JPS63118296A - Laminate thermal transfer material - Google Patents
Laminate thermal transfer materialInfo
- Publication number
- JPS63118296A JPS63118296A JP61263950A JP26395086A JPS63118296A JP S63118296 A JPS63118296 A JP S63118296A JP 61263950 A JP61263950 A JP 61263950A JP 26395086 A JP26395086 A JP 26395086A JP S63118296 A JPS63118296 A JP S63118296A
- Authority
- JP
- Japan
- Prior art keywords
- heat
- protective layer
- perfluoroalkyl
- transfer material
- film
- 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.)
- Granted
Links
- 239000000463 material Substances 0.000 title claims abstract description 21
- 229920005989 resin Polymers 0.000 claims abstract description 22
- 239000011347 resin Substances 0.000 claims abstract description 22
- 239000011241 protective layer Substances 0.000 claims abstract description 21
- 125000005010 perfluoroalkyl group Chemical group 0.000 claims abstract description 18
- 239000002985 plastic film Substances 0.000 claims abstract description 10
- 229920006255 plastic film Polymers 0.000 claims abstract description 10
- 239000010410 layer Substances 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 4
- 239000000155 melt Substances 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 abstract description 5
- 125000001153 fluoro group Chemical group F* 0.000 abstract description 2
- 239000012260 resinous material Substances 0.000 abstract description 2
- 239000000470 constituent Substances 0.000 abstract 1
- 239000000976 ink Substances 0.000 description 10
- 239000011248 coating agent Substances 0.000 description 8
- 238000000576 coating method Methods 0.000 description 8
- 239000000203 mixture Substances 0.000 description 6
- 239000000049 pigment Substances 0.000 description 6
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 5
- 125000004432 carbon atom Chemical group C* 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 229910000077 silane Inorganic materials 0.000 description 5
- 229920000877 Melamine resin Polymers 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical group FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 description 4
- -1 polyethylene Polymers 0.000 description 4
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 239000011247 coating layer Substances 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000000975 dye Substances 0.000 description 3
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 229920006267 polyester film Polymers 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 150000004756 silanes Chemical class 0.000 description 3
- 229920001187 thermosetting polymer Polymers 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000004734 Polyphenylene sulfide Substances 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 150000003926 acrylamides Chemical class 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 235000019270 ammonium chloride Nutrition 0.000 description 2
- 239000004203 carnauba wax Substances 0.000 description 2
- 235000013869 carnauba wax Nutrition 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000007756 gravure coating Methods 0.000 description 2
- 229920006015 heat resistant resin Polymers 0.000 description 2
- 239000012943 hotmelt Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 239000010954 inorganic particle Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000004200 microcrystalline wax Substances 0.000 description 2
- 235000019808 microcrystalline wax Nutrition 0.000 description 2
- 229920006289 polycarbonate film Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920000069 polyphenylene sulfide Polymers 0.000 description 2
- 229920002545 silicone oil Polymers 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- 239000001993 wax Substances 0.000 description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- RGCKGOZRHPZPFP-UHFFFAOYSA-N Alizarin Natural products C1=CC=C2C(=O)C3=C(O)C(O)=CC=C3C(=O)C2=C1 RGCKGOZRHPZPFP-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920000298 Cellophane Polymers 0.000 description 1
- 229920002284 Cellulose triacetate Polymers 0.000 description 1
- 241000600169 Maro Species 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- 239000004697 Polyetherimide Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- NNLVGZFZQQXQNW-ADJNRHBOSA-N [(2r,3r,4s,5r,6s)-4,5-diacetyloxy-3-[(2s,3r,4s,5r,6r)-3,4,5-triacetyloxy-6-(acetyloxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6s)-4,5,6-triacetyloxy-2-(acetyloxymethyl)oxan-3-yl]oxyoxan-2-yl]methyl acetate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](OC(C)=O)[C@H]1OC(C)=O)O[C@H]1[C@@H]([C@@H](OC(C)=O)[C@H](OC(C)=O)[C@@H](COC(C)=O)O1)OC(C)=O)COC(=O)C)[C@@H]1[C@@H](COC(C)=O)O[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@H]1OC(C)=O NNLVGZFZQQXQNW-ADJNRHBOSA-N 0.000 description 1
- 229920006397 acrylic thermoplastic Polymers 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- HFVAFDPGUJEFBQ-UHFFFAOYSA-M alizarin red S Chemical compound [Na+].O=C1C2=CC=CC=C2C(=O)C2=C1C=C(S([O-])(=O)=O)C(O)=C2O HFVAFDPGUJEFBQ-UHFFFAOYSA-M 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 229920003235 aromatic polyamide Polymers 0.000 description 1
- 239000000981 basic dye Substances 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 229910052799 carbon Chemical group 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000008119 colloidal silica Substances 0.000 description 1
- 238000003851 corona treatment Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000000986 disperse dye Substances 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- HDERJYVLTPVNRI-UHFFFAOYSA-N ethene;ethenyl acetate Chemical group C=C.CC(=O)OC=C HDERJYVLTPVNRI-UHFFFAOYSA-N 0.000 description 1
- 229920001038 ethylene copolymer Polymers 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 235000011167 hydrochloric acid Nutrition 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000002075 main ingredient Substances 0.000 description 1
- 125000005397 methacrylic acid ester group Chemical group 0.000 description 1
- SQDFHQJTAWCFIB-UHFFFAOYSA-N n-methylidenehydroxylamine Chemical compound ON=C SQDFHQJTAWCFIB-UHFFFAOYSA-N 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 235000019809 paraffin wax Nutrition 0.000 description 1
- 235000019271 petrolatum Nutrition 0.000 description 1
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 125000003367 polycyclic group Chemical group 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920001601 polyetherimide Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は、感熱転写材に関し、特に感熱転写リボンとし
ての利用に適する感熱転写材に関する。DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a thermal transfer material, and particularly to a thermal transfer material suitable for use as a thermal transfer ribbon.
（従来の技術）
従来、プラスチックフィルムからなる基材の一方の面に
加熱により溶融もしくは昇華する転写インキ層を有する
感熱転写材において、基材の他方の面としては、蒸着層
を設けたもの、熱硬化性樹脂の耐熱保護層を設けたもの
、フッ素系樹脂と水性高分子および／または反応性低分
子量体よりなる耐熱保護層を設けたもの、あるいは熱可
塑性の耐熱樹脂層を設けたもの、さらにはこれらの樹脂
層に無機粒子を添加したものなどが提案されている。(Prior Art) Conventionally, heat-sensitive transfer materials have a transfer ink layer that melts or sublimates when heated on one side of a base material made of a plastic film, and a vapor-deposited layer is provided on the other side of the base material. Those provided with a heat-resistant protective layer made of thermosetting resin, those provided with a heat-resistant protective layer made of fluororesin, water-based polymer and/or reactive low molecular weight substance, or those provided with a thermoplastic heat-resistant resin layer, Furthermore, those in which inorganic particles are added to these resin layers have been proposed.
（発明が解決しようとする問題点）
しかし、蒸着層を設けたものにあっては金属の蒸着がバ
ッチ処理のためコスト高を免れないし、スティッキング
の防止に有効なほど厚くすると、熱伝導性が大きく、熱
の拡散が進むため解像度が悪化するという欠点がある。(Problems to be Solved by the Invention) However, in the case of products with a vapor-deposited layer, the metal vapor deposition is a batch process, so the cost is inevitably high, and if the thickness is made thick enough to be effective in preventing sticking, the thermal conductivity will be low. The drawback is that the resolution deteriorates due to the large size and increased heat diffusion.
一方熱硬化性樹脂あるいは耐熱性樹脂をコートしたもの
は、スティッキングはしないものの高温になるにつれ程
度の差はあるが、すべり性が悪化するという欠点がある
。On the other hand, those coated with a thermosetting resin or a heat-resistant resin do not cause sticking, but have the disadvantage that their slipperiness worsens as the temperature increases, although the degree varies.
この欠点を改良する目的で無機系の滑剤を添加する試み
もなされているが、この場合には表面が粗れすぎるため
、加熱ヘッドへの密着不良を発生したり、あるいは伝熱
効率が悪化するという欠点があった。Attempts have been made to add inorganic lubricants to improve this drawback, but in this case, the surface becomes too rough, resulting in poor adhesion to the heating head or poor heat transfer efficiency. There were drawbacks.
またフッ素系樹脂を使用した場合は塗膜の強靭性に欠け
るという欠点があった。Furthermore, when a fluororesin is used, there is a drawback that the coating film lacks toughness.
本発明の目的は、上記欠点のないもの、すなわち、ステ
ィッキングがなく、また伝熱効率、すべり性、塗膜強靭
性に優れた感熱転写リボンに好適である感熱転写材を提
供することにある。An object of the present invention is to provide a thermal transfer material that does not have the above-mentioned drawbacks, that is, is suitable for a thermal transfer ribbon that is free from sticking and has excellent heat transfer efficiency, slipperiness, and coating toughness.
（問題点を解決するための手段）
上記本発明の目的は、プラスチックフィルムからなる基
材の一方の面に加熱により溶融もしくは昇華する転写イ
ンキ層を有し、他方の面に耐熱保護層を有する感熱転写
材において、該耐熱保護層がパーフロロアルキル基含有
樹脂を少なくとも１０重量％含有することを特徴とする
感熱転写材によって達成される。(Means for Solving the Problems) The object of the present invention is to have a transfer ink layer that melts or sublimates when heated on one side of a base material made of a plastic film, and a heat-resistant protective layer on the other side. This is achieved by a heat-sensitive transfer material in which the heat-resistant protective layer contains at least 10% by weight of a perfluoroalkyl group-containing resin.
本発明の感熱転写材における基材プラスチックフィルム
としては適宜公知のプラスチックフィルムを用いうる。As the base plastic film in the thermal transfer material of the present invention, any known plastic film may be used as appropriate.
代表的なものとして、ポリエステルフィルム、ポリカー
ボネートフィルム、トリアセチルセルロースフィルム、
セロハンフィルム、ポリアミドフィルム、ポリイミドフ
ィルム、ポリフェニレンスルフィドフィルム、ホリエー
テルイミドフイルム、ポリエーテルスルホンフィルム、
芳香族ポリアミドフィルム、ポリスルホンフィルム、ポ
リオレフィンフィルムなどを挙げろことができる。しか
し、価格、耐熱性の面からポリエステルフィルム、ポリ
カーボネートフィルム、ポリフェニレンスルフィドフィ
ルムを用いるのが特に好ましい。またプラスチックフィ
ルム厚みは、特に限定されないが、通常０．５μｍ以上
４０μｍ以下である。Typical examples include polyester film, polycarbonate film, triacetylcellulose film,
Cellophane film, polyamide film, polyimide film, polyphenylene sulfide film, polyetherimide film, polyether sulfone film,
Examples include aromatic polyamide film, polysulfone film, and polyolefin film. However, from the viewpoint of cost and heat resistance, it is particularly preferable to use polyester film, polycarbonate film, and polyphenylene sulfide film. The thickness of the plastic film is not particularly limited, but is usually 0.5 μm or more and 40 μm or less.
基材プラスチックフィルムの一方の面に設けろ転写イン
キ層を構成する溶融もしくは昇華する転写インキも特に
限定されず、適宜公知のものを用いることができろ。熱
溶融性インキとしては、（１）パラフィンワックス、マ
イクロクリスタリンワックス、カルナウバワックスなど
の適当な融点をもったワックス、（２）顔料、（３）オ
イルなどの柔軟剤、を主成分とし、必要に応じ種々の添
加剤を加えたものをその代表例として挙げることができ
る。この際使用する顔料としてはアゾ顔料、フタロシア
ニン顔料、染付はレーキ、縮合多環顔料、ニトロン顔料
、アリザリンレーキ等の有機顔料をその代表として挙げ
ることができる。一方昇華性インキとしては、（１）と
ドロキシエチルセルロースのようなセルロース系水溶性
アクリル、ポリビニルアルコールあるいはポリアミド系
樹脂、（２）イエロー、マゼンタ、シアンの昇華性染料
を主体とし、必要に応じ種々の添加剤を加えたものをそ
の代表例として挙げろことができる。昇華性染料として
は、分散染料、塩基性染料および油溶性染料をその代表
として挙げることができる。またその厚みは特に限定さ
れないが通常は０．１〜１５μ１１好ましくは１〜６μ
ｍである。The melting or sublimating transfer ink constituting the transfer ink layer provided on one surface of the base plastic film is also not particularly limited, and any known transfer ink may be used as appropriate. The main ingredients of the hot-melt ink are (1) a wax with an appropriate melting point such as paraffin wax, microcrystalline wax, or carnauba wax, (2) a pigment, and (3) a softener such as oil. Typical examples include those to which various additives are added depending on the requirements. Typical pigments used in this case include organic pigments such as azo pigments, phthalocyanine pigments, dyeing lakes, condensed polycyclic pigments, nitrone pigments, and alizarin lakes. On the other hand, sublimable inks mainly include (1) cellulose-based water-soluble acrylics such as droxyethyl cellulose, polyvinyl alcohol, or polyamide resins, and (2) sublimable dyes of yellow, magenta, and cyan. A typical example is one containing additives. Representative examples of sublimable dyes include disperse dyes, basic dyes, and oil-soluble dyes. The thickness is not particularly limited, but is usually 0.1 to 15μ, preferably 1 to 6μ.
It is m.
本発明の感熱転写材は基材プラスチックフィルムの他方
の面にパーフロロアルキルｉ 含Ｗ ｍ Ｍｌを少なく
とも１０重量％含有する耐熱保１！層を設けたことを特
徴とするが、ここでパー７０ロアルキル基含有樹脂とは
アルキル基を構成する水素原子がフッ素原子で置換した
基を有する樹脂状物をいう。パーフロロアルキル基の例
としてはテトラフルオロエチレンオリゴマー残基やヘキ
サフルオロプロピレンオリゴマー残基がある。ここに例
示したテトラブルオロエチレンオリゴマー残基としては
炭素原子数２〜１０のものがまたへキサフルオロプロピ
レンオリゴマー残基としては炭素原子数３〜９のものが
好適である。かかるパーフロロアルキル基含有樹脂の例
としてはパーフロロアルキル基含有ビニルモノマーを単
独又は共重合したものやバーフロ四アルキル官能シラン
等がある。パーフロロアルキル基含有ビニルモノマーを
アクリル酸、メタクリル酸又はそのエステルと共重合し
たものは塗膜の強靭性が良好であるという利点を有する
。かかる共重合体の具体例としては、ＣＨ＝ＣＨ０ＣＯ
Ｒ’ 又は ＣＨ＝Ｃ−Ｃ０ＯＲ’ との共重合体
（式中Ｒは水素原子又は炭素原子数１〜６のアルキル基
、ｎは１〜８の整数、Ｒｆはテトラフルオロエチレンオ
リゴマー残基および／またはヘキサフルオロプロピレン
オリゴマー残基、Ｒ′は水素又は炭素原子数１〜１４の
アルキル基）を挙げることができる。またパーフロロア
ルキル基、特にテトラフルオロエチレンオリゴマー残基
および／またはへキサフルオロプロピレンオリゴマー残
基を有するアクリル酸又はメタクリル酸エステル系重合
体も好ましいものの一つである。The heat-sensitive transfer material of the present invention contains at least 10% by weight of perfluoroalkyl i-containing W m Ml on the other side of the base plastic film. The per-70-roalkyl group-containing resin herein refers to a resinous material having a group in which the hydrogen atoms constituting the alkyl group are substituted with fluorine atoms. Examples of perfluoroalkyl groups include tetrafluoroethylene oligomer residues and hexafluoropropylene oligomer residues. The tetrafluoroethylene oligomer residues exemplified herein are preferably those having 2 to 10 carbon atoms, and the hexafluoropropylene oligomer residues are preferably those having 3 to 9 carbon atoms. Examples of such perfluoroalkyl group-containing resins include those obtained by singly or copolymerizing perfluoroalkyl group-containing vinyl monomers, and barfluoro-tetraalkyl-functional silanes. A product obtained by copolymerizing a perfluoroalkyl group-containing vinyl monomer with acrylic acid, methacrylic acid, or an ester thereof has the advantage that the toughness of the coating film is good. Specific examples of such copolymers include CH=CHOCO
Copolymer with R' or CH=C-COOR' (wherein R is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, n is an integer of 1 to 8, Rf is a tetrafluoroethylene oligomer residue and/or or a hexafluoropropylene oligomer residue (R' is hydrogen or an alkyl group having 1 to 14 carbon atoms). Also preferred are acrylic acid or methacrylic acid ester polymers having perfluoroalkyl groups, particularly tetrafluoroethylene oligomer residues and/or hexafluoropropylene oligomer residues.
これらの具体例としては、
す
を挙げることができる。（式中Ｒは水素又は炭素数１〜
５のアルキル基、麿は０〜２０の整ｆｉ、ｍは１〜２０
の整数、ｎは１以上、通常は１０００以上の１０００万
以下の整数）を挙げることができる。Specific examples of these include: (In the formula, R is hydrogen or carbon number 1-
5 alkyl group, Maro is an integer from 0 to 20, m is from 1 to 20
n is an integer of 1 or more, usually an integer of 1,000 or more and 10,000,000 or less).
またパーフロロアルキル官能シランも好ましいものの一
つであり、特に高温でのスティッキング性及び塗膜強靭
性の面からみて、パーフロロアルキル官能シランを使用
するのが最も好ましい。Perfluoroalkyl-functional silanes are also preferred, and from the viewpoint of sticking properties and coating toughness, particularly at high temperatures, perfluoroalkyl-functional silanes are most preferably used.
パーフロロアルキル官能シランはパーフロロアルキル基
含有シランであり、その構造は特に限定されないが、代
表的なものとして次のようなものを挙げることができろ
。The perfluoroalkyl-functional silane is a silane containing a perfluoroalkyl group, and its structure is not particularly limited, but the following are representative examples.
Ｃ，Ｆ□、Ｃ０ＮＨ（ＣＨ，）３Ｓ ｉ （ＱＣ，ＨＪ
３Ｃ，Ｆ、５ｏ２ＮＨ（ＣＨ２）３Ｓ ｉ （ＱＣ，Ｈ
Ｊ。C,F□,C0NH(CH,)3S i (QC,HJ
3C,F,5o2NH(CH2)3S i (QC,H
J.
Ｃ，ＦｉｓＣＯＮ）ＩｃＨ２Ｃ１（、ＮＨＣＯＣ，Ｆ、
。C, FisCON) IcH2C1 (, NHCOC, F,
.
ＣＦ、ＣＨ２ＣＨ２５ｉ （ＯＣＨ３）３ＣＦ、（ＣＦ
２）３ＣＨ２ＣＨ２Ｓ ｉ （ＯＣＨつ）３ＣＦ、（Ｃ
Ｆ２）７ＣＨ２０Ｈ２Ｓ ｉ （ＯＣＨ３）。CF, CH2CH25i (OCH3)3CF, (CF
2) 3CH2CH2S i (OCH)3CF, (C
F2)7CH20H2S i (OCH3).
ＣＦ、（ＣＦρ６ＣＯＯ（ＣＨ，）３Ｓ ｉ （ＯＣＨ
，）３ＣＦ３（ＣＦ２）６ＣＯ５（ＣＨ八へｔ（ＯＣＨ
，）３ＣＦ、（ＣＦ２）、ＣＨ２ＣＨ２５ＣＨ２ＣＨ２
Ｓ ｉ （ＯＣＨ３）３ＣＦ３（ＣＦ入ＣＨ２ＣＨ，Ｓ
ＣＨ，ＣＨ，Ｓ ｉ （ＯＣＨ５）３このようなパー７
０ロアルキル官能シランは単体で使用してもよいが、他
の化合物、特に熱硬化型化合物、例えばシランカップリ
ング剤メラミン系樹脂と併用してもよい。特にアクリル
アミド誘導体を主鎖中に有するアクリルアミド系重合体
、その中でもアクリルアミド誘導体とアクリル酸又はメ
タクリル酸のエステルとの共重合体を主成分とするもの
と併用すると塗膜強度が更に向上するため好ましい。こ
れらの樹脂は熱架橋してもよいし、触媒を用いて架橋し
てもよい。使用する触媒は特に限定されないが、塩化ア
ンモニウム、蓚酸、塩酸、スルホン酸化合物、水酸化リ
チウムなどを挙げろことができろ。また必要に応じてメ
チロール化メラミン等のメラミン系樹脂（化合物）を使
用してもよい。CF, (CFρ6COO(CH,)3S i (OCH
,)3CF3(CF2)6CO5(CH8het(OCH
,)3CF, (CF2), CH2CH25CH2CH2
S i (OCH3)3CF3 (CH2CH with CF, S
CH,CH,S i (OCH5)3 Such a par 7
The 0-roalkyl-functional silane may be used alone, but it may also be used in combination with other compounds, especially thermosetting compounds, such as melamine-based resins as silane coupling agents. In particular, it is preferable to use an acrylamide-based polymer having an acrylamide derivative in the main chain, especially one whose main component is a copolymer of an acrylamide derivative and an ester of acrylic acid or methacrylic acid, because the strength of the coating film is further improved. These resins may be thermally crosslinked or crosslinked using a catalyst. The catalyst used is not particularly limited, but examples include ammonium chloride, oxalic acid, hydrochloric acid, sulfonic acid compounds, and lithium hydroxide. Furthermore, melamine resins (compounds) such as methylolated melamine may be used if necessary.
本発明の耐熱保護層中におけるパーフロロアルキル基含
有樹脂の占める割合は、１０重量％以上、好ましくは３
０重量％以上、更に好ましくは５０１！量％以上１００
重量％以下である。１０重量％より少ない場合には、ス
ティック改良効果が十分でない。The proportion of the perfluoroalkyl group-containing resin in the heat-resistant protective layer of the present invention is 10% by weight or more, preferably 3% by weight or more.
0% by weight or more, more preferably 501! Amount% more than 100
% by weight or less. If it is less than 10% by weight, the stick improvement effect will not be sufficient.
耐熱保護層を構成しうるパーフロロアルキル基含有樹脂
以外の成分は耐熱保護層としての機能を示しうろもので
あればいずれでもよく適宜公知の保護層素材が用いられ
うるが、熱硬化性樹脂又はその前駆体（オリゴマー又は
モノマー）がスティッキングの面から好適である。又必
要に応じて各種界面活性剤、炭酸カルシウム、コロイダ
ルシリ −カ、二酸化チタン等の無機粒子あるいはポリ
エチレンワックス等の低分子量有機物を添加してもよい
。The components other than the perfluoroalkyl group-containing resin that can constitute the heat-resistant protective layer may be any components that can function as a heat-resistant protective layer, and known protective layer materials may be used as appropriate. Its precursor (oligomer or monomer) is suitable from the viewpoint of sticking. If necessary, various surfactants, inorganic particles such as calcium carbonate, colloidal silica, titanium dioxide, etc., or low molecular weight organic substances such as polyethylene wax may be added.
特に炭素原子数１８〜３３の高級脂肪酸モノカルボン酸
からなる化合物の金属塩又は部分金属塩化合物、あるい
はシリコーンオイル、特に変性シリコーンオイルを添加
するのがスティッキング性改良効果が顕著であるため好
適である。In particular, it is preferable to add a metal salt or partial metal salt compound of a compound consisting of a higher fatty acid monocarboxylic acid having 18 to 33 carbon atoms, or a silicone oil, especially a modified silicone oil, because the sticking property improving effect is remarkable. .
次に本発明の代表的な感熱転写製造方法について説明す
るが、当然これに限定されるものではない。まず基材と
するプラスチックフィルムを用意する。このフィルムは
、必要に応じ、空気中その他種々の雰囲気中でコロナ放
電処理を施しておいてもよい。またウレタン樹脂、エポ
キシ樹脂など公知のアンカー処理剤を用いてアンカー処
理を施しておいてもよいが通常は特に必要ではない。該
フィルム上に耐熱保護層を、グラビアコート、リバース
コート、スプレーコート等公知の方法を用いてコーティ
ングした後、６０℃〜２５０℃で１ｓｅｃ〜１５分程度
乾燥させる。この場合ｉ１！Ｆｖｘは特に限定されない
が通常は水、アルコールあるいは水とアルコールの混合
系が使用されろ。続いて熱溶融性もしくは昇華性のイン
キを同様の方法で反対面にコートした後、所定の温度で
乾燥する。これらのコートは順不同で行えばよく、勿論
同時に行ってもよい。又コーティング層を別途製膜して
おき、あとからラミネートしても良いが、コーティング
層は、やや強度が不足である点から、直接基材フィルム
上にコーティングする方が好ましい。Next, a typical thermal transfer manufacturing method of the present invention will be described, but the present invention is not limited thereto. First, prepare a plastic film as a base material. This film may be subjected to corona discharge treatment in air or other various atmospheres, if necessary. Anchor treatment may be performed using a known anchor treatment agent such as urethane resin or epoxy resin, but this is usually not necessary. A heat-resistant protective layer is coated on the film using a known method such as gravure coating, reverse coating, or spray coating, and then dried at 60° C. to 250° C. for about 1 sec to 15 minutes. In this case i1! Although Fvx is not particularly limited, water, alcohol, or a mixture of water and alcohol is usually used. Subsequently, heat-melting or sublimation ink is coated on the opposite side in the same manner, and then dried at a predetermined temperature. These coats may be performed in any order, and of course may be performed at the same time. Alternatively, a coating layer may be formed separately and laminated later, but it is preferable to coat the coating layer directly onto the base film since the strength of the coating layer is somewhat insufficient.
転写インキ層は、バーコード、リバースコート、グラビ
アコート等の公知の方法で、耐熱保護層塗布の前後を問
わずコートすることができる。The transfer ink layer can be coated by a known method such as barcode coating, reverse coating, gravure coating, etc., regardless of whether or not the heat-resistant protective layer is coated.
また基材フィルムが２軸延坤されている場合、その製造
工程で塗布することも可能である。すなわちその−例を
具体的に述べれば、一方向に延伸後のポリエステルフィ
ルムの少なくとも片面に耐熱保護層を塗布し、乾燥した
後あるいは乾燥しつつ直角方向に延伸した後、熱処理を
行うか、あるいは直角方向に延伸を行った後、前記一方
向に再延伸し熱処理を行う方法がある。Further, when the base film is biaxially stretched, it is also possible to apply it during the manufacturing process. Specifically, a heat-resistant protective layer is applied to at least one side of the polyester film after being stretched in one direction, and after drying or after being stretched in the right angle direction while drying, heat treatment is performed. There is a method of stretching in the perpendicular direction, then re-stretching in the one direction, and then heat-treating.
（発明の効果）
本発明はパーフロロアルキル基含有樹脂を必須成分とす
る耐熱保護層を設けたことにより、スティッキングが起
こらない感熱転写材を得ることが可能となった。(Effects of the Invention) By providing a heat-resistant protective layer containing a perfluoroalkyl group-containing resin as an essential component, the present invention has made it possible to obtain a heat-sensitive transfer material that does not cause sticking.
本発明の感熱転写材は、スティッキング性にすぐれるた
め、ファクシミリ、バーコードプリンター、グラフィッ
クプリンター、自動発券機用等に特に好適に用いられろ
。Since the thermal transfer material of the present invention has excellent sticking properties, it is particularly suitable for use in facsimiles, barcode printers, graphic printers, automatic ticket issuing machines, and the like.
（特性の測定方法並びに効果の評価方法）（１）スティ
ック性： 七−トシーラを用いてガラス板とのスティッ
ク性を評価する。まず上下の熱板を２００℃あるいは２
３５℃（上下同温）に設定し、その間に厚さ１＋ｍの石
英ガラス板と感熱転写材を重ね合わせヒートシールする
。ｔ′−だし耐熱保護層が石英ガラスと接する様に重ね
合わせろこととし、ヒートシール条件としては面圧１．
Ｏｋｇ／ｃＩｌで、１０秒間熱圧着することとする。こ
のようにしてヒートシールしたサンプルを常温まで徐冷
した後、剥離して、その剥離状態によりスティック性を
判定することとする。即ち冷却したときに、既にはがれ
てしまっているものを「０」、密着しているが全く抵抗
なくはがれるものを「Ｏ」、剥離する際抵抗感（剥離強
度１０ｇ／ｃｍ以上）があるものを「×」と判定する。(Method of Measuring Properties and Evaluating Effects) (1) Stickiness: Evaluate stickiness with a glass plate using a 7-toshira. First, heat the upper and lower heating plates to 200℃ or 2
The temperature was set at 35°C (same temperature on top and bottom), and a 1+m thick quartz glass plate and a heat-sensitive transfer material were overlapped and heat-sealed. The heat-resistant protective layer was placed on top of the quartz glass so that it was in contact with the quartz glass, and the heat sealing conditions were a surface pressure of 1.
Thermocompression bonding is performed for 10 seconds at Okg/cIl. After the sample heat-sealed in this manner is slowly cooled to room temperature, it is peeled off, and the stickiness is determined based on the peeled state. In other words, "0" means that it has already peeled off when cooled, "O" means that it adheres but peels off without any resistance, and "O" means that it peels off without any resistance (peel strength of 10 g/cm or more). It is judged as "x".
（実施例） 本発明を実施例に基づいて説明する。(Example) The present invention will be explained based on examples.
実施例１〜４．比較例１〜２
厚さ５μ重のポリエチレンテレツクレート２軸延伸フィ
ルムの一方の面に、カルナウバワックス１００１ｉ量部
、マイクロクリスタリンワックス３０重量部、酢酸ビニ
ル−エチレン共重合体１５重量部、カーボンブラック２
０重量部からなる熱溶融性インクを５μ■塗布する。反
対の面に次の組成の耐熱保：４１Ｐｌを乾燥後の厚みに
して０．２μｍ塗布する。Examples 1-4. Comparative Examples 1 and 2 On one side of a polyethylene telescrate biaxially stretched film having a thickness of 5μ, 1001i parts of carnauba wax, 30 parts by weight of microcrystalline wax, 15 parts by weight of vinyl acetate-ethylene copolymer, and carbon black were added. 2
Apply 5 .mu.m of hot-melt ink consisting of 0 parts by weight. On the opposite side, apply a heat-resistant adhesive having the following composition: 41Pl to a thickness of 0.2 μm after drying.
ただし乾燥は各々１６０℃熱風中で行った。However, each sample was dried in hot air at 160°C.
（耐熱保護層組成）
構造 組成比上記組
成物に硬化触媒としてＮＨ４Ｃｌを５部添加する。(Heat-resistant protective layer composition) Structure Composition ratio 5 parts of NH4Cl is added as a curing catalyst to the above composition.
表中にみる如りパーフロロアルキル基をもつシランが全
くないかあるいは少なすぎる場合（比較例１，２）はス
ティック性が十分とはいえないのである。As shown in the table, when there is no silane having a perfluoroalkyl group or there is too little silane (Comparative Examples 1 and 2), the stick property cannot be said to be sufficient.
実・雄側５．比較例３
パーフロロアルキル基をもつ樹脂を以下のものに変更し
、実施例１と同様にして製造・評価した。Fruit/male side 5. Comparative Example 3 A resin having a perfluoroalkyl group was changed to the following resin, and the same procedure as in Example 1 was carried out to produce and evaluate the resin.
構造
ＣＨ１ＣＨ２（ＣＦ２）ＳＣＦ３
表中にみる如くパーフロロアルキル基をもつ樹脂が少な
すぎる場合（比較例３）スティック性は十分とはいえず
、本発明範囲においてはじめて耐スティック性を得ろこ
とができることが判る。しかし本実施例の如き熱可塑型
樹脂に比べて、硬化型樹脂（実施例１〜４）の場合の方
が耐スティック性によりすぐれていることがわかる。Structure CH1CH2(CF2)SCF3 As shown in the table, when there is too little resin having perfluoroalkyl groups (Comparative Example 3), the stick property cannot be said to be sufficient, and it is not possible to obtain stick resistance for the first time within the scope of the present invention. I understand. However, it can be seen that the stick resistance of the curable resins (Examples 1 to 4) is better than that of the thermoplastic resin as in this example.
実施例６
実施例２と他の条件は全く同一で、たｔ！耐熱保護層に
メチロール化メラミン（住人化学■製スミマールＭ５０
Ｗ）を８０重量部（従来組成１００重量部に対し）加え
同様に評価した。スティック性は同様にすぐれており、
表中には示さなかったが「もみ」に対する亀裂の発生が
実施例２に比べより良好であった。Example 6 The other conditions were exactly the same as in Example 2. The heat-resistant protective layer is methylolized melamine (Sumimar M50 manufactured by Juju Chemical Co., Ltd.)
80 parts by weight (relative to 100 parts by weight of the conventional composition) of W) were added and evaluated in the same manner. The stickiness is also excellent,
Although not shown in the table, the occurrence of cracks due to "massage" was better than in Example 2.
Claims (1)
より溶融もしくは昇華する転写インキ層を有し、他方の
面に耐熱保護層を有する感熱転写材において、該耐熱保
護層がパーフロロアルキル基含有樹脂を少なくとも１０
重量％含有することを特徴とする感熱転写材。In a heat-sensitive transfer material having a transfer ink layer that melts or sublimes by heating on one side of a base material made of a plastic film and a heat-resistant protective layer on the other side, the heat-resistant protective layer is made of a perfluoroalkyl group-containing resin. at least 10
A heat-sensitive transfer material characterized by containing % by weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61263950A JP2661022B2 (en) | 1986-11-07 | 1986-11-07 | Laminated thermal transfer material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61263950A JP2661022B2 (en) | 1986-11-07 | 1986-11-07 | Laminated thermal transfer material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63118296A true JPS63118296A (en) | 1988-05-23 |
| JP2661022B2 JP2661022B2 (en) | 1997-10-08 |
Family
ID=17396503
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61263950A Expired - Fee Related JP2661022B2 (en) | 1986-11-07 | 1986-11-07 | Laminated thermal transfer material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2661022B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5141915A (en) * | 1991-02-25 | 1992-08-25 | Minnesota Mining And Manufacturing Company | Dye thermal transfer sheet with anti-stick coating |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6230082A (en) * | 1985-07-31 | 1987-02-09 | Tdk Corp | Thermal sensitive recording transfer medium |
| JPS6233684A (en) * | 1985-08-07 | 1987-02-13 | Ricoh Co Ltd | Thermal transfer sheet |
| JPS6233683A (en) * | 1985-08-06 | 1987-02-13 | Ricoh Co Ltd | Thermal transfer sheet |
| JPS62227786A (en) * | 1986-03-31 | 1987-10-06 | Toyo Ink Mfg Co Ltd | Thermal transfer material |
| JPS6374687A (en) * | 1986-09-17 | 1988-04-05 | Canon Inc | Thermal transfer material |
-
1986
- 1986-11-07 JP JP61263950A patent/JP2661022B2/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6230082A (en) * | 1985-07-31 | 1987-02-09 | Tdk Corp | Thermal sensitive recording transfer medium |
| JPS6233683A (en) * | 1985-08-06 | 1987-02-13 | Ricoh Co Ltd | Thermal transfer sheet |
| JPS6233684A (en) * | 1985-08-07 | 1987-02-13 | Ricoh Co Ltd | Thermal transfer sheet |
| JPS62227786A (en) * | 1986-03-31 | 1987-10-06 | Toyo Ink Mfg Co Ltd | Thermal transfer material |
| JPS6374687A (en) * | 1986-09-17 | 1988-04-05 | Canon Inc | Thermal transfer material |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5141915A (en) * | 1991-02-25 | 1992-08-25 | Minnesota Mining And Manufacturing Company | Dye thermal transfer sheet with anti-stick coating |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2661022B2 (en) | 1997-10-08 |
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