EP0137982A1 - Feuille d'enregistrement sensible à la chaleur - Google Patents
Feuille d'enregistrement sensible à la chaleur Download PDFInfo
- Publication number
- EP0137982A1 EP0137982A1 EP84110091A EP84110091A EP0137982A1 EP 0137982 A1 EP0137982 A1 EP 0137982A1 EP 84110091 A EP84110091 A EP 84110091A EP 84110091 A EP84110091 A EP 84110091A EP 0137982 A1 EP0137982 A1 EP 0137982A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- phthalic acid
- heat
- sensitive recording
- recording sheet
- color developing
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims abstract description 51
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 26
- 229910052751 metal Inorganic materials 0.000 claims abstract description 23
- 239000002184 metal Substances 0.000 claims abstract description 23
- 239000000463 material Substances 0.000 claims abstract description 12
- -1 alkyl radical Chemical class 0.000 claims description 25
- 150000003839 salts Chemical class 0.000 claims description 16
- 239000006185 dispersion Substances 0.000 claims description 12
- 239000011248 coating agent Substances 0.000 claims description 8
- 238000000576 coating method Methods 0.000 claims description 8
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 239000011230 binding agent Substances 0.000 claims description 5
- 230000015572 biosynthetic process Effects 0.000 claims description 4
- 239000000945 filler Substances 0.000 claims description 4
- 125000005843 halogen group Chemical group 0.000 claims description 4
- XIKIUQUXDNHBFR-UHFFFAOYSA-N monobenzyl phthalate Chemical compound OC(=O)C1=CC=CC=C1C(=O)OCC1=CC=CC=C1 XIKIUQUXDNHBFR-UHFFFAOYSA-N 0.000 claims description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- 239000000654 additive Substances 0.000 claims description 3
- 229910052791 calcium Inorganic materials 0.000 claims description 3
- 239000011575 calcium Substances 0.000 claims description 3
- 239000008199 coating composition Substances 0.000 claims description 3
- 239000000314 lubricant Substances 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 239000011777 magnesium Substances 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 239000011701 zinc Substances 0.000 claims description 3
- SLRMQYXOBQWXCR-UHFFFAOYSA-N 2154-56-5 Chemical compound [CH2]C1=CC=CC=C1 SLRMQYXOBQWXCR-UHFFFAOYSA-N 0.000 claims description 2
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 238000000227 grinding Methods 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 125000006539 C12 alkyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims 1
- 230000000996 additive effect Effects 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 claims 1
- 238000000034 method Methods 0.000 claims 1
- 238000002156 mixing Methods 0.000 claims 1
- XOSNGXNHDRYFEF-UHFFFAOYSA-N monohexyl phthalate Chemical compound CCCCCCOC(=O)C1=CC=CC=C1C(O)=O XOSNGXNHDRYFEF-UHFFFAOYSA-N 0.000 claims 1
- 238000002360 preparation method Methods 0.000 claims 1
- 125000001174 sulfone group Chemical group 0.000 claims 1
- 239000000975 dye Substances 0.000 description 19
- 239000000243 solution Substances 0.000 description 18
- 229920002451 polyvinyl alcohol Polymers 0.000 description 11
- 239000004372 Polyvinyl alcohol Substances 0.000 description 8
- 239000003381 stabilizer Substances 0.000 description 8
- 239000003921 oil Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 150000002148 esters Chemical class 0.000 description 5
- 150000003457 sulfones Chemical class 0.000 description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical class C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 4
- 239000004359 castor oil Substances 0.000 description 4
- 235000019438 castor oil Nutrition 0.000 description 4
- 239000003086 colorant Substances 0.000 description 4
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical compound C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 description 4
- FWQHNLCNFPYBCA-UHFFFAOYSA-N fluoran Chemical compound C12=CC=CC=C2OC2=CC=CC=C2C11OC(=O)C2=CC=CC=C21 FWQHNLCNFPYBCA-UHFFFAOYSA-N 0.000 description 4
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 4
- MXOGJBKTZBIWOT-UHFFFAOYSA-N 2-phenoxycarbonylbenzoic acid Chemical compound OC(=O)C1=CC=CC=C1C(=O)OC1=CC=CC=C1 MXOGJBKTZBIWOT-UHFFFAOYSA-N 0.000 description 3
- 125000004203 4-hydroxyphenyl group Chemical group [H]OC1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- MOZDKDIOPSPTBH-UHFFFAOYSA-N Benzyl parahydroxybenzoate Chemical compound C1=CC(O)=CC=C1C(=O)OCC1=CC=CC=C1 MOZDKDIOPSPTBH-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000010419 fine particle Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 150000003751 zinc Chemical class 0.000 description 3
- GOVBKFNXUNXORO-UHFFFAOYSA-N 2-(4-methylphenoxy)carbonylbenzoic acid Chemical compound C1=CC(C)=CC=C1OC(=O)C1=CC=CC=C1C(O)=O GOVBKFNXUNXORO-UHFFFAOYSA-N 0.000 description 2
- TXFPEBPIARQUIG-UHFFFAOYSA-N 4'-hydroxyacetophenone Chemical compound CC(=O)C1=CC=C(O)C=C1 TXFPEBPIARQUIG-UHFFFAOYSA-N 0.000 description 2
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 2
- MSOMKPVOBYNJIP-UHFFFAOYSA-N 4-chloro-3-n,3-n-diethyl-1-n-fluoro-6-methylbenzene-1,3-diamine Chemical compound CCN(CC)C1=CC(NF)=C(C)C=C1Cl MSOMKPVOBYNJIP-UHFFFAOYSA-N 0.000 description 2
- 229940090248 4-hydroxybenzoic acid Drugs 0.000 description 2
- KQSLVMWNPNVKEO-UHFFFAOYSA-N 4-methyl-2-phenylmethoxycarbonylbenzoic acid Chemical compound CC1=CC=C(C(O)=O)C(C(=O)OCC=2C=CC=CC=2)=C1 KQSLVMWNPNVKEO-UHFFFAOYSA-N 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 235000012211 aluminium silicate Nutrition 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- 239000013256 coordination polymer Substances 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
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 description 2
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 2
- 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 2
- 238000005259 measurement Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- PMDKYLLIOLFQPO-UHFFFAOYSA-N monocyclohexyl phthalate Chemical compound OC(=O)C1=CC=CC=C1C(=O)OC1CCCCC1 PMDKYLLIOLFQPO-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- QELSKZZBTMNZEB-UHFFFAOYSA-N propylparaben Chemical compound CCCOC(=O)C1=CC=C(O)C=C1 QELSKZZBTMNZEB-UHFFFAOYSA-N 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 2
- LIZLYZVAYZQVPG-UHFFFAOYSA-N (3-bromo-2-fluorophenyl)methanol Chemical compound OCC1=CC=CC(Br)=C1F LIZLYZVAYZQVPG-UHFFFAOYSA-N 0.000 description 1
- UEXAQQULOLUJRX-UHFFFAOYSA-N 1-N,1-N-dibutyl-2-chloro-3-N-fluoro-4-methylbenzene-1,3-diamine Chemical compound C(CCC)N(C=1C(=C(NF)C(=CC=1)C)Cl)CCCC UEXAQQULOLUJRX-UHFFFAOYSA-N 0.000 description 1
- RYHQDYUGPBZCFQ-UHFFFAOYSA-N 2'-anilino-3'-methyl-6'-piperidin-1-ylspiro[2-benzofuran-3,9'-xanthene]-1-one Chemical compound CC1=CC=2OC3=CC(N4CCCCC4)=CC=C3C3(C4=CC=CC=C4C(=O)O3)C=2C=C1NC1=CC=CC=C1 RYHQDYUGPBZCFQ-UHFFFAOYSA-N 0.000 description 1
- SOMMOMFRWWYPHK-UHFFFAOYSA-N 2-(4-ethylphenoxy)carbonylbenzoic acid Chemical compound C1=CC(CC)=CC=C1OC(=O)C1=CC=CC=C1C(O)=O SOMMOMFRWWYPHK-UHFFFAOYSA-N 0.000 description 1
- FDGRQDBPWFICIN-UHFFFAOYSA-N 2-cyclohexyloxycarbonyl-5-methylbenzoic acid Chemical compound OC(=O)C1=CC(C)=CC=C1C(=O)OC1CCCCC1 FDGRQDBPWFICIN-UHFFFAOYSA-N 0.000 description 1
- DPWWASPVUYKSAS-UHFFFAOYSA-N 2-methyl-6-phenylmethoxycarbonylbenzoic acid Chemical compound CC1=CC=CC(C(=O)OCC=2C=CC=CC=2)=C1C(O)=O DPWWASPVUYKSAS-UHFFFAOYSA-N 0.000 description 1
- PYSRRFNXTXNWCD-UHFFFAOYSA-N 3-(2-phenylethenyl)furan-2,5-dione Chemical compound O=C1OC(=O)C(C=CC=2C=CC=CC=2)=C1 PYSRRFNXTXNWCD-UHFFFAOYSA-N 0.000 description 1
- XHQYAMKBTLODDV-UHFFFAOYSA-N 4-[2-(4-hydroxyphenyl)heptan-2-yl]phenol Chemical compound C=1C=C(O)C=CC=1C(C)(CCCCC)C1=CC=C(O)C=C1 XHQYAMKBTLODDV-UHFFFAOYSA-N 0.000 description 1
- HJSPWKGEPDZNLK-UHFFFAOYSA-N 4-benzylphenol Chemical compound C1=CC(O)=CC=C1CC1=CC=CC=C1 HJSPWKGEPDZNLK-UHFFFAOYSA-N 0.000 description 1
- 229940073735 4-hydroxy acetophenone Drugs 0.000 description 1
- MWTMXYXPZGPRJQ-UHFFFAOYSA-N 5-hydroxy-2-phenylmethoxycarbonylbenzoic acid Chemical compound OC(=O)C1=CC(O)=CC=C1C(=O)OCC1=CC=CC=C1 MWTMXYXPZGPRJQ-UHFFFAOYSA-N 0.000 description 1
- IFMQLIICBTZKBU-UHFFFAOYSA-N 5-methyl-2-phenylmethoxycarbonylbenzoic acid Chemical compound OC(=O)C1=CC(C)=CC=C1C(=O)OCC1=CC=CC=C1 IFMQLIICBTZKBU-UHFFFAOYSA-N 0.000 description 1
- SDDLEVPIDBLVHC-UHFFFAOYSA-N Bisphenol Z Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)CCCCC1 SDDLEVPIDBLVHC-UHFFFAOYSA-N 0.000 description 1
- 101100282617 Bovine herpesvirus 1.1 (strain Cooper) gC gene Proteins 0.000 description 1
- QFOHBWFCKVYLES-UHFFFAOYSA-N Butylparaben Chemical compound CCCCOC(=O)C1=CC=C(O)C=C1 QFOHBWFCKVYLES-UHFFFAOYSA-N 0.000 description 1
- YZCKVEUIGOORGS-UHFFFAOYSA-N Hydrogen atom Chemical compound [H] YZCKVEUIGOORGS-UHFFFAOYSA-N 0.000 description 1
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 1
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 1
- XPJVKCRENWUEJH-UHFFFAOYSA-N Isobutylparaben Chemical compound CC(C)COC(=O)C1=CC=C(O)C=C1 XPJVKCRENWUEJH-UHFFFAOYSA-N 0.000 description 1
- CMHMMKSPYOOVGI-UHFFFAOYSA-N Isopropylparaben Chemical compound CC(C)OC(=O)C1=CC=C(O)C=C1 CMHMMKSPYOOVGI-UHFFFAOYSA-N 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 229920000147 Styrene maleic anhydride Polymers 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 239000002518 antifoaming agent 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
- 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
- IUGQFMIATSVYLK-UHFFFAOYSA-N benzyl 2-(4-hydroxyphenyl)acetate Chemical compound C1=CC(O)=CC=C1CC(=O)OCC1=CC=CC=C1 IUGQFMIATSVYLK-UHFFFAOYSA-N 0.000 description 1
- BPLKDVGMXNZCQO-UHFFFAOYSA-N benzyl 4-phenylmethoxybenzoate Chemical compound C=1C=C(OCC=2C=CC=CC=2)C=CC=1C(=O)OCC1=CC=CC=C1 BPLKDVGMXNZCQO-UHFFFAOYSA-N 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
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 150000005690 diesters Chemical class 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 229940015043 glyoxal Drugs 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000011256 inorganic filler 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
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 235000010981 methylcellulose Nutrition 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000012766 organic filler Substances 0.000 description 1
- 150000003021 phthalic acid derivatives Chemical class 0.000 description 1
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 1
- 238000001454 recorded image Methods 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 210000004243 sweat Anatomy 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- 238000004078 waterproofing Methods 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
- B41M5/30—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using chemical colour formers
- B41M5/32—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using chemical colour formers one component being a heavy metal compound, e.g. lead or iron
Definitions
- the invention relates to a heat-sensitive recording sheet which has a superior stability of the color image and the whiteness of the background to hair oil, grease, oil, etc.
- a heat-sensitive recording sheet using a heat color reaction between a basic colorless or lightly colored chromogenic dye and an organic color developing agent such as a phenolic substance or an organic acid is disclosed in Japanese Patent Publication Nos. 4160/1968 and 14039 / 1970, and described in Japanese Patent Laid-Open No. 27736/1973. It has many practical uses.
- a heat-sensitive recording sheet is generally prepared by applying a coating composition to the surface of the support such as paper, film, etc., which can be finely divided by individually grinding and dispersing a colorless chromogenic dye and a color developing material such as phenolic substances into fine particles dispersions obtained and by adding a binder, filler, sensitizer, lubricant and other auxiliaries.
- the oily materials are the color-forming layer consisting of a basic colorless chromogenic dye of fine particles and an organic color developing agent of fine particles, or the color-forming reaction product which is made of a basic colorless chromogenic Dye and an organic color developing agent is formed, partially dissolve or destabilize.
- the heat-sensitive recording sheets using 4-hydroxybenzoic acid ester or 4-hydroxyphthalic acid diester are generally satisfactory, but in terms of oily stability, the heat-sensitive recording sheets in which bisphenol compounds are used as color developing agents are used in previous heat-sensitive recording sheets inferior.
- the invention has for its object to provide a heat-sensitive recording sheet in which the recording image is very stable against the action of oily materials.
- R 1 is preferably a CH 3 , C 2 H 5 , C 3 H 7 , iso-C 3 H 7 , tert-C 4 H 9 9 C 5 H 11 or C 6 H 13 group; if R 29 R 3 and / or R 4 represent an alkyl group, this is preferably a methyl or ethyl group.
- halogen substituents these are preferably F, Cl and Br atoms, in particular Cl atoms.
- the amount and kind of the color developing agent to be used in the present invention are not particularly limited, but the effects of this invention are significant when monophenolic 4-hydroxyphenyl compounds and / or phthalic acid monoesters are used as the color developing agent because they are essential for improving the quality of the heat-sensitive recording sheets contribute; e.g. clear recording with high image density, no residue adhering to the thermal head, no sticking of the heat-sensitive recording sheet to the thermal head, superior recording suitability, less color formation of the background over time, etc.
- Examples of monophenolic 4-hydroxyphenyl compounds are 4-hydroxybenzoic acid esters, for example 4-hydroxybenzoic acid propyl ester, 4-hydroxybenzoic acid isopropyl ester, 4-hydroxybenzoic acid butyl ester, 4-hydroxybenzoic acid isobutyl ester, 4-hydroxybenzoic acid benzyl ester, 4-hydroxybenzyl ester; 4-hydroxyphthalic diesters, for example dimethyl 4-hydroxyphthalate, diisopropyl 4-hydroxy phthalate, dibenzyl 4-hydroxy phthalate, di-4-hydroxy phthalate, etc .; 4-hydroxyacetophenone; p-phenylphenol; Benzyl 4-hydroxyphenylacetate; p-benzylphenol; 4-hydroxyphenyl-4'-n-sulfone, 4-hydroxyphenyl-4'-n-butyloxyphenyl sulfone, 4-hydroxyphenyl-4'-n-hexyloxy-phenyl sulfone, 4-hydroxyphenyl-4'-n-
- phthalic acid monoesters are phthalic acid monophenyl ester, phthalic acid monobenzyl ester, phthalic acid monocyclohexyl ester, phthalic acid monomethylphenyl ester, phthalic acid monoethylphenyl ester, phthalic acid monoalkylbenzyl esters, phthalic acid monohalobenzyl esters, phthalic acid monoalkoxybenzyl esters and the like.
- bisphenol compounds examples include 4,4'-isopropylidene diphenol (bisphenol A), 4,4 '(1-methyl-n-hexylidene) diphenol, 4,4'-cyclohexylidene diphenol, 4,4'-thiobis-4-tert-butyl -3-methylphenol and the like. These color developing agents used in combination are unsatisfactory in stability against oily materials.
- colorless or slightly colored chromogenic dyes are useful for the invention and are not particularly limited.
- thermochromic phenomenon occurs in which the color image is extinguished immediately or slowly. Therefore, these dyes cannot be used in heat-sensitive recording sheets.
- this thermochromic phenomenon is eliminated by using the metal salts of the phthalic acid monoesters as stabilizers, which means that the above basic colorless dyes can be used.
- metal salts according to the invention of the phthalic acid monoesters of the general formula I are metal salts of phthalic acid monophenyl ester, phthalic acid monobenzyl ester, phthalic acid monocyclohexyl ester, phthalic acid monomethylphenyl ester, phthalic acid monophenyl ester, phthalic acid monoalkylbenzyl ester, phthalic acid mono ester benzyl ester, phthalic acid monoalkoxy benzyl ester, 4-methyl phthalic acid monobenzyl ester, 3-methyl phthalic acid monobenzyl ester, 5-methyl phthalic acid monobenzyl ester, 4-methyl phthalic acid monocyclohexyl ester, 5-methyl phthalic acid monobenzyl ester, and the like, methyl mono cyclohexyl ester,
- metals e.g. polyvalent metals, such as zinc, calcium, magnesium, barium and lead, preferably zinc, calcium and magnesium.
- These stabilizers can be used individually or in a mixture.
- the above-mentioned organic color developing agent, the above-mentioned organic colorless chromogenic dye and the metal salt derivative of the phthalic acid monoester are ground to a particle size of several microns or smaller by means of a grinder such as a ball mill, grinder, sand grinder, etc. or by means of a suitable emulsifying machine.
- a grinder such as a ball mill, grinder, sand grinder, etc. or by means of a suitable emulsifying machine.
- additives are added to this, depending on the intended use, in order to produce the coating color.
- the additives which can be used according to the invention are, for example, the following: binders, such as polyvinyl alcohol, are more modified Polyvinyl alcohol, hydroxyethyl cellulose, methyl cellulose, starch, styrene-maleic anhydride copolymers, vinyl acetate-maleic anhydride copolymers, styrene-butadiene copolymers, etc .; inorganic or organic fillers such as kaolin, baked kaolin, diatomaceous earth, talc, titanium dioxide, calcium carbonate, magnesium carbonate, aluminum hydroxide, etc .; Release agents such as metal salts of fatty acids; Lubricants such as waxes; UV absorbers of the benzophenone and triazole series; waterproofing agents such as glyoxal, etc .; Dispersing agents, anti-foaming agents, etc.
- the amount of the metal salt derivatives of the phthalic acid monoester according to the invention and the type and the amount of the other constituents which are determined depending on the desired effect and the suitability for recording purposes are not particularly limited.
- Solution B (dispersion of a color developing agent): benzyl p-hydroxybenzoate
- the image density of the unrecorded part is left under strong conditions of 60 ° C and 45% RH for 24 hours, and then measured with a Macbeth densimeter.
- the examples according to the invention in which metal derivatives of phthalic acid monoester were used as stabilizer, gave a very good recording image even after standing for 7 days after being contaminated with castor oil, i.e. good stabilization was achieved, which is expressed in a residual image density of more than 70%.
- the stabilizers according to the invention have superior effects even when using phthalic acid monobenzyl ester as color developing agent.
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Heat Sensitive Colour Forming Recording (AREA)
- Color Printing (AREA)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58153083A JPS6046293A (ja) | 1983-08-24 | 1983-08-24 | 感熱記録紙 |
| JP153083/83 | 1983-08-24 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0137982A1 true EP0137982A1 (fr) | 1985-04-24 |
| EP0137982B1 EP0137982B1 (fr) | 1987-12-23 |
Family
ID=15554599
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP84110091A Expired EP0137982B1 (fr) | 1983-08-24 | 1984-08-23 | Feuille d'enregistrement sensible à la chaleur |
Country Status (4)
| Country | Link |
|---|---|
| US (1) | US4590500A (fr) |
| EP (1) | EP0137982B1 (fr) |
| JP (1) | JPS6046293A (fr) |
| DE (1) | DE3468196D1 (fr) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4630080A (en) * | 1984-11-16 | 1986-12-16 | Jujo Paper Co., Ltd. | Heat-sensitive recording sheet |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62148288A (ja) * | 1985-12-24 | 1987-07-02 | Kanzaki Paper Mfg Co Ltd | 感熱記録体 |
| JPS62196179A (ja) * | 1986-02-24 | 1987-08-29 | Kanzaki Paper Mfg Co Ltd | 感熱記録体 |
| DE3715724A1 (de) * | 1987-05-12 | 1988-11-24 | Bayer Ag | Thermoreaktives aufzeichnungsmaterial |
| GB2216676A (en) * | 1988-03-10 | 1989-10-11 | Sugai Chemical Ind Co Ltd | Fading inhibitor for color former |
| US7314704B2 (en) * | 2005-10-24 | 2008-01-01 | Hewlett-Packard Development Company, L.P. | Image recording media and image layers |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2243830A1 (fr) * | 1973-09-14 | 1975-04-11 | Agfa Gevaert |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5841760B2 (ja) * | 1976-05-29 | 1983-09-14 | 神崎製紙株式会社 | 呈色剤の製造方法 |
| JPS57129785A (en) * | 1981-02-06 | 1982-08-11 | Jujo Paper Co Ltd | Heat sensitive recording paper |
| JPS5898285A (ja) * | 1981-12-09 | 1983-06-11 | Shin Nisso Kako Co Ltd | 感熱発色性組成物 |
| JPS5939593A (ja) * | 1982-08-30 | 1984-03-03 | Jujo Paper Co Ltd | 感熱記録紙 |
| JPS59167294A (ja) * | 1983-03-15 | 1984-09-20 | Jujo Paper Co Ltd | 感熱記録シ−ト |
-
1983
- 1983-08-24 JP JP58153083A patent/JPS6046293A/ja active Granted
-
1984
- 1984-08-21 US US06/642,788 patent/US4590500A/en not_active Expired - Lifetime
- 1984-08-23 EP EP84110091A patent/EP0137982B1/fr not_active Expired
- 1984-08-23 DE DE8484110091T patent/DE3468196D1/de not_active Expired
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2243830A1 (fr) * | 1973-09-14 | 1975-04-11 | Agfa Gevaert |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4630080A (en) * | 1984-11-16 | 1986-12-16 | Jujo Paper Co., Ltd. | Heat-sensitive recording sheet |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6046293A (ja) | 1985-03-13 |
| US4590500A (en) | 1986-05-20 |
| EP0137982B1 (fr) | 1987-12-23 |
| JPH0239993B2 (fr) | 1990-09-07 |
| DE3468196D1 (en) | 1988-02-04 |
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