WO2025008400A1

WO2025008400A1 - Enzymatic detergent bars having improved enzyme stability

Info

Publication number: WO2025008400A1
Application number: PCT/EP2024/068728
Authority: WO
Inventors: Ole Simonsen; Shilpa Ramani; Sanjoli Doneria; Rajendra Kulothungan SAINATHAN; Prashant Jain; Ramya Subramaniam; Premchand S. CHIGADANNAVAR
Original assignee: Novozymes A/S
Priority date: 2023-07-03
Filing date: 2024-07-03
Publication date: 2025-01-09

Abstract

The invention provides enzymatic detergent bars exhibiting improved enzyme stability after repeated wetting and drying when used for hand washing of laundry or dishware.

Description

ENZYMATIC DETERGENT BARS HAVING IMPROVED ENZYME STABILITY

FIELD OF THE INVENTION

The present invention relates to detergent bars comprising enzyme granules with a hydrophobic coating, which exhibit improved enzyme stability during repeated wetting and drying. Such detergent bars are useful for hand washing of laundry or dishware.

BACKGROUND

Detergent bars are more common in emerging markets where body grime and tough stains are still consumer pain points. Unlike detergent powders and liquids, laundry and dishwash bars are still whitespace for enzyme inclusion. The basic wash practice in case of bars is to wet and use, contrary to detergent powders and liquid, resulting in repeated wetting and drying cycles. Detergent bars are also referred to as syndet bars (or non-soap bars) and distinguish from soap bars by containing synthetic surfactant, while soap bars contain natural soaps (sodium salts of fatty acids) made by saponification.

Enzymes can be added to detergent bars in the form of a liquid enzyme product, or as a granulated enzyme product, which dissolves and releases the enzyme during use.

Granulated enzymes have excellent stability during manufacture and storage, but when the granules dissolve during wet-dry cycle, the protection is lost, and the enzyme activity will decline.

Because of how detergent bars are used, enzyme granules in the outer layers of the detergent bar will fully or partly dissolve during rubbing of the bar on the fabric in the washing process, resulting in loss of enzyme stability during the following storage until the next wash cycle.

We have found that enzyme granules become more resistant to the repeated wetting and drying cycles by adding a coating that does not dissolve in water, but which releases the enzyme during the rubbing phase in the washing process.

SUMMARY OF THE INVENTION

The present invention provides, in a first aspect, a detergent bar comprising an anionic surfactant, a builder, water, and an enzyme-containing granule having a hydrophobic coating.

Other aspects and embodiments of the invention are apparent from the description and examples.

Unless otherwise indicated, or if it is apparent from the context that something else is meant, all percentages are percentage by weight (% w/w).

As used herein, the term "consists essentially of" (and grammatical variants thereof), as applied to the compositions and methods of the invention, means that the compositions/methods may contain additional components so long as the additional components do not materially alter the composition/method.

As used herein, the term "essentially free of' (and grammatical variants thereof), as applied to the compositions and methods of the invention, means that the compositions/methods may contain minor amounts of the specified component so long as the amount of the component does not materially alter, or provide any material effect on, the composition/method. In an embodiment, "essentially free of" means 0% w/w.

Particle size distribution may be measured using laser diffraction methods or optical digital imaging methods or sieve analysis. Unless otherwise indicated, the particle size is the volume based particle diameter (and the average particle size, Dso, is the volume average particle diameter), which is the same as the weight based particle diameter if the densities of the particles are the same

DETAILED DESCRIPTION

We have found that it is advantageous to apply a hydrophobic coating to enzyme granules used in detergent bars. Enzyme granules located below the surface of a detergent bar will experience a wet/humid environment during use, and this is detrimental to the structural stability of detergent enzyme granules designed to quickly dissolve in water. By applying a hydrophobic coating, the enzyme granules will be more resistant to dissolution and only break after application of the mechanical action associated with the washing process.

The present invention is particularly useful in the production of (syndet) detergent bars because such detergent bars require a lower temperature in the manufacturing process than soap bars. This provides for a better enzyme stability during manufacturing and avoids melting of the hydrophobic coating, in particular hydrophobic coatings made from vegetable oils or fats.

Detergent bars

The present invention relates to a (syndet) detergent bar comprising enzyme granules having a hydrophobic coating, as described below. In particular, the present invention relates to a detergent bar comprising an (synthetic) anionic surfactant, a builder, water, and enzyme granules having a hydrophobic coating; where the anionic surfactant is selected from the group consisting of alkyl sulfonic acids, alkyl sulfates, alkyl sulfonates, alkyl benzene sulfonic acid, alkyl benzene sulfates, alkyl benzene sulfonates, alkyl ether sulfonic acids, alkyl ether sulfates, alkyl ether sulfonates, paraffin sulfonic acids, paraffin sulfates, paraffin sulfonates, olefin sulfonic acids, olefin sulfates, olefin sulfonates, alpha-sulfocarboxylates, esters of alphasulfocarboxylates, alkyl glyceryl ether sulfonic acids, alkyl glyceryl ether sulfates, alkyl glyceryl ether sulfonates, sulfates of fatty acids, sulfonates of fatty acids, sulfonates of fatty acid esters, alkyl phenol polyethoxy ether sulfates, 2-acryloxy-alkane-l-sulfonic acid, 2-acryloxy-alkane-l - sulfonate, beta-alkyloxy alkane sulfonic acid, beta-alkyloxy alkane sulfonate, and salts and mixtures thereof.

The detergent bar is a solid and homogenous mixture of the ingredients.

Detergent bars remain popular with consumers for cleansing laundry and dish ware.

Laundry detergent bars are used in many locales for cleaning clothes. Technical developments in the field of laundry detergent bars have involved the formulation of laundry detergent bars which are effective in cleaning clothes; have acceptable sudsing characteristics in warm and cool water, and in both hard and soft water; and also have acceptable in-use wear rates, hardness, durability, feel, have low slough and rapid drying. Contrary to powder detergents, detergent bars are free of bleaching agents, like bleach catalysts, bleach activators, and sources of organic peroxyacids (e.g., percarbonates).

The present invention also provides a method of making a detergent bar, comprising providing a surfactant; providing a builder; providing enzyme granules having a hydrophobic coating (optionally also providing a fragrance and/or a colorant) and providing water; mixing these constituents to form a combination; milling the combination; and extruding the milled combination to provide the detergent bar.

In an embodiment, the detergent bar of the invention comprises 5-30% w/w of a surfactant (preferably 5-25% w/w, 5-20% w/w, or 5-15% w/w); 5-50% w/w of a builder (preferably 10-40% w/w, 10-30% w/w, or 10-15% w/w); 10-30% w/w of water (preferably 10-25% w/w or 10-20% w/w); and 0.01-5% of enzyme granules having a hydrophobic coating (preferably 0.01-2% w/w, 0.05-2% w/w, or 0.05-1 % w/w); wherein the detergent bar is a solid (/.e., wherein the detergent bar does not perceptibly change shape when placed on a rigid surface and left to stand at room temperature, 22°C, and pressure, 101.4 kPa, for 24 hours).

In an embodiment, the detergent bar has an acceptable in-use wear rate, hardness, durability, rapid drying, low smear and/or improved eco-friendliness.

The detergent bar may have a wear rate of 0.5-9% w/w (such as 1-8% w/w), wherein the wear rate is the loss in weight of the detergent bar after 4 days of use.

Preferably, the detergent bar of the present invention is selected from a personal care bar, a dishwash bar and a laundry bar; preferably the detergent bar is a dishwash bar or a laundry bar.

Surfactant

The detergent bar of the invention may comprise 5-30% w/w of the (synthetic) anionic surfactant; preferably 5-25% w/w, more preferably 5-20% w/w, and most preferably 5-15% w/w of a surfactant.

Preferably, the anionic surfactant is selected from the group consisting of Cs-2o alkyl benzene sulfonic acid, Cs-2o alkyl benzene sulfates, Cs-2o alkyl benzene sulfonate, Cs-2o alkyl ether sulfonic acids, Cs-2o alkyl ether sulfates, Cs-2o alkyl ether sulfonates, paraffin sulfonic acid, paraffin sulfates, paraffin sulfonate, alpha-olefin sulfonic acid, alpha-olefin sulfate, alpha-olefin sulfonate, sulfonates of fatty acids, sulfonates of fatty acid esters, and salts and mixtures thereof.

More preferably, the anionic surfactant is selected from the group consisting of C10-16 alkyl benzene sulfonic acid, C10-16 alkyl benzene sulfonate, C10-16 alkyl polyethoxy sulfonic acids, C10- 16 alkyl polyethoxy sulfates, C10-16 alkyl polyethoxy sulfonates, and salts and mixtures thereof.

Even more preferably, the anionic surfactant is selected from the group consisting of Cn-14 alkyl benzene sulfonic acid, Cn-14 alkyl benzene sulfonate, Cn-14 alkyl polyethoxy sulfonic acids, C11-14 alkyl polyethoxy sulfates, Cn-14 alkyl polyethoxy sulfonates, and salts and mixtures thereof.

In particular, the anionic surfactant includes (preferably, is) Cn-14 alkyl benzene sulfonic acid.

The detergent bar may further comprise a non-ionic surfactant, preferably in an amount of 1-10% w/w.

Builder

The detergent bar of the invention may comprise 5-50% w/w of a builder; preferably 10- 40% w/w, more preferably 10-30% w/w, and most preferably 10-20% w/w of a builder.

The builder may be selected from the group consisting of hydratable alkali metal phosphates, alkalis (including carbonates and bicarbonates), zeolites, ethylenediaminetetraacetate, nitrilotriacetate, and mixtures thereof.

Preferably, the builder is selected from the group consisting of zeolite, sodium citrate, sodium silicate, sodium carbonate, calcium carbonate, sodium bicarbonate, calcium bicarbonate and mixtures thereof.

More preferably, the builder includes at least one of sodium carbonate and calcium carbonate.

Water

The detergent bar of the invention may comprise 10-30% w/w of water; preferably 10-25% w/w or 10-20% w/w of water.

The detergent bar may further comprise one or more ingredients selected from the group consisting of humectants; processing aids (e.g., titanium dioxide); preservatives (e.g., benzoic acid, sorbic acid, phenoxyethanol); antioxidants (e.g., butylated hydroxy toluene); viscosity modifiers; polymers; free fatty acids; foam stabilizers; foam enhancers; chelating agents; antimicrobial agents (e.g., biocides); pH adjusting agents; pH buffering agents; fragrances/perfumes; colorants (e.g., dyes), and mixtures thereof.

Preferably, the detergent bar comprises a fragrance and/or a colorant. Humectant

The detergent bar may comprise a humectant, such as in an amount of 0.1-5% w/w; preferably 0.25-2% w/w, more preferably 0.5-1.5% w/w, and most preferably 0.75-1.25% w/w of a humectant.

The humectant may be a polyhydric alcohol selected from the group consisting of glycerol, sorbitol, propylene glycol, butylene glycol, hexylene glycol, ethoxylated glucose, 1,2-hexane diol, hexanetriol, dipropylene glycol, erythritol, trehalose, diglycerin, xylitol, maltitol, maltose, glucose, fructose, and mixtures thereof.

Preferably, the humectant includes, or is, glycerol.

Processing aid

The detergent bar may comprise a processing aid, such as in an amount of 0.05-2% w/w; preferably 0.1 -1.5% w/w, more preferably 0.25-1.5% w/w, and most preferably 0.5-1% w/w of a processing aid.

The processing aid may be an inorganic powdery material selected from the group consisting of talc, calcite, kaolin, silicon dioxide, titanium dioxide, diatomaceous earth, and mixtures thereof.

Preferably, the processing aid is selected from the group consisting of talc, calcite, titanium dioxide, and mixtures thereof. In particular, the processing aid includes titanium dioxide.

Chelating agent

The detergent bar may comprise a chelating agent, such as in an amount of 0.01-5% w/w; preferably 0.05-3% w/w, more preferably 0.05-1% w/w, and most preferably 0.1- 1 % w/w of a chelating agent.

The chelating agent may be selected from the group consisting of diethylenetriamine pentaacetic acid; 1 -hydroxy ethane 1,1-diphosphonic acid; citric acid; ethylene diamine tetraacetic acid (EDTA), and salts and mixtures thereof.

Preferably, the chelating agent is selected from the group consisting of diethylenetriamine pentaacetic acid pentasodium salt, 1 -hydroxy ethane 1,1-diphosphonic acid disodium salt; citric acid, ethylene diamine tetraacetic acid (EDTA), ethylene diamine tetraacetic acid tetrasodium, and salts and mixtures thereof. In particular, the chelating agent includes ethylene diamine tetraacetic acid tetrasodium salt.

Fragrance

The detergent bar may comprise a fragrance, such as in an amount of 0.01-3% w/w; preferably 0.01 to 1% w/w or 0.05-0.1% w/w of a fragrance. Colorant

The detergent bar may comprise a colorant, such as in an amount of 0.01-3% w/w; preferably 0.02-2% w/w, more preferably 0.03-1 % w/w, and most preferably 0.03-0.5% w/w of a colorant.

Enzyme-containing granules

The detergent bar of the invention may comprise 0.01-5% of enzyme granules having a hydrophobic coating; preferably 0.01-2% w/w, more preferably 0.05-2% w/w, and most preferably 0.05-1 % w/w of enzyme granules having a hydrophobic coating.

The enzyme granules having a hydrophobic coating, used in the detergent bar of the invention, comprise a core and a coating.

The core comprises the enzyme and may also include binders (such as synthetic polymer, wax, fat, or carbohydrate). The core may further include additional materials such as fillers, fibre materials (cellulose or synthetic fibres), stabilizing agents, solubilizing agents, suspension agents, viscosity regulating agents, light spheres, plasticizers, salts, lubricants and fragrances.

The core can be prepared by granulation, e.g. by use of granulation techniques including: crystallization, precipitation, pan-coating, fluid bed coating, fluid bed agglomeration, rotary atomization, extrusion, prilling, spheronization, size reduction methods, drum granulation, and/or high shear granulation. Such granulation techniques are, for example, described on page 5-6 of WO 2022/171872.

The core may consist of an inert particle with the enzyme absorbed into it, or with the enzyme applied on to the surface, for example, via fluid bed coating.

The particle size, measured as equivalent spherical diameter (volume based average particle size), of the granule may be 50-2000 pm, preferably 100-1500 pm or 250-1200 pm.

Hydrophobic coating

The enzyme granules have a coating which comprises a hydrophobic substance, such as a high-melting wax or fat, particularly in an amount of 1-50% or 5-15% by weight. The coating may comprise a fine particulate matter in an amount of 25-80% w/w, preferably 40-80% w/w or 50-80% w/w, which typically has an average volume-based particle size, Dso, of less than 50 pm or less than 25 pm. Examples of fine particulate matter is talc, kaolin, titanium dioxide, calcium carbonate, calcium sulphate, starch, diatomaceous earth, amorphous silica, bentonite, and mixtures thereof. The fine particulate matter improves the production process of applying the hydrophobic coating onto the uncoated enzyme granules by reducing agglomeration of the coated granules. When included, the fine particulate matter is an integrated part of the hydrophobic coating (a mixture of the hydrophobic substance and the fine particulate matter), and as such it can also reduce/substitute some of the hydrophobic substance which is more expensive. Such particulate matter may also be or comprise a water-insoluble substance, e.g. kaolin, talc or calcium carbonate, e.g. in an amount of 60-75% by weight.

The hydrophobic coating may constitute 15-35% by weight of the coated granule. The hydrophobic substance may be a fat, wax or paraffin. The coating may be as described in WO 92/12645 or WO 97/16076.

The hydrophobic substance is a substance which is not readily wetted by water, i.e. which tends to repel water. Such substances - examples of which are oils, fats, hydrocarbon waxes and numerous types of resins - are in general essentially completely insoluble in water.

Hydrophobic substances which are of particular relevance in the context of the present invention are normally substances which are soluble in organic solvents of the hydrocarbon type (e.g., hexane, heptane and the like) or chlorinated hydrocarbon type (e.g., dichloromethane, chloroform and the like). Suitable examples hereof include various glyceride lipids (j.e., mono-, di- or triglycerides), such as animal tallow (e.g., beef or mutton tallow) and vegetable oils, and certain derivatives thereof.

Particularly well-suited hydrophobic substances are those which are solid at ambient temperature, and which have a melting point of about 40°C or above. Examples hereof include substances such as certain native or hardened (hydrogenated) vegetable oils or fats, such as hydrogenated palm oil, hydrogenated palm kernel oil or hydrogenated soya bean oil, as well as materials such as hydrogenated tallow (e.g. hydrogenated beef tallow or mutton tallow). The coating agent comprises a high melting fat or wax, particularly with a melting point between 30 and 100°C preferably between 40 and 60°C. The fat may be a glycerol ester (mono-, di- or triester or a mixture thereof). The wax may be a waxy substance which is of tough and not brittle nature and possesses substantial plasticity at room temperature.

The paraffin (paraffin wax) is a white or colorless soft solid which may be used as a lubricant and for other applications. It is derived from petroleum and consists of a mixture of hydrocarbon molecules containing between twenty and forty carbon atoms.

In addition to the hydrophobic coating, the granules may optionally comprise one or more additional coatings, either as an undercoat or a topcoat, e.g. to reduce dust formation. Such a coating may comprise polyethylene glycol (PEG), polyvinyl alcohol (PVA) or hydroxypropyl methyl cellulose (HPMC).

Enzymes

The enzymes comprised in the granules are catalytic proteins, and the term “active enzyme protein” is defined herein as the amount of catalytic protein(s), which exhibits enzymatic activity. This can be determined using an activity based analytical enzyme assay. In such assays, the enzyme typically catalyzes a reaction generating a colored compound. The amount of the colored compound can be measured and correlated to the concentration of the active enzyme protein. This technique is well-known in the art. The enzyme(s) may be selected from the group consisting of protease, lipase, cutinase, amylase, carbohydrase, cellulase, pectinase, mannanase, arabinase, galactanase, xylanase, nuclease (DNase, RNase), dispersin, catalase, perhydrolase, and oxidase (such as laccase and/or peroxidase). Preferably, the enzyme(s) is a detergent enzyme selected from the group consisting of protease, lipase, amylase, cellulase, pectinase, mannanase, xylanase, nuclease (DNase, RNase), dispersin, catalase, perhydrolase, and combinations thereof. In particularly preferred embodiment, the enzyme is a protease or an amylase.

The protease may be a serine protease, for example a subtilisin. The amylase may be an alpha-amylase or a glucoamylase. The cellulase may be an endo-1 ,4-beta-glucanase, also referred to as endoglucanase.

The enzyme may be a naturally occurring enzyme of bacterial or fungal origin, or it may be a variant derived from one or more naturally occurring enzymes by gene shuffling and/or by substituting, deleting or inserting one or more amino acids. Chemically modified or protein engineered mutants are included.

The enzyme-containing granule having a hydrophobic coating may comprises at least one enzyme in an amount of 0.1-25% w/w active enzyme protein; preferably in an amount of 0.5- 25% w/w active enzyme protein; and more preferably in an amount of 0.5-20% w/w active enzyme protein or 1-20% w/w active enzyme protein.

Further embodiments of the invention include:

Embodiment 1. A solid detergent bar comprising

(a) an anionic surfactant selected from the group consisting of alkyl sulfonic acids, alkyl sulfates, alkyl sulfonates, alkyl benzene sulfonic acid, alkyl benzene sulfates, alkyl benzene sulfonates, alkyl ether sulfonic acids, alkyl ether sulfates, alkyl ether sulfonates, paraffin sulfonic acids, paraffin sulfates, paraffin sulfonates, olefin sulfonic acids, olefin sulfates, olefin sulfonates, alpha-sulfocarboxylates, esters of alpha-sulfocarboxylates, alkyl glyceryl ether sulfonic acids, alkyl glyceryl ether sulfates, alkyl glyceryl ether sulfonates, sulfates of fatty acids, sulfonates of fatty acids, sulfonates of fatty acid esters, alkyl phenol polyethoxy ether sulfates, 2-acryloxy- alkane-l-sulfonic acid, 2-acryloxy-alkane-l -sulfonate, beta-alkyloxy alkane sulfonic acid, betaalkyloxy alkane sulfonate, and salts and mixtures thereof;

(b) a builder;

(c) water; and

(d) an enzyme-containing granule having a hydrophobic coating.

Embodiment 2. The detergent bar of any of the preceding embodiments, which is free of bleaching agents selected from the group consisting of bleach catalysts, bleach activators, and sources of organic peroxyacids Embodiment 3. The detergent bar of any of the preceding embodiments, which comprises 5-30% w/w of the anionic surfactant.

Embodiment 4. The detergent bar of any of the preceding embodiments, which comprises 5-25% w/w of the anionic surfactant.

Embodiment 5. The detergent bar of any of the preceding embodiments, which comprises 5-20% w/w of the anionic surfactant.

Embodiment 6. The detergent bar of any of the preceding embodiments, which comprises 5-15% w/w of the anionic surfactant.

Embodiment 7. The detergent bar of any of the preceding embodiments, which further comprises a non-ionic surfactant, preferably in an amount of 1-10% w/w.

Embodiment 8. The detergent bar of any of the preceding embodiments, which comprises 10-40% w/w of the builder.

Embodiment 9. The detergent bar of any of the preceding embodiments, which comprises 10-30% w/w of the builder.

Embodiment 10. The detergent bar of any of the preceding embodiments, which comprises 10-20% w/w of the builder.

Embodiment 11. The detergent bar of any of the preceding embodiments, wherein the builder is selected from the group consisting of hydratable alkali metal phosphates, alkalis (including carbonates and bicarbonates), zeolites, ethylenediaminetetraacetate, nitrilotriacetate, and mixtures thereof.

Embodiment 12. The detergent bar of any of the preceding embodiments, wherein the builder is selected from the group consisting of zeolite, sodium citrate, sodium silicate, sodium carbonate, sodium bicarbonate, and mixtures thereof.

Embodiment 13. The detergent bar of any of the preceding embodiments, wherein the builder comprises at least one of sodium carbonate and calcium carbonate.

Embodiment 14. The detergent bar of any of the preceding embodiments, which comprises 10-30% w/w of water.

Embodiment 15. The detergent bar of any of the preceding embodiments, which comprises 10-25% w/w of water.

Embodiment 16. The detergent bar of any of the preceding embodiments, which comprises 10-20% w/w of water.

Embodiment 17. The detergent bar of any of the preceding embodiments, which comprises 0.01-5% w/w of the enzyme-containing granule having a hydrophobic coating.

Embodiment 18. The detergent bar of any of the preceding embodiments, which comprises 0.01-2% w/w of the enzyme-containing granule having a hydrophobic coating.

Embodiment 19. The detergent bar of any of the preceding embodiments, which comprises 0.05-2% w/w of the enzyme-containing granule having a hydrophobic coating. Embodiment 20. The detergent bar of any of the preceding embodiments, which comprises 0.05-1% w/w of the enzyme-containing granule having a hydrophobic coating.

Embodiment 21. The detergent bar of the preceding embodiment, wherein the hydrophobic coating comprises an oil or fat, wax, or paraffin.

Embodiment 22. The detergent bar of any of the preceding embodiments, wherein the hydrophobic coating comprises an oil, fat, wax, or paraffin having a melting point in the range of 30-100°C; preferably in the range of 40-60°C.

Embodiment 23. The detergent bar of any of the preceding embodiments, wherein the hydrophobic coating comprises a vegetable oil or fat; such as a mono-, di- or triglyceride, or a mixture thereof.

Embodiment 24. The detergent bar of any of the preceding embodiments, wherein the hydrophobic coating comprises hydrogenated palm oil, hydrogenated palm kernel oil, hydrogenated soya bean oil, or hydrogenated tallow.

Embodiment 25. The detergent bar of any of the preceding embodiments, wherein the enzyme is selected from the group consisting of protease, amylase, carbohydrase, lipase, nuclease, oxidoreductases, and combinations thereof.

Embodiment 26. The detergent bar of any of the preceding embodiments, wherein the enzyme is protease and/or amylase.

Embodiment 27. The detergent bar of any of the preceding embodiments, wherein the granule comprises 0.1-25% w/w of active enzyme protein.

Embodiment 28. The detergent bar of any of the preceding embodiments, wherein the granule comprises 0.5-25% w/w of active enzyme protein.

Embodiment 29. The detergent bar of any of the preceding embodiments, wherein the granule comprises 0.5-20% w/w of active enzyme protein.

Embodiment 30. The detergent bar of any of the preceding embodiments, wherein the volume based average particle size of the granule is 50-2000 pm.

Embodiment 31. The detergent bar of any of the preceding embodiments, wherein the volume based average particle size of the granule is 100-1500 pm.

Embodiment 32. The detergent bar of any of the preceding embodiments, wherein the volume based average particle size of the granule is 250-1200 pm.

Embodiment 33. The detergent bar of any of the preceding embodiments, which further comprises 0.1-5% w/w of a humectant.

Embodiment 34. The detergent bar of any of the preceding embodiments, which further comprises 0.25-2% w/w of a humectant.

Embodiment 35. The detergent bar of any of the preceding embodiments, which further comprises 0.5-1.5% w/w of a humectant.

Embodiment 36. The detergent bar of any of the preceding embodiments, which further comprises 0.75-1.25% w/w of a humectant. Embodiment 37. The detergent bar of any of the preceding embodiments, which further comprises a humectant selected from the group consisting of glycerol, sorbitol, propylene glycol, butylene glycol, hexylene glycol, ethoxylated glucose, 1,2-hexane diol, hexanetriol, dipropylene glycol, erythritol, trehalose, diglycerin, xylitol, maltitol, maltose, glucose, fructose, and mixtures thereof.

Embodiment 38. The detergent bar of any of the preceding embodiments, wherein the humectant comprises glycerol.

Embodiment 39. The detergent bar of any of the preceding embodiments, which further comprises 0.05-2% w/w of a processing aid.

Embodiment 40. The detergent bar of any of the preceding embodiments, which further comprises 0.1 -1.5% w/w of a processing aid.

Embodiment 41. The detergent bar of any of the preceding embodiments, which further comprises 0.25-1.5% w/w of a processing aid.

Embodiment 42. The detergent bar of any of the preceding embodiments, which further comprises 0.5-1% w/w of a processing aid.

Embodiment 43. The detergent bar of any of the preceding embodiments, which further comprises a processing aid selected from the group consisting of talc, calcite, kaolin, silicon dioxide, titanium dioxide, diatomaceous earth, and mixtures thereof.

Embodiment 44. The detergent bar of any of the preceding embodiments, which further comprises 0.01-5% w/w of a chelating agent.

Embodiment 45. The detergent bar of any of the preceding embodiments, which further comprises 0.05-3% w/w of a chelating agent.

Embodiment 46. The detergent bar of any of the preceding embodiments, which further comprises 0.05-1% w/w of a chelating agent.

Embodiment 47. The detergent bar of any of the preceding embodiments, which further comprises 0.1-1% w/w of a chelating agent.

Embodiment 48. The detergent bar of any of the preceding embodiments, which further comprises a chelating agent selected from the group consisting of diethylenetriamine pentaacetic acid; 1 -hydroxy ethane 1,1-diphosphonic acid; citric acid; ethylene diamine tetraacetic acid (EDTA), and salts and mixtures thereof.

Embodiment 49. The detergent bar of any of the preceding embodiments, which further comprises 0.01-3% w/w of a fragrance.

Embodiment 50. The detergent bar of any of the preceding embodiments, which further comprises 0.01 to 1% w/w of a fragrance.

Embodiment 51. The detergent bar of any of the preceding embodiments, which further comprises 0.05-0.1% w/w of a fragrance.

Embodiment 52. The detergent bar of any of the preceding embodiments, which further comprises 0.01-3% w/w of a colorant. Embodiment 53. The detergent bar of any of the preceding embodiments, which further comprises 0.01-3% w/w of a colorant.

Embodiment 54. The detergent bar of any of the preceding embodiments, which further comprises 0.02-2% w/w of a colorant.

Embodiment 55. The detergent bar of any of the preceding embodiments, which further comprises 0.03-1 % w/w of a colorant.

Embodiment 56. The detergent bar of any of the preceding embodiments, wherein the hydrophobic coating comprises a fine particulate matter in an amount of 25-80% w/w, preferably 40-80% w/w or 50-80% w/w, which has an average volume-based particle size, Dso, of less than 50 pm or less than 25 pm.

Embodiment 57. The detergent bar of the preceding embodiment, wherein the fine particulate matter comprises talc, kaolin, titanium dioxide, calcium carbonate, calcium sulphate, starch, diatomaceous earth, amorphous silica, bentonite, or mixtures thereof.

Embodiment 58. A method of making the detergent bar of any of the preceding embodiments, comprising

(a) mixing a surfactant, a builder; water, and enzyme-containing granules having a hydrophobic coating,

(b) milling the mixture, and

(c) extruding the milled mixture.

Embodiment 59. The method of the preceding embodiment, wherein the surfactant, builder, and water are premixed before adding the enzyme-containing granules having a hydrophobic coating.

The present invention is further described by the following examples that should not be construed as limiting the scope of the invention.

EXAMPLES

Chemicals were commercial products of at least reagent grade.

The enzymes used in the examples were commercial enzyme granulates. The protease was Savinase Evity 12T (SE12T), and the amylase was Stainzyme 12T (ST12T), both from Novonesis (former Novozymes).

Commercial laundry or dishwash syndet bars, ~5 kg, were broken with hammer to get smaller bar particles of size in the range of 1-2 cm. These bar particles were added to a Sigma mixer and mixed for 5 minutes at about 40°C. Enzyme granulates were added to the bar particles in the Sigma mixer in an amount of 0.05-0.3% w/w and mixing was continued for 5 minutes. This mixture was then transferred to two stage single screw plodder and extruded to get the noodles of bars and then further plodded through an eye-plate, to form a continuous rectangular rod, which was cut into 80 g bars. EXAMPLE 1

The re-plodded laundry bars containing protease enzyme granules were taken for wash performance evaluation every day for seven days, simulating typical hand wash laundry consumer washing habit. Polyester/cotton (65/35) strip soiled with blood/milk/ink (EMPA-117, SWISSATEST) was used to evaluate the performance of protease in laundry bar. The bar was dipped in water and rubbed five times on the pre-wetted stained strip. This was followed by rubbing the stained fabric against itself for 5 times and rinsing twice in bucket of water. The fabric was left for drying and observed for removal of color or the fabric turning whiter. The used bar was left on the case till the next day and the same washing process was repeated.

Table 1 shows the ability of different laundry bar samples to remove blood/milk/ink, measured by delta reflectance at 460 nm wavelength. Control refers to re-plodded bar without enzyme, SE12T refers to re-plodded bar containing enzyme with conventional coating and SE12T + HC refers to the enzyme granules with hydrophobic coating. Bar containing SE12T + HC was able to retain the ability to remove blood/milk/ink even after 7 days, while the bar containing enzyme with conventional coating lost this ability after 3 days.

Table 1. Stability and performance of enzyme in laundry bar during use, measured as delta reflectance at 460 nm.

EXAMPLE 2

For evaluating the stability and performance of amylase enzyme granules in dishwash bar, the re-plodded dishwash bars containing enzyme granules were taken for wash performance evaluation for seven consecutive days, simulating typical dishwash consumer washing habits. Technical tiles from Centre for Test Materials (CFT), soiled with mixed starch (DM-177) was used to evaluate the performance of amylase in dishwash bar. 2 ml of water was added on top of the bar and 1 gram of bar was picked up by the yellow side of the sponge. The sponge was then mounted on the Auto-scrubber and the tile was placed in the groves of Auto-scrubber and 20 scrubs were done using yellow side of the scrubber.

Table 2 shows the performance of dishwash bars with and without enzyme. ST12T refers to re-plodded bar containing enzyme with conventional coating and ST12T + HC refers to enzyme granules with hydrophobic coating. Bar containing ST12T + HC was able to retain the ability to remove starch soil even after 7 days of use, while the bar containing enzyme with conventional coating started to show decrease in performance even after the third day.

Table 2. Stability and performance of enzyme in dishwash bar during use, measured as delta reflectance at 460 nm.

Claims

1 . A solid detergent bar comprising

(b) a builder;

(c) water; and

(d) an enzyme-containing granule having a hydrophobic coating.

2. The detergent bar of claim 1 , which is free of bleaching agents selected from the group consisting of bleach catalysts, bleach activators, and sources of organic peroxyacids.

3. The detergent bar of any of the preceding claims, which comprises 5-30% w/w of the anionic surfactant; preferably 5-20% w/w of the anionic surfactant.

4. The detergent bar of any of the preceding claims, which further comprises a non-ionic surfactant; preferably in an amount of 1-10% w/w.

5. The detergent bar of any of the preceding claims, which comprises 10-40% w/w of the builder; preferably the builder is selected from the group consisting of hydratable alkali metal phosphates, carbonates, bicarbonates, zeolites, ethylenediaminetetraacetate, nitrilotriacetate, and mixtures thereof.

6. The detergent bar of any of the preceding claims, which comprises 10-30% w/w of water.

7. The detergent bar of any of the preceding claims, which comprises 0.01-5% w/w of the enzyme-containing granule having a hydrophobic coating.

8. The detergent bar of any of the preceding claims, wherein the hydrophobic coating comprises an oil, fat, wax, or paraffin; such as a vegetable oil or fat.

9. The detergent bar of any of the preceding claims, wherein the hydrophobic coating comprises a vegetable oil or fat, which is a mono-, di- or triglyceride, or a mixture thereof; such as hydrogenated palm oil, hydrogenated palm kernel oil, or hydrogenated soya bean oil.

10. The detergent bar of any of the preceding claims, wherein the hydrophobic coating comprises an oil, fat, wax, or paraffin having a melting point in the range of 30-100°C; preferably in the range of 40-60°C.

11. The detergent bar of any of the preceding claims, wherein the hydrophobic coating comprises 25-80% w/w, preferably 40-80% w/w, of fine particulate matter having an average volume based particle size, Dso, of less than 50 pm; preferably the fine particulate matter comprises talc, kaolin, titanium dioxide, calcium carbonate, calcium sulphate, starch, diatomaceous earth, amorphous silica, bentonite, or mixtures thereof.

12. The detergent bar of any of the preceding claims, wherein the enzyme is selected from the group consisting of protease, amylase, carbohydrase, lipase, nuclease, oxidoreductase, and combinations thereof; preferably the enzyme is protease or amylase.

13. The detergent bar of any of the preceding claims, wherein the granule comprises 0.5-25% w/w of active enzyme protein; preferably 1-20% w/w of active enzyme protein.

14. A method of making the detergent bar of any of the preceding claims, comprising

(a) mixing a surfactant; a builder; water, and enzyme-containing granules having a hydrophobic coating,

(b) milling the mixture, and

(c) extruding the milled mixture.

15. The method of the preceding claim, wherein the surfactant, builder, and water are premixed before adding the enzyme-containing granules having a hydrophobic coating.