Water-soluble film

Abstract

The present invention relates to a water-soluble film containing a polysaccharide, a plasticizer A, and a plasticizer B, wherein the plasticizer A has a glass transition temperature (Tg) of -30°C or lower, the plasticizer B has a glass transition temperature (Tg) of 0°C or higher, the total content of the plasticizer A and the plasticizer B is more than 20 mass % and 90 mass % or less with respect to the mass of the water-soluble film, and the content of a polyvinyl alcohol-based resin is less than 30 mass % with respect to the mass of the water-soluble film.

Description

Water-soluble film

[0001] This patent application claims priority under the Paris Convention to Japanese Patent Application No. 2024-092945 (filing date: June 7, 2024), the entire contents of which are incorporated herein by reference. The present invention relates to a water-soluble film and a pouch comprising the water-soluble film.

[0002] Water-soluble films have been widely used in applications such as pouches for containing detergents, fragrances, medicines, etc., and demand for them is expanding due to their convenience. Known examples of water-soluble films include those containing polyvinyl alcohol or polysaccharides (see, for example, Patent Documents 1 and 2).

[0003] JP 2014-177654 A, WO 2004 / 041926 B, Pamphlet

[0004] Water-soluble films containing polysaccharides often lack sufficient processability and mechanical strength, and plasticizers are typically used to improve these properties. However, increasing the amount of plasticizer added for this purpose can lead to the plasticizer precipitating (bleeding out) on the film surface, resulting in stickiness and poor appearance. For this reason, it has been difficult to sufficiently improve the mechanical strength of conventional water-soluble films without causing bleed-out.

[0005] Therefore, an object of the present invention is to provide a water-soluble film having improved mechanical strength while suppressing bleeding out of a plasticizer, and a pouch comprising the water-soluble film.

[0006] The present inventors have conducted extensive research to solve the above problems, and as a result have found that the above problems can be solved, leading to the completion of the present invention. That is, the present invention includes the following preferred embodiments.

[0007] [1] A water-soluble film comprising a polysaccharide, a plasticizer A, and a plasticizer B, wherein the plasticizer A has a glass transition temperature (Tg) of -30°C or lower, and the plasticizer B has a glass transition temperature (Tg) of 0°C or higher, the total content of the plasticizers A and B is more than 20% by mass and not more than 90% by mass relative to the mass of the water-soluble film, and the content of the polyvinyl alcohol-based resin is less than 30% by mass relative to the mass of the water-soluble film. [2] The water-soluble film according to [1], wherein the plasticizer is selected from the group consisting of polyhydric alcohols, hydroxy acids, monosaccharides, disaccharides, and amino acids. [3] The water-soluble film according to [1] or [2], wherein the plasticizer A is at least one selected from the group consisting of glycerin, polyglycerin having a molecular weight of 2000 or less, ethylene glycol, polyethylene glycol having a molecular weight of 650 or less, propylene glycol, polypropylene glycol having a molecular weight of 3000 or less, 2-methyl-1,3-propanediol, and derivatives thereof. [4] The water-soluble film according to any one of [1] to [3], wherein the content of the plasticizer A is 5 to 85% by mass relative to the mass of the water-soluble film. [5] The water-soluble film according to any one of [1] to [4], wherein the plasticizer B is at least one selected from the group consisting of xylitol, maltitol, mannitol, xylose, fructose, mannose, sucrose, galactose, trehalose, lysine, glycine, and derivatives thereof. [6] The water-soluble film according to any one of [1] to [5], wherein the content of the plasticizer B is 5 to 85% by mass relative to the mass of the water-soluble film. [7] The water-soluble film according to any one of [1] to [6], wherein the blending ratio of the plasticizer A and the plasticizer B, by mass, is plasticizer A / plasticizer B, ranging from 10 / 90 to 90 / 10. [8] The water-soluble film according to any one of [1] to [7], wherein the polysaccharide is at least one selected from the group consisting of starch, carrageenan, alginic acid, guar gum, xanthan gum, pectin, hydroxyalkyl cellulose, alkyl cellulose, tamarind seed gum, agar, pullulan, locust bean gum, tara gum, and derivatives thereof.[9] A packaging material comprising the water-soluble film according to any one of [1] to [8].

[10] A pouch comprising the water-soluble film according to any one of [1] to [8].

[11] The pouch according to

[10] , which contains therein at least one selected from the group consisting of a cleaning agent, a fabric softener, and a fragrance.

[12] A molded article comprising the water-soluble film according to any one of [1] to [8].

[13] A laminate comprising the water-soluble film according to any one of [1] to [8].

[0008] According to the present invention, it is possible to provide a water-soluble film that has improved mechanical strength while suppressing bleeding out of a plasticizer, and a pouch comprising the water-soluble film.

[0009] 1 is a photograph showing the appearance of a water-soluble film obtained in Example 1. 2 is a photograph showing the appearance of a water-soluble film obtained in Comparative Example 4.

[0010] Hereinafter, embodiments of the present invention will be described in detail. Note that the following description is merely illustrative of embodiments of the present invention, and is not intended to limit the present invention to the following embodiments. Note that the upper and lower limits described in this specification can be arbitrarily combined to form a suitable numerical range.

[0011] [Water-soluble film] The water-soluble film of the present invention comprises a polysaccharide, a plasticizer A, and a plasticizer B, wherein the plasticizer A has a glass transition temperature (Tg) of -30°C or lower, and the plasticizer B has a glass transition temperature (Tg) of 0°C or higher, the total content of the plasticizers A and B is more than 20% by mass and 90% by mass or lower relative to the mass of the water-soluble film, and the content of the polyvinyl alcohol-based resin is less than 30% by mass relative to the mass of the water-soluble film. In this specification, mechanical strength means mechanical strength including "toughness," which is the product of the maximum stress (MPa) and the breaking elongation (%).

[0012] The present inventors have conducted research into methods for improving the mechanical strength of a film while suppressing bleed-out of the plasticizer, and have unexpectedly found that the above-mentioned problems can be solved by a water-soluble film comprising a polysaccharide, a plasticizer A having a glass transition temperature (Tg) of −30° C. or lower, and a plasticizer B having a glass transition temperature (Tg) of 0° C. or higher, wherein the total content of plasticizer A and plasticizer B is more than 20% by mass but not more than 90% by mass, based on the mass of the water-soluble film, and the content of polyvinyl alcohol is less than 30% by mass, based on the mass of the water-soluble film. While the reason for this is unclear, it is believed that the combined use of plasticizer A, which has a low glass transition temperature and contributes to improved processability and mechanical strength but is prone to bleed-out, and plasticizer B, which has a high glass transition temperature, results in the interaction between the plasticizers, whereby plasticizer B reduces the molecular mobility of plasticizer A and improves the compatibility between the plasticizer and the polysaccharide. Furthermore, by mixing multiple plasticizers, the glass transition temperature of the plasticizers as a whole was increased above the glass transition temperature of plasticizer A alone, which is thought to have contributed to suppressing bleed-out and improving processability and mechanical strength.

[0013] <Plasticizer> The water-soluble film of the present invention contains plasticizer A and plasticizer B (plasticizer A and plasticizer B may be collectively referred to simply as "plasticizers"). In the water-soluble film of the present invention, the total content of plasticizer A and plasticizer B is more than 20% by mass and not more than 90% by mass relative to the mass of the water-soluble film. If the total content of plasticizer A and plasticizer B is 20% by mass or less, the water-soluble film becomes brittle and its processability and mechanical strength decrease. Furthermore, if the total content of plasticizer A and plasticizer B exceeds 90% by mass, the plasticizer is likely to bleed out. The total content of plasticizer A and plasticizer B is preferably 23 to 87% by mass, more preferably 25 to 85% by mass, and even more preferably 30 to 85% by mass. From the viewpoint of improving the breaking elongation of the film, it is even more preferably 35 to 83% by mass, particularly preferably 40 to 80% by mass, 42 to 78% by mass, 45 to 75% by mass, 50 to 72% by mass, or 55 to 71% by mass. From the viewpoint of suppressing stickiness of the film, it is even more preferably 25 to 80% by mass, particularly preferably 25 to 70% by mass, 27 to 65% by mass, 30 to 60% by mass, or 35 to 55% by mass. When the total content of plasticizer A and plasticizer B is within the above range, the mechanical strength of the water-soluble film can be further improved while suppressing bleed-out of the plasticizer.

[0014] In one embodiment of the present invention, the blending ratio of plasticizer A to plasticizer B by mass is preferably 10 / 90 to 90 / 10, more preferably 15 / 85 to 85 / 15, even more preferably 20 / 80 to 82 / 17, still more preferably 25 / 75 to 81 / 19, and particularly preferably 30 / 70 to 80 / 20, 32 / 68 to 78 / 22, 40 / 60 to 75 / 25, or 45 / 55 to 70 / 30. When the blending ratio of plasticizer A to plasticizer B is within the above range, the mechanical strength of the water-soluble film can be improved while suppressing bleed-out of the plasticizer.

[0015] In the present invention, the plasticizer is preferably at least one selected from the group consisting of polyhydric alcohols, hydroxy acids, monosaccharides, disaccharides, and amino acids. Plasticizers can aggregate polysaccharides by dehydrating them. Furthermore, they can form a high-order network by hydrogen bonding with polysaccharides, thereby improving processability and increasing the mechanical strength of the water-soluble film.

[0016] Examples of the polyhydric alcohol include glycerin, diglycerin, polyglycerin having a molecular weight of 2000 or less, sorbitol, alkylene glycol (e.g., alkylene glycols having 2 to 10 carbon atoms such as ethylene glycol, propylene glycol, and neopentyl glycol), polyalkylene glycol (e.g., diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol having a molecular weight of 650 or less, and polypropylene glycol having a molecular weight of 3000 or less), trimethylolpropane, erythritol, xylitol, 2-methyl-1,3-propanediol, maltitol, mannitol, and pentaerythritol.

[0017] Examples of the hydroxy acid include lactic acid, glycolic acid, malic acid, and tartaric acid.

[0018] Examples of the monosaccharides include glucose, mannose, galactose, fructose, and xylose.

[0019] Examples of the disaccharides include maltose, trehalose, sucrose, and lactose.

[0020] Examples of the amino acid include lysine, leucine, isoleucine, proline, arginine, arginic acid, glycine, asparagine, and aspartic acid.

[0021] <Plasticizer A> The water-soluble film of the present invention contains a plasticizer A having a glass transition temperature (Tg) of -30°C or lower. By containing a plasticizer A having a glass transition temperature (Tg) of -30°C or lower, the mechanical strength of the water-soluble film can be improved. When the water-soluble film contains plasticizer A, the breaking elongation in particular can be increased, and therefore toughness can be improved. Furthermore, processability can be improved, such as film formation becoming easier.

[0022] In the present invention, the glass transition temperature (Tg) of plasticizer A is preferably −40°C or lower, more preferably −50°C or lower, even more preferably −60°C or lower, and even more preferably −70°C or lower. If the glass transition temperature (Tg) of plasticizer A exceeds −30°C, the flexibility of the water-soluble film may be impaired. The lower limit of the glass transition temperature (Tg) of plasticizer A is not particularly limited, but is, for example, −110°C or higher, or −100°C or higher. Therefore, the glass transition temperature (Tg) of plasticizer A is preferably −110 to −30°C, more preferably −110 to −40°C, even more preferably −110 to −50°C, and even more preferably −100 to −60°C, or −100 to −70°C. The glass transition temperature (Tg) of the plasticizer can be measured by differential scanning calorimetry (DSC), for example, by the method described in the examples.

[0023] In the present invention, from the viewpoint of further increasing the mechanical strength of the water-soluble film, plasticizer A is preferably selected from the group consisting of glycerin, polyglycerin having a molecular weight of 2000 or less, ethylene glycol, polyethylene glycol having a molecular weight of 650 or less, propylene glycol, polypropylene glycol having a molecular weight of 3000 or less, 2-methyl-1,3-propanediol, and derivatives thereof, and more preferably selected from the group consisting of glycerin, polyglycerin having a molecular weight of 2000 or less, 2-methyl-1,3-propanediol, and derivatives thereof. The molecular weights of polyglycerin, polyethylene glycol, and polypropylene glycol may be determined, for example, by gas chromatography mass spectrometry.

[0024] Derivatives of these plasticizers A include, for example, derivatives modified with an alkyl group having 1 to 10 carbon atoms. Plasticizers A may be used alone or in combination of two or more. Polyglycerin, polyethylene glycol, and polypropylene glycol having different molecular weights may also be used.

[0025] In the water-soluble film of the present invention, the content of plasticizer A is preferably 5 to 85 mass%, more preferably 8 to 83 mass%, even more preferably 10 to 80 mass%, still more preferably 13 to 77 mass%, and particularly preferably 15 to 70 mass%, 18 to 67 mass%, 20 to 67 mass%, or 25 to 65 mass%, relative to the mass of the water-soluble film. When the content of plasticizer A is within the above range, the mechanical strength of the water-soluble film can be further improved while suppressing bleed-out of the plasticizer.

[0026] <Plasticizer B> The water-soluble film of the present invention contains a plasticizer B having a glass transition temperature (Tg) of 0° C. or higher. By containing a plasticizer B having a glass transition temperature (Tg) of 0° C. or higher, it is possible to suppress bleed-out while ensuring a particularly high maximum stress.

[0027] In the present invention, the glass transition temperature (Tg) of plasticizer B is preferably 5°C or higher, more preferably 10°C or higher, even more preferably 15°C or higher, still more preferably 18°C ​​or higher, and particularly preferably 20°C or higher, 30°C or higher, 40°C or higher, 50°C or higher, 60°C or higher, or 65°C or higher. If the glass transition temperature (Tg) of plasticizer B is lower than 0°C, the plasticizer tends to bleed out from the film. The upper limit of the glass transition temperature (Tg) of plasticizer B is not particularly limited, but is, for example, 180°C or lower, or 150°C or lower. Therefore, the glass transition temperature (Tg) of plasticizer B is preferably 0 to 180° C., more preferably 5 to 180° C., even more preferably 10 to 180° C., still more preferably 15 to 180° C., and particularly preferably 18 to 180° C., 20 to 180° C., 30 to 150° C., 40 to 150° C., 50 to 150° C., 60 to 150° C., or 65 to 150° C. The glass transition temperature (Tg) of the plasticizer can be measured by differential scanning calorimetry (DSC), for example, by the method described in the examples.

[0028] In the present invention, from the viewpoint of increasing the mechanical strength of the water-soluble film while further suppressing bleed-out, the plasticizer B is preferably at least one selected from the group consisting of xylitol, maltitol, mannitol, xylose, fructose, mannose, sucrose, galactose, trehalose, lysine, glycine, and derivatives thereof, and more preferably selected from the group consisting of fructose, sucrose, trehalose, xylose, and derivatives thereof. Examples of derivatives of these plasticizers B include acetamide-modified products, azide-modified products, and alkyl (e.g., alkyl having 1 to 10 carbon atoms)-modified products. Plasticizers B may be used singly or in combination of two or more.

[0029] In the water-soluble film of the present invention, the content of plasticizer B is preferably 5 to 85 mass%, more preferably 8 to 80 mass%, even more preferably 9 to 75 mass%, still more preferably 10 to 70 mass%, and particularly preferably 15 to 65 mass%, 20 to 60 mass%, 25 to 55 mass%, 30 to 50 mass%, or 34 to 50 mass%, relative to the mass of the water-soluble film. When the content of plasticizer B is within the above range, the mechanical strength of the water-soluble film can be further improved while suppressing bleed-out of the plasticizer.

[0030] <Polysaccharides> Polysaccharides refer to hydrocarbons composed of 10 or more monosaccharides bonded together. Examples of polysaccharides include starch, carrageenan, chitin, chitosan, cellulose, hemicellulose, dextrin, gum arabic, carrageenan, alginic acid, guar gum, xanthan gum, pectin, hydroxyalkyl cellulose, alkyl cellulose, carboxyalkyl cellulose, tamarind seed gum, agar, pullulan, locust bean gum, tara gum, karaya gum, succinoglycan, and derivatives thereof. These polysaccharides may be used alone or in combination of two or more. Among these, from the viewpoint of further improving the mechanical strength of the water-soluble film while suppressing bleed-out of the plasticizer, the polysaccharide is preferably at least one selected from the group consisting of starch, carrageenan, alginic acid, guar gum, xanthan gum, pectin, hydroxyalkyl cellulose, alkyl cellulose, tamarind seed gum, agar, pullulan, locust bean gum, tara gum, and derivatives thereof, more preferably at least one selected from the group consisting of starch, carrageenan, guar gum, xanthan gum, tamarind seed gum, locust bean gum, tara gum, and derivatives thereof, even more preferably at least one selected from the group consisting of starch, tamarind seed gum, and carrageenan, and particularly preferably contains tamarind seed gum.

[0031] In one embodiment of the present invention, the number-average molecular weight (sometimes referred to as Mn) of the polysaccharide is preferably 5 to 50,000 kDa, more preferably 7 to 10,000 kDa, and even more preferably 10 to 5,000 kDa, for example, 5 to 3,000 kDa, 10 to 1,000 kDa, or 15 to 700 kDa. The weight-average molecular weight (sometimes referred to as Mw) of the polysaccharide is preferably 5 to 150,000 kDa, more preferably 10 to 50,000 kDa, and even more preferably 20 to 30,000 kDa, for example, 30 to 10,000 kDa, 50 to 7,000 kDa, or 70 to 5,000 kDa. When the Mn and / or Mw of the polysaccharide are within the above ranges, the mechanical strength of the water-soluble film can be further improved while suppressing bleed-out of the plasticizer. When a polysaccharide is composed of two or more polysaccharides, the Mn of the polysaccharide is a weighted average of the Mn of the two or more polysaccharides. The same applies to the Mw. The polysaccharide may also contain polysaccharides of the same type but with different Mn and / or Mw. In this specification, the Mn and Mw of a polysaccharide can be determined by gel filtration HPLC, for example, by the method described in the Examples below.

[0032] In one embodiment of the present invention, the polysaccharide content may be selected appropriately depending on the type of polysaccharide, but is, for example, 10% by mass or more but less than 80% by mass, more preferably 13 to 77% by mass, even more preferably 15 to 75% by mass, even more preferably 15 to 70% by mass, even more preferably 17 to 65% by mass, and particularly preferably 20 to 60% by mass, 22 to 58% by mass, 25 to 55% by mass, 28 to 50% by mass, or 29 to 45% by mass, relative to the mass of the water-soluble film. Furthermore, from the viewpoint of suppressing stickiness of the film, the polysaccharide content is preferably 20 to 75% by mass, more preferably 30 to 75% by mass, even more preferably 35 to 73% by mass, even more preferably 40 to 60% by mass, and even more preferably 45 to 65% by mass. When the polysaccharide content is within the above range, the mechanical strength of the water-soluble film can be further improved while suppressing bleed-out of the plasticizer.

[0033] In the present invention, starch is preferably derived from plants, such as from plant bulbs, seeds, stems, leaves, etc. Starches suitable for the present invention include, for example, potato starch, arrowhead starch, sweet potato starch, tapioca starch, cassava starch, kudzu starch, lily of the valley starch, taro starch, konjac starch, Chinese yam starch, Japanese yam starch, lotus root starch, bracken starch, and corn starch, with potato starch and tapioca starch being preferred. Starch derivatives such as hydroxypropyl-modified starch and carboxymethyl-modified starch may also be used. The Mn of the starch is preferably 10 to 2,000 kDa, more preferably 20 to 1,000 kDa, and the Mw is preferably 30 to 300,000 kDa, more preferably 50 to 200,000 kDa. The starch content may be, for example, 10% by mass or more and less than 80% by mass, more preferably 13 to 77% by mass, even more preferably 15 to 75% by mass, even more preferably 15 to 70% by mass, and even more preferably 17 to 68% by mass, relative to the mass of the water-soluble film. When the starch content is within the above range, the mechanical strength of the water-soluble film can be further improved while suppressing bleed-out of the plasticizer.

[0034] Carrageenan is a polysaccharide obtained from red algae and contains repeating units of D-galactose or 3,6-anhydro-D-galactose and sulfate groups. Carrageenan is classified into κ (kappa) carrageenan, ι (iota) carrageenan, and λ (lambda) carrageenan. These can be used alone or in combination. Commercially available carrageenan products such as "GENUGEL carrageenan type JPE-126" (manufactured by Sansho Co., Ltd.) and "GENUTINE VCS-J" (manufactured by Sansho Co., Ltd.) may be used. The Mn of carrageenan is preferably 5 to 5,000 kDa, more preferably 10 to 3,000 kDa, and even more preferably 20 to 1,000 kDa, and may be, for example, 25 to 500 kDa or 30 to 200 kDa. The Mw of the carrageenan is preferably 5 to 15,000 kDa, more preferably 10 to 10,000 kDa, and even more preferably 20 to 5,000 kDa, for example, 50 to 2,000 kDa or 100 to 1,000 kDa. The carrageenan content may be, for example, 10% by mass or more but less than 80% by mass, more preferably 11 to 77% by mass, even more preferably 12 to 75% by mass, even more preferably 13 to 70% by mass, and even more preferably 14 to 65% by mass, relative to the mass of the water-soluble film. When the carrageenan content is within the above range, the mechanical strength of the water-soluble film can be further improved while suppressing bleed-out of the plasticizer.

[0035] The Mn of alginic acid is preferably 5 to 50,000 kDa, more preferably 7 to 10,000 kDa, even more preferably 10 to 5,000 kDa, for example, 15 to 1,000 kDa or 20 to 300 kDa. The Mw of alginic acid is preferably 5 to 150,000 kDa, more preferably 10 to 30,000 kDa, even more preferably 15 to 15,000 kDa, for example, 20 to 5,000 kDa, 30 to 1,000 kDa, or 50 to 500 kDa. The alginic acid content may be, for example, 10% by mass or more but less than 80% by mass, more preferably 13 to 77% by mass, even more preferably 15 to 75% by mass, even more preferably 15 to 70% by mass, even more preferably 17 to 65% by mass, and particularly preferably 20 to 60% by mass, 22 to 58% by mass, 25 to 55% by mass, 28 to 50% by mass, 29 to 45% by mass, 20 to 75% by mass, 30 to 75% by mass, 35 to 73% by mass, 40 to 60% by mass, or 45 to 65% by mass, relative to the mass of the water-soluble film. When the alginic acid content is within the above range, the mechanical strength of the water-soluble film can be further improved while suppressing bleed-out of the plasticizer.

[0036] Guar gum is a polysaccharide obtained from the endosperm of guar beans (Cyamopsis tetragonoloba) and has a structure in which mannose is the main chain and galactose is bonded to the side chain. Commercially available guar gums may be used, such as "SUPERGEL CSA200 / 50" (manufactured by Sansho Co., Ltd.), "Guapak (registered trademark)" (manufactured by MP Gokyo Food & Chemical Co., Ltd.), and "RG100" (manufactured by Mitsubishi Chemical Corporation). The Mn of guar gum is preferably 5 to 20,000 kDa, more preferably 5 to 10,000 kDa, and even more preferably 7 to 5,000 kDa, and may be, for example, 10 to 1,000 kDa or 15 to 100 kDa. The Mw of the guar gum is preferably 5 to 100,000 kDa, more preferably 5 to 50,000 kDa, and even more preferably 7 to 20,000 kDa, for example, 10 to 5,000 kDa, 30 to 1,000 kDa, or 50 to 500 kDa. The content of guar gum relative to the mass of the water-soluble film may be, for example, 10% by mass or more but less than 80% by mass, more preferably 13 to 77% by mass, even more preferably 15 to 75% by mass, even more preferably 15 to 70% by mass, still more preferably 17 to 65% by mass, particularly preferably 20 to 60% by mass, 22 to 58% by mass, 25 to 55% by mass, 28 to 50% by mass, 29 to 45% by mass, 20 to 75% by mass, 30 to 75% by mass, 35 to 73% by mass, 40 to 60% by mass, or 45 to 65% by mass. When the content of guar gum is within the above range, the mechanical strength of the water-soluble film can be further improved while suppressing bleeding out of the plasticizer.

[0037] Xanthan gum is a polysaccharide produced by fermenting starch with the bacterium Xanthomonas campestris. It has a glucose backbone and a side chain containing one glucuronic acid between two mannose units. Commercially available xanthan gums may be used, such as "Kimika Xanthan PH-R3EC" (manufactured by Kimika Co., Ltd.), "Echo Gum (registered trademark)" (manufactured by MP Gokyo Food & Chemical Co., Ltd.), and "Soaxan" (manufactured by Mitsubishi Chemical Corporation). The Mn of xanthan gum is preferably 5 to 50,000 kDa, more preferably 7 to 10,000 kDa, and even more preferably 10 to 5,000 kDa, and may be, for example, 10 to 1,000 kDa or 15 to 100 kDa. The Mw of xanthan gum is preferably 5 to 150,000 kDa, more preferably 7 to 50,000 kDa, and even more preferably 10 to 30,000 kDa, for example, 10 to 5,000 kDa, 30 to 1,000 kDa, or 50 to 500 kDa. The content of xanthan gum relative to the mass of the water-soluble film may be, for example, 10% by mass or more but less than 80% by mass, more preferably 13 to 77% by mass, even more preferably 15 to 75% by mass, even more preferably 15 to 70% by mass, still more preferably 17 to 65% by mass, particularly preferably 20 to 60% by mass, 22 to 58% by mass, 25 to 55% by mass, 28 to 50% by mass, 29 to 45% by mass, 20 to 75% by mass, 30 to 75% by mass, 35 to 73% by mass, 40 to 60% by mass, or 45 to 65% by mass. When the content of xanthan gum is within the above range, the mechanical strength of the water-soluble film can be further improved while suppressing bleeding out of the plasticizer.

[0038] Pectin is a polysaccharide found in plants and has an α-1,4 bond structure consisting of galacturonic acid and methyl-esterified galacturonic acid, which is methyl-esterified galacturonic acid. Commercially available pectin products, such as "H&F Pectin Classic AM201" (MP Gokyo Food & Chemical Co., Ltd.), may be used. The Mn of pectin is preferably 1 to 1,000 kDa, more preferably 5 to 500 kDa, and the Mw is preferably 3 to 3,000 kDa, more preferably 10 to 1,000 kDa. The pectin content may be, for example, 10% by mass or more but less than 80% by mass, more preferably 13 to 77% by mass, even more preferably 15 to 75% by mass, even more preferably 15 to 70% by mass, still more preferably 17 to 65% by mass, and particularly preferably 20 to 60% by mass, 22 to 58% by mass, 25 to 55% by mass, 28 to 50% by mass, 29 to 45% by mass, 20 to 75% by mass, 30 to 75% by mass, 35 to 73% by mass, 40 to 60% by mass, or 45 to 65% by mass, relative to the mass of the water-soluble film. When the pectin content is within the above range, the mechanical strength of the water-soluble film can be further improved while suppressing bleed-out of the plasticizer.

[0039] Examples of hydroxyalkyl cellulose include hydroxyalkyl celluloses having 2 to 10 carbon atoms in the hydroxyalkyl group, such as hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxypropyl methyl cellulose, and hydroxyethyl methyl cellulose, preferably hydroxyalkyl celluloses having 2 to 6 carbon atoms in the hydroxyalkyl group. Examples of alkyl cellulose include alkyl celluloses having 2 to 10 carbon atoms in the alkyl group, such as methyl cellulose, ethyl cellulose, propyl cellulose, and butyl cellulose, and alkyl celluloses having 2 to 6 carbon atoms in the alkyl group. The hydroxyalkyl cellulose refers to cellulose in which one or more hydroxyl groups are modified with a hydroxyalkyl group, and the alkyl cellulose refers to cellulose in which one or more hydroxyl groups are modified with an alkyl group. The carbon numbers of the hydroxyalkyl group and the alkyl group refer to the carbon numbers of one hydroxyalkyl group and one alkyl group, respectively. The hydroxyalkyl cellulose content may be, for example, 10% by mass or more but less than 80% by mass, more preferably 13 to 77% by mass, even more preferably 15 to 75% by mass, even more preferably 15 to 70% by mass, even more preferably 17 to 65% by mass, and particularly preferably 20 to 60% by mass, 22 to 58% by mass, 25 to 55% by mass, 28 to 50% by mass, 29 to 45% by mass, 20 to 75% by mass, 30 to 75% by mass, 35 to 73% by mass, 40 to 60% by mass, or 45 to 65% by mass, relative to the mass of the water-soluble film. When the hydroxyalkyl cellulose content is within the above range, the mechanical strength of the water-soluble film can be further improved while suppressing bleed-out of the plasticizer.

[0040] Tamarind seed gum is a polysaccharide obtained from the seeds of tamarind (Tamarindus indica) and has a structure in which glucose is the main chain and xylose and galactose are bonded to the side chains. Commercially available tamarind seed gum, such as "Glyloid (registered trademark)" and "Glyate (registered trademark)" (manufactured by MP Gokyo Food & Chemical Co., Ltd.), and "TG120" (manufactured by Mitsubishi Chemical Corporation), may be used. The Mn of the tamarind seed gum is preferably 10 to 3,000 kDa, more preferably 30 to 1,000 kDa, and even more preferably 50 to 500 kDa, and may be, for example, 100 to 500 kDa. The Mw of the tamarind seed gum is preferably 10 to 50,000 kDa, more preferably 30 to 10,000 kDa, and even more preferably 50 to 5,000 kDa, for example, 500 to 4,500 kDa or 1,000 to 4,000 kDa. The content of the tamarind seed gum may be, for example, 10% by mass or more but less than 80% by mass, more preferably 10 to 77% by mass, even more preferably 10 to 75% by mass, even more preferably 10 to 70% by mass, still more preferably 11 to 65% by mass, particularly preferably 12 to 60% by mass, 12 to 58% by mass, 12 to 55% by mass, 13 to 50% by mass, 13 to 45% by mass, 13 to 40% by mass, or 14 to 35% by mass, based on the mass of the water-soluble film. When the content of tamarind seed gum is within the above range, the mechanical strength of the water-soluble film can be further improved while suppressing bleeding out of the plasticizer.

[0041] Agar is a polysaccharide obtained from red algae, and has a structure in which D-galactose and anhydro-L-galactose are alternately bonded, and partially contains sulfate groups, methoxyl groups, and pyruvic acid groups. Commercially available agar, such as "Ina Agar (registered trademark)" (manufactured by Ina Food Industry Co., Ltd.), may be used. The Mn of the agar is preferably 5 to 500 kDa, more preferably 15 to 200 kDa, and the Mw is preferably 10 to 1000 kDa, more preferably 30 to 400 kDa. The content of agar may be, for example, 10% by mass or more but less than 80% by mass, more preferably 13 to 77% by mass, even more preferably 15 to 75% by mass, even more preferably 15 to 70% by mass, still more preferably 17 to 65% by mass, and particularly preferably 20 to 60% by mass, 22 to 58% by mass, 25 to 55% by mass, 28 to 50% by mass, 29 to 45% by mass, 20 to 75% by mass, 30 to 75% by mass, 35 to 73% by mass, 40 to 60% by mass, or 45 to 65% by mass, relative to the mass of the water-soluble film. When the content of agar is within the above range, the mechanical strength of the water-soluble film can be further improved while suppressing bleed-out of the plasticizer.

[0042] Pullulan is a polysaccharide obtained by fermenting the black yeast Aureobasidium pullulans in the presence of starch, and has a structure in which three glucose molecules are linked in an α-1,4 bond to maltotriose linked in an α-1,6 bond. Commercially available pullulan products, such as "Pullulan PI-20" (manufactured by Hayashibara Co., Ltd.), may be used. The Mn of pullulan is preferably 1 to 300 kDa, more preferably 2.5 to 100 kDa, and the Mw is preferably 2 to 600 kDa, more preferably 5 to 200 kDa. The pullulan content may be preferably 10% by mass or more but less than 30% by mass, more preferably 12 to 25% by mass, relative to the mass of the water-soluble film. When the pullulan content is within the above range, the mechanical strength of the water-soluble film can be further improved while suppressing bleed-out of the plasticizer.

[0043] Locust bean gum is a polysaccharide obtained from the seeds of carob (Celatonia siliqua) and has a structure in which mannose is the main chain and galactose is bound to the side chain. Commercially available locust bean gums may be used, such as "GENU (registered trademark) GUM type RL-200Z" (manufactured by Sansho Co., Ltd.), "Soarlocast A120," and "MC1000" (manufactured by Mitsubishi Chemical Corporation). The Mn of locust bean gum is preferably 5 to 50,000 kDa, more preferably 7 to 10,000 kDa, and even more preferably 10 to 5,000 kDa, and may be, for example, 15 to 1,000 kDa or 20 to 300 kDa. The Mw of the locust bean gum is preferably 5 to 150,000 kDa, more preferably 10 to 30,000 kDa, and even more preferably 15 to 15,000 kDa, for example, 20 to 5,000 kDa, 30 to 1,000 kDa, or 50 to 500 kDa. The content of locust bean gum relative to the mass of the water-soluble film may be, for example, 10% by mass or more but less than 80% by mass, more preferably 13 to 77% by mass, even more preferably 15 to 75% by mass, even more preferably 15 to 70% by mass, even more preferably 17 to 65% by mass, particularly preferably 20 to 60% by mass, 22 to 58% by mass, 25 to 55% by mass, 28 to 50% by mass, 29 to 45% by mass, 20 to 75% by mass, 30 to 75% by mass, 35 to 73% by mass, 40 to 60% by mass, or 45 to 65% by mass. When the content of locust bean gum is within the above range, the mechanical strength of the water-soluble film can be further improved while suppressing the bleeding out of the plasticizer.

[0044] Tara gum is a polysaccharide obtained from the seeds of tara (Caesalpinia spinosa) and has a structure in which mannose is the main chain and galactose is bound to the side chain. Commercially available tara gum, such as "MT120" (manufactured by Mitsubishi Chemical Corporation), may be used. The Mn of tara gum is preferably 5 to 10,000 kDa, more preferably 5 to 5,000 kDa, and even more preferably 10 to 1,000 kDa. The Mw of tara gum is preferably 5 to 30,000 kDa, more preferably 10 to 15,000 kDa, and even more preferably 15 to 10,000 kDa. The content of tara gum is, for example, 10% by mass or more and less than 80% by mass, more preferably 13 to 77% by mass, even more preferably 15 to 75% by mass, even more preferably 15 to 70% by mass, even more preferably 17 to 65% by mass, particularly preferably 20 to 60% by mass, 22 to 58% by mass, 25 to 55% by mass, 28 to 50% by mass, 29 to 45% by mass, 20 to 75% by mass, 30 to 75% by mass, 35 to 73% by mass, 40 to 60% by mass, or 45 to 65% by mass, relative to the mass of the water-soluble film. When the content of tara gum is within the above range, the mechanical strength of the water-soluble film can be further improved while suppressing bleed-out of the plasticizer.

[0045] Derivatives of these polysaccharides include, for example, sodium salts, potassium salts, calcium salts, enzyme-treated products, acid hydrolysates, etherified products, carboxyl alkylated products, aminated products and their hydrochlorides, phosphates, esterified products, crosslinked products, and oxides. One type of polysaccharide may be used alone, or two or more types may be used in combination.

[0046] In one embodiment of the present invention, the water-soluble film may contain two or more polysaccharides. When two or more polysaccharides are contained, the two or more polysaccharides can form a higher-order network through hydrogen bonding or the like, thereby improving the mechanical strength. The water-soluble film may preferably contain two or more or three or more polysaccharides, and may preferably contain five or fewer, more preferably four or fewer, polysaccharides.

[0047] In one embodiment of the present invention, when the water-soluble film contains two or more polysaccharides, it is preferable that a different type of polysaccharide be further contained in order to further improve the mechanical strength of the water-soluble film. In one embodiment of the present invention, the combination of two different polysaccharides is preferably tamarind seed gum / carrageenan; tamarind seed gum / xanthan gum; tamarind seed gum / guar gum; tamarind seed gum / locust bean gum; tamarind seed gum / starch; tamarind gum / pullulan, etc., in order to further improve the mechanical strength of the water-soluble film. Furthermore, when three different polysaccharides are contained, the combination is preferably tamarind seed gum / carrageenan / pullulan; starch / carrageenan / pectin, etc., in order to further improve the mechanical strength of the water-soluble film.

[0048] In a preferred embodiment of the present invention, when the water-soluble film contains two types of ingredients, for example, tamarind seed gum and carrageenan, the blending ratio by mass of tamarind seed gum / carrageenan is preferably 10 / 90 to 90 / 10, more preferably 20 / 80 to 90 / 10, even more preferably 30 / 70 to 90 / 10, still more preferably 40 / 60 to 90 / 10, and particularly preferably 45 / 55 to 85 / 15, or 48 / 52 to 85 / 15. When the blending ratio of tamarind seed gum to carrageenan is within the above range, the mechanical strength of the water-soluble film can be further improved.

[0049] In one embodiment of the present invention, the blending ratio of the polysaccharide and the plasticizer by mass is preferably 10 / 90 to 90 / 10, more preferably 15 / 85 to 88 / 12, even more preferably 18 / 82 to 85 / 15, still more preferably 20 / 80 to 82 / 18, and particularly preferably 23 / 77 to 80 / 20, 25 / 75 to 77 / 23, 27 / 73 to 75 / 25, 28 / 72 to 70 / 30, or 29 / 71 to 68 / 32. When the blending ratio of the polysaccharide and the plasticizer is within the above range, the mechanical strength of the water-soluble film can be further improved while suppressing bleed-out of the plasticizer.

[0050] <Additives> The water-soluble film of the present invention may contain additives other than polysaccharides and plasticizers to the extent that the effects of the present invention are not impaired. Examples of additives include water, plasticizers having a glass transition temperature (Tg) of more than -30°C and less than 0°C, antioxidants, ultraviolet absorbers, lubricants, colorants, preservatives, fillers, crosslinking agents, etc. One type of additive may be used alone, or two or more types may be used in combination.

[0051] Examples of crosslinking agents include tannic acid and its salts, tannins other than tannic acid, catechin, anthocyanin, gallic acid and its salts, phenols, and hydroquinone.

[0052] The content of the additive is not particularly limited as long as it does not interfere with the effects of the present invention, but is, for example, about 0 to 30% by mass, preferably about 0.001 to 10% by mass, more preferably about 0.01 to 5% by mass, and even more preferably about 0.1 to 1% by mass, relative to the mass of the water-soluble film.

[0053] In one embodiment of the present invention, the content of the polyvinyl alcohol-based resin in the water-soluble film is less than 30% by mass relative to the mass of the water-soluble film. If the content of the polyvinyl alcohol-based resin in the water-soluble film is 30% by mass or more, the film's GHG (Green House Gas) emissions will increase, resulting in a greater environmental impact. Furthermore, the film will be susceptible to degradation by alkaline substances such as detergents. The content of the polyvinyl alcohol-based resin in the water-soluble film is preferably 20% by mass or less, more preferably 10% by mass or less, even more preferably 5% by mass or less, even more preferably 1% by mass or less, particularly preferably 0.1% by mass or less, and may even be 0% by mass. That is, the content is preferably 0 to less than 30% by mass, more preferably 0 to 20% by mass, even more preferably 0 to 10% by mass, even more preferably 0 to 5% by mass, particularly preferably 0 to 1% by mass, and particularly preferably 0 to 0.1% by mass. The polyvinyl alcohol resin used in the present invention can be made from vinyl acetate made from petroleum-derived carbon, vinyl acetate made from biomass-derived carbon, or a mixture thereof.

[0054] In one embodiment of the present invention, the total content of the polysaccharide and plasticizer contained in the water-soluble film is preferably 30% by mass or more, more preferably 50% by mass or more, even more preferably 70% by mass or more, even more preferably 80% by mass or more, particularly preferably 90% by mass or more, particularly preferably 95% by mass or more, and especially preferably 98% by mass or more, based on the mass of the water-soluble film. That is, it is preferably 30 to 100% by mass, more preferably 50 to 100% by mass, even more preferably 70 to 100% by mass, even more preferably 80 to 100% by mass, particularly preferably 90 to 100% by mass, especially more preferably 95 to 100% by mass, and especially preferably 98 to 100% by mass. When the total content of the polysaccharide and plasticizer contained in the water-soluble film is within the above range, the mechanical strength of the water-soluble film can be further improved while suppressing bleed-out of the plasticizer.

[0055] [Water-Soluble Film] The water-soluble film of the present invention contains the polysaccharide, plasticizer A, and plasticizer B, and thus exhibits improved mechanical strength while suppressing bleed-out of the plasticizer. In this specification, "water-soluble" means soluble in water, preferably having a solubility of 90% by mass or more in 90°C hot water. That is, a water-soluble film can be evaluated as water-soluble if, after adding the film to 90°C hot water and stirring for 5 minutes to dissolve the film, the amount of solids that do not pass through a filter (21 μm) is 10% by mass or less. The mass of the water-soluble film to be dissolved in 90°C hot water is 0.1 parts by mass per 100 parts by mass of 90°C hot water. The solubility of the water-soluble film in 90°C hot water is 90% by mass or more, preferably 95% by mass or more, and more preferably 98% by mass or more. When the solubility is above the lower limit, for example, residue is less likely to remain when the water-soluble film is dissolved in water. The upper limit of the solubility of the water-soluble film is 100% by mass. That is, the solubility of the water-soluble film is 90 to 100% by mass, preferably 95 to 100% by mass, and more preferably 98 to 100% by mass. The solubility of the water-soluble film can be adjusted to be equal to or higher than the above lower limit by, for example, appropriately adjusting the types and / or amounts of components contained in the water-soluble film.

[0056] In one embodiment of the present invention, the water-soluble film has high cold water solubility. Cold water solubility refers to the solubility of the water-soluble film in cold water (e.g., 10°C). In one embodiment of the present invention, the water-soluble film of the present invention can be dissolved in water at 10°C preferably within 1000 seconds. That is, when a water-soluble film measuring 30 mm in length, 40 mm in width, and 50 μm in thickness is immersed in 500 mL of water at 10°C, the time required for complete dissolution is preferably within 1000 seconds, more preferably within 700 seconds, even more preferably within 600 seconds, and even more preferably within 500 seconds, and may be, for example, within 300 seconds or within 180 seconds. When the complete dissolution time of the water-soluble film in water at 10°C is equal to or less than the upper limit, the water-soluble film can be quickly dissolved even when dissolved in cold water for use. For example, in the case of a pouch containing the water-soluble film, this is preferable because the contents are quickly released even when dissolved in cold water for use. Furthermore, residue is less likely to remain. Note that there is no particular lower limit on the complete dissolution time, and the shorter the time required for complete dissolution, the better. The time required for complete dissolution of the water-soluble film in water at 10°C can be adjusted to the above upper limit or less by appropriately adjusting, for example, the types and / or amounts of components contained in the water-soluble film, the production conditions of the water-soluble film (drying conditions, etc.), etc. The time required for complete dissolution in water at 10°C can be determined, for example, by the method described in the Examples below.

[0057] In one embodiment of the present invention, the maximum stress of the water-soluble film may vary depending on the polysaccharide used, but is, for example, 3 MPa or more, 4 MPa or more, 8 MPa or more, 10 MPa or more, 12 MPa or more, 14 MPa or more, 15 MPa or more, 16 MPa or more, 17 MPa or more, 18 MPa or more, or 19 MPa or more. The upper limit of the maximum stress of the water-soluble film is usually 150 MPa or less, preferably 140 MPa or less. Specifically, the maximum stress of a water-soluble film containing tamarind seed gum as the polysaccharide is preferably 10 to 150 MPa, more preferably 12 to 150 MPa, even more preferably 14 to 150 MPa, still more preferably 15 to 150 MPa, particularly preferably 16 to 140 MPa, 17 to 140 MPa, 18 to 140 MPa, or 19 to 140 MPa. In another embodiment of the present invention, the maximum stress of a water-soluble film containing starch as a polysaccharide is preferably 3 to 150 MPa, more preferably 4 to 150 MPa, even more preferably 8 to 140 MPa, and still more preferably 10 to 140 MPa.

[0058] In one embodiment of the present invention, the breaking elongation of the water-soluble film varies depending on the polysaccharide used, but is, for example, 20% or more, 30% or more, 40% or more, 45% or more, 70% or more, 80% or more, 90% or more, 93% or more, 94% or more, 95% or more, 100% or more, 102% or more, 107% or more, or 109% or more. The upper limit of the breaking elongation of the water-soluble film is usually 300% or less, preferably 200% or less. Specifically, the breaking elongation of a water-soluble film containing tamarind seed gum as the polysaccharide is preferably 70 to 300%, more preferably 80 to 300%, even more preferably 90 to 300%, even more preferably 93 to 300%, particularly preferably 94 to 300%, 95 to 200%, 100 to 200%, 102 to 200%, 107 to 200%, or 109 to 200%. In another embodiment of the present invention, the breaking elongation of a water-soluble film containing starch as a polysaccharide is preferably 20 to 300%, more preferably 30 to 300%, even more preferably 40 to 200%, and still more preferably 45 to 200%. The maximum stress and breaking elongation of the water-soluble film can be determined by a tensile test, for example, by the method described in the Examples below.

[0059] In one embodiment of the present invention, the toughness of the water-soluble film may vary depending on the type of polysaccharide used, but may be, for example, 250 or more, 300 or more, 400 or more, 450 or more, 1500 or more, 1550 or more, 1580 or more, 1600 or more, 1650 or more, 1700 or more, 1730 or more, 1800 or more, 1870 or more, or 1900 or more. The upper limit of the toughness is usually 4000 or less, preferably 3000 or less. When the toughness of the water-soluble film of the present invention is equal to or greater than the lower limit, the mechanical strength of the water-soluble film is improved. For example, when a pouch containing the water-soluble film of the present invention is produced, the water-soluble film is set in a pouch mold and heated, and then a vacuum is created between the pouch mold and the film to prevent breakage during the formation of the bottom of the pouch. Specifically, the toughness of a water-soluble film containing tamarind seed gum as a polysaccharide is preferably 1500 to 4000, more preferably 1550 to 4000, even more preferably 1580 to 4000, still more preferably 1600 to 4000, and particularly preferably 1650 to 4000, 1700 to 3000, 1730 to 3000, 1800 to 3000, 1870 to 3000, or 1900 to 3000. In another embodiment of the present invention, the toughness of a water-soluble film containing starch as a polysaccharide is preferably 250 to 4000, more preferably 300 to 4000, even more preferably 400 to 3000, and still more preferably 450 to 3000. The toughness of a water-soluble film can be determined by multiplying the maximum stress in a tensile test by the elongation at break.

[0060] In the present invention, by combining a plasticizer B having a high glass transition temperature (Tg) with a plasticizer A having a relatively low glass transition temperature (Tg), it is possible to improve the mechanical strength (e.g., toughness) of the water-soluble film while suppressing bleed-out, compared to the case where the same amount of plasticizer A is used alone. The increase in toughness of the water-soluble film of the present invention containing plasticizer A and plasticizer B is, for example, 20% or more, preferably 25% or more, more preferably 30% or more, even more preferably 45% or more, and particularly preferably 55% or more, 60% or more, 75% or more, 80% or more, or 85% or more, compared to a water-soluble film using plasticizer A alone.

[0061] The water-soluble film may be a single-layer film or a multi-layer film in which a plurality of the water-soluble films are laminated. From the viewpoints of water solubility, mechanical strength, cold water solubility, and production efficiency, a single-layer film is preferred.

[0062] In one embodiment of the present invention, the thickness of the water-soluble film is preferably 1 to 500 μm, more preferably 5 to 300 μm, even more preferably 10 to 150 μm, and even more preferably 20 to 110 μm. When the thickness of the water-soluble film is within the above range, the water-soluble film can have good water solubility, mechanical strength, and cold water solubility. The thickness of the water-soluble film can be determined, for example, using a thickness meter, and can be determined by the method described in the Examples below. Note that, when the water-soluble film is a multilayer film, the thickness of the water-soluble film refers to the thickness of one water-soluble film.

[0063] The surface of the water-soluble film of the present invention may be flat, or from the viewpoint of preventing adhesion of products to each other, one or both sides of the water-soluble film may be provided with a textured finish such as an embossed pattern or a textured pattern. For such textured finish, methods known in the art can be used.

[0064] <Method for Producing Water-Soluble Film> The method for producing the water-soluble film of the present invention is not particularly limited, and the film can be produced by a method known in the art. For example, the water-soluble film can be produced by a method including the steps of: obtaining a coating liquid by stirring a polysaccharide, a plasticizer, a solvent, and optionally additives at a predetermined temperature; forming a coating film; and drying the coating film to form a dried coating film.

[0065] The solids concentration of the coating solution is preferably 1 to 15% by mass, more preferably 2 to 10% by mass, and indicates the total mass of components other than the solvent (e.g., polysaccharides, plasticizers, additives, etc.) relative to the mass of the coating solution.

[0066] The temperature at which the polysaccharide, plasticizer, solvent, and, if necessary, additives are stirred is usually 15 to 100° C., preferably 30 to 98° C. The stirring method is not particularly limited, and stirring can be carried out by a conventionally known method.

[0067] The solvent is not particularly limited, but water, ethanol, methanol, 1-propanol, 2-propanol, etc. are preferred because they easily dissolve polysaccharides and are easy to dry afterwards.

[0068] The coating film can be formed, for example, by applying the coating liquid onto a substrate, such as a polyolefin (e.g., polyethylene, polypropylene, etc.), a polyester (e.g., polyethylene terephthalate, etc.), a polyamide (e.g., nylon 6, nylon 66, etc.), a fluororesin (e.g., Teflon, etc.), or a metal plate.

[0069] Examples of a method for applying the coating liquid to a substrate or the like include known methods such as spin coating, extrusion, bar coating, applicator, etc. Examples of coaters that can be used include blade coaters, bar coaters, roll coaters, gravure coaters, reverse gravure coaters, comma coaters, air knife coaters, reverse roll coaters, curtain coaters, spray coaters, size press coaters, and gate roll coaters.

[0070] The solvent is then removed by drying or the like to form a dry coating film. Examples of drying methods include natural drying, ventilation drying, heat drying, and reduced pressure drying.

[0071] Alternatively, the water-soluble film can be produced by a melt extrusion film-forming method in which a film-forming solution obtained using an extruder or the like is extruded through a T-die or the like to form a film, or an inflation molding method, etc. After the water-soluble film is formed on the substrate, the substrate may be peeled off before use, or the film may be used as is without being peeled off.

[0072] In one embodiment of the present invention, when a water-soluble film is produced by extrusion molding, a conventional extruder, preferably a twin-screw extruder, can be used to produce the molded article.

[0073] When the water-soluble film is a laminate, it can be molded by adjusting the temperature of the obtained water-soluble composition (e.g., pellets) as needed, extruding the molten water-soluble composition through a T-die or the like onto a known substrate with releasability, and then cooling. A single-layer molded product can be produced, and a multilayer film can also be produced by co-extrusion or by laminating the obtained molded product by a known method. Alternatively, it can be molded by adjusting the temperature of the obtained water-soluble composition (e.g., pellets) as needed, subjecting it to inflation molding, and cooling. By employing co-extrusion in inflation molding, a multilayer film can also be produced.

[0074] The above method can be used to produce a laminate (multilayer molded article) containing a multilayer (two or more layers) laminate (film) of the present invention, or one or more layers of the laminate (film) of the present invention and one or more layers other than the laminate (film) (for example, any layer described as a support in the section [Laminate] below). When a multilayer molded article contains two or more layers of the laminate (film) of the present invention, the films may be the same as or different from each other. When a multilayer laminate contains two or more layers other than the laminate (film), the two or more layers may be the same as or different from each other. When a multilayer molded article contains any of the above-mentioned layers and the any of the layers is a resin layer, a multilayer laminate containing the any of the layers can also be produced by coating a solution containing a material for forming the resin layer and a solvent using a general method, and then removing the solvent.

[0075] [Molded Article] The present invention also encompasses a molded article comprising the water-soluble film of the present invention. In the present invention, a molded article refers to a solid object molded into a desired shape. The dimensions of the molded article in the present invention are not limited. In one embodiment of the present invention, the minimum dimension of the molded article is preferably 1 cm or less, more preferably 0.1 μm to 1 cm, even more preferably 0.5 μm to 1 mm, and particularly preferably 1 μm to 200 μm. The minimum dimension refers to the smallest dimension in the outer shape of the molded article. For example, in the case of a rectangular parallelepiped molded article, this refers to the smallest dimension among the length, width, and height. For example, in the case of a cup with a circular bottom, this refers to the smallest dimension among the diameter of the bottom, the height of the cup, the thickness of the cup bottom, and the thickness of the cup side. In one embodiment of the present invention, the maximum dimension of the molded article is preferably 0.5 cm or more, more preferably 1 cm or more, even more preferably 10 cm to 10,000 m, and particularly preferably 1 cm to 1,000 m. The maximum dimension refers to the largest dimension in the outer shape of the molded article. Dimensions such as length, diameter, height and thickness can be measured using contact measuring methods such as vernier calipers or thickness gauges, or optical measuring methods such as laser displacement meters.

[0076] The shape of the molded article is not particularly limited. In one embodiment of the present invention, the molded article is a fiber, a pellet, a foam, a disc, or a rod.

[0077] When the molded article is a fiber, the single filament fineness of the fiber is preferably 0.01 to 10,000 dtex, more preferably 0.3 to 5,000 dtex, and even more preferably 1 to 10 dtex. When the single filament fineness is within the above range, the fiber can have excellent breaking elongation and texture. The single filament fineness can be adjusted to within the above range, for example, by appropriately adjusting the size of the spinneret during spinning, the draw ratio, the draw speed, etc. The single filament fineness can be calculated by measuring the total fiber fineness in accordance with JIS L 1013 and dividing this by the number of filaments. The total fiber fineness is preferably 10 to 100,000 dtex, more preferably 100 to 10,000 dtex, and even more preferably 1,000 to 5,000 dtex. When the total fineness is equal to or less than the above upper limit, the fiber can have excellent handleability. The total fineness can be adjusted within the above range by, for example, appropriately adjusting the single yarn fineness during spinning, the number of filaments, etc. The total fineness can be determined in accordance with JIS L 1013. The cross-sectional shape of the fiber is not particularly limited and may be, for example, round, elliptical, flower-shaped, leaf-shaped, polygonal, star-shaped, Y-shaped, snowman-shaped, hollow, cross-shaped, etc. The fiber may be in the form of continuous fiber (monofilament, multifilament), staple fiber, thread, string, rope, etc. It may also be in the form of a textile product containing the fiber, such as a woven fabric, knitted fabric, or nonwoven fabric. These forms may consist solely of the molded body (fiber) of the present invention, or may be composed in combination with other fibers other than the molded body (fiber) of the present invention. In one embodiment, the present invention preferably has a nonwoven fabric form.

[0078] When the molded product is a pellet, the pellet may have one or more shapes selected from the group consisting of, for example, a sphere, an ellipsoid, a cylinder, an elliptical cylinder, a polygonal cylinder, a rugby ball shape, a flattened shape, and a cylindrical shape, and these shapes may have a missing portion or a convex portion. The pellet typically has an average outer dimension of 0.1 to 20 mm, preferably 1 to 10 mm, and more preferably 2 to 8 mm. The average outer dimension of the pellet refers to the average outer dimension of the pellet, such as diameter, length, and width, and can be determined by measuring the outer dimensions at at least four points for each of any 10 pellets and calculating the average value.

[0079] When the molded article is a foam, the cell size of the foam is preferably 0.1 to 500 μm in diameter, more preferably 1 to 300 μm, even more preferably 5 to 100 μm, and particularly preferably 10 to 80 μm.

[0080] When the molded article is a disk, its average thickness is usually 10 to 10,000 μm, preferably 100 to 1,000 μm, and more preferably 200 to 500 μm, and the average diameter of the disk is usually 1 to 10 mm, preferably 2 to 8 mm, and more preferably 3 to 5 mm.

[0081] When the molded article is a rod, its diameter is usually 0.1 to 10 mm, preferably 0.2 to 5 mm, more preferably 0.5 to 2 mm, and the average length of the rod is usually 1 to 10 mm, preferably 2 to 8 mm, more preferably 3 to 5 mm.

[0082] The average outer dimensions of the pellets, the average thickness and diameter of the disks, and the average diameter and length of the rods can be determined using a contact measurement method such as a vernier caliper or a thickness meter, or an optical measurement method such as a laser displacement meter.

[0083] The method for producing the molded article is not particularly limited, and the molded article can be produced by a method known in the art. When the molded article is a fiber, for example, the molded article can be produced by a method including the steps of: obtaining a composition by stirring a polysaccharide, a plasticizer, a solvent, and optionally an additive at a predetermined temperature; adjusting the temperature of the obtained composition as necessary, discharging the molten composition from a nozzle, and cooling it.

[0084] When the molded article is a pellet, a disk, or a rod, it can be produced by a method including, for example, a step of obtaining a composition by stirring a polysaccharide, a plasticizer, a solvent, and optionally an additive at a predetermined temperature, and a step of adjusting the temperature of the obtained composition as necessary, extruding the molten composition from an extruder into a desired shape, cutting it, and cooling it.

[0085] In one embodiment of the present invention, the surface of the molded article may be flat, or from the viewpoint of preventing adhesion of the molded articles to each other, a part or the entire surface of the molded article may be subjected to a textured finish such as an embossed pattern or a textured pattern. For such textured finish, a method known in the art can be adopted.

[0086] [Laminate] The present invention also encompasses a laminate comprising the water-soluble film of the present invention and a support, wherein the support is a fiber, a textile product, paper, metal foil, or film (hereinafter also referred to as a "support film"). In the present invention, the term "laminate" may refer to a laminate comprising the water-soluble film of the present invention having a desired shape and a support, which are integrated together. The support is preferably paper or a film. In such an embodiment, the laminate of the present invention comprises the water-soluble film, and therefore has excellent water solubility and mechanical strength.

[0087] When the support is a fiber, examples of the fiber include spun yarn, staple, and filament yarn. The average fiber diameter of the fiber is, for example, 0.1 to 500 μm, preferably 0.5 to 100 μm, and more preferably 1 to 50 μm. The fiber may be in the form of continuous fiber (monofilament, multifilament), staple fiber, thread, string, rope, or the like. When the support is a textile product, examples of the textile product include woven fabrics, knitted fabrics, nonwoven fabrics, and fiber-reinforced plastics. The fibers constituting the textile product are, for example, the fibers listed above as examples of fibers when the support is a fiber. The plastic contained in the fiber-reinforced plastic is not particularly limited and may be, for example, an epoxy resin, a polyester resin, or a phenolic resin. The average thickness of the textile product is, for example, 1 to 500 μm, preferably 5 to 300 μm, and more preferably 10 to 100 μm. When the support is a fiber or a textile product, the film can act as a sizing agent for the fiber or textile product. In this case, the film can improve the lubricity of the support surface and prevent thread breakage or fluffing.

[0088] When the support is paper, examples of the paper include kraft paper, one-side glossy kraft paper, one-side glossy bleached kraft paper, bleached kraft paper, unbleached kraft paper, fine paper, medium-quality paper, coated paper, one-side glossy paper, construction paper, glassine paper, graphene paper, parchment paper, synthetic paper, white cardboard, manila cardboard, milk carton base paper, cup base paper, ivory paper, silver paper, tissue paper, paperboard, rayon paper, wax paper, liner paper, etc. The basis weight of the paper is 20 to 400 g / m from the viewpoint of suitability for packaging applications. ２ It is preferable that the density is 25 to 150 g / m ２ From the viewpoint of suitability for use as a flexible packaging material, which will be described later, the basis weight of the paper is 30 to 100 g / m ２ More preferably, it is 40 to 70 g / m ２ The basis weight of the paper is measured in accordance with JIS P 8124:2011.

[0089] The above-mentioned paper can generally be produced by papermaking a stock containing pulp, fillers, and various auxiliaries. Examples of pulp include chemical pulps such as bleached hardwood kraft pulp (LBKP), bleached softwood kraft pulp (NBKP), unbleached hardwood kraft pulp (LUKP), unbleached softwood pulp (NUKP), and sulfite pulp; mechanical pulps such as stone-ground pulp and thermomechanical pulp; wood fibers such as deinked pulp and recycled paper pulp; and non-wood fibers obtained from kenaf, bamboo, hemp, etc. These can be used alone or in combination of two or more. Among these, chemical pulp from wood fibers and mechanical pulp are preferred, and chemical pulp is more preferred, from the viewpoints of reducing the possibility of foreign matter being mixed into the base paper and the possibility of discoloration over time when recycled after use, achieving good printing due to high brightness, and increasing the useful value (especially when used as a packaging material). Materials other than pulp can also be used as the secondary paper material as long as they do not impair the effects of the present invention. Examples of such materials include synthetic fibers such as rayon and nylon.

[0090] Examples of fillers include white carbon, talc, kaolin, clay, heavy calcium carbonate, light calcium carbonate, titanium oxide, zeolite, and synthetic resin fillers. These can be used alone or in combination of two or more. Examples of various auxiliaries include aluminum sulfate, various anionic, cationic, nonionic, or amphoteric retention aids, drainage aids, paper strength agents, and internal sizing agents, which can be used alone or in combination of two or more. Optionally, dyes, fluorescent whitening agents, pH adjusters, defoamers, pitch control agents, slime control agents, and additives consisting of two or more of these can also be used.

[0091] The method for producing paper is not particularly limited, and paper can be produced, for example, according to the following procedure. First, a stock is prepared by mixing a pulp slurry with a filler and various auxiliaries. The pulp slurry can be prepared by beating pulp in the presence of water. The pulp beating method and beating device are not particularly limited, and known beating methods and beating devices can be used. The pulp content in the stock is not particularly limited. For example, it is 60% by mass or more but less than 100% by mass relative to the total mass of the stock. Next, the prepared stock is made into paper by an acidic, neutral, or alkaline papermaking method using a known Fourdrinier former, on-top hybrid former, gap former, or the like. Multiple sheets of wet paper obtained after dewatering are stacked as necessary, and one or more sheets of wet paper are pressed and dried to obtain paper. In this case, if multiple wet paper sheets are not stacked, a single-layer paper is obtained, and if multiple wet paper sheets are stacked, a multi-layer paper is obtained. When multiple wet papers are stacked, adhesive may be applied to the surface of the wet paper (the surface on which other wet papers are stacked).

[0092] The paper surface may be treated with various chemicals. Examples of such chemicals include oxidized starch, hydroxyethyl etherified starch, enzyme-modified starch, polyacrylamide, polyvinyl alcohol, surface sizing agents, water-resistant agents, water-retention agents, thickeners, and lubricants. These may be used alone or in combination. Furthermore, these chemicals may be used in combination with pigments. Examples of pigments include inorganic pigments such as kaolin, clay, engineered kaolin, delaminated clay, ground calcium carbonate, light calcium carbonate, mica, talc, titanium dioxide, barium sulfate, calcium sulfate, zinc oxide, silicic acid, silicates, colloidal silica, and satin white, as well as organic pigments such as solid, hollow, and core-shell pigments. These may be used alone or in combination.

[0093] The method for treating the surface of paper is not particularly limited, and can be performed using a known coating device such as a rod metering size press, a pond type size press, a gate roll coater, a spray coater, a blade coater, or a curtain coater.

[0094] A laminate comprising a water-soluble film and a support selected from the group consisting of paper, a support film, and a metal foil may have, at any location in the layer structure, one or more layers selected from the group consisting of a barrier layer, a protective layer, and a heat-seal layer. When the laminate has a protective layer and / or a heat-seal layer, the layer is preferably disposed as the outermost layer of the laminate. The barrier layer may be a gas barrier layer or a water vapor barrier layer, and such barrier layers are known in the art. Examples of barrier layers include resin layers and metal foils. More specific examples include resin layers containing polyvinyl alcohol, ethylene-vinyl alcohol copolymers, and / or polyvinylidene chloride; layers containing glucan; aluminum foils; aluminum vapor-deposited films (aluminum vapor-deposited on a substrate such as polyethylene, polypropylene, nylon, polyethylene terephthalate, or ethylene-vinyl alcohol copolymer); alumina vapor-deposited films (alumina vapor-deposited on a substrate such as polyethylene, polypropylene, nylon, polyethylene terephthalate, or ethylene-vinyl alcohol copolymer); and silica vapor-deposited films (silica vapor-deposited on a substrate such as polyethylene, polypropylene, nylon, polyethylene terephthalate, or ethylene-vinyl alcohol copolymer). The protective layer, by being present as at least a part of the outermost layer of the laminate, can reduce the influence of the surrounding environment on the components present below the protective layer (deterioration of the components). Therefore, the protective layer may have one or more functions selected from the group consisting of barrier properties, oil resistance, solvent resistance, heat resistance, abrasion resistance, impact resistance, weather resistance, and light resistance. By covering the entire outermost layer of the laminate with the protective layer, the above functions can be more effectively exhibited. Examples of protective layers include a resin layer, a paper layer, and a metal foil. Heat-seal layers known in the art can be used. The heat-seal layer is preferably a resin layer having heat-sealability. The heat-seal layer preferably contains a water-dispersible resin and, optionally, an additive.Examples of water-dispersible resins include polyolefin resins, styrene / acrylic copolymers, acrylic resins such as ethylene-(meth)acrylic acid copolymers, ethylene-vinyl acetate copolymers, polyester resins, rubber-based resins, urethane resins, polyamide resins, and combinations thereof. Examples of optional additives include lubricants such as paraffin wax, carnauba wax, and polyolefin waxes, pigments such as silica and kaolin, and combinations thereof. The heat-seal layer may have barrier properties, in which case the layer can function as both a heat-seal layer and a barrier layer. When the support is a film having barrier or protective properties, the film can also function as a barrier or protective layer.

[0095] Specific layer configurations of the laminate of the present invention, which includes a water-soluble film and one or more supports selected from the group consisting of paper, film (support film), and metal foil, and which may have any layer (barrier layer, protective layer, heat seal layer), include, for example, the following configurations: Note that the following configurations are each described starting from the layer that will become the outermost layer (the layer on the opposite side to the layer that comes into contact with the contents) when used as, for example, a packaging material. Molded body film / paper or support film or metal foil, Gas barrier layer or water vapor barrier layer / water soluble film / paper or support film or metal foil, Water vapor barrier layer / gas barrier layer / water soluble film / paper or support film or metal foil, Gas barrier layer / water vapor barrier layer / water soluble film / paper or support film or metal foil, Protective layer / water soluble film / paper or support film or metal foil, Protective layer / gas barrier layer or water vapor barrier layer / water soluble film / paper or support film or metal foil, Protective layer / water vapor barrier layer / gas barrier layer / water soluble film / paper or support film or metal foil, Protective layer / gas barrier layer / water vapor barrier layer / water soluble film / paper or support film or metal foil, Protective layer / water soluble film / gas barrier layer or water vapor barrier layer / paper or support film or metal foil, Protective layer / water soluble film / gas barrier layer or water vapor barrier layer / paper or support film or metal foil, Protective layer / water soluble film / water vapor barrier layer / gas barrier layer / paper or support film or metal foil, Protective layer / gas barrier layer or water vapor barrier layer / water soluble film / paper or support film or metal foil / gas barrier layer or water vapor barrier layer, Protective layer / water vapor barrier layer / gas barrier layer / water soluble film / paper or support film or metal foil / gas barrier layer or water vapor barrier layer, Protective layer / gas barrier layer / water vapor barrier layer / water soluble film / paper or support film or metal foil / gas barrier layer or water vapor barrier layer, Protective layer / water vapor barrier layer / gas barrier layer / water soluble film / paper or support film or metal foil / gas barrier layer / water vapor barrier layer, Protective layer / water vapor barrier layer / gas barrier layer / water soluble film / paper or support film or metal foil / gas barrier layer / water vapor barrier layer, Protective layer / water vapor barrier layer / gas barrier layer / water soluble film / paper or support film or metal foil / water vapor barrier layer / gas barrier layer,protective layer / gas barrier layer / water vapor barrier layer / water-soluble film / paper or support film or metal foil / gas barrier layer / water vapor barrier layer; protective layer / gas barrier layer / water vapor barrier layer / water-soluble film / paper or support film or metal foil / water vapor barrier layer / gas barrier layer; a layer configuration in which a heat seal layer is provided on the side opposite to the outermost layer in the above layer configuration; a layer configuration in which a heat seal layer is provided in place of a protective layer in the above layer configuration, for example, heat seal layer / water-soluble film / paper or support film or metal foil; a layer configuration in which an adhesive layer is provided in one or more locations between each layer in the above layer configuration, for example, heat seal layer / adhesive layer / water-soluble film / paper or support film or metal foil.

[0096] More specific examples of the layer structure include the following: Water-soluble film / paper, LLDPE / water-soluble film / paper, LLDPE / adhesive layer / water-soluble film / paper, LDPE / water-soluble film / paper, LDPE / adhesive layer / water-soluble film / paper, HDPE / water-soluble film / paper, HDPE / adhesive layer / water-soluble film / paper, CPE (non-oriented polyethylene) / water-soluble film / paper, CPE (non-oriented polyethylene) / adhesive layer / water-soluble film / paper, Polyethylene formed from polyethylene emulsion / water-soluble film / paper, Polyethylene formed from polyethylene emulsion / adhesive layer / water-soluble film / paper, Uniaxially oriented polyethylene / water-soluble film / paper, Uniaxially oriented polyethylene / adhesive layer / water-soluble film / paper, Biaxially oriented polyethylene / water-soluble film / paper, Biaxially oriented polyethylene / adhesive layer / water-soluble film / paper, Polypropylene / water-soluble film / paper, Polypropylene / adhesive layer / water-soluble film / paper, Uniaxially oriented polypropylene / water-soluble film / paper, Uniaxially oriented polypropylene / adhesive layer / water-soluble film / paper, Biaxially oriented polypropylene / water-soluble film / paper, Biaxially oriented polypropylene / adhesive layer / water-soluble film / paper, PLA / water-soluble film / paper, PLA / adhesive layer / water-soluble film / paper, PHA / water-soluble film / paper, PHA / adhesive layer / water-soluble film / paper, PHBH / water-soluble film / paper, PHBH / adhesive layer / water-soluble film / paper, PCL / water-soluble film / paper, PCL / adhesive layer / water-soluble film / paper, PBAT / water-soluble film / paper, PBAT / adhesive layer / water-soluble film / paper, PBS / water-soluble film / paper, PBS / adhesive layer / water-soluble film / paper.

[0097] <Method for Producing Laminate> The method for producing the laminate of the present invention is not particularly limited, and the laminate can be produced by a method known in the art.

[0098] The laminate of the present invention can be produced, for example, by coating a coating liquid on a support and removing water, and the coating film in the laminate may be a single layer or multiple layers. By repeatedly coating a support with a coating liquid and removing water, a multilayer laminate containing any layers in any stacking order can also be produced.

[0099] The laminate of the present invention can also be produced by laminating a molded film produced by, for example, a melt extrusion film-forming method, in which a film-forming solution (aqueous composition) obtained using an extruder or the like is extruded through a T-die or the like to form a film, or an inflation molding method, with a support. The lamination method is not limited, and examples include a method in which water is applied to the surface of the molded film and the coated surface is adhered to the support; a method in which the molded film and the support are laminated by thermocompression bonding; a method in which the molded film and the support are laminated via a pressure-sensitive adhesive or adhesive; and an inflation method in which the material for forming the molded film and the material for forming the support (film) are co-extruded. When laminating by thermocompression bonding, the conditions may be appropriately selected depending on the type and amount of starch, tamarind seed gum, and plasticizer contained in the molded film. For example, lamination can be performed by compression bonding at a temperature of 80 to 200°C, at a pressure of 0.1 to 30 MPa, for 0.1 to 10 seconds. When laminating via a pressure-sensitive adhesive or adhesive, such pressure-sensitive adhesive or adhesive is known in the art. The laminate of the present invention can also be produced as a multi-layer laminate by laminating a plurality of molded films obtained by melt extrusion film formation, inflation molding or the like onto a support by a known method.

[0100] When the laminate contains multiple molded films, it may contain a combination of molded films (coated films) produced by coating and molded films (molten films) produced by melt extrusion film forming, inflation molding, or the like.

[0101] [Packaging Material] The present invention also encompasses a packaging material comprising the water-soluble film of the present invention. In such an embodiment, the packaging material of the present invention comprises the water-soluble film, and therefore has high water solubility, suppresses bleed-out of the plasticizer, and improves mechanical strength. The packaging material preferably has the same properties as the pouch described in the section [Pouch] below.

[0102] The packaging material is a film used for packaging, and may include a thin film, a thick film, etc., and may be in the form of a container, a cup, a tube, a tray, a bottle, etc. In one embodiment of the present invention, the packaging material may contain a substance therein, similar to the pouch described below, preferably at least one selected from the group consisting of a cleaning agent, a fabric softener, and a fragrance.

[0103] [Pouch] The present invention includes a pouch comprising the water-soluble film of the present invention. Because the pouch of the present invention comprises the water-soluble film, it has high water solubility, suppresses bleeding of the plasticizer, and improves mechanical strength.

[0104] In one embodiment of the present invention, the pouch of the present invention dissolves in water at 10°C preferably within 2000 seconds, more preferably within 1500 seconds, even more preferably within 1000 seconds, even more preferably within 700 seconds, particularly preferably within 600 seconds, and especially preferably within 500 seconds. The lower limit of the dissolution time is not particularly limited, and the shorter the dissolution time, the more preferable it is. The solubility of the pouch in water at 10°C (cold water solubility) can be adjusted to below the upper limit by, for example, appropriately adjusting the type and / or amount of components contained in the water-soluble film constituting the pouch; the pouch manufacturing conditions (e.g., the amount of water applied, temperature, and pressure during water sealing, the temperature and pressure during heat sealing), etc. The solubility of the pouch in water at 10°C can be determined, for example, by the method described in the Examples below.

[0105] The film contained in the pouch may be a monolayer film or a multilayer film. When the pouch comprises (or is composed of) a monolayer film, the monolayer film is the water-soluble film. When the pouch comprises (or is composed of) a multilayer film, the multilayer film may be a laminate of a plurality of the water-soluble films, or may be a laminate of the water-soluble film and another water-soluble film other than the water-soluble film. From the viewpoint of improving the water solubility, mechanical strength, and cold water solubility of the pouch, it is preferable that the pouch be composed of a monolayer or multilayer water-soluble film, and further from the viewpoint of production efficiency, it is more preferable that the pouch be composed of a monolayer water-soluble film.

[0106] The pouch is not particularly limited as long as it is capable of packaging a substance (preferably a content), and may be sealed or partially open. The pouch may be, for example, a two-sided pouch, a three-sided pouch, a flat pouch, a standing pouch, a gusset pouch, a bottom gusset pouch, a twin pouch, a spout pouch, a side-seal pouch, a bottom-seal pouch, or the like, or may be in the form of a container, a cup, or the like. In one embodiment of the present invention, the pouch may be partially open, but is preferably sealed. In such an embodiment, the pouch more preferably contains a content and is sealed.

[0107] [Method for manufacturing pouch] The method for manufacturing the pouch of the present invention from a water-soluble film is not particularly limited, and it can be manufactured by a method known in the art. The pouch of the present invention can be manufactured, for example, by a method including a step of sealing one or more sheets of water-soluble film to form a bag. Furthermore, a pouch containing a content can be manufactured, for example, by a method including a step of pouring the content into a film formed into a bag shape and sealing the pouring opening.

[0108] Methods for sealing a water-soluble film include a method of sealing by applying water to the film surface and adhering the coated surface (also called water sealing), a method of sealing by thermocompression bonding (also called heat sealing), a method of sealing with an adhesive, etc. Heat sealing is preferred from the viewpoint of not requiring an additional agent, and water sealing is preferred from the viewpoint of not requiring heat.

[0109] In one embodiment of the present invention, the water-soluble film has high adhesive strength due to moisture, and therefore can be suitably used for water sealing. In another embodiment of the present invention, the water-soluble film has high water-sealing properties and low heat-sealing properties. The low heat-sealing properties make it difficult for the film to adhere to the roll when the film is produced by a roll-to-roll method, effectively preventing damage during production. Furthermore, the high water-sealing properties allow the produced water-soluble film to be simply and easily formed into a pouch using moisture.

[0110] [Uses of the Pouch] The pouch of the present invention has excellent water solubility and mechanical properties, and also suppresses bleeding out of plasticizers. In one embodiment of the present invention, the pouch may contain at least one substance selected from the group consisting of beverage powders such as energy drink powders, hydration drink powders, sports drink powders and concentrates thereof, protein powders, hot cocoa, concentrated tea, tea leaves, mocha, concentrated fruit drinks, coffee, and chicory; flavor and texture improvers, instant foods such as spice packs for instant noodles, and concentrated soups; bread; confectionery; kimchi; pickles; salsa; tomato paste; seasonings or preservatives such as taco powder, dried pepper, pepper paste, miso, and spices; liquid, solid, or concentrated bouillon; food ingredients such as yeast, salt, spices, food coloring, texture adjusters, wheat flour, sugar, and powdered milk; egg products such as liquid eggs, egg whites, and egg yolks; and additives such as cream, gelatin, fruit fillings, and soybean paste. Furthermore, in a preferred embodiment of the present invention, the pouch of the present invention has excellent cold water solubility and is therefore particularly suitable for use in applications where the pouch is dissolved in cold water. Therefore, the pouch of the present invention preferably contains at least one selected from the group consisting of a cleaning agent, a fabric softener, and a fragrance. The physical properties of the contents are not particularly limited, and the contents may be acidic, neutral, or alkaline. The contents may be in any form, such as powder, block, gel, or liquid.

[0111] [Other Uses] The water-soluble film of the present invention can also be suitably used as a laundry sheet or fabric softener sheet. A laundry sheet is a sheet-shaped detergent in which detergent ingredients are wrapped in a film or impregnated into a film. A fabric softener sheet is a sheet-shaped fabric softener in which softener ingredients are wrapped in a film or impregnated into a film. A laundry sheet or fabric softener sheet can contain one or more layers of the water-soluble film of the present invention. A laundry sheet or fabric softener sheet can contain one or more layers of the water-soluble film of the present invention and one or more layers of a known water-soluble film or water-dispersible film. A laundry sheet or fabric softener sheet can further contain laundry additives such as detergent, bleach, or bleach ingredients.

[0112] The water-soluble film of the present invention can also be suitably used as a cosmetic mask. A cosmetic mask is a sheet in which cosmetic ingredients are wrapped in or impregnated into a film. The cosmetic mask can be used as a variety of face masks, such as a sheet shaped to fit a person's face. The face mask can contain various active ingredients for moisturizing, wrinkle reduction, and the like as cosmetic ingredients. The face mask delivers the active agent to the target organ and decomposes and dissolves over time with use. Water may be applied to the face mask before application. The face mask may contain one or more personal care compositions.

[0113] The present invention will be described in more detail below based on examples and comparative examples, but the present invention is not limited to the following examples.

[0114] Approximately 20 μg of each polysaccharide used in the Examples and Comparative Examples was subjected to gel filtration HPLC under the following conditions to measure the weight-average molecular weight (Mw) and number-average molecular weight (Mn). The measurement solvent was selected from water or dimethyl sulfoxide (DMSO) in consideration of the solubility of each polysaccharide.

[0115] (Gel filtration HPLC conditions) Eluent: 0.1 M aqueous sodium nitrate Column: One TSK GEL α-M column used Column temperature: 40°C Flow rate: 1 mL / min Sample concentration: 0.1 w / v% Sample preparation: The sample was dissolved by stirring at 80°C for 2.5 hours, and then stirred at 90°C for an additional 30 minutes. Filtration filter: 0.45 μm PP filter (Whatman) Injection volume: 100 μL Standard: PEO / PEG Measurement time: 18 minutes Solution delivery section: GPC-101 (Shodex) Detector: RI or

[0116] Eluent: 5 mM Na nitrate / DMSO Column: One TSK GEL α-M column used Column temperature: 60°C Flow rate: 0.8 mL / min Sample concentration: 0.2 w / v% Sample preparation: After leaving the column to stand overnight, the sample was dissolved by stirring at 60°C for 1 hour and then at 65°C for 1.5 hours. Filtration: 0.45 μm PP filter (Whatman) Injection volume: 100 μL Standard: PMMA-R, Y, G Measurement time: 18 minutes Solution delivery section: GPC-101 (Shodex) Detector: RI

[0117] Glass Transition Temperature of Plasticizers About 5 mg of each of the plasticizers used in the Examples and Comparative Examples was subjected to differential scanning calorimetry (DSC) under the following conditions to measure the glass transition temperature.

[0118] The glass transition temperature was evaluated by the midpoint method from a chart measured using a differential scanning calorimeter (DSC) (manufactured by TA Instruments). The glass transition temperature was measured at a temperature rise rate of 10°C / min in the measurement temperature range of -85 to 250°C.

[0119] Preparation of Water-Soluble Film Example 1 3 g of tamarind seed gum (weight average molecular weight 3,700 kDa, number average molecular weight 429 kDa; Glyloid (registered trademark) 6C, MP Gokyo Food & Chemical Co., Ltd.) as a polysaccharide was added to water, and the mixture was heated and stirred at 95°C for 2 hours to obtain an aqueous solution with a concentration of 4%. To this solution, 3 g of glycerin as plasticizer A and 4 g of fructose as plasticizer B were added to prepare a coating liquid. The coating liquid was applied to a polyethylene terephthalate film using a bar coater, and the film was dried with hot air at 60°C for 1 hour. The resulting dried coating film was peeled off from the polyethylene terephthalate film substrate to obtain a film with a thickness of approximately 80 μm.

[0120] Examples 2 to 4 Films were obtained in the same manner as in Example 1, except that the blending amounts of glycerin and fructose were changed to the amounts shown in Table 1.

[0121] Example 5 A film was obtained in the same manner as in Example 1, except that when tamarind seed gum (weight average molecular weight 261 kDa, number average molecular weight 80 kDa; Greate (registered trademark), MP manufactured by Gokyo Food & Chemical Co., Ltd.) was added as a polysaccharide, ι-carrageenan (weight average molecular weight 688 kDa, number average molecular weight 32 kDa; GENU CARRAGEENAN GENUTINE VCS-J, manufactured by Sansho Co., Ltd.) was used in addition to tamarind seed gum, and the respective components were blended in the amounts shown in Table 1.

[0122] Example 6 A film was obtained in the same manner as in Example 5, except that sucrose was added as plasticizer B instead of fructose, and the amounts of each component were changed as shown in Table 1.

[0123] Example 7 A film was obtained in the same manner as in Example 5, except that trehalose was added as plasticizer B instead of fructose, and the amounts of each component were changed as shown in Table 1.

[0124] Example 8 A film was obtained in the same manner as in Example 5, except that xylose was added as plasticizer B instead of fructose, and the amounts of each component were changed as shown in Table 1.

[0125] Examples 9 and 10 Films were obtained in the same manner as in Example 1, except that nonion-modified starch was used as the polysaccharide, and glycerin and trehalose were used as the plasticizers A and B in the amounts shown in Table 1.

[0126] Example 11 A film was obtained in the same manner as in Example 1, except that nonionic modified starch and ι-carrageenan (weight average molecular weight 688 kDa, number average molecular weight 32 kDa; GENU CARRAGEENAN GENUTINE VCS-J, manufactured by Sansho Co., Ltd.) were added as polysaccharides, and polyglycerin and PEG 4000 were added as plasticizers A and B in the amounts shown in Table 1.

[0127] Comparative Example 1 A film was obtained in the same manner as in Example 1, except that tamarind seed gum (weight average molecular weight 3,700 kDa, number average molecular weight 429 kDa; Glyloid (registered trademark) 6C, manufactured by MP Gokyo Food & Chemical Co., Ltd.) and glycerin were added in the amounts shown in Table 1.

[0128] Comparative Example 2 A film was obtained in the same manner as in Comparative Example 1, except that fructose was added instead of glycerin and the amounts of each component were changed as shown in Table 1.

[0129] Comparative Example 3 A film was obtained in the same manner as in Comparative Example 1, except that when tamarind seed gum (weight average molecular weight 261 kDa, number average molecular weight 80 kDa; Greate (registered trademark), MP manufactured by Gokyo Food & Chemical Co., Ltd.) was added, ι-carrageenan (weight average molecular weight 688 kDa, number average molecular weight 32 kDa; GENU CARRAGEENAN GENUTINE VCS-J, manufactured by Sansho Co., Ltd.) was used in addition to tamarind seed gum, and glycerin was added in the amount shown in Table 1.

[0130] Comparative Example 4 A film was obtained in the same manner as in Comparative Example 3, except that sucrose was added instead of glycerin and the amounts of each component were changed as shown in Table 1.

[0131] Comparative Example 5 A film was obtained in the same manner as in Comparative Example 3, except that trehalose was added instead of glycerin and the amounts of each component were changed as shown in Table 1.

[0132] Comparative Example 6 A film was obtained in the same manner as in Comparative Example 3, except that polyglycerin was added in addition to glycerin, and the amounts of each component were changed as shown in Table 1.

[0133] Comparative Example 7 A film was obtained in the same manner as in Comparative Example 2, except that sucrose and trehalose were added instead of fructose and the amounts of each component were changed as shown in Table 1.

[0134] Comparative Example 8 A film was obtained in the same manner as in Comparative Example 1, except that nonionic modified starch and glycerin were added in the amounts shown in Table 1.

[0135] Comparative Example 9 A film was obtained in the same manner as in Comparative Example 8, except that trehalose was added instead of glycerin and the amounts of each component were changed as shown in Table 1.

[0136] Comparative Example 10 A film was obtained in the same manner as in Comparative Example 1, except that nonionic modified starch and ι-carrageenan (weight average molecular weight 688 kDa, number average molecular weight 32 kDa; GENU CARRAGEENAN GENUTINE VCS-J, manufactured by Sansho Co., Ltd.) were added as polysaccharides, and polyglycerin was added in the amounts shown in Table 1.

[0137] Comparative Example 11 A film was obtained in the same manner as in Comparative Example 10, except that glycerin was added in the amount shown in Table 1 instead of polyglycerin.

[0138] Comparative Example 12 A film was obtained in the same manner as in Comparative Example 10, except that glycerin and diglycerin were added in the amounts shown in Table 1.

[0139]

[0140] Evaluation of Water-Soluble Films <Film Thickness> The film thickness of the water-soluble films prepared in the Examples and Comparative Examples was measured using a micrometer (Shinwa Measurement Co., Ltd., digital micrometer 0 to 25 mm (model number: 79523)). The thickness of the film was measured at any five or more points, and the average value of the measured values ​​was taken as the film thickness.

[0141] <Water Solubility> The water-soluble films prepared in the Examples and Comparative Examples were added to hot water at 90°C, and the films were dissolved by stirring for 5 minutes. The amount of solids that did not pass through a filter (21 µm) was measured, and was found to be 10 mass% or less in all Examples and Comparative Examples. The mass of the water-soluble film added was 0.1 mass parts per 100 mass parts of hot water at 90°C.

[0142] <Cold Water Solubility> The water-soluble films prepared in the Examples and Comparative Examples were cut into 30 mm x 40 mm rectangles and sandwiched between slide mounts. A 600 ml glass beaker with a body diameter of 90 mm and containing 500 ml of distilled water was placed in a separate thermostatic bath adjusted to 10°C, and stirred at 400 rpm using a cylindrical rotor with a length of 50 mm and a diameter of 8 mm. After the distilled water in the beaker reached 10°C, the slide mount was immersed in the stirred water. The dissolution state of the film was visually observed, and the time (seconds) from the start of immersion of the film in water was set to 0 seconds. The time (seconds) until the film was completely dissolved, i.e., until the film fragments that had broken apart in the distilled water could no longer be seen, was measured and evaluated according to the following evaluation criteria. When a film with a thickness other than 50 μm was used, the time was converted to a value for a film thickness of 50 μm according to the following formula: Converted complete dissolution time (seconds) = [50 / film thickness (μm)] ２ x Sample complete dissolution time (seconds) When the converted complete dissolution time was 600 seconds or less, it was rated as A, and when it was more than 600 seconds, it was rated as B.

[0143] <Toughness> The water-soluble films prepared in the Examples and Comparative Examples were stored for 7 days under an environment of 23°C and 50% RH, and then five test pieces measuring 10 mm in width and 120 mm in length were cut out. For each test piece, the maximum stress and elongation at break were measured using an autograph (apparatus name: AG-5000B, manufactured by Shimadzu Corporation) at a chuck distance of 70 mm and a tensile speed of 500 mm / min, and the average value was calculated. The value obtained by multiplying the maximum stress by the elongation at break was taken as the toughness of the water-soluble film. Furthermore, for each type of polysaccharide used, the increase in toughness of the water-soluble film obtained in each Example and Comparative Example was calculated according to the following formula, based on the toughness of the water-soluble film when plasticizer A was used alone. Examples 1 to 4 and Comparative Example 2 (when tamarind seed gum was used as polysaccharide A) Increase in toughness = {(toughness of each Example and Comparative Example) - (toughness of Comparative Example 1)} / (toughness of Comparative Example 1) x 100 Examples 5 to 8 and Comparative Example 6 (when tamarind seed gum and ι-carrageenan were used as polysaccharide A) Increase in toughness = {(toughness of each Example and Comparative Example) - (toughness of Comparative Example 3)} / (toughness of Comparative Example 3) x 100 Examples 9 to 10 (when starch was used as polysaccharide A) Increase in toughness = {(toughness of each Example) - (toughness of Comparative Example 8)} / (toughness of Comparative Example 8) x 100 Example 11 (when starch and ι-carrageenan were used as polysaccharide A and polyglycerin was used as plasticizer A) Increase in toughness = {(toughness of each Example and Comparative Example) - (toughness of Comparative Example 10)} / (toughness of Comparative Example 10) x 100 Comparative Example 12 (when starch and ι-carrageenan were used as polysaccharide A, and glycerin and diglycerin were used as plasticizer A) Increase in toughness = {(toughness of each Example and Comparative Example) - (toughness of Comparative Example 11)} / (toughness of Comparative Example 11) x 100

[0144] <Bleeding Out> The water-soluble films produced in the Examples and Comparative Examples were visually observed, and those in which the plasticizer did not bleed out onto the water-soluble film surface were rated A, and those in which the plasticizer bled out onto the water-soluble film surface were rated B.

[0145] The evaluation results are shown in Table 2.

[0146] As shown in Table 2, when the polysaccharides were the same, the water-soluble films prepared in the Examples were confirmed to have improved mechanical strength while suppressing the bleeding of the plasticizer. On the other hand, the Comparative Examples containing only Plasticizer A or Plasticizer B did not have a sufficient improvement in mechanical strength, or the plasticizer bleed out, or both.

[0147] Pouch Fabrication Example 12 A benchtop pouch molding machine (DD-SR12-1, manufactured by Dada) was used to form the pouch. The film obtained in Example 1 was cut into two pieces measuring 15 x 15 cm, which were used as the bottom film and the top film, respectively. The bottom film was placed in a pouch mold with a base of 40 x 45 mm and a depth of 18 mm, and heated at 100°C for 4 seconds. A vacuum was then created between the bottle film and the pouch mold to form the bottom of the pouch. Water was then brushed onto the four sides of the bottom film, and the top film was placed on top of it, overlapping the four corners. The overlapping portion of the bottom film and top film was heated and compressed at 100°C for 10 seconds to bond the top film to the bottom film. Air was then injected between the pouch mold and the bottom film, and the formed pouch was removed from the mold. The surrounding film was then cut and removed, leaving a 1.5 cm adhesive area.

[0148] Examples 13 to 16 Pouches were obtained in the same manner as in Example 12, except that the films obtained in Examples 3, 6, 9 and 11 were used, respectively.

[0149] Evaluation of Pouch <Formability of Bottom Film in Pouch> The state of the bottom film during bottom formation was visually evaluated. When the film was not damaged, it was marked A, and when the film was damaged, it was marked B.

[0150] <Air Leakage from Pouch> The obtained pouch was left for 24 hours in an environment of 23°C and 50% RH, and air leakage from the pouch was evaluated. A was given for no air leakage, and B was given for air leakage.

[0151] <Water Solubility of Pouch> A water solubility test was conducted using the obtained pouch. The obtained pouch was placed in a wire frame cage (10 cm x 9 cm x 6.4 cm, wire gauge 1.25 mm, opening 1.27 cm). 1200 ml of distilled water was placed in a 2-liter beaker and stirred at 400 rpm using a 5 cm rotor. After the distilled water in the beaker reached 10°C, the wire frame cage and pouch were placed in the beaker so that the cage was 1 inch (2.54 cm) from the bottom. The dissolution state of the film was visually observed to confirm whether the film was completely dissolved. Cases without residue were marked A, and cases with residue were marked B.

[0152] <Appearance of pouch (presence or absence of bleed-out)> The obtained pouches were visually observed, and those in which the plasticizer did not bleed out onto the surface of the pouch were rated A, and those in which the plasticizer bled out onto the surface of the pouch were rated B.

[0153] The evaluation results are shown in Table 3.

[0154] Evaluation of Laminate Example 17 3 g of tamarind seed gum (weight-average molecular weight 261 kDa, number-average molecular weight 80 kDa; Greate (registered trademark), MP Gokyo Food & Chemical Co., Ltd.) as a polysaccharide, 1 g of glycerin as plasticizer A, and 6 g of fructose as plasticizer B were added to water, and the resulting mixture was added to purified water so that the total concentration was 15% by mass. The mixture was then heated and stirred at 90°C for 1 hour to dissolve the mixture. The solution (coating solution) was cooled to 25°C. The resulting coating solution was applied to a paper support (Soluble 62 gsm) using a bar coater so that the thickness of the coating solution after application (hereinafter sometimes simply referred to as "coating solution thickness") was 3.3 μm, forming a coating film. The wet coating film on the support was dried in a hot air dryer at 80°C for 30 minutes to obtain a laminate consisting of a coating film integrated with the support.

[0155] Example 18: Using trehalose as plasticizer B, the blending amounts of each component were as shown in Table 4, and these were added to pure water to give a total concentration of 15% by mass. The resulting coating solution was applied to a paper support (Soluble 62 gsm) using a bar coater so that the thickness of the coating solution after application was 4.4 μm, forming a coating film. The wet coating film on the support was dried in a hot air dryer at 80° C. for 30 minutes to obtain a laminate consisting of a coating film integrated with the support.

[0156] Example 19 Nonionic modified starch as polysaccharide, glycerin as plasticizer A, and trehalose as plasticizer B were added to pure water in the amounts shown in Table 4 so that the total concentration was 20% by mass, and the mixture was dissolved by heating and stirring at 90°C for 1 hour. The solution (coating liquid) was cooled to 25°C. The resulting coating liquid was applied to 80 g of bleached kraft paper (B-F) as a support using a bar coater, resulting in a coating thickness of 6.2 μm after application, to form a coating film. The wet coating film on the support was dried in a hot air dryer at 80°C for 30 minutes, yielding a laminate consisting of a coating film integrated with the support.

[0157] [Coating Film Thickness] The coating film thickness was calculated using the following formulas: Coating film thickness [μm] = Concentration of coating liquid [mass %] × Thickness of coating liquid [μm] / 100 Coating liquid concentration [mass %] = {(Mass of coating liquid [g] - Mass of water contained in coating liquid [g]) / Mass of coating liquid [g]} × 100 The total thickness of the coating film when coating was performed twice was calculated by substituting "total thickness of coating liquid" for "thickness of coating liquid" in the above formulas.

[0158] [Flexibility] The laminate was folded with the coated side facing inward. A 2 kg rubber roller was rolled back and forth once from one end of the folded area (crease) to the other to create a crease. Toluene colored with food coloring was applied to a 10 cm area of ​​the crease on the coated side, and then the back side (uncoated side) was checked for bleed-through (small red spots or full coloring of the coated surface). If no bleed-through was found, the same procedure was repeated to check for bleed-through. The maximum number of folds without bleed-through was defined as flexibility [times], with a maximum of 5 times. The higher this value, the better the mechanical strength of the coating layer and the less likely it is to crack when bent.

[0159] [Oxygen Transmission Rate (OTR)] The oxygen transmission rate (cc / m) of the laminate was measured using an oxygen transmission rate measuring device (OXYSENSE MODEL 8101e manufactured by Systech Illinois) under the following conditions: ２ The oxygen pressure was measured at 1.0 atm. The oxygen pressure was 1.0 atm. The oxygen supply humidity was 50% RH at 23°C, the carrier gas humidity was 50% RH at 23°C, the carrier gas flow rate was 10 mL / min, and the carrier gas pressure was 1.0 atm.

[0160] The evaluation results are shown in Table 4.

Claims

1. A water-soluble film comprising a polysaccharide, a plasticizer A, and a plasticizer B, wherein the plasticizer A has a glass transition temperature (Tg) of -30°C or lower, and the plasticizer B has a glass transition temperature (Tg) of 0°C or higher, the total content of the plasticizers A and B is more than 20% by mass and 90% by mass or lower relative to the mass of the water-soluble film, and the content of a polyvinyl alcohol-based resin is less than 30% by mass relative to the mass of the water-soluble film.

2. The water-soluble film of claim 1, wherein the plasticizer is selected from the group consisting of polyhydric alcohols, hydroxy acids, monosaccharides, disaccharides, and amino acids.

3. The water-soluble film according to claim 1, wherein the plasticizer A is at least one selected from the group consisting of glycerin, polyglycerin having a molecular weight of 2000 or less, ethylene glycol, polyethylene glycol having a molecular weight of 650 or less, propylene glycol, polypropylene glycol having a molecular weight of 3000 or less, 2-methyl-1,3-propanediol, and derivatives thereof.

4. The water-soluble film according to claim 1, wherein the content of said plasticizer A is 5 to 85% by mass relative to the mass of said water-soluble film.

5. The water-soluble film according to claim 1, wherein the plasticizer B is at least one selected from the group consisting of xylitol, maltitol, mannitol, xylose, fructose, mannose, sucrose, galactose, trehalose, lysine, glycine, and derivatives thereof.

6. The water-soluble film according to claim 1, wherein the content of said plasticizer B is 5 to 85% by mass relative to the mass of said water-soluble film.

7. The water-soluble film according to claim 1, wherein the blending ratio of the plasticizer A and the plasticizer B by mass is plasticizer A / plasticizer B of 10 / 90 to 90 / 10.

8. The water-soluble film of claim 1, wherein the polysaccharide is at least one selected from the group consisting of starch, carrageenan, alginic acid, guar gum, xanthan gum, pectin, hydroxyalkyl cellulose, alkyl cellulose, tamarind seed gum, agar, pullulan, locust bean gum, tara gum, and derivatives thereof.

9. A packaging material comprising the water-soluble film of claim 1.

10. A pouch comprising the water-soluble film of claim 1.

11. The pouch of claim 10, containing therein at least one selected from the group consisting of cleaning agents, fabric softeners, and fragrances.

12. A molded article comprising the water-soluble film of claim 1.

13. A laminate comprising the water-soluble film of claim 1.

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