JP4446671B2 - Electrophotographic label - Google Patents

Description

【００６０】
（実施例１）
＜基材層（Ａ）＞
ＰＰ（表１に記載）６重量％とＨＳＢＲ（表１に記載）８４重量％との混合物に、炭カル（表１に記載）１０重量％を配合した組成物［▲１▼］を、２５０℃に設定した押出機にて混練し、ストランド状に押出し、カッティングしてペレットとした。この組成物［▲１▼］を２５０℃に設定した押出機に接続したＴダイよりフィルム状に押出し、これを冷却装置により冷却して無延伸フィルムを得た（厚み：５５μｍ、結晶化熱：６Ｊ／ｃｍ³ ）。
このフィルムの両面に、印加エネルギー密度９０Ｗ・分／ｍ² にてコロナ放電処理を行った。
【００６１】
尚、各実施例及び比較例中の樹脂成分ないしはこれと微細粉末との混合物の溶融混練において、樹脂成分と微細粉末の合計重量を１００重量部として、これに加えて、酸化防止剤として、ＢＨＴ（４−メチル−２，６−ジ−ｔ−ブチルフェノール）０．２重量部と、イルガノックス１０１０（フェノール系酸化防止剤、チバガイギー社製、商品名）０．１重量部を添加した。
また、本明細書の実施例に使用した炭酸カルシウム粉末の粒子径は、レーザー回折式粒子計測装置「マイクロトラック」（（株）日機装製、商品名）により測定した累積５０％粒径である。
【００６２】
＜粘着剤層（Ｂ）の形成と離型紙（Ｃ）の貼合＞
上質紙の両面にポリエチレンフィルムをラミネートし、更に片面にシリコン処理を施した厚さ１００μｍ、密度０．９ｇ／ｃｍ³ の離型紙（Ｃ）のシリコン処理面に、感圧粘着剤「オリバイン ＢＰＳ−１１０９」（東洋インキ化学工業（株）製、商品名）を固形分量で２５ｇ／ｍ² となるようにコンマコーターで塗工、乾燥して粘着剤層とし（Ｂ）とした。得られた離型紙（Ｃ）上の粘着剤層（Ｂ）を基材層（Ａ）と貼合して、本発明の電子写真ラベルを得た。
得られた電子写真ラベルにつき、以下の要領で評価を行った。評価結果を表２にまとめて示す。
【００６３】
＜評価＞
ｉ．カール高さの評価
得られた本発明の電子写真ラベルをＡ−４サイズ（２１０ｍｍ×２９７ｍｍ）に断裁し、温度２３℃、相対湿度５０％の恒温恒湿室内で１日間放置した。次に、市販の熱ロール定着式電子写真プリンター「ＬＡＳＥＲ ＳＨＯＴ ＬＢＰ−９５０」（キャノン（株）製、商品名）にて、基材層（Ａ）を上向きに印刷面として通紙し、排紙時も印刷面が上になる経路で印刷を行った。
プリンターの通紙後、電子写真ラベルを湿度２３℃、相対湿度５０％の雰囲気下、平らな台の上に放置し、通紙２分後の４隅のカール高さを評価した。
ii．静電容量の測定
得られた本発明の電子写真ラベルの静電容量は、２３℃、相対湿度５０％の恒温恒湿室内で、「４１９２ＡＬＦＩＭＰＥＤＡＮＣＥＡＮＡＬＹＺＥＲ」（ＨＥＷＬＥＴＴＰＡＣＫＡＲＤ社、商品名）を用いて、直径３８ｍｍの電極に電極直径より大きい試料を挟み込み５Ｖの電圧を印可して、周波数３００Ｈｚで評価した。
【００６４】
iii ．印刷品質の評価
印刷後の画像及び文字の太りや変形、印刷濃度不足、地汚れについて、目視観察し、以下の基準で評価した。
非常に良好（◎）画像及び文字が鮮明である。（実使用可能）
良好（○）太りや変形、印刷濃度不足、地汚れが少ない。（実使用可能）
不良（×）太りや変形、印刷濃度不足、地汚れが目立つ。（実使用困難）
【００６５】
iv．耐水強度の評価
得られた電子写真ラベルを５０ｍｍ×５０ｍｍの正方形に断裁し、２０℃の水に１日間浸水させた後、離型紙を剥がし、基材を手で引き裂いたとき状態について、以下の基準で評価した。
非常に良好（◎）基材が破れない。（実使用可能）
良好（○）基材が破れにくい。（実使用可能）
不良（×）基材が容易に破れる。（実使用困難）
【００６６】
（実施例２）
組成物［▲２▼］の配合成分の種類及び量を表２記載のものとし、実施例１と同様の操作により無延伸フィルムを得た後、この無延伸フィルムを１４５℃（温度ａ）に加熱した後、縦方向に５倍延伸して延伸フィルムを得た（厚み：６０μｍ、結晶化熱：３１Ｊ／ｃｍ³ ）。その後、実施例１と同様の操作により電子写真ラベルを作製し、評価を行った。評価結果を表２に示す。
【００６７】
（実施例３）
組成物［▲３▼］の配合成分の種類及び量を表２記載のものとし、実施例１と同様の操作により無延伸フィルムを得た後、この無延伸フィルムを１４０℃（温度ａ）に加熱した後、縦方向に５倍延伸して延伸フィルムを得た。
組成物［▲３▼］を２４０℃に設定した押出機に接続したＴダイよりフィルム状に押出した。得られたフィルムを上記の操作により調製した５倍延伸フィルムの両面に積層し、５５℃にまで冷却した後、１６０℃（温度ｂ）に加熱してテンターで横方向に８倍延伸した。その後、１６５℃（温度ｃ）でアニーリング処理し、５０℃にまでに冷却し、耳部をスリットして３層構造（１軸延伸／２軸延伸／１軸延伸）のフィルムを得た（厚み：１０／４０／１０μｍ＝６０μｍ、結晶化熱：４６Ｊ／ｃｍ³ ）。その後、実施例１と同様の操作により電子写真ラベルを作製し、評価を行った。評価結果を表２に示す。
【００６８】
（実施例４〜６）
組成物［▲４▼］〜組成物［▲６▼］の配合成分の種類及び量を表２記載のものとしたほかは、実施例１と同様の操作により電子写真ラベルを作製し、評価を行った。評価結果を表２に示す。
（実施例７）
組成物［▲７▼］の配合成分の種類及び量を表２記載のものとし、２５０℃に設定された２台の異なる押出機が接続された多層ダイを用い、３層構造になるようダイ内で積層されるようにしてフィルム状に押出し、これを冷却装置により冷却して無延伸フィルムを得た。
次いで、この無延伸フィルムを１４０℃（温度ａ）に加熱した後、縦方向に５倍延伸したのち冷却し、延伸フィルムを得た。
再度、１６０℃（温度ｂ）に加熱してテンターで横方向に８倍延伸した。その後、１６５℃（温度ｃ）でアニーリング処理し、５０℃にまでに冷却し、耳部をスリットして３層構造（２軸延伸／２軸延伸／２軸延伸）のフィルムを得た（厚み：１０／４５／１０μｍ＝６５μｍ、結晶化熱：４４Ｊ／ｃｍ³ ）。その後、実施例１と同様の操作により電子写真ラベルを作製し、評価を行った。評価結果を表２に示す。
【００６９】
（実施例８）
表２に記載される成形条件以外は、実施例３と同様の操作にて作製したコロナ放電処理フィルムを支持体（片面指定）として、下記のトナー受理層用塗工液を固形分含有量が５ｇ／ｍ² になるように塗工し、その後９０℃で１分間硬化させてフィルムを得た。その後、実施例１と同様の操作による離型紙をトナー受理層が形成されている反対面側に貼合した電子写真ラベルを作製し、評価を行った。評価結果を表２に示す。
【００７０】
《トナー受理層用塗工液》
トナー受理層用塗工液としては、２−ヒドロキシエチルメタクリレート１５部、メチルメタクリレート５０部、エチルアクリレート３５部およびトルエン１００部を、攪拌機、環流冷却管および温度計を装着した三ツ口フラスコに仕込み、窒素置換後、２，２’−アゾビスイソブチロニトリル０．６部を開始剤として８０℃で４時間重合させた。得られた溶液は、水酸基価６５の水酸基含有メタクリル酸エステル重合体の５０％トルエン溶液であった。
【００７１】
次いで、これにヘキサメチレンジイソシアネート（日本ポリウレタン工業（株）製：コロネートＨＬ）７５％酢酸エチル溶液、２次粒子径の平均が３μｍのシリカ粉末（富士シリシア（株）製：サイリシア３７０）、平均粒径１．５μｍの重質炭酸カルシウム粉末（白石カルシウム製）を次に示す固形分比で配合した。
《固形分比》
メタクリル酸エステル重合体 ４８重量％
ヘキサメチレンジイソシアネート ２重量％
シリカ ２５重量％
重質炭酸カルシウム ２５重量％
この混合物に酢酸ブチルを添加して固形分を３５重量％に調整した。
【００７２】
（比較例１）
組成物［▲８▼］の配合成分の種類及び量を表２記載のものとしたほかは、実施例１と同様の操作により電子写真ラベルを作製し、評価を行った。評価結果を表２に示す。
（比較例２）
組成物［▲９▼］の配合成分の種類及び量を表２記載のものとしたほかは、実施例３と同様の操作により電子写真ラベルを作製し、評価を行った。評価結果を表２に示す。
【００７３】
（比較例３）
厚さ２５０μｍ、密度０．９ｇ／ｃｍ³ の上質紙の両面にポリエチレンフィルムをラミネートし、更に片面にシリコン処理を施した離型紙を用いた以外は、比較例２と同様の操作により電子写真ラベルを作製し、評価を行った。評価結果を表２に示す。
（比較例４）
市販のパルプ紙「マイリサイクルペーパー１００ｗ」（（株）ＮＢＳリコー、商品名）を使用し、実施例１と同様の操作により電子写真ラベルを作製し、評価を行った。評価結果を表２に示す。
【００７４】
【表２】

【００７５】
（実施例９）
組成物［○10］の配合成分の種類及び量を表３記載のものとし、層間剥離を可能とする層（Ｅ）としての組成物［○10］と基材層（Ａ）としての組成物［▲３▼］とを２５０℃に設定された２台の異なる押出機が接続された多層ダイを用い、２層構造になるようダイ内で積層されるようにしてフィルム状に押出し、これを冷却装置により冷却して無延伸フィルムを得た。
次いで、この無延伸フィルムを１５０℃（温度ａ）に加熱した後、縦方向に５倍延伸したのち冷却し、延伸フィルムを得た。
再度、１４０℃（温度ｂ）に加熱してテンターで横方向に８倍延伸した。その後、１６０℃（温度ｃ）でアニーリング処理し、５０℃にまでに冷却し、耳部をスリットして２層（（Ｅ）／（Ａ）：肉厚３０／４５μｍ）構造のフィルムを得た（厚み：７５μｍ）。その後、実施例１と同様の操作による表面酸化処理を施し、粘着剤層が形成された離型紙を層間剥離を可能とする層（Ｅ）側に貼合した電子写真ラベルを得た。
得られた電子写真ラベルにつき、以下の要領で評価を行った。評価結果を表３にまとめて示す。
【００７６】
＜評価＞
ｖ．剥離開始性
層間剥離を可能とする層（Ｅ）の剥離強度、及び表面層（Ｆ）の破断強度は、それぞれ上記＜剥離強度＞、及び＜破断強度＞に記載の方法で測定した。
得られた電子写真ラベルを５ｃｍ×５ｃｍの正方形に切り取って離型紙を剥がし、官製ハガキの上に貼着した後、樹脂フィルムの４辺の内１辺を手で持ち、官製ハガキより引き剥がし、層間剥離を可能とする層（Ｅ）ないしは表面層（Ｆ）の剥離が開始するまでの状態について、以下の基準で評価した。
非常に良好（◎）剥離がすぐに開始する。（実使用可能）
良好（○）剥離が開始するまでに２ｍｍ以上要する。（実使用可能）
やや不良（△）剥離が部分的に開始する。（実使用困難）
不良（×）剥離が開始するまでに１０ｍｍ以上要する。（実使用困難）
【００７７】
vi．剥離伝播性
得られた電子写真ラベルを５ｃｍ×５ｃｍの正方形に切り取って離型紙を剥がし、官製ハガキの上に貼着した後、基材層（Ａ）面４辺の内１辺に粘着テープ「セロテープ」（ニチバン（株）製、商品名）を貼り、層間剥離を可能とする層（Ｅ）ないしは表面層（Ｆ）での剥離が開始し易い状態にし、基材層（Ａ）を官製ハガキより引き剥がし、層間剥離を可能とする層（Ｅ）ないしは表面層（Ｆ）の伝播状態と剥離力について、目視観察し、以下の基準で評価した。
非常に良好（◎）剥離力が軽く、全面綺麗に伝播する。（実使用可能）
良好（○）剥離力はやや重いが、全面綺麗に伝播する。（実使用可能）
やや不良（△）剥離力が非常に重いが、全面綺麗に伝播する。（実使用困難）
不良（×）全面伝播できずに途中で切れてしまう。（実使用困難）
【００７８】
vii ．情報隠蔽性
官製ハガキに文字サイズ１０ポイントのアルファベット２６文字を印字して、電子写真ラベルの離型紙（Ｃ）を剥がした後アルファベットの印字面に貼着し、作製フィルムを透して見える文字の隠蔽性について、目視観察し、以下の基準で評価した。
非常に良好（◎）実使用可能。
良好（○）実使用可能。
やや不良（△）実使用困難。
不良（×）実使用困難。
【００７９】
viii．情報認識性
合成紙「ＶＥＳ８５」（（株）ユポ・コーポレーション製、商品名）にバーコードプンター「Ｂ３０」（（株）テック製、商品名）にてバーコード（ＣＯＤＥ３９）を印字してバーコード読みとり用サンプルを作成した。
電子写真ラベルの離型紙（Ｃ）を剥がし、合成紙上のバーコード印字面上に貼り、バーコードを隠蔽したサンプルを１０個作成し、基材層（Ａ）を引き剥がした後のバーコードをバーコードリーダー「ＬＡＳＥＲＣＨＥＫ II」（富士電気冷凍機（株）製、商品名）にて読みとり、バーコード認識に成功した回数について、以下の基準で評価した。
非常に良好（◎）１０回成功。（実使用可能）
良好（○）８〜９回成功。（実使用可能）
やや不良（△）２〜７回成功。（実使用困難）
不良（×）成功回数１回以下。（実使用困難）
【００８０】
（実施例１０）
ＥＶＡ（表１に記載）を１６０℃に設定した押出機に接続したＴダイよりフィルム状に押出した。得られたフィルムを実施例９と同様の操作により調製した５倍延伸フィルムの層間剥離を可能とする層（Ｅ）面に積層し表面層（Ｆ）を設け、５５℃にまで冷却した後、１４３℃（温度ｂ）に加熱してテンターで横方向に８倍延伸した。その後、１６０℃（温度ｃ）でアニーリング処理し、５０℃にまでに冷却し、耳部をスリットして３層（（Ｆ）／（Ｅ）／（Ａ）：肉厚５／３０／４５μｍ）構造のフィルムを得た（厚み：８０μｍ）。その後、実施例１と同様の操作による表面酸化処理を施し、粘着剤層が形成された離型紙を表面層（Ｆ）側に貼合した電子写真ラベルを作製し、評価を行った。評価結果を表３に示す。
（比較例５）
樹脂フィルム層（Ａ）に組成物（▲８▼）（表２に記載）、層間剥離を可能とする層（Ｅ）に組成物［○11］（表３に記載）、表面層（Ｆ）にＬＤＰＥ（表１に記載）を用い、基材層（Ａ）としての組成物［▲９▼］と表３に記載される成形条件以外は、実施例１０と同様の操作により電子写真ラベルを作製し、評価を行った。評価結果を表３に示す。
【００８１】
【表３】

【００８２】
【発明の効果】
本発明の電子写真ラベルは、熱定着式電子写真プリンター又は熱定着式電子写真複写機印刷後のカールを低減させ、多数枚の連続印刷にて良好な印刷性を実現させ、記録された用紙は耐水性、機械特性に優れるので屋内外産業用として有用である。また、剥離を開始するための特殊な加工を必要とせず、小さな力で表面層が剥離するので配送伝表、隠蔽シール、貼り替え防止用ラベル、改ざん防止シール、応募シール、クーポン等の幅広い用途にも有効に利用できる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to an electrophotographic label based on a thermoplastic resin film that can be used in a heat fixing type electrophotographic printer or a heat fixing type electrophotographic copying machine. Furthermore, the present invention is superior in water resistance compared to natural paper labels, and is suitable for paper for industrial products (labels with usage instructions and precautions), indoor and outdoor advertising stickers, and labels for frozen food containers. It relates to an electrophotographic label. The present invention also relates to an electrophotographic label that is useful as a base material for a delivery slip having no adhesive residue, a postcard or passbook concealment seal, an anti-paste label, a tamper-proof seal, an application seal, a coupon, etc. by providing a release layer.
[0002]
[Prior art]
Conventionally, coated paper or the like has been used as a sticker for outdoor advertising stickers or frozen food containers, but because it has poor water resistance, it is a resin film with good water resistance, especially polyolefin synthetic paper. Is used.
Such a resin film is a publicly known film, and details thereof can be referred to, for example, Patent Document 1, Patent Document 2, Patent Document 3, Patent Document 4, and Patent Document 5.
[0003]
However, these polyolefin synthetic papers are used as printing labels in electrophotographic printers that fix toner by thermal energy (thermal fixing type) such as ordinary electrophotographic copying machines (PPC) or laser beam printers (LBP). As a result, the resin film curls greatly due to the shrinkage difference between the resin film and the release paper that occurs when the toner is heat-fixed, so the paper discharge performance is poor and the continuous printing of a large number of sheets is hindered. Met.
Further, an adhesive label for preventing tampering or an adhesive label that cannot be replaced is required and put into practical use. However, these adhesive labels for preventing re-sticking are expensive, and there is a problem that when the label is peeled off, the adhesive remains on the peeled surface and sticks and dust adheres.
JP-A-8-99377, JP-A-10-258476, etc. can be referred to as solutions to this problem, but the water resistance is inferior and special processing such as notches is used to easily start peeling. There are disadvantages that you need.
[0004]
[Patent Document 1]
Japanese Examined Patent Publication No. 46-40794
[Patent Document 2]
Japanese Patent Publication No.49-1782
[Patent Document 3]
Japanese Patent Laid-Open No. 56-118437
[Patent Document 4]
JP-A-57-12642
[Patent Document 5]
JP-A-57-56224
[0005]
[Problems to be solved by the invention]
This invention made it the subject which should be solved to eliminate the problem of these prior arts. That is, the present invention is an electrophotographic label that is excellent in water resistance, has a smaller thermal curl when used as a printing label by a heat fixing type electrophotographic printer or a heat fixing type electrophotographic copying machine, and can continuously print a large number of sheets. It was an issue to provide.
Another object of the present invention is to provide an electrophotographic label that is excellent in water resistance as a base material such as a concealment seal and an anti-replacement label and does not require special processing to start peeling.
[0006]
[Means for Solving the Problems]
As a result of intensive studies aimed at solving the above problems, the present inventors have found that the heat of crystallization is 60 J / cm. ^Three By selecting the following base material layer (A), the curl height after printing by the heat fixing type electrophotographic printer or the heat fixing type electrophotographic copying machine is reduced, and good printability is obtained by continuous printing of a large number of sheets. In order to start peeling, if a layer (E) capable of delamination with a peeling strength of 5 to 150 g / cm width and a surface layer (F) with a breaking strength of 500 g / cm width or less can be formed. The present invention has been completed by finding that it is suitable as an electrophotographic label that does not require special processing.
[0007]
That is, the present invention has a crystallization heat of 60 J / cm. ^Three An electrophotographic label having a pressure-sensitive adhesive layer (B) and a release paper (C) on one side of a base material layer (A), which is as follows: A by a heat fixing type electrophotographic printer or heat fixing type electrophotographic copying machine -4 size (210 mm x 297 mm) The average curl height at the four corners after printing for 2 minutes or more after printing is 50 mm or less, and the capacitance is 5 pF / cm ² An electrophotographic label as described above is provided.
In a preferred embodiment of the present invention, the base material layer (A) contains 30 to 100% by weight of the thermoplastic resin and 70 to 0% by weight of the inorganic fine powder and / or the organic filler, and the thermoplastic resins 35 to 97. It is preferable to contain 65 to 3% by weight of inorganic fine powder and / or organic filler by weight.
[0008]
The thermoplastic resin may be composed of only a crystalline resin, an amorphous resin, or an elastomer, or may be a mixture of two or more of these. Preferably, it is a mixture of a crystalline resin and an amorphous resin or a mixture of a crystalline resin and an elastomer.
The crystalline resin is an olefin resin, more preferably a propylene resin. Preferably, the amorphous resin is selected from terpene resins, carboxylic acid vinyl ester resins, acrylic acid esters, methacrylic acid esters, and petroleum resins, and the elastomer is a styrene thermoplastic elastomer or olefinic heat. It is preferably one selected from a plastic elastomer, a urethane thermoplastic elastomer, and an ester thermoplastic elastomer.
Moreover, it is preferable that the base material layer (A) is extended | stretched by at least 1 axial direction. It is preferable that the porosity of the base material layer (A) is 75% or less. The base material layer (A) preferably has a multilayer structure.
[0009]
Further, it is preferable to provide the toner receiving layer (D) on the opposite surface of the base material layer (A) that is in contact with the pressure-sensitive adhesive layer (B). Furthermore, a layer (E) that enables delamination with a peel strength of 5 to 150 g / cm width is preferably provided on the surface of the base material layer (A) where the pressure-sensitive adhesive layer (B) is provided, and the crystallization heat. 60J / cm ^Three More preferably, a surface layer (F) having a breaking strength of 500 g / cm width or less is provided on the surface of the layer (E) enabling delamination, and the crystallization heat is 60 J / cm. ^Three It is as follows. Moreover, the layer (E) which enables delamination can be provided by a coating method.
The electrophotographic label of the present invention is printed by a heat fixing type electrophotographic printer or a heat fixing type electrophotographic copying machine, and includes a recorded matter using the electrophotographic label. The present invention also includes the electrophotographic label. And a printing method for printing with a heat-fixing electrophotographic printer or a heat-fixing electrophotographic copying machine.
[0010]
[Form of the present invention]
Even if the electrophotographic label of the present invention is a base material layer (A) alone or a laminate of the base material layer (A) and another thermoplastic film, the base material layer (A) is delaminated. It is also possible to have a structure having a layer (E) that enables delamination, or a layer (E) that enables delamination and a surface layer (F).
For the electrophotographic label of the present invention, a base material layer (A), an adhesive layer (B), a release paper (C), a toner receiving layer (D), a layer (E) capable of delamination, and a surface layer (F ) In the following order.
(1) Base material layer (A)
The heat of crystallization of the base material layer (A) of the present invention is 60 J / cm. ^Three Below, preferably 55 J / cm ^Three Or less, more preferably 50 J / cm ^Three It is as follows. The heat of crystallization is 60 J / cm ^Three If it exceeds 1, the curl after passing through the heat fixing type electrophotographic printer or the heat fixing type electrophotographic copying machine in the state of being bonded to the release paper (C) will be large, curved, or cylindrical, and many It is difficult to print continuously.
The average curl height capable of continuous printing of a large number of sheets is 50 mm or less, preferably 40 mm or less, more preferably 35 mm or less. If it exceeds 50 mm, it is difficult to stably stack paper at the time of printing and discharging, which causes a discharging problem.
[0011]
The heat of crystallization is measured according to JIS-K-7122. In the present invention, the measured value at a cooling rate of 20 ° C./min [transition heat per gram (J / g)] Raw material density (g / cm ^Three ) Is the heat of crystallization (J / cm ^Three ).
The raw material density is measured in accordance with JIS-K-7112. In the present invention, the base material layer (A) or the resin film is remelted on the heater plate to remove the voids. The density of the cooled film.
Examples of the crystallization heat measuring device include a differential scanning calorimeter (DSC6200, manufactured by Seiko Instruments Inc., trade name).
The base material layer (A) of the present invention preferably has a porous structure having fine pores therein from the viewpoint of helping to reduce the weight of the electrophotographic label. The porosity is 75% or less, preferably 1 to 70%, more preferably 5 to 65%. If the porosity is 75% or less, the material strength of the film is at a good level. The presence of pores in the interior can be confirmed by observing the cross section with an electron microscope.
[0012]
In addition, the porosity in this invention shows the area ratio (%) which a void | occupies in the area | region observed by the electron micrograph of the porosity shown by following Formula, or a cross section. The porosity and area ratio represented by the following formula (1) are the same. Specifically, the area ratio indicated by the pores is obtained by embedding and solidifying a porous resin film with an epoxy resin, and then using a microtome, for example, a cut surface parallel to the thickness direction of the film and perpendicular to the surface direction. And metallizing the cut surface, and then observing with an arbitrary magnification that is easy to observe with a scanning electron microscope, for example, 500 to 2000 times, or taking an electron microscope image and analyzing the image You can ask for it. As an example of how to determine the area ratio, the void portion was traced on the tracing film and painted, and the image was processed with an image analyzer (Nireco Corp. model: Luzex IID). ) To obtain the porosity.
[0013]
Porosity (%) = 100 × (ρ ₀ -Ρ) / ρ ₀ ... (1)
(Where ρ ₀ : Density of non-porous portion of base material layer (A), ρ: density of base material layer (A)]
Moreover, in the case of the laminated body which has the base material layer (A) of this invention on the surface, the thickness and basic weight (g / m) of this part which removed this laminated body and the base material layer (A) of this invention from this ² ), The thickness and basis weight of the resin film layer of the present invention are calculated, the density (ρ) is obtained from this, and the density of the non-porous portion (ρ ₀ ) And the above equation (1).
[0014]
The heat shrinkage ratio after heating for 30 minutes at 120 ° C. of the base material layer (A) of the present invention is 10% or less, preferably 8% or less, more preferably 5% or less, in both vertical and horizontal directions. . When the thermal shrinkage rate exceeds 10%, the curl after passing through the electrophotographic printer is large in a state of being bonded to the release paper (C), and the curl or the cylindrical shape is formed. Have difficulty. This heat shrinkage ratio is determined by cutting the base material layer (A) into a square of a certain size, for example, 100 mm both vertically and horizontally, and measuring its dimensions in a constant temperature and humidity chamber at an air temperature of 23 ° C. and a relative humidity of 50%. After heat-treating in a ventilated oven at 0 ° C. for 30 minutes and taking out, it is allowed to cool in the same constant temperature and humidity chamber for 1 hour, and the dimensions are measured and calculated by comparison with that before the oven heat treatment.
[0015]
<Composition>
The amount of each of the crystalline resin, amorphous resin, elastomer, inorganic fine powder and / or organic filler of the base material layer (A) of the present invention is such that the heat of crystallization of the base material layer (A) is 60 J / cm. ^Three It can be arbitrarily selected within the following range so as to be as follows.
Among the base material layer (A) of the present invention, preferably 30 to 100% by weight of thermoplastic resin, 70 to 0% by weight of inorganic fine powder and / or organic filler, preferably 35 to 97% by weight of thermoplastic resin, The inorganic fine powder and / or the organic filler is 65 to 3% by weight, more preferably 40 to 95% by weight of the thermoplastic resin, and the inorganic fine powder and / or the organic filler is 60 to 5% by weight.
The thermoplastic resin may be composed of only a crystalline resin, an amorphous resin, or an elastomer, or may be a mixture of two or more of these. The thermoplastic resin is preferably a mixture of a crystalline resin and an amorphous resin or a mixture of a crystalline resin and an elastomer. More preferably, it is a mixture of a crystalline resin and an elastomer.
[0016]
The kind of thermoplastic resin used for the base material layer (A) of the present invention is not particularly limited.
As for the crystalline resin, for example, ethylene resins such as high density polyethylene, low density polyethylene and linear polyethylene, olefin resins such as propylene resin; polyethylene terephthalate and copolymers thereof, polyethylene naphthalate, aliphatic polyester And thermoplastic resins such as polyester resins. These may be used in combination of two or more.
Among these, from the viewpoint of chemical resistance, low specific gravity, cost and the like, an olefin resin such as an ethylene resin or a propylene resin is preferable, and a high density polyethylene and a propylene resin are more preferable.
[0017]
Examples of the propylene-based resin include propylene homopolymers such as an isotactic polymer obtained by homopolymerizing propylene, a syndiotactic polymer, or an atactic polymer. In addition, the main component is polypropylene having various stereoregularities obtained by copolymerizing propylene with an α-olefin such as ethylene, 1-butene, 1-hexene, 1-heptene, 4-methyl-1-pentene. Copolymers can also be used. The copolymer may be a binary system or a ternary or higher multi-element system, and may be a random copolymer, a block copolymer, or a graft copolymer.
[0018]
As for amorphous resins, for example, terpene resins such as hydrogenated terpene resins and aromatic modified terpene resins; vinyl ester resins such as vinyl acetate resins and vinyl stearates; acrylic resins, methacrylic resins, methyl (Meth) acrylate resins such as (meth) acrylate resins and ethyl (meth) acrylate resins ((meth) acrylate esters refer to acrylate and methacrylate esters); polycarbonate; atactic polystyrene, syndiotactic Examples include polystyrene resins such as tick polystyrene; thermoplastic resins such as hydrogenated petroleum resins, aliphatic petroleum resins, aromatic petroleum resins, and cyclopentadiene petroleum resins. Among them, preferred are petroleum resins such as hydrogenated petroleum resins, aliphatic petroleum resins, aromatic petroleum resins, and cyclopentadiene petroleum resins. These may be used in combination of two or more.
[0019]
As for the elastomer, for example, isoprene rubber, butadiene rubber, 1,2-polybutadiene, styrene-butadiene rubber, chloroprene rubber, nitrile rubber, ethylene-propylene rubber, ethylene-propylene-ethylidene norbornene rubber, chlorosulfonated polyethylene, acrylic rubber, Examples thereof include epichlorohydrin rubber, silicone rubber, fluorine rubber, urethane rubber, and a thermoplastic elastomer having both incompatible soft segment and hard segment components in the molecule.
[0020]
Examples of thermoplastic elastomers include styrene thermoplastic elastomer (SBC), olefin thermoplastic elastomer (TPO), urethane thermoplastic elastomer (TPU), ester thermoplastic elastomer, vinyl chloride thermoplastic elastomer, and butyl rubber graft polyethylene. , Trans 1,4-polyisoprene, ionomer and the like. Among these, styrene thermoplastic elastomer (SBC) and olefin thermoplastic elastomer (TPO) are preferable, and olefin thermoplastic elastomer (TPO) is more preferable. These may be used in combination of two or more.
[0021]
The base material layer (A) of the present invention preferably has a porous structure having fine pores therein by containing an inorganic fine powder and / or an organic filler.
The amount of the inorganic fine powder or organic filler is 0 to 70% by weight, preferably 3 to 65% by weight, more preferably 5 to 60% by weight. In order to increase the pores, it is better that the amount of the inorganic fine powder and / or the organic filler is large, but for the purpose of improving the surface property of the base material layer (A), it is 70% by weight or less. Is good.
[0022]
The kind of inorganic fine powder and / or organic filler is not particularly limited.
Inorganic fine powders include heavy calcium carbonate, precipitated calcium carbonate, calcined clay, talc, titanium oxide, barium sulfate, aluminum sulfate, silica, zinc oxide, magnesium oxide, diatomaceous earth, silicon oxide, silica and other hydroxyl group-containing inorganic fine powders Examples thereof include composite inorganic fine powders having aluminum oxides or hydroxides around the cores, hollow glass beads and the like. Moreover, the surface treatment goods by the various surface treatment agent of the said inorganic fine powder can also be illustrated.
[0023]
As the surface treatment agent, for example, resin acid, fatty acid, organic acid, sulfate ester type anionic surfactant, sulfonic acid type anionic surfactant, petroleum resin acid, salts thereof such as sodium, potassium, ammonium, or These fatty acid esters, resin acid esters, waxes, paraffins and the like are preferable, and nonionic surfactants, diene polymers, titanate coupling agents, silane coupling agents, and phosphoric acid coupling agents are also preferable. Examples of sulfate-type anionic surfactants include long-chain alcohol sulfates, polyoxyethylene alkyl ether sulfates, sulfated oils, and their salts such as sodium and potassium, and sulfonate-type anionic surfactants. Examples of the agent include alkylbenzene sulfonic acid, alkyl naphthalene sulfonic acid, alkane sulfonic acid, paraffin sulfonic acid, α-olefinic phonic acid, alkyl sulfosuccinic acid and the like, and salts thereof such as sodium and potassium.
[0024]
Examples of fatty acids include caproic acid, caprylic acid, pelargonic acid, capric acid, undecanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, hebenic acid, oleic acid, linoleic acid, linolenic acid, and eleostearic acid. Examples of the organic acid include carboxylic acid and sulfonic acid, and examples of the nonionic surfactant include a polyethylene glycol ester type surfactant. These surface treatment agents can be used alone or in combination of two or more.
Among these, use of heavy calcium carbonate, clay, or diatomaceous earth is preferable because it is inexpensive and has good pore forming properties when formed by stretching.
[0025]
The organic filler is selected from incompatible resins having a melting point or glass transition point higher than those of the above-mentioned thermoplastic resin for the purpose of forming pores. Specific examples include polyethylene terephthalate, polybutylene terephthalate, polyamide, polycarbonate, polyethylene naphthalate, polystyrene, acrylic acid ester or methacrylic acid ester polymer or copolymer, melamine resin, polyphenylene sulfite, polyimide, poly ether ether ketone. And polyphenylene sulfide, a homopolymer of cyclic olefin, and a copolymer of cyclic olefin and ethylene [cyclic olefin copolymer (COC)]. Among these, when an olefin resin is used as the thermoplastic resin of the base layer (A), polyethylene terephthalate, polybutylene terephthalate, polyamide, polycarbonate, polyethylene naphthalate, polystyrene, cyclic olefin homopolymer and cyclic Those selected from copolymers of olefin and ethylene are preferred.
[0026]
Among inorganic fine powders or organic fillers, inorganic fine powders are more preferable from the viewpoint that the amount of heat generated during combustion is small.
The average particle size of the inorganic fine powder used in the present invention or the average dispersed particle size of the organic filler is preferably 0.01 to 30 μm, more preferably 0.1 to 20 μm, and still more preferably 0.5 to 15 μm. It is. In view of ease of mixing with the thermoplastic resin, 0.1 μm or more is preferable. In addition, when pores are generated in the interior by stretching to improve printability, the thickness is preferably 20 μm or less from the viewpoint of making it difficult to cause troubles such as sheet breakage during stretching and a decrease in strength of the surface layer.
[0027]
The average particle size of the inorganic fine powder used in the present invention is, for example, a particle measuring device, for example, a particle corresponding to 50% cumulatively measured by a laser diffraction particle measuring device “Microtrack” (trade name, manufactured by Nikkiso Co., Ltd.). It can be measured by the diameter (cumulative 50% particle diameter). Further, the particle diameter of the organic filler dispersed in the thermoplastic resin by melt kneading and dispersion is obtained as an average value of the particle diameter by measuring at least 10 particles by observing the cross section of the base material layer (A). It is also possible.
The fine powder used for the base material layer (A) of the present invention may be selected from the above and used alone or in combination of two or more. Good. When two or more types are used in combination, a combination of an inorganic fine powder and an organic filler may be used.
[0028]
When these fine powders are blended and kneaded in a thermoplastic resin, an antioxidant, an ultraviolet stabilizer, a dispersant, a lubricant, a compatibilizer, a flame retardant, a color pigment, and the like can be added as necessary. Moreover, when using the base material layer (A) of this invention as a durable material, it is preferable to add antioxidant, a ultraviolet stabilizer, etc. When an antioxidant is added, it is usually added within a range of 0.001 to 1% by weight. Specifically, sterically hindered phenol-based, phosphorus-based, amine-based stabilizers, and the like can be used. When using an ultraviolet stabilizer, it is usually used within the range of 0.001 to 1% by weight. Specifically, sterically hindered amines, benzotriazole-based, benzophenone-based light stabilizers, and the like can be used.
[0029]
A dispersant or a lubricant is used for the purpose of dispersing inorganic fine powder, for example. The amount used is usually in the range of 0.01 to 4% by weight. Specifically, silane coupling agents, higher fatty acids such as oleic acid and stearic acid, metal soaps, polyacrylic acid, polymethacrylic acid or salts thereof can be used. Furthermore, when using an organic filler, the type and amount of the compatibilizer are important because they determine the particle form of the organic filler. Preferred compatibilizers for organic fillers include epoxy modified polyolefins and maleic acid modified polyolefins. Moreover, it is preferable that the addition amount of a compatibilizing agent shall be 0.05-10 weight part with respect to 100 weight part of organic fillers.
[0030]
As a method for mixing the constituent components of the base material layer (A) of the present invention, various known methods can be applied and are not particularly limited, but the temperature and time of mixing are also appropriately selected according to the properties of the components used. . Mixing in a state dissolved or dispersed in a solvent or a melt kneading method can be mentioned. The melt kneading method has good production efficiency. After mixing thermoplastic resin, inorganic fine powder and / or organic filler and dispersant in powder or pellet form with Henschel mixer, ribbon blender, super mixer, etc., melt knead with twin screw kneading extruder, strand Examples include a method of extruding into a shape and cutting to form a pellet, and a method of extruding into water from a strand die and cutting with a rotary blade attached to the tip of the die. Further, there may be mentioned a method in which a dispersant in a state of being dissolved in powder, liquid or water or an organic solvent is once mixed with an inorganic fine powder and / or an organic filler and further mixed with other components such as a thermoplastic resin.
[0031]
The thickness of the base material layer (A) of the present invention is not particularly limited. For example, it can be adjusted to 10 to 500 μm, preferably 30 to 300 μm.
The base material layer (A) of the present invention may have a single layer structure, a two layer structure, or a multilayer structure of three or more layers. Although the base material layer (A) of the present invention may or may not be stretched, it can be reduced in weight by forming pores inside the film by stretching, and a flexible film can be formed. It is preferable that the film is stretched at least in a uniaxial direction.
The number of stretching axes of this multilayer structure is 1 axis / 1 axis, 1 axis / 2 axis, 2 axis / 1 axis, 1 axis / 1 axis / 2 axis, 1 axis / 2 axis / 1 axis, 2 axis / 1 axis / 1 axis, 1 axis / 2 axes / 2 axes, 2 axes / 2 axes / 1 axis, 2 axes / 2 axes / 2 axes may be used. The multilayering of the base material layer (A) makes it possible to add various functions such as writability, printability, thermal transfer suitability, scratch resistance, and secondary processing suitability.
[0032]
The electrophotographic label of the present invention may be a laminate in which the base material layer (A) is laminated on at least one surface of another thermoplastic film, laminated paper, pulp paper, nonwoven fabric, cloth, wood board, metal plate, or the like. Good. Furthermore, as another thermoplastic film to laminate | stack, it can laminate | stack on transparent or opaque films, such as a polyester film, a polyamide film, a polystyrene film, a polyolefin film, for example. The heat of crystallization of the electrophotographic label made of the obtained laminate is 60 J / cm. ^Three Below, preferably 55 J / cm ^Three Or less, more preferably 50 J / cm ^Three It is as follows.
There is no restriction | limiting in particular in the thickness of a laminated body, According to a use, it selects suitably. As an example, it is 15-2000 micrometers, Preferably it is 35-1000 micrometers, More preferably, it is 50-500 micrometers.
[0033]
<Production method>
The base material layer (A) of the present invention can be produced by combining various methods known to those skilled in the art. Any resin film produced by any method is included in the scope of the present invention as long as the resin film satisfying the conditions of the present invention is used.
As a manufacturing method of the base material layer (A) of the present invention, various known film manufacturing techniques and combinations thereof are possible. For example, a cast molding method in which a molten resin is extruded into a sheet using a single-layer or multi-layer T-die connected to a screw-type extruder, a stretched film method using void generation by stretching, and pores during rolling Rolling method and calender molding method for generating water, a foaming method using a foaming agent, a method using pore-containing particles, an inflation molding method, a solvent extraction method, a method of dissolving and extracting mixed components, and the like. Of these, the stretched film method is preferred.
[0034]
When stretching, it is not always necessary to stretch only the base material layer (A) of the present invention. For example, when it is going to finally manufacture the electrophotographic label which formed the layer (E) and surface layer (F) etc. which enable the below-mentioned delamination on the base material layer (A) of this invention The base layer (A), the layer (E) capable of delamination and the surface layer (F) may be laminated and then stretched together. If the layers are laminated in advance and stretched together, the cost becomes simpler and cheaper than the case of stretching separately and laminating. In addition, it becomes easier to control the pores formed in the base layer (A) of the electrophotographic label of the present invention and the layer (E) and the surface layer (F) enabling delamination.
[0035]
Various known methods can be used for stretching. In the case of a non-crystalline resin, the stretching temperature is not less than the glass transition temperature of the thermoplastic resin to be used. In the case of a crystalline resin, the stretching temperature is not less than the glass transition temperature of the non-crystalline portion to the melting point of the crystal portion. It can be performed within a suitable temperature range. Specifically, longitudinal stretching using the peripheral speed difference of the roll group, transverse stretching using a tenter oven, rolling, inflation stretching using a mandrel for a tubular film, simultaneous biaxial stretching by a combination of a tenter oven and a linear motor It can be stretched by, for example.
[0036]
The draw ratio is not particularly limited, and is appropriately determined in consideration of the purpose of use of the resin film of the present invention and the characteristics of the thermoplastic resin used. For example, when a propylene homopolymer or a copolymer thereof is used as a thermoplastic resin, it is about 1.2 to 12 times, preferably 2 to 10 times when stretched in one direction, and biaxially stretched. The area magnification is 1.5 to 60 times, preferably 10 to 50 times. When using other thermoplastic resins, it is 1.2 to 10 times, preferably 2 to 7 times in the case of stretching in one direction, and 1.5 to 20 times in area magnification in the case of biaxial stretching. Preferably it is 4 to 12 times.
[0037]
Furthermore, heat treatment at a high temperature can be performed as necessary. The stretching temperature is a temperature 2 to 160 ° C. lower than the melting point of the thermoplastic resin to be used. When a propylene homopolymer or a copolymer thereof is used as the thermoplastic resin, it is preferably a temperature 2 to 60 ° C. lower than the melting point, The stretching speed is preferably 20 to 350 m / min.
The film thus obtained has a lot of fine pores having a porosity calculated by the above formula (1) of 75% or less, preferably 1 to 70%, more preferably 5 to 65% inside the film. It is what you have. The presence of pores makes it more supple compared to a stretched film that does not have pores.
[0038]
In order to improve adhesion and coating properties between the base material layer (A), the pressure-sensitive adhesive layer (B) and the toner receiving layer (D) described below, at least one surface of the base material layer (A) is subjected to a surface treatment. It is preferable.
Examples of the surface treatment method include surface oxidation treatment and treatment with a surface treatment agent. It is preferable to carry out a combination of surface oxidation and treatment with a surface treatment agent.
Specific examples of the surface oxidation treatment include a treatment method selected from corona discharge treatment, flame treatment, plasma treatment, glow discharge treatment and ozone treatment, preferably corona treatment and flame treatment, more preferably corona treatment. It is processing.
[0039]
The treatment amount is 600 to 12,000 J / m in the case of corona treatment. ² (10-200W / min / m ² ), Preferably 1,200 to 9,000 J / m ² (20-180W ・ min / m ² ). 600 J / m to fully obtain the effect of corona discharge treatment ² (10W / min / m ² ) Above, 12,000 J / m ² (200W / min / m ² ) Since the effect of processing reaches a peak at over 1,2,000 J / m ² (200W / min / m ² ) The following is sufficient. 8,000 to 200,000 J / m for frame processing ² , Preferably 20,000-100,000 J / m ² Is used. 8,000 J / m for clear frame processing effect ² Above, 200,000 J / m ² Since the effect of the treatment will reach its peak at over 200,000 J / m ² The following is sufficient.
[0040]
As the surface treatment agent, one or a mixture of two or more selected from the materials described below can be used. In particular, it is preferable to use a surface treating agent combined with a primer as a main component because adhesion between the pressure-sensitive adhesive layer (B) and the toner receiving layer (D) can be improved. Specific examples thereof include polyethyleneimines such as polyethyleneimine, butylated polyethyleneimine, hydroxypropylated polyethyleneimine, hydroxyethylated polyethyleneimine, 2,3-dihydroxypropylated polyethyleneimine, poly (ethyleneimine-urea), and polyaminepolyamide. Examples thereof include water-soluble primers selected from the group consisting of adducts, epichlorohydrin adducts such as polyamine polyamide, acrylic emulsions, and tertiary or quaternary nitrogen-containing acrylic resins.
[0041]
The method for forming the surface treatment layer using these surface treatments is not particularly limited. For example, using a roll coater, blade coater, bar coater, air knife coater, size press coater, gravure coater, reverse coater, die coater, lip coater, spray coater, etc., smoothing if necessary or extra after drying process It can be formed by removing water or a hydrophilic solvent.
When the base material layer (A) is a stretched film, the coating of the surface treatment agent may be performed in one step or in multiple steps regardless of the longitudinal or lateral stretching.
[0042]
(2) Adhesive layer (B)
The type and thickness (coating amount) of the pressure-sensitive adhesive layer (B) provided on one side of the base material layer (A) can be variously selected depending on the type of adherend, the environment in which it is used, the strength of adhesion, etc. is there.
Typical water-based or solvent-based pressure-sensitive adhesives include rubber-based pressure-sensitive adhesives, acrylic pressure-sensitive pressure-sensitive adhesives, and silicone-based pressure-sensitive adhesives. Specific examples of rubber-based pressure-sensitive adhesives include polyisobutylene rubber and butyl rubber. Or a mixture of these rubber adhesives with tackifiers such as abietic rosin ester, terpene / phenol copolymer, terpene / indene copolymer, and the like. As specific examples of the acrylic pressure-sensitive adhesive, the glass transition point of 2-ethylhexyl acrylate / n-butyl acrylate copolymer, 2-ethylhexyl acrylate / ethyl acrylate / methyl methacrylate copolymer, or the like is −20 ° C. or lower. Things. These synthetic polymer pressure-sensitive adhesives can be used in a form dispersed in water such as an organic solvent solution, a dispersion or an emulsion.
In order to improve the opacity of the label, it is possible to use a pressure sensitive adhesive containing a pigment such as titanium white.
[0043]
The pressure-sensitive adhesive layer (B) can be formed by coating on a bonding surface of the base material layer (A) and a release paper (C) described later in a solution state. Coating is done by roll coater, blade coater, bar coater, air knife coater, gravure coater, reverse coater, die coater, lip coater, spray coater, comma coater, etc., smoothing or drying process if necessary A pressure-sensitive adhesive layer (B) is formed.
The pressure-sensitive adhesive layer (B) is formed by applying a pressure-sensitive adhesive to the release paper (C) described later, drying as necessary, and forming the pressure-sensitive adhesive layer (B) on the base material layer (A). Although the method of laminating is common, depending on the case, it can also form by apply | coating an adhesive directly to a base material layer (A).
The coating amount of the pressure-sensitive adhesive is not particularly limited, but usually 3 to 60 g / m in solid content. ² , Preferably 10 to 40 g / m ² Range.
[0044]
(3) Release paper (C)
The release paper (C) provided with the pressure-sensitive adhesive layer sandwiched between the base material layer (A) and the pressure-sensitive adhesive layer ( Generally, the silicon contact is applied to the surface in contact with B).
The release paper (C) can be a general one, and it can be used for high-quality paper or kraft paper as it is, or for calendering, resin coating or film lamination, glassine paper, coated paper, plastic film, etc. A siliconized product can be used.
[0045]
(4) Toner receiving layer (D)
In order to improve the reproducibility of images and characters on the printing surface side of the base material layer (A) of the present invention, a toner receiving layer (D) comprising an inorganic and / or organic pigment and a binder may be provided. For example, acrylic resin, polyester resin, urethane resin, vinyl acetate copolymer, maleic acid copolymer resin and silica, talc, titanium oxide, heavy calcium carbonate, precipitated calcium carbonate, etc. An inorganic fine powder is mentioned. Further, various materials can be added as necessary. The material to be added can be appropriately selected from materials usually used for the toner receiving layer (D). For example, a curing agent, an ultraviolet absorber, a surfactant, or the like can be used, but the amount of these used must be within a range that does not excessively impair the water resistance and weather resistance of the toner receiving layer (D).
[0046]
The method for forming the toner receiving layer (D) is not particularly limited. Examples thereof include a dry lamination method, an extrusion lamination method, a wet lamination method, and a coating method. Among these, the coating method is preferable, and each component constituting the toner receiving layer (D) is dispersed and diluted in a solvent using a non-aqueous solvent such as toluene, ethyl acetate, methyl ethyl ketone, isopropyl alcohol alone or in combination. A method of coating and applying can be exemplified. Further, in a range where the water resistance of the toner-receiving layer (D) can be maintained, it can be dispersed and diluted with a diluent solvent mainly composed of water, optionally in combination with methanol, ethanol, etc. to form a paint and can be applied. . The solid content concentration of the prepared coating solution is usually 10 to 60% by weight, preferably 15 to 50% by weight. If the amount is less than 10% by weight, energy is required to evaporate the diluted solvent, which tends to be uneconomical. On the other hand, if it exceeds 60% by weight, the coating suitability tends to deteriorate.
[0047]
The method for applying the toner receiving layer (D) paint is not particularly limited. For example, a roll coater, a blade coater, a bar coater, an air knife coater, a gravure coater, a reverse coater, a die coater, a lip coater, a spray coater, a size press coater or the like can be used. After these coatings, if necessary, the toner receiving layer can be formed by smoothing and drying to remove excess solvent. The coating amount is 0.005 to 35 g / m as a solid content after drying. ² , Preferably 0.01-20 g / m ² It is. 35 g / m ² Above this, the cost tends to be high and the economy is inferior.
[0048]
(5) Layer enabling delamination (E)
The electrophotographic label of the present invention has a layer (E) capable of delamination, or a layer (E) and surface capable of delamination on the surface on which the pressure-sensitive adhesive layer (B) of the base material layer (A) is provided. You may have a layer (F).
Crystallization of a laminated film having a base layer (A) and a layer (E) capable of delamination, or a base layer (A) and a layer (E) and a surface layer (F) capable of delamination Heat is 60 J / cm ^Three Below, preferably 55 J / cm ^Three Or less, more preferably 50 J / cm ^Three It is as follows.
The layer (E) enabling delamination according to the present invention is a layer having a lower strength than the base layer (A) and the surface layer (F), and the delamination of the surface layer (F) according to the present invention is possible. Is performed by destroying the layer (E).
The preferred form of the layer (E) that enables delamination is 10 to 80% by weight, preferably 15 to 70% by weight, preferably 90 to 20% by weight, and preferably 85 to 30% by weight of the thermoplastic resin. It is a stretched thermoplastic resin film containing 10% by weight, or 10 to 80% by weight of inorganic fine powder and / or organic filler, preferably 15 to 70% by weight, 90 to 20% by weight of thermoplastic resin, preferably 85 to 30%. A binder resin containing% by weight can be provided by a coating method. When the content of the inorganic fine powder and / or organic filler in the layer (E) capable of delamination is less than 10% by weight, sufficient peelability cannot be obtained, and when it exceeds 80% by weight, molding stability is impaired. It is.
[0049]
As a thermoplastic resin, the thermoplastic resin quoted by the base material layer (A) term can be used, and it is preferable to use polyolefin resin similarly to a base material layer (A). As the binder resin, acrylic ester resin, chlorinated polypropylene or the like is used. As the inorganic fine powder and / or the organic filler, those mentioned in the paragraph of the base material layer (A) can be used.
The thickness of the layer (E) that enables delamination is 0.1 to 500 μm, preferably 0.2 to 200 μm, and more preferably 0.5 to 100 μm. If it is less than 0.1 μm, sufficient releasability cannot be obtained, and if it is 500 μm or more, the peeled surface is not uniform and becomes uneven, which causes printing defects when printing on the peeled surface.
When the layer (E) capable of delamination is a stretched resin film layer, it is possible to obtain a layer (E) capable of delamination with a small thickness and uniform uniformity by stretch molding. Further, by stretching the layer (E) capable of delamination containing the inorganic fine powder and / or organic filler, fine voids are formed in the layer (E) capable of delamination to reduce the strength. The peel strength described later of the surface layer (F) targeted by the present invention can be obtained.
[0050]
(6) Surface layer (F)
The surface layer (F) in this invention is a layer provided so that it may peel from a base material layer (A) by destruction of the layer (E) which enables delamination.
As the thermoplastic resin constituting the surface layer (F), the thermoplastic resins mentioned in the paragraph of the substrate layer (A) can be used, and it is preferable to use a polyolefin-based resin similarly to the substrate layer (A). . Furthermore, in order to set the breaking strength of the surface layer (F) to 500 g / cm or less which is the object of the present invention, the thermoplastic resin used for the surface layer (F) is desirably a resin having a low breaking strength, Specific examples include ethylene resins, propylene resins, ethylene / unsaturated carboxylic acid copolymers, and ethylene / acrylic acid copolymers.
[0051]
The surface layer (F) may or may not contain the inorganic fine powder and / or organic filler, and does not contain the inorganic fine powder and / or organic filler or has a small content. The surface layer (F) excellent in transparency can be obtained, and when the base material layer (A) is peeled off, the information recognition under the surface layer (F) is excellent and preferable.
The surface layer (F) is preferably a stretched resin film layer, and it is possible to obtain a surface layer (F) that is thin and has a uniform thickness by stretch molding.
The film thickness of the surface layer (F) is 20 μm or less, more preferably 0.1 to 10 μm, still more preferably 0.5 to 6 μm. When the film thickness exceeds 20 μm, it becomes difficult to obtain the surface layer (F) having the intended breaking strength of the present invention.
[0052]
<Capacitance>
The capacitance of the electrophotographic label of the present invention is 5 pF / cm per unit electrode area. ² Or more, preferably 6 to 1000 pF / cm ² , More preferably 8 to 800 pF / cm ² It is. Capacitance of 5 pF / cm ² If it is less than 1, the toner transfer rate is low and sufficient print density cannot be obtained in any printing mode of the printer. Also, the capacitance is 1000 pF / cm ² If the value exceeds 1, the charge applied to transfer the toner to the paper in the printer will remain on the electrophotographic label when the printer is discharged, and the sheet and the electrophotographic label will attract each other on the discharge tray, and blocking will easily occur. Tend.
[0053]
1000pF / cm ² In order to obtain a capacitance exceeding 1, it is necessary to add a large amount of capacitance modifier to the electrophotographic label, which tends to increase the production cost. For the measurement of the electrostatic capacity of the electrophotographic label of the present invention, “4192ALFIMPEDEANEANALYZER” (HEWLETTPACKARD, trade name) is used, and the temperature is 23 ° C. and the relative humidity is 50%. A sample larger than the electrode diameter was sandwiched, a voltage of 5 V was applied, measurement was performed at a frequency in the range of 10 Hz to 1 MHz, and a measurement value at a frequency of 300 Hz was used as a representative value.
[0054]
<Peel strength>
Peel strength means that a laminated film provided with a layer (E) and a surface layer (F) capable of delamination on the base material layer (A) of the present invention is placed in a temperature-controlled room (temperature 20 ° C., relative humidity 65%). After storage for 12 hours, an adhesive tape (made by Nichiban Co., Ltd., trade name “Cerotape”) is pasted on the surface layer (F), cut into a width of 10 mm and a length of 100 mm, and a tensile tester (manufactured by Shimadzu) The substrate layer (A) and the surface layer (F) are peeled off at an angle of 180 ° at a pulling speed of 300 mm / min. Measured and expressed with average values in the horizontal and vertical directions. The peel strength of the present invention is 5 to 150 g / cm, preferably 7 to 100 g / cm. When the peel strength is less than 5 g / cm, there is a defect that peeling easily occurs in paper feeding and discharging at the time of secondary processing such as printing, printing, and injuries, and there is a problem in secondary workability. If the width exceeds 150 g / cm, the surface layer (F) does not peel or it is necessary to increase the stress required for peeling, which is not practical. In addition, material destruction occurs in places other than the layer (E) that enables delamination, and fluffing occurs on the peeled surface.
[0055]
<Break strength>
After storing the laminated film provided with the layer (E) and the surface layer (F) capable of delamination on the base material layer (A) of the present invention in a thermostatic chamber (temperature 20 ° C., relative humidity 65%) for 12 hours , Cut to 10mm width and 100mm length, and further surface layer (F) Reinforce with adhesive tape (made by Nichiban Co., Ltd., trade name “Cellotape”) to half the length of the surface. The surface layer (F) of the portion reinforced with the adhesive tape is peeled off from the base material layer (A) by hand to prepare a sample for measuring the breaking strength. The part of the prepared sample where the surface layer (F) is not peeled off and the peeled surface layer (F) are set in a tensile tester (manufactured by Shimadzu Corporation, AUTOGRAPH), and the surface layer (at a tensile rate of 300 mm / min) F) reads the load at the time of fracture, and expresses it with the average value in the horizontal and vertical directions.
The breaking strength of the surface layer (F) of the present invention is 500 g / cm or less, preferably 400 g / cm or less, more preferably 300 g / cm or less. When the breaking strength of the surface layer (F) is higher than 500 g / cm, in order to peel off the surface layer (F) from the base material layer (A), a special notch or slit is provided only on the surface layer (F). Processing is required, and the desired performance of the present invention is not exhibited.
[0056]
<Curl after printing by thermal fixing type electrophotographic printer or thermal fixing type electrophotographic copying machine>
When the electrophotographic label of the present invention is cut into A-4 size (210 mm × 297 mm) and printed by a heat fixing type electrophotographic printer or a heat fixing type electrophotographic copying machine, curling at four corners after two minutes or more from printing. The average height is preferably 50 mm or less. The heat fixing method is generally a fixing method using a heat roll or a heat belt.
More specifically, the electrophotographic label is cut into an A-4 size (210 mm × 297 mm), left in a constant temperature and humidity room at a temperature of 23 ° C. and a relative humidity of 50% for one day, and then a commercially available heat roll fixing type electrophotographic printer ( By using LASER SHOT LBP-950 (trade name, manufactured by Canon Inc.), printing is performed through a paper passing route with the base material layer (A) or the toner receiving layer (D) as the printing surface. In the print test model diagram, an object having a pattern in which heavy colors and single colors are mixed is selected. After passing through the printer, leave the electrophotographic label on a flat surface at a humidity of 23 ° C and a relative humidity of 50%, and place the curls at the four corners upward 2 minutes after passing the paper. The average value of the heights of the four corners is measured with the plus when the label is lifted to the label side and the minus when the label is lifted to the release paper side. The average value is preferably 50 mm or less. If it exceeds 50 mm, it is difficult to continuously print a large number of sheets.
[0057]
<Printing>
The electrophotographic label of the present invention is not only used as a sheet for a heat fixing type electrophotographic printer or heat fixing type electrophotographic copying machine, but also as a product name, manufacturer, expiration date, character picture, entry field, barcode. Etc. can be printed and printed by letterpress printing, gravure printing, flexographic printing, solvent-type offset printing, UV-curing offset printing, roll-type rotary printing, and the like.
Moreover, after providing a coating layer such as an inkjet receptive layer on the front surface and back surface of the base material layer (A) and / or the layer (E) or the surface layer (F) that enables delamination as necessary, inkjet recording is performed. It is possible to create printed matter by printing.
These printing and printing may be performed in the state of the base material layer (A) or the laminated film alone, or may be performed in a state having a release paper.
[0058]
【Example】
Hereinafter, the present invention will be described more specifically with reference to Examples, Comparative Examples and Test Examples. The materials, amounts used, ratios, operations, and the like shown in the following examples and the like can be appropriately changed without departing from the gist of the present invention. Therefore, the scope of the present invention is not limited by the specific examples shown below.
The electrophotographic label of the present invention and a comparative electrophotographic label were produced according to the following procedure. Table 1 summarizes the thermoplastic resin, inorganic fine powder, and organic filler used.
[0059]
[Table 1]

[0060]
Example 1
<Base material layer (A)>
A composition [▲ 1 ▼] in which 10% by weight of charcoal cal (described in Table 1) is blended with a mixture of 6% by weight of PP (described in Table 1) and 84% by weight of HSBR (described in Table 1), 250 The mixture was kneaded with an extruder set at 0 ° C., extruded into a strand, and cut into pellets. This composition [(1)] was extruded into a film form from a T-die connected to an extruder set at 250 ° C., and cooled with a cooling device to obtain an unstretched film (thickness: 55 μm, heat of crystallization: 6J / cm ^Three ).
The applied energy density is 90 W · min / m on both sides of this film. ² The corona discharge treatment was performed at
[0061]
In addition, in the melt-kneading of the resin component or the mixture of the fine powder and the resin component in each Example and Comparative Example, the total weight of the resin component and the fine powder is 100 parts by weight, and in addition to this, BHT is used as an antioxidant. 0.2 parts by weight of (4-methyl-2,6-di-t-butylphenol) and 0.1 parts by weight of Irganox 1010 (phenolic antioxidant, manufactured by Ciba Geigy Corporation) were added.
The particle diameter of the calcium carbonate powder used in the examples of the present specification is a cumulative 50% particle diameter measured by a laser diffraction particle measuring device “Microtrack” (trade name, manufactured by Nikkiso Co., Ltd.).
[0062]
<Formation of pressure-sensitive adhesive layer (B) and bonding of release paper (C)>
Polyethylene film is laminated on both sides of fine paper, and silicon treatment is applied on one side. Thickness 100μm, density 0.9g / cm ^Three Pressure sensitive adhesive “Olivein BPS-1109” (trade name, manufactured by Toyo Ink Chemical Co., Ltd.) in a solid content of 25 g / m on the silicon treated surface of the release paper (C) ² Then, it was coated with a comma coater and dried to obtain an adhesive layer (B). The pressure-sensitive adhesive layer (B) on the obtained release paper (C) was bonded to the base material layer (A) to obtain the electrophotographic label of the present invention.
The obtained electrophotographic label was evaluated in the following manner. The evaluation results are summarized in Table 2.
[0063]
<Evaluation>
i. Evaluation of curl height
The obtained electrophotographic label of the present invention was cut into A-4 size (210 mm × 297 mm) and left in a constant temperature and humidity room at a temperature of 23 ° C. and a relative humidity of 50% for 1 day. Next, with a commercially available heat roll fixing type electrophotographic printer “LASER SHOT LBP-950” (trade name, manufactured by Canon Inc.), the base material layer (A) is passed upward as the printing surface, and discharged. Even at that time, printing was performed along the path with the print side up.
After passing through the printer, the electrophotographic label was left on a flat table in an atmosphere of humidity 23 ° C. and relative humidity 50%, and the curl height at the four corners after 2 minutes of paper passing was evaluated.
ii. Capacitance measurement
The obtained electrophotographic label of the present invention has an electrostatic capacity of 23 mm and a relative humidity of 50% in a constant temperature and humidity chamber using “4192 ALFIMPEDANCE ANALYZER” (HEWLETTPACKARD, trade name) and an electrode diameter of 38 mm. A larger sample was inserted and a voltage of 5 V was applied, and evaluation was performed at a frequency of 300 Hz.
[0064]
iii. Evaluation of print quality
The printed image and characters were thickened and deformed, the print density was insufficient, and the background was visually observed and evaluated according to the following criteria.
Very good (◎) Images and characters are clear. (Actual use possible)
Good (O) Thickness and deformation, insufficient print density, and little soiling. (Actual use possible)
Defective (x) thickening and deformation, insufficient print density, and background staining are conspicuous. (Difficult to use)
[0065]
iv. Evaluation of water resistance
The obtained electrophotographic label was cut into a 50 mm × 50 mm square, immersed in water at 20 ° C. for 1 day, then the release paper was peeled off, and the state when the substrate was torn by hand was evaluated according to the following criteria. .
Very good (◎) The substrate is not broken. (Actual use possible)
Good (◯) The substrate is difficult to tear. (Actual use possible)
A defective (x) substrate is easily broken. (Difficult to use)
[0066]
(Example 2)
The types and amounts of the composition components of the composition [(2)] are as shown in Table 2, and after obtaining an unstretched film by the same operation as in Example 1, the unstretched film was brought to 145 ° C. (temperature a). After heating, the film was stretched 5 times in the longitudinal direction to obtain a stretched film (thickness: 60 μm, crystallization heat: 31 J / cm ^Three ). Thereafter, an electrophotographic label was produced by the same operation as in Example 1 and evaluated. The evaluation results are shown in Table 2.
[0067]
(Example 3)
The types and amounts of the components of the composition [3] were as shown in Table 2, and after obtaining an unstretched film by the same operation as in Example 1, the unstretched film was heated to 140 ° C. (temperature a). After heating, the film was stretched 5 times in the longitudinal direction to obtain a stretched film.
The composition [3] was extruded into a film form from a T-die connected to an extruder set at 240 ° C. The obtained film was laminated on both sides of the 5-fold stretched film prepared by the above operation, cooled to 55 ° C., heated to 160 ° C. (temperature b), and stretched 8 times in the transverse direction with a tenter. Then, it annealed at 165 degreeC (temperature c), cooled to 50 degreeC, slit the ear | edge part, and obtained the film of 3 layer structure (uniaxial stretching / biaxial stretching / uniaxial stretching) (thickness) : 10/40/10 μm = 60 μm, heat of crystallization: 46 J / cm ^Three ). Thereafter, an electrophotographic label was produced by the same operation as in Example 1 and evaluated. The evaluation results are shown in Table 2.
[0068]
(Examples 4 to 6)
An electrophotographic label was prepared and evaluated in the same manner as in Example 1 except that the types and amounts of the components of Composition [4] to Composition [6] were as shown in Table 2. went. The evaluation results are shown in Table 2.
(Example 7)
The type and amount of the composition component of the composition [7] are as shown in Table 2, and a die having a three-layer structure is used by using a multilayer die to which two different extruders set at 250 ° C. are connected. It was extruded into a film shape so as to be laminated inside, and cooled with a cooling device to obtain an unstretched film.
Next, this unstretched film was heated to 140 ° C. (temperature a), then stretched 5 times in the longitudinal direction, and then cooled to obtain a stretched film.
Again, it was heated to 160 ° C. (temperature b) and stretched 8 times in the transverse direction with a tenter. Then, it annealed at 165 degreeC (temperature c), cooled to 50 degreeC, slit the ear | edge part, and obtained the film of 3 layer structure (biaxial stretching / biaxial stretching / biaxial stretching) (thickness) : 10/45/10 μm = 65 μm, heat of crystallization: 44 J / cm ^Three ). Thereafter, an electrophotographic label was produced by the same operation as in Example 1 and evaluated. The evaluation results are shown in Table 2.
[0069]
(Example 8)
Except for the molding conditions listed in Table 2, a corona discharge treatment film produced by the same operation as in Example 3 was used as a support (single side designation), and the following toner receiving layer coating solution had a solid content. 5g / m ² And then cured at 90 ° C. for 1 minute to obtain a film. Thereafter, an electrophotographic label in which a release paper by the same operation as in Example 1 was bonded to the opposite surface side on which the toner receiving layer was formed was prepared and evaluated. The evaluation results are shown in Table 2.
[0070]
<Coating liquid for toner receiving layer>
As a toner receiving layer coating solution, 15 parts of 2-hydroxyethyl methacrylate, 50 parts of methyl methacrylate, 35 parts of ethyl acrylate and 100 parts of toluene were charged into a three-necked flask equipped with a stirrer, a reflux condenser and a thermometer, and nitrogen was added. After substitution, 0.6 part of 2,2′-azobisisobutyronitrile was polymerized at 80 ° C. for 4 hours using an initiator. The resulting solution was a 50% toluene solution of a hydroxyl group-containing methacrylate polymer having a hydroxyl value of 65.
[0071]
Subsequently, hexamethylene diisocyanate (manufactured by Nippon Polyurethane Industry Co., Ltd .: Coronate HL) 75% ethyl acetate solution, silica powder having an average secondary particle size of 3 μm (manufactured by Fuji Silysia Co., Ltd .: Cylicia 370), average particles A heavy calcium carbonate powder having a diameter of 1.5 μm (made of calcium Shiroishi) was blended at a solid content ratio shown below.
《Solid content ratio》
Methacrylic acid ester polymer 48% by weight
Hexamethylene diisocyanate 2% by weight
Silica 25% by weight
Heavy calcium carbonate 25% by weight
Butyl acetate was added to this mixture to adjust the solid content to 35% by weight.
[0072]
(Comparative Example 1)
An electrophotographic label was prepared and evaluated in the same manner as in Example 1, except that the types and amounts of the components of the composition [8] were as shown in Table 2. The evaluation results are shown in Table 2.
(Comparative Example 2)
An electrophotographic label was prepared and evaluated in the same manner as in Example 3, except that the types and amounts of the components of the composition [9] were as shown in Table 2. The evaluation results are shown in Table 2.
[0073]
(Comparative Example 3)
250 μm thick, 0.9 g / cm density ^Three An electrophotographic label was prepared and evaluated in the same manner as in Comparative Example 2 except that a release paper having a polyethylene film laminated on both sides of the high-quality paper and a silicon treatment on one side was used. The evaluation results are shown in Table 2.
(Comparative Example 4)
Using commercially available pulp paper “My Recycle Paper 100w” (NBS Ricoh Co., Ltd., trade name), an electrophotographic label was prepared and evaluated in the same manner as in Example 1. The evaluation results are shown in Table 2.
[0074]
[Table 2]

[0075]
Example 9
The composition and composition of the composition [○ 10] as the layer (E) and the base material layer (A) are as follows. Using [3] and a multilayer die to which two different extruders set at 250 ° C. are connected, they are extruded in a film shape so as to be laminated in the die so as to have a two-layer structure. The film was cooled by a cooling device to obtain an unstretched film.
Next, this unstretched film was heated to 150 ° C. (temperature a), then stretched 5 times in the longitudinal direction, and then cooled to obtain a stretched film.
Again, it was heated to 140 ° C. (temperature b) and stretched 8 times in the transverse direction with a tenter. Then, it annealed at 160 degreeC (temperature c), cooled to 50 degreeC, slit the ear | edge part, and obtained the film of the 2 layer ((E) / (A): wall thickness 30/45 micrometer) structure. (Thickness: 75 μm). Then, the surface oxidation process by operation similar to Example 1 was given, and the electrophotographic label which bonded the release paper in which the adhesive layer was formed to the layer (E) side which enables delamination was obtained.
The obtained electrophotographic label was evaluated in the following manner. The evaluation results are summarized in Table 3.
[0076]
<Evaluation>
v. Peeling initiation
The peel strength of the layer (E) enabling delamination and the breaking strength of the surface layer (F) were measured by the methods described in <Peel strength> and <Rupture strength>, respectively.
The obtained electrophotographic label is cut into a 5 cm × 5 cm square, the release paper is peeled off, and is stuck on a government-made postcard. Then, one of the four sides of the resin film is held by hand, and is peeled off from the government-made postcard. The state until peeling of the layer (E) or the surface layer (F) enabling delamination was evaluated according to the following criteria.
Very good (◎) peeling starts immediately. (Actual use possible)
It takes 2 mm or more before good (◯) peeling starts. (Actual use possible)
Slightly poor (Δ) peeling starts partially. (Difficult to use)
It takes 10 mm or more before defective (x) peeling starts. (Difficult to use)
[0077]
vi. Delamination propagation
The obtained electrophotographic label was cut into a 5 cm × 5 cm square, the release paper was peeled off, and was stuck on a postcard made by the government. Nichiban Co., Ltd., trade name) is attached, the layer (E) or the surface layer (F) that enables delamination is easily started, and the base material layer (A) is peeled off from the government-made postcard. The propagation state and peeling force of the layer (E) or surface layer (F) enabling delamination were visually observed and evaluated according to the following criteria.
Very good (◎) Peeling force is light and the entire surface is transmitted cleanly. (Actual use possible)
Good (○) Peeling force is slightly heavy, but propagates cleanly on the entire surface. (Actual use possible)
Slightly poor (△) peeling force is very heavy, but it propagates cleanly on the whole surface. (Difficult to use)
Defective (x) cannot be propagated all over and is cut off halfway. (Difficult to use)
[0078]
vii. Information hiding
About 26 characters of alphabet letter size of 10 points printed on a government-made postcard, peeled off the release paper (C) of the electrophotographic label, then stuck on the printed surface of the alphabet, and the concealment of the characters seen through the produced film The samples were visually observed and evaluated according to the following criteria.
Very good (◎) Actual use possible.
Good (○) can be used.
Somewhat bad (△) difficult to use.
Defective (×) difficult to use.
[0079]
viii. Information recognition
For barcode reading, barcode (CODE39) is printed on the synthetic paper “VES85” (trade name, manufactured by Yupo Corporation) with barcode printer “B30” (trade name, manufactured by Tech Co., Ltd.). A sample was created.
Remove the release paper (C) of the electrophotographic label, paste it on the barcode printing surface on the synthetic paper, create 10 samples with the barcode hidden, and remove the barcode after peeling off the base material layer (A). A barcode reader “LASERCHEK II” (trade name, manufactured by Fuji Electric Refrigerator Co., Ltd.) was used to evaluate the number of successful barcode recognitions according to the following criteria.
Very good (◎) Successful 10 times. (Actual use possible)
Good (◯) 8-9 successes. (Actual use possible)
Slightly bad (△) 2-7 successes. (Difficult to use)
Defect (x) Success count is 1 or less. (Difficult to use)
[0080]
(Example 10)
EVA (described in Table 1) was extruded into a film from a T-die connected to an extruder set at 160 ° C. The obtained film was laminated on the layer (E) surface that enables delamination of the 5-fold stretched film prepared by the same operation as in Example 9, and a surface layer (F) was provided, and after cooling to 55 ° C., It heated to 143 degreeC (temperature b), and extended | stretched 8 times in the horizontal direction with the tenter. Then, it anneals at 160 degreeC (temperature c), cools to 50 degreeC, slits the ear | edge part, and is 3 layers ((F) / (E) / (A): thickness 5/30/45 micrometer) A film having a structure was obtained (thickness: 80 μm). Then, the surface oxidation process by the operation similar to Example 1 was performed, the electrophotographic label which bonded the release paper in which the adhesive layer was formed to the surface layer (F) side was produced, and evaluation was performed. The evaluation results are shown in Table 3.
(Comparative Example 5)
Composition (8) (described in Table 2) on the resin film layer (A), composition [○ 11] (described in Table 3) on the layer (E) enabling delamination, and surface layer (F) The LDPE (described in Table 1) was used for the electrophotographic label in the same manner as in Example 10 except for the composition [9] as the base material layer (A) and the molding conditions described in Table 3. Fabricated and evaluated. The evaluation results are shown in Table 3.
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[Table 3]

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【The invention's effect】
The electrophotographic label of the present invention reduces curling after printing by a heat fixing type electrophotographic printer or heat fixing type electrophotographic copying machine, and realizes good printability by continuous printing of a large number of sheets. It is useful for indoor and outdoor industries because of its excellent water resistance and mechanical properties. In addition, it does not require special processing to start peeling, and the surface layer peels off with a small force, so it can be used in a wide range of applications such as delivery tables, concealment seals, anti-stick labels, tamper-proof seals, application seals, coupons, etc. It can also be used effectively.

Claims (9)

A base material layer (A) comprising a thermoplastic resin film containing 35 to 97% by weight of a thermoplastic resin composed of a mixture of an olefin resin and an elastomer which is a crystalline resin, and 65 to 3% by weight of an inorganic fine powder and / or an organic filler. ) Is provided with an adhesive layer (B) and a release paper (C) on one side, wherein the base layer (A) has a heat of crystallization of 60 J / cm ³ or less. Electrophotographic label.   The average curl height of the four corners after 2 minutes or more after printing of A-4 size (210 mm × 297 mm) paper by a heat fixing type electrophotographic printer or heat fixing type electrophotographic copying machine is 50 mm or less. The electrophotographic label according to claim 1. The electrophotographic label according to claim 1 or 2, wherein the olefin resin is a propylene resin. The electron according to any one of claims 1 to 3, wherein the elastomer is selected from a styrene thermoplastic elastomer, an olefin thermoplastic elastomer, a urethane thermoplastic elastomer, and an ester thermoplastic elastomer. Photo label. The electrophotographic label according to any one of claims 1 to 4 , wherein the electrostatic capacity is 5 pF / cm ² or more. It consists of a laminated film which has the layer (E) which makes the delamination strength which is 5 to 150 g / cm width on the surface which provides the adhesive layer (B) of the base material layer (A), and this laminated film heat of crystallization is 60 J / cm ³ or less, the electrophotographic label according to any one of claims 1 to 5. The electrophotographic label according to claim 1 , wherein the electrophotographic label is printed by a heat fixing type electrophotographic printer or a heat fixing type electrophotographic copying machine. Recorded material, which comprises using an electrophotographic label according to any one of claims 1 to 7. A printing method comprising printing on the electrophotographic label according to claim 1 with a heat fixing type electrophotographic printer or a heat fixing type electrophotographic copying machine.