JP4142147B2 - Release paper - Google Patents
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- JP4142147B2 JP4142147B2 JP05588398A JP5588398A JP4142147B2 JP 4142147 B2 JP4142147 B2 JP 4142147B2 JP 05588398 A JP05588398 A JP 05588398A JP 5588398 A JP5588398 A JP 5588398A JP 4142147 B2 JP4142147 B2 JP 4142147B2
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【０００１】
【発明の属する技術分野】
本発明は、剥離紙に関し、更に詳しくは、グラシン紙等を基紙とし、離型性、リサイクル性、（塗布される離型剤に対する）耐溶剤性等に優れた剥離紙に関する。
【０００２】
【従来の技術】
従来より、剥離紙は、粘着ラベル、粘着テープ、粘着シート等の基材として多方面に利用されている。
かかる剥離紙は、一般的には、基紙の表面に離型剤の層を設けた構成であり、通常はかかる離型剤が紙の中に侵透せずに基紙の表面で良好な離型剤の層を形成できるように、その界面にポリエチレン等のポリオレフィン系樹脂層を設けたり、或いはポリビニルアルコール系樹脂、カルボキシメチルセルロース、ガゼイン、ポリ酢酸ビニルエマルジョン等のバリヤー層を設けることが行われている。
【０００３】
【発明が解決しようとする問題点】
しかしながら、ポリオレフィン系樹脂層を設けた場合には、バリヤー効果は十分であるが、最近の紙のリサイクルを考えると該樹脂の処理が大きな問題となる。一方、従来のポリビニルアルコール系樹脂等による層の場合には、リサイクル問題はクリアするもののバリヤー性能が十分ではなく、リサイクル性とバリヤー性を同時に満足するバリヤー層が設けられ、更には離型性にも優れた剥離紙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、本発明者がかかる事情に鑑みて鋭意検討した結果、基紙に、カルボキシル基含有ポリビニルアルコール系樹脂１００重量部に対して、親水基含有フッ素系化合物を０．０１〜５．０重量部配合した樹脂組成物（ａ）が塗工されてなる剥離紙であって、特に該親水基含有フッ素系化合物が下記一般式（１）で表される化合物であるとき、本発明の作用効果を顕著に得ることを見いだし本発明を完成するに至った。
【化２】
ＣnＦ2n+1−(Ｘ)l−(ＣＨ2−ＣＨ2−Ｏ)m−Ｈ ・・・（１）
（但し、Ｘは、−ＳＯ2ＮＲ（アルキル基）−またはカルボニル基で、
ｎは１〜４０の整数で、ｍは１〜１００の整数で、ｌは０または１）
【０００５】
【発明の実施の形態】
本発明を以下に詳しく説明する。
本発明の剥離紙は、カルボキシル基含有ポリビニルアルコール系樹脂及び親水基含有フッ素系化合物からなる樹脂組成物（ａ）が基紙に塗工されてなるもので、かかるカルボキシル基含有ポリビニルアルコール系樹脂としては、カルボキシル基を含有しているポリビニルアルコール系樹脂であれば特に限定されず、その製造も特に限定されず、例えば、カルボキシル基を有する不飽和単量体及びビニルエステル系化合物より共重合体を得た後、該共重合体をケン化する方法、カルボキシル基を有するポリビニルアルコール系樹脂にオキシアルキレン基を有する単量体をグラフト重合させる方法等が挙げられるが、前者の方法が樹脂の製造面、性能面から実用的である。
以下、前者の方法について具体的に説明する。
【０００６】
カルボキシル基を有する不飽和単量体としては、エチレン性不飽和ジカルボン酸（マレイン酸、フマル酸、イタコン酸）、又はエチレン性不飽和カルボン酸モノエステル（マレイン酸モノアルキルエステル、フマル酸モノアルキルエステル、イタコン酸モノアルキルエステル）、又はエチレン性不飽和ジカルボン酸ジエステル（マレイン酸ジアルキルエステル、フマル酸ジアルキルエステル、イタコン酸ジアルキルエステル）、又はエチレン性不飽和カルボン酸無水物（無水マレイン酸、無水イタコン酸）、あるいは（メタ）アクリル酸等の単量体、及びこれらの塩が挙げられ、エチレン性不飽和カルボン酸モノエステル又はその塩が好適に使用される。
また、ビニルエステル系化合物としては、ギ酸ビニル、酢酸ビニル、プロピオン酸ビニル、酪酸ビニル、カプリン酸ビニル、ラウリル酸ビニル、バーサティック酸ビニル、パルミチン酸ビニル、ステアリン酸ビニル等が単独又は併用で用いることができるが、酢酸ビニルが特に実用性が高い。
【０００７】
本発明においては、かかる重合の際に上記の如きカルボキシル基を有する単量体、ビニルエステル系化合物以外に、飽和カルボン酸のアリルエステル（ステアリン酸アリル、ラウリン酸アリル、ヤシ油脂肪酸アリル、オクチル酸アリル、酪酸アリル等）、α−オレフィン（エチレン、プロピレン、α−ヘキセン、α−オクテン、α−デセン、α−ドデセン、α−ヘキサデセン、α−オクタデセン等）、アルキルビニルエーテル（プロピルビニルエーテル、ブチルビニルエーテル、ヘキシルビニルエーテル、オクチルビニルエーテル、デシルビニルエーテル、ドデシルビニルエーテル、テトラデシルビニルエーテル、ヘキサデシルビニルエーテル、オクタデシルビニルエーテル等）、アルキルアリルエーテル（プロピルアリルエーテル、ブチルアリルエーテル、ヘキシルアリルエーテル、オクチルアリルエーテル、デシルアリルエーテル、ドデシルアリルエーテル、テトラデシルアリルエーテル、ヘキサデシルアリルエーテル、オクタデシルアリルエーテル等）、更には、（メタ）アクリルアミド、（メタ）アクリロニトリル、（メタ）アリルスルホン酸塩、エチレン性不飽和スルホン酸塩、スチレン、塩化ビニルなどの（ビニルエステルと）共重合しうる単量体を５０モル％以下存在せしめて重合を行なっても良い。
共重合するに当たっては特に制限はなく、公知の重合方法が任意に用いられるが、普通メタノールあるいはエタノール等のアルコールを溶媒とする溶液重合が実施される。
【０００８】
かかる方法において単量体の仕込み方法としては、まずビニルエステル系化合物の全量と前記カルボキシル基含有不飽和単量体の一部を仕込んで重合を開始し、残りの不飽和単量体を重合期間中に連続的に又は分割的に添加する方法、一括仕込みする方法等任意の手段を用いて良い。共重合反応は、アゾビスイソブチロニトリル、過酸化アセチル、過酸化ベンゾイル、過酸化ラウロイルなどの公知のラジカル重合触媒を用いて行なわれる。又反応温度は５０℃〜沸点程度の範囲から選択される。
上記の如くして得られた共重合体は、次にケン化されてカルボキシル基含有ポリビニルアルコール系樹脂となる。
【０００９】
ケン化に当たっては、共重合体をアルコールや酢酸エステルまたはこれらの混合溶媒に溶解しアルカリ触媒の存在下に行なわれる。アルコールとしてはメタノール、エタノール、ブタノール等が挙げられ、また、酢酸エステルとしては酢酸メチル、酢酸エチル等が挙げられる。
アルコール中の共重合体の濃度は２０〜５０重量％の範囲から選ばれる。ケン化触媒としては水酸化ナトリウム、水酸化カリウム、ナトリウムメチラート、ナトリウムエチラート、カリウムメチラート等のアルカリ金属の水酸化物やアルコラートの如きアルカリ触媒を用いることが必要である。かかる触媒の使用量はビニルエステル系化合物に対して１〜１００ミリモル当量にすることが必要である。
かかる場合、ケン化温度は特に制限はないが、通常は１０〜７０℃、更には３０〜４０℃の範囲から選ぶのが好ましい。反応は通常２〜３時間にわたって行なわれ、好ましいケン化度は１０〜１００モル％で、特に好ましくは５０〜１００モル％、殊に好ましくは７０〜１００モル％の範囲から選択される。
尚、ビニルアルコール成分を含有させる場合は上記方法に限られるものではなく、例えばポリビニルアルコール（部分ケン化物、完全ケン化物）に酸化アルキレン類を後反応させる方法等も実施可能である。
【００１０】
かくして、カルボキシル基含有ポリビニルアルコール系樹脂が得られるわけであるが、かかるカルボキシル基の含有量は０．１〜１０モル％が好ましく、更には０．５〜５モル％で、かかるカルボキシル基の含有量が０．１モル％未満では塗布される溶剤系の離型剤に対する耐溶剤性が低く、逆に１０モル％を越えると塗工液とした時の溶解性が不良となって好ましくない。
また、本発明においては、カルボキシル基含有ポリビニルアルコール系樹脂の平均重合度は１００〜１００００が好ましく、更には３００〜３０００で、かかる平均重合度が１００未満では紙のバリヤー性が低下して離型剤の浸透量が多くなり、逆に１００００を越えると塗工液の塗工性が低下して好ましくない。
また、上記のカルボキシル基含有ポリビニルアルコール系樹脂と共に配合される親水基含有フッ素系化合物は、下記一般式（１）で表される如きパーフルオロアルキル基（ＣnＦ2n+1−；ｎは１〜４０の整数）及びアルキレンオキサイドを含有する化合物である。
【００１１】
【化３】
ＣnＦ2n+1−(Ｘ)l−(ＣＨ2−ＣＨ2−Ｏ)m−Ｈ ・・・（１）
（但し、Ｘは、−ＳＯ2ＮＲ（アルキル基）−またはカルボニル基で、
ｎは１〜４０の整数で、ｍは１〜１００の整数で、ｌは０または１）
上記一般式（１）においては、ｎ＝３〜２０、ｍ＝３〜３０が好ましく、更にはｎ＝５〜１０、ｍ＝５〜２０が好ましい。
尚、上記の化合物としては、大日本インキ化学工業(株)製の『メガファックＦ−１４２Ｄ』や『メガファックＦ−１４４Ｄ』等を挙げることができる。
【００１２】
本発明においては、上記の如きカルボキシル基含有ポリビニルアルコール系樹脂及び親水基含有フッ素系化合物からなる樹脂組成物（ａ）を用いるのであるが、かかる親水基含有フッ素系化合物の配合量は、カルボキシル基含有ポリビニルアルコール系樹脂１００重量部に対して、０．０１〜５．０重量部であることが必要で、かかる配合量が０．０１重量部未満では、添加効果がなく、逆に５．０重量部を越えると紙のバリヤー性が低下して離型剤の浸透量が多くなると同時にその上に塗布される離型剤との接着性が低下して本発明の目的を達成することができない。かかる配合量は、好ましくは０．０５〜３．０重量部で、更に好ましくは０．１〜２．０重量部である。
【００１３】
かかる樹脂組成物（ａ）を基紙に塗工するにあたっては、一般には水に溶解した塗工液として用いられるが、溶剤系でも使用可能である。溶剤の種類は、カルボキシル基含有ポリビニルアルコール系樹脂の特性、カルボキシル基含有ポリビニルアルコール系樹脂及び親水基含有フッ素系化合物の配合割合等に応じて適宜選択すれば良い。例えば、比較的ケン化度の低いものはペースト状で得られるので重合又はケン化に用いた溶媒をそのまま用いても良いし、必要ならば溶媒置換を行なっても良い。
かかる塗工液の調製に当たっては特に制限はなく、要するに水（または溶剤）と上記の樹脂組成物（ａ）を混合すれば良い。濃度は適宜調節すれば良いが、特に好ましい樹脂組成物（ａ）の濃度は作業性等を考慮して、通常は０．１〜２０重量％、更には１〜１０重量％程度の範囲から選ばれる。また、本発明においては、かかる塗工液に、更に必要に応じてグリオキザール、エピクロルヒドリン、尿素樹脂等の耐水化剤、消泡剤、界面活性剤（上記の親水基含有フッ素系化合物以外）、防腐剤、防虫剤、防錆剤、増粘剤等の公知の添加剤を添加することもでき、又本発明の特徴を損なわない範囲でならば他の紙加工剤、例えば、従来公知の他のポリビニルアルコール、澱粉、カルボキシメチルセルロース、アクリル系ラテックス、ＳＢＲラテックス等の樹脂も混合することができる。
【００１４】
かくして、かかる塗工液が基紙に塗工されるのであるが、塗工にあたっては、サイズプレスコート、ロールコーター法、エヤードクター法、ブレードコーター法、ゲートロールコーター法等の公知の任意の方法が採用され、その塗工量は、カルボキシル基含有ポリビニルアルコール系樹脂と親水基含有フッ素系化合物の合計量が０．１〜１０ｇ／ｍ2（固形分換算）、特に好ましくは０．５〜５ｇ／ｍ2（同上）程度になるようにするのが適当である。
また、基紙としては、特に限定されず、グラシン紙、セミグラシン紙、クラフト紙、和紙、上質紙、不織布等を挙げることができ、特にグランシン紙、セミグラシン紙が好適に用いられる。
かくして基紙に樹脂組成物（ａ）の層が形成されるのであるが、通常はこの表面に離型剤の層が形成されて剥離紙となる。かかる離型剤としては、特に限定されず、シリコーン系樹脂、フッ素系樹脂等が用いられる。
【００１５】
【実施例】
以下、実施例を挙げて本発明を具体的に説明する。
尚、実施例中、「部」、「％」とあるのは、特にことわりのない限り重量基準を示す。
実施例１
［カルボキシル基含有ポリビニルアルコール系樹脂の調製］
重合缶に酢酸ビニル５００部、マレイン酸３．４部、メタノール８５部を仕込んで、系内を撹拌下、窒素気流中で昇温して６０℃で３０分間還流後、アゾビスイソブチロニトリルを酢酸ビニルに対して０．０８モル％加え、マレイン酸のメタノール溶液を仕込み変性度が１．０モル％になるように滴下して６時間重合を行って反応終了後メタノール蒸気を吹き込んで未反応のモノマーを除去し、共重合体のメタノール溶液を得た。
次いで、得られたメタノール溶液を４０％にメタノールで希釈した。更に共重合体中の酢酸ビニルに対して水酸化ナトリウムを４０ミリモル％加えてケン化して、得られたケン化物を濾過し、７０℃で乾燥してカルボキシル基含有ポリビニルアルコール系樹脂（ケン化度９４．０モル％、平均重合度１７００）を得た。
【００１６】
上記のカルボキシル基含有ポリビニルアルコール系樹脂６部を水９４部に溶解させた後、親水基含有フッ素系化合物（Ｃ8Ｆ17−(ＣＨ2−ＣＨ2−Ｏ)10−Ｈ）［大日本インキ工業社製、『メガファックＦ−１４２Ｄ』］０．０４８部（ポリビニルアルコール系樹脂１００部に対し０．８部）添加して、塗工液とし、該塗工液を坪量６５ｇ／ｍ2、透気度１００秒のグラシン紙の片面に樹脂固形分で０．７ｇ／ｍ2になるように塗工し、円筒回転式ドライヤーにて１０５℃で２分間乾燥し、更にスーパーカレンダー（温度：８０℃，線圧：４０ｋｇ／ｃｍ）を通し、次いで、塗工・乾燥面に離型剤液（電子線硬化型無溶剤シリコーン［信越化学工業（株）製、『Ｘ−５２−１３１』］１００部及び白金触媒３０部）を固形分換算で１．０ｇ／ｍ2になるように塗工した後、電子線を照射して離型剤層を形成させて剥離紙を得た。
得られた剥離紙について、バリヤー性（透気度）及び離型性の評価を以下の要領で行った。
【００１７】
（バリヤー性）
ＪＩＳ Ｐ ８１１７の透気度に準拠して、王研式透気度試験器（旭精工(株)製）に試験片を固定し、１００ｍｌの空気が通過する時間（秒）を測定した。
（離型性）
剥離紙の離型剤層表面にアクリル系エマルジョン粘着剤（日本カーバイド社製、『ニカゾール Ｌ−１４５』）を塗工量が２５ｇ／ｍ2になるようにリバースロールコーターで塗工し、１３０℃で熱風乾燥した後、坪量６５ｇ／ｍ2の上質紙を張り合わせて、標準状態で０．３ｍ／ｍｉｎで剥離させた時の剥離強度（ｇ／５０ｍｍ）を測定して、以下のとおり評価した。
○ −−−１００ｇ／５０ｍｍ未満
△ −−−１００〜２００ｇ／５０ｍｍ未満
× −−−２００ｇ／５０ｍｍ以上
また、得られた剥離紙は、通常のリサイクル作業により容易に水に溶解し、古紙として回収することも可能であった。
【００１８】
実施例２〜６、比較例１〜３
実施例１に準じて表１に示される如きカルボキシル基含有ポリビニルアルコール系樹脂及び親水基含有フッ素系化合物を用いて、同様に評価を行った。
尚、実施例５、６では、マレイン酸に変えてイタコン酸を用いた。
実施例及び比較例の評価結果を表２に示す。
【００１９】
【表１】
【表２】
【発明の効果】
本発明の剥離紙は、基紙に特定の樹脂組成物（ａ）が塗工されているため、バリヤー性が良好なため離型剤の浸透性を防ぐことができ、離型性も良好で、更には通常のリサイクル作業により容易に水に溶解し、古紙として回収することができ、粘着ラベル、感熱ラベル、粘着テープ、粘着シート等の基材として有用である。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a release paper, and more particularly to a release paper having glassine paper or the like as a base paper and excellent in releasability, recyclability, solvent resistance (to the applied release agent), and the like.
[0002]
[Prior art]
Conventionally, release paper has been used in many fields as a substrate for adhesive labels, adhesive tapes, adhesive sheets and the like.
Such release paper generally has a structure in which a release agent layer is provided on the surface of the base paper. Usually, the release agent does not penetrate into the paper and is good on the surface of the base paper. In order to form a release agent layer, a polyolefin resin layer such as polyethylene is provided at the interface, or a barrier layer such as polyvinyl alcohol resin, carboxymethyl cellulose, casein, polyvinyl acetate emulsion is provided. ing.
[0003]
[Problems to be solved by the invention]
However, when the polyolefin resin layer is provided, the barrier effect is sufficient, but the treatment of the resin becomes a big problem in consideration of recent paper recycling. On the other hand, in the case of a layer made of a conventional polyvinyl alcohol resin or the like, although the recycling problem is cleared, the barrier performance is not sufficient, and a barrier layer satisfying both recyclability and barrier property is provided, and further, release property is improved. Therefore, an excellent release paper is desired.
[0004]
[Means for Solving the Problems]
Therefore, as a result of intensive studies by the present inventors in view of such circumstances, 0.01 to 5.0 parts by weight of the hydrophilic group-containing fluorine compound is added to the base paper with respect to 100 parts by weight of the carboxyl group-containing polyvinyl alcohol resin. When the blended resin composition (a) is applied to a release paper, and particularly when the hydrophilic group-containing fluorine-based compound is a compound represented by the following general formula (1), the effects of the present invention are obtained. The inventors have found that the invention can be obtained remarkably and have completed the present invention.
[Chemical 2]
C n F 2n + 1 - ( X) l - (CH 2 -CH 2 -O) m -H ··· (1)
(Wherein, X is, -SO 2 NR (alkyl) - or carbonyl group,
n is an integer of 1 to 40, m is an integer of 1 to 100, and l is 0 or 1)
[0005]
DETAILED DESCRIPTION OF THE INVENTION
The present invention is described in detail below.
The release paper of the present invention is obtained by coating a base paper with a resin composition (a) comprising a carboxyl group-containing polyvinyl alcohol resin and a hydrophilic group-containing fluorine compound, and as such a carboxyl group-containing polyvinyl alcohol resin. Is not particularly limited as long as it is a polyvinyl alcohol resin containing a carboxyl group, and its production is not particularly limited, for example, a copolymer from an unsaturated monomer having a carboxyl group and a vinyl ester compound. Examples thereof include a method of saponifying the copolymer, a method of graft polymerization of a monomer having an oxyalkylene group to a polyvinyl alcohol resin having a carboxyl group, and the former method is a production surface of the resin. It is practical in terms of performance.
Hereinafter, the former method will be specifically described.
[0006]
As an unsaturated monomer having a carboxyl group, an ethylenically unsaturated dicarboxylic acid (maleic acid, fumaric acid, itaconic acid), or an ethylenically unsaturated carboxylic acid monoester (maleic acid monoalkyl ester, fumaric acid monoalkyl ester) , Itaconic acid monoalkyl ester), or ethylenically unsaturated dicarboxylic acid diester (maleic acid dialkyl ester, fumaric acid dialkyl ester, itaconic acid dialkyl ester), or ethylenically unsaturated carboxylic acid anhydride (maleic anhydride, itaconic anhydride) ), Or a monomer such as (meth) acrylic acid, and a salt thereof, and an ethylenically unsaturated carboxylic acid monoester or a salt thereof is preferably used.
As vinyl ester compounds, vinyl formate, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl caprate, vinyl laurate, vinyl versatate, vinyl palmitate, vinyl stearate, etc. should be used alone or in combination. However, vinyl acetate is particularly useful.
[0007]
In the present invention, in addition to the monomer having a carboxyl group and the vinyl ester compound as described above, allyl ester of saturated carboxylic acid (allyl stearate, allyl laurate, allyl coconut oil fatty acid, octylic acid) Allyl, allyl butyrate, etc.), α-olefins (ethylene, propylene, α-hexene, α-octene, α-decene, α-dodecene, α-hexadecene, α-octadecene, etc.), alkyl vinyl ethers (propyl vinyl ether, butyl vinyl ether, Hexyl vinyl ether, octyl vinyl ether, decyl vinyl ether, dodecyl vinyl ether, tetradecyl vinyl ether, hexadecyl vinyl ether, octadecyl vinyl ether, etc.), alkyl allyl ether (propyl allyl ether, butyl allyl) Ether, hexyl allyl ether, octyl allyl ether, decyl allyl ether, dodecyl allyl ether, tetradecyl allyl ether, hexadecyl allyl ether, octadecyl allyl ether, etc.), (meth) acrylamide, (meth) acrylonitrile, (meth) The polymerization may be carried out in the presence of 50 mol% or less of a copolymerizable monomer (with vinyl ester) such as allyl sulfonate, ethylenically unsaturated sulfonate, styrene, and vinyl chloride.
The copolymerization is not particularly limited, and a known polymerization method is arbitrarily used. Usually, solution polymerization using methanol or alcohol such as ethanol as a solvent is carried out.
[0008]
In this method, the monomer is charged as follows. First, the whole amount of the vinyl ester compound and a part of the carboxyl group-containing unsaturated monomer are charged to start polymerization, and the remaining unsaturated monomer is removed during the polymerization period. Arbitrary means such as a method of adding continuously or in a divided manner and a method of batch charging may be used. The copolymerization reaction is performed using a known radical polymerization catalyst such as azobisisobutyronitrile, acetyl peroxide, benzoyl peroxide, or lauroyl peroxide. The reaction temperature is selected from the range of about 50 ° C. to the boiling point.
The copolymer obtained as described above is then saponified into a carboxyl group-containing polyvinyl alcohol resin.
[0009]
In the saponification, the copolymer is dissolved in an alcohol, an acetate ester or a mixed solvent thereof in the presence of an alkali catalyst. Examples of the alcohol include methanol, ethanol, butanol and the like, and examples of the acetate ester include methyl acetate and ethyl acetate.
The concentration of the copolymer in the alcohol is selected from the range of 20 to 50% by weight. As the saponification catalyst, it is necessary to use an alkali catalyst such as an alkali metal hydroxide or alcoholate such as sodium hydroxide, potassium hydroxide, sodium methylate, sodium ethylate or potassium methylate. The amount of the catalyst used must be 1 to 100 millimole equivalents relative to the vinyl ester compound.
In such a case, the saponification temperature is not particularly limited, but is usually selected from the range of 10 to 70 ° C, more preferably 30 to 40 ° C. The reaction is usually carried out over 2 to 3 hours, and the preferred degree of saponification is 10 to 100 mol%, particularly preferably 50 to 100 mol%, particularly preferably 70 to 100 mol%.
In addition, when it contains a vinyl alcohol component, it is not restricted to the said method, For example, the method etc. which post-react an alkylene oxide with polyvinyl alcohol (partially saponified product, complete saponified product) etc. are also feasible.
[0010]
Thus, a carboxyl group-containing polyvinyl alcohol-based resin is obtained. The content of the carboxyl group is preferably 0.1 to 10 mol%, and more preferably 0.5 to 5 mol%. If the amount is less than 0.1 mol%, the solvent resistance to the solvent-based mold release agent to be applied is low. Conversely, if it exceeds 10 mol%, the solubility when used as a coating liquid is unfavorable.
In the present invention, the average polymerization degree of the carboxyl group-containing polyvinyl alcohol resin is preferably from 100 to 10,000, and more preferably from 300 to 3000. When the average polymerization degree is less than 100, the barrier property of the paper is lowered and the mold release is performed. If the penetration amount of the agent increases and exceeds 10,000, the coating property of the coating solution is undesirably lowered.
Further, the hydrophilic group-containing fluorine-based compound mixed with the above carboxyl group-containing polyvinyl alcohol-based resin, such as represented by the following general formula (1) perfluoroalkyl group (C n F 2n + 1 - ; n is a compound containing 1 to 40 integer) and an alkylene oxide.
[0011]
[Chemical 3]
C n F 2n + 1 - ( X) l - (CH 2 -CH 2 -O) m -H ··· (1)
(Wherein, X is, -SO 2 NR (alkyl) - or carbonyl group,
n is an integer of 1 to 40, m is an integer of 1 to 100, and l is 0 or 1)
In the said General formula (1), n = 3-20 and m = 3-30 are preferable, Furthermore, n = 5-10 and m = 5-20 are preferable.
Examples of the compound include “Megafac F-142D” and “Megafac F-144D” manufactured by Dainippon Ink and Chemicals, Inc.
[0012]
In the present invention, the resin composition (a) comprising the carboxyl group-containing polyvinyl alcohol resin and the hydrophilic group-containing fluorine compound as described above is used. The blending amount of the hydrophilic group-containing fluorine compound is a carboxyl group. It is necessary to be 0.01 to 5.0 parts by weight with respect to 100 parts by weight of the contained polyvinyl alcohol-based resin. If it exceeds the parts by weight, the barrier property of the paper is lowered and the amount of penetration of the release agent is increased. At the same time, the adhesiveness to the release agent applied thereon is lowered and the object of the present invention cannot be achieved. . The amount is preferably 0.05 to 3.0 parts by weight, more preferably 0.1 to 2.0 parts by weight.
[0013]
When the resin composition (a) is applied to the base paper, it is generally used as a coating solution dissolved in water, but it can also be used in a solvent system. The type of the solvent may be appropriately selected according to the characteristics of the carboxyl group-containing polyvinyl alcohol resin, the blending ratio of the carboxyl group-containing polyvinyl alcohol resin and the hydrophilic group-containing fluorine compound, and the like. For example, since a product having a relatively low saponification degree is obtained in a paste form, the solvent used for polymerization or saponification may be used as it is, or solvent substitution may be performed if necessary.
There is no particular limitation on the preparation of such a coating solution, and in short, water (or solvent) and the above resin composition (a) may be mixed. The concentration may be adjusted as appropriate, but the particularly preferable concentration of the resin composition (a) is usually selected from the range of about 0.1 to 20% by weight, more preferably about 1 to 10% by weight in consideration of workability and the like. It is. In the present invention, if necessary, the coating liquid may further comprise a water-resistant agent such as glyoxal, epichlorohydrin, urea resin, antifoaming agent, surfactant (other than the above-mentioned hydrophilic group-containing fluorine-based compounds), antiseptic, and the like. Known additives such as additives, insect repellents, rust preventives, thickeners can also be added, and other paper processing agents such as other conventionally known ones can be added as long as they do not impair the characteristics of the present invention. Resins such as polyvinyl alcohol, starch, carboxymethyl cellulose, acrylic latex, and SBR latex can also be mixed.
[0014]
Thus, the coating liquid is applied to the base paper. In the coating, any known method such as size press coating, roll coater method, airy coater method, blade coater method, gate roll coater method, etc. The total coating amount of the carboxyl group-containing polyvinyl alcohol resin and the hydrophilic group-containing fluorine compound is 0.1 to 10 g / m 2 (in terms of solid content), particularly preferably 0.5 to 5 g. / M 2 (same as above) is appropriate.
The base paper is not particularly limited, and examples thereof include glassine paper, semi-glassine paper, kraft paper, Japanese paper, high-quality paper, non-woven fabric, and the like. Gransin paper and semi-glassine paper are particularly preferably used.
Thus, a layer of the resin composition (a) is formed on the base paper. Usually, a release agent layer is formed on this surface to form a release paper. Such a release agent is not particularly limited, and silicone resins, fluorine resins, and the like are used.
[0015]
【Example】
Hereinafter, the present invention will be specifically described with reference to examples.
In the examples, “parts” and “%” are based on weight unless otherwise specified.
Example 1
[Preparation of carboxyl group-containing polyvinyl alcohol resin]
A polymerization can was charged with 500 parts of vinyl acetate, 3.4 parts of maleic acid, and 85 parts of methanol. The system was stirred and heated in a nitrogen stream and refluxed at 60 ° C. for 30 minutes, followed by azobisisobutyronitrile. 0.08 mol% of vinyl acetate is added, a methanolic solution of maleic acid is added dropwise so that the degree of modification is 1.0 mol%, polymerization is carried out for 6 hours, and after completion of the reaction, methanol vapor is blown into the solution. The monomer of the reaction was removed to obtain a methanol solution of the copolymer.
The resulting methanol solution was then diluted to 40% with methanol. Further, 40 mmol% of sodium hydroxide was added to vinyl acetate in the copolymer to saponify, and the resulting saponified product was filtered and dried at 70 ° C. to obtain a carboxyl group-containing polyvinyl alcohol resin (degree of saponification). 94.0 mol%, average polymerization degree 1700).
[0016]
After dissolving 6 parts of the above-mentioned carboxyl group-containing polyvinyl alcohol resin in 94 parts of water, a hydrophilic group-containing fluorine compound (C 8 F 17 — (CH 2 —CH 2 —O) 10 —H) [Dainippon Ink “Megafac F-142D” manufactured by Kogyo Co., Ltd.] was added in an amount of 0.048 parts (0.8 parts relative to 100 parts of polyvinyl alcohol resin) to form a coating liquid, and the coating liquid had a basis weight of 65 g / m 2 , Coated on one side of glassine paper with an air permeability of 100 seconds to a resin solid content of 0.7 g / m 2 , dried at 105 ° C. for 2 minutes with a cylindrical rotary dryer, and then super calender (temperature: 80 ° C., linear pressure: 40 kg / cm), and then a release agent solution (electron beam curable solvent-free silicone [X-52-131], manufactured by Shin-Etsu Chemical Co., Ltd.] 100 parts and 30 parts of platinum catalyst) in terms of solid content of 1.0 g / After coating at 2 to obtain a release paper by irradiating an electron beam to form a release agent layer.
The obtained release paper was evaluated for barrier properties (air permeability) and releasability in the following manner.
[0017]
(Barrier properties)
In accordance with the air permeability of JIS P 8117, a test piece was fixed to an Oken type air permeability tester (manufactured by Asahi Seiko Co., Ltd.), and the time (seconds) through which 100 ml of air passed was measured.
(Releasability)
Acrylic emulsion adhesive (“Nicazole L-145” manufactured by Nippon Carbide Co., Ltd.) was applied to the surface of the release agent layer of the release paper with a reverse roll coater so that the coating amount was 25 g / m 2 , and 130 ° C. After drying with hot air, a high-quality paper having a basis weight of 65 g / m 2 was laminated, and the peel strength (g / 50 mm) when peeled at 0.3 m / min in a standard state was measured and evaluated as follows. .
○ --- Less than 100 g / 50 mm Δ --- 100 to less than 200 g / 50 mm x ---- 200 g / 50 mm or more In addition, the obtained release paper is easily dissolved in water by ordinary recycling and recovered as used paper It was also possible to do.
[0018]
Examples 2-6, Comparative Examples 1-3
According to Example 1, the same evaluation was performed using a carboxyl group-containing polyvinyl alcohol resin and a hydrophilic group-containing fluorine compound as shown in Table 1.
In Examples 5 and 6, itaconic acid was used instead of maleic acid.
Table 2 shows the evaluation results of Examples and Comparative Examples.
[0019]
[Table 1]
[Table 2]
【The invention's effect】
Since the release paper of the present invention is coated with the specific resin composition (a) on the base paper, the barrier property is good, so that the permeability of the release agent can be prevented, and the release property is also good. Furthermore, it can be easily dissolved in water by ordinary recycling work and recovered as used paper, and is useful as a substrate for adhesive labels, heat-sensitive labels, adhesive tapes, adhesive sheets and the like.
Claims (3)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP05588398A JP4142147B2 (en) | 1998-02-19 | 1998-02-19 | Release paper |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP05588398A JP4142147B2 (en) | 1998-02-19 | 1998-02-19 | Release paper |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH11229298A JPH11229298A (en) | 1999-08-24 |
| JP4142147B2 true JP4142147B2 (en) | 2008-08-27 |
Family
ID=13011511
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP05588398A Expired - Lifetime JP4142147B2 (en) | 1998-02-19 | 1998-02-19 | Release paper |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP4142147B2 (en) |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5751897A (en) * | 1980-09-08 | 1982-03-26 | Meisei Chemical Works Ltd | Oil resistant treatment of paper |
| JPS59144693A (en) * | 1983-02-02 | 1984-08-18 | 山陽国策パルプ株式会社 | Production of base paper for direct coating of release agent |
| FR2683535B1 (en) * | 1991-11-12 | 1994-10-28 | Atochem | NOVEL FLUORINATED COPOLYMERS AND THEIR USE FOR COATING AND IMPREGNATION OF VARIOUS SUBSTRATES. |
| JPH0718599A (en) * | 1993-07-01 | 1995-01-20 | Kuraray Co Ltd | Production of coated paper |
| JPH08209590A (en) * | 1995-01-30 | 1996-08-13 | Nippon Paper Ind Co Ltd | Oil-resistant paper and its production |
| JPH09137399A (en) * | 1995-11-08 | 1997-05-27 | Oji Paper Co Ltd | Production of release paper |
| JPH09176999A (en) * | 1995-12-22 | 1997-07-08 | Oji Paper Co Ltd | Production of glassine paper |
| JP4142148B2 (en) * | 1997-03-26 | 2008-08-27 | 日本合成化学工業株式会社 | Paper processing composition |
-
1998
- 1998-02-19 JP JP05588398A patent/JP4142147B2/en not_active Expired - Lifetime
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| Publication number | Publication date |
|---|---|
| JPH11229298A (en) | 1999-08-24 |
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