JPH0356677B2 - - Google Patents
Info
- Publication number
- JPH0356677B2 JPH0356677B2 JP60153483A JP15348385A JPH0356677B2 JP H0356677 B2 JPH0356677 B2 JP H0356677B2 JP 60153483 A JP60153483 A JP 60153483A JP 15348385 A JP15348385 A JP 15348385A JP H0356677 B2 JPH0356677 B2 JP H0356677B2
- Authority
- JP
- Japan
- Prior art keywords
- heat
- polyvinyl alcohol
- recording layer
- methyl
- sensitive recording
- 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
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 37
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 35
- 239000000463 material Substances 0.000 claims description 26
- LTXYFELJDAARCU-UHFFFAOYSA-N ethyl n-(hydroxymethyl)carbamate Chemical compound CCOC(=O)NCO LTXYFELJDAARCU-UHFFFAOYSA-N 0.000 claims description 3
- 239000010410 layer Substances 0.000 description 51
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 36
- 229920005989 resin Polymers 0.000 description 30
- 239000011347 resin Substances 0.000 description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 25
- 239000011248 coating agent Substances 0.000 description 24
- 238000000576 coating method Methods 0.000 description 24
- 239000007788 liquid Substances 0.000 description 17
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 description 16
- 239000007864 aqueous solution Substances 0.000 description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 11
- 239000003086 colorant Substances 0.000 description 11
- 239000000126 substance Substances 0.000 description 10
- 239000011230 binding agent Substances 0.000 description 9
- 239000000975 dye Substances 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- 150000003839 salts Chemical class 0.000 description 9
- 230000002776 aggregation Effects 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 8
- 229940015043 glyoxal Drugs 0.000 description 8
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 7
- 229920000877 Melamine resin Polymers 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- -1 p-nitroanilino Chemical group 0.000 description 7
- 239000003973 paint Substances 0.000 description 7
- 230000002378 acidificating effect Effects 0.000 description 6
- 238000004220 aggregation Methods 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- FWQHNLCNFPYBCA-UHFFFAOYSA-N fluoran Chemical compound C12=CC=CC=C2OC2=CC=CC=C2C11OC(=O)C2=CC=CC=C21 FWQHNLCNFPYBCA-UHFFFAOYSA-N 0.000 description 6
- 239000004927 clay Substances 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 229920003169 water-soluble polymer 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
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical group OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 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
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 229920000609 methyl cellulose Polymers 0.000 description 4
- 239000001923 methylcellulose Substances 0.000 description 4
- 235000010981 methylcellulose Nutrition 0.000 description 4
- 229920006122 polyamide resin Polymers 0.000 description 4
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 4
- 239000004576 sand Substances 0.000 description 4
- 239000001993 wax Substances 0.000 description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 3
- 239000004202 carbamide Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 239000001023 inorganic pigment Substances 0.000 description 3
- 150000003951 lactams Chemical class 0.000 description 3
- 239000012860 organic pigment Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 150000002989 phenols Chemical class 0.000 description 3
- 239000011241 protective layer Substances 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- OAGNKYSIOSDNIG-UHFFFAOYSA-N 1-methyl-3-[2-(3-methylphenoxy)ethoxy]benzene Chemical compound CC1=CC=CC(OCCOC=2C=C(C)C=CC=2)=C1 OAGNKYSIOSDNIG-UHFFFAOYSA-N 0.000 description 2
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 2
- WNZQDUSMALZDQF-UHFFFAOYSA-N 2-benzofuran-1(3H)-one Chemical compound C1=CC=C2C(=O)OCC2=C1 WNZQDUSMALZDQF-UHFFFAOYSA-N 0.000 description 2
- JWAZRIHNYRIHIV-UHFFFAOYSA-N 2-naphthol Chemical compound C1=CC=CC2=CC(O)=CC=C21 JWAZRIHNYRIHIV-UHFFFAOYSA-N 0.000 description 2
- OMNHTTWQSSUZHO-UHFFFAOYSA-N 4-hydroxy-3,5-dimethylbenzoic acid Chemical compound CC1=CC(C(O)=O)=CC(C)=C1O OMNHTTWQSSUZHO-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 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
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical class OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- 229920002472 Starch Polymers 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 229920001807 Urea-formaldehyde Polymers 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000006096 absorbing agent Substances 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 239000002518 antifoaming agent Substances 0.000 description 2
- 239000000981 basic dye Substances 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical compound C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- YXVFYQXJAXKLAK-UHFFFAOYSA-N biphenyl-4-ol Chemical compound C1=CC(O)=CC=C1C1=CC=CC=C1 YXVFYQXJAXKLAK-UHFFFAOYSA-N 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 239000008199 coating composition Substances 0.000 description 2
- 239000008119 colloidal silica Substances 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- JJXVDRYFBGDXOU-UHFFFAOYSA-N dimethyl 4-hydroxybenzene-1,2-dicarboxylate Chemical compound COC(=O)C1=CC=C(O)C=C1C(=O)OC JJXVDRYFBGDXOU-UHFFFAOYSA-N 0.000 description 2
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical compound OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- FATBGEAMYMYZAF-KTKRTIGZSA-N oleamide Chemical compound CCCCCCCC\C=C/CCCCCCCC(N)=O FATBGEAMYMYZAF-KTKRTIGZSA-N 0.000 description 2
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 2
- 229960004889 salicylic acid Drugs 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 235000019698 starch Nutrition 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- SXJSETSRWNDWPP-UHFFFAOYSA-N (2-hydroxy-4-phenylmethoxyphenyl)-phenylmethanone Chemical compound C=1C=C(C(=O)C=2C=CC=CC=2)C(O)=CC=1OCC1=CC=CC=C1 SXJSETSRWNDWPP-UHFFFAOYSA-N 0.000 description 1
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 description 1
- XBYRMPXUBGMOJC-UHFFFAOYSA-N 1,2-dihydropyrazol-3-one Chemical compound OC=1C=CNN=1 XBYRMPXUBGMOJC-UHFFFAOYSA-N 0.000 description 1
- ZRHUHDUEXWHZMA-UHFFFAOYSA-N 1,4-dihydropyrazol-5-one Chemical compound O=C1CC=NN1 ZRHUHDUEXWHZMA-UHFFFAOYSA-N 0.000 description 1
- XZVMMJJKLCWXRK-UHFFFAOYSA-N 1-methyl-4-(2-phenoxyethoxy)benzene Chemical compound C1=CC(C)=CC=C1OCCOC1=CC=CC=C1 XZVMMJJKLCWXRK-UHFFFAOYSA-N 0.000 description 1
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 description 1
- KGRVJHAUYBGFFP-UHFFFAOYSA-N 2,2'-Methylenebis(4-methyl-6-tert-butylphenol) Chemical compound CC(C)(C)C1=CC(C)=CC(CC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O KGRVJHAUYBGFFP-UHFFFAOYSA-N 0.000 description 1
- ALLSOOQIDPLIER-UHFFFAOYSA-N 2,3,4-trichlorobenzoic acid Chemical compound OC(=O)C1=CC=C(Cl)C(Cl)=C1Cl ALLSOOQIDPLIER-UHFFFAOYSA-N 0.000 description 1
- FXNDIJDIPNCZQJ-UHFFFAOYSA-N 2,4,4-trimethylpent-1-ene Chemical group CC(=C)CC(C)(C)C FXNDIJDIPNCZQJ-UHFFFAOYSA-N 0.000 description 1
- RJKPEKIHHFNMGS-UHFFFAOYSA-N 2,4-ditert-butyl-3-methylphenol Chemical compound CC1=C(C(C)(C)C)C=CC(O)=C1C(C)(C)C RJKPEKIHHFNMGS-UHFFFAOYSA-N 0.000 description 1
- DZZPJWJPJJNWHM-UHFFFAOYSA-N 2-hydroxy-3-(1-phenylethyl)benzoic acid Chemical compound C=1C=CC(C(O)=O)=C(O)C=1C(C)C1=CC=CC=C1 DZZPJWJPJJNWHM-UHFFFAOYSA-N 0.000 description 1
- YBXZFYBYIPONRP-UHFFFAOYSA-N 2-hydroxy-3-phenyl-5-(2-phenylpropan-2-yl)benzoic acid Chemical compound C=1C(C(O)=O)=C(O)C(C=2C=CC=CC=2)=CC=1C(C)(C)C1=CC=CC=C1 YBXZFYBYIPONRP-UHFFFAOYSA-N 0.000 description 1
- XGAYQDWZIPRBPF-UHFFFAOYSA-N 2-hydroxy-3-propan-2-ylbenzoic acid Chemical compound CC(C)C1=CC=CC(C(O)=O)=C1O XGAYQDWZIPRBPF-UHFFFAOYSA-N 0.000 description 1
- XCSGHNKDXGYELG-UHFFFAOYSA-N 2-phenoxyethoxybenzene Chemical compound C=1C=CC=CC=1OCCOC1=CC=CC=C1 XCSGHNKDXGYELG-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
- PFANXOISJYKQRP-UHFFFAOYSA-N 2-tert-butyl-4-[1-(5-tert-butyl-4-hydroxy-2-methylphenyl)butyl]-5-methylphenol Chemical compound C=1C(C(C)(C)C)=C(O)C=C(C)C=1C(CCC)C1=CC(C(C)(C)C)=C(O)C=C1C PFANXOISJYKQRP-UHFFFAOYSA-N 0.000 description 1
- GPNYZBKIGXGYNU-UHFFFAOYSA-N 2-tert-butyl-6-[(3-tert-butyl-5-ethyl-2-hydroxyphenyl)methyl]-4-ethylphenol Chemical compound CC(C)(C)C1=CC(CC)=CC(CC=2C(=C(C=C(CC)C=2)C(C)(C)C)O)=C1O GPNYZBKIGXGYNU-UHFFFAOYSA-N 0.000 description 1
- ZWQBZEFLFSFEOS-UHFFFAOYSA-N 3,5-ditert-butyl-2-hydroxybenzoic acid Chemical compound CC(C)(C)C1=CC(C(O)=O)=C(O)C(C(C)(C)C)=C1 ZWQBZEFLFSFEOS-UHFFFAOYSA-N 0.000 description 1
- RCXHRHWRRACBTK-UHFFFAOYSA-N 3-(oxiran-2-ylmethoxy)propane-1,2-diol Chemical compound OCC(O)COCC1CO1 RCXHRHWRRACBTK-UHFFFAOYSA-N 0.000 description 1
- MQJTWPAGXWPEKU-UHFFFAOYSA-N 3-[4-(dimethylamino)phenyl]-3-(1,2-dimethylindol-3-yl)-2-benzofuran-1-one Chemical compound C1=CC(N(C)C)=CC=C1C1(C=2C3=CC=CC=C3N(C)C=2C)C2=CC=CC=C2C(=O)O1 MQJTWPAGXWPEKU-UHFFFAOYSA-N 0.000 description 1
- ZKUWHPNJONEJEE-UHFFFAOYSA-N 3-[4-(dimethylamino)phenyl]-3-(2-methyl-1h-indol-3-yl)-2-benzofuran-1-one Chemical compound C1=CC(N(C)C)=CC=C1C1(C=2C3=CC=CC=C3NC=2C)C2=CC=CC=C2C(=O)O1 ZKUWHPNJONEJEE-UHFFFAOYSA-N 0.000 description 1
- YUVVASYGZFERRP-UHFFFAOYSA-N 3-benzyl-2-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=CC(CC=2C=CC=CC=2)=C1O YUVVASYGZFERRP-UHFFFAOYSA-N 0.000 description 1
- RWVOCFCXPXXMMJ-UHFFFAOYSA-N 3-butan-2-yl-4-hydroxybenzoic acid Chemical compound CCC(C)C1=CC(C(O)=O)=CC=C1O RWVOCFCXPXXMMJ-UHFFFAOYSA-N 0.000 description 1
- HINSTNAJIHVPOM-UHFFFAOYSA-N 3-cyclohexyl-4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C(C2CCCCC2)=C1 HINSTNAJIHVPOM-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
- BOTKTAZUSYVSFF-UHFFFAOYSA-N 4-(2,4,4-trimethylpentan-2-yl)benzene-1,2-diol Chemical compound CC(C)(C)CC(C)(C)C1=CC=C(O)C(O)=C1 BOTKTAZUSYVSFF-UHFFFAOYSA-N 0.000 description 1
- PRWJPWSKLXYEPD-UHFFFAOYSA-N 4-[4,4-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)butan-2-yl]-2-tert-butyl-5-methylphenol Chemical compound C=1C(C(C)(C)C)=C(O)C=C(C)C=1C(C)CC(C=1C(=CC(O)=C(C=1)C(C)(C)C)C)C1=CC(C(C)(C)C)=C(O)C=C1C PRWJPWSKLXYEPD-UHFFFAOYSA-N 0.000 description 1
- XURABDHWIADCPO-UHFFFAOYSA-N 4-prop-2-enylhepta-1,6-diene Chemical compound C=CCC(CC=C)CC=C XURABDHWIADCPO-UHFFFAOYSA-N 0.000 description 1
- KDVYCTOWXSLNNI-UHFFFAOYSA-N 4-t-Butylbenzoic acid Chemical compound CC(C)(C)C1=CC=C(C(O)=O)C=C1 KDVYCTOWXSLNNI-UHFFFAOYSA-N 0.000 description 1
- QHPQWRBYOIRBIT-UHFFFAOYSA-N 4-tert-butylphenol Chemical compound CC(C)(C)C1=CC=C(O)C=C1 QHPQWRBYOIRBIT-UHFFFAOYSA-N 0.000 description 1
- RNRINRUTVAFUCG-UHFFFAOYSA-N 5-(dimethylamino)-3,3-bis(1,2-dimethylindol-3-yl)-2-benzofuran-1-one Chemical compound C1=CC=C2C(C3(C=4C5=CC=CC=C5N(C)C=4C)OC(=O)C4=CC=C(C=C43)N(C)C)=C(C)N(C)C2=C1 RNRINRUTVAFUCG-UHFFFAOYSA-N 0.000 description 1
- WYWMJBFBHMNECA-UHFFFAOYSA-N 6-(dimethylamino)-3,3-bis(1,2-dimethylindol-3-yl)-2-benzofuran-1-one Chemical compound C1=CC=C2C(C3(C=4C5=CC=CC=C5N(C)C=4C)OC(=O)C=4C3=CC=C(C=4)N(C)C)=C(C)N(C)C2=C1 WYWMJBFBHMNECA-UHFFFAOYSA-N 0.000 description 1
- VUPFPYYWAFXPEE-UHFFFAOYSA-N 6-(dimethylamino)-3,3-bis(2-phenyl-1h-indol-3-yl)-2-benzofuran-1-one Chemical compound C=1C(N(C)C)=CC=C2C=1C(=O)OC2(C=1C2=CC=CC=C2NC=1C=1C=CC=CC=1)C(C1=CC=CC=C1N1)=C1C1=CC=CC=C1 VUPFPYYWAFXPEE-UHFFFAOYSA-N 0.000 description 1
- MUWBLPSPEGTPEH-UHFFFAOYSA-N 6-(dimethylamino)-3,3-bis(9-ethylcarbazol-3-yl)-2-benzofuran-1-one Chemical compound C1=CC=C2C3=CC(C4(C5=CC=C(C=C5C(=O)O4)N(C)C)C=4C=C5C6=CC=CC=C6N(C5=CC=4)CC)=CC=C3N(CC)C2=C1 MUWBLPSPEGTPEH-UHFFFAOYSA-N 0.000 description 1
- CRKAWLFCMDKQIT-UHFFFAOYSA-N 6-(dimethylamino)-3h-2-benzofuran-1-one Chemical compound CN(C)C1=CC=C2COC(=O)C2=C1 CRKAWLFCMDKQIT-UHFFFAOYSA-N 0.000 description 1
- FHVDTGUDJYJELY-UHFFFAOYSA-N 6-{[2-carboxy-4,5-dihydroxy-6-(phosphanyloxy)oxan-3-yl]oxy}-4,5-dihydroxy-3-phosphanyloxane-2-carboxylic acid Chemical compound O1C(C(O)=O)C(P)C(O)C(O)C1OC1C(C(O)=O)OC(OP)C(O)C1O FHVDTGUDJYJELY-UHFFFAOYSA-N 0.000 description 1
- 244000215068 Acacia senegal Species 0.000 description 1
- 229920002126 Acrylic acid copolymer Polymers 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- MOZDKDIOPSPTBH-UHFFFAOYSA-N Benzyl parahydroxybenzoate Chemical compound C1=CC(O)=CC=C1C(=O)OCC1=CC=CC=C1 MOZDKDIOPSPTBH-UHFFFAOYSA-N 0.000 description 1
- HTVITOHKHWFJKO-UHFFFAOYSA-N Bisphenol B Chemical compound C=1C=C(O)C=CC=1C(C)(CC)C1=CC=C(O)C=C1 HTVITOHKHWFJKO-UHFFFAOYSA-N 0.000 description 1
- WRAGBEWQGHCDDU-UHFFFAOYSA-M C([O-])([O-])=O.[NH4+].[Zr+] Chemical compound C([O-])([O-])=O.[NH4+].[Zr+] WRAGBEWQGHCDDU-UHFFFAOYSA-M 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 244000060011 Cocos nucifera Species 0.000 description 1
- 235000013162 Cocos nucifera Nutrition 0.000 description 1
- IPAJDLMMTVZVPP-UHFFFAOYSA-N Crystal violet lactone Chemical compound C1=CC(N(C)C)=CC=C1C1(C=2C=CC(=CC=2)N(C)C)C2=CC=C(N(C)C)C=C2C(=O)O1 IPAJDLMMTVZVPP-UHFFFAOYSA-N 0.000 description 1
- MDNWOSOZYLHTCG-UHFFFAOYSA-N Dichlorophen Chemical compound OC1=CC=C(Cl)C=C1CC1=CC(Cl)=CC=C1O MDNWOSOZYLHTCG-UHFFFAOYSA-N 0.000 description 1
- 239000004716 Ethylene/acrylic acid copolymer Chemical class 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 description 1
- 229920000084 Gum arabic Polymers 0.000 description 1
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 1
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- WSMYVTOQOOLQHP-UHFFFAOYSA-N Malondialdehyde Chemical compound O=CCC=O WSMYVTOQOOLQHP-UHFFFAOYSA-N 0.000 description 1
- 239000004640 Melamine resin Substances 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- PCSMJKASWLYICJ-UHFFFAOYSA-N Succinic aldehyde Chemical compound O=CCCC=O PCSMJKASWLYICJ-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- MBHRHUJRKGNOKX-UHFFFAOYSA-N [(4,6-diamino-1,3,5-triazin-2-yl)amino]methanol Chemical compound NC1=NC(N)=NC(NCO)=N1 MBHRHUJRKGNOKX-UHFFFAOYSA-N 0.000 description 1
- ZKURGBYDCVNWKH-UHFFFAOYSA-N [3,7-bis(dimethylamino)phenothiazin-10-yl]-phenylmethanone Chemical compound C12=CC=C(N(C)C)C=C2SC2=CC(N(C)C)=CC=C2N1C(=O)C1=CC=CC=C1 ZKURGBYDCVNWKH-UHFFFAOYSA-N 0.000 description 1
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 description 1
- YGCOKJWKWLYHTG-UHFFFAOYSA-N [[4,6-bis[bis(hydroxymethyl)amino]-1,3,5-triazin-2-yl]-(hydroxymethyl)amino]methanol Chemical compound OCN(CO)C1=NC(N(CO)CO)=NC(N(CO)CO)=N1 YGCOKJWKWLYHTG-UHFFFAOYSA-N 0.000 description 1
- 239000000205 acacia gum Substances 0.000 description 1
- 235000010489 acacia gum Nutrition 0.000 description 1
- 229920006322 acrylamide copolymer Polymers 0.000 description 1
- 238000007754 air knife coating Methods 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 229940072056 alginate Drugs 0.000 description 1
- 235000010443 alginic acid Nutrition 0.000 description 1
- 229920000615 alginic acid Polymers 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 235000011126 aluminium potassium sulphate Nutrition 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- VEQOALNAAJBPNY-UHFFFAOYSA-N antipyrine Chemical compound CN1C(C)=CC(=O)N1C1=CC=CC=C1 VEQOALNAAJBPNY-UHFFFAOYSA-N 0.000 description 1
- 229960000892 attapulgite Drugs 0.000 description 1
- 239000011805 ball Substances 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- BJFLSHMHTPAZHO-UHFFFAOYSA-N benzotriazole Chemical compound [CH]1C=CC=C2N=NN=C21 BJFLSHMHTPAZHO-UHFFFAOYSA-N 0.000 description 1
- FQUNFJULCYSSOP-UHFFFAOYSA-N bisoctrizole Chemical compound N1=C2C=CC=CC2=NN1C1=CC(C(C)(C)CC(C)(C)C)=CC(CC=2C(=C(C=C(C=2)C(C)(C)CC(C)(C)C)N2N=C3C=CC=CC3=N2)O)=C1O FQUNFJULCYSSOP-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 1
- 235000013539 calcium stearate Nutrition 0.000 description 1
- 239000008116 calcium stearate Substances 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 239000004203 carnauba wax Substances 0.000 description 1
- 235000013869 carnauba wax Nutrition 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
- 239000003054 catalyst Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001989 diazonium salts Chemical class 0.000 description 1
- MHDVGSVTJDSBDK-UHFFFAOYSA-N dibenzyl ether Chemical compound C=1C=CC=CC=1COCC1=CC=CC=C1 MHDVGSVTJDSBDK-UHFFFAOYSA-N 0.000 description 1
- GOPWOUQJIMLDDM-UHFFFAOYSA-N dibutyl benzene-1,3-dicarboxylate Chemical compound CCCCOC(=O)C1=CC=CC(C(=O)OCCCC)=C1 GOPWOUQJIMLDDM-UHFFFAOYSA-N 0.000 description 1
- 235000019329 dioctyl sodium sulphosuccinate Nutrition 0.000 description 1
- CZZYITDELCSZES-UHFFFAOYSA-N diphenylmethane Chemical compound C=1C=CC=CC=1CC1=CC=CC=C1 CZZYITDELCSZES-UHFFFAOYSA-N 0.000 description 1
- YHAIUSTWZPMYGG-UHFFFAOYSA-L disodium;2,2-dioctyl-3-sulfobutanedioate Chemical compound [Na+].[Na+].CCCCCCCCC(C([O-])=O)(C(C([O-])=O)S(O)(=O)=O)CCCCCCCC YHAIUSTWZPMYGG-UHFFFAOYSA-L 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- OJLOUXPPKZRTHK-UHFFFAOYSA-N dodecan-1-ol;sodium Chemical compound [Na].CCCCCCCCCCCCO OJLOUXPPKZRTHK-UHFFFAOYSA-N 0.000 description 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000007850 fluorescent dye Substances 0.000 description 1
- FRIPRWYKBIOZJU-UHFFFAOYSA-N fluorone Chemical compound C1=CC=C2OC3=CC(=O)C=CC3=CC2=C1 FRIPRWYKBIOZJU-UHFFFAOYSA-N 0.000 description 1
- JGEMYUOFGVHXKV-OWOJBTEDSA-N fumaraldehyde Chemical compound O=C\C=C\C=O JGEMYUOFGVHXKV-OWOJBTEDSA-N 0.000 description 1
- 229940074391 gallic acid Drugs 0.000 description 1
- 235000004515 gallic acid Nutrition 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- HSEMFIZWXHQJAE-UHFFFAOYSA-N hexadecanamide Chemical compound CCCCCCCCCCCCCCCC(N)=O HSEMFIZWXHQJAE-UHFFFAOYSA-N 0.000 description 1
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- XHQSLVIGPHXVAK-UHFFFAOYSA-K iron(3+);octadecanoate Chemical compound [Fe+3].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XHQSLVIGPHXVAK-UHFFFAOYSA-K 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 229940118019 malondialdehyde Drugs 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- CXKWCBBOMKCUKX-UHFFFAOYSA-M methylene blue Chemical compound [Cl-].C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 CXKWCBBOMKCUKX-UHFFFAOYSA-M 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 229960000907 methylthioninium chloride Drugs 0.000 description 1
- 239000011806 microball Substances 0.000 description 1
- VYQNWZOUAUKGHI-UHFFFAOYSA-N monobenzone Chemical compound C1=CC(O)=CC=C1OCC1=CC=CC=C1 VYQNWZOUAUKGHI-UHFFFAOYSA-N 0.000 description 1
- 229960000990 monobenzone Drugs 0.000 description 1
- RQAQWBFHPMSXKR-UHFFFAOYSA-N n-(4-chlorophenyl)-3-(phosphonooxy)naphthalene-2-carboxamide Chemical compound OP(O)(=O)OC1=CC2=CC=CC=C2C=C1C(=O)NC1=CC=C(Cl)C=C1 RQAQWBFHPMSXKR-UHFFFAOYSA-N 0.000 description 1
- FTQWRYSLUYAIRQ-UHFFFAOYSA-N n-[(octadecanoylamino)methyl]octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCNC(=O)CCCCCCCCCCCCCCCCC FTQWRYSLUYAIRQ-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 239000010680 novolac-type phenolic resin Substances 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- LYRFLYHAGKPMFH-UHFFFAOYSA-N octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(N)=O LYRFLYHAGKPMFH-UHFFFAOYSA-N 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- QUBQYFYWUJJAAK-UHFFFAOYSA-N oxymethurea Chemical compound OCNC(=O)NCO QUBQYFYWUJJAAK-UHFFFAOYSA-N 0.000 description 1
- 229950005308 oxymethurea Drugs 0.000 description 1
- 229910052625 palygorskite Inorganic materials 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- WMIWKXQBBHIBDO-UHFFFAOYSA-N phenyl 1-hydroxy-2h-naphthalene-1-carboxylate Chemical compound C1C=CC2=CC=CC=C2C1(O)C(=O)OC1=CC=CC=C1 WMIWKXQBBHIBDO-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229940050271 potassium alum Drugs 0.000 description 1
- GRLPQNLYRHEGIJ-UHFFFAOYSA-J potassium aluminium sulfate Chemical compound [Al+3].[K+].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O GRLPQNLYRHEGIJ-UHFFFAOYSA-J 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000001454 recorded image Methods 0.000 description 1
- KIWUVOGUEXMXSV-UHFFFAOYSA-N rhodanine Chemical compound O=C1CSC(=S)N1 KIWUVOGUEXMXSV-UHFFFAOYSA-N 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 230000001568 sexual effect Effects 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 1
- 239000001016 thiazine dye Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 239000013053 water resistant agent Substances 0.000 description 1
- 238000004078 waterproofing Methods 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
- B41M5/40—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used characterised by the base backcoat, intermediate, or covering layers, e.g. for thermal transfer dye-donor or dye-receiver sheets; Heat, radiation filtering or absorbing means or layers; combined with other image registration layers or compositions; Special originals for reproduction by thermography
- B41M5/42—Intermediate, backcoat, or covering layers
- B41M5/44—Intermediate, backcoat, or covering layers characterised by the macromolecular compounds
-
- 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
- B41M5/382—Contact thermal transfer or sublimation processes
- B41M5/392—Additives, other than colour forming substances, dyes or pigments, e.g. sensitisers, transfer promoting agents
- B41M5/395—Macromolecular additives, e.g. binders
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M2205/00—Printing methods or features related to printing methods; Location or type of the layers
- B41M2205/04—Direct thermal recording [DTR]
Landscapes
- Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Heat Sensitive Colour Forming Recording (AREA)
- Thermal Transfer Or Thermal Recording In General (AREA)
Description
「産業上の利用分野」
本発明は感熱記録体に関し、特に耐水性に優れ
た感熱記録体に関するものである。
「従来の技術」
従来、発色剤と該発色剤と接触して呈色する呈
色剤との呈色反応を利用し、熱により両発色物質
を接触せしめて発色像を得るようにした感熱記録
体は良く知られている。かかる感熱記録体は比較
的安価であり、また記録機器がコンパクトでかつ
その保守も比較的容易であるため、フアクシミリ
や各種計算機等の記録媒体としてのみならず巾広
い分野において使用されている。
一方、使用分野の拡大に伴い、感熱記録体が水
分と接触するような条件下で用いられるケースが
増大し、耐水性に優れた感熱記録体への要望が高
まつている。即ち、一般に感熱記録体は、その記
録層を構成する結合剤として水溶性高分子化合物
が用いられるため、得られた記録層は甚だ耐水性
に劣るという欠点がある。例えば、記録層に水が
付着した状態で擦られると、記録層が脱落するの
みならず記録層自体が剥がれてしまうなどの欠陥
を有する。
このような欠陥を改善する方法として、例え
ば、水溶性高分子化合物にカリ明礬、ホルマリ
ン、アミド樹脂等の耐水化剤を併用する方法が提
案されている。しかし、従来から使用されている
水溶性高分子化合物と耐水化剤の併用にあつては
必ずしも充分な効果が得られないばかりか、塗料
調整時に塗料が凝集したり、地肌カブリを生じた
り、あるいは減感作用を呈する等の新たな問題を
引き起こし、実用には供し得ないものである。ま
た、結合剤としてポリアクリルアミドを用い、こ
れにグリオキサールを併用する提案（特公昭59−
53192号）もあるが、通常の感熱記録体の製造工
程における乾燥条件下では硬化が不充分なため
か、特に非記録部の耐水性について甚だ不満足な
結果しか得られない。
さらに、感熱記録層上に樹脂成分を主体とする
保護層を設ける方法も提案されているが、かかる
樹脂成分としても、通常の水溶性高分子化合物が
用いられるため、やはり充分な耐水性を有する記
録体は得られない。
「発明が解決しようとする問題点」
本発明の目的は、塗料の凝集や地肌カブリを伴
うことなく、しかも通常の乾燥条件下で製造され
ても記録部および非記録部の双方において充分な
耐水性を発揮し得る感熱記録体を提供することで
ある。
「問題点を解決するための手段」
本発明は、支持体上に発色剤および該発色剤と
接触して呈色する呈色剤を含有する感熱記録層を
設けた感熱記録体において、該記録層中もしくは
該記録層上にＮ−メチロールウレタン化ポリビニ
ルアルコールを存在せしめたことを特徴とする感
熱記録体である。
「作用」
本発明は、上記の如く感熱記録層を構成する結
合剤もしくは記録層上に設けられる保護層を構成
する樹脂成分としてＮ−メチロールウレタン化ポ
リビニルアルコールを選択的に使用したところに
重大な特徴を有するものである。
かかるＮ−メチロールウレタン化ポリビニルア
ルコールは、例えば、ポリビニルアルコールを加
熱下で尿素と反応させてウレタン化ポリビニルア
ルコールを調製し、次いでこれをホルムアルデヒ
ドと反応させてメチロール化を行う等の方法で合
成される。
本発明において、Ｎ−メチロールウレタン化ポ
リビニルアルコールのウレタン化率およびメチロ
ール化率については、得られるポリビニルアルコ
ールの粘度、適用する感熱記録体に要求される耐
水性の度合などに応じて適宜選択すべきものであ
り、特に限定するものではないが、一般に、ポリ
ビニルアルコール分子中のビニルアルコール単位
の５〜30％がウレタン化されており、且つウレタ
ン化されたビニルアルコール単位の３％以上がメ
チロール化されたポリビニルアルコールが望まし
い。これらのＮ−メチロールウレタン化ポリビニ
ルアルコールのうちでも、ビニルアルコール単位
の５〜15％がウレタン化されており、且つウレタ
ン化されたビニルアルコール単位の４〜55％がメ
チロール化されたポリビニルアルコールは、塗料
の凝集などの弊害を伴うことがなく、しかも充分
な耐水性を発揮するため、より好ましく用いられ
る。
なお、原料となるポリビニルアルコールの重合
度についても特に限定するものではないが、一般
に1000〜2500程度のものが好ましい。また、鹸化
度も限定するのではなく、完全鹸化ポリビニルア
ルコールのみならず、部分鹸化ポリビニルアルコ
ール等も使用し得るものである。
本発明は、上述の如く記録層を構成する結合剤
もしくは保護層を構成する樹脂成分としてＮ−メ
チロールウレタン化ポリビニルアルコールを選択
的に使用するものであるが、本発明の効果を阻害
しない範囲で他の水溶性または水分散性の結合剤
を併用することもできる。かかる水溶性または水
分散性の結合剤としては、例えばデンプン類、ヒ
ドロキシエチルセルロース、メチルセルロース、
カルボキシメチルセルロース、ゼラチン、カゼイ
ン、アラビアゴム、ポリビニルアルコール、カル
ボキシ変性ポリビニルアルコール、アセトアセチ
ル化ポリビニルアルコール、ジイソブチレン・無
水マレイン酸共重合体塩、スチレン・無水マレイ
ン酸共重合体塩、エチレン・アクリル酸共重合体
塩、スチレン・アクリル酸共重合体塩、スチレ
ン・ブタジエン共重合体エマリジヨン等が例示で
きる。なお、Ｎ−メチロールウレタン化ポリビニ
ルアルコールと他の結合剤とを併用する際には、
全結合剤（または全樹脂成分）におけるＮ−メチ
ロールウレタン化ポリビニルアルコールの割合が
50％以上、好ましくは60％以上となるように配合
するのが望ましい。
本発明は、上述の如くＮ−メチロールウレタン
化ポリビニルアルコールを使用することで、塗料
の凝集や地肌カブリを伴うことなく、耐水性に優
れた感熱記録体の製造を可能にしたものである
が、さらに硬化剤を併用すると、より耐水性に優
れた感熱記録体が得られるため好ましい。
かかる硬化剤としては、グリオキサール、マロ
ンジアルデヒド、スクシンジアルデヒド、グルタ
ルアルデヒド、アジピンアルデヒド、マレインジ
アルデヒドなどの脂肪族ジアルデヒド、ポリアミ
ド樹脂、ポリアミド−エピクロルヒドリン樹脂な
どのポリアミド系樹脂、グリセリン−グリシジル
エーテル樹脂、ソルビトール−ポリグリシジルエ
ーテル樹脂などのエポキシ系樹脂、メラミン樹
脂、メチロールメラミン樹脂、エーテル化メラミ
ン樹脂、メチルエーテル化ヘキサメチロールメラ
ミン樹脂などのメラミン系樹脂、尿素樹脂、尿素
ホルマリン樹脂、ジメチロール尿素樹脂などの尿
素系樹脂等が例示される。これらの硬化剤のうち
でも脂肪族ジアルデヒド、ポリアミド系樹脂、メ
ラミン系樹脂が好ましく、特にグリオキサール
は、Ｎ−メチロールウレタン化ポリビニルアルコ
ールとの組み合わせにおいて、とりわけ耐水性に
優れた感熱記録体が得られるため好ましく用いら
れるものである。
なお、硬化剤の使用量は、特に限定するもので
はないが、Ｎ−メチロールウレタン化ポリビニル
アルコールに対して１重量％以上、好ましくは２
〜60重量％の範囲となるように添加するのが望ま
しい。
また、本発明においては、かかる硬化剤と共に
塩化アンモニウム、塩化マグネシウム、塩化カル
シウム、硫酸アルミニウム、硫酸マグネシウム、
硝酸亜鉛、水酸化カルシウム、炭酸ジルコニウム
アンモニウム、Ti、Zn、Alなどのアルコキシド
等の触媒を使用することもできる。
本発明において、Ｎ−メチロールウレタン化ポ
リビニルアルコールが存在せしめられる層構成に
ついては、特に限定されるものではなく、上述の
如く感熱記録層中および感熱記録層上に設けられ
る樹脂層中のいずれか一方に存在せしめればその
効果を発揮し得るものである。勿論、感熱記録層
と樹脂層の双方にＮ−メチロールウレタン化ポリ
ビニルアルコールを存在せしめた形態を排除する
ものではなく、また、感熱記録層にＮ−メチロー
ルウレタン化ポリビニルアルコールを使用したう
えで樹脂層には他の水溶性高分子化合物等を用い
た形態をも包含するものである。
本発明において、記録層に含有される発色剤と
呈色剤の組合せについては特に限定されるもので
はなく、熱によつて両者が接触して呈色反応を起
こすような組合せなら何れも使用可能であり、例
えば無色ないし淡色の塩基性染料と無機ないし有
機の酸性物質との組合せ、ステアリン酸第二鉄な
どの高級脂肪酸金属塩と没食子酸のようなフエノ
ール類との組合せなどが例示される。さらに、ジ
アゾニウム化合物、カプラー及び塩基性物質を組
合せた感熱記録体など、熱によつて顕食像（記録
像）を得るようにした各種の感熱記録体への適用
も可能であり、本発明はこれらの記録体をも包含
するものである。
無色ないし淡色の塩基性染料としては各種のも
のが公知であり、例えば下記が例示される。
３，３−ビス（ｐ−ジメチルアミノフエニル）
−６−ジメチルアミノフタリド、３，３−、ビス
（ｐ−ジメチルアミノフエニル）フタリド、３−
（ｐ−ジメチルアミノフエニル）−３−（１，２−
ジメチルインドール−３−イル）フタリド、３−
（ｐ−−ジメチルアミノフエニル）−３−（２−メ
チルインドール−３−イル）フタリド、３，３−
ビス（１，２−ジメチルインドール−３−イル）
−５−ジメチルアミノフタリド、３，３−ビス
（１，２−ジメチルインドール−３−イル）−６−
ジメチルアミノフタリド、３，３−ビス（９−エ
チルカルバゾール−３−イル）−６−ジメチルア
ミノフタリド、３，３−ビス（２−フエニルイン
ドール−３−イル）−６−ジメチルアミノフタリ
ド、３−ｐ−ジメチルアミノフエニル−３−（１
−メチルピロール−３−イル）６−ジメチルアミ
ノフタリド等のトリアリルメタン系染料、４，
4′−ビス−ジメチルアミノベンズヒドリルベンジ
ルエーテル、Ｎ−ハロフエニル−ロイコオーラミ
ン、Ｎ−２，４，５−トリクロロフエニルロイコ
オーラミン等のジフエニルメタン系染料、ベンゾ
イルロイコメチレンブルー、ｐ−ニトロベンゾイ
ルロイコメチレンブルー等のチアジン系染料、３
−メチル−スピロ−ジナフトピラン、３−エチル
−スピロ−ジナフトピラン、３−フエニル−スピ
ロ−ジナフトピラン、３−ベンジル−スピロ−ジ
ナフトピラン、３−メチル−ナフト（6′−メトキ
シベンゾ）スピロピラン、３−プロピル−スピロ
−ジベンゾピラン等のスピロ系染料、ローダミン
−Ｂ−アニリノラクタム、ローダミン（ｐ−ニト
ロアニリノ）ラクタム、ローダミン（ｏ−クロロ
アニリノ）ラクタム等のラクタム系染料、３−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−６−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、３−ジ
エチルアミノ−７−クロロフルオラン、３−ジエ
チルアミノ−６−メチル−７−クロロフルオラ
ン、３−ジエチルアミノ−６，７−ジエチルフル
オラン、３−（Ｎ−エチル−ｐ−トルイジノ）−７
−メチルフルオラン、３−ジエチルアミノ−７−
Ｎ−アセチル−Ｎ−メチルアミノフルオラン、３
−ジエチルアミノ−７−Ｎ−メチルアミノフルオ
ラン、３−ジエチルアミノ−７−ジベンジルアミ
ノフルオラン、３−ジエチルアミノ−７−Ｎ−メ
チル−Ｎ−ベンジルアミノフルオラン、３−ジエ
チルアミノ−７−Ｎ−クロロエチル−Ｎ−メチル
アミノフルオラン、３−ジエチルアミノ−７−Ｎ
−ジエチルアミノフルオラン、３−（Ｎ−エチル
−ｐ−トルイジノ）−６−メチル−７−フエニル
アミノフルオラン、３−（Ｎ−エチル−ｐ−トル
イジノ）−６−メチル−７−（ｐ−トルイジノ）フ
ルオラン、３−ジエチルアミノ−６−メチル−７
−フエニルアミノフルオラン、３−ジエチルアミ
ノ−７−（２カルボメトキシ−フエニルアミノ）
フルオラン、３−（Ｎ−シクロヘキシル−Ｎ−メ
チルアミノ）−６−メチル−７−フエニルアミノ
フルオラン、３−ピロリジノ−６−メチル−７−
フエニルアミノフルオラン、３−ピロリジノ−６
−メチル−７−ｐ−ブチルフエニルアミノフルオ
ラン、３−ビペリジノ−６−メチル−７−フエニ
ルアミノフルオラン、３−ジエチルアミノ−６−
メチル−７−キシリジノフルオラン、３−ジエチ
ルアミノ−７−（ｏ−クロロフエニルアミノ）フ
ルオラン、３−ジブチルアミノ−７−（ｏ−クロ
ロフエニルアミノ）フルオロン、３−ジエチルア
ミノ−７−（ｏ−フルオロフエニルアミノ）フル
オラン、３−ジブチルアミノ−７−（ｏ−フルオ
ロフエニルアミノ）フルオラン、３−（Ｎ−メチ
ル−Ｎ−ｎ−アミルアミノ）−６−メチル−７−
フエニルアミノフルオラン、３−（Ｎ−エチル−
Ｎ−イソアミルアミノ）−６−メチル−７−フエ
ニルアミノフルオラン、３−（Ｎ−メチル−Ｎ−
ｎ−ヘキシルアミノ）−６−メチル−７−フエニ
ルアミノフルオラン、３−（Ｎ−エチル−Ｎ−ｎ
−ヘキシルアミノ）−６−メチル−７−フエニル
アミノフルオラン、３−（Ｎ−エチル−Ｎ−β−
エチルヘキシルアミノ）−６−メチル−７−フエ
ニルアミノフルオラン、３−（Ｎ−メチル−Ｎ−
テトラヒドロフルフリルアミノ）−６−メチル−
７−アニリノフルオラン、３−（Ｎ−エチル−Ｎ
−テトラヒドロフルフリルアミノ）−６−メチル
−７−アニリノフルオラン等のフルオラン系染料
等。
また塩基性無色染料と接触して呈色する無機な
いし有機の酸性物質も各種のものが公知であり、
例えば、活性白土、酸性白土、アタパルジヤイ
ト、ベントナイト、コロイダルシリカ、珪酸アル
ミニウムなどの無機酸性物質、４−tert−ブチル
フエノール、４−ヒドロキシジフエノキシド、α
−ナフトール、β−ナフトール、４−ヒドロキシ
アセトフエノール、４−tert−オクチルカテコー
ル、２，2′−ジヒドロキシジフエノール、２，
2′−メチレンビス（４−メチル−６−tert−イソ
ブチルフエノール）、４，4′−（イソプロピリデン
ビス（２−tert−ブチルフエノール）、４，4′−
sec−ブチリデンジフエノール、４−フエニルフ
エノール、４，4′−イソプロピリデンジフエノー
ル（ビスフエノールＡ）、２，2′−メチレンビス
（４−クロルフエノール）ハイドロキノン、４，
4′−シクロヘキシリデンジフエノール、４−ヒド
ロキシ安息香酸ベンジル、４−ヒドロキシフタル
酸ジメチル、ヒドロキノンモノベンジルエーテ
ル、ノボラツク型フエノール樹脂、フエノール重
合体などのフエノール性化合物、安息香酸、ｐ−
tert−ブチル安息香酸、トリクロル安息香酸、テ
レフタル酸、３−sec−ブチル−４−ヒドロキシ
安息香酸、３−シクロヘキシル−４−ヒドロキシ
安息香酸、３，５−ジメチル−４−ヒドロキシ安
息香酸、サリチル酸、３−イソプロピルサリチル
酸、３−tert−ブチルサリチル酸、３−ベンジル
サリチル酸、３−（α−メチルベンジル）サリチ
ル酸、３−クロル−５−（α−メチルベンジル）
サリチル酸、３，５−ジ−tert−ブチルサリチル
酸、３−フエニル−５−（α，α−ジメチルベン
ジル）サリチル酸、３，５−ジ−α−メチルベン
ジルサリチル酸などの芳香族カルボン酸、および
これらフエノール酸化合物、芳香族カルボン酸と
例えば亜鉛、マグネシウム、アルミニウム、カル
シウム、チタン、マンガン、スズ、ニツケルなど
の多価金属との塩、さらには、ハロゲン原子、
C1〜4アルキル基、C1〜4アルコキシル基または置換
もしくは未置換のフエニル基を置換基として１個
以上有していてもよいピリジン、イミダゾール、
ベンゾイミダゾール、３−ピラゾロン、５−ピラ
ゾロン、ベンゾチアゾールまたはキノリンなどと
ロダン酸多価金属塩との錯化合物などの有機酸性
物質等が例示される。
本発明の感熱記録体において、記録層中の発色
剤と呈色剤の使用比率は用いられる発色剤、呈色
剤の種類に応じて適宜選択されるもので、特に限
定するものではないが、例えば塩基性無色染料と
酸性物質を用いる場合には、一般に塩基性無色染
料１重量部に対して１〜50重量部、好ましくは１
〜10重量部の酸性物質が使用される。
これらの物質を含む塗布液の調製には、一般に
水を分散媒体とし、ボールミル、アタライター、
サンドミル等の撹拌・粉砕機により発色剤と呈色
剤とを一緒に又は別々に分散し、塗液として調製
される。
本発明において、Ｎ−メチロールウレタン化ポ
リビニルアルコールを記録層中に存在せしめる場
合には、上記塗液中に、全固形分にして10〜70重
量％、好ましくは15〜50重量％の範囲となるよう
に、かかるポリビニルアルコールを添加するもの
である。
本発明の感熱記録体において、記録層中には必
要に応じて増感剤が添加される。増感剤について
は各種の物質が知られており、例えばステアリン
酸アミド、ステアリン酸メチレンビスアミド、オ
レイン酸アミド、パルチミン酸アミド、抹香オレ
イン酸アミド、ヤシ脂肪酸アミド等の脂肪酸アミ
ド類、２，2′−メチレンビス（４−メチル−６−
tert−ブチルフエノール）、２，2′−メチレンビス
（４−エチル−６−tert−ブチルフエノール）、
４，4′−ブチリデンビス（６−tert−ブチル−３
−メチルフエノール）、１，１，３−トリス（２
−メチル−４−ヒドロキシ−５−tert−ブチルフ
エニル）ブタン、２，４−ジ−tert−ブチル−３
−メチルフエノール、４，4′−チオビス（３−メ
チル−6′−tert−ブチルフエノール）等のヒンダ
ードフエノール類、２−（2′−ヒドロキシ−5′−
メチルフエニル）ベンゾトリアゾール、２−ヒド
ロキシ−４−ベンジルオキシベンゾフエノン等の
紫外線吸収剤、１，２−ジ（３−メチルフエノキ
シ）エタン、１，２−ジフエノキシエタン、１−
フエノキシ−２−（４−メチルフエノキシ）エタ
ン、テレフタル酸ジメチルエステル、テレフタル
酸ジフチルエステル、テレフタル酸ジベンジルエ
ステル、イソフタル酸ジブチルエステル、１−ヒ
ドロキシナフトエ酸フエニルエステル等やその他
各種公知の熱可融性物質などが例示される。なお
増感剤の添加量については特に限定するものでは
なく、一般に呈色剤１重量部に対して４重量部以
下の範囲で調節するのが望ましい。
さらに、塗液中には各種の助剤を添加すること
ができ、例えば、ジオクチルスルフオコハク酸ナ
トリウム、ドデシルベンゼンスルフオン酸ナトリ
ウム、ラウリルアルコール硫酸エステル・ナトリ
ウム塩、アルギン酸塩、脂肪酸金属塩などの分散
剤、ベンゾフエノン系などの紫外線吸収剤、その
他消泡剤、蛍光染料、着色染料などが挙げられ
る。また必要に応じてステアリン酸亜鉛、ステア
リン酸カルシウム、ポリエチレンワツクス、カル
ナバロウ、パラフインワツクス、エステルワツク
スなどのワツクス類、炭酸カルシウム、酸化亜
鉛、酸化アルミニウム、二酸化チタン、二酸化珪
素、水酸化アルミニウム、硫酸バリウム、硫酸亜
鉛、タルク、カオリン、クレー、焼成クレー、コ
ロイダルシリカ、珪藻土、微粒子状無水シリカ、
活性白土等の無機顔料、スチレンマイクロボー
ル、ナイロンパウダー、ポリエチレンパウダー、
尿素・ホルマリン樹脂フイラー、生澱粉粒等の有
機顔料等を添加することもできる。
本発明の感熱記録体において、記録層の形成方
法等については特に限定されるものではなく、従
来から周知慣用の技術に従つて形成することがで
き、例えばエアーナイフコーテイング、ブリバー
ブレードコーテイング、ピユアーブレードコーテ
イング、シヨート・ドウエルコーテイング等によ
り塗液を塗布・乾燥する方法等によつて形成され
る。また塗液の塗布量についても特に限定される
ものではないが、通常乾燥重量で２乃至12ｇ／
m2、好ましくは３乃至10ｇ／m2の範囲である。な
お、かかる記録層が形成される支持体としては紙
が一般的であるが、合成樹脂フイルム、ラミネー
ト紙、合成繊維シート、不織布シート等にも適用
できる。
一方、本発明において、Ｎ−メチロールウレタ
ン化ポリビニルアルコールを記録層上に設けられ
る樹脂層中に存在せしめる場合には、かかるポリ
ビニルアルコールを水溶液とし、必要に応じて前
述の如き他の水溶性または水分散性結合剤、硬化
剤、無機ないしは有機顔料、ワツクス類、分散
剤、消泡剤などを適宜添加して樹脂層用の塗液が
調製される。なお、無機ないしは有機顔料の使用
量については一般に樹脂成分100重量部に対して
５〜500重量部の範囲で配合されるのが望ましい。
かくして調製された樹脂層用の塗液は、必要に応
じてミキサー、アトライター、ホールミル、ロー
ルミル等の混合・撹拌機によつて十分混合分散さ
れた後、公知の塗布装置により感熱記録層上に塗
布される。樹脂層用塗液の塗布量は、特に限定さ
れるものではないが、0.1ｇ／m2未満では充分な
効果を得ることができず、また、20ｇ／m2を越す
と感熱記録体の記録感度を著しく低下させる恐れ
があるため、一般には乾燥重量で0.1〜20ｇ／m2、
好ましくは0.5〜10ｇ／m2の範囲で調節されるの
が望ましい。
かくして、本発明の感熱記録体は、特定のポリ
ビニルアルコールが記録層中または樹脂層中に存
在せしめられているため、塗料の凝集や地肌カブ
リを伴うことなく、しかも通常の乾燥条件下で製
造されても優れた耐水性を発揮するものである。
なお、必要に応じて感熱記録体の裏面側にも樹
脂層を設けることによつて一層保存性を高めるこ
とも可能である。さらに、支持体に下塗り層を設
けたり、記録体裏面に粘着剤処理を施し、粘着ラ
ベルに加工する等、感熱記録体製造分野における
各種の公知技術が必要に応じて付加し得るもので
ある。
「実施例」
以下に実施例を示し、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。また、特に断らない限り例中の部および％は
それぞれ重量部及び重量％を示す。
実施例 １
Ａ液調製
３−（Ｎ−エチル−Ｎ−イソアミル）アミノ−
６−メチル−７−フエニルアミノフルオラン
10部
メチルセルロース５％水溶液 ５部
水 40部
この組成物をサンドミルで平均粒子径が3μ
ｍとなるまで粉砕した。
Ｂ液調製
４，4′−イソプロピリデンジフエノール 30部
メチルセルロース５％水溶液 ５部
水 80部
この組成物をサンドミルで平均粒子径が3μ
ｍとなるまで粉砕した。
Ｃ液調製
１，２−ジ（３−メチルフエノキシ）エタン
20部
メチルセルロース５％水溶液 ５部
水 55部
この組成物をサンドミルで平均粒子径が3μ
ｍとなるまで粉砕した。
記録層の形成
Ａ液55部、Ｂ液115部、Ｃ液80部、Ｎ−メチロ
ールウレタン化ポリビニルアルコール（商品
名：ユーラミンXP−66、三井東圧化学社製）
の10％水溶液200部、５％グリオキサール水溶
液100部、および炭酸カルシウム35部を混合・
撹拌し、塗液とした。得られた塗液を50ｇ／m2
の原紙に乾燥後の塗布量が６ｇ／m2となるよう
に塗布乾燥して感熱記録紙を得た。
実施例 ２
実施例１の記録層の形成において、５％グリオ
キサール水溶液の代わりに、ポリアミド樹脂（商
品名：エピノツクスＰ−800、デイツク・ハーキ
ユレス社製）の５％水溶液を用いた以外は実施例
１と同様に行つて感熱記録紙を得た。
実施例 ３
実施例１の記録層の形成において、５％グリオ
キサール水溶液の代わりに、メラミン樹脂（商品
名：スミレーツ・レジン613、住友化学社製）の
５％水溶液を用いた以外は実施例１と同様にして
感熱記録紙を得た。
実施例 ４
実施例１の記録層の形成において、５％グリオ
キサール水溶液を用いなかつた以外は実施例１と
同様に行つて感熱記録紙を得た。
実施例 ５
実施例１のＢ液調製において、４，4′−イソプ
ロピリデンジフエノールの代わりに、ロダン酸亜
鉛と２，３−ジメチル−１−フエニル−５−ピラ
ゾロンとの錯化合物を使用した以外は実施例１と
同様にして感熱記録紙を得た。
実施例 ６
実施例１の記録層の形成において、Ｎ−メチロ
ールウレタン化ポリビニルアルコールの代わり
に、ポリビニルアルコール（商品名：PVA−
110、クラレ社製）の10％水溶液200部を用いた以
外は実施例１と同様にして記録層を形成した。次
いで、かかる記録層上に下記組成からなる樹脂塗
液を、乾燥後の塗布量が４ｇ／m2となるように塗
布乾燥して樹脂層を有する感熱記録紙を得た。
樹脂塗液組成
Ｎ−メチロールウレタン化ポリビニルアルコール
（商品名：ユーラミンXP−66、三井東圧化学社
製）の10％水溶液 500部
５％グリオキサール水溶液 160部
炭酸カルシウム 100部
比較例 １
実施例１の記録層の形成において、Ｎ−メチロ
ールウレタン化ポリビニルアルコールの代わり
に、アクリルアミド系共重合体（商品名：Ｆ−
007、昭和電工社製）の10％水溶液を使用した以
外は実施例１と同様にして感熱記録紙を得た。
比較例 ２
実施例６の樹脂塗液組成において、Ｎ−メチロ
ールウレタン化ポリビニルアルコールの代わり
に、ポリビニルアルコール（商品名：PVA−
110、クラレ社製）の10％水溶液を使用した以外
は実施例６と同様に行つて樹脂層を有する感熱記
録紙を得た。
かくして得られた８種類の感熱記録紙を感熱プ
リンターにて印字発色せしめ、その地肌部濃度お
よび発色濃度をマクベス濃度計（マクベス社製、
RD−914型、アンバーフイルター使用）で測定
し、その結果を第１表に示した。また、非記録部
および記録部の耐水性を以下の方法で評価し、そ
の結果を第１表に掲げた。更に、これらの感熱記
録紙を調製する際に用いた記録層用塗液および樹
脂層用塗液の塗料性状（凝集状態）を評価し、そ
の結果を第１表に併記した。
耐水性の評価方法
〔非記録部の耐水性〕
印字前の感熱記録紙の記録層上に水を１滴落と
して30秒経過後、指先で10回擦つた後、記録紙を
乾燥した。次いで、評価を容易にするために、記
録紙を130℃の熱板に５秒間押し付けて発色させ、
記録層の剥がれ具合を目視で評価した。
〔記録部の耐水性〕
感熱記録紙を130℃の熱板に５秒間押し付けて
発色させた後、その発色部に水を１滴落とし、30
秒後に指先で10回擦り、発色濃度の変化によつて
記録部の耐水性を目視評価した。
〔評価基準〕
◎：非常に良好 ○：良好
Δ：やや不良 ×：不良
"Industrial Application Field" The present invention relates to a heat-sensitive recording material, and particularly to a heat-sensitive recording material having excellent water resistance. "Prior Art" Conventionally, heat-sensitive recording utilizes a coloring reaction between a coloring agent and a coloring agent that develops color when it comes into contact with the coloring agent, and a colored image is obtained by bringing both coloring materials into contact with each other using heat. The body is well known. Such thermosensitive recording media are relatively inexpensive, the recording equipment is compact, and maintenance is relatively easy, so they are used not only as recording media for facsimile machines and various computers, but also in a wide range of fields. On the other hand, with the expansion of the field of use, the number of cases in which heat-sensitive recording bodies are used under conditions where they come into contact with moisture has increased, and the demand for heat-sensitive recording bodies with excellent water resistance is increasing. That is, since thermosensitive recording materials generally use a water-soluble polymer compound as a binder constituting the recording layer, the resulting recording layer has a drawback of extremely poor water resistance. For example, if the recording layer is rubbed with water attached to it, there will be defects such as not only the recording layer falling off but also the recording layer itself peeling off. As a method for improving such defects, for example, a method has been proposed in which a water-soluble polymer compound is used in combination with a water-resistant agent such as potassium alum, formalin, or amide resin. However, when conventionally used water-soluble polymer compounds and waterproofing agents are used together, not only is the sufficient effect not always obtained, but the paint may aggregate during paint preparation, cause fogging, or This causes new problems such as a desensitizing effect and cannot be put to practical use. In addition, a proposal was made to use polyacrylamide as a binder in combination with glyoxal (Japanese Patent Publication No. 1983-
No. 53192), but this method yields extremely unsatisfactory results, especially in terms of water resistance in non-recording areas, probably because curing is insufficient under dry conditions in the normal manufacturing process of heat-sensitive recording materials. Furthermore, a method of providing a protective layer mainly composed of a resin component on the heat-sensitive recording layer has been proposed, but since the resin component is also a normal water-soluble polymer compound, it still has sufficient water resistance. No records are available. "Problems to be Solved by the Invention" The object of the present invention is to provide sufficient water resistance in both recorded and non-recorded areas even when manufactured under normal drying conditions without causing paint aggregation or background fog. It is an object of the present invention to provide a heat-sensitive recording material that can exhibit excellent properties. "Means for Solving the Problems" The present invention provides a heat-sensitive recording material in which a heat-sensitive recording layer containing a coloring agent and a coloring agent that develops a color upon contact with the coloring agent is provided on a support. This is a heat-sensitive recording material characterized by the presence of N-methylolurethanized polyvinyl alcohol in or on the recording layer. "Function" As described above, the present invention has an important feature in that N-methylolurethanized polyvinyl alcohol is selectively used as the binder constituting the heat-sensitive recording layer or the resin component constituting the protective layer provided on the recording layer. It has characteristics. Such N-methylol urethanized polyvinyl alcohol is synthesized, for example, by reacting polyvinyl alcohol with urea under heat to prepare urethanized polyvinyl alcohol, and then reacting this with formaldehyde to perform methylolation. . In the present invention, the urethanization rate and methylol conversion rate of N-methylolurethanized polyvinyl alcohol should be appropriately selected depending on the viscosity of the obtained polyvinyl alcohol, the degree of water resistance required of the applied heat-sensitive recording material, etc. Although not particularly limited, generally 5 to 30% of the vinyl alcohol units in the polyvinyl alcohol molecule are urethanized, and 3% or more of the urethanized vinyl alcohol units are methylolated. Polyvinyl alcohol is preferred. Among these N-methylolurethanized polyvinyl alcohols, polyvinyl alcohols in which 5 to 15% of the vinyl alcohol units are urethanized and 4 to 55% of the urethanized vinyl alcohol units are methylolated are: It is more preferably used because it does not cause problems such as agglomeration of the paint and exhibits sufficient water resistance. The degree of polymerization of polyvinyl alcohol as a raw material is not particularly limited either, but it is generally preferably about 1000 to 2500. Furthermore, the degree of saponification is not limited, and not only fully saponified polyvinyl alcohol but also partially saponified polyvinyl alcohol and the like can be used. The present invention selectively uses N-methylolurethanized polyvinyl alcohol as the binder constituting the recording layer or the resin component constituting the protective layer, as described above, but it may be used as long as it does not impede the effects of the present invention. Other water-soluble or water-dispersible binders can also be used in combination. Examples of such water-soluble or water-dispersible binders include starches, hydroxyethylcellulose, methylcellulose,
Carboxymethylcellulose, gelatin, casein, gum arabic, polyvinyl alcohol, carboxy-modified polyvinyl alcohol, acetoacetylated polyvinyl alcohol, diisobutylene/maleic anhydride copolymer salt, styrene/maleic anhydride copolymer salt, ethylene/acrylic acid copolymer salt Examples include polymer salts, styrene/acrylic acid copolymer salts, styrene/butadiene copolymer emulsions, and the like. In addition, when using N-methylolurethanized polyvinyl alcohol and other binders together,
The proportion of N-methylolurethanized polyvinyl alcohol in the total binder (or total resin component) is
It is desirable that the content be 50% or more, preferably 60% or more. The present invention uses N-methylolurethanized polyvinyl alcohol as described above to make it possible to produce a heat-sensitive recording medium with excellent water resistance without causing paint aggregation or background fog. Furthermore, it is preferable to use a curing agent in combination because a heat-sensitive recording material with even better water resistance can be obtained. Examples of such curing agents include aliphatic dialdehydes such as glyoxal, malondialdehyde, succindialdehyde, glutaraldehyde, adipine aldehyde, maleic dialdehyde, polyamide resins, polyamide resins such as polyamide-epichlorohydrin resin, and glycerin-glycidyl ether resins. , epoxy resins such as sorbitol-polyglycidyl ether resins, melamine resins such as melamine resins, methylol melamine resins, etherified melamine resins, methyl etherified hexamethylol melamine resins, urea resins, urea-formalin resins, dimethylol urea resins, etc. Examples include urea-based resins. Among these curing agents, aliphatic dialdehydes, polyamide resins, and melamine resins are preferable, and glyoxal in particular can provide a thermosensitive recording material with particularly excellent water resistance when combined with N-methylolurethanized polyvinyl alcohol. Therefore, it is preferably used. The amount of the curing agent used is not particularly limited, but is 1% by weight or more, preferably 2% by weight based on the N-methylolurethanized polyvinyl alcohol.
It is desirable to add it in a range of ~60% by weight. In addition, in the present invention, ammonium chloride, magnesium chloride, calcium chloride, aluminum sulfate, magnesium sulfate,
Catalysts such as zinc nitrate, calcium hydroxide, ammonium zirconium carbonate, alkoxides of Ti, Zn, Al, etc. can also be used. In the present invention, the layer structure in which N-methylolurethanized polyvinyl alcohol is present is not particularly limited, and as described above, it can be present either in the heat-sensitive recording layer or in the resin layer provided on the heat-sensitive recording layer. If it is made to exist, the effect can be exerted. Of course, this does not exclude a form in which N-methylol urethane polyvinyl alcohol is present in both the heat-sensitive recording layer and the resin layer, and it is also possible to use N-methylol urethane polyvinyl alcohol in the heat-sensitive recording layer and then add the resin layer to the resin layer. This also includes forms using other water-soluble polymer compounds. In the present invention, there are no particular limitations on the combination of the coloring agent and the coloring agent contained in the recording layer, and any combination that causes a coloring reaction when the two come into contact with each other due to heat can be used. Examples include a combination of a colorless or light-colored basic dye and an inorganic or organic acidic substance, and a combination of a higher fatty acid metal salt such as ferric stearate and a phenol such as gallic acid. Furthermore, it is also possible to apply the present invention to various heat-sensitive recording materials that obtain an eclipsed image (recorded image) by heat, such as a heat-sensitive recording material that combines a diazonium compound, a coupler, and a basic substance. These recording bodies are also included. Various types of colorless to light-colored basic dyes are known, and examples include the following. 3,3-bis(p-dimethylaminophenyl)
-6-dimethylaminophthalide, 3,3-,bis(p-dimethylaminophenyl)phthalide, 3-
(p-dimethylaminophenyl)-3-(1,2-
dimethylindol-3-yl)phthalide, 3-
(p--dimethylaminophenyl)-3-(2-methylindol-3-yl)phthalide, 3,3-
Bis(1,2-dimethylindol-3-yl)
-5-dimethylaminophthalide, 3,3-bis(1,2-dimethylindol-3-yl)-6-
Dimethylaminophthalide, 3,3-bis(9-ethylcarbazol-3-yl)-6-dimethylaminophthalide, 3,3-bis(2-phenylindol-3-yl)-6-dimethylaminophthalide 3-p-dimethylaminophenyl-3-(1
-methylpyrrol-3-yl) 6-dimethylaminophthalide and other triallylmethane dyes, 4,
Diphenylmethane dyes such as 4'-bis-dimethylaminobenzhydryl benzyl ether, N-halophenyl-leucoauramine, N-2,4,5-trichlorophenylleucoauramine, benzoylleucomethylene blue, p-nitrobenzoylleuco Thiazine dyes such as methylene blue, 3
-Methyl-spiro-dinaphthopyran, 3-ethyl-spiro-dinaphthopyran, 3-phenyl-spiro-dinaphthopyran, 3-benzyl-spiro-dinaphthopyran, 3-methyl-naphtho(6'-methoxybenzo)spiropyran, 3-propyl-spiro - Spiro dyes such as dibenzopyran, lactam dyes such as rhodamine-B-anilinolactam, rhodamine (p-nitroanilino) lactam, rhodamine (o-chloroanilino) lactam, 3-dimethylamino-7-methoxyfluoran, 3 -diethylamino-6-methoxyfluorane, 3-diethylamino-7-methoxyfluorane, 3-diethylamino-7-chlorofluorane, 3-diethylamino-6-methyl-7-chlorofluorane, 3-diethylamino-6,7 -diethylfluorane, 3-(N-ethyl-p-toluidino)-7
-Methylfluorane, 3-diethylamino-7-
N-acetyl-N-methylaminofluorane, 3
-diethylamino-7-N-methylaminofluorane, 3-diethylamino-7-dibenzylaminofluorane, 3-diethylamino-7-N-methyl-N-benzylaminofluorane, 3-diethylamino-7-N-chloroethyl -N-methylaminofluorane, 3-diethylamino-7-N
-diethylaminofluorane, 3-(N-ethyl-p-toluidino)-6-methyl-7-phenylaminofluorane, 3-(N-ethyl-p-toluidino)-6-methyl-7-(p- toluidino)fluoran, 3-diethylamino-6-methyl-7
-phenylaminofluorane, 3-diethylamino-7-(2carbomethoxy-phenylamino)
Fluoran, 3-(N-cyclohexyl-N-methylamino)-6-methyl-7-phenylaminofluoran, 3-pyrrolidino-6-methyl-7-
Phenylaminofluorane, 3-pyrrolidino-6
-Methyl-7-p-butylphenylaminofluoran, 3-biperidino-6-methyl-7-phenylaminofluoran, 3-diethylamino-6-
Methyl-7-xylidinofluorane, 3-diethylamino-7-(o-chlorophenylamino)fluoran, 3-dibutylamino-7-(o-chlorophenylamino)fluorone, 3-diethylamino-7-(o-fluoro phenylamino)fluoran, 3-dibutylamino-7-(o-fluorophenylamino)fluoran, 3-(N-methyl-N-n-amylamino)-6-methyl-7-
Phenylaminofluorane, 3-(N-ethyl-
N-isoamylamino)-6-methyl-7-phenylaminofluorane, 3-(N-methyl-N-
n-hexylamino)-6-methyl-7-phenylaminofluorane, 3-(N-ethyl-N-n
-hexylamino)-6-methyl-7-phenylaminofluorane, 3-(N-ethyl-N-β-
ethylhexylamino)-6-methyl-7-phenylaminofluorane, 3-(N-methyl-N-
Tetrahydrofurfurylamino)-6-methyl-
7-anilinofluorane, 3-(N-ethyl-N
Fluoran dyes such as -tetrahydrofurfurylamino)-6-methyl-7-anilinofluorane, etc. In addition, various inorganic or organic acidic substances that change color when they come into contact with basic colorless dyes are known.
For example, activated clay, acid clay, attapulgite, bentonite, colloidal silica, inorganic acidic substances such as aluminum silicate, 4-tert-butylphenol, 4-hydroxydiphenooxide, α
-naphthol, β-naphthol, 4-hydroxyacetophenol, 4-tert-octylcatechol, 2,2'-dihydroxydiphenol, 2,
2'-methylenebis(4-methyl-6-tert-isobutylphenol), 4,4'-(isopropylidenebis(2-tert-butylphenol), 4,4'-
sec-butylidene diphenol, 4-phenylphenol, 4,4'-isopropylidene diphenol (bisphenol A), 2,2'-methylenebis(4-chlorophenol)hydroquinone, 4,
Phenolic compounds such as 4'-cyclohexylidene diphenol, benzyl 4-hydroxybenzoate, dimethyl 4-hydroxyphthalate, hydroquinone monobenzyl ether, novolac type phenolic resin, phenolic polymer, benzoic acid, p-
tert-butylbenzoic acid, trichlorobenzoic acid, terephthalic acid, 3-sec-butyl-4-hydroxybenzoic acid, 3-cyclohexyl-4-hydroxybenzoic acid, 3,5-dimethyl-4-hydroxybenzoic acid, salicylic acid, 3 -isopropylsalicylic acid, 3-tert-butylsalicylic acid, 3-benzylsalicylic acid, 3-(α-methylbenzyl)salicylic acid, 3-chloro-5-(α-methylbenzyl)
Aromatic carboxylic acids such as salicylic acid, 3,5-di-tert-butylsalicylic acid, 3-phenyl-5-(α,α-dimethylbenzyl)salicylic acid, 3,5-di-α-methylbenzylsalicylic acid, and these phenols acid compounds, salts of aromatic carboxylic acids and polyvalent metals such as zinc, magnesium, aluminum, calcium, titanium, manganese, tin, and nickel; furthermore, halogen atoms,
Pyridine, imidazole, which may have one or more C 1-4 alkyl group, C 1-4 alkoxyl group, or substituted or unsubstituted phenyl group as a substituent;
Examples include organic acidic substances such as benzimidazole, 3-pyrazolone, 5-pyrazolone, benzothiazole, or a complex compound of quinoline and a polyvalent metal salt of rhodanic acid. In the heat-sensitive recording material of the present invention, the ratio of the color former and color former in the recording layer is appropriately selected depending on the type of color former and color former used, and is not particularly limited. For example, when using a basic colorless dye and an acidic substance, generally 1 to 50 parts by weight, preferably 1 part by weight, per 1 part by weight of the basic colorless dye.
~10 parts by weight of acidic substance are used. To prepare a coating solution containing these substances, generally water is used as a dispersion medium and a ball mill, attaliter,
A coating liquid is prepared by dispersing a coloring agent and a coloring agent together or separately using a stirring/pulverizing machine such as a sand mill. In the present invention, when N-methylolurethanized polyvinyl alcohol is present in the recording layer, the total solid content in the coating liquid is 10 to 70% by weight, preferably 15 to 50% by weight. Thus, such polyvinyl alcohol is added. In the heat-sensitive recording material of the present invention, a sensitizer is added to the recording layer as necessary. Various substances are known as sensitizers, such as fatty acid amides such as stearic acid amide, stearic acid methylene bisamide, oleic acid amide, palmitic acid amide, matcha oleic acid amide, coconut fatty acid amide, 2,2' -methylenebis(4-methyl-6-
tert-butylphenol), 2,2'-methylenebis(4-ethyl-6-tert-butylphenol),
4,4'-Butylidene bis(6-tert-butyl-3
-methylphenol), 1,1,3-tris(2
-Methyl-4-hydroxy-5-tert-butylphenyl)butane, 2,4-di-tert-butyl-3
- Methylphenol, hindered phenols such as 4,4'-thiobis(3-methyl-6'-tert-butylphenol), 2-(2'-hydroxy-5'-
UV absorbers such as methylphenyl)benzotriazole, 2-hydroxy-4-benzyloxybenzophenone, 1,2-di(3-methylphenoxy)ethane, 1,2-diphenoxyethane, 1-
Phenoxy-2-(4-methylphenoxy)ethane, dimethyl terephthalate, diphthyl terephthalate, dibenzyl terephthalate, dibutyl isophthalate, phenyl 1-hydroxynaphthoate, etc., and various other known thermofusible materials. Examples include sexual substances. Note that the amount of the sensitizer added is not particularly limited, and is generally desirably adjusted within a range of 4 parts by weight or less per 1 part by weight of the coloring agent. Furthermore, various auxiliaries can be added to the coating solution, such as sodium dioctyl sulfosuccinate, sodium dodecylbenzenesulfonate, sodium lauryl alcohol sulfate, alginate, fatty acid metal salt, etc. Examples include dispersants, ultraviolet absorbers such as benzophenone, antifoaming agents, fluorescent dyes, and coloring dyes. In addition, waxes such as zinc stearate, calcium stearate, polyethylene wax, carnauba wax, paraffin wax, and ester wax, calcium carbonate, zinc oxide, aluminum oxide, titanium dioxide, silicon dioxide, aluminum hydroxide, and sulfuric acid are also available. Barium, zinc sulfate, talc, kaolin, clay, calcined clay, colloidal silica, diatomaceous earth, fine particulate anhydrous silica,
Inorganic pigments such as activated clay, styrene microballs, nylon powder, polyethylene powder,
It is also possible to add organic pigments such as urea/formalin resin fillers and raw starch granules. In the heat-sensitive recording material of the present invention, there are no particular limitations on the method of forming the recording layer, and the recording layer can be formed according to conventionally well-known and commonly used techniques, such as air knife coating, bribber blade coating, pin coating, etc. It is formed by applying and drying a coating liquid using your blade coating, shoot/dwell coating, or the like. The amount of coating liquid applied is not particularly limited, but it is usually 2 to 12 g/dry weight.
m 2 , preferably in the range 3 to 10 g/m 2 . The support on which such a recording layer is formed is generally paper, but it can also be applied to synthetic resin films, laminated papers, synthetic fiber sheets, nonwoven fabric sheets, and the like. On the other hand, in the present invention, when N-methylolurethanized polyvinyl alcohol is present in the resin layer provided on the recording layer, such polyvinyl alcohol is made into an aqueous solution, and if necessary, other water-soluble or water-soluble A coating liquid for the resin layer is prepared by appropriately adding a dispersible binder, a curing agent, an inorganic or organic pigment, a wax, a dispersant, an antifoaming agent, and the like. The amount of inorganic or organic pigment to be used is generally desirably in the range of 5 to 500 parts by weight per 100 parts by weight of the resin component.
The coating liquid for the resin layer prepared in this manner is thoroughly mixed and dispersed using a mixer, attritor, whole mill, roll mill, etc., as necessary, and then applied onto the heat-sensitive recording layer using a known coating device. applied. The coating amount of the coating liquid for the resin layer is not particularly limited, but if it is less than 0.1 g/m 2 , sufficient effect cannot be obtained, and if it exceeds 20 g/m 2 , the recording of the thermal recording material will be impaired. Generally, the dry weight is 0.1 to 20g/ m2 , as it may significantly reduce sensitivity.
Preferably, it is adjusted within the range of 0.5 to 10 g/m 2 . In this way, the heat-sensitive recording material of the present invention, in which the specific polyvinyl alcohol is present in the recording layer or the resin layer, can be produced under normal drying conditions without causing paint aggregation or background fog. It also exhibits excellent water resistance. Note that it is also possible to further improve the storage stability by providing a resin layer on the back side of the heat-sensitive recording material, if necessary. Furthermore, various known techniques in the field of heat-sensitive recording material production may be added as necessary, such as providing an undercoat layer on the support, applying an adhesive treatment to the back surface of the recording material, and processing it into an adhesive label. "Example" The present invention will be described in more detail with reference to Examples below, but the present invention is of course not limited to these. Further, unless otherwise specified, parts and % in the examples indicate parts by weight and % by weight, respectively. Example 1 Preparation of liquid A 3-(N-ethyl-N-isoamyl)amino-
6-Methyl-7-phenylaminofluorane
10 parts 5% methylcellulose aqueous solution 5 parts water 40 parts This composition was milled in a sand mill until the average particle size was 3μ.
It was ground to m. Preparation of Solution B 4,4'-Isopropylidene diphenol 30 parts Methyl cellulose 5% aqueous solution 5 parts Water 80 parts This composition was milled in a sand mill until the average particle size was 3 μm.
It was ground to m. Preparation of liquid C 1,2-di(3-methylphenoxy)ethane
20 parts 5% methylcellulose aqueous solution 5 parts water 55 parts This composition was milled in a sand mill until the average particle size was 3μ.
It was ground to m. Formation of recording layer: 55 parts of liquid A, 115 parts of liquid B, 80 parts of liquid C, N-methylolurethanized polyvinyl alcohol (trade name: Euramin XP-66, manufactured by Mitsui Toatsu Chemical Co., Ltd.)
Mix 200 parts of a 10% aqueous solution of , 100 parts of a 5% glyoxal aqueous solution, and 35 parts of calcium carbonate.
The mixture was stirred to form a coating liquid. 50g/m 2 of the obtained coating liquid
A heat-sensitive recording paper was obtained by coating and drying the mixture on base paper so that the coating amount after drying was 6 g/m 2 . Example 2 Example 1 except that in forming the recording layer of Example 1, a 5% aqueous solution of polyamide resin (trade name: Epinox P-800, manufactured by Deik Hercules) was used instead of the 5% glyoxal aqueous solution. A thermosensitive recording paper was obtained in the same manner as above. Example 3 Same as Example 1 except that in forming the recording layer of Example 1, a 5% aqueous solution of melamine resin (trade name: Sumirates Resin 613, manufactured by Sumitomo Chemical Co., Ltd.) was used instead of the 5% glyoxal aqueous solution. A thermosensitive recording paper was obtained in the same manner. Example 4 A thermosensitive recording paper was obtained in the same manner as in Example 1 except that the 5% glyoxal aqueous solution was not used in the formation of the recording layer in Example 1. Example 5 In the preparation of Solution B in Example 1, a complex compound of zinc rhodanate and 2,3-dimethyl-1-phenyl-5-pyrazolone was used instead of 4,4'-isopropylidene diphenol. A thermosensitive recording paper was obtained in the same manner as in Example 1. Example 6 In forming the recording layer of Example 1, polyvinyl alcohol (trade name: PVA-) was used instead of N-methylolurethanized polyvinyl alcohol.
A recording layer was formed in the same manner as in Example 1, except that 200 parts of a 10% aqueous solution of 110 (manufactured by Kuraray Co., Ltd.) was used. Next, a resin coating liquid having the following composition was applied onto the recording layer so that the coating amount after drying was 4 g/m 2 and dried to obtain a thermosensitive recording paper having a resin layer. Resin coating composition 500 parts of 10% aqueous solution of N-methylol urethanized polyvinyl alcohol (trade name: Euramin XP-66, manufactured by Mitsui Toatsu Chemical Co., Ltd.) 160 parts of 5% aqueous glyoxal solution In forming the recording layer, an acrylamide copolymer (trade name: F-
A thermosensitive recording paper was obtained in the same manner as in Example 1, except that a 10% aqueous solution of 007 (manufactured by Showa Denko K.K.) was used. Comparative Example 2 In the resin coating composition of Example 6, polyvinyl alcohol (trade name: PVA-
A thermosensitive recording paper having a resin layer was obtained in the same manner as in Example 6 except that a 10% aqueous solution of 110 (manufactured by Kuraray Co., Ltd.) was used. The 8 types of thermal recording paper obtained in this way were printed in color using a thermal printer, and the background density and color density were measured using a Macbeth densitometer (manufactured by Macbeth Co., Ltd.,
The results are shown in Table 1. In addition, the water resistance of the non-recorded area and the recorded area was evaluated by the following method, and the results are listed in Table 1. Furthermore, the coating properties (aggregation state) of the recording layer coating liquid and the resin layer coating liquid used in preparing these heat-sensitive recording papers were evaluated, and the results are also listed in Table 1. Method for evaluating water resistance [Water resistance of non-recording area] One drop of water was dropped on the recording layer of the heat-sensitive recording paper before printing, and after 30 seconds, the recording paper was rubbed 10 times with a fingertip, and then the recording paper was dried. Next, to facilitate evaluation, the recording paper was pressed against a hot plate at 130°C for 5 seconds to develop color.
The degree of peeling of the recording layer was visually evaluated. [Water resistance of the recording area] After pressing the thermal recording paper against a 130°C heating plate for 5 seconds to develop color, drop one drop of water on the colored area and heat it for 30 minutes.
After a few seconds, it was rubbed 10 times with a fingertip, and the water resistance of the recorded area was visually evaluated based on the change in color density. [Evaluation criteria] ◎: Very good ○: Good Δ: Slightly poor ×: Poor
【表】
○：凝集なし ×：凝集あり
「効果」
第１表の結果から明らかな如く、本発明による
感熱記録体は塗料の凝集や地肌カブリを伴うこと
がなく、しかも記録部および非記録部の双方にお
いて耐水性に優れた感熱記録体であつた。[Table] ○: No aggregation ×: Agglomeration “Effect” As is clear from the results in Table 1, the heat-sensitive recording material according to the present invention is free from aggregation of paint and background fog, and moreover, both recorded and non-recorded areas The heat-sensitive recording material had excellent water resistance in both respects.
Claims (1)
呈色する呈色剤を含有する感熱記録層を設けた感
熱記録体において、該記録層中もしくは該記録層
上にＮ−メチロールウレタン化ポリビニルアルコ
ールを存在せしめたことを特徴とする感熱記録
体。1 In a heat-sensitive recording material provided with a heat-sensitive recording layer containing a color former and a color former that develops a color when in contact with the color former on a support, N-methylol urethane is formed in or on the recording layer. A heat-sensitive recording material characterized by the presence of polyvinyl alcohol.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60153483A JPS6213390A (en) | 1985-07-11 | 1985-07-11 | Thermal recording material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60153483A JPS6213390A (en) | 1985-07-11 | 1985-07-11 | Thermal recording material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6213390A JPS6213390A (en) | 1987-01-22 |
| JPH0356677B2 true JPH0356677B2 (en) | 1991-08-28 |
Family
ID=15563557
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP60153483A Granted JPS6213390A (en) | 1985-07-11 | 1985-07-11 | Thermal recording material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6213390A (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2528905B2 (en) * | 1987-10-27 | 1996-08-28 | 三菱製紙株式会社 | Method for manufacturing thermosensitive recording medium |
| JPH0756217Y2 (en) * | 1988-04-08 | 1995-12-25 | 凸版印刷株式会社 | Information card |
| EP1315043A1 (en) * | 2001-11-27 | 2003-05-28 | Fujitsu Limited | Resist pattern thickening material, resist pattern and forming process thereof, and semiconductor device and manufacturing process thereof |
| US7189783B2 (en) | 2001-11-27 | 2007-03-13 | Fujitsu Limited | Resist pattern thickening material, resist pattern and forming process thereof, and semiconductor device and manufacturing process thereof |
| JP2007245379A (en) * | 2006-03-14 | 2007-09-27 | Oji Paper Co Ltd | Thermosensitive recording body |
-
1985
- 1985-07-11 JP JP60153483A patent/JPS6213390A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6213390A (en) | 1987-01-22 |
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