JP2005008160A - Aseptic rice filling and packaging container and aseptic packaging rice using the same - Google Patents

Abstract

An object of the present invention is to provide aseptic packaged rice, particularly as a plastic lid material, having strength and the like, and having excellent heat resistance, moisture resistance, heat sealability, pinhole resistance, puncture resistance, transparency, etc. It has excellent barrier properties to prevent permeation of oxygen gas, water vapor, etc., has the contents suitable for filling and packaging, storage, etc., and also does not generate harmful substances when incineration disposal after use An object of the present invention is to provide a lid for aseptic rice filling and packaging container that is extremely excellent in disposal processing suitability, environmental suitability, etc., and to provide aseptic packaging cooked rice using the same.
An inorganic oxide vapor-deposited film and a gas barrier coating film are provided on one surface of a base film, and a printed pattern layer and a laminating adhesive are further formed on the gas barrier coating film. The present invention relates to a lid for aseptic rice filling and packaging container characterized by providing layers sequentially, and then providing a heat-sealable resin layer via the laminating adhesive layer, and aseptic packaging rice using the same. is there.
[Selection] Figure 1

Description

などのメルカプチド型有機スズ化合物；

などのスルフィド型有機スズ化合物；
【００４２】
（Ｃ_４ Ｈ_９ ）_２ ＳｎＯ、（Ｃ_８ Ｈ_１７）_２ ＳｎＯ、または（Ｃ_４ Ｈ_９ ）_２ ＳｎＯＨ_１７）_２ ＳｎＯなどの有機スズオキサイドとエチルシリケート、マレイン酸ジメチル、マレイン酸ジエチル、フタル酸ジオクチルなどのエステル化合物との反応生成物などの有機スズ化合物などが使用される。
これらの（Ｄ）硬化促進剤のガスバリア性組成物中における割合は、本発明のガスバリア性組成物の固形分１００重量部に対して、通常、０．５〜５０重量部、好ましくは０．５〜３０重量部用いられる。
【００４３】
さらに、本発明のガスバリア性組成物には、安定性向上剤として、先に挙げたβ−ジケトン類および／またはβ−ケトエステル類を添加することができる。
すなわち、上記の（Ｂ）成分としてガスバリア性組成物中に存在する上記の金属アルコレート中の金属原子に配位することにより、（Ａ）成分と（Ｂ）成分との縮合反応をコントロールする作用をし、得られるガスバリア性組成物の保存安定性を向上させる作用をなすものと考えられる。
β−ジケトン類および／またはβ−ケトエステル類の使用量は、上記（Ｂ）成分における金属原子１モルに対し、好ましくは２モル以上、さらに好ましくは、３〜２０モルである。
【００４４】
本発明のガスバリア性組成物は、通常、上記（Ａ）〜（Ｄ）成分および場合により上記任意成分を、水および／または親水性有機溶媒中で溶解、分散することによって得られる。
ここで、親水性有機溶媒の具体例としては、メタノール、エタノール、ｎ−プロパノール、ｉ−プロパノール、ｎ−ブチルアルコール、ｓｅｃ−ブチルアルコール、ｔｅｒｔ−ブチルアルコール、ジアセトンアルコール、エチレングリコール、ジエチレングリコール、トリエチレングリコールなどの炭素数１〜８の飽和脂肪族の１価アルコールまたは２価アルコール；エチレングリコールモノブチルエーテル、酢酸エチレングリコールモノエチルエーテルなどの炭素数１〜８の飽和脂肪族のエーテル化合物；エチレングリコールモノメチルエーテルアセテート、エチレングリコールモノエチルエーテルアセテート、エチレングリコールモノブチルエーテルアセテートなどの炭素数１〜８の飽和脂肪族の２価アルコールのエステル化合物；Ｎ，Ｎ−ジメチルアセトアミド、Ｎ，Ｎ−ジメチルホルムアミド、γ−ブチロラクトン、Ｎ−メチルピロリドン、ピリジンなどの含窒素化合物（含窒素有機溶媒）；ジメチルスルホキシドなどの含硫黄化合物；乳酸、乳酸メチル、乳酸エチル、サリチル酸、サリチル酸メチルなどのヒドロキシカルボン酸またはヒドロキシカルボン酸エステルなどを挙げることができる。これらのうち、好ましいものとしては、メタノール、エタノール、ｎ−プロパノール、ｉ−プロパノール、ｎ−ブチルアルコール、ｓｅｃ−ブチルアルコール、ｔｅｒｔ−ブチルアルコールなどの炭素数１〜８の飽和脂肪族の１価アルコール；Ｎ，Ｎ−ジメチルアセトアミド、Ｎ，Ｎ−ジメチルホルムアミド、γ−ブチロラクトン、Ｎ−メチルピロリドン、ピリジンなどの含窒素化合物（含窒素有機溶媒）を挙げることができる。
【００４５】
これらの水および／または親水性有機溶媒は、水と親水性有機溶媒とを混合して用いられることがより好ましい。
好ましい溶媒の組成としては、水／炭素数１〜８の飽和脂肪族の１価アルコール、水／含窒素化合物（含窒素有機溶媒）である。
さらに好ましくは、水／炭素数１〜８の飽和脂肪族の１価アルコール／含窒素化合物（含窒素有機溶媒）である。
含窒素有機溶媒を混合することで、薄膜でのコーティングにおいて外観が透明で良好な塗膜が得られる。
【００４６】
水および／または親水性有機溶媒の使用量は、ガスバリア性組成物の全固形分濃度が好ましくは６０重量％以下となるように用いられる。
例えば、薄膜形成を目的に用いられる場合には、通常、５〜４０重量％、好ましくは、１０〜３０重量％であり、また厚膜形成を目的に使用する場合には、通常、２０〜５０重量％、好ましくは、３０〜４５重量％である。
ガスバリア性組成物の全固形分濃度が６０重量％を超えると、組成物の保存安定性が低下する傾向にある。
また、上記含窒素有機溶媒の割合は、溶媒全量中に、通常、１〜７０重量％、好ましくは５〜５０重量％である。
【００４７】
なお、有機溶媒としては、上記の水および／または親水性有機溶媒が好ましいが、親水性有機溶媒以外に、例えばベンゼン、トルエン、キシレンなどの芳香族炭化水素類、テトラヒドロフラン、ジオキサンなどのエーテル類、アセトン、メチルエチルケトンなどのケトン類、酢酸エチル、酢酸ブチルなどのエステル類なども使用できる。
【００４８】
このように、本発明のガスバリア性組成物は、上記（Ａ）〜（Ｂ）成分および場合により上記任意成分を、水および／または親水性有機溶媒中で混合することによって得られ、好ましくは上記（Ａ）成分と（Ｂ）成分、必要に応じて（Ｃ）成分を、水および／または親水性有機溶媒中で、加水分解および／または縮合することによって得られる。
この際、反応条件は、温度は２０〜１００℃、好ましくは３０〜８０℃、時間は０．１〜２０時間、好ましくは１〜１０時間である。
得られるガスバリア性組成物の重量平均分子量は、一般的なＧＰＣ法によるポリメチルメタクリレート換算値で、通常、５００〜１００万、好ましくは１，０００〜３０万である。
【００４９】
なお、本発明のガスバリア性組成物には、得られる塗膜の着色、厚膜化、下地への紫外線透過防止、防蝕性の付与、耐熱性などの諸特性を発現させるために、別途、充填材を添加・分散させることも可能である。
ただし、充填材は、上記（Ｃ）成分を除く。
充填材としては、例えば、有機顔料、無機顔料などの非水溶性の顔料または顔料以外の、粒子状、繊維状もしくは鱗片状の金属および合金ならびにこれらの酸化物、水酸化物、炭化物、窒化物、硫化物などが挙げられる。
この充填材の具体例としては、粒子状、繊維状もしくは鱗片状の、鉄、銅、アルミニウム、ニッケル、銀、亜鉛、フェライト、カーボンブラック、ステンレス鋼、二酸化ケイ素、酸化チタン、酸化アルミニウム、酸化クロム、酸化マンガン、酸化鉄、酸化ジルコニウム、酸化コバルト、合成ムライト、水酸化アルミニウム、水酸化鉄、炭化ケイ素、窒化ケイ素、窒化ホウ素、クレー、ケイソウ土、消石灰、石膏、タルク、炭酸バリウム、炭酸カルシウム、炭酸マグネシウム、硫酸バリウム、ベントナイト、雲母、亜鉛緑、クロム緑、コバルト緑、ビリジアン、ギネー緑、コバルトクロム緑、シェーレ緑、緑土、マンガン緑、ピグメントグリーン、群青、紺青、ピグメントグリーン、岩群青、コバルト青、セルリアンブルー、ホウ酸銅、モリブデン青、硫化銅、コバルト紫、マルス紫、マンガン紫、ピグメントバイオレット、亜酸化鉛、鉛酸カルシウム、ジンクエロー、硫化鉛、クロム黄、黄土、カドミウム黄、ストロンチウム黄、チタン黄、リサージ、ピグメントイエロー、亜酸化銅、カドミウム赤、セレン赤、クロムバーミリオン、ベンガラ、亜鉛白、アンチモン白、塩基性硫酸鉛、チタン白、リトポン、ケイ酸鉛、酸化ジルコン、タングステン白、鉛亜鉛華、バンチソン白、フタル酸鉛、マンガン白、硫酸鉛、黒鉛、ボーン黒、ダイヤモンドブラック、サーマトミック黒、植物性黒、チタン酸カリウムウィスカー、二硫化モリブデンなどが挙げられる。
【００５０】
これらの充填材の平均粒径または平均長さは、通常、５０〜５０，０００ｎｍ、好ましくは１００〜５，０００ｎｍである。
充填材の組成物中の割合は、充填材以外の成分の全固形分１００重量部に対し、好ましくは、０．１〜３００重量部、さらに好ましくは、１〜２００重量部である。
【００５１】
なお、本発明のガスバリア性組成物には、そのほか、オルトギ酸メチル、オルト酢酸メチル、テトラエトキシシランなどの公知の脱水剤、各種の界面活性剤、上記以外の、シランカップリング剤、チタンカップリング剤、染料、分散剤、増粘剤、レベリング剤などの添加剤を配合することもできる。
【００５２】
本発明のガスバリア性組成物を調製するに際しては、上記（Ａ）〜（Ｂ）成分、好ましくは（Ａ）〜（Ｃ）成分を含有する組成物を調製すればよいが、好ましくは、上記（Ｂ）成分を水または水と親水性有機溶媒を含む混合溶媒中で加水分解したのち、（Ａ）成分を混合する。
このようにすると、ガスバリア性組成物の経時的な粘度変化がなく、取り扱い性に優れたガスバリア性組成物が得られる。
（Ｃ）成分を用いる場合の本発明のガスバリア性組成物の調製方法の具体例としては、例えば、下記の方法が挙げられる。
これらの調製方法において用いられる（Ｂ）成分は、水または水と親水性有機溶媒を含む混合溶媒中であらかじめ加水分解したものを用いてもよい。
水および／または親水性有機溶剤に溶解させた（Ａ）成分に（Ｃ）成分を添加したのち、（Ｂ）成分を添加する方法。
水および／または親水性有機溶剤に溶解させた（Ａ）成分に（Ｃ）成分を添加したのち、（Ｂ）成分を添加し、加水分解および／または縮合する方法。
水および／または親水性有機溶剤に溶解させた（Ｂ）成分に、（Ｃ）成分を添加し、加水分解および／または縮合を行ない、そののちに（Ａ）成分を添加する方法。
水および／または親水性有機溶剤に（Ａ）〜（Ｃ）成分を一括添加し、溶解・分散する方法。または、そののちに加水分解および／または縮合を行う方法。
【００５３】
而して、本発明においては、上記で調製したガスバリア性組成物を使用し、これを、前述の無機酸化物の蒸着膜の上に塗布することにより、ガスバリア性塗布膜を形成することができる。
本発明においては、無機酸化物の蒸着膜とガスバリア性塗布膜とが、例えば、加水分解・共縮合反応による化学結合、水素結合、あるいは、配位結合などを形成し、無機酸化物の蒸着膜とガスバリア性塗布膜との密着性が向上し、その２層の相乗効果により、より良好なガスバリア性の効果を発揮し得るものである。
上記の本発明のガスバリア性組成物を塗布する方法としては、例えば、グラビアコーターなどのロールコート、スプレーコート、スピンコート、ディッピング、刷毛、バーコード、アプリケータなどの塗装手段により、１回あるいは複数回の塗装で、乾燥膜厚が０．０１〜３０μｍ、好ましくは、０．１〜１０μｍの本発明のガスバリア性塗布膜を形成することができ、通常の環境下、５０〜３００℃、好ましくは７０〜２００℃の温度で、０．００５〜６０分間、好ましくは、０．０１〜１０分間、加熱・乾燥することにより、縮合が行われ、本発明のガスバリア性塗布膜を形成することができる。
また、必要ならば、本発明のガスバリア性組成物を塗布する際に、予め、無機酸化物の蒸着膜の上に、プライマ−剤等を塗布することもできるものである。
【００５４】
次に、本発明において、本発明にかかる無菌米飯充填包装容器用蓋材、無菌包装米飯等を構成する印刷模様層について説明すると、かかる印刷模様層としては、通常のインキビヒクルの１種ないし２種以上を主成分とし、これに、必要ならば、可塑剤、安定剤、酸化防止剤、光安定剤、紫外線吸収剤、硬化剤、架橋剤、滑剤、帯電防止剤、充填剤、その他等の添加剤の１種ないし２種以上を任意に添加し、更に、染料・顔料等の着色剤を添加し、溶媒、布釈剤等で充分に混練してインキ組成物を調整し、次いで、該インキ組成物を使用し、これを、例えば、グラビア印刷、オフセット印刷、凸版印刷、スクリーン印刷、転写印刷、フレキソ印刷、その他等の印刷方式を使用し、前述のガスバリア性塗布膜を含む面の上に、文字、図形、記号、模様、その他等からなる所望の印刷模様を印刷して、本発明にかかる印刷模様層を形成することができるものである。
【００５５】
上記において、インキビヒクルとしては、企知のもの、例えば、あまに油、きり油、大豆油、炭化水素油、ロジン、ロジンエステル、ロジン変性樹脂、シエラック、アルキッド樹脂、フェノール系樹脂、マレイン酸樹脂、天然樹脂、炭化水素樹脂、ポリ塩化ビニル系樹脂、ポリ酢酸ビニル系樹脂、ポリスチレン系樹胎、ポリビニルプチラール樹脂、アクリルまたはメタクリル系樹脂、ポリアミド系樹脂、ポリエステル系樹脂、ポリウレタン系樹脂、エポキシ系樹脂、尿素樹脂、メラミン樹脂、アミノアルキッド系樹脂、ニトロセルロース、エチルセルロース、塩化ゴム、環化ゴム、その他等の１種ないし２種以上を使用することができる。
【００５６】
次に、本発明において、本発明にかかる無菌米飯充填包装容器用蓋材、無菌包装米飯等を構成するラミネート用接着剤層について説明すると、かかるラミネート用接着剤層を構成する接着剤としては、例えば、ポリ酢酸ビニル系接着剤、アクリル酸のエチル、プチル、２−エチルヘキシルエステル等のホモポリマー、あるいは、これらとメタクリル酸メチル、アクリロニトリル、スチレン等との共重合体等からなるポリアクリル酸エステル系接着剤、シアノアクリレート系接着剤、エチレンと酢酸ビニル、アクリル酸エチル、アクリル酸、メタクリル酸等のモノマーとの共重合体等からなるエチレン共重合体系接着剤、セルロース系接着剤、ポリエステル系接着剤、ポリアミド系接着剤、ポリイミド系接着剤、尿素樹脂またはメラミン樹脂等からなるアミノ樹脂系接着剤、フェノール樹脂系接着剤、エポキシ系接着剤、ポリウレタン系接着剤、反応型（メタ）アクリル系接着剤、クロロプレンゴム、ニトリルゴム、スチレンーブタジェンゴム等からなるゴム系接着剤、シリコーン系接着剤、アルカリ金属シリケート、低融点ガラス等からなる無機系接着剤、その他等の接着剤を使用することがてきる。
上記の接着剤の組成系は、水性型、溶液型、エマルジョン型、分散型等のいずれの組成物形態でもよく、また、その性状は、フィルム・シート状、粉末状、固形状等のいずれの形態でもよく、更に、接着機構については、化学反応型、溶剤揮発型、熱溶融型、熱圧型等のいずれの形態でもよいものである。
而して、本発明においては、前述の印刷模様層を含む全面に、上記の接着剤を、例えば、ロールコート法、グラビアロールコート法、キスコート法、その他等のコート法、あるいは、印刷法等によって施し、次いで、溶剤等を乾燥させてラミネート用接着剤層を形成すことができ、そのコーティングないし印刷量としては、０．１〜１０ｇ／ｍ^２ （乾燥状態）位が望ましい。
【００５７】
次に、本発明において、本発明にかかる無菌米飯充填包装容器用蓋材、無菌包装米飯等を構成するヒ−トシール性樹脂層について説明すると、かかるヒ−トシール性樹脂層を構成するヒートシール性樹脂としては、熱によって溶融し相互に融着し得るものであればよく、例えば、低密度ポリエチレン、中密度ポリエチレン、高密度ポリエチレン、直鎖状（線状）低密度ポリエチレン、ポリプロピレ、エチレンー酢酸ビニル共重合体、アイオノマー樹脂、エチレンーアクリル酸エチル共重合体、エチレンーアクリル酸共重合体、エチレンーメタクリル酸共重合体、エチレンープロピレン共重合体、メチルペンテンポリマー、ポリエチレン、ポリプロピレン等のポリオレフイン系樹脂をアクリル酸、メタクリル酸、無水マレイン酸、フマール酸、その他等の不飴和カルボン酸で変性した酸変性ポリオレフイン系樹脂、その他等の樹脂の一種ないしそれ以上からなる樹脂のフィルムないしシートを使用することができる。
而して、本発明においては、前述のラミネート用接着剤層の面に、上記の樹脂のフィルムないしシートをドライラミネートして、本発明にかかるヒ−トシール性樹脂層を形成することができるものである。
上記の樹脂のフィルムないしシートは、単層ないし多層で使用することができ、また、上記の樹脂のフィルムないしシートの厚さとしては、５μｍ 〜３００μｍ 位、好ましくは、１０μｍ 〜１１０μｍ 位が望ましい。
更に、本発明において、上記の樹脂のフィルムないしシートの厚さとしては、無菌米飯充填包装容器用蓋材をトレー状の充填包装用容器の開口部のフランジ部にヒ一トシールするとき等において、無機酸化物の蒸着膜を有する基材フィルムを構成する無機酸化物の蒸着膜に、擦り傷、あるいは、クラック等を発生するすることを防止するために、その膜厚を厚くすることが好ましく、具体的には、７０μｍ 〜１１０μｍ 位、望ましくは、８０μｍ 〜１００μｍ 位であることが好ましいものである。
【００５８】
ところで、本発明においては、上記のような樹脂のフィルムないしシートの中でも、特に、線状低密度ポリエチレンを使用することが好ましいものである。
すなわち、上記の線状低密度ポリエチレンは、粘着性を有することから破断の伝搬が少なく耐衝撃性を向上させるという利点があるものであり、また、内層は常時内容物に接触していることから、耐環境ストレスクラッキング性の劣化を防止するためにも有効なものである。
また、本発明においては、線状低密度ポリエチレンに、他の樹脂をブレンドすることもでき、例えば、エチレンーブテン共重合体等をブレンドすることにより、若干、耐熱性に劣り高温環境下ではシール安定性が劣化する傾向があるものの、引き裂き性が向上し、易開封性に寄与するという利点がある。
【００５９】
更に、本発明において、上記のようなヒ−トシール性を有する樹脂のフィルムないしシートとしての線状低密度ポリエチレンとしては、具体的には、メタロセン触媒を用いて重合したエチレンーα・オレフイン共重合体のフィルムないしシートを同様に使用することができる。
上記のメタロセン触媒を用いて重合したエチレンーα・オレフイン共重合体のフィルムないしシートとしては、例えば、二塩化ジルコノセンとメチルアルモキサンの組み合わせによる触媒等のメタロセン錯体とアルモキサンとの組み合わせによる触媒、すなわち、メタロセン触媒を使用して重合してなるエチレンーα．オレフイン共重合体のフィルムないしシートを使用することができる。
メタロセン触媒は、現行の触媒が、活性点が不均一でマルチサイト触媒と呼ばれているのに対し、活性点が均一であることからシングルサイト触媒とも呼ばれているものである。
具体的には、メタロセン触媒を使用して重合したエチレン−α・オレフィン共重合体としては、三菱化学株式会社製の商品名「カ−ネル」、三井石油化学工業株式会社製の商品名「エボリュ−」、米国、エクソン・ケミカル（ＥＸＸＯＮ ＣＨＥＭＩＣＡＬ）社製の商品名「エクザクト（ＥＸＡＣＴ）」、米国、ダウ・ケミカル（ＤＯＷ ＣＨＥＭＩＣＡＬ）社製の商品名「アフィニティ−（ＡＦＦＩＮＩＴＹ）、商品名「エンゲ−ジ（ＥＮＧＡＧＥ）」等のメタロセン触媒を用いて重合したエチレン−α−オレフィン共重合体を使用することができる。
そのフィルムないしシートとしては、単層ないし多層で使用することができ、その厚さとしては、５μｍ ないし３００μｍ 位、好ましくは、１０μｍ ないし１００μｍ 位が望ましい。
本発明において、上記のようなヒートシール性を有する樹脂のフィルムとして、メタロセン触媒を用いて重合したエチレンーα・オレフイン共重合体のフィルムないしシートを使用する場合には、無菌米飯充填包装容器用蓋材をトレー状の包装用容器の開口部のフランジ部にヒ−トシールするときに、低温ヒートシール性が可能であるという利点を有するものである。
【００６０】
次にまた、本発明において、本発明にかかる無菌米飯充填包装容器用蓋材、無菌装米飯等を構成するラミネート用接着剤層とヒートシール性樹脂層との層間に積層する、強度を有し、耐突き刺し性等に優れた樹脂のフィルムとしては、機械的、物理的、化学的、その他等において優れた強度を有し、耐突き刺し性等に優れ、その他、耐熱性、防湿性、耐ピンホール性、透明性、その他等に優れた樹脂のフィルムないしシートを使用することができる。
具体的には、例えば、ポリエステル系樹脂、ポリアミド系樹胎、ポリアラミド系樹脂、ポリプロピレン系樹脂、ポリカーボネート系樹脂、ポリアセタール系樹脂、フッ素系樹脂、その他等の強靭な樹脂のフィルムないしシートを使用することができる。
而して、本発明においては、上記の樹脂のフィルムないしシートを使用し、これを、例えば、前述のラミネート用接着剤等を使用してドライラミネート法等を用いて、ラミネート用接着剤層とヒ−トシール性樹脂層との層間に積層することができるものである。
上記において、上記の樹脂のフィルムないしシートとしては、未延伸フィルム、あるいは一軸方向または二軸方向に延伸した延伸フィルム等のいずれのものでも使用することができる。
また、本発明において、その樹脂のフィルムないしシートの厚さとしては、強度、耐突き刺し性、その他等について、必要最低限に保持され得る厚さであればよく、厚すぎると、コストを上昇するとい欠点もあり、逆に、薄すぎると、強度、耐突き刺し性、その他等が低下して好ましくないものである。
本発明においては、上記のような理由から、約１０μｍ ないし１００μｍ 位、好ましくは、約１２μｍ ないし５０μｍ 位が最も望ましい。
【００６１】
ところで、通常、内容物を充填包装した包装製品は、物理的にも化学的にも過酷な条件におかれることから、包装用容器、蓋材等を構成する積層材には、厳しい包装適性が要求され、変形防止強度、落下衝撃強度、耐ピンホール性、耐熱性、密封性、品質保全性、作業性、衛生性、その他等の種々の条件が要求され、このために、本発明においては、上記のような材料の他に、上記のような諸条件を充足するその他の材料を任意に使用することができ、具体的には、例えば、低密度ポリエチレン、中密度ポリエチレン、高密度ポリエチレン、線状低密度ポリエチレン、ポリプロピレン、エチレンープロピレン共重合体、エチレンー酢酸ビニル共重合体、アイオノマー樹脂、エチレンーアクリル酸エチル共重合体、エチレンーアクリル酸またはメタクリル酸共重合体、メチルペンテンポリマー、ポリブテン系樹脂、ポリ塩化ビニル系樹脂、ポリ酢酸ビニル系樹脂、ポリ塩化ビニリデン系樹脂、塩化ビニルー塩化ビニリデン共重合体、ポリ（メタ）アクリル系樹脂、ポリアクリルニトリル系樹脂、ポリスチレン系樹脂、アクリロニトリルースチレン共重合体（ＡＳ系樹脂）、アクリロニトリループタジェンースチレン共重合体（ＡＢＳ 系樹脂）、ポリエステル系樹脂、ポリアミド系樹脂、ポリカーボネート系樹脂、ポリビニルアルコール系樹脂、エチレンー酢酸ビニル共重合体のケン化物、フッ素系樹脂、ジェン系樹脂、ポリアセタール系樹脂、ポリウレタン系樹脂、ニトロセルロース、その他等の既知の樹脂のフィルムないしシートを任意に選択して使用することができる。 その他、例えば、合成紙等も使用することが
できる。
本発明において、上記のフィルムないしシートは、未延伸、一軸ないし二軸方向に延伸されたもの等のいずれのものでも使用することができる。
また、その厚さは、任意であるが、数μｍから３００μｍ位の範囲から選択して使用することができる。
更に、本発明においては、フィルムないしシートとしては、押し出し成膜、インフレーション成膜、コーティング膜等のいずれの性状の膜でもよい。
【００６２】
特に、本発明において、その他の基材としては、例えば、水蒸気、水等の透過を阻止するバリア性を有する低密度ポリエチレン、中密度ポリエチレン、高密度ポリエチレン、直鎖状低密度ポリエチレン、ポリプロピレン、エチレンープロピレン共重合体等の樹脂のフィルムないしシート、酸素ガス、水蒸気等の透過を阻止するバリア性を有するナイロンＭＸＤ６樹脂等の樹脂のフィルムないしシート、樹脂に顔料等の着色剤を、その他、所望の添加剤を加えて混練してフィルム化してなる遮光性を有する各種の着色樹脂のフィルムないしシート等を使用することができる。
これらの材料は、一種ないしそれ以上を組み合わせて使用することができる。
また、上記のフィルムないしシートの厚さとしては、任意であるが、通常、５μｍないし３００μｍ位、更には、１０μｍないし１００μｍ位が望ましい。
【００６３】
本発明は、以上において説明したように、基材フィルムの一方の面に、無機酸化物の蒸着膜およびガスバリア塗布膜を設け、次いで、該ガスバリア性塗布膜の上に、印刷模様層、および、ラミネート用接着剤層を順次に設け、更に、該ラミネート用接着剤層を介して、ヒートシール性樹脂層を設け、更には、上記のラミネート用接着剤層とヒ−トシール性樹脂層との間に、強度を有し、耐突き刺し性に優れた樹脂のフィルムを積層することにより、本発明にかかる 無菌米飯充填包装容器用蓋材を製造することができるものである。
【００６４】
次に、本発明において、本発明にかかる無菌米飯充填包装容器用蓋材を使用して製造する無菌包装米飯を構成するトレー状の充填包装容器について説明すると、かかるトレー状の充填包装容器としては、例えば、ポリエチレン系樹脂、ポリプロピレン系樹脂、ポリスチレン系樹脂、ポリカーボネート系樹脂、ポリアクリロニトリル系樹脂、ポリエステル系樹脂、ポリアミド系樹脂、アクリロニトリルースチレン共重合体、アクリロニトリループタジェンースチレン共重合体、ポリビニルアセタール系樹脂、（メタ）アクリル系樹脂、その他等の成形用樹脂を使用し、これを、例えば、射出成形、押出成形、その他等の成形法を用いて成形して製造してなるトレー状の充填包装容器を使用することができる。
あるいは、本発明においては、上記のトレー状の充填包装用容器としては、例えば、上記に例示した樹脂の１種ないし２種以上を使用し、それらを、例えば、Ｔダイ押出法、あるいは、インフレーション押出法、その他等を用いて単独ないし共押出してそれらの樹脂の単独フィルムないし共押出フィルム等を製造し、次いで、その単独フィルムないし共押出フィルムを使用し、これを、真空・圧空成形等の熱成形法を用いて成形して製造してなるトレー状の充填包装容器等を使用することができる。
【００６５】
更に、本発明においては、上記のトレー状の充填包装容器としては、例えば、上記のような例えば、ポリエチレン系樹脂、ポリプロピレン系樹脂、ポリスチレン系樹脂、ポリカーボネート系樹胎、ポリアクリロニトリル系樹胎、ポリエステル系樹脂、ポリアミド系樹脂、アクリロニトリルースチレン共重合体、アクリロニトリループタジェンースチレン共重合体、ポリビニルアセタール系樹脂、（メタ）アクリル系樹脂、その他等の成形用樹脂と、例えば、エチレンービニルアルコール共重合体、ポリアクリロニトリル系樹脂、ナイロンＭＸＤ６樹脂、その他等の酸素ガス、水蒸気等の透過を阻止する性質を有するバリア性樹脂等を使用し、これらを、Ｔダイ共押出法、あるいは、インフレーション共押出法、その他等を用いて共押出して、例えば、ポリプロピレン系樹脂層／エチレンービニルアルコール共重合体、ポリアクリロニトリル系樹脂、あるいは、ナイロンＭＸＤ６樹脂層／ポリプロピレン系樹脂層等の３〜５層からなる共押出フィルム等を製造し、該共押出フィルムを使用し、これを、真空・圧空成形等の熱成形法を用いて成形して製造してなるトレー状の充填包装容器等を使用することができる。
【００６６】
次に、本発明においては、上記で製造したトレー状の充填包装容器を使用し、そのトレー状の充填包装容器の中に、その開口部から、炊飯した御飯を計量して充填し、しかる後、上記で御飯を充填したトレー状の充填包装容器の開口部のフランジ部の面に、本発明にかかる無菌米飯充填包装容器用蓋材のヒ−トシール性樹脂層の面を対向させて重ね合わせ、しかる後、そのフランジ部の面とヒ−トシール性樹脂層の面とをヒ−トシールしてシール部を形成して、本発明にかかる無菌包装米飯を製造することができる。
勿論、本発明において、上記のような製造プロセスは、前述のように、クリーンルームあるいはクリーンブース等において実施されるものである。
上記において、ヒートシールの方法としては、例えば、バーシール、回転ロールシール、ベルトシール、インパルスシール、高周波シール、超音波シール等の企知の方法で行うことができる。
また、上記において、充填包装する御飯としては、通常の米飯、赤飯、玄米等を混入した御飯、お粥、その他公知のものを充填包装することができるものである。
而して、上記の本発明にかかる無菌米飯充填包装容器用蓋材およびそれを使用した無菌包装米飯は、強度等を有して耐久性に優れ、かつ、耐熱性、防湿性、ヒートシール性、耐ピンホール性、耐突き刺し性、透明性等にも優れ、更に、酸素ガス、水蒸気等の透過を阻止するバリア性に優れ、その内容物の充填包装適性、保存適性等を有し、更にまた、使用後において包装用袋は、焼却廃棄処理する際に有害物質等を発生することなく、廃棄処理適性、環境適性等に極めて優れているという利点を有するものである。
【００６７】
【実施例】
上記の本発明について実施例を挙げて更に具体的に説明する。
実施例１
（１）．厚さ１５μｍの二軸延伸ナイロン６フィルムを使用し、これをプラズマ化学気相成長装置の送り出しロールに装着し、下記に示す条件で、上記の二軸延伸ナイロン６フィルムのコロナ処理面に、厚さ２００Åの酸化珪素の蒸着膜を形成した。
（蒸着条件）
蒸着面；コロナ処理面
反応ガス混合比；ヘキサメチルジシロキサン：酸素ガス：ヘリウム＝１．２：５．０：２．５（単位：ｓｌｍ）
到達圧力；５．０×１０^−５ｍｂａｒ
製膜圧力；７．０×１０^−２ｍｂａｒ
パワ−；３５ｋＷ
ライン速度；３００ｍ／ｍｉｎ
次に、上記で膜厚２００Åの酸化珪素の蒸着膜を形成した直後に、その酸化珪素の蒸着膜面に、グロ−放電プラズマ発生装置を使用し、パワ−９ｋｗ、酸素ガス（Ｏ_２ ）：アルゴンガス（Ａｒ）＝７．０：２．５（単位：ｓｌｍ）からなる混合ガスを使用し、混合ガス圧６×１０^−２ｍｂａｒで酸素／アルゴン混合ガスプラズマ処理を行って、酸化珪素の蒸着膜面の表面張力を５４ｄｙｎｅ／ｃｍ以上向上させたプラズマ処理面を形成した。
（２）．他方、還流冷却器、攪拌機を備えた反応器に、テトラ−ｉ−プロポキシチタン１００部、アセチルアセトン７０部を加え、６０℃で３０分間攪拌し、チタンキレート化合物を得た。
この反応生成物の純度は７５％であった。
次に、（Ａ）成分として、エチレン・ビニルアルコール共重合体〔日本合成化学株式会社製、商品名、ソアノールＤ２９３５、ケン化度；９８％以上、エチレン含量；２９モル％、メルトフローインデックス；３５ｇ／１０分〕、および、ポリビニルピロリドン〔和光純薬株式会社製、Ｍｗ＝２５，０００〕を、それぞれ、５％含む水／ｎ−プロピルアルコール溶液（水／ｎ−プロピルアルコール重量比＝４０／６０）１００部と、ならびに、上記で調製したチタンキレート化合物２部とｎ−プロピルアルコール１６．８部、および水１１．２部を混合して、５５℃で４時間加水分解した（Ｂ）成分と、更に、Ｎ，Ｎ−ジメチルホルムアミド１２．１部とを、４０℃で混合して２時間攪拌し、本発明のガスバリア性組成物を得た。
次に、上記の（１）で形成したプラズマ処理面に、上記で製造したガスバリア性組成物を使用し、これをグラビアロールコート法によりコーティングして、次いで、１２０℃で１分間、加熱処理して、厚さ１．０ｇ／ｍ^２ （乾燥状態）のガスバリア性塗布膜を形成して、バリア性基材を製造した。
（３）．次に、上記で製造したバリア性基材のガスバリア性塗布膜の面に、通常のグラビアインキ組成物を使用し、グラビア印刷方式により、文字、図形、記号、絵柄、その他等からなる所定の印刷模様を印刷して印刷模様層を形成した。
次に、上記で形成した印刷模様層を含む全面に、ウレタン系接着剤（武田薬品工業株式会社製、商品名、Ａ６１６）を使用し、これをグラビアロ−ルコ−ト法でコ−ティングし、乾燥被膜が４ｇ／ｍ^２ であるラミネ−ト用接着剤層を形成し、次いで、そのラミネ−ト用接着剤層の面に、厚さ５０μｍの直鎖状低密度ポリエチレンフィルムを、そのコロナ処理面の面を対向させて重ね合わせ、しかる後、その両者をドライラミネ−ト積層して、本発明にかかる無菌米飯充填包装容器用蓋材を製造した。
（４）．他方、厚さ１５０μｍのポリプロピレン樹脂フィルムを使用し、これを真空・圧空成形方式を用いて熱成形して、ポリプロピレン製のトレー状の成形容器を製造した。
次に、上記で製造したポリプロピレン製のトレー状の成形容器を十分に洗浄し、更に、過酸化水素液等で殺菌処理した後、クラス１０、０００程度のクリーンルームに搬入し、次いで、クリーンルームにおいて、上記で殺菌処理したポリプロピレン製のトレー状の成形容器の中に、同じくクリーンルームにおいて炊飯した御飯を定量して充填し、しかる後、そのトレー状の成形容器の開口部のフランジ部に、上記の（３）で製造し、上記と同様に洗浄し、過酸化水素液等で殺菌処理した無菌米飯充填包装容器用蓋材の直鎖状低密度ポリエチレンフィルムの面を対向させて重ね合わせ、次いで、その両者をヒートシールして密閉包装し、そのまま放冷して、無菌包装米飯を製造した。
上記で製造した無菌包装米飯からなる包装製品は、酸素ガス、水蒸気等に対するバリア性に優れ、また、ラミネート強度等に優れ、市場における流通に耐え、かつ、貯蔵保存等に優れているものであった。
【００６８】
実施例２
（１）．上記の実施例２と同様にして、厚さ１５μｍの２軸延伸ナイロン６フィルムのコロナ処理面に、厚さ２００Åの酸化珪素の蒸着膜を形成し、更に、その酸化珪素の蒸着膜のプラズマ処理面の面に、ガスバリア性塗布膜を形成して、本発明にかかるバリア性基材を製造した。
（２）．次に、上記の（１）で形成した酸化珪素の蒸着膜のガスバリア性塗布膜の面に、更に、上記の実施例１と同様にして、印刷模様層、および、ラミネート用接着剤層を形成した。
次いで、上記で形成したラミネート用接着剤層の面に、厚さ１５μｍの２軸延伸ナイロン６フィルムを、そのコロナ処理面を対向させて重ね合わせ、しかる後、ドライラミネート積層した。
更に、上記で積層した厚さ１５μｍの２軸延伸ナイロン６フィルムの他方の面に、２液硬化型のポリウレタン系ラミネート用接着剤を使用し、これを、上記の実施例１と同様に、グラビアロールコート法により、膜厚４ｇ／ｍ^２ （乾燥状態）になるようにコーティングしてラミネート用接着剤層を形成した。
次いで、上記で形成したラミネート用接着剤層面に、厚さ５０μｍの直鎖状低密度ポリエチレンフィルムを、そのコロナ処理面を対向させて重ね合わせ、しかる後、その両者をドライラミネート積層して、本発明にかかる無菌米飯充填包装容器用蓋材を製造した。
（３）．以下、上記で製造した無菌米飯充填包装容器用蓋材を使用し、上記の実施例１と全く同様にして、上記の実施例１と同様に、本発明にかかる無菌包装米飯を製造した。
上記で製造した無菌包装米飯からなる包装製品は、酸素ガス、水蒸気等に対するバリア性に優れ、また、ラミネート強度等に優れ、市場における流通に耐え、かつ、貯蔵保存等に優れているものであった。
【００６９】
実施例３
（１）．基材フィルムとして、厚さ１２μｍの二軸延伸ポリエチレンテレフタレ−トフィルムを使用し、これをプラズマ化学気相成長装置の送り出しロ−ルに装着し、次いで、これを繰り出して、下記に示す条件で、上記の二軸延伸ポリエチレンテレフタレ−トフィルムのコロナ処理面に、厚さ２００Åの酸化珪素の蒸着膜を形成した。
（蒸着条件）
蒸着面；コロナ処理面
反応ガス混合比；ヘキサメチルジシロキサン：酸素ガス：ヘリウム＝１：１１：１０（単位：ｓｌｍ）
真空チヤンバー内の真空度；５．２×１０^−６ｍｂａｒ
蒸着チヤンバー内の真空度；５．１×１０^−２ｍｂａｒ
冷却・電極ドラム供給電力；６０ｗ・分／ｍ^２
フィルムの搬送速度；９０ｍ／ｍｉｎ
次に、上記で膜厚２００Åの酸化珪素の蒸着膜を形成した直後に、その酸化珪素の蒸着膜面に、上記の実施例１と同様にしてプラズマ処理を行って、酸化珪素の蒸着膜面の表面張力を５４ｄｙｎｅ／ｃｍ以上向上させたプラズマ処理面を形成した。
（２）．次に、上記の（１）で形成した酸化硅素のプラズマ処理面の面に、更に、上記の実施例１と同様にして、ガスバリア性塗布膜、印刷模様層、および、ラミネート用接着剤層を形成した。
次いで、上記で形成したラミネート用接着剤層の面に、厚さ１５μｍの２軸延伸ナイロン６フィルムを、そのコロナ処理面を対向させて重ね合わせ、しかる後、ドライラミネート積層した。
更に、上記で積層した厚さ１５μｍの２軸延伸ナイロン６フィルムの他方の面に、２液硬化型のポリウレタン系ラミネート用接着剤を使用し、これを、上記の実施例１と同様に、グラビアロールコート法により、膜厚４．０ｇ／ｍ^２ （乾燥状態）になるようにコーティングしてラミネート用接着剤層を形成した。
次いで、上記で形成したラミネート用接着剤層面に、厚さ５０μｍの直鎖状低密度ポリエチレンフィルムを、そのコロナ処理面を対向させて重ね合わせ、しかる後、その両者をドライラミネート積層して、本発明にかかる無菌米飯充填包装容器用蓋材を製造した。
（３）．他方、ポリプロピレン樹脂を使用し、これを射出成形方式を用いて熱成形して、ポリプロピレン製のトレー状の成形容器を製造した。
次に、上記で製造したポリプロピレン製のトレー状の成形容器を十分に洗浄し、更に、過酸化水素液等で殺菌処理した後、クラス１０、０００程度のクリーンルームに搬入し、次いで、クリーンルームにおいて、上記で殺菌処理したポリプロピレン製のトレー状の成形容器の中に、同じくクリーンルームにおいて炊飯した御飯を定量して充填し、しかる後、そのトレー状の成形容器の開口部のフランジ部に、上記の（２）で製造し、上記と同様に洗浄し、過酸化水素液等で殺菌処理した無菌米飯充填包装容器用蓋材の直鎖状低密度ポリエチレンフィルムの面を対向させて重ね合わせ、次いで、その両者をヒ−トシールして密閉包装し、そのまま放冷して、無菌包装米飯を製造した。
上記で製造した無菌包装米飯からなる包装製品は、酸素ガス、水蒸気等に対するバリア性に優れ、また、ラミネート強度等に優れ、市場における流通に耐え、かつ、貯蔵保存等に優れているものであった。
【００７０】
実施例４
（１）．基材フィルムとして、厚さ１５μｍの２軸延伸ナイロン６フィルムを使用し、まず、上記の２軸延伸ナイロン６フィルムを巻き取り式の真空蒸着装置の送り出しロ−ルにに装着し、次いで、これを繰り出し、その２軸延伸ナイロン６フィルムのコロナ処理面に、アルミニウムを蒸着源に用いて、酸素ガスを供給しながら、エレクトロンビ−ム（ＥＢ）加熱方式による真空蒸着法により、下記の蒸着条件により、膜厚２００Åの酸化アルミニウムの蒸着膜を形成した。
（蒸着条件）
蒸着チャンバ−内の真空度：２×１０^−４ｍｂａｒ
巻き取りチャンバ−内の真空度：２×１０^−２ｍｂａｒ
電子ビ−ム電力：２５ｋＷ
フィルムの搬送速度：２４０ｍ／分
蒸着面：コロナ処理面
次に、上記で厚さ２００Åの酸化アルミニウムの蒸着膜を形成した直後に、その酸化アルミニウムの蒸着膜面に、上記の実施例１と同様にして、プラズマ処理面を形成した。
（２）．他方、還流冷却器、攪拌機を備えた反応器に、テトラ−ｉ−プロポキシチタン１００部、アセチルアセトン７０部を加え、６０℃で３０分間攪拌し、チタンキレート化合物を得た。
この反応生成物の純度は７５％であった。
次に、（Ａ）成分として、エチレン・ビニルアルコール共重合体〔日本合成化学株式会社製、商品名、ソアノールＤ２９３５、ケン化度；９８％以上、エチレン含量；２９モル％、メルトフローインデックス；３５ｇ／１０分〕、および、ポリビニルピロリドン〔和光純薬株式会社製、Ｍｗ＝２５，０００〕を、それぞれ、５％含む水／ｎ−プロピルアルコール溶液（水／ｎ−プロピルアルコール重量比＝４０／６０）１００部と、ならびに、上記で調製したチタンキレート化合物２部とｎ−プロピルアルコール１６．８部、および水１１．２部を混合して、５５℃で４時間加水分解した（Ｂ）成分と、更に、Ｎ，Ｎ−ジメチルホルムアミド１２．１部とを、４０℃で混合して２時間攪拌し、本発明のガスバリア性組成物を得た。
次に、上記の（１）で形成したプラズマ処理面に、上記で製造したガスバリア性組成物を使用し、これをグラビアロールコート法によりコーティングして、次いで、１２０℃で１分間、加熱処理して、厚さ１．０ｇ／ｍ^２ （乾燥状態）のガスバリア性塗布膜を形成して、バリア性基材を製造した。
（３）．更に、上記で形成したバリア性基材を構成するガスバリア性塗布膜の面に、通常のグラビアインキ組成物を使用し、グラビア印刷方式により、文字、図形、記号、絵柄、その他等からなる所定の印刷模様を印刷して印刷模様層を形成した。
次に、上記で形成した印刷模様層を含む全面に、２液硬化型のポリウレタン系ラミネート用接着剤を使用し、これを、上記と同様に、グラビアロールコート法により、膜厚４．０ｇ／ｍ^２ （乾燥状態）になるようにコーティングしてラミネート用接着剤層を形成した。
次いで、上記で形成したラミネート用接着剤層面に、厚さ５０μｍの直鎖状低密度ポリエチレンフィルムを、そのコロナ処理面を対向させて重ね合わせ、しかる後、その両者をドライラミネート積層して、本発明にかかる無菌米飯充填包装容器用蓋材を製造した。
（４）．他方、ポリプロピレン樹脂とナイロンＭＸＤ６樹脂とを使用し、これらをインフレーション共押出成形方式を使用して共押出して、厚さ１５０μｍのポリプロピレン樹脂層／厚さ１００μｍのナイロンＭＸＤ６樹脂層／厚さ５０μｍのポリプロピレン樹脂層からなる３層共押出フィルムを製造した。
次いで、上記で製造した３層共押出フィルムを使用し、これを真空・圧空成形方式を用いて熱成形して、トレー状の成形容器を製造した。
次に、上記で製造したトレー状の成形容器を十分に洗浄し、更に、過酸化水素液等で殺菌処理した後、クラス１０、０００程度のクリーンルームに搬入し、次いで、クリーンルームにおいて、上記で殺菌処理したトレー状の成形容器の中に、同じくクリーンル〜ムにおいて炊飯した御飯を定量して充填し、しかる後、そのトレー状の成形容器の開口部のフランジ部に、上記の（３）で製造し、上記と同様に洗浄し、過酸化水素液等で殺菌処理した無菌米飯充填包装容器用蓋材の直鎖状低密度ポリエチレンフィルムの面を対向させて重ね合わせ、次いで、その両者をヒ−トシールして密閉包装し、そのまま放冷して、無菌包装米飯を製造した。
上記で製造した無菌包装米飯からなる包装製品は、酸素ガス、水蒸気等に対するバリア性に優れ、また、ラミネート強度等に優れ、市場における流通に耐え、かつ、貯蔵保存等に優れているものであった。
【００７１】
実施例５
（１）．基材フィルムとして、厚さ１２μｍの２軸延伸ポリエチレンテレフタレ−トフィルムを使用し、まず、上記の２軸延伸ポリエチレンテレフタレ−トフィルムを巻き取り式の真空蒸着装置の送り出しロ−ルにに装着し、次いで、これを繰り出し、その２軸延伸ポリエチレンテレフタレ−トフィルムのコロナ処理面に、アルミニウムを蒸着源に用いて、酸素ガスを供給しながら、エレクトロンビ−ム（ＥＢ）加熱方式による真空蒸着法により、下記の蒸着条件により、膜厚２００Åの酸化アルミニウムの蒸着膜を形成した。
（蒸着条件）
蒸着チャンバ−内の真空度：２×１０^−４ｍｂａｒ
巻き取りチャンバ−内の真空度：２×１０^−２ｍｂａｒ
電子ビ−ム電力：２５ｋＷ
フィルムの搬送速度：２４０ｍ／分
蒸着面：コロナ処理面
次に、上記で厚さ２００Åの酸化アルミニウムの蒸着膜を形成した直後に、その酸化アルミニウムの蒸着膜面に、上記の実施例１と同様にして、プラズマ処理面を形成した。
（２）．次に、上記の（１）で形成した酸化アルミニウムの蒸着膜のプラズマ処理面に、更に、上記の実施例４と同様にして、ガスバリア性塗布膜、印刷模様層、および、ラミネート用接着剤層を形成した。
次いで、上記で形成したラミネート用接着剤層面に、厚さ１５μｍの２軸延伸ナイロン６フィルムを、そのコロナ処理面を対向させて重ね合わせ、しかる後、ドライラミネート積層した。
更に、上記で積層した厚さ１５μｍの２軸延伸ナイロン６フィルムの他方の面に、２液硬化型のポリウレタン系ラミネート用接着剤を使用し、これを、上記の実施例２と同様に、グラビアロールコート法により、膜厚４．０ｇ／ｍ^２ （乾操状態）になるようにコーティングしてラミネート用接着剤層を形成した。
次いで、上記で形成したラミネート用接着剤層の面に、厚さ５０μｍの直鎖状低密度ポリエチレンフィルムを、そのコロナ処理面を対向させて重ね合わせ、しかる後、その両者をドライラミネート積層して、本発明にかかる無菌米飯充填包装容器用蓋材を製造した。
（３）．以下、上記で製造した無菌米飯充填容器用蓋材を使用し、上記の実施例１と全く同様にして、上記の実施例１と同様に、本発明にかかる無菌包装米飯を製造した。
上記で製造した無菌包装米飯からなる包装製品は、酸素ガス、水蒸気等に対するバリア性に優れ、また、ラミネート強度等に優れ、市場における流通に耐え、かつ、貯蔵保存等に優れているものであった。
【００７２】
実験例
上記の実施例１〜５で製造した無菌米飯充填包装容器用蓋材について、酸素透過度、水蒸気透過度、および、耐突き刺し強度を測定した。
（１）．酸素透過度の測定
これは、温度２３℃、湿度９０％ＲＨの条件で、米国、モコン（ＭＯＣＯＮ）社製の測定機〔機種名、オクストラン（ＯＸＴＲＡＮ）〕にて測定した。
（２）．水蒸気透過度の測定
これは、温度４０℃、湿度９０％ＲＨの条件で、米国、モコン（ＭＯＣＯＮ）社製の測定機〔機種名、パ−マトラン（ＰＥＲＭＡＴＲＡＮ）〕にて測定した。
（３）．耐突き刺し強度の測定
これは、半径０．５ｍｍの針先端により５０ｍｍ／分の圧縮速度での蓋材の突き刺し強度を引っ張り試験機により測定した。
上記の測定結果について、下記の表１に示す。
【００７３】
（表１）

上記の表１において、酸素透過度の単位は、〔ｃｃ／ｍ^２ ／ｄａｙ・２３℃・９０％ＲＨ〕であり、水蒸気透過度の単位は、〔ｇ／ｍ^２ ／ｄａｙ・４０℃・１００％ＲＨ〕であり、耐突き刺し強度の単位は、〔ｇｆ〕である。
【００７４】
上記の表１に示す測定結果より明らかなように、本発明にかかる無菌米飯充填包装容器用蓋材は、酸素バリア性、および、水蒸気バリア性等に優れ、また、耐突き刺し強度においても優れているものであった。
【００７５】
【発明の効果】
以上の説明で明らかなように、本発明は、基材フィルムの一方の面に、酸化珪素、酸化アルミニウム等の無機酸化物の蒸着膜を設けた構成からなるバリア性フィルムに着目し、まず、該バリア性フィルムを構成する酸化珪素、酸化アルミニウム等の無機酸化物の蒸着膜の上に、更に、ガスバリア性塗布膜、印刷模様層、および、ラミネート用接着剤層を順次に設け、更にまた、該ラミネート用接着剤層を介して、ヒートシール性樹脂層を設けて蓋材を製造し、而して、該蓋材を使用し、これを、例えば、ポリプロピレン系樹脂を使用し、これを成形してなるポリプロピレン系樹脂製のトレー状の充填包装容器に炊飯した御飯を充填した後、その包装用容器の開口部のフランジ部に、その蓋材を構成するヒートシール性樹脂層の面を対向させて重ね合わせ、しかる後、その両者をヒートシール等により密接着させて密閉包装して無菌包装米飯を製造して、強度等を有し、かつ、耐熱性、防湿性、ヒートシール性、耐ピンホール性、耐突き刺し性、透明性等に優れ、更に、酸素ガス、水蒸気等の透過を阻止するバリア性に優れ、その内容物の充填包装適性、保存適性等を有し、更にまた、使用後に焼却廃棄処理する際に有害物質等を発生することなく、廃棄処理適性、環境適性等に極めて優れた蓋材およびそれを使用した無菌包装米飯を製造し得ることができるというものである。
【図面の簡単な説明】
【図１】本発明にかかる無菌米飯充填包装容器用蓋材についてその一例の層構成の概略を示す概略的断面図である。
【図２】本発明にかかる無菌米飯充填包装容器用蓋材についてその一例の層構成の概略を示す概略的断面図である。
【図３】本発明にかかる無菌包装米飯に使用する充填包装容器についてその構成の一例を示す概略的斜視図である。
【図４】図３に示す本発明にかかる無菌包装米飯に使用する充填包装容器に炊飯した御飯を充填し、その充填包装容器の開口部のフランジ部に図１に示す本発明にかかる無菌米飯充填包装容器用蓋材を使用し、これをヒ−トシールして密閉包装して製造した無菌包装米飯についてその構成の一例を示す概略的断面図である。
【図５】低温プラズマ化学蒸着装置の一例を示す枕略的構成図である。
【図６】巻き取り式真空蒸着装置の一例を示す概略的横成図である。
【符号の説明】
Ａ 無菌米飯充填包装容器用蓋材
Ａ_１ 無菌米飯充填包装容器用蓋材
Ｂ トレー状の充填包装容器
Ｃ 無菌包装米飯
１ 基材フィルム
２ 無機酸化物の蒸着膜
３ ガスバリア性塗布膜
４ 印刷模様層
５ ラミネート用接着剤層
６ ヒートシール性樹脂層
７ 強度を有し、耐突き刺し性に優れた樹脂のフィルム
１１ 開口部
１２ フランジ部
１３ 側壁
１４ 底壁
１５ 御飯
１６ シ−ル部[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a lid for aseptic rice filling and packaging container and aseptic packaging rice using the same, and more particularly has strength and the like, and has heat resistance, moisture resistance, heat sealability, pinhole resistance, Excellent piercing property, transparency, etc. Furthermore, it has excellent barrier properties to prevent the permeation of oxygen gas, water vapor, etc., its contents are suitable for packing and storage, storage suitability, etc. Furthermore, it is incinerated and discarded after use. In particular, the present invention relates to a lid for aseptic rice filling and packaging container that is extremely excellent in waste disposal suitability, environmental suitability, etc. without generating harmful substances, and aseptic packaging cooked rice using the same.
[0002]
[Prior art]
In recent years, rice cooked aseptically at normal pressure is filled into a packaging container consisting of a plastic tray sterilized in a sterile atmosphere, and then the opening is sealed with a plastic lid or the like Aseptically packaged cooked rice is marketed and its market is growing rapidly.
Thus, the above-mentioned aseptically packaged cooked rice usually undergoes a process consisting of rice milling, rice washing / dipping, draining, etc., and then, in a clean room or clean booth, etc. After filling a filling and packaging container composed of, etc., then, a rice cooking / packaging process consisting of hermetic packaging or the like that seals the opening of the filling and packaging container filled with the cooked rice with a plastic lid material, etc., then, Manufactured through a process consisting of cooling, boxing, inspection, etc.
In the aseptic packaged rice manufacturing process as described above, for example, a polypropylene resin is used as a filling and packaging container made of a plastic tray or the like, and this is molded by a thermoforming method such as vacuum or pneumatic molding. Tray-shaped filled packaging container made of polypropylene resin, or a polypropylene resin layer / polyvinylidene chloride resin layer or ethylene-vinyl alcohol copolymer layer as a barrier material that blocks permeation of oxygen, water vapor, etc. / A three-layer coextruded film made of a polypropylene resin layer or the like is used, and a tray-shaped filling and packaging container formed by vacuum or pressure forming of the film is used.
In addition, after filling cooked rice into a filling and packaging container made of a plastic tray or the like, the plastic lid material that seals and seals the opening thereof, for example, a gas barrier that prevents permeation of oxygen gas, water vapor, etc. Laminate laminated using a single-layer film of polyvinylidene chloride resin with excellent properties, laminated material laminated using co-extruded film also using polyvinylidene chloride resin, or polychlorinated A lid member made of a laminated material or the like laminated by using a coat film made of a vinylidene resin composition is used (see, for example, Patent Document 1 and Patent Document 2).
In addition, a lid material made of a laminated material obtained by using an ethylene-vinyl alcohol copolymer film and laminating it with another plastic film or the like is also used as a barrier material (see, for example, Patent Document 3). ).
[0003]
[Patent Document 1]
Japanese Patent Publication No.57-30745 (Claims, Examples)
[Patent Document 2]
Japanese Utility Model Publication No. 62-123920 (Scope of Claim for Utility Model Registration, Examples)
[Patent Document 3]
JP-A-9-239911 (Claims, Examples)
[0004]
[Problems to be solved by the invention]
By the way, in the aseptic packaging cooked rice as described above, for example, a polypropylene resin is used as a filling and packaging container including a plastic tray as described above, and a polypropylene resin tray formed by molding the resin is used. When using a filled packaging container, if it is used and disposed of as waste by incineration, etc., it is composed of polyolefin resin, which generates harmful substances and destroys the environment. It is said that there are relatively few problems such as impairing environmental suitability.
However, as a barrier material, in the case of a tray-like filling and packaging container using a polyvinylidene chloride resin as described above, or a plastic lid material using a polyvinylidene chloride resin or the like, oxygen gas, water vapor In the gas barrier property that prevents the permeation of etc., it has the desired effect, but after using it as a filling packaging container or lid material etc., when discarding these as garbage, for example, by incineration processing etc. Because it contains chlorine atoms, it causes generation of toxic gases such as dioxins at the time of incineration disposal, and there is concern about the impact on the human body. There is a problem that the environmental suitability and the like are impaired.
Similarly to the above, as a barrier material, a tray-like filling and packaging container using an ethylene-vinyl alcohol copolymer, or a lid material using an ethylene-vinyl alcohol copolymer film, etc. In the state, it has excellent gas barrier properties that prevent the permeation of oxygen gas, water vapor, etc., and has the desired effect, but in the wet state, the gas barrier properties that block the permeation of oxygen gas, water vapor, etc. are significantly reduced. There is a problem that it can no longer withstand its use.
Therefore, the present invention is an aseptic packaged cooked rice, particularly as a plastic lid, having strength and the like, and excellent in heat resistance, moisture resistance, heat sealability, pinhole resistance, puncture resistance, transparency, etc. In addition, it has excellent barrier properties to prevent the permeation of oxygen gas, water vapor, etc., has the contents suitable for filling and packaging, storage, etc. Furthermore, it generates harmful substances when incinerated after use. The object is to provide a lid for aseptic rice filling and packaging container which is extremely excellent in disposal processing suitability, environmental suitability, etc., and to provide aseptic packaging cooked rice using the same.
[0005]
[Means for Solving the Problems]
As a result of various studies to solve the above problems, the present inventor has a barrier property comprising a structure in which a vapor deposition film of an inorganic oxide such as silicon oxide or aluminum oxide is provided on one surface of a base film. Focusing on the film, first, a gas barrier coating film, a printed pattern layer, and an adhesive layer for laminating are further formed on the deposited film of inorganic oxide such as silicon oxide and aluminum oxide constituting the barrier film. Providing sequentially, and furthermore, providing a heat sealing resin layer through the adhesive layer for laminating to produce a lid material, and thus using the lid material, for example, polypropylene resin After filling the cooked rice into a tray-shaped filling packaging container made of polypropylene resin, which is molded from this, the heat seal constituting the lid material on the flange portion of the opening of the packaging container sex When the surfaces of the fat layers are placed facing each other and then laminated, the two are tightly bonded by heat sealing or the like and hermetically wrapped to produce aseptically packaged cooked rice, which has strength, etc., heat resistance, moisture resistance Excellent heat sealability, pinhole resistance, puncture resistance, transparency, etc.Further, it has excellent barrier properties to prevent permeation of oxygen gas, water vapor, etc. Furthermore, it has been found that it is possible to produce a lid material that is extremely excellent in disposal and environmental suitability and aseptically packaged rice using the same without generating harmful substances when incinerated and discarded after use. This completes the present invention.
[0006]
That is, the present invention provides an inorganic oxide vapor-deposited film and a gas barrier coating film on one surface of a base film, and further, a printed pattern layer and a laminate layer on the gas barrier coating film. The present invention relates to a lid for aseptic rice filling and packaging container, characterized in that an adhesive layer is sequentially provided, and then a heat-sealable resin layer is provided via the adhesive layer for laminating, and aseptic packaging rice using the same Is.
[0007]
DETAILED DESCRIPTION OF THE INVENTION
The lid for aseptic rice filling container according to the present invention and the aseptic packaged rice using the same will be described below in more detail with reference to the drawings.
FIG. 1 and FIG. 2 are schematic cross-sectional views showing one example of the layer structure of the lid for aseptic rice filling and packaging container according to the present invention, and FIG. 3 is used for the aseptic packaging rice according to the present invention. FIG. 4 is a schematic perspective view showing an example of the configuration of the filling and packaging container, and FIG. 4 is a diagram illustrating the filling and filling of cooked rice in the filling and packaging container used for the aseptic packaging rice according to the present invention shown in FIG. About the aseptic packaged rice produced by using the lid for aseptic rice filling and packaging container according to the present invention shown in FIG. It is a schematic sectional drawing which shows an example of a structure.
[0008]
First, as the lid A for aseptic cooked rice filling and packaging container according to the present invention, as shown in FIG. 1, an inorganic oxide vapor-deposited film 2 is provided on one surface of a base film 1, and the inorganic oxidation is further performed. A gas barrier coating film 3 and further a printed pattern layer 4 are provided on the vapor deposition film 2 of the object, and then an adhesive layer 5 for laminating is provided on the entire surface including the printed pattern layer 4, The basic structure is a structure in which the heat-sealable resin layers 6 are sequentially provided via the laminating adhesive layer 5.
Thus, as another example of the lid for aseptic rice filling and packaging container according to the present invention, as shown in FIG. 2, the lid for aseptic rice filling and packaging container according to the present invention shown in FIG. In A, the sterilized cooked rice according to the present invention having a structure in which a resin film 7 having strength and excellent puncture resistance is further laminated between the adhesive layer 5 for laminating and the heat-sealable resin layer 6 Filling packaging container lid A₁Can be illustrated.
In FIG. 2, reference numerals 1, 2, 3, 4, 5, etc. represent the same meaning as the reference numerals shown in FIG.
The above illustrations illustrate one or two examples of the lid for aseptic cooked rice filling and packaging container according to the present invention, and the present invention is not limited thereto.
For example, although not shown in the drawings, in the lid for aseptic rice filling and packaging container according to the present invention, as the inorganic oxide vapor deposition film, two or more inorganic oxide vapor deposition films of the same type or different types are laminated. It can be configured.
Furthermore, in the present invention, other plastic films, paper base materials, etc. can be arbitrarily laminated as the lid for aseptic cooked rice filling and packaging container according to the present invention.
[0009]
Next, in the present invention, aseptic packaging rice using the above-described lid for aseptic rice filling and packaging container according to the present invention will be described. First, in the present invention, as shown in FIG. Using a resin or the like, for example, injection molding, extrusion molding, or using a single film or a co-extrusion film, etc., by thermoforming such as vacuum / compression molding, etc., the flange portion around the opening 11 12, and further, a tray-shaped filling and packaging container B having a quadrangular shape having a side wall 13 and a bottom wall 14 depending from the flange portion 12 is manufactured.
Thus, in the present invention, as shown in FIG. 4, the cooked rice 15 is weighed and filled into the tray-shaped packaging container B produced as described above, and then the rice 15 is added as described above. On the surface of the flange portion 12 of the opening 11 of the tray-shaped packaging container B filled, the surface of the heat-sealable resin layer 6 of the lid A for aseptic cooked rice packaging container according to the present invention shown in FIG. The surface of the flange portion 12 and the surface of the heat-sealable resin layer 6 are heat-sealed to form a seal portion 16, and the aseptic packaged rice C according to the present invention is obtained. Can be manufactured.
Of course, in the present invention, the manufacturing process as described above is performed in a clean room or a clean booth as described above.
The above exemplification is an example of aseptic packaged rice using the lid for aseptic rice filling and packaging container according to the present invention, and the present invention is not limited thereto.
For example, in the present invention, although not shown, the aseptic rice filling packaging container according to the present invention shown in FIG. 2 is used, and the same as above, the aseptic rice filling according to the present invention is performed. Aseptic packaged cooked rice using a packaging container lid can be produced.
Further, in the present invention, although not shown in the drawings, the tray-like packaging container has a rectangular shape as described above, for example, a triangle, a pentagon, a hexagon, other polygons, a circle, a rhombus, Of course, it can take any other form.
[0010]
Next, in the present invention, the lid for aseptic rice filling and packaging container according to the present invention, the material constituting the aseptic packaging rice and the production method thereof will be described. First, aseptic rice filling and packaging container according to the present invention As a base film that constitutes cover materials, aseptically packaged cooked rice, etc., it has excellent chemical or physical strength, can withstand the conditions for forming a vapor-deposited film of inorganic oxide, and the properties of such a vapor-deposited film of inorganic oxide It is possible to use a resin film or sheet that can be satisfactorily held without impairing the resistance.
Thus, in the present invention, the resin film or sheet specifically includes, for example, a polyolefin resin such as a polyethylene resin or a polypropylene resin, a cyclic polyolefin resin, a polystyrene resin, and acrylonitrile-styrene. Copolymer (AS resin), acrylonitrile loop tagene-styrene copolymer (ABS resin), poly (meth) acrylic resin, polycarbonate resin, polyester resin such as polyethylene terephthalate, polyethylene naphthalate, various nylons, etc. Various resin films or sheets such as polyamide resins, polyurethane resins, acetal resins, cellulose resins, and the like can be used.
In the present invention, it is particularly preferable to use a polyester resin, a polyolefin resin, or a polyamide resin film or sheet among the above-described resin films or sheets.
[0011]
In the present invention, as the above-mentioned various resin films or sheets, for example, one or more of the above-mentioned various resins are used, extrusion method, cast molding method, T-die method, cutting method, inflation method, Using other film-forming methods, a method of forming the above-mentioned various resins alone, or a method of forming a multilayer co-extrusion film using two or more kinds of resins, Using two or more kinds of resins, by mixing and forming a film before forming a film, various resin films or sheets are manufactured, and if necessary, for example, a tenter method, or Various resin films or sheets that are stretched uniaxially or biaxially using a tubular method or the like can be used.
In the present invention, the film thickness of various resin films or sheets is preferably about 6 to 2000 μm, more preferably about 9 to 100 μm.
[0012]
It should be noted that one or more of the above-mentioned various resins are used, and in forming the film, for example, film processability, heat resistance, weather resistance, mechanical properties, dimensional stability, antioxidant properties, slipperiness Various plastic compounding agents and additives can be added for the purpose of improving and modifying mold release properties, flame retardancy, antifungal properties, electrical properties, strength, etc. Can be optionally added from a very small amount to several tens of percent depending on the purpose.
In the above, as a general additive, for example, a lubricant, a crosslinking agent, an antioxidant, an ultraviolet absorber, a light stabilizer, a filler, a reinforcing agent, an antistatic agent, a pigment, and the like can be used. Furthermore, a modifying resin or the like can be used.
[0013]
In addition, in the present invention, the surface of various resin films or sheets is provided with a desired surface treatment layer in advance, if necessary, in order to improve close adhesion with an inorganic oxide vapor-deposited film. It is something that can be done.
In the present invention, examples of the surface treatment layer include corona discharge treatment, ozone treatment, low temperature plasma treatment using oxygen gas or nitrogen gas, glow discharge treatment, oxidation treatment using chemicals, etc. For example, a corona treatment layer, an ozone treatment layer, a plasma treatment layer, an oxidation treatment layer, or the like can be formed and provided.
The surface pretreatment is carried out as a method for improving the close adhesion between various resin films or sheets and the inorganic oxide vapor-deposited film. In addition, for example, a primer coat agent layer, an undercoat agent layer, an anchor coat agent layer, an adhesive layer, or a deposition anchor coat agent layer is arbitrarily formed in advance on the surface of various resin films or sheets. And it can also be set as a surface treatment layer.
Examples of the pretreatment coating agent layer include polyester resins, polyamide resins, polyurethane resins, epoxy resins, phenol resins, (meth) acrylic resins, polyvinyl acetate resins, polyethylene, and polypropylene. A resin composition having a vehicle as a main component of a polyolefin resin or a copolymer or modified resin thereof, a cellulose resin, or the like can be used.
[0014]
Next, in the present invention, the inorganic oxide vapor deposition film constituting the lid for aseptic rice filling and packaging container according to the present invention, the aseptic packaged rice, etc. will be described. Specifically, for example, a chemical vapor deposition method such as a plasma chemical vapor deposition method, a thermal chemical vapor deposition method, or a photochemical vapor deposition method (Chemical Vapor Deposition method) can be used. , A CVD method) or the like can be used to form an inorganic oxide vapor-deposited film.
In the present invention, specifically, a vapor deposition monomer gas such as an organosilicon compound is used as a raw material on one surface of a base film, and an inert gas such as argon gas or helium gas is used as a carrier gas. Furthermore, it is possible to form a vapor deposition film of an inorganic oxide such as silicon oxide by using a low temperature plasma chemical vapor deposition method using an oxygen gas or the like as an oxygen supply gas and using a low temperature plasma generator or the like. .
In the above, for example, a high-frequency plasma, a pulse wave plasma, a microwave plasma, or the like can be used as the low-temperature plasma generator. Thus, in the present invention, a highly active and stable plasma is obtained. For this purpose, it is desirable to use a high-frequency plasma generator.
[0015]
Specifically, an example of the formation method of the deposited film of the inorganic oxide by the low temperature plasma chemical vapor deposition method will be described as an example. FIG. It is a schematic block diagram of the low temperature plasma chemical vapor deposition apparatus which shows the outline | summary about the formation method of a vapor deposition film.
As shown in FIG. 5 above, in the present invention, the base film 1 is fed out from the unwinding roll 23 disposed in the vacuum chamber 22 of the plasma chemical vapor deposition apparatus 21, and the base material 1 is further fed. The film 1 is conveyed onto the circumferential surface of the cooling / electrode drum 25 at a predetermined speed via the auxiliary roll 24.
Thus, in the present invention, oxygen gas, inert gas, a monomer gas for vapor deposition such as an organosilicon compound, and the like are supplied from the gas supply devices 26 and 27 and the raw material volatilization supply device 28, and the like. The vapor deposition mixed gas composition was introduced into the vacuum chamber 22 through the raw material supply nozzle 29 without adjusting the vapor deposition mixed gas composition, and was conveyed onto the cooling / electrode drum 25 peripheral surface. Plasma is generated by the glow discharge plasma 30 on the base film 1 and irradiated to form a deposited film of an inorganic oxide such as silicon oxide.
In the present invention, at that time, the cooling / electrode drum 25 is applied with a predetermined power from the power source 31 disposed outside the vacuum chamber 22, and the cooling / electrode drum 25 is disposed in the vicinity of the cooling / electrode drum 25. The generation of plasma is promoted by arranging the magnet 32.
Next, the base film 1 on which the vapor-deposited film of inorganic oxide such as silicon oxide is formed is wound on the winding roll 34 via the auxiliary roll 33, and the plasma chemical vapor phase according to the present invention is applied. A vapor-deposited film of an inorganic oxide can be formed by a growth method.
In the figure, 35 represents a vacuum pump.
The above exemplification is an example, and it is needless to say that the present invention is not limited thereby.
Although not shown, in the present invention, the inorganic oxide vapor deposition film may be not only one layer of the inorganic oxide vapor deposition film but also a multilayer film in which two or more layers are laminated, and is used. The material may be used alone or as a mixture of two or more, and an inorganic oxide vapor deposition film mixed with different materials may be formed.
[0016]
In the above, the inside of the vacuum chamber is depressurized by a vacuum pump, and the degree of vacuum is 1 × 10.^-1~ 1x10^-8Torr position, preferably vacuum degree 1 × 10^-3~ 1x10^-7It is desirable to prepare it at the Torr position.
In the raw material volatilization supply device, the organic silicon compound as the raw material is volatilized and mixed with oxygen gas, inert gas, etc. supplied from the gas supply device, and this mixed gas is supplied to the vacuum chamber through the raw material supply nozzle. It is introduced in the inside.
In this case, the content of the organosilicon compound in the mixed gas is about 1 to 40%, the content of oxygen gas is about 10 to 70%, and the content of inert gas is about 10 to 60%. For example, the mixing ratio of the organosilicon compound, oxygen gas, and inert gas can be about 1: 6: 5 to 1:17:14.
On the other hand, since a predetermined voltage is applied to the cooling / electrode drum from the power source, glow discharge plasma is generated in the vicinity of the opening of the raw material supply nozzle in the vacuum chamber and the cooling / electrode drum. The glow discharge plasma is derived from one or more gas components in the mixed gas. In this state, the substrate film is conveyed at a constant speed, and the glow discharge plasma is used to cool the electrode drum peripheral surface. A vapor deposition film of an inorganic oxide such as silicon oxide can be formed on the upper base film.
The degree of vacuum in the vacuum chamber at this time is 1 × 10^-1~ 1x10^-4Torr position, preferably vacuum degree 1 × 10^-1~ 1x10^-2It is desirable to adjust to the Torr position, and it is desirable to adjust the conveying speed of the resin film to about 10 to 300 m / min, preferably about 50 to 150 m / min.
[0017]
In addition, in the plasma chemical vapor deposition apparatus described above, an inorganic oxide vapor deposition film such as silicon oxide is formed on a base film by oxidizing plasma source gas with oxygen gas._XTherefore, the formed vapor-deposited film of inorganic oxide such as silicon oxide is a continuous layer having high density, few gaps, and high flexibility. The barrier property of a vapor-deposited film of inorganic oxide such as silicon is much higher than that of a vapor-deposited film of inorganic oxide such as silicon oxide formed by a conventional vacuum vapor deposition method, and a thin film thickness is sufficient. A barrier property can be obtained.
In the present invention, SiO_XSince the surface of the base film is cleaned by the plasma, and polar groups, free radicals, etc. are generated on the surface of the base film, a deposited film of inorganic oxide such as silicon oxide and the base film are formed. It has the advantage that it becomes a thing with high close adhesiveness.
Furthermore, the degree of vacuum when forming a continuous film of an inorganic oxide such as silicon oxide as described above is 1 × 10^-1~ 1x10^-4Torr position, preferably 1 × 10^-1~ 1x10^-2Since the Torr position is prepared, the degree of vacuum when forming a deposited film of an inorganic oxide such as silicon oxide by a conventional vacuum deposition method is 1 × 10.^-4~ 1x10^-5Since the degree of vacuum is lower than that of the Torr position, it is possible to shorten the time for setting the vacuum state when replacing the base film with the original film, to easily stabilize the degree of vacuum, and to stabilize the film forming process. .
[0018]
In the present invention, a vapor deposition film of silicon oxide formed using a vapor deposition monomer gas such as an organosilicon compound chemically reacts with a vapor deposition monomer gas such as an organic silicon compound and oxygen gas, and the reaction product. However, it is closely bonded to one surface of the base film to form a dense, flexible thin film, usually with the general formula SiO_X(Where X represents a number from 0 to 2), and is a continuous thin film mainly composed of silicon oxide.
Thus, the silicon oxide vapor-deposited film has a general formula SiO in terms of transparency and barrier properties._X(However, X represents the number of 1.3-1.9.) It is preferable that it is a thin film which mainly has the vapor deposition film | membrane of the silicon oxide represented.
In the above, the value of X varies depending on the molar ratio of the vapor-deposited monomer gas and oxygen gas, the energy of the plasma, etc. Generally, the gas permeability decreases as the value of X decreases, but the film itself Becomes yellowish and the transparency is poor.
[0019]
In addition, the silicon oxide vapor-deposited film is mainly composed of silicon oxide, and further, at least one kind of compound composed of one kind of carbon, hydrogen, silicon, or oxygen, or two or more kinds thereof is chemically used. It consists of a vapor deposition film contained by bonding or the like.
For example, when a compound having a C—H bond, a compound having a Si—H bond, or a carbon unit is in the form of graphite, diamond, fullerene, etc. A derivative may be contained by a chemical bond or the like.
For example, CH₃Hydrocarbon with part, SiH₃Cyril, SiH₂Hydrosilica such as silylene, SiH₂Examples include hydroxyl derivatives such as OH silanol.
In addition to the above, the type, amount, etc., of the compound contained in the deposited film of silicon oxide can be changed by changing the conditions of the vapor deposition process.
Thus, the content of the above compound in the deposited film of silicon oxide is about 0.1 to 50%, preferably about 5 to 20%.
In the above, if the content is less than 0.1%, the impact resistance, spreadability, flexibility, etc. of the deposited silicon oxide film become insufficient, and scratches, cracks, etc. are likely to occur due to bending. It is difficult to stably maintain a high barrier property, and if it exceeds 50%, the barrier property is lowered, which is not preferable.
Furthermore, in the present invention, in the silicon oxide vapor deposition film, the content of the above-mentioned compound is preferably decreased from the surface of the silicon oxide vapor deposition film in the depth direction. On the surface, the impact resistance and the like can be enhanced by the above compound and the like. On the other hand, at the interface with the base film, the content of the above compound is small. This has the advantage that the tight adhesion of the material becomes strong.
[0020]
Thus, in the present invention, the above silicon oxide vapor deposition film is subjected to surface analysis such as an X-ray photoelectron spectrometer (Xray Photoelectron Spectroscopy, XPS), a secondary ion mass spectrometer (Secondary Ion Mass Spectroscopy, SIMS), etc. The physical properties as described above can be confirmed by conducting an elemental analysis of the deposited film of silicon oxide using a method of analyzing by ion etching in the depth direction using an apparatus.
In the present invention, the film thickness of the above-described silicon oxide vapor deposition film is preferably about 50 to 4000 mm, and specifically, the film thickness is preferably about 100 to 1000 mm. In the above, if it is thicker than 1000 mm, and more preferably 4000 mm, it is not preferable because cracks and the like are likely to occur in the film, and if it is less than 100 mm, further less than 50 mm, there is an effect of barrier properties. Is not preferable because it becomes difficult.
In the above, the film thickness can be measured by a fundamental parameter method using, for example, a fluorescent X-ray analyzer (model name, RIX2000 type) manufactured by Rigaku Corporation.
In the above, as means for changing the film thickness of the silicon oxide vapor deposition film, the volume velocity of the vapor deposition film is increased, that is, the method of increasing the amount of monomer gas and oxygen gas and the vapor deposition rate. This can be done by a method of slowing down.
[0021]
Next, in the above, as a vapor deposition monomer gas such as an organic silicon compound for forming a vapor deposition film of an inorganic oxide such as silicon oxide, for example, 1.1.3.3-tetramethyldisiloxane, hexamethyldisiloxane Siloxane, vinyltrimethylsilane, methyltrimethylsilane, hexamethyldisilane, methylsilane, dimethylsilane, trimethylsilane, diethylsilane, propylsilane, phenylsilane, vinyltriethoxysilane, vinyltrimethoxysilane, tetramethoxysilane, tetraethoxysilane, phenyl Trimethoxysilane, methyltriethoxysilane, octamethylcyclotetrasiloxane, etc. can be used.
In the present invention, among the organic silicon compounds as described above, use of 1.1.3.3-tetramethyldisiloxane or hexamethyldisiloxane as a raw material is easy to handle and formed continuous film. In view of the above characteristics and the like, it is a particularly preferable raw material.
Moreover, in the above, as an inert gas, argon gas, helium gas, etc. can be used, for example.
[0022]
Next, in the present invention, as the vapor deposition film of inorganic oxide constituting the lid for aseptic rice filling and packaging container according to the present invention, aseptic packaging rice, etc., for example, vacuum deposition method, sputtering method, ion plating method, etc. Further, a vapor deposition film of an inorganic oxide can be formed using a physical vapor deposition method (Physical Vapor Deposition method, PVD method) such as an ion cluster beam method.
In the present invention, specifically, a metal oxide is used as a raw material, this is heated and vaporized, and this is vapor-deposited on one of the base film, or a metal or metal oxidation as a raw material. Vapor deposition film using oxidation reaction deposition method in which oxygen is introduced to oxidize and deposited on one side of base film, and plasma-assisted oxidation reaction deposition method in which oxidation reaction is supported by plasma Can be formed.
In the above, as a heating method of the vapor deposition material, for example, a resistance heating method, a high frequency induction heating method, an electron beam heating method (EB), or the like can be used.
[0023]
In the present invention, specific examples of a method for forming a thin film of an inorganic oxide by physical vapor deposition are given. FIG. 6 is a schematic configuration diagram showing an example of a take-up vacuum deposition apparatus.
As shown in FIG. 6, the base film 1 fed out from the unwinding roll 43 in the vacuum chamber 42 of the wind-up type vacuum deposition apparatus 41 is cooled through the guide rolls 44 and 45. -Guided to the dating drum 46;
Thus, the evaporation source 48 heated by the crucible 47, for example, metal aluminum or aluminum oxide is evaporated on the base film 1 guided on the cooled coating drum 46, Further, if necessary, an oxygen gas or the like is ejected from the oxygen gas outlet 49 and an inorganic oxide vapor deposition film such as aluminum oxide is formed through the masks 50 and 50 while supplying the oxygen gas. Next, in the above, for example, the base film 1 on which a vapor-deposited film of an inorganic oxide such as aluminum oxide is formed is sent out through the guide rolls 51 and 52 and wound up on the take-up roll 53. An inorganic oxide vapor-deposited film can be formed by physical vapor deposition according to the invention.
In the present invention, the first-layer inorganic oxide vapor deposition film is first formed using the above-described take-up vacuum vapor deposition apparatus, and then the inorganic oxide vapor deposition film is formed in the same manner. Further, an inorganic oxide vapor deposition film is formed on the substrate, or by using the above-described take-up vacuum vapor deposition apparatus, these are connected in series, and the inorganic oxide vapor deposition is continuously performed. By forming the film, it is possible to form an inorganic oxide vapor-deposited film composed of two or more multilayer films.
[0024]
In the above, as a vapor deposition film of an inorganic oxide, any thin film in which a metal oxide is vapor deposited can be used. For example, silicon (Si), aluminum (Al), magnesium (Mg), calcium ( Deposition of metal oxides such as Ca), potassium (K), tin (Sn), sodium (Na), boron (B), titanium (Ti), lead (Pb), zirconium (Zr), yttrium (Y) A membrane can be used.
Thus, preferable examples include vapor-deposited films of metal oxides such as silicon (Si) and aluminum (Al).
Thus, the above metal oxide vapor deposition film can be referred to as a metal oxide such as silicon oxide, aluminum oxide, magnesium oxide, etc._XAlO_X, MgO_XMO etc._X(In the formula, M represents a metal element, and the value of X varies depending on the metal element.)
Moreover, as a range of said X value, silicon (Si) is 0-2, aluminum (Al) is 0-1.5, magnesium (Mg) is 0-1, calcium (Ca) is 0 to 1, potassium (K) is 0 to 0.5, tin (Sn) is 0 to 2, sodium (Na) is 0 to 0.5, boron (B) is 0 to 1, 5, Titanium (Ti) can take values in the range of 0 to 2, lead (Pb) in the range of 0 to 1, zirconium (Zr) in the range of 0 to 2, and yttrium (Y) in the range of 0 to 1.5.
In the above, when X = 0, it is a complete metal and is not transparent and cannot be used at all. The upper limit of the range of X is a completely oxidized value.
In the present invention, generally, examples other than silicon (Si) and aluminum (Al) are scarce, silicon (Si) is 1.0 to 2.0, and aluminum (Al) is 0.5. Those with values in the range of -1.5 can be used.
In the present invention, the thickness of the vapor-deposited film of the inorganic oxide as described above varies depending on the type of metal or metal oxide used, but is, for example, about 50 to 2000 mm, preferably about 100 to 1000 mm. It is desirable to select and form arbitrarily within the range.
Further, in the present invention, the inorganic oxide vapor-deposited film is a metal to be used, or the metal oxide is one or a mixture of two or more, and mixed with different materials. A vapor deposition film can also be comprised.
[0025]
By the way, in the present invention, as the inorganic oxide vapor deposition film as described above, for example, two or more layers of different inorganic oxide vapor deposition films using both physical vapor deposition and chemical vapor deposition are combined. It is also possible to form and use a composite film.
Thus, as a composite film composed of two or more layers of the above-mentioned different types of inorganic oxide vapor-deposited films, first, on the base film, it is dense and flexible by chemical vapor deposition. An inorganic oxide vapor deposition film capable of preventing the occurrence of cracks is provided, and then an inorganic oxide vapor deposition film formed by physical vapor deposition is provided on the inorganic oxide vapor deposition film to form two or more layers. It is desirable to constitute an inorganic oxide vapor-deposited film made of a composite film made of
Of course, in the present invention, contrary to the above, an inorganic oxide vapor-deposited film is first provided on the base film by physical vapor deposition, and then dense by chemical vapor deposition. It is also possible to provide an inorganic oxide vapor deposition film composed of a composite film composed of two or more layers by providing an inorganic oxide vapor deposition film that is highly flexible and can relatively prevent the occurrence of cracks. is there.
[0026]
Next, in the present invention, the gas barrier coating film constituting the lid for aseptic rice filling and packaging container according to the present invention, aseptic packaging cooked rice, etc. will be described. As the gas barrier coating film, at least a polyvinyl alcohol system is used. Resin [hereinafter referred to as component (A). ] And the general formula R¹ _mM (OR²)_n(1) (wherein M represents a metal atom and R¹Are the same or different and each represents an organic group having 1 to 8 carbon atoms, R²Are the same or different and each represents an alkyl group having 1 to 5 carbon atoms or an acyl group or phenyl group having 1 to 6 carbon atoms, m and n each represents an integer of 0 or more, and m + n represents the valence of M. To express. A metal alcoholate, a hydrolyzate of the metal alcoholate, a condensate of the metal alcoholate, a chelate compound of the metal alcoholate, a hydrolyzate of the chelate compound, and At least one selected from the group of metal acylates (hereinafter referred to as component (B). And a gas barrier coating film made of a gas barrier composition containing
In the above, the gas barrier composition preferably contains a nitrogen-containing organic solvent, and is also referred to as inorganic fine particles [hereinafter referred to as component (C). ] Is also preferable.
In the above, as the component (B), the component (B) is hydrolyzed in water or a mixed solvent containing water and a hydrophilic organic solvent, and then mixed with the component (A) to prepare a gas barrier composition. Is something that can be done.
[0027]
In the above gas barrier composition, as the polyvinyl alcohol-based resin constituting the component (A), at least one selected from the group of polyvinyl alcohol and ethylene / vinyl alcohol copolymer can be used. .
Among the components (A), polyvinyl alcohol is generally obtained by saponifying polyvinyl acetate.
The polyvinyl alcohol may be partially saponified polyvinyl alcohol in which several tens% of acetic acid groups remain, completely saponified polyvinyl alcohol in which no acetic acid groups remain, or modified polyvinyl alcohol in which OH groups have been modified. There is no particular limitation.
Specific examples of the polyvinyl alcohol include RS-110 (degree of saponification = 99%, degree of polymerization = 1,000) manufactured by Kuraray Co., Ltd., and Kuraray Poval LM-20SO (degree of saponification = 40%, polymerization degree = 2,000), Gohsenol NM-14 manufactured by Nippon Synthetic Chemical Industry Co., Ltd. (degree of saponification = 99%, polymerization degree = 1,400) and the like can be used.
Among the components (A), the ethylene-vinyl alcohol copolymer is obtained by saponifying a copolymer of ethylene and vinyl acetate, that is, an ethylene-vinyl acetate random copolymer. , Including a partially saponified product in which several tens mol% of acetic acid groups remain to a complete saponified product in which acetic acid groups remain only several mol% or no acetic acid groups remain, but is not particularly limited. A preferable saponification degree from the viewpoint of gas barrier properties is 80 mol% or more, more preferably 90 mol% or more, and still more preferably 95 mol% or more.
The content of repeating units derived from ethylene in the ethylene / vinyl alcohol copolymer (hereinafter also referred to as “ethylene content”) is usually 0 to 50 mol%, preferably 20 to 45 mol%.
Specific examples of the ethylene-vinyl alcohol copolymer include Kuraray Co., Ltd., Eval EP-F101 (ethylene content: 32 mol%), Nippon Synthetic Chemical Industry Co., Ltd., Soarnol D2908 (ethylene content: 29 mol%). Etc. can be used.
[0028]
The melt flow index of the polyvinyl alcohol resin constituting the component (A) is 1 to 20 g / 10 minutes, preferably 1 to 18 g / 10 minutes under the conditions of 210 ° C. and a load of 21.168N.
These polyvinyl alcohol resins constituting (A) can be used singly or as a mixture of two or more.
In addition, the polyvinyl alcohol-based resin constituting the component (A) itself is excellent in gas barrier properties, weather resistance, organic solvent resistance, transparency, gas barrier properties after heat treatment, and the like.
In addition, when the coating film obtained from the gas barrier composition of the present invention is cured with the polyvinyl alcohol resin constituting the component (A), the hydroxyl group present in the repeating unit derived from the polyvinyl alcohol is described later ( Co-condensation with the component (B) and / or the component (C) can provide excellent coating performance.
The proportion of the component (A) in the gas barrier composition of the present invention is 10 to 10,000 parts by weight, preferably 20 to 5,000 parts by weight, more preferably, based on 100 parts by weight of the component (B) described later. 100 to 1,000 parts by weight.
If it is less than 10 parts by weight, cracks are likely to occur in the resulting coating film, and the gas barrier property is lowered. On the other hand, if it exceeds 10,000 parts by weight, the resulting coating film is unfavorably deteriorated under high humidity. Is.
[0029]
Next, as the component (B) used in the present invention, a metal alcoholate, a hydrolyzate of the metal alcoholate, a condensate of the metal alcoholate represented by the general formula (1), the metal At least one selected from the group consisting of an alcoholate chelate compound, a hydrolyzate of the chelate compound and a metal acylate can be used, and therefore only one of them may be used as the component (B). Any two or more mixtures may be used.
In addition, as a hydrolyzate of said metal alcoholate, OR contained in metal alcoholate²Need not be hydrolyzed. For example, only one of them may be hydrolyzed, two or more may be hydrolyzed, or a mixture thereof.
In addition, the metal alcoholate condensate described above is a product in which the M-OH group of the metal alcoholate hydrolyzate is condensed to form an M-O-M bond. It is not necessary for all to be condensed, but a concept including a mixture of a small part of M-OH groups, a mixture of those having different degrees of condensation, and the like.
Further, the metal alcoholate chelate compound is at least selected from metal alcoholates and β-diketones, β-ketoesters, hydroxycarboxylic acids, hydroxycarboxylic acid salts, hydroxycarboxylic acid esters, ketoalcohols and aminoalcohols. Obtained by reaction with one compound.
Among these compounds, β-diketones or β-ketoesters are preferably used, and specific examples thereof include acetylacetone, methyl acetoacetate, ethyl acetoacetate, acetoacetate-n-propyl, acetoacetate-i- Propyl, acetoacetate-n-butyl, acetoacetate-sec-butyl, acetoacetate-t-butyl, 2,4-hexane-dione, 2,4-heptane-dione, 3,5-heptane-dione, 2,4 -Octane-dione, 2,4-nonane-dione, 5-methyl-hexane-dione and the like can be mentioned.
Further, the hydrolyzate of the above chelate compound is the same as the hydrolyzate of the above metal alcoholate, and the OR contained in the chelate compound.²It is not necessary that all the groups are hydrolyzed, and for example, only one of them may be hydrolyzed, two or more may be hydrolyzed, or a mixture thereof.
In the present invention, the component (B) is considered to act to form a cocondensate with the component (A).
[0030]
In the general formula (1), examples of the metal atom represented by M include zirconium, titanium, and aluminum, and titanium is particularly preferable.
R¹The monovalent organic group having 1 to 8 carbon atoms differs depending on whether the compound represented by the general formula (1) is a metal alcoholate or a metal acylate.
In the case of a metal alcoholate, for example, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group, t-butyl group, n-hexyl Group, n-heptyl group, n-octyl group, alkyl group such as 2-ethylhexyl group; acyl group such as acetyl group, propionyl group, butyryl group, valeryl group, benzoyl group, trioyl group; vinyl group, allyl group, cyclohexyl In addition to groups, phenyl groups, glycidyl groups, (meth) acryloxy groups, ureido groups, amide groups, fluoroacetamide groups, isocyanate groups, etc., substituted derivatives of these groups, and the like can be mentioned.
R¹Examples of the substituent in the substituted derivative include, for example, a halogen atom, a substituted or unsubstituted amino group, a hydroxyl group, a mercapto group, an isocyanate group, a glycidoxy group, a 3,4-epoxycyclohexyl group, a (meth) acryloxy group, and a ureido Groups, ammonium bases and the like.
However, R consisting of these substituted derivatives¹The carbon number of is 8 or less including the carbon atom in a substituent.
In the case of metal acylate, R¹Examples of the monovalent organic group having 1 to 8 carbon atoms include acyloxyl groups such as acetoxyl group, propionyloxyl group, butyryloxyl group, valeryloxyl group, benzoyloxyl group, and trioyloxyl group.
In general formula (1), R¹When two are present, they may be the same or different from each other.
[0031]
R²Examples of the alkyl group having 1 to 5 carbon atoms include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, sec-butyl group, t-butyl group, and n-pentyl group. Examples of the acyl group having 1 to 6 carbon atoms include an acetyl group, a propionyl group, a butyryl group, a valeryl group, and a caproyl group.
A plurality of R present in the general formula (1)²May be the same as or different from each other.
[0032]
Among these (B) components, as specific examples of metal alcoholates and metal alcoholate chelate compounds,
(I). Tetra-n-butoxyzirconium, tri-n-butoxyethylacetoacetatezirconium, di-n-butoxybis (ethylacetoacetate) zirconium, n-butoxytris (ethylacetoacetate) zirconium, tetrakis (n-propylacetate) Zirconium compounds such as acetate) zirconium, tetrakis (acetylacetoacetate) zirconium, tetrakis (ethylacetoacetate) zirconium;
[0033]
(B). Tetra-i-propoxy titanium, tetra-n-butoxy titanium, tetra-t-butoxy titanium, di-i-propoxy bis (ethylacetoacetate) titanium, di-i-propoxy bis (acetylacetate) titanium, di- Titanium compounds such as i-propoxy bis (acetylacetonato) titanium, di-n-butoxy bis (triethanolaminato) titanium, dihydroxy bislactatetitanium, dihydroxytitanium lactate, tetrakis (2-ethylhexyloxy) titanium ;
[0034]
(C). Tri-i-propoxyaluminum, di-i-propoxyethyl acetoacetate aluminum, di-i-propoxy acetylacetonate aluminum, i-propoxy bis (ethylacetoacetate) aluminum, i-propoxy bis (acetylacetonate) ) Aluminum compounds such as aluminum, tris (ethylacetoacetate) aluminum, tris (acetylacetonate) aluminum, monoacetylacetonate bis (ethylacetoacetate) aluminum;
And so on.
Among these metal alcoholates and metal alcoholate chelate compounds, preferred are tri-n-butoxy ethylacetoacetate zirconium, di-i-propoxy bis (acetylacetonato) titanium, di-n-butoxy Bis (triethanolaminato) titanium, dihydroxy bislactate titanium, di-i-propoxy-ethyl acetoacetate aluminum and tris (ethyl acetoacetate) aluminum can be mentioned, and particularly preferred compounds are di-i-propoxy Titanium compounds such as bis (acetylacetonato) titanium, di-n-butoxy bis (triethanolaminato) titanium, dihydroxy bislactatetotitanium.
[0035]
Specific examples of the metal acylate include dihydroxy titanium dibutyrate, di-i-propoxy titanium diacetate, di-i-propoxy titanium dipropionate, di-i-propoxy titanium dimalonate, di- i-propoxy-titanium dibenzoylate, di-n-butoxy-zirconium diacetate, di-i-propylaluminum monomalonate, and the like. Particularly preferred compounds are dihydroxy-titanium dibutyrate, di-i-propoxy. -Titanium compounds such as titanium diacetate.
These components (B) are used singly or in combination of two or more.
[0036]
As the component (B), the viscosity of the coating solution does not change with time and is easy to handle. Therefore, it is hydrolyzed in water or a mixed solvent containing water and a hydrophilic organic solvent described in a hydrophilic solvent described later. Is preferably used.
In this case, the amount of water used is the general formula R¹ _mM (OR²)_nIt is 0.1-1000 mol with respect to 1 mol of compounds represented by (1), Preferably, it is 0.5-500 mol.
In the case of a mixed solvent, the mixing ratio of water and the hydrophilic organic solvent is such that water / hydrophilic organic solvent = 10-90 / 90-10 (weight ratio), preferably 30-70 / 70-30, Preferably, it is 40-60 / 60-40.
[0037]
Next, the gas barrier composition of the present invention preferably contains inorganic fine particles as component (C).
The inorganic fine particles are particulate inorganic substances having an average particle size of 0.2 μm or less and substantially free of carbon atoms, and examples thereof include metals or silicon oxides, metals or silicon nitrides, and metal borides.
The method for producing inorganic fine particles includes, for example, a gas phase method in which silicon tetrachloride is obtained by hydrolysis in a flame of oxygen and hydrogen to obtain silicon oxide, a liquid phase method in which sodium silicate ion exchange is performed, a silica gel mill Examples of the production method include a solid phase method obtained by pulverization, etc., but are not limited to these methods.
[0038]
Specific examples of compounds include SiO₂, Al₂O₃TiO₂, WO₃, Fe, ZnO, NiO, RuO₂, CdO, SnO₂, Bi₂O₃3Al₂O₃・ O₂, Sn-In₂O₃, Sb-In₂O₃, Oxides such as CoFeOx, Si, Fe₄N, AlN, TiN, ZrN, TaN and other nitrides, Ti₂B, ZrB, TaB₂, W₂Borides such as B may be mentioned.
Examples of the form of the inorganic fine particles include powder, water, or a colloid or sol dispersed in an organic solvent, but these are not limited.
Of these, colloidal silica, colloidal alumina, alumina sol, tin sol, zirconium sol, pentoxide are preferred in order to obtain excellent coating performance by co-condensing with component (A) and / or component (B). Colloidal oxides having a hydroxyl group on the particle surface, such as antimony sol, cerium oxide sol, zinc oxide sol, and titanium oxide sol, are used.
The average particle size of the inorganic fine particles is 0.2 μm or less, preferably 0.1 μm or less. If the average particle size exceeds 0.2 μm, the gas barrier property may be inferior from the viewpoint of the denseness of the film.
[0039]
The proportion of the component (C) in the composition of the present invention is preferably 10 to 900 parts by weight, particularly preferably 20 to 400 parts by weight based on 100 parts by weight of the total amount of the components (A) and (B). Part.
In the above, when it exceeds 900 weight part, the gas barrier property of the coating film obtained may fall.
[0040]
Next, in the present invention, for the purpose of more quickly curing the gas barrier coating film by the gas barrier composition of the present invention and for the purpose of easily forming a cocondensate of the component (A) and the component (B) ( D) A curing accelerator may be used, and it is more effective to use this (D) curing accelerator in combination in order to cure at a relatively low temperature and to obtain a denser coating film.
[0041]
As the above (D) curing accelerator, inorganic acids such as hydrochloric acid; alkali metal salts such as naphthenic acid, octylic acid, nitrous acid, sulfurous acid, aluminate, and carbonic acid; alkaline compounds such as sodium hydroxide and potassium hydroxide; Acidic compounds such as alkyl titanic acid, phosphoric acid, methanesulfonic acid, p-toluenesulfonic acid, phthalic acid; ethylenediamine, hexanediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, piperidine, piperazine, metaphenylenediamine, ethanolamine , Triethylamine, various modified amines used as curing agents for epoxy resins, γ-aminopropyltriethoxysilane, γ- (2-aminoethyl) -aminopropyltrimethoxysilane, γ- (2-aminoethyl) -aminopropylmethyl The Tokishishiran, amine compounds such as γ- anilino trimethoxysilane,
(C₄H₉)₂Sn (OCOC₁₁H₂₃)₂
(C₄H₉)₂Sn (OCOCH = CHCOOCH₃)₂,
(C₄H₉)₂Sn (OCOCH = CHCOOC₄H₉)₂,
(C₈H₁₇)₂Sn (OCOC₁₁H₂₃)₂,
(C₈H₁₇)₂Sn (OCOCH = CHCOOCH₃)₂,
(C₈H₁₇)₂Sn (OCOCH = CHCOOC₄H₉)₂,
(C₈H₁₇)₂Sn (OCOCH = CHCOOC₈H₁₇)₂,
Sn (OCOCC₈H₁₇)₂Carboxylic acid type organotin compounds such as;

Mercaptide-type organotin compounds such as

Sulfide-type organotin compounds such as;
[0042]
(C₄H₉)₂SnO, (C₈H₁₇)₂SnO or (C₄H₉)₂SnOH₁₇)₂Organic tin compounds such as reaction products of organotin oxides such as SnO and ester compounds such as ethyl silicate, dimethyl maleate, diethyl maleate and dioctyl phthalate are used.
The proportion of these (D) curing accelerators in the gas barrier composition is usually 0.5 to 50 parts by weight, preferably 0.5 to 100 parts by weight of the solid content of the gas barrier composition of the present invention. ~ 30 parts by weight are used.
[0043]
Furthermore, the β-diketones and / or β-ketoesters mentioned above can be added as a stability improver to the gas barrier composition of the present invention.
That is, by coordinating to the metal atom in the metal alcoholate present in the gas barrier composition as the component (B), the effect of controlling the condensation reaction between the component (A) and the component (B). Thus, it is considered that the gas barrier composition obtained has the effect of improving the storage stability.
The amount of β-diketone and / or β-ketoester used is preferably 2 mol or more, more preferably 3 to 20 mol, per 1 mol of the metal atom in the component (B).
[0044]
The gas barrier composition of the present invention is usually obtained by dissolving and dispersing the above components (A) to (D) and optionally the above optional components in water and / or a hydrophilic organic solvent.
Here, specific examples of the hydrophilic organic solvent include methanol, ethanol, n-propanol, i-propanol, n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol, diacetone alcohol, ethylene glycol, diethylene glycol, triglyceride. C1-C8 saturated aliphatic monohydric alcohol or dihydric alcohol such as ethylene glycol; C1-C8 saturated aliphatic ether compound such as ethylene glycol monobutyl ether or ethylene glycol monoethyl ether; ethylene glycol Ester compounds of saturated aliphatic dihydric alcohols having 1 to 8 carbon atoms such as monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate; N, -Nitrogen-containing compounds (nitrogen-containing organic solvents) such as dimethylacetamide, N, N-dimethylformamide, γ-butyrolactone, N-methylpyrrolidone, pyridine; sulfur-containing compounds such as dimethyl sulfoxide; lactic acid, methyl lactate, ethyl lactate, salicylic acid And hydroxycarboxylic acid or hydroxycarboxylic acid ester such as methyl salicylate. Of these, preferred are saturated aliphatic monohydric alcohols having 1 to 8 carbon atoms such as methanol, ethanol, n-propanol, i-propanol, n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol, and the like. And nitrogen-containing compounds (nitrogen-containing organic solvents) such as N, N-dimethylacetamide, N, N-dimethylformamide, γ-butyrolactone, N-methylpyrrolidone, and pyridine.
[0045]
These water and / or hydrophilic organic solvent are more preferably used by mixing water and a hydrophilic organic solvent.
The preferred solvent composition is water / saturated aliphatic monohydric alcohol having 1 to 8 carbon atoms, water / nitrogen-containing compound (nitrogen-containing organic solvent).
More preferably, it is water / a saturated aliphatic monohydric alcohol having 1 to 8 carbon atoms / nitrogen-containing compound (nitrogen-containing organic solvent).
By mixing the nitrogen-containing organic solvent, a good coating film having a transparent appearance can be obtained in coating with a thin film.
[0046]
The amount of water and / or hydrophilic organic solvent used is such that the total solid concentration of the gas barrier composition is preferably 60% by weight or less.
For example, when used for the purpose of forming a thin film, it is usually 5 to 40% by weight, preferably 10 to 30% by weight. When used for the purpose of forming a thick film, it is usually 20 to 50%. % By weight, preferably 30 to 45% by weight.
When the total solid concentration of the gas barrier composition exceeds 60% by weight, the storage stability of the composition tends to be lowered.
Moreover, the ratio of the said nitrogen-containing organic solvent is 1 to 70 weight% normally in the solvent whole quantity, Preferably it is 5 to 50 weight%.
[0047]
As the organic solvent, the above water and / or hydrophilic organic solvent is preferable, but in addition to the hydrophilic organic solvent, for example, aromatic hydrocarbons such as benzene, toluene and xylene, ethers such as tetrahydrofuran and dioxane, Ketones such as acetone and methyl ethyl ketone, and esters such as ethyl acetate and butyl acetate can also be used.
[0048]
Thus, the gas barrier composition of the present invention is obtained by mixing the above components (A) to (B) and optionally the above optional components in water and / or a hydrophilic organic solvent, preferably the above It is obtained by hydrolyzing and / or condensing the component (A), the component (B), and optionally the component (C) in water and / or a hydrophilic organic solvent.
Under the present circumstances, as for reaction conditions, temperature is 20-100 degreeC, Preferably it is 30-80 degreeC, Time is 0.1 to 20 hours, Preferably it is 1 to 10 hours.
The weight average molecular weight of the obtained gas barrier composition is a polymethylmethacrylate conversion value by a general GPC method, and is usually 500 to 1,000,000, preferably 1,000 to 300,000.
[0049]
In addition, the gas barrier composition of the present invention is separately filled in order to develop various properties such as coloring of the obtained coating film, thickening of the coating film, prevention of UV transmission to the base, provision of corrosion resistance, and heat resistance. It is also possible to add and disperse the material.
However, the filler excludes the component (C).
Examples of the filler include water-insoluble pigments such as organic pigments and inorganic pigments, and particles, fibers, scale-like metals and alloys, and oxides, hydroxides, carbides, and nitrides thereof. And sulfides.
Specific examples of the filler include particulate, fibrous or scale-like iron, copper, aluminum, nickel, silver, zinc, ferrite, carbon black, stainless steel, silicon dioxide, titanium oxide, aluminum oxide, chromium oxide. , Manganese oxide, iron oxide, zirconium oxide, cobalt oxide, synthetic mullite, aluminum hydroxide, iron hydroxide, silicon carbide, silicon nitride, boron nitride, clay, diatomaceous earth, slaked lime, gypsum, talc, barium carbonate, calcium carbonate, Magnesium carbonate, Barium sulfate, Bentonite, Mica, Zinc green, Chrome green, Cobalt green, Viridian, Guinea green, Cobalt chromium green, Shere green, Green earth, Manganese green, Pigment green, Ultramarine, Bituminous, Pigment green, Rock ultramarine, Cobalt blue, cerulean blue, copper borate, molyb Blue, Copper sulfide, Cobalt purple, Mars purple, Manganese purple, Pigment violet, Lead oxide, Calcium lead acid, Zinc yellow, Lead sulfide, Chrome yellow, Ocher, Cadmium yellow, Strontium yellow, Titanium yellow, Resurge, Pigment yellow, Cuprous oxide, cadmium red, selenium red, chromium vermilion, bengara, zinc white, antimony white, basic lead sulfate, titanium white, lithopone, lead silicate, zircon oxide, tungsten white, lead zinc white, bunchison white, phthalate Lead acid, manganese white, lead sulfate, graphite, bone black, diamond black, thermatomic black, vegetable black, potassium titanate whisker, molybdenum disulfide, and the like.
[0050]
The average particle diameter or average length of these fillers is usually 50 to 50,000 nm, preferably 100 to 5,000 nm.
The proportion of the filler in the composition is preferably 0.1 to 300 parts by weight, and more preferably 1 to 200 parts by weight with respect to 100 parts by weight of the total solid content of components other than the filler.
[0051]
In addition, the gas barrier composition of the present invention includes other known dehydrating agents such as methyl orthoformate, methyl orthoacetate, tetraethoxysilane, various surfactants, silane coupling agents, titanium couplings other than the above. Additives such as agents, dyes, dispersants, thickeners and leveling agents can also be blended.
[0052]
In preparing the gas barrier composition of the present invention, a composition containing the above components (A) to (B), preferably (A) to (C) may be prepared. The component (B) is hydrolyzed in water or a mixed solvent containing water and a hydrophilic organic solvent, and then the component (A) is mixed.
If it does in this way, the viscosity of a gas barrier composition does not change with time, and a gas barrier composition excellent in handleability can be obtained.
Specific examples of the method for preparing the gas barrier composition of the present invention in the case of using the component (C) include the following methods.
The component (B) used in these preparation methods may be hydrolyzed in advance in water or a mixed solvent containing water and a hydrophilic organic solvent.
A method of adding the component (B) after adding the component (C) to the component (A) dissolved in water and / or a hydrophilic organic solvent.
A method in which the component (C) is added to the component (A) dissolved in water and / or a hydrophilic organic solvent, and then the component (B) is added, followed by hydrolysis and / or condensation.
A method in which the component (C) is added to the component (B) dissolved in water and / or a hydrophilic organic solvent, followed by hydrolysis and / or condensation, and then the component (A).
A method in which the components (A) to (C) are added all at once to water and / or a hydrophilic organic solvent and dissolved and dispersed. Or the method of performing hydrolysis and / or condensation after that.
[0053]
Thus, in the present invention, a gas barrier coating film can be formed by using the above-prepared gas barrier composition and applying the composition onto the inorganic oxide vapor deposition film. .
In the present invention, the inorganic oxide vapor-deposited film and the gas barrier coating film form, for example, a chemical bond, a hydrogen bond, or a coordinate bond by hydrolysis / co-condensation reaction, and the like. And the gas barrier coating film can be improved, and the synergistic effect of the two layers can provide a better gas barrier effect.
Examples of the method for applying the gas barrier composition of the present invention include one or more by coating means such as a roll coat such as a gravure coater, spray coat, spin coat, dipping, brush, bar code, applicator and the like. The gas barrier coating film of the present invention having a dry film thickness of 0.01 to 30 μm, preferably 0.1 to 10 μm, can be formed by one-time coating, and 50 to 300 ° C., preferably in a normal environment Condensation is performed by heating and drying at a temperature of 70 to 200 ° C. for 0.005 to 60 minutes, preferably 0.01 to 10 minutes, and the gas barrier coating film of the present invention can be formed. .
If necessary, when applying the gas barrier composition of the present invention, a primer agent or the like can be applied on the inorganic oxide vapor-deposited film in advance.
[0054]
Next, in the present invention, the printed pattern layer constituting the aseptic packaged rice container cover, aseptic packaged rice, etc. according to the present invention will be described. As the printed pattern layer, one or two kinds of ordinary ink vehicles are used. Mainly composed of seeds or more, and if necessary, plasticizers, stabilizers, antioxidants, light stabilizers, UV absorbers, curing agents, crosslinking agents, lubricants, antistatic agents, fillers, etc. One or more additives are optionally added, and further, colorants such as dyes and pigments are added, and the ink composition is prepared by sufficiently kneading with a solvent, a cloth, etc. The ink composition is used, and this is applied to the surface including the gas barrier coating film by using a printing method such as gravure printing, offset printing, letterpress printing, screen printing, transfer printing, flexographic printing, etc. , Letters, shapes, symbols, Like, by printing a desired print pattern consisting of other like, it is capable of forming a printed pattern layer according to the present invention.
[0055]
In the above, the ink vehicle may be a known one, such as sesame oil, drill oil, soybean oil, hydrocarbon oil, rosin, rosin ester, rosin-modified resin, shellac, alkyd resin, phenolic resin, maleic acid resin. , Natural resin, Hydrocarbon resin, Polyvinyl chloride resin, Polyvinyl acetate resin, Polystyrene resin, Polyvinyl propylar resin, Acrylic or methacrylic resin, Polyamide resin, Polyester resin, Polyurethane resin, Epoxy One or more of resins, urea resins, melamine resins, aminoalkyd resins, nitrocellulose, ethylcellulose, chlorinated rubber, cyclized rubber, etc. can be used.
[0056]
Next, in the present invention, when describing the adhesive layer for laminating constituting the lid for aseptic rice filling and packaging container according to the present invention, aseptic packaging rice, etc., as the adhesive constituting the adhesive layer for laminating, For example, polyvinyl acetate adhesives, homopolymers of ethyl acrylate, butyl, 2-ethylhexyl ester, etc., or copolymers of these with methyl methacrylate, acrylonitrile, styrene, etc. Adhesives, cyanoacrylate adhesives, ethylene copolymer adhesives composed of copolymers of ethylene and monomers such as vinyl acetate, ethyl acrylate, acrylic acid, methacrylic acid, cellulose adhesives, polyester adhesives , Polyamide adhesive, polyimide adhesive, urea resin or melamine resin, etc. Rubber system consisting of amino resin adhesive, phenol resin adhesive, epoxy adhesive, polyurethane adhesive, reactive (meth) acrylic adhesive, chloroprene rubber, nitrile rubber, styrene-butadiene rubber, etc. Adhesives such as adhesives, silicone adhesives, alkali metal silicates, low melting point glass, etc., and other adhesives can be used.
The composition system of the above-mentioned adhesive may be any composition form such as an aqueous type, a solution type, an emulsion type, and a dispersion type, and the property is any of film / sheet form, powder form, solid form, etc. Further, the bonding mechanism may be any of a chemical reaction type, a solvent volatilization type, a heat melting type, and a hot pressure type.
Thus, in the present invention, the above-mentioned adhesive is applied to the entire surface including the above-described printed pattern layer, for example, a coating method such as a roll coating method, a gravure roll coating method, a kiss coating method, or the like, or a printing method. Then, the solvent or the like is dried to form an adhesive layer for lamination, and the coating or printing amount is 0.1 to 10 g / m.²(Dry state) is desirable.
[0057]
Next, in the present invention, the heat-sealability constituting the heat-sealable resin layer will be described when the heat-sealable resin layer constituting the lid for aseptic rice-filled packaging container and the aseptically packaged cooked rice according to the present invention is described. The resin may be any resin that can be melted by heat and fused to each other, such as low density polyethylene, medium density polyethylene, high density polyethylene, linear (linear) low density polyethylene, polypropylene, ethylene-vinyl acetate. Polyolefins such as copolymers, ionomer resins, ethylene-ethyl acrylate copolymers, ethylene-acrylic acid copolymers, ethylene-methacrylic acid copolymers, ethylene-propylene copolymers, methylpentene polymers, polyethylene, and polypropylene Acrylic acid, methacrylic acid, maleic anhydride, fumaric acid, Acid-modified polyolefin resin modified with unsaturated candy sum carboxylic acids other like kind or resin comprising more resins other such film or sheet can be used for.
Thus, in the present invention, the heat-sealable resin layer according to the present invention can be formed by dry laminating the above resin film or sheet on the surface of the above-mentioned laminating adhesive layer. It is.
The resin film or sheet can be used in a single layer or multiple layers, and the thickness of the resin film or sheet is about 5 μm to 300 μm, preferably about 10 μm to 110 μm.
Furthermore, in the present invention, the thickness of the resin film or sheet is as follows: When the heat-sealed lid for aseptic rice filling and packaging container is heat sealed to the flange portion of the opening of the tray-shaped filling and packaging container, etc. In order to prevent the generation of scratches or cracks in the inorganic oxide vapor deposition film constituting the base film having the inorganic oxide vapor deposition film, it is preferable to increase the film thickness. Specifically, it is preferably about 70 μm to 110 μm, desirably about 80 μm to 100 μm.
[0058]
By the way, in the present invention, among the resin films or sheets as described above, it is particularly preferable to use linear low density polyethylene.
That is, the above-mentioned linear low density polyethylene has the advantage of improving impact resistance with less propagation of breakage because it has adhesiveness, and the inner layer is always in contact with the contents. It is also effective for preventing deterioration of environmental stress cracking resistance.
Further, in the present invention, other resins can be blended with the linear low density polyethylene. For example, by blending an ethylene-butene copolymer or the like, the heat resistance is slightly inferior, and the seal stability is maintained in a high temperature environment. Although there is a tendency to deteriorate, there is an advantage that the tearability is improved and it contributes to easy opening.
[0059]
Furthermore, in the present invention, the linear low density polyethylene as a film or sheet of the resin having the above heat-sealing property is specifically an ethylene-α / olefin copolymer polymerized using a metallocene catalyst. The same film or sheet can be used as well.
As the film or sheet of ethylene-α-olefin copolymer polymerized using the above metallocene catalyst, for example, a catalyst by a combination of a metallocene complex and an alumoxane such as a catalyst by a combination of zirconocene dichloride and methylalumoxane, that is, Ethylene-α. Polymerized using a metallocene catalyst. An olefin copolymer film or sheet can be used.
The metallocene catalyst is also called a single site catalyst because the current catalyst is called a multi-site catalyst with heterogeneous active sites, while the active sites are uniform.
Specifically, as an ethylene-α / olefin copolymer polymerized using a metallocene catalyst, trade names “Carnel” manufactured by Mitsubishi Chemical Corporation and trade names “Evolu” manufactured by Mitsui Petrochemical Industries, Ltd. -", Trade name" EXACT "manufactured by EXXON CHEMICAL, USA, trade name" Affinity ", trade name" ENGE- "manufactured by Dow Chemical, USA An ethylene-α-olefin copolymer polymerized using a metallocene catalyst such as “ENGAGE” can be used.
The film or sheet can be used as a single layer or multiple layers, and the thickness is preferably about 5 μm to 300 μm, preferably about 10 μm to 100 μm.
In the present invention, when a film or sheet of an ethylene-α / olefin copolymer polymerized using a metallocene catalyst is used as the resin film having heat sealability as described above, a lid for a sterile cooked rice filled packaging container When the material is heat-sealed to the flange portion of the opening of the tray-like packaging container, there is an advantage that low temperature heat sealability is possible.
[0060]
Next, in the present invention, the laminate for the paste for aseptic rice filling and packaging container according to the present invention, the laminating adhesive layer constituting the aseptic rice and the heat-sealable resin layer has a strength. As a resin film with excellent puncture resistance, etc., it has excellent strength in mechanical, physical, chemical, etc., excellent in puncture resistance, etc., in addition, heat resistance, moisture resistance, pin resistance A resin film or sheet excellent in hole property, transparency, and the like can be used.
Specifically, for example, a film or sheet of a tough resin such as a polyester resin, a polyamide resin, a polyaramid resin, a polypropylene resin, a polycarbonate resin, a polyacetal resin, a fluorine resin, or the like is used. Can do.
Thus, in the present invention, the above-described resin film or sheet is used, and this is used, for example, by using the above-mentioned laminating adhesive or the like using a dry laminating method or the like, It can be laminated between the heat-sealable resin layers.
In the above, as the resin film or sheet, any of an unstretched film or a stretched film stretched in a uniaxial direction or a biaxial direction can be used.
In the present invention, the thickness of the resin film or sheet may be a thickness that can be kept to the minimum necessary for strength, puncture resistance, and the like. If it is too thick, the cost increases. On the other hand, if it is too thin, the strength, puncture resistance, and the like are undesirably lowered.
In the present invention, for the reasons described above, about 10 μm to 100 μm, preferably about 12 μm to 50 μm is most desirable.
[0061]
By the way, packaging products filled and packed with contents are usually subjected to severe physical and chemical conditions. Therefore, laminated materials constituting packaging containers and lid materials have severe packaging suitability. Various requirements such as deformation prevention strength, drop impact strength, pinhole resistance, heat resistance, sealing performance, quality maintenance, workability, hygiene, etc. are required, and for this reason, in the present invention In addition to the above materials, other materials satisfying the above conditions can be arbitrarily used. Specifically, for example, low density polyethylene, medium density polyethylene, high density polyethylene, Linear low density polyethylene, polypropylene, ethylene-propylene copolymer, ethylene-vinyl acetate copolymer, ionomer resin, ethylene-ethyl acrylate copolymer, ethylene-acrylic acid or Tacrylic acid copolymer, methylpentene polymer, polybutene resin, polyvinyl chloride resin, polyvinyl acetate resin, polyvinylidene chloride resin, vinyl chloride-vinylidene chloride copolymer, poly (meth) acrylic resin, polyacrylic Nitrile resin, polystyrene resin, acrylonitrile-styrene copolymer (AS resin), acrylonitrile-butadiene-styrene copolymer (ABS resin), polyester resin, polyamide resin, polycarbonate resin, polyvinyl alcohol Resin, saponified ethylene-vinyl acetate copolymer, fluorine resin, gen resin, polyacetal resin, polyurethane resin, nitrocellulose, etc. Can do. In addition, for example, synthetic paper may be used.
it can.
In the present invention, the film or sheet may be any of unstretched, uniaxially or biaxially stretched.
The thickness is arbitrary, but can be selected from a range of several μm to 300 μm.
Furthermore, in the present invention, the film or sheet may be a film having any property such as extrusion film formation, inflation film formation, and coating film.
[0062]
In particular, in the present invention, as other base materials, for example, low density polyethylene, medium density polyethylene, high density polyethylene, linear low density polyethylene, polypropylene, ethylene having a barrier property to prevent permeation of water vapor, water, etc. -A film or sheet of resin such as propylene copolymer, a film or sheet of resin such as nylon MXD6 resin having a barrier property to prevent permeation of oxygen gas, water vapor, etc., and a colorant such as a pigment to the resin, and other desired It is possible to use various colored resin films or sheets having light-shielding properties obtained by adding the above additives and kneading to form a film.
These materials can be used alone or in combination.
The thickness of the film or sheet is arbitrary, but is usually about 5 μm to 300 μm, more preferably about 10 μm to 100 μm.
[0063]
In the present invention, as described above, an inorganic oxide vapor-deposited film and a gas barrier coating film are provided on one surface of the base film, and then a printed pattern layer is formed on the gas barrier coating film, and A laminating adhesive layer is provided in sequence, a heat-sealable resin layer is further provided via the laminating adhesive layer, and further between the laminating adhesive layer and the heat-sealable resin layer. Moreover, the lid | cover material for aseptic rice filling packaging containers concerning this invention can be manufactured by laminating | stacking the resin film which has intensity | strength and was excellent in puncture resistance.
[0064]
Next, in the present invention, the tray-shaped filling and packaging container constituting the aseptic packaged rice produced using the lid for aseptic rice filling and packaging container according to the present invention will be described. As such a tray-shaped filling and packaging container, For example, polyethylene resin, polypropylene resin, polystyrene resin, polycarbonate resin, polyacrylonitrile resin, polyester resin, polyamide resin, acrylonitrile-styrene copolymer, acrylonitrile-pagetene-styrene copolymer, polyvinyl A tray-shaped resin produced by molding a resin such as an acetal resin, a (meth) acrylic resin, or the like using a molding method such as injection molding, extrusion molding, or the like. Filled packaging containers can be used.
Alternatively, in the present invention, as the tray-shaped filling and packaging container, for example, one or more of the above-exemplified resins are used, and for example, the T-die extrusion method or inflation is used. A single film or a co-extruded film of these resins is produced by single or co-extrusion using an extrusion method, etc., and then the single film or co-extruded film is used. A tray-shaped filling and packaging container or the like formed by molding using a thermoforming method can be used.
[0065]
Furthermore, in the present invention, as the above-mentioned tray-shaped filling and packaging container, for example, as described above, for example, polyethylene resin, polypropylene resin, polystyrene resin, polycarbonate-based embryo, polyacrylonitrile-based embryo, polyester Resins, polyamide resins, acrylonitrile-styrene copolymers, acrylonitrile-butadiene-styrene copolymers, polyvinyl acetal resins, (meth) acrylic resins, and other molding resins, such as ethylene-vinyl alcohol Copolymers, polyacrylonitrile resins, nylon MXD6 resins, and other barrier resins having the property of blocking the permeation of oxygen gas, water vapor, etc. are used, and these are used for T-die coextrusion or inflation. Co-extrusion using extrusion method, etc., For example, a coextruded film comprising 3 to 5 layers such as a polypropylene resin layer / ethylene-vinyl alcohol copolymer, a polyacrylonitrile resin, or a nylon MXD6 resin layer / polypropylene resin layer is manufactured. It is possible to use a tray-like filling and packaging container formed by using a film and molding it using a thermoforming method such as vacuum / pressure forming.
[0066]
Next, in the present invention, the tray-shaped filling and packaging container produced above is used, and the cooked rice is weighed and filled into the tray-shaped filling and packaging container from the opening, and thereafter The surface of the heat-sealable resin layer of the lid for aseptic rice filling and packaging container according to the present invention is overlapped with the surface of the flange portion of the opening of the tray-shaped filling and packaging container filled with rice as described above. Thereafter, the surface of the flange portion and the surface of the heat-sealable resin layer are heat-sealed to form a seal portion, and the aseptic packaged rice according to the present invention can be manufactured.
Of course, in the present invention, the manufacturing process as described above is performed in a clean room or a clean booth as described above.
In the above, as a heat sealing method, for example, a bar seal, a rotary roll seal, a belt seal, an impulse seal, a high frequency seal, an ultrasonic seal, or the like can be used.
Moreover, in the above, as the rice to be filled and packaged, ordinary rice, red rice, brown rice mixed with rice, rice cake, and other known items can be filled and packaged.
Thus, the lid for aseptic rice filling and packaging container according to the present invention and the aseptic packaging rice using the same have strength and the like, and have excellent durability, heat resistance, moisture resistance, and heat sealability. Excellent in pinhole resistance, puncture resistance, transparency, etc., and also has excellent barrier properties to prevent permeation of oxygen gas, water vapor, etc. In addition, the packaging bag after use does not generate harmful substances when incinerated and discarded, and has the advantage of being extremely excellent in disposal and environmental suitability.
[0067]
【Example】
The present invention will be described more specifically with reference to examples.
Example 1
(1). A biaxially stretched nylon 6 film having a thickness of 15 μm was used, and this was mounted on a feeding roll of a plasma chemical vapor deposition apparatus, and the corona treatment surface of the above biaxially stretched nylon 6 film was thickened under the conditions shown below. A 200 nm thick silicon oxide vapor deposition film was formed.
(Deposition conditions)
Deposition surface: Corona-treated surface
Reaction gas mixing ratio: hexamethyldisiloxane: oxygen gas: helium = 1.2: 5.0: 2.5 (unit: slm)
Ultimate pressure: 5.0 × 10^-5mbar
Film-forming pressure: 7.0 × 10^-2mbar
Power: 35kW
Line speed: 300m / min
Next, immediately after the silicon oxide vapor deposition film having a thickness of 200 mm is formed as described above, a glow discharge plasma generator is used on the silicon oxide vapor deposition film surface, and the power is 9 kw, oxygen gas (O₂): Argon gas (Ar) = 7.0: 2.5 (unit: slm) is used, and the mixed gas pressure is 6 × 10.^-2Oxygen / argon mixed gas plasma treatment was performed with mbar to form a plasma treated surface in which the surface tension of the deposited silicon oxide film surface was improved by 54 dyne / cm or more.
(2). On the other hand, 100 parts of tetra-i-propoxytitanium and 70 parts of acetylacetone were added to a reactor equipped with a reflux condenser and a stirrer, and stirred at 60 ° C. for 30 minutes to obtain a titanium chelate compound.
The purity of this reaction product was 75%.
Next, as component (A), an ethylene / vinyl alcohol copolymer [manufactured by Nippon Synthetic Chemical Co., Ltd., trade name, Soarnol D2935, saponification degree: 98% or more, ethylene content: 29 mol%, melt flow index: 35 g / 10 minutes] and polyvinyl pyrrolidone [manufactured by Wako Pure Chemical Industries, Ltd., Mw = 25,000], 5% water / n-propyl alcohol solution (water / n-propyl alcohol weight ratio = 40/60) ) 100 parts, and 2 parts of the titanium chelate compound prepared above, 16.8 parts of n-propyl alcohol, and 11.2 parts of water, and hydrolyzed at 55 ° C. for 4 hours; Further, 12.1 parts of N, N-dimethylformamide was mixed at 40 ° C. and stirred for 2 hours to obtain a gas barrier composition of the present invention.
Next, the plasma-treated surface formed in the above (1) is coated with the gas barrier composition produced above by the gravure roll coating method, and then heat-treated at 120 ° C. for 1 minute. 1.0g / m in thickness²A (barrier state) gas barrier coating film was formed to produce a barrier substrate.
(3). Next, on the surface of the gas barrier coating film of the barrier substrate produced as described above, a normal gravure ink composition is used, and predetermined printing consisting of letters, figures, symbols, patterns, etc. is performed by a gravure printing method. The pattern was printed to form a printed pattern layer.
Next, on the entire surface including the printed pattern layer formed as described above, a urethane adhesive (trade name, A616, manufactured by Takeda Pharmaceutical Company Limited) is used, and this is coated by a gravure roll coating method. Dry film 4g / m²A laminating adhesive layer is formed, and then a 50 μm-thick linear low-density polyethylene film is placed on the surface of the laminating adhesive layer, and the corona-treated surface is opposed to the laminating adhesive layer. After overlapping and then laminating both layers, a lid for a sterile cooked rice filling and packaging container according to the present invention was produced.
(4). On the other hand, a polypropylene resin film having a thickness of 150 μm was used, and this was thermoformed using a vacuum / pressure forming method to produce a tray-shaped molded container made of polypropylene.
Next, thoroughly wash the polypropylene tray-shaped molded container produced above, and further sterilize with a hydrogen peroxide solution or the like, then carry it into a clean room of class 10,000, and then in a clean room, In the tray-shaped molded container made of polypropylene sterilized as described above, the rice cooked in the same clean room is quantified and filled, and then the flange part of the opening of the tray-shaped molded container has the above ( 3), washed in the same manner as described above, and sterilized with hydrogen peroxide solution or the like. Both were heat-sealed and hermetically packaged and allowed to cool as it was to produce aseptically packaged cooked rice.
The packaged product made of aseptically packaged cooked rice produced above has excellent barrier properties against oxygen gas, water vapor, etc., has excellent laminate strength, etc., withstands distribution in the market, and is excellent in storage and storage. It was.
[0068]
Example 2
(1). In the same manner as in Example 2 above, a silicon oxide vapor deposition film having a thickness of 200 mm was formed on the corona treatment surface of a biaxially stretched nylon 6 film having a thickness of 15 μm, and the plasma treatment of the silicon oxide vapor deposition film was further performed. A gas barrier coating film was formed on the surface to produce a barrier substrate according to the present invention.
(2). Next, a printed pattern layer and an adhesive layer for laminating are further formed in the same manner as in Example 1 above on the surface of the gas barrier coating film of the silicon oxide vapor deposition film formed in (1) above. did.
Next, a biaxially stretched nylon 6 film having a thickness of 15 μm was laminated on the surface of the adhesive layer for lamination formed above with the corona-treated surfaces facing each other, and then dry laminated.
Further, a two-component curable polyurethane-based laminating adhesive was used on the other surface of the 15 μm thick biaxially stretched nylon 6 film laminated as described above, and this was used in the same manner as in Example 1 above. Film thickness of 4 g / m by roll coating method²An adhesive layer for lamination was formed by coating so as to be (dry state).
Next, a linear low-density polyethylene film having a thickness of 50 μm is laminated on the surface of the adhesive layer for laminating as described above with the corona-treated surfaces facing each other. The lid | cover material for aseptic cooked rice filling packaging containers concerning invention was manufactured.
(3). Hereinafter, the aseptic packaged rice according to the present invention was produced in the same manner as in Example 1 above, using the lid material for the aseptic cooked rice filling and packaging container produced above.
The packaged product made of aseptically packaged cooked rice produced above has excellent barrier properties against oxygen gas, water vapor, etc., has excellent laminate strength, etc., withstands distribution in the market, and is excellent in storage and storage. It was.
[0069]
Example 3
(1). A biaxially stretched polyethylene terephthalate film having a thickness of 12 μm is used as a base film, and this is attached to a delivery roll of a plasma chemical vapor deposition apparatus, and then fed out under the conditions shown below. On the corona-treated surface of the biaxially stretched polyethylene terephthalate film, a silicon oxide vapor deposition film having a thickness of 200 mm was formed.
(Deposition conditions)
Deposition surface: Corona-treated surface
Reaction gas mixing ratio: hexamethyldisiloxane: oxygen gas: helium = 1: 11: 10 (unit: slm)
Degree of vacuum in the vacuum chamber; 5.2 × 10^-6mbar
Degree of vacuum in the deposition chamber; 5.1 × 10^-2mbar
Cooling / electrode drum power supply: 60 w · min / m²
Film transport speed: 90 m / min
Next, immediately after forming the silicon oxide vapor-deposited film having a thickness of 200 mm as described above, the silicon oxide vapor-deposited film surface was subjected to plasma treatment in the same manner as in Example 1 to obtain a silicon oxide vapor-deposited film surface. A plasma-treated surface having a surface tension of 54 dyne / cm or more was formed.
(2). Next, on the surface of the silicon oxide plasma-treated surface formed in (1) above, a gas barrier coating film, a printed pattern layer, and a laminating adhesive layer are further formed in the same manner as in Example 1 above. Formed.
Next, a biaxially stretched nylon 6 film having a thickness of 15 μm was laminated on the surface of the adhesive layer for lamination formed above with the corona-treated surfaces facing each other, and then dry laminated.
Further, a two-component curable polyurethane-based laminating adhesive was used on the other surface of the 15 μm thick biaxially stretched nylon 6 film laminated as described above, and this was used in the same manner as in Example 1 above. Film thickness of 4.0 g / m by roll coating method²An adhesive layer for lamination was formed by coating so as to be (dry state).
Next, a linear low-density polyethylene film having a thickness of 50 μm is laminated on the surface of the adhesive layer for laminating as described above with the corona-treated surfaces facing each other. The lid | cover material for aseptic cooked rice filling packaging containers concerning invention was manufactured.
(3). On the other hand, a polypropylene resin was used and thermoformed using an injection molding method to produce a polypropylene tray-shaped molded container.
Next, thoroughly wash the polypropylene tray-shaped molded container produced above, and further sterilize with a hydrogen peroxide solution or the like, then carry it into a clean room of class 10,000, and then in a clean room, In the tray-shaped molded container made of polypropylene sterilized as described above, the rice cooked in the same clean room is quantified and filled, and then the flange part of the opening of the tray-shaped molded container has the above ( 2), washed in the same manner as described above, and sterilized with a hydrogen peroxide solution or the like, and the surfaces of the linear low-density polyethylene film of the lid for aseptic rice filling and packaging container facing each other, Both were heat sealed and hermetically packaged and allowed to cool as they were to produce aseptically packaged cooked rice.
The packaged product made of aseptically packaged cooked rice produced above has excellent barrier properties against oxygen gas, water vapor, etc., has excellent laminate strength, etc., withstands distribution in the market, and is excellent in storage and storage. It was.
[0070]
Example 4
(1). A biaxially stretched nylon 6 film having a thickness of 15 μm is used as a base film. First, the above biaxially stretched nylon 6 film is mounted on a delivery roll of a take-up vacuum deposition apparatus, and then The following vapor deposition conditions were applied by vacuum deposition using an electron beam (EB) heating method while supplying oxygen gas to the corona-treated surface of the biaxially stretched nylon 6 film using aluminum as the vapor deposition source. Thus, a vapor deposition film of aluminum oxide having a thickness of 200 mm was formed.
(Deposition conditions)
Degree of vacuum in the deposition chamber: 2 × 10^-4mbar
Degree of vacuum in winding chamber: 2 × 10^-2mbar
Electronic beam power: 25 kW
Film transport speed: 240 m / min
Deposition surface: Corona-treated surface
Next, immediately after the above-described aluminum oxide vapor deposition film having a thickness of 200 mm was formed, a plasma-treated surface was formed on the aluminum oxide vapor deposition film surface in the same manner as in Example 1 above.
(2). On the other hand, 100 parts of tetra-i-propoxytitanium and 70 parts of acetylacetone were added to a reactor equipped with a reflux condenser and a stirrer, and stirred at 60 ° C. for 30 minutes to obtain a titanium chelate compound.
The purity of this reaction product was 75%.
Next, as component (A), an ethylene / vinyl alcohol copolymer [manufactured by Nippon Synthetic Chemical Co., Ltd., trade name, Soarnol D2935, saponification degree: 98% or more, ethylene content: 29 mol%, melt flow index: 35 g / 10 minutes] and polyvinyl pyrrolidone [manufactured by Wako Pure Chemical Industries, Ltd., Mw = 25,000], 5% water / n-propyl alcohol solution (water / n-propyl alcohol weight ratio = 40/60) ) 100 parts, and 2 parts of the titanium chelate compound prepared above, 16.8 parts of n-propyl alcohol, and 11.2 parts of water, and hydrolyzed at 55 ° C. for 4 hours; Furthermore, 12.1 parts of N, N-dimethylformamide was mixed at 40 ° C. and stirred for 2 hours to obtain a gas barrier composition of the present invention.
Next, the plasma-treated surface formed in the above (1) is coated with the gas barrier composition produced above by the gravure roll coating method, and then heat-treated at 120 ° C. for 1 minute. 1.0g / m in thickness²A gas barrier coating film (dried state) was formed to produce a barrier substrate.
(3). Furthermore, a normal gravure ink composition is used on the surface of the gas barrier coating film constituting the barrier base material formed as described above, and a predetermined gravure printing method is used that includes characters, figures, symbols, patterns, etc. A printed pattern was printed to form a printed pattern layer.
Next, on the entire surface including the printed pattern layer formed as described above, a two-component curing type polyurethane-based laminating adhesive is used, and the film thickness is adjusted to 4.0 g / g by a gravure roll coating method as described above. m²An adhesive layer for lamination was formed by coating so as to be (dry state).
Next, a linear low-density polyethylene film having a thickness of 50 μm is laminated on the surface of the adhesive layer for laminating as described above with the corona-treated surfaces facing each other. The lid | cover material for aseptic cooked rice filling packaging containers concerning invention was manufactured.
(4). On the other hand, polypropylene resin and nylon MXD6 resin were used, and these were coextruded using an inflation coextrusion molding method, and a polypropylene resin layer having a thickness of 150 μm / nylon MXD6 resin layer having a thickness of 100 μm / polypropylene having a thickness of 50 μm. A three-layer coextruded film consisting of a resin layer was produced.
Subsequently, the three-layer coextruded film produced above was used and thermoformed using a vacuum / pressure forming method to produce a tray-shaped molded container.
Next, after thoroughly washing the tray-shaped molded container produced above and further sterilizing with a hydrogen peroxide solution etc., it is carried into a clean room of about class 10,000, and then sterilized as described above in a clean room. In the treated tray-shaped molded container, the rice cooked in the clean room is also quantified and filled, and then the flange part of the opening of the tray-shaped molded container is filled with the above (3). The lid of a sterile rice-filled packaging container lid that has been manufactured, washed in the same manner as described above, and sterilized with hydrogen peroxide solution or the like is placed facing each other, and then the two are laminated together. -Sealed and hermetically packaged, and allowed to cool as it was to produce aseptically packaged cooked rice.
The packaged product made of aseptically packaged cooked rice produced above has excellent barrier properties against oxygen gas, water vapor, etc., has excellent laminate strength, etc., withstands distribution in the market, and is excellent in storage and storage. It was.
[0071]
Example 5
(1). A biaxially stretched polyethylene terephthalate film with a thickness of 12 μm is used as the base film. First, the above-mentioned biaxially stretched polyethylene terephthalate film is mounted on a delivery roll of a take-up vacuum deposition apparatus. Then, this is drawn out, and the vacuum deposition method by the electron beam (EB) heating method while supplying oxygen gas to the corona-treated surface of the biaxially stretched polyethylene terephthalate film using aluminum as a deposition source. Thus, an aluminum oxide vapor deposition film having a thickness of 200 mm was formed under the following vapor deposition conditions.
(Deposition conditions)
Degree of vacuum in the deposition chamber: 2 × 10^-4mbar
Degree of vacuum in winding chamber: 2 × 10^-2mbar
Electronic beam power: 25 kW
Film transport speed: 240 m / min
Deposition surface: Corona-treated surface
Next, immediately after the above-described aluminum oxide vapor deposition film having a thickness of 200 mm was formed, a plasma-treated surface was formed on the aluminum oxide vapor deposition film surface in the same manner as in Example 1 above.
(2). Next, a gas barrier coating film, a printed pattern layer, and an adhesive layer for laminating are further formed on the plasma-treated surface of the aluminum oxide vapor deposition film formed in (1) above in the same manner as in Example 4 above. Formed.
Next, a biaxially stretched nylon 6 film having a thickness of 15 μm was superimposed on the surface of the adhesive layer for lamination formed above with the corona-treated surfaces facing each other, and then dry laminated.
Further, a two-component curable polyurethane-based laminating adhesive was used on the other surface of the 15 μm-thick biaxially stretched nylon 6 film laminated as described above. Film thickness of 4.0 g / m by roll coating method²An adhesive layer for lamination was formed by coating so as to be in a (dry operation state).
Next, a 50 μm-thick linear low-density polyethylene film is superimposed on the surface of the laminating adhesive layer formed above with the corona-treated surfaces facing each other, and then both are laminated by dry lamination. The lid material for aseptic rice filling and packaging containers according to the present invention was produced.
(3). Hereinafter, the aseptic packaged rice according to the present invention was produced in the same manner as in Example 1 above, using the lid material for a sterile cooked rice filling container produced above.
The packaged product made of aseptically packaged cooked rice produced above has excellent barrier properties against oxygen gas, water vapor, etc., has excellent laminate strength, etc., withstands distribution in the market, and is excellent in storage and storage. It was.
[0072]
Experimental example
About the lid | cover for aseptic cooked rice filling packaging containers manufactured in said Examples 1-5, oxygen permeability, water vapor permeability, and puncture resistance were measured.
(1). Measurement of oxygen permeability
This was measured with a measuring instrument (model name, OXTRAN) manufactured by MOCON, USA under the conditions of a temperature of 23 ° C. and a humidity of 90% RH.
(2). Measurement of water vapor transmission rate
This was measured under the conditions of a temperature of 40 ° C. and a humidity of 90% RH with a measuring instrument (model name, PERMATRAN) manufactured by MOCON, USA.
(3). Measurement of puncture resistance
This was measured by a tensile tester for the piercing strength of the lid material at a compression speed of 50 mm / min with a needle tip having a radius of 0.5 mm.
The measurement results are shown in Table 1 below.
[0073]
(Table 1)

In Table 1 above, the unit of oxygen permeability is [cc / m.²/ Day · 23 ° C. · 90% RH], and the unit of water vapor permeability is [g / m²/ Day · 40 ° C. · 100% RH], and the unit of puncture resistance is [gf].
[0074]
As is clear from the measurement results shown in Table 1 above, the lid for aseptic rice-filled packaging container according to the present invention is excellent in oxygen barrier properties, water vapor barrier properties, etc., and also excellent in puncture resistance. It was a thing.
[0075]
【The invention's effect】
As apparent from the above description, the present invention focuses on a barrier film comprising a structure in which a vapor deposition film of an inorganic oxide such as silicon oxide or aluminum oxide is provided on one surface of a base film. A gas barrier coating film, a printed pattern layer, and an adhesive layer for laminating are sequentially provided on the vapor-deposited film of inorganic oxide such as silicon oxide and aluminum oxide constituting the barrier film. A lid is produced by providing a heat-sealable resin layer through the laminating adhesive layer, and thus using the lid, for example, using a polypropylene resin, and molding the lid After filling cooked rice in a tray-shaped filling packaging container made of polypropylene resin, the surface of the heat-sealable resin layer constituting the lid material is opposed to the flange portion of the opening of the packaging container Let me After bonding, the two are tightly bonded by heat sealing or the like and hermetically wrapped to produce aseptically packaged cooked rice that has strength, etc., and has heat resistance, moisture resistance, heat sealing properties, and pinhole resistance. Excellent in puncture resistance, puncture resistance, transparency, etc. In addition, it has excellent barrier properties to prevent permeation of oxygen gas, water vapor, etc. It is possible to produce a lid material that is extremely excellent in waste disposal suitability, environmental suitability and the like, and aseptically packaged cooked rice using the same, without generating harmful substances during disposal.
[Brief description of the drawings]
FIG. 1 is a schematic cross-sectional view showing an outline of an example of a layer structure of a lid for a sterile cooked rice filling and packaging container according to the present invention.
FIG. 2 is a schematic sectional view showing an outline of an example of the layer structure of the lid for a sterile cooked rice filling and packaging container according to the present invention.
FIG. 3 is a schematic perspective view showing an example of the configuration of a filling and packaging container used for aseptically packaged cooked rice according to the present invention.
FIG. 4 is a diagram illustrating the filling of the cooked rice used in the aseptic packaged rice according to the present invention shown in FIG. 3 with the cooked rice, and the aseptic rice according to the present invention as shown in FIG. It is a schematic sectional drawing which shows an example of the structure about the aseptic packaging cooked rice manufactured by using the lid | cover material for filling packaging containers, and heat-sealing and sealing-packing this.
FIG. 5 is a schematic block diagram showing an example of a low-temperature plasma chemical vapor deposition apparatus.
FIG. 6 is a schematic horizontal view showing an example of a take-up vacuum deposition apparatus.
[Explanation of symbols]
A Cover for aseptic rice filling and packaging container
A₁  Aseptic rice filling and packaging container
B Tray-shaped filling and packaging container
C Aseptic packaging rice
1 Base film
2 Vapor deposition film of inorganic oxide
3 Gas barrier coating film
4 Print pattern layer
5 Adhesive layer for laminating
6 Heat-sealable resin layer
7 Resin film with strength and excellent puncture resistance
11 opening
12 Flange
13 Side wall
14 Bottom wall
15 Rice
16 Seal part

Claims (11)

An inorganic oxide vapor-deposited film and a gas barrier coating film are provided on one surface of the base film, and a printed pattern layer and a laminating adhesive layer are sequentially formed on the gas barrier coating film. Next, a lid for a sterile cooked rice filling and packaging container, wherein a heat-sealable resin layer is provided through the adhesive layer for laminating. 2. The aseptic cooked rice package according to claim 1, wherein a resin film having strength and excellent puncture resistance is laminated between the adhesive layer for laminating and the heat-sealable resin layer. Container lid. The base film is made of a biaxially stretched polyester resin film, a biaxially stretched polyamide resin film, or a biaxially stretched polyolefin resin film. The aseptic rice filling and packaging container to be described. The sterile cooked rice according to any one of claims 1 to 3, wherein the inorganic oxide vapor-deposited film comprises an inorganic oxide vapor-deposited film formed by chemical vapor deposition or physical vapor deposition. Cover material for filling and packaging containers. The lid for a sterile cooked rice filling and packaging container according to any one of claims 1 to 4, wherein the vapor-deposited film of the inorganic oxide is a vapor-deposited film of silicon oxide by chemical vapor deposition. The aseptic rice-filled packaging container lid according to any one of claims 1 to 4, wherein the inorganic oxide vapor-deposited film is an aluminum oxide vapor-deposited film formed by physical vapor deposition. The gas barrier coating film is at least a polyvinyl alcohol-based resin and a general formula R ¹ _m M (OR ² ) _n (wherein M represents a metal atom, R ¹ is the same or different and has 1 carbon atom Represents an organic group having ˜8, R ² is the same or different and represents an alkyl group having 1 to 5 carbon atoms, an acyl group having 1 to 6 carbon atoms or a phenyl group, and m and n each represents an integer of 0 or more. M + n represents the valence of M.) metal alcoholate, hydrolyzate of the metal alcoholate, condensate of the metal alcoholate, chelate of the metal alcoholate 2. A gas barrier coating film comprising a gas barrier composition comprising a compound, a hydrolyzate of the chelate compound and at least one selected from the group of metal acylates. Any one of -6 Sterile rice filling and packaging container lid as described. The heat-sealing resin layer is made of a polyolefin resin layer, and the lid for aseptic rice-filled packaging container according to any one of claims 1 to 7, wherein the heat-sealing resin layer is a polyolefin resin layer. An inorganic oxide vapor-deposited film and a gas barrier coating film are provided on one surface of the base film, and a printed pattern layer and a laminating adhesive layer are sequentially formed on the gas barrier coating film. Then, the surface of the heat-sealable resin layer was cooked using a lid for aseptic rice-filled packaging container having a structure in which a heat-sealable resin layer was provided via the adhesive layer for laminating. Filling the cooked packaging container filled with cooked rice, facing the surface of the flange part and overlaying it, heat-sealing the surface of the heat-sealable resin layer and the surface of the flange part to form a sealed part and filling the cooked rice Aseptic packaged cooked rice characterized by packaging. 10. The aseptic packaged rice according to claim 9, wherein a resin film having strength and excellent puncture resistance is laminated between an adhesive layer for laminating and a heat-sealable resin layer. . The filling and packaging container is composed of a polypropylene resin-made tray-shaped filling and packaging container formed by using a polypropylene resin, and the filling and packaging container is described in any one of claims 9 to 10 above. Aseptically packaged cooked rice.

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