WO2026012798A1

WO2026012798A1 - Water-soluble film and washing or cleaning agent portion unit comprising such film

Info

Publication number: WO2026012798A1
Application number: PCT/EP2025/068527
Authority: WO
Inventors: Frank Meier; Thorsten Ott; Juliette MADEDDU; Jona SCHUESSLER; Niklas Siepler; Uwe Trebbe
Original assignee: Henkel AG and Co KGaA
Current assignee: Henkel AG and Co KGaA
Priority date: 2024-07-12
Filing date: 2025-06-30
Publication date: 2026-01-15
Anticipated expiration: 2027-01-12

Abstract

The invention relates to a water-soluble film, in particular water-soluble film for washing and/or cleaning agent portion units, wherein the film comprises, based on the total weight of the film composition, (A) 50 to 75 wt.%, preferably 60 to 70 wt.%, of at least one PVOH (co-)polymer, wherein the PVOH (co-)polymer is selected from at least one polyvinyl alcohol homopolymer, at least one polyvinyl alcohol copolymer or a mixture thereof, (B) 2.5 to 30 wt.%, preferably, 5 to 25 wt.%, of at least one biopolymer, (C) 0.2 to 15 wt.%, preferably 0.5 to 10 wt.%, of at least one alkyl polyglycoside, wherein the alkyl polyglycoside has the formula R⁵O-[G]_p, in which R⁵ represents a linear or branched alkyl or alkenyl having 4 to 24, preferably 5 to 20, C atoms, G represents a sugar residue having 5 or 6 C atoms and p represents numbers from 1 to 10. The invention also relates to a pre-portioned washing or cleaning composition comprising at least one receiving chamber with a washing or cleaning composition, in particular a highly concentrated washing or cleaning composition, and a water-soluble film. Furthermore, the invention relates to a method for producing such a water-soluble film and such a washing or cleaning agent portion unit, and to a method for washing textiles and/or for cleaning hard surfaces, in particular dishes, using such a washing or cleaning agent portion unit.

Description

WATER-SOLUBLE FILM AND WASHING OR CLEANING AGENT PORTION UNIT COMPRISING SUCH FILM

DESCRIPTION

The invention is in the field of washing and cleaning compositions, in particular in the field of water-soluble films for washing and cleaning compositions. The invention relates to a water-soluble film. In particular, the invention relates to a water-soluble film for a washing or cleaning agent portion unit. The invention also relates to a pre-portioned washing or cleaning composition comprising at least one receiving chamber with a washing or cleaning composition, in particular a highly concentrated washing or cleaning composition, and a water-soluble film. Furthermore, the invention relates to a method for producing such a water-soluble film and such a washing or cleaning agent portion unit, and to a method for washing textiles and/or for cleaning hard surfaces, in particular dishes, using such a washing or cleaning agent portion unit.

Constantly changing requirements are being imposed on the packaging and supply forms of washing and cleaning compositions. For some time now, the main focus has been on the convenient dosing of washing and cleaning compositions by the consumer and the simplification of the steps required to carry out a washing or cleaning process. One technical solution is offered by pre-portioned washing or cleaning compositions, e.g. film bags or pouches with one or more receiving chambers for solid and/or liquid washing or cleaning compositions. Such washing or cleaning agent portion units (or unit dose articles) are becoming increasingly popular with consumers, not only because they are easy and practical to use, but also because of their aesthetic presentation.

One trend relevant to the production of these film pouches is the miniaturization of these film bags or pouches, i.e., the reduction of their fillable inner volume. In addition to greater consumer acceptance due to simplified handling, the background to this development is sustainability aspects in particular, e.g., in relation to transport volumes and costs and the quantity of packaging materials used.

The formulation of high-performance washing or cleaning agent formulations for film bags or pouches with reduced internal volume is a challenge for developers. The concentration of modern washing and cleaning compositions requires the progressive optimization of existing formulations and the development of new, more efficient formulations. One aim of these developments, which are generally based on known active washing and cleaning agents, is to increase the washing or cleaning performance of the formulations while maintaining or reducing the dosing quantity. Corresponding film bags or pouches can only contain small amounts of non-wash-active ingredients, which is why the use of stabilizing but non-wash-active solvent systems, for example, must be limited in liquid formulations. In the resulting highly concentrated gels, on the other hand, storage stability is often reduced due to incompatibilities between different active ingredients. Furthermore, solid active ingredients often cannot be suspended with sufficient stability.

One solution to the problem described above is to package the washing or cleaning compositions in multi-chamber portion units, in which the chambers allow both the separation of incompatible active ingredients and the separate packaging of liquid and solid active ingredients.

The receiving chambers of the pre-portioned washing or cleaning agent portion units are enclosed by at least one water-soluble film. The receiving chambers are preferably formed by molding a water-soluble film into a deep-drawing matrix. After being filled, the receiving chambers are sealed with a water-soluble film in a subsequent step. In a preferred embodiment due to its efficiency and ease of implementation, the receiving chambers of the washing or cleaning agent portion unit (or unit dose article) are formed by two water-soluble films joined together in a sealing plane.

Typically, the water-soluble film comprises one or more structurally different water-soluble polymer(s). In particular, polymers from the group of (possibly acetalized) polyvinyl alcohols (PVOH) and their copolymers are used as water-soluble polymer(s). Suitable water-soluble films are commercially available, e.g., from MonoSol LLC, Aicello Chemical Europe GmbH or Mitsubishi Chemicals Group, and described in, e.g., US 3374195 A, US 3413229 A, US 6787512 B2, US 6821590 B2, WO 2004/074351 A2, WO 2018/081494 A2, and EP 1158016 A2.

One point of consumer criticism of the commercially available washing or cleaning agent unit dose articles is the prejudice that the water-soluble films could be "microplastics", although the water- soluble films mentioned and commonly used are completely water-soluble and biodegradable and therefore do not meet any of the criteria for the definition of "microplastics".

A commercially available PVOH film formulation typically contains 25-30% plant-based ingredients (e.g., glycerol, polypropylene glycol, sorbitol and the like). To further improve consumer perception of sustainability and biodegradability, it is desirable to replace some or all of the PVOH in the film with biopolymers that can be largely or completely plant-based. It is also desirable to increase the proportion of other components of the film composition (solvents, plasticizers, processing aids and the like) that can be obtained from renewable raw materials. It would be particularly desirable to provide a water-soluble film, in particular for washing or cleaning agent unit dose articles, whose ingredients are obtained largely or even entirely from renewable and/or plant-based raw materials. In e.g., WO 2023/072703 a water-soluble film comprising protein is described, and in US 2021/0079223 a water-soluble film comprising casein is described.

However, the use of biopolymers in water-soluble film compositions unfortunately leads to disadvantages with regard to the required technical properties such as stretching behavior or solubility, mechanical properties and/or optical and haptic properties such as color, stickiness, viscosity or haze. It is assumed that these disadvantages are based on a possible incompatibility of the biopolymers with the PVOH (co-)polymers, e.g., due to a different hydroxyl group density or the resulting different polarity, which can lead to segregation and island formation in the film. Unfortunately, no biopolymers are yet known that make it possible to avoid PVOH (co-)polymers largely or even completely in water-soluble films for washing and/or cleaning agent portion units, in particular for wrapping liquid washing and/or cleaning compositions.

Therefore, the aim of the present invention was to reduce the proportion of PVOH (co-)polymers in water-soluble film compositions and to increase the proportion of biopolymers, in particular water- soluble films for washing and/or cleaning agent portion units. A further aim of the present invention was to improve the mechanical properties of PVOH (co-)polymer, in particular PVOH (co-)polymer and biopolymer, containing water-soluble films, in particular water-soluble films for washing and/or cleaning agent portion units.

The inventors of the present invention have surprisingly found that the addition of alkyl polyglycosides, in particular alkyl polyglucosides (APG) and/or alkyl polypentosides (APP), makes it possible to increase the proportion of biopolymers in PVOH-based water-soluble film compositions without the disadvantages mentioned before. The inventors of the present invention also have surprisingly found that the addition of alkyl polyglycosides, in particular alkyl polyglucosides (APG) and/or alkyl polypentosides (APP), makes it possible to produce water-soluble films at higher draw ratios. This is in particular advantageous because water-soluble films produced at higher draw ratios increase production efficiency and film material can be saved, which in turn is good for sustainability. Hence, the inventors have surprisingly found film compositions which are more sustainable in comparison to conventional PVOH-based films, while overcoming the above-mentioned drawbacks of biopolymer-based films.

In a first aspect the invention relates to a water-soluble film, in particular water-soluble film for washing and/or cleaning agent portion units, wherein the film comprises, based on the total weight of the film composition,

(A) 50 to 75 wt.%, preferably 60 to 70 wt.%, of at least one PVOH (co-)polymer, wherein the PVOH (co-)polymer is selected from at least one polyvinyl alcohol homopolymer, at least one polyvinyl alcohol copolymer or a mixture thereof,

(B) 2.5 to 30 wt.%, preferably, 5 to 25 wt.%, of at least one biopolymer,

(C) 0.2 to 15 wt.%, preferably 0.5 to 10 wt.%, of at least one alkyl polyglycoside, wherein the alkyl polyglycoside has the formula (I)

R⁵O-[G]_P (I), in which R⁵ represents a linear or branched alkyl or alkenyl having 4 to 24, preferably 5 to 20, C atoms, G represents a sugar residue having 5 or 6 C atoms and p represents numbers from 1 to 10.

In a further aspect the invention relates to a water-soluble film, in particular water-soluble film for washing and/or cleaning agent portion units, as described herein, wherein the at least one PVOH (co-)polymer is selected from

(i) a vinyl alcohol vinyl acetate copolymer; and/or (ii) a vinyl alcohol maleate copolymer, wherein the vinyl alcohol maleate copolymer comprises a maleate monomer unit derived from the group consisting of maleic acid, monoalkyl maleate, dialkyl maleate, maleic anhydride, and a mixture thereof; and/or

(iii) a sulfonated polyvinyl alcohol copolymer; and/or

(iv) a carboxylated polyvinyl alcohol copolymer, wherein the the carboxylated polyvinyl alcohol copolymer comprises a carboxylate monomer unit derived from the group consisting of acrylate, methacrylate, maleate, and a mixture thereof; and/or

(v) a PVOH (co-)polymer comprising an anionic monomer unit, wherein the anionic monomer is selected from the group consisting of vinyl acetic acid, alkyl acrylates, maleic acid, monoalkyl maleate, dialkyl maleate, monomethyl maleate, dimethyl maleate, maleic anhydride, fumaric acid, monoalkyl fumarate, dialkyl fumarate, monomethyl fumarate, dimethyl fumarate, itaconic acid, monomethyl itaconate, dimethyl itaconate, itaconic anhydride, citraconic acid, monoalkyl citraconate, dialkyl citraconate, citraconic anhydride, mesaconic acid, monoalkyl mesaconate, dialkyl mesaconate, glutaconic acid, monoalkyl glutaconate, dialkyl glutaconate, glutaconic anhydride, vinyl sulfonic acid, alkyl sulfonic acid, ethylene sulfonic acid, 2-acryl amido-1 -methyl propane sulfonic acid, 2-acryl amide- 2-methyl propane sulfonic acid, 2-methyl acryl amido-2-methyl propane sulfonic acid, 2-sulfoethyl acrylate, alkali metal salts of the foregoing, esters of the foregoing, and mixtures thereof; and/or

(vi) mixtures thereof.

In a further aspect the invention relates to a water-soluble film, in particular water-soluble film for washing and/or cleaning agent portion units, as described herein, wherein

(i) the at least one biopolymer is derived from natural sources like animals, plants, algae, insects, Crustacea, fungi or microorganisms; and/or

(ii) the at least one biopolymer is selected from the group consisting of polysaccharides, peptides, proteins, glycoproteins, proteoglycans, poly(amino acids), derivatives of the foregoing, and mixtures thereof; and/or

(iii) the at least one biopolymer is selected from the group consisting of galactomannans, xyloglucans, galactoglucomannans, starches, amylose and amylopectin, glucans, p-glucans, pectins, protopectin, pectin polysaccharides, arabinans, galactans, and arabinogalactans, a-glucans, a1-4- glucans, a-1 ,6-glucans, glucomannans, celluloses, carboxy methyl cellulose (CMC), hydroxyethyl cellulose (HEC), hydroxypropyl cellulose (HPC), hydroxypropyl methyl cellulose (HPMC), methyl cellulose (MC), ethyl cellulose (EC), hemicelluloses, gum arabic, gum tragacanth, karaya gum, carrageenans, alginates, alginic acid (heteropolysaccharide comprised of D-mannuronic acid and L- guluronic acid), agar, agarose, furcellaran, chitin, chitosan, hyaluron, xanthan, gellan, dextran, curdlan, scleroglucan, schizophyllan, dextrins, cyclodextrins, glycogen, hydroxypropyl starch phosphate (HSP), hyaluronic acid, glycosaminoglycans, pullulan, gelatin, chrysolaminarin, laminarin, lentinan, lichenin, pleuran, zymosan, wheat proteins, soy proteins, pea proteins, potato proteins, whey proteins, corn proteins, caseins, aS1-, aS2-, p- and K-casein, caseinates, bovine casein salts, goat casein salts, sheep casein salts, p-lactoglobulin, a-lactalbumin, serum albumin, immunoglobulin, casein macropeptides, elastins, fibrins, collagens, aggrecans, chitins, chondroitin sulphate, keratan sulphate, heparin, dermatan sulphate and hyaluronate (hyaluronic acid), cyanophycin, poly(a-L-lysin), poly(y-glutamic acid), derivatives of the foregoing, and mixtures thereof.

In a further aspect the invention relates to a water-soluble film, in particular water-soluble film for washing and/or cleaning agent portion units, as described herein, wherein the at least one alkyl polyglycoside is selected from

(i) alkyl polyglycosides described by the formula (II) in which R¹ and R² are same or different and independently selected from H or OH, R³ is selected from H or CH2OH, represents branched or unbranched alkyl or alkenyl group, n represents 4 to 18, in particular 5 to 15, and p represents numbers from 1 to 10; and/or

(ii) alkyl polyglucosides (APG) derived from glucose and described by the formula (III) in which represents branched or unbranched alkyl or alkenyl group, n represents 7 to 18, in particular 10 to 15, and p represents numbers from 1 to 10; and/or

(iii) alkyl polypentosides (APP) derived from xylose and described by the formula (IV) in which represents branched or unbranched alkyl or alkenyl group, n represents 4 to 15, in particular s to 10, and p represents numbers from 1 to 10; and/or

(iv) an alkyl polyglycoside which is an alkyl polypentoside (APP) and/or being selected from formula (V) or formula (VI)

(v) alkyl polyglycosides having a hydrophilic-lipophilic balance (HLB) value equal or greater than 10, preferably equal or greater than 12, more preferably equal or greater than 15.

In a further aspect the invention relates to a water-soluble film, in particular water-soluble film for washing and/or cleaning agent portion units, as described herein, wherein the at least one biopolymer is selected from the group consisting of starches, amylose and amylopectin, celluloses, carboxy methyl cellulose (CMC), hydroxyethyl cellulose (HEC), hydroxypropyl cellulose (HPC), hydroxypropyl methyl cellulose (HPMC), methyl cellulose (MC), ethyl cellulose (EC), glucans, p-glucans, a-glucans, wheat proteins, soy proteins, pea proteins, potato proteins, whey proteins, corn proteins, caseins, aS1-, aS2-, p- and K-casein, caseinates, bovine casein salts, goat casein salts, sheep casein salts, derivatives of the foregoing, and mixtures thereof, preferably starches, amylose and amylopectin, carrageenans, wheat proteins, soy proteins, pea proteins, potato proteins, whey proteins, corn proteins, caseins, aS1-, aS2-, p- and K-casein, caseinates, bovine casein salts, goat casein salts, sheep casein salts, derivatives of the foregoing, and mixtures thereof.

In a further aspect the invention relates to a water-soluble film, in particular water-soluble film for washing and/or cleaning agent portion units, as described herein, wherein the film comprises at least two biopolymers, wherein the at least two biopolymers are selected from the group consisting of starches, amylose and amylopectin, celluloses, carboxy methyl cellulose (CMC), hydroxyethyl cellulose (HEC), hydroxypropyl cellulose (HPC), hydroxypropyl methyl cellulose (HPMC), methyl cellulose (MC), ethyl cellulose (EC), glucans, p-glucans, a-glucans, wheat proteins, soy proteins, pea proteins, potato proteins, whey proteins, corn proteins, caseins, aS1-, aS2-, p- and K-casein, caseinates, bovine casein salts, goat casein salts, sheep casein salts, derivatives of the foregoing, and mixtures thereof, preferably starches, amylose and amylopectin, carrageenans, wheat proteins, soy proteins, pea proteins, potato proteins, whey proteins, corn proteins, caseins, aS1-, aS2-, p- and K-casein, caseinates, bovine casein salts, goat casein salts, sheep casein salts, derivatives of the foregoing, and mixtures thereof.

In a further aspect the invention relates to a water-soluble film, in particular water-soluble film for washing and/or cleaning agent portion units, as described herein, wherein the total amount of PVOH (co-)polymers and biopolymers is 52.5 to 80 wt.%, preferably 60 to 75 wt.%; and/or the ratio of the at least one PVOH (co-)polymer and the at least one biopolymer is between 20:1 and 2.5:1 , preferably between 15:1 and 10:1.

In a further aspect the invention relates to a water-soluble film, in particular water-soluble film for washing and/or cleaning agent portion units, as described herein, wherein the film also comprises at least one further ingredient, wherein the at least one further ingredient is selected from the group consisting of bittering agents, solvents, in particular water, as well processing agents, in particular plasticizers, lubricants, release agents, fillers, extenders, cross-linking agents, antiblocking agents, antioxidants, detackifying agents, and antifoam.

In a further aspect the invention relates to a water-soluble film, in particular water-soluble film for washing and/or cleaning agent portion units, as described herein, wherein the film has a thickness of 30 to 100 pm, preferably 50 to 95 pm, more preferably 60 to 90 pm; and/or the film has a draw ratio of 1 .5 to 3.0, preferably 1 .8 to 2.6, more preferably 1 .8 to 2.3.

In a further aspect the invention relates to a washing and/or cleaning agent portion units comprising at least one film, as described herein, and at least one washing and/or cleaning composition, wherein the washing/or cleaning composition is incorporated into at least one receiving chamber surrounded by the at least one film.

In a further aspect the invention relates to a method for producing a water-soluble film, as described herein, comprising the steps of a) providing a PVOH slurry, wherein the PVOH solution comprises at least one PVOH (co-)polymer and wherein the PVOH (co-)polymer is selected from at least one polyvinyl alcohol homopolymer, at least one polyvinyl alcohol copolymer or a mixture thereof, b) adding additives as required, in particular adding at least one biopolymer, as described herein, and/or at least one alkyl polyglycoside, preferably selected from alkyl polyglucosides (APG), alkyl polypentosides (APP) and mixtures thereof, and/or further ingredients, as described herein, c) heating the slurry to form a solution, and d) casting the solution of step c) on a suitable surface to create a film having a thickness in the range of 30 to 100 pm, preferably 50 to 95 pm, more preferably 60 to 90 pm.

In a further aspect the invention relates to a method for producing a washing and/or cleaning agent portion unit, as described herein, comprising the steps of a) transporting a first water-soluble film, which is a film according to any of claims 1 to 12, in the direction of a dosing station at a speed above 0.04 m/s, preferably above 0.08 m/s, b) molding the first water-soluble film into the cavities of a deep-drawing die located below the water-soluble film, so as to form at least one cavity having a maximum diameter in the direction of travel of the film of between 3 and 75 mm, wherein the film has a draw ratio of 1 .5 to 3.0, preferably

1 .8 to 2.6, more preferably 1 .8 to 2.3, c) filling the cavity by means of the dosing station with a first cleaning or washing composition, d) further transporting the filled cavity in the direction of a sealing station at a speed above 0.04 m/s, preferably above 0.08 m/s, and e) sealing the filled cavity with a second water-soluble film, wherein the first water-soluble film and the second water-soluble film are the same or different.

In a further aspect the invention relates to a method for increasing the proportion of biopolymers in PVOH-containing water-soluble films, comprising the step of adding at least one alkyl polyglycoside, wherein the alkyl polyglycoside has the formula (I)

In a further aspect the invention relates to the use of at least one alkyl polyglycoside for improving the compatibility of the mixture of at least one biopolymer and at least one PVOH (co-)polymer in water-soluble films, wherein the alkyl polyglycoside has the formula (I)

In a further aspect the invention relates to the use of at least one alkyl polyglycoside for improving the mechanical properties of PVOH- and/or biopolymer containing water-soluble films, in particular increasing the draw ratio, wherein the alkyl polyglycoside has the formula (I)

In preferred embodiments, the film has a thickness in the range of 30 to 100 pm, preferably 50 to 95 pm, more preferably 60 to 90 pm and/or a draw ratio of 1 .5 to 3.0, preferably 1 .8 to 2.6, more preferably 1 .8 to 2.3.

These and other aspects, features and advantages of the invention will become apparent to the person skilled in the art from a study of the following detailed description and claims. Any feature from one aspect of the invention may be used in any other aspect of the invention. Furthermore, it is understood that the examples contained herein are intended to describe and illustrate the invention, but are not limiting thereto and, in particular, the invention is not limited to these examples.

All percentages are percent by weight (wt.%) unless otherwise stated. Numerical ranges given in the format "from x to y" include the stated values. Where multiple preferred numerical ranges are specified in this format, it is understood that all ranges resulting from the combination of the various endpoints are also included.

"At least one" as used herein means one or more, i.e., 1 , 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 , 12, 13, 14 or more.

The term "washing and cleaning compositions" or "washing or cleaning compositions" as used herein is synonymous with the term "agent" or "detergent" or "composition" and means a composition for cleaning textiles and/or hard surfaces, in particular dishes, as explained in the description (unless expressly stated otherwise).

The term "washing or cleaning agent portion unit" or "washing or cleaning agent unit dose (article)" are used synonymously herein and means a pre-portioned washing or cleaning agent comprising one or more receiving chamber(s), the one or more receiving chamber(s) comprising at least one washing or cleaning composition, the chambers being separated by a water-soluble film as described herein.

"Approximately" or "about" as used herein with respect to a numerical value refers to the corresponding numerical value ±10%, preferably ±5%.

A substance, e.g., a composition or an agent, is solid according to the definition of the invention if it is in the solid state at 25°C and 1 ,013 mbar.

A substance, e.g., a composition or an agent, is liquid according to the definition of the invention if it is in the liquid state of aggregation at 25°C and 1 ,013 mbar. In this context, liquid also includes gellike. "Liquid" as used herein includes liquids and gels as well as pasty compositions. It is preferred that the liquid compositions are flowable and pourable at room temperature, but it is also possible that they have a yield point.

The present invention is based on the surprising finding of the inventors that the addition of alkyl polyglycosides, in particular alkyl polyglucosides (APG) and/or alkyl polypentosides (APP), makes it possible to increase the proportion of biopolymers in PVOH-based water-soluble film compositions without the disadvantages mentioned before, in particular water-soluble films for washing and/or cleaning agent portion units. In particular, it is surprising that alkyl polyglycosides, in particular alkyl polyglucosides (APG) and/or alkyl polypentosides (APP), seem to be able to improve the compatibility of PVOH (co-)polymers and biopolymers. Although it is known to use alkyl polyglycosides as surfactants in washing and cleaning compositions, it has not been described to use them in water- soluble films in order to improve the compatibility of PVOH (co-)polymers and biopolymers. It is even more surprising that usage of alkyl polyglycosides, in particular alkyl polyglucosides (APG) and/or alkyl pentosides (APP), in film compositions enables reduction of PVOH (co-)polymer content in such film compositions. A further surprising finding is that alkyl polyglycosides, in particular alkyl polyglucosides (APG) and/or alkyl polypentosides (APP) improves the mechanical properties of water-soluble films, in particular water-soluble films for washing and/or cleaning agent portion units. A particular further surprising finding is that alkyl polyglycosides, in particular alkyl polyglucosides (APG) and/or alkyl polypentosides (APP), make it possible to produce water-soluble films, in particular water-soluble films for washing and/or cleaning agent portion units, at higher draw ratios.

Water-soluble film compositions according to the invention comprise, based on the total weight of the film composition,

(B) 2.5 to 30 wt.%, preferably, 5 to 25 wt.%, of at least one biopolymer,

PVOH (co-)polymers

Water-soluble films for washing and/or cleaning agent portion units comprise one or more structurally different water-soluble polymer(s). Usually, polymers from the group of (optionally acetalized) polyvinyl alcohols (PVOH) and copolymers thereof are used as water-soluble polymer(s) in such films. Such polymers are usually polyvinyl alcohol polymers or polyvinyl alcohol copolymers whose molecular weight is in the range from 10,000 to 1 ,000,000 g/mol, preferably from 20,000 to 500,000 g/mol, particularly preferably from 30,000 to 100,000 g/mol and especially from 40,000 to 80,000 g/mol.

The production of polyvinyl alcohols and polyvinyl alcohol copolymers generally involves the hydrolysis of intermediate polyvinyl acetate. Preferred polyvinyl alcohols and polyvinyl alcohol copolymers have a degree of hydrolysis (expressed as percentage of vinyl acetate units converted to vinyl alcohol units) of 70 to 100 mol%, preferably 80 to 90 mol%, more preferably 81 to 89 mol% and in particular 82 to 88 mol%. In case, PVOH is fully hydrolyzed, i.e., virtually all acetate groups have been converted to alcohol groups, it only dissolves in water having a temperature greater than 60°C. In case, a sufficient number of acetate groups are allowed to remain, i.e., PVOH only being partially hydrolyzed, then it already dissolves at lower temperatures. Hence, partially hydrolyzed PVOH is particularly preferred. Although, both fully and partially hydrolyzed PVOH types are commonly referred to as PVOH homopolymers, the partially hydrolyzed type is technically a vinyl alcohol vinyl acetate copolymer.

The PVOH may comprise a partially or fully hydrolyzed PVOH copolymer that comprises an anionic monomer unit, a vinyl alcohol monomer unit, and optionally a vinyl acetate monomer unit. In various embodiments, the anionic monomer unit can be selected from the group consisting of vinyl acetic acid, alkyl acrylates, maleic acid, monoalkyl maleate, dialkyl maleate, monomethyl maleate, dimethyl maleate, maleic anhydride, fumaric acid, monoalkyl fumarate, dialkyl fumarate, monomethyl fumarate, dimethyl fumarate, itaconic acid, monomethyl itaconate, dimethyl itaconate, itaconic anhydride, citraconic acid, monoalkyl citraconate, dialkyl citraconate, citraconic anhydride, mesaconic acid, monoalkyl mesaconate, dialkyl mesaconate, glutaconic acid, monoalkyl glutaconate, dialkyl glutaconate, glutaconic anhydride, vinyl sulfonic acid, alkyl sulfonic acid, ethylene sulfonic acid, 2-acryl amido-1 -methyl propane sulfonic acid, 2-acryl amide-2-methyl propane sulfonic acid, 2-methyl acryl amido-2-methyl propane sulfonic 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, ethyl, or other C1-4 or Ce alkyl esters), and mixtures thereof. For example, the anionic monomer may comprise one or more of monomethyl maleate and alkali metal salts thereof (e.g., sodium salts).

Preferred polyvinyl alcohol copolymers comprise, in addition to vinyl alcohol, an ethylenically unsaturated carboxylic acid, its salt or its ester. In addition to vinyl alcohol, such polyvinyl alcohol copolymers particularly preferably contain sulfonic acids such as 2-acrylamido-2-methyl-1 - propanesulfonic acid (AMPS), acrylic acid, methacrylic acid, acrylic acid esters, methacrylic acid esters or mixtures thereof. Among the esters, Ci-4-alkyl esters or hydroxyalkyl esters are preferred. Other suitable monomers are ethylenically unsaturated dicarboxylic acids, e.g., itaconic acid, maleic acid, fumaric acid and mixtures thereof. Particular preferred derivatives of PVOH are those selected from copolymers of polyvinyl alcohol with a monomer, in particular selected from the group of monoalkyl maleates (in particular monomethyl maleate), dialkyl maleates (in particular dimethyl maleate), maleic anhydride, and combinations thereof, and the alkali metal salts or esters of the above-mentioned monomers.

The manufacture of water-soluble films for forming receiving chambers for liquids poses a unique concern, as they must be free of bubbles and pin holes, and capable of resisting problems such as physical incompatibility exemplified by "weeping" - a condition whereby the liquid seep from the film over a prolonged storage period - caused by certain components typically used in liquid detergent products. Conversely, powdered products are far more forgiving when it comes to packaging. Pin holes and micro bubbles in the film do not present problems for wrapping powdered products. Physical compatibility is less problematic, due in part to the non-existence of migrating materials in powdered detergents. Finally, weeping and early film decomposition do not commonly occur with the packaging of powdered products. For these reasons the type and quality of water-soluble films used to package powered products can be significantly varied from that for the liquid products.

Suitable water-soluble films comprising such polymers for use in producing washing or cleaning agent portion units are sold by MonoSol LLC, e.g., under the names M8630, M8720, M8310, C8400 or M8900. Other suitable films include films named Solublon® PT, Solublon® GA, Solublon® KC or Solublon® KL from Aicello Chemical Europe GmbH or the films from Mitsubishi Chemicals Group. The water-soluble films according to the invention comprise at least one PVOH (co-)polymer, wherein the at least one PVOH (co-)polymer is selected from the group consisting of polyvinyl alcohol homopolymer, polyvinyl alcohol copolymer or a blend thereof.

In preferred embodiments, the water-soluble films according to the invention may comprise at least one PVOH (co-)polymer, wherein the at least one PVOH (co-)polymer is selected from

(i) a vinyl alcohol vinyl acetate copolymer; and/or

(ii) a vinyl alcohol maleate copolymer, wherein the vinyl alcohol maleate copolymer comprises a maleate monomer unit derived from the group consisting of maleic acid, monoalkyl maleate, dialkyl maleate, maleic anhydride, and a mixture thereof; and/or

(iii) a sulfonated polyvinyl alcohol copolymer; and/or

(iv) a carboxylated polyvinyl alcohol copolymer, wherein the carboxylated polyvinyl alcohol copolymer comprises a carboxylate monomer unit derived from the group consisting of acrylate, methacrylate, maleate, and a mixture thereof; and/or

(vi) mixtures thereof.

In preferred embodiments, the water-soluble films according to the invention may comprise at least one PVOH (co-)polymer, wherein the at least one PVOH (co-)polymer is selected from a vinyl alcohol vinyl acetate copolymer.

In preferred embodiments, the water-soluble films according to the invention may comprise at least one PVOH (co-)polymer, wherein the at least one PVOH (co-)polymer is selected from a vinyl alcohol maleate copolymer, wherein the vinyl alcohol maleate copolymer comprises a maleate monomer unit derived from the group consisting of maleic acid, monoalkyl maleate, dialkyl maleate, maleic anhydride, and a mixture thereof.

In preferred embodiments, the water-soluble films according to the invention may comprise at least one PVOH (co-)polymer, wherein the at least one PVOH (co-)polymer is selected from a sulfonated polyvinyl alcohol copolymer.

In preferred embodiments, the water-soluble films according to the invention may comprise at least one PVOH (co-)polymer, wherein the at least one PVOH (co-)polymer is selected from a carboxylated polyvinyl alcohol copolymer, wherein the carboxylated polyvinyl alcohol copolymer comprises a carboxylate monomer unit derived from the group consisting of acrylate, methacrylate, maleate, and a mixture thereof.

In preferred embodiments, the water-soluble films according to the invention may comprise at least one PVOH (co-)polymer, wherein the at least one PVOH (co-)polymer is selected from a PVOH (co-)polymer comprising an anionic monomer unit, wherein the anionic monomer is selected from the group consisting of vinyl acetic acid, alkyl acrylates, maleic acid, monoalkyl maleate, dialkyl maleate, monomethyl maleate, dimethyl maleate, maleic anhydride, fumaric acid, monoalkyl fumarate, dialkyl fumarate, monomethyl fumarate, dimethyl fumarate, itaconic acid, monomethyl itaconate, dimethyl itaconate, itaconic anhydride, citraconic acid, monoalkyl citraconate, dialkyl citraconate, citraconic anhydride, mesaconic acid, monoalkyl mesaconate, dialkyl mesaconate, glutaconic acid, monoalkyl glutaconate, dialkyl glutaconate, glutaconic anhydride, vinyl sulfonic acid, alkyl sulfonic acid, ethylene sulfonic acid, 2-acryl amido-1 -methyl propane sulfonic acid, 2-acryl amide-2-methyl propane sulfonic acid, 2-methyl acryl amido-2-methyl propane sulfonic acid, 2-sulfoethyl acrylate, alkali metal salts of the foregoing, esters of the foregoing, and mixtures thereof.

Biopolymers

The term "biopolymer(s)" or "bio-derived polymer(s)" as used herein refers to polymers derived from natural sources, in particular from natural sources like animals, plants, algae, insects, Crustacea, fungi or microorganisms. The term "polymer" in the context of the present invention refers to long chain organic molecules comprising repeating monomers. Biopolymers in the context of the present invention are biodegradable or compostable. "Biodegradable" in the context of the present invention means that the biodegradable polymer (i.e., biopolymer) is degraded in vivo and in vitro either into products that are normal molecules in the environment or into products that can be completely eliminated from the environment with or without further metabolic transformations, wherein the degradation products are nontoxic for environment and human health. Although the biopolymer industry is growing, up to now there are no biopolymer-based films available which have adequate mechanical properties for being processed to form water-soluble washing or cleaning agent portion units showing the required handling and safety requirements. For example, PLA (poly lactic acid)- based films are commercially available, however so far only suitable for use in packaging of food but not for use in wrapping (flowable) washing or cleaning compositions, or PHA (poly hydroxyalkanolate)- based films, polyesters derived from bacteria, are available for use as agricultural mulch films but not for use in wrapping (flowable) washing or cleaning compositions. Films comprising starch and/or cellulose have been described to have good wet hand moisture resistance but need to be rather thin to achieve good cold-water solubility, however in such case, its mechanical properties, including those relating to processability, are compromised and they are not nearly as readily processable given their relative lack of mechanical stretchability or elongation as compared to films of like thickness comprising polyvinyl alcohol polymers. Films comprising casein have been described to have good transparency and good biodegradability but being rather sticky. A good overview on biopolymers might be found in Plackett (ed.), Biopolymers - New Materials for Sustainable Films and Coatings, John Wiley and Sons Ltd., 2011 , or Thomas et al. (ed.), Handbook of Biopolymer-Based Materials, From Blends and Composites to Gels and Complex Networks, Wiley-VCH, 2013.

The water-soluble films according to the invention comprise at least one biopolymer.

The water-soluble films according to the invention comprise at least one biopolymer, wherein the biopolymer is derived from natural sources like animals, plants, algae, insects, Crustacea, fungi or microorganisms.

The water-soluble films according to the invention comprise at least one biopolymer, wherein the biopolymer is selected from the group consisting of polysaccharides, peptides, proteins, glycoproteins, proteoglycans, poly(amino acids), derivatives of the foregoing, and mixtures thereof.

The water-soluble films according to the invention comprise at least one biopolymer, wherein the biopolymer is derived from natural sources like animals, plants, algae, insects, Crustacea, fungi or microorganisms, and wherein the biopolymer is selected from the group consisting of polysaccharides, peptides, proteins, glycoproteins, proteoglycans, poly(amino acids), derivatives of the foregoing, and mixtures thereof.

Polysaccharides are comprised of monosaccharides linked by glycosidic bonds, wherein the monomers (i.e., monosaccharides) may be the same or different. Typical monosaccharides comprise, e.g., glucose, fructose, galactose, mannose, ribose, desoxyribose, xylose, rhamnose. The polysaccharide also may be comprised of alternating linked disaccharides (e.g., saccharose, lactose, maltose). For example, cellulose is an unbranched polysaccharide comprised of glucose-units linked by p-1 ,4-glycosidic bonds, glycogen is a highly branched polysaccharide comprised of glucose-units linked by a-1 ,4-glycosidic bonds and comprising branched chains linked by a-1 ,6-glycosidic bonds every approx. 10 glucose units, starch is a polysaccharide comprised of glucose units, wherein amylose is the unbranched form having a-1 ,4-glycosidic bonds and wherein amylopectin is the branched form comprising branched chains linked by a-1 ,6-glycosidic bonds every approx. 30 glucose units, agar is a polysaccharide comprised of galactose units with some sparse sulfate groups, xanthan is a branched polysaccharide comprised of a backbone of glucose units linked by p-D-(1 ,4)-glycosidic bonds and side chains comprising mannose, glucuronic acid, and ketalized pyruvic acid, pectins are a family of polysaccharides which are comprised of partially methyl esterified galacturonic acid chains, gum arabic is a highly branched polysaccharide comprised of different monosaccharides like galactose, arabinose as well as glucuronic acid derived from glucose. Suitable polysaccharides comprise glucans which are dericed from D-glucose, linked by glycosidic bonds, wherein two forms are available, i.e., a-glucans and p-glucans. Glucans comprise, e.g., dextran (a-1 ,6-glucans with a-

1 .3-branches), floridean starch (a-1 ,4- and a-1 ,6-glucan), glycogen (a-1 ,4- and a-1 ,6-glucan), pullulan (a-1 ,4- and a-1 ,6-glucan), starch (mixture of amylose and amylopectin, both being a-1 ,4- and a-1 ,6- glucans), cellulose (p-1 ,4-glucan), chrysolaminarin (p-1 ,3-glucan), curdlan (p-1 ,3-glucan), laminarin (p-

1 .3- and p-1 ,6-glucan), lentinan (strictly purified p-1 ,6:p-1 ,3-glucan from Lentinus edodes), lichenin (p- 1 ,3- and p-1 ,4-glucan), oat p-glucan (p-1 ,3- and p-1 ,4-glucan), pleuran (p-1 ,3- and p-1 ,6-glucan isolated from Pleurotus ostreatus), and zymosan (p-1 ,3-glucan).

Polysaccharides suitable to be used in water-soluble films according to the invention can be derived from natural sources like animals, plants, algae, insects, Crustacea, fungi or microorganisms and may be selected from the group consisting of galactomannans, xyloglucans, galactoglucomannans, starches (e.g., amylose and amylopectin), glucans, p-glucans, pectins (e.g., protopectin, pectin polysaccharides, arabinans, galactans, and arabinogalactans), a1-4-glucan, a-1 ,6- glucan, glucomannans, celluloses, hemicelluloses, gum arabic, gum tragacanth, karaya gum, carrageenans, alginates, alginic acid (heteropolysaccharide comprised of D-mannuronic acid and L- guluronic acid), agar, agarose, furcellaran, chitin, chitosan, hyaluron, xanthan, gellan, dextran, curdlan, scleroglucan, schizophyllan, dextrins, cyclodextrins, glycogen, hydroxypropyl starch phosphate (HSP), hyaluronic acid, glycosaminoglycans, pullulan, gelatin, chrysolaminarin, laminarin, lentinan, lichenin, pleuran, zymosan, derivatives of the foregoing, and mixtures thereof.

Cellulose derivatives suitable to be used in water-soluble films according to the invention may be selected from the group consisting of carboxy methyl cellulose (CMC), hydroxyethyl cellulose (HEC), hydroxypropyl cellulose (HPC), hydroxypropyl methyl cellulose (HPMC), methyl cellulose (MC), ethyl cellulose (EC), derivatives of the foregoing, and mixtures thereof.

Carrageenans are linear sulphated polysaccharides with high molecular weights consisting of alternating a-(1 ,3)- and p-(1 ,4)-linked galactose and 3,6-anhydrogalactose units. Several types of carrageenans with different structures, properties and various contents of ester sulphate exist, depending on the type of monomer and glycosidic bond.

A "peptide" in the context of the present invention is to be understood as a polymer composed of amino acids, preferably the 20 proteinogenic L-amino acids, preferably of linear structure, which has up to 100 amino acids which are linked to one another via peptide bonds. In this context, the term "polypeptide" or "protein" refers in particular to peptides comprising 100 or more amino acids. Peptides, proteins and other amino acid-derived polymers are easily degradable via enzymatic processes.

Peptides and proteins suitable to be used in water-soluble films according to the invention can be derived from natural sources like animals (e.g., milk, rennet, meat, egg, gelatin), plants (e.g., soy, pea, wheat (gluten), potato), algae, insects, Crustacea, fungi (hydrophobins) or microorganisms and may be selected from the group consisting of wheat proteins, soy proteins, pea proteins, caseins, aS1-, aS2-, p- and K-casein, caseinates, whey proteins, b-lactoglobulin, a-lactalbumin, serum albumin, immunoglobulin, casein macropeptides, elastins, fibrins, derivatives of the foregoing, and mixtures thereof.

Caseins are natural occurring macromolecules comprised of amino acids linked by peptide bonds. The family of caseins comprise four main types of caseins, which differ in amino acid distribution and their supramolecular organization: aS1-, aS2-, p- and K-casein. Caseinate is to be understood as the salt form of casein, wherein the counterion is selected from the group consisting of alkali metal ions or earth alkali metal ions or ammonium, preferably selected from calcium, potassium, ammonium, sodium and magnesium, or mixtures thereof. Typically, caseinate has a rather low solubility in water, and is obtained by precipitation with acid addition from milk or rennet. Typical caseinate mixtures also comprise some kind of casein impurities. Caseins resp. caseinates are natural components of milk from, e.g., cows, goats and sheeps.

Glycoproteins are glycoslated proteins, wherein the mono-, di-, oligo- or polysaccharides are linked to a peptide or protein by N-glycosidic bonds (via amid group of side chain of protein/peptide) or O-glycosidic bonds (via oxygen atom of amino acid side chain of protein/peptide).

Proteoglycans are comprised of carbohydrates and peptides or proteins, in particular they are proteins comprising glycosaminoglycans, wherein the weight proportion of glycosaminoglycan in such molecules might be up to 95%, and wherein the glycosaminoglycans are carbohydrates comprising at least one amino group, the carbohydrate being selected from any mono-, di-, oligo- or polysaccharides. Typical proteoglycans can be found in animals, e.g., collagens, aggrecans, chitins, chondroitin sulphate, keratan sulphate, heparin, dermatan sulphate and hyaluronate (hyaluronic acid).

Poly(amino acids) in the context of the invention means a polymer comprised of mainly one type of amino acid, such as cyanophycin, poly(a-L-lysin), poly(y-glutamic acid).

The water-soluble films according to the invention comprise at least one biopolymer, wherein the biopolymer is selected from the group consisting of galactomannans, xyloglucans, galactoglucomannans, starches, amylose and amylopectin, glucans, p-glucans, pectins, protopectin, pectin polysaccharides, arabinans, galactans, and arabinogalactans, a-glucans, a1-4-glucans, a-1 ,6- glucans, glucomannans, celluloses, carboxy methyl cellulose (CMC), hydroxyethyl cellulose (HEC), hydroxypropyl cellulose (HPC), hydroxypropyl methyl cellulose (HPMC), methyl cellulose (MC), ethyl cellulose (EC), hemicelluloses, gum arabic, gum tragacanth, karaya gum, carrageenans, alginates, alginic acid (heteropolysaccharide comprised of D-mannuronic acid and L-guluronic acid), agar, agarose, furcellaran, chitin, chitosan, hyaluron, xanthan, gellan, dextran, curdlan, scleroglucan, schizophyllan, dextrins, cyclodextrins, glycogen, hydroxypropyl starch phosphate (HSP), hyaluronic acid, glycosaminoglycans, pullulan, gelatin, chrysolaminarin, laminarin, lentinan, lichenin, pleuran, zymosan, wheat proteins, soy proteins, pea proteins, potato proteins, whey proteins, corn proteins, caseins, aS1-, aS2-, p- and K-casein, caseinates, bovine casein salts, goat casein salts, sheep casein salts, p-lactoglobulin, a-lactalbumin, serum albumin, immunoglobulin, casein macropeptides, elastins, fibrins, collagens, aggrecans, chitins, chondroitin sulphate, keratan sulphate, heparin, dermatan sulphate and hyaluronate (hyaluronic acid), cyanophycin, poly(a-L-lysin), poly(y-glutamic acid), derivatives of the foregoing, and mixtures thereof.

The water-soluble films according to the invention comprise at least one biopolymer, wherein the biopolymer is derived from natural sources like animals, plants, algae, insects, Crustacea, fungi or microorganisms and selected from the group consisting of galactomannans, xyloglucans, galactoglucomannans, starches, amylose and amylopectin, glucans, p-glucans, pectins, protopectin, pectin polysaccharides, arabinans, galactans, and arabinogalactans, a-glucans, a1-4-glucans, a-1 ,6- glucans, glucomannans, celluloses, carboxy methyl cellulose (CMC), hydroxyethyl cellulose (HEC), hydroxypropyl cellulose (HPC), hydroxypropyl methyl cellulose (HPMC), methyl cellulose (MC), ethyl cellulose (EC), hemicelluloses, gum arabic, gum tragacanth, karaya gum, carrageenans, alginates, alginic acid (heteropolysaccharide comprised of D-mannuronic acid and L-guluronic acid), agar, agarose, furcellaran, chitin, chitosan, hyaluron, xanthan, gellan, dextran, curdlan, scleroglucan, schizophyllan, dextrins, cyclodextrins, glycogen, hydroxypropyl starch phosphate (HSP), hyaluronic acid, glycosaminoglycans, pullulan, gelatin, chrysolaminarin, laminarin, lentinan, lichenin, pleuran, zymosan, wheat proteins, soy proteins, pea proteins, potato proteins, whey proteins, corn proteins, caseins, aS1-, aS2-, p- and K-casein, caseinates, bovine casein salts, goat casein salts, sheep casein salts, p-lactoglobulin, a-lactalbumin, serum albumin, immunoglobulin, casein macropeptides, elastins, fibrins, collagens, aggrecans, chitins, chondroitin sulphate, keratan sulphate, heparin, dermatan sulphate and hyaluronate (hyaluronic acid), cyanophycin, poly(a-L-lysin), poly(y-glutamic acid), derivatives of the foregoing, and mixtures thereof.

In preferred embodiments, the water-soluble films according to the invention comprise at least one biopolymer, wherein

(iii) the at least one biopolymer is selected from the group consisting of galactomannans, xyloglucans, galactoglucomannans, starches, amylose and amylopectin, glucans, p-glucans, pectins, protopectin, pectin polysaccharides, arabinans, galactans, and arabinogalactans, a-glucans, a1-4- glucans, a-1 ,6-glucans, glucomannans, celluloses, carboxy methyl cellulose (CMC), hydroxyethyl cellulose (HEC), hydroxypropyl cellulose (HPC), hydroxypropyl methyl cellulose (HPMC), methyl cellulose (MC), ethyl cellulose (EC), hemicelluloses, gum arabic, gum tragacanth, karaya gum, carrageenans, alginates, alginic acid (heteropolysaccharide comprised of D-mannuronic acid and L- guluronic acid), agar, agarose, furcellaran, chitin, chitosan, hyaluron, xanthan, gellan, dextran, curdlan, scleroglucan, schizophyllan, dextrins, cyclodextrins, glycogen, hydroxypropyl starch phosphate (HSP), hyaluronic acid, glycosaminoglycans, pullulan, gelatin, chrysolaminarin, laminarin, lentinan, lichenin, pleuran, zymosan, wheat proteins, soy proteins, pea proteins, potato proteins, whey proteins, corn proteins, caseins, aS1-, aS2-, p- and K-casein, caseinates, bovine casein salts, goat casein salts, sheep casein salts, p-lactoglobulin, a-lactalbumin, serum albumin, immunoglobulin, casein macropeptides, elastins, fibrins, collagens, aggrecans, chitins, chondroitin sulphate, keratan sulphate, heparin, dermatan sulphate and hyaluronate (hyaluronic acid), cyanophycin, poly(a-L-lysin), poly(y-glutamic acid), derivatives of the foregoing, and mixtures thereof. In preferred embodiments, the water-soluble films according to the invention comprise at least one glucan (e.g., starch, a-glucan, p-glucan) (or derivatives thereof) and/or at least one milk protein (e.g., casein, caseinate, in particular bovine casein salts) (or derivatives thereof) and/or at least one plant protein (e.g., soy protein, pea protein, whey protein, corn protein, wheat protein, potato protein) (or derivatives thereof) and/or at least one carrageenan (or derivatives thereof).

In preferred embodiments, the water-soluble films according to the invention comprise at least one glucan or derivatives thereof.

In preferred embodiments, the water-soluble films according to the invention comprise at least one milk protein (e.g., casein or caseinate, in particular bovine casein salts, or derivatives thereof). In preferred embodiments, the water-soluble films according to the invention comprise at least on casein or derivatives thereof.

In preferred embodiments, the water-soluble films according to the invention comprise at least one carrageenan or derivatives thereof.

In preferred embodiments, the water-soluble films according to the invention comprise at least one plant protein or derivatives thereof. In preferred embodiments, the water-soluble films according to the invention comprise at least one plant protein or derivatives thereof, wherein the plant protein is selected from the group consisting of soy protein, pea protein, wheat protein, whey protein, corn protein, and potato protein.

In preferred embodiments, the water-soluble films according to the invention comprise at least one glucan or derivatives thereof and at least one casein or caseinate or derivatives thereof.

In preferred embodiments, the water-soluble films according to the invention comprise at least one glucan or derivatives thereof and at least one carrageenan or derivatives thereof.

In preferred embodiments, the water-soluble films according to the invention comprise at least one glucan or derivatives thereof and at least one plant protein or derivatives thereof. In preferred embodiments, the water-soluble films according to the invention comprise at least one glucan or derivatives thereof and at least one plant protein or derivatives thereof, wherein the plant protein is selected from the group consisting of soy protein, pea protein, wheat protein, whey protein, corn protein, and potato protein.

In preferred embodiments, the water-soluble films according to the invention comprise at least one casein or caseinate or derivatives thereof and at least one carrageenan or derivatives thereof.

In preferred embodiments, the water-soluble films according to the invention comprise at least one casein or caseinate or derivatives thereof and at least one plant protein or derivatives thereof. In preferred embodiments, the water-soluble films according to the invention comprise at least one casein or caseinate or derivatives thereof and at least one plant protein or derivatives thereof, wherein the plant protein is selected from the group consisting of soy protein, pea protein, wheat protein, whey protein, corn protein, and potato protein. In preferred embodiments, the water-soluble films according to the invention comprise at least one glucan or derivatives thereof and at least one casein or caseinate or derivatives thereof and at least one carrageenan or derivatives thereof.

In preferred embodiments, the water-soluble films according to the invention comprise at least one glucan or derivatives thereof and at least one casein or caseinate or derivatives thereof and at least one plant protein or derivatives thereof. In preferred embodiments, the water-soluble films according to the invention comprises at least one glucan or derivatives thereof and at least one casein or caseinate or derivatives thereof and at least one plant protein or derivatives thereof, wherein the plant protein is selected from the group consisting of soy protein, pea protein, wheat protein, whey protein, corn protein, and potato protein.

In preferred embodiments, the water-soluble films according to the invention comprise at least one glucan or derivatives thereof and at least one plant protein or derivatives thereof and at least one carrageenan or derivatives thereof. In preferred embodiments, the water-soluble films according to the invention comprise at least one glucan or derivatives thereof and at least one casein or caseinate or derivatives thereof and at least one plant protein or derivatives thereof, wherein the plant protein is selected from the group consisting of soy protein, pea protein, wheat protein, whey protein, corn protein, and potato protein.

In preferred embodiments, the water-soluble films according to the invention comprise at least one plant protein or derivatives thereof and at least one casein or caseinate or derivatives thereof and at least one carrageenan or derivatives thereof. In preferred embodiments, the water-soluble films according to the invention comprise at least one starch or derivatives thereof and at least one casein or derivatives thereof and at least one plant protein or derivatives thereof, wherein the plant protein is selected from the group consisting of soy protein, pea protein, wheat protein, whey protein, corn protein, and potato protein.

Alkyl polyqlycosides

Alkyl polyglycosides are known to be widely used as non-ionic surfactants in, e.g., detergents. Since they can be produced without use of petrochemical raw materials and/or without palm oil, they are considered ecofriendly. Moreover, they are fully biodegradable. They are derived from sugars and derivatives thereof, such as polyols, saccharic acids, amides, etc. In particular they are derived from sugars and fatty alcohols.

In various embodiments, the alkyl polyglycoside has the formula (I)

R⁵O-[G]_P (I), in which R⁵ represents a linear or branched alkyl or alkenyl having 4 to 24, preferably 5 to 20, more preferably 4 to 15, 7 to 18 or 5 to 15 C atoms, G represents a sugar residue having 5 or 6 C atoms and p represents numbers from 1 to 10. For example, the alkyl and alkenyl radical R⁵ can be derived from primary alcohols with 6 to 24 C atoms such as caproic alcohol, caprylic alcohol, capric alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, petroselinyl alcohol, arachidyl alcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol, brassidyl alcohol and technical mixtures thereof.

G represents residues of sugars having 5 (pentoses) or 6 (hexoses) C atoms, it being possible for the sugars to be ketoses or aldoses. Preferred monosaccharides include, but are not limited to, glucose, galactose, fructose, mannose or ribose, in particular glucose or xylose. In case, the alkyl polyglycoside is derived from pentose, it is also known as "alkyl pentoglycosid" (APP). In case, the alkyl polyglycoside is derived from glucose, it is also known as "alkyl polyglucoside" (APG). In addition to the monosaccharides, however, G can also represent sugar derivatives, in particular sugar alcohols, saccharic acids, amino sugars (glycosamines) or thiosugars. Sugar alcohols are obtained from the corresponding monosaccharide by reduction of the aldehyde or ketone function, e.g. sorbitol (glucitol) is obtained from glucose and mannitol is obtained from mannose. Saccharic acids are obtained from the corresponding monosaccharide by oxidation of the aldehyde function (aldonic acids) or of a terminal hydroxyl function (uronic acids) or both (aldaric acids), e.g., gluconic acid, glucuronic acid or glucaric acid is obtained from glucose. Amino sugars are obtained by substitution of a hydroxyl function by an amino function. A preferred example is glucosamine. Thiosugars are obtained by the substitution of a hydroxyl function by a thiol function. An example is thioglucose. It is self-evident that, even if the sugars and sugar derivatives are described as such above, these are found as sugar residues in the alkyl polyglycosides of the above-mentioned formula and the R⁵ functional group substitutes a hydrogen atom in the corresponding sugar or sugar derivative.

The index number p in the formula R⁵O-[G]_P indicates the degree of oligomerization (DP), i.e. the distribution of monoglycosides and oligoglycosides, and stands for a number between 1 and 10, it being possible for each G independently to represent a simple sugar. If p is 2 or more, the different G units are preferably bonded to one another by means of glycosidic bonds. It may be preferable for the R⁵ functional group to be bonded to a terminal sugar residue, but it may also be bonded to a nonterminal sugar unit in a corresponding oligomer.

While p in the individual molecule must always be an integer and, in particular, can have values of p = 1 to 6, the value p for a specific alkyl polyglycoside is an analytically determined arithmetic quantity, which is usually a fractional number. Preferred are alkyl polyglycosides with an average degree of oligomerization p of 1 .1 to 3. From the point of view of application technology, those alkyl polyglycosides are preferred whose degree of oligomerization is less than 1 .7 and in particular between 1 .2 and 1 .4.

If p = 2, the sugar residue is a disaccharide residue. For example, one G may be glucose and the second G may be fructose and thus form sucrose (a-D-glucopyranosyl-(1-2)-b-D-fructofuranoside). However, it is preferred for all G in one molecule to be the same simple sugar, e.g., glucose or xylose. Examples of suitable disaccharides are, without limitation, maltose (a-D-glucopyranosyl-(1-4)-a-D- glucopyranose), isomaltose (a-D-glucopyranosyl-(1-6)-a-D-glucopyranose) and lactose (b-D- galactopyranosyl-(1-4)-D-glucopyranose).

If p = 3, the sugar residue is a trisaccharide residue. Examples of suitable trisaccharides include, but are not limited to, raffinose, panose, and in particular maltotriose.

If p = 4, the sugar residue is a tetrasaccharide residue, particularly preferably is maltotetraose.

If p = 5 or more, the units are preferably glucose units, in particular those which are 1 ,4- glycosidically linked.

In all embodiments in which p is 2 or more, single, multiple or all sugar units can be substituted by the corresponding above-defined sugar derivatives. For example, aminoglycosides and thioglycosides in which the bond to the nearest unit is carried out via the nitrogen atom or the sulfur atom can be used.

Preferred are alkyl polyglucosides in which R⁵ stands for C10-16 alkyl radicals and which have a DP of 1 to 3. Particularly preferred are the alkyloligoglucosides known under the INCI names caprylyl/capryl glucoside, decyl glucosides and/or coco glucosides.

In preferred embodiments, the water-soluble films according to the invention comprise at least one alkyl polyglycoside which is described by the formula (II) in which R¹ and R² are same or different and independently selected from H or OH, R³ is selected from H or CH2OH, represents branched or unbranched alkyl or alkenyl group, n represents 4 to 18, in particular s to 15, e.g., n = 4, 5, 6, 7, 8, 9, 10, 11 , 12, 13, 14, 15, 16, 17 or 18, preferably n = 5, 6, 7, 8, 9, 10, 11 , 12, 13, 14 or 15, and p represents numbers from 1 to 10. The degree of oligomerization (DP) is preferably p < 8, more preferably p < 6, even more preferably p < 4 and in particular p < 2. Particularly preferred are alkyl polyglycosides in which p represents numbers from 1 .4 to 1 .8. These fractional degrees of oligomerization are achieved by mixtures which contain varying amounts of alkyl polyglycosides of the above formula, in which p represents an integer, preferably 1 , 2, 3 or 4, for the single molecule.

In preferred embodiments, the water-soluble films according to the invention comprise at least one alkyl polyglycoside which is derived from glucose and is described by the formula (III)

(HI), in which represents branched or unbranched alkyl or alkenyl group, n represents 7 to 18, preferably 10 to 15, e.g., n = 7, 8, 9, 10, 11 , 12, 13, 14, 15, 16, 17 or 18, preferably N = 10, 11 , 12, 13, 14 or 15, and p represents numbers from 1 to 10. Such alkyl polyglycosides are also known as alkyl polyglucosides (APG). The degree of oligomerization (DP) is preferably p < 8, more preferably p < 6, even more preferably p < 4 and in particular p < 2. Particularly preferred p represents numbers from 1 .4 to 1 .8. These fractional degrees of oligomerization are achieved by mixtures which contain varying amounts of alkyl polyglucosides of the above formula, in which p represents an integer, preferably 1 , 2, 3 or 4, for the single molecule.

In preferred embodiments, the water-soluble films according to the invention comprise at least one alkyl polyglycoside which is derived from xylose and is described by the formula (IV) in which represents branched or unbranched alkyl or alkenyl group, n represents 4 to 15, in particular s to 10, e.g., n = 4, 5, 6, 7, 8, 9, 10, 11 , 12, 13, 14 or 15, preferably n = 5, 6, 7, 8, 9 or 10, and p represents numbers from 1 to 10. The degree of oligomerization (DP) is preferably p < 8, more preferably p < 6, even more preferably p < 4 and in particular p < 2. Particularly preferred p represents numbers from 1 .4 to 1 .8. These fractional degrees of oligomerization are achieved by mixtures which contain varying amounts of alkyl polypentosides of the above formula, in which p represents an integer, preferably 1 , 2, 3 or 4, for the single molecule.

In preferred embodiments, the water-soluble films according to the invention comprise at least one alkyl polypentoside (APP) which is selected from formula (V) or formula (VI), wherein in formula (V) p = 1 and in formula (VI) p = 2.

Examples of particularly suitable alkyl polyglycosides include, without limitation, n-decyl- or n- dodecyl-p-D-maltoside; n-octyl-, 2-ethylhexyl-, n-decyl- or n-dodecyl-p-D-glucoside; n-octyl-, 2- ethylhexyl-, n-decyl- or n-dodecyl-a-D-glucoside; amyl xylosides; lauryl glucosides; myristyl glucosides; D-glucopyranose; (3S,5R)-2-(2,3-dirutherfordiobutoxy)-5-(hydroxymethyl)oxolane-3,4-diol; (3S,5R)-2-(2,3-dirutherfordiobutoxy)oxane-3,4,5-triol; D-xylofuranose oligomeric 3-methylbutyl glycosides (DP = 1); and D-xylofuranose oligomeric 3-methylbutyl glycosides (DP = 2).

In preferred embodiments, the water-soluble films according to the invention comprise at least one alkyl polyglycoside which is selected from Cs-16, in particular Cs-io or C12-16 alkyl poly-(1 ,4)- glucosides.

In preferred embodiments, the water-soluble films according to the invention comprise at least one alkyl polyglycoside which has a hydrophilic-lipophilic balance (HLB) value equal or greater than 10. In preferred embodiments, the water-soluble films according to the invention comprise at least one alkyl polyglycoside which has a HLB value between 10 and 20, e.g., HLB value of 10, 11 , 12, 13, 14, 15, 16, 17, 18, 19, 20. In preferred embodiments, the water-soluble films according to the invention comprise at least one alkyl polyglycoside which has a HLB value of equal or greater than 10, in particular equal or greater than 12, more preferably equal or greater than 15. In preferred embodiments, the water-soluble films according to the invention comprise at least one alkyl polyglycoside which has a HLB value of equal or greater than 10 and 20 or less, in particular equal or greater than 12 and 20 or less, more preferably equal or greater than 15 and 20 or less. The hydrophilic-lipophilic balance (HLB) of a molecule is a measure of its degree of hydrophilicity or lipophilicity, determined by calculating percentages of molecular weights for the hydrophilic and lipophilic portions of the molecule, as described by Griffin (1949), Classification of Surface-Active Agents by 'HLB', Journal of the Society of Cosmetic Chemists, 1 (5):311-326; Griffin (1954), Calculation of HLB Values of Non-lonic Surfactants, Journal of the Society of Cosmetic Chemists, 5(4):249-256).

Suitable alkyl polyglycosides are available, e.g., under the trade names Plantacare® or Plantaren® or Glucopon® from BASF SE, DE and include, i.a., Plantacare® 220 UP (APG 220 UP) and Plantaren® 1200 UP NP (APG 600 UP) or Glucopon® 425N, Glucopon® 215 UP or Glucopon® 600 UP, as well as under the trade name Appyclean™ from Wheatoleo, FR and include, i.a., Appyclean™ 6505 or Appyclean™ 6505C.

Optional further ingredients

The water-soluble films according to the invention may comprise additional active ingredients or fillers as well as plasticizers and/or solvents, in particular water, as well processing agents, comprising but not limited to plasticizers, lubricants, release agents, fillers, extenders, cross-linking agents, antiblocking agents, antioxidants, detackifying agents, antifoam and the like.

The group of additional active ingredients includes, e.g., materials that protect the ingredients enclosed by the film material from decomposition or deactivation light irradiation. Antioxidants, UV absorbers and fluorescent dyes have proven to be particularly suitable here.

Glycerol, ethylene glycol, diethylene glycol, propanediol, 2-methyl-1 ,3-propanediol, sorbitol or mixtures thereof, for example, can be used as plasticizers.

To reduce coefficient of friction, the surface of the water-soluble film can optionally be powder- coated with fine powder. Sodium aluminosilicate, silicon dioxide, silica, talc and amylose are examples of suitable powdering agents.

Water-soluble film

Water-soluble film according to the invention comprise, based on the total weight of the film composition,

(B) 2.5 to 30 wt.%, preferably, 5 to 25 wt.%, of at least one biopolymer,

R⁵O-[G]_P (I), in which R⁵ represents a linear or branched alkyl or alkenyl having 4 to 24, preferably 5 to 20, C atoms, G represents a sugar residue having 5 or 6 C atoms and p represents numbers from 1 to 10. The water-soluble films according to the invention comprise as a first essential ingredient at least one PVOH (co-)polymer, wherein the PVOH (co-)polymer is selected from the group consisting of PVOH polymers, PVOH co-polymers and mixtures thereof, as described herein.

The water-soluble films according to the invention comprise at least one PVOH (co-)polymer, the PVOH (co-)polymer being selected from the group consisting of PVOH polymers, PVOH co-polymers and mixtures thereof, as described herein, in an amount of 50 to 75 wt.%, preferably 60 to 70 wt.%, more preferably 65 to 68 wt.%, based on the total weight of the film composition.

The water-soluble films according to the invention comprise as a second essential ingredient at least one biopolymer, wherein the biopolymer is derived from natural sources like animals, plants, algae, insects, Crustacea, fungi or microorganisms; and/or wherein the biopolymer is selected from the group consisting of polysaccharides, peptides, proteins, glycoproteins, proteoglycans, poly(amino acids), derivatives of the foregoing, and mixtures thereof, as described herein.

The water-soluble films according to the invention comprise at least one biopolymer, the biopolymer being derived from natural sources like animals, plants, algae, insects, Crustacea, fungi or microorganisms; and/or the biopolymer being selected from the group consisting of polysaccharides, peptides, proteins, glycoproteins, proteoglycans, poly(amino acids), derivatives of the foregoing, and mixtures thereof, as described herein, in an amount of 2.5 to 30 wt.%, preferably 3 to 28 wt.%, more preferably 5 to 25 wt.%, based on the total weight of the film composition.

The water-soluble films according to the invention comprise at least one biopolymer, wherein the biopolymer is selected from the group consisting of starches, amylose and amylopectin, celluloses, carboxy methyl cellulose (CMC), hydroxyethyl cellulose (HEC), hydroxypropyl cellulose (HPC), hydroxypropyl methyl cellulose (HPMC), methyl cellulose (MC), ethyl cellulose (EC), glucans, p- glucans, a-glucans, wheat proteins, soy proteins, pea proteins, potato proteins, whey proteins, corn proteins, caseins, aS1-, aS2-, p- and K-casein, caseinates, bovine casein salts, goat casein salts, sheep casein salts, derivatives of the foregoing, and mixtures thereof, preferably starches, amylose and amylopectin, carrageenans, wheat proteins, soy proteins, pea proteins, potato proteins, whey proteins, corn proteins, caseins, aS1-, aS2-, p- and K-casein, caseinates, bovine casein salts, goat casein salts, sheep casein salts, derivatives of the foregoing, and mixtures thereof, as described herein.

The water-soluble films according to the invention comprise at least one biopolymer, wherein the biopolymer is selected from the group consisting of starches, amylose and amylopectin, celluloses, carboxy methyl cellulose (CMC), hydroxyethyl cellulose (HEC), hydroxypropyl cellulose (HPC), hydroxypropyl methyl cellulose (HPMC), methyl cellulose (MC), ethyl cellulose (EC), glucans, p- glucans, a-glucans, wheat proteins, soy proteins, pea proteins, potato proteins, whey proteins, corn proteins, caseins, aS1-, aS2-, p- and K-casein, caseinates, bovine casein salts, goat casein salts, sheep casein salts, derivatives of the foregoing, and mixtures thereof, preferably starches, amylose and amylopectin, carrageenans, wheat proteins, soy proteins, pea proteins, potato proteins, whey proteins, corn proteins, caseins, aS1-, aS2-, p- and K-casein, caseinates, bovine casein salts, goat casein salts, sheep casein salts, derivatives of the foregoing, and mixtures thereof, as described herein, in an amount of 2.5 to 30 wt.%, preferably 3 to 28 wt.%, more preferably 5 to 25 wt.%, based on the total weight of the film composition.

The water-soluble films according to the invention comprise at least one PVOH (co-)polymer, the PVOH (co-)polymer being selected from the group consisting of PVOH polymers, PVOH co-polymers and mixtures thereof, as described herein, in an amount of 50 to 75 wt.%, preferably 60 to 70 wt.%, more preferably 65 to 68 wt.%, based on the total weight of the film composition, and at least one biopolymer, the biopolymer being derived from natural sources like animals, plants, algae, insects, Crustacea, fungi or microorganisms; and/or the biopolymer being selected from the group consisting of polysaccharides, peptides, proteins, glycoproteins, proteoglycans, poly(amino acids), derivatives of the foregoing, and mixtures thereof, as described herein, in an amount of 2.5 to 30 wt.%, preferably 3 to 8 wt.%, more preferably 5 to 25 wt.%, based on the total weight of the film composition, wherein the total amount of polymer is 52.5 to 80 wt.%, preferably 60 to 75 wt.%, more preferably 68 to 73 wt.%, based on the total weight of the film composition.

The water-soluble films according to the invention comprise at least one PVOH (co-)polymer, the PVOH (co-)polymer being selected from the group consisting of PVOH polymers, PVOH co-polymers and mixtures thereof, as described herein, in an amount of 50 to 75 wt.%, preferably 60 to 70 wt.%, more preferably 65 to 68 wt.%, based on the total weight of the film composition, and at least one biopolymer, the biopolymer being selected from the group consisting of starches, amylose and amylopectin, celluloses, carboxy methyl cellulose (CMC), hydroxyethyl cellulose (HEC), hydroxypropyl cellulose (HPC), hydroxypropyl methyl cellulose (HPMC), methyl cellulose (MC), ethyl cellulose (EC), glucans, p-glucans, a-glucans, wheat proteins, soy proteins, pea proteins, potato proteins, whey proteins, corn proteins, caseins, aS1-, aS2-, p- and K-casein, caseinates, bovine casein salts, goat casein salts, sheep casein salts, derivatives of the foregoing, and mixtures thereof, preferably starches, amylose and amylopectin, carrageenans, wheat proteins, soy proteins, pea proteins, potato proteins, whey proteins, corn proteins, caseins, aS1-, aS2-, p- and K-casein, caseinates, bovine casein salts, goat casein salts, sheep casein salts, derivatives of the foregoing, and mixtures thereof, as described herein, in an amount of 2.5 to 30 wt.%, preferably 3 to 28 wt.%, more preferably 5 to 25 wt.%, based on the total weight of the film composition, wherein the total amount of polymer is 52.5 to 80 wt.%, preferably 60 to 75 wt.%, more preferably 68 to 73 wt.%, based on the total weight of the film composition.

The water-soluble films according to the invention comprise at least one PVOH (co-)polymer, the PVOH (co-)polymer being selected from the group consisting of PVOH polymers, PVOH co-polymers and mixtures thereof, as described herein, in an amount of 50 to 75 wt.%, preferably 60 to 70 wt.%, more preferably 65 to 68 wt.%, based on the total weight of the film composition, and at least one biopolymer, the biopolymer being derived from natural sources like animals, plants, algae, insects, Crustacea, fungi or microorganisms; and/or the biopolymer being selected from the group consisting of polysaccharides, peptides, proteins, glycoproteins, proteoglycans, poly(amino acids), derivatives of the foregoing, and mixtures thereof, as described herein, in an amount of 2.5 to 30 wt.%, preferably 3 to 28 wt.%, more preferably 5 to 25 wt.%, based on the total weight of the film composition, wherein the ratio of the at least on PVOH (co-)polymerto the at least one biopolymer is between 20:1 and 1 :20, preferably between 15:1 to 5:1 , more preferably between 15:1 and 10:1 , e.g., 20:1 , 19.5:1 , 19:1 , 18.5:1, 18:1, 17.5:1, 17:1, 16.5:1, 16:1, 15.5:1, 15:1, 14.5:1, 14:1, 13.5:1, 13:1, 12.5:1, 12:1, 11.5:1, 11:1, 10.5:1, 10:1, 9.5:1, 9:1, 8.5:1, 8:1, 7.5:1, 7:1, 6.5:1, 6:1, 5.5:1, 5:1, 4.5:1, 4:1, 3.5:1, 3:1, 2.5:1, 2:1, 1.5:1, 1:1, 1:1.5, 1:2, 1:2.5, 1:3, 1:3.5, 1:4, 1:4.5, 1:5, 1:5.5, 1:6, 1:6.5, 1:7, 1:7.5, 1:8, 1:8.5, 1:9, 1:9.5, 1:10, 1:10.5, 1:11, 1:11.5, 1:12, 1:12.5, 1:13, 1:13.5, 1:14, 1:14.5, 1:15, 1:15.5., 1:16, 1:16.5, 1:17, 1:17.5, 1:18, 1:18.5, 1:19, 1:19.5, 1:20.

The water-soluble films according to the invention comprise at least one PVOH (co-)polymer, the PVOH (co-)polymer being selected from the group consisting of PVOH polymers, PVOH co-polymers and mixtures thereof, as described herein, in an amount of 50 to 75 wt.%, preferably 60 to 70 wt.%, more preferably 65 to 68 wt.%, based on the total weight of the film composition, and at least one biopolymer, the biopolymer being derived from natural sources like animals, plants, algae, insects, Crustacea, fungi or microorganisms; and/or the biopolymer being selected from the group consisting of polysaccharides, peptides, proteins, glycoproteins, proteoglycans, poly(amino acids), derivatives of the foregoing, and mixtures thereof, as described herein, in an amount of 2.5 to 30 wt.%, preferably 3 to 28 wt.%, more preferably 5 to 25 wt.%, based on the total weight of the film composition, wherein the total amount of polymer is 52.5 to 80 wt.%, preferably 60 to 75 wt.%, more preferably 68 to 73 wt.%, based on the total weight of the film composition, and wherein the ratio of the at least on PVOH (co-)polymer to the at least one biopolymer is between 20:1 and 1 :20, preferably between 15:1 to 5:1 , more preferably between 15:1 and 10:1, e.g., 20:1, 19.5:1, 19:1, 18.5:1, 18:1, 17.5:1, 17:1, 16.5:1, 16:1, 15.5:1, 15:1, 14.5:1, 14:1, 13.5:1, 13:1, 12.5:1, 12:1, 11.5:1, 11:1, 10.5:1, 10:1 , 9.5:1 , 9:1 , 8.5:1 , 8:1, 7.5:1, 7:1, 6.5:1, 6:1, 5.5:1, 5:1, 4.5:1, 4:1, 3.5:1, 3:1, 2.5:1, 2:1, 1.5:1, 1:1, 1:1.5, 1:2, 1:2.5, 1:3, 1:3.5, 1:4, 1:4.5, 1:5, 1:5.5, 1:6, 1:6.5, 1:7, 1:7.5, 1:8, 1:8.5, 1:9, 1:9.5, 1:10, 1:10.5, 1:11, 1:11.5, 1:12, 1:12.5, 1:13, 1:13.5, 1:14, 1:14.5, 1:15, 1:15.5., 1:16, 1:16.5, 1:17, 1:17.5, 1:18, 1:18.5, 1:19, 1:19.5, 1:20.

The water-soluble films according to the invention comprise at least one PVOH (co-)polymer, the PVOH (co-)polymer being selected from the group consisting of PVOH polymers, PVOH co-polymers and mixtures thereof, as described herein, in an amount of 50 to 75 wt.%, preferably 60 to 70 wt.%, more preferably 65 to 68 wt.%, based on the total weight of the film composition, and at least one biopolymer, the biopolymer being selected from the group consisting of starches, amylose and amylopectin, celluloses, carboxy methyl cellulose (CMC), hydroxyethyl cellulose (HEC), hydroxypropyl cellulose (HPC), hydroxypropyl methyl cellulose (HPMC), methyl cellulose (MC), ethyl cellulose (EC), glucans, p-glucans, a-glucans, wheat proteins, soy proteins, pea proteins, potato proteins, whey proteins, corn proteins, caseins, aS1-, aS2-, p- and K-casein, caseinates, bovine casein salts, goat casein salts, sheep casein salts, derivatives of the foregoing, and mixtures thereof, preferably starches, amylose and amylopectin, carrageenans, wheat proteins, soy proteins, pea proteins, potato proteins, whey proteins, corn proteins, caseins, aS1-, aS2-, p- and K-casein, caseinates, bovine casein salts, goat casein salts, sheep casein salts, derivatives of the foregoing, and mixtures thereof, as described herein, in an amount of 2.5 to 30 wt.%, preferably 3 to 28 wt.%, more preferably 5 to 25 wt.%, based on the total weight of the film composition, wherein the ratio of the at least on PVOH (copolymer to the at least one biopolymer is between 20:1 and 1 :20, preferably between 15:1 to 5:1 , more preferably between 15:1 and 10:1, e.g., 20:1, 19.5:1, 19:1, 18.5:1, 18:1, 17.5:1, 17:1, 16.5:1, 16:1, 15.5:1, 15:1, 14.5:1, 14:1, 13.5:1, 13:1, 12.5:1, 12:1, 11.5:1, 11:1, 10.5:1, 10:1 , 9.5:1 , 9:1 , 8.5:1 , 8:1, 7.5:1, 7:1, 6.5:1, 6:1, 5.5:1, 5:1, 4.5:1, 4:1, 3.5:1, 3:1, 2.5:1, 2:1, 1.5:1, 1:1, 1:1.5, 1:2, 1:2.5, 1:3, 1:3.5, 1:4, 1:4.5, 1:5, 1:5.5, 1:6, 1:6.5, 1:7, 1:7.5, 1:8, 1:8.5, 1:9, 1:9.5, 1:10, 1:10.5, 1:11, 1:11.5, 1:12, 1:12.5, 1:13, 1:13.5, 1:14, 1:14.5, 1:15, 1:15.5., 1:16, 1:16.5, 1:17, 1:17.5, 1:18, 1:18.5, 1:19, 1:19.5, 1:20.

The water-soluble films according to the invention comprise as a third essential ingredient at least one alkyl polyglycoside, wherein the alkyl polyglycoside is selected from the group consisting of alkyl polyglucosides (APG), alkyl polypentosides (APP) and mixtures thereof, as described herein.

The water-soluble films according to the invention comprise at least one alkyl polyglycoside, the alkyl polyglycoside being selected from the group consisting of alkyl polyglucosides (APG), alkyl polypentosides (APP) and mixtures thereof, as described herein, in an amount of 0.2 to 15 wt.%, preferably 0.5 to 10 wt.%, more preferably 1 to 6 wt.%, based on the total weight of the film composition.

The water-soluble films according to the invention may comprise at least one further ingredient, wherein the at least one further ingredient is selected from the group consisting of bittering agents, solvents, in particular water, as well processing agents, in particular plasticizers, lubricants, release agents, fillers, extenders, cross-linking agents, antiblocking agents, antioxidants, detackifying agents, and antifoam.

The water-soluble films according to the invention may comprise at least one further ingredient, in particular auxiliary agents and processing agents, as described herein. The amount of such agents might be up to 30 wt.%, e.g., up to 29 wt.%, 28 wt.%, 27 wt.%, 26 wt.%, 25 wt.%, 24 wt.%, 23 wt.%, 22 wt.%, 21 wt.%, 20 wt.%, individually or collectively, based on the total weight of the film composition.

The water-soluble films according to the invention may comprise 10 to 30 wt.%, preferably 12 to 25 wt.%, more preferably 12 to 20 wt.%, of water, based on the total weight of the film composition.

The water-soluble films according to the invention are soluble or dispersible in water.

The water-soluble films according to the invention have a thickness of 5 to 200 pm, preferably 20 pm to 150 pm, or 35 pm to 125 pm, or 50 pm to 110 pm, more preferably 30 to 100 pm, even more preferably 50 to 95 pm, most preferably 60 to 90 pm, e.g., 60 pm, 61 pm, 62 pm, 63 pm, 64 pm, 65 pm, 66 pm, 67 pm, 68 pm, 69 pm, 70 pm, 71 pm, 72 pm, 73 pm, 74 pm, 75 pm, 76 pm, 77 pm, 78 pm, 79 pm, 80 pm, 81 pm, 82 pm, 83 pm, 84 pm, 85 pm, 86 pm, 87 pm, 88 pm, 89 pm, or 90 pm. The water-soluble films according to the invention, at a thickness of approx. 80 pm dissolve in 60 seconds or less in water at a temperature of 20°C in accordance with Test Method as described in Example 3.4.

While good water-solubility is advantageous for use of the washing or cleaning agent portion units in washing or cleaning processes, for safety reasons immediate release of the washing or cleaning composition contained in the portion unit has to be prevented, e.g., in case a child places such portion unit into the mouth. Hence, according to safety regulations the water-soluble film has to retain its content for at last 30 seconds when the water-soluble washing or cleaning portion unit is placed in water at 20°C (liquid release time).

In preferred embodiments, the water-soluble films according to the invention have a liquid release time of more than 30 s but less than 180 s, as determined by Test Method described in Example 3.7.

Without wishing to be bound by theory, it is believed that the inventive combination of PVOH, biopolymer and alkyl polyglycosides lead to improved mechanical properties with respect to processability and/or improving compatibility of PVOH and biopolymers and/or enabling reducing PVOH content in the film and/or improved stretchability.

Without wishing to be bound by theory, it is believed that using alkyl polyglycosides, in particular alkyl polyglucoside (APG) and/or alkyl polypentosides (APP), bring a unique set of properties, which are beneficial for the water-soluble film formulations, since they act as hydrotropes and have surfactant properties. Since they are liquid at room temperature, have good water-solubility and show only low foaming in film formulations (no air bubble formation during film casting), they are easy to handle. They are not only highly water-soluble, plant-based and biodegradable. Without wishing to be bound by theory it is believed that, since they act as “high-molecular” weight plasticizers which will remain in the water-soluble film after casting and particular after contact with liquid laundry formulations, they will not leach out, and hence, the resulting detergent filled capsules will maintain their chemical and mechanical properties even during storage. Further without wishing to be bound by theory, it is believed that alkyl polyglycosides, in particular alkyl polyglucoside (APG) and/or alkyl polypentosides (APP), might even reduce stress in the film after thermoforming, which might result in better flexibility of the film once the equilibrium of the constituents is reached after forming and filling the capsules.

Method for producing water-soluble films

Methods for producing such water-soluble films are known in the art and include, e.g., mixing the ingredients and casting of the film composition to form a film, in particular as described in Example 1 , or e.g., in WO 2004/074351 .

Methods for producing water-soluble films according to the invention comprise the steps of a) providing a PVOH slurry, wherein the PVOH solution comprises at least one PVOH (co-)polymer and wherein the PVOH (co-)polymer is selected from at least one polyvinyl alcohol homopolymer, at least one polyvinyl alcohol copolymer or a mixture thereof, b) adding additives as required, in particular adding at least one biopolymer, as described herein, and/or at least one alkyl polyglycoside, preferably selected from alkyl polyglucosides (APG), alkyl polypentosides (APP) and mixtures thereof, and/or further ingredients, as described herein, c) heating the slurry to form a solution, and d) casting the solution of step c) on a suitable surface to create a film having a thickness in the range of 5 to 200 pm, preferably 20 pm to 150 pm, or 35 pm to 125 pm, or 50 pm to 110 pm, more preferably 70 to 100 pm, even more preferably 50 to 95 pm, most preferably 60 to 90 pm.

In preferred embodiments, methods for producing water-soluble films according to the invention comprise the steps of a) providing a PVOH slurry, wherein the PVOH solution comprises at least one PVOH (co-)polymer and wherein the PVOH (co-)polymer is selected from at least one polyvinyl alcohol homopolymer, at least one polyvinyl alcohol copolymer or a mixture thereof, b) adding at least one biopolymer, as described herein, c) adding at least one alkyl polyglycoside, preferably selected from alkyl polyglucosides (APG), alkyl polypentosides (APP) and mixtures thereof, as described herein, d) optionally, adding further ingredients, as described herein, e) heating the slurry to form a solution, and f) casting the solution of step e) on a suitable surface to create a film having a thickness in the range of 5 to 200 pm, preferably 20 pm to 150 pm, or 35 pm to 125 pm, or 50 pm to 110 pm, more preferably 70 to 100 pm, even more preferably 50 to 95 pm, most preferably 60 to 90 pm.

In preferred embodiments, methods for producing water-soluble films according to the invention comprise the steps of a) providing a PVOH slurry, wherein the PVOH solution comprises at least one PVOH (co-)polymer and wherein the PVOH (co-)polymer is selected from at least one polyvinyl alcohol homopolymer, at least one polyvinyl alcohol copolymer or a mixture thereof, in an amount of 50 to 75 wt.%, preferably 60 to 70 wt.%, more preferably 65 to 68 wt.%, based on the total weight of the film composition, b) adding at least one biopolymer, as described herein, in an amount of 2.5 to 30 wt.%, preferably 3 to 28 wt.%, more preferably 5 to 25 wt.%, based on the total weight of the film composition, c) adding at least one alkyl polyglycoside, preferably selected from alkyl polyglucosides (APG), alkyl polypentosides (APP) and mixtures thereof, as described herein, in an amount of 0.2 to 15 wt.%, preferably 0.5 to 10 wt.%, more preferably 1 to 6 wt.%, based on the total weight of the film composition, d) optionally, adding further ingredients, as described herein, in an amount up to 30 wt.%, based on the total weight of the film composition, wherein the at least one further ingredient is selected from the group consisting of bittering agents, solvents, in particular water, as well processing agents, in particular plasticizers, lubricants, release agents, fillers, extenders, cross-linking agents, antiblocking agents, antioxidants, detackifying agents, and antifoam, e) heating the slurry to form a solution, and f) casting the solution of step c) on a suitable surface to create a film having a thickness in the range of 5 to 200 pm, preferably 20 pm to 150 pm, or 35 pm to 125 pm, or 50 pm to 110 pm, more preferably 70 to 100 pm, even more preferably 50 to 95 pm, most preferably 60 to 90 pm.

In preferred embodiments, methods for producing water-soluble films according to the invention comprise the steps of a) providing a PVOH slurry, wherein the PVOH solution comprises at least one PVOH (co-)polymer and wherein the at least one PVOH (co-)polymer is selected from

(i) a vinyl alcohol vinyl acetate copolymer; and/or

(iii) a sulfonated polyvinyl alcohol copolymer; and/or

(v) a PVOH (co-)polymer comprising an anionic monomer unit, wherein the anionic monomer is selected from the group consisting of vinyl acetic acid, alkyl acrylates, maleic acid, monoalkyl maleate, dialkyl maleate, monomethyl maleate, dimethyl maleate, maleic anhydride, fumaric acid, monoalkyl fumarate, dialkyl fumarate, monomethyl fumarate, dimethyl fumarate, itaconic acid, monomethyl itaconate, dimethyl itaconate, itaconic anhydride, citraconic acid, monoalkyl citraconate, dialkyl citraconate, citraconic anhydride, mesaconic acid, monoalkyl mesaconate, dialkyl mesaconate, glutaconic acid, monoalkyl glutaconate, dialkyl glutaconate, glutaconic anhydride, vinyl sulfonic acid, alkyl sulfonic acid, ethylene sulfonic acid, 2-acryl amido-1 -methyl propane sulfonic acid, 2-acryl amide-2-methyl propane sulfonic acid, 2-methyl acryl amido-2-methyl propane sulfonic acid, 2- sulfoethyl acrylate, alkali metal salts of the foregoing, esters of the foregoing, and mixtures thereof; and/or

(vi) mixtures thereof, in an amount of 50 to 75 wt.%, preferably 60 to 70 wt.%, more preferably 65 to 68 wt.%, based on the total weight of the film composition, b) adding at least one biopolymer, wherein

(ii) the at least one biopolymer is selected from the group consisting of polysaccharides, peptides, proteins, glycoproteins, proteoglycans, poly(amino acids), derivatives of the foregoing, and mixtures thereof; and/or (iii) the at least one biopolymer is selected from the group consisting of galactomannans, xyloglucans, galactoglucomannans, starches, amylose and amylopectin, glucans, p-glucans, pectins, protopectin, pectin polysaccharides, arabinans, galactans, and arabinogalactans, a-glucans, a1-4- glucans, a-1 ,6-glucans, glucomannans, celluloses, carboxy methyl cellulose (CMC), hydroxyethyl cellulose (HEC), hydroxypropyl cellulose (HPC), hydroxypropyl methyl cellulose (HPMC), methyl cellulose (MC), ethyl cellulose (EC), hemicelluloses, gum arabic, gum tragacanth, karaya gum, carrageenans, alginates, alginic acid (heteropolysaccharide comprised of D-mannuronic acid and L- guluronic acid), agar, agarose, furcellaran, chitin, chitosan, hyaluron, xanthan, gellan, dextran, curdlan, scleroglucan, schizophyllan, dextrins, cyclodextrins, glycogen, hydroxypropyl starch phosphate (HSP), hyaluronic acid, glycosaminoglycans, pullulan, gelatin, chrysolaminarin, laminarin, lentinan, lichenin, pleuran, zymosan, wheat proteins, soy proteins, pea proteins, potato proteins, whey proteins, corn proteins, caseins, aS1-, aS2-, p- and K-casein, caseinates, bovine casein salts, goat casein salts, sheep casein salts, p-lactoglobulin, a-lactalbumin, serum albumin, immunoglobulin, casein macropeptides, elastins, fibrins, collagens, aggrecans, chitins, chondroitin sulphate, keratan sulphate, heparin, dermatan sulphate and hyaluronate (hyaluronic acid), cyanophycin, poly(a-L-lysin), poly(y-glutamic acid), derivatives of the foregoing, and mixtures thereof; and/or

(iv) starches, amylose and amylopectin, celluloses, carboxy methyl cellulose (CMC), hydroxyethyl cellulose (HEC), hydroxypropyl cellulose (HPC), hydroxypropyl methyl cellulose (HPMC), methyl cellulose (MC), ethyl cellulose (EC), glucans, p-glucans, a-glucans, wheat proteins, soy proteins, pea proteins, potato proteins, whey proteins, corn proteins, caseins, aS1-, aS2-, p- and K- casein, caseinates, bovine casein salts, goat casein salts, sheep casein salts, derivatives of the foregoing, and mixtures thereof, preferably starches, amylose and amylopectin, carrageenans, wheat proteins, soy proteins, pea proteins, potato proteins, whey proteins, corn proteins, caseins, aS1-, aS2- , p- and K-casein, caseinates, bovine casein salts, goat casein salts, sheep casein salts, derivatives of the foregoing, and mixtures thereof, in an amount of 2.5 to 30 wt.%, preferably 3 to 28 wt.%, more preferably 5 to 25 wt.%, based on the total weight of the film composition, c) adding at least one alkyl polyglycoside, wherein the at least one alkyl polyglycoside is selected from

(i) alkyl polyglycosides described by the formula (II) in which R¹ and R² are same or different and independently selected from H or OH, R³ is selected from H or CH2OH, represents branched or unbranched alkyl or alkenyl group, n represents 4 to 18, in particular 5 to 15, and p represents numbers from 1 to 10; and/or (ii) alkyl polyglucosides (APG) derived from glucose and described by the formula (III)

LX/J n in which represents branched or unbranched alkyl or alkenyl group, n represents 7 to 18, preferably 10 to 15, and p represents numbers from 1 to 10; and/or

(iii) alkyl polypentosides (APP) derived from xylose and described by the formula (IV) (IV), in which represents branched or unbranched alkyl or alkenyl group, n represents 4 to 15, in particular 5 to 10, and p represents numbers from 1 to 10; and/or

(iv) formula (V) or formula (VI)

(V) (VI), in an amount of 0.2 to 15 wt.%, preferably 0.5 to 10 wt.%, more preferably 1 to 6 wt.%, based on the total weight of the film composition, d) optionally, adding further ingredients, as described herein, in an amount up to 30 wt.%, based on the total weight of the film composition, wherein the at least one further ingredient is selected from the group consisting of bittering agents, solvents, in particular water, as well processing agents, in particular plasticizers, lubricants, release agents, fillers, extenders, cross-linking agents, antiblocking agents, antioxidants, detackifying agents, and antifoam, e) heating the slurry to form a solution, and f) casting the solution of step c) on a suitable surface to create a film having a thickness in the range of 5 to 200 pm, preferably 20 pm to 150 pm, or 35 pm to 125 pm, or 50 pm to 110 pm, more preferably 70 to 100 pm, even more preferably 50 to 95 pm, most preferably 60 to 90 pm.

In preferred embodiments, the film comprises at least two biopolymers, wherein the at least two biopolymers are as described herein, preferably being selected from the group consisting of starches, amylose and amylopectin, celluloses, carboxy methyl cellulose (CMC), hydroxyethyl cellulose (HEC), hydroxypropyl cellulose (HPC), hydroxypropyl methyl cellulose (HPMC), methyl cellulose (MC), ethyl cellulose (EC), glucans, p-glucans, a-glucans, wheat proteins, soy proteins, pea proteins, potato proteins, whey proteins, corn proteins, caseins, aS1-, aS2-, p- and K-casein, caseinates, bovine casein salts, goat casein salts, sheep casein salts, derivatives of the foregoing, and mixtures thereof, preferably starches, amylose and amylopectin, carrageenans, wheat proteins, soy proteins, pea proteins, potato proteins, whey proteins, corn proteins, caseins, aS1-, aS2-, p- and K-casein, caseinates, bovine casein salts, goat casein salts, sheep casein salts, derivatives of the foregoing, and mixtures thereof, derivatives of the foregoing, and mixtures thereof.

In preferred embodiments, the film comprises at least one PVOH (co-)polymer and at least one biopolymer, wherein the total amount of PVOH (co-)polymers and biopolymers is 52.5 to 80 wt.%, preferably 60 to 75 wt.%; and/or the ratio of the at least one PVOH (co-)polymer and the at least one biopolymer is between 20:1 and 2.5:1 , preferably between 15:1 and 10:1.

All facts, objects and embodiments described for the water-soluble film according to the invention are also applicable to this object of the invention. Therefore, explicit reference is made at this point to the disclosure at the appropriate place with the indication that this disclosure also applies to the above methods according to the invention.

Method for producing washing or cleaning agent portion units

The invention also relates to a method for producing a washing or cleaning agent portion unit having at least one filled receiving chamber surrounded by a water-soluble film, comprising the steps of a) transporting a first water-soluble film in the direction of a dosing station at a speed above 0.04 m/s, preferably above 0.08 m/s, b) molding the first water-soluble film into the cavities of a deep-drawing die located below the water-soluble film, so as to form at least one cavity having a maximum diameter in the direction of travel of the film of between 3 and 75 mm, c) filling the cavity by means of the dosing station with a first cleaning or washing composition, d) further transporting the filled cavity in the direction of a sealing station at a speed above 0.04 m/s, preferably above 0.08 m/s, and e) sealing the filled cavity with a second water-soluble film, wherein the first water-soluble film and the second water-soluble film are the same or different.

In preferred embodiments, the method for producing a washing or cleaning agent portion unit having at least one filled receiving chamber surrounded by a water-soluble film, comprise the steps of a) transporting a first water-soluble film in the direction of a dosing station at a speed above 0.04 m/s, preferably above 0.08 m/s, b) molding the first water-soluble film into the cavities of a deep-drawing die located below the water-soluble film, so as to form at least one cavity having a maximum diameter in the direction of travel of the film of between 3 and 75 mm, c) filling the cavity by means of the dosing station with a first cleaning or washing composition, d) further transporting the filled cavity in the direction of a sealing station at a speed above 0.04 m/s, preferably above 0.08 m/s, and e) sealing the filled cavity with a second water-soluble film, wherein the first water-soluble film and the second water-soluble film are the same or different and are water-soluble films according to the invention as described herein.

In the context of the method described herein, water-soluble films according to the invention are formed in a deep-drawing apparatus and combined with washing or cleaning compositions to form washing or cleaning agent portion units.

The deep-drawing apparatus used can be operated continuously or discontinuously. A continuous procedure is preferred for increasing the efficiency of production. In particularly preferred embodiments, the water-soluble film is continuously transported from step a) to step e).

With regard to economy and safety, it is preferred that the transportation speed for the first water- soluble film is from 0.08 to 0.3 m/s, preferably from 0.1 to 0.2 m/s.

In step b), the water-soluble film is molded into the cavity of a deep-drawing die. The molding can be preceded by optional pre-treatment of the film by heat and/or solvents. The water-soluble film can be molded into the cavity, e.g., by means of a tool, by the action of a vacuum, by the action of compressed air and/or by the action of its own weight.

With respect to deep-drawing, methods are preferred in which the water-soluble film is transported above the cavities of a deep-drawing die and is molded there into the recesses in the die by the action of compressed air on the upper side of the film or by the action of a vacuum on the underside of the film, particularly preferably by the simultaneous action of compressed air and vacuum. Particularly advantageous methods are characterized in that the film is pre-treated by the action of heat and/or solvents before the molding.

In preferred embodiments, the water-soluble film is pre-treated by the action of heat before the molding, such process also known as thermoforming.

In preferred embodiments, the first water-soluble film is drawn into the cavities via vacuum thermoforming. The action of heat and/or solvents on the water-soluble film facilitates the plastic deformation thereof. The film can be heated, e.g., by heat radiation, hot air or, particularly preferably, by direct contact with a hotplate. The duration of the heat treatment as well as the temperature of the heat radiation, hot air or hotplate surface used is of course dependent on the type of shell material used. For water-soluble or water-dispersible materials such as PVOH-containing polymers or copolymers, a temperature between 90°C and 130°C, in particular between 105°C and 115°C, is preferred. The duration of the heat treatment, in particular the contact time when using a hotplate, is preferably between 0.1 and 7 s, particularly preferably between 0.2 and 6 s and in particular between 0.3 and 4 s. Contact times below one second, in particular in the range of from 400 to 900 ms, preferably between 500 and 800 ms, have proven to be particularly advantageous for materials made of polyvinyl alcohol. For water-soluble materials containing biopolymers, in particular protein-based biopolymers, a temperature less than 60°C, preferably approx. 55°C, is preferred.

In general, thermoforming of films results in thinning of the film as the film is drawn into the cavity or mold, relative to the film thickness before thermoforming. Hence, increasing the draw ratio of the film leads to decrease of film thickness. Such thinning of the film is expected to result in faster release of the composition contained in the portion unit surrounded by such film. Furthermore, thermoforming might lead to polymer chain alignment and stress within in the polymer matrix, which can result in decreased disintegration time as well as decreased liquid release time.

The inventors have surprisingly found that the addition of alkyl polyglycosides, in particular alkyl polyglucosides (APG) and/or alkyl polypentosides (APP), to PVOH-based films improves the mechanical properties of the film so that the film is less sensitive, and/or the disintegration time and/or liquid release time, as described herein, can be improved.

The inventors have surprisingly found that the addition of alkyl polyglycosides, in particular alkyl polyglucosides (APG) and/or alkyl polypentosides (APP), to films comprising PVOH as well as biopolymers improves the mechanical properties of the film so that the film is less sensitive, and/or the disintegration time and/or liquid release time, as described herein, can be improved.

The deep-drawing die itself can be designed in the form of a horizontally rotating belt or in the form of a rotating drum.

The cavities of the deep-drawing die may have any shape, length, width and depth, depending on the required dimensions of the water-soluble portion unit to be produced, but preferably having an oval or circular opening, particularly preferably a circular opening. The volume of the final portion unit might be, e.g., 5 to 300 ml, or 10 to 150 ml, or 20 to 100 ml, preferably it is 5 to 50 ml, more preferably it is 10 to 25 ml, even more preferably 10 to 20 ml, most preferably 10 to 18 ml, e.g., 30 ml or less, 25 ml or less, 20 ml or less, 15 ml or less, 10 ml or less, e.g., 5 ml, 6 ml, 7 ml, 8 ml, 9 ml, 10 ml, 11 ml, 12 ml, 13 ml, 14 ml, 15 ml, 16 ml, 17 ml, 18 ml, 19 ml, 20 ml, 21 ml, 22 ml, 23 ml, 24 ml, 25 ml, 26 ml, 27 ml, 28 ml, 29 ml, or 30 ml. Moreover, the water-soluble portion units may have one or more receiving chamber, which may differ in size and shape. In such case, the cavities to be filled may also vary in size and shape from one to another. Each of the receiving chamber might have a volume of 0.5 to 10 ml, preferably 1 to 7.5 ml, more preferably 2 to 7.5 ml, e.g., 0.5 ml, 0.75 ml, 1 ml, 1 .25 ml, 1 .5 ml, 1 .75 ml, 2 ml, 2.25 ml, 2.5 ml, 2.75 ml, 3 ml, 3.25 ml, 3.5 ml, 3.75 ml, 4 ml, 4.25 ml, 4.5 ml, 4.75 ml, 5 ml, 5.25 ml, 5.5 ml, 5.75 ml, 6 ml, 6.25 ml, 6.5 ml, 6.75 ml, 7 ml, 7.25 ml, 7.5 ml, 7.75 ml, 8 ml, 8.25 ml,

8.5 ml, 8.75 ml, 9 ml, 9.25 ml, 9.5 ml, 9.75 ml, or 10 ml.

The cavities of the deep-drawing die preferably have a maximum diameter in the direction of travel of the film of between 3 and 40 mm, preferably between 3 and 20 mm and in particular between 3 and 15 mm. These diameters are particularly preferred for cavities having a circular opening.

The volume of the cavities of the deep-drawing die is preferably from 0.5 to 30 cm³, particularly preferably from 1 to 10 cm³ and in particular from 1 .5 to 4 cm³. These volumes are particularly preferred for cavities having a circular opening.

The cavities of the deep-drawing die preferably have a depth of 10 to 30 mm, preferably 11 to 20 mm, more preferably 12 to 15 mm, e.g., 10 mm, 10.5 mm, 1 1 mm, 11 .5 mm, 12 mm, 12.5 mm, 13 mm,

13.5 mm, 14 mm, 14.5 mm, 15 mm, 15.5 mm, 16 mm, 16.5 mm, 17 mm, 17.5 mm, 18 mm, 18.5 mm,

19 mm, 19.5 mm, 20 mm, 20.5 mm, 21 mm, 21.5 mm, 22 mm, 22.5 mm, 23 mm, 23.5 mm, 24 mm,

24.5 mm, 25 mm, 25.5 mm, 26 mm, 26.5 mm, 27 mm, 27.5 mm, 28 mm, 28.5 mm, 29 mm, 29.5 mm, or 30 mm. In preferred embodiments, the cavities of the deep-drawing die have a depth of 11 to 15 mm, in particular 11 mm, 11 .5 mm, 12 mm, 12.5 mm, 13 mm, 13.5 mm, 14 mm, 14.5 mm, or 15 mm, particularly preferred 11 to 13.5 mm.

In preferred embodiments, the size and shape of the cavity or mold refers to one allowing a draw ratio of at least 1 .5, preferably 1 .8, more preferably 2.0, e.g., 1 .5, 1 .6, 1 .7, 1 .8, 1 .9, 2.0, 2.1 , 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3.0, 3.1 , 3.2, 3.3, 3.4, 3.5, 3.6, 3.7, 3.8, 3.9, or 4.0. In preferred embodiments, the size and shape of the cavity or mold refers to one allowing a draw ratio of 1 .5 to 3.0, preferably 1 .8 to 2.6, most preferably 1 .8 to 2.3, in particular 1 .5, 1 .6, 1 .7, 1 .8, 1 .9, 2.0, 2.1 , 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, or 3.0.

In step c), the previously molded cavities are filled with a first cleaning or washing composition. The degree of filling of the cavity is preferably at least 60 vol.%, preferably at least 80 vol.% and in particular at least 90 vol.%. Such a high degree of filling reduces the proportion of water-soluble packaging film with respect to the total weight of the cleaning or washing agent portion unit and improves the ecological profile of said film. Moreover, the visual impression thereof is also improved due to the smaller air bubble in the closed receiving chamber. Preferably, the first cleaning or washing composition is flowable under standard conditions (20°C, 1 ,013 mbar).

In step d), the water-soluble film provided with the filled cavities is transported in the direction of a sealing station. The speed of the film transport is preferably 0.08 to 0.3 m/s, particularly preferably 0.1 to 0.2 m/s.

In step e), the filled cavities are sealed with a second water-soluble film. This second water- soluble film may be identical to the first water-soluble film but may also differ from the first film with regard to the composition or thickness thereof. Any suitable method for sealing may be utilized, e.g., heat sealing, solvent welding, solvent or wet sealing. Heat sealing is preferred.

In various embodiments, the first water-soluble film is a film according to the invention, and the second water-soluble film is different from the first water-soluble film, wherein the second water- soluble film is substantially based on PVOH-based film composition. In various embodiments, the first water-soluble film is a film according to the invention, and the second water-soluble film is different from the first water-soluble film, wherein the second water-soluble film is substantially based on biopolymer-based film composition. In various embodiments, the first water-soluble film is a film according to the invention, and the second water-soluble film is different from the first water-soluble film, wherein the second water-soluble film is substantially based on PVOH-biopolymer-blend film composition. In various embodiments, the first water-soluble film and the second water-soluble film are different from each other, wherein both films are according to the invention. In various embodiments, the first water-soluble film and the second water-soluble film are the same and according to the invention.

Following the sealing, the filled cavities (receiving chambers) are preferably separated into washing or cleaning agent portion units, e.g., by a cutting device. The cutting device may be of any suitable form, e.g., a sharp item, a hot item, or a laser.

The resulting washing or cleaning agent portion units can have a single filled receiving chamber, but preferably have at least two, particularly preferably at least three or even more preferably at least four or more filled receiving chambers.

In case of multi-chamber portion units, the different compartments can be filled simultaneously or subsequently.

The process described above works with flowable washing or cleaning compositions. However, at least one of the receiving chambers might also be filled with a solid or powdery washing or cleaning composition. In preferred embodiments, the water-soluble washing or cleaning portion units according to the invention comprise one or more receiving chamber(s), the receiving chamber(s) being filled with flowable washing or cleaning compositions. In case of multi-chamber portion units, the flowable washing or cleaning compositions in the several receiving chamber might be the same or might differ from one another.

Such a deep-drawing process is described in more detail in, e.g., WO 2022/017727 A1 , EP 2528955 B1 , or WO 2023/107585 A1 .

All facts, objects and embodiments described for the water-soluble film according to the invention as well as for the method for producing water-soluble films as well as for water-soluble washing or cleaning agent portion unit are also applicable to this object of the invention. Therefore, explicit reference is made at this point to the disclosure at the appropriate place with the indication that this disclosure also applies to the above methods according to the invention. Washing and/or cleaning compositions

The washing or cleaning compositions to be used in washing or cleaning agent portion units according to the invention include all conceivable types of washing or cleaning compositions, both concentrates and undiluted compositions, for use on a commercial scale, in the washing machine or for hand washing or cleaning. These include, e.g., detergents for textiles, carpets or natural fibers, for which the term detergent is used. This also includes, e.g., dishwashing detergents for dishwashers (automatic dishwashing detergents) or manual dishwashing detergents, for which the term cleaning agent is used. The washing or cleaning compositions according to the invention also include washing aids which are added to the actual washing agent during manual or mechanical textile washing in order to achieve a further effect. Furthermore, washing or cleaning compositions according to the invention also include textile pre- and post-treatment agents, i.e., agents with which the laundry item is brought into contact before the actual washing, e.g., to dissolve stubborn soiling, and also agents which, in a step downstream of the actual textile washing, impart further desirable properties to the laundry item, such as a pleasant feel, crease resistance or low static charge, like e.g., fabric softeners.

The washing or cleaning compositions to be used in washing or cleaning agent portion units according to the invention may comprise all known ingredients that are customary in such compositions. In particular, the compositions may comprise surfactants, builders, complexing agents, polymers, glass corrosion inhibitors, corrosion inhibitors, bleaching agents such as peroxygen compounds, bleach activators or bleach catalysts, water-miscible organic solvents, enzymes, enzyme stabilizers, sequestering agents, electrolytes, pH regulators and/or other auxiliaries such as optical brighteners, greying inhibitors, color transfer inhibitors, foam regulators as well as dyes and fragrances. Advantageous ingredients of such compositions are disclosed in, e.g., WO 2009/121725 A1 , beginning on page 5, penultimate paragraph, and ending on page 13 after the second paragraph.

The washing or cleaning compositions to be used in washing or cleaning agent portion units according to the invention may comprise at least one surfactant, which is comprised in the composition in an amount of 20 to 80 wt.%, preferably 30 to 75 wt.% and in particular 40 to 70 wt.%.

The group of surfactants comprise nonionic, anionic, cationic and amphoteric surfactants. The group of surfactants also comprises co-surfactants as described below. The compositions may comprise one or more of the surfactants mentioned. Particularly preferred compositions may comprise at least one anionic surfactant as the surfactant.

The anionic surfactant is preferably selected from the group comprising C9-13 alkylbenzene sulfonates, olefin sulfonates, C12-18 alkane sulfonates, ester sulfonates, alk(en)yl sulfates, fatty alcohol ether sulfates and mixtures thereof. Compositions which comprise C9-13 alkylbenzene sulfonates and fatty alcohol ether sulfates as the anionic surfactant have particularly good dispersing properties. Surfactants of the sulfonate type that can be used are preferably C9-13 alkylbenzene sulfonates, olefin sulfonates, i.e., mixtures of alkene and hydroxyalkane sulfonates, and disulfonates, as obtained, e.g., from C12-18 monoolefins having a terminal or internal double bond by way of sulfonation with gaseous sulfur trioxide and subsequent alkaline or acid hydrolysis of the sulfonation products. C12-18 alkane sulfonates and the esters of a-sulfo fatty acids (ester sulfonates) are also suitable, e.g., the a- sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids.

The alkali salts and in particular the sodium salts of the sulfuric acid half-esters of C12-18 fatty alcohols, e.g., from coconut fatty alcohol, tallow fatty alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol or stearyl alcohol, or of C10-20 oxo alcohols and the half-esters of secondary alcohols having these chain lengths are preferred as alk(en)yl sulfates. From a washing perspective, C12-16 alkyl sulfates, C12-15 alkyl sulfates and C14-15 alkyl sulfates are preferred. 2,3-alkyl sulfates are also suitable anionic surfactants.

Fatty alcohol ether sulfates, such as the sulfuric acid monoesters of straight-chain or branched C7-21 alcohols ethoxylated with 1 to 6 mol ethylene oxide (EO), such as 2-methyl-branched C9-11 alcohols having, on average, 3.5 mol ethylene oxide or C s fatty alcohols having 1 to 4 EO, are also suitable. Alkyl ether sulfates of formula (VII) are preferred

R¹-O-(AO)_n-SO₃- X⁺ (VII)

In formula (VII), R¹ represents a linear or branched, substituted or unsubstituted alkyl functional group, preferably a linear, unsubstituted alkyl functional group, particularly preferably a fatty alcohol functional group. Preferred functional groups R¹ of formula (VII) are selected from decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl functional groups and mixtures thereof, the representatives having an even number of C atoms being preferred. Particularly preferred functional groups R¹ of formula (VII) are derived from fatty alcohols having 12 to 18 C atoms, e.g., from coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol, or from oxo alcohols having 10 to 20 C atoms. In formula (VII), AO represents an ethylene oxide (EO) or propylene oxide (PO) group, preferably an ethylene oxide group. The index n in formula (VII) is an integer of from 1 to 50, preferably from 1 to 20, and in particular from 2 to 10. Very particularly preferably, n is 2, 3, 4, 5, 6, 7 or 8. X⁺ is a monovalent cation or the n-th part of an n- valent cation, the alkali metal ions, including Na⁺ or K⁺, being preferred in this case, with Na⁺ being most preferred. Further cations X⁺ may be selected from NHT, % Zn²⁺, % Mg²⁺, % Ca²⁺, % Mn²⁺, and mixtures thereof.

Preferred compositions may comprise an alkyl ether sulfate selected from fatty alcohol ether sulfates of formula (VIII) where k = 11 to 19, and n = 2, 3, 4, 5, 6, 7 or 8. Very particularly preferred representatives are Na fatty alcohol ether sulfates having 12 to 18 C atoms and 2 EO (k = 11 to 13, n = 2 in formula (VIII)). The degree of ethoxylation indicated represents a statistical average that can correspond to an integer or a fractional number for a specific product. The degrees of alkoxylation indicated represent statistical averages that can correspond to an integer or a fractional number for a specific product. Preferred alkoxylates/ethoxylates have a narrowed homolog distribution (narrow range ethoxylates, NRE). In preferred embodiments, the compositions may comprise C9-13 alkylbenzene sulfonates and optionally also fatty alcohol ether sulfates as the anionic surfactant.

In preferred embodiments, the compositions may comprise at least one anionic surfactant of formula (IX) in which R’ and R” are, independently of one another, H or alkyl, and together contain 9 to 19, preferably 9 to 15 and in particular 9 to 13, C atoms, and Y⁺ denotes a monovalent cation or the n-th part of an n-valent cation (in particular Na⁺).

In summary, preferred compositions may comprise, as the surfactant, at least one anionic surfactant, preferably at least one anionic surfactant from the group consisting of Cs-is alkylbenzene sulfonates, Cs-is olefin sulfonates, C12-18 alkane sulfonates, Cs-is ester sulfonates, Cs-is alkyl sulfates, Cs-is alkenyl sulfates, fatty alcohol ether sulfates, in particular at least one anionic surfactant from the group of Cs-is alkylbenzene sulfonates.

The proportion by weight of the anionic surfactant with respect to the total weight of the compositions is preferably 20 to 60 wt.% and in particular 22 to 50 wt.%.

The washing or cleaning compositions to be used in washing or cleaning agent portion units according to the invention, alternatively or in addition to the anionic surfactant, may comprise at least one nonionic surfactant in an amount of, based on the total weight thereof, 12 to 30 wt.%, preferably 15 to 25 wt.%, and also particularly preferably 0.3 to 5 wt.% of a nonionic co-surfactant that differs from the nonionic surfactant.

Suitable nonionic surfactants are in particular alkyl glycosides and ethoxylation and/or propoxylation products of alkyl glycosides or linear or branched alcohols each having 8 to 18 C atoms in the alkyl moiety and 3 to 20, preferably 4 to 10 alkyl ether groups. Furthermore, corresponding ethoxylation and/or propoxylation products of N-alkylamines, vicinal diols, fatty acid esters and fatty acid amides, which correspond to the long-chain alcohol derivatives mentioned with regard to the alkyl moiety, and of alkylphenols with 5 to 12 C atoms in the alkyl residue are also useful.

Preferably alkoxylated, preferably ethoxylated, in particular primary alcohols with preferably 8 to 18 C atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol are suitable as nonionic surfactants, in which the alcohol residue can be linear or preferably methyl-branched in the 2-position or may comprise linear and methyl-branched residues in the mixture, as they are usually present in oxoalcohol residues. However, alcohol ethoxylates with linear residues from alcohols of native origin with 12 to 18 C atoms, e.g., from coconut, palm, tallow fat or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol are particularly preferred. Preferred ethoxylated alcohols include, e.g., C12-14 alcohols with 3 EO or 4 EO, C9-11 alcohol with 7 EO, C13-15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C12-18 alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C12-14 alcohol with 3 EO and C12-18 alcohol with 5 EO. The stated degrees of ethoxylation represent statistical mean values, which can be a whole or a fractional number for a specific product. Preferred alcohol ethoxylates have a narrowed homolog distribution (narrow range ethoxylates, NRE). Alternatively or in addition to these nonionic surfactants, fatty alcohols with more than 12 EO can also be used. Examples of this are tallow fatty alcohols with 14 EO, 25 EO, 30 EO or 40 EO.

Preferred nonionic surfactants are selected from the group of alkoxylated primary Cs-18 alcohols having a degree of alkoxylation of > 4, particularly preferably the C12-14 alcohols having 4 EO or 7 EO, the C9-11 alcohols having 7 EO, the C13-15 alcohols having 5 EO, 7 EO or 8 EO, the C13-15 oxo alcohols having 7 EO, the C12-18 alcohols having 5 EO or 7 EO, the C13-15 oxo alcohols having 7 EO, in particular the primary C12-18 alcohols having a degree of alkoxylation of > 4, very particularly preferably the primary C12-18 alcohols having 7 EO.

A further class of suitable nonionic surfactants, which may be used alternatively or in addition, are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably with 1 to 4 C atoms in the alkyl chain, in particular fatty acid methyl esters.

A further class of suitable nonionic surfactants are alkyl polyglycosides of the formula

RO(G)_Z (X), in which R is a linear or branched, in particular methyl-branched in the 2-position, saturated or unsaturated, aliphatic residue with 8 to 22, preferably 12 to 18, C atoms and G stands for a sugar unit with 5 or 6 C atoms, preferably for glucose. The degree of glycosidation z is between 1 and 4, preferably between 1 and 2 and in particular between 1.1 and 1.4. Linear alkyl polyglycosides, i.e., alkyl polyglycosides in which the polyglycosyl residue is a glucose residue and the alkyl residue is an n-alkyl residue, are preferably used.

Nonionic surfactants of the amine oxide type, e.g., N-cocoalkyl-N,N-dimethylamine oxide and N- tallowalkyl-N,N-dihydroxyethylamine oxide, and fatty acid alkanolamides may also be suitable. The amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, in particular not more than half thereof.

Suitable surfactants may comprise alkoxylated non-ionic surfactants, in particular the ethoxylated primary alcohols and mixtures of these surfactants with structurally complex surfactants such as polyoxypropylene/polyoxyethylene/polyoxypropylene ((PO/EO/PO) surfactants). Such (PO/EO/PO) non-ionic surfactants are also characterized by good foam control. In the context dishwashing detergents, low-foaming non-ionic surfactants which have alternating ethylene oxide and alkylene oxide units have proven to be especially preferred, in particular surfactants having EO-AO-EO-AO blocks with 1 to 10 EO groups and AO groups being bonded to each other in each case, before a block follows from the respective other groups, e.g., non-ionic surfactants of formula (XI) in which R¹ represents a straight-chain or branched, saturated or mono- or polyunsaturated C6-24 alkyl or alkenyl functional group; each R² and R³ group is selected, independently of one another, from -CH3, -CH2CH3, -CH2CH2-CH3, -CH(CH₃)₂, and the indices w, x, y, z, independently of one another, represent integers from 1 to 6. Preferred non-ionic surfactants of formula (XI) can be produced using known methods from the corresponding alcohols R¹-OH and ethylene or alkylene oxide. Besides propylene oxide, butylene oxide in particular is worthy of consideration as an alkylene oxide unit that is contained alternately with the ethylene oxide unit in non-ionic surfactants. However, other alkylene oxides in which R² and R³ are selected, independently of one another, from -CH2CH2-CH3 and - CH(CH₃)₂ are also suitable. Preferably, non-ionic surfactants of the formula (XI) are used in which R² and R³ represent a functional group -CH3; w and x, independently of one another, represent values of 3 or 4; and y and z, independently of one another, represent values of 1 or 2.

Suitable non-ionic surfactants may have the formula (XII)

R¹O(AlkO)xM(OAIk)_yOR² (XII), where R¹ and R², independently of one another, represent a branched or unbranched, saturated or unsaturated, optionally hydroxylated, alkyl functional group having 4 to 22 C atoms; Aik represents a branched or unbranched alkyl functional group having 2 to 4 C atoms; x and y represent, independently of one another, values of between 1 and 70; and M represents an alkyl functional group from the group -CH2, -CHR³, -CR³R⁴, -CH2CHR³ and -CHR³CHR⁴, where R³ and R⁴, independently of one another, represent a branched or unbranched, saturated or unsaturated, alkyl functional group having 1 to 18 C atoms.

Suitable non-ionic surfactants may have the formula (XIII)

R¹-CH(OH)CH2-O(CH2CH₂O)xCH₂CHR(OCH₂CH₂)y-CH₂CH(OH)-R² ₍ (xm), where R, R¹ and R², independently of one another, represent an alkyl functional group or alkenyl functional group having 6 to 22 C atoms; x and y, independently of one another, represent values of between 1 and 40.

Suitable non-ionic surfactants may have the formula (XIV)

R¹-CH(OH)CH₂-O(CH2CH₂O)xCH2CHR(OCH₂CH2)_yO-CH₂CH(OH)-R² _{> (X|V)} in which R represents a linear, saturated alkyl functional group having 8 to 16 C atoms, preferably 10 to 14 C atoms, and n and m represent, independently of one another, values of from 20 to 30. Such compounds can be obtained, e.g., by reacting alkyl diols HO-CHR-CH2-OH with ethylene oxide, with a reaction with an alkyl epoxide being performed subsequently in order to close the free OH functions whilst forming a dihydroxy ether.

Suitable non-ionic surfactants may have the formula (XV)

R¹-CH(OH)CH₂O-(AO)w-(AO)x-(A"O)y-(A'"O)z-R² (XV), in which R¹ represents a straight-chain or branched, saturated or mono- or polyunsaturated C6-24 alkyl functional group or alkenyl functional group; R² represents hydrogen or a linear or branched hydrocarbon functional group having 2 to 26 C atoms; A, A', A" and A'" represent, independently of one another, a functional group from the group -CH2CH2, -CH2CH2-CH2, -CH2-CH(CH3), -CH2-CH2- CH2-CH2, -CH2-CH(CH3)-CH2-, -CH2-CH(CH2-CH3); W, X, y and z represent values of between 0.5 and 120, where x, y and/or z can also be 0.

Suitable end-capped poly(oxyalkylated) non-ionic surfactants may have the formula (XVI) besides a functional group R¹, which represents linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon functional groups having 2 to 30 C atoms, preferably having 4 to 22 C atoms, also have a linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon functional group R² having 1 to 30 C atoms, where n represents values of between 1 and 90, preferably values of between 10 and 80, and in particular values of between 20 and 60. Surfactants of the formula (XVI) are particularly preferred in which R¹ represents C7 to C13, n represents a whole natural number from 16 to 28, and R² represents Cs to C12.

Suitable surfactants may have the formula (XVII)

R¹O[CH2CH(CH3)O]x[CH2CH2O]_yCH₂CH(OH)R² (XVII), in which R¹ represents a linear or branched aliphatic hydrocarbon functional group having 4 to 18 C atoms or mixtures thereof, R² represents a linear or branched hydrocarbon functional group having 2 to 26 C atoms or mixtures thereof, and x represents values of between 0.5 and 1 .5, and y represents a value of at least 15. The group of these non-ionic surfactants includes, e.g., the C2-26 fatty alcohol (PO)i-(EO) 15-40-2-hydroxyalkyl ethers, in particular including the Cs-io fatty alcohol (PO)I-(EO)22-2- hydroxydecyl ethers.

Suitable end-capped poly(oxyalkylated) non-ionic surfactants may have the formula (XVIII) R¹O[CH2CH2O]x[CH₂CH(R³)O]_yCH2CH(OH)R² (XVIII), in which R¹ and R², independently of one another, represent a linear or branched, saturated or mono- or polyunsaturated hydrocarbon functional group having 2 to 26 C atoms, R³, independently of one another, is selected from -CH3, -CH2CH3, -CH2CH2-CH3, -CH(CH3)2, but preferably represents - CH3, and x and y, independently of one another, represent values between 1 and 32, with non-ionic surfactants in which R³ = -CH3 and having values for x of from 15 to 32 and for y of from 0.5 and 1 .5 being very preferred.

Suitable end-capped poly(oxyalkylated) non-ionic surfactants may have the formula (XIX)

R¹O[CH₂CH(R³)O]x[CH2]kCH(OH)[CH₂]jOR² (XIX), in which R¹ and R² represent linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon functional groups having 1 to 30 C atoms, R³ represents H or a methyl, ethyl, n-propyl, iso-propyl, n-butyl, 2-butyl or 2-methyl-2-butyl functional group, x represents values between 1 and 30, and k and j represent values between 1 and 12, preferably between 1 and 5. If the value is x > 2, each R³ in the formula (XIX) can be different. R¹ and R² are preferably linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon functional groups having 6 to 22 C atoms, with functional groups having 8 to 18 C atoms being particularly preferred. For the functional group R³, H, - CH3 or -CH2CH3 are particularly preferred. Especially preferred values for x lie in the range of from 1 to 20, in particular from 6 to 15. As described above, each R³ in the formula (XIX) can be different if x > 2. As a result, the alkylene oxide unit in the square brackets can be varied. For example, if x represents 3, the functional group R³ can be selected in order to form ethylene oxide (R³ = H) or propylene oxide (R³ = CH3) units, which can be joined together in any sequence, e.g., (EO)(PO)(EO), (EO)(EO)(PO), (EO)(EO)(EO), (PO)(EO)(PO), (PO)(PO)(EO) and (PO)(PO)(PO). The value 3 for x has been selected here by way of example and can by all means be greater, in which case the range of variation increases as the values for x increase and includes a large number of (EO) groups combined with a small number of (PO) groups, for example, or vice versa. Particularly suitable endcapped poly(oxyalkylated) alcohols of the formula (XIX) have values of k = 1 and j = 1 , and therefore the formula (XIX) is simplified to the formula (XX)

R¹O[CH2CH(R³)O]XCH₂CH(OH)CH₂OR² (XX), in which R¹, R² and R³ are as defined above with respect to formula (XIX) and x represents numbers from 1 to 30, preferably 1 to 20, and in particular s to 18. Surfactants in which the functional groups R¹ and R² have 9 to 14 C atoms, R³ represents H, and x assumes values from 6 to 15 are particularly suitable.

Suitable non-ionic surfactants may have the formula (XXI)

R¹-CH(OH)CH₂O-(AO)_W-R² (XXI), in which R¹ represents a straight-chain or branched, saturated or mono- or polyunsaturated C6-24 alkyl functional group or alkenyl functional group; R² represents a linear or branched hydrocarbon functional group having 2 to 26 C atoms; A represents a functional group from the group -CH2CH2, - CH2CH2CH2, -CH₂CH(CH3), preferably -CH2CH2, and w represents values between 1 and 120, preferably 10 to 80, particularly 20 to 40. The group of these non-ionic surfactants includes, E:G:, the C4-22 fatty alcohol-(EO)io-8o-2-hydroxyalkyl ethers, in particular including the C8-12 fatty alcohol-(EO)₂₂- 2-hydroxydecyl ethers and the C4-22 fatty alcohol-(EO)4o-so-2-hydroxyalkyl ethers.

Suitable amphoteric surfactants are, e.g., betaines of the formula (XXII) (R¹)(R²)(R³)N⁺CH₂COO- (XXII), in which R¹ is an alkyl residue having 8 to 25, preferably 10 to 21 , C atoms, which may be interrupted by heteroatoms or heteroatom groups, and R² and R³ are identical or different alkyl residues having 1 to 3 C atoms, in particular Cio-is-alkyl dimethyl carboxymethyl betaine and C11-17- alkylamidopropyldimethyl carboxymethyl betaine.

Suitable cationic surfactants include the quaternary ammonium compounds of the formula (XXIII) (R¹)(R²)(R³)(R⁴)N⁺X- (XXIII), in which R¹ to R⁴ stand for four identical or different, in particular two long-chain and two shortchain, alkyl residues and X- stands for an anion, in particular a halide ion, e.g., dodecyl dimethyl ammonium chloride, alkylbenzyl dodecyl ammonium chloride and mixtures thereof. Other suitable cationic surfactants are the quaternary surface-active compounds, in particular with a sulfonium, phosphonium, iodonium or arsonium group, which are also known as antimicrobial agents. By using quaternary surface-active compounds with antimicrobial activity, the composition can be designed with an antimicrobial effect or its antimicrobial effect, which may already be present due to other ingredients, can be improved.

With regard to the rheological properties of the composition and the processability thereof, it has proven to be advantageous to use anionic surfactant and nonionic surfactant in a weight ratio of from 3:1 to 1 :2, preferably from 2:1 to 1 :1 .5 and in particular from 1 .4:1 to 1 :1 .

It has proven to be technically advantageous to supplement the previously described surfactant system consisting of anionic and nonionic surfactant with a further co-surfactant. The proportion by weight of the co-surfactant with respect to the total weight of the composition is preferably 0.3 to 5 wt.%. Preferred co-surfactants are selected from the group consisting of alkoxylated primary Cs-18 alcohols having a degree of alkoxylation of < 3, aliphatic Ce-14 alcohols, aromatic Ce-14 alcohols, aliphatic C6-12 dialcohols, monoglycerides of C12-18 fatty acids, monoglycerol ethers of Cs-18 fatty alcohols, in particular from the group of alkoxylated primary C12-18 alcohols having a degree of alkoxylation of < 3.

In addition to the surfactants described above, the washing or cleaning compositions to be used in washing or cleaning agent portion units according to the invention may comprise at least one fatty acid. For the optical properties, the viscosity profile and the cleaning performance of the composition, it has proven advantageous for the compositions to comprise, based on the total weight thereof, 4 to 12 wt.%, preferably 6 to 10 wt.%, fatty acid. Preferred fatty acids are selected from the group of caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, linoleic acid and mixtures thereof.

It has proven to be advantageous for cold wash cleaning performance if the compositions also comprise soap(s). Preferred compositions may comprise therefore soap(s). Saturated fatty acid soaps, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid, as well as soap mixtures derived in particular from natural fatty acids, e.g., coconut, palm kernel or tallow fatty acids, are suitable.

The washing or cleaning compositions to be used in washing or cleaning agent portion units according to the invention may comprise one or more phosphonates, provided that their use is permitted by regulation, from the group consisting of amino trimethylene phosphonic acid (ATMP) and/or salts thereof; ethylene diamine tetra(methylene phosphonic acid) (EDTMP) and/or salts thereof; diethylene triamine penta(methylene phosphonic acid) (DTPMP) and/or salts thereof; 1- hydroxyethane-1 ,1-diphosphonic acid (HEDP) and/or salts thereof; 2-phosphonobutane-1 ,2,4- tricarboxylic acid (PBTC) and/or salts thereof; hexamethylene diamine tetra(methylene phosphonic acid) (HDTMP) and/or salts thereof; nitrilotri(methylene phosphonic acid) (NTMP) and/or salts thereof. Preferred are 1-hydroxyethane-1 ,1-diphosphonic acid (HEDP) or diethylene triamine penta(methylene phosphonic acid) (DTPMP). Of course, the compositions may comprise two or more different phosphonates. If present, the compositions comprise the phosphonate, preferably HEDP and/or DTPMP, in an amount of, based on the total weight of the composition, 0.1 to 8.0 wt.%, preferably 0.2 to 5.0 wt.%, more preferably 0.3 to 3.0 wt.% and particularly preferably 0.5 to 2.0 wt.%.

In preferred embodiments, the washing or cleaning compositions to be used in washing or cleaning agent portion units according to the invention are substantially free of phosphonate- containing compounds. "Substantially free of phosphonate-containing compounds" in this context means that the corresponding compositions comprise less than 2 wt.%, preferably less than 1 wt.%, more preferably less than 0.5 wt.% and particularly preferably less than 0.1 wt.%, of phosphonate- containing compounds, based on the total weight of the composition. In particularly preferred embodiments, these compositions are free of phosphonate-containing compounds.

The washing or cleaning compositions to be used in washing or cleaning agent portion units according to the invention may comprise builder substances. Organic builders include, in particular, polycarboxylates/polycarboxylic acids, polymeric polycarboxylates, aspartic acid, polyacetals, dextrins, other organic builders and phosphonates. Useful organic building substances are, e.g., polycarboxylic acids which can be used in the form of the free acid and/or their sodium salts, whereby polycarboxylic acids are understood to be those carboxylic acids which carry more than one acid function. Examples include citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids and carboxymethyl inulinulines, monomeric and polymeric amino polycarboxylic acids, in particular glycine diacetic acid, methyl glycine diacetic acid, glutamine diacetic acid, nitrile triacetic acid (NTA), imino disuccinate such as ethylene diamine-N,N'-disuccinic acid and hydroxyamino disuccinates, ethylene diamine tetraacetic acid and polyaspartic acid, polyphosphonic acids, in particular aminotris(methylene phosphonic acid), ethylene diamine tetrakis(methylene phosphonic acid), lysine tetra(methylene phosphonic acid) and 1-hydroxyethane-1 ,1-diphosphonic acid, polymeric hydroxy compounds such as dextrin and polymeric (poly)carboxylic acids, in particular those accessible by oxidation of polysaccharides or dextrins, and/or polymeric acrylic acids, methacrylic acids, maleic acids and mixed polymers of these, which may also contain small amounts of polymerizable substances without carboxylic acid functionality in polymerized form. If desired, such organic builder substances may be present in quantities of up to 50 wt.%, in particular up to 25 wt.%, preferably from 10 to 20 wt.% and particularly preferably from 1 to 5 wt.%. In addition to their builder effect, the free acids typically also have the property of an acidifying component and thus also serve to adjust a lower and milder pH value of such compositions. In particular, citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any mixtures of these should be mentioned. With particular preference, citric acid or salts of citric acid are used as the builder substance. Further particularly preferred builder substances are selected from methyl glycine diacetic acid (MGDA), glutamic acid diacetate (GLDA), aspartic acid diacetate (ASDA), hydroxyethyl imino diacetate (HEIDA), imino disuccinate (IDS) and ethylene diamine disuccinate (EDDS), carboxy methyl inulin and poly aspartate. In preferred embodiments, citric acid and/or citrate is used as a water-soluble organic builder. Particularly preferred is the use of 0.5 to 25 wt.%, preferably 0.75 to 12.5 wt.%, more preferably 1 to 4 wt.% of citric acid and/or 0.5 to 25 wt.%, preferably 0.75 to 12.5 wt.%, more preferably 1 to 4 wt.% of citrate, preferably alkali citrate, more preferably sodium citrate. Citric acid/citrate can each be used in the form of their hydrates, e.g., citric acid can be used in the form of the monohydrate, citrate in the form of the trisodium citrate dihydrate. MGDA is preferably used as MGDA trisodium salt (MGDA-Nas). GLDA is preferably used as tetrasodium salt (GLDA-Na4).

Polymeric polycarboxylates are also suitable as builders, these are, e.g., the alkali metal salts of polyacrylic acid or polymethacrylic acid, e.g., those with a relative molecular mass of 500 to 70,000 g/mol. In the context of the present disclosure, the molecular masses indicated for polymeric polycarboxylates are weight-average molecular masses M_w of the respective acid form, which were basically determined by gel permeation chromatography (GPC), using a UV detector. The measurement was carried out against an external polyacrylic acid standard, which provides realistic molar weight values due to its structural relationship with the polymers under investigation. This data differs significantly from the molar weight data in which polystyrene sulfonic acids are used as a standard. The molar masses measured against polystyrene sulfonic acids are generally significantly higher than the molar masses stated in this application. Suitable polymers are in particular polyacrylates, which preferably have a molecular mass of 2,000 to 20,000 g/mol. Due to their superior solubility, the short-chain polyacrylates from this group, which have molecular masses of 2,000 to 10,000 g/mol, and particularly preferably of 3,000 to 5,000 g/mol, may be preferred. Also suitable are copolymeric polycarboxylates, in particular those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid. Copolymers of acrylic acid with maleic acid which contain 50 to 90 wt.% of acrylic acid and 50 to 10 wt.% of maleic acid have proved to be particularly suitable. Their relative molecular mass, based on free acids, is generally 2,000 to 70,000 g/mol, preferably 20,000 to 50,000 g/mol and in particular 30,000 to 40,000 g/mol.

The washing or cleaning compositions to be used in washing or cleaning agent portion units according to the invention are preferably free of phosphate builder, i.e., they comprise less than 1 wt.%, preferably no intentionally added phosphate builder.

The washing or cleaning compositions to be used in washing or cleaning agent portion units according to the invention, in particular automatic dishwashing detergents, may comprise, as a builder, crystalline layered silicates of general formula NaMSi_xO2x+i y H2O, where M represents sodium or hydrogen, x is a number from 1 .9 to 22, preferably from 1 .9 to 4, with 2, 3, or 4 being especially preferred values forx, and y represents a number from 0 to 33, preferably from 0 to 20. It is also possible to use amorphous sodium silicates with a module Na2O:SiO2 modulus of 1 :2 to 1 .3.3, preferably 1 :2 to 1 :2.8, and particularly 1 :2 to 1 :2.6 can also be used which preferably have retarded dissolution and secondary washing properties. In preferred embodiments, the silicate content, based on the total weight of the composition, is limited to amounts below 10 wt.%, preferably below 5 wt.%, and in particular below 2 wt.%.

In addition to the aforementioned builders, the washing or cleaning compositions to be used in washing or cleaning agent portion units according to the invention may comprise alkali metal hydroxides. These alkali carriers are preferably used only in small amounts, preferably in amounts below 10 wt.%, preferably below 6 wt.%, more preferably below 5 wt.%, especially preferably between 0.1 and 5 wt.%, and in particular between 0.5 and 5 wt.%, in each case based on the total weight of the composition. Alternative washing or cleaning compositions may be free of alkali metal hydroxides.

The washing or cleaning compositions to be used in washing or cleaning agent portion units according to the invention may comprise cleaning-active polymers. The proportion by weight of the cleaning-active polymers in the total weight of the composition is preferably 0.1 to 20 wt.%, preferably 1 .0 to 15 wt.% and more preferably 2.0 to 12 wt.%. Such cleaning-active polymers may comprise but not limited to anti-graying agents, soil release agents, optical brighteners, dyes, foam regulators and the like.

Suitable graying inhibitors or soil release active ingredients (soil release polymers, SRP) are cellulose ethers, such as carboxymethyl cellulose, methyl cellulose, hydroxyalkyl celluloses and mixed cellulose ethers, such as methyl hydroxyethyl cellulose, methyl hydroxypropyl cellulose and methyl carboxy methyl cellulose. Preferably, sodium carboxy methyl cellulose, hydroxypropyl methyl cellulose and mixtures thereof and, optionally, mixtures thereof with methyl cellulose are used. The soil release active ingredients commonly used include copolyesters containing dicarboxylic acid units, alkylene glycol units and polyalkylene glycol units. The proportion of graying inhibitors and/or soil release active ingredients in washing or cleaning compositions to be used in washing or cleaning agent portion units according to the invention is generally no greater than 2 wt.% and is preferably 0.5 to 1 .5 wt.%, particularly preferably 0.5 to 2 wt.%, based on the total weight of the composition.

As optical brighteners for textiles made of cellulose fibers (e.g. cotton) in particular, derivatives of diamino stilbene disulfonic acid or its alkali metal salts can be included. Suitable are, e.g., salts of 4,4'- bis(2-anilino-4-morpholino-1 ,3,5-triazin-6-yl-amino)-stilbene-2,2'-disulfonic acid or similarly structured compounds which carry a diethanol amino group, a methyl amino group or a 2-methoxy ethyl amino group instead of the morpholino group. Furthermore, brighteners of the substituted 4,4'-distyryl- diphenyl type may be present, e.g. 4,4'-bis-(4-chloro-3-sulfostyryl)-diphenyl. Mixtures of brighteners can also be used. Brighteners of the 1 ,3-diaryl-2-pyrazoline type, e.g. 1-(p-sulfoamoylphenyl)-3-(p- chlorophenyl)-2-pyrazoline and compounds with a similar structure, are particularly suitable for polyamide fibers. The content of optical brighteners or brightener mixtures in the compositions generally does not exceed 1 wt.%, and is preferably 0.05 to 0.5 wt.%, based on the total weight of the composition. In a preferred embodiment, the composition is free of such active ingredients.

The washing or cleaning compositions to be used in washing or cleaning agent portion units according to the invention may comprise at least one blue or violet dye. This is comprised in the compositions, based on the total weight thereof, in an amount above 0 wt.%, but preferably in an amount below 0.1 wt.%, particularly preferably below 0.02 wt.%, e.g., between 0.001 and 0.01 wt.%. A dye of this kind is used, e.g., for the purpose of masking a possible yellowish hue in the preparation.

Foam regulators which can be used in washing or cleaning compositions to be used in washing or cleaning agent portion units according to the invention include, e.g., polysiloxane-silica mixtures, the finely divided silica contained therein preferably being silanized or otherwise hydrophobized. The polysiloxanes can consist of linear compounds as well as cross-linked polysiloxane resins and mixtures thereof. Further defoamers are kerosene hydrocarbons, in particular microparaffins and kerosene waxes whose melting point is above 40°C, saturated fatty acids or soaps with in particular 20 to 22 C atoms, e.g., sodium behenate, and alkali metal salts of phosphoric acid mono- and/or dialkyl esters in which the alkyl chains each have 12 to 22 C atoms. Among these, sodium monoalkyl phosphate and/or dialkyl phosphate with C16-18 alkyl groups is preferably used. The amount of foam regulators can preferably be, based on the total weight of the composition, 0.2 to 2 wt.%, particularly preferably not more than 1 wt.%.

In order to adjust the desired pH value, the washing or cleaning compositions to be used in washing or cleaning agent portion units according to the invention may comprise system-compatible and environmentally compatible acids, in particular citric acid, acetic acid, tartaric acid, malic acid, lactic acid, glycolic acid, succinic acid, glutaric acid and/or adipic acid, but also mineral acids, in particular sulphuric acid or alkali metal hydrogen sulphates, or bases, in particular ammonium or alkali metal hydroxides, preferably sodium hydroxide. Such pH regulators are preferably not comprised in the compositions in excess of 10 wt.%, and are in particular from 0.5 to 6 wt.%, particularly preferably from 0.3 to 2 wt.%, based on the total weight of the composition.

The washing or cleaning compositions to be used in washing or cleaning agent portion units according to the invention comprise at least one solvent. The proportion by weight of the solvent with respect to the total weight of the composition is preferably 12 to 32 wt.% and in particular 15 to 30 wt.%. With regard to processability, in particular the dosing ability of the composition during producing the washing or cleaning agent portion units, it has proven to be advantageous for the composition to comprise, based on the total weight thereof, 7 to 20 wt.%, preferably 10 to 18 wt.%, organic solvent. Preferred organic solvents are selected from the group of ethanol, n-propanol, i-propanol, butanols, glycol, propanediol, butanediol, methyl propanediol, glycerol, diglycol, propyl diglycol, butyl diglycol, hexylene glycol, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol methyl ether, diethylene glycol ethyl ether, propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol propyl ether, dipropylene glycol mono methyl ether, dipropylene glycol mono ethyl ether, methoxytriglycol, ethoxytriglycol, butoxytriglycol, 1-butoxyethoxy-2-propanol, 3-methyl-3-methoxybutanol, propylene-glycol-t-butylether, di-n-octylether and mixtures thereof, preferably from the group of propanediol, glycerol and mixtures thereof. The compositions may comprise such solvents in an amount of, based on the total weight of the composition, 0.1 to 25 wt.%, preferably 1 to 20 wt.% and more preferably 5 to 18 wt.%. A particularly preferred organic solvent which is particularly effective in terms of stabilizing the compositions is glycerol and 1 ,2 propylene glycol. Further preferred organic solvents are the organic amines and alkanolamines. The alkanolamine is preferably selected from the group consisting of mono-, di-, triethanol- and propanolamine and mixtures thereof. A particularly preferred alkanolamine is ethanolamine.

The washing or cleaning compositions to be used in washing or cleaning agent portion units according to the inventions are preferably low-water substance mixtures. Washing or cleaning compositions of this kind which comprise, based on the total weight thereof, less than 20 wt.% of water, preferably less than 18 wt.%, more preferably 15 wt.% or less, are preferred.

In preferred embodiments, washing or cleaning compositions to be used in washing or cleaning agent portion units is a washing or cleaning composition.

In preferred embodiments, washing or cleaning compositions to be used in washing or cleaning agent portion units is a washing composition for textile cleaning.

In preferred embodiments, washing or cleaning compositions to be used in washing or cleaning agent portion units is a cleaning composition, in particular dishwashing detergent.

The washing or cleaning compositions to be used in washing or cleaning agent portion units according to the invention may comprise one or more enzyme(s). All enzymes which can develop catalytic activity in such compositions, in particular proteases, lipases, amylases, cellulases, hemicellulases, mannanases, tannases, xylanases, xanthanases, xyloglucanases, B-glucosidases, pectinases, carrageenases, perhydrolases, oxidases, oxidoreductases, as well as mixtures thereof, are preferably usable as enzymes. Such enzymes are advantageously comprised in the composition in an amount of 1 x 10^-8 to 5 wt.% based on active protein. Increasingly preferably, each enzyme is present in an amount of from 1 x 10^-7 to 3 wt.%, from 0.00001 to 1 wt.%, from 0.00005 to 0.5 wt.%, from 0.0001 to 0.1 wt.% and particularly preferably from 0.0001 to 0.05 wt.% in the compositions, based on active protein. Particularly preferably, the enzymes exhibit synergistic cleaning performance with respect to certain soiling or stains, i.e., the enzymes comprised in the composition support each other in their cleaning performance.

The washing or cleaning compositions to be used in washing or cleaning agent portion units according to the invention may comprise one or more reversible enzyme inhibitor(s)/stabilizer(s), preferably in an amount of, based on the total weight of the composition, 0.1 to 2 wt.%, preferably 0.3 to 1 .5 wt.%. The inhibitors/stabilizers may be selected from the group consisting of polyols, such as glycerol or 1 ,2-ethylene glycol, benzamidine hydrochloride, borax, boric acids, boronic acids or their salts or esters or derivatives, in particular phenylboronic acid derivatives or 4-formylphenylboronic acid (4-FPBA), antioxidants, special peptide compounds and combinations thereof.

In particularly preferred embodiments, the washing or cleaning compositions to be used in washing or cleaning agent portion units according to the invention are substantially free of boron- containing compounds. "Substantially free of boron-containing compounds" in this context means that the compositions comprise less than 2 wt.%, preferably less than 1 wt.%, more preferably less than 0.5 wt.% and particularly preferably less than 0.1 wt.%, of boron-containing compounds, based on the total weight of the composition. In particularly preferred embodiments, the washing or cleaning compositions to be used in washing or cleaning agent portion units according to the invention are free of boron-containing compounds, i.e., in particular they contain no boric acid and/or phenylboronic acid derivatives. The washing or cleaning compositions to be used in washing or cleaning agent portion units according to the invention may comprise additional ingredients. For example, these include bleaching agents, bleach activators, bleach catalysts, thickeners, sequestering agents, electrolytes, corrosion inhibitors, in particular silver protection agents, glass corrosion inhibitors, fragrances, additives for improving the flow and drying behavior, for adjusting the viscosity, for stabilization, UV stabilizers, pearlescing agents resp. opacifying agents (e.g., glycol distearate, such as Cutina® AGS by Cognis, or mixtures containing same, such as Euperlane® by Cognis), preservatives (e.g., 2-bromo-2- nitropropane-1 ,3-diol, which is also known as Bronopol, commercially available as Myacide® BT or as Boots Bronopol BT), antimicrobial active ingredients (disinfectants), and pH adjusters in amounts of usually no more than 5 wt.%.

The washing or cleaning compositions to be used in washing or cleaning agent portion units according to the invention, in particular dishwashing detergents, may comprise at least one zinc salt as a glass corrosion inhibitor. The zinc salt can be an inorganic or organic zinc salt. The zinc salt to be used has a solubility in water of greater than 100 mg/l, preferably greater than 500 mg/l, more preferably greater than 1 g/l, and particularly greater than 5 g/l (all solubilities at 20°C water temperature). The inorganic zinc salt is preferably selected from the group consisting of zinc bromide, zinc chloride, zinc iodide, zinc nitrate, and zinc sulfate. The organic zinc salt is preferably selected from the group consisting of zinc salts of monomeric or polymeric organic acids, particularly from the group of zinc acetate, zinc acetyl acetonate, zinc benzoate, zinc formate, zinc lactate, zinc gluconate, zinc ricinoleate, zinc abietate, zinc valerate, and zinc-p-toluene sulfonate. In preferred embodiments, zinc acetate is used as a zinc salt. The zinc salt is preferably comprised in an amount of from 0.01 to 5 wt.%, more preferably 0.05 to 3 wt.%, in particular 0.1 to 2 wt.%, based on the total weight of the composition. In addition or alternatively to the above-mentioned salts (particularly the zinc salts), polyethyleneimines such as those which are available under the name Lupasol® (BASF) are preferably used as glass corrosion inhibitors in an amount of from 0 to 5 wt.%, in particular 0.01 to 2 wt.%.

Polymers that are suitable as additives are in particular maleic acid acrylic acid copolymer Na salt (e.g., Sokalan® CP 5, BASF), modified polyacrylic acid Na salt (e.g., Sokalan® CP 10, BASF), modified polycarboxylate Na salt (e.g., Sokalan® HP 25, BASF), polyalkylene oxide, modified heptamethyl trisiloxane (e.g., Silwet® L-77, BASF), polyalkylene oxide, modified heptamethyl trisiloxane (e.g., Silwet® L-7608, BASF), as well as polyethersiloxane (copolymers of polymethyl siloxanes with ethylene oxide/propylene oxide segments (polyether blocks)), preferably water-soluble, linear polyether siloxanes with terminal polyether blocks, such as Tegopren® 5840, Tegopren® 5843, Tegopren® 5847, Tegopren® 5851 , Tegopren® 5863, or Tegopren® 5878 (all from Evonik). Builder substances that are suitable as additives are particularly polyaspartic acid Na salt, ethylene diamine triacetate cocoalkyl acetamide (e.g., Rewopol® CHT 12, Evonik), methyl glycine diacetic acid tri-Na salt, and acetophosphonic acid. In the case of Tegopren® 5843 and Tegopren® 5863, mixtures with surface-active or polymeric additives exhibit synergisms. However, the use of Tegopren types 5843 and 5863 on hard surfaces made of glass, in particular glass dishes, is less preferred, since these silicone surfactants can adhere to glass. In preferred embodiments, they are omitted. The washing or cleaning compositions to be used in washing or cleaning agent portion units according to the invention, in particular dishwashing detergents, may comprise bleaching agent, in particular an oxygen bleaching agent, as well as, optionally, a bleach activator and/or bleach catalyst.

The washing or cleaning compositions to be used in washing or cleaning agent portion units according to the invention, in particular dishwashing detergents, may comprise an oxygen bleaching agent from the group of sodium percarbonate, sodium perborate tetrahydrate, and sodium perborate monohydrate. Further examples of bleaching agents which may be used are peroxypyrophosphates, citrate perhydrates as well as H2O2-yielding peracid salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid or diperdodecane diacid. Moreover, bleaching agents from the group of the organic bleaching agents can also be used. Typical organic bleaching agents are the diacyl peroxides, such as dibenzoyl peroxide. Other typical organic bleaching agents are the peroxy acids, with the alkylperoxy acids and the arylperoxy acids meriting special mention as examples. Due to its good bleaching performance, sodium percarbonate is especially preferred. One especially preferred oxygen bleaching agent is sodium percarbonate.

The washing or cleaning compositions to be used in washing or cleaning agent portion units according to the invention, in particular dishwashing detergents, may comprise at least one bleach activator. Compounds which, under perhydrolysis conditions, result in aliphatic peroxocarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and/or optionally substituted perbenzoic acid, may be used as bleach activators. Substances that carry the 0- and/or N-acyl groups of the stated number of C atoms and/or optionally substituted benzoyl groups are suitable. Multiply acylated alkylene diamines are preferred, with tetraacetyl ethyl ethylene diamine (TAED) having proven to be especially suitable.

The washing or cleaning compositions to be used in washing or cleaning agent portion units according to the invention, in particular dishwashing detergents, may comprise at least one bleach catalyst. The bleach catalysts are bleach-boosting transition metal salts or transition metal complexes such as, for example, Mn-, Fe-, Co-, Ru-, or Mo-salene complexes or -carbonyl complexes. Mn-, Fe-, Co-, Ru-, Mo-, Ti-, V-, and Cu-complexes with N-containing tripod ligands as well as Co-, Fe- Cu-, and Ru-ammine complexes can also be used as bleach catalysts. Complexes of manganese in oxidation stage II, III, IV, or IV are especially preferably used which preferably contain one or more macrocyclic ligands with the donor functions N, NR, PR, O and/or S. Preferably, ligands are used which have nitrogen donor functions. It is especially preferred to use bleach catalyst(s) which contain(s), as macromolecular ligands, 1 ,4,7-trimethyl-1 ,4,7-triazacyclononane (Me-TACN), 1 ,4,7-triazacyclononane (TACN), 1 ,5,9-trimethyl-1 ,5,9-triazacyclododecane (Me-TACD), 2-methyl-1-1 ,4, 7-trimethyl-1 ,4,7- triazacyclononane (Me/Me-TACN), and/or 2-methyl-1 ,4,7-triazacyclononane (Me/TACN). Suitable manganese complexes are, e.g., [Mn^lll2(p-O)i(p-OAc)2(TACN)2](CIO₄)2, [Mn'"Mn^lv(p-O)2(p- OAc)i(TACN)₂](BPh₄)2, [Mn^lv ₄(p-O)6(TACN)₄](CIO₄)₄, [Mn^lll2(p-O)i(p-OAc)2(Me-TACN)₂](CIO₄)2, [Mn^lllMn^lv(p-O)i(p-OAc)2(Me-TACN)2](CIO₄)₃, [Mn^lv2(p-O)₃(Me-TACN)₂](PF6)2 and [Mn^lv ₂(p- O)₃(Me/Me-TACN)₂](PF₆)2 (where OAc = OC(O)CH₃). When benzoic acid, salicylic acid, or lactic acid are used as pH regulators and/or buffer substances, these compounds can support or potentiate the antibacterial effect of the silver and/or of the silver compound.

Water-soluble washing or cleaning agent portion units

The invention also relates to water-soluble washing or cleaning agent unit dose articles, i.e., washing or cleaning agent portion units comprising at least one washing or cleaning composition surrounded by at least one water-soluble film according to the invention.

The water-soluble washing or cleaning agent portion unit comprises at least one water-soluble film according to the invention, which is shaped such that the portion unit comprises at least one receiving chamber surrounded by the water-soluble film. The portion unit may comprise a first water- soluble film and a second water-soluble film sealed to one another such to define (and close) the at least one receiving chamber. The water-soluble washing or cleaning agent portion unit is constructed such that the washing or cleaning composition does not leak out of the receiving chamber during storage. However, upon addition of the water-soluble washing or cleaning portion unit to water, the water-soluble film dissolves and releases the contents of the at least one receiving chamber into the wash liquor.

The at least one receiving chamber should be understood as meaning a closed internal space within the portion unit, which holds the washing or cleaning composition. During manufacture, a first water-soluble film may be shaped to comprise an open receiving chamber into which the washing or cleaning 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 receiving chamber. The first and second films are then sealed together along a seal region.

The washing or cleaning agent portion units according to the invention may comprise more than one receiving chamber, preferably two or more receiving chambers, more preferably three or more receiving chambers, even more preferably four or more receiving chambers. The two, three, four or more receiving chambers may be arranged in superposed orientation, i.e., one positioned on top of the other. In such orientation the portion unit will comprise at least three films (top, middle and bottom). Alternatively or in addition, the two, three, four or more receiving chambers may be positioned in a side-by-side orientation, i.e., one orientated next to the other. The receiving chambers may even be orientated in a ’tyre and rim’ arrangement, i.e., a first receiving chamber is positioned next to a second receiving chamber, the first receiving chamber at least partially surrounding the second receiving chamber but not completely enclosing. Alternatively or in addition, one receiving chamber may be completely enclosed within one or more other receiving chamber(s).

In various embodiments, the receiving chambers of washing or cleaning agent portion units according to the invention enclose one another at least partially. Preferred are therefore washing or cleaning agent portion units in which the receiving chambers are arranged in at least one sectional plane about a common n-numbered axis of rotation perpendicular to the sectional plane and wherein at least one receiving chamber is arranged as a central chamber in the central region of the washing or cleaning agent portion unit and the other receiving chamber(s) are arranged around the central chamber.

In case, the portion units comprise two or more receiving chambers, one or more of them may be smaller than the other one.

In case of multi-chamber portion units, each receiving chamber may comprise the same or different compositions. The different compositions could all be in the same form, or they may be in different forms. In various embodiments, at least one of the receiving chambers might be filled with a solid or powdery washing or cleaning composition. In preferred embodiments, the water-soluble washing or cleaning portion units according to the invention comprise one or more receiving chambers), the receiving chamber(s) being filled with washing or cleaning compositions. In various embodiments, the washing or cleaning compositions in the several receiving chamber might be the same or might differ from one another.

In preferred embodiments, the receiving chambers of the washing or cleaning agent portion units are formed by two water-soluble films joined together in a sealing plane, wherein the two water-soluble films have the same composition or may also have a different composition.

In various embodiments, the washing or cleaning agent portion unit may comprise a plurality of receiving chambers each enclosed by at least one water-soluble film according to the invention, wherein the receiving chambers are formed by water-soluble films interconnected in a sealing plane and separated from each other by sealing portions lying in the sealing plane, and wherein the receiving chambers are each filled with a washing or cleaning composition, wherein a plurality of receiving chambers with the number n > 3 is provided, the total internal volume of all the receiving chambers is 10 to 25 ml, and at least one receiving chamber is filled with a powdery washing or cleaning composition.

In various embodiments, the washing or cleaning agent portion unit may comprise a plurality of receiving chambers each enclosed by at least one water-soluble film according to the invention, wherein the receiving chambers are formed by water-soluble films interconnected in a sealing plane and separated from each other by sealing portions lying in the sealing plane, and wherein the receiving chambers are each filled with a washing or cleaning composition, wherein a plurality of receiving chambers with the number n > 3 is provided, the total internal volume of all the receiving chambers is 10 to 25 ml, and at least one receiving chamber is filled with a washing or cleaning composition.

The internal volume of a receiving chamber is defined as the volume of the receiving chamber enclosed by the water-soluble film. Preferred washing or cleaning portion units have three receiving chambers or four receiving chambers or five receiving chambers. The structure of the washing or cleaning agent portion units has technical advantages as the number of receiving chambers increases. Washing or cleaning agent portion units with a plurality of receiving chambers with the number n > 4, preferably with the number n > 5 are therefore preferred.

In various embodiments, the volume of the final washing or cleaning portion unit might be, e.g., 5 to 300 ml, or 10 to 150 ml, or 20 to 100 ml, preferably it is 5 to 50 ml, more preferably it is 10 to 25 ml, even more preferably 10 to 20 ml, most preferably 10 to 18 ml, e.g., 30 ml or less, 25 ml or less, 20 ml or less, 15 ml or less, 10 ml or less, e.g., 5 ml, 6 ml, 7 ml, 8 ml, 9 ml, 10 ml, 11 ml, 12 ml, 13 ml, 14 ml, 15 ml, 16 ml, 17 ml, 18 ml, 19 ml, 20 ml, 21 ml, 22 ml, 23 ml, 24 ml, 25 ml, 26 ml, 27 ml, 28 ml, 29 ml, or 30 ml.

In various embodiments, the washing or cleaning agent portion unit may comprise two or more receiving chambers, and each of the receiving chamber may have a volume of 0.5 to 10 ml, preferably 1 to 7.5 ml, more preferably 2 to 7.5 ml, e.g., 0.5 ml, 0.75 ml, 1 ml, 1 .25 ml, 1 .5 ml, 1 .75 ml, 2 ml, 2.25 ml, 2.5 ml, 2.75 ml, 3 ml, 3.25 ml, 3.5 ml, 3.75 ml, 4 ml, 4.25 ml, 4.5 ml, 4.75 ml, 5 ml, 5.25 ml, 5.5 ml, 5.75 ml, 6 ml, 6.25 ml, 6.5 ml, 6.75 ml, 7 ml, 7.25 ml, 7.5 ml, 7.75 ml, 8 ml, 8.25 ml, 8.5 ml, 8.75 ml, 9 ml, 9.25 ml, 9.5 ml, 9.75 ml, or 10 ml.

All facts, objects and embodiments described for the water-soluble film according to the invention as well as for washing or cleaning agent portion unit are also applicable to this object of the invention. Therefore, explicit reference is made at this point to the disclosure at the appropriate place with the indication that this disclosure also applies to the above washing or cleaning agent portion unit according to the invention.

Cleaning methods & uses

The invention also relates to a method for washing or cleaning an item, in particular textiles or hard surfaces, in particular dishes, wherein in at least one method step a washing or cleaning agent portion unit according to the invention is used.

In various embodiments, the method is characterized in that it is carried out at a temperature of 0°C to 100°C, preferably 20°C to 60°C, particularly preferably 20°C to 40°C. 20°C represents low washing temperature, while 40°C is the preferred/average washing temperature in Europe. This includes both manual and machine methods, with machine methods being preferred due to their more precise controllability, e.g., in terms of the quantities used and exposure times. Methods for cleaning textiles are generally characterized by the fact that various cleaning-active substances are applied to the items to be cleaned in several method steps and washed off after the exposure time, or that the items to be cleaned are otherwise treated with a washing composition or a solution or dilution of this composition.

In preferred embodiments, the washing agent portion unit according to the invention is introduced into the washing liquor of a textile washing machine. In preferred embodiments, the washing agent portion unit is dosed directly into the drum of the textile washing machine.

The washing liquor is the working solution containing the washing composition that acts on the textiles or fabrics and thus comes into contact with the soiling present on the textiles or fabrics. The wash liquor is usually created when the washing process begins and the washing composition is diluted with water, e.g., in a washing machine or in another suitable container.

This object of the invention also comprises a machine dishwashing method. In such method, the cleaning agent portion unit according to the invention can be dosed into the cleaning liquor, e.g., by means of the dosing chamber in the door or by means of an additional dosing container in the interior of the dishwasher. Alternatively, the agent can also be applied directly to the soiled dishes or to one of the inner walls of the dishwasher, e.g. the inside of the door. The method according to the invention is carried out in the interior of a commercially available dishwasher. In a dishwasher, the cleaning program can generally be selected and defined by the consumer before the dishwashing method is carried out. The cleaning program of the dishwasher used in the method according to the invention comprises at least one pre-rinse cycle and one cleaning cycle. Cleaning programs which comprise further cleaning or rinsing cycles, e.g., a rinse cycle, are preferred according to the invention. The method according to the invention is a particularly preferred component of a cleaning program comprising a pre-rinse cycle, a cleaning cycle and a rinse cycle. The method according to the invention is preferably used in conjunction with cleaning programs in which the wash liquor is heated in the course of the cleaning cycle. In preferred embodiments, the cleaning cycle in the course of which the agent is dosed into the interior of the dishwasher is characterized in that in its course the temperature of the cleaning liquor rises to values above 30°C, preferably above 40°C and in particular above 50°C.

Alternative embodiments of this object of the invention also represent methods for the treatment of textile raw materials or for textile care, in which an agent according to the invention becomes active in at least one method step. Preferred among these are methods for textile raw materials, fibers or textiles with natural components, and particularly forthose with wool or silk.

The invention also relates to a method for increasing the proportion of biopolymers in PVOH- containing water-soluble films, comprising the step of adding at least one alkyl polyglycoside, wherein the alkyl polyglycoside has the formula (I)

The invention also relates to the use of at least one alkyl polyglycoside for improving the compatibility of the mixture of at least one biopolymer and at least one PVOH (co-)polymer in water- soluble films, wherein the alkyl polyglycoside has the formula (I)

The invention also relates to the use of at least one alkyl polyglycoside for improving the mechanical properties of PVOH- and/or biopolymer containing water-soluble films, in particular increasing the draw ratio, wherein the alkyl polyglycoside has the formula (I)

All facts, objects and embodiments described for the water-soluble film according to the invention as well as for the method for producing water-soluble films as well as for water-soluble washing or cleaning agent portion unit are also applicable to this object of the invention. Therefore, explicit reference is made at this point to the disclosure at the appropriate place with the indication that this disclosure also applies to the above methods and uses according to the invention.

EXAMPLES

Example 1 : Preparation of water-soluble films

Film compositions according to table 1a and table 1 b have been prepared. First, respective amount of polymer resin has been dissolved in demineralized water in order to achieve 20% total polymer concentration (PVOH and/or biopolymer) in the film. If present, APP is successively incorporated (final concentration of APP in film composition: 0 wt.%, 1 wt.%, 2 wt.%, 3 wt.%, 4 wt.%, 5 wt.%, 6 wt.%, 7 wt.%, 8 wt.%, 9 wt.%, or 10 wt.%). The mixture is stirred at 600 rpm for 1 h in a preheated water bath at 82°C (Film A, B, C, E, F, G, I, J, K, L, N, O, P, R) resp. 55°C (Film D, H, M, Q). Afterwards the solution is degassed in that it is allowed to rest in the water bath until no more bubbles are present.

Afterwards, the films are hand-cast onto a 30 x 40 cm glass plate which is preheated to 90°C using the MULTICATOR 411 Erichsen coating knife. The squeegee is placed on the plate and is filled with approximately 50 g of the respective film composition to be cast. The clearance between the applicator and the glass is 645 pm. The doctor blade is then moved slowly, at a constant speed (4 sec 140 cm) in a straight line over the plate. Immediately after casting the glass plate with the film is placed in a preheated oven at 90°C for 10 min. Afterwards, the films are placed at room temperature for 24 h for drying. Finally, the dried films are stored in a closed cardboard box.

In case of film compositions C, D, G, L, M and P, a commercially available film was dissolved and mixed with additives, before hand-casting as described, wherein the total polymer content was 73 wt.%, based on the total weight of the film composition. The films with 0% APP were also hand-cast in order to be comparable with the admixed ones.

The films produced in such way were then used for producing detergent-filled caps, and/or for performing test methods in order to evaluate physical and mechanical properties as described herein.

Table 1a: Film compositions with APP

* Polyvinyl alcohol polyvinyl acetate copolymer; ** PVOH-based water-soluble film, commercially available from Mitsubishi Chemicals Group; *** PVOH-based water-soluble film, commercially available from Monosol LLC; Y = being present in film

Table 1 b: Film compositions with APG * Polyvinyl alcohol polyvinyl acetate copolymer; ** PVOH-based water-soluble film, commercially available from Mitsubishi Chemicals Group; *** PVOH-based water-soluble film, commercially available from Monosol LLC; Y = being present in film

Example 2: Preparation of detergent-filled caps

Water-soluble films prepared according to Example 1 were used to prepare detergent-filled caps. A piece of the water-soluble film was put above a mold of a deep-drawing apparatus, heated for 1-4 s at 90-110°C (depending on the specific type of film) and drawn into the cavity at an absolute vacuum of 300-700 mbar. The individual film-lined cavities are then filled with a liquid washing composition according to table 2 and then sealed with another film using water sealing, whereby the top film layer is sprayed with 1-4 mg water/cm² and pressed onto the bottom film at 0.5-3 bar. Typically, the resulting cap has a filling volume of approx. 12-25 g.

Table 2: Washing composition

Example 3: Evaluation of physical and mechanical properties of films resp. caps

The following test methods were used for evaluating physical and mechanical properties of films prepared according to example 1 resp caps prepared according to example 2.

Firstly, viscosity will be studied as an important parameter. Different mixtures exhibit varying viscosities, potentially leading to the formation of non-uniform films, particularly concerning thickness, which will also be investigated. Studying the solubility of the film in water is also essential. The film should dissolve adequately to release the detergent into the washing machine without leaving residue. However, it should also maintain integrity, ensuring it does not dissolve before the 30-second threshold set by ASTM for consumer protection. To achieve this, disintegration tests of the film in water in bead and film form will be carried out. Tension tests and measurements of contact angles will also be carried out to measure the resistance of the films. 3.1 . Viscosity

The viscosity of the film composition (20% polymer solution), kept in hot water bath at 82°C (Film C) resp. 55°C (Film D), once the solution is free from any bubbles, is measured using a rotary viscometer (Brookfield Ametek®, No. 4 spindle, preheated to 90°C resp. 60°C). Measurements are taken at 0.5 rpm, 1 rpm, 2 rpm, 4 rpm, 5 rpm, 10 rpm, 20 rpm and 50 rpm. The results are shown in tables 3 and 4 as well as in figures 1 and 2.

Table 3: Viscosity of film compositions out of range

Table 4: Viscosity of film compositions out of range

The addition of APP tends to decrease viscosity of the solution of the film composition (tables 3 and 4, figures 1 and 2).

Since solutions with higher concentrations of APP demonstrate lower viscosities, they can be further concentrated in raw materials to achieve a viscosity like the standard viscosity, which would use less water and energy in the process. Use of APP lead to reduction of viscosity of the film compositions. Hence, the film compositions can be more concentrated leading to improved cost efficiency and less energy; whereas other properties are not negatively affected.

However, it is important to note that this viscosity measurement at different rotations is not precise and have a high percentage of error. It simply provides an approximate idea of the mixture's behavior. For example, at 0.5 rpm, spindle 4 can measure viscosity up to 37,500mPa.s. The values measured at this rotation represent between 1 and 2% of the maximum limit value, which is very small and falls within the margin of error. This also explains the non-linear behavior of the solutions at small rotations. The viscosity values recorded at a rotation of 20 rpm are more accurate and meaningful since at this rotation, spindle 4 can measure a viscosity of up to 937.5mPas, with the measured values then representing 30 to 45% of the maximum value.

The ideal resp. max. casting viscosity is 500 mPas at 20 rpm.

3.2. Film thickness

The thickness of the film is measured at 10 random points using the digital micrometer (Wurth, DE), with 0.001 mm sensitivity. An average value is reported.

The films prepared according to example 1 have an average thickness of approx. 75 to 80 pm.

Commercially available films (e.g., S-2100 from Mitsubishi) have a thickness of 87 pm. Hence, the hand-cast films are slightly thinner.

3.3. Color of film

The color of the films is evaluated by the naked eye, comparing the color of the 87 pm S-2100 film (commercially available from Mitsubishi Chemical Group) with those prepared according to the example 1 . Some films are left to rest under natural light to assess whether UV rays have an impact on any potential color change.

3.4. Film solubility in water

The film is cut into squares measuring 5.5 x 5.5 cm and placed in a 4 x 4 cm frame. The frame is then immersed in 500 ml of water maintained at 23°C, at 285 rpm (magnetic stirrer). The time it takes for the first hole to appear (td) and the complete disappearance of the film from the frame (t_s) are measured. Four trials are conducted, and an average is reported.

Table 5: Film solubility in water (time in sec, together with standard deviation) only one trial

In case of PVOH-based films (Film C) as well as in case of PVOH-casein-blend films (Film D), addition of APP does not have any impact on the water-solubility of the film. In case of casein-based films (Film H), addition of APP improved the water-solubility of the film.

3.5. Tensile strength

Tensile properties indicate the behavior of a material when subjected to tension. Tensile testing is a mechanical test in which the specimen in strip form is clamped into the grips of a tensile testing machine and is stretched at a specific speed until a break occurs, while the applied force is measured.

The main product of a tensile test is a load versus elongation curve which is then converted into a stress versus strain curve. Each material has its own unique stress-strain curve. Different parameters can be obtained from stress-strain diagrams, such as the ultimate tensile strength, stress at break and strain at break.

The mechanical properties are evaluated utilizing Universal tensile tester (Zwick) and the Temperature test chamber with blower (Zwick). Initially, the films (having thickness approx. 80-90 pm) are cut into rectangular pieces (sample width: 15 mm, gauge length: 20 mm). The film pieces are then clamped in the jaws of the tensile tester, which has been heated to 100°C. While the film strip is being stretched, the force is measured. Elongation (mm) and force (N) of the specimen are then recorded. The test has been conducted at 38-40% relative humidity. The test has been performed 4 times, and an average value is reported. The results are shown in tables 8 to 11 . Table 6: Rupture at elongation (mm) & maximum stress (N)

All films according to the invention shows good tensile strength. Film H without APP is very stiff and brittle, hence failed and ruptured immediately. Addition of APP to film H showed major improvements with respect to mechanical properties.

3.6. Sessile drop method

The sessile drop method is the standard method to measure contact angles. Contact angle measurements provide information about the wetting behavior of a liquid on a solid. For that, a drop of liquid is deposited on a solid surface. This drop is then illuminated from one side with a diffuse light source and the contour of the drop is observed from the other side. The contact angle 0c is the angle formed by the liquid at the three-phase boundary where the liquid, gas and solid intersect. With a contact angle of 0°, the drop is completely spread out on the solid surface: this phenomenon is called complete wetting. To get a sessile drop (angle > 0°) on a surface, the surface tension of the liquid must be higher than the surface free energy of the solid. At an angle of 180°, the drop touches the solid at one point only: this phenomenon is called complete dewetting.

The film, cut beforehand, is placed on the surface of the device to obtain as smooth a surface as possible. The dosing syringe is placed above the frame. A light source is placed on one side of the film. This must then be aligned so that the experiment can be easily observed. Finally, the objective of the microscope is fixed perpendicularly to the film. After the light source and objective have been correctly aligned, video acquisition is started at the microscope control panel. 2.5 pl of water is dispensed onto the film surface via the dosing device. The drop is observed via the microscope.

The measurement starts as soon as the droplet touches the film surface. The drop initially lies in the form of a hemisphere on the film surface and spreads out, depending on how hydrophobic or hydrophilic the surface is. The contact angle 0c, ellipse fitting and circle fitting is measured. The results are shown in table 9 as well as in figures 3 and 4.

Table 7: Contact angles 3.7. Liquid retention time of agent portion units

The caps prepared according to example 2 is completely immersed in a container of water maintained at 20°C. The burst time of each cap is measured. The test is conducted 24 hours after the caps is made, and then again 7 days later. The test was repeated three times and the average value is reported.

The caps prepared according to example 2 are placed in a 4 x 4 cm frame. The frame is then immersed in 500 ml of water maintained at 23°C, at 285 rpm (magnetic stirrer). The time it takes for the first holes to appear (t) are measured with freshly prepared caps as well as with caps stored for 7 days at room temperature. Four trials are conducted, and an average is reported.

Success criteria is a liquid retain over 30s and it should not take longer than 180s for fresh samples.

Table 8: Liquid retention time (LRT)

3.8. Draw Ratio test

With the so-called "Draw ratio test", the liquid retention time of water-soluble films having different draw ratios are evaluated. While using a plate having several cavities of different depth, a film deepdrawn into such cavities, undergoes different stretch intensities depending on the depth of the cavity. Advantageously, the same film can be evaluated with respect to different stretch intensities resp. draw ratios. By using this test method, it is possible to determine the relation between stretchability of a water-soluble film and its solubility in water. In particular, it is possible to determine how much a water- soluble film can be stretched before a detergent cap made from it can no longer remain stable in water at 20°C for the 30 s required by law. While good water-solubility is advantageous for use of the washing or cleaning agent portion units in washing or cleaning processes, for safety reasons immediate release of the washing or cleaning composition contained in the portion unit has to be prevented, e.g., in case a child places such portion unit into the mouth. Hence, according to safety regulations the water-soluble film has to retain its content for at last 30 s when the water-soluble washing or cleaning portion unit is placed in water at 20°C.

The test was carried out at different draw ratios ranging from 2.6 to 1 .8. The draw ratio is the ratio between the length of the material before and after a stretching process. A draw ratio of 2.6 means that the film has been stretched to a length 2.6 times greater than its original length. The stretch is therefore greater than at a draw ratio of 1 .8. A higher draw ratio indicates that the film is more stretched, thinner, and therefore its properties such as water resistance may be altered.

The plate to be used has nine hemispherical cavities (diameter 20 mm), wherein each of the cavities become deeper in steps of 0.5 mm, i.e., the first cavity has a depth of 10.5 mm, the second cavity has a depth of 11 mm, the third cavity has a depth of 11 .5 mm, and so forth, the ninth cavity has a depth of 14.5 mm. Each 0.5 mm step leads to an average factor between the projected and inner surface increasing in steps of 0.1 . The first cavity with depth of 10.5 mm corresponds to draw ratio of 1 .8, the second cavity with depth of 11 mm corresponds to draw ratio of 1 .9, the third cavity with depth of 11.5 mm corresponds to draw ratio of 2.0, and so forth, the ninth cavity with depth of 14.5 mm corresponds to draw ratio of 2.6.

A piece of the water-soluble film to be tested is put above the plate, heated for 1-4 seconds at 90- 110°C (or higher, depending on the specific type of film) and drawn into the cavity at an absolute vacuum of 300-700 mbar. The individual film-lined cavities are then filled with liquid (e.g., liquid washing or cleaning composition according to table 2) and then sealed with another film using water sealing, whereby the top film layer is sprayed with 1-4 mg water/cm² and pressed onto the bottom film at 0.5-3 bar.

The chambers/caps are individually released and evaluated. The liquid retention times after 1 day as well as 7 day storage have been evaluated (storage at room temperature in closed cardboard box). The test has been performed four times, and an average value is reported. The results are shown in tables 11 to 14.

Table 9: Liquid retention time (sec) after 1 day

Table 10: Liquid retention time (sec) after 7 days Table 11 : Draw ratio test after 1 day

4/4 means that four of four trials have passed the test; passed = the water-soluble film retains its content for at last 30 s when the film is placed in water

Table 12: Draw ratio test after 7 days

Addition of APP leads to films which can be stretched at higher ratios while keeping the liquid for at least 30 seconds.

3.9. Burst strength

According to European regulations, the mechanical resistance to compression must be at least 300 N. That is why, in the caps burst test, a force of 350 N is applied to the caps prepared according to example 2 to see if it withstands. The test is conducted at 38-40% relative humidity and 20°C. The test is conducted 24 hours after the caps was made, and then again 7 days later. The test was conducted in four replicates. The test is considered passed when all of the replicates have withstood a force of 350 N.

Table 13: Burst strength results

Addition of APP in various amounts does not affect the burst strength of the caps made of films according to the invention.

Example 4: Exemplary washing and cleaning compositions

Water-soluble films according to the invention can be used to produce various washing or cleaning agent portion units.

Table 14: Textile washing detergent unit dose (single phase) Table 15: Two-phase automatic dishwashing detergent Table 16: Solid automatic dishwashing detergent, wrapped in water-soluble film

Claims

1 . A water-soluble film, in particular water-soluble film for washing and/or cleaning agent portion units, wherein the film comprises, based on the total weight of the film composition,

(B) 2.5 to 30 wt.%, preferably, 5 to 25 wt.%, of at least one biopolymer,

2. The water-soluble film according to claim 1 , wherein the at least one PVOH (co-)polymer is selected from

(i) a vinyl alcohol vinyl acetate copolymer; and/or

(iii) a sulfonated polyvinyl alcohol copolymer; and/or

(vi) mixtures thereof.

3. The water-soluble film according to claim 1 or 2, wherein

4. The water-soluble film according to any of claims 1 to 3, wherein the at least one alkyl polyglycoside is selected from alkyl polyglycosides described by the formula (II) (II), in which R¹ and R² are same or different and independently selected from H or OH, R³ is selected from H or CH2OH, represents branched or unbranched alkyl or alkenyl group, n represents 4 to 18, in particular 5 to 15, and p represents numbers from 1 to 10.

5. The water-soluble film according to any of claims 1 to 4, wherein the at least one alkyl polyglycoside is selected from

(i) alkyl polyglucosides (APG) derived from glucose and described by the formula (III) in which represents branched or unbranched alkyl or alkenyl group, n represents 7 to 18, preferably 10 to 15, and p represents numbers from 1 to 10; and/or

(ii) alkyl polypentosides (APP) derived from xylose and described by the formula (IV) (IV), in which represents branched or unbranched alkyl or alkenyl group, n represents 4 to 15, in particular 5 to 10, and p represents numbers from 1 to 10.

6. The water-soluble film according to any of claims 1 to 5, wherein the at least one alkyl polyglycoside is an alkyl polypentoside (APP) and/or being selected from formula (V) or formula (VI)

7. The water-soluble film according to any of the claims 1 to 6, wherein the at least one alkyl polyglycoside is selected from alkyl polyglycosides having a hydrophilic-lipophilic balance (HLB) value equal or greater than 10, preferably equal or greater than 12, more preferably equal or greater than 15.

8. The water-soluble film according to any of the claims 1 to 7, wherein the at least one biopolymer is selected from the group consisting of starches, amylose and amylopectin, celluloses, carboxy methyl cellulose (CMC), hydroxyethyl cellulose (HEC), hydroxypropyl cellulose (HPC), hydroxypropyl methyl cellulose (HPMC), methyl cellulose (MC), ethyl cellulose (EC), glucans, p- glucans, a-glucans, wheat proteins, soy proteins, pea proteins, potato proteins, whey proteins, corn proteins, caseins, aS1-, aS2-, p- and K-casein, caseinates, bovine casein salts, goat casein salts, sheep casein salts, derivatives of the foregoing, and mixtures thereof, preferably starches, amylose and amylopectin, carrageenans, wheat proteins, soy proteins, pea proteins, potato proteins, whey proteins, corn proteins, caseins, aS1-, aS2-, p- and K-casein, caseinates, bovine casein salts, goat casein salts, sheep casein salts, derivatives of the foregoing, and mixtures thereof.

9. The water-soluble film according to any of the claims 1 to 8, wherein the film comprises at least two biopolymers, wherein the at least two biopolymers are as described in claim 3, preferably being selected from the group consisting of starches, amylose and amylopectin, celluloses, carboxy methyl cellulose (CMC), hydroxyethyl cellulose (HEC), hydroxypropyl cellulose (HPC), hydroxypropyl methyl cellulose (HPMC), methyl cellulose (MC), ethyl cellulose (EC), glucans, p-glucans, a-glucans, wheat proteins, soy proteins, pea proteins, potato proteins, whey proteins, corn proteins, caseins, aS1-, aS2-, p- and K-casein, caseinates, bovine casein salts, goat casein salts, sheep casein salts, derivatives of the foregoing, and mixtures thereof, preferably starches, amylose and amylopectin, carrageenans, wheat proteins, soy proteins, pea proteins, potato proteins, whey proteins, corn proteins, caseins, aS1-, aS2-, p- and K-casein, caseinates, bovine casein salts, goat casein salts, sheep casein salts, derivatives of the foregoing, and mixtures thereof.

10. The water-soluble film according to any of the claims 1 to 9, wherein the total amount of PVOH (co-)polymers and biopolymers is 52.5 to 80 wt.%, preferably 60 to 75 wt.%; and/or the ratio of the at least one PVOH (co-)polymer and the at least one biopolymer is between 20:1 and 2.5:1 , preferably between 15:1 and 10:1.

11. The water-soluble film according to any of the claims 1 to 10, wherein the film also comprises at least one further ingredient, wherein the at least one further ingredient is selected from the group consisting of bittering agents, solvents, in particular water, as well processing agents, in particular plasticizers, lubricants, release agents, fillers, extenders, cross-linking agents, antiblocking agents, antioxidants, detackifying agents, and antifoam.

12. The water-soluble film according to any of the claims 1 to 11 , wherein the film has a thickness of 30 to 100 pm, preferably 50 to 95 pm, more preferably 60 to 90 pm; and/or the film has a draw ratio of 1 .5 to 3.0, preferably 1 .8 to 2.6, more preferably 1 .8 to 2.3.

13. A washing and/or cleaning agent portion units comprising at least one film according to any of the claims 1 to 12 and at least one washing and/or cleaning composition, wherein the washing/or cleaning composition is incorporated into at least one receiving chamber surrounded by the at least one film.

14. A method for producing a water-soluble film according to any of the claims 1 to 12, comprising the steps of a) providing a PVOH slurry, wherein the PVOH solution comprises at least one PVOH (co-)polymer and wherein the PVOH (co-)polymer is selected from at least one polyvinyl alcohol homopolymer, at least one polyvinyl alcohol copolymer or a mixture thereof, b) adding additives as required, in particular adding at least one biopolymer, as described herein, and/or at least one alkyl polyglycoside, preferably selected from alkyl polyglucosides (APG), alkyl polypentosides (APP) and mixtures thereof, and/or further ingredients, as described herein, c) heating the slurry to form a solution, and d) casting the solution of step c) on a suitable surface to create a film having a thickness in the range of 30 to 100 pm, preferably 50 to 95 pm, more preferably 60 to 90 pm.

15. Method for producing a washing and/or cleaning agent portion unit according to claim 13, comprising the steps of a) transporting a first water-soluble film, which is a film according to any of claims 1 to 12, in the direction of a dosing station at a speed above 0.04 m/s, preferably above 0.08 m/s, b) molding the first water-soluble film into the cavities of a deep-drawing die located below the water-soluble film, so as to form at least one cavity having a maximum diameter in the direction of travel of the film of between 3 and 75 mm, wherein the film has a draw ratio of 1 .5 to 3.0, preferably

16. Method for increasing the proportion of biopolymers in PVOH-containing water-soluble films, comprising the step of adding at least one alkyl polyglycoside, wherein the alkyl polyglycoside has the formula (I)

17. Use of at least one alkyl polyglycoside for improving the compatibility of the mixture of at least one biopolymer and at least one PVOH (co-)polymer in water-soluble films, wherein the alkyl polyglycoside has the formula (I)

18. Use of at least one alkyl polyglycoside for improving the mechanical properties of PVOH- and/or biopolymer containing water-soluble films, in particular increasing the draw ratio, wherein the alkyl polyglycoside has the formula (I)

19. The use according to claim 15, wherein the film has a thickness in the range of 30 to 100 pm, preferably 50 to 95 pm, more preferably 60 to 90 pm and/or a draw ratio of 1 .5 to 3.0, preferably 1 .8 to 2.6, more preferably 1 .8 to 2.3.