Water-soluble unit dose products

Abstract

A water-soluble unit-dosage product containing laundry detergent or automatic dishwashing detergent, and a method for preparing the same.

Description

Technical Field

[0001] A water-soluble unit dosage product suitable for laundry and automatic dishwashing, and its preparation method. Background Technology

[0002] Water-soluble unit-dose products suitable for laundry and automatic dishwashing are popular with consumers due to their ease of use and high efficiency. These water-soluble unit-dose products typically contain a laundry detergent composition or an automatic dishwashing composition. Unbound by theory, when the water-soluble unit-dose product is added to water, the membrane dissolves / disintegrates, releasing its internal contents into the surrounding water to produce a laundry detergent liquid or an automatic dishwashing liquid. The membrane used must meet two criteria: providing sufficient strength so that it will not tear or rupture prematurely during storage and transportation, and dissolving sufficiently during the laundry or automatic dishwashing cycle to minimize unwanted membrane residue at the end of the wash operation. Membranes composed of polyvinyl alcohol have been used to meet these requirements. A preferred method for preparing such unit-dose products is to deform a first water-soluble membrane in a mold to create an open cavity, fill the open cavity with a laundry detergent composition or an automatic dishwashing composition, and then close the open cavity with a second water-soluble membrane, sealing the first and second water-soluble membranes together to produce the water-soluble unit-dose product.

[0003] However, the problem encountered with this type of unit-dose product is not a failure of the structural integrity of the membrane itself, but rather a potential failure of the seal between the first and second water-soluble membranes. Such failure can lead to premature rupture of the water-soluble unit-dose product.

[0004] Furthermore, there is a growing desire to wash fabrics or dishes under more environmentally friendly conditions, such as shorter wash cycles and lower wash temperatures. Under such conditions, known water-soluble unit-dose products may suffer incomplete dissolution during wash cycles, resulting in undissolved film material residue that deposits on the fabrics or dishes to be washed.

[0005] Therefore, there is a need in the art for a water-soluble unit-dose product that provides reduced seal failure while maintaining acceptable structural integrity and solubility characteristics of the membrane itself.

[0006] Surprisingly, the water-soluble unit-dose article according to the invention achieves this objective. This is even more surprising, considering that the second water-soluble film contains a higher degree of polyvinyl alcohol homopolymer, as those skilled in the art would expect it to result in reduced solubility under short and cold washing cycles. Summary of the Invention

[0007] A first aspect of the present invention is a water-soluble unit-dose article comprising at least two compartments and a laundry detergent composition or an automatic dishwashing detergent composition, wherein the laundry detergent composition or automatic dishwashing detergent composition is contained in at least one of the compartments, wherein the unit-dose article comprises:

[0008] a. A first water-soluble membrane, wherein the first water-soluble membrane has a first side and a second side, and wherein the first water-soluble membrane comprises a first polyvinyl alcohol (PVOH) resin, wherein the first polyvinyl alcohol resin comprises polyvinyl alcohol composed of a polyvinyl alcohol homopolymer, an anionic polyvinyl alcohol copolymer, or a blend thereof;

[0009] b. A second water-soluble membrane, wherein the second water-soluble membrane has a first side and a second side, and wherein the second water-soluble membrane comprises a second polyvinyl alcohol resin, wherein the second polyvinyl alcohol resin comprises:

[0010] i. Less than 15% by weight of the second polyvinyl alcohol resin of a polyvinyl alcohol polymer, the polyvinyl alcohol polymer comprising a carboxylated anionic monomer unit, a vinyl alcohol monomer unit and optionally a vinyl acetate monomer unit, wherein the carboxylated anionic monomer unit is derived from a member selected from the group consisting of maleic acid, monoalkyl maleate, dialkyl maleate, maleic anhydride and combinations thereof.

[0011] ii. 85% to 100% by weight of the second polyvinyl alcohol resin, of a polyvinyl alcohol homopolymer or homopolymer blend, wherein the homopolymer is composed of ethylene alcohol monomer units and optionally vinyl acetate monomer units;

[0012] The second polyvinyl alcohol resin has an average 4% solution viscosity in deionized water at 20°C, between 8 mPa·s and less than 12 mPa·s.

[0013] c. A third water-soluble membrane, wherein the third water-soluble membrane has a first side and a second side, and wherein the third water-soluble membrane comprises a third polyvinyl alcohol (PVOH) resin, wherein the third polyvinyl alcohol resin preferably comprises polyvinyl alcohol composed of a polyvinyl alcohol homopolymer, an anionic polyvinyl alcohol copolymer, or a blend thereof.

[0014] The first side of the first water-soluble membrane is sealed to the second side of the second water-soluble membrane to create a first compartment between the first water-soluble membrane and the second water-soluble membrane, and the first side of the second water-soluble membrane is sealed to the second side of the third water-soluble membrane to create at least a second compartment between the second water-soluble membrane and the third water-soluble membrane, wherein the second compartment is positioned above the first compartment.

[0015] A second aspect of the present invention is a method for preparing a water-soluble unit dose product, the method comprising the following steps:

[0016] a. The first water-soluble film is deformed in a mold by thermoforming, vacuum forming, or a combination thereof to produce an open mouth body;

[0017] b. Fill the oral cavity with the laundry detergent composition or the automatic dishwashing detergent composition;

[0018] c. The third water-soluble film is individually deformed in a mold by thermoforming, vacuum forming, or a combination thereof to produce at least one open cavity;

[0019] d. Fill the at least one open cavity from step c with a laundry detergent composition or an automatic dishwashing detergent composition;

[0020] e. Seal the filled oral cavity from step c with a second water-soluble membrane;

[0021] f. Seal the second water-soluble membrane and the third water-soluble membrane to produce a closed intermediate, preferably wherein the second water-soluble membrane and the third water-soluble membrane are sealed by solvent sealing, more preferably wherein a solvent sealing solution is applied to a first side of the second water-soluble membrane before sealing the membranes together, the first side being the side facing the third water-soluble membrane;

[0022] g. Close the filled oral cavity from step b with the closed intermediate from step f;

[0023] h. Sealing the first water-soluble film and the second water-soluble film to produce a water-soluble unit dose article, preferably wherein the first water-soluble film and the second water-soluble film are sealed by solvent sealing, more preferably wherein a solvent sealing solution is applied to a second side of the second water-soluble film before sealing the films together, the second side being the side facing the first water-soluble film. Attached Figure Description

[0024] Figure 1 It is a water-soluble unit dose product according to the present invention.

[0025] Figure 2 A schematic diagram of the basic configuration for the bag strength pass rate % and seal failure % test is shown. Detailed Implementation

[0026] Water-soluble unit dose products

[0027] A first aspect of the present invention is a water-soluble unit-dose article. The water-soluble unit-dose article comprises at least two compartments and a laundry detergent composition or an automatic dishwashing detergent composition. The laundry detergent composition or automatic dishwashing detergent composition is contained in at least one of the compartments. The laundry detergent composition or automatic dishwashing detergent composition is described in more detail below. The water-soluble unit-dose article comprises a first water-soluble membrane, a second water-soluble membrane, and a third water-soluble membrane. The first water-soluble membrane, the second water-soluble membrane, and the third water-soluble membrane are described in more detail below.

[0028] The water-soluble unit-dose 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 article is configured such that a laundry detergent composition or an automatic dishwashing liquid composition does not leak out of the compartments during storage. However, when the water-soluble unit-dose article is added to water, the water-soluble membrane dissolves, releasing the contents of the internal compartments into the washing liquid.

[0029] The compartment should be understood as a sealed internal space within a unit dose of the product, which holds the laundry detergent composition or the automatic dishwashing detergent composition.

[0030] The first water-soluble membrane has a first side and a second side. The second water-soluble membrane has a first side and a second side. The third water-soluble membrane has a first side and a second side.

[0031] A first side of the first water-soluble membrane is sealed to a second side of the second water-soluble membrane to create a first compartment between the first water-soluble membrane and the second water-soluble membrane, and a first side of the second water-soluble membrane is sealed to a second side of the third water-soluble membrane to create at least a second compartment between the second water-soluble membrane and the third water-soluble membrane, wherein the second compartment is positioned above the first compartment.

[0032] 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, 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, a spray nozzle, or a combination thereof; more preferably, via a felt roller. Preferably, the solvent sealing solution is applied to a second side of the second water-soluble membrane, the second side of the second water-soluble membrane facing the first side of the first water-soluble membrane.

[0033] 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. 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.

[0034] Surprisingly, it has been found that when membranes according to the prior art are sealed by solvent sealing, there is a tendency for the solvent sealing solution to be unevenly deposited on the water-soluble membrane before sealing. Not wanting to be bound by theory, where two membranes are intended to be sealed together, a solvent sealing solution needs to be applied to at least one membrane. If the solvent sealing solution does not provide a uniform layer on the membrane to which it is applied, this then results in a weaker seal between the two membranes, leading to seal failure and premature rupture in the water-soluble unit-dose article. Surprisingly, it has been found that in the unit-dose article according to the invention, a more homogeneous / uniform solvent sealing solution layer is obtained between the water-soluble membranes to be sealed, resulting in reduced seal failure. Not bound by theory, it is believed that adding a solvent sealing solution to the water-soluble membrane can produce a thin foam layer. This thin foam layer results in a non-uniform solvent sealing solution layer present on the water-soluble membrane, leading to premature seal failure. Surprisingly, it has been found that adding a solvent sealing solution to a second water-soluble membrane according to the invention results in a reduced or even absent foam layer, and thus reduces the likelihood of seal failure.

[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 laundry detergent composition or automatic dishwashing detergent composition according to the invention may be contained in at least one compartment. 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 laundry detergent compositions or automatic dishwashing detergent compositions. The different laundry detergent compositions or automatic dishwashing detergent compositions may all be in the same form, or they may be in different forms.

[0038] Figure 1 A water-soluble unit-dosage 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 laundry detergent composition or an automatic dishwashing detergent composition (5) is included within the water-soluble unit-dosage 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, the 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 two or more compositions do not leak from two or more compartments during storage. However, when the water-soluble unit-dose article is added to water, the water-soluble membrane dissolves and releases the contents of the internal compartments, 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, preferably wherein 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 product includes a first water-soluble membrane. The first water-soluble membrane of the present invention is soluble or dispersible in water. The first water-soluble membrane, before deformation, preferably 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 first water-soluble membrane has a first side and a second side.

[0043] Preferably, as measured by the method described herein after using a glass filter with a maximum pore size of 20 micrometers, the first water-soluble membrane has a water solubility of at least 50%, preferably at least 75%, or even at least 95%: 5 g ± 0.1 g of membrane material is added to a pre-weighed 3 L beaker, and 2 L ± 5 ml of distilled water is added. This is vigorously stirred for 30 minutes at 30°C on a Labline magnetic stirrer (model 1250) or equivalent and a 5 cm magnetic stirrer (set to 600 rpm). The mixture is then filtered through a pleated qualitative porous glass filter having the aforementioned specified pore size (maximum 20 micrometers). The water in the collected filtrate is dried by any conventional method, and the weight of the remaining material (the dissolved or dispersed portion) is determined. The percentage of solubility or dispersion can then be calculated.

[0044] 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.

[0045] The first water-soluble film comprises a first polyvinyl alcohol (PVOH) resin, wherein the first polyvinyl alcohol resin comprises polyvinyl alcohol composed of a polyvinyl alcohol homopolymer, an anionic polyvinyl alcohol copolymer, or a blend thereof.

[0046] Preferably, the first water-soluble film comprises a blend of polyvinyl alcohol homopolymer and / or anionic polyvinyl alcohol copolymer. Preferably, the first water-soluble film comprises a blend of polyvinyl alcohol homopolymer and anionic polyvinyl alcohol copolymer, wherein the polyvinyl alcohol homopolymer and the anionic polyvinyl alcohol copolymer are preferably present in a relative weight ratio of 90 / 10 to 10 / 90, preferably 80 / 20 to 20 / 80, and more preferably 70 / 30 to 50 / 50.

[0047] Preferably, the first water-soluble film comprises anionic polyvinyl alcohol copolymer, said anionic polyvinyl alcohol copolymer comprising anionic monomer units, preferably wherein the anionic monomer units are present in the anionic polyvinyl alcohol copolymer in an average amount ranging from 1 mol% to 10 mol%, preferably from 2 mol% to 5 mol%. Preferably, the anionic polyvinyl alcohol copolymer is selected from sulfonated and carboxylated anionic polyvinyl alcohol copolymers, especially carboxylated anionic polyvinyl alcohol copolymers.

[0048] Most preferably, the first water-soluble membrane comprises a blend of a polyvinyl alcohol homopolymer and a carboxylated anionic polyvinyl alcohol copolymer, preferably wherein the carboxylic ester is selected from acrylates, methacrylates, maleic esters, or mixtures thereof, preferably maleic esters. Preferably, the carboxylated anionic monomer unit in the first water-soluble membrane is derived from a monoalkyl maleate ester unit, which is preferably selected from the group consisting of monomethyl maleate, its salts, preferably alkali metal salts, and combinations thereof. Not wishing to be bound by theory, the polyvinyl alcohol polymer comprising carboxylated anionic monomer units, vinyl alcohol monomer units, and optionally vinyl acetate monomer units is an anionic polyvinyl alcohol copolymer. Preferably, each carboxylated anionic monomer unit is present in the carboxylated anionic polyvinyl alcohol copolymer in an average amount of 3 mol% to 6 mol%, or 3 mol% to 5 mol%, or 3.5 mol% to 4.5 mol%, or 4 mol% to 4.5 mol%.

[0049] To avoid being bound by theory, the term "homopolymer" generally includes polymers having a single type of repeating monomer unit (e.g., polymer chains containing or consisting of a single repeating monomer unit). In the specific case of polyvinyl alcohol polymers, the term "homopolymer" also includes copolymers having a distribution of vinyl alcohol monomer units and optionally vinyl acetate monomer units (depending on the degree of hydrolysis) (e.g., polymer chains containing or consisting of vinyl alcohol and vinyl acetate monomer units). In the example of 100% hydrolysis, the polyvinyl alcohol homopolymer may contain only vinyl alcohol units. To avoid being bound by theory, the term "copolymer" generally includes polymers having two or more types of repeating monomer units (e.g., polymer chains containing or consisting of two or more different repeating monomer units, whether they are random copolymers, block copolymers, etc.). With regard to the specific case of polyvinyl alcohol polymers, the term "copolymer" (or "polyvinyl alcohol copolymer") can include copolymers having a distribution of vinyl alcohol monomer units and vinyl acetate monomer units (depending on the degree of hydrolysis), and at least one other type of repeating monomer unit (e.g., a ternary (or longer) polymer chain comprising or consisting of vinyl alcohol monomer units, vinyl acetate monomer units, and one or more other monomer units (e.g., anionic monomer units). In the example of 100% hydrolysis, a polyvinyl alcohol copolymer can include a copolymer having vinyl alcohol units and one or more other monomer units, but no vinyl acetate units. Not wishing to be bound by theory, the term "anionic copolymer" includes copolymers having anionic monomer units containing anionic moieties. Generally, anionic monomer units include vinyl polymeric units corresponding to monocarboxylic acid vinyl monomers, their esters and anhydrides, dicarboxylic acid monomers having polymerizable double bonds, their esters and anhydrides, vinyl sulfonic acid monomers, and alkali metal salts of any of the foregoing. Examples of anionic monomer units include vinyl polymerization units corresponding to vinyl anionic monomers, said vinyl anionic monomers including vinylacetic acid, maleic acid, monoalkyl maleate, dialkyl maleate, monomethyl maleate, dimethyl maleate, maleic anhydride, fumaric acid, monoalkyl fumarate, dialkyl fumarate, monomethyl fumarate, dimethyl fumarate, fumaric anhydride, itaconic acid, monomethyl itaconic acid, dimethyl itaconic acid, itaconic anhydride, vinyl sulfonic acid, allyl sulfonic acid, vinyl sulfonic acid, 2- Acrylamido-1-methylpropanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, 2-methylacrylamido-2-methylpropanesulfonic acid, 2-sulfoethyl acrylate, alkali metal salts of the foregoing (e.g., sodium, potassium or other alkali metal salts), esters of the foregoing (e.g., methyl ester, ethyl ester or other C1-C4 or C6 alkyl esters), and combinations thereof (e.g., multiple types of anionic monomers or equivalent forms of the same anionic monomer).Anionic monomers may include one or more acrylamidomethylpropanesulfonic acids (e.g., 2-acrylamido-1-methylpropanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, 2-methacrylamido-2-methylpropanesulfonic acid), their alkali metal salts (e.g., sodium salts), and combinations thereof.

[0050] Preferably, the first polyvinyl alcohol resin is present in the range of 50% to 95%, or 50% to 80%, more preferably 60% to 75% by weight of the first water-soluble film.

[0051] Preferably, the first polyvinyl alcohol resin comprises:

[0052] i. A first polyvinyl alcohol polymer comprising a carboxylated anionic monomer unit, a vinyl alcohol monomer unit, and optionally a vinyl acetate monomer unit, wherein the carboxylated anionic monomer unit is derived from a member selected from the group consisting of: maleic acid, monoalkyl maleate, dialkyl maleate, maleic anhydride, and combinations thereof.

[0053] ii. A second PVOH polymer, wherein the second PVOH polymer is a homopolymer, wherein the homopolymer comprises vinyl alcohol monomer units and optionally vinyl acetate monomer units.

[0054] Preferably, the first polyvinyl alcohol polymer in the first water-soluble film is characterized by:

[0055] a. The average viscosity (deionized water) of a 4% aqueous solution at 20°C is 10 mPa·s to 40 mPa·s, or 10 mPa·s to 30 mPa·s, or 12 mPa·s to 25 mPa·s, or 14 mPa·s to 20 mPa·s, or

[0056] b. The average degree of hydrolysis is 60% to 99%, preferably 80% to 98%, preferably 83% to 95%, preferably 85% to 92%, or

[0057] c. A mixture of them.

[0058] Preferably, the second polyvinyl alcohol polymer in the first water-soluble film is characterized by:

[0059] a. The average viscosity (deionized water) of a 4% aqueous solution at 20°C is 3 mPa·s to 30 mPa·s, or 7 mPa·s to 30 mPa·s, or 10 mPa·s to 30 mPa·s, or 12 mPa·s to 25 mPa·s; or

[0060] b. The average degree of hydrolysis is 60% to 99%, preferably 80% to 98%, preferably 85% to 95%, preferably 87% to 92%; or

[0061] c. A mixture of them.

[0062] 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.

[0063] Preferably, in the first water-soluble membrane, the relative weight ratio of the first PVOH polymer and the second PVOH polymer is between 90 / 10 and 10 / 90, more preferably between 80 / 20 and 20 / 80, and more preferably between 70 / 30 and 50 / 50.

[0064] 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 with a single membrane sheet thickness of 75 µm are prepared. The specimens are then transferred to the INSTRON tensile testing machine for testing, while minimizing exposure to the 35% relative humidity environment. 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 are 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).

[0065] The first water-soluble membrane is characterized by a minimum of approximately 20 N / mm², as measured by MOD testing at 35% RH. 2The MOD value is 100%. 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 membrane's ability to maintain stiffness rather than slack and sag when in contact with the contents of a liquid pouch. Specifically, a membrane with a higher MOD value corresponds to a pouch that is 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. In various embodiments, the MOD value of the first water-soluble membrane is at least about 20 N / mm². 2 21N / mm 2 22N / mm 2 23N / mm 2 24N / mm 2 25N / mm 2 Or 27N / mm 2 And / or at most about 24 N / mm 2 25N / mm 2 27N / mm 2 28N / mm 2 29N / mm 2 or 30N / mm 2 (For example, approximately 20 N / mm) 2 Approximately 30 N / mm 2 or approximately 20 N / mm 2 Approximately 28 N / mm 2 or approximately 22 N / mm 2 Approximately 25 N / mm 2 ).

[0066] Preferably, the first water-soluble film comprises between 0.1% and 3.5% by weight, or between 0.1% and 2.5%, or within the range of 1% to 2%, or within 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, the nonionic surfactant may be selected from alcohol ethoxylates; the cationic surfactant may be selected from quaternary ammonium salts; and the zwitterionic surfactant 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.

[0067] Preferably, as determined by Karl Fischer titration, the first water-soluble membrane has a residual moisture content of at least 4%, more preferably from 4% to 15%, and even more preferably from 5% to 10% based on the weight of the first water-soluble membrane.

[0068] Preferably, the first water-soluble film comprises 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, aversive agents, surfactants, and combinations thereof.

[0069] Preferably, the first water-soluble film contains one or more plasticizers, and the amount of plasticizer is between 5% and 50% by weight of the first water-soluble film, preferably between 10% and 40%, and most preferably between 20% and 30%. Preferably, the plasticizer in the first 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, polyethylene glycol, trimethylolpropane, and mixtures thereof.

[0070] Preferably, the first water-soluble film according to the invention comprises 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 in the range of 0.02% to 1.5% by weight, preferably 0.1% to 1%.

[0071] Preferably, the first water-soluble film comprises filler, expander, anti-blocking agent, anti-sticking agent, or mixture 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 filler, expander, anti-blocking agent, anti-sticking agent, or mixture thereof in the first water-soluble film is from 0.1% to 25% by weight, preferably from 1% to 10%, more preferably from 2% to 8%, and most preferably from 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 from 0.1% to 1% by weight of the first water-soluble film, preferably 4%, more preferably 6%, even more preferably 1% to 4%, and most preferably 1% to 2.5%.

[0072] The first water-soluble film may include a printing area. The printing area can be achieved using standard techniques such as flexographic printing or inkjet printing.

[0073] The first water-soluble membrane 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.

[0074] Preferably, the first water-soluble membrane and its respective individual components are independently contained between 0 ppm and 20 ppm, more preferably between 0 ppm and 15 ppm, more preferably between 0 ppm and 10 ppm, even more preferably between 0 ppm and 5 ppm, even more preferably between 0 ppm and 1 ppm, even more preferably between 0 ppb and 100 ppb, and most preferably between 0 ppb. Alkane. Those skilled in the art will understand the determination of dialkyl in water-soluble membranes and their components. Known methods and techniques for alkyl content analysis.

[0075] Second water-soluble membrane

[0076] The water-soluble unit-dose product may include a second water-soluble film. The second water-soluble film has a first side and a second side. The second water-soluble film comprises a second polyvinyl alcohol resin.

[0077] The second water-soluble membrane of the present invention is soluble or dispersible in water. The second water-soluble membrane preferably has an average 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 before deformation.

[0078] Preferably, as measured by the method described herein after using a glass filter with a maximum pore size of 20 micrometers, the second water-soluble membrane has a water solubility of at least 50%, preferably at least 75%, or even at least 95%: 5 g ± 0.1 g of membrane material is added to a pre-weighed 3 L beaker, and 2 L ± 5 ml of distilled water is added. This is vigorously stirred for 30 minutes at 30°C on a Labline magnetic stirrer (model 1250) or equivalent and a 5 cm magnetic stirrer (set to 600 rpm). The mixture is then filtered through a pleated qualitative porous glass filter with the aforementioned specified pore size (maximum 20 micrometers). The water in the collected filtrate is dried by any conventional method, and the weight of the remaining material (the dissolved or dispersed portion) is determined. The percentage of solubility or dispersion can then be calculated.

[0079] As is known in the art, the second water-soluble membrane material can be obtained by casting, blow molding, extrusion or blow extrusion of polymer materials, and preferably the second water-soluble membrane is a solvent-cast water-soluble membrane.

[0080] The second water-soluble film comprises polyvinyl alcohol resin. The polyvinyl alcohol resin may be between 50% and 95% by weight of the second water-soluble film, preferably between 50% and 80%, and more preferably between 60% and 75%.

[0081] The second polyvinyl alcohol resin comprises less than 15% by weight of a polyvinyl alcohol polymer, the polyvinyl alcohol polymer comprising carboxylated anionic monomer units, ethylene alcohol monomer units, and optionally vinyl acetate monomer units, wherein the carboxylated anionic monomer units are derived from members selected from the group consisting of: maleic acid, monoalkyl maleate, dialkyl maleate, maleic anhydride, and combinations thereof. Not wishing to be bound by theory, the polyvinyl alcohol polymer comprising carboxylated anionic monomer units, ethylene alcohol monomer units, and optionally vinyl acetate monomer units is an anionic polyvinyl alcohol copolymer. The second polyvinyl alcohol resin further comprises 85% to 100% by weight of a polyvinyl alcohol homopolymer or a polyvinyl alcohol homopolymer blend, wherein the polyvinyl alcohol homopolymer is composed of ethylene alcohol monomer units and optionally vinyl acetate monomer units.

[0082] The present invention includes a second water-soluble membrane comprising a second polyvinyl alcohol resin, wherein the second polyvinyl alcohol resin comprises less than 15% by weight of a polyvinyl alcohol polymer, the polyvinyl alcohol polymer comprising a carboxylated anionic monomer unit derived from a monoalkyl maleate unit, the monoalkyl maleate unit preferably selected from the group consisting of monomethyl maleate, its salts, preferably alkali metal salts, and combinations thereof. If present, preferably, the carboxylated anionic monomer unit is present in the polyvinyl alcohol polymer comprising the carboxylated anionic monomer unit in an average amount of at least 3 mol%, or 3 mol% to 6 mol%, or 3 mol% to 5 mol%, or 3.5 mol% to 4.5 mol%, or 4 mol% to 4.5 mol%. If present, the polyvinyl alcohol resin of the second water-soluble film is characterized by a polyvinyl alcohol polymer comprising carboxylated anionic monomer units, ethylene alcohol monomer units, and optionally vinyl acetate monomer units, preferably having an average 4% aqueous solution viscosity (deionized water) of 10 mPa·s to 40 mPa·s, or 10 mPa·s to 30 mPa·s, or 12 mPa·s to 25 mPa·s, or 14 mPa·s to 20 mPa·s at 20°C, or an average degree of hydrolysis of 60% to 99%, preferably 80% to 98%, preferably 83% to 95%, preferably 85% to 92%, or a mixture thereof.

[0083] Preferably, the carboxyl anion unit is derived from maleic acid, monoalkyl maleate, dialkyl maleate, monomethyl maleate, dimethyl maleate, maleic anhydride, or mixtures thereof. More preferably, the maleic acid unit is derived from the monoalkyl maleate unit, which is preferably selected from the group consisting of monomethyl maleate, its salts, preferably alkali metal salts, and combinations thereof.

[0084] The second polyvinyl alcohol resin further comprises 85% to 100% by weight of polyvinyl alcohol homopolymer or polyvinyl alcohol homopolymer blend, wherein the polyvinyl alcohol homopolymer is composed of ethylene alcohol monomer units and optionally vinyl acetate monomer units. More preferably, the second water-soluble film comprises polyvinyl alcohol resin, which comprises between 90% and 100%, more preferably 100% by weight of polyvinyl alcohol homopolymer or polyvinyl alcohol homopolymer blend.

[0085] Most preferably, the polyvinyl alcohol resin of the second water-soluble film comprises a blend of a first polyvinyl alcohol homopolymer and a second polyvinyl alcohol homopolymer, the blend of the first polyvinyl alcohol homopolymer and the second polyvinyl alcohol homopolymer having an average viscosity of 8 mPa·s or greater but less than 12 mPa·s, preferably 10 mPa·s or greater but less than 12 mPa·s, as measured in a 4% polyvinyl alcohol solution in deionized water at 20°C, and preferably, wherein the first polyvinyl alcohol homopolymer and the second polyvinyl alcohol homopolymer are present in a relative weight ratio of 90 / 10 to 10 / 90, preferably 80 / 20 to 20 / 80, more preferably 70 / 30 to 50 / 50. In this document, as measured in a 4% polyvinyl alcohol polymer solution in deionized water at 20°C, the first polyvinyl alcohol homopolymer has an average viscosity in the range of 11 mPa·s to 20 mPa·s, preferably between 11 mPa·s and 15 mPa·s; and as measured in a 4% polyvinyl alcohol polymer solution in deionized water at 20°C, the second polyvinyl alcohol homopolymer has an average viscosity in the range of 1 mPa·s to 10 mPa·s, preferably between 5 mPa·s and 10 mPa·s; more preferably, as measured in a 4% polyvinyl alcohol polymer solution in deionized water at 20°C, the Δ average viscosity between the first and second polyvinyl alcohol homopolymers is at least 1 mPa·s, preferably between 2 mPa·s and 10 mPa·s, more preferably between 3 mPa·s and 8 mPa·s. More preferably, the first and second polyvinyl alcohol homopolymers independently have an average degree of hydrolysis ranging from 75% to 99%, preferably from 80% to 95%, and most preferably from 85% to 95%. Most preferably, the polyvinyl alcohol resin of the second water-soluble film has an average degree of hydrolysis ranging from 75% to 99%, preferably from 80% to 95%, and most preferably from 85% to 95%. A suitable test method for measuring the degree of hydrolysis is according to standard method JIS K6726.

[0086] The second water-soluble membrane is characterized by a strength of less than 20 N / mm², as measured by MOD testing at 35% RH. 2 The 100% modulus value. Generally speaking, a higher MOD value (e.g., 20 N / mm) is associated with higher modulus. 2(or higher) is desirable because it corresponds to a membrane with greater stiffness and a lower likelihood of deformation and sticking together when loaded on top of each other during production or final consumption packaging. Furthermore, the MOD value at 100% elongation corresponds to the membrane's ability to maintain stiffness rather than slack and sag when in contact with the contents of the liquid pouch. Specifically, a membrane with a higher MOD value corresponds to a pouch that is less likely to soften and exhibit a slack and sag appearance when in contact with the contents of a liquid pouch containing a low molecular weight polyol. However, it is determined that the second polyvinyl alcohol membrane can advantageously have a lower 100% modulus as described herein. Furthermore, when used as an intermediate membrane in a stacked pouch construction as described herein, the relatively low MOD value and the resulting sagging tendency of the membrane are offset by the pouch construction, where the second membrane is substantially entirely within the pouch product. In various embodiments, the MOD value of the second water-soluble membrane can be less than about 20 N / mm. 2 or less than approximately 19 N / mm 2 or less than approximately 18 N / mm 2 or less than approximately 17 N / mm 2 or less than approximately 16 N / mm 2 or less than approximately 15 N / mm 2 or less than approximately 14 N / mm 2 and optionally at least about 9 N / mm 2 or at least about 10 N / mm 2 or at least about 11 N / mm 2 At least approximately 12 N / mm 2 or at least about 13 N / mm 2 For example, at approximately 10 N / mm 2 Approximately 16 N / mm 2 or approximately 11 N / mm 2 Approximately 15 N / mm 2 or approximately 12 N / mm 2 Approximately 14 N / mm 2 Within the range. In one related aspect, the second water-soluble membrane may be characterized in that its 100% modulus value is at least about 1 N / mm, which is different from the 100% modulus value of the first water-soluble membrane. 2 or at least about 2N / mm 2 or at least about 3N / mm 2 or at least about 4 N / mm 2 or at least about 5 N / mm 2 or at least about 6 N / mm 2 or at least about 7 N / mm 2 or at least about 10 N / mm 2 or at least about 20 N / mm 2 or at least about 25 N / mm 2Furthermore, it is optionally at least about 1 N / mm², which is different from the 100% modulus value of the third water-soluble film. 2 or at least about 2N / mm 2 or at least about 3N / mm 2 or at least about 4 N / mm 2 or at least about 5 N / mm 2 or at least about 6 N / mm 2 or at least about 7 N / mm 2 or at least about 10 N / mm 2 or at least about 20 N / mm 2 Furthermore, it is optionally at least about 1 N / mm², which is different from the 100% modulus value of both the first and third water-soluble membranes. 2 or at least about 2N / mm 2 or at least about 3N / mm 2 or at least about 4 N / mm 2 or at least about 5 N / mm 2 or at least about 6 N / mm 2 or at least about 7 N / mm 2 or at least about 10 N / mm 2 or at least about 20 N / mm 2 .

[0087] The viscosity of the second polyvinyl alcohol resin, as measured in a 4% polyvinyl alcohol solution in deionized water at 20°C, is 8 mPa·s or greater but less than 12 mPa·s, preferably 10 mPa·s or greater but less than 12 mPa·s. The viscosity of the polyvinyl alcohol polymer is determined by measuring a freshly prepared solution 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 of a 4% aqueous solution of polyvinyl alcohol (deionized water) at 20°C. It is well known in the art that the viscosity of aqueous solutions of water-soluble polymers (polyvinyl alcohol or other polymers) is related to the weight-average molecular weight of the same polymer, and viscosity is generally used as a representative of weight-average molecular weight.

[0088] Preferably, the second water-soluble membrane comprises between 0.1% and 3.5% by weight, or between 0.1% and 2.5%, or within the range of 1% to 2%, or within the range of 0.5% to 2% of the water-soluble membrane. 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, the nonionic surfactant may be selected from alcohol ethoxylates; the cationic surfactant may be selected from quaternary ammonium salts; and the zwitterionic surfactant 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.

[0089] Preferably, as determined by Karl Fischer titration, the second water-soluble membrane has a residual moisture content of at least 4%, more preferably from 4% to 15%, and even more preferably from 5% to 10% based on the weight of the second water-soluble membrane.

[0090] Preferably, the second water-soluble membrane comprises one or more components 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, odorants, surfactants, and combinations thereof.

[0091] Preferably, the second water-soluble film contains one or more plasticizers, and the amount of plasticizer is between 5% and 50% by weight of the second water-soluble film, preferably between 10% and 40%, and most preferably between 20% and 30%. Preferably, the plasticizer in the second 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, polyethylene glycol, trimethylolpropane, and mixtures thereof.

[0092] Preferably, the second water-soluble film according to the invention comprises 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 second water-soluble film is from 0.02% to 1.5% by weight, preferably from 0.1% to 1%.

[0093] Preferably, the second water-soluble film comprises 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 second water-soluble film is from 0.1% to 25% by weight, preferably from 1% to 10%, more preferably from 2% to 8%, and most preferably from 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 from 0.1% to 1% by weight of the second water-soluble film, preferably 4%, more preferably 6%, even more preferably 1% to 4%, and most preferably 1% to 2.5%.

[0094] The second water-soluble film may include a printing area. The printing area can be achieved using standard techniques such as flexographic printing or inkjet printing.

[0095] The second water-soluble membrane 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.

[0096] Preferably, the second water-soluble membrane and its respective individual components are independently contained between 0 ppm and 20 ppm, more preferably between 0 ppm and 15 ppm, more preferably between 0 ppm and 10 ppm, even more preferably between 0 ppm and 5 ppm, even more preferably between 0 ppm and 1 ppm, even more preferably between 0 ppb and 100 ppb, and most preferably at 0 ppb. Alkane. Those skilled in the art will understand the determination of dialkyl in water-soluble membranes and their components. Known methods and techniques for alkyl content analysis.

[0097] Third water-soluble membrane

[0098] The water-soluble unit-dosage product may include a third water-soluble membrane. The third water-soluble membrane of the present invention is soluble or dispersible in water. The third water-soluble membrane, before deformation, preferably 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 membrane has a first side and a second side.

[0099] Preferably, as measured by the method described herein after using a glass filter with a maximum pore size of 20 micrometers, the third water-soluble membrane has a water solubility of at least 50%, preferably at least 75%, or even at least 95%: 5 g ± 0.1 g of membrane material is added to a pre-weighed 3 L beaker, and 2 L ± 5 ml of distilled water is added. It is then vigorously stirred at 30°C for 30 minutes on a Labline magnetic stirrer (model 1250) or equivalent and a 5 cm magnetic stirrer (set to 600 rpm). The mixture is then filtered through a pleated qualitative porous glass filter with the aforementioned specified pore size (maximum 20 micrometers). The water in the collected filtrate is dried by any conventional method, and the weight of the remaining material (the dissolved or dispersed portion) is determined. The percentage of solubility or dispersion can then be calculated.

[0100] As is known in the art, a third water-soluble membrane material can be obtained by casting, blow molding, extrusion or blow extrusion of a polymer material, and preferably the third water-soluble membrane is a solvent-cast water-soluble membrane.

[0101] The third water-soluble film is a third polyvinyl alcohol (PVOH) resin, wherein the third polyvinyl alcohol resin comprises polyvinyl alcohol composed of polyvinyl alcohol homopolymer, anionic polyvinyl alcohol copolymer, or blends thereof.

[0102] Preferably, the third water-soluble membrane comprises a blend of polyvinyl alcohol homopolymer and / or anionic polyvinyl alcohol copolymer. Preferably, the third water-soluble membrane comprises a blend of polyvinyl alcohol homopolymer and anionic polyvinyl alcohol copolymer, wherein the polyvinyl alcohol homopolymer and the anionic polyvinyl alcohol copolymer are preferably present in a relative weight ratio of 90 / 10 to 10 / 90, preferably 80 / 20 to 20 / 80, and more preferably 70 / 30 to 50 / 50.

[0103] The third 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 100%. 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 membrane's ability to maintain stiffness rather than slack and sag when in contact with the contents of a liquid pouch. Specifically, membranes with higher MOD values ​​correspond to pouches that are less likely to soften and exhibit a slack and sagging appearance when in contact with liquid pouch contents containing low molecular weight polyols. In various embodiments, the MOD value of the third water-soluble membrane is at least about 20 N / mm. 2 21N / mm 2 22N / mm 2 23N / mm 2 24N / mm 2 25N / mm 2 Or 27N / mm 2 And / or at most about 24 N / mm 2 25N / mm 2 27N / mm 2 28N / mm 2 29N / mm 2 or 30N / mm 2 (For example, approximately 20 N / mm) 2 Approximately 30 N / mm 2 or approximately 20 N / mm 2 Approximately 28 N / mm 2 or approximately 22 N / mm 2 Approximately 25 N / mm 2 ).

[0104] Preferably, the third water-soluble membrane comprises anionic polyvinyl alcohol copolymer, said anionic polyvinyl alcohol copolymer comprising anionic monomer units, preferably wherein the anionic monomer units are present in the anionic polyvinyl alcohol copolymer in an average amount ranging from 1 mol% to 10 mol%, preferably from 2 mol% to 5 mol%. Preferably, the anionic polyvinyl alcohol copolymer is selected from sulfonated and carboxylated anionic polyvinyl alcohol copolymers, especially carboxylated anionic polyvinyl alcohol copolymers.

[0105] Most preferably, the third water-soluble membrane comprises a blend of polyvinyl alcohol homopolymer and a carboxylated anionic polyvinyl alcohol copolymer, preferably wherein the carboxylic ester is selected from acrylates, methacrylates, maleic esters, or mixtures thereof, preferably maleic esters. Preferably, the carboxylated anionic monomer unit in the third water-soluble membrane is derived from a monoalkyl maleate ester unit, which is preferably selected from the group consisting of monomethyl maleate, its salts, preferably alkali metal salts, and combinations thereof. Not wishing to be bound by theory, the polyvinyl alcohol polymer comprising carboxylated anionic monomer units, vinyl alcohol monomer units, and optionally vinyl acetate monomer units is an anionic polyvinyl alcohol copolymer. Preferably, each carboxylated anionic monomer unit is present in the carboxylated anionic polyvinyl alcohol copolymer in an average amount of 3 mol% to 6 mol%, or 3 mol% to 5 mol%, or 3.5 mol% to 4.5 mol%, or 4 mol% to 4.5 mol%.

[0106] Preferably, the third polyvinyl alcohol resin is present in the range of 50% to 95%, or 50% to 80%, more preferably 60% to 75% by weight of the third water-soluble film.

[0107] Preferably, the third polyvinyl alcohol resin comprises:

[0108] i. A first polyvinyl alcohol polymer comprising a carboxylated anionic monomer unit, a vinyl alcohol monomer unit, and optionally a vinyl acetate monomer unit, wherein the carboxylated anionic monomer unit is derived from a member selected from the group consisting of: maleic acid, monoalkyl maleate, dialkyl maleate, maleic anhydride, and combinations thereof.

[0109] ii. A second PVOH polymer, wherein the second PVOH polymer is a homopolymer, wherein the homopolymer comprises vinyl alcohol monomer units and optionally vinyl acetate monomer units.

[0110] Preferably, the first polyvinyl alcohol polymer in the third water-soluble membrane is characterized by:

[0111] a. The average viscosity (deionized water) of a 4% aqueous solution at 20°C is 10 mPa·s to 40 mPa·s, or 10 mPa·s to 30 mPa·s, or 12 mPa·s to 25 mPa·s, or 14 mPa·s to 20 mPa·s, or

[0112] b. The average degree of hydrolysis is 60% to 99%, preferably 80% to 98%, preferably 83% to 95%, preferably 85% to 92%, or

[0113] c. A mixture of them.

[0114] Preferably, the second polyvinyl alcohol polymer in the third water-soluble film is characterized by:

[0115] a. The average viscosity (deionized water) of a 4% aqueous solution at 20°C is 3 mPa·s to 30 mPa·s, or 7 mPa·s to 30 mPa·s, or 10 mPa·s to 30 mPa·s, or 12 mPa·s to 25 mPa·s; or

[0116] b. The average degree of hydrolysis is 60% to 99%, preferably 80% to 98%, preferably 85% to 95%, preferably 87% to 92%; or

[0117] c. A mixture of them.

[0118] Preferably, in the third water-soluble membrane, the relative weight ratio of the first PVOH polymer and the second PVOH polymer is between 90 / 10 and 10 / 90, more preferably between 80 / 20 and 20 / 80, and more preferably between 70 / 30 and 50 / 50.

[0119] Preferably, the third water-soluble membrane comprises between 0.1% and 3.5% by weight, or between 0.1% and 2.5%, or within the range of 1% to 2%, or within the range of 0.5% to 2% of the water-soluble membrane. 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, the nonionic surfactant may be selected from alcohol ethoxylates; the cationic surfactant may be selected from quaternary ammonium salts; and the zwitterionic surfactant 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.

[0120] Preferably, as determined by Karl Fischer titration, the third water-soluble membrane has a residual moisture content of at least 4%, more preferably from 4% to 15%, and even more preferably from 5% to 10% based on the weight of the first water-soluble membrane.

[0121] Preferably, the third water-soluble membrane comprises 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, anaerobic agents, surfactants, and combinations thereof.

[0122] Preferably, the third water-soluble film contains one or more plasticizers, and the amount of plasticizer is between 5% and 50% by weight of the third water-soluble film, preferably between 10% and 40%, and most preferably between 20% and 30%. Preferably, the plasticizer in the third water-soluble membrane 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, polyethylene glycol, trimethylolpropane, and mixtures thereof.

[0123] Preferably, the third water-soluble film according to the invention comprises 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 third water-soluble film is from 0.02% to 1.5% by weight of the first water-soluble film, preferably from 0.1% to 1%.

[0124] Preferably, the third water-soluble membrane comprises 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 third water-soluble membrane is from 0.1% to 25% by weight, preferably from 1% to 10%, more preferably from 2% to 8%, and most preferably from 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 from 0.1% to 1% by weight of the third water-soluble membrane, preferably 4%, more preferably 6%, even more preferably 1% to 4%, and most preferably 1% to 2.5%.

[0125] The third water-soluble film may include a printing area. The printing area can be achieved using standard techniques such as flexographic printing or inkjet printing.

[0126] The third water-soluble membrane 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.

[0127] Preferably, the third water-soluble membrane and its respective individual components are independently contained between 0 ppm and 20 ppm, more preferably between 0 ppm and 15 ppm, more preferably between 0 ppm and 10 ppm, even more preferably between 0 ppm and 5 ppm, even more preferably between 0 ppm and 1 ppm, even more preferably between 0 ppb and 100 ppb, and most preferably between 0 ppb. Alkane. Those skilled in the art will understand the determination of dialkyl in water-soluble membranes and their components. Known methods and techniques for alkyl content analysis.

[0128] Preferably, the first water-soluble membrane and the third water-soluble membrane are identical. The term "identical" in this document means that, during the manufacturing of a unit dose product before deformation, the first and third water-soluble membranes are physically and chemically identical, and "same" refers to standard treatments for manufacturing specification changes.

[0129] Methods for preparing water-soluble membranes

[0130] 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.

[0131] 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.

[0132] 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).

[0133] 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.

[0134] 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.

[0135] 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 for 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.

[0136] 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.

[0137] Typically, a release coating may comprise one or more surfactants and an optional carrier, such as water. The release coating may comprise one or more surfactants, such as those selected from fluorinated surfactants, non-fluorinated anionic surfactants, non-fluorinated amphoteric surfactants, their salts, or any combination thereof. In embodiments, the anionic or amphoteric surfactant may be non-fluorinated and contain C6-C. 30 Phosphate ester, C6-C 30 Phosphodiester, C6-C 30 Carboxylic esters, C6-C 30 Dicarboxylic acid esters, C6-C 30 Sulfate, C6-C 30 Disulfates or their salts. In embodiments, the release coating comprises a nonfluorinated amphoteric surfactant or a salt thereof. In embodiments, the release coating comprises a nonfluorinated anionic surfactant or a salt thereof. In embodiments, the nonfluorinated anionic surfactant comprises C6-C... 30 Phosphate ester, or C8-C 16 Phosphate ester, C6-C 60 Phosphodiester, C 16 -C 32 Phosphodiester, C6-C 30 Carboxylic esters, C6-C 30 Dicarboxylic acid esters, C6-C 30 Sulfate, C6-C 30 Disulfates or their salts. In embodiments, the nonfluorinated anionic surfactant comprises C6-C 30 Phosphate ester, or C6-C 18 Phosphate ester, C6-C 60 Phosphodiester, C 18 -C 32 Phosphate diesters or their salts. In embodiments, the anionic surfactant may be selected from one or more of the following: C6-based fluorinated aliphatic ammonium phosphate; tridecyl ethoxylated phosphate, POE-12, tridecyl ethoxylated phosphate, POE-3, lauryl ether-11 carboxylic acid; crypto-anionic surfactant - lauryl ether-6 carboxylic acid; or sodium lauryl ether sulfate, POE-4.

[0138] As used herein, the term "non-fluorinated" refers to a surfactant having less than 0.01% by weight of fluorine based on the total molecular weight of the compound, or less than 0.001% by weight of fluorine based on the total molecular weight of the compound, or less than 0.0001% by weight of fluorine based on the total molecular weight of the compound.

[0139] In embodiments, the release coating may include a fluorinated surfactant, such as a perfluoroalkyl compound. In embodiments, the fluorinated surfactant may include a solution of ZONYL FSP surfactant (EI du Pont de Nemours and Company). The use of a surfactant in the range of about 0.05% to about 5.0% by weight in the release coating is considered. The amount of surfactant required to provide adequate wetting may vary depending on the film coated on the strip. Other products may require higher concentrations to improve release properties. Using higher surfactant concentrations will result in more efficient spreading and wetting of hard surfaces before the surfactant solution reaches the critical micelle concentration (CMC). This concentration represents a threshold beyond which additional surfactant will not produce any further spreading and wetting efficiency. However, increasing the concentration above the CMC can improve wetting via the polymer solution and improve the release properties of some film formulations.

[0140] A release coating can be applied to a substrate surface and optionally subsequently dried, followed by casting a polymeric resin or polymeric resin solution onto the surface-coated substrate. In embodiments, the release coating may have a pH of about 1 to about 5 when applied to the substrate surface before drying. In embodiments where the surfactant comprises a non-fluorinated anionic surfactant, a non-fluorinated zwitterionic surfactant, salts thereof, or combinations thereof, the release coating may have a pH of about 1 to about 8 or a pH of about 1 to about 5 when applied to the substrate surface before drying. For example, the release coating may have a pH of about 1, about 1.5, about 2, about 2.5, about 3, about 3.5, about 4, about 5, about 6, about 7, or about 8 when applied to the substrate surface. In an embodiment, prior to the release coating on the dry substrate surface, the release coating may have a pH of about 1 to about 7, or about 1 to about 6, or about 1 to about 4, or about 1 to about 3, or about 2 to about 7, or about 2 to about 6, or about 2 to about 5, or about 2 to about 4, or about 2 to about 3, or about 3 to about 7, or about 3 to about 5, or about 1.5 to about 3.5, or about 4 to about 7.

[0141] 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 one 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 another 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%. In yet another embodiment, after the release coating on the dried substrate surface, the release coating may have a surfactant concentration ranging from about 4.7 wt% to about 100 wt% based on the total weight of the release coating. For example, based on the total weight of the release coating, the release coating may contain ZONYL surfactant in the range of about 0.05% to about 5.0% by weight.

[0142] 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.

[0143] 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.

[0144] Laundry detergent composition or automatic dishwashing detergent composition

[0145] The water-soluble unit dose product comprises a laundry detergent composition or an automatic dishwashing detergent composition, preferably comprising a laundry detergent composition.

[0146] The laundry detergent composition is preferably a liquid laundry detergent composition.

[0147] 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.

[0148] 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.

[0149] Preferably, the liquid laundry detergent composition comprises 15% to 55% of a non-soap anionic surfactant by weight of the laundry detergent composition. More preferably, the detergent composition comprises between 20% and 55%, more preferably between 25% and 50%, of a non-soap anionic surfactant.

[0150] 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 comprises between 1% and 40%, preferably between 3% and 40%, and more preferably between 6% and 35% by weight of the liquid laundry detergent composition.

[0151] 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 naturally derived materials, synthetically derived materials, or mixtures thereof. Preferably, synthetically derived materials 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.

[0152] 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.

[0153] The liquid laundry detergent composition contains 2.5% to 30% of a nonionic surfactant by weight of the liquid laundry detergent composition. The nonionic surfactant is described in more detail below.

[0154] 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.

[0155] Preferably, the liquid laundry detergent composition comprises a nonionic surfactant. 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 can be a primary alkoxylated alcohol, a secondary alkoxylated alcohol, or a mixture thereof, preferably a primary alkoxylated alcohol. Preferably, the alkoxylated alcohol includes ethoxylated alcohols, propoxylated alcohols, mixed ethoxylated / propoxylated alcohols, or mixtures thereof, more preferably ethoxylated alcohols. Alternatively, the alkoxylated alcohol may also include higher alkoxy groups, such as butoxy groups. When alkoxy groups are mixed, the alkoxy groups can be randomly ordered or present in blocks, preferably present in blocks. For example, the mixed ethoxy (EO) / propoxy (PO) groups can 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 15. 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 20%. 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 synthetically sourced materials 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 the most preferred. Preferably, the liquid laundry detergent composition comprises between 0.5% and 20% by weight of the liquid laundry detergent composition, preferably between 1% and 15%, more preferably between 3% and 12%, of a nonionic surfactant, preferably wherein the nonionic surfactant is composed of an alkoxylated alcohol. Not wishing to be bound by theory, nonionic surfactants, especially alkoxylated alcohol nonionic surfactants, provide excellent effects in cleaning body grime and suspending dirt.

[0156] Preferably, the weight ratio of the non-soap anionic surfactant to the nonionic surfactant is 1:1 to 20:1, 1.5:1 to 17.5:1, 2:1 to 15:1, or 2.5:1 to 13:1.

[0157] 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 fatty acids at a weight of between 1.5% and 20%, between 2% and 15%, between 3% and 12%, or between 4% and 10% of the liquid detergent composition.

[0158] Preferably, the liquid laundry detergent composition comprises between 1% and 20%, and more preferably between 5% and 15%, of water by weight of the liquid laundry detergent composition.

[0159] 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.

[0160] 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.

[0161] Preferably, the laundry detergent composition comprises other enzymes selected from the group consisting of: hemicellulase, peroxidase, protease, cellulase, xylanase, lipase, phospholipase, esterase, keratinase, pectinase, keratinase, reductase, oxidase, phenol oxidase, lipoxygenase, ligninase, amylopectinase, tannic acidase, pentosanase, melanase, β-glucanase, arabinase, hyaluronidase, chondroitinase, laccase, xyloglucanase, mannanase, and amylase, nuclease, or mixtures thereof, preferably comprising other enzymes selected from the group consisting of: protease, amylase, cellulase, lipase, xyloglucanase, mannanase, and mixtures thereof. Preferably, the other enzyme is a lipase.

[0162] As used herein, the term lipase includes enzymes that catalyze the hydrolysis of fats (lipids). Lipases are a subclass of esterases. Lipases suitable for use in this invention include phospholipases, acyltransferases, or perhydrolases, such as acyltransferases homologous to Candida antarctica lipase A, acyltransferases from Mycobacterium smegmatis, perhydrolases from the CE 7 family, and variants of Mycobacterium smegmatis perhydrolases, particularly the S54V variant used in the commercial product Gentle Power Bleach from Huntsman Textile Effects Pte Ltd. Suitable esterases and keratinases include those of bacterial or fungal origin. Chemically modified or protein-engineered mutant enzymes are also included. Examples include lipases from the genus *Thermomyces*, such as *T. lanuginosus* (formerly named *Humicola lanuginosa*); keratinases from the genus *Humicola*, such as *H. insolens*; lipases from strains of the genus *Pseudomonas* (some of which are now renamed *Burkholderia*), such as *P. alcaligenes* or *P. pseudoalcaligenes*, *P. cepacia*, *P. sp. strain* SD705, and *P. wisconsinensis*; lipases from *Streptomyces* of type GDSL; and lipases from *Magnaporthe*. The composition includes lipases from *Grisaema grisea*, *Pseudomonas mendocina*, *Thermobifida fusca*, *Geobacillus stearothermophilus*, *Bacillus subtilis*, *Streptomyces griseus*, and *S. pristinaespiralis*. Typically, the lipases are present in the composition at an amount of 0.001% to 0.03%, preferably 0.0025% to 0.025%, and more preferably 0.005% to 0.02% of the enzyme-active protein by weight of the composition. Unbound by theory, the enzymes are provided in the form of formulations containing the enzyme and other ingredients. The enzyme itself is a protein that catalyzes a reaction.In this article, enzyme-active proteins refer to enzymes that can actively catalyze related reactions.

[0163] 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.

[0164] 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.

[0165] 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.

[0166] 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., POLY-TERGENT from Olin Corporation). ® SLF18), epoxy-terminated poly(alkoxylated) alcohols (e.g., Olin Corporation's POLY-TERGENT) ® SLF18B), ether-terminated poly(alkoxylated) alcohol surfactants, and block polyoxyethylene-polyoxypropylene polymers such as BASF-Wyandotte Corp.'s (Wyandotte, Michigan) PLURONIC. ® REVERSED PLURONIC ® and TETRONIC ®The range includes: 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™ C2M; and zwitterionic surfactants such as betaine and sulfobetaine; and mixtures thereof. The surfactants may be present at levels of 0.2% to 30%, more preferably 0.5% to 10%, and most preferably 1% to 5% by weight of the detergent composition.

[0167] 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.

[0168] Enzymes suitable for use in the detergent compositions described herein include bacterial and fungal cellulases, including CAREZYME. ® and CELLUZYME ® (Novo Nordisk A / S); peroxidase; lipase, including AMANO-P ® (AmanoPharmaceutical Co.), M1 LIPASE ® and LIPOMAX ® (Gist-Brocades) and LIPOLASE ® And LIPOLASE ULTRA ® (Novo); keratinase; protease, including ESPERASE ® ALCALASE ® DURAZYM ® and SAVINASE ® (Novo) and MAXATASE ® MAXACAL ® PROPERASE ® and MAXAPEM ® (Gist-Brocades); βδ and αδ amylases, including PURAFECT ® OX AM (Genencor) and TERMAMYL ® BAN ® FUNGAMYL ® DURAMYL ® and NATALASE ®(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.

[0169] Defoamers 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 POLY-TERGENT). ® SLF18) and epoxy-terminated poly(alkoxylated) alcohols (e.g., BASFPOLY-TERGENT) ® SLF18B series nonionic compounds).

[0170] 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 polymers such as SOKALAN. ® PA30, PA20, PA15, PA10 and SOKALAN ® CP10 (BASF GmbH), ACUSL ® 45N, 480N, 460N (Rohmand Haas), acrylic / maleic acid copolymers such as SOKALAN ® CP5, and acrylic / methacrylic acid copolymers. Other suitable polymers include amine-based polymers such as alkoxylated polyalkylimides (e.g., PEI600 EO20 and / or ethoxylated hexamethylenediamine dimethyl quaternary ammonium salt), which may optionally be quaternized. Detergent polymers that may 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.

[0171] 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.

[0172] Corrosion inhibitors, such as organic silver coating agents (especially paraffins, such as WINGOG 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).

[0173] Other components applicable to the detergent compositions described herein include enzyme stabilizers such as calcium ions, boric acid, and propylene glycol.

[0174] 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 drain from the rinsed surface as a thin cohesive film, thus leaving no water droplets, streaks, or films after the subsequent drying process.

[0175] Method for preparing water-soluble unit dose products

[0176] Another aspect of the present invention is a method for preparing a water-soluble unit dose product according to the present invention, the method comprising the following steps:

[0177] a. The first water-soluble film is deformed in a mold by thermoforming, vacuum forming, or a combination thereof to produce an open mouth body;

[0178] b. Fill the oral cavity with the laundry detergent composition or the automatic dishwashing detergent composition;

[0179] c. To produce at least one open cavity by individually deforming the third water-soluble film in a mold through thermoforming, vacuum forming, or a combination thereof;

[0180] d. Fill the at least one opening from step c with the laundry detergent composition or automatic dishwashing detergent composition;

[0181] e. Seal the filled oral cavity from step c with a second water-soluble membrane;

[0182] f. Seal the second water-soluble membrane and the third water-soluble membrane to produce a closed intermediate, preferably wherein the second water-soluble membrane and the third water-soluble membrane are sealed by solvent sealing, more preferably wherein a solvent sealing solution is applied to a first side of the second water-soluble membrane before sealing the membranes together, the first side being the side facing the third water-soluble membrane;

[0183] g. Close the filled oral cavity from step b with the closed intermediate from step f;

[0184] h. Sealing the first water-soluble film and the second water-soluble film to produce a water-soluble unit dose article, preferably wherein the first water-soluble film and the second water-soluble film are sealed by solvent sealing, more preferably wherein a solvent sealing solution is applied to a second side of the second water-soluble film before sealing the films together, the second side being the side facing the first water-soluble film.

[0185] Preferably, the first water-soluble film in step a and the third water-soluble film in step c are identical before deformation. The term "identical" herein means that, during the manufacture of a unit dose article, the first and third water-soluble films are physically and chemically identical before deformation, while the term "same" refers to a standard process involving changes in manufacturing specifications.

[0186] 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.

[0187] 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.

[0188] 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.

[0189] 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.

[0190] 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.

[0191] 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, nonwovens, 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. 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, a spray nozzle, a metering nozzle, or a combination thereof, more preferably via a felt roller. 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 concentration of 1g to 30g per square meter, more preferably between 5g and 20g per square meter.

[0192] The water-soluble membrane can be preheated before deformation by a hot plate, an infrared lamp, or a combination thereof, preferably an infrared lamp.

[0193] The mold in which the article is prepared can have any shape, length, width, and depth, depending on the required pouch size. If desired, the molds can also differ from one another 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 20 ml to about 100 ml, and the mold size can be adjusted accordingly.

[0194] 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 a range around which it is functionally equivalent. For example, a dimension disclosed as “40 mm” is intended to represent “approximately 40 mm”.

[0195] 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 a range around which it is functionally equivalent. For example, a dimension disclosed as “40 mm” is intended to represent “approximately 40 mm”.

[0196] Example

[0197] The effects of the presence or absence of anionic polyvinyl alcohol copolymers have been investigated, as well as the effects of different average molecular weights (expressed as 4% viscosity of polymer aqueous solution (deionized water)) of polyvinyl alcohol homopolymer blends containing polymer resins on 1) the sensitivity of the corresponding water-soluble membrane to the formation of a foam layer on the membrane surface after the application of a sealing solvent, 2) the strength of the resulting seal and unit dose article, and 3) the dissolution characteristics of the membrane / unit dose article.

[0198] Test materials :

[0199] Water-soluble membrane :

[0200] The solvent-cast water-soluble test membranes, with varying polyvinyl alcohol types, were supplied by MonoSol. The test membranes comprise 65% water-soluble polyvinyl alcohol resin, with the remainder consisting of water, plasticizers, surfactants, and other materials typically present in water-soluble membranes. Comparative Examples 1 to 4 comprise 15% to 30% anionic copolymers by weight of the polyvinyl alcohol polymer resin, and are therefore outside the scope of this invention. Comparative Examples 5 to 7 comprise polyvinyl alcohol homopolymer blends, but their average viscosity is outside the scope of this invention.

[0201] Example 1 of the present invention comprises a polyvinyl alcohol homopolymer blend having an average viscosity according to the present invention.

[0202] • Anionic polyvinyl alcohol copolymers constituting the resin (by weight of polyvinyl alcohol polymer resin):

[0203] Comparative Example 1: A polyvinyl alcohol blend comprising 70% polyvinyl alcohol homopolymer (13 mPa.s, dH 86%) and 30% anionic polyvinyl alcohol copolymer based on methyl maleate (4% anionic substitution, 18 mPa.s, 90% dH).

[0204] Comparative Example 2: A polyvinyl alcohol blend comprising 85% polyvinyl alcohol homopolymer (13 mPa.s, dH 86%) and 15% anionic polyvinyl alcohol copolymer based on methyl maleate (4% anionic substitution, 18 mPa.s, 90% dH).

[0205] Comparative Example 3: A polyvinyl alcohol blend comprising 85% polyvinyl alcohol homopolymer (8 mPa.s, dH 88%) and 15% anionic polyvinyl alcohol copolymer based on methyl maleate (4% anionic substitution, 18 mPa.s, 90% dH).

[0206] Comparative Example 4: A polyvinyl alcohol blend comprising 85% polyvinyl alcohol homopolymer (18 mPa.s, dH 88%) and 15% anionic polyvinyl alcohol copolymer based on methyl maleate (4% anionic substitution, 18 mPa.s, 90% dH).

[0207] • Resins composed of polyvinyl alcohol homopolymer (by weight %):

[0208] Comparative Example 5: 100% polyvinyl alcohol homopolymer (13 mPa.s, dH 86%)

[0209] Comparative Example 6: Polyvinyl alcohol homopolymer blend containing 80% polyvinyl alcohol homopolymer (13 mPa·s, dH 86%) and 20% polyvinyl alcohol homopolymer (8 mPa·s, dH 88%) - Average viscosity: 12 mPa·s

[0210] Comparative Example 7: Polyvinyl alcohol homopolymer blend containing 80% polyvinyl alcohol homopolymer (13 mPa·s, dH 86%) - 20% polyvinyl alcohol homopolymer (18 mPa·s, dH 88%) - Average viscosity: 14 mPa·s

[0211] Example 1 of the present invention: A polyvinyl alcohol homopolymer blend comprising 60% polyvinyl alcohol homopolymer (13 mPa·s, dH 86%) and 40% polyvinyl alcohol homopolymer (8 mPa·s, dH 88%) - average viscosity: 11 mPa·s

[0212] Water-soluble unit dose products :

[0213] These water-soluble test membranes are used to produce water-soluble unit dose products. A first water-soluble membrane, supplied by MonoSol, comprising a polyvinyl alcohol blend of 60% polyvinyl alcohol homopolymer (23 mPa·s, 87% dH) and 40% anionic polyvinyl alcohol copolymer based on methyl maleate (4% anionic substitution, 18 mPa·s, 90% dH), is drawn under vacuum in a mold containing two side-by-side cavities to create open compartments. A liquid laundry detergent composition is metered into these open compartments, and then the filled open compartments are sealed with the aforementioned test membrane. The side-by-side configuration indicates a top compartment configuration, as shown below. Figure 1 As shown in the diagram. Two membranes are sealed together with water, and the sealing water is pre-applied to the surface of the test membrane facing the first water-soluble membrane using a pre-wetted felt roller. The target sealing water coating weight is 9 grams of water per square meter of water-soluble membrane. A third water-soluble membrane with the same composition as the first water-soluble membrane is drawn under vacuum in a separate mold containing a single cavity to create an open compartment. Before closing the open compartment of the unit dose article having the side-by-side compartments created above, a detergent composition is metered into the open compartment to create as shown in the diagram. Figure 1 The water-soluble unit-dosage product shown and marketed by Procter and Gamble in the UK under the brand name Fairy NonBio in July 2020 is as follows. Therefore, sealing water is pre-applied to the surface of the test membrane facing the third water-soluble membrane via a pre-wetted felt roller. The target sealing water coating weight is 13 grams of water per square meter of water-soluble membrane. All water-soluble membranes used have an initial thickness of 76 micrometers prior to product production.

[0214] Liquid laundry detergent composition:

[0215] The corresponding liquid laundry detergent compositions added to the separate compartments described in the above-described water-soluble unit dose product section are summarized in Table 1. The liquid laundry detergent compositions are prepared by mixing the individual components in a batch process.

[0216] Table 1: Liquid Laundry Detergent Formulations

[0217]

[0218] *Ethoxylated polyethyleneimine, having an average degree of ethoxylation of 20 per EO chain and a polyethyleneimine backbone with a MW of approximately 600.

[0219] **Lutensit Z96: Partially sulfated polyoxyethylene ether hexamethylenediamine, available from BASF.**

[0220] ***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.

[0221] Test Results :

[0222] The presence or absence of a foam layer :

[0223] Before contact with the third water-soluble membrane, and after the sealing water application step on the test membrane, a visual evaluation was performed on the water-soluble test membranes according to the invention and those outside the scope of the invention to determine whether a foam layer was present or absent at the surface of the water-soluble membrane. The results summarized in Table 2 below clearly show that water-soluble membranes containing water-soluble resins with 15% to 30% anionic copolymers (Comparative Examples 1 to 4) are sensitive to the formation of a foam layer at the surface of the water-soluble membrane upon application of sealing water, which is the opposite of water-soluble membranes containing polymer resins composed of polyvinyl alcohol homopolymers (blends) (Examples 1 of the invention and Comparative Examples 5 to 7). This foam layer is believed to drive uneven diffusion of the sealing water, thus resulting in poor sealing quality after the presence of weak sealing points.

[0224] Table 2: Presence or Absence of Foam Layer

[0225]

[0226] Small bag strength pass rate % and seal failure % :

[0227] Test methods :

[0228] This test method describes the practice of determining the bag strength pass rate (%) and seal failure rate (%) using a Mark-10 test instrument ESM750SLCE (JJ BOS BV, Marconistraat 1, NL-2809 PH Gouda, The Nederlands) with a pressure-sensing element of up to 100 kN (kilonewtons). Under external compressive force, the bag deforms, thereby generating stress on the membrane and sealing area. The internal pressure within the bag depends on the external force applied across the entire surface area of ​​the bag. Bag strength (in Newtons) is defined as the maximum compressive force required to increase the internal pressure of the bag to the burst point using two parallel plates. A bag bursting at the sealing area is reported as a "seal failure," used to calculate the seal failure rate (%) for 18 repetitions (seal failure = 1, no seal failure = 0). A bag bursting at a pressure equal to that generated by compression of less than 300 N is reported as a "failure," used to calculate the bag strength pass rate (%) for 18 repetitions (failure = 0, pass = 1).

[0229] After storing the water-soluble pouches under ambient conditions for 7 days and pre-conditioning them for 16 to 24 hours at 23°C / 50% RH, the pouch strength pass rate (%) and seal failure (%) were measured. This 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 within 1 hour. Inside Test it.

[0230] Figure 2 A schematic diagram of the basic configuration for testing bag strength pass rate (%) and seal failure rate (%) is shown. To measure bag strength pass rate (%) and seal failure rate (%), a 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., Raja clamp RGP6B) to prevent contamination of the working environment should the bag break. The bag 510 is centered within the bag and placed between two compression plates 520 and 530 of the instrument. The bag 510 is placed in an upright 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 located between the compression plates (x-direction), so that stress will be applied to the width seal. Therefore, the diameter of the compression plates needs to be large enough to prevent the bag from being crushed when it deforms (here, D = 116mm). For compression, the distance between plates 520 and 530 is reduced at a rate of 200mm / min. Each test segment was repeated 18 times, and the bag strength pass rate % and seal failure rate data for these 18 repetitions were reported.

[0231] Test Results :

[0232] The results summarized in Table 3 clearly demonstrate that, compared to water-soluble unit-dose products containing a water-soluble test film (comparative Examples 5 to 7, comprising a polyvinyl alcohol-based polymer resin composed of a homopolymer blend with an average viscosity distribution outside the scope of the present invention), and compared to water-soluble unit-dose products containing a water-soluble test film (comparative Examples 1 to 4, comprising a polyvinyl alcohol-based polymer resin composed of a homopolymer blend having an average viscosity distribution according to the present invention), the water-soluble unit-dose product containing a water-soluble test film (comprising a polyvinyl alcohol-based polymer resin containing 15% to 30% anionic polyvinyl alcohol copolymer) (Example 1 of the present invention) exhibits superior pouch strength and seal failure characteristics.

[0233] Table 3: Bag Strength and Sealing Failure

[0234]

[0235] *The higher the better

[0236] **The lower the better**

[0237] Water-soluble unit dose product dissolution-film residue

[0238] Test methods :

[0239] This test method describes a dissolution test for water-soluble unit dose products, in which the amount of undissolved water-soluble film residue is evaluated. More specifically, the method is designed to evaluate the relative solubility characteristics of water-soluble unit dose products in laundry under stressed washing machine conditions. For this method, a W565H Electrolux programmable washing machine was used, which includes a ballast containing a mixture of cotton and polyester-cotton sheets (from Calderon Textiles, LLC 6131 W 80th Street Indianapolis, IN 46278). The ballast consisted of cotton and polyester-cotton knitted fabrics, with a double-layer sample size of approximately 50 cm × 50 cm.

[0240] Orange pouch Divide brand new white cotton ballast from Calderon (50cm x 50cm) into portions up to 3.0kg each (approximately 25 ballasts) and dye them orange using a commercially available dyeing solution via a machine dyeing process. For dyeing the ballasts, any standard household washing machine can be used at 40°C using a standard cotton cycle. Add 350g of Dylon Fresh Orange Machine Dye All-in-One to the drum of the washing machine. Salt may be added according to the dye packaging instructions.

[0241] Therefore, manually move the roller left and right until the dye is no longer visible. Then, evenly distribute 25 cotton ballasts (50cm x 50cm) on the roller without folding the items. Run a standard cotton cycle at 40°C with a water hardness of 15gpg. After the cycle, add 75g of Ariel Professional powder to the dispenser and run a normal cotton cycle at 40°C with a water hardness of 15gpg. After this cycle, run two more normal cotton cycles at 40°C without any detergent with a water hardness of 15gpg, and then air dry the items.

[0242] Note: Brand new Calderon loads must be desized before coloring by adding 25 cotton loads to a pre-loaded Miele washing machine and running two short cotton cycles (approximately 1 hour and 30 minutes) at 60°C with 50g Ariel sensitive powder and 15gpg water hardness, followed by two more short cotton cycles (approximately 1 hour and 30 minutes) at 60°C with 15gpg water hardness without detergent, and then tumble drying.

[0243] The orange fabric was then cut into 48cm x 48cm pieces, folded in half, cut in half again, and sawn into four identical 22cm x 22cm pouches, each with an opening at the top. One pre-conditioned test product of the water-soluble unit dose was placed in the lower right corner of each orange pouch, and the pouch was sewn closed. The water-soluble unit dose product must be pre-conditioned at 23°C and 50% rH for at least two weeks prior to testing.

[0244] Loading material: Four 3kg loads of blended cotton (13 sheets) and polyester-cotton (10 sheets) were washed in a short cotton cycle at 60°C with 79g Ariel Professional detergent and 15gpg water hardness before use, followed by another short cotton cycle at 60°C with 15gpg water hardness without any detergent, and finally desizing by drum drying. Each 3.0kg load was pretreated twice by washing with 4 Ariel pods in a "pre-wetting" cycle, followed by washing without detergent in a "dissolving procedure" as described below, and finally drum drying.

[0245] The Electrolux W565 programmable washing machine is programmed with two programs. The first program is designed to equally wet the load (pre-wetting program). The second program (dissolving program) simulates a 15-minute Western European pressure cycle setting, followed by pumping out water and spinning for 3 minutes starting at 1100 rpm.

[0246]

[0247] The load (weighing 3.0 + / - 0.15 kg) consisting of 13 pieces of 50cm × 50cm cotton and 10 pieces of 27cm × 27cm polyester-cotton blends is evenly introduced into the Electrolux W565 washing machine, and the pre-wetting program is run twice.

[0248] After the pre-wetting process, the wet ballast is removed from the drum, and four orange pouches, each containing a different test section of water-soluble unit dose, are arranged at the bottom of the drum. This allows for testing four different test products simultaneously in the same washing machine, ensuring the test environment is as reproducible as possible within the test section. 10g of defoamer (Dowsil GP-4314 siloxane defoamer, commercially available from Dow Corning) is added to the dispenser, and the wet load is placed on top of the orange pouches, preventing drum movement. The dissolving process is then initiated. At the end of the entire process, the orange pouches are transferred to a grading chamber (equipped with D65 lighting conditions) for evaluation of residues by an expert grader.

[0249] Within 30 minutes of each run, the orange bag was cut open and visually graded according to a scale of 0 to 7 (0 = no film residue, 7 = full bag of residue). The final score was calculated as the average of 4 external replicates, i.e., 4 different washing machine runs, repeated 2 times (the average of 8 scores).

[0250] Test Results :

[0251] The results summarized in Table 4 clearly show that, compared with the tested water-soluble unit-dose products containing a water-soluble test film (comparative Examples 5 to 6, comprising a polyvinyl alcohol-based polymer resin composed of a polyvinyl alcohol homopolymer blend with an average viscosity distribution outside the scope of the present invention), and compared with the tested water-soluble unit-dose products containing a water-soluble test film (comprising a polyvinyl alcohol-based polymer resin containing 15% anionic polyvinyl alcohol copolymer) (comparative Examples 2 to 3), the water-soluble unit-dose product containing a water-soluble test film (comprising a polyvinyl alcohol-based polymer resin composed of a homopolymer blend having an average viscosity distribution according to the present invention) (Example 1 of the present invention), despite having excellent pouch strength, did not exhibit reduced solubility.

[0252] Table 4: Classification of Membrane Residues

[0253]

[0254] *The lower the better

[0255] Overall Conclusion :

[0256] The data compiled from the different embodiments clearly show that, compared with comparative water-soluble film compositions outside the scope of the present invention, water-soluble films comprising polyvinyl alcohol-based resins consisting of polyvinyl alcohol homopolymer blends having the viscosity distribution according to the present invention do not form a foam layer after the application of a sealing solvent, resulting in excellent sealing and pouch strength distribution, without causing a decrease in solubility.

[0257] Example 2

[0258] The peel strength of various films sealed in Comparative Example 1 and various films sealed in film 1 of the present invention was compared.

[0259] Test methods :

[0260] This method is used to determine the tensile force (seal peel strength) required for a water-soluble membrane to be sealed with a peel solution. Membrane data are collected using an INSTRON tensile testing apparatus or equivalent. Two membranes are fixed in deionized water using an ESIPROOF prototyping apparatus with an anilox roller 140 / 10 or equivalent. At least three test samples are tested in the longitudinal direction (MD) for each measurement, with each cut performed using a reliable cutting tool to ensure dimensional stability and reproducibility. Tests are conducted in a standard laboratory atmosphere at 23 ± 2.0 °C and 35 ± 5% relative humidity.

[0261] To determine seal peel strength, test samples were prepared by cutting two 12" (30.5cm) 4" × 12" (10.2cm × 30.5cm) membrane sheets in the longitudinal (MD) direction (where applicable). For one sheet, the four corners were taped to the surface with the matte surface of the membrane facing up. The other sheet was placed on top of the tapered sheet, with the matte surfaces in contact. The 4-inch (10.2cm) end of the top sheet was taped to secure it to the bottom sheet. The loose end of the top sheet was passed through the ESIPROOF sample roller using a 140 / 10 anilox roller. 0.5mL of test seal solution (water) was applied to the doctor blade. The roller was pulled at a constant speed (3" 7.6cm / s) to coat the upper membrane and secure it to the lower sheet. The membrane was allowed to weld for approximately 10 to 15 minutes to form a seal, but two unsealed (free) membrane flaps were left at one end of the test sample for subsequent peel testing. The sealed samples were then transferred to an INSTRON tensile testing machine for testing, while minimizing exposure to an environment with 35% relative humidity. The tensile testing machine, equipped with a calibrated 500N load cell, was prepared according to the manufacturer's instructions. The correct clamps and faces were then fitted.

[0262] For the peel test, there is a 0.50" (1.27cm) gap between the rubber clamps, and all four are flat and square. Cut three (or more) 1" wide (2.54cm) samples longitudinally (MD). Place the unsealed flap of each sample into the clamp of the testing machine, ensuring that the sample is aligned with and parallel to the clamp, and that the sample is not pulled too tightly in the jaws of the tester. Balance the load and start the test according to the equipment manufacturer's instructions. At the end of the test, record the absolute positive force (APF, in Newtons) required to tear or separate each layer as the seal peel strength.

[0263] Additional test materials :

[0264] Solvent-cast water-soluble test membranes with varying levels of copolymer content were prepared. The test membranes contained approximately 65%-77% of one or more water-soluble polyvinyl alcohol resins in the following ratios, with the remainder being water, plasticizers, surfactants, and other materials typically present in water-soluble membranes. The test membranes of Comparative Examples 8-9 were sealed in the manner contemplated as the “first water-soluble membrane” or “third water-soluble membrane” described above as part of this invention, wherein the membrane of Comparative Example 1 or Example 1 of this invention served as the “second water-soluble membrane.”

[0265] Comparative Example 8: A polyvinyl alcohol blend comprising 60% polyvinyl alcohol homopolymer (23 mPa.s, dH 87%) and 40% anionic polyvinyl alcohol copolymer based on methyl maleate (4% anionic substitution, 18 mPa.s, dH 90%).

[0266] Comparative Example 9: A polyvinyl alcohol blend comprising 32% polyvinyl alcohol homopolymer (23 mPa.s, dH 88%) and 68% methyl maleate-based anionic polyvinyl alcohol copolymer (4% anionic substitution, 18 mPa.s, dH 90%).

[0267] Comparative Example 10: Polyvinyl alcohol homopolymer blends comprising 75% polyvinyl alcohol homopolymer (23 mPa.s, dH 88%) and 25% polyvinyl alcohol homopolymer (6 mPa.s, dH 88%).

[0268] Comparative Example 11: 100% anionic polyvinyl alcohol copolymer based on methyl maleate (4% anionic substitution, 18 mPa.s, dH 90%).

[0269] Test Results :

[0270] The peel strength results of each of Comparative Examples 8-11 sealed to Comparative Example 1 (C.Ex.1) and each of Comparative Examples 8-11 sealed to the membrane 1 (I.Ex.1) of the present invention are shown in Table 5 below.

[0271] Table 5

[0272]

[0273] Overall conclusions of Example 2

[0274] In each case, the membrane of Embodiment 1 of the present invention exhibits a higher average seal peel strength, regardless of whether the first water-soluble membrane contains no anionic polyvinyl alcohol copolymer, contains 100% anionic polyvinyl alcohol copolymer, or contains a moderate amount of anionic polyvinyl alcohol copolymer.

Claims

1. A water-soluble unit-dose product comprising at least two compartments and a laundry detergent composition or an automatic dishwashing liquid composition, wherein the laundry detergent composition or automatic dishwashing liquid composition is contained in at least one of the compartments, wherein the unit-dose product comprises: a. A first water-soluble membrane, wherein the first water-soluble membrane has a first side and a second side, and wherein the first water-soluble membrane comprises a first polyvinyl alcohol (PVOH) resin, wherein the first polyvinyl alcohol resin comprises polyvinyl alcohol composed of a polyvinyl alcohol homopolymer, an anionic polyvinyl alcohol copolymer, or a blend thereof, and the first water-soluble membrane comprises a blend of a polyvinyl alcohol homopolymer and an anionic polyvinyl alcohol copolymer, wherein the polyvinyl alcohol homopolymer and the anionic polyvinyl alcohol copolymer are present in a relative weight ratio of 90 / 10 to 10 / 90; b. A second water-soluble membrane, wherein the second water-soluble membrane has a first side and a second side, and wherein the second water-soluble membrane comprises a second polyvinyl alcohol resin, wherein the second polyvinyl alcohol resin comprises: ii. 100% by weight of the second polyvinyl alcohol resin, of a polyvinyl alcohol homopolymer or homopolymer blend, wherein the homopolymer is composed of ethylene alcohol monomer units and optionally vinyl acetate monomer units; The second polyvinyl alcohol resin comprises a blend of a first polyvinyl alcohol homopolymer and a second polyvinyl alcohol homopolymer; for example, as measured in a 4% polyvinyl alcohol polymer solution in deionized water at 20°C, the first polyvinyl alcohol homopolymer has an average viscosity in the range of 11 mPa·s to 20 mPa·s. As measured in a 4% polyvinyl alcohol polymer solution in deionized water at 20°C, the second polyvinyl alcohol homopolymer has an average viscosity in the range of 1 mPa·s to 10 mPa·s; and the first polyvinyl alcohol homopolymer and the second polyvinyl alcohol homopolymer are present in a relative weight ratio of 70 / 30 to 50 / 50. The second polyvinyl alcohol resin has an average 4% solution viscosity in deionized water at 20°C, between 8 mPa·s and less than 12 mPa·s. c. A third water-soluble membrane, wherein the third water-soluble membrane has a first side and a second side, and wherein the third water-soluble membrane comprises a third polyvinyl alcohol (PVOH) resin, wherein the third polyvinyl alcohol resin comprises polyvinyl alcohol composed of a polyvinyl alcohol homopolymer, an anionic polyvinyl alcohol copolymer, or a blend thereof, and the third water-soluble membrane comprises a blend of a polyvinyl alcohol homopolymer and an anionic polyvinyl alcohol copolymer, wherein the polyvinyl alcohol homopolymer and the anionic polyvinyl alcohol copolymer are present in a relative weight ratio of 90 / 10 to 10 / 90; The anionic polyvinyl alcohol copolymer is a carboxylated anionic polyvinyl alcohol copolymer, wherein the carboxylic acid ester is selected from acrylates, methacrylates, maleic esters, or mixtures thereof, and The first side of the first water-soluble membrane is sealed to the second side of the second water-soluble membrane to create a first compartment between the first water-soluble membrane and the second water-soluble membrane, and the first side of the second water-soluble membrane is sealed to the second side of the third water-soluble membrane to create at least a second compartment between the second water-soluble membrane and the third water-soluble membrane, wherein the second compartment is positioned above the first compartment.

2. The water-soluble unit dose product according to claim 1, wherein: a. As measured in a 4% polyvinyl alcohol polymer solution in deionized water at 20°C, the first polyvinyl alcohol homopolymer has an average viscosity in the range of 11 mPa·s to 15 mPa·s; b. As measured in a 4% polyvinyl alcohol polymer solution in deionized water at 20°C, the second polyvinyl alcohol homopolymer has an average viscosity in the range of 5 mPa·s to 10 mPa·s; For example, when measured in a 4% polyvinyl alcohol polymer solution in deionized water at 20°C, the Δ average viscosity of the first polyvinyl alcohol homopolymer and the second polyvinyl alcohol homopolymer is at least 1 mPa·s.

3. The water-soluble unit dose product according to claim 1, wherein each polyvinyl alcohol homopolymer independently has an average degree of hydrolysis in the range of 75% to 99%.

4. The water-soluble unit dose product according to claim 1, wherein... a. The first polyvinyl alcohol resin is present in the range of 50% to 95% by weight of the first water-soluble film, or c. The third polyvinyl alcohol resin is present in the range of 50% to 95% by weight of the third water-soluble film; or d. Their mixture.

5. The water-soluble unit dose product according to claim 1, wherein the anionic polyvinyl alcohol copolymer comprises anionic monomer units.

6. The water-soluble unit dose product according to claim 5, wherein the anionic monomer unit is present in the anionic polyvinyl alcohol copolymer in an average amount ranging from 1 mol% to 10 mol%.

7. The water-soluble unit dose product according to claim 1, wherein the first water-soluble film, the second water-soluble film and the third water-soluble film each independently contain a surfactant at a concentration between 0.1% and 2.5% by weight of the water-soluble film.

8. The water-soluble unit dose product according to claim 1, wherein, as determined by Karl Fischer titration, the first water-soluble membrane, the second water-soluble membrane, and the third water-soluble membrane each individually have a residual moisture content of at least 4% by weight of the water-soluble membrane.

9. The water-soluble unit-dosage article of claim 1, wherein each film independently comprises one or more components 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, anaerobic agents, surfactants, and combinations thereof.

10. The water-soluble unit dose article of claim 1, wherein each film independently contains one or more plasticizers, the amount of said plasticizer being in the range of 5% to 50% by weight of a single film.

11. The water-soluble unit dose article according to claim 10, wherein the plasticizer is selected from polyols, sugar alcohols, or mixtures thereof.

12. The water-soluble unit-dose article of claim 11, wherein the polyol comprises a polyol 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, wherein the sugar alcohol comprises a sugar alcohol selected from the group consisting of: isomaltitol, maltitol, sorbitol, xylitol, erythritol, arbutinol, galactitol, pentaerythritol, and mannitol or mixtures thereof.

13. The water-soluble unit dose article according to claim 10, wherein the plasticizer is selected from the group consisting of sorbitol, glycerol, dipropylene glycol, polyethylene glycol, trimethylolpropane, and mixtures thereof.

14. The water-soluble unit-dosage article of claim 1, wherein the first water-soluble film and the second water-soluble film are sealed by solvent sealing, heat sealing, or a mixture thereof, wherein the solvent sealing solution comprises an aqueous solvent, a non-aqueous solvent, or a mixture thereof; and The second and third water-soluble membranes are sealed by solvent sealing, heat sealing, or a mixture thereof, wherein the solvent sealing solution comprises an aqueous solvent, a non-aqueous solvent, or a mixture thereof.

15. The water-soluble unit-dose product according to claim 1, wherein the unit-dose product comprises at least a third compartment, or at least a third compartment and a fourth compartment, between the second water-soluble membrane and the third water-soluble membrane; The second compartment and the third compartment, or the second compartment, the third compartment and the fourth compartment, are positioned side by side, and the second compartment and the third compartment, or the second compartment, the third compartment and the fourth compartment, are positioned above the first compartment.

16. The water-soluble unit dosage product according to claim 1, wherein the laundry detergent composition or automatic dishwashing detergent composition is a laundry detergent composition.

17. The water-soluble unit dosage product according to claim 1, wherein the laundry detergent composition or automatic dishwashing detergent composition is a liquid laundry detergent composition.

18. A method for preparing a water-soluble unit dose article according to any one of the preceding claims, the method comprising the following steps: a. The first water-soluble film is deformed in a mold by thermoforming, vacuum forming, or a combination thereof to produce an open mouth body; b. Fill the oral cavity with the laundry detergent composition or the automatic dishwashing detergent composition; c. The third water-soluble film is individually deformed in a mold by thermoforming, vacuum forming, or a combination thereof to produce at least one open cavity; d. Fill the at least one open cavity from step c with a laundry detergent composition or an automatic dishwashing detergent composition; e. Seal the filled oral cavity from step c with a second water-soluble membrane; f. Seal the second water-soluble membrane and the third water-soluble membrane to produce a closed intermediate; g. Close the filled oral cavity from step b with the closed intermediate from step f; h. Seal the first water-soluble membrane and the second water-soluble membrane to produce a water-soluble unit dose product.

19. The method of claim 18, wherein the second water-soluble membrane and the third water-soluble membrane are sealed by solvent sealing.

20. The method of claim 19, wherein a solvent sealing solution is applied to a first side of the second water-soluble membrane before the membranes are sealed together, the first side being the side facing the third water-soluble membrane.

21. The method of claim 18, wherein the first water-soluble membrane and the second water-soluble membrane are sealed by solvent sealing.

22. The method of claim 21, wherein a solvent sealing solution is applied to a second side of the second water-soluble membrane prior to sealing the membranes together, the second side being the side facing the first water-soluble membrane.

23. The method of claim 18, wherein the first water-soluble membrane in step a and the third water-soluble membrane in step c are identical before deformation.

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