JP4128376B2 - Vinylidene chloride copolymer latex - Google Patents
Vinylidene chloride copolymer latex Download PDFInfo
- Publication number
- JP4128376B2 JP4128376B2 JP2002050220A JP2002050220A JP4128376B2 JP 4128376 B2 JP4128376 B2 JP 4128376B2 JP 2002050220 A JP2002050220 A JP 2002050220A JP 2002050220 A JP2002050220 A JP 2002050220A JP 4128376 B2 JP4128376 B2 JP 4128376B2
- Authority
- JP
- Japan
- Prior art keywords
- vinylidene chloride
- parts
- copolymer latex
- chloride copolymer
- monomer
- 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 - Lifetime
Links
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Polymerisation Methods In General (AREA)
Description
【０００１】
【発明の属する技術分野】
本発明は、両面粘着テープや粘着シート、粘着ラベルなどに使用される紙を基材とした剥離ライナーにおけるシリコーン剥離剤の下地被覆層として用いられる塩化ビニリデン系共重合ラテックスに関する。
【０００２】
【従来の技術】
塩化ビニリデン系共重合体ラテックスは、該ラテックスから得られる皮膜の優れたガス不透過性や防湿性のため、食品包装用または工業用のポリプロピレン、ポリエステル、ナイロン等のプラスチックフィルムやセロハンあるいは紙などにコートされ広く使用されている。
しかし、従来の塩化ビニリデン系共重合体ラテックスを紙基材にコート、乾燥したものは、その上にシリコーン系剥離剤をコートするシリコーン剥離剤アンダー層として使用する場合、以下の性能向上が切望されていた。
【０００３】
第一に、付加タイプシリコーン剥離剤をコートするシリコーン剥離剤アンダー層として使用するとき、取り扱い時に剥離剤が脱落して剥離性が低下しないことが切望されていた。
第二に、シリコーンコート面から剥離した後の粘着剤の残留接着力が低下しないことが切望されていた。
【０００４】
第一に対しては、特開平８−２３９５３６号公報には、ＯＨ基を含む単量体ユニット由来のＯＨ価が５〜５０ｍｇ／ｇである塩化ビニリデン系共重合体ラテックスが提案されている。しかしながら、このラテックスから得られた皮膜は高湿度雰囲気下でのシリコーン系剥離剤との密着性についてさらなる向上が望まれていた。また、特開２０００−３１９４６９号公報には、反応性乳化剤を使用して高湿度雰囲気下でのシリコーン系剥離剤との密着性を向上させる塩化ビニリデン系共重合体ラテックスが提案されている。しかし、１６０℃という高温でシリコンを硬化させたシリコーン系剥離剤との高湿度雰囲気下での密着性には問題が無いが、１１０℃でシリコンを硬化させたシリコーン系剥離剤との高湿度雰囲気下での密着性が十分でないという問題があった。
次に、第二に対しては、剥離した後の粘着剤の残留接着力が低下するメカニズムが未解明であり、未だ有効な解決方法が提案されていなかった。
【０００５】
【発明が解決しようとする課題】
本発明は、紙に塗工して防湿性、付加タイプシリコーン剥離剤の密着性が優れ、剥離後の粘着剤の残留接着力が低下しない皮膜を形成する塩化ビニリデン系共重合体ラテックスを提供するものである。
【０００６】
【課題を解決するための手段】
本発明者らは、上記の問題点に鑑み鋭意検討した結果、塩化ビニリデン単量体の量と２個以上の二重結合を有するアクリル酸エステルまたはメタクリル酸エステル単量体の量とエポキシ基を有するビニル系単量体の量、シリコーン密着性、及び、粘着剤の残留接着力との関係を明らかにして本発明を成すに至った。
すなわち、本発明は、塩化ビニリデン単量体８０〜９３質量％、２個以上の二重結合を有するアクリル酸エステルまたはメタクリル酸エステル単量体０．５〜１０質量％、エポキシ基を有するビニル系単量体１〜１０質量％、およびこれらと共重合可能なビニル系単量体１〜１８．５質量％からなるモノマー混合物を乳化重合して得られることを特徴とする塩化ビニリデン系共重合体ラテックスに関する。
【０００７】
【発明の実施の形態】
以下、本発明について詳述する。本発明における塩化ビニリデン単量体は８０〜９３質量％が適当である。塩化ビニリデン単量体が８０質量％以上では組成物から得られる皮膜の防湿性が十分であり、９３質量％以下では結晶性が適切で成膜性が良い。より好ましくは８８〜９２質量％である。
本発明者らは、シリコーン系剥離剤との高湿度雰囲気下での密着性を改良する手段として、２個以上の二重結合を有するアクリル酸エステルまたはメタクリル酸エステル単量体を特定量含有するモノマー混合物を乳化重合して得られる塩化ビニリデン系共重合体ラテックスを用いたところ、シリコーン系剥離剤との密着性向上に対して、驚くべき効果があった。このことは、塩化ビニリデン系共重合体ポリマー中に残された上記単量体由来の二重結合がシリコーン剥離剤と付加反応を起こし密着力が向上したと考えられる。
【０００８】
本発明における２個以上の二重結合を有するアクリル酸エステルまたはメタクリル酸エステル単量体とは、分子中に２個以上の二重結合を有するビニル系単量体で有り、具体例を上げれば、アリル（メタ）アクリレート、ビニル（メタ）アクリレート、１ーブテン（メタ）アクリレート、２ーブテン（メタ）アクリレート、３ーブテン（メタ）アクリレート等がある。特に好ましいのはアリル（メタ）アクリレートである。
【０００９】
本発明における２個以上の二重結合を有するアクリル酸エステルまたはメタクリル酸エステル単量体は０．５〜１０質量％である。２個以上の二重結合を有するアクリル酸エステルまたはメタクリル酸エステル単量体が０．５質量％以上で付加タイプシリコーン剥離剤との密着性が十分であり、１０質量％以下でガスや水蒸気のバリヤー性が十分である。より好ましい含有量は０．７〜４質量％である。
【００１０】
本発明者らは、剥離した後の粘着剤の残留接着力が低下するメカニズムについて次のような仮説を立てた。すなわち、塩化ビニリデン系共重合体ラテックスからの脱塩酸により発生する塩素イオンがシリコン硬化反応の触媒毒として働き、その結果、シリコーン未硬化物が生じ、そのシリコーン未硬化物が粘着剤へ移行して残留接着力が低下するという仮説である。そこで、発生した塩素イオンを減少させるため、塩素と反応する基、特に、エポキシ基を有するビニル系単量体を導入したところ、驚くべきことに、剥離した後の粘着剤の残留接着力低下を防ぐことに絶大な効果を発現した。
【００１１】
本発明におけるエポキシ基を有するビニル系単量体は１〜１０質量％である。質量１％以上で剥離後の粘着剤の残留接着力が十分であり、質量１０％以下でガスや水蒸気のバリヤー性が十分である。より好ましい含有量は３〜８質量％である。
本発明における塩化ビニリデン単量体ユニット、置換基の異なる２個以上の二重結合を有するビニル系単量体、およびエポキシ基を有するビニル系単量体と共重合可能なビニル系単量体は１〜１８．５質量％である。
【００１２】
これらのビニル系単量体は塩化ビニリデン系共重合体ラテックスやアクリル系共重合体ラテックス、ＳＢ系共重合体ラテックス等の製造に使用されているものであれば何でもよいが、例示すれば、メチル（メタ）アクリレート、エチル（メタ）アクリレート、ブチル（メタ）アクリレート、ヒドロキシエチル（メタ）アクリレート、ヒドロキシブチル（メタ）アクリレート、２ーエチルヘキシル（メタ）アクリレート等の（メタ）アクリル酸エステル類、（メタ）アクリル酸、（メタ）アクリロニトリル、塩化ビニル、スチレン等がある。
【００１３】
共重合可能なビニル系単量体は１質量％未満では高結晶性のために成膜性に問題があり、１８．５質量％を越えるとガスや水蒸気のバリヤー性が不十分になり好ましくない。より好ましい含有量は３〜１０質量％である。
塩化ビニリデン系共重合体ラテックスを有効固形分で５ｇ／ｍ2コートしたときの水蒸気透過率は１００ｇ／（ｍ2・２４時間）以下が好まし。１００ｇ／（ｍ2・２４時間）以上では、防湿性が不十分であり、シリコーン剥離剤アンダー層として使用する場合、湿度等の外気条件により寸法変化やカールなどが発生してしまう。より好ましくは５０ｇ／（ｍ2・２４時間）以下である。
【００１４】
本発明の塩化ビニリデン系共重合体ラテックスは、主成分である共重合体ラテックスの他に、本発明の目的を損なわない範囲で各種の添加剤を含有させることができる。添加剤の例としては、水酸化ナトリウム、アンモニア水等のｐＨ調節剤、炭酸カルシウム、クレー、タルク、シリカ、合成樹脂微小粒等の充填剤、耐ブロッキング剤、艶消し剤、シリコーン、ワックス類等の消泡剤、界面活性剤、カーボンブラック等の帯電防止剤、ポリビニルアルコール、水溶性セルロース誘導体、アクリル酸系共重合体塩等の増粘剤等が挙げられる。
【００１５】
本発明の塩化ビニリデン系共重合体ラテックスの製造法については、公知の乳化重合の方法が問題なく応用可能である。該ラテックスの製造において、公知の開始剤が使用可能であるが、より好ましくは過硫酸アンモニウム、ナトリウム、カリウム等の過硫酸塩である。更に、本発明の塩化ビニリデン系共重合体ラテックスには、撹拌機付きの容器に入れて撹拌しつつ、上記の添加剤をそのまま、または水に溶解または分散させて追加することができる。
【００１６】
本発明の塩化ビニリデン系共重合体ラテックスをコートする方法としてはエアーナイフコーター、バーコーター、ロールコーター等の公知の方法を用いることができる。コートした後の乾燥は、８０℃〜１９０℃の範囲で２０秒から５分間おこなうのが好ましい。また、コート量は有効固形分で３〜２５ｇ／ｍ2が好ましい。３ｇ／ｍ2未満では防湿性が不十分となり得られた剥離紙の寸法安定性が乏しい場合がある。２５ｇ／ｍ2を越えると古紙回収プラント内の離解行程において解離性が低下する場合がある。
塩化ビニリデン系共重合体ラテックス塗膜の上に設けるシリコーン系剥離剤層の厚みは従来の技術に準じることができ、０．０５〜５μｍが一般的である。
【００１７】
【実施例】
以下、実施例などを用いて本発明を更に詳細に説明する。なお、以下の実施例において、剥離紙の作成方法、シリコーン密着性、残留接着力、防湿性の測定方法は以下に記載する方法により行い、実施例中の部数は特に断らない限り質量部である。
（１） 剥離紙の作成方法
坪量１０４．２ｇの塗工紙に、塩化ビニリデン共重合体ラテックスをメイヤーバーで有効固形分が５ｇ／ｍ2となるようにコートし、１００℃で１分乾燥後、４０℃で２日養生してラテックスコート紙を得た。この上に付加タイプシリコーンＫＮＳ３０５／ＣＡＴ−ＰＬ−５６（信越シリコーン製）をメイヤーバーで３ｇ／ｍ2コートして、１１０℃で３０秒加熱硬化して剥離紙を得た。
【００１８】
（２）シリコーン密着性の測定方法
上記（１）で得た剥離紙を４０℃９０％ＲＨ雰囲気下に４日放置した後、シリコーン面を指先でこすってシリコーン脱落の有無を判定した。
＜判定基準＞ ○：脱落無し ×：脱落あり
【００１９】
（３）残留接着率の測定方法
上記（１）で得た剥離紙にルミラー３１Bテープを張り合わせ、０．００２MPaの荷重が掛かるように重りを載せ、７０℃で２０時間に渡って圧着処理を行った。その後、テープを剥ぎ取り、ＪＩＳ Ｚ０２３７法にて処理したＳＵＳ３０４製の金属板の上に、しわができないようにローラーで荷重０．２MPaが掛かるように約３００mm/minの速度で一往復させ張り合わせた。張り合わせた後、２０〜４０分の間に下記の条件で、引っ張り試験を行いテープとＳＵＳ版との剥離強度を測定した。
【００２０】
（引っ張り試験条件）
測定機械：ＡＧＳ−５００Ｇ（島津製作所（株）製）
測定雰囲気：２０℃、５５％ＲＨ
引張速度：３００ｍｍ／分
残留接着力は次式により求め、下記の基準により判定した。
（剥離紙接着後の剥離強度）／（剥離紙接着前の剥離強度）×１００
○：残留接着力９５％以上
△：残留接着力９０％以上〜９５％未満
×：残留接着力９０％未満
【００２１】
（４）防湿性の測定方法
上記（１）で得た剥離紙の透湿量をＪＩＳ−Ｚ−０２０８（カップ法）にて測定した。
測定条件；４０℃ ９０％ＲＨ
【００２２】
【実施例１】
塩化ビニリデン（ＶＤＣ）９０部、メチルアクリレート（ＭＡ）４部、ヒドロキシエチルアクリレート（ＨＥＡ）２部、アリルメタクリレート（ＡＭＡ）１部、グリシジルメタクリレート（ＧＭＡ）３部からなる単量体混合物の内の１０質量部をイオン交換水１００部、ドデシルベンゼンスルフォン酸ナトリウム０．１部とオートクレーブ中で混合し、過硫酸ナトリウム０．０７質量部を定量連続添加して５０℃で２時間シード重合を行った。続いてエーテルサルフェート型の反応性乳化剤ＳＥ１０２５Ａ（旭電化社製）２．０質量部と単量体混合物の残り９０質量部を５０℃で１０時間定量連続添加し、更に５０℃で１８時間重合した。重合収率は９９．９％であった。重合収率はほぼ１００％なので、共重合体の組成は仕込比にほぼ等しい。
得られた塩化ビニリデン系共重合体ラテックスについて、上記（１）の方法により剥離紙を作成した。この剥離紙について物性測定した結果を表１に示す。
【００２３】
【実施例２】
単量体混合物の組成をＶＤＣ９３部、ＭＡ１部、ＨＥＡ２部、ＡＭＡ１部、ＧＭＡ３部に変えて、以下実施例１と同様に実施した。重合収率は９９．９％であった。
得られた塩化ビニリデン系共重合体ラテックスについて、上記（１）の方法により剥離紙を作成した。この剥離紙について物性測定した結果を表１に示す。
【００２４】
【実施例３】
単量体混合物の組成をＶＤＣ８０部、ＭＡ１４部、ＨＥＡ２部、ＡＭＡ１部、ＧＭＡ３部に変えて、以下実施例１と同様に実施した。重合収率は９９．９％であった。
得られた塩化ビニリデン系共重合体ラテックスについて、上記（１）の方法により剥離紙を作成した。この剥離紙について物性測定した結果を表１に示す。
【００２５】
【実施例４】
単量体混合物の組成をＶＤＣ８１部、ＭＡ４部、ＨＥＡ２部、ＡＭＡ１０部、ＧＭＡ３部に変えて、以下実施例１と同様に実施した。重合収率は９９．９％であった。
得られた塩化ビニリデン系共重合体ラテックスについて、上記（１）の方法により剥離紙を作成した。この剥離紙について物性測定した結果を表１に示す。
【００２６】
【実施例５】
単量体混合物の組成をＶＤＣ９０部、ＭＡ４．５部、ＨＥＡ２部、ＡＭＡ０．５部、ＧＭＡ３部に変えて、以下実施例１と同様に実施した。重合収率は９９．９％であった。
得られた塩化ビニリデン系共重合体ラテックスについて、上記（１）の方法により剥離紙を作成した。この剥離紙について物性測定した結果を表１に示す。
【００２７】
【実施例６】
単量体混合物の組成をＶＤＣ８１部、ＭＡ６部、ＨＥＡ２部、ＡＭＡ１部、ＧＭＡ１０部に変えて、以下実施例１と同様に実施した。重合収率は９９．９％であった。
得られた塩化ビニリデン系共重合体ラテックスについて、上記（１）の方法により剥離紙を作成した。この剥離紙について物性測定した結果を表１に示す。
【００２８】
【実施例７】
単量体混合物の組成をＶＤＣ９０部、ＭＡ６部、ＨＥＡ２部、ＡＭＡ１部、ＧＭＡ１部に変えて、以下実施例１と同様に実施した。重合収率は９９．９％であった。
得られた塩化ビニリデン系共重合体ラテックスについて、上記（１）の方法により剥離紙を作成した。この剥離紙について物性測定した結果を表１に示す。
【００２９】
【比較例１】
単量体混合物の組成をＶＤＣ７８部、ＭＡ１６部、ＨＥＡ２部、ＡＭＡ１部、ＧＭＡ３部に変えて、以下実施例１と同様に実施した。重合収率は９９．９％であった。
得られた塩化ビニリデン系共重合体ラテックスについて、上記（１）の方法により剥離紙を作成した。この剥離紙について物性測定した結果を表１に示す。
【００３０】
【比較例２】
単量体混合物の組成をＶＤＣ９４部、ＭＡ１部、ＨＥＡ１部、ＡＭＡ１部、ＧＭＡ３部に変えて、以下実施例１と同様に実施した。重合収率は９９．９％であった。
得られた塩化ビニリデン系共重合体ラテックスについて、上記（１）の方法により剥離紙を作成した。この剥離紙について物性測定した結果を表１に示す。
【００３１】
【比較例３】
単量体混合物の組成をＶＤＣ８１部、ＭＡ３部、ＨＥＡ２部、ＡＭＡ１１部、ＧＭＡ３部に変えて、以下実施例１と同様に実施した。重合収率は９９．９％であった。
得られた塩化ビニリデン系共重合体ラテックスについて、上記（１）の方法により剥離紙を作成した。この剥離紙について物性測定した結果を表１に示す。
【００３２】
【比較例４】
単量体混合物の組成をＶＤＣ９０部、ＭＡ４．７部、ＨＥＡ２部、ＡＭＡ０．３部、ＧＭＡ３部に変えて、以下実施例１と同様に実施した。重合収率は９９．９％であった。
得られた塩化ビニリデン系共重合体ラテックスについて、上記（１）の方法により剥離紙を作成した。この剥離紙について物性測定した結果を表１に示す。
【００３３】
【比較例５】
単量体混合物の組成をＶＤＣ８３部、ＭＡ３部、ＨＥＡ２部、ＡＭＡ１部、ＧＭＡ１１部に変えて、以下実施例１と同様に実施した。重合収率は９９．９％であった。
得られた塩化ビニリデン系共重合体ラテックスについて、上記（１）の方法により剥離紙を作成した。この剥離紙について物性測定した結果を表１に示す。
【００３４】
【比較例６】
単量体混合物の組成をＶＤＣ９０部、ＭＡ６．５部、ＨＥＡ２部、ＡＭＡ１部、ＧＭＡ０．５部に変えて、以下実施例１と同様に実施した。重合収率は９９．９％であった。
得られた塩化ビニリデン系共重合体ラテックスについて、上記（１）の方法により剥離紙を作成した。この剥離紙について物性測定した結果を表１に示す。
【００３５】
【表１】
【発明の効果】
本発明の塩化ビニリデン系共重合体ラテックスは、紙基材にコートして、シリコーン剥離剤との密着性に優れ、剥離後の粘着剤接着力の低下が無く、優れた防湿性を有する皮膜を形成するものであり、剥離材用の下塗り剤として極めて有用なものである。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a vinylidene chloride copolymer latex used as an undercoat layer for a silicone release agent in a release liner based on paper used for double-sided pressure-sensitive adhesive tapes, pressure-sensitive adhesive sheets, pressure-sensitive adhesive labels, and the like.
[0002]
[Prior art]
Vinylidene chloride copolymer latex is used for food packaging or industrial plastic films such as polypropylene, polyester, nylon, cellophane, paper, etc. because of the excellent gas impermeability and moisture resistance of the film obtained from the latex. Coated and widely used.
However, when the conventional vinylidene chloride copolymer latex is coated on a paper substrate and dried, the following performance improvement is eagerly desired when used as a silicone release agent underlayer that coats a silicone release agent on it. It was.
[0003]
First, when used as a silicone release agent under layer for coating an addition type silicone release agent, it has been eagerly desired that the release agent will not fall off during handling and the releasability will not deteriorate.
Secondly, it has been eagerly desired that the residual adhesive strength of the pressure-sensitive adhesive after peeling from the silicone-coated surface does not decrease.
[0004]
First, JP-A-8-239536 proposes a vinylidene chloride copolymer latex having an OH value of 5 to 50 mg / g derived from a monomer unit containing an OH group. However, it has been desired that the film obtained from the latex be further improved in adhesion with the silicone-based release agent in a high humidity atmosphere. Japanese Patent Laid-Open No. 2000-319469 proposes a vinylidene chloride copolymer latex that uses a reactive emulsifier to improve adhesion with a silicone-based release agent in a high-humidity atmosphere. However, there is no problem with the adhesion in a high humidity atmosphere with a silicone-based release agent that has cured silicon at a high temperature of 160 ° C., but a high humidity atmosphere with a silicone-based release agent that has cured silicon at 110 ° C. There was a problem that the adhesion below was not sufficient.
Next, for the second, the mechanism by which the residual adhesive strength of the pressure-sensitive adhesive after peeling is lowered has not been elucidated, and no effective solution has been proposed yet.
[0005]
[Problems to be solved by the invention]
The present invention provides a vinylidene chloride copolymer latex that forms a film that is coated on paper and has excellent moisture resistance and adhesion of an additional type silicone release agent and does not reduce the residual adhesive strength of the adhesive after release. Is.
[0006]
[Means for Solving the Problems]
As a result of intensive studies in view of the above problems, the present inventors have determined the amount of the vinylidene chloride monomer, the amount of the acrylate or methacrylate ester monomer having two or more double bonds, and the epoxy group. The present invention was accomplished by clarifying the relationship between the amount of the vinyl-based monomer, the silicone adhesion, and the residual adhesive strength of the pressure-sensitive adhesive.
That is, the present invention relates to vinylidene chloride monomer 80 to 93% by mass, acrylic ester or methacrylic ester monomer 0.5 to 10% by mass having two or more double bonds, and vinyl group having an epoxy group. A vinylidene chloride copolymer obtained by emulsion polymerization of a monomer mixture comprising 1 to 10% by mass of a monomer and 1 to 18.5% by mass of a vinyl monomer copolymerizable therewith Regarding latex.
[0007]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the present invention will be described in detail. 80-93 mass% is suitable for the vinylidene chloride monomer in this invention. When the vinylidene chloride monomer is 80% by mass or more, the film obtained from the composition has sufficient moisture resistance, and when it is 93% by mass or less, the crystallinity is appropriate and the film formability is good. More preferably, it is 88-92 mass%.
The inventors of the present invention contain a specific amount of an acrylate or methacrylate monomer having two or more double bonds as a means for improving adhesion with a silicone-based release agent in a high humidity atmosphere. When a vinylidene chloride copolymer latex obtained by emulsion polymerization of the monomer mixture was used, it had a surprising effect on improving the adhesion to the silicone release agent. This is considered that the double bond derived from the monomer left in the vinylidene chloride copolymer polymer caused an addition reaction with the silicone release agent, thereby improving the adhesion.
[0008]
The acrylic acid ester or methacrylic acid ester monomer having two or more double bonds in the present invention is a vinyl monomer having two or more double bonds in the molecule. , Allyl (meth) acrylate, vinyl (meth) acrylate, 1-butene (meth) acrylate, 2-butene (meth) acrylate, 3-butene (meth) acrylate, and the like. Particularly preferred is allyl (meth) acrylate.
[0009]
The acrylic acid ester or methacrylic acid ester monomer having two or more double bonds in the present invention is 0.5 to 10% by mass. Adhesiveness with an addition type silicone release agent is sufficient when the acrylic acid ester or methacrylic acid ester monomer having two or more double bonds is 0.5% by mass or more. The barrier property is sufficient. A more preferable content is 0.7 to 4% by mass.
[0010]
The present inventors made the following hypothesis about the mechanism by which the residual adhesive strength of the pressure-sensitive adhesive after peeling is reduced. That is, chlorine ions generated by dehydrochlorination from the vinylidene chloride copolymer latex act as a catalyst poison for the silicon curing reaction, resulting in an uncured silicone product, and the uncured silicone product is transferred to the adhesive. This is a hypothesis that the residual adhesive strength is reduced. Therefore, in order to reduce the generated chlorine ions, when a vinyl monomer having a group that reacts with chlorine, particularly an epoxy group, was introduced, surprisingly, the residual adhesive strength of the adhesive after peeling was reduced. It had a tremendous effect on prevention.
[0011]
The vinyl-type monomer which has an epoxy group in this invention is 1-10 mass%. When the mass is 1% or more, the residual adhesive strength of the pressure-sensitive adhesive after peeling is sufficient, and when the mass is 10% or less, the barrier property of gas or water vapor is sufficient. A more preferable content is 3 to 8% by mass.
In the present invention, vinylidene chloride monomer unit, vinyl monomer having two or more double bonds with different substituents, and vinyl monomer copolymerizable with vinyl monomer having epoxy group are: It is 1-18.5 mass%.
[0012]
These vinyl monomers may be anything as long as they are used for the production of vinylidene chloride copolymer latex, acrylic copolymer latex, SB copolymer latex, and the like. (Meth) acrylates such as (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, hydroxyethyl (meth) acrylate, hydroxybutyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, (meta ) Acrylic acid, (meth) acrylonitrile, vinyl chloride, styrene and the like.
[0013]
If the copolymerizable vinyl monomer is less than 1% by mass, there is a problem in film formability due to high crystallinity, and if it exceeds 18.5% by mass, the barrier property of gas and water vapor becomes insufficient. . A more preferable content is 3 to 10% by mass.
The water vapor transmission rate is preferably 100 g / (m 2 · 24 hours) or less when the vinylidene chloride copolymer latex is coated at an effective solid content of 5 g / m 2 . When it is 100 g / (m 2 · 24 hours) or more, the moisture resistance is insufficient, and when used as a silicone release agent under layer, dimensional changes, curls, and the like occur depending on outside air conditions such as humidity. More preferably, it is 50 g / (m 2 · 24 hours) or less.
[0014]
The vinylidene chloride copolymer latex of the present invention can contain various additives in addition to the copolymer latex as the main component within a range not impairing the object of the present invention. Examples of additives include pH regulators such as sodium hydroxide and aqueous ammonia, fillers such as calcium carbonate, clay, talc, silica, synthetic resin fine particles, anti-blocking agents, matting agents, silicone, waxes, etc. Anti-foaming agents, surfactants, antistatic agents such as carbon black, thickeners such as polyvinyl alcohol, water-soluble cellulose derivatives, and acrylic acid copolymer salts.
[0015]
As a method for producing the vinylidene chloride copolymer latex of the present invention, a known emulsion polymerization method can be applied without any problem. In the production of the latex, known initiators can be used, and more preferred are persulfates such as ammonium persulfate, sodium and potassium. Furthermore, the above-mentioned additives can be added to the vinylidene chloride copolymer latex of the present invention as it is or dissolved or dispersed in water while stirring in a container equipped with a stirrer.
[0016]
As a method for coating the vinylidene chloride copolymer latex of the present invention, a known method such as an air knife coater, a bar coater, or a roll coater can be used. Drying after coating is preferably performed in the range of 80 ° C. to 190 ° C. for 20 seconds to 5 minutes. The coating amount is preferably 3 to 25 g / m 2 in terms of effective solid content. If it is less than 3 g / m 2 , the moisture resistance may be insufficient and the resulting release paper may have poor dimensional stability. If it exceeds 25 g / m 2 , the dissociation property may decrease in the disaggregation process in the used paper recovery plant.
The thickness of the silicone release agent layer provided on the vinylidene chloride copolymer latex coating film can be in accordance with conventional techniques, and is generally 0.05 to 5 μm.
[0017]
【Example】
Hereinafter, the present invention will be described in more detail with reference to examples. In the following examples, the method for preparing release paper, silicone adhesion, residual adhesive strength, and moisture resistance are measured by the methods described below, and the parts in the examples are parts by mass unless otherwise specified. .
(1) Release paper preparation method A coated paper having a basis weight of 104.2 g is coated with a vinylidene chloride copolymer latex with a Mayer bar so that the effective solid content is 5 g / m 2 and dried at 100 ° C. for 1 minute. Thereafter, it was cured at 40 ° C. for 2 days to obtain a latex-coated paper. On top of this, addition type silicone KNS305 / CAT-PL-56 (manufactured by Shin-Etsu Silicone) was coated at 3 g / m 2 with a Mayer bar and heat cured at 110 ° C. for 30 seconds to obtain a release paper.
[0018]
(2) Method for measuring silicone adhesion The release paper obtained in (1) above was left in an atmosphere of 40 ° C. and 90% RH for 4 days, and then the silicone surface was rubbed with a fingertip to determine whether or not silicone had fallen off.
<Criteria> ○: No dropout ×: With dropout [0019]
(3) Measuring method of residual adhesion rate Lumirror 31B tape is attached to the release paper obtained in (1) above, a weight is placed so that a load of 0.002 MPa is applied, and pressure bonding is performed at 70 ° C. for 20 hours. It was. After that, the tape was peeled off and pasted on a metal plate made of SUS304 treated by JIS Z0237 method so as to reciprocate at a speed of about 300 mm / min so that a load of 0.2 MPa was applied with a roller so as not to wrinkle. . After bonding, a tensile test was performed between 20 and 40 minutes under the following conditions to measure the peel strength between the tape and the SUS plate.
[0020]
(Tensile test conditions)
Measuring machine: AGS-500G (manufactured by Shimadzu Corporation)
Measurement atmosphere: 20 ° C., 55% RH
Tensile speed: 300 mm / min The residual adhesive force was determined by the following formula and judged according to the following criteria.
(Peeling strength after adhesion of release paper) / (Peeling strength before adhesion of release paper) × 100
○: Residual adhesive strength 95% or more Δ: Residual adhesive strength 90% or more to less than 95% ×: Residual adhesive strength less than 90%
(4) Measuring method of moisture resistance The moisture permeability of the release paper obtained in the above (1) was measured by JIS-Z-0208 (cup method).
Measurement conditions: 40 ° C 90% RH
[0022]
[Example 1]
10 of the monomer mixture consisting of 90 parts vinylidene chloride (VDC), 4 parts methyl acrylate (MA), 2 parts hydroxyethyl acrylate (HEA), 1 part allyl methacrylate (AMA) and 3 parts glycidyl methacrylate (GMA) A mass part was mixed with 100 parts of ion-exchanged water and 0.1 part of sodium dodecylbenzenesulfonate in an autoclave, 0.07 part by mass of sodium persulfate was continuously added, and seed polymerization was carried out at 50 ° C. for 2 hours. Subsequently, 2.0 parts by mass of ether sulfate type reactive emulsifier SE1025A (Asahi Denka Co., Ltd.) and the remaining 90 parts by mass of the monomer mixture were continuously added at 50 ° C. for 10 hours, and further polymerized at 50 ° C. for 18 hours. . The polymerization yield was 99.9%. Since the polymerization yield is almost 100%, the composition of the copolymer is almost equal to the charge ratio.
With respect to the obtained vinylidene chloride copolymer latex, a release paper was prepared by the above method (1). Table 1 shows the results of measuring physical properties of this release paper.
[0023]
[Example 2]
The composition of the monomer mixture was changed to 93 parts of VDC, 1 part of MA, 2 parts of HEA, 1 part of AMA, 3 parts of GMA, and the same procedure as in Example 1 was carried out. The polymerization yield was 99.9%.
With respect to the obtained vinylidene chloride copolymer latex, a release paper was prepared by the above method (1). Table 1 shows the results of measuring physical properties of this release paper.
[0024]
[Example 3]
The composition of the monomer mixture was changed to 80 parts of VDC, 14 parts of MA, 2 parts of HEA, 1 part of AMA, 3 parts of GMA, and the same procedure as in Example 1 was carried out. The polymerization yield was 99.9%.
With respect to the obtained vinylidene chloride copolymer latex, a release paper was prepared by the above method (1). Table 1 shows the results of measuring physical properties of this release paper.
[0025]
[Example 4]
The composition of the monomer mixture was changed to 81 parts of VDC, 4 parts of MA, 2 parts of HEA, 10 parts of AMA, and 3 parts of GMA, and then the same procedure as in Example 1 was performed. The polymerization yield was 99.9%.
With respect to the obtained vinylidene chloride copolymer latex, a release paper was prepared by the above method (1). Table 1 shows the results of measuring physical properties of this release paper.
[0026]
[Example 5]
The composition of the monomer mixture was changed to 90 parts of VDC, 4.5 parts of MA, 2 parts of HEA, 0.5 part of AMA, and 3 parts of GMA, and then the same procedure as in Example 1 was performed. The polymerization yield was 99.9%.
With respect to the obtained vinylidene chloride copolymer latex, a release paper was prepared by the above method (1). Table 1 shows the results of measuring physical properties of this release paper.
[0027]
[Example 6]
The composition of the monomer mixture was changed to 81 parts of VDC, 6 parts of MA, 2 parts of HEA, 1 part of AMA, and 10 parts of GMA, and the same procedure as in Example 1 was followed. The polymerization yield was 99.9%.
With respect to the obtained vinylidene chloride copolymer latex, a release paper was prepared by the above method (1). Table 1 shows the results of measuring physical properties of this release paper.
[0028]
[Example 7]
The composition of the monomer mixture was changed to 90 parts of VDC, 6 parts of MA, 2 parts of HEA, 1 part of AMA, and 1 part of GMA. The polymerization yield was 99.9%.
With respect to the obtained vinylidene chloride copolymer latex, a release paper was prepared by the above method (1). Table 1 shows the results of measuring physical properties of this release paper.
[0029]
[Comparative Example 1]
The composition of the monomer mixture was changed to 78 parts of VDC, 16 parts of MA, 2 parts of HEA, 1 part of AMA, 3 parts of GMA, and the same procedure as in Example 1 was carried out. The polymerization yield was 99.9%.
With respect to the obtained vinylidene chloride copolymer latex, a release paper was prepared by the above method (1). Table 1 shows the results of measuring physical properties of this release paper.
[0030]
[Comparative Example 2]
The composition of the monomer mixture was changed to 94 parts of VDC, 1 part of MA, 1 part of HEA, 1 part of AMA, 3 parts of GMA, and the same procedure as in Example 1 was carried out. The polymerization yield was 99.9%.
With respect to the obtained vinylidene chloride copolymer latex, a release paper was prepared by the above method (1). Table 1 shows the results of measuring physical properties of this release paper.
[0031]
[Comparative Example 3]
The composition of the monomer mixture was changed to 81 parts of VDC, 3 parts of MA, 2 parts of HEA, 11 parts of AMA, 3 parts of GMA, and the same procedure as in Example 1 was performed. The polymerization yield was 99.9%.
With respect to the obtained vinylidene chloride copolymer latex, a release paper was prepared by the above method (1). Table 1 shows the results of measuring physical properties of this release paper.
[0032]
[Comparative Example 4]
The composition of the monomer mixture was changed to 90 parts of VDC, 4.7 parts of MA, 2 parts of HEA, 0.3 part of AMA, and 3 parts of GMA, and then the same procedure as in Example 1 was performed. The polymerization yield was 99.9%.
With respect to the obtained vinylidene chloride copolymer latex, a release paper was prepared by the above method (1). Table 1 shows the results of measuring physical properties of this release paper.
[0033]
[Comparative Example 5]
The composition of the monomer mixture was changed to 83 parts of VDC, 3 parts of MA, 2 parts of HEA, 1 part of AMA, and 11 parts of GMA, and the same procedure as in Example 1 was followed. The polymerization yield was 99.9%.
With respect to the obtained vinylidene chloride copolymer latex, a release paper was prepared by the above method (1). Table 1 shows the results of measuring physical properties of this release paper.
[0034]
[Comparative Example 6]
The composition of the monomer mixture was changed to 90 parts of VDC, 6.5 parts of MA, 2 parts of HEA, 1 part of AMA, and 0.5 part of GMA, and then the same procedure as in Example 1 was performed. The polymerization yield was 99.9%.
With respect to the obtained vinylidene chloride copolymer latex, a release paper was prepared by the above method (1). Table 1 shows the results of measuring physical properties of this release paper.
[0035]
[Table 1]
【The invention's effect】
The vinylidene chloride copolymer latex of the present invention is coated on a paper substrate, has excellent adhesion to a silicone release agent, has no decrease in adhesive adhesive strength after release, and has a film having excellent moisture resistance. It is formed and is extremely useful as a primer for a release material.
Claims (2)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002050220A JP4128376B2 (en) | 2002-02-26 | 2002-02-26 | Vinylidene chloride copolymer latex |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002050220A JP4128376B2 (en) | 2002-02-26 | 2002-02-26 | Vinylidene chloride copolymer latex |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2003246821A JP2003246821A (en) | 2003-09-05 |
| JP4128376B2 true JP4128376B2 (en) | 2008-07-30 |
Family
ID=28662518
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2002050220A Expired - Lifetime JP4128376B2 (en) | 2002-02-26 | 2002-02-26 | Vinylidene chloride copolymer latex |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP4128376B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105294913A (en) * | 2015-11-25 | 2016-02-03 | 海南赛诺实业有限公司 | PVDC copolymerization emulsion for flame-retardant carpets, preparation method and applications thereof |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4486340B2 (en) * | 2003-10-22 | 2010-06-23 | 本田技研工業株式会社 | Method for producing fuel cell electrode-membrane assembly |
| CN101528788B (en) * | 2006-10-25 | 2012-09-26 | 陶氏环球技术有限责任公司 | Vinylidene chloride copolymer and preparation method thereof for displaying improvements in bubble stability |
| CN103059200B (en) * | 2012-12-26 | 2015-12-23 | 海南聚能功能薄膜技术开发有限公司 | Glassine paper coating PVDC emulsion and its preparation method and application |
| CN105669890B (en) * | 2016-02-02 | 2017-07-28 | 惠州市惠阳区嘉泰涂料有限公司 | Anticorrosive metal paint polyvinylidene emulsions and preparation method and application |
-
2002
- 2002-02-26 JP JP2002050220A patent/JP4128376B2/en not_active Expired - Lifetime
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105294913A (en) * | 2015-11-25 | 2016-02-03 | 海南赛诺实业有限公司 | PVDC copolymerization emulsion for flame-retardant carpets, preparation method and applications thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2003246821A (en) | 2003-09-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP6133331B2 (en) | Aqueous polymer dispersion that can be used as a tackifier for adhesives that can be produced by emulsion polymerization based on C1-C20-alkyl (meth) acrylates | |
| EP2580254B1 (en) | Multistage preparation of aqueous polymer dispersions for producing composite films | |
| JP5755241B2 (en) | Cold-sealed and resealable packaging and composition for its manufacture | |
| US11015091B2 (en) | Use of a single-component laminating adhesive for composite film lamination | |
| US8722829B2 (en) | Cold-sealed, recloseable pack and composition for producing it | |
| EP3725485B1 (en) | Method of recycling film-to-film laminates | |
| AU2014243273A1 (en) | Use of a polymer dispersion for cold sealing | |
| JPH10265534A (en) | Aqueous poly (meth)acrylate dispersion, heat-sealably coated substrate, production of polymer dispersion and its use | |
| WO2007007499A1 (en) | (meth)acrylic emulsion type pressure-sensitive adhesive composition and pressure-sensitive adhesive sheet | |
| JP2019506467A (en) | Aqueous polymer dispersions with low emulsifier content for the production of composite films | |
| JP4128376B2 (en) | Vinylidene chloride copolymer latex | |
| JP6789967B6 (en) | Oxazoline-containing aqueous polymer dispersion for laminating composite films | |
| US20090020225A1 (en) | Autoadhesive | |
| JP3560380B2 (en) | Vinylidene chloride copolymer latex | |
| WO2013092864A1 (en) | Synthetic cold seal adhesive | |
| JPS61266420A (en) | Aqueous dispersion composition | |
| EP0590886B1 (en) | Laminating construction adhesive compositions with improved performance | |
| JP2004203997A (en) | Removable type aqueous pressure-sensitive adhesive composition | |
| US9062233B2 (en) | Multistage preparation of aqueous polymer dispersions for producing composite films | |
| EP3286274B1 (en) | Aqueous cold seal adhesive | |
| JP3221689B2 (en) | Removable pressure-sensitive adhesive aqueous composition | |
| JP2003238924A (en) | Delayed tack type sticking agent composition and sticking label | |
| JP4183334B2 (en) | Vinylidene chloride copolymer latex | |
| JP2001131503A (en) | Pressure-sensitive adhesive sheet | |
| JP2000355680A (en) | Production of molded product |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20050221 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20071219 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20080219 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20080321 |
|
| 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: 20080513 |
|
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20080514 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20110523 Year of fee payment: 3 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 4128376 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20110523 Year of fee payment: 3 |
|
| 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: 20110523 Year of fee payment: 3 |
|
| 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: 20110523 Year of fee payment: 3 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20120523 Year of fee payment: 4 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20120523 Year of fee payment: 4 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130523 Year of fee payment: 5 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130523 Year of fee payment: 5 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20140523 Year of fee payment: 6 |
|
| S111 | Request for change of ownership or part of ownership |
Free format text: JAPANESE INTERMEDIATE CODE: R313111 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| S531 | Written request for registration of change of domicile |
Free format text: JAPANESE INTERMEDIATE CODE: R313531 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| EXPY | Cancellation because of completion of term |