Water-soluble unit dose articles

Abstract

The present disclosure relates to water soluble unit dose articles. Water soluble unit dose articles comprising fabric care or home care detergent compositions and methods of making the same.

Description

Technical Field

[0001] Water-soluble unit-dose detergent products and their preparation methods. Background Technology

[0002] Water-soluble unit-dose detergent products are widely used in automatic dishwashing and laundry, especially those made from water-soluble films containing polyvinyl alcohol. Film-encapsulated detergent: The water-soluble unit-dose detergent product is added to water and the film dissolves, releasing the detergent.

[0003] Rapid dissolution of detergent products is highly desirable; however, in some cases, the interaction between the detergent and polyvinyl alcohol during initial dissolution and contact with water can cause gelation, which slows further dissolution, leading to a delay in the start of cleaning and, in some cases, leaving residue on the treated items. This is more pronounced when the cleaning process is carried out in short, cold cleaning cycles. When water-soluble unit-dose detergent products are used in the laundry process, residues may deposit on the fabric or the washing machine. Residues can be redissolved, but may require further steps by the user. Therefore, an object of the present invention is to provide unit-dose detergent products with improved dissolution. Another object of the present invention is to provide unit-dose detergent products with improved dissolution in short, cold washing cycles. Summary of the Invention

[0004] A first aspect of the present invention is a water-soluble unit-dose article. The water-soluble unit-dose article comprises a water-soluble film and a detergent composition. The detergent composition is encapsulated by the water-soluble film. The detergent composition includes a surfactant, and the water-soluble film includes a first film. The first film comprises a polyvinyl alcohol polymer blend, wherein the polyvinyl alcohol polymer blend comprises:

[0005] i) 1% to 30%, preferably 5% to 25%, more preferably 10% to 20% of polymer A by weight of the polymer blend, wherein polymer A comprises anionic monomer units, vinyl alcohol monomer units and vinyl acetate monomer units, and wherein the anionic monomer units comprise monomers derived from itaconic acid, itaconic acid monoalkyl ester, itaconic acid dialkyl ester, itaconic anhydride and mixtures thereof, preferably itaconic acid, itaconic acid monomethyl ester, itaconic acid dimethyl ester, itaconic anhydride and mixtures thereof, more preferably monomers of the group consisting of itaconic acid;

[0006] Polymer A has

[0007] An average degree of hydrolysis of 60% to less than 80%, preferably 70% to less than 80%, more preferably 75% to less than 80%; and

[0008] A 4% solution viscosity at 20°C of 3 cP to 20 cP, preferably 3 cP to 15 cP, more preferably 3 cP to 10 cP; and

[0009] ii) 70% to 99%, preferably 75% to 95%, more preferably 80% to 90% of polymer B by weight of the polymer blend, wherein polymer B is substantially composed of vinyl alcohol monomer units and vinyl acetate monomer units.

[0010] Polymer B has

[0011] An average degree of hydrolysis of 70% to less than 80%, preferably 72% to less than 80%, more preferably 75% to less than 80%; and

[0012] A 4% solution viscosity at 20°C of 10 cP to 40 cP, preferably 10 cP to 30 cP, and more preferably 10 cP to 20 cP.

[0013] A second aspect of the present invention is a method for manufacturing the water-soluble unit-dosage detergent article of the present invention, the method comprising the following steps:

[0014] i) Thermoforming and / or vacuum forming of the film to create a cavity;

[0015] ii) Filling the cavity with a detergent composition or a portion thereof; and

[0016] iii) To close the cavity with another membrane and / or a pre-formed compartment containing a detergent composition or a portion thereof to produce a single-compartment or multi-compartment water-soluble unit dose detergent article. Attached Figure Description

[0017] Figure 1 It is a water-soluble unit dose product according to the present invention.

[0018] Figure 2 The setup for measuring the gelling factor G is described.

[0019] Figure 3 A schematic diagram of the basic configuration for a small bag strength test is shown. Detailed Implementation

[0020] As used herein, when used in claims or the specification, the articles including “the,” “an,” and “a” are understood to refer to one or more substances protected or described in the claims.

[0021] As used herein, the term "including" is intended to be non-restrictive.

[0022] Unless otherwise specified, all percentages, ratios, and proportions used herein are by weight percentage of the composition. Unless otherwise expressly stated, all average values ​​are by weight of the composition.

[0023] Unless otherwise specified, all measurements were performed at 25°C.

[0024] Unless otherwise specified, all component or composition levels refer to the active portion of the component or composition and do not include impurities, such as residual solvents or byproducts, that may be present in commercially available sources of such components or compositions.

[0025] Water-soluble unit dose products

[0026] A first aspect of the invention is a water-soluble unit-dose detergent article. The water-soluble unit-dose detergent article includes at least one compartment and a fabric care product (preferably a laundry detergent composition) or a household care product (preferably an automatic dishwashing detergent composition). The detergent composition is encapsulated by a water-soluble film. The detergent composition is described in more detail below. The water-soluble unit-dose article may include one or more compartments. It includes a first water-soluble film and optionally a second and a third water-soluble film. The first, second, and third water-soluble films are described in more detail below.

[0027] In cases where a water-soluble unit-dose detergent article comprises at least two compartments, the article includes a water-soluble membrane shaped such that the unit-dose article comprises at least two internal compartments surrounded by the water-soluble membrane. The water-soluble unit-dose detergent article is configured such that the detergent composition (preferably laundry detergent or automatic dishwashing) does not leak out of the compartments during storage. However, when the water-soluble unit-dose detergent article is added to water, the water-soluble membrane dissolves, releasing the contents of the internal compartments into the washing liquid.

[0028] The compartment should be understood to mean an enclosed internal space within a unit dose of the product, which holds the detergent composition, preferably a laundry detergent composition or an automatic dishwashing detergent composition.

[0029] The first water-soluble membrane has a first side and a second side. If present, the second water-soluble membrane has a first side and a second side. If present, the third water-soluble membrane has a first side and a second side.

[0030] In the case of a water-soluble unit-dose detergent product comprising only a single compartment, a first side of a first water-soluble membrane is sealed to a second side of a second water-soluble membrane to create a single compartment between the first and second water-soluble membranes.

[0031] In the case of a water-soluble unit dose article comprising at least two compartments arranged side by side, a first side of a first water-soluble membrane is sealed to a second side of a second water-soluble membrane to create at least two compartments between the first water-soluble membrane and the second water-soluble membrane.

[0032] In the case of a water-soluble unit-dose detergent article comprising at least two compartments in an overlapping configuration, a first side of a first water-soluble film is sealed to a second side of a second water-soluble film to create at least a first compartment between the first and second water-soluble films, and a first side of the second water-soluble film is sealed to a second side of a third water-soluble film to create at least a second compartment between the second and third water-soluble films, and the at least second compartment is preferably positioned above the at least first compartment.

[0033] Preferably, the first and second water-soluble membranes are sealed by solvent sealing, heat sealing, or a mixture thereof, preferably by solvent sealing. More preferably, the solvent sealing solution comprises an aqueous solvent, a non-aqueous solvent, or a mixture thereof. Even more preferably, the solvent sealing solution comprises water. Preferably, the solvent sealing solution comprises at least 95%, or even at least 98%, or even at least 99%, or even 100% water by weight of the solvent sealing solution. The solvent sealing solution can be applied to the membrane by any suitable method, including contact and / or non-contact methods. For example, the solvent solution can be applied during contact transfer, for example using contact members comprising non-absorbent or substantially impermeable materials, such as using an anilox roller, a rubber (e.g., EPDM) roller, or any combination thereof, optionally in combination with a doctor blade. The sealing solution can be applied using a doctor blade, Mayer's blade, or similar device. The sealing solution can be applied using contact members comprising absorbent materials, such as natural felt, synthetic felt, porous plastics, foam, sponge, microfiber, cotton, polyester, extruded polyester fibers, nonwoven webs, etc., for example in the form of a pad or roller. The sealing solution can be applied via a metering nozzle or a spray nozzle. Combinations of any of the foregoing methods and apparatus can be considered. Preferably, the solvent sealing solution is applied via a felt roller, via a metering nozzle, via a spray nozzle, or a combination thereof; more preferably via a felt roller; and alternatively via a spray nozzle. Preferably, the solvent sealing solution is applied to a second side of a second water-soluble membrane, the second side of the second water-soluble membrane facing the first side of the first water-soluble membrane.

[0034] Preferably, the second and third water-soluble membranes are sealed by solvent sealing, heat sealing, or a mixture thereof, preferably by solvent sealing. More preferably, the solvent sealing solution comprises an aqueous solvent, a non-aqueous solvent, or a mixture thereof. Even more preferably, the solvent sealing solution comprises water. Preferably, the solvent sealing solution comprises at least 95%, or even at least 98%, or even at least 99%, or even 100% water by weight of the solvent sealing solution. The solvent sealing solution can be applied to the membrane by any suitable method, including contact and / or non-contact methods. For example, the solvent solution can be applied during contact transfer, for example using contact members comprising non-absorbent or substantially impermeable materials, such as using an anilox roller, a rubber (e.g., EPDM) roller, or any combination thereof, optionally in combination with a doctor blade. The sealing solution can be applied using a doctor blade, Mayer's blade, or similar device. The sealing solution can be applied using contact members comprising absorbent materials, such as natural felt, synthetic felt, porous plastics, foam, sponge, microfiber, cotton, polyester, extruded polyester fibers, nonwovens, etc., for example in the form of a pad or roller. The sealing solution can be applied via a metering nozzle or a spray nozzle. Combinations of any of the foregoing methods and apparatus can be considered. Preferably, the solvent sealing solution is applied via a felt roller, via a metering nozzle or a spray nozzle, or a combination thereof; more preferably via a felt roller; and alternatively via a spray nozzle. Preferably, the solvent sealing solution is applied to a first side of a second water-soluble membrane, the first side of the second water-soluble membrane facing the second side of a third water-soluble membrane.

[0035] Preferably, the unit dose article includes at least a third compartment between the second and third water-soluble films, preferably at least a third compartment and a fourth compartment. Preferably, the second and third compartments, or the second, third, and fourth compartments, are positioned side-by-side, and the second and third compartments, or the second, third, and fourth compartments, are positioned above the first compartment. Preferably, the second and third compartments, or the second, third, and fourth compartments, are smaller than the first compartment. The second and third compartments, or the second, third, and fourth compartments, may have the same size or may have different sizes. Some of the compartments may have the same size, and some may have different sizes.

[0036] The detergent composition according to the invention may be contained in at least one compartment of the compartments. It may be contained, for example, in only one compartment, or in two compartments, or even in three compartments, or even in four compartments.

[0037] Each compartment may contain the same or different detergent compositions. The different detergent compositions may all be in the same form, or they may be in different forms. Preferably, at least one of the compositions, and more preferably, all compositions, are in liquid form.

[0038] Figure 1 A water-soluble unit-dose detergent article (1) according to the present invention is disclosed. A first water-soluble membrane (2) and a third water-soluble membrane (3) sealed together at a sealing region (4) are shown. A second water-soluble membrane positioned between the first water-soluble membrane (2) and the third water-soluble membrane (3) is not shown. A detergent composition (5) (preferably for laundry or automatic dishwashing) is included within the water-soluble unit-dose article (1).

[0039] Intermediate structures contemplated as aspects of this disclosure may include elements or portions of an article in an unsealed state, for example, to allow the composition to be supplied into the intermediate structure before final filling of each compartment. Thus, for example, an intermediate structure may include a first sealed compartment and a second partially open compartment ready for filling. Water-soluble unit-dose articles are configured such that one, two, or more compositions do not leak from two or more compartments during storage. However, when a water-soluble unit-dose article is added to water, the water-soluble membrane dissolves, causing the contents of the internal compartments to be released, for example, into washing liquids, large volumes of water, or other environments.

[0040] Preferably, the water-soluble unit dose product is coated with a lubricant, and preferably, the lubricant is selected from talc, zinc oxide, silicon dioxide, siloxane, zeolite, silicic acid, alumina, sodium sulfate, potassium sulfate, calcium carbonate, magnesium carbonate, sodium citrate, sodium tripolyphosphate, potassium citrate, potassium tripolyphosphate, calcium stearate, zinc stearate, magnesium stearate, starch, modified starch, clay, kaolin, gypsum, cyclodextrin, or mixtures thereof.

[0041] First water-soluble membrane

[0042] The water-soluble unit-dosage detergent product includes a first water-soluble film. The first water-soluble film of the present invention is soluble or dispersible in water. The first water-soluble film preferably has a thickness of 20 micrometers to 150 micrometers, more preferably 35 micrometers to 125 micrometers, even more preferably 50 micrometers to 110 micrometers, and most preferably about 76 micrometers. The first water-soluble film has a first side and a second side.

[0043] As is known in the art, the first water-soluble film material can be obtained by casting, blow molding, extrusion or blow extrusion of polymer materials, and preferably the first water-soluble film is a solvent-cast water-soluble film.

[0044] The first water-soluble membrane comprises a polyvinyl alcohol polymer blend. The polymer blend comprises two polymers: polymer A and polymer B. Preferably, the polyvinyl alcohol polymer blend consists essentially of polymer A and polymer B. Preferably, the first membrane comprises 50% to 90%, more preferably 55% to 85%, and more preferably 60% to 80% of the polyvinyl alcohol polymer blend by weight.

[0045] Preferably, the difference in average degree of hydrolysis between polymer A and polymer B is at most 10%, more preferably at most 5%, and more preferably between 1% and 3%.

[0046] Preferably, the difference in viscosity between polymer A and polymer B at 20°C for a 4% solution is 1 cP to 20 cP, more preferably 3 cP to 15 cP, and even more preferably 5 cP to 12 cP.

[0047] Preferably, the weight-average degree of hydrolysis of the polyvinyl alcohol resin blend is less than 84%, or less than 80%, or less than 75%, or in the range of 74% to 79%. Preferably, the weight-average viscosity of the polyvinyl alcohol resin blend is at least 9 cP, or at least 10 cP, or at least 12 cP, or in the range of 9 cP to 15 cP, or 10 cP to 15 cP, or 12 cP to 14 cP.

[0048] Preferably, the first membrane has a tensile strength (maximum breaking stress) of at least 36 MPa, or at least 38 MPa, or at least 40 MPa up to 50 MPa. Preferably, the first membrane has a residual value of 54 wt% or less, as measured by a dissolution chamber test at room temperature. Preferably, the first membrane has a residual value of 75 wt% or less, preferably 65 wt% or less, as measured by a dissolution chamber test at 5°C.

[0049] Preferably, according to OECD 301B testing, the first membrane has a biodegradability of at least 60% after 60 days, or at least 60% after 28 days. The first membrane meets the OECD 301B biodegradability requirements.

[0050] Preferably, according to OECD 301B testing, the polymer blend exhibits a biodegradability of at least 60% after 60 days, or at least 60% after 28 days. The polymer blend meets the OECD 301B biodegradability requirements.

[0051] Preferably, for a 76-micrometer-thick film, according to MSTM-205 at 5°C, the first film has a dissolution time of less than 120 seconds, preferably less than 70 seconds, and more preferably less than 60 seconds.

[0052] Preferably, the aqueous solution containing the first film and detergent composition dissolved therein has a gelling factor of less than 1.25, preferably less than 1.2, and more preferably less than 1.15, wherein

[0053] G = G' / G”

[0054] in

[0055] G' is the "energy storage" or "elasticity" modulus; and

[0056] "G" stands for "loss" or "plastic" modulus;

[0057] An aqueous solution was prepared as described in this paper, and G' and G' were measured.

[0058] Polymer A

[0059] Polymer A comprises anionic monomer units, vinyl alcohol monomer units, and vinyl acetate monomer units. The anionic monomer units comprise monomers derived from itaconic acid, itaconic acid monoalkyl ester, itaconic acid dialkyl ester, itaconic anhydride, and mixtures thereof, preferably itaconic acid, itaconic acid monomethyl ester, itaconic acid dimethyl ester, itaconic anhydride, and mixtures thereof, more preferably monomers of the group consisting of itaconic acid.

[0060] Polymer A comprises 0.1 mol% to 4.0 mol%, preferably 0.5 mol% to 3.0 mol%, more preferably 1.0 mol% to 2.0 mol% of anionic monomer units, preferably itaconic acid.

[0061] Based on the weight of the polyvinyl alcohol polymer blend, the polyvinyl alcohol blend contains 1% to 30%, preferably 5% to 25%, more preferably 10% to 20% of polymer A. Polymer A has an average degree of hydrolysis of 60% to less than 80%, preferably 70% to less than 80%, more preferably 75% to less than 80%; and a 4% solution viscosity at 20°C of 3cP to 20cP, preferably 3cP to 15cP, more preferably 3cP to 10cP.

[0062] Preferably, the polyvinyl alcohol blend contains 10% to 20% polymer A by weight of the polyvinyl alcohol polymer blend.

[0063] Preferably, polymer A comprises anionic monomer units derived from itaconic acid, and preferably the anionic monomer units are present in an amount between 1.0 mol% and 2.0 mol%.

[0064] Preferably, polymer A has an average degree of hydrolysis of 75% to less than 80%. Preferably, polymer A has a 4% solution viscosity at 20°C of 3 to 10 cP.

[0065] Preferably, the polyvinyl alcohol blend comprises 10% to 20% polymer A by weight, and polymer A has 1.0 mol% to 2.0 mol% of anionic monomer units derived from itaconic acid, an average degree of hydrolysis of 75% to less than 80%, and a solution viscosity of 4% at 20°C of 3 cP to 10 cP.

[0066] Polymer B

[0067] Polymer B is basically composed of vinyl alcohol monomer units and vinyl acetate monomer units.

[0068] The polyvinyl alcohol polymer blend comprises, by weight, 70% to 99%, preferably 75% to 95%, more preferably 80% to 90% of polymer B. Polymer B has an average degree of hydrolysis of 70% to less than 80%, preferably 72% to less than 80%, more preferably 75% to less than 80%; and a 4% solution viscosity at 20°C of 10 cP to 40 cP, preferably 10 cP to 30 cP, more preferably 10 cP to 20 cP.

[0069] Preferably, the polyvinyl alcohol blend contains 80% to 90% polymer B by weight.

[0070] Preferably, polymer B has an average degree of hydrolysis of 75% to less than 80%. Polymer B preferably has a 4% solution viscosity at 20°C of 10 to 20 cP.

[0071] Preferably, the polyvinyl alcohol blend comprises 80% to 90% polymer B by weight, and polymer B has an average degree of hydrolysis of 75% to less than 80% and a 4% solution viscosity at 20°C of 10 cP to 20 cP.

[0072] Second water-soluble membrane

[0073] Water-soluble unit-dosage detergent articles may include a second water-soluble film. The second water-soluble film is soluble or dispersible in water. Preferably, it has a thickness of 20 to 150 micrometers, more preferably 35 to 125 micrometers, even more preferably 50 to 110 micrometers, and most preferably about 76 micrometers. The second water-soluble film has a first side and a second side.

[0074] As is known in the art, the second water-soluble film material can be obtained by casting, blow molding, extrusion, or blow extrusion of polymer materials. Preferably, the second water-soluble film is a solvent-cast water-soluble film. More preferably, the first and second water-soluble films are solvent-cast water-soluble films.

[0075] The second membrane comprises a polymer selected from the group consisting of polymer A, polymer B, polymer C, and mixtures thereof. Polymer C comprises polyvinyl alcohol and is different from the polymer blends of polymer A, polymer B, and the first membrane.

[0076] Polymer C

[0077] Polymer C contains polyvinyl alcohol and is different from polymer blends of polymers A, B, and the first film. The term "different" in this document means that the polymers differ in at least one physical or chemical characteristic, such as having the same monomer units but different ratios, the same monomer units but different degrees of hydrolysis, different molecular weights, different viscosities, different anionic monomer units, different polymer blends, or different polymer blend ratios.

[0078] Polymer C is preferably selected from:

[0079] i) A polymer essentially composed of vinyl alcohol monomer units, vinyl acetate monomer units, and carboxyl monomer units. Preferably, the carboxylic acid ester monomer units are selected from acrylates, methacrylates, maleates, or mixtures thereof, more preferably acrylates.

[0080] ii) Blends of polymers consisting essentially of vinyl alcohol monomer units and vinyl acetate monomer units; and

[0081] iii) Polymer blends consisting essentially of: polymers consisting of vinyl alcohol monomer units and vinyl acetate monomer units and polymers consisting essentially of vinyl alcohol monomer units, vinyl acetate monomer units and carboxyl monomer units.

[0082] Preferably, polymer C comprises a polymer essentially composed of vinyl alcohol monomer units, vinyl acetate monomer units, and carboxyl monomer units, more preferably composed of this polymer, wherein the carboxyl monomer units are selected from acrylates, methacrylates, maleic esters, or mixtures thereof, more preferably acrylates, and wherein the polymer has an average degree of hydrolysis of 80% to 99%, preferably 88% to 99%, and a 4% solution viscosity at 20°C of 13 cP to 28 cP, preferably 18 cP to 26 cP, and an average degree of anionic substitution of 1% to 10%, preferably 1% to 4%. Preferably, polymer C comprises essentially vinyl alcohol monomer units, vinyl acetate monomer units, and carboxyl monomer units, wherein the carboxyl monomer unit is acrylic acid, and wherein the polymer has an average degree of hydrolysis of 88% to 99%, and a 4% solution viscosity at 20°C of 18 cP to 26 cP, and an average degree of anionic substitution of 1% to 4%.

[0083] Preferably, polymer C comprises the following items, more preferably it consists of the following items:

[0084] i) 1% to 70%, preferably 30% to 70% by weight of polymer C, of ​​a polymer substantially composed of vinyl alcohol monomer units and vinyl acetate monomer units, wherein the polymer has an average degree of hydrolysis of 80% to 99.7%, preferably 85% to 93%, more preferably 87% to 89%, and a 4% solution viscosity at 20°C of 14.5 cP to 25 cP, preferably 17 cP to 24 cP; and

[0085] ii) 30% to 99%, preferably 30% to 70% by weight of polymer C, consisting essentially of vinyl alcohol monomer units, vinyl acetate monomer units and carboxyl monomer units, wherein the carboxyl monomer units are preferably derived from maleic acid monomer units and their salts, esters or anhydrides, most preferably maleic acid monomethyl ester monomer units, wherein the polymer has an average degree of hydrolysis of 80% to 99.7%, preferably 85% to 95%, more preferably 88% to 92%, and a 4% solution viscosity at 20°C of 4 cP to 40 cP, preferably 10 cP to 25 cP, more preferably 15 cP to 20 cP, and an average degree of anionic substitution of 1% to 10%, more preferably 1% to 8%, more preferably 1% to 4%.

[0086] Preferably, polymer C consists of the following:

[0087] i) A polymer, by weight of polymer C, consisting of 30% to 70% substantially of vinyl alcohol monomer units and vinyl acetate monomer units, wherein the polymer has an average degree of hydrolysis of 87% to 89% and a 4% solution viscosity at 20°C of 17 cP to 24 cP; and

[0088] ii) By weight of polymer C, 30% to 70% of the polymer is essentially composed of vinyl alcohol monomer units, vinyl acetate monomer units and carboxyl monomer units, wherein the carboxyl monomer unit is monomethyl maleate, wherein the polymer has an average degree of hydrolysis of 88% to 92%, a solution viscosity of 4% at 20°C of 15 cP to 20 cP, and an average degree of anionic substitution of 1% to 4%.

[0089] Preferably, polymer C comprises the following items, more preferably it consists of the following items:

[0090] i) A first polymer consisting essentially of vinyl alcohol monomer units and vinyl acetate monomer units, wherein the first polymer has an average degree of hydrolysis of 80% to 92%, preferably 84% to 92%, and a 4% solution viscosity at 20°C of 8 cP to 40 cP, preferably 10 cP to 20 cP, more preferably 12 cP to 14 cP; and

[0091] ii) A second polymer consisting essentially of vinyl alcohol monomer units and vinyl acetate monomer units, wherein the second polymer has an average degree of hydrolysis of 80% to 92%, preferably 84% to 92%, and a solution viscosity of 4% at 20°C of 1 to 20 cP, preferably 3 to 15 cP, more preferably 5 to 10 cP; and

[0092] The first polymer and the second polymer are present in a weight ratio of about 9:1 to about 1:9, preferably about 6:4 to about 4:6.

[0093] Preferably, polymer C consists of the following:

[0094] i) A first polymer consisting essentially of vinyl alcohol monomer units and vinyl acetate monomer units, wherein the first polymer has an average degree of hydrolysis of 84% to 92% and a 4% solution viscosity at 20°C of 12 to 14 cP; and

[0095] ii) A second polymer consisting essentially of vinyl alcohol monomer units and vinyl acetate monomer units, wherein the second polymer has an average degree of hydrolysis of 84% to 92% and a solution viscosity of 4% at 20°C of 5 to 10 cP; and

[0096] The first polymer and the second polymer are present in a weight ratio of about 6:4 to about 4:6.

[0097] Third water-soluble membrane

[0098] Water-soluble unit-dosage detergent articles may include a third water-soluble film. This third water-soluble film is soluble or dispersible in water. Preferably, it has a thickness of 20 to 150 micrometers, more preferably 35 to 125 micrometers, even more preferably 50 to 110 micrometers, and most preferably about 76 micrometers. The third water-soluble film has a first side and a second side.

[0099] As is known in the art, the third water-soluble membrane material can be obtained by casting, blow molding, extrusion, or blow extrusion of polymer materials. Preferably, the third water-soluble membrane is a solvent-cast water-soluble membrane. More preferably, the first, second, and third water-soluble membranes are solvent-cast water-soluble membranes.

[0100] The third membrane differs from the first and second membranes and contains polymers selected from the group consisting of polymer A, polymer B, polymer C, and mixtures thereof.

[0101] Water-soluble unit-dose detergent products include single-compartment pouches made of two films (where both films are first films) and side-by-side pouches made of two films (where both films are first films). Water-soluble unit-dose detergent products include single-compartment pouches and side-by-side pouches made of two films, where one of the two films is a first film and the other is a second film.

[0102] Water-soluble unit-dosage detergent products comprise overlapping pouches made of three films. The three films may be identical or different. When the three films are identical, all three films constitute the first film. When the three films are different, one film is the first film, another is the second film, and the third film is the third film, and any of these films may be the bottom film, the middle film, or the top film. Alternatively, two films may be identical and one film may be different, wherein the two identical films are the first film and the different film is the second film, or alternatively, the different film is the first film and the two identical films are the second film. The different film may be the top film, the middle film, or the bottom film.

[0103] Measurement methods

[0104] The average degree of hydrolysis was measured using the standard method JIS K6726.

[0105] The viscosity of polyvinyl alcohol polymers is determined by measuring freshly prepared solutions using a Brookfield LV viscometer with a UL adapter, as described in British Standard EN ISO 15023-2:2006 Annex E Brookfield Test Method. International convention specifies the viscosity as a 4% aqueous solution of polyvinyl alcohol (deionized water) at 20°C.

[0106] Water-soluble membranes (including the first, second, and third water-soluble membranes) can be characterized by the following modulus (MOD) test or by testing their tensile stress. The procedure involves determining the modulus at 10% elongation according to ASTM D 882 (“Standard Test Method for Tensile Properties of Thin Plastic Sheeting”) or an equivalent. Membrane data are collected using an INSTRON tensile testing apparatus (Model 5544 Tensile Tester or equivalent). At least three test specimens are tested in the longitudinal (MD) direction (where applicable), with each cut performed using reliable cutting tools to ensure dimensional stability and reproducibility. Tests are conducted under standard laboratory conditions of 23 ± 2.0 °C and 35 ± 5% relative humidity. One-inch-wide (2.54 cm) specimens of a single membrane sheet with a thickness of 76 μm are prepared. The specimens are then transferred to the INSTRON tensile testing machine for testing, while minimizing exposure to an environment of 35% relative humidity. Prepare the tensile testing machine according to the manufacturer's instructions, equipped with a calibrated 500N load cell. Properly assemble the fixtures and face (NSTRON fixtures have model 2702-032 face or equivalent, which is rubber-coated and 25mm wide). Mount the sample into the tensile testing machine and analyze it to determine the 100% modulus (i.e., the stress required to achieve 100% membrane elongation).

[0107] The first water-soluble membrane is characterized by a minimum of approximately 20 N / mm², as measured by MOD testing at 35% RH. 2 The MOD value is the 100% modulus value. Generally, higher MOD values ​​are desirable because they correspond to pouches with greater stiffness and a lower likelihood of deformation and sticking together when loaded on top of each other during production or end-consumer packaging. Furthermore, an MOD value at 10% elongation corresponds to the film's ability to maintain stiffness rather than slack and sag when in contact with the contents of a liquid pouch. Specifically, films with higher MOD values ​​correspond to pouches that are less likely to soften and exhibit a slack and sagging appearance when in contact with the contents of a liquid pouch containing low molecular weight polyols.

[0108] Dissolution chamber test method .

[0109] In this DC residue testing method, for each membrane to be tested, three test samples are cut from a selected test membrane with a thickness of 76 μm using a cutting punch. If cutting from a membrane web produced by a continuous method, the samples should be cut from web regions that are evenly spaced along the transverse direction of the web (i.e., perpendicular to the longitudinal direction), if applicable. The membrane sample weight is weighed and the sample is tracked through testing. The initial membrane weight (F) is recorded. oWeigh the two ultrasonically treated, clean, and dried sieves for each sample and track their weight throughout the test. Record the initial sieve weight (therefore, for both sets of sieves, the total S). o Assemble the sample dissolution chamber by clamping the membrane sample flat between the centers of the two sieves, then assemble two rubber gaskets (one gasket on each side between the sieves and the gaskets), followed by two more gaskets. Secure the dissolution chamber assembly with four clamps evenly spaced around the gaskets and fold the clamps back away from the sieves. Dissolve the sample at room temperature (22℃ ± 2℃) or at 5℃ ± 2℃ using 1,500 ml of R... O Fill the beaker with (e.g., demineralized water). Set the timer to a specified immersion time of 10 minutes. Place the dissolving chamber assembly in the beaker and immediately start the timer, inserting the dissolving chamber assembly into the water surface at an approximately 45-degree entry angle. This entry angle helps remove air bubbles from the chamber. The dissolving chamber assembly is positioned at the bottom of the beaker so that the test sample membrane is horizontally positioned approximately 10 mm from the bottom. The four fold-back clamps of the dissolving chamber assembly are adapted to maintain a membrane gap of approximately 10 mm from the bottom of the beaker; however, any other equivalent support components can be used. At the end of 10 minutes, slowly remove the dissolving chamber assembly from the beaker at approximately a 45-degree angle. Hold the dissolving chamber assembly horizontally on the aluminum tray to catch any drips from the screen and carefully remove the clamps, gaskets, and rubber gaskets. Do not open the clamped screen. Place the clamped screen (i.e., screen / residual undissolved membrane / screen) on the aluminum tray and place it in an oven at 100°C for 30 minutes to dry. Weigh the set of dried clamped screens, including any residual undissolved membrane. When the dissolution chamber assembly is first removed from the beaker and during drying, measure the weight of the dried screens and add the weight of any dried membrane drips collected and recovered (e.g., by scraping) from the pan. Record the final clamped screen weight (total Sf, including dried membrane drips). Calculate the % residue remaining in the membrane sample (“DC residue”):

[0110] DC residue = 100 × (S f -S o ) / F0)

[0111] Clean the clamped screens by soaking them in RO water in a beaker for about 20 minutes. Then, separate them and finally rinse them in an ultrasonic bath (start and inject RO water) for at least 5 minutes, or until there are no visible residues on the screens.

[0112] Gelation Factor (G) Method

[0113] The gelling factor method measures the strength of the gel formed between the encapsulated detergent composition and the polyvinyl alcohol film upon initial dissolution in wash water. This method is designed to provide laboratory characterization (using very low volumes of water) of uncommon or extreme household processes where gelation may occur. It serves as a representative measure of when detergent is released into the wash water. If residues are generated during laundry washing, these residues can be redissolved, but this may imply further steps, and the purpose of this invention is to reduce the amount of touching required by the user during the laundry washing process.

[0114] Gelation factor was measured using a plate-to-plate rotational rheometer (TA Discovery Hybrid Rheometer) with a 60 mm flat mandrel. The substrate temperature was set to 5°C. An aluminum cross frame (6 mm wide for each crossbar) was placed on the substrate to divide it into four equal quadrants. At room temperature (e.g., 20°C ± 2°C), 1 ml of detergent composition was added to two opposite quadrants, creating substantially triangular shapes along the corresponding crossbars of the frame, as shown. Figure 1 As shown. At room temperature (e.g., 20°C + / - 2°C), 1 ml of the dissolved water-soluble membrane in a 10% by weight solution in demineralized water was metered into the remaining two opposite quadrants. The cross frame was then removed, allowing the four liquids to remain separated. The mandrel was then rotated to the measurement conditions, allowing the liquids to flow slightly out from the entire periphery of the mandrel. The subsequent measurement procedure consisted of a 30-second temperature adjustment, a 180-second peak hold at 40 rad / s, and a gradual logarithmic scan of the oscillating angular frequency (from 100 rad / s to 0.016 rad / s over approximately 38 minutes via a logarithmic scan at a constant and controlled stress of 0.1 Pa, ensuring the gel was always within the linear viscoelastic range). Storage modulus (G') and loss modulus (G”) were measured at 5 points per decimal place, resulting in a total of twenty data points. The average storage modulus (in Pa) and average loss modulus (in Pa) were calculated from the corresponding values ​​at 0.040 rad / s, 0.025 rad / s, and 0.015 rad / s, for example, the last three data points measured. Therefore, the gelling factor was calculated by dividing the average storage modulus by the average loss modulus value. It is a dimensionless value. Three measurements were performed, and the average was taken as the gelling factor.

[0115] Dissolution framework method

[0116] Based on the MSTM2O5 disintegration / dissolution protocol, the cold water solubility characteristics of different polyvinyl alcohol-based water-soluble films were determined in demineralized water at 10°C.

[0117] Small bag strength method

[0118] This test method describes the practice of determining pouch strength using a Mark-10 testing instrument ESM750SLCE (JJBOS BV, Marcostraat 1, NL-2809 PH Gouda, The Nederlands) with a pressure-sensing element having a maximum pressure of 100 kN (kilonewtons). Under external compressive force, the pouch deforms, thereby generating stress on the membrane and sealing areas. The internal pressure within the pouch depends on the external force applied across the entire surface area of ​​the pouch. Pouch strength (in Newtons) is defined as the maximum compressive force required to increase the internal pressure of the pouch to its burst point using two parallel plates. Pouch rupture at the sealing area is reported as "seal failure" and is not considered when determining pouch strength. The average of 18 replicates is reported.

[0119] The strength of the water-soluble pouches was measured after storing them under ambient conditions for 7 days and pre-conditioning them at 23°C / 50% RH for 16 to 24 hours. The method was conducted in an indoor environment with 40% to 50% relative humidity (RH) and 22 to 24°C. The water-soluble pouches were removed from pre-conditioning and tested within one hour.

[0120] Figure 2 A schematic diagram of the basic configuration for a small bag strength test is shown. To measure small bag strength, a small bag 510 is sealed in a plastic bag and then sealed with a seal 500 (150mm × 124mm, with a closure, 60 micrometers thick – e.g., a Raja clamp RGP6B) to prevent contamination of the working environment should the small bag break. The small bag 510 is centered within the bag and placed between two compression plates 520, 530 of the instrument. The small bag 510 is placed in a flat position such that the width seal dimension 540 (e.g., the minimum dimension within a defined rectangular plane that only surrounds the seal area, 41mm in the actual bag being tested) is placed horizontally between the compression plates (x-direction), such that stress will be applied to the width seal. The diameter of the compression plates needs to be large enough to prevent the small bag from being crushed when it deforms (here, D = 116mm). For compression, the rate at which the distance between plates 520 and 530 decreases is set to 225mm / min. Each test segment is repeated 18 times, and the average small bag strength data from these 18 repetitions is reported.

[0121] Additional membrane components

[0122] Based on the weight of the water-soluble membrane, the first, second, and / or third water-soluble membranes contain surfactants ranging from 0.1% to 3.5%, or from 0.1% to 2.5%, or in the range of 1% to 2%, or in the range of 0.5% to 2%. Suitable surfactants may include nonionic, cationic, anionic, and zwitterionic categories. Suitable surfactants include, but are not limited to, nonionic surfactants, including but not limited to polyoxyethylene polyoxypropylene glycol, alcohol ethoxylates, alkylphenol ethoxylates, tertiary acetylenols, and alkanolamides; cationic surfactants, including but not limited to polyoxyethylene amines, quaternary ammonium salts, and quaternized polyoxyethylene amines; and zwitterionic surfactants, including but not limited to amine oxides, N-alkyl betaine, and sulfobetaine. For example, nonionic surfactants may be selected from alcohol ethoxylates; cationic surfactants may be selected from quaternary ammonium salts; and zwitterionic surfactants may be selected from amine oxides. Other suitable surfactants include sodium sulfosuccinate, acylated fatty acid esters of glycerol and propylene glycol, lactams of fatty acids, sodium alkyl sulfate, polysorbate 20, polysorbate 60, polysorbate 65, polysorbate 80, lecithin, acetylated fatty acid esters of glycerol and propylene glycol, acetylated fatty acid esters, and combinations thereof.

[0123] As measured by Karl Fischer titration, the first, second, and / or third water-soluble membranes, by weight of the first water-soluble membrane, have a residual moisture content of at least 4%, more preferably between 4% and 15%, and even more preferably between 5% and 10%.

[0124] The first water-soluble membrane, the second water-soluble membrane, and / or the third water-soluble membrane may contain one or more components selected from the group consisting of: plasticizers, plasticizer compatibilizers, lubricants, stripping agents, fillers, extenders, crosslinking agents, antiblocking agents, antioxidants, anti-sticking agents, defoamers, nanoparticles, bleaching agents, odorants, surfactants, and combinations thereof.

[0125] The first water-soluble film, the second water-soluble film, and / or the third water-soluble film may contain one or more plasticizers, wherein the amount of plasticizer is between 5% and 50% by weight of the water-soluble film, preferably between 10% and 40%, and most preferably between 20% and 30%. Preferably, the plasticizer in the water-soluble film is selected from polyols, sugar alcohols, or mixtures thereof. Preferably, the polyols include those selected from the group consisting of: glycerol, diglycerol, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, up to 400 MW of polyethylene glycol, neopentyl glycol, 1,2-propanediol, 1,3-propanediol, dipropylene glycol, polypropylene glycol, 2-methyl-1,3-propanediol, trimethylolpropane, and polyether polyols or mixtures thereof. The sugar alcohols include those selected from the group consisting of: isomaltitol, maltitol, sorbitol, xylitol, erythritol, arbutinol, galactitol, pentaerythritol, and mannitol or mixtures thereof. Most preferably, the plasticizer is selected from the group consisting of: sorbitol, glycerol, dipropylene glycol, and mixtures thereof.

[0126] Preferably, the first water-soluble film, the second water-soluble film, and / or the third water-soluble film contain a lubricant / stripping agent. Suitable lubricants / stripping agents may include, but are not limited to, fatty acids and their salts, fatty alcohols, fatty acid esters, fatty amines, fatty amine acetates, and fatty amides. Preferred lubricants / stripping agents are fatty acids, fatty acid salts, and fatty amine acetates. The amount of lubricant / stripping agent in the first water-soluble film is from 0.02% to 1.5% by weight, preferably from 0.1% to 1%.

[0127] Preferably, the first, second, and / or third water-soluble films comprise fillers, expanders, anti-blocking agents, anti-sticking agents, or mixtures thereof. Suitable fillers, expanders, anti-blocking agents, anti-sticking agents, or mixtures thereof include, but are not limited to, starch, modified starch, cross-linked polyvinylpyrrolidone, cross-linked cellulose, microcrystalline cellulose, silica, metal oxides, calcium carbonate, talc, and mica. Preferred materials are starch, modified starch, and silica. Preferably, the amount of fillers, expanders, anti-blocking agents, anti-sticking agents, or mixtures thereof in the first water-soluble film, based on the weight of the water-soluble film, is in the range of 0.1% to 25%, preferably 1% to 10%, more preferably 2% to 8%, and most preferably 3% to 5%. In the absence of starch, a preferred range for suitable fillers, expanders, anti-blocking agents, anti-sticking agents, or mixtures thereof is 0.1% to 1% based on the weight of the water-soluble film, preferably 4%, more preferably 6%, even more preferably 1% to 4%, and most preferably 1% to 2.5%.

[0128] The first, second, and / or third water-soluble films may include printing areas. The printing areas may be implemented using standard techniques such as flexographic printing or inkjet printing. The printing areas may face the internal compartment of the unit dose article, or may face the external environment, or both, preferably facing the internal compartment of the unit dose article. Preferred inks for printing the articles of the present invention include red, white, and black pigments, such as red: Pigment Red 254, white: titanium dioxide, and black: lampblack or carbon black (Pigment Black 6).

[0129] The first, second, and / or third water-soluble membranes may contain an aversive agent, such as a bittering agent. Suitable bittering agents include, but are not limited to, naringin, sucrose octaacetate, quinine hydrochloride, benzyl dinatamide, or mixtures thereof. Any suitable amount of the aversive agent may be used in the membrane. Suitable amounts include, but are not limited to, 1 ppm to 5000 ppm, or even 100 ppm to 2500 ppm, or even 250 rpm to 2000 rpm.

[0130] Methods for preparing water-soluble membranes

[0131] The water-soluble membrane used in the water-soluble unit-dose articles of the membrane disclosed herein can be prepared by any suitable method. Methods for preparing the water-soluble membrane include solvent casting, blow molding, extrusion, and blow extrusion, as commonly known in the art. Methods for solvent casting are well known in the art. For example, in film-forming methods, a resin and minor additives are dissolved in a solvent (typically water), metered onto a surface, allowed to dry substantially (or forced dry) to form a cast film, and then the resulting cast film is removed from the cast surface. This process can be carried out in batches and is more efficient when carried out in a continuous manner.

[0132] In the formation of continuous films, the conventional practice is to meter a solution of resin and minor components onto a moving casting surface, such as a continuously moving metal drum or belt, allowing the solvent to be substantially removed from the liquid, thereby forming a self-supporting cast film, and then peeling the resulting cast film off the casting surface. Optionally, the solution can be metered or coated onto a carrier film, release liner, or removable backing, whereby, after solvent removal, the resulting cast film or coating can be separated from the carrier film, release liner, or removable backing (e.g., immediately after drying or at a later point in time, e.g., before use) or remain attached to the carrier film, release liner, or removable backing. The film or coating prepared on the carrier film, release liner, or removable backing can be self-supporting or non-self-supporting.

[0133] Typically, the amount of water in the metering solution of polyvinyl alcohol, additional resins, and / or minor components used for film casting is selected such that the solution has the highest solids level below the viscosity inflection point when heated to the casting temperature. Methods for determining the amount of solids at the viscosity inflection point are known in the art. Typically, the water content of the metering solution may contain between 60% and 85% water, or between 60% and 75% water, to provide a suitable solution for casting with typical casting solutions. The viscosity of the casting solution may be, for example, at least about 20,000 cps at 185℉ (85°C), at least 30,000 cps at 185℉ (85°C), and for example, from about 40,000 cps to about 50,000 cps at 185℉ (85°C).

[0134] The casting solution can be poured at any suitable temperature, such that the membrane has a temperature range, for example, from about 50°C to about 105°C, during drying. It is undesirable to be bound by theory, but it is believed that when the casting solution and membrane temperatures decrease below about 50°C, the amount of time required to dry the membrane undesirably increases, and the length of the drying chamber required to completely dry the casting solution undesirably increases. Furthermore, it is undesirable to be bound by theory, but it is believed that when the solution and membrane temperatures rise above about 105°C, the solvent may rapidly evaporate from the membrane, leading to defects on the membrane surface, such as pores or bubbles in the finished membrane, and / or promoting undesirable reactions between adjacent PVOH backbones, resulting in reduced membrane solubility.

[0135] In continuous or semi-continuous casting processes, the moving casting surface can have a linear velocity ranging from approximately 5 m / min to approximately 50 m / min. Linear velocity affects the properties of the resulting film, such as physical properties, thickness, residual moisture content, and film quality. Generally, as the linear velocity decreases, the resulting film thickness increases, while as the linear velocity increases, the resulting film thickness decreases, assuming a constant solution delivery rate. Typically, as the linear velocity increases, the residence time of the film in the dryer decreases, thus requiring higher drying temperatures, which may lead to drying defects or adhesion at sufficiently high temperatures. Conversely, as the linear velocity decreases, the residence time of the film in the dryer increases.

[0136] Any of the first, second, third, or additional films disclosed herein may be produced by solvent casting, for example, using a solvent belt casting system. This system may include a tank for mixing and / or storing a polymer solution with optional minor additives, used in conjunction with a belt casting machine having at least a first and a second rotating drum, around which a continuous belt (e.g., a metal belt) is tensioned to travel as the drums rotate. A tableting die applies the polymer solution from the tank onto the metal belt, wherein, as the polymer solution travels in sheet form on the metal belt, a drying chamber surrounding at least a portion of the metal belt downstream of the tableting die removes the solvent from the polymer solution. Furthermore, the use of a release coating may provide one or more advantages to the film and / or the method. For example, a release coating may significantly reduce or eliminate air bubbles in the produced polymer film, or a release coating may improve the ease with which the produced film can be peeled off the casting surface. A roll coater release coating applicator, in communication with a supply source of the release coating and a portion of the belt, may transfer the fluid release coating to the casting surface before applying the polymer solution to the belt. A suitable solvent-based casting system and related materials are further described in U.S. Patent Application Publication 2006 / 0081176 A1, the entire disclosure of which is incorporated herein by reference.

[0137] Typically, for those skilled in the art, the casting surface can be any suitable substrate used for producing polymer films. In embodiments, the substrate can be a casting roller or drum, a casting belt, or a combination thereof. As used herein, the substrate is used to produce polymer films from polymer resins or polymer resin solutions. The substrate includes a substrate surface and the substrate surface is coated with a release coating. The polymer resin solution can be cast onto the substrate while it is being moved (e.g., rotated). In embodiments, the substrate is a casting drum. In embodiments, the substrate is a casting belt. The substrate may comprise stainless steel and optionally may have a stainless steel surface. The substrate may comprise stainless steel, which may optionally be plated, for example, chromium plated, nickel plated, zinc plated, or a combination thereof.

[0138] Typically, release coatings may contain one or more surfactants and an optional carrier, such as water.

[0139] A release coating can be applied to a substrate surface and optionally subsequently dried, after which a polymer resin or polymer resin solution is cast onto the surface-coated substrate. In an embodiment, the release coating may have a pH of about 1 to about 5 when applied to the substrate surface before drying the release coating on the substrate surface.

[0140] Typically, based on the total weight of the release coating, the release coating may have a surfactant concentration of about 0.001 wt% to about 100 wt%. In an embodiment, prior to the release coating on the dried substrate surface, the release coating may have a surfactant concentration in the range of about 0.001 wt% to about 20 wt%. For example, prior to the release coating on the dried substrate surface, the release coating may have a surfactant concentration in the range of about 0.001 wt% to about 10 wt%, or about 0.01 wt% to about 5 wt%, or about 0.01 wt% to about 4 wt%, or about 0.01 wt% to about 3 wt%, or about 0.01 wt% to about 2 wt%, or about 0.05 wt% to about 2 wt%, or about 0.1 wt% to about 2 wt%, or about 0.5 wt% to about 2 wt%. In an embodiment, prior to the release coating on the dried substrate surface, based on the total weight of the release coating, the release coating may have a surfactant concentration in the range of about 0.01 wt% to about 4.00 wt%. In an embodiment, prior to the release coating on the dried substrate surface, the release coating may have a surfactant concentration ranging from about 0.05 wt% to about 2.00 wt% based on the total weight of the release coating. In an embodiment, after the release coating on the dried substrate surface, the release coating may have a surfactant concentration ranging from about 2.5 wt% to about 100 wt% based on the total weight of the release coating. For example, after the release coating on the dried substrate surface, the release coating may have a surfactant concentration ranging from about 3 wt% to about 100 wt%, or about 4 wt% to about 90 wt%, or about 4 wt% to about 80 wt%, or about 4 wt% to about 70 wt%, or about 4 wt% to about 50 wt%, or about 4 wt% to about 30 wt%, or about 4 wt% to about 20 wt%, or about 4.7 wt% to about 100 wt%, or about 5 wt% to about 90 wt% based on the total weight of the release coating. In an embodiment, after the release coating is applied to the surface of the dried substrate, the release coating may have a surfactant concentration ranging from about 4.7% by weight to about 100% by weight, based on the total weight of the release coating. For example, the release coating may contain ZONYL surfactant ranging from about 0.05% by weight to about 5.0% by weight, based on the total weight of the release coating.

[0141] Typically, the release coating described herein may have a hydrophilic-lipophilic balance in the range of about 1 to about 30. In embodiments, the release coating may have a hydrophilic-lipophilic balance in the range of about 1 to about 20, or about 1 to about 18, or about 1 to about 17, or about 1 to about 16, or about 1 to about 15, or about 2 to about 17, or about 3 to about 17, or about 4 to about 15, or about 5 to about 12, or about 8 to about 12. In embodiments, the release coating may have a hydrophilic-lipophilic balance in the range of about 1 to about 20. In embodiments, the release coating may have a hydrophilic-lipophilic balance in the range of about 3 to about 17.

[0142] Typically, the release coating has a thickness of about 0.1 nm to about 100 nm on the substrate surface. In embodiments, the release coating has a thickness of about 0.1 nm to about 80 nm, or about 0.1 nm to about 60 nm, or about 0.1 nm to about 40 nm, or about 0.1 nm to about 40 nm, or about 0.1 nm to about 20 nm, or about 0.1 nm to about 10 nm, or about 1 nm to about 10 nm, or about 1 nm to about 5 nm on the substrate surface. In embodiments, the release coating has a thickness of about 0.1 nm to about 40 nm on the substrate surface. In embodiments, the release coating has a thickness of about 0.1 nm to about 10 nm on the substrate surface.

[0143] Laundry or automatic dishwashing detergent composition

[0144] Water-soluble unit-dose detergent products contain fabric care or household care detergent compositions, preferably laundry or automatic dishwashing detergent compositions, more preferably laundry detergent compositions.

[0145] The laundry detergent composition is preferably a liquid laundry detergent composition.

[0146] The term "liquid laundry detergent composition" refers to any laundry detergent composition comprising a liquid capable of wetting and treating fabrics, and includes, but is not limited to, liquids, gels, pastes, dispersions, etc. Liquid compositions may include solids or gases in appropriately subdivided forms, but liquid compositions do not include forms that are generally non-fluid, such as tablets or granules.

[0147] The liquid detergent composition can be used in hand washing of fabrics or in automatic machine washing of fabrics, preferably in automatic machine washing of fabrics.

[0148] Preferably, the liquid laundry detergent composition contains 5% to 60%, more preferably 15% to 55% of a non-soap anionic surfactant, based on the weight of the laundry detergent composition. More preferably, the detergent composition contains between 20% and 55%, more preferably between 25% and 50%, of a non-soap anionic surfactant.

[0149] Preferably, the non-soap anionic surfactant comprises a linear alkylbenzene sulfonate. Preferably, the linear alkylbenzene sulfonate comprises C 10 -C 16 Alkylbenzene sulfonates, C 11 -C 14 Alkylbenzene sulfonates or mixtures thereof. Preferably, the alkylbenzene sulfonate is an amine-neutralized alkylbenzene sulfonate, an alkali metal-neutralized alkylbenzene sulfonate, or a mixture thereof. The amine is preferably selected from monoethanolamine, triethanolamine, or a mixture thereof. The alkali metal is preferably selected from sodium, potassium, magnesium, or a mixture thereof. Preferably, the liquid laundry detergent composition contains between 1% and 40%, preferably between 3% and 40%, and more preferably between 6% and 35% by weight of the liquid laundry detergent composition.

[0150] Preferably, the non-soap anionic surfactant comprises an alkyl sulfate anionic surfactant, wherein the alkyl sulfate anionic surfactant is selected from alkyl sulfates, alkoxylated alkyl sulfates, or mixtures thereof. The alkyl sulfate anionic surfactant can be a primary alkyl sulfate anionic surfactant or a secondary alkyl sulfate anionic surfactant, or a mixture thereof, preferably a primary alkyl sulfate anionic surfactant. Preferably, the alkoxylated alkyl sulfate includes ethoxylated alkyl sulfates, propoxylated alkyl sulfates, mixed ethoxylated / propoxylated alkyl sulfates, or mixtures thereof, more preferably ethoxylated alkyl sulfates. Preferably, the ethoxylated alkyl sulfate has an average degree of ethoxylation between 0.1 and 5, preferably between 0.5 and 3. Preferably, the ethoxylated alkyl sulfate has an average alkyl chain length between 8 and 18, more preferably between 10 and 16, and most preferably between 12 and 15. Preferably, the alkyl chain of the alkyl sulfate anionic surfactant is straight-chain or branched, or a mixture thereof. Preferably, the branched alkyl sulfate anionic surfactant is a branched primary alkyl sulfate, a branched secondary alkyl sulfate, or a mixture thereof, preferably a branched primary alkyl sulfate, wherein the branch is preferably at the 2-position, or alternatively may be further present under the alkyl chain, or may be multi-branched, wherein the branch is distributed along the alkyl chain. The weight-average branching degree of the alkyl sulfate anionic surfactant can be 0% to 100%, preferably 0% to 95%, more preferably 0% to 60%, and most preferably 0% to 20%. Alternatively, the weight-average branching degree of the alkyl sulfate anionic surfactant can be 70% to 100%, preferably 80% to 90%. Preferably, the alkyl chain is selected from materials of natural origin, materials of synthetic origin, or mixtures thereof. Preferably, the materials of synthetic origin include oxosynthesized materials, Ziegler-synthesized materials, Guerbet-synthesized materials, Fischer-Tropsch-synthesized materials, isoalkyl-synthesized materials, or mixtures thereof, preferably oxosynthesized materials. Preferably, the liquid laundry detergent composition comprises between 1% and 35% by weight of the liquid laundry detergent composition, preferably between 3% and 30%, and more preferably between 6% and 20%, of an alkyl sulfate anionic surfactant.

[0151] Preferably, the non-soap anionic surfactant includes linear alkylbenzene sulfonate and alkoxylated alkyl sulfate. More preferably, the weight ratio of linear alkylbenzene sulfonate to alkoxylated alkyl sulfate is 1:2 to 9:1, preferably 1:1 to 7:1, more preferably 1:1 to 5:1, and most preferably 1:1 to 4:1.

[0152] The liquid laundry detergent composition contains, by weight, 2.5% to 30%, preferably between 4% and 25%, more preferably between 8% and 20% of a nonionic surfactant, preferably composed of alkoxylated alcohols. The nonionic surfactant is described in more detail below.

[0153] Preferably, the weight ratio of the non-soap anionic surfactant to the nonionic surfactant is 1:1 to 13:1, more preferably 1.25:1 to 10:1, and even more preferably 1.5:1 to 7.5:1.

[0154] Preferably, the nonionic surfactant comprises an alkoxylated alcohol, wherein the alkoxylated alcohol is derived from synthetic alcohols, natural alcohols, or mixtures thereof. The alkoxylated alcohol may be a primary alkoxylated alcohol, a secondary alkoxylated alcohol, or a mixture thereof, preferably a primary alkoxylated alcohol. Preferably, the alkoxylated alcohol comprises an ethoxylated alcohol, a propoxylated alcohol, a mixed ethoxylated / propoxylated alcohol, or a mixture thereof, more preferably an ethoxylated alcohol. Alternatively, the alkoxylated alcohol may also include a higher alkoxy group, such as a butoxy group. When alkoxy groups are mixed, the alkoxy groups may be randomly ordered or present in blocks, preferably present in blocks. For example, the mixed ethoxy (EO) / propoxy (PO) groups may be ordered in the form of EO / PO blocks, PO / EO blocks, EO / PO / EO blocks, or PO / EO / PO blocks. Preferably, the ethoxylated alcohol has an average degree of ethoxylation between 0.1 and 20, preferably between 5 and 15, and most preferably between 6 and 10. If propoxylation is present, the average degree of propoxylation is preferably between 0.1 and 25, more preferably between 2 and 20, and most preferably between 5 and 10. Preferably, the alkoxylated (preferably ethoxylated) alcohol has an average alkyl chain length between 8 and 18, more preferably between 10 and 16, and most preferably between 12 and 16. Preferably, the alkyl chain of the alkoxylated alcohol is straight-chain, branched, or a mixture thereof, wherein the branched alkyl-oxidized alcohol is a branched primary alkoxylated alcohol, a branched secondary alkoxylated alcohol, or a mixture thereof, preferably a branched primary alkoxylated alcohol. Preferably, the weight-average branching degree of the alkoxylated alcohol is 0% to 100%, preferably 0% to 95%, more preferably 0% to 60%, and most preferably 0% to 40%. Branching may be at the 2-alkyl position, or alternatively further below the alkyl chain, or may be multi-branched, wherein individual branches are distributed along the alkyl chain. Preferably, the materials from which the synthesis is derived include oxo-synthesized materials, Ziegler-synthesized materials, Gerbert-synthesized materials, Fischer-Tropsch-synthesized materials, isoalkyl-branched materials, or mixtures thereof, with oxo-synthesized materials being preferred. Preferably, the nonionic surfactant is composed of alkoxylated alcohols. It is undesirable to be bound by theory; nonionic surfactants, especially alkoxylated alcohol nonionic surfactants, provide excellent effects in cleaning body deposits and suspending dirt.

[0155] Preferably, the liquid laundry detergent composition comprises fatty acids, preferably neutralized fatty acid soaps, more preferably fatty acid salts, and more preferably amine-neutralized fatty acid salts. Preferably, the amine is an alkanolamine, more preferably selected from monoethanolamine, diethanolamine, triethanolamine, or mixtures thereof, and more preferably monoethanolamine. The liquid detergent composition may contain between 1.5% and 20%, between 2% and 15%, between 3% and 12%, or between 4% and 10% fatty acids by weight of the liquid detergent composition.

[0156] Preferably, the liquid laundry detergent composition contains between 1% and 20%, preferably between 5% and 15%, of water based on the weight of the liquid laundry detergent composition.

[0157] Preferably, the liquid laundry detergent composition comprises between 10% and 40%, preferably between 15% and 30% by weight of the liquid laundry detergent composition, and preferably, the non-aqueous solvent is selected from 1,2-propanediol, dipropylene glycol, tripropylene glycol, glycerin, sorbitol, polyethylene glycol, or mixtures thereof.

[0158] Preferably, the liquid laundry detergent composition comprises auxiliary ingredients selected from the group consisting of: builders, fragrances, enzymes, citrates, bleaching agents, bleaching catalysts, dyes, tinting dyes, brighteners, cleaning polymers including alkoxylated polyamines and polyethyleneimine, detergency polymers, fabric care polymers including cationic hydroxyethyl cellulose and cationic polyglucans, surfactants, solvents, dye transfer inhibitors, chelating agents, encapsulated fragrances, polycarboxylate esters, structural agents, pH adjusters, antioxidants including Ralox 35, and mixtures thereof.

[0159] Preferably, the laundry detergent composition comprises an enzyme selected from the group consisting of hemicellulase, peroxidase, protease (including metalloproteinase), cellulase, xylanase, lipase, phospholipase, esterase, keratinase, pectinase, keratinase, reductase, oxidase, phenol oxidase, lipoxygenase, ligninase, amylopectinase, tannic acidase, pentosanase, melaninase, β-glucanase, arabinosease, hyaluronidase, chondroitinase, laccase, xyloglucanase, mannanase, and amylase, nuclease, or mixtures thereof, preferably comprising an enzyme selected from the group consisting of protease (including metalloproteinase), amylase, cellulase, lipase, xyloglucanase, mannanase, nuclease, or mixtures thereof.

[0160] Preferably, the liquid laundry detergent composition has a pH between 6 and 10, more preferably between 6.5 and 8.9, and most preferably between 7 and 8, wherein the pH of the laundry detergent composition is measured at 20°C with a product concentration of 10% in deionized water.

[0161] Liquid laundry detergent compositions can be Newtonian or non-Newtonian. Preferably, the liquid laundry detergent composition is non-Newtonian. Unbound by theory, non-Newtonian liquids have different properties than Newtonian liquids; more specifically, the viscosity of a non-Newtonian liquid depends on the shear rate, while a Newtonian liquid has a constant viscosity independent of the applied shear rate. The decrease in viscosity when shear is applied to a non-Newtonian liquid is considered to further favor the dissolution of the liquid detergent. The liquid laundry detergent compositions described herein can have any suitable viscosity, depending on factors such as the formulation ingredients and the purpose of the composition.

[0162] The composition may be an automatic dishwashing liquid composition, which preferably contains ingredients selected from the following: surfactants, builders, sulfonated / carboxylated polymers, siloxane defoamers, silicates, metal and / or glass care agents, enzymes, bleaching agents, bleaching activators, bleaching catalysts, alkalinity sources, fragrances, dyes, solvents, fillers, and mixtures thereof.

[0163] The surfactants preferably used in automatic dishwashing detergents are low-foaming, either on their own or in combination with other components (e.g., defoamers). Preferably used herein are low-cloud-point and high-cloud-point nonionic surfactants and mixtures thereof, including nonionic alkoxylated surfactants (especially ethoxylated derivatives derived from C6-C18 primary alcohols), ethoxylated-propoxylated alcohols (e.g., those from Olin Corporation). SLF18), epoxy-terminated poly(alkoxylated) alcohols (e.g., those from Olin Corporation) SLF18B), ether-terminated poly(alkoxylated) alcohol surfactants, and block polyoxyethylene-polyoxypropylene polymers such as those from BASF-Wyandotte Corp. (Wyandotte, Michigan). REVERSED and Series; amphoteric surfactants such as C12-C20 alkylamine oxides (preferably lauryl dimethylamine oxide and hexadecyl dimethylamine oxide are used herein), and alkyl amphoteric carboxylic acid surfactants such as MIRANOL TM C2M; and zwitterionic surfactants such as betaine and sulfobetaine; and mixtures thereof. The surfactant may be present at a level of 0.2% to 30%, more preferably 0.5% to 10%, and most preferably 1% to 5% by weight of the detergent composition.

[0164] Builders suitable for the detergent compositions described herein include water-soluble builders, including citrates, carbonates, silicates, and polyphosphates, such as sodium tripolyphosphate and sodium tripolyphosphate hexahydrate, potassium tripolyphosphate, and mixtures of sodium tripolyphosphate and potassium tripolyphosphate.

[0165] Enzymes suitable for use in the detergent compositions described herein include bacterial and fungal cellulases, including and (Novo Nordisk A / S); peroxidase; lipase, including (Amano Pharmaceutical Co.), M1 and (Gist-Brocades) and and LIPOLASE (Novo); keratinase; protease, including and (Novo) and and (Gist-Brocades); β and α amylases, including OX AM (Genencor) and and (Novo); pectinase; and mixtures thereof. In this document, the enzyme may be added in the form of spheres, granules, or co-granules at levels typically ranging from 0.0001% to 2% pure enzyme by weight of the clean composition.

[0166] Defoaming agents suitable for the detergent compositions described herein include nonionic surfactants with low cloud point. As used herein, "cloud point" is a well-known characteristic of nonionic surfactants, which is the temperature at which a second phase can be observed as the surfactant becomes less soluble with increasing temperature. As used herein, a "low cloud point" nonionic surfactant is defined as a component of a nonionic surfactant system having a cloud point of less than 30°C, preferably less than about 20°C, and even more preferably less than about 10°C, and most preferably less than about 7.5°C. Low cloud point nonionic surfactants may include nonionic alkoxylated surfactants, especially ethoxylated derivatives derived from primary alcohols and polyoxypropylene / polyoxyethylene / polyoxypropylene (PO / EO / PO) reverse block polymers. Furthermore, such low cloud point nonionic surfactants may include, for example, ethoxylated-propoxylated alcohols (e.g., BASF). SLF18) and epoxy-terminated poly(alkoxylated) alcohols (e.g., BASF) SLF18B series nonionic compounds).

[0167] Other components suitable for use in the detergent compositions described herein include cleaning polymers having anti-redeposition, detergency, or other detergency properties. Anti-redeposition polymers that may be used herein include acrylic-containing polymers such as… PA30, PA20, PA15, PA10 and CP10 (BASF GmbH) 45N, 480N, 460N (Rohmand Haas), acrylic / maleic acid copolymers, etc. CP5, and acrylic / methacrylic acid copolymers. Other suitable polymers include amine-based polymers such as alkoxylated polyalkylene imides (e.g., PEI600 EO20 and / or ethoxylated hexamethylenediamine dimethyl quaternary ammonium salt), which may optionally be quaternized. Detergent polymers that can be used herein include alkyl and hydroxyalkyl celluloses, polyethylene oxide, polypropylene oxide and copolymers thereof, as well as nonionic and anionic polymers based on polyethylene terephthalate, propylene terephthalate and mixtures thereof.

[0168] Heavy metal polyvalent chelating agents and crystal growth inhibitors are also suitable for detergents, such as salts and free acid forms of diethylenetriaminepenta (methylenephosphonate), ethylenediaminetetra(methylenephosphonate), hexamethylenediaminetetra(methylenephosphonate), ethylenediphosphonate, hydroxy-ethylene-1,1-diphosphonate, hypozinotriacetate, ethylenediaminetetraacetate, and ethylenediamine-N,N'-disuccinate.

[0169] Corrosion inhibitors, such as organic silver coating agents (especially paraffins, such as those sold by Wintershall (Salzbergen, Germany), are also suitable for the detergent compositions described herein. 70) Nitrogen-containing corrosion inhibitor compounds (e.g., benzotriazole and benzimidazole, as well as Mn(II) compounds, especially Mn(II) salts of organic ligands).

[0170] Other components applicable to the detergent compositions described herein include enzyme stabilizers such as calcium ions, boric acid, and propylene glycol.

[0171] Suitable rinsing additives are known in the art. Commercial rinsing aids for dishwashing are typically mixtures of low-foaming fatty alcohol polyethylene / polypropylene glycol ethers, solubilizers (e.g., isopropylbenzene sulfonate), organic acids (e.g., citric acid), and solvents (e.g., ethanol). These rinsing aids work by influencing the interfacial tension of water in a manner that allows it to escape from the rinsed surface as a thin cohesive film, thus leaving no water droplets, streaks, or films after the subsequent drying process.

[0172] Method for preparing water-soluble unit dose products

[0173] Another aspect of the present invention is a method for preparing a water-soluble unit dose article according to the present invention, the method comprising the following steps:

[0174] i) Thermoforming and / or vacuum forming of water-soluble films to create cavities;

[0175] ii) Filling the cavity with a detergent composition or a portion thereof; and

[0176] iii) To close the cavity with another membrane and / or a pre-formed compartment containing a detergent composition or a portion thereof to produce a single-compartment or multi-compartment water-soluble unit dose detergent article.

[0177] Preferably, the method includes the following steps:

[0178] i) Thermoforming and / or vacuum forming can be a first membrane, a second membrane, or a third membrane to create a cavity;

[0179] ii) Filling the cavity with a detergent composition or a portion thereof; and

[0180] iii) To produce a single-compartment or multi-compartment water-soluble unit-dose detergent article by closing the cavity with another membrane, which may be a first membrane, a second membrane, or a third membrane, and / or a pre-formed compartment containing a detergent composition or a portion thereof. The membrane and / or pre-formed compartment may be sealed, for example, by solvent sealing. The water-soluble unit-dose detergent article may be made of two or more first membranes, or a first membrane and one or more second membranes, or a first membrane, a second membrane, and one or more third membranes, etc.

[0181] Methods for preparing water-soluble unit-dose articles can be automated, such as conveyor belts, a series of conveyor belts, drums, a series of drums, or a combination thereof. Alternatively, methods for preparing water-soluble unit-dose articles can be manual production lines, wherein one or more sequences or steps are performed manually. Most preferably, the method is automated.

[0182] Preferably, the method for preparing the water-soluble unit dose product is a continuous method. Alternatively, the method for preparing the water-soluble unit dose product can be an intermittent method or a batch method. Preferably, the method for preparing the water-soluble unit dose product is a continuous preparation method.

[0183] Preferably, the closed intermediate is prepared on a rotating drum or a horizontal belt, more preferably on a rotating drum. Preferably, the filled open cavity body in steps a and b is prepared on a horizontal belt or a rotating drum, more preferably on a horizontal belt. When using a rotating drum, the water-soluble film is preferably held in place by vacuum. When using a horizontal belt, the water-soluble film is preferably held in place by vacuum.

[0184] Preferably, multiple unit-dose articles are formed that are interconnected by flat regions. Not wishing to be bound by theory, such methods involve preparing multiple water-soluble unit-dose articles bonded together by non-deformable membranes to create a water-soluble network of unit-dose articles. The non-deformable membrane is a flat region of the water-soluble network between the unit-dose articles. Thus, the flat region may comprise two or more water-soluble membranes sealed together.

[0185] The resulting mesh of water-soluble unit-dose articles connected by flat areas is then transferred to a cutting station for cutting to produce individual unit-dose articles. Preferably, the cutting station cuts the mesh longitudinally and transversely. Preferably, a rotary blade is used for cutting. It is also preferable that the cutting is performed continuously, preferably at a constant linear speed, and preferably in a horizontal position. The cutting device may be, for example, a sharp object, a hot object, or a laser, in which case the hot object or laser “burns” through the film / sealing area. Cutting can be performed by one or more rotary blades. Preferably, cutting is performed by one or more rotary blades, wherein the rotary blades cut longitudinally, transversely, or a combination thereof. Preferably, the rotary blades rotate at a variable speed.

[0186] Solvent-sealing solutions can be applied by any suitable method, including contact and / or non-contact methods. For example, solvent solutions can be applied during contact transfer, such as using contact members comprising non-absorbent or substantially impermeable materials, such as anilox rollers, rubber (e.g., EPDM) rollers, or any combination thereof, optionally in combination with a doctor blade. Doctor blades, Mayer's blades, or similar devices can be used to apply the sealing solution. In another type of embodiment, contact members comprising absorbent materials can be used to apply the sealing solution, such as natural felt, synthetic felt, porous plastics, foam, sponge, microfiber, cotton, polyester, extruded polyester fibers, nonwoven webs, etc., for example in the form of pads or rollers. Specifically, application of solvent-sealing solutions via felt rollers is considered. Solvent-sealing solutions can be applied via felt rollers, spray nozzles, metering nozzles, or combinations thereof, preferably via felt rollers or spray nozzles. Preferably, the solvent-sealing solution comprises an aqueous solvent, a non-aqueous solvent, or a mixture thereof. Even more preferably, the solvent-sealing solution comprises water. Preferably, the solvent sealing solution comprises at least 95%, or even at least 98%, or even at least 99%, or even 100% water by weight of the solvent sealing solution. Preferably, the solvent sealing solution is applied via a felt roller, via a spray nozzle, a metering nozzle, or a combination thereof, more preferably via a felt roller or via a spray nozzle. Preferably, the solvent sealing solution is applied to a second water-soluble membrane. Preferably, the solvent sealing solution is present on the water-soluble membrane at a sealing solution concentration between 1 g and 30 g per square meter, more preferably between 5 g and 20 g per square meter.

[0187] The water-soluble membrane can be preheated before deformation by a hot plate, an infrared lamp, or a combination thereof, preferably an infrared lamp.

[0188] The mold in which the article is prepared can have any shape, length, width, and depth depending on the desired pouch size. If desired, the molds can also differ from each other in size and shape. For example, the volume of the final unit dose article can be from about 5 ml to about 300 ml, or from about 10 ml to 150 ml, or from about 10 ml to about 50 ml, and the mold size can be adjusted accordingly. Preferably, the surface of the mold has a rough texture.

[0189] The resulting water-soluble unit dose product preferably has a strength of at least 200 N, preferably at least 300 N, and more preferably at least 400 N, as measured by the test methods described herein.

[0190] The dimensions and values ​​disclosed herein should not be construed as strictly limited to the precise numerical values ​​cited. Rather, unless otherwise specified, each such dimension is intended to represent the stated value and the range around which it is functionally equivalent. For example, a dimension disclosed as “40 mm” is intended to mean “about 40 mm”.

[0191] Example

[0192] The interaction between conventional soluble unit-dose liquid laundry detergent formulations and water-soluble films according to the invention and those outside the scope of the invention was studied in the initial dissolution in wash water, following the gelling factor test method described herein.

[0193] Table 1 illustrates water-soluble unit-dosage detergent products according to the present invention. The liquid detergent compositions placed in each compartment have been prepared by mixing individual detergent components in an intermittent process.

[0194] Table 2 describes water-soluble membranes according to the present invention, as well as water-soluble membranes outside the scope of the present invention. The membranes compared are outside the scope of the present invention due to their excessively high average degree of hydrolysis; these are representative membranes conforming to the prior art of WO2017218408.

[0195] Table 3 shows the gelling factor data obtained using the test methods described herein for combinations of bottom-compartment liquid detergents from Table 1 with different membranes from Table 2. It can be seen that the combination of the liquid detergent composition according to the invention with a water-soluble membrane produces a much lower gelling factor than related compositions having membranes outside the scope of the invention.

[0196] Table 1: Liquid Detergent Compositions (wt% - based on 100% active ingredient)

[0197]

[0198]

[0199] *Ethoxylated polyethyleneimine, having an average degree of ethoxylation of 20 per EO chain and a polyethyleneimine backbone with a MW of approximately 600.

[0200] **Lutensit Z96: Partially sulfated polyoxyethylene ether hexamethylenediamine, available from BASF.**

[0201] ***Premixed composition: 37% by weight cationic hydroxyethyl cellulose, 60% by weight PPG400, 3% by weight Acusol 880 - the premixed components reflected in the above formulation composition.

[0202] Table 2: Water-soluble membrane compositions

[0203]

[0204] Table 3: Gelation Factor Data

[0205] gelling agent The membrane of the present invention 1.09 Comparison membrane 1.71

Claims

1. A water-soluble unit-dose detergent article comprising a water-soluble film encapsulating a fabric care or household care detergent composition, wherein the detergent composition comprises a cleaning surfactant, and the water-soluble film comprises a first film comprising a polyvinyl alcohol polymer blend, wherein the polymer blend comprises: i) 1% to 30%, preferably 5% to 25%, more preferably 10% to 20% of polymer A by weight of the polymer blend, wherein polymer A comprises anionic monomer units, vinyl alcohol monomer units and vinyl acetate monomer units, and wherein the anionic monomer units comprise monomers derived from itaconic acid, itaconic acid monoalkyl ester, itaconic acid dialkyl ester, itaconic anhydride and mixtures thereof, preferably itaconic acid, itaconic acid monomethyl ester, itaconic acid dimethyl ester, itaconic anhydride and mixtures thereof, more preferably monomers of the group consisting of itaconic acid; Polymer A has The average degree of hydrolysis is 60% to less than 80%, preferably 70% to less than 80%, and more preferably 75% to less than 80%. as well as The viscosity of a 4% solution at 20°C is 3cP to 20cP, preferably 3cP to 15cP, and more preferably 3cP to 10cP. as well as ii) 70% to 99%, preferably 75% to 95%, more preferably 80% to 90% of polymer B by weight of the polymer blend, wherein polymer B is substantially composed of vinyl alcohol monomer units and vinyl acetate monomer units. Polymer B has An average degree of hydrolysis of 70% to less than 80%, preferably 72% to less than 80%, more preferably 75% to less than 80%; and A 4% solution viscosity at 20°C of 10 cP to 40 cP, preferably 10 cP to 30 cP, and more preferably 10 cP to 20 cP.

2. The article of claim 1, wherein the anionic monomer unit comprises itaconic acid.

3. The article of any one of the preceding claims, wherein the polymer blend comprises: i) 10% to 20% of polymer A, based on the weight of the polymer blend, wherein polymer A comprises anionic monomer units derived from itaconic acid. Polymer A has An average degree of hydrolysis of 75% to less than 80%; and Viscosities of 4% solutions at 20°C ranging from 3 cP to 10 cP; and ii) Based on the weight of the polymer blend, 80% to 90% of polymer B, Polymer B has An average degree of hydrolysis of 75% to less than 80%; and Viscosity of a 4% solution at 20°C with a viscosity of 10 cP to 20 cP.

4. The article according to any one of the preceding claims, wherein polymer A comprises 0.1 mol% to 4.0 mol%, preferably 0.5 mol% to 3.0 mol%, more preferably 1.0 mol% to 2.0 mol% of the anionic monomer unit.

5. The article of any one of the preceding claims, wherein the polymer blend is substantially composed of polymer A and polymer B.

6. The article according to any one of the preceding claims, wherein the difference in viscosity between polymer A and polymer B at 20°C for a 4% solution is 1 cP to 20 cP, preferably 3 cP to 15 cP, more preferably 5 cP to 12 cP.

7. The article according to any one of the preceding claims, wherein the difference in the average degree of hydrolysis between polymer A and polymer B is at most 10%, preferably at most 5%, more preferably between 1% and 3%.

8. The article according to any one of the preceding claims, wherein the first membrane comprises 50% to 90%, preferably 55% to 85%, more preferably 60% to 80% of the polymer blend by weight of the membrane.

9. The article according to any one of the preceding claims, wherein the first membrane has a tensile strength (maximum breaking stress) of at least 36 MPa, or at least 38 MPa, or at least 40 MPa up to 50 MPa.

10. The article according to any one of the preceding claims, wherein the first film has a residual value of 75% by weight or less, preferably 65% ​​by weight or less, as measured by a dissolution chamber test at 5°C.

11. The article of any one of the preceding claims, wherein the first membrane has a biodegradability of at least 60% after 60 days or at least 60% after 28 days, as determined by OECD 301B testing.

12. The article of any one of the preceding claims, wherein the polymer blend has a biodegradability of at least 60% after 60 days or at least 60% after 28 days, as determined by OECD 301B testing.

13. The article according to any one of the preceding claims, wherein for a 76-micrometer-thick film, according to MSTM-205 at 5°C, the first film has a dissolution time of less than 120 seconds, preferably less than 70 seconds, and more preferably less than 60 seconds.

14. The article according to any one of the preceding claims, wherein the aqueous solution of the first film and the detergent composition dissolved therein has a gelling factor of less than 1.25, preferably less than 1.2, more preferably less than 1.15, wherein G = G' / G” in G' is the "energy storage" or "elasticity" modulus; and "G" stands for "loss" or "plastic" modulus; The aqueous solution was prepared as described herein, and G' and G' were measured.

15. The article according to any one of the preceding claims, wherein the water-soluble film comprises a second film, and wherein the second film comprises a polymer selected from the group consisting of polymer A, polymer B, polymer C and mixtures thereof, and wherein polymer C comprises polyvinyl alcohol and is different from the polymer blend of polymer A, polymer B and the first film.

16. The article of claim 1, wherein the first membrane and the second membrane are sealed to form a first enclosed compartment, the first enclosed compartment comprising a fabric or household care detergent composition or a portion thereof.

17. The article of claim 15 or 16, wherein polymer C is selected from: i) Polymers that are basically composed of vinyl alcohol monomer units, vinyl acetate monomer units, and carboxyl monomer units. ii) Blends of polymers consisting essentially of vinyl alcohol monomer units and vinyl acetate monomer units; and iii) Polymer blends consisting essentially of: polymers consisting of vinyl alcohol monomer units and vinyl acetate monomer units and polymers consisting essentially of vinyl alcohol monomer units, vinyl acetate monomer units and carboxyl monomer units.

18. The article according to any one of claims 15 to 17, wherein polymer C comprises a polymer essentially consisting of vinyl alcohol monomer units, vinyl acetate monomer units, and carboxyl monomer units, preferably composed of said polymer, wherein said carboxyl monomer units are selected from acrylates, methacrylates, maleates, or mixtures thereof, more preferably acrylates, and wherein said polymer has a content of 80% to 99%, preferably 88% to 99%. The average degree of hydrolysis, and the 4% solution viscosity at 20°C of 13 cP to 28 cP, preferably 18 cP to 26 cP, and the average degree of anionic substitution of 1% to 10%, preferably 1% to 4%.

19. The article of any one of claims 15 to 17, wherein polymer C comprises, preferably, the following: i) 1% to 70%, preferably 30% to 70% by weight of polymer C, of ​​a polymer substantially composed of vinyl alcohol monomer units and vinyl acetate monomer units, wherein the polymer has an average degree of hydrolysis of 80% to 99.7%, preferably 85% to 93%, more preferably 87% to 89%, and a 4% solution viscosity at 20°C of 14.5 cP to 25 cP, preferably 17 cP to 24 cP; as well as ii) Based on the weight of polymer C, 30% to 99%, preferably 30% to 70%, of a polymer substantially composed of vinyl alcohol monomer units, vinyl acetate monomer units, and carboxyl monomer units, wherein the carboxyl monomer units are preferably derived from maleic acid monomer units and their salts, esters, or anhydrides, most preferably monomethyl maleate monomer units, wherein the polymer has 80% to 99.7%, preferably 85% to 95%, more preferably 88%. The solution has an average degree of hydrolysis of up to 92%, and a solution viscosity of 4% at 20°C of 4 cP to 40 cP, preferably 10 cP to 25 cP, more preferably 15 cP to 20 cP, and an average degree of anionic substitution of 1% to 10%, preferably 1% to 8%, more preferably 1% to 4%.

20. The article of any one of claims 15 to 17, wherein polymer C comprises, preferably, the following: i) A first polymer consisting essentially of vinyl alcohol monomer units and vinyl acetate monomer units, wherein the first polymer has an average degree of hydrolysis of 80% to 92%, preferably 84% to 92%, and a 4% solution viscosity at 20°C of 8 cP to 40 cP, preferably 10 cP to 20 cP, more preferably 12 cP to 14 cP; and ii) A second polymer consisting essentially of vinyl alcohol monomer units and vinyl acetate monomer units, wherein the second polymer has an average degree of hydrolysis of 80% to 92%, preferably 84% to 92%, and a solution viscosity of 4% at 20°C of 1 to 20 cP, preferably 3 to 15 cP, more preferably 5 to 10 cP; and The first polymer and the second polymer are present in a weight ratio of about 9:1 to about 1:9, preferably about 6:4 to about 4:

6.

21. The article according to any one of the preceding claims, wherein the water-soluble membrane comprises a third membrane, and wherein the third membrane comprises a polymer selected from the group consisting of polymer A, polymer B, polymer C and mixtures thereof, and wherein the third membrane is different from the first membrane and the second membrane.

22. The article of any one of the preceding claims, wherein the first film and, if present, the second film and, if present, the third film comprises additives selected from the group consisting of: plasticizers, plasticizer compatibilizers, lubricants, release agents, fillers, extenders, crosslinking agents, antiblocking agents, antioxidants, anti-sticking agents, defoamers, nanoparticles, bleaching agents, surfactants, and combinations thereof.

23. The article of any one of the preceding claims, wherein the article has a strength of at least 200 N, preferably at least 300 N, more preferably at least 400 N, as measured according to the method described herein.

24. The article of manufacture according to any one of the preceding claims, wherein the detergent composition comprises between 5% and 60% of a non-soap anionic surfactant based on the weight of the detergent composition.

25. The article of manufacture according to any one of the preceding claims, wherein the detergent composition comprises between 1% and 25% nonionic surfactant based on the weight of the detergent composition.

26. The article of manufacture according to any one of the preceding claims, wherein the detergent composition contains between 0.5% and 15% water based on the weight of the detergent composition.

27. A method for preparing an article according to any one of the preceding claims, the method comprising the following steps: i) The membrane is thermoformed and / or vacuum-formed to create a cavity; ii) Fill the cavity with a detergent composition or a portion thereof; as well as iii) The cavity is closed with another membrane and / or a pre-formed compartment containing a detergent composition or a portion thereof to produce a single-compartment or multi-compartment water-soluble unit-dose detergent article.

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