JP4294534B2 - Writing instrument - Google Patents
Writing instrument Download PDFInfo
- Publication number
- JP4294534B2 JP4294534B2 JP2004119869A JP2004119869A JP4294534B2 JP 4294534 B2 JP4294534 B2 JP 4294534B2 JP 2004119869 A JP2004119869 A JP 2004119869A JP 2004119869 A JP2004119869 A JP 2004119869A JP 4294534 B2 JP4294534 B2 JP 4294534B2
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- JP
- Japan
- Prior art keywords
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- temperature
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- 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
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- -1 ester compound Chemical class 0.000 claims description 56
- 239000003094 microcapsule Substances 0.000 claims description 40
- 239000000203 mixture Substances 0.000 claims description 39
- 239000000049 pigment Substances 0.000 claims description 36
- 150000001875 compounds Chemical class 0.000 claims description 18
- 125000000217 alkyl group Chemical group 0.000 claims description 7
- 125000004432 carbon atom Chemical group C* 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 6
- 150000002894 organic compounds Chemical class 0.000 claims description 4
- 125000003342 alkenyl group Chemical group 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 239000012429 reaction media Substances 0.000 claims description 3
- 239000012456 homogeneous solution Substances 0.000 claims description 2
- 230000035945 sensitivity Effects 0.000 claims description 2
- 230000008859 change Effects 0.000 description 18
- 238000004042 decolorization Methods 0.000 description 17
- 238000002845 discoloration Methods 0.000 description 14
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 12
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- 239000000725 suspension Substances 0.000 description 11
- 230000014759 maintenance of location Effects 0.000 description 10
- 230000006399 behavior Effects 0.000 description 9
- 239000007788 liquid Substances 0.000 description 9
- 229910052751 metal Inorganic materials 0.000 description 9
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- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 9
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- 230000002265 prevention Effects 0.000 description 7
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- 125000003118 aryl group Chemical group 0.000 description 6
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- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 5
- 125000001931 aliphatic group Chemical group 0.000 description 5
- 150000001412 amines Chemical class 0.000 description 5
- DMSMPAJRVJJAGA-UHFFFAOYSA-N benzo[d]isothiazol-3-one Chemical compound C1=CC=C2C(=O)NSC2=C1 DMSMPAJRVJJAGA-UHFFFAOYSA-N 0.000 description 5
- 150000004665 fatty acids Chemical class 0.000 description 5
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- 239000012948 isocyanate Substances 0.000 description 5
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
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- 150000005215 alkyl ethers Chemical class 0.000 description 4
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- 235000019425 dextrin Nutrition 0.000 description 4
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- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 4
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- QNSFPYSRPPFJGJ-UHFFFAOYSA-N spiro[2-benzofuran-3,5'-chromeno[2,3-d]pyrimidine]-1-one Chemical compound C12=CC=CC=C2OC2=NC=NC=C2C11OC(=O)C2=CC=CC=C21 QNSFPYSRPPFJGJ-UHFFFAOYSA-N 0.000 description 4
- MKSNYWIILLZWOY-UHFFFAOYSA-N 2-(4-phenylmethoxyphenyl)ethyl decanoate Chemical compound C1=CC(CCOC(=O)CCCCCCCCC)=CC=C1OCC1=CC=CC=C1 MKSNYWIILLZWOY-UHFFFAOYSA-N 0.000 description 3
- QEQQAFXMPDXVSV-UHFFFAOYSA-N 4-[1,2,2,3,3,3-hexafluoro-1-(4-hydroxyphenyl)propyl]phenol Chemical compound C1=CC(O)=CC=C1C(F)(C(F)(F)C(F)(F)F)C1=CC=C(O)C=C1 QEQQAFXMPDXVSV-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 3
- 150000001408 amides Chemical class 0.000 description 3
- 239000004202 carbamide Substances 0.000 description 3
- 239000004359 castor oil Substances 0.000 description 3
- 235000019438 castor oil Nutrition 0.000 description 3
- 125000001664 diethylamino group Chemical group [H]C([H])([H])C([H])([H])N(*)C([H])([H])C([H])([H])[H] 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 238000011049 filling Methods 0.000 description 3
- 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 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 239000000314 lubricant Substances 0.000 description 3
- 239000002736 nonionic surfactant Substances 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
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- 230000002335 preservative effect Effects 0.000 description 3
- 230000002441 reversible effect Effects 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 229920003002 synthetic resin Polymers 0.000 description 3
- 239000000057 synthetic resin Substances 0.000 description 3
- GRWFGVWFFZKLTI-IUCAKERBSA-N (-)-α-pinene Chemical compound CC1=CC[C@@H]2C(C)(C)[C@H]1C2 GRWFGVWFFZKLTI-IUCAKERBSA-N 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 2
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 2
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 2
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 2
- 239000004166 Lanolin Substances 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 2
- LLEMOWNGBBNAJR-UHFFFAOYSA-N biphenyl-2-ol Chemical compound OC1=CC=CC=C1C1=CC=CC=C1 LLEMOWNGBBNAJR-UHFFFAOYSA-N 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
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- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- GHVNFZFCNZKVNT-UHFFFAOYSA-N decanoic acid Chemical compound CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000001804 emulsifying effect Effects 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- XLLIQLLCWZCATF-UHFFFAOYSA-N ethylene glycol monomethyl ether acetate Natural products COCCOC(C)=O XLLIQLLCWZCATF-UHFFFAOYSA-N 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 239000008103 glucose Substances 0.000 description 2
- 229920000591 gum Polymers 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 235000019388 lanolin Nutrition 0.000 description 2
- 229940039717 lanolin Drugs 0.000 description 2
- HQKMJHAJHXVSDF-UHFFFAOYSA-L magnesium stearate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQKMJHAJHXVSDF-UHFFFAOYSA-L 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 2
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 238000005191 phase separation Methods 0.000 description 2
- 239000005011 phenolic resin Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920001083 polybutene Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000000717 retained effect Effects 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000000600 sorbitol Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- SZHOJFHSIKHZHA-UHFFFAOYSA-N tridecanoic acid Chemical compound CCCCCCCCCCCCC(O)=O SZHOJFHSIKHZHA-UHFFFAOYSA-N 0.000 description 2
- 239000004711 α-olefin Substances 0.000 description 2
- HDTRYLNUVZCQOY-UHFFFAOYSA-N α-D-glucopyranosyl-α-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OC1C(O)C(O)C(O)C(CO)O1 HDTRYLNUVZCQOY-UHFFFAOYSA-N 0.000 description 1
- WTARULDDTDQWMU-RKDXNWHRSA-N (+)-β-pinene Chemical compound C1[C@H]2C(C)(C)[C@@H]1CCC2=C WTARULDDTDQWMU-RKDXNWHRSA-N 0.000 description 1
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 1
- WTARULDDTDQWMU-IUCAKERBSA-N (-)-Nopinene Natural products C1[C@@H]2C(C)(C)[C@H]1CCC2=C WTARULDDTDQWMU-IUCAKERBSA-N 0.000 description 1
- HZVFRKSYUGFFEJ-YVECIDJPSA-N (2r,3r,4s,5r)-7-phenylhept-6-ene-1,2,3,4,5,6-hexol Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=CC1=CC=CC=C1 HZVFRKSYUGFFEJ-YVECIDJPSA-N 0.000 description 1
- VKFWQGFYGLIANZ-WOPDTQHZSA-N (2r,3s,4r)-6-phenylhex-5-ene-1,2,3,4,5-pentol Chemical compound OC[C@@H](O)[C@H](O)[C@@H](O)C(O)=CC1=CC=CC=C1 VKFWQGFYGLIANZ-WOPDTQHZSA-N 0.000 description 1
- LUEWUZLMQUOBSB-FSKGGBMCSA-N (2s,3s,4s,5s,6r)-2-[(2r,3s,4r,5r,6s)-6-[(2r,3s,4r,5s,6s)-4,5-dihydroxy-2-(hydroxymethyl)-6-[(2r,4r,5s,6r)-4,5,6-trihydroxy-2-(hydroxymethyl)oxan-3-yl]oxyoxan-3-yl]oxy-4,5-dihydroxy-2-(hydroxymethyl)oxan-3-yl]oxy-6-(hydroxymethyl)oxane-3,4,5-triol Chemical compound O[C@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@H]1O[C@@H]1[C@@H](CO)O[C@@H](O[C@@H]2[C@H](O[C@@H](OC3[C@H](O[C@@H](O)[C@@H](O)[C@H]3O)CO)[C@@H](O)[C@H]2O)CO)[C@H](O)[C@H]1O LUEWUZLMQUOBSB-FSKGGBMCSA-N 0.000 description 1
- DRTUZXVHUZFJCX-UHFFFAOYSA-N (4-phenylmethoxyphenyl) decanoate Chemical compound C1=CC(OC(=O)CCCCCCCCC)=CC=C1OCC1=CC=CC=C1 DRTUZXVHUZFJCX-UHFFFAOYSA-N 0.000 description 1
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- NSGXIBWMJZWTPY-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropane Chemical compound FC(F)(F)CC(F)(F)F NSGXIBWMJZWTPY-UHFFFAOYSA-N 0.000 description 1
- HCNHNBLSNVSJTJ-UHFFFAOYSA-N 1,1-Bis(4-hydroxyphenyl)ethane Chemical compound C=1C=C(O)C=CC=1C(C)C1=CC=C(O)C=C1 HCNHNBLSNVSJTJ-UHFFFAOYSA-N 0.000 description 1
- RWNUSVWFHDHRCJ-UHFFFAOYSA-N 1-butoxypropan-2-ol Chemical compound CCCCOCC(C)O RWNUSVWFHDHRCJ-UHFFFAOYSA-N 0.000 description 1
- QWENRTYMTSOGBR-UHFFFAOYSA-N 1H-1,2,3-Triazole Chemical compound C=1C=NNN=1 QWENRTYMTSOGBR-UHFFFAOYSA-N 0.000 description 1
- CHHHXKFHOYLYRE-UHFFFAOYSA-M 2,4-Hexadienoic acid, potassium salt (1:1), (2E,4E)- Chemical compound [K+].CC=CC=CC([O-])=O CHHHXKFHOYLYRE-UHFFFAOYSA-M 0.000 description 1
- SBASXUCJHJRPEV-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethanol Chemical compound COCCOCCO SBASXUCJHJRPEV-UHFFFAOYSA-N 0.000 description 1
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- VQWGCFKMUFNLIK-UHFFFAOYSA-N 2-[2-(4-dodecoxy-3-methoxyphenyl)ethenyl]quinoline Chemical compound C1=C(OC)C(OCCCCCCCCCCCC)=CC=C1C=CC1=CC=C(C=CC=C2)C2=N1 VQWGCFKMUFNLIK-UHFFFAOYSA-N 0.000 description 1
- UXGVMFHEKMGWMA-UHFFFAOYSA-N 2-benzofuran Chemical compound C1=CC=CC2=COC=C21 UXGVMFHEKMGWMA-UHFFFAOYSA-N 0.000 description 1
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- USPURJZIFMFHCR-UHFFFAOYSA-N 2-chloro-4-methylsulfonylpyridine Chemical compound CS(=O)(=O)C1=CC=NC(Cl)=C1 USPURJZIFMFHCR-UHFFFAOYSA-N 0.000 description 1
- CYEJMVLDXAUOPN-UHFFFAOYSA-N 2-dodecylphenol Chemical group CCCCCCCCCCCCC1=CC=CC=C1O CYEJMVLDXAUOPN-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- DUIOKRXOKLLURE-UHFFFAOYSA-N 2-octylphenol Chemical group CCCCCCCCC1=CC=CC=C1O DUIOKRXOKLLURE-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- GRIKUIPJBHJPPN-UHFFFAOYSA-N 3',6'-dimethoxyspiro[2-benzofuran-3,9'-xanthene]-1-one Chemical compound O1C(=O)C2=CC=CC=C2C21C1=CC=C(OC)C=C1OC1=CC(OC)=CC=C21 GRIKUIPJBHJPPN-UHFFFAOYSA-N 0.000 description 1
- YMTYZTXUZLQUSF-UHFFFAOYSA-N 3,3'-Dimethylbisphenol A Chemical compound C1=C(O)C(C)=CC(C(C)(C)C=2C=C(C)C(O)=CC=2)=C1 YMTYZTXUZLQUSF-UHFFFAOYSA-N 0.000 description 1
- JZEPXWWZAJGALH-UHFFFAOYSA-N 3,3-bis(1-butyl-2-methylindol-3-yl)-2-benzofuran-1-one Chemical compound C1=CC=C2C(C3(C4=CC=CC=C4C(=O)O3)C3=C(C)N(C4=CC=CC=C43)CCCC)=C(C)N(CCCC)C2=C1 JZEPXWWZAJGALH-UHFFFAOYSA-N 0.000 description 1
- XBCTUDRVBSOUQD-UHFFFAOYSA-N 3-(1h-indol-2-yl)-3-phenyl-2-benzofuran-1-one Chemical class C12=CC=CC=C2C(=O)OC1(C=1NC2=CC=CC=C2C=1)C1=CC=CC=C1 XBCTUDRVBSOUQD-UHFFFAOYSA-N 0.000 description 1
- UYMBCDOGDVGEFA-UHFFFAOYSA-N 3-(1h-indol-2-yl)-3h-2-benzofuran-1-one Chemical class C12=CC=CC=C2C(=O)OC1C1=CC2=CC=CC=C2N1 UYMBCDOGDVGEFA-UHFFFAOYSA-N 0.000 description 1
- HOUWRQXIBSGOHF-UHFFFAOYSA-N 3-[4-(diethylamino)phenyl]-3-(1-ethyl-2-methylindol-3-yl)-2-benzofuran-1-one Chemical compound C1=CC(N(CC)CC)=CC=C1C1(C=2C3=CC=CC=C3N(CC)C=2C)C2=CC=CC=C2C(=O)O1 HOUWRQXIBSGOHF-UHFFFAOYSA-N 0.000 description 1
- BJEMXPVDXFSROA-UHFFFAOYSA-N 3-butylbenzene-1,2-diol Chemical group CCCCC1=CC=CC(O)=C1O BJEMXPVDXFSROA-UHFFFAOYSA-N 0.000 description 1
- SVAPVDMWXJVISW-UHFFFAOYSA-N 3h-2-benzofuran-1-one;benzylbenzene Chemical class C1=CC=C2C(=O)OCC2=C1.C=1C=CC=CC=1CC1=CC=CC=C1 SVAPVDMWXJVISW-UHFFFAOYSA-N 0.000 description 1
- ZGZVGZCIFZBNCN-UHFFFAOYSA-N 4,4'-(2-Methylpropylidene)bisphenol Chemical compound C=1C=C(O)C=CC=1C(C(C)C)C1=CC=C(O)C=C1 ZGZVGZCIFZBNCN-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
- NMWKWBPNKPGATC-UHFFFAOYSA-N 4,5,6,7-tetrachloro-2-benzofuran-1(3H)-one Chemical compound ClC1=C(Cl)C(Cl)=C2COC(=O)C2=C1Cl NMWKWBPNKPGATC-UHFFFAOYSA-N 0.000 description 1
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- FKRCODPIKNYEAC-UHFFFAOYSA-N propionic acid ethyl ester Natural products CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
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- JWVCLYRUEFBMGU-UHFFFAOYSA-N quinazoline Chemical compound N1=CN=CC2=CC=CC=C21 JWVCLYRUEFBMGU-UHFFFAOYSA-N 0.000 description 1
- GRWFGVWFFZKLTI-UHFFFAOYSA-N rac-alpha-Pinene Natural products CC1=CCC2C(C)(C)C1C2 GRWFGVWFFZKLTI-UHFFFAOYSA-N 0.000 description 1
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 1
- 229960001755 resorcinol Drugs 0.000 description 1
- 238000000518 rheometry Methods 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 239000010979 ruby Substances 0.000 description 1
- 229910001750 ruby Inorganic materials 0.000 description 1
- 229930182490 saponin Natural products 0.000 description 1
- 150000007949 saponins Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 150000004671 saturated fatty acids Chemical class 0.000 description 1
- HFHDHCJBZVLPGP-UHFFFAOYSA-N schardinger α-dextrin Chemical compound O1C(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(O)C2O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC2C(O)C(O)C1OC2CO HFHDHCJBZVLPGP-UHFFFAOYSA-N 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- WXMKPNITSTVMEF-UHFFFAOYSA-M sodium benzoate Chemical compound [Na+].[O-]C(=O)C1=CC=CC=C1 WXMKPNITSTVMEF-UHFFFAOYSA-M 0.000 description 1
- 239000004299 sodium benzoate Substances 0.000 description 1
- 235000010234 sodium benzoate Nutrition 0.000 description 1
- 229960003885 sodium benzoate Drugs 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000019259 sodium dehydroacetate Nutrition 0.000 description 1
- 229940079839 sodium dehydroacetate Drugs 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- DSOWAKKSGYUMTF-GZOLSCHFSA-M sodium;(1e)-1-(6-methyl-2,4-dioxopyran-3-ylidene)ethanolate Chemical compound [Na+].C\C([O-])=C1/C(=O)OC(C)=CC1=O DSOWAKKSGYUMTF-GZOLSCHFSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 125000003003 spiro group Chemical group 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- YODZTKMDCQEPHD-UHFFFAOYSA-N thiodiglycol Chemical compound OCCSCCO YODZTKMDCQEPHD-UHFFFAOYSA-N 0.000 description 1
- 150000005691 triesters Chemical class 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 1
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
- 229920001285 xanthan gum Polymers 0.000 description 1
- 235000010493 xanthan gum Nutrition 0.000 description 1
- 239000000230 xanthan gum Substances 0.000 description 1
- 229940082509 xanthan gum Drugs 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
- UHVMMEOXYDMDKI-JKYCWFKZSA-L zinc;1-(5-cyanopyridin-2-yl)-3-[(1s,2s)-2-(6-fluoro-2-hydroxy-3-propanoylphenyl)cyclopropyl]urea;diacetate Chemical compound [Zn+2].CC([O-])=O.CC([O-])=O.CCC(=O)C1=CC=C(F)C([C@H]2[C@H](C2)NC(=O)NC=2N=CC(=CC=2)C#N)=C1O UHVMMEOXYDMDKI-JKYCWFKZSA-L 0.000 description 1
Images
Landscapes
- Pens And Brushes (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
Description
本発明は筆記具に関する。更に詳細には、温度変化により大きなヒステリシス特性を示して可逆的変色を呈し、変色に要した熱又は冷熱の適用を取り去った後にあっても、いずれかの状態を保持する機能を備えた感温変色性色彩記憶性筆記具用インキ組成物を収容し、且つ、摩擦体を備えた筆記具に関する。 The present invention relates to a writing instrument . More specifically, it exhibits a reversible discoloration with a large hysteresis characteristic due to a temperature change, and has a function of maintaining either state even after the application of heat or cold heat required for the discoloration is removed. The present invention relates to a writing instrument that contains an ink composition for a color-changing color-memory writing instrument and includes a friction body .
従来より、（イ）電子供与性呈色性有機化合物、（ロ）電子受容性化合物（ハ）前記（イ）、（ロ）による電子授受反応を可逆的に生起させる反応媒体である化合物からなる感温変色性色彩記憶性組成物を溶剤中に分散した筆記具用インキ組成物が開示されている（例えば、特許文献１参照）。
前記インキ組成物は、変色前後の両状態のうち常温域では一方の状態しか存在せず、いずれかを選択的に視認できるものである。
しかしながら、前記インキを筆記具に充填して実用に供した場合、常温域で色調を保持する機能を必ずしも満足させるものではなく、冬場や夏場の環境温度によってはインキ中で感温変色性色彩記憶性組成物が変色したり、或いは、前記インキにより筆記して得られた記録物が変色して所期の機能を発現できない場合がある。
In the ink composition, only one of the two states before and after the color change is present in the normal temperature range, and either one can be selectively visually recognized.
However, when the ink is filled into a writing instrument and put to practical use, it does not necessarily satisfy the function of maintaining the color tone in the normal temperature range. Depending on the environmental temperature in winter and summer, the temperature-sensitive color change color memory property in the ink The composition may be discolored, or the recorded material obtained by writing with the ink may be discolored to exhibit the desired function.
本発明は、熱又は冷熱の適用を取り去った後にあっても、変色前後のいずれかの状態を常温域において択一的に発現できる感温変色性色彩記憶性筆記具用インキ組成物に関する。 The present invention relates to an ink composition for a temperature-sensitive color-changing color memory writing instrument capable of alternatively expressing any state before and after the color change in a normal temperature range even after the application of heat or cold is removed.
本発明は、（イ）電子供与性呈色性有機化合物、（ロ）電子受容性化合物、（ハ）前記（イ）、（ロ）の呈色反応をコントロールする反応媒体として、下記一般式（１）で示されるエステル化合物の均質相溶体からなる感温変色性色彩記憶性組成物を内包したマイクロカプセル顔料と、溶剤とから少なくともなり、前記マイクロカプセル顔料は、色濃度−温度曲線に関して４０℃乃至７０℃のヒステリシス幅（ΔＨ）を示し、完全消色温度（Ｔ４）が５０℃以上であり、且つ、消色保持温度（Ｔ２）が−５℃以下である有色から無色に可逆的に変色する感温変色性色彩記憶性筆記具用インキ組成物を収容し、且つ、摩擦体を備えた筆記具を要件とする。
更には、前記ヒステリシス幅（ΔＨ）が５０〜７０℃であることを要件とする。
The present invention, (a) an electron-donating coloring organic compound, (b) an electron-accepting compound, (c) said (a), as the reaction medium to control the color reaction (B), the following general formula ( 1) A microcapsule pigment containing a temperature-sensitive color-changing color memory composition composed of a homogeneous solution of an ester compound represented by 1) and a solvent, and the microcapsule pigment has a color density-temperature curve of 40 ° C. to indicate the 70 ° C. hysteresis width ([Delta] H), complete decoloring temperature (T 4) is not less 50 ° C. or more and decoloring holding temperature (T 2) is - reversible colorless from 5 ° C. or less colored A writing instrument that contains a temperature-sensitive color-changing color-memory ink composition for a writing instrument and that includes a friction body is a requirement.
Furthermore, the hysteresis width ([Delta] H) is a 50-70 ° C. Dearuko and requirements.
本発明は、色濃度−温度曲線に関して広いヒステリシス幅（ΔＨ）を示して可逆的変色を生起させ、常温域において変色温度より低温側の色と高温側の色の両方を明瞭且つ互変的に記憶保持でき、必要に応じて熱又は冷熱を適用することにより、いずれかの色を可逆的に再現させて記憶保持できる特性を効果的に発現させることができる実用性に優れた筆記具用インキ組成物を収容し、且つ、摩擦体を備えた筆記具を提供できる。 The present invention exhibits reversible discoloration by exhibiting a wide hysteresis width (ΔH) with respect to the color density-temperature curve, and in the normal temperature range, both the color on the lower temperature side and the color on the higher temperature side are clear and interchangeable. Ink composition for writing instruments with excellent practicality that can be stored and retained, and by applying heat or cold as needed, any color can be reversibly reproduced and stored and retained effectively. It is possible to provide a writing instrument that accommodates an object and includes a friction body .
以下に本発明に用いられる感温変色性色彩記憶性組成物の色濃度−温度曲線におけるヒステリシス特性を図１のグラフによって説明する。
図１において、縦軸に色濃度、横軸に温度が表されている。温度変化による色濃度の変化は矢印に沿って進行する。ここで、Ａは完全消色状態に達する温度Ｔ４（以下、完全消色温度と称す）における濃度を示す点であり、Ｂは完全発色状態を保持できる温度Ｔ３（以下、発色保持温度と称す）における濃度を示す点であり、Ｃは完全消色状態を保持できる最低温度Ｔ２（以下、消色保持温度と称す）における濃度を示す点であり、Ｄは完全発色状態に達する温度Ｔ１（以下、完全発色温度と称す）における濃度を示す点である。
また、線分ＥＦの長さが変色のコントラストを示す尺度であり、線分ＨＧの長さがヒステリシスの程度を示す温度幅（以下、ヒステリシス幅ΔＨと記す）であり、このΔＨ値が大きい程、変色前後の各状態の保持が容易である。
ここで、Ｔ４とＴ３の差、或いは、Ｔ２とＴ１の差であるΔｔが変色の鋭敏性を示す尺度である。
本発明において変色前後の各状態の保持できるΔＨ値は４０℃乃至７０℃の範囲であり、好ましくは５０乃至７０℃、更に好ましくは６０乃至７０℃である。
更に、変色前後の両状態のうち常温域では特定の一方の状態のみ存在させるためには、完全消色温度（Ｔ４）が５０℃以上であり、且つ、消色保持温度（Ｔ２）が−５℃以下である。
ここで、発色状態と消色状態の両相が常温域で共存できるために何故完全消色温度（Ｔ４）が５０℃以上、且つ、消色保持温度（Ｔ２）が−５℃以下であるかを説明すると、発色状態から発色保持温度（Ｔ３）を経て完全消色温度（Ｔ４）に達しない状態で加温を止めると、再び発色状態に復する現象を生じること、及び、消色状態から消色保持温度（Ｔ２）を経て完全発色温度（Ｔ１）に達しない状態で冷却を中止しても発色を生じた状態が維持されることから、完全消色温度（Ｔ４）が常温域を越える５０℃以上であれば、発色状態は通常の使用状態において維持されることになり、消色保持温度（Ｔ２）が常温域を下回る−５℃以下であれば消色状態は通常の使用において維持される。
よって、前記温度設定は筆記面に発色前後の筆跡を選択して択一的に視認させる筆記具用インキには重要な要件であり、利便性と実用性を満足させることができる。
The hysteresis characteristics in the color density-temperature curve of the temperature-sensitive color-changing color memory composition used in the present invention will be described below with reference to the graph of FIG.
In FIG. 1, the vertical axis represents color density and the horizontal axis represents temperature. The change in color density due to the temperature change proceeds along the arrow. Here, A is a point indicating a density at a temperature T 4 reaching a complete color erasing state (hereinafter referred to as a complete color erasing temperature), and B is a temperature T 3 (hereinafter referred to as a color development holding temperature) at which a complete color development state can be maintained. C is a point indicating the density at the minimum temperature T 2 (hereinafter referred to as the decoloring holding temperature) at which the completely decolored state can be maintained, and D is a temperature T at which the fully colored state is reached. 1 (hereinafter referred to as complete color development temperature).
The length of the line segment EF is a scale indicating the discoloration contrast, and the length of the line segment HG is a temperature width indicating the degree of hysteresis (hereinafter referred to as hysteresis width ΔH). It is easy to maintain each state before and after the color change.
Here, Δt, which is the difference between T 4 and T 3 , or the difference between T 2 and T 1 , is a scale indicating the sensitivity of discoloration.
In the present invention, the ΔH value that can be maintained in each state before and after the color change is in the range of 40 ° C. to 70 ° C., preferably 50 to 70 ° C., more preferably 60 to 70 ° C.
Furthermore, in order to present only the specific one of the state in the normal temperature range, of the two states before and after discoloration, the complete decoloring temperature (T 4) is the 50 ° C. or more, and, decoloring holding temperature (T 2) There is under -5 ° C. or less.
Here, since both the colored state and the decolored state can coexist in the normal temperature range, the reason why the complete decoloring temperature (T 4 ) is 50 ° C. or more and the decoloring holding temperature (T 2 ) is −5 ° C. or less. Explaining whether or not there is a phenomenon in which when the heating is stopped without reaching the complete decoloring temperature (T 4 ) from the color developing state through the color developing holding temperature (T 3 ), Even if the cooling is stopped in a state where the temperature does not reach the complete color development temperature (T 1 ) through the color erasure holding temperature (T 2 ) from the color erasure state, the color development state is maintained. 4 ) If the temperature exceeds 50 ° C. exceeding the normal temperature range, the colored state will be maintained in the normal use state, and if the decolorization holding temperature (T 2 ) is below the normal temperature range and −5 ° C. or lower, the color disappears. The color state is maintained during normal use.
Therefore, the temperature setting is an important requirement for the ink for a writing instrument that selectively displays the handwriting before and after color development on the writing surface and can satisfy convenience and practicality.
以下に前記した変色挙動を示す感温変色性色彩記憶性組成物の（イ）、（ロ）、（ハ）の各成分について具体的に化合物を例示する。
前記（イ）成分、即ち電子供与性呈色性有機化合物としては、従来より公知のジフェニルメタンフタリド類、フェニルインドリルフタリド類、インドリルフタリド類、ジフェニルメタンアザフタリド類、フェニルインドリルアザフタリド類、フルオラン類、スチリノキノリン類、ジアザローダミンラクトン類等が挙げられ、以下にこれらの化合物を例示する。
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−（４−ジエチルアミノフェニル）−３−（１−エチル−２−メチルインドール−３−イル）フタリド、３，３−ビス（１−ｎ−ブチル−２−メチルインドール−３−イル）フタリド、３，３−ビス（２−エトキシ−４−ジエチルアミノフェニル）−４−アザフタリド、３−〔２−エトキシ−４−（Ｎ−エチルアニリノ）フェニル〕−３−（１−エチル−２−メチルインドール−３−イル）−４−アザフタリド、３，６−ジフェニルアミノフルオラン、３，６−ジメトキシフルオラン、３，６−ジ−ｎ−ブトキシフルオラン、２−メチル−６−（Ｎ−エチル−Ｎ−ｐ−トリルアミノ）フルオラン、３−クロロ−６−シクロヘキシルアミノフルオラン、２−メチル−６−シクロヘキシルアミノフルオラン、２−（２−クロロアニリノ）−６−ジ−ｎ−ブチルアミノフルオラン、２−（３−トリフルオロメチルアニリノ）−６−ジエチルアミノフルオラン、２−（Ｎ−メチルアニリノ）−６−（Ｎ−エチル−Ｎ−ｐ−トリルアミノ）フルオラン、１，３−ジメチル−６−ジエチルアミノフルオラン、２−クロロ−３−メチル−６−ジエチルアミノフルオラン、２−アニリノ−３−メチル−６−ジエチルアミノフルオラン、２−アニリノ−３−メチル−６−ジ−ｎ−ブチルアミノフルオラン、２−キシリジノ−３−メチル−６−ジエチルアミノフルオラン、１，２−ベンツ−６−ジエチルアミノフルオラン、１，２−ベンツ−６−（Ｎ−エチル−Ｎ−イソブチルアミノ）フルオラン、１，２−ベンツ−６−（Ｎ−エチル−Ｎ−イソアミルアミノ）フルオラン、２−（３−メトキシ−４−ドデコキシスチリル）キノリン、スピロ〔５Ｈ−（１）ベンゾピラノ（２，３−ｄ）ピリミジン−５，１′（３′Ｈ）イソベンゾフラン〕−３′−オン，２−（ジエチルアミノ）−８−（ジエチルアミノ）−４−メチル−、スピロ〔５Ｈ−（１）ベンゾピラノ（２，３−ｄ）ピリミジン−５，１′（３′Ｈ）イソベンゾフラン〕−３′−オン，２−（ジ−ｎ−ブチルアミノ）−８−（ジ−ｎ−ブチルアミノ）−４−メチル−、スピロ〔５Ｈ−（１）ベンゾピラノ（２，３−ｄ）ピリミジン−５，１′（３′Ｈ）イソベンゾフラン〕−３′−オン，２−（ジ−ｎ−ブチルアミノ）−８−（ジエチルアミノ）−４−メチル−、スピロ〔５Ｈ−（１）ベンゾピラノ（２，３−ｄ）ピリミジン−５，１′（３′Ｈ）イソベンゾフラン〕−３′−オン，２−（ジ−ｎ−ブチルアミノ）−８−（Ｎ−エチル−Ｎ−ｉ−アミルアミノ）−４−メチル−、スピロ〔５Ｈ−（１）ベンゾピラノ（２，３−ｄ）ピリミジン−５，１′（３′Ｈ）イソベンゾフラン〕−３′−オン，２−（ジ−ｎ−ブチルアミノ）−８−（ジ−ｎ−ブチルアミノ）−４−フェニル、３−（２−メトキシ−４−ジメチルアミノフェニル）−３−（１−ブチル−２−メチルインドール−３−イル）−４，５，６，７−テトラクロロフタリド、３−（２−エトキシ−４−ジエチルアミノフェニル）−３−（１−エチル−２−メチルインドール−３−イル）−４，５，６，７−テトラクロロフタリド、３−（２−エトキシ−４−ジエチルアミノフェニル）−３−（１−ペンチル−２−メチルインドール−３−イル）−４，５，６，７−テトラクロロフタリド等を挙げることができる。
更には、蛍光性の黄色〜赤色の発色を発現させるのに有効な、ピリジン系、キナゾリン系、ビスキナゾリン系化合物等を挙げることができる。
Specific examples of the compounds for the components (A), (B), and (C) of the temperature-sensitive color-changing color memory composition showing the above-mentioned color change behavior are shown below.
As the component (a), that is, the electron donating color-forming organic compound, conventionally known diphenylmethane phthalides, phenyl indolyl phthalides, indolyl phthalides, diphenyl methane azaphthalides, phenyl indolyl aza Examples thereof include phthalides, fluorans, styrinoquinolines, diazarhodamine lactones, and the like.
3,3-bis (p-dimethylaminophenyl) -6-dimethylaminophthalide, 3- (4-diethylaminophenyl) -3- (1-ethyl-2-methylindol-3-yl) phthalide, 3,3 -Bis (1-n-butyl-2-methylindol-3-yl) phthalide, 3,3-bis (2-ethoxy-4-diethylaminophenyl) -4-azaphthalide, 3- [2-ethoxy-4- ( N-ethylanilino) phenyl] -3- (1-ethyl-2-methylindol-3-yl) -4-azaphthalide, 3,6-diphenylaminofluorane, 3,6-dimethoxyfluorane, 3,6-di -N-butoxyfluorane, 2-methyl-6- (N-ethyl-Np-tolylamino) fluorane, 3-chloro-6-cyclohexylaminofluorane, 2-methyl -6-cyclohexylaminofluorane, 2- (2-chloroanilino) -6-di-n-butylaminofluorane, 2- (3-trifluoromethylanilino) -6-diethylaminofluorane, 2- (N- Methylanilino) -6- (N-ethyl-Np-tolylamino) fluorane, 1,3-dimethyl-6-diethylaminofluorane, 2-chloro-3-methyl-6-diethylaminofluorane, 2-anilino-3- Methyl-6-diethylaminofluorane, 2-anilino-3-methyl-6-di-n-butylaminofluorane, 2-xylidino-3-methyl-6-diethylaminofluorane, 1,2-benz-6-diethylamino Fluorane, 1,2-benz-6- (N-ethyl-N-isobutylamino) fluorane, 1,2-benz-6 N-ethyl-N-isoamylamino) fluorane, 2- (3-methoxy-4-dodecoxystyryl) quinoline, spiro [5H- (1) benzopyrano (2,3-d) pyrimidine-5,1 ′ (3 'H) isobenzofuran] -3'-one, 2- (diethylamino) -8- (diethylamino) -4-methyl-, spiro [5H- (1) benzopyrano (2,3-d) pyrimidine-5,1' (3′H) isobenzofuran] -3′-one, 2- (di-n-butylamino) -8- (di-n-butylamino) -4-methyl-, spiro [5H- (1) benzopyrano ( 2,3-d) pyrimidine-5,1 '(3'H) isobenzofuran] -3'-one, 2- (di-n-butylamino) -8- (diethylamino) -4-methyl-, spiro [ 5H- (1) benzopyrano (2, 3-d) Pyrimidine-5,1 '(3'H) isobenzofuran] -3'-one, 2- (di-n-butylamino) -8- (N-ethyl-Ni-amylamino) -4 -Methyl-, spiro [5H- (1) benzopyrano (2,3-d) pyrimidine-5,1 '(3'H) isobenzofuran] -3'-one, 2- (di-n-butylamino)- 8- (Di-n-butylamino) -4-phenyl, 3- (2-methoxy-4-dimethylaminophenyl) -3- (1-butyl-2-methylindol-3-yl) -4,5 6,7-tetrachlorophthalide, 3- (2-ethoxy-4-diethylaminophenyl) -3- (1-ethyl-2-methylindol-3-yl) -4,5,6,7-tetrachlorophthalide 3- (2-ethoxy-4-diethylaminophenyl) 3- (1-pentyl-2-methylindole-3-yl) -4,5,6,7 can be given tetrachloro phthalide like.
Furthermore, there can be mentioned pyridine-based, quinazoline-based, bisquinazoline-based compounds and the like that are effective in developing fluorescent yellow to red color development.
成分（ロ）の電子受容性化合物としては、活性プロトンを有する化合物群、偽酸性化合物群（酸ではないが、組成物中で酸として作用して成分（イ）を発色させる化合物群）、電子空孔を有する化合物群等がある。
活性プロトンを有する化合物を例示すると、フェノール性水酸基を有する化合物としては、モノフェノール類からポリフェノール類があり、さらにその置換基としてアルキル基、アリール基、アシル基、アルコキシカルボニル基、カルボキシ基及びそのエステル又はアミド基、ハロゲン基等を有するもの、及びビス型、トリス型フェノール等、フェノール−アルデヒド縮合樹脂等が挙げられる。又、前記フェノール性水酸基を有する化合物の金属塩であってもよい。
As the electron-accepting compound of component (b), a group of compounds having active protons, a group of pseudo-acidic compounds (a group of compounds that are not acids but act as an acid in the composition and cause component (a) to develop color), electrons There is a group of compounds having pores.
Examples of compounds having active protons include monophenols to polyphenols as compounds having phenolic hydroxyl groups, and alkyl groups, aryl groups, acyl groups, alkoxycarbonyl groups, carboxy groups and esters thereof as substituents. Or what has an amide group, a halogen group, etc., phenol-aldehyde condensation resin etc., such as a bis type and a tris type phenol, are mentioned. Moreover, the metal salt of the compound which has the said phenolic hydroxyl group may be sufficient.
以下に具体例を挙げる。
フェノール、ｏ−クレゾール、ターシャリーブチルカテコール、ノニルフェノール、ｎ−オクチルフェノール、ｎ−ドデシルフェノール、ｎ−ステアリルフェノール、ｐ−クロロフェノール、ｐ−ブロモフェノール、ｏ−フェニルフェノール、ｐ−ヒドロキシ安息香酸ｎ−ブチル、ｐ−ヒドロキシ安息香酸ｎ−オクチル、レゾルシン、没食子酸ドデシル、２，２−ビス（４′−ヒドロキシフェニル）プロパン、４，４−ジヒドロキシジフェニルスルホン、１，１−ビス（４′−ヒドロキシフェニル）エタン、２，２−ビス（４′−ヒドロキシ−３−メチルフェニル）プロパン、ビス（４−ヒドロキシフェニル）スルフィド、１−フェニル−１，１−ビス（４′−ヒドロキシフェニル）エタン、１，１−ビス（４′−ヒドロキシフェニル）−３−メチルブタン、１，１−ビス（４′−ヒドロキシフェニル）−２−メチルプロパン、１，１−ビス（４′−ヒドロキシフェニル）ｎ−ヘキサン、１，１−ビス（４′−ヒドロキシフェニル）ｎ−ヘプタン、１，１−ビス（４′−ヒドロキシフェニル）ｎ−オクタン、１，１−ビス（４′−ヒドロキシフェニル）ｎ−ノナン、１，１−ビス（４′−ヒドロキシフェニル）ｎ−デカン、１，１−ビス（４′−ヒドロキシフェニル）ｎ−ドデカン、２，２−ビス（４′−ヒドロキシフェニル）ブタン、２，２−ビス（４′−ヒドロキシフェニル）エチルプロピオネート、２，２−ビス（４′−ヒドロキシフェニル）−４−メチルペンタン、２，２−ビス（４′−ヒドロキシフェニル）ヘキサフルオロプロパン、２，２−ビス（４′−ヒドロキシフェニル）ｎ−ヘプタン、２，２−ビス（４′−ヒドロキシフェニル）ｎ−ノナン等がある。
前記フェノール性水酸基を有する化合物が最も有効な熱変色特性を発現させることができるが、芳香族カルボン酸及び炭素数２〜５の脂肪族カルボン酸、カルボン酸金属塩、酸性リン酸エステル及びそれらの金属塩、１、２、３−トリアゾール及びその誘導体から選ばれる化合物等であってもよい。
Specific examples are given below.
Phenol, o-cresol, tertiary butylcatechol, nonylphenol, n-octylphenol, n-dodecylphenol, n-stearylphenol, p-chlorophenol, p-bromophenol, o-phenylphenol, n-butyl p-hydroxybenzoate N-octyl p-hydroxybenzoate, resorcin, dodecyl gallate, 2,2-bis (4′-hydroxyphenyl) propane, 4,4-dihydroxydiphenyl sulfone, 1,1-bis (4′-hydroxyphenyl) Ethane, 2,2-bis (4'-hydroxy-3-methylphenyl) propane, bis (4-hydroxyphenyl) sulfide, 1-phenyl-1,1-bis (4'-hydroxyphenyl) ethane, 1,1 -Bis (4'-hydroxyphenyl) -3 Methylbutane, 1,1-bis (4'-hydroxyphenyl) -2-methylpropane, 1,1-bis (4'-hydroxyphenyl) n-hexane, 1,1-bis (4'-hydroxyphenyl) n- Heptane, 1,1-bis (4′-hydroxyphenyl) n-octane, 1,1-bis (4′-hydroxyphenyl) n-nonane, 1,1-bis (4′-hydroxyphenyl) n-decane, 1,1-bis (4′-hydroxyphenyl) n-dodecane, 2,2-bis (4′-hydroxyphenyl) butane, 2,2-bis (4′-hydroxyphenyl) ethyl propionate, 2,2 -Bis (4'-hydroxyphenyl) -4-methylpentane, 2,2-bis (4'-hydroxyphenyl) hexafluoropropane, 2,2-bis (4'-hydroxyphenyl) Sulfonyl) n- heptane, there is 2,2-bis (4'-hydroxyphenyl) n- nonane.
The compound having a phenolic hydroxyl group can develop the most effective thermochromic property, but aromatic carboxylic acids and aliphatic carboxylic acids having 2 to 5 carbon atoms, carboxylic acid metal salts, acidic phosphate esters and their It may be a compound selected from metal salts, 1,2,3-triazole and derivatives thereof.
次に（ハ）成分のエステル化合物について具体的に例示する。
本発明に用いられる一般式（１）で示されるエステル化合物は、分子内に芳香環を２個有するアルコール化合物と、炭素数４以上の飽和又は不飽和脂肪酸とから構成されるエステル化合物である。
式中のＲは炭素数４以上のアルキル基又はアルケニル基を示すが、好ましくは炭素数６〜２０のアルキル基、更に好ましくは炭素数８〜１８のアルキル基である。
前記化合物として具体的には、ブタン酸−４−ベンジルオキシフェニルエチル、ペンタン酸−４−ベンジルオキシフェニルエチル、ヘキサン酸−４−ベンジルオキシフェニルエチル、ヘプタン酸−４−ベンジルオキシフェニルエチル、オクタン酸−４−ベンジルオキシフェニルエチル、ノナン酸−４−ベンジルオキシフェニルエチル、デカン酸−４−ベンジルオキシフェニルエチル、ウンデカン酸−４−ベンジルオキシフェニルエチル、ドデカン酸−４−ベンジルオキシフェニルエチル、トリデカン酸−４−ベンジルオキシフェニルエチル、テトラデカン酸−４−ベンジルオキシフェニルエチル、ペンタデカン酸−４−ベンジルオキシフェニルエチル、ヘキサデカン酸−４−ベンジルオキシフェニルエチル、ヘプタデカン酸−４−ベンジルオキシフェニルエチル、オクタデカン酸−４−ベンジルオキシフェニルエチル、ノナデカン酸−４−ベンジルオキシフェニルエチル、エイコサン酸−４−ベンジルオキシフェニルエチル、トリコサン酸−４−ベンジルオキシフェニルエチル、テトラコサン酸−４−ベンジルオキシフェニルエチル、ペンタコサン酸−４−ベンジルオキシフェニルエチル、ヘキサコサン酸−４−ベンジルオキシフェニルエチル、ヘプタコサン酸−４−ベンジルオキシフェニルエチル、オクタコサン酸−４−ベンジルオキシフェニルエチル、ノナコサン酸−４−ベンジルオキシフェニルエチル、トリアコンタン酸−４−ベンジルオキシフェニルエチル、ヘントリアコンタン酸−４−ベンジルオキシフェニルエチルを例示できる。
Next, the ester compound of component (c) will be specifically exemplified.
The ester compound represented by the general formula (1) used in the present invention is an ester compound composed of an alcohol compound having two aromatic rings in the molecule and a saturated or unsaturated fatty acid having 4 or more carbon atoms.
R in the formula represents an alkyl group or alkenyl group having 4 or more carbon atoms, preferably an alkyl group having 6 to 20 carbon atoms, more preferably an alkyl group having 8 to 18 carbon atoms.
Specific examples of the compound include butanoic acid-4-benzyloxyphenylethyl, pentanoic acid-4-benzyloxyphenylethyl, hexanoic acid-4-benzyloxyphenylethyl, heptanoic acid-4-benzyloxyphenylethyl, and octanoic acid. -4-benzyloxyphenylethyl, nonanoic acid-4-benzyloxyphenylethyl, decanoic acid-4-benzyloxyphenylethyl, undecanoic acid-4-benzyloxyphenylethyl, dodecanoic acid-4-benzyloxyphenylethyl, tridecanoic acid -4-benzyloxyphenylethyl, tetradecanoic acid-4-benzyloxyphenylethyl, pentadecanoic acid-4-benzyloxyphenylethyl, hexadecanoic acid-4-benzyloxyphenylethyl, heptadecanoic acid-4-benzylo Cyphenylethyl, octadecanoic acid-4-benzyloxyphenylethyl, nonadecanoic acid-4-benzyloxyphenylethyl, eicosanoic acid-4-benzyloxyphenylethyl, tricosanoic acid-4-benzyloxyphenylethyl, tetracosanoic acid-4-benzyl Oxyphenylethyl, pentacosanoic acid-4-benzyloxyphenylethyl, hexacosanoic acid-4-benzyloxyphenylethyl, heptacosanoic acid-4-benzyloxyphenylethyl, octacosanoic acid-4-benzyloxyphenylethyl, nonacosanoic acid-4-benzyl Examples thereof include oxyphenyl ethyl, triacontanoic acid-4-benzyloxyphenylethyl, and hentriacontanoic acid-4-benzyloxyphenylethyl.
前記エステル化合物は、従来の感温変色性色彩記憶性液状組成物に用いられているエステル化合物を用いた場合と同程度、或いは、それ以上の広いヒステリシス幅が得られるため、実用性に富み、応用性に優れる。 The ester compound has a wide hysteresis width equivalent to or higher than the case of using an ester compound used in a conventional temperature-sensitive color-changing color-memory liquid composition. Excellent applicability.
本発明の（ハ）成分は前記エステル化合物を用いるが、必要に応じてヒステリシス特性を大きく変動しない範囲で他のエステル類、アルコール類、カルボン酸類、ケトン類、アミド類等を加えることができる。この場合、その添加量は本発明のエステル１００に対して２０以下（重量部）が所期の色彩記憶性効果を有効に発現させるうえで好ましい。 As the component (c) of the present invention, the ester compound is used, and other esters, alcohols, carboxylic acids, ketones, amides, and the like can be added as long as the hysteresis characteristics do not greatly change. In this case, the addition amount is preferably 20 or less (parts by weight) with respect to the ester 100 of the present invention in order to effectively exhibit the desired color memory effect.
本発明における（イ）、（ロ）、（ハ）３成分の構成成分割合は、濃度、変色温度、変色形態や各成分の種類に左右されるが、一般的に所望の特性が得られる成分比は、（イ）成分１に対して、（ロ）成分０．１〜５０、好ましくは０．５〜２０、（ハ）成分１〜８００、好ましくは５〜２００の範囲である（前記割合はいずれも重量部である）。
又、各成分は各々二種以上の混合であってもよく、機能に支障のない範囲で酸化防止剤、紫外線吸収剤、赤外線吸収剤、溶解助剤等を添加することができる。
In the present invention, the proportions of the three components (A), (B), and (C) depend on the concentration, the color change temperature, the color change form, and the type of each component, but in general, components that provide desired characteristics. The ratio is in the range of (b) component 1 to (b) component 0.1 to 50, preferably 0.5 to 20, (c) component 1 to 800, preferably 5 to 200 (the ratio). Are all parts by weight).
Each component may be a mixture of two or more, and an antioxidant, an ultraviolet absorber, an infrared absorber, a dissolution aid, etc. can be added as long as the function is not hindered.
前記三成分からなる均質相溶混合物はマイクロカプセルに内包して使用される。それは、酸性物質、塩基性物質、過酸化物等の化学的に活性な物質又は他の溶剤成分と接触しても、その機能を低下させることがないことは勿論、耐熱安定性が保持できるためであり、種々の使用条件において感温変色性色彩記憶性組成物は同一の組成に保たれ、同一の作用効果を奏することができるからである。
前記マイクロカプセルは、平均粒子径０．５〜２０μｍ、好ましくは０．５〜１０μｍ、更に好ましくは０．５〜５μｍの範囲が実用性を満たす。
前記マイクロカプセルは、最大外径の平均値が、２０μｍを越える系では、インキへの使用に対して、分散安定性に欠ける。
一方、最大外径の平均値が０．５μｍ以下の系では、高濃度の発色性を示し難い。
また、前記マイクロカプセルは、内包物／壁膜＝７／１〜１／１（重量比）の範囲が有効であり、内包物の比率が前記範囲より大になると発色時の色濃度及び鮮明性の低下を免れず、好適には、内包物／壁膜＝６／１〜１／１（重量比）である。
前記マイクロカプセル化は、従来より公知のイソシアネート系の界面重合法、メラミン−ホルマリン系等のｉｎ Ｓｉｔｕ重合法、液中硬化被覆法、水溶液からの相分離法、有機溶媒からの相分離法、融解分散冷却法、気中懸濁被覆法、スプレードライング法等があり、用途に応じて適宜選択される。更にマイクロカプセルの表面には、目的に応じて更に二次的な樹脂皮膜を設けて耐久性を付与させたり、表面特性を改質させて実用に供することもできる。
The three-component homogeneous compatible mixture is used by being encapsulated in microcapsules. It does not deteriorate its function even when it comes in contact with chemically active substances such as acidic substances, basic substances, peroxides, or other solvent components. This is because the temperature-sensitive color-changing color memory composition can be maintained in the same composition and exhibit the same effects under various usage conditions.
The microcapsules satisfy the practicality in the range of an average particle size of 0.5 to 20 μm, preferably 0.5 to 10 μm, more preferably 0.5 to 5 μm.
When the average value of the maximum outer diameter exceeds 20 μm, the microcapsule lacks dispersion stability for use in ink.
On the other hand, in a system having an average value of the maximum outer diameter of 0.5 μm or less, it is difficult to exhibit high density color development.
In addition, the range of inclusion / wall membrane = 7/1 to 1/1 (weight ratio) is effective for the microcapsule. When the ratio of inclusion is larger than the above range, the color density and sharpness at the time of color development. However, the inclusion / wall membrane = 6/1 to 1/1 (weight ratio) is preferable.
The microencapsulation includes conventionally known isocyanate-based interfacial polymerization methods, in-situ polymerization methods such as melamine-formalin, in-liquid curing coating methods, phase separation methods from aqueous solutions, phase separation methods from organic solvents, melting There are a dispersion cooling method, an air suspension coating method, a spray drying method, and the like, which are appropriately selected according to use. Further, a secondary resin film may be provided on the surface of the microcapsule according to the purpose to impart durability, or the surface characteristics may be modified for practical use.
本発明においては、前記マイクロカプセル顔料を溶剤中に分散してインキ組成物が得られる。
前記インキに用いられる溶剤としては、水と必要により水溶性有機溶剤が用いられる。
前記水溶性有機溶剤としては、例えば、エタノール、プロパノール、ブタノール、グリセリン、ソルビトール、トリエタノールアミン、ジエタノールアミン、モノエタノールアミン、エチレングリコール、ジエチレングリコール、チオジエチレングリコール、ポリエチレングリコール、プロピレングリコール、ブチレングリコール、エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、エチレングリコールモノブチルエーテル、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテル、ジエチレングリコールモノブチルエーテル、プロピレングリコールモノブチルエーテル、エチレングリコールモノメチルエーテルアセテート、スルフォラン、２−ピロリドン、Ｎ−メチル−２−ピロリドン等が挙げられる。
In the present invention, the microcapsule pigment is dispersed in a solvent to obtain an ink composition.
As a solvent used for the ink, water and, if necessary, a water-soluble organic solvent are used.
Examples of the water-soluble organic solvent include ethanol, propanol, butanol, glycerin, sorbitol, triethanolamine, diethanolamine, monoethanolamine, ethylene glycol, diethylene glycol, thiodiethylene glycol, polyethylene glycol, propylene glycol, butylene glycol, and ethylene glycol monomethyl. Ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monobutyl ether, ethylene glycol monomethyl ether acetate, sulfolane, 2-pyrrolidone, N-methyl-2- Pyrrolidone, and the like.
樹脂としては、ケトン樹脂、ケトン−ホルムアルデヒド樹脂、アミド樹脂、アルキッド樹脂、ロジン変性樹脂、ロジン変性フェノール樹脂、フェノール樹脂、キシレン樹脂、ポリビニルピロリドン、α−及びβ−ピネン・フェノール重縮合樹脂、ポリビニルブチラール樹脂、アクリル樹脂、スチレンマレイン酸共重合物、セルロース誘導体、ポリビニルピロリドン、ポリビニルアルコール、デキストリン等を添加することができ、被筆記体への固着性や粘性付与のために用いられる。 Examples of resins include ketone resins, ketone-formaldehyde resins, amide resins, alkyd resins, rosin-modified resins, rosin-modified phenol resins, phenol resins, xylene resins, polyvinylpyrrolidone, α- and β-pinene / phenol polycondensation resins, and polyvinyl butyral. Resins, acrylic resins, styrene maleic acid copolymers, cellulose derivatives, polyvinyl pyrrolidone, polyvinyl alcohol, dextrin, and the like can be added, and are used for fixing to a writing material and imparting viscosity.
更に、必要により剪断減粘性付与剤を添加することもできる。
前記剪断減粘性付与剤を添加することによって筆跡の滲みを抑制することができるため、紙面は勿論、浸透性の高い布帛等の繊維材料に筆記しても筆跡は滲むことなく、良好な筆跡を形成できる。
更に、前記インキを充填する筆記具がボールペン形態の場合、不使用時のボールとチップの間隙からのインキ漏れだしを防止したり、筆記先端部を上向き（正立状態）で放置した場合のインキの逆流を防止することができる。
尚、前記剪断減粘性付与剤を添加したインキ組成物の粘度は、２０℃でのＥ型回転粘度計による３．８４Ｓ−１の剪断速度におけるインキ粘度が２０〜３００ｍＰａ・ｓを示し、且つ、剪断減粘指数が０．１〜０．９を示すことが好ましい。
なお、剪断減粘指数（ｎ）は、剪断応力値（Ｔ）及び剪断速度値（ｊ）の如き粘度計による流動学測定から得られる実験式Ｔ＝Ｋｊｎ（Ｋは非ニュートン粘性係数）にあてはめることによって計算される値である。
Further, if necessary, a shear thinning agent can be added.
By adding the shear thinning agent, it is possible to suppress blotting of the handwriting, so that even if writing on a fiber material such as a highly penetrating cloth as well as paper, the handwriting does not bleed and a good handwriting is achieved. Can be formed.
Furthermore, when the writing instrument to be filled with the ink is in the form of a ballpoint pen, it prevents ink leakage from the gap between the ball and the tip when not in use, or the ink when the writing tip is left upward (upright state). Backflow can be prevented.
The viscosity of the ink composition to which the shear thinning agent is added is 20 to 300 mPa · s at a shear rate of 3.84S −1 by an E-type rotational viscometer at 20 ° C., and It is preferable that the shear thinning index is 0.1 to 0.9.
The shear thinning index (n) is expressed by an empirical formula T = Kj n (K is a non-Newtonian viscosity coefficient) obtained from rheological measurement by a viscometer such as a shear stress value (T) and a shear rate value (j). It is a value calculated by fitting.
前記剪断減粘性付与剤としては、キサンタンガム、ウェランガム、構成単糖がグルコースとガラクトースの有機酸修飾ヘテロ多糖体であるサクシノグリカン（平均分子量約１００乃至８００万）、アルカガム、グアーガム、ローカストビーンガム及びその誘導体、ヒドロキシエチルセルロース、アルギン酸アルキルエステル類、メタクリル酸のアルキルエステルを主成分とする分子量１０万〜１５万の重合体、グルコマンナン、寒天やカラゲニン等の海藻より抽出されるゲル化能を有する増粘多糖類、ベンジリデンソルビトール及びベンジリデンキシリトール又はこれらの誘導体、架橋性アクリル酸重合体、無機質微粒子、ポリグリセリン脂肪酸エステル、ポリオキシエチレンソルビタン脂肪酸エステル、ポリエチレングリコール脂肪酸エステル、ポリオキシエチレンヒマシ油、ポリオキシエチレンラノリン・ラノリンアルコール・ミツロウ誘導体、ポリオキシエチレンアルキルエーテル、ポリオキシプロピレンアルキルエーテル、ポリオキシエチレンアルキルフェニルエーテル、脂肪酸アミド等のＨＬＢ値が８〜１２のノニオン系界面活性剤、ジアルキル又はジアルケニルスルホコハク酸の塩類、Ｎ−アルキル−２−ピロリドンとアニオン系界面活性剤の混合物、ポリビニルアルコールとアクリル系樹脂の混合物を例示できる。 Examples of the shear thinning agent include xanthan gum, welan gum, succinoglycan (average molecular weight of about 1 to 8 million) whose constituent monosaccharide is an organic acid-modified heteropolysaccharide of glucose and galactose, alka gum, guar gum, locust bean gum and A gel having a gelling ability extracted from seaweeds such as glucomannan, agar and carrageenan, polymers having a molecular weight of 100,000 to 150,000 mainly composed of derivatives thereof, hydroxyethyl cellulose, alginic acid alkyl esters, and alkyl esters of methacrylic acid. Viscous polysaccharides, benzylidene sorbitol and benzylidene xylitol or derivatives thereof, crosslinkable acrylic acid polymer, inorganic fine particles, polyglycerin fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyethylene glycol fatty acid ester , Polyoxyethylene castor oil, polyoxyethylene lanolin, lanolin alcohol, beeswax derivative, polyoxyethylene alkyl ether, polyoxypropylene alkyl ether, polyoxyethylene alkylphenyl ether, fatty acid amide, etc. Examples of the surfactant include salts of dialkyl or dialkenylsulfosuccinic acid, a mixture of N-alkyl-2-pyrrolidone and an anionic surfactant, and a mixture of polyvinyl alcohol and an acrylic resin.
本発明のインキ組成物をボールペンに充填して用いる場合は、オレイン酸等の高級脂肪酸、長鎖アルキル基を有するノニオン性界面活性剤、ポリエーテル変性シリコーンオイル、チオ亜燐酸トリ（アルコキシカルボニルメチルエステル）やチオ亜燐酸トリ（アルコキシカルボニルエチルエステル）等のチオ亜燐酸トリエステル、ポリオキシエチレンアルキルエーテル又はポリオキシエチレンアルキルアリールエーテルのリン酸モノエステル、ポリオキシエチレンアルキルエーテル又はポリオキシエチレンアルキルアリールエーテルのリン酸ジエステル、或いは、それらの金属塩、アンモニウム塩、アミン塩、アルカノールアミン塩等の潤滑剤を添加してボール受け座の摩耗防止効果を付与することが好ましい。 When the ink composition of the present invention is used by being filled into a ballpoint pen, a higher fatty acid such as oleic acid, a nonionic surfactant having a long chain alkyl group, a polyether-modified silicone oil, a thiophosphorous acid tri (alkoxycarbonylmethyl ester) ) And thiophosphite triester (alkoxycarbonylethyl ester), etc., polyoxyethylene alkyl ether or polyoxyethylene alkyl aryl ether phosphate monoester, polyoxyethylene alkyl ether or polyoxyethylene alkyl aryl ether It is preferable to add a lubricant such as a phosphoric acid diester or a metal salt, an ammonium salt, an amine salt, an alkanolamine salt thereof to give the ball seat an antiwear effect.
その他、必要に応じて炭酸ナトリウム、燐酸ナトリウム、酢酸ソーダ等の無機塩類、水溶性のアミン化合物等の有機塩基性化合物等のｐＨ調整剤、ベンゾトリアゾール、トリルトリアゾール、ジシクロヘキシルアンモニウムナイトライト、ジイソプロピルアンモニウムナイトライト、サポニン等の防錆剤、石炭酸、１、２−ベンズチアゾリン３−オンのナトリウム塩、安息香酸ナトリウム、デヒドロ酢酸ナトリウム、ソルビン酸カリウム、パラオキシ安息香酸プロピル、２，３，５，６−テトラクロロ−４−（メチルスルフォニル）ピリジン等の防腐剤或いは防黴剤、尿素、ノニオン系界面活性剤、還元又は非還元デンプン加水分解物、トレハロース等のオリゴ糖類、ショ糖、サイクロデキストリン、ぶどう糖、デキストリン、ソルビット、マンニット、ピロリン酸ナトリム等の湿潤剤、消泡剤、分散剤、インキの浸透性を向上させるフッ素系界面活性剤やノニオン系の界面活性剤を使用してもよい。 In addition, pH adjusters such as inorganic salts such as sodium carbonate, sodium phosphate and sodium acetate, organic basic compounds such as water-soluble amine compounds, benzotriazole, tolyltriazole, dicyclohexylammonium nitrite, diisopropylammonium night as necessary Rust prevention agent such as light, saponin, coalic acid, sodium salt of 1,2-benzthiazolin-3-one, sodium benzoate, sodium dehydroacetate, potassium sorbate, propyl paraoxybenzoate, 2,3,5,6-tetra Preservatives or fungicides such as chloro-4- (methylsulfonyl) pyridine, urea, nonionic surfactants, reduced or non-reduced starch hydrolysates, oligosaccharides such as trehalose, sucrose, cyclodextrin, glucose, dextrin , Sorbit, N'nitto, wetting agents such as pyrophosphate sodium, defoamers, may be used a dispersing agent, a fluorine based surfactant to improve ink permeability and nonionic surfactants.
前記インキ組成物は、チップを筆記先端部に装着したマーキングペンやボールペンに充填して実用に供される。
マーキングペンに充填する場合、マーキングペン自体の構造、形状は特に限定されるものではなく、例えば、繊維チップ、フェルトチップ、プラスチックチップを筆記先端部に装着し、軸筒内部に収容した繊維束からなるインキ吸蔵体にインキを含浸させ、筆記先端部にインキを供給する構造、軸筒内部に直接インキを収容し、櫛溝状のインキ流量調節部材や繊維束からなるインキ流量調節部材を介在させる構造のマーキングペンが挙げられる。
ボールペンに充填する場合、ボールペン自体の構造、形状は特に限定されるものではなく、例えば、軸筒内部に収容した繊維束からなるインキ吸蔵体にインキを含浸させ、筆記先端部にインキを供給する構造、軸筒内部に直接インキを収容し、櫛溝状のインキ流量調節部材や繊維束からなるインキ流量調節部材を介在させる構造、軸筒内にインキ組成物を充填したインキ収容管を有し、該インキ収容管はボールを先端部に装着したチップに連通しており、さらにインキの端面には逆流防止用の液栓が密接している構造のボールペンが挙げられる。
The ink composition is put into practical use by filling a marking pen or ballpoint pen with a tip attached to the writing tip.
When filling the marking pen, the structure and shape of the marking pen itself are not particularly limited. For example, a fiber tip, felt tip, plastic tip is attached to the writing tip, and the fiber bundle contained in the shaft cylinder is used. The ink occlusion body is impregnated with ink, the ink is supplied to the tip of the writing, the ink is directly stored inside the shaft cylinder, and the ink flow rate adjustment member consisting of a comb groove-like ink flow rate adjustment member or fiber bundle is interposed The marking pen of structure is mentioned.
When filling the ball-point pen, the structure and shape of the ball-point pen itself are not particularly limited. For example, an ink occlusion body composed of a fiber bundle housed in the shaft tube is impregnated with ink and supplied to the writing tip. Structure, ink is stored directly inside the shaft cylinder, and there is an ink storage tube filled with the ink composition in the shaft cylinder, with a comb groove-shaped ink flow control member and an ink flow control member consisting of fiber bundles interposed The ink storage tube communicates with a chip having a ball attached to the tip, and a ballpoint pen having a structure in which a liquid stopper for backflow prevention is in intimate contact with the end surface of the ink.
前記ボールペンチップについて更に詳しく説明すると、金属製のパイプの先端近傍を外面より内方に押圧変形させたボール抱持部にボールを抱持してなるチップ、或いは、金属材料をドリル等による切削加工により形成したボール抱持部にボールを抱持してなるチップ、金属又はプラスチック製チップ内部に樹脂製のボール受け座を設けたチップ、或いは、前記チップに抱持するボールをバネ体により前方に付勢させたもの等を適用できる。
又、前記ボールは、超硬合金、ステンレス鋼、ルビー、セラミック、樹脂、ゴム等の０．３〜３ｍｍ径程度のものが適用できる。
なお、本発明のインキを充填する筆記具は、ボールと同様の転動作用により筆跡を形成させる、ローラー等の転動機構を筆記先端部に備えたものを含む。
The ballpoint pen tip will be described in more detail. A tip formed by holding a ball in a ball holding portion obtained by pressing and deforming the vicinity of the tip of a metal pipe inward from the outer surface, or a metal material is cut by a drill or the like A chip formed by holding the ball in the ball holding part formed by the above, a chip provided with a resin ball receiving seat inside a metal or plastic chip, or a ball held by the chip is moved forward by a spring body Energized items can be applied.
Moreover, the said ball | bowl can use a thing about 0.3-3 mm diameter, such as a cemented carbide alloy, stainless steel, a ruby, a ceramic, resin, rubber | gum.
In addition, the writing instrument filled with the ink of the present invention includes those provided with a rolling mechanism such as a roller at the tip of the writing for forming a handwriting by the same rolling operation as that of the ball.
インキ組成物を収容するインキ収容管は、例えば、ポリエチレン、ポリプロピレン、ポリエチレンテレフタレート、ナイロン等の熱可塑性樹脂からなる成形体が用いられる。
更に、インキ収容管として透明、着色透明、或いは半透明の成形体を用いることにより、インキ色やインキ残量等を確認できる。
前記インキ収容管にはチップを直接連結する他、接続部材を介して前記インキ収容管とチップを連結してもよい。
尚、インキ収容管はレフィルの形態として、前記レフィルを軸筒内に収容するものでもよいし、先端部にチップを装着した軸筒自体をインキ収容体として、前記軸筒内に直接インキを充填してもよい。
For example, a molded body made of a thermoplastic resin such as polyethylene, polypropylene, polyethylene terephthalate, or nylon is used as the ink storage tube that stores the ink composition.
Furthermore, by using a transparent, colored transparent, or translucent molded body as the ink containing tube, the ink color, the remaining amount of ink, and the like can be confirmed.
In addition to directly connecting the chip to the ink storage tube, the ink storage tube and the chip may be connected via a connecting member.
The ink storage tube may be a refill type in which the refill is accommodated in the shaft cylinder, or the shaft cylinder itself having a tip mounted on the tip is used as an ink container to directly fill the shaft cylinder with ink. May be.
前記インキ収容管に収容したインキ組成物の後端にはインキ逆流防止体を充填することもできる。
前記インキ逆流防止体組成物は不揮発性液体又は難揮発性液体からなる。
具体的には、ワセリン、スピンドル油、ヒマシ油、オリーブ油、精製鉱油、流動パラフィン、ポリブテン、α−オレフィン、α−オレフィンのオリゴマーまたはコオリゴマー、ジメチルシリコーンオイル、メチルフェニルシリコーンオイル、アミノ変性シリコーンオイル、ポリエーテル変性シリコーンオイル、脂肪酸変性シリコーンオイル等があげられ、一種又は二種以上を併用することもできる。
The back end of the ink composition accommodated in the ink accommodating tube may be filled with an ink backflow prevention body.
The ink backflow prevention body composition is composed of a non-volatile liquid or a hardly volatile liquid.
Specifically, petroleum jelly, spindle oil, castor oil, olive oil, refined mineral oil, liquid paraffin, polybutene, α-olefin, α-olefin oligomer or co-oligomer, dimethyl silicone oil, methylphenyl silicone oil, amino-modified silicone oil, Examples thereof include polyether-modified silicone oil and fatty acid-modified silicone oil, and one or more can be used in combination.
前記不揮発性液体及び／又は難揮発性液体には、ゲル化剤を添加して好適な粘度まで増粘させることが好ましく、表面を疎水処理したシリカ、表面をメチル化処理した微粒子シリカ、珪酸アルミニウム、膨潤性雲母、疎水処理を施したベントナイトやモンモリロナイトなどの粘土系増粘剤、ステアリン酸マグネシウム、ステアリン酸カルシウム、ステアリン酸アルミニウム、ステアリン酸亜鉛等の脂肪酸金属石鹸、トリベンジリデンソルビトール、脂肪酸アマイド、アマイド変性ポリエチレンワックス、水添ひまし油、脂肪酸デキストリン等のデキストリン系化合物、セルロース系化合物を例示できる。
更に、前記液状のインキ逆流防止体組成物と、固体のインキ逆流防止体を併用することもできる。
It is preferable to add a gelling agent to the nonvolatile liquid and / or the hardly volatile liquid to increase the viscosity to a suitable viscosity. The surface of the silica is hydrophobized, the surface is methylated fine particle silica, and aluminum silicate. , Swellable mica, hydrophobic thickeners such as bentonite and montmorillonite, fatty acid metal soaps such as magnesium stearate, calcium stearate, aluminum stearate, zinc stearate, tribenzylidene sorbitol, fatty acid amide, amide modified Examples include dextrin compounds such as polyethylene wax, hydrogenated castor oil, fatty acid dextrin, and cellulose compounds.
Furthermore, the liquid ink backflow prevention body composition and a solid ink backflow prevention body composition can be used in combination.
以下に本発明の実施例を示すが、本発明はこれに限定されるものではない。
実施例１
感温変色性色彩記憶性マイクロカプセル顔料の調製
（イ）成分として２−（２−クロロアニリノ）−６−ジ−ｎ−ブチルアミノフルオラン４．５重量部、（ロ）成分として１，１−ビス（４′−ヒドロキシフェニル）ｎ−デカン４．５重量部、１，１−ビス（４′−ヒドロキシフェニル）ヘキサフルオロプロパン７．５重量部、（ハ）成分としてカプリン酸４−ベンジルオキシフェニルエチル５０．０重量部からなる感温変色性色彩記憶性組成物を均一に加温溶解し、壁膜材料として芳香族多価イソシアネートプレポリマー３０．０重量部、助溶剤４０．０重量部を混合した溶液を、８％ポリビニルアルコール水溶液中で微小滴になるように乳化分散し、７０℃で約１時間攪拌を続けた後、水溶性脂肪族変性アミン２．５重量部を加え、更に６時間攪拌を続けて感温変色性色彩記憶性マイクロカプセル顔料懸濁液を得た。
前記懸濁液を遠心分離して感温変色性色彩記憶性マイクロカプセル顔料を単離した。
なお、前記マイクロカプセル顔料のヒステリシス幅（ΔＨ）は６３℃、完全発色温度（Ｔ１）は−２０℃、消色保持温度（Ｔ２）は−９℃、発色保持温度（Ｔ３）は４０℃、完全消色温度（Ｔ４）は５７℃であり、温度変化により黒色から無色に変色する。
Examples of the present invention are shown below, but the present invention is not limited thereto.
Example 1
Preparation of temperature-sensitive color-changing color-memory microcapsule pigment (i) 4.5 parts by weight of 2- (2-chloroanilino) -6-di-n-butylaminofluorane as component (1,) 1,1- Bis (4'-hydroxyphenyl) n-decane 4.5 parts by weight, 1,1-bis (4'-hydroxyphenyl) hexafluoropropane 7.5 parts by weight, (C) 4-benzyloxyphenyl caprate as component A temperature-sensitive color-changing color memory composition composed of 50.0 parts by weight of ethyl is uniformly heated and dissolved. The mixed solution is emulsified and dispersed in 8% aqueous polyvinyl alcohol solution so as to form fine droplets. After stirring at 70 ° C. for about 1 hour, 2.5 parts by weight of a water-soluble aliphatic modified amine is added. Stirring was continued for 6 hours to obtain a temperature-sensitive color-change color-memory microcapsule pigment suspension.
The suspension was centrifuged to isolate a thermochromic color memory microcapsule pigment.
The microcapsule pigment has a hysteresis width (ΔH) of 63 ° C., a complete color development temperature (T 1 ) of −20 ° C., a decolorization retention temperature (T 2 ) of −9 ° C., and a color development retention temperature (T 3 ) of 40. The complete decolorization temperature (T 4 ) is 57 ° C., and the color changes from black to colorless according to the temperature change.
感温変色性色彩記憶性インキの調製
前記マイクロカプセル顔料２５．７重量部、サクシノグリカン（剪断減粘性付与剤）０．２重量部、尿素５．５重量部、グリセリン７．５重量部、ノニオン系浸透性付与剤〔サンノプコ（株）社製、商品名：ノプコＳＷ−ＷＥＴ−３６６〕０．０３重量部、変性シリコーン系消泡剤〔日本シリコーン（株）製、商品名：ＦＳアンチフォーム０１３Ｂ〕０．１５重量部、防腐剤〔ゼネカ（株）製、商品名：プロキセルＸＬ−２〕０．１部、潤滑剤〔第一工業製薬（株）製プライサーフＡ２１２Ｃ〕０．５重量部、トリエタノールアミン０．５重量部、水５９．８２重量部からなる感温変色性色彩記憶性インキを調製した。
Preparation of temperature-sensitive color-changing color memory ink 25.7 parts by weight of the microcapsule pigment, 0.2 parts by weight of succinoglycan (shear thinning agent), 5.5 parts by weight of urea, 7.5 parts by weight of glycerin, Nonionic permeability imparting agent [manufactured by San Nopco Co., Ltd., trade name: Nopco SW-WET-366] 0.03 parts by weight, modified silicone antifoaming agent [manufactured by Nippon Silicone Co., Ltd., trade name: FS Antifoam 013B] 0.15 parts by weight, preservative [Zeneca Co., Ltd., trade name: Proxel XL-2] 0.1 parts, lubricant [Daiichi Kogyo Seiyaku Plysurf A212C] 0.5 parts by weight A temperature-sensitive color-changing color memory ink comprising 0.5 parts by weight of triethanolamine and 59.82 parts by weight of water was prepared.
筆記具の作製
前記インキ（予め−２０℃以下に冷却してマイクロカプセル顔料を黒色に発色させた後、室温下で放置したもの）を内径４．４ｍｍのポリプロピレン製パイプに０．９７ｇ吸引充填し、樹脂製ホルダーを介してボールペンチップと連結させた。
次いで、前記ポリプロピレン製パイプの後部より、ポリブテンを主成分とする粘弾性を有するインキ逆流防止体（液栓）を充填し、更に尾栓をパイプの後部に嵌合させ、先軸胴、後軸胴を組み付け、キャップを嵌めた後、遠心処理により脱気処理を行なってボールペンを得た。
なお、前記ボールペンチップは、金属製のパイプの先端近傍を外面より内方に押圧変形させたチップの先端部に直径０．７ｍｍのステンレス鋼ボールを抱持させてなり、且つ、前記ボールはバネ体により前方に付勢させたものであり、キャップは頂部に摩擦体としてシリコーンゴムを装着してなる。
Preparation of writing instrument 0.97 g of the ink (previously cooled to −20 ° C. or lower and allowed to stand at room temperature after coloring the microcapsule pigment in black) was sucked and filled in 0.97 g of a polypropylene pipe having an inner diameter of 4.4 mm, It connected with the ball-point pen tip through the resin holder.
Next, from the rear part of the polypropylene pipe, an ink backflow prevention body (liquid stopper) having viscoelasticity mainly composed of polybutene is filled, and a tail plug is fitted to the rear part of the pipe. After the cylinder was assembled and the cap was fitted, a deaeration process was performed by a centrifugal process to obtain a ballpoint pen.
The ball-point pen tip has a stainless steel ball having a diameter of 0.7 mm held at the tip end of a tip formed by pressing and deforming the vicinity of the tip of a metal pipe inward from the outer surface, and the ball is a spring. The cap is biased forward by the body, and the cap is formed by mounting silicone rubber as a friction body on the top.
前記ボールペンを用いて紙面に筆記して黒色の文字（筆跡）を形成した。
前記筆跡は、室温（２５℃）で黒色を呈しており、消色保持温度（−９℃）以上、完全消色温度（５７℃）以下の温度でこの状態を保持していた。
前記文字をキャップに装着した摩擦体を用いて擦過すると、該文字は消色して無色となり、消色保持温度（−９℃）以上、完全消色温度（５７℃）以下の温度でこの状態を保持していた。
なお、前記紙面を冷凍庫に入れて完全発色温度以下に冷却すると、再び文字は黒色になる変色挙動を示し、前記変色挙動は繰り返し再現することができた。
Black characters (handwriting) were formed by writing on the paper using the ballpoint pen.
The handwriting was black at room temperature (25 ° C.), and this state was maintained at a temperature not lower than the decolorization holding temperature (−9 ° C.) and not higher than the complete decoloring temperature (57 ° C.).
When the character is abraded with a friction body attached to a cap, the character is decolored and colorless, and this state is maintained at a temperature equal to or higher than the decolorization holding temperature (−9 ° C.) and below the complete decoloring temperature (57 ° C.). Was holding.
When the paper surface was placed in a freezer and cooled below the full color development temperature, the characters again showed a discoloration behavior that turned black, and the discoloration behavior could be reproduced repeatedly.
実施例２
感温変色性色彩記憶性マイクロカプセル顔料の調製
（イ）成分として３−（４−ジエチルアミノ−２−ヘキシルオキシフェニル）−３−（１−エチル−２−メチルインドール−３−イル）−４−アザフタリド２．０重量部、（ロ）成分として１，１−ビス（４′−ヒドロキシフェニル）ｎ−デカン３．０重量部、１，１−ビス（４′−ヒドロキシフェニル）ヘキサフルオロプロパン５．０重量部、（ハ）成分としてカプリン酸４−ベンジルオキシフェニルエチル５０．０重量部からなる感温変色性色彩記憶性組成物を均一に加温溶解し、壁膜材料として芳香族多価イソシアネートプレポリマー３０．０重量部、助溶剤４０．０重量部を混合した溶液を、８％ポリビニルアルコール水溶液中で微小滴になるように乳化分散し、７０℃で約１時間攪拌を続けた後、水溶性脂肪族変性アミン２．５重量部を加え、更に６時間攪拌を続けて感温変色性色彩記憶性マイクロカプセル顔料懸濁液を得た。
前記懸濁液を遠心分離して感温変色性色彩記憶性マイクロカプセル顔料を単離した。
なお、前記マイクロカプセル顔料のヒステリシス幅（ΔＨ）は６４℃、完全発色温度（Ｔ１）は−１４℃、消色保持温度（Ｔ２）は−６℃、発色保持温度（Ｔ３）は４８℃、完全消色温度（Ｔ４）は６０℃であり、温度変化により青色から無色に変色する。
Example 2
Preparation of thermosensitive color-changing color memory microcapsule pigment (a) As component (3- (4-diethylamino-2-hexyloxyphenyl) -3- (1-ethyl-2-methylindol-3-yl) -4- 4. 2.0 parts by weight of azaphthalide, 3.0 parts by weight of 1,1-bis (4′-hydroxyphenyl) n-decane as component (b), 1,1-bis (4′-hydroxyphenyl) hexafluoropropane A thermosensitive color-changing color memory composition comprising 0 parts by weight and 50.0 parts by weight of 4-benzyloxyphenylethyl caprate as the component (c) is uniformly heated and dissolved, and an aromatic polyvalent isocyanate is used as a wall film material. A solution prepared by mixing 30.0 parts by weight of the prepolymer and 40.0 parts by weight of the co-solvent is emulsified and dispersed in an 8% aqueous solution of polyvinyl alcohol so as to form fine droplets. After continuing stirring, 2.5 parts by weight of a water-soluble aliphatic modified amine was added, and stirring was further continued for 6 hours to obtain a temperature-sensitive color-changing color memory microcapsule pigment suspension.
The suspension was centrifuged to isolate a thermochromic color memory microcapsule pigment.
The microcapsule pigment has a hysteresis width (ΔH) of 64 ° C., a complete color development temperature (T 1 ) of −14 ° C., a decolorization retention temperature (T 2 ) of −6 ° C., and a color development retention temperature (T 3 ) of 48. ° C., complete decoloring temperature (T 4) is 60 ° C., changes color from blue to colorless through a change in temperature.
感温変色性色彩記憶性インキの調製
前記マイクロカプセル顔料２０．０重量部、尿素５．０重量部、グリセリン１５．０重量部、石炭酸５．０重量部、潤滑剤〔第一工業製薬（株）製プライサーフＡＬ〕０．５重量部、トリエタノールアミン０．５重量部、水５４．０重量部からなる感温変色性色彩記憶性インキを調製した。
Preparation of temperature-sensitive color-changing color memory ink 20.0 parts by weight of the above microcapsule pigment, 5.0 parts by weight of urea, 15.0 parts by weight of glycerin, 5.0 parts by weight of carboxylic acid, a lubricant [Daiichi Kogyo Seiyaku Co., Ltd. Plysurf AL] A thermochromic color memory ink comprising 0.5 parts by weight, 0.5 parts by weight of triethanolamine and 54.0 parts by weight of water was prepared.
筆記具の作製
前記インキ（予め−１４℃以下に冷却してマイクロカプセル顔料を青色に発色させた後、室温下で放置したもの）を軸筒内に直接収容し、軸筒内の前方に櫛溝状のインキ調節部材を有し、且つ、直径０．５ｍｍのステンレス鋼ボールが切削加工によりボール受け座を形成した金属部材に抱持されたボールペンチップを備えたボールペンを得た。
なお、前記ボールペンには着脱自在のキャップを備えてなり、前記キャップには頂部に摩擦体としてシリコーンゴムを装着してなる。
Preparation of a writing instrument The ink (which has been cooled to -14 ° C. or less in advance to develop a blue color of the microcapsule pigment and then left at room temperature) is directly stored in the shaft tube, and the comb groove is placed in front of the shaft tube. A ballpoint pen provided with a ballpoint pen tip held by a metal member having a cylindrical ink adjusting member and having a stainless steel ball having a diameter of 0.5 mm formed by ball machining on a ball receiving seat was obtained.
The ballpoint pen is provided with a detachable cap, and the cap is provided with silicone rubber as a friction body on the top.
前記ボールペンを用いて紙面に筆記して青色の文字（筆跡）を形成した。
前記筆跡は、室温（２５℃）で青色を呈しており、消色保持温度（−６℃）以上、完全消色温度（６０℃）以下の温度でこの状態を保持していた。
前記文字をキャップに装着した摩擦体を用いて擦過すると、該文字は消色して無色となり、消色保持温度（−６℃）以上、完全消色温度（６０℃）以下の温度でこの状態を保持していた。
なお、前記紙面を冷凍庫に入れて完全発色温度以下に冷却すると、再び文字は青色になる変色挙動を示し、前記変色挙動は繰り返し再現することができた。
Blue letters (handwriting) were formed by writing on the paper using the ballpoint pen.
The handwriting exhibited a blue color at room temperature (25 ° C.), and this state was maintained at a temperature not lower than the decolorization holding temperature (−6 ° C.) and not higher than the complete decoloring temperature (60 ° C.).
When the character is abraded with a friction body attached to a cap, the character is decolored and colorless, and this state is maintained at a temperature not lower than the decolorization holding temperature (−6 ° C.) and not higher than the complete decolorization temperature (60 ° C.). Was holding.
When the paper surface was placed in a freezer and cooled below the complete color development temperature, the characters again showed a color change behavior that turned blue, and the color change behavior could be reproduced repeatedly.
実施例３
感温変色性色彩記憶性マイクロカプセル顔料の調製
（イ）成分として、４−［２，６−ビス（２−エトキシフェニル）−４−ピリジニル］−Ｎ，Ｎ−ジメチルベンゼンアミン３．０重量部、（ロ）成分として１，１−ビス（４′−ヒドロキシフェニル）ヘキサフルオロプロパン１０．０重量部、（ハ）成分としてカプリン酸４−ベンジルオキシフェニルエチル５０．０重量部からなる感温変色性色彩記憶性組成物を均一に加温溶解し、壁膜材料として芳香族多価イソシアネートプレポリマー３０．０重量部、助溶剤４０．０重量部を混合した溶液を、８％ポリビニルアルコール水溶液中で微小滴になるように乳化分散し、７０℃で約１時間攪拌を続けた後、水溶性脂肪族変性アミン２．５重量部を加え、更に６時間攪拌を続けて感温変色性色彩記憶性マイクロカプセル顔料懸濁液を得た。
前記懸濁液を遠心分離して感温変色性色彩記憶性マイクロカプセル顔料を単離した。
なお、前記マイクロカプセル顔料のヒステリシス幅（ΔＨ）は６９．５℃、完全発色温度（Ｔ１）は−２５℃、消色保持温度（Ｔ２）は−１５℃、発色保持温度（Ｔ３）は４０℃、完全消色温度（Ｔ４）は５９℃であり、温度変化により黄色から無色に変色する。
Example 3
Preparation of thermosensitive color-change color memory microcapsule pigment (i) As component (4), 3.0 parts by weight of 4- [2,6-bis (2-ethoxyphenyl) -4-pyridinyl] -N, N-dimethylbenzenamine The temperature-sensitive discoloration comprising 10.0 parts by weight of 1,1-bis (4′-hydroxyphenyl) hexafluoropropane as the component (b) and 50.0 parts by weight of 4-benzyloxyphenylethyl caprate as the component (c). The color color memory composition was uniformly heated and dissolved, and a solution prepared by mixing 30.0 parts by weight of an aromatic polyvalent isocyanate prepolymer and 40.0 parts by weight of a co-solvent as a wall film material was added to an aqueous 8% polyvinyl alcohol solution. After emulsifying and dispersing to form fine droplets, stirring at 70 ° C. for about 1 hour, adding 2.5 parts by weight of water-soluble aliphatic modified amine, and further stirring for 6 hours, temperature-sensitive discoloration color A chromatic memory microcapsule pigment suspension was obtained.
The suspension was centrifuged to isolate a thermochromic color memory microcapsule pigment.
The microcapsule pigment has a hysteresis width (ΔH) of 69.5 ° C., a complete color development temperature (T 1 ) of −25 ° C., a decolorization retention temperature (T 2 ) of −15 ° C., and a color development retention temperature (T 3 ). Is 40 ° C. and the complete color erasing temperature (T 4 ) is 59 ° C., and the color changes from yellow to colorless according to temperature change.
感温変色性色彩記憶性インキの調製
前記マイクロカプセル顔料１８．８重量部、ヒドロキシエチルセルロース〔ユニオンカーバイド日本（株）製、商品名：セロサイズＷＰ−０９Ｂ〕０．４重量部、グリセリン５．０重量部、変性シリコーン系消泡剤〔日本シリコーン（株）製、商品名：ＦＳアンチフォーム０１３Ｂ〕０．０２重量部、防腐剤〔ゼネカ（株）製、商品名：プロキセルＸＬ−２〕１．０部、水７４．７８重量部からなる感温変色性色彩記憶性インキを調製した。
Preparation of temperature-sensitive color-changing color memory ink 18.8 parts by weight of the microcapsule pigment, hydroxyethyl cellulose [manufactured by Union Carbide Japan Co., Ltd., trade name: Cellosize WP-09B], 0.4 parts by weight, glycerin 5.0 parts by weight Parts, modified silicone antifoaming agent [manufactured by Nippon Silicone Co., Ltd., trade name: FS Antifoam 013B] 0.02 parts by weight, preservative [manufactured by Zeneca Co., Ltd., trade name: Proxel XL-2] 1.0 Part, and 74.78 parts by weight of water were prepared.
筆記具の作製
前記インキ（予め−２５℃以下に冷却してマイクロカプセル顔料を黄色に発色させた後、室温下で放置したもの）を、ポリエステルスライバーを合成樹脂フィルムで被覆した繊維集束インキ吸蔵体（気孔率約８０％）に２．０ｇ含浸させて軸筒内に収容し、軸筒先端部にチゼル型繊維ペン体（気孔率約５０％）を取り付けてマーキングペンを得た。
なお、前記マーキングペンには着脱自在のキャップを備えてなり、前記キャップには頂部に摩擦体としてシリコーンゴムを装着してなる。
Fabrication of writing instrument A fiber-focused ink occlusion body in which the above-mentioned ink (previously cooled to −25 ° C. or lower and the microcapsule pigment is colored yellow and then left at room temperature) is coated with a polyester sliver with a synthetic resin film ( A marking pen was obtained by impregnating 2.0 g of the porosity (about 80%) into the shaft cylinder and storing it in the shaft cylinder, and attaching a chisel-type fiber pen body (porosity about 50%) to the tip of the shaft cylinder.
The marking pen is provided with a detachable cap, and the cap is provided with silicone rubber as a friction body at the top.
前記マーキングペンを用いて紙面に筆記して黄色の文字（筆跡）を形成した。
前記筆跡は、室温（２５℃）で黄色を呈しており、消色保持温度（−１５℃）以上、完全消色温度（５９℃）以下の温度でこの状態を保持していた。
前記文字をキャップに装着した摩擦体を用いて擦過すると、該文字は消色して無色となり、消色保持温度（−１５℃）以上、完全消色温度（５９℃）以下の温度でこの状態を保持していた。
なお、前記紙面を冷凍庫に入れて完全発色温度以下に冷却すると、再び文字は黄色になる変色挙動を示し、前記変色挙動は繰り返し再現することができた。
A yellow character (handwriting) was formed by writing on the paper using the marking pen.
The handwriting had a yellow color at room temperature (25 ° C.), and this state was maintained at a temperature not lower than the decolorization holding temperature (−15 ° C.) and not higher than the complete decoloring temperature (59 ° C.).
When the character is abraded with a friction body attached to a cap, the character is decolored and colorless, and this state is maintained at a temperature equal to or higher than the decolorization holding temperature (−15 ° C.) and lower than the complete decolorization temperature (59 ° C.). Was holding.
When the paper surface was placed in a freezer and cooled below the complete color development temperature, the characters again showed a discoloration behavior that turned yellow, and the discoloration behavior could be reproduced repeatedly.
実施例４
感温変色性色彩記憶性マイクロカプセル顔料ａの調製
（イ）成分として１，３−ジメチル−６−ジエチルアミノフルオラン２，５重量部、（ロ）成分として１，１−ビス（４′−ヒドロキシフェニル）ヘキサフルオロプロパン５．０重量部、１，１−ビス（４′−ヒドロキシフェニル）ｎ−デカン３．０重量部、（ハ）成分としてカプリン酸４−ベンジルオキシフェニルエチル５０．０重量部からなる感温変色性色彩記憶性組成物を均一に加温溶解し、壁膜材料として芳香族多価イソシアネートプレポリマー３０．０重量部、助溶剤４０．０重量部を混合した溶液を、８％ポリビニルアルコール水溶液中で微小滴になるように乳化分散し、７０℃で約１時間攪拌を続けた後、水溶性脂肪族変性アミン２．５重量部を加え、更に６時間攪拌を続けて感温変色性色彩記憶性マイクロカプセル顔料懸濁液を得た。
前記懸濁液を遠心分離して感温変色性色彩記憶性マイクロカプセル顔料ａを単離した。 なお、前記マイクロカプセル顔料のヒステリシス幅（ΔＨ）は６２．５℃、完全発色温度（Ｔ１）は−２０℃、消色保持温度（Ｔ２）は−９℃、発色保持温度（Ｔ３）は４２℃、完全消色温度（Ｔ４）は５４℃であり、温度変化によりオレンジ色から無色に変色する。
Example 4
Preparation of thermosensitive color-changing color memory microcapsule pigment a (i) 2,5-part by weight of 1,3-dimethyl-6-diethylaminofluorane as component, 1,1-bis (4'-hydroxy) as component (b) Phenyl) hexafluoropropane 5.0 parts by weight, 1,1-bis (4'-hydroxyphenyl) n-decane 3.0 parts by weight, and (c) component 4-benzyloxyphenylethyl caprate 50.0 parts by weight A solution in which 30.0 parts by weight of an aromatic polyvalent isocyanate prepolymer and 40.0 parts by weight of a co-solvent are mixed as a wall film material is uniformly dissolved in a temperature-sensitive color-changing color memory composition comprising 8 After emulsifying and dispersing in fine water in a polyvinyl alcohol solution to form fine droplets, stirring was continued at 70 ° C. for about 1 hour, 2.5 parts by weight of a water-soluble aliphatic modified amine was added, and stirring was further continued for 6 hours. A temperature-sensitive color-change color-memory microcapsule pigment suspension was obtained.
The suspension was centrifuged to isolate thermochromic color memory microcapsule pigment a. The microcapsule pigment has a hysteresis width (ΔH) of 62.5 ° C., a complete color development temperature (T 1 ) of −20 ° C., a decolorization retention temperature (T 2 ) of −9 ° C., and a color development retention temperature (T 3 ). Is 42 ° C. and the complete color erasing temperature (T 4 ) is 54 ° C., and the color changes from orange to colorless with temperature change.
感温変色性色彩記憶性マイクロカプセル顔料ｂの調製
（イ）成分として３，３−ビス−（２−エトキシ−４−ジエチルアミニアミノ）４−アザフタリド２．５重量部、（ロ）成分として１，１−ビス（４′−ヒドロキシフェニル）ヘキサフルオロプロパン５．０重量部、１，１−ビス（４′−ヒドロキシフェニル）ｎ−デカン３．０重量部、（ハ）成分としてカプリン酸４−ベンジルオキシフェニルエチル５０．０重量部からなる感温変色性色彩記憶性組成物を均一に加温溶解し、壁膜材料として芳香族多価イソシアネートプレポリマー３０．０重量部、助溶剤４０．０重量部を混合した溶液を、８％ポリビニルアルコール水溶液中で微小滴になるように乳化分散し、７０℃で約１時間攪拌を続けた後、水溶性脂肪族変性アミン２．５重量部を加え、更に６時間攪拌を続けて感温変色性色彩記憶性マイクロカプセル顔料懸濁液を得た。
前記懸濁液を遠心分離して感温変色性色彩記憶性マイクロカプセル顔料ｂを単離した。
なお、前記マイクロカプセル顔料のヒステリシス幅（ΔＨ）は６２．５℃、完全発色温度（Ｔ１）は−２０℃、消色保持温度（Ｔ２）は−９℃、発色保持温度（Ｔ３）は４２℃、完全消色温度（Ｔ４）は５４℃であり、青緑色から無色に変色する。
Preparation of thermosensitive color-changing color memory microcapsule pigment b (a) 2.5 parts by weight of 3,3-bis- (2-ethoxy-4-diethylaminiamino) 4-azaphthalide as component (b) 1 as component (b) , 1-bis (4′-hydroxyphenyl) hexafluoropropane 5.0 parts by weight, 1,1-bis (4′-hydroxyphenyl) n-decane 3.0 parts by weight, (c) capric acid 4- A temperature-sensitive color-changing color memory composition comprising 50.0 parts by weight of benzyloxyphenylethyl is uniformly heated and dissolved, and 30.0 parts by weight of an aromatic polyvalent isocyanate prepolymer as a wall film material, 40.0% of a co-solvent The mixed solution is emulsified and dispersed in 8% aqueous polyvinyl alcohol so as to form fine droplets, and after stirring at 70 ° C. for about 1 hour, 2.5 parts by weight of a water-soluble aliphatic modified amine is added. The mixture was further stirred for 6 hours to obtain a temperature-sensitive color-change color memory microcapsule pigment suspension.
The suspension was centrifuged to isolate thermochromic color memory microcapsule pigment b.
The microcapsule pigment has a hysteresis width (ΔH) of 62.5 ° C., a complete color development temperature (T 1 ) of −20 ° C., a decolorization retention temperature (T 2 ) of −9 ° C., and a color development retention temperature (T 3 ). Is 42 ° C. and the complete color erasing temperature (T 4 ) is 54 ° C., and the color changes from blue-green to colorless.
感温変色性色彩記憶性インキの調製
前記マイクロカプセル顔料ａ１８．８重量部、ヒドロキシエチルセルロース〔ユニオンカーバイド日本（株）製、商品名：セロサイズＷＰ−０９Ｂ〕０．４重量部、グリセリン５．０重量部、変性シリコーン系消泡剤〔日本シリコーン（株）製、商品名：ＦＳアンチフォーム０１３Ｂ〕０．０２重量部、防腐剤〔ゼネカ（株）製、商品名：プロキセルＸＬ−２〕１．０部、水７４．７８重量部からなる感温変色性色彩記憶性インキＡを調製した。
これとは別に、マイクロカプセル顔料ｂ１８．８重量部、ヒドロキシエチルセルロース〔ユニオンカーバイド日本（株）製、商品名：セロサイズＷＰ−０９Ｂ〕０．４重量部、グリセリン５．０重量部、変性シリコーン系消泡剤〔日本シリコーン（株）製、商品名：ＦＳアンチフォーム０１３Ｂ〕０．０２重量部、防腐剤〔ゼネカ（株）製、商品名：プロキセルＸＬ−２〕１．０部、水７４．７８重量部からなる感温変色性色彩記憶性インキＢを調製した。
Preparation of temperature-sensitive color-changing color memory ink 18.8 parts by weight of the above microcapsule pigment a, hydroxyethyl cellulose [manufactured by Union Carbide Japan Co., Ltd., trade name: cellosize WP-09B], 0.4 parts by weight, glycerin 5.0 parts by weight Parts, modified silicone antifoaming agent [manufactured by Nippon Silicone Co., Ltd., trade name: FS Antifoam 013B] 0.02 parts by weight, preservative [manufactured by Zeneca Co., Ltd., trade name: Proxel XL-2] 1.0 Temperature-sensitive color-change color memory ink A comprising 74 parts by weight of water and 74.78 parts by weight of water was prepared.
Separately from this, 18.8 parts by weight of microcapsule pigment b, hydroxyethyl cellulose (manufactured by Union Carbide Japan Co., Ltd., trade name: Cellosize WP-09B), 0.4 parts by weight, glycerin 5.0 parts by weight, modified silicone-based pigment 0.02 part by weight of a foaming agent [manufactured by Nippon Silicone Co., Ltd., trade name: FS Antifoam 013B], 1.0 part of an antiseptic [manufactured by Zeneca Co., Ltd., trade name: Proxel XL-2], 74.78 water A thermochromic color memory ink B consisting of parts by weight was prepared.
筆記具の作製
前記インキＡ（予め−２０℃以下に冷却してマイクロカプセル顔料を橙色に発色させた後、室温下で放置したもの）を、ポリエステルスライバーを合成樹脂フィルムで被覆した繊維集束インキ吸蔵体（気孔率約８９％）に１．０ｇ含浸させ、内部の中央部分に仕切りを設けた軸筒の一方に収容し、軸筒先端部にチゼル型繊維ペン体（気孔率約５３％）を取り付けた。
更に、インキＢ（予め−２０℃以下に冷却してマイクロカプセル顔料を青緑色に発色させた後、室温下で放置したもの）を、ポリエステルスライバーを合成樹脂フィルムで被覆した繊維集束インキ吸蔵体（気孔率約８９％）に１．０ｇ含浸させ、前記軸筒の他方に収容し、軸筒先端部にチゼル型繊維ペン体（気孔率約５３％）を取り付けて両頭式のマーキングペンを得た。
なお、前記マーキングペンには着脱自在のキャップを備えてなり、前記キャップには頂部に摩擦体としてシリコーンゴムを装着してなる。
Fabrication of a writing instrument A fiber-focused ink occlusion body in which the ink A (previously cooled to −20 ° C. or lower and the microcapsule pigment is colored orange and left at room temperature) is coated with a polyester sliver with a synthetic resin film. (Porosity of about 89%) is impregnated with 1.0 g, accommodated in one of the shaft cylinders provided with a partition in the central part inside, and a chisel-type fiber pen (porosity of about 53%) is attached to the tip of the shaft cylinder It was.
In addition, a fiber-focused ink occlusion body in which ink B (cooled to −20 ° C. or less in advance to develop a microcapsule pigment in blue-green color and allowed to stand at room temperature) covered with a polyester sliver with a synthetic resin film ( (Porosity of about 89%) was impregnated with 1.0 g, accommodated in the other end of the shaft tube, and a chisel-type fiber pen body (porosity of about 53%) was attached to the end of the shaft tube to obtain a double-headed marking pen. .
The marking pen is provided with a detachable cap, and the cap is provided with silicone rubber as a friction body at the top.
前記マーキングペンを用いて紙面に筆記して橙色の文字（筆跡）と青緑色の文字（筆跡）を形成した。
前記筆跡は、室温（２５℃）で橙色と青緑色を呈しており、消色保持温度（−９℃）以上、完全消色温度（５４℃）以下の温度でこの状態を保持していた。
前記文字をキャップに装着した摩擦体を用いて擦過すると、該文字は消色して無色となり、消色保持温度（−９℃）以上、完全消色温度（５４℃）以下の温度でこの状態を保持していた。
なお、前記紙面を冷凍庫に入れて完全発色温度以下に冷却すると、再び文字は橙色と青緑色になる変色挙動を示し、前記変色挙動は繰り返し再現することができた。
An orange character (handwriting) and a blue-green character (handwriting) were formed by writing on the paper using the marking pen.
The handwriting exhibited an orange color and a bluish green color at room temperature (25 ° C.), and this state was maintained at a temperature not lower than the decolorization holding temperature (−9 ° C.) and not higher than the complete color erasing temperature (54 ° C.).
When the character is abraded with a friction body attached to a cap, the character is decolored and colorless, and this state is maintained at a temperature equal to or higher than the decolorization holding temperature (−9 ° C.) and equal to or lower than the complete decoloring temperature (54 ° C.). Was holding.
When the paper surface was placed in a freezer and cooled below the complete color development temperature, the characters again showed a discoloration behavior that turned orange and blue-green, and the discoloration behavior could be reproduced repeatedly.
Ｔ１ 完全発色温度
Ｔ２ 消色保持温度
Ｔ３ 発色保持温度
Ｔ４ 完全消色温度
ΔＨ ヒステリシス幅
T 1 complete color developing temperature T 2 color erasing holding temperature T 3 color developing holding temperature T 4 complete color erasing temperature ΔH hysteresis width
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| JP2004119869A JP4294534B2 (en) | 2004-04-15 | 2004-04-15 | Writing instrument |
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| JP4294534B2 true JP4294534B2 (en) | 2009-07-15 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006137886A (en) * | 2004-11-15 | 2006-06-01 | Pilot Ink Co Ltd | Thermochromic color-memory composition and thermochromic color-memory microcapsule pigment containing the same |
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| JP4782402B2 (en) * | 2004-10-21 | 2011-09-28 | パイロットインキ株式会社 | Writing instrument using reversible thermochromic water-based ink composition |
| JP2007126554A (en) * | 2005-11-03 | 2007-05-24 | Pilot Ink Co Ltd | Ink composition for thermosensitive, erasable writing utensil and writing utensil and writing utensil set containing the same |
| JP4874886B2 (en) * | 2007-07-19 | 2012-02-15 | パイロットインキ株式会社 | Mark sheet writing instrument, Mark sheet writing instrument set |
| US8182596B2 (en) | 2007-11-09 | 2012-05-22 | Sakura Color Products Corporation | Discolorable ink composition and writing utensils |
| EP2500778B1 (en) | 2009-11-13 | 2017-10-25 | The Pilot Ink Co., Ltd. | Thermochromic color-memorization type toner, cartridge including same housed therein, image formation apparatus, cartridge set, and image formation apparatus set |
| WO2011115046A1 (en) * | 2010-03-16 | 2011-09-22 | パイロットインキ株式会社 | Reversibly thermochromic aqueous ink composition for use in ballpoint pen, and ballpoint pen refill and ballpoint pen each using same |
| JP5508645B2 (en) * | 2011-05-06 | 2014-06-04 | パイロットインキ株式会社 | Reversible thermochromic water-based ink composition and writing instrument using the same |
| CN111592823B (en) * | 2020-04-29 | 2021-10-26 | 西北工业大学 | Two-color-change irreversible temperature indicating paint based on isotherm identification and coating manufacturing method |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006137886A (en) * | 2004-11-15 | 2006-06-01 | Pilot Ink Co Ltd | Thermochromic color-memory composition and thermochromic color-memory microcapsule pigment containing the same |
| JP4527501B2 (en) * | 2004-11-15 | 2010-08-18 | パイロットインキ株式会社 | Temperature-sensitive color-change color memory composition and temperature-sensitive color-change color memory microcapsule pigment containing the same |
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