percent contents based on the weight of the total composition unless otherwise specified.

[0033] Liquid detergent composition

[0034] The present invention relates to a liquid detergent composition. Liquid detergent compositions are generally used to clean fabrics and other articles in washing machines and related devices, although in many parts of the world they are also washed by "hand". Liquid detergent compositions can be liquids, gels or pastes. They are sold as aqueous solutions or dispersions packaged in buckets, bottles, single-dose packages or other containers. They are different from solid detergent compositions sold in more traditional powder form or as soluble solid products.

[0035] Liquid detergent compositions generally comprise an aqueous solution of a detersive surfactant. So far, detersive surfactants are the most commonly used cleaning materials. Such surfactants may be anionic, nonionic, amphoteric, zwitterionic, cationic or mixtures thereof. Detersive surfactants are capable of reducing the surface tension of water, which is a feature of providing the ability to remove dirt from fabrics and other articles. The most common detersive surfactants are synthetic compounds made from petroleum-based or natural-based starting materials. Naturally occurring biosurfactants are also available, but their use in commercial detergent compositions is rare due to their high cost.

[0036] The liquid detergent composition of the present invention comprises a continuous phase. The continuous phase comprises about 1 wt % to about 50 wt % of one or more detersive surfactants of the liquid detergent composition and about 40 wt % to about 99 wt % of water of the liquid detergent composition. The liquid detergent composition of the present invention may comprise about 10 wt % to about 40 wt % of one or more detersive surfactants of the liquid detergent composition, or about 15 wt % to about 35 wt % of one or more detersive surfactants of the liquid detergent composition. The liquid detergent composition may comprise about 60 wt % to about 90 wt % of water of the liquid detergent composition, or about 65 wt % to about 85 wt % of water of the liquid detergent composition.

[0037] The pH of the liquid detergent composition is from about 4 to about 12. The pH of the liquid detergent composition may be from about 6 to about 10.

[0038] Other ingredients commonly used in liquid detergent compositions include perfumes, bleaches or other oxidizing agents, bleach activators, foam or suds boosters, foam or suds suppressants, preservatives, soil suspending or dispersing agents, soil release agents, dyes, bluing agents, optical brighteners, fillers, antimicrobial agents, fabric softeners, pH control agents, hydrotropes, chelating agents and other ingredients.

[0039] Enzyme capsule

[0040] The liquid detergent composition comprises a capsule, wherein the capsule comprises a core and a shell, and wherein the shell surrounds the core.

[0041] The liquid detergent composition comprises about 0.01% to about 10% by weight of the liquid detergent composition of capsules. The liquid detergent composition may comprise about 0.05% to about 5% by weight of the liquid detergent composition of capsules. The liquid detergent composition may comprise about 0.1% to about 1% by weight of the liquid detergent composition of capsules.

[0042] The average diameter of the capsules in the liquid detergent composition may be from about 0.1 mm to about 5 mm. The average diameter of the capsules may range from about 0.5 mm to about 5 mm. The average diameter of the capsules may range from about 1 mm to about 4 mm.

[0043] The average thickness of the shell of the capsules in the liquid detergent composition may be from about 0.1 micrometers to about 100 micrometers. The average thickness of the shell of the capsules may be from about 1 micrometers to about 50 micrometers. The average thickness of the shell of the capsules may be from about 4 micrometers to about 20 micrometers.

[0044] The shell content of the shell-core capsule is about 2 wt % to about 40 wt % of the shell-core capsule, or about 4 wt % to about 30 wt % of the shell-core capsule, or about 8 wt % to about 25 wt % of the shell-core capsule.

[0045] The shell of the capsule is formed of a material selected from the group consisting of proteins, polysaccharides, lipids, waxes and mixtures thereof.

[0046] The protein, polysaccharide, lipid and wax that are suitable for forming the capsule shell of liquid detergent composition of the present invention must be insoluble in the continuous phase of the liquid detergent composition. The shell can be formed by naturally occurring or synthetic materials. The material can include protein, cross-linked protein, polysaccharide, modified polysaccharide, lipid, organic wax, other polymers such as acrylate, polyester, etc. The material can also include its mixture. Non-limiting examples include zein, casein, albumin, gelatin, gum, cellulose, functionalized cellulose, chitosan and derivatives and natural wax.

[0047] The shell encapsulates an effective amount of one or more enzymes, wherein the enzyme is selected from the group consisting of proteases, lipases, carbohydrases, and mixtures thereof.

[0048] The capsule core of the enzyme comprising the effective amount also comprises one or more water-insoluble materials. The water-insoluble material can be one or more hydrophobic oils or waxes. The non-limiting examples of the hydrophobic oils and waxes include glycerides of hydrocarbons, fatty acids, other fatty acid esters, fatty amides, fatty acids, fatty alcohols, silicone oils and other hydrophobic materials. The capsule core can also include a thickener to improve the viscosity of the mixture of water-insoluble materials and enzyme. The fact that the core of the capsule is actually anhydrous environment can contribute to the long-term stability of the enzyme inside the capsule. The non-limiting examples of the thickener for hydrophobic oils are polymeric thickeners, such as stearic acid, 12-hydroxystearic acid, sorbitan monostearate, sorbitan monopalmitate, sucrose stearate, polyester homopolymers or copolymers, castor oil derivatives such as hydrogenated castor oil or solids such as wax, clay, organoclay and silicon dioxide. The core of the shell-core material can be shear-thinning, which can be beneficial to the capsule rupture during the washing process.

[0049] The fact that proteases, lipases and carbohydrases effectively degrade proteins, lipids, oils, fats, waxes and polysaccharides contributes to their ability to remove dirt and stains from fabrics and other articles. The vast majority of typical dirt and stains in dirty fabrics and other articles are composed of proteins, lipids, oils, fats, waxes, and polysaccharides. The degradation of dirt and stain molecules makes them more soluble or dispersible in the wash water inside the washing machine, facilitating their removal from articles cleaned by the wash water and by the rinse water.

[0050] From the time of manufacturing the liquid detergent composition until the time when the consumer uses it for cleaning, the dirt and stain removal ability of the liquid detergent composition comprising the enzyme needs to preserve the chemical and configuration structure of the enzyme. Therefore, it is important to protect the active properties of the enzyme during this time period. As is well known, when exposed to harsh environments, such as being exposed to medium alkaline aqueous heavy-duty liquid detergents, enzymes tend to lose their active properties. In this environment, many useful enzymes are denatured, and their ability to degrade other molecules is significantly reduced. Many detergent manufacturers stabilize the enzyme in the liquid detergent composition by including enzyme stabilizers, such as boric compounds (i.e., boric acid or borates) generally combined with polyols such as propylene glycol and glycerol. However, the toxicity of those additives makes this technical method less desirable, and other technical methods are being used, such as the encapsulation of enzymes.

[0051] As mentioned above, it is important to protect the enzyme during storage of the liquid detergent composition. This in turn requires that the capsule is not soluble in water or impermeable to water in the environment of the liquid detergent composition. In addition, the contents of the core of the capsule must not leak from the capsule into the continuous phase of the liquid detergent composition during storage.

[0052] The integrity of the capsules can be preserved during the storage of the liquid detergent composition by selecting the shell material, the average thickness and the average diameter of the capsules. Crosslinking of the shell material can improve the integrity of the capsules. The crosslinking can be physical (non-covalent interactions between molecules) or chemical (forming covalent bonds between molecules). For example, in the case of proteins, crosslinking with bifunctional agents such as glutaraldehyde, formaldehyde or other dialdehydes improves the integrity of the capsules under storage. In general, larger average capsule size, larger average thickness and higher crosslinking show improved capsule integrity in the liquid detergent composition.

[0053] As mentioned above, various methods are used in the art to trigger the release of enzymes from the corresponding capsules during the washing process. They include changing (a) ionic strength, (b) dilution of the water used, (c) temperature, (d) pH, etc. However, these triggering mechanisms do not affect the material of the shell, which can be deposited on the fabrics and other articles being washed, leaving undesirable residues on them, which makes washing less effective.

[0054] The present invention solves this problem because the material of the capsule shell is degraded by the encapsulated enzyme after the enzyme is released into the wash water. Thus, the enzyme will not only aid in the degradation and removal of dirt and stains from fabrics and other articles, but it will also aid in the degradation and removal of the shell material. As a result, the washing process becomes more efficient because reduced residue from the capsule shell can be deposited on fabrics and other articles.

[0055] Another benefit of the present invention is the rapid and efficient release of enzymes from capsules during the washing process. The capsules will initially release at least some of the encapsulated enzymes, as many of them will rupture with the increase in shear stress generated by the movement of the washed article during the agitation step of the washing process. However, due to the composition of the capsules, even if the rupture is incomplete, the release will still be effective, and not all capsules are ruptured due to shear stress. The small release caused by the initial shear stress-induced rupture may be sufficient to trigger the release of some enzymes into the wash water, which may trigger other capsules to be degraded, releasing their contents. This is a result of the fact that the material of the capsule shell can be degraded by the enzyme after the enzyme is released into the wash water. Those skilled in the art understand that in view of the fact that the enzyme reacts quickly and specifically and that it does not consume the biocatalyst, a small amount of the initially released enzyme will result in the rapid degradation of the corresponding shell material of many capsule shells, which can survive the shear stress-induced rupture, release more enzymes into the wash water, and accelerate the release process of the enzyme. This process can be described as a similar autocatalytic process.

[0056] The liquid detergent composition may contain only one type of core-shell capsule. Figure 1 1 is a schematic diagram of an example of such a scenario, wherein capsule shell 100 comprises shell 101, and capsule core 102 comprises enzymes (and water-insoluble materials) that can degrade the material of shell 101. A specific example is a capsule in which shell 101 is made of protein and core 102 comprises a protease. The core 102 in this example may also comprise a carbohydrase, a lipase, or a mixture thereof. The core 102 may be a solid, a viscous liquid, or a gel.

[0057] Another example is a capsule in which the shell 101 is formed of a polysaccharide and the core 102 comprises a carbohydrase; the core 102 may further comprise a protease, a lipase, or a mixture thereof. Another example is a capsule in which the shell 101 is formed of a lipid and the core 102 comprises a lipase; the core 102 may further comprise a carbohydrase, a protease, or a mixture thereof. The core 102 may be a solid, a viscous liquid, or a gel.

[0058] The liquid detergent composition may comprise two or more types of shell-core capsules. An example of a liquid detergent composition comprising two types of capsules is described in Figure 2. The corresponding liquid detergent composition comprises a first capsule type 210 and a second capsule type 220. The shell 211 of the first capsule type 210 is made of material S1; the core 212 of the first capsule type 210 comprises an enzyme E1, which is capable of degrading the material S1 of the shell 211 of the first capsule type 210. The core 211 of the first capsule type 210 may be a solid, a viscous liquid or a gel. The shell 221 of the second capsule type 220 is formed of material S2, which is different from material S1. The core 222 of the second capsule type 220 comprises an enzyme E2, which is different from enzyme E1, and the material S2 of the shell 211 of the second capsule type 220. The core 222 of the second capsule type 220 may be a solid, a viscous liquid or a gel. In one example of this case, S1 is a protein and E1 is a protease, while S2 is a polysaccharide and E2 is a carbohydrase.

[0059] Another example of a liquid detergent composition comprising two types of capsules is described in Figure 3 . The corresponding liquid detergent composition comprises a first capsule type 310 and a second capsule type 320. The shell 211 of the first capsule type 310 is formed of material S2; the core 222 of the first capsule type 310 comprises enzyme E1. The core 222 of the first capsule type 310 may be solid, liquid or gel. The shell 221 of the second capsule type 320 comprises material S1, and the core 212 of the second capsule type 320 comprises enzyme E2. The core 212 of the second capsule type 320 may be solid, liquid or gel. Enzyme E1 (in the core 222 of the first capsule type 310) is capable of degrading material S1 (the material of the shell 221 of the second capsule type 320). Similarly, enzyme E2 (in the core 212 of the second capsule type 320) is capable of degrading material S2 (the material of the shell 211 of the first capsule type 310). In one example of this case, S1 is a protein and E1 is a protease, while S2 is a polysaccharide and E2 is a carbohydrase. The shear stress induced rupture of at least some of the capsules will result in the release of at least some enzyme molecules (E1, E2) into the wash water. This can accelerate the rupture of more capsules 310 and 320, if necessary. It also degrades the protein and polysaccharides of the shell so that less of these materials can be deposited on the fabrics and other articles being washed. It is easy to understand that in a similar situation, multiple types of capsules are included in the liquid detergent composition, but only one type of capsule may need to be ruptured by shear stress in order to be able to release all the encapsulated enzymes of all capsule types.

[0060] The time required to release the initial effective amount of enzyme through the shear stress generated by the washing process can be controlled by the average diameter of the capsule and / or the average shell thickness of the capsule. In general, capsules with a larger average diameter and a smaller average shell thickness will open more quickly due to the shear force applied to the capsule.

[0061] Capsule rupture caused by shear stress generated during the agitation step of the washing process can be further favored by controlling the mechanical properties of the capsule shell. Ideally, the capsule should remain intact at zero (or very low shear rate) during the transportation and storage of the liquid detergent composition. Then at higher shear (washing process), at least some capsules should rupture. The shell can be ruptured in the presence of a force greater than 100mN, or in the presence of a force greater than 500mN, or in the presence of a force greater than 1,000mN, or in the presence of a force greater than 10,000mN. The shell can also be ruptured in the presence of a force that causes an elongation of any one of its dimensions by more than 8%.

[0062] The composition of the invention may contain capsules comprising (a) a shell made of protein or cross-linked protein, and (b) a core comprising a protease in a water-insoluble oil thickened by hydrogenated castor oil. The oil may be a terpene, such as limonene.

[0063] The composition of the present invention may contain two types of capsules A and B. Capsule A may comprise (a) a shell made of protein or cross-linked protein, and (b) a core of a polysaccharide contained in a water-insoluble oil thickened by hydrogenated castor oil. Capsule B may comprise (a) a shell made of polysaccharide or cross-linked polysaccharide, and (b) a core of a protease contained in a water-insoluble oil thickened by hydrogenated castor oil. The oil may be a terpene, such as limonene.

[0064] In addition to enzymes, the composition of the core of the liquid detergent composition may contain one or more additional benefit agents or other ingredients such as oxidants, dyes, brighteners, chelants, builders, perfumes, antimicrobials, fabric softeners, pH control agents or other benefit agents.

[0065] Inclusion of one or more additional beneficial agents (in addition to enzymes) in the capsule core may be particularly useful in situations where there are incompatible ingredients and at least one of them may degrade or become inactive during storage of the product. An example is described in Figure 4 If benefit agent 431 and benefit agent 432 are incompatible, then including 431 in the core of the capsule and 432 in the continuous phase of the liquid detergent composition 400 will alleviate the incompatibility problem. Figure 4In the example of, the capsule shell 411 of the capsule 450 is formed by material S1. The core 421 contains enzyme E1 and benefit agent 431. The benefit agent 432 incompatible with the benefit agent 431 is contained in the continuous phase of the liquid detergent composition 400. The shear stress generated in the agitation step of the washing process will release E1 and 431 from the shell-core capsule 450 into the continuous phase of the liquid detergent composition 400. This will make it possible to degrade the material S1 of the shell 411 and the benefit effect of the benefit agent 431. This method makes it possible to use incompatible benefit agents 431 and 432 in the same product without harmful interactions between the two benefit agents during product storage.

[0066] The additional incompatible beneficial agents may be contained in (a) the core of the capsule containing the enzyme, as described in the preceding paragraph, or (b) they may be contained in the core of a separate capsule that does not contain any enzyme. An example of the latter is described in Figure 5 . The liquid detergent composition 500 of the example comprises two capsule types, a first capsule type 550 and a second capsule type 560. The shell 511 of the first capsule type 550 is formed of material S1, and the core 521 of the first capsule type 511 comprises enzyme E1. The shell 561 of the second capsule type 560 is formed of material S1, and the core 571 of the second capsule type 560 comprises benefit agent 531, which is incompatible with benefit agent 532 contained in the continuous phase of the liquid detergent composition 500. Enzyme E1 is capable of degrading the material of the shell 511 of capsule type 550 and the material of the shell 561 of capsule type 560. In this case, the desired results (protection of enzyme E1 and benefit agent 531 during storage, release of enzyme E1 and benefit agent 531 during the washing process, and degradation of the materials of shells 511 and 561) are possible even if the second capsule type 560 is not ruptured by the shear stress generated during the agitation step of the washing process. This is possible because the enzyme E1 released from the first capsule type 550 is able to degrade the shell 561 of the second capsule type 560 and rupture it via a degradation mechanism. Figure 5 In the example shown, the shell 511 of the first capsule type 550 is formed of material S1, and the core 521 of the first capsule type 511 contains enzyme E2. The shell 561 of the second capsule type 560 is formed of material S2, and the core 571 of the second capsule type 560 contains benefit agent 531 and enzyme E2. The benefit agent 531 can be present together with the benefit agent 532, which is contained in the continuous phase of the liquid detergent composition 500. The enzyme E1 is capable of degrading the material of the shell 511 of the capsule type 550, and the enzyme E2 is capable of degrading the material of the shell 561 of the capsule type 560. In this case, the desired results (protection of enzymes E1, E2 and benefit agent 531 during storage, release of enzymes E1, E2 and benefit agent 531 during the washing process, and degradation of the materials of the shells 511 and 561) are possible.

[0067] Methods of washing fabrics and other articles

[0068] In another aspect, various embodiments of the present invention provide a method for washing fabrics or other articles, comprising the steps of: (a) providing a liquid detergent composition comprising a continuous phase and shell-core capsules, (b) combining the liquid detergent composition with water and with fabrics or other articles to be washed, (c) agitating the combination obtained from step (b), and (d) removing the wash water. The method for washing fabrics or other articles may further include step (e), wherein step (e) comprises (1) adding rinse water to a wash container, (2) agitating the contents of the wash container, and (3) removing the rinse water from the wash container, wherein step (e) is after step (d). The liquid detergent composition comprises about 90% to about 99.99% by weight of the continuous phase of the liquid detergent composition, and about 0.01% to about 10% by weight of the shell-core capsules of the liquid detergent composition, wherein each of the shell-core capsules comprises a shell and a core. The continuous phase comprises one or more detersive surfactants of about 1 wt % to about 50 wt % of the liquid detergent composition, and about 40 wt % to about 99 wt % of the water of the liquid detergent composition. The core of the shell-core capsule comprises (i) an effective amount of one or more enzymes selected from proteases, lipases, carbohydrases and mixtures thereof, and (ii) a water-insoluble material, which is solid, liquid or gel at room temperature. The shell of the shell-core capsule surrounds the capsule core. The shell is formed by a material selected from proteins, polysaccharides, lipids, waxes and mixtures thereof. The shell is insoluble in the continuous phase of the liquid detergent composition. The shell breaks in the presence of shear stress generated during the stirring step of the washing process. The shell material is degradable by the action of one or more enzymes.

[0069] Method for making enzyme capsules

[0070] The enzyme capsule of the present invention comprises a core having an enzyme and a water-insoluble material. The enzyme is generally mixed with the water-insoluble material in a high-speed mixer at room temperature or high temperature. A thickener is also added if necessary. The resulting mixture, which is solid or liquid or gel at room temperature, is then dispersed into particles (or drops) of a desired size. The particles or drops have an average size of the maximum dimension of the particles or drops of about 0.01 mm to about 5 mm, or about 0.1 mm to about 5 mm. An extruder equipped with a knife or other suitable equipment can be used for this step. The particles or drops are then coated with a material as a shell. This step can be performed by precipitating the shell material on the particles. A variety of methods can be used for this step, such as (a) treating the particles with a solution of the shell material and evaporating the solvent, (b) treating the particles with a solution of the shell material and then treating with a medium in which the shell material is insoluble, (c) treating the particles with a solution of the shell material and then adding a complexing agent for precipitating the shell material, (d) spraying the particles with a melt of the shell material, (d) precipitating the shell material in a dispersion of the particles by polymerization or copolymerization, or (e) other related methods known in the art.

[0071] An example of an encapsulation method for making protease capsules using a shell containing a protein is provided below. This example includes three main steps: (a) preparation of gel precursor, (b) gel preparation and pelletization, and (c) enzyme pellet encapsulation. Fig. 6A , 6B 6C provide a diagrammatic illustration of the three main steps. In the first step, a water-insoluble material 610 is mixed with a thickener in a container to prepare a gel precursor 630, such as Fig. 6A As shown. The gel precursor 630 is mixed with the enzyme (or enzyme solution) 640 to form an enzyme gel 650. The enzyme gel 650 is extruded using an extruder 670. The enzyme pellets 660 are collected at the orifice of the extruder, as shown in FIG. Figure 6B As shown. The enzyme particles 660 are combined with a polymer solution 630, such as a protein solution in propylene glycol, under agitation to form a dispersion 680 of the enzyme particles in the protein solution. Finally, the dispersion 680 of the enzyme particles in the protein solution is mixed with water to form an aqueous dispersion of the shell-core capsule 695, such as Figure 6C The resulting dispersion of core-shell capsules 695 can be added to the continuous phase of a detergent to form a liquid detergent composition (this step is not shown).

[0072] Example of a method for making enzyme capsules

[0073] At a temperature of 60°C, 9.6 grams of limonene (supplied by Florida Chemical Company, Winter Haven, Florida) and 0.8 grams of hydrogenated castor oil (Thixcin ) supplied by Elements Specialties, East Windsor, NJ) was mixed at 10,000 rpm for 10 minutes. A 0.08 gram amount of solid protease ( Supplied by Millipore-Sigma; P0029) was added to the solution and mixed for 2 minutes under the same conditions. When the above mixture was still fluid, it was extruded into a rod with a diameter of about 3 mm using a single screw extruder. The rod was cooled at room temperature to provide a gel structure, which was cut into particles each of which had a size of about 4 mm. The mechanical properties of the particles were tested by applying a force of 0.2 N. The particles maintained their physical form, and the particles broke by applying a force of 4 N.

[0074] The water-insoluble shell was deposited on the above pellets using the following method: A solution of zein (supplied by Millipore-Sigma; W555025) in propylene glycol (supplied by Aldrich; 81380) was made by mixing 98 grams of propylene glycol with 2 grams of zein and mixing vigorously at room temperature for 3 minutes using a high-speed mixer. The gel pellets were immersed in the zein-propylene glycol solution and then transferred to a beaker containing 100 milliliters of water, which resulted in the precipitation of zein on the enzyme pellets and the preparation of shell-core capsules.

[0075] Evaluation of membrane properties of cross-linked corn protein

[0076] The evaluations described in the following two paragraphs were conducted to determine whether the film properties of the cross-linked protein material were suitable as shells in enzyme capsules for liquid detergent compositions. A solution of 3 grams of zein in 60 grams of ethanol / water (80 / 20 weight %) was added to a Petri dish and allowed to dry at room temperature. A film having a thickness of approximately 150 microns was cross-linked by adding 450 microliters of a 50% aqueous glutaraldehyde solution and placing on a hot plate set at 50° C. for 2 hours. The film (approximately 1 cm in size) was cross-linked by placing on a hot plate set at 50° C. for 2 hours. The film ... 2 The insolubility of glutaraldehyde cross-linked zein films was tested by immersing the films in vials containing 20 ml of Orange House laundry detergent liquid (Yuen Foong Yu Consumer Products Co., LTD) and placing them in an oven at 45° C. The films were still present in the vials after 7 days.

[0077] The membrane was prepared by placing approximately 0.03 g of the membrane in a solution containing 10 ml of wash water (water hardness 250 ppm, pH = 8.6), 0.05 g of Orange House laundry detergent liquid (Yuen Foong Yu Consumer Products Co., LTD), and 0.05 g of solid protease ( The degradability of the cross-linked zein film was tested in vials of 1% zein (supplied by Millipore-Sigma; P0029). The vials were mixed in an orbital mixer at room temperature and the integrity of the film was visually monitored over time. The size of the film was observed to decrease over time. No film remained in the solution after 210 minutes, indicating that the entire film had disintegrated. A control sample with the same composition but without the protease was run in parallel. In that case, the film remained intact.

[0078] The elongation at break of the zein film was 9% as measured by ASTM D-882.

[0079] It will be obvious to those skilled in the art that many changes and modifications may be made to the specific embodiments of the invention described above without departing from the scope of the invention.Thus the entire description above will be interpreted as illustrative rather than restrictive.

[0080] Wash water is the liquid mixture present in the washing container during the end of the agitation process in the presence of the liquid detergent composition.

[0081] Unless otherwise indicated, all ingredient or composition levels are in reference to the active portion of such ingredient or composition and are exclusive of impurities, for example, residual solvents or by-products, which may be present in commercially available sources of such ingredients or compositions.

Claims

1. A liquid detergent composition comprising: a. 90% to 99.99% by weight of a liquid detergent composition of a continuous phase comprising: 1% to 50% by weight of the liquid detergent composition of one or more detersive surfactants; and 40% to 99% by weight of the liquid detergent composition water; b. 0.01% to 10% by weight of the liquid detergent composition of two or more shell-core capsule types, wherein each of the shell-core capsule types comprises a shell and a core, wherein the shell surrounds the core, wherein the core is an anhydrous environment that is a gel at room temperature, the gel comprising an enzyme mixed with a water-insoluble material, the water-insoluble material comprising limonene and hydrogenated castor oil, wherein the shell is insoluble in the continuous phase of the liquid detergent composition, and wherein the shell ruptures in the presence of shear stress generated during a washing process, wherein the force is greater than 100 mN, the two or more shell-core capsule types comprising: (1) the core of the first capsule type comprises an effective amount of lipase, and the shell of the first capsule type is formed of a polysaccharide; (2) the core of the second capsule type comprises an effective amount of a carbohydrase, and the shell of the second capsule type is formed of a material selected from the group consisting of a lipid, a wax, and mixtures thereof; wherein the polysaccharide of the shell of the first capsule type is degradable by the action of a carbohydrase of the core of the second capsule type, and the lipid, wax or mixture thereof of the shell of the second capsule type is degradable by the action of a lipase of the core of the first capsule type; or (1') the core of the first capsule type comprises an effective amount of lipase, and the shell of the first capsule type is formed of a protein, and (2') the core of the second capsule type comprises an effective amount of a protease, and the shell of the second capsule type is formed of a material selected from the group consisting of a lipid, a wax, and mixtures thereof; wherein the protein of the shell of the first capsule type is degradable by the action of a protease of the core of the second capsule type, and the lipid, wax or mixture thereof of the shell of the second capsule type is degradable by the action of a lipase of the core of the first capsule type; or (1'') the core of the first capsule type comprises an effective amount of a carbohydrase, and the shell of the first capsule type is formed of a protein, and (2'') the core of the second capsule type comprises an effective amount of a protease, and the shell of the second capsule type is formed of a polysaccharide; wherein the protein of the shell of the first capsule type is degradable by the action of a protease of the core of the second capsule type, and the polysaccharide of the shell of the second capsule type is degradable by the action of a carbohydrase of the core of the first capsule type.

2. A liquid detergent composition according to claim 1, wherein said continuous phase further comprises at least one benefit agent other than said one or more detersive surfactants.

3. A liquid detergent composition according to claim 2, wherein the at least one benefit agent other than the one or more detersive surfactants is selected from oxidants, dyes, brighteners, chelants, builders, perfumes, antimicrobials, fabric softeners and pH control agents.

4. The liquid detergent composition according to claim 1, wherein said core further comprises at least one benefit agent other than said enzyme.

5. A liquid detergent composition according to claim 4, wherein the at least one benefit agent other than the enzyme is selected from oxidants, dyes, brighteners, chelants, builders, perfumes, antimicrobials, fabric softeners and pH control agents. 6 . The liquid detergent composition according to claim 1 , wherein the shell content of the shell-core capsule is 2 to 40 wt % of the shell-core capsule.

7. The liquid detergent composition according to claim 1, wherein the core of the first capsule type (1') further comprises a carbohydrase.

8. The liquid detergent composition according to claim 1, wherein the core of the first capsule type (1 '') further comprises a lipase.

9. The liquid detergent composition of claim 1, wherein the liquid detergent composition comprises three shell-core capsule types, a first capsule type, a second capsule type, and a third capsule type, wherein the shell of the first capsule type is formed of a protein, the shell of the second capsule type is formed of a polysaccharide, and the shell of the third capsule type is formed of a lipid.

10. The liquid detergent composition according to claim 1, wherein the average diameter of the shell-core capsule is 0.1 mm to 5 mm.

11. The liquid detergent composition according to claim 1, wherein the average thickness of the shell of the core-shell capsule is 0.1 micrometer to 100 micrometers.

12. A method of washing fabrics and other articles using a detergent composition comprising the steps of: a. Providing a liquid detergent composition comprising: (1) 90% to 99.99% by weight of the continuous phase of the liquid detergent composition, comprising: 1% to 50% by weight of the liquid detergent composition of one or more detersive surfactants; and 40% to 99% by weight of the liquid detergent composition water; (2) 0.01% to 10% by weight of the liquid detergent composition of two or more types of shell-core capsules, wherein each of the shell-core capsules comprises a shell and a core, wherein the shell surrounds the core, wherein the core is an anhydrous environment that is a gel at room temperature, the gel comprising an enzyme mixed with a water-insoluble material, the water-insoluble material comprising limonene and hydrogenated castor oil, wherein the shell is insoluble in the continuous phase of the liquid detergent composition, and wherein the shell ruptures in the presence of shear stress generated during a washing process, wherein the force is greater than 100 mN, (a) the core of a first capsule type comprises an effective amount of a lipase, and the shell of said first capsule type is formed from a polysaccharide; (b) the core of the second capsule type comprises an effective amount of a carbohydrase, and the shell of the second capsule type is formed from a material selected from the group consisting of a lipid, a wax, and mixtures thereof; or (a') the core of a first capsule type comprises an effective amount of a lipase, and the shell of said first capsule type is formed from a protein, and (b') the core of the second capsule type comprises an effective amount of a protease, and the shell of the second capsule type is formed from a material selected from the group consisting of a lipid, a wax, and mixtures thereof; wherein the protein of the shell of the first capsule type is degradable by the action of a protease of the core of the second capsule type, and the lipid, wax or mixture thereof of the shell of the second capsule type is degradable by the action of a lipase of the core of the first capsule type; or (a'') the core of the first capsule type comprises an effective amount of a carbohydrase, and the shell of the first capsule type is formed of a protein, and (b'') the core of the second capsule type comprises an effective amount of a protease, and the shell of the second capsule type is formed from a polysaccharide; wherein the protein of the shell of the first capsule type is degradable by the action of a protease of the core of the second capsule type, and the polysaccharide of the shell of the second capsule type is degradable by the action of a carbohydrase of the core of the first capsule type; b. combining the liquid detergent composition with water and with fabrics or other articles to be washed in a washing container; c. stirring the combination obtained in step b; and d. Removing wash water from the wash container.

13. The method of laundering fabrics and other articles of claim 12, wherein the method further comprises step e, wherein step e comprises (1) adding rinse water to the wash container, (2) agitating the contents of the wash container, and (3) removing the rinse water from the wash container, wherein step e is subsequent to step d.

14. A method for producing a liquid detergent composition comprising the steps of: a. Fabricate the shell-core capsule by the following steps: (1) mixing a water-insoluble material with an effective amount of one or more enzymes selected from the group consisting of proteases, lipases, carbohydrases and mixtures thereof, wherein the water-insoluble material comprises limonene and hydrogenated castor oil, wherein the water-insoluble material is a gel at room temperature; (2) separating the mixture obtained in step (1) into particles, wherein the average size of the largest dimension of the particles is 0.01 mm to 5 mm; (3) coating the particles with a shell material to form a shell-core capsule, wherein the shell comprises a material selected from the group consisting of proteins, polysaccharides, lipids, waxes and mixtures thereof; b. The shell-core capsule prepared in step a is mixed with water and a detersive surfactant; wherein the liquid detergent composition comprises (i) 90% to 99.99% by weight of a continuous phase, wherein the continuous phase comprises 1% to 50% by weight of the liquid detergent composition of one or more detersive surfactants and 40% to 90% by weight of the liquid detergent composition of water, and (ii) 0.01% to 10% by weight of two or more shell-core capsules, wherein each of the shell-core capsules comprises a shell and a core, wherein the shell is insoluble in the continuous phase of the liquid detergent composition, wherein the shell material is degradable by the action of the one or more enzymes, wherein the shell ruptures in the presence of shear stress generated during an agitation step of a washing process, wherein the force is greater than 100 mN, (a) the core of a first capsule type comprises an effective amount of a lipase, and the shell of said first capsule type is formed from a polysaccharide; (b) the core of the second capsule type comprises an effective amount of a carbohydrase, and the shell of the second capsule type is formed from a material selected from the group consisting of a lipid, a wax, and mixtures thereof; wherein the polysaccharide of the shell of the first capsule type is degradable by the action of a carbohydrase of the core of the second capsule type, and the lipid, wax or mixture thereof of the shell of the second capsule type is degradable by the action of a lipase of the core of the first capsule type; or (a') the core of a first capsule type comprises an effective amount of a lipase, and the shell of said first capsule type is formed from a protein, and (b') the core of the second capsule type comprises an effective amount of a protease, and the shell of the second capsule type is formed from a material selected from the group consisting of a lipid, a wax, and mixtures thereof; wherein the protein of the shell of the first capsule type is degradable by the action of a protease of the core of the second capsule type, and the lipid, wax or mixture thereof of the shell of the second capsule type is degradable by the action of a lipase of the core of the first capsule type; or (a'') the core of the first capsule type comprises an effective amount of a carbohydrase, and the shell of the first capsule type is formed of a protein, and (b'') the core of the second capsule type comprises an effective amount of a protease, and the shell of the second capsule type is formed from a polysaccharide; wherein the protein of the shell of the first capsule type is degradable by the action of a protease of the core of the second capsule type, and the polysaccharide of the shell of the second capsule type is degradable by the action of a carbohydrase of the core of the first capsule type.

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