JPWO2004041926A1 - Water-soluble film - Google Patents

Abstract

The present invention provides a water-soluble film that can perform a good heat seal and can maintain a good heat seal state even under a dry environment, and a food, cosmetic, pharmaceutical, or chemical product using the same. It is an object to provide a package, and one or more water-soluble polysaccharides having no sulfate group and one or more water-soluble polysaccharides having a sulfate group, and one or more hydroxy compounds as a humidity control material By providing a water-soluble film that is blended, substantially contains no cross-linking agent, and does not peel substantially under heat equilibrium conditions of a relative humidity of 25% or less when heat sealed. , Solve the problem.

Description

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

Films made mainly of water-soluble polysaccharides such as pullulan are edible and water-soluble, so that the packaged contents can be removed from the package by simply putting them in an aqueous solvent without opening them. Can be released. Among water-soluble polysaccharides, films made mainly of pullulan have extremely excellent oxygen impermeability, so if they can be packaged in a sufficiently sealed form, It is also possible to prevent oxidative degradation.
When packaging an article using a film, heat sealing is an extremely useful technique because it can easily perform sealing with excellent sealing properties and strength, and is a film mainly composed of a water-soluble polysaccharide. The use of it has been demanded. Films mainly composed of water-soluble polysaccharides such as pullulan were recognized as relatively heat-sealing films at the time they were developed, but even if heat sealing was actually applied to the films, Various inconveniences such as excessive heat melting, air bubbles and pinholes occur, and heat seal may be peeled off or cracked during use and storage or transportation, so that it can withstand commercial use. The stable heat-sealing technology has not yet been completed for films made mainly of water-soluble polysaccharides.
As a method for improving the heat sealability of a film containing pullulan as a main raw material, in Japanese Patent Application Laid-Open No. 53-79972 by the same applicant, water is applied to the heat seal part of a film containing pullulan as a main raw material. There has been proposed a method of heat sealing without increasing the temperature of the heat seal portion above the evaporation temperature. According to this method, although heat sealing can be performed satisfactorily, it is necessary to apply water to the site to be sealed, so it is not suitable for stable and continuous heat sealing in large quantities. . Japanese Patent Application Laid-Open No. 5-308910 discloses a film using heat-sealable pullulan as a main raw material, but the film is a water-resistant film combined with a crosslinking agent.
In addition, 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 it is used and stored. In a dry environment, the film dries, heat sealing becomes difficult, and the heat seal portion may peel off or crack. The techniques described in the above prior art documents do not solve this problem.

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 food, cosmetic, pharmaceutical or chemical package using the same. Let it be an issue.
As a result of repeated research to solve the above-mentioned problems, the present inventors first realized a water-soluble film having good heat sealability by using a water-soluble polysaccharide such as pullulan. ▼ In the environment where heat sealing is performed, the moisture content of the film is in the range of 11 to 14%, and (2) In the dry environment where the moisture content of the film is lowered, it has flexibility and good It is concluded that the heat seal is maintained, and further, (3) it is necessary to have the property that the adhesiveness of the film surface does not become too high even in a high humidity environment. In order to realize a water-soluble film, trial and error were repeated, and it was possible to increase the water content if a moisture conditioning material having moisture retention was added to the film, and to add a water-soluble polysaccharide having a sulfate group. If blended in an amount, it has sufficient flexibility even in a dry environment, a good heat seal is maintained, and the required amount of humidity conditioning material can be reduced. Even if the film contains a large amount of film, as a water-soluble polysaccharide having no sulfate group, pullulan, locust bean gum and xanthan gum are blended, and further, by blending an appropriate amount of fatty acid esters such as glycerin fatty acid ester, It was discovered that the strength and heat seal strength could be improved, and a water-soluble film excellent in heat sealability in a dry environment and a method for producing the same were established, and the present invention was completed.
According to the water-soluble film of the present invention as described above, excellent heat-sealability is achieved despite the fact that no cross-linking agent that has been considered necessary for obtaining a film having excellent heat-seal properties has been used. In addition, since a crosslinked structure is not formed, a film having excellent water solubility can be realized.
That is, the present invention is a water-soluble film based on a water-soluble polysaccharide, the water-soluble polysaccharide having no sulfate group, a water-soluble polysaccharide having a sulfate group, and a humidity control material. The problem is solved by providing a water-soluble film substantially containing no crosslinking agent by blending fatty acid esters as required.

本発明で用いる調湿用材としては、各種ヒドロキシ化合物、特に揮発性でないヒドロキシ化合物であり、例えば、エリスリトール、キシリトール、ソルビトール、マルチトール、α，α−トレハロース、グリコシルα，α−トレハロース、環状オリゴ糖、グリコシル環状オリゴ糖、グリセリンなどのポリオール類、またはこれらの誘導体などが挙げられ、これらを一種または二種以上を組み合わせて用いることができる。これらのうち、グリセリンを含有させるのが好ましく、さらに、これらに加えて、ソルビトール又はα，α−トレハロースを含有させるのが好ましい。
上記調湿用材の配合比率が比較的高い場合、レシチン、パーム油などの脂質類、ショ糖ステアリン酸エステルなどの糖脂肪酸エステル、グリセリン脂肪酸エステル、プロピレングリコール脂肪酸エステルなどの脂肪酸エステル類を配合することにより、フィルム表面の粘着性を減少させることができる。このうち、グリセリン脂肪酸エステル及び糖脂肪酸エステルを含有させるのが好ましい。
本発明の水溶性フィルムにおける各配合成分の比率としては、硫酸基を有しない水溶性多糖類に対して、硫酸基を有する水溶性多糖類を１５乃至１５０質量％の範囲内で配合する。また、ヒドロキシ化合物を水溶性多糖類全量に対して１乃至５０質量％の範囲内で配合する。ただし、水溶性多糖類全量に対するヒドロキシ化合物の配合比率が２０質量％を超える場合、フィルム強度の低下及びフィルム表面の粘着性が顕著になるので、フィルム強度を高めるために、硫酸基を有しない水溶性多糖類としてプルラン、ローカストビーンガム及びキサンタンガムを用いるのが望ましく、ローカストビーンガム及びキサンタンガムの総量を、プルランに対して０．５乃至４０質量％の範囲内とするのが好ましい。さらに、水溶性多糖類全量に対するヒドロキシ化合物の配合比率が２０質量％を超える場合、硫酸基を有しない水溶性多糖類に対する硫酸基を有する水溶性多糖類の比率を５０乃至１５０質量％、好ましくは６０乃至１２０質量％の範囲内とするか、及び／又は、脂質類又は脂肪酸エステル類を水溶性多糖類及びヒドロキシ化合物の総量に対し、１乃至１０質量％の範囲内で配合することにより、フィルム強度及びフィルム表面の粘着性を低減させることができる。
本発明の水溶性フィルムには、上記の成分に加えて、本発明の目的を妨げない範囲で、他の成分を適宜含有させてもよい。含有させることができる物質としては、大豆蛋白質、ゼラチンなどのタンパク質及びその分解物、エタノールなどの揮発性のアルコール類、色素類、香料類、又はそれらの誘導体などがあげられる。
本発明のフィルムの製造方法としては、水やエタノールなどの水性溶媒により適度な粘性の溶液状態とし、これを常法にしたがい、流延法、押出成形法、スプレー法、ロールコーティング法、ディッピング法などの方法により、薄膜を形成後、室温若しくは室温を越える温度で乾燥することにより、フィルムに成形する方法が挙げられる。
かくして得られるフィルムは、通常、包装した後、水性溶媒に浸漬して溶解させる目的を有している。したがって、フィルムは水溶性を有する必要がある。水性媒体への溶解速度は、溶媒の種類、量及び温度、撹拌の強度、溶解時におけるフィルムの水分含量などを考慮して、フィルムの厚さ、大きさなどの形状、水溶性多糖類の重量平均分子量、水溶性多糖類の分子量分布、各種水溶性多糖類の比率、各種ヒドロキシ化合物の混合比率を適宜選択することにより行うことができる。本発明のフィルムにおいては、用途にもよるが、８０℃の温水に投入した場合、通常、５分以内、より好ましくは３分以内にフィルムに密封包装された内容物が放出されるような水溶性を与えるように構成するのが望ましい。なお、本発明のフィルムにおいては、水溶性がより高いことが望まれるので、フィルムの水溶性を低下させる原因となる非水溶性の架橋構造を形成する架橋剤を含有させてはならない。含有させる水溶性多糖類によっては、非水溶性の架橋構造を形成する作用のある、例えばカルシウムなどのミネラル類などの物質を各配合成分から排除しておくことが望ましい。
本発明の水溶性フィルムの厚さは、用途に応じて決定すればよいが、通常、１μｍ乃至１００μｍ、好ましくは、１０μｍ乃至５０μｍの範囲から選ばれる。厚さが１μｍ未満だと、破れやすいので好ましくなく、厚さが１００μｍを越えると、水などの溶媒への溶解時間が長くなりすぎたり、溶媒中に溶出するフィルムの成分量が多くなりすぎ、好ましくない場合がある。
本発明の水溶性フィルムは、フィルムが使用及び保存される乾燥環境下、具体的には、相対湿度約２５％、好ましくは約１０％の環境下におけるフィルムの平衡水分含量が約１０乃至約１５％、好ましくは約１１乃至約１４％に維持できるように配合成分の比率を調整することによって、ヒートシール性、フィルムの強度、柔軟性などの特性を有することとなる。
本発明でいうヒートシールとは、２枚以上が重なりあったフィルムあるいは部分的に２枚以上が重なりあったフィルム部分を加熱圧着することによって接着することであり、その形状としては、２枚のフィルムを重ね合わせ、あるいは、１枚のフィルムを折り曲げたものの周囲部にヒートシールを施して袋状に成形したものが一般的である。このような形状は、例えば、内容物が粉末状、顆粒状、脂性ペースト状または脂性液体状の場合に有利に適用される。また、通常は、ヒートシールはフィルムの一部に対して行うが、内容物が耐熱性のシート状のものであれば、内容物を含めて、フィルムの全面にヒートシールすることも可能である。また、複数個を連結したままヒートシール包装した場合は、包装後にそれぞれを切り離したり、切り離しを容易にするためミシン目を入れたりすることができる。比較的大型の固体の場合は、１枚又は複数枚のフィルムで包装対象物を包んだ後に、重なった部分のフィルムをヒートシールにより接着させて包装体とすることができる。また、必要ならば、酸素や水蒸気などの包装対象物の品質を劣化させる気体を包装内部に封入することを防ぐために、不活性ガスや真空中で包装することも、さらには、無菌的に包装することも随意である。
ヒートシール装置としては、加熱圧着する装置、例えば、ヒートバータイプ、ロールタイプ、ピロータイプ、インパルス包装機、高周波包装機などを用いて行うことができる。より良好なヒートシールを行うためには、ヒートシール部の温度を制御できる機種が望ましく、例えば、市販のヒートシール装置としては、（株）富士インパルス販売の商品名『富士インパルスシーラーＯＰＬ−２００−１０』などを用いることができる。このような温度制御可能なヒートシール装置を用いる場合は、シールを施す部分の温度を、通常、１００乃至２００℃、好ましくは１１０乃至１６０℃、好ましくは１２０℃乃至１４０℃の範囲内になるように設定し、ヒートシールする時間を１乃至４秒間の範囲内で行うと、ヒートシールを失敗することがほどんどなくなる。
本発明のフィルムによる包装体は、保存中において実質的に内容物が包装体から包装外にこぼれないように十分に封止されている必要があり、フィルムに負荷されることが想定される圧力、張力、せん断力、振動などに耐える十分な強度を有していることが望まれる。フィルムの強度およびヒートシール部の強度としては、日本工業規格ＪＩＳＺ１７０７に準拠し、例えば、レオメーター（（株）レオテック製造、商品名『ＲＴ−２０１０Ｊ−ＣＷ』）を用いて測定することができる。用途にもよるが、保存環境の相対湿度において、通常、フィルムの強度は１００ｇｆ以上、好ましくは１５０ｇｆ以上、かつ、ヒートシール強度は１５０ｇｆ／１５ｍｍ幅以上、好ましくは２５０ｇｆ／１５ｍｍ幅以上を有することが望まれる。
本発明のフィルムの用途としては、固体、粉末、顆粒、錠剤、クリーム、エマルジョン、マスキット、ペースト、油性液体などの形態の食品、化粧品、医薬品、化学品の包装などに用いられ、特に、密封することにより、空気中の酸素による内容物の酸化を防ぐことができ、さらに、包装された状態のまま、食したり、適宜の溶媒にそのまま投入したり、溶媒を包装体に注いだりしても、包装が溶解して、内容物を溶媒中に放出させることができる。また、フィルムの内容物に接触する側に、油脂などの耐水性の物質をコーティングすれば、水分を多く含むものや水性液体を内容物とすることができる。本発明のフィルムは、包装の開封をかならずしも要しないので、開封する手間が省け、さらに、開封時に包装対象物を飛散させる危険性を有しないので、使用者は、手、指、衣服などの汚染、呼吸器への吸引に注意を払うことなく使用できる。したがって、食品、化粧品、医薬品分野のみならず、毒薬、劇薬、発ガン性物質などの危険度の高い物質の包装に適用すれば、それらの物質の取扱いを安全かつ容易にすることができる。なお、本発明の水溶性フィルムの別の使用形態として、一部が開放された状態、例えば、袋状、筒状の形態で用いることもできる。また、ヒートシール以外の方法、例えば、澱粉、タンパク質などの接着剤を用いて繋ぎ合わせる方法、フィルムを重ねたり折り曲げたりした後、留め具などで固定するなどの方法を採用することもできる。また、所望により、本発明の一枚または二枚以上のフィルムで多重包装したり、他の包装材を併用して多重包装してもよい。また、ヒートシール性は劣るものの、他のフィルムと本発明のフィルムとをヒートシールしてラミネートフィルムにしたりすることもできる。また、本発明のフィルムを製造する際に、本発明のフィルムの原料を他のフィルム、例えば、ポリエチレン、ナイロン、紙などの上で流延したり、塗布、透漬したのち、乾燥してフィルムを作製すれば、２重フィルムが製造でき、本来ヒートシールが出来なかったフィルムにもヒートシール性を付与できる。特に、網目構造を有するフィルム状物、例えば、布、ガーゼ、濾紙、不織布、網などに適用すれば、隙間を埋めることができるので、これらによる包装物に気密性を付与することができ、茶類、だし類などの取り出し袋に有利に適用できる。
本発明のフィルムにより包装可能な食品分野の物品としては、例えば、生果、野菜、根菜、種、球根などの農産物、ジュース、ドライフルーツ、野菜エキス、野菜粉末、漬物など果物・野菜加工品、胡麻ペースト、ナッツペースト、コーンペーストなど種実ペースト、生餡、粉末こし餡など餡、サツマイモ粉、ヤマイモ粉などのいも粉、胡麻、玄米、小麦、大麦、ライ麦、大豆、コーン、ピーナッツ、アーモンド、コーヒー豆、ココア豆など種実又はこれらの粉砕物、精白米（白米）、胚芽米、無洗米、精白大麦、精白ハト麦、精白キビなど精白穀類、米粉、小麦粉、大麦粉、ライ麦粉、ハト麦粉、大豆粉、大豆胚芽粉、ソバ粉、コーンフラワーなど粉末穀類、すり胡麻、はったい粉、きな粉、荒挽きコーヒーなど種実加工物などの農産品、イワシペースト、カキ肉エキス、ウニペースト、アジの開き、魚肉、削りカツオブシ、昆布、魚粉などの水産品、畜肉、牛乳、乳クリーム、鶏肉、鶏卵などの畜産品、醤油、味噌、ソース、マヨネーズ、ドレッシングなどペースト状乃至液状調味料、粉末油脂、香辛料、ふりかけなど粉末調味料などの調味料、求肥、おかき、はじき豆、揚豆、かりんとう、揚せんべい、カステラなどの和菓子、チョコレート、チューインガム、パン、ケーキ、乳菓、クリーム菓子、スナック菓子などの洋菓子、アイスクリーム、シャーベットなどの冷菓、緑茶、ほうじ茶、紅茶、ウーロン茶、玄米茶、麦茶、ハト麦茶などの茶類、米飯、蒸米、米粉、餅、おにぎり、おかゆ、α化米、チャーハン、ピラフなどの米加工品、パスタ、パン、ピザ、ナン、パン粉、プレミックスなどの小麦加工品、豆乳、豆腐、厚揚、おから、おからハンバーグ、豆乳プリンなどの大豆加工品、麹、甘酒、清酒、みりん、ビール、蒸留酒、酢、味噌、醤油、糠漬、麹漬、粕漬、味噌漬、たまり漬などの発酵飲食物、ハム、ソーセージなどの畜肉加工品、かまぼこ、ちくわ、はんぺんなどの魚肉練製品、ウニ、イカなどを用いた塩辛、肉、魚の干物、小魚、エビ、イカ、貝、畜肉などを用いた珍味、佃煮、煮豆、サラダ、炒め物、揚げ物、煮物、卵焼、焼肉、焼き鳥、ハンバーグ、ぎょうざ、天ぷら、天かすなどの惣菜食品、練乳、粉乳、ヨーグルト、チーズ、コーヒーフレッシュなどの乳加工品、ババロア、ムース、マシュマロ、プリン、シュークリーム、錦糸卵、だし巻卵、茶碗蒸し、マヨネーズなど卵加工品、各種茶類から製造される茶飲料、甘酒、コーヒー飲料、乳飲料、乳酸菌飲料などの清涼飲料の粉末、サラダ油、オリーブ油、椿油などの液体状油脂、バター、マーガリンなどの固体状油脂、清酒、ワイン、リキュールなどのアルコール飲料の粉末、冷凍食品、離乳食、治療食、健康食品、ペプチド食品などがあり、更には、例えば、穀類ペレット、穀類粉末、植物油粕、発酵粕、米糠、小麦麸、大麦糠、脱脂糠、脱脂大豆、フィシュミール、フィシュソリュブル、肉粉、血粉、羽毛粉、脱脂粉乳、乾燥ホエー、さなぎ粕、アルファミールなどの飼料原料又はこれらを含有する配合飼料、撒き餌、寄せ餌などの釣りの餌、種苗などが挙げられる。
本発明のフィルムにより包装可能な化粧品分野の物品としては、例えば、練り歯磨き、口紅、リップクリーム、口中香剤、うがい剤、入浴剤、制汗剤、石けん、シャンプー、リンス、ボディーソープ、ボディーローション、デオドラント剤、ヘアクリーム、色白剤、美肌剤、美毛剤、育毛剤などが挙げられる。
本発明のフィルムにより包装可能な医薬品分野の物品としては、例えば、ドリンク剤、経口栄養剤、経管栄養剤、注射用脂肪乳剤、トローチ、肝油ドロップなどの医薬品、臓器、人工臓器などが挙げられる。
本発明のフィルムにより包装可能な化学品分野の物品としては、例えば、防虫剤、防鼠剤、除草剤などの農薬、現像液などの写真用薬剤、柔軟剤、漂白剤、洗剤などの洗濯用剤、医学、化学又は生物学研究用試薬などに用いられる薬剤全般、さらには、生物、岩石、土壌などの標本が挙げられ、とりわけ、毒物、劇物、発ガン性物質、放射性物質などの人体に害のある物質などが挙げられる。
以下、実験により、本発明の水溶性フィルムについて詳細に説明する。
実験１：各種フィルムの比較
＜試料１＞
プルラン（（株）林原商事販売、商品名『ＰＩ２０』）１２質量部、κ型のみからなるカラギーナン（三晶（株）販売、商品名『ＧＥＮＵＧＥＬ ＷＧ−１１５』）３質量部に、ソルビトール１質量部、ショ糖ステアリン酸エステル（三菱化学フーズ（株）、商品名『シュガーエステルＳ１６７０』）０．０１質量部、グリセリン２質量部、及びエタノール１質量部を脱イオン水１００質量部に溶解し、これをアプリケーター（ヨシミツ精機（株）販売、商品名『ベーカーアプリケーターＹＢＡ型』を使用して、ガラス平板上にポリエチレンテレフタレートを密着させたものの上に適量滴下し展延し、８５℃で１０分間加熱乾燥した後、２５℃、相対湿度５５％で１６時間放置し、フィルムを製造した。その結果、平衡水分約１３％の厚さ３０μｍのフィルム試料１を得た。
＜試料２＞
プルラン（（株）林原商事販売、商品名『ＰＩ２０』）１２質量部、κ：λ＝７：３の比率で含有するカラギーナン（三晶（株）販売、商品名『ＧＥＮＵＶＩＳＣＯ ＣＳＷ−２』）３質量部に、ソルビトール１質量部、ショ糖ステアリン酸エステル（三菱化学フーズ（株）、商品名『シュガーエステルＳ１６７０』）０．０１質量部、グリセリン２貿量部、及びエタノール１質量部を脱イオン水１００質量部に溶解し、試料１と同様の方法でフィルムを製造した。その結果、平衡水分約１３％の厚さ３０μｍのフィルム試料２を得た。
＜試料３＞
プルラン（（株）林原商事販売、商品名『ＰＩ２０』）１２質量部、ι型のみからなるカラギーナン（三晶（株）販売、商品名『ＧＥＮＵＶＩＳＣＯ ＰＪ』）３質量部に、ソルビトール１質量部、ショ糖ステアリン酸エステル（三菱化学フーズ（株）、商品名『シュガーエステルＳ１６７０』）０．０１質量部、グリセリン２質量部、及びエタノール１質量部を脱イオン水１００質量部に溶解し、試料１と同様の方法でフィルムを製造した。その結果、平衡水分約１３％の厚さ３０μｍのフィルム試料３を得た。
＜試料４＞
プルラン（（株）林原商事販売、商品名『ＰＩ２０』）１２質量部、κ型のみからなるカラギーナン（三晶（株）販売、商品名『ＧＥＮＵＧＥＬ ＷＧ−１１５』）、κ：λ＝７：３の比率で含有するカラギーナン（三晶（株）販売、商品名『ＧＥＮＵＶＩＳＣＯ ＣＳＷ−２』）、及びι型のみからなるカラギーナン（三晶（株）販売、商品名『ＧＥＮＵＶＩＳＣＯ ＰＪ』）をそれぞれ１質量部に、ソルビトール１質量部、ショ糖ステアリン酸エステル（三菱化学フーズ（株）、商品名『シュガーエステルＳ１６７０』）０．０１質量部、グリセリン２質量部、及びエタノール１質量部を脱イオン水１００質量部に溶解し、試料１と同様の方法でフィルムを製造した。その結果、平衡水分約１３％の厚さ３０μｍのフィルム試料４を得た。
＜試料５＞
プルラン（（株）林原商事販売、商品名『ＰＩ２０』）１２質量部、κ型のみからなるカラギーナン（三晶（株）販売、商品名『ＧＥＮＵＧＥＬ ＷＧ−１１５』）、及びι型のみからなるカラギーナン（三晶（株）販売、商品名『ＧＥＮＵＶＩＳＣＯ ＰＪ』）をそれぞれ２質量部にソルビトール１質量部、ショ糖ステアリン酸エステル（三菱化学フーズ（株）、商品名『シュガーエステルＳ１６７０』）０．０１質量部、グリセリン２質量部、及びエタノール１質量部を脱イオン水１００質量部に溶解し、試料１と同様の方法でフィルムを製造した。その結果、平衡水分約１３％の厚さ３０μｍのフィルム試料５を得た。
＜試料６＞
アミロース（シグマ社販売、商品名『タイプスリー』）６質量部、寒天（松木寒天産業（株）販売）６質量部、κ型のみからなるカラギーナン（三晶（株）販売、商品名『ＧＥＮＵＧＥＬ ＷＧ−１１５』）、及びι型のみからなるカラギーナン（三晶（株）販売、商品名『ＧＥＮＵＶＩＳＣＯ ＰＪ』）をそれぞれ２質量部にソルビトール１質量部、ショ糖ステアリン酸エステル（三菱化学フーズ（株）、商品名『シュガーエステルＳ１６７０』）０．０１質量部、グリセリン２質量部、及びエタノール１質量部を脱イオン水１００質量部に溶解し、試料１と同様の方法でフィルムを製造した。その結果、平衡水分約１３％の厚さ３０μｍのフィルム試料６を得た。
＜試料７＞
アミロース（シグマ社販売、商品名『タイプスリー』）６質量部、寒天（松木寒天産業（株）販売）６質量部、コンドロイチン硫酸ナトリウム（マルハ（株）販売）３質量部にソルビトール１質量部、ショ糖ステアリン酸エステル（三菱化学フーズ（株）、商品名『シュガーエステルＳ１６７０』）０．０１質量部、グリセリン２質量部、及びエタノール１質量部を脱イオン水１００質量部に溶解し、試料１と同様の方法でフィルムを製造した。その結果、平衡水分約１３％の厚さ３０μｍのフィルム資料７を得た。
＜試料８＞
プルラン（（株）林原商事販売、商品名『ＰＩ２０』）１０質量部、アルギン酸ナトリウム（君津化学工業（株）販売、商品名『君津アルギンＵＬＶ−２０』２質量部、コンドロイチン硫酸ナトリウム（（株）マルハ販売）３質量部にソルビトール１質量部、ショ糖ステアリン酸エステル（三菱化学フーズ（株）、商品名『シュガーエステルＳ１６７０』）０．０１質量部、グリセリン２質量部、及びエタノール１質量部を脱イオン水１００質量部に溶解し、試料１と同様の方法でフィルムを製造した。その結果、平衡水分約１３％の厚さ３０μｍのフィルム試料８を得た。
＜試料９＞
プルラン（（株）林原商事販売、商品名『ＰＩ２０』）１５質量部、ショ糖ステアリン酸エステル（三菱化学フーズ（株）、商品名『シュガーエステルＳ１６７０』）０．０１質量部、及びエタノール１質量部を脱イオン水１００質量部に溶解し、試料１と同様の方法でフィルムを製造した。その結果、平衡水分約９％の厚さ３０μｍのフィルム試料９を得た。
＜試料１０＞
プルラン（（株）林原商事販売、商品名『ＰＩ２０』）１５質量部、ショ糖ステアリン酸エステル（三菱化学フーズ（株）、商品名『シュガーエステルＳ１６７０』）０．０１質量部、グリセリン５質量部、及びエタノール１質量部を脱イオン水１００質量部に溶解し、試料１と同様の方法でフィルムを製造した。その結果、平衡水分約１４％の厚さ３０μｍのフィルム試料１０を得た。
＜試料１１＞
プルラン（（株）林原商事販売、商品名『ＰＩ２０』）１２質量部、κ型のみからなるカラギーナン（三晶（株）販売、商品名『ＧＥＮＵＧＥＬ ＷＧ−１１５』）、３質量部に、ショ糖ステアリン酸エステル（三菱化学フーズ（株）、商品名『シュガーエステルＳ１６７０』）０．０１質量部、及びエタノール１質量部を脱イオン水１００質量部に溶解し、試料１と同様の方法でフィルムを製造した。その結果、平衡水分約１０％の厚さ３０μｍのフィルム試料１１を得た。
＜試料１２＞
プルラン（（株）林原商事販売、商品名『ＰＩ２０』）１２質量部、κ：λ＝７：３の比率で含有するカラギーナン（三晶（株）販売、商品名『ＧＥＮＵＶＩＳＣＯ ＣＳＷ−２』）３質量部に、ショ糖ステアリン酸エステル（三菱化学フーズ（株）、商品名『シュガーエステルＳ１６７０』）０．０１質量部、及びエタノール１質量部を脱イオン水１００質量部に溶解し、試料１と同様の方法でフィルムを製造した。その結果、平衡水分約１１％の厚さ３０μｍのフィルム試料１２を得た。
＜試料１３＞
特開平５−３０８９１０号公報の実施例３に記載されている組成に準拠しフィルムを製造した。すなわち、プルラン（（株）林原商事販売、商品名『ＰＩ２０』）１２質量部、κ型のみからなるカラギーナン（三晶（株）販売、商品名『ＧＥＮＵＧＥＬ ＷＧ−１１５』）２質量部に、アルギン酸ナトリウム（君津化学工業（株）販売、商品名『君津アルギンＵＬＶ−２０』）２質量部、ショ糖ステアリン酸エステル（三菱化学フーズ（株）、商品名『シュガーエステルＳ１６７０』）０．０１質量部、及びグリセリン４質量部を脱イオン水１００質量部に溶解し、アプリケーター（ヨシミツ精機（株）販売、商品名『ベーカーアプリケーターＹＢＡ型』を用い、ガラス平板上にポリエチレンテレフタレートを密着させたものの上に、適量滴下し、流延したのち、その表面に５％塩化カルシウム溶液をスプレーし、８５℃で１０分間加熱乾燥した後、２５℃、相対湿度５５％で１６時間乾燥して平衡水分約１３％の厚さ３０μｍのフィルム試料１３を得た。
＜試料１４＞
アミロース（シグマ社販売、商品名『タイプスリー』）８質量部、寒天（松木寒天産業販売（株））８質量部に、ソルビトール１質量部、ショ糖ステアリン酸エステル（三菱化学フーズ（株）、商品名『シュガーエステルＳ１６７０』）０．０１質量部、グリセリン２質量部、及びエタノール１質量部を脱イオン水１００質量部に溶解し、試料１と同様の方法でフィルムを製造した。その結果、平衡水分約１３％の厚さ３０μｍのフィルム試料１４を得た。
＜試料１５＞
プルラン（（株）林原商事販売、商品名『ＰＩ２０』）８質量部、アミロース（シグマ社販売、商品名『タイプスリー』）４質量部、ソルビトール１質量部、ショ糖ステアリン酸エステル（三菱化学フーズ（株）、商品名『シュガーエステルＳ１６７０』）０．０１質量部、グリセリン２質量部、及びエタノール１質量部を脱イオン水１００質量部に溶解し、試料１と同様の方法でフィルムを製造した。その結果、平衡水分約１３％の厚さ３０μｍのフィルム試料１５を得た。
試料１ないし１５のフィルムを、１０ｃｍ平方に切断し、２枚重ねにした後、（株）富士インパルス販売のヒートシール装置である商品名『富士インパルスシーラーＦＩ−２００−１０Ｗ型』を使用して、１４０℃で３秒間の条件で、周辺部３辺をヒートシールし、袋状に成形した。次に、市販のグラニュー糖をすり鉢で細かく砕き、メッシュパスにより、粒径０．０６３乃至０．１２５ｍｍのものを分画し、その２ｇを入れた後、空気を極力除去しつつ手で押さえながら、残りの一辺を同様にヒートシールして封止し、包装体を作製した。これを２５℃、相対湿度５５％、２５％、１０％の乾燥環境下で１週間放置した。
各フィルム試料の水分含量は、電気抵抗により水分含量を測定する装置である（株）ケット科学研究所販売の紙水分計、商品名『Ｋ−２００』を用いて、ライナー紙の設定で測定した。また、ヒートシールの剥離の評価は、５５％、２５％、１０％で放置したものを、１５ｃｍ×２０ｃｍ×５ｃｍの紙製の箱にいれ、蓋をしめた後、左右上下に１０回ずつ回転させた場合、内容物のグラニュー糖が包装外にこぼれていなければ、実質的にヒートシール部に剥離がないと判断した（剥離がない場合を「○」、ある場合を「×」）。また、溶解性の評価は、８０℃の温水３００ｍｌが入っている５００ｍｌビーカーに投入し、５分以内に内容物のグラニュー糖が完全に溶解するかどうかで判定した（溶解すれば「○」、しなければ「×」）。粘着性は、相対湿度８０％で１６時間保存し、水分が平衡化したフィルムを２枚重ね合わせ、手で軽く押さえつけた後、付着しているか（付着してなければ「○」、していれば「×」）により評価した。各フィルムの成分を表２、結果を表３に示す。

表３に示すとおり、本発明による試料１乃至８は、どれもが、相対湿度２５％の環境下で放置したとき、ヒートシール部に剥離が起こっておらず、溶解性及び粘着性も良好であった。また、ヒートシールされていないフィルム部分についても、柔軟性が保持されており、十分な強度を有していた。一方、試料９は、ヒートシール部に剥離のないヒートシールをすることができず、試料１０は、相対湿度２５％の環境下でヒートシール部に剥離が起きなかったが、相対湿度８０％の環境下において、粘着性が強いという欠点を有していた。試料１１及び１２では、相対湿度２５％の環境下でヒートシール部の剥離が起こった。また、特開平５−３０８９１０号公報の実施例３に開示されるフィルムの組成に準拠し再現した試料１３のフィルムは、相対湿度２５％の環境下で剥離が起き、さらに、８０℃の温水には溶解せず、水溶性を有していなかった。また、試料１４では、硫酸基を有しない水溶性多糖類として、プルラン以外のもの、すなわち、アミロース及び寒天を用いた場合でも、硫酸基を有する水溶性多糖類を含有していなければ、好適なヒートシールをすることはできず、試料１５では、プルランと硫酸基を有しないアミロースを組み合わせた場合でも、硫酸基を有する水溶性多糖類の配合がなければ好適なヒートシールをすることはできなかった。また、硫酸基を有する水溶性多糖類の配合がないフィルムは、ヒートシール部分のみならず、ヒートシールされていないフィルム部分の柔軟性がなく、極めて脆くなっていた。したがって、本発明のフィルムは、乾燥環境下での保存に有利であることから、内容物として、水分を含まないもの、例えば粉体、顆粒、固体、乾物などの包装に適しており、さらにそれを水性媒体に溶解させる用途において、対照品と比較して、優れた物性を有していることが判明した。
実験２：ヒドロキシ化合物含量の多い各種フィルムの比較
実験１におけるグリセリンが水溶性多糖類に対して３３質量％配合されている「試料１０」のフィルムは、フィルム表面の粘着性の点で高湿度での保存に適さないものの、乾燥環境下において有利であると考えられた。そこで、プルラン１５質量部のうち、その一部を他の水溶性多糖類であるκ型カラギーナン（三晶（株）販売、商品名『ＧＥＮＵＶＩＳＣＯ ＳＷＧ−Ｊ』）、ローカストビーンガム（（三晶（株）販売））、キサンタンガム（大日本製薬（株）販売）、グリセリン脂肪酸エステル（理研ビタミン（株）、商品名『ポエム Ｇ−００２』）に置き換え、ソルビトール１質量部、ショ糖ステアリン酸エステル（三菱化学フーズ（株）、商品名『シュガーエステルＳ１６７０』）０．０１質量部、グリセリン５質量部、及びエタノール１質量部を加えて、８５℃で１５分間加熱乾燥して、実験１の試料１の方法に準じてフィルムを作製した。作製したフィルムを、（株）富士インパルス販売のヒートシール装置である商品名『富士インパルスシーラー ＦＩ−２００−１０Ｗ型』を使用して、相対湿度４０％の環境下で、１８０℃で１秒間の条件で、周辺部３辺をヒートシールし、相対湿度２５％及び１０％の環境下での保存状況を実験１と同様にして評価した。また、フィルム強度およびヒートシール部の強度を、日本工業規格ＪＩＳＺ１７０７に準拠し、レオメーター（（株）レオテック製造、商品名『ＲＴ−２０１０Ｊ−ＣＷ』）を用いて常法にしたがい測定した。
その結果、プルランとカラギーナンの比率が１０：６乃至６：９の範囲内の場合、相対湿度２５％及び１０％の環境下でも剥離が起きることがなかった。さらに、ローカストビーンガムをプルランに対して０．４乃至３０質量％、キサンタンガムをプルランに対して０．１乃至約１０質量％、及び、グリセリン脂肪酸エステルをプルラン、カラギーナン及びグリセリンの総量に対して１乃至１０質量％配合すると、フィルム強度及びヒートシール強度が著しく高められた。また、相対湿度６０％を超える環境下でヒートシールを行うことに適していないものの、相対湿度８０％の環境下に保存してもフィルム表面の粘着性は弱く、また、１８０℃以上の温度であってもヒートシールが可能となった。この結果は、調湿用材としてのグリセリンが比較的多く（水溶性多糖類の２０質量％以上）配合されているフィルムにおいて、水溶性多糖類としてプルラン、カラギーナンを配合すると、極めて乾燥環境下における使用及び保存に優れ、さらに、ローカストビーンガム、キサンタンガム及びグリセリン脂肪酸エステルを配合すると、フィルム強度が著しく改善された乾燥環境に適した水溶性フィルムを製造できることを示している。
以下、実施例により、本発明の水溶性フィルムについて更に詳細に説明する。
実施例１：水溶性フィルム
下記に示す組成のプルラン水溶液を調製し、アプリケーター（ヨシミツ精機（株）販売、商品名『ベーカーアプリケーターＹＢＡ型』を使用して、ガラス平板上にポリエチレンテレフタレートを密着させたものの上に適量滴下し展延し、８５℃で１０分間加熱乾燥した後、２５℃、相対湿度５５％で１６時間放置し、平衡水分約１１％の厚さ３０μｍのフィルムを製造した。
プルラン（（株）林原商事販売、商品名『ＰＩ２０』） ２０質量部
カラギーナン（κ及びλ）
（三晶（株）販売、商品名『ＧＥＮＵＶＩＳＣＯ ＣＳＷ−２』） ３質量部
ソルビトール １質量部
ショ糖ステアリン酸エステル
（三菱化学フーズ（株）、商品名『シュガーエステルＳ１６７０』）０．０１質量部
グリセリン ２質量部
脱イオン水 ７２質量部
本品は水溶性に優れており、これによる包装体は、内容物を開封することなく、水性媒体に浸漬するだけで、内容物を取り出すことができる。また、乾燥環境下でヒートシールに適した水分を保持しており、ヒートシール部が実質的に剥離することがない。また、プルランを主原料としているので、酸素非透過性の特性を有しており、酸化し易い対象物の包装に適している。
実施例２：水溶性フィルム
下記に示す組成のプルラン水溶液を調製し、アプリケーター（ヨシミツ精機（株）販売、商品名『ベーカーアプリケーターＹＢＡ型』を使用して、ガラス平板上にポリエチレンテレフタレートを密着させたものの上に適量滴下し展延し、８５℃で１０分間加熱乾燥した後、２５℃、相対湿度５５％で１６時間放置し、平衡水分約１２％の厚さ３０μｍのフィルムを製造した。
プルラン（（株）林原商事販売、商品名『ＰＩ２０』） ２０質量部
カラギーナン（ι）
（三晶（株）販売、商品名『ＧＥＮＵＶＩＳＣＯ ＰＪ』） ２．２質量部
粉末状大豆蛋白（不二製油（株）、商品名『フジプロ』） １質量部
α，α−トレハロース（（株）林原商事販売、商品名『トレハ』） １質量部
ショ糖ステアリン酸エステル
（三菱化学フーズ（株）、商品名『シュガーエステルＳ１６７０』）０．０１質量部
グリセリン ２質量部
脱イオン水 ７２質量部
本品は水溶性に優れており、これによる包装体は、内容物を開封することなく、水性媒体に浸漬するだけで、内容物を取り出すことができる。また、乾燥環境下でヒートシールに適した水分を保持しており、ヒートシール部が実質的に剥離することがない。また、プルランを主原料としているので、酸素非透過性の特性を有しており、酸化し易い対象物の包装に適している。
実施例３：水溶性フィルム
下記に示す組成のプルラン水溶液を調製し、アプリケーター（ヨシミツ精機（株）販売、商品名『ベーカーアプリケーターＹＢＡ型』を使用して、ガラス平板上にポリエチレンテレフタレートを密着させたものの上に適量滴下し展延し、８５℃で１０分間加熱乾燥した後、２５℃、相対湿度５５％で１６時間放置し、平衡水分約１１％の厚さ３０μｍのフィルムを製造した。
プルラン（（株）林原商事販売、商品名『ＰＩ２０』） ２０質量部
カラギーナン（κ）
（三晶（株）販売、商品名『ＧＥＮＵＧＥＬ ＷＧ−１１５』） １質量部
カラギーナン（κ及びλ）
（三晶（株）販売、商品名『ＧＥＮＵＶＩＳＣＯ ＣＳＷ−２』） １質量部
カラギーナン（ι）
（三晶（株）販売、商品名『ＧＥＮＵＶＩＳＣＯ ＰＪ』） １質量部
ソルビトール １質量部
ショ糖ステアリン酸エステル
（三菱化学フーズ（株）、商品名『シュガーエステルＳ１６７０』）０．０１質量部
グリセリン ２質量部
脱イオン水 ７２質量部
本品は水溶性に優れており、これによる包装体は、内容物を開封することなく、水性媒体に浸漬するだけで、内容物を取り出すことができる。また、乾燥環境下でヒートシールに適した水分を保持しており、ヒートシール部が実質的に剥離することがない。また、プルランを主原料としているので、酸素非透過性の特性を有しており、酸化し易い対象物の包装に適している。
実施例４：水溶性フィルム
下記に示す組成のプルラン水溶液を調製し、アプリケーター（ヨシミツ精機（株）販売、商品名『ベーカーアプリケーターＹＢＡ型』を使用して、ガラス平板上にポリエチレンテレフタレートを密着させたものの上に適量滴下し展延し、８５℃で１５分間加熱乾燥した後、２５℃、相対湿度５５％で１６時間放置し、平衡水分約１３％の厚さ３０μｍのフィルムを製造した。
プルラン（（株）林原商事販売、商品名『ＰＩ２０』） ４質量部
ローカストビーンガム（三晶（株）販売） ０．７質量部
キサンタンガム（大日本製薬（株）販売） ０．１質量部
カラギーナン（κ）
（三晶（株）販売、商品名『ＧＥＮＵＶＩＳＣＯ ＳＷＧ−Ｊ』） ３質量部
グリセリン ３．５質量部
グリセリン脂肪酸エステル
（理研ビタミン（株）、商品名『ポエム Ｇ−００２』） ０．１５質量部
ショ糖ステアリン酸エステル
（三菱化学フーズ（株）、商品名『シュガーエステルＳ１６７０』）０．０１質量部
脱イオン水 ８４質量部
本品は水溶性に優れており、これによる包装体は、内容物を開封することなく、水性媒体に浸漬するだけで、内容物を取り出すことができる。また、乾燥環境下でヒートシールに適した水分を保持しており、ヒートシール部が実質的に剥離することがない。本品は、相対湿度６０％を超えるような高湿度環境下においては使用及び保存に適していないものの、相対湿度１０％以下の厳しい乾燥環境下において使用及び保存可能であり、さらに、１８０℃以上の温度でヒートシールすることも可能なフィルムである。
実施例５：水溶性フィルムでコートされたガーゼ
下記に示す組成のプルラン水溶液を調製し、これを刷毛でガーゼに塗布し、ガラス平板上にポリエチレンテレフタレートを密着させたものの上によく延ばして置き、さらに上記溶解液を加え、よく浸漬させた後、８５℃で１５分間加熱乾燥した後、２５℃、相対湿度５５％で１６時間放置し、平衡水分約１１％の水溶性フィルムでコートされたガーゼを製造した。
プルラン（（株）林原商事販売、商品名『ＰＩ２０』） １４質量部
カラギーナン（κ及びλ）
（三晶（株）販売、商品名『ＧＥＮＵＶＩＳＣＯ ＣＳＷ−２』） ７質量部
ソルビトール １質量部
ショ糖ステアリン酸エステル
（三菱化学フーズ（株）、商品名『シュガーエステルＳ１６７０』）０．０１質量部
グリセリン ２質量部
脱イオン水 ７２質量部
本品は水溶性フィルムによって、ガーゼの目が埋められているので、ヒートシールが可能であり、密封性に優れている。また、内容物を開封することなく、水性媒体に浸漬するだけで、内容物を取り出すことができる。また、乾燥環境下でヒートシールに適した水分を保持しており、ヒートシール部が実質的に剥離することがない。また、プルランを主原料としているので、酸素非透過性の特性を有しており、酸化し易い対象物の包装に適している。
実施例６：インスタントコーヒー
実施例１又は実施例４で製造したフィルムを１辺が４ｃｍの正方形に切り取り、２枚重ねとしたのちに、ヒートシール装置（（株）富士インパルス販売、商品名『富士インパルスシーラーＯＰＬ−２００−１０』）を用いて、実施例１のフィルムは１３０℃、３秒間のヒートシール条件下、実施例４のフィルムは１８０℃、１秒間のヒートシール条件下、３辺をヒートシールし、袋状としたもののなかに、市販のインスタントコーヒーを、２乃至５ｇを入れた後に、残る一辺を同じ条件でヒートシールした。
本品は、開封することなく、そのままコーヒーカップに入れ、熱湯を注ぐことができるので、開封する手間、及び、コーヒー粉末の計量する手間が省け、かつ粉末が飛散することがないので、取扱いが簡便である。
実施例７：紅茶パック
紅茶パック用のネット基材を、実施例２で製造したフィルム２枚で挟み、アイロンを用いて高熱高圧下でフィルムの全面をヒートシールし、ネット基材をフィルムによって網目の隙間を埋めた。これを用いて、常法により紅茶パックを製造した。
本品において用いたフィルムは、可食性かつ水溶性であるため、本品を湯又は水に浸漬することにより、容易に紅茶が抽出でき、かつ抽出残渣の廃棄処理も容易である。また、本品は、気密性に優れるので紅茶の品質劣化を防止することができる。また、フィルムにより隙間を埋められたネット基材を用いる封入物は、紅茶以外にも、例えば、緑茶、ハーブ茶、ウーロン茶などの茶類、シイタケ、削カツオブシ、昆布などのダシ類などにも有利に適用できる。
実施例８：洗剤
実施例３又は４で製造したフィルムを、縦１０ｃｍ、横７ｃｍの長方形になるように、実施例３のフィルムは１３０℃、３秒間のヒートシール条件下、実施例４のフィルムは１８０℃、１秒間のヒートシール条件下でヒートシールした後に、切り離し、一辺のヒール部を切り離し、袋状とした。これに市販の粉末洗剤を５ｇ入れ、再度ヒートシールして密封した。これを５袋一組で、適度の大きさのポリエチレン袋に入れた後に、ポリエチレン袋をヒートシールして密封した。
本品は、ポリエチレン袋から取り出した後に、封を切らずに洗濯機などの水槽に投入すればよいので、計量する手間が省けるうえに、洗剤を手に付着することがなく、また、飛散させることなく取り扱うことができる。また、密封性、酸素非透過性にすぐれるので、洗剤の効力を持続させることができる。
実施例９：入浴剤
硫酸ナトリウム粉末６０質量部、炭酸水素ナトリウム粉末２７質量部、二酸化チタン粉末１質量部、ラウリル硫酸ナトリウム粉末１質量部、シリコン樹脂消泡剤を適量及び香料を適量混合し、入浴剤を作製した。一方、実施例５で製造したガーゼを、１辺が１２ｃｍの正方形に切り取り、２枚重ねとしたのちに、ヒートシール装置（（株）富士インパルス販売、商品名『富士インパルスシーラーＯＰＬ−２００−１０』）を用いて、１３０℃、３秒間のヒートシール条件下、３辺をヒートシールし、袋状としたもののなかに、上記入浴剤を１０乃至１５ｇを入れた後に、残る一辺を同じ条件でヒートシールした。
本品は、開封することなく、そのまま浴槽に投入することができるので、開封する手間が省け、入浴剤の粉末が飛散することがないので、取扱いが簡便である。The water-soluble film of the present invention comprises one or more water-soluble polysaccharides having no sulfate group and 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 in an environment with a relative humidity of 25%, and is a water-soluble film substantially free of a crosslinking agent.
The water-soluble polysaccharides having no sulfate group used in the present invention are all edible polysaccharides, such as pullulan, erucinan, sodium alginate, agar, pectin, tamarind gum, xanthan gum, guar gum, tara gum, Locust bean gum, arabinogalactan, gum arabic, chitosan, amylose, amylopectin, dextran and the like. Among these, polysaccharides having maltotriose as a repeating unit, that is, pullulan or erucinan are preferable, and pullulan which is easily available is particularly preferable for use in the present invention. In addition to pullulan, it is preferable to use one or more water-soluble polysaccharides other than pullulan having no sulfate group, and it is particularly 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 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 suitably used. However, the present invention is not limited thereto, and other pullulan products can be used, or polysaccharides having other maltotriose as a repeating unit, such as erucinan, can be used without departing from the object of the present invention. Moreover, if necessary, a polysaccharide having maltotriose as a repeating unit derivatized by modification such as esterification with an arbitrary degree of substitution may 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, more preferably 50,000. Selected from the range of 500,000 daltons. Note that the weight average molecular weight and molecular weight distribution of a polysaccharide having maltotriose as a repeating unit are factors that determine the dissolution rate of the film. Therefore, an appropriate weight average molecular weight and molecular weight distribution maltotriose should be used depending on the application. A polysaccharide as a repeating unit may be used. Although it depends on other ingredients to be blended, generally, when the weight average molecular weight of the polysaccharide having maltotriose as a repeating unit is less than 10,000 Dalton, film formation becomes difficult, and 1,000,000 Dalton If it exceeds, the dissolution rate in the aqueous solvent will be too low, which may be undesirable.
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 sufficiently exhibit the effect in the water-soluble film of the present invention, those having 0.5 or more sulfate groups per constituent monosaccharide, more preferably those having 1 or more are preferable. Natural polysaccharides such as carrageenan, chondroitin sulfate, heparan sulfate, deltaman sulfate, and heparin, or salts thereof, or water-soluble polysaccharides that originally do not have sulfate groups, and have sulfate groups. In addition, it is possible to use a water-soluble polysaccharide whose number of sulfate groups per constituent monosaccharide does not reach 0.5 by sulfation by an appropriate method, for example, using an enzyme reaction or a chemical reaction. it can. In the present invention, carrageenan is preferably used because it is easily available and excellent in imparting physical properties such as strength and flexibility of the film. Water-soluble polysaccharides with sulfate groups can increase the moisture retention, flexibility, film strength, and heat seal strength of the film in a dry environment, and are especially heat-sealed with the heat seal portion, which tends to be brittle. It is possible to increase the strength of the boundary portion of the portion that is not. Moreover, it has the effect of reducing the adhesiveness of the film surface resulting from mix | blending a humidity control material in large quantities.
Carrageenan is a water-soluble polysaccharide whose unit structure is a disaccharide composed of D-galactose and 3,6-anhydro-D-galactose contained in the red algae extract. The type of sugar and the number of sulfate groups Depending on the position, five types of κ (kappa) type, ι (iota) type, λ (lambda) type, μ (mu) type, and ν (new) type are known (see Table 1). As the carrageenan used in the present invention, a commercially available carrageenan product can be used regardless of the type, origin and production method. In particular, κ-type having 0.5 sulfate groups per constituent monosaccharide and λ and ι-type carrageenans having one sulfate group per constituent monosaccharide are easily available and can be advantageously used in the present invention. The κ-type carrageenan is excellent in improving the strength of the film, and the λ and ι-type carrageenan is excellent in improving the water retention and flexibility of the film. Therefore, in the film of the present invention, it is preferable to contain various types of carrageenan in combination.

The humidity control material used in the present invention includes various hydroxy compounds, particularly non-volatile hydroxy compounds, such as erythritol, xylitol, sorbitol, maltitol, α, α-trehalose, glycosyl α, α-trehalose, and cyclic oligosaccharides. , Glycosyl cyclic oligosaccharides, polyols such as glycerin, or derivatives thereof. These can be used alone or in combination of two or more. Among these, it is preferable to contain glycerin, and in addition to these, it is preferable to contain sorbitol or α, α-trehalose.
When the blending ratio of the humidity control material is relatively high, blend fats such as lecithin and palm oil, sugar fatty acid esters such as sucrose stearate, fatty acid esters such as glycerin fatty acid ester and propylene glycol fatty acid ester. Thereby, the adhesiveness of the film surface can be reduced. Among these, it is preferable to contain glycerol fatty acid ester and sugar fatty acid ester.
As a ratio of each compounding component in the water-soluble film of the present invention, a water-soluble polysaccharide having a sulfate group is blended within a range of 15 to 150% by mass with respect to a water-soluble polysaccharide having no sulfate group. Moreover, a hydroxy compound is mix | blended within the range of 1-50 mass% with respect to water-soluble polysaccharide whole quantity. However, when the compounding ratio of the hydroxy compound with respect to the total amount of the water-soluble polysaccharide exceeds 20% by mass, the film strength is lowered and the adhesiveness on the surface of the film becomes remarkable. It is desirable to use pullulan, locust bean gum and xanthan gum as the active polysaccharide, and the total amount of locust bean gum and xanthan gum is preferably in the range of 0.5 to 40% by mass with respect to the pullulan. Furthermore, when the mixing ratio of the hydroxy compound with respect 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 preferably 50 to 150% by mass, preferably By blending lipids or fatty acid esters in the range of 1 to 10% by mass with respect to the total amount of water-soluble polysaccharides and hydroxy compounds, and / or within the range of 60 to 120% by mass Strength and adhesiveness of the film surface can be reduced.
In addition to the above-described components, the water-soluble film of the present invention may appropriately contain other components within a range that does not interfere with the object of the present invention. Examples of substances that can be contained include proteins such as soybean protein and gelatin and their degradation products, volatile alcohols such as ethanol, pigments, fragrances, and derivatives thereof.
As a method for producing the film of the present invention, an appropriately viscous solution state is obtained with an aqueous solvent such as water or ethanol, and according to a conventional method, a casting method, an extrusion method, a spray method, a roll coating method, a dipping method. After forming a thin film by such a method, a method of forming a film by drying at room temperature or a temperature exceeding room temperature can be mentioned.
The film thus obtained usually has the purpose of being dissolved by immersing in an aqueous solvent after packaging. Therefore, the film needs to have water solubility. The rate of dissolution in an aqueous medium takes into account the type, amount and temperature of the solvent, the strength of stirring, the moisture content of the film during dissolution, the shape of the film, such as the thickness and size, and the weight of the water-soluble polysaccharide. It can be carried out by appropriately selecting the average molecular weight, the molecular weight distribution of the water-soluble polysaccharide, the ratio of various water-soluble polysaccharides, and the mixing ratio of various hydroxy compounds. In the film of the present invention, depending on the use, when it is poured into warm water at 80 ° C., it is usually water-soluble so that the contents hermetically packaged in the film is released within 5 minutes, more preferably within 3 minutes. It is desirable to configure so as to give sex. In addition, in the film of this invention, since it is desired that water solubility is higher, you must not contain the crosslinking agent which forms the water-insoluble crosslinked structure which causes the water solubility of a film to fall. Depending on the water-soluble polysaccharide to be contained, it is desirable to exclude substances such as minerals such as calcium, which have an action of forming a water-insoluble crosslinked structure, from each compounding component.
The thickness of the water-soluble film of the present invention may be determined according to the application, but is usually selected from the range of 1 μm to 100 μm, preferably 10 μm to 50 μm. If the thickness is less than 1 μm, it is not preferable because it is easy to break. If the thickness exceeds 100 μm, the dissolution time in a solvent such as water becomes too long, or the amount of components of the film eluted in the solvent increases too much. It may not be preferable.
The water-soluble film of the present invention has an equilibrium water content of about 10 to about 15 in a dry environment in which the film is used and stored, specifically in an environment with a relative humidity of about 25%, preferably about 10%. %, Preferably about 11 to about 14%, by adjusting the ratio of the blending components, it will have characteristics such as heat sealability, film strength and flexibility.
In the present invention, heat sealing refers to bonding by heating and press-bonding a film in which two or more sheets are overlapped or a film part in which two or more sheets are partially overlapped. In general, a film is formed in a bag shape by superimposing films or folding a single film and heat-sealing the periphery. Such a shape is advantageously applied, for example, when the content is in the form of powder, granules, oily paste, or oily liquid. Usually, heat sealing is performed on a part of the film. However, if the content is a heat-resistant sheet, the entire surface of the film including the content can be heat sealed. . In addition, when heat sealing packaging is performed with a plurality connected, each can be separated after packaging, or perforations can be inserted to facilitate separation. In the case of a relatively large solid, after wrapping an object to be wrapped with one or a plurality of films, the overlapped film can be adhered by heat sealing to form a package. In addition, if necessary, it can be packaged in an inert gas or vacuum to prevent the gas such as oxygen and water vapor from deteriorating the quality of the packaged object, and it can be packaged aseptically. It is also optional to do.
As a heat seal apparatus, it can carry out using the apparatus which carries out thermocompression bonding, for example, a heat bar type, a roll type, a pillow type, an impulse packaging machine, a high frequency packaging machine, etc. In order to perform better heat sealing, a model that can control the temperature of the heat sealing portion is desirable. For example, as a commercially available heat sealing device, a product name “Fuji Impulse Sealer OPL-200-” sold by Fuji Impulse Corporation. 10 ”or the like can be used. When using such a heat-controllable heat sealing device, the temperature of the part to be sealed is usually in the range of 100 to 200 ° C., preferably 110 to 160 ° C., preferably 120 to 140 ° C. When the heat sealing time is set within a range of 1 to 4 seconds, the heat sealing is hardly failed.
The packaging body of the film of the present invention needs to be sufficiently sealed so that the contents do not substantially spill out of the packaging body during storage, and the pressure assumed to be applied to the film It is desirable to have sufficient strength to withstand tension, shearing force, vibration and the like. The strength of the film and the strength of the heat seal part can be measured using, for example, a rheometer (manufactured by Rheotech Co., Ltd., trade name “RT-2010J-CW”) in accordance with Japanese Industrial Standard JISZ1707. Depending on the application, the relative strength of the storage environment usually has a film strength of 100 gf or more, preferably 150 gf or more, and a heat seal strength of 150 gf / 15 mm width or more, preferably 250 gf / 15 mm width or more. desired.
The film of the present invention is used for foods, cosmetics, pharmaceuticals, chemical packaging, etc. in the form of solids, powders, granules, tablets, creams, emulsions, mass kits, pastes, oily liquids, etc. In this way, it is possible to prevent the oxidation of the contents due to oxygen in the air, and even if it is in a packaged state, it can be eaten, put into an appropriate solvent as it is, or even if the solvent is poured into the package, The package can dissolve and the contents can be released into the solvent. In addition, if a water-resistant substance such as fat or oil is coated on the side in contact with the content of the film, a content containing a lot of moisture or an aqueous liquid can be used. Since the film of the present invention does not always require opening of the package, it saves the trouble of opening the package, and further, there is no risk of scattering the packaged object at the time of opening, so the user can contaminate hands, fingers, clothes, etc. Can be used without paying attention to the suction to the respiratory organs. Therefore, if it is applied not only to the food, cosmetics, and pharmaceutical fields but also to packaging of highly dangerous substances such as poisons, powerful drugs, and carcinogenic substances, the handling of these substances can be made safe and easy. In addition, as another usage pattern of the water-soluble film of the present invention, it can be used in a partially opened state, for example, in a bag shape or a cylindrical shape. In addition, a method other than heat sealing, for example, a method of joining using an adhesive such as starch or protein, a method of stacking or folding the film, and fixing with a fastener or the like can also be employed. In addition, if desired, multiple packaging may be performed with one or more films of the present invention, or multiple packaging may be performed using other packaging materials in combination. Moreover, although heat sealability is inferior, another film and the film of the present invention can be heat sealed to form a laminate film. In addition, when the film of the present invention is produced, the raw material of the film of the present invention is cast on another film, such as polyethylene, nylon, paper, etc., coated, soaked and then dried. If a film is prepared, a double film can be produced, and heat sealability can be imparted even to a film that could not be heat sealed originally. In particular, when applied to a film-like material having a network structure, such as cloth, gauze, filter paper, non-woven fabric, and net, the gap can be filled. It can be advantageously applied to take-out bags such as potatoes and soups.
Examples of food products 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, processed products such as pickles, Sesame paste such as sesame paste, nut paste, corn paste, ginger, powdered rice cake, potato flour, sweet potato flour, yam flour, sesame, brown rice, wheat, barley, rye, soybeans, corn, peanuts, almonds, coffee beans , Seeds such as cocoa beans or pulverized products thereof, polished rice (white rice), germinated rice, washed rice, polished white barley, polished white wheat, polished millet such as millet, rice flour, wheat flour, barley flour, rye flour, pigeon flour, soybean Agricultural products such as flour, soybean germ powder, buckwheat flour, corn flour and other cereal grains, ground sesame seeds, potato flour, kinako flour, seeded processed products such as coarsely ground coffee, Seafood products such as eagle paste, oyster meat extract, sea urchin paste, horse mackerel, fish meat, shaved cutlet, kelp, fish meal, livestock products such as livestock meat, milk, milk cream, chicken, chicken eggs, soy sauce, miso, sauce, mayonnaise, Paste or liquid seasonings such as dressings, powdered fats and oils, spices, seasonings such as powdered seasonings such as sprinkles, fertilizer, rice crackers, fried beans, fried beans, karinto, fried rice crackers, castella and other Japanese sweets, chocolate, chewing gum, bread, Cakes, confectionery, cream confectionery, snack confectionery and other confectionery, ice cream, sherbet and other frozen confectionery, green tea, roasted tea, black tea, oolong tea, brown rice tea, barley tea, pigeon tea and other teas, cooked rice, steamed rice, rice flour, rice cake, rice balls Processed rice products such as porridge, rice porridge, fried rice, pilaf, pasta, bread, pizza, naan, bread crumbs, Processed wheat products such as premixes, soy milk, tofu, thickened, okara, okara hamburg, soy milk pudding and other processed soybean products, koji, amazake, sake, mirin, beer, distilled liquor, vinegar, miso, soy sauce, pickles , Fermented foods and drinks such as pickles, pickles, miso pickles, tamari pickles, processed meat products such as ham and sausage, fish paste products such as kamaboko, chikuwa, hanpen, salted fish using sea urchin, squid, meat, dried fish , Delicacies using small fish, shrimp, squid, shellfish, livestock meat, boiled beans, boiled beans, salad, fried food, fried food, boiled food, fried egg, grilled meat, yakitori, hamburger, gyoza, tempura, tempura Milk processed products such as condensed milk, powdered milk, yogurt, cheese, coffee fresh, etc., Bavaria, mousse, marshmallow, pudding, cream puff, broiled egg, broiled egg, steamed egg, mayonnaise, and other tea products Powdered soft drinks such as tea drinks, amazake, coffee drinks, milk drinks, lactic acid bacteria drinks, liquid oils such as salad oil, olive oil, and koji oil, solid fats such as butter and margarine, sake, wine, liqueur, etc. Alcoholic beverage powders, frozen foods, baby food, therapeutic foods, health foods, peptide foods, etc., for example, cereal pellets, cereal powder, vegetable oil cake, fermented rice cake, rice cake, wheat cake, barley cake, defatted rice cake Feed ingredients such as defatted soybeans, fish meal, fish soluble, meat powder, blood powder, feather powder, skim milk powder, dried whey, pupa lees, alfa meal, etc. Examples include seedlings.
Examples of cosmetic articles that can be packaged with the film of the present invention include toothpaste, lipstick, lip balm, fragrance in mouth, mouthwash, bathing agent, antiperspirant, soap, shampoo, rinse, body soap, body lotion. , Deodorant agents, hair creams, fairing agents, skin beautifiers, hair cleansing agents, hair restorers and the like.
Examples of articles in the pharmaceutical field that can be packaged with the film of the present invention include drinks, oral nutrients, tube feedings, injectable fat emulsions, troches, liver oil drops and other pharmaceuticals, organs, artificial organs, and the like. .
Examples of chemical products that can be packaged with the film of the present invention include pesticides such as insect repellents, fungicides, and herbicides, photographic agents such as developers, softeners, bleaches, detergents, and other laundry products. Drugs, drugs used in medicine, chemistry or biological research reagents in general, and specimens such as organisms, rocks, soil, etc., including humans such as poisonous substances, deleterious substances, carcinogenic substances, radioactive substances, etc. And harmful 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>
Pullulan (trade name “PI20” sold by Co., Ltd., trade name “PI20”) 12 parts by mass, carrageenan (trade name “GENUGEL WG-115”) consisting only of κ type, 3 parts by mass, sorbitol 1 mass Part, sucrose stearate ester (Mitsubishi Chemical Foods Co., Ltd., trade name “Sugar Ester S1670”) 0.01 parts by mass, glycerin 2 parts by mass, and ethanol 1 part by mass in deionized water 100 parts by mass, Using an applicator (Yoshimitsu Seiki Co., Ltd., trade name “Baker Applicator YBA type”), apply and drop an appropriate amount onto a glass plate with polyethylene terephthalate adhered, and heat at 85 ° C. for 10 minutes. After drying, it was allowed to stand for 16 hours at 25 ° C. and 55% relative humidity to produce a film, resulting in a thickness of 30 with an equilibrium moisture content of about 13%. To obtain a film sample 1 of the m.
<Sample 2>
Pullulan (sales of Hayashibara Corporation, trade name “PI20”) 12 parts by mass, carrageenan contained in a ratio of κ: λ = 7: 3 (sales of Sanki Co., Ltd., trade name “GENUVISCO CSW-2”) 3 Deionize 1 part by mass of sorbitol, 0.01 parts by mass of sucrose stearate (Mitsubishi Chemical Foods, Inc., trade name “Sugar Ester S1670”), 2 parts by mass of glycerin, and 1 part by mass of ethanol. It melt | dissolved in 100 mass parts of water, and the film was manufactured by the method similar to the 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 (sales of Hayashibara Corporation, trade name “PI20”) 12 parts by mass, carrageenan consisting only of ι type (sales of Sanki Co., Ltd., trade name “GENUVISCO PJ”), 1 part by weight of sorbitol, Sample 1 was prepared by dissolving 0.01 part by mass of sucrose stearate ester (Mitsubishi Chemical Foods Co., Ltd., trade name “Sugar Ester S1670”), 2 parts by mass of glycerin, and 1 part by mass of ethanol in 100 parts by mass of deionized water. A film was produced in the same manner as described above. As a result, a film sample 3 having a thickness of 30 μm and an equilibrium water content of about 13% was obtained.
<Sample 4>
Pullulan (sales of Hayashibara Corporation, trade name “PI20”) 12 parts by mass, carrageenan consisting only of κ type (sales of Sanki Co., Ltd., trade name “GENUGEL WG-115”), κ: λ = 7: 3 1% each of carrageenan (trade name “GENUVISCO CSW-2”) and carrageenan consisting only of ι type (trade name “GENUVISO PJ”) 1 part by weight of sorbitol, 0.01 parts by weight of sucrose stearate (Mitsubishi Chemical Foods Co., Ltd., trade name “Sugar Ester S1670”), 2 parts by weight of glycerin, and 1 part by weight of ethanol are added to 100 parts of deionized water. It melt | dissolved in the mass part and the film was manufactured by the method similar to the sample 1. As a result, a film sample 4 having a thickness of 30 μm and an equilibrium water content of about 13% was obtained.
<Sample 5>
Pullulan (sales of Hayashibara Corporation, trade name “PI20”) 12 parts by mass, carrageenan consisting only of κ type (sales of Sanki Co., Ltd., trade name “GENUGEL WG-115”), carrageenan consisting only of ι type (Sanki Co., Ltd., trade name “GENUVISCO PJ”) is each 2 parts by weight of sorbitol 1 part by weight, sucrose stearate (Mitsubishi Chemical Foods Co., Ltd., trade name “Sugar Ester S1670”) 0.01 A film was produced in the same manner as Sample 1 by dissolving 1 part by mass, 2 parts by mass of glycerin, and 1 part by mass of ethanol in 100 parts by mass of deionized water. As a result, a film sample 5 having a thickness of 30 μm and an equilibrium water content of about 13% was obtained.
<Sample 6>
6 parts by mass of amylose (sold by Sigma, trade name "Type Three"), 6 parts by weight of agar (sold by Matsuki Agar Sangyo Co., Ltd.), carrageenan (sold by Sanki Co., Ltd., trade name "GENUGEL WG") -115 ”), and carrageenan consisting only of ι type (sold by Sanki Co., Ltd., trade name“ GENUVISO PJ ”), 2 parts by mass of sorbitol and 1 part of sucrose stearate (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 Sample 1. As a result, a film sample 6 having a thickness of 30 μm and an equilibrium water content of about 13% was obtained.
<Sample 7>
6 parts by weight of amylose (sold by Sigma, trade name “Type Three”), 6 parts by weight of agar (sold by Matsuki Agar Sangyo Co., Ltd.), 3 parts by weight of sodium chondroitin sulfate (sold by Maruha Corporation), 1 part by weight of sorbitol, Sample 1 was prepared by dissolving 0.01 part by mass of sucrose stearate ester (Mitsubishi Chemical Foods Co., Ltd., trade name “Sugar Ester S1670”), 2 parts by mass of glycerin, and 1 part by mass of ethanol in 100 parts by mass of deionized water. A film was produced in the same manner as described above. As a result, a film material 7 having a thickness of 30 μm and an equilibrium water content of about 13% was obtained.
<Sample 8>
Pullulan (sales of Hayashibara Corporation, trade name “PI20”), 10 parts by mass, sodium alginate (sales by Kimitsu Chemical Co., Ltd.), 2 parts by weight of trade name “Kimitsu Argin ULV-20”, chondroitin sodium sulfate (stock) Maruha Sales) 3 parts by weight, 1 part by weight of sorbitol, 0.01 parts by weight of sucrose stearate (Mitsubishi Chemical Foods, Inc., trade name “Sugar Ester S1670”), 2 parts by weight of glycerin, and 1 part by weight of ethanol The film was dissolved in 100 parts by mass of deionized water, and a film was produced in the same manner as Sample 1. As a result, a film sample 8 having a thickness of 30 μm and an equilibrium water content of about 13% was obtained.
<Sample 9>
15 parts by weight of pullulan (trade name “PI20” sold by Hayashibara Corporation), 0.01 parts by weight of sucrose stearate (Mitsubishi Chemical Foods, Inc., trade name “Sugar Ester S1670”), and 1 part by weight of ethanol A part was melt | dissolved in 100 mass parts of deionized water, and the film was manufactured by the method similar to the sample 1. As a result, a film sample 9 having a thickness of 30 μm and an equilibrium water content of about 9% was obtained.
<Sample 10>
Pullulan (trade name “PI20”, sold by Hayashibara Corporation) 15 parts by mass, sucrose stearate (Mitsubishi Chemical Foods, Inc., trade name “Sugar Ester S1670”) 0.01 parts by mass, glycerin 5 parts by mass And 1 mass part of ethanol was melt | dissolved in 100 mass parts of deionized water, and the film was manufactured by the method similar to the sample 1. As a result, a film sample 10 having a thickness of 30 μm and an equilibrium water content of about 14% was obtained.
<Sample 11>
Pullulan (sales by Hayashibara Corporation, trade name “PI20”), 12 parts by mass, carrageenan consisting only of κ type (sales by Sanki Co., Ltd., trade name “GENUGEL WG-115”), 3 parts by weight, sucrose Dissolve 0.01 parts by mass of stearic acid ester (Mitsubishi Chemical Foods Co., Ltd., trade name “Sugar Ester S1670”) and 1 part by mass of ethanol in 100 parts by mass of deionized water. Manufactured. As a result, a film sample 11 having a thickness of 30 μm and an equilibrium water content of about 10% was obtained.
<Sample 12>
Pullulan (sales of Hayashibara Corporation, trade name “PI20”) 12 parts by mass, carrageenan contained in a ratio of κ: λ = 7: 3 (sales of Sanki Co., Ltd., trade name “GENUVISCO CSW-2”) 3 In parts by mass, 0.01 part by mass of sucrose stearate 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 a result, a film sample 12 having a thickness of 30 μm and an equilibrium water content of about 11% was obtained.
<Sample 13>
A film was produced in accordance with the composition described in Example 3 of JP-A-5-308910. That is, pullulan (trade name “PI20” sold by Co., Ltd., trade name “PI20”) 12 parts by mass, carrageenan consisting only of κ type (trade name “GENUGEL WG-115”) 2 parts by mass, alginic acid 2 parts by mass of sodium (Kimitsu Chemical Industry Co., Ltd., trade name “Kimitsu Argin ULV-20”), 0.01 parts by mass of sucrose stearate (Mitsubishi Chemical Foods Co., Ltd., trade name “Sugar Ester S1670”) , And 4 parts by weight of glycerin dissolved in 100 parts by weight of deionized water, and using an applicator (Yoshimitsu Seiki Co., Ltd., trade name “Baker Applicator YBA type”), with polyethylene terephthalate adhered to a glass plate After dropping a suitable amount and casting, spray a 5% calcium chloride solution on the surface and heat dry at 85 ° C for 10 minutes. After afford 25 ° C., and dried at 55% relative humidity for 16 hours of equilibrium water content of about 13% of the thickness of 30μm film samples 13.
<Sample 14>
8 parts by mass of amylose (sold by Sigma, trade name “Type Three”), 8 parts by mass of agar (Matsugi Agar Industrial Sales Co., Ltd.), 1 part by mass of sorbitol, sucrose stearate (Mitsubishi Chemical Foods, Inc.) Product 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 Sample 1. As a result, a film sample 14 having a thickness of 30 μm and an equilibrium water content of about 13% was obtained.
<Sample 15>
Pullulan (trade name “PI20” sold by Hayashibara Corporation), 8 parts by weight, amylose (sold by Sigma, trade name “Type Three”), 4 parts by weight, sorbitol 1 part by weight, sucrose stearate (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 Sample 1. . As a result, a film sample 15 having a thickness of 30 μm and an equilibrium water content of about 13% was obtained.
Samples 1 to 15 were cut into 10 cm squares, stacked in two, and then used as a product name “Fuji Impulse Sealer FI-200-10W” which is a heat seal device sold by Fuji Impulse Corporation. Under the conditions of 140 ° C. for 3 seconds, three sides of the peripheral part were heat-sealed and formed into a bag shape. Next, the commercially available granulated sugar is finely crushed in a mortar, fractionated with a particle size of 0.063 to 0.125 mm by a mesh pass, and 2 g of that is added, while holding the hand while removing air as much as possible. The remaining one side was similarly heat-sealed and sealed to produce a package. This was left to stand for one week in a dry environment of 25 ° C., relative humidity 55%, 25%, and 10%.
The moisture content of each film sample was measured by setting the liner paper using a paper moisture meter, trade name “K-200” sold by Kett Science Laboratory, which is a device for measuring moisture content by electrical resistance. . In addition, the evaluation of heat seal peeling was 55%, 25%, 10% left in a 15cm x 20cm x 5cm paper box, and after closing the lid, it was rotated 10 times horizontally and vertically In this case, if the granulated sugar of the contents was not spilled out of the package, it was determined that there was substantially no peeling at the heat seal part (“◯” when there was no peeling, “X” when there was no peeling). In addition, the solubility was evaluated by whether or not the granulated sugar of the content was completely dissolved within 5 minutes after being put into a 500 ml beaker containing 300 ml of 80 ° C. warm water (“○”, Otherwise, “×”). Tackiness is stored for 16 hours at 80% relative humidity, and two films with water equilibrated are stacked on top of each other and lightly pressed by hand, then attached (“○” if not attached) And “×”). Table 2 shows the components of each film, and Table 3 shows the results.

As shown in Table 3, none of the samples 1 to 8 according to the present invention was peeled off at the heat seal part when left in an environment with a relative humidity of 25%, and the solubility and tackiness were also good. there were. Moreover, the flexibility of the film portion that was not heat-sealed was maintained, and the film portion had sufficient strength. On the other hand, the sample 9 could not be heat-sealed without peeling at the heat seal portion, and the sample 10 did not peel at the heat seal portion in an environment with a relative humidity of 25%, but the relative humidity was 80%. Under the environment, it had a drawback of strong tackiness. In samples 11 and 12, peeling of the heat seal portion occurred in an environment with a relative humidity of 25%. 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 with a relative humidity of 25%, and further heated to 80 ° C. hot water. Did not dissolve and did not have water solubility. Moreover, in the sample 14, even when other than pullulan, that is, amylose and agar, is used as the water-soluble polysaccharide having no sulfate group, it is preferable if it does not contain the water-soluble polysaccharide having a sulfate group. Heat sealing cannot be performed, and in Sample 15, even when pullulan and amylose having no sulfate group are combined, a suitable heat seal cannot be performed unless a water-soluble polysaccharide having a sulfate group is added. It was. Moreover, the film which does not contain the water-soluble polysaccharide having a sulfate group has not only the heat-sealed part but also the film part which is not heat-sealed, and is very brittle. Therefore, since the film of the present invention is advantageous for storage in a dry environment, the contents are suitable for packaging that does not contain moisture, such as powders, granules, solids, and dry matter. It has been found that, in an application in which saponin is dissolved in an aqueous medium, it has excellent physical properties as compared with a control product.
Experiment 2: Comparison of various films with high hydroxy compound content
The film of “Sample 10” in which 33% by mass of glycerin in Experiment 1 is blended with respect to the water-soluble polysaccharide is not suitable for storage at high humidity in terms of the adhesiveness of the film surface, but is advantageous in a dry environment. It was thought that. Therefore, of 15 parts by mass of pullulan, some of the water-soluble polysaccharide, κ-type carrageenan (sold by Sanki Co., Ltd., trade name “GENUVISCO SWG-J”), locust bean gum ((Sanki ( Sales)), xanthan gum (Dainippon Pharmaceutical Co., Ltd.), glycerin fatty acid ester (RIKEN VITAMIN Co., Ltd., trade name “Poem G-002”), 1 part by mass of sorbitol, sucrose stearate ( Mitsubishi Chemical Foods Co., Ltd., trade name “Sugar Ester S1670”) 0.01 parts by mass, 5 parts by mass of glycerin and 1 part by mass of ethanol were added and dried by heating at 85 ° C. for 15 minutes. A film was prepared according to the method. Using the product name “Fuji Impulse Sealer FI-200-10W” which is a heat seal device sold by Fuji Impulse Co., Ltd., the produced film is heated at 180 ° C. for 1 second under an environment with a relative humidity of 40%. Under conditions, three sides of the peripheral part were heat-sealed, and the storage conditions in an environment with a relative humidity of 25% and 10% were evaluated in the same manner as in Experiment 1. Further, the film strength and the strength of the heat seal part were measured according to a conventional method using a rheometer (manufactured by Rheotech Co., Ltd., trade name “RT-2010J-CW”) in accordance with Japanese Industrial Standard JISZ1707.
As a result, when the ratio of pullulan to carrageenan was within the range of 10: 6 to 6: 9, peeling did not occur even in an environment with a relative humidity of 25% and 10%. Furthermore, locust bean gum is 0.4 to 30% by weight with respect to pullulan, xanthan gum is 0.1 to about 10% by weight with respect to pullulan, and glycerin fatty acid ester is 1 with respect to the total amount of pullulan, carrageenan and glycerin. When blended to 10% by mass, the film strength and the heat seal strength were remarkably enhanced. In addition, although it is not suitable for heat sealing in an environment where the relative humidity exceeds 60%, the film surface has low adhesiveness even when stored in an environment where the relative humidity is 80%, and at a temperature of 180 ° C. or higher. Even if there was, heat sealing became possible. As a result, in a film in which a relatively large amount of glycerin as a humidity control material is blended (20% by mass or more of the water-soluble polysaccharide), when pullulan or carrageenan is blended as the water-soluble polysaccharide, it is used in an extremely dry environment. In addition, it shows that when a locust bean gum, a xanthan gum and a glycerin fatty acid ester are blended, a water-soluble film suitable for a dry environment can be produced 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 solution of pullulan having the composition shown below, and drop it onto an applicator (Yoshimitsu Seiki Co., Ltd., brand name “Baker Applicator YBA type”). The film was heated and dried at 85 ° C. for 10 minutes and then allowed to stand at 25 ° C. and a relative humidity of 55% for 16 hours to produce a film having a thickness of 30 μm and an equilibrium water content of about 11%.
Pullulan (trade name “PI20” sold by Hayashibara Corporation) 20 parts by mass
Carrageenan (κ and λ)
(Sanki Co., Ltd., trade name “GENUVISCO CSW-2”) 3 parts by mass
1 part by weight of sorbitol
Sucrose stearate
(Mitsubishi Chemical Foods Co., Ltd., trade name “Sugar Ester S1670”) 0.01 parts by mass
2 parts by mass of glycerin
72 parts by weight of deionized water
This product is excellent in water-solubility, and the package according to this product can be taken out by simply immersing it in an aqueous medium without opening the contents. Moreover, the water | moisture content suitable for heat sealing is hold | maintained in a dry environment, and a heat seal part does not peel substantially. Moreover, since pullulan is used as the main raw material, it has oxygen-impermeable characteristics and is suitable for packaging of objects that are easily oxidized.
Example 2: Water-soluble film
Prepare an aqueous solution of pullulan having the composition shown below, and drop it onto an applicator (Yoshimitsu Seiki Co., Ltd., brand name “Baker Applicator YBA type”). The film was heated and dried at 85 ° C. for 10 minutes, and then allowed to stand at 25 ° C. and a relative humidity of 55% for 16 hours to produce a film having a thickness of 30 μm and an equilibrium water content of about 12%.
Pullulan (trade name “PI20” sold by Hayashibara Corporation) 20 parts by mass
Carrageenan (ι)
(Sanki Co., Ltd., trade name "GENUVISCO PJ") 2.2 parts by mass
1 part by weight of powdered soybean protein (Fuji Oil Co., Ltd., trade name “Fujipro”)
α, α-trehalose (sales by Hayashibara Shoji Co., Ltd., trade name “Treha”) 1 part by mass
Sucrose stearate
(Mitsubishi Chemical Foods Co., Ltd., trade name “Sugar Ester S1670”) 0.01 parts by mass
2 parts by mass of glycerin
72 parts by weight of deionized water
This product is excellent in water-solubility, and the package according to this product can be taken out by simply immersing it in an aqueous medium without opening the contents. Moreover, the water | moisture content suitable for heat sealing is hold | maintained in a dry environment, and a heat seal part does not peel substantially. Moreover, since pullulan is used as the main raw material, it has oxygen-impermeable characteristics and is suitable for packaging of objects that are easily oxidized.
Example 3: Water-soluble film
Prepare an aqueous solution of pullulan having the composition shown below, and drop it onto an applicator (Yoshimitsu Seiki Co., Ltd., brand name “Baker Applicator YBA type”). The film was heated and dried at 85 ° C. for 10 minutes and then allowed to stand at 25 ° C. and a relative humidity of 55% for 16 hours to produce a film having a thickness of 30 μm and an equilibrium water content of about 11%.
Pullulan (trade name “PI20” sold by Hayashibara Corporation) 20 parts by mass
Carrageenan (κ)
(Sanki Co., Ltd., trade name “GENUGEL WG-115”) 1 part by mass
Carrageenan (κ and λ)
(Sanki Co., Ltd., trade name “GENUVISCO CSW-2”) 1 part by mass
Carrageenan (ι)
(Sanki Co., Ltd., trade name "GENUVISCO PJ") 1 part by mass
1 part by weight of sorbitol
Sucrose stearate
(Mitsubishi Chemical Foods Co., Ltd., trade name “Sugar Ester S1670”) 0.01 parts by mass
2 parts by mass of glycerin
72 parts by weight of deionized water
This product is excellent in water-solubility, and the package according to this product can be taken out by simply immersing it in an aqueous medium without opening the contents. Moreover, the water | moisture content suitable for heat sealing is hold | maintained in a dry environment, and a heat seal part does not peel substantially. Moreover, since pullulan is used as the main raw material, it has oxygen-impermeable characteristics and is suitable for packaging of objects that are easily oxidized.
Example 4: Water-soluble film
Prepare an aqueous solution of pullulan having the composition shown below, and drop it onto an applicator (Yoshimitsu Seiki Co., Ltd., brand name “Baker Applicator YBA type”). The film was heated and dried at 85 ° C. for 15 minutes, and then allowed to stand at 25 ° C. and a relative humidity of 55% for 16 hours to produce a film having a thickness of 30 μm and an equilibrium water content of about 13%.
Pullulan (Hayashibara Corporation, trade name "PI20") 4 parts by mass
Locust bean gum (sold by Sanki Co., Ltd.) 0.7 parts by mass
Xanthan gum (sold by Dainippon Pharmaceutical Co., Ltd.) 0.1 parts by mass
Carrageenan (κ)
(Sanki Co., Ltd., trade name “GENUVISCO SWG-J”) 3 parts by mass
Glycerin 3.5 parts by mass
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., trade name “Sugar Ester S1670”) 0.01 parts by mass
84 parts by weight of deionized water
This product is excellent in water-solubility, and the package according to this product can be taken out by simply immersing it in an aqueous medium without opening the contents. Moreover, the water | moisture content suitable for heat sealing is hold | maintained in a dry environment, and a heat seal part does not peel substantially. Although this product is not suitable for use and storage in high humidity environments exceeding 60% relative humidity, it can be used and stored in severe dry environments with a relative humidity of 10% or less. It is a film that can also be heat-sealed at a temperature of.
Example 5: Gauze coated with a water-soluble film
After preparing a pullulan aqueous solution of the composition shown below, applying this to gauze with a brush, placing it well on a glass flat plate with polyethylene terephthalate in close contact, and adding the above-mentioned solution and thoroughly immersing it And dried at 85 ° C. for 15 minutes and then allowed to stand at 25 ° C. and 55% relative humidity for 16 hours to produce a gauze coated with a water-soluble film having an equilibrium moisture content of about 11%.
Pullulan (trade name “PI20” sold by Hayashibara Corporation) 14 parts by mass
Carrageenan (κ and λ)
(Sanki Co., Ltd., trade name “GENUVISCO CSW-2”) 7 parts by mass
1 part by weight of sorbitol
Sucrose stearate
(Mitsubishi Chemical Foods Co., Ltd., trade name “Sugar Ester S1670”) 0.01 parts by mass
2 parts by mass of glycerin
72 parts by weight of deionized water
Since the gauze eyes are filled with a water-soluble film, this product can be heat-sealed and has excellent sealing properties. Further, the contents can be taken out only by being immersed in an aqueous medium without opening the contents. Moreover, the water | moisture content suitable for heat sealing is hold | maintained in a dry environment, and a heat seal part does not peel substantially. Moreover, since pullulan is used as the main raw material, it has oxygen-impermeable characteristics and is suitable for packaging of objects that are easily oxidized.
Example 6: Instant coffee
The film produced in Example 1 or Example 4 was cut into a square with a side of 4 cm, and two sheets were stacked. Then, a heat sealer (Fuji Impulse Sales Co., Ltd., trade name “Fuji Impulse Sealer OPL-200- 10 ”), the film of Example 1 was heat-sealed under conditions of 130 ° C. for 3 seconds, the film of Example 4 was heat-sealed under conditions of 180 ° C. for 1 second, and the three sides were heat-sealed. After putting 2 to 5 g of commercially available instant coffee, the remaining side was heat-sealed under the same conditions.
This product can be put into a coffee cup as it is without opening it, and hot water can be poured into it, so the trouble of opening and measuring the coffee powder can be saved and the powder will not scatter. Convenient.
Example 7: Tea pack
A net base material for a tea pack was sandwiched between two films produced in Example 2, and the entire surface of the film was heat-sealed under high heat and high pressure using an iron, and the net base material was filled with a film to fill a gap in the mesh. Using this, the tea pack was manufactured by the conventional method.
Since the film used in this product is edible and water-soluble, black tea can be easily extracted by immersing the product in hot water or water, and the disposal of the extraction residue is easy. Moreover, since this product is excellent in airtightness, it can prevent quality deterioration of black tea. In addition to black tea, inclusions using a net base material with gaps filled with film are also advantageous for teas such as green tea, herb tea, oolong tea, and dashi such as shiitake mushrooms, cutlet cuts, and kelp Applicable to.
Example 8: Detergent
The film produced in Example 3 or 4 was formed into a rectangle having a length of 10 cm and a width of 7 cm, the film of Example 3 was heated at 130 ° C. for 3 seconds, and the film of Example 4 was 180 ° C. After heat-sealing under heat-sealing conditions for a second, it was cut off, and the heel part on one side was cut off to form a bag. 5 g of a commercial powder detergent was added to this, and it was heat-sealed again and sealed. A set of five bags was put into a polyethylene bag of an appropriate size, and then the polyethylene bag was heat-sealed and sealed.
After removing the product from the polyethylene bag, it can be put into a water tank such as a washing machine without opening the seal. This saves you the trouble of weighing and prevents the detergent from adhering to your hand. Can be handled without any problems. Moreover, since it is excellent in sealing performance and oxygen impermeability, the effectiveness of the detergent can be maintained.
Example 9: Bath salt
An appropriate amount of sodium sulfate powder 60 parts by mass, sodium hydrogen carbonate powder 27 parts by mass, titanium dioxide powder 1 part by mass, sodium lauryl sulfate powder 1 part by mass, and a silicone resin antifoam were mixed in an appropriate amount to prepare a bath agent. On the other hand, after cutting the gauze manufactured in Example 5 into a square having a side of 12 cm and stacking two sheets, a heat seal device (Fuji Impulse Sales Co., Ltd., trade name “Fuji Impulse Sealer OPL-200-10” )) At 130 ° C. for 3 seconds under heat sealing conditions, 3 sides are heat sealed, and after putting 10-15 g of the above bathing agent into a bag, the remaining side is kept under the same conditions. Heat sealed.
Since this product can be put into the bathtub as it is without opening it, the trouble of opening it is saved, and the powder of the bathing agent is not scattered, so that the handling is simple.

  As described above, the film of the present invention maintains sufficient film strength and flexibility even in a dry environment, for example, in an environment with a relative humidity of 25%, and the heat seal portion does not substantially peel. 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. Therefore, it can be used in a wide range of fields such as food, cosmetics, pharmaceuticals, and chemicals.

Claims (12)

One or more water-soluble polysaccharides having no sulfate group and one or more water-soluble polysaccharides having a sulfate group, and one or more hydroxy compounds as a humidity control material are blended, and are substantially cross-linking agents. A water-soluble film that does not substantially peel off the heat-sealed portion under a water equilibrium condition of a relative humidity of 25% or less when heat-sealed. 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. 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. The water-soluble film according to claim 3, wherein the polysaccharide having maltotriose as a repeating unit is pullulan. The water-soluble film according to claim 1 or 2, wherein pullulan, locust bean gum and xanthan gum are blended as a water-soluble polysaccharide having no sulfate group. The water-soluble composition according to claim 5, comprising a hydroxy compound in an amount of 20% by mass or more and a total amount of locust bean gum and xanthan gum in an amount of 0.5 to 40% by mass based on the pullulan based on the total amount of the water-soluble polysaccharide. Sex film. 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. The water-soluble film according to claim 1, 2, 3, 4, 5, 6, or 7, wherein the hydroxy compound is a polyol. Furthermore, glycerin fatty acid ester is contained, Claims 1st, 2nd, 3rd, 4th, 5th, 6th, 7th, or 8th claim Water-soluble film. Claims 1, 2, 3, 4, 5, 6, 7, 8, which dissolve substantially within 5 minutes when immersed in warm water at 80 ° C. Item or a water-soluble film according to Item 9. Claims 1, 2, 3, 4, 5, 6, 7, 8, 9 are partially or wholly heat sealed. Item, or a packaging material using the water-soluble film according to Item 10. A method for producing a packaged article, comprising packaging with the packaging material according to claim 11.