JPS6384978A - Reversible thermal recording material - Google Patents
Reversible thermal recording materialInfo
- Publication number
- JPS6384978A JPS6384978A JP61231598A JP23159886A JPS6384978A JP S6384978 A JPS6384978 A JP S6384978A JP 61231598 A JP61231598 A JP 61231598A JP 23159886 A JP23159886 A JP 23159886A JP S6384978 A JPS6384978 A JP S6384978A
- Authority
- JP
- Japan
- Prior art keywords
- temperature
- heat
- sensitive layer
- thermosensible
- color
- 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 54
- 230000002441 reversible effect Effects 0.000 title claims abstract description 24
- 239000000126 substance Substances 0.000 claims abstract description 19
- 229920005989 resin Polymers 0.000 claims abstract description 18
- 239000011347 resin Substances 0.000 claims abstract description 18
- 239000011159 matrix material Substances 0.000 claims description 3
- 238000004040 coloring Methods 0.000 abstract 2
- 238000010276 construction Methods 0.000 abstract 1
- 239000000758 substrate Substances 0.000 abstract 1
- 229920001577 copolymer Polymers 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- 239000002253 acid Substances 0.000 description 8
- 150000002148 esters Chemical class 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- 239000006185 dispersion Substances 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 5
- 150000007513 acids Chemical class 0.000 description 4
- 150000001408 amides Chemical class 0.000 description 4
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- -1 ammonium salts Salts Chemical class 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 235000014113 dietary fatty acids Nutrition 0.000 description 3
- 229930195729 fatty acid Natural products 0.000 description 3
- 239000000194 fatty acid Substances 0.000 description 3
- 150000004665 fatty acids Chemical class 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- HPEUJPJOZXNMSJ-UHFFFAOYSA-N Methyl stearate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC HPEUJPJOZXNMSJ-UHFFFAOYSA-N 0.000 description 2
- 235000021355 Stearic acid Nutrition 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- UKMSUNONTOPOIO-UHFFFAOYSA-N docosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCC(O)=O UKMSUNONTOPOIO-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical class C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 2
- VKOBVWXKNCXXDE-UHFFFAOYSA-N icosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCC(O)=O VKOBVWXKNCXXDE-UHFFFAOYSA-N 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 2
- ISYWECDDZWTKFF-UHFFFAOYSA-N nonadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCCC(O)=O ISYWECDDZWTKFF-UHFFFAOYSA-N 0.000 description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 2
- 229920001225 polyester resin Polymers 0.000 description 2
- 239000004645 polyester resin Substances 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000008117 stearic acid Substances 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- LIZLYZVAYZQVPG-UHFFFAOYSA-N (3-bromo-2-fluorophenyl)methanol Chemical compound OCC1=CC=CC(Br)=C1F LIZLYZVAYZQVPG-UHFFFAOYSA-N 0.000 description 1
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- 229940090248 4-hydroxybenzoic acid Drugs 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 235000021357 Behenic acid Nutrition 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 1
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 1
- 239000005639 Lauric acid Substances 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- 235000021314 Palmitic acid Nutrition 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 229920002433 Vinyl chloride-vinyl acetate copolymer Polymers 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 125000003158 alcohol group Chemical group 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000001345 alkine derivatives Chemical class 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- JPIYZTWMUGTEHX-UHFFFAOYSA-N auramine O free base Chemical compound C1=CC(N(C)C)=CC=C1C(=N)C1=CC=C(N(C)C)C=C1 JPIYZTWMUGTEHX-UHFFFAOYSA-N 0.000 description 1
- 229940116224 behenate Drugs 0.000 description 1
- UKMSUNONTOPOIO-UHFFFAOYSA-M behenate Chemical compound CCCCCCCCCCCCCCCCCCCCCC([O-])=O UKMSUNONTOPOIO-UHFFFAOYSA-M 0.000 description 1
- 229940116226 behenic acid Drugs 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229920006026 co-polymeric resin Polymers 0.000 description 1
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 150000001924 cycloalkanes Chemical class 0.000 description 1
- 150000001925 cycloalkenes Chemical class 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- CAMHHLOGFDZBBG-UHFFFAOYSA-N epoxidized methyl oleate Natural products CCCCCCCCC1OC1CCCCCCCC(=O)OC CAMHHLOGFDZBBG-UHFFFAOYSA-N 0.000 description 1
- 125000002573 ethenylidene group Chemical group [*]=C=C([H])[H] 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- FWQHNLCNFPYBCA-UHFFFAOYSA-N fluoran Chemical compound C12=CC=CC=C2OC2=CC=CC=C2C11OC(=O)C2=CC=CC=C21 FWQHNLCNFPYBCA-UHFFFAOYSA-N 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 1
- 239000004312 hexamethylene tetramine Substances 0.000 description 1
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 1
- YAQXGBBDJYBXKL-UHFFFAOYSA-N iron(2+);1,10-phenanthroline;dicyanide Chemical compound [Fe+2].N#[C-].N#[C-].C1=CN=C2C3=NC=CC=C3C=CC2=C1.C1=CN=C2C3=NC=CC=C3C=CC2=C1 YAQXGBBDJYBXKL-UHFFFAOYSA-N 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- TZXYSEYEGNHPQI-UHFFFAOYSA-N octadecyl dodecanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCCCCCCCCCC TZXYSEYEGNHPQI-UHFFFAOYSA-N 0.000 description 1
- NKBWPOSQERPBFI-UHFFFAOYSA-N octadecyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCCCCCCCCCCCCCCCC NKBWPOSQERPBFI-UHFFFAOYSA-N 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229950000688 phenothiazine Drugs 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 229920001490 poly(butyl methacrylate) polymer Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- NPSSWQJHYLDCNV-UHFFFAOYSA-N prop-2-enoic acid;hydrochloride Chemical compound Cl.OC(=O)C=C NPSSWQJHYLDCNV-UHFFFAOYSA-N 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002195 soluble material Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- MHXBHWLGRWOABW-UHFFFAOYSA-N tetradecyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCCCCCCCCCCCCCC MHXBHWLGRWOABW-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- AAAQKTZKLRYKHR-UHFFFAOYSA-N triphenylmethane Chemical compound C1=CC=CC=C1C(C=1C=CC=CC=1)C1=CC=CC=C1 AAAQKTZKLRYKHR-UHFFFAOYSA-N 0.000 description 1
- 229920002554 vinyl polymer Polymers 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
- B41M5/36—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using a polymeric layer, which may be particulate and which is deformed or structurally changed with modification of its' properties, e.g. of its' optical hydrophobic-hydrophilic, solubility or permeability properties
- B41M5/363—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using a polymeric layer, which may be particulate and which is deformed or structurally changed with modification of its' properties, e.g. of its' optical hydrophobic-hydrophilic, solubility or permeability properties using materials comprising a polymeric matrix containing a low molecular weight organic compound such as a fatty acid, e.g. for reversible recording
Landscapes
- Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Thermal Transfer Or Thermal Recording In General (AREA)
Abstract
Description
【発明の詳細な説明】
技術分野
本発明は温度による透明度及び色調の可逆的変化を利用
して記録及び消去を行なう可逆性感熱記録材料に関する
。DETAILED DESCRIPTION OF THE INVENTION Technical Field The present invention relates to a reversible thermosensitive recording material that performs recording and erasing by utilizing reversible changes in transparency and color tone depending on temperature.
従来技術
近年、ブラウン管のような比較的高価なディスプレーが
市場に出回っているが、一方、低価格の簡易型ディスプ
レーや電子黒板も普及し始めた。しかし電子黒板は油性
ペンのようなマーカーで書込む方式であり、光学的読取
装置や磁気記録装置等からの画像を直接表示できないの
で不便である。一方、簡易型ディスプレー、例えばサー
マルディスプレー（１９８０年５月２６日発行「日経エ
レクトロニクス」６３頁）の場合はサーマルヘッドのよ
うな加熱手段で書込む方式で１）、比較的容易に書込み
できる上、使用材料によっては可逆的な要素も含んでい
るため、注目されてきた。このような可逆的感熱記録方
式に用いられる記録材料としては金属錯塩系サーモクロ
ミック材料を用いた可逆発色性感熱記録材料（１９８０
年５月２６日発行「日経エレクトロニクス」６３頁）、
電子供与体〜電子受容体系サーモクロミック材料を用い
た可逆発色性感熱記録材料（特開昭５８−１９１１９０
号、同６０−１９３６９１号）等が提案されているが、
まだコントラストの点で不充分である。BACKGROUND OF THE INVENTION In recent years, relatively expensive displays such as cathode ray tubes have been on the market, but low-cost simple displays and electronic whiteboards have also started to become popular. However, electronic blackboards require writing using markers such as oil-based pens, and are inconvenient because images from optical reading devices, magnetic recording devices, etc. cannot be directly displayed. On the other hand, in the case of a simple display, such as a thermal display (Nikkei Electronics, May 26, 1980, p. 63), writing is done using a heating means such as a thermal head (1), which allows writing to be done relatively easily. It has attracted attention because it may contain reversible elements depending on the materials used. As a recording material used in such a reversible heat-sensitive recording method, there is a reversible color-developing heat-sensitive recording material (1980) using a metal complex-based thermochromic material.
"Nikkei Electronics" published on May 26, 2015, p. 63),
Reversible color-developing thermosensitive recording material using electron donor-electron acceptor system thermochromic material (Japanese Patent Application Laid-Open No. 191190-1982)
No. 60-193691) etc. have been proposed.
The contrast is still insufficient.
一方、温度による透明度変化を利用した可逆性感熱記録
材料として樹脂〜有機低分子物質（例えば高級脂肪酸）
系のもの（％開昭５８−１９１１９０号、特開昭６０−
１９３６９１号）が知られているが、この記録材料の場
合は無色（透明）又は白色（不透明）画像が形成される
ので、視覚に訴えるディスプレーや電子黒板には不向き
であった。On the other hand, resins to organic low-molecular substances (e.g. higher fatty acids) are used as reversible thermosensitive recording materials that utilize transparency changes due to temperature.
series (% 1987-191190, JP 1987-1999-
No. 193691) is known, but since this recording material forms a colorless (transparent) or white (opaque) image, it is not suitable for visually appealing displays or electronic blackboards.
目 的
本発明の目的は高コントラストの画像を形成でき、従っ
て光学的読取装置や磁気記録装置からの画像を直接表示
するディスプレーや電子黒板用として好適な可逆性感熱
記録材料を提供することである。Object The object of the present invention is to provide a reversible thermosensitive recording material that can form a high-contrast image and is therefore suitable for use in displays and electronic blackboards that directly display images from optical reading devices and magnetic recording devices. .
構成
本発明の可逆性感熱記録材料は第１図に示すように、透
明支持体１の一方の面に樹脂母材とこの樹脂母材中に分
散された有機低分子物質とを主成分とし、温度に依存し
て透明度が可逆的に変化する第一感熱層２′５：設け、
他方の面に可逆性サーモクロミック材料を主成分とし、
温度に依存して色調が可逆的に変化する第二感熱層３を
設けてなることを特徴とするものである。ここで「色調
が可逆的に変化する」とは「可逆的に発色又は消色する
か、或いは変色する」ことを意味する。Structure As shown in FIG. 1, the reversible thermosensitive recording material of the present invention has a resin base material on one side of a transparent support 1 and an organic low-molecular substance dispersed in the resin base material as main components. a first heat-sensitive layer 2'5 whose transparency changes reversibly depending on temperature;
Mainly composed of reversible thermochromic material on the other side,
It is characterized by being provided with a second heat-sensitive layer 3 whose color tone changes reversibly depending on the temperature. Here, "the color tone changes reversibly" means "color develops, disappears, or changes color reversibly."
本発明記録材料の記録及び消去原理は第一感熱層につい
ては温度による透明度変化を利用したものであり、また
第二感熱層については温度による色調変化を利用したも
のである。更に詳しく説明すると、第一感熱層における
記録及び消去原理は次の通９である。The principle of recording and erasing of the recording material of the present invention is that the first heat-sensitive layer utilizes a change in transparency due to temperature, and the second heat-sensitive layer utilizes a change in color tone due to temperature. To explain in more detail, the principle of recording and erasing in the first heat-sensitive layer is as follows.
第２図において樹脂母材とこの樹脂母材中に分散された
有機低分子物質とを主成分とする第一感熱層は例えばＴ
、以下の常温で白濁不透明状態にある。これｔ”Ｔ＊〜
Ｔ３間の温度に加熱すると、透明になり、この状態でで
、以下の常温に戻しても透明のままである。更に１８以
上の温度に加熱すると、最大透明度と最大不透明度との
中間の半透明状態になる。次にこの温度を下げて行くと
再び透明状態をとることなく、最初の白濁不透明状態に
戻る。なお、この不透明状態のものをＴ０〜Ｔ１間の温
度に加熱した後、常温、即ちＴ。In FIG. 2, the first heat-sensitive layer whose main components are a resin base material and an organic low-molecular substance dispersed in the resin base material is, for example, T
It is cloudy and opaque at room temperature below. This is t"T*~
When heated to a temperature between T3, it becomes transparent, and in this state, it remains transparent even if it is returned to room temperature below. Further heating to a temperature of 18 or higher results in a translucent state intermediate between maximum transparency and maximum opacity. Next, when this temperature is lowered, it returns to its initial cloudy and opaque state without becoming transparent again. Note that after heating this opaque state to a temperature between T0 and T1, it is heated to room temperature, that is, T.
以下の温度に冷却した場合には透明と不透明との間の状
態をとることができる。また前記、常温で透明になった
ものも再びＴ１以上の温度に加熱し、常温に戻せば、再
び白濁不透明状態に戻る。即ち常温で不透明及び透明の
両形態並びにその中間状態をとることができる。When cooled to temperatures below, it can assume a state between transparent and opaque. Moreover, if the above-mentioned material that becomes transparent at room temperature is heated again to a temperature higher than T1 and returned to room temperature, it will return to a cloudy and opaque state. That is, it can take both opaque and transparent forms, as well as intermediate states, at room temperature.
従って例えばこのような感熱層全体をＴ１〜Ｔ。Therefore, for example, the entire heat-sensitive layer is T1 to T.
間の温度に加熱後、Ｔ、以下の常温に冷却して透明化し
、ついでこれをサーマルヘッド等で部分的にＴ、以上の
温度に加熱しその部分を不透明化すれば、透明部を背景
に白色画像が形成される。After heating to temperatures between A white image is formed.
またこの感熱層全体を熱ローラー等で１８以上の温度に
加熱した後、Ｔ、以下の常温に戻し白濁、不透明化した
後、サーマルヘッド等で部分的に１１〜７１間の温度に
加熱してその部分を透明化すれば白色面に透明画像が形
成される。なおこのような第一感熱層への記録及び消去
は、少なくとも１０４回程口縁り返すことができる。In addition, the entire heat-sensitive layer is heated to a temperature of 18 or more with a heat roller, etc., then returned to room temperature below T, and becomes cloudy and opaque, and then partially heated to a temperature of 11 to 71 with a thermal head, etc. If that part is made transparent, a transparent image will be formed on the white surface. Note that such recording and erasing on the first heat-sensitive layer can be repeated at least 104 times.
一方、第二感熱層における記録及び消去ぶ理は従来の可
逆発色性サーモクロミック材料を用いた記録材料と同様
、サーモクロミック材料の化学反応、例えば１）結晶水
の脱水反応、２）結晶の転移反応、３）電子供与体及び
電子受容体の電子授受、即ち酸化還元反応等によるもの
である。ここでサーモクロミック材料が例えば第２図の
１１以上の温度で発色又は変色し、１８以上の温度では
消色するか、又は元の色に戻るものとすれば、第二感熱
層をサーマルヘッド等で部分的ＫＴ、以上の温度に加熱
すると、その部分は発色又は変色し、無色部又はある色
ｔＪＩ４ｔ−背景に発色又は変色画像が形成される。次
にこの感熱層を１３以上の温度にすると、この画像は消
色又は元の色に戻る。なおこのような第二感熱層への記
録及び消去は少なくとも１０１回程波線返すことができ
る。On the other hand, the recording and erasing processes in the second heat-sensitive layer are similar to those of conventional recording materials using reversible color-forming thermochromic materials, and are based on chemical reactions of the thermochromic material, such as 1) dehydration reaction of crystal water, 2) transition of crystals. 3) electron transfer between an electron donor and an electron acceptor, that is, an oxidation-reduction reaction, etc. Here, if the thermochromic material develops or changes color at a temperature of 11 or higher as shown in FIG. When a portion is heated to a temperature above KT, that portion develops or changes color, and a colored or discolored image is formed in a colorless area or a certain color tJI4t-background. Next, when this heat-sensitive layer is heated to a temperature of 13 or above, the image disappears or returns to its original color. Note that such recording and erasing on the second heat-sensitive layer can be repeated at least 101 times.
従って以上のような第−及び第二感熱層を有する可逆性
感熱記録材料のいずれかの面（通常、第一感熱層面）全
体を１３以上の温度に加熱した後、Ｔ、以下の常温に戻
して第一感熱層全体を白濁不透明化した後、いずれかの
面（通常、第一感熱層面）ｔ−サーｉルヘッド等でＴ１
〜Ｔ３の温度に加熱すれば第一感熱層の加熱部分は透明
化し、一方、第二感熱層の加熱部分は発色又は変色する
ので、結局、第一感熱層側から見れば第一感熱層の白地
を背景に第二感熱層の発色又は変色画像が形成されたこ
とになる。Therefore, after heating either side (usually the first heat-sensitive layer side) of the reversible heat-sensitive recording material having the above-mentioned first and second heat-sensitive layers to a temperature of 13 or higher, the temperature is returned to room temperature below T. After making the entire first heat-sensitive layer cloudy and opaque, apply T1 on either side (usually the first heat-sensitive layer side) using a T-circle head or the like.
When heated to a temperature of ~T3, the heated portion of the first heat-sensitive layer becomes transparent, while the heated portion of the second heat-sensitive layer develops or changes color. This means that a colored or discolored image of the second heat-sensitive layer is formed against a white background.
第一感熱層の形成方法としては１）樹脂母材及び有機低
分子物質の両者を溶解した溶液を支持体上に塗布乾燥す
る方法、２）樹脂母材を溶解した溶液（この場合の溶剤
としては有機低分子物質を溶解しないものを用いる）に
、微粒子状に粉砕した有機低分子物質を分散し、これを
支持体上に塗布乾燥する方法、或いは３）樹脂母材及び
有機低分子物質を加熱、溶融、混練し、これを支持体上
にフィルム状に流延、放冷する方法等が挙げられる。な
おこうして形成される第一感熱層中では有機低分子物質
は２）の方法の場合は勿論、１）及び３）の方法の場合
も微粒子状に析出し、分散状態で存在する。第一感熱層
の厚さは５〜２０μｚ程度が適当である。The first heat-sensitive layer can be formed by 1) applying and drying a solution in which both a resin base material and an organic low-molecular substance are dissolved on a support, and 2) a method in which a solution in which a resin base material is dissolved (in this case, the solvent is 3) A method of dispersing the organic low-molecular substance crushed into fine particles in a material that does not dissolve the organic low-molecular substance, and applying and drying this onto a support; or 3) dispersing the resin base material and the organic low-molecular substance. Examples include methods of heating, melting, and kneading, casting the mixture onto a support in the form of a film, and allowing it to cool. In the first heat-sensitive layer thus formed, the organic low-molecular substance precipitates in the form of fine particles and exists in a dispersed state not only in the case of the method 2) but also in the methods 1) and 3). The thickness of the first heat-sensitive layer is suitably about 5 to 20 μz.
第一感熱層に使用される樹脂母材は有機低分子物質を均
一に分散保持した層又はフィルムを形成すると共に、最
大透明時の透明度に影響を与える材料である。このため
樹脂母材は透明性が良く、機械的に安定で、且つ成膜性
の良い樹脂が好ましい。このような樹脂としてはイリ塩
化ｆニル、塩化ぜニル−酢酸ビニル共重合体、塩化セニ
ル軸酢酸ビニル〜ビニルアルコール共重合体、塩化ビニ
ルへ酢酸ビニル〜マレイン酸共重合体、塩化♂ニルルア
クリレート共重合体等の塩化ビニル系共重合体；イリ塩
化ビニリデン、塩化ビニリデン軸塩化ビニル共重合体、
塩化ビニリデン−アクリロニトリル共重合体等の塩化ｔ
ニリデン系共重合体；４リエステル；ポリアミド；４リ
アクリレート又はイリメタクリレート或いはアクリレ−
トルメタクリレート共重合体、シリコン樹脂等が挙げら
れる。これらは単独で或いは２種以上混合して使用され
る。The resin matrix used for the first heat-sensitive layer forms a layer or film in which a low-molecular-weight organic substance is uniformly dispersed, and is a material that influences the transparency at maximum transparency. Therefore, the resin base material is preferably a resin that has good transparency, is mechanically stable, and has good film-forming properties. Examples of such resins include f-nyl chloride, zenyl chloride-vinyl acetate copolymer, cenyl chloride-vinyl acetate-vinyl alcohol copolymer, vinyl chloride-vinyl acetate-maleic acid copolymer, and ♂nyl chloride acrylate. Vinyl chloride copolymers such as copolymers; irivinylidene chloride, vinylidene chloride-axis vinyl chloride copolymers,
T chloride such as vinylidene chloride-acrylonitrile copolymer
Nylidene copolymer; 4-lyester; polyamide; 4-lyacrylate or irimethacrylate or acrylate
Examples include tol methacrylate copolymer and silicone resin. These may be used alone or in combination of two or more.
一方、有機低分子物質は第１図の温度Ｔ、〜ちを選定す
ることに応じて適宜選定すればよいが、融点３０〜２０
０℃、特に５０〜１５０℃１度のものが好ましい。この
ような有機低分子物質としてはアルカノール；アルカン
ジオール；ハロゲンアルカノール又はハロゲンアルカン
ジオール；アルキルアミン；アルカン；アルケン；アル
キン；ハロゲンアルカン；ハロゲンアルケン、ハロゲン
アルキン；シクロアルカン；シクロアルケン；シクロア
ルキン；飽和又は不飽和上ノ又はジカルゼン酸又はこれ
らのエステル、アミド、又はアンモニウム塩；飽和又は
不飽和ハロゲン脂肪酸又はこれらのエステル、アミド、
又はアンそニウム塩；アリルカルゼン酸又はそれらのエ
ステル、アミド又はアンそニウム塩；ハロゲンアリルカ
ル−ン酸又はそれらのエステル、アミド、又はアンモニ
ウム塩；チオアルーール；チオカルーン酸又はそれらの
エステル、アミン、又はアンモニクム塩；チオアルコー
ルのカルゼン酸エステル等が挙げられる。これらは単独
で又は２種以上混合して使用される。これらの化合物の
炭素数はｌＯ〜６Ｇ、好ましくは１０〜３８、特に１０
〜３０が好ましい。エステル中のアルコール基部分は飽
和していても飽和していなくてもよく、またハロゲン置
換すれていてもよい。いずれにしても有機低分子物質は
分子中にに酸素、窒素、硫黄及びハロゲンの少なくとも
１１！、例えば−ＯＨ、−Ｃ０ＯＨ。On the other hand, the organic low-molecular substance may be selected as appropriate depending on the temperature T shown in FIG.
A temperature of 0°C, particularly 50 to 150°C, is preferred. Such organic low-molecular substances include alkanols; alkanediols; halogenalkanols or halogenalkanediols; alkylamines; alkanes; alkenes; alkynes; halogenalkanes; halogenalkenes, halogenalkynes; cycloalkanes; cycloalkenes; cycloalkynes; unsaturated dicarzenic acids or their esters, amides, or ammonium salts; saturated or unsaturated halogenated fatty acids or their esters, amides,
or amsonium salts; allylcarzenic acid or their esters, amides, or anthonium salts; halogenallycarzenic acids or their esters, amides, or ammonium salts; thioarul; thiocarunic acids or their esters, amines, or ammonium salts Salts; examples include carzenate esters of thioalcohols. These may be used alone or in a mixture of two or more. The carbon number of these compounds is 10 to 6G, preferably 10 to 38, especially 10
~30 is preferred. The alcohol group moiety in the ester may be saturated or unsaturated, and may be halogen-substituted. In any case, organic low-molecular substances contain at least 11 molecules of oxygen, nitrogen, sulfur, and halogen! , for example -OH, -COOH.
−ＣＯＮＨ，−ＣＯＯＲ，−ＮＨ−、−ＮＨ，、−８−
−Ｓ−Ｓ−、−Ｏ−、ハロゲン等を含む化合物であるこ
とが好ましい。-CONH, -COOR, -NH-, -NH,, -8-
A compound containing -S-S-, -O-, halogen, etc. is preferable.
更に具体的にはこれら化合物にはラウリン酸、ドデカン
酸、きりステン酸、ペンタデカン酸、パルミチン酸、ス
テアリン酸、ベヘン酸、ノナデカン酸、アラキン酸、オ
レイン酸等の高級脂層酸；ステアリン酸メチル、ステア
リン酸テトラデシル、ステアリン酸オクタデシル、ラウ
リン酸オクタデシル、ノルミテン酸テトラデシル、べへ
ン酸トコシル等の高級脂肪酸のエステル；ＣｕＨｏ −
０−Ｃ工Ｈ３＊ ｖ ｃ、、ｕ３．− Ｓ −ｃｔ
ｓＨｓｓＣｓ、Ｈｓｔ −８−（：□、Ｈ，，、Ｃ，、
Ｈ，、−８−Ｃ，、Ｈ，。More specifically, these compounds include higher lipid acids such as lauric acid, dodecanoic acid, kistonic acid, pentadecanoic acid, palmitic acid, stearic acid, behenic acid, nonadecanoic acid, arachidic acid, and oleic acid; methyl stearate; Ester of higher fatty acids such as tetradecyl stearate, octadecyl stearate, octadecyl laurate, tetradecyl normitate, tocosyl behenate; CuHo −
0-C engineering H3* v c,, u3. -S-ct
sHssCs, Hst -8-(:□, H,,,C,,
H,,-8-C,,H,.
Ｃ，、）！、、−８−Ｃ，，Ｈｎ、 Ｃ１，Ｈ，、−
８−８−Ｃ１，Ｈ，、。C,,)! ,,-8-C,,Hn, C1,H,,-
8-8-C1,H,.
ＣＨ。CH.
占Ｈ。Zhan H.
ＣＨ。CH.
ＣＨ。CH.
品− 等のエーテル又はチオエーテル等がある。Goods There are ethers and thioethers such as
なお感熱層又は感熱シート中の樹脂母材と有機低分子物
質との割合は重量比でｉ：ｏ、ｓ 〜１：１６程度が好
ましい。母材の比率がこれ以下になると、有機低分子物
質を母材中に保持した膜を形成することが困難となシ、
一方、これ以上になると、有機低分子物質の量が少々い
ため、不透明化が困難となる。また感熱層形成用溶剤と
しては母材及び有機低分子物質の種類によって種々選択
できるが、例えばテトラヒドロ７ラン、メチルエチルケ
トン、メチルイソブチルケトン、クロロホルム、四塩化
炭素、エタノール、トルエン、ベンゼン等が挙ケラレル
。The weight ratio of the resin base material to the organic low-molecular substance in the heat-sensitive layer or heat-sensitive sheet is preferably about i:o,s to 1:16. If the ratio of the base material is less than this, it will be difficult to form a film that retains the organic low molecular weight substance in the base material.
On the other hand, if the amount is more than this, the amount of organic low-molecular substance is small, making it difficult to make it opaque. Various solvents for forming the heat-sensitive layer can be selected depending on the type of base material and organic low-molecular substance, and examples thereof include tetrahydro7ran, methyl ethyl ketone, methyl isobutyl ketone, chloroform, carbon tetrachloride, ethanol, toluene, and benzene.
一方、第二感熱層の形成方法としては通常、可逆性サー
モクロミック材料を生成−分とする溶液を支持体上に塗
布乾燥する方法が採用される。On the other hand, as a method for forming the second heat-sensitive layer, a method is usually adopted in which a solution containing a reversible thermochromic material is applied onto a support and dried.
なおこの溶液には必要に応じて樹脂結着剤を添加するこ
とができる。第二感熱層の厚さは３〜１５μＩＩＬ程度
が適当である。Note that a resin binder can be added to this solution if necessary. The thickness of the second heat-sensitive layer is suitably about 3 to 15 μL.
第二感熱層に使用されるサーモクロミック材料は第１図
の温度Ｔ□（発色又は変色する温度）を選定することに
応じて適宜選定すればよいが、一般にこの温度は５０〜
１５０℃程度のものが使用される。このようなサーモク
ロミック材料の具体例としては脱水型ではへキサメチレ
ンテトラミンの金属塩、転移型ではＡｇ、ＨｇＩ、 。The thermochromic material used for the second heat-sensitive layer may be appropriately selected depending on the temperature T□ (temperature at which color develops or changes color) in Figure 1, but generally this temperature is 50 to 50°C.
A temperature of about 150°C is used. Specific examples of such thermochromic materials include metal salts of hexamethylenetetramine in the dehydrated type, and Ag, HgI, and the like in the transition type.
ＣｕｌＨｇＩ４ 、 Ｈｇ１１等があり、また電子授受
型では従来、感圧紙や感熱紙に使用されているトリフェ
ニルメタン系、フルオラン系、フェノチアジン系、オー
ラミン系、スピロぜラン系等のロイコ染料（発色剤とし
て）とフェノール類、カルゼン酸類等の酸性物質（顕色
剤として）と固体アルコール類のような消色剤との組合
せがある。CulHgI4, Hg11, etc., and in the electronic transfer type, leuco dyes (as coloring agents) such as triphenylmethane, fluoran, phenothiazine, auramine, and spirozeran, which are conventionally used in pressure-sensitive paper and thermal paper, are used. ), acidic substances such as phenols and calzenic acids (as color developers), and color erasing agents such as solid alcohols.
なお電子授受型のサーモクロミック材料を用いた場合は
第二感熱層は消色剤層と発色剤〜顕色剤混合層とく分け
ることが好ましい。In addition, when an electron exchange type thermochromic material is used, it is preferable that the second heat-sensitive layer is divided into a color erasing agent layer and a color former-color developer mixed layer.
樹脂結着剤としては水溶性ポリエステル樹脂、／ ＩＪ
ヒニルアルコール、メトキシセルロース、ヒドロキシ
エチルセルロース、カル２キシメチルセルロース、−リ
アクリルアミド、４リアクリル酸、澱粉等の水溶性のも
のやポリスチレン、塩化ｅニル−酢酸ビニル共重合体、
ポリブチルメタクリレート等の水性エマルジョン等が使
用される。As a resin binder, water-soluble polyester resin, /IJ
Hynyl alcohol, methoxycellulose, hydroxyethylcellulose, cal-2xymethylcellulose, -lyacrylamide, 4-lyacrylic acid, starch and other water-soluble materials, polystyrene, e-enyl chloride-vinyl acetate copolymer,
Aqueous emulsions such as polybutyl methacrylate are used.
第二感熱層の形成に使用される溶剤としてはサーモクロ
ミック材料の種類に応じて種々選択できるが、例えば水
、エタノール、トルエン、メチルエチルケトン、ベンゼ
ン等が挙げられる。The solvent used to form the second heat-sensitive layer can be selected from various solvents depending on the type of thermochromic material, and examples thereof include water, ethanol, toluene, methyl ethyl ketone, benzene, and the like.
透明支持体としては各種プラスチックフィルム、ガラス
板等が使用される。Various plastic films, glass plates, etc. are used as the transparent support.
以下に本発明を実施例によって更に詳しく説明する。な
お部及び％はいずれも重量基準である。The present invention will be explained in more detail below with reference to Examples. Note that both parts and percentages are based on weight.
実施例１
ステアリン酸 ５部塩化ぎニル
−酢酸ビニル共重合体 １８部（ＵＣＣ社製ＶＹ
ＨＨ）
テトラヒドロフラン ７７部よりなる成
分を混合し、均一に溶解し、これを厚さ２５μ電のＩリ
エステルフィルムの一方ノ面にワイヤーノｑ−で塗布し
、１５０℃で乾燥して厚さ１２μ寓の第一感熱層を設け
た。この感熱層は白色であった。Example 1 Stearic acid 5 parts Vinyl chloride-vinyl acetate copolymer 18 parts (VY manufactured by UCC)
HH) Components consisting of 77 parts of tetrahydrofuran were mixed and dissolved uniformly, and this was applied to one side of a 25 μm thick I-rester film using a wire spray, and dried at 150°C to a 12 μm thick film. A first heat-sensitive layer was provided. This heat-sensitive layer was white.
次に
Ｃｏ（Ｊｌ ・２Ｃ＠Ｈ１２・Ｎ４ ・１０Ｈ＠０
１０部ト ル エ ン
３７部よシなる成分を
混合し、ボールミルで充分く分散し、この分散液を前記
フィルムの他方の面にワイヤーパーで塗布し、５０℃で
乾燥して厚さ７μｍの第二感熱層を設けた。この感熱層
は無色でめった。Next, Co(Jl ・2C@H12・N4 ・10H@0
Part 10
37 parts of the above ingredients were mixed, sufficiently dispersed using a ball mill, and this dispersion was applied to the other side of the film using a wire paring machine, and dried at 50°C to form a second heat-sensitive layer with a thickness of 7 μm. Ta. This heat-sensitive layer was colorless and dull.
こうして得られた可逆性感熱記録材料の第一感熱層面に
サーマルヘッドを用いて７０℃で印字したところ、第一
感熱層の印字部分は透明になり、そＯ反対面の第二感熱
層部分は青色に発色し、こうして第一感熱層側には白色
を背景に鮮明な高コントラストの青色画像、が形成され
た。When printing was performed at 70°C using a thermal head on the first heat-sensitive layer surface of the thus obtained reversible heat-sensitive recording material, the printed portion of the first heat-sensitive layer became transparent, and the second heat-sensitive layer portion on the opposite side became transparent. A blue color developed, and thus a clear, high-contrast blue image was formed on the first heat-sensitive layer side against a white background.
実施例２
、第二感熱層形成用分散液に
ＣｏＳＯ４・Ｃ５Ｈ１０・Ｎ４ ・９ＨＨＯ１２部ト
ル エ ン
３５部よシなる成分を用いた他は実施例１と同じ方
法で可逆性感熱記録材料を作った。なお第二感熱層は実
施例１と同様無色であった。Example 2 12 parts of CoSO4.C5H10.N4.9HHO was added to the dispersion liquid for forming the second heat-sensitive layer.
Le en
A reversible thermosensitive recording material was prepared in the same manner as in Example 1, except that 35 parts of the ingredients were used. Note that the second heat-sensitive layer was colorless as in Example 1.
以下この記録材料に実施例１と同様に印字上行なったと
ころ、第一感熱層側圧は白地を背景に鮮明な高コントラ
スＦの紅紫色画像が形成された。Thereafter, printing was carried out on this recording material in the same manner as in Example 1, and a clear high contrast F reddish-purple image was formed with the first heat-sensitive layer lateral pressure against a white background.
実施例３
水溶性ポリエステル樹脂の２０％水溶液 ２５部
（日本合成化学社製ＷＲ−９０１）
消色剤としてトリグロビルカルピノール ２５
部水 ３０部よ
ルなる成分を混合し、ボールミルで充分に分散して消色
剤分散液で作った。一方、
発色剤としてクリスタルバイオレットラクトン ５部
顕色剤として４−ヒドロキシ安息香酸 ２０部ベン
ジルエステル
ポリビニルアルコールの１０％水ａ液 ａａｍ
水 ４５部よシ
なる成分を混合し、２−ルミルで充分に分散して発色剤
〜顕色剤混合分散液を作った。Example 3 25 parts of a 20% aqueous solution of water-soluble polyester resin (WR-901 manufactured by Nippon Gosei Kagaku Co., Ltd.) Triglovircarpinol as a decolorizing agent 25 parts
30 parts of water were mixed and thoroughly dispersed in a ball mill to prepare a decolorizing agent dispersion. On the other hand, 5 parts crystal violet lactone as a color former 20 parts 4-hydroxybenzoic acid as a color developer 10% aqueous solution of benzyl ester polyvinyl alcohol aam
45 parts of water were mixed together and sufficiently dispersed with 2-lumil to prepare a mixed dispersion of color former and color developer.
次に実施例１で作った第一感熱層を有する透明支持体の
第一感熱層の反対面に前記消色剤分散液をワイヤーパー
で塗布し、１００℃で乾燥して厚さ２μ気の消色剤層を
設けた後その上に前記発色剤〜顕色剤混合分散液をワイ
ヤー、Ｊ−で塗布し、５０℃で乾燥して厚さ３μ罵の発
色剤〜顕色剤混合層を設けることにより第二感熱層を形
成した。なおこの第二感熱層も無色でめった。Next, the decolorizing agent dispersion was applied to the opposite side of the first heat-sensitive layer of the transparent support having the first heat-sensitive layer prepared in Example 1 using a wire spar, and dried at 100°C to a thickness of 2 μm. After providing the color erasing agent layer, the above-mentioned color former/color developer mixed dispersion was applied thereon using a wire and dried at 50°C to form a color former/color developer mixed layer with a thickness of 3 μm. By providing this, a second heat-sensitive layer was formed. Note that this second heat-sensitive layer was also colorless and amorphous.
以下こうして得られた可逆性感熱記録材料に実施例１と
同様に印字を行なったところ、第一感熱層側には白地を
背景に鮮明な高コントラストの青色画像が形成された。Thereafter, printing was carried out on the thus obtained reversible heat-sensitive recording material in the same manner as in Example 1, and a clear, high-contrast blue image was formed on the first heat-sensitive layer side against a white background.
次に各実施例の発色画像を有する記録材料の第一感熱層
面全体を１４０℃に加熱すると、いずれの第一感熱層の
透明部分は消失し、全体が白色不透明化されると共に、
第二感熱層は実施例１の場合は全体が青色に発色し、実
施例２の場合は全体が紅紫色に発色し、また実施例３の
場合は全体が消色した。しかし実施例１及び２の第二感
熱層も５時間放置すると、全体が消色した。Next, when the entire surface of the first heat-sensitive layer of the recording material having the colored image of each example is heated to 140°C, the transparent portion of any of the first heat-sensitive layers disappears, and the entire surface becomes white and opaque.
In Example 1, the entire second heat-sensitive layer developed a blue color, in Example 2, the entire second heat-sensitive layer developed a reddish-purple color, and in Example 3, the entire second heat-sensitive layer discolored. However, when the second heat-sensitive layers of Examples 1 and 2 were left for 5 hours, the color completely disappeared.
更にこうして元に戻った実施例１〜３の記録材料を再び
７０℃で印字したところ、夫々実施例１〜３の場合と同
様々印字結果が得られた。Furthermore, when the recording materials of Examples 1 to 3 returned to their original state were printed again at 70 DEG C., the same printing results as in Examples 1 to 3 were obtained, respectively.
効果
以上の如く本発明の可逆性感熱記録は白地に発色又は変
色画像が現われるので、高コントラストの画像を形成で
き、従って光学的読取装置や磁気記録装置からの画像な
直接表示するディスプレーや電子黒板用として好適であ
る。Effects As described above, since the reversible thermosensitive recording of the present invention shows a colored or discolored image on a white background, it is possible to form a high-contrast image, and therefore it can be used to directly display images from an optical reader or magnetic recording device on a display or an electronic blackboard. suitable for use.
第１図は本発明可逆性感熱記録材料の構成図、第２図は
この記録材料の第一感熱層における記録及び消去原理の
説明図である。
ｌ・・・透明支持体 ２・・・第一感熱層３・・
・第二感熱層
特許出願人 株式会社 リ コ −
代理人弁理士 月 村 茂外１名５ｊＬＸ
手続補正書
昭和６２年１月２３日
２、発明の名称
可逆性感熱記録材料
３、補正をする者
事件との関係 特許出願人
東京都大田区中馬込１丁目３番６号
（６７４）株式会社 リ コー
代表者 浜 １） 広
４、代理人
明細書の［発明の詳細な説明」の欄
６、補正の内容FIG. 1 is a block diagram of the reversible thermosensitive recording material of the present invention, and FIG. 2 is an explanatory diagram of the principle of recording and erasing in the first thermosensitive layer of this recording material. l...Transparent support 2...First heat-sensitive layer 3...
・Second heat-sensitive layer patent applicant Ricoh Co., Ltd. - Representative patent attorney Tsukimura Shigegai 1 person 5jLX Procedural amendment January 23, 1988 2 Name of the invention Reversible heat-sensitive recording material 3 Person making the amendment Relationship to the case Patent applicant 1-3-6 Nakamagome, Ota-ku, Tokyo (674) Ricoh Co., Ltd. Representative Hama 1) Hiro 4, [Detailed description of the invention] column 6 of the agent's specification, Contents of correction
Claims (1)
に分散された有機低分子物質とを主成分とし、温度に依
存して透明度が可逆的に変化する第一感熱層を設け、他
方の面に可逆性サーモクロミック材料を主成分とし、温
度に依存して色調が可逆的に変化する第二感熱層を設け
てなる可逆性感熱記録材料。1. On one side of the transparent support, a first heat-sensitive layer is formed, which is mainly composed of a resin matrix and an organic low-molecular substance dispersed in the resin matrix, and whose transparency changes reversibly depending on the temperature. A reversible heat-sensitive recording material comprising: a second heat-sensitive layer comprising a reversible thermochromic material as a main component and whose color tone changes reversibly depending on temperature;
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61231598A JPH0764119B2 (en) | 1986-09-30 | 1986-09-30 | Reversible thermosensitive recording material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61231598A JPH0764119B2 (en) | 1986-09-30 | 1986-09-30 | Reversible thermosensitive recording material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6384978A true JPS6384978A (en) | 1988-04-15 |
| JPH0764119B2 JPH0764119B2 (en) | 1995-07-12 |
Family
ID=16926021
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61231598A Expired - Lifetime JPH0764119B2 (en) | 1986-09-30 | 1986-09-30 | Reversible thermosensitive recording material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0764119B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1993007004A1 (en) * | 1991-09-30 | 1993-04-15 | Fujitsu Limited | Thermoreversible recording material, production thereof, and thermal recording medium |
| JP2009302101A (en) * | 2008-06-10 | 2009-12-24 | Denso Corp | Electronic component mounting structure |
| CN108299515A (en) * | 2018-03-15 | 2018-07-20 | 南阳师范学院 | Cobalt complex and its preparation method and application with reversible thermochromic characteristic |
-
1986
- 1986-09-30 JP JP61231598A patent/JPH0764119B2/en not_active Expired - Lifetime
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1993007004A1 (en) * | 1991-09-30 | 1993-04-15 | Fujitsu Limited | Thermoreversible recording material, production thereof, and thermal recording medium |
| JP2009302101A (en) * | 2008-06-10 | 2009-12-24 | Denso Corp | Electronic component mounting structure |
| CN108299515A (en) * | 2018-03-15 | 2018-07-20 | 南阳师范学院 | Cobalt complex and its preparation method and application with reversible thermochromic characteristic |
| CN108299515B (en) * | 2018-03-15 | 2020-04-17 | 南阳师范学院 | Cobalt complex with reversible thermochromism characteristic and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0764119B2 (en) | 1995-07-12 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EXPY | Cancellation because of completion of term |