JP6654604B2 - Aqueous pigment ink composition for writing implements and batting type felt-tip pen equipped with the ink composition - Google Patents
Aqueous pigment ink composition for writing implements and batting type felt-tip pen equipped with the ink composition Download PDFInfo
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- JP6654604B2 JP6654604B2 JP2017130463A JP2017130463A JP6654604B2 JP 6654604 B2 JP6654604 B2 JP 6654604B2 JP 2017130463 A JP2017130463 A JP 2017130463A JP 2017130463 A JP2017130463 A JP 2017130463A JP 6654604 B2 JP6654604 B2 JP 6654604B2
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- ink composition
- resin emulsion
- aqueous pigment
- pigment ink
- resin
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- 239000000049 pigment Substances 0.000 title claims description 139
- 239000000203 mixture Substances 0.000 title claims description 92
- 239000000839 emulsion Substances 0.000 claims description 84
- 229920005989 resin Polymers 0.000 claims description 84
- 239000011347 resin Substances 0.000 claims description 83
- 239000006185 dispersion Substances 0.000 claims description 45
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 33
- 229920002050 silicone resin Polymers 0.000 claims description 20
- 239000007788 liquid Substances 0.000 claims description 12
- 239000007787 solid Substances 0.000 claims description 12
- 229920005749 polyurethane resin Polymers 0.000 claims description 10
- 238000003860 storage Methods 0.000 claims description 8
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 claims description 5
- 229920000178 Acrylic resin Polymers 0.000 claims description 5
- 239000004925 Acrylic resin Substances 0.000 claims description 5
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 claims description 4
- XLLIQLLCWZCATF-UHFFFAOYSA-N 2-methoxyethyl acetate Chemical compound COCCOC(C)=O XLLIQLLCWZCATF-UHFFFAOYSA-N 0.000 claims description 4
- SVTBMSDMJJWYQN-UHFFFAOYSA-N 2-methylpentane-2,4-diol Chemical compound CC(O)CC(C)(C)O SVTBMSDMJJWYQN-UHFFFAOYSA-N 0.000 claims description 4
- VXQBJTKSVGFQOL-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethyl acetate Chemical compound CCCCOCCOCCOC(C)=O VXQBJTKSVGFQOL-UHFFFAOYSA-N 0.000 claims description 2
- FPZWZCWUIYYYBU-UHFFFAOYSA-N 2-(2-ethoxyethoxy)ethyl acetate Chemical compound CCOCCOCCOC(C)=O FPZWZCWUIYYYBU-UHFFFAOYSA-N 0.000 claims description 2
- NQBXSWAWVZHKBZ-UHFFFAOYSA-N 2-butoxyethyl acetate Chemical compound CCCCOCCOC(C)=O NQBXSWAWVZHKBZ-UHFFFAOYSA-N 0.000 claims description 2
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 claims description 2
- MFKRHJVUCZRDTF-UHFFFAOYSA-N 3-methoxy-3-methylbutan-1-ol Chemical compound COC(C)(C)CCO MFKRHJVUCZRDTF-UHFFFAOYSA-N 0.000 claims description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 2
- 239000005977 Ethylene Substances 0.000 claims description 2
- XXJWXESWEXIICW-UHFFFAOYSA-N diethylene glycol monoethyl ether Chemical compound CCOCCOCCO XXJWXESWEXIICW-UHFFFAOYSA-N 0.000 claims description 2
- 229940075557 diethylene glycol monoethyl ether Drugs 0.000 claims description 2
- 229940051250 hexylene glycol Drugs 0.000 claims description 2
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 claims description 2
- 239000000976 ink Substances 0.000 description 122
- 229920002799 BoPET Polymers 0.000 description 14
- 238000011156 evaluation Methods 0.000 description 13
- 239000002904 solvent Substances 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- 229920001296 polysiloxane Polymers 0.000 description 10
- 229920000742 Cotton Polymers 0.000 description 9
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 9
- 239000000178 monomer Substances 0.000 description 8
- 239000004094 surface-active agent Substances 0.000 description 8
- 238000005299 abrasion Methods 0.000 description 7
- -1 primary Chemical class 0.000 description 7
- 239000000080 wetting agent Substances 0.000 description 7
- 230000002950 deficient Effects 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 5
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 5
- 239000000654 additive Substances 0.000 description 5
- 239000000835 fiber Substances 0.000 description 5
- 239000003112 inhibitor Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 5
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- WDQMWEYDKDCEHT-UHFFFAOYSA-N 2-ethylhexyl 2-methylprop-2-enoate Chemical compound CCCCC(CC)COC(=O)C(C)=C WDQMWEYDKDCEHT-UHFFFAOYSA-N 0.000 description 4
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 4
- 239000003086 colorant Substances 0.000 description 4
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 4
- SDGKUVSVPIIUCF-UHFFFAOYSA-N 2,6-dimethylpiperidine Chemical compound CC1CCCC(C)N1 SDGKUVSVPIIUCF-UHFFFAOYSA-N 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 239000006229 carbon black Substances 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 239000011362 coarse particle Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 239000002274 desiccant Substances 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 2
- 239000003995 emulsifying agent Substances 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 239000003550 marker Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- 150000003673 urethanes Chemical class 0.000 description 2
- QGKMIGUHVLGJBR-UHFFFAOYSA-M (4z)-1-(3-methylbutyl)-4-[[1-(3-methylbutyl)quinolin-1-ium-4-yl]methylidene]quinoline;iodide Chemical compound [I-].C12=CC=CC=C2N(CCC(C)C)C=CC1=CC1=CC=[N+](CCC(C)C)C2=CC=CC=C12 QGKMIGUHVLGJBR-UHFFFAOYSA-M 0.000 description 1
- CUVLMZNMSPJDON-UHFFFAOYSA-N 1-(1-butoxypropan-2-yloxy)propan-2-ol Chemical compound CCCCOCC(C)OCC(C)O CUVLMZNMSPJDON-UHFFFAOYSA-N 0.000 description 1
- IBLKWZIFZMJLFL-UHFFFAOYSA-N 1-phenoxypropan-2-ol Chemical compound CC(O)COC1=CC=CC=C1 IBLKWZIFZMJLFL-UHFFFAOYSA-N 0.000 description 1
- FMVOPJLFZGSYOS-UHFFFAOYSA-N 2-[2-(2-ethoxypropoxy)propoxy]propan-1-ol Chemical compound CCOC(C)COC(C)COC(C)CO FMVOPJLFZGSYOS-UHFFFAOYSA-N 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- JQXYBDVZAUEPDL-UHFFFAOYSA-N 2-methylidene-5-phenylpent-4-enoic acid Chemical compound OC(=O)C(=C)CC=CC1=CC=CC=C1 JQXYBDVZAUEPDL-UHFFFAOYSA-N 0.000 description 1
- QCDWFXQBSFUVSP-UHFFFAOYSA-N 2-phenoxyethanol Chemical compound OCCOC1=CC=CC=C1 QCDWFXQBSFUVSP-UHFFFAOYSA-N 0.000 description 1
- QCAHUFWKIQLBNB-UHFFFAOYSA-N 3-(3-methoxypropoxy)propan-1-ol Chemical compound COCCCOCCCO QCAHUFWKIQLBNB-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 241000283070 Equus zebra Species 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 229920005692 JONCRYL® Polymers 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- 241000282320 Panthera leo Species 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 229920001214 Polysorbate 60 Polymers 0.000 description 1
- NRCMAYZCPIVABH-UHFFFAOYSA-N Quinacridone Chemical compound N1C2=CC=CC=C2C(=O)C2=C1C=C1C(=O)C3=CC=CC=C3NC1=C2 NRCMAYZCPIVABH-UHFFFAOYSA-N 0.000 description 1
- 229920006328 Styrofoam Polymers 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 1
- 150000004056 anthraquinones Chemical class 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- AOJOEFVRHOZDFN-UHFFFAOYSA-N benzyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC1=CC=CC=C1 AOJOEFVRHOZDFN-UHFFFAOYSA-N 0.000 description 1
- GCTPMLUUWLLESL-UHFFFAOYSA-N benzyl prop-2-enoate Chemical compound C=CC(=O)OCC1=CC=CC=C1 GCTPMLUUWLLESL-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- PPSZHCXTGRHULJ-UHFFFAOYSA-N dioxazine Chemical compound O1ON=CC=C1 PPSZHCXTGRHULJ-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 230000000855 fungicidal effect Effects 0.000 description 1
- 239000000417 fungicide Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- YAMHXTCMCPHKLN-UHFFFAOYSA-N imidazolidin-2-one Chemical compound O=C1NCCN1 YAMHXTCMCPHKLN-UHFFFAOYSA-N 0.000 description 1
- 239000001023 inorganic pigment Substances 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- PXZQEOJJUGGUIB-UHFFFAOYSA-N isoindolin-1-one Chemical compound C1=CC=C2C(=O)NCC2=C1 PXZQEOJJUGGUIB-UHFFFAOYSA-N 0.000 description 1
- GWVMLCQWXVFZCN-UHFFFAOYSA-N isoindoline Chemical compound C1=CC=C2CNCC2=C1 GWVMLCQWXVFZCN-UHFFFAOYSA-N 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229920003145 methacrylic acid copolymer Polymers 0.000 description 1
- 229940117841 methacrylic acid copolymer Drugs 0.000 description 1
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000007764 o/w emulsion Substances 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- 239000003002 pH adjusting agent Substances 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- DGBWPZSGHAXYGK-UHFFFAOYSA-N perinone Chemical compound C12=NC3=CC=CC=C3N2C(=O)C2=CC=C3C4=C2C1=CC=C4C(=O)N1C2=CC=CC=C2N=C13 DGBWPZSGHAXYGK-UHFFFAOYSA-N 0.000 description 1
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 description 1
- CSHWQDPOILHKBI-UHFFFAOYSA-N peryrene Natural products C1=CC(C2=CC=CC=3C2=C2C=CC=3)=C3C2=CC=CC3=C1 CSHWQDPOILHKBI-UHFFFAOYSA-N 0.000 description 1
- 229960005323 phenoxyethanol Drugs 0.000 description 1
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- QMYDVDBERNLWKB-UHFFFAOYSA-N propane-1,2-diol;hydrate Chemical compound O.CC(O)CO QMYDVDBERNLWKB-UHFFFAOYSA-N 0.000 description 1
- FYNROBRQIVCIQF-UHFFFAOYSA-N pyrrolo[3,2-b]pyrrole-5,6-dione Chemical compound C1=CN=C2C(=O)C(=O)N=C21 FYNROBRQIVCIQF-UHFFFAOYSA-N 0.000 description 1
- IZMJMCDDWKSTTK-UHFFFAOYSA-N quinoline yellow Chemical compound C1=CC=CC2=NC(C3C(C4=CC=CC=C4C3=O)=O)=CC=C21 IZMJMCDDWKSTTK-UHFFFAOYSA-N 0.000 description 1
- 125000005372 silanol group Chemical group 0.000 description 1
- 239000008261 styrofoam Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
Description
本発明は、筆記具用の水性顔料インキ組成物及び該インキ組成物を搭載した中綿式サインペンに関し、詳しくは、筆記した描線が耐擦過性に優れたものになる水性顔料インキ組成物及び該インキ組成物を搭載した中綿式サインペンに関する。 The present invention relates to a water-based pigment ink composition for a writing instrument and a batting-type felt-tip pen equipped with the ink composition, and more particularly, to a water-based pigment ink composition and a water-based pigment ink having a drawn line with excellent scratch resistance. A batting-type felt-tip pen equipped with an object.
いわゆるサインペンは、ペン先に繊維質を用いて、その毛細管現象によって、ペン体にあるインキ貯蔵部からインキをペン先に誘導して筆記するペンであり、インキ貯蔵部の構造の違いによって、直液式と中綿式の２種類がある。直液式は、ペン体にインキタンクが搭載され、該インキタンクにインキを直接貯蔵する様式である。このため、高粘度のインキを使用することが可能であり、筆記された描線の耐擦過性は、筆記する面の材質にもよるが、比較的良好なものになる。 A so-called felt-tip pen is a pen that uses a fiber material for the pen tip and guides the ink from the ink storage section in the pen body to the pen tip by a capillary phenomenon to write the pen. There are two types: liquid type and batting type. The direct liquid type is a type in which an ink tank is mounted on a pen body and ink is directly stored in the ink tank. For this reason, it is possible to use a high-viscosity ink, and the abrasion resistance of the drawn lines is relatively good, depending on the material of the surface to be written.
一方、中綿式は、ペン体に内蔵した綿にインキを充填し、その綿に直接、繊維質のペン先が取り付けられている構造の、綿に充填されたインキを、毛細管現象によって綿からペン先に染み込ませて筆記する様式のものである。中綿式のペンは、直液式のペンと比べて構成する部品数が少ないため、コストを低く抑えることができる。また、綿に充填されたインキをペン先に染み込ませる様式であるため、気圧の影響を受けずに筆記することができるという利点もある。しかし、中綿式のペンでは、インキ吸蔵体や繊維束状からなる部材（綿）を使用し、この綿にインキを充填しているため、直液式のペンと比べて搭載できるインキの粘度の範囲が狭く、低粘度のインキを搭載させる必要がある。このため、例えば、低粘度のインキを充填した中綿式のサインペンで、ＰＥＴフィルム等の非吸収面に筆記した場合には、十分な液量のインキが描線にのらず、乾燥後の膜厚が薄くなり、描線の耐擦過性が悪いという問題点がある。 On the other hand, in the batting type, the ink is filled into the cotton built in the pen body, and the cotton-filled ink is directly attached to the cotton. It is a style of writing soaked in first. The batting pen has a smaller number of components than the direct liquid pen, so that the cost can be reduced. In addition, since the pen is filled with ink filled with cotton, there is an advantage that writing can be performed without being affected by atmospheric pressure. However, the batting pen uses a material (cotton) made of an ink occluding body or a fiber bundle, and the cotton is filled with ink. It is necessary to mount ink with a narrow range and low viscosity. For this reason, for example, when writing on a non-absorbing surface such as a PET film with a batting-type felt-tip pen filled with low-viscosity ink, a sufficient amount of ink is not drawn on the drawing line, and the film thickness after drying is reduced. And the scratch resistance of the drawn lines is poor.
中綿式のペンにおける上記した問題点を解消するために、種々の筆記具用のインキ組成物が提案されている。例えば、着色剤、有機溶剤、樹脂及びグラフト共重合体のシリコーン系界面活性剤を含有するインキ組成物（特許文献１）や、樹脂、界面活性剤、溶剤及びクロム錯塩染料を着色剤として含有するインキ組成物（特許文献２）などが提案されている。 Various ink compositions for writing implements have been proposed in order to solve the above-mentioned problems in the batting pen. For example, an ink composition containing a colorant, an organic solvent, a resin and a silicone surfactant of a graft copolymer (Patent Document 1), or a resin, a surfactant, a solvent, and a chromium complex dye as a colorant. An ink composition (Patent Document 2) and the like have been proposed.
ここで、筆記具用のサインペンに搭載するインキには、有機溶剤を用いた油性インキと、水系の溶媒を用いた水性インキがあり、使用する着色剤の観点からは、顔料を用いた顔料インキと染料を用いた染料インキがある。これに対して、近年、より環境保全性の高い製品や、より安全性の高い製品を求める傾向が強くなってきており、優れた水性インキの提供が待望されている。また、染料インキは、高い発色性を示すものの、顔料インキに比べて耐光性に劣るという課題がある。このため、中綿式のサインペンにおいても、搭載した場合に、優れた性能を発揮できる水性の顔料インキの提供が待望されている。また、水性の顔料インキでありながら、特にＰＥＴフィルム等の非吸収面に筆記した場合に、良好なインキ皮膜を形成することができ、しかも筆記した描線が高い耐擦過性を示すものになる優れた性能のインキが得られれば極めて有用である。 Here, the ink to be mounted on the writing pen for a writing implement includes an oil-based ink using an organic solvent and a water-based ink using a water-based solvent.From the viewpoint of the colorant used, a pigment ink using a pigment is used. There is a dye ink using a dye. On the other hand, in recent years, there has been a strong tendency to seek a product with higher environmental protection and a product with higher safety, and the provision of an excellent water-based ink has been expected. In addition, although dye inks exhibit high coloring properties, they have a problem that they are inferior in light resistance as compared with pigment inks. For this reason, there is a long-awaited need to provide a water-based pigment ink that can exhibit excellent performance when mounted on a batting-type felt-tip pen. In addition, although it is a water-based pigment ink, it is possible to form a good ink film, especially when writing on a non-absorbing surface such as a PET film, and the drawn lines show high scratch resistance. It would be very useful if an ink with good performance could be obtained.
これに対し、前記した特許文献１のインキ組成物は、油性インキであり、環境上の課題がある。また、特許文献２のインキ組成物は、着色剤として染料を使用しているため、顔料を使用したインキの場合と比較して耐候性が不十分であり、更に、重金属を含む染料を使用しており、環境上の課題もある。 On the other hand, the ink composition of Patent Document 1 described above is an oil-based ink and has environmental problems. Further, since the ink composition of Patent Document 2 uses a dye as a coloring agent, it has insufficient weather resistance compared to the case of an ink using a pigment, and further uses a dye containing a heavy metal. And there are also environmental issues.
本発明は、上記した従来技術の課題に鑑みてなされたものであり、本発明の目的は、中綿式のサインペンに搭載可能な程度に低粘度の顔料インキでありながら、中綿式サインペンに搭載した際に、ＰＥＴフィルム等の非吸収面に筆記した描線が、従来のサインペンで筆記したものに比べて優れた耐擦過性を実現したものになる、水性顔料インキ組成物及び該インキ組成物を搭載した中綿式サインペンを提供することである。 The present invention has been made in view of the above-described problems of the prior art, and an object of the present invention is to install a batting-type felt-tip pen while using a low-viscosity pigment ink that can be mounted on a batting-type felt-tip pen. At the time, the drawing line written on a non-absorbing surface of a PET film or the like has an excellent abrasion resistance as compared with the one drawn with a conventional felt-tip pen, and is provided with the aqueous pigment ink composition and the ink composition. It is to provide a batting-type felt-tip pen.
上記目的は以下の本発明によって達成される。すなわち、本発明は、顔料、水、分散樹脂、シリコーン系樹脂エマルジョン及びそれ以外の樹脂エマルジョンを含有してなる筆記具用の水性顔料インキ組成物であって、前記シリコーン系樹脂エマルジョンと、前記それ以外の樹脂エマルジョンとが、その固形分の質量比が、シリコーン系樹脂エマルジョン／それ以外の樹脂エマルジョン＝０．１〜０．８の範囲内となる量で併用されており、且つ、円錐平板型回転粘度計で、２５℃、５０ｒｐｍの条件において測定したときの粘度が、２．０ｍＰａ・ｓを超えて８ｍＰａ・ｓ以下であることを特徴とする筆記具用の水性顔料インキ組成物を提供する。 The above object is achieved by the present invention described below. That is, the present invention is an aqueous pigment ink composition for a writing implement comprising a pigment, water, a dispersion resin, a silicone resin emulsion and another resin emulsion, wherein the silicone resin emulsion and the other And the resin emulsion is used in an amount such that the mass ratio of the solid content thereof is within a range of 0.1 to 0.8 of the silicone resin emulsion / other resin emulsion, and the conical flat plate type rotation is used. Provided is an aqueous pigment ink composition for a writing implement, wherein the viscosity measured at 25 ° C. and 50 rpm with a viscometer is more than 2.0 mPa · s and 8 mPa · s or less.
本発明の筆記具用の水性顔料インキ組成物の好ましい形態としては、下記のものが挙げられる。すなわち、前記それ以外の樹脂エマルジョンが、ポリウレタン系樹脂エマルジョン又はアクリル系樹脂エマルジョンの少なくともいずれかであって、且つ、その粘度が１０〜３０００ｍＰａ・ｓであること；前記それ以外の樹脂エマルジョンの含有量が、固形分換算で、２〜１８質量％であり、且つ、前記シリコーン系樹脂エマルジョンの含有量が、固形分換算で、１〜５質量％であること；顔料の含有量が、５〜１５質量％であること；前記顔料及び前記分散樹脂が、円錐平板型回転粘度計を用いて、２５℃、５０ｒｐｍの条件において測定したときの粘度が２〜５ｍＰａ・ｓである、顔料と分散樹脂とを含んでなる顔料分散液で含有されていること；が挙げられる。 Preferred embodiments of the aqueous pigment ink composition for a writing instrument of the present invention include the following. That is, the other resin emulsion is at least one of a polyurethane resin emulsion and an acrylic resin emulsion, and has a viscosity of 10 to 3000 mPa · s; the content of the other resin emulsion Is 2 to 18% by mass in terms of solid content, and the content of the silicone resin emulsion is 1 to 5% by mass in terms of solid content; the content of the pigment is 5 to 15%. % By mass; the pigment and the dispersion resin have a viscosity of 2 to 5 mPa · s when measured at 25 ° C. and 50 rpm using a conical flat plate type rotational viscometer. Is contained in a pigment dispersion liquid comprising:
また、本発明は、別の実施形態として、インキ貯蔵部材に、上記のいずれかに記載の水性顔料インキ組成物が充填されていることを特徴とする中綿式サインペンを提供する。 The present invention also provides, as another embodiment, a batting-type felt-tip pen, characterized in that an ink storage member is filled with any of the aqueous pigment ink compositions described above.
本発明によれば、中綿式のサインペンに搭載可能な程度に低粘度の顔料インキであり、しかも、中綿式サインペンに搭載した際に、例えば、ＰＥＴフィルム等の非吸収面に筆記した描線が、従来のサインペンで筆記したものに比べて優れた耐擦過性を実現したものになる、水性顔料インキ組成物及び該インキ組成物を搭載した中綿式サインペンが提供される。 According to the present invention, it is a pigment ink having a viscosity as low as it can be mounted on a batting type pens, and when mounted on a batting type pens, for example, a drawing line written on a non-absorbing surface such as a PET film, A water-based pigment ink composition and a batting-type signature pen equipped with the ink composition are provided, which achieve excellent scratch resistance as compared with those written by a conventional signature pen.
以下に、好ましい実施の形態を挙げて本発明を更に詳細に説明する。本発明者は、上記の問題を解決すべく鋭意研究を重ねた結果、少なくとも、顔料、水、分散樹脂に、シリコーン系樹脂エマルジョンに、それ以外の樹脂エマルジョンを併用し、且つ、これらの２種類の樹脂エマルジョンを特定の比率で含有させることで、中綿式サインペンに搭載可能な低粘度の水性顔料インキ組成物とでき、しかも、搭載した中綿式サインペンでＰＥＴフィルム等の非吸収面に筆記した描線が、表面の摩擦抵抗を低減することができ、耐擦過性が向上したものになることを見出して、本発明を完成するに至った。以下、本発明の水性顔料インキ組成物を構成する各材料について詳細に説明する。 Hereinafter, the present invention will be described in more detail with reference to preferred embodiments. The present inventor has conducted intensive studies to solve the above-mentioned problems. As a result, at least pigment, water, and a dispersion resin, a silicone-based resin emulsion, and other resin emulsions were used in combination, and these two types were used. By incorporating the resin emulsion in a specific ratio, a low-viscosity water-based pigment ink composition that can be mounted on a batting-type sign pen can be obtained, and the drawing line written on a non-absorbing surface such as a PET film with the mounted batting-type sign pen However, they have found that the frictional resistance of the surface can be reduced and the scratch resistance is improved, and the present invention has been completed. Hereinafter, each material constituting the aqueous pigment ink composition of the present invention will be described in detail.
＜顔料＞
本発明の水性顔料インキ組成物を構成する顔料としては、従来公知の、分散樹脂によって分散させる樹脂分散型の顔料を使用することができ、特に限定されない。例えば、カーボンブラック等の無機顔料や、溶性・不溶性アゾ顔料、高分子量アゾ顔料、フタロシアニン系顔料、キナクリドン系顔料、アントラキノン系顔料、ジオキサジン系顔料、ジケトピロロピロール顔料、キノフタロン系顔料、メチン・アゾメチン系顔料、ペリレン系顔料、ペリノン系顔料、イソインドリノン系顔料、イソインドリン系顔料等の有機顔料等が挙げられる。
<Pigment>
As the pigment constituting the aqueous pigment ink composition of the present invention, a conventionally known resin-dispersed pigment dispersed by a dispersing resin can be used, and there is no particular limitation. For example, inorganic pigments such as carbon black, soluble / insoluble azo pigments, high molecular weight azo pigments, phthalocyanine pigments, quinacridone pigments, anthraquinone pigments, dioxazine pigments, diketopyrrolopyrrole pigments, quinophthalone pigments, methine azomethine And organic pigments such as perylene pigments, perinone pigments, isoindolinone pigments, and isoindoline pigments.
本発明の水性顔料インキ組成物における顔料の含有量（顔料濃度）は、保存安定性や他の成分の溶解性との関係から、水性顔料インキ組成物の全量に対して、５〜１５質量％であることが好ましく、より好ましくは５〜１０質量％である。 The content (pigment concentration) of the pigment in the aqueous pigment ink composition of the present invention is 5 to 15% by mass based on the total amount of the aqueous pigment ink composition, from the relationship with storage stability and solubility of other components. And more preferably 5 to 10% by mass.
本発明の水性顔料インキ組成物を製造する場合、顔料及び分散樹脂を、予め、顔料を分散樹脂で、溶媒である水に高濃度で分散させた顔料分散液を使用することが好ましい。本発明者の検討によれば、顔料分散液を使用することで、水性顔料インキ組成物の粘度を安定して低くすることができ、その結果、中綿式サインペンに搭載するのに好適な低粘度の顔料インキの調製が可能になることがわかった。本発明で使用する顔料分散液における顔料濃度は、１０〜１８質量％であることが好ましく、より好ましくは１２〜１５質量％である。その際に使用する分散樹脂としては、次に挙げるようなものを適宜に使用できる。顔料分散液を調製するための水としては、イオン交換水を用いることが好ましい。 When producing the aqueous pigment ink composition of the present invention, it is preferable to use a pigment dispersion in which the pigment and the dispersing resin are previously dispersed in a high concentration in water as a solvent with the dispersing resin. According to the study of the present inventors, by using a pigment dispersion, the viscosity of the aqueous pigment ink composition can be stably reduced, and as a result, a low viscosity suitable for mounting on a batting type felt pen It was found that the preparation of the pigment ink of Example 1 was possible. The pigment concentration in the pigment dispersion used in the present invention is preferably from 10 to 18% by mass, and more preferably from 12 to 15% by mass. As the dispersing resin used at that time, the following resins can be appropriately used. As the water for preparing the pigment dispersion, it is preferable to use ion-exchanged water.
また、本発明者の検討によれば、特に、円錐平板型回転粘度計を用いて、２５℃、５０ｒｐｍの条件において測定したときの粘度が２〜５ｍＰａ・ｓと低粘度である顔料分散液を用いることで、より良好な水性顔料インキ組成物とすることができる。 According to the study of the present inventor, in particular, a pigment dispersion having a low viscosity of 2 to 5 mPa · s when measured at 25 ° C. and 50 rpm using a conical flat plate type rotary viscometer is used. By using it, a better aqueous pigment ink composition can be obtained.
＜分散樹脂＞
本発明の水性顔料インキ組成物は、上記したように、分散樹脂を用いて前記したような顔料を、予め溶媒である水に分散させた顔料分散液を用いたことにより、本発明の水性顔料インキ組成物の粘度を低粘度化することができる。本発明者の検討によれば、更に、分散樹脂を用いることで、経時での粘度も低く保つことができ、水性顔料インキ組成物の保存安定性をよくすることができることがわかった。
<Dispersion resin>
As described above, the aqueous pigment ink composition of the present invention uses the pigment dispersion obtained by previously dispersing the above-described pigment using a dispersing resin in water as a solvent, thereby obtaining the aqueous pigment of the present invention. The viscosity of the ink composition can be reduced. According to the study of the present inventor, it was further found that by using a dispersing resin, the viscosity over time can be kept low, and the storage stability of the aqueous pigment ink composition can be improved.
一般的に、顔料を分散するための分散樹脂の構造は、顔料吸着に寄与する顔料吸着部と溶媒に親和して分散性に寄与する溶媒親和性部からなる。その構造中の溶媒親和性部の分子鎖が長いと、顔料同士の立体的反発が大きくなるため、分散安定性がよくなる傾向がある。しかし、その一方で、分散樹脂自体の粘度が高くなり、結果としてインキ組成物の粘度が高くなる傾向がある。これに対し、その構造中の溶媒親和性部の分子鎖が短いと、分散樹脂自体の粘度は低くなるが、顔料同士の立体的反発が小さくなり、顔料の分散性が悪くなる傾向がある。本発明を構成する分散樹脂は、これらの点を考慮して選択することが好ましい。 Generally, the structure of a dispersion resin for dispersing a pigment is composed of a pigment adsorbing portion contributing to pigment adsorption and a solvent affinity portion contributing to the solvent and contributing to dispersibility. When the molecular chain of the solvent affinity portion in the structure is long, the steric repulsion between the pigments increases, and the dispersion stability tends to be improved. However, on the other hand, the viscosity of the dispersion resin itself increases, and as a result, the viscosity of the ink composition tends to increase. On the other hand, if the molecular chain of the solvent affinity portion in the structure is short, the viscosity of the dispersion resin itself is low, but the steric repulsion between the pigments is small, and the dispersibility of the pigment tends to be poor. It is preferable that the dispersion resin constituting the present invention is selected in consideration of these points.
本発明で使用する分散樹脂の構造中の顔料吸着部としては、分散対象の顔料の表面性状に適宜に設計すればよく、特に限定はない。例えば、形成材料のモノマーに、メタクリル酸（ＭＡＡ）やアクリル酸（ＡＡｃ）などの酸性基を含有するモノマーが含まれていることが好ましい。また、水中で顔料を分散させるためには、これらの酸性基は、アンモニア、水酸化カリウム、水酸化ナトリウムなどの塩基で中和されている必要がある。 The pigment adsorption portion in the structure of the dispersion resin used in the present invention may be appropriately designed according to the surface properties of the pigment to be dispersed, and is not particularly limited. For example, it is preferable that the monomer of the forming material contains a monomer having an acidic group such as methacrylic acid (MAA) or acrylic acid (AAc). Further, in order to disperse the pigment in water, these acidic groups need to be neutralized with a base such as ammonia, potassium hydroxide, and sodium hydroxide.
本発明で使用する分散樹脂の構造中の顔料吸着部以外の部分も、上記に挙げた顔料吸着部との兼ね合いで適宜に設計すればよく、特に限定はない。例えば、形成材料のモノマーに、メタクリル酸メチル（ＭＭＡ）、メタクリル酸ベンジル、メタクリル酸ヒドロキシエチル（ＨＥＭＡ）、メタクリル酸エチル（ＥＭＡ）、メタクリル酸２−エチルヘキシル（２ｅｈＭＡ）等のメタクリレート系のモノマーや、アクリル酸メチル、アクリル酸ベンジル、アクリル酸ヒドロキシエチル、アクリル酸エチル等のアクリレート系のモノマーや、スチレン（Ｓｔ）等の付加重合性モノマーを用いることができる。 The portion other than the pigment adsorption portion in the structure of the dispersion resin used in the present invention may be appropriately designed in consideration of the above-described pigment adsorption portion, and is not particularly limited. For example, methacrylate monomers such as methyl methacrylate (MMA), benzyl methacrylate, hydroxyethyl methacrylate (HEMA), ethyl methacrylate (EMA), 2-ethylhexyl methacrylate (2ehMA), Acrylic monomers such as methyl acrylate, benzyl acrylate, hydroxyethyl acrylate, and ethyl acrylate, and addition polymerizable monomers such as styrene (St) can be used.
本発明に用いられる分散樹脂の構造は、ランダム構造、グラフト構造、ブロック構造、スター構造など特に限定されるものではなく、種々の構造のものを用いることができる。中でもランダム構造やブロック構造のものが好ましい。 The structure of the dispersion resin used in the present invention is not particularly limited, such as a random structure, a graft structure, a block structure, and a star structure, and various structures can be used. Among them, those having a random structure or a block structure are preferable.
本発明を構成する分散樹脂の数平均分子量は、５０００〜２５０００程度のものであることが好ましく、より好ましくは１００００〜２００００のものである。数平均分子量が５０００未満では、顔料同士の立体的反発が小さくなり、顔料同士が凝集してしまい、顔料分散液の粘度が高くなるため好ましくない。一方、数平均分子量が２５０００を超えると、分散樹脂自体の粘度が高くなり、顔料分散液の粘度が高くなってしまうため、好ましくない。 The number average molecular weight of the dispersion resin constituting the present invention is preferably about 5,000 to 25,000, more preferably 10,000 to 20,000. If the number average molecular weight is less than 5,000, the steric repulsion between the pigments becomes small, the pigments aggregate, and the viscosity of the pigment dispersion becomes undesirably high. On the other hand, if the number average molecular weight exceeds 25,000, the viscosity of the dispersion resin itself increases, and the viscosity of the pigment dispersion increases, which is not preferable.
本発明の水性顔料インキ組成物を、上記したような顔料分散液を用いて調製する場合には、上記したような構成の分散樹脂を、アルカリによって中和して用いる。この際に、中和するために用いられるアルカリとしては、特に限定されないが、例えば、アンモニア、第一級、第二級又は第三級等の有機アミン（塩基性含窒素複素環化合物を含む）や、水酸化アルカリ金属等の化合物が挙げられる。これらは、単独で又は２種以上を組み合わせて用いることができる。 When the aqueous pigment ink composition of the present invention is prepared using the above-described pigment dispersion, the dispersion resin having the above-described configuration is used after being neutralized with an alkali. At this time, the alkali used for neutralization is not particularly limited, but for example, ammonia, organic amines such as primary, secondary and tertiary (including basic nitrogen-containing heterocyclic compounds) And compounds such as alkali metal hydroxides. These can be used alone or in combination of two or more.
＜シリコーン系樹脂エマルジョン＞
本発明の水性顔料インキ組成物は、上記した顔料分散液に、シリコーン系樹脂エマルジョンと、それ以外の樹脂エマルジョンとを、特定割合で併用して含有させた構成としたことを特徴とする。特に、シリコーン系樹脂エマルジョンを併用したことで、良好なインキ皮膜が形成され、その耐擦過性が極めて良好になるという新たな知見を得て、本発明を達成した。本発明でいう「シリコーン系樹脂エマルジョン」とは、樹脂骨格にポリシロキサン骨格を有する樹脂エマルジョンのことを意味する。本発明者の検討によれば、シリコーン系樹脂エマルジョンは、粘度が高いものが多いものの、粘度の低い、シリコーン系樹脂エマルジョン以外の樹脂エマルジョンを併用し、且つ、その固形分の質量比が、シリコーン系樹脂エマルジョン／それ以外の樹脂エマルジョン＝０．１〜０．８の範囲内、より好ましくは、シリコーン系樹脂エマルジョン／それ以外の樹脂エマルジョン＝０．１〜０．５となるように構成したことで、本発明の顕著な効果を達成している。
<Silicone resin emulsion>
The water-based pigment ink composition of the present invention is characterized in that the above-mentioned pigment dispersion liquid contains a silicone resin emulsion and another resin emulsion in combination at a specific ratio. In particular, the present inventors have obtained a new finding that a good ink film is formed by using a silicone-based resin emulsion in combination, and the rub resistance is extremely good, thereby achieving the present invention. The “silicone resin emulsion” in the present invention means a resin emulsion having a polysiloxane skeleton in the resin skeleton. According to the study of the present inventors, silicone-based resin emulsions often have a high viscosity, but have a low viscosity, a resin emulsion other than the silicone-based resin emulsion is used in combination, and the mass ratio of the solid content is silicone. Resin resin emulsion / other resin emulsion = 0.1 to 0.8, more preferably silicone resin emulsion / other resin emulsion = 0.1 to 0.5 Thus, the remarkable effects of the present invention are achieved.
すなわち、シリコーン系樹脂エマルジョンと、それ以外の樹脂エマルジョンの２種類のエマルジョンを併用してなる本発明の水性顔料インキ組成物は、中綿式のサインペンに搭載させることができる程度に低粘度になる。更に、このサインペンで描線等を筆記した際に、形成するインキ皮膜の摩擦抵抗を低減してスリップ性を与え、耐摩擦性を向上させたものになる。本発明の水性顔料インキ組成物を構成するシリコーン系樹脂エマルジョンのインキ中における含有量は、好ましくは、水性顔料インキ組成物の全量に対して固形分換算で１〜５質量％程度、より好ましくは１〜３質量％程度であればよく、この程度の範囲内で使用することで、筆記具用である本発明の水性顔料インキ組成物を、より安定して低粘度化することができる。 That is, the water-based pigment ink composition of the present invention, which comprises two types of emulsions, a silicone-based resin emulsion and another resin emulsion, has a low viscosity so that it can be mounted on a batting-type sign pen. Furthermore, when drawing lines and the like are written with this felt-tip pen, the frictional resistance of the ink film to be formed is reduced to provide slip properties, and the friction resistance is improved. The content of the silicone resin emulsion constituting the aqueous pigment ink composition of the present invention in the ink is preferably about 1 to 5% by mass in terms of solid content based on the total amount of the aqueous pigment ink composition, more preferably The amount may be about 1 to 3% by mass, and by using the amount in this range, the viscosity of the aqueous pigment ink composition of the present invention for a writing instrument can be reduced more stably.
本発明を構成するシリコーン系樹脂エマルジョンには、下記に挙げるような市販品を適宜に使用することができる。具体的には、例えば、アクリルエマルジョンを、ポリシロキサン骨格を有するオリゴマーで複合化したＮＡＮＯＦＩＮＥ ＫＰＸ−０２−０１４、ＮＡＮＯＦＩＮＥ ＫＰＸ−９７−０４８及びＮＡＮＯＦＩＮＥ ＫＰＸ−９７−０５１（以上、商品名、トーヨーケム社〔旧：東洋インキ製造社）製〕等や、シラノール基を持ったシリコーンのエマルジョンである５２Ａｄｄｉｔｉｖｅや、ＢＹ２２−０５０Ａ（以上、商品名、東レ・ダウコーニング社製）、ノニオン系エマルジョンであるＸ−５２−２１６０（信越化学工業社製）、レオフローＤＭＳ−５５（ライオン社製）等が挙げられる。 As the silicone resin emulsion constituting the present invention, commercially available products listed below can be appropriately used. Specifically, for example, NANOFINE KPX-02-014, NANOFINE KPX-97-048 and NANOFINE KPX-97-051 in which an acrylic emulsion is complexed with an oligomer having a polysiloxane skeleton (the above are trade names, manufactured by Toyochem Co., Ltd.) Old: Toyo Ink Mfg. Co., Ltd.), 52Additive which is a silicone emulsion having a silanol group, BY22-050A (both trade names, manufactured by Dow Corning Toray), and X-52 which is a nonionic emulsion. -2160 (manufactured by Shin-Etsu Chemical Co., Ltd.) and Leoflow DMS-55 (manufactured by Lion Corporation).
＜それ以外の樹脂エマルジョン＞
上記したように、本発明の水性顔料インキ組成物は、先に述べたように、上記したシリコーン系樹脂エマルジョンと、それ以外の樹脂エマルジョンとを併用し、これらが特定割合で含有されているように構成したことを特徴する。すなわち、本発明は、中綿式のサインペンに搭載可能な低粘度のインキの開発を一つの目的としており、本発明の水性顔料インキ組成物では、この目的を、それ以外の樹脂エマルジョンを併用してインキに含有したことで達成している。その際に用いる、バインダーとして機能するそれ以外の樹脂エマルジョン（以下、単に「樹脂エマルジョン」とも呼ぶ）は、インキ皮膜の成膜性を確保することに加えて、前記した形成したシリコーン系樹脂エマルジョンと併用することで、描線の耐擦過性を向上させること及びインクの経時安定性に寄与するため、比較的低粘度の樹脂エマルジョンを使用することが好ましい。
<Other resin emulsions>
As described above, the aqueous pigment ink composition of the present invention, as described above, uses the above-mentioned silicone-based resin emulsion and other resin emulsions in combination, and these are contained in a specific ratio. It is characterized by having comprised in. That is, one object of the present invention is to develop a low-viscosity ink that can be mounted on a batting-type felt-tip pen. In the aqueous pigment ink composition of the present invention, this object is achieved by using another resin emulsion in combination. Achieved by inclusion in ink. The other resin emulsion that functions as a binder used at that time (hereinafter, also simply referred to as “resin emulsion”) is, in addition to ensuring the film formability of the ink film, combined with the silicone resin emulsion formed above. When used in combination, a resin emulsion having a relatively low viscosity is preferably used because it contributes to improving the scratch resistance of drawn lines and to the stability over time of the ink.
本発明者の検討によれば、本発明で使用する樹脂エマルジョンは、上記した目的から、好ましくは１０〜３０００ｍＰａ・ｓ、より好ましくは１０００ｍＰａ・ｓ以下、更に好ましくは１００ｍＰａ・ｓ以下、の低粘度のものを使用するとよい。本発明において特に好適に用いられる樹脂エマルジョンとしては、アクリル系樹脂エマルジョンやポリウレタン系樹脂エマルジョン等が挙げられ、中でもポリウレタン系樹脂エマルジョンがより好適に用いられる。 According to the study of the present inventors, the resin emulsion used in the present invention has a low viscosity of preferably 10 to 3000 mPa · s, more preferably 1000 mPa · s or less, and still more preferably 100 mPa · s or less, for the above-described purpose. It is better to use The resin emulsion particularly preferably used in the present invention includes an acrylic resin emulsion and a polyurethane resin emulsion, among which a polyurethane resin emulsion is more preferably used.
また、本発明の水性顔料インキ組成物を構成する樹脂エマルジョンは、その最低造膜温度（ＭＦＴ）が２５℃（室温）以下の、室温で成膜するものであることが好ましい。すなわち、本発明者の検討によれば、バインダーとして機能する樹脂エマルジョンに、ＭＦＴが室温以下のものを用いることで、成膜性に優れた水性顔料インキ組成物になり、結果として、筆記した描線の耐擦過性がより優れたものになる中綿式サインペンの提供が可能となる。このため、本発明を構成する樹脂エマルジョンに、ＭＦＴが高めの材料を使用する場合は、造膜助剤等を併用して、水性顔料インキ組成物のＭＦＴが２５℃以下となるように設計することが好ましい。 In addition, the resin emulsion constituting the aqueous pigment ink composition of the present invention is preferably one that forms a film at room temperature with a minimum film formation temperature (MFT) of 25 ° C. (room temperature) or less. That is, according to the study of the present inventor, the use of a resin emulsion that functions as a binder and a resin emulsion having an MFT of room temperature or lower results in an aqueous pigment ink composition having excellent film formability. It is possible to provide a batting-type felt-tip pen in which the scratch resistance is more excellent. For this reason, when a material having a high MFT is used for the resin emulsion constituting the present invention, a water-based pigment ink composition is designed so that the MFT of the aqueous pigment ink composition is 25 ° C. or lower by using a film-forming aid or the like in combination. Is preferred.
なお、本発明で用いる「エマルジョン」は、液体（水）に、粒径の小さい液体（樹脂）が分散したものを意味し、水性重合体（樹脂）の水分散液（ディスパージョン）と呼ばれるものも含む。２種類のエマルジョンのいずれのものについても、乳化剤（界面活性剤）を用いて乳化したものであっても、乳化剤（界面活性剤）を用いずに自己乳化させたものであってもよい。 The "emulsion" used in the present invention means a liquid (water) in which a liquid (resin) having a small particle size is dispersed, and is called an aqueous dispersion (dispersion) of an aqueous polymer (resin). Including. Any of the two types of emulsions may be emulsified using an emulsifier (surfactant) or self-emulsified without using an emulsifier (surfactant).
本発明の水性顔料インキ組成物における、樹脂エマルジョンの配合量は、水性顔料インキ組成物の全量に対して、固形分換算で２〜１８質量％であることが好ましい。樹脂エマルジョンの配合量が２質量％未満であると、少な過ぎてインキ皮膜の形成が難しくなり、１８質量％を超えると、インキ中の樹脂分が多くなりすぎて、本発明の水性顔料インキ組成物の粘度が増大し過ぎてしまい、中綿式のサインペンへの搭載に適さなくなるため、好ましくない。 The amount of the resin emulsion in the aqueous pigment ink composition of the present invention is preferably 2 to 18% by mass in terms of solid content based on the total amount of the aqueous pigment ink composition. If the amount of the resin emulsion is less than 2% by mass, the amount of the resin pigment in the ink is too large, and if the amount is more than 18% by mass, the resin content in the ink becomes too large. It is not preferable because the viscosity of the product becomes too high, which makes the product unsuitable for mounting on a batting type felt pen.
本発明を構成するシリコーン系樹脂エマルジョン以外の樹脂エマルジョンとしては、例えば、以下に挙げるような市販品等を適宜に使用することができる。アクリル系樹脂エマルジョンとしては、主成分がアクリル−スチレン共重合体であるボンコートＮＳＴ−１００ＥＦ（商品名、ＤＩＣ社製、Ｔｇ：１７℃、ＭＦＴ：１３℃）や、アクリル樹脂の水中油型エマルジョンであるサイビノールＳＫ−２００（商品名、サイデン化学社製、ＭＦＴ：８０℃以上）や、スチレン−アクリル酸共重合物であるジョンクリル １５３５（商品名、ＢＡＳＦ社製）等を使用することができる。 As the resin emulsion other than the silicone-based resin emulsion constituting the present invention, for example, the following commercial products can be appropriately used. Examples of the acrylic resin emulsion include Boncoat NST-100EF (trade name, manufactured by DIC, Tg: 17 ° C., MFT: 13 ° C.) whose main component is an acrylic-styrene copolymer, and an oil-in-water emulsion of an acrylic resin. Certain Cybinol SK-200 (trade name, manufactured by Seiden Chemical Co., MFT: 80 ° C. or more), styrene-acrylic acid copolymer Joncryl 1535 (trade name, manufactured by BASF) and the like can be used.
また、ポリウレタン系樹脂エマルジョンとしては、ポリカーボネートポリウレタンの水分散液である、バイヒドロール（登録商標）ＵＨ２６０６（住化バイエルウレタン社製、不揮発分３５％、ＭＦＴ：４５℃）や、主成分がアクリル変性ウレタンである、アニオン性ポリウレタン樹脂のリカボンドＳＵ−１００Ｎ〔商品名、ジャパンコーティングレジン社（旧：中央理化工業社）製、Ｔｇ：６０℃〕等を使用することができる。 Examples of the polyurethane resin emulsion include an aqueous dispersion of polycarbonate polyurethane such as Bihydrol (registered trademark) UH2606 (manufactured by Sumika Bayer Urethane Co., Ltd., nonvolatile content: 35%, MFT: 45 ° C.), and acrylic-modified urethane whose main component is acrylic-modified urethane. Likabond SU-100N of an anionic polyurethane resin (trade name, manufactured by Japan Coating Resin Co., Ltd. (former: Chuo Rika Kogyo Co., Ltd.), Tg: 60 ° C.) can be used.
＜その他の添加剤＞
本発明の水性顔料インキ組成物は、必要に応じて、下記に挙げるような、造膜助剤、乾燥防止剤及び濡れ剤といった添加剤を用いることができる。これらに限らず、後述するような添加剤も使用することができる。いずれの添加剤も、必要に応じて、１種又は２種以上を混合して用いることができる。
<Other additives>
In the aqueous pigment ink composition of the present invention, additives such as a film-forming aid, a drying inhibitor and a wetting agent as described below can be used as necessary. Not limited to these, additives as described below can also be used. Any of these additives can be used alone or in combination of two or more as necessary.
（造膜助剤）
本発明の水性顔料インキ組成物において、造膜助剤を使用することで、該組成物中のエマルジョンの塗膜形成性を高めることができる。先述したように、造膜助剤を用い、本発明の水性顔料インキ組成物の構成を、確実に、ＭＦＴが２５℃（室温）以下である、室温でバインダー樹脂が成膜するように設計することが好ましい。すなわち、このように構成すれば、形成した塗膜は、耐擦過性に優れたものになり、中綿式のサインペンに使用した場合には、記載した描線も耐擦過性に優れたものとなる。造膜助剤としては、例えば、ベンジルアルコール、３−メトキシ−３−メチルブタノール、ヘキシレングリコール、ジエチレングリコール−モノ−ｎ−ブチルエーテル、ブチルセロソルブアセテート、ジエチレングリコール−モノ−エチルエーテル、ブチルカルビトール、エチルセロソルブ、カルビトールアセテート、ブチルカルビトールアセテート、ブチルセロソルブ、エチレングリコール−モノ−ｎ−エチルエーテル、エチレングリコール−モノ−ｎ−ブチルエーテル、エチレングリコールメチルエーテルアセテート等が挙げられる。
(Film forming aid)
In the aqueous pigment ink composition of the present invention, the use of a film-forming aid can enhance the film-forming properties of the emulsion in the composition. As described above, the composition of the aqueous pigment ink composition of the present invention is designed so that the MFT is 25 ° C. (room temperature) or less and the binder resin is formed at room temperature using the film-forming aid. Is preferred. That is, with such a configuration, the formed coating film has excellent scratch resistance, and when used for a batting-type felt-tip pen, the drawn line also has excellent scratch resistance. Examples of the film-forming aid include benzyl alcohol, 3-methoxy-3-methylbutanol, hexylene glycol, diethylene glycol-mono-n-butyl ether, butyl cellosolve acetate, diethylene glycol-mono-ethyl ether, butyl carbitol, ethyl cellosolve, Examples thereof include carbitol acetate, butyl carbitol acetate, butyl cellosolve, ethylene glycol-mono-n-ethyl ether, ethylene glycol-mono-n-butyl ether, and ethylene glycol methyl ether acetate.
（乾燥防止剤）
本発明の水性顔料インキ組成物は、特に、インキ貯蔵部材を有する中綿式のサインペンに用いるのに優れている。インキ吸蔵部材である綿等に染み込ませたインキが乾燥するのを防止するためには、本発明の水性顔料インキ組成物中に、乾燥防止剤として、親水性溶剤を存在させておくのが好ましい。この際に用いる乾燥防止剤としては、例えば、ポリオキシエチレンソルビタン脂肪酸エステル、ポリオキシエチレンソルビット脂肪酸エステル、尿素、チオ尿素、エチレン尿素又はそれらの誘導体、エチレングリコール、ポリエチレングリコール、グリセリン、プロピレングリコール、ジエチレングリコール、エチレングリコールモノフェニルエーテル、プロピレングリコールモノフェニルエーテル、ジプロピレングリコールモノメチルエーテル、ジプロピレングリコールモノブチルエーテル、トリプロピレングリコールモノエチルエーテル等が挙げられる。これらは、単独で又は２種以上を組み合わせて用いることができる。
(Anti-drying agent)
The aqueous pigment ink composition of the present invention is particularly excellent for use in a batting type felt pen having an ink storage member. In order to prevent the ink impregnated in cotton or the like, which is an ink storage member, from drying out, it is preferable that a hydrophilic solvent is present as a drying inhibitor in the aqueous pigment ink composition of the present invention. . Examples of the anti-drying agent used in this case include polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbite fatty acid ester, urea, thiourea, ethylene urea or derivatives thereof, ethylene glycol, polyethylene glycol, glycerin, propylene glycol, and diethylene glycol. , Ethylene glycol monophenyl ether, propylene glycol monophenyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monobutyl ether, tripropylene glycol monoethyl ether and the like. These can be used alone or in combination of two or more.
（濡れ剤）
また、本発明の水性顔料インキ組成物に濡れ剤を併用することで、特に、中綿式のサインペンに用いた場合には、滑らかな描線を記載できるため好ましい。濡れ剤としては、フッ素系界面活性剤や、ポリエーテル変性シロキサン等を用いることができる。フッ素系界面活性剤としては、例えば、フロラードＦＣ−４３０、４３１（以上、住友スリーエム社製）、メガファックＦ−４４４、４７２、４７７、５５２、５５３、５５４、４４３、４７０、４７５、４８２、４８３、４８９、３０（以上、ＤＩＣ社製）、アサヒガードＡＧ７１０、サーフロンＳ−３８２、ＳＣ−１０１、ＳＣ−１０２、ＳＣ−１０３、ＳＣ−１０４、ＳＣ−１０５、ＳＣ−１０６（以上、旭硝子社製）を挙げることができる。ポリエーテル変性シロキサン系界面活性剤としては、例えば、ＢＹＫ−３４５、ＢＹＫ−３４６、ＢＹＫ−３４７、ＢＹＫ−３４８、ＵＶ３５３０（以上、ビックケミー・ジャパン社製）等を挙げることができる。
(Wetting agent)
In addition, it is preferable to use a wetting agent in combination with the aqueous pigment ink composition of the present invention, particularly when used for a batting-type felt pen, since a smooth drawing line can be described. As the wetting agent, a fluorine-based surfactant, a polyether-modified siloxane, or the like can be used. Examples of the fluorinated surfactant include Florad FC-430, 431 (all manufactured by Sumitomo 3M), Megafac F-444, 472, 477, 552, 553, 554, 443, 470, 475, 482, 483. , 489, 30 (all manufactured by DIC), Asahi Guard AG710, Surflon S-382, SC-101, SC-102, SC-103, SC-104, SC-105, SC-106 (all manufactured by Asahi Glass Co., Ltd.) ). The polyether-modified siloxane-based surfactants, for example, BYK-345, BYK-346 , BYK-347, BYK-348, UV3530 ( manufactured by bit click Chemie Japan KK), and the like.
（その他）
本発明の水性顔料インキ組成物には、防腐剤、防黴剤、消泡剤、防錆剤、ｐＨ調整剤等の添加剤を、必要に応じて、１種又は２種以上を混合して用いることもできる。
(Other)
The aqueous pigment ink composition of the present invention may contain additives such as a preservative, a fungicide, an antifoaming agent, a rust inhibitor, and a pH adjuster, if necessary, by mixing one or more kinds. It can also be used.
＜用途＞
本発明の水性顔料インキ組成物は、筆記具用のインキであり、例えば、低粘度のインキが要求される中綿式のサインペンに搭載することができる。特に、中綿式のサインペンに搭載した場合に、前述したように、筆記した描線は、従来のペンに比べて格段に耐擦過性に優れたものになる。
<Application>
The aqueous pigment ink composition of the present invention is an ink for writing implements, and can be mounted, for example, on a batting-type felt-tip pen that requires a low-viscosity ink. In particular, when the pen is mounted on a batting-type felt-tip pen, as described above, the drawn lines are much more excellent in abrasion resistance than the conventional pen.
（中綿式サインペン）
本発明の水性顔料インキ組成物を搭載した中綿式サインペンは、サインペン自体の形状については特に限定されるものでなく、従来と同様のものが使用できる。例えば、ペン体である軸筒内部に収容したインキ吸蔵部材としては、従来公知の、綿や繊維束からなる部材が使用できる。インキ吸蔵部材に直接取り付けられるペン先も、従来公知の、繊維チップ、フェルトチップ、プラスチックチップ等が使用できる。本発明の水性顔料インキ組成物をインキ吸蔵部材に充填した中綿式のサインペンは、ＰＥＴフィルムの他、ガラス、金属表面等の非吸収面に筆記した場合は勿論、皮革製品、発泡スチロール、紙等にも筆記でき、筆記文字は、耐擦過性に優れたものとなる。
(Batting type felt pen)
The batting-type felt-tip pens on which the aqueous pigment ink composition of the present invention is mounted are not particularly limited in the shape of the felt-tip pens themselves, and those similar to conventional ones can be used. For example, a conventionally known member made of cotton or a fiber bundle can be used as the ink occluding member housed in the shaft cylinder which is a pen body. As the pen tip directly attached to the ink occluding member, a conventionally known fiber tip, felt tip, plastic tip, or the like can be used. The batting-type felt-tip pens filled with the aqueous pigment ink composition of the present invention in the ink occluding member may be used not only for PET films, but also for writing on non-absorbing surfaces such as glass and metal surfaces, as well as leather products, styrofoam, and paper. Can be written, and the written characters have excellent scratch resistance.
次に、実施例、比較例及び参考例を挙げて、本発明を更に具体的に説明する。なお、文中「部」及び「％」とあるのは、いずれも質量基準である。 Next, the present invention will be described more specifically with reference to Examples, Comparative Examples, and Reference Examples. In the following description, “parts” and “%” are based on mass.
実施例及び比較例では、分散樹脂に、以下のモノマー組成よりなる、重量平均分子量が２５０００である、スチレン−メタクリル酸コポリマーを、下記の溶媒を用いて溶液として用いた。以下、これを「分散樹脂溶液」と呼ぶ。 In Examples and Comparative Examples, a styrene-methacrylic acid copolymer having the following monomer composition and having a weight average molecular weight of 25,000 was used as a dispersion resin as a solution by using the following solvent. Hereinafter, this is referred to as “dispersed resin solution”.
（分散樹脂溶液）
・モノマー組成：スチレン（Ｓｔ）／メタクリル酸メチル（ＭＭＡ）／メタクリル酸エチル（ＥＭＡ）／メタクリル酸２−エチルヘキシル（２ｅｈＭＡ）／メタクリル酸ヒドロキシエチル（ＨＥＭＡ）／メタクリル酸（ＭＡＡ）＝２０／１５／１５／２０／２０／１０
・溶媒：全体のモノマー１００質量部に対して、ジエチレングリコールモノノルマルブチルエーテル／プロピレングリコールメチルエーテル／水／アンモニア水（２８％）＝５０／５０／７０／７．７の混合溶媒
・ｐＨ：８．３〜９．３
・固形分：３６％
(Dispersed resin solution)
Monomer composition: styrene (St) / methyl methacrylate (MMA) / ethyl methacrylate (EMA) / 2-ethylhexyl methacrylate (2ehMA) / hydroxyethyl methacrylate (HEMA) / methacrylic acid (MAA) = 20/15 / 15/20/20/10
Solvent: A mixed solvent of diethylene glycol mono-n-butyl ether / propylene glycol methyl ether / water / aqueous ammonia (28%) = 50/50/70 / 7.7 based on 100 parts by mass of the whole monomers. PH: 8.3 ~ 9.3
・ Solid content: 36%
＜実施例１＞
前記した分散樹脂溶液を１１４部、カーボンブラック＃１０００（商品名、三菱化学社製）を７９部、２５％のアンモニア水１．９部及びイオン交換水１８７部を、横型メディア分散機の、ＤＹＮＯ−ＭＩＬＬ Ｔｙｐ ＫＤＬ型（商品名、ＷＡＢ社製）を使用して分散を行なった。分散後、水を加え、遠心分離により粗大粒子を除去し、顔料濃度１４％の水性顔料分散液Ａを得た。この水性顔料分散液Ａの不揮発分（Ｎ．Ｖ＝固形分）は、１７．５％であり、円錐平板型回転粘度計を用い、２５℃、５０ｒｐｍの条件において測定したときの粘度は、２．４〜２．９ｍＰａ・ｓであった。また、上記で使用した市販のカーボンブラック＃１０００は、粒子径１８ｎｍ、窒素吸着比表面積１８０ｍ2／ｇ、ｐＨ３．５のものである。
<Example 1>
114 parts of the above-mentioned dispersed resin solution, 79 parts of carbon black # 1000 (trade name, manufactured by Mitsubishi Chemical Corporation), 1.9 parts of 25% ammonia water and 187 parts of ion-exchanged water were added to a DYNO horizontal media dispersing machine. -Dispersion was performed using MILL Type KDL type (trade name, manufactured by WAB). After the dispersion, water was added, and coarse particles were removed by centrifugation to obtain an aqueous pigment dispersion A having a pigment concentration of 14%. The non-volatile content (NV = solid content) of the aqueous pigment dispersion A is 17.5%, and the viscosity measured at 25 ° C. and 50 rpm using a conical plate type viscometer is 2%. 0.4 to 2.9 mPa · s. The commercially available carbon black # 1000 used above has a particle diameter of 18 nm, a nitrogen adsorption specific surface area of 180 m 2 / g, and a pH of 3.5.
次いで、上記で得た水性顔料分散液Ａの５５．４部に、ポリウレタン系樹脂エマルジョンとして、バイヒドロール（登録商標）ＵＨ２６０６（住化バイエルウレタン社製）を４０部（樹脂分＝１４部）、造膜助剤としてソルフィット（登録商標、クラレ社製）を１部、乾燥防止剤としてプロピレングリコール（ＰＧ）を０．５部、シリコーン系樹脂エマルジョンとして、５２Ａｄｄｉｔｉｖｅ（商品名、東レ・ダウコーニング社製、不揮発分６４％）を３部、及び、濡れ剤としてフッ素系界面活性剤であるメガファック（登録商標）Ｆ−４４４（ＤＩＣ社製）を０．１部加えて、本実施例のインキの配合とした。更に、この配合物を、ディゾルバーで分散して本実施例の水性顔料インキ組成物を得た。表１に、得られた水性顔料インキ組成物の組成を示した。上記で使用したポリウレタン樹脂エマルジョンの粘度は、１００ｍＰａ・ｓ未満であり、低粘度であった。また、シリコーン樹脂エマルジョンの粘度は、３０００〜５０００ｍＰａ・ｓであった。後述する表３に示したように、本実施例の水性顔料インキ組成物の粘度は、５．６ｍＰａ・ｓと低粘度であった。 Next, 40 parts (resin content = 14 parts) of Bihydrol (registered trademark) UH2606 (manufactured by Sumika Bayer Urethane Co., Ltd.) was prepared as a polyurethane resin emulsion in 55.4 parts of the aqueous pigment dispersion A obtained above. 1 part of Solfit (registered trademark, manufactured by Kuraray Co., Ltd.) as a film aid, 0.5 part of propylene glycol (PG) as a drying inhibitor, and 52Addive (trade name, manufactured by Dow Corning Toray Co., Ltd.) as a silicone resin emulsion , A nonvolatile content of 64%) and 0.1 part of Megafac (registered trademark) F-444 (manufactured by DIC) as a wetting agent as a wetting agent. It was blended. Further, this composition was dispersed with a dissolver to obtain an aqueous pigment ink composition of this example. Table 1 shows the composition of the obtained water-based pigment ink composition. The viscosity of the polyurethane resin emulsion used above was less than 100 mPa · s and was low. In addition, the viscosity of the silicone resin emulsion was 3000 to 5000 mPa · s. As shown in Table 3 below, the viscosity of the aqueous pigment ink composition of this example was as low as 5.6 mPa · s.
表１中に、使用したシリコーン系樹脂エマルジョンと、ポリウレタン系樹脂エマルジョンとを、その固形分の質量比である、シリコーン系樹脂エマルジョン／ポリウレタン系樹脂エマルジョンの値を、２種のエマルジョン比として記載した。 In Table 1, the values of the silicone resin emulsion / polyurethane resin emulsion, which is the mass ratio of the solid content of the silicone resin emulsion and the polyurethane resin emulsion used, are described as two types of emulsion ratios. .
＜実施例２〜６＞
実施例１の配合物を表１に示す配合としたこと以外は実施例１と同様にして、各実施例の水性顔料インキ組成物を得た。
<Examples 2 to 6>
A water-based pigment ink composition of each example was obtained in the same manner as in Example 1 except that the composition of Example 1 was changed to the composition shown in Table 1.
＜実施例７＞
前記した分散樹脂溶液を１１４部、シアニンブルークロモファインブルー Ａ−２２０ＪＣ（商品名、大日精化工業社製）を７９部、２５％のアンモニア水１．９部及びイオン交換水１８７部を、横型メディア分散機のＤＹＮＯ−ＭＩＬＬ Ｔｙｐ ＫＤＬ型（同上）を使用して分散を行なった。分散後、水を加え、遠心分離により粗大粒子を除去し、顔料濃度１４％の水性の顔料分散液Ｂを得た。この水性顔料分散液Ｂの不揮発分（Ｎ．Ｖ）も水性顔料分散液Ａと同様、１７．５％である。また、円錐平板型回転粘度計を用いて、２５℃、５０ｒｐｍの条件において測定したときの粘度は、２．７〜３．０ｍＰａ・ｓであった。
<Example 7>
114 parts of the above-mentioned dispersed resin solution, 79 parts of cyanine blue chromofine blue A-220JC (trade name, manufactured by Dainichi Seika Kogyo Co., Ltd.), 1.9 parts of 25% ammonia water and 187 parts of ion-exchanged water, Dispersion was performed using a DYNO-MILL Type KDL type media idler (as described above). After dispersion, water was added, and coarse particles were removed by centrifugation to obtain an aqueous pigment dispersion B having a pigment concentration of 14%. The nonvolatile content (N.V.) of this aqueous pigment dispersion B is 17.5% as in the case of the aqueous pigment dispersion A. The viscosity measured at 25 ° C. and 50 rpm using a conical flat plate type rotary viscometer was 2.7 to 3.0 mPa · s.
次いで、上記で得た顔料分散液Ｂの５５．４部に、ポリウレタン系樹脂エマルジョンとして、バイヒドロール（登録商標）ＵＨ２６０６（同上）を４０部（樹脂分１４部）、造膜助剤としてソルフィット（同上）を１部、乾燥防止剤としてポリプロピレングリコール０．５部、シリコーン系樹脂エマルジョンとして５２Ａｄｄｉｔｉｖｅ（同上）を３部及び濡れ剤としてフッ素系界面活性剤であるメガファックＦ−４４４（同上）を０．１部加えて、本実施例のインキの配合とした。更に、この配合物を、ディゾルバーで分散して本発明の水性顔料インキ組成物を得た。表１に、得られた水性顔料インキ組成物の組成を示した。後述する表３に示したように、本実施例の水性顔料インキ組成物の粘度は、５．８１ｍＰａ・ｓと低粘度であった。 Then, in 55.4 parts of the pigment dispersion B obtained above, 40 parts (resin content: 14 parts) of Bihydrol (registered trademark) UH2606 (same as above) as a polyurethane-based resin emulsion, and Solfit (as a film-forming auxiliary). 1 part), 0.5 parts of polypropylene glycol as a drying inhibitor, 3 parts of 52Additive (same as above) as a silicone resin emulsion, and 0 parts of Megafac F-444 (same as above) as a wetting agent as a fluorinated surfactant. .1 part in addition to the ink of this example. Further, this formulation was dispersed with a dissolver to obtain an aqueous pigment ink composition of the present invention. Table 1 shows the composition of the obtained water-based pigment ink composition. As shown in Table 3 below, the viscosity of the aqueous pigment ink composition of this example was as low as 5.81 mPa · s.
＜比較例１〜６＞
実施例１の配合物を表２に示す配合としたこと以外は実施例１と同様にして、各比較例の水性顔料インキ組成物を得た。
<Comparative Examples 1 to 6>
An aqueous pigment ink composition of each comparative example was obtained in the same manner as in Example 1 except that the composition of Example 1 was changed to the composition shown in Table 2.
［水性顔料インキ組成物の評価］
＜粘度＞
上記で調製した実施例及び比較例の各水性顔料インキ組成物を撹拌し、その温度を２５±１℃に調整して測定用試料とした。そして、これらの測定用試料について、円錐平板型回転粘度計ＲＥ−８０Ｌ型（商品名、東機産業社製）を用い、５０ｒｐｍで回転開始から２分経過時の指針の示度を読み取り粘度を測定した。粘度は、製造直後の各インキ組成物についてと、５０℃で３か月保存後の各インキ組成物について、それぞれ測定した。測定結果を、実施例については表３に、比較例については表４に、まとめて示した。また、これらの表中に、実施例及び比較例の各水性顔料インキ組成物を構成する２種のエマルジョンの使用比率を示した。
[Evaluation of aqueous pigment ink composition]
<Viscosity>
The aqueous pigment ink compositions of the Examples and Comparative Examples prepared above were stirred, and the temperature was adjusted to 25 ± 1 ° C. to obtain a measurement sample. Then, for these measurement samples, using a cone-plate type rotary viscometer RE-80L (trade name, manufactured by Toki Sangyo Co., Ltd.), read the indication of the pointer at 2 minutes after the start of rotation at 50 rpm and read the viscosity. It was measured. The viscosity was measured for each ink composition immediately after production and for each ink composition after storage at 50 ° C. for 3 months. The measurement results are collectively shown in Table 3 for Examples and Table 4 for Comparative Examples. Further, in these tables, the use ratios of the two types of emulsions constituting the aqueous pigment ink compositions of the examples and comparative examples are shown.
＜耐擦過性試験＞
試験用に、実施例及び比較例の各水性顔料インキ組成物をそれぞれ、繊維束の芯を有するペン体に詰めたペンを用意した。この際、ペン先が、角芯と、丸芯の、２種類のペンを用意した。これらのペンを用いて、ＰＥＴフィルムにそれぞれ描線を書き、これを２４時間保管した。そして、保管後のものを評価用試料として、摩擦堅牢度試験機ＲＴ−２００（商品名、大栄科学精器製作所社製）で、形成した画像（描線）の耐擦過性を評価した。試験は、摩擦子に綿布（平織）又はデニム布を取り付け、これらの摩擦子に対する耐擦過性を調べた。具体的には、荷重１．１ｋｇで、上記摩擦子による往復１００回の摩擦運動をして、描線に生じた傷や剥離具合を目視で観察して評価した。評価は、往復１０回毎に観察して評価したが、結果については、５０回と１００回の時点における結果を記載した。評価結果を、実施例については表３に、比較例については表４に、まとめて示した。
<Scratch resistance test>
For the test, a pen was prepared in which each of the aqueous pigment ink compositions of Examples and Comparative Examples was packed in a pen body having a core of a fiber bundle. At this time, two types of pens, a square core and a round core, were prepared. Each of these pens was used to draw a line on a PET film, which was stored for 24 hours. The image (drawing line) formed was evaluated for abrasion resistance using a friction fastness tester RT-200 (trade name, manufactured by Daiei Kagaku Seiki Seisakusho Co., Ltd.) using the stored sample as an evaluation sample. In the test, a cotton cloth (plain weave) or a denim cloth was attached to the friction elements, and the scratch resistance to these friction elements was examined. Specifically, a frictional motion was performed 100 times reciprocally by the friction element under a load of 1.1 kg, and the scratches and peeling state generated on the drawn lines were visually observed and evaluated. The evaluation was performed by observing every 10 reciprocations, and the results were described at 50 and 100 times. The evaluation results are collectively shown in Table 3 for Examples and Table 4 for Comparative Examples.
具体的には、以下の規準で評価した。無傷或いは、評価が３の３０％の欠損迄を実用レベルと評価した。総合評価として、４〜６が１つでもある場合を×、４〜６の評価が１つもないが、３の評価が１つでもある場合を△、３〜６の評価が１つもない場合を○とした。
（評価基準）
◎：無傷
１：１〜５％欠損
２：６〜１０％欠損
３：１１〜３０％欠損
４：３１〜６０％欠損
５：６１〜９９％欠損
６：１００％欠損
Specifically, evaluation was made according to the following criteria. Practical levels were evaluated as intact or up to a 30% loss of rating 3. As a comprehensive evaluation, x is the case where there is at least one of 4 to 6, x is none of the evaluations of 4 to 6, but is at least one of the evaluation of △, and there is no evaluation of 3 to 6 ○
(Evaluation criteria)
：: intact 1: 1-5% defective 2: 6-10% defective 3: 11-30% defective 4: 31-60% defective 5: 61-99% defective 6: 100% defective
＜書き味＞
試験用に、実施例及び比較例の各水性顔料インキ組成物をそれぞれ、繊維束の芯を有するペン体に詰めたペンを用意した。そして、このペンを用いて、ＰＥＴフィルム上に描線を書き、その際の書き味について得た感覚を、１〜５の５段階で相対評価した。書き味の評価は、異なる５人でそれぞれ行い、表３及び表４中に、最も多くの人が付けた点数を評価結果として示した。その結果、表３及び表４に示されているように、インキ組成物の粘度の低いものは書き味がよく、粘度の高いものは書き味が劣ると評価される傾向があることが確認された。このことは、形成した画像（描線）の耐擦過性が同じであれば、より粘度の低いインキを設計することで、筆記具として重要な、書き味がより優れたものになることを意味している。
<Writing taste>
For the test, a pen was prepared in which each of the aqueous pigment ink compositions of Examples and Comparative Examples was packed in a pen body having a core of a fiber bundle. Then, using this pen, drawing lines were drawn on a PET film, and the feeling obtained with respect to the writing taste at that time was relatively evaluated on a scale of 1 to 5. The evaluation of writing taste was performed by five different persons, respectively, and in Tables 3 and 4, the score given by the most persons was shown as the evaluation result. As a result, as shown in Tables 3 and 4, it was confirmed that ink compositions having a low viscosity tend to be evaluated as having good writing taste, and ink compositions having a high viscosity tend to be evaluated as having a poor writing taste. Was. This means that if the formed images (drawing lines) have the same abrasion resistance, designing an ink with a lower viscosity will make writing, which is important as a writing instrument, more excellent. I have.
参考として、水性又は油性の各種の市販品の筆記用のペンについて上記と同様の耐擦過性試験を行い、同様の方法で評価して本発明の実施例のペンと比較した。
＜参考例１＞
市販品の水性の中綿式のペンであるプロッキー（商品名、三菱鉛筆社製）を用いてＰＥＴフィルム上に描線を書き、実施例で行ったと同様にして、描線の耐擦過性を評価した。その結果、いずれの条件でも、参考例１の市販の水性ペンは、往復摩擦で３回もたずにフィルム上の描線は剥離した。
As a reference, the same scratch resistance test as described above was performed on various commercially available water-based or oil-based writing pens, and evaluated by the same method, and compared with the pens of Examples of the present invention.
<Reference Example 1>
Drawing lines were drawn on the PET film using a commercially available water-based batting pen Prockey (trade name, manufactured by Mitsubishi Pencil Co.), and the scratch resistance of the drawing lines was evaluated in the same manner as in Examples. As a result, the line drawn on the film of the commercially available aqueous pen of Reference Example 1 was peeled off in less than three times due to reciprocating friction under any conditions.
＜参考例２＞
市販品の油性の中綿式のペンであるマッキー（登録商標、ゼブラ社製）を用いて、参考例１と同様に、ＰＥＴフィルム上に描線を書き、実施例で行ったと同様にして描線の耐擦過性を評価した。その結果、いずれの条件でも、参考例２の市販の油性ペンは、往復摩擦で３回程度から傷がつきはじめ、２０回程度でフィルム上の描線は剥離した。
<Reference Example 2>
Using Mackey (registered trademark, manufactured by Zebra Corp.), a commercially available oil-based batting pen, drawing lines were drawn on a PET film in the same manner as in Reference Example 1, and the drawing line resistance was evaluated in the same manner as in Example. The abrasion was evaluated. As a result, under any conditions, the commercially available oil-based pen of Reference Example 2 began to be scratched from about 3 times by reciprocating friction, and the drawing line on the film was peeled off after about 20 times.
＜参考例３＞
市販品の油性の中綿式のペンであるｅｄｄｉｎｇ（登録商標、ｅｄｄｉｎｇ社製）を用いて、参考例１と同様に、ＰＥＴフィルム上に描線を書き、実施例で行ったと同様にして描線の耐擦過性を評価した。その結果、いずれの条件でも、参考例３の市販の油性ペンは、往復摩擦で３回程度から傷がつきはじめ、２０回程度でフィルム上の描線は剥離した。
<Reference Example 3>
Using a commercially available oil-based batting pen, edding (registered trademark, manufactured by edding Co.), drawing lines were drawn on a PET film in the same manner as in Reference Example 1, and the drawing line resistance was measured in the same manner as in Example. The abrasion was evaluated. As a result, under any conditions, the commercially available oil-based pen of Reference Example 3 began to be scratched from about 3 times by reciprocating friction, and the drawing line on the film was peeled off after about 20 times.
＜参考例４＞
直液式のペンである水性ペイントマーカー（三菱鉛筆社製）を用いてＰＥＴフィルム上に描線を書き、参考例１と同様に、ＰＥＴフィルム上に描線を書き、実施例で行ったと同様にして描線の耐擦過性を評価した。その結果、いずれの条件でも、参考例４の市販の直液式の水性ペンは、往復摩擦で３回もたずにフィルム上の描線は剥離した。
<Reference example 4>
Using a water-based paint marker (manufactured by Mitsubishi Pencil), which is a direct liquid pen, draw a line on the PET film, and draw a line on the PET film in the same manner as in Reference Example 1 in the same manner as in Example. The scratch resistance of the drawn lines was evaluated. As a result, the line drawn on the film of the commercially available direct liquid type aqueous pen of Reference Example 4 was peeled off in less than three times due to reciprocating friction under any conditions.
＜参考例５＞
直液式のペンである油性ペイントマーカー（三菱鉛筆社製）を用いて、参考例１と同様に、ＰＥＴフィルム上に描線を書き、実施例で行ったと同様にして描線の耐擦過性を評価した。その結果、いずれの条件でも、参考例５の市販の直液式の油性ペンは、往復摩擦２０回程度でフィルム上の描線は剥離した。
<Reference Example 5>
Using an oil-based paint marker (manufactured by Mitsubishi Pencil), which is a direct liquid pen, draw a line on the PET film in the same manner as in Reference Example 1, and evaluate the scratch resistance of the drawn line in the same manner as in Example. did. As a result, the line drawn on the film of the commercially available direct liquid type oil-based pen of Reference Example 5 was peeled off with about 20 reciprocal rubs under any conditions.
参考例１〜５のペンの評価結果を表５にまとめて記載した。なお、参考例で使用したペンはいずれも市販品であり、充填されたインキの粘度を測定することができなかった。
Claims (8)
前記それ以外の樹脂エマルジョンが、ポリウレタン系樹脂エマルジョン又はアクリル系樹脂エマルジョンの少なくともいずれかであり、
前記シリコーン系樹脂エマルジョンと、前記それ以外の樹脂エマルジョンとが、その固形分の質量比が、シリコーン系樹脂エマルジョン／それ以外の樹脂エマルジョン＝０．１〜０．８の範囲内となる量で併用されており、且つ、
円錐平板型回転粘度計で、２５℃、５０ｒｐｍの条件において測定したときの粘度が、２．０ｍＰａ・ｓを超えて８ｍＰａ・ｓ以下であることを特徴とする筆記具用の水性顔料インキ組成物。 An aqueous pigment ink composition for a writing implement comprising a pigment, water, a dispersion resin, a silicone resin emulsion and another resin emulsion,
The other resin emulsion is at least one of a polyurethane resin emulsion or an acrylic resin emulsion,
The silicone resin emulsion and the other resin emulsion are used together in an amount such that the mass ratio of the solid content of the silicone resin emulsion / the other resin emulsion is in the range of 0.1 to 0.8. Has been done, and
An aqueous pigment ink composition for a writing instrument, wherein the viscosity when measured with a conical plate type rotary viscometer at 25 ° C. and 50 rpm is more than 2.0 mPa · s and 8 mPa · s or less.
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