JPS63179788A - Thermal recording material - Google Patents
Thermal recording materialInfo
- Publication number
- JPS63179788A JPS63179788A JP62009939A JP993987A JPS63179788A JP S63179788 A JPS63179788 A JP S63179788A JP 62009939 A JP62009939 A JP 62009939A JP 993987 A JP993987 A JP 993987A JP S63179788 A JPS63179788 A JP S63179788A
- Authority
- JP
- Japan
- Prior art keywords
- color
- heat
- recording material
- color developer
- thermal
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000463 material Substances 0.000 title claims abstract description 30
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 9
- 239000011701 zinc Substances 0.000 claims abstract description 9
- -1 vinyl ether compound Chemical class 0.000 claims abstract description 8
- 238000004040 coloring Methods 0.000 claims description 11
- 239000000126 substance Substances 0.000 claims description 7
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims description 2
- 125000005843 halogen group Chemical group 0.000 claims description 2
- 125000005842 heteroatom Chemical group 0.000 claims description 2
- 239000013110 organic ligand Substances 0.000 claims description 2
- 239000007788 liquid Substances 0.000 abstract description 22
- 230000035945 sensitivity Effects 0.000 abstract description 8
- 239000003921 oil Substances 0.000 abstract description 5
- 239000004014 plasticizer Substances 0.000 abstract description 5
- 239000011248 coating agent Substances 0.000 abstract description 4
- 238000000576 coating method Methods 0.000 abstract description 4
- 238000001035 drying Methods 0.000 abstract description 3
- 239000002985 plastic film Substances 0.000 abstract description 3
- 229920006255 plastic film Polymers 0.000 abstract description 3
- 239000003795 chemical substances by application Substances 0.000 abstract description 2
- 239000000470 constituent Substances 0.000 abstract 1
- 238000010276 construction Methods 0.000 abstract 1
- 239000003925 fat Substances 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 21
- 239000000975 dye Substances 0.000 description 12
- 239000010410 layer Substances 0.000 description 11
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- FWQHNLCNFPYBCA-UHFFFAOYSA-N fluoran Chemical compound C12=CC=CC=C2OC2=CC=CC=C2C11OC(=O)C2=CC=CC=C21 FWQHNLCNFPYBCA-UHFFFAOYSA-N 0.000 description 9
- 229920001577 copolymer Polymers 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 6
- 229920000609 methyl cellulose Polymers 0.000 description 6
- 239000001923 methylcellulose Substances 0.000 description 6
- 235000010981 methylcellulose Nutrition 0.000 description 6
- 238000000034 method Methods 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- WNZQDUSMALZDQF-UHFFFAOYSA-N 2-benzofuran-1(3H)-one Chemical compound C1=CC=C2C(=O)OCC2=C1 WNZQDUSMALZDQF-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 235000019198 oils Nutrition 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- RLFWWDJHLFCNIJ-UHFFFAOYSA-N Aminoantipyrine Natural products CN1C(C)=C(N)C(=O)N1C1=CC=CC=C1 RLFWWDJHLFCNIJ-UHFFFAOYSA-N 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 3
- VEQOALNAAJBPNY-UHFFFAOYSA-N antipyrine Chemical compound CN1C(C)=CC(=O)N1C1=CC=CC=C1 VEQOALNAAJBPNY-UHFFFAOYSA-N 0.000 description 3
- 239000003086 colorant Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 235000014113 dietary fatty acids Nutrition 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000194 fatty acid Substances 0.000 description 3
- 229930195729 fatty acid Natural products 0.000 description 3
- 150000004665 fatty acids Chemical class 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 229960005222 phenazone Drugs 0.000 description 3
- 238000001454 recorded image Methods 0.000 description 3
- MLVWCBYTEFCFSG-UHFFFAOYSA-L zinc;dithiocyanate Chemical compound [Zn+2].[S-]C#N.[S-]C#N MLVWCBYTEFCFSG-UHFFFAOYSA-L 0.000 description 3
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 2
- 229920002125 Sokalan® Polymers 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 150000001447 alkali salts Chemical class 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 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 2
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 235000010980 cellulose Nutrition 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000002845 discoloration Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 239000010408 film Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- LYRFLYHAGKPMFH-UHFFFAOYSA-N octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(N)=O LYRFLYHAGKPMFH-UHFFFAOYSA-N 0.000 description 2
- 239000004584 polyacrylic acid Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 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
- LIZLYZVAYZQVPG-UHFFFAOYSA-N (3-bromo-2-fluorophenyl)methanol Chemical compound OCC1=CC=CC(Br)=C1F LIZLYZVAYZQVPG-UHFFFAOYSA-N 0.000 description 1
- RSWGJHLUYNHPMX-UHFFFAOYSA-N 1,4a-dimethyl-7-propan-2-yl-2,3,4,4b,5,6,10,10a-octahydrophenanthrene-1-carboxylic acid Chemical compound C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 description 1
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 description 1
- PGAAZCXJMPDCHO-UHFFFAOYSA-N 3-(4-chloro-2-hydroxy-5-methylphenyl)-3-[4-(dimethylamino)-2-methoxyphenyl]-2-benzofuran-1-one Chemical compound COC1=CC(N(C)C)=CC=C1C1(C=2C(=CC(Cl)=C(C)C=2)O)C2=CC=CC=C2C(=O)O1 PGAAZCXJMPDCHO-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-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
- 239000005977 Ethylene Substances 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
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 206010057040 Temperature intolerance Diseases 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- ZKURGBYDCVNWKH-UHFFFAOYSA-N [3,7-bis(dimethylamino)phenothiazin-10-yl]-phenylmethanone Chemical compound C12=CC=C(N(C)C)C=C2SC2=CC(N(C)C)=CC=C2N1C(=O)C1=CC=CC=C1 ZKURGBYDCVNWKH-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 229920006243 acrylic copolymer Polymers 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 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
- 150000001408 amides Chemical class 0.000 description 1
- 239000012164 animal wax Substances 0.000 description 1
- JPIYZTWMUGTEHX-UHFFFAOYSA-N auramine O free base Chemical compound C1=CC(N(C)C)=CC=C1C(=N)C1=CC=C(N(C)C)C=C1 JPIYZTWMUGTEHX-UHFFFAOYSA-N 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- ZYGHJZDHTFUPRJ-UHFFFAOYSA-N benzo-alpha-pyrone Natural products C1=CC=C2OC(=O)C=CC2=C1 ZYGHJZDHTFUPRJ-UHFFFAOYSA-N 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 150000004074 biphenyls Chemical class 0.000 description 1
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 1
- 239000008116 calcium stearate Substances 0.000 description 1
- 235000013539 calcium stearate Nutrition 0.000 description 1
- 238000003490 calendering Methods 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
- 239000005018 casein Substances 0.000 description 1
- 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 1
- 235000021240 caseins Nutrition 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 235000012343 cottonseed oil Nutrition 0.000 description 1
- 239000002385 cottonseed oil Substances 0.000 description 1
- 235000001671 coumarin Nutrition 0.000 description 1
- 150000004775 coumarins Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000000994 depressogenic effect Effects 0.000 description 1
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical class C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 229920001249 ethyl cellulose Polymers 0.000 description 1
- 235000019325 ethyl cellulose Nutrition 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 230000008543 heat sensitivity Effects 0.000 description 1
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 1
- 150000003951 lactams Chemical class 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229920003145 methacrylic acid copolymer Polymers 0.000 description 1
- 229940117841 methacrylic acid copolymer Drugs 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 239000012184 mineral wax Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000012169 petroleum derived wax Substances 0.000 description 1
- 235000019381 petroleum wax Nutrition 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229950000688 phenothiazine Drugs 0.000 description 1
- 229920001490 poly(butyl methacrylate) polymer Polymers 0.000 description 1
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920005990 polystyrene resin Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 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
- ZNNZYHKDIALBAK-UHFFFAOYSA-M potassium thiocyanate Chemical compound [K+].[S-]C#N ZNNZYHKDIALBAK-UHFFFAOYSA-M 0.000 description 1
- 229940116357 potassium thiocyanate Drugs 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 230000004043 responsiveness Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000001568 sexual effect Effects 0.000 description 1
- 239000000661 sodium alginate Substances 0.000 description 1
- 235000010413 sodium alginate Nutrition 0.000 description 1
- 229940005550 sodium alginate Drugs 0.000 description 1
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 229940037312 stearamide Drugs 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 229920006027 ternary co-polymer Polymers 0.000 description 1
- 238000007651 thermal printing Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- AAAQKTZKLRYKHR-UHFFFAOYSA-N triphenylmethane Chemical compound C1=CC=CC=C1C(C=1C=CC=CC=1)C1=CC=CC=C1 AAAQKTZKLRYKHR-UHFFFAOYSA-N 0.000 description 1
- 239000012178 vegetable wax Substances 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- UGZADUVQMDAIAO-UHFFFAOYSA-L zinc hydroxide Chemical compound [OH-].[OH-].[Zn+2] UGZADUVQMDAIAO-UHFFFAOYSA-L 0.000 description 1
- 229940007718 zinc hydroxide Drugs 0.000 description 1
- 229910021511 zinc hydroxide Inorganic materials 0.000 description 1
- 239000011787 zinc oxide Substances 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
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
- B41M5/30—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using chemical colour formers
- B41M5/32—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using chemical colour formers one component being a heavy metal compound, e.g. lead or iron
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Heat Sensitive Colour Forming Recording (AREA)
Abstract
Description
【発明の詳細な説明】
〔技術分野〕
本発明は感熱記録材料に関し、特に発色性その他の記録
性にすぐれると共に、画像の安定性の良好な感熱記録材
料に関する。DETAILED DESCRIPTION OF THE INVENTION [Technical Field] The present invention relates to a heat-sensitive recording material, and particularly to a heat-sensitive recording material that is excellent in color development and other recording properties, and has good image stability.
一般の感熱記録材料は紙、フィルム等の支持体−ヒに発
色剤としてロイコ染料のような無色又は淡色の発色性染
料及びこれを熱時発色せしめる顕色剤としてフェノール
性化合物(特にビスフェノールA)、有機酸等の酸性物
質からなる発色系に更に結合剤、充填剤、感度向上剤、
滑剤、その他の助剤を分散した感熱発色層を設けたもの
で、例えば、特公昭43−4160号、特公昭45−1
4039号、特開昭48−27736号に紹介され、広
く実用に供されている。この種の感熱記録シートは加熱
時(加熱には熱ヘッドを内蔵したサーマルプリンターや
ファクシミリ等が利用される。)の発色剤と顕色剤との
瞬間的な化学反応により発色画像を得るものであるから
、他の記録材料に比べて現像、定着等の煩雑な処理を施
すことなく、比較的簡単な装置で短時間に記録が得られ
ること、騒音の発生及び環境汚染が少ないこと、コスト
が安いことなどの利点により、図書、文書などの複写に
用いられる他、電子計算機、ファクシミリ、テレックス
、医療計測機等の種々の情報並びに計測機器の記録材料
として有用である。General heat-sensitive recording materials include a support such as paper or film, a colorless or light-colored dye such as a leuco dye as a coloring agent, and a phenolic compound (especially bisphenol A) as a coloring agent that causes the dye to develop color when heated. In addition to the color forming system consisting of acidic substances such as organic acids, binders, fillers, sensitivity improvers,
It is provided with a heat-sensitive coloring layer in which a lubricant and other auxiliary agents are dispersed.
No. 4039 and Japanese Unexamined Patent Publication No. 48-27736, it has been widely put into practical use. This type of thermal recording sheet produces a colored image through an instantaneous chemical reaction between a coloring agent and a color developer during heating (a thermal printer or facsimile machine with a built-in thermal head is used for heating). Because of this, compared to other recording materials, recording can be obtained in a short time using relatively simple equipment without complicated processes such as development and fixing, there is less noise generation and environmental pollution, and the cost is lower. Due to its low cost, it is used for copying books, documents, etc., and is also useful as a recording material for various information and measuring instruments such as electronic computers, facsimiles, telex machines, and medical measuring instruments.
しかしながら、この種のロイコ系感熱記録材料の場合、
記録画像の安定性が悪く、例えば、油類あるいはプラス
チックフィルム中に含まれるジオクチルフタレート等の
可塑剤等と接触すると、その記録画像が消色し易いとい
う欠点がある。However, in the case of this type of leuco-based heat-sensitive recording material,
The disadvantage is that the stability of the recorded image is poor and, for example, the recorded image is easily discolored when it comes into contact with oils or plasticizers such as dioctyl phthalate contained in plastic films.
従来、記録画像の安定性を高めるため、例えば、耐水性
及び耐薬品性樹脂を大意に含有させた感熱発色層や、熱
又は光によって硬化する樹脂を含有させた感熱発色層、
又は表面に樹脂保護層を形成して感熱発色層を薬品や水
の作用から保護したもの等が提案されているが、処理が
煩雑化し、コスト高となる上、熱応答性をも低下させて
しまうという問題を有する。Conventionally, in order to improve the stability of recorded images, for example, a thermosensitive coloring layer containing a large amount of water-resistant and chemical-resistant resin, a thermosensitive coloring layer containing a resin that hardens by heat or light,
Alternatively, a method has been proposed in which a resin protective layer is formed on the surface to protect the heat-sensitive coloring layer from the effects of chemicals and water, but this method complicates processing, increases costs, and also reduces thermal responsiveness. It has the problem of being stored away.
この問題を解決するために1本発明者は、鋭意努力した
結果、先に一般式(I)で表わされる亜鉛錯体をロイコ
染料に対する顕色剤として用いることにより、極めて画
像安定性の高ず感熱記録材料が得られることを見出した
。In order to solve this problem, the inventors made extensive efforts and found that by using a zinc complex represented by the general formula (I) as a color developer for leuco dyes, the present inventors achieved extremely high image stability and heat sensitivity. It has been found that recording material can be obtained.
一方、近年、社会の発展と共に記録の高速化及び高密度
化に対する要求が高まってきた。このため、記録装置自
体の高速化は勿論、これに対応し得る記録材料の開発が
強く望まれている。従来、感熱記録材料を高速記録用と
して適したものとするためには1例えば、特開昭53−
39139号、特開昭53−26139号、特開昭53
−5636号、特開昭53−11036号公報等に記載
されているように、感熱発色層に各種ワックス類、脂肪
酸アミド、アルキル化ビフェニル、置換ビフェニルアル
カン、クマリン類、ジフェニルアミン類等の低融点の熱
溶融性物質を増感剤(あるいは融点降下剤)として添加
する方法がある。しかし、これらの方法を前記一般式(
1)の亜鉛錯体を顕色剤として使用する感熱記録材料に
適用した場合、発色濃度、発色感度、地肌白色度、画像
の耐水性等の点で未だ充分なものであるとは言い難い。On the other hand, in recent years, along with the development of society, there has been an increasing demand for higher speed and higher density recording. For this reason, there is a strong desire not only to increase the speed of the recording apparatus itself, but also to develop recording materials that can handle this. Conventionally, in order to make heat-sensitive recording materials suitable for high-speed recording, for example,
No. 39139, JP-A-53-26139, JP-A-53
As described in JP-A-5636, JP-A-53-11036, etc., various waxes, fatty acid amides, alkylated biphenyls, substituted biphenylalkanes, coumarins, diphenylamines, etc., are used in the heat-sensitive coloring layer. There is a method of adding a heat-melting substance as a sensitizer (or melting point depressant). However, these methods cannot be combined with the general formula (
When applied to a heat-sensitive recording material using the zinc complex 1) as a color developer, it is still not sufficient in terms of color density, color sensitivity, background whiteness, water resistance of images, etc.
本発明の目的は1発色濃度1発色感度が充分で。 For the purpose of the present invention, one color development density and one color development sensitivity are sufficient.
高速記録用として適し、更に地肌白色度が高く、しかも
、油類、可塑剤類との接触によっても地肌部の発色や発
色部の消色がなく、水中への浸漬等水との接触でも画像
濃度が低下しない極めて実用性の高い感熱記録材料を提
供することである。It is suitable for high-speed recording, has a high background whiteness, and does not develop color on the background or discoloration of colored areas even when it comes into contact with oils or plasticizers, and can retain images even when it comes in contact with water, such as when immersed in water. An object of the present invention is to provide an extremely practical heat-sensitive recording material that does not have a decrease in density.
本発明によれば、支持体上に、ロイコ染料と顕色剤を含
有する感熱発色層を設けた感熱記録材料において、該顕
色剤として、一般式(I)(R)k Z n (X)!
(1)(式中、Rはへテロ原子を介
して亜鉛イオンと結合して錯体を形成しうる有機配位子
を示し、kは2又は4を示し、XはSCNまたはハロゲ
ン原子を示す。)
で表わされる亜鉛錯体を用いると共に、一般式(II)
、で表わされるビニルエーテル化合物の少なくとも一種
を用いたことを特徴とする感熱記録材料が提供される。According to the present invention, in a heat-sensitive recording material in which a heat-sensitive coloring layer containing a leuco dye and a color developer is provided on a support, the color developer is composed of general formula (I)(R)k Z n (X )!
(1) (wherein R represents an organic ligand capable of bonding with zinc ion to form a complex via a heteroatom, k represents 2 or 4, and X represents SCN or a halogen atom. ) Using a zinc complex represented by the general formula (II)
Provided is a heat-sensitive recording material characterized in that it uses at least one vinyl ether compound represented by the following.
以下に本発明の亜鉛錯体及びエーテル化合物の具体例を
示すが、本発明はこれらに限定されるものではない。Specific examples of the zinc complex and ether compound of the present invention are shown below, but the present invention is not limited thereto.
化合物No 構 造 式本発明において
用いるロイコ染料は単独又は2種以上混合して適用され
るが、このようなロイコ染料としては、この種の感熱材
料に適用されているものが任意に適用され、例えば、ト
リフェニルメタン系、フルオラン系、フェノチアジン系
、オーラミン系、スピロピラン系、インドリノフタリド
系等の染料のロイコ化合物が好ましく用いられる。この
ようなロイコ染料の具体例としては、例えば、以下に示
すようなものが挙げられる。Compound No. Structural Formula The leuco dyes used in the present invention may be applied alone or in a mixture of two or more types, and as such leuco dyes, those applied to this type of heat-sensitive material may be arbitrarily applied, For example, leuco compounds of triphenylmethane-based, fluoran-based, phenothiazine-based, auramine-based, spiropyran-based, and indolinophthalide-based dyes are preferably used. Specific examples of such leuco dyes include those shown below.
3.3−ビス(p−ジメチルアミノフェニル)−フタリ
ド、
3.3−ビス(P−ジメチルアミノフェニル)−6−シ
メチルアミノフタリド(別名クリスタルバイオレットラ
クトン)、
3.3−ビス(p−ジメチルアミノフェニル)−6−ジ
エチルアミノフェニル、
3.3− ヒス(p−ジメチルアミノフェニル)−6−
クロルフタリド、
3.3−ビス(p−ジブチルアミノフェニル)フタリド
、
3−シクロへキシルアミノ−6−クロルフルオラン。3.3-bis(p-dimethylaminophenyl)-phthalide, 3.3-bis(p-dimethylaminophenyl)-6-dimethylaminophthalide (also known as crystal violet lactone), 3.3-bis(p- dimethylaminophenyl)-6-diethylaminophenyl, 3.3-his(p-dimethylaminophenyl)-6-
Chlorphthalide, 3.3-bis(p-dibutylaminophenyl)phthalide, 3-cyclohexylamino-6-chlorofluoran.
3−ジメチルアミノ−5,7−シメチルフルオラン、3
−ジエチルアミノ−7−クロロフルオラン、3−ジエチ
ルアミノ−7−メチルフルオラン、3−ジエチルアミノ
−7,8−ベンズフルオラン、3−ジエチルアミノ−6
−メチル−7−クロルフルオラン、
3−(N−p−トリル−N−二チルアミノ)−6−メチ
ル−7−アニリノフルオラン。3-dimethylamino-5,7-dimethylfluorane, 3
-diethylamino-7-chlorofluorane, 3-diethylamino-7-methylfluorane, 3-diethylamino-7,8-benzfluorane, 3-diethylamino-6
-Methyl-7-chlorofluorane, 3-(N-p-tolyl-N-ditylamino)-6-methyl-7-anilinofluorane.
3−ピロリジノ−6−メチル−7−アニリノフルオラン
、
2− (N−(3’ −トリフルオルメチルフェニル)
アミノ)−6−ジニチルアミノフルオラン、2− (3
,6−ビス(ジエチルアミノ)−9−(o−クロルアニ
リノ)キサンチル安息香酸ラクタム)、3−ジエチルア
ミノ−6−メチル−7−(−一トリクロロメチルアニリ
ノ)フルオラン。3-pyrrolidino-6-methyl-7-anilinofluorane, 2-(N-(3'-trifluoromethylphenyl)
amino)-6-dinithylaminofluorane, 2-(3
, 6-bis(diethylamino)-9-(o-chloroanilino)xantylbenzoic acid lactam), 3-diethylamino-6-methyl-7-(-monotrichloromethylanilino)fluoran.
3−ジエチルアミノ−7−(0−クロルアニリノ)フル
オラン、
3−ジブチルアミノ−7−(0−クロルアニリノ)フル
オラン、
3−N−メチル−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−(N、N−ジエチルアミノ)−5−メチル−7−(
N。3-diethylamino-7-(0-chloroanilino)fluoran, 3-dibutylamino-7-(0-chloroanilino)fluoran, 3-N-methyl-N-isoamylamino-6-methyl-
7-anilinofluorane, 3-N-methyl-N-cyclohexylamino-6-methyl-7-anilinofluorane, 3-diethylamino-6-methyl-7-anilinofluorane, 3-(N,N -diethylamino)-5-methyl-7-(
N.
N−ジベンジルアミノ)フルオラン、
ベンゾイルロイコメチレンブルー、
6′−クロロ−8′−メトキシ−ベンゾインドリノ−ビ
リロスビラン、
6′−ブロモ−3′−メトキシ−ベンゾインドリノ−ピ
リロスピラン、
3−(2’ −ヒドロキシ−4′−ジメチルアミノフェ
ニル)−3−(2’ −メトキシ−5′−クロルフェニ
ル)フタリド、
3−(2’ −ヒドロキシ−4′−ジメチルアミノフェ
ニル)−3−(2’ −メトキシ−5′−ニトロフェニ
ル)フタリド、
3−(2’ −ヒドロキシ−4′−ジエチルアミノフェ
ニル)−3−(2’ −メトキシ−51−メチルフェニ
ル)フタリド。N-dibenzylamino)fluoran, benzoylleucomethylene blue, 6'-chloro-8'-methoxy-benzoindolino-pyrylosbilane, 6'-bromo-3'-methoxy-benzoindolino-pyrylospirane, 3-(2'- 3-(2'-hydroxy-4'-dimethylaminophenyl)-3-(2'-methoxy- 5'-nitrophenyl) phthalide, 3-(2'-hydroxy-4'-diethylaminophenyl)-3-(2'-methoxy-51-methylphenyl) phthalide.
3−(2’ −メトキシ−4′−ジメチルアミノフェニ
ル)−3−(2’ −ヒドロキシ−4′−クロル−5′
−メチルフエニル)フタリド、
3−モルホリノ−7−(N−プロピル−トリフルオロメ
チルアニリノ)フルオラン、
3−ピロリジノ−7−トリフルオロメチルアニリノフル
オラン、
3−ジエチルアミノ−5−クロロ−7−(N−ベンジル
−トリフルオロメチルアニリノ)フルオラン。3-(2'-methoxy-4'-dimethylaminophenyl)-3-(2'-hydroxy-4'-chloro-5'
-methylphenyl)phthalide, 3-morpholino-7-(N-propyl-trifluoromethylanilino)fluorane, 3-pyrrolidino-7-trifluoromethylanilinofluorane, 3-diethylamino-5-chloro-7-(N -benzyl-trifluoromethylanilino)fluorane.
3−ピロリジノ−7−(ジ−p−クロルフェニル)メチ
ルアミノフルオラン、
3−ジエチルアミノ−5−クロル−7−(α−)工二ル
エチルアミノ)フルオラン、
3−(N−エチル−p−トルイジノ)−7−(α−フェ
ニルエチルアミノ)フルオラン。3-Pyrrolidino-7-(di-p-chlorophenyl)methylaminofluorane, 3-diethylamino-5-chloro-7-(α-)dimethylethylamino)fluoran, 3-(N-ethyl-p-toluidino) -7-(α-phenylethylamino)fluoran.
3−ジエチルアミノ−7−(o−メトキシカルボニルフ
ェニルアミノ)フルオラン、
3−ジエチルアミノ−5−メチル−7−(α−フェニル
エチルアミノ)フルオラン、
3−ジエチルアミノ−7−ピペリジノフルオラン。3-diethylamino-7-(o-methoxycarbonylphenylamino)fluoran, 3-diethylamino-5-methyl-7-(α-phenylethylamino)fluoran, 3-diethylamino-7-piperidinofluorane.
2−クロロ−3−(N−メチルトルイジノ)−7−(p
−〇−ブチルアニリノ)フルオラン、
3−(N−ベンジル−N−シクロヘキシルアミノ)−5
,6−ペンゾー7−α−ナフチルアミノ−4′−ブロモ
フルオラン、
3−ジエチルアミノ−6−クロル−7−アニリノフルオ
ラン。2-chloro-3-(N-methyltoluidino)-7-(p
-〇-butylanilino)fluorane, 3-(N-benzyl-N-cyclohexylamino)-5
, 6-penzo 7-α-naphthylamino-4'-bromofluorane, 3-diethylamino-6-chloro-7-anilinofluorane.
3−N−エチル−N−(2−エトキシプロピル)アミノ
−6−メチル−7−アニリノフルオラン、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−メ
チル−7−メシチジノー4’、5’−ベンゾフルオラン
等。3-N-ethyl-N-(2-ethoxypropyl)amino-6-methyl-7-anilinofluorane, 3-N-ethyl-N-tetrahydrofurfurylamino-6-methyl-
7-anilinofluorane, 3-diethylamino-6-methyl-7-mesitidino 4', 5'-benzofluorane, and the like.
本発明においては、前記ロイコ染料、顕色剤及び補助成
分を支持体上に結合支持させるために、慣用の種々の結
合剤を適宜用いることができ、例えば、ポリビニルアル
コール、デンプン及びその誘導体、メトキシセルロース
、ヒドロキシエチルセルロース、カルボキシメチルセル
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、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3元共重合体、スチレン/無水マレイン酸共重合体
アルカリ塩、イソブチレン/無水マレイン酸共重合体ア
ルカリ塩、ポリアクリルアミド、アルギン酸ソーダ、ゼ
ラチン、カゼイン等の水溶性高分子の他、ポリ酢酸ビニ
ル、ポリウレタン、スチレン/ブタジェン共重合体、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/ブタジェン/ア
クリル系共重合体等のラテックスを用いることができる
。In the present invention, in order to bind and support the leuco dye, color developer and auxiliary components on the support, various conventional binders can be used as appropriate, such as polyvinyl alcohol, starch and its derivatives, methoxy Cellulose derivatives such as cellulose, hydroxyethylcellulose, carboxymethylcellulose, methylcellulose, and ethylcellulose, sodium polyacrylate, polyvinylpyrrolidone, acrylic amide/acrylic ester copolymer, acrylic amide/acrylic ester/methacrylic acid ternary copolymer , styrene/maleic anhydride copolymer alkali salt, isobutylene/maleic anhydride copolymer alkali salt, polyacrylamide, sodium alginate, gelatin, casein, and other water-soluble polymers, as well as polyvinyl acetate, polyurethane, styrene/butadiene. Copolymer, polyacrylic acid, polyacrylic acid ester, vinyl chloride/
Latex such as vinyl acetate copolymer, polybutyl methacrylate, ethylene/vinyl acetate copolymer, styrene/butadiene/acrylic copolymer, etc. can be used.
また、本発明においては、前記ロイコ染料、顕色剤及び
補助成分と共に、必要に応じ、更に、この種の感熱記録
材料に慣用される補助添加成分、例えば、填料、界面活
性剤、熱可融性物質(又は滑剤)等を併用することがで
きる。この場合、填料としては、例えば、炭酸カルシウ
ム、シリカ、酸化亜鉛、酸化チタン、水酸化アルミニウ
ム、水酸化亜鉛、硫酸バリウム、クレー、タルク、表面
処理されたカルシウムやシリカ等の無機系微粉末の他、
尿素−ホルマリン樹脂、スチレン/メタクリル酸共重合
体、°ポリスチレン樹脂等の有機系の微粉末を挙げるこ
とができる。熱可融性物質としては、ステアリン酸亜鉛
、ステアリン酸カルシウム、ステアリン酸アルミニウム
等の高級脂肪酸金属塩、動植物ワックス、鉱物性ワック
ス、石油系ワックス、高級脂肪酸及びそのエステルやア
ミド等が挙げられる。In the present invention, in addition to the leuco dye, color developer, and auxiliary components, if necessary, auxiliary additive components commonly used in this type of heat-sensitive recording material, such as fillers, surfactants, thermofusible A sexual substance (or lubricant), etc. can be used in combination. In this case, fillers include, for example, calcium carbonate, silica, zinc oxide, titanium oxide, aluminum hydroxide, zinc hydroxide, barium sulfate, clay, talc, and surface-treated inorganic fine powders such as calcium and silica. ,
Examples include organic fine powders such as urea-formalin resin, styrene/methacrylic acid copolymer, and polystyrene resin. Examples of the thermofusible substance include higher fatty acid metal salts such as zinc stearate, calcium stearate, and aluminum stearate, animal and vegetable waxes, mineral waxes, petroleum waxes, higher fatty acids, and their esters and amides.
本発明の感熱記録材料は、例えば、前記した各成分を含
む感熱層形成用塗液を、紙、合成紙、プラスチックフィ
ルムなどの適当な支持体上に塗布し、乾燥することによ
って製造される。この場合。The heat-sensitive recording material of the present invention is produced, for example, by applying a coating liquid for forming a heat-sensitive layer containing the above-mentioned components onto a suitable support such as paper, synthetic paper, or plastic film, and drying the coated liquid. in this case.
ロイコ染料、顕色剤、発色感度増加剤の使用址は、それ
ぞれ5〜40重量%、20〜60重量%、20〜60重
量%が適当である。The appropriate amounts of the leuco dye, color developer, and color development sensitivity increasing agent are 5 to 40% by weight, 20 to 60% by weight, and 20 to 60% by weight, respectively.
本発明の感熱記録材料は、感度の向上されたもので、高
速記録用として適すると共に、地肌白色度も高く、しか
も、油類、可塑剤類との接触によっても地肌部の発色や
発色部の消色がなく、水中への浸漬等、水との接触でも
画像濃度が低下しない極めて実用性の高いものである。The heat-sensitive recording material of the present invention has improved sensitivity, is suitable for high-speed recording, has a high degree of whiteness of the background, and is also resistant to coloring of the background and coloring of the colored area when it comes into contact with oils and plasticizers. It is highly practical as it does not fade and the image density does not decrease even when it comes into contact with water, such as when immersed in water.
これらの効果は前記式(1)で表わされる亜鉛錯体を特
定のエーテル系化合物と併用することによって得られる
ものである。These effects can be obtained by using the zinc complex represented by the above formula (1) in combination with a specific ether compound.
次に、本発明を実施例によりさらに詳細に説明する。な
お、以下に示す部及び%はいずれも重量基準である。Next, the present invention will be explained in more detail with reference to Examples. Note that all parts and percentages shown below are based on weight.
また、後記実施例で用いたチオシアン酸亜鉛のアンチピ
リン錯体(化合物N01)は、次のようにして合成され
たものである。Furthermore, the antipyrine complex of zinc thiocyanate (compound N01) used in the Examples described later was synthesized as follows.
硫酸亜鉛(ZnSO,* 7H−0) 14−4gとチ
オシアン酸カリウム29.2gを水200m mに溶解
した。別に、アンチピリン8.8gを水200m Qに
溶解した溶液を用意し。14-4 g of zinc sulfate (ZnSO, *7H-0) and 29.2 g of potassium thiocyanate were dissolved in 200 mm of water. Separately, a solution of 8.8 g of antipyrine dissolved in 200 mQ of water was prepared.
上記溶液に攪拌下に滴下すると直ちに白色沈殿が生じた
。この沈殿を濾別水洗後、乾燥し、得られた白色粉末を
水−エタノールの混合溶媒で再結晶すると、融点118
〜120℃のチオシアン酸亜鉛のアンチピリン錯体の白
色結晶24.2gが得られた。When it was added dropwise to the above solution while stirring, a white precipitate was immediately generated. This precipitate was filtered, washed with water, dried, and the resulting white powder was recrystallized from a mixed solvent of water and ethanol, with a melting point of 118
24.2 g of white crystals of antipyrine complex of zinc thiocyanate were obtained at ~120°C.
実施例1
下記組成よりなる混合物を各々別々に磁性ボールミルを
用いて2日間粉砕1分散して、下記(A)〜(D)液を
調製した。Example 1 The following solutions (A) to (D) were prepared by separately pulverizing and dispersing mixtures having the following compositions for two days using a magnetic ball mill.
水
6011〔B液〕
水
60/I〔C液〕
1.4−ジ(ビニルオキシエトキシ)ベンゼン 20部
メチルセルロースの5%水溶液2011水
60n〔D
液〕
深索−ホルマリン樹脂の微粉末 20部メチル
セルロース5%水溶液 20〃水
601/
次にA液lO部、B液30部、C液30部、D液20部
及びイソブチレン−無水マレイン酸共重合体の20%ア
ルカリ水溶液10部を混合して感熱発色層形成液とし、
これを坪150g/rdの上質紙上に乾燥付着量が4〜
5g/ rdとなるように塗布乾燥して感熱発色層を設
けた後、更にその表面平滑度が500〜600秒になる
よう層表面をカレンダー掛けして感熱記録材料(a)を
作成した
実施例2
実施例1の(C)液のかわりに下記(E)液を用いた他
は実施例1と同様にして感熱記録材料(b)を作成した
。water
6011 [Liquid B] Water
60/I [Liquid C] 1.4-di(vinyloxyethoxy)benzene 20 parts 5% aqueous solution of methylcellulose 2011 water
60n [D
Liquid] Shinsaku-Fine powder of formalin resin 20 parts Methyl cellulose 5% aqueous solution 20 parts Water
601/
Next, 10 parts of liquid A, 30 parts of liquid B, 30 parts of liquid C, 20 parts of liquid D, and 10 parts of a 20% alkaline aqueous solution of isobutylene-maleic anhydride copolymer were mixed to prepare a thermosensitive coloring layer forming liquid.
This was applied to a high-quality paper of 150 g/rd with a dry adhesion of 4 to 4
An example in which a heat-sensitive coloring layer was provided by coating and drying to give a coating weight of 5 g/rd, and then the layer surface was calendered to have a surface smoothness of 500 to 600 seconds to prepare a heat-sensitive recording material (a). 2 A heat-sensitive recording material (b) was prepared in the same manner as in Example 1, except that the following liquid (E) was used instead of liquid (C) in Example 1.
(E)液
1.3−ジ(ビニルオキシエトキシ)ベンゼン 20部
メチルセルロースの5%水溶液 20〃水
6
0〃実施例3
実施例1の(C)液のかわりに下記(F)液を用いた還
は実施例1と同様にして感熱記録材料(C)を作成した
。(E) Solution 1. 20 parts of 3-di(vinyloxyethoxy)benzene 5% aqueous solution of methylcellulose 20 parts of water
6
Example 3 A heat-sensitive recording material (C) was prepared in the same manner as in Example 1 except that the following liquid (F) was used instead of liquid (C) in Example 1.
(F)液
1.2−ジ(ビニルオキシエトキシ)ベンゼン 20部
メチルセルロースの非水溶液 20部水
6
0〃比較例1
実施例1の〔C〕液のかわりに水を用いた他は実施例1
と同様にして感熱記録材料(d)を作成した。(F) Liquid 1. 2-di(vinyloxyethoxy)benzene 20 parts Non-aqueous solution of methyl cellulose 20 parts Water
6
0 Comparative Example 1 Example 1 except that water was used instead of liquid [C] in Example 1.
A thermosensitive recording material (d) was prepared in the same manner as above.
比較例2
実施例1の(C)液のかわりに下記(G)液を用いた以
外は実施例1と同様にして感熱記録材料(e)を作成し
た。Comparative Example 2 A heat-sensitive recording material (e) was produced in the same manner as in Example 1, except that the following liquid (G) was used instead of liquid (C) in Example 1.
(G)液
ステアリン酸アミド 20部メチル
セルロースの5%水溶液 20/!水
6011
以上のようにして得た感熱記録材料(a)〜(e)を、
松下電子部品■製薄膜ヘッドを有する感熱印字実験装置
にてヘッド電力0.451/ドツト、1ライン記録時間
20m5ec/ Q 、走査線密度8 X 3.85ド
ツト/1IIIlの条件でパルス巾を1.6.2.0.
2.4(msec)で印字し、その印字濃度をマクベス
濃度計RD −514(フィルターリ−106)で測定
した。その結果を表−1に示す。(G) Liquid stearamide 20 parts 5% aqueous solution of methylcellulose 20/! water
6011
The heat-sensitive recording materials (a) to (e) obtained as above are
Using a thermal printing experimental device with a thin film head manufactured by Matsushita Electronics Co., Ltd., the pulse width was set to 1.5 cm under the conditions of head power of 0.451/dot, recording time of one line of 20 m5ec/Q, and scanning line density of 8 x 3.85 dots/1IIIl. 6.2.0.
2.4 (msec), and the print density was measured using a Macbeth densitometer RD-514 (Filterly-106). The results are shown in Table-1.
表−1
次に、感熱記録材料(a)〜(e)を熱傾斜試験機(東
洋精機製)にて圧力2kg、接触時間1秒、150℃の
条件で印字し、印字部を中心に4cm四方に切抜き、こ
れにポリ塩化ビニルフィルム(信越ポリマー■製ポリラ
ップV −300)を1枚重ね、室温で荷重500g/
*を24時間かけた後、取り出して地肌部の濃度と発
色部の濃度をマクベス濃度計(RD−514)で測定し
、試験前の濃度と比較した。その結果は表−2の通りで
ある。Table 1 Next, thermal recording materials (a) to (e) were printed using a thermal gradient tester (manufactured by Toyo Seiki) at a pressure of 2 kg, a contact time of 1 second, and a temperature of 150°C, with a distance of 4 cm centered around the printed area. Cut it out on all sides, overlap it with a sheet of polyvinyl chloride film (Polywrap V-300 manufactured by Shin-Etsu Polymer ■), and apply a load of 500 g/cm at room temperature.
* After being left on for 24 hours, it was taken out, and the density of the background area and the density of the colored area were measured using a Macbeth densitometer (RD-514) and compared with the density before the test. The results are shown in Table-2.
表−2
次に、同様に印字したサンプルの地肌部と発色部に綿実
油を薄く塗布し、室温で24時間保存したところ、サン
プル(、)〜(6)すべて、地肌部の発色、発色部の消
色はみられなかった。Table 2 Next, when a thin layer of cottonseed oil was applied to the background and colored areas of the similarly printed samples and the samples were stored at room temperature for 24 hours, samples (,) to (6) all showed coloration in the background area and color development in the colored area. No discoloration was observed.
次に、同様に印字したサンプルを印字部を中心に4CI
11四方に切抜き、水道水80ra Qを入れた100
m Qのビーカーに室温で24時間浸漬させ、取り出し
て乾燥後1発色部の濃度変化を測定した。その結果を表
−3に示す。Next, take a sample printed in the same way and print 4 CIs around the printed part.
100 with 11 square cutouts and 80ra Q of tap water
The sample was immersed in a mQ beaker at room temperature for 24 hours, taken out and dried, and the change in density of one colored area was measured. The results are shown in Table-3.
表−3
以上より、本発明の感熱記録材料は、高感度で地肌白色
も高く、油類、可塑剤類との接触によっても地肌部の発
色、発色部の消色がなく、水中への浸漬等、水との接触
でも画像濃度が低下しない、極めて実用性の高いもので
あることがわかる。Table 3 From the above, the heat-sensitive recording material of the present invention has high sensitivity and white background, does not develop color on the background or decolorize the colored area even when in contact with oils or plasticizers, and can be immersed in water. It can be seen that the image density does not decrease even when it comes in contact with water, making it extremely practical.
Claims (1)
発色層を設けた感熱記録材料において、該顕色剤として
、一般式( I ) (R)kZn(X)_2( I ) (式中、Rはヘテロ原子を介して亜鉛イオンと結合して
錯体を形成しうる有機配位子を示し、kは2又は4を示
し、XはSCNまたはハロゲン原子を示す。) で表わされる亜鉛錯体を用いると共に、一般式(II)、
▲数式、化学式、表等があります▼(II) で表わされるビニルエーテル化合物の少なくとも一種を
用いたことを特徴とする感熱記録材料。(1) In a heat-sensitive recording material in which a heat-sensitive coloring layer containing a leuco dye and a color developer is provided on a support, the color developer is of the general formula (I) (R)kZn(X)_2(I) (In the formula, R represents an organic ligand capable of bonding with a zinc ion to form a complex via a hetero atom, k represents 2 or 4, and X represents SCN or a halogen atom.) While using a zinc complex, general formula (II),
▲There are mathematical formulas, chemical formulas, tables, etc.▼(II) A heat-sensitive recording material characterized by using at least one vinyl ether compound represented by the following.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP62009939A JP2555337B2 (en) | 1987-01-21 | 1987-01-21 | Thermal recording material |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP62009939A JP2555337B2 (en) | 1987-01-21 | 1987-01-21 | Thermal recording material |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS63179788A true JPS63179788A (en) | 1988-07-23 |
JP2555337B2 JP2555337B2 (en) | 1996-11-20 |
Family
ID=11733983
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP62009939A Expired - Lifetime JP2555337B2 (en) | 1987-01-21 | 1987-01-21 | Thermal recording material |
Country Status (1)
Country | Link |
---|---|
JP (1) | JP2555337B2 (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1993004433A1 (en) * | 1991-08-15 | 1993-03-04 | Datacard Corporation | Modular card processing system |
-
1987
- 1987-01-21 JP JP62009939A patent/JP2555337B2/en not_active Expired - Lifetime
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1993004433A1 (en) * | 1991-08-15 | 1993-03-04 | Datacard Corporation | Modular card processing system |
US5451037A (en) * | 1991-08-15 | 1995-09-19 | Datacard Corporation | Modular card processing system |
Also Published As
Publication number | Publication date |
---|---|
JP2555337B2 (en) | 1996-11-20 |
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