JP6878054B2 - Ink composition for stationery - Google Patents
Ink composition for stationery Download PDFInfo
- Publication number
- JP6878054B2 JP6878054B2 JP2017048697A JP2017048697A JP6878054B2 JP 6878054 B2 JP6878054 B2 JP 6878054B2 JP 2017048697 A JP2017048697 A JP 2017048697A JP 2017048697 A JP2017048697 A JP 2017048697A JP 6878054 B2 JP6878054 B2 JP 6878054B2
- Authority
- JP
- Japan
- Prior art keywords
- color
- microcapsule pigment
- dye
- ink composition
- pyridine
- 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.)
- Active
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- 239000000203 mixture Substances 0.000 title claims description 58
- 239000000049 pigment Substances 0.000 claims description 79
- 239000003094 microcapsule Substances 0.000 claims description 76
- 239000003795 chemical substances by application Substances 0.000 claims description 21
- 238000002845 discoloration Methods 0.000 claims description 16
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 4
- 239000000975 dye Substances 0.000 description 62
- 239000000976 ink Substances 0.000 description 46
- 238000004519 manufacturing process Methods 0.000 description 39
- -1 pyridine compound Chemical class 0.000 description 25
- 229920005989 resin Polymers 0.000 description 21
- 239000011347 resin Substances 0.000 description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 18
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 15
- 239000002904 solvent Substances 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 13
- 150000001875 compounds Chemical class 0.000 description 12
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 12
- 238000000034 method Methods 0.000 description 12
- 238000011161 development Methods 0.000 description 11
- 239000003921 oil Substances 0.000 description 11
- 239000000306 component Substances 0.000 description 10
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 8
- 150000003839 salts Chemical class 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 7
- 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 7
- JECYUBVRTQDVAT-UHFFFAOYSA-N 2-acetylphenol Chemical compound CC(=O)C1=CC=CC=C1O JECYUBVRTQDVAT-UHFFFAOYSA-N 0.000 description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 229920003180 amino resin Polymers 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000011258 core-shell material Substances 0.000 description 5
- 235000014113 dietary fatty acids Nutrition 0.000 description 5
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 5
- 239000000194 fatty acid Substances 0.000 description 5
- 229930195729 fatty acid Natural products 0.000 description 5
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 5
- 239000000314 lubricant Substances 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 230000003449 preventive effect Effects 0.000 description 5
- BGNGWHSBYQYVRX-UHFFFAOYSA-N 4-(dimethylamino)benzaldehyde Chemical compound CN(C)C1=CC=C(C=O)C=C1 BGNGWHSBYQYVRX-UHFFFAOYSA-N 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 4
- 229920000877 Melamine resin Polymers 0.000 description 4
- 239000004640 Melamine resin Substances 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- 229920002125 Sokalan® Polymers 0.000 description 4
- VYHBFRJRBHMIQZ-UHFFFAOYSA-N bis[4-(diethylamino)phenyl]methanone Chemical compound C1=CC(N(CC)CC)=CC=C1C(=O)C1=CC=C(N(CC)CC)C=C1 VYHBFRJRBHMIQZ-UHFFFAOYSA-N 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- GPLRAVKSCUXZTP-UHFFFAOYSA-N diglycerol Chemical compound OCC(O)COCC(O)CO GPLRAVKSCUXZTP-UHFFFAOYSA-N 0.000 description 4
- 239000002270 dispersing agent Substances 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 150000002894 organic compounds Chemical class 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 229920001451 polypropylene glycol Polymers 0.000 description 4
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 4
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 4
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 4
- 239000003755 preservative agent Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 230000002441 reversible effect Effects 0.000 description 4
- 229940002520 2'-hydroxyacetophenone Drugs 0.000 description 3
- GZVHEAJQGPRDLQ-UHFFFAOYSA-N 6-phenyl-1,3,5-triazine-2,4-diamine Chemical compound NC1=NC(N)=NC(C=2C=CC=CC=2)=N1 GZVHEAJQGPRDLQ-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 229930185605 Bisphenol Natural products 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000003377 acid catalyst Substances 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 239000002775 capsule Substances 0.000 description 3
- 239000008358 core component Substances 0.000 description 3
- 238000004042 decolorization Methods 0.000 description 3
- 239000003822 epoxy resin Substances 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- 150000002576 ketones Chemical class 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 238000005191 phase separation Methods 0.000 description 3
- 229920000647 polyepoxide Polymers 0.000 description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 description 3
- 230000001681 protective effect Effects 0.000 description 3
- 150000003222 pyridines Chemical class 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- PXSUMUYPXZEXDT-UHFFFAOYSA-M 1-phenyl-2-pyridin-1-ium-1-ylethanone;bromide Chemical compound [Br-].C=1C=CC=CC=1C(=O)C[N+]1=CC=CC=C1 PXSUMUYPXZEXDT-UHFFFAOYSA-M 0.000 description 2
- OQQJOLFBCWRLPF-UHFFFAOYSA-N 2-[4-[4-(dimethylamino)phenyl]-6-phenylpyridin-2-yl]phenol Chemical compound OC1=C(C=CC=C1)C1=NC(=CC(=C1)C1=CC=C(C=C1)N(C)C)C1=CC=CC=C1 OQQJOLFBCWRLPF-UHFFFAOYSA-N 0.000 description 2
- LUJMEECXHPYQOF-UHFFFAOYSA-N 3-hydroxyacetophenone Chemical compound CC(=O)C1=CC=CC(O)=C1 LUJMEECXHPYQOF-UHFFFAOYSA-N 0.000 description 2
- NWKIYBPNACDLOB-UHFFFAOYSA-N 4-(2,6-diphenylpyridin-4-yl)-n,n-dimethylaniline Chemical compound C1=CC(N(C)C)=CC=C1C1=CC(C=2C=CC=CC=2)=NC(C=2C=CC=CC=2)=C1 NWKIYBPNACDLOB-UHFFFAOYSA-N 0.000 description 2
- XXHIPRDUAVCXHW-UHFFFAOYSA-N 4-[2-ethyl-1-(4-hydroxyphenyl)hexyl]phenol Chemical compound C=1C=C(O)C=CC=1C(C(CC)CCCC)C1=CC=C(O)C=C1 XXHIPRDUAVCXHW-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 2
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 2
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 229920001807 Urea-formaldehyde Polymers 0.000 description 2
- XAKBSHICSHRJCL-UHFFFAOYSA-N [CH2]C(=O)C1=CC=CC=C1 Chemical group [CH2]C(=O)C1=CC=CC=C1 XAKBSHICSHRJCL-UHFFFAOYSA-N 0.000 description 2
- 239000003242 anti bacterial agent Substances 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 239000011362 coarse particle Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 229940105990 diglycerin Drugs 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- 229920000591 gum Polymers 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 125000000654 isopropylidene group Chemical group C(C)(C)=* 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229940078812 myristyl myristate Drugs 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 2
- 229920001748 polybutylene Polymers 0.000 description 2
- BBFCIBZLAVOLCF-UHFFFAOYSA-N pyridin-1-ium;bromide Chemical compound Br.C1=CC=NC=C1 BBFCIBZLAVOLCF-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000012429 reaction media Substances 0.000 description 2
- 230000027756 respiratory electron transport chain Effects 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- DZKXJUASMGQEMA-UHFFFAOYSA-N tetradecyl tetradecanoate Chemical compound CCCCCCCCCCCCCCOC(=O)CCCCCCCCCCCCC DZKXJUASMGQEMA-UHFFFAOYSA-N 0.000 description 2
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 2
- 239000002562 thickening agent Substances 0.000 description 2
- 238000006276 transfer reaction Methods 0.000 description 2
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 1
- LNAZSHAWQACDHT-XIYTZBAFSA-N (2r,3r,4s,5r,6s)-4,5-dimethoxy-2-(methoxymethyl)-3-[(2s,3r,4s,5r,6r)-3,4,5-trimethoxy-6-(methoxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6r)-4,5,6-trimethoxy-2-(methoxymethyl)oxan-3-yl]oxyoxane Chemical compound CO[C@@H]1[C@@H](OC)[C@H](OC)[C@@H](COC)O[C@H]1O[C@H]1[C@H](OC)[C@@H](OC)[C@H](O[C@H]2[C@@H]([C@@H](OC)[C@H](OC)O[C@@H]2COC)OC)O[C@@H]1COC LNAZSHAWQACDHT-XIYTZBAFSA-N 0.000 description 1
- DTCCVIYSGXONHU-CJHDCQNGSA-N (z)-2-(2-phenylethenyl)but-2-enedioic acid Chemical compound OC(=O)\C=C(C(O)=O)\C=CC1=CC=CC=C1 DTCCVIYSGXONHU-CJHDCQNGSA-N 0.000 description 1
- YGSJJDVZOUGHFG-UHFFFAOYSA-N 1,4-bis(propylamino)cyclohexa-2,4-diene-1-carbaldehyde Chemical compound CCCNC1=CCC(NCCC)(C=O)C=C1 YGSJJDVZOUGHFG-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical class C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 description 1
- 239000005695 Ammonium acetate Substances 0.000 description 1
- VLMZVBOGAACNGU-UHFFFAOYSA-N C(CCC)NC1(C=O)CC=C(C=C1)NCCCC Chemical compound C(CCC)NC1(C=O)CC=C(C=C1)NCCCC VLMZVBOGAACNGU-UHFFFAOYSA-N 0.000 description 1
- KNFMVRDIXLDJRH-UHFFFAOYSA-N CCNC1=CCC(NCC)(C=O)C=C1 Chemical compound CCNC1=CCC(NCC)(C=O)C=C1 KNFMVRDIXLDJRH-UHFFFAOYSA-N 0.000 description 1
- IARVLPRMEYCJNF-UHFFFAOYSA-N CN(C)C(C=C1)=CC=C1C1=CC(C2=CC(C3=CC=CC=C3)=CC=C2)=NC(C2=CC=CC=C2)=C1 Chemical compound CN(C)C(C=C1)=CC=C1C1=CC(C2=CC(C3=CC=CC=C3)=CC=C2)=NC(C2=CC=CC=C2)=C1 IARVLPRMEYCJNF-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 229920002307 Dextran Polymers 0.000 description 1
- 239000001856 Ethyl cellulose Substances 0.000 description 1
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- 229920002907 Guar gum Polymers 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 238000012696 Interfacial polycondensation Methods 0.000 description 1
- 238000012695 Interfacial polymerization Methods 0.000 description 1
- 229920000161 Locust bean gum Polymers 0.000 description 1
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- 229920002472 Starch Polymers 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 229920002310 Welan gum Polymers 0.000 description 1
- MBHRHUJRKGNOKX-UHFFFAOYSA-N [(4,6-diamino-1,3,5-triazin-2-yl)amino]methanol Chemical compound NC1=NC(N)=NC(NCO)=N1 MBHRHUJRKGNOKX-UHFFFAOYSA-N 0.000 description 1
- 235000010489 acacia gum Nutrition 0.000 description 1
- 239000001785 acacia senegal l. willd gum Substances 0.000 description 1
- 238000012644 addition polymerization Methods 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 235000010443 alginic acid Nutrition 0.000 description 1
- 229920000615 alginic acid Polymers 0.000 description 1
- 239000000783 alginic acid Substances 0.000 description 1
- 229960001126 alginic acid Drugs 0.000 description 1
- 150000004781 alginic acids Chemical class 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 235000019257 ammonium acetate Nutrition 0.000 description 1
- 229940043376 ammonium acetate Drugs 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 150000001449 anionic compounds Chemical class 0.000 description 1
- 230000002421 anti-septic effect Effects 0.000 description 1
- 125000003785 benzimidazolyl group Chemical class N1=C(NC2=C1C=CC=C2)* 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- 230000008033 biological extinction Effects 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- OHJMTUPIZMNBFR-UHFFFAOYSA-N biuret Chemical compound NC(=O)NC(N)=O OHJMTUPIZMNBFR-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- QHIWVLPBUQWDMQ-UHFFFAOYSA-N butyl prop-2-enoate;methyl 2-methylprop-2-enoate;prop-2-enoic acid Chemical compound OC(=O)C=C.COC(=O)C(C)=C.CCCCOC(=O)C=C QHIWVLPBUQWDMQ-UHFFFAOYSA-N 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 235000010418 carrageenan Nutrition 0.000 description 1
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- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- FZWBNHMXJMCXLU-BLAUPYHCSA-N isomaltotriose Chemical compound O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@@H]1OC[C@@H]1[C@@H](O)[C@H](O)[C@@H](O)[C@@H](OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C=O)O1 FZWBNHMXJMCXLU-BLAUPYHCSA-N 0.000 description 1
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- 235000010420 locust bean gum Nutrition 0.000 description 1
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- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
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- 229920000609 methyl cellulose Polymers 0.000 description 1
- XJRBAMWJDBPFIM-UHFFFAOYSA-N methyl vinyl ether Chemical compound COC=C XJRBAMWJDBPFIM-UHFFFAOYSA-N 0.000 description 1
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- 235000010981 methylcellulose Nutrition 0.000 description 1
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- XGXKNJKGLCFDGK-UHFFFAOYSA-N n-[(4-methylphenyl)methyl]-2-pyridin-4-ylaniline Chemical compound C1=CC(C)=CC=C1CNC1=CC=CC=C1C1=CC=NC=C1 XGXKNJKGLCFDGK-UHFFFAOYSA-N 0.000 description 1
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- 150000007524 organic acids Chemical class 0.000 description 1
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- 235000010409 propane-1,2-diol alginate Nutrition 0.000 description 1
- 239000000770 propane-1,2-diol alginate Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 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
- 230000002829 reductive effect Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
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- 235000003441 saturated fatty acids Nutrition 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 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
- 235000002639 sodium chloride Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
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- 239000008107 starch Substances 0.000 description 1
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- 150000008163 sugars Chemical class 0.000 description 1
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- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- YODZTKMDCQEPHD-UHFFFAOYSA-N thiodiglycol Chemical compound OCCSCCO YODZTKMDCQEPHD-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 229920001285 xanthan gum Polymers 0.000 description 1
- 235000010493 xanthan gum Nutrition 0.000 description 1
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- 229940082509 xanthan gum Drugs 0.000 description 1
- JLQFVGYYVXALAG-CFEVTAHFSA-N yasmin 28 Chemical compound OC1=CC=C2[C@H]3CC[C@](C)([C@](CC4)(O)C#C)[C@@H]4[C@@H]3CCC2=C1.C([C@]12[C@H]3C[C@H]3[C@H]3[C@H]4[C@@H]([C@]5(CCC(=O)C=C5[C@@H]5C[C@@H]54)C)CC[C@@]31C)CC(=O)O2 JLQFVGYYVXALAG-CFEVTAHFSA-N 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
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B57/00—Other synthetic dyes of known constitution
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/16—Writing inks
- C09D11/17—Writing inks characterised by colouring agents
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
Description
本発明は、色素、それを用いたマイクロカプセル顔料及び筆記具用インク組成物に関し、更に詳しくは、優れた発色濃度と明るい色相が得られるロイコ色素からなる色素、この色素の顕色、消色機構を利用した熱変色性のマイクロカプセル顔料及びこのマイクロカプセル顔料を含有した筆記具用インク組成物に関する。 The present invention relates to a dye, a microcapsule pigment using the same, and an ink composition for writing utensils. The present invention relates to a thermochromic microcapsule pigment using the above, and an ink composition for writing utensils containing the microcapsule pigment.
従来より、ロイコ色素（染料）の顕色、消色機構を利用した熱変色性の色剤を用いた筆記具用インク組成物は、通常、上記色素をマイクロカプセル化した顔料を使用している。上記ロイコ色素を熱変色性マイクロカプセル顔料として用いるためには、マイクロカプセル顔料のコア成分を構成する媒体に対して十分な溶解性を有さなければならず、この溶解性が小さい場合には、満足する発色濃度が得られないものであった。 Conventionally, an ink composition for a writing instrument using a thermochromic colorant utilizing a color-developing and decolorizing mechanism of a leuco dye (dye) usually uses a pigment in which the above-mentioned dye is microencapsulated. In order to use the leuco dye as a thermochromic microcapsule pigment, it must have sufficient solubility in a medium constituting the core component of the microcapsule pigment, and if this solubility is small, it must have sufficient solubility. A satisfactory color development density could not be obtained.
従来の熱変色性マイクロカプセル顔料において、発色時に蛍光性を有する黄色等の色調を有するロイコ色素及びこれを用いたマイクロカプセル顔料としては、例えば、
１）（イ）ピリジン系、キナゾリン系、及びビスキナゾリン系化合物から選ばれる電子供与性呈色性有機化合物、（ロ）前記電子供与性呈色性有機化合物に対して電子受容性である化合物、（ハ）前記（イ）、（ロ）成分による電子授受反応を特定温度域において可逆的に生起させる反応媒体である化合物の３成分を必須成分とする相溶体からなる可逆熱変色性組成物、これをマイクロカプセル内に内包してなるマイクロカプセル顔料（例えば、特許文献１参照）、
２）（イ）電子供与性呈色性有機化合物として特定式で示されるピリジン誘導体と、前記電子供与性呈色性有機化合物に対して電子受容性である化合物と、（ハ）前記（イ）、（ロ）成分による電子授受反応を特定温度域において可逆的に生起させる反応媒体である化合物とからなる可逆熱変色性組成物、これをマイクロカプセル内に内包してなるマイクロカプセル顔料（例えば、特許文献２参照）、
３）（イ）ロイコ色素、（ロ）顕色性物質、及び（ハ）変色温度調整剤をマイクロカプセルに内包されてなる可逆感温変色性組成物において、（ロ）顕色性物質が特定式で示される化合物であり、且つ（ハ）変色温度調整剤が特定式で示される化合物であることを特徴とする可逆感温変色性ヒステリシス組成物（例えば、特許文献３参照）などが知られている。
上記特許文献１のピリジン系化合物として、具体的には、４−（４’−メチルベンジルアミノフェニル）−ピリジン、２，６−ジフェニル−４−（４’−ジメチルアミノフェニル）−ピリジン、２，６−ジフェニル−４−（４’−フェニル、メチルアミノフェニル）−ピリジンなどが例示されており、また、上記特許文献２のピリジン誘導体としては、２，６−ビス（２’，４’−ジメチルオキシフェニル）−４−（４’−ジメチルアミノフェニル）−ピリジンなどが例示されており、上記特許文献３のロイコ色素としては、４，４’−ビス（ジエチルアミノ）ベンゾフェノンなどが例示されている。
In the conventional thermochromic microcapsule pigment, as a leuco pigment having a color tone such as yellow having fluorescence at the time of color development and a microcapsule pigment using the same, for example,
1) (a) an electron-donating color-developing organic compound selected from pyridine-based, quinazoline-based, and bisquinazoline-based compounds, and (b) a compound that is electron-accepting to the electron-donating color-developing organic compound. (C) A reversible thermochromic composition comprising a compatible compound containing three components of a compound, which is a reaction medium that reversibly causes an electron transfer reaction by the components (a) and (b) above in a specific temperature range, as essential components. A microcapsule pigment obtained by encapsulating this in a microcapsule (see, for example, Patent Document 1),
2) (a) A pyridine derivative represented by a specific formula as an electron-donating color-forming organic compound, a compound that is electron-accepting to the electron-donating color-forming organic compound, and (c) the above-mentioned (a). , (B) A reversible thermochromic composition composed of a compound which is a reaction medium that reversibly causes an electron transfer reaction by a component in a specific temperature range, and a microcapsule pigment (for example, a microcapsule pigment formed by encapsulating the compound in microcapsules. See Patent Document 2),
3) In the reversible temperature-sensitive color-changing composition in which (a) leuco dye, (b) color-developing substance, and (c) color-changing temperature adjusting agent are encapsulated in microcapsules, (b) color-developing substance is specified. A reversible temperature-sensitive discoloration hysteresis composition (see, for example, Patent Document 3), which is a compound represented by the formula and (c) the discoloration temperature adjusting agent is a compound represented by a specific formula, is known. ing.
Specific examples of the pyridine compound of Patent Document 1 include 4- (4'-methylbenzylaminophenyl) -pyridine, 2,6-diphenyl-4- (4'-dimethylaminophenyl) -pyridine, 2, 6-Diphenyl-4- (4'-phenyl, methylaminophenyl) -pyridine and the like are exemplified, and 2,6-bis (2', 4'-dimethyl) as the pyridine derivative of Patent Document 2 above. Oxyphenyl) -4- (4'-dimethylaminophenyl) -pyridine and the like are exemplified, and 4,4'-bis (diethylamino) benzophenone and the like are exemplified as the leuco dye of Patent Document 3 above.
しかしながら、上記特許文献１〜３に記載のロイコ色素（染料）となるピリジン系化合物・誘導体、または、４，４’−ビス（ジエチルアミノ）ベンゾフェノンを用いた熱変色性マイクロカプセル顔料は、マイクロカプセル顔料のコア成分を構成する媒体に対して溶解性が未だ十分でなく、満足する発色濃度、並びに明るい色相が得られない点などに課題がある。 However, the heat-discolorable microcapsule pigment using the pyridine compound / derivative as the leuco dye (dye) described in Patent Documents 1 to 3 or 4,4'-bis (diethylamino) benzophenone is a microcapsule pigment. Solubility is still insufficient for the medium constituting the core component of the above, and there are problems such as a satisfactory color development density and a point that a bright hue cannot be obtained.
本発明は、上記従来技術の課題等に鑑み、これを解消しようとするものであり、優れた発色濃度と明るい色相が得られるロイコ色素からなる色素、この色素の顕色、消色機構を利用した熱変色性のマイクロカプセル顔料及びこのマイクロカプセル顔料を含有した筆記具用インク組成物を提供することを目的とする。 The present invention has been made in view of the above-mentioned problems of the prior art, and is intended to solve this problem by utilizing a dye made of a leuco dye capable of obtaining an excellent color density and a bright hue, and a color-developing and decolorizing mechanism of this dye. It is an object of the present invention to provide a thermochromic microcapsule pigment and an ink composition for a writing instrument containing the microcapsule pigment.
本発明者らは、上記従来の課題等に鑑み、鋭意研究を行った結果、特定のロイコ色素、この色素を用いたマイクロカプセル顔料を用いることにより、上記目的の色素、それを用いたマイクロカプセル顔料及び筆記具用インク組成物が得られることを見出し、本発明を完成するに至ったのである。 As a result of diligent research in view of the above-mentioned conventional problems and the like, the present inventors have obtained a specific leuco dye, a microcapsule pigment using this dye, the above-mentioned target dye, and a microcapsule using the same. They have found that pigments and ink compositions for writing instruments can be obtained, and have completed the present invention.
すなわち、本発明の色素は、下記式（Ｉ）で示されるロイコ色素からなることを特徴とする。
本発明のマイクロカプセル顔料は、上記色素、顕色剤及び変色温度調整剤を少なくとも含むことを特徴とする。また、本発明の筆記具用インク組成物は、上記マイクロカプセル顔料を含有することを特徴とする。
That is, the dye of the present invention is characterized by being composed of a leuco dye represented by the following formula (I).
The microcapsule pigment of the present invention is characterized by containing at least the above dye, a color developer and a discoloration temperature adjusting agent. Further, the ink composition for a writing instrument of the present invention is characterized by containing the above-mentioned microcapsule pigment.
本発明によれば、優れた発色濃度と明るい色相が得られるロイコ色素からなる色素、この色素の顕色、消色機構を利用した熱変色性のマイクロカプセル顔料及びこのマイクロカプセル顔料を含有した筆記具用インク組成物が提供される。 According to the present invention, a dye composed of a leuco pigment that can obtain an excellent color density and a bright hue, a thermochromic microcapsule pigment utilizing the color development and decolorization mechanism of this dye, and a writing instrument containing the microcapsule pigment. An ink composition for use is provided.
以下に、本発明の実施形態を詳しく説明する。
〔色素〕
本発明の色素は、下記式（Ｉ）で示されるロイコ色素からなることを特徴とするものである。
[Dye]
The dye of the present invention is characterized by comprising a leuco dye represented by the following formula (I).
本発明に用いる上記式（Ｉ）で示される色素は、黄色のロイコ色素として発色濃度及び明るい黄色の色調となるものである。
黄色のロイコ色素としては、特許文献１、２で例示したピリジン化合物・誘導体、フルオラン類などが知られているが、本発明では、上記式（Ｉ）で示される色素を用いることで、更に、発色濃度に優れ、濃度が高く明るい色調となるものである。
上記式（Ｉ）中において、Ｒ１、Ｒ２はメチル基、エチル基、ｎ−プロピル基、イソプロピル基、ｎ−ブチル基、ｓｅｃ−ブチル基、イソブチル基、ｔｅｒｔ−ブチル基などからなる炭素数１〜４のアルキル基である。また、３つのＲ３のうち、何れか一つが−ＯＨ基（ヒドロキシ基）であり、残りの２つが水素原子を表す。
上記式（Ｉ）中において、Ｒ１、Ｒ２は、互いに同一であっても異なっていてもよく、好ましくは、本発明の効果の更なる発揮、製造性などから互いに同一なものがよい。また、３つのＲ３のうち、２位の位置に−ＯＨ基（ヒドロキシ基）を有することが好ましい。
The dye represented by the above formula (I) used in the present invention is a yellow leuco dye having a color density and a bright yellow color tone.
As the yellow leuco dye, pyridine compounds / derivatives, fluorans and the like exemplified in Patent Documents 1 and 2 are known, but in the present invention, by using the dye represented by the above formula (I), further It has excellent color development density, high density, and bright color tone.
In the above formula (I), R1 and R2 have 1 to 1 carbon atoms composed of a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, an isobutyl group, a tert-butyl group and the like. It is an alkyl group of 4. Further, any one of the three R3s is a −OH group (hydroxy group), and the remaining two represent a hydrogen atom.
In the above formula (I), R1 and R2 may be the same or different from each other, and preferably they are the same from each other in terms of further exertion of the effects of the present invention, manufacturability and the like. Further, it is preferable to have a -OH group (hydroxy group) at the 2-position of the three R3s.
上記式（Ｉ）で示される具体的なロイコ色素としては、例えば、２−（２’−ヒドロキシフェニル）−６−フェニル−４−（４’−ジメチルアミノフェニル）ピリジン、２−（２’−ヒドロキシフェニル）−６−フェニル−４−（４’−ジエチルアミノフェニル）ピリジン、２−（２’−ヒドロキシフェニル）−６−フェニル−４−（４’−ジプロピルアミノフェニル）ピリジン、２−（２’−ヒドロキシフェニル）−６−フェニル−４−（４’−ジブチルアミノフェニル）ピリジン、２−（３’−ヒドロキシフェニル）−６−フェニル−４−（４’−ジメチルアミノフェニル）ピリジン、２−（４’−ヒドロキシフェニル）−６−フェニル−４−（４’−ジメチルアミノフェニル）ピリジン、２−（３’−ヒドロキシフェニル）−６−フェニル−４−（４’−ジエチルアミノフェニル）ピリジン、２−（４’−ヒドロキシフェニル）−６−フェニル−４−（４’−ジエチルアミノフェニル）ピリジン、２−（３’−ヒドロキシフェニル）−６−フェニル−４−（４’−ジプロピルアミノフェニル）ピリジン、２−（４’−ヒドロキシフェニル）−６−フェニル−４−（４’−ジプロピルアミノフェニル）ピリジン、２−（３’−ヒドロキシフェニル）−６−フェニル−４−（４’−ジブチルアミノフェニル）ピリジン、２−（４’−ヒドロキシフェニル）−６−フェニル−４−（４’−ジブチルアミノフェニル）ピリジンなどを挙げることができ、これらは１種または２種以上を混合して用いることができる。
好ましくは、発色濃度、明るい色調、製造性等の点から、Ｒ１、Ｒ２が、共にメチル基、エチル基、ｎ−プロピル基、ｎ−ブチル基であるものが好ましく、また、３つのＲ３のうち、２位又は４位の位置に−ＯＨ基（ヒドロキシ基）を有することが好ましく、特に２位の位置に有することが好ましい。上記の各アルキル基、３つのＲ３のうち、何れか一つに−ＯＨ基（ヒドロキシ基）を導入することにより、高い発色濃度と明るい色調を実現することが可能となる。
Specific leuco dyes represented by the above formula (I) include, for example, 2- (2'-hydroxyphenyl) -6-phenyl-4- (4'-dimethylaminophenyl) pyridine and 2- (2'-). Hydroxyphenyl) -6-Phenyl-4- (4'-diethylaminophenyl) pyridine, 2- (2'-hydroxyphenyl) -6-Phenyl-4- (4'-dipropylaminophenyl) pyridine, 2- (2) '-Hydroxyphenyl) -6-Phenyl-4- (4'-dibutylaminophenyl) pyridine, 2- (3'-Phenylphenyl) -6-Phenyl-4- (4'-dimethylaminophenyl) pyridine, 2- (4'-Hydroxyphenyl) -6-Phenyl-4- (4'-Dimethylaminophenyl) pyridine, 2- (3'-Hydrenylphenyl) -6-Phenyl-4- (4'-diethylaminophenyl) pyridine, 2 -(4'-Hydroxyphenyl) -6-Phenyl-4- (4'-diethylaminophenyl) pyridine, 2- (3'-hydroxyphenyl) -6-Phenyl-4- (4'-dipropylaminophenyl) pyridine , 2- (4'-Hydroxyphenyl) -6-Phenyl-4- (4'-dipropylaminophenyl) pyridine, 2- (3'-Hydroxyphenyl) -6-Phenyl-4- (4'-dibutylamino) Phenyl) pyridine, 2- (4'-hydroxyphenyl) -6-phenyl-4- (4'-dibutylaminophenyl) pyridine and the like can be mentioned, and these may be used alone or in admixture of two or more. Can be done.
Preferably, R1 and R2 are both a methyl group, an ethyl group, an n-propyl group, and an n-butyl group from the viewpoints of color density, bright color tone, manufacturability, and the like, and among the three R3s, it is preferable. It is preferable to have a −OH group (hydroxy group) at the 2-position or 4-position, and particularly preferably at the 2-position. By introducing a -OH group (hydroxy group) into any one of the above alkyl groups and three R3s, it is possible to realize a high color density and a bright color tone.
上記式（Ｉ）で示される各ロイコ色素の製造は、市販の又は汎用の合成手段により得られた２’−ヒドロキシアセトフェノンと、アミノベンズアルデヒド化合物と、フェナシルピリジニウムブロミドとを酸触媒の存在下で加熱反応させることなどにより、容易に上記式（Ｉ）で示される発色濃度及び明るい色調となるロイコ色素を得ることができる。例えば、２−（２’−ヒドロキシフェニル）−６−フェニル−４−（４’−ジメチルアミノフェニル）ピリジンを製造する場合は、２’−ヒドロキシアセトフェノンと、４−ジメチルアミノベンズアルデヒド化合物と、フェナシルピリジニウムブロミドとを酸触媒の存在下で加熱反応させることなどにより得ることができる。また、２−（３’−ヒドロキシフェニル）−６−フェニル−４−（４’−ジメチルアミノフェニル）ピリジンを製造する場合は、３’−ヒドロキシアセトフェノンと、４−ジメチルアミノベンズアルデヒド化合物と、フェナシルピリジニウムブロミドとを酸触媒の存在下で加熱反応させることなどにより得ることができる。 In the production of each leuco dye represented by the above formula (I), 2'-hydroxyacetophenone obtained by a commercially available or general-purpose synthetic means, an aminobenzaldehyde compound, and phenacylpyridinium bromide are used in the presence of an acid catalyst. By subjecting to a heating reaction or the like, a leuco dye having a color-developing density and a bright color tone represented by the above formula (I) can be easily obtained. For example, when producing 2- (2'-hydroxyphenyl) -6-phenyl-4- (4'-dimethylaminophenyl) pyridine, 2'-hydroxyacetophenone, a 4-dimethylaminobenzaldehyde compound, and phenacyl are used. It can be obtained by subjecting pyridinium bromide to a heating reaction in the presence of an acid catalyst. When producing 2- (3'-hydroxyphenyl) -6-phenyl-4- (4'-dimethylaminophenyl) pyridine, 3'-hydroxyacetophenone, a 4-dimethylaminobenzaldehyde compound, and phenacyl are used. It can be obtained by subjecting pyridinium bromide to a heating reaction in the presence of an acid catalyst.
〔マイクロカプセル顔料〕
次に、本発明のマイクロカプセル顔料は、上記式（Ｉ）で示される色素、顕色剤、変色温度調整剤から少なくとも構成される熱変色性組成物を内包させたものである。
[Microcapsule pigment]
Next, the microcapsule pigment of the present invention contains at least a thermochromic composition composed of a dye represented by the above formula (I), a color developer, and a color change temperature adjusting agent.
＜顕色剤＞
用いる顕色剤は、上記式（Ｉ）で示される色素を発色させる能力を有する成分となるものである。用いられる顕色剤は、従来公知のものが使用可能であり、例えば、無機酸、芳香族カルボン酸及びその無水物又は金属塩類、有機スルホン酸、その他の有機酸、フェノール性化合物や、ビスフェノール又はその誘導体等が挙げられる。
<Color developer>
The color developer used is a component having an ability to develop a color of the dye represented by the above formula (I). As the color developer used, conventionally known ones can be used, for example, inorganic acids, aromatic carboxylic acids and their anhydrides or metal salts, organic sulfonic acids, other organic acids, phenolic compounds, bisphenols or Examples thereof include derivatives thereof.
本発明においては、これらの顕色剤を１種又は２種以上組み合わせて用いることにより、発色時の色彩濃度を自由に調節することができる。従って、その使用量は、所望される色彩濃度に応じて任意に選択すればよく、特に限定されるものではないが、通常、前記した式（Ｉ）で示される色素１質量部に対して、０．１〜１００質量部程度の範囲内で選択するのが好適である。 In the present invention, the color density at the time of color development can be freely adjusted by using one or a combination of two or more of these color developeres. Therefore, the amount to be used may be arbitrarily selected according to the desired color density, and is not particularly limited, but is usually based on 1 part by mass of the dye represented by the above formula (I). It is preferable to select in the range of about 0.1 to 100 parts by mass.
＜変色温度調整剤＞
本発明に用いる変色温度調整剤は、前記式（Ｉ）で示される色素と顕色剤の呈色において変色温度をコントロールする物質である。
用いることができる変色温度調整剤は、従来公知のものが使用可能である。具体的には、アルコール類、エステル類、ケトン類、エーテル類、酸アミド類、アゾメチン類、脂肪酸類、炭化水素類、ビスフェノール誘導体等の化学構造中に水酸基を有する化合物と、炭素数８〜２２の飽和脂肪酸とから構成されるエステル化合物などが挙げられる。
<Discoloration temperature adjuster>
The discoloration temperature adjusting agent used in the present invention is a substance that controls the discoloration temperature in the coloration of the dye and the color developer represented by the above formula (I).
As the discoloration temperature adjusting agent that can be used, conventionally known ones can be used. Specifically, compounds having a hydroxyl group in the chemical structure such as alcohols, esters, ketones, ethers, acid amides, azomethines, fatty acids, hydrocarbons, and bisphenol derivatives, and 8 to 22 carbon atoms. Examples thereof include ester compounds composed of saturated fatty acids of the above.
この変色温度調整剤の使用量は、所望されるヒステリシス幅及び発色時の色彩濃度等に応じて適宜選択すればよく、特に限定されるものではないが、通常、色素１質量部に対して、１〜１００質量部程度の範囲内で使用するのが好ましい。 The amount of the discoloration temperature adjusting agent used may be appropriately selected according to the desired hysteresis width, the color density at the time of color development, and the like, and is not particularly limited, but is usually, with respect to 1 part by mass of the dye. It is preferably used within the range of about 1 to 100 parts by mass.
＜マイクロカプセル顔料＞
本発明に用いるマイクロカプセル顔料は、少なくとも上記式（Ｉ）で示される色素、顕色剤、変色温度調整剤からなる熱変色性組成物を、所定の平均粒子径（例えば、筆記具用インクでは、平均粒子径が０．３〜５μｍ）となるように、マイクロカプセル化することにより製造することができる。
なお、本発明で規定する「平均粒子径」は、粒子径分布解析装置ＨＲＡ９３２０−Ｘ１００（日機装株式会社性）を用いて、体積基準により算出されたＤ５０の値である。
<Microcapsule pigment>
The microcapsule pigment used in the present invention is a thermochromic composition composed of at least a dye represented by the above formula (I), a color developer, and a color change temperature adjusting agent, and has a predetermined average particle size (for example, in a writing instrument ink). It can be produced by microencapsulating so that the average particle size is 0.3 to 5 μm).
The "average particle size" defined in the present invention is a value of D50 calculated on a volume basis using the particle size distribution analyzer HRA9320-X100 (Nikki So Co., Ltd.).
マイクロカプセル化法としては、例えば、界面重合法、界面重縮合法、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、スプレードライニング法などを挙げることができ、用途に応じて適宜選択することができる。
好ましいマイクロカプセル顔料としては、安定性、より充実した機能を発揮せしめる,から、コアシェル型のマイクロカプセル顔料が望ましい。
Examples of the microencapsulation method include an interfacial polymerization method, an interfacial polycondensation method, an insitu polymerization method, an in-liquid curing coating method, a phase separation method from an aqueous solution, a phase separation method from an organic solvent, a melt dispersion cooling method, and a gas. Examples thereof include a medium suspension coating method and a spray drying method, which can be appropriately selected depending on the intended use.
As a preferable microcapsule pigment, a core-shell type microcapsule pigment is desirable because it exhibits stability and more fulfilling functions.
例えば、水溶液からの相分離法では、上記式（Ｉ）で示される色素、顕色剤、変色温度調整剤を加熱溶融後、乳化剤溶液に投入し、加熱攪拌して油滴状に分散させ、次いで、カプセル膜剤として、樹脂原料などを使用、例えば、アミノ樹脂溶液、具体的には、メチロールメラミン水溶液、尿素溶液、ベンゾグアナミン溶液などの各液を徐々に投入し、引き続き反応させて調製後、この分散液を濾過することにより目的の色素を用いた熱変色性のマイクロカプセル顔料を製造することができる。 For example, in the phase separation method from an aqueous solution, the dye, the color developer, and the discoloration temperature adjusting agent represented by the above formula (I) are heated and melted, then put into an emulsifier solution, heated and stirred to disperse in the form of oil droplets. Next, a resin raw material or the like is used as the capsule membrane agent, for example, each solution such as an amino resin solution, specifically, a methylol melamine solution, a urea solution, or a benzoguanamine solution is gradually added, and the reaction is continued to prepare the mixture. By filtering this dispersion, a thermochromic microcapsule pigment using the desired dye can be produced.
本発明のマイクロカプセル顔料では、描線濃度、保存安定性、筆記性の更なる向上の点から、壁膜がウレタン樹脂、エポキシ樹脂、あるいはアミノ樹脂で形成されることが好ましい。ウレタン樹脂としては、例えば、イソシアネートとポリオールとの化合物が挙げられる。エポキシ樹脂としては、例えば、エポキシ樹脂とアミンの化合物が挙げられる。アミノ樹脂としては、例えば、メラミン樹脂、尿素樹脂、ベンゾグアナミン樹脂などで形成されること、更に好ましくは、製造性、保存安定性、筆記性の点から、メラミン樹脂で形成されることが望ましい。マイクロカプセル顔料の壁膜の厚さは、必要とする壁膜の強度や描線濃度に応じて適宜決められる。
なお、壁膜がアミノ樹脂で形成するためには、各マイクロカプセル化法を用いる際に、好適なアミノ樹脂原料（メラミン樹脂、尿素樹脂、ベンゾグアナミン樹脂等）、並びに、分散剤、保護コロイド剤などを選択する。
In the microcapsule pigment of the present invention, the wall film is preferably formed of a urethane resin, an epoxy resin, or an amino resin from the viewpoint of further improving the drawing density, storage stability, and writability. Examples of the urethane resin include compounds of isocyanate and polyol. Examples of the epoxy resin include a compound of an epoxy resin and an amine. The amino resin is preferably formed of, for example, a melamine resin, a urea resin, a benzoguanamine resin, or the like, and more preferably formed of a melamine resin from the viewpoints of manufacturability, storage stability, and writability. The thickness of the wall film of the microcapsule pigment is appropriately determined according to the required strength of the wall film and the drawing density.
In order to form the wall film with amino resin, suitable amino resin raw materials (melamine resin, urea resin, benzoguanamine resin, etc.), dispersants, protective colloidal agents, etc. are used when each microencapsulation method is used. Select.
本発明のマイクロカプセル顔料では、上記式（Ｉ）で示される色素、顕色剤及び変色温度調整剤の種類、上記各成分の範囲の量などを好適に組み合わせることにより、黄色の発色温度、消色温度を好適な温度に設定することができる。
好ましくは、マイクロカプセル顔料（全量）中の上記式（Ｉ）で示される色素の含有量は、コア成分（ロイコ色素、顕色剤、変色温度調整剤、必要に応じてその他の成分）を基準に１〜２０質量％（以下、単に「％」という）となることが望ましい。この範囲の量とすることにより、更に、発色の際には、発色濃度に優れ、明るい色調となる。
In the microcapsule pigment of the present invention, the yellow color development temperature and extinction are achieved by appropriately combining the types of the dye represented by the above formula (I), the color developer and the color change temperature adjusting agent, the amount in the range of each of the above components, and the like. The color temperature can be set to a suitable temperature.
Preferably, the content of the dye represented by the above formula (I) in the microcapsule pigment (total amount) is based on the core component (leuco dye, color developer, discoloration temperature adjuster, and other components if necessary). It is desirable that the content is 1 to 20% by mass (hereinafter, simply referred to as "%"). By setting the amount in this range, the color density is excellent and the color tone becomes bright at the time of color development.
このように構成される本発明のマイクロカプセル顔料は、発色濃度に優れ、明るい色調を有すると共に、易消色性、安定性に優れ、筆記具用インクなどの熱変色性の顔料として好適に用いることができ、後述するように、溶媒種が水性、または、油性の筆記具用インク組成物の顔料として用いても、その溶媒種等に影響を受けずに、上記効果を発揮することができるものである。 The microcapsule pigment of the present invention configured as described above has excellent color density, bright color tone, easy decolorization and stability, and is suitably used as a heat-discoloring pigment for writing instrument inks and the like. As will be described later, even if the solvent type is used as a pigment in an aqueous or oil-based ink composition for writing instruments, the above effect can be exhibited without being affected by the solvent type or the like. is there.
＜筆記具用インク組成物＞
本発明の筆記具用インク組成物は、上記構成のマイクロカプセル顔料を含有することを特徴とするものであり、水性、または、油性のボールペン用、マーキングペン用等の筆記具用インク組成物として用いることをできる。
本発明のマイクロカプセル顔料の含有量は、各水性又は油性のインク組成物全量に対して、好ましくは、５〜３０％、更に好ましくは、１０〜２５％とすることが望ましい。
このマイクロカプセル顔料の含有量が５％未満であると、着色力、発色性が不十分となり、一方、３０％を超えると、カスレが生じやすくなり、好ましくない。
<Ink composition for writing tools>
The ink composition for writing instruments of the present invention is characterized by containing the microcapsule pigment having the above-mentioned composition, and is used as an ink composition for writing instruments such as water-based or oil-based ballpoint pens and marking pens. Can be done.
The content of the microcapsule pigment of the present invention is preferably 5 to 30%, more preferably 10 to 25%, based on the total amount of each aqueous or oily ink composition.
If the content of the microcapsule pigment is less than 5%, the coloring power and the coloring property are insufficient, while if it exceeds 30%, blurring is likely to occur, which is not preferable.
＜筆記具用水性インク組成物＞
本発明の筆記具用インク組成物において、水性では、上記マイクロカプセル顔料の他、残部として溶媒である水（水道水、精製水、蒸留水、イオン交換水、純水等）の他、各筆記具用（ボールペン用、マーキングペン用等）の用途に応じて、本発明の効果を損なわない範囲で、水溶性有機溶剤、増粘剤、潤滑剤、防錆剤、防腐剤もしくは防菌剤などを適宜含有することができる。
<Aqueous ink composition for writing tools>
In the ink composition for writing instruments of the present invention, in the case of water-based ink, in addition to the above-mentioned microcapsule pigment, water (tap water, purified water, distilled water, ion-exchanged water, pure water, etc.) as a solvent as a balance, and other writing instruments Depending on the application (for ballpoint pens, marking pens, etc.), water-soluble organic solvents, thickeners, lubricants, rust preventives, preservatives, antibacterial agents, etc. are appropriately used as long as the effects of the present invention are not impaired. Can be contained.
用いることができる水溶性有機溶剤としては、例えば、エチレングリコール、ジエチレングリコール、トリエチレングリコール、プロピレングリコール、ポリエチレングリコール、３−ブチレングリコール、チオジエチレングリコール、グリセリン等のグリコール類や、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メチルエーテル、単独或いは混合して使用することができる。 Examples of the water-soluble organic solvent that can be used include glycols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, polyethylene glycol, 3-butylene glycol, thiodiethylene glycol, and glycerin, and ethylene glycol monomethyl ether and diethylene glycol monomethyl. Ether can be used alone or in combination.
用いることができる増粘剤としては、例えば、合成高分子、セルロースおよび多糖類からなる群から選ばれた少なくとも一種が望ましい。具体的には、アラビアガム、トラガカントガム、グアーガム、ローカストビーンガム、アルギン酸、カラギーナン、ゼラチン、キサンタンガム、ウェランガム、サクシノグリカン、ダイユータンガム、デキストラン、メチルセルロース、エチルセルロース、ヒドロキシエチルセルロース、カルボキシメチルセルロース、デンプングリコール酸及びその塩、アルギン酸プロピレングリコールエステル、ポリビニルアルコール、ポリビニルピロリドン、ポリビニルメチルエーテル、ポリアクリル酸及びその塩、カルボキシビニルポリマー、ポリエチレオキサイド、酢酸ビニルとポリビニルピロリドンの共重合体、架橋型アクリル酸重合体及びその塩、非架橋型アクリル酸重合体及びその塩、スチレン−アクリル酸共重合体及びその塩などが挙げられる。 As the thickener that can be used, for example, at least one selected from the group consisting of synthetic polymers, cellulose and polysaccharides is desirable. Specifically, Arabic gum, tragacant gum, guar gum, locust bean gum, alginic acid, carrageenan, gelatin, xanthan gum, welan gum, succinoglycan, dieutan gum, dextran, methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, carboxymethyl cellulose, starch glycolic acid and The salt, propylene glycol alginate, polyvinyl alcohol, polyvinylpyrrolidone, polyvinylmethyl ether, polyacrylic acid and its salt, carboxyvinyl polymer, polyethyleoxide, copolymer of vinyl acetate and polyvinylpyrrolidone, crosslinked acrylic acid polymer and its salt. Examples thereof include salts, non-crosslinked acrylic acid polymers and salts thereof, styrene-acrylic acid copolymers and salts thereof.
潤滑剤としては、顔料の表面処理剤にも用いられる多価アルコールの脂肪酸エステル、糖の高級脂肪酸エステル、ポリオキシアルキレン高級脂肪酸エステル、アルキル燐酸エステルなどのノニオン系や、高級脂肪酸アミドのアルキルスルホン酸塩、アルキルアリルスルホン酸塩などのアニオン系、ポリアルキレングリコールの誘導体やフッ素系界面活性剤、ポリエーテル変性シリコーンなどが挙げられる。また、防錆剤としては、ベンゾトリアゾール、トリルトリアゾール、ジシクロへキシルアンモニウムナイトライト、サポニン類など、防腐剤もしくは防菌剤としては、フェノール、ナトリウムオマジン、安息香酸ナトリウム、ベンズイミダゾール系化合物などが挙げられる。 As lubricants, nonionics such as fatty acid esters of polyhydric alcohols used as surface treatment agents for pigments, higher fatty acid esters of sugars, polyoxyalkylene higher fatty acid esters, and alkyl phosphate esters, and alkyl sulfonic acids of higher fatty acid amides. Examples thereof include salts, anionic compounds such as alkylallyl sulfonates, derivatives of polyalkylene glycols, fluorine-based surfactants, and polyether-modified silicones. In addition, rust preventives include benzotriazole, triltriazole, dicyclohexylammonium nitrate, saponins, etc., and preservatives or antibacterial agents include phenol, sodium omadin, sodium benzoate, benzimidazole compounds, etc. Can be mentioned.
この筆記具用水性インク組成物を製造するには、従来から知られている方法が採用可能であり、例えば、上記マイクロカプセル顔料の他、上記水性における各成分を所定量配合し、ホモミキサー、もしくはディスパー等の攪拌機により攪拌混合することによって得られる。更に必要に応じて、ろ過や遠心分離によってインク組成物中の粗大粒子を除去してもよい。 In order to produce this water-based ink composition for writing utensils, a conventionally known method can be adopted. It is obtained by stirring and mixing with a stirrer such as a disper. Further, if necessary, coarse particles in the ink composition may be removed by filtration or centrifugation.
＜筆記具用油性インク組成物＞
本発明の筆記具用インク組成物において、油性では、上記構成のマイクロカプセル顔料を含有すると共に、主溶剤として、ポリプロピレングリコール、ポリブチレングリコール、ポリオキシプロピレンジグリセリルエーテルから選ばれる少なくとも一つとを含有することが好ましい。これらの溶剤を主溶剤として選択、使用することで、上記マイクロカプセル顔料の経時的な凝集を発生しないように作用するものである。
<Oil-based ink composition for writing tools>
In the oil-based ink composition for writing instruments of the present invention, the microcapsule pigment having the above composition is contained, and at least one selected from polypropylene glycol, polybutylene glycol, and polyoxypropylene diglyceryl ether is contained as a main solvent. Is preferable. By selecting and using these solvents as the main solvent, the microcapsule pigments act so as not to agglomerate over time.
用いるポリプロピレングリコール、ポリブチレングリコールは、各重合度のものが使用できるが、本発明の効果を更に発揮せしめる点から、ポリプロピレングリコールでは重合度（重量平均）４００〜７００の範囲の使用が好ましく、ポリブチレングリコールでは重合度（重量平均）５００〜７００の範囲の使用が好ましい。
また、本発明で用いるポリオキシプロピレンジグリセリルエーテル〔ＰＯＰ（ｎ）ジグリセリルエーテル〕はジグリセリンの水酸基にポリオキシプロピレンが付加重合したものである。本発明においてポリオキシプロピレンジグリセリルエーテル〔ＰＯＰ（ｎ）ジグリセリルエーテル〕におけるオキシプロピレンの付加モル数（ｎ）は、本発明の効果を更に発揮せしめる点から、４〜２５が好ましく、更に好ましくは４〜１４である。
As the polypropylene glycol and polybutylene glycol to be used, those having each degree of polymerization can be used, but from the viewpoint of further exerting the effect of the present invention, polypropylene glycol is preferably used in the range of degree of polymerization (weight average) of 400 to 700, and is poly. Butylene glycol is preferably used with a degree of polymerization (weight average) in the range of 500 to 700.
Further, the polyoxypropylene diglyceryl ether [POP (n) diglyceryl ether] used in the present invention is obtained by addition polymerization of polyoxypropylene to the hydroxyl group of diglycerin. In the present invention, the number of added moles (n) of oxypropylene in the polyoxypropylene diglyceryl ether [POP (n) diglyceryl ether] is preferably 4 to 25, more preferably 4 to 25, from the viewpoint of further exerting the effects of the present invention. 4 to 14.
これらの主溶剤の含有量は、インク組成物中の全溶剤量に対して、５０〜１００％とすることが好ましく、更に好ましくは、８０〜１００％とすることが望ましい。この主溶剤の含有量が、５０％以上とすることにより、経時的な凝集の発生を極力抑制することができる。なお、本発明の効果を損なわない範囲で、上記主溶剤の他、主溶剤と相溶する性質を有する溶剤、例えば、グリセリン、ジグリセリン、プロピレングリコールなどの溶剤を適宜含有することができる。 The content of these main solvents is preferably 50 to 100%, more preferably 80 to 100%, based on the total amount of the solvent in the ink composition. By setting the content of this main solvent to 50% or more, the occurrence of aggregation over time can be suppressed as much as possible. In addition to the above-mentioned main solvent, a solvent having a property of being compatible with the main solvent, for example, a solvent such as glycerin, diglycerin, or propylene glycol can be appropriately contained as long as the effect of the present invention is not impaired.
この筆記具用油性インク組成物では、上記マイクロカプセル顔料、主溶剤の他、各筆記具用（ボールペン用、マーキングペン用等）の用途に応じて、また、必要に応じて、油性インクに悪影響を及ぼさず相溶することができる樹脂や分散剤、防錆剤、防腐剤、潤滑剤等を含有することができる。
用いることができる樹脂としては、例えば、ケトン樹脂、スチレン樹脂、スチレン−アクリル樹脂、テルペンフェノール樹脂、ロジン変性マレイン酸樹脂、ロジンフェノール樹脂、アルキルフェノール樹脂、フェノール系樹脂、スチレン−マレイン酸樹脂、ロジン系樹脂、アクリル系樹脂、尿素アルデヒド系樹脂、マレイン酸系樹脂、シクロヘキサノン系樹脂、ポリビニルブチラール、ポリビニルピロリドン等に代表される樹脂が挙げられる。
In this oil-based ink composition for writing instruments, in addition to the above-mentioned microcapsule pigment and main solvent, the oil-based ink is adversely affected according to the application for each writing instrument (for ballpoint pens, marking pens, etc.) and, if necessary. It can contain a resin, a dispersant, a rust preventive, an antiseptic, a lubricant and the like that can be compatible with each other.
Examples of the resin that can be used include ketone resin, styrene resin, styrene-acrylic resin, terpenphenol resin, rosin-modified maleic acid resin, rosinphenol resin, alkylphenol resin, phenol-based resin, styrene-maleic acid resin, and rosin-based resin. Examples thereof include resins typified by resins, acrylic resins, ureaaldehyde-based resins, maleic acid-based resins, cyclohexanone-based resins, polyvinyl butyral, and polyvinylpyrrolidone.
用いることができる分散剤として、上記に挙げたような樹脂の中からマイクロカプセル顔料を分散できるものを選択して使用することができ、界面活性剤やオリゴマーでも目的に沿うものであれば、含有することができる。
具体的な分散剤としては、例えば、ポリビニルアルコール、ポリビニルピロリドン、ポリビニルブチラール、ポリビニルエーテル、スチレン−マレイン酸共重合体、ケトン樹脂、ヒドロキシエチルセルロースやその誘導体、スチレン−アクリル酸共重合体等の合成樹脂やＰＯ・ＥＯ付加物やポリエステルのアミン系オリゴマー等が挙げることができる。
また、防錆剤、防腐剤、潤滑剤としては、上述の水性で用いた各種の防錆剤、防腐剤、潤滑剤を用いることができる。
As the dispersant that can be used, those that can disperse the microcapsule pigment can be selected and used from the resins listed above, and if the surfactant or oligomer is also suitable for the purpose, it is contained. can do.
Specific examples of the dispersant include synthetic resins such as polyvinyl alcohol, polyvinyl pyrrolidone, polyvinyl butyral, polyvinyl ether, styrene-maleic acid copolymer, ketone resin, hydroxyethyl cellulose and its derivatives, and styrene-acrylic acid copolymer. , PO / EO adducts, polyester amine-based oligomers, and the like.
Further, as the rust preventive, preservative, and lubricant, various rust preventives, preservatives, and lubricants used in the above-mentioned aqueous solution can be used.
この筆記具用油性インク組成物を製造するには、従来から知られている方法が採用可能であり、例えば、上記マイクロカプセル顔料の他、上記油性における各成分を所定量配合し、ホモミキサー、もしくはディスパー等の攪拌機により攪拌混合することによって得られる。更に必要に応じて、ろ過や遠心分離によってインク組成物中の粗大粒子を除去してもよい。 In order to produce this oil-based ink composition for writing utensils, a conventionally known method can be adopted. For example, in addition to the above-mentioned microcapsule pigment, a predetermined amount of each component in the above-mentioned oiliness is blended, and a homomixer or a homomixer or It is obtained by stirring and mixing with a stirrer such as a disper. Further, if necessary, coarse particles in the ink composition may be removed by filtration or centrifugation.
このように構成される本発明の筆記具用インク組成物では、上記式（Ｉ）で示される発色濃度に優れ、明るい色調となる色素、顕色剤及び変色温度調整剤を少なくとも含むマイクロカプセル顔料を含有する水性、または、油性のインクを処方し、このインクを搭載したボールペン体、マーキングペン体などの筆記具にて紙面等に筆記しても、経時的なマイクロカプセル顔料の凝集が発生せず、筆跡を良好に変色（発色：黄色、消色：無色）させることができ筆記具用インク組成物が得られるものとなる。 In the ink composition for writing instruments of the present invention configured as described above, a microcapsule pigment containing at least a dye, a color developer, and a discoloration temperature adjusting agent having an excellent color density represented by the above formula (I) and a bright color tone is used. Even if a water-based or oil-based ink to be contained is prescribed and writing is performed on a paper surface or the like with a writing instrument such as a ballpoint pen or a marking pen equipped with this ink, the microcapsule pigment does not aggregate over time. The brush stroke can be satisfactorily discolored (color development: yellow, decolorization: colorless), and an ink composition for writing instruments can be obtained.
次に、製造例、実施例及び比較例により本発明を更に詳細に説明するが、本発明は下記実施例等に限定されるものではない。なお、以下において、配合単位である「部」は質量部を意味する。 Next, the present invention will be described in more detail with reference to Production Examples, Examples and Comparative Examples, but the present invention is not limited to the following Examples and the like. In the following, the compounding unit "parts" means parts by mass.
下記製造例１〜４により、上記（Ｉ）で示される各色素を製造し、下記製造例５〜１１によりマイクロカプセル顔料１〜７を製造した。
〔製造例１：上記式（Ｉ）で示される色素（Ｒ１、Ｒ２が共にメチル基、Ｒ３のうち、２位の位置に−ＯＨ基（ヒドロキシ基））の製造〕
還流管を備えたフラスコに２’−ヒドロキシアセトフェノン２．７ｇ、４−ジメチルアミノベンズアルデヒド３．０ｇ、フェナシルピリジニウムブロミド７．２ｇ、酢酸アンモニウム３８．５ｇ、酢酸１０ｍｌを入れ、１４０℃で３時間攪拌した。反応終了後、６０℃でメタノールを加え、室温で析出物を濾過した。得られた個体を酢酸エチルに溶解して不要物を除去し、減圧して溶媒を留去した。残渣をアセトニトリルで再結晶することにより、目的物〔２−（２’−ヒドロキシフェニル）−６−フェニル−４−（４’−ジメチルアミノフェニル）ピリジン〕３．２ｇを得た。
The dyes shown in (I) above were produced according to Production Examples 1 to 4 below, and microcapsule pigments 1 to 7 were produced according to Production Examples 5 to 11 below.
[Production Example 1: Production of a dye represented by the above formula (I) (both R1 and R2 are methyl groups and R3 is a -OH group (hydroxy group) at the 2-position position)]
Put 2.7 g of 2'-hydroxyacetophenone, 3.0 g of 4-dimethylaminobenzaldehyde, 7.2 g of phenacylpyridinium bromide, 38.5 g of ammonium acetate and 10 ml of acetic acid in a flask equipped with a reflux tube, and stir at 140 ° C. for 3 hours. did. After completion of the reaction, methanol was added at 60 ° C., and the precipitate was filtered at room temperature. The obtained solid was dissolved in ethyl acetate to remove unnecessary substances, and the pressure was reduced to distill off the solvent. The residue was recrystallized from acetonitrile to obtain 3.2 g of the desired product [2- (2'-hydroxyphenyl) -6-phenyl-4- (4'-dimethylaminophenyl) pyridine].
〔製造例２：上記式（Ｉ）で示される色素（Ｒ１、Ｒ２が共にエチル基、Ｒ３のうち、２位の位置に−ＯＨ基（ヒドロキシ基））の製造〕
上記製造例１において、４−ジメチルアミノベンズアルデヒドに代えて４−ジエチルアミノベンズアルデヒドを用いて、製造例１と同様にして目的物〔２−（２’−ヒドロキシフェニル）−６−フェニル−４−（４’−ジエチルアミノフェニル）ピリジン〕３．２ｇを得た。
[Production Example 2: Production of a dye represented by the above formula (I) (R1 and R2 are both ethyl groups and R3 is a -OH group (hydroxy group) at the 2-position position)]
In Production Example 1, 4-diethylaminobenzaldehyde was used instead of 4-dimethylaminobenzaldehyde, and the target product [2- (2'-hydroxyphenyl) -6-phenyl-4- (4) was used in the same manner as in Production Example 1. '-Diethylaminophenyl) pyridine] 3.2 g was obtained.
〔製造例３：上記式（Ｉ）で示される色素（Ｒ１、Ｒ２が共にプロピル基、Ｒ３のうち、２位の位置に−ＯＨ基（ヒドロキシ基））の製造〕
上記製造例１において、４−ジメチルアミノベンズアルデヒドに代えて４−ジプロピルアミノベンズアルデヒドを用いて、製造例１と同様にして目的物〔２−（２’−ヒドロキシフェニル）−６−フェニル−４−（４’−ジプロピルアミノフェニル）ピリジン〕３．２ｇを得た。
[Production Example 3: Production of a dye represented by the above formula (I) (both R1 and R2 are propyl groups, and -OH group (hydroxy group) at the 2-position position of R3)]
In Production Example 1, 4-dipropylaminobenzaldehyde was used instead of 4-dimethylaminobenzaldehyde, and the target product [2- (2'-hydroxyphenyl) -6-phenyl-4- (4'-Dipropylaminophenyl) Pyridine] 3.2 g was obtained.
〔製造例４：上記式（Ｉ）で示される色素（Ｒ１、Ｒ２が共にブチル基、Ｒ３のうち、２位の位置に−ＯＨ基（ヒドロキシ基））の製造〕
上記製造例１において、４−ジメチルアミノベンズアルデヒドに代えて４−ジブチルアミノベンズアルデヒドを用いて、製造例１と同様にして目的物〔２−（２’−ヒドロキシフェニル）−６−フェニル−４−（４’−ジブチルアミノフェニル）ピリジン〕３．２ｇを得た。
[Production Example 4: Production of a dye represented by the above formula (I) (both R1 and R2 are butyl groups, and a -OH group (hydroxy group) at the 2-position position of R3)]
In Production Example 1, 4-dibutylaminobenzaldehyde was used instead of 4-dimethylaminobenzaldehyde, and the target product [2- (2'-hydroxyphenyl) -6-phenyl-4- (2'-hydroxyphenyl) -6-phenyl-4- ( 4'-Dibutylaminophenyl) pyridine] 3.2 g was obtained.
〔製造例５：熱変色性マイクロカプセル顔料１の製造〕
ロイコ色素として、製造例１の色素４質量部、顕色剤として、ビスフェノールＡ２部、及び変色性温度調整剤として、ミリスチン酸ミリスチル２４部を１００℃に加熱溶融して、均質な組成物３０部を得た。
上記で得た組成物３０部の均一な熱溶液にカプセル膜剤として、ヘキサメチレンジイソシアネートビウレット変性体（Ｄ−１６５Ｎ、三井化学社）１０部を加えて攪拌混合した。次いで、保護コロイドとして１２％ポリビニルアルコール（ＰＶＡ−２０５、クラレ社）水溶液６０部を用いて、２５℃で乳化して分散液を調製した。次いで、５％の多価アミン５部を用いて、８０℃で６０分間処理してコアシェル型のマイクロカプセル顔料を得た。色相は、発色状態においては濃厚な黄色を呈し、消色状態においては残色がなく完全に無色となるものであった。
[Production Example 5: Production of Thermochromic Microcapsule Pigment 1]
As a leuco dye, 4 parts by mass of the dye of Production Example 1, 2 parts of bisphenol A as a color developer, and 24 parts of myristyl myristate as a discoloration temperature adjusting agent are heated and melted at 100 ° C. to 30 parts of a homogeneous composition. Got
To a uniform thermal solution of 30 parts of the composition obtained above, 10 parts of a modified hexamethylene diisocyanate biuret (D-165N, Mitsui Chemicals, Inc.) was added as a capsule membrane agent, and the mixture was stirred and mixed. Then, 60 parts of a 12% polyvinyl alcohol (PVA-205, Kuraray) aqueous solution was used as a protective colloid and emulsified at 25 ° C. to prepare a dispersion. Then, using 5 parts of 5% polyvalent amine, it was treated at 80 ° C. for 60 minutes to obtain a core-shell type microcapsule pigment. The hue was a deep yellow color in the color-developed state, and was completely colorless in the decolorized state with no residual color.
（製造例６：熱変色性マイクロカプセル顔料２の製造）
ロイコ色素として、製造例２の色素３部、顕色剤として、４，４’−（２−エチルヘキシリデン）ビスフェノール２部、及び変色性温度調整剤として、４，４’−（ヘキサフルオロイソプロピリデン）ビスフェノールジミリステート２４部を１００℃に加熱溶融して、均質な組成物２９部を得た。
上記で得た組成物２９部の均一な熱溶液を、保護コロイド剤として、メチルビニルエーテル・無水マレイン酸共重合樹脂〔ガンツレッツＡＮ−１７９：ＩＳＰ（株）社製〕４０部をＮａＯＨにてｐＨ４に溶解させた９０℃の水溶液１００部中に徐々に添加しながら、加熱攪拌して直径約０．５〜１．０μｍの油滴状に分散させ、次いでカプセル膜剤として、メラミン樹脂（スミテックスレジンＭ−３、（株）住友化学製）２０部を徐々に添加し、９０℃で３０分間処理してコアシェル型のマイクロカプセル顔料を得た。色相は、発色状態においては濃厚な黄色を呈し、消色状態においては残色がなく完全に無色となるものであった。
(Production Example 6: Production of Thermochromic Microcapsule Pigment 2)
As a leuco dye, 3 parts of the dye of Production Example 2, as a color developer, 2 parts of 4,4'-(2-ethylhexylidene) bisphenol, and as a discoloration temperature control agent, 4,4'-(hexafluoro). 24 parts of the isopropylidene) bisphenol dimyristate was heated and melted at 100 ° C. to obtain 29 parts of a homogeneous composition.
Using the uniform thermal solution of 29 parts of the composition obtained above as a protective colloidal agent, 40 parts of a methyl vinyl ether / maleic anhydride copolymer resin [Ganzlets AN-179: manufactured by ISP Co., Ltd.] was adjusted to pH 4 with NaOH. While gradually adding to 100 parts of the dissolved aqueous solution at 90 ° C., the mixture is heated and stirred to disperse in the form of oil droplets having a diameter of about 0.5 to 1.0 μm, and then as a capsule film agent, a melamine resin (Sumitex resin). 20 parts of M-3 (manufactured by Sumitomo Chemical Co., Ltd.) was gradually added and treated at 90 ° C. for 30 minutes to obtain a core-shell type microcapsule pigment. The hue was a deep yellow color in the color-developed state, and was completely colorless in the decolorized state with no residual color.
〔製造例７：熱変色性マイクロカプセル顔料３の製造〕
ロイコ色素として、製造例３の色素２質量部、顕色剤として、ビスフェノールＡ２部、及び変色性温度調整剤として、ミリスチン酸ミリスチル２４部を１００℃に加熱溶融して、均質な組成物２８部を得た。
上記で得た組成物２８部を用いて上記製造例５と同様に処理してコアシェル型のマイクロカプセル顔料を得た。色相は、発色状態においては濃厚な黄色を呈し、消色状態においては残色がなく完全に無色となるものであった。
[Production Example 7: Production of Thermochromic Microcapsule Pigment 3]
28 parts of a homogeneous composition is obtained by heating and melting 2 parts by mass of the dye of Production Example 3 as a leuco dye, 2 parts of bisphenol A as a color developer, and 24 parts of myristyl myristate as a discoloration temperature adjusting agent at 100 ° C. Got
Using 28 parts of the composition obtained above, the same treatment as in Production Example 5 was performed to obtain a core-shell type microcapsule pigment. The hue was a deep yellow color in the color-developed state, and was completely colorless in the decolorized state with no residual color.
〔製造例８：熱変色性マイクロカプセル顔料４の製造〕
ロイコ色素として、製造例４の色素１部、顕色剤として、４，４’−（２−エチルヘキシリデン）ビスフェノール２部、及び変色性温度調整剤として、４，４’−（ヘキサフルオロイソプロピリデン）ビスフェノールジミリステート２４部を１００℃に加熱溶融して、均質な組成物２７部を得た。
上記で得た組成物２７部を用いて上記製造例７と同様に処理してコアシェル型のマイクロカプセル顔料４を得た。色相は、発色状態においては濃厚な黄色を呈し、消色状態においては残色がなく完全に無色となるものであった。
[Production Example 8: Production of Thermochromic Microcapsule Pigment 4]
As a leuco dye, 1 part of the dye of Production Example 4, as a color developer, 2 parts of 4,4'-(2-ethylhexylidene) bisphenol, and as a discoloration temperature control agent, 4,4'-(hexafluoro). 24 parts of the isopropylidene) bisphenol dimyristate was heated and melted at 100 ° C. to obtain 27 parts of a homogeneous composition.
Using 27 parts of the composition obtained above, the same treatment as in Production Example 7 was performed to obtain a core-shell type microcapsule pigment 4. The hue was a deep yellow color in the color-developed state, and was completely colorless in the decolorized state with no residual color.
（製造例９：比較例用の熱変色性マイクロカプセル顔料５の製造）
比較例用マイクロカプセル顔料は、ロイコ染料として３’，６’−ジメトキシフルオランを２質量部に変更して用いた以外は、製造例５と同様にしてマイクロカプセル顔料５を得た。色相は、発色状態においては黄色を呈し、消色状態においては無色となるものであった。なお、２質量部に変更したのは、４質量部ではロイコ染料の溶解性が不足して、良好なマイクロカプセル顔料が製造できなかったことによる。
(Production Example 9: Production of Thermochromic Microcapsule Pigment 5 for Comparative Example)
As the microcapsule pigment for Comparative Example, a microcapsule pigment 5 was obtained in the same manner as in Production Example 5, except that 3', 6'-dimethoxyfluorane was changed to 2 parts by mass as a leuco dye. The hue was yellow in the color-developed state and colorless in the decolorized state. The reason for changing to 2 parts by mass is that the solubility of the leuco dye was insufficient at 4 parts by mass, and a good microcapsule pigment could not be produced.
（製造例１０：比較例用の熱変色性マイクロカプセル顔料６の製造）
比較例用マイクロカプセル顔料は、ロイコ染料として従来技術の欄で示した特許文献１で開示の２，６−ジフェニル−４−（４’−ジメチルアミノフェニル）−ピリジンを２質量部に変更して用いた以外は、製造例６と同様にしてマイクロカプセル顔料６を得た。色相は、発色状態においては黄色を呈し、消色状態においては無色となるものであった。なお、２質量部に変更したのは、３質量部ではロイコ染料の溶解性が不足して、良好なマイクロカプセル顔料が製造できなかったことによる。
(Production Example 10: Production of Thermochromic Microcapsule Pigment 6 for Comparative Example)
In the microcapsule pigment for comparative example, 2,6-diphenyl-4- (4'-dimethylaminophenyl) -pyridine disclosed in Patent Document 1 shown in the column of the prior art as a leuco dye was changed to 2 parts by mass. A microcapsule pigment 6 was obtained in the same manner as in Production Example 6 except that it was used. The hue was yellow in the color-developed state and colorless in the decolorized state. The reason for changing to 2 parts by mass is that the solubility of the leuco dye was insufficient at 3 parts by mass, and a good microcapsule pigment could not be produced.
（製造例１１：比較例用の熱変色性マイクロカプセル顔料７の製造）
比較例用マイクロカプセル顔料は、ロイコ染料として従来技術の欄で示した特許文献３で開示の４，４’−ビス（ジエチルアミノ）ベンゾフェノンを用いた以外は、製造例７と同様にしてマイクロカプセル顔料７を得た。色相は、発色状態においては黄色を呈し、消色状態においては無色となるものであった。
(Production Example 11: Production of Thermochromic Microcapsule Pigment 7 for Comparative Example)
The microcapsule pigment for the comparative example is the same as that in Production Example 7 except that 4,4'-bis (diethylamino) benzophenone disclosed in Patent Document 3 shown in the column of the prior art is used as the leuco dye. I got 7. The hue was yellow in the color-developed state and colorless in the decolorized state.
〔実施例１〜４及び比較例１〜３〕
（筆記具用インク組成物の処方）
下記表１に示す配合処方（マイクロカプセル顔料１〜７、水性インクの各成分）にしたがって、常法により各筆記具用水性インク組成物を調製した。なお、各マイクロカプセル顔料１〜７は、各マイクロカプセル分散液を濾過し、乾燥することによりマイクロカプセル顔料として取り出し使用した。なお、得られたマイクロカプセル顔料１〜７の平均粒子径は各々１．５〜２．１μｍであった。
[Examples 1 to 4 and Comparative Examples 1 to 3]
(Prescription of ink composition for writing tools)
Each water-based ink composition for writing instruments was prepared by a conventional method according to the formulation (microcapsule pigments 1 to 7 and each component of water-based ink) shown in Table 1 below. Each microcapsule pigment 1 to 7 was taken out and used as a microcapsule pigment by filtering each microcapsule dispersion liquid and drying it. The average particle size of the obtained microcapsule pigments 1 to 7 was 1.5 to 2.1 μm, respectively.
（水性ボールペンの作製）
上記で得られた各筆記具用水性インク組成物を用いて水性ボールペンを作製した。具体的には、ボールペン〔三菱鉛筆株式会社製、商品名：シグノＵＭ−１００〕の軸を使用し、内径３．８ｍｍ、長さ１１３ｍｍポリプロピレン製インク収容管とステンレス製チップ（超硬合金ボール、ボール径０．５ｍｍ）及び該収容管と該チップを連結する継手からなるリフィールに上記各筆記具用水性インク組成物を充填し、インク後端に鉱油を主成分とするインク追従体を装填し、水性ボールペンを作製した。
得られた実施例１〜４及び比較例１〜３の各ボールペンを用いて、下記評価方法で彩度（色濃度）、筆記性の評価を行った。
これらの結果を下記表１に示す。
(Making a water-based ballpoint pen)
A water-based ballpoint pen was produced using each of the water-based ink compositions for writing tools obtained above. Specifically, using the shaft of a ballpoint pen [Mitsubishi Pencil Co., Ltd., trade name: Signo UM-100], an inner diameter of 3.8 mm, a length of 113 mm, a polypropylene ink storage tube and a stainless steel tip (cemented carbide ball, A refill consisting of a ballpoint pen (0.5 mm in diameter) and a joint connecting the accommodating tube and the chip is filled with the above-mentioned water-based ink composition for writing tools, and an ink follower containing mineral oil as a main component is loaded at the rear end of the ink. A water-based ballpoint pen was produced.
Saturation (color density) and writability were evaluated by the following evaluation methods using the obtained ballpoint pens of Examples 1 to 4 and Comparative Examples 1 to 3.
These results are shown in Table 1 below.
（１）彩度の測定方法
主な性能（色濃度≒彩度）は展色で評価した。
得られた筆記具用水性インク組成物を、バーコータ（ＲＤＳ０６、株式会社安田精機製作所）を用い、クラークケント紙（連量 １６０ｋｇ）に展色した。
ＪＩＳ Ｚ ８７８１に準拠するＬ＊ａ＊ｂ＊表色系に準拠した彩度（Ｃ＊ａｂ）の値は、ａ＊値及びｂ＊値を用いて、以下の式で表される。
分光測色計（ＳＣ−Ｔ（Ｐ）、スガ試験機社製）
光学条件：拡散照明８°受光 ｄ８方式（正反射を除く）
光源：１２Ｖ５０Ｗハロゲンランプ
測色条件：Ｄ６５光、２°視野
測定領域：５φ（３か所測定の平均）
(1) Saturation measurement method The main performance (color density ≒ saturation) was evaluated by color development.
The obtained water-based ink composition for writing tools was colored on Clark Kent paper (ream weight 160 kg) using a bar coater (RDS06, Yasuda Seiki Seisakusho Co., Ltd.).
The value of the saturation (C * ab) conforming to the L * a * b * color system conforming to JIS Z 8781 is expressed by the following formula using the a * value and the b * value.
Spectrophotometer (SC-T (P), manufactured by Suga Test Instruments Co., Ltd.)
Optical conditions: Diffuse illumination 8 ° light reception d8 method (excluding specular reflection)
Light source: 12V 50W halogen lamp Color measurement condition: D65 light, 2 ° field of view Measurement area: 5φ (average of 3 measurement points)
（２）筆記性の評価方法
得られた各ボールペンをＩＳＯ規格に準拠した筆記用紙に、フリーハンドで螺旋筆記し、目視により筆記性を下記の基準で評価した。
評価基準：
○：カスレを生じることなく筆記可能。
△：部分的にカスレが生じる。
×：全体的に大きくカスレが生じる。
(2) Evaluation method of writability Each of the obtained ballpoint pens was spirally written on a writing paper conforming to the ISO standard by freehand, and the writability was visually evaluated according to the following criteria.
Evaluation criteria:
◯: Writing is possible without causing blurring.
Δ: Blurring occurs partially.
X: Large blurring occurs as a whole.
上記表１の結果から明らかなように、本発明となる実施例１〜４のマイクロカプセル顔料１〜４を用いた筆記具用インク組成物は、本発明の範囲外となるマイクロカプセル顔料５〜７を用いた比較例１〜３の筆記具用インク組成物に較べて、彩度に優れ、筆記性も満足することが判明した。
これに対して、比較例１は、ロイコ色素として３’，６’−ジメトキシフルオランを用いたマイクロカプセル顔料５を含有した筆記具用インク組成物であり、比較例２は、２，６−ジフェニル−４−（４’−ジメチルアミノフェニル）−ピリジンを用いたマイクロカプセル顔料６を含有した筆記具用インク組成物であり、比較例３は４，４’−ビス（ジエチルアミノ）ベンゾフェノンを用いたマイクロカプセル顔料７を含有した筆記具用インク組成物であり、これらの筆記具用インク組成物では、満足のいく十分な彩度が得られないものであった。
As is clear from the results in Table 1 above, the ink composition for writing instruments using the microcapsule pigments 1 to 4 of Examples 1 to 4 according to the present invention is outside the scope of the present invention. It was found that, as compared with the ink compositions for writing instruments of Comparative Examples 1 to 3 using the above, the saturation was excellent and the writing property was also satisfied.
On the other hand, Comparative Example 1 is an ink composition for writing instruments containing a microcapsule pigment 5 using 3', 6'-dimethoxyfluorane as a leuco dye, and Comparative Example 2 is 2,6-diphenyl. An ink composition for writing instruments containing a microcapsule pigment 6 using -4- (4'-dimethylaminophenyl) -pyridine, and Comparative Example 3 is a microcapsule using 4,4'-bis (diethylamino) benzophenone. These are writing instrument ink compositions containing the pigment 7, and these writing instrument ink compositions have not been able to obtain satisfactory and sufficient saturation.
水性、または、油性のボールペン、マーキングペンなどの筆記具に好適な色素、それを用いたマイクロカプセル顔料及び筆記具用インク組成物が得られる。 A dye suitable for writing instruments such as water-based or oil-based ballpoint pens and marking pens, microcapsule pigments using the same, and ink compositions for writing instruments can be obtained.
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