JP3815849B2 - Laminated body - Google Patents
Laminated body Download PDFInfo
- Publication number
- JP3815849B2 JP3815849B2 JP12338497A JP12338497A JP3815849B2 JP 3815849 B2 JP3815849 B2 JP 3815849B2 JP 12338497 A JP12338497 A JP 12338497A JP 12338497 A JP12338497 A JP 12338497A JP 3815849 B2 JP3815849 B2 JP 3815849B2
- Authority
- JP
- Japan
- Prior art keywords
- layer
- ethylene
- vinyl acetate
- acetate copolymer
- resin composition
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Landscapes
- Laminated Bodies (AREA)
Description
【０００１】
【発明の属する技術分野】
本発明は、エチレン−酢酸ビニル共重合体ケン化物（以下、ＥＶＯＨと略記する）組成物の積層体に関し、更に詳しくは耐汚染性（汚染除去性）、耐薬品性等に優れた積層体に関する。
【０００２】
【従来の技術】
従来より、塩化ビニル樹脂のシートやフィルムは、建築内装用の壁紙や家具等の仕上げ用の化粧シート、農業用資材、自動車の内装用資材、日用雑貨（ビニルマット、傘等）などに利用されており、更にはデスクマット、ファイル表紙、手帳表紙等の事務用品や文房具などにも多用されている。
しかしながら、かかる塩化ビニル樹脂中には多量の可塑剤が含有されており、塩化ビニル樹脂中の可塑剤の悪影響を防ぐために塩化ビニル樹脂層にＥＶＯＨを積層した壁紙（実公平２−４７０１５号公報）や可塑剤を２５〜５５重量％含有するポリ塩化ビニル系フィルムに２〜５０μｍ厚みのＥＶＯＨを積層した積層体（特開昭６０−２２４５４２号公報）が提案されている。
【０００３】
【発明が解決しようとする課題】
しかしながら、上記のいずれの積層体（壁紙）も短期間の可塑剤抑制効果は認められるものの、高湿度下で、かつ３０〜４０℃程度の温度で長期間放置された場合には、かかる抑制効果も低下することが推察され、新なる改善が望まれるところである。
【０００４】
【課題を解決するための手段】
そこで、本発明者はかかる問題を解決するため鋭意研究を重ねた結果、エチレン含有量２０〜６０モル％，ケン化度９０モル％以上のＥＶＯＨ（Ａ１）及びエチレン−酢酸ビニル共重合体（以下、ＥＶＡと略記する）（Ａ２）からなり、ＥＶＯＨ（Ａ１）とＥＶＡ（Ａ２）の配合重量比（Ａ１）／（Ａ２）が９０／１０〜７０／３０である樹脂組成物（Ａ）層とカルボキシル基含有ＥＶＡ（Ｂ）層を積層してなり、カルボキシ基含有エチレン−酢酸ビニル共重合体（Ｂ）の外側に更に熱可塑性樹脂（Ｃ）を積層してなり、かかる熱可塑性樹脂（Ｃ）が塩化ビニル樹脂である積層体が上記の課題を解決することができ、更には該樹脂組成物（Ａ）層がＥＶＯＨ（Ａ１）中にＥＶＡ（Ａ２）が分散してるとき、本発明の作用効果を顕著に得られることを見出し本発明を完成するに至った。
【０００５】
【発明の実施の形態】
以下、本発明について具体的に説明する。
本発明のＥＶＯＨ（A1）は、エチレン含量２０〜６０モル％（更には２５〜５０モル％）で、酢酸ビニル成分のケン化度が９０モル％以上（更には９５モル％以上）のものが用いられ、エチレン含量が２０モル％未満では、高湿度下における可塑剤抑制効果が不十分となり、逆に６０モル％を越えると、ＥＶＯＨのバリヤー性が低下して本発明の目的を達成することはできず、また、ケン化度が９０モル％未満でも高湿度下における可塑剤抑制効果が不十分となって本発明の目的を達成することはできない。
【０００６】
また、該ＥＶＯＨは更に少量のプロピレン、イソブテン、α−オクテン、α−ドデセン、α−オクタデセン等のα−オレフィン、不飽和カルボン酸又はその塩・部分アルキルエステル・完全アルキルエステル・ニトリル・アミド・無水物、不飽和スルホン酸又はその塩等のコモノマーを含んでいても差支えない。
また、ＥＶＯＨ（A1）のメルトインデックス（ＭＩ）は、０．５〜５０ｇ／１０分（２１０℃、２１６０ｇ荷重）が好ましく、更には１〜３５ｇ／１０分（同上）が好ましい。かかるＭＩが０．５ｇ／１０分（同上）未満では溶液或いは押出コーティングする際の加工性が不良となり、逆に５０ｇ／１０分（同上）を越えると汚染除去性が不十分となって好ましくない。
【０００７】
また、上記のＥＶＯＨ（Ａ１）に含有されるエチレン−酢酸ビニル共重合体（Ａ２）は、酢酸ビニル含有量が、３０〜７０重量％が好ましく、更には３５〜６５重量％が好ましく、かかる含有量が３０重量％未満では可塑剤抑制効果が不十分となり、逆に７０重量％を越えると積層体の外観が不良となって好ましくない。
かかるＥＶＯＨ（Ａ１）とＥＶＡ（Ａ２）の配合重量比（Ａ１）／（Ａ２）は、９０／１０〜７０／３０であり、かかる配合重量比が９０／１０を越えると可塑剤抑制効果が不十分となり 逆に７０／３０未満では積層体の外観が不良となって好ましくない。
【０００８】
ＥＶＯＨ（A1）とＥＶＡ（A2）の配合に当たっては、特に限定されないが、ＥＶＯＨ（A1）中にＥＶＡ（A2）が分散されるように混合配合することにより、本発明の作用効果を顕著に発揮することができ、具体的には、溶融状態の（A1）に溶融状態の（A2）を溶融混合すればよく、（A1）を溶融状態にするにあたっては、特に限定されないが、２軸押出機等の多軸押出機、単軸押出機などにより、その融点より２０〜８０℃高い温度（ＥＶＯＨの種類にもよるが、通常は１９０℃〜２５０℃程度）で溶融すればよく、また（A2）を溶融するにあたっても、（A1）と同様に２軸押出機等の多軸押出機、単軸押出機などにより、その融点より２０〜８０℃高い温度で溶融すればよい。
【０００９】
かかる溶融状態の（A1）と（A2）を混合するには、（A2）の押出機から（A1）の押出機にメルトサイドフィードしながら溶融混合する方法、（A1）の押出機に（A2）を計量しながら、ソリッドサイドフィードして溶融混合する方法、（A1）の押出機から（A2）の押出機にメルトサイドフィードしながら溶融混合する方法、（A2）の押出機に（A1）を計量しながら、ソリッドサイドフィードして溶融混合する方法等が挙げられ、特に限定はされないが、（A1）中への（A2）の分散性の点で、（A2）の押出機から（A1）の押出機にメルトサイドフィードしながら溶融混合する方法が好適に実施される。
かかる方法により、（A1）中に（A2）が、島状、粒子状、ロッド状等の形状で分散するのである。
【００１０】
また、カルボキシル基含有ＥＶＡ（Ｂ）としては、酢酸ビニル含有量が、１〜４０重量％が好ましく、更には２〜３０モル％が好ましく、かかる含有量が１重量％未満では層（Ａ）との接着性が低下し、逆に４０重量％を越えると積層体の外観が不良となって好ましく、更にカルボキシル基の含有量としては、０．５〜２０モル％が好ましく、更には１〜１０モル％が好ましく、かかる含有量が０．５モル％未満では層（Ａ）との接着性が低下し、逆に２０モル％を越えると積層体の外観が不良となって好ましくない。
また、かかるカルボキシル基の導入にあたっては、アクリル酸、メタクリル酸、クロトン酸、マレイン酸、フマル酸、イタコン酸、或いはこれらの無水物等の不飽和カルボン酸含有単量体をＥＶＡあるいはエチレン及び酢酸ビニルと共重合させればよい。
【００１１】
上記の樹脂組成物（Ａ）層とカルボキシル基含有ＥＶＡ（Ｂ）層を積層するに当たっては、予めフィルム状或いはシート状に成形されたカルボキシル基含有ＥＶＡ（Ｂ）層に樹脂組成物（Ａ）を積層すればよく、かかる積層方法としては、▲１▼溶液コーティング、▲２▼溶融押出コーティング、▲３▼フィルムラミネート（ドライラミネート）等の積層方法が挙げられる。
▲１▼溶液コーティングにおいては、樹脂組成物（Ａ）の溶液或いは分散液が用いられ、その際の溶媒としては水とアルコールの混合溶媒が使用され、水の量は３０〜７０重量％（アルコールの量は７０〜３０重量％）、好ましくは４０〜６０重量％（アルコールの量は６０〜４０重量％）であり、３０重量％未満又は７０重量％を越えると均一な溶液が得難く塗膜が不透明となるという問題点が生じる。またアルコールとしては メタノール、エタノール、n−プロピルアルコール、 iso−プロピルアルコール、 n−ブチルアルコール、iso−ブチルアルコール、sec−ブチルアルコール、tert−ブチルアルコール等が挙げられ、n−プロピルアルコール、iso −プロピルアルコールが好適に使用される。
【００１２】
かかる樹脂組成物（Ａ）溶液或いは分散液中の樹脂組成物（Ａ）濃度は特に制限はなく任意の範囲で塗工可能で通常は０.５〜２５重量％程度が好ましいが、本発明の効果を効率よく発揮するためには１０〜２０重量％が最も好ましい。
かかる樹脂組成物（Ａ）溶液或いは分散液を（Ｂ）層の表面にコーティングするに当たっては公知の方法を採用することができ、例えばグラビアコーター、リバースロールコーター、エアナイフコーター、ロータースクリーンコーター、フラットスクリーンコーター、スプレー、ハケ塗り、バーコーター等が挙げられ、好適にはグラビアコーターやリバースロールコーターが使用される。その後加熱乾燥されて（Ｂ）層の表面に樹脂組成物（Ａ）の塗膜層が形成される訳であるが、かかる樹脂組成物（Ａ）溶液或いは分散液を紙に塗布・乾燥する際の理想的な樹脂組成物（Ａ）溶液或いは分散液塗布時の溶液粘度とその後の乾燥温度は、樹脂組成物（Ａ）溶液塗布時の溶液粘度が５０〜１０００ｃｐｓ、その後の乾燥温度が８０〜１２０℃程度の範囲よりそれぞれ任意に選択すればよい。また、乾燥時の時間は特に限定されないが、通常は１０秒〜１０分（更には３０秒〜５分）の範囲より適宜選択される。
【００１３】
また、樹脂組成物（Ａ）塗膜層の（乾燥後の）厚みは特に限定されないが、１〜５０μｍが好ましく、特に２〜１０μｍとすることが好ましく、樹脂組成物（Ａ）の着量（乾燥後の付着量）は、１〜５０ｇ／ｍ2が好ましく、更には２〜１０ｇ／ｍ2が好ましい。（樹脂組成物（Ａ）の着量は、下記の▲２▼、▲３▼についても同様である。）かかる樹脂組成物（Ａ）溶液或いは分散液の塗布に当たって、通常は基材の表面には接着剤（アンカーコート）層が設けられる。かかる接着剤としては、有機チタン系接着剤、２液反応型ポリウレタン系接着剤、ポリエステル／イソシアネート系接着剤等が挙げられ、好適には２液反応型ポリウレタン系接着剤が使用される。
【００１４】
▲２▼溶融押出コーティングにおいては、（Ｂ）層の表面に必要に応じてプライマー処理を施しておくことが好ましく、該プライマー処理剤としては上記の▲１▼に記載の有機チタン系接着剤、２液反応型ポリウレタン系接着剤、ポリエステル／イソシアネート系接着剤等が挙げられ、好適には２液反応型ポリウレタン系接着剤が使用され、かかるプライマー処理剤の使用量は０．１〜１０ｇ／ｍ2、好ましくは０．３〜５ｇ／ｍ2である。樹脂組成物（Ａ）の溶融押出に際しては公知の溶融押出機を用いることができ、（必要によりプライマー処理された）（Ｂ）層の表面に溶融押出コーティングすることが好ましい。また、溶融押出コーティングの際には、樹脂組成物（Ａ）の安定したコーティングを行うために必要に応じてポリオレフィン系樹脂等のサポート層を入れて、２種２層以上の溶融押出コーティングを行ってもよい。
【００１５】
▲３▼フィルムラミネート（ドライラミネート）においては、（Ｂ）層の表面に必要に応じて上記の如きプライマー処理を行った後、有機チタン系接着剤、２液反応型ポリウレタン系接着剤、ポリエステル／イソシアネート系接着剤等の接着剤を介して行うのであるが、この場合の樹脂組成物（Ａ）のフィルムは延伸、無延伸どちらでもよく、延伸の場合は短時間の熱処理と配向の効果で後述する融解熱を上げることができるが、後でエンボス処理等が施されるのであれば、収縮する可能性もあり、この場合には無延伸フィルムが好ましい。また、このときの樹脂組成物（Ａ）フィルムの厚みは５〜５０μｍが好ましく、更には１０〜２０μｍが好ましい。
【００１６】
本発明においては、かかる樹脂組成物（Ａ）層／カルボキシル基含有エチレン−酢酸ビニル共重合体（Ｂ）層なる積層体の該（Ｂ）層の更に外側に熱可塑性樹脂（Ｃ）層を設け、かかる熱可塑性樹脂（Ｃ）としては、具体的には、塩化ビニル樹脂、が使用される。
【００１８】
かかる（Ａ）層／（Ｂ）層／（Ｃ）層の層構成を有する積層体を作製するに当たっては、（Ａ）層／（Ｂ）層からなる積層体を（Ｃ）層にラミネートする方法、（Ｂ）層／（Ｃ）層からなる積層体に（Ａ）を上記の▲１▼〜▲３▼等の方法によって積層する方法、（Ｃ）層に（Ｂ）及び（Ａ）をラミネートする方法、（Ａ）〜（Ｃ）を共押出する方法等によって行うことができる。
【００１９】
かくして樹脂組成物（Ａ）層／カルボキシル基含有ＥＶＡ（Ｂ）層または樹脂組成物（Ａ）層／カルボキシル基含有ＥＶＡ（Ｂ）層／熱可塑性樹脂（Ｃ）層の層構成を有する積層体が得られるわけであるが、本発明においてはこれ以外にも、樹脂組成物（Ａ）層をａ、カルボキシル基含有ＥＶＡ（Ｂ）層をｂ、熱可塑性樹脂（Ｃ）層をｃとすると、ａ／ｂ／ｃ（塩化ビニル樹脂）、ａ／ｂ／ｃ（ポリオレフィン系樹脂）／ｃ（塩化ビニル樹脂）、ａ／ｂ／ｃ（ポリエステル系樹脂）／ｃ（塩化ビニル樹脂）、ｃ（アクリル系樹脂）／ａ／ｂ／ｃ（塩化ビニル樹脂）等の積層構造を挙げることができ、特に（表側）ａ／ｂ／ｃ（塩化ビニル樹脂）（裏側）、（表側）ａ／ｂ／ｃ（ポリオレフィン系樹脂）／ｃ（塩化ビニル樹脂）（裏側）の積層構造を有するものは、壁紙や化粧用シート等の内装材用途に有用で、これらの積層体の熱可塑性樹脂（Ｃ）層の裏面には洋紙、和紙、不織布、アスベスト、紙、ガラス、繊維、布等の壁紙用の基材を粘（接）着剤を塗布し、カレンダー法、ラミネート法等の方法で張り合わせることも可能で、また紙にナイフコーターやロールコーター、フラットスクリーンコーターで塩化ビニル樹脂（Ｃ）を塗布し、その後樹脂組成物（Ａ）及びカルボキシル基含有ＥＶＡ（Ｂ）の積層体を積層させることもできる。かかる壁紙を壁に貼着する場合には、一般に用いられる水系澱粉糊等の公知の接着剤を基材に塗布し、壁面に圧着させればよく、また、意匠性等の付加価値を高めるためにこれらの積層体の少なくとも一方の表面にエンボス加工を施して凹凸模様を形成することも有用であり、凹凸模様としては木目導管模様、塗装板の表面を模したもの、抽象模様、石目模様、布目模様、万線模様、木肌模様及びそれらを組み合わせたもの等を用いることができ、かかるエンボス加工により形成される凹凸模様の深さは模様により異なるが、壁紙用途の場合、通常１〜２００μｍ程度に形成するのが、良好な立体感を付与することとなり好ましい。
【００２０】
また、壁紙等の意匠性を付与するために塩化ビニル樹脂（Ｃ）等の層を発泡させることも有用で、この場合の樹脂組成物（Ａ）とカルボキシル基含有ＥＶＡ（Ｂ）の積層体の積層工程は発泡処理の前後どちらでもよいが、実質的には溶液コーティングの時は樹脂組成物（Ａ）積層後に発泡処理を行うことが好ましく、溶融コーティング或いはフィルムラミネート法の時は発泡処理後に樹脂組成物（Ａ）を積層することが好ましい。また、（Ｂ）層は溶液コーティングの場合は順次行うことが好ましく、フィルムラミネートの場合は予め（Ａ）層と積層しておくことが好ましい。
【００２１】
エンボス加工により凹凸模様を形成する方法としては、所望の凹凸模様を形成した通常の熱エンボス機を用いてエンボス加工を施す方法やエクストルージョンコート装置の冷却ロール等に所望の凹凸模様を付与したエンボスロールを用い、樹脂組成物（Ａ）及びカルボキシル基含有ＥＶＡ（Ｂ）の積層体を形成するのと同時にエンボス加工を行う所謂ダブリングエンボス法等いわゆるメカニカルエンボス法あるいは発泡抑制剤や発泡促進剤を含むインクを印刷し、発泡工程で凹凸模様をつけるケミカルエンボス法等が用いられる。
また、ａ／ｂ／ｃ（塩化ビニル樹脂）、ａ／ｂ／ｃ（塩化ビニル樹脂）／ａ、等の積層構造を有するものは、農業用フィルム（シート）として有用である。
【００２２】
本発明では積層体の各層に可塑剤（軟質塩化ビニル樹脂層には当然のことながら含有されている）、安定剤、界面活性剤、架橋性物質（エポキシ化合物、多価金属、無機又は有機の多塩基酸又はその塩等）、充填剤、着色剤、補強材としての繊維（ガラス繊維、炭素繊維等）、艶消剤（タルク、シリカ系粉末、ポリエチレン、ポリウレタン等の樹脂微粒子粉末）等を本発明の効果を阻害しない範囲において配合することもできる。
尚、上記の如きａ／ｂ、ａ／ｂ／ｃ、・・・・・等の積層体におけるａ、ｂおよびｃの厚みはその用途等により一概に規定できないが、通常はａが１〜５０μｍ、ｂが０．１〜１０μｍ、ｃが５０〜１００００μｍ程度の範囲から任意に選択される。
【００２３】
かくして得られた本発明の積層体は、建築内装用の壁紙や家具等の仕上げ用の化粧シートなどをはじめデスクマット等の事務用品、塩ビレザーの表紙を用いた手帳やファイル等の文房具、自動車用の内装用資材、農業用フィルム等の農業用資材、日用雑貨（ビニルマット、傘等）などに利用することができ、中でも上記で詳述したように壁紙や化粧シート等の内装材や農業用フィルム（シート）に大変有用であり、殊に耐汚染性（汚染除去性）に優れた壁紙に有用である。
【００２４】
【実施例】
以下に、実施例を挙げて本発明の方法を具体的に説明する。
なお、「％」、「部」とあるのは特にことわりのない限り、いずれも重量基準を意味する。
実施例１
エチレン含有量４４モル％，ケン化度９９．７モル％，ＭＩ１２ｇ／１０分（２１０℃、２１６０ｇ荷重）のＥＶＯＨ（A1）８０部を約２２０℃の二軸押出機に入れ、別途単軸押出機を用いて約１９０℃に溶融した酢酸ビニル含有量３３％のＥＶＡ（A2）２０部をかかる二軸押出機の側面からメルトサイドフィード法により溶融混合して樹脂組成物（Ａ）を得た（尚、上記の（A1）及び（A2）の配合割合は吐出量より算出した）。
尚、樹脂組成物（Ａ）のペレットを走査型電子顕微鏡で観察したところ、約３μｍ程度の（A2）粒子が（A1）中に分散していた。
次いでかかる樹脂組成物（Ａ）を単軸押出機にて厚さ２０μｍのフィルムに成形した。
更に、片面にイソシアネート反応型ポリウレタン系接着剤（東洋モートン社製、ＡＤ−３３５Ａ／ｃａｔ−１０）が１．５ｇ／ｍ2塗工された厚み１０μｍで、酢酸ビニル含有量３３％，カルボキシル基含有量１．５モル％の無水マレイン酸変性ＥＶＡ（Ｂ）のシートの接着剤面に上記のフィルムをドライラミネートして積層体を作製した。
得られた積層体を用いて以下の評価を行った。
【００２５】
（汚染除去性）
積層体の樹脂組成物（Ａ）層表面に約７０℃のホットコーヒーを直径２ｃｍ程度の大きさに塗布あるいは滴下し、２０℃で２４時間放置後に水を含ませたさらし木綿で拭き取った後の積層体の表面状態を目視により以下の通り評価した。なお、軟質ポリ塩化ビニル樹脂シート単独層についても同様に行った。
また、別途、得られた積層体を４０℃で１日間放置処理して同様の評価を行った。
尚、靴墨（中性洗剤で拭き取った）、和がらし、水性マジック（市販の洗剤（マジックリン）で拭き取った）についても同様に評価した。
（可塑剤移行性）
積層体（１０ｃｍ×１０ｃｍ）を樹脂組成物（Ａ）層が上になるように平坦な厚さ４００μｍの塩化ビニル樹脂のシート（可塑剤含有量５０％）の上に置き、樹脂組成物（Ａ）層表面と接するように厚さ３ｍｍ，直径５ｃｍの可塑剤無添加の塩化ビニル樹脂板を置いた後、均一に５０ｇ／ｃｍ２の荷重をかけて、７０℃、９０％ＲＨで１０日放置後の該塩化ビニル樹脂板の重量変化（可塑剤移行量）（ｇ／ｍ２）を測定して、以下の通り評価した。
○ −−− 重量変化が２ｇ／ｍ２未満
× −−− 重量変化が２ｇ／ｍ２以上
（耐薬品性）
エタノールを約１ｃｃを積層体の樹脂組成物（Ａ）層表面に滴下し、常態で１時間放置後の表面状態を目視観察して、以下の通り評価した。
○ −−− 異状無し
× −−− 膨潤が認められる
【００２７】
実施例２
実施例１の積層体において、（無水マレイン酸変性）カルボキシル基含有ＥＶＡ（Ｂ）の表面に更にイソシアネート反応型ポリエステル系接着剤（日本合成化学工業社製の『ポリエスターＬＰ０３３』／日本ポリウレタン社製の『コロネートＬ』）を１．５ｇ／ｍ2塗工して、厚さ４００μｍの塩化ビニル樹脂（Ｃ）のシート（可塑剤含有量５０％）を積層した以外は同様に行って、同様に評価をした。
【００２８】
実施例３
実施例１において、（Ｂ）として、酢酸ビニル含有量７％，カルボキシル基含有量３モル％の無水マレイン酸変性ＥＶＡ（Ｂ）を用いた以外は同様に行って、同様に評価をした。
実施例４
実施例２において、ＥＶＯＨ（A1）及びＥＶＡ（A2）の配合重量比を（A1）／（A2）＝７０部／３０部とした以外は同様に行って積層体を得て、同様に評価をした。
【００２９】
実施例５
実施例１において、ＥＶＯＨ（A1）をエチレン含有量３２モル％，ケン化度９９．８モル％，ＭＩ１２ｇ／１０分（同上）のＥＶＯＨとした以外は同様に行って積層体を得て、同様に評価を行した。
【００３０】
比較例１
実施例１において、樹脂組成物（Ａ）をＥＶＯＨ（A1）単独とした以外は同様に行って積層体を得て、同様に評価を行った。
比較例２
実施例１において、（無水マレイン酸変性）カルボキシル基含有ＥＶＡ（Ｂ）に代えて、酢酸ビニル含有量３３％の未変性ＥＶＡを用いた以外は同様に行って積層体を得て、同様に評価を行った。
実施例及び比較例の評価結果を表１に示す。
【００３１】
【表１】
──────────────────────────────────────
汚染除去性 可塑剤移行性 耐薬品性
──────────────────────────────────────
無処理 放置処理後
──────────────────────────────────────
実施例１ ○ ○ ○ ○
〃 ２ ○ ○ ○ ○
〃 ３ ○ ○ ○ ○
〃 ４ ○ ○ ○ ○
〃 ５ ○ ○ ○ ○
──────────────────────────────────────
比較例１ ○ × × ×
〃 ２ ○ × × ×
──────────────────────────────────────
【００３２】
【発明の効果】
本発明の積層体は、ＥＶＯＨとＥＶＡからなる樹脂組成物層とカルボキシル基含有ＥＶＡ層を積層しているため、耐防汚性（汚染除去性）、耐薬品性等に優れ、建築内装用の壁紙や家具等の仕上げ用の化粧シートなどをはじめデスクマット等の事務用品、塩ビレザーの表紙を用いた手帳やファイル等の文房具、自動車用の内装用資材、農業用フィルム等の農業用資材、日用雑貨（ビニルマット、傘等）などの積層体にも大変有用である。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a laminate of a saponified ethylene-vinyl acetate copolymer (hereinafter abbreviated as EVOH) composition, and more particularly to a laminate excellent in stain resistance (contamination removal property), chemical resistance, and the like. .
[0002]
[Prior art]
Conventionally, vinyl chloride resin sheets and films have been used for decorative interior sheets for furniture and furniture for architectural interiors, agricultural materials, automotive interior materials, daily goods (vinyl mats, umbrellas, etc.) It is also widely used for office supplies such as desk mats, file covers, notebook covers, and stationery.
However, such a vinyl chloride resin contains a large amount of plasticizer, and a wallpaper in which EVOH is laminated on the vinyl chloride resin layer in order to prevent the adverse effect of the plasticizer in the vinyl chloride resin (Japanese Utility Model Publication No. 2-47015). In addition, a laminate (JP-A-60-224542) in which EVOH having a thickness of 2 to 50 μm is laminated on a polyvinyl chloride film containing 25 to 55% by weight of a plasticizer has been proposed.
[0003]
[Problems to be solved by the invention]
However, although any of the above laminates (wallpaper) has a short-term plasticizer-inhibiting effect, it is effective when left at high temperatures and at temperatures of about 30 to 40 ° C. for a long time. Therefore, a new improvement is desired.
[0004]
[Means for Solving the Problems]
Therefore, as a result of intensive studies to solve such problems, the present inventor has found that EVOH (A1) having an ethylene content of 20 to 60 mol% and a saponification degree of 90 mol% or more and an ethylene-vinyl acetate copolymer (hereinafter referred to as “the saponification copolymer”) , abbreviated as EVA) (A2) Tona Ri, EVOH (A1) and the ratio by weight of EVA (A2) (A1) / (A2) is 90 / 10-70 / 30 der Ru resin composition (a) Layer and a carboxyl group-containing EVA (B) layer, and a thermoplastic resin (C) is further laminated outside the carboxyl group-containing ethylene-vinyl acetate copolymer (B), and the thermoplastic resin ( The laminate in which C) is a vinyl chloride resin can solve the above-mentioned problems, and furthermore, when the resin composition (A) layer has EVA (A2) dispersed in EVOH (A1), the present invention The effect of This has led to the completion of the present invention found a door.
[0005]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the present invention will be specifically described.
The EVOH (A1) of the present invention has an ethylene content of 20 to 60 mol% (more preferably 25 to 50 mol%) and a vinyl acetate component having a saponification degree of 90 mol% or more (further 95 mol% or more). When the ethylene content is less than 20 mol%, the plasticizer suppressing effect under high humidity becomes insufficient. Conversely, when the ethylene content exceeds 60 mol%, the barrier property of EVOH is lowered and the object of the present invention is achieved. Moreover, even if the degree of saponification is less than 90 mol%, the effect of suppressing the plasticizer under high humidity is insufficient and the object of the present invention cannot be achieved.
[0006]
In addition, the EVOH is further composed of a small amount of an α-olefin such as propylene, isobutene, α-octene, α-dodecene, α-octadecene, unsaturated carboxylic acid or salt thereof, partial alkyl ester, complete alkyl ester, nitrile, amide, anhydrous Or a comonomer such as unsaturated sulfonic acid or a salt thereof.
The melt index (MI) of EVOH (A1) is preferably 0.5 to 50 g / 10 min (210 ° C., 2160 g load), and more preferably 1 to 35 g / 10 min (same as above). If the MI is less than 0.5 g / 10 min (same as above), the processability during solution or extrusion coating is poor, and conversely if it exceeds 50 g / 10 min (same as above), the decontamination property is insufficient, which is not preferable. .
[0007]
The ethylene-vinyl acetate copolymer (A2) contained in the EVOH (A1) preferably has a vinyl acetate content of 30 to 70% by weight, more preferably 35 to 65% by weight. If the amount is less than 30% by weight, the effect of suppressing the plasticizer becomes insufficient.
Such EVOH (A1) and the ratio by weight of EVA (A2) (A1) / (A2) is 9 0 / 10-70 / 30, such mixing weight ratio plasticizers suppression effect exceeds 90/10 On the contrary, if it is less than 70/30 , the appearance of the laminate is poor, which is not preferable.
[0008]
The blending of EVOH (A1) and EVA (A2) is not particularly limited, but by mixing and blending so that EVA (A2) is dispersed in EVOH (A1), the effects of the present invention are remarkably exhibited. Specifically, the melted (A1) may be melt-mixed with the melted (A1), and there is no particular limitation in bringing (A1) into the melted state. It may be melted at a temperature 20 to 80 ° C. higher than the melting point (normally about 190 ° C. to 250 ° C. depending on the type of EVOH) by a multi-screw extruder, single-screw extruder, etc. In the case of melting a), similarly to (A1), it may be melted at a temperature 20 to 80 ° C. higher than its melting point by a multi-screw extruder such as a twin-screw extruder or a single-screw extruder.
[0009]
In order to mix (A1) and (A2) in such a molten state, a method of melt mixing while melt-side feeding from an extruder (A2) to an extruder (A1), (A2) ) With solid side feed while measuring, melt mixing with (A1) extruder to (A2) melt side feed, (A1) with (A1) extruder Although there is no particular limitation, such as a method of solid-side feed and melt mixing while weighing, from the point of view of dispersibility of (A2) in (A1) (A1) The method of melt mixing while melt side feeding to the extruder is preferably carried out.
By this method, (A2) is dispersed in (A1) in the form of islands, particles, rods, or the like.
[0010]
Further, as the carboxyl group-containing EVA (B), the vinyl acetate content is preferably 1 to 40% by weight, more preferably 2 to 30% by mole, and when the content is less than 1% by weight, the layer (A) and On the other hand, when the content exceeds 40% by weight, the appearance of the laminate is poor, and the carboxyl group content is preferably 0.5 to 20 mol%, more preferably 1 to 10%. If the content is less than 0.5 mol%, the adhesiveness with the layer (A) is lowered. Conversely, if it exceeds 20 mol%, the appearance of the laminate is unfavorable.
In addition, when introducing such a carboxyl group, an unsaturated carboxylic acid-containing monomer such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, or an anhydride thereof is replaced with EVA or ethylene and vinyl acetate. And may be copolymerized.
[0011]
In laminating the resin composition (A) layer and the carboxyl group-containing EVA (B) layer, the resin composition (A) is applied to the carboxyl group-containing EVA (B) layer previously formed into a film or sheet. The lamination may be carried out, and examples of the lamination method include (1) solution coating, (2) melt extrusion coating, and (3) film lamination (dry lamination).
(1) In solution coating, a solution or dispersion of the resin composition (A) is used, and a mixed solvent of water and alcohol is used as a solvent at that time, and the amount of water is 30 to 70% by weight (alcohol). The coating amount is 70 to 30% by weight), preferably 40 to 60% by weight (the amount of alcohol is 60 to 40% by weight). When the amount is less than 30% or exceeds 70% by weight, it is difficult to obtain a uniform solution. The problem arises that becomes opaque. Examples of alcohol include methanol, ethanol, n-propyl alcohol, iso-propyl alcohol, n-butyl alcohol, iso-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol, and the like. N-propyl alcohol, iso-propyl Alcohol is preferably used.
[0012]
The concentration of the resin composition (A) in the resin composition (A) solution or dispersion is not particularly limited and can be applied within an arbitrary range, and is usually preferably about 0.5 to 25% by weight. In order to exhibit an effect efficiently, 10 to 20 weight% is the most preferable.
In coating the surface of the layer (B) with such a resin composition (A) solution or dispersion, a known method can be employed, such as a gravure coater, reverse roll coater, air knife coater, rotor screen coater, flat screen. Examples include a coater, spray, brush coating, bar coater, and a gravure coater and a reverse roll coater are preferably used. Then, it is heated and dried to form a coating layer of the resin composition (A) on the surface of the layer (B). When the resin composition (A) solution or dispersion is applied to paper and dried. The solution viscosity at the time of coating the ideal resin composition (A) or dispersion and the subsequent drying temperature are 50 to 1000 cps at the time of coating the resin composition (A) solution, and the subsequent drying temperature is 80 to What is necessary is just to select arbitrarily from the range of about 120 degreeC, respectively. Moreover, the time at the time of drying is not particularly limited, but it is usually appropriately selected from the range of 10 seconds to 10 minutes (more preferably 30 seconds to 5 minutes).
[0013]
The thickness of the resin composition (A) coating layer (after drying) is not particularly limited, but is preferably 1 to 50 μm, particularly preferably 2 to 10 μm, and the amount of resin composition (A) applied ( deposition amount after drying) is preferably from 1 to 50 g / m 2, more preferably from 2 to 10 g / m 2. (The amount of the resin composition (A) applied is the same for the following (2) and (3).) In applying the resin composition (A) solution or dispersion, it is usually applied to the surface of the substrate. Is provided with an adhesive (anchor coat) layer. Examples of such an adhesive include an organic titanium adhesive, a two-component reactive polyurethane adhesive, a polyester / isocyanate-based adhesive, and the like, and preferably a two-component reactive polyurethane adhesive is used.
[0014]
(2) In the melt extrusion coating, the surface of the layer (B) is preferably subjected to a primer treatment as necessary, and as the primer treatment agent, the organic titanium-based adhesive described in (1) above, A two-component reactive polyurethane adhesive, a polyester / isocyanate-based adhesive, and the like can be mentioned. A two-component reactive polyurethane adhesive is preferably used. The amount of the primer treatment agent used is 0.1 to 10 g / m. 2 , preferably 0.3 to 5 g / m 2 . In the melt extrusion of the resin composition (A), a known melt extruder can be used, and the surface of the layer (B) (primed if necessary) is preferably melt extrusion coated. In addition, in the case of melt extrusion coating, in order to perform stable coating of the resin composition (A), a support layer such as a polyolefin-based resin is inserted as necessary to perform two or more types of melt extrusion coating. May be.
[0015]
(3) In film laminating (dry laminating), the surface of the layer (B) is subjected to the primer treatment as necessary, and then an organic titanium adhesive, a two-component reactive polyurethane adhesive, polyester / The film of the resin composition (A) in this case may be either stretched or non-stretched, and in the case of stretching, the effect of short-time heat treatment and orientation will be described later. However, if an embossing treatment or the like is performed later, there is a possibility of shrinkage. In this case, an unstretched film is preferable. The thickness of the resin composition (A) film at this time is preferably 5 to 50 μm, more preferably 10 to 20 μm.
[0016]
In the present invention, a thermoplastic resin (C) layer is provided on the outer side of the (B) layer of the laminate comprising the resin composition (A) layer / carboxyl group-containing ethylene-vinyl acetate copolymer (B) layer. only, Examples of such a thermoplastic resin (C), specifically, vinyl chloride resins, but is used.
[0018]
In producing a laminate having the layer structure of (A) layer / (B) layer / (C) layer, a method of laminating a laminate comprising the (A) layer / (B) layer on the (C) layer , (A) is laminated on the laminate composed of (B) layer / (C) layer by the above methods (1) to (3), and (B) and (A) are laminated on the (C) layer. Or a method of coextrusion of (A) to (C).
[0019]
Thus, a laminate having a layer structure of resin composition (A) layer / carboxyl group-containing EVA (B) layer or resin composition (A) layer / carboxyl group-containing EVA (B) layer / thermoplastic resin (C) layer is obtained. However, in the present invention, if the resin composition (A) layer is a, the carboxyl group-containing EVA (B) layer is b, and the thermoplastic resin (C) layer is c , / B / c (vinyl chloride resin) , a / b / c (polyolefin resin) / c (vinyl chloride resin), a / b / c (polyester resin) / c (vinyl chloride resin), c (acrylic) Resin) / a / b / c (vinyl chloride resin) and the like, and in particular (front side) a / b / c (vinyl chloride resin) (back side), (front side) a / b / c ( Polyolefin resin) / c (vinyl chloride resin) (back side) product Those having a structure are useful for interior materials such as wallpaper and cosmetic sheets, and on the back side of the thermoplastic resin (C) layer of these laminates are Western paper, Japanese paper, non-woven fabric, asbestos, paper, glass, fiber, It is possible to apply a base material for wallpaper such as cloth to a sticky (adhesive) adhesive and paste it together by a calendering method, a laminating method, etc., and vinyl chloride with a knife coater, roll coater or flat screen coater on paper. The resin (C) can be applied, and then a laminate of the resin composition (A) and the carboxyl group-containing EVA (B) can be laminated. When pasting such a wallpaper on a wall, a known adhesive such as a water-based starch paste generally used may be applied to a base material and bonded to a wall surface, and in order to increase added value such as design properties. It is also useful to form an uneven pattern by embossing at least one surface of these laminates. As the uneven pattern, a wood grain conduit pattern, a model of the surface of a painted plate, an abstract pattern, a stone pattern , Texture patterns, line patterns, bark patterns and combinations thereof can be used, and the depth of the concavo-convex pattern formed by such embossing varies depending on the pattern, but for wallpaper applications, usually 1 to 200 μm Forming to the extent is preferable because it gives a good stereoscopic effect.
[0020]
It is also useful to foam a layer such as a vinyl chloride resin (C) in order to impart design properties such as wallpaper. In this case, the laminate of the resin composition (A) and carboxyl group-containing EVA (B) The lamination process may be performed either before or after the foaming treatment, but in practice, the foaming treatment is preferably carried out after the resin composition (A) is laminated at the time of solution coating, and the resin after the foaming treatment at the time of melt coating or film laminating method. It is preferable to laminate the composition (A). In addition, the (B) layer is preferably sequentially applied in the case of solution coating, and is preferably laminated in advance with the (A) layer in the case of film lamination.
[0021]
As a method for forming a concavo-convex pattern by embossing, a method for embossing using a normal hot embossing machine on which a desired concavo-convex pattern is formed, or an embossing having a desired concavo-convex pattern provided on a cooling roll of an extrusion coating apparatus, etc. It includes a so-called mechanical embossing method such as a so-called doubling embossing method, which performs embossing at the same time as forming a laminate of the resin composition (A) and carboxyl group-containing EVA (B) using a roll, or includes a foaming inhibitor or a foaming accelerator. The chemical embossing method etc. which print an ink and give an uneven | corrugated pattern by a foaming process are used.
Moreover, what has laminated structure , such as a / b / c (vinyl chloride resin) and a / b / c (vinyl chloride resin) / a , is useful as an agricultural film (sheet).
[0022]
In the present invention, each layer of the laminate has a plasticizer (naturally contained in the soft vinyl chloride resin layer), a stabilizer, a surfactant, and a crosslinkable substance (epoxy compound, polyvalent metal, inorganic or organic). Polybasic acids or salts thereof), fillers, colorants, fibers as reinforcing materials (glass fibers, carbon fibers, etc.), matting agents (talc, silica-based powders, resin fine particle powders such as polyethylene and polyurethane), etc. It can also mix | blend in the range which does not inhibit the effect of this invention.
In addition, although the thickness of a, b, and c in the laminates such as a / b, a / b / c,... As described above cannot be defined unconditionally depending on the use, etc., normally, a is 1 to 50 μm. , B is 0.1 to 10 μm, and c is arbitrarily selected from the range of about 50 to 10,000 μm.
[0023]
The laminate of the present invention thus obtained is made up of wallpaper for architectural interiors, decorative sheets for finishing furniture etc., office supplies such as desk mats, stationery such as notebooks and files using the cover of PVC leather, automobiles Can be used for interior materials, agricultural materials such as agricultural films, and daily goods (vinyl mats, umbrellas, etc.). Among them, as detailed above, interior materials such as wallpaper and decorative sheets It is very useful for agricultural films (sheets), and particularly useful for wallpaper having excellent stain resistance (decontamination).
[0024]
【Example】
Hereinafter, the method of the present invention will be specifically described with reference to examples.
Note that “%” and “parts” are based on weight unless otherwise specified.
Example 1
Eighty parts of EVOH (A1) with an ethylene content of 44 mol%, a saponification degree of 99.7 mol%, and MI of 12 g / 10 min (210 ° C, 2160 g load) were put into a twin screw extruder at about 220 ° C, and separately single screw extrusion A resin composition (A) was obtained by melting and mixing 20 parts of EVA (A2) having a vinyl acetate content of 33% melted at about 190 ° C. by a melt side feed method from the side of the twin screw extruder. (Note that the blending ratio of (A1) and (A2) above was calculated from the discharge amount).
When pellets of the resin composition (A) were observed with a scanning electron microscope, (A2) particles of about 3 μm were dispersed in (A1).
Subsequently, the resin composition (A) was formed into a film having a thickness of 20 μm with a single screw extruder.
Furthermore, an isocyanate-reactive polyurethane adhesive (AD-335A / cat-10, manufactured by Toyo Morton Co., Ltd.) was applied to 1.5 g / m 2 on one side, the thickness was 10 μm, the vinyl acetate content was 33%, and the carboxyl group content The above film was dry laminated on the adhesive surface of a 1.5 mol% maleic anhydride-modified EVA (B) sheet to prepare a laminate.
The following evaluation was performed using the obtained laminated body.
[0025]
(Decontamination)
After applying or dripping hot coffee of about 70 ° C. to a diameter of about 2 cm on the surface of the resin composition (A) layer of the laminate and leaving it to stand at 20 ° C. for 24 hours, it was wiped with exposed cotton soaked in water. The surface state of the laminate was evaluated visually as follows. In addition, it carried out similarly about the soft polyvinyl chloride resin sheet single layer.
Separately, the obtained laminate was allowed to stand at 40 ° C. for 1 day for the same evaluation.
Shoe ink (wiped with a neutral detergent), softening and aqueous magic (wiped with a commercially available detergent (Magicrin)) were also evaluated in the same manner.
(Plasticizer migration)
The laminate (10 cm × 10 cm) is placed on a flat sheet of vinyl chloride resin (plasticizer content 50%) having a thickness of 400 μm so that the resin composition (A) layer is on top , and the resin composition (A ) After placing a plasticizer-free vinyl chloride resin plate with a thickness of 3 mm and a diameter of 5 cm in contact with the surface of the layer, uniformly apply a load of 50 g / cm 2 and leave it at 70 ° C. and 90% RH for 10 days. The weight change (plasticizer migration amount) (g / m 2 ) of the later vinyl chloride resin plate was measured and evaluated as follows.
○ ---- Weight change is less than 2 g / m 2 × --- Weight change is 2 g / m 2 or more (chemical resistance)
About 1 cc of ethanol was dropped onto the surface of the resin composition (A) layer of the laminate, and the surface state after standing for 1 hour in a normal state was visually observed and evaluated as follows.
○ −−− No abnormality × −−− Swelling is observed [0027]
Example 2
In the laminate of Example 1, an isocyanate-reactive polyester-based adhesive (“Polyester LP033” manufactured by Nippon Gosei Kagaku Kogyo Co., Ltd./manufactured by Nippon Polyurethane Co., Ltd.) was further applied to the surface of the (maleic anhydride-modified) carboxyl group-containing EVA (B). "Coronate L") was applied in the same manner except that 1.5 g / m 2 was applied and a sheet of vinyl chloride resin (C) having a thickness of 400 µm (plasticizer content 50%) was laminated. Evaluated.
[0028]
Example 3
In Example 1, the same evaluation was performed except that maleic anhydride-modified EVA (B) having a vinyl acetate content of 7% and a carboxyl group content of 3 mol% was used as (B).
Example 4
In Example 2, a laminate was obtained in the same manner except that the blending weight ratio of EVOH (A1) and EVA (A2) was (A1) / (A2) = 70 parts / 30 parts. did.
[0029]
Example 5
A laminate was obtained in the same manner as in Example 1 except that EVOH (A1) was changed to EVOH having an ethylene content of 32 mol%, a saponification degree of 99.8 mol%, and MI of 12 g / 10 min (same as above). Was evaluated .
[0030]
Comparative Example 1
A laminate was obtained in the same manner as in Example 1 except that the resin composition (A) was EVOH (A1) alone, and evaluation was performed in the same manner.
Comparative Example 2
In Example 1, a laminate was obtained in the same manner except that unmodified EVA having a vinyl acetate content of 33% was used instead of (maleic anhydride-modified) carboxyl group-containing EVA (B), and a laminate was similarly evaluated. Went.
The evaluation results of Examples and Comparative Examples are shown in Table 1.
[0031]
[Table 1]
──────────────────────────────────────
Decontamination Plasticizer migration Chemical resistance ──────────────────────────────────────
No treatment After neglected treatment ──────────────────────────────────────
Example 1 ○ ○ ○ ○
〃 2 ○ ○ ○ ○
〃 3 ○ ○ ○ ○
４ 4 ○ ○ ○ ○
５ 5 ○ ○ ○ ○
──────────────────────────────────────
Comparative Example 1 ○ × × ×
〃 2 ○ × × ×
──────────────────────────────────────
[0032]
【The invention's effect】
Since the laminate of the present invention is formed by laminating a resin composition layer composed of EVOH and EVA and a carboxyl group-containing EVA layer, it is excellent in antifouling resistance (contamination removal), chemical resistance, etc. Office supplies such as finishing sheets for wallpaper and furniture, desk mats and other office supplies, stationery such as notebooks and files using the cover of PVC leather, interior materials for automobiles, agricultural materials such as agricultural films, It is also very useful for laminates such as daily goods (vinyl mats, umbrellas, etc.).
Claims (6)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12338497A JP3815849B2 (en) | 1997-04-25 | 1997-04-25 | Laminated body |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12338497A JP3815849B2 (en) | 1997-04-25 | 1997-04-25 | Laminated body |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH10296923A JPH10296923A (en) | 1998-11-10 |
| JP3815849B2 true JP3815849B2 (en) | 2006-08-30 |
Family
ID=14859254
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP12338497A Expired - Fee Related JP3815849B2 (en) | 1997-04-25 | 1997-04-25 | Laminated body |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3815849B2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001279032A (en) * | 2000-01-28 | 2001-10-10 | Sumitomo Chem Co Ltd | Resin composition and laminate |
| JP5574174B2 (en) * | 2009-09-11 | 2014-08-20 | 共同印刷株式会社 | Resin composition, sealant film, laminated film, packaging bag and tube container |
-
1997
- 1997-04-25 JP JP12338497A patent/JP3815849B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH10296923A (en) | 1998-11-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP3815849B2 (en) | Laminated body | |
| JP3781512B2 (en) | Laminated body | |
| EP0164594B1 (en) | Heat-laminatable composite film and laminated material using the same | |
| JP3815851B2 (en) | Laminated body | |
| JP3888737B2 (en) | Production method of resin composition | |
| JP3888731B2 (en) | Resin composition and use thereof | |
| JP2002096422A (en) | Multi-layer resin oriented film | |
| JP3781507B2 (en) | Laminated body | |
| JPH0255742A (en) | Preparation of foamed polyvinyl alcohol film | |
| JPS645073B2 (en) | ||
| JP6789870B2 (en) | Laminates, wallpaper and wall structures | |
| JPH09193314A (en) | Production of laminate | |
| JP4059561B2 (en) | Laminated body | |
| JPH10305535A (en) | Laminate | |
| JP3250749B2 (en) | Saponified ethylene-vinyl acetate copolymer solution and use thereof | |
| JP3040713B2 (en) | Laminate | |
| JP2975888B2 (en) | Laminate | |
| JP4077526B2 (en) | Manufacturing method of laminate | |
| JP3815824B2 (en) | Laminated body | |
| JPH09193315A (en) | Production of laminate | |
| JP3716006B2 (en) | Manufacturing method of laminated film | |
| JP3148462B2 (en) | Laminate | |
| JP4060385B2 (en) | Manufacturing method of laminate | |
| JP2975887B2 (en) | Manufacturing method of laminate | |
| JP2544753B2 (en) | Polyvinyl chloride laminated structure |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20040323 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20051202 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20051215 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20060213 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20060302 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20060428 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20060525 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20060606 |
|
| R150 | Certificate of patent or registration of utility model |
Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20090616 Year of fee payment: 3 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20090616 Year of fee payment: 3 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20100616 Year of fee payment: 4 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20100616 Year of fee payment: 4 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20110616 Year of fee payment: 5 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20120616 Year of fee payment: 6 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20120616 Year of fee payment: 6 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130616 Year of fee payment: 7 |
|
| S531 | Written request for registration of change of domicile |
Free format text: JAPANESE INTERMEDIATE CODE: R313531 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130616 Year of fee payment: 7 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130616 Year of fee payment: 7 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130616 Year of fee payment: 7 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| LAPS | Cancellation because of no payment of annual fees |