Water-soluble film

Abstract

The present invention relates to a water-soluble film comprising a plurality of protrusions on at least a portion of the film, the protrusions extending from or into at least a portion of the surface of the film, where the portion of the water-soluble film comprising the protrusions transmits no more than 30% of light having a wavelength of 350-800 nm.

Description

Technical Field

[0001] The invention relates to a translucent water-soluble film, a translucent water-soluble package and a manufacturing method thereof. Background Art

[0002] Water-soluble films are known for packaging chemical compositions that may be hazardous or irritating, such as detergent compositions. The contents of the package are dissolved or dispersed in the water simply by adding the package to the water.

[0003] In some cases, it is desirable that the packaging be translucent to reduce the visibility of any internal component degradation.

[0004] It is known to provide multi-chamber bags comprising three layers of water-soluble film with a white layer printed on the bottom of the bag to reduce the visibility of the internal components. Notably, this reduces the visibility of discoloration of the formulation (e.g., yellowing of MGDA or degradation of the bleach catalyst). However, this approach requires additional processing steps and increases the complexity of the manufacturing process.

[0005] It is also known to create a white, translucent appearance in water-soluble films by adding colorants and opacifiers, such as dyes and pigments. In some cases, colorants and opacifiers can be hazardous. One example is the addition of TiO2, which is suspected of causing health problems and may require separate disposal procedures.

[0006] It is therefore an object of the present invention to provide a water-soluble film having a translucent appearance without the need for added colorants and opacifiers.

[0007] Furthermore, it is an object of the present invention to provide a method for producing a water-soluble film having a translucent appearance by means of a less complicated manufacturing process.

[0008] Furthermore, it is an object of embodiments of the present invention to provide an improved water-soluble package comprising a water-soluble film having a translucent appearance.

[0009] It is also an object of embodiments of the present invention to overcome at least one problem of the prior art, whether explicitly disclosed herein or not. Summary of the Invention

[0010] According to a first aspect of the present invention, there is provided a water-soluble film comprising a plurality of protrusions on at least a portion of the film, the protrusions extending from or into at least a portion of the film surface, wherein the portion of the water-soluble film comprising the protrusions transmits no more than 30% of light having a wavelength of 350-800 nm.

[0011] In the context of the present invention, the expression "protrusions" may also be understood as meaning a highly irregular surface of the corresponding film.

[0012] The inventors have surprisingly discovered that a water-soluble film having a plurality of protrusions on at least a portion of the film forms a translucent film that transmits no more than 30% of visible light through the portion of the film containing the protrusions. This is believed to be due to the ability of the surface protrusions to scatter light. Advantageously, this means that the inventors have discovered a translucent water-soluble film that does not require the addition of colorants or undesirable opacifiers.

[0013] This allows the film to omit conventional whitening agents, such as titanium oxide, in coatings and / or packaging to mask degradation of encapsulated ingredients and maintain the original aesthetic characteristics of the product.

[0014] The portion of the film containing the protrusions may transmit no more than 25%, 20%, 19%, 18%, 17%, 16%, 15%, 14%, 13%, 12%, 11%, 10%, 9%, 8%, 7%, 6%, 5%, 4%, 3%, 2% or 1% of light having a wavelength of 300-800 nm, 350-800 nm, 400-750 nm or 400-700 nm.

[0015] The portion of the film comprising the protrusions can reflect and / or scatter at least 70, 80%, 85%, 90%, 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98%, or 99% of incident light having a wavelength of 300-800 nm. In some embodiments, the portion of the film comprising the protrusions is opaque or substantially opaque.

[0016] Preferably, the portion of the film surface containing the projections has a white color.

[0017] It is believed that the white color is caused by the reflection and / or scattering of light with a wavelength of 300-800 nm.

[0018] The protrusion may have one or more rounded sides. Preferably, the protrusion may have all rounded sides.

[0019] Preferably, the protrusion is substantially hemispherical, spherical or spherical.

[0020] The projections may cover at least 1%, 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, or 95%. In some embodiments, the projections may be present in an amount not exceeding 99%, 95%, 90%, 85%, 80%, 75%, 70%, 65%, 60%, or 55%. The projections may cover 1 to 100% of the surface of the water-soluble film, or 1-75%, or 1-50% of the surface of at least one side of the water-soluble film.

[0021] The projections may be present on the entire surface of the water-soluble film.

[0022] The protrusions may be present on at least one surface of the water-soluble film. The protrusions may cover both sides of the water-soluble film. In embodiments where the protrusions cover at least one surface of the film, the film will transmit no more than 30% of light having a wavelength of 350-800 nm across the entire film.

[0023] The peak height of one or more protrusions may be less than 2000 nm. The peak height may be at least 100 nm, 200 nm, 300 nm, 400 nm, or at least 500 nm. In some embodiments, the peak height may be no more than 1500 nm, 1250 nm, 1000 nm, 900 nm, 800 nm, or no more than 700 nm. Preferably, the peak height may be between 100 and 1000 nm, between 200 and 1000 nm, between 300 and 900 nm, or between 400 and 800 nm.

[0024] The average diameter of the one or more protrusions may be less than 2000 nm. The average diameter may be at least 100 nm, 200 nm, 300 nm, 400 nm, or at least 500 nm. In some embodiments, the average diameter may be no more than 1500 nm, 1250 nm, 1000 nm, 900 nm, 800 nm, or no more than 700 nm. Preferably, the average diameter may be between 100 and 1000 nm, between 200 and 1000 nm, between 300 and 900 nm, or between 400 and 800 nm.

[0025] The depth of the one or more protrusions may be less than 2000 nm. The depth may be at least 100 nm, 200 nm, 300 nm, 400 nm, or at least 500 nm. In some embodiments, the depth may be no more than 1500 nm, 1250 nm, 1000 nm, 900 nm, 800 nm, or no more than 700 nm. Preferably, the depth may be 100-1000 nm, 200-1000 nm, 300-900 nm, or 400-800 nm.

[0026] The water-soluble film preferably comprises a water-soluble polymer.

[0027] Preferred polymers suitable for use as films (including copolymers, terpolymers or derivatives thereof) are one or more polymers selected from the group consisting of: polyvinyl alcohol (PVA), polyvinyl pyrrolidone, polyalkylene oxide, acrylamide, acrylic acid, cellulose, cellulose ethers, cellulose esters, cellulose amide, polyvinyl acetate, polycarboxylic acids and salts, polyamino acids or peptides, polyamides, polyacrylamides, maleic acid / acrylic acid copolymers, polysaccharides (including starch and gelatin), natural gums (such as xanthan gum and carrageenan). More preferred polymers are selected from polyacrylates and water-soluble acrylate copolymers, methylcellulose, sodium carboxymethylcellulose, dextrin, ethylcellulose, hydroxyethylcellulose, hydroxypropyl methylcellulose, maltodextrin, polymethacrylate, most preferably selected from polyvinyl alcohol, polyvinyl alcohol copolymers and hydroxypropyl methylcellulose (HPMC) and combinations thereof. Preferably, the polymer of the membrane material does not contain carboxylate groups.

[0028] The polymer may be present in an amount of at least 40%, 45%, 50%, 55%, 60%, 65%, 75%, 80%, 85%, 90% or 95% by weight of the film. In some embodiments, the polymer may be present in an amount of no more than 99%, 95%, 90%, 85%, 80%, 75%, 70%, 65%, 60%, 55% or 50% by weight of the film. The water-soluble polymer may be present in an amount of 40 to 99%, 50 to 95%, 50 to 90% or 60 to 90% by weight of the film.

[0029] The polymer can have any weight average molecular weight, preferably from about 1000 to 1,000,000, more preferably from about 10,000 to 300,000, and even more preferably from about 20,000 to 150,000.

[0030] Preferably, the water-soluble film comprises, consists essentially of, or consists of polyvinyl alcohol (PVOH).

[0031] The PVOH film may be partially or completely alcoholized or hydrolyzed, for example, it may be a polyvinyl acetate film that is 40 to 100%, preferably 70 to 92%, and most preferably about 85% to about 92% alcoholized or hydrolyzed. It is known that the degree of hydrolysis affects the temperature at which the PVOH begins to dissolve in water. 88% hydrolysis corresponds to a film that is soluble in cold (i.e., room temperature) water, while 92% hydrolysis corresponds to a film that is soluble in warm water. 88% hydrolysis corresponds to a film that is soluble in cold (i.e., room temperature) water, while 92% hydrolysis corresponds to a film that is soluble in warm water.

[0032] The water-soluble film may comprise a non-solvent.

[0033] The non-solvent can be any liquid that cannot dissolve the water-soluble polymer.

[0034] The non-solvent may be a non-polar solvent.

[0035] The non-solvent may be a glycol ether.

[0036] The glycol ether may be selected from the group consisting of propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate, propylene glycol n-butyl ether, dipropylene glycol n-butyl ether, propylene glycol monophenyl ether, ethylene glycol monobutyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, triethylene glycol monomethyl ether and ethylene glycol monophenyl ether.

[0037] In a preferred embodiment of the present invention, the non-solvent must be less volatile than the solvent (eg, water) and exhibit slower evaporation kinetics in comparison, to allow for (relative) enrichment of the non-solvent in the film.

[0038] Of course, typically, the non-solvent should also not significantly dissolve or plasticize the water-soluble film.The projections may be at least partially filled with the non-solvent.

[0039] The protrusions may be completely filled with the non-solvent.

[0040] The water-soluble film may contain a solvent.

[0041] The solvent can be any liquid that can dissolve the water-soluble polymer.

[0042] Preferably, the solvent is water.

[0043] The thickness of the film may be at least 5, 10, 15, 20, 25, 30, 40, or 50 μm. In some embodiments, the thickness of the film may not exceed 150, 140, 130, 120, 110, 100, 90, 80, 70, 60, or 50 μm. The thickness of the film may be 10 to 150 μm, 20 to 100 μm, 20 to 75 μm, or 20 to 40 μm. Alternatively, the thickness of the film may be 30 to 120 μm, preferably 40 to 110 μm, and more preferably 50 to 100 μm.

[0044] Suitable additives may also be added to the film, such as plasticizers, one or more processing aids, lubricants, antiblocking agents, and colorants.

[0045] The usage amount of plasticizer is generally up to 20 weight %, for example 10 to 20 weight %.The usage amount of lubricant is generally 0.5 to 5 weight %.Therefore, based on the total amount of molding composition, the usage amount of PVOH is generally 75 to 84.5 weight %.Suitable plasticizer is for example pentaerythritol such as dipentaerythritol, sorbitol, mannitol, glycerine and glycols such as glycerine, ethylene glycol and polyethylene glycol.Solids such as talcum, stearic acid, magnesium stearate, silicon dioxide, zinc stearate or colloidal silicon dioxide can be used as lubricants.Suitable processing aid includes mono, di, tricarboxylic acid / its salt, fatty acid (such as stearic acid) / its salt, mono, di or triglyceride / its salt, fumed silica and inorganic and organic pigment.Antiblocking agent can also be present in the film.Suitable antiblocking agent includes silicon dioxide, talcum, zeolite and starch.

[0046] According to a second aspect of the present invention, there is provided a method for producing the water-soluble film of the first aspect of the present invention, the method comprising the following steps:

[0047] a) providing a substrate;

[0048] b) preparing a polymer solution comprising a water-soluble polymer, a solvent, and a non-solvent;

[0049] c) depositing the solution on the substrate; and

[0050] d) drying the solution to form a water-soluble film comprising a plurality of protrusions on at least a portion of the film, the protrusions extending from or into at least a portion of the film surface, wherein the portion of the water-soluble film comprising the protrusions transmits no more than 30% of light having a wavelength of 350-800 nm.

[0051] The present invention provides a simpler method for producing translucent water-soluble films, which allows the formation of translucent water-soluble films without substantial modification of existing manufacturing processes (such as solution casting or cast extrusion, preferably solution casting).

[0052] The water-soluble polymer may be present in an amount of at least 0.5%, 1%, 1.2%, 1.4%, 1.6%, 1.8%, 2%, 2.2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, or 6% by weight of the polymer solution. In some embodiments, the water-soluble polymer may be present in an amount of no more than 10%, 9.5%, 9%, 8.5%, 8%, 7.5%, 7%, 6.5%, or 6%, 5.5%, 5%, 4.5%, 4%, 3.5%, 3%, 2.5%, or 2% by weight of the polymer solution.

[0053] The water-soluble polymer may be present in an amount of 0.5 to 10%, 1 to 10%, 1.5 to 10%, 1.75 to 10%, or 1-2% by weight of the polymer solution.

[0054] The non-solvent may be present in an amount of at least 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 1.2%, 1.4%, 1.6%, 1.8%, or 2% by weight of the polymer solution. In some embodiments, the non-solvent may be present in an amount of no more than 3%, 2.9%, 2.8%, 2.7%, 2.6%, 2.5%, 2.4%, 2.3%, 2.2%, 2.1%, or 2% by weight of the polymer solution.

[0055] The non-solvent may be present in an amount of 0.2 to 3 weight percent, 0.2 to 1 weight percent, or 1 to 3 weight percent of the polymer solution.

[0056] The inventors found that non-solvents added in an amount greater than 3% could not form a dry film after drying for one week under ambient conditions.

[0057] The inventors also found that low amounts of non-solvent, less than 0.2%, could not form a film with the desired protrusions.

[0058] The solvent may be present in an amount of at least 80%, 85%, 90%, 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98%, 99%, 99.1%, 99.2%, 99.3%, 99.4%, 99.5%, 99.6%, 99.7%, 99.8%, or 99.9% by weight of the polymer solution. In some embodiments, the solvent may be present in an amount of no more than 99.9%, 99.8%, 99.7%, 99.6%, 99.5%, 99.4%, 99.3%, 99.2%, 99.1%, 99%, 98%, 97%, 96%, 95%, or 90% by weight of the polymer solution.

[0059] The solvent may be present in an amount of 80 to 99.9%, 85 to 99.9%, 90 to 99.9%, 95 to 99.9%, 98 to 99.9%, 99 to 99.9% by weight of the polymer solution.

[0060] Including smaller amounts of solvent will shorten the drying time of the film.

[0061] The weight ratio of solvent to nonsolvent in the polymer solution may be at least 30: 1, 50: 1, 100: 1, or 200: 1. In some embodiments, the weight ratio of solvent to nonsolvent in the polymer solution may not exceed 500: 1, 400: 1, 300: 1, 200: 1, 100: 1, or 50: 1.

[0062] The weight ratio of solvent to non-solvent in the polymer solution may be from 30:1 to 500:1.

[0063] The weight ratio of the water-soluble polymer to the non-solvent in the polymer solution may be at least 5: 1, 3: 1, 2: 1, or 1: 1. In some embodiments, the weight ratio of the water-soluble polymer to the non-solvent in the polymer solution may not exceed 10: 1, 9: 1, 8: 1, 7: 1, 6: 1, 5: 1, 4: 1, 3: 1, or 2: 1.

[0064] The weight ratio of the water-soluble polymer to the non-solvent in the polymer solution may be 1:1 to 10:1, or 1:1 to 8:1, 1:1 to 6:1, or 1:1 to 5:1.

[0065] The substrate may be any suitable material that can serve as a casting surface.

[0066] The substrate can be metal, glass or a polymer material.

[0067] The substrate may be silicon or a silicon derivative.

[0068] The metal can be any metal that can serve as a casting surface, such as nickel, aluminum, and silver.

[0069] The polymeric material may be any polymeric material that can serve as a casting surface, such as polyethylene terephthalate (PET), polyethylene, polytetrafluoroethylene, polypropylene, thermosets, polyvinyl chloride, polytetrafluoroethylene, polycarbonate, cyclic olefin copolymers or poly(methyl methacrylate) and polyamides.

[0070] In a third aspect of the present invention, a water-soluble package comprising the water-soluble film of the present invention is provided. The water-soluble film can be produced using the method of the second aspect of the present invention.

[0071] At least a portion of the water-soluble package may be translucent, and in some embodiments, the entire water-soluble package may be translucent.

[0072] Advantageously, the use of the water-soluble film of the first aspect of the invention in water-soluble packaging can mask the degradation of any encapsulated ingredients. This can preserve the original aesthetic appearance of the packaging.

[0073] The water-soluble packaging may be a detergent packaging.

[0074] The water-soluble package may be a detergent package having one or more compartments.

[0075] The detergent package may be a multi-compartment package.

[0076] The projections of the water-soluble film may be located on areas of the film which constitute one or more compartments. Preferably, the projections will be present on more than one compartment, more preferably on all compartments.

[0077] The detergent package may comprise a flange or rim.

[0078] The protrusions may be located on areas of the film that form the flange or rim of the detergent package.

[0079] In one embodiment, the protrusions may be present only on one or more compartments of the detergent package.

[0080] Alternatively, the protrusions may be present only on the flange or edge of the detergent package.

[0081] Still as an alternative, the protrusions may be present on one or more compartments and the flange or edge. More preferably, the protrusions may be present on the flange or edge and all compartments.

[0082] In a fourth aspect of the present invention, there is provided a water-soluble package according to the third aspect of the present invention containing the composition.

[0083] In a fifth aspect of the present invention, there is provided a method for preparing the water-soluble package of the third aspect of the present invention, the method comprising:

[0084] a) thermoforming a first film of the present invention to produce at least one bag;

[0085] b) at least partially filling the or each bag with the composition; and

[0086] c) placing a second film, preferably a polyvinyl alcohol film, on top of the or each filled bag; and

[0087] d) sealing the first film and the second film together.

[0088] In some embodiments, the second film is also a film of the present invention.

[0089] The bag may comprise a flange or rim, and the second film may be sealed to the first film at least at the flange or rim.

[0090] The composition may be placed in the bag in step b) and the second film placed over the flange or rim and across the bag.

[0091] Step a) may comprise thermoforming more than one bag in the film, for example two, three or four bags. Each bag may be filled with a different composition, the same composition or any combination of compositions.

[0092] In step b), the or each bag may be completely filled with the composition. Partial filling of each bag may reduce the risk of rupture of the package if it is subjected to impact and may reduce the risk of leakage if it is subjected to high temperatures.

[0093] In step d), the films are sealed together, for example, by heat sealing across the flange or edge. Suitable heat sealing temperatures are, for example, 120°C to 195°C, for example, 140°C to 190°C. Suitable sealing pressures are, for example, 250 to 800 kPa. Depending on the heat sealer used, examples of sealing pressures are 276 to 552 kPa (40 to 80 psi), especially 345 to 483 kPa (50 to 70 psi) or 400 to 800 kPa (58 to 116 psi), especially 500 to 700 kPa (72.5 to 101.5 psi). Suitable sealing dwell times are at least 0.4 seconds, for example, 0.4 to 2.5 seconds. Other methods of sealing the films together can be used, for example, infrared, radio frequency, ultrasonic, laser, solvent, vibration, electromagnetic, hot air, hot plate, insert bonding, segmented sealing, or spin welding. Adhesives can also be used, for example, aqueous solutions of water or polyvinyl alcohol. The adhesive may be applied to the membrane by spraying, transfer coating, roller coating or other application, or the membrane may be sprayed with the adhesive. The sealant is also desirably water soluble.

[0094] The thickness of the first film of the present invention prior to thermoforming can typically be 20 to 500 μm, particularly 50 to 400 μm, for example 70 to 300 μm, most preferably 70 to 160 μm, and particularly 80 to 150 μm. The thickness of the second film can be less than that of the first film, as the second film is typically not thermoformed, so localized thinning of the film does not occur. The thickness of the second film can typically be 20 to 150 μm, preferably 40 to 90 or 100 μm, and more preferably 30 to 90 μm. However, films with a thickness of 70 to 150 μm can also be used.

[0095] The composition for filling the package is not particularly limited and can be any composition to be added to an aqueous system or used in an aqueous environment.

[0096] The composition may be a dishwashing composition, a water-softening composition, a laundry composition, a hard surface cleaning composition, a concentrated cleaning composition, a dilutable cleaning composition or a detergent composition or a rinse aid. In this case, it is particularly suitable for use in domestic washing machines, such as laundry washing machines, or in particular in dishwashing machines, including automatic dishwashing machines.

[0097] The properties of the composition in each bag are not limited. For example, each bag can be independently solid, liquid or gel. If it is in solid form, it can be, for example, in the form of a powder, granules, extruded tablets, compressed tablets or solidified gel. If it is in liquid form, it can optionally be thickened or gelled with a thickener or gelling agent. One or more phases can be present. For example, each bag can be independently filled with a liquid composition, an independent solid composition (for example, in the form of balls, pills, granules or spots) and an independent gel composition. Alternatively, two or more solid phases can be present, or two or more immiscible liquid phases can be present.

[0098] Therefore, the composition in each bag does not need to be consistent. For example, during the manufacturing process, at least one bag can be first filled with a curable composition (e.g., a gel) and then filled with a different composition (e.g., a liquid, particularly an aqueous composition), or these compositions can be filled in separate bags. The first composition can dissolve slowly (e.g., during the wash process) to provide long-term delivery of its contents. This can be helpful, for example, to provide immediate, delayed, or sustained delivery of components such as softeners.

[0099] If more than one package is formed simultaneously, the packaged compositions can be separated from one another subsequently.

[0100] Alternatively, they may remain connected and, for example, be provided with perforations between the individual packages so that they can be easily separated at a later stage, for example by the consumer or during further processing of the packages.

[0101] If the package is separated, the flange can remain in place. However, it may be desirable to partially remove the flange to provide a more attractive three-dimensional appearance. Generally, for aesthetic purposes, the remaining flange should be as small as possible, while also considering that some flange is required to ensure that the two films remain adhered to each other. Desirably, the flange is 0.1 mm to 5 mm, preferably 0.5 mm to 4 mm, more preferably 1 mm to 3 mm, and most preferably about 2 mm.

[0102] The package can then be left to absorb moisture from the atmosphere, or can be immediately packaged into boxes for retail sale. If desired, the package itself can be wrapped in an outer packaging, such as a non-water-soluble outer packaging material that is removed before using the water-soluble packaging.

[0103] Depending on its intended use, the package of the present invention generally contains 5 to 100 g of a composition, for example an aqueous composition, in particular 5 to 40 g. For example, a dishwashing composition may weigh 8 to 30 g, a water softening composition may weigh 10 to 30 g, a laundry composition may weigh 10 to 40 g, in particular 10 to 30 g.

[0104] The bag can have any shape. For example, it can take the form of an envelope, a sachet, a sphere, a hemisphere, a segment of a sphere, a cylinder, a cube (including a cube with rounded corners), or a cuboid (including a cuboid with rounded corners), i.e., a rectangular parallelepiped whose faces are not all equal; or an irregular shape. Typically, because the package is not rigid and expands, the sides are not flat but convex. If the package is formed from a thermoformed film and a flat film, the seam between the two films will appear closer to one side of the package than to the other. In addition to deformation of the package due to shrinkage of the polyvinyl alcohol film after manufacture, deformation can also occur during the manufacturing stage if necessary. For example, if the bag is filled with a solid or gel composition (e.g., in tablet form) that is taller than the bag, deformation will occur when the second film is placed on top of the bag.

[0105] Typically, the maximum dimensions of the filled portion (bag) of the package (excluding any flange) are 10 cm x 10 cm, preferably 8 cm x 8 cm. For laundry detergent compositions, the maximum dimensions of the filled portion of the package are preferably 8 cm x 8 cm, while for automatic dishwashing detergent compositions the maximum dimensions may be smaller, for example not exceeding 6 cm x 6 cm.

[0106] The composition may contain a surfactant, such as an anionic, nonionic, cationic, amphoteric or zwitterionic surfactant, or a mixture thereof.

[0107] The dishwashing composition may include a detergent builder. The builder is preferably a phosphate-free builder. The builder may include one or more small molecule builders selected from hydroxycarboxylates (e.g., citrates, such as trisodium citrate, which may be anhydrous), aminocarboxylates (e.g., methylglycine diacetic acid (MGDA) or N,N-dicarboxymethylglutamic acid (GLDA)), dicarboxylic acid amines (e.g., iminodisuccinic acid (IDS)), and / or phosphates (e.g., tripolyphosphates) or salts thereof.

[0108] The compositions, particularly when used as laundry or dishwashing compositions, may also contain enzymes such as proteases, lipases, amylases, cellulases and peroxidases.

[0109] If desired, the composition may contain a thickening or gelling agent.

[0110] The composition can also comprise one or more additional ingredients optionally.These additional ingredients comprise conventional detergent composition components, for example other surfactant, bleaching agent, bleach activator, bleach catalyst, bleach enhancer, auxiliary agent, foaming agent or foam suppressor, rust inhibitor and anticorrosive, organic solvent, cosolvent, phase stabilizer, emulsifying agent, preservative, soil suspending agent (soil suspending agent), soil release agent, bactericide, pH adjusting agent or buffer, non-auxiliary alkaline source, chelating agent, clay (for example montmorillonite clay), enzyme stabilizer, anti-scalant (anti-limescale agent), coloring agent, dye, hydrotrope, dye transfer inhibitor, brightening agent and spices.If used, then this type of optional ingredient accounts for no more than 10 weight % of the composition gross weight conventionally, for example 1 to 6 weight %.

[0111] The composition comprising the enzyme may optionally contain materials that maintain enzyme stability. Such enzyme stabilizers include, for example, polyols (e.g., propylene glycol), boric acid, and borax. Combinations of these enzyme stabilizers can also be used. If used, the enzyme stabilizer typically accounts for 0.1 to 1% by weight of the composition.

[0112] The composition may optionally contain a component that adjusts or maintains the pH of the composition at an optimal level. Examples of pH adjusters are NaOH and citric acid. Depending on the nature of the composition, the pH may be, for example, 1 to 13, such as 8 to 11. For example, dishwashing compositions desirably have a pH of 8 to 11, laundry compositions desirably have a pH of 7 to 9, and water softening compositions desirably have a pH of 7 to 9.

[0113] Preferably, the composition is an automatic dishwashing composition.

[0114] In another aspect of the invention there is provided an enzyme granule coated with the membrane of the first aspect of the invention.

[0115] The enzyme may be a protease, lipase, amylase, cellulase and / or peroxidase.

[0116] In another aspect of the present invention there is provided a bleach catalyst co-particle coated with a membrane according to the first aspect of the present invention.

[0117] The bleach catalyst co-particle may be a manganese bleach catalyst or a co-particle of a bleach catalyst with a bleach booster or other builder.

[0118] In another aspect of the present invention, there is provided the use of a water-soluble film of the present invention for packaging a detergent or laundry composition, which may be as described above.

[0119] In another aspect of the present invention, there is provided a use of the water-soluble film of the present invention in a coating. The coating may be a coating for an enzyme granule or a bleach catalyst co-granule as described above.

[0120] Another aspect of the invention may combine any features of the other aspects of the invention described herein as necessary or appropriate. DETAILED DESCRIPTION

[0121] In order that the present invention may be more clearly understood, one or more embodiments of the present invention will now be described, by way of example only, with reference to the accompanying drawings, in which:

[0122] Figure 1 A-1D shows Example 4 ( Figure 1 A) and Example 5 ( Figure 1 B) of the present invention and the water-soluble film of Reference Example 6 ( Figure 1 C) and Reference Example 7 ( Figure 1 D) is an image of a water-soluble film not according to the invention.

[0123] Figure 2 A-2B shows an optical microscope image (Keyence VHX-7000, including VHX-E100 lens) of the film of the present invention described in Example 1. Figure 2 A) and 3D images ( Figure 2 B).

[0124] Figure 3 A-3D is the water-soluble film of the present invention described in Example 1 at 840 times magnification ( Figure 3 A) and 4900x magnification ( Figure 3 B) Scanning electron microscope image (Phenom TM ProX desktop scanning electron microscope) and the non-inventive water-soluble film described in Reference Example 8 at 840 times magnification ( Figure 3 C) and 4900x magnification ( Figure 3 D) Scanning electron microscope image (Phenom TM ProX desktop scanning electron microscope).

[0125] Figure 4 A-4C is a graph showing the water-soluble film of the present invention described in Example 4 before the film surface is contacted with a non-solvent ( Figure 4 A) After the membrane surface contacts the non-solvent ( Figure 4 B) and non-solvent from Figure 4 After evaporation of B in the film ( Figure 4 C) Image of translucency differences.

[0126] Example 1

[0127] 0.3 g polyvinyl alcohol water-soluble polymer (Solublon GA 90) was dissolved in 49.6 g deionized water solvent and 0.1 g propylene glycol phenyl ether non-solvent (Dowanol TM PPH) to form a polymer solution. The polymer solution contains 99.2% solvent, 0.2% non-solvent and 0.6% water-soluble polymer by weight of the polymer solution. The polymer solution is then deposited in a 3500 mL glass crystallization dish and allowed to stand for 24 hours under environmental conditions of 21°C and 34% relative humidity to form a translucent water-soluble film with protrusions and a thickness of 30 μm. Figure 2 As shown in A-2B and 3A-3B, the surface structure comprises a plurality of spherical protrusions filled with a non-solvent.

[0128] Example 2

[0129] 0.3 g polyvinyl alcohol water-soluble polymer (Solublon GA 90) was dissolved in 24.8 g deionized water solvent and 0.1 g propylene glycol phenyl ether non-solvent (Dowanol TM A polymer solution was formed by adding a solvent (98.4%) to a mixture of polyvinylpyrrolidone (PPH) and polyvinylpyrrolidone (PVP). The polymer solution comprised 98.4% solvent, 0.4% non-solvent, and 1.2% water-soluble polymer by weight. The polymer solution was then deposited into a 3500 mL glass crystallizing dish and allowed to stand for 24 hours at 21°C and 34% relative humidity to form a translucent, water-soluble film with protrusions. The surface structure consisted of numerous spherical protrusions filled with non-solvent.

[0130] Example 3

[0131] 0.3 g polyvinyl alcohol water-soluble polymer (Solublon GA 90) was dissolved in 2.96 g deionized water solvent and 0.1 g propylene glycol phenyl ether non-solvent (Dowanol TM A polymer solution was formed by adding a solvent (88.1%) to a mixture of polyvinylpyrrolidone (PPH) and polyvinylpyrrolidone (PVP). The polymer solution comprised 88.1% solvent, 2.98% non-solvent, and 8.9% water-soluble polymer by weight. The polymer solution was then deposited into a 3500 mL glass crystallizing dish and allowed to stand for 24 hours at 21°C and 34% relative humidity to form a translucent, water-soluble film with protrusions. The surface structure consisted of numerous spherical protrusions filled with non-solvent.

[0132] Example 4

[0133] 0.3 g polyvinyl alcohol water-soluble polymer (Solublon GA 90) was dissolved in 15 g deionized water solvent and 0.1 g propylene glycol phenyl ether non-solvent (Dowanol TM The polymer solution was deposited in a 3500 mL glass crystallizing dish and allowed to stand for 24 hours at 21°C and 34% relative humidity to form a translucent water-soluble film with protrusions, as shown in FIG. Figure 1 As shown in A. The surface structure consists of multiple spherical protrusions filled with non-solvent.

[0134] Example 5

[0135] 0.3 g polyvinyl alcohol water-soluble polymer (Solublon GA 90) was dissolved in 15 g deionized water solvent and 0.3 g propylene glycol phenyl ether non-solvent (Dowanol TM The polymer solution was deposited in a 3500 mL glass crystallizing dish and allowed to stand for 24 hours at 21°C and 34% relative humidity to form a translucent water-soluble film having protrusions, such as Figure 1 As shown in B, the surface structure consists of multiple spherical protrusions filled with non-solvent.

[0136] Reference Example 6

[0137] 0.3 g polyvinyl alcohol water-soluble polymer (Solublon GA 90) was dissolved in 15 g deionized water solvent and 0.5 g propylene glycol phenyl ether non-solvent (Dowanol TM The polymer solution was then deposited into a 3500 mL glass crystallizing dish and allowed to stand for 24 hours at 21°C and 34% relative humidity. After 24 hours, the composition remained wet due to the increased amount of non-solvent present, and thus was unable to form a water-soluble film. Figure 1 As shown in C.

[0138] Reference Example 7

[0139] 0.3 g polyvinyl alcohol water-soluble polymer (Solublon GA 90) was dissolved in 15 g deionized water solvent and 0.03 g propylene glycol phenyl ether non-solvent (DowanolTM The polymer solution was deposited in a 3500 mL glass crystallizing dish and allowed to stand for 24 hours under ambient conditions of 21°C and 34% relative humidity to form a transparent water-soluble film, as shown in FIG. Figure 1 D. This water-soluble film does not contain a plurality of protrusions on the surface of the film. This is believed to be due to the low amount of non-solvent present during the manufacturing process.

[0140] Reference Example 8

[0141] 0.3 g of polyvinyl alcohol water-soluble polymer (Solublon GA 90) was dissolved in 15 g of deionized water solvent to form a polymer solution. The polymer solution was then deposited in a 3500 mL glass crystallization dish and allowed to stand for 24 hours under environmental conditions of 21°C and 34% relative humidity to form a transparent water-soluble film. The water-soluble film did not contain a plurality of protrusions on the surface of the film, such as Figure 3 As shown in C and 3D.

[0142] Example 9

[0143] Water-soluble packaging with protrusions on the film surface is prepared according to the method of the present invention. A first PVOH film having protrusions on the film surface is thermoformed to produce a pouch, which is then filled with a detergent composition. A second PVOH film is then placed on top of the filled pouch. A hot plate is pressed against the first film at 165°C for 2 seconds to seal the first and second films, thereby forming a translucent water-soluble package.

[0144] Optical analysis

[0145] A METROHM 662 photometer was used to measure the translucency of the films of Example 4 and Reference Example 8. Five measurements were recorded at wavelengths of 500 μm and 700 μm, and the average light transmission is shown in Table 1 below.

[0146]

[0147] As shown in the table, the film of the present invention reflects and / or scatters a significant amount of incident light. In contrast, the reference example does not reflect and / or scatter a significant amount of incident light. This is due to the protrusions formed on the surface of the film of the present invention.

[0148] like Figure 2 As shown, the surface of the film of Example 1 was analyzed under an optical microscope, and spherical protrusions were found on the surface.

[0149] Without being bound by theory, it is believed that the spherical protrusions are due to the inclusion of solvent on the membrane surface.

[0150] As a result, the protrusions are filled with non-solvent.

[0151] The surface of Example 1 was analyzed under a scanning electron microscope. Figure 1 A-1B shows what appear to be numerous cracked protrusions. This is believed to be due to the high vacuum conditions used in SEM sample preparation or the gold sputtering process. However, the presence of these cracked protrusions provides evidence of the presence of multiple protrusions on the film surface.

[0152] Methods for determining whether surface scattering is caused by surface structure

[0153] To prove that the translucency of the film was due to surface protrusions rather than the inherent bulk of the water-soluble film, a drop of propylene glycol phenyl ether nonsolvent (Dowanol TM A PPH (Polypropylene glycol) was placed on the surface of the film of Example 4. Upon contact with the non-solvent, the film changed from translucent, as shown in FIG5A , to transparent, as shown in FIG5B . This is believed to be due to the addition of the non-solvent destroying the surface protrusions. Subsequently, after the non-solvent dried and evaporated, the film's original translucency was restored. This is believed to be due to the reformation of the surface protrusions.

[0154] One or more embodiments have been described above by way of example only. Numerous changes may be made without departing from the scope of protection provided by the appended claims.

Claims

1. A water-soluble film comprising a plurality of protrusions on at least a portion of the film, the protrusions extending from or into at least a portion of the film surface, wherein the portion of the water-soluble film comprising the protrusions transmits no more than 30% of light having a wavelength of 350-800 nm.

2. The film according to claim 1, wherein The protrusion is substantially hemispherical, spherical or spherical.

3. The film according to claim 1 or 2, wherein The protrusions extend over at least 50% of the surface of the film; preferably, the protrusions extend over 100% of the surface of the film.

4. A membrane according to any one of the preceding claims, wherein The average diameter of the protrusions is less than 1000 nm.

5. A membrane according to any one of the preceding claims, wherein The film comprises a water-soluble polymer; wherein preferably, the water-soluble polymer is PVA.

6. A membrane according to any one of the preceding claims, wherein The film comprises a solvent; wherein preferably, the solvent is water.

7. A membrane according to any one of the preceding claims, wherein The film comprises a non-solvent; wherein preferably, the non-solvent is a glycol ether.

8. A membrane according to any one of the preceding claims, wherein The projections are at least partially filled with a non-solvent.

9. The method for producing a water-soluble film according to any one of claims 1 to 8, comprising the steps of: a) providing a substrate; b) preparing a polymer solution comprising a water-soluble polymer, a solvent, and a non-solvent; c) depositing the solution on the substrate; as well as d) drying the solution to form a water-soluble film comprising a plurality of protrusions on at least a portion of the film, the protrusions extending from or into at least a portion of the film surface, wherein the portion of the water-soluble film comprising the protrusions transmits no more than 30% of light having a wavelength of 350-800 nm.

10. The method according to claim 9, wherein: The water-soluble polymer is present in an amount of 0.5% to 10% by weight of the polymer solution.

11. The method according to claim 9 or 10, wherein: The non-solvent is present in an amount of 0.2% to 3% by weight of the polymer solution.

12. The method according to any one of the preceding claims 9 to 11, wherein The solvent is present in an amount of 80% to 99.9% by weight of the polymer solution.

13. A water-soluble package comprising the water-soluble film according to any one of claims 1 to 8; wherein preferably, the package is a detergent package.

14. The package according to claim 13, wherein The package is a multi-compartment package; wherein preferably, the protrusion is located on more than one compartment of the multi-compartment package.

15. Use of a water soluble film as claimed in any one of claims 1 to 8 for packaging detergent or laundry compositions, or as a coating for granules or bleach catalyst co-granules.

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