JPH0686154B2 - Thermal recording material - Google Patents
Thermal recording materialInfo
- Publication number
- JPH0686154B2 JPH0686154B2 JP60097188A JP9718885A JPH0686154B2 JP H0686154 B2 JPH0686154 B2 JP H0686154B2 JP 60097188 A JP60097188 A JP 60097188A JP 9718885 A JP9718885 A JP 9718885A JP H0686154 B2 JPH0686154 B2 JP H0686154B2
- Authority
- JP
- Japan
- Prior art keywords
- color
- heat
- recording material
- acid
- parts
- 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.)
- Expired - Lifetime
Links
- 239000000463 material Substances 0.000 title claims description 48
- 239000003094 microcapsule Substances 0.000 claims description 41
- 238000006243 chemical reaction Methods 0.000 claims description 10
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 229920000538 Poly[(phenyl isocyanate)-co-formaldehyde] Polymers 0.000 claims description 6
- 239000000126 substance Substances 0.000 description 38
- 238000000576 coating method Methods 0.000 description 21
- 239000011248 coating agent Substances 0.000 description 19
- 150000008049 diazo compounds Chemical class 0.000 description 16
- 238000000034 method Methods 0.000 description 15
- 239000011162 core material Substances 0.000 description 12
- 239000002245 particle Substances 0.000 description 11
- 239000003795 chemical substances by application Substances 0.000 description 10
- 229920000642 polymer Polymers 0.000 description 10
- -1 spiropyran Chemical class 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 150000001875 compounds Chemical class 0.000 description 8
- 239000010410 layer Substances 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 229920003169 water-soluble polymer Polymers 0.000 description 8
- 239000004372 Polyvinyl alcohol Substances 0.000 description 7
- 239000012954 diazonium Substances 0.000 description 7
- 239000006185 dispersion Substances 0.000 description 7
- 229920002451 polyvinyl alcohol Polymers 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 238000005859 coupling reaction Methods 0.000 description 6
- 150000001989 diazonium salts Chemical class 0.000 description 6
- 229920005862 polyol Polymers 0.000 description 6
- 150000003077 polyols Chemical class 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 5
- 125000001931 aliphatic group Chemical group 0.000 description 5
- 125000003118 aryl group Chemical group 0.000 description 5
- 230000008878 coupling Effects 0.000 description 5
- 238000010168 coupling process Methods 0.000 description 5
- 239000000975 dye Substances 0.000 description 5
- 150000002148 esters Chemical class 0.000 description 5
- 239000012948 isocyanate Substances 0.000 description 5
- 150000002513 isocyanates Chemical class 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- RTTZISZSHSCFRH-UHFFFAOYSA-N 1,3-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC(CN=C=O)=C1 RTTZISZSHSCFRH-UHFFFAOYSA-N 0.000 description 4
- 108010010803 Gelatin Proteins 0.000 description 4
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 description 4
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 4
- 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 4
- 230000008859 change Effects 0.000 description 4
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 4
- 229920000159 gelatin Polymers 0.000 description 4
- 239000008273 gelatin Substances 0.000 description 4
- 235000019322 gelatine Nutrition 0.000 description 4
- 235000011852 gelatine desserts Nutrition 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- VYQNWZOUAUKGHI-UHFFFAOYSA-N monobenzone Chemical compound C1=CC(O)=CC=C1OCC1=CC=CC=C1 VYQNWZOUAUKGHI-UHFFFAOYSA-N 0.000 description 4
- 229920000768 polyamine Polymers 0.000 description 4
- 239000000376 reactant Substances 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 239000004576 sand Substances 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 4
- FUPAJKKAHDLPAZ-UHFFFAOYSA-N 1,2,3-triphenylguanidine Chemical compound C=1C=CC=CC=1NC(=NC=1C=CC=CC=1)NC1=CC=CC=C1 FUPAJKKAHDLPAZ-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 239000002775 capsule Substances 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 239000011247 coating layer Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- 235000014113 dietary fatty acids Nutrition 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000000839 emulsion Substances 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
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 229910052751 metal Chemical class 0.000 description 3
- 239000002184 metal Chemical class 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 150000007524 organic acids Chemical class 0.000 description 3
- 239000005056 polyisocyanate Substances 0.000 description 3
- 229920001228 polyisocyanate Polymers 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- NXQMCAOPTPLPRL-UHFFFAOYSA-N 2-(2-benzoyloxyethoxy)ethyl benzoate Chemical compound C=1C=CC=CC=1C(=O)OCCOCCOC(=O)C1=CC=CC=C1 NXQMCAOPTPLPRL-UHFFFAOYSA-N 0.000 description 2
- YZYFPMLAGIGAJJ-UHFFFAOYSA-N 4-diazo-n,n-diethylcyclohexa-1,5-dien-1-amine Chemical compound CCN(CC)C1=CCC(=[N+]=[N-])C=C1 YZYFPMLAGIGAJJ-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
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- FZERHIULMFGESH-UHFFFAOYSA-N N-phenylacetamide Chemical compound CC(=O)NC1=CC=CC=C1 FZERHIULMFGESH-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 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
- 150000001408 amides Chemical class 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 229920006318 anionic polymer Polymers 0.000 description 2
- 150000001450 anions 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
- 239000002585 base Substances 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- OWBTYPJTUOEWEK-UHFFFAOYSA-N butane-2,3-diol Chemical compound CC(O)C(C)O OWBTYPJTUOEWEK-UHFFFAOYSA-N 0.000 description 2
- VHRGRCVQAFMJIZ-UHFFFAOYSA-N cadaverine Chemical compound NCCCCCN VHRGRCVQAFMJIZ-UHFFFAOYSA-N 0.000 description 2
- 239000004202 carbamide Substances 0.000 description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 description 2
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 2
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-O diazynium Chemical group [NH+]#N IJGRMHOSHXDMSA-UHFFFAOYSA-O 0.000 description 2
- JBSLOWBPDRZSMB-FPLPWBNLSA-N dibutyl (z)-but-2-enedioate Chemical compound CCCCOC(=O)\C=C/C(=O)OCCCC JBSLOWBPDRZSMB-FPLPWBNLSA-N 0.000 description 2
- FLKPEMZONWLCSK-UHFFFAOYSA-N diethyl phthalate Chemical compound CCOC(=O)C1=CC=CC=C1C(=O)OCC FLKPEMZONWLCSK-UHFFFAOYSA-N 0.000 description 2
- 230000001804 emulsifying effect Effects 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000004816 latex Substances 0.000 description 2
- 229920000126 latex Polymers 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000001923 methylcellulose Substances 0.000 description 2
- 235000010981 methylcellulose Nutrition 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 2
- 238000007639 printing Methods 0.000 description 2
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 description 2
- 238000010791 quenching Methods 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 230000004043 responsiveness Effects 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 150000005846 sugar alcohols Polymers 0.000 description 2
- XFNJVJPLKCPIBV-UHFFFAOYSA-N trimethylenediamine Chemical compound NCCCN XFNJVJPLKCPIBV-UHFFFAOYSA-N 0.000 description 2
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 1
- VTWGIDKXXZRLGH-HJWRWDBZSA-N (z)-4-octoxy-4-oxobut-2-enoic acid Chemical compound CCCCCCCCOC(=O)\C=C/C(O)=O VTWGIDKXXZRLGH-HJWRWDBZSA-N 0.000 description 1
- FTWMCSGJSZWKCR-UHFFFAOYSA-N 1,2,3-tricyclohexylguanidine Chemical compound C1CCCCC1NC(NC1CCCCC1)=NC1CCCCC1 FTWMCSGJSZWKCR-UHFFFAOYSA-N 0.000 description 1
- ZWVMLYRJXORSEP-UHFFFAOYSA-N 1,2,6-Hexanetriol Chemical compound OCCCCC(O)CO ZWVMLYRJXORSEP-UHFFFAOYSA-N 0.000 description 1
- OPNUROKCUBTKLF-UHFFFAOYSA-N 1,2-bis(2-methylphenyl)guanidine Chemical compound CC1=CC=CC=C1N\C(N)=N\C1=CC=CC=C1C OPNUROKCUBTKLF-UHFFFAOYSA-N 0.000 description 1
- MPUAUPQFSLHOHQ-UHFFFAOYSA-N 1,2-dicyclohexylguanidine Chemical compound C1CCCCC1NC(=N)NC1CCCCC1 MPUAUPQFSLHOHQ-UHFFFAOYSA-N 0.000 description 1
- UYBWIEGTWASWSR-UHFFFAOYSA-N 1,3-diaminopropan-2-ol Chemical compound NCC(O)CN UYBWIEGTWASWSR-UHFFFAOYSA-N 0.000 description 1
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 1
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 1
- ITWBWJFEJCHKSN-UHFFFAOYSA-N 1,4,7-triazonane Chemical compound C1CNCCNCCN1 ITWBWJFEJCHKSN-UHFFFAOYSA-N 0.000 description 1
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- VYOWNYLBHHBVDR-UHFFFAOYSA-N 1-(3-methylbutyl)-2-phenylbenzene Chemical group CC(C)CCC1=CC=CC=C1C1=CC=CC=C1 VYOWNYLBHHBVDR-UHFFFAOYSA-N 0.000 description 1
- PWMWNFMRSKOCEY-UHFFFAOYSA-N 1-Phenyl-1,2-ethanediol Chemical compound OCC(O)C1=CC=CC=C1 PWMWNFMRSKOCEY-UHFFFAOYSA-N 0.000 description 1
- JJEAHXPPYZKVHZ-UHFFFAOYSA-N 1-hydroxy-n-(3-morpholin-4-ylpropyl)naphthalene-2-carboxamide Chemical compound C1=CC2=CC=CC=C2C(O)=C1C(=O)NCCCN1CCOCC1 JJEAHXPPYZKVHZ-UHFFFAOYSA-N 0.000 description 1
- HKTCLPBBJDIBGF-UHFFFAOYSA-N 1-phenyl-2-propan-2-ylbenzene Chemical group CC(C)C1=CC=CC=C1C1=CC=CC=C1 HKTCLPBBJDIBGF-UHFFFAOYSA-N 0.000 description 1
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 1
- ZFFMLCVRJBZUDZ-UHFFFAOYSA-N 2,3-dimethylbutane Chemical group CC(C)C(C)C ZFFMLCVRJBZUDZ-UHFFFAOYSA-N 0.000 description 1
- VWGVUCWHPBULRD-UHFFFAOYSA-N 2,4,5-tris(furan-2-yl)-4,5-dihydro-1h-imidazole Chemical compound N1C(C=2OC=CC=2)C(C=2OC=CC=2)N=C1C1=CC=CO1 VWGVUCWHPBULRD-UHFFFAOYSA-N 0.000 description 1
- UFBJCMHMOXMLKC-UHFFFAOYSA-N 2,4-dinitrophenol Chemical compound OC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O UFBJCMHMOXMLKC-UHFFFAOYSA-N 0.000 description 1
- NSMWYRLQHIXVAP-UHFFFAOYSA-N 2,5-dimethylpiperazine Chemical compound CC1CNC(C)CN1 NSMWYRLQHIXVAP-UHFFFAOYSA-N 0.000 description 1
- QUWAJPZDCZDTJS-UHFFFAOYSA-N 2-(2-hydroxyphenyl)sulfonylphenol Chemical compound OC1=CC=CC=C1S(=O)(=O)C1=CC=CC=C1O QUWAJPZDCZDTJS-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- PTPIRFSXRFIROJ-UHFFFAOYSA-N 2-(3-hydroxyphenoxy)ethane-1,1-diol Chemical compound OC(O)COC1=CC=CC(O)=C1 PTPIRFSXRFIROJ-UHFFFAOYSA-N 0.000 description 1
- YEVQZPWSVWZAOB-UHFFFAOYSA-N 2-(bromomethyl)-1-iodo-4-(trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=C(I)C(CBr)=C1 YEVQZPWSVWZAOB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- WTPYFJNYAMXZJG-UHFFFAOYSA-N 2-[4-(2-hydroxyethoxy)phenoxy]ethanol Chemical compound OCCOC1=CC=C(OCCO)C=C1 WTPYFJNYAMXZJG-UHFFFAOYSA-N 0.000 description 1
- UHGULLIUJBCTEF-UHFFFAOYSA-N 2-aminobenzothiazole Chemical compound C1=CC=C2SC(N)=NC2=C1 UHGULLIUJBCTEF-UHFFFAOYSA-N 0.000 description 1
- NAPDOWNULRULLI-UHFFFAOYSA-N 2-benzyl-1h-imidazole Chemical compound C=1C=CC=CC=1CC1=NC=CN1 NAPDOWNULRULLI-UHFFFAOYSA-N 0.000 description 1
- VMSBGXAJJLPWKV-UHFFFAOYSA-N 2-ethenylbenzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1C=C VMSBGXAJJLPWKV-UHFFFAOYSA-N 0.000 description 1
- PQLFCHDUACQEPJ-UHFFFAOYSA-N 2-hydroxy-3-(2,4,4-trimethylpentan-2-yl)benzoic acid Chemical compound CC(C)(C)CC(C)(C)C1=CC=CC(C(O)=O)=C1O PQLFCHDUACQEPJ-UHFFFAOYSA-N 0.000 description 1
- MSOVRVJXGBFBNF-UHFFFAOYSA-N 2-hydroxy-5-(1-phenylethyl)benzoic acid Chemical compound C=1C=C(O)C(C(O)=O)=CC=1C(C)C1=CC=CC=C1 MSOVRVJXGBFBNF-UHFFFAOYSA-N 0.000 description 1
- JOMNTHCQHJPVAZ-UHFFFAOYSA-N 2-methylpiperazine Chemical compound CC1CNCCN1 JOMNTHCQHJPVAZ-UHFFFAOYSA-N 0.000 description 1
- BKCCAYLNRIRKDJ-UHFFFAOYSA-N 2-phenyl-4,5-dihydro-1h-imidazole Chemical compound N1CCN=C1C1=CC=CC=C1 BKCCAYLNRIRKDJ-UHFFFAOYSA-N 0.000 description 1
- HXIQYSLFEXIOAV-UHFFFAOYSA-N 2-tert-butyl-4-(5-tert-butyl-4-hydroxy-2-methylphenyl)sulfanyl-5-methylphenol Chemical compound CC1=CC(O)=C(C(C)(C)C)C=C1SC1=CC(C(C)(C)C)=C(O)C=C1C HXIQYSLFEXIOAV-UHFFFAOYSA-N 0.000 description 1
- FQHUDZKKDCTQET-UHFFFAOYSA-N 2-undecyl-4,5-dihydro-1h-imidazole Chemical compound CCCCCCCCCCCC1=NCCN1 FQHUDZKKDCTQET-UHFFFAOYSA-N 0.000 description 1
- WDNBURPWRNALGP-UHFFFAOYSA-N 3,4-Dichlorophenol Chemical compound OC1=CC=C(Cl)C(Cl)=C1 WDNBURPWRNALGP-UHFFFAOYSA-N 0.000 description 1
- JFGQHAHJWJBOPD-UHFFFAOYSA-N 3-hydroxy-n-phenylnaphthalene-2-carboxamide Chemical compound OC1=CC2=CC=CC=C2C=C1C(=O)NC1=CC=CC=C1 JFGQHAHJWJBOPD-UHFFFAOYSA-N 0.000 description 1
- FEHMRWVXXGFLDM-UHFFFAOYSA-N 3-hydroxy-n-tetradecylnaphthalene-2-carboxamide Chemical compound C1=CC=C2C=C(O)C(C(=O)NCCCCCCCCCCCCCC)=CC2=C1 FEHMRWVXXGFLDM-UHFFFAOYSA-N 0.000 description 1
- SXFJDZNJHVPHPH-UHFFFAOYSA-N 3-methylpentane-1,5-diol Chemical compound OCCC(C)CCO SXFJDZNJHVPHPH-UHFFFAOYSA-N 0.000 description 1
- XRZDIHADHZSFBB-UHFFFAOYSA-N 3-oxo-n,3-diphenylpropanamide Chemical compound C=1C=CC=CC=1NC(=O)CC(=O)C1=CC=CC=C1 XRZDIHADHZSFBB-UHFFFAOYSA-N 0.000 description 1
- ZAAMQANODYDRDF-UHFFFAOYSA-N 3-tert-butyl-2-hydroxybenzoic acid Chemical compound CC(C)(C)C1=CC=CC(C(O)=O)=C1O ZAAMQANODYDRDF-UHFFFAOYSA-N 0.000 description 1
- MDWVSAYEQPLWMX-UHFFFAOYSA-N 4,4'-Methylenebis(2,6-di-tert-butylphenol) Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 MDWVSAYEQPLWMX-UHFFFAOYSA-N 0.000 description 1
- MKYLPTKRHKDSKP-UHFFFAOYSA-N 4-(6-diazocyclohexa-2,4-dien-1-yl)morpholine Chemical compound [N-]=[N+]=C1C=CC=CC1N1CCOCC1 MKYLPTKRHKDSKP-UHFFFAOYSA-N 0.000 description 1
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- 229940043267 rhodamine b Drugs 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 229960004889 salicylic acid Drugs 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 239000007962 solid dispersion Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000011115 styrene butadiene Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 229940124530 sulfonamide Drugs 0.000 description 1
- 150000003456 sulfonamides Chemical class 0.000 description 1
- 150000008053 sultones Chemical class 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 150000001911 terphenyls Chemical class 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 1
- 150000003557 thiazoles Chemical class 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- LMYRWZFENFIFIT-UHFFFAOYSA-N toluene-4-sulfonamide Chemical compound CC1=CC=C(S(N)(=O)=O)C=C1 LMYRWZFENFIFIT-UHFFFAOYSA-N 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- IELLVVGAXDLVSW-UHFFFAOYSA-N tricyclohexyl phosphate Chemical compound C1CCCCC1OP(OC1CCCCC1)(=O)OC1CCCCC1 IELLVVGAXDLVSW-UHFFFAOYSA-N 0.000 description 1
- WEAPVABOECTMGR-UHFFFAOYSA-N triethyl 2-acetyloxypropane-1,2,3-tricarboxylate Chemical compound CCOC(=O)CC(C(=O)OCC)(OC(C)=O)CC(=O)OCC WEAPVABOECTMGR-UHFFFAOYSA-N 0.000 description 1
- JNXDCMUUZNIWPQ-UHFFFAOYSA-N trioctyl benzene-1,2,4-tricarboxylate Chemical compound CCCCCCCCOC(=O)C1=CC=C(C(=O)OCCCCCCCC)C(C(=O)OCCCCCCCC)=C1 JNXDCMUUZNIWPQ-UHFFFAOYSA-N 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
- 239000011787 zinc oxide Substances 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
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)
Description
【発明の詳細な説明】 「産業上の利用分野」 本発明は感熱記録材料に関するものであり、詳しくは、
熱記録前の保存性が優れ、特に地肌カブリの少ない感熱
記録材料に関するものである。DETAILED DESCRIPTION OF THE INVENTION "Industrial field of application" The present invention relates to a heat-sensitive recording material.
The present invention relates to a heat-sensitive recording material which is excellent in preservability before heat recording and particularly has less background fog.
「従来の技術」 感熱記録方法は、（１）現像が不要である、（２）支持
体が紙の場合は紙質が一般紙に近い、（３）取り扱いが
容易である、（４）発色濃度が高い、（５）記録装置が
簡単であり安価である、（６）記録時の騒音がない等の
利点があるため、フアクシミリやプリンターの分野で近
年急速に普及している。"Prior art" The thermal recording method (1) does not require development, (2) when the support is paper, the quality of the paper is similar to general paper, (3) is easy to handle, (4) color density It is rapidly popularized in recent years in the fields of facsimiles and printers because of its advantages such as high cost, (5) simple and inexpensive recording device, and (6) no noise during recording.
またこの様な記録分野においても種々の新しい機能が要
求されてきており、例えばカラー原稿を伝送するフアク
シミリやカラープリンターが開発されてきている。これ
らの印字方式としてインクジエツト方式や熱転写方式が
用いられている。しかし、これらはインクノズルに目詰
りを起こしたり、不要のインクシートが多量に出る等の
欠点を有している。感熱方式で多色発色が可能な感熱紙
は知られている。例えば、ジアゾスルホネートを応用し
たものや、ジアゾスルホネートとロイコ発色系とを組合
わせたものなどがある。これらは、発色反応を生じる化
合物で熱応答性に差をもたせる必要がある為使用できる
発色素材が非常に限定され、記録材料を設計、製造する
上で大きく制約される。Also, various new functions are required in such a recording field, and, for example, facsimiles and color printers for transmitting color originals have been developed. An ink jet method and a thermal transfer method are used as these printing methods. However, these have drawbacks such as clogging of ink nozzles and a large amount of unnecessary ink sheets. Thermal paper is known that is capable of multicolor development with a thermal system. For example, there are those to which diazosulfonate is applied, those in which diazosulfonate and leuco coloring system are combined, and the like. These are compounds that cause a color-forming reaction and it is necessary to have a difference in thermal responsiveness, so that the color-forming materials that can be used are very limited, and this is greatly restricted in designing and manufacturing recording materials.
また、一般に、感熱記録には文字記録が主として行われ
るが、近年テレビ画像のハードコピーの様な階調性のあ
る画像記録の要求が増している。階調性の表現方法とし
ては、記録濃度を一定にして記録面積を変える方法と、
記録面積を一定にして記録濃度を変える方法があるが、
前者は解像力が低下するうえ、中間調の表現に限界があ
るので、後者の方が優れている。ところが従来の感熱紙
では前者の方法に適正があるが、後者の方法にはあまり
適正がない。なぜなら後者の方法に対しては、感熱紙と
して中間濃度の印字が要求される。すなわち、印加エネ
ルギーの変化に対してある程度のなだらかさをもつて変
化すること（変化率が大きすぎないこと）が要求され
る。In general, character recording is mainly performed for heat-sensitive recording, but in recent years, there has been an increasing demand for image recording with gradation such as a hard copy of a television image. As a method of expressing gradation, a method of changing the recording area while keeping the recording density constant,
There is a method to change the recording density while keeping the recording area constant,
The former is superior to the latter because the resolution is lowered and the halftone expression is limited. However, conventional thermal paper is suitable for the former method, but not so suitable for the latter method. This is because the latter method requires printing with an intermediate density as thermal paper. That is, it is required that the applied energy changes with a certain degree of graduality (the change rate is not too large).
しかし、従来のロイコ発色型感熱記録紙は、ロイコ染料
とフエノール系顕色剤とをミクロンオーダーのサイズに
微分散し、混合して紙支持体に塗布したものであり、サ
ーマルヘツドで加熱されると、前記発色成分がお互いに
熔融混合し発色するものであるが、粒子間ないし塗布層
部位間に温度特性の差をつけることは容易ではない。However, the conventional leuco color-developing thermal recording paper is one in which a leuco dye and a phenol-based color developer are finely dispersed in a size of micron order, mixed and applied to a paper support, and heated by a thermal head. The above-mentioned color-forming components are melt-mixed with each other to form a color, but it is not easy to make a difference in temperature characteristics between particles or between coating layer portions.
そこで、我々はこれらの問題を解決するために発色反応
にかかわる成分のうちの少なくとも１種を芯物質に含有
し、この芯物質の周囲に重合によつて壁を形成してマイ
クロカプセル化する方法（特開昭58−65043号）によつ
て優れた感熱記録材料を見いだした。Therefore, in order to solve these problems, we have proposed a method in which at least one of the components involved in the coloring reaction is contained in the core substance, and a wall is formed around this core substance by polymerization to form microcapsules. (JP-A-58-65043) found an excellent thermal recording material.
そして、このマイクロカプセルの壁材等を考えた熱応答
性の異なる複数のマイクロカプセルを組合せることによ
り、以上の、中間調が再現できる感熱記録材料及び／又
は多色感熱記録材料が実現できることも見出し、各々、
特願昭59−89781及び特願昭59−99489に提示した。Then, by combining a plurality of microcapsules having different thermal responsiveness in consideration of the wall material of the microcapsules, it is possible to realize the above-described heat-sensitive recording material and / or multicolor heat-sensitive recording material capable of reproducing halftone. Headings, each,
It is presented in Japanese Patent Application No. 59-89781 and Japanese Patent Application No. 59-99489.
「発明が解決しようとしてする問題点」 ところが、このマイクロカプセル化の方法による感熱記
録材料においても、感度が充分でなく、地肌カブリが若
干つよく、また、保存中にしばしば予想外のカブリが発
生することがあつた。"Problems to be solved by the invention" However, even in the heat-sensitive recording material by the microencapsulation method, the sensitivity is not sufficient, the background fog is slightly strong, and unexpected fog often occurs during storage. That's right.
「発明の目的」 そこで、本発明の第１の目的は、地肌カブリが小さく生
保存性が優れ、かつ熱発色性の高い感熱記録材料を提供
することにある。"Object of the Invention" Therefore, a first object of the present invention is to provide a heat-sensitive recording material having a small background fog, excellent raw storability, and high thermochromic property.
本発明の第２の目的は、製造適性の優れた感熱記録材料
を提供することにある。A second object of the present invention is to provide a heat-sensitive recording material having excellent manufacturing suitability.
「問題点を解決するための手段」 本発明者等は鋭意研究の結果、発色反応を起す成分の少
くとも一つを内包したマイクロカプセルと、該発色反応
を起す成分と反応して発色する他方の成分を有する感熱
層を支持体上に設けた感熱記録材料において、該マイク
ロカプセルの壁材として脂肪族多価イソシアネートと芳
香族多価イソシアネートの混合物を用いることより成る
感熱記録材料によつて解決した。"Means for Solving Problems" The inventors of the present invention have as a result of earnest studies, and as a result, microcapsules containing at least one of the components that cause a color reaction and the other that develops a color by reacting with the component that causes the color reaction. A heat-sensitive recording material comprising a support and a heat-sensitive layer having the component (1) is solved by a heat-sensitive recording material comprising a mixture of an aliphatic polyvalent isocyanate and an aromatic polyvalent isocyanate as a wall material of the microcapsules. did.
「作用」 本発明のマイクロカプセルは、従来の記録材料に用いら
れているように熱や圧力によつて破壊してマイクロカプ
セルの芯に含有されている反応性物質とマイクロカプセ
ル外の反応性物質を接触させて発色反応を生じさせるも
のではなく、マイクロカプセルの芯及び外に存在する反
応性物質を加熱することによつて、主としてマイクロカ
プセル壁を透過して反応させるものである。"Function" The microcapsule of the present invention is a reactive substance that is destroyed by heat or pressure and is contained in the core of the microcapsule and a reactive substance outside the microcapsule as used in conventional recording materials. It does not cause a color development reaction by contacting with each other, but by heating the reactive substance existing on the core and the outside of the microcapsule, the reaction mainly passes through the microcapsule wall.
本発明のマイクロカプセルは、反応性物質を含有した芯
物質を乳化した後、その油滴の周囲に高分子物質の壁を
形成して作られる。高分子物質を形成するリアクタント
は油滴の内部に添加される。The microcapsules of the present invention are produced by emulsifying a core substance containing a reactive substance and then forming a wall of a polymer substance around the oil droplets. The reactant forming the polymeric material is added inside the oil droplet.
本発明のマイクロカプセル壁の作り方は油滴内部からの
リアクタントの重合によるマイクロカプセル化法を使用
するが短時間内に、均一な粒径をもち、生保存性のすぐ
れた感熱記録材料として好ましいカプセルを得ることが
できる。この手法及び化合物の具体例については、米国
特許3,726,804号、同3,796,669号の明細書に記載されて
いる。例えばポリウレアをカプセル壁材として用いる場
合には、多価イソシアネートをカプセル化すべき油性液
体中に混合し、水中に乳化分散し、次に温度を30〜80℃
に上昇することにより、油滴界面で水と高分子反応を起
してマイクロカプセル壁を形成させることができる。The method for producing the microcapsule wall of the present invention uses a microencapsulation method by polymerizing a reactant from the inside of oil droplets, but within a short time, it has a uniform particle size and is preferable as a heat-sensitive recording material having excellent raw storage stability. Can be obtained. Specific examples of this technique and compounds are described in the specifications of US Pat. Nos. 3,726,804 and 3,796,669. For example, when using polyurea as a capsule wall material, polyisocyanate is mixed in an oily liquid to be encapsulated, emulsified and dispersed in water, and then the temperature is 30 to 80 ° C.
As a result, the polymer can react with water at the oil droplet interface to form a microcapsule wall.
また、ポリウレタンをマイクロカプセル壁材として用い
る場合には、多価イソシアネートをリアクタントの第１
物質としてマイクロカプセル化すべき油性液体中に混合
しこれと反応してマイクロカプセル壁を形成する第２物
質（例えばポリオール，ポリアミン）を溶解した水中に
乳化分散するか、あるいは第２物質も多価イソシアネー
トと共にマイクロカプセル化すべき油性液体中に混合
し、水中に乳化分散し、次に温度を30〜80℃に上昇する
ことにより、油滴界面で高分子形成反応を起してマイク
ロカプセル壁を形成する。この時の温度は40〜60℃が好
ましく、また反応率は90％以上が好ましい。When polyurethane is used as the microcapsule wall material, polyvalent isocyanate is used as the first reactant.
As a substance, the second substance (for example, polyol or polyamine) which is mixed with an oily liquid to be microencapsulated and reacts with it to form a microcapsule wall is emulsified and dispersed in water, or the second substance is also a polyisocyanate. Together with an oily liquid to be microencapsulated, emulsified and dispersed in water, and then by raising the temperature to 30 to 80 ° C, a polymer forming reaction occurs at the oil droplet interface to form a microcapsule wall. . The temperature at this time is preferably 40 to 60 ° C., and the reaction rate is preferably 90% or more.
本発明のマイクロカプセルの壁材のリアクタントの第１
物質としては、キシリレンジイソシアネートとポリメチ
レンポリフエニルイソシアネートの混合物を用いるもの
であつて、これらとジアゾ化合物をカプセル化すべき油
性液体中に混合し、水中に乳化分散し、次に温度を上昇
することにより、油滴界面で高分子形成反応を起して、
マイクロカプセル壁を形成する。First Reactant for Wall Material of Microcapsule of the Present Invention
As the substance, a mixture of xylylene diisocyanate and polymethylene polyphenyl isocyanate is used, and these and the diazo compound are mixed in an oily liquid to be encapsulated, emulsified and dispersed in water, and then the temperature is raised. Causes a polymer formation reaction at the oil drop interface,
Form microcapsule walls.
これらの中、キシリレンジイソシアネートとトリメチロ
ールプロパンの付加物とポリメチレンポリフエニルイソ
シアネートの混合物が好ましい。これらの混合比は、キ
シリレンジイソシアネート／ポリメチレンポリフエニル
イソシアネートは20〜１の範囲である。そして、この混
合比は10〜５の範囲が特に好ましい。Among these, a mixture of an addition product of xylylene diisocyanate and trimethylolpropane and polymethylene polyphenyl isocyanate is preferable. The mixing ratio of these is in the range of 20 to 1 for xylylene diisocyanate / polymethylene polyphenyl isocyanate. The mixing ratio is particularly preferably in the range of 10-5.
すなわち、これらの壁材を使うと保存時の地肌カブリが
少く、ジアゾ化合物の包接性が良好なのでジアゾ化合物
を増量することができ画像濃度が高い。また、低沸点の
補助溶剤を必要としないので製造工程中に、回収設備を
設ける必要がなく、製造適性が優れている。That is, when these wall materials are used, the background fog during storage is small and the inclusion property of the diazo compound is good, so that the amount of the diazo compound can be increased and the image density is high. In addition, since a low boiling auxiliary solvent is not required, it is not necessary to provide a recovery facility during the manufacturing process, and the manufacturing suitability is excellent.
第２の物質であるポリオールとしては、脂肪族、芳香族
の多価アルコール、ヒドロキシポリエステル、ヒドロキ
シポリアルキレンエーテルのごときものがある。好まし
いポリオールとしては、２個の水酸基の間に下記
（Ｉ），（II），（III）又は（IV）の基を分子構造中
に有する分子量が5000以下のポリヒドロキシ化合物があ
げられる。Examples of the second substance, polyol, include aliphatic and aromatic polyhydric alcohols, hydroxypolyesters, and hydroxypolyalkylene ethers. Examples of preferable polyols include polyhydroxy compounds having a molecular weight of 5000 or less and having the following group (I), (II), (III) or (IV) in the molecular structure between two hydroxyl groups.
（Ｉ）炭素数２〜８の脂肪族炭化水素基 ここで、（II）、（III）、（IV）のArは置換あるい
は、無置換の芳香族部分を表わし、（Ｉ）の脂肪族炭化
水素基とは、−ＣｎH2n−を基方骨格とし、水素基が他
の元素と置換されていてもよい。(I) Aliphatic hydrocarbon group having 2 to 8 carbon atoms Here, (II), (III) , Ar is a substituted or a (IV), represents an aromatic moiety unsubstituted, aliphatic and hydrocarbon group, -C n H 2 n-groups of (I) It may have a rectangular skeleton, and the hydrogen group may be substituted with another element.
その具体例をあげると、（Ｉ）の例としては、エチレン
グリコール、1,3−プロパンジオール、1,4−ブタンジオ
ール、1,5−ペンタンジオール、1,6−ヘキサンジオー
ル、1,7−ヘプタンジノール、1,8−オクタンジオール、
プロピレングリコール、2,3−ジヒドロキシブタン、1,2
−ジヒドロキシブタン、1,3−ジヒドロキシブタン、2,2
−ジメチル−1,3−プロパンジオール、2,4−ペンタンジ
オール、2,5−ヘキサンジオール、３−メチル−1,5−ペ
ンタンジオール、1,4−シクロヘキサンジメタノール、
ジヒドロキシシクロヘキサン、ジエチレングリコール、
1,2,6−トリヒドロキシヘキサン、フエニルエチレング
リコール、1,1,1−トリメチロールプロパン、ヘキサン
トリオール、ペンタエリスリトール、グリセリンなどが
あげられる。Specific examples thereof include (I) ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7- Heptanedinol, 1,8-octanediol,
Propylene glycol, 2,3-dihydroxybutane, 1,2
-Dihydroxybutane, 1,3-dihydroxybutane, 2,2
-Dimethyl-1,3-propanediol, 2,4-pentanediol, 2,5-hexanediol, 3-methyl-1,5-pentanediol, 1,4-cyclohexanedimethanol,
Dihydroxycyclohexane, diethylene glycol,
Examples thereof include 1,2,6-trihydroxyhexane, phenylethylene glycol, 1,1,1-trimethylolpropane, hexanetriol, pentaerythritol, and glycerin.
（II）の例としては、1,4−ジ（２−ヒドロキシエトキ
シ）ベンゼン、レゾルシノールジヒドロキシエチルエー
テル等の芳香族多価アルコールとアルキレンオキサイド
との縮合生成物があげられる。Examples of (II) include condensation products of aromatic polyhydric alcohols such as 1,4-di (2-hydroxyethoxy) benzene and resorcinol dihydroxyethyl ether with alkylene oxides.
（III）の例としては、ｐ−キシリレングリコール、ｍ
−キシリレングリコール、α，α′−ジヒドロキシ−ｐ
−ジイソブロビルベンゼン等があげられる。Examples of (III) include p-xylylene glycol, m
-Xylylene glycol, α, α'-dihydroxy-p
-Diisobrovir benzene and the like.
（IV）の例としては、4,4′−ジヒドロキシ−ジフエニ
ルメタン、２−（p,p′−ジヒドロキシジフエニルメチ
ル）ベンジルアルコール、ビスフエノールＡにエチレン
オキサイドの付加物、ビスフエノールＡにプロピレンオ
キサイドの付加物などがあげられる。ポリオールはイソ
シアネート基１モルに対して、水酸基の割合が0.02〜２
モルで使用するのが好ましい。Examples of (IV) include 4,4'-dihydroxy-diphenylmethane, 2- (p, p'-dihydroxydiphenylmethyl) benzyl alcohol, an adduct of ethylene oxide with bisphenol A, and propylene oxide with bisphenol A. Examples include adjuncts. The proportion of hydroxyl groups in polyol is 0.02 to 2 per mol of isocyanate group.
It is preferably used in moles.
第２物質としてポリオールの代りにポリアミンを用いる
ことができるが、ポリアミンとしてはエチレンジアミ
ン、トリメチレンジアミン、テトラメチレンジアミン、
ペンタメチレンジアミン、ヘキサメチレンジアミン、ｐ
フエニレンジアミン、ｍ−フエニレンジアミン、ピペラ
ジン、２−メチルピペラジン、2,5−ジメチルピペラジ
ン、２−ヒドロキシトリメチレンジアミン、ジエチレン
トリアミン、トリエチレントリアミン、トリエチレンテ
トラミン、ジエチルアミノプロピルアミン、テトラエチ
レンペンタミン、エポキシ化合物のアミン付加物等があ
げられる。As the second substance, polyamine can be used instead of polyol, and as the polyamine, ethylenediamine, trimethylenediamine, tetramethylenediamine,
Pentamethylenediamine, hexamethylenediamine, p
Phenylenediamine, m-phenylenediamine, piperazine, 2-methylpiperazine, 2,5-dimethylpiperazine, 2-hydroxytrimethylenediamine, diethylenetriamine, triethylenetriamine, triethylenetetramine, diethylaminopropylamine, tetraethylenepentamine, Examples thereof include amine adducts of epoxy compounds.
多価イソシアネート、ポリオール、ポリアミンの添加量
をかえることで、他の条件が同一なら壁厚が変る。乳化
分散時の撹拌をかえることにより粒子サイズを、従つて
他の条件が同一なら壁厚みを変えることができる。By changing the amounts of polyvalent isocyanate, polyol, and polyamine added, the wall thickness will change if the other conditions are the same. By changing the stirring during emulsification and dispersion, it is possible to change the particle size, and thus the wall thickness under the same other conditions.
本発明においては発色剤として塩基性無色染料、ジアゾ
化合物のいずれを用いてもよい。In the present invention, either a basic colorless dye or a diazo compound may be used as the color former.
塩基性無色染料はエレクトロンを供与して、或いは酸な
どのプロトンを受容して発色する性質を有するものであ
つて、とくに限定されないが、通常ほぼ無色で、ラクト
ン、ラクタム、サルトン、スピロピラン、エステル、ア
ミドなどの部分骨格を有し、顕色剤と接触してこれらの
部分骨格が開環もしくは開裂する化合物が用いられる。
具体的には、クリスタルバイオレツトラクトン、ベンゾ
イルロイコメチレンブルー、マラカイトグリーンラクト
ン、ローダミンＢラクタム、1,3,3−トリメチル−６′
−エチル−８′−ブトキシインドリノベンゾスピロピラ
ン、２−ジメチルアミノ−７−メトキシフルオラン、３
−ジエチルアミノ−７−メトキシフルオラン、２−メチ
ル−３−アニリノ−７−シクロヘキシル−Ｎ−メチルア
ミノフルオラン、２−クロル−３−アニリノ−７−ジエ
チルアミノフルオラン等がある。The basic colorless dye has a property of developing a color by donating an electron or accepting a proton such as an acid, and is not particularly limited, but it is usually almost colorless, and lactone, lactam, sultone, spiropyran, ester, A compound having a partial skeleton such as an amide and being opened or cleaved by contact with a color developer is used.
Specifically, crystal violet lettactone, benzoyl leuco methylene blue, malachite green lactone, rhodamine B lactam, 1,3,3-trimethyl-6 '.
-Ethyl-8'-butoxyindolinobenzospiropyran, 2-dimethylamino-7-methoxyfluorane, 3
-Diethylamino-7-methoxyfluorane, 2-methyl-3-anilino-7-cyclohexyl-N-methylaminofluorane, 2-chloro-3-anilino-7-diethylaminofluorane and the like.
これらの発色剤を発色させる顕色剤としては、フエノー
ル化合物、有機酸もしくはその金属塩、オキシ安息香酸
エステル、などが用いられる。As a color developer for developing these color formers, a phenol compound, an organic acid or a metal salt thereof, an oxybenzoic acid ester, etc. are used.
特に融点が50゜〜250℃であり、特に好ましくは60゜〜2
00℃の水に難溶性のフエノール、有機酸が望ましい。In particular, the melting point is 50 ° to 250 ° C, particularly preferably 60 ° to 2 °
Phenols and organic acids, which are sparingly soluble in water at 00 ° C, are desirable.
フエノール化合物の例を示せば、4,4′−イソプロピリ
デン−ジフエノール（ビスフエノールＡ）、Ｐ−tert−
ブチルフエノール、2,4−ジニトロフエノール、3,4−ジ
クロロフエノール、4,4′−メチレン−ビス（2,6−ジ−
tert−ブチルフエノール）、ｐ−フエニルフエノール、
4,4−シクロヘキシリデンジフエノール、2,2′−メチレ
ンビス（４−tert−ブチルフエノール）、2,2′−メチ
レンビス（α−フエニル−ｐ−クレゾール）チオジフエ
ノール、4,4′−チオビス（６−tert−ブチル−ｍ−ク
レゾール）、スルホニルジフエノール、1,1−ビス（４
−ヒドロキシフエニル）−ｎ−ドデカン、4,4−ビス
（４−ヒドロキシフエニル）−１−ペンタン酸エチルエ
ステルのほか、ｐ−tert−ブチルフエノール−ホルマリ
ン縮合物、ｐ−フエニルフエノール−ホルマリン縮合物
などがある。Examples of phenol compounds are 4,4'-isopropylidene-diphenol (bisphenol A), P-tert-
Butylphenol, 2,4-dinitrophenol, 3,4-dichlorophenol, 4,4'-methylene-bis (2,6-di-
tert-butylphenol), p-phenylphenol,
4,4-Cyclohexylidenediphenol, 2,2'-methylenebis (4-tert-butylphenol), 2,2'-methylenebis (α-phenyl-p-cresol) thiodiphenol, 4,4'-thiobis ( 6-tert-butyl-m-cresol), sulfonyldiphenol, 1,1-bis (4
-Hydroxyphenyl) -n-dodecane, 4,4-bis (4-hydroxyphenyl) -1-pentanoic acid ethyl ester, p-tert-butylphenol-formalin condensate, p-phenylphenol-formalin There are condensates and the like.
有機酸もしくはその金属塩としては、３−tert−ブチル
サリチル酸、3,5−tert−ブチルサリチル酸、５−α−
メチルベンジルサリチル酸、3,5−ジ−α−メチルベン
ジルサリチル酸、３−tert−オクチルサリチル酸、５−
α，γ−ジメチル−α−フエニル−γ−フエニルプロピ
ルサリチル酸等及びその亜鉛塩、鉛塩、アルミニウム
塩、マグネシウム塩、ニツケル塩が有用である。Examples of the organic acid or its metal salt include 3-tert-butylsalicylic acid, 3,5-tert-butylsalicylic acid and 5-α-
Methylbenzyl salicylic acid, 3,5-di-α-methylbenzyl salicylic acid, 3-tert-octyl salicylic acid, 5-
[alpha], [gamma] -dimethyl- [alpha] -phenyl- [gamma] -phenylpropylsalicylic acid and the like and their zinc salts, lead salts, aluminum salts, magnesium salts and nickel salts are useful.
オキシ安息香酸エステルとしては、ｐ−オキシ安息香酸
エチル、ｐ−オキシ安息香酸ブチル、ｐ−オキシ安息香
酸ヘプチル、ｐ−オキシ安息香酸ベンジル等がある。Examples of the oxybenzoic acid ester include ethyl p-oxybenzoate, butyl p-oxybenzoate, heptyl p-oxybenzoate, benzyl p-oxybenzoate and the like.
また本発明において、発色剤としてジアゾ化合物を用い
ることも可能である。この場合には光安着可能な感熱記
録材料ができる。ジアゾ化合物は、一般式ArN2＋X-で示
されるジアゾニウム塩であり、カツプリング成分とカツ
プリング反応を起して発色することができるし、また光
によつて分解することができる化合物である。（式中、
Arは置換あるいは無置換の芳香族部分を表わし、N2 +は
ジアゾニウム基を表わし、X-は酸アニオンを表わす。） 塩を形成するジアゾニウムの具体例としては、４−ジア
ゾ−１−ジメチルアミノベンゼン、４−ジアゾ−１−ジ
エチルアミノベンゼン、４−ジアゾ−１−ベンゾイルア
ミノ−2,5−ジエトキシベンゼン、４−ジアゾ−１−モ
ルホリノベンゼン、４−ジアゾ−1,4−メトキシベンゾ
イルアミノ−2,5−ジエトキシベンゼン等が挙げられ
る。In the present invention, it is also possible to use a diazo compound as a color former. In this case, a heat-sensitive recording material which can be light-fastened can be obtained. The diazo compound is a diazonium salt represented by the general formula ArN 2 + X − , and is a compound capable of causing a coupling reaction with a coupling component to develop a color and capable of being decomposed by light. (In the formula,
Ar represents a substituted or unsubstituted aromatic moiety, N 2 + represents a diazonium group, and X − represents an acid anion. ) Specific examples of the diazonium which forms a salt include 4-diazo-1-dimethylaminobenzene, 4-diazo-1-diethylaminobenzene, 4-diazo-1-benzoylamino-2,5-diethoxybenzene, and 4-diazo-1-diethylaminobenzene. Examples thereof include diazo-1-morpholinobenzene and 4-diazo-1,4-methoxybenzoylamino-2,5-diethoxybenzene.
酸アニオンの具体例としては、ＣｎＦ2n＋１COO-（ｎは
３〜９の整数）、ＣｍＦ2m＋１SO3 -（ｍは２〜８の整
数）、（ClF2l＋1SO2）2CH-（ｌは１〜18の整数）、 BF4 -、PF6 -等が挙げられる。Specific examples of the anion, C n F 2n + 1 COO - (n is 3-9 integer), C m F 2m + 1 SO 3 - (m an integer of 2~8), (ClF 2l + 1 SO 2) 2 CH - (l 1 to 18 integer), BF 4 -, PF 6 -, and the like.
ジアゾ化合物（ジアゾニウム塩）の具体例としては、例
えば下記の例が挙げられる。Specific examples of the diazo compound (diazonium salt) include the following examples.
これらのジアゾニウム塩として反応して発色させる顕色
剤としては、塩基性雰囲気でジアゾニウム塩とカツプリ
ングして色素を形成するもの（カツプリング成分）であ
り、具体例としてはレゾルシン、フロログシン、2,3−
ジヒドロキシナフタレン−６−スルホン酸ナトリウム、
１−ヒドロキシ−２−ナフトエ酸モルホリノプロピルア
ミド、２−ヒドロキシ−３−ナフトエ酸−Ｎ−ドデシル
−オキシ−プロピルアミド、２−ヒドロキシ−３−ナフ
トエ酸テトラデシルアミド、アセトアニリド、アセトア
セトアニリド、ベンゾイルアセトアニリド、１−
（２′,4′,6′−トリクロロフエニル）−３−アニリノ
−５−ピラゾロン、１−フエニル−３−フエニルアセト
アミド−５−ピラゾロン等が挙げられる。更にこれらの
カツプリング成分を２種以上併用することによつて任意
の色調の画像を得ることができる。 The color developer which reacts as a diazonium salt to develop a color is one which forms a dye by coupling with a diazonium salt in a basic atmosphere (a coupling component), and specific examples thereof include resorcin, phlorogcine, and 2,3-
Sodium dihydroxynaphthalene-6-sulfonate,
1-hydroxy-2-naphthoic acid morpholinopropylamide, 2-hydroxy-3-naphthoic acid-N-dodecyl-oxy-propylamide, 2-hydroxy-3-naphthoic acid tetradecylamide, acetanilide, acetoacetanilide, benzoylacetanilide, 1-
(2 ', 4', 6'-trichlorophenyl) -3-anilino-5-pyrazolone, 1-phenyl-3-phenylacetamido-5-pyrazolone and the like can be mentioned. Further, by using two or more of these coupling components in combination, an image of any color tone can be obtained.
ジアゾニウム塩を発色剤として用いた系では、発色促進
の目的で塩基性物質が併用される。In a system using a diazonium salt as a color former, a basic substance is used together for the purpose of promoting color development.
塩基性物質としては、水難溶性ないしは、水不溶性の塩
基性物質や加熱によりアルカリを発生する物質が用いら
れる。As the basic substance, a poorly water-soluble or water-insoluble basic substance or a substance which generates an alkali upon heating is used.
塩基性物質としては、無機及び有機アンモニウム塩、有
機アミン、アミド、尿素やチオ尿素及びその誘導体、チ
アゾール類、ピロール類、ピリミジン類、ピペラジン
類、グアニジン類、インドール類、イミダゾール類、イ
ミダゾリン類、トリアゾール類、モルホリン類、ピペリ
ジン類、アミジン類、フオルムアジン類、ピリジン類等
の含窒素化合物が挙げられる。これらの具体例として
は、例えば酢酸アンモニウム、トリシクロヘキシルアミ
ン、トリベンジルアミン、オクタデシルベンジルアミ
ン、ステアリルアミン、アリル尿素、チオ尿素、メチル
チオ尿素、アリルチオ尿素、エチレンチオ尿素、２−ベ
ンジルイミダゾール、４−フエニルイミダゾール、２−
フエニル−４−メチル−イミダゾール、２−ウンデシル
−イミダゾリン、2,4,5−トリフリル−２−イミダゾリ
ン、1,2−ジフエニル−4,4−ジメチル−２−イミダゾリ
ン、２−フエニル−２−イミダゾリン、1,2,3−トリフ
エニルグアニジン、1,2−ジトリルグアニジン、1,2−ジ
シクロヘキシルグアニジン、1,2,3−トリシクロヘキシ
ルグアニジン、グアニジントリクロロ酢酸塩、N,N′−
ジベンジルピペラジン、4,4′−ジチオモルホリン、モ
ルホリニウムトリクロロ酢酸塩、２−アミノ−ベンゾチ
アゾール、２−ベンゾイルヒドラジノ−ベンゾチアゾー
ルがある。これらの塩基性物質は、２種以上併用して用
いることもできる。また塩基性無色染料とジアゾ化合の
両方に効果のある発色促進剤として、Ｐ−ベンジルオキ
シフエノール等のヒドロキシ化合物、フエニルカルバミ
ン酸エチル等のカルバミン酸エステル、Ｐ−トルエンス
ルホンアミド等のスルホンアミド、等を添加することが
できる。As the basic substance, inorganic and organic ammonium salts, organic amines, amides, urea and thiourea and their derivatives, thiazoles, pyrroles, pyrimidines, piperazines, guanidines, indoles, imidazoles, imidazolines, triazoles. And nitrogen-containing compounds such as morpholines, piperidines, amidines, formazines and pyridines. Specific examples thereof include ammonium acetate, tricyclohexylamine, tribenzylamine, octadecylbenzylamine, stearylamine, allylurea, thiourea, methylthiourea, allylthiourea, ethylenethiourea, 2-benzylimidazole, 4-phenyl. Imidazole, 2-
Phenyl-4-methyl-imidazole, 2-undecyl-imidazoline, 2,4,5-trifuryl-2-imidazoline, 1,2-diphenyl-4,4-dimethyl-2-imidazoline, 2-phenyl-2-imidazoline, 1,2,3-triphenylguanidine, 1,2-ditolylguanidine, 1,2-dicyclohexylguanidine, 1,2,3-tricyclohexylguanidine, guanidine trichloroacetic acid salt, N, N'-
There are dibenzylpiperazine, 4,4'-dithiomorpholine, morpholinium trichloroacetate, 2-amino-benzothiazole, 2-benzoylhydrazino-benzothiazole. These basic substances can be used in combination of two or more. Further, as a color-developing accelerator effective for both basic colorless dyes and diazo compounds, hydroxy compounds such as P-benzyloxyphenol, carbamate esters such as ethyl phenylcarbamate, sulfonamides such as P-toluenesulfonamide, Etc. can be added.
本発明は、マイクロカプセルの芯物質に含有する発色剤
もしくは顕色剤及びマイクロカプセルの壁材を水に不溶
性の有機溶媒によつて溶解または分散し、乳化した後そ
の回りにマイクロカプセル壁材重合によつて形成する
が、有機溶媒としては180℃以上の沸点のものが好まし
い。具体的には、リン酸エステル、フタル酸エステル、
その他のカルボン酸エステル、脂肪酸アミド、アルキル
化ビフエニル、アルキル化ターフエニル、塩素化パラフ
イン、アルキル化ナフタレン、ジアリールエタン等が用
いられる。具体例としてはリン酸トリクレジル、リン酸
トリオクチル、リン酸オクチルジフエニル、リン酸トリ
シクロヘキシル、フタル酸ジブチル、フタル酸ジオクチ
ル、フタル酸ジラウリル、フタル酸ジシクロヘキシル、
オレイン酸ブチル、ジエチレングリコールジベンゾエー
ト、セバシン酸ジオクチル、セバシン酸ジブチル、アジ
ピン酸ジオクチル、トリメリツト酸トリオクチル、クエ
ン酸アセチルトリエチル、マレイン酸オクチル、マレイ
ン酸ジブチル、イソプロピルビフエニル、イソアミルビ
フエニル、塩素化パラフイン、ジイソプロピルナフタレ
ン、1,1′−ジトリルエタン、2,4−ジターシヤリアミノ
フエノール、N,N−ジブチル−２−ブトキシ−５−ター
シヤリオクチルアニリン等が挙げられる。The present invention is to dissolve or disperse a color former or a developer contained in a core substance of a microcapsule and a wall material of the microcapsule with an organic solvent insoluble in water, and after emulsifying, polymerize the microcapsule wall material around it. However, the organic solvent preferably has a boiling point of 180 ° C. or higher. Specifically, phosphoric acid ester, phthalic acid ester,
Other carboxylic acid esters, fatty acid amides, alkylated biphenyls, alkylated terphenyls, chlorinated paraffins, alkylated naphthalenes, diarylethanes and the like can be used. Specific examples include tricresyl phosphate, trioctyl phosphate, octyl diphenyl phosphate, tricyclohexyl phosphate, dibutyl phthalate, dioctyl phthalate, dilauryl phthalate, dicyclohexyl phthalate,
Butyl oleate, diethylene glycol dibenzoate, dioctyl sebacate, dibutyl sebacate, dioctyl adipate, trioctyl trimellitate, acetyltriethyl citrate, octyl maleate, dibutyl maleate, isopropyl biphenyl, isoamyl biphenyl, chlorinated paraffin, diisopropyl Examples thereof include naphthalene, 1,1′-ditolylethane, 2,4-ditersialyaminophenol, N, N-dibutyl-2-butoxy-5-tersialyoctylaniline.
これらのうち、フタル酸ジブチル、リン酸トリクレジ
ル、フタル酸ジエチル、マレイン酸ジブチル等のエステ
ル系の溶媒が特に好ましい。Of these, ester solvents such as dibutyl phthalate, tricresyl phosphate, diethyl phthalate, and dibutyl maleate are particularly preferable.
また、発色剤としてジアゾ化合物を用いる場合、ジアゾ
ニウム塩の定着のための光照射処理により生成すると思
われるラジカルを消減させるために、トリメチロールプ
ロパントリアクリレート等のラジカル消滅剤を溶剤と共
に加えることができる。Further, when a diazo compound is used as a color former, a radical quenching agent such as trimethylolpropane triacrylate can be added together with a solvent in order to quench the radicals which are considered to be generated by the light irradiation treatment for fixing the diazonium salt. .
マイクロカプセルを作るときに、水溶性高分子を用いる
ことができるが水溶性高分子は水溶性のアニオン性高分
子、ノニオン性高分子、両性高分子のいずれでも良い。
アニオン性高分子としては、天然のものでも合成のもの
でも用いることができ、例えば−COO-、−SO▲- 3▼基等
を有するものが挙げられる。具体的なアニオン性の天然
高分子としてはアラビヤゴム、アルギン酸などがあり、
半合成品としてはカルボキシメチルセルローズ、フタル
化ゼラチン、硫酸化デンプン、硫酸化セルロース、リグ
ニンスルホン酸などがある。When making the microcapsules, a water-soluble polymer can be used, and the water-soluble polymer may be any of a water-soluble anionic polymer, nonionic polymer and amphoteric polymer.
As the anionic polymer, a natural one or a synthetic one can be used, and examples thereof include those having a —COO − , —SO 3 − 3 group or the like. Specific examples of anionic natural polymers include arabic gum and alginic acid.
Semi-synthetic products include carboxymethyl cellulose, phthalated gelatin, sulfated starch, sulfated cellulose and lignin sulfonic acid.
又合成品としては無水マレイン酸系（加水分解したもの
も含む）共重合体、アクリル酸系（メタクリル酸系も含
む）重合体及び共重合体、ビニルベンゼンスルホン酸系
重合体及び共重合体、カルボキシ変性ポリビニルアルコ
ールなどがある。ノニオン性高分子としては、ポリビニ
ルアルコール、ヒドロキシエチルセルロース、メチルセ
ルロース等がある。Further, synthetic products include maleic anhydride-based (including hydrolyzed) copolymers, acrylic acid-based (including methacrylic acid-based) polymers and copolymers, vinylbenzenesulfonic acid-based polymers and copolymers, Examples include carboxy-modified polyvinyl alcohol. Examples of the nonionic polymer include polyvinyl alcohol, hydroxyethyl cellulose, methyl cellulose and the like.
両性の化合物としてはゼラチン等がある。Examples of amphoteric compounds include gelatin.
これらの水溶性高分子は0.01〜10wt％の水溶液として用
いられる。マイクロカプセルの粒径は20μ以下に調整さ
れる。一般に粒径が20μを越えると印字画質が劣りやす
い。These water-soluble polymers are used as 0.01-10 wt% aqueous solutions. The particle size of the microcapsules is adjusted to 20 μm or less. Generally, if the particle size exceeds 20μ, the print quality tends to be poor.
特に、サーマルヘツドによる加熱を塗布層側から行う場
合には圧力カブリを避けるために８μ以下が好ましい。In particular, when heating with a thermal head is performed from the coating layer side, it is preferably 8 μm or less in order to avoid pressure fog.
本発明に用いられる主成分である発色剤及び顕色剤は、
その内のいずれか１種をマイクロカプセルの芯物質とし
て用いる。２種をマイクロカプセルの芯物質に含有させ
る場合は、別々のマイクロカプセルに内包すれば良い。
マイクロカプセルの芯物質に含有されない他の成分は、
マイクロカプセルの外の感熱層に用いられる。The color developing agent and the color developing agent, which are the main components used in the present invention,
Any one of them is used as the core substance of the microcapsule. When two kinds are contained in the core substance of the microcapsule, they may be encapsulated in separate microcapsules.
Other ingredients that are not contained in the core material of the microcapsules are:
Used for the heat sensitive layer outside the microcapsules.
マイクロカプセルを作るとき、マイクロカプセル化すべ
き成分を0.2wt％以上含有した乳化液から作ることがで
きる。When making a microcapsule, it can be made from an emulsion containing 0.2 wt% or more of the component to be microencapsulated.
本発明に用いられる発色剤、顕色剤及び必要により用い
る塩基性物質、発色促進剤は、マイクロカプセルの内部
に含有されても、あるいはマイクロカプセルの外部の感
熱層に含有されても、発色剤１重量部に対して顕色剤は
0.1〜10重量部、塩基性物質、発色促進剤はそれぞれ0.1
〜20重量部の割合いで使用することが好ましい。また発
色剤は0.05〜5.0g/m2塗布することが好ましい。The color-forming agent, the color-developing agent used in the present invention, and the basic substance and the color-promoting agent used as necessary are contained in the microcapsules or contained in the heat-sensitive layer outside the microcapsules. 1 part by weight of developer
0.1-10 parts by weight, basic substance, color-promoting agent 0.1
It is preferably used in a proportion of from about 20 parts by weight. The color former is preferably applied in an amount of 0.05 to 5.0 g / m 2 .
本発明に用いる発色剤、顕色剤及び必要により用いる塩
基性物質、発色促進剤はマイクロカプセル化されないと
きは、サンドミル等により水溶性高分子と共に固体分散
して用いるのがよい。好ましい水溶性高分子としてはマ
イクロカプセルを作るときに用いられる水溶性高分子が
挙げられる。このとき水溶性高分子の濃度は２〜30wt％
であり、この水溶性高分子溶液に対して発色剤、顕色
剤、塩基性物質等の芯物質は、それぞれ５〜40wt％にな
るように投入される。When the color-forming agent, the color-developing agent, the basic substance and the color-accelerating accelerator used in the present invention are not microencapsulated, it is preferable to use them by solid dispersion with a water-soluble polymer by a sand mill or the like. Preferred water-soluble polymers include water-soluble polymers used when making microcapsules. At this time, the concentration of the water-soluble polymer is 2 to 30 wt%
The core substances such as the color former, the color developer, and the basic substance are added to the water-soluble polymer solution in an amount of 5 to 40 wt%.
分散された粒子サイズは10μ以下が好ましい。The dispersed particle size is preferably 10 μm or less.
本発明の感熱記録材料には熱ヘツドに対するステイツキ
ングの防止や筆記性を改良する目的で、シリカ、硫酸バ
リウム、酸化チタン、水酸化アルミニウム、酸化亜鉛、
炭酸カルシウム等の顔料や、スチレンビーズ、尿素−メ
ラミン樹脂等の微粉末を使用することができる。The heat-sensitive recording material of the present invention contains silica, barium sulfate, titanium oxide, aluminum hydroxide, zinc oxide, for the purpose of preventing sticking to the thermal head and improving the writability.
Pigments such as calcium carbonate and fine powders such as styrene beads and urea-melamine resin can be used.
また同様に、ステイツキング防止のために金属石けん類
も使用することができる。これらの使用量としては0.2
〜7g/m2である。Similarly, metal soaps can be used to prevent staking. The usage of these is 0.2
~ 7 g / m 2 .
更に本発明の感熱記録材料には、熱記録濃度を上げるた
めに熱融解性物質を用いることができる。熱融解性物質
としては常温では固体で、サーマルヘツドによる加熱で
融解する融点50〜150℃の物質であり、発色剤、顕色剤
あるいは塩基性物質、発色促進剤を溶かす物質である。
熱融解性物質は0.1〜10μの粒子状に分散して、固形分
0.2〜7g/m2の量で使用される。熱融解性物質の具体例と
しては、脂肪酸アミド、Ｎ置換脂肪酸アミド、ケトン化
合物、尿素化合物、エステル等が挙げられる。Further, in the heat-sensitive recording material of the present invention, a heat-melting substance can be used to increase the heat-recording density. The heat-fusible substance is a substance that is solid at room temperature and has a melting point of 50 to 150 ° C. that is melted by heating with a thermal head, and is a substance that dissolves a color former, a developer or a basic substance, and a color accelerator.
The heat-fusible substance is dispersed in the form of particles of 0.1 to 10μ,
Used in an amount of 0.2 to 7 g / m 2 . Specific examples of the heat-fusible substance include fatty acid amide, N-substituted fatty acid amide, ketone compound, urea compound, ester and the like.
本発明の感熱記録材料には適当なバインダーを用いて塗
工することができる。The heat-sensitive recording material of the present invention can be coated with a suitable binder.
バインダーとしてはポリビニルアルコール、メチルセル
ロース、カルボキシメチルセルロース、ヒドロキシプロ
ピルセルロース、アラビヤゴム、ゼラチン、ポリビニル
ピロリドン、カゼイン、スチレン−ブタジエンラテツク
ス、アクリロニトリル−ブタジエンラテツクス、ポリ酢
酸ビニル、ポリアクリル酸エステル、エチレン−酢酸ビ
ニル共重合体、の各種エマルジヨンを用いることができ
る。使用量は固形分0.5〜5g/m2である。As the binder, polyvinyl alcohol, methyl cellulose, carboxymethyl cellulose, hydroxypropyl cellulose, arabic rubber, gelatin, polyvinyl pyrrolidone, casein, styrene-butadiene latex, acrylonitrile-butadiene latex, polyvinyl acetate, polyacrylic ester, ethylene-vinyl acetate copolymer Various emulsions of polymers can be used. The amount used is 0.5 to 5 g / m 2 of solid content.
本発明では以上の素材の他に酸安定剤としてクエン酸、
酒石酸、シユウ酸、ホウ酸、リン酸、ピロリン酸、を添
加することができる。In the present invention, in addition to the above materials, citric acid as an acid stabilizer,
Tartaric acid, oxalic acid, boric acid, phosphoric acid, pyrophosphoric acid can be added.
本発明の感熱記録材料は、発色剤、顕色剤、必要により
用いる塩基性物質、発色促進剤及びその他の添加物を含
有した塗布液を作り、紙や合成樹脂フイルム等の支持体
の上にバー塗布、ブレード塗布、エアナイフ塗布、グラ
ビア塗布、ロールコーテイング塗布、スプレー塗布、デ
イツプ塗布等の塗布法により塗布乾燥して固形分2.5〜2
5g/m2の感熱層を設ける。また別な方法として顕色剤及
びその他の添加物をマイクロカプセルの芯物質として添
加するか、あるいは固体分散するか、あるいは水溶液と
して溶解した後混合して塗布液を作り、支持体上に塗
布、乾燥して固形分２〜10g/m2のプレコート層を設け、
更にその上に主成分である発色剤とその他の添加物をマ
イクロカプセルの芯物質として添加するか、あるいは固
体分散するかあるいは水溶液として溶解した後混合して
作つた塗布液を塗布、乾燥して固形分１〜15g/m2の塗布
層を設けた積層型にすることも可能である。いずれにし
ても発色剤及び顕色剤のうちのいずれかひとつをマイク
ロカプセルに内包する必要がある。積層型の感熱記録材
料は積層の順序が前記の積層が逆のものも可能であり、
塗布方法としては積層の遂次塗布あるいは同時塗布も可
能である。この積層型の感熱記録材料は特に長期の生保
存性に優れた性能が得られる。The heat-sensitive recording material of the present invention is prepared by preparing a coating solution containing a color former, a color developer, a basic substance used if necessary, a color accelerator and other additives, and coating it on a support such as paper or a synthetic resin film. Solid content of 2.5 to 2 after coating and drying by coating methods such as bar coating, blade coating, air knife coating, gravure coating, roll coating coating, spray coating, and dip coating.
Provide a heat-sensitive layer of 5g / m 2 . As another method, a color developer and other additives are added as a core substance of microcapsules, or they are solid-dispersed, or they are dissolved as an aqueous solution and mixed to prepare a coating solution, which is coated on a support, Provide a precoat layer with a solid content of 2 to 10 g / m 2 by drying,
Furthermore, a coloring agent as a main component and other additives are added as a core substance of the microcapsules, or they are dispersed in a solid or dissolved in an aqueous solution and mixed to prepare a coating solution, which is then dried. It is also possible to use a laminated type in which a coating layer having a solid content of 1 to 15 g / m 2 is provided. In any case, it is necessary to encapsulate any one of the color former and the developer in the microcapsule. The laminated thermal recording material can be formed by laminating the layers in the reverse order,
As a coating method, successive coating of layers or simultaneous coating is possible. This laminated-type heat-sensitive recording material is particularly excellent in long-term storability.
支持体に用いられる紙としてはアルキルケテンダイマー
等の中性サイズ剤によりサイジングされた熱抽出pH6〜
９の中性紙（特開昭55−14281号記載のもの）を用いる
と経時保存性の点で有利である。The paper used for the support is heat-extracted pH 6 to 6 sized with a neutral sizing agent such as alkyl ketene dimer.
Use of 9 neutral paper (described in JP-A-55-14281) is advantageous in terms of storage stability over time.
また紙への塗液の浸透を防ぎ、また、記録熱ヘツドと感
熱記録層との接触をよくするには、特開昭57−116687号
に記載の、 かつ、ベツク平滑度90秒以上の紙が有利である。In order to prevent the coating liquid from penetrating into the paper and to improve the contact between the recording heat head and the heat-sensitive recording layer, it is described in JP-A-57-116687. Moreover, paper having a smoothness of 90 seconds or more is advantageous.
また特開昭58−136492号に記載の光学的表面粗さが８μ
以下、かつ厚みが40〜75μの紙、特開昭58−69091号記
載の密度0.9g/cm3以下でかつ光学的接触率が15％以上の
紙、特開昭58−69097号に記載のカナダ標準水度（JIS
P8121）で400cc以上に叩解処理したパルプより抄造
し、塗布液のしみ込みを防止した後、特開昭58−65695
号に記載の、ヤンキーマシンにより抄造された原紙の光
沢面を塗布面とし発色濃度及び解像力を改良するもの、
特開昭59−35985号に記載の、原紙にコロナ放電処理を
施し、塗布適性を改良した紙等も本発明に用いられ、良
好な結果を与える。これらの他通常の感熱記録紙の分野
で用いられる支持体はいずれも本発明の支持体として使
用することができる。The optical surface roughness described in JP-A-58-136492 is 8 μm.
Paper having a thickness of 40 to 75 μ, a paper having a density of 0.9 g / cm 3 or less and an optical contact ratio of 15% or more as described in JP-A-58-69091, and JP-A-58-69097. Canadian Standard Water (JIS
P8121) was used to make paper from pulp that had been beaten to 400 cc or more to prevent the coating liquid from seeping in.
In order to improve the color density and resolution by using the glossy surface of the base paper produced by the Yankee machine as the coating surface,
The paper described in JP-A-59-35985, which is obtained by subjecting the base paper to corona discharge treatment to improve the coating suitability, is also used in the present invention and gives good results. In addition to these, any of the supports generally used in the field of heat-sensitive recording paper can be used as the support of the present invention.
本発明の感熱記録材料は、高速記録の要求されるフアク
シミリや電子計算機のプリンター用紙として用いること
ができる。この他に熱現像型複写紙としても用いること
ができる。The heat-sensitive recording material of the present invention can be used as printer paper for facsimiles and electronic computers that require high-speed recording. In addition to this, it can also be used as a heat-developing copying paper.
「実施例」 以下に実施例を示すが、本発明はこれに限定されるもの
ではない。なお添加量を示す「部」は「重量部」を表わ
す。"Examples" Examples will be shown below, but the present invention is not limited thereto. In addition, "part" indicating the addition amount represents "part by weight".
実施例１ 下記ジアゾ化合物４部及び脂肪族多価イソシアネートで
あるキシリレンジイソシアネートとトリメチロールプロ
パンの（3:1）の付加物（武田製薬（株）製商品名「タ
ケネートD110N」）12部と芳香族系多価イソシアネート
であるポリメチレンポリフエニルイソシアネート（日本
ポリウレタン（株）製、商品名「ミリオネートMR40
0」）12部の混合物をリン酸トリクレジル12部とトリメ
チロールプロパントリアクリレート12部混合溶媒に添
加、混合した。このジアゾ化合物の溶液をポリビニルア
ルコール3.5部、ゼラチン1.7部、水58部に溶解されてい
る水溶液に混合し20℃で乳化分散した。Example 1 4 parts of the following diazo compound, 12 parts of an adduct of (3: 1) of trimethylolpropane and xylylenediisocyanate, which is an aliphatic polyisocyanate (trade name “Takenate D110N” manufactured by Takeda Pharmaceutical Co., Ltd.), and an aroma. Polymethylene polyphenyl isocyanate, which is a group polyvalent isocyanate (manufactured by Nippon Polyurethane Co., Ltd., trade name "Millionate MR40
0 ") 12 parts of the mixture was added to and mixed with 12 parts of tricresyl phosphate 12 parts and trimethylolpropane triacrylate 12 parts. A solution of this diazo compound was mixed with an aqueous solution prepared by dissolving 3.5 parts of polyvinyl alcohol, 1.7 parts of gelatin and 58 parts of water, and emulsified and dispersed at 20 ° C.
得られた乳化液に水100部を加え撹拌しながら60℃に加
温し２時間後にジアゾ化合物を内包する平均粒径３μの
カプセルを得た。100 parts of water was added to the obtained emulsion, and the mixture was heated to 60 ° C. with stirring and after 2 hours, capsules having an average particle size of 3 μm and containing a diazo compound were obtained.
（ジアゾ化合物） 次に、２−ヒドロキシ−３−ナフトエ酸アニリド20部を
５％ポリビニルアルコール水溶液100部に加え、サンド
ミルで約24時間分散し平均粒径３μの分散物を得た。(Diazo compound) Next, 20 parts of 2-hydroxy-3-naphthoic acid anilide was added to 100 parts of a 5% aqueous polyvinyl alcohol solution and dispersed in a sand mill for about 24 hours to obtain a dispersion having an average particle diameter of 3 μm.
次にトリフエニルグアニジン20部を５％ポリビニルアル
コール水溶液100部に加えてサンドミルで約24時間分散
し、平均粒径３μの分散物を得た。Next, 20 parts of triphenylguanidine was added to 100 parts of a 5% aqueous solution of polyvinyl alcohol and dispersed by a sand mill for about 24 hours to obtain a dispersion having an average particle size of 3μ.
さらに、Ｐ−ベンジルオキシフエノール20部を５％ポリ
ビニルアルコール水溶液100部に加えて、サンドミルで
約24時間分子し、平均粒径約３μのＰ−ベンジルオキシ
フエノールの分散液を得た。Further, 20 parts of P-benzyloxyphenol was added to 100 parts of a 5% polyvinyl alcohol aqueous solution, and the mixture was subjected to a sand mill for about 24 hours to obtain a dispersion liquid of P-benzyloxyphenol having an average particle size of about 3 μm.
以上のようにして得られたジアゾ化合物のカプセル液50
部にカツプリング成分分散物15部、トリフエニルグアニ
ジン分散物15部、Ｐ−ベンジルオキシフエノールの分散
物30部を加えて塗布液とした。The diazo compound capsule liquid obtained as described above 50
15 parts of coupling component dispersion, 15 parts of triphenylguanidine dispersion, and 30 parts of P-benzyloxyphenol dispersion were added to 10 parts to prepare a coating solution.
この塗布液を平滑な上質紙（50g/m2）にコーテイングロ
ツドを用いて乾燥重量で20g/m2になるようにバー塗布し
45℃で30分間乾燥して感熱記録材料を得た。This coating solution was applied to a smooth high-quality paper (50 g / m 2 ) using a coating grind bar with a dry weight of 20 g / m 2 by bar coating.
A thermosensitive recording material was obtained by drying at 45 ° C for 30 minutes.
（試験方法） 得られた感熱記録材料にGIIIモードサーマルプリンター
（ハイフアツクス 700;日立製作所（株）製）を用いて
熱記録し、次にリコピースーパードライ100（リコー
（株）製）を用いて全面露光して、定着した。得られた
記録画像をマスクベス反射濃度計によりブルー濃度を測
定した。又、同じく地肌部の黄色濃度を測定した。それ
らの結果を第１表にしめす。一方、定着部分に対し再度
熱記録を行つたところいずれも画像記録されず定着され
ていることが確認された。(Test method) Thermal recording was performed on the obtained thermal recording material using a GIII mode thermal printer (Hyfax 700; manufactured by Hitachi, Ltd.), and then the entire surface was recorded using Ricopy Super Dry 100 (manufactured by Ricoh Co., Ltd.). It was exposed and fixed. The obtained recorded image was measured for blue density with a Maskbeth reflection densitometer. In addition, the yellow density of the background part was also measured. The results are shown in Table 1. On the other hand, when heat recording was performed again on the fixed portion, it was confirmed that no image was recorded on any of the fixed portions.
次に、生保存性をみるために、感熱記録材料の地肌濃度
（地肌カブリ）と、更に感熱記録材料を40℃、相対湿度
90％RHの条件で暗所に24時間保存し、強制劣化テストを
行つた後の地肌カブリをマクベス反射濃度計で測定し、
地肌カブリの変化をみた。それらの結果を第１表に示
す。Next, in order to check the raw storability, the background density (background fog) of the thermosensitive recording material and the thermosensitive recording material at 40 ° C and relative humidity
Stored in a dark place for 24 hours under the condition of 90% RH and measured the background fog after conducting a forced deterioration test with a Macbeth reflection densitometer,
I saw changes in the background fog. The results are shown in Table 1.
実施例２ 実施例１のタケネートD110N12部、ミリオネートMR400
12部、リン酸トリクレジル12部、トリメチロールプロパ
ン12部を用いる代りに各々、18部、16部、６部及び18部
を用いる以外は実施例１と同様にして感熱記録材料を作
製し、試験した。得られた結果を第１表に示す。Example 2 12 parts of Takenate D110N, Millionate MR400 of Example 1
A thermosensitive recording material was prepared and tested in the same manner as in Example 1 except that 18 parts, 16 parts, 6 parts and 18 parts were used instead of using 12 parts, 12 parts tricresyl phosphate and 12 parts trimethylolpropane, respectively. did. The results obtained are shown in Table 1.
実施例３ 実施例１のジアゾ化合物を４部用いる代りにジアゾ化合
物６部用いる以外は実施例１と同様にして、感熱記録材
料を作製し、試験した。得られた結果を第１表に示す。Example 3 A thermosensitive recording material was prepared and tested in the same manner as in Example 1 except that 6 parts of the diazo compound was used instead of 4 parts of the diazo compound of Example 1. The results obtained are shown in Table 1.
比較例１ マイクロカプセル壁材としてタケネートD110N24部、溶
剤としてリン酸トリクレジルエステル６部、トリメチロ
ールプロパントリアクリレート18部を用いる以外は実施
例１と同様にして感熱記録材料を作製し、試験した。結
果を第１表に示す。Comparative Example 1 A thermosensitive recording material was prepared and tested in the same manner as in Example 1 except that 24 parts of Takenate D110N was used as the microcapsule wall material, 6 parts of tricresyl phosphate ester and 18 parts of trimethylolpropane triacrylate were used as the solvent. The results are shown in Table 1.
比較例２ マイクロカプセル壁材として、タケネートD110N24部を
用いる以外は実施例３と同様にして感熱記録材料を作製
し、試験した。結果を第１表に示す。Comparative Example 2 A thermosensitive recording material was prepared and tested in the same manner as in Example 3 except that 24 parts of Takenate D110N was used as the microcapsule wall material. The results are shown in Table 1.
「発明の効果」 第１表からわかるように、マイクロカプセルの壁材とし
てキシリレンジイソシアネートとポリメチレンポリフエ
ニルイソシアネートの化合物を用いた実施例１〜３は地
肌カブリが少なく、強制劣化によつても地肌カブリの増
加が少い。しかしマイクロカプセルの壁材としてキシリ
レンジイソシアネートのみを用いた比較例１〜２は地肌
カブリが高く、強制劣化によつて更に地肌カブリが増加
す。 "Effects of the invention" As can be seen from Table 1, Examples 1 to 3 using the compounds of xylylene diisocyanate and polymethylene polyphenyl isocyanate as the wall material of the microcapsules have little background fog and are also caused by forced deterioration. Little increase in background fog. However, Comparative Examples 1 and 2 using only xylylene diisocyanate as the wall material of the microcapsules have high background fog, and the background fog further increases due to forced deterioration.
Claims (1)
したマイクロカプセルと該発色反応を起す成分と反応し
て発色する他方の成分を有する感熱層を支持体上に設け
た感熱記録材料において、該マイクロカプセルの壁材と
してキシリレンジイソシアネートとポリメチレンポリフ
エニルイソシアネートの混合物を用いることを特徴とす
る感熱記録材料。1. A heat-sensitive recording material comprising a support and a heat-sensitive layer having microcapsules containing at least one of the components that cause a color-forming reaction and the other component that develops a color by reacting with the component that causes the color-forming reaction. 2. A heat-sensitive recording material characterized in that a mixture of xylylene diisocyanate and polymethylene polyphenyl isocyanate is used as the wall material of the microcapsule.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60097188A JPH0686154B2 (en) | 1985-05-08 | 1985-05-08 | Thermal recording material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60097188A JPH0686154B2 (en) | 1985-05-08 | 1985-05-08 | Thermal recording material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS61254389A JPS61254389A (en) | 1986-11-12 |
| JPH0686154B2 true JPH0686154B2 (en) | 1994-11-02 |
Family
ID=14185599
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP60097188A Expired - Lifetime JPH0686154B2 (en) | 1985-05-08 | 1985-05-08 | Thermal recording material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0686154B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| LT1840145T (en) * | 2006-03-30 | 2018-02-26 | Fmc Corporation | Acetylene carbamide derivatives-polyurea polymers and microcapsules and formulations thereof for controlled release |
-
1985
- 1985-05-08 JP JP60097188A patent/JPH0686154B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS61254389A (en) | 1986-11-12 |
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Legal Events
| Date | Code | Title | Description |
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| R250 | Receipt of annual fees |
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| EXPY | Cancellation because of completion of term |