RU2776483C2 - Water-soluble films with low friction coefficient - Google Patents

Abstract

FIELD: chemistry; packaging.

SUBSTANCE: invention relates to water-soluble films based on polyvinyl alcohol and packages related to them. Water-soluble film with low static friction coefficient for the production of packaging is described, containing a mixture of (i) water-soluble polyvinyl alcohol, (ii) plasticizer selected from a group consisting of glycerin, propylene glycol, sorbitol, trimethylolpropane, polyethylene glycols, polymers of glycerin and propylene oxide, 2-methyl-1,3-propanediol, xylitol and combinations of the above-mentioned, and (iii) hydroxypropyl-modified starch with amylose content in the range from 65% to 95%. In this case, polyvinyl alcohol is present in the amount from 20% by wt. to 95% by wt. per the total weight of film, and oxy-propylated starch is present in the amount from 5 wt. pts. to 30 wt. pts. per 100 wt. pts. of resin.

EFFECT: creation of water-soluble films, from which water-soluble packaging can be produced, preserving water solubility along with reduced tendency to adhesion to other water-soluble films.

69 cl, 2 dwg, 6 tbl, 47 ex

Description

FIELD OF TECHNOLOGY

[0001] The present invention relates generally to water-soluble films and related packages. More specifically, the invention relates to polyvinyl alcohol based water soluble films which can have low coefficients of friction and consequently reduced tendency to adhere to surfaces such as processing equipment or other water soluble films.

BACKGROUND OF THE INVENTION

[0002] Water-soluble polymeric films are commonly used as packaging materials to facilitate dispersion, filling, dissolution and dosing of the material to be delivered. The consumer may add the sachet composition directly to a mixing container such as a bucket, sink, or any container suitable for filling with water. This provides the advantage of accurate dosing and elimination of the need for the consumer to determine the quantitative content of the composition. By using a bagged composition, it is also possible to reduce the error associated with the supply of material from the container containing it, for example, when pouring or withdrawing material. In view of the above, the use of soluble polymer film bags with a predetermined quantitative content of substances provides the consumer with convenience in various areas of their application.

[0003] However, water-soluble films derived from water-soluble polymers may adhere to the surfaces on which they are formed (or which are formed on their basis, for example, the surface of bags), and/or other water-soluble films. Such problems may arise, in particular, when the film is formed into bags that are stored together in secondary packaging. In order to eliminate sticking to technological surfaces and sticking of bags during storage, anti-adhesives were used to reduce the degree of stickiness of water-soluble films. However, the introduction of release agents into the composition, primarily under conditions of work with a significant level of load, as a rule, has a negative effect on the mechanical properties of the resulting films. In particular, as a rule, the tensile strength of water-soluble films is reduced, which leads to difficulties in the manufacture of dosed bags from films. Alternative solutions include dusting the films with talc, starch or similar particles; however, the dusting process is generally messy and results in wastage of powder materials and equipment downtime.

[0004] As a result, there is a need in the art for water soluble films from which water soluble packages can be made that retain the property of water solubility along with a reduced tendency to stick to other water soluble films.

SUMMARY OF THE INVENTION

[0005] In one aspect of the invention, a water-soluble film is provided that contains a mixture of water-soluble polyvinyl alcohol, a plasticizer and starch, with polyvinyl alcohol contained in an amount of from about 20% of the mass. up to about 95% of the mass. based on the total weight of the film, and the starch contains hydroxypropyl-modified starch, the amount of which is in the range from about 5 m.h. up to about 30 m.h. per 100 m.h. resins.

[0006] In a related aspect of the invention, there is provided a sealed article containing a water-soluble film in the form of a bag, the internal volume of which is defined by the film, while the water-soluble film contains a mixture of water-soluble polyvinyl alcohol, a plasticizer and starch, and the polyvinyl alcohol is contained in an amount of from about 20% of the mass. up to about 95% of the mass. based on the total weight of the film, and the starch contains hydroxypropyl-modified starch, the amount of which is in the range from about 5 m.h. up to about 30 m.h. per 100 m.h. resins.

[0007] In another aspect of the invention, a water-soluble film is provided that contains a mixture of water-soluble polyvinyl alcohol, a plasticizer and modified starch, with polyvinyl alcohol contained in an amount of from about 20% of the mass. up to about 95% of the mass. based on the total weight of the film, and the modified starch has a degree of modification of more than about 2%, and its amount is in the range from about 2.5 m.h. up to about 30 m.h. per 100 m.h. resins.

[0008] In a related aspect of the invention, a sealed article is provided comprising a water-soluble film in the form of a bag, the internal volume of which is defined by the film, while the water-soluble film contains a mixture of water-soluble polyvinyl alcohol, a plasticizer and modified starch, and the polyvinyl alcohol is contained in an amount of from about 20% of the mass . up to about 95% of the mass. based on the total weight of the film, and the modified starch has a degree of modification of more than about 2%, and at the same time its amount is in the range from about 2.5 m.h. up to about 30 m.h. per 100 m.h. resins.

[0009] In another aspect of the invention, a water-soluble film is provided that contains a mixture of water-soluble polyvinyl alcohol, a plasticizer and unmodified starch, with polyvinyl alcohol contained in an amount of from about 20% of the mass. up to about 95% of the mass. based on the total weight of the film, and the content of amylose in starch is from about 20% to about 80%.

[0010] In a related aspect of the invention, there is provided a sealed product comprising a water-soluble film in the form of a bag, the internal volume of which is defined by the film, while the water-soluble film contains a mixture of water-soluble polyvinyl alcohol, a plasticizer and unmodified starch, and the polyvinyl alcohol is contained in an amount of from about 20% of the mass . up to about 95% of the mass. based on the total weight of the film, and the content of amylose in starch is from about 20% to about 80%.

[0011] In another aspect of the invention, a water-soluble film is provided that contains a mixture of water-soluble polyvinyl alcohol, a plasticizer and hydroxypropyl-modified starch, with polyvinyl alcohol contained in an amount of from about 20% of the mass. up to about 95% of the mass. based on the total weight of the film, and the content of amylose in the starch is from about 23% to about 95%, while the polyvinyl alcohol contains either unmodified polyvinyl alcohol or an anion modified polyvinyl alcohol copolymer, provided that the anionic modifier is not an acrylate.

[0012] In a related aspect of the invention, a sealed article is provided comprising a water-soluble film in the form of a bag, the internal volume of which is defined by the film, while the water-soluble film contains a mixture of water-soluble polyvinyl alcohol, a plasticizer and hydroxypropyl-modified starch, and the polyvinyl alcohol is contained in an amount of from about 20 % wt. up to about 95% of the mass. based on the total weight of the film, and the content of amylose in the starch is from about 23% to about 95%, while the polyvinyl alcohol contains either unmodified polyvinyl alcohol or an anion modified polyvinyl alcohol copolymer with the proviso that the anionic modifier is not an acrylate.

[0013] In another aspect of the invention, there is provided a sealed article containing a water-soluble film in the form of a bag, the internal volume of which is defined by the film, the water-soluble film being selected according to any aspect or embodiment of the present invention described herein.

[0014] It is contemplated that additional characteristics of the compositions described herein, which include, but are not limited to, the types of components used and their concentration ranges, may be selected from various aspects, embodiments, and examples provided herein. For example, any additional characteristics presented in the description in this document can be used in conjunction with the embodiments of the invention and the methods for selecting the compositions described in examples 6 to 45.

[0015] Additional aspects and advantages of the invention will become apparent to those skilled in the art upon reading the following detailed description. While the films and bags of the present specification contemplate various forms of the invention, the following description contains specific embodiments, with the understanding that the description is illustrative and does not limit the invention to the particular embodiments described herein.

BRIEF DESCRIPTION OF GRAPHICS

[0016] To further improve the understanding of the present invention, two graphic figures are attached hereto.

[0017] In FIG. 1 shows visual interpretations of amylose and amylopectin.

[0018] In FIG. 2 shows an example of a device for measuring the coefficient of friction of a film sample.

DETAILED DESCRIPTION OF THE INVENTION

[0019] In one aspect of the invention, a water-soluble film is provided that contains a mixture of water-soluble polyvinyl alcohol, a plasticizer and starch, with polyvinyl alcohol contained in an amount of from about 20% of the mass. up to about 95% of the mass. based on the total weight of the film, and the starch contains hydroxypropyl-modified starch, the amount of which is in the range from about 5 m.h. up to about 30 m.h. per 100 m.h. resins.

[0020] The films of this aspect of the invention can surprisingly be made to provide a combination of (1) excellent bag convertibility (convertibility) using automated equipment at high starch concentrations, characterized by tensile strength values ranging from about 45 MPa to about 60 MPa in accordance with the Tensile Strength Test procedure described below; (2) excellent water solubility, characterized by a cold water (10°C) dissolution time of 100 seconds or less according to MSTM-205; and (3) good inter-film release properties, characterized by a relatively low static coefficient of friction (COF) of about 5 or less, measured using the Friction Coefficient Test procedure described below.

[0021] In a related aspect of the invention, a sealed article is provided comprising a water-soluble film in the form of a bag, the internal volume of which is defined by the film, while the water-soluble film contains a mixture of water-soluble polyvinyl alcohol, a plasticizer and starch, and the polyvinyl alcohol is contained in an amount of from about 20% of the mass. up to about 95% of the mass. based on the total weight of the film, and the starch contains hydroxypropyl-modified starch, the amount of which is in the range from about 5 m.h. up to about 30 m.h. per 100 m.h. resins.

[0022] In embodiments, the amylose content of the hydroxypropyl modified starch is in the range of about 65% to about 95%. In the context of this document, and unless otherwise indicated, the percentage of amylose is a weight percent based on the total weight of amylose and amylopectin in starch, consisting largely of water, amylose and amylopectin, and containing about 12% of the mass. water. For example, starch containing 65% amylose contains 35% amylopectin. As shown in Figure 1, amylose is a linear helical polymer built from α-D-glucose units linked by α(1→4) glycosidic bonds, while amylopectin is a highly branched glucose polymer linked linearly via (1→ 4) glycosidic bonds, while branching occurs due to α(1→6) bonds and is observed, for example, every 24-30 glucose units. Regardless of theory, typical modified starches (eg, hydroxypropyl modified, oxyethylated starches, or acetate modified starches) are expected to contain modifications (eg, hydroxypropyl, hydroxyethyl, or acetate groups) distributed randomly or substantially randomly throughout the amylose and amylopectin chains. In one aspect of the invention, the modified starch (eg, hydroxypropyl-modified or oxyethylated starch) used in the present invention has modifications distributed randomly or substantially randomly throughout the amylose and amylopectin chains. In an alternative aspect of the invention, the modified starch (eg, hydroxypropyl-modified or oxyethylated starch) used in the present invention has modifications distributed non-randomly or substantially non-randomly throughout the amylose and amylopectin chains.

[0023] In embodiments, the hydroxypropyl modified starch may have a degree of modification ranging from about 4% to about 8%. In the context of this document, and unless otherwise indicated, the degree of modification of starch is a mass percent. Starch modification can also be characterized as a degree of substitution (DS) with a value from 0 to 3, with DS equal to 0 in the absence of modified OH groups in each glucose ring, and DS equal to 3 in the case of modification of all 3 OH groups in each glucose ring. ring. In embodiments, the DS for hydroxypropyl modified starch may be, for example, in the range of about 0.05 to about 0.4, or about 0.1 to about 0.3, or about 0.1, about 0.2 , about 0.3, or about 0.4. In embodiments of the invention, the amount of starch is in the range from about 6 m.h. up to about 16 m.h. per 100 m.h. resins. In embodiments of the invention, the amount of starch is in the range from about 6 m.h. up to about 10 m.h. per 100 m.h. resins. In some embodiments of the invention, the content of starch in the water-soluble film is in the range from about 12 m.h. up to about 16 m.h. per 100 m.h. resins. In embodiments of the invention, the tensile strength of the water soluble film is at least 40 MPa as measured in accordance with the Tensile Strength Test methodology described herein. In embodiments, the polyvinyl alcohol is a polyvinyl alcohol selected from the group consisting of a polyvinyl alcohol homopolymer, an anionically modified polyvinyl alcohol copolymer, and combinations of the foregoing.

[0024] In embodiments of the invention, the values of the static coefficient of friction of glossy surfaces (GG) for a water-soluble film are about 5 or less, or from about 0.1 to about 5, or from about 0.5 to about 5 as measured in accordance with by the Tensile Strength Test procedure described in this document. The glossy side of the water soluble film indicates the outside of the water soluble film cast on the mold surface. The matte side of the water-soluble film refers to the side adjacent to the molding surface of the water-soluble film, obtained by casting on the molding surface. In embodiments of the invention, the water-soluble film has a reduced static friction coefficient GG compared to a film of the same composition that does not contain starch. The reduction in the static friction coefficient GG leads to a decrease in the likelihood of the film (or the bag formed from it) sticking to the surface on which it was formed (or converted, for example, into bags) and/or to other water-soluble films. In the context of this document, the term "static coefficient of friction of glossy surfaces (GG)" refers to the static coefficient of friction between the glossy sides of two water-soluble films of the same composition. In the context of this document, the term "static coefficient of friction glossy and matte surface)" refers to the static coefficient of friction between the glossy and matte side of two water-soluble films of the same composition. In the context of this document, the term "static coefficient of friction matte surfaces)" refers to the static coefficient of friction between the matte sides of two water-soluble films of the same composition. The coefficients of friction described in this document are the static friction coefficients of glossy surfaces. For a given cast-formed water-soluble film, the static friction coefficient of glossy surfaces is generally higher than the static friction coefficient of glossy and matte surfaces and the static friction coefficient of matte surfaces. Regardless of the theory, it is assumed that the value of the static friction coefficient of the glossy surfaces of the cast film reflects the static friction coefficient of the blown film, the composition of which is similar to the composition of the cast film, while the blown films are not cast on the forming surface and hence all sides of such films can be considered outer or "glossy" sides.

[0025] In embodiments of the invention, the sealed product contains the composition placed in the interior of the bag. In embodiments of the invention, the composition placed in the interior of the bag is a synthetic detergent composition. In embodiments of the invention, the synthetic detergent composition contains a surfactant, a bleach, an enzyme, a perfume, a dye or pigment, a solvent, and combinations of the foregoing.

[0026] In another aspect of the invention, a water-soluble film is provided that contains a mixture of water-soluble polyvinyl alcohol, a plasticizer and a modified starch, with polyvinyl alcohol contained in an amount of from about 20% of the mass. up to about 95% of the mass. based on the total weight of the film, and the modified starch has a degree of modification of more than about 2%, and at the same time its amount is in the range from about 2.5 m.h. up to about 30 m.h. per 100 m.h. resins.

[0027] The films of this aspect of the invention can surprisingly be made to provide a combination of (1) excellent bag convertibility (convertibility) using automated equipment at high starch concentrations, characterized by tensile strength values ranging from about 45 MPa to about 60 MPa in accordance with the Tensile Strength Test procedure described below; (2) excellent water solubility, characterized by a cold water (10°C) dissolution time of 100 seconds or less according to MSTM-205; and (3) good inter-film release properties, characterized by a relatively low static coefficient of friction (COF) of about 5 or less, measured using the Friction Coefficient Test procedure described below.

[0028] In a related aspect of the invention, a sealed article is provided comprising a water-soluble film in the form of a bag, the internal volume of which is defined by the film, while the water-soluble film contains a mixture of water-soluble polyvinyl alcohol, a plasticizer and modified starch, and the polyvinyl alcohol is contained in an amount of from about 20% of the mass . up to about 95% of the mass. based on the total weight of the film, and the modified starch has a degree of modification of more than about 2%, and at the same time its amount is in the range from about 2.5 m.h. up to about 30 m.h. per 100 m.h. resins.

[0029] In embodiments of the invention, the modified starch has a degree of modification from about 4% to about 8%. In embodiments of the invention, the amylose content of the modified starch ranges from about 65% to about 95%. In embodiments of the invention, the modified starch contains a hydroxyalkyl modification with an alkyl chain length of three or more carbon atoms, or three to eight carbon atoms, or three to five carbon atoms, or three carbon atoms. As used herein, the term "alkyls" refers to straight chain and branched saturated hydrocarbon radicals containing from one to thirty carbon atoms, for example, from one to twenty carbon atoms or from one to ten carbon atoms. Non-limiting examples of alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl (1-methylpropyl), tert-butyl (1,1-dimethylethyl), 3,3-dimethylpentyl, and 2-ethylhexyl. Unless otherwise indicated, an alkyl group may be an unsubstituted alkyl group or a substituted alkyl group. In the context of this document, the term "hydroxyalkyl" means an alkyl group that is substituted with a hydroxyl group. Non-limiting examples of hydroxyalkyl groups include hydroxymethyl, hydroxyethyl, hydroxypropyl, hydroxybutyl, and the like.

[0030] In embodiments, the polyvinyl alcohol is a polyvinyl alcohol selected from the group consisting of a polyvinyl alcohol homopolymer, an anionically modified polyvinyl alcohol copolymer, and combinations of the foregoing. In embodiments of the invention, the amount of starch is in the range from about 6 m.h. up to about 16 m.h. per 100 m.h. resins. In embodiments of the invention, the amount of starch is in the range from about 6 m.h. up to about 10 m.h. per 100 m.h. resins. In embodiments of the invention, the amount of starch is in the range of about 12 m.h. up to about 16 m.h. per 100 m.h. resins. In embodiments of the invention, the tensile strength of the water-soluble film is at least about 40 MPa to about 60 MPa, as measured in accordance with the Tensile Test methodology described herein. In embodiments of the invention, the values of the static coefficient of friction of glossy surfaces (GG) for a water-soluble film are about 5 or less, or from about 0.1 to about 5, or from about 0.5 to about 5, or from about 0.1 to about 3, or from about 0.1 to about 2 as measured in accordance with the Tensile Strength Test methodology described herein. In embodiments of the invention, the water-soluble film is characterized by a reduced static coefficient of friction of glossy surfaces (GG) compared to a film of the same composition that does not contain starch.

[0031] In embodiments of the invention, the sealed article contains the composition located in the interior of the bag. In embodiments of the invention, the composition placed in the interior of the bag is a synthetic detergent composition. In embodiments of the invention, the synthetic detergent composition contains a surfactant, a bleach, an enzyme, a perfume, a dye or pigment, a solvent, and combinations of the foregoing.

[0032] In another aspect of the invention, a water-soluble film is provided containing a mixture of water-soluble polyvinyl alcohol, a plasticizer and unmodified starch, with polyvinyl alcohol contained in an amount of from about 20 wt%. up to about 95% of the mass. based on the total weight of the film, and the content of amylose in starch is from about 20% to about 80%.

[0033] Films according to this aspect of the invention can surprisingly be made with the ability to obtain the combination of (1) excellent water solubility, characterized by a dissolution time in cold water (10 ° C) equal to 100 seconds or less in accordance with MSTM-205; (2) excellent inter-film release properties, characterized by a relatively low static coefficient of friction (COF) of smooth surfaces of about 1 or less, as measured by the Friction Coefficient Test procedure described below; (3) good bag convertibility (convertibility) using automated equipment at high starch concentrations, characterized by tensile strength values ranging from about 40 MPa to about 60 MPa in accordance with the Tensile Strength Test procedure described below.

[0034] In a related aspect of the invention, a sealed article is provided comprising a water-soluble film in the form of a bag, the internal volume of which is defined by the film, while the water-soluble film contains a mixture of water-soluble polyvinyl alcohol, a plasticizer and unmodified starch, and polyvinyl alcohol is contained in an amount of from about 20% of the mass . up to about 95% of the mass. based on the total weight of the film, and the content of amylose in starch is from about 20% to about 80%.

[0035] In embodiments of the invention, the content of polyvinyl alcohol in a water-soluble film is in the range from about 85% wt. up to about 95% wt. based on the total weight of the film. In embodiments of the invention, the amount of unmodified starch is in the range of about 2 m.h. up to about 30 m.h. per 100 m.h. resins. In embodiments of the invention, the amount of unmodified starch is in the range of about 2 m.h. up to about 5 m.h. per 100 m.h. resins. In embodiments of the invention, the values of the static coefficient of friction of glossy surfaces (GG) for a water-soluble film are about 1 or less. In embodiments of the invention, the water-soluble film is characterized by a reduced static coefficient of friction of glossy surfaces compared to a film of the same composition that does not contain starch.

[0036] In embodiments of the invention, the sealed article contains the composition located in the interior of the bag. In embodiments of the invention, the composition placed in the interior of the bag is a synthetic detergent composition. In embodiments of the invention, the synthetic detergent composition contains a surfactant, a bleach, an enzyme, a perfume, a dye or pigment, a solvent, and combinations of the foregoing.

[0037] In another aspect of the invention, a water-soluble film is provided that contains a mixture of water-soluble polyvinyl alcohol, a plasticizer and hydroxypropyl-modified starch, with polyvinyl alcohol contained in an amount of from about 20 wt%. up to about 95% of the mass. based on the total weight of the film, and the content of amylose in the starch is from about 23% to about 95%, while the polyvinyl alcohol contains either unmodified polyvinyl alcohol or an anion modified polyvinyl alcohol copolymer, provided that the anionic modifier is not an acrylate.

[0038] The films of this aspect of the invention can surprisingly be made capable of obtaining a combination of (1) excellent bag convertibility (convertibility) using automated equipment at high starch concentrations, characterized by tensile strength values ranging from about 45 MPa to about 60 MPa in accordance with the Tensile Strength Test procedure described below; (2) excellent solubility in water, characterized by a dissolution time in cold water (10 °C) of 100 seconds or less; and (3) good inter-film release properties, characterized by a relatively low static coefficient of friction (COF) of about 5 or less, measured using the Friction Coefficient Test procedure described below.

[0039] In a related aspect of the invention, a sealed article is provided comprising a water-soluble film in the form of a bag, the internal volume of which is formed by the film, while the water-soluble film contains a mixture of water-soluble polyvinyl alcohol, a plasticizer and hydroxypropyl-modified starch, and the polyvinyl alcohol is contained in an amount of from about 20 % wt. up to about 95% wt. based on the total weight of the film, and the content of amylose in the starch is from about 23% to about 95%, while the polyvinyl alcohol contains either unmodified polyvinyl alcohol or an anionically modified polyvinyl alcohol copolymer with the proviso that the anionic modifier is not an acrylate.

[0040] In embodiments of the invention, the amount of starch is in the range from about 5 m.h. up to about 12 m.h. per 100 m.h. resins. In embodiments of the invention, the values of the static coefficient of friction of glossy surfaces (GG) for a water-soluble film are about 5 or less, or from about 0.1 to about 5, or from about 0.5 to about 5, or from about 0.1 to about 3, or from about 0.1 to about 2. In embodiments, the amylose content of the modified starch ranges from about 50% to about 95%. In embodiments of the invention, the hydroxypropyl-modified starch contains more than 2% hydroxypropyl modification, for example, from 2.1% to 8% hydroxypropyl modification. In embodiments, the hydroxypropyl modified starch contains from about 4% to about 8% hydroxypropyl modification. In embodiments of the invention, the water-soluble film is characterized by a reduced static coefficient of friction of glossy surfaces compared to a film of the same composition that does not contain starch.

[0041] In embodiments of the invention, the sealed article contains the composition located in the interior of the bag. In embodiments of the invention, the composition placed in the interior of the bag is a synthetic detergent composition. In embodiments of the invention, the synthetic detergent composition contains a surfactant, a bleach, an enzyme, a perfume, a dye or pigment, a solvent, and combinations of the foregoing.

[0042] A water-soluble film as used herein is a film about 1.5 mils (about 0.038 mm) thick that dissolves in water in 300 seconds or less at 20°C (68°F) in accordance with the MonoSol Test Method - MSTM -205.

[0043] As used herein, the term "comprising" refers to various components, ingredients, or steps that can be used together in the practice of the present invention. Accordingly, the expression "comprising" includes the more restrictive terms "primarily consisting of" and "consisting of". The present compositions may contain, predominantly consist of, or consist of the essential and optional elements described herein. For example, a thermoformed bag may "predominantly consist of" a thermoformable film as described herein, while containing a non-thermoformable film (e.g., a lid element) and additional markings on the film, such as by inkjet printing. . The invention illustratively disclosed in this document can be properly implemented in virtually the absence of any element or step that is not described specifically in this document.

[0044] All percentages, parts, and ratios herein are based on the total dry weight of the film composition or, as appropriate, the total dry weight of the composition of the contents of the package according to the present description, with all measurements taken at a temperature of about 25 ° C unless otherwise noted. All weights given that refer to the listed ingredients are based on active substance content and are therefore not related to carriers or by-products that may be contained in commercially available materials, unless otherwise noted.

[0045] All ranges of values set forth herein include all possible selections of ranges and any combination of such selected ranges. As a general rule, value ranges contain the specified endpoints unless otherwise specified. For the specified ranges of values, it should be understood that the present description extends to any intermediate value between the upper and lower limit value of the specified range, as well as any other specified or intermediate value in the specified range. The present description also covers the upper and lower limits of these smaller ranges, which may be independently included in the smaller ranges, unless the limit is intentionally removed from the specified range. It is envisaged that for given ranges containing one or both of the limit values, ranges excluding one or both of these limit values are also part of the present description.

[0046] This expressly provides that for any numerical value given in this document, for example, as a parameter of the subject matter of the invention or part of the range associated with the considered subject matter, the alternative, which is part of the description, is a functionally equivalent range of values around a certain numerical value (eg, for a size described as "40 mm", the provided alternative is "about 40 mm"). Similarly, a parameter described by "about" explicitly contains its exact value as an alternative (eg, for an endpoint described as "about 40", the provided alternative is "40").

[0047] In the context of this document, the terms "package(s)" and "bag(s)" should be considered interchangeable. In some embodiments, the terms "pouch(s)" and "pouch(s)", respectively, are used to refer to a container made using a film and a sealed container, preferably containing a material in a hermetically sealed manner, for example, in the form of a dosage system. delivery. Sealed bags can be made by any suitable method, including such methods and tools as heat sealing, solvent welding and adhesive sealing (for example, using a water-soluble adhesive).

[0048] In the context of this document, and unless otherwise indicated, the term "% wt." is intended to indicate the composition of the identified element in "dry" (non-aqueous) parts by weight of the entire film (if applicable) or parts by weight of the entire composition contained within the bag (if applicable).

[0049] In the context of this document, and unless otherwise indicated, the term "m.ch. per 100 m.h. resin" is intended to denote the composition of the identified element in parts per hundred parts of a water-soluble polymer resin (either PVA resin or other polymer resin, excluding starch) in a water-soluble film.

[0050] The film can be obtained by any suitable method, including the method of pouring from a solution. The film can be used to form a container (bag) by any suitable method, including vertical filling and sealing (VFFS), horizontal drum filling and sealing, thermoforming, and, for example, solvent sealing or heat sealing film layers around the periphery of the container. Bags can be used, for example, for the purpose of dosing materials for their introduction into the water body.

[0051] In any embodiment of the invention, the water-soluble bag may contain (contain) the composition in a given internal volume of the bag. The composition may be a liquid, a solid, or combinations of the above. In the context of this document, the term "liquid" includes free-flowing liquids, as well as pastes, gels, foams and mousses. Non-limiting examples of liquids include synthetic detergent compositions such as low and high strength liquid synthetic detergents, powdered synthetic detergent compositions, hand and/or machine dishwashing detergents; cleaning compositions for hard surfaces, fabric conditioners, washing gels commonly used for washing clothes, as well as bleaching and washing additives, shaving creams, skin care products, hair care compositions (shampoo and conditioners) and detergents for body. Such detergent compositions may contain surfactants, bleaches, enzymes, perfumes, dyes or pigments, solvents, and combinations of the foregoing. Optionally, the detergent composition is selected from the group consisting of washing powder, dishwashing detergent, hard surface cleaning composition, fabric conditioner compositions, shaving creams, skin care products, hair care compositions (shampoo and conditioners) and body cleansers, and combinations of the foregoing.

[0052] Additional non-limiting examples of liquids include non-household compositions, including compositions for agricultural use, compositions for vehicles, compositions for aviation, food and nutritional compositions, compositions for industry, compositions for animal husbandry, marine transport compositions, medical compositions, commercial compositions, military and quasi-military compositions, office compositions, recreational and park compositions, pet compositions, including cleaning and washing compositions suitable for any such use. In embodiments of the invention, the composition contained in the interior of the bag is a synthetic detergent composition.

[0053] Liquids may contain gases, for example, in the form of bubbles in suspension, or solids, for example, in the form of particles. In the context of this document, the term "solid" includes, among other things, powders, agglomerates and mixtures of the above products. Non-limiting examples of solids include granules, microcapsules, beads, ribbon-like particles, and pearlescent beads. Solid compositions can provide technical benefits including, but not limited to, laundry benefits, pretreatment benefits, and/or aesthetic effects such as perfume microcapsules or enzyme microcapsules.

[0054] Unless otherwise noted, films, bags, and related methods of making and using them are intended to include embodiments with any combination of one or more of the additional optional elements, tools, and steps described in more detail below (including those presented in the examples).

Water soluble film

[0055] The water-soluble film described herein contains a polyvinyl alcohol (PVA) resin, a modified polyvinyl alcohol resin, or combinations of the above products. In embodiments, the PVA comprises a PVA resin selected from the group consisting of a PVA homopolymer, an anionically modified PVA copolymer, and combinations of the foregoing. The film may be of any suitable thickness, with a typical and contemplated film thickness being about 76 microns (μm). Other contemplated values and ranges include values in the range of about 5 µm to about 200 µm, or in the range of about 20 µm to about 100 µm, or about 40 µm to about 90 µm, or about 50 µm to 80 µm, or from about 60 µm to 65 µm, for example, 65 µm, 76 µm or 88 µm.

PVA resin

[0056] The film described herein contains one or more PVA polymers to complement the PVA resin content of the film, and may contain a PVA copolymer.

[0057] Polyvinyl alcohol is a synthetic resin typically obtained by alcoholysis, commonly referred to as hydrolysis or saponification, of polyvinyl acetate. Fully hydrolyzed PVA, in which substantially all of the acetate groups have been converted to alcohol groups, is a highly hydrogen-bonded, highly crystalline polymer that dissolves only in hot water at temperatures greater than about 140°F (about 60°C). If sufficient acetate groups are left after hydrolysis of the polyvinyl acetate, i.e. the PVA polymer is partially hydrolysed, then such a polymer exhibits weaker hydrogen bonding, is less crystalline, and is generally soluble in cold water - at temperatures lower than about 50°F (about 10°C). C). Therefore, the partially hydrolyzed polymer is a vinyl acetate-vinyl alcohol copolymer, which is a PVA copolymer, but is generally referred to as PVA.

[0058] As used herein, the term "homopolymer" generally refers to polymers having the same type of monomeric repeating unit (eg, a polymer chain consisting or predominantly consisting of an individual monomeric repeating unit). For a particular PVA selected, the term "homopolymer" (or "PVA homopolymer" or "PVA polymer") further refers to copolymers having distributed vinyl alcohol monomer units and vinyl acetate monomer units depending on the degree of hydrolysis (e.g., a polymer chain consisting of or predominantly consisting of monomer units of vinyl alcohol and vinyl acetate). In the limiting case of 100% hydrolysis, the PVA homopolymer may be a true homopolymer having only vinyl alcohol units.

[0059] PVA polymer viscosity (μ) is determined by measuring the viscosity of a fresh solution using a Brookfield LV type viscometer with UL adapter as described in British Standard EN ISO 15023-2: 2006 Appendix E - Brookfield Test Method. International practice indicates the viscosity of 4% aqueous solutions of polyvinyl alcohol at 20 °C. It should be understood that all viscosity values given in this document in centipoise (cP) refer to the viscosity of a 4% aqueous solution of polyvinyl alcohol at 20 °C, unless otherwise indicated. Similarly, if a resin is described as having (or not having) a specific viscosity, then, unless otherwise indicated, the stated viscosity value is the average value of the viscosity value for that resin, which is inherently characterized by the appropriate molecular weight distribution.

. Значения

для смолы ПВС, которая содержит два или более полимеров ПВС, рассчитываются по формуле

где

- вязкость соответствующих полимеров ПВС. [0060] If the PVA resin is a mixture of PVA polymers, the resin can be selected based on the values of the weighted logarithm of the viscosity

. Values

for a PVA resin that contains two or more PVA polymers, are calculated by the formula

where

is the viscosity of the respective PVA polymers.

). В различных вариантах реализации изобретения значения вязкости

могут находиться в пределах от около 4 сП до около 30 сП, от около 5 сП до около 28 сП, от около 12 сП до около 25 сП, от около 18 сП до около 26 CP, от около 14 сП до около 23 сП, от около 22 сП до около 26 сП или от около 15 сП до около 20 сП, например, около 10 сП, около 11 сП, около 12 сП, около 13 сП, около 14 сП, около 14,5 сП, около 15 сП, около 16 сП, около 16,5 сП, около 17 сП, около 17,5 сП, около 18 сП, около 18,5 сП, около 19 сП, около 19,5 сП, около 20 сП, около 21 сП, около 22 сП, около 23 сП, около 24 сП, около 25 сП, около 26 сП, около 27 сП, около 28 сП, около 29 сП, или около 30 сП. В данной области техники хорошо известно, что вязкость смол ПВС коррелирует со средневесовой молекулярной массой

смолы ПВС, и значения вязкости часто используют в качестве суррогатных значений массы

. [0061] For information, the water-soluble film contains a PVA resin or a mixture of resins having a viscosity of a 4% solution at 20°C (

). In various embodiments of the invention, the viscosity values

may range from about 4 cP to about 30 cP, from about 5 cP to about 28 cP, from about 12 cP to about 25 cP, from about 18 cP to about 26 cP, from about 14 cP to about 23 cP, from about 22 cP to about 26 cP, or about 15 cP to about 20 cP, for example, about 10 cP, about 11 cP, about 12 cP, about 13 cP, about 14 cP, about 14.5 cP, about 15 cP, about 16 cP, about 16.5 cP, about 17 cP, about 17.5 cP, about 18 cP, about 18.5 cP, about 19 cP, about 19.5 cP, about 20 cP, about 21 cP, about 22 cP , about 23 cps, about 24 cps, about 25 cps, about 26 cps, about 27 cps, about 28 cps, about 29 cps, or about 30 cps. It is well known in the art that the viscosity of PVA resins correlates with the weight average molecular weight

PVA resins, and viscosity values are often used as surrogate weight values

.

[0062] For PVA resins, the degree of hydrolysis (H) is at least 80%, 84%, or 85%, and not more than about 99.7%, 98%, 96%, or 80%, for example, ranging from about 84% to about 90%, or 85% to 88%, or 86.5%, or in the range of 85% to 99.7%, about 88% to 98%, or 90% to 96%, e.g. , 90%, 91%, 92%, 93%, 94%, 95%, or 96%, or ranging from about 87% to 93%. In the context of this document, the degree of hydrolysis is expressed as the molar concentration of vinyl acetate units converted to units of vinyl alcohol.

) находится в пределах от около 80% до около 99,7%, от около 85% до около 98%, или от около 87% до около 93%, или от около 96% до 98%, например, около 85%, или около 86%, или около 87%, или около 87,5%, или около 88%, или около 88,5%, или около 89%, или около 89,5%, или около 90%, или около 91%, или около 92%, или около 93%, или около 94%, или около 95%, или около 96%, или около 96,5%, или около 97%, или около 97,5%, или около 98%. Например,

для смолы ПВС, которая содержит два или более полимеров ПВС, рассчитывается по формуле

, где W_i представляет собой массовую процентную долю соответствующего полимера ПВС, а H_i представляет собой соответствующую степень гидролиза. [0063] In addition, if the PVA resin is a mixture of PVA polymers, it is desirable to select a PVA mixture for which the weighted average of the degree of hydrolysis (

) is in the range of about 80% to about 99.7%, about 85% to about 98%, or about 87% to about 93%, or about 96% to 98%, such as about 85%, or about 86%, or about 87%, or about 87.5%, or about 88%, or about 88.5%, or about 89%, or about 89.5%, or about 90%, or about 91%, or about 92%, or about 93%, or about 94%, or about 95%, or about 96%, or about 96.5%, or about 97%, or about 97.5%, or about 98%. For example,

for a PVA resin that contains two or more PVA polymers, is calculated by the formula

, where W _i is the weight percentage of the corresponding PVA polymer, and H _i is the corresponding degree of hydrolysis.

[0064] Water-soluble films may contain PVA copolymers, which may be PVA terpolymers containing vinyl alcohol monomer units, vinyl acetate monomer units (i.e., if it is not completely hydrolyzed), and anionic monomer units of the same type (monomer units of the same type may contain, for example, , equivalent acid forms, salt forms, and optionally ester forms of the anionic monomer unit). In some aspects, the PVA copolymer may contain two or more types of anionic monomer units. General classes of anionic monomer units that can be used for the PVA copolymer include vinyl polymer units corresponding to vinyl monomers of a monocarboxylic acid, their esters and anhydrides, dicarboxylic monomers having a polymerizable double bond, their esters and anhydrides, and alkali salts. metals of any of the above compounds. Examples of suitable anionic monomer units include vinyl polymer units corresponding to vinyl anion monomers, including vinylacetic acid, maleic acid, monoalkyl maleate, dialkyl maleate, maleic anhydride, fumaric acid, monoalkyl fumarate, dialkyl fumarate, fumaric anhydride, taconic acid, monoalkyl itaconate, dialkyl itaconate, taconic anhydride, acid, monoalkyl citraconate, dialkyl citraconate, citraconic anhydride, mesaconic acid, monoalkyl mesaconate, dialkyl mesaconate, mesaconic anhydride, glutaconic acid, monoalkyl glutaconate, dialkyl glutaconate, glutaconic anhydride, alkyl acrylates, alkyl alkacrylates, vinyl sulfonic acids, alkali metal salts of the above compounds, esters of the above compounds, as well as combinations of the above . In embodiments of the invention, the anionic monomer unit is not an acrylate or an alkyl alkacrylate.

[0065] In embodiments, the anionic monomer unit is selected from the group consisting of vinylacetic 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, fumaric anhydride, itaconic acid, monomethyl itaconate, dimethyl itaconate, itaconic anhydride, citraconic acid, monoalkyl citraconate, dialkyl citraconate, citraconic anhydride, mesaconic acid, monoalkyl meconate, dialkyl meconate, mesaconic anhydride, glutaconic acid, monoalkyl glutaconate, dialkyl glutaconate, glutaconic anhydride, vinyl sulfonic acid, ethylene sulfonic acid, ethylene sulfonic acid, ethylene sulfonic acid, ethylene sulfonic acid, 2 alkyl sulfonic acid -methylpropanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, 2-methylacrylamido-2-methylpropanesulfonic acid, 2-sulfoethylacrylate, alkali metal salts of the above compounds, esters the above compounds, as well as combinations of the above. In embodiments, the anionic monomer unit is selected from the group consisting of vinylacetic acid, maleic acid, monoalkyl maleate, dialkyl maleate, monomethyl maleate, dimethyl maleate, maleic anhydride, fumaric acid, monoalkyl fumarate, dialkyl fumarate, monomethyl fumarate, dimethyl fumarate, fumaric anhydride, itaconic acid, monomethyl itaconate, dimethyl itaconate , itaconic anhydride, citraconic acid, monoalkyl citraconate, dialkyl citraconic acid, citraconic anhydride, mesaconic acid, monoalkyl mesaconate, dialkyl mesaconate, mesaconic anhydride, glutaconic acid, monoalkyl glutaconate, dialkyl glutaconate, glutaconic anhydride, vinyl sulfonic acid, alkyl sulfonic acid, alkyl sulfonic acid, 1-propanrylonic acid, 2-ethylene sulfonic acid, 2-ethylene sulfonic acid, 2 -acrylamido-2-methylpropanesulfonic acid, 2-methylacrylamido-2-methylpropanesulfonic acid, alkali metal salts of the above compounds, esters of the above compounds, as well as combinations of the above. In embodiments, the anionic monomer unit is selected from the group consisting of maleic acid, monoalkyl maleate, dialkyl maleate, monomethyl maleate, dimethyl maleate, maleic anhydride, fumaric acid, monoalkyl fumarate, dialkyl fumarate, monomethyl fumarate, dimethyl fumarate, fumaric anhydride, itaconic acid, monomethyl itaconate, dimethyl itaconate, itaconic anhydride , citraconic acid, monoalkyl citraconate, dialkyl citraconate, citraconic anhydride, mesaconic acid, monoalkyl mesaconate, dialkyl mesaconate, mesaconic anhydride, glutaconic acid, monoalkyl glutaconate, dialkyl glutaconate, glutaconic anhydride, alkali metal salts of the above compounds, esters of the above compounds, as well as combinations of the above. In embodiments of the invention, the anionic monomer unit is not an acrylate or an alkyl alkacrylate.

[0066] In one type of embodiment of the invention, the PVA is a copolymer modified with a carboxyl group. In another aspect, the PVA may be modified with a dicarboxylic type monomer. In one class of these embodiments, the α-carbon of both carbonyl groups is linked by an unsaturated bond (eg, maleic acid, fumaric acid). In another class of these embodiments of the invention, the α-carbon of both carbonyl groups is linked by an unsaturated bond, and the unsaturated bond is substituted, for example, by a methyl branch (eg, citraconic acid, mesaconic acid). In another class of these embodiments, the β-carbon of one of the carbonyl groups and the α-carbon of the second carbonyl group are linked by an unsaturated bond (eg, itaconic acid, cis-glutonic acid, trans-glutonic acid). The use of monomers which provide alkyl carboxyl groups is contemplated. Particularly contemplated is the use of comonomers based on compounds of the maleic acid type (eg maleic acid, dialkyl maleate (including dimethyl maleate), monoalkyl maleate (including monomethyl maleate) or maleic anhydride).

[0067] In embodiments of the invention, the anionic monomeric unit is a monomer derived from maleic acid. Monomeric derivatives of maleic acid may include one or more compounds from the group consisting of maleic acid, monoalkyl maleate, dialkyl maleate, monomethyl maleate, dimethyl maleate, maleic anhydride, alkali metal salts of the above compounds (for example, sodium, potassium or other alkali metal salts ), esters of the above compounds (for example, methyl, ethyl or other C ₁ -C ₄ or C ₆ alkyl esters), as well as combinations of the above compounds (for example, more than one type of anionic monomers or equivalent forms of one anionic monomer). For example, a monomer derived from maleic acid may contain one or more compounds of the group consisting of monoalkyl maleate, dialkyl maleate, and alkali metal salts of the above compounds (eg, sodium salts). Similarly, the anionic monomer may contain one or more compounds of the group consisting of monomethyl maleate, dimethyl maleate, and alkali metal salts of the above compounds (eg, sodium salts).

[0068] As a solvent for saponification of polyvinyl acetate to polyvinyl alcohol, as a rule, methanol is used, the remains of which can be in the finished PVA powder even after drying. When PVA is dissolved, methanol is released into the atmosphere. Therefore, it is desirable to reduce the methanol content of the PVA powder to less than 3% wt. or even less than 1% wt. Methods for removing volatile organic compounds include introducing a wet gas during the drying step to replace the volatile organic compounds in the PVA polymers with water. However, PVA modified with monoesters, diesters, or ethylenically unsaturated dicarboxylic acid anhydrides has a high affinity for water, and the use of wet gas causes the surface of the powder particles to dissolve and the particles to agglomerate, which makes PVA difficult to process. In alternative embodiments, prolonged heating at high temperatures is used to remove residual methanol. However, such high temperatures promote crosslinking between the PVA hydroxyl groups and the monoester, diester and/or anhydride units, resulting in insoluble components.

[0069] To reduce the amount of residual methanol in the PVA copolymers, the saponified copolymer is washed in a mixture of methanol/methyl acetate with a methyl acetate content of about 45% by volume. or more, 60% vol. or more, or 70% vol. or more. For example, the PVA gel obtained after the saponification step can be triturated with methanol/methyl acetate in a ratio of 15/85 (v/v).

[0070] Additionally, to reduce the methanol content, you can reduce the particle size of the finished PVA resin, so that more than 95% wt. particles passed through a sieve of 1.0 mm, or more than 30% wt. particles passed through a sieve of 500 μm, or more than 45% wt. particles passed through a 500 µm sieve. If the particle size of the finished PVA resin is too large, the evaporation of methanol becomes difficult.

[0071] For a PVA copolymer containing monoesters, diesters, or ethylenically unsaturated dicarboxylic acid anhydrides, the amount of insoluble components can be reduced by adjusting the ratio of lactone ring formation to copolymer modification upon partial saponification. The ratio of lactone ring formation to copolymer modification can be described by equation (Q):

0.05 ≤ Y/X < 0.98, (Q)

where X is a modification of the copolymer, and Y is the formation of a lactone ring. To reduce the amount of insoluble materials, the Y/X ratio is about 0.80 or less, about 0.60 or less, or about 0.40 or less.

[0072] If the PVA resin contains a PVA copolymer including an anionic monomer, the level of incorporation of one or more anionic monomer units into the PVA copolymer is not specifically limited. In embodiments of the invention, the content of one or more anionic monomer units in the PVA copolymer is in the range from about 1 mol%. up to 10% mol. or from 1.5% mol. up to about 8% mol., or from about 2% mol. up to about 6% mol., or from about 3% mol. up to about 5% mol., or from about 1% mol. up to about 4% mol. (for example, at least 1.0, 1.5, 2.0, 2.5, 3.0, 3.5, or 4.0 mole % and/or up to about 3.0, 4.0, 4.5, 5.0, 6.0, 8.0, or 10 mole % in various embodiments).

[0073] The water-soluble film may comprise at least about 20% wt., 30% wt., 40% wt., 50% wt., 55% wt., 60% wt., 65% wt., 70% wt. ., 75% wt., 80% wt., 85% wt. or 90% wt., and/or up to about 60% wt., 70% wt., 80% wt., 90% wt., 95% wt. or 99% wt. PVA resin or working mixture based on the total weight of the film. In embodiments of the invention, the content of the PVA resin or the working mixture in the film is in the range from about 20% wt. up to about 95% wt. based on the total weight of the film. In embodiments of the invention, the content of the PVA resin or the working mixture in the film is in the range from about 60% wt. up to about 95% wt. based on the total weight of the film. In embodiments of the invention, the content of the PVA resin or the working mixture in the film is in the range from about 85% wt. up to about 95% wt. based on the total weight of the film.

[0074] In embodiments of the invention, the PVA resin contains a mixture of PVA polymers. In embodiments of the invention, the PVA resin working mixture contains an anionically modified PVA polymer. In refinements to the above embodiment, the PVA resin working mixture further comprises a second PVA polymer selected from the group consisting of a second anionically modified PVA polymer and a PVA homopolymer. In embodiments of the invention, characterized in that the PVA resin working mixture contains two anionically modified PVA polymers, the two anionically modified PVA polymers may have the same anionic modification or different anionic modifications. For example, each of the two anionically modified PVA polymers may be a maleic-type modified polymer. For example, the two anionically modified PVA polymers may be a maleic-type modified polymer and an acetate-type modified polymer, respectively. In embodiments of the invention, characterized in that the two anionically modified PVA polymers have an anionic modification of the same type, for two anionically modified PVA polymers, at least one of the properties selected from viscosity, degree of hydrolysis, and/or degree of anionic modification, can take on different values.

STARCH

[0075] The water-soluble film described herein contains starch and/or modified starch. Non-limiting examples of modified starches include ethylated starch, ethoxylated starch, propylated starch, hydroxypropyl modified (hydroxypropylated) starch, and acetate modified starch.

[0076] The amount of starch can range from at least about 2 ppm, 2.5 ppm, 5 ppm, 6 ppm, 7 ppm, 10 ppm ., 12 m.h., 15 m.h., 20 m.h. or 22 m.h. and/or up to about 5 p.m., 10 p.m., 12 p.m., 16 p.m., 20 p.m., 22 p.m., 24 p.m., 26 p.m. h. or 30 m.h. based on the total amount of PVA resin. For example, the amount of starch may be in the range of at least about 2.5 ppm. up to about 30 m.h. per 100 m.h. resin, or from about 5 m.h. up to about 30 m.h. per 100 m.h. resin, or from about 5 m.h. up to about 30 m.h. per 100 m.h. resin, or from about 5 m.h. up to about 15 m.h. per 100 m.h. resin, or from about 6 m.h. up to about 10 m.h. per 100 m.h. resin, or from about 12 m.h. up to about 16 m.h. per 100 m.h. resin, or from about 2 m.h. up to about 5 m.h. per 100 m.h. resin, or from about 5 m.h. up to about 12 m.h. per 100 m.h. resin, or from about 2 m.h., about 2.5 m.h., about 3 m.h., about 7 m.h., about 8 m.h., about 9 m.h., about 13 m.h., about 14 m.h., about 16 m.h., about 20 m.h., about 22 m.h., about 24 m.h., about 25 m.h. or about 26 m.h. per 100 m.h. resins.

[0077] The amylose content of the starch can be at least about 20%, about 23%, about 25%, about 30%, about 40%, about 50%, about 60%, about 65%, or about 75%, and/ or up to about 60%, about 70%, about 80%, about 85%, or about 95%, and for example, be in the range from about 65% to about 95%, or from about 75% to about 85%, or from about 20% to about 80%, or about 25% to about 70%, or about 30% to about 70%, or about 40% to about 60%, or about 23% to about 95%.

[0078] Sources of starch with an amylose content ranging from about 20% to about 80% include acorns, apples, arrowroot, barley, longiflora, elm, sapwood, toffee bulbs, corn, amylose corn, oats, peas, potatoes, sago, and wheat. Starch sources with an amylose content ranging from about 23% to about 95% include acorns, apples, longiflora, iris bulbs, corn, amylocorn, oats, peas, sago, and wheat.

[0079] Determination of amylose content can be performed by iodine complex formation, as described in "Amylose and Amylopectin Content of Starches Determined by their Iodine Complex Formation", FL Bates, D. French, and RE Rundle, J . Am. Chem. soc. , 1943, 65 (2), p. 142-148.

[0080] For high amylose starches containing less than 45% amylopectin, measurements are more conveniently made using the modified potentiometric iodine method described in US Pat. line 68. Starches with a high amylose content, for which the amount of amylose is more than 55%, more than 70% and more than 89%, belong to the embodiments of the invention included in this document.

[0081] Amylopectin present in starches suitable for this invention may contain a high molecular weight fraction, an intermediate molecular weight fraction, and a low molecular weight fraction. The molecular weight fraction can be determined using gel permeation chromatography, reviewed in Journal of Cereal Science 27 (1998) 289-299, Shi, Y., Capitani, T., Trzasko, P. and Jeffoat, R. High amylose starches containing amylopectin in all three weight fractions, refer to the embodiment of the invention included in this document. For example, for high amylose starch, the amount of the high molecular weight amylopectin fraction may be between 2-32% (e.g., 31.1%), the amount of the intermediate molecular weight linear and branched polymer fraction (mixture of amylopectin and amylose) may be be between 59-71% (eg 59.5%) and the low molecular weight fraction (amylose) may be between 9-27% (eg 9.4%).

[0082] The average particle size of starch in the solid state should not exceed 6 microns, for example, starch particles can have a size in the range from about 1 micron to about 6 microns, from about 1 micron to about 5.5 microns, from about 1.5 µm to about 5 µm, about 2 µm to about 5 µm, about 2 µm to about 4 µm, about 3 µm to about 5 µm, about 3 µm to about 4 µm, e.g., about 1, 2, 3, 4, 5 or 6 µm. Regardless of the theory, it is believed that increasing the average starch particle size above 6 microns adversely affects the physical properties of the resulting film, such as tensile strength and tensile elongation. It is well known in the art that in the presence of water and heat, starch grains expand to some extent by swelling (eg, from about 6 microns to about 8 microns) and then break down over time. In this regard, in the context of this document, the expression "average particle size" of starch refers to dry particles of starch raw materials. Methods for determining the average particle size of dry starch are well known in the art.

[0083] If starch is heated in the presence of water to temperatures below the starch gelatinization temperature, the starch swells. If starch is heated in the presence of water to a temperature higher than or equal to the starch gelatinization temperature, the starch is destroyed and a gel is formed. The gelatinization temperature for a given starch depends on various properties of the starch, including, but not limited to, the type of plant from which the starch is derived, the degree of crosslinking in the starch, the degree of starch modification, and the amylose content. In embodiments of the invention, the starch gelatinization temperature is higher than the mixing temperature in water of the feedstock to form water-soluble films. In embodiments, the gelatinization temperature of starch in water is greater than about 75°C, greater than about 80°C, greater than about 85°C, greater than about 90°C, or greater than about 95°C, and less than about 300 °C, less than about 250 °C, 200 °C or 150 °C, for example, is in the range from about 80 °C to about 200 °C, or from about 85 °C to about 150 °C. The presence of other chemicals in the aqueous solution can affect the gelling properties of the starch.

[0084] The degree of starch modification may be at least about 2%, about 4%, about 5%, or about 6%, and/or not more than about 4%, about 6%, about 7%, or about 8%, for example, be greater than about 2%, or be in the range of about 2% to about 8%, about 4% to about 8%, or about 5% to about 7%.

[0085] In embodiments of the invention, two or more starches can be used together to form a mixture of starches. Starch mixtures may contain combinations such as two unmodified starches, two modified starches, or an unmodified starch and a modified starch. For example, two or more unmodified starches may be blended together to achieve an average amylose content in the range of about 20% to about 95%, or about 40% to about 60%. Surprisingly, it has been found that when using a mixture of starches, each starch in the mixture has an independent effect on the properties of the final film in the same way as when used as a single starch. In this regard, each starch from the mixture corresponds to individual values for the degree of modification, gelatinization temperature, particle size and/or amylose content, as described in this document.

[0086] In embodiments of the invention, the starch contains hydroxypropyl-modified starch, and its content in the water-soluble film is in the range from about 5 m.h. up to about 30 m.h. per 100 m.h. resin, optionally from about 6 m.h. up to about 10 m.h. per 100 m.h. resin or from about 12 m.h. up to about 16 m.h. per 100 m.h. resins. Optionally, the amylose content of the hydroxypropylated starch ranges from about 65% to about 95%. or from about 75% to about 85%. Optionally, the degree of modification of the hydroxypropyl modified starch is from about 4% to about 8%, or from about 5% to about 7%. In embodiments of the invention, a water soluble film containing hydroxypropyl modified starch and having a thickness of about 76 microns has a cold water solubility of less than about 90 seconds as measured by MSTM-205.

[0087] Regardless of theory, one skilled in the art will appreciate that as the amount of starch in the film increases, there will be deterioration in the mechanical properties of the film (eg, tensile strength and tear strength). As shown below, at a ratio of PVA resin to unmodified starch in a water-soluble film of about 80:20 (i.e., about 25 ppm starch per 100 ppm resin), or at a higher starch content (e.g., for a ratio of 70:30) there is a sharp decrease in the values of tensile strength and tear strength compared to the values for a similar water-soluble film with a lower starch content than in the case of a ratio of PVA resin to starch equal to 80:20, for example, at a ratio 97:3.

[0088] Unexpectedly, it was found that for a film containing hydroxypropyl-modified starch, it provides the advantage that with an increase in the amount of hydroxypropyl-modified starch in the film in the range from about 2.5 m.h. up to about 30 m.h. per 100 m.h. resin, the mechanical properties of the film are preserved (that is, they do not significantly deteriorate). In embodiments of the invention, the water-soluble film contains hydroxypropyl-modified starch, and its content is in the range from about 5 m.h. up to about 30 m.h. per 100 m.h. resin, while the values of tensile strength are at least about 40 MPa or at least 45 MPa, and not more than about 60 MPa. Regardless of theory, it is assumed that if the modified starch is a hydroxyalkyl modified starch in which the alkyl contains 3 or more carbon atoms, for example, from 3 to 8 carbon atoms, the hydroxyalkyl chain breaks the helical structure of the amylose, which allows establish a closer bond between amylose and polyvinyl alcohol chains and provide increased mechanical strength of the resulting films compared to a film containing unmodified starch.

[0089] Regardless of the theory, it is assumed that for a water-soluble film containing starch, with an increase in the amount of starch in the film, the value of the static coefficient of friction of glossy surfaces (GG) decreases. In embodiments of the invention, the water-soluble film contains hydroxypropyl-modified starch in the range from about 5 m.h. up to about 30 m.h. per 100 m.h. resin, wherein the values of the static coefficient of friction of glossy surfaces (GG) are about 5 or less, about 3 or less, about 2 or less, or about 1 or less. In embodiments of the invention, the water-soluble film contains hydroxypropyl-modified starch in the range from about 5 m.h. up to about 30 m.h. per 100 m.h. resin, and at the same time the film is characterized by a reduced value of the static coefficient of friction of glossy surfaces compared to a film of the same composition that does not contain starch.

[0090] In embodiments of the invention, the starch contains a modified starch with a degree of modification of more than about 2%, and its content is in the range from about 2.5 m.h. up to about 30 m.h. per 100 m.h. resin, optionally from about 6 m.h. up to about 16 m.h. per 100 m.h. resin or from about 6 m.h. up to about 10 m.h. per 100 m.h. resin, or from about 12 m.h. up to about 16 m.h. per 100 m.h. resins. Optionally, the degree of modification is from about 4% to about 8%, or from about 5% to about 7%. Optionally, the amylose content of the modified starch is in the range of about 65% to about 95%. or from about 75% to about 85%. Optionally, the modified starch contains a hydroxyalkyl modification with an alkyl chain length of three or more carbon atoms. In embodiments, a water-soluble film containing modified starch with a degree of modification greater than about 2% and having a thickness of about 76 microns has a cold water solubility of less than about 90 seconds as measured by MSTM-205.

[0091] Regardless of the theoretical justification, it is assumed that if the modified starch has a degree of modification of more than about 2%, then with an increase in the amount of starch in the film in the range from about 2.5 m.h. up to about 30 m.h. per 100 m.h. resin, the mechanical properties of the film are preserved (that is, they do not significantly deteriorate). In embodiments of the invention, the water-soluble film contains modified starch with a degree of modification of more than about 2%, and its content is in the range from about 2.5 m.h. up to about 30 m.h. per 100 m.h. resin, and the values of tensile strength are at least about 40 MPa or at least 45 MPa, and not more than about 60 MPa. Regardless of the theory, it is believed that if the degree of modification of the modified starch is greater than about 2%, for example, from 4% to 8%, then the modifications break the helical structure of the amylose, which allows the amylose to be more closely linked to the polyvinyl alcohol chains and provides increased mechanical strength of the obtained films in comparison with the film containing unmodified starch.

[0092] In embodiments of the invention, the water-soluble film contains modified starch with a degree of modification of more than about 2%, the amount of which is in the range from about 2.5 m.h. up to about 30 m.h. per 100 m.h. resin, wherein the values of the static coefficient of friction of glossy surfaces (GG) are about 5 or less, about 3 or less, about 2 or less, or about 1 or less. In embodiments of the invention, the water-soluble film contains modified starch with a degree of modification of more than about 2%, the amount of which is in the range from about 2.5 m.h. up to about 30 m.h. per 100 m.h. resin, while the film is characterized by a reduced value of the static coefficient of friction of glossy surfaces compared to a film of a similar composition that does not contain starch.

[0093] In embodiments, the water-soluble film contains unmodified starch, wherein the amylose content of the starch is in the range of about 20% to about 80%, optionally about 25% to about 70%, about 30% to about 70%, or from about 40% to about 60%. Optionally, the amount of unmodified starch is in the range of about 2 m.h. up to about 30 m.h. per 100 m.h. resin or from about 2 m.h. up to about 5 m.h. per 100 m.h. resins. It has been found that a water-soluble film containing unmodified starch with an amylose content ranging from about 20% to about 80% provides the advantage that the static coefficient of friction of glossy surfaces GG for the film is about 1 or less even at low starch concentrations (eg, about 2 ppm to about 5 ppm per 100 ppm resin). In embodiments, the water soluble film contains unmodified starch, wherein the amylose content of the starch is in the range of about 20% to about 80%, optionally about 25% to about 70%, about 30% to about 70%, or about 40%. up to about 60%, while the film is characterized by a reduced value of the static coefficient of friction of glossy surfaces compared to a film of a similar composition that does not contain starch.

[0094] In embodiments of the invention, the water-soluble film contains hydroxypropyl-modified starch, and the amylose content of the starch is in the range from about 23% to about 95%, while the PVA resin contains unmodified polyvinyl alcohol, an anionic modified polyvinyl alcohol copolymer, or a combination of the above compounds with the proviso that the anionic modifier is not an acrylate. Optionally, the amount of hydroxypropyl-modified starch is in the range of about 5 m.h. up to about 12 m.h. per 100 m.h. resins. Optionally, the amylose content of the hydroxypropyl modified starch is in the range of about 50% to about 95%. Optionally, the hydroxypropyl modified starch contains more than 2% hydroxypropyl modification, for example 4% to 8% hydroxypropyl modification. Regardless of the theoretical justification, it is assumed that the negative nature of the interaction of acrylate groups with hydroxyalkyl-modified starches leads to the production of films with high values of the static friction coefficient of glossy surfaces (GG). In embodiments of the invention, the water-soluble film contains hydroxypropyl-modified starch, and the amylose content of the starch is in the range from about 23% to about 95%, while the PVA resin contains unmodified polyvinyl alcohol, an anionic modified polyvinyl alcohol copolymer, or a combination of the above compounds, with the caveat, that the anionic modifier is not an acrylate, and that the static coefficient of friction of glossy surfaces is about 5 or less. In embodiments of the invention, the water-soluble film contains hydroxypropyl-modified starch, and the amylose content of the starch is in the range from about 23% to about 95%, while the PVA resin contains unmodified polyvinyl alcohol, an anionic modified polyvinyl alcohol copolymer, or a combination of the above compounds, with the caveat, that the anionic modifier is not an acrylate, and that the film has a reduced static coefficient of friction of glossy surfaces compared to a film of the same composition that does not contain starch.

Other water soluble polymers

[0095] Other water-soluble polymers for use in addition to the PVA resin or resin mix may include, but are not limited to: vinyl alcohol-vinyl acetate copolymer, sometimes referred to as PVA homopolymer, polyacrylates, water-soluble acrylate copolymers, polyvinylpyrrolidone, polyethyleneimine, pullulan, water-soluble natural polymers, including but not limited to guar gum, gum arabic, xanthan gum, carrageenan and starch (not previously discussed), water-soluble polymeric modified starches (not discussed above), including but not limited to ethylated starch, hydroxyethyl starch and hydroxypropylated starch, copolymers of the above compounds, and combinations of any the above compounds. In addition, other water-soluble polymers may include polyalkylene oxides, polyacrylamides, polyacrylic acids and their salts, celluloses, cellulose ethers, cellulose esters, cellulose amides, polyvinyl acetates, polycarboxylic acids and their salts, polyamino acids, polyamides, gelatins, methylcelluloses, carboxymethylcelluloses and their salts, dextrins, ethylcelluloses, hydroxyethylcelluloses, hydroxypropylmethylcelluloses, maltodextrins, polymethacrylates and combinations of any of the above compounds. Water soluble polymers such as PVA and other compounds are commercially available from a number of sources. In embodiments of the invention, the water-soluble film does not contain polyacrylates, water-soluble acrylate copolymers, polyacrylic acids, or salts thereof.

[0096] The water-soluble film may contain other auxiliaries and processing aids, such as plasticizers, plasticizer compatibilizers, surfactants, lubricants, release agents, fillers, diluents, cross-linking agents, release agents, anti-oxidants that reduce tackifiers, defoamers, nanoparticles such as layered silicate type nanoclays (e.g. sodium montmorillonite), bleaching agents (e.g. sodium metabisulphite, sodium bisulfite or others), aversive agents such as bittering agents (e.g. denatonium salts such as denatonium benzoate, denatonium saccharide and denatonium chloride, sucrose octaacetate, quinine, flavonoids such as quercetin and naringen, and quasinoids such as quassin and brucine) and caustic components (such as capsaicin, piperine, allyl isothiocyanate and resiniferatoxin), as well as other functional components in quantities data for the intended purposes. Preferred are embodiments of the invention containing plasticizers. In embodiments, the water-soluble film contains a surfactant, an antioxidant, a bittering agent, a polymer, an anti-staining agent, an anti-pollution agent, a chelating agent, a base agent, a perfume, or combinations of the foregoing. The number of auxiliary components can be up to about 50% wt., 20% wt., 15% wt., 10% wt., 5% wt., 4% wt. and/or at least 0.01% wt., 0.1% wt., 1% wt. or 5% wt., alone or together.

[0097] In processes such as solvent casting, in which water-soluble film components are added to a solvent and mixed or held at high temperature, the composition may take on a dark color. This discoloration is undesirable for most waterborne film applications since a clear film is required. Therefore, the methods and compositions described herein to prevent darkening of the heated composition may further include adding bisulfite or metabisulfite to the composition in an amount of from about 0.10 wt%. up to about 0.75% of the mass. based on the weight of the resulting film, for example, in the range from about 0.4% of the mass. up to about 0.7% of the mass.

PLASTICIZERS

[0098] A plasticizer is a liquid, solid, or semi-solid substance that is added to a material (usually a resin or elastomer) to make the material soft and supple (by lowering the glass transition temperature of the polymer) and to facilitate its processing. In addition, the polymer can be subjected to internal plasticization by chemical modification of the polymer or monomer. In addition, the polymer can be additionally subjected to external plasticization by adding the necessary plasticizing component.

[0099] The plasticizer may contain, among other things, glycerin, diglycerin, sorbitol, ethylene glycol, diethylene glycol, triethylene glycol, dipropylene glycol, tetraethylene glycol, propylene glycol, polyethylene glycols up to 400 Mm, neopentyl glycol, trimethylol propane, polyether polyols, 2-methyl-1,3-propanediol (MPDiol ^® ), ethanolamines, polymers of glycerol and propylene oxide (such as, for example, Voranol ^TM from The Dow Chemical Company) and mixtures of the above compounds. In embodiments of the invention, the plasticizer is selected from the group consisting of glycerol, propylene glycol, sorbitol, trimethylol propane, polyethylene glycols with Mm up to 400, polymers of glycerol and propylene oxide (such as, for example, Voranol ^TM manufactured by The Dow Chemical Company), 2-methyl-1 ,3-propanediol, xylitol and combinations of the above. In embodiments of the invention, the plasticizer is selected from the group consisting of glycerol, sorbitol, 2-methyl-1,3-propanediol, and a combination of the above.

[00100] The total amount of plasticizer can be in the range from about 10% of the mass. up to about 45% of the mass. or from about 15% of the mass. up to about 35% wt., or from about 20% wt. up to about 30% wt., or from about 20% wt. up to about 45% wt., for example, 25% wt. based on the total weight of the film. In embodiments of the invention, the amount of plasticizer in the water-soluble film is expressed in parts by weight per 100 parts by weight of the total water-soluble polymer in the water-soluble film and corresponds to, for example, at least 1 ppm, at least 5 ppm, at least 10 m.h., at least 15 m.h., at least 20 m.h., at least 25 m.h., at least 30 m.h. or at least 35 m.h. For example, the total amount of plasticizer may be up to 40 ppm. or 45 m.h., or 50 m.h. per 100 m.h. polymer. For example, the total amount of plasticizer may range from about 1 ppm. up to about 40 m.h. per 100 m.h. resin, or from about 10 m.h. up to about 40 m.h. per 100 m.h. resin, or from about 30 m.h. up to about 50 m.h. per 100 m.h. resin, or from about 32.5 m.h. up to about 42.5 m.h. per 100 m.h. resin, or from about 35 m.ch. up to about 45 m.h. per 100 m.h. resin, or from about 35 m.ch. up to about 40 m.h. per 100 m.h. resin, or from more than 30 m.ch. up to less than 45 m.h. per 100 m.h. resin, or from 40 m.h. up to 50 m.h. per 100 m.h. resins. Certain amounts of plasticizers can be selected in a particular embodiment of the invention based on the desired elasticity of the film and the characteristics of the processing of the water-soluble film. At low levels of plasticizer concentration, films can become brittle, difficult to machine, or weakly break resistant. At elevated levels of plasticizer concentration, films may be too soft, brittle, or difficult to process for the desired use.

SURFACTANTS

[00101] Surfactants for use in water-soluble films are well known in the art. Optionally, surfactants are added to facilitate dispersion of the resin solution during the casting process. Suitable surfactants may include the nonionic, cationic, anionic and zwitterionic classes of compounds. Suitable surfactants include, but are not limited to, polyoxyethylated polyoxypropylene glycols, alcohol ethoxylates, alkylphenol ethoxylates, tertiary acetylenic glycols and alkanolamides (nonionic), polyoxyethylated amines, quaternary ammonium salts and quaternized polyoxyethylated amines (cationic) and amine oxides, N-alkyl betaines and sulfobetaines ( zwitterionic). Other useful surfactants include: sodium dioctylsulfosuccinate, lactyl esters of fatty acids of glycerol and propylene glycol, lactyl esters of fatty acids, sodium alkyl sulfates, polysorbate 20, polysorbate 60, polysorbate 65, polysorbate 80, lecithin, acetylated fatty acid esters of glycerol and propylene glycol, and acetylated fatty acid esters, as well as combinations of the above compounds. In embodiments of the invention, the surfactant is selected from the group consisting of polyoxyethylated polyoxypropylene glycols, alcohol ethoxylates, alkylphenol ethoxylates, tertiary acetylenic glycols and alkanolamides, polyoxyethylated amines, quaternary ammonium salts and quaternized polyoxyethylated amines and amine oxides, N-alkyl betaines and sulfobetaines, as well as combinations the above compounds.

[00102] In various embodiments of the invention, the amount of surfactant in the water-soluble film is in the range from about 0.1% of the mass. up to about 8.0% of the mass. or from about 1.0% of the mass. up to about 7.0% wt., or from about 3% wt. up to about 7% wt., or from about 5% wt. up to about 7% of the mass. In embodiments of the invention, the amount of plasticizer in the water-soluble film is expressed in parts by weight per 100 parts by weight of the total water-soluble polymer in the water-soluble film and ranges from about 0.5 m.h. up to about 12 m.h., from about 1.0 m.h. up to about 11.0 m.h, from about 3.0 m.h. up to about 10.5 m.h., from about 1.0 m.h. up to about 2.0 m.h.

[00103] Suitable lubricants/release agents may include, among others, fatty acids and their salts, fatty alcohols, fatty esters, fatty amines, fatty amine acetates, and fatty amides. Preferred lubricants/release agents are fatty acids, fatty acid salts and fatty amine acetates. In one type of embodiment of the invention, the amount of lubricant/ release agent in the water-soluble film is in the range of about 0.02% of the mass. up to about 1.5% of the mass. and, optionally, from about 0.1% of the mass. up to about 1% of the mass.

[00104] Suitable fillers/diluents/anti-adhesives/tackifiers include, but are not limited to: cross-linked polyvinylpyrrolidone, cross-linked cellulose, microcrystalline cellulose, silicon dioxide, metal oxides, calcium carbonate, talc, mica, stearic acid, and the metals of the above compounds, for example, magnesium stearate. Optionally, the water-soluble film may contain additional unmodified starch or modified starch in addition to the specific starch components described above, for example, hydroxypropyl modified starch, the amount of which is in the range from about 5 m.h. up to about 30 m.h. per 100 m.h. resins or modified starch with a degree of modification of more than about 2%, the amount of which is in the range from about 2.5 m.h. up to about 30 m.h. per 100 m.h. gum, or unmodified starch with an amylose content ranging from about 20% to about 80%, or hydroxypropyl-modified starch with an amylose content ranging from about 23% to about 95%, if the polyvinyl alcohol contains either unmodified polyvinyl alcohol or anionically modified copolymer of polyvinyl alcohol with the proviso that the anionic modifier is not an acrylate. Preferred materials are starches, modified starches and silica. In one type of embodiment of the invention, the amount of filler/diluent/anti-adhesive/detackifier in the water-soluble film may range from about 1 wt%. up to about 6% of the mass. or from about 1% of the mass. up to about 4% wt., or from about 2% wt. up to about 4% wt., or, for example, from about 1 m.h. up to about 6 m.h. per 100 m.h. resin, or from about 1 m.h. up to about 4 m.h. per 100 m.h. resin, or from about 2 m.h. up to about 4 m.h. per 100 m.h. resin, In embodiments of the invention, if the water-soluble film contains starch or modified starch as an addition to one of the above specific starch components, then the content of the additional starch component will be no more than about 50% of the mass. based on the total weight of all starches contained in the film. Regardless of theory, it is believed that the addition of an additional starch component to the film formulation that does not provide additional benefits to the water-soluble film does not affect any benefit provided by the addition of the main starch component as described herein.

[00105] The water-soluble film may additionally contain residual moisture in an amount of at least 4% wt., for example, from about 4% wt. up to about 10 wt. %, as measured by Karl Fischer titration.

Film production method

[00106] One contemplated class of embodiments of the invention features a water-soluble film of water-soluble bags, for example, by casting from a solution. Solution casting methods for PVA are well known in the art. For example, in the film forming process, polyvinyl alcohol-based polymers and auxiliary additives are dissolved in a solvent, usually water, and applied in a measured amount to the surface, dried thoroughly (or forced drying is carried out) until a cast film is obtained, and then the resulting cast film removed from the mold surface. The process can be carried out serially, and greater productivity is achieved by its continuous implementation. For example, water or solvent is heated to a temperature in the range of about 80°C to 90°C, with plasticizers, starches and auxiliary additives first added to the water or solvent, and then surfactants are added. The mixture is stirred until a homogeneous mixture is obtained. Then, film-forming resins are added to the mixture and stirred at a temperature of 80 °C to 90 °C until a homogeneous state is reached.

[00107] In the production of continuous films from polyvinyl alcohol, it is common practice to dose the solution onto a moving casting surface, such as a continuously rotating metal drum or conveyor belt, which results in substantially complete removal of the solvent from the liquid to form a self-contained cast film, followed by stripping the resulting cast film from the forming surface.

[00108] Optionally, the water-soluble film may be a single film consisting of one layer or a number of such layers.

[00109] Residual moisture content

[00110] The water-soluble film may additionally contain residual moisture in an amount of at least 4% wt., for example, from about 4% wt. up to about 10 wt. %, as measured by Karl Fischer titration.

Bags/Packs

[00111] The water-soluble film described herein is suitable for creating a sealed product in the form of a bag and sets the internal volume of the bag to contain the composition. "Sealed product" includes sealed compartments having a vent, for example, in embodiments of the invention, characterized in that the compartment contains a solid that releases gases. The bag composition may take any form such as powders, gels, pastes, liquids, tablets, or any combination of the foregoing. The film is also suitable for any other application where improved wet performance and low residue in cold water are desired.

[00112] The film described herein can also be used to form a bag with two or more compartments made from the same film or in combination with films of other polymeric materials. It is known in the art that additional films can be obtained, for example, by casting, blow molding, extrusion or blow molding from the same or different polymeric materials. In one embodiment, the polymers, copolymers, or derivatives thereof which are suitable for use as an additional film are selected from polyvinyl alcohols, polyvinylpyrrolidone, polyalkylene oxides, polyacrylic acid, cellulose, cellulose ethers, cellulose esters, cellulose amides, polyvinyl acetates, polycarboxylic acids. and salts, polyamino acids or peptides, polyamides, polyacrylamide, maleic/acrylic acid copolymers, polysaccharides including starch and gelatin, natural gums such as xanthan, and carrageenans. For example, the polymers may be selected from polyacrylates and water-soluble acrylate copolymers, methylcellulose, sodium carboxymethylcellulose, dextrin, ethylcellulose, hydroxyethylcellulose, hydroxypropylmethylcellulose, maltodextrin, polymethacrylates, and a combination of the foregoing, or selected from polyvinyl alcohols, polyvinyl alcohol-hydroxypropylmethylcellulose (HPMC) copolymers, and combinations of the above compounds. One contemplated class of embodiments of the invention is characterized by a polymer content in the bag material, such as the PVA copolymer described above, and as described above being at least 60%.

[00113] The bags of the present disclosure may include at least one sealed compartment. Therefore, the bags may contain one compartment or several compartments. The water soluble bag can be made from two layers of water soluble polymeric film sealed at the interface, or from a single film folded and sealed. One or both of the films are PVA films as described above. Films define the internal volume of the bag, which contains any desired composition for release in the aquatic environment. There is no particular limitation for said composition, and it may contain, for example, any of the various compositions described below. In embodiments of the invention containing multiple compartments, each compartment may contain identical and/or different compositions. In turn, the compositions may take any suitable form, including liquids, solids, and combinations of the foregoing (eg, a solid suspended in a liquid). In some embodiments, the bags comprise first, second, and third compartments, each containing a different first, second, and third composition, respectively.

[00114] The compartments in multi-compartment bags may be of the same or different size(s) and/or volume(s). The compartments of such multi-compartment bags may be separated or connected in any suitable manner. In some embodiments of the invention, the second and/or third and/or subsequent compartments are aligned with the first compartment. In embodiments of the invention, the second and/or third and/or subsequent compartments have a linear or concentric orientation. The compartments can be packed as a strip, with each compartment individually separable by means of a perforation line. Therefore, the end user can tear off each individual compartment from the rest of the tape.

[00115] The geometry of the compartments may be the same or different. In embodiments of the invention, optionally, the geometry and shape of the third and subsequent compartments differ from those of the first and second compartments. In these embodiments of the invention, optionally, the third and subsequent compartments are located in the structure on the first or second compartment. The design may be decorative, educational, or illustrative, such as to illustrate a concept or explanation and/or indicate the origin of a product.

[00116] The bags/or bags of the present disclosure may contain one or more different films. For example, in single-compartment embodiments, the bag may be made from a single wall that is folded in half and sealed at the edges, or alternatively, from two walls that are sealed at the edges. In multi-compartment embodiments, the pouch may be made from one or more films such that any given pouch compartment may comprise walls made from a single film or from multiple films having different compositions.

[00117] Bags and bags can be made using any suitable equipment and method. For example, single compartment pouches can be made using vertical fill and seal, horizontal fill and seal, or rotary drum fill and seal methods commonly known in the art. Such methods may be continuous or discontinuous. The film can be moistened and/or heated to improve its pliability. The method may also include using a vacuum to draw the film into a suitable shape. Vacuum drawing the film into the mold can be applied for about 0.2 seconds to 5 seconds, or about 0.3 seconds to about 3 seconds, or about 0.5 seconds to 1.5 seconds after the film is on the horizontal part of the surface. The vacuum may be such as to provide a reduced pressure in the range of 10 mbar to 1000 mbar or, for example, 100 mbar to 600 mbar.

[00118] The forms in which the bags can be made can be of any shape, length, width and depth, depending on the required dimensions of the bags. Forms can also vary in size and shape if required. For example, the volume of the finished bags may be from about 5 ml to about 300 ml, or from about 10 ml to 150 ml, or from about 20 ml to about 100 ml, and the sizes of the molds are selected accordingly.

Forming, sealing and thermoforming

[00119] A thermoformable film is a film that can be formed using heat and mechanical action.

[00120] Film thermoforming is the process of heating a film, shaping it (eg, in a profile shape), and then cooling the film, as a result of which the film takes its shape, for example, the shape of a profile. The heating may be carried out by any suitable means. For example, the film can be heated directly by passing it under a heating element or through a source of hot air before it is applied to the surface or after it is placed on the surface. Alternatively, it can be heated indirectly, such as by surface heating or by placing a hot element on the film. In some embodiments of the invention, the film is heated using infrared radiation. The film can be heated to temperatures ranging from about 50°C to about 150°C, from about 50°C to about 120°C, from about 60°C to about 130°C, from about 70°C to about 120°C. or from about 60°C to about 90°C. Thermoforming can be carried out by one or more of the following methods: manual molding with mechanical prestretching of the thermally softened film on the mold, or molding the softened film in the mold under pressure (e.g., vacuum forming), or by automatic high-speed feeding of an extruded sheet with an accurate known temperature. to a forming and cutting station, or by automatic placement, punching and/or pneumatic stretching and pressure forming of the film.

[00121] In alternative embodiments, the film may be wetted in any suitable manner, such as directly by spraying a wetting agent (including water, a film composition solution, a plasticizer for the film composition, or any combination of the above) onto the film before it is applied to a surface or after it has been placed on a surface. surface, or indirectly by wetting the surface or applying a wet element to the film.

[00122] After heating and/or wetting the film, it can be drawn into a suitable shape, preferably by vacuum. Filling of the formed film can be accomplished by any suitable means. In some embodiments of the invention, the most preferred method depends on the shape of the product and the desired filling rate. In some embodiments of the invention, the formed film is filled using an inline filling system. The filled, open pouches are then closed with a second film to form pouches in any suitable manner. This can be done in a horizontal arrangement and in continuous, constant motion. Closing can be carried out by continuously feeding a second film, preferably a water-soluble film, over and onto the opened pouches, followed by the preferred co-welding of the first and second film, usually in the area between the profile shapes and hence between the pouches.

[00123] Any suitable method can be used to seal the pouch and/or its individual compartments. Non-limiting examples of such methods include thermal sealing, solvent welding, or wet welding, as well as combinations of the above. As a rule, only the area intended for the formation of the sealing seam is thermally treated or treated with a solvent. The heat or solvent may be applied in any manner, generally to the closure material, and generally only to the areas to be sealed. When using welding or welding with a solvent or water, the simultaneous use of heat may be preferred. Preferred methods of sealing/welding with water or solvent include selectively applying the solvent to the areas between the molds or to the cover material, for example, by spraying or printing in these areas, followed by applying pressure to these areas to obtain a sealing seam. For example, you can use rollers and tapes for sealing, as described above (optionally with simultaneous heating).

[00124] The formed bags can then be cut with a cutting device. The cutting can be carried out by any known method. It may be preferable to perform continuous cutting, and preferably perform it at a constant speed, and preferably in a horizontal position. The cutting device can be, for example, a sharp element or a hot element, or a laser, whereby in the latter two cases the hot element or laser "burns through" the area of the film seal.

[00125] The different compartments of a multi-compartment pouch may be made together in a linear or concentric orientation, and the resulting bonded pouches may or may not be separated by cutting. In alternative embodiments, departments may be created separately.

[00126] In embodiments of the invention, bags can be made according to a method comprising the following steps: a) forming a first compartment (as described above); b) forming a recess within some or all of the closed compartments made in step (a) to create a second molded compartment located above the first compartment; c) filling and closing the second compartments with a third film; d) sealing the first, second and third films; and e) cutting the films to make a multi-compartment bag. The recesses formed in step (b) can be obtained by applying a vacuum to the compartments obtained in step (a).

[00127] The second and/or third compartment(s) can be made in a separate step and then combined with the first compartment, as described in European patent application No. 08101442.5 or in US patent application No. 2013/240388 A1 or document WO 2009/ 152031.

[00128] In embodiments of the invention, bags can be made according to a method comprising the following steps: a) forming a first compartment, optionally using heat and/or vacuum, using a first film on a first molding machine; b) filling the first compartment with the first composition; c) optionally filling the second compartment with the second composition; d) sealing the first and optionally the second compartment by sealing the second film to the first film; and e) cutting the films to make a multi-compartment bag.

[00129] In embodiments of the invention, bags can be made according to a method comprising the following steps: a) forming a first compartment, optionally using heat and/or vacuum, using a first film on a first molding machine; b) filling the first compartment with the first composition c) deforming the second film on a second forming machine, optionally using heat and/or vacuum to form the second and optionally third compartments; d) filling the second and optionally the third compartments; e) sealing the second and optionally the third compartment using a third film; f) placing sealed second and optionally third compartments on the first compartment; g) sealing the first, second and optionally third compartment; and h) cutting the films to form a multi-compartment bag.

[00130] The first and second molding machines may be selected based on their suitability for performing the above method. In some embodiments, the first molding machine is preferably a horizontal molding machine and the second molding machine is preferably a rotary drum molding machine, preferably positioned above the first molding machine.

[00131] It should be understood that by using appropriate feed stations it may be possible to manufacture multi-compartment bags containing a plurality of different or specific compositions and/or different or specific liquid, gel or paste compositions.

[00132] In some embodiments, the film and/or bag is sprayed or dusted with a suitable material, such as an active ingredient, a lubricant, an aversive ingredient, or mixtures of the foregoing. In some embodiments of the invention, printed information is applied to the film and/or bag, for example, using ink and/or an active ingredient.

Vertical forming, filling and sealing

[00133] In embodiments of the invention, the water-soluble film of the present disclosure may be formed into a sealed article. In embodiments of the invention, the sealed article is a vertically shaped, filled, and sealed article. The vertical form, fill and seal (VFFS) method is a conventional automated method. VFFS includes devices such as an assembly machine that winds a single piece of film around a vertically oriented feed tube. The machine heat seals or otherwise seals opposite edges of the film to create a side seal seal and form the film into a hollow sleeve. The machine then heat seals or otherwise creates a bottom seal, thereby forming part of an open top container for which a top seal will subsequently be created. Through the open top, the machine introduces a certain amount of fluid product into the container part. After filling the container with the desired amount of product, the machine sends the film to another heat sealer, for example to create a top seal. Finally, the machine sends the film to a cutter which cuts the film just above the top seam to produce a filled package.

[00134] During operation, the assembly machine picks up a film from a roll to form a package. Therefore, the film should easily pass through the machine and not stick to machine components or break during processing due to low strength.

[00135] Water soluble films can be processed with VFFS on a Rovema VFFS or equivalent. The bags/bags are prepared in a standard laboratory atmosphere at 78°F (about 25.5°C) and 24% relative humidity. We produce both empty bags and bags filled with salt. The salt-containing bags are filled to a weight of 1.2 pounds (about 550 g) at the maximum fill level. The temperature of the horizontal seal is 225°F (about 107°C) and the temperature of the vertical seal varies as needed to obtain a good seal, for example from about 255°F (about 124°C) to 280°F (about 138°C). ).

The contents of the bags

[00136] These articles (eg, in the form of bags or pouches) may contain various compositions, such as household compositions (detergents) or non-household compositions. Multi-compartment bags in each individual compartment may contain the same or different compositions. The composition is close to the water-soluble film. The composition may be less than about 10 cm from the film, or less than about 5 cm, or less than about 1 cm. Typically, the composition is in close proximity to or in contact with the film. The film may be in the form of a bag or compartment containing the composition.

[00137] The inner film of the bag can be used as a barrier to physically separate compositions containing incompatible ingredients. It is believed that such a separation may increase the period of normal operation and/or reduce the physical instability of such ingredients. Additionally or alternatively, such separation may provide aesthetic benefits, as described in US Patent Application No. 8,835,372.

[00138] In embodiments of the invention, the composition may be selected from the group of synthetic detergent compositions, such as low-power and high-power liquid synthetic detergent compositions, powdered synthetic detergent compositions, hand and/or machine dishwashing detergents; cleaning compositions for hard surfaces, fabric conditioners, washing gels commonly used for washing clothes, as well as bleaching and washing additives, shaving creams, skin care products, hair care compositions (shampoo and conditioners) and detergents for body. Such detergent compositions may contain surfactants, bleaches, enzymes, perfumes, dyes or pigments, solvents, and combinations of the foregoing.

[00139] In embodiments of the invention, the composition may be selected from a group of non-household compositions, including compositions for agricultural use, compositions for vehicles, compositions for aviation, food and nutritional compositions, compositions for industry, compositions for animal husbandry, marine transport compositions, medical compositions, commercial compositions, military and quasi-military compositions, office compositions, recreational and park compositions, pet compositions, including cleaning and washing compositions suitable for any such use.

[00140] In embodiments of the invention, the composition contained in the interior of the bag is a synthetic detergent composition. Optionally, the detergent composition is selected from the group consisting of washing powder, dishwashing detergent, hard surface cleaning composition, fabric conditioner compositions, shaving creams, skin care products, hair care compositions (shampoo and conditioners) , body cleansers and combinations of the above.

[00141] Non-limiting examples of useful non-household compositions include compositions for agricultural use, compositions for motor vehicles, compositions for aviation, food and nutritional compositions, compositions for industry, compositions for animal husbandry, compositions for maritime, medical compositions, commercial compositions, military and quasi-military compositions, office compositions, recreational and park compositions, pet compositions, water treatment compositions, including cleaning and washing compositions suitable for any such use. Compositions suitable for use in the proposed bags may be in the form of a liquid, solid or powder. Liquid compositions may contain a solid. The solids may contain powder or agglomerates such as microcapsules, beads, strips, or one or more pearlescent beads, or mixtures of the foregoing. Such solids may provide technical advantage through laundering advantage, preconditioning advantage, use of delayed or sequential action components; additionally or alternatively, they can provide an aesthetic effect (for example, perfumed microcapsules).

[00142] The compositions encapsulated by the films described herein, if they are liquid compositions, may have any suitable viscosity values depending on such factors as the components of the composition and the purpose of the composition. In one embodiment of the invention, for high shear values, the viscosity values of the composition at a shear rate of 20 s ^-1 and a temperature of 20 ° C are from 100 cP to 3000 cP, alternatively from 300 cP to 2000 cP, alternatively from 500 cP up to 1000 cP, while for low shear values of the viscosity of the composition at a shear rate of 1 s ^-1 and a temperature of 20 ° C range from 500 cP to 100000 cP, alternatively - from 1000 cP to 10000 cP, alternatively - from 1300 cP up to 5000 cP. Methods for measuring viscosity are known in the art. According to the present invention, viscosity measurements were made using a rotational viscometer, such as the AR550 from TA instruments. The device contains a 40 mm cone fixture with a 2° or 1° taper angle and a gap of about 50-60 µm for isotropic liquids, or a 40 mm flat steel plate with a 1000 µm gap for particles containing liquids. The measurement is performed using a flow detection method that includes conditioning, peak hold, and continuous ramp steps. The conditioning step includes setting the measurement temperature at 20 ^° C, preshifting for 10 seconds at a shear rate of 10 s ^-1 , and equilibrating for 60 seconds at the selected temperature. Peak hold includes setting a shear rate of 0.05 s ^-1 at 20°C for 3 min with sampling every 10 seconds. The continuous step step is performed at a shear rate of 0.1 s ^-1 to 1200 s ^-1 for 3 minutes at 20° C. to obtain a complete flow profile.

[00143] As described above, the composition may be a non-household composition. For example, the non-domestic composition may be selected from the group consisting of an agricultural composition, an automotive composition, an aviation composition, food and nutrition compositions, an industrial composition, an animal husbandry composition, a marine composition. transport, medical compositions, commercial compositions, military and quasi-military compositions, office compositions, recreational and park compositions, pet compositions, water treatment compositions, including cleaning and washing compositions suitable for any such use.

[00144] In one embodiment of the invention, the composition may contain agrochemicals, for example, one or more insecticides, fungicides, herbicides, pesticides, miticides, repellents, attractants, defoliants, plant growth regulators, fertilizers, bactericides, trace elements and trace elements. Suitable agrochemicals and adjuncts are described in US Pat. Nos. 6,204,223 and 4,681,228 and EP 0989803 A1. For example, suitable herbicides include paraquat salts (e.g. paraquat dichloride or paraquat bis(methyl sulfate), diquat salts (e.g. diquat dibromide or diquat alginate), glyphosate or a salt or ester thereof (e.g. isopropylammonium glyphosate, sesquisol glyphosate, or trimesium glyphosate). , also known as sulfosate.) Incompatible crop protection chemical pairs can be used in separated compartments, for example, as described in US Patent No. 5,558,228 Incompatible crop protection chemical pairs that can be used include, for example, bensulfuron-methyl and molinate; 2,4-D and thifensulfuron-methyl; 2,4-D and methyl 2-[[[N-4-methoxy-6-methyl-1,3,5-triazin-2-yl) -N- methylamino]carbonyl]amino]sulfonyl]benzoate; 2,4-D and metsulfuron-methyl; maneb or mancozeb and benomyl; glyphosate and metsulfuron-methyl; tralometrin and any organophosphate such as monocrotophos or dimethoate; bromoxynil and N-[[4,6-dimethoxypyrimidin-2-yl)amino]carbonyl]-3-(ethylsulfonyl)-2-pyridinesulfonamide; bromoxynil and methyl 2-[[[((4-methyl-6-methoxy)-1,3,5-triazin-2-yl)amino]carbonyl]amino]sulfonyl]benzoate; bromoxynil and methyl 2-[[[N-(4-methoxy-6-methyl-1,3,5-triazin-2-yl)-N-methylamino]carbonyl]amino]sulfonyl]benzoate. In another closely related type of embodiment of the invention, the composition may include one or more seeds, optionally together with soil and, additionally, optionally together with one or more additional components selected from mulch, sand, peat, water jelly crystals and fertilizers, for example, including the types of embodiments described in US Pat. No. 8,333,333.

[00145] In another embodiment, the composition is a water treatment agent. Such components include harsh oxidizing chemicals, such as those described in US Patent Application Publication No. 2014/0110301 and US Patent No. 8,728,593. For example, disinfectants may include hypochlorite salts such as sodium hypochlorite, calcium hypochlorite, and lithium hypochlorite; chlorinated isocyanurates such as dichloroisocyanuric acid (also referred to as "dichlor" or dichloro-s-triazinetrione, 1,3-dichloro-1,3,5-triazinane-2,4,6-trione) and trichloroisocyanuric acid (also referred to as "trichlor" or 1,3,5-trichloro-1,3,5-triazinan-2,4,6-trione). The use of salts and hydrates of disinfectant compounds is also envisaged. For example, dichloroisocyanuric acid can be used in the form of sodium dichloroisocyanurate, sodium dichloroisocyanurate dihydrate, among others. Brominated disinfectants may also be suitable for use in unit dose packages such as 1,3-dibromo-5,5-dimethylhydantoin (DBDMH), 2,2-dibromo-3-nitrilopropionamide (DBNPA), dibromocyanoacetic acid amide 1- bromine-3-chloro-5,5-dimethylhydantoin; and 2-bromo-2-nitro-1,3-propanediol, among others. The oxidizing agent may be one of those described in US Pat. No. 7,476,325, such as potassium hydrogen peroxymonosulfate. The composition may be a pH adjusting chemical, for example as described in U.S. Patent Application Publication No. 2008/0185347, and may contain, for example, an acidic component and an alkaline component such that the composition reacts violently upon contact with water and adjusts the pH of the water. . Suitable ingredients include sodium bicarbonate, sodium bisulfate, potassium hydroxide, sulfamic acid, organic carboxylic acids, sulfonic acids, and potassium dihydrogen phosphate. The buffer mixture may include, for example, boric acid, sodium carbonate, glycolic acid and oxone monopersulfate.

[00146] The water treatment agent may be or may contain a flocculant, for example, as described in US Patent Application Publication No. 2014/0124454. The flocculant may comprise a polymeric flocculant, for example polyacrylamide, a polyacrylamide copolymer such as acrylamide copolymers of diallylmethylammonium chloride (DADMAC), dimethylaminoethyl acrylate (DMAEA), dimethylaminoethyl methacrylate (DMAEM), 3-methylamidopropyltrimethylammonium chloride (MAPTAC), or acrylic acid; cationic polyacrylamide; anionic polyacrylamide; neutral polyacrylamide; polyamine; polyvinylamine; polyethyleneimine; polydimethyldiallylammonium chloride; polyoxyethylene; polyvinyl alcohol; polyvinylpyrrolidone; polyacrylic acid; polyphosphoric acid; polystyrenesulfonic acid; or any combination of the above compounds. The flocculant may be selected from chitosan acetate, chitosan lactate, chitosan adipate, chitosan glutamate, chitosan succinate, chitosan malate, chitosan citrate, chitosan fumarate, chitosan hydrochloride, and combinations of the above compounds. The water treatment composition may include a phosphate removing agent, such as one or more selected from zirconium compounds, rare earth lanthanide salts, aluminum compounds, iron compounds, or any combination of the foregoing.

[00147] The composition may be a descaling composition, eg citric or maleic acid or its sulfate salt, or any mixture thereof, eg as described in US Patent Application No. 2006/0172910.

[00148] Various other types of compositions are contemplated for use in the pouches described herein, including particulate matter, such as down feathers, for example, as described in US RE29059 E; superabsorbent polymers, for example, as described in US Patent Application Publication Nos. 2004/0144682 and 2006/0173430; pigments and highlights, for example, as described in US Patent No. 3,580,390 and US Patent Application Publication No. 2011/0054111; soldering flux (eg, alkali metal fluoroaluminates, alkali metal fluorosilicates, and alkali metal fluorozincates), for example, as described in US Pat. No. 8,163,104; food products (eg coffee powder or dried soup) as described in US Patent Application Publication No. 2007/0003719; and wound dressings, for example, as described in US Pat. No. 4,466,431.

Dissolution and disintegration test (MSTM 205)

[00149] The film can be characterized or tested for dissolution time and disintegration time in accordance with the MonoSol 205 (MSTM 205) test method known in the art. See, for example, US Pat. No. 7,022,656.

[00150] Equipment and materials:

1. Chemical glass 600 ml

2. Magnetic Stirrer (Labline Model #1250 or equivalent)

3. Magnetic stirrer bar (5 cm)

4. Thermometer (0°C to 100°C ± 1°C)

5. Stencil, stainless steel (3.8 cm x 3.2 cm)

6. Timer (0-300 seconds, accurate to the nearest second)

7. Polaroid 35mm slide frame (or equivalent)

8. Frame holder for MonoSol 35 mm slide (or equivalent)

9. Distilled water

[00151] For each film tested, three test specimens are cut from the film sample using a stainless steel stencil (i.e., 3.8 cm x 3.2 cm samples). When cutting from a film web, samples should be cut from areas of the web that are evenly spaced along the transverse direction of the web. Then, each experimental sample is analyzed using the following method.

1. Fix each specimen in a separate 35 mm slide frame.

2. Pour 500 ml of distilled water into a glass. Measure the temperature of the water with a thermometer and, if necessary, heat or cool the water to maintain the temperature at 20°C (approximately 68°F).

3. Mark the height of the water column. Install the magnetic stirrer on the base of the holder. The beaker is placed on a magnetic stirrer, the magnetic stirrer bar is placed in the beaker, the stirrer is turned on and the stirring speed is adjusted until a funnel is formed, which is approximately one-fifth of the height of the water column. Mark the depth of the funnel.

4. Attach the 35mm slide frame to the alligator clip of the 35mm MonoSol slide frame holder with the long end of the slide frame parallel to the surface of the water. The depth adjuster of the holder must be set so that when lowered, the end of the clamp is 0.6 cm below the surface of the water. One of the short sides of the slide frame should be positioned next to the side wall of the beaker and the other should be positioned directly above the center of the stirrer bar so that the film surface is perpendicular to the water flow.

5. In one motion, lower the fixed slide and clip into the water and start the timer. Destruction occurs when the film is torn off. When the entire visible part of the film is separated from the slide frame, remove the slide from the water, continuing to visually determine the content of undissolved film fragments in the solution. Dissolution occurs when all film fragments visually disappear and the solution becomes transparent.

[00152] The results should include the following: complete identification of the sample; individual and average time of destruction and dissolution; and the temperature of the water at which the samples were tested.

[00153] Breakdown time (I) of the film and dissolution time (S) of the film can be corrected for a standard or reference film thickness using the exponential algorithms presented in Equation 1 and Equation 2, respectively, below.

I _correct. =I _measured. /(reference thickness/measured thickness) ^1.83 [1]

S _correct. =S _measured. /(reference thickness/measured thickness) ^1.93 [2]

Tensile strength test

[00154] Tests of the film being investigated or to be tested for tensile strength according to the Tensile Strength Test were analyzed as follows. The method includes the determination of tensile strength according to ASTM D 882 ("Standard Test Method for Tensile Mechanical Properties of Thin Plastic Film Material") or equivalent. An ^INSTRON® Tensile Tester (Model 5544 Tensile Tester or equivalent) is used to obtain film data. A minimum of three test specimens are used for each measurement, each cut with robust cutting tools to ensure dimensional stability and reproducibility, and tested in the machine direction of travel (MD) (if applicable) for each measurement. The tests are carried out at a standard laboratory temperature of 23 ± 2.0°C and a relative humidity of 35 ± 5%. To determine the tensile strength, 1 inch (2.54 cm) wide samples are prepared from a single film tape having a thickness of 3.0 ± 0.15 mils (or 76.2 ± 3.8 microns). The sample is then transferred to the ^INSTRON® Tensile Tester to continue testing while minimizing exposure under 35% relative humidity conditions. The tensile tester is prepared according to the manufacturer's instructions, fitted with a 500 N strain gauge and calibrated. Install the correct clamps and surfaces ( ^INSTRON® clamps have model number 2702-032 rubber coated surfaces 25mm wide or equivalent). The samples are installed in a tensile tester and analyzed to determine the value of the tensile strength (ie the force required to break the film).

[00155] Suitable properties of the films according to the present description are characterized by values of tensile strength (in machine direction (MD)), constituting at least about 40 MPa, measured according to the Tensile Strength Test. In various embodiments of the invention, the tensile strength values for the film are from at least 40 MPa and or up to about 60 MPa (for example, about 40 MPa, about 45 MPa, about 60 MPa, about 55 MPa, or about 60 MPa).

Tensile strength test

[00156] This method includes determining the average force, in grams per mil, of sample thickness required to propagate a tear along a specified length of a polyvinyl alcohol (PVA) film. The force in grams required to propagate a tear through the film is measured using a finely calibrated pendulum device. Under the influence of gravitational force, the pendulum swings in an arc, breaking the sample located in the pre-created slot. The sample is held motionless on one side, while the other side is fixed on the pendulum. The pointer on the scale indicates the energy loss of the swing of the pendulum. The scale indication depends on the force required to break the sample. This method is suitable for determining the relative tear resistance of PVA films. Water-soluble films were evaluated with the Elmendorf Tensile Tester Model No. 40043 according to the MSTM 107RD standard test method for polyvinyl alcohol film for tear propagation resistance.

[00157] Before testing, water-soluble films were conditioned at a temperature of about 23°C +/- 3°C (73 ^o F +/- 5 ^o F) and a relative humidity of about 35%±5% for at least 8 hours. The tests were carried out in a standard laboratory atmosphere at a temperature of 23°C +/- 3°C (73 ^o F +/- 5 ^o F) and a relative humidity of 35%±5%. The average breaking force in grams per mil was calculated as follows:

Breaking force, g/mil=(additional weight g/100) x scale reading

Film thickness in mils

[00158] Suitable characteristics of the films according to the present description are characterized by values of tensile strength (in machine direction (MD)) of at least about 800 g/mil, measured using Test Tensile Strength. In various embodiments, the machine direction (MD) tensile strength values for the film are at least 500 g/mil and/or at least about 2000 g/mil (e.g., about 500 g/mil, about 800 g/mil). mil, about 1000 g/mil, about 1200 g/mil, or about 1500 g/mil).

Friction coefficient tests

[00159] A method for measuring the coefficient of friction is to test the mutual friction of two parts of the material, while measuring the force required to move one part of the material relative to the other. The force to start the sled (static friction) and the force to keep the sled moving (dynamic friction) are measured with a strain gauge according to ASTM D1894 "Plastic Film and Film Material Friction Test".

[00160] This procedure uses an Instron® friction coefficient tester model ^2810-005 or equivalent. A schematic representation of the apparatus is shown in Figure 2. An ^Instron® Model No. 5543 test apparatus or equivalent is also used.

[00161] The test apparatus includes a friction jig 10 which serves as a support for a friction slide 12 with a fixed film sample 14. The slide 12 is connected to the top clamp 18 via a tension cable 20 that passes through a roller block 22 attached to the friction jig 10. The bottom a withdrawal sleeve 24 secures the test fixture to an Instron® tester (not shown).

[00162] According to the Instron ^® "Blue Hill" application methodology, "The system: in the specified channel, searches for the maximum values for the data array from the start value to the end value; as a percentage of the maximum value, determines the first point at which the measurement data changes from rising to falling, and assigns the value of the first peak to this point; uses the following equation to determine the coefficient of static friction: static friction=first peak/sled weight; to calculate the average load in the area from the first peak to the final value uses the following equation: average load=energy/change in distance; and uses the following equation to determine the coefficient of dynamic friction: dynamic friction=average load/sled weight".

[00163] The test sample consists of samples having dimensions (5 inch by 5 inch square (12.7 cm by 12.7 cm square) for the sled and a 5 inch by 8 inch rectangle (12.7 cm by 20.3 cm ) for the surface that will form the test area. Since the film thickness is believed to have no effect on the static coefficient of friction, the film thickness may be 3.0 ± 0.10 mils (or 76.2 μm ± 2.5 μm). Samples may be cut using, for example, a razor blade and appropriately sized templates.If necessary, the sample should be cut with a larger size parallel to the machine direction of the cast film.As in the previous example, if necessary, the machine direction of the 5" x 5" sample should be marked and oriented during testing so that the pull direction of the sled is parallel to the machine direction of the film sample.

[00164] Test samples must be conditioned at 75 oF ± 5 oF and 35% ± 5% relative humidity for at least 8 hours prior to testing, and the test is carried out under the same conditions of temperature and relative humidity.

[00165] COF Friction Measuring Device Mounting Procedure

1. Remove the pin from the lower jaw on the Instron® Friction Coefficient Tester model ^2810-005 and remove it.

2. Remove the pin from the top clip and remove it.

3. Place lower friction tool turnbuckle on ^Instron® Model #5543 Tester Base Adapter

4. Install it with a hairpin.

5. Loop one end of the tension cable over the top pin and replace the locking latch.

6. Calibrate Tester Model No. 5543

7. Hook the loop at the other end of the tension cable to the hook of the friction slide.

8. Make sure the roller block can rotate freely.

9. Move the slide until the tension cord is no longer slack and is located in the groove of the roller block.

10. Install the movable slider (top) of the ^Instron® Friction Coefficient Tester, model 2810-005, so that there is enough clearance for the full slide travel in the 50 mm test zone without resting against the roller block.

11. During the movement of the slider, keep the cable taut.

12. Using the JOG control on the Instron #5543 control panel, set the extension limit so that the far end of the friction sled does not extend beyond the test plane (the plane perpendicular to the axis of motion and farthest from the roller block) of the friction fixture. To set the travel limit, press the GL button. This prevents the friction slide from colliding with the roller block during the test and ensures that the coefficient of friction of the test specimen is measured correctly.

13. The test fixture is now ready to go.

Sample placement procedure

1. Place the surface sample in the appropriate orientation on the aluminum friction fixture.

2. Stretch the surface sample over the edges of the aluminum surface and attach the sample to the underside of the friction fixture.

3. It is important to fasten the band along the end of the friction tool furthest from the withdrawal sleeve to avoid the sled sticking to the surface.

4. Make sure the material is taut but not stretched.

5. Wrap the friction slide with a 5" x 5" pattern so that the machine direction of the film is parallel to the direction of travel of the slide.

6. Attach the edges of the sample to the top of the slide, making sure that no excess material is left on the surface sample.

7. Attach the other edges of the specimen to the friction slide so that the specimen is taut and in contact with the measurement surface.

8. Make sure that there is no residue of the fastening tape in the measurement area on the sled and on the friction device.

9. The samples on the friction surface and on the friction slide must be flattened without wrinkles or bulges to avoid errors in the measurement of the coefficient of friction COF .

10. Inspect the sled to ensure that there are no foreign materials that are in contact with the surfaces to be tested.

11. Attach the sled to the cable and very lightly and carefully place the sled on the friction table in order to prevent an unnatural bond between the two specimens. Start testing immediately.

12. Ensure that when fully extended, the sled is fully positioned over the sample placed on the friction fixture and is not in contact with the belt or hanging over the edges of the friction fixture.

Carrying out tests to determine the coefficient of friction COF

1. Test at least three samples for the desired orientation (for example, outside - outside or mold side - mold side).

2. For combined tests for out-to-mould orientations, the outer side is a film sample placed on an aluminum test surface, with the material wrapped around the sled as the mold side.

3. When working with film samples, be sure to use powder-free, moisture-proof gloves; powder or moisture may affect the measurement accuracy.

4. Cut the sample as described above, eg using a template.

5. Place the friction slide wrapped in the first sample on the end of the friction fixture furthest from the roller block.

6. Check cable tension.

7. On the test run screen, open the "friction coefficient test" window titled "COF.im ptf".

8. To start testing, press the "Start" button on the screen.

9. After the test run of the sample test is completed, press the OK button and return the friction slide to its original position, then replace the film sample on the friction slide and fixture. Repeat test.

[00166] The film may have a static coefficient of friction (COF) with values in the range of 4.0 or less, or 2.0 or less, or 1.5 or less, or 1.25 or less, or 1.0 or less, for example 1.0, 0.9, 0.8, 0.7, 0.6 or even less. In another aspect, static COF values may be less than 4.0, or less than about 2.5, or less than 2, or less than 1.

[00167] In one or more aspects, the film may have static COF values for smooth surfaces GG of less than 5 and a tensile strength ranging from 40 MPa to 60 MPa.

[00168] The water soluble films as described herein may be better understood in light of the following examples, which are only intended to illustrate water soluble films and are in no way intended to limit their scope.

Examples

Example 1

[00169] Were prepared water-soluble films containing water-soluble polyvinyl alcohol, plasticizer and modified starch. The film compositions contained a polyvinyl alcohol copolymer having about 4% maleate modification. The three film compositions additionally included about 26 m.h. plasticizers per 100 m.h. resins, minor amounts of processing aids, such as surfactants, antioxidants, etc., in a total amount of about 1 m.h. per 100 m.h. resins, as well as hydroxypropyl-modified starch containing 80% amylose and about 6% hydroxypropyl modification, the amount of which was at the level of 2.66 m.h. per 100 m.h. resin ( 1a ), about 7.98 m.h. per 100 m.h. resin ( 1b ) or 23.94 m.h. per 100 m.h. resin ( 1c ). These films contained about 77% of the mass. ( 1a ), about 74% wt. ( 1b ) and about 66% wt. ( 1c ) PVA resin based on total film weight. Three additional film formulations, in addition to the PVA resin, contained about 26 ppm. plasticizers per 100 m.h. resins, minor amounts of processing aids such as surfactants, antioxidants, etc. in a total amount of about 1 m.h. per 100 m.h. resins, as well as ethoxylated starch containing about 20% amylose and 2% hydroxypropyl modification, the amount of which was at the level of 2.66 m.h. per 100 m.h. resin ( 1d ), about 7.98 m.h. per 100 m.h. resin ( 1e ) or 23.94 m.h. per 100 m.h. resin ( 1f ). These films contained about 77% of the mass. ( 1d ), about 74% wt. ( 1e ) and about 66 wt. ( 1f ) PVA resins based on total film weight. Films with a thickness of about 75 μm were obtained. The films were tested for cold water solubility at 10°C according to MSTM-205, tensile strength according to the Tensile Strength Test and coefficient of friction according to the Friction Coefficient Test. Films with solubility up to 100 seconds are marked with (+) in Table 1 below, and films with solubility up to 300 seconds but more than 100 seconds are marked with (*) in Table 1. Films for which tensile strength values were about 45 MPa or more are marked with (+) in Table 1 below, and films for which tensile strength values were less than about 45 MPa but at least about 40 MPa or more are marked with (*) in Table 1, while films for which the tensile strength was less than 40 MPa are marked with (-) in Table 1. Films for which the values of the static coefficient of friction of the glossy surfaces were about 1 or less are marked with a (+) sign in Table 1 below, films for which the values for the coefficient of friction of the glossy surfaces were about 5 or less, but more than about 1, in are marked with (*) in Table 1, with films having glossy friction coefficient values greater than about 5 are marked with (-) in Table 1.

Table 1
Sample (m.h. starch per 100 m.h. resin) Solubility Tensile strength (MPa) Friction coefficient 1a (2.66) + + (49.84) * 1b (7.98) + + (55.78) + 1s (23.94) + + (48.48) + 1d(2.66) + + (55.44) - 1st (7.98) + + (52.22) - 1f(23.94) + + (44.87) +

[00170] Table 1 shows that the films according to the present description, containing a mixture of water-soluble polyvinyl alcohol, a plasticizer and hydroxypropyl-modified starch, present in an amount of from about 5 m.h. up to about 30 m.h. per 100 m.h. resins exhibit good cold water solubility, high tensile strength and excellent coefficient of friction. Table 1 additionally shows that the films of the present description containing a mixture of water-soluble polyvinyl alcohol, a plasticizer and hydroxypropyl-modified starch present in an amount of less than about 5 m.h. per 100 m.h. resins exhibit good cold water solubility, high tensile strength and an acceptable coefficient of friction. Table 1 additionally shows that the tensile strength for a water-soluble film containing hydroxypropyl-modified starch is maintained or increased as the starch content increases from about 2.5 ppm. up to about 24 m.h. per 100 m.h. resin, while the tensile strength for a water-soluble film containing ethoxylated starch decreases with increasing starch content.

[00171] Table 1 further shows that the films of the present disclosure, containing a mixture of water-soluble polyvinyl alcohol, plasticizer and modified starch with a degree of modification of more than about 2%, present in an amount of from about 2.5 m.h. up to about 30 m.h. per 100 m.h. resins show good solubility in cold water, high tensile strength and an acceptable coefficient of friction, while films with a starch content of about 5 m.h. up to about 30 m.h. per 100 m.h. resins exhibit a combination of good cold water solubility, high tensile strength and excellent coefficient of friction. Table 1 additionally shows that water-soluble films containing modified starch, with a degree of modification of about 2%, present in low concentrations, for example, not more than 12 m.h. per 100 m.h. resins show increased coefficients of friction compared to films containing modified starch with a degree of modification of more than 2% at the same concentrations. Table 1 further shows that the tensile strength of a modified starch-containing water-soluble film with a degree of modification greater than about 2% is maintained or increased as the starch content increases from about 2.5 ppm to about 2.5 ppm. up to about 24 m.h. per 100 m.h. resin, while the tensile strength of a water-soluble film containing modified starch with a degree of modification of less than about 2% decreases with increasing starch content.

[00172] Thus, Example 1 provides water-soluble films of the present disclosure containing a mixture of water-soluble polyvinyl alcohol, a plasticizer, and hydroxypropyl-modified starch present in an amount of from about 5 m.h. up to about 30 m.h. per 100 m.h. resins, while water-soluble films according to the present description, containing a mixture of water-soluble polyvinyl alcohol, plasticizer and modified starch with a degree of modification of more than about 2%, present in an amount of from about 5 m.h. up to about 30 m.h. per 100 m.h. resins are distinguished by good solubility in cold water, high convertibility and good interfilm anti-adhesion properties, as evidenced by the low coefficient of friction of smooth surfaces.

Example 2

[00173] Were prepared water-soluble films containing water-soluble polyvinyl alcohol, plasticizer and unmodified starch. The film compositions contained a polyvinyl alcohol copolymer having about 4% maleate modification. The film compositions additionally contained about 26 m.h. plasticizers per 100 m.h. resins, minor amounts of processing aids such as surfactants, antioxidants, etc. in a total amount of about 1 m.h. per 100 m.h. resins, as well as unmodified starch, the amount of which was at the level of about 2.66 m.h. per 100 m.h. resins ( 2a, 2d, 2g, 2j ), about 7.98 m.h. per 100 m.h. resins ( 2b, 2e, 2h, 2k ) or 23.94 m.h. per 100 m.h. pitches ( 2c, 2f, 2i, 2l ). Three films contained unmodified starch with an amylose content of 1% ( 2a, 2b, 2c ), three films contained unmodified starch with an amylose content of 25% ( 2d, 2e, 2 ), three films contained unmodified starch with an amylose content of 50% ( 2g, 2h , 2 ), and three films contained unmodified starch with an amylose content of 80% ( 2j, 2k, 2l ). These films contained about 77% of the mass. ( 2a, 2d, 2g, 2j ), about 74 wt. ( 2b, 2e, 2h, 2k ) and about 66 wt. ( 2c, 2c, 2f, 2i, 2l ) PVA resins based on total film weight. Films with a thickness of about 75 μm were obtained. The films were tested for cold water solubility at 10°C according to MSTM-205, tensile strength according to the Tensile Strength Test and coefficient of friction according to the Friction Coefficient Test. Films with a solubility of not more than 100 seconds are marked with (+) in Table 2 below, and films with a solubility of not more than 300 seconds but more than 100 seconds are marked with (*) in Table 2. Films for which tensile strength values were 45 MPa or more are marked with (+) in Table 2 below, and films for which tensile strength values were less than about 45 MPa, but at least about 40 MPa or more are marked with (*) in Table 2, while films for which the tensile strength was less than 40 MPa are marked with (-) in Table 2. Films for which the values of the static coefficient of friction of the glossy surfaces were about 1 or less in the following table 2 are marked with a (+), films for which the values for the coefficient of friction of the glossy surfaces were about 5 or less, but more than about 1, in the table 2 are marked with (*), while films for which the coefficient of friction of glossy surfaces was more than about 5 are marked with (-) in table 2.

table 2
Sample (m.h. starch per 100 m.h. resin) Solubility Tensile strength (MPa) Friction coefficient 2a (2.66) * + (51.82) - 2b (7.98) * + (49.23) * 2s (23.94) * * (44.49) * 2d(2.66) * + (50.83) + 2nd (7.98) * + (45.07) + 2f (23.94) * * (39.65) + 2g (2.66) + + (47.85) + 2 hours (7.98) + * (41.08) + 2i (23.94) * - (33.87) + 2j (2.66) + + (55.47) - 2k (7.98) + + (44.53) + 2l (23.94) + - (33.69) +

[00174] Table 2 shows that water-soluble films according to the present description, containing water-soluble polyvinyl alcohol, a plasticizer and unmodified starch with an amylose content ranging from about 20% wt. to about 80 wt . 2g ). Table 2 additionally shows that for water-soluble films according to the present description, containing unmodified starch with an amylose content ranging from about 20% wt. up to about 80% wt., the tensile strength decreases with increasing starch content. Thus, table 2 presents water-soluble films according to the present description, containing a mixture of water-soluble polyvinyl alcohol, plasticizer and unmodified starch with an amylose content in the range from about 20% of the mass. up to about 80% wt., present in an amount of from about 5 m.h. up to about 30 m.h. per 100 m.h. resins that are characterized by high convertibility and good inter-film release properties, as evidenced by the low friction coefficient GG of smooth surfaces.

Example 3

[00175] Water -soluble films containing various polyvinyl alcohol resins were prepared and their static coefficient of friction of glossy surfaces was tested. Each composition of the water-soluble film contained a resin of polyvinyl alcohol in an amount of about 74% of the mass. based on the total weight of the film. The used polyvinyl alcohol resins contained a PVA homopolymer with a viscosity of about 13 cP and a hydrolysis degree of about 88 ( 3a ), a PVA homopolymer with a viscosity of about 23 cP and a hydrolysis degree of about 88 ( 3b ), a polyvinyl alcohol copolymer with a 5% content of methyl acrylate modification ( 3c ), a polyvinyl alcohol copolymer with 4% maleate modification ( 3d ), a polyvinyl alcohol copolymer with about 2% maleate modification ( 3e ), and a polyvinyl alcohol copolymer with about 4% 2-acrylamido-2-methylpropanesulfonic acid modification. Each film composition additionally contained about 26 m.p. plasticizers per 100 m.h. resins, minor amounts of processing aids such as surfactants, antioxidants, etc. in a total amount of about 1 m.h. per 100 m.h. resins, as well as starch in an amount of about 7.98 m.h. per 100 m.h. resins. In starches, unmodified starch with an amylose content of 50% ( 3a ¹ -3e ¹ ) or hydroxypropyl-modified starch with an amylose content of about 80% ( 3a ² -3e ² ) was used. Films for which the values of the static friction coefficient of the glossy surfaces were about 1 or less are marked with a (+) sign in Table 3, films for which the values for the coefficient of friction of the glossy surfaces were about 5 or less, but more than about 1, are marked in Table 3 (*), while films for which the values of the coefficient of friction of the glossy surfaces were more than about 5, in table 3 are marked with a (-). Below.

Table 3
Sample 3a ^one 3b ^one 3c ^one 3d ^one 3e ^one 3f ^one COF + + + + + + Sample 3a ² 3b ² 3c ² 3d ² 3e ² 3f ² COF + * - * + *

[00176] Table 3 shows that the effect of unmodified starch on the coefficient of friction of glossy surfaces does not depend on the type of polyvinyl alcohol or the degree of modification of polyvinyl alcohol copolymers. Table 3 additionally shows that hydroxypropyl-modified starch provides acceptable coefficients of friction for all types of resins, except for PVA modified with methyl acrylate. Thus, the effect of hydroxypropyl-modified starch does not differ significantly for different types of resins, with the exception of acrylate-modified PVA.

Example 4

[00177] Water -soluble films containing various starches were prepared and tested for their tensile strength and tear strength according to the Tensile Strength Test and the Tensile Strength Test. Each water-soluble film composition contained a polyvinyl alcohol copolymer having a maleate modification in an amount of about 77 % wt. based on the total weight of the film. The film compositions additionally contained about 26 m.h. plasticizers per 100 m.h. resins, minor amounts of processing aids such as surfactants, antioxidants, etc. in a total amount of about 1 m.h. per 100 m.h. resins, as well as starch in an amount of about 2.66 m.h. per 100 m.h. resins. The films contained unmodified starch with an amylose content of 1% ( 4a ), acid hydrolyzed starch with an amylose content of 1% ( 4b ), unmodified starch with an amylose content of about 25% ( 4c ), hydroxyethyl modified starch with an amylose content of 25% ( 4d ), unmodified starch with 50% amylose ( 4e ), unmodified starch with 80% amylose ( 4f ), and hydroxypropyl modified starch with 80% amylose ( 4g ). Tensile strength values and tensile strength values are shown in Table 4 below.

Table 4
Sample 4a 4b 4c 4d 4e 4f 4g Ultimate tensile strength
(N/ ^mm2 ) 51.82 47.25 50.83 53.53 47.85 55.47 49.84 Tensile strength
(g/mil) 1797.22 1984.6 1803.01 1954.97 1673.16 1442.5 1302.07

[00178] Table 4 shows that the values of tensile strength (about 45-55 N/mm ² ) and tensile strength (about 1300-2000 g/mil) of water-soluble films are relatively comparable for all films. Consequently, Table 4 shows that the amylose content and the type of modification do not have a significant effect on the mechanical properties of water-soluble films.

Example 5

[00179] Water soluble films of formulations with different ratios of polyvinyl alcohol to starch were prepared and tested for their tensile strength and tear strength as described above. Each water-soluble film formulation contained a maleate-modified polyvinyl alcohol copolymer. The film compositions additionally contained about 26 m.h. plasticizers per 100 m.h. resins, minor amounts of processing aids such as surfactants, antioxidants, etc. in a total amount of about 1 m.h. per 100 m.h. resins, as well as starch with an amylose content of about 50%. The amount of PVA in the resin based on the total weight of the film and the ratio of PVA: starch was 79% of the mass. PVA and 100:0 ( 5a ), 77% wt. and 97:3 ( 5b ), 63% wt. and 80:20 ( 5s ), 47% wt. and 60:40 ( 5d ) or 32% wt. and 40:60 ( 5e ). Films for which the tensile strength values were about 45 MPa or more are marked with (+) in Table 5 below, and films for which the tensile strength values were about 40 MPa or more, but less than about 45 MPa , in table 5 are marked with (*), while films for which the tensile strength was less than 40 MPa are marked with (-) in table 5. Films for which the tensile strength values were about 1500 g/mil or more are marked with (+) in Table 5 below, and films for which the tensile strength values were about 500 g/mil or more, but less than about 1500 g/mil are marked with (*) in Table 5, while films for which the tensile strength was less than 500 g/mil are marked with (-) in Table 5.

Table 5
Sample 5a 5b 5c 5d 5e Tensile strength MPa) +(47,16) + (51.06) - (33.50) - (23.28) - (24.14) Tensile Strength (g/mil) + (1774.61) + (1844.24) - (159.07) - (0) - (0)

[00180] Table 5 shows that when the ratio of PVA resin to unmodified starch in the water-soluble film is about 80:20, or at a higher starch content, there is a sharp decrease in the values of tensile strength and tear strength compared to the values for the same water-soluble film with less starch than in the case of a ratio of 80:20, for example, with a ratio of 97:3.

Examples 6-45

[00181] Water-soluble films containing different polyvinyl alcohols in an amount of from about 20% of the mass. up to 95% wt., different starches in an amount of from about 2.5 m.h. up to 30 m.h. per 100 m.h. resins, plasticizers in an amount of about 10% of the mass. up to about 45% wt., surfactants in an amount of from about 0.1% wt. up to 8.0% wt., bitter additives in an amount of from about 0.01% wt. up to 10% wt. and whitening components in an amount of from about 0.01% of the mass. up to 10% wt. Film compositions are shown in Table 6 below.

Resin in an amount of from about 20% of the mass. up to about 95% of the mass. based on the total weight of the film Starch in an amount of about 2.5 m.h. up to 30 m.h. per 100 m.h. resin Plasticizer in an amount of from about 10% of the mass. up to about 45% of the mass. based on the total weight of the film Surface-active substances amount from about 0.1% of the mass. up to 8.0% wt. based on the total weight of the film from 0.01% wt. up to 10% wt. based on the total weight of the film Example BUT AT FROM D E F G H I J To L M N O P Glycerol Optional, one or more plasticizers* non-ionic Optional, one or more surfactants** Bitrex® Sodium Metabisulphite Film Moisture Content one X X X X X X X X 4-9% wt. 2 X X X X X X X X 4-9% wt. 3 X X X X X X X X 4-9% wt. four X X X X X X X X X 4-9% wt. 5 X X X X X X X X 4-9% wt. 6 X X X X X X X X 4-9% wt. 7 X X X X X X X X X 4-9% wt. eight X X X X X X X X 4-9% wt. 9 X X X X X X X X 4-9% wt. ten X X X X X X X X 4-9% wt. eleven X X X X X X X X 4-9% wt. 12 X X X X X X X X 4-9% wt. 13 X X X X X X X X 4-9% wt. fourteen X X X X X X X X 4-9% wt. fifteen X X X X X X X X 4-9% wt. 16 X X X X X X X X 4-9% wt. 17 X X X X X X X X X 4-9% wt. eighteen X X X X X X X X X 4-9% wt. 19 X X X X X X X X X 4-9% wt. twenty X X X X X X X X X 4-9% wt. 21 X X X X X X X X X X 4-9% wt. 22 X X X X X X X X X X 4-9% wt. 23 X X X X X X X X X X 4-9% wt. 24 X X X X X X X X 4-9% wt. 25 X X X X X X X X 4-9% wt. 26 X X X X X X X X 4-9% wt. 27 X X X X X X X X 4-9% wt. 28 X X X X X X X X 4-9% wt. 29 X X X X X X X X 4-9% wt. thirty X X X X X X X X 4-9% wt. 31 X X X X X X X X 4-9% wt. 32 X X X X X X X X 4-9% wt. 33 X X X X X X X X 4-9% wt. 34 X X X X X X X X 4-9% wt. 35 X X X X X X X X 4-9% wt. 36 X X X X X X X X 4-9% wt. 37 X X X X X X X X X 4-9% wt. 38 X X X X X X X X X 4-9% wt. 39 X X X X X X X X X X 4-9% wt. 40 X X X X X X X X X 4-9% wt.

* selected from one or more of the following components: polyethylene glycol, sorbitol, trimethylolpropane, 2-methyl-1,3-propanediol, dulcite, erythritol, glycerol-propylene oxide polymers, hexylene glycol, propylene glycol, triethylene glycol, voranol, xylitol

** selected from one or more of the following classes: cationic, anionic, zwitterionic

A is an alkyl acrylate PVA terpolymer

B is a PVA terpolymer with a monomer unit of 2-acrylamide-2-methylpropanesulfonic acid

C is a PVA terpolymer with a monoalkyl maleate monomer unit in an amount of 1.75 mol %.

D is a PVA terpolymer with a monoalkyl maleate monomer unit in an amount of 4.00 mol %.

E is a PVA homopolymer (viscosity 3; H 85)

F is a PVA homopolymer (viscosity 4; H 88)

G is a PVA homopolymer (viscosity 8; DH 88)

H is a PVA homopolymer (viscosity 13; DH 88)

I is a PVA homopolymer (viscosity 15; H 79)

J is a PVA homopolymer (viscosity 23; H 88)

K is a PVA homopolymer (viscosity 32; H 88)

L is a PVA homopolymer (viscosity 40; H 88)

M is a PVA homopolymer (viscosity 56; H 98)

N is Casco's corn products (25% amylose, native) (provided by Ingredion)

O is Hylon® V (50% amylose, native) (provided by Ingredion)

P is Eco-Film® (80% amylose, hydroxypropyl modified, ~2.5% mod) (provided by Ingredion)

[00182] Thus, Examples 6 through 45 represent film formulations specifically contemplated for preparing the water-soluble films of the present disclosure.

Example 46

[00183] Bags are made from the water soluble films of Examples 1-45. In particular, water-soluble bags may be formed from two layers of water-soluble polymeric film sealed at the interface, or from a single film folded and sealed. In both methods, the film forms an inner container for the bag, which is sealed at matte surfaces, with the glossy side of the film forming the outside of the bag.

[00184] Formed bags are additionally filled with compositions containing liquids, powders, gels, or combinations of the above components. The compositions contain components such as surfactants, bleaches, enzymes, perfumes, dyes or pigments, and/or solvents (for liquid and gel compositions).

Example 47

[00185] The water soluble film of the present disclosure was thermoformed into filled bags using commercial high speed equipment. On the example of the obtained bags, real practical results of reducing the coefficient of friction of a water-soluble film were demonstrated. In particular, for commercially available films of a similar composition, but not containing starch according to the present description, in order to avoid sticking of the formed bags when working with them, it is necessary to use powders (for example, talc, as described in US patent No. 9,290,727), while for bags on Based on the films of the present invention, the use of powders to prevent blocking is not required. The observed benefit was provided by the use of the film according to the present description with a reduced coefficient of friction.

[00186] The foregoing description is for clarity of understanding only, and is not intended to be unduly restrictive of any of the following, as various modifications will be apparent to those skilled in the art within the scope of the present invention.

All patents, publications, and references cited in this document are incorporated herein by reference in their entirety. In the event of any conflict between the present disclosure and the included patents, publications, and references, the present disclosure shall govern.

Claims (69)

1. Water-soluble film with a low static coefficient of friction for packaging, containing a mixture of (i) water-soluble polyvinyl alcohol, (II) a plasticizer selected from the group consisting of diglycerin, propylene glycol, sorbitol, trimethylol propane, polyethylene glycols, polymers of glycerol and propylene oxide, 2- methyl-1,3-propanediol, xylitol and combinations of the above, and (iii) hydroxypropyl-modified starch having an amylose content in the range from 65% to 95%, and polyvinyl alcohol is contained in an amount of 20% of the mass. up to 95% wt. based on the total weight of the film, and hydroxypropylated starch is contained in an amount ranging from 5 m.h. up to 30 m.h. per 100 m.h. resins. 2. Water-soluble film according to claim 1, characterized in that the degree of modification of hydroxypropyl-modified starch is from 4% to 8%. 3. Water-soluble film according to claim. 1 or 2, characterized in that the amount of hydroxypropyl-modified starch is in the range of 6 m.h. up to 10 m.h. per 100 m.h. resins. 4. A water-soluble film according to any one of the preceding claims, characterized in that the amount of hydroxypropyl-modified starch is 8 m.h. per 100 m.h. resin, while the water solubility of the film thickness of 76 microns is less than 90 seconds as measured by the method MSTM-205. 5. Water-soluble film according to claim. 1 or 2, characterized in that the amount of hydroxypropyl-modified starch is in the range from 12 m.h. up to 16 hours per 100 m.h. resins. 6. A water-soluble film according to any one of the preceding claims, characterized in that the tensile strength of the film is at least 40 MPa. 7. A water-soluble film according to any one of the preceding claims, characterized in that the tensile strength of the film is more than 45 MPa. 8. A water-soluble film according to any one of the preceding claims, characterized in that the static coefficient of friction of the glossy surfaces of the film is 5 MPa or less. 9. Water-soluble film according to any one of the preceding paragraphs, characterized in that the amount of plasticizer is in the range from 1 m.h. up to 40 m.h. per 100 m.h. resins. 10. A water soluble film according to any one of the preceding claims, characterized in that the plasticizer is selected from the group consisting of 2-methyl-1,3-propanediol, sorbitol, glycerin, and combinations of the foregoing. 11. A water-soluble film according to any one of the preceding claims, further comprising a surfactant, an antioxidant, a bitter agent, a soil repellent agent, anti-pollution agents, chelating agents, fillers, perfumes, or combinations of the foregoing. 12. A water soluble film according to any one of the preceding claims, characterized in that the film has a reduced static coefficient of friction of the glossy surfaces compared to a starch-free film of the same composition. 13. A water-soluble film according to any one of the preceding claims, wherein the polyvinyl alcohol comprises a polyvinyl alcohol selected from the group consisting of a polyvinyl alcohol homopolymer, an anionically modified polyvinyl alcohol copolymer, and a combination of the foregoing. 14. A sealed product in the form of a bag containing a water-soluble film according to any one of the preceding paragraphs, forming the internal volume of the bag. 15. A sealed product according to claim 14, additionally containing a composition placed in the internal volume of the bag. 16. Sealed product according to claim 15, characterized in that the composition is a detergent composition. 17. Sealed article according to claim 16, characterized in that the cleaning composition is selected from the group consisting of laundry detergent, dishwashing detergent, hard surface cleaning composition, fabric conditioner compositions, shaving creams, skin care products. , shampoos, body cleansers and combinations of the above. 18. Water-soluble film with a low static coefficient of friction for packaging, containing a mixture of (i) water-soluble polyvinyl alcohol, (II) a plasticizer selected from the group consisting of diglycerin, propylene glycol, sorbitol, trimethylol propane, polyethylene glycols, glycerol and propylene oxide polymers, 2- methyl-1,3-propanediol, xylitol and combinations of the above, and (iii) hydroxypropyl-modified starch, and polyvinyl alcohol is contained in an amount of 20% wt. up to 95% wt. based on the total weight of the film, while the hydroxypropyl-modified starch has a degree of modification from 2% to 8%, and the hydroxypropyl-modified starch is present in an amount ranging from 2.5 m.h. up to 30 m.h. per 100 m.h. resins. 19. Water-soluble film according to claim 18, characterized in that the degree of modification of the modified starch is from 4% to 8%. 20. A water-soluble film according to claim 18 or 19, characterized in that the amylose content of the modified starch is in the range from 65% to 95%. 21. Water-soluble film according to any one of paragraphs. 18-20, characterized in that the modified starch contains a hydroxyalkyl modification with an alkyl chain length of three or more carbon atoms. 22. Water-soluble film according to any one of paragraphs. 18-21, characterized in that the polyvinyl alcohol contains a polyvinyl alcohol selected from the group consisting of a polyvinyl alcohol homopolymer, an anionically modified polyvinyl alcohol copolymer, and combinations of the above. 23. A water-soluble film according to claim 21, characterized in that the polyvinyl alcohol contains a polyvinyl alcohol copolymer having an anionic modification. 24. Water-soluble film according to any one of paragraphs. 18-23, characterized in that the amount of starch is in the range from 6 m.h. up to 10 m.h. per 100 m.h. resins. 25. Water-soluble film according to any one of paragraphs. 18-24, characterized in that the amount of starch is 8 m.h. per 100 m.h. resin, while the water solubility of the film with a thickness of 76 microns in cold water is less than 90 seconds as measured by the method MSTM-205. 26. Water-soluble film according to any one of paragraphs. 18-23, characterized in that the amount of starch is in the range of 12 m.h. up to 16 hours per 100 m.h. resins. 27. Water-soluble film according to any one of paragraphs. 18-26, characterized in that the tensile strength for the film is at least 40 MPa. 28. Water-soluble film according to any one of paragraphs. 18-27, characterized in that the tensile strength for the film is at least 45 MPa. 29. A water-soluble film according to any one of claims 18 to 28, characterized in that the static coefficient of friction of the glossy surfaces of the film is about 5 MPa or less. 30. Water-soluble film according to any one of paragraphs. 18-29, characterized in that the amount of plasticizer is in the range from 1 m.h. up to 40 m.h. per 100 m.h. resins. 31. Water-soluble film according to any one of paragraphs. 18-30, characterized in that the plasticizer is selected from the group consisting of 2-methyl-1,3-propanediol, sorbitol, glycerin, and combinations of the above. 32. Water-soluble film according to any one of paragraphs. 18-31, additionally containing a surfactant, an antioxidant, a bitter component, soil-repellent components, anti-secondary pollution agents, chelating agents, fillers, fragrances, or combinations of the above. 33. Water-soluble film according to any one of paragraphs. 18-32, characterized in that the film is characterized by a reduced static coefficient of friction of glossy surfaces compared to a film of a similar composition that does not contain starch. 34. Sealed product in the form of a bag containing a water-soluble film according to any one of paragraphs. 18-33, forming the inner volume of the bag. 35. A sealed product according to claim 34, additionally containing a composition placed in the internal volume of the bag. 36. A sealed product according to claim 35, characterized in that the composition is a detergent composition. 37. Leak-proof article according to claim 36, characterized in that the cleaning composition is selected from the group consisting of laundry detergent, dishwashing detergent, hard surface cleaning composition, fabric conditioner compositions, shampoos, body cleansers, and combinations of the foregoing. . 38. Water-soluble film with a low static coefficient of friction for packaging, containing a mixture of (i) water-soluble polyvinyl alcohol, (ii) a plasticizer selected from the group consisting of diglycerin, propylene glycol, sorbitol, trimethylol propane, polyethylene glycols, polymers of glycerol and propylene oxide, 2- methyl-1,3-propanediol, xylitol and combinations of the above, and (iii) unmodified starch, while polyvinyl alcohol is contained in an amount of 20% wt. up to 95% wt. based on the total weight of the film, and the content of amylose in starch is from 20% to 80%. 39. Water-soluble film according to claim 38, characterized in that the content of polyvinyl alcohol is in the range of 60 wt%. up to 95% wt. based on the total weight of the film. 40. Water-soluble film under item 38 or 39, characterized in that the content of polyvinyl alcohol is in the range from 85% of the mass. up to 95% wt. based on the total weight of the film. 41. Water-soluble film according to any one of paragraphs. 38-40, characterized in that the amount of starch is in the range from 2 m.h. up to 30 m.h. per 100 m.h. resins. 42. Water-soluble film according to any one of paragraphs. 38-41, characterized in that the amount of starch is in the range of 2 m.h. up to 5 m.h. per 100 m.h. resins. 43. Water-soluble film according to any one of paragraphs. 38-42, characterized in that the static coefficient of friction of the glossy surfaces of the film is 1 or less. 44. Water-soluble film according to any one of paragraphs. 38-43, characterized in that the content of amylose in starch is in the range of 40% of the mass. up to 60% wt. 45. Water-soluble film according to any one of paragraphs. 38-44, characterized in that the amount of plasticizer is in the range from 1 m.h. up to 40 m.h. per 100 m.h. resins. 46. Water-soluble film according to any one of paragraphs. 38-45, characterized in that the plasticizer is selected from the group consisting of 2-methyl-1,3-propanediol, sorbitol and glycerin. 47. Water-soluble film according to any one of paragraphs. 38-46, additionally containing a surfactant, an antioxidant, a bitter component, soil-repellent components, anti-secondary pollution agents, chelating agents, fillers, fragrances, or combinations of the above. 48. Water-soluble film according to any one of paragraphs. 38-47, characterized in that the film is characterized by a reduced static coefficient of friction of glossy surfaces compared to a film of a similar composition that does not contain starch. 49. Sealed product in the form of a bag containing a water-soluble film according to any one of paragraphs. 38-48, forming the internal volume of the bag. 50. A sealed product according to claim 49, additionally containing a composition placed in the internal volume of the bag. 51. Sealed product according to claim 50, characterized in that the composition is a detergent composition. 52. Leak-proof article according to claim 51, characterized in that the cleaning composition is selected from the group consisting of laundry detergent, dishwashing detergent, hard surface cleaning composition, fabric conditioner compositions, shampoos, body cleansers, and combinations of the foregoing. . 53. Water-soluble film with a low static coefficient of friction for packaging, containing a mixture of (i) water-soluble polyvinyl alcohol, where the polyvinyl alcohol contains either unmodified polyvinyl alcohol or an anionically modified polyvinyl alcohol copolymer, provided that the anionic modifier is not an acrylate, with (ii ) a plasticizer selected from the group consisting of diglycerin, propylene glycol, sorbitol, trimethylol propane, polyethylene glycols, polymers of glycerol and propylene oxide, 2-methyl-1,3-propanediol, xylitol and combinations of the above, and (iii) hydroxypropyl-modified starch, and polyvinyl alcohol is contained in an amount of 60% of the mass. up to 95% wt. based on the total weight of the film, and where hydroxypropyl-modified starch has an amylose content of from 23% to 95%. 54. A water-soluble film according to claim 53, characterized in that the content of polyvinyl alcohol is in the range of 85% of the mass. up to 95% wt. based on the total weight of the film. 55. A water-soluble film according to claim 53 or 54, characterized in that the amount of starch is in the range of 5 m.h. up to 12 m.h. per 100 m.h. resins. 56. Water-soluble film according to any one of paragraphs. 53-55, characterized in that the static coefficient of friction of the glossy surfaces of the film is 5 or less. 57. Water-soluble film according to any one of paragraphs. 53-56, characterized in that the content of amylose in starch is in the range of 50% of the mass. up to 95% wt. 58. Water-soluble film according to any one of paragraphs. 53-57, characterized in that the hydroxypropyl-modified starch contains more than 2% hydroxypropyl modification. 59. Water-soluble film according to any one of paragraphs. 53-58, characterized in that the hydroxypropyl-modified starch contains from 4% to 8% hydroxypropyl modification. 60. Water-soluble film according to any one of paragraphs. 53-59, characterized in that the amount of plasticizer is in the range from 1 m.h. up to 40 m.h. per 100 m.h. resins. 61. Water-soluble film according to any one of paragraphs. 53-59, characterized in that the plasticizer is selected from the group consisting of 2-methyl-1,3-propanediol, sorbitol and glycerin. 62. Water-soluble film according to any one of paragraphs. 53-61, additionally containing a surfactant, an antioxidant, a bitter component, soil-repellent components, anti-secondary pollution agents, chelating agents, fillers, fragrances, or combinations of the above. 63. Water-soluble film according to any one of paragraphs. 53-62, characterized in that the film is characterized by a reduced static coefficient of friction of glossy surfaces compared to a film of a similar composition that does not contain starch. 64. Sealed product in the form of a bag containing a water-soluble film according to any one of paragraphs. 53-63, forming the internal volume of the bag. 65. A sealed product according to claim 64, additionally containing a composition placed in the internal volume of the bag. 66. A sealed product according to claim 65, characterized in that the composition is a detergent composition. 67. Leak-proof article according to claim 66, wherein the detergent composition is selected from the group consisting of washing powder, dishwashing detergent, hard surface cleaning composition, fabric conditioner compositions, shampoos, body cleansers, and combinations of the foregoing. . 68. Water-soluble film according to any one of paragraphs. 1-13, 18-33, 38-48 and 53-63, characterized in that the average particle size of starch is in the range from 1 μm to 6 μm in a dry state. 69. Water-soluble film according to any one of paragraphs. 1-13, 18-33, 38-48, 53-63 and 68, characterized in that the starch gelatinization temperature is in the range from 75 °C to 300 °C.

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