WO2004041926A1 - Water-soluble film - Google Patents

Abstract

A water-soluble film with which satisfactory heat sealing can be conducted to give a heat-sealed part which can satisfactorily retain the heat-sealed state even in a dry atmosphere; and a food, cosmetic, medicine, or chemical-product package made with the water-soluble film. The water-soluble film comprises one or more water-soluble polysaccharides containing no sulfate group, one or more water-soluble polysaccharides containing sulfate groups, and one or more hydroxy compounds as a material for humidification and contains substantially no crosslinking agent. When heat-sealed, the film gives a heat-sealed part which undergoes substantially no separation under moisture equilibrium conditions with a relative humidity of 25% or lower.

Description

 Description Water-soluble film Technical field

 The present invention relates to a water-soluble film, and more particularly, to a water-soluble film having excellent heat sealability in a dry environment. Background art

 Films made mainly from water-soluble polysaccharides such as pullulan are edible and water-soluble, so that the packaged contents can be packaged by simply inserting them into an aqueous solvent without opening the package. Can be released outside. Among the water-soluble polysaccharides, films made from pullulan as the main raw material have extremely excellent oxygen impermeability, so if they can be packaged in a well-sealed package, It is also possible to prevent oxidation deterioration of the product.

 Heat sealing is an extremely useful technique when packaging goods using a film because it can easily perform sealing with excellent sealing properties and strength, and uses water-soluble polysaccharides as the main raw material. Its use has been demanded for films. Films based on water-soluble polysaccharides such as pullulan were considered to be films that were relatively easy to heat seal at the time of development, and even if heat seal was applied to the film, Various inconveniences such as over-melting, bubbles and pinholes, and peeling or cracking of the heat seal during use and storage, or during transportation, are sufficient for commercial use. Heat-sealing technology that is extremely stable has not yet been completed for films using water-soluble polysaccharides as the main raw material.

The same application was filed as a method for improving the heat sealability of a film made of pullulan as the main material. In Japanese Patent Application Laid-Open No. 53-799972, water is applied to the heat-sealed portion of a film mainly made of pullulan, and the temperature of the heat-sealed portion is raised to a temperature higher than the evaporation temperature of water. There has been proposed a method of heat sealing without performing the heat sealing. Although this method enables good heat sealing, it is necessary to apply water to the area to be sealed, so it is suitable for stable, continuous and large-scale heat sealing. Not. Also, Japanese Patent Application Laid-Open No. 5-309910 discloses a film mainly composed of heat-sealable pullulan, but the film is a water-resistant film combined with a crosslinking agent.

 The water content of a film mainly composed of a water-soluble polysaccharide such as pullulan varies depending on the relative humidity of the environment in which the film is used and stored. In a dry environment, the film dries and heat sealing becomes difficult, and the heat sealed part may peel off or crack. The techniques described in the above prior art documents do not solve this problem. Disclosure of the invention

 The present invention provides a water-soluble film capable of maintaining a good heat-sealed state even when used and stored in a dry environment, and a package of food, cosmetics, pharmaceuticals or chemicals using the same. That is the task.

As a result of repeated studies to solve the above problems, the present inventors have found that, in order to realize a water-soluble film having good heat sealing properties using a water-soluble polysaccharide such as pullulan, Under the environment where the sealing is performed, the moisture content of the film is in the range of 11 to 14%, and the film has good flexibility even in a dry environment where the moisture content of the film is reduced. It was concluded that it was necessary to maintain the heat seal, and ③ it was necessary for the film surface to have the property of not being too sticky even in a high humidity environment. After repeated trials and errors in order to realize a water-soluble film, the humidity control of the film The addition of ingredients makes it possible to increase the water content, and the addition of an appropriate amount of a water-soluble polysaccharide having a sulfate group provides sufficient flexibility and good heat sealing even in a dry environment. Is maintained, and the required amount of the humidity control material can be reduced.Moreover, even if the film contains a large amount of the humidity control material, as a water-soluble polysaccharide having no sulfate group, pullulan, It was discovered that blending locust bean gum and xanthan gum together with an appropriate amount of a fatty acid ester such as glycerin fatty acid ester could improve the strength of the film and the heat seal strength. A water-soluble film having excellent heat sealing properties and a method for producing the same have been established, and the present invention has been completed.

 According to the water-soluble film of the present invention as described above, excellent heat-sealing properties can be obtained despite the fact that a cross-linking agent, which is conventionally considered necessary for obtaining a film having excellent heat-sealing properties, is not used. Since it can be realized and the crosslinked structure is not formed, a film having excellent water solubility can be realized.

That is, the present invention solves the above problem by blending a water-soluble polysaccharide having no sulfate group, a water-soluble polysaccharide having a sulfate group, and a humidity control material in a water-soluble film based on a water-soluble polysaccharide. such Li, blended fatty acid esters if necessary, the best mode for carrying out the Oh ₀ invention solves by providing a water-soluble film that does not contain substantive crosslinking agent

 The water-soluble film of the present invention contains one or more water-soluble polysaccharides having no sulfate group, one or more water-soluble polysaccharides having a sulfate group, and one or more hydroxy compounds as a humidity control material. Thus, when heat-sealed, the heat-sealed portion does not substantially peel off under an environment of a relative humidity of 25%, and is a water-soluble film substantially containing no crosslinking agent.

All of the water-soluble polysaccharides having no sulfate group used in the present invention are edible Sex polysaccharides such as pullulan, ercinan, sodium alginate, agar, pectin, tamarind gum, xanthan gum, guar gum, tara gum, locust bin gum, arabinogalactan, gum arabic, chitosan, amylose, amylose Kuching, dextran and the like. Among them, a polysaccharide having maltotriose as a repeating unit, that is, pullulan or ercinan is preferable, and particularly, pullulan, which is easily available, is more preferably used in the present invention. It is also preferable to use one or more of water-soluble polysaccharides having no sulfate group other than pullulan in combination with pullulan. In particular, it is desirable to use locust bean gum and xanthan gum in combination.

As the pullulan used in the present invention, pullulan produced by culturing yeast such as Aureobasidium in a medium containing a starch degradation product is generally advantageous in terms of availability and price. Therefore, it is advantageously used in the present invention. For example, pullulan (trade name "PI20" or "PF20", etc.) sold by Hayashibara Shoji Co., Ltd. can be preferably used. However, the present invention is not limited thereto, and other pullulan products can be used, and other polysaccharides having maltotriose as a repeating unit, for example, ercinan, can be used without departing from the purpose of the present invention. Further, if necessary, a polysaccharide having maltotriose as a repeating unit which is derivatized by performing modification such as esterification of an arbitrary degree of substitution can be used. The weight average molecular weight of the polysaccharide having maltotriose as a repeating unit used in the present invention is usually 5,000 daltons or more, preferably 10,000 to 1,000,000 daltons, and more preferably 50,000 daltons. From 500 to 500,000 daltons. The weight average molecular weight and molecular weight distribution of the polysaccharide having maltotriose as a repeating unit are factors that determine the dissolution rate of the film. A polysaccharide having trioise as a repeating unit may be used. Generally, depending on the other components to be blended, it is difficult to form a film if the weight average molecular weight of the polysaccharide having maltotriose as a repeating unit is less than 10,000 daltons, and 1,000,000 daltons. If it exceeds, the dissolution rate in aqueous solvent will decrease It is not preferable because it is too much.

 As the water-soluble polysaccharide having a sulfate group used in the present invention, any water-soluble polysaccharide having a sulfate group can be used without particular limitation. In order to exert its effect sufficiently in the water-soluble film of the present invention, those having 0.5 or more sulfate groups, more preferably those having one or more sulfate groups per constituent monosaccharide are preferable. Natural polysaccharides such as carrageenan, chondroitin sulfate, heparan sulfate, deltaman sulfate and heparin, which are edible polysaccharides, or salts thereof, or water-soluble polysaccharides originally having no sulfate group, or sulfate groups Water-soluble polysaccharides having a number of sulfate groups of less than 0.5 per constituent monosaccharide, even if they have the same, are sulfated by an appropriate method, for example, by utilizing an enzyme reaction or a chemical reaction. Can be used. In the present invention, carrageenan is preferably used because it is easily available and excellent in imparting physical properties such as film strength and flexibility. A water-soluble polysaccharide having a sulfate group can enhance the moisture retention, flexibility, film strength, and strength of the heat-sealed portion of the film in a dry environment, and particularly, the heat-sealed portion, which tends to become brittle. And the strength of the boundary portion of the portion that is not heat-sealed. It also has the effect of reducing the adhesiveness of the film surface due to the large amount of the humidity control material.

Carrageenan is a water-soluble polysaccharide that has a unit structure of a disaccharide composed of D-galax I and 3,6-anhydro D-galactose contained in a red algae extract. Number of groups-Five types, K (kappa) type, L (iota) type, λ (lambda) type, (mu) type, and Ζ / (new) type, are known depending on the position (see Table 1). ). As the carrageenan used in the present invention, commercially available carrageenan products can be used irrespective of type, origin and production method. In particular, the carrageenan monosaccharide having 0.5 sulfate groups / 、, and the carrageenan I and carrageenan having one sulfate group per constituent monosaccharide are available and can be advantageously used in the present invention. it can. Type carrageenan is excellent in improving the strength of the film, while i-type carrageenan is Excellent for improving sex. Therefore, in the film of the present invention, it is preferable to contain various types of carrageenans in combination.

table 1

 Gal: D-Garaku I ^ One

 ADGal: 3,6-anhydro-D-galactose

Examples of the humidity control material used in the present invention include various hydroxy compounds, particularly volatile hydroxy compounds, such as erythryl Ixyl, xylitol, sorbitol, maltitol,, 1 trehalose, glycosyl, 1 trehalose, Examples include cyclic oligosaccharides, glycosyl cyclic oligosaccharides, polyols such as glycerin, and derivatives thereof, and these can be used alone or in combination of two or more. Of these, glycerin is preferably contained, and in addition to these, sorbitol or, -trehalose is preferably contained.

 When the mixing ratio of the humidity control material is relatively high, fats such as lecithin and palm oil, sugar fatty acid esters such as sucrose spearic acid ester, and fatty acid esters such as glycerin fatty acid ester and propylene glycol fatty acid ester are used. Incorporation of these compounds can reduce the tackiness of the film surface. Of these, glycerin fatty acid esters and sugar fatty acid esters are preferably contained.

The ratio of each component in the water-soluble film of the present invention is such that the water-soluble polysaccharide having a sulfate group is 15 to 150 It is blended within the range of mass%. Further, the hydroxy compound is blended within a range of 1 to 50% by mass based on the total amount of the water-soluble polysaccharide. However, when the mixing ratio of the hydroxy compound to the total amount of the water-soluble polysaccharide exceeds 20% by mass, the film strength is reduced and the adhesiveness of the film surface becomes remarkable. It is desirable to use pullulan, locust bean gum and xanthan gum as water-soluble polysaccharides that do not have it, and the total amount of locust bean gum and xanthan gum should be in the range of 0.5 to 40% by mass with respect to pullulan. preferable. Further, when the mixing ratio of the hydroxy compound to the total amount of the water-soluble polysaccharide exceeds 20% by mass, the ratio of the water-soluble polysaccharide having a sulfate group to the water-soluble polysaccharide having no sulfate group is increased to 50 to 150%. % By mass, preferably 60 to 120% by mass. / ₀ , and blending the lipids or fatty acid esters within the range of 1 to 10% by mass with respect to the total amount of the water-soluble polysaccharide and the hydroxy compound to obtain the film strength and the film strength. The adhesiveness of the film surface can be reduced. The water-soluble film of the present invention may appropriately contain other components in addition to the above components, as long as the object of the present invention is not hindered. Examples of the substance that can be contained include proteins such as soybean protein and gelatin and their degradation products, volatile alcohols such as ethanol, pigments, flavors, and derivatives thereof.

 The method for producing the film of the present invention is as follows: an aqueous solvent such as water or ethanol is used to prepare an appropriate viscous solution, which is then cast, cast, sprayed, sprayed, roll-coated, and dipped in a conventional manner. After forming a thin film by a method such as a method, the film is dried at room temperature or at a temperature exceeding room temperature to form a film.

The film thus obtained usually has the purpose of being immersed in an aqueous solvent and dissolved after packaging. Therefore, the film needs to be water-soluble. The dissolution rate in an aqueous medium depends on the type, amount and temperature of the solvent, stirring intensity, In consideration of the water content of the film, the shape of the film such as thickness and size, the weight-average molecular weight of the water-soluble polysaccharide, the molecular weight distribution of the water-soluble polysaccharide, the ratio of various water-soluble polysaccharides, and various hydroxy compounds The mixing can be carried out by appropriately selecting the mixing ratio. In the film of the present invention, although it depends on the application, when the film is put into hot water at 80 ° C, the content sealed and packaged in the film is usually released within 5 minutes, more preferably within 3 minutes. It is desirable to provide such a water solubility. Since the film of the present invention is desired to have higher water solubility, it should not contain a crosslinking agent which forms a water-insoluble crosslinked structure which causes a decrease in the water solubility of the film. Depending on the water-soluble polysaccharides to be contained, it is desirable to exclude substances having a function of forming a water-insoluble crosslinked structure, such as minerals such as calcium, from each of the components.

 The thickness of the water-soluble film of the present invention may be determined according to the intended use, and is usually selected from the range of 1〃m to 100〃m, preferably from 10〃m to 50im. If the thickness is less than 1 m, the film is easily broken, and if it is more than 100 m, the dissolution time in a solvent such as water becomes too long, or the amount of the film component eluted in the solvent becomes too long. It may be too much and may not be desirable.

 The water-soluble film of the present invention has an equilibrium water content of about 1% in a dry environment where the film is used and stored, specifically, in an environment having a relative humidity of about 25%, preferably about 10%. By adjusting the proportions of the components so that the ratio can be maintained at 0 to about 15%, preferably about 11 to about 14%, properties such as heat sealability, film strength, and flexibility can be obtained. It becomes.

The heat sealing in the present invention means that two or more overlapping films or two or more partially overlapping film portions are bonded by thermocompression bonding. It is common to form a bag by laminating films or bending a single film and heat-sealing the periphery. Such a shape is, for example, that the content is powdery, granular, or greasy base. It is advantageously applied in the case of a single-stroke or oily liquid. Usually, heat sealing is performed on a part of the film, but if the content is a heat-resistant sheet, heat sealing may be applied to the entire surface of the film including the content. It is possible. When a plurality of pieces are connected and heat-sealed and packaged, they can be cut and separated after packaging, or perforated to facilitate separation. In the case of a relatively large solid, after wrapping an object to be packaged with one or a plurality of films, the film in the overlapping portion can be bonded by heat sealing to form a package. If necessary, packing may be performed in an inert gas or vacuum to prevent gas that deteriorates the quality of the packaged object such as oxygen or water vapor from being enclosed inside the package. Packaging is optional.

 As the heat sealing device, it is possible to use a heat press device, for example, a heat bar type, a mouth type, a pillow type, an impulse packaging machine, a high frequency packaging machine and the like. In order to perform better heat sealing, a model that can control the temperature of the heat sealing section is desirable. For example, as a commercially available heat sealing device, a product name of “Fuji Impulse Sealer OPL” sold by Fuji Impulse Co., Ltd. — 200—10 ”can be used. When using such a heat-sealable device capable of controlling the temperature, the temperature of the portion to be sealed is usually 100 to 200 ° C, preferably 110 to 160 ° C, preferably 120 to 140 ° C. If the heat sealing time is set within the range of 1 to 4 seconds, the heat sealing will hardly fail.

The package made of the film of the present invention must be sufficiently sealed so that the contents do not substantially fall out of the package from the package during storage, and the pressure is assumed to be applied to the film. It is desirable to have sufficient strength to withstand tension, shear force, vibration and the like. The strength of the film and the strength of the heat-sealed part are based on Japanese Industrial Standard JISZ1707, for example, using a rheometer (manufactured by Rheotech Co., Ltd., trade name "RT-201 OJ-CW"). Can be measured. Use Depending on the relative humidity of the storage environment, the film usually has a strength of at least 100 gf, preferably at least 150 gf, and a heat seal strength of at least 150 gf Z 15 mm width, preferably. Should have a width of at least 250 gf 15 mm.

The film of the present invention is used for packaging foods, cosmetics, pharmaceuticals, and chemicals in the form of solids, powders, granules, tablets, creams, emulsions, masks, pastes, oily liquids, etc. By doing so, it is possible to prevent oxidation of the contents due to the oxygen in the air, and to eat, pour directly into an appropriate solvent, or pour the solvent into the package in the packaged state. Even so, the packaging can dissolve and release the contents into the solvent. In addition, if a water-resistant substance such as oil or fat is coated on the side of the film that comes into contact with the contents, a water-rich liquid or an aqueous liquid can be used as the contents. The film of the present invention does not necessarily require the package to be opened, so that it is not necessary to open the package, and since there is no danger of the object to be packaged being scattered at the time of opening, the user can prevent contamination of hands, fingers, clothes, etc. , Can be used without paying attention to respiratory suction. Therefore, if it is applied to the packaging of high-risk substances such as poisons, powerful drugs, and carcinogens as well as food, cosmetics and pharmaceuticals, the handling of those substances can be made safe and easy. As another usage of the water-soluble film of the present invention, the water-soluble film may be used in a partially open state, for example, in a bag shape or a cylindrical shape. It is also possible to adopt a method other than heat sealing, for example, a method of bonding using an adhesive such as starch or protein, a method of stacking or folding a film, and then fixing it with a fastener. it can. If desired, multiple packaging may be performed with one or two or more films of the present invention, or multiple packaging may be performed in combination with another packaging material. Further, although the heat sealing property is inferior, it is also possible to heat seal another film with the film of the present invention to form a laminated film. Further, when producing the film of the present invention, the raw material of the film of the present invention is cast on another film, for example, polyethylene, nylon, paper, or the like, applied, crushed, and then dried to obtain a film. If you make Film can be manufactured, and heat sealing properties can be imparted to films that could not be heat sealed. In particular, when applied to a film-like material having a network structure, for example, cloth, gauze, filter paper, non-woven fabric, and a net, the gap can be filled, so that a package made of these can be provided with airtightness. It can be applied advantageously to take-out bags for tea and soup stock.

Articles in the food field that can be packaged with the film of the present invention include, for example, agricultural products such as fresh fruits, vegetables, root vegetables, seeds, bulbs, juices, dried fruits, vegetable extracts, vegetable powders, pickles, and other processed fruits and vegetables. , Sesame paste, nut paste, seed paste such as corn paste, raw bean paste, bean paste, etc., potato flour such as sweet potato flour, yam flour, sesame, brown rice, wheat, barley, rye, soybean, corn, peanut, a Seeds such as mond, coffee beans, cocoa beans or crushed products thereof, polished rice (white rice), germ rice, unwashed rice, polished grains such as polished barley, polished barley, polished millet, rice flour, flour flour, barley flour; Agricultural products such as rye flour, pigeon flour, soy flour, soy germ flour, buckwheat flour, corn flour, etc., powdered cereals, ground sesame seeds, ground flour, kinako, rough ground coffee, etc. Products, sardine paste, oyster meat extract, squid paste, fish mackerel, fish meat, cut rikkobushi, kelp, fish meal and other fishery products, livestock products such as meat, milk, milk cream, chicken, eggs, soy sauce, miso, sauce, Seasonings such as paste or liquid seasonings such as mayonnaise and dressing, powdered oils and fats, spices, seasonings such as powdered seasonings such as flour, Japanese confectionery such as fertilizer, oysters, spring beans, fried beans, karinto, fried rice crackers, and castella. Chocolate, chewing gum, bread, cake, confectionery, cream confectionery, snack confectionery and other sweets, ice cream, sherbet and other frozen desserts, green tea, houjicha, black tea, oolong tea, brown rice tea, barley tea, pigeon barley tea and other teas, rice cooked rice, Steamed rice, rice flour, rice cakes, rice balls, rice porridge, rice, fried rice, pilaf and other rice products, pasta, bread, pizza, na Processed wheat products such as rice, bread crumbs, premixes, soymilk, tofu, atsuage, okara, okara hamburger, soybean processed products such as soymilk pudding, koji, amazake, sake, mirin, beer, distilled spirits, vinegar , Miso, soy sauce, bran mash, koji-zuke, kasu-zuke, miso mash, tamari mash, etc. Fermented foods and drinks, processed meat products such as ham and sausage, fish meat products such as kamaboko, chikuwa, and hampon, salted meat using squid, squid, dried fish, small fish, shrimp, squid, shellfish, meat Delicacies using tsukudani, boiled beans, salads, stir-fried foods, fried foods, boiled foods, fried eggs, grilled meat, yakitori, hamburgers, gyoza, tempura, tempura, etc., condensed milk, milk powder, yogurt, cheese, coffee fresh Dairy products such as bavarois, mousse, marshmallow, pudding, cream puff, broiled egg, broiled egg, chawanmushi, egg processed products such as mayonnaise, tea drinks made from various teas, amazake, coffee drinks, milk drinks Powders of soft drinks such as lactic acid bacteria drinks, liquid fats such as salad oil, olive oil, camellia oil, solid fats such as butter and margarine, sake, wine, recycle, etc. Alcohol beverage powders, frozen foods, baby foods, therapeutic foods, health foods, peptide foods, etc. Further, for example, cereal pellets, cereal powder, vegetable oil cake, fermented cake, rice bran, wheat bran, barley bran, defatted bran , Defatted soybeans, fishmeal, fish fusible, meat meal, blood meal, feather meal, skim milk powder, dried whey, pupal meal, alpha meal, etc. or feeds containing these, such as mixed feed, sowed bait, and bait bait. And seedlings.

 Articles in the cosmetics field that can be packaged with the film of the present invention include, for example, toothpaste, lipstick, lip balm, mouth balm, gargle, bath agent, antiperspirant, soap, shampoo, rinse, body soap , Body lotions, deodorants, hair creams, fair-skins, skin-care agents, hair-care agents, hair-growth agents and the like.

 Articles in the pharmaceutical field that can be packaged with the film of the present invention include, for example, drugs, organs, and artificial oils such as drinks, oral nutrients, tube feeds, fat emulsion for injections, troches, and liver oil drops. Organs and the like.

Articles in the chemical field that can be packaged with the film of the present invention include, for example, pesticides such as insect repellents, rodents, herbicides, photographic agents such as developers, softeners, bleaching agents, detergents and the like. Laundry agents, medical, chemical or biological research reagents in general, as well as specimens of living organisms, rocks, soil, etc. Substances that are harmful to the human body, such as poisons, deleterious substances, carcinogens, and radioactive substances.

 Hereinafter, the water-soluble film of the present invention will be described in detail by experiments. Experiment 1: Comparison of various films

<Sample 1>

 12 parts by weight of pullulan (Hayashibara Shoji Co., Ltd., trade name "PI20"), Carrageenan consisting only of K type (Sansei Co., Ltd., trade name "GENUGEL WG-115") 3 parts by mass 1 part by mass of sorbitol, sucrose stearic acid ester (Mitsubishi Chemical Foods Co., Ltd., trade name "Sugar Ester S1670") 0.01 parts by mass, 2 parts by mass of glycerin, and 1 part by mass of ethanol to 100 parts by mass of deionized water After dissolving, use an applicator (Yoshimitsu Seiki Co., Ltd., trade name “Baker Applicator YBA type”), apply an appropriate amount of drops onto a glass plate with polyethylene terephthalate adhered to it, and spread. After heating and drying at 10 ° C for 10 minutes, the film was allowed to stand at 25 ° C and a relative humidity of 55% for 16 hours to produce a film, and as a result, a film sample 1 having a thickness of 30% and an equilibrium water content of about 13% was obtained.

<Sample 2>

Pullulan (Hayashibara Shoji Co., Ltd., trade name "120") 12 parts by mass,: Carrageenan containing 1 _: 7 _: 3 ratio (Sansei Co., Ltd. trade name, "GENUVISCO CSW I-2") 3 1 part by weight of Sorbi! 1 part by weight, sucrose stearic acid ester (Mitsubishi Chemical Foods Co., Ltd., trade name "Sugar Ester S1670") 0.01 parts by weight, 2 parts by weight of glycerin, and 1 part by weight of ethanol Was dissolved in 100 parts by mass of deionized water, and a film was produced in the same manner as in Sample 1. As a result, a film sample 2 having a thickness of 30 μm and an equilibrium water content of about 13% was obtained.

<Sample 3>

Pullulan (Hayashibara Shoji Co., Ltd., trade name "PI20") 12 parts by mass, only ί type 3 parts by weight of carrageenan (Sansei Co., Ltd., trade name “GENUVISCO PJ”), 1 part by weight of sorbitol, sucrose spearic acid ester (Mitsubishi Chemical Foods Co., Ltd., trade name “Sugar ester”) S1670 ”) 0.01 parts by mass, 2 parts by mass of glycerin, and 1 part by mass of ethanol were dissolved in 100 parts by mass of deionized water, and a film was produced in the same manner as in Sample 1. As a result, a film sample 3 having a thickness of 30 m and an equilibrium water content of about 13% was obtained.

<Sample 4>

 Pullulan (marketed by Hayashibara Corporation, trade name "PI20") 12 parts by mass, carrageenan consisting only of mold (sold by Sansei Corporation, trade name "GENUGEL WG-115"),: S = 7: Carrageenan (sales from Sansei Co., Ltd., trade name "GENUVISCO CSW-2") and Carrageenan consisting of L-type only (sales from Sansei Co., Ltd., trade name "GE NUVISCO PJ") 1 part by weight of sorbitol, 1 part by weight of sorbitol, sucrose stearic acid ester (Mitsubishi Chemical Foods Co., Ltd., trade name “Sugar Ester S1670”) 0.01 part by weight, 2 parts by weight of glycerin, and 1 part by weight of ethanol A part by mass was dissolved in 100 parts by mass of deionized water, and a film was produced in the same manner as in Sample 1. As a result, a film sample 4 having a thickness of 30 m and an equilibrium water content of about 13% was obtained.

<Sample 5>

 Pullulan (Hayashibara Shoji Co., Ltd., trade name “PI20”) 12 parts by mass, carrageenan consisting of K type only (Sansei Co., Ltd., trade name “GENUGEL WG-115”) and carragee consisting of type only 2 parts by weight of Ichinan (Sansei Co., Ltd., trade name "GENUVISCO PJ"), 1 part by weight of sorbitol, sucrose stearic acid ester (Mitsubishi Kagaku Foods Co., Ltd., trade name "Sugar Ester S1670") 0.01 parts by mass, 2 parts by mass of glycerin, and 1 part by mass of ethanol were dissolved in 100 parts by mass of deionized water, and a film was produced in the same manner as in Sample 1. As a result, a film having an equilibrium water content of about 13% was obtained. Film sample 5 having a length of 30 m was obtained.

<Sample 6> 6 parts by mass of amylose (sold by Sigma, product name “Type Three”), 6 parts by mass of agar (sold by Matsuki Agar Sangyo Co., Ltd.) Carrageenan consisting of K type only (Sansei Co., Ltd., product name: “GENUGEL WG”) —115 ”), and carrageenan consisting of only i-type (sold by Sansei Co., Ltd., trade name:“ GENUVISCO PJ ”), 2 parts by weight, 1 part by weight of sorbitol, and sucrose stearate (Mitsubishi Chemical Foods, Inc.) Co., Ltd., trade name “Sugar Ester S1670”) 0.011 parts by mass, 2 parts by mass of glycerin, and 1 part by mass of ethanol were dissolved in 100 parts by mass of deionized water, and a film was produced in the same manner as in Sample 1. . As a result, a film sample 6 having a thickness of 30 jU m and an equilibrium water content of about 13% was obtained.

<Sample F>

 6 parts by mass of amylose (sold by Sigma, product name "Type Three"), 6 parts by mass of agar (sold by Matsuki Agar Sangyo Co., Ltd.), 3 parts by mass of sodium chondroitin sulfate (sold by Maruha Corporation), 1 part by mass of sorbitol, Dissolve 0.01 parts by mass, 2 parts by mass of glycerin, and 1 part by mass of ethanol in 100 parts by mass of deionized water, and Shosperic acid ester (Mitsubishi Chemical Foods Co., Ltd., trade name: Sugar Ester S1670) A film was produced in the same manner as in Sample 1. As a result, film material 7 with a thickness of 30 m and an equilibrium water content of about 13% was obtained.

<Sample 8>

 Pullulan (Hayashibara Shoji Co., Ltd., trade name "PI20") 10 parts by mass, sodium alginate (Kimitsu Chemical Industry Co., Ltd. sales, trade name "Kimitsu Algin ULV-20" 2 parts by mass, sodium chondroitin sulfate ( 3 parts by weight) 1 part by weight of sorbitol, 1 part by weight of sucrose stearic acid ester (Mitsubishi Chemical Foods Co., Ltd., trade name "Sugar Estel S1670") 0.01 parts by weight, 2 parts by weight of glycerin, and 1 part by weight of ethanol A portion was dissolved in 100 parts by mass of deionized water, and a film was produced in the same manner as in Sample 1. As a result, a film sample 8 having a thickness of 30 jW m and an equilibrium water content of about 13% was obtained.

<Sample 9>

Pullulan (Hayashibara Shoji Co., Ltd., trade name "PI20") 15 parts by mass, sucrose stearin Acid ester (Mitsubishi Chemical Foods Co., Ltd., product name "Sugar Ester S1670") 0.01 parts by mass and 1 part by mass of ethanol are dissolved in 100 parts by mass of deionized water, and a film is produced in the same manner as in Sample 1. did. As a result, a film sample 9 having a thickness of 30 m and an equilibrium water content of about 90/0 was obtained.

 <Sample 10>

Pullulan (Hayashibara Shoji Co., Ltd., trade name "PI20") 15 parts by mass, sucrose stearate (Mitsubishi Chemical Foods Co., Ltd., trade name "Sugar Ester S1670") 0.01 parts by mass, glycerin 5 parts by mass , as well as;! 1 part by mass of ethanol was dissolved in 100 parts by mass of deionized water, and a film was produced in the same manner as in Sample 1. As a result, to obtain a film sample 10 having a thickness of 30JU m of equilibrium water content of about 14 ⁰ / o.

<Sample 11>

 Pullulan (marketed by Hayashibara Shoji Co., Ltd., trade name: PI20) 12 parts by mass, carrageenan consisting only of molds (sales by Sansei Co., Ltd., trade name: “GENU GEL WG-115”), 3 parts by mass , Sucrose spearic acid ester (Mitsubishi Chemical Foods Co., Ltd., trade name “Sugar Ester S1670”) 0.01 parts by mass and 1 part by mass of ethanol were dissolved in 100 parts by mass of deionized water. A film was produced in a similar manner. As a result, a film sample 11 having a thickness of 30 m and an equilibrium water content of about 10% was obtained.

<Sample 12>

 Pullulan (Hayashibara Shoji Co., Ltd., trade name: PI20) 12 parts by mass, carrageenan containing 7: 3 ratio (Sansei Co., Ltd., trade name: GENUVISCO CSW-12) In 3 parts by mass, 0.01 parts by mass of sucrose spearic acid ester (Mitsubishi Chemical Foods Co., Ltd., trade name "Sugar Ester S1670") and 1 part by mass of ethanol are dissolved in 100 parts by mass of deionized water, A film was produced in the same manner as in Sample 1. As a result, a film sample 12 having a thickness of 30 m and an equilibrium water content of about 11% was obtained.

<Sample 13>

The composition is based on the composition described in Example 3 of JP-A-5-308910. Manufactured. In other words, 12 parts by weight of pullulan (Hayawara Shoji Co., Ltd., trade name "PI20"), carrageenan consisting of K-type only (Sansei Co., Ltd., trade name "GENUGEL WG-115") 2 parts by mass of alginic acid Sodium (Kimitsu Chemical Industry Co., Ltd., trade name: Kimitsu Algin ULV-20) 2 parts by mass, sucrose stearic acid ester (Mitsubishi Chemical Foods Co., Ltd., trade name: Sugar Ester S1670) 0.01 parts by mass , And 4 parts by weight of glycerin are dissolved in 100 parts by weight of deionized water, and applied to a glass plate using an applicator (sold by Yoshimitsu Seiki Co., Ltd., trade name: “Beichiriki Applicator YBA type”). After dropping an appropriate amount on a piece of polyethylene phthalate in close contact with it and casting it, spray a 50/0 calcium chloride solution on the surface and heat dry at 85 ° C for 10 minutes, then 25 ° C. C, dry at 55% relative humidity for 16 hours To obtain a film sample 13 water about 13% of the thickness 30〃 m.

<Sample 14>

 8 parts by mass of amylose (sold by Sigma, product name "Typesuri"), 8 parts by mass of agar (Matsuki Agar Sangyo Co., Ltd.), 1 part by mass of sorbitol, esucrose stearate esotere (Mitsubishi Chemical Foods Corporation) 0.01 parts by weight, 2 parts by weight of glycerin, and 1 part by weight of ethanol were dissolved in 100 parts by weight of deionized water, and a film was produced in the same manner as in Sample 1. As a result, a film sample 14 having a thickness of 30 jUm and an equilibrium water content of about 13% was obtained.

<Sample 15>

 8 parts by weight of pullulan (Hayashibara Shoji Co., Ltd., trade name "PI20"), 4 parts by weight of amylose (sale of Sigma, trade name "Type 3"), 1 part by weight of sorbitol, sucrose stearate phosphate (Mitsubishi Chemical Foods Co., Ltd., trade name “Sugar Ester S1670”) Dissolve 0.01 parts by mass, 2 parts by mass of glycerin, and 1 part by mass of ethanol in 100 parts by mass of deionized water, and use the same method as for sample 1. A film was manufactured. As a result, a film sample 15 having an equilibrium water content of about 13% and a thickness of 30 jU m was obtained.

Cut the films of samples 1 to 15 into 1 Ocm squares and stack them on two sheets. Using a heat sealing device sold by Fuji Impulse, "Fuji Impulse Sealer FI-200-1 OW Model", heat seals three sides at 140 ° C for 3 seconds. And molded into a bag. Next, commercially available granulated sugar is finely ground with a mortar, and fractionated with a mesh pass into particles having a particle size of 0.063 to 0.125 mm. The other side was similarly heat-sealed and sealed, and a package was prepared. This was allowed to stand for 1 week in a dry environment at 25 ° C, a relative humidity of 55 o / o, 25 o / o and 10%.

The moisture content of each film sample was determined using a paper moisture meter (K-200) sold by Kett Scientific Research Institute, a device that measures moisture content by electrical resistance, using a single liner setting. It was measured. The evaluation of the peeling of the heat seal was 55% and 25% .Leave the sample left at 10% in a 15cm X 20cm X 5cm paper box, close the lid, and rotate it 10 times left, right, up and down. When the granulated sugar in the contents was not spilled out of the package, it was judged that there was substantially no peeling at the heat seal portion (“〇” when there was no peeling, and “Γ” when there was). In addition, the solubility was evaluated by placing the mixture in a 500 ml beaker containing 300 ml of hot water at 80 ° C and dissolving the granulated sugar in the contents within 5 minutes. "Oj, otherwise ΓX"). Adhesion was measured by storing the film at 80% relative humidity for 16 hours, stacking two films equilibrated with water, pressing them lightly by hand, and then checking if they adhered ("な け れ ば" if not adhered. X)). Table 2 shows the components of each film, and Table 3 shows the results. Table 2

Note: In the table, “κ J is a carrageenan consisting only of type _K (sold by Sansei Co., Ltd., trade name“ G ENUGEL WG-115 ”), and“ κ; ΐ ”is κ: λ = 7: 3 Carrageenan (sold by Sansei Co., Ltd., trade name “GENUVISCO CSW-2”), “J is a carrageenan consisting of only ί-type (sold by Sansei Co., Ltd., trade name: GENUVISCO PJ ”). Table 3

As shown in Table 3, all of the samples 1 to 8 according to the present invention did not peel at the t-seal portion when left in an environment with a relative humidity of 25%, and had good solubility and adhesion. Met. In addition, the film portions that were not heat-sealed also maintained flexibility and had sufficient strength. On the other hand, sample 9 could not be heat-sealed without exfoliation in the heat seal area, and sample 10 did not exfoliate in the heat-sealed area in an environment with a relative humidity of 25%. In an environment with a humidity of 80%, it had the disadvantage of strong adhesiveness. Sample 11 and 1 ^2, the peeling of the heating Bok seal portion occurs under a relative humidity of 25% RH. Further, the film of Sample 13 reproduced in accordance with the composition of the film disclosed in Example 3 of JP-A-5-308910 was peeled off in an environment of a relative humidity of 25%, and further, at 80 ° C. Warm It did not dissolve in water and did not have water solubility. In addition, in Sample 14, even if a water-soluble polysaccharide having no sulfate group other than pullulan, i.e., amylose and agar was used, it was preferable if the water-soluble polysaccharide having a sulfate group was not contained. Sample 15 cannot be heat-sealed.For sample 15, even if pullulan is combined with amylose having no sulfate group, a suitable heat seal should be used without the addition of a water-soluble polysaccharide having a sulfate group. Could not. In addition, the film without a water-soluble polysaccharide having a sulfate group had extremely low brittleness not only in the heat-sealed portion but also in the non-heat-sealed film portion. Therefore, since the film of the present invention is advantageous for storage in a dry environment, it is suitable for packaging water-free contents such as powders, granules, solids, and dry matter. In addition, it was found that it had excellent physical properties as compared with the control product in the use of dissolving it in an aqueous medium. Experiment 2: Comparison of various films with high hydroxy compound content

33% by mass of glycerin in water-soluble polysaccharide in Experiment 1 ΓSample 1 Oj film is not suitable for storage in high humidity due to the adhesiveness of the film surface, but is advantageous in a dry environment. Was thought to be. Therefore, out of 15 parts by mass of pullulan, part of it was carrageenan, a type of other water-soluble polysaccharide (sold by Sansei Co., Ltd., trade name "GENUVISCO SWG-J"), Xanthan gum (sold by Dainippon Pharmaceutical Co., Ltd.), glycerin fatty acid ester (RIKEN Vitamin Co., Ltd., trade name “Poem G-002”), sorbitol 1 mass P, sucrose亍 Add 0.01 parts by weight of an acrylate ester (Mitsubishi Chemical Foods Co., Ltd., trade name "Sugar monoester S1670"), 5 parts by weight of glycerin, and 1 part by weight of ethanol, and heat and dry at 85 for 15 minutes. A film was prepared according to the method of Sample 1 of Experiment 1. The produced film was used with the heat sealer “Fuji Impulse Sealer FI-200-10W Model” sold by Fuji Impulse Co., Ltd. Heat seal three sides at 180 ° C for 1 second in an environment with a relative humidity of 40%, and store the sample in an environment with a relative humidity of 25% and 10% in the same manner as in Experiment 1. evaluated. In addition, the film strength and the strength of the heat seal portion were measured in accordance with a standard method using a rheometer (manufactured by Leotech Co., Ltd., trade name "RT-2010 J-CW") in accordance with Japanese Industrial Standards JISZ1707. .

 As a result, when the ratio of pullulan to carrageenan was in the range of 10: 5 to 6: 9, no delamination occurred even in an environment with a relative humidity of 25% and 10%. In addition, the mouth—cast bean gum is 0.4 to 30% by weight based on pullulan, xanthan gum is 0.1 to about 10% by weight based on pullulan, and glycerin fatty acid ester is the total amount of pullulan, carrageenan and glycerin. When the content was 1 to 10% by mass, the film strength and the heat sealing strength were remarkably increased. Although it is not suitable for heat sealing in an environment with a relative humidity of more than 60%, the film surface has low adhesiveness even when stored in an environment with a relative humidity of 80%. Heat sealing was possible even at the above temperatures. This result indicates that if a film containing relatively large amounts of glycerin (20% by mass or more of water-soluble polysaccharide) as a humidity control material and pullulan and carrageenan as water-soluble polysaccharides are mixed, the film becomes extremely dry. It is excellent in use and preservation under environmental conditions, and shows that the addition of lipstick cast bean gum, xanthan gum and glycerin fatty acid ester can produce a water-soluble film suitable for a dry environment with significantly improved film strength. . Hereinafter, the water-soluble film of the present invention will be described in more detail with reference to Examples. Example 1: Water-soluble film

Prepare an aqueous pullulan solution having the composition shown below, and use an applicator (sold by Yoshimitsu Seiki Co., Ltd., trade name: "Beriki-ichi Applicator YBA type") on a glass plate. Qs dropped is spread over those obtained by contact of polyethylene亍terephthalate, after drying by heating for 10 minutes at 85 ° C, 25 ° C, left for 16 hours at 55% relative humidity, the equilibrium water content of about _110/0 A film having a thickness of 30 m was produced.

Pullulan (Hayashibara Shoji Co., Ltd., trade name "PI20") 20 parts by mass Carrageenan (ΛΓ and I)

 (Sansei Co., Ltd., product name "GENUVISCO CSW-2") 3 parts by mass Sorbi!

 (Mitsubishi Chemical Foods Co., Ltd., product name "Sugar Ester S1670") 0.01 parts by mass Glycerin 2 parts by mass Deionized water 72 parts by mass This product is excellent in water solubility, and the package is made up of the contents. The contents can be removed simply by immersion in an aqueous medium without opening the container. In addition, it holds moisture suitable for a heat seal in a dry environment, and the heat seal portion does not substantially peel. In addition, since pullulan is used as a main raw material, it has the property of being impermeable to oxygen and is suitable for packaging of easily oxidizable objects. Example 2: water-soluble film

 An aqueous pullulan solution having the composition shown below was prepared, and polyethylene terephthalate was adhered onto a glass plate using an applicator (sold by Yoshimitsu Seiki Co., Ltd., trade name: Baker Applicator-YBA type). An appropriate amount of the solution is dropped on a plate, spread, heated and dried at 85 ° C for 10 minutes, and then left at 25 ° C and a relative humidity of 55 <16 for 16 hours.The equilibrium water content is about 12 o / o and the thickness is 30 jUm. A film was produced.

Pullulan (Hayashibara Shoji Co., Ltd., product name "PI20") 20 parts by mass Carrageenan (L) (Sansei Co., Ltd., trade name "GENUVISCO PJ") 2.2 parts by mass powdered soybean protein (Fuji Oil Co., Ltd., trade name "Fujipro") 1 part by mass, one trehalose (Hayashibara Corporation) Sales, trade name "Treha") 1 part by mass sucrose stearate

 (Mitsubishi Chemical Foods Co., Ltd., product name "Sugar Ester S1670") 0.01 parts by mass Glycerin 2 parts by mass Deionized water 72 parts by mass This product is excellent in water solubility, and the package is made up of the contents. The contents can be removed simply by immersion in an aqueous medium without opening the container. In addition, it retains moisture suitable for heat sealing in a dry environment, and the heat sealed portion does not substantially peel off. In addition, since pullulan is used as a main raw material, it has the property of being impermeable to oxygen and is suitable for packaging of easily oxidizable objects. Example 3: Water-soluble film

 Prepare an aqueous pullulan solution having the composition shown below, and use an applicator (sold by Yoshimitsu Seiki Co., Ltd., trade name “Baker Applicator-YB A type”) on a glass plate with polyethylene phthalate adhered to it. An appropriate amount was dropped, spread, heated and dried at 85 ° C for 10 minutes, and then left at 25 ° C and a relative humidity of 55% for 16 hours to produce a film having a thickness of 30 m and an equilibrium water content of about 11%.

Pullulan (Hayashibara Shoji Co., Ltd., trade name "PI20") 20 parts by mass

Carrageenan (K)

 (Sansei Co., Ltd., product name "GENUGEL WG-115") 1 part by mass carrageenan (/ ί and λ)

(Sansei Co., Ltd., product name "GENUVISCO CSW-2") 1 part by weight Carrageenan (ί) (Sansei Co., Ltd., product name “GENUVISCO PJ”) 1 part by weight Sorubi! 1 part by weight sucrose stearate

 (Mitsubishi Chemical Foods Co., Ltd., product name "Sugar Ester S1670") 0.01 parts by mass Glycerin 2 parts by mass Deionized water 72 parts by mass This product has excellent water solubility, and the package The contents can be taken out by simply immersing the contents in an aqueous medium without opening the contents. In addition, it retains moisture suitable for heat sealing in a dry environment, and the heat sealed portion does not substantially peel off. In addition, since pullulan is used as a main raw material, it has the property of being impermeable to oxygen and is suitable for packaging of easily oxidizable objects. Example 4: water-soluble film

 Prepare an aqueous pullulan solution of the composition shown below and apply it to an applicator (Yoshimitsu Seiki

Using “Baker Applicator-YBA Type” sold by Co., Ltd., apply an appropriate amount onto a glass plate with polyethylene terephthalate in close contact with it, spread it, and heat and dry at 85 ° C for 15 minutes. The film was allowed to stand at 25 ° C and a relative humidity of 55% for 16 hours to produce a film having a thickness of about 13% in equilibrium water.

Pullulan (Hayashibara Shoji Co., Ltd., trade name "PI20") 4 parts by mass Locust bean gum (Sansei Co., Ltd.) 0.7 parts by mass Xanthan gum (Dai Nippon Pharmaceutical Co., Ltd.) 0.1 parts by mass Karagi One Nan ()

(Sansei Co., Ltd., product name "GENUVISCO SWG-J") 3 parts by weight glycerin 3.5 parts by weight glycerin fatty acid ester (RIKEN Vitamin Co., Ltd., trade name "Poem G-002") 0.15 parts by mass sucrose stearate

(Mitsubishi Chemical Foods Co., Ltd., product name "Sugar Ester S1670") 0.01 parts by mass Deionized water 84 parts by mass This product has excellent water solubility, and the package using this product can be used without opening the contents. However, the contents can be taken out simply by dipping in the aqueous medium. In addition, it retains moisture suitable for heat sealing in a dry environment, and the heat sealed portion does not substantially peel off. Although this product is not suitable for use and storage in high humidity environments where the relative humidity exceeds 60%, it can be used and stored in a severe dry environment with a relative humidity of 10% or less. It is a film that can be heat-sealed at a temperature of C or higher. Example 5 _: Gauze coated with a water-soluble film

 Prepare an aqueous pullulan solution of the composition shown below, apply it to gauze with a brush, place it on a glass plate with polyethylene terephthalate closely adhered, place it well, add the above solution, and immerse it well Thereafter, the resultant was dried by heating at 85 ° C for 15 minutes, and then allowed to stand at 25 ° C and a relative humidity of 55 ° / o for 16 hours to produce a gauze coated with a water-soluble film having an equilibrium water content of about 11%.

Pullulan (Sales by Hayashibara Corporation, trade name "PI20") 14 parts by mass Carrageenan (and λ)

 (Sansei Co., Ltd., product name "GENUVISCO CSW-2") 7 parts by mass Sorbi! -Rol 1 part by mass sucrose spearic acid ester

(Mitsubishi Chemical Foods Co., Ltd., product name "Sugar Ester S1670") 0.01 parts by mass Glycerin 2 parts by mass Deionized water 2 parts by mass This product has gauze eyes filled with a water-soluble film, so it can be heat-sealed and has excellent sealing properties. Further, the contents can be taken out by simply immersing the contents in an aqueous medium without opening the contents. Also, it holds moisture suitable for heat sealing in a dry environment, and the heat-sealed portion does not substantially peel off. In addition, since pullulan is used as a main raw material, it has an oxygen-impermeable property and is suitable for packaging of easily oxidizable objects. Example 6: Instant coffee

 The film manufactured in Example 1 or Example 4 was cut into squares each measuring 4 cm on a side, and two sheets were stacked. Then, a heat sealing device (trade name: Fuji Impulse Sealer, sold by Fuji Impulse Co., Ltd.) 1 OPL—200—10 ”), the film of Example 1 was heated at 130 ° C. for 3 seconds, and the film of Example 4 was heated at 180 ° C. for 1 second. Under heat-sealing conditions, three sides were heat-sealed, and into a bag-shaped one, 2 to 5 g of a commercially available instant coffee was put, and the other side was heat-sealed under the same conditions.

 This product can be put in a coffee cup and poured with hot water without opening it.This saves the trouble of opening and measuring the coffee powder, and the powder does not scatter. Handling is simple. Example 7: Tea pack

The net base material for the tea pack was sandwiched between the two films manufactured in Example 2, and the entire surface of the film was heat-sealed under high heat and pressure using an eye opening, and the net base material was used to fill the mesh gap with the film. . Using this, a tea pack was manufactured by a conventional method. The film used in this product is edible and water-soluble. Black tea can be easily extracted by immersion in water, and the extraction residue can be easily disposed of. In addition, since this product has excellent airtightness, it is possible to prevent the deterioration of the quality of black tea. In addition, in addition to black tea, sealed materials using a net base material with gaps filled with a film include, for example, green tea, herbal tea, oolong tea and other teas, shiitake mushrooms, shaved katsubushi, kelp and other dashes. Can also be applied advantageously. Example 8: Detergent

 The film of Example 3 was heat-sealed at 130 ° C. for 3 seconds so that the film produced in Example 3 or 4 became a rectangle having a length of 1 O cm and a width of 7 cm. The film was heat-sealed under a heat-sealing condition of 180 ° C for 1 second, then cut off, and the heel was cut off to form a bag. 5 g of a commercially available powder detergent was added thereto, and heat-sealed again to seal. A set of five bags was put in a polyethylene bag of an appropriate size, and then the polyethylene bag was heat-sealed.

 After removing the product from the polyethylene bag, it is sufficient to put it in a water tank such as a washing machine without opening the seal.This saves the labor of weighing and prevents the detergent from adhering to the hands. It can be handled without scattering. In addition, since the sealant and the oxygen impermeability are excellent, the effectiveness of the detergent can be maintained. Example 9 Bath Salt

60 parts by mass of sodium sulfate powder, 27 parts by mass of sodium hydrogen carbonate powder, 1 part by mass of titanium dioxide powder, 1 part by mass of sodium lauryl sulfate powder, an appropriate amount of silicone resin defoamer and an appropriate amount of perfume Was prepared. On the other hand, the gauze manufactured in Example 5 was cut into a square having a side of 12 cm and cut into two squares. After that, a heat seal device (trade name: Fuji Impulse, sold by Fuji Impulse Co., Ltd.) Using a sealer OPL 200—10 ”), the above bath agent was heat-sealed on three sides under a heat-sealing condition of 130 and 3 seconds to form a bag. After putting in 5 g, The other side was heat-sealed under the same conditions.

 This product can be put into a bathtub without opening it, so that it is not necessary to open it and the powder of the bathing agent is not scattered, so it is easy to handle. Industrial applicability

 As described above, the film of the present invention maintains sufficient film strength and flexibility even in a dry environment, for example, an environment with a relative humidity of 25%, and does not substantially peel off the heat seal portion. Further, since the film of the present invention is water-soluble, the contents can be dissolved by putting it in an aqueous medium without opening the film. Therefore, it can be used in a wide range of fields such as foods, cosmetics, pharmaceuticals, and chemicals.

Claims

The scope of the claims

1. One or more water-soluble polysaccharides having no sulfate group and one or more water-soluble polysaccharides having a sulfate group are blended with one or more hydroxy compounds as a humidity control material. A water-soluble film that does not contain a cross-linking agent and does not substantially exfoliate under heat and moisture equilibrium conditions of a relative humidity of 25% or less when heat-sealed.

 2. The water-soluble film according to claim 1, wherein the water-soluble polysaccharide having no sulfate group and the water-soluble polysaccharide having a sulfate group are edible polysaccharides.

3. The water-soluble film according to claim 1 or 2, wherein the water-soluble polysaccharide having no sulfate group is a polysaccharide having maltotriose as a repeating unit.

 4. The water-soluble film according to claim 3, wherein the polysaccharide having maltotriose as a repeating unit is pullulan.

5. The water-soluble film according to claim 1 or 2, wherein pullulan, locust bean gum and xanthan gum are blended as the water-soluble polysaccharide having no sulfate group.

 6. The amount of the hydroxy compound is 200/0% by mass or more based on the total amount of the water-soluble polysaccharide, and the total amount of cast bean gum and xanthan gum is 0.5 to 40% by mass with respect to pullulan. Item 6. The water-soluble film according to item 5 above.

 7. The water-soluble film according to claim 1, 2, 3, 4, 5, or 6, wherein the water-soluble polysaccharide having a sulfate group is carrageenan.

 8. The water-soluble film according to any one of claims 1, 2, 3, 4, 5, 6, or 7, wherein the hydroxy compound is a polyol.

9. Claims characterized by further containing a glycerin fatty acid ester, claim 1, claim 2, claim 3, claim 4, claim 5, paragraph 6, paragraph 7, or paragraph 8. Described in Water-soluble film.

 10.When immersed in warm water at 80 ° C, it dissolves substantially within 5 minutes.Claims 1, 2, 3, 3, 4, 5, 6, 7 Item 8. The water-soluble film according to item 9, or 9.

11Claims 1, 2, 3, 4, 5, 5, 6, 7, 8, A packaging material using the water-soluble film according to paragraph 9 or 10.

 12. A method for producing a packaged article, characterized by packaging with the packaging material according to claim 11.