JPH02235685A - Thermally sensitive recording material - Google Patents
Thermally sensitive recording materialInfo
- Publication number
- JPH02235685A JPH02235685A JP1057316A JP5731689A JPH02235685A JP H02235685 A JPH02235685 A JP H02235685A JP 1057316 A JP1057316 A JP 1057316A JP 5731689 A JP5731689 A JP 5731689A JP H02235685 A JPH02235685 A JP H02235685A
- Authority
- JP
- Japan
- Prior art keywords
- weight
- heat
- recording material
- dye
- thermally sensitive
- 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 20
- 238000004040 coloring Methods 0.000 claims description 50
- 150000002903 organophosphorus compounds Chemical class 0.000 claims description 20
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- 239000000975 dye Substances 0.000 abstract description 20
- 150000003839 salts Chemical class 0.000 abstract description 14
- -1 phosphor compound Chemical class 0.000 abstract description 10
- 150000005690 diesters Chemical class 0.000 abstract description 9
- 230000000694 effects Effects 0.000 abstract description 5
- 230000002411 adverse Effects 0.000 abstract description 4
- 239000000981 basic dye Substances 0.000 abstract description 3
- 150000002148 esters Chemical class 0.000 abstract description 3
- AAAQKTZKLRYKHR-UHFFFAOYSA-N triphenylmethane Chemical compound C1=CC=CC=C1C(C=1C=CC=CC=1)C1=CC=CC=C1 AAAQKTZKLRYKHR-UHFFFAOYSA-N 0.000 abstract description 3
- 239000004927 clay Substances 0.000 abstract description 2
- CZZYITDELCSZES-UHFFFAOYSA-N diphenylmethane Chemical compound C=1C=CC=CC=1CC1=CC=CC=C1 CZZYITDELCSZES-UHFFFAOYSA-N 0.000 abstract description 2
- 239000002985 plastic film Substances 0.000 abstract description 2
- 229920006255 plastic film Polymers 0.000 abstract description 2
- 230000003578 releasing effect Effects 0.000 abstract 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract 1
- 239000003513 alkali Substances 0.000 abstract 1
- 239000008119 colloidal silica Substances 0.000 abstract 1
- 239000001993 wax Substances 0.000 description 15
- 229910052751 metal Inorganic materials 0.000 description 14
- 239000002184 metal Substances 0.000 description 14
- PORPEXMDRRVVNF-UHFFFAOYSA-L zinc;octadecyl phosphate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCCOP([O-])([O-])=O PORPEXMDRRVVNF-UHFFFAOYSA-L 0.000 description 12
- 238000000576 coating method Methods 0.000 description 11
- 239000000203 mixture Substances 0.000 description 11
- 229920005989 resin Polymers 0.000 description 11
- 239000011347 resin Substances 0.000 description 11
- 239000011230 binding agent Substances 0.000 description 9
- 239000011248 coating agent Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- 239000007788 liquid Substances 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 150000007524 organic acids Chemical class 0.000 description 5
- 239000004372 Polyvinyl alcohol Substances 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical compound OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 description 4
- 229940114930 potassium stearate Drugs 0.000 description 4
- ANBFRLKBEIFNQU-UHFFFAOYSA-M potassium;octadecanoate Chemical compound [K+].CCCCCCCCCCCCCCCCCC([O-])=O ANBFRLKBEIFNQU-UHFFFAOYSA-M 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 150000003751 zinc Chemical class 0.000 description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical class OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 239000000314 lubricant Substances 0.000 description 3
- UHGIMQLJWRAPLT-UHFFFAOYSA-N octadecyl dihydrogen phosphate Chemical compound CCCCCCCCCCCCCCCCCCOP(O)(O)=O UHGIMQLJWRAPLT-UHFFFAOYSA-N 0.000 description 3
- 235000021317 phosphate Nutrition 0.000 description 3
- 239000000049 pigment Substances 0.000 description 3
- RYYKJJJTJZKILX-UHFFFAOYSA-M sodium octadecanoate Chemical compound [Na+].CCCCCCCCCCCCCCCCCC([O-])=O RYYKJJJTJZKILX-UHFFFAOYSA-M 0.000 description 3
- 239000003381 stabilizer Substances 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 235000021355 Stearic acid Nutrition 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- RUQVDTINGPMNNK-UHFFFAOYSA-H [Al+3].[Al+3].CCCCCCCCCCCCOP([O-])([O-])=O.CCCCCCCCCCCCOP([O-])([O-])=O.CCCCCCCCCCCCOP([O-])([O-])=O Chemical compound [Al+3].[Al+3].CCCCCCCCCCCCOP([O-])([O-])=O.CCCCCCCCCCCCOP([O-])([O-])=O.CCCCCCCCCCCCOP([O-])([O-])=O RUQVDTINGPMNNK-UHFFFAOYSA-H 0.000 description 2
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 2
- VFJUCHICZXDEEY-UHFFFAOYSA-L barium(2+);hexadecyl phosphate Chemical compound [Ba+2].CCCCCCCCCCCCCCCCOP([O-])([O-])=O VFJUCHICZXDEEY-UHFFFAOYSA-L 0.000 description 2
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical class [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 2
- XVCYJJSHYKJNHB-UHFFFAOYSA-L calcium;octadecyl phosphate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCCOP([O-])([O-])=O XVCYJJSHYKJNHB-UHFFFAOYSA-L 0.000 description 2
- 239000004203 carnauba wax Substances 0.000 description 2
- 235000013869 carnauba wax Nutrition 0.000 description 2
- 239000005018 casein Substances 0.000 description 2
- BECPQYXYKAMYBN-UHFFFAOYSA-N casein, tech. Chemical compound NCCCCC(C(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(CC(C)C)N=C(O)C(CCC(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(C(C)O)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(COP(O)(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(N)CC1=CC=CC=C1 BECPQYXYKAMYBN-UHFFFAOYSA-N 0.000 description 2
- 235000021240 caseins Nutrition 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- TVACALAUIQMRDF-UHFFFAOYSA-N dodecyl dihydrogen phosphate Chemical compound CCCCCCCCCCCCOP(O)(O)=O TVACALAUIQMRDF-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- NUVBSKCKDOMJSU-UHFFFAOYSA-N ethylparaben Chemical compound CCOC(=O)C1=CC=C(O)C=C1 NUVBSKCKDOMJSU-UHFFFAOYSA-N 0.000 description 2
- 229940074391 gallic acid Drugs 0.000 description 2
- 235000004515 gallic acid Nutrition 0.000 description 2
- ZUVCYFMOHFTGDM-UHFFFAOYSA-N hexadecyl dihydrogen phosphate Chemical compound CCCCCCCCCCCCCCCCOP(O)(O)=O ZUVCYFMOHFTGDM-UHFFFAOYSA-N 0.000 description 2
- XHQSLVIGPHXVAK-UHFFFAOYSA-K iron(3+);octadecanoate Chemical compound [Fe+3].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XHQSLVIGPHXVAK-UHFFFAOYSA-K 0.000 description 2
- HQKMJHAJHXVSDF-UHFFFAOYSA-L magnesium stearate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQKMJHAJHXVSDF-UHFFFAOYSA-L 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical class CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000008117 stearic acid Substances 0.000 description 2
- 235000010215 titanium dioxide Nutrition 0.000 description 2
- LNAZSHAWQACDHT-XIYTZBAFSA-N (2r,3r,4s,5r,6s)-4,5-dimethoxy-2-(methoxymethyl)-3-[(2s,3r,4s,5r,6r)-3,4,5-trimethoxy-6-(methoxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6r)-4,5,6-trimethoxy-2-(methoxymethyl)oxan-3-yl]oxyoxane Chemical compound CO[C@@H]1[C@@H](OC)[C@H](OC)[C@@H](COC)O[C@H]1O[C@H]1[C@H](OC)[C@@H](OC)[C@H](O[C@H]2[C@@H]([C@@H](OC)[C@H](OC)O[C@@H]2COC)OC)O[C@@H]1COC LNAZSHAWQACDHT-XIYTZBAFSA-N 0.000 description 1
- PYSRRFNXTXNWCD-UHFFFAOYSA-N 3-(2-phenylethenyl)furan-2,5-dione Chemical compound O=C1OC(=O)C(C=CC=2C=CC=CC=2)=C1 PYSRRFNXTXNWCD-UHFFFAOYSA-N 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000001856 Ethyl cellulose Substances 0.000 description 1
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 1
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 1
- 239000004640 Melamine resin Substances 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 229920001800 Shellac Polymers 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 229920000147 Styrene maleic anhydride Polymers 0.000 description 1
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 description 1
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- CEGOLXSVJUTHNZ-UHFFFAOYSA-K aluminium tristearate Chemical compound [Al+3].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CEGOLXSVJUTHNZ-UHFFFAOYSA-K 0.000 description 1
- 229940063655 aluminum stearate Drugs 0.000 description 1
- VHNFAQLOVBWGGB-UHFFFAOYSA-N benzhydrylbenzene;3h-2-benzofuran-1-one Chemical compound C1=CC=C2C(=O)OCC2=C1.C1=CC=CC=C1C(C=1C=CC=CC=1)C1=CC=CC=C1 VHNFAQLOVBWGGB-UHFFFAOYSA-N 0.000 description 1
- 150000001622 bismuth compounds Chemical class 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000008116 calcium stearate Substances 0.000 description 1
- 235000013539 calcium stearate Nutrition 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000003851 corona treatment Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003623 enhancer Substances 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 229920001249 ethyl cellulose Polymers 0.000 description 1
- 235000019325 ethyl cellulose Nutrition 0.000 description 1
- 235000010228 ethyl p-hydroxybenzoate Nutrition 0.000 description 1
- FWQHNLCNFPYBCA-UHFFFAOYSA-N fluoran Chemical compound C12=CC=CC=C2OC2=CC=CC=C2C11OC(=O)C2=CC=CC=C21 FWQHNLCNFPYBCA-UHFFFAOYSA-N 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-M hexanoate Chemical compound CCCCCC([O-])=O FUZZWVXGSFPDMH-UHFFFAOYSA-M 0.000 description 1
- 238000007757 hot melt coating Methods 0.000 description 1
- 239000012943 hotmelt Substances 0.000 description 1
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 1
- 150000003951 lactams Chemical class 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 235000019359 magnesium stearate Nutrition 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 235000010981 methylcellulose Nutrition 0.000 description 1
- 231100000989 no adverse effect Toxicity 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 229910001414 potassium ion Inorganic materials 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000007761 roller coating Methods 0.000 description 1
- ZLGIYFNHBLSMPS-ATJNOEHPSA-N shellac Chemical compound OCCCCCC(O)C(O)CCCCCCCC(O)=O.C1C23[C@H](C(O)=O)CCC2[C@](C)(CO)[C@@H]1C(C(O)=O)=C[C@@H]3O ZLGIYFNHBLSMPS-ATJNOEHPSA-N 0.000 description 1
- 239000004208 shellac Substances 0.000 description 1
- 235000013874 shellac Nutrition 0.000 description 1
- 229940113147 shellac Drugs 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical class [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 125000003003 spiro group Chemical group 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000010186 staining Methods 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 235000018553 tannin Nutrition 0.000 description 1
- 229920001864 tannin Polymers 0.000 description 1
- 239000001648 tannin Substances 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000001016 thiazine dye Substances 0.000 description 1
- 150000003585 thioureas Chemical class 0.000 description 1
- GTBVJMPLFBELEF-UHFFFAOYSA-N tricosyl dihydrogen phosphate Chemical compound CCCCCCCCCCCCCCCCCCCCCCCOP(O)(O)=O GTBVJMPLFBELEF-UHFFFAOYSA-N 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
Landscapes
- Heat Sensitive Colour Forming Recording (AREA)
Abstract
Description
【発明の詳細な説明】
く産業上の利用分野〉
本発明は、サーマルプリンタ等の熱記録装置に使用され
る、感熱紙等の感熱記録材料に関するものである。DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a thermal recording material such as thermal paper used in a thermal recording device such as a thermal printer.
〈従来の技術と発明が解決しようとする課題〉一般に、
上記感熱記録材料は、紙類等からなる支持体層の表面に
、無色または淡色の感熱発色層を形成することで構成さ
れており、感熱発色層の種類によって、゜染料タイプ、
金属塩タイプ、ワックスタイプ等に分類される。そして
、この感熱記録材料においては、上記感熱発色層に熱記
録装置のサーマルヘッドやサーマルペンを接触させて加
熱すると、加熱部分が発色して記録が行われるようにな
っている。<Problems to be solved by conventional technology and inventions> In general,
The above heat-sensitive recording material is constructed by forming a colorless or light-colored heat-sensitive coloring layer on the surface of a support layer made of paper or the like, and depending on the type of the heat-sensitive coloring layer,
It is classified into metal salt type, wax type, etc. In this thermosensitive recording material, when a thermal head or a thermal pen of a thermal recording device is brought into contact with the thermosensitive coloring layer and heated, the heated portion develops color and recording is performed.
また、上記感熱記録材料においては、熱転写の際に感熱
発色層がサーマルヘッドやサーマルペンに融着する、い
わゆる「スティック」を防止し、且つ、感熱記録材料の
、熱記録装置との接触時の滑性、離型性を向上するため
、上記感熱発色層中に滑剤を含有させることが行われて
いる。In addition, in the above-mentioned heat-sensitive recording material, it is possible to prevent so-called "stick" in which the heat-sensitive coloring layer fuses to the thermal head or thermal pen during thermal transfer, and to prevent the heat-sensitive coloring layer from fusing to the thermal head or thermal pen when the heat-sensitive recording material comes into contact with the thermal recording device. In order to improve lubricity and mold releasability, a lubricant is included in the heat-sensitive coloring layer.
滑剤としては、通常、ステアリン酸金属塩等の金属セッ
ケン類が使用されるが、例えばステアリン酸アルミニウ
ム、ステアリン酸マグネシウム、ステアリン酸カルシウ
ムは前記スティック発生の防止効果（以下「耐スティッ
ク性」という）が悪く、また、ステアリン酸亜鉛は耐ス
ティック性に優れるものの、滑性が悪い等の問題があっ
た。Metal soaps such as metal stearates are usually used as lubricants, but aluminum stearate, magnesium stearate, and calcium stearate have poor stick prevention effects (hereinafter referred to as "stick resistance"). Furthermore, although zinc stearate has excellent stick resistance, it has problems such as poor lubricity.
そこで、比較的融点が高く、耐スティック性、滑性、離
型性に優れたステアリン酸ナトリウム、ステアリン酸カ
リウムを用いることが試みられた。Therefore, attempts were made to use sodium stearate and potassium stearate, which have a relatively high melting point and excellent stick resistance, lubricity, and mold release properties.
しかし、感熱記録材料は、転写時に、ごく短時間（数Ｉ
ｓ〜数十ｍｓ程度）ではあるが、４５０℃以上に加熱さ
れるため、上記ステアリン酸ナトリウム、ステアリン酸
カリウムが熱分解して、ナトリウムイオン、カリウムイ
オンを遊離し、サーマルヘッド、サーマルベン、電極、
リード線等の、熱記録装置の金属類を腐蝕するという新
たな問題を生じることが判明した。However, heat-sensitive recording materials can be transferred for a very short time (several I
s to several tens of milliseconds), but because it is heated to 450°C or higher, the above-mentioned sodium stearate and potassium stearate thermally decompose, liberating sodium ions and potassium ions, and causing damage to the thermal head, thermal vent, and electrodes. ,
It has been found that a new problem arises in that the metal parts of the thermal recording device, such as lead wires, are corroded.
本発明は、以上の事情に鑑みてなされたものであって、
耐スティック性、滑性、離型性に優れ、しかも、熱記録
装置に悪影響を与えない感熱記録材料を提供することを
目的としている。The present invention has been made in view of the above circumstances, and
The object of the present invention is to provide a heat-sensitive recording material that has excellent stick resistance, slipperiness, and mold releasability, and does not adversely affect a heat recording device.
〈課題を解決するための手段〉
上記課題を解決するための、本発明に係る感熱記録材料
は、支持体層の表面に少なくとも感熱発色層を備えた感
熱記録材料において、上記感熱発色層が、下記一般式（
Ｉ）および／または一般式（Ｉ［）で表わされる有機り
ん化合物（以下「特定有機りん化合物」という）を含有
することを特徴としている。<Means for Solving the Problems> To solve the above problems, a heat-sensitive recording material according to the present invention is a heat-sensitive recording material comprising at least a heat-sensitive coloring layer on the surface of a support layer, in which the heat-sensitive coloring layer comprises: The following general formula (
I) and/or an organic phosphorus compound represented by the general formula (I[) (hereinafter referred to as "specific organic phosphorus compound").
（上記式中、Ｒは炭素数８以上のアルキル基を表わし、
Ｍはアルカリ土類金属、アルミニウムまたは亜鉛を表わ
し、ｍはＭの原子価と同じ整数を表わす）
上記構成からなる感熱記録材料においては、肩剤として
の上記一般式（Ｉ）および／または一般式（Ｉ［）で表
わされる特定有機りん化合物が、耐スティック性、滑性
、離型性に優れると共に、耐熱性にも優れており、しか
も、分子中に、金属類を腐蝕するアルカリ金属を含まな
いので、熱記録装置に悪影響を与えることがない。(In the above formula, R represents an alkyl group having 8 or more carbon atoms,
(M represents an alkaline earth metal, aluminum or zinc, and m represents the same integer as the valence of M) In the heat-sensitive recording material having the above structure, the general formula (I) and/or the general formula The specific organic phosphorus compound represented by (I[) has excellent stick resistance, slipperiness, and mold releasability as well as heat resistance, and also contains alkali metals that corrode metals in the molecule. There is no negative effect on the thermal recording device.
上記特定有機りん化合物としては、前記一般式（Ｉ）で
表わされるアルキルりん酸モノエステルおよび／または
一般式（ＩＩ）で表わされるアルキルりん酸ジエステル
の、アルカリ土類金属塩、アルミニウム塩または亜鉛塩
が用いられる。なお、上記両式中、Ｒで表わされるアル
キル基の炭素数は８以上である必要がある。炭素数が８
未満では滑性が不充分で、耐スティック性等を改善する
ことが困難になるからである。The specific organic phosphorus compound is an alkaline earth metal salt, aluminum salt, or zinc salt of the alkyl phosphate monoester represented by the general formula (I) and/or the alkyl phosphate diester represented by the general formula (II). is used. In addition, in both the above formulas, the number of carbon atoms in the alkyl group represented by R must be 8 or more. Number of carbons is 8
This is because if it is less than that, the slipperiness will be insufficient and it will be difficult to improve stick resistance and the like.
特定有機りん化合物としては、上記一般式（Ｉ）および
／または一般式（Ｉ）に該当する種々の化合物を使用で
きるが、．特に、ラウリルりん酸エステル（ドデシルり
ん酸エステル）、セチルりん酸エステル（ヘキサデシル
りん酸エステル）、ステアリルりん酸エステル（オクタ
デシルりん酸エステル）トリコシルりん酸エステル等の
りん酸エステルのアルカリ土類金属塩、アルミニウム塩
または亜鉛塩が好ましいものとして挙げられる。As the specific organic phosphorus compound, various compounds corresponding to the above general formula (I) and/or general formula (I) can be used. In particular, alkaline earth metal salts of phosphates such as lauryl phosphate (dodecyl phosphate), cetyl phosphate (hexadecyl phosphate), stearyl phosphate (octadecyl phosphate) and tricosyl phosphate; Aluminum salts or zinc salts are preferred.
なお、上記特定有機りん化合物は、アルキル基の炭素数
が多いほど滑性に優れているが、供給量や価格等を考慮
すれば、炭素数が２３以下のものが好ましく、特に、上
記ステアリルりん酸エステルの亜鉛塩が最も好ましく用
いられる。The above-mentioned specific organic phosphorus compound has better lubricity as the number of carbon atoms in the alkyl group increases, but in consideration of supply amount and price, it is preferable that the above-mentioned organic phosphorus compound has 23 or less carbon atoms. Zinc salts of acid esters are most preferably used.
また、上記特定有機りん化合物は、一般に、前記一般式
ｍで表されるモノエステルと、一般式（Ｉ［）で表され
るジエステルとの混合物として製造されるものであり、
この混合物における、上記両者の比率は特に限定されな
いが、上記ステアリルりん酸エステルの亜鉛塩の場合に
は、ジエステルとモノエステルの比が、モル比で、１：
２．７〜２．７＝１の範囲内であることが好ましい。Further, the specific organic phosphorus compound is generally produced as a mixture of a monoester represented by the general formula m and a diester represented by the general formula (I[),
The ratio of the two in this mixture is not particularly limited, but in the case of the zinc salt of stearyl phosphate, the molar ratio of diester to monoester is 1:
It is preferably within the range of 2.7 to 2.7=1.
上記特定有機りん化合物が配合され不感熱発色層として
は、前記染料タイプ、金属塩タイプ、およびワックスタ
イプ等の、現在用いられている種々の感熱発色層が用い
られる。As the heat-insensitive color-forming layer containing the specific organic phosphorus compound, various currently used heat-sensitive color-forming layers such as the dye type, metal salt type, and wax type may be used.
染料タイプの感熱発色層は、単体では無色または淡色の
染料と、この染料と反応して発色させるための顕色剤と
を結着樹脂中に分散させたもので、加熱されたサーマル
ヘッド等が感熱発色層に接触すると、上記染料および顕
色剤のうちの少なくとも一方が溶融して、層中において
両者が接触し、反応して、加熱部分を発色させるもので
ある。そして、上記特定有機りん化合物は、染料および
顕色剤と共に、結着樹脂中に含有される。A dye-type thermosensitive coloring layer consists of a colorless or light-colored dye and a color developer that reacts with the dye to develop color, dispersed in a binder resin. When it comes into contact with the heat-sensitive coloring layer, at least one of the dye and the color developer melts, and the two come into contact in the layer and react, causing the heated portion to develop color. The specific organic phosphorus compound is contained in the binder resin together with the dye and the color developer.
染料としては、ジフエニルメタン系染料、トリフエニル
メタン系染料、チアジン系染料、スピロ系染料、ラクタ
ム系染料、フルオラン系染料等の塩基性染料が好ましく
用いられ、この塩基性染料と反応する顕色剤としては、
活性白土、コロイダルシリ力、珪酸アルミニウム、ビス
フェノールＡ１トリフェニルメタンフタリド、４−ヒド
ロキシ安息香酸エチル等の無機または有機の酸性物質が
好ましく用いられる。As the dye, basic dyes such as diphenylmethane dyes, triphenylmethane dyes, thiazine dyes, spiro dyes, lactam dyes, and fluoran dyes are preferably used, and as a color developer that reacts with the basic dyes. teeth,
Inorganic or organic acidic substances such as activated clay, colloidal silicate, aluminum silicate, bisphenol A1 triphenylmethane phthalide, and ethyl 4-hydroxybenzoate are preferably used.
また、上記染料と顕色剤とが分散される結着樹脂として
は、シリコーン樹脂、エボキシ樹脂、メラミン樹脂、フ
ェノール樹脂、フッ素樹脂等の熱硬化性樹脂；ヒドロキ
シエチルセルロース、エチルセルロース、メチルセルロ
ース、カルボキシメチルセルロース、ポリビニルアルコ
ール、ポリアクリルアミド、ポリビニルピロリドン、で
んぷんおよびその誘導体、カゼイン、ゼラチン、シエラ
ック、スチレンー無水マレイン酸共重合体等の水溶性樹
脂が用いられる。なお、上記結着樹脂中には、増感剤、
安定化剤、充填剤等が配合されていても良い。In addition, examples of the binder resin in which the dye and developer are dispersed include thermosetting resins such as silicone resin, epoxy resin, melamine resin, phenol resin, and fluororesin; hydroxyethyl cellulose, ethyl cellulose, methyl cellulose, carboxymethyl cellulose, Water-soluble resins such as polyvinyl alcohol, polyacrylamide, polyvinylpyrrolidone, starch and its derivatives, casein, gelatin, shellac, and styrene-maleic anhydride copolymer are used. Note that the binder resin contains a sensitizer,
Stabilizers, fillers, etc. may be added.
金属塩タイプの感熱発色層は、有機酸金属塩と、この有
機酸金属塩と反応して錯塩を形成する発色反応試薬とを
結着樹脂中に分散させたもので、先の染料タイプの感熱
発色層と同様に、上記有機酸金属塩および発色反応試薬
のうちの少なくとも一方が加熱時に溶融して、層中にお
いて両者が接触し、反応して発色するようになっている
。そして、前記特定有機りん化合物は、染料および顕恒
剤と共に、結着樹脂中に含有される。The metal salt type heat-sensitive coloring layer is made by dispersing an organic acid metal salt and a coloring reaction reagent that reacts with the organic acid metal salt to form a complex salt in a binder resin. Similar to the color-forming layer, at least one of the organic acid metal salt and the color-forming reaction reagent melts when heated, and the two come into contact in the layer, reacting, and developing color. The specific organic phosphorus compound is contained in the binder resin together with the dye and the enhancer.
有機酸金属塩と発色反応試薬との組み合わせとしては、
ステアリン酸第二鉄とタンニンまたは没食子酸；ステア
リン酸のＮＬ， Ｃｏ， Ｃｕ塩とアルカリ土類金属硫
化物；シュウ酸の重金属塩とチオ硫酸ナトリウム；カプ
ロン酸鉛とチオ尿素誘導体；ビスマス化合物とスズ化合
物等、従来公知の種々の組み合わせ゛を採用することが
できる。また、゛結着樹脂としては、先の染料タイプの
感熱発色層において例示した樹脂材料を使用することが
でき、上記結着樹脂中には、増感剤、安定化剤、充填剤
等が配合されていても良い。Combinations of organic acid metal salts and coloring reaction reagents include:
Ferric stearate and tannin or gallic acid; NL, Co, and Cu salts of stearic acid and alkaline earth metal sulfides; Heavy metal salts of oxalic acid and sodium thiosulfate; Lead caproate and thiourea derivatives; Bismuth compounds and tin Various conventionally known combinations of compounds and the like can be employed. Further, as the binder resin, the resin materials exemplified in the dye-type heat-sensitive coloring layer above can be used, and the binder resin contains sensitizers, stabilizers, fillers, etc. It's okay if it's done.
上記染料タイプおよび金属塩タイプの感熱発色層におい
ては、層中の特定有機りん化合物の含有割合は、０．Ｏ
ｌ〜１５重量％の範囲内であることが好ましい。含有割
合が０．０１重量％未満では、耐スティック性、滑性、
離型性を十分に発揮することができず、１５重量％を超
えると、特定有機りん化合物が感熱発色層から滲出して
、熱記録装置等を汚したり、サーマルヘッドにカスがた
まり易くなったりする。In the dye-type and metal salt-type heat-sensitive coloring layers described above, the content ratio of the specific organic phosphorus compound in the layer is 0. O
It is preferably within the range of 1 to 15% by weight. If the content is less than 0.01% by weight, stick resistance, slipperiness,
If the amount exceeds 15% by weight, the specific organic phosphorus compound may ooze out from the heat-sensitive coloring layer, staining the thermal recording device, etc., or causing residue to accumulate in the thermal head. do.
上記両タイプの感熱発色層は、各成分を含有する塗工液
を、スプレーコーティング法、ローラーコーティング法
、ブレードコーティング法等、従来慣用のコーティング
法により、支持体層の表面に塗布することで形成される
。なお、支持体層への密着性を向上し、感熱発色層をよ
り一層強固なものとするためには、上記塗布に先立ち、
支持体層の表面に、コロナ放電処理等の前処理を施すこ
とが好ましい。Both types of heat-sensitive coloring layers mentioned above are formed by applying a coating solution containing each component onto the surface of the support layer using conventional coating methods such as spray coating, roller coating, and blade coating. be done. In addition, in order to improve the adhesion to the support layer and make the thermosensitive coloring layer even stronger, prior to the above coating,
Preferably, the surface of the support layer is subjected to a pretreatment such as corona discharge treatment.
一方、ワックスタイプの感熱発色層は、着色層と、この
着色層の上に積層された不透明ワックス層とからなり、
サーマルヘッドが接触した部分の不透明ワックス層が溶
融除去されて、下層の着色層が露出することで加熱部分
が発色するものである。特定有機りん化合物は、サーマ
ルヘッドと直接に接触する不透明ワックス層中に含有さ
れるが、さらに、下層の着色層にも特定有機りん化合物
を含有させることができる。On the other hand, a wax type thermosensitive coloring layer consists of a colored layer and an opaque wax layer laminated on the colored layer.
The opaque wax layer in the area in contact with the thermal head is melted and removed, exposing the underlying colored layer, causing the heated area to develop color. The specific organic phosphorus compound is contained in the opaque wax layer that comes into direct contact with the thermal head, but the specific organic phosphorus compound can also be contained in the lower colored layer.
上記不透明ワックス層における、特定有機りん化合物の
含有割合は、０，０１〜１５重量％の範囲内であること
が好ましい。含有割合が０．０１重量％未満では、耐ス
ティック性、滑性、離型性を十分に発揮することができ
ず、１５重量％を超えると、特定有機りん化合物が感熱
発色層から滲出して、熱記録装置等を汚したり、サーマ
ルヘッドにカスがたまり易くなったりする。また、着色
層にも特定有機りん化合物を含有させる場合には、上記
と同様の理由により、その含有割合は、０．０１〜１５
重量％の範囲内であることが好ましい。The content of the specific organic phosphorus compound in the opaque wax layer is preferably in the range of 0.01 to 15% by weight. If the content is less than 0.01% by weight, the stick resistance, slipperiness, and mold release properties cannot be sufficiently exhibited, and if the content exceeds 15% by weight, the specific organic phosphorus compound will ooze out from the thermosensitive coloring layer. , it may stain the thermal recording device, etc., and it may become easy for debris to accumulate on the thermal head. In addition, when the colored layer also contains a specific organic phosphorus compound, the content ratio should be 0.01 to 15 for the same reason as above.
Preferably, it is within the range of % by weight.
なお、不透明ワックスとしては、バラフィンワックス、
カルナウバワックス等のワックスに、チタン白等の顔料
を分散させたものが例示される。In addition, as opaque wax, paraffin wax,
An example is one in which a pigment such as titanium white is dispersed in a wax such as carnauba wax.
上記、ワックスタイプの感熱発色層は、支持体層の表面
に着色層を形成した後、上記不透明ワックスを、ホット
メルトコーティング、溶剤コーティング、エマルジョン
コーティング等の塗工方法により、着色層の表面に塗布
積層することで形成される。The above-mentioned wax-type thermosensitive coloring layer is formed by forming a colored layer on the surface of the support layer, and then applying the above-mentioned opaque wax to the surface of the colored layer by a coating method such as hot melt coating, solvent coating, emulsion coating, etc. It is formed by laminating layers.
上記例示の各感熱発色層の膜厚は、発色層の種類によっ
て異なるが、それぞれの感熱発色層に最適の、従来公知
の膜厚範囲を適用することができる。The film thickness of each of the above-mentioned heat-sensitive coloring layers varies depending on the type of coloring layer, but a conventionally known film thickness range that is optimal for each heat-sensitive coloring layer can be applied.
また、上記各種感熱発色層を支持する支持体層としては
、感熱記録材料に通常用いられている種々の素材を使用
することができ、好ましい素材としては、天然紙、合成
紙等の紙類の他、プラスチックフィルム等が挙げられる
。Furthermore, as the support layer that supports the various heat-sensitive coloring layers mentioned above, various materials commonly used for heat-sensitive recording materials can be used, and preferred materials include paper such as natural paper and synthetic paper. Other examples include plastic films.
く実施例〉
以下、本発明を、実施例並びに比較例に基づいて説明す
る。Examples> The present invention will be described below based on Examples and Comparative Examples.
（実施例１）
下記各配合のＡ液５重量部、Ｂ液４０重量部、Ｃ液１５
重量部を２０重量％ポリビニルアルコール水溶液３０重
量部と混合して、感熱発色層用塗工液を調製した。(Example 1) 5 parts by weight of liquid A, 40 parts by weight of liquid B, and 15 parts by weight of liquid C in each of the following formulations.
Parts by weight were mixed with 30 parts by weight of a 20% by weight polyvinyl alcohol aqueous solution to prepare a coating liquid for a heat-sensitive coloring layer.
Ａ液
クリスタルバイオレット粉末（※）・・・２０．０重量
部１０重量％ボリビニルアルコール
水溶液・・・５０．０重量部
水 ・・・３０．０
重量部※：トリフエニルメタン系染料
・ Ｂ？＆
ビスフェノールＡ（顕色剤） ・・・１０．０重量
部炭酸カルシウム粉末（充填剤） ・・・２０．０重
量部１０重量％ボリビニルアルコール
水溶液・・・５０．０重量部
水 ・・・２０．０
重量部・Ｃ液
ステアリルりん酸エステル亜鉛塩（＊）・・・２０．０
重量部
１０重量％カゼイン水溶液 ・・・２０．０重
量部水 ・・・６
０，０重量部＊：ジエステルとモノエステルの比が、モ
ル比で１ ７ ２．７〜２．７：１の混合物（堺化学社
製、商品名ｒＬＢＴ−１８３０Ｊ ）
次に、上記塗工液を、乾燥後の厚みが約ｌＯＫ／ゴにな
るように、坪量５０ｇ／ｄのＢ５判一般紙の表面に塗布
、乾燥して、染料タイプの感熱発色層を有する感熱記録
紙を作製した。感熱発色層中におけるステアリルりん酸
エステル亜鉛塩の含有割合は１２．２重量％であった。Liquid A crystal violet powder (*)...20.0 parts by weight 10% by weight aqueous polyvinyl alcohol solution...50.0 parts by weight Water...30.0
Part by weight*: Triphenylmethane dye/B? & Bisphenol A (color developer)...10.0 parts by weight Calcium carbonate powder (filler)...20.0 parts by weight 10% by weight aqueous vorivinyl alcohol solution...50.0 parts by weight Water... 20.0
Part by weight・Liquid C stearyl phosphate ester zinc salt (*)...20.0
Parts by weight 10% by weight casein aqueous solution...20.0 parts by weight Water...6
0.0 parts by weight *: A mixture with a molar ratio of diester and monoester of 1 7 2.7 to 2.7:1 (manufactured by Sakai Chemical Co., Ltd., trade name rLBT-1830J) Next, the above coating liquid was coated on the surface of B5 size general paper with a basis weight of 50 g/d so that the thickness after drying was about 1 OK/g, and dried to produce a thermosensitive recording paper having a dye type thermosensitive coloring layer. The content of stearyl phosphate zinc salt in the heat-sensitive coloring layer was 12.2% by weight.
（実施例２）
Ａ液中のステアリルりん酸エステル亜鉛塩の配合量を０
．５重量部としたこと以外は、上記実施例１と同様にし
て、染料タイプの感熱発色層を有する感熱記録紙を作製
した。感熱発色層中におけるステアリルりん酸エステル
亜鉛塩の含有割合は１．２重量％であった。(Example 2) The amount of stearyl phosphate zinc salt in liquid A was 0.
．． A thermosensitive recording paper having a dye-type thermosensitive coloring layer was produced in the same manner as in Example 1 above, except that the amount was 5 parts by weight. The content of stearyl phosphate zinc salt in the heat-sensitive coloring layer was 1.2% by weight.
（実施例３）
Ａ液中のステアリルりん酸エステル亜鉛塩２０．０重量
部に代えて、セチルりん酸エステルバリウム塩（ジエス
テルとモノエステルの比が、モル比で１：１の混合物）
２０．０重量部を用いたこと以外は、上記実施例１と
同様にして、染料タイプの感熱発色層を有する感熱記録
紙を作製した。感熱発色層中におけるセチルりん酸エス
テルバリウム塩の含有割合は１２．２重量％であった。(Example 3) Instead of 20.0 parts by weight of stearyl phosphate zinc salt in Solution A, cetyl phosphate barium salt (mixture of diester and monoester in a molar ratio of 1:1)
A thermosensitive recording paper having a dye-type thermosensitive coloring layer was produced in the same manner as in Example 1 above, except that 20.0 parts by weight was used. The content of cetyl phosphate barium salt in the heat-sensitive coloring layer was 12.2% by weight.
（実施例４）
Ａ液中のステアリルりん酸エステル亜鉛塩２０．０重量
部に代えて、ラウリルりん酸エステルアルミニウム塩（
ジエステルとモノエステルの比が、モル比で１：１の混
合物） ２０．０重量部を用いたこと以外は、上記実施
例１と同様にして、染料タイプの感熱発色層を有する感
熱記録紙を作製した。感熱発色層中におけるラウリルり
ん酸エステルアルミニウム塩の含有割合は１２．２重量
％であった。(Example 4) In place of 20.0 parts by weight of stearyl phosphate zinc salt in Solution A, lauryl phosphate aluminum salt (
A thermosensitive recording paper having a dye-type thermosensitive coloring layer was prepared in the same manner as in Example 1 above, except that 20.0 parts by weight of a mixture (with a molar ratio of diester and monoester of 1:1) was used. Created. The content of lauryl phosphate aluminum salt in the heat-sensitive coloring layer was 12.2% by weight.
（実施例５）
Ａ液中のステアリルりん酸エステル亜鉛塩２０。０重量
部に代えて、ステアリルりん酸エステルカルシウム塩（
ジエステルとモノエステルの比が、モル比で１：２の混
合物） ２０．０重量部を用いたこと以外は、上記実施
例１と同様にして、染料タイプの感熱発色層を有する感
熱記録紙を作製した。感熱発色層中におけるステアリル
りん酸エステルカルシウム塩の含有割合は１２．２重量
％であった。(Example 5) In place of 20.0 parts by weight of stearyl phosphate zinc salt in Solution A, stearyl phosphate calcium salt (
A thermosensitive recording paper having a dye-type thermosensitive coloring layer was prepared in the same manner as in Example 1 above, except that 20.0 parts by weight of a mixture (with a molar ratio of diester and monoester of 1:2) was used. Created. The content of stearyl phosphate calcium salt in the heat-sensitive coloring layer was 12.2% by weight.
（比較例１）
Ａ液中のステアリルりん酸エステル亜鉛塩２０．０重量
部に代えて、ステアリン酸カリウム２０．０重量部を用
いたこと以外は、上記実施例１と同様にして、染料タイ
プの感熱発色層を有する感熱記録紙を作製した。感熱発
色層中におけるステアリン酸カリウムの含有割合は１２
．２重量％であった。(Comparative Example 1) Dye type A thermosensitive recording paper having a thermosensitive coloring layer was produced. The content ratio of potassium stearate in the heat-sensitive coloring layer is 12
．． It was 2% by weight.
（比較例２）
感熱発色層用塗工液にステアリルりん酸エステル亜鉛塩
を配合しなかったこと以外は、上記実施例１と同様にし
て、染料タイプの感熱発色層を有する感熱記録紙を作製
した。(Comparative Example 2) A thermosensitive recording paper having a dye-type thermosensitive coloring layer was produced in the same manner as in Example 1 above, except that stearyl phosphate zinc salt was not blended into the coating solution for the thermosensitive coloring layer. did.
（実施例６）
坪量５０ｇ／ｒｄのＢ５判一般紙の表面に、ステアリル
りん酸エステル亜鉛塩（ジエステルとモノエステルの比
が、モル比で１ ： ２．７〜２．７：ｌの混合物、堺
化学社製、商品名ｒＬＢＴ−１８３０Ｊ ）２．０重量
部、有機酸金属塩としてのステアリン酸第二鉄３．０重
量部、発色反応試薬としての没食子酸２．０重量部、１
０重量％ボリビニルアルコール水溶液ｔｏｏ．ｏ重量部
、および水２０．０重量部からなる感熱発色層用塗工液
を、乾燥後の厚みが約ＬＯｇ／イになるように塗布し乾
燥して、金属塩タイプの感熱発色層を有する感熱記録紙
を得た。感熱発色層中におけるステアリルりん酸エステ
ル亜鉛塩の含有割合は１１．８重量％であった。(Example 6) A stearyl phosphate ester zinc salt (a mixture of diester and monoester in a molar ratio of 1:2.7 to 2.7:l) was applied to the surface of B5 size general paper with a basis weight of 50 g/rd. , manufactured by Sakai Chemical Co., Ltd., trade name rLBT-1830J) 2.0 parts by weight, 3.0 parts by weight of ferric stearate as an organic acid metal salt, 2.0 parts by weight of gallic acid as a coloring reaction reagent, 1
0% by weight polyvinyl alcohol aqueous solution too. A coating solution for a heat-sensitive coloring layer consisting of 0 parts by weight and 20.0 parts by weight of water is applied so that the thickness after drying is about LOg/a, and dried to form a metal salt type heat-sensitive coloring layer. A thermosensitive recording paper was obtained. The content of stearyl phosphate zinc salt in the heat-sensitive coloring layer was 11.8% by weight.
（実施例７）
坪量５０ｇ／ｒｄのＢ５判一般紙の表面に、カーボンブ
ラックを顔料として含有する黒色着色層を形成した後、
この黒色着色層の表面に、ステアリルりん酸エステル亜
鉛塩（ジエステルとモノエステルの比が、モル比で１
： ２．７〜２．７：ｌの混合物、堺化学社製、商品名
ｒＬＢＴ−１８３０Ｊ ）１５．０重量部、バインダー
としてのカルナウバワックス６０．０重量部、顔料とし
てのチタン白２０．０重量部、柔軟剤としてのステアリ
ン酸１０．０重量部、そして、安定剤等の添加剤ＩＯ．
０重量部からなる不透明ワックス組成物を、ホットメル
トコーターを用いて溶融塗布し冷却して、厚み約１０ｇ
／ｒｄの不透明ワックス層を積層形成し、ワックスタイ
プの感熱発色層を有する感熱記録紙を作製した。不透明
ワックス層中におけるステアリルりん酸エステル亜鉛塩
の含有割合は１３．０重量％であった。(Example 7) After forming a black colored layer containing carbon black as a pigment on the surface of B5 size general paper with a basis weight of 50 g/rd,
The surface of this black colored layer is coated with stearyl phosphate zinc salt (the molar ratio of diester to monoester is 1).
: 2.7 to 2.7:l mixture, manufactured by Sakai Chemical Co., Ltd., trade name rLBT-1830J) 15.0 parts by weight, 60.0 parts by weight of carnauba wax as a binder, 20.0 parts by weight of titanium white as a pigment parts by weight, 10.0 parts by weight of stearic acid as a softener, and IO. parts by weight of additives such as stabilizers.
An opaque wax composition consisting of 0 parts by weight was melt coated using a hot melt coater and cooled to a thickness of approximately 10 g.
/rd opaque wax layers were laminated to produce a thermosensitive recording paper having a wax type thermosensitive coloring layer. The content of stearyl phosphate zinc salt in the opaque wax layer was 13.0% by weight.
（比較例３）
ステアリルりん酸エステル亜鉛塩１５．０重量部に代え
て、ステアリン酸ナトリウムｌ５，０重量部を用いたこ
と以外は、上記実施例７と同様にして、ワックスタイプ
の感熱発色層を有する感熱記録紙を作製した。感熱発色
層中におけるステアリン酸カリウムの含有割合は１３．
０重量％であった。(Comparative Example 3) A wax-type thermosensitive coloring layer was prepared in the same manner as in Example 7, except that 15.0 parts by weight of sodium stearate was used in place of 15.0 parts by weight of stearyl phosphate zinc salt. A thermosensitive recording paper having the following properties was prepared. The content ratio of potassium stearate in the heat-sensitive coloring layer is 13.
It was 0% by weight.
（比較例４）
不透明ワックス組成物にステアリルりん酸エステル亜鉛
塩を配合しなかったこと以外は、上記実施例７と同様に
して、ワックスタイプの感熱発色層を有する感熱記録紙
を作製した。(Comparative Example 4) A thermosensitive recording paper having a wax-type thermosensitive coloring layer was produced in the same manner as in Example 7 except that stearyl phosphate zinc salt was not blended into the opaque wax composition.
（実用試験）
上記実施例１〜７並びに比較例１〜４で作製した８５判
の感熱記録紙５０００枚を、サーマルプリンタを用いて
連続印字した際のスティック等の有無を観察したところ
、滑剤を含有しない比較例２．４の感熱記録紙ではステ
ィックや他の機械部分での用紙送りの不良が多発したが
、実施例１〜７並びに比較例１．３の感熱記録紙ではス
ティック、用紙送りの不良共に発生しなかった。(Practical test) When 5000 sheets of 85-size thermal recording paper produced in Examples 1 to 7 and Comparative Examples 1 to 4 were continuously printed using a thermal printer, the presence or absence of sticks was observed. In the thermal recording paper of Comparative Example 2.4, which did not contain the compound, there were many paper feeding defects due to sticks and other mechanical parts, but in the thermal recording paper of Examples 1 to 7 and Comparative Example 1.3, there were no stick or paper feeding defects. It did not occur.
また、感熱記録紙５０００枚の印字後にサーマルブリン
クを検査したところ、比較例１．３の熱転写リボンを用
いたサーマルプリンタでは、窒化チタン製のサーマルヘ
ッドや、このサーマルヘッドの周辺に配置された錫製の
電極類、ア！レミニウム製のリード線類等に腐蝕が観察
されたが、実施例１〜７の感熱記録紙を用いたサーマル
プリンタにおいては腐蝕は全く観察されなかった。In addition, when thermal blink was inspected after printing on 5,000 sheets of thermal recording paper, it was found that in the thermal printer using the thermal transfer ribbon of Comparative Example 1.3, the thermal head made of titanium nitride and the tin Electrodes made by A! Corrosion was observed in lead wires made of reminium, but no corrosion was observed in the thermal printers using the heat-sensitive recording papers of Examples 1 to 7.
以上のことから、実施例１〜７の感熱記録紙は、耐ステ
ィック性、滑性、離型性に優れると共に、熱記録装置に
悪影響を与えないことが判明した。From the above, it was found that the thermal recording papers of Examples 1 to 7 were excellent in stick resistance, slipperiness, and mold releasability, and did not adversely affect thermal recording devices.
く発明の効果〉
本発明に係る熱転写記録材料は、上記のように構成され
ており、滑剤として特定有機りん化合物を用いているの
で、耐スティック性、滑性、離型性に優れ、しかも、熱
記録装置に悪影響を与えることのないものとなっている
。Effects of the Invention The thermal transfer recording material according to the present invention is configured as described above, and since a specific organic phosphorus compound is used as a lubricant, it has excellent stick resistance, lubricity, and mold releasability, and also has It has no adverse effect on the thermal recording device.
Claims (1)
熱記録材料において、上記感熱発色層が、下記一般式（
I ）および／または一般式（II）で表わされる有機り
ん化合物を含有することを特徴とする感熱記録材料。 ▲数式、化学式、表等があります▼・・・（ I ） ▲数式、化学式、表等があります▼・・・（II） （上記式中、Ｒは炭素数８以上のアルキル基を表わし、
Ｍはアルカリ土類金属、アルミニウムまたは亜鉛を表わ
し、ｍはＭの原子価と同じ整数を表わす）[Claims] 1. In a heat-sensitive recording material having at least a heat-sensitive coloring layer on the surface of the support layer, the heat-sensitive coloring layer has the following general formula (
1) and/or an organic phosphorus compound represented by general formula (II). ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(II) (In the above formula, R represents an alkyl group with 8 or more carbon atoms,
M represents an alkaline earth metal, aluminum or zinc, m represents the same integer as the valence of M)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1057316A JPH02235685A (en) | 1989-03-08 | 1989-03-08 | Thermally sensitive recording material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1057316A JPH02235685A (en) | 1989-03-08 | 1989-03-08 | Thermally sensitive recording material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH02235685A true JPH02235685A (en) | 1990-09-18 |
Family
ID=13052166
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1057316A Pending JPH02235685A (en) | 1989-03-08 | 1989-03-08 | Thermally sensitive recording material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02235685A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02310084A (en) * | 1989-05-24 | 1990-12-25 | Adeka Argus Chem Co Ltd | Thermal recording material |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60101079A (en) * | 1983-11-07 | 1985-06-05 | Matsumoto Yushi Seiyaku Kk | Treating agent for thermal recording paper |
| JPS62149478A (en) * | 1985-12-25 | 1987-07-03 | Ricoh Co Ltd | Thermal recording material |
-
1989
- 1989-03-08 JP JP1057316A patent/JPH02235685A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60101079A (en) * | 1983-11-07 | 1985-06-05 | Matsumoto Yushi Seiyaku Kk | Treating agent for thermal recording paper |
| JPS62149478A (en) * | 1985-12-25 | 1987-07-03 | Ricoh Co Ltd | Thermal recording material |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02310084A (en) * | 1989-05-24 | 1990-12-25 | Adeka Argus Chem Co Ltd | Thermal recording material |
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