JPH02111585A - Thermal recording material - Google Patents
Thermal recording materialInfo
- Publication number
- JPH02111585A JPH02111585A JP63265714A JP26571488A JPH02111585A JP H02111585 A JPH02111585 A JP H02111585A JP 63265714 A JP63265714 A JP 63265714A JP 26571488 A JP26571488 A JP 26571488A JP H02111585 A JPH02111585 A JP H02111585A
- Authority
- JP
- Japan
- Prior art keywords
- heat
- sensitive layer
- compounds
- sensitive
- 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.)
- Pending
Links
- 239000000463 material Substances 0.000 title claims abstract description 37
- 239000010410 layer Substances 0.000 claims abstract description 41
- 238000000576 coating method Methods 0.000 claims abstract description 18
- 229920000642 polymer Polymers 0.000 claims abstract description 17
- 239000011248 coating agent Substances 0.000 claims abstract description 16
- 239000003094 microcapsule Substances 0.000 claims abstract description 16
- 239000011241 protective layer Substances 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000006185 dispersion Substances 0.000 claims abstract description 13
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 12
- 239000011737 fluorine Substances 0.000 claims abstract description 12
- 239000003960 organic solvent Substances 0.000 claims description 9
- 239000002243 precursor Substances 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 abstract description 9
- 150000002148 esters Chemical class 0.000 abstract description 9
- 229920002451 polyvinyl alcohol Polymers 0.000 abstract description 9
- 239000007788 liquid Substances 0.000 abstract description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 6
- 229920001577 copolymer Polymers 0.000 abstract description 6
- 239000002904 solvent Substances 0.000 abstract description 6
- 239000011230 binding agent Substances 0.000 abstract description 4
- 239000008119 colloidal silica Substances 0.000 abstract description 3
- 229920001519 homopolymer Polymers 0.000 abstract description 3
- 239000000654 additive Substances 0.000 abstract description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 abstract 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 abstract 1
- 239000000758 substrate Substances 0.000 abstract 1
- -1 spiropyrans Chemical class 0.000 description 33
- 125000000217 alkyl group Chemical group 0.000 description 21
- 125000004432 carbon atom Chemical group C* 0.000 description 17
- 150000001875 compounds Chemical class 0.000 description 15
- 239000003921 oil Substances 0.000 description 13
- 239000000975 dye Substances 0.000 description 7
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- 239000000243 solution Substances 0.000 description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- 239000002775 capsule Substances 0.000 description 6
- 150000005690 diesters Chemical class 0.000 description 6
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- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 6
- 238000002844 melting Methods 0.000 description 6
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- 125000005010 perfluoroalkyl group Chemical group 0.000 description 5
- 108010010803 Gelatin Proteins 0.000 description 4
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- 239000008346 aqueous phase Substances 0.000 description 4
- 239000000084 colloidal system Substances 0.000 description 4
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical class C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 4
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- 235000011852 gelatine desserts Nutrition 0.000 description 4
- 238000000034 method Methods 0.000 description 4
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- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 4
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- 239000004094 surface-active agent Substances 0.000 description 4
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 description 3
- 229920002396 Polyurea Polymers 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 239000003086 colorant Substances 0.000 description 3
- 230000009477 glass transition Effects 0.000 description 3
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- 239000004816 latex Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- OMNKZBIFPJNNIO-UHFFFAOYSA-N n-(2-methyl-4-oxopentan-2-yl)prop-2-enamide Chemical compound CC(=O)CC(C)(C)NC(=O)C=C OMNKZBIFPJNNIO-UHFFFAOYSA-N 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 150000002989 phenols Chemical class 0.000 description 3
- 229920000139 polyethylene terephthalate Polymers 0.000 description 3
- 239000005020 polyethylene terephthalate Substances 0.000 description 3
- 239000004814 polyurethane Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- QNLZIZAQLLYXTC-UHFFFAOYSA-N 1,2-dimethylnaphthalene Chemical compound C1=CC=CC2=C(C)C(C)=CC=C21 QNLZIZAQLLYXTC-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Natural products CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- IRIAEXORFWYRCZ-UHFFFAOYSA-N Butylbenzyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCC1=CC=CC=C1 IRIAEXORFWYRCZ-UHFFFAOYSA-N 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- BJQHLKABXJIVAM-UHFFFAOYSA-N Diethylhexyl phthalate Natural products CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 2
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- 229920000877 Melamine resin Polymers 0.000 description 2
- 239000004640 Melamine resin Substances 0.000 description 2
- JKRZOJADNVOXPM-UHFFFAOYSA-N Oxalic acid dibutyl ester Chemical compound CCCCOC(=O)C(=O)OCCCC JKRZOJADNVOXPM-UHFFFAOYSA-N 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- 229920006361 Polyflon Polymers 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- ZFOZVQLOBQUTQQ-UHFFFAOYSA-N Tributyl citrate Chemical compound CCCCOC(=O)CC(O)(C(=O)OCCCC)CC(=O)OCCCC ZFOZVQLOBQUTQQ-UHFFFAOYSA-N 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 125000005907 alkyl ester group Chemical group 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- 125000003710 aryl alkyl group Chemical group 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical class OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 2
- 239000001273 butane Substances 0.000 description 2
- XSIFPSYPOVKYCO-UHFFFAOYSA-N butyl benzoate Chemical compound CCCCOC(=O)C1=CC=CC=C1 XSIFPSYPOVKYCO-UHFFFAOYSA-N 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
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- 238000004040 coloring Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000011162 core material Substances 0.000 description 2
- 238000003851 corona treatment Methods 0.000 description 2
- 238000004031 devitrification Methods 0.000 description 2
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 2
- FLKPEMZONWLCSK-UHFFFAOYSA-N diethyl phthalate Chemical compound CCOC(=O)C1=CC=CC=C1C(=O)OCC FLKPEMZONWLCSK-UHFFFAOYSA-N 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 2
- 238000004945 emulsification Methods 0.000 description 2
- 230000001804 emulsifying effect Effects 0.000 description 2
- MTZQAGJQAFMTAQ-UHFFFAOYSA-N ethyl benzoate Chemical compound CCOC(=O)C1=CC=CC=C1 MTZQAGJQAFMTAQ-UHFFFAOYSA-N 0.000 description 2
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- WRKCIHRWQZQBOL-UHFFFAOYSA-N octyl dihydrogen phosphate Chemical compound CCCCCCCCOP(O)(O)=O WRKCIHRWQZQBOL-UHFFFAOYSA-N 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
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- 235000019422 polyvinyl alcohol Nutrition 0.000 description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 2
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- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 2
- 229920003002 synthetic resin Polymers 0.000 description 2
- 239000000057 synthetic resin Substances 0.000 description 2
- URAYPUMNDPQOKB-UHFFFAOYSA-N triacetin Chemical compound CC(=O)OCC(OC(C)=O)COC(C)=O URAYPUMNDPQOKB-UHFFFAOYSA-N 0.000 description 2
- 229920003169 water-soluble polymer Polymers 0.000 description 2
- WZBFYJGNLGQBBL-UHFFFAOYSA-N (1-methylcyclohexa-2,4-dien-1-yl)methylbenzene Chemical compound C=1C=CC=CC=1CC1(C)CC=CC=C1 WZBFYJGNLGQBBL-UHFFFAOYSA-N 0.000 description 1
- 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
- WSWCOQWTEOXDQX-MQQKCMAXSA-M (E,E)-sorbate Chemical class C\C=C\C=C\C([O-])=O WSWCOQWTEOXDQX-MQQKCMAXSA-M 0.000 description 1
- IAUKWGFWINVWKS-UHFFFAOYSA-N 1,2-di(propan-2-yl)naphthalene Chemical compound C1=CC=CC2=C(C(C)C)C(C(C)C)=CC=C21 IAUKWGFWINVWKS-UHFFFAOYSA-N 0.000 description 1
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- HAYWMMHKIFBJNB-UHFFFAOYSA-N 1,3-dimethoxyurea Chemical compound CONC(=O)NOC HAYWMMHKIFBJNB-UHFFFAOYSA-N 0.000 description 1
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- TVBYFUMVFJKKNJ-UHFFFAOYSA-N 1-cyclohex-2-en-1-yl-4-cyclohex-3-en-1-ylbenzene Chemical group C1CCC=CC1C1=CC=C(C2CC=CCC2)C=C1 TVBYFUMVFJKKNJ-UHFFFAOYSA-N 0.000 description 1
- UMSGIWAAMHRVQI-UHFFFAOYSA-N 1-ethyl-4-(4-ethylphenyl)benzene Chemical group C1=CC(CC)=CC=C1C1=CC=C(CC)C=C1 UMSGIWAAMHRVQI-UHFFFAOYSA-N 0.000 description 1
- RZTDESRVPFKCBH-UHFFFAOYSA-N 1-methyl-4-(4-methylphenyl)benzene Chemical group C1=CC(C)=CC=C1C1=CC=C(C)C=C1 RZTDESRVPFKCBH-UHFFFAOYSA-N 0.000 description 1
- AMBHHSBRXZAGDZ-UHFFFAOYSA-N 1-phenyl-2,3-di(propan-2-yl)benzene Chemical group CC(C)C1=CC=CC(C=2C=CC=CC=2)=C1C(C)C AMBHHSBRXZAGDZ-UHFFFAOYSA-N 0.000 description 1
- LTMRRSWNXVJMBA-UHFFFAOYSA-L 2,2-diethylpropanedioate Chemical compound CCC(CC)(C([O-])=O)C([O-])=O LTMRRSWNXVJMBA-UHFFFAOYSA-L 0.000 description 1
- JKAPWXKZLYJQJJ-UHFFFAOYSA-N 2,4-dichloro-6-methoxy-1,3,5-triazine Chemical compound COC1=NC(Cl)=NC(Cl)=N1 JKAPWXKZLYJQJJ-UHFFFAOYSA-N 0.000 description 1
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- QJIVRICYWXNTKE-UHFFFAOYSA-N 4-(8-methylnonoxy)-4-oxobutanoic acid Chemical compound CC(C)CCCCCCCOC(=O)CCC(O)=O QJIVRICYWXNTKE-UHFFFAOYSA-N 0.000 description 1
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- 239000004593 Epoxy Substances 0.000 description 1
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- 239000005977 Ethylene Substances 0.000 description 1
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Classifications
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- 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
- B41M5/40—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used characterised by the base backcoat, intermediate, or covering layers, e.g. for thermal transfer dye-donor or dye-receiver sheets; Heat, radiation filtering or absorbing means or layers; combined with other image registration layers or compositions; Special originals for reproduction by thermography
- B41M5/42—Intermediate, backcoat, or covering layers
- B41M5/44—Intermediate, backcoat, or covering layers characterised by the macromolecular compounds
- B41M5/446—Fluorine-containing polymers
-
- 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
- B41M5/40—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used characterised by the base backcoat, intermediate, or covering layers, e.g. for thermal transfer dye-donor or dye-receiver sheets; Heat, radiation filtering or absorbing means or layers; combined with other image registration layers or compositions; Special originals for reproduction by thermography
- B41M5/42—Intermediate, backcoat, or covering layers
- B41M5/44—Intermediate, backcoat, or covering layers characterised by the macromolecular compounds
- B41M5/443—Silicon-containing polymers, e.g. silicones, siloxanes
Landscapes
- Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Heat Sensitive Colour Forming Recording (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は感熱記録材料に関し、特に透明性の良い感熱層
を有する透明感熱記録材料に関する。DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a heat-sensitive recording material, and particularly to a transparent heat-sensitive recording material having a heat-sensitive layer with good transparency.
（従来の技術）
感熱記録方法は、（１）現像が不要、（２）支持体が紙
の場合は紙質が一般紙に近い、（３）取り扱いが容易、
（４）発色濃度が高い、（５）記録装置が簡単であり安
価である、（６）記録時の騒音がない等の利点があるた
め、ファクシミリやプリンターの分野で近年急速に普及
し、ＰＯＳ等におけるラベル分野、０）（Ｐ、多色記録
分野等、感熱記録材料に対するニーズも拡大している。(Prior art) The thermal recording method has the following advantages: (1) no development is required; (2) when the support is paper, the quality of the paper is similar to that of ordinary paper; (3) it is easy to handle;
(4) High color density, (5) Simple and inexpensive recording device, and (6) No noise during recording. The need for heat-sensitive recording materials is also expanding in the label field, etc., 0) (P, multicolor recording field, etc.).
この場合、ＯＨＰは勿論、発色層を重層して多色化を図
るため、或いは、既に貼られたラベルの上に更に必要事
項を熱記録した透明ラベルを貼り足したいという要求に
答えるためには感熱層を透明にすることが必要である。In this case, in addition to OHP, in order to achieve multiple colors by layering coloring layers, or to respond to the request to add a transparent label with heat-recorded necessary information on top of the already pasted label, It is necessary that the heat-sensitive layer be transparent.
しかしながら、従来の透明な感熱記録材料は原稿と密着
させて光を照射することにより、原稿の画像部に赤外線
を吸収せしめて画像部の温度を高め、これにより感熱記
録フィルムを発色せしめるという、所謂透明感熱フィル
ムであり、ファクシミリ等で使用するサーマルヘッドで
直接記録できる熱感度を有するというものではない。However, with conventional transparent thermosensitive recording materials, when the image area of the original is brought into close contact with the original and irradiated with light, the image area of the original absorbs infrared rays, raising the temperature of the image area, which causes the thermal recording film to develop color. It is a transparent heat-sensitive film and does not have the thermal sensitivity to be directly recorded with a thermal head used in facsimile machines.
又、サーマルヘッドで熱記録できる従来の感熱記録材料
の感熱層は失透しており、これを単に透明支持体上に塗
布しても望まれる透明度を実現することはできなかった
。Furthermore, the heat-sensitive layer of a conventional heat-sensitive recording material that can be thermally recorded with a thermal head is devitrified, and it is not possible to achieve the desired transparency even if the material is simply coated on a transparent support.
本発明者等は、従来の係る欠点を解決することのできる
感熱記録材料として、発色系として無色又は淡色の電子
供与性染料前駆体と顕色剤の組み合わせを採用し、前者
をマイクロカプセルに含有せしめ、後者を水に難溶又は
不溶の有機溶剤に溶解して乳化分散液した後両者を混合
し、これを支持体上に塗布することによって得ることの
できる新規な透明感熱記録材料を提案した（特願昭６２
−８８１９７号）。The present inventors have adopted a combination of a colorless or light-colored electron-donating dye precursor and a color developer as a color-forming system as a heat-sensitive recording material that can solve these conventional drawbacks, and the former is contained in microcapsules. Therefore, we proposed a new transparent heat-sensitive recording material that can be obtained by dissolving the latter in an organic solvent that is sparingly soluble or insoluble in water to form an emulsified dispersion, then mixing the two and coating this on a support. (Special application 1986
-88197).
（発明が解決しようとする問題点）
しかしながら、上記の透明感熱層は耐傷性が不十分で、
擦り傷等によって失透し易いのみならず、表面に油類そ
の他の有機溶剤等が付着した場合には変色し、水滴が付
着した場合にはその部分が失透し、記録画像の品質を著
しく損なうという欠点があった。(Problems to be Solved by the Invention) However, the above-mentioned transparent heat-sensitive layer has insufficient scratch resistance;
Not only is it susceptible to devitrification due to scratches, etc., but it also changes color when oil or other organic solvents adhere to the surface, and devitrification occurs when water droplets adhere to the surface, significantly impairing the quality of recorded images. There was a drawback.
係る欠点は、透明感熱層の上に透明な保護層を設けるこ
とによって改善される（特開昭６３−９２４８９号）が
、保護層の透明性を十分に確保することを優先すると、
サーマルヘッドのスティッキングを十分に防止すること
ができないという欠点があった。Such drawbacks can be improved by providing a transparent protective layer on the transparent heat-sensitive layer (Japanese Patent Laid-Open No. 63-92489), but if priority is given to ensuring sufficient transparency of the protective layer,
There was a drawback that sticking of the thermal head could not be sufficiently prevented.
本発明者等は従来のかかる欠点を解決すべく鋭意検討し
た結果、透明保護層中に弗素系高分子を含有せしめた場
合には、透明性を十分に確保した上で更にスティッキン
グを十分に防止することができることを見い出し本発明
に到達した。The inventors of the present invention have made extensive studies to solve these conventional drawbacks, and have found that when a fluorine-based polymer is contained in the transparent protective layer, it is possible to sufficiently prevent sticking while ensuring sufficient transparency. The inventors have discovered that it is possible to do this, and have arrived at the present invention.
従って本発明の第１の目的は、耐傷性はもとより、耐溶
剤性、耐水性及び耐ステイツキング性に優れた、透明な
感熱層を有する感熱記録材料を提供することにある。Therefore, a first object of the present invention is to provide a heat-sensitive recording material having a transparent heat-sensitive layer that has excellent not only scratch resistance but also solvent resistance, water resistance, and staking resistance.
本発明の第２の目的は、透明な感熱層の上に設けること
のできる、耐傷性、耐溶剤性、耐水性及び耐ステイツキ
ング性に優れた透明な保護層を提供することにある。A second object of the present invention is to provide a transparent protective layer that can be provided on a transparent heat-sensitive layer and has excellent scratch resistance, solvent resistance, water resistance, and staking resistance.
（課題を解決するための手段）
本発明の上記の諸口的は、少なくとも支持体、該支持体
の一方の面に無色又は淡色の電子供与性染料前駆体を含
有するマイクロカプセル、及び、水に難溶又は不溶の有
機溶剤に溶解せしめた顕色剤を乳化分散し得られた乳化
分散物とを含む塗布液を塗布乾燥して形成せしめた透明
感熱層、並びに該透明感熱層の上に設けられた弗素系高
分子を含む保護層からなることを特徴とする感熱記録材
料によって達成された。(Means for Solving the Problems) The above aspects of the present invention include at least a support, a microcapsule containing a colorless or light-colored electron-donating dye precursor on one side of the support, and A transparent heat-sensitive layer formed by coating and drying a coating solution containing an emulsified dispersion obtained by emulsifying and dispersing a color developer dissolved in a poorly soluble or insoluble organic solvent, and a transparent heat-sensitive layer provided on the transparent heat-sensitive layer. This was achieved using a heat-sensitive recording material characterized by a protective layer containing a fluorine-based polymer.
本発明で使用する電子供与性染料前駆体としては、電子
を供与して、又は酸等のプロトンを受容して発色する公
知の化合物の中から無色又は淡色のものを適宜選択する
。このような化合物は、ラクトン、ラクタム、サルトン
、スピロピラン、エステル、アミド等の部分骨格を有し
、顕色剤と接触してこれらの部分骨格が開環若しくは開
裂するものであり、好ましい化合物としては、例えばト
リアリールメタン系化合物、ジフェニルメタン系化合物
、キサンチン系化合物、チアジン系化合物、スピロピラ
ン系化合物等を挙げることができる。As the electron-donating dye precursor used in the present invention, a colorless or light-colored one is appropriately selected from known compounds that develop color by donating electrons or accepting protons such as acids. Such compounds have partial skeletons such as lactones, lactams, sultones, spiropyrans, esters, and amides, and these partial skeletons are ring-opened or cleaved upon contact with a color developer. Preferred compounds include Examples include triarylmethane compounds, diphenylmethane compounds, xanthine compounds, thiazine compounds, and spiropyran compounds.
特に好ましい化合物は、次の一般式で表わされる化合物
である。Particularly preferred compounds are those represented by the following general formula.
式中、Ｒ１は炭素原子数１〜８のアルキル基、Ｒ２は炭
素原子数４〜１８のアルキル基又はアルコキシル基若し
くはテトラヒドロフルフリル基、Ｒ１は水素原子又は炭
素原子数１〜１５のアルキル基若しくはハロゲン原子、
Ｒ４は炭素数６〜２０の置換又は無置換のアリール基を
表わす。Ｒ４の置換基としては、炭素原子数１〜５のア
ルキル基、アルコキシ基、ハロゲン化アルキル基及びハ
ロゲン原子が好ましい。In the formula, R1 is an alkyl group having 1 to 8 carbon atoms, R2 is an alkyl group having 4 to 18 carbon atoms, an alkoxyl group, or a tetrahydrofurfuryl group, and R1 is a hydrogen atom, an alkyl group having 1 to 15 carbon atoms, or halogen atom,
R4 represents a substituted or unsubstituted aryl group having 6 to 20 carbon atoms. As the substituent for R4, an alkyl group having 1 to 5 carbon atoms, an alkoxy group, a halogenated alkyl group, and a halogen atom are preferable.
本発明においては、上記の発色剤をマイクロカプセル中
に内包せしめることにより、感熱材料製造時のカブリを
防止すると同時に、感熱材料の生保存性及び記録保存性
を良好なものとすることができる。この場合マイクロカ
プセルの壁材料及び製造方法を選択することにより、記
録時の画像濃度を高くすることができる。発色剤の使用
量は、０．０５〜５．０ｇ／％であることが好ましい。In the present invention, by encapsulating the above-mentioned color forming agent in microcapsules, it is possible to prevent fogging during the production of the heat-sensitive material, and at the same time, to improve the shelf life and recordability of the heat-sensitive material. In this case, by selecting the wall material and manufacturing method of the microcapsules, it is possible to increase the image density during recording. The amount of color former used is preferably 0.05 to 5.0 g/%.
マイクロカプセルの壁材料としては、ポリウレタン、ポ
リウレア、ポリエステル、ポリカーボネート、尿素−ホ
ルムアルデヒド樹脂、メラミン樹脂、ポリスチレン、ス
チレンメタクリレート共重合体、スチレン−アクリレー
ト共重合体、ゼラチン、ポリビニルピロリドン、ポリビ
ニルアルコール等が挙げられる。本発明においてはこれ
らの高分子物質を２種以上併用することもできる。Examples of the wall material of the microcapsule include polyurethane, polyurea, polyester, polycarbonate, urea-formaldehyde resin, melamine resin, polystyrene, styrene methacrylate copolymer, styrene-acrylate copolymer, gelatin, polyvinylpyrrolidone, polyvinyl alcohol, etc. . In the present invention, two or more of these polymeric substances can also be used in combination.
本発明においては、上記の高分子物質のうちポリウレタ
ン、ポリウレア、ポリアミド、ポリエステル、ポリカー
ボネート等が好ましく、特にポリウレタン及びポリウレ
アが好ましい。In the present invention, among the above-mentioned polymeric substances, polyurethane, polyurea, polyamide, polyester, polycarbonate, etc. are preferable, and polyurethane and polyurea are particularly preferable.
本発明で使用するマイクロカプセルは、発色剤等の反応
性物質を含有した芯物質を乳化した後、その油滴の周囲
に高分子物質の壁を形成してマイクロカプセル化するこ
とが好ましく、この場合高分子物質を形成するりアクタ
ントを油滴の内部及び／又は油滴の外部に添加する。マ
イクロカプセルの好ましい製造方法等、本発明で好まし
く使用することのできるマイクロカプセルについての詳
細は、例えば特開昭５９−２２２７１６号に記載されて
いる。The microcapsules used in the present invention are preferably microencapsulated by emulsifying a core material containing a reactive substance such as a coloring agent, and then forming a wall of a polymer material around the oil droplets. In this case, a polymeric material is formed or an actant is added to the interior of the oil droplet and/or to the exterior of the oil droplet. Details of microcapsules that can be preferably used in the present invention, such as a preferred method for producing microcapsules, are described in, for example, JP-A-59-222716.
ここで、油滴を形成するための有機溶剤としては、公知
の高沸点オイルの中から適宜選択することができる。Here, the organic solvent for forming oil droplets can be appropriately selected from known high boiling point oils.
好ましいオイルとしては、エステル類の他、下記一般式
（１）〜（ＩＩＩ）で表される化合物及びトリアリルメ
タン（例えば、トリトルイルメタン。In addition to esters, preferred oils include compounds represented by the following general formulas (1) to (III) and triallylmethane (for example, tritolylmethane).
トルイルジフェニールメタン）、ターフェニル化合物（
例えば、ターフェニル）、アルキル化ジフェニルエーテ
ル（例えば、プロピルジフェニルエーテル、水添ターフ
ェニル（例えば、ヘキサヒドロターフェニル）、ジフェ
ニルエーテル、塩素化パラフィン等が挙げられる。tolyldiphenylmethane), terphenyl compounds (
Examples include terphenyl), alkylated diphenyl ethers (eg, propyl diphenyl ether, hydrogenated terphenyl (eg, hexahydroterphenyl), diphenyl ether, chlorinated paraffin, etc.).
エステル類としては、燐酸エステル類（例えば、燐酸ト
リフエニル、燐酸トリクレジル、燐酸ブチル、燐酸オク
チル、燐酸タレジルジフェニル）、フタル酸エステル（
フタル酸ジブチル、フタル酸２−エチルヘキシル、フタ
ル酸エチル、フタル酸オクチル、フタル酸ブチルベンジ
ル）テトラヒドロフタル酸ジオクチル、安息香酸エステ
ル（安息香酸エチル、安息香酸プロピル、安息香酸ブチ
ル、安息香酸イソペンチル、安息香酸ベンジル）、アビ
エチン酸エステル（アビエチン酸エチル、アビエチン酸
ベンジル）、アジピン酸ジオクチル、コハク酸イソデシ
ル、アゼライン酸ジオークチル、シュウ酸エステル（シ
ュウ酸ジブチル、シュウ酸ジペンチル）、マロン酸ジエ
チル、マレイン酸エステル（、マレイン酸ジメチル、マ
レイン酸ジエチル、マレイン酸ジブチル）、クエン酸ト
リブチル、ソルビン酸エステル（ソルビン酸メチル、ソ
ルビン酸エチル、ソルビン酸ブチル）、セバシン酸エス
テル（セバシン酸ジブチル、セバシン酸ジオクチル）、
エチレングリコールエステル類（ギ酸モノエステル及び
ジエステル、酪酸モノエステル及びジエステル、ラウリ
ン酸モノエステル及びジエステル、パルミチン酸モノエ
ステル及びジエステル、ステアリン酸モノエステル及び
ジエステル、オレイン酸モノエステル及びジエステル）
、トリアセチン、炭酸ジエチル、炭酸ジフェニル、炭酸
エチレン、炭酸プロピレン、ホウ酸エステル（ホウ酸ト
リブチル、ホウ酸トリペンチル）等が挙げられる。Examples of esters include phosphoric esters (for example, triphenyl phosphate, tricresyl phosphate, butyl phosphate, octyl phosphate, talesyl diphenyl phosphate), phthalic esters (
Dibutyl phthalate, 2-ethylhexyl phthalate, ethyl phthalate, octyl phthalate, butylbenzyl phthalate) dioctyl tetrahydrophthalate, benzoate ester (ethyl benzoate, propyl benzoate, butyl benzoate, isopentyl benzoate, benzoic acid) benzyl), abietate ester (ethyl abietate, benzyl abietate), dioctyl adipate, isodecyl succinate, dioctyl azelate, oxalate ester (dibutyl oxalate, dipentyl oxalate), diethyl malonate, maleate ester (, dimethyl maleate, diethyl maleate, dibutyl maleate), tributyl citrate, sorbate esters (methyl sorbate, ethyl sorbate, butyl sorbate), sebacate esters (dibutyl sebacate, dioctyl sebacate),
Ethylene glycol esters (formic acid monoesters and diesters, butyric acid monoesters and diesters, lauric acid monoesters and diesters, palmitic acid monoesters and diesters, stearic acid monoesters and diesters, oleic acid monoesters and diesters)
, triacetin, diethyl carbonate, diphenyl carbonate, ethylene carbonate, propylene carbonate, boric acid esters (tributyl borate, tripentyl borate), and the like.
／
／
ン
式中、Ｒ１は水素又は炭素数１〜１８のアルキル基を、
Ｒ１は炭素数１〜１８のアルキル基を表わす。ｐ ｌ
、ｑ ＋ は１〜４の整数を表し、且つアルキル基の総
和は４個以内とする。/ / In the formula, R1 is hydrogen or an alkyl group having 1 to 18 carbon atoms,
R1 represents an alkyl group having 1 to 18 carbon atoms. pl
, q + represents an integer of 1 to 4, and the total number of alkyl groups is 4 or less.
なお、Ｒ１、Ｒ１のアルキル基は炭素数１〜８のアルキ
ル基が好ましい。In addition, the alkyl group of R1 and R1 is preferably an alkyl group having 1 to 8 carbon atoms.
（ＩＩ）
式中、Ｒ３は水素原子又は炭素数１〜１２のアルキル基
、Ｒ４は炭素数１〜１２のアルキル基、ｎはｌ又は２を
表わす。(II) In the formula, R3 represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, R4 represents an alkyl group having 1 to 12 carbon atoms, and n represents 1 or 2.
ｐ ２ 、ｑ Ｎは１〜４の整数を表わす。ｎ＝１の場
合には、アルキル基の総和は４個以内であり、ｎ＝２の
ときアルキル基の総和は６個以内である。p 2 and q N represent integers from 1 to 4. When n=1, the total number of alkyl groups is 4 or less, and when n=2, the total number of alkyl groups is 6 or less.
（［［）
式中、Ｒｓ 、Ｒ６は水素原子又は、炭素数１〜１８の
同種もしくは異種のアルキル基を表わす。([[) In the formula, Rs and R6 represent a hydrogen atom or the same or different alkyl group having 1 to 18 carbon atoms.
ｍは１〜１３の整数を表わす。Ｒ３、ｑ３は１〜３の整
数を表し、かつアルキル基の総和は３個以内である。m represents an integer from 1 to 13. R3 and q3 represent an integer of 1 to 3, and the total number of alkyl groups is 3 or less.
なお、Ｒ’、Ｒ−のアルキル基は炭素数２〜４のアルキ
ル基が特に好ましい。In addition, the alkyl group of R' and R- is particularly preferably an alkyl group having 2 to 4 carbon atoms.
式、（Ｉ）で表わされる化合物例としては、ジメチルナ
フタレン、ジエチルナフタレン、ジイソプロピルナフタ
レンが挙げられる。Examples of the compound represented by formula (I) include dimethylnaphthalene, diethylnaphthalene, and diisopropylnaphthalene.
式（Ｉｔ）で表される化合物例としては、ジメチルビフ
ェニル、ジエチルビフェニル、ジイソプロピルビフェニ
ル、ジイソブチルビフェニルが挙げられる。Examples of the compound represented by formula (It) include dimethylbiphenyl, diethylbiphenyl, diisopropylbiphenyl, and diisobutylbiphenyl.
式（ＩＩＩ）で表わされる化合物例としては、１メチル
−１−ジメチルフェニル−１−フェニルメタン、ｌ−エ
チル−１−ジメチルフェニル−１−フェニルメタン、１
−プロピル−１−ジメチルフェニル−１−フェニルメタ
ンが挙げられる。Examples of the compound represented by formula (III) include 1-methyl-1-dimethylphenyl-1-phenylmethane, 1-ethyl-1-dimethylphenyl-1-phenylmethane, and 1-methylphenyl-1-phenylmethane.
-propyl-1-dimethylphenyl-1-phenylmethane.
上記のオイル同士、又は他のオイルとの併用も可能であ
る。It is also possible to use the above oils together or with other oils.
上記の如く製造される好ましいマイクロカプセルは、従
来の記録材料に用いられているような熱や圧力によって
破壊するものではなく、マイクロカプセルの芯及び外に
含有されている反応性物質は、マイクロカプセル壁を透
過して反応することができる。The preferred microcapsules produced as described above are not destroyed by heat or pressure as used in conventional recording materials, and the reactive substances contained in the core and outside of the microcapsules are Can react by penetrating walls.
本発明においては、マイクロカプセルの壁材を選択し、
必要によりガラス転移点調整剤（例えば、特願昭６０−
１１９８６２号に記載の可塑剤）を添加することによっ
て、ガラス転移点の異なる壁からなるマイクロカプセル
を調製し、色相の異なる塩基性無色染料前駆体とその顕
色剤の組み合わせを選択することにより多色の中間色を
実現することができる。従って、本発明は単色の感熱記
録材料に限定されるものではなく、２色或いは多色の感
熱記録材料にも応用することができる。In the present invention, the wall material of the microcapsule is selected,
If necessary, a glass transition point adjusting agent (for example, Japanese patent application 1986-
119862) to prepare microcapsules consisting of walls with different glass transition points, and by selecting combinations of basic colorless dye precursors with different hues and their color developers. It is possible to achieve intermediate colors. Therefore, the present invention is not limited to single-color heat-sensitive recording materials, but can also be applied to two-color or multi-color heat-sensitive recording materials.
又、必要に応じて、例えば特開昭６１−２８３５８９号
、同６１−２８３５９０号、同６１−２８３５９１号に
記載された光退色防止剤を適宜加えることができる。Further, if necessary, a photofading inhibitor described in, for example, JP-A-61-283589, JP-A-61-283590, and JP-A-61-283591 can be appropriately added.
本発明で使用する塩基性無色染料との熱溶融において発
色反応を起こす顕色剤としては、公知のものの中から適
宜使用することができる。例えば、ロイコ染料に対する
顕色剤としては、フェノール化合物、トリフェニルメタ
ン系化合物、含硫フェノール系化合物、カルボン酸系化
合物、スルホン系化合物、尿素系又はチオ尿素系化合物
等が挙げられ、その詳細は、例えば、祇バルブ技術タイ
ムス（１９８５年）４９−５４頁及び６５−Ｔｏ頁に記
載されている。これらの中でも、特に融点が５０“０〜
２５０℃の物が好ましく、中でも６０°Ｃ〜２００°Ｃ
の、水に難溶性のフェノール及び有機酸が望ましい。顕
色剤を２種以上併用した場合には溶解性が増加するので
好ましい。As a color developer that causes a color-forming reaction when heated and melted with the basic colorless dye used in the present invention, any known color developer can be used as appropriate. For example, color developers for leuco dyes include phenolic compounds, triphenylmethane compounds, sulfur-containing phenol compounds, carboxylic acid compounds, sulfone compounds, urea or thiourea compounds, etc. , for example, in Gi Valve Technology Times (1985), pages 49-54 and 65-To. Among these, especially those with a melting point of 50"0~
250°C is preferable, especially 60°C to 200°C
Preferred are phenols and organic acids that are sparingly soluble in water. It is preferable to use two or more color developers in combination because the solubility increases.
本発明で使用する顕色剤のうち特に好ましいものは、下
記一般式（ＩＶ）〜〔■〕で表される。Among the color developers used in the present invention, particularly preferred ones are represented by the following general formulas (IV) to [■].
Ｃ＊Ｈ！ｌＩ＊１
（Ｖ）
Ｒはアルキル基、アリール基、アリールオキシアル基又
はアラルキル基であり特にメチル基、エチル基及びブチ
ル基が好ましい。C*H! lI*1 (V) R is an alkyl group, an aryl group, an aryloxyal group, or an aralkyl group, with methyl, ethyl, and butyl groups being particularly preferred.
（Ｖｌ）
Ｒ２はアルキル基であり、特にブチル基、ペンチル基、
ヘプチル基及びオクチル基が好ましい。(Vl) R2 is an alkyl group, especially a butyl group, a pentyl group,
Heptyl and octyl groups are preferred.
Ｒ１は水素原子又はメチル基であり、ｎはＯ〜２である
。R1 is a hydrogen atom or a methyl group, and n is O-2.
〔■］
Ｒ４はアルキル基、アリールオキシアルキル基又はアラ
ルキル基である。[■] R4 is an alkyl group, an aryloxyalkyl group or an aralkyl group.
本発明においては、顕色剤を水に難溶又は不溶性の有機
溶剤に溶解せしめた後、これを界面活性剤を含有し水溶
性高分子を保護コロイドとして有する水相と混合し、乳
化分散した分散物の形で使用する。In the present invention, a color developer is dissolved in an organic solvent that is sparingly soluble or insoluble in water, and then mixed with an aqueous phase containing a surfactant and having a water-soluble polymer as a protective colloid to emulsify and disperse it. Use in the form of a dispersion.
顕色剤を溶解する有機溶剤としては、前記したマイクロ
カプセル製造時に使用するオイルを用いる。As the organic solvent for dissolving the color developer, the oil used in producing the microcapsules described above is used.
本発明においては、これらの中でもエステル類を使用す
ることが、顕色剤の溶解性及び顕色剤の乳化分散物の乳
化安定性の観点から特に好ましい。In the present invention, among these, it is particularly preferable to use esters from the viewpoint of the solubility of the color developer and the emulsion stability of the emulsified dispersion of the color developer.
本発明においては、更に補助溶剤として、沸点１５０°
Ｃ以下の有機溶媒を使用することできる。In the present invention, as an auxiliary solvent, a boiling point of 150°
Organic solvents below C can be used.
このような有機溶媒としては、酢酸のアルキルエステル
又はアルキレンクロライドが好ましく、その具体例とし
ては、例えば、酢酸エチル、酢酸ブチル、酢酸プロピル
、メチレンクロライド等を挙げることができる。Such organic solvents are preferably acetic acid alkyl esters or alkylene chlorides, and specific examples thereof include ethyl acetate, butyl acetate, propyl acetate, methylene chloride, and the like.
顕色剤を溶解した油相と混合する水相に、保護コロイド
として含有せしめる水溶性高分子は、公知のアニオン性
高分子、ノニオン性高分子、両性高分子の中から適宜選
択することができるが、ポリビニルアルコール、ゼラチ
ン、セルロース誘導体等が好ましく、特に、ポリビニル
アルコールの部分けん化物が好ましい。The water-soluble polymer to be contained as a protective colloid in the aqueous phase to be mixed with the oil phase in which the color developer is dissolved can be appropriately selected from known anionic polymers, nonionic polymers, and amphoteric polymers. However, polyvinyl alcohol, gelatin, cellulose derivatives, etc. are preferred, and partially saponified polyvinyl alcohol is particularly preferred.
又、水相に含有せしめる界面活性剤としては、アニオン
性又はノニオン性の界面活性剤の中から、上記保護コロ
イドと作用して沈澱や凝集を起こさないものを適宜選択
して使用することができる。Further, as the surfactant to be contained in the aqueous phase, one can be appropriately selected from anionic or nonionic surfactants that do not cause precipitation or aggregation by interacting with the above-mentioned protective colloid. .
好ましい界面活性剤としては、アルキルベンゼンスルホ
ン酸ソーダ（例えば、ドデシルベンゼンスルホン酸ソー
ダ）、アルキル硫酸ナトリウム、スルホコハク酸ジオク
チルナトリウム塩、ポリアルキレングリコール（例えば
、ポリオキシエチレンノニルフェニルエーテル）等を挙
げることができる。Preferred surfactants include sodium alkylbenzenesulfonate (e.g., sodium dodecylbenzenesulfonate), sodium alkylsulfate, dioctyl sodium sulfosuccinate, polyalkylene glycol (e.g., polyoxyethylene nonylphenyl ether), and the like. .
本発明における顕色剤の乳化分散物は、顕色剤を含有す
る油相と保護コロイド及び界面活性剤を含有する水相を
、高速撹拌、超音波分散等、通常の微粒子乳化に用いら
れる手段を使用して混合分散せしめ容易に得ることがで
きる。The emulsified dispersion of a color developer in the present invention is produced by mixing an oil phase containing a color developer and an aqueous phase containing a protective colloid and a surfactant by means commonly used for fine particle emulsification, such as high-speed stirring and ultrasonic dispersion. It can be easily mixed and dispersed using.
この乳化分散物には、適宜顕色剤の融点降下剤を添加す
ることもできる。このような融点降下剤の中の一部は、
前記カプセル壁のガラス転移点調節剤の機能をも有する
。このような化合物としては、例えばヒドロキシ化合物
、カルバミン酸エステル化合物、スルホンアミド化合物
、芳香族メトキシ化合物等があり、それらの詳細は、例
えば特願昭５９−２４４１９０号に記載されている。A melting point depressant for a color developer may be added to this emulsified dispersion as appropriate. Some of these melting point depressants are
It also functions as a glass transition point regulator for the capsule wall. Examples of such compounds include hydroxy compounds, carbamate ester compounds, sulfonamide compounds, aromatic methoxy compounds, etc., and details thereof are described in, for example, Japanese Patent Application No. 59-244190.
これらの融点降下剤は、融点を降下せしめる顕色剤１重
量部に対し０．１〜２重量部、好ましくは０．５〜１重
量部の範囲で適宜使用することができるが、融点降下剤
とそれによって融点が降下する顕色剤等は、同一の箇所
に使用することが好ましい。異なった個所に添加する場
合には、上記の添加量の１〜３倍量を添加することが好
ましい。These melting point depressants can be used in an amount of 0.1 to 2 parts by weight, preferably 0.5 to 1 part by weight, per 1 part by weight of the color developer that lowers the melting point. It is preferable that the color developer and the color developer whose melting point is lowered thereby are used at the same location. When adding to different locations, it is preferable to add 1 to 3 times the above amount.
本発明に係わる感熱層は適当なバインダーを用いて塗工
することができる。The heat-sensitive layer according to the present invention can be coated using a suitable binder.
バインダーとしてはポリビニルアルコール、メチルセル
ロース、カルボキシメチルセルロース、ヒドロキシプロ
ピルセルロース、アラビヤゴム、ゼラチン、ポリビニル
ピロリドン、カゼイン、スチレン−ブタジェンラテック
ス、アクリロニトリル−ブタジェンラテックス、ポリ酢
酸ビニル、ポリアクリル酸エステル、エチレン−酢酸ビ
ニル共重合体等の各種エマルジョンを用いることができ
る。使用量は固形分として０．５〜５ｇ／ｒｄである。Binders include polyvinyl alcohol, methylcellulose, carboxymethylcellulose, hydroxypropylcellulose, gum arabic, gelatin, polyvinylpyrrolidone, casein, styrene-butadiene latex, acrylonitrile-butadiene latex, polyvinyl acetate, polyacrylic acid ester, ethylene-vinyl acetate, etc. Various emulsions such as polymers can be used. The amount used is 0.5 to 5 g/rd as solid content.
本発明の感熱記録材料を製造するためには、先ず、発色
剤を内包したマイクロカプセル及び少なくとも顕色剤を
乳化分散した分散物の主成分、及びバインダー等その他
の添加物を含有した塗布液を作り、紙や合成樹脂フィル
ム等の支持体の上にバー塗布、ブレード塗布、エアナイ
フ塗布、グラビア塗布、ロールコーティング塗布、スプ
レー塗布、デイツプ塗布等の塗布法により塗布乾燥して
、固形分が２．５〜２５ｇ／ｎｆの感熱層を設ける。In order to produce the heat-sensitive recording material of the present invention, first, a coating liquid containing microcapsules encapsulating a color former, main components of a dispersion in which at least a color developer is emulsified and dispersed, and other additives such as a binder is prepared. It is coated on a support such as paper or synthetic resin film by a coating method such as bar coating, blade coating, air knife coating, gravure coating, roll coating, spray coating, dip coating, etc. and dried to a solid content of 2. A heat sensitive layer of 5 to 25 g/nf is provided.
このようにして設けた感熱材料の感熱層は、理由は明ら
かではないが、極めて良好な透明性を有する。The heat-sensitive layer of the heat-sensitive material thus provided has extremely good transparency, although the reason is not clear.
本発明においては、上記透明性の良好な感熱層の表面を
保護するために、透明性が良好で且つ、熱ヘツドに対す
るスティッキングを改良することのできる透明保護層を
１層以上設ける。透明な保護層は、主としてシリカ変性
ポリビニルアルコール（特開昭６３−９２４８９号）及
び／又はカルボキシ変性メチルセルロースとコロイダル
シリカを用いて構成することができるが、本発明におい
ては、スティッキングを改善するために更に弗素系高分
子を含有させる。In the present invention, in order to protect the surface of the heat-sensitive layer having good transparency, one or more transparent protective layers are provided which have good transparency and can improve sticking to a thermal head. The transparent protective layer can be mainly composed of silica-modified polyvinyl alcohol (JP-A No. 63-92489) and/or carboxy-modified methylcellulose and colloidal silica, but in the present invention, in order to improve sticking, Furthermore, a fluorine-based polymer is contained.
本発明で使用する弗素系高分子は、従来公知のものの中
から適宜選択して使用することができる。The fluorine-based polymer used in the present invention can be appropriately selected from conventionally known polymers.
このような弗素系高分子としては、例えば炭素数３〜２
０個のパーフルオロアルキル基を含有しアクリレート又
はメタクリレートで代表される不飽和エステル類の単独
重合体、又は共重合体等の他、
牙
ＣＦｊ
Ｈ（ＣＦりｌ。ＣＨ！ ０ＣＯＣＨ＝ＣＨ２、ＣＦｔ
ｃＩ！、（ＣＦｚ）＋。ＣＨ。Such fluorine-based polymers include, for example, those having 3 to 2 carbon atoms.
In addition to homopolymers or copolymers of unsaturated esters containing 0 perfluoroalkyl groups and represented by acrylates or methacrylates, CFj H(CFRIl.CH! 0COCH=CH2, CFt
cI! , (CFz)+. CH.
蒼 Ｃｏ−Ｃ（ＣＨ，）＝ＣＨ。blue Co-C(CH,)=CH.
の様なポリフルオロアルキル基含有化合物の重合体又は
共重合体等を挙げることができるが、特にパーフルオロ
アルキル基を含有するものが好ましい
更に、入手容易性その他を考慮すると、−Ｓ式Ｒｆ Ｒ
ＯＣＯＣＲ’ ＝ ＣＨｔ （但し、式中Ｒｆは３〜
２０個の炭素原子を有する直鎖状又は分岐状のパーフル
オロアルキル基、Ｒは１〜ｌＯ個の炭素原子を有する直
鎖状又は分岐状のアルキレン基、Ｒ″は水素原子又はメ
チル基を示す）で表わされる末端パーフルオロアルキル
基を含有するアクリレート又はメタクリレートの単独重
合体又は共重合体等が特に好ましい。Ｒｆは炭素数６〜
１２個のパーフルオロアルキル基であることが好ましく
、Ｒは炭素数２〜４個のアルキレン基であることが好ま
しい。Examples include polymers or copolymers of polyfluoroalkyl group-containing compounds such as, but those containing perfluoroalkyl groups are particularly preferred.Furthermore, in consideration of availability and other considerations, -S formula Rf R
OCOCR' = CHt (However, in the formula, Rf is 3 to
a straight-chain or branched perfluoroalkyl group having 20 carbon atoms; R is a straight-chain or branched alkylene group having 1 to 10 carbon atoms; R'' represents a hydrogen atom or a methyl group; ) Homopolymers or copolymers of acrylates or methacrylates containing a terminal perfluoroalkyl group are particularly preferred. Rf has 6 to 6 carbon atoms.
Preferably, it is a 12 perfluoroalkyl group, and R is preferably an alkylene group having 2 to 4 carbon atoms.
一般に前記ポリフルオロアルキル基含有の化合物の他に
、エチレン、酢酸ビニル、塩化ビニル、弗化ビニル、ハ
ロゲン化ビニリデン、アクリロニトリル、メタクリレー
トリル、スチレン、α−メチルスチレン、Ｐ−メチルス
チレン、アクリル酸とそのアルキルエステル、メタクリ
ル酸とそのアルキルエステル、アクリルアミド、メタク
リルアミド、ジアセトンアクリルアミド、メチロール化
ジアセトンアクリルアミド、メチロール化ジアセトンア
クリルアミド、Ｎ−メチロールアクリルアミド、ビニル
アルキルエーテル、ハロゲン化アルキルビニルエーテル
、ビニルアルキルケトン、フタジエン、イソプレン、ク
ロロプレン、グリシジルアクリレート、無水マレイン酸
の様なフルオロアルキル基を含まない化合物の一種又は
二種以上を構成単位として共重合させたものを使用する
ことができる。In general, in addition to the polyfluoroalkyl group-containing compounds mentioned above, ethylene, vinyl acetate, vinyl chloride, vinyl fluoride, vinylidene halide, acrylonitrile, methacrylateryl, styrene, α-methylstyrene, P-methylstyrene, acrylic acid and Alkyl esters, methacrylic acid and its alkyl esters, acrylamide, methacrylamide, diacetone acrylamide, methylolated diacetone acrylamide, methylolated diacetone acrylamide, N-methylol acrylamide, vinyl alkyl ether, halogenated alkyl vinyl ether, vinyl alkyl ketone, phtadiene , isoprene, chloroprene, glycidyl acrylate, and maleic anhydride, which are copolymerized as constituent units of one or more compounds that do not contain fluoroalkyl groups, can be used.
これらの弗素系高分子は、保護層成分中に単に添加する
ことができるのみならず、例えば旭ガード、ＡＣ−５５
０（いずれも商品名、旭硝子■製）、スコッチパン、Ｆ
Ｃ−８０８（いずれも商品名、米国３Ｍ社製）及びＦ−
６０（大日本インキ社製商品名）、ポリフロン、ネオフ
ロン（いずれも■ダイキン製商品名）等の市販品に代表
されるエマルジョンとして使用することもできる。These fluorine-based polymers can not only be simply added to the protective layer components, but can also be added to, for example, Asahi Guard, AC-55
0 (all product names, manufactured by Asahi Glass), Scotch bread, F
C-808 (all product names, manufactured by 3M Company in the United States) and F-
It can also be used as an emulsion, typified by commercial products such as 60 (trade name, manufactured by Dainippon Ink Co., Ltd.), Polyflon, and Neoflon (all brand names, manufactured by Daikin).
弗素系高分子の使用量は、保護層成分中の１〜６０重量
％であり、特に、透明性及び耐水、耐溶剤性及びスティ
ッキング防止のバランスの観点から２０〜４０重量％と
することが好ましい。The amount of the fluorine-based polymer used is 1 to 60% by weight in the protective layer components, and preferably 20 to 40% by weight from the viewpoint of transparency, water resistance, solvent resistance, and a balance between sticking prevention. .
スティッキングの改良は、例えば、シリカ、硫酸バリウ
ム、酸化チタン、水酸化アルミニウム、酸化亜鉛、炭酸
カルシウム等の顔料や、スチレンビーズ、尿素−メラミ
ン樹脂等の微粉末を添加することによって更に完全にす
ることができる。The improvement of sticking can be further perfected by adding pigments such as silica, barium sulfate, titanium oxide, aluminum hydroxide, zinc oxide, calcium carbonate, etc., or fine powders such as styrene beads, urea-melamine resin, etc. Can be done.
又同様に、スティッキング防止のためにフックス類や金
属石鹸類を添加することもできる。これらの使用量は０
．２〜７ｇ／ｍ”である。Similarly, hooks or metal soaps may be added to prevent sticking. The usage of these is 0
．． 2 to 7 g/m''.
支持体に用いられる紙としてはアルキルケテンダイマー
等の中性サイズ剤によりサイジングされた熱抽出ｐＨ６
〜９の中性紙（特開昭５５−１４２８１号記載のもの）
を用いると、経時保存性の点で有利である。The paper used for the support is heat extracted pH 6 sized with a neutral sizing agent such as an alkyl ketene dimer.
~9 Neutral paper (described in JP-A-55-14281)
The use of is advantageous in terms of storage stability over time.
紙への塗液の浸透を防ぎ、又、記録熱ヘツドと感熱記録
層との接触を良くするためには、特開昭５７−１１６６
８７号に記載の、
且つ、ベック平滑度９０秒以上の紙が有利である。In order to prevent the coating liquid from penetrating the paper and to improve the contact between the recording heat head and the heat-sensitive recording layer, Japanese Patent Application Laid-Open No. 57-1166
The paper described in No. 87 and having a Bekk smoothness of 90 seconds or more is advantageous.
又特開昭５８−１３６４９２号に記載の光学的表面粗さ
が８μ以下、且つ厚みが４０〜７５μの紙、特開昭５８
−６９０９７号記載の密度０．９ｇ／ｃｍ’以下で且つ
光学的接触率が１５％以上の紙、特開昭５８−６９０９
７号に記載のカナダ標準濾水度（ＪＩＳ Ｐ８１２１
）で４００ｃｃ以上に叩解したパルプより抄造し、塗布
液のしみ込みを防止した紙、特開昭５８−６５６９５号
に記載の、ヤンキーマシンにより抄造された原紙の光沢
面を塗布面とし、発色濃度及び解像力を改良するもの、
特開昭５９−３５９８５号に記載されている、原紙コロ
ナ放電処理を施して塗布適正を改良した紙等も本発明に
用いられ、良好な結果を与える。これらの他通常の感熱
記録紙の分野で用いられる支持体はいずれも本発明の支
持体として使用することができる。Also, paper having an optical surface roughness of 8μ or less and a thickness of 40 to 75μ, described in JP-A-58-136492, JP-A-58-136492.
Paper with a density of 0.9 g/cm' or less and an optical contact ratio of 15% or more as described in No. 69097, JP-A-58-6909
Canadian standard freeness described in No. 7 (JIS P8121
) is paper made from pulp beaten to 400 cc or more with a paper that prevents the coating solution from seeping in. The coated surface is the glossy side of the base paper made by a Yankee machine, as described in JP-A No. 58-65695, and the color density is and those that improve resolution;
The paper described in JP-A No. 59-35985, which has been subjected to a corona discharge treatment to improve its suitability for coating, can also be used in the present invention and gives good results. In addition to these, any support commonly used in the field of heat-sensitive recording paper can be used as the support of the present invention.
本発明で支持体として使用する合成樹脂フィルムは、耐
摩耗性、耐水性、耐薬品性に優れ、感熱層の塗布によっ
てカールを生じない程度の厚み及び／又は剛性を有し、
発色過程での加熱等に対しても変形せず、寸法安定性を
有する公知の材料の中から任意に選択することができる
。The synthetic resin film used as a support in the present invention has excellent abrasion resistance, water resistance, and chemical resistance, and has a thickness and/or rigidity that does not cause curling when the heat-sensitive layer is applied.
Any material can be selected from known materials that are dimensionally stable and do not deform even when heated during the coloring process.
このようなフィルムとしては、ポリエチレンテレフタレ
ートやポリブチレンテレフタレート等のポリエステルの
フィルム、三酢酸セルロースフィルム等のセルロース誘
導体のフィルム、ポリスチレンフィルム、ポリプロピレ
ンフィルム、ポリエチレン等のポリオレフィンのフィル
ム等があり、これらを単体で或いは貼り合わせて用いる
ことができる。Examples of such films include polyester films such as polyethylene terephthalate and polybutylene terephthalate, cellulose derivative films such as cellulose triacetate films, polystyrene films, polypropylene films, and polyolefin films such as polyethylene. Alternatively, they can be used by bonding them together.
透明支持体の厚みとしては２０〜２００μのものが用い
られ、特に５０〜１００μのものが好ましい。The thickness of the transparent support used is 20 to 200 .mu.m, particularly preferably 50 to 100 .mu.m.
支持体には、印字時に精度よく支持体が搬送できるよう
に、パーフォレーションを設けても良い。The support may be provided with perforations so that the support can be conveyed with high precision during printing.
本発明においては、透明支持体と感熱層の接着を高める
ために両層の間に下塗層を設けることができる。下塗層
の素材としては、ゼラチンや合成高分子ラテックス、ニ
トロセルロース等が用いられる。下塗層の塗布量は０．
１ｇ／ｍ”〜２． Ｏｇ／ｍ”の範囲にあることが好
ましく、特に０゜２ ｇ／ｍ” 〜１．Ｏｇ／ｍ” ０
）範囲が好ましい。In the present invention, an undercoat layer can be provided between the transparent support and the heat-sensitive layer in order to enhance adhesion between the two layers. Gelatin, synthetic polymer latex, nitrocellulose, etc. are used as the material for the undercoat layer. The coating amount of the undercoat layer is 0.
It is preferably in the range of 1 g/m" to 2.0 g/m", particularly 0.2 g/m" to 1.0 g/m" 0
) range is preferred.
０．１ｇ／ｍ”より少ないと支持体と感熱層との接着が
充分でなく、又２．Ｏｇ／ｍ”以上にふやしても支持体
と感熱層との接着力は飽和に達しているのでコスト的に
不利となる。If it is less than 0.1 g/m", the adhesion between the support and the heat-sensitive layer will not be sufficient, and even if it is increased to more than 2.0 g/m", the adhesion between the support and the heat-sensitive layer will reach saturation. This is disadvantageous in terms of cost.
下塗層は、感熱層がその上に塗布された時に感熱層中に
含まれる水により下塗層が膨潤する場合には感熱層の画
質が悪化することがあるので、硬膜剤」を用いて硬化さ
せることが望ましい。For the undercoat layer, if the undercoat layer swells due to the water contained in the heat-sensitive layer when it is coated on top of it, the image quality of the heat-sensitive layer may deteriorate, so a hardening agent is used. It is desirable to harden the material.
本発明に用いることができる硬膜剤としては、下記のも
のを挙げることができる。As hardeners that can be used in the present invention, the following can be mentioned.
■ジビニルスルホンーＮ、 Ｎ’ −エチレンビス（
ビニルスルホニルアセタミド）、１．３−ビス（ビニル
スルホニル）−２−プロパツール、メチレンビスマレイ
ミド、５−アセチル−・ｌ、３−ジアクリロイル−へキ
サヒドロ＝Ｓ−）リアジン、１．３．５−１−リアクリ
ロイル−へキサヒドロ−５−トリアジン、１，３．５−
トリビニルスルホニル−へキサヒドロ−８−トリアジン
、の如き活性ビニル系化合物。■Divinylsulfone-N, N'-ethylenebis(
(vinylsulfonylacetamide), 1.3-bis(vinylsulfonyl)-2-propatol, methylenebismaleimide, 5-acetyl-.l,3-diacryloyl-hexahydro=S-)riazine, 1.3. 5-1-lyacryloyl-hexahydro-5-triazine, 1,3.5-
Active vinyl compounds such as trivinylsulfonyl-hexahydro-8-triazine.
■２，４−ジクロロ−６−ヒドロキシ−３−トリアジン
・ナトリウム塩、２．４−ジクロロ−６メトキシーｓ−
トリアジン、２．４−ジクロロ６−（４−スルホアニリ
ノ）−Ｓ−トリアジン・ナトリウム塩、２，４−ジクロ
ロ−６７（２＝スルホエチルアミノ）−Ｓ−）リアジン
、Ｎ−Ｎ’−ビス（２−クロロエチルカルバミル）ピペ
ラジンの如き活性ハロゲン系化合物。■2,4-dichloro-6-hydroxy-3-triazine sodium salt, 2,4-dichloro-6methoxys-
Triazine, 2,4-dichloro-6-(4-sulfoanilino)-S-triazine sodium salt, 2,4-dichloro-67(2=sulfoethylamino)-S-)riazine, N-N'-bis(2 -Activated halogen compounds such as chloroethylcarbamyl)piperazine.
■ビス（２，３−エポキシプロビル）メチルプロピルア
ンモニウム・ｐ−）ルエンスルホン酸塩、１．４−ビス
（２“、３゛−エポキシプロピルオキシ）ブタン、１，
３．５−トリグリシジルイソシアヌレート、１，３−ジ
グリシジル−５−（γ−アセトキシーβ−オキシプロピ
ル）イソシアヌレートの如きエポキシ系化合物。■Bis(2,3-epoxypropyl)methylpropylammonium p-)luenesulfonate, 1,4-bis(2",3"-epoxypropyloxy)butane, 1,
Epoxy compounds such as 3.5-triglycidyl isocyanurate and 1,3-diglycidyl-5-(γ-acetoxyβ-oxypropyl)isocyanurate.
■２，４．６−ドリエチレンーＳ−トリアジン、１．６
−へキサメチレン−Ｎ、Ｎ’ −ビスエチレン尿素、ビ
ス−β−エチレンイミノエチルチオエーテルの如きエチ
レンイミノ系化合物。■2,4.6-doriethylene-S-triazine, 1.6
Ethyleneimino compounds such as -hexamethylene-N,N'-bisethyleneurea and bis-β-ethyleneiminoethylthioether.
■１，２−ジ（メタンスルホンオキシ）エタン、１．４
−ジ（メタンスルホンオキシ）ブタン、■。■1,2-di(methanesulfonoxy)ethane, 1.4
-di(methanesulfonoxy)butane, ■.
５−ジ（メタンスルホンオキシ）ペンタンの如きメタン
スルホン酸エステル系化合物。Methanesulfonic acid ester compounds such as 5-di(methanesulfonoxy)pentane.
■ジシクロへキシルカルボジイミド、１−シフｏへ＋シ
ルー３− （３−）リメチルアミノプロビル）カルボジ
イミド−Ｐ−）リエンスルホン酸塩、１−エチル−３−
（３−ジメチルアミノプロピル）カルボジイミド塩酸塩
の如きカルボジイミド系化合物。■Dicyclohexylcarbodiimide, 1-Schifo + Silu 3- (3-)limethylaminoprobyl)carbodiimide-P-) Lienesulfonate, 1-ethyl-3-
Carbodiimide compounds such as (3-dimethylaminopropyl)carbodiimide hydrochloride.
■２．５−ジメチルイソオキサゾール・過塩素ｌ塩、２
−エチル−５−フェニルイソオキサゾール−３°−スル
ホネート、５，５°−（バラフヱニレン）ビスイソオキ
サゾールの如きイソオキサゾール系化合物。■2.5-dimethylisoxazole/perchlorine salt, 2
-Isoxazole compounds such as ethyl-5-phenylisoxazole-3°-sulfonate and 5,5°-(varaphenylene)bisisoxazole.
■クロム明ばん、酢酸クロム、ホウ酸ジルコニウム塩の
如き無機系化合物。■Inorganic compounds such as chromium alum, chromium acetate, and zirconium borate.
■Ｎ−カルボエトキシー２−イソプロポキシ−１，２−
ジヒドロキノリン、Ｎ−（１−モルホリノカルボキシ）
−４−メチルピリジニウムクロリドの如き脱水縮合型ペ
プチド試薬、Ｎ、Ｎ″−アジボイルジオキシジサクシン
イミド、Ｎ、Ｎ’テレフタロイルジオキシジサクシンイ
ミドの如き活性エステル系化合物。■N-carboethoxy-2-isopropoxy-1,2-
Dihydroquinoline, N-(1-morpholinocarboxy)
Dehydration condensation type peptide reagents such as -4-methylpyridinium chloride; active ester compounds such as N,N''-aziboyldioxydisuccinimide and N,N'terephthaloyldioxydisuccinimide.
［相］トルエンー２．４−ジイソシアネート、１゜６−
へキサメチレンジイソシアネートの如きイソシアネート
類。[Phase] Toluene-2.4-diisocyanate, 1°6-
Isocyanates such as hexamethylene diisocyanate.
０グルタルアルデヒド、グリオキザール、ジメトキシ尿
素、２，３−ヒドロキシ−１，４−ジオキサン等のジア
ルデヒド類。0 Dialdehydes such as glutaraldehyde, glyoxal, dimethoxyurea, and 2,3-hydroxy-1,4-dioxane.
これらのうち、特に、グルタルアルデヒド、２゜３−ジ
ヒドロキシ−１，４−ジオキサン等のジアルデヒド類及
びホウ酸が好ましい。Among these, dialdehydes such as glutaraldehyde and 2°3-dihydroxy-1,4-dioxane, and boric acid are particularly preferred.
これらの硬膜剤の添加量は、下塗素材の重量に対して、
０．２０重量％から３．０重量％の範囲で、塗布方法や
希望の硬化度に合わせて適切な添加量を選ぶことができ
る。The amount of these hardeners added is based on the weight of the base coat material.
An appropriate addition amount can be selected in the range of 0.20% by weight to 3.0% by weight depending on the coating method and desired degree of curing.
添加量が０．２０重量％より少ないといくら経時させて
も硬化度が不足し、感熱層の塗布時に下塗層が膨潤する
欠点を有し、又逆に、３．０重量％よりも多いと硬化度
が進みすぎ、下塗層と支持体との接着がかえって悪化し
、下塗層が膜状になって支持体より剥離する欠点を有す
る。If the amount added is less than 0.20% by weight, the degree of curing will be insufficient no matter how long it is allowed to last, and the undercoat layer will swell when applying the heat-sensitive layer, and conversely, if it is more than 3.0% by weight. The problem is that the degree of curing progresses too much, the adhesion between the undercoat layer and the support worsens, and the undercoat layer becomes film-like and peels off from the support.
用いる硬化剤によっては、必要ならば、更に苛性ソーダ
を加えて、液のｐＨをアルカリ側にする事も、或いはク
エン酸等により液のｐＨを酸性側にする事もできる。Depending on the curing agent used, if necessary, the pH of the solution can be made alkaline by adding caustic soda, or the pH of the solution can be made acidic by using citric acid or the like.
又、塗布時に発生する泡を消すために、消泡剤を添加す
る事も、或いは、液のレベリングを良くして塗布筋の発
生を防止するために、活性剤を添加する事も可能である
。It is also possible to add an antifoaming agent to eliminate foam generated during coating, or to add an activator to improve liquid leveling and prevent coating streaks. .
又、必要に応じて、帯電防止剤を添加することも可能で
ある。Moreover, it is also possible to add an antistatic agent if necessary.
更に、下塗層を塗布する前に、支持体の表面を公知の方
法により活性化処理する事が望ましい。Furthermore, before applying the undercoat layer, it is desirable to activate the surface of the support by a known method.
活性化処理の方法としては、酸によるエツチング処理、
ガスバーナーによる火焔処理、或いはコロナ処理、グロ
ー放電処理等が用いられるが、コストの面或いは簡便さ
の点から、米国特許第２，７１５．０７５号、同第２，
８４６，７２７号、同第３．５４９，４０６号、同第３
，５９０，１０７号等に記載されたコロナ放電処理が最
も好んで用いられる。Activation treatment methods include acid etching treatment,
Flame treatment using a gas burner, corona treatment, glow discharge treatment, etc. are used, but from the point of view of cost or simplicity, U.S. Pat.
No. 846,727, No. 3.549,406, No. 3
, 590, 107, etc., is most preferably used.
（発明の効果）
本発明の感熱記録材料は、感熱層、保護層とも透明な上
、耐傷性、耐溶剤性、耐水性及び耐ステイツキング性に
優れているので、ＯＨＰはもとより、多色感熱記録材料
や、感熱ラベルへの応用に好適である。(Effects of the Invention) The heat-sensitive recording material of the present invention is transparent in both the heat-sensitive layer and the protective layer, and has excellent scratch resistance, solvent resistance, water resistance, and staining resistance. Suitable for application to recording materials and heat-sensitive labels.
（実施例）
以下、本発明を実施例により更に詳述するが、本発明は
これによって限定されるものではない。(Examples) Hereinafter, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited thereto.
クリスタルバイオレットラクトン１４ｇ（ロイコ色素）
、クケネー）Ｄ−１１ＯＮ （武田薬品■製カプセル壁
材）６０ｇ及びスミソーブ２００（住人化学■製紫外線
吸収剤）２ｇを１−フェニル−１−キシリルエタン５５
ｇと、メチレンクロライド５５ｇの混合溶媒に添加し、
溶解した。このロイコ染料の溶液を、８％のポリビニル
アルコール水溶液１００ｇと水４０ｇ及び２％のスルホ
コハク酸ジオクチルのナトリウム塩（分散剤）１゜４ｇ
の水溶液に混合し、日本精機■製の、エースホモジナイ
ザーでｔｏ、ＯＯＯｒｐｍで５分間乳化し、更Ｇこ水１
５０ｇを加えて、４０°Ｃで３時間反応させてカプセル
サイズ０． ７μのカプセル液を製造した。Crystal violet lactone 14g (leuco pigment)
, Kukene) 60 g of D-11ON (capsule wall material manufactured by Takeda Pharmaceutical ■) and 2 g of Sumisorb 200 (ultraviolet absorber manufactured by Jumen Kagaku ■) were mixed with 55 g of 1-phenyl-1-xylylethane.
g and 55 g of methylene chloride in a mixed solvent,
Dissolved. This leuco dye solution was mixed with 100 g of 8% polyvinyl alcohol aqueous solution, 40 g of water, and 1.4 g of 2% sodium salt of dioctyl sulfosuccinate (dispersing agent).
Mix with an aqueous solution of
Add 50g and react at 40°C for 3 hours until the capsule size is 0. A 7μ capsule solution was produced.
下記構造式で表わされる顕色剤（ａ）８ ｇ、 （ｂ）
４ ｇ、及び（ｃ） ３０ ｇをノーフェニル−１−キ
シリルエタン８ｇと酢酸エチル３０ｇに溶解した。得ら
れた顕色剤の溶液を、８％のポリビニルアルコール水溶
液１００ｇと水１５０ｇ、及びドデシルベンゼンスルホ
ン酸ソーダ０．５ｇの水溶液に混合し、日本精機■製の
エースホモジナイザーを用いて、１０、ＯＯＯｙｐｍ常
温で５分間乳化し、粒子サイズ０．５μの乳化分散物を
得た。Color developer represented by the following structural formula (a) 8 g, (b)
4 g and 30 g of (c) were dissolved in 8 g of nophenyl-1-xylylethane and 30 g of ethyl acetate. The obtained developer solution was mixed with an aqueous solution of 100 g of 8% polyvinyl alcohol aqueous solution, 150 g of water, and 0.5 g of sodium dodecylbenzenesulfonate, and was mixed with an aqueous solution of 10,000 ypm using an Ace homogenizer manufactured by Nippon Seiki ■. Emulsification was carried out for 5 minutes at room temperature to obtain an emulsified dispersion with a particle size of 0.5 μm.
顕色剤（ａ）
顕色剤（ｂ）
／
／
／
〔感熱記録材料の作製〕
上記カプセル液５．０ｇ、顕色剤乳化分散物１０．０ｇ
、及び水５．０ｇを撹拌混合し、厚さ７５μの透明なポ
リエチレンテレフタレート（ＰＥＴ）支持体の片面に、
固形分が１５ｇ／ｍ”になるように塗布し乾燥して感熱
層を形成させ、次いで、下記組成の保護層を感熱層の上
に厚さ２μとなるように形成させて感熱記録材料を作製
した。Color developer (a) Color developer (b) / / / [Preparation of heat-sensitive recording material] 5.0 g of the above capsule liquid, 10.0 g of color developer emulsion dispersion
, and 5.0 g of water were stirred and mixed, and the mixture was coated on one side of a transparent polyethylene terephthalate (PET) support with a thickness of 75 μm.
A heat-sensitive recording material was prepared by applying the product to a solid content of 15 g/m'' and drying to form a heat-sensitive layer, and then forming a protective layer having the following composition on the heat-sensitive layer to a thickness of 2 μm. did.
〔保護層の組成］
シリカ変性ポリビニルアルコール（−クラレ製Ｒ２１０
５） １重量部（固形分）コロイダルシリ
カ（日産化学■製スノーテックス３０）
１．５重量部（固形分）パラフィンワックスエマル
ジョン（中東油脂■製セロゾール４２８） ０．３重
量部（固形分）ポリ４フツ化エチレン粒子（ダイキン工
業■製ポリフロンＤ−１） ０．５重量部（固形分
）得られた感熱記録材料を３０゛Ｃ１相対湿度８５％の
環境下で、スティッキングの発生し易いＧＩ［Ｉモード
のファクシミリで印字したところ、ちぢみやとびが殆ど
なく、良好に印字が行われた。[Composition of protective layer] Silica-modified polyvinyl alcohol (-Kuraray R210
5) 1 part by weight (solid content) colloidal silica (Snowtex 30 manufactured by Nissan Chemical ■)
1.5 parts by weight (solid content) Paraffin wax emulsion (Cellosol 428 manufactured by Middle East Oil Company) 0.3 parts by weight (solid content) Polytetrafluoroethylene particles (Polyflon D-1 manufactured by Daikin Industries ■) 0.5 parts by weight (Solid content) The obtained heat-sensitive recording material was printed in an environment of 30゛C1 relative humidity of 85% using a GI [I mode facsimile machine in which sticking is likely to occur. It was conducted.
比較例。Comparative example.
４−弗化エチレン粒子を使用しなかった他は、実施例１
と全く同様にして感熱記録材料を得、同様に印字テスト
を行ったところ、ちぢみやとびが多発した。4-Example 1 except that fluorinated ethylene particles were not used.
When a heat-sensitive recording material was obtained in exactly the same manner as above and a printing test was conducted in the same manner, there were many occurrences of shrinkage and skipping.
これらの実施例及び比較例の結果は、保護層に弗素系高
分子を入れたことにより、透明感熱記録材料のスティッ
キングを透明性を劣化させることなく著しく改善するこ
とができることを実証するものである。The results of these Examples and Comparative Examples demonstrate that by incorporating a fluorine-based polymer into the protective layer, the sticking of transparent heat-sensitive recording materials can be significantly improved without deteriorating the transparency. .
Claims (1)
淡色の電子供与性染料前駆体を含有するマイクロカプセ
ル、及び、水に難溶又は不溶の有機溶剤に溶解せしめた
顕色剤を乳化分散し得られた乳化分散物とを含む塗布液
を塗布乾燥して形成せしめた透明感熱層、並びに該透明
感熱層の上に設けられた弗素系高分子を含む保護層から
なることを特徴とする感熱記録材料。1) Emulsify at least a support, microcapsules containing a colorless or light-colored electron-donating dye precursor on one side of the support, and a color developer dissolved in an organic solvent that is sparingly soluble or insoluble in water. It is characterized by comprising a transparent heat-sensitive layer formed by applying and drying a coating solution containing an emulsified dispersion obtained by dispersion, and a protective layer containing a fluorine-based polymer provided on the transparent heat-sensitive layer. heat-sensitive recording material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63265714A JPH02111585A (en) | 1988-10-20 | 1988-10-20 | Thermal recording material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63265714A JPH02111585A (en) | 1988-10-20 | 1988-10-20 | Thermal recording material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH02111585A true JPH02111585A (en) | 1990-04-24 |
Family
ID=17420991
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63265714A Pending JPH02111585A (en) | 1988-10-20 | 1988-10-20 | Thermal recording material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02111585A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003039852A (en) * | 2001-07-31 | 2003-02-13 | Horizon International Inc | Cover for coil binding and coil-bound booklet with the cover |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62251187A (en) * | 1986-04-25 | 1987-10-31 | Fuji Photo Film Co Ltd | Thermal recording material |
| JPS6392489A (en) * | 1986-10-08 | 1988-04-22 | Fuji Photo Film Co Ltd | Thermal recording material |
-
1988
- 1988-10-20 JP JP63265714A patent/JPH02111585A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62251187A (en) * | 1986-04-25 | 1987-10-31 | Fuji Photo Film Co Ltd | Thermal recording material |
| JPS6392489A (en) * | 1986-10-08 | 1988-04-22 | Fuji Photo Film Co Ltd | Thermal recording material |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003039852A (en) * | 2001-07-31 | 2003-02-13 | Horizon International Inc | Cover for coil binding and coil-bound booklet with the cover |
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| Publication | Publication Date | Title |
|---|---|---|
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