JP2530901C - - Google Patents
Info
- Publication number
- JP2530901C JP2530901C JP2530901C JP 2530901 C JP2530901 C JP 2530901C JP 2530901 C JP2530901 C JP 2530901C
- Authority
- JP
- Japan
- Prior art keywords
- undercoat layer
- parts
- methyl
- layer
- oil
- 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
- 239000000049 pigment Substances 0.000 claims description 20
- 238000010521 absorption reaction Methods 0.000 claims description 10
- 239000000853 adhesive Substances 0.000 claims description 9
- 230000001070 adhesive Effects 0.000 claims description 9
- 239000002562 thickening agent Substances 0.000 claims description 9
- 229920000126 Latex Polymers 0.000 claims description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 8
- 239000004816 latex Substances 0.000 claims description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 5
- PZZYQPZGQPZBDN-UHFFFAOYSA-N Aluminium silicate Chemical compound O=[Al]O[Si](=O)O[Al]=O PZZYQPZGQPZBDN-UHFFFAOYSA-N 0.000 claims description 4
- 239000005995 Aluminium silicate Substances 0.000 claims description 3
- 235000012211 aluminium silicate Nutrition 0.000 claims description 3
- 239000010410 layer Substances 0.000 description 64
- 238000000576 coating method Methods 0.000 description 34
- 239000011248 coating agent Substances 0.000 description 31
- 239000007788 liquid Substances 0.000 description 13
- -1 silver halide Chemical class 0.000 description 13
- 239000000126 substance Substances 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- 230000035945 sensitivity Effects 0.000 description 11
- 239000000975 dye Substances 0.000 description 10
- 239000000203 mixture Substances 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- 230000000694 effects Effects 0.000 description 9
- 239000002609 media Substances 0.000 description 9
- 230000002378 acidificating Effects 0.000 description 7
- 239000004927 clay Substances 0.000 description 7
- 229910052570 clay Inorganic materials 0.000 description 7
- 229920001577 copolymer Polymers 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 7
- 229920002472 Starch Polymers 0.000 description 6
- 239000000981 basic dye Substances 0.000 description 6
- VTYYLEPIZMXCLO-UHFFFAOYSA-L calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 235000019698 starch Nutrition 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 5
- 239000008107 starch Substances 0.000 description 5
- LNAZSHAWQACDHT-XIYTZBAFSA-N (2R,3R,4S,5R,6S)-4,5-dimethoxy-2-(methoxymethyl)-3-[(2S,3R,4S,5R,6R)-3,4,5-trimethoxy-6-(methoxymethyl)oxan-2-yl]oxy-6-[(2R,3R,4S,5R,6R)-4,5,6-trimethoxy-2-(methoxymethyl)oxan-3-yl]oxyoxane Chemical compound CO[C@@H]1[C@@H](OC)[C@H](OC)[C@@H](COC)O[C@H]1O[C@H]1[C@H](OC)[C@@H](OC)[C@H](O[C@H]2[C@@H]([C@@H](OC)[C@H](OC)O[C@@H]2COC)OC)O[C@@H]1COC LNAZSHAWQACDHT-XIYTZBAFSA-N 0.000 description 4
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-Hydroxybenzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 4
- 229940090248 4-hydroxybenzoic acid Drugs 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000011247 coating layer Substances 0.000 description 4
- 230000001965 increased Effects 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
- 229920002451 polyvinyl alcohol Polymers 0.000 description 4
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 4
- 229960003563 Calcium Carbonate Drugs 0.000 description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 description 3
- 238000007906 compression Methods 0.000 description 3
- 239000000839 emulsion Substances 0.000 description 3
- 238000005755 formation reaction Methods 0.000 description 3
- 150000003951 lactams Chemical class 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 229920002225 poly(styrene-co-butadiene) Polymers 0.000 description 3
- 239000004576 sand Substances 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 125000005274 4-hydroxybenzoic acid group Chemical group 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N Benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- MOZDKDIOPSPTBH-UHFFFAOYSA-N Benzyl parahydroxybenzoate Chemical compound C1=CC(O)=CC=C1C(=O)OCC1=CC=CC=C1 MOZDKDIOPSPTBH-UHFFFAOYSA-N 0.000 description 2
- 229920002134 Carboxymethyl cellulose Polymers 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
- YGSDEFSMJLZEOE-UHFFFAOYSA-N Salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 2
- 229940005550 Sodium alginate Drugs 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N TiO Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 2
- 238000007792 addition Methods 0.000 description 2
- 150000001447 alkali salts Chemical class 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N benzohydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 description 2
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 2
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- IWGFEQWCMAADJZ-UHFFFAOYSA-N dibenzyl benzene-1,4-dicarboxylate Chemical compound C=1C=C(C(=O)OCC=2C=CC=CC=2)C=CC=1C(=O)OCC1=CC=CC=C1 IWGFEQWCMAADJZ-UHFFFAOYSA-N 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 239000001023 inorganic pigment Substances 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000001254 oxidized starch Substances 0.000 description 2
- 235000013808 oxidized starch Nutrition 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- MSXHSNHNTORCAW-UHFFFAOYSA-M sodium 3,4,5,6-tetrahydroxyoxane-2-carboxylate Chemical compound [Na+].OC1OC(C([O-])=O)C(O)C(O)C1O MSXHSNHNTORCAW-UHFFFAOYSA-M 0.000 description 2
- 235000010413 sodium alginate Nutrition 0.000 description 2
- 239000000661 sodium alginate Substances 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 229910001929 titanium oxide Inorganic materials 0.000 description 2
- OKJFKPFBSPZTAH-UHFFFAOYSA-N (2,4-dihydroxyphenyl)-(4-hydroxyphenyl)methanone Chemical compound C1=CC(O)=CC=C1C(=O)C1=CC=C(O)C=C1O OKJFKPFBSPZTAH-UHFFFAOYSA-N 0.000 description 1
- 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
- LGXVIGDEPROXKC-UHFFFAOYSA-N 1,1-Dichloroethene Chemical compound ClC(Cl)=C LGXVIGDEPROXKC-UHFFFAOYSA-N 0.000 description 1
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-Naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 1
- AGPLQTQFIZBOLI-UHFFFAOYSA-N 1-benzyl-4-phenylbenzene Chemical group C=1C=C(C=2C=CC=CC=2)C=CC=1CC1=CC=CC=C1 AGPLQTQFIZBOLI-UHFFFAOYSA-N 0.000 description 1
- UIFAEJQCFLEWCF-UHFFFAOYSA-N 1-methyl-4-[2-(4-methylphenoxy)ethoxy]benzene Chemical compound C1=CC(C)=CC=C1OCCOC1=CC=C(C)C=C1 UIFAEJQCFLEWCF-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
- ZXDDPOHVAMWLBH-UHFFFAOYSA-N 2,4-Dihydroxybenzophenone Chemical compound OC1=CC(O)=CC=C1C(=O)C1=CC=CC=C1 ZXDDPOHVAMWLBH-UHFFFAOYSA-N 0.000 description 1
- JWAZRIHNYRIHIV-UHFFFAOYSA-N 2-Naphthol Chemical compound C1=CC=CC2=CC(O)=CC=C21 JWAZRIHNYRIHIV-UHFFFAOYSA-N 0.000 description 1
- MQXNNWDXHFBFEB-UHFFFAOYSA-N 2-[2-(2-hydroxyphenyl)propan-2-yl]phenol Chemical compound C=1C=CC=C(O)C=1C(C)(C)C1=CC=CC=C1O MQXNNWDXHFBFEB-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
- WLTCCDHHWYAMCG-UHFFFAOYSA-N 2-phenylmethoxynaphthalene Chemical compound C=1C=C2C=CC=CC2=CC=1OCC1=CC=CC=C1 WLTCCDHHWYAMCG-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
- KGRVJHAUYBGFFP-UHFFFAOYSA-N 2-tert-butyl-6-[(3-tert-butyl-2-hydroxy-5-methylphenyl)methyl]-4-methylphenol 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
- QUINKWASVQHVID-UHFFFAOYSA-N 3,3-bis[4-(dimethylamino)phenyl]-2-benzofuran-1-one Chemical compound C1=CC(N(C)C)=CC=C1C1(C=2C=CC(=CC=2)N(C)C)C2=CC=CC=C2C(=O)O1 QUINKWASVQHVID-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
- DCDJMTJURABFMR-UHFFFAOYSA-N 3-(2-methyl-1H-indol-3-yl)-3H-2-benzofuran-1-one Chemical compound O1C(=O)C2=CC=CC=C2C1C1=C(C)NC2=CC=CC=C21 DCDJMTJURABFMR-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
- 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
- JCGRUCSGOUFSCY-UHFFFAOYSA-N 3-chloro-2-hydroxy-5-(1-phenylethyl)benzoic acid Chemical compound C=1C(Cl)=C(O)C(C(O)=O)=CC=1C(C)C1=CC=CC=C1 JCGRUCSGOUFSCY-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
- SDDLEVPIDBLVHC-UHFFFAOYSA-N 4,4'-cyclohexane-1,1-diyldiphenol Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)CCCCC1 SDDLEVPIDBLVHC-UHFFFAOYSA-N 0.000 description 1
- VWGKEVWFBOUAND-UHFFFAOYSA-N 4,4'-thiodiphenol Chemical compound C1=CC(O)=CC=C1SC1=CC=C(O)C=C1 VWGKEVWFBOUAND-UHFFFAOYSA-N 0.000 description 1
- ZTILAOCGFRDHBH-UHFFFAOYSA-N 4-(4-propan-2-yloxyphenyl)sulfonylphenol Chemical compound C1=CC(OC(C)C)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 ZTILAOCGFRDHBH-UHFFFAOYSA-N 0.000 description 1
- NPFYZDNDJHZQKY-UHFFFAOYSA-N 4-Hydroxybenzophenone Chemical compound C1=CC(O)=CC=C1C(=O)C1=CC=CC=C1 NPFYZDNDJHZQKY-UHFFFAOYSA-N 0.000 description 1
- VHLLJTHDWPAQEM-UHFFFAOYSA-N 4-[2-(4-hydroxyphenyl)-4-methylpentan-2-yl]phenol Chemical compound C=1C=C(O)C=CC=1C(C)(CC(C)C)C1=CC=C(O)C=C1 VHLLJTHDWPAQEM-UHFFFAOYSA-N 0.000 description 1
- KFMASHHCLJTUDI-UHFFFAOYSA-N 4-[2-[2,2-bis[4-(dimethylamino)phenyl]-1-phenylethoxy]-1-[4-(dimethylamino)phenyl]-2-phenylethyl]-N,N-dimethylaniline Chemical compound C1=CC(N(C)C)=CC=C1C(C=1C=CC(=CC=1)N(C)C)C(C=1C=CC=CC=1)OC(C=1C=CC=CC=1)C(C=1C=CC(=CC=1)N(C)C)C1=CC=C(N(C)C)C=C1 KFMASHHCLJTUDI-UHFFFAOYSA-N 0.000 description 1
- PVFQHGDIOXNKIC-UHFFFAOYSA-N 4-[2-[3-[2-(4-hydroxyphenyl)propan-2-yl]phenyl]propan-2-yl]phenol Chemical compound C=1C=CC(C(C)(C)C=2C=CC(O)=CC=2)=CC=1C(C)(C)C1=CC=C(O)C=C1 PVFQHGDIOXNKIC-UHFFFAOYSA-N 0.000 description 1
- 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 1
- ISAVYTVYFVQUDY-UHFFFAOYSA-N 4-tert-Octylphenol Chemical compound CC(C)(C)CC(C)(C)C1=CC=C(O)C=C1 ISAVYTVYFVQUDY-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
- CWSZBVAUYPTXTG-UHFFFAOYSA-N 5-[6-[[3,4-dihydroxy-6-(hydroxymethyl)-5-methoxyoxan-2-yl]oxymethyl]-3,4-dihydroxy-5-[4-hydroxy-3-(2-hydroxyethoxy)-6-(hydroxymethyl)-5-methoxyoxan-2-yl]oxyoxan-2-yl]oxy-6-(hydroxymethyl)-2-methyloxane-3,4-diol Chemical compound O1C(CO)C(OC)C(O)C(O)C1OCC1C(OC2C(C(O)C(OC)C(CO)O2)OCCO)C(O)C(O)C(OC2C(OC(C)C(O)C2O)CO)O1 CWSZBVAUYPTXTG-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
- IPAJDLMMTVZVPP-UHFFFAOYSA-N 6-(dimethylamino)-3,3-bis[4-(dimethylamino)phenyl]-2-benzofuran-1-one 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
- WNROFYMDJYEPJX-UHFFFAOYSA-K Aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- PXKLMJQFEQBVLD-UHFFFAOYSA-N Bis(4-hydroxyphenyl)methane Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 1
- 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 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
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N Bisphenol S Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N Butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- 229960005069 Calcium Drugs 0.000 description 1
- JHLNERQLKQQLRZ-UHFFFAOYSA-N Calcium silicate Chemical compound [Ca+2].[Ca+2].[O-][Si]([O-])([O-])[O-] JHLNERQLKQQLRZ-UHFFFAOYSA-N 0.000 description 1
- 235000013162 Cocos nucifera Nutrition 0.000 description 1
- 240000007170 Cocos nucifera Species 0.000 description 1
- MDNWOSOZYLHTCG-UHFFFAOYSA-N Dichlorophene Chemical compound OC1=CC=C(Cl)C=C1CC1=CC(Cl)=CC=C1O MDNWOSOZYLHTCG-UHFFFAOYSA-N 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
- SDIXRDNYIMOKSG-UHFFFAOYSA-L Disodium methyl arsenate Chemical compound [Na+].[Na+].C[As]([O-])([O-])=O SDIXRDNYIMOKSG-UHFFFAOYSA-L 0.000 description 1
- 239000001856 Ethyl cellulose Substances 0.000 description 1
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 1
- NUVBSKCKDOMJSU-UHFFFAOYSA-N Ethylparaben Chemical compound CCOC(=O)C1=CC=C(O)C=C1 NUVBSKCKDOMJSU-UHFFFAOYSA-N 0.000 description 1
- FWQHNLCNFPYBCA-UHFFFAOYSA-N Fluoran Chemical compound C12=CC=CC=C2OC2=CC=CC=C2C11OC(=O)C2=CC=CC=C21 FWQHNLCNFPYBCA-UHFFFAOYSA-N 0.000 description 1
- MDQRDWAGHRLBPA-UHFFFAOYSA-N Fluoroamine Chemical compound FN MDQRDWAGHRLBPA-UHFFFAOYSA-N 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- 240000008528 Hevea brasiliensis Species 0.000 description 1
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 1
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L Magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000004368 Modified starch Substances 0.000 description 1
- 229920000881 Modified starch Polymers 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
- 229910000503 Na-aluminosilicate Inorganic materials 0.000 description 1
- FATBGEAMYMYZAF-KTKRTIGZSA-N Oleamide Chemical compound CCCCCCCC\C=C/CCCCCCCC(N)=O FATBGEAMYMYZAF-KTKRTIGZSA-N 0.000 description 1
- KDVYCTOWXSLNNI-UHFFFAOYSA-N Para-tert-Butylbenzoic acid Chemical compound CC(C)(C)C1=CC=C(C(O)=O)C=C1 KDVYCTOWXSLNNI-UHFFFAOYSA-N 0.000 description 1
- TXFPEBPIARQUIG-UHFFFAOYSA-N Piceol Chemical compound CC(=O)C1=CC=C(O)C=C1 TXFPEBPIARQUIG-UHFFFAOYSA-N 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- QELSKZZBTMNZEB-UHFFFAOYSA-N Propylparaben Chemical compound CCCOC(=O)C1=CC=C(O)C=C1 QELSKZZBTMNZEB-UHFFFAOYSA-N 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N Sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M Sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 1
- 239000002174 Styrene-butadiene Substances 0.000 description 1
- FKHIFSZMMVMEQY-UHFFFAOYSA-N Talc Chemical compound [Mg+2].[O-][Si]([O-])=O FKHIFSZMMVMEQY-UHFFFAOYSA-N 0.000 description 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 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
- 239000006096 absorbing agent Substances 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
- 238000007754 air knife coating Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminum Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229920002892 amber Polymers 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- JPIYZTWMUGTEHX-UHFFFAOYSA-N auramine O free base Chemical compound C1=CC(N(C)C)=CC=C1C(=N)C1=CC=C(N(C)C)C=C1 JPIYZTWMUGTEHX-UHFFFAOYSA-N 0.000 description 1
- 125000005605 benzo group Chemical group 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- YXVFYQXJAXKLAK-UHFFFAOYSA-N biphenyl-4-ol Chemical compound C1=CC(O)=CC=C1C1=CC=CC=C1 YXVFYQXJAXKLAK-UHFFFAOYSA-N 0.000 description 1
- WXNRYSGJLQFHBR-UHFFFAOYSA-N bis(2,4-dihydroxyphenyl)methanone Chemical compound OC1=CC(O)=CC=C1C(=O)C1=CC=C(O)C=C1O WXNRYSGJLQFHBR-UHFFFAOYSA-N 0.000 description 1
- QUEICCDHEFTIQD-UHFFFAOYSA-N buta-1,3-diene;2-ethenylpyridine;styrene Chemical compound C=CC=C.C=CC1=CC=CC=C1.C=CC1=CC=CC=N1 QUEICCDHEFTIQD-UHFFFAOYSA-N 0.000 description 1
- KLIYQWXIWMRMGR-UHFFFAOYSA-N buta-1,3-diene;methyl 2-methylprop-2-enoate Chemical compound C=CC=C.COC(=O)C(C)=C KLIYQWXIWMRMGR-UHFFFAOYSA-N 0.000 description 1
- NTXGQCSETZTARF-UHFFFAOYSA-N buta-1,3-diene;prop-2-enenitrile Chemical compound C=CC=C.C=CC#N NTXGQCSETZTARF-UHFFFAOYSA-N 0.000 description 1
- ZUOTXZHOGPQFIU-UHFFFAOYSA-N butan-2-yl 4-hydroxybenzoate Chemical compound CCC(C)OC(=O)C1=CC=C(O)C=C1 ZUOTXZHOGPQFIU-UHFFFAOYSA-N 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- 235000012241 calcium silicate Nutrition 0.000 description 1
- 239000005018 casein Substances 0.000 description 1
- 235000021240 caseins Nutrition 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 235000010980 cellulose Nutrition 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007766 curtain coating Methods 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- CRPOUZQWHJYTMS-UHFFFAOYSA-N dialuminum;magnesium;disilicate Chemical compound [Mg+2].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-] CRPOUZQWHJYTMS-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 239000002612 dispersion media Substances 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 230000002708 enhancing Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 235000019325 ethyl cellulose Nutrition 0.000 description 1
- 229920001249 ethyl cellulose Polymers 0.000 description 1
- 235000010228 ethyl p-hydroxybenzoate Nutrition 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000007850 fluorescent dye Substances 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
- 238000007756 gravure coating Methods 0.000 description 1
- HSEMFIZWXHQJAE-UHFFFAOYSA-N hexadecanamide Chemical compound CCCCCCCCCCCCCCCC(N)=O HSEMFIZWXHQJAE-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 1
- 230000001771 impaired Effects 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- VQTUBCCKSQIDNK-UHFFFAOYSA-N isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 239000011776 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 239000000391 magnesium silicate Substances 0.000 description 1
- 229910052919 magnesium silicate Inorganic materials 0.000 description 1
- 235000019792 magnesium silicate Nutrition 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 238000002156 mixing Methods 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
- 229920001194 natural rubber Polymers 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- LYRFLYHAGKPMFH-UHFFFAOYSA-N octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(N)=O LYRFLYHAGKPMFH-UHFFFAOYSA-N 0.000 description 1
- 239000012169 petroleum derived wax Substances 0.000 description 1
- 235000019381 petroleum wax Nutrition 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- QHDYIMWKSCJTIM-UHFFFAOYSA-N phenyl 1-hydroxynaphthalene-2-carboxylate Chemical compound C1=CC2=CC=CC=C2C(O)=C1C(=O)OC1=CC=CC=C1 QHDYIMWKSCJTIM-UHFFFAOYSA-N 0.000 description 1
- GJLNWLVPAHNBQN-UHFFFAOYSA-N phenyl 4-hydroxybenzoate Chemical compound C1=CC(O)=CC=C1C(=O)OC1=CC=CC=C1 GJLNWLVPAHNBQN-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- HXHCOXPZCUFAJI-UHFFFAOYSA-N prop-2-enoic acid;styrene Chemical compound OC(=O)C=C.C=CC1=CC=CC=C1 HXHCOXPZCUFAJI-UHFFFAOYSA-N 0.000 description 1
- 235000010232 propyl p-hydroxybenzoate Nutrition 0.000 description 1
- 229960003415 propylparaben Drugs 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 238000001454 recorded image Methods 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 229960004889 salicylic acid Drugs 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 231100000489 sensitizer Toxicity 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000000429 sodium aluminium silicate Substances 0.000 description 1
- 235000012217 sodium aluminium silicate Nutrition 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-M stearate Chemical compound CCCCCCCCCCCCCCCCCC([O-])=O QIQXTHQIDYTFRH-UHFFFAOYSA-M 0.000 description 1
- 239000011115 styrene butadiene Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 229920001897 terpolymer Polymers 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
- ATJFFYVFTNAWJD-UHFFFAOYSA-N tin hydride Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
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- 229920003169 water-soluble polymer Polymers 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
Description
【発明の詳細な説明】
【産業上の利用分野】
本発明は感熱記録体に関し、特に記録感度が極めて高く、優れた印字画素再現
性を有する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よく知ら
れている。
かかる感熱記録体は比較的安価であり、記録機器がコンパクトで且つその保守
も比較的容易である為、ファ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。
そして用途の多様化に伴い、低渡度から高濃度に至るいずれの領域においても
印字画素の再現性に優れ、かつ銀塩写真に匹敵する様な高画質の記録像が得られ
る感熱記録体への要望が高まりつつある。また、記録機器の高速化に伴い、動的
記録感度に優れた感熱記録体に対する要求も益々高まっている。
その為、支持体と記録層との間に下塗り層を形成する方法が各種提案されてお
り、例えば特開昭61-35281号公報には、２μｍ以下の一般顔料に石油系ワックス
を併用した下塗り層を形成し、下塗り層の平滑性を高め、記録層とヘッドとの密
着性を改良することによって高感度化する方法が提案されている。また、特開昭
61-274989 号公報には、吸油量が100cc/100g以上の吸油性顔料に記録層と同し呈
色剤を配合して動的感度を高める方法が提案されている。
【発明が解決しようとする課題】
しかし、これらの方法で下塗り層を形成しても必ずしも満足すべき感度を有す
る記録体は得られず、印字画素の再現性も不充分で、なお改良の余地が残されて
いる。
その為、本発明者等は下塗り層の組成等について鋭意研究の結果、上記の如き
方法で形成される下塗り層では、ワックスや呈色剤といった微細化物が顔料の空
隙を埋めて下塗り層を緻密化する為、下塗り層の断熱効果が損なわれ、結果的に
期待する程の高感度が得られないことを碓認するに至った。
そこで、主成分として使用される吸油性顔料の空隙性を最大限に活用し得る下
塗り層を形成して優れた断熱効果を発揮させ、しかも、均一な圧縮弾性を持たせ
ることによって、より一層の高画質化と高感度化を図る方法について、更に鋭意
研究の結果、本発明を完成するに至った。
【課題を解決するための手段】
本発明は、支持体と記録層との間に下塗り層を有する感熱記録体において、下
塗り層の主成分がJIS K 5101法に基づく吸油量が100cc/100g以上の吸油性顔料で
あり、下塗り層の全接着剤の５０重量％以上が０℃以下のTg点を有するラテック
スであり、下塗り層中に該吸油性顔料１００重量部に対して０．０５〜５重量部
のアクリル系増粘剤が含有し、且つ乾燥後の下塗り層の塗布量が１２ｇ／ｍ2以
上で、その密度が０．７５ｇ／ｃｍ3以下であることを特徴とする感熱記録体で
ある。
【作用】
本発明の感熱記録体において、下塗り層を構成する吸油性顔料としては、JIS
k 5101法に基づく吸油量が100cc/100g以上のものが選択的に使用される。具体的
には、例えば焼成クレー、珪酸アルミニウム、珪酸カルシウム、珪酸マグネシウ
ム、アルミノ珪酸ソーダ、アルミノ珪酸マグネシウム、無定形シリカ等で上記特
定の吸油量を有するもの、或いは一般の顔料を物理的、化学的に処理して特定の
吸油量を有するようにした無機や有機の顔料が挙げられるが、中でも、焼成クレ
ーと無定形シリカは断熱性と圧縮弾性に優れている為、最も好ましく使用される
。
因みに、一般的なクレー、炭酸カルシウム、炭酸マグネシウム、酸化チタン、
水酸化アルミニウム等の顔料を主成分として使用しても、充分な断熱性と圧縮弾
性は得られず、記録層とサーマルヘッドとの密着性も悪く、満足すべき動的感度
を得ることはできない。
本発明では、上記の如き吸油性顔料の接着剤として、０℃以下のTg点を有する
ラテックスを使用するものである。その配合割合を全接着剤の５０重量％以上と
する必要がある。このような配合によってラテックスの有する優れたゴム弾性と
強い接着力が有効に作用し、ポーラスな吸油性顔料の空隙性をさほど損なうこと
なく、少ない接着剤量で顔料を支持体に結着し、しかも、ラテックスの有する柔
軟性も作用して記録層とサーマルヘッドとめ密着性が改善されるため、高画質で
高感度な感熱記録体が得られるものである。
０℃以下のTg点を有するラテックスの具体例としては、例えば天然ゴム、ポリ
ブタジエン、スチレン−ブタジエン系共重合体、アクリロニトリル−ブタジエン
系共重合体、メチルメタクリレート−ブタジエン系共重合体、２−ビニルピリジ
ン−スチレン−ブタジエン共重合体、アクリレート系重合体、アクリレート−ス
チレン系共重合体、塩化ビニル系重合体、塩化ビニリデン系重合体等が挙げられ
るが、勿論、これらに限定されるものではない。
また、これらのラテックス類と併用される接着剤も特に限定されず、例えば酸
化澱粉、酸素変性澱粉、カチオン澱粉、エステル化澱粉、エーテル化澱粉などの
澱粉類、メチルセルロース、エチルセルロース、カルボキシメチルセルロース、
メトキシセルロース、ヒドロキシエチルセルロースなどのセルロース誘導体、完
全（又は部分）鹸化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などのポリビニルアルコール類、ポ
リアクリル酸ソーダ、ポリアクリルアミド、ポリビニルピロリドン、アクリル酸
アミド／アクリル酸エステル共重合体、アクリル酸アミド／アクリル酸エステル
／メタクリル酸３元共重合体、スチレン／無水マレイン酸共重合体アルカリ塩、
イソブチレン／無水マレイン酸共重合体アルカリ塩、アルギン酸ソーダ、ゼラチ
ン、カゼイン等の水溶性高分子等が例示される。
なお、接着剤の使用量は上記特定のラテックスを含め、下塗り層塗液全固形分
の２〜４０重量％、好ましくは５〜２０重量％程度の範囲で調節するのが望まし
い。
下塗り層塗液中には、さらに必要に応じて分散剤、消泡剤、着色染料、蛍光染
料などの各種助剤を適宜添加することができるが、本発明の特殊な塗液配合との
関連で、アクリル系の増粘剤が吸油性顔料１００重量部に対して、０．０５〜５
重量％程度添加される。特定量のアクリル系の増粘剤を添加することにより動的
感度や高画質化が極めて顕著に改良される。
アクリル系増粘剤としては、非架橋型のアルカリ可溶性エマルジョンや架橋型
のアルカリ膨潤性エマルジョンをアクリル系ポリマーの主成分とする材料があり
、これらはアンモニアやカセイソーダ等のアルカリ添加によって、溶解或いは膨
潤してポリマーと水との水素結合或いはポリマーへの水分子の包含といった物理
作用によって増粘現象を起こす物質である。
特に、これらのアクリル系増粘剤は、エマルジョンタイプである為、比較的固
形分濃度が高く、結果的に高濃度塗液の調製が可能であり、しかも少量の添加で
充分な増粘効果を発揮する為、カルボキシメチルセルロース、メチルセルロース
、アルギン酸ソーダといった通常の増粘剤に比較して顔料の空隙性を損なう度合
いが極めて低い。
かくして調製された下塗り層塗液は支持体上に塗布されるが、乾燥後の塗布量
が１２ｇ／ｍ2未満では、本発明の所望の効果を得ることはできず、さらに形成
された下塗り層の密度が０．７５ｇ／ｃｍ3を越えると、やはり所望の効果を得
ることができない。その為、１２ｇ／ｍ2以上の下塗り層を形成する必要がある
が、過度に塗布量を上げ、例えば２５ｇ／ｍ2を越えるような下塗り層を形成す
ると、得られる記録体の取扱適性が低下し、例えばカッティング時に紙粉が多量
に発生するといった問題が派生する。その為、下塗り層の塗布量は１２〜２５ｇ
／ｍ2の範囲でで調節するのが望ましい。
また、下塗り層の密度が０．７５ｇ／ｃｍ3を越えると、下塗り層の主成分で
ある吸油性顔料の空隙性が最大限に活用されず、結果的に動的感度の改良効果が
不充分となる為、０．７５ｇ／ｃｍ3以下の密度となるように下塗り層を形成す
る必要がある。
その為、下塗り層の塗工方法も塗布層の緻密化が促進されるブレードコーティ
ング等は避けるのが望ましく、エアーナイフコーティング、バーコーティング、
グラビアコーティング、カーテンコーティング等の塗工方法が好ましく適用され
るが、もちろん密度が０．７５ｇ／ｃｍ3以下となるようにブレードのチューブ
圧を調節したブレードコーティングは本発明の有効な塗工方法である。また、記
録層を形成する前に下塗り層表面をスーパーキャレンダー等で処理するのも、本
発明の感熱記録体では避けるのが望ましい。
なお、本発明でいう下塗り層の密度は、下塗り層の乾燥塗布量をその下塗り層
の厚さ（支持体込みの厚さから支持体の厚さを引いた値）で割った値として算出
される。
本発明の感熱記録体は、かくして形成された特定の下塗り層上に記録層を設け
ることによって製造されるが、記録層を構成する発色剤と呈色剤としては、無色
ないしは淡色の塩基性染料と酸性物質との組合わせが好ましく使用される。
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−ジメチルアミノフェニル）−６−ジメチルアミノフタリド、
３，３−ビス（ｐ−ジメチルアミノフェニル）フタリド、３−（ｐ−ジメチルア
ミノフェニル）−３−（１，２−ジメチルインドール−３−イル）フタリド、３
−（ｐ−ジメチルアミノフェニル）−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−フェニルインドール
−３−イル）−６−ジメチルアミノフタリド、３−ｐ−ジメチルアミノフェニル
−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−ハロフェニル−ロイコオーラミン、Ｎ−２，４，５−トリクロ
ロフェニルロイコオーラミン等のジフェニルメタン系染料、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−フェニル−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−ジメチルフルオラン、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−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−フェニルアミノ
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−フェニルアミノ
フルオラン、３−ジブチルアミノ−６−メチル−７−フェ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−フェニルアミノ）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−フェニ
ルアミノフルオラン、３−ピロリジノ−６−メチル−７−フェニルアミノフルオ
ラン、３−ピペリジノ−６−メチル−７−フェ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−クロロフェニルアミノ）フルオラン、３−ジブチルアミノ−７−（ｏ−
クロロフェニルアミノ）フルオラン、３−ピロリジノ−６−メチル−７−ｐ−ブ
チルフェ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−フェニルアミノフルオラン、３−（Ｎ−エチル−Ｎ−ｎ−アミ
ル）アミノ−６−メチル−７−フェ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−フェ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−フェニルアミノフル
オラン、３−（Ｎ−エチル−Ｎ−ｎ−ヘキシル）アミノ−６−メチル−７−フェ
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−フェニルアミノフルオラン等のフルオラン系染料等
勿論、これらの染料に限定されるものではなく、二種以上の染料の併用も可能
である。
また、上記塩基性染料と組合せて使用される酸性物質についても各種の化合物
が知られており、例えば下記が例示される。
４−tert−ブチルフェノール、α−ナフトール、β−ナフトール、４−アセチル
フェノール、４−tert−オクチルフェノール、４，４′−sec −ブチリデンジフ
ェノール、４−フェニルフェノール、ハイドロキノン、４，４′−ジヒドロキシ
−ジフェニルメタン、４，４′−イソプロピリデンジフェノール、２，２−ビス
（４−ヒドロキシフェニル）−４−メチルペンタン、４，４′−シクロヘキシリ
デンジフェノール、４，４′−ジヒドロキシジフェニルサルファイド、４，４′
−チオビス（６−tert−ブチル−３−メチルフェノール）、４，４′−ジヒドロ
キシジフェニルスルホン、４−ヒドロキシ−４′−メチルジフェニルスルホン、
４−ヒドロキシ−４′−メトキシジフェニルスルホン、４−ヒドロキシ−４′−
イソプロポキシジフェニルスルホン、ヒドロキノンモノベンジルエーテル、４−
ヒドロキシベンゾフェノン、２，４−ジヒドロキシベンゾフェノン、２，４，４
′−トリヒドロキシベンゾフェノン、２，２′，４，４′−テトラヒドロキシベ
ンゾフェノン、２，２′−メチレンビス（４−クロルフェノール）、１，３−ジ
〔２−（４−ヒドロキシフェニル）−２−プロピル〕ベンゼン、ビス（３−アリ
ル−４−ヒドロキシフェニル）スルホン、４−ヒドロキシフタル酸ジメチル、４
−ヒドロキシ安息香酸メチル、４−ヒドロキシ安息香酸エチル、４−ヒドロキシ
安息香酸プロピル、４−ヒドロキシ安息香酸−sec −ブチル、４−ヒドロキシ安
息香酸ベンチル、４−ヒドロキシ安息香酸フェニル、４−ヒドロキシ安息香酸ベ
ンジル、４−ヒドロキシ安息香酸トリル、４−ヒドロキシ安息香酸クロロフェニ
ル、４−ヒドロキシ安息香酸フェニルアプロピル、４−ヒドロキシ安息香酸フェ
ネチル、４−ヒドロキシ安息香酸−ｐ−クロロベンジル、４−ヒドロキシ安息香
酸−ｐ−メトキシベンジル、ノボラック型フェノール樹脂、フェノール重合体等
のフェノール性化合物、安息香酸、ｐ−tert−ブチル安息香酸、トリクロル安息
香穀、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、
３，５−ジ−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−フェニル−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等の芳香族カルボン酸、およびこれらフェノー
ル性化合物、芳香族カルボン酸と例えば亜銘、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、ニッケル等の多価金属との塩等の有機酸性
物質等。なお、これらの酸性物質も勿論必要に応じて２種以上を併用することが
できる。
塩基性染料と酸性物質の使用比率は用いられる塩基性染料や酸性物質の種類に
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、一般に塩基性染料
１００重量部に対して１００〜７００重量部、好ましくは１５０〜４００重量部
程度の酸性物質が使用される。
これらを含む記録層用塗液の調製は、一般に水を分散媒体とし、ボールミル、
アトライター、サンドダラインダー等の攪拌・粉砕機により、染料と酸性物質と
を一緒に又は別々に分散するなどして調製される。
さらに、本発明の所望の効果を阻害しない範囲で、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、パルミチン酸アミド、
ヤシ脂肪酸アミド等の脂肪酸アミド、２，２′−メチレンビス（４−メチル−６
−tert−ブチルフェノール）、４，４′−ブチリデンビス（６−tert−ブチル− ３−メチルフェノール）
、１，１，３−トリス（２−メチル−４−ヒドロキシ−
５−tert−ブチルフェニル）ブタン等のヒンダードフェノール類、ｐ−ベンジル
ビフェニル、１，２−ビス（フェノキシ）エタン、１，２−ビス（４−メチルフ
ェノキシ）エタン、１，２−ビス（３−メチルフェノキシ）エタン、２−ナフト
ールベンジルエーテル等のエーテル類、ジベンジルテレフタレート、１−ヒドロ
キシ−２−ナフトエ酸フェニルエステル等のエステル類、２−（２′−ヒドロキ
シ−５′−メチルフェニル）ベンゾトリアゾール、２−ヒドロキシ−４−ベンジ
ルオキシベンゾフェノン等の紫外線吸収剤、および各種公知の熱可融性物質を増
感剤として添加することもできる。
加えて、記録ヘッドへのカス付着を改善するためにカオリン、クレー、タルク
、炭酸カルシウム、焼成クレー、酸化チタン、珪藻土、微粒子状無水シリカ、活
性白土等の無機顔料を添加することもできる。
本発明において、記録層の形成方法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って形成することができ、例えばエアーナイフコー
ター、ブレードコーター、バーコーター、グラビアコーター、カーテンコーター
等の適当な塗布装置が用いられる。また、塗液の塗布量についても特に限定され
るものではなく、一般に乾燥重量で２〜１２ｇ／ｍ2好ましくは３〜１０ｇ／ｍ2
の範囲で調節される。
なお、記録層上には記録層を保護する等の目的でオーバーコート層を設けるこ
とも可能であり、支持体の裏面に保護層を設けたり、さらには粘着加工を施すな
ど感熱記録体製造分野における各種の公知技術が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、特に断らない限り別中の部および％はそれぞれ重量部
および重量％を示す。
比較例１
〔下塗り層塗液の調製〕
吸油量160cc/100gの無定形シリカ（商品名：ミズカシールＰ−５２７、水沢化
学社製） １００部
スチレン−ブタジエン共重合体ラテックス（Tg点：−３５℃）（固形分換算）
１５部
ヒドロキシプロピル化澱粉（固形分換算） ５部
分散剤（固形分換算） ０．５部
この組成物を均一に混合し、固形分濃度３０％の下塗り層塗液を得た。
〔下塗り層の形成〕
４５ｇ／ｍ2の上質紙に上記下塗り層塗液を乾燥後の塗布量が１５ｇ／ｍ2とな
るようにバーコーターで塗布乾燥し、塗布層密度が０．６５ｇ／ｃｍ3の下塗り
塗布紙を得た。
〔記録層用塗液の調製〕
Ａ液調製
３−（Ｎ−シクロヘキシル−Ｎ−メチルアミノ）−６−メチル−７−フェニル
アミノフルオラン １０部
ジベンジルテレフタレート ２０部
メチルセルロース５％水溶液 １５部
水 ８０部
この組成物をサンドミルで平均粒子径が２μｍになるまで粉砕した。
Ｂ液調製
４，４′−イソプロピリデンジフェノール ３０部
メチルセルロース５％水溶液 ３０部
水 ７０部
この組成物をサンドミルで平均粒子経が２μｍになるまで粉砕した。
Ａ液１２５部、Ｂ液１３０部、無定形シリカ（吸油量180cc/100g）３０部、２
０％酸化澱粉水溶液１５０部、水５５部を攪拌・混合して記録層用塗液を調製し
た。
〔記録層の形成〕
得られた記録層用塗液を、前記下塗り塗布紙上に乾燥後の塗布量が５ｇ／ｍ2
となるようにマイヤーバーで塗布・乾燥して感熱記録紙を得た。
実施例１
下塗り層塗液の調製において、アクリル系増粘剤（非架橋型、商品名：ソマレ
ックス５０、ソマール社製）０．６部とアンモニア０．０２部を更に添加して塗
液調製を行った以外は比較例１と同様にして感熱記録紙を得た。なお、下塗り層
の塗布層密度は０．６２であった。
実施例２
アクリル系増粘剤を架橋型のアクリル系増粘剤（商品名：ビスカレックスＨＶ
３０、協和産業社製）を用いた以外は比較例１と同様にして感熱記録紙を得た。
なお、下塗り層の塗布層密度は０．６２ｇ／ｃｍ3であった。比較例２
下塗り層塗液の吸油性顔料を吸油量35cc/100g の通常の炭酸カルシウムに替え
る以外は比較例１と同様にして感熱記録紙を得た。なお、下塗り層の塗布層密度
は１．０３ｇ／ｃｍ3であった。比較例３ 下塗り層塗液の吸油性顔料を吸油量110cc/100gの焼成カオリンに替え、下塗り
層塗液をブレードコーターで塗布し、塗布層密度０．９３ｇ／ｃｍ3の下塗り層
を形成した以外は比較例１と同様にして感熱記録紙を得た。比較例４
下塗り層塗液の塗布量が１０ｇ／ｍ2で、塗布層密度が０．６７ｇ／ｃｍ3であ
る下塗り塗布紙を使用した以外は比較例１と同様にして感熱記録紙を得た。比較例５
下塗り層塗液の調製において、スチレン−ブタジエン共重合体ラテックスの配
合量を５部とし、ヒドロキシプロピル化澱粉の配合量を１５部に替えた以外は比
較例１と同様にして感熱記録紙を得た。なお、下塗り層の塗布層密度は０．７６
／ｃｍ3であった。
かくして得られた７種類の感熱記録紙を感熱プリンター（SONY VP−103、ビ
デオプリンター）を使用して、印字パルス時間５msecと８msecで記録し、各々の
発色濃度をマクベス濃度計（RD−100R型、アンバーフィルター使用）で測定し、
結果を表に記載した。また、得られた記録像の印字画素（ドット）再現性の評価
として、感熱ヘッドの１ドットの面積に対する印字されたドットの面積の割合（
ドット再現性）を以下の基準で評価し、その結果を表に併記した。
◎：ドット再現率８６％以上
○：ドット再現率７１〜８５％
△：ドット再現率６１〜７０％
×：ドット再現率６０％以下 【効果】
表の結果から明らかなように、本発明の実施例で得られた感熱記録紙は低濃度
から高濃度に至るいづれの領域においても印字画素の再現性に優れており、動的
感度も優れたいた。Description: BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermosensitive recording medium, and more particularly to a thermosensitive recording medium having extremely high recording sensitivity and excellent print pixel reproducibility. 2. Description of the Related Art Conventionally, a thermosensitive recording method in which a color-forming image is obtained by contacting both color-forming substances by heat using a color-forming reaction between a color-forming agent and a color-forming agent that forms a color by contacting the color-forming agent. The body is well known. Such a thermosensitive recording medium is relatively inexpensive, and its recording equipment is compact and its maintenance is relatively easy. Therefore, it is used not only as a recording medium for facsimile machines and various computers but also in a wide range of fields. With the diversification of applications, the heat-sensitive recording material excels in print pixel reproducibility and obtains high-quality recorded images comparable to silver halide photographs in any region from low passing to high density. Are increasing. Further, with the increase in the speed of the recording apparatus, a demand for a thermosensitive recording medium having excellent dynamic recording sensitivity is increasing. For this reason, various methods for forming an undercoat layer between the support and the recording layer have been proposed. For example, Japanese Patent Application Laid-Open No. 61-35281 discloses an undercoat using a petroleum wax in combination with a general pigment of 2 μm or less. A method has been proposed in which a layer is formed, the smoothness of the undercoat layer is increased, and the adhesion between the recording layer and the head is improved to increase the sensitivity. In addition,
Japanese Patent Application Laid-Open No. 61-274989 proposes a method for enhancing dynamic sensitivity by blending a color former with an oil absorbing pigment having an oil absorption of 100 cc / 100 g or more in the same manner as a recording layer. However, even if an undercoat layer is formed by these methods, it is not always possible to obtain a recording medium having a satisfactory sensitivity, the print pixel reproducibility is insufficient, and there is still room for improvement. Is left. Therefore, the present inventors have conducted intensive studies on the composition of the undercoat layer and the like. As a result, in the undercoat layer formed by the above-described method, a fine substance such as a wax or a coloring agent fills the voids of the pigment and densifies the undercoat layer. As a result, the heat insulating effect of the undercoat layer is impaired, and as a result, it has been confirmed that high sensitivity as expected cannot be obtained. Therefore, by forming an undercoat layer capable of maximizing the porosity of the oil-absorbing pigment used as a main component to exhibit an excellent heat-insulating effect, and by having a uniform compression elasticity, a further improvement is achieved. As a result of further intensive studies on a method for achieving high image quality and high sensitivity, the present invention has been completed. Means for Solving the Problems The present invention provides a thermosensitive recording medium having an undercoat layer between a support and a recording layer, wherein the main component of the undercoat layer has an oil absorption of 100 cc / 100 g or more based on JIS K 5101 method. Which has an Tg point of 0 ° C. or less in which 50% by weight or more of the total adhesive in the undercoat layer is an oil absorbing pigment.
Wherein the undercoat layer contains 0.05 to 5 parts by weight of an acrylic thickener based on 100 parts by weight of the oil-absorbing pigment, and the applied amount of the undercoat layer after drying is 12 g / m 2 or more. Wherein the density is 0.75 g / cm 3 or less. In the heat-sensitive recording material of the present invention, the oil absorbing pigment constituting the undercoat layer is JIS
Those having an oil absorption of 100 cc / 100 g or more based on the k 5101 method are selectively used. Specifically, for example, calcined clay, aluminum silicate, calcium silicate, magnesium silicate, sodium aluminosilicate, magnesium aluminosilicate, amorphous silica or the like having the above specific oil absorption amount, or a general pigment is physically or chemically. Inorganic or organic pigments having a specific oil absorption by treating the clay are preferred. Among them, calcined clay and amorphous silica are most preferably used because of their excellent heat insulating properties and compression elasticity. By the way, general clay, calcium carbonate, magnesium carbonate, titanium oxide,
Even if a pigment such as aluminum hydroxide is used as a main component, sufficient heat insulation and compression elasticity cannot be obtained, and the adhesion between the recording layer and the thermal head is poor, and satisfactory dynamic sensitivity cannot be obtained. . In the present invention, a latex having a Tg point of 0 ° C. or lower is used as an adhesive for the oil-absorbing pigment as described above. It is necessary that the compounding ratio be 50% by weight or more of the total adhesive. By such a composition, the excellent rubber elasticity and strong adhesive force of the latex effectively act, without significantly impairing the porosity of the porous oil-absorbing pigment, binding the pigment to the support with a small amount of adhesive, Moreover, the flexibility of the latex acts to improve the adhesion between the recording layer and the thermal head, so that a high-sensitivity thermosensitive recording medium with high image quality can be obtained. Specific examples of the latex having a Tg point of 0 ° C. or lower include, for example, natural rubber, polybutadiene, styrene-butadiene-based copolymer, acrylonitrile-butadiene-based copolymer, methyl methacrylate-butadiene-based copolymer, 2-vinylpyridine -Styrene-butadiene copolymer, acrylate-based polymer, acrylate-styrene-based copolymer, vinyl chloride-based polymer, vinylidene chloride-based polymer, and the like, but are not limited to these. Further, the adhesive used in combination with these latexes is not particularly limited, for example, oxidized starch, oxygen-modified starch, cationic starch, esterified starch, starches such as etherified starch, methylcellulose, ethylcellulose, carboxymethylcellulose,
Cellulose derivatives such as methoxycellulose and hydroxyethylcellulose, polyvinyl alcohols such as completely (or partially ) saponified polyvinyl alcohol, carboxy-modified polyvinyl alcohol, acetoacetylated polyvinyl alcohol, sodium polyacrylate, polyacrylamide, polyvinylpyrrolidone, acrylamide / Acrylic acid ester copolymer, acrylic acid amide / acrylic acid ester / methacrylic acid terpolymer, styrene / maleic anhydride copolymer alkali salt,
Water-soluble polymers such as isobutylene / maleic anhydride copolymer alkali salt, sodium alginate, gelatin and casein are exemplified. The amount of the adhesive used, including the specific latex described above, is desirably adjusted within the range of about 2 to 40% by weight, preferably about 5 to 20% by weight of the total solids of the undercoat layer coating solution. In the undercoat layer coating liquid, various auxiliary agents such as a dispersant, an antifoaming agent, a coloring dye, and a fluorescent dye can be appropriately added as needed. The acrylic thickener is used in an amount of 0.05 to 5 parts by weight based on 100 parts by weight of the oil absorbing pigment.
It is added in the order of% by weight. Dynamic by adding specific amount of acrylic thickener
Sensitivity and high image quality are significantly improved. Acrylic thickeners include non-crosslinkable alkali-soluble emulsions and crosslinkable alkali-swellable emulsions whose main component is an acrylic polymer, which are dissolved or swelled by the addition of alkali such as ammonia or caustic soda. It is a substance that causes a thickening phenomenon by a physical action such as hydrogen bonding between a polymer and water or inclusion of water molecules in the polymer. In particular, since these acrylic thickeners are emulsion types, they have a relatively high solids concentration, and as a result, a high-concentration coating solution can be prepared, and a sufficient thickening effect can be obtained with a small amount of addition. Since it exerts its effect, the degree of impairing the porosity of the pigment is extremely low as compared with ordinary thickeners such as carboxymethylcellulose, methylcellulose and sodium alginate. The undercoat layer coating solution thus prepared is coated on a support, but if the coating amount after drying is less than 12 g / m 2 , the desired effects of the present invention cannot be obtained, and the further formed undercoat layer If the density exceeds 0.75 g / cm 3 , the desired effect cannot be obtained. For this reason, it is necessary to form an undercoat layer of 12 g / m 2 or more. However, if the coating amount is excessively increased and, for example, an undercoat layer exceeding 25 g / m 2 is formed, the handleability of the obtained recording medium deteriorates. However, for example, a problem arises that a large amount of paper dust is generated during cutting. Therefore, the coating amount of the undercoat layer is 12 to 25 g.
/ M 2 is desirable. On the other hand, if the density of the undercoat layer exceeds 0.75 g / cm 3 , the porosity of the oil-absorbing pigment, which is the main component of the undercoat layer, is not utilized to the utmost, and as a result, the effect of improving the dynamic sensitivity is insufficient. Therefore, it is necessary to form an undercoat layer to have a density of 0.75 g / cm 3 or less. For this reason, it is desirable to avoid the undercoat layer coating method such as blade coating that promotes densification of the coating layer, such as air knife coating, bar coating, and the like.
Coating methods such as gravure coating and curtain coating are preferably applied. Of course, blade coating in which the tube pressure of the blade is adjusted so that the density is 0.75 g / cm 3 or less is an effective coating method of the present invention. is there. Further, it is desirable that the surface of the undercoat layer be treated with a super calender or the like before the formation of the recording layer in the heat-sensitive recording material of the present invention. The density of the undercoat layer in the present invention is calculated as a value obtained by dividing the dry coating amount of the undercoat layer by the thickness of the undercoat layer (the value obtained by subtracting the thickness of the support from the thickness including the support). You. The heat-sensitive recording material of the present invention is produced by providing a recording layer on the specific undercoat layer thus formed, and as a color former and a color former constituting the recording layer, a colorless or light-colored basic dye is used. And a combination of an acidic substance are preferably used. Various types of colorless or light-colored basic dyes are known, and examples thereof 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,
-(P-dimethylaminophenyl) -3- (2-methylindol-3-ylphthalide, 3,3-bis (1,2-dimethylindol-3-yl) -5-dimethylaminophthalide, 3,3- Bis (1,2-dimethylindol-3-yl)
-6-dimethylaminophthalide, 3,3-bis (9-ethylcarbazole-3-
Yl) -6-dimethylaminophthalide, 3,3-bis (2-phenylindol-3-yl) -6-dimethylaminophthalide, 3-p-dimethylaminophenyl-3- (1-methylpyrrole-3 -Yl) -6-dimethylaminophthalide and other triallylmethane dyes, 4,4'-bis-dimethylaminobenzhydrylbenzyl ether, N-halophenyl-leucouramine, N-2,4,5-tri Diphenylmethane dyes such as chlorophenylleuco auramine, thiazine dyes such as benzoyl leucomethylene blue, p-nitrobenzoyl leucomethylene blue, 3-methyl-spiro-dinaphthopyran, 3-ethyl-spiro-dinaphthopyran, 3-phenyl-spiro-dinaphthopyran, 3-benzyl-spiro-dinaphthopyran, 3-methyl- Spiro-based dyes such as ft (6'-methoxybenzo) spiropyran and 3-propyl-spiro-dibenzopyran; lactams such as rhodamine-B-anilinolactam, rhodamine (p-nitroanilino) lactam and rhodamine (o-chloroanilino) lactam Dyes, 3-dimethylamino-7-methoxyfluoran, 3-diethylamino-6-methoxyfluoran, 3-diethylamino-
7-methoxyfluoran, 3-diethylamino-7-chlorofluorane, 3-diethylamino-6-methyl-7-chlorofluoran, 3-diethylamino-6
7-dimethylfluoran, 3- (N-ethyl-p-toluidino) -7-methylfluoran, 3-diethylamino-7-N-acetyl-N-methylaminofluoran, 3-diethylamino-7-N-methyl Aminofluorane, 3-diethylamino-7-dibenzylaminofluoran, 3-diethylamino-7-N-methyl-
N-benzylaminofluoran, 3-diethylamino-7-N-chloroethyl-
N-methylaminofluoran, 3-diethylamino-7-diethylaminofluoran, 3- (N-ethyl-p-toluidino) -6-methyl-7-phenylaminofluoran, 3- (N-ethyl-p-toluidino ) -6-Methyl-7- (p-toluidino) fluoran, 3-diethylamino-6-methyl-7-phenylaminofluoran, 3-dibutylamino-6-methyl-7-phenylaminofluoran, 3-diethylamino- 7- (2-carbomethoxy-phenylamino) fluoran, 3- (N-cyclohexyl-N-methylamino) -6-methyl-7-phenylaminofluoran, 3-pyrrolidino-6-methyl-7-phenylaminofluor Oran, 3-piperidino-6-methyl-7-phenylaminofluoran, 3-diethylamino-6-methyl Le-7-xylylene Gino full Oran, 3-diethylamino -7
-(O-chlorophenylamino) fluoran, 3-dibutylamino-7- (o-chlorophenylamino) fluoran, 3-pyrrolidino-6-methyl-7-p-butylphenylaminofluoran, 3- (N-methyl-N -N-amyl) amino-
6-methyl-7-phenylaminofluoran, 3- (N-ethyl-NNn-amyl) amino-6-methyl-7-phenylaminofluoran, 3- (N-ethyl-
N-isoamyl) amino-6-methyl-7-phenylaminofluoran, 3- (
N-methyl-NN-hexyl) amino-6-methyl-7-phenylaminofluoran, 3- (N-ethyl-Nn-hexyl) amino-6-methyl-7-phenylaminofluoran, 3 -(N-ethyl-N-β-ethylhexyl) amino-
Fluorane-based dyes such as 6-methyl-7-phenylaminofluoran, etc. Of course, the dyes are not limited to these dyes, and two or more dyes can be used in combination. Also, various compounds are known for acidic substances used in combination with the basic dyes, and examples thereof include the following. 4-tert-butylphenol, α-naphthol, β-naphthol, 4-acetylphenol, 4-tert-octylphenol, 4,4′-sec-butylidenediphenol, 4-phenylphenol, hydroquinone, 4,4′-dihydroxy- Diphenylmethane, 4,4'-isopropylidenediphenol, 2,2-bis (4-hydroxyphenyl) -4-methylpentane, 4,4'-cyclohexylidenediphenol, 4,4'-dihydroxydiphenylsulfide, 4, 4 '
-Thiobis (6-tert-butyl-3-methylphenol), 4,4'-dihydroxydiphenylsulfone, 4-hydroxy-4'-methyldiphenylsulfone,
4-hydroxy-4'-methoxydiphenylsulfone, 4-hydroxy-4'-
Isopropoxydiphenyl sulfone, hydroquinone monobenzyl ether, 4-
Hydroxybenzophenone, 2,4-dihydroxybenzophenone, 2,4,4
'-Trihydroxybenzophenone, 2,2', 4,4'-tetrahydroxybenzophenone, 2,2'-methylenebis (4-chlorophenol), 1,3-di [2- (4-hydroxyphenyl) -2- Propyl] benzene, bis (3-allyl-4-hydroxyphenyl) sulfone, dimethyl 4-hydroxyphthalate,
-Methyl hydroxybenzoate, ethyl 4-hydroxybenzoate, propyl 4-hydroxybenzoate, sec-butyl 4-hydroxybenzoate, benzyl 4-hydroxybenzoate, phenyl 4-hydroxybenzoate, benzyl 4-hydroxybenzoate , 4-Hydroxybenzoic acid tolyl, 4-hydroxybenzoic acid chlorophenyl, 4-hydroxybenzoic acid phenylpropyl, 4-hydroxybenzoic acid phenethyl, 4-hydroxybenzoic acid-p-chlorobenzyl, 4-hydroxybenzoic acid-p- Phenolic compounds such as methoxybenzyl, novolak type phenolic resin, and phenolic polymer, benzoic acid, p-tert-butylbenzoic acid, trichlorobenzoic acid, terephthalic acid, 3-sec-butyl-4-hydroxybenzoic acid, 3-cyclohexyl -4-hydroxy Benzoic acid, 3,5-dimethyl-4-hydroxybenzoic acid, salicylic acid, 3-isopropyl salicylic acid, 3-tert-butyl salicylic acid,
3,5-di-tert-butylsalicylic acid, 3-benzylsalicylic acid, 3- (α-methylbenzyl) salicylic acid, 3-chloro-5- (α-methylbenzyl) salicylic acid, 3-phenyl-5- (α, α -Dimethylbenzyl) salicylic acid, aromatic carboxylic acids such as 3,5-di-α-methylbenzylsalicylic acid, and these phenolic compounds and aromatic carboxylic acids, for example, magnesium, aluminum, calcium, titanium, manganese, tin And organic acidic substances such as salts with polyvalent metals such as nickel. Of course, two or more of these acidic substances can be used as needed. Using the ratio of basic dye and an acidic substance as it is appropriately selected depending on the type of the basic dye or an acid substance to be used is not particularly limited, generally 100 to 100 parts by weight of the basic dye About 700 parts by weight, preferably about 150 to 400 parts by weight of an acidic substance is used. Preparation of the recording layer coating solution containing these, generally using water as a dispersion medium, ball mill,
It is prepared by, for example, dispersing the dye and the acidic substance together or separately using a stirrer / pulverizer such as an attritor or a sand liner. Further, as long as the desired effect of the present invention is not inhibited , for example, stearic acid amide, methylene bisamide stearate, oleic acid amide, palmitic acid amide,
Fatty acid amides such as coconut fatty acid amide, 2,2'-methylenebis (4-methyl-6
-Tert -butylphenol), 4,4'-butylidenebis (6-tert-butyl- 3-methylphenol) , 1,1,3-tris (2-methyl-4-hydroxy-
Hindered phenols such as 5-tert-butylphenyl) butane, p-benzylbiphenyl, 1,2-bis (phenoxy) ethane, 1,2-bis (4-methylphenoxy) ethane, 1,2-bis (3 Ethers such as -methylphenoxy) ethane and 2-naphthol benzyl ether; esters such as dibenzyl terephthalate and phenyl 1-hydroxy-2-naphthoate; 2- (2'-hydroxy-5'-methylphenyl) benzo UV absorbers such as triazole and 2-hydroxy-4-benzyloxybenzophenone, and various known heat-fusible substances can also be added as sensitizers. In addition, inorganic pigments such as kaolin, clay, talc, calcium carbonate, calcined clay, titanium oxide, diatomaceous earth, fine anhydrous silica, and activated clay can be added to improve the adhesion of scum to the recording head. In the present invention, the method for forming the recording layer is not particularly limited,
It can be formed according to a conventionally known and commonly used technique. For example, an appropriate coating device such as an air knife coater, a blade coater, a bar coater, a gravure coater, and a curtain coater is used. Also, there are no particular limitation on the coating amount of the coating liquid, 2~12g / m 2, preferably in generally dry weight 3 to 10 g / m 2
Is adjusted in the range. It is also possible to provide an overcoat layer on the recording layer for the purpose of protecting the recording layer, etc., and to provide a protective layer on the back surface of the support or to perform an adhesive process, for example. Various known techniques can be added. EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Examples, but it is needless to say that the present invention is not limited thereto. Unless otherwise specified, parts and% in the following mean parts and% by weight, respectively. Comparative Example 1 [Preparation of Undercoat Layer Coating Liquid] Amorphous silica having an oil absorption of 160 cc / 100 g (trade name: Mizuka Seal P-527, manufactured by Mizusawa Chemical Co., Ltd.) 100 parts Styrene-butadiene copolymer latex (Tg point: -35 ° C.) ) (Solid content) 15 parts Hydroxypropylated starch (solid content) 5 parts Dispersant (solid content) 0.5 parts This composition was uniformly mixed, and the undercoat layer coating solution having a solid concentration of 30% was prepared. Obtained. The quality paper of [Undercoat formation of layer] 45 g / m 2 the undercoat layer coating solution coating amount after drying was dried at a bar coater so that the 15 g / m 2, the coating layer density 0.65 g / cm 3 undercoated papers were obtained. [Preparation of Coating Solution for Recording Layer] Preparation of Solution A 3- (N-cyclohexyl-N-methylamino) -6-methyl-7-phenylaminofluoran 10 parts Dibenzyl terephthalate 20 parts Methyl cellulose 5% aqueous solution 15 parts Water 80 Part of this composition was pulverized with a sand mill until the average particle size became 2 μm. Solution B Preparation 4, 4 '- a isopropylidenediphenol 30 parts methyl cellulose 5% aqueous solution 30 parts Water 70 parts This composition is the mean particle through a sand mill and ground to a 2 [mu] m. Liquid A 125 parts, Liquid B 130 parts, amorphous silica (oil absorption 180cc / 100g) 30 parts, 2
150 parts of a 0% oxidized starch aqueous solution and 55 parts of water were stirred and mixed to prepare a coating liquid for a recording layer. [Formation of Recording Layer] The coating amount of the obtained recording layer coating solution after drying on the undercoated paper was 5 g / m 2.
The resultant was coated with a Meyer bar and dried to obtain a thermosensitive recording paper. Example 1 In the preparation of the undercoat layer coating liquid, 0.6 part of an acrylic thickener (non-crosslinked type, trade name: Somalex 50, manufactured by Somar) and 0.02 part of ammonia were further added to prepare the coating liquid. A thermosensitive recording paper was obtained in the same manner as in Comparative Example 1 except that the test was performed. The density of the undercoat layer was 0.62. Example 2 Crosslinkable acrylic thickener (trade name: Biscarex HV)
30, manufactured by Kyowa Sangyo Co., Ltd.), except that thermal recording paper was obtained in the same manner as in Comparative Example 1 .
The density of the undercoat layer was 0.62 g / cm 3 . Comparative Example 2 A thermosensitive recording paper was obtained in the same manner as in Comparative Example 1 , except that the oil-absorbing pigment in the undercoat layer coating liquid was replaced with ordinary calcium carbonate having an oil absorption of 35 cc / 100 g. The density of the undercoat layer was 1.03 g / cm 3 . Comparative Example 3 Except that the oil absorbing pigment in the undercoat layer coating liquid was changed to calcined kaolin with an oil absorption of 110 cc / 100 g , and the undercoat layer coating liquid was applied using a blade coater to form an undercoat layer having a coating layer density of 0.93 g / cm 3. Was obtained in the same manner as in Comparative Example 1. Comparative Example 4 A thermosensitive recording paper was obtained in the same manner as in Comparative Example 1, except that the undercoat layer coating liquid was applied in an amount of 10 g / m 2 and the coating layer density was 0.67 g / cm 3 . . Comparative Example 5 Thermal recording was performed in the same manner as in Comparative Example 1 except that the amount of the styrene-butadiene copolymer latex was changed to 5 parts and the amount of the hydroxypropylated starch was changed to 15 parts in the preparation of the undercoat layer coating liquid. I got the paper. The coating density of the undercoat layer was 0.76.
/ Cm 3 . Using the thermal printer (SONY VP-103, video printer), the seven types of thermal recording paper thus obtained were recorded with a print pulse time of 5 msec and 8 msec, and the color density of each was measured using a Macbeth densitometer (RD-100R type). , Using an amber filter)
The results are shown in the table. In addition, as an evaluation of print pixel (dot) reproducibility of the obtained recorded image, the ratio of the area of the printed dot to the area of one dot of the thermal head (dot reproducibility) was evaluated based on the following criteria. Are also shown in the table. ◎: 86% or more dot reproducibility ○: 71 to 85% dot reproducibility △: 61 to 70% dot reproducibility ×: 60% or less dot reproducibility [Effect] As is clear from the results in the table, the thermal recording paper obtained in the examples of the present invention has excellent print pixel reproducibility in any region from low density to high density, and has a high dynamic sensitivity. Was also excellent.
Claims (1)
下塗り層の主成分がJIS K 5101法に基づく吸油量が100cc/100g以上の吸油性顔料
であり、下塗り層の全接着剤の５０重量％以上が０℃以下のTg点を有するラテッ
クスであり、下塗り層中に該吸油性顔料１００重量部に対して０．０５〜５重量
部のアクリル系増粘剤が含有し、且つ乾燥後の下塗り層の塗布量が１２ｇ／ｍ2
以上で、その密度が０．７５ｇ／ｃｍ3以下であることを特徴とする感熱記録体
。 【請求項２】吸油性顔料が焼成カオリン又は無定形シリカである請求項１記載の
感熱記録体。Claims: 1. A thermosensitive recording medium having an undercoat layer between a support and a recording layer,
The main component of the undercoat layer is an oil-absorbing pigment having an oil absorption of 100 cc / 100 g or more based on the JIS K 5101 method, and 50% by weight or more of the entire adhesive of the undercoat layer is a latex having a Tg point of 0 ° C. or less, 0.05 to 5 parts by weight based on 100 parts by weight of the oil absorbing pigment in the undercoat layer
Parts of an acrylic thickener and the applied amount of the undercoat layer after drying is 12 g / m 2.
As described above, the thermosensitive recording medium has a density of 0.75 g / cm 3 or less. 2. The heat-sensitive recording material according to claim 1, wherein the oil-absorbing pigment is calcined kaolin or amorphous silica.
Family
ID=
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