JPS62212190A - Thermal recording material - Google Patents
Thermal recording materialInfo
- Publication number
- JPS62212190A JPS62212190A JP61056004A JP5600486A JPS62212190A JP S62212190 A JPS62212190 A JP S62212190A JP 61056004 A JP61056004 A JP 61056004A JP 5600486 A JP5600486 A JP 5600486A JP S62212190 A JPS62212190 A JP S62212190A
- Authority
- JP
- Japan
- Prior art keywords
- compound
- diisocyanate
- group
- microcapsules
- heat
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000000463 material Substances 0.000 title claims abstract description 36
- 150000001989 diazonium salts Chemical class 0.000 claims abstract description 23
- 150000001875 compounds Chemical class 0.000 claims abstract description 17
- 239000003094 microcapsule Substances 0.000 claims abstract description 15
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 9
- 239000000126 substance Substances 0.000 claims abstract description 8
- 125000003710 aryl alkyl group Chemical group 0.000 claims abstract description 3
- 125000003118 aryl group Chemical group 0.000 claims abstract description 3
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims abstract description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 3
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 claims abstract description 3
- 239000012948 isocyanate Substances 0.000 claims description 13
- -1 isocyanate compound Chemical class 0.000 claims description 11
- 239000012298 atmosphere Substances 0.000 claims description 6
- 125000006165 cyclic alkyl group Chemical group 0.000 claims description 2
- 125000005843 halogen group Chemical group 0.000 claims description 2
- 125000004957 naphthylene group Chemical group 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 11
- 230000035945 sensitivity Effects 0.000 abstract description 10
- 238000007639 printing Methods 0.000 abstract description 4
- VGHSXKTVMPXHNG-UHFFFAOYSA-N 1,3-diisocyanatobenzene Chemical compound O=C=NC1=CC=CC(N=C=O)=C1 VGHSXKTVMPXHNG-UHFFFAOYSA-N 0.000 abstract description 3
- ALQLPWJFHRMHIU-UHFFFAOYSA-N 1,4-diisocyanatobenzene Chemical compound O=C=NC1=CC=C(N=C=O)C=C1 ALQLPWJFHRMHIU-UHFFFAOYSA-N 0.000 abstract description 3
- 239000012736 aqueous medium Substances 0.000 abstract description 3
- 150000002009 diols Chemical class 0.000 abstract description 3
- 238000004321 preservation Methods 0.000 abstract description 3
- VWGKEVWFBOUAND-UHFFFAOYSA-N 4,4'-thiodiphenol Chemical compound C1=CC(O)=CC=C1SC1=CC=C(O)C=C1 VWGKEVWFBOUAND-UHFFFAOYSA-N 0.000 abstract description 2
- 229920001228 polyisocyanate Polymers 0.000 abstract 3
- 239000005056 polyisocyanate Substances 0.000 abstract 3
- BLDLRWQLBOJPEB-UHFFFAOYSA-N 2-(2-hydroxyphenyl)sulfanylphenol Chemical compound OC1=CC=CC=C1SC1=CC=CC=C1O BLDLRWQLBOJPEB-UHFFFAOYSA-N 0.000 abstract 1
- 125000000753 cycloalkyl group Chemical group 0.000 abstract 1
- 230000002349 favourable effect Effects 0.000 abstract 1
- 125000001188 haloalkyl group Chemical group 0.000 abstract 1
- 229910052736 halogen Inorganic materials 0.000 abstract 1
- 150000002367 halogens Chemical class 0.000 abstract 1
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 description 13
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 12
- 239000002609 medium Substances 0.000 description 11
- 238000000576 coating method Methods 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- 239000011248 coating agent Substances 0.000 description 8
- 238000001454 recorded image Methods 0.000 description 7
- JWAZRIHNYRIHIV-UHFFFAOYSA-N 2-naphthol Chemical compound C1=CC=CC2=CC(O)=CC=C21 JWAZRIHNYRIHIV-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- 125000005442 diisocyanate group Chemical group 0.000 description 6
- 150000002513 isocyanates Chemical class 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 239000004372 Polyvinyl alcohol Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000011162 core material Substances 0.000 description 5
- 229920002451 polyvinyl alcohol Polymers 0.000 description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- 150000007514 bases Chemical class 0.000 description 4
- 238000004040 coloring Methods 0.000 description 4
- 235000014113 dietary fatty acids Nutrition 0.000 description 4
- 239000000194 fatty acid Substances 0.000 description 4
- 229930195729 fatty acid Natural products 0.000 description 4
- 150000004665 fatty acids Chemical class 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 3
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 229950011260 betanaphthol Drugs 0.000 description 3
- 238000006243 chemical reaction Methods 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
- 238000011161 development Methods 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 239000000839 emulsion Substances 0.000 description 3
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 150000003568 thioethers Chemical group 0.000 description 3
- SIZPGZFVROGOIR-UHFFFAOYSA-N 1,4-diisocyanatonaphthalene Chemical compound C1=CC=C2C(N=C=O)=CC=C(N=C=O)C2=C1 SIZPGZFVROGOIR-UHFFFAOYSA-N 0.000 description 2
- DTZHXCBUWSTOPO-UHFFFAOYSA-N 1-isocyanato-4-[(4-isocyanato-3-methylphenyl)methyl]-2-methylbenzene Chemical compound C1=C(N=C=O)C(C)=CC(CC=2C=C(C)C(N=C=O)=CC=2)=C1 DTZHXCBUWSTOPO-UHFFFAOYSA-N 0.000 description 2
- NJLLALPCADBTIS-UHFFFAOYSA-N 2,5-dibutoxy-4-morpholin-4-ylbenzenediazonium Chemical compound C1=C([N+]#N)C(OCCCC)=CC(N2CCOCC2)=C1OCCCC NJLLALPCADBTIS-UHFFFAOYSA-N 0.000 description 2
- 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 2
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 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
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 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 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 235000003560 Valerianella locusta Nutrition 0.000 description 2
- 240000004668 Valerianella locusta Species 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 239000007864 aqueous solution Substances 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
- 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
- JFIOVJDNOJYLKP-UHFFFAOYSA-N bithionol Chemical compound OC1=C(Cl)C=C(Cl)C=C1SC1=CC(Cl)=CC(Cl)=C1O JFIOVJDNOJYLKP-UHFFFAOYSA-N 0.000 description 2
- 229960002326 bithionol Drugs 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 239000004202 carbamide Substances 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 description 2
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 150000002357 guanidines Chemical class 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 1
- FTWMCSGJSZWKCR-UHFFFAOYSA-N 1,2,3-tricyclohexylguanidine Chemical compound C1CCCCC1NC(NC1CCCCC1)=NC1CCCCC1 FTWMCSGJSZWKCR-UHFFFAOYSA-N 0.000 description 1
- 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 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
- IKYNWXNXXHWHLL-UHFFFAOYSA-N 1,3-diisocyanatopropane Chemical compound O=C=NCCCN=C=O IKYNWXNXXHWHLL-UHFFFAOYSA-N 0.000 description 1
- CDMDQYCEEKCBGR-UHFFFAOYSA-N 1,4-diisocyanatocyclohexane Chemical compound O=C=NC1CCC(N=C=O)CC1 CDMDQYCEEKCBGR-UHFFFAOYSA-N 0.000 description 1
- FRASJONUBLZVQX-UHFFFAOYSA-N 1,4-dioxonaphthalene Natural products C1=CC=C2C(=O)C=CC(=O)C2=C1 FRASJONUBLZVQX-UHFFFAOYSA-N 0.000 description 1
- BOKGTLAJQHTOKE-UHFFFAOYSA-N 1,5-dihydroxynaphthalene Chemical compound C1=CC=C2C(O)=CC=CC2=C1O BOKGTLAJQHTOKE-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
- RIQXULCAEXVXDY-UHFFFAOYSA-N 2,5-dimethyl-4-(morpholin-4-ylmethyl)phenol Chemical compound C1=C(O)C(C)=CC(CN2CCOCC2)=C1C RIQXULCAEXVXDY-UHFFFAOYSA-N 0.000 description 1
- WXHLLJAMBQLULT-UHFFFAOYSA-N 2-[[6-[4-(2-hydroxyethyl)piperazin-1-yl]-2-methylpyrimidin-4-yl]amino]-n-(2-methyl-6-sulfanylphenyl)-1,3-thiazole-5-carboxamide;hydrate Chemical compound O.C=1C(N2CCN(CCO)CC2)=NC(C)=NC=1NC(S1)=NC=C1C(=O)NC1=C(C)C=CC=C1S WXHLLJAMBQLULT-UHFFFAOYSA-N 0.000 description 1
- VYHNSPUVKZPCDZ-UHFFFAOYSA-N 3-hydroxy-n-(2-hydroxyethyl)naphthalene-2-carboxamide Chemical compound C1=CC=C2C=C(O)C(C(=O)NCCO)=CC2=C1 VYHNSPUVKZPCDZ-UHFFFAOYSA-N 0.000 description 1
- OTEFEXJNJQIESQ-UHFFFAOYSA-N 3-hydroxy-n-(3-morpholin-4-ylpropyl)naphthalene-2-carboxamide Chemical compound OC1=CC2=CC=CC=C2C=C1C(=O)NCCCN1CCOCC1 OTEFEXJNJQIESQ-UHFFFAOYSA-N 0.000 description 1
- NHLAPJMCARJFOG-UHFFFAOYSA-N 3-methyl-1,4-dihydropyrazol-5-one Chemical compound CC1=NNC(=O)C1 NHLAPJMCARJFOG-UHFFFAOYSA-N 0.000 description 1
- ADOGRHNJEKVFAC-UHFFFAOYSA-N 3-methyl-4-pyrrolidin-1-ylbenzenediazonium Chemical compound CC1=CC([N+]#N)=CC=C1N1CCCC1 ADOGRHNJEKVFAC-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
- AUEZBGYRLDFFHZ-UHFFFAOYSA-N 4-(4-hydroxyphenyl)sulfanyl-3-methylphenol Chemical compound CC1=CC(O)=CC=C1SC1=CC=C(O)C=C1 AUEZBGYRLDFFHZ-UHFFFAOYSA-N 0.000 description 1
- MOXBCYIWIODTKI-UHFFFAOYSA-N 4-(dimethylamino)benzenediazonium Chemical compound CN(C)C1=CC=C([N+]#N)C=C1 MOXBCYIWIODTKI-UHFFFAOYSA-N 0.000 description 1
- GKJYBFYQBAAAQV-UHFFFAOYSA-N 4-[2-(diazonioamino)-4-methylphenyl]morpholine Chemical compound N#[N+]NC1=CC(C)=CC=C1N1CCOCC1 GKJYBFYQBAAAQV-UHFFFAOYSA-N 0.000 description 1
- GMICNERLJRJXAS-UHFFFAOYSA-N 4-morpholin-4-yl-2,5-di(propan-2-yloxy)benzenediazonium Chemical compound C1=C([N+]#N)C(OC(C)C)=CC(N2CCOCC2)=C1OC(C)C GMICNERLJRJXAS-UHFFFAOYSA-N 0.000 description 1
- NJYDJNRTEZIUBS-UHFFFAOYSA-N 4-morpholin-4-ylbenzenediazonium Chemical compound C1=CC([N+]#N)=CC=C1N1CCOCC1 NJYDJNRTEZIUBS-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 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
- FCSHMCFRCYZTRQ-UHFFFAOYSA-N N,N'-diphenylthiourea Chemical compound C=1C=CC=CC=1NC(=S)NC1=CC=CC=C1 FCSHMCFRCYZTRQ-UHFFFAOYSA-N 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- DYRDKSSFIWVSNM-UHFFFAOYSA-N acetoacetanilide Chemical compound CC(=O)CC(=O)NC1=CC=CC=C1 DYRDKSSFIWVSNM-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000012164 animal wax Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 235000006708 antioxidants Nutrition 0.000 description 1
- 150000008430 aromatic amides Chemical class 0.000 description 1
- 239000012752 auxiliary agent Substances 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
- 150000001638 boron Chemical class 0.000 description 1
- 150000001733 carboxylic acid esters Chemical class 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
- 235000015165 citric acid Nutrition 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000012954 diazonium Substances 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-O diazynium Chemical compound [NH+]#N IJGRMHOSHXDMSA-UHFFFAOYSA-O 0.000 description 1
- VNEBWJSWMVTSHK-UHFFFAOYSA-L disodium;3-hydroxynaphthalene-2,7-disulfonate Chemical compound [Na+].[Na+].C1=C(S([O-])(=O)=O)C=C2C=C(S([O-])(=O)=O)C(O)=CC2=C1 VNEBWJSWMVTSHK-UHFFFAOYSA-L 0.000 description 1
- PTEWEFISOFMTTD-UHFFFAOYSA-L disodium;naphthalene-1,2-disulfonate Chemical compound [Na+].[Na+].C1=CC=CC2=C(S([O-])(=O)=O)C(S(=O)(=O)[O-])=CC=C21 PTEWEFISOFMTTD-UHFFFAOYSA-L 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000005755 formation reaction Methods 0.000 description 1
- 229940083094 guanine derivative acting on arteriolar smooth muscle Drugs 0.000 description 1
- 229920000591 gum Polymers 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- TZMQHOJDDMFGQX-UHFFFAOYSA-N hexane-1,1,1-triol Chemical compound CCCCCC(O)(O)O TZMQHOJDDMFGQX-UHFFFAOYSA-N 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 239000004922 lacquer Substances 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 239000001630 malic acid Substances 0.000 description 1
- 235000011090 malic acid Nutrition 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- WIBFFTLQMKKBLZ-SEYXRHQNSA-N n-butyl oleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OCCCC WIBFFTLQMKKBLZ-SEYXRHQNSA-N 0.000 description 1
- 150000005209 naphthoic acids Chemical class 0.000 description 1
- YAFOVCNAQTZDQB-UHFFFAOYSA-N octyl diphenyl phosphate Chemical compound C=1C=CC=CC=1OP(=O)(OCCCCCCCC)OC1=CC=CC=C1 YAFOVCNAQTZDQB-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000012169 petroleum derived wax Substances 0.000 description 1
- 235000019381 petroleum wax Nutrition 0.000 description 1
- QCDYQQDYXPDABM-UHFFFAOYSA-N phloroglucinol Chemical compound OC1=CC(O)=CC(O)=C1 QCDYQQDYXPDABM-UHFFFAOYSA-N 0.000 description 1
- 229960001553 phloroglucinol Drugs 0.000 description 1
- 235000011007 phosphoric acid Nutrition 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical class OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000001397 quillaja saponaria molina bark Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 229930182490 saponin Natural products 0.000 description 1
- 150000007949 saponins Chemical class 0.000 description 1
- 235000017709 saponins Nutrition 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- IAAKNVCARVEIFS-UHFFFAOYSA-M sodium;4-hydroxynaphthalene-1-sulfonate Chemical compound [Na+].C1=CC=C2C(O)=CC=C(S([O-])(=O)=O)C2=C1 IAAKNVCARVEIFS-UHFFFAOYSA-M 0.000 description 1
- HIEHAIZHJZLEPQ-UHFFFAOYSA-M sodium;naphthalene-1-sulfonate Chemical compound [Na+].C1=CC=C2C(S(=O)(=O)[O-])=CC=CC2=C1 HIEHAIZHJZLEPQ-UHFFFAOYSA-M 0.000 description 1
- 239000002904 solvent Substances 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
- 238000003756 stirring Methods 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- 239000012178 vegetable wax Substances 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C1/00—Photosensitive materials
- G03C1/52—Compositions containing diazo compounds as photosensitive substances
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Heat Sensitive Colour Forming Recording (AREA)
Abstract
Description
【発明の詳細な説明】
「産業上の利用分野」
本発明は光定着可能な感熱記録体に関し、特に地肌の色
調が白く、記録前の記録体保存安定性に優れ、しかも記
録感度の良好な光定着型感熱記録体に関するものである
。Detailed Description of the Invention "Field of Industrial Application" The present invention relates to a heat-sensitive recording medium that can be photofixed, and in particular has a white background tone, excellent recording storage stability before recording, and good recording sensitivity. This invention relates to a photofixable thermosensitive recording medium.
「従来の技術」
従来、塩基性無色染料と該染料と接触して呈色し得る呈
色剤の呈色反応を利用し、熱によって再発色物質を接触
せしめて記録像を得るようにした感熱記録体はよく知ら
れている。``Prior Art'' Conventionally, heat-sensitive technology utilizes the coloring reaction of a basic colorless dye and a coloring agent that can change color when it comes into contact with the dye, and brings a recoloring substance into contact with the dye to obtain a recorded image. Records are well known.
かかる感熱記録体は熱によって記録像を得る構造になっ
ている為、熱印加記録した後も誤って熱源を近づけると
熱上昇郡全体が発色してしまい、必要な記録が判読出来
なくなるという欠陥を有している。従って保存を必要と
するような重要な記録への適用は困難であった。Since such a thermal recording medium has a structure in which a recorded image is obtained by heat, there is a defect that if the heat source is mistakenly brought close even after applying heat and recording, the entire heat source will develop color, making the necessary record unreadable. have. Therefore, it has been difficult to apply it to important records that require preservation.
そのため、定着可能な感熱記録体としてジアゾニウム化
合物とカプラーとの発色反応を利用したジアゾ系の感熱
記録体の開発が進められている。Therefore, as a fixable heat-sensitive recording material, a diazo-based heat-sensitive recording material that utilizes a color-forming reaction between a diazonium compound and a coupler is being developed.
一般に、ジアゾ系の感熱記録体においては、ジアゾニウ
ム化合物とカプラーが不連続な粒子状態で記録層中に分
散されており、加熱によってアルカリを発生する発色助
剤を併用して記録像を形成し、その後光照射によって未
反応のジアゾニウム化合物を分解して発色を停止させる
ように構成されている。Generally, in a diazo thermosensitive recording material, a diazonium compound and a coupler are dispersed in the recording layer in the form of discontinuous particles, and a coloring aid that generates alkali upon heating is used in combination to form a recorded image. The structure is such that unreacted diazonium compounds are then decomposed by light irradiation to stop color development.
然るに、かかる記録体では印字、定着前のプレカップリ
ングによる地肌カブリ（不要な着色現象）が発生する傾
向が強いため、その改良が望まれており、各種の改良方
法が提案されている。例えば塩基性化合物として疎水性
の高いグアニジン誘導体を使用する方法（特開昭５７−
４５０９４号、特開昭５７−１２５０９１号）、水不溶
性のジアゾニウム化合物を使用する方法（特開昭５８−
５５２９０号）、さらにはジアゾニウム化合物、カプラ
ー、塩基性化合物の一種又は二種をマイクロカプセル化
する方法（特開昭５９−１９０８８６号）等が提案され
ている。However, such a recording medium has a strong tendency to cause background fogging (unnecessary coloring phenomenon) due to pre-coupling before printing and fixing, so improvements are desired, and various improvement methods have been proposed. For example, a method using a highly hydrophobic guanidine derivative as a basic compound (Japanese Patent Application Laid-open No.
45094, JP-A-57-125091), a method using a water-insoluble diazonium compound (JP-A-58-125091);
55290), and a method of microencapsulating one or both of a diazonium compound, a coupler, and a basic compound (Japanese Patent Application Laid-Open No. 190886/1986).
「発明が解決しようとする問題点」
しかしながら、これらの改良方法で得られる感熱記録体
は、印字、定着前のプレカップリングの改良に伴って記
録感度が低下し、高速記録装置への適用が困難となるた
め、記録体の保存安定性と記録感度の両方を満足し得る
光定着型感熱記録体は得られておらず、しかも、光定着
後の地肌部が若干黄色味を帯びるという欠点も付随する
のが現状である。``Problems to be Solved by the Invention'' However, the thermal recording materials obtained by these improved methods have lower recording sensitivity due to improvements in pre-coupling before printing and fixing, making it difficult to apply them to high-speed recording devices. Because of this difficulty, a light-fixed heat-sensitive recording material that satisfies both storage stability and recording sensitivity has not been obtained, and it also has the disadvantage that the background part becomes slightly yellowish after light fixation. Accompanying this is the current situation.
本発明の目的は、光定着型の感熱記録体における上記の
如き難点を克服し、地肌の色調が白く、印字、定着前の
記録体の保存安定性に優れ、しかも記録感度の良好な記
録体を提供することである。It is an object of the present invention to overcome the above-mentioned difficulties in light-fixing type thermal recording materials, to provide a recording material with a white background tone, excellent storage stability before printing and fixing, and good recording sensitivity. The goal is to provide the following.
本発明者等は、かかる目的を達成するために、特にジア
ゾニウム化合物をマイクロカプセルに内包せしめて使用
する方法について鋭意研究の結果、カプセルの壁膜材と
してチオエーテル構造を有する特定の多価イソシアネー
ト化合物を選択的に使用すると、極めて優れた特性を有
する光定着型の感熱記録体が得られることを見出し本発
明を完成するに至った。In order to achieve this objective, the present inventors have conducted intensive research on the method of using diazonium compounds by encapsulating them in microcapsules. The present inventors have discovered that, when used selectively, a photofixable heat-sensitive recording material having extremely excellent properties can be obtained, leading to the completion of the present invention.
「問題点を解決するための手段」
本発明は、ジアゾニウム化合物を内包するマイクロカプ
セル、カプラー化合物、及び熱溶融時に塩基性雰囲気を
呈する化合物を含有する記録層を設けた光定着型感熱記
録体において、該マイクロカプセルの壁膜材として下記
の一般式で示される多価イソシアネート化合物を含有せ
しめたことを特徴とする感熱記録体である。"Means for Solving the Problems" The present invention provides a photofixable thermosensitive recording material provided with a recording layer containing a microcapsule containing a diazonium compound, a coupler compound, and a compound that exhibits a basic atmosphere when thermally melted. , is a heat-sensitive recording material characterized by containing a polyvalent isocyanate compound represented by the following general formula as a wall material of the microcapsules.
〔式中、Ｒ，、Ｒ，はそれぞれ少なくとも一つのイソシ
アネート基を有する０１〜ＣＩＳのアルキル基、ハロゲ
ン化アルキル基、環状アルキル基、アリール基又はアル
アルキル基を示し、Ｒｚ、Ｒ１はそれぞれハロゲン原子
、Ｃ３〜Ｃ４のアルキル基又はフェニル恭で置換されて
いてもよいフェニレン基又はナフチレン基を示す。〕「
作用」
本発明において用いられる上記の一般式で示される多価
イソシアネート化合物の具体例としては、例えば下記の
化合物が例示されるが、勿論これらに限定されるもので
はなく、これらは二種以上を併用することも可能である
。[In the formula, R,, R, each represent an alkyl group of 01 to CIS having at least one isocyanate group, a halogenated alkyl group, a cyclic alkyl group, an aryl group, or an aralkyl group, and Rz and R1 each represent a halogen atom , represents a phenylene group or naphthylene group which may be substituted with a C3-C4 alkyl group or phenyl group. ] “
Specific examples of the polyvalent isocyanate compound represented by the above general formula used in the present invention include the following compounds, but are not limited to these, and two or more of these may be used in combination. It is also possible to use them together.
４．４′−チオビスフェノール、２．２′−チオビスフ
ェノール、１．１′−チオビス（２−ナフトール）、１
．１’−チオビス（４−ナフトール）ビチオノール、３
，３′−クロル−４，４′−チオビスフェノール、３，
３′−メチル−４，４′−チオビスフェノール等のジオ
ール類と、ｍ−フェニレンジイソシアネート、ｐ−フェ
ニレンジイソシアネート、２．６−ドリレンジイソシア
ネート、２．４−１−リレンジイソシアネート、ナフタ
レン−１，４−ジイソシアネート、ジフェニルメタン−
４，４′−ジイソシアネート、３．３’−ジメチルジフ
ェニルメタン−４，４′−ジイソシアネート、キシリレ
ン−１，４−ジイソシアネート、４．４′−ジフェニル
プロパンジイソシアネート、ヘキサメチレンジイソシア
ネート、プロピレン−１，２−ジイソシアネート、ブチ
レン−１゜２−ジイソシアネート、シクロヘキシレン−
１゜２−ジイソシアネート、シクロヘキサン−１，４−
ジイソシアネート等の多価イソシアネート類との付加物
等。4.4'-thiobisphenol, 2.2'-thiobisphenol, 1.1'-thiobis(2-naphthol), 1
．． 1'-thiobis(4-naphthol)bithionol, 3
,3'-chloro-4,4'-thiobisphenol, 3,
Diols such as 3'-methyl-4,4'-thiobisphenol, m-phenylene diisocyanate, p-phenylene diisocyanate, 2,6-lylene diisocyanate, 2,4-1-lylene diisocyanate, naphthalene-1,4 -Diisocyanate, diphenylmethane-
4,4'-diisocyanate, 3,3'-dimethyldiphenylmethane-4,4'-diisocyanate, xylylene-1,4-diisocyanate, 4,4'-diphenylpropane diisocyanate, hexamethylene diisocyanate, propylene-1,2-diisocyanate , butylene-1゜2-diisocyanate, cyclohexylene-
1゜2-diisocyanate, cyclohexane-1,4-
Adducts with polyvalent isocyanates such as diisocyanates, etc.
上記一般式で示されるチオエーテル構造を有する多価イ
ソシアネートは、例えば酢酸エチル等の溶剤に溶かした
ジオール類に、２倍モル量の多価イソシアネート類を滴
下した後、２〜３時間還流する方法等で容易に調製する
ことができる。A polyvalent isocyanate having a thioether structure represented by the above general formula can be obtained by, for example, adding dropwise twice the molar amount of the polyvalent isocyanate to a diol dissolved in a solvent such as ethyl acetate, and then refluxing the mixture for 2 to 3 hours. can be easily prepared.
本発明では、ジアゾニウム化合物を内包するマイクロカ
プセルの壁膜材に上記特定のチオエーテル構造を有する
多価イソシアネート化合物を含有せしめるものであるが
、カプセルの壁膜材として従来から知られている各種の
多価イソシアネート化合物を併用することも可能である
。In the present invention, the wall material of microcapsules containing a diazonium compound is made to contain the polyvalent isocyanate compound having the above-mentioned specific thioether structure. It is also possible to use a divalent isocyanate compound in combination.
かかる多価イソシアネート化合物としては、例えばｍ−
フェニレンジイソシアネート、ｐ−フェニレンジイソシ
アネート、２．６−）リレンジイソシアネート、２．４
−）リレンジイソシアネート、ナフタレン−１，４−ジ
イソシアネート、ジフェニルメタン−４，４′−ジイソ
シアネート、３．３′−ジメチルジフェニルメタン−４
，４′−ジイソシアネート、キシリレン−１，４−ジイ
ソシアネート、４．４′−ジフェニルプロパンジイソシ
アネート、トリメチレンジイソシアネート、ヘキサメチ
レンジイソシアネート、プロピレン−１，２−ジイソシ
アネート、ブチレン−１，２−ジイソシアネート、シク
ロヘキシレン−１，２−ジイソシアネート、シクロヘキ
サン−１，４−ジイソシアネート等のジイソシアネート
類、４，４′４ ″−１−リフェニルメタントリイソシ
アネート、トルエン−２，４，６−トリイソシアネート
等のトリイソシアネート類、４，４′−ジメチルジフェ
ニルメタン−２，２′、ｓ、ｓ’−テトライソシアネー
ト等のテトライソシアネート類、ヘキサメチレンジイソ
シアネートとトリメチロールプロパンとの付加物、２．
４−１−リレンジイソシアネートとトリメチロールプロ
パンとの付加物、キシリレンジイソシアネートとトリメ
チロールプロパンとの付加物、トリレンジイソシアネー
トとヘキサントリオールとの付加物等のイソシアネート
プレポリマー等が挙げられる。Such polyvalent isocyanate compounds include, for example, m-
phenylene diisocyanate, p-phenylene diisocyanate, 2.6-) lylene diisocyanate, 2.4
-) lylene diisocyanate, naphthalene-1,4-diisocyanate, diphenylmethane-4,4'-diisocyanate, 3,3'-dimethyldiphenylmethane-4
, 4'-diisocyanate, xylylene-1,4-diisocyanate, 4,4'-diphenylpropane diisocyanate, trimethylene diisocyanate, hexamethylene diisocyanate, propylene-1,2-diisocyanate, butylene-1,2-diisocyanate, cyclohexylene- Diisocyanates such as 1,2-diisocyanate and cyclohexane-1,4-diisocyanate; triisocyanates such as 4,4'4''-1-rephenylmethane triisocyanate and toluene-2,4,6-triisocyanate; 4 , tetraisocyanates such as 4'-dimethyldiphenylmethane-2,2', s, s'-tetraisocyanate, adducts of hexamethylene diisocyanate and trimethylolpropane, 2.
Examples include isocyanate prepolymers such as adducts of 4-1-lylene diisocyanate and trimethylolpropane, adducts of xylylene diisocyanate and trimethylolpropane, and adducts of tolylene diisocyanate and hexanetriol.
本発明において用いられるジアゾニウム化合物全内包し
たマイクロカプセルは、各種公知の方法で調製すること
ができるが、一般にジアゾニウム化合物を含有した芯物
質を水性媒体中に乳化分散し、得られた芯物質の油滴の
周りに高分子物質膜を形成する方法によって調製される
。The microcapsules fully encapsulating the diazonium compound used in the present invention can be prepared by various known methods, but generally a core material containing the diazonium compound is emulsified and dispersed in an aqueous medium, and the resulting core material is It is prepared by a method that forms a polymeric material film around the droplet.
例えば上記特定のチオエーテル構造を有する多価イソシ
アネート化合物を含有する多価イソシアネートをカプセ
ル化すべき芯物質中に混合し、ポリビニルアルコール等
の保護コロイド物質を溶解した水性媒体中に乳化分散し
、液温を上昇させて、油滴界面で高分子形成反応を起こ
すことによって製造される。なお、マイクロカプセルの
粒子径は記録感度、得られる記録像の画質を考慮すると
０゜１〜１０μｍ程度の範囲で調節するのが望ましい。For example, a polyvalent isocyanate containing a polyvalent isocyanate compound having the above-described specific thioether structure is mixed into the core material to be encapsulated, emulsified and dispersed in an aqueous medium in which a protective colloid material such as polyvinyl alcohol is dissolved, and the liquid temperature is lowered. It is produced by raising the oil droplet to cause a polymer formation reaction at the interface of the oil droplet. Note that the particle diameter of the microcapsules is desirably adjusted within a range of about 0.1 to 10 μm in consideration of the recording sensitivity and the quality of the recorded image obtained.
芯物質の具体例としては、リン酸トリクレジル、リン酸
オクチルジフェニル等のリン酸エステル、フタル酸ジブ
チル、フタル酸ジオクチル等のフタル酸エステル、オレ
イン酸ブチル等のカルボン酸エステル、各種脂肪酸アミ
下、ジエチレングリコールジベンゾエート、イソプロピ
ルビフェニル等のアルキル化ビフェニル、塩素化パラフ
ィン等が挙げられるが、勿論これらに限定されるもので
はない。Specific examples of core substances include phosphate esters such as tricresyl phosphate and octyl diphenyl phosphate, phthalate esters such as dibutyl phthalate and dioctyl phthalate, carboxylic acid esters such as butyl oleate, various fatty acids, and diethylene glycol. Examples include dibenzoate, alkylated biphenyls such as isopropylbiphenyl, chlorinated paraffins, and the like, but are not limited thereto.
マイクロカプセル中に内包されるジアゾニウム化合物に
ついても、各種の材料が知られており、例えばｐ−Ｎ、
Ｎ−ジメチルアミノベンゼンジアゾニウム、４−モルホ
リノ−２，５−ジブトキシベンゼンジアゾニウム、４−
モルホリノ−２，５−ジイソプロポキシベンゼンジアゾ
ニウム、４−（４′−メトキシベンゾイルアミノ）−２
，５−ジェトキシベンゼンジアゾニウム、４−モルホリ
ノベンゼンジアゾニウム、４−ピロリジノ−３−メチル
ベンゼンジアゾニウム、ｐ−Ｎ−エチル−Ｎ−ヒドロキ
シエチルアニリンジアゾニウム、４−ベンズアミド−２
，５−ジェトキシベンゼンジアゾニウム、２−Ｎ、Ｎ−
ジエチル−ｍ−トルイジンジアゾニウム、６−モルホリ
ノ−ｍ−トルイジンジアゾニウム等のテトラフェニル硼
素塩、テトラフッ化硼素塩、六フッ化リン塩等が挙げら
れるが、中でも六フフ化リン塩が特に好ましく用いられ
る。Various materials are known for diazonium compounds to be encapsulated in microcapsules, such as p-N,
N-dimethylaminobenzenediazonium, 4-morpholino-2,5-dibutoxybenzenediazonium, 4-
Morpholino-2,5-diisopropoxybenzenediazonium, 4-(4'-methoxybenzoylamino)-2
, 5-jethoxybenzenediazonium, 4-morpholinobenzenediazonium, 4-pyrrolidino-3-methylbenzenediazonium, p-N-ethyl-N-hydroxyethylaniline diazonium, 4-benzamide-2
,5-jethoxybenzenediazonium, 2-N,N-
Examples include tetraphenyl boron salts such as diethyl-m-toluidine diazonium and 6-morpholino-m-toluidine diazonium, tetrafluoroboron salts, and phosphorus hexafluoride salts, among which phosphorus hexafluoride salts are particularly preferably used.
なお、これらのジアゾニウム化合物は、一般に芯物質で
ある有機溶媒中に１〜５０重量％程度の割合で溶解ない
しは混合して使用される。These diazonium compounds are generally used by being dissolved or mixed in an organic solvent as a core substance at a ratio of about 1 to 50% by weight.
かくして調製されるジアゾニウム化合物を内包したマイ
クロカプセルと併用されるカプラー化合物は、塩基性雰
囲気下でジアゾニウム化合物とカフブリング反応して色
素を形成する材料であるが、具体例としてはレゾルシノ
ール、カテコール、フロログルシン、α−ナフトール、
１．５−ジヒドロキシナフタレン、２，５−ジメチル−
４−モルホリノメチルフェノール、１−ヒドロキシナフ
タレン−４−スルホン酸ナトリウム、Ｎ−（３−モルホ
リノプロピル）−３−ヒドロキシ−２−ナフトアミド、
２−ヒドロキシ−３−（β−ヒドロキシエチルアミドカ
ルボニル）ナフタレン、２−ヒドロキシナフタレン−３
−カルボニルジェタノールアミン、２−ヒドロキシナフ
タレン−３，６−ジスルホン酸ナトリウム、アセトアセ
トアニリド、３−メチル−５−ピラゾロン、ｌ−フェニ
ル−３−メチル−５−ピラゾロン、２−ヒドロキシ−３
ナフトエ酸ヒドロキシエチルアミド、２−ヒドロキシ−
３ナフトエ酸アニリド、２−ヒドロキシ−３ナフトエ酸
−α−ナフタリド、２−ヒドロキシ−３ナフトエ酸−β
−ナフタリド、２−ヒドロキシ−３ナフトエ酸−４′−
クロロ７ニリド、２−ヒドロキシ−３ナフトエ酸−４′
−フロロアニリド、２−ヒドロキシ−３ナフトエ酸−２
’、６’−ジクロロアニリド、２−ヒドロキシ−３ナフ
トエ酸−２’、６’−ジクロロアニリド、４，４′−ジ
ーＯ−アセトアセトトルイシド、ベンゾイルアセトアニ
リド等が挙げられるが、勿論これらに限定されるもので
はなく、二種以上を併用することもできる。The coupler compound used in combination with the thus prepared microcapsules containing a diazonium compound is a material that forms a pigment by cuffing reaction with the diazonium compound in a basic atmosphere, and specific examples include resorcinol, catechol, phloroglucin, α-naphthol,
1,5-dihydroxynaphthalene, 2,5-dimethyl-
4-morpholinomethylphenol, sodium 1-hydroxynaphthalene-4-sulfonate, N-(3-morpholinopropyl)-3-hydroxy-2-naphthamide,
2-hydroxy-3-(β-hydroxyethylamide carbonyl)naphthalene, 2-hydroxynaphthalene-3
-carbonylgetanolamine, sodium 2-hydroxynaphthalene-3,6-disulfonate, acetoacetanilide, 3-methyl-5-pyrazolone, l-phenyl-3-methyl-5-pyrazolone, 2-hydroxy-3
naphthoic acid hydroxyethylamide, 2-hydroxy-
3-naphthoic acid anilide, 2-hydroxy-3-naphthoic acid-α-naphthalide, 2-hydroxy-3-naphthoic acid-β
-naphthalide, 2-hydroxy-3naphthoic acid-4'-
Chloro 7nilide, 2-hydroxy-3-naphthoic acid-4'
-Fluoroanilide, 2-hydroxy-3-naphthoic acid-2
',6'-dichloroanilide, 2-hydroxy-3naphthoic acid-2',6'-dichloroanilide, 4,4'-di-O-acetoacetotoluide, benzoylacetanilide, etc., but of course it is limited to these. It is also possible to use two or more types together.
カプラー化合物の記録層中への配合量は、用いられる化
合物の種類によって異なるため一概には定められないが
、−ａにジアゾニウム化合物１ｆｆｉ量部に対して０，
１〜ＩＯ重量部、より好ましくは０．３〜５重量部程度
配合される。The amount of the coupler compound to be incorporated into the recording layer cannot be determined unconditionally as it varies depending on the type of compound used;
It is blended in an amount of about 1 to IO parts by weight, more preferably about 0.3 to 5 parts by weight.
本発明において用いられる、熱溶融時に塩基性雰囲気を
呈する化合物としては、加熱によってアルカリを発生す
る物質であれば特に限定するものではな（、各種の熱溶
融性塩基性化合物が好ましく用いられるが、特に１，２
．３−）リフェニルグアニジン、１，２−ジトリルグア
ニジン、ｌ。The compound used in the present invention that exhibits a basic atmosphere when melted is not particularly limited as long as it generates alkali when heated (although various heat-melting basic compounds are preferably used, Especially 1,2
．． 3-) Riphenylguanidine, 1,2-ditolylguanidine, l.
２−ジシクロへキシルグアニジン、１，２．３−トリシ
クロへキシルグアニジン等のグアニジン誘導体は、本発
明の各種材料との組合せにおいて、とりわけ記録前の記
録体保存安定性に優れ、しかも記録感度、記録時のイン
スタント発色性の極めて良好な光定着型感熱記録体が得
られるため、最も好ましく用いられる。In combination with the various materials of the present invention, guanidine derivatives such as 2-dicyclohexylguanidine and 1,2,3-tricyclohexylguanidine have particularly excellent recording storage stability before recording, as well as recording sensitivity and recording properties. This method is most preferably used because a light-fixable heat-sensitive recording material with extremely good instant color development can be obtained.
なお、熱溶融性塩基性化合物の配合割合は、用いられる
化合物の種類によって異なるため一概には定められない
が、−Ｃにジアゾニウム化合物１重量部に対して０．１
〜１５重量部、より好ましくは１〜１０重量部程度配合
される。The blending ratio of the heat-melting basic compound varies depending on the type of compound used, so it cannot be determined unconditionally, but it is 0.1 part by weight of the diazonium compound in -C.
It is blended in an amount of about 15 parts by weight, more preferably about 1 to 10 parts by weight.
本発明において用いられる、カプラー化合物、熱溶融時
に塩基性雰囲気を呈する化合物は、ジアゾニウム化合物
と同様にカプセル化して使用することもできるが、カプ
セル化しない場合には、ボールミル、サンドグラインダ
ー、アトライター等の適当な攪拌粉砕装置によって粒子
径が１０μｍ以下となるよう処理して使用するのが好ま
しい。The coupler compound used in the present invention, a compound that exhibits a basic atmosphere when melted by heat, can be encapsulated and used in the same manner as the diazonium compound, but if it is not encapsulated, it can be used using a ball mill, sand grinder, attritor, etc. It is preferable to use a suitable stirring and pulverizing device to reduce the particle size to 10 μm or less.
かくして、本発明においては、ジアゾニウム化合物を内
包したマイクロカプセル、カプラー化合物、及び熱溶融
時に塩基性雰囲気を呈する化合物のそれぞれ少なくとも
一種を含有する感熱記録層が支持体に形成されるもので
あるが、−ｇに、かかる感熱記録層は上記の如き物質を
含有する塗被液を調製し、これを支持体に塗被する方法
で形成される。Thus, in the present invention, a heat-sensitive recording layer containing at least one of each of microcapsules containing a diazonium compound, a coupler compound, and a compound that exhibits a basic atmosphere when melted by heat is formed on a support. -g, such a heat-sensitive recording layer is formed by a method of preparing a coating solution containing the above-mentioned substances and coating it on a support.
塗被液中には必要に応じてナフタレンスルホン酸ソーダ
、ナフタレンジスルホン酸ソーダ、スルホサリチル酸、
硫酸マグネシウム、塩化亜鉛等の保存性向上剤、千オ尿
素、ジフェニルチオ尿素、尿素等の酸化防止剤、クエン
酸、リンゴ酸、酒石酸、リン酸、サポニン等の酸安定剤
、澱粉、カゼイン、アラビアガム、ポリビニルアルコー
ル、ポＩＪｉ［ビニルエマルジョン、スチレン・ブタジ
ェン共重合体ラテックス等の水溶性ないし水分散性の各
種接着剤、シリカ、クレー、硫酸バリウム、酸化チタン
、炭酸カルシウム等の顔料類、さらには動植物性ワック
ス類、石油ワックス類、高級脂肪酸の多価アルコールエ
ステル類、高級脂肪酸アミド類、芳香族アミド類、高級
脂肪酸とアミンの縮合物、合成パラフィン、塩素化パラ
フィン、ナフトエ酸のアルキルまたは了り−ルエステル
等の融点降下剤等の各種助剤が適宜配合されるものであ
る。The coating liquid contains sodium naphthalene sulfonate, sodium naphthalene disulfonate, sulfosalicylic acid,
Preservation improvers such as magnesium sulfate and zinc chloride, antioxidants such as urea, diphenylthiourea, and urea, acid stabilizers such as citric acid, malic acid, tartaric acid, phosphoric acid, and saponin, starch, casein, and Arabica. Gum, polyvinyl alcohol, polyvinyl alcohol, various water-soluble or water-dispersible adhesives such as vinyl emulsion and styrene-butadiene copolymer latex, pigments such as silica, clay, barium sulfate, titanium oxide, and calcium carbonate, and even Animal and vegetable waxes, petroleum waxes, polyhydric alcohol esters of higher fatty acids, higher fatty acid amides, aromatic amides, condensates of higher fatty acids and amines, synthetic paraffins, chlorinated paraffins, alkyl or naphthoic acids - Various auxiliary agents such as melting point depressants such as esters are appropriately blended.
このようにして調製された塗被液は、紙、プラスチック
フィルム、合成紙、金属フィルム等適当な支持体に塗被
されるが、塗被方法についても特に限定されるものでは
なく、常法に従って例えばエアーナイフコーター、ロー
ルコータ−、ブレードコーター等の如き適当な塗被装置
によって、乾燥重量で３〜２０ｇ／ｎｆ程度（少なくと
もジアゾニウム化合物の塗被量が０．０５〜２．０ ｇ
／ ｍ程度となるように）塗被乾燥される。The coating solution prepared in this way is coated on a suitable support such as paper, plastic film, synthetic paper, metal film, etc., but the coating method is not particularly limited and can be applied using a conventional method. For example, by using a suitable coating device such as an air knife coater, roll coater, blade coater, etc., the dry weight is about 3 to 20 g/nf (at least the coating amount of the diazonium compound is 0.05 to 2.0 g).
/ m) is coated and dried.
なお、本発明の記録体は通常の感熱記録体と同様に熱ペ
ン、熱ヘッド等により記録像を形成せしめた後、蛍光燈
や水銀燈などにより紫外光を全面に照射し、非記録部分
の未反応ジアゾニウム化合物を分解することによって、
記録像を定着することが出来るものである。In addition, in the recording medium of the present invention, a recorded image is formed using a thermal pen, a thermal head, etc. in the same way as a normal thermal recording medium, and then the entire surface is irradiated with ultraviolet light using a fluorescent lamp, a mercury lamp, etc. to eliminate the unrecorded areas. By decomposing the reactive diazonium compound,
It is capable of fixing recorded images.
「実施例」
以下に実施例を挙げて本発明をより具体的に説明するが
、勿論これらに限定されるものではない。"Example" The present invention will be described in more detail with reference to Examples below, but it is of course not limited to these.
また、特に断らない限り例中の部及び％は、それぞれ重
量部及び重量％を示す。Further, unless otherwise specified, parts and % in the examples indicate parts by weight and % by weight, respectively.
実施例Ｉ
Ａ液調製
４−モルホリノ−２，５−ジブトキシベンゼンジアゾニ
ウム六フッ化リン塩３部とキシリレンジイソシアネート
のトリメチロールプロパン、４゜４′−チオビスフェノ
ール付加物〔キシリレンジイソシアネート：トリメチロ
ールプロパン：４゜４′−チオビスフェノール＝９：１
：３（モル）〕９部をリン酸トリクレジル１５部に溶解
し、得られた溶液をポリビニルアルコールの８％水溶液
６０部中に乳化分散して平均粒子径が１．４μｍの乳化
液を得た。Example I Preparation of Solution A Trimethylolpropane, 4°4'-thiobisphenol adduct of 3 parts of 4-morpholino-2,5-dibutoxybenzenediazonium phosphorous hexafluoride salt and xylylene diisocyanate [xylylene diisocyanate: trimethylol] Propane: 4°4'-thiobisphenol = 9:1
:3 (mol)] was dissolved in 15 parts of tricresyl phosphate, and the resulting solution was emulsified and dispersed in 60 parts of an 8% aqueous solution of polyvinyl alcohol to obtain an emulsion with an average particle size of 1.4 μm. .
得られた乳化液に７０部の水を加え、５５℃で２時間反
応させてジアゾニウム化合物を内包したマイクロカプセ
ル分散液をＡ液として調製した。70 parts of water was added to the obtained emulsion and reacted at 55° C. for 2 hours to prepare a microcapsule dispersion containing a diazonium compound as Liquid A.
Ｂ漆調製
２−ヒドロキシ−３−ナフトエ酸アニリド８部Ｎ、Ｎ’
Ｎ″−トリフェニルグアニジン ４部ｐ−アセトトルイ
シド １３部炭酸カルシウム
２０部ポリビニルアルコールの１０％水溶
液１００部上記の組成物をボールミルで４８時間分散し
、Ｂ液を調製した。B Lacquer preparation 2-hydroxy-3-naphthoic acid anilide 8 parts N, N'
N″-Triphenylguanidine 4 parts p-acetotoluicide 13 parts Calcium carbonate
20 parts 100 parts of a 10% aqueous solution of polyvinyl alcohol The above composition was dispersed in a ball mill for 48 hours to prepare Solution B.
上記の分散液Ａ？ｖ、５０部とＢ液１００部を混合して
得られた塗液をワイヤーバーを用いて４９ｇ／ｍ′の上
質紙に乾燥重量が８ ｇ ／ ｔｒｉとなるように塗被
乾燥して感熱記録体を得た。The above dispersion A? A coating liquid obtained by mixing 50 parts of liquid B and 100 parts of liquid B was coated on 49 g/m' high-quality paper using a wire bar so that the dry weight was 8 g/tri, and then dried to make a thermal recording. I got a body.
実施例２
実施例１のＡ液調製において、壁膜材としてキシリレン
ジイソシアネートの４．４′−チオビスフェノール付加
物〔キシリレンジイソシアネート：４．４′−チオビス
フェノール−２：ｌ （モル）〕６．５部とキシリレン
ジイソシアネートのトリメチロールプロパン付加物〔キ
シリレンジイソシアネート：トリメチロール、プロパン
＝２：１（モル）〕（武出葉品社製５商品名タケネー）
Ｄ−１１ＯＮ）３．４部（７５％酢酸エチル溶液）の混
合物を用いた以外は実施例１と同様にして感熱記録体を
得た。Example 2 In the preparation of Solution A of Example 1, a 4.4'-thiobisphenol adduct of xylylene diisocyanate [xylylene diisocyanate:4.4'-thiobisphenol-2:l (mol)]6 was used as a wall film material. .5 parts and trimethylolpropane adduct of xylylene diisocyanate [xylylene diisocyanate: trimethylol, propane = 2:1 (mol)] (manufactured by Takedehahin Co., Ltd., 5 product name: Takene)
A thermosensitive recording material was obtained in the same manner as in Example 1 except that a mixture of 3.4 parts (75% ethyl acetate solution) of D-11ON was used.
実施例３
実施例１のＡ液調製において、壁膜材としてキシリレン
ジイソシアネートのトリメチロールプロパン、ビチオノ
ール付加物〔キシリレンジイソシアネート：トリメチロ
ールプロパン：ビチオノール−１８：４：３ （モル
）〕 ９部を用いた以外は実施例１と同様にして感熱記
録体を得た。Example 3 In the preparation of Solution A of Example 1, 9 parts of trimethylolpropane and bithionol adduct of xylylene diisocyanate [xylylene diisocyanate:trimethylolpropane:bithionol-18:4:3 (mol)] was added as a wall film material. A thermosensitive recording material was obtained in the same manner as in Example 1 except that the following was used.
実施例４
実施例１のＡ液調製において、壁膜材としてキシリレン
ジイソシアネートのトリメチロールプロパン、ｌ、１′
−チオビス（２−ナフトール）付加物〔キシリレンジイ
ソシアネート：トリメチロールプロパン：ｔ、１’−チ
オビス（２−ナフトール）＝１８：４：３（モル）〕
９部を用いた以外は実施例１と同様にして感熱記録体を
得た。Example 4 In the preparation of Solution A of Example 1, xylylene diisocyanate trimethylolpropane, 1, 1' was used as the wall material.
-Thiobis(2-naphthol) adduct [xylylene diisocyanate:trimethylolpropane:t,1'-thiobis(2-naphthol)=18:4:3 (mol)]
A thermosensitive recording material was obtained in the same manner as in Example 1 except that 9 parts were used.
比較例１
実施例１のＡ波調製において、壁膜材として４゜４′−
チオビスフェノールの代わりにビスフェノールＡを付加
した多価イソシアネート９部を用いた以外は実施例１と
同様にして感熱記録体を得た。Comparative Example 1 In the A wave preparation of Example 1, 4°4'-
A thermosensitive recording material was obtained in the same manner as in Example 1 except that 9 parts of polyvalent isocyanate to which bisphenol A was added was used instead of thiobisphenol.
比較例２
実施例１のＡ？ｐｉ調製において、壁膜材としてキシリ
レンジイソシアネートのトリメチロールプロパン付加物
〔キシリレンジイソシアネート：トリメチロールプロパ
ン＝２：ｌ （モル）〕 ９部ヲ用いた以外は実施例１
と同様にして感熱記録体を得た。Comparative Example 2 A of Example 1? Example 1 except that 9 parts of trimethylolpropane adduct of xylylene diisocyanate [xylylene diisocyanate:trimethylolpropane=2:l (mol)] was used as the wall film material in preparing pi.
A thermosensitive recording material was obtained in the same manner as above.
かくして得られた６種類の感熱記録体について、記録感
度および記録体の保存安定性、定着後の地肌の着色性に
ついて比較試験を行った。記録感度については、Ｇｌタ
イプの実用ファクシミリ （ＵＦ−２，転子電送製）で
熱記録し、紫外光を露光して像を定着せしめた後、記録
部のブルー濃度と地肌部の黄色濃度をマクヘス濃度計で
測定した。Comparative tests were conducted on the six types of heat-sensitive recording bodies thus obtained in terms of recording sensitivity, storage stability of the recording bodies, and coloring properties of the background after fixing. Regarding recording sensitivity, thermal recording is performed using a Gl type practical facsimile (UF-2, manufactured by Troshi Densen), and after the image is fixed by exposure to ultraviolet light, the blue density of the recorded area and the yellow density of the background area are measured. It was measured with a Maches densitometer.
記録体の保存安定性については、塗工直後の感熱記録体
と４０℃−９０％ＲＨの条件下に２４時間放置した記録
体の記録層のカブリ濃度（ブルー濃度）をそれぞれマク
ヘス濃度計で測定して比較し、得られた試験結果を下表
に示した。Regarding the storage stability of the recording medium, the fog density (blue density) of the recording layer of the heat-sensitive recording medium immediately after coating and the recording medium left for 24 hours under conditions of 40°C and 90% RH was measured using a Maches densitometer. The test results obtained are shown in the table below.
「効果」
表の結果から明らかなように、本発明の各実施例で得ら
れた感熱記録体は、いずれも優れた記録感度を有してお
り、地肌部の黄色着色も少なく、しかも記録体の保存安
定性に優れていた。"Effects" As is clear from the results in the table, the heat-sensitive recording materials obtained in each example of the present invention all had excellent recording sensitivity, had little yellowing in the background, and It had excellent storage stability.
しかし、比較例１の記録体は地肌部の黄色着色が高く、
経時によってブルー発色も高くなるため記録体の保存安
定性に劣っていた。また、比較例２の記録体は地肌部の
黄色着色が目立ち、記録画像の発色濃度も極めて低かっ
た。However, the recording medium of Comparative Example 1 had high yellow coloration in the background area;
The storage stability of the recording medium was poor because the blue color development increased over time. Further, in the recording material of Comparative Example 2, yellow coloration in the background portion was noticeable, and the color density of the recorded image was also extremely low.
Claims (1)
ラー化合物、及び熱溶融時に塩基性雰囲気を呈する化合
物を含有する記録層を設けた光定着型感熱記録体におい
て、該マイクロカプセルの壁膜材として下記の一般式で
示される多価イソシアネート化合物を含有せしめたこと
を特徴とする感熱記録体。 ▲数式、化学式、表等があります▼ 〔式中、Ｒ＿１、Ｒ＿４はそれぞれ少なくとも一つのイ
ソシアネート基を有するＣ＿１〜Ｃ＿１＿５のアルキル
基、ハロゲン化アルキル基、環状アルキル基、アリール
基又はアルアルキル基を示しＲ＿２、Ｒ＿３はそれぞれ
ハロゲン原子、Ｃ＿１〜Ｃのアルキル基又はフェニル基
で置換されていてもよいフェニレン基又はナフチレン基
を示す。〕[Scope of Claims] A photofixable thermosensitive recording material provided with a recording layer containing microcapsules containing a diazonium compound, a coupler compound, and a compound that exhibits a basic atmosphere when melted by heat, a wall material of the microcapsules. 1. A heat-sensitive recording material comprising a polyvalent isocyanate compound represented by the following general formula. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, R_1 and R_4 each represent a C_1 to C_1_5 alkyl group, halogenated alkyl group, cyclic alkyl group, aryl group, or aralkyl group, each having at least one isocyanate group. R_2 and R_3 each represent a phenylene group or a naphthylene group which may be substituted with a halogen atom, a C_1 to C alkyl group, or a phenyl group. ]
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61056004A JPS62212190A (en) | 1986-03-13 | 1986-03-13 | Thermal recording material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61056004A JPS62212190A (en) | 1986-03-13 | 1986-03-13 | Thermal recording material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS62212190A true JPS62212190A (en) | 1987-09-18 |
Family
ID=13014914
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61056004A Pending JPS62212190A (en) | 1986-03-13 | 1986-03-13 | Thermal recording material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62212190A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1087188C (en) * | 1995-01-19 | 2002-07-10 | 拜尔公司 | Microcapsules having walls made of polyisocyanate/guanidine reaction products |
| US6881810B2 (en) | 2002-07-15 | 2005-04-19 | Fuji Photo Film Co., Ltd. | Microcapsule and process for manufacturing the same |
| WO2006063165A2 (en) | 2004-12-08 | 2006-06-15 | Fuji Hunt Photographic Chemicals, Inc. | Composition for forming a laser-markable coating and process for forming a marking by laser exposure |
| US7163997B2 (en) | 2002-10-21 | 2007-01-16 | Fuji Photo Film Co., Ltd. | Polyether derivative and process for producing the same |
| EP1768119A2 (en) | 2005-08-25 | 2007-03-28 | FUJIFILM Corporation | Optical information recording medium, optical information recording method and optical information reproducing method |
| US7270928B2 (en) | 2004-01-08 | 2007-09-18 | Fujifilm Corporation | Isocyanate composition, microcapsule and production method thereof, and recording material |
| WO2014124052A1 (en) | 2013-02-06 | 2014-08-14 | Fujifilm Hunt Chemicals, Inc. | Chemical coating for a laser-markable material |
-
1986
- 1986-03-13 JP JP61056004A patent/JPS62212190A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1087188C (en) * | 1995-01-19 | 2002-07-10 | 拜尔公司 | Microcapsules having walls made of polyisocyanate/guanidine reaction products |
| US6881810B2 (en) | 2002-07-15 | 2005-04-19 | Fuji Photo Film Co., Ltd. | Microcapsule and process for manufacturing the same |
| US7163997B2 (en) | 2002-10-21 | 2007-01-16 | Fuji Photo Film Co., Ltd. | Polyether derivative and process for producing the same |
| US7270928B2 (en) | 2004-01-08 | 2007-09-18 | Fujifilm Corporation | Isocyanate composition, microcapsule and production method thereof, and recording material |
| WO2006063165A2 (en) | 2004-12-08 | 2006-06-15 | Fuji Hunt Photographic Chemicals, Inc. | Composition for forming a laser-markable coating and process for forming a marking by laser exposure |
| EP1768119A2 (en) | 2005-08-25 | 2007-03-28 | FUJIFILM Corporation | Optical information recording medium, optical information recording method and optical information reproducing method |
| WO2014124052A1 (en) | 2013-02-06 | 2014-08-14 | Fujifilm Hunt Chemicals, Inc. | Chemical coating for a laser-markable material |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JPS62212190A (en) | Thermal recording material | |
| US4895826A (en) | Heat-sensitive recording material with diazonium salt and coupler precursor with ester or urethane group | |
| US5213939A (en) | Light- and heat-sensitive recording material | |
| JPS62146678A (en) | Thermal recording material | |
| JPS6315786A (en) | Two-color thermal recording material | |
| JPH04135787A (en) | Light-and heat-sensitive recording material | |
| JPS62142686A (en) | Thermal recording material | |
| DE3704627A1 (en) | HEAT SENSITIVE RECORDING MATERIAL | |
| JPS62242582A (en) | Thermal recording material | |
| JPH0655546B2 (en) | Thermal recording material | |
| JPH04144784A (en) | Photosensitive thermal recording material | |
| JPS62253486A (en) | Manufacture of heat sensitive recording material | |
| JPS62148286A (en) | Thermal recording material | |
| JPH0469554B2 (en) | ||
| JPS62251189A (en) | Thermal recording body | |
| JP2517372B2 (en) | Diazo thermal recording material | |
| JPH0645260B2 (en) | Thermal recording material | |
| JPS6141595A (en) | Thermal recording body | |
| JPH0645262B2 (en) | Thermal recording material | |
| JPH06104381B2 (en) | Thermal recording material | |
| JP3611669B2 (en) | Thermal recording material | |
| JPH10264532A (en) | Thermal recording material | |
| JPH043758B2 (en) | ||
| JPH0341358B2 (en) | ||
| JPH0643146B2 (en) | Thermal recording material |