EP4650427A1

EP4650427A1 - Unit dose article

Info

Publication number: EP4650427A1
Application number: EP24175486.0A
Authority: EP
Inventors: Francesc Corominas; Florence Catherine Courchay; Karel Jozef Maria Depoot; Robby Renilde Francois Keuleers; Shigeng Li; Neda Sanatkaran
Original assignee: Procter and Gamble Co
Current assignee: Procter and Gamble Co
Priority date: 2024-05-13
Filing date: 2024-05-13
Publication date: 2025-11-19
Also published as: WO2025240281A1

Abstract

A unit dose article comprising a water-soluble film and at least one detergent composition, wherein the detergent composition is encapsulated within a compartment formed by the water-soluble film;
wherein the water-soluble film comprises polyvinyl alcohol polymer and wherein the polyvinyl alcohol polymer comprises an anionic polyvinyl alcohol copolymer, a polyvinyl alcohol homopolymer, or a blend thereof;
wherein the detergent composition comprises a non-soap surfactant system; and
wherein an aqueous solution comprising the water-soluble film and the detergent composition dissolved therein has a gelling factor G of less than 1.25.

Description

FIELD OF THE INVENTION

Unit dose article comprising a detergent composition enclosed by a water-soluble film.

BACKGROUND OF THE INVENTION

Water-soluble unit dose detergent articles have become very popular for use in automatic dishwashing and laundry, in particular articles made from a water-soluble film comprising polyvinyl alcohol. The film envelops the detergent. The water-soluble unit-dose detergent article is added to water and the film dissolves releasing the detergent.
Fast dissolution of the articles is highly desirable, however in some cases the interaction between the detergent and the polyvinyl alcohol during initial dissolution and contact with the water can give rise to gelling that slows down further dissolution, leading to a delay in the cleaning onset and in some cases leaving residues on the treated items. This is more acute in cases in which the cleaning process takes place in short and cold temperature cleaning programs. When the water-soluble unit-dose detergent article is used in a laundry process, residues can be deposited on fabrics or the washing machine. The residues can be redissolved but it might require a further step from the user. Thus, the object of the present invention is to provide a unit-dose detergent article with improved dissolution. It is another object of the present invention to provide a unit-dose detergent article with improved dissolution in short and cold washing programs.

SUMMARY OF THE INVENTION

A water-soluble unit dose article comprising a water-soluble film and at least one detergent composition. The detergent composition is encapsulated within a compartment formed by the water-soluble film;

the water-soluble film comprises polyvinyl alcohol polymer and wherein the polyvinyl alcohol polymer comprises: an anionic polyvinyl alcohol copolymer or a polyvinyl alcohol homopolymer or a blend of polyvinyl alcohol homopolymers or a blend of an anionic polyvinyl alcohol copolymer and a polyvinyl alcohol homopolymer or a blend of anionic polyvinyl alcohol copolymers;
the detergent composition comprises a non-soap surfactant system; and
wherein an aqueous solution comprising the water-soluble film and the detergent composition dissolved therein has a gelling factor G of less than 1.25, preferably less than 1.2 and more preferably less than 1.15, wherein $G = G' / G "$ wherein
- G'is the "storage" or "elastic" modulus; and
- G" is the "loss" or "plastic" modulus;
- wherein the aqueous solution is prepared and G' and G" are measured as described below.

Unit dose articles according to the invention present very good dissolution profile, even at low temperature and in short and/or low water laundry cycles.
Preferably, the non-soap surfactant system comprises anionic non-soap surfactant and nonionic surfactant. Preferably the detergent composition is a liquid detergent composition. Preferably, the composition comprises organic solvent; and from 5% to 25% by weight of the composition of water.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a water-soluble unit dose article according to the present invention.
FIG.2 depicts the set up to measure the gelling factor G.

DETAILED DESCRIPTION OF THE INVENTION

As used herein, the articles including "the," "a" and "an" when used in a claim or in the specification, are understood to mean one or more of what is claimed or described.
As used herein, the terms "include," "includes" and "including" are meant to be non-limiting. All percentages, ratios and proportions used herein are by weight percent of the composition, unless otherwise specified. All average values are calculated "by weight" of the composition, unless otherwise expressly indicated.
All measurements are performed at 25°C unless otherwise specified.
Unless otherwise noted, all component or composition levels are in reference to the active portion of that component or composition, and are exclusive of impurities, for example, residual solvents or by-products, which may be present in commercially available sources of such components or compositions.

Water-soluble unit dose article

The present invention discloses a water-soluble unit dose article comprising a water-soluble film and a detergent composition, preferably a laundry detergent composition. The water-soluble film and the laundry detergent composition are described in more detail below. The laundry detergent composition preferably is a liquid laundry detergent composition.
The water-soluble unit dose detergent article comprises the water-soluble film shaped such that the unit-dose article comprises at least one internal compartment surrounded by the water-soluble film. The unit dose article may comprise a first water-soluble film and a second water-soluble film sealed to one another such to define the internal compartment. The water-soluble unit dose article is constructed such that the detergent composition does not leak out of the compartment during storage. However, upon addition of the water-soluble unit dose article to water, the water-soluble film dissolves and releases the contents of the internal compartment into the wash liquor.
The compartment should be understood as meaning a closed internal space within the unit dose article, which holds the detergent composition. During manufacture, a first water-soluble film may be shaped to comprise an open compartment into which the detergent composition is added. A second water-soluble film is then laid over the first film in such an orientation as to close the opening of the compartment. The first and second films are then sealed together along a seal region.
The unit dose article may comprise more than one compartment, even at least two compartments, or even at least three compartments, or even at least four compartments. The compartments may be arranged in superposed orientation, i.e. one positioned on top of the other. In such an orientation the unit dose article will comprise at least three films, top, one or more middle, and bottom. Alternatively, the compartments may be positioned in a side-by-side orientation, i.e. one orientated next to the other. The compartments may even be orientated in a `tyre and rim' arrangement, i.e. a first compartment is positioned next to a second compartment, but the first compartment at least partially surrounds the second compartment but does not completely enclose the second compartment. Alternatively, one compartment may be completely enclosed within another compartment.
Wherein the unit dose article comprises at least two compartments, one of the compartments may be smaller than the other compartment. Wherein the unit dose article comprises at least three compartments, two of the compartments may be smaller than the third compartment, and preferably the smaller compartments are superposed on the larger compartment. The superposed compartments preferably are orientated side-by-side. The unit dose article may comprise at least four compartments, three of the compartments may be smaller than the fourth compartment, and preferably the smaller compartments are superposed on the larger compartment. The superposed compartments preferably are orientated side-by-side.
In a multi-compartment orientation, the detergent composition according to the present invention may be comprised in at least one of the compartments. It may for example be comprised in just one compartment, or may be comprised in two compartments, or even in three compartments, or even in four compartments.
Each compartment may comprise the same or different compositions. The different compositions could all be in the same form, or they may be in different forms.
The water-soluble unit dose article may comprise at least two internal compartments, wherein the laundry detergent composition is comprised in at least one of the compartments, preferably wherein the unit dose article comprises at least three compartments, wherein the detergent composition is comprised in at least one of the compartments.
The water-soluble unit dose article may comprise from 1 gram up to 60 gram, preferably from 5 gram up to 50 gram, more preferably from 10 gram up to 40 gram, most preferably from 12 gram up to 25 gram alternatively from 30 gram to 40 gram of the laundry detergent composition. The water-soluble unit dose article may comprise from 1 ml up to 60 ml, preferably from 5 ml up to 50 ml, more preferably from 10 ml up to 40 ml, most preferably from 12 ml up to 25 ml, alternatively from 30 ml to 40ml of the liquid laundry detergent composition.

Water-soluble film

The film of the present invention is soluble or dispersible in water. The water-soluble film preferably has a thickness of from 20 to 150 micron, preferably 35 to 125 micron, even more preferably 50 to 110 micron, most preferably about 76 micron.
The water-soluble film material may be obtained by casting, blow-moulding, extrusion or blown extrusion of the polymeric material, as known in the art, preferably the water-soluble film is obtained by solvent casting.
The water-soluble film comprises polyvinylalcohol. The polyvinylalcohol may be present between 50% and 95%, preferably between 55% and 90%, more preferably between 60% and 80% by weight of the water-soluble film. The polyvinylalcohol preferably comprises polyvinyl alcohol homopolymer, polyvinylalcohol copolymer, or a mixture thereof. Preferably, the water-soluble film comprises a blend of polyvinylalcohol homopolymers and/or anionic polyvinylalcohol copolymers, preferably wherein the polyvinylalcohol copolymers are selected from sulphonated and carboxylated anionic polyvinylalcohol copolymers especially carboxylated anionic polyvinylalcohol copolymers. Most preferably the water-soluble film comprises a blend of a polyvinylalcohol homopolymer and a carboxylated anionic polyvinylalcohol copolymer, or a blend of polyvinylalcohol homopolymers. Alternatively, the polyvinylalcohol comprises an anionic polyvinyl alcohol copolymer, most preferably a carboxylated anionic polyvinylalcohol copolymer. When the polyvinylalcohol in the water-soluble film is a blend of a polyvinylalcohol homopolymer and a carboxylated anionic polyvinylalcohol copolymer, the homopolymer and the anionic copolymer are present in a relative weight ratio of 90/10 to 10/90. Without wishing to be bound by theory, the term "homopolymer" generally includes polymers having a single type of monomeric repeating unit (e.g., a polymeric chain comprising or consisting of a single monomeric repeating unit). For the particular case of polyvinylalcohol, the term "homopolymer" further includes copolymers having a distribution of vinyl alcohol monomer units and optionally vinyl acetate monomer units, depending on the degree of hydrolysis (e.g., a polymeric chain comprising or consisting of vinyl alcohol and vinyl acetate monomer units). In the case of 100% hydrolysis, a polyvinylalcohol homopolymer can include only vinyl alcohol units. Without wishing to be bound by theory, the term "copolymer" generally includes polymers having two or more types of monomeric repeating units (e.g., a polymeric chain comprising or consisting of two or more different monomeric repeating units, whether as random copolymers, block copolymers, etc.). For the particular case of polyvinylalcohol, the term "copolymer" (or "polyvinylalcohol copolymer") further includes copolymers having a distribution of vinyl alcohol monomer units and vinyl acetate monomer units, depending on the degree of hydrolysis, as well as at least one other type of monomeric repeating unit (e.g., a ter- (or higher) polymeric chain comprising or consisting of vinyl alcohol monomer units, vinyl acetate monomer units, and one or more other monomer units, for example anionic monomer units). In the case of 100% hydrolysis, a polyvinylalcohol copolymer can include a copolymer having vinyl alcohol units and one or more other monomer units, but no vinyl acetate units. Without wishing to be bound by theory, the term "anionic copolymer" includes copolymers having an anionic monomer unit comprising an anionic moiety. General classes of anionic monomer units which can be used for the anionic polyvinyl alcohol copolymer include the vinyl polymerization units corresponding to monocarboxylic acid vinyl monomers, their esters and anhydrides, dicarboxylic monomers having a polymerizable double bond, their esters and anhydrides, vinyl sulfonic acid monomers, and alkali metal salts of any of the foregoing, preferably monocarboxylic acid vinyl monomers, their esters and anhydrides, dicarboxylic monomers having a polymerizable double bond, their esters and anhydrides, and alkali metal salts of any of the foregoing, most preferably dicarboxylic monomers having a polymerizable double bond, their esters and anhydrides, and alkali metal salts of any of the foregoing. Examples of suitable anionic monomer units include the vinyl polymerization units corresponding to vinyl anionic monomers including vinyl acetate, maleate, monoalkyl maleate, dialkyl maleate, monomethyl maleate, dimethyl maleate, maleic anyhydride, fumarate, monoalkyl fumarate, dialkyl fumarate, monomethyl fumarate, dimethyl fumarate, fumaric any hydride, itaconate, monoalkyl itaconate, dialkyl itaconate, monomethyl itaconate, dimethyl itaconate, itaconic anhydride, vinyl sulfonate, allyl sulfonate, ethylene sulfonate, 2-acrylamido-1-methylpropanesulfonate, 2-acrylamido-2-methylpropanesulfonate, 2-methylacrylamido-2-methylpropanesulfonate, 2-sufoethyl acrylate, alkali metal salts of the foregoing (e.g., sodium, potassium, or other alkali metal salts), esters of the foregoing (e.g., methyl, ethyl, 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). The anionic monomer may be one or more acrylamido methylpropanesulfonate (e.g., 2-acrylamido-1-methylpropanesulfonate, 2-acrylamido-2-methylpropanesulfonate, 2-methylacrylamido-2-methylpropanesulfonate), alkali metal salts thereof (e.g., sodium salts), and combinations thereof. Preferably, the anionic moiety of the first anionic monomer unit is selected from a sulphonate, a carboxylate, or a mixture thereof, more preferably a carboxylate, even more preferably a monocarboxylate, a dicarboxylate, or a mixture thereof, most preferably, an acrylate, a methacrylate, a maleate, an itaconate, or a mixture thereof. Preferably, the anionic monomer unit is present in the anionic polyvinyl alcohol copolymer in an average amount in a range of between 0.5 mol.% and 10 mol.%, preferably between 1 mol.% and 5 mol.%. Preferably, the polyvinyl alcohol, and/or in case of polyvinylalcohol blends the individual polyvinylalcohol polymers, have an average viscosity in a range of between 4 cP and 30 cP, preferably between 5 cP and 20 cP, most preferably between 5 cP and 15 cP measured as a 4% polyvinyl alcohol copolymer solution in demineralized water at 20 degrees C. The viscosity of a polyvinyl alcohol polymer is determined by measuring a freshly made solution using a Brookfield LV type viscometer with UL adapter as described in British Standard EN ISO 15023-2:2006 Annex E Brookfield Test method. It is international practice to state the viscosity of 4% aqueous polyvinyl alcohol solutions at 20 °C. It is well known in the art that the viscosity of an aqueous water-soluble polymer solution (polyvinylalcohol or otherwise) is correlated with the weight-average molecular weight of the same polymer, and often the viscosity is used as a proxy for weight-average molecular weight. Thus, the weight-average molecular weight of the polyvinylalcohol can be in a range of 30,000 to 175,000, or 30,000 to 100,000, or 55,000 to 80,000. Preferably, the polyvinyl alcohol, and/or in case of polyvinylalcohol blends the individual polyvinylalcohol polymers, have an average degree of hydrolysis in a range of between 60% and 99%, preferably between 65% and 90%, most preferably between 70% and 80%. A suitable test method to measure the degree of hydrolysis is as according to standard method JIS K6726.
Without wishing to be bound by theory, it is believed that water-soluble polymeric resin related composition elements impacting the gelling factor include the average degree of hydrolysis of the individual polyvinyl alcohol polymers and of the eventual blend, the viscosity of the individual polyvinyl alcohol polymers and of the eventual blend, as well as the relative ratio between the individual polyvinyl alcohol polymers in the case of a blend. The type and average degree of anionic substitution will also impact. A lower average degree of hydrolysis is thought to help gelling prevention due to a lower affinity to water hydration in view of the lower relative alcohol functional groups content, resulting in limiting viscosity increases in presence of detergent juice including surfactants accordingly. As such an average degree of hydrolysis of between 70% and 80% is most preferred to prevent strong gel formation. A lower viscosity indicating a lower molecular weight polymer is thought to improve gelling prevention due to a lower degree of polymer entanglement to be expected. As such an average viscosity of between 3 cP and 20 cP or even between 5 cP and 15 cP is most preferred to prevent strong gel formation. Presence of anionic modification is thought to help gelling prevention through an increased sterical hindrance impact, favouring chain disentanglement and decreased polymer-surfactant interaction accordingly. A preferred type of anionic modification to prevent gel formation are dicarboxylates, preferably itaconates. A too high anionic content however is equally to be avoided as it is thought to again promote gel formation through a higher degree of hydration water binding. As such, when present, an average degree of anionic modification of between 1% and 3% is most preferred to prevent strong gel formation. A combination of polymers is regularly chosen by a water-soluble film formulator to balance amongst others mechanical properties, strength, dissolution and sealability. While gel promoting polymers following above hypotheses may be preferred to deliver against one or more of these highlighted film properties, careful attention needs to be taken to its relative content in the overall water-soluble polymer in order to prevent formation of strong gels upon initial contact with the dissolving water and detergent composition.
Examples of two especially suitable polyvinyl alcohol polymer blends, designed following above highlighted principles, for use in the current application are described below.
First polyvinyl alcohol polymer blend suitable for use in current application:

A first polyvinyl alcohol polymer blend comprises:
1. i) from 1% to 30%, preferably from 5% to 25%, more preferably from 10% to 20% by weight of the polymer blend of polymer A, wherein polymer A comprises an anionic monomer unit, a vinyl alcohol monomer unit and a vinyl acetate monomer unit,
  wherein polymer A has
  - an average degree of hydrolysis of from 60% to less than 80%, preferably of from 70% to less than 80%, more preferably of from 75% to less than 80%; and
  - a 4% solution viscosity at 20°C of from 3 cP to 20 cP, preferably from 3 cP to 15 cP, more preferably of from 3 cP to 10 cP;
  - an anionic monomer unit comprising a monomer derived from the group consisting of itaconic acid, monoalkyl itaconate, dialkyl itaconate, itaconic anhydride, and mixtures thereof;
  - from 0.1 mol% to 4.0 mol%, preferably of from 0.5 mol% to 3.0 mol%, more preferably from 1.0 mol% to 2.0 mol% of the anionic monomer unit;
    and
2. ii) from 70% to 99%, preferably from 75% to 95%, more preferably from 80% to 90% by weight of the polymer blend of polymer B, wherein polymer B consists essentially of a vinyl alcohol monomer unit and a vinyl acetate monomer unit,
  wherein polymer B has
  - an average degree of hydrolysis of from 70% to less than 80%, preferably of from 72% to less than 80%, more preferably of from 75% to less than 80%; and
  - a 4% solution viscosity at 20°C of from 10 cP to 40 cP, preferably from 10 cP to 30 cP, more preferably of from 10 cP to 20 cP.

Preferably, the difference in the average degree of hydrolysis between polymer A and polymer B is at most 10%, preferably at most 5%, more preferably between 1% and 3%.
Preferably, the difference of the 4% solution viscosity at 20°C between polymer A and polymer B is from 1cP to 20 cP, preferably from 3 cP to 15cP and more preferably from 5 cP to 12 cP.
Preferably, the polymer blend has a biodegradation rate of at least 60%, preferably at least 65%, more preferably at least 70%, after 60 days, or at least 60%, preferably at least 65%, more preferably at least 70%, after 28 days according to OECD 301B testing. The polymer blend meets the OECD 301B biodegradability requirements.
More specifically:
Polymer A
Polymer A comprises an anionic monomer unit, a vinyl alcohol monomer unit and a vinyl acetate monomer unit. The anionic monomer unit comprises a monomer derived from the group consisting of itaconic acid, monoalkyl itaconate, dialkyl itaconate, itaconic anhydride, and mixtures thereof, preferably itaconic acid, monomethyl itaconate, dimethyl itaconate, itaconic anhydride, and mixtures thereof, more preferably itaconic acid.
Polymer A comprises from 0.1 mol% to 4.0 mol%, preferably of from 0.5 mol% to 3.0 mol%, more preferably from 1.0 mol% to 2.0 mol% of the anionic monomer unit, preferably the anionic monomer unit is itaconic acid.
The polyvinyl alcohol blend comprises from 1% to 30%, preferably from 5% to 25%, more preferably from 10% to 20% by weight of the polyvinyl alcohol polymer blend of polymer A. Polymer A has an average degree of hydrolysis of from 60% to less than 80%, preferably of from 70% to less than 80%, more preferably of from 75% to less than 80%; and a 4% solution viscosity at 20°C of from 3 cP to 20 cP, preferably from 3 cP to 15 cP, more preferably of from 3 cP to 10 cP.
Preferably, the polyvinyl alcohol blend comprises from 10% to 20% by weight of the polyvinyl alcohol polymer blend of polymer A.
Preferably, Polymer A comprises an anionic monomer unit derived from itaconic acid, preferably the anionic monomer unit is present from between 1.0 mol% and 2.0 mol%.
Preferably, Polymer A has an average degree of hydrolysis of from 75% to less than 80%. Preferably, Polymer A has a 4% solution viscosity at 20°C of from 3 cP to 10 cP.
Preferably, the polyvinyl alcohol blend comprises from 10% to 20% by weight of the polymer blend of polymer A and Polymer A has from 1.0 mol% to 2.0 mol% of an anionic monomer unit derived from itaconic acid, an average degree of hydrolysis of from 75% to less than 80% and a 4% solution viscosity at 20°C of from 3 cP to 10 cP.

Polymer B

Polymer B consists essentially of a vinyl alcohol monomer unit and a vinyl acetate monomer unit.
The polyvinyl alcohol blend comprises from 70% to 99%, preferably from 75% to 95%, more preferably from 80% to 90% by weight of the polyvinyl alcohol polymer blend of polymer B. Polymer B has an average degree of hydrolysis of from 70% to less than 80%, preferably of from 72% to less than 80%, more preferably of from 75% to less than 80%; and a 4% solution viscosity at 20°C of from 10cP to 40cP, preferably from 10 cP to 30 cP, more preferably of from 10 cP to 20 cP.
Preferably, the polyvinyl alcohol blend comprises from 80% to 90% by weight of the polyvinyl alcohol polymer blend of polymer B.
Preferably, Polymer B has an average degree of hydrolysis of from 75% to less than 80%. Polymer B preferably has a 4% solution viscosity at 20°C of from 10 cP to 20 cP.
Preferably, the polyvinyl alcohol blend comprises from 80% to 90% by weight of the polyvinyl alcohol polymer blend of polymer B and polymer B has an average degree of hydrolysis of from 75% to less than 80% and has a 4% solution viscosity at 20°C of from 10 cP to 20 cP.
Second polyvinyl alcohol polymer blend suitable for use in current application:
The second polyvinyl alcohol polymer blend comprises two polyvinyl alcohol polymers, polymer A and polymer B. Both polymer A and polymer B consist essentially of a vinyl alcohol monomer unit and a vinyl acetate monomer unit. The polyvinyl alcohol polymer blend comprises:

i) from 1% to 50%, preferably from 5% to 30%, more preferably from 10% to 20% by weight of the polymer blend of polymer A, wherein polymer A has
- an average degree of hydrolysis of from 60% to less than 75%, preferably of from 65% to less than 75%, more preferably of from 70% to less than 75%; and
- a 4% solution viscosity at 20°C of from 3 cP to 20 cP, preferably from 3 cP to 15 cP, more preferably of from 3 cP to 10 cP; and
ii) from 50% to 99%, preferably from 70% to 95%, more preferably from 80% to 90% by weight of the polymer blend of polymer B, wherein polymer B has
- an average degree of hydrolysis of from 60% to less than 80%, preferably of from 70% to less than 80%, more preferably of from 75% to less than 80%; and
- a 4% solution viscosity at 20°C of from 10cP to 40cP, preferably from 10 cP to 30 cP, more preferably of from 10 cP to 20 cP.

Preferably, the difference in the average degree of hydrolysis between polymer A and polymer B is at most 10%, preferably at most 8.5%, more preferably between 1% and 7%.
Preferably, the difference of the 4% solution viscosity at 20°C between polymer A and polymer B is from 1 cP to 20 cP, preferably from 3 cP to 15 cP and more preferably from 5 cP to 12 cP.
Preferably, the polymer blend has a biodegradation rate of at least 60%, preferably at least 65%, more preferably at least 70%, after 60 days, or at least 60%, preferably at least 65%, more preferably at least 70%, after 28 days according to OECD 301B testing. The polymer blend meets the OECD 301B biodegradability requirements.
More specifically:

Polymer A

Polymer A consists essentially of a vinyl alcohol monomer unit and a vinyl acetate monomer unit.
The polyvinyl alcohol polymer blend comprises from 1% to 50%, preferably from 5% to 30%, more preferably from 10% to 20% by weight of the polymer blend of polymer A. Polymer A has: i) an average degree of hydrolysis of from 60% to less than 75%, preferably of from 65% to less than 75%, more preferably of from 70% to less than 75%; and ii) a 4% solution viscosity at 20°C of from 3 cP to 20 cP, preferably from 3 cP to 15 cP, more preferably of from 3 cP to 10 cP.
Preferably, the blend comprises from 10% to 20% by weight of the polymer blend of polymer A.
Preferably, Polymer A has an average degree of hydrolysis of from 70% to less than 75%. Polymer A preferably has a 4% solution viscosity at 20°C of from 3 cP to 10 cP.
Preferably, the blend comprises from 10% to 20% by weight of the polymer blend of polymer A and polymer A has an average degree of hydrolysis of from 70% to less than 75% and has a 4% solution viscosity at 20°C of from 3cP to 10 cP.

Polymer B

Polymer B consists essentially of a vinyl alcohol monomer unit and a vinyl acetate monomer unit.
The blend comprises from 50% to 99%, preferably from 70% to 95%, more preferably from 80% to 90% by weight of the polymer blend of polymer B. Polymer B has an average degree of hydrolysis of from 60% to less than 80%, preferably of from 70% to less than 80%, more preferably of from 75% to less than 80%; and a 4% solution viscosity at 20°C of from 10 cP to 40 cP, preferably from 10 cP to 30 cP, more preferably of from 10 cP to 20 cP.
Preferably, the blend comprises from 80% to 90% by weight of the polymer blend of polymer B.
Preferably, Polymer B has an average degree of hydrolysis of from 75% to less than 80%. Polymer B preferably has a 4% solution viscosity at 20°C of from 10 cP to 20 cP.
Preferably, the blend comprises from 80% to 90% by weight of the polymer blend of polymer B and polymer B has an average degree of hydrolysis of from 75% to less than 80% and has a 4% solution viscosity at 20°C of from 10 cP to 20 cP.
Further components to be formulated in a water-soluble film comprising a polymeric resin according to the invention:
Preferably, the water-soluble film comprises a non-aqueous plasticizer. Preferably, the non-aqueous plasticizer is selected from polyols, sugar alcohols, and mixtures thereof. Suitable polyols include polyols selected from the group consisting of glycerol, diglycerin, ethylene glycol, diethylene glycol, triethyleneglycol, tetraethylene glycol, polyethylene glycols up to 400 molecular weight, neopentyl glycol, 1,2-propylene glycol, 1,3-propanediol, dipropylene glycol, polypropylene glycol, 2-methyl-1,3-propanediol, trimethylolpropane and polyether polyols, or a mixture thereof. Suitable sugar alcohols include sugar alcohols selected from the group consisting of isomalt, maltitol, sorbitol, xylitol, erythritol, adonitol, dulcitol, pentaerythritol and mannitol, or a mixture thereof. More preferably the non-aqueous plasticizer is selected from glycerol, 1,2-propanediol, dipropylene glycol, 2-methyl-1,3-propanediol, trimethylolpropane, triethyleneglycol, polyethyleneglycol, sorbitol, or a mixture thereof, most preferably selected from glycerol, sorbitol, trimethylolpropane, dipropylene glycol, and mixtures thereof. One particularly suitable plasticizer system includes a blend of glycerol, sorbitol and trimethylol propane. Another particularly suitable plasticizer system includes a blend of glycerin, dipropylene glycol, and sorbitol. Preferably, the film comprises between 5% and 50%, preferably between 10% and 40%, more preferably between 20% and 30% by weight of the film of the non-aqueous plasticizer. Without wishing to be bound by theory, presence of such a plasticizer system inside the water-soluble film is believed to help preventing gelling upon initial dissolution of the polymeric resin of the water-soluble film in presence of the surfactant system of the detergent composition through acting as a dissolution aid behind its solvency properties.
Preferably, the water-soluble film comprises a surfactant. Preferably, the water-soluble film comprises a surfactant in an amount between 0.1% and 2.5%, preferably between 1% and 2% by weight of the water-soluble film. Suitable surfactants can include the nonionic, cationic, anionic and zwitterionic classes. Suitable surfactants include, but are not limited to, polyoxyethylenated polyoxypropylene glycols, alcohol ethoxylates, alkylphenol ethoxylates, tertiary acetylenic glycols and alkanolamides (nonionics), polyoxyethylenated amines, quaternary ammonium salts and quaternized polyoxyethylenated amines (cationics), and amine oxides, N-alkylbetaines and sulfobetaines (zwitterionics). Other suitable surfactants include dioctyl sodium sulfosuccinate, lactylated fatty acid esters of glycerol and propylene glycol, lactylic esters of fatty acids, sodium alkyl sulfates, polysorbate 20, polysorbate 60, polysorbate 65, polysorbate 80, lecithin, acetylated fatty acid esters of glycerol and propylene glycol, and acetylated esters of fatty acids, and combinations thereof.
Preferably the water-soluble film according to the invention comprises lubricants / release agents. Suitable lubricants/release agents can include, but are not limited to, fatty acids and their salts, fatty alcohols, fatty esters, fatty amines, fatty amine acetates and fatty amides. Preferred lubricants/release agents are fatty acids, fatty acid salts, and fatty amine acetates. The amount of lubricant/release agent in the water-soluble film is in a range of from 0.02% to 1.5%, preferably from 0.1% to 1% by weight of the water-soluble film.
Preferably, the water-soluble film comprises fillers, extenders, antiblocking agents, detackifying agents or a mixture thereof. Suitable fillers, extenders, antiblocking agents, detackifying agents or a mixture thereof include, but are not limited to, starches, modified starches, crosslinked polyvinylpyrrolidone, crosslinked cellulose, microcrystalline cellulose, silica, metallic oxides, calcium carbonate, talc and mica. Preferred materials are starches, modified starches and silica. Preferably, the amount of filler, extender, antiblocking agent, detackifying agent or mixture thereof in the water-soluble film is in a range of from 0.1% to 25%, preferably from 1% to 10%, more preferably from 2% to 8%, most preferably from 3% to 5% by weight of the water-soluble film. In the absence of starch, one preferred range for a suitable filler, extender, antiblocking agent, detackifying agent or mixture thereof is from 0.1% to 1%, preferably 4%, more preferably 6%, even more preferably from 1% to 4%, most preferably from 1% to 2.5%, by weight of the water-soluble film.
Preferably the water-soluble film according to the invention has a residual moisture content of at least 4%, more preferably in a range of from 4% to 15%, even more preferably of from 5% to 10% by weight of the water-soluble film as measured by Karl Fischer titration. Without wishing to be bound by theory it is believed that presence of such water inside of the water-soluble film will improve the dissolution kinetics of the polymeric resin, helping to prevent gel formation accordingly.
Preferred films exhibit good dissolution in cold water, meaning unheated distilled water.
The film may be opaque, transparent or translucent. The film may comprise a printed area. The area of print may face an internal compartment of the unit dose article, or may face the outside environment, or both, preferably the area of print faces an internal compartment of the unit dose article. Preferred inks used for printing the articles of the invention include red, white and black pigments, for example, red: Pigment Red 254, white: titanium dioxide and black: lampblack or carbon black (pigment black 6). The area of print may be achieved using standard techniques, such as flexographic printing or inkjet printing.
The film may comprise an aversive agent, for example a bittering agent. Suitable bittering agents include, but are not limited to, naringin, sucrose octaacetate, quinine hydrochloride, denatonium benzoate, or mixtures thereof. Any suitable level of aversive agent may be used in the film. Suitable levels include, but are not limited to, 1 to 5000ppm, or even 100 to 2500ppm, or even 250 to 2000rpm.
Preferably, the water-soluble film or water-soluble unit dose article or both are coated with a lubricating agent, preferably, wherein the lubricating agent is selected from talc, zinc oxide, silicas, siloxanes, zeolites, silicic acid, alumina, sodium sulphate, potassium sulphate, calcium carbonate, magnesium carbonate, sodium citrate, sodium tripolyphosphate, potassium citrate, potassium tripolyphosphate, calcium stearate, zinc stearate, magnesium stearate, starch, modified starches, clay, kaolin, gypsum, cyclodextrins or mixtures thereof.

Detergent composition

The detergent composition may be a laundry detergent composition, an automatic dishwashing composition or a hard surface cleaning composition. Preferably the detergent composition is a laundry detergent composition. A laundry detergent composition can be used in a fabric hand wash operation or more preferably may be used in an automatic machine fabric wash operation, for example in an automatic machine fabric wash operation.
The detergent composition may comprise a solid, a liquid or a mixture thereof. The term liquid includes a gel, a solution, a dispersion, a paste, or a mixture thereof. The solid may be a powder. By powder we herein mean that the detergent composition may comprise solid particulates or may be a single homogenous solid. In some examples, the powder detergent composition comprises particles. This means that the powder detergent composition comprises individual solid particles as opposed to the solid being a single homogenous solid. The particles may be free-flowing or may be compacted. Preferably the laundry detergent is a liquid detergent composition. Without wishing to be bound by theory, a liquid composition is believed to diffuse faster into the wash solution upon initial rupture of the water-soluble film, reducing the time spent, hence degree of gel formation through interaction with the dissolved water-soluble film polymeric resin, at the detergent - film - wash water interface accordingly.
Example laundry detergent compositions comprise a non-soap surfactant, wherein the non-soap surfactant preferably comprises an anionic non-soap surfactant and a non-ionic surfactant. In some examples, the laundry detergent composition comprises between 10% and 60%, or between 15% and 55%, or between 20% and 45%, or alternative combinations thereof, by weight of the laundry detergent composition of the non-soap surfactant. Without wishing to be bound by theory, it is believed that lower non-soap surfactant levels are preferred in order to reduce surfactant - water-soluble polymeric resin interaction at the detergent-film-wash water interface upon initial rupture of the water-soluble film. Example non-soap anionic surfactants comprises linear alkylbenzene sulphonate, alkyl sulphate anionic surfactant, or a mixture thereof. Example linear alkylbenzene sulphonates are C10-C16 alkyl benzene sulfonic acids, or C11-C14 alkyl benzene sulfonic acids. By `linear', we herein mean the alkyl group is linear. Example alkyl sulphate anionic surfactant may comprise alkoxylated alkyl sulphate or non-alkoxylated alkyl sulphate or a mixture thereof. Example alkoxylated alkyl sulphate anionic surfactant comprises an ethoxylated alkyl sulphate anionic surfactant. Example alkyl sulphate anionic surfactant may comprise an ethoxylated alkyl sulphate anionic surfactant with a mol average degree of ethoxylation from 1 to 5, from 1 to 3, or from 2 to 3. Example alkyl sulphate anionic surfactant may comprise a non-ethoxylated alkyl sulphate and an ethoxylated alkyl sulphate wherein the mol average degree of ethoxylation of the alkyl sulphate anionic surfactant is from 1 to 5, from 1 to 3, or from 2 to 3. Example alkyl fraction of the alkyl sulphate anionic surfactant are derived from fatty alcohols, oxo-synthesized alcohols, Guerbet alcohols, or mixtures thereof. In some examples, the non-ionic surfactant is selected from fatty alcohol alkoxylate, an oxo-synthesised alcohol alkoxylate, Guerbet alcohol alkoxylates, alkyl phenol alcohol alkoxylates, or a mixture thereof. Without wishing to be bound by theory, it is thought that proper selection of non-soap surfactant type and formulated ratio between non-soap surfactants are core contributors to prevent strong gel formation at the detergent-film-wash water interface. Such a proper choice may enable a faster diffusion of the surfactant into the wash water, and/or sterically hinder surfactant-polymer packing, reducing the time to interact and degree of interaction with dissolved water-soluble polymeric resin accordingly.
In some examples, the laundry detergent composition comprises between 1% and 20%, between 1.5% and 15%, between 2% and 10%, or between 2.5% and 8% by weight of the laundry detergent composition of soap, in some examples a fatty acid salt, in some examples an amine neutralized fatty acid salt, wherein in some examples the amine is an alkanolamine for example selected from monoethanolamine, diethanolamine, triethanolamine or a mixture thereof, in some examples monoethanolamine. Without wishing to be bound by theory higher levels of fatty acid are less preferred as they are found to thicken detergent viscosity upon initial contact with incoming wash water, slowing down product diffusion into the wash water hence enabling more time for surfactant - water-soluble polymeric resin interaction accordingly. A minimal level of fatty acid however may be required to protect the overall surfactant system from water hardness in the wash solution.
In some examples, the laundry detergent composition is a liquid laundry detergent composition. In some examples the liquid laundry detergent composition comprises not more than 25% of water, preferably less than 15%, or even less than 12%, and more preferably more than 5%, by weight of the liquid laundry detergent composition of water. Without wishing to be bound by theory higher levels of detergent water are to be avoided as these may start preliminary dissolving the water-soluble polymeric resin at the inner side of the water-soluble film facing the detergent composition, inducing preliminary gel formation already within the detergent composition prior to exposure of the unit dose article to the wash water accordingly, while having some water can help facilitating initial dissolution and as such faster diffusion of detergent surfactant actives, reducing time to interact and as such formation of gels with dissolved polymeric resin accordingly.
In some examples, the laundry detergent composition is a liquid laundry detergent composition comprising a non-aqueous solvent selected from 1,2-propanediol, dipropylene glycol, tripropyleneglycol, glycerol, sorbitol, polyethylene glycol, or a mixture thereof. Polyol based organic solvents are especially preferred for use in the present invention. In some examples, the liquid laundry detergent composition comprises between 10% and 40%, or between 15% and 30% by weight of the liquid laundry detergent composition of the non-aqueous solvent. Without wishing to be bound by theory, it is thought that higher levels of such organic solvents especially polyol solvents can help improving overall surfactant solubility, positively impacting surfactant diffusion kinetics into the wash water accordingly. A too high level of organic solvent however is to be avoided in order not to over-plasticize the water-soluble film, compromising unit dose article strength accordingly.
In some examples, the laundry detergent composition comprises a perfume. In some examples, the laundry detergent composition comprises an adjunct ingredient which can be selected from the group comprising builders including citrate, (encapsulated) enzymes including but not limited to proteases, amylases, lipases, cellulases, mannanases, xyloglucanases, DNA'ses, and mixtures thereof, bleach, bleach catalyst, aesthetic dye, hueing dye, brightener, cleaning polymers including alkoxylated polyamines and polyethyleneimines, soil release polymers, fabric conditioning polymers including Polyquaternium 10 (CathEC), further surfactant including amine oxide and solvent, chelants including aminocarboxylate and aminophosphonate chelants, dye transfer inhibitors, encapsulated perfume, polycarboxylates, structurant, pH trimming agents, antioxidants, preservatives, antibacterial agents including Tinosan HP100, probiotics, and mixtures thereof.
In some examples, the laundry detergent composition has a pH between 6 and 10, between 6.5 and 8.9, or between 7 and 8, wherein the pH of the laundry detergent composition is measured as a 10% product concentration in demineralized water at 20°C. Without wishing to be bound by theory, a too high or too low finished product pH may negatively impact water-soluble film dissolution kinetics, reducing detergent diffusion kinetics in the wash water and as such allowing more time for surfactant-water-soluble polymeric resin interaction accordingly.
When liquid, the laundry detergent composition may be Newtonian or non-Newtonian. In some examples, the liquid laundry detergent composition is non-Newtonian. Without wishing to be bound by theory, a non-Newtonian liquid has properties that differ from those of a Newtonian liquid, more specifically, the viscosity of non-Newtonian liquids is dependent on shear rate, while a Newtonian liquid has a constant viscosity independent of the applied shear rate. The decreased viscosity upon shear application for non-Newtonian liquids is thought to further facilitate liquid detergent dissolution and as such counter eventual gel formation with the dissolved water-soluble polymeric resin. The liquid laundry detergent composition described herein can have any suitable viscosity depending on factors such as formulated ingredients and purpose of the composition.

Process of making

Those skilled in the art will be aware of standard techniques to make the detergent composition and the water-soluble unit dose article according to the present invention. Those skilled in the art will also be aware of standard techniques and methods to make the ingredients of the detergent composition of the present invention.

Process of use

A further aspect of the present invention is a process of laundering fabrics comprising the steps of diluting between 200 and 3000 fold, preferably between 300 and 2000 fold, the water-soluble unit dose article according to the present invention with water to make a wash liquor, contacting fabrics to be treated with the wash liquor.
Preferably the wash liquor comprises between 5L and 75L, preferably between 7L and 40L, more preferably between 10L and 20L of water. Alternatively, the wash liquor may comprise between 35L and 65L of water. Preferably, the wash liquor is at a temperature of between 5°C and 90°C, preferably between 10°C and 60°C, more preferably between 12°C and 45°C, most preferably between 15°C and 40°C. Preferably, washing the fabrics in the wash liquor takes between 5 minutes and 60 minutes, preferably between 5 minutes and 40 minutes, more preferably between 5 minutes and 30 minutes, even more preferably between 5 minutes and 20 minutes, most preferably between 6 minutes and 18 minutes to complete. Alternatively, washing the fabrics in the wash liquor may take between 30 minutes and 60 minutes. Preferably, the wash liquor comprises between 1kg and 20 kg, preferably between 3kg and 15kg, most preferably between 5 and 10 kg of fabrics. The wash liquor may comprise water of any hardness preferably varying between 0 gpg to 40gpg.
The dimensions and values disclosed herein are not to be understood as being strictly limited to the exact numerical values recited. Instead, unless otherwise specified, each such dimension is intended to mean both the recited value and a functionally equivalent range surrounding that value. For example, a dimension disclosed as "40 mm" is intended to mean "about 40 mm."

EXAMPLES

Test methods

Detergent composition viscosity

The viscosity measurements are carried out using a rotational rheometer e.g. TA instruments HR10. The instrument includes a 40mm 2° cone fixture with a 52µ η gap. The measurement is carried out using a flow procedure that contains a conditioning step, a peak hold and a continuous ramp step. The conditioning step involves the setting of the measurement temperature at 20°C, a pre-shear of 10 seconds at a shear rate of 10s^-1, and an equilibration of 60 seconds at the selected temperature. The peak hold involves applying a shear rate of 0.05s^-1 at 20°C for 3min with sampling every 10s. The continuous ramp step is performed at a shear rate from 0.1 to 1200s^-1 for 3min at 20°C to obtain the full flow profile. The viscosity value at a shear rate of 20s^-1 is extracted and reported.

Gelling Factor (G)

The gelling factor method measures the strength of the gel formed between the enclosed detergent composition and the polyvinylalcohol comprised in the water-soluble film upon initial dissolution in the wash water. This method is designed to provide a lab characterization (using very low water amounts) of the infrequent or extreme in-home process where gelling can occur. It is used as a proxy to assess when the detergent is released into the washing water. If residues are created during the laundry process these residues can be redissolved but it might imply a further step and the purpose of this invention is to reduce the touches needed by the user during the laundry process.
The gelling factor is measured using a plate to plate rotational rheometer (TA Discovery Hybrid Rheometer) using a 60 mm flat spindle. The temperature of the bottom plate is set to 5 °C. An aluminium made cross-based frame (width of each crossbar is 6 mm) is placed on the bottom plate in order to divide the bottom plate in 4 equal quadrants. 1 ml of the detergent composition at room temperature, e.g. 20°C +/- 2°C, is respectively added at two opposing quadrants, creating a substantial triangular shape along the respective crossbars of the frame, as shown in FIG 2. 1 ml of a 10wt% solution of dissolved water-soluble film in demineralized water at room temperature, e.g. 20°C +/- 2°C, is dosed in the remaining 2 opposing quadrants. The cross-based frame is hence removed such that the 4 liquids remain separate. The rotating spindle is hence lowered to measurement condition such that the liquid comes out slightly off the entire perimeter of the spindle. The consequent measurement procedure includes a 30 second temperature conditioning, a peak hold of 180 seconds at 40/s and a gradual oscillatory angular frequency logarithmic sweep (from 100 to 0.016 rad/s within about 38 minutes through a logarithmic sweep at a constant and controlled stress of 0.1Pa, to ensure that the gel is always within the linear visco-elastic regime). The storage modulus (G') and loss modulus (G") are measured at 5 points per decade, which produces 20 data points in total. The average storage modulus (in Pa) and average loss modulus (in Pa) are calculated of the respective values at 0.040, 0.025 and 0.015 rad/s, e.g. the 3 last data points measured. The gelling factor is consequently calculated through dividing the average storage modulus by the average loss modulus value. It is a dimensionless value. Three measurements were taken and the average is taken as the gelling factor.

Water-soluble unit dose article dissolution - film residue

This test method describes a water-soluble unit dose article dissolution test, in which the amount of undissolved water-soluble film residues is assessed. More particularly, this method is designed to assess the relative dissolution properties of laundry water-soluble unit dose articles under stressed washing machine conditions. For this method Electrolux Programmable Washing machines type W565H comprising a ballast load with a mix of Cotton and Polycotton pieces (from Calderon Textiles, LLC 6131 W 80th Street Indianapolis, IN 46278) were used. Ballast loads are comprised of cotton and polycotton knit, double-ply swatches approximately 50x50cm in size.

Orange unit-dose articles (pouches)

Orange fabric is purchased from the Lubrizol-Equest company and must be desized before use by adding 25 items into a front loading Miele washing machine and running 1 short cotton cycle at 60°C (approximate duration of 1h30) with 50g of Ariel sensitive powder and a water hardness of 15gpg, followed by running 1 more short cotton cycles at 60°C (approximate duration of 1h30) with no detergent and a water hardness of 15gpg, followed by tumble drying.
The orange fabrics are then cut into 48X48cm pieces, folded in half, cut in half and sawn to the sides into 4 equivalent pouches of 22X22cm with the top side open. 1 test product of a pre-conditioned water-soluble unit dose article is placed at the bottom right corner of the orange pouch, and the pouch is stitched closed. The water-soluble unit dose article must be pre-conditioned for a minimum of 2 weeks at 23°C, 50%rH before testing.
Load: 4 loads of 3 kg of mixed cotton (13 pieces) and polycotton (10 pieces) were desized before use by washing in a short cotton cycle at 60°C with 79g of Ariel Professional detergent at a water hardness of 15gpg, followed by another short cotton cycle at 60°C without any detergent at a water hardness of 15gpg, and finally tumble-dried. Each load of 3.0kg is pretreated 2 times by washing with 4 Ariel pods in the "prewet" cycle, followed by a wash without detergent in the "dissolution program" described below, and finally tumble-dried.

The Electrolux W565 programmable washing machines were programmed with 2 programs. The first program was designed to equally wet the load (pre-wet program). The second program (dissolution program) was utilized to simulate 15min of a Western Europe stressed cycle setting, followed by pumping out the water and starting a spin of 3min at 1100rpm.

		Pre-wet program	Dissolution program
Wash	Time	5min	15min
	Motor rotation	49rpm	59rpm
	Water intake	12L	13.4L
	Heating	20°C	20°C
	Water Hardness	15gpg	15gpg
	Motor action time clockwise	28s	20s
	Motor resting time	12s	20s
	Motor action time Counterclockwise	28s	28s
Drain	Draining time	1min	20s
Drain	Motor rotation	20rpm	49rpm
Extraction	Time	30s	3min
Extraction	Motor rotation	900rpm	1100rpm

A load consisting of 13 pieces of 50X50cm of cotton and 10 pieces of 27X27cm of poly cotton (weighed at 3.0 +/- 0.15kg) was evenly introduced in the Electrolux W565 washing machine and the pre-wet program was run 2 times.
After the pre-wet program, the wet ballast was taken out of the drum and 4 orange pouches containing each a different test leg water soluble unit dose article were aligned at the bottom of the drum, hence 4 different test products are tested at once in the same washing machine in order to render the testing environment as reproducible as possible across the test legs. 10g of suds suppressor (Dowsil GP-4314 silicone suds suppressor, commercially available from the Dow Corning company) was added in the dispenser, and the wet load was placed on top of the orange pouches, without allowing the drum to move. The dissolution program was initiated. At the end of the full program, the orange pouches were transferred to a grading room (equipped with D65 lighting conditions) to be assessed for residues by expert graders.
The orange pouches are cut and graded visually, within 30min after the end of each run, according to a scale of 0 to 7 (0= No film residue, 7=Full pouch residue). The final score is calculated as the average of 4 external replicates, i.e. 4 different washing machine runs, and repeated 2 times (average of 8 scores).

Examples

The unit dose article dissolution profile and linked film residue risk was assessed for film - liquid detergent combinations with a gelling factor G according to the invention and cross-compared with film -liquid detergent combinations with a gelling factor G outside the scope of the invention, following the test method described herein.

Detergent composition

Table 1 describes the liquid laundry detergent composition tested. The liquid detergent composition has been prepared through mixing of the individual detergent components in a batch process.

Table 1: Liquid detergent composition (wt% - 100% active basis)

100% active	Bottom compartment	Top compartment 1	Top compartment 2
Neodol 24/7 ethoxylated alcohol nonionic surfactant	3.2	2.5	1.3
Linear alkylbenzene sulphonic acid	27.6	26.3	17.1
A24E3S	7.9	10.5	6.7
Citric acid	0.7	0.7	0.4
Fatty acid	11.5	5.2	3.3
Ethoxylated polyethyleneimine*	1.5	1.5	1.0
Zwitterionic polyamine **	1.5	1.8	1.2
HEDP	0.7	2.2	1.4
Texcare SRA300	-	2.2	2.2
Polyquaternium 10***	-	-	7.8
FWA 49	0.35	-	-
Antifoam (AF8017)	0.25	-	-
1,2-propanediol	15.6	20.3	24.1
Glycerol	5.0	6.7	4.9
PPG (MW 400)	-	-	12.7
Monoethanolamine (pH trimming agent)	9.7	10.2	6.6
K2SO3	0.4	0.2	0.4
MgCl2	0.1	0.3	0.2
Water	10.1	8.1	7.8
Acusol 880	-	-	0.2
Hueing dye	-	0.4	-
Hydrogenated castor oil	0.1	0.1	0.1
Minors (perfume, dyes, antioxidant, preservative...)	Balance to 100%	Balance to 100%	Balance to 100%
pH (as 10% aqueous solution)	7.4	7.4	7.4

*ethoxylated polyethyleneimine having an average degree of ethoxylation of 20 per EO chain and a polyethyleneimine backbone with MW of about 600
** Lutensit Z96: partially sulfate polyethoxylated hexamethylenediamine, as available from the BASF company
*** premix composition: 37wt% cationic hydroxyethyl cellulose, 60wt% PPG400, 3wt% Acusol 880 - premix components reflected in above formula composition

Film/resin compositions

Table 2 describes a range of water-soluble film/related water-soluble resins used within the gelling factor and pouch dissolution tests described herein, as received from the MonoSol company. Film/resin composition 3 represents the outer films of Ariel All-in one product, as commercially available in the UK in January 2024.

Table 2: Water-soluble film/resin compositions

	Film/resin composition 1	Film/resin composition 2	Film/resin composition 3
Polymer A (PVOH polymer)	PVOH - PVAcetate	PVOH - PVAcetate - itaconic acid	PVOH - PVAcetate monomethylmaleate
Polymer B (PVOH polymer	PVOH - PVAcetate	PVOH - PV Acetate	PVOH - PVAcetate
A/B wt%-ratio	15/85	15/85	40/60
Average dH (A/B)	74/79	77/79	90/87
4% viscosity (cps)	5/15	6/15	17/21
% anionic substitution	0	1.25	4.00

Table 3 shows the gelling factor G and pouch dissolution data obtained using the test methods described herein. For the gelling factor G data the bottom compartment liquid detergent ex Table 1 was combined with the different water-soluble resins ex Table 2. For the pouch dissolution test, a 3-compartment pouch following the Ariel All-in one superposed design, as commercially available in the UK in January 2024, made of the different water-soluble resins ex Table 2 and comprising the detergent composition ex Table 1 has been tested. It can be seen that the combination of the liquid detergent composition with a water-soluble film yielding a lower gelling factor G according to the invention also yields a strongly better pouch dissolution hence reduced film residue risk on fabrics at the end of a wash cycle.

Table 3: Gelling factor G and pouch dissolution

	Gelling factor G	Pouch dissolution
Film/resin composition 1	1.01 (inventive)	1.4
Film/resin composition 2	1.09 (inventive)	1.3
Film/resin composition 3	1.71 (comparative)	2.9

Table 4 summarizes the gelling factor G for a range of commercial product formulations combined with water-soluble resin composition 3, as well as with the water-soluble resin from their respective commercially used film (e.g. M8630 ex the MonoSol company). It can be seen that when exchanging the liquid detergent composition ex Table 1 with commercially available alternatives, that none of these commercially available alternative formulations nor commercially available film resin -formulation combinations yield in a gelling factor G according to the invention, independent whether these commercially available formulations are tested with their respective commercial film resin, or with the comparative test resin used within this testing.

Table 4: Gelling factor of commercially available liquid detergents

Commercially available liquid detergent	Production code	Gelling factor G Resin composition 3	Gelling factor G M8630
Persil Unilever 3in1 BIO blue	232126P3 from November 2022	3.45	3.34
Persil Unilever 3in1 BIO violet		2.51	4.07
Persil Unilever 3in1 BIO white		3.06	2.57
Persil Henkel 4in1 Discs	KO 18 Y 2 00 34 09:02 from November 2022	2.53	2.55
Universal Dark Blue
Persil Henkel 4in1 Discs		3.04	3.5
Universal Green
Persil Henkel 4in1 Discs		3.04	3.91
Universal Light Blue
Persil Henkel 4in1 Discs		1.73	2.37
Universal White

Claims

A unit dose article comprising a water-soluble film and at least one detergent composition,
wherein the detergent composition is encapsulated within a compartment formed by the water-soluble film;

wherein the water-soluble film comprises polyvinyl alcohol polymer and wherein the polyvinyl alcohol polymer comprises an anionic polyvinyl alcohol copolymer, a polyvinyl alcohol homopolymer, or a blend thereof;

wherein the detergent composition comprises a non-soap surfactant system; and

wherein an aqueous solution comprising the water-soluble film and the detergent composition dissolved therein has a gelling factor G of less than 1.25, preferably less than 1.2 and more preferably less than 1.15, wherein $G = G' / G "$ wherein
G' is the "storage" or "elastic" modulus; and

G" is the "loss" or "plastic" modulus;

wherein the aqueous solution is prepared and G' and G" are measured as described herein.
The unit dose article according to claim 1 wherein the surfactant system comprises anionic non-soap surfactant and nonionic surfactant.
The unit dose article according to the preceding claim wherein the anionic non-soap surfactant is selected from the group consisting of linear alkyl benzene sulphonate, alkyl ethoxy sulphate, alkyl sulphate, and mixtures thereof, and wherein the nonionic surfactant is selected from the group consisting of primary alcohol alkoxylate, secondary alcohol alkoxylate, and mixtures thereof.
The unit dose article according to any of the preceding claims wherein the detergent composition is in liquid from.
The unit dose article according to any of the preceding claims further comprising fatty acid.
The unit dose article according to any of the preceding claims further comprising an organic solvent selected from the group consisting of 1,2-propanediol, dipropylene glycol, tripropyleneglycol, glycerol, sorbitol, polyethylene glycol, ethoxylated glycerin, or a mixture thereof.
The unit dose article according to any of claims 4 to 6 wherein the liquid detergent composition comprises between 5% and 25% by weight of the liquid detergent composition of water.
The unit dose article according to any of claims 4 to 7 wherein the liquid detergent composition has a pH of from 6 to 10, preferably from 6.5 to 8.9, preferably from 7 to 8 as measured in a 10% weight solution in distilled water at 20°C.
The unit dose article according to any of the preceding claims wherein the polyvinyl alcohol comprises a blend of a polyvinylalcohol homopolymer and a carboxylated anionic polyvinylalcohol copolymer, or a blend of polyvinylalcohol homopolymers.
The unit dose article according to any of the preceding claim wherein the carboxylated anionic polyvinylalcohol copolymer comprises an anionic monomer unit derived from a dicarboxylate, preferably derived from the group consisting of itaconic acid, monoalkyl itaconate, dialkyl itaconate, itaconic anhydride, and mixtures thereof, most preferably itaconic acid.
The unit dose article according to any of the preceding claims wherein the anionic polyvinyl alcohol copolymer has an average degree of anionic modification of between 1% and 3%.
The unit dose article according to any of the preceding claims wherein the polyvinyl alcohol has an average degree of hydrolysis of between 70% and 80%.
The unit dose article according to any of the preceding claims wherein the polyvinyl alcohol has a 4% solution viscosity at 20°C of between 3 cP and 20 cP, preferably between 5 cP and 15 cP.
The unit dose article according to any of claims 1 to 9 wherein the polyvinyl alcohol comprises a polyvinyl alcohol polymer blend comprising a polymer A and a polymer B, both consisting essentially of a vinyl alcohol monomer unit and a vinyl acetate monomer unit:
i) from 1% to 50%, preferably from 5% to 30%, more preferably from 10% to 20% by weight of the polymer blend of polymer A, wherein polymer A has
an average degree of hydrolysis of from 60% to less than 75%, preferably of from 65% to less than 75%, more preferably of from 70% to less than 75%; and

a 4% solution viscosity at 20°C of from 3 cP to 20 cP, preferably from 3 cP to 15 cP, more preferably of from 3 cP to 10 cP; and

ii) from 50% to 99%, preferably from 70% to 95%, more preferably from 80% to 90% by weight of the polymer blend of polymer B, wherein polymer B has
an average degree of hydrolysis of from 60% to less than 80%, preferably of from 70% to less than 80%, more preferably of from 75% to less than 80%; and

a 4% solution viscosity at 20°C of from 10cP to 40cP, preferably from 10 cP to 30 cP, more preferably of from 10 cP to 20 cP.
The unit dose article according to any of claims 1 to 9 wherein the polyvinyl alcohol comprises a polyvinyl alcohol polymer blend comprising:
i) from 1% to 30%, preferably from 5% to 25%, more preferably from 10% to 20% by weight of the polymer blend of polymer A, wherein polymer A comprises an anionic monomer unit, a vinyl alcohol monomer unit and a vinyl acetate monomer unit,
wherein polymer A has
an average degree of hydrolysis of from 60% to less than 80%, preferably of from 70% to less than 80%, more preferably of from 75% to less than 80%; and

a 4% solution viscosity at 20°C of from 3 cP to 20 cP, preferably from 3 cP to 15 cP, more preferably of from 3 cP to 10 cP;

an anionic monomer unit comprising a monomer derived from the group consisting of itaconic acid, monoalkyl itaconate, dialkyl itaconate, itaconic anhydride, and mixtures thereof;

from 0.1 mol% to 4.0 mol%, preferably of from 0.5 mol% to 3.0 mol%, more preferably from 1.0 mol% to 2.0 mol% of the anionic monomer unit; and

ii) from 70% to 99%, preferably from 75% to 95%, more preferably from 80% to 90% by weight of the polymer blend of polymer B, wherein polymer B consists essentially of a vinyl alcohol monomer unit and a vinyl acetate monomer unit,
wherein polymer B has
an average degree of hydrolysis of from 70% to less than 80%, preferably of from 72% to less than 80%, more preferably of from 75% to less than 80%; and
a 4% solution viscosity at 20°C of from 10 cP to 40 cP, preferably from 10 cP to 30 cP, more preferably of from 10 cP to 20 cP.