WO2011070966A1 - 水性ボールペン用インキ組成物及び水性ボールペン - Google Patents
水性ボールペン用インキ組成物及び水性ボールペン Download PDFInfo
- Publication number
- WO2011070966A1 WO2011070966A1 PCT/JP2010/071576 JP2010071576W WO2011070966A1 WO 2011070966 A1 WO2011070966 A1 WO 2011070966A1 JP 2010071576 W JP2010071576 W JP 2010071576W WO 2011070966 A1 WO2011070966 A1 WO 2011070966A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- water
- ballpoint pen
- ink composition
- based ballpoint
- microcapsule pigment
- Prior art date
Links
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 239000000203 mixture Substances 0.000 title claims abstract description 48
- 239000000049 pigment Substances 0.000 claims abstract description 71
- 239000003094 microcapsule Substances 0.000 claims abstract description 55
- 239000000126 substance Substances 0.000 claims abstract description 23
- 229920003180 amino resin Polymers 0.000 claims abstract description 14
- 229920000642 polymer Polymers 0.000 claims abstract description 12
- 239000002253 acid Substances 0.000 claims abstract description 11
- 150000002576 ketones Chemical class 0.000 claims abstract description 11
- 230000002378 acidificating effect Effects 0.000 claims abstract description 9
- 125000000524 functional group Chemical group 0.000 claims abstract description 9
- 239000002245 particle Substances 0.000 claims description 33
- -1 polyoxyethylene Polymers 0.000 claims description 28
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 18
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 125000001931 aliphatic group Chemical group 0.000 claims description 4
- 238000003860 storage Methods 0.000 abstract description 15
- 239000002775 capsule Substances 0.000 abstract description 10
- 239000012528 membrane Substances 0.000 abstract description 2
- 239000000975 dye Substances 0.000 description 18
- 239000003795 chemical substances by application Substances 0.000 description 15
- 238000000034 method Methods 0.000 description 14
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 12
- 230000008859 change Effects 0.000 description 12
- 239000007864 aqueous solution Substances 0.000 description 10
- 239000006185 dispersion Substances 0.000 description 10
- 230000000694 effects Effects 0.000 description 7
- 238000011156 evaluation Methods 0.000 description 7
- 230000002441 reversible effect Effects 0.000 description 7
- 150000003839 salts Chemical class 0.000 description 7
- IPAJDLMMTVZVPP-UHFFFAOYSA-N Crystal violet lactone Chemical compound C1=CC(N(C)C)=CC=C1C1(C=2C=CC(=CC=2)N(C)C)C2=CC=C(N(C)C)C=C2C(=O)O1 IPAJDLMMTVZVPP-UHFFFAOYSA-N 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000003921 oil Substances 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- GHLCBKCJXDNLTC-UHFFFAOYSA-N CCCCCCCCCCCC(O)=O.CCCCCCCCCCCC(O)=O.C1=CC(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C=C1 Chemical compound CCCCCCCCCCCC(O)=O.CCCCCCCCCCCC(O)=O.C1=CC(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C=C1 GHLCBKCJXDNLTC-UHFFFAOYSA-N 0.000 description 5
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 5
- 238000004220 aggregation Methods 0.000 description 5
- 230000002776 aggregation Effects 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 235000014113 dietary fatty acids Nutrition 0.000 description 5
- 239000000194 fatty acid Substances 0.000 description 5
- 229930195729 fatty acid Natural products 0.000 description 5
- 229920000647 polyepoxide Polymers 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 4
- 239000003822 epoxy resin Substances 0.000 description 4
- 238000009472 formulation Methods 0.000 description 4
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 4
- 238000005191 phase separation Methods 0.000 description 4
- 239000002562 thickening agent Substances 0.000 description 4
- 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
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 3
- 229920000877 Melamine resin Polymers 0.000 description 3
- 239000004640 Melamine resin Substances 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 229920002125 Sokalan® Polymers 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 3
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- 239000003755 preservative agent Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000005639 Lauric acid Substances 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229920001807 Urea-formaldehyde Polymers 0.000 description 2
- 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 2
- 150000001412 amines Chemical class 0.000 description 2
- SESFRYSPDFLNCH-UHFFFAOYSA-N benzyl benzoate Chemical compound C=1C=CC=CC=1C(=O)OCC1=CC=CC=C1 SESFRYSPDFLNCH-UHFFFAOYSA-N 0.000 description 2
- 125000000649 benzylidene group Chemical group [H]C(=[*])C1=C([H])C([H])=C([H])C([H])=C1[H] 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
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 2
- 239000004202 carbamide Substances 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- MWKFXSUHUHTGQN-UHFFFAOYSA-N decan-1-ol Chemical compound CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- NOPFSRXAKWQILS-UHFFFAOYSA-N docosan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCCCCCO NOPFSRXAKWQILS-UHFFFAOYSA-N 0.000 description 2
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 2
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 2
- GULIJHQUYGTWSO-UHFFFAOYSA-N dodecyl palmitate Chemical compound CCCCCCCCCCCCCCCC(=O)OCCCCCCCCCCCC GULIJHQUYGTWSO-UHFFFAOYSA-N 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000000417 fungicide Substances 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- 150000002334 glycols Chemical class 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- BXWNKGSJHAJOGX-UHFFFAOYSA-N hexadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCO BXWNKGSJHAJOGX-UHFFFAOYSA-N 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- XJRBAMWJDBPFIM-UHFFFAOYSA-N methyl vinyl ether Chemical compound COC=C XJRBAMWJDBPFIM-UHFFFAOYSA-N 0.000 description 2
- GOQYKNQRPGWPLP-UHFFFAOYSA-N n-heptadecyl alcohol Natural products CCCCCCCCCCCCCCCCCO GOQYKNQRPGWPLP-UHFFFAOYSA-N 0.000 description 2
- KPSSIOMAKSHJJG-UHFFFAOYSA-N neopentyl alcohol Chemical compound CC(C)(C)CO KPSSIOMAKSHJJG-UHFFFAOYSA-N 0.000 description 2
- ZWRUINPWMLAQRD-UHFFFAOYSA-N nonan-1-ol Chemical compound CCCCCCCCCO ZWRUINPWMLAQRD-UHFFFAOYSA-N 0.000 description 2
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- RZXMPPFPUUCRFN-UHFFFAOYSA-N p-toluidine Chemical compound CC1=CC=C(N)C=C1 RZXMPPFPUUCRFN-UHFFFAOYSA-N 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 2
- 230000002335 preservative effect Effects 0.000 description 2
- 125000002294 quinazolinyl group Chemical class N1=C(N=CC2=CC=CC=C12)* 0.000 description 2
- 239000012429 reaction media Substances 0.000 description 2
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 2
- BILPUZXRUDPOOF-UHFFFAOYSA-N stearyl palmitate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCCCCCCCCCCCCCC BILPUZXRUDPOOF-UHFFFAOYSA-N 0.000 description 2
- HLZKNKRTKFSKGZ-UHFFFAOYSA-N tetradecan-1-ol Chemical compound CCCCCCCCCCCCCCO HLZKNKRTKFSKGZ-UHFFFAOYSA-N 0.000 description 2
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 2
- KJIOQYGWTQBHNH-UHFFFAOYSA-N undecanol Chemical compound CCCCCCCCCCCO KJIOQYGWTQBHNH-UHFFFAOYSA-N 0.000 description 2
- 239000003021 water soluble solvent Substances 0.000 description 2
- 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
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-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
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 1
- LTSWUFKUZPPYEG-UHFFFAOYSA-N 1-decoxydecane Chemical compound CCCCCCCCCCOCCCCCCCCCC LTSWUFKUZPPYEG-UHFFFAOYSA-N 0.000 description 1
- HBXWUCXDUUJDRB-UHFFFAOYSA-N 1-octadecoxyoctadecane Chemical compound CCCCCCCCCCCCCCCCCCOCCCCCCCCCCCCCCCCCC HBXWUCXDUUJDRB-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- SBASXUCJHJRPEV-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethanol Chemical compound COCCOCCO SBASXUCJHJRPEV-UHFFFAOYSA-N 0.000 description 1
- FLPJVCMIKUWSDR-UHFFFAOYSA-N 2-(4-formylphenoxy)acetamide Chemical compound NC(=O)COC1=CC=C(C=O)C=C1 FLPJVCMIKUWSDR-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-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
- 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
- UYMBCDOGDVGEFA-UHFFFAOYSA-N 3-(1h-indol-2-yl)-3h-2-benzofuran-1-one Chemical compound 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
- 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
- SRFHDEQOIMRMHH-UHFFFAOYSA-N 4-[1-(4-hydroxyphenyl)-3-methylbutyl]phenol Chemical compound C=1C=C(O)C=CC=1C(CC(C)C)C1=CC=C(O)C=C1 SRFHDEQOIMRMHH-UHFFFAOYSA-N 0.000 description 1
- ICYDRUIZSPKQOH-UHFFFAOYSA-N 4-[1-(4-hydroxyphenyl)decyl]phenol Chemical compound C=1C=C(O)C=CC=1C(CCCCCCCCC)C1=CC=C(O)C=C1 ICYDRUIZSPKQOH-UHFFFAOYSA-N 0.000 description 1
- YMZDMPPYBDUSMI-UHFFFAOYSA-N 4-[1-(4-hydroxyphenyl)dodecyl]phenol Chemical compound C=1C=C(O)C=CC=1C(CCCCCCCCCCC)C1=CC=C(O)C=C1 YMZDMPPYBDUSMI-UHFFFAOYSA-N 0.000 description 1
- CZCLTCVIZZPPBW-UHFFFAOYSA-N 4-[1-(4-hydroxyphenyl)heptyl]phenol Chemical compound C=1C=C(O)C=CC=1C(CCCCCC)C1=CC=C(O)C=C1 CZCLTCVIZZPPBW-UHFFFAOYSA-N 0.000 description 1
- WKGVDZYQWLBSQC-UHFFFAOYSA-N 4-[1-(4-hydroxyphenyl)hexyl]phenol Chemical compound C=1C=C(O)C=CC=1C(CCCCC)C1=CC=C(O)C=C1 WKGVDZYQWLBSQC-UHFFFAOYSA-N 0.000 description 1
- OUKOUEHLRVEKCJ-UHFFFAOYSA-N 4-[1-(4-hydroxyphenyl)nonyl]phenol Chemical compound C=1C=C(O)C=CC=1C(CCCCCCCC)C1=CC=C(O)C=C1 OUKOUEHLRVEKCJ-UHFFFAOYSA-N 0.000 description 1
- NBKVULRGDSYCGP-UHFFFAOYSA-N 4-[1-(4-hydroxyphenyl)octyl]phenol Chemical compound C=1C=C(O)C=CC=1C(CCCCCCC)C1=CC=C(O)C=C1 NBKVULRGDSYCGP-UHFFFAOYSA-N 0.000 description 1
- VHLLJTHDWPAQEM-UHFFFAOYSA-N 4-[2-(4-hydroxyphenyl)-4-methylpentan-2-yl]phenol Chemical compound C=1C=C(O)C=CC=1C(C)(CC(C)C)C1=CC=C(O)C=C1 VHLLJTHDWPAQEM-UHFFFAOYSA-N 0.000 description 1
- XHQYAMKBTLODDV-UHFFFAOYSA-N 4-[2-(4-hydroxyphenyl)heptan-2-yl]phenol Chemical compound C=1C=C(O)C=CC=1C(C)(CCCCC)C1=CC=C(O)C=C1 XHQYAMKBTLODDV-UHFFFAOYSA-N 0.000 description 1
- KBWOAGGPYKQCAO-UHFFFAOYSA-N 4-[2-(4-hydroxyphenyl)nonan-2-yl]phenol Chemical compound C=1C=C(O)C=CC=1C(C)(CCCCCCC)C1=CC=C(O)C=C1 KBWOAGGPYKQCAO-UHFFFAOYSA-N 0.000 description 1
- GVTFIGQDTWPFTA-UHFFFAOYSA-N 4-bromo-2-chloro-1-isothiocyanatobenzene Chemical compound ClC1=CC(Br)=CC=C1N=C=S GVTFIGQDTWPFTA-UHFFFAOYSA-N 0.000 description 1
- GZFGOTFRPZRKDS-UHFFFAOYSA-N 4-bromophenol Chemical compound OC1=CC=C(Br)C=C1 GZFGOTFRPZRKDS-UHFFFAOYSA-N 0.000 description 1
- TTWBMGNNEJOEOJ-UHFFFAOYSA-N 4-chloro-n-fluorocyclohexan-1-amine Chemical compound FNC1CCC(Cl)CC1 TTWBMGNNEJOEOJ-UHFFFAOYSA-N 0.000 description 1
- WXNZTHHGJRFXKQ-UHFFFAOYSA-N 4-chlorophenol Chemical compound OC1=CC=C(Cl)C=C1 WXNZTHHGJRFXKQ-UHFFFAOYSA-N 0.000 description 1
- CMGDVUCDZOBDNL-UHFFFAOYSA-N 4-methyl-2h-benzotriazole Chemical compound CC1=CC=CC2=NNN=C12 CMGDVUCDZOBDNL-UHFFFAOYSA-N 0.000 description 1
- RCVMSMLWRJESQC-UHFFFAOYSA-N 7-[4-(diethylamino)-2-ethoxyphenyl]-7-(1-ethyl-2-methylindol-3-yl)furo[3,4-b]pyridin-5-one Chemical compound CCOC1=CC(N(CC)CC)=CC=C1C1(C=2C3=CC=CC=C3N(CC)C=2C)C2=NC=CC=C2C(=O)O1 RCVMSMLWRJESQC-UHFFFAOYSA-N 0.000 description 1
- 244000215068 Acacia senegal Species 0.000 description 1
- 241000416162 Astragalus gummifer Species 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- VOWWYDCFAISREI-UHFFFAOYSA-N Bisphenol AP Chemical compound C=1C=C(O)C=CC=1C(C=1C=CC(O)=CC=1)(C)C1=CC=CC=C1 VOWWYDCFAISREI-UHFFFAOYSA-N 0.000 description 1
- HTVITOHKHWFJKO-UHFFFAOYSA-N Bisphenol B Chemical compound C=1C=C(O)C=CC=1C(C)(CC)C1=CC=C(O)C=C1 HTVITOHKHWFJKO-UHFFFAOYSA-N 0.000 description 1
- QFOHBWFCKVYLES-UHFFFAOYSA-N Butylparaben Chemical compound CCCCOC(=O)C1=CC=C(O)C=C1 QFOHBWFCKVYLES-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 241000694440 Colpidium aqueous Species 0.000 description 1
- 229920002307 Dextran Polymers 0.000 description 1
- GHKOFFNLGXMVNJ-UHFFFAOYSA-N Didodecyl thiobispropanoate Chemical compound CCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCC GHKOFFNLGXMVNJ-UHFFFAOYSA-N 0.000 description 1
- 239000003508 Dilauryl thiodipropionate Substances 0.000 description 1
- RPWFJAMTCNSJKK-UHFFFAOYSA-N Dodecyl gallate Chemical compound CCCCCCCCCCCCOC(=O)C1=CC(O)=C(O)C(O)=C1 RPWFJAMTCNSJKK-UHFFFAOYSA-N 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
- 108010010803 Gelatin Proteins 0.000 description 1
- 229920002907 Guar gum Polymers 0.000 description 1
- 229920000084 Gum arabic Polymers 0.000 description 1
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 1
- 229920000663 Hydroxyethyl cellulose 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
- AFBPFSWMIHJQDM-UHFFFAOYSA-N N-methyl-N-phenylamine Natural products CNC1=CC=CC=C1 AFBPFSWMIHJQDM-UHFFFAOYSA-N 0.000 description 1
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Chemical group CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 1
- REYJJPSVUYRZGE-UHFFFAOYSA-N Octadecylamine Chemical compound CCCCCCCCCCCCCCCCCCN REYJJPSVUYRZGE-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- HDSBZMRLPLPFLQ-UHFFFAOYSA-N Propylene glycol alginate Chemical compound OC1C(O)C(OC)OC(C(O)=O)C1OC1C(O)C(O)C(C)C(C(=O)OCC(C)O)O1 HDSBZMRLPLPFLQ-UHFFFAOYSA-N 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 239000003490 Thiodipropionic acid Substances 0.000 description 1
- 229920001615 Tragacanth Polymers 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- DOOTYTYQINUNNV-UHFFFAOYSA-N Triethyl citrate Chemical compound CCOC(=O)CC(O)(C(=O)OCC)CC(=O)OCC DOOTYTYQINUNNV-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- GKXVJHDEWHKBFH-UHFFFAOYSA-N [2-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC=C1CN GKXVJHDEWHKBFH-UHFFFAOYSA-N 0.000 description 1
- 235000010489 acacia gum Nutrition 0.000 description 1
- 239000000205 acacia gum Substances 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000002411 adverse Effects 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
- 150000008064 anhydrides Chemical class 0.000 description 1
- 150000001449 anionic compounds Chemical class 0.000 description 1
- 239000002199 base oil Substances 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
- XVNLXQKEGAWCFW-UHFFFAOYSA-N benzyl 3-(3-oxo-3-phenylmethoxypropyl)sulfanylpropanoate Chemical compound C=1C=CC=CC=1COC(=O)CCSCCC(=O)OCC1=CC=CC=C1 XVNLXQKEGAWCFW-UHFFFAOYSA-N 0.000 description 1
- 229960002903 benzyl benzoate Drugs 0.000 description 1
- BPSLVNCMKDXZPC-UHFFFAOYSA-N benzyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC1=CC=CC=C1 BPSLVNCMKDXZPC-UHFFFAOYSA-N 0.000 description 1
- ZFVMWEVVKGLCIJ-UHFFFAOYSA-N bisphenol AF Chemical compound C1=CC(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C=C1 ZFVMWEVVKGLCIJ-UHFFFAOYSA-N 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 235000010418 carrageenan Nutrition 0.000 description 1
- 239000000679 carrageenan Substances 0.000 description 1
- 229920001525 carrageenan Polymers 0.000 description 1
- 229940113118 carrageenan Drugs 0.000 description 1
- 239000005018 casein Substances 0.000 description 1
- BECPQYXYKAMYBN-UHFFFAOYSA-N casein, tech. Chemical compound NCCCCC(C(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(CC(C)C)N=C(O)C(CCC(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(C(C)O)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(COP(O)(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(N)CC1=CC=CC=C1 BECPQYXYKAMYBN-UHFFFAOYSA-N 0.000 description 1
- 235000021240 caseins Nutrition 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 229960000541 cetyl alcohol Drugs 0.000 description 1
- 229940074979 cetyl palmitate Drugs 0.000 description 1
- 239000011362 coarse particle Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 1
- 238000004042 decolorization Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- XAKXZZPEUKNHMA-UHFFFAOYSA-N decyl decanoate Chemical compound CCCCCCCCCCOC(=O)CCCCCCCCC XAKXZZPEUKNHMA-UHFFFAOYSA-N 0.000 description 1
- BOUIEBMBWBCUPB-UHFFFAOYSA-N decyl tetradecanoate Chemical compound CCCCCCCCCCCCCC(=O)OCCCCCCCCCC BOUIEBMBWBCUPB-UHFFFAOYSA-N 0.000 description 1
- ZFAKTZXUUNBLEB-UHFFFAOYSA-N dicyclohexylazanium;nitrite Chemical compound [O-]N=O.C1CCCCC1[NH2+]C1CCCCC1 ZFAKTZXUUNBLEB-UHFFFAOYSA-N 0.000 description 1
- 229940028820 didecyl ether Drugs 0.000 description 1
- HCQHIEGYGGJLJU-UHFFFAOYSA-N didecyl hexanedioate Chemical compound CCCCCCCCCCOC(=O)CCCCC(=O)OCCCCCCCCCC HCQHIEGYGGJLJU-UHFFFAOYSA-N 0.000 description 1
- 235000019304 dilauryl thiodipropionate Nutrition 0.000 description 1
- MQKMBXOZOISLIV-UHFFFAOYSA-N dioctadecyl benzene-1,2-dicarboxylate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCCCCCCCCCCCC MQKMBXOZOISLIV-UHFFFAOYSA-N 0.000 description 1
- CZZYITDELCSZES-UHFFFAOYSA-N diphenylmethane Chemical compound C=1C=CC=CC=1CC1=CC=CC=C1 CZZYITDELCSZES-UHFFFAOYSA-N 0.000 description 1
- 229940085632 distearyl ether Drugs 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 229960000735 docosanol Drugs 0.000 description 1
- ILRSCQWREDREME-UHFFFAOYSA-N dodecanamide Chemical compound CCCCCCCCCCCC(N)=O ILRSCQWREDREME-UHFFFAOYSA-N 0.000 description 1
- 239000000555 dodecyl gallate Substances 0.000 description 1
- 229940080643 dodecyl gallate Drugs 0.000 description 1
- 235000010386 dodecyl gallate Nutrition 0.000 description 1
- JRTVEUGOGWTHTR-UHFFFAOYSA-N dodecyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCCCCCCCCCCCC JRTVEUGOGWTHTR-UHFFFAOYSA-N 0.000 description 1
- DFQOCHPHORLRID-UHFFFAOYSA-N dodecyl tetradecanoate Chemical compound CCCCCCCCCCCCCC(=O)OCCCCCCCCCCCC DFQOCHPHORLRID-UHFFFAOYSA-N 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 235000019325 ethyl cellulose Nutrition 0.000 description 1
- 229920001249 ethyl cellulose Polymers 0.000 description 1
- 230000000855 fungicidal effect Effects 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 229940014259 gelatin Drugs 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 235000010417 guar gum Nutrition 0.000 description 1
- 239000000665 guar gum Substances 0.000 description 1
- 229960002154 guar gum Drugs 0.000 description 1
- KCNOEZOXGYXXQU-UHFFFAOYSA-N heptatriacontan-19-one Chemical compound CCCCCCCCCCCCCCCCCCC(=O)CCCCCCCCCCCCCCCCCC KCNOEZOXGYXXQU-UHFFFAOYSA-N 0.000 description 1
- PXDJXZJSCPSGGI-UHFFFAOYSA-N hexadecanoic acid hexadecyl ester Natural products CCCCCCCCCCCCCCCCOC(=O)CCCCCCCCCCCCCCC PXDJXZJSCPSGGI-UHFFFAOYSA-N 0.000 description 1
- QAKXLTNAJLFSQC-UHFFFAOYSA-N hexadecyl tetradecanoate Chemical compound CCCCCCCCCCCCCCCCOC(=O)CCCCCCCCCCCCC QAKXLTNAJLFSQC-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 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
- 150000002596 lactones Chemical group 0.000 description 1
- 235000010420 locust bean gum Nutrition 0.000 description 1
- 239000000711 locust bean gum Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- SLLMDHBKALJDBW-UHFFFAOYSA-N methyl 3-(4-hydroxyphenyl)-2-(phenylmethoxycarbonylamino)propanoate Chemical compound C=1C=CC=CC=1COC(=O)NC(C(=O)OC)CC1=CC=C(O)C=C1 SLLMDHBKALJDBW-UHFFFAOYSA-N 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 235000010981 methylcellulose Nutrition 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 229940043348 myristyl alcohol Drugs 0.000 description 1
- FIIGZGVXXBOCPL-UHFFFAOYSA-N n-fluoro-3-methylcyclohexan-1-amine Chemical compound CC1CCCC(NF)C1 FIIGZGVXXBOCPL-UHFFFAOYSA-N 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical group CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 1
- LYRFLYHAGKPMFH-UHFFFAOYSA-N octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(N)=O LYRFLYHAGKPMFH-UHFFFAOYSA-N 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- ITAWVWUURIEPJF-UHFFFAOYSA-N octadecyl 4-methoxybenzoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)C1=CC=C(OC)C=C1 ITAWVWUURIEPJF-UHFFFAOYSA-N 0.000 description 1
- KPWVFNOPNOTYNJ-UHFFFAOYSA-N octadecyl benzoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)C1=CC=CC=C1 KPWVFNOPNOTYNJ-UHFFFAOYSA-N 0.000 description 1
- RIKCMEDSBFQFAL-UHFFFAOYSA-N octyl 4-hydroxybenzoate Chemical compound CCCCCCCCOC(=O)C1=CC=C(O)C=C1 RIKCMEDSBFQFAL-UHFFFAOYSA-N 0.000 description 1
- HRPZGPXWSVHWPB-UHFFFAOYSA-N octyl decanoate Chemical compound CCCCCCCCCC(=O)OCCCCCCCC HRPZGPXWSVHWPB-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 235000010292 orthophenyl phenol Nutrition 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 229920002432 poly(vinyl methyl ether) polymer Polymers 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920001515 polyalkylene glycol Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 150000004804 polysaccharides Chemical class 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000003449 preventive effect Effects 0.000 description 1
- 235000010409 propane-1,2-diol alginate Nutrition 0.000 description 1
- 239000000770 propane-1,2-diol alginate Substances 0.000 description 1
- FKRCODPIKNYEAC-UHFFFAOYSA-N propionic acid ethyl ester Natural products CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000008213 purified water Substances 0.000 description 1
- 150000003222 pyridines Chemical class 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
- 229930182490 saponin Natural products 0.000 description 1
- 150000007949 saponins Chemical class 0.000 description 1
- 235000017709 saponins Nutrition 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 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
- 235000010234 sodium benzoate Nutrition 0.000 description 1
- 239000004299 sodium benzoate Substances 0.000 description 1
- 235000002639 sodium chloride Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 229940012831 stearyl alcohol Drugs 0.000 description 1
- 235000000346 sugar Nutrition 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 150000008163 sugars Chemical class 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 239000012756 surface treatment agent Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- LVEOKSIILWWVEO-UHFFFAOYSA-N tetradecyl 3-(3-oxo-3-tetradecoxypropyl)sulfanylpropanoate Chemical compound CCCCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCCCC LVEOKSIILWWVEO-UHFFFAOYSA-N 0.000 description 1
- YODZTKMDCQEPHD-UHFFFAOYSA-N thiodiglycol Chemical compound OCCSCCO YODZTKMDCQEPHD-UHFFFAOYSA-N 0.000 description 1
- 235000019303 thiodipropionic acid Nutrition 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- 229940078499 tricalcium phosphate Drugs 0.000 description 1
- 229910000391 tricalcium phosphate Inorganic materials 0.000 description 1
- 235000019731 tricalcium phosphate Nutrition 0.000 description 1
- 239000001069 triethyl citrate Substances 0.000 description 1
- VMYFZRTXGLUXMZ-UHFFFAOYSA-N triethyl citrate Natural products CCOC(=O)C(O)(C(=O)OCC)C(=O)OCC VMYFZRTXGLUXMZ-UHFFFAOYSA-N 0.000 description 1
- 235000013769 triethyl citrate Nutrition 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- AAAQKTZKLRYKHR-UHFFFAOYSA-N triphenylmethane Chemical compound C1=CC=CC=C1C(C=1C=CC=CC=1)C1=CC=CC=C1 AAAQKTZKLRYKHR-UHFFFAOYSA-N 0.000 description 1
- 229940057402 undecyl alcohol Drugs 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
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B43—WRITING OR DRAWING IMPLEMENTS; BUREAU ACCESSORIES
- B43K—IMPLEMENTS FOR WRITING OR DRAWING
- B43K7/00—Ball-point pens
-
- 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
-
- 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
- C09D11/18—Writing inks specially adapted for ball-point writing instruments
-
- 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
- C09D11/50—Sympathetic, colour changing or similar inks
Definitions
- the present invention relates to a water-based ballpoint pen ink composition containing a microcapsule pigment and an aqueous ballpoint pen, and more specifically, a sufficient line density can be obtained even when a thermochromic microcapsule pigment having a small average particle diameter is used,
- the present invention relates to a water-based ballpoint pen ink composition and a water-based ballpoint pen excellent in ink storage stability and writing performance.
- thermochromic microcapsule pigments utilizing the development and decoloring mechanisms of leuco dyes.
- an electron-donating color-forming organic compound that is a leuco dye (b) an electron-accepting compound that is a developer, and (c) a color-change temperature adjusting agent that determines the temperature at which the color reaction occurs.
- a reversible thermochromic microcapsule pigment encapsulating a reversible thermochromic composition comprising the reaction medium, and at least water, and the average particle size of the reversible thermochromic microcapsule pigment is 2.5-4.
- a water-based ink composition for reversible thermochromic writing instruments characterized in that particles in the range of 0.0 ⁇ m and 2.0 ⁇ m or less are 30% by volume or less in the total microcapsule pigment (see, for example, Patent Document 1) ), Water, (a) an electron-donating color-forming organic compound that is a leuco dye, (b) an electron-accepting compound that is a developer, and (c) a color change that determines the temperature at which the color reaction occurs. Is the reaction medium a temperature regulator?
- thermochromic microcapsule pigment encapsulating a reversible thermochromic composition
- a polymer flocculant a polymer flocculant
- a comb polymer dispersant having a carboxyl group in the side chain and a water-soluble resin.
- a water-based ink composition for reversible thermochromic writing instruments having an average maximum outer diameter of capsule pigments of 0.5 to 5.0 ⁇ m is known (for example, see Patent Document 2).
- the above microcapsule pigment tends to be unfavorable because the color density decreases as the average particle size decreases. It is described that it is difficult to exhibit the color developability of density, and it is described that particles having a size of 2.0 ⁇ m or less are 30% by volume or less, more preferably 10% by volume or less in the total microcapsule pigment. Also, in the above-mentioned Patent Document 2, it is described that the average value of the maximum outer diameter of the microcapsule pigment is 0.5 to 5.0 ⁇ m. 5 ⁇ m microcapsule pigment is used. This is because the capsule thickness in the microcapsule pigment is relatively increased.
- the microcapsule pigment when used in an aqueous ballpoint pen, it is preferable to use a pigment having a small average particle diameter from the viewpoint of writing property and ink storage stability.
- a pigment having a small average particle diameter from the viewpoint of writing property and ink storage stability.
- JP 2008-280440 A (Claims, Examples, etc.)
- JP 2009-227954 A (Claims, Examples, etc.)
- an object of the present invention is to provide a water-based ballpoint pen ink composition and a water-based ballpoint pen which can provide a sufficient drawn line density and are excellent in ink storage stability and writing performance.
- the present invention resides in the following (1) to (4).
- a water-based ballpoint pen ink composition comprising at least a chemical substance having an acid value of 3 to 40 (mgKOH / g).
- thermochromic microcapsule pigment having a small average particle size of 0.1 to 1.0 ⁇ m is used, a sufficient line density can be obtained, and the storage stability of the ink can be obtained.
- An aqueous ballpoint pen ink composition and an aqueous ballpoint pen excellent in writing performance are provided.
- the ink composition for water-based ballpoint pens of the present invention comprises a microcapsule pigment having a wall film formed of an amino resin having an average particle size of 0.1 to 1.0 ⁇ m, a polymer having a ketone as the main chain, It contains at least a chemical substance having an acidic functional group in the structure and an acid value of 3 to 40 (mgKOH / g).
- the microcapsule pigment used in the present invention has a wall film having an average particle size of 0.1 to 1.0 ⁇ m formed of an amino resin, and is composed of at least a leuco dye, a developer, and a color change temperature adjusting agent. Encapsulating a thermochromic composition.
- the leuco dye that can be used is not particularly limited as long as it is an electron-donating dye and functions as a color former.
- pyridine compounds, quinazoline compounds, bisquinazoline compounds and the like that develop yellow to red color development can also be used.
- These leuco dyes have a lactone skeleton, a pyridine skeleton, a quinazoline skeleton, a bisquinazoline skeleton, etc., and develop color when these skeletons (rings) are opened.
- Developers that can be used are those that develop leuco dyes, such as inorganic acids, aromatic carboxylic acids and anhydrides or metal salts thereof, organic sulfonic acids, other organic acids, and phenolic compounds. It is done. Particularly preferred are compounds having a phenolic hydroxyl group such as bisphenol A.
- the color change temperature adjusting agent that can be used is one that causes the reaction between the leuco dye and the developer to reversibly occur in a specific temperature range, and is not particularly limited as long as it has this function. Examples include esters, ketones, ethers, acid amides, azomethines, fatty acids, hydrocarbons and the like.
- the microcapsule pigment used in the present invention comprises a thermochromic composition comprising at least the above leuco dye, a color developer, and a color change temperature adjusting agent so that the average particle diameter is 0.1 to 1.0 ⁇ m and a wall film.
- a thermochromic composition comprising at least the above leuco dye, a color developer, and a color change temperature adjusting agent so that the average particle diameter is 0.1 to 1.0 ⁇ m and a wall film.
- the microencapsulation method include interfacial polymerization method, interfacial polycondensation method, in situ polymerization method, liquid curing coating method, phase separation method from aqueous solution, phase separation method from organic solvent, melt dispersion cooling method, air A suspension coating method, a spray drying method, etc. can be mentioned, and can be appropriately selected according to the application.
- a leuco dye, a developer, and a color change temperature adjusting agent are heated and melted, then charged into an emulsifier solution, heated and stirred to disperse into oil droplets, and then as a capsule film agent.
- a resin raw material that can be formed of an amino resin for the wall film for example, after adding amino resin solution, specifically, methylol melamine aqueous solution, urea solution, benzoguanamine solution, etc.
- the desired thermochromic microcapsule pigment can be produced by filtering the dispersion.
- the content of these leuco dyes, developers, and color change temperature adjusters varies depending on the type of leuco dye, developer, color change temperature adjuster used, microencapsulation method, etc.
- the developer is 0.1 to 100 developer and 1 to 100 color changing temperature adjusting agent in mass ratio.
- the capsule membrane agent is 0.1 to 1 in mass ratio with respect to the capsule contents.
- it is possible to obtain the color of each pigment, an arbitrary color development temperature, and a decoloration temperature by suitably combining the types and amounts of the leuco dye, the developer, and the color change temperature adjusting agent. .
- the wall film needs to be formed of an amino resin, and is preferably formed of, for example, a melamine resin, a urea resin, a benzoguanamine resin, and more preferably, a manufacturability and storage. It is desirable to form with a melamine resin from the point of stability and writing property.
- a resin other than an amino resin such as a urethane resin or an epoxy resin
- at least one of drawn line density, storage stability, and writing property is inferior.
- the thickness of the wall film of the microcapsule pigment is appropriately determined according to the required strength of the wall film and the drawn line density.
- a suitable amino resin raw material melamine resin, urea resin, benzoguanamine resin, etc.
- dispersant a protective colloid Select etc.
- the average particle size of the obtained microcapsule pigment is more preferably 0.1 to 1.0 ⁇ m, from the viewpoints of colorability, color developability, easy decolorization, stability, and suppression of adverse effects on writability. Is preferably 0.2 to 0.9 ⁇ m.
- the “average particle size” defined in the present invention is a value obtained by measuring the average particle size with a particle size distribution measuring device [particle size measuring instrument N4Plus (manufactured by COULTER)]. If the average particle size is less than 0.1 ⁇ m, sufficient drawn line density cannot be obtained. On the other hand, if it exceeds 1.0 ⁇ m, the writability is deteriorated and the dispersion stability of the microcapsule pigment is decreased.
- the microcapsule pigment having an average particle diameter in the above range varies depending on the microencapsulation method.
- the microcapsule pigment is produced by It can be prepared by suitably combining stirring conditions.
- the content of the microcapsule pigment is preferably 5 to 30% by mass (hereinafter simply referred to as “%”), more preferably 10 to 25%, based on the total amount of the ink composition. desirable. If the content of the colorant (developed particles) is less than 5%, the coloring power and color developability become insufficient. On the other hand, if it exceeds 30%, blurring tends to occur, which is not preferable.
- the chemical substance used in the present invention is a polymer having a ketone as the main chain, has an acidic functional group in the chemical structure, and has an acid value of 3 to 40 (mgKOH / g). It exhibits functions such as improving the line density by interacting with the capsule pigment.
- the chemical substance that can be used is a polymer having a ketone as the main chain, and examples of the acidic functional group in the chemical structure include a carboxylic acid group and a phosphoric acid group. If the acid value is less than 3 mgKOH / g, the writing property tends to be blurred, whereas if it exceeds 40 mgKOH / g, the stability of the ink is lowered and precipitates are easily generated, which is not preferable. A more preferred acid value is 5 to 15 mg KOH / g.
- Solsperse 44000 main chain: ketone, acidic functional group: carboxylic acid, acid value of about 12 mg KOH / g, manufactured by Nippon Lubrizol
- Solsperse 46000 main chain: ketone, acidic functional group: carboxylic acid, acid
- 12 mg KOH / g manufactured by Nippon Lubrizol Co., Ltd.
- the content of this chemical substance is preferably 0.1 to 10%, more preferably 0.3 to 5%, based on the total amount of the ink composition.
- the content is less than 0.1%, a satisfactory drawn line density cannot be obtained, and the stability of the microcapsule pigment is lowered. On the other hand, if it exceeds 10%, blurring tends to occur during writing, which is not preferable.
- the polyoxyethylene aliphatic amine (hereinafter referred to as “POE aliphatic amine”) used in the present invention has an aliphatic carbon number of 10 to 20, and exhibits functions such as dispersion stabilization of microcapsule pigments. is there. If the aliphatic carbon number is less than 10, the adsorptivity to the pigment is deteriorated and the pigment dispersion effect is insufficient. On the other hand, if the carbon number exceeds 20, the solubility in water becomes insufficient. It is not preferable.
- Preferable POE aliphatic amines are preferably those having an addition mole number of POE in the POE aliphatic amine of 10 to 50, more preferably 10 to 20 mol, from the viewpoint of solubility in water and writing property.
- Examples of the POE aliphatic amine that can be used include POE (15) oleylamine and POE (15) stearylamine, and at least one of them can be used.
- the content of these POE aliphatic amines is preferably 0.1 to 10%, more preferably 0.3 to 5%, based on the total amount of the ink composition.
- the content is less than 0.1%, the pigment dispersion effect is insufficient.
- the content exceeds 10%, blurring tends to occur during writing, which is not preferable.
- the water-based ink composition for ballpoint pens of the present invention in addition to the microcapsule pigment, the chemical substance, the POE aliphatic amine, and the balance as water (tap water, purified water, distilled water, ion-exchanged water, pure water, etc.) As long as the effects of the present invention are not impaired, a water-soluble solvent, a thickener, a lubricant, a rust inhibitor, a preservative, or a fungicide can be appropriately contained.
- water-soluble solvents examples include glycols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, polyethylene glycol, 3-butylene glycol, thiodiethylene glycol, glycerin, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, and the like. These can be used alone or in combination.
- the thickener for example, at least one selected from the group consisting of synthetic polymers, natural rubber, cellulose, and polysaccharides is desirable.
- gum arabic ethyl cellulose, hydroxyethyl cellulose, carboxymethyl cellulose, starch glycolic acid and its salts, propylene glycol alginate
- Lubricants include nonionics such as fatty acid esters of polyhydric alcohols, higher fatty acid esters of sugars, polyoxyalkylene higher fatty acid esters, and alkyl phosphates, which are also used in pigment surface treatment agents, and alkyl sulfonic acids of higher fatty acid amides. Examples thereof include salts, anionic compounds such as alkyl allyl sulfonates, polyalkylene glycol derivatives, fluorosurfactants, and polyether-modified silicones.
- benzotriazole As rust preventives, benzotriazole, tolyltriazole, dicyclohexylammonium nitrite, saponins, etc., as preservatives or fungicides, phenol, sodium omadin, sodium benzoate, benzimidazole compounds, etc. Can be mentioned.
- the water-based ink composition for ballpoint pens of the present invention conventionally known methods can be employed. For example, a predetermined amount of each of the above components is blended and stirred and mixed with a stirrer such as a homomixer or a disper. It is obtained by doing. Furthermore, if necessary, coarse particles in the ink composition may be removed by filtration or centrifugation.
- a stirrer such as a homomixer or a disper. It is obtained by doing.
- coarse particles in the ink composition may be removed by filtration or centrifugation.
- a microcapsule pigment in which a wall film having an average particle size of at least 0.1 to 1.0 ⁇ m is formed of an amino resin, and a ketone as a main chain A polymer containing an acidic functional group in the chemical structure and a chemical substance having an acid value of 3 to 40 (mgKOH / g) and containing a microcapsule pigment having a small average particle size Even when writing on paper or the like with a ballpoint pen equipped with the ink to be used, a sufficient drawing line density can be obtained, and an ink composition for water-based ballpoint pens excellent in ink storage stability and writing performance can be obtained. .
- the ink composition for water-based ballpoint pens of the present invention uses a small microcapsule pigment having an average particle size of 0.1 to 1.0 ⁇ m, a sufficient line density can be obtained, and the storage stability of the ink can be obtained. It is assumed that the writing performance is excellent for the following reasons. That is, in the present invention, the chemical substance improves the drawn line density by causing gradual aggregation with respect to the microcapsule pigment, and further, the polyoxyethylene aliphatic amine serves to keep this aggregation state stable. It is.
- the water-based ballpoint pen of the present invention has a general configuration as a water-based ballpoint pen, for example, a resin-made ink storage tube provided with a metal tip, and the water-based ink composition for a ballpoint pen of the present invention incorporated therein and Various types of ballpoint pen configurations of a knock type and a non-knock type (cap type) including a writing instrument main body (shaft body) can be adopted, and the production thereof can be performed according to a conventional method.
- the ink composition for water-based ballpoint pens having the above configuration is mounted, it is preferable to employ various ballpoint pen configurations on which an ink follower is mounted.
- the ink follower used in the aqueous ballpoint pen of the present invention is pre-kneaded at room temperature with all ink follower components such as a base oil and a surfactant, A very simple method of kneading with a disperser such as a roll mill or a kneader can be adopted.
- a disperser such as a roll mill or a kneader
- it can be heated, stirred, kneaded, and the like, if necessary.
- It is also possible to adjust the manufactured ink follower by re-kneading with a disperser such as a roll mill or a kneader, or by heating.
- Example 1 to 8 and Comparative Examples 1 and 2 [Microcapsule pigment: formulation of A-1 to A-6] (Pigment A-1) Leuco dye: 6- (dimethylamino) -3,3-bis [4- (dimethylamino) phenyl] -1 (3H) -isobenzofuranone 1 part, developer: 2 parts of bisphenol A, and a color change temperature adjusting agent : 24 parts of 4,4 ′-(hexafluoroisopropylidene) bisphenol dilaurate heated and melted, then adjusted to 95 ° C.
- Leuco dye 6- (dimethylamino) -3,3-bis [4- (dimethylamino) phenyl] -1 (3H) -isobenzofuranone 1 part
- developer 2 parts of bisphenol A
- a color change temperature adjusting agent 24 parts of 4,4 ′-(hexafluoroisopropylidene) bisphenol dilaurate heated and
- aqueous solution of methyl vinyl ether / maleic anhydride copolymer (GANTREZAN-179: manufactured by GAF CHEMICALS) The mixture was heated and stirred to disperse into oil droplets, and then 20 parts of a 50% methylolmelamine aqueous solution was gradually added as a capsule film agent, followed by reaction for 1 hour. The dispersion was filtered to obtain a microcapsule pigment.
- the finished microcapsule pigment had an average particle size of 0.3 ⁇ m.
- Pigment A-2 A microcapsule pigment having an average particle size of 0.6 ⁇ m was obtained by changing the stirring conditions in accordance with the formulation of Pigment A-1.
- Pigment A-3 A microcapsule pigment having an average particle size of 0.9 ⁇ m was obtained by changing the stirring conditions in accordance with the formulation of Pigment A-1.
- a solution obtained by adding 17 parts of formalin (formaldehyde 37% aqueous solution) to 10 parts of urea and 73 parts of water was added to the liquid dispersed in the above-mentioned oil droplets and adjusted to 80 ° C., and then a 20% acetic acid aqueous solution was added. 5 parts were added and reacted for 2 hours.
- the dispersion was filtered to obtain a microcapsule pigment.
- the finished microcapsule pigment had an average particle size of 0.8 ⁇ m.
- microcapsule pigment had an average particle size of 0.8 ⁇ m.
- a methyl vinyl ether / maleic anhydride copolymer heavy resin GANTREZAN-179: GAF CHEMICALS
- the finished microcapsule pigment had an average particle size of 0.6 ⁇ m.
- each water-based ink composition for water-based ballpoint pens was prepared by a conventional method.
- a water-based ballpoint pen was produced using each ink composition obtained above. Specifically, a ball pen [Mitsubishi Pencil Co., Ltd., trade name: Signo UM-100] shaft is used, an inner diameter of 3.8 mm, a length of 113 mm, a polypropylene ink containing tube, and a stainless tip (carbide) Each ink is filled in a refill comprising a ball, a ball diameter of 0.5 mm) and a joint connecting the receiving tube and the tip, and an ink follower mainly composed of mineral oil is loaded at the rear end of the ink. Produced. Using the obtained aqueous ballpoint pens of Examples 1 to 8 and Comparative Examples 1 to 3, the drawing density, storage stability, and writing property were evaluated by the following evaluation methods. These results are shown in Table 1 below.
- Examples 1 to 8 according to the present invention are superior in line density, storage stability, and writing properties as compared with Comparative Examples 1 to 3 that are outside the scope of the present invention.
- Comparative Examples 1 and 2 even when a microcapsule pigment having an average particle size of 0.1 to 1.0 ⁇ m is used, the wall film is formed of a urethane resin other than an amino resin or an epoxy resin. Therefore, the target effect cannot be exhibited, and even in the case of Comparative Example 3, the microcapsule pigment of the present invention does not contain a chemical substance composed of a polymer having the ketone of the present invention as a main chain, so that the target effect is exhibited. I knew it was possible.
- microcapsule pigments with an average particle size of 0.1 to 1.0 ⁇ m are used, excellent line drawing density is achieved, and ink storage stability and writing performance are excellent. It is most suitable for ink compositions and water-based ballpoint pens.
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
- Pens And Brushes (AREA)
Abstract
Description
例えば、(イ)ロイコ染料である電子供与性呈色性有機化合物、(ロ)顕色剤である電子受容性化合物、(ハ)前記両者の呈色反応の生起温度を決める変色温度調整剤となる反応媒体からなる可逆熱変色性組成物を内包させた可逆熱変色性マイクロカプセル顔料と、水を少なくとも含有してなり、前記可逆熱変色性マイクロカプセル顔料の平均粒子径が2.5~4.0μmの範囲にあり、且つ、2.0μm以下の粒子が全マイクロカプセル顔料中の30体積%以下であることを特徴とする可逆熱変色性筆記具用水性インキ組成物(例えば、特許文献1参照)や、水と、(イ)ロイコ染料である電子供与性呈色性有機化合物、(ロ)顕色剤である電子受容性化合物、(ハ)前記両者の呈色反応の生起温度を決める変色温度調整剤となる反応媒体からなる可逆熱変色性組成物を内包させた可逆熱変色性マイクロカプセル顔料と、高分子凝集剤と、側鎖にカルボキシル基を有する櫛形高分子分散剤と、水溶性樹脂とからなり、上記マイクロカプセル顔料の最大外径の平均値が0.5~5.0μmである可逆熱変色性筆記具用水性インキ組成物(例えば、特許文献2参照)が知られている。
(1) 平均粒子径が0.1~1.0μmである壁膜がアミノ樹脂で形成されたマイクロカプセル顔料と、ケトンを主鎖とするポリマーであって、化学構造内に酸性官能基を持ち、かつ酸価3~40(mgKOH/g)である化学物質とを少なくとも含有することを特徴とする水性ボールペン用インキ組成物。
(2) 更に、ポリオキシエチレン脂肪族アミン(脂肪族の炭素数が10~20である)を含有することを特徴とする上記(1)記載の水性ボールペン用インキ組成物。
(3) 前記ポリオキシエチレン脂肪族アミンにおけるポリオキシエチレンの付加モル数が10~50であることを特徴とする上記(2)記載の水性ボールペン用インキ組成物。
(4) 上記(1)~(3)の何れか一つに記載の水性ボールペン用インキ組成物を搭載したことを特徴とする水性ボールペン
本発明の水性ボールペン用インキ組成物は、平均粒子径が0.1~1.0μmである壁膜がアミノ樹脂で形成されたマイクロカプセル顔料と、ケトンを主鎖とするポリマーであって、化学構造内に酸性官能基を持ち、かつ酸価3~40(mgKOH/g)である化学物質とを少なくとも含有することを特徴とするものである。
用いることができるロイコ染料としては、電子供与性染料で、発色剤としての機能するものであれば、特に限定されものではない。具体的には、発色特性に優れるインキを得る点から、トリフェニルメタン系、スピロピラン系、フルオラン系、ジフェニルメタン系、ローダミンラクタム系、インドリルフタリド系、ロイコオーラミン系等従来公知のものが、単独(1種)で又は2種以上を混合して(以下、単に「少なくとも1種」という)用いることができる。
具体的には、6-(ジメチルアミノ)-3,3-ビス[4-(ジメチルアミノ)フェニル]-1(3H)-イソベンゾフラノン、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-(4-ジエチルアミノ-2-エトキシフェニル)-3-(1-エチル-2-メチルインドール-3-イル)-4-アザフタリド、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-ジメチルアミノフルオラン、3-ジブチルアミノ-6-メチル-7-アニリノフルオラン、3-ジエチルアミノ-6-メチル-7-アニリノフルオラン、3-ジエチルアミノ-6-メチル-7-キシリジノフルオラン、2-(2-クロロアニリノ)-6-ジブチ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、1,2-ベンツ-6-ジエチルアミノフルオラン、1,2-ベンツ-6-ジブチルアミノフルオラン、1,2-ベンツ-6-エチルイソアミルアミノフルオラン、2-メチル-6-(N-p-トリル-N-エチルアミノ)フルオラン、2-(N-フェニル-N--メチルアミノ)-6-(N-p-トリル-N-エチルアミノ)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、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、3-メトキシ-4-ドデコキシスチリノキノリンなどが挙げられ、これらは、少なくとも1種用いることができる。
更に、黄色~赤色の発色を発現させるピリジン系化合物、キナゾリン系化合物、ビスキナゾリン系化合物等も用いることができる。
これらのロイコ染料は、ラクトン骨格、ピリジン骨格、キナゾリン骨格、ビスキナゾリン骨格等を有するものであり、これらの骨格(環)が開環することで発色を発現するものである。
具体的には、ビスフェノールA、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、ヘキサフルオロビスフェノール、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-ノナンなどが挙げられ、これらは、少なくとも1種用いることができる。
具体的には、ベヘニルアルコール、ステアリルアルコール、セチルアルコール、ミリスチルアルコール、ラウリルアルコール、ウンデシルアルコール、デシルアルコール、ノニルアルコール、オクチルアルコール、ヘキシルアルコール、ネオペンチルアルコール、ブチルアルコール、メチルアルコール、エチレングリコール、ポリエチレングリコール、セロソルブ、グリセリン、ペンタエリスリトール、ベンジルアルコール、シクロヘキシルアルコール、カプリン酸オクチル、カプリン酸デシル、ラウリン酸ラウリル、ラウリン酸ミリスチル、ミリスチン酸デシル、ミリスチン酸ラウリル、ミリスチン酸セチル、パルミチン酸ラウリル、パルミチン酸セチル、パルミチン酸ステアリル、ステアリン酸ラウリル、p-t-ブチル安息香酸セチル、4-メトキシ安息香酸ステアリル、4,4’-(ヘキサフルオロイソプロピリデン)ビスフェノールジラウレート、チオジプロピオン酸ジラウリル、チオジプロピオン酸ジミリスチル、ステアリルベンゾエート、ベンジルステアレート、チオジプロピオン酸ジベンジル、チオジプロピオン酸時ステアリル、安息香酸ベンジル、トリラウレート、トリエチルシトレート、フタル酸ジステアリル、アジピン酸ジデシル、ジデシルエーテル、ジステアリルエーテル、ジステアリルケトン、アセトン、アセトフェノン、ステアリン酸アマイド、ラウリン酸アマイド、ラウリルアルコール・アクリロニトリル付加物、ステアリルアルコール・アクリロニトリル付加物、ベンジリデン・p-トルイジン、ベンジリデン・ブチルアミン、ステアリン酸、パルミチン酸、ラウリン酸、ラウリン酸、シクロパラフィンなどが挙げられ、これらは、少なくとも1種用いることができる。
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、insitu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。
例えば、水溶液からの相分離法では、ロイコ染料、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、壁膜がアミノ樹脂で形成できる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。
これらのロイコ染料、顕色剤、変色温度調整剤の含有量は、用いるロイコ染料、顕色剤、変色温度調整剤の種類、マイクロカプセル化法などにより変動するが、ロイコ染料1に対して、質量比で顕色剤0.1~100、変色温度調整剤1~100である。また、カプセル膜剤は、カプセル内容物に対して、質量比で0.1~1である。
本発明のマイクロカプセル顔料では、上記ロイコ染料、顕色剤及び変色温度調整剤の種類、量などを好適に組み合わせることにより、各顔料の色、任意の発色温度、消色温度とすることができる。
壁膜がアミノ樹脂以外の樹脂、例えば、ウレタン樹脂、エポキシ樹脂などで形成された場合は、描線濃度、保存安定性、筆記性の少なくとも1つ以上が劣ることとなり、好ましくない。
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、ベンゾグアンアミン樹脂等)、並びに、分散剤、保護コロイドなどを選択する。
この平均粒子径が0.1μm未満であると、十分な描線濃度が得られず、一方、1.0μmを越えると、筆記性の劣化やマイクロカプセル顔料の分散安定性の低下が発生し、好ましくない。
なお、上記範囲(0.1~1.0μm)となる平均粒子径のマイクロカプセル顔料は、マイクロカプセル化法により変動するが、水溶液からの相分離法などでは、マイクロカプセル顔料を製造する際の攪拌条件を好適に組み合わせることにより調製することができる。
この着色剤(顕色粒子)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。
用いることができる化学物質は、ケトンを主鎖とするポリマーであって、化学構造内の酸性官能基としては、カルボン酸基、リン酸基などが挙げられる。
この酸価が3mgKOH/g未満であると、筆記性においてカスレが生じやすくなり、一方、40mgKOH/gを超えると、インクの安定性が低下して析出物が発生しやすくなり、好ましくない。より好ましい酸価は5~15mgKOH/gである。
この含有量が0.1%未満であると、満足する描線濃度が得られず、またマイクロカプセル顔料の安定性が低下する。一方、10%を超えると、筆記時にカスレが生じやすくなり好ましくない。
この脂肪族の炭素数が10未満であると、顔料への吸着性が悪くなり、顔料分散効果が不十分となり、一方、炭素数が20を超えると、水への溶解性が不十分となり、好ましくない。
好ましいPOE脂肪族アミンは、水への溶解性、筆記性の点から、POE脂肪族アミンにおけるPOEの付加モル数は10~50であるものが望ましく、さらに望ましくは10~20モルである。
用いることができるPOE脂肪族アミンとしては、例えば、POE(15)オレイルアミン、POE(15)ステアリルアミンを挙げることができ、これらは、少なくとも1種用いることができる。
この含有量が0.1%未満であると、顔料分散効果が不十分となり、一方、10%を超えると、筆記時にカスレが生じやすくなり、好ましくない。
用いることができる増粘剤としては、例えば、合成高分子、天然ゴム、セルロースおよび多糖類からなる群から選ばれた少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、カゼイン、キサンタンガム、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、ポリエチレシオキサイド、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。
本発明の水性ボールペン用インキ組成物が何故平均粒子径が0.1~1.0μmとなる小さいマイクロカプセル顔料を使用しても、十分な描線濃度が得られ、かつ、インキの保存安定性、筆記性能に優れるかは以下の理由によるものと推察される。
すなわち、本発明では、上記化学物質が、マイクロカプセル顔料に対して緩やかな凝集を引き起こすことで描線濃度を向上させ、更にポリオキシエチレン脂肪族アミンがこの凝集状態を安定に保つ役目を果たしているためである。
本発明では、上記構成の水性ボールペン用インキ組成物を搭載するので、インキ追従体が搭載された各種ボールペン構成を採用することが好ましい。
〔マイクロカプセル顔料:A-1~A-6の処方〕
(顔料A-1)
ロイコ色素:6-(ジメチルアミノ)-3,3-ビス[4-(ジメチルアミノ)フェニル]-1(3H)-イソベンゾフラノン1部、顕色性物質:ビスフェノールA2部、及び変色温度調整剤:4,4’-(ヘキサフルオロイソプロピリデン)ビスフェノールジラウレート24部を加熱溶融後、95℃、pH4に調整したメチルビニルエーテル・無水マレイン酸共重樹脂(GANTREZAN-179:GAF CHEMICALS社製)水溶液400部に投入し、過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、50%メチロールメラミン水溶液20部を徐々に投入し、引き続き1時間反応させて調製した。この分散液を濾過することによりマイクロカプセル顔料を得た。なお、出来上がったマイクロカプセル顔料の平均粒子径は0.3μmであった。
顔料A-1の処方に準じて、攪拌条件を変えることにより平均粒子径0.6μmのマイクロカプセル顔料を得た。
顔料A-1の処方に準じて、攪拌条件を変えることにより平均粒子径0.9μmのマイクロカプセル顔料を得た。
ロイコ色素:6-(ジメチルアミノ)-3,3-ビス[4-(ジメチルアミノ)フェニル]-1(3H)-イソベンゾフラノン1部、顕色性物質:ビスフェノールA2部、及び変色温度調整剤:4,4’-(ヘキサフルオロイソプロピリデン)ビスフェノールジラウレート24部を加熱溶融後、ドデシルベンゼンスルホン酸ナトリウム0.1部を含む60℃の水276部に攪拌しながら投入し油滴状に分散した。さらに尿素10部にホルマリン(ホルムアルデヒド37%水溶液)17部、 水を73部加えた溶解液を前述の油滴状に分散した液中に投入して80℃に調整した後、酢酸20%水溶液を5部添加し、2時間反応させた。この分散液を濾過することによりマイクロカプセル顔料を得た。なお、出来上がったマイクロカプセル顔料の平均粒子径は0.8μmであった。
ロイコ色素:6-(ジメチルアミノ)-3,3-ビス[4-(ジメチルアミノ)フェニル]-1(3H)-イソベンゾフラノン1部、顕色性物質:ビスフェノールA2部、及び変色温度調整剤:4,4’-(ヘキサフルオロイソプロピリデン)ビスフェノールジラウレート24部及びイソシアネート(MR-200:日本ポリウレタン工業社製)5部を加熱溶融後、リン酸三カルシウム2部とドデシルベンゼンスルホン酸ナトリウム0.04部を含む60℃の水溶液400部に投入し、加熱攪拌して油滴状に分散させ、次いでキシリレンジアミン2部を滴下し、60℃で約3時間攪拌して反応を終了させた後、塩酸処理を行った。この分散液を濾過することによりマイクロカプセル顔料を得た。なお、出来上がったマイクロカプセル顔料の平均粒子径は0.8μmであった。
ロイコ色素:6-(ジメチルアミノ)-3,3-ビス[4-(ジメチルアミノ)フェニル]-1(3H)-イソベンゾフラノン1部、顕色性物質:ビスフェノールA2部、及び変色温度調整剤:4,4’-(ヘキサフルオロイソプロピリデン)ビスフェノールジラウレート24部及びエポキシ樹脂(jER828:ジャパンエポキシレジン社製)を加熱溶融後、95℃、pH4に調整したメチルビニルエーテル・無水マレイン酸共重樹脂(GANTREZAN-179:GAF CHEMICALS社)水溶液400部に投入し、過熱攪拌して油滴状に分散させ、次いでアミン系硬化剤(jER U:ジャパンエポキシレジン社製)3部を投入し、引き続き4時間反応させた。この分散液を濾過することによりマイクロカプセル顔料を得た。なお、出来上がったマイクロカプセル顔料の平均粒子径は0.6μmであった。
下記表1に示す配合処方(マイクロカプセル顔料:A-1~A-6、アミン類:トリエタノールアミン、B-1~B-3、増粘剤、防錆剤、防腐剤、溶剤、水)にしたがって、常法により各水性ボールペン用水性インキ組成物を調製した。
上記で得られた各インキ組成物を用いて水性ボールペンを作製した。具体的には、ボールぺン〔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キ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インキを充填し、インキ後端に鉱油を主成分とするインキ追従体を装填し、水性ボールペンを作製した。
得られた実施例1~8及び比較例1~3の水性ボールペンを用いて、下記各評価方法で描線濃度、保存安定性、筆記性の評価を行った。
これらの結果を下記表1に示す。
各ペン体を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、目視により描線濃度を下記の基準で評価した。
評価基準:
○:本願発明の化学物質を配合していないインクにより得られた筆記描線と比較して十分に濃い描線濃度。
△:本願発明の化学物質を配合していないインクにより得られた筆記描線と比較して濃い描線濃度。
×:本願発明の化学物質を配合していないインクにより得られた筆記描線と比較して同等以下の描線濃度。
得られた各インキを15mlのガラス製蓋付き瓶に充填し、密封した後に、50℃の条件下で
3ヶ月保存した後、夫々のインキの状態を目視で確認し、下記の基準で評価した。
評価基準:
○:分離、凝集は発生していない。
△:僅かな分離または凝集。
×:分離または凝集がある。
各ペン体を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。
これに対して、比較例1~2では、平均粒子径が0.1~1.0μmとしたマイクロカプセル顔料を用いても、壁膜がアミノ樹脂以外のウレタン樹脂、エポキシ樹脂で形成されているため、目的の効果を発揮できず、また、比較例3では本発明のマイクロカプセル顔料を用いても本発明のケトンを主鎖とするポリマーからなる化学物質を含有しないため、目的の効果を発揮できことがわかった。
Claims (4)
- 平均粒子径が0.1~1.0μmである壁膜がアミノ樹脂で形成されたマイクロカプセル顔料と、ケトンを主鎖とするポリマーであって、化学構造内に酸性官能基を持ち、かつ酸価が3~40(mgKOH/g)である化学物質とを少なくとも含有することを特徴とする水性ボールペン用インキ組成物。
- 更に、ポリオキシエチレン脂肪族アミン(脂肪族の炭素数が10~20である)を含有することを特徴とする請求項1記載の水性ボールペン用インキ組成物。
- 前記ポリオキシエチレン脂肪族アミンにおけるポリオキシエチレンの付加モル数が10~50であることを特徴とする請求項2記載の水性ボールペン用インキ組成物。
- 請求項1~3の何れか一つに記載の水性ボールペン用インキ組成物を搭載したことを特徴とする水性ボールペン。
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US13/514,766 US8562235B2 (en) | 2009-12-08 | 2010-12-02 | Ink composition for aqueous ink ball point pen and aqueous ink ball point pen |
EP10835887.0A EP2511353B1 (en) | 2009-12-08 | 2010-12-02 | Ink composition for a water-based ballpoint pen, and water-based ballpoint pen |
CN201080063095.1A CN102753632B (zh) | 2009-12-08 | 2010-12-02 | 水性墨圆珠笔用墨组合物和水性墨圆珠笔 |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2009278763A JP5534794B2 (ja) | 2009-12-08 | 2009-12-08 | 水性ボールペン用インキ組成物及び水性ボールペン |
JP2009-278763 | 2009-12-08 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2011070966A1 true WO2011070966A1 (ja) | 2011-06-16 |
Family
ID=44145511
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2010/071576 WO2011070966A1 (ja) | 2009-12-08 | 2010-12-02 | 水性ボールペン用インキ組成物及び水性ボールペン |
Country Status (6)
Country | Link |
---|---|
US (1) | US8562235B2 (ja) |
EP (1) | EP2511353B1 (ja) |
JP (1) | JP5534794B2 (ja) |
KR (1) | KR101576329B1 (ja) |
CN (1) | CN102753632B (ja) |
WO (1) | WO2011070966A1 (ja) |
Families Citing this family (16)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP5444061B2 (ja) * | 2010-03-18 | 2014-03-19 | パイロットインキ株式会社 | 感温変色性色彩記憶性トナー及びそれを収容したカートリッジ、画像形成装置、カートリッジセット、画像形成装置セット |
JP5885965B2 (ja) * | 2011-08-19 | 2016-03-16 | 株式会社パイロットコーポレーション | 水性ボールペン用インキ組成物およびそれを用いた水性ボールペン |
JP6231351B2 (ja) * | 2013-09-03 | 2017-11-15 | 三菱鉛筆株式会社 | マイクロカプセル色材及び筆記具用インク組成物 |
CN104130627B (zh) * | 2014-07-23 | 2016-12-07 | 王勇 | 稳定的变色墨水 |
JP6533833B2 (ja) * | 2015-10-21 | 2019-06-19 | 株式会社日立製作所 | 温度検知体 |
CN108463514B (zh) * | 2016-01-06 | 2021-03-09 | 三菱铅笔株式会社 | 微胶囊颜料和书写工具用水性墨组合物 |
JP6626369B2 (ja) * | 2016-02-29 | 2019-12-25 | 三菱鉛筆株式会社 | 筆記具用水性インク組成物 |
JP6888925B2 (ja) * | 2016-08-24 | 2021-06-18 | 三菱鉛筆株式会社 | 筆記具 |
US10851252B2 (en) * | 2016-08-29 | 2020-12-01 | Mitsubishi Pencil Company, Limited | Aqueous ink composition for writing instruments |
JP6763746B2 (ja) * | 2016-10-28 | 2020-09-30 | 株式会社パイロットコーポレーション | 熱変色性筆記具インキ組成物及びそれを内蔵した筆記具 |
JP6811626B2 (ja) * | 2017-01-25 | 2021-01-13 | 三菱鉛筆株式会社 | ボールペン用水性インク組成物 |
CA3165595A1 (en) * | 2019-12-24 | 2021-07-01 | Mitsubishi Pencil Company, Limited | Ink composition for water-based ballpoint pens |
EP3858925B1 (en) * | 2020-01-28 | 2023-01-11 | Société BIC | Irreversibly erasable ink composition comprising a discoloration agent |
EP3904468B1 (en) | 2020-04-30 | 2022-10-19 | Société BIC | Method for preparing thermochromic water-based gel ink compositions, and thermochromic water-based gel ink compositions thereof |
JP2021181515A (ja) * | 2020-05-18 | 2021-11-25 | 三菱鉛筆株式会社 | 水性ボールペン用インク組成物 |
CN116426163A (zh) * | 2023-04-04 | 2023-07-14 | 合肥金龙浩科技有限公司 | 一种温致变色油墨及其应用 |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2005132884A (ja) * | 2003-10-28 | 2005-05-26 | Pilot Ink Co Ltd | インキ用着色樹脂粒状体及びそれを用いた筆記具用インキ組成物 |
JP2006007766A (ja) * | 2004-05-28 | 2006-01-12 | Pentel Corp | ボールペン |
JP2006206786A (ja) * | 2005-01-31 | 2006-08-10 | Pentel Corp | ボールペン用水性インキ組成物 |
JP2008280440A (ja) | 2007-05-11 | 2008-11-20 | Pilot Ink Co Ltd | 可逆熱変色性筆記具用水性インキ組成物及びそれを収容した筆記具 |
JP2009227954A (ja) | 2008-02-29 | 2009-10-08 | Pilot Ink Co Ltd | 可逆熱変色性水性インキ組成物及びそれを用いた筆記具、筆記具セット |
JP2010132822A (ja) * | 2008-12-05 | 2010-06-17 | Matsui Shikiso Chem Co Ltd | 可逆感温変色性ヒステリシス組成物 |
Family Cites Families (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
TW429267B (en) * | 1996-02-05 | 2001-04-11 | Pilot Ink Co Ltd | Preparation method for shear-thinning water-based ball-point pen inks, shear-thinning water-based ball-point pen ink compositions, and ball-point pens employing the same |
EP0987304A4 (en) * | 1996-12-12 | 2000-10-25 | Mitsubishi Pencil Co | WATERBASE PEN INK INK, WHICH HAS METALLIC SHINY COLOR |
JP4303396B2 (ja) * | 2000-04-13 | 2009-07-29 | パイロットインキ株式会社 | 可逆熱変色性紫外線硬化型インキ及びそれを用いた可逆熱変色性積層体 |
US6548174B2 (en) * | 2000-06-30 | 2003-04-15 | Kansai Paint Co., Ltd. | Pigment dispersing resins |
US6609934B2 (en) * | 2001-12-03 | 2003-08-26 | Industrial Technology Research Institute | Rear-end electromagnetic shielding component of an electronic connector |
EP1657073B1 (en) * | 2004-11-15 | 2008-02-27 | The Pilot Ink Co., Ltd. | Reversible thermochromic composition and microcapsules containing the same |
US20070082977A1 (en) * | 2005-10-07 | 2007-04-12 | The Pilot Ink Co., Ltd. | Ink composition for color-memorizing photochromic writing instrument and writing instrument using the same |
CN101959979B (zh) * | 2008-03-04 | 2014-05-07 | 大日本涂料株式会社 | 非水性喷墨用油墨组合物 |
JP5240992B2 (ja) * | 2008-03-31 | 2013-07-17 | 大日本塗料株式会社 | 非水系インクジェット用インク組成物 |
JP5651389B2 (ja) * | 2010-06-30 | 2015-01-14 | 富士フイルム株式会社 | 顔料組成物、インクジェット記録用インク、カラーフィルター用着色組成物及びカラーフィルター |
-
2009
- 2009-12-08 JP JP2009278763A patent/JP5534794B2/ja not_active Expired - Fee Related
-
2010
- 2010-12-02 CN CN201080063095.1A patent/CN102753632B/zh not_active Expired - Fee Related
- 2010-12-02 WO PCT/JP2010/071576 patent/WO2011070966A1/ja active Application Filing
- 2010-12-02 KR KR1020127017535A patent/KR101576329B1/ko active IP Right Grant
- 2010-12-02 US US13/514,766 patent/US8562235B2/en not_active Expired - Fee Related
- 2010-12-02 EP EP10835887.0A patent/EP2511353B1/en not_active Not-in-force
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2005132884A (ja) * | 2003-10-28 | 2005-05-26 | Pilot Ink Co Ltd | インキ用着色樹脂粒状体及びそれを用いた筆記具用インキ組成物 |
JP2006007766A (ja) * | 2004-05-28 | 2006-01-12 | Pentel Corp | ボールペン |
JP2006206786A (ja) * | 2005-01-31 | 2006-08-10 | Pentel Corp | ボールペン用水性インキ組成物 |
JP2008280440A (ja) | 2007-05-11 | 2008-11-20 | Pilot Ink Co Ltd | 可逆熱変色性筆記具用水性インキ組成物及びそれを収容した筆記具 |
JP2009227954A (ja) | 2008-02-29 | 2009-10-08 | Pilot Ink Co Ltd | 可逆熱変色性水性インキ組成物及びそれを用いた筆記具、筆記具セット |
JP2010132822A (ja) * | 2008-12-05 | 2010-06-17 | Matsui Shikiso Chem Co Ltd | 可逆感温変色性ヒステリシス組成物 |
Non-Patent Citations (1)
Title |
---|
See also references of EP2511353A4 |
Also Published As
Publication number | Publication date |
---|---|
EP2511353A4 (en) | 2014-03-12 |
KR20120103685A (ko) | 2012-09-19 |
KR101576329B1 (ko) | 2015-12-09 |
CN102753632A (zh) | 2012-10-24 |
EP2511353B1 (en) | 2015-09-16 |
JP5534794B2 (ja) | 2014-07-02 |
JP2011122010A (ja) | 2011-06-23 |
EP2511353A1 (en) | 2012-10-17 |
US8562235B2 (en) | 2013-10-22 |
CN102753632B (zh) | 2014-04-09 |
US20120251222A1 (en) | 2012-10-04 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP5534794B2 (ja) | 水性ボールペン用インキ組成物及び水性ボールペン | |
TWI572679B (zh) | A pigment, an ink composition using a microcapsule pigment and a writing instrument | |
JP6231351B2 (ja) | マイクロカプセル色材及び筆記具用インク組成物 | |
JP7170087B2 (ja) | 色素、マイクロカプセル顔料 | |
JP6000686B2 (ja) | 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 | |
JP5713800B2 (ja) | 筆記具用油性インク組成物 | |
KR102593856B1 (ko) | 수성 볼펜용 잉크 조성물 | |
JP2022138651A (ja) | 熱変色性マイクロカプセル及び熱変色性インク組成物 | |
JP5754966B2 (ja) | 筆記具用水性インク組成物 | |
JP6817151B2 (ja) | 筆記具用水性インク組成物 | |
JP6718259B2 (ja) | ボールペン用水性インク組成物 | |
JPH09124993A (ja) | 熱変色性水性ボールペンインキ及びそれを用いたボールペン | |
JP6245511B2 (ja) | マイクロカプセル色材及び筆記具用インク組成物 | |
JP6622073B2 (ja) | 筆記具用インク組成物 | |
JP7323332B2 (ja) | 水性ボールペン用インク組成物 | |
JP6239933B2 (ja) | マイクロカプセル色材及び筆記具用インク組成物 | |
WO2022071113A1 (ja) | マイクロカプセル顔料及び筆記具用インク組成物 | |
JP2022175433A (ja) | マイクロカプセル顔料、これを含有した筆記具用インク組成物 | |
JP5921087B2 (ja) | 筆記具用水性インク組成物 | |
JP2012219160A (ja) | 筆記具用水性インク組成物 | |
JP2013091750A (ja) | 筆記具用水性インキ組成物及びそれを内蔵した筆記具 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
WWE | Wipo information: entry into national phase |
Ref document number: 201080063095.1 Country of ref document: CN |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 10835887 Country of ref document: EP Kind code of ref document: A1 |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
WWE | Wipo information: entry into national phase |
Ref document number: 13514766 Country of ref document: US |
|
ENP | Entry into the national phase |
Ref document number: 20127017535 Country of ref document: KR Kind code of ref document: A |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2010835887 Country of ref document: EP |