Film

Abstract

The present invention relates to a film containing a polysaccharide A and a polysaccharide B, wherein the polysaccharide A has an ionic functional group, and the polysaccharide B is composed only of a β-1,4-bond in the main chain.

Description

film

[0001] This patent application claims priority under the Paris Convention to Japanese Patent Application No. 2024-092943 (filing date: June 7, 2024), the entire contents of which are incorporated herein by reference. The present invention relates to a film and a pouch comprising the film.

[0002] Compositions containing polyols have been widely used for molding applications. For example, Patent Document 1 describes a film containing polyvinyl alcohol and a sugar alcohol. Patent Document 2 describes a resin composition containing a vinyl alcohol polymer and starch.

[0003] JP 2019-81901 A, WO 2022 / 270620 B, Pamphlet

[0004] The properties required for a molded article obtained from a composition containing a polyol vary depending on its form and application. For example, when the molded article is a film and is used as a pouch containing contents, it is required that the solution for preparing the film has good coatability to ensure uniformity of the film, that the film has excellent elongation to avoid breakage when filling the film with contents, and that the film has excellent stress to avoid breakage during transportation.

[0005] That is, the present inventors have found that when the molded article is used as a pouch, it is particularly important to increase the mechanical strength of the film. Accordingly, an object of the present invention is to provide a film having high mechanical strength and a pouch comprising the 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 film comprising polysaccharide A and polysaccharide B, wherein polysaccharide A has an ionic functional group, and polysaccharide B has a main chain composed solely of β-1,4-bonds. [2] The film according to [1], wherein polysaccharide A is at least one selected from the group consisting of pectin, carrageenan, gum arabic, alginic acid, agar, and derivatives thereof. [3] The film according to [1] or [2], wherein the content of polysaccharide A is 0.1 to 50% by mass relative to the mass of the film. [4] The film according to any one of [1] to [3], wherein polysaccharide B is at least one selected from the group consisting of tamarind seed gum, cellulose, guar gum, tara gum, locust bean gum, and derivatives thereof. [5] The film according to any one of [1] to [4], wherein the content of polysaccharide B is 5 to 80% by mass relative to the mass of the film. [6] The film according to any one of [1] to [5], wherein the total content of the polysaccharide A and the polysaccharide B is 20 to 90% by mass relative to the mass of the film. [7] The film according to any one of [1] to [6], further comprising a plasticizer. [8] The film according to [7], wherein the plasticizer is at least one selected from the group consisting of polyhydric alcohols, hydroxy acids, monosaccharides, and disaccharides. [9] The film according to [7] or [8], wherein the content of the plasticizer is 20 to 95% by mass relative to the mass of the film.

[10] The film according to any one of [1] to [9], wherein the content of the polyvinyl alcohol-based resin is less than 30% by mass relative to the mass of the film.

[11] The film according to any one of [1] to

[10] , wherein the toughness is 1500 or more.

[12] The film according to any one of [1] to

[11] , wherein the film is water-soluble.

[13] A packaging material comprising the film according to any one of [1] to

[12] .

[14] A pouch comprising the film according to any one of [1] to

[12] .

[15] The pouch according to

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

[16] A molded article comprising the film according to any one of [1] to

[12] .

[17] A laminate comprising the film according to any one of [1] to

[12] .

[0008] According to the present invention, it is possible to provide a film having high mechanical strength and a pouch comprising said film.

[0009] 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.

[0010] [Film] The film of the present invention contains polysaccharide A and polysaccharide B, wherein polysaccharide A has an ionic functional group and polysaccharide B has a main chain composed only of β-1,4-bonds. In this specification, mechanical strength refers to mechanical strength including "toughness," which is the product of maximum stress (MPa) and breaking elongation (%).

[0011] The present inventors have conducted further studies on the mechanical strength of films and have unexpectedly found that a film containing a polysaccharide A having ionic functional groups and a polysaccharide B having a main chain composed exclusively of β-1,4-bonds can solve the above-mentioned problems. The reason for this is unclear, but is thought to be as follows: Generally, polysaccharide A having ionic functional groups forms a dense cross-linked structure due to interactions between the charges of the polymer chains and counterions, resulting in a hard but brittle state. Furthermore, polysaccharides whose main chains mainly contain α-1,4-bonds form regular helical structures by themselves and are less likely to interact with each other. In contrast, polysaccharide B having a main chain composed exclusively of β-1,4-bonds can form a polymer network due to hydrophobic interactions between molecular chains (on the surfaces lacking hydroxyl groups), resulting in a gel that is more flexible and has a lower elastic modulus than polysaccharide A having ionic functional groups. Therefore, when polysaccharide A, which has ionic functional groups, is combined with polysaccharide B, whose main chain is composed only of β-1,4-bonds, the charged polysaccharide A penetrates into the polymer network formed by polysaccharide B. This can also be seen as polysaccharide A and polysaccharide B forming gels of different strengths within the film. When force is applied to the film, the hard but brittle gel of polysaccharide A is sacrificed (broken) and absorbs the energy, stopping the progression of cracks, which is presumably why the film achieves high strength.

[0012] Furthermore, polysaccharide A can penetrate into the polymer network formed by polysaccharide B, thereby reducing interactions between polysaccharides B. Compared to a film, the presence of a solvent suppresses gelation in a low-concentration solution state, so a solution containing polysaccharide A and polysaccharide B can have a lower viscosity than a solution containing only polysaccharide B. This can improve coatability, for example, during film production.

[0013] <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.

[0014] (Polysaccharide A) In the present invention, polysaccharide A has an ionic functional group. Examples of the ionic functional group include cationic functional groups such as amino groups, imino groups, quaternary ammonium groups, imidazolium groups, and pyridinium groups; and anionic functional groups such as carboxyl groups, sulfate groups, and phosphate groups. Polysaccharide A may have only one type of functional group, or two or more types of functional groups. Polysaccharide A may be used alone, or two or more types of polysaccharides A having different ionic functional groups may be combined. However, mixing one or more types of polysaccharides A having cationic functional groups with one or more types of polysaccharides A having anionic functional groups may reduce the water solubility of the film due to ionic interactions.

[0015] In one embodiment of the present invention, the number-average molecular weight (sometimes referred to as Mn) of polysaccharide A 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, 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 polysaccharide A is preferably 5 to 150,000 kDa, more preferably 10 to 50,000 Da, and even more preferably 20 to 30,000 kDa, and may be, 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 polysaccharide A are within the above ranges, the mechanical strength of the film can be further increased. When polysaccharide A is composed of two or more polysaccharides, the Mn of polysaccharide A is a weighted average of the Mn of the two or more polysaccharides. The same applies to Mw. Polysaccharide A may also contain polysaccharides of the same type but with different Mn and / or Mw. In this specification, the Mn and Mw of polysaccharide A can be determined by gel filtration HPLC, for example, by the method described in the Examples below.

[0016] In the present invention, examples of polysaccharide A include pectin, carrageenan, gum arabic, alginic acid, agar, gellan gum, and derivatives thereof, as well as polysaccharides into which ionic functional groups have been introduced by chemical modification (excluding polysaccharides whose main chains are composed only of β-1,4-bonds). From the viewpoint of further increasing the mechanical strength of the film, however, it is preferable that the polysaccharide A be at least one selected from the group consisting of pectin, carrageenan, gum arabic, alginic acid, agar, and derivatives thereof.

[0017] Examples of derivatives of polysaccharide A include 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.

[0018] Pectin is a polysaccharide found in plants, and has an α-1,4-bond structure of galacturonic acid and methyl-esterified galacturonic acid, in which galacturonic acid is methyl-esterified, and a carboxyl group based on galacturonic acid as an ionic functional group. 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.

[0019] Carrageenan is a polysaccharide obtained from red algae and has repeating units of D-galactose or 3,6-anhydro-D-galactose, and a sulfate group as an ionic functional group. Carrageenan is classified into κ (kappa) carrageenan, ι (iota) carrageenan, and λ (lambda) carrageenan. These can be used alone or in combination. From the viewpoint of coatability and cold water solubility, it is preferable to contain ι (iota) carrageenan. As carrageenan, for example, commercially available 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 the carrageenan is preferably 5 to 5,000 kDa, more preferably 10 to 3,000 kDa, even more preferably 20 to 1,000 kDa, 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, even more preferably 20 to 5,000 kDa, for example, 50 to 2,000 kDa or 100 to 1,000 kDa.

[0020] Gum arabic is a polysaccharide obtained from the sap of the gum arabic tree (Acacia senegal), and contains structural units such as galactose, arabinose, and rhamnose, and a carboxyl group based on glucuronic acid as an ionic functional group. Commercially available gum arabic, such as "Gum Arabic HP" (manufactured by MP Gokyo Food & Chemical Co., Ltd.), may be used. The Mn of gum arabic is preferably 1 to 1,000 kDa, more preferably 5 to 5,000 kDa, and the Mw is preferably 3 to 3,000 kDa, more preferably 10 to 1,000 kDa.

[0021] Alginic acid is a polysaccharide found in brown algae and the like, and has a structure in which mannuronic acid and guluronic acid are bonded, and has a carboxyl group as an ionic functional group. The Mn of alginic acid 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 alginic acid is preferably 5 to 150,000 kDa, more preferably 10 to 30,000 kDa, and even more preferably 15 to 15,000 kDa, and may be, for example, 20 to 5,000 kDa, 30 to 1,000 kDa, or 50 to 500 kDa.

[0022] Agar is a polysaccharide obtained from red algae, and has a structure in which D-galactose and anhydro-L-galactose are alternately bonded, and has sulfate groups and / or carboxyl groups as ionic functional 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.

[0023] In the film of the present invention, the content of polysaccharide A is preferably 0.1 to 50% by mass, more preferably 0.5 to 48% by mass, even more preferably 1.0 to 45% by mass, even more preferably 1.5 to 43% by mass, and particularly preferably 2.0 to 40% by mass, 2.5 to 38% by mass, 3.0 to 35% by mass, 4.0 to 33% by mass, 5.0 to 30% by mass, 7.5 to 28% by mass, 10 to 25% by mass, or 11 to 20% by mass, based on the mass of the film. When the content of polysaccharide A is within the above range, the mechanical strength of the film can be further increased. Furthermore, the viscosity of a solution containing polysaccharide A and polysaccharide B can be reduced.

[0024] (Polysaccharide B) In the present invention, the main chain of polysaccharide B is composed exclusively of β-1,4-bonds. "The main chain is composed exclusively of β-1,4-bonds" means that the relatively longest bond chain in the polysaccharide molecule is composed exclusively of β-1,4-bonds, and its side chain may contain bonds other than β-1,4-bonds. One type of polysaccharide B may be used alone, or two or more types of polysaccharide B may be used in combination. In the present invention, a polysaccharide having an ionic functional group and a main chain composed exclusively of β-1,4-bonds falls under the category of polysaccharide B, since the structure of the main chain can have a significant effect on the properties of the polysaccharide.

[0025] In one embodiment of the present invention, the number-average molecular weight (sometimes referred to as Mn) of polysaccharide B 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, 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 polysaccharide B is preferably 5 to 150,000 kDa, more preferably 10 to 50,000 kDa, and even more preferably 20 to 30,000 kDa, and may be, 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 polysaccharide B are within the above ranges, the mechanical strength of the film can be further increased. When polysaccharide B is composed of two or more polysaccharides, the Mn of polysaccharide B is a weighted average of the Mn of the two or more polysaccharides. The same applies to Mw. Polysaccharide B may also contain the same type of polysaccharides but with different Mn and / or Mw. In this specification, the Mn and Mw of polysaccharide B can be determined by gel filtration HPLC, for example, by the method described in the Examples below.

[0026] In the present invention, examples of polysaccharide B include tamarind seed gum, cellulose, guar gum, tara gum, locust bean gum, fenugreek gum, cassia gum, xanthan gum, mannan, glucomannan, chitin, chitosan, and derivatives thereof. From the viewpoint of further increasing the mechanical strength of the film, however, it is preferably at least one selected from the group consisting of tamarind seed gum, cellulose, guar gum, tara gum, locust bean gum, and derivatives thereof.

[0027] Derivatives of polysaccharide B 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.

[0028] Tamarind seed gum is a polysaccharide obtained from the seeds of tamarind (Tamarindus indica) and has a structure in which β-1,4-linked glucose is the main chain and xylose and galactose are bonded to the side chains. Commercially available tamarind seed gums may be used, such as Glyloid (registered trademark), Glyate (registered trademark) (manufactured by MP Gokyo Food & Chemical Co., Ltd.), and TG120 (manufactured by Mitsubishi Chemical Corporation). The Mn of the tamarind seed gum is preferably 10 to 3,000 kDa, more preferably 30 to 1,000 kDa, even more preferably 50 to 500 kDa, and even more preferably 55 to 400 kDa, 55 to 300 kDa, or 60 to 100 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, 60 to 4,000 kDa, 70 to 3,600 kDa, 80 to 2,000 kDa, 90 to 1,000 kDa, or 100 to 500 kDa, for example, 1,000 to 4,000 kDa or 100 to 400 kDa.

[0029] Cellulose is a polysaccharide that constitutes the cell walls and fibers of trees and plants, and is a polysaccharide formed by the polymerization of glucose through β-1,4-bonds. Examples of cellulose derivatives include hydroxyalkyl cellulose and alkyl cellulose. Examples of hydroxyalkyl cellulose include hydroxyalkyl celluloses in which the hydroxyalkyl group has 2 to 10 carbon atoms, such as hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxypropyl methyl cellulose, and hydroxyethyl methyl cellulose, and preferably hydroxyalkyl celluloses in which the hydroxyalkyl group has 2 to 6 carbon atoms. Examples of alkyl cellulose include alkyl celluloses in which the alkyl group has 2 to 10 carbon atoms, such as methyl cellulose, ethyl cellulose, propyl cellulose, and butyl cellulose, and alkyl celluloses in which the alkyl group has 2 to 6 carbon atoms. The hydroxyalkyl cellulose refers to cellulose in which one or more hydroxyl groups have been modified with a hydroxyalkyl group, and the alkyl cellulose refers to cellulose in which one or more hydroxyl groups have been modified with an alkyl group. The carbon number of the hydroxyalkyl group and the carbon number of the alkyl group refer to the carbon number of one hydroxyalkyl group and the carbon number of one alkyl group, respectively. As cellulose and its derivatives, commercially available products such as "Metolose (registered trademark)" (manufactured by Shin-Etsu Chemical Co., Ltd.), "HEC Daicel" (manufactured by Daicel Corporation), "HEC A Grade", "HEC S Grade", and "HEC CF Grade" (manufactured by Sumitomo Seika Chemicals Co., Ltd.) may be used. The Mn of cellulose and its derivatives 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 cellulose and its derivatives is preferably 10 to 50,000 kDa, more preferably 30 to 10,000 kDa, and even more preferably 50 to 5,000 kDa, and may be, for example, 500 to 4,500 kDa or 1,000 to 4,000 kDa.

[0030] Guar gum is a polysaccharide obtained from the endosperm of guar beans (Cyamopsis tetragonoloba) and has a structure in which β-1,4-linked mannose is the main chain and galactose is bound 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.

[0031] Tara gum is a polysaccharide obtained from the seeds of tara (Caesalpinia spinosa) and has a structure in which β-1,4-linked 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.

[0032] Locust bean gum is a polysaccharide obtained from the seeds of carob (Celatonia siliqua) and has a structure in which β-1,4-linked mannose is the main chain and galactose is bound to the side chain. Commercially available locust bean gum, such as "GENU (registered trademark) GUM type RL-200Z" (manufactured by Sansho Co., Ltd.), "Soarlocust A120," and "MC1000" (manufactured by Mitsubishi Chemical Corporation), may be used. 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.

[0033] Xanthan gum is a polysaccharide produced by fermenting starch with the bacterium Xanthomonas campestris. It has a main chain of β-1,4-linked glucose 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.

[0034] In the film of the present invention, the content of polysaccharide B is preferably 3 to 82 mass%, more preferably 5 to 80 mass%, even more preferably 10 to 75 mass%, even more preferably 15 to 70 mass%, and particularly preferably 20 to 65 mass%, 25 to 60 mass%, 30 to 55 mass%, 33 to 50 mass%, 35 to 48 mass%, or 38 to 45 mass%, based on the mass of the film. When the content of polysaccharide B is within the above range, the mechanical strength of the film can be further increased. Furthermore, the viscosity of a solution containing polysaccharide A and polysaccharide B can be reduced.

[0035] In the film of the present invention, the total content of polysaccharide A and polysaccharide B is preferably 20 to 90% by mass, more preferably 23 to 85% by mass, even more preferably 25 to 80% by mass, even more preferably 27 to 75% by mass, and particularly preferably 30 to 70% by mass, 33 to 65% by mass, 35 to 60% by mass, or 35 to 55% by mass, based on the mass of the film. When the total content of polysaccharide A and polysaccharide B is within the above range, the mechanical strength of the film can be further increased. Furthermore, the viscosity of a solution containing polysaccharide A and polysaccharide B can be reduced.

[0036] In the film of the present invention, the blending ratio of polysaccharide A to polysaccharide B by mass is preferably 0.5:99.5 to 99.5:0.5, more preferably 1:99 to 99:1, even more preferably 3:97 to 97:3, even more preferably 5:95 to 95:5, and particularly preferably 7:93 to 93:7, 10:90 to 90:10, 13:87 to 87:13, 15:85 to 85:15, 20:80 to 80:20, 25:75 to 75:25, 30:70 to 70:30, or 40:60 to 60:40. When the blending ratio of polysaccharide A to polysaccharide B is within the above range, the mechanical strength of the film can be further increased. Furthermore, the viscosity of a solution containing polysaccharide A and polysaccharide B can be reduced.

[0037] In a preferred embodiment of the present invention, from the viewpoint of further improving the mechanical strength of the film, preferred combinations of polysaccharide A and polysaccharide B include, for example, pectin / tamarind seed gum; carrageenan / tamarind seed gum; gum arabic / tamarind seed gum; carrageenan / guar gum; etc., more preferred are pectin / tamarind seed gum; iota-carrageenan / tamarind seed gum; gum arabic / tamarind seed gum; carrageenan / guar gum; and even more preferred are pectin / tamarind seed gum; gum arabic / tamarind seed gum; and carrageenan / guar gum.

[0038] (Polysaccharides other than polysaccharide A and polysaccharide B) The film of the present invention may further contain a polysaccharide other than polysaccharide A and polysaccharide B. That is, the polysaccharide other than polysaccharide A and polysaccharide B may be a polysaccharide that does not have an ionic functional group and whose main chain contains a bond other than a β-1,4-bond. Examples of polysaccharides other than polysaccharide A and polysaccharide B include starch and pullulan. The polysaccharides other than polysaccharide A and polysaccharide B may be used alone or in combination of two or more.

[0039] The starch is preferably derived from plants, such as from plant bulbs, seeds, leaves, or stems. Examples of starches suitable for the present invention include 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, tapioca starch, and corn starch being preferred. 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.

[0040] 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 by α-1,4-bonds and maltotriose is linked by α-1,6-bonds. 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.

[0041] In the present invention, the content of polysaccharides other than polysaccharide A and polysaccharide B is preferably 0 to 50% by mass, more preferably 0 to 45% by mass, even more preferably 0 to 42% by mass, and even more preferably 0 to 40% by mass, 0 to 39% by mass, 0 to 35% by mass, 0 to 30% by mass, 0 to 25% by mass, 0 to 20% by mass, 0 to 15% by mass, 0.5 to 10% by mass, 1 to 8% by mass, or 1.5 to 5% by mass, relative to the mass of the film. When the content of polysaccharides other than polysaccharide A and polysaccharide B is within the above range, the mechanical strength of the film can be further increased.

[0042] <Plasticizer> The film of the present invention preferably further contains a plasticizer. The plasticizer can aggregate polysaccharides by dehydrating them. Furthermore, it can form a higher-order network by hydrogen bonding with polysaccharides. Therefore, when the film of the present invention further contains a plasticizer, the mechanical strength of the film can be further increased and processability can also be improved.

[0043] In the present invention, from the viewpoint of further increasing the mechanical strength of the film, the plasticizer is preferably at least one selected from the group consisting of polyhydric alcohols, hydroxy acids, monosaccharides, and disaccharides. One type of plasticizer may be used alone, or two or more types may be used in combination.

[0044] Examples of the polyhydric alcohol include glycerin, diglycerin, sorbitol, alkylene glycols (e.g., alkylene glycols having 2 to 10 carbon atoms, such as ethylene glycol, propylene glycol, and neopentyl glycol), polyalkylene glycols (e.g., diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycols having a molecular weight of up to 400, and polypropylene glycols having a molecular weight of up to 400), trimethylolpropane, erythritol, xylitol, 2-methyl-1,3-propanediol, maltitol, mannitol, and pentaerythritol.

[0045] Examples of the hydroxy acid include lactic acid, glycolic acid, malic acid, and tartaric acid.

[0046] Examples of the monosaccharides include glucose, mannose, galactose, fructose, and xylose.

[0047] Examples of the disaccharides include maltose, trehalose, sucrose, and lactose.

[0048] Among these, from the viewpoint of further increasing the mechanical strength of the film, the plasticizer is preferably glycerin, sorbitol, polyalkylene glycol, glucose, fructose, or trehalose, and more preferably glycerin, sorbitol, or fructose.

[0049] In the film of the present invention, the content of the plasticizer is preferably 20 to 95% by mass, more preferably 25 to 93% by mass, even more preferably 30 to 90% by mass, even more preferably 35 to 88% by mass, and particularly preferably 40 to 85% by mass, 43 to 83% by mass, 45 to 80% by mass, or 48 to 78% by mass, based on the mass of the film. When the content of the plasticizer is within the above range, the mechanical strength of the film can be further increased. Furthermore, the viscosity of the solution containing polysaccharide A and polysaccharide B can be reduced.

[0050] In one embodiment of the present invention, the mass ratio of the total amount of polysaccharide A and polysaccharide B to the plasticizer is preferably (polysaccharide A + polysaccharide B):(plasticizer) = 10:90 to 90:10, more preferably 20:80 to 80:20, even more preferably 25:75: to 75:25, and particularly preferably 27:78 to 87:27. When the mass ratio of the total amount of polysaccharide A and polysaccharide B to the plasticizer is within the above range, the mechanical strength of the film can be further increased. Furthermore, the viscosity of the solution containing polysaccharide A and polysaccharide B can be reduced.

[0051] <Additives> The 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 moisture, antioxidants, UV 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.

[0052] 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.

[0053] 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 10% by mass, preferably 0.001 to 10% by mass, more preferably 0.01 to 5% by mass, and even more preferably 0.1 to 1% by mass, relative to the mass of the film.

[0054] In one embodiment of the present invention, the content of the polyvinyl alcohol-based resin in the film is preferably less than 30% by mass, more preferably 20% by mass or less, even more preferably 10% by mass or less, even more preferably 5% by mass or less, particularly preferably 1% by mass or less, or 0.1% by mass or less, and may even be 0% by mass. That is, it 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. When the content of the polyvinyl alcohol-based resin in the film is within the above range, the film's GHG (Green House Gas) emissions can be reduced, thereby reducing the environmental impact. Furthermore, film degradation due to alkaline substances such as detergents can be reduced. The polyvinyl alcohol-based resin used in the present invention can be made from vinyl acetate derived from petroleum-derived carbon, vinyl acetate derived from biomass-derived carbon, or a mixture thereof.

[0055] In one embodiment of the present invention, the total content of polysaccharide A, polysaccharide B, and plasticizer contained in the film is preferably 30% by mass or more, more preferably 50% by mass or more, even more preferably 60% by mass or more, even more preferably 70% by mass or more, particularly preferably 80% by mass or more, particularly preferably 90% by mass or more, 95% by mass or more, or 98% by mass or more, based on the mass of the film. That is, it is preferably 30 to 100% by mass, more preferably 50 to 100% by mass, even more preferably 60 to 100% by mass, even more preferably 70 to 100% by mass, particularly preferably 80 to 100% by mass, particularly preferably 90 to 100% by mass, 95 to 100% by mass, or 98 to 100% by mass. When the total content of polysaccharide A, polysaccharide B, and plasticizer contained in the film is within the above range, the mechanical strength of the film can be further increased. Furthermore, the viscosity of a solution containing polysaccharide A and polysaccharide B can be reduced.

[0056] The film of the present invention has high mechanical strength because it contains the above-mentioned polysaccharide A, polysaccharide B, and plasticizer. Furthermore, the film of the present invention is preferably water-soluble. In this specification, "water-soluble" means that it can be dissolved in water, preferably having a solubility of 90% by mass or more in 90°C hot water. That is, a 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 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 film of the present invention 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 film is dissolved in water. The upper limit of the solubility of the film is 100% by mass. That is, the solubility of the film is preferably 90 to 100% by mass, more preferably 95 to 100% by mass, and even more preferably 98 to 100% by mass. The solubility of the 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 film.

[0057] In one embodiment of the present invention, the film preferably has high cold water solubility. Cold water solubility refers to the solubility of the film in cold water (e.g., 10°C). In one embodiment of the present invention, the film of the present invention can be dissolved in water at 10°C preferably within 1000 seconds. That is, when a 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 film in water at 10°C is equal to or less than the upper limit, the film can be quickly dissolved even when dissolved in cold water for use. For example, in the case of a pouch containing the 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 the film to completely dissolve in water at 10°C can be adjusted to be equal to or less than the upper limit by, for example, appropriately adjusting the types and / or amounts of components contained in the film, the film production conditions (drying conditions, etc.), etc. The time required for the film to completely dissolve in water at 10°C can be determined, for example, by the method described in the Examples below.

[0058] In one embodiment of the present invention, the maximum stress of the film is preferably 5 MPa or more, 10 MPa or more, 12 MPa or more, 14 MPa or more, 15 MPa or more, 17 MPa or more, 20 MPa or more, 20.5 MPa or more, 21 MPa or more, 22 MPa or more, 23 MPa or more, or 24 MPa or more. The upper limit of the maximum stress of the film is usually 150 MPa or less, preferably 140 MPa or less. Therefore, the maximum stress of the film is preferably 5 to 150 MPa, more preferably 10 to 150 MPa, even more preferably 12 to 150 MPa, still more preferably 14 to 150 MPa, particularly preferably 15 to 140 MPa, 17 to 140 MPa, 20 to 140 MPa, 20.5 to 140 MPa, 21 to 140 MPa, 22 to 140 MPa, 23 to 140 MPa, or 24 to 140 MPa.

[0059] In one embodiment of the present invention, the breaking elongation of the film is preferably 45% or more, 50% or more, 60% or more, 70% or more, 75% or more, 80% or more, 85% or more, 90% or more, 95% or more, 100% or more, 102% or more, or 130% or more. The upper limit of the breaking elongation of the film is usually 300% or less, preferably 200% or less. Therefore, the breaking elongation of the film is preferably 45 to 300%, more preferably 50 to 300%, even more preferably 60 to 300%, even more preferably 70 to 300%, particularly preferably 75 to 300%, 80 to 200%, 85 to 200%, 90 to 200%, 95 to 200%, 100 to 200%, 102 to 200%, or 130 to 200%. The maximum stress and breaking elongation of the film can be determined by a tensile test, for example, by the method described in the Examples below.

[0060] In one embodiment of the present invention, the toughness of the film is preferably 1500 or more, 1550 or more, 1560 or more, 1580 or more, 1600 or more, 1650 or more, 1680 or more, 1710 or more, 1870 or more, 1900 or more, 1950 or more, 2000 or more, 2050 or more, or 2100 or more. The upper limit of the toughness is usually 4000 or less, preferably 3000 or less. When the toughness of the film of the present invention is equal to or greater than the lower limit, the mechanical strength of the film is improved. For example, when a pouch containing the film of the present invention is produced, the 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. Therefore, the toughness of the film is preferably 1500 to 4000, more preferably 1550 to 4000, even more preferably 1560 to 4000, still more preferably 1580 to 4000, particularly preferably 1600 to 4000, 1650 to 4000, 1680 to 3000, 1710 to 3000, 1870 to 3000, 1900 to 3000, 1950 to 3000, 2000 to 3000, 2050 to 3000, or 2100 to 3000. The toughness of the film can be determined by the maximum stress in a tensile test x the elongation at break.

[0061] The film of the present invention may be a single-layer film or a multi-layer film in which a plurality of the above-mentioned films are laminated, but is preferably a single-layer film from the viewpoints of mechanical strength and production efficiency.

[0062] In one embodiment of the present invention, the film thickness 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, 30 to 100 μm, 35 to 95 μm, 40 to 92 μm, 42 to 90 μm, 45 to 87 μm, or 47 to 84 μm. When the film thickness is within the above range, the film can have good water solubility, mechanical strength, and cold water solubility. The film thickness can be determined, for example, using a film thickness meter, and can be determined by the method described in the Examples below. When the film is a multilayer film, the above film thickness refers to the thickness of a single film.

[0063] The surface of the film of the present invention may be flat, or from the viewpoint of preventing adhesion between products, one or both sides of the 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] <Film Manufacturing Method> The method for manufacturing the film of the present invention is not particularly limited, and the film can be manufactured by a method known in the art. For example, the film can be manufactured by a method including the steps of: obtaining a coating solution by stirring a polysaccharide and a solvent, and optionally a plasticizer, additives, etc., 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 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 forming the film 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 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 film is a laminate, the temperature of the obtained composition (e.g., pellets) can be adjusted as needed, and the molten composition can be extruded through a T-die or the like onto a known substrate with releasability, followed by cooling to form the film. 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, the temperature of the obtained composition (e.g., pellets) can be adjusted as needed, followed by inflation molding and cooling to form the film. 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 film of the present invention. In the present invention, the 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, the minimum dimension refers to the smallest dimension among the length, width, and height. For example, in the case of a cup with a circular bottom, the minimum dimension 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 film of the present invention and a support, wherein the support is a fiber, a textile product, paper, a metal foil, or a film (hereinafter also referred to as a "support film"). In the present invention, the term "laminate" may refer to a laminate comprising the film of the present invention having a desired shape and a support, which are integrated together. The support is preferably paper or a film. The laminate of the present invention in such an embodiment has excellent mechanical strength because it comprises the film.

[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 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 film and one or more supports selected from the group consisting of paper, film (support film), and metal foil, and may have any layers (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. Film / paper or support film or metal foil, Gas barrier layer or water vapor barrier layer / film / paper or support film or metal foil, Water vapor barrier layer / gas barrier layer / film / paper or support film or metal foil, Gas barrier layer / water vapor barrier layer / film / paper or support film or metal foil, Protective layer / film / paper or support film or metal foil, Protective layer / gas barrier layer or water vapor barrier layer / film / paper or support film or metal foil, Protective layer / water vapor barrier layer / gas barrier layer / film / paper or support film or metal foil, Protective layer / gas barrier layer / water vapor barrier layer / film / paper or support film or metal foil, Protective layer / film / gas barrier layer or water vapor barrier layer / paper or support film or metal foil, Protective layer / film / gas barrier layer or water vapor barrier layer / paper or support film or metal foil, Protective layer / film / water vapor barrier layer / gas barrier layer / paper or support film or metal foil, Protective layer / 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 / 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 / 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 / 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 / film / paper or support film or metal foil / gas barrier layer / water vapor barrier layer, Protective layer / water vapor barrier layer / gas barrier layer / film / paper or support film or metal foil / water vapor barrier layer / gas barrier layer, Protective layer / water vapor barrier layer / gas barrier layer / film / paper or support film or metal foil / water vapor barrier layer / gas barrier layer, Protective layer / gas barrier layer / water vapor barrier layer / film / paper or support film or metal foil / gas barrier layer / water vapor barrier layer,protective layer / gas barrier layer / water vapor barrier layer / 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 / 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 / film / paper or support film or metal foil.

[0096] More specific examples of the layer structure include the following: Film / paper, LLDPE / film / paper, LLDPE / adhesive layer / film / paper, LDPE / film / paper, LDPE / adhesive layer / film / paper, HDPE / film / paper, HDPE / adhesive layer / film / paper, CPE (non-oriented polyethylene) / film / paper, CPE (non-oriented polyethylene) / adhesive layer / film / paper, Polyethylene formed from polyethylene emulsion / film / paper, Polyethylene formed from polyethylene emulsion / adhesive layer / film / paper, Uniaxially oriented polyethylene / film / paper, Uniaxially oriented polyethylene / adhesive layer / film / paper, Biaxially oriented polyethylene / film / paper, Biaxially oriented polyethylene / adhesive layer / film / paper, Polypropylene / film / paper, Polypropylene / adhesive layer / film / paper, Uniaxially oriented polypropylene / film / paper, Uniaxially oriented polypropylene / adhesive layer / film / paper, Biaxially oriented polypropylene / film / paper, Biaxially oriented polypropylene / adhesive layer / film / paper, PLA / film / paper, PLA / adhesive layer / film / paper, PHA / film / paper, PHA / adhesive layer / film / paper, PHBH / film / paper, PHBH / adhesive layer / film / paper, PCL / film / paper, PCL / adhesive layer / film / paper, PBAT / film / paper, PBAT / adhesive layer / film / paper, PBS / film / paper, PBS / adhesive layer / 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 (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 polysaccharides and plasticizers 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, and for 0.1 to 10 seconds. When laminating via a pressure-sensitive adhesive or adhesive, such pressure-sensitive adhesives or adhesives are 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 a film containing polysaccharide A having an ionic functional group and polysaccharide B whose main chain is composed exclusively of β-1,4-bonds. The packaging material of the present invention in this embodiment has excellent mechanical strength because it contains specific polysaccharide A and polysaccharide B. The film constituting the packaging material is preferably similar to the film described above in the [Film] section, and preferably has similar properties. Furthermore, the packaging material preferably has similar properties to the pouch described in the [Pouch] section 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 film of the present invention. Since the pouch of the present invention comprises the film, it has high mechanical strength and is preferably water-soluble.

[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. There is no particular lower limit to the dissolution time, and shorter dissolution times are preferable. 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 film constituting the pouch; the manufacturing conditions of the pouch (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 above-mentioned film. When the pouch comprises (or is composed of) a multilayer film, the multilayer film may be a laminate of a plurality of the above-mentioned films, or may be a laminate of the above-mentioned film and another film other than the above-mentioned 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 the above-mentioned monolayer or multilayer film, and further from the viewpoint of production efficiency, it is more preferable that the pouch be composed of the above-mentioned monolayer 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 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 films 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 a step of sealing the opening.

[0108] Methods for sealing a 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 (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 film has high adhesive strength due to moisture, and therefore water sealing can be suitably used. In another embodiment of the present invention, the 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 using a roll-to-roll process, effectively preventing damage during production. Furthermore, the high water sealing properties allow the produced film to be simply and easily formed into a pouch using moisture.

[0110] <Uses of Pouch> The pouch of the present invention has excellent mechanical strength. In one embodiment of the present invention, the pouch may contain at least one substance, preferably a food, inside thereof, preferably beverage powder such as energy drink powder, hydration drink powder, sports drink powder and concentrates thereof, protein powder, hot cocoa, concentrated tea, tea leaves, mocha, concentrated fruit drinks, coffee, chicory, etc.; instant foods such as flavor / texture improvers, 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 egg, egg white, and egg yolk; and additives such as cream, gelatin, fruit filling, and soy 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 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 or impregnated into a film. A fabric softener sheet is a sheet-shaped fabric softener in which softener ingredients are wrapped in or impregnated into a film. A laundry sheet or fabric softener sheet can contain one or more layers of the film of the present invention. A laundry sheet or fabric softener sheet can contain one or more layers of the film of the present invention and one or more layers of a known water-soluble 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 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, etc. 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 applying it to the face. 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] Film Preparation Example 1 0.4 g of pectin (Classic CF501, manufactured by MP Gokyo Food & Chemical Co., Ltd.) as polysaccharide A and 39.6 g of tamarind seed gum (weight-average molecular weight 261 kDa, number-average molecular weight 80 kDa; Greate (registered trademark), manufactured by MP Gokyo Food & Chemical Co., Ltd.) (hereinafter referred to as Tamarind Seed Gum I) as polysaccharide B were added to water and heated and stirred at 95°C for 2 hours to obtain an aqueous solution. 38.6 g of glycerin (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) and 21.4 g of fructose (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) were added as plasticizers to prepare a coating solution. The coating solution was applied to a polyethylene terephthalate film using a bar coater and 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.

[0118] Examples 2 to 4 Films were obtained in the same manner as in Example 1, except that the amounts of each component were changed to those shown in Table 1.

[0119] Examples 5 and 11 Films were obtained in the same manner as in Example 1, except that 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 as polysaccharide A and tamarind seed gum I was used as polysaccharide B, and the blending amounts of each component were changed to the amounts shown in Table 1.

[0120] Example 6 A film was obtained in the same manner as in Example 1, except that pectin and ι-carrageenan were used as polysaccharide A, and tamarind seed gum was used as polysaccharide B, and the blending amounts of each component were changed to the amounts shown in Table 1.

[0121] Example 7 A film was obtained in the same manner as in Example 1, except that κ-carrageenan (weight average molecular weight 827 kDa, number average molecular weight 48 kDa; GENUGEL carrageenan type JPE-126, manufactured by MP Gokyo Food & Chemical Co., Ltd.) was used as polysaccharide A, a 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.) (hereinafter referred to as tamarind seed gum II) different from the tamarind seed gum I used in Example 1 was used as polysaccharide B, and glycerin was used as a plasticizer, and the blending amounts of each component were changed to the amounts shown in Table 1.

[0122] Examples 8 and 9 Films were obtained in the same manner as in Example 7, except that the amounts of each component were changed to those shown in Table 1.

[0123] Example 10 A film was obtained in the same manner as in Example 7, except that ι-carrageenan was used as polysaccharide A and guar gum (weight average molecular weight 688 kDa, number average molecular weight 32 kDa; GENU CARRAGEENAN GENUTINE VCS-J, manufactured by Sansho Co., Ltd.) was used as polysaccharide B, and the blending amounts of each component were changed to the amounts shown in Table 1.

[0124] Example 12 A film was obtained in the same manner as in Example 7, except that gum arabic was used as polysaccharide A, tamarind seed gum I was used as polysaccharide B, and the blending amounts of each component were changed to the amounts shown in Table 1.

[0125] Example 13 A film was obtained in the same manner as in Example 7, except that gum arabic and ι-carrageenan were used as polysaccharide A, tamarind seed gum I was used as polysaccharide B, and glycerin and sorbitol were used as plasticizers, and the blending amounts of each component were changed to the amounts shown in Table 1.

[0126] Example 14 A film was obtained in the same manner as in Example 7, except that ι-carrageenan was used as polysaccharide A, tamarind seed gum I was used as polysaccharide B, and hydroxypropylated starch was used as a polysaccharide other than polysaccharide A and polysaccharide B, and the blending amounts of each component were changed to the amounts shown in Table 1.

[0127] Example 15 A film was obtained in the same manner as in Example 13, except that ι-carrageenan was used as polysaccharide A, tamarind seed gum I was used as polysaccharide B, and hydroxypropylated starch was used as a polysaccharide other than polysaccharide A and polysaccharide B, and the blending amounts of each component were changed to the amounts shown in Table 1.

[0128] Comparative Example 1: 40.0 g of tamarind seed gum I (polysaccharide B) was added to water and heated and stirred at 95°C for 2 hours to obtain an aqueous solution. 38.6 g of glycerin as a plasticizer and 21.4 g of fructose were added to the aqueous solution to prepare a coating solution. The coating solution was applied to a polyethylene terephthalate film using a bar coater, followed by hot air drying at 60°C for 1 hour. The resulting dried coating film was peeled off from the polyethylene terephthalate film substrate to obtain a film.

[0129] Comparative Example 2: 40.0 g of pectin as polysaccharide A was added to water, and the mixture was heated and stirred at 95°C for 2 hours to obtain an aqueous solution. 38.6 g of glycerin as a plasticizer and 21.4 g of fructose were added to the aqueous solution 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.

[0130] Comparative Example 3: 40.0 g of tamarind seed gum I (polysaccharide B) was added to water and heated and stirred at 95°C for 2 hours to obtain an aqueous solution. 60.0 g of glycerin was added thereto as a plasticizer to prepare a coating solution. The coating solution was applied to a polyethylene terephthalate film using a bar coater, followed by hot air drying at 60°C for 1 hour. The resulting dried coating film was peeled off from the polyethylene terephthalate film substrate to obtain a film.

[0131] Comparative Examples 4 and 5 Films were obtained in the same manner as in Comparative Example 3, except that tamarind seed gum II was used as polysaccharide B and the blending amounts of each component were changed to those shown in Table 1.

[0132] Comparative Example 6 A film was obtained in the same manner as in Comparative Example 2, except that ι-carrageenan was used as polysaccharide A and the blending amounts of each component were changed to those shown in Table 1.

[0133] Comparative Examples 7 and 8 Films were obtained in the same manner as in Comparative Example 2, except that κ-carrageenan was used as polysaccharide A and the blending amounts of each component were changed to those shown in Table 1.

[0134] Comparative Example 9 A film was obtained in the same manner as in Comparative Example 3, except that guar gum was used as polysaccharide B and the blending amounts of each component were changed to those shown in Table 1.

[0135] Comparative Example 10 A film was obtained in the same manner as in Comparative Example 6, except that gum arabic was used as polysaccharide A and the blending amounts of each component were changed to those shown in Table 1.

[0136] Comparative Example 11 21.0 g of pectin as polysaccharide A and hydroxypropylated starch as a polysaccharide other than polysaccharide A and polysaccharide B were added to water and heated and stirred at 95°C for 2 hours to obtain an aqueous solution. 30.0 g of sorbitol (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was added thereto as a plasticizer to prepare a coating liquid. The coating liquid was applied to a polyethylene terephthalate film using a bar coater, followed by hot air drying at 60°C for 1 hour, and the resulting dried coating film was peeled off from the polyethylene terephthalate film substrate to obtain a film.

[0137] Comparative Example 12 Hydroxypropylated starch was added to water as a polysaccharide other than polysaccharide A and polysaccharide B, and the mixture was heated and stirred at 95°C for 2 hours to obtain an aqueous solution. 30.0 g of sorbitol was added thereto as a plasticizer to prepare a coating solution. The coating solution was applied to a polyethylene terephthalate film using a bar coater, followed by hot air drying at 60°C for 1 hour, and the resulting dried coating film was peeled off from the polyethylene terephthalate film substrate to obtain a film.

[0138] Comparative Example 13 10.0 g of hydroxyethyl cellulose as polysaccharide B and 60.0 g of hydroxypropylated starch as a polysaccharide other than polysaccharide A and polysaccharide B were added to water and heated and stirred at 95°C for 2 hours to obtain an aqueous solution. 30.0 g of sorbitol was added thereto as a plasticizer to prepare a coating liquid. The coating liquid was applied to a polyethylene terephthalate film using a bar coater, followed by hot air drying at 60°C for 1 hour, and the resulting dried coating film was peeled off from the polyethylene terephthalate film substrate to obtain a film.

[0139] Comparative Example 14: 70.0 g of hydroxypropylated starch as a polysaccharide other than polysaccharide A and polysaccharide B was added to water and heated and stirred at 95°C for 2 hours to obtain an aqueous solution. 30.0 g of sorbitol was added thereto as a plasticizer to prepare a coating solution. The coating solution was applied to a polyethylene terephthalate film using a bar coater, followed by hot air drying at 60°C for 1 hour, and the resulting dried coating film was peeled off from the polyethylene terephthalate film substrate to obtain a film.

[0140] Comparative Example 15 A film was obtained in the same manner as in Comparative Example 3, except that tamarind seed gum I was used as polysaccharide B and the blending amounts of each component were changed to those shown in Table 1.

[0141]

[0142] Evaluation <Viscosity of Aqueous Solution> The aqueous solutions used for viscosity measurement were prepared as follows: Water was added to the polysaccharide and plasticizer ratios shown in Table 1 so that the solids concentration (calculated as polysaccharide and plasticizer as solids) was 29% by mass, and the solution was dissolved at 95°C. The viscosity was measured using a Brookfield viscometer (TVB-10, manufactured by Toki Sangyo Co., Ltd.) at 85°C, 0.5 to 100 rpm, and spindle Nos. M1 to M4 (the rotation speed and spindle were changed depending on the viscosity).

[0143] <Film Thickness> The film thickness of the films produced 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 thicknesses was taken as the film thickness.

[0144] <Toughness> The 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 with a width of 10 mm and a length of 120 mm were cut out. For each test piece prepared, the maximum stress and breaking elongation were measured using an autograph (apparatus name: AG-5000B, manufactured by Shimadzu Corporation) at a chuck distance of 70 mm and a pulling speed of 500 mm / min, and the average value was calculated. The value of the maximum stress x the breaking elongation was taken as the toughness of the film.

[0145] <Cold Water Solubility> The 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 (body diameter: φ90 mm) containing 500 ml of distilled water was placed in a separate thermostatic bath adjusted to 10°C, and the water was stirred at 400 rpm using a cylindrical rotor 5 cm long and φ8 mm in diameter. 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 × Time to completely dissolve the sample (seconds)

[0146] The evaluation results are shown in Table 2.

[0147] As shown in Table 2, the films of the Examples were confirmed to have excellent mechanical strength. On the other hand, the Comparative Examples, which contained only Polysaccharide A or Polysaccharide B, or neither, had low mechanical strength.

[0148] Pouch Fabrication Example 16 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.

[0149] Examples 17 to 20 Pouches were obtained in the same manner as in Example 16, except that the films obtained in Examples 5, 6, 12, and 15 were used.

[0150] 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 rated as A, and when the film was damaged, it was rated as B.

[0151] <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.

[0152] <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 state of dissolution of the film was visually observed to confirm whether the film was completely dissolved. Cases without residue were designated A, and cases with residue were designated B.

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

[0154] Evaluation of Molded Articles Example 21 0.5 g of pectin (Classic CF501, MP Gokyo Food & Chemical Co., Ltd.) as polysaccharide A, 2 g of tamarind seed gum I as polysaccharide B, and 7.5 g of fructose as a plasticizer were added to water, and the resulting mixture was added to purified water to a total concentration of 20% by mass. The mixture was then heated and stirred at 90°C for 1 hour to dissolve the mixture. The resulting solution (coating solution) was cooled to 25°C. The resulting coating solution 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 (hereinafter, sometimes simply referred to as "coating solution thickness"), 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 22 The blending amounts of each component were as shown in Table 4, and these were added to pure water so that the total concentration was 25% by mass. The resulting coating solution was applied to 80 g of bleached kraft B-F paper as a support using a bar coater so that the thickness of the coating solution after application was 7.8 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, yielding a laminate consisting of a coating film integrated with the support.

[0156] Example 23 A laminate was obtained in the same manner as in Example A, except that ι-carrageenan was used as polysaccharide A and the blending amounts of each component were set to the values ​​shown in Table 4.

[0157] Example 24: ι-Carrageenan as polysaccharide A, tamarind seed gum I as polysaccharide B, hydroxypropylated starch as other polysaccharide, and sorbitol as plasticizer were added to water in the amounts shown in Table 4. These components were then added to purified water to a total concentration of 27% by mass, and dissolved by heating and stirring at 90°C for 1 hour. The solution (coating solution) was cooled to 25°C. The resulting coating solution was applied to 80 g of bleached kraft B-F paper as a support using a bar coater, resulting in a coating thickness of 27.5 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, yielding a laminate consisting of a coating film integrated with the support.

[0158] [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.

[0159] [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 value of 10. The higher this value, the better the mechanical strength of the coating layer and the less likely it is to crack when bent.

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

Claims

1. A film comprising polysaccharide A and polysaccharide B, wherein said polysaccharide A has an ionic functional group, and said polysaccharide B has a main chain composed only of β-1,4-bonds.

2. The film according to claim 1, wherein the polysaccharide A is at least one selected from the group consisting of pectin, carrageenan, gum arabic, alginic acid, agar, and derivatives thereof.

3. The film according to claim 1, wherein the content of said polysaccharide A is 0.1 to 50% by mass relative to the mass of said film.

4. The film according to claim 1, wherein the polysaccharide B is at least one selected from the group consisting of tamarind seed gum, cellulose, guar gum, tara gum, locust bean gum, and derivatives thereof.

5. The film according to claim 1, wherein the content of said polysaccharide B is 5 to 80% by mass relative to the mass of said film.

6. The film according to claim 1, wherein the total content of the polysaccharide A and the polysaccharide B is 20 to 90% by mass based on the mass of the film.

7. The film of claim 1 further comprising a plasticizer.

8. The film of claim 7, wherein the plasticizer is at least one selected from the group consisting of polyhydric alcohols, hydroxy acids, monosaccharides, and disaccharides.

9. The film according to claim 7, wherein the content of the plasticizer is 20 to 95% by weight based on the weight of the film.

10. The film according to claim 1, wherein the content of polyvinyl alcohol resin is less than 30% by weight based on the weight of the film.

11. The film of claim 1, having a toughness of 1500 or greater.

12. The film of claim 1, which is water-soluble.

13. A packaging material comprising the film of claim 1.

14. A pouch comprising the film of claim 1.

15. The pouch of claim 14, containing therein at least one selected from the group consisting of cleaning agents, fabric softeners, and fragrances.

16. A molded article comprising the film of claim 1.

17. A laminate comprising the film of claim 1.

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