JP7392641B2 - Transparent heat-sensitive recording material - Google Patents
Transparent heat-sensitive recording material Download PDFInfo
- Publication number
- JP7392641B2 JP7392641B2 JP2020217731A JP2020217731A JP7392641B2 JP 7392641 B2 JP7392641 B2 JP 7392641B2 JP 2020217731 A JP2020217731 A JP 2020217731A JP 2020217731 A JP2020217731 A JP 2020217731A JP 7392641 B2 JP7392641 B2 JP 7392641B2
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- JP
- Japan
- Prior art keywords
- parts
- protective layer
- recording material
- sensitive recording
- manufactured
- 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.)
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- MHDVGSVTJDSBDK-UHFFFAOYSA-N dibenzyl ether Chemical compound C=1C=CC=CC=1COCC1=CC=CC=C1 MHDVGSVTJDSBDK-UHFFFAOYSA-N 0.000 description 1
- 238000007607 die coating method Methods 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical class OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- WASQWSOJHCZDFK-UHFFFAOYSA-N diketene Chemical compound C=C1CC(=O)O1 WASQWSOJHCZDFK-UHFFFAOYSA-N 0.000 description 1
- OEIWPNWSDYFMIL-UHFFFAOYSA-N dioctyl benzene-1,4-dicarboxylate Chemical compound CCCCCCCCOC(=O)C1=CC=C(C(=O)OCCCCCCCC)C=C1 OEIWPNWSDYFMIL-UHFFFAOYSA-N 0.000 description 1
- CZZYITDELCSZES-UHFFFAOYSA-N diphenylmethane Chemical compound C=1C=CC=CC=1CC1=CC=CC=C1 CZZYITDELCSZES-UHFFFAOYSA-N 0.000 description 1
- YHAIUSTWZPMYGG-UHFFFAOYSA-L disodium;2,2-dioctyl-3-sulfobutanedioate Chemical compound [Na+].[Na+].CCCCCCCCC(C([O-])=O)(C(C([O-])=O)S(O)(=O)=O)CCCCCCCC YHAIUSTWZPMYGG-UHFFFAOYSA-L 0.000 description 1
- UQGFMSUEHSUPRD-UHFFFAOYSA-N disodium;3,7-dioxido-2,4,6,8,9-pentaoxa-1,3,5,7-tetraborabicyclo[3.3.1]nonane Chemical compound [Na+].[Na+].O1B([O-])OB2OB([O-])OB1O2 UQGFMSUEHSUPRD-UHFFFAOYSA-N 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- OJLOUXPPKZRTHK-UHFFFAOYSA-N dodecan-1-ol;sodium Chemical compound [Na].CCCCCCCCCCCCO OJLOUXPPKZRTHK-UHFFFAOYSA-N 0.000 description 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- 238000002296 dynamic light scattering Methods 0.000 description 1
- 150000002169 ethanolamines Chemical class 0.000 description 1
- MFGZXPGKKJMZIY-UHFFFAOYSA-N ethyl 5-amino-1-(4-sulfamoylphenyl)pyrazole-4-carboxylate Chemical compound NC1=C(C(=O)OCC)C=NN1C1=CC=C(S(N)(=O)=O)C=C1 MFGZXPGKKJMZIY-UHFFFAOYSA-N 0.000 description 1
- 235000010944 ethyl methyl cellulose Nutrition 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000001046 green dye Substances 0.000 description 1
- 238000009499 grossing Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 1
- 229920003063 hydroxymethyl cellulose Polymers 0.000 description 1
- 229940031574 hydroxymethyl cellulose Drugs 0.000 description 1
- 239000001863 hydroxypropyl cellulose Substances 0.000 description 1
- 235000010977 hydroxypropyl cellulose Nutrition 0.000 description 1
- 239000001866 hydroxypropyl methyl cellulose Chemical class 0.000 description 1
- 229920003088 hydroxypropyl methyl cellulose Chemical class 0.000 description 1
- 235000010979 hydroxypropyl methyl cellulose Nutrition 0.000 description 1
- UFVKGYZPFZQRLF-UHFFFAOYSA-N hydroxypropyl methyl cellulose Chemical class OC1C(O)C(OC)OC(CO)C1OC1C(O)C(O)C(OC2C(C(O)C(OC3C(C(O)C(O)C(CO)O3)O)C(CO)O2)O)C(CO)O1 UFVKGYZPFZQRLF-UHFFFAOYSA-N 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 229920006276 ketonic resin Polymers 0.000 description 1
- 238000007561 laser diffraction method Methods 0.000 description 1
- HGPXWXLYXNVULB-UHFFFAOYSA-M lithium stearate Chemical compound [Li+].CCCCCCCCCCCCCCCCCC([O-])=O HGPXWXLYXNVULB-UHFFFAOYSA-M 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 159000000003 magnesium salts Chemical class 0.000 description 1
- 235000019359 magnesium stearate Nutrition 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- ZSYJMXLJNPEAGP-UHFFFAOYSA-N methyl n-cyanocarbamate Chemical compound COC(=O)NC#N ZSYJMXLJNPEAGP-UHFFFAOYSA-N 0.000 description 1
- 235000010270 methyl p-hydroxybenzoate Nutrition 0.000 description 1
- 229920003087 methylethyl cellulose Chemical class 0.000 description 1
- 239000003094 microcapsule Substances 0.000 description 1
- 239000004200 microcrystalline wax Substances 0.000 description 1
- 235000019808 microcrystalline wax Nutrition 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- VYQNWZOUAUKGHI-UHFFFAOYSA-N monobenzone Chemical compound C1=CC(O)=CC=C1OCC1=CC=CC=C1 VYQNWZOUAUKGHI-UHFFFAOYSA-N 0.000 description 1
- 229960000990 monobenzone Drugs 0.000 description 1
- RQAQWBFHPMSXKR-UHFFFAOYSA-N n-(4-chlorophenyl)-3-(phosphonooxy)naphthalene-2-carboxamide Chemical compound OP(O)(=O)OC1=CC2=CC=CC=C2C=C1C(=O)NC1=CC=C(Cl)C=C1 RQAQWBFHPMSXKR-UHFFFAOYSA-N 0.000 description 1
- MJGLMEMIYDUEHA-UHFFFAOYSA-N n-(4-methylphenyl)-3-oxobutanamide Chemical compound CC(=O)CC(=O)NC1=CC=C(C)C=C1 MJGLMEMIYDUEHA-UHFFFAOYSA-N 0.000 description 1
- FTQWRYSLUYAIRQ-UHFFFAOYSA-N n-[(octadecanoylamino)methyl]octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCNC(=O)CCCCCCCCCCCCCCCCC FTQWRYSLUYAIRQ-UHFFFAOYSA-N 0.000 description 1
- HETBCUMLBCUVKC-UHFFFAOYSA-N n-[2-(dodecanoylamino)ethyl]dodecanamide Chemical compound CCCCCCCCCCCC(=O)NCCNC(=O)CCCCCCCCCCC HETBCUMLBCUVKC-UHFFFAOYSA-N 0.000 description 1
- LCZJLVYYBRTSAQ-UHFFFAOYSA-N n-[4-(octadecanoylamino)butyl]octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCCCCNC(=O)CCCCCCCCCCCCCCCCC LCZJLVYYBRTSAQ-UHFFFAOYSA-N 0.000 description 1
- SLZWSYPJQQIDJB-UHFFFAOYSA-N n-[6-(octadecanoylamino)hexyl]octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCCCCCCNC(=O)CCCCCCCCCCCCCCCCC SLZWSYPJQQIDJB-UHFFFAOYSA-N 0.000 description 1
- OSJJOWRIYDWQPO-UHFFFAOYSA-N n-[[2-[(octadecanoylamino)methyl]phenyl]methyl]octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCC1=CC=CC=C1CNC(=O)CCCCCCCCCCCCCCCCC OSJJOWRIYDWQPO-UHFFFAOYSA-N 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- DVVFBRPYROBXHJ-UHFFFAOYSA-N n-octadecanoylbenzamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NC(=O)C1=CC=CC=C1 DVVFBRPYROBXHJ-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- FATBGEAMYMYZAF-KTKRTIGZSA-N oleamide Chemical compound CCCCCCCC\C=C/CCCCCCCC(N)=O FATBGEAMYMYZAF-KTKRTIGZSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 229950005308 oxymethurea Drugs 0.000 description 1
- 229910052625 palygorskite Inorganic materials 0.000 description 1
- 235000019809 paraffin wax Nutrition 0.000 description 1
- 235000019271 petrolatum Nutrition 0.000 description 1
- CPJSUEIXXCENMM-UHFFFAOYSA-N phenacetin Chemical compound CCOC1=CC=C(NC(C)=O)C=C1 CPJSUEIXXCENMM-UHFFFAOYSA-N 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- QHDYIMWKSCJTIM-UHFFFAOYSA-N phenyl 1-hydroxynaphthalene-2-carboxylate Chemical compound C1=CC2=CC=CC=C2C(O)=C1C(=O)OC1=CC=CC=C1 QHDYIMWKSCJTIM-UHFFFAOYSA-N 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 229920002647 polyamide Chemical class 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920005990 polystyrene resin Polymers 0.000 description 1
- 159000000001 potassium salts Chemical class 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 235000010232 propyl p-hydroxybenzoate Nutrition 0.000 description 1
- QELSKZZBTMNZEB-UHFFFAOYSA-N propylparaben Chemical compound CCCOC(=O)C1=CC=C(O)C=C1 QELSKZZBTMNZEB-UHFFFAOYSA-N 0.000 description 1
- 229960003415 propylparaben Drugs 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000005871 repellent Substances 0.000 description 1
- 230000002940 repellent Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 230000008313 sensitization Effects 0.000 description 1
- 235000010413 sodium alginate Nutrition 0.000 description 1
- 239000000661 sodium alginate Substances 0.000 description 1
- 229940005550 sodium alginate Drugs 0.000 description 1
- APSBXTVYXVQYAB-UHFFFAOYSA-M sodium docusate Chemical compound [Na+].CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC APSBXTVYXVQYAB-UHFFFAOYSA-M 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 229940037312 stearamide Drugs 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- FRKHZXHEZFADLA-UHFFFAOYSA-L strontium;octadecanoate Chemical compound [Sr+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O FRKHZXHEZFADLA-UHFFFAOYSA-L 0.000 description 1
- 239000011115 styrene butadiene Substances 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 150000003585 thioureas Chemical class 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- KAKZBPTYRLMSJV-UHFFFAOYSA-N vinyl-ethylene Natural products C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 1
- 239000004034 viscosity adjusting agent Substances 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 229920003170 water-soluble synthetic polymer Polymers 0.000 description 1
- 238000004078 waterproofing Methods 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- LPEBYPDZMWMCLZ-CVBJKYQLSA-L zinc;(z)-octadec-9-enoate Chemical compound [Zn+2].CCCCCCCC\C=C/CCCCCCCC([O-])=O.CCCCCCCC\C=C/CCCCCCCC([O-])=O LPEBYPDZMWMCLZ-CVBJKYQLSA-L 0.000 description 1
- MLVWCBYTEFCFSG-UHFFFAOYSA-L zinc;dithiocyanate Chemical compound [Zn+2].[S-]C#N.[S-]C#N MLVWCBYTEFCFSG-UHFFFAOYSA-L 0.000 description 1
Landscapes
- Heat Sensitive Colour Forming Recording (AREA)
Description
本発明は、ロイコ染料と呈色剤との発色反応を利用した透明感熱記録体に関するものである。 The present invention relates to a transparent thermosensitive recording material that utilizes a color-forming reaction between a leuco dye and a coloring agent.
ロイコ染料と呈色剤との発色反応を利用した感熱記録体は比較的安価であり、記録機器がコンパクトで、且つその保守も容易であるため、ファクシミリ、各種計算機、ＣＡＤ用プロッター等の記録媒体としてのみならず、超音波画像診断用、Ｘ線画像診断用、ＮＭＲ断層画像診断用等の医療用機器の記録媒体としても使用されている。 Thermosensitive recording materials that utilize the color reaction between leuco dyes and coloring agents are relatively inexpensive, and the recording equipment is compact and easy to maintain, so they are widely used as recording media in facsimiles, various calculators, CAD plotters, etc. It is also used as a recording medium for medical equipment such as ultrasonic image diagnosis, X-ray image diagnosis, and NMR tomographic image diagnosis.
中でも、医療診断用途であるシャウカステン用の感熱記録体は、高い透明性と記録濃度が必要とされている。 Among these, heat-sensitive recording materials for Schaukasten, which are used for medical diagnosis, are required to have high transparency and recording density.
そのため、医療用機器の記録媒体として使用される感熱記録体は、サーマルヘッドで印加する熱エネルギーが大きくなり、記録時にスティッキングや騒音が発生し易くなる。このような問題を改善する観点から、感熱記録層上には一般的に保護層が設けられる。 Therefore, in a thermal recording medium used as a recording medium for medical equipment, the thermal energy applied by the thermal head is large, and sticking and noise are likely to occur during recording. From the viewpoint of improving such problems, a protective layer is generally provided on the heat-sensitive recording layer.
一般に、スティッキングを効果的に抑制させるために、感熱記録体の最上層中に５質量％以上の炭酸カルシウムを配合することが提案されている（特許文献１）。また、透明な感熱記録体について、透明性を向上させるために、感熱記録層上のトップコート層中に、充填剤として粒子径の小さいコロイダルシリカを配合することが提案されている（特許文献２）。 Generally, in order to effectively suppress sticking, it has been proposed to incorporate 5% by mass or more of calcium carbonate into the uppermost layer of a heat-sensitive recording material (Patent Document 1). Furthermore, in order to improve the transparency of transparent heat-sensitive recording materials, it has been proposed to incorporate colloidal silica with a small particle size as a filler into the top coat layer on the heat-sensitive recording layer (Patent Document 2). ).
しかしながら、このような無機顔料を透明感熱記録体の保護層（オーバーコート層）に用いた場合には、サーマルヘッドの摩耗が生じるという問題がある。そのため、スティッキングの抑制に加えて、サーマルヘッドの摩耗が起き難い透明感熱記録体が強く求められている。 However, when such an inorganic pigment is used in a protective layer (overcoat layer) of a transparent thermosensitive recording material, there is a problem in that the thermal head is abraded. Therefore, in addition to suppressing sticking, there is a strong demand for a transparent thermosensitive recording material that is less likely to cause abrasion of the thermal head.
本発明は、サーマルヘッドの摩耗を抑制し、耐スティッキング性にも優れる透明感熱記録体を提供することを主な目的とする。 The main object of the present invention is to provide a transparent thermosensitive recording material that suppresses wear of a thermal head and has excellent sticking resistance.
本発明者らは、上記目的を解決すべく鋭意検討を重ねた結果、保護層中に接着剤を保護層の全固形量中６０質量％以上の割合で含有させ、滑剤としてアルキルリン酸エステル塩を配合することにより、上記課題が解決されることを見出し、本発明を解決するに至った。すなわち、本発明は、下記の透明感熱記録体に係る。 As a result of intensive studies to solve the above object, the present inventors have found that the protective layer contains an adhesive at a ratio of 60% by mass or more based on the total solid amount of the protective layer, and an alkyl phosphate ester salt is used as a lubricant. It has been found that the above problems can be solved by blending the above, and the present invention has been achieved. That is, the present invention relates to the following transparent thermosensitive recording material.
項１．透明支持体の一方の面に、ロイコ染料及び呈色剤を含有する少なくとも１層の感熱記録層、並びに接着剤及び滑剤を含有する保護層をこの順に有する透明感熱記録体であって、
前記接着剤の含有割合が保護層の全固形量中６０質量％以上であり、
前記滑剤として少なくともアルキルリン酸エステル塩を含有する
透明感熱記録体。
項２．前記アルキルリン酸エステル塩の含有割合が、保護層の全固形量中０．５～２０質量％である、項１に記載の透明感熱記録体。
項３．前記保護層中に顔料を含有しない、項１又は２に記載の透明感熱記録体。
項４．前記滑剤としてステアリン酸塩を更に含有し、前記ステアリン酸塩の含有割合が保護層の全固形量中１．０～１０質量％である、項１～３のいずれか一項に記載の透明感熱記録体。
項５．前記滑剤としてＮ置換脂肪酸アミドを更に含有し、前記Ｎ置換脂肪酸アミドの含有割合が保護層の全固形量中１．０～１０質量％である、項４に記載の透明感熱記録体。
項６．前記保護層に含有される前記接着剤が、ポリビニルアルコール、変性ポリビニルアルコール、ポリウレタン樹脂、及びアクリル樹脂からなる群から選ばれる少なくとも１種を含有する、項１～５のいずれか一項に記載の透明感熱記録体。
Item 1. A transparent thermosensitive recording material having, on one side of a transparent support, at least one thermosensitive recording layer containing a leuco dye and a coloring agent, and a protective layer containing an adhesive and a lubricant in this order,
The content of the adhesive is 60% by mass or more in the total solid amount of the protective layer,
A transparent thermosensitive recording material containing at least an alkyl phosphate ester salt as the lubricant.
Item 2. Item 2. The transparent heat-sensitive recording material according to item 1, wherein the content of the alkyl phosphate ester salt is 0.5 to 20% by mass based on the total solid amount of the protective layer.
Item 3. Item 3. The transparent thermosensitive recording material according to item 1 or 2, wherein the protective layer does not contain a pigment.
Item 4. 4. The transparent thermosensitive material according to any one of Items 1 to 3, further comprising a stearate as the lubricant, and the content of the stearate is 1.0 to 10% by mass based on the total solid amount of the protective layer. record body.
Item 5. Item 5. The transparent thermosensitive recording material according to Item 4, further comprising an N-substituted fatty acid amide as the lubricant, and the content of the N-substituted fatty acid amide is 1.0 to 10% by mass based on the total solid amount of the protective layer.
Item 6. Item 5. The adhesive contained in the protective layer contains at least one selected from the group consisting of polyvinyl alcohol, modified polyvinyl alcohol, polyurethane resin, and acrylic resin. Transparent heat-sensitive recording material.
本発明の透明感熱記録体は、サーマルヘッドの摩耗を抑制し、耐スティッキング性にも優れる。 The transparent thermosensitive recording material of the present invention suppresses wear of the thermal head and has excellent sticking resistance.
本明細書中において、「含む、含有する」なる表現については、「含む」、「実質のみからなる」、及び「のみからなる」旨の概念を含む。 In this specification, the expression "comprising" includes the concepts of "containing", "consisting only of substance", and "consisting only".
本明細書において「～」を用いて表される数値範囲は、「～」前後に記載される数値を下限値及び上限値として含む範囲を意味する。 In this specification, a numerical range expressed using "~" means a range that includes the numerical values written before and after "~" as lower and upper limits.
また、本発明では「平均粒子径」は、レーザー回析法によって測定される体積基準のメジアン径をいう。より簡単には、電子顕微鏡を使用し、粒子画像（ＳＥＭ画像）から粒子径をそれぞれ測定し、１０個の平均値で示しても構わない。 Furthermore, in the present invention, the "average particle diameter" refers to the volume-based median diameter measured by laser diffraction. More simply, the particle diameter may be measured from each particle image (SEM image) using an electron microscope, and the average value of 10 values may be shown.
本発明は、透明支持体の一方の面に、ロイコ染料及び呈色剤を含有する少なくとも１層の感熱記録層、並びに接着剤及び滑剤を含有する保護層をこの順に有する透明感熱記録体であって、
前記接着剤の含有割合が保護層の全固形量中６０質量％以上であり、
前記滑剤として少なくともアルキルリン酸エステル塩を含有する
ことを特徴とする。
The present invention provides a transparent heat-sensitive recording material having, on one side of a transparent support, at least one heat-sensitive recording layer containing a leuco dye and a coloring agent, and a protective layer containing an adhesive and a lubricant in this order. hand,
The content of the adhesive is 60% by mass or more in the total solid amount of the protective layer,
It is characterized in that it contains at least an alkyl phosphate ester salt as the lubricant.
［透明支持体］
透明支持体としては、限定的でないが、例えば厚さ３０～３００μｍ程度の二軸延伸されたポリエチレンテレフタレートフィルム（ＰＥＴフィルム）、ポリプロピレンフィルム、ポリスチレンフィルム、塩化ビニルフィルム等が挙げられる。
[Transparent support]
Examples of the transparent support include, but are not limited to, biaxially stretched polyethylene terephthalate film (PET film), polypropylene film, polystyrene film, vinyl chloride film, etc. having a thickness of about 30 to 300 μm.
また、透明支持体は着色体又は無着色体のいずれであってもよい。支持体が無着色フィルムである場合、感熱記録層及び保護層の少なくとも１層を着色してもよい。 Moreover, the transparent support may be either a colored body or an uncolored body. When the support is an uncolored film, at least one of the heat-sensitive recording layer and the protective layer may be colored.
透明支持体は、コロナ放電処理や導電剤による導電処理を施したものであってもよい。 The transparent support may be one that has been subjected to a corona discharge treatment or a conductive treatment using a conductive agent.
［感熱記録層］
本発明の感熱記録体における感熱記録層には、無色又は淡色の各種公知のロイコ染料を含有させることができる。そのようなロイコ染料の具体例を以下に挙げる。
[Thermosensitive recording layer]
The heat-sensitive recording layer of the heat-sensitive recording material of the present invention can contain various known colorless or light-colored leuco dyes. Specific examples of such leuco dyes are listed below.
ロイコ染料の具体例としては、例えば、３，３－ビス（ｐ－ジメチルアミノフェニル）－６－ジメチルアミノフタリド、３－（４－ジエチルアミノ－２－メチルフェニル）－３－（４－ジメチルアミノフェニル）－６－ジメチルアミノフタリド、フルオラン等の青発色性染料、３－（Ｎ－エチル－Ｎ－ｐ－トリル）アミノ－７－Ｎ－メチルアニリノフルオラン、３－ジエチルアミノ－７－アニリノフルオラン、３－ジエチルアミノ－７－ジベンジルアミノフルオラン、ローダミンＢ－アニリノラクタム等の緑発色性染料、３，６－ビス（ジエチルアミノ）フルオラン－γ－アニリノラクタム、３－シクロヘキシルアミノ－６－クロロフルオラン、３－ジエチルアミノ－６－メチル－７－クロロフルオラン、３－ジエチルアミノ－７－クロロフルオラン等の赤発色性染料、３－（Ｎ－エチル－Ｎ－イソアミル）アミノ－６－メチル－７－アニリノフルオラン、３－（Ｎ－メチル－Ｎ－シクロヘキシル）アミノ－６－メチル－７－アニリノフルオラン、３－ジエチルアミノ－６－メチル－７－アニリノフルオラン、３－ジ（ｎ－ブチル）アミノ－６－メチル－７－アニリノフルオラン、３－ジ（ｎ－ペンチル）アミノ－６－メチル－７－アニリノフルオラン、３－（Ｎ－エチル－Ｎ－イソアミルアミノ）－６－メチル－７－アリニノフルオラン、３－ジエチルアミノ－７－（ｍ－トリフルオロメチルアニリノ）フルオラン、３－（Ｎ－イソアミル－Ｎ－エチルアミノ）－７－（ｏ－クロロアニリノ）フルオラン、３－（Ｎ－エチル－Ｎ－２－テトラヒドロフルフリルアミノ）－６－メチル－７－アニリノフルオラン、３－（Ｎ－ｎ－ヘキシル－Ｎ－エチルアミノ）－６－メチル－７－アニリノフルオラン、３－〔Ｎ－（３－エトキシプロピル）－Ｎ－エチルアミノ〕－６－メチル－７－アニリノフルオラン、３－〔Ｎ－（３－エトキシプロピル）－Ｎ－メチルアミノ〕－６－メチル－７－アニリノフルオラン、３－ジエチルアミノ－７－（２－クロロアニリノ）フルオラン、３－ジ（ｎ－ブチルアミノ）－７－（２－クロロアニリノ）フルオラン、４，４’－ビス－ジメチルアミノベンズヒドリンベンジルエーテル、Ｎ－２，４，５－トリクロロフェニルロイコオーラミン、３－ジエチルアミノ－７－ブチルアミノフルオラン、３－エチル－トリルアミノ－６－メチル－７－アニリノフルオラン、３－シクロヘキシル－メチルアミノ－６－メチル－７－アニリノフルオラン、３－ジエチルアミノ－６－クロロ－７－（β－エトキシエチル）アミノフルオラン、３－ジエチルアミノ－６－クロロ－７－（γ－クロロプロピル）アミノフルオラン、３－ジエチルアミノ－６－メチル－７－アニリノフルオラン、３－（Ｎ－イソアミル－Ｎ－エチルアミノ）－６－メチル－７－アニリノフルオラン、３－ジブチルアミノ－７－クロロアニリノフルオラン、３－ジエチルアミノ－７－（ｏ－クロロフェニルアミノ）フルオラン、３－（Ｎ－エチル－ｐ－トルイジノ）－６－メチル－７－アニリノフルオラン、３－（Ｎ－エチル－ｐ－トルイジノ）－６－メチル－７－（ｐ－トルイジノ）フルオラン、３－（Ｎ－エチル－Ｎ－テトラヒドロフルフリルアミノ）－６－メチル－７－アニリノフルオラン、３－ジエチルアミノ－６－クロロ－７－アニリノフルオラン、３－ジメチルアミノ－６－メチル－７－アニリノフルオラン、３－ピロリジノ－６－メチル－７－アニリノフルオラン、３－ピペリジノ－６－メチル－７－アニリノフルオラン、２，２－ビス｛４－〔６’－（Ｎ－シクロヘキシル－Ｎ－メチルアミノ）－３’－メチルスピロ〔フタリド－３，９’－キサンテン〕－２’－イルアミノ〕フェニル｝プロパン、３－ジエチルアミノ－７－（３’－トリフルオロメチルフェニル）アミノフルオラン等の黒発色性染料、３，３－ビス〔１－（４－メトキシフェニル）－１－（４－ジメチルアミノフェニル）エチレン－２－イル〕－４，５，６，７－テトラクロロフタリド、３，３－ビス〔１－（４－メトキシフェニル）－１－（４－ピロリジノフェニル）エチレン－２－イル〕－４，５，６，７－テトラクロロフタリド、３－ｐ－（ｐ－ジメチルアミノアニリノ）アニリノ－６－メチル－７－クロロフルオラン、３－ｐ－（ｐ－クロロアニリノ）アニリノ－６－メチル－７－クロロフルオラン、３，６－ビス（ジメチルアミノ）フルオレン－９－スピロ－３’－（６’－ジメチルアミノ）フタリド等の近赤外領域に吸収波長を有する染料等が挙げられる。もちろん、これらに制限されるものではなく、また必要に応じて２種以上の化合物を併用することもできる。 Specific examples of leuco dyes include 3,3-bis(p-dimethylaminophenyl)-6-dimethylaminophthalide, 3-(4-diethylamino-2-methylphenyl)-3-(4-dimethylamino Phenyl)-6-dimethylaminophthalide, blue coloring dyes such as fluoran, 3-(N-ethyl-Np-tolyl)amino-7-N-methylanilinofluorane, 3-diethylamino-7-ani Green dyes such as linofluoran, 3-diethylamino-7-dibenzylaminofluoran, rhodamine B-anilinolactam, 3,6-bis(diethylamino)fluoran-γ-anilinolactam, 3-cyclohexylamino- Red coloring dyes such as 6-chlorofluoran, 3-diethylamino-6-methyl-7-chlorofluoran, 3-diethylamino-7-chlorofluoran, 3-(N-ethyl-N-isoamyl)amino-6 -Methyl-7-anilinofluorane, 3-(N-methyl-N-cyclohexyl)amino-6-methyl-7-anilinofluorane, 3-diethylamino-6-methyl-7-anilinofluorane, 3 -di(n-butyl)amino-6-methyl-7-anilinofluorane, 3-di(n-pentyl)amino-6-methyl-7-anilinofluorane, 3-(N-ethyl-N- isoamylamino)-6-methyl-7-alininofluorane, 3-diethylamino-7-(m-trifluoromethylanilino)fluorane, 3-(N-isoamyl-N-ethylamino)-7-(o- chloroanilino)fluorane, 3-(N-ethyl-N-2-tetrahydrofurfurylamino)-6-methyl-7-anilinofluorane, 3-(Nn-hexyl-N-ethylamino)-6-methyl -7-anilinofluorane, 3-[N-(3-ethoxypropyl)-N-ethylamino]-6-methyl-7-anilinofluorane, 3-[N-(3-ethoxypropyl)-N -Methylamino]-6-methyl-7-anilinofluoran, 3-diethylamino-7-(2-chloroanilino)fluoran, 3-di(n-butylamino)-7-(2-chloroanilino)fluoran, 4, 4'-bis-dimethylaminobenzhydrin benzyl ether, N-2,4,5-trichlorophenylleucoauramine, 3-diethylamino-7-butylaminofluorane, 3-ethyl-tolylamino-6-methyl-7- Anilinofluorane, 3-cyclohexyl-methylamino-6-methyl-7-anilinofluorane, 3-diethylamino-6-chloro-7-(β-ethoxyethyl)aminofluorane, 3-diethylamino-6-chloro -7-(γ-chloropropyl)aminofluorane, 3-diethylamino-6-methyl-7-anilinofluorane, 3-(N-isoamyl-N-ethylamino)-6-methyl-7-anilinofluoran Oran, 3-dibutylamino-7-chloroanilinofluorane, 3-diethylamino-7-(o-chlorophenylamino)fluorane, 3-(N-ethyl-p-toluidino)-6-methyl-7-anilinofluorane Oran, 3-(N-ethyl-p-toluidino)-6-methyl-7-(p-toluidino)fluorane, 3-(N-ethyl-N-tetrahydrofurfurylamino)-6-methyl-7-anilino Fluoran, 3-diethylamino-6-chloro-7-anilinofluoran, 3-dimethylamino-6-methyl-7-anilinofluoran, 3-pyrrolidino-6-methyl-7-anilinofluoran, 3 -piperidino-6-methyl-7-anilinofluorane, 2,2-bis{4-[6'-(N-cyclohexyl-N-methylamino)-3'-methylspiro[phthalide-3,9'-xanthene ]-2'-ylamino]phenyl}propane, black coloring dyes such as 3-diethylamino-7-(3'-trifluoromethylphenyl)aminofluorane, 3,3-bis[1-(4-methoxyphenyl) -1-(4-dimethylaminophenyl)ethylene-2-yl]-4,5,6,7-tetrachlorophthalide, 3,3-bis[1-(4-methoxyphenyl)-1-(4- pyrrolidinophenyl)ethylene-2-yl]-4,5,6,7-tetrachlorophthalide, 3-p-(p-dimethylaminoanilino)anilino-6-methyl-7-chlorofluorane, 3- Near-infrared rays such as p-(p-chloroanilino)anilino-6-methyl-7-chlorofluorane, 3,6-bis(dimethylamino)fluorene-9-spiro-3'-(6'-dimethylamino)phthalide, etc. Examples include dyes having an absorption wavelength in this region. Of course, the compounds are not limited to these, and two or more kinds of compounds can be used in combination if necessary.
かかるロイコ染料の含有割合は、特に制限されず、感熱記録層の全固形量中、３～３０質量％程度が好ましく、５～２５質量％程度がより好ましく、７～２５質量％程度が更に好ましい。３質量％以上とすることにより発色能力を高めて、印字濃度を向上できる。３０質量％以下とすることにより、耐熱性を向上できる。 The content ratio of such leuco dye is not particularly limited, and is preferably about 3 to 30% by mass, more preferably about 5 to 25% by mass, and even more preferably about 7 to 25% by mass, based on the total solid amount of the heat-sensitive recording layer. . By setting the content to 3% by mass or more, coloring ability can be enhanced and print density can be improved. Heat resistance can be improved by setting the content to 30% by mass or less.
呈色剤の具体例としては、例えば、４－ｔｅｒｔ－ブチルフェノール、４－アセチルフェノール、４－ｔｅｒｔ－オクチルフェノール、４，４’－ｓｅｃ－ブチリデンジフェノール、４－フェニルフェノール、４，４’－ジヒドロキシジフェニルメタン、４，４’－イソプロピリデンジフェノール、４，４’－シクロヘキシリデンジフェニル、４，４’－シクロヘキシリデンジフェノール、１，１－ビス（４－ヒドロキシフェニル）－エタン、１，１－ビス（４－ヒドロキシフェニル）－１－フェニルエタン、４，４’－ビス（ｐ－トリルスルホニルアミノカルボニルアミノ）ジフェニルメタン、１，１－ビス（４－ヒドロキシフェニル）シクロヘキサン、２，２’－ビス〔４－（４－ヒドロキシフェニル）フェノキシ〕ジエチルエーテル、４，４’－ジヒドロキシジフェニルスルフィド、４，４’－チオビス（３－メチル－６－ｔｅｒｔ－ブチルフェノール）、４，４’－ジヒドロキシジフェニルスルホン、２，４’－ジヒドロキシジフェニルスルホン、２，２－ビス（４－ヒドロキシフェニル）－４－メチルペンタン、２，４’－ジヒドロキシジフェニルスルホン、４－ヒドロキシ－４’－イソプロポキシジフェニルスルホン、４－ヒドロキシ－４’－ｎ－プロポキシジフェニルスルホン、４－ヒドロキシ－４’－アリルオキシジフェニルスルホン、４－ヒドロキシ－４’－ベンジルオキシジフェニルスルホン、３，３’－ジアリル－４，４’－ジヒドロキシジフェニルスルホン、ビス（ｐ－ヒドロキシフェニル）酢酸ブチル、ビス（ｐ－ヒドロキシフェニル）酢酸メチル、ヒドロキノンモノベンジルエーテル、ビス（３－アリル－４－ヒドロキシフェニル）スルホン、４－ヒドロキシ－４’－メチルジフェニルスルホン、４－アリルオキシ－４’－ヒドロキシジフェニルスルホン、３，４－ジヒドロキシフェニル－４’－メチルフェニルスルホン、４－ヒドロキシベンゾフェノン、４－ヒドロキシフタル酸ジメチル、４－ヒドロキシ安息香酸メチル、４－ヒドロキシ安息香酸プロピル、４－ヒドロキシ安息香酸－ｓｅｃ－ブチル、４－ヒドロキシ安息香酸フェニル、４－ヒドロキシ安息香酸ベンジル、４－ヒドロキシ安息香酸ベンジルエステル、４－ヒドロキシ安息香酸トリル、４－ヒドロキシ安息香酸クロロフェニル、４，４’－ジヒドロキシジフェニルエーテル等のフェノール性化合物、又は安息香酸、ｐ－クロロ安息香酸、ｐ－ｔｅｒｔ－ブチル安息香酸、トリクロル安息香酸、テレフタル酸、サリチル酸、３－ｔｅｒｔ－ブチルサリチル酸、３－イソプロピルサリチル酸、３－ベンジルサリチル酸、３－（α－メチルベンジル）サリチル酸、３，５－ジ－ｔｅｒｔ－ブチルサリチル酸、４－〔２－（ｐ－メトキシフェノキシ）エチルオキシ〕サリチル酸、４－〔３－（ｐ－トリルスルホニル）プロピルオキシ〕サリチル酸、５－〔ｐ－（２－ｐ－メトキシフェノキシエトキシ）クミル〕サリチル酸、４－〔３－（ｐ－トリルスルホニル）プロピルオキシ〕サリチル酸亜鉛等の芳香族カルボン酸、及びこれらフェノール性化合物、芳香族カルボン酸と例えば亜鉛、マグネシウム、アルミニウム、カルシウム、チタン、マンガン、スズ、ニッケル等の多価金属との塩、更にはチオシアン酸亜鉛のアンチピリン錯体、テレフタルアルデヒド酸と他の芳香族カルボン酸との複合亜鉛塩等の有機酸性物質、Ｎ－ｐ－トルエンスルホニル－Ｎ’－３－（ｐ－トルエンスルホニルオキシ）フェニルウレア、Ｎ－ｐ－トルエンスルホニル－Ｎ’－ｐ－ブトキシカルボニルフェニルウレア、Ｎ－ｐ－トリルスルホニル－Ｎ’－フェニルウレア、４，４’－ビス（ｐ－トルエンスルホニルアミノカルボニルアミノ）ジフェニルメタン、４，４’－ビス［（４－メチル－３－フェノキシカルボニルアミノフェニル）ウレイド］ジフェニルスルホン等のウレア化合物、Ｎ，Ｎ’－ジ－ｍ－クロロフェニルチオウレア等のチオ尿素化合物、Ｎ－（ｐ－トルエンスルホニル）カルバモイル酸ｐ－クミルフェニルエステル、Ｎ－（ｐ－トルエンスルホニル）カルバモイル酸ｐ－ベンジルオキシフェニルエステル、Ｎ－［２－（３－フェニルウレイド）フェニル］ベンゼンスルホンアミド、Ｎ－（ｏ－トルオイル）－ｐ－トルエンスルホアミド等の分子内に－ＳＯ２ＮＨ－結合を有する有機化合物、活性白土、アタパルジャイト、コロイダルシリカ、珪酸アルミニウム等の無機酸性物質等が挙げられる。 Specific examples of coloring agents include 4-tert-butylphenol, 4-acetylphenol, 4-tert-octylphenol, 4,4'-sec-butylidene diphenol, 4-phenylphenol, 4,4'-dihydroxy Diphenylmethane, 4,4'-isopropylidene diphenol, 4,4'-cyclohexylidene diphenyl, 4,4'-cyclohexylidene diphenol, 1,1-bis(4-hydroxyphenyl)-ethane, 1,1- Bis(4-hydroxyphenyl)-1-phenylethane, 4,4'-bis(p-tolylsulfonylaminocarbonylamino)diphenylmethane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 2,2'-bis[ 4-(4-hydroxyphenyl)phenoxy]diethyl ether, 4,4'-dihydroxydiphenyl sulfide, 4,4'-thiobis(3-methyl-6-tert-butylphenol), 4,4'-dihydroxydiphenyl sulfone, 2 , 4'-dihydroxydiphenylsulfone, 2,2-bis(4-hydroxyphenyl)-4-methylpentane, 2,4'-dihydroxydiphenylsulfone, 4-hydroxy-4'-isopropoxydiphenylsulfone, 4-hydroxy- 4'-n-propoxydiphenylsulfone, 4-hydroxy-4'-allyloxydiphenylsulfone, 4-hydroxy-4'-benzyloxydiphenylsulfone, 3,3'-diallyl-4,4'-dihydroxydiphenylsulfone, bis (p-hydroxyphenyl)butyl acetate, bis(p-hydroxyphenyl)methyl acetate, hydroquinone monobenzyl ether, bis(3-allyl-4-hydroxyphenyl)sulfone, 4-hydroxy-4'-methyldiphenylsulfone, 4- Allyloxy-4'-hydroxydiphenylsulfone, 3,4-dihydroxyphenyl-4'-methylphenylsulfone, 4-hydroxybenzophenone, dimethyl 4-hydroxyphthalate, methyl 4-hydroxybenzoate, propyl 4-hydroxybenzoate, 4 -sec-butyl hydroxybenzoate, phenyl 4-hydroxybenzoate, benzyl 4-hydroxybenzoate, benzyl 4-hydroxybenzoate, tolyl 4-hydroxybenzoate, chlorophenyl 4-hydroxybenzoate, 4,4'- Phenolic compounds such as dihydroxydiphenyl ether, or benzoic acid, p-chlorobenzoic acid, p-tert-butylbenzoic acid, trichlorobenzoic acid, terephthalic acid, salicylic acid, 3-tert-butylsalicylic acid, 3-isopropylsalicylic acid, 3-benzyl Salicylic acid, 3-(α-methylbenzyl)salicylic acid, 3,5-di-tert-butylsalicylic acid, 4-[2-(p-methoxyphenoxy)ethyloxy]salicylic acid, 4-[3-(p-tolylsulfonyl)propyl Aromatic carboxylic acids such as oxy]salicylic acid, 5-[p-(2-p-methoxyphenoxyethoxy)cumyl]salicylic acid, 4-[3-(p-tolylsulfonyl)propyloxy]zinc salicylate, and these phenolic compounds , salts of aromatic carboxylic acids with polyvalent metals such as zinc, magnesium, aluminum, calcium, titanium, manganese, tin, nickel, as well as antipyrine complexes of zinc thiocyanate, terephthalaldehydic acid and other aromatic carboxylic acids. organic acidic substances such as composite zinc salts with N-p-tolylsulfonyl-N'-phenylurea, 4,4'-bis(p-toluenesulfonylaminocarbonylamino)diphenylmethane, 4,4'-bis[(4-methyl-3-phenoxycarbonylaminophenyl)ureido ] Urea compounds such as diphenylsulfone, thiourea compounds such as N,N'-di-m-chlorophenylthiourea, N-(p-toluenesulfonyl)carbamoylic acid p-cumylphenyl ester, N-(p-toluenesulfonyl) -SO 2 NH- bond in the molecule of carbamoylic acid p-benzyloxyphenyl ester, N-[2-(3-phenylureido)phenyl]benzenesulfonamide, N-(o-toluoyl)-p-toluenesulfonamide, etc. and inorganic acidic substances such as activated clay, attapulgite, colloidal silica, and aluminum silicate.
さらに、下記一般式（１）で表される４，４’－ビス〔（４－メチル－３－フェノキシカルボニルアミノフェニル）ウレイド〕ジフェニルスルホン、４，４’－ビス〔（２－メチル－５－フェノキシカルボニルアミノフェニル）ウレイド〕ジフェニルスルホン、４－（２－メチル－３－フェノキシカルボニルアミノフェニル）ウレイド－４’－（４－メチル－５－フェノキシカルボニルアミノフェニル）ウレイドジフェニルスルホン等のウレアウレタン誘導体、下記一般式（２）で表されるジフェニルスルホン誘導体等が挙げられる。もちろん、これらに制限されるものではなく、また必要に応じて２種以上の化合物を併用することもできる。 Furthermore, 4,4'-bis[(4-methyl-3-phenoxycarbonylaminophenyl)ureido]diphenylsulfone, 4,4'-bis[(2-methyl-5- urea urethane derivatives such as phenoxycarbonylaminophenyl) ureido] diphenyl sulfone, 4-(2-methyl-3-phenoxycarbonylaminophenyl) ureido-4'-(4-methyl-5-phenoxycarbonylaminophenyl) ureido diphenyl sulfone, Examples include diphenylsulfone derivatives represented by the following general formula (2). Of course, the compounds are not limited to these, and two or more kinds of compounds can be used in combination if necessary.
かかる呈色剤の含有量は、特に制限されず、使用されるロイコ染料に応じて調整すればよく、一般にロイコ染料１質量部に対して０．５質量部以上が好ましく、０．８質量部以上がより好ましく、１質量部以上が更に好ましく、１．２質量部以上がより一層好ましく、１．４質量部以上が特に好ましい。また、呈色剤の含有量はロイコ染料１質量部に対して、１０質量部以下が好ましく、５質量部以下がより好ましく、４質量部以下が更に好ましく、３．５質量部以下が特に好ましい。０．５質量部以上とすることにより、記録性能を高めることができる。一方、１０質量部以下とすることにより、高温環境下での地肌カブリを効果的に抑えることができる。 The content of such a coloring agent is not particularly limited and may be adjusted depending on the leuco dye used, and is generally preferably 0.5 parts by mass or more, and 0.8 parts by mass based on 1 part by mass of the leuco dye. The above is more preferable, 1 part by weight or more is still more preferable, even more preferably 1.2 parts by weight or more, and particularly preferably 1.4 parts by weight or more. Further, the content of the coloring agent is preferably 10 parts by mass or less, more preferably 5 parts by mass or less, even more preferably 4 parts by mass or less, particularly preferably 3.5 parts by mass or less, per 1 part by mass of the leuco dye. . By setting the amount to 0.5 parts by mass or more, recording performance can be improved. On the other hand, by setting the amount to 10 parts by mass or less, background fogging in a high-temperature environment can be effectively suppressed.
本発明では、感熱記録層中に、主に発色像の保存性をより一層高めるために、保存性改良剤を更に含有させることができる。このような保存性改良剤としては、例えば、１，１，３－トリス（２－メチル－４－ヒドロキシ－５－シクロヘキシルフェニル）ブタン、１，１，３－トリス（２－メチル－４－ヒドロキシ－５－ｔｅｒｔ－ブチルフェニル）ブタン、１，１－ビス（２－メチル－４－ヒドロキシ－５－ｔｅｒｔ－ブチルフェニル）ブタン、４，４’－〔１，４－フェニレンビス（１－メチルエチリデン）〕ビスフェノール、４，４’－〔１，３－フェニレンビス（１－メチルエチリデン）〕ビスフェノール等のフェノール化合物；４－ベンジルオキシフェニル－４’－（２－メチル－２，３－エポキシプロピルオキシ）フェニルスルホン、４－（２－メチル－１，２－エポキシエチル）ジフェニルスルホン、４－（２－エチル－１，２－エポキシエチル）ジフェニルスルホン等のエポキシ化合物；並びに１，３，５－トリス（２，６－ジメチルベンジル－３－ヒドロキシ－４－ｔｅｒｔ－ブチル）イソシアヌル酸等のイソシアヌル酸化合物から選ばれる少なくとも１種以上を用いることができる。もちろん、これらに制限されるものではなく、また必要に応じて２種以上の化合物を併用することもできる。 In the present invention, a preservability improver can be further included in the heat-sensitive recording layer, mainly in order to further enhance the preservability of the colored image. Examples of such storage improvers include 1,1,3-tris(2-methyl-4-hydroxy-5-cyclohexylphenyl)butane, 1,1,3-tris(2-methyl-4-hydroxy -5-tert-butylphenyl)butane, 1,1-bis(2-methyl-4-hydroxy-5-tert-butylphenyl)butane, 4,4'-[1,4-phenylenebis(1-methylethylidene) )] Bisphenol, 4,4'-[1,3-phenylenebis(1-methylethylidene)] Phenol compounds such as bisphenol; 4-benzyloxyphenyl-4'-(2-methyl-2,3-epoxypropyloxy ) Epoxy compounds such as phenylsulfone, 4-(2-methyl-1,2-epoxyethyl)diphenylsulfone, 4-(2-ethyl-1,2-epoxyethyl)diphenylsulfone; and 1,3,5-tris At least one kind selected from isocyanuric acid compounds such as (2,6-dimethylbenzyl-3-hydroxy-4-tert-butyl)isocyanuric acid can be used. Of course, the compounds are not limited to these, and two or more kinds of compounds can be used in combination if necessary.
保存性改良剤を使用する場合、その使用量は、保存性改良のために有効な量とすればよく、通常は、感熱記録層の全固形量中、１～３０質量％程度が好ましく、５～２０質量％程度がより好ましい。 When using a preservability improver, the amount used may be an amount effective for improving preservability, and is usually preferably about 1 to 30% by mass based on the total solid amount of the heat-sensitive recording layer. About 20% by mass is more preferable.
本発明における感熱記録層中には増感剤を含有させることもできる。これにより、記録感度を高めることができる。増感剤としては、例えば、ステアリン酸アミド、メトキシカルボニル－Ｎ－ステアリン酸ベンズアミルド、Ｎ－ベンゾイルステアリン酸アミド、Ｎ－エイコサン酸アミド、エチレンビスステアリン酸アミド、ベヘン酸アミド、メチレンビスステアリン酸アミド、Ｎ－メチロールステアリン酸アミド、テレフタル酸ジベンジル、テレフタル酸ジメチル、テレフタル酸ジオクチル、ジフェニルスルホン、ｐ－ベンジルオキシ安息香酸ベンジル、１－ヒドロキシ－２－ナフトエ酸フェニル、２－ナフチルベンジルエーテル、ｍ－ターフェニル、ｐ－ベンジルビフェニル、シュウ酸ジ－ｐ－クロロベンジルエステル、シュウ酸ジ－ｐ－メチルベンジルエステル、シュウ酸ジベンジルエステル、ｐ－トリルビフェニルエーテル、ジ（ｐ－メトキシフェノキシエチル）エーテル、１，２－ジ（３－メチルフェノキシ）エタン、１，２－ジ（４－メチルフェノキシ）エタン、１，２－ジ（４－メトキシフェノキシ）エタン、１，２－ジ（４－クロロフェノキシ）エタン、１，２－ジフェノキシエタン、１－（４－メトキシフェノキシ）－２－（３－メチルフェノキシ）エタン、ｐ－メチルチオフェニルベンジルエーテル、１，４－ジ（フェニルチオ）ブタン、ｐ－アセトトルイジド、ｐ－アセトフェネチジド、Ｎ－アセトアセチル－ｐ－トルイジン、１，２－ジフェノキシメチルベンゼン、ジ（β－ビフェニルエトキシ）ベンゼン、ｐ－ジ（ビニルオキシエトキシ）ベンゼン、１－イソプロピルフェニル－２－フェニルエタン、アジピン酸ジ－ｏ－クロルベンジル、１，２－ビス（３，４－ジメチルフェニル）エタン、１，３－ビス（２－ナフトキシ）プロパン、ジフェニル、ベンゾフェノン等が挙げられる。これらは支障のない範囲で併用できる。増感剤の含有割合は、増感のために有効な量とすればよく、通常は、感熱記録層の全固形量中、２～４０質量％程度が好ましく、５～２５質量％程度がより好ましい。 A sensitizer can also be contained in the heat-sensitive recording layer in the present invention. Thereby, recording sensitivity can be increased. Examples of the sensitizer include stearamide, methoxycarbonyl-N-benzamide stearate, N-benzoylstearamide, N-eicosanoic acid amide, ethylenebisstearamide, behenic acid amide, methylenebisstearamide, N-methylolstearamide, dibenzyl terephthalate, dimethyl terephthalate, dioctyl terephthalate, diphenyl sulfone, benzyl p-benzyloxybenzoate, phenyl 1-hydroxy-2-naphthoate, 2-naphthylbenzyl ether, m-terphenyl , p-benzylbiphenyl, di-p-chlorobenzyl oxalate, di-p-methylbenzyl oxalate, dibenzyl oxalate, p-tolylbiphenyl ether, di(p-methoxyphenoxyethyl) ether, 1, 2-di(3-methylphenoxy)ethane, 1,2-di(4-methylphenoxy)ethane, 1,2-di(4-methoxyphenoxy)ethane, 1,2-di(4-chlorophenoxy)ethane, 1,2-diphenoxyethane, 1-(4-methoxyphenoxy)-2-(3-methylphenoxy)ethane, p-methylthiophenylbenzyl ether, 1,4-di(phenylthio)butane, p-acetotoluidide, p- Acetophenetidide, N-acetoacetyl-p-toluidine, 1,2-diphenoxymethylbenzene, di(β-biphenylethoxy)benzene, p-di(vinyloxyethoxy)benzene, 1-isopropylphenyl-2-phenyl Examples include ethane, di-o-chlorobenzyl adipate, 1,2-bis(3,4-dimethylphenyl)ethane, 1,3-bis(2-naphthoxy)propane, diphenyl, and benzophenone. These can be used together as long as there is no problem. The content of the sensitizer may be an effective amount for sensitization, and is usually preferably about 2 to 40% by mass, more preferably about 5 to 25% by mass, based on the total solid amount of the heat-sensitive recording layer. preferable.
感熱記録層の白色度向上、及び画像の均一性向上のため、白色度が高く、平均粒子径が１０μｍ以下の微粒子顔料を感熱記録層に含有させることができる。例えば、炭酸カルシウム、炭酸マグネシウム、カオリン、クレー、タルク、焼成クレー、シリカ、珪藻土、合成珪酸アルミニウム、酸化亜鉛、酸化チタン、水酸化アルミニウム、硫酸バリウム、表面処理された炭酸カルシウム、シリカ等の無機顔料、並びに、尿素－ホルマリン樹脂、スチレン－メタクリル酸共重合樹脂、ポリスチレン樹脂等の有機顔料が使用できる。顔料の含有割合は、発色濃度を低下させない程度の量、すなわち、感熱発色層の全固形量中５０質量％以下であることが好ましい。 In order to improve the whiteness of the heat-sensitive recording layer and the uniformity of the image, a fine particle pigment having a high whiteness and an average particle diameter of 10 μm or less can be included in the heat-sensitive recording layer. For example, inorganic pigments such as calcium carbonate, magnesium carbonate, kaolin, clay, talc, calcined clay, silica, diatomaceous earth, synthetic aluminum silicate, zinc oxide, titanium oxide, aluminum hydroxide, barium sulfate, surface-treated calcium carbonate, and silica. , and organic pigments such as urea-formalin resin, styrene-methacrylic acid copolymer resin, and polystyrene resin can be used. The content ratio of the pigment is preferably an amount that does not reduce the coloring density, that is, 50% by mass or less based on the total solid amount of the heat-sensitive coloring layer.
感熱記録層を構成する他の成分材料としては接着剤を用い、更に必要により、架橋剤、ワックス類、金属石鹸、耐水化剤、分散剤、有色染料、蛍光染料等を用いることができる。 Other components constituting the heat-sensitive recording layer include adhesives, and if necessary, crosslinking agents, waxes, metal soaps, waterproofing agents, dispersants, colored dyes, fluorescent dyes, and the like may be used.
感熱記録層用塗液に使用される接着剤としては、例えば、水溶性接着剤及び水分散性接着剤のいずれの水性接着剤も使用できる。水溶性接着剤としては、例えば、ポリビニルアルコール、カルボキシ変性ポリビニルアルコール、アセトアセチル変性ポリビニルアルコール、ジアセトン変性ポリビニルアルコール、珪素変性ポリビニルアルコール等の変性ポリビニルアルコール、澱粉及びその誘導体、メトキシセルロース、カルボキシメチルセルロース、ヒドロキシエチルセルロース、ヒドロキシプロピルメチルセルロース、メチルセルロース、エチルセルロース等のセルロース誘導体、ポリアクリル酸ソーダ、ポリビニルピロリドン、ポリアミド、ジイソブチレン－無水マレイン酸共重合体塩、スチレン－アクリル酸共重合体塩、スチレン－無水マレイン酸共重合体塩、エチレン－無水マレイン酸共重合体塩、アクリル酸アミド－アクリル酸エステル共重合体、アクリル酸アミド－アクリル酸エステル－メタクリル酸共重合体、ポリアクリルアミド、アルギン酸ソーダ、ゼラチン、カゼイン、アラビアガム等が挙げられる。水分散性接着剤としては、ポリ酢酸ビニル、ポリウレタン、ポリアクリル酸、ポリアクリル酸エステル、塩化ビニル－酢酸ビニル共重合体、ポリブチルメタクリレート、エチレン－酢酸ビニル共重合体等のエマルジョン、又はスチレン－ブタジエン共重合体、スチレン－ブタジエン－アクリル系共重合体等の水不溶性重合体のラテックス等が挙げられる。これらは、１種単独又は２種以上を併用して使用することができる。これらの少なくとも１種を、感熱記録層の全固形量中、好ましくは５～５０質量％程度、より好ましくは１０～４０質量％程度の範囲で配合される。 As the adhesive used in the coating liquid for the heat-sensitive recording layer, for example, any water-based adhesive such as a water-soluble adhesive or a water-dispersible adhesive can be used. Examples of water-soluble adhesives include modified polyvinyl alcohols such as polyvinyl alcohol, carboxy-modified polyvinyl alcohol, acetoacetyl-modified polyvinyl alcohol, diacetone-modified polyvinyl alcohol, silicon-modified polyvinyl alcohol, starch and its derivatives, methoxy cellulose, carboxymethyl cellulose, hydroxy Cellulose derivatives such as ethyl cellulose, hydroxypropyl methyl cellulose, methyl cellulose, and ethyl cellulose, sodium polyacrylate, polyvinyl pyrrolidone, polyamide, diisobutylene-maleic anhydride copolymer salt, styrene-acrylic acid copolymer salt, styrene-maleic anhydride copolymer salt Polymer salt, ethylene-maleic anhydride copolymer salt, acrylic amide-acrylic ester copolymer, acrylic amide-acrylic ester-methacrylic acid copolymer, polyacrylamide, sodium alginate, gelatin, casein, Arabic Examples include gum and the like. Examples of water-dispersible adhesives include emulsions such as polyvinyl acetate, polyurethane, polyacrylic acid, polyacrylic ester, vinyl chloride-vinyl acetate copolymer, polybutyl methacrylate, ethylene-vinyl acetate copolymer, or styrene-vinyl acetate copolymer. Examples include latex of water-insoluble polymers such as butadiene copolymer and styrene-butadiene-acrylic copolymer. These can be used alone or in combination of two or more. At least one of these is blended in an amount of preferably about 5 to 50% by mass, more preferably about 10 to 40% by mass, based on the total solid amount of the heat-sensitive recording layer.
感熱記録層又はその他の層の接着剤を硬化させる架橋剤を感熱記録層中に含有させることができる。これにより、感熱記録層の耐水性を向上させることができる。架橋剤としては、例えば、グリオキザール等のアルデヒド系化合物、ポリエチレンイミン等のポリアミン系化合物、エポキシ系化合物、ポリアミド樹脂、メラミン樹脂、グリオキシル酸塩、ジメチロールウレア化合物、アジリジン化合物、ブロックイソシアネート化合物；過硫酸アンモニウム、塩化第二鉄、塩化マグネシウム、四硼酸ソーダ、四硼酸カリウム等の無機化合物；硼酸、硼酸トリエステル、硼素系ポリマー、ヒドラジド化合物、グリオキシル酸塩等が挙げられる。これらは１種単独で用いてもよいし、２種以上を組合せて使用してもよい。架橋剤の使用量は、感熱記録層の全固形量１００質量部に対し、１～１０質量部程度の範囲が好ましい。これにより、感熱記録層の耐水性を向上させることができる。 A crosslinking agent that cures the adhesive of the heat-sensitive recording layer or other layers can be included in the heat-sensitive recording layer. Thereby, the water resistance of the heat-sensitive recording layer can be improved. Examples of crosslinking agents include aldehyde compounds such as glyoxal, polyamine compounds such as polyethyleneimine, epoxy compounds, polyamide resins, melamine resins, glyoxylates, dimethylol urea compounds, aziridine compounds, blocked isocyanate compounds; ammonium persulfate. , ferric chloride, magnesium chloride, sodium tetraborate, potassium tetraborate, and other inorganic compounds; boric acid, boric acid triesters, boron-based polymers, hydrazide compounds, glyoxylates, and the like. These may be used alone or in combination of two or more. The amount of the crosslinking agent used is preferably in the range of about 1 to 10 parts by weight based on 100 parts by weight of the total solid amount of the heat-sensitive recording layer. Thereby, the water resistance of the heat-sensitive recording layer can be improved.
ワックスとしては、パラフィンワックス、カルナバワックス、マイクロクリスタリンワックス、ポリオレフィンワックス、ポリエチレンワックス等のワックス類；例えば、ステアリン酸アミド、エチレンビスステアリン酸アミド等の高級脂肪酸アミド、高級脂肪酸エステル、及びその誘導体等を挙げることができる。 Examples of waxes include waxes such as paraffin wax, carnauba wax, microcrystalline wax, polyolefin wax, and polyethylene wax; for example, higher fatty acid amides such as stearic acid amide and ethylene bisstearic acid amide, higher fatty acid esters, and derivatives thereof. can be mentioned.
金属石鹸としては、高級脂肪酸多価金属塩、例えば、ステアリン酸亜鉛、ステアリン酸アルミニウム、ステアリン酸カルシウム、及びオレイン酸亜鉛等を挙げることができる。また、必要に応じて、本発明の効果を損なわない範囲で、感熱記録層中に、更に撥油剤、消泡剤、粘度調節剤等の各種助剤を添加することができる。 Examples of metal soaps include polyvalent metal salts of higher fatty acids, such as zinc stearate, aluminum stearate, calcium stearate, and zinc oleate. Further, if necessary, various auxiliary agents such as an oil repellent, an antifoaming agent, a viscosity modifier, etc. can be further added to the heat-sensitive recording layer within a range that does not impair the effects of the present invention.
感熱記録層は、一般に水を分散媒体とし、ロイコ染料と呈色剤、必要により増感剤と保存性改良剤を一緒に、又は別々にボールミル、コボールミル、アトライター、縦型及び横型のサンドミル等の各種撹拌・湿式粉砕機によりポリアクリルアミド、ポリビニルピロリドン、ポリビニルアルコール、メチルセルロース、スチレン－無水マレイン酸共重合体塩等のような水溶性合成高分子化合物、その他界面活性剤と共に分散して分散液とした後、平均粒子径が２μｍ以下となるように分散して得た分散液を用いて、必要により顔料、接着剤、助剤等を混合することにより調製された感熱記録層用塗液を塗布した後、透明支持体上に形成される。感熱記録層の塗布量は、特に制限されず、乾燥質量で１～１２ｇ／ｍ２程度が好ましく、２～１０ｇ／ｍ２がより好ましく、２．５～８ｇ／ｍ２が更に好ましく、３～５．５ｇ／ｍ２が特に好ましい。なお、感熱記録層は必要に応じて２層以上に分けて形成することができ、各層の組成と塗布量は、同一であってもよく、また異なっていてもよい。 The heat-sensitive recording layer is generally prepared by using water as a dispersion medium, and adding a leuco dye, a coloring agent, and optionally a sensitizer and a preservability improver together or separately using a ball mill, coball mill, attritor, vertical and horizontal sand mill, etc. Water-soluble synthetic polymer compounds such as polyacrylamide, polyvinylpyrrolidone, polyvinyl alcohol, methylcellulose, styrene-maleic anhydride copolymer salt, etc., and other surfactants are dispersed using various types of stirring/wet grinders to form a dispersion. Then, using the dispersion obtained by dispersing so that the average particle size is 2 μm or less, a coating liquid for a heat-sensitive recording layer prepared by mixing pigments, adhesives, auxiliaries, etc. as necessary is applied. After that, it is formed on a transparent support. The coating amount of the heat-sensitive recording layer is not particularly limited, and is preferably about 1 to 12 g/ m2 in terms of dry mass, more preferably 2 to 10 g/ m2 , even more preferably 2.5 to 8 g/ m2 , and even more preferably 3 to 12 g/m2. Particularly preferred is 5.5 g/m 2 . The heat-sensitive recording layer can be formed into two or more layers if necessary, and the composition and coating amount of each layer may be the same or different.
［保護層］
本発明の感熱記録体では、感熱記録層上に接着剤及び滑剤を含有する保護層を有する。接着剤の含有割合は、保護層の全固形量中６０質量％以上であり、好ましくは７０質量％以上であり、より好ましくは８０～９５質量％である。６０質量％以上とすることにより、サーマルヘッドの摩耗を減少させることができる。保護層は水を媒体とし、接着剤と滑剤を主成分として、必要により添加される各種助剤を混合して得られる保護層用塗液を、感熱記録層上に塗布及び乾燥して得ることができる。
[Protective layer]
The heat-sensitive recording material of the present invention has a protective layer containing an adhesive and a lubricant on the heat-sensitive recording layer. The content of the adhesive is 60% by mass or more, preferably 70% by mass or more, and more preferably 80 to 95% by mass based on the total solid amount of the protective layer. By setting the content to 60% by mass or more, wear of the thermal head can be reduced. The protective layer is obtained by applying and drying a protective layer coating liquid obtained by using water as a medium and mixing an adhesive and a lubricant as main components with various auxiliary agents added as necessary on the heat-sensitive recording layer. I can do it.
保護層用塗液に使用する接着剤としては、特に制限されず、水溶性接着剤及び水分散性接着剤のいずれの水性接着剤も使用できる。接着剤は、感熱記録層に使用できるものの中から適宜選択することができる。中でも、耐熱性に起因する印画焼けが良好であることから、ポリビニルアルコール、変性ポリビニルアルコール、ポリウレタン樹脂、及びアクリル樹脂が好ましく用いられる。 The adhesive used in the protective layer coating solution is not particularly limited, and any water-based adhesive such as a water-soluble adhesive or a water-dispersible adhesive can be used. The adhesive can be appropriately selected from those that can be used in the heat-sensitive recording layer. Among them, polyvinyl alcohol, modified polyvinyl alcohol, polyurethane resin, and acrylic resin are preferably used because they have good print scorch due to their heat resistance.
変性ポリビニルアルコールとしては、例えばアセトアセチル変性ポリビニルアルコール、ジアセトン変性ポリビニルアルコール、カルボキシ変性ポリビニルアルコール、珪素変性ポリビニルアルコール等が挙げられる。変性ポリビニルアルコールの鹸化度については、８５モル％から完全鹸化の１００モル％程度が好ましく、９０～１００モル％程度がより好ましい。平均重合度については、３００～３０００程度が好ましく、４００～２０００程度がより好ましい。変性度は、耐水性を高める観点から０.５～１０モル％程度が好ましく、１～９モル％程度がより好ましい。重合度、鹸化度が高いほど耐水性が良好になるが、塗料濃度、粘度、塗工性又は乾燥性から状況に応じて選択する必要がある。 Examples of the modified polyvinyl alcohol include acetoacetyl-modified polyvinyl alcohol, diacetone-modified polyvinyl alcohol, carboxy-modified polyvinyl alcohol, and silicon-modified polyvinyl alcohol. The degree of saponification of the modified polyvinyl alcohol is preferably about 85 mol% to about 100 mol%, which is complete saponification, and more preferably about 90 to 100 mol%. The average degree of polymerization is preferably about 300 to 3,000, more preferably about 400 to 2,000. The degree of modification is preferably about 0.5 to 10 mol%, more preferably about 1 to 9 mol%, from the viewpoint of improving water resistance. The higher the degree of polymerization and saponification, the better the water resistance, but it is necessary to select depending on the situation from the viewpoint of coating concentration, viscosity, coating properties, or drying properties.
滑剤としては、少なくともアルキルリン酸エステル塩を含有する。これにより、スティッキングを効果的に抑制できる。 The lubricant contains at least an alkyl phosphate ester salt. Thereby, sticking can be effectively suppressed.
アルキルリン酸エステル塩は、リン酸が有する３つのヒドロキシ基のうちの１以上における水素原子がアルキル基に置換した化合物であり、中でも、モノエステル体（モノアルキルリン酸エステル）が好ましい。アルキルリン酸エステルにおけるエステル部分のアルキル基の炭素数は、好ましくは１２～３６、より好ましくは１２～３０、更に好ましくは１４～２２である。当該アルキル基は、直鎖状であってもよく、分岐鎖状であってもよい。アルキルリン酸エステル塩としては、例えば、無機塩、有機アミン塩、塩基性アミノ酸塩等が挙げられる。無機塩としては、例えば、ナトリウム塩、カリウム塩等のアルカリ金属塩；マグネシウム塩、カルシウム塩等のアルカリ土類金属塩；アンモニウム塩；アルミニウム塩；亜鉛塩等が挙げられる。有機アミン塩としては、例えば、モノエタノールアミン塩、ジエタノールアミン塩、トリエタノールアミン塩等が挙げられる。塩基性アミノ酸塩としては、例えば、アルギニン塩、リジン塩等が挙げられる。 Alkyl phosphate ester salts are compounds in which one or more hydrogen atoms of the three hydroxy groups of phosphoric acid are substituted with alkyl groups, and monoesters (monoalkyl phosphates) are particularly preferred. The number of carbon atoms in the alkyl group of the ester moiety in the alkyl phosphate ester is preferably 12 to 36, more preferably 12 to 30, and even more preferably 14 to 22. The alkyl group may be linear or branched. Examples of the alkyl phosphate salts include inorganic salts, organic amine salts, and basic amino acid salts. Examples of inorganic salts include alkali metal salts such as sodium salts and potassium salts; alkaline earth metal salts such as magnesium salts and calcium salts; ammonium salts; aluminum salts; zinc salts, and the like. Examples of organic amine salts include monoethanolamine salts, diethanolamine salts, triethanolamine salts, and the like. Examples of basic amino acid salts include arginine salts and lysine salts.
アルキルリン酸エステル塩の含有割合は、保護層の全固形量中０．５～２０質量％程度が好ましく、１．０～２０質量％程度がより好ましく、１．０～１０質量％程度が更に好ましい。０．５質量％以上とすることにより、耐スティッキング性を向上できる。２０質量％以下とすることにより、耐可塑剤性の低下を抑えることができる。 The content of the alkyl phosphate ester salt is preferably about 0.5 to 20% by mass, more preferably about 1.0 to 20% by mass, and even more preferably about 1.0 to 10% by mass based on the total solid amount of the protective layer. preferable. Sticking resistance can be improved by setting the content to 0.5% by mass or more. By controlling the content to 20% by mass or less, deterioration in plasticizer resistance can be suppressed.
滑剤として、スティッキングを更に抑制するために、アルキルリン酸エステル塩に加えて、ステアリン酸塩を更に含有させることができる。ステアリン酸塩の具体例としては、ステアリン酸亜鉛、ステアリン酸リチウム、ステアリン酸マグネシウム、ステアリン酸アルミニウム、ステアリン酸カルシウム、ステアリン酸ストロンチウム、ステアリン酸バリウム、ステアリン酸カドミウム、ステアリン酸鉛等が挙げられ、好ましくはステアリン酸亜鉛である。ステアリン酸塩の含有割合は、保護層の全固形量中、１．０～１０質量％程度が好ましく、１．０～５質量％程度がより好ましい。１．０質量％以上とすることにより、耐スティッキング性を向上できる。１０質量％以下とすることにより、塗料の泡立ちを抑制することができる。 In addition to the alkyl phosphate ester salt, a stearate salt can be further included as a lubricant in order to further suppress sticking. Specific examples of stearates include zinc stearate, lithium stearate, magnesium stearate, aluminum stearate, calcium stearate, strontium stearate, barium stearate, cadmium stearate, lead stearate, etc., and preferably stearate. Zinc stearate. The content of stearate is preferably about 1.0 to 10% by mass, more preferably about 1.0 to 5% by mass, based on the total solid amount of the protective layer. Sticking resistance can be improved by setting the content to 1.0% by mass or more. By setting the content to 10% by mass or less, foaming of the paint can be suppressed.
滑剤として、スティッキングを更に抑制するために、アルキルリン酸エステル塩及びステアリン酸塩に加えて、Ｎ置換脂肪酸アミドを更に含有させることができる。Ｎ置換脂肪酸アミドの含有割合は、保護層の全固形量中、１．０～１０質量％程度が好ましく、１．０～５質量％程度がより好ましい。１．０質量％以上とすることにより、耐スティッキング性を向上できる。１０質量％以下とすることにより、耐可塑剤性を向上できる。 In addition to the alkyl phosphate salt and the stearate salt, an N-substituted fatty acid amide may be further contained as a lubricant in order to further suppress sticking. The content of the N-substituted fatty acid amide is preferably about 1.0 to 10% by mass, more preferably about 1.0 to 5% by mass, based on the total solid amount of the protective layer. Sticking resistance can be improved by setting the content to 1.0% by mass or more. By controlling the content to 10% by mass or less, plasticizer resistance can be improved.
Ｎ置換脂肪酸アミドの具体例としては、Ｎ，Ｎ’－エチレンビスラウリン酸アミド、Ｎ，Ｎ’－メチレビスステアリン酸アミド、Ｎ，Ｎ’－エチレンビスステアリン酸アミド、Ｎ，Ｎ’－エチレンビスオレイン酸アミド、Ｎ，Ｎ’－エチレンベヘン酸アミド、Ｎ，Ｎ’－エチレンビス-１２ヒドロキシステアリン酸アミド、Ｎ，Ｎ’－ブチレンビスステアリン酸アミド、Ｎ，Ｎ’－ヘキサメチレンビスステアリン酸アミド、Ｎ，Ｎ’－ヘキサメチレンビスオレイン酸アミド、Ｎ，Ｎ’－キシリレンビスステアリン酸アミド、ステアリン酸モノメチロールアミド、Ｎ，Ｎ’－ジオレイルアジピン酸アミド、Ｎ，Ｎ’－ジステアリルアジピン酸アミド、Ｎ，Ｎ’－ジステアリルセバシン酸アミド、Ｎ，Ｎ’－ジステアリルテレフタル酸アミド、Ｎ，Ｎ’－ジステアリルイソタル酸アミド等が挙げられる。 Specific examples of N-substituted fatty acid amides include N,N'-ethylenebislauric acid amide, N,N'-methylbisstearic acid amide, N,N'-ethylenebisstearic acid amide, and N,N'-ethylenebisstearic acid amide. Oleic acid amide, N,N'-ethylene behenic acid amide, N,N'-ethylenebis-12hydroxystearic acid amide, N,N'-butylene bisstearic acid amide, N,N'-hexamethylene bisstearic acid amide , N,N'-hexamethylenebisoleic acid amide, N,N'-xylylene bisstearic acid amide, stearic acid monomethylolamide, N,N'-dioleyladipic acid amide, N,N'-distearyladipine Examples include acid amide, N,N'-distearyl sebacic acid amide, N,N'-distearyl terephthalic acid amide, N,N'-distearyl isotalic acid amide, and the like.
本発明における保護層中には、サーマルヘッドの摩耗を抑制するため、顔料を含有しないことが望ましい。顔料を含有しない場合であっても、保護層中に滑剤として少なくともアルキルリン酸エステル塩を含有することで、スティッキングを効果的に抑制できる。 In the present invention, the protective layer preferably does not contain any pigment in order to suppress wear of the thermal head. Even when no pigment is contained, sticking can be effectively suppressed by containing at least an alkyl phosphate ester salt as a lubricant in the protective layer.
その他、保護層中に公知の助剤、例えば、消泡剤、濡れ剤、防腐剤、蛍光増白剤、分散剤、増粘剤、着色剤、帯電防止剤、架橋剤等の各種助剤を適宜添加してもよい。 In addition, various known auxiliaries such as antifoaming agents, wetting agents, preservatives, optical brighteners, dispersants, thickeners, colorants, antistatic agents, and crosslinking agents may be added to the protective layer. It may be added as appropriate.
保護層用塗液の塗布量は、乾燥質量で０．５～１０ｇ／ｍ２程度、好ましくは０．５～５ｇ／ｍ２程度である。なお、保護層は、必要に応じて２層以上に分けて形成することができ、各層の組成と塗布量は、同一であってもよく、また異なっていてもよい。 The coating amount of the coating liquid for the protective layer is approximately 0.5 to 10 g/m 2 in terms of dry mass, preferably approximately 0.5 to 5 g/m 2 . Note that the protective layer can be formed into two or more layers if necessary, and the composition and coating amount of each layer may be the same or different.
［その他の層］
本発明では、必要に応じて、透明支持体と感熱記録層との間に、アンカーコート層を設けることもできる。
[Other layers]
In the present invention, an anchor coat layer may be provided between the transparent support and the heat-sensitive recording layer, if necessary.
アンカーコート層は、水分散性接着剤を主成分として含有し、透明支持体上に設けられる。水分散性接着剤としては、例えば、ポリ酢酸ビニル、ポリウレタン、ポリアクリル酸、ポリアクリル酸エステル、塩化ビニル－酢酸ビニル共重合体、ポリブチルメタクリレート、エチレン－酢酸ビニル共重合体、スチレン－ブタジエン共重合体、スチレン－ブタジエン－アクリル系共重合体等の水不溶性重合体等が挙げられる。なお、水不溶性重合体はラテックスの状態で用いればよい。これらの水分散性接着剤は併用することもできる。 The anchor coat layer contains a water-dispersible adhesive as a main component and is provided on a transparent support. Examples of water-dispersible adhesives include polyvinyl acetate, polyurethane, polyacrylic acid, polyacrylic ester, vinyl chloride-vinyl acetate copolymer, polybutyl methacrylate, ethylene-vinyl acetate copolymer, and styrene-butadiene copolymer. Examples include water-insoluble polymers such as polymers and styrene-butadiene-acrylic copolymers. Note that the water-insoluble polymer may be used in the form of latex. These water-dispersible adhesives can also be used together.
透明支持体との密着性及び耐水性が向上する観点から、アンカーコート層が少なくとも一相にウレタン樹脂成分を有する異相粒子構造のポリマーラテックスから得られる水分散性接着剤を含有することが好ましい。 From the viewpoint of improving adhesion to the transparent support and water resistance, it is preferable that the anchor coat layer contains a water-dispersible adhesive obtained from a polymer latex having a heterophasic particle structure having a urethane resin component in at least one phase.
水分散性接着剤の含有割合は、アンカーコート層の全固形量に対して７５～９５質量％であることが好ましい。７５質量％以上とすることにより、より一層優れた密着性を得ることができる。一方、９５質量％以下とすることにより、塗布適性を付与することができる。 The content of the water-dispersible adhesive is preferably 75 to 95% by mass based on the total solid content of the anchor coat layer. By setting the content to 75% by mass or more, even better adhesion can be obtained. On the other hand, by setting the content to 95% by mass or less, coating suitability can be imparted.
アンカーコート層は、本発明の効果を損なわない範囲において、水溶性接着剤を含有することもできる。水溶性接着剤としては、例えば、ポリビニルアルコール及びその誘導体、澱粉及びその誘導体、ヒドロキシメチルセルロース、ヒドロキシエチルセルロース、ヒドロキシプロピルセルロース、メチルセルロース、エチルセルロース等のセルロース誘導体、ポリアクリル酸ソーダ、ポリビニルピロリドン、アクリル酸アミド－アクリル酸エステル共重合体、アクリル酸アミド－アクリル酸エステル－メタクリル酸共重合体、スチレン－無水マレイン酸共重合体、イソブチレン－無水マレイン酸共重合体、カゼイン、ゼラチン及びそれらの誘導体等が挙げられる。 The anchor coat layer can also contain a water-soluble adhesive within a range that does not impair the effects of the present invention. Examples of water-soluble adhesives include polyvinyl alcohol and its derivatives, starch and its derivatives, cellulose derivatives such as hydroxymethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, methylcellulose, and ethylcellulose, sodium polyacrylate, polyvinylpyrrolidone, and acrylic acid amide. Examples include acrylic ester copolymer, acrylic amide-acrylic ester-methacrylic acid copolymer, styrene-maleic anhydride copolymer, isobutylene-maleic anhydride copolymer, casein, gelatin, and derivatives thereof. .
更に、アンカーコート層には助剤として、ジオクチルスルホコハク酸ナトリウム、ドデシルベンゼンスルホン酸ナトリウム、ラウリルアルコール硫酸エステル・ナトリウム塩、脂肪酸金属塩等の界面活性剤、パーフルオロアルキルエチレンオキシド付加物等のフッ素系界面活性剤、ポリエチレンワックス、カルナバロウ、パラフィンワックス、エステルワックス等のワックス類、カオリン、クレー、タルク、炭酸カルシウム、焼成カオリン、酸化チタン、無定形シリカ、水酸化アルミニウム等の顔料、グリオキザール、ホルマリン、グリシン、グリシジルエステル、グリシジルエーテル、ジメチロール尿素、ケテンダイマー、ジアルデヒド澱粉、メラミン樹脂、ポリアミド樹脂、ポリアミド－エピクロルヒドリン樹脂、ケトン－アルデヒド樹脂、硼砂、硼酸、炭酸ジルコニウムアンモニウム、エポキシ系化合物等の架橋剤、消泡剤、蛍光染料、有色染料等を必要に応じて使用することができる。 Furthermore, the anchor coat layer contains surfactants such as sodium dioctyl sulfosuccinate, sodium dodecylbenzenesulfonate, sodium lauryl alcohol sulfate, fatty acid metal salts, and fluorine-based interfaces such as perfluoroalkyl ethylene oxide adducts. Activators, waxes such as polyethylene wax, carnauba wax, paraffin wax, ester wax, kaolin, clay, talc, calcium carbonate, calcined kaolin, pigments such as titanium oxide, amorphous silica, aluminum hydroxide, glyoxal, formalin, glycine, Crosslinking agents such as glycidyl ester, glycidyl ether, dimethylol urea, ketene dimer, dialdehyde starch, melamine resin, polyamide resin, polyamide-epichlorohydrin resin, ketone-aldehyde resin, borax, boric acid, ammonium zirconium carbonate, epoxy compounds, antifoaming Agents, fluorescent dyes, colored dyes, etc. can be used as necessary.
アンカーコート層は、水を媒体とし、例えば前述の異相粒子構造のポリマーラテックス、ポリビニルアルコール、助剤等を混合することにより調製されたアンカーコート層用塗液を、乾燥後の塗布量が０．５～５ｇ／ｍ２程度となるように、透明支持体上に塗布及び乾燥して得ることができる。 The anchor coat layer is prepared by applying a coating liquid for the anchor coat layer prepared by using water as a medium and mixing, for example, the aforementioned polymer latex having a different phase particle structure, polyvinyl alcohol, an auxiliary agent, etc., so that the coating amount after drying is 0. It can be obtained by coating and drying on a transparent support to a weight of about 5 to 5 g/m 2 .
本発明では、必要に応じて透明支持体の感熱記録層とは反対面に、透明感熱記録体の走行性を改良するため、樹脂粒子等の顔料と接着剤を含有する裏面層を設けることもできる。 In the present invention, if necessary, a back layer containing a pigment such as resin particles and an adhesive may be provided on the opposite side of the transparent support from the heat-sensitive recording layer in order to improve the running properties of the transparent heat-sensitive recording material. can.
さらに、感熱記録層とは反対側の裏面に粘着剤、再湿接着剤、ディレードタック型の粘着剤等を塗布し、粘着加工を施すことにより、粘着紙、再湿接着紙、ディレードタック紙などとして使用することができる。粘着加工を施したものは感熱ラベル等の用途に有用である。 Furthermore, by applying an adhesive, rewetting adhesive, delayed tack type adhesive, etc. to the back side opposite to the heat-sensitive recording layer and applying adhesive processing, it can be used as adhesive paper, rewet adhesive paper, delayed tack paper, etc. It can be used as Those that have been subjected to adhesive processing are useful for applications such as heat-sensitive labels.
［感熱記録体］
感熱記録層、保護層、必要により設けるアンカーコート層及び裏面層の形成方法については特に限定されず、例えば、バーコーティング、エアナイフコーティング、バリバーブレードコーティング、ピュアブレードコーティング、ロッドブレードコーティング、ショートドウェルコーティング、カーテンコーティング、ダイコーティング等の適当な塗布方法により、透明支持体上に感熱記録層用塗液、更に保護層用塗液を塗布及び乾燥する等の方法で形成される。
[Thermosensitive recording material]
There are no particular limitations on the method of forming the heat-sensitive recording layer, protective layer, anchor coat layer provided if necessary, and back layer, and examples include bar coating, air knife coating, variver blade coating, pure blade coating, rod blade coating, and short dwell coating. The heat-sensitive recording layer coating liquid and the protective layer coating liquid are coated on a transparent support by an appropriate coating method such as , curtain coating, die coating, etc., and then dried.
本発明では、透明支持体上に形成された少なくとも１層がカーテン塗布法により形成された層であることが好ましい。これにより、均一な厚みを有する層を形成することができ、記録感度を高めたり、油、可塑剤、アルコール等に対するバリア性を高めたりすることができる。カーテン塗布法は、塗液を流下して自由落下させ、透明支持体に非接触で塗布する方法であり、スライドカーテン法、カップルカーテン法、ツインカーテン法等の公知のものを採用することができ、特に制限されるものではない。カーテン塗布法では、同時多層塗布することにより、より均一な厚みを有する層を形成することができる。同時多層塗布では、各塗液を積層した後、塗布し、その後、乾燥させて各層を形成してもよいし、下層を形成する塗液を塗布した後、乾燥することなく下層塗布面が湿潤状態のうちに、下層塗布面上に上層を形成する塗液を塗布し、その後、乾燥させて各層を形成してもよい。本発明では、感熱記録層と保護層を同時多層塗布する態様がバリア性向上の観点から好ましい。 In the present invention, it is preferable that at least one layer formed on the transparent support is a layer formed by a curtain coating method. Thereby, a layer having a uniform thickness can be formed, and recording sensitivity can be increased and barrier properties against oil, plasticizer, alcohol, etc. can be improved. The curtain coating method is a method in which the coating liquid is allowed to fall freely and coated on the transparent support without contact, and known methods such as the slide curtain method, couple curtain method, and twin curtain method can be adopted. , but is not particularly limited. In the curtain coating method, layers having a more uniform thickness can be formed by simultaneously applying multiple layers. In simultaneous multi-layer coating, each layer may be formed by laminating each coating liquid, then coating and then drying, or after coating the coating liquid forming the lower layer, the lower layer coated surface is moistened without drying. In this state, a coating liquid for forming an upper layer may be applied onto the lower layer coating surface, and then dried to form each layer. In the present invention, a mode in which the heat-sensitive recording layer and the protective layer are simultaneously applied in multiple layers is preferred from the viewpoint of improving barrier properties.
本発明では、記録感度を高めて、画像均一性を向上させる観点から、各層を形成し終えた後、又は全ての層を形成し終えた後の任意の過程で、スーパーカレンダーやソフトカレンダー等の既知の方法を用いて平滑化処理することが好ましい。 In the present invention, from the viewpoint of increasing recording sensitivity and improving image uniformity, a super calender, soft calender, etc. Preferably, the smoothing process is performed using a known method.
本発明においては、より製品の付加価値を高めるため、多色感熱記録体とすることもできる。一般に多色感熱記録体は、加熱温度の差、又は熱エネルギーの差を利用する試みであり、一般に、透明支持体上に異なる色調に発色する高温発色層と低温発色層を順次積層して構成されたものであって、これらを大別すると消色型と加色型の２種類があり、マイクロカプセルを用いた方法及び有機高分子とロイコ染料からなる複合粒子を使用して多色感熱記録体を製造する方法がある。 In the present invention, in order to further increase the added value of the product, a multicolor thermosensitive recording material can also be used. In general, multicolor thermosensitive recording materials are attempts to utilize differences in heating temperature or thermal energy, and are generally constructed by sequentially laminating a high temperature coloring layer and a low temperature coloring layer that develop colors in different tones on a transparent support. Broadly speaking, there are two types: decolorizing type and coloring type. Multicolor thermal recording is performed using a method using microcapsules and composite particles consisting of organic polymer and leuco dye. There is a way to manufacture the body.
本発明を実施例により更に詳しく説明するが、本発明はこれらにより限定されるものではない。なお、特に断わらない限り、「部」及び「％」は、それぞれ「質量部」及び「質量％」を示す。 The present invention will be explained in more detail with reference to Examples, but the present invention is not limited thereto. Note that unless otherwise specified, "parts" and "%" refer to "parts by mass" and "% by mass," respectively.
実施例１
・Ａ液（ロイコ染料分散液）の調製
３－ジ（ｎ－ブチル）アミノ－６－メチル－７－アニリノフルオラン１００部、スルホン変性ポリビニルアルコール（商品名：ゴーセネックスＬ－３２６６、日本合成化学社製）の２０％水溶液５０部、天然油脂系消泡剤（商品名：ノプコ１４０７Ｈ、サンノプコ社製）の５％エマルジョン１０部、及び水９０部からなる組成物を、サンドミルによりレーザー回折式粒度分布測定装置ＳＡＬＤ２２００（島津製作所社製）によるメジアン径が０．５μｍとなるまで粉砕してＡ液を得た。
Example 1
・Preparation of liquid A (leuco dye dispersion) 100 parts of 3-di(n-butyl)amino-6-methyl-7-anilinofluorane, sulfone-modified polyvinyl alcohol (product name: Gosenex L-3266, Nippon Gohsen Kagaku) A composition consisting of 50 parts of a 20% aqueous solution of San Nopco Co., Ltd.), 10 parts of a 5% emulsion of a natural oil-based antifoaming agent (trade name: Nopco 1407H, manufactured by San Nopco Co., Ltd.), and 90 parts of water was milled using a sand mill to obtain a particle size determined by laser diffraction method. A liquid A was obtained by pulverizing the mixture until the median diameter was 0.5 μm using a distribution measuring device SALD2200 (manufactured by Shimadzu Corporation).
・Ｂ液（呈色剤分散液）の調製
１，１－ビス（４－ヒドロキシフェニル）－１－フェニルエタン１００部、スルホン変性ポリビニルアルコール（商品名：ゴーセネックスＬ－３２６６、日本合成化学社製）の２０％水溶液４０部、天然油脂系消泡剤（商品名：ノプコ１４０７Ｈ、サンノプコ社製）の５％エマルジョン１部、及び水８０部からなる組成物を、ウルトラビスコミルにより動的光散乱式粒径分布測定装置ＬＢ－５００（堀場製作所製）によるメジアン径が０．２μｍとなるまで粉砕してＢ液を得た。
・Preparation of liquid B (coloring agent dispersion) 100 parts of 1,1-bis(4-hydroxyphenyl)-1-phenylethane, sulfone-modified polyvinyl alcohol (trade name: Gosenex L-3266, manufactured by Nippon Gosei Kagaku Co., Ltd.) A composition consisting of 40 parts of a 20% aqueous solution of , 1 part of a 5% emulsion of a natural oil-based antifoaming agent (trade name: Nopco 1407H, manufactured by San Nopco), and 80 parts of water was subjected to dynamic light scattering using an Ultra Visco Mill. The mixture was ground using a particle size distribution analyzer LB-500 (manufactured by Horiba, Ltd.) until the median diameter was 0.2 μm to obtain liquid B.
・感熱記録層用塗液の調製
Ａ液３６部、Ｂ液４７．８部、コロイダルシリカ（商品名：スノーテックスＮ、平均粒子径１０～１５ｎｍ、日産化学社製、固形分濃度２０％）３３．５部、スチレン－ブタジエン系ラテックス（商品名：スマーテックスＰＡ９２８１、日本Ａ＆Ｌ社製、固形分濃度４８％）１３．９部、ジアセトン変性ポリビニルアルコール（商品名：ＤＦ－１７、日本酢ビ・ポバール社製）の１０％水溶液３８部、ポリエステル系ポリウレタン樹脂（商品名：ハイドランＡＭ－１、ＤＩＣ社製、固形分濃度２０％）３５部、ポリエステル系ポリウレタン（商品名：メトローズ６０ＳＨ－０３、信越化学社製）の１０％水溶液１０部、ポリエチレンワックスエマルジョン（商品名：ノプコートＰＥＭ１７、サンノプコ社製、固形分濃度４０％）１部、ジオクチルスルホコハク酸ナトリウム塩（商品名：ＳＮウェットＯＴ－７０、サンノプコ社製）の１０％水溶液６部、及び水１８部からなる組成物を混合攪拌して感熱記録層用塗液を調製した。
・Preparation of coating liquid for heat-sensitive recording layer 36 parts of liquid A, 47.8 parts of liquid B, colloidal silica (trade name: Snowtex N, average particle size 10 to 15 nm, manufactured by Nissan Chemical Co., Ltd., solid content concentration 20%) 33 .5 parts, 13.9 parts of styrene-butadiene latex (product name: Smartex PA9281, manufactured by Japan A&L Co., Ltd., solid content concentration 48%), diacetone-modified polyvinyl alcohol (product name: DF-17, Japanese acetate/poval) 38 parts of a 10% aqueous solution of Polyester Polyurethane (trade name: Hydran AM-1, manufactured by DIC, solid content 20%), 35 parts of polyester polyurethane (trade name: Metrose 60SH-03, Shin-Etsu Chemical) 10 parts of a 10% aqueous solution of San Nopco Co., Ltd.), 1 part of polyethylene wax emulsion (product name: Nopcoat PEM17, manufactured by San Nopco Co., Ltd., solid content concentration 40%), dioctyl sulfosuccinate sodium salt (product name: SN Wet OT-70, San Nopco Co., Ltd.) A coating solution for a heat-sensitive recording layer was prepared by mixing and stirring a composition consisting of 6 parts of a 10% aqueous solution of the product manufactured by Co., Ltd.) and 18 parts of water.
・保護層用塗液の調製
アセトアセチル変性ポリビニルアルコール（ゴーセネックスＺ－２００、日本合成化学社製、完全ケン化、重合度１１００）の１４％水溶液４２７．０部、ステアリルリン酸エステルカリウム塩エマルジョン（商品名：ウーポール１８００、松本油脂社製、固形分濃度３５％）０．３部、ポリエステル系ポリウレタン樹脂（商品名：ハイドランＡＭ－１、ＤＩＣ社製、固形分濃度２０％）２００．６部、及び水１００．０部からなる組成物を混合攪拌して保護層用塗液を調製した。
・Preparation of coating liquid for protective layer 427.0 parts of a 14% aqueous solution of acetoacetyl-modified polyvinyl alcohol (Gosenex Z-200, manufactured by Nippon Gosei Kagaku Co., Ltd., completely saponified, degree of polymerization 1100), stearyl phosphate potassium salt emulsion ( Product name: Woopol 1800, manufactured by Matsumoto Yushi Co., Ltd., solid content concentration 35%) 0.3 parts, polyester polyurethane resin (trade name: Hydran AM-1, manufactured by DIC Corporation, solid content concentration 20%) 200.6 parts, and 100.0 parts of water were mixed and stirred to prepare a coating liquid for a protective layer.
・透明感熱記録体の作製
透明なポリエチレンテレフタレートフィルムの片面上に、乾燥後の塗布量が４．０ｇ／ｍ２となるように感熱記録層用塗液を塗布及び乾燥して感熱記録層を形成した。更に感熱記録層上に乾燥後の塗布量が３．０ｇ／ｍ２となるように保護層用塗液を塗布及び乾燥して保護層を形成し、透明感熱記録体を得た。
・Preparation of transparent heat-sensitive recording material A heat-sensitive recording layer coating liquid was applied on one side of a transparent polyethylene terephthalate film so that the coating amount after drying was 4.0 g/m 2 and dried to form a heat-sensitive recording layer. did. Furthermore, a coating liquid for a protective layer was applied onto the heat-sensitive recording layer so that the coated amount after drying was 3.0 g/m 2 and dried to form a protective layer, thereby obtaining a transparent heat-sensitive recording material.
実施例２
実施例１の保護層用塗液の調製において、アセトアセチル変性ポリビニルアルコール（ゴーセネックスＺ－２００、日本合成化学社製、完全ケン化、重合度１１００）の１４％水溶液４２７．０部を４２１．０部に、ステアリルリン酸エステルカリウム塩エマルジョン（商品名：ウーポール１８００、松本油脂社製、固形分濃度３５％）０．３部を４．３部に、ポリエステル系ポリウレタン樹脂（商品名：ハイドランＡＭ－１、ＤＩＣ社製、固形分濃度２０％）２００．６部を１９７．８部にそれぞれ変更した以外は実施例１と同様にして透明感熱記録体を得た。
Example 2
In preparing the coating liquid for the protective layer in Example 1, 427.0 parts of a 14% aqueous solution of acetoacetyl-modified polyvinyl alcohol (Gosenex Z-200, manufactured by Nippon Gosei Kagaku Co., Ltd., completely saponified, degree of polymerization 1100) was added to 421.0 parts. 0.3 parts of stearyl phosphate potassium salt emulsion (product name: Woopol 1800, manufactured by Matsumoto Yushi Co., Ltd., solid content concentration 35%) was added to 4.3 parts of polyester polyurethane resin (product name: Hydran AM-). A transparent thermosensitive recording material was obtained in the same manner as in Example 1, except that 200.6 parts (1, manufactured by DIC Corporation, solid content concentration 20%) were changed to 197.8 parts.
実施例３
実施例１の保護層用塗液の調製において、アセトアセチル変性ポリビニルアルコール（ゴーセネックスＺ－２００、日本合成化学社製、完全ケン化、重合度１１００）の１４％水溶液４２７．０部を３６３．３部に、ステアリルリン酸エステルカリウム塩エマルジョン（商品名：ウーポール１８００、松本油脂社製、固形分濃度３５％）０．３部を４２．９部に、ポリエステル系ポリウレタン樹脂（商品名：ハイドランＡＭ－１、ＤＩＣ社製、固形分濃度２０％）２００．６部を１７０．７部にそれぞれ変更した以外は実施例１と同様にして透明感熱記録体を得た。
Example 3
In preparing the coating liquid for the protective layer in Example 1, 363.3 parts of 427.0 parts of a 14% aqueous solution of acetoacetyl-modified polyvinyl alcohol (Gosenex Z-200, manufactured by Nippon Gosei Kagaku Co., Ltd., completely saponified, degree of polymerization 1100) was added. 0.3 part of stearyl phosphate potassium salt emulsion (trade name: Woopor 1800, manufactured by Matsumoto Yushi Co., Ltd., solid content concentration 35%) was added to 42.9 parts of polyester polyurethane resin (trade name: Hydran AM-). A transparent thermosensitive recording material was obtained in the same manner as in Example 1, except that 200.6 parts (1, manufactured by DIC Corporation, solid content concentration 20%) was changed to 170.7 parts.
実施例４
実施例１の保護層用塗液の調製において、アセトアセチル変性ポリビニルアルコール（ゴーセネックスＺ－２００、日本合成化学社製、完全ケン化、重合度１１００）の１４％水溶液４２７．０部を２５６．４部に、ステアリルリン酸エステルカリウム塩エマルジョン（商品名：ウーポール１８００、松本油脂社製、固形分濃度３５％）０．３部を１１４．３部に、ポリエステル系ポリウレタン樹脂（商品名：ハイドランＡＭ－１、ＤＩＣ社製、固形分濃度２０％）２００．６部を１２０．５部にそれぞれ変更した以外は実施例１と同様にして透明感熱記録体を得た。
Example 4
In the preparation of the coating liquid for the protective layer of Example 1, 427.0 parts of a 14% aqueous solution of acetoacetyl-modified polyvinyl alcohol (Gosenex Z-200, manufactured by Nippon Gosei Kagaku Co., Ltd., completely saponified, degree of polymerization 1100) was added to 256.4 parts. 1 part, 0.3 part of stearyl phosphate potassium salt emulsion (trade name: Woopol 1800, manufactured by Matsumoto Yushi Co., Ltd., solid content concentration 35%) to 114.3 parts, polyester polyurethane resin (trade name: Hydran AM-) A transparent heat-sensitive recording material was obtained in the same manner as in Example 1, except that 200.6 parts (manufactured by DIC Corporation, solid content concentration 20%) were changed to 120.5 parts.
実施例５
実施例１の保護層用塗液の調製において、アセトアセチル変性ポリビニルアルコール（ゴーセネックスＺ－２００、日本合成化学社製、完全ケン化、重合度１１００）の１４％水溶液４２７．０部を４１４．６部に、ステアリルリン酸エステルカリウム塩エマルジョン（商品名：ウーポール１８００、松本油脂社製、固形分濃度３５％）０．３部を４．３部に、ポリエステル系ポリウレタン樹脂（商品名：ハイドランＡＭ－１、ＤＩＣ社製、固形分濃度２０％）２００．６部を１９４．８部にそれぞれ変更し、更にステアリン酸亜鉛（商品名：ハイミクロンＬ－１１１、中京油脂社製、固形分濃度２０％）７．５部を添加した以外は実施例１と同様にして透明感熱記録体を得た。
Example 5
In preparing the coating solution for the protective layer in Example 1, 427.0 parts of a 14% aqueous solution of acetoacetyl-modified polyvinyl alcohol (Gosenex Z-200, manufactured by Nippon Gosei Kagaku Co., Ltd., completely saponified, degree of polymerization 1100) was added to 414.6 parts. 0.3 parts of stearyl phosphate potassium salt emulsion (product name: Woopol 1800, manufactured by Matsumoto Yushi Co., Ltd., solid content concentration 35%) was added to 4.3 parts of polyester polyurethane resin (product name: Hydran AM-). 1. Manufactured by DIC Corporation, solid content concentration 20%) 200.6 parts were changed to 194.8 parts, and zinc stearate (product name: Himicron L-111, manufactured by Chukyo Yushi Co., Ltd., solid content concentration 20%) was added. ) A transparent heat-sensitive recording material was obtained in the same manner as in Example 1 except that 7.5 parts of the resin was added.
実施例６
実施例５の保護層用塗液の調製において、アセトアセチル変性ポリビニルアルコール（ゴーセネックスＺ－２００、日本合成化学社製、完全ケン化、重合度１１００）の１４％水溶液４１４．６部を３８８．９部に、ポリエステル系ポリウレタン樹脂（商品名：ハイドランＡＭ－１、ＤＩＣ社製、固形分濃度２０％）１９４．８部を１８２．７部に、ステアリン酸亜鉛（商品名：ハイミクロンＬ－１１１、中京油脂社製、固形分濃度２０％）７．５部を３７．５部に変更した以外は実施例５と同様にして透明感熱記録体を得た。
Example 6
In preparing the coating solution for the protective layer in Example 5, 414.6 parts of a 14% aqueous solution of acetoacetyl-modified polyvinyl alcohol (Gosenex Z-200, manufactured by Nippon Gosei Kagaku Co., Ltd., completely saponified, degree of polymerization 1100) was added to 388.9 parts. 194.8 parts of polyester polyurethane resin (product name: Hydran AM-1, manufactured by DIC Corporation, solid content concentration 20%) was added to 182.7 parts, zinc stearate (product name: Himicron L-111, A transparent thermosensitive recording material was obtained in the same manner as in Example 5 except that 7.5 parts (manufactured by Chukyo Yushi Co., Ltd., solid content concentration 20%) was changed to 37.5 parts.
実施例７
実施例５の保護層用塗液の調製において、アセトアセチル変性ポリビニルアルコール（ゴーセネックスＺ－２００、日本合成化学社製、完全ケン化、重合度１１００）の１４％水溶液４１４．６部を３６７．６部に、ポリエステル系ポリウレタン樹脂（商品名：ハイドランＡＭ－１、ＤＩＣ社製、固形分濃度２０％）１９４．８部を１７２．７部に、ステアリン酸亜鉛（商品名：ハイミクロンＬ－１１１、中京油脂社製、固形分濃度２０％）７．５部を６２．５部に変更した以外は実施例５と同様にして透明感熱記録体を得た。
Example 7
In preparing the coating liquid for the protective layer in Example 5, 414.6 parts of a 14% aqueous solution of acetoacetyl-modified polyvinyl alcohol (Gosenex Z-200, manufactured by Nippon Gosei Kagaku Co., Ltd., completely saponified, degree of polymerization 1100) was added to 367.6 parts. 194.8 parts of polyester polyurethane resin (product name: Hydran AM-1, manufactured by DIC Corporation, solid content concentration 20%) was added to 172.7 parts, zinc stearate (product name: Himicron L-111, A transparent thermosensitive recording material was obtained in the same manner as in Example 5 except that 7.5 parts (manufactured by Chukyo Yushi Co., Ltd., solid content concentration 20%) was changed to 62.5 parts.
実施例８
実施例６の保護層用塗液の調製において、アセトアセチル変性ポリビニルアルコール（ゴーセネックスＺ－２００、日本合成化学社製、完全ケン化、重合度１１００）の１４％水溶液３８８．９部を３８２．５部に、ポリエステル系ポリウレタン樹脂（商品名：ハイドランＡＭ－１、ＤＩＣ社製、固形分濃度２０％）１８２．７部を１７９．７部にそれぞれ変更し、更にエチレンビスステアリン酸アミドエマルジョン（商品名：ハイミクロンＧ－１１０、中京油脂社製、固形分濃度２７％）５．６部を添加した以外は実施例６と同様にして透明感熱記録体を得た。
Example 8
In preparing the coating solution for the protective layer in Example 6, 382.5 parts of a 14% aqueous solution of 14% aqueous solution of acetoacetyl-modified polyvinyl alcohol (Gosenex Z-200, manufactured by Nippon Gosei Kagaku Co., Ltd., completely saponified, degree of polymerization 1100) was added. 182.7 parts of polyester polyurethane resin (trade name: Hydran AM-1, manufactured by DIC Corporation, solid content concentration 20%) was changed to 179.7 parts, and ethylene bisstearic acid amide emulsion (trade name: A transparent thermosensitive recording material was obtained in the same manner as in Example 6, except that 5.6 parts of Himicron G-110 (manufactured by Chukyo Yushi Co., Ltd., solid content concentration 27%) was added.
実施例９
実施例８の保護層用塗液の調製において、アセトアセチル変性ポリビニルアルコール（ゴーセネックスＺ－２００、日本合成化学社製、完全ケン化、重合度１１００）の１４％水溶液３８２．５部を３５６．９部に、ポリエステル系ポリウレタン樹脂（商品名：ハイドランＡＭ－１、ＤＩＣ社製、固形分濃度２０％）１７９．７部を１６７．７部に、エチレンビスステアリン酸アミドエマルジョン（商品名：ハイミクロンＧ－１１０、中京油脂社製、固形分濃度２７％）５．６部を２７．８部にそれぞれ変更した以外は実施例８と同様にして透明感熱記録体を得た。
Example 9
In preparing the coating liquid for the protective layer in Example 8, 382.5 parts of a 14% aqueous solution of acetoacetyl-modified polyvinyl alcohol (Gosenex Z-200, manufactured by Nippon Gosei Kagaku Co., Ltd., completely saponified, degree of polymerization 1100) was added to 356.9 parts. 179.7 parts of polyester polyurethane resin (product name: Hydran AM-1, manufactured by DIC Corporation, solid content concentration 20%) was added to 167.7 parts of ethylene bisstearic acid amide emulsion (product name: Himicron G). -110, manufactured by Chukyo Yushi Co., Ltd., solid content concentration 27%) A transparent thermosensitive recording material was obtained in the same manner as in Example 8, except that 5.6 parts were changed to 27.8 parts.
実施例１０
実施例８の保護層用塗液の調製において、アセトアセチル変性ポリビニルアルコール（ゴーセネックスＺ－２００、日本合成化学社製、完全ケン化、重合度１１００）の１４％水溶液３８２．５部を３３５．５部に、ポリエステル系ポリウレタン樹脂（商品名：ハイドランＡＭ－１、ＤＩＣ社製、固形分濃度２０％）１７９．７部を１５７．６部に、エチレンビスステアリン酸アミドエマルジョン（商品名：ハイミクロンＧ－１１０、中京油脂社製、固形分濃度２７％）５．６部を４６．３部にそれぞれ変更した以外は実施例８と同様にして透明感熱記録体を得た。
Example 10
In preparing the coating liquid for the protective layer in Example 8, 382.5 parts of a 14% aqueous solution of acetoacetyl-modified polyvinyl alcohol (Gosenex Z-200, manufactured by Nippon Gosei Kagaku Co., Ltd., completely saponified, degree of polymerization 1100) was added to 335.5 parts. 179.7 parts of polyester polyurethane resin (product name: Hydran AM-1, manufactured by DIC Corporation, solid content concentration 20%) was added to 157.6 parts of ethylene bisstearamide emulsion (product name: Himicron G). -110, manufactured by Chukyo Yushi Co., Ltd., solid content concentration 27%) A transparent thermosensitive recording material was obtained in the same manner as in Example 8, except that 5.6 parts were changed to 46.3 parts.
実施例１１
実施例９の保護層用塗液の調製において、アセトアセチル変性ポリビニルアルコール（ゴーセネックスＺ－２００、日本合成化学社製、完全ケン化、重合度１１００）の１４％水溶液３５６．９部の代わりに、同量のジアセトン変性ポリビニルアルコール（ＤＦ－１０、日本酢ビ・ポバール社製、重合度１０００）の１４％水溶液を用いた以外は実施例９と同様にして透明感熱記録体を得た。
Example 11
In the preparation of the coating liquid for the protective layer of Example 9, instead of 356.9 parts of a 14% aqueous solution of acetoacetyl-modified polyvinyl alcohol (Gosenex Z-200, manufactured by Nippon Gosei Kagaku Co., Ltd., completely saponified, degree of polymerization 1100), A transparent thermosensitive recording material was obtained in the same manner as in Example 9, except that the same amount of a 14% aqueous solution of diacetone-modified polyvinyl alcohol (DF-10, manufactured by Nihon Acetate Vinyl Poval Co., Ltd., polymerization degree 1000) was used.
比較例１
実施例１の保護層用塗液の調製において、アセトアセチル変性ポリビニルアルコール（ゴーセネックスＺ－２００、日本合成化学社製、完全ケン化、重合度１１００）の１４％水溶液４２７．０部を３５６．９部に、ステアリルリン酸エステルカリウム塩エマルジョン（商品名：ウーポール１８００、松本油脂社製、固形分濃度３５％）０．３部を０部に、ポリエステル系ポリウレタン樹脂（商品名：ハイドランＡＭ－１、ＤＩＣ社製、固形分濃度２０％）２００．６部を１６７．７部にそれぞれ変更し、更にステアリン酸亜鉛（商品名：ハイミクロンＬ－１１１、中京油脂社製、固形分濃度２０％）８２．５部を添加した以外は実施例１と同様にして透明感熱記録体を得た。
Comparative example 1
In preparing the coating liquid for the protective layer in Example 1, 427.0 parts of a 14% aqueous solution of acetoacetyl-modified polyvinyl alcohol (Gosenex Z-200, manufactured by Nippon Gosei Kagaku Co., Ltd., completely saponified, degree of polymerization 1100) was added to 356.9 parts. 0 parts, 0.3 parts of stearyl phosphate potassium salt emulsion (trade name: Woopol 1800, manufactured by Matsumoto Yushi Co., Ltd., solid content concentration 35%), 0 parts of polyester polyurethane resin (trade name: Hydran AM-1, DIC Co., Ltd., solid content concentration 20%) 200.6 parts were changed to 167.7 parts, and zinc stearate (product name: Himicron L-111, Chukyo Yushi Co., Ltd., solid content concentration 20%) 82 A transparent heat-sensitive recording material was obtained in the same manner as in Example 1, except that .5 parts were added.
比較例２
実施例１の保護層用塗液の調製において、アセトアセチル変性ポリビニルアルコール（ゴーセネックスＺ－２００、日本合成化学社製、完全ケン化、重合度１１００）の１４％水溶液４２７．０部を３５６．９部に、ステアリルリン酸エステルカリウム塩エマルジョン（商品名：ウーポール１８００、松本油脂社製、固形分濃度３５％）０．３部を０部に、ポリエステル系ポリウレタン樹脂（商品名：ハイドランＡＭ－１、ＤＩＣ社製、固形分濃度２０％）２００．６部を１６７．７部にそれぞれ変更し、更にエチレンビスステアリン酸アミドエマルジョン（商品名：ハイミクロンＧ－１１０、中京油脂社製、固形分濃度２７％）６１．１部を添加した以外は実施例１と同様にして透明感熱記録体を得た。
Comparative example 2
In preparing the coating liquid for the protective layer in Example 1, 427.0 parts of a 14% aqueous solution of acetoacetyl-modified polyvinyl alcohol (Gosenex Z-200, manufactured by Nippon Gosei Kagaku Co., Ltd., completely saponified, degree of polymerization 1100) was added to 356.9 parts. 0 parts, 0.3 parts of stearyl phosphate potassium salt emulsion (trade name: Woopol 1800, manufactured by Matsumoto Yushi Co., Ltd., solid content concentration 35%), 0 parts of polyester polyurethane resin (trade name: Hydran AM-1, (manufactured by DIC Corporation, solid content concentration 20%) was changed from 200.6 parts to 167.7 parts, and further ethylene bisstearic acid amide emulsion (trade name: Himicron G-110, manufactured by Chukyo Yushi Co., Ltd., solid content concentration 27) A transparent heat-sensitive recording material was obtained in the same manner as in Example 1 except that 61.1 parts (%) was added.
比較例３
実施例９の保護層用塗液の調製において、アセトアセチル変性ポリビニルアルコール（ゴーセネックスＺ－２００、日本合成化学社製、完全ケン化、重合度１１００）の１４％水溶液３５６．９部を２３５．１部に、ポリエステル系ポリウレタン樹脂（商品名：ハイドランＡＭ－１、ＤＩＣ社製、固形分濃度２０％）１６７．７部を１１０．４部にそれぞれ変更し、更にコロイダルシリカ（商品名：スノーテックスＯ、平均粒子径１０～１５ｎｍ、日産化学社製、固形分濃度２０％）１４２．５部を添加した以外は実施例９と同様にして透明感熱記録体を得た。
Comparative example 3
In preparing the coating liquid for the protective layer in Example 9, 356.9 parts of a 14% aqueous solution of acetoacetyl-modified polyvinyl alcohol (Gosenex Z-200, manufactured by Nippon Gosei Kagaku Co., Ltd., completely saponified, degree of polymerization 1100) was added to 235.1 parts. 167.7 parts of polyester polyurethane resin (product name: Hydran AM-1, manufactured by DIC Corporation, solid content concentration 20%) was changed to 110.4 parts, and colloidal silica (product name: Snowtex O) was added to the parts. A transparent heat-sensitive recording material was obtained in the same manner as in Example 9, except that 142.5 parts of the powder (average particle size: 10 to 15 nm, manufactured by Nissan Chemical Co., Ltd., solid content concentration: 20%) were added.
比較例４
実施例９の保護層用塗液の調製において、アセトアセチル変性ポリビニルアルコール（ゴーセネックスＺ－２００、日本合成化学社製、完全ケン化、重合度１１００）の１４％水溶液３５６．９部を１４９．６部に、ポリエステル系ポリウレタン樹脂（商品名：ハイドランＡＭ－１、ＤＩＣ社製、固形分濃度２０％）１６７．７部を７０．３部にそれぞれ変更し、更にコロイダルシリカ（商品名：スノーテックスＯ、平均粒子径１０～１５ｎｍ、日産化学社製、固形分濃度２０％）２４２．５部を添加した以外は実施例９と同様にして透明感熱記録体を得た。
Comparative example 4
In preparing the coating solution for the protective layer in Example 9, 356.9 parts of a 14% aqueous solution of acetoacetyl-modified polyvinyl alcohol (Gosenex Z-200, manufactured by Nippon Gosei Kagaku Co., Ltd., completely saponified, degree of polymerization 1100) was added to 149.6 parts. 167.7 parts of polyester polyurethane resin (product name: Hydran AM-1, manufactured by DIC Corporation, solid content concentration 20%) was changed to 70.3 parts, and colloidal silica (product name: Snowtex O) was added to the parts. A transparent heat-sensitive recording material was obtained in the same manner as in Example 9, except that 242.5 parts of 242.5 parts (10 to 15 nm, average particle size, manufactured by Nissan Chemical Co., Ltd., solid content concentration 20%) were added.
以上の実施例１～１１、及び比較例１～４で作製した透明感熱記録体を下記の評価に供し、その結果を表１に示す。 The transparent thermosensitive recording bodies produced in Examples 1 to 11 and Comparative Examples 1 to 4 above were subjected to the following evaluation, and the results are shown in Table 1.
〔ヘッド磨耗性の評価〕
直径０．３１７５ｃｍの真鍮球に９００ｇの荷重をかけ、各透明感熱記録体の保護層表面を３７５ｍ走行させたときの真鍮球の磨耗深さをキーエンス社製形状測定装置Ｐｒｏｆｌｅ Ｍｅａｓｕｒｅｍｅｎｔ ｕｎｉｔ ＶＨＸ－Ｓ１５を用いて測定した。磨耗深さが小さいほど、ヘッド磨耗性が良好であるといえる。
[Evaluation of head abrasion]
A load of 900 g was applied to a brass ball with a diameter of 0.3175 cm, and the wear depth of the brass ball was measured by running it for 375 m on the surface of the protective layer of each transparent heat-sensitive recording material using a Profile Measurement Unit VHX-S15 manufactured by Keyence Corporation. It was measured using It can be said that the smaller the abrasion depth, the better the head abrasion resistance.
〔スティッキングの評価〕
感熱プリンター（商品名：Ａｔｌａｎｔｅｋ４００、Ｇｌｏｂａｌ Ｍｅｄｉａ Ｉｎｓｔｒｕｍｅｎｔｓ社製）を用い、Ｐａｔｔｅｒｎ４、Ｅｎｅｒｇｙ ＭｉｄにてＤｙｎａｍｉｃ Ｒｅｓｐｏｎｓｅの印字を行い、Ｓｔｅｐ２の印字上部から、Ｓｔｅｐ１０の印字下部までの印字長を測定した。実用上、印字長は１５．０ｃｍ以上必要である。
[Sticking evaluation]
Using a thermal printer (product name: Atlantek400, manufactured by Global Media Instruments), Dynamic Response was printed in Pattern 4 and Energy Mid, and the print length from the top of the print in Step 2 to the bottom of the print in Step 10 was measured. . Practically, the print length needs to be 15.0 cm or more.
〔印画部の耐可塑剤性評価〕
感熱記録評価機（商品名：ＴＨ－ＰＭＤ、大倉電機社製）を用い、各透明感熱記録体をについて印加エネルギー：０．２４ｍＪ／ｄｏｔ、印字速度４ｉｐｓにて各透明感熱記録体を記録し、記録部を可塑フィルム（商品名：ハイエスソフトＴＭＨ、日本カーバイド社製）に接触させ、４０℃２４時間処理した後、記録部をＸ－ｒｉｔｅ分光濃度計（商品名：Ｘ－ｒｉｔｅ５３０、Ｘ－ｒｉｔｅ社製）のビジュアルモードで測定した。そして、下記式により、記録部の保存率を求めた。
保存率（％）＝（処理後の記録濃度／処理前の記録濃度）×１００
[Evaluation of plasticizer resistance of printed area]
Using a thermal recording evaluation machine (trade name: TH-PMD, manufactured by Okura Electric Co., Ltd.), each transparent thermal recording medium was recorded at an applied energy of 0.24 mJ/dot and a printing speed of 4 ips, The recording area was brought into contact with a plastic film (product name: HIESSOFT TMH, manufactured by Nippon Carbide Co., Ltd.) and treated at 40°C for 24 hours, and then the recording area was exposed to an X-rite spectrodensitometer (product name: Measurements were made using the visual mode of the Then, the retention rate of the recording section was determined using the following formula.
Preservation rate (%) = (Recording density after processing/Recording density before processing) x 100
〔塗料の泡立ち〕
保護層用塗液１００ｍｌを２５０ｍｌのポリ瓶に入れ、試験用分散機（東洋精機社製）で１分間振とうした後、塗料の泡立ちを以下の基準で判定した。
○・・・殆ど泡立ちが見られず、塗料ハンドリングの問題なし。
△・・・やや泡立ちが見られるが、塗料ハンドリングの問題なし。
×・・・相当な泡立ちが見られ、塗料のハンドリングの問題がある。
[Paint bubbling]
100 ml of the coating solution for the protective layer was placed in a 250 ml plastic bottle, and after shaking for 1 minute using a test dispersion machine (manufactured by Toyo Seiki Co., Ltd.), the foaming of the paint was evaluated according to the following criteria.
○...Almost no foaming was observed, and there were no problems with paint handling.
△: Slight bubbling is observed, but there are no problems with paint handling.
×: Considerable bubbling is observed, and there is a problem with paint handling.
Claims (4)
前記接着剤の含有割合が保護層の全固形量中６０質量％以上であり、
前記滑剤としてアルキルリン酸エステル塩、ステアリン酸塩及びＮ置換脂肪酸アミドを含有し、
前記ステアリン酸塩の含有割合が保護層の全固形量中１．０～１０質量％であり、
前記Ｎ置換脂肪酸アミドの含有割合が保護層の全固形量中１．０～１０質量％である
透明感熱記録体。 A transparent thermosensitive recording material having, on one side of a transparent support, at least one thermosensitive recording layer containing a leuco dye and a coloring agent, and a protective layer containing an adhesive and a lubricant in this order,
The content of the adhesive is 60% by mass or more in the total solid amount of the protective layer,
Containing an alkyl phosphate ester salt , a stearate and an N-substituted fatty acid amide as the lubricant,
The content of the stearate is 1.0 to 10% by mass based on the total solid amount of the protective layer,
The content of the N-substituted fatty acid amide is 1.0 to 10% by mass based on the total solid amount of the protective layer.
Transparent heat-sensitive recording material.
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| JP2002326456A (en) | 2001-04-27 | 2002-11-12 | Oji Paper Co Ltd | Heat-sensitive recording medium |
| JP2011037189A (en) | 2009-08-17 | 2011-02-24 | Oji Paper Co Ltd | Transparent thermal recording body and manufacturing method therefor |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2002326456A (en) | 2001-04-27 | 2002-11-12 | Oji Paper Co Ltd | Heat-sensitive recording medium |
| JP2011037189A (en) | 2009-08-17 | 2011-02-24 | Oji Paper Co Ltd | Transparent thermal recording body and manufacturing method therefor |
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