JP4239290B2 - Transparent laminated film for metal can lid bonding coating and metal can lid - Google Patents
Transparent laminated film for metal can lid bonding coating and metal can lid Download PDFInfo
- Publication number
- JP4239290B2 JP4239290B2 JP11489199A JP11489199A JP4239290B2 JP 4239290 B2 JP4239290 B2 JP 4239290B2 JP 11489199 A JP11489199 A JP 11489199A JP 11489199 A JP11489199 A JP 11489199A JP 4239290 B2 JP4239290 B2 JP 4239290B2
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- Prior art keywords
- metal
- lid
- film
- base film
- resin
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- 230000001699 photocatalysis Effects 0.000 claims description 36
- 239000000203 mixture Substances 0.000 claims description 33
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 28
- 239000010410 layer Substances 0.000 claims description 26
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- 230000007062 hydrolysis Effects 0.000 claims description 17
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- 125000004432 carbon atom Chemical group C* 0.000 claims description 13
- 239000002245 particle Substances 0.000 claims description 11
- 229920006267 polyester film Polymers 0.000 claims description 11
- 230000007704 transition Effects 0.000 claims description 11
- 238000002844 melting Methods 0.000 claims description 9
- 230000008018 melting Effects 0.000 claims description 9
- 239000004925 Acrylic resin Substances 0.000 claims description 8
- 229920000178 Acrylic resin Polymers 0.000 claims description 8
- 229920001225 polyester resin Polymers 0.000 claims description 7
- 239000004645 polyester resin Substances 0.000 claims description 7
- 230000001954 sterilising effect Effects 0.000 claims description 7
- 238000004659 sterilization and disinfection Methods 0.000 claims description 7
- 125000003545 alkoxy group Chemical group 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 6
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- 238000010030 laminating Methods 0.000 claims description 2
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- RXOHFPCZGPKIRD-UHFFFAOYSA-N naphthalene-2,6-dicarboxylic acid Chemical compound C1=C(C(O)=O)C=CC2=CC(C(=O)O)=CC=C21 RXOHFPCZGPKIRD-UHFFFAOYSA-N 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
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- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
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- 238000003756 stirring Methods 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 2
- 229920005992 thermoplastic resin Polymers 0.000 description 2
- 239000005029 tin-free steel Substances 0.000 description 2
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 description 2
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- PXGZQGDTEZPERC-UHFFFAOYSA-N 1,4-cyclohexanedicarboxylic acid Chemical compound OC(=O)C1CCC(C(O)=O)CC1 PXGZQGDTEZPERC-UHFFFAOYSA-N 0.000 description 1
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- 239000005995 Aluminium silicate Substances 0.000 description 1
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
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- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
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- 241001122767 Theaceae Species 0.000 description 1
- ORLQHILJRHBSAY-UHFFFAOYSA-N [1-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1(CO)CCCCC1 ORLQHILJRHBSAY-UHFFFAOYSA-N 0.000 description 1
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- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
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Description
【０００１】
【発明の属する技術分野】
本発明は、金属缶蓋貼合せ被覆用透明積層フィルムに関し、さらに詳しくは金属缶の蓋外面に貼合せてレトルト処理した際、白斑が発生せず、耐腐食性に優れる金属缶蓋貼合せ被覆用透明積層フィルム及び金属缶蓋に関する。
【０００２】
【従来の技術】
コーヒー、紅茶などの各種飲料および食品用の金属缶は、通常、レトルト殺菌処理を行うが、この処理時に缶に負圧がかかる。この負圧が缶変形をもたらすことがあるため、金属缶は厚さの厚いティンフリースチールなどで作られることが多い。かかる金属缶は、通常、製造の容易さの点から、缶胴および天地蓋からなるスリーピース缶、または缶胴と蓋よりなるツーピース缶として形成される。
【０００３】
一方、金属缶の腐食を防止する為に施す塗装の代替として熱可塑性樹脂フィルムを缶表面に貼合せ被覆することが行われている。この方法は、塗布・乾燥工程を省略し排気・排水などによる環境汚染を防止するために極めて好ましいものである。熱可塑性樹脂フィルムとしては、ポリエステルフィルム、特にポリエチレンテレフタレートフィルムがバランスのとれた特性を有するとして注目され、これをベースとしたいくつかの提案がされている。
【０００４】
缶材、特に缶蓋などでは、意匠的見地から金属の外観をそのまま生かした材料が求められることが多くあるが、この場合は金属板に透明ポリエステルフィルムを融着被覆させて用いることによりその目的を達成することができる。
【０００５】
しかし、かかる従来のポリエステルフィルムを融着被覆させた、スリーピース缶の天地蓋では、レトルト殺菌処理（通常１２０〜１３０℃のスチーム処理）時に、該缶の地蓋に水滴が付着し、融着被覆の際溶融して非晶状態となったフィルムまたはその表面層の水滴付着部分が結晶化して、白斑が発生する問題がある。この現象は、レトルトブラッシングと呼ばれ、商品の美観を害するため、このような現象の起こらないフィルム、中でも天地蓋外面被覆用の透明フィルムの開発が強く求められている。
【０００６】
【発明が解決しようとする課題】
本発明の目的は、金属缶の蓋外面に貼合せてレトルト処理した際、水滴による白斑の発生しない、すなわちレトルトブラッシングが起こらない、さらに耐腐食性に優れる金属缶蓋貼合せ被覆用透明積層フィルム及び金属缶蓋を提供することである。
【０００７】
【課題を解決するための手段】
本発明は、二軸配向を有するポリエステルフィルムから成る基材フィルムと、該基材フィルムの片面に、下記式（１）で表わされる加水分解性ケイ素化合物の加水分解縮合物を主成分とする中間層、及び平均粒径０．００１〜０．５μｍのチタン酸化物および下記式（１）で表わされる加水分解性ケイ素化合物の加水分解縮合物から構成される組成物からなる光触媒機能層が、この順で積層され、レトルト殺菌処理される金属缶蓋に、前記基材フィルムの前記光触媒機能層と反対側の表面が貼り合わされることを特徴とする金属缶蓋貼合せ被覆用透明積層フィルムである。
【化３】
【０００８】
本発明はまた、金属缶の蓋に形成された金属板に貼り合わされた、二軸配向を有するポリエステルフィルムから成る基材フィルムと、該基材フィルムの片面に、下記式（１）で表わされる加水分解性ケイ素化合物の加水分解縮合物を主成分とする中間層、及び平均粒径０．００１〜０．５μｍのチタン酸化物および下記式（１）で表わされる加水分解性ケイ素化合物の加水分解縮合物から構成される組成物からなる光触媒機能層が、この順で積層され、レトルト殺菌処理されることを特徴とする金属缶蓋である。
【化４】
【０００９】
以下、本発明を詳細に説明する。
【００１０】
［光触媒機能層］
本発明の積層フィルムは、光触媒機能層が基材フィルムの片面に、特に金属缶蓋と貼合せる面と反対側の最表面に積層されていることが最も重要な特徴である。
【００１１】
光触媒機能層の主成分であるチタン酸化物は、それ自体が光半導体であり、そのバンドギャップ以上のエネルギーを持つ光を照射すると伝導帯に電子が励起され、価電子帯には正孔（ホール）が生じる。この励起電子および正孔によって生じる電子移動に基づく酸化還元作用により近傍の物質を分解するという光触媒活性が知られている。また特許２７５６４７４号公報に記載されているように、励起されたチタン酸化物表面に吸着結合した水に由来するといわれる水酸基が多数生じることによる、いわゆる「超親水化」という現象が知られている。これらの効果は、０．１ｍＷ／ｃｍ2という通常室内の蛍光灯から得られる程度の光エネルギーによって発現し、この効果は一旦発現すると遮光状態でも数日間持続させることができる。
【００１２】
本発明者は、前述の技術的課題を解決すべく研究した結果、上記光触媒活性を有する光触媒機能層を積層したフィルムを金属缶の蓋に貼合せることにより、蓋に付着した水分が水滴を形成することなく缶蓋全面に濡れ広がり、しかもその状態が金属缶のレトルト処理の間も持続される結果、フィルムに結晶化による斑の発生を抑制する効果を見出した。さらに、本発明者は、光触媒機能層のもう１つの構成成分である加水分解性ケイ素化合物の加水分解縮合物は、レトルト処理時に付着する水分が基材フィルムへ浸透するのを抑制する結果、フィルム全体の結晶化も起こりにくくなる効果を見出した。従って、上記２つの効果により、レトルトブラッシングの発生は完全に防止でき、さらに蓋を構成する金属の腐食を防止する効果も見出した。
【００１３】
以下、本発明の積層フィルムにおける光触媒機能層について詳細に説明する。本発明の光触媒機能層は平均粒径０．００１〜０．５μｍのチタン酸化物および式（１）で表わされる加水分解性ケイ素化合物の加水分解縮合物から構成される組成物からなることを特徴とする。
【００１４】
【化３】
（式（１）中、ｎは０〜８の整数、Ｘ1、Ｘ2、Ｘ3、Ｘ4は、それぞれハロゲン原子、水酸基、炭素数１〜８のアルコキシ基または炭素数１〜８の炭化水素基を表わす。ただし、Ｘ1、Ｘ2、Ｘ3、Ｘ4は互いに同一あるいは異なっていてもよい。）
【００１６】
本発明における光触媒機能層を構成するチタン酸化物とは、特定エネルギーを持つ光の照射で有機物の酸化還元に対して触媒作用を示すものであり、純粋なチタン酸化物の他、含水酸化チタン、水和酸化チタン、メタチタン酸、オルトチタン酸、水酸化チタンと呼ばれているものを含む。二酸化チタンまたはこれより低次酸化状態にあるものが特に好ましく用いられる。二酸化チタンの結晶型はアナターゼ型、ルチル型、フルッカイト型のいずれでもよくまたこれらの混合体でも良いが、特にアナターゼ型が好ましい。
【００１７】
これらのチタン酸化物は微粉末状であり、その粒径は光触媒活性の強さから見て０．００１〜０．５μｍである必要がある。この微粉末は乾燥状態の粉末として用いても良いが、加水分解性ケイ素化合物の加水分解縮合物と均一分散させるために予め分散体としておくことが望ましい。本発明の組成物中においてチタン酸化物が良好に分散されているか否かは塗膜を形成したときの光触媒機能に大きく影響してくる。
【００１８】
チタン酸化物は種々の公知の方法で製造される。例えばＡ．硫酸チタニル、塩化チタン、有機チタン化合物などのチタン化合物を必要に応じて核形成種の存在下に加水分解する方法、Ｂ．硫酸チタニル、塩化チタン、有機チタン化合物などのチタン化合物に、必要に応じて核成形種の存在下にアルカリを添加し、中和する方法、Ｃ．塩化チタン、有機チタン化合物などを気相酸化する方法、Ｄ．上記Ａ、Ｂの方法で得られたチタン酸化物を焼成する方法などが挙げられる。特に、前記Ａ、Ｂの方法で得られたチタン酸化物は光触媒機能が高いため好ましい。光触媒機能をさらに向上させるためにチタン酸化物表面に白金、金、銀、銅、パラジウム、ロジウム、ルテニウムなどの金属、酸化ルテニウム、酸化ニッケル等の金属酸化物を被覆しても良い。
【００１９】
これらのチタン酸化物は水などの溶媒に高度に分散させて使用される。超微粒子となっているチタン酸化物を二次凝集させずに水などの溶媒と均一分散させておくためには、溶液を酸性またはアルカリ性として保存しておくことが好ましい。酸性とする場合、ｐＨ０．５〜４、特に１〜３．５とするのが好ましい。分散媒体としては水の他、水とアルコールの混合物を用いても良い。
【００２０】
本発明で用いられる前記式（１）で表わされる加水分解性ケイ素化合物としては、アルキルシリケートまたはハロゲン化ケイ素が挙げられ、そしてこれらの部分加水分解物も含まれる。アルキルシリケートとしてはメチル、エチル、イソプロピルシリケートなどが好ましく用いられる。これらのシリケートはいずれも単独でもしくは部分加水分解によって生成するオリゴマーの形で用いられ、オリゴマーとしては一般式ＳｉnＯn-1（ＯＲ）2n+2（ただしｎは２〜６，Ｒは炭素数１〜４のアルキル基）で表わされるアルキルシリケートオリゴマーが特に好ましい。これらのオリゴマーは混合物でも用いられる。
【００２１】
部分加水分解するときの触媒としては酸、アルカリのいずれもが使用できる。チタン酸化物分散体が酸性のときは酸で部分加水分解した加水分解性ケイ素化合物が好ましい。部分加水分解液の分散溶媒は水または炭素数が１〜４のアルコールが用いられる。酢酸エチルなどのエステル類は、組成物液を不安定にするので好ましくない。本発明において用いられる加水分解性ケイ素化合物および／またはその部分加水分解物は、チタン酸化物を結合させる目的で用いられるので以下においてシリカバインダーと呼ぶ。
【００２２】
チタン酸化物とシリカバインダーとの混合は、適宜に出来るが、一例を示すと酸性下にある所定量の二酸化チタン水性分散液を１０〜５０℃の液温に保持し、これに秤量したシリカバインダーを一定時間かけて滴下添加する。滴下終了後、１〜５時間撹拌下に反応させて組成物液を調製する。シリカバインダー添加の際に加水分解触媒を同時に加えても良いし、二酸化チタン分散液中に存在する酸分を利用して加水分解を進めても良い。分散媒体としてアルコール系の媒体を用いる場合は、二酸化チタンの水／アルコール混合媒体分散液と、アルコール媒体中でシリカバインダーを５０〜１５００％加水分解した液とを撹拌下に混合して本組成物を得ることもできる。上記操作により、シリカバインダーは加水分解縮合物を形成する。
【００２３】
本発明において加水分解率とは、シリカバインダー１モルに対し水２モルの割合で使用した場合を加水分解率１００％として水の使用量によって算出したものである。一般式ＳｉnＯn-1（ＯＲ）2n+2の形の部分加水分解物を用いた場合は、この縮合体１モルに対し水ｎ＋１モルの割合で使用した場合を加水分解率１００％として算出する。
【００２４】
本発明の組成物中のチタンとシリカバインダーとの割合は、各々二酸化チタンと二酸化ケイ素に換算した重量割合（ＳｉＯ2／（ＴｉＯ2＋ＳｉＯ2））で４〜７０％とすることが好ましい。シリカバインダーの割合が７０％を超えるとチタン酸化物の光触媒機能が小さくなってしまい実用性が乏しくなる。これはチタン酸化物粒子表面を覆うシリカバインダーの割合が大きくなり、チタン酸化物と酸化分解されるべき物質との接触を妨害することになるからと思われる。一方、シリカバインダーの混合割合が４％以下であると基材フィルムおよびチタン酸化物同士の接着強度が充分でなく指触や振動で容易に脱落してしまい、塗膜として工業的に使用しにくいものになる。シリカバインダーのさらに好ましい割合は１０〜５０％である。
【００２５】
本発明の組成物中の固形分濃度は重量で３０％以下であると好ましい。ここで固形分とは全組成物中におけるチタン酸化物とシリカバインダーの合計量を言い、チタン酸化物は二酸化チタンに、シリカバインダーは組成物中のケイ素（Ｓｉ）分をＳｉＯ2に換算した値を用いる。その他の成分は水分および／または有機溶媒が主体であり、組成物を基材面上へ塗布後、乾燥により実質的に除去されるべきものである。好ましい固形分濃度は５〜２０％であり、５％以下になると基材との接着性は強固になるが１回の塗布では塗膜の厚さが不十分、つまりチタン酸化物量が不十分で光触媒機能を充分発揮できる塗膜を形成できない。ただし、光触媒機能を犠牲にしても強固な薄い塗膜を必要とする場合、あるいは手間をかけて２回以上重ね塗りして厚くかつ強固な塗膜を必要とする場合など特殊な用途には用いることができる。
【００２６】
一方、固形分濃度が３０％を超えると組成物の粘度が高くなり、均一で透明性に優れた塗膜が得られにくく、また加水分解、縮合反応が進行しやすくなるため組成物の保存安定性が著しく低下し、僅かな日数でゲル化が生じ易くなる場合がある。
【００２７】
本発明の組成物には少量のチタンアルコキシド、四塩化チタンを加えても良い。またチタン、あるいはシランカップリング剤などを加えても良い。さらに、組成物の安定性確保および濡れ特性改善のために各種界面活性剤を加えても良い。また、アルコキシ基を２個以上含むアルキシランもしくはハイドロシランを少量添加しても良いがこれらのチタン化合物、シラン化合物は固形分算出の際のシリカ換算に加えるものとする。
【００２８】
かかる組成物からなる塗膜を設ける方法としては、かかる組成物を含むコーティング剤を基材上または基材上に設けた層上に塗布し、乾燥、場合によって低温焼成されて塗膜化される方法が好ましい。塗布方法は塗布すべき基材の形状によってスピンコーティング、スプレーコーティング、バーコーティング、ロールコーティング、ダイコーティング、ディップコーティングなどが適宜に使用される。塗膜の厚さは０．００１〜３μｍ、特に０．０１〜２μｍが適当である。チタン酸化物の光触媒活性は、表面に露光し酸化分解されるべき化合物と接触可能なチタン酸化物の量に関係するので本来は塗膜の厚さは理論的には関係ないが、現実には塗膜中には微小な孔が存在し、ある程度の厚さを持つことで適度な表面積を有することが可能となり十分な光触媒活性を得ることができるので前記程度の厚さにすることが好ましい。上記厚さ範囲であると塗膜の透明性確保にも有利であり、基材の持つ透明性や色などを損なうことなく、その表面に光活性を持つ被膜を形成することが出来る。上記の方法で設けられた塗膜は１００〜１８０℃の乾燥によってより強固な被膜を形成することができる。
【００２９】
［基材フィルム］
本発明の積層フィルムの基材フィルムとしては、ポリエステルフィルムが好ましい。
本発明におけるポリエステルとは、芳香族二塩基酸またはそのエステル形成性誘導体とジオールまたはそのエステル形成性誘導体とから製造される結晶性の線状飽和ポリエステルであり、具体的には、エチレンテレフタレート、プロピレンテレフタレート、ブチレンテレフタレート、エチレン−２，６−ナフタレート、プロピレン−２，６−ナフタレート、１，４−シクロヘキシレンジメチレンテレフタレートなどを主たる繰返し単位とするものを好ましいものとして例示することができ、エチレンテレフタレートを主たる繰返し単位とするものが中でも好ましいものとして挙げることができる。
【００３０】
また、本発明におけるポリエステルは、繰返し単位の一部が他成分に置換された共重合体や、他のポリエステルあるいは他の種類の樹脂との混合体であっても良い。
【００３１】
共重合体の場合の共重合成分は、酸成分でもアルコール成分でもよく、具体的には、酸成分の場合は、イソフタル酸、フタル酸、ナフタレン−２，６−ジカルボン酸の如き芳香族ジカルボン酸、アジピン酸、アゼライン酸、セバシン酸、デカンジカルボン酸の如き脂肪族ジカルボン酸、シクロヘキサン−１，４−ジカルボン酸の如き脂環族ジカルボン酸等を例示でき、また、アルコール成分としては、ブタンジオール、ヘキサンジオールの如き脂肪族ジオール、シクロヘキサンジメタノールの如き脂環族ジオール、複数のジオールがエーテル結合を介して縮合したポリアルキレングリコール類（ジエチレングリコール等はこの中の特殊な例である）等を例示できる。これらの共重合成分は、単独での使用でも二種以上の併用でもよい。
【００３２】
これらの共重合成分の割合、あるいは他のポリエステルまたは他の種類の樹脂との混合体の場合の配合割合は、後述する二次転移温度、融解温度を満足するようにすることが好ましい。
【００３３】
本発明におけるポリエステルの製法は、特に限定されないが、酸成分およびアルコール成分の主成分および共重合成分をエステル化反応させ、次いで得られる反応生成物を重縮合反応させてポリエステルとする方法、あるいは酸成分のジメチルエステル等とアルコール成分の主成分および共重合成分をエステル交換反応させ、次いで得られる反応生成物を重縮合反応させてポリエステルとする方法、等が好ましく用いられる。本発明におけるポリエステル中には、必要に応じ、他の添加剤、たとえば、酸化防止剤、熱安定剤、紫外線吸収剤、帯電防止剤なども含有させることができる。
【００３４】
本発明における積層フィルムの基材フィルムが上記ポリエステルを主成分とする場合、そのポリエステル中には表面粗さを制御し滑り性や耐スクラッチ性を付与するために滑剤、例えば炭酸カルシウム、カオリン、シリカ等の如き無機微粒子、触媒残渣の析出微粒子、および／またはシリコーン、ポリスチレン架橋体の如き有機微粒子等を含有させることが好ましく、その粒径は４μｍ以下であることが粗大粒子によるピンホールやフィルム製膜時の破断等を防止するために好ましい。特に、平均粒径１．５μｍ以下の真球状シリカが好適である。
【００３５】
本発明における積層フィルムの基材フィルムとして、二次転移温度が４０℃以上、融解温度が２７０℃以下のポリエステル組成物からなるものが特に好ましい。二次転移温度が４０℃未満の場合、水分がフィルムを透過しやすくなり、金属板に錆が発生する恐れがあり、また、フィルム製膜時に粘着が発生し取扱いが困難となる可能性がある。二次転移温度は、通常４５〜１２０℃が適当である。
【００３６】
融解温度が２７０℃を超えると、フィルムを金属板に融着積層させる時の接着性が不足する恐れがある。金属板への接着処理の容易さの点から、融解温度は２４０〜２６０℃であることが好ましい。
【００３７】
本発明におけるポリエステルフィルムは、従来から知られている方法、例えば、上記ポリエステルを乾燥後溶融し、ダイから冷却ドラム上に押出し冷却して未延伸フィルムとし、該未延伸フィルムを二軸方向に延伸し、さらに熱固定することによって製造することができる。この場合の二軸延伸の度合は、面積倍率で９倍以上であることが好ましく、２５℃、ナトリウムＤ線を用いてアッベ屈折計で測定した屈折率から下記式によって計算される面配向係数が０．１以上となるようにすることが好ましい。また、フィルムの厚みは、１２〜５０μｍが好ましい。
ｆ＝［（ｎX＋ｎY）／２］−ｎZ
（ここで、ｆは面配向係数、ｎX、ｎY、ｎZはそれぞれ、フィルムの横、縦、厚さ方向の屈折率（アッベ法）を表わす）
【００３８】
本発明の積層フィルムは、光触媒活性機能層と基材フィルムとの間に接着性向上または光触媒作用による基材の酸化分解防止による長期耐久性向上を目的として、プライマー層または中間層を設けることが好ましい。
【００３９】
プライマー層の成分としては、ポリウレタン樹脂、ポリエステル樹脂、アクリル樹脂、ならびにアクリル系樹脂およびビニル系樹脂変性ポリエステル樹脂から選ばれた少なくとも１種類の樹脂、もしくはシランカップリング剤を主成分とする組成物が挙げられる。かかる組成物を含む塗液を、基材フィルムに塗布、乾燥してプライマー層を形成する。このプライマー層の上に、光触媒機能層もしくは後述の中間層を設ける。なお、層間の接着性向上の方策としては、上記のプライマー層を設ける方法の他に、コロナ放電処理、プラズマ処理、火炎処理などを適用することもできる。
【００４０】
中間層の成分としては、前述の式（１）で表わされる加水分解性ケイ素化合物の加水分解縮合物が挙げられる。中間層を設けることで、光触媒機能層の光触媒作用による基材フィルムもしくはプライマー層の酸化分解を防止することができる。
【００４１】
さらに、本発明の積層フィルムには、本発明の効果を阻害しない限りにおいて、本発明の光触媒機能層の他に、ガスバリア層、光線反射層、導電層、磁気などの記録層などを設けたり、あるいは着色や印刷を施してもよい。
【００４２】
本発明の積層フィルムは、スリーピース缶の天地蓋やツーピース缶の蓋を成形する金属板に貼合せて使用されるが、特に蓋の缶外面を貼合せ被覆する用途に有用である。
【００４３】
【実施例】
以下、実施例を掲げて本発明をさらに詳細に説明する。なお、例中の「部」は重量部」を意味する。また、例中に記載した諸物性、特性は以下の方法で測定、評価した。
【００４４】
（１）固有粘度
ｏ−クロロフェノール中、３５℃にて測定した。
【００４５】
（２）融解温度、二次転移温度
ＤｕＰｏｎｔ Ｉｎｓｔｒｕｍｅｎｔ ９１０ ＤＳＣを用い、該フィルムを２０℃／分の速度で昇温しながら測定し、融解ピークから融解温度を求めた。また、該フィルムを２０℃／分の速度で昇温した後２９０℃で３分間保持し、急冷後再度２０℃／分の速度で昇温しながら測定し、ガラス転移点から二次転移温度を求めた。
【００４６】
（３）レトルトブラッシング評価
積層フィルムを、２００℃に加熱したティンフリースチール（厚み２５０μｍ）に光触媒機能層を設けた面と反対側の面で貼合せ、水冷して得られたフィルム積層金属板について、１３０℃にて３０分間のレトルト処理を行い、外観変化について下記の基準で評価した。
○：外観変化なし
△：外観にかすかに曇りあり
×：白斑（ブラッシング）発生
××：白斑に加え表面にざらつき発生
【００４７】
［実施例１］
固有粘度０．６５、二次転移温度７８℃のポリエチレンテレフタレート（平均粒径１．５μｍ真球状シリカ含有）を２０℃に維持した回転冷却ドラム上に溶融押出して未延伸フィルムを得、次に機械軸方向に３．５倍延伸したのち、横方向に３．９倍延伸し、さらに２００℃で熱処理し、厚み１２μｍの二軸延伸ポリエステルフィルムを得た。
【００４８】
該フィルム上に、コロナ放電処理を施し、その上に加水分解性ケイ素化合物の部分加水分解物としてエチルシリケートを部分加水分解した塗布液（コルコート１０３Ｘ，コルコート株式会社製）を塗布液にして５ｇ／ｍ2の塗布量でコーティングし、１５０℃で１分間乾燥して加水分解縮合物を形成させて中間層を設けた。さらにその上に、平均粒径０．０７〜０．１μｍのアナターゼ型二酸化チタンとエチルシリケートの組成物として、ＴｉＯ2／ＳｉＯ2に換算して５０部／５０部となる割合の組成物を溶媒に溶解し、固形分濃度１０％の溶液とした塗布液（ＳＴ−Ｋ０３、コルコート株式会社製）を塗布液にして５ｇ／ｍ2の塗布量でコーティングし、１５０℃２分間乾燥して加水分解縮合物を形成させて、光触媒機能層を設けた積層フィルムを得た。得られた積層フィルムの特性を表１に示す。
【００４９】
［実施例２］
二軸延伸ポリエステルフィルム製膜の際、機械軸方向に３．５倍延伸して得られた一軸延伸フィルムの片面に、アクリル系樹脂水分散体（メチルメタクリレート成分（６５モル％）、エチルアクリレート成分（２８モル％）、２−ヒドロキシエチルメタクリレート成分（２モル％）、およびＮ−メチロールアクリルアミド成分（５モル％）の共重合体、Ｔｇ＝４５℃）を固形分として４０重量部、ポリエステル系樹脂水分散体（高松油脂（株）製、ペスレジン２０００、Ｔｇ＝６８℃）を固形分として５０重量部、ならびに、平均粒径０．０３μｍの架橋アクリル系樹脂微粒子水分散体を固形分として１０重量部、からなる組成物をイオン交換水で希釈して固形分濃度２．７重量％とした水性塗布液を、キスコート法にてフィルム１ｍ2当たり塗布液重量として約３ｇの平均塗布量で塗布し、引続き乾燥しながら横方向に３．９倍延伸した以外は、また、光触媒機能層塗設の際コロナ放電処理を行わなかった以外は、実施例１と同様にして積層フィルムを得た。得られた積層フィルムの特性を表１に示す。
【００５０】
［実施例３］
ポリエステルとして、イソフタル酸を１２モル％共重合したポリエチレンテレフタレート共重合体（固有粘度０．７０、二次転移温度７４℃、平均粒径１．５μｍ真球状シリカ含有）を使用した以外は、実施例１と同様にして積層フィルムを得た。得られた積層フィルムの特性を表１に示す。
【００５１】
［実施例４］
ポリエステルとして、２，６−ナフタレンジカルボン酸を１２モル％共重合したポリエチレンテレフタレート共重合体（固有粘度０．７０、二次転移温度８２℃、平均粒径１．５μｍ真球状シリカ含有）を使用した以外は、実施例１と同様にして積層フィルムを得た。得られた積層フィルムの特性を表１に示す。
【００５２】
［比較例１〜４］
光触媒機能層および中間層の塗設を行わなかった以外は、それぞれ実施例１〜４と同様にして積層フィルムを得た。得られた積層フィルムの特性を表１に示す。
【００５３】
【表１】
【００５４】
【発明の効果】
本発明によれば、レトルト殺菌処理時に白斑（レトルトブラッシング）が発生せず、製品の美観を害することのない金属缶蓋貼合せ被覆用透明積層フィルム及び金属缶蓋を提供することができる。また、本発明の積層フィルムを用いることにより派生する効果として、光触媒効果に起因する抗菌機能の発揮を挙げることができ、その点においても本発明の積層フィルムは金属缶蓋貼合せ被覆用として極めて好ましいものである。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a transparent laminated film for metal can lid bonding coating, and more specifically, when a metal can lid is bonded to the outer surface of the lid and subjected to retort treatment, no white spots occur and the corrosion resistance of the metal can lid bonding coating is excellent. The present invention relates to a transparent laminated film and a metal can lid .
[0002]
[Prior art]
Various beverages such as coffee and tea and metal cans for food are usually subjected to retort sterilization treatment, and negative pressure is applied to the cans during this treatment. Since this negative pressure can cause can deformation, metal cans are often made of thick tin-free steel or the like. Such a metal can is usually formed as a three-piece can including a can body and a top cover or a two-piece can including a can body and a lid from the viewpoint of ease of manufacture.
[0003]
On the other hand, as an alternative to coating applied to prevent corrosion of metal cans, a thermoplastic resin film is laminated and coated on the can surface. This method is extremely preferable in order to omit the coating / drying process and prevent environmental pollution due to exhaust and drainage. As a thermoplastic resin film, a polyester film, particularly a polyethylene terephthalate film, has attracted attention as having balanced characteristics, and several proposals based on this have been made.
[0004]
For can materials, especially can lids, materials that take advantage of the metal appearance as they are are often required from a design standpoint. In this case, the purpose is to use a transparent polyester film fused to the metal plate. Can be achieved.
[0005]
However, in the three-piece can top cover that is fusion-coated with such a conventional polyester film, water droplets adhere to the top of the can during retort sterilization treatment (usually steam treatment at 120 to 130 ° C.). In this case, there is a problem that white spots occur due to crystallization of the film melted into an amorphous state or the water droplet adhering portion of the surface layer thereof. This phenomenon, called retort brushing, is detrimental to the aesthetics of merchandise, so there is a strong demand for the development of a film that does not cause such a phenomenon, especially a transparent film for covering the outer surface of the top cover.
[0006]
[Problems to be solved by the invention]
An object of the present invention is to provide a transparent laminated film for covering a metal can lid that is excellent in corrosion resistance, without causing white spots due to water droplets, i.e., no retort brushing when it is bonded to the outer surface of the lid of a metal can and subjected to retort processing. And providing a metal can lid .
[0007]
[Means for Solving the Problems]
The present invention relates to a base film composed of a polyester film having biaxial orientation, and an intermediate composed mainly of a hydrolysis condensate of a hydrolyzable silicon compound represented by the following formula (1) on one side of the base film. layer, and a flat Hitoshitsubu径0.001~0.5μm titanium oxide and the photocatalytic functional layer from a hydrolysis condensate of a hydrolyzable silicon compound represented comprising the composition consisting of the following formula (1) is, A metal can lid laminated in this order, the surface opposite to the photocatalytic functional layer of the base film is laminated to a metal can lid that is subjected to retort sterilization treatment. is there.
[Chemical 3]
[0008]
The present invention is also represented by the following formula (1) on a base film made of a polyester film having a biaxial orientation bonded to a metal plate formed on a lid of a metal can, and on one side of the base film. hydrolysis of the intermediate layer, and a flat Hitoshitsubu径titanium oxide 0.001~0.5μm and hydrolyzable silicon compound represented by the following formula (1) composed mainly of the hydrolyzed condensate of the hydrolyzable silicon compound A metal can lid characterized in that a photocatalytic functional layer composed of a composition composed of a decomposition condensate is laminated in this order and subjected to a retort sterilization treatment.
[Formula 4]
[0009]
Below, the present invention will be described in detail.
[0010]
[Photocatalytic functional layer]
The most important feature of the laminated film of the present invention is that the photocatalytic functional layer is laminated on one surface of the base film, particularly on the outermost surface opposite to the surface to be bonded to the metal can lid.
[0011]
Titanium oxide, the main component of the photocatalytic functional layer, is an optical semiconductor itself. When irradiated with light having energy higher than its band gap, electrons are excited in the conduction band and holes (holes) are present in the valence band. ) Occurs. A photocatalytic activity is known in which a nearby substance is decomposed by an oxidation-reduction action based on electron transfer caused by excited electrons and holes. Further, as described in Japanese Patent No. 2756474, a so-called “superhydrophilization” phenomenon is known due to the generation of many hydroxyl groups that are said to be derived from water adsorbed and bonded to the surface of the excited titanium oxide. . These effects are manifested by light energy of 0.1 mW / cm 2 which is obtained from a normal indoor fluorescent lamp, and once this effect is manifested, it can be maintained for several days even in a light-shielded state.
[0012]
As a result of researches to solve the above-mentioned technical problems, the present inventor has adhered a film on which a photocatalytic functional layer having photocatalytic activity is laminated to a lid of a metal can, so that moisture attached to the lid forms water droplets. As a result, the entire surface of the can lid was wet and spread, and the state was maintained during the retort treatment of the metal can. As a result, the effect of suppressing the occurrence of spots due to crystallization on the film was found. Furthermore, the present inventors have found that the hydrolysis condensate of the hydrolyzable silicon compound, which is another constituent of the photocatalytic functional layer, suppresses the penetration of moisture adhering during retort treatment into the base film. We found an effect that the entire crystallization hardly occurs. Therefore, the above two effects have completely prevented the occurrence of retort brushing, and also found the effect of preventing corrosion of the metal constituting the lid.
[0013]
Hereinafter, the photocatalytic functional layer in the laminated film of the present invention will be described in detail. The photocatalytic functional layer of the present invention comprises a composition comprising a titanium oxide having an average particle size of 0.001 to 0.5 μm and a hydrolytic condensate of a hydrolyzable silicon compound represented by the formula (1). And
[0014]
[Chemical 3]
(In formula (1), n is an integer of 0 to 8, X 1 , X 2 , X 3 and X 4 are each a halogen atom, a hydroxyl group, an alkoxy group having 1 to 8 carbon atoms, or a carbon atom having 1 to 8 carbon atoms. Represents a hydrogen group, provided that X 1 , X 2 , X 3 and X 4 may be the same or different from each other.
[0016]
The titanium oxide constituting the photocatalytic functional layer in the present invention is a catalyst that exhibits a catalytic action against redox of organic matter by irradiation with light having a specific energy. In addition to pure titanium oxide, hydrous titanium oxide, Including what is called hydrated titanium oxide, metatitanic acid, orthotitanic acid, titanium hydroxide. Titanium dioxide or a material in a lower oxidation state is particularly preferably used. The crystal form of titanium dioxide may be any one of anatase type, rutile type, and flukeite type, or a mixture thereof, but anatase type is particularly preferable.
[0017]
These titanium oxides are in the form of fine powder, and the particle size thereof needs to be 0.001 to 0.5 μm in view of the strength of photocatalytic activity. This fine powder may be used as a dry powder, but it is desirable to prepare a dispersion in advance for uniform dispersion with the hydrolyzable condensate of the hydrolyzable silicon compound. Whether the titanium oxide is well dispersed in the composition of the present invention greatly affects the photocatalytic function when a coating film is formed.
[0018]
Titanium oxide is produced by various known methods. For example, A. A method of hydrolyzing a titanium compound such as titanyl sulfate, titanium chloride, or an organic titanium compound in the presence of a nucleating species, if necessary; A method in which an alkali is added to a titanium compound such as titanyl sulfate, titanium chloride, or an organic titanium compound in the presence of a nuclear forming species as necessary, and neutralized; A method for vapor phase oxidation of titanium chloride, an organic titanium compound, and the like; Examples thereof include a method of firing the titanium oxide obtained by the methods A and B. In particular, the titanium oxide obtained by the methods A and B is preferable because of its high photocatalytic function. In order to further improve the photocatalytic function, the surface of the titanium oxide may be coated with a metal such as platinum, gold, silver, copper, palladium, rhodium or ruthenium, or a metal oxide such as ruthenium oxide or nickel oxide.
[0019]
These titanium oxides are used by being highly dispersed in a solvent such as water. In order to uniformly disperse the titanium oxide as ultrafine particles with a solvent such as water without causing secondary aggregation, the solution is preferably stored as acidic or alkaline. When making it acidic, it is preferable to set it as pH 0.5-4, especially 1-3.5. As a dispersion medium, a mixture of water and alcohol may be used in addition to water.
[0020]
Examples of the hydrolyzable silicon compound represented by the formula (1) used in the present invention include alkyl silicates and silicon halides, and partial hydrolysates thereof are also included. As the alkyl silicate, methyl, ethyl, isopropyl silicate and the like are preferably used. These silicates are used alone or in the form of oligomers formed by partial hydrolysis. The oligomers are represented by the general formula Si n O n-1 (OR) 2n + 2 (where n is 2 to 6 and R is carbon). Alkyl silicate oligomers represented by formula (1-4) are particularly preferred. These oligomers are also used in a mixture.
[0021]
Either acid or alkali can be used as the catalyst for partial hydrolysis. When the titanium oxide dispersion is acidic, a hydrolyzable silicon compound partially hydrolyzed with an acid is preferred. Water or an alcohol having 1 to 4 carbon atoms is used as a dispersion solvent for the partial hydrolysis liquid. Esters such as ethyl acetate are not preferred because they make the composition liquid unstable. The hydrolyzable silicon compound and / or partial hydrolyzate thereof used in the present invention is used for the purpose of binding titanium oxide, and hence is hereinafter referred to as a silica binder.
[0022]
Mixing of the titanium oxide and the silica binder can be performed as appropriate. For example, a predetermined amount of the aqueous titanium dioxide dispersion under acidity is maintained at a liquid temperature of 10 to 50 ° C., and the silica binder weighed in the aqueous solution. Is added dropwise over a period of time. After completion of the dropwise addition, a composition liquid is prepared by reacting with stirring for 1 to 5 hours. When adding a silica binder, a hydrolysis catalyst may be added at the same time, or hydrolysis may be advanced by utilizing an acid component present in the titanium dioxide dispersion. When an alcohol-based medium is used as the dispersion medium, this composition is prepared by mixing, with stirring, a water / alcohol mixed medium dispersion of titanium dioxide and a liquid obtained by hydrolyzing 50 to 1500% of a silica binder in the alcohol medium. You can also get By the above operation, the silica binder forms a hydrolysis condensate.
[0023]
In the present invention, the hydrolysis rate is calculated based on the amount of water used with a hydrolysis rate of 100% when used at a ratio of 2 mol of water to 1 mol of silica binder. When a partial hydrolyzate of the general formula Si n O n-1 (OR) 2n + 2 is used, the case where it is used in a ratio of n + 1 mol of water to 1 mol of this condensate is regarded as a hydrolysis rate of 100%. calculate.
[0024]
The ratio of titanium and silica binder in the composition of the present invention is preferably 4 to 70% by weight ratio (SiO 2 / (TiO 2 + SiO 2 )) converted to titanium dioxide and silicon dioxide, respectively. When the ratio of the silica binder exceeds 70%, the photocatalytic function of the titanium oxide becomes small and the practicality becomes poor. This seems to be because the ratio of the silica binder covering the surface of the titanium oxide particles is increased, and the contact between the titanium oxide and the substance to be oxidatively decomposed is obstructed. On the other hand, if the mixing ratio of the silica binder is 4% or less, the adhesive strength between the base film and the titanium oxide is not sufficient, and it easily falls off by touch or vibration, making it difficult to use industrially as a coating film. Become a thing. A more desirable ratio of the silica binder is 10% to 50%.
[0025]
The solid content concentration in the composition of the present invention is preferably 30% or less by weight. Here, the solid content refers to the total amount of titanium oxide and silica binder in the entire composition. Titanium oxide is converted to titanium dioxide, and the silica binder is a value obtained by converting the silicon (Si) content in the composition into SiO 2. Is used. The other components are mainly water and / or an organic solvent, and should be substantially removed by drying after the composition is applied onto the substrate surface. The preferable solid content concentration is 5 to 20%, and if it is 5% or less, the adhesion to the substrate becomes strong, but the coating thickness is insufficient in one application, that is, the amount of titanium oxide is insufficient. A coating film that can sufficiently exhibit the photocatalytic function cannot be formed. However, it is used for special applications such as when a strong thin coating is required even at the expense of the photocatalytic function, or when a thick and strong coating is required by repeated coating twice or more. be able to.
[0026]
On the other hand, when the solid content concentration exceeds 30%, the viscosity of the composition increases, it is difficult to obtain a uniform and excellent transparency coating film, and the hydrolysis and condensation reaction easily proceeds. In some cases, gelation is likely to occur in a few days.
[0027]
A small amount of titanium alkoxide or titanium tetrachloride may be added to the composition of the present invention. Further, titanium or a silane coupling agent may be added. Furthermore, various surfactants may be added to ensure the stability of the composition and improve the wetting characteristics. A small amount of an alkoxysilane or hydrosilane containing two or more alkoxy groups may be added, but these titanium compounds and silane compounds are added in terms of silica when calculating the solid content.
[0028]
As a method of providing a coating film composed of such a composition, a coating agent containing such a composition is applied onto a substrate or a layer provided on the substrate, dried, and optionally baked at a low temperature to form a coating film. The method is preferred. As the coating method, spin coating, spray coating, bar coating, roll coating, die coating, dip coating and the like are appropriately used depending on the shape of the substrate to be coated. The thickness of the coating film is suitably 0.001 to 3 μm, particularly 0.01 to 2 μm. Since the photocatalytic activity of titanium oxide is related to the amount of titanium oxide that can be exposed to the surface and contacted with the compound to be oxidatively decomposed, the thickness of the coating film is not theoretically related. In the coating film, there are minute pores, and since it has a certain thickness, it can have an appropriate surface area, and sufficient photocatalytic activity can be obtained. When the thickness is within the above range, it is advantageous for ensuring the transparency of the coating film, and a film having photoactivity can be formed on the surface without impairing the transparency or color of the substrate. The coating film provided by the above method can form a stronger coating film by drying at 100 to 180 ° C.
[0029]
[Base film]
A polyester film is preferable as the base film of the laminated film of the present invention.
The polyester in the present invention is a crystalline linear saturated polyester produced from an aromatic dibasic acid or an ester-forming derivative thereof and a diol or an ester-forming derivative thereof, specifically, ethylene terephthalate, propylene Preferred examples include those containing terephthalate, butylene terephthalate, ethylene-2,6-naphthalate, propylene-2,6-naphthalate, 1,4-cyclohexylenedimethylene terephthalate as the main repeating unit, and ethylene terephthalate. Among them, preferred are those having a main repeating unit.
[0030]
In addition, the polyester in the present invention may be a copolymer in which a part of the repeating unit is substituted with another component, or a mixture with other polyester or other types of resins.
[0031]
The copolymer component in the case of a copolymer may be an acid component or an alcohol component. Specifically, in the case of an acid component, an aromatic dicarboxylic acid such as isophthalic acid, phthalic acid, or naphthalene-2,6-dicarboxylic acid. , Aliphatic dicarboxylic acids such as adipic acid, azelaic acid, sebacic acid and decanedicarboxylic acid, alicyclic dicarboxylic acids such as cyclohexane-1,4-dicarboxylic acid, etc., and the alcohol component includes butanediol, Examples include aliphatic diols such as hexanediol, alicyclic diols such as cyclohexanedimethanol, and polyalkylene glycols in which a plurality of diols are condensed via an ether bond (diethylene glycol and the like are special examples thereof). . These copolymerization components may be used alone or in combination of two or more.
[0032]
The proportions of these copolymer components, or the blending proportions in the case of a mixture with other polyesters or other types of resins, preferably satisfy the secondary transition temperature and melting temperature described later.
[0033]
The method for producing the polyester in the present invention is not particularly limited, but a method in which the main component and copolymer component of the acid component and the alcohol component are esterified, and then the resulting reaction product is subjected to a polycondensation reaction to obtain a polyester, or an acid. A method in which a dimethyl ester as a component, a main component of an alcohol component, and a copolymer component are transesterified, and then a reaction product obtained is polycondensed to form a polyester is preferably used. In the polyester in the present invention, other additives such as an antioxidant, a heat stabilizer, an ultraviolet absorber, an antistatic agent and the like can be contained as necessary.
[0034]
When the base film of the laminated film in the present invention contains the polyester as a main component, a lubricant such as calcium carbonate, kaolin, or silica is used in the polyester to control the surface roughness and impart slipperiness or scratch resistance. It is preferable to contain inorganic fine particles such as, fine particles precipitated from catalyst residues, and / or organic fine particles such as silicone and crosslinked polystyrene, and the particle size should be 4 μm or less. This is preferable for preventing breakage during film formation. In particular, spherical silica having an average particle size of 1.5 μm or less is suitable.
[0035]
As the base film of the laminated film in the present invention, a film composed of a polyester composition having a secondary transition temperature of 40 ° C. or higher and a melting temperature of 270 ° C. or lower is particularly preferable. If the secondary transition temperature is less than 40 ° C., moisture tends to permeate the film, there is a risk of rusting on the metal plate, and adhesion may occur during film formation, which may make handling difficult. . The secondary transition temperature is usually 45 to 120 ° C.
[0036]
When the melting temperature exceeds 270 ° C., there is a possibility that the adhesiveness when the film is fused and laminated to the metal plate is insufficient. The melting temperature is preferably 240 to 260 ° C. from the viewpoint of easy adhesion treatment to the metal plate.
[0037]
The polyester film in the present invention is a conventionally known method, for example, the above polyester is dried and melted, extruded from a die onto a cooling drum to cool to an unstretched film, and the unstretched film is stretched in a biaxial direction. In addition, it can be manufactured by heat fixing. The degree of biaxial stretching in this case is preferably 9 times or more in terms of area magnification, and the plane orientation coefficient calculated by the following formula from the refractive index measured with an Abbe refractometer using a sodium D line at 25 ° C. It is preferable to be 0.1 or more. The film thickness is preferably 12 to 50 μm.
f = [(n X + n Y ) / 2] −n Z
(Where f is the plane orientation coefficient, and n X , n Y , and n Z are the refractive indexes (Abbe method) in the horizontal, vertical, and thickness directions of the film, respectively)
[0038]
In the laminated film of the present invention, a primer layer or an intermediate layer may be provided between the photocatalytically active functional layer and the base film for the purpose of improving long-term durability by improving adhesion or preventing oxidative decomposition of the base material by photocatalytic action. preferable.
[0039]
As a component of the primer layer, a polyurethane resin, a polyester resin, an acrylic resin, and at least one resin selected from an acrylic resin and a vinyl resin-modified polyester resin, or a composition mainly composed of a silane coupling agent is used. Can be mentioned. A coating solution containing such a composition is applied to a substrate film and dried to form a primer layer. On this primer layer, a photocatalytic functional layer or an intermediate layer described later is provided. As a measure for improving the adhesion between the layers, corona discharge treatment, plasma treatment, flame treatment and the like can be applied in addition to the method of providing the primer layer.
[0040]
Examples of the component of the intermediate layer include hydrolysis condensates of hydrolyzable silicon compounds represented by the above formula (1). By providing the intermediate layer, it is possible to prevent oxidative decomposition of the base film or primer layer due to the photocatalytic action of the photocatalytic functional layer.
[0041]
Furthermore, in the laminated film of the present invention, as long as the effects of the present invention are not impaired, in addition to the photocatalytic functional layer of the present invention, a gas barrier layer, a light reflecting layer, a conductive layer, a recording layer such as magnetism, etc. are provided, Alternatively, coloring or printing may be performed.
[0042]
The laminated film of the present invention is used by being bonded to a metal plate for molding the top cover of a three-piece can or the cover of a two-piece can, and is particularly useful for use in bonding and coating the outer surface of the can.
[0043]
【Example】
Hereinafter, the present invention will be described in more detail with reference to examples. In the examples, “parts” means “parts by weight”. Further, various physical properties and characteristics described in the examples were measured and evaluated by the following methods.
[0044]
(1) Intrinsic viscosity Measured in o-chlorophenol at 35 ° C.
[0045]
(2) Melting temperature, secondary transition temperature Using a DuPont Instrument 910 DSC, the film was measured while being heated at a rate of 20 ° C./min, and the melting temperature was determined from the melting peak. Further, the film was heated at a rate of 20 ° C./min, held at 290 ° C. for 3 minutes, measured while being rapidly cooled and then heated again at a rate of 20 ° C./min, and the secondary transition temperature was determined from the glass transition point. Asked.
[0046]
(3) Retort brushing evaluation A laminated film obtained by laminating a laminated film on a surface opposite to a surface provided with a photocatalytic functional layer on tin-free steel (thickness 250 μm) heated to 200 ° C. and cooling with water The retort treatment for 30 minutes was performed at 130 ° C., and the appearance change was evaluated according to the following criteria.
○: No change in appearance △: Slightly cloudy on appearance ×: Occurrence of white spots (brushing) XX: Occurrence of roughness on the surface in addition to white spots [0047]
[Example 1]
Polyethylene terephthalate (containing an average particle size of 1.5 μm true spherical silica) having an intrinsic viscosity of 0.65 and a secondary transition temperature of 78 ° C. is melt-extruded on a rotating cooling drum maintained at 20 ° C. to obtain an unstretched film, and then machine After stretching 3.5 times in the axial direction, the film was stretched 3.9 times in the transverse direction and further heat treated at 200 ° C. to obtain a biaxially stretched polyester film having a thickness of 12 μm.
[0048]
A coating solution (Colcoat 103X, manufactured by Colcoat Co., Ltd.) obtained by subjecting the film to a corona discharge treatment and partially hydrolyzing ethyl silicate as a hydrolyzable silicon compound partially hydrolyzed thereon was used as a coating solution. Coating was performed at a coating amount of m 2 and dried at 150 ° C. for 1 minute to form a hydrolysis-condensation product, thereby providing an intermediate layer. Furthermore, as a composition of anatase-type titanium dioxide having an average particle size of 0.07 to 0.1 μm and ethyl silicate, a composition having a ratio of 50 parts / 50 parts in terms of TiO 2 / SiO 2 is used as a solvent. Coating solution (ST-K03, manufactured by Colcoat Co., Ltd.) with a solid content concentration of 10% as a coating solution, coating at a coating amount of 5 g / m 2 , drying at 150 ° C. for 2 minutes, and hydrolysis A condensate was formed to obtain a laminated film provided with a photocatalytic functional layer. Table 1 shows the characteristics of the obtained laminated film.
[0049]
[Example 2]
When forming a biaxially stretched polyester film, an acrylic resin water dispersion (methyl methacrylate component (65 mol%), ethyl acrylate component) is formed on one side of a uniaxially stretched film obtained by stretching 3.5 times in the machine axis direction. (28 mol%), 2-hydroxyethyl methacrylate component (2 mol%), and N-methylolacrylamide component (5 mol%) copolymer, Tg = 45 ° C.) as solids, 40 parts by weight, polyester resin 50 parts by weight of an aqueous dispersion (Takamatsu Yushi Co., Ltd., Pesresin 2000, Tg = 68 ° C.) as a solid content, and 10 wt% of a crosslinked acrylic resin fine particle aqueous dispersion having an average particle size of 0.03 μm as a solid content An aqueous coating solution having a solid content concentration of 2.7% by weight diluted with ion-exchanged water was prepared by kiss coating method per 1 m 2 of film. The coating solution was applied at an average coating amount of about 3 g, and was continuously stretched 3.9 times in the transverse direction while being dried. Also, the corona discharge treatment was not performed when the photocatalytic functional layer was applied. A laminated film was obtained in the same manner as in Example 1. Table 1 shows the characteristics of the obtained laminated film.
[0050]
[Example 3]
Except that polyethylene terephthalate copolymer (inherent viscosity 0.70, secondary transition temperature 74 ° C., average particle size 1.5 μm true spherical silica contained) copolymerized with 12 mol% of isophthalic acid was used as polyester. 1 was used to obtain a laminated film. Table 1 shows the characteristics of the obtained laminated film.
[0051]
[Example 4]
As the polyester, a polyethylene terephthalate copolymer (inherent viscosity 0.70, secondary transition temperature 82 ° C., average particle diameter 1.5 μm containing true spherical silica) copolymerized with 12 mol% of 2,6-naphthalenedicarboxylic acid was used. Except for the above, a laminated film was obtained in the same manner as in Example 1. Table 1 shows the characteristics of the obtained laminated film.
[0052]
[Comparative Examples 1-4]
A laminated film was obtained in the same manner as in Examples 1 to 4 except that the photocatalytic functional layer and the intermediate layer were not applied. Table 1 shows the characteristics of the obtained laminated film.
[0053]
[Table 1]
[0054]
【The invention's effect】
According to the present invention, it is possible to provide a transparent laminated film and a metal can lid for covering a metal can lid that do not cause white spots (retort brushing) during retort sterilization and do not impair the appearance of the product. In addition, as an effect derived from the use of the laminated film of the present invention, the antibacterial function due to the photocatalytic effect can be exhibited. Also in this respect, the laminated film of the present invention is extremely suitable for coating a metal can lid. It is preferable.
Claims (8)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11489199A JP4239290B2 (en) | 1999-04-22 | 1999-04-22 | Transparent laminated film for metal can lid bonding coating and metal can lid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11489199A JP4239290B2 (en) | 1999-04-22 | 1999-04-22 | Transparent laminated film for metal can lid bonding coating and metal can lid |
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| Publication Number | Publication Date |
|---|---|
| JP2000301666A JP2000301666A (en) | 2000-10-31 |
| JP4239290B2 true JP4239290B2 (en) | 2009-03-18 |
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| JP11489199A Expired - Fee Related JP4239290B2 (en) | 1999-04-22 | 1999-04-22 | Transparent laminated film for metal can lid bonding coating and metal can lid |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110920167A (en) * | 2018-09-19 | 2020-03-27 | 宝山钢铁股份有限公司 | Boiling-resistant discoloring iron-clad film and metal plate clad with same |
-
1999
- 1999-04-22 JP JP11489199A patent/JP4239290B2/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110920167A (en) * | 2018-09-19 | 2020-03-27 | 宝山钢铁股份有限公司 | Boiling-resistant discoloring iron-clad film and metal plate clad with same |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2000301666A (en) | 2000-10-31 |
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