JP3882959B2 - Antibacterial laminated packaging material and package - Google Patents

Description

【００１３】
（Ｒ₁ ，Ｒ₂ ，Ｒ₃ は水素原子、炭素原子数１〜１８個の直鎖または分岐のアルキル基、アリール基、ヒドロキシル基、またはアルコキシ基で置換されたアルキル基、アリール基またはアラルキル基を表し、Ｘ−はアニオン、ｎは２以上の整数を示す）
上記Ｒ₁ 、Ｒ₂ 、Ｒ₃ の具体例としてはメチル、エチル、プロピル、ブチル、ペンチル、ヘキシル、ヘプチル、オクチル、ドデシル等のアルキル基、フェニル、トリル、キシリル等のアリール基、ベンジル、フェニチル等のアラルキル基、ヒドロシキル基、アルコシキ基等で置換されたもので、アルキル基、アリール基等が特に好ましい。Ｒ₁ 、Ｒ₂ 、Ｒ₃ は同一の基でも、異なった基でもよい。Ｘ−はアニオンであり、たとえばフッ素、塩素、臭素またはヨウ素等のハロゲンイオン、硫酸イオン、リン酸イオン、過塩素酸イオンが挙げられハロゲンイオンが好ましい。ｎは特に限定しないが、２〜５００、好ましくは１０〜３００である。他のホスホニウム塩基含有高分子化合物の例は、主としてジカルボン酸成分及びスルホン酸基含有芳香族ジカルボン酸のホスホニウム塩を１ｍｏｌ％以上５０ｍｏｌ％以下及びグリコール成分からなる共重合ポリエステルである。
【００１４】
該共重合ポリエステルのジカルボン酸成分としては、芳香族ジカルボン酸、脂環族ジカルボン酸、脂肪族ジカルボン酸、複素環式ジカルボン酸、などが挙げられる。芳香族ジカルボン酸としては、テレフタル酸、イソフタル酸、フタル酸、２，６−ナフタレンジカルボン酸、４，４−ジカルボキシルフェニール、４，４−ジカルボキシルベンゾフェノン、ビス（４−カルボキシルフェニル）エタン及びそれらの誘導体などがあり、脂環式ジカルボン酸はシクロヘキサノン−１，４−ジカルボン酸及びその誘導体などがあり、脂肪族ジカルボン酸としては、アジピン酸、セバシン酸、ドデカンジオン酸、エイコ酸、ダイマー酸及びそれらの誘導体などがあり、複素環式ジカルボン酸としてはピリジンカルボン酸及びその誘導体が挙げられる。このようなジカルボン酸成分以外にｐ−オキシ安息香酸などのオキシカルボン酸類、トリメリット酸、ピロメリット酸及びその誘導体の多官能酸を含むことも可能である。
【００１５】
グリコール成分としては、エチレングリコール、１，２−プロピレングリコール、１，３−プロピレングリコール、１，４−ブタンジオール、１，６−ヘキサンジオール、ネオペンチルグリコール、ジエチレングリコール、１，４−シクロヘキサンジメタノール、ビスフェノールＡのエチレンオキサイド付加物、ポリエチレングリコール、ポリプロピレングリコール、ポリテトラメチレングリコール等が挙げられる。このほか少量のアミド結合、ウレタン結合、エーテル結合、カーボネート結合等を含有する化合物を含んでいてもよい。スルホン酸基含有芳香族ジカルボン酸のホスホニウム塩としては、スルホイソフタル酸トリ−ｎ−ブチルオクタデシルホスホニウム塩、スルホイソフタル酸トリ−ｎ−ブチルオクタデシルホスホニウム塩、スルホイソフタル酸トリ−ｎ−ブチルヘキサデシルホスホニウム塩、スルホイソフタル酸トリ−ｎ−ブチルテトラデシルホスホニウム塩、スルホイソフタル酸−ｎ−ブチルドデシルホスホニウム塩、４−スルホナフタレン−２，７−ジカルボン酸トリ−ｎ−ブチルデシルホスホニウム塩、４−スルホナフタレン−２，７−ジカルボン酸トリ−ｎ−ブチルオクタデシルホスホニウム塩、４−スルホナフタレン−２，７−ジカルボン酸トリ−ｎ−ブチルヘキサデシルホスホニウム塩、４−スルホナフタレン−２，７−ジカルボン酸トリ−ｎ−ブチルテトラデシルホスホニウム塩、４−スルホナフタレン−２，７−ジカルボン酸トリ−ｎ−ブチルドデシルホスホニウム塩等が挙げられ、抗菌活性の点からはスルホイソフタル酸トリ−ｎ−ブチルヘキサデシルホスホニウム塩、スルホイソフタル酸トリ−ｎ−ブチルテトラデシルホスホニウム塩、スルホイソフタル酸トリ−ｎ−ブチルドデシルホスホニウム塩が特に好ましい。
【００１６】
上記芳香族ジカルボン酸ホスホニウム塩はスルホ芳香族ジカルボン酸またはそのナトリウム塩、カリウム塩、アンモニウム塩等にトリ−ｎ−ブチルヘキサデシルホスホニウムブロマイド、トリ−ｎ−ブチルテトラデシルホスホニウムブロマイド、トリ−ｎ−ブチルドデシルホスホニウムブロマイド等のホスホニウム塩を反応させることにより得られる。このときの反応溶媒は特に限定しないが、水が最も好ましい。該共重合ポリエステルには着色度及びゲル発生度等の耐熱性改善の目的で、酸化アンチモン、酸化ゲルモニウム、チタン化合物等の重合触媒以外に酢酸マグネシウム、塩化マグネシウム等のＭｇ塩、酢酸カルシウム、塩化カルシウム等のＣａ塩、酢酸マンガン、塩化マンガン等のＭｎ塩、塩化亜鉛、酢酸亜鉛等のＺｎ塩、塩化コバルト、酢酸コバルト等のＣｏ塩 を各々金属イオンとして３００ｐｐｍ以下、リン酸またはリン酸トリメチルエステル、リン酸トリエチルエステル等のリン酸エステル誘導体をＰとして２００ｐｐｍ以下添加することも可能である。
【００１７】
上記重合触媒以外の金属イオンの総量が３００ｐｐｍ、またＰ量が２００ｐｐｍを越えるとポリマーの着色が顕著になるのみならず、ポリマーの耐熱性及び耐加水分解性も著しく低下する。このとき、耐熱性、耐加水分解性等の点で、総Ｐ量と総金属イオン量とのモル比は、０．４〜１．０であることが好ましい。
【００１８】
【数１】

【００１９】
上記モル原子比が０．４未満または１．０を越える場合には、本発明の組成物の着色、粗大粒子発生が顕著となり、好ましくない。
有機高分子系抗菌剤の分子量は特に限定しないが、共重合ポリエステルの場合には分子量５０００以上５００００以下、好ましくは１００００以上３００００以下、さらに好ましくは１５０００以上２５０００以下である。分子量が５０００以下では本発明の抗菌組成物の力学的強度が不十分で実用上好ましくない。該共重合ポリエステルの製造法は特に限定しないが、ジカルボン酸類とグリコール類とを直接反応させ得られたオリゴマーを重縮合する、いわゆる直接重合法、ジカルボン酸のジメチルエステル体とグリコールとをエステル交換反応させたのちに重縮合する、いわゆるエステル交換法などが挙げられ、任意の製造法を適用することができる。
【００２０】
上記金属イオン及びリン酸及びその誘導体の添加時期は特に限定しないが、一般的には金属イオン類は原料仕込み時、すなわちエステル交換前またはエステル化前に、リン酸類の添加は重縮合反応前に添加するのが好ましい。
ホスホニウム塩基含有ポリマーの合成は上記の方法に限定されるものではなく、他の合成方法としては、スルホン酸（または塩）基含有ポリマーに、トリ−ｎ−ブチルテトラデシルホスホニウムブロマイド、トリ−ｎ−テトラデシルホスホニウムブロマイド、トリ−ｎ−ブチルドデシルホスホニウムブロマイド等のホスホニウム塩を反応させることが挙げられる。
【００２１】
本発明における親水性物質とは水と親和性に優れた物質で、水に溶解、分散あるいは保水、保湿性、膨潤可能な物質であり、一般的には水酸基、アミノ基、アミド基、カルボキシル基またはそのアルカリ金属塩、スルホン酸基またはそのアルカリ金属塩、第４級アンモニウム塩基、アミン塩基の少なくとも１種を含む有機化合物または高分子化合物で、例えばポリオキシメチレン鎖、ポリオキシエチレン鎖、ポリオキシプロピレン鎖が代表的に挙げられる。ポリアミンとは主鎖の中に塩基性の窒素原子を含む高分子で、代表的なものにポリエチレンイミン、ポリアルキレンポリアミン（例えばポリエチレンポリアミン）がある。
【００２２】
親水性物質の具体例としては、ポリビニルアルコール、ポリアクリルイミド、ポリ（Ｎ，Ｎ−ジメチルアミノメチルアクリルアミド）、ポリ（Ｎ，Ｎ−ジメチルアミノエチルアクリレート）、ポリ（Ｎ，Ｎ−ジメチルアミノエチルメタクリレート）、ポリビニルアミン、ポリビニルピリジン、ポリビニルピロリドン、ポリビニルイミダゾール、ポリアクリル酸のホモポリマーまたは共重合体、ポリメタクリル酸のホモポリマーまたは共重合体、無水マレイン酸のホモポリマーまたは共重合体（例えば、無水マレイン酸・スチレン共重合体）、ポリビニルスルホン酸またはその共重合体またはそれらのアルカリ金属塩、ポリスチレンスルホン酸またはその共重合体またはそれらのアルカリ金属塩、ポリスチレンの第４級アンモニウム塩誘導体、ポリビニルイミダゾリン塩、ポリアリルアミン塩、ポリエチレングリコール（別名 ポリエチレンオキサイド）ポリプロピレングリコール、ポリエチレン・プロピレングリコール、ポリテトラメチレングリコール等のポリアルキレングリコール、グリセリン、ポリグリセリン等のポリオールまたはその重合体、スルホイソフタル酸のアルカリ塩またはアンモニウム塩を１ｍｏｌ％以上１０ｍｏｌ％以下共重合したポリエステルを挙げることができる。
【００２３】
またこれらのポリアルキレングリコール、ポリグリセリンの末端がアルコール、アルキフェノール、脂肪酸、アミン類等で封鎖されたポリエーテル誘導体でもよく、例えば、ポリエチレングリコールモノメチルエーテル、ポリエチレングリコールジメチルエーテル、ポリグリセリンアルキレンオキサイド付加物、その脂肪酸エステルまたは脂肪族アルコールエーテル、ポリグリセリン脂肪族脂肪酸エステル、ポリグリセリン脂肪族アルコールエーテル、ポリグリセリングリシジルエーテル、その反応物等の誘導体が挙げられる。中でもポリエチレングリコール、ポリグリセリン及びそれらの誘導体がポリエステルへの相溶性及び抗菌性の向上の点で好ましい。
【００２４】
該親水性物質の分子量は特に限定しないが、ポリエチレングリコールの場合には数平均分子量で２００以上３００００以下が好ましく、さらには１０００以上２５０００以下が好ましい。該親水性物質（共重合体の場合は、共重合体中にしめる親水性物質をさす）の添加量は特に限定しないが、ポリエチレングリコールを親水性物質として添加する場合には、無機系と有機系抗菌剤の総量に対して０．１〜２０重量％好ましくは０．５〜１０重量％さらに好ましくは１〜５重量％である。０．１重量％以下では抗菌活性増大効果が不十分で、２０重量％を越えると抗菌組成物の機械的特性及び耐熱性・耐候性が低下し、好ましくない。親水性物質の無機系及び又は有機系抗菌剤に含ませる方法は特に限定せず、無機系及び又は有機系抗菌剤の製造方法、化学的性質、物理的性質により、混合、溶融混練り、イオン結合、共有結合、共重合等任意の方法を採用できる。
【００２５】
特に有機高分子系抗菌剤への親水性物質の添加は、混合はもちろんのこと共重合の形をとることも可能である。
例えば、前記グリコール、ポリオール、スルホイソフタル酸のアルカリ塩またはアンモニウム塩、ビニルピロリドン、アクリル酸、スチレンスルホン酸等のような共重合可能な親水性物質（モノマー）を前記抗菌成分を有するポリエステル、ポリアミド、ポリオレフィン等のポリマー主鎖または側鎖に結合させることは、親水性物質の系外へのブリードアウト防止、すなわち本発明の抗菌性組成物の高抗菌活性の長期維持の点から好ましい。
【００２６】
さらに、無機系及び又は有機系抗菌剤と親水性物質を押し出し機等を用いて加熱溶融混合させる方法、有機高分子系抗菌剤の製造時、重合反応前にモノマー中に、あるいは重合反応の途中もしくは反応終了後に反応系内に親水性物質あるいはモノマーを添加する方法、また、無機系及び又は有機系抗菌剤と親水性物質類を適当な溶媒中、例えば水、水／アルコール混合溶媒、アセトン、メチルエチルケトン等の有機溶媒等に混合溶解又は分散した後、該溶媒を乾固する等の方法がある。
【００２７】
上記の工程により得られた抗菌性組成物中の親水性物質が無機系抗菌剤及び有機系抗菌剤と、共有結合、イオン結合、共重合、また混合等のいかなる形態で存在していてもよいが、有機系抗菌剤の場合には親水性物質は共重合の形で存在することが、抗菌活性の寿命の点からも好ましい。
【００２８】
本発明の抗菌性組成物に滑り性、耐摩耗性、耐ブロッキング性、隠蔽性等の物理的特性の向上を目的として、抗菌性組成物中に予め炭酸カルシウム（ＣａＣＯ₃ ）、リン酸カルシウム、アパタイト、硫酸バリウム（ＢａＳＯ₄ ）、フッ化カルシウム（ＣａＦ₂ ）、タルク、カオリン、酸化珪素（ＳｉＯ₂ ）、アルミナ（Ａｌ₂ Ｏ₃ ）、二酸化チタン、酸化ジルコニウム（ＺｒＯ₂ ）、酸化鉄（Ｆｅ₂ Ｏ₃ ）、アルミナ／シリカ複合酸化物などの無機粒子、ポリスチレン、ポリメタクリル酸エステル、ポリアクリル酸エステル、それらの共重合体、あるいはそれらの架橋体などの有機粒子等を添加することも可能である。上記粒子についてさらに詳細に述べると以下の如くなる。
【００２９】
炭酸カルシウム粒子は、その結晶構造により三方または六方晶系に分類されるカルサイト、斜方晶系に分類されるアラゴナイト、六方または擬六方晶系に分類されるバテライトの３つの結晶型に分類されるが、いかなる結晶型でもよく、その形状も、連球状、立方球状、紡錘状、柱状、針状、球形、卵形など任意に選択できる。
【００３０】
上記アルミナとしては、ジブサイト、バイヤライト、ノルトストランダイト、ベーマイト、ダイアスボア、トーダイトなどの結晶性アルミナ水和物；無定型ゲル、ベーマイトゲル、バイヤライトゲルなどの非晶性アルミナ水和物；及びρ、η、γ、χ、κ、δ、θ型などの中間活性アルミナまたはα型アルミナ等が挙げられる。これらの平均粒径は目的に応じて変更する必要があるので、特に限定しないが、一般的には平均１次粒子径が０．０１μ以上５μ以下が好ましく、その添加量は５重量％以下が好ましい。粒子の添加量が５０００ｐｐｍを越える場合には、無機系及び又は有機系抗菌剤中の粗大粒子が顕著になり、それから得られる抗菌フィルム表面に粗大突起が目立ち、粒子の脱落が起こりやすくなり、フィルムの品位の低下を招く。上記微粒子の抗菌性組成物への充填混合方法は特に限定しないが、有機系抗菌剤を所定の溶媒に分散あるいは溶解させ、その系に上記粒子を分散させる方法、また有機系抗菌剤の合成重合反応系中に該微粒子を添加し分散させる方法と、特に有機系抗菌剤が熱可塑性ポリマーの場合にはそのポリマー中に該粒子を添加し溶融混合する方法当がある。
【００３１】
有機系抗菌剤がポリエステルの場合には、粒子は、通常、エチレングリコールに加えて、スラリーとしてポリエステルの重合反応系中へ添加される。その添加時期は、使用する微粒子種類、粒子径、塩素イオン濃度、さらにスラリー濃度、スラリーの温度などに依存するが、通常、ポリエステル重合反応開始前またはオリゴマー生成段階が好ましい。スラリーの反応系への添加時、スラリーをエチレングリコールの沸点まで加熱することが、粒子の分散性の向上の点で好ましい。また抗菌性組成物に微粒子を添加する場合、あらかじめ微粒子を添加した所定の熱可塑性樹脂を無機系及び又は有機系抗菌剤と混合することも可能である。
【００３２】
本発明の抗菌性積層体を積層する方法としては従来よりある、エキストルージョンラミネート法、ホットメルトラミネート法、ドライラミネート法、ウエットラミネート法等の方式を採用することができる。プラスチックフィルムの加工においては、前記方法の中でもエキストルージョンラミネート法及びドライラミネート法が一般的に行われており現実的である。エキストルージョンラミネート法においては、熱溶融フィルムとしてポリエチレン、ポリプロピレン、エチレン共重合体等が用いられ、接着力を向上させる為にテトラアルキルチタネート化合物、ポリエチレンイミン、あるいはイミン化合物等をプライマーコートした後にメルトインデックス４〜７程度の高温安定性の良い品種を使う方法が推奨される。ドライラミネート法においては、接着剤として酢酸ビニル、塩化ビニル、塩化ビニリデン樹脂等のビニール系樹脂、ニトロセルロース、エチルセルロース、セルロースアセテート等のセルロース系樹脂、エポキシ系樹脂、合成ゴムとアクリル系樹脂との共重合物等が用いられ、コーティング方法としてはグラビヤロールコーティング、リバースロールコーティング、ディップコーティング、ドクターブレード、エアーナイフコーティング等の方法が使用される。
【００３３】
本発明の抗菌性積層体の構成は、使用目的及び用途に応じて特許請求項１〜７の範囲内で任意の構成を選択することができる。ポリオレフィン層には、低密度ポリエチレン、高密度ポリエチレン等のポリエチレン、ポリプロピレン、ポリブテン等を用いることができる。前記ポリマーを用いることにより、包装材料として必要なヒートシール性、耐油性、防湿性等の機能を付加することができ、また必要に応じて前記ポリマーに帯電防止剤、防曇剤等を添加することにより帯電防止性能、防曇性能を付加することもできる。これらのポリオレフィンの性能を最大限に発揮させる為には積層体の片側最外層に積層させることが望ましい。
【００３４】
さらに本発明の抗菌性積層体に上記以外の性能を付加する為に３層以上の構成を取ることも可能である。例えばポリエステル／アルミニウム箔／ポリエチレン、ポリエステル／ポリ塩化ビニリデン／ポリエチレン等の構成でガスバリヤー性を付与する事が可能で、ポリエステル／ナイロン６／アルミニウム箔／ポリプロピレン等の構成で耐レトルト性に優れた包装材料を得ることができる。
【００３５】
本発明の抗菌性積層体を用いて抗菌性を有する包装袋を得る方法としては、シール方法としてバーシール法、回転ロールシール法、インパルスシール法、溶断シール法、熱溶融シール法、超音波シール法、高周波シール法等があり任意の方法を選択することが可能であり、得られる袋の形態としてはピロー包装袋、三方シール袋、四方シール袋等目的に応じて任意の形態を選択することができる。
但し、上記抗菌性積層体構成及び抗菌性積層体よりなる包装袋を得る方法例は一例であり、上記例に限定されるものではない。
【００３６】
（実施例）
次に実施例及び比較例を用いて本発明を更に詳細に説明するが、以下の実施例に限定されるものではない。以下に実施例及び比較例で得られた抗菌性組成物の物性の測定方法を示す。
抗菌性テスト
１／５０ブロースで希釈したＳ．ａｕｒｅｕｓ（黄色ブドウ球菌）の菌液（濃度：１０7 個／ｍｌ）の０．１ｍｌを予め高圧蒸気殺菌した５ｃｍ×５ｃｍの大きさのフィルム上に滴下し、そのフィルムに高圧蒸気滅菌したサランラップフィルムを密着させた。その試験片を滅菌シャーレに移し、３７℃で２４時間培養した。それからフィルム上の菌をＳＣＤＬＰ培地１０ｍｌで洗い出し、１０倍希釈し、普通寒天平板にまいた後２４時間後に菌数を計測した。
【００３７】
（実施例１）
テレフタル酸ジメチルエステル９モル、５−スルホイソフタル酸ジメチルエステルのトリ−ｎ−ブチルヘキサデシルホスホニウム塩１モル、エチレングリコール２２モル、共重合ポリエステル理論生成量に対して酢酸亜鉛を亜鉛（Ｚｎ）として２００ｐｐｍ加え、１４０から２２０℃まで昇温して生成するメタノールを系外に留去しながらエステル交換反応を行った。
エステル交換反応終了後、２５０℃にて、分子量１００００（ナカライ（株））のポリエチレングリコールを０．１２モル、さらに生成共重合ポリエステル理論量に対して酸化アンチモンをアンチモン（Ｓｂ）として２５０ｐｐｍ及びトリメチルホスフェノートをＰ量として８０ｐｐｍ加え１５分撹拌し、続いて平均粒径０．９ミクロンの球状シリカを２０００ｐｐｍ添加した。２６０℃、真空下で６０分間重縮合反応を行い、極限粘度０．５０の共重合ポリエステル樹脂を得た。
【００３８】
上記ポリマーを２軸押し出し機を用いて２５０℃で溶融押し出しし、３０℃の冷却ロールで冷却して、厚さ１８０μｍの未延伸フィルムを得た。
この未延伸フィルムを８０℃に加熱された周速の異なる一対のロール間で縦方向に３．５倍延伸し、次いでテンターにより１２０℃で横方向に３．５倍延伸した後、１９０〜２００℃で熱固定し、厚さ１４．５μｍの２軸延伸ポリエステルフィルムを得た。
【００３９】
上記２軸延伸ポリエステルフィルムとポリエチレンフィルム（ＬＩＸ−２ 厚さ４０μｍ、（東洋紡績（株））をドライラミネート法により、接着剤（主剤：ＡＤ５９０，硬化剤ＲＴ８６（東洋モートン（株））にてラミネート後、得られた積層フィルムのポリエステル面側の抗菌性評価結果を表１に示した。
【００４０】
（実施例２〜８）
実施例１においてポリエチレングリコールの種類及び量を表１に示すようにした以外は実施例１と同様にして抗菌性積層フィルムを得、実施例１と同様にして抗菌性評価を行い、得られた結果を表１に示した。
【００４１】
（実施例９〜１０）
実施例１においてホスホニウム塩の種類及び量を表１に示すようにした以外は実施例１と同様にして抗菌性積層フィルムを得、実施例１と同様にして抗菌性評価を行い、得られた結果を表１に示した。
【００４２】
（比較例１〜３）
実施例１，９，１０において、ポリエチレングリコール無添加の条件以外は実施例１，９，１０と全く同様にして、抗菌性積層フィルムを得、実施例１と同様に抗菌性評価を行い、結果を表１に示した。
【００４３】
（実施例１１）
（Ａ）基材フィルムの調整
平均粒径０．５μｍの炭酸カルシウム微粒子が４０００ｐｐｍの濃度で分散されたポリエスチレンテレフタレートを２９０℃で溶融押し出しし、３０℃の冷却ロールで冷却して、厚さ約１８０μｍの未延伸フィルムを得た。
（Ｂ）抗菌組成物塗布液の調整
実施例４においてテレフタル酸ジメチルエステル９モルの代わりにテレフタル酸ジメチルエステル５モル及びイソフタル酸ジメチルエステル４モルの混合物を用いた以外は実施例１と同様にして抗菌性組成物を得た。本抗菌性組成物を市販特級試薬メチルエチルケトンに溶解し３重量％の溶液とした。
（Ｃ）積層フィルムの調整
上記（Ｂ）で得た抗菌組成物塗布液を孔径１．０μｍのフィルターに通した後、上記（Ａ）で得た未延伸ポリエステルフィルムの表面にバーコーター法によって塗布し、７０℃で熱風乾燥した。次いでテンターにより１３０℃で横方向に３．５倍延伸した後、２００〜２１０℃で熱固定し、厚さ１４．５μｍの２軸延伸積層ポリエステルフィルムを得た。
上記２軸延伸積層ポリエステルフィルムの抗菌組成物塗布面と反対側の面にポリエチレンフィルム（ＬＩＸ−２厚さ４０μｍ、（東洋紡績（株））をドライラミネート法により、接着剤（主剤：ＡＤ５９０，硬化剤ＲＴ８６（東洋モートン（株））にてラミネートした。該フィルムの最終的な被覆剤（抗菌組成物）の付着量は約０．２ｇ／ｍ² であった。得られた積層フィルムの抗菌組成物塗布面側の抗菌性評価結果を表２に示した。
【００４４】
（実施例１２）
実施例１１において得られた抗菌組成物塗布液を７５μｍ厚の２軸延伸透明ＰＥＴフィルム（東洋紡績（株））に固形分０．３μｍ厚になるように塗布した。実施例１１と同様にしてラミネート後、抗菌組成物塗布面側の抗菌性評価結果を表２に示した。
【００４５】
（実施例１３）
実施例１１において得られた抗菌組成物塗布液を７５μ厚の白色ＰＥＴ合成紙クリスパー（東洋紡績（株））に固形分０．３μｍ厚になるように塗布した。実施例１１と同様にしてラミネート後、抗菌性組成物塗布面側の抗菌性評価結果を表２に示した。
【００４６】
（実施例１４〜１６）
実施例１１においてホスホニウムの塩の種類及び量を表２に示すようにした以外は実施例１１と同様にして抗菌性積層フィルムを得、抗菌性組成物塗布面側の評価結果を表２に示した。
【００４７】
（比較例４〜６）
実施例１１においてポリエチレングリコールを無添加とした以外は実施例１と全く同様にして共重合体の合成を行い、実施例１１，１２，１３と同様な基体にコート後、同様にラミネートを行い、積層フィルムの抗菌性組成物塗布面側の評価結果を表２に示した。
【００４８】
（参考例１）
平均粒径０．５μｍの炭酸カルシウム微粒子が４０００ｐｐｍの濃度で分散されたテレフタル酸／／エチレングリコール／ポリエチレングリコール（分子量１０００）（１００／／９５／５モル比）共重合体１００重量部に１重量部の銀／リン酸ジルコニウム系抗菌フィラー、ノバロン（東亜合成（株））を添加混合した後、２８０℃で溶融押し出しし、３０℃の冷却ロールで冷却して、厚さ約１８０μｍの未延伸フィルムを得た。この未延伸フィルムを、８５℃に加熱された周速の異なる一対のロール間で縦方向に３．５倍延伸し、次いでテンターにより１３０℃で横方向に３．５倍延伸した後、２００〜２１０℃で熱固定し、厚さ１４．５μｍの２軸延伸ポリエステルフィルムを得た。得られたフィルムとポリエチレンフィルム（ＬＩＸ−２ 厚さ４０μｍ （東洋紡績（株））をドライラミネート法により、接着剤（主剤：ＡＤ５９０，硬化剤：ＲＴ８６（東洋モートン（株））にてラミネート後、得られた積層フィルムのポリエステル面側の抗菌性評価結果を表３に示した。
【００４９】
（参考例２〜３）
参考例１において銀／リン酸ジルコニウム系抗菌フィラー（東亜合成（株））の代わりに表３に示した無機抗菌剤を用いた以外は参考例１と同様にして抗菌性積層フィルムを得、参考例１と同様にして得られた積層フィルムのポリエステル面側の抗菌性評価結果を表３に示した。尚、Ｐ−２５含有系の抗菌性評価はブラックライトを４０ｃｍの距離で照らしながら行った。
【００５０】
（比較例７〜９）
参考例１において共重合体の代わりにポリエチレンテレフタレートＰＥＴを用いた以外は参考例１，２，３と全く同様にして抗菌性積層フィルムを得、参考例１と同様にして得られた積層フィルムのポリエステル面側の抗菌性評価結果を表３に示した。
【００５１】
（参考例４）
（Ａ）スルホン酸基含有ポリエステル及び水分散液の調整
まずスルホン酸基含有ポリエステルを次の方法により調整した。ジカルボン酸成分としてジメチルテレフタレート９５モル％及び５−スルホイソフタル酸ナトリウム５モル％を使用し、常法によりエステル交換反応及び重縮合を行った。
得られたスルホン酸基含有ポリエステル（ＰＥＳ−ＳＯ３Ｎａ）のガラス転移温度は６９℃であった。このスルホン酸基含有ポリエステル３００部とｎ−ブチルセロソルブ１５０部とを加熱撹拌して粘ちょうな溶液とし、更に撹拌しつつ水５５０部を徐々に加えて、固形分３０％の均一な淡白色の水分散液を得た。この分散液をさらに水とイソプロパノールの等量混合液中に加え、固形分が５％のスルホン酸含有ポリエステル水分散液を調整した。
（Ｂ）混合塗布液の調整
銀／リン酸ジルコニウム系抗菌フィラー、ノバロン（東亜合成（株））０．１重量部を上記（Ａ）スルホン酸基含有ポリエステル水分散液１００重量部に添加混合、微分散させ塗布液とした。
（Ｃ）フィルムの調整
塗布液を変える以外は実施例１１と同様に基材フィルムを調整し、塗布液を塗布後同様にラミネートを行い積層フィルムを作成した。該フィルムの最終的な被覆剤の付着量は０．５ｇ／ｍ² であった。得られたフィルムの被覆剤塗布面の抗菌性評価結果を表４に示した。
【００５２】
（参考例５〜６）
参考例４において銀／リン酸ジルコニウム系抗菌フィラー（東亜合成（株））の代わりに表４に示した無機抗菌剤を用いた以外は参考例４と同様にして抗菌性積層フィルムを得、参考例１と同様にフィルムの被覆剤塗布面の抗菌性評価結果を表４に示した。
尚、Ｐ−２５含有系の抗菌性評価はブラックライトを４０ｃｍの距離で照らしながら行った。
【００５３】
（参考例７）
平均粒径０．５μｍの炭酸カルシウム微粒子が４０００ｐｐｍの濃度で分散されたポリエチレンテレフタレート（ＰＥＴ、分子量２００００）９５重量部にポリエチレングリコール（分子量２００００）５重量部の銀／リン酸ジルコニウム系抗菌フィラー（東亜合成（株））２重量部を添加した後、２８０℃で溶融押し出しし、３０℃の冷却ロールで冷却して、厚さ約１８０μｍの未延伸フィルムを得た。この未延伸フィルムを８５℃に加熱された周速の異なる一対のロール間で縦方向に３．５倍延伸し、次いでテンターにより１３０℃で横方向に３．５倍延伸した後、２００〜２１０℃で熱固定し、厚さ１４．５μｍの２軸延伸ポリエステルフィルムを得た。得られたフィルムとポリエチレンフィルム（ＬＩＸ−２ 厚さ４０μｍ（東洋紡績（株））をドライラミネート法により、接着剤（主剤：ＡＤ５９０，硬化剤：ＲＴ８６（東洋モートン（株））にてラミネート後、得られた積層フィルムのポリエステル面側の抗菌性評価結果を表５に示した。
【００５４】
（参考例８〜９）
参考例７において銀／リン酸ジルコニウム系抗菌フィラー（東亜合成（株））の代わりに表３に示した無機抗菌剤を用いた以外は参考例１と同様にして抗菌性積層フィルムを得、参考例１と同様にフィルムの被覆剤塗布面の抗菌性評価結果を表５に示した。
尚、Ｐ−２５含有系の抗菌性評価はブラックライトを４０ｃｍの距離で照らしながら行った。
【００５５】
（比較例１０〜１２）
参考例７，８，９において共重合体の代わりにポリエチレンテレフタレートＰＥＴを用いた以外は参考例７，８，９と全く同様に抗菌性積層フィルムの作成、抗菌性評価を行い、表５の結果を得た。
【００５６】
（参考例１０〜１５）
参考例７，８，９において、ポリエチレングリコールの代わりに表１に示したポリグリセリン３種、ポリグリセリン＃３１０、ポリグリセリン＃５００、ポリグリセリン＃７５０（坂本薬品工業（株））、ポリビニルアルコール（ＰＶＡ）を使用した以外は参考例７，８，９と全く同様に抗菌性積層フィルムの作成、抗菌性評価を行い、表６の結果を得た。
【００５７】
（実施例１７）
実施例１〜１６と参考例１〜１５に示した抗菌性積層フィルムを抗菌性組成物含有ポリエステル面を袋外面として、インパルスシール法により三方をシール後、袋内部にメチレンブルー試験液を満たしその後に残る一方を同様にインパルスシール法によりシールして試験液を充填した四方シール袋とし、４５℃±２℃の恒温槽中に２４時間放置した後液漏れの有無を調べたが、全て液漏れ無く良好であった。
以上のように本発明よる抗菌性積層体よりなる包装材料及び包装袋を用いて被覆、包装することによって本来抗菌性を有さない物品に抗菌性を付与することができると共に本発明よる高度な抗菌活性を有する様々な物品を提供できることとなる。従って滅菌を必要とする分野においてはその効果を維持する等の付加価値を与えた物品を製造することができる。
【００５８】
【発明の効果】
本発明の抗菌性積層体よりなる包装材料及び包装袋を用いることにより、抗菌性を有さない物品に高度な抗菌性を後付けの形で付与することが出来、すなわち本発明に特徴的な抗菌剤を表面に有する包装体を提供できる。加えて光触媒機能の付加により、任意の工程で近紫外光を当てることにより更に強力な抗菌性を発揮する包装材料、包装袋及び包装体としうる。
【００５９】
【表１】

【００６０】
【表２】

【００６１】
【表３】

【００６２】
【表４】

【００６３】
【表５】

[0001]
BACKGROUND OF THE INVENTION
The present invention provides a packaging material and a packaging body comprising an antibacterial laminate containing an antibacterial composition comprising an inorganic and / or organic antibacterial agent and a hydrophilic substance. Therefore, the present invention can be applied to all fields of use in which the laminated packaging material is used, that is, industrial films and packaging films, and new antibacterial properties can be imparted. In particular, it is suitably used in foods that require sterilization, medical instruments, medical facilities, and packaging coatings in the pharmaceutical field.
[0002]
[Prior art]
Thermoplastic resins, among which polyethylene, polypropylene, polyvinylidene chloride, nylon, polyethylene terephthalate and ethylene terephthalate have excellent physical and chemical properties, are used in fibers, plastics, films, sheets, adhesives and the like. Recently, antibacterial products have been devised in which these are filled or coated with inorganic or organic antibacterial agents.
Antibacterial agents currently being studied or used mainly include natural products such as chitin, chitosan, horseradish extract mustard extract, hinokitiol, tea extract antibacterial agent, photo-oxidation catalyst titanium oxide particles, zinc oxide ultrafine particles, silver Examples thereof include inorganic compound products such as zeolite containing zeolite and silver-containing zirconium phosphate, and synthetic products such as organic ammonium salt compounds and organic phosphonium salt compounds.
[0003]
Inorganic antibacterial agents typified by natural and silver are safe and safe in terms of toxicity, and the following inventions have already been disclosed.
JP-A-3-83905 discloses a silver ion-containing phosphate antibacterial agent, and JP-A-3-161409 discloses an antibacterial agent obtained by substituting a certain volume in a zeolite having a specific ion exchange capacity with silver ions. Has been. Films, sheets, fibers and plastics were prepared according to the inventions disclosed in these, and their antibacterial properties against Staphylococcus aureus, Escherichia coli, etc. were evaluated, but antibacterial activity was reduced if the amount added was relatively modest to maintain transparency. When the antibacterial activity was insufficient, transparency had to be sacrificed, and there was room for improvement in practice. On the other hand, the antibacterial agents of organic synthetic products generally have antibacterial activity superior to natural products and inorganic products against fungi etc., but when those antibacterial agents are surface-coated or filled on a substrate such as a film, Since the antibacterial agent has a low molecular weight, it is easily volatilized, desorbed and separated from a substrate such as a film, which is not preferable from the viewpoint of antibacterial long-term stability and safety to the human body. When an antibacterial agent is used for a film, etc., the antibacterial agent does not dissolve in water or an organic solvent, and it is difficult to release, detach, peel off, and drop off from the film surface. It is preferable from the viewpoint of safety. Under such circumstances, recently, an immobilized antibacterial agent in which an organic antibacterial agent is bound to a polymer material as a raw material such as a film or fiber by an ionic bond or a covalent bond has been disclosed.
[0004]
Japanese Patent Application Laid-Open No. 54-86584 describes an antibacterial material mainly composed of a polymer substance containing an antibacterial component having a quaternary ammonium base ionically bonded to an acidic group such as a carboxyl group or sulfonic acid. ing. Japanese Patent Application Laid-Open No. 61-245378 describes a fiber made of a polyester copolymer containing an antibacterial component having a polar group such as an amidine group or a quaternary ammonium base.
In JP-A-57-204286, 63-60903, 62-114903, JP-A-1-93596, JP-A-2-240090, etc., as well as various nitrogen-containing compounds, phosphonium salt compounds are widely active against bacteria. It is known as a biologically active chemical substance with a spectrum.
[0005]
An invention has been disclosed in which the above phosphonium salt is immobilized on a polymer substance to try to expand the application. JP-A-4-266912 discloses an antibacterial agent of a phosphonium salt vinyl polymer, and JP-A-4-814365 discloses an antibacterial agent of a vinylbenzylphosphonium salt vinyl polymer. Further, JP-A-5-310820 describes an antibacterial material mainly composed of a polymer substance containing an antibacterial component having an acidic group and a phosphonium base ionically bonded to the acidic group. In the examples, polyesters using phosphonium salts of sulfoisophthalic acid are disclosed.
[0006]
JP-A-6-41408 does not mention any antibacterial action, but phosphonium sulfonate copolymer polyester and polyalkylene glycol for photographic support, packaging, general industrial use, magnetic tape, etc. A modified polyester and a polyester film are disclosed.
Unlike the aforementioned JP-A-5-310820, the alkyl group bonded to the phosphonium salt described in the specification of the above patent is a type having a relatively short carbon number such as a butyl group, a phenyl group, and a benzyl group. JP-A-4-266912, JP-A-4-814365, and JP-A-5-310820 have been intensively studied, and phosphonium base-containing vinyl copolymers and copolyesters are synthesized according to the examples to form fibers, films, sheets, etc. Also, a laminate was formed by applying the antibacterial polymer thereof onto the fiber or film sheet surface, and the antibacterial activity was evaluated, but the antibacterial activity was insufficient. Furthermore, in order to improve antibacterial properties, we synthesized a polyester with 50 mol% or more of tri-normal butyl dodecyl phosphonium base, and made films and sheets from it. Antibacterial properties as well as deterioration of physical properties were insufficient.
Furthermore, the above-mentioned inorganic antibacterial agent and organic antibacterial agent were used alone or in combination to form fibers, fabrics, films, sheets, etc., and their antibacterial activity against Staphylococcus aureus, Escherichia coli, etc. was evaluated. Insufficient and insufficient for practical use.
[0007]
[Problems to be solved by the invention]
The present invention solves the above-mentioned conventional problems and improves the antibacterial activity without increasing the amount of the inorganic and / or organic antibacterial agent in the substrate or the surface of the substrate. It is an object of the present invention to provide a laminated packaging material and a packaging body to which an antibacterial agent that can be applied is applied, and to provide an article that can be easily imparted with antibacterial properties by coating and packaging with the laminated packaging material and the packaging body .
[0008]
[Means for Solving the Problems]
The object of the present invention is achieved by an antibacterial composition containing an inorganic and / or organic antibacterial agent and a hydrophilic substance. In a preferred embodiment, this is achieved by an antibacterial composition in which the organic antibacterial agent and the hydrophilic substance are copolymerized.
In a further preferred embodiment, the inorganic antibacterial agent is an inorganic compound in which at least one metal fine particle of silver (Ag), zinc (Zn), copper (Cu) and / or metal ions are supported, or titanium oxide ( TiO ₂ ) And / or zinc oxide (ZnO) ₂ ).
[0009]
In a more preferred embodiment, it is achieved by an antibacterial composition in which the organic antibacterial agent is a polymer compound containing an ammonium base and / or a phosphonium base and / or a sulfonium base in the main chain or side chain. In a particularly preferred embodiment, the hydrophilic substance contains at least one of a hydroxyl group, an amino group, an amide group, a carboxyl group or an alkali metal salt thereof, a quaternary ammonium base, an amine base, a polyether chain, and a polyamine chain. This is achieved by an antibacterial composition that is a molecular compound.
The antibacterial composition of the present invention is characterized in that its antibacterial activity is remarkably enhanced by including a hydrophilic substance in an inorganic and / or organic antibacterial agent.
Next, the present invention will be described in detail.
[0010]
The inorganic antibacterial agent of the present invention is a general term for inorganic compounds having antibacterial activity against Staphylococcus aureus and Escherichia coli containing metal or metal ions, and the form thereof may be gas, liquid or solid. Examples include metal particles such as silver, zinc and copper having antibacterial activity or metal oxide species such as silica, metal oxides such as silica, zeolite, synthetic zeolite, calcium calcium phosphate phosphate, zinc calcium phosphate, ceramic, and soluble glass. Fine particles supported on inorganic substances such as powder, alumina silicon, titanium zeolite, apatite, calcium carbonate, and sol-gel thin films of metal oxides having photo-oxidation catalytic functions such as zinc oxide, titanium oxide, molybdenum oxide or the like Fine particles, sol-gel thin films and fine particles are surface-treated with inorganic or organic compound reagents, and composite particles in which the surface is laminated, coated, packaged or embedded with other inorganic oxides, composite oxides, etc. by sol-gel method etc. Can be given. It is also possible to add the above-mentioned inorganic antibacterial agent to the metal alcoholate as a raw material when forming the metal sol-gel body and use it as a composite system.
[0011]
Specific examples of such inorganic antibacterial agents include Novalon (manufactured by Toa Gosei Co., Ltd.), Bact killer (manufactured by Kanebo Kasei Co., Ltd.), and antibacterial true spherical ceramic particles S1, S2, S5 (manufactured by Admatech). ), Holon Killer (manufactured by Nikko Co., Ltd.), Zeomic (manufactured by Shinagawa Fuel Co., Ltd.), Amenitop (manufactured by Matsushita Electric Industrial Co., Ltd.), and Ion Pure (manufactured by Ishizuka Glass Co., Ltd.) , P-25 (manufactured by Nippon Aerosil Co., Ltd.), ST-135 (manufactured by Ishihara Sangyo Co., Ltd.) and the like, and the like, but are not limited thereto. Examples of the composite particles include fine particles obtained by coating titanium dioxide with silica, GYT (manufactured by Goyo Paper Industries Co., Ltd.), but are not limited thereto.
One of the polymer antibacterial agents is a phosphonium salt vinyl polymer represented by the following general formula.
[0012]
[Chemical 1]

[0013]
(R ₁ , R ₂ , R _Three Represents a hydrogen atom, a linear or branched alkyl group having 1 to 18 carbon atoms, an aryl group, a hydroxyl group, or an alkyl group substituted with an alkoxy group, an aryl group or an aralkyl group, X- represents an anion, n Represents an integer of 2 or more)
R above ₁ , R ₂ , R _Three Specific examples of these include alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl and dodecyl, aryl groups such as phenyl, tolyl and xylyl, aralkyl groups such as benzyl and phenethyl, hydroxy groups and alkoxy groups. An alkyl group, an aryl group and the like are particularly preferable. R ₁ , R ₂ , R _Three May be the same group or different groups. X- is an anion, and examples thereof include halogen ions such as fluorine, chlorine, bromine and iodine, sulfate ions, phosphate ions and perchlorate ions, and halogen ions are preferable. n is not particularly limited, but is 2 to 500, preferably 10 to 300. Examples of other phosphonium base-containing polymer compounds are copolyesters mainly composed of 1 mol% to 50 mol% of a phosphonium salt of a dicarboxylic acid component and a sulfonic acid group-containing aromatic dicarboxylic acid and a glycol component.
[0014]
Examples of the dicarboxylic acid component of the copolymer polyester include aromatic dicarboxylic acids, alicyclic dicarboxylic acids, aliphatic dicarboxylic acids, and heterocyclic dicarboxylic acids. Aromatic dicarboxylic acids include terephthalic acid, isophthalic acid, phthalic acid, 2,6-naphthalenedicarboxylic acid, 4,4-dicarboxylphenyl, 4,4-dicarboxylbenzophenone, bis (4-carboxylphenyl) ethane and the like And alicyclic dicarboxylic acids include cyclohexanone-1,4-dicarboxylic acid and derivatives thereof. Examples of aliphatic dicarboxylic acids include adipic acid, sebacic acid, dodecanedioic acid, eicoic acid, dimer acid and Examples of the heterocyclic dicarboxylic acid include pyridinecarboxylic acid and derivatives thereof. In addition to such a dicarboxylic acid component, oxycarboxylic acids such as p-oxybenzoic acid, trimellitic acid, pyromellitic acid, and polyfunctional acids such as derivatives thereof may be included.
[0015]
Examples of the glycol component include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, diethylene glycol, 1,4-cyclohexanedimethanol, Examples include ethylene oxide adducts of bisphenol A, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, and the like. In addition, a small amount of a compound containing an amide bond, a urethane bond, an ether bond, a carbonate bond, or the like may be included. Examples of phosphonium salts of sulfonic acid group-containing aromatic dicarboxylic acids include sulfo-isophthalic acid tri-n-butyloctadecylphosphonium salt, sulfoisophthalic acid tri-n-butyloctadecylphosphonium salt, sulfoisophthalic acid tri-n-butylhexadecylphosphonium salt , Sulfoisophthalic acid tri-n-butyltetradecylphosphonium salt, sulfoisophthalic acid-n-butyldodecylphosphonium salt, 4-sulfonaphthalene-2,7-dicarboxylic acid tri-n-butyldecylphosphonium salt, 4-sulfonaphthalene- 2,7-dicarboxylic acid tri-n-butyloctadecylphosphonium salt, 4-sulfonaphthalene-2,7-dicarboxylic acid tri-n-butylhexadecylphosphonium salt, 4-sulfonaphthalene-2,7-dicarboxylic acid tri-n − Examples thereof include tiltetradecylphosphonium salt, 4-sulfonaphthalene-2,7-dicarboxylic acid tri-n-butyldodecylphosphonium salt, and sulfoisophthalic acid tri-n-butylhexadecylphosphonium salt, sulfo Particularly preferred are tri-n-butyltetradecylphosphonium salt of isophthalic acid and tri-n-butyldodecylphosphonium salt of sulfoisophthalic acid.
[0016]
The aromatic dicarboxylic acid phosphonium salt may be sulfo-aromatic dicarboxylic acid or its sodium salt, potassium salt, ammonium salt, etc., tri-n-butylhexadecylphosphonium bromide, tri-n-butyltetradecylphosphonium bromide, tri-n-butyl. It can be obtained by reacting a phosphonium salt such as dodecylphosphonium bromide. The reaction solvent at this time is not particularly limited, but water is most preferable. In addition to polymerization catalysts such as antimony oxide, germanium oxide, and titanium compounds, the copolyester has Mg salts such as magnesium acetate and magnesium chloride, calcium acetate, and calcium chloride for the purpose of improving heat resistance such as coloring and gel generation. Mn salt such as manganese acetate and manganese chloride, Zn salt such as zinc chloride and zinc acetate, Co salt such as cobalt chloride and cobalt acetate, each of which is 300 ppm or less, phosphoric acid or phosphoric acid trimethyl ester, It is also possible to add a phosphate ester derivative such as phosphoric acid triethyl ester as P in an amount of 200 ppm or less.
[0017]
When the total amount of metal ions other than the above polymerization catalyst exceeds 300 ppm and the amount of P exceeds 200 ppm, not only the coloring of the polymer becomes remarkable, but also the heat resistance and hydrolysis resistance of the polymer are remarkably lowered. At this time, it is preferable that the molar ratio of the total P amount and the total metal ion amount is 0.4 to 1.0 in terms of heat resistance, hydrolysis resistance, and the like.
[0018]
[Expression 1]

[0019]
When the molar atomic ratio is less than 0.4 or exceeds 1.0, coloring of the composition of the present invention and generation of coarse particles become remarkable, which is not preferable.
The molecular weight of the organic polymer antibacterial agent is not particularly limited, but in the case of a copolyester, the molecular weight is from 5,000 to 50,000, preferably from 10,000 to 30,000, more preferably from 15,000 to 25,000. When the molecular weight is 5000 or less, the mechanical strength of the antibacterial composition of the present invention is insufficient, which is not preferable for practical use. The method for producing the copolyester is not particularly limited, but a so-called direct polymerization method in which an oligomer obtained by directly reacting a dicarboxylic acid and a glycol is polycondensed, a transesterification reaction between a dimethyl ester of a dicarboxylic acid and a glycol. A so-called transesterification method, in which polycondensation is performed after the formation, can be used, and any production method can be applied.
[0020]
The timing of adding the metal ions and phosphoric acid and derivatives thereof is not particularly limited. Generally, metal ions are added to the raw material, that is, before transesterification or esterification, and phosphoric acid is added before the polycondensation reaction. It is preferable to add.
The synthesis of the phosphonium base-containing polymer is not limited to the above method, and other synthetic methods include a sulfonic acid (or salt) group-containing polymer, tri-n-butyltetradecylphosphonium bromide, tri-n- Examples include reacting phosphonium salts such as tetradecylphosphonium bromide and tri-n-butyldodecylphosphonium bromide.
[0021]
The hydrophilic substance in the present invention is a substance having an excellent affinity with water, and is a substance that can be dissolved, dispersed or retained in water, moisturized, swelled, and generally has a hydroxyl group, an amino group, an amide group, a carboxyl group. Or an organic compound or polymer compound containing at least one of an alkali metal salt, a sulfonic acid group or an alkali metal salt thereof, a quaternary ammonium base, and an amine base, such as a polyoxymethylene chain, a polyoxyethylene chain, a polyoxy A propylene chain is typically mentioned. The polyamine is a polymer containing a basic nitrogen atom in the main chain, and representative examples include polyethyleneimine and polyalkylenepolyamine (for example, polyethylenepolyamine).
[0022]
Specific examples of hydrophilic substances include polyvinyl alcohol, polyacrylimide, poly (N, N-dimethylaminomethyl acrylamide), poly (N, N-dimethylaminoethyl acrylate), poly (N, N-dimethylaminoethyl methacrylate). ), Polyvinylamine, polyvinylpyridine, polyvinylpyrrolidone, polyvinylimidazole, polyacrylic acid homopolymer or copolymer, polymethacrylic acid homopolymer or copolymer, maleic anhydride homopolymer or copolymer (eg, anhydrous Maleic acid / styrene copolymer), polyvinyl sulfonic acid or copolymer thereof or alkali metal salt thereof, polystyrene sulfonic acid or copolymer thereof or alkali metal salt thereof, quaternary ammonium salt derivative of polystyrene, Livinylimidazoline salt, polyallylamine salt, polyethylene glycol (also known as polyethylene oxide) polypropylene glycol, polyalkylene glycols such as polyethylene propylene glycol, polytetramethylene glycol, polyols such as glycerin and polyglycerin or polymers thereof, sulfoisophthalic acid Mention may be made of polyesters in which an alkali salt or an ammonium salt is copolymerized in an amount of 1 mol% to 10 mol%.
[0023]
These polyalkylene glycols may be polyether derivatives whose polyglycerin ends are blocked with alcohol, alkylphenol, fatty acid, amines, etc., for example, polyethylene glycol monomethyl ether, polyethylene glycol dimethyl ether, polyglycerin alkylene oxide adduct, The fatty acid ester or aliphatic alcohol ether, polyglycerin aliphatic fatty acid ester, polyglycerin fatty alcohol ether, polyglycerin glycidyl ether, and derivatives thereof such as the reaction product thereof may be mentioned. Among these, polyethylene glycol, polyglycerin and derivatives thereof are preferable in terms of improving compatibility with polyester and antibacterial properties.
[0024]
The molecular weight of the hydrophilic substance is not particularly limited, but in the case of polyethylene glycol, the number average molecular weight is preferably 200 or more and 30000 or less, and more preferably 1000 or more and 25000 or less. The addition amount of the hydrophilic substance (in the case of a copolymer, the hydrophilic substance incorporated in the copolymer) is not particularly limited, but when polyethylene glycol is added as a hydrophilic substance, inorganic and organic substances are added. It is 0.1-20 weight% with respect to the total amount of an antibacterial agent, Preferably it is 0.5-10 weight%, More preferably, it is 1-5 weight%. If the content is less than 0.1% by weight, the effect of increasing the antibacterial activity is insufficient, and if it exceeds 20% by weight, the mechanical properties, heat resistance and weather resistance of the antibacterial composition are lowered, which is not preferable. There are no particular restrictions on the method of including the hydrophilic substance in the inorganic and / or organic antibacterial agent, and mixing, melt-kneading, and ionization depending on the production method, chemical properties, and physical properties of the inorganic and / or organic antibacterial agent. Arbitrary methods such as bonding, covalent bonding, and copolymerization can be employed.
[0025]
In particular, the addition of a hydrophilic substance to an organic polymer antibacterial agent can take the form of copolymerization as well as mixing.
For example, a polyester, polyamide having the antibacterial component as a copolymerizable hydrophilic substance (monomer) such as glycol, polyol, alkali salt or ammonium salt of sulfoisophthalic acid, vinylpyrrolidone, acrylic acid, styrenesulfonic acid, etc. Binding to a polymer main chain or side chain such as polyolefin is preferable from the viewpoint of preventing bleeding out of the hydrophilic substance to the outside of the system, that is, maintaining the high antibacterial activity of the antibacterial composition of the present invention for a long period of time.
[0026]
Further, a method of heating and melt mixing an inorganic and / or organic antibacterial agent and a hydrophilic substance using an extruder, etc., during production of an organic polymer antibacterial agent, in the monomer before the polymerization reaction, or in the middle of the polymerization reaction Alternatively, after completion of the reaction, a method of adding a hydrophilic substance or monomer to the reaction system, or an inorganic and / or organic antibacterial agent and hydrophilic substances in a suitable solvent such as water, water / alcohol mixed solvent, acetone, There is a method of mixing and dissolving or dispersing in an organic solvent such as methyl ethyl ketone and then drying the solvent.
[0027]
The hydrophilic substance in the antibacterial composition obtained by the above steps may be present in any form such as covalent bond, ionic bond, copolymerization, and mixing with inorganic antibacterial agent and organic antibacterial agent. However, in the case of an organic antibacterial agent, it is preferable from the viewpoint of the lifetime of the antibacterial activity that the hydrophilic substance is present in a copolymerized form.
[0028]
In order to improve physical properties such as slipperiness, abrasion resistance, blocking resistance, and hiding properties, the antibacterial composition of the present invention is preliminarily incorporated with calcium carbonate (CaCO _Three ), Calcium phosphate, apatite, barium sulfate (BaSO) _Four ), Calcium fluoride (CaF) ₂ ), Talc, kaolin, silicon oxide (SiO2) ₂ ), Alumina (Al ₂ O _Three ), Titanium dioxide, zirconium oxide (ZrO) ₂ ), Iron oxide (Fe ₂ O _Three ), Inorganic particles such as alumina / silica composite oxide, organic particles such as polystyrene, polymethacrylic acid ester, polyacrylic acid ester, copolymers thereof, and cross-linked materials thereof can also be added. The particles will be described in detail as follows.
[0029]
Calcium carbonate particles are classified into three crystal types according to their crystal structures: calcite classified as trigonal or hexagonal, aragonite classified as orthorhombic, and vaterite classified as hexagonal or pseudohexagonal. However, any crystal type may be used, and the shape thereof can be arbitrarily selected from a continuous spherical shape, a cubic spherical shape, a spindle shape, a columnar shape, a needle shape, a spherical shape, an oval shape, and the like.
[0030]
Examples of the alumina include crystalline alumina hydrates such as dibsite, bayerite, nordstrandite, boehmite, dicebore, and todite; amorphous alumina hydrates such as amorphous gel, boehmite gel, and bayerite gel; and ρ , Η, γ, χ, κ, δ, θ-type intermediate activated alumina or α-type alumina. Since these average particle diameters need to be changed according to the purpose, there is no particular limitation. Generally, the average primary particle diameter is preferably 0.01 μm or more and 5 μm or less, and the addition amount is 5% by weight or less. preferable. When the added amount of the particles exceeds 5000 ppm, coarse particles in the inorganic and / or organic antibacterial agent become prominent, and coarse protrusions are conspicuous on the surface of the antibacterial film obtained therefrom, and the particles are likely to fall off. This leads to a decline in quality. The method of filling and mixing the fine particles into the antibacterial composition is not particularly limited, but a method of dispersing or dissolving the organic antibacterial agent in a predetermined solvent and dispersing the particles in the system, or synthetic polymerization of the organic antibacterial agent There are a method of adding and dispersing the fine particles in the reaction system, and a method of adding the particles into the polymer and melt-mixing them especially when the organic antibacterial agent is a thermoplastic polymer.
[0031]
When the organic antibacterial agent is polyester, the particles are usually added as a slurry into the polyester polymerization reaction system in addition to ethylene glycol. The timing of addition depends on the kind of fine particles used, the particle diameter, the chlorine ion concentration, the slurry concentration, the temperature of the slurry, etc., but usually the polyester polymerization reaction is preferably started or the oligomer formation stage is preferred. When adding the slurry to the reaction system, it is preferable to heat the slurry to the boiling point of ethylene glycol from the viewpoint of improving the dispersibility of the particles. Moreover, when adding microparticles | fine-particles to an antibacterial composition, it is also possible to mix the predetermined thermoplastic resin to which microparticles | fine-particles were added previously with an inorganic type and / or an organic type antibacterial agent.
[0032]
As a method for laminating the antibacterial laminate of the present invention, conventional methods such as an extrusion laminating method, a hot melt laminating method, a dry laminating method, and a wet laminating method can be employed. In the processing of plastic films, the extrusion laminating method and the dry laminating method are generally performed among the above methods, and are practical. In the extrusion laminating method, polyethylene, polypropylene, ethylene copolymer, etc. are used as a heat-melt film, and a melt index is applied after primer coating with a tetraalkyl titanate compound, polyethyleneimine, or imine compound to improve adhesion. A method using a variety having a high temperature stability of about 4 to 7 is recommended. In the dry lamination method, vinyl resins such as vinyl acetate, vinyl chloride, and vinylidene chloride resins as adhesives, cellulose resins such as nitrocellulose, ethyl cellulose, and cellulose acetate, epoxy resins, synthetic rubbers, and acrylic resins Polymers and the like are used, and as a coating method, methods such as gravure roll coating, reverse roll coating, dip coating, doctor blade, air knife coating and the like are used.
[0033]
The composition of the antibacterial laminate of the present invention can be selected from any composition within the scope of claims 1 to 7 according to the purpose of use and application. For the polyolefin layer, polyethylene such as low density polyethylene and high density polyethylene, polypropylene, polybutene and the like can be used. By using the polymer, it is possible to add functions such as heat sealability, oil resistance, and moisture resistance necessary as a packaging material, and if necessary, an antistatic agent, an antifogging agent, etc. are added to the polymer. Accordingly, antistatic performance and antifogging performance can be added. In order to maximize the performance of these polyolefins, it is desirable to laminate them on the outermost layer on one side of the laminate.
[0034]
Furthermore, in order to add performances other than the above to the antibacterial laminate of the present invention, it is possible to take a structure of three or more layers. For example, it is possible to provide gas barrier properties with a configuration such as polyester / aluminum foil / polyethylene, polyester / polyvinylidene chloride / polyethylene, etc., and a packaging with excellent retort resistance in a configuration such as polyester / nylon 6 / aluminum foil / polypropylene. Material can be obtained.
[0035]
As a method for obtaining a packaging bag having antibacterial properties using the antibacterial laminate of the present invention, a bar seal method, a rotary roll seal method, an impulse seal method, a fusing seal method, a hot melt seal method, an ultrasonic seal are used as the seal method. Method, high-frequency sealing method, etc., and any method can be selected, and the form of the resulting bag can be selected according to the purpose, such as a pillow packaging bag, three-side seal bag, four-side seal bag, etc. Can do.
However, the example of the method of obtaining the packaging bag which consists of the said antibacterial laminated body structure and an antibacterial laminated body is an example, and is not limited to the said example.
[0036]
(Example)
EXAMPLES Next, although this invention is demonstrated further in detail using an Example and a comparative example, it is not limited to a following example. The measuring method of the physical property of the antibacterial composition obtained by the Example and the comparative example is shown below.
Antibacterial test
D. diluted with 1/50 broth. 0.1 ml of aureus (Staphylococcus aureus) bacterial solution (concentration: 10 7 cells / ml) is dropped on a 5 cm × 5 cm film previously sterilized by high-pressure steam, and a Saran wrap film sterilized by high-pressure steam is applied to the film. Adhered. The test piece was transferred to a sterile petri dish and cultured at 37 ° C. for 24 hours. Then, the bacteria on the film were washed with 10 ml of SCDLP medium, diluted 10 times, and spread on a normal agar plate, and the number of bacteria was counted 24 hours later.
[0037]
Example 1
9 mol of dimethyl terephthalate, 1 mol of tri-n-butylhexadecylphosphonium salt of dimethyl ester of 5-sulfoisophthalic acid, 22 mol of ethylene glycol, 200 ppm of zinc acetate as zinc (Zn) with respect to the theoretical amount of copolymerized polyester In addition, the ester exchange reaction was carried out while the methanol produced by heating from 140 to 220 ° C. was distilled out of the system.
After completion of the transesterification reaction, at 250 ° C., 0.12 mol of polyethylene glycol having a molecular weight of 10,000 (Nacalai Co., Ltd.), and 250 ppm of trimethylphosphine as antimony oxide as antimony (Sb) with respect to the theoretical amount of the copolymerized polyester produced. 80 ppm of fenote was added and stirred for 15 minutes, and then 2000 ppm of spherical silica having an average particle size of 0.9 microns was added. A polycondensation reaction was performed at 260 ° C. under vacuum for 60 minutes to obtain a copolyester resin having an intrinsic viscosity of 0.50.
[0038]
The polymer was melt extruded at 250 ° C. using a biaxial extruder and cooled with a cooling roll at 30 ° C. to obtain an unstretched film having a thickness of 180 μm.
This unstretched film was stretched 3.5 times in the machine direction between a pair of rolls heated at 80 ° C. and having different peripheral speeds, and then stretched 3.5 times in the transverse direction at 120 ° C. by a tenter. The film was heat-set at 0 ° C. to obtain a biaxially stretched polyester film having a thickness of 14.5 μm.
[0039]
The above biaxially stretched polyester film and polyethylene film (LIX-2 thickness 40 μm, (Toyobo Co., Ltd.) are laminated with an adhesive (main agent: AD590, curing agent RT86 (Toyo Morton Co., Ltd.)) by a dry laminating method. Thereafter, the antibacterial evaluation results on the polyester surface side of the obtained laminated film are shown in Table 1.
[0040]
(Examples 2 to 8)
An antibacterial laminated film was obtained in the same manner as in Example 1 except that the type and amount of polyethylene glycol in Example 1 were as shown in Table 1, and the antibacterial property was evaluated and obtained in the same manner as in Example 1. The results are shown in Table 1.
[0041]
(Examples 9 to 10)
An antibacterial laminated film was obtained in the same manner as in Example 1 except that the type and amount of the phosphonium salt shown in Table 1 were used in Example 1, and the antibacterial property was evaluated and obtained in the same manner as in Example 1. The results are shown in Table 1.
[0042]
(Comparative Examples 1-3)
In Examples 1, 9, and 10, the antibacterial laminated film was obtained in exactly the same manner as in Examples 1, 9, and 10 except that polyethylene glycol was not added, and antibacterial evaluation was performed in the same manner as in Example 1. Are shown in Table 1.
[0043]
(Example 11)
(A) Adjustment of base film
Polystyrene terephthalate in which calcium carbonate fine particles having an average particle size of 0.5 μm were dispersed at a concentration of 4000 ppm was melt extruded at 290 ° C. and cooled with a cooling roll at 30 ° C. to obtain an unstretched film having a thickness of about 180 μm. .
(B) Preparation of antibacterial composition coating solution
An antibacterial composition was obtained in the same manner as in Example 1 except that a mixture of 5 mol of dimethyl terephthalate and 4 mol of dimethyl phthalate was used instead of 9 mol of dimethyl terephthalate in Example 4. This antibacterial composition was dissolved in a commercially available special grade reagent methyl ethyl ketone to prepare a 3% by weight solution.
(C) Adjustment of laminated film
After passing the antibacterial composition coating solution obtained in (B) above through a filter having a pore size of 1.0 μm, it was applied to the surface of the unstretched polyester film obtained in (A) above by the bar coater method and dried with hot air at 70 ° C. did. Next, the film was stretched 3.5 times in the transverse direction at 130 ° C. by a tenter and then heat-set at 200 to 210 ° C. to obtain a biaxially stretched laminated polyester film having a thickness of 14.5 μm.
A polyethylene film (LIX-2 thickness 40 μm, (Toyobo Co., Ltd.) is applied to the surface opposite to the antibacterial composition coated surface of the biaxially stretched laminated polyester film by an adhesive (main agent: AD590, cured). The film was laminated with the agent RT86 (Toyo Morton Co., Ltd.) The final coating agent (antibacterial composition) attached to the film was about 0.2 g / m. ² Met. Table 2 shows the antibacterial evaluation results on the surface of the obtained laminated film on which the antibacterial composition was applied.
[0044]
(Example 12)
The antibacterial composition coating solution obtained in Example 11 was applied to a 75 μm-thick biaxially stretched transparent PET film (Toyobo Co., Ltd.) so as to have a solid content of 0.3 μm. After laminating in the same manner as in Example 11, antibacterial evaluation results on the antibacterial composition application surface side are shown in Table 2.
[0045]
(Example 13)
The antibacterial composition coating solution obtained in Example 11 was applied to a white PET synthetic paper crisper (Toyobo Co., Ltd.) having a thickness of 75 μm so as to have a solid content of 0.3 μm. Table 2 shows the antibacterial evaluation results on the side coated with the antibacterial composition after lamination in the same manner as in Example 11.
[0046]
(Examples 14 to 16)
An antibacterial laminated film was obtained in the same manner as in Example 11 except that the types and amounts of phosphonium salts in Example 11 were as shown in Table 2, and the evaluation results on the antibacterial composition application surface side were shown in Table 2. It was.
[0047]
(Comparative Examples 4-6)
A copolymer was synthesized in exactly the same manner as in Example 1 except that polyethylene glycol was not added in Example 11, and the same substrate as in Examples 11, 12, and 13 was coated, and then laminated in the same manner. Table 2 shows the evaluation results of the laminated film on the side coated with the antibacterial composition.
[0048]
( Reference example 1 )
1 weight per 100 parts by weight of terephthalic acid // ethylene glycol / polyethylene glycol (molecular weight 1000) (100 // 95/5 molar ratio) copolymer in which calcium carbonate fine particles having an average particle size of 0.5 μm are dispersed at a concentration of 4000 ppm Part of silver / zirconium phosphate antibacterial filler, Novalon (Toa Gosei Co., Ltd.) was added and mixed, then melt extruded at 280 ° C., cooled with a cooling roll at 30 ° C., and an unstretched film having a thickness of about 180 μm Got. This unstretched film was stretched 3.5 times in the machine direction between a pair of rolls heated at 85 ° C. and having different peripheral speeds, and then stretched 3.5 times in the transverse direction at 130 ° C. by a tenter. The film was heat-set at 210 ° C. to obtain a biaxially stretched polyester film having a thickness of 14.5 μm. After laminating the obtained film and polyethylene film (LIX-2 thickness 40 μm (Toyobo Co., Ltd.)) with an adhesive (main agent: AD590, curing agent: RT86 (Toyo Morton Co., Ltd.), Table 3 shows the antibacterial evaluation results on the polyester surface side of the obtained laminated film.
[0049]
( Reference Examples 2-3 )
Reference example 1 Except that the inorganic antibacterial agent shown in Table 3 was used instead of silver / zirconium phosphate antibacterial filler (Toa Gosei Co., Ltd.) Reference example 1 To obtain an antibacterial laminated film, Reference example 1 Table 3 shows the antibacterial evaluation results on the polyester surface side of the laminated film obtained in the same manner as above. In addition, the antibacterial evaluation of the P-25 containing system was performed while illuminating a black light at a distance of 40 cm.
[0050]
(Comparative Examples 7-9)
Reference example 1 Except that polyethylene terephthalate PET was used instead of copolymer in Reference examples 1, 2, 3 To obtain an antibacterial laminated film in exactly the same way as Reference example 1 Table 3 shows the antibacterial evaluation results on the polyester surface side of the laminated film obtained in the same manner as above.
[0051]
( Reference example 4 )
(A) Preparation of sulfonic acid group-containing polyester and aqueous dispersion
First, the sulfonic acid group-containing polyester was prepared by the following method. Using 95 mol% of dimethyl terephthalate and 5 mol% of sodium 5-sulfoisophthalate as the dicarboxylic acid component, transesterification and polycondensation were performed by conventional methods.
The glass transition temperature of the obtained sulfonic acid group-containing polyester (PES-SO3Na) was 69 ° C. 300 parts of this sulfonic acid group-containing polyester and 150 parts of n-butyl cellosolve are heated and stirred to make a viscous solution, and further 550 parts of water are gradually added while stirring to obtain uniform light white water having a solid content of 30%. A dispersion was obtained. This dispersion was further added to an equal volume mixture of water and isopropanol to prepare a sulfonic acid-containing polyester aqueous dispersion having a solid content of 5%.
(B) Adjustment of mixed coating solution
A silver / zirconium phosphate antibacterial filler, 0.1 part by weight of Novalon (Toagosei Co., Ltd.) was added to, mixed and finely dispersed in 100 parts by weight of the above-mentioned (A) sulfonic acid group-containing polyester aqueous dispersion to prepare a coating solution.
(C) Film adjustment
A substrate film was prepared in the same manner as in Example 11 except that the coating solution was changed, and after the coating solution was applied, lamination was performed in the same manner to produce a laminated film. The final coating coverage of the film is 0.5 g / m ² Met. Table 4 shows the antibacterial evaluation results of the coating surface of the obtained film.
[0052]
( Reference Examples 5-6 )
Reference example 4 Except that the inorganic antibacterial agent shown in Table 4 was used instead of silver / zirconium phosphate antibacterial filler (Toa Gosei Co., Ltd.) Reference example 4 To obtain an antibacterial laminated film, Reference example 1 Table 4 shows the antibacterial evaluation results on the coating surface of the film in the same manner as above.
In addition, the antibacterial evaluation of the P-25 containing system was performed while illuminating a black light at a distance of 40 cm.
[0053]
( Reference Example 7 )
Silver / zirconium phosphate antibacterial filler (Toa) containing 95 parts by weight of polyethylene terephthalate (PET, molecular weight 20000) and 5 parts by weight of polyethylene glycol (molecular weight 20000) in which calcium carbonate fine particles having an average particle size of 0.5 μm are dispersed at a concentration of 4000 ppm. After adding 2 parts by weight of Synthetic Co., Ltd., it was melt extruded at 280 ° C. and cooled with a cooling roll at 30 ° C. to obtain an unstretched film having a thickness of about 180 μm. This unstretched film was stretched 3.5 times in the longitudinal direction between a pair of rolls heated at 85 ° C. and having different peripheral speeds, and then stretched 3.5 times in the transverse direction at 130 ° C. by a tenter. The film was heat-set at 0 ° C. to obtain a biaxially stretched polyester film having a thickness of 14.5 μm. The obtained film and polyethylene film (LIX-2 thickness 40 μm (Toyobo Co., Ltd.)) were laminated by an adhesive (main agent: AD590, curing agent: RT86 (Toyo Morton Co., Ltd.) by a dry laminating method, Table 5 shows antibacterial evaluation results on the polyester surface side of the obtained laminated film.
[0054]
( Reference Examples 8-9 )
Reference Example 7 Except that the inorganic antibacterial agent shown in Table 3 was used instead of silver / zirconium phosphate antibacterial filler (Toa Gosei Co., Ltd.) Reference example 1 To obtain an antibacterial laminated film, Reference example 1 Table 5 shows the results of antibacterial evaluation of the coated surface of the film in the same manner as above.
In addition, the antibacterial evaluation of the P-25 containing system was performed while illuminating a black light at a distance of 40 cm.
[0055]
(Comparative Examples 10-12)
Reference examples 7, 8, 9 Except that polyethylene terephthalate PET was used instead of copolymer in Reference examples 7, 8, 9 The antibacterial laminated film was prepared and the antibacterial evaluation was performed in the same manner as above, and the results shown in Table 5 were obtained.
[0056]
( Reference Examples 10-15 )
Reference examples 7, 8, 9 In Table 1, except that polyglycerin 3 types shown in Table 1, polyglycerin # 310, polyglycerin # 500, polyglycerin # 750 (Sakamoto Pharmaceutical Co., Ltd.), and polyvinyl alcohol (PVA) were used instead of polyethylene glycol. Reference examples 7, 8, 9 The antibacterial laminated film was prepared and the antibacterial evaluation was performed in exactly the same manner as above, and the results in Table 6 were obtained.
[0057]
(Example 17 )
Example 1 16 and Reference Examples 1-15 After sealing the antibacterial laminated film shown in (3) with the polyester side containing the antibacterial composition on the outer side of the bag by the impulse seal method, the bag is filled with methylene blue test solution and the remaining one is sealed by the impulse seal method. A four-side sealed bag filled with the test solution was left in a constant temperature bath at 45 ° C. ± 2 ° C. for 24 hours, and then the presence or absence of liquid leakage was examined.
As described above, the antibacterial property can be imparted to an article that does not originally have antibacterial properties by coating and packaging using the packaging material and the packaging bag made of the antibacterial laminate according to the present invention, and the advanced level according to the present invention. Various articles having antibacterial activity can be provided. Therefore, in a field where sterilization is required, an article having added value such as maintaining its effect can be manufactured.
[0058]
【The invention's effect】
By using the packaging material and the packaging bag comprising the antibacterial laminate of the present invention, it is possible to impart a high level of antibacterial properties to an article having no antibacterial properties in a retrofit manner, that is, the antibacterial characteristic of the present invention. The package which has an agent on the surface can be provided. In addition, by adding a photocatalytic function, it is possible to obtain a packaging material, a packaging bag, and a packaging body that exhibit stronger antibacterial properties by applying near-ultraviolet light in an arbitrary process.
[0059]
[Table 1]

[0060]
[Table 2]

[0061]
[Table 3]

[0062]
[Table 4]

[0063]
[Table 5]

Claims (4)

A polyester layer and a polyolefin layer, and a laminate of at least two layers, and a laminate of at least two layers, wherein the outermost layer on at least one side of the laminate is mainly An organic antibacterial agent selected from any of tri-n-butylhexadecylphosphonium salt of sulfoisophthalic acid, tri-n-butyltetradecylphosphonium salt of sulfoisophthalic acid and tri-n-butyldodecylphosphonium salt of sulfoisophthalic acid; An antibacterial laminated packaging material comprising a polyester containing an antibacterial composition obtained by copolymerizing a hydrophilic substance containing at least one of hydroxyl group / sulfonic acid group or alkali metal salt / polyether chain thereof. 2. The antibacterial laminated packaging material, wherein the hydrophilic substance according to claim 1 is a polymer compound containing at least one of a hydroxyl group / sulfonic acid group or an alkali metal salt / polyether chain thereof. The antibacterial laminated packaging material having antibacterial properties according to claim 1 or 2 , wherein the outermost layer on one side of the laminate is a polyolefin layer. The package which consists of an antibacterial laminated packaging material in any one of Claims 1-3 .