JP2000168018A - Thermoplastic resin-laminated structure and its production - Google Patents
Thermoplastic resin-laminated structure and its productionInfo
- Publication number
- JP2000168018A JP2000168018A JP10345205A JP34520598A JP2000168018A JP 2000168018 A JP2000168018 A JP 2000168018A JP 10345205 A JP10345205 A JP 10345205A JP 34520598 A JP34520598 A JP 34520598A JP 2000168018 A JP2000168018 A JP 2000168018A
- Authority
- JP
- Japan
- Prior art keywords
- thermoplastic resin
- composition
- weight
- layer
- laminated structure
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Landscapes
- Laminated Bodies (AREA)
- Paints Or Removers (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は長期持続する帯電防
止性と良好な印刷性を備えた熱可塑性樹脂積層構造物及
びその製法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermoplastic resin laminated structure having long-lasting antistatic properties and good printability, and a method for producing the same.
【０００２】[0002]
【背景技術】従来筆記や印刷されるシート類の大部分と
して紙が使用されているが、紙は強度、耐水性、保存性
が十分でない為、プラスチックフィルムをベースとす
る、いわゆる合成紙が紙に代わって使用される様になっ
てきた。かかる合成紙としてはプラスチック原料に無機
又は有機充填材を混練してシート化し、これを１軸又は
２軸方向に延伸してフィルム内部にボイドを形成せし
め、不透明化すると共に、筆記性を付与したものや、プ
ラスチックフィルム表面に顔料等を含む多孔質の層を設
けてインキ受容性を付与したもの等が開発されている。2. Description of the Related Art Conventionally, paper is used as a large part of sheets to be written or printed. However, since paper has insufficient strength, water resistance, and storage stability, so-called synthetic paper based on a plastic film is used. It has come to be used in place of. Such a synthetic paper is formed into a sheet by kneading an inorganic or organic filler with a plastic raw material, stretching this uniaxially or biaxially to form a void inside the film, making the film opaque, and imparting writability. And those in which a porous layer containing a pigment or the like is provided on the surface of a plastic film to impart ink receptivity have been developed.
【０００３】これら合成紙に共通する問題点はプラスチ
ック特有の帯電性に起因する静電気による印刷障害や、
オフセット印刷におけるセット性（インキの吸い込み
性）不良である。静電気障害を防止する手段として従来
合成紙原料素材に低分子量の帯電防止剤を練り込んだ
り、高分子帯電防止剤の溶液を合成紙表面に塗布したり
する事が行われた。しかしこれらは帯電防止剤の浸み出
しによるベタツキや、帯電防止効果が持続しないといっ
た欠点があり、満足すべきものではなかった。又、オフ
セット印刷性不良の対策として比表面積の大きい充填剤
を表面層に使用（特開昭62-227933号公報）してインキ
吸収速度を早めたり、合成紙表面にポリエチレンイミン
から成る被膜を形成（特開平1-141736号公報）してイン
キ接着性を改善する試みがあるが、必ずしも十分でな
く、又上記帯電防止効果を兼備する事は困難であった。[0003] Problems common to these synthetic papers are printing failure due to static electricity due to the charging property peculiar to plastic,
The setting property (ink suction property) is poor in offset printing. As means for preventing electrostatic damage, conventionally, a low molecular weight antistatic agent has been kneaded into a synthetic paper raw material, or a solution of a polymeric antistatic agent has been applied to the surface of synthetic paper. However, these have been unsatisfactory because of their drawbacks such as stickiness due to seepage of the antistatic agent and the inability to maintain the antistatic effect. In addition, as a countermeasure against offset printability failure, a filler having a large specific surface area is used for the surface layer (Japanese Patent Laid-Open No. 62-227933) to increase the ink absorption rate, or to form a film made of polyethylene imine on the surface of synthetic paper. Attempts have been made to improve ink adhesion (Japanese Patent Application Laid-Open No. 1-141736), but it has not always been sufficient, and it has been difficult to combine the above antistatic effect.
【０００４】[0004]
【発明が解決しようとする課題】紙用オフセットインキ
の使用が可能で、優れた筆記性を有し、かつ持続性のあ
る帯電防止効果を備えた合成紙の出現が待望されてい
た。There has been a long-awaited demand for synthetic paper which can use offset ink for paper, has excellent writability, and has a long-lasting antistatic effect.
【０００５】[0005]
【課題を解決する為の手段】本発明者等は上記課題を解
決すべく鋭意検討を進めた結果、熱可塑性合成樹脂から
主として成るシート基材、静電誘導防止性組成物層及び
架橋ポリウレタン系樹脂塗布剤とから成る塗膜表面層で
構成された熱可塑性樹脂積層構造物が上記課題を解決し
得る事を知り、本発明を完成した。The present inventors have made intensive studies to solve the above-mentioned problems, and as a result, have found that a sheet substrate mainly composed of a thermoplastic synthetic resin, an anti-static induction-preventing composition layer, and a crosslinked polyurethane-based resin. The inventors have found that a thermoplastic resin laminated structure composed of a coating film surface layer composed of a resin coating agent can solve the above-mentioned problems, and have completed the present invention.
【０００６】[0006]
【発明の実施の形態】以下、本発明につき詳細に説明す
る。本発明の特徴は、シート基材と印刷・筆記生に優れ
た塗膜表面層の中間に、静電誘導防止性組成物層を介在
せしめた、少なくとも３層の構成を有する点である。本
発明において「静電誘導」とは「静電感応」とも言わ
れ、帯電体の近傍に導体又は誘電体があるとき、その帯
電体に近い側の面にこれと反対の電荷、遠い側の面に同
種の電荷が現れる現象を言う（岩波書店発光、理化学辞
典）。そしてこの現象を防止する機能を「静電誘導防止
性」という。本発明に用いる静電誘導防止性組成物は側
鎖に少なくとも４級アンモニウム塩基を有する共重合高
分子から主として成るものが好ましい。この様な共重合
高分子は公知であって、例えばジメチルアミノエチルメ
タクリレートをメチルメタクリレート及びエチルアクリ
レートと共重合させた後、塩化メチルやジメチル硫酸等
のカチオン化剤で処理して４級化する事によって得られ
る（特開昭47-18780）。４級アンモニウム塩基は双極子
を有しているので、表面に発生した静電気を打ち消す方
向に作用（減極現象）する。又高分子である為、低分子
帯電防止剤を練り込んだ場合の様に表面に浸出したりベ
タつく事がない。DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail. A feature of the present invention is that it has a configuration of at least three layers in which an electrostatic induction preventing composition layer is interposed between a sheet substrate and a coating film surface layer excellent in printing and writing. In the present invention, "electrostatic induction" is also referred to as "electrostatic response", and when there is a conductor or dielectric near a charged body, the opposite charge is applied to the surface near the charged body, This phenomenon refers to the appearance of the same kind of charge on the surface (Iwanami Shoten Luminescence, RIKEN Dictionary). The function of preventing this phenomenon is called "static induction prevention". The composition for preventing electrostatic induction used in the present invention is preferably composed mainly of a copolymer having at least a quaternary ammonium base in the side chain. Such copolymers are known in the art. For example, dimethylaminoethyl methacrylate is copolymerized with methyl methacrylate and ethyl acrylate and then quaternized by treatment with a cationizing agent such as methyl chloride or dimethyl sulfate. (JP-A-47-18780). Since the quaternary ammonium base has a dipole, it acts in a direction to cancel static electricity generated on the surface (depolarization phenomenon). Also, since it is a polymer, it does not leach or stick to the surface unlike a case where a low-molecular antistatic agent is kneaded.
【０００７】更に好ましい静電誘導防止性組成物は側鎖
に少なくともカルボキシル基及び４級アンモニウム塩基
を有する架橋性共重合高分子から主として成るものであ
る。この様な高分子も公知であって、例えばジメチルア
ミノエチルメタクリレートをアクリル酸、メチルメタク
リレート及びエチルアクリレートと共重合させた後、塩
化メチルやジメチル硫酸等のカチオン化剤で処理して４
級化する事によって得られる（特許第2608383号）。こ
れに両末端にエポキシ基を有する化合物例えばグリセリ
ンジグリシジルエーテルを配合しておき、塗布する際に
アミン触媒を添加すれば乾燥時硬化して一層耐久性を向
上させる事が出来る。[0007] A more preferred composition for preventing static induction is mainly composed of a crosslinkable copolymer having at least a carboxyl group and a quaternary ammonium group in the side chain. Such polymers are also known. For example, dimethylaminoethyl methacrylate is copolymerized with acrylic acid, methyl methacrylate and ethyl acrylate and then treated with a cationizing agent such as methyl chloride or dimethyl sulfate to obtain a polymer.
It is obtained by grading (Patent No. 2608383). A compound having an epoxy group at both terminals, such as glycerin diglycidyl ether, is added thereto, and if an amine catalyst is added at the time of coating, the composition can be cured during drying to further improve durability.
【０００８】熱可塑性樹脂シート基材への静電誘導防止
性組成物の塗布はグラビアコーター、各種ロールコータ
ー、ロッドコーター、ダイコーター、ナイフコーター等
何れの塗工手段でも良い。塗布液は該静電誘導防止性組
成物を有機溶剤溶液又は水系エマルジョンとして用い
る。塗布量は塗膜厚み0.01乃至3μm程度で良く、これに
より、次に塗膜表面層を設ける場合の接着性も大幅に改
善される。[0008] The application of the composition for preventing static induction to the thermoplastic resin sheet substrate may be performed by any coating means such as a gravure coater, various roll coaters, a rod coater, a die coater and a knife coater. As the coating liquid, the composition for preventing electrostatic induction is used as an organic solvent solution or an aqueous emulsion. The coating amount may be about 0.01 to 3 μm in the thickness of the coating film, thereby greatly improving the adhesiveness when the coating film surface layer is next provided.
【０００９】本発明に用いる塗膜表面層は架橋ポリウレ
タンを主体とするものであって、更に酸化チタンやシリ
カ等の顔料を含むものである。又更に水酸基含有塩化ビ
ニル/酢酸ビニル共重合体を含有したものが好ましい。
水酸基含有塩化ビニル/酢酸ビニル共重合体の配合量は
ポリオール成分とポリイソシアネート成分の合計100重
量部当たり約10乃至40重量部であるのが適当である。表
面層の形成は、ポリイソシアネート成分を除く全ての成
分を溶剤に溶解した液に、ポリイソシアネート成分を使
用直前に混合して塗布・硬化させれば良い。塗布は上記
何れの塗工手段も用いる事が出来る。塗布量は用途によ
り適宜変更出来るが、1μmから30μm程度が好ましい。The surface layer of the coating film used in the present invention is mainly composed of a crosslinked polyurethane and further contains a pigment such as titanium oxide or silica. Further, those containing a hydroxyl group-containing vinyl chloride / vinyl acetate copolymer are preferred.
The amount of the hydroxyl group-containing vinyl chloride / vinyl acetate copolymer is suitably about 10 to 40 parts by weight per 100 parts by weight of the total of the polyol component and the polyisocyanate component. The surface layer may be formed by mixing the polyisocyanate component with a solution in which all components except the polyisocyanate component are dissolved in a solvent immediately before use, and coating and curing the mixture. Any of the above-mentioned coating means can be used for coating. The coating amount can be appropriately changed depending on the application, but is preferably about 1 μm to 30 μm.
【００１０】シート基材の主成分である熱可塑性樹脂
は、合成紙として一般的に用いられているポリエステル
でもポリオレフィンでも良いが、ポリオレフィンの方が
コスト的に有利である。その中でも結晶性ポリプロピレ
ンは高軟化点の石油樹脂を混合して溶融押出ししたシー
トを延伸すると、微細なボイド形成が得られ、隠蔽性、
表面平滑性に優れ、かつ高い剛性が得られる事から好ま
しい。この場合用いる石油樹脂は環球法で測定した軟化
点が160℃以上200℃以下のシクロペンタジエン系石油樹
脂が特に好ましい。要求特性やコスト面で石油樹脂の一
部又は全部を無機充填材で置き換える事も出来る。The thermoplastic resin, which is the main component of the sheet substrate, may be a polyester or a polyolefin generally used as synthetic paper, but the polyolefin is more advantageous in cost. Among them, crystalline polypropylene is obtained by mixing a petroleum resin having a high softening point and stretching a melt-extruded sheet, whereby fine voids are formed, concealing properties,
It is preferable because it has excellent surface smoothness and high rigidity can be obtained. The petroleum resin used in this case is particularly preferably a cyclopentadiene-based petroleum resin having a softening point measured by a ring and ball method of 160 ° C. or more and 200 ° C. or less. Part or all of the petroleum resin can be replaced with an inorganic filler in terms of required characteristics and cost.
【００１１】[0011]
【発明の効果】本発明の熱可塑性樹脂積層構造物は半永
久的に持続する帯電防止性を備えている。これは中間層
を成す共重合高分子の側鎖に含まれる４級アンモニウム
塩基のイオン対（双極子）が誘電分極緩和性（減極現
象）を発揮する為表面電荷が中和され、しかも該イオン
は積層構造物内部に閉じこめられている為表面に浸出す
る事なく、表面特性を損なわないと考えられる。同時に
帯電防止機能が長期間持続して保たれる。The thermoplastic resin laminated structure of the present invention has a semi-permanent antistatic property. This is because the surface charge is neutralized because the ion pair (dipole) of the quaternary ammonium base contained in the side chain of the copolymer forming the intermediate layer exhibits dielectric polarization relaxation (depolarization phenomenon). Since the ions are confined inside the laminated structure, they do not leach to the surface and do not impair the surface characteristics. At the same time, the antistatic function is maintained for a long time.
【００１２】更に本発明の熱可塑性樹脂積層構造物は各
種筆記具、スタンプ、朱肉、印刷等に対して筆記性、印
捺性、印刷性等に優れた表面を形成する事が出来る。こ
れは顔料を含む架橋ポリウレタン表面層が適度のインク
吸収性、筆記性、クッション性を備えている為である。Further, the thermoplastic resin laminated structure of the present invention can form a surface excellent in writing, printing, printing, etc. on various writing tools, stamps, vermilion, printing and the like. This is because the crosslinked polyurethane surface layer containing the pigment has appropriate ink absorption, writing properties, and cushioning properties.
【００１３】[0013]
【実施例】以下、実施各例および比較各例によって本発
明を具体的に説明するが、本発明はこれらにより限定さ
れるべきものではない。尚、実施例における「％」は特
に断りがない限り「重量％」である。また、本発明の特
性は、下記評価方法により調べた。EXAMPLES Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples, but the present invention should not be limited by these. In the examples, "%" is "% by weight" unless otherwise specified. The characteristics of the present invention were examined by the following evaluation methods.
【００１４】[評価方法] １）帯電防止性（表面抵抗率） 安藤電気（株）製セル（SE-1000）及びアドバンテスト
社製Ultra High Resistance Meter R8340Aを用いてJIS
K 6911に準拠して表面抵抗率（Ω）を測定した。 ２）オフセット印刷性 石川島産業機械（株）製印刷適正試験機(RI-2型)を用い
て、本発明の積層構造体表面に酸化重合型用紙用インキ
（東洋インキ製TKハイエコー）をインキ盛り量0.3ccの
条件で印刷した後、温度23℃、湿度50%で１日間状態調
節を行い、下記の評価をした。 ２−１）密着性（セロテープテスト） ニチバンセロテープ（日東電工（株）商品名）（巾25m
m）を印刷面に貼り合わせ、指で２回こすり、テープを
引き剥がしてインキの残存割合を観察した。 ○：90%以上残存 △：75 90%未満 ×：75%未満 ２−２）セット性 印刷面に指で触れて、指にインキが移らなくなる迄の時
間を測定した。 ２−３）鉛筆筆記性 塗工面に鉛筆硬度HB、加重20gにて線を引き、コピー用
紙（コクヨ11B）と比較した。 ○：紙と同等又はそれ以上 △：紙と比較してやや劣る ×：紙に比較して劣る[Evaluation Method] 1) Antistatic Property (Surface Resistivity) JIS using a cell (SE-1000) manufactured by Ando Electric Co., Ltd. and Ultra High Resistance Meter R8340A manufactured by Advantest Co., Ltd.
The surface resistivity (Ω) was measured according to K6911. 2) Offset printability Oxidation polymerization type paper ink (TK High Echo manufactured by Toyo Ink) is applied to the surface of the laminated structure of the present invention using a printability tester (RI-2 type) manufactured by Ishikawajima Sangyo Kikai Co., Ltd. After printing under the condition of an amount of 0.3 cc, the condition was adjusted for one day at a temperature of 23 ° C. and a humidity of 50%, and the following evaluation was made. 2-1) Adhesion (Cellotape test) Nichiban Cellotape (Nitto Denko Corporation) (25m width)
m) was attached to the printing surface, rubbed twice with a finger, the tape was peeled off, and the remaining ratio of the ink was observed. ：: 90% or more remaining Δ: 75 less than 90% ×: less than 75% 2-2) Setability The printing surface was touched with a finger, and the time until ink did not transfer to the finger was measured. 2-3) Pencil Writability A line was drawn on the coated surface with a pencil hardness of HB and a weight of 20 g, and compared with copy paper (Kokuyo 11B). ：: equivalent or higher than paper △: slightly inferior to paper ×: inferior to paper
【００１５】[熱可塑性樹脂シート基材] （シート基材Ｋ−１の製造）ｎ−ヘプタン不溶部を９６
％含有するＭＦＲが２ｇ／10分の結晶性ポリプロピレン
粉末１００重量部に対して、フェノール系酸化防止剤Ｂ
ＨＴ（商品名）を０．２重量部、ステアリン酸カルシウ
ム０．１重量部、グリセリンモノステアレート０．１重
量部、軟化点１７２℃のシクロペンタジエン系石油樹脂
（以下、ＤＣＰＤという）１０重量部、および炭酸カル
シウム（平均粒径１．５μｍ）１０重量部を、ヘンシェ
ルミキサー（商品名）に投入し混合攪拌した後、同方向
回転型二軸押出機に供給し２４０℃で溶融混練してスト
ランドとして押出し、これを冷却しカットしてペレット
状の組成物を得た。多層Ｔダイを備えた３種３層フィル
ム押出装置（押出機は、口径６５ｍｍφ中間層用単軸押
出機が１台、口径５０ｍｍφの積層用単軸押出機が２
台）およびテンター法逐次二軸延伸機を用いて、前記の
組成物を中間層用単軸押出機に供給し、Ｔダイ温度２４
０℃で溶融して押出を行ない、表面温度３０℃の鏡面冷
却ロールで急冷して、未延伸フィルムを得た。得られた
未延伸フィルムを縦延伸機に導き加熱ロール間で１４０
℃の温度で５倍延伸し、次にテンター内温度１６０〜２
１０℃で横方向に８倍延伸した後、巻取り、厚みが１５
０μｍの単層空洞含有延伸フィルムであるシート基材を
得た。 （シート基材Ｙ−１の製造）ＤＣＰＤを配合しなかった
以外は、前記シート基材Ｋ−１の製造に準じて組成物を
得、厚みが１５０μｍの単層空洞含有延伸フィルムであ
るシート基材を得た。 （シート基材Ｙ−２の製造）ＤＣＰＤを配合せず、グリ
セリンモノステアレート０．１重量部とＮ，Ｎ−ビス
（２−ヒドロキシエチル）アルキルアミン０．２重量部
から成る練り込み用帯電防止剤（Ｂ−１）を配合した以
外は、前記シート基材Ｋ−１の製造に準じて組成物を
得、厚みが１５０μｍの単層空洞含有延伸フィルムであ
るシート基材を得た。 （シート基材Ｋ−２の製造）ＤＣＰＤを１０重量部から
５０重量部に、炭酸カルシウムを１０重量部から５０重
量部に代えた以外は、前記シート基材Ｋ−１の製造に準
じて組成物（基層フィルム用組成物）を得た。また、こ
れとは別に、ｎ−ヘプタン不溶部を９６％含有するＭＦ
Ｒが２ｇ／10分の結晶性ポリプロピレン粉末１００重量
部に対して、フェノール系酸化防止剤ＢＨＴ（商品名）
を０．２重量部、ステアリン酸カルシウム０．１重量
部、およびグリセリンモノステアレート０．１重量部
を、ヘンシェルミキサー（商品名）に投入し混合攪拌し
た後、同方向回転型二軸押出機に供給し２４０℃で溶融
混練してストランドとして押出し、これを冷却しカット
してペレット状の積層フィルム用組成物を得た。次に、
実施例１に記載の多層Ｔダイを備えた３種３層フィルム
押出装置（押出機は、口径６５ｍｍφ中間層用単軸押出
機が１台、口径５０ｍｍφの積層用単軸押出機が２台）
およびテンター法逐次二軸延伸機を用いて、前記の組成
物を中間層用単軸押出機に、前記の積層フィルム用組成
物を積層用単軸押出機に供給し、Ｔダイ温度２４０℃で
溶融して共押出を行ない、表面温度３０℃の鏡面冷却ロ
ールで急冷して、積層／基層／積層、の順に、厚み比
１：３：１で積層された２種３層の未延伸フィルムを得
た。得られた未延伸フィルムを縦延伸機に導き加熱ロー
ル間で１４０℃の温度で５倍延伸し、次にテンター内温
度１６０〜２１０℃で横方向に８倍延伸した後、巻取
り、合計の厚みが１５０μｍの積層空洞含有延伸フィル
ムを得た。引続き前記の積層空洞含有延伸フィルムを、
１１０℃に加熱された一対の金属ロールを用いて、線圧
５０〜４００kg／cmにて加熱圧縮し、厚みが加熱圧縮前
の８０％に当る圧縮処理済み空洞含有延伸フィルムであ
るシート基材を得た。[Thermoplastic resin sheet base material] (Production of sheet base material K-1)
% Phenolic antioxidant B based on 100 parts by weight of crystalline polypropylene powder having an MFR of 2 g / 10 min.
0.2 parts by weight of HT (trade name), 0.1 part by weight of calcium stearate, 0.1 part by weight of glycerin monostearate, 10 parts by weight of a cyclopentadiene-based petroleum resin having a softening point of 172 ° C. (hereinafter referred to as DCPD), And 10 parts by weight of calcium carbonate (average particle size: 1.5 μm) were charged into a Henschel mixer (trade name), mixed and stirred, and then supplied to a co-rotating twin-screw extruder to be melt-kneaded at 240 ° C. to form a strand. It was extruded, cooled and cut to obtain a pellet-shaped composition. A three-layer three-layer film extruder equipped with a multi-layer T die (one extruder is a single-screw extruder for a 65 mm diameter intermediate layer, and two single-screw extruders for lamination are 50 mm diameter.
The above composition was supplied to a single-screw extruder for an intermediate layer using a
It was melted at 0 ° C., extruded, and quenched with a mirror-cooled roll having a surface temperature of 30 ° C. to obtain an undrawn film. The obtained unstretched film is guided to a longitudinal stretching machine, and 140
At a temperature of 150 ° C., and then a temperature of 160 to 2 in the tenter.
After stretching 8 times in the transverse direction at 10 ° C, winding, thickness 15
A sheet substrate which was a single-layer void-containing stretched film having a thickness of 0 μm was obtained. (Production of Sheet Base Y-1) Except that DCPD was not blended, a composition was obtained in the same manner as in the production of the sheet base K-1, and the sheet base was a single-layer cavity-containing stretched film having a thickness of 150 μm. Wood was obtained. (Production of sheet base material Y-2) Charge for kneading without mixing DCPD, consisting of 0.1 part by weight of glycerin monostearate and 0.2 part by weight of N, N-bis (2-hydroxyethyl) alkylamine Except for compounding the inhibitor (B-1), a composition was obtained in the same manner as in the production of the sheet substrate K-1, and a sheet substrate as a single-layer cavity-containing stretched film having a thickness of 150 μm was obtained. (Production of sheet base material K-2) The composition was the same as in the production of the sheet base material K-1, except that DCPD was changed from 10 parts by weight to 50 parts by weight and calcium carbonate was changed from 10 parts by weight to 50 parts by weight. (Composition for base layer film) was obtained. Separately, MF containing 96% of n-heptane insoluble portion
R is 2 g / 10 min and 100 parts by weight of the crystalline polypropylene powder is phenolic antioxidant BHT (trade name)
, 0.2 parts by weight of calcium stearate, 0.1 parts by weight of calcium stearate, and 0.1 parts by weight of glycerin monostearate were put into a Henschel mixer (trade name), mixed and stirred, and then placed in a co-rotating twin-screw extruder. The mixture was melt-kneaded at 240 ° C., extruded as a strand, cooled and cut to obtain a pellet-shaped composition for a laminated film. next,
Three-layer, three-layer film extruder equipped with the multilayer T-die described in Example 1 (one extruder is a single-screw extruder for an intermediate layer having a diameter of 65 mmφ and two single-screw extruders for lamination having a diameter of 50 mmφ)
And using a tenter method sequential biaxial stretching machine, the above composition was supplied to a monoaxial extruder for an intermediate layer, and the composition for a laminated film was supplied to a monoaxial extruder for lamination. Fused and co-extruded, quenched with a mirror cooling roll having a surface temperature of 30 ° C., and laminated two / three-layer unstretched films having a thickness ratio of 1: 3: 1 in the order of lamination / base layer / lamination. Obtained. The obtained unstretched film was guided to a longitudinal stretching machine, stretched 5 times at a temperature of 140 ° C. between heating rolls, and then stretched 8 times in a transverse direction at a temperature in a tenter of 160 to 210 ° C., and wound up. A laminated cavity-containing stretched film having a thickness of 150 μm was obtained. Subsequently, the laminated cavity-containing stretched film,
Using a pair of metal rolls heated to 110 ° C., heat-compressing is performed at a linear pressure of 50 to 400 kg / cm. Obtained.
【００１６】[静電誘導防止性組成物層]得られたシート
基材の片面に対して、次の静電誘導防止性組成物を、混
合物中の固形分が１％になるように水で希釈した後、こ
の希釈液をバーコーターで塗布し、９０℃で１０分間乾
燥・硬化させて静電誘導防止性組成物層を得た。塗工量
は固形分として０．０２ｇ／ｍ2で行った。 （組成物Ａ−１） ボンディップPA-100（コニシ株式会社商品名） （４級アンモニウム塩基とカルボキシル基含有架橋性高
分子を含む） （組成物Ａ−２） ＳＰＰー５（松本油脂製薬株式会社商品名） （４級アンモニウム塩基含有非架橋性高分子を含む）[Electrostatic induction-preventing composition layer] The following antistatic induction-inhibiting composition was applied to one surface of the obtained sheet substrate with water so that the solid content in the mixture was 1%. After dilution, this diluted solution was applied with a bar coater, and dried and cured at 90 ° C. for 10 minutes to obtain an antistatic induction-preventive composition layer. The coating amount was 0.02 g / m 2 as a solid content. (Composition A-1) Bondip PA-100 (trade name of Konishi Co., Ltd.) (Including quaternary ammonium base and carboxyl group-containing crosslinkable polymer) (Composition A-2) SPP-5 (Matsumoto Yushi Pharmaceutical Co., Ltd.) (Company name) (Including non-crosslinkable polymer containing quaternary ammonium base)
【００１７】[塗膜表面層]得られたシート基材の片面も
しくは静電誘導防止性組成物層の表面に対して、次の塗
膜表面層用組成物をバーコーターを用いて塗布した。固
形分厚み5μm（Ｍ−２層）の場合８番バー、2μmの場合
（Ｍ−１層）３番バーで塗布し、100℃で2分乾燥後、温
度23℃、湿度50%の室内で2日間状態調節を行った。（Ｃ
−１の場合8番バー使用、状態調節は同様にした） （組成物Ｍ−１、２） ＶＭ-ＦＩＴマット(Ｍ-16)（大日精化株式会社商品名） （ホ゜リオール成分、水酸基含有塩化ビニル/酢酸ビニル共重
合体、顔料等を含む主剤溶液とホ゜リイソシアネート溶液から成る
副剤から成り、混合塗布するもの）Ｍ−１層は乾燥後厚
み2μm、Ｍ−２層は乾燥後厚み5μmとなる様に塗布し
た。 （組成物Ｃ−１）クレー（白石カルシウム（株）製オプ
チホワイトＰ[商品名]）70重量％、炭酸カルシウム（同
和カルファイン（株）製KSS-1000）30重量％から成る顔
料100重量部に対し、SBRラテックス（日本合成ゴム
（株）製JSR0696）11重量部、水18重量部配合の乳化水
溶液の塗布剤を作成した。Ｃ−１層は乾燥後厚み6μmと
なる様に塗布した。[Coating film surface layer] The following coating film surface layer composition was applied to one surface of the obtained sheet substrate or the surface of the electrostatic induction preventing composition layer using a bar coater. Solid thickness 5μm (M-2 layer) No. 8 bar, 2μm (M-1 layer) No. 3 bar, dry at 100 ° C for 2 minutes, room temperature 23 ° C, humidity 50% Conditioning was performed for two days. (C
In the case of -1, No. 8 bar was used and the condition was adjusted in the same manner.) (Composition M-1, 2) VM-FIT mat (M-16) (trade name of Dainichi Seika Co., Ltd.) (Polyol component, hydroxyl-containing chloride) A main agent solution containing a vinyl / vinyl acetate copolymer, a pigment, etc., and an auxiliary agent consisting of a polyisocyanate solution, which are mixed and coated) The M-1 layer has a thickness of 2 μm after drying, and the M-2 layer has a thickness of 5 μm after drying. Was applied. (Composition C-1) 100 parts by weight of a pigment composed of 70% by weight of clay (Optiwhite P [trade name] manufactured by Shiraishi Calcium Co., Ltd.) and 30% by weight of calcium carbonate (KSS-1000 manufactured by Dowa Calfine Co., Ltd.) On the other hand, a coating solution of an emulsified aqueous solution containing 11 parts by weight of SBR latex (JSR0696 manufactured by Nippon Synthetic Rubber Co., Ltd.) and 18 parts by weight of water was prepared. The C-1 layer was applied to a thickness of 6 μm after drying.
【００１８】[熱可塑性樹脂積層構造物]各熱可塑性樹脂
積層構造物の構成（熱可塑性樹脂シート基材、静電誘導
防止性組成物層及び塗膜表面層）及び前記評価方法に基
づいて得られる評価結果を表１に示す。[Layer Structure of Thermoplastic Resin] The structure of each thermoplastic resin laminate structure (thermoplastic resin sheet base material, antistatic composition layer and coating film surface layer) and the evaluation method described above are obtained. Table 1 shows the evaluation results obtained.
【００１９】[0019]
【表１】 [Table 1]
───────────────────────────────────────────────────── フロントページの続き Ｆターム(参考） 4F100 AA01H AA08 AH00H AH02B AH02C AH03B AJ01A AK01A AK03A AK07A AK07D AK15C AK15J AK15K AK22C AK22J AK51C AK51K AL01B AL01C AL05B AL05C AL06B AL06C AR00B BA04 BA07 CA13C CA23A CC00C DE01H EA061 EG002 EH132 EH462 EJ05C EJ371 GB90 HB31 JA11A JA11D JB16A JD14 JG03 JG03B 4J038 CD062 CF042 DG051 DG261 GA03 GA06 GA08 KA08 NA02 NA12 PA13 PC08 ──────────────────────────────────────────────────の Continued on the front page F-term (reference) 4F100 AA01H AA08 AH00H AH02B AH02C AH03B AJ01A AK01A AK03A AK07A AK07D AK15C AK15J AK15K AK22C AK22J AK51C AK51K AL01B04 AL01CAL05B05 AL01C AL05B05 GB90 HB31 JA11A JA11D JB16A JD14 JG03 JG03B 4J038 CD062 CF042 DG051 DG261 GA03 GA06 GA08 KA08 NA02 NA12 PA13 PC08
Claims (10)
材、静電誘導防止性組成物層及び顔料と架橋ポリウレタ
ン系樹脂塗布剤とから成る塗膜表面層で構成される印刷
性の優れた熱可塑性樹脂積層構造物。An excellent printability thermoplastic comprising a sheet substrate mainly composed of a thermoplastic resin, a layer of a composition for preventing static induction and a coating film surface layer composed of a pigment and a crosslinked polyurethane resin coating agent. Resin laminate structure.
の少なくとも片面に静電誘導防止性組成物層を有し、該
組成物層の表面に、顔料を含む柔軟性の架橋ポリウレタ
ン系樹脂塗布剤から成る塗膜表面層を有する事を特徴と
する請求項１記載の熱可塑性樹脂積層構造物。2. A flexible cross-linked polyurethane-based resin coating material containing a pigment, having a composition layer having an antistatic induction property on at least one surface of a sheet substrate mainly composed of a thermoplastic resin. The thermoplastic resin laminated structure according to claim 1, further comprising a coating film surface layer comprising:
くとも４級アンモニウム塩基を有する共重合高分子から
主として成る事を特徴とする、請求項１もしくは請求項
２記載の熱可塑性樹脂積層構造物。3. The thermoplastic material according to claim 1, wherein the antistatic induction-preventing composition layer mainly comprises a copolymer having at least a quaternary ammonium base in a side chain. Resin laminate structure.
くともカルボキシル基及び４級アンモニウム塩基を有す
る架橋性共重合高分子から主として成る事を特徴とする
請求項１もしくは請求項２記載の熱可塑性樹脂積層構造
物。4. The composition according to claim 1, wherein the antistatic induction-preventing composition layer mainly comprises a crosslinkable copolymer having at least a carboxyl group and a quaternary ammonium group in a side chain. The thermoplastic resin laminated structure according to the above.
オール成分とポリイソシアネート成分の合計100重量部
に対し、水酸基含有塩化ビニル/酢酸ビニル共重合体約1
0乃至40重量部を含有する組成物から主として成る事を
特徴とする請求項１乃至４の何れか１項記載の熱可塑性
樹脂積層構造物。5. The coating film surface layer contains a pigment, and a hydroxyl group-containing vinyl chloride / vinyl acetate copolymer is used in an amount of about 1 part by weight based on 100 parts by weight of a total of a polyol component and a polyisocyanate component.
The thermoplastic resin laminated structure according to any one of claims 1 to 4, wherein the thermoplastic resin laminated structure is mainly composed of a composition containing 0 to 40 parts by weight.
m以上3μm以下であり、該塗膜表面層の厚みが1μm以上3
0μm以下である事を特徴とする請求項１乃至５の何れか
１項に記載の熱可塑性樹脂積層構造物。6. The composition according to claim 1, wherein the thickness of the composition layer is 0.01 μm.
m or more and 3 μm or less, and the thickness of the coating film surface layer is 1 μm or more and 3 μm or more.
The thermoplastic resin laminated structure according to any one of claims 1 to 5, wherein the thickness is 0 µm or less.
ィン系樹脂に無機及び/又は有機充填材を配合した組成
物シートを延伸する事により得られたものである事を特
徴とする請求項１乃至６の何れか１項に記載の熱可塑性
樹脂積層構造物。7. The thermoplastic resin sheet base material is obtained by stretching a composition sheet in which a polyolefin resin is mixed with an inorganic and / or organic filler. 7. The thermoplastic resin laminated structure according to any one of items 1 to 6.
プロピレン系樹脂100重量部に対して、軟化点（環球
法）160乃至200℃のシクロペンタジエン系石油樹脂０乃
至180重量部と無機充填材粉末０乃至170重量部との合計
0乃至200重量部が配合された組成物シートを面積倍率9
倍以上に延伸する事により得られたものである事を特徴
とする請求項１乃至７の何れか１項に記載の熱可塑性樹
脂積層構造物。8. The thermoplastic resin sheet substrate is prepared by adding 0 to 180 parts by weight of a cyclopentadiene-based petroleum resin having a softening point (ring and ball method) of 160 to 200 ° C. to 100 parts by weight of a crystalline polypropylene-based resin and inorganic filler. Total of 0 to 170 parts by weight of material powder
0 to 200 parts by weight of the composition sheet was blended with an area magnification of 9
The thermoplastic resin laminate according to any one of claims 1 to 7, wherein the thermoplastic resin laminate is obtained by stretching by a factor of two or more.
しくは請求項８記載の組成物シートの少なくとも片面に
結晶性ポリプロピレン系樹脂が更に積層された複合シー
トを面積倍率９倍以上に延伸する事により得られたもの
である事を特徴とする、請求項１乃至８の何れか１項に
記載の熱可塑性樹脂積層構造物。9. A composite sheet comprising the composition sheet according to claim 7 or 8, wherein a crystalline polypropylene resin is further laminated on at least one side of the composition sheet according to claim 7 or 8, wherein the area magnification is 9 times or more. The thermoplastic resin laminated structure according to any one of claims 1 to 8, wherein the thermoplastic resin laminated structure is obtained by performing the following.
片面に請求項３もしくは請求項４記載の静電誘導防止性
組成物を塗布乾燥して厚み0.01μm以上3μm以下の静電
誘導防止性組成物層を形成せしめた後、該静電誘導防止
性組成物層の上に、顔料を含有し、かつポリオール成分
とポリイソシアネート成分の合計100重量部に対し、水
酸基含有塩化ビニル/酢酸ビニル共重合体約10乃至40重
量部を含有する組成物を塗布乾燥して厚み1μm以上30μ
m以下の塗膜表面層を形成せしめる事を特徴とする、熱
可塑性樹脂積層構造物の製造方法。10. An anti-static induction composition having a thickness of 0.01 μm or more and 3 μm or less, wherein the composition of claim 3 or 4 is coated on at least one surface of the thermoplastic resin sheet substrate and dried. After the formation of the product layer, the pigment-containing vinyl chloride / vinyl acetate copolymer containing the pigment and the polyol component and the polyisocyanate component is added to the total of 100 parts by weight on the electrostatic induction preventing composition layer. A composition containing about 10 to 40 parts by weight of the coalesced is applied and dried to a thickness of 1 μm or more and 30 μm or more.
A method for producing a thermoplastic resin laminated structure, comprising forming a coating surface layer having a thickness of not more than m.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10345205A JP2000168018A (en) | 1998-12-04 | 1998-12-04 | Thermoplastic resin-laminated structure and its production |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10345205A JP2000168018A (en) | 1998-12-04 | 1998-12-04 | Thermoplastic resin-laminated structure and its production |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2000168018A true JP2000168018A (en) | 2000-06-20 |
Family
ID=18375019
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10345205A Pending JP2000168018A (en) | 1998-12-04 | 1998-12-04 | Thermoplastic resin-laminated structure and its production |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2000168018A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005178073A (en) * | 2003-12-17 | 2005-07-07 | Shin Etsu Polymer Co Ltd | Cover tape and package |
| US9315064B2 (en) | 2012-02-20 | 2016-04-19 | Avery Dennison Corporation | Multilayer film for multi-purpose inkjet systems |
| US9752022B2 (en) | 2008-07-10 | 2017-09-05 | Avery Dennison Corporation | Composition, film and related methods |
| CN110696474A (en) * | 2019-10-23 | 2020-01-17 | 广东鑫瑞新材料科技有限公司 | Paper-plastic compounding-transferring process adopting single-component solvent-free glue |
| US10703131B2 (en) | 2010-03-04 | 2020-07-07 | Avery Dennison Corporation | Non-PVC film and non-PVC film laminate |
| US11485162B2 (en) | 2013-12-30 | 2022-11-01 | Avery Dennison Corporation | Polyurethane protective film |
-
1998
- 1998-12-04 JP JP10345205A patent/JP2000168018A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005178073A (en) * | 2003-12-17 | 2005-07-07 | Shin Etsu Polymer Co Ltd | Cover tape and package |
| US9752022B2 (en) | 2008-07-10 | 2017-09-05 | Avery Dennison Corporation | Composition, film and related methods |
| US10703131B2 (en) | 2010-03-04 | 2020-07-07 | Avery Dennison Corporation | Non-PVC film and non-PVC film laminate |
| US9315064B2 (en) | 2012-02-20 | 2016-04-19 | Avery Dennison Corporation | Multilayer film for multi-purpose inkjet systems |
| US11485162B2 (en) | 2013-12-30 | 2022-11-01 | Avery Dennison Corporation | Polyurethane protective film |
| US11872829B2 (en) | 2013-12-30 | 2024-01-16 | Avery Dennison Corporation | Polyurethane protective film |
| CN110696474A (en) * | 2019-10-23 | 2020-01-17 | 广东鑫瑞新材料科技有限公司 | Paper-plastic compounding-transferring process adopting single-component solvent-free glue |
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