JP2023138596A - Aqueous ballpoint pen ink composition - Google Patents
Aqueous ballpoint pen ink composition Download PDFInfo
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- JP2023138596A JP2023138596A JP2023122654A JP2023122654A JP2023138596A JP 2023138596 A JP2023138596 A JP 2023138596A JP 2023122654 A JP2023122654 A JP 2023122654A JP 2023122654 A JP2023122654 A JP 2023122654A JP 2023138596 A JP2023138596 A JP 2023138596A
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- ballpoint pen
- ink composition
- resin particles
- polyvinylpyrrolidone
- colored resin
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- 239000000203 mixture Substances 0.000 title claims abstract description 70
- 239000002245 particle Substances 0.000 claims abstract description 100
- 229920005989 resin Polymers 0.000 claims abstract description 66
- 239000011347 resin Substances 0.000 claims abstract description 66
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims abstract description 54
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims abstract description 54
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims abstract description 50
- 229920001285 xanthan gum Polymers 0.000 claims abstract description 38
- 239000000230 xanthan gum Substances 0.000 claims abstract description 36
- 235000010493 xanthan gum Nutrition 0.000 claims abstract description 36
- 229940082509 xanthan gum Drugs 0.000 claims abstract description 36
- 230000008859 change Effects 0.000 abstract description 5
- 230000007423 decrease Effects 0.000 abstract description 5
- 239000000976 ink Substances 0.000 description 82
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 29
- 239000000975 dye Substances 0.000 description 18
- 239000000049 pigment Substances 0.000 description 17
- 239000000243 solution Substances 0.000 description 15
- -1 etc. Substances 0.000 description 13
- 239000003086 colorant Substances 0.000 description 12
- 239000003094 microcapsule Substances 0.000 description 10
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- 238000004519 manufacturing process Methods 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
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- 239000000126 substance Substances 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 7
- 239000003921 oil Substances 0.000 description 7
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 239000003960 organic solvent Substances 0.000 description 6
- 239000004372 Polyvinyl alcohol Substances 0.000 description 5
- 238000004040 coloring Methods 0.000 description 5
- 239000007850 fluorescent dye Substances 0.000 description 5
- 239000012071 phase Substances 0.000 description 5
- 229920002451 polyvinyl alcohol Polymers 0.000 description 5
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- 235000014113 dietary fatty acids Nutrition 0.000 description 4
- 239000002270 dispersing agent Substances 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N ethyl acetate Substances CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 239000000194 fatty acid Substances 0.000 description 4
- 229930195729 fatty acid Natural products 0.000 description 4
- 239000000314 lubricant Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 239000004908 Emulsion polymer Substances 0.000 description 3
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
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- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
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- 238000009826 distribution Methods 0.000 description 3
- 239000003112 inhibitor Substances 0.000 description 3
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 3
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- 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 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
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- 239000004743 Polypropylene Substances 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 239000000980 acid dye Substances 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 229920003180 amino resin Polymers 0.000 description 2
- 239000000981 basic dye Substances 0.000 description 2
- 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 2
- 239000002775 capsule Substances 0.000 description 2
- 239000004202 carbamide Substances 0.000 description 2
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- 239000012528 membrane Substances 0.000 description 2
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- 229940078812 myristyl myristate Drugs 0.000 description 2
- 239000012860 organic pigment Substances 0.000 description 2
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- 150000003505 terpenes Chemical class 0.000 description 2
- 235000007586 terpenes Nutrition 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- DZKXJUASMGQEMA-UHFFFAOYSA-N tetradecyl tetradecanoate Chemical compound CCCCCCCCCCCCCCOC(=O)CCCCCCCCCCCCC DZKXJUASMGQEMA-UHFFFAOYSA-N 0.000 description 2
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 2
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- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 description 1
- IXHBSOXJLNEOPY-UHFFFAOYSA-N 2'-anilino-6'-(n-ethyl-4-methylanilino)-3'-methylspiro[2-benzofuran-3,9'-xanthene]-1-one Chemical compound C=1C=C(C2(C3=CC=CC=C3C(=O)O2)C2=CC(NC=3C=CC=CC=3)=C(C)C=C2O2)C2=CC=1N(CC)C1=CC=C(C)C=C1 IXHBSOXJLNEOPY-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
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- CUZKCNWZBXLAJX-UHFFFAOYSA-N 2-phenylmethoxyethanol Chemical compound OCCOCC1=CC=CC=C1 CUZKCNWZBXLAJX-UHFFFAOYSA-N 0.000 description 1
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-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
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 229910000851 Alloy steel Inorganic materials 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 241000237858 Gastropoda Species 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
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- SJEYSFABYSGQBG-UHFFFAOYSA-M Patent blue Chemical compound [Na+].C1=CC(N(CC)CC)=CC=C1C(C=1C(=CC(=CC=1)S([O-])(=O)=O)S([O-])(=O)=O)=C1C=CC(=[N+](CC)CC)C=C1 SJEYSFABYSGQBG-UHFFFAOYSA-M 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- 229920002310 Welan gum Polymers 0.000 description 1
- MBHRHUJRKGNOKX-UHFFFAOYSA-N [(4,6-diamino-1,3,5-triazin-2-yl)amino]methanol Chemical compound NC1=NC(N)=NC(NCO)=N1 MBHRHUJRKGNOKX-UHFFFAOYSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 150000008055 alkyl aryl sulfonates Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 230000002421 anti-septic effect Effects 0.000 description 1
- 239000004599 antimicrobial Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000011324 bead Substances 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
- 239000006229 carbon black Substances 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical class OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
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- 238000011161 development Methods 0.000 description 1
- ZFAKTZXUUNBLEB-UHFFFAOYSA-N dicyclohexylazanium;nitrite Chemical compound [O-]N=O.C1CCCCC1[NH2+]C1CCCCC1 ZFAKTZXUUNBLEB-UHFFFAOYSA-N 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
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- 235000011187 glycerol Nutrition 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
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- 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
- 229920002587 poly(1,3-butadiene) polymer Polymers 0.000 description 1
- 229920000233 poly(alkylene oxides) Polymers 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920001515 polyalkylene glycol Polymers 0.000 description 1
- 229920001083 polybutene Polymers 0.000 description 1
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- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920006316 polyvinylpyrrolidine Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
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- 150000007949 saponins Chemical class 0.000 description 1
- 235000017709 saponins Nutrition 0.000 description 1
- 230000035936 sexual power Effects 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
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- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- WXMKPNITSTVMEF-UHFFFAOYSA-M sodium benzoate Chemical compound [Na+].[O-]C(=O)C1=CC=CC=C1 WXMKPNITSTVMEF-UHFFFAOYSA-M 0.000 description 1
- 235000010234 sodium benzoate Nutrition 0.000 description 1
- 239000004299 sodium benzoate Substances 0.000 description 1
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Landscapes
- Inks, Pencil-Leads, Or Crayons (AREA)
- Pens And Brushes (AREA)
Abstract
Description
本発明は、筆記を休止した直後の書き出し時にインクが出渋る現象（初筆性の低下）を解消することができる水性ボールペン用インク組成物に関する。 The present invention relates to an ink composition for an aqueous ballpoint pen that can eliminate the phenomenon of ink reluctance to flow (decreased first-time writing ability) when starting to write immediately after stopping writing.
従来より、水性ボールペン等に用いられている熱変色性マイクロカプセルのような粒子径の大きい着色樹脂粒子などの着色剤は、一般的な染料・顔料と比較してインク中での流動性が低いものである。したがって、静から動、或いは動から静状態への応答性がやや鈍いものである。
ボールペンのような動作の切り替えが頻繁で、インクに対する剪断力の変化が大きい筆記具においては、その特性が描線に現れやすく、特に、筆記を休止した直後の書き出しに時にインクが出渋る現象（初筆性の低下）が見られている。
Conventionally, colorants such as colored resin particles with large particle diameters such as thermochromic microcapsules used in water-based ballpoint pens, etc. have lower fluidity in ink than general dyes and pigments. It is something. Therefore, the responsiveness from a still state to a moving state or from a moving state to a still state is somewhat slow.
In writing instruments such as ballpoint pens, which change their movements frequently and have large changes in the shearing force applied to the ink, these characteristics tend to appear in the lines drawn, and in particular, there is a phenomenon in which the ink sometimes slugs out when starting to write immediately after a pause (first stroke). A decline in sexual performance has been observed.
一方、従来の水性ボールペン用インク組成物において、着色剤、キサンタンガムやポリビニルアルコールなどを用いたものとしては、例えば、
（１）水と着色剤と樹脂とから少なくともなるボールペン用水性インキにおいて、前記樹脂がキサンタンガムとポリビニルピロリドンであり、このキサンタンガムとポリビニルピロリドンの含有比が１：５．７～１：７．０であるボールペン用水性インキ（例えば、特許文献１参照）、
（２）一種又は二種以上のビニル系単量体を少なくとも原料とする乳化重合体であって、呈色性化合物と顕色剤とを含有することにより発色していることを特徴とする乳化重合体、この乳化重合体をインキとして、実施例２には、平均粒子径０．１７μｍ、粘度３．９ｍＰａ・ｓ（２５℃、１５０ｓ－１）の鮮明な緑色の乳化重合体の微粒子分散液５０ｇと、ＰＶＰ Ｋ－１５（アイエスピー・ジャパン株式会社製、ポリビニルピロリドン、消色剤、商品名）２ｇ、キサンタンガム０．２５ｇを加え撹拌混合されたジェルインキボールペン用インキ（例えば、特許文献２参照）、
（３）キサンタンガム又はサクシノグリカンから選ばれる剪断減粘性付与剤と、ポリビニルピロリドンと、着色剤と、水溶性有機溶剤と、水とを少なくとも含むボールペン用水性インキ組成物であって、前記剪断減粘性付与剤とポリビニルピロリドンの含有比率が１：１～１：５．５であるボールペン用水性インキ組成物（例えば、特許文献３参照）、
（４）着色剤と、水と、水溶性有機溶剤と、キサンタンガム、ウェランガム、サクシノグリカンから選ばれる剪断減粘性付与剤と、増粘抑制剤と、イオン性物質とから少なくともなり、インキ中のイオン性物質の含有量がインキ組成物全量に対し１質量％以上であり、水溶性有機溶剤がインキ組成物中１０質量％以下であり、且つ、増粘抑制剤がポリビニルアルコール、ポリビニルピロリドン、セルロース系高分子化合物、ポリアルキレンオキサイド基を有する高分子化合物から選ばれるボールペン用水性インキ組成物、及び、それを収容したボールペン（例えば、特許文献４参照）
などが知られている。
On the other hand, conventional aqueous ballpoint pen ink compositions using colorants such as xanthan gum and polyvinyl alcohol include, for example,
(1) A water-based ballpoint pen ink comprising at least water, a colorant, and a resin, wherein the resins are xanthan gum and polyvinylpyrrolidone, and the content ratio of xanthan gum and polyvinylpyrrolidone is 1:5.7 to 1:7.0. A certain water-based ink for ballpoint pens (for example, see Patent Document 1),
(2) An emulsion polymer made from at least one or more vinyl monomers as a raw material, which is characterized by being colored by containing a color-forming compound and a color developer. Using this emulsion polymer as an ink, in Example 2, a clear green microparticle dispersion of the emulsion polymer with an average particle diameter of 0.17 μm and a viscosity of 3.9 mPa·s (25° C., 150 s −1 ) was prepared. 50 g of gel ink ballpoint pen ink (for example, see Patent Document 2), 2 g of PVP K-15 (manufactured by ISP Japan Co., Ltd., polyvinylpyrrolidone, decolorizer, trade name), and 0.25 g of xanthan gum were added and mixed with stirring. ),
(3) A water-based ink composition for a ballpoint pen, comprising at least a shear thinning agent selected from xanthan gum or succinoglycan, polyvinylpyrrolidone, a colorant, a water-soluble organic solvent, and water, A water-based ink composition for ballpoint pens in which the content ratio of viscosity imparting agent and polyvinylpyrrolidone is 1:1 to 1:5.5 (see, for example, Patent Document 3),
(4) Consisting of at least a colorant, water, a water-soluble organic solvent, a shear thinning agent selected from xanthan gum, welan gum, and succinoglycan, a thickening inhibitor, and an ionic substance; The content of the ionic substance is 1% by mass or more based on the total amount of the ink composition, the water-soluble organic solvent is 10% by mass or less in the ink composition, and the thickening inhibitor is polyvinyl alcohol, polyvinylpyrrolidone, or cellulose. A water-based ink composition for a ballpoint pen selected from a polymer compound having a polyalkylene oxide group, and a ballpoint pen containing the same (for example, see Patent Document 4)
etc. are known.
上記特許文献１～４は、本発明の水性ボールペン用インク組成物の近接技術等を開示するものであるが、特許文献１は、平均粒子径が小さい蛍光顔料等を用いるものであり、平均粒子径が０．５μｍ超過の着色樹脂粒子を用いることの記載や示唆等はなく、また、発明の課題は、ボールペンチップのボールの回転によるボール受け座の摩耗や変形を極力防止することによって良好なインキの吐出性を確保し、長筆記距離を可能となしたものであり、本発明とは、発明の課題及び構成が相違するものである。
上記特許文献２は、平均粒子径０．１７μｍと小さな熱変色性粒子等を用いるものであり、平均粒子径が０．５μｍ超過の着色樹脂粒子を用いることの記載や示唆等はなく、ま
た、発明の課題は、消色手段として加熱のみでなく、有機溶剤を利用することができるボールペン用インキであり、本発明とは、発明の課題及び構成が相違するものである。
上記特許文献３は、平均粒子径が小さい顔料等を用いるものであり、平均粒子径が０．５μｍ超過の着色樹脂粒子を用いることの記載や示唆等はなく、また、発明の課題は、ペン先近傍でのインキの乾燥固化を抑制（ペン先を露出した状態で横向き状態にて２５℃、３０日放置した後で良好な筆記できるか否かの試験：耐ドライアップ性）等であり、本発明とは、発明の課題及び構成が相違するものである。
上記特許文献４の実施例６、７では、平均粒子径が２μｍ、３μｍの可逆熱変色性顔料（熱変色性マイクロカプセル）を用いるものであるが、発明の課題は、キャップを外した状態での５０℃、３０日放置した後で良好な筆記できるか否かの試験：耐ドライアップ性）等であり、しかも、ポリビニルピロリドンとキサンタンガムの質量比は本発明の範囲から外れるものであり、本発明とは、発明の課題及び構成が相違するものである。
The above-mentioned Patent Documents 1 to 4 disclose the proximate technology of the aqueous ballpoint pen ink composition of the present invention, but Patent Document 1 uses a fluorescent pigment etc. with a small average particle size, and the average particle size is small. There is no description or suggestion of using colored resin particles with a diameter exceeding 0.5 μm, and an object of the invention is to prevent wear and deformation of the ball receiving seat of a ballpoint pen tip as much as possible due to the rotation of the ball. This ensures ink ejection performance and enables a long writing distance, and is different from the present invention in its subject and structure.
The above-mentioned Patent Document 2 uses small thermochromic particles with an average particle diameter of 0.17 μm, and there is no description or suggestion of using colored resin particles with an average particle diameter of more than 0.5 μm. The object of the invention is to provide an ink for a ballpoint pen that can utilize not only heating but also an organic solvent as a decoloring means, and the object and structure of the invention are different from the present invention.
Patent Document 3 mentioned above uses a pigment etc. with a small average particle diameter, and there is no description or suggestion of using colored resin particles with an average particle diameter exceeding 0.5 μm. Suppressing the drying and solidification of ink near the tip (test to see if good writing is possible after being left horizontally at 25°C with the pen tip exposed for 30 days: dry-up resistance), etc. The present invention is different from the present invention in its subject matter and structure.
In Examples 6 and 7 of the above-mentioned Patent Document 4, reversible thermochromic pigments (thermochromic microcapsules) with average particle diameters of 2 μm and 3 μm are used. A test to determine whether or not good writing is possible after being left at 50°C for 30 days (dry-up resistance), etc. Moreover, the mass ratio of polyvinylpyrrolidone and xanthan gum is outside the scope of the present invention, and is not included in the present invention. Inventions are different in their subject matter and structure.
以上のように、上記特許文献１～４は、本発明の水性ボールペン用インク組成物の近接技術等を開示するものであるが、本発明とは、発明の課題及び構成などが相違するものといえる。
本発明の課題は、水性ボールペンにおいて、上記特許文献３や４に記載される、キャップを外した状態で、長期間放置した後でのペン先近傍でのインクの乾燥固化を抑制（耐ドライアップ性）でなく、熱変色性マイクロカプセル等のような平均粒子径の大きい着色樹脂粒子を用いた場合に発生する現象であり、動作の切り替えが多く、剪断力の変化が大きいボールペンにおいては、その特性が描線に現れやすく、特に、筆記を休止した直後（数分間後）の書き出しに時にインクが出渋る現象（初筆性の低下）の解消であり、上記耐ドライアップ性と本発明の書き出し時にインクが出渋る現象（初筆性の低下）はその発生原因、その解決手段などが明確に区別化できるものである。
As mentioned above, the above-mentioned Patent Documents 1 to 4 disclose the related technology of the aqueous ballpoint pen ink composition of the present invention, but they differ from the present invention in the problem and structure of the invention. I can say that.
The problem of the present invention is to suppress the drying and solidification of ink near the pen tip (dry-up resistance) in water-based ballpoint pens, which is described in Patent Documents 3 and 4 mentioned above. This is a phenomenon that occurs when colored resin particles with a large average particle size such as thermochromic microcapsules are used, rather than using thermochromic microcapsules. This is to eliminate the phenomenon that ink tends to appear in drawn lines, especially when starting to write immediately after stopping writing (several minutes) (decreased first-time writing ability), and the above dry-up resistance and the beginning of writing of the present invention. The phenomenon in which ink sometimes does not come out well (decreased first-time writing ability) can be clearly distinguished by its causes and solutions.
本発明は、上記従来技術の課題及び現状に鑑み、これを解消しようとするものであり、筆記を休止した直後の書き出し時にインクが出渋る現象、すなわち、初筆性の低下を解消することができる水性ボールペン用インク組成物を提供することを目的とする。 The present invention is intended to solve the above-mentioned problems and current state of the prior art, and it is possible to solve the phenomenon that ink is difficult to come out when starting to write immediately after stopping writing, that is, the decrease in first-time writing ability. The purpose of the present invention is to provide an ink composition for an aqueous ballpoint pen that can be used.
本発明者らは、上記従来の課題等に鑑み、鋭意研究を行った結果、少なくとも、平均粒子径が０．５～６μｍの着色樹脂粒子と、キサンタンガム及びポリビニルピロリドンを含有し、前記ポリビニルピロリドン／キサンタンガムの質量比を特定の範囲とすることにより、上記目的の水性ボールペン用インク組成物が得られることを見出し、本発明を完成するに至ったのである。 In view of the above-mentioned conventional problems, the present inventors conducted intensive research and found that the present invention contains at least colored resin particles having an average particle diameter of 0.5 to 6 μm, xanthan gum, and polyvinylpyrrolidone, and the polyvinylpyrrolidone/ The inventors have discovered that the above-described aqueous ballpoint pen ink composition can be obtained by adjusting the mass ratio of xanthan gum within a specific range, and have completed the present invention.
すなわち、本発明の水性ボールペン用インク組成物は、少なくとも、平均粒子径が０．５～６μｍの着色樹脂粒子と、キサンタンガム及びポリビニルピロリドンを含有し、前記ポリビニルピロリドン／キサンタンガムの質量比が１～９であることを特徴とする。
前記ポリビニルピロリドンのＫ値は１０～４０であることが好ましい。
前記ポリビニルピロリドンの含有量は、インク組成物全量に対して、０．５～５質量％
が好ましい。
本発明の水性ボールペンは、上記組成の水性ボールペン用インク組成物を搭載したことを特徴とする。
That is, the aqueous ballpoint pen ink composition of the present invention contains at least colored resin particles having an average particle diameter of 0.5 to 6 μm, xanthan gum and polyvinylpyrrolidone, and the mass ratio of polyvinylpyrrolidone/xanthan gum is 1 to 9. It is characterized by
The K value of the polyvinylpyrrolidone is preferably 10 to 40.
The content of the polyvinylpyrrolidone is 0.5 to 5% by mass based on the total amount of the ink composition.
is preferred.
The aqueous ballpoint pen of the present invention is characterized by being equipped with the ink composition for an aqueous ballpoint pen having the above composition.
本発明によれば、筆記を休止した直後の書き出し時にインクが出渋る現象（初筆性の低下）を解消することができる水性ボールペン用インク組成物、このインク組成物を搭載した水性ボールペンが提供される。 According to the present invention, there is provided an ink composition for a water-based ballpoint pen that can eliminate the phenomenon of ink reluctance to flow when starting to write immediately after stopping writing (deterioration in first-time writing ability), and a water-based ballpoint pen equipped with this ink composition. be done.
以下に、本発明の実施形態を詳しく説明する。
本発明の水性ボールペン用インク組成物は、少なくとも、平均粒子径が０．５～６μｍの着色樹脂粒子と、キサンタンガム及びポリビニルピロリドンを含有し、前記ポリビニルピロリドン／キサンタンガムの質量比が１～９であることを特徴とするものである。
Embodiments of the present invention will be described in detail below.
The aqueous ballpoint pen ink composition of the present invention contains at least colored resin particles having an average particle diameter of 0.5 to 6 μm, xanthan gum and polyvinylpyrrolidone, and the mass ratio of the polyvinylpyrrolidone/xanthan gum is 1 to 9. It is characterized by this.
〈着色樹脂粒子〉
本発明に用いる着色樹脂粒子としては、着色された樹脂粒子から構成されるものであれば特に限定されず、例えば、１）樹脂粒子中にカーボンブラック、酸化チタン等の無機顔料、フタロシアニン系顔料、アゾ系顔料等の有機顔料などの顔料からなる着色剤が分散された着色樹脂粒子、２）樹脂粒子の表面が上記顔料からなる着色剤で被覆された着色樹脂粒子、３）樹脂粒子に直接染料、酸性染料、塩基性染料、食料染料、蛍光染料などの染料からなる着色剤が染着された着色樹脂粒子、４）ロイコ色素等を用いて熱変色性とした着色樹脂粒子、５）光変色性色素となるフォトクロミック色素（化合物）、蛍光色素等を用いて光変色性とした着色樹脂粒子などが挙げられる。
上記１）～３）の着色樹脂粒子の樹脂成分としては、例えば、アクリル酸、メタクリル酸、アクリル酸エステル、メタクリル酸エステル、スチレン、アクリロニトリル、ブタジエン等の重合体もしくはこれらの共重合体、ベンゾグアナミン、フェノール樹脂、エポキシ樹脂、ウレタン樹脂等から選択される少なくとも１種が挙げられ、必要に応じて架橋などの処理を行ったものであってもよい。これらの樹脂への着色方法としては、従来公知の懸濁重合、分散重合などの手法が用いられる。
<Colored resin particles>
The colored resin particles used in the present invention are not particularly limited as long as they are composed of colored resin particles.For example, 1) inorganic pigments such as carbon black and titanium oxide, phthalocyanine pigments, etc. in the resin particles, 2) Colored resin particles in which a colorant made of a pigment such as an organic pigment such as an azo pigment is dispersed; 2) Colored resin particles in which the surface of the resin particle is coated with a colorant made of the above pigment; 3) Direct dye on the resin particle. , colored resin particles dyed with a coloring agent such as acid dye, basic dye, food dye, fluorescent dye, etc., 4) colored resin particles made thermochromic using leuco dye, etc., 5) photochromic Examples include colored resin particles that have photochromic properties using photochromic dyes (compounds), fluorescent dyes, and the like.
Examples of resin components of the colored resin particles in 1) to 3) above include acrylic acid, methacrylic acid, acrylic esters, methacrylic esters, polymers such as styrene, acrylonitrile, butadiene, or copolymers thereof, benzoguanamine, At least one selected from phenol resins, epoxy resins, urethane resins, etc. may be used, and they may be treated with crosslinking or the like if necessary. As a method for coloring these resins, conventionally known techniques such as suspension polymerization and dispersion polymerization are used.
上記４）の熱変色性の着色樹脂粒子としては、電子供与性染料であって、発色剤としての機能するロイコ色素と、該ロイコ色素を発色させる能力を有する成分となる顕色剤及び上記ロイコ色素と顕色剤の呈色において変色温度をコントロールすることができる変色温度調整剤を少なくとも含む熱変色性組成物を、所定の平均粒子径となるように、マイクロカプセル化することにより製造された熱変色性の着色樹脂粒子などを挙げることができる。
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、ロイコ色素、顕色剤、変色温度調整剤を加熱溶融後、乳化剤溶液に投入し、加熱攪拌して油滴状に分散させ、次いで、カプセル膜剤として、壁膜がウレタン樹脂、エポキシ樹脂、アミノ樹脂等となる樹脂原料を使用、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熱変色性のマイクロカプセル顔料からなる熱変色性の着色樹脂粒子を製造することができる。この熱変色性の着色樹脂粒子では、ロイコ色素、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、各色の発色温度、消色温度を好適な温度に設定することができる。
なお、前記熱変色性の着色樹脂粒子は、可逆熱変色性となるものが好ましい。可逆熱変
色性となるものは、発色状態から加熱により消色する加熱消色型、発色状態又は消色状態を互変的に特定温度域で記憶保持する色彩記憶保持型、又は、消色状態から加熱により発色し、発色状態からの冷却により消色状態に復する加熱発色型等、種々のタイプを単独又は併用して構成することができる。
The thermochromic colored resin particles in 4) include a leuco dye which is an electron-donating dye and functions as a coloring agent, a color developer which is a component having the ability to color the leuco dye, and the leuco dye mentioned above. Manufactured by microencapsulating a thermochromic composition containing at least a color change temperature regulator capable of controlling the color change temperature in the color development of the dye and color developer to a predetermined average particle size. Examples include thermochromic colored resin particles.
Examples of microencapsulation methods include interfacial polymerization, interfacial polycondensation, in situ polymerization, in-liquid curing coating, phase separation from aqueous solutions, phase separation from organic solvents, melting and dispersion cooling, and in-air cooling. Examples include a suspension coating method and a spray drying method, which can be appropriately selected depending on the application. For example, in the phase separation method from an aqueous solution, a leuco dye, a color developer, and a discoloration temperature regulator are heated and melted, then added to an emulsifier solution, heated and stirred to disperse in the form of oil droplets, and then, as a capsule membrane agent, Use a resin raw material whose wall film is urethane resin, epoxy resin, amino resin, etc. For example, gradually add each solution such as amino resin solution, specifically methylolmelamine aqueous solution, urea solution, benzoguanamine solution, etc. After reaction and preparation, the dispersion is filtered to produce thermochromic colored resin particles comprising thermochromic microcapsule pigments. In these thermochromic colored resin particles, the coloring temperature and decoloring temperature of each color can be set to suitable temperatures by suitably combining the types and amounts of the leuco dye, color developer, and color change temperature regulator. can.
The thermochromic colored resin particles are preferably ones that exhibit reversible thermochromic properties. Types that are reversible thermochromic include: heating color erasing type that erases the color from the colored state by heating, color memory retention type that tautomically stores the colored state or colorless state within a specific temperature range, or color erasing state. Various types can be used alone or in combination, such as a heated coloring type that develops color by heating and returns to a decolorized state by cooling from the colored state.
上記５）の光変色性の着色樹脂粒子としては、例えば、少なくともフォトクロミック色素（化合物）、蛍光色素などから選択される１種以上と、テルペンフェノール樹脂などの樹脂とにより構成される光変色性の着色樹脂粒子や、少なくともフォトクロミック色素（化合物）、蛍光色素などから選択される１種以上と、有機溶媒と、酸化防止剤、光安定剤、増感剤などの添加剤とを含む光変色性組成物を、所定の平均粒子径となるように、マイクロカプセル化することにより製造された光変色性の着色樹脂粒子などを挙げることができる。マイクロカプセル化法としては、上述の熱変色性の樹脂粒子の製造と同様に調製することができる。
この光変色性の着色樹脂粒子樹脂粒子は、フォトクロミック色素（化合物）、蛍光色素などを好適に用いることにより、例えば、室内照明環境（室内での白熱灯、蛍光灯、ランプ、白色ＬＥＤなどから選ばれる照明器具）において無色であり、紫外線照射環境（２００～４００ｎｍ波長の照射、紫外線を含む太陽光での照射環境）で発色する性質を有するものとすることができる。
上記１）～５）の各着色樹脂粒子は、蛍光顔料、熱変色性顔料や光変色性顔料のマイクロカプセル顔料など（色材）として使用することができる。また、上記１）～５）の各樹脂粒子は、公知の各製造法により製造した各樹脂粒子を使用することができ、市販品があれば、それらを使用してもよいものである。
これらの着色樹脂粒子は、着色力、分散安定性などの点から、平均粒子径が０．５～６μｍとなるものが使用され、好ましくは、１～５μｍの使用が望ましい。
本発明において、「平均粒子径」とは、レーザー回折法で測定される体積基準により算出された粒度分布の体積累積５０％時の粒子径（Ｄ５０）の値である。ここで、レーザー回折法による平均粒子径の測定は、例えば、日機装株式会社の粒子径分布解析装置ＨＲＡ９３２０－Ｘ１００を用いて行うことができる。
The photochromic colored resin particles mentioned in 5) above are, for example, photochromic particles composed of at least one kind selected from photochromic dyes (compounds), fluorescent dyes, etc., and a resin such as terpene phenol resin. A photochromic composition containing colored resin particles, at least one or more selected from photochromic dyes (compounds), fluorescent dyes, etc., an organic solvent, and additives such as antioxidants, light stabilizers, and sensitizers. Examples include photochromic colored resin particles produced by microencapsulating a substance to a predetermined average particle diameter. As for the microencapsulation method, it can be prepared in the same manner as the above-mentioned production of thermochromic resin particles.
These photochromic colored resin particles resin particles can be produced by suitably using photochromic dyes (compounds), fluorescent dyes, etc. It can be colorless in an ultraviolet irradiation environment (irradiation with a wavelength of 200 to 400 nm, or an irradiation environment with sunlight containing ultraviolet light).
Each of the colored resin particles 1) to 5) above can be used as a microcapsule pigment (coloring material) such as a fluorescent pigment, a thermochromic pigment, or a photochromic pigment. Further, each of the resin particles 1) to 5) above can be produced by a known production method, and if there is a commercially available product, it may be used.
These colored resin particles have an average particle diameter of 0.5 to 6 μm, preferably 1 to 5 μm, from the viewpoint of coloring power and dispersion stability.
In the present invention, the "average particle diameter" is the value of the particle diameter (D50) when the cumulative volume of the particle size distribution is 50%, calculated based on the volume measured by a laser diffraction method. Here, the average particle size can be measured by laser diffraction using, for example, a particle size distribution analyzer HRA9320-X100 manufactured by Nikkiso Co., Ltd.
これらの着色樹脂粒子の含有量は、インク組成物全量に対して、３～３０％とすることが好ましく、更に好ましくは、１０～３０％とすることが望ましい。この着色樹脂粒子の含有量が３％未満であると、好ましい描線濃度が得られなくなり、また、３０％を越えると、筆記感が重くなったり、描線にカスレが生じやすくなり、好ましくない。 The content of these colored resin particles is preferably 3 to 30%, more preferably 10 to 30%, based on the total amount of the ink composition. If the content of the colored resin particles is less than 3%, a desirable density of drawn lines cannot be obtained, and if it exceeds 30%, the writing feels heavy and the drawn lines tend to become blurred, which is not preferable.
〈キサンタンガム〉
本発明に用いるキサンタンガムは、増粘剤として用いるものであり、ポリビニルピロリドンとの併用等により、本発明の効果を発揮せしめるものとなる。
用いることができるキサンタンガムとしては、市販品では、三晶社製のＫＥＬＳＡＮ Ｓ、ＫＥＬＳＡＮ ＡＲ ＫＥＬＳＡＮ Ｔ、ＫＥＬＳＡＮ ＲＤ、ＫＥＬＳＡＮ ＳＴ、ＫＥＬＳＡＮ Ｍ、ＫＥＬＳＡＮ ＨＰ、ＫＥＬＳＡＮ ＡＳＸ、大日本製薬社製のエコーガム、モナートガムＧＳなどが挙げられ、これらは少なくとも１種（各単独で又は２種以上の混合）用いることができる。
これらのキサンタンガムの含有量は、後述するポリビニルピロリドンの含有量、含有割合により設定される。
<Xanthan gum>
The xanthan gum used in the present invention is used as a thickener, and when used in combination with polyvinylpyrrolidone, etc., the effects of the present invention are brought out.
Commercially available xanthan gums that can be used include KELSAN S, KELSAN AR, KELSAN T, KELSAN RD, KELSAN ST, KELSAN M, KELSAN HP, KELSAN ASX manufactured by Sansho Co., Ltd., Echo Gum and Monart Gum GS manufactured by Dainippon Pharmaceutical Co., Ltd. At least one type of these (each alone or a mixture of two or more types) can be used.
The content of these xanthan gums is set based on the content and content ratio of polyvinylpyrrolidone, which will be described later.
〈ポリビニルピロリドン〉
本発明に用いるポリビニルピロリドンは、Ｎ－ビニル－２－ピロリドンを重合して得られる高分子化合物である。本発明では、ポリビニルピロリドンとキサンタンガムとの併用及びその含有割合（質量比）を特定範囲とすることにより、初めて本発明の効果を発揮せしめるものとなる。
用いるポリビニルピロリドンの中でも、そのＫ値が１０～４０のものを用いることが望ましい。
ポリビニルピロリドンのＫ値は、分子量と相関する粘度特性値である。本発明におけるＫ値は、毛細管粘度計によって測定される相対粘度値（２５℃）を下記の式（１）に適用して算出される粘性特性値をいう。
〔式〕
Ｋ＝（１．５ｌｏｇηｒｅｌ－１）／（０．１５＋０．００３ｃ）＋［３００ｃｌｏｇηｒｅｌ＋（ｃ＋１．５ｃｌｏｇηｒｅｌ）２］１／２／（０．１５ｃ＋０．００３ｃ２） …（１）
ηｒｅｌ：ポリビニルピロリドン水溶液の水に対する相対粘度
ｃ：ポリビニルピロリドン水溶液中のポリビニルピロリドン濃度（％）
<Polyvinylpyrrolidone>
Polyvinylpyrrolidone used in the present invention is a polymer compound obtained by polymerizing N-vinyl-2-pyrrolidone. In the present invention, the effects of the present invention can only be exhibited by using polyvinylpyrrolidone and xanthan gum in combination and by controlling their content (mass ratio) within a specific range.
Among the polyvinylpyrrolidone used, it is desirable to use one having a K value of 10 to 40.
The K value of polyvinylpyrrolidone is a viscosity characteristic value that correlates with molecular weight. The K value in the present invention refers to a viscosity characteristic value calculated by applying the relative viscosity value (25° C.) measured by a capillary viscometer to the following equation (1).
〔formula〕
K=(1.5logη rel -1)/(0.15+0.003c)+[300logη rel +(c+1.5logη rel ) 2 ] 1/2 /(0.15c+0.003c 2 )...(1)
η rel : Relative viscosity of polyvinylpyrrolidone aqueous solution to water c: Polyvinylpyrrolidone concentration (%) in polyvinylpyrrolidone aqueous solution
用いるポリビニルピロリドンの中でも、そのＫ値が１０～４０のもの用いることにより、着色樹脂粒子の凝集を抑え、分散安定性をより向上するので好ましい使用となるものである。
具体的に用いることができるポリビニルピロリドンとしては、市販品では、ＡＳＨＬＡＮＤ社製のＰＶＰ Ｋ－１５（Ｋ値：１３～１９）、ＰＶＰ Ｋ－３０（Ｋ値：２６～３５）、第一工業製薬社製のピッツコールＫ－１７（Ｋ値：１５～１９）、ピッツコールＫ－３０（Ｋ値：２７～３３）、日本触媒社製のポリビニルピロリドンＫ－３０（Ｋ値：２７～３３）などの少なくとも１種（各単独、２種以上の混合物）が挙げられる。
Among the polyvinylpyrrolidones used, those having a K value of 10 to 40 are preferably used because they suppress aggregation of colored resin particles and further improve dispersion stability.
As polyvinylpyrrolidone that can be specifically used, commercially available products include PVP K-15 (K value: 13 to 19), PVP K-30 (K value: 26 to 35) manufactured by ASHLAND, and Daiichi Kogyo Seiyaku Co., Ltd. Pitzkol K-17 (K value: 15-19), Pitzkol K-30 (K value: 27-33) manufactured by Nippon Shokubai Co., Ltd., polyvinylpyrrolidone K-30 (K value: 27-33), etc. manufactured by Nippon Shokubai Co., Ltd. (each singly or a mixture of two or more).
これらのポリビニルピロリドンの含有量は、インク組成物全量に対して、０．５～５％とすることが好ましく、更に好ましくは、０．５～３．０％とすることが望ましい。このポリビニルピロリドンの含有量が０．５％未満であると、本発明の効果を十分に発揮することができず、一方、５％を越えると、着色樹脂粒子の凝集が強くなり、分散安定性が低下するので、好ましくない。 The content of polyvinylpyrrolidone is preferably 0.5 to 5%, more preferably 0.5 to 3.0%, based on the total amount of the ink composition. If the content of polyvinylpyrrolidone is less than 0.5%, the effects of the present invention cannot be fully exhibited, while if it exceeds 5%, the aggregation of the colored resin particles becomes strong, resulting in poor dispersion stability. This is not preferable because it reduces the
本発明では、用いるポリビニルピロリドンとキサンタンガムの含有割合、すなわち、ポリビニルピロリドン／キサンタンガム（質量比）を１～９とすることが必要であり、好ましくは、２～８とすることが望ましい。
この割合が１未満、並びに、９超過であると、本発明の効果を発揮できないものとなる。この配合割合（１～９）の範囲とする理由は、ポリビニルピロリドンとキサンタンガムは共にインクの増粘剤ではあるが、物理的特性が異なる。これらを併用すると、お互いの物理的特性を打ち消しあうことなく、剪断減粘性を有しながら着色樹脂粒子の凝集を抑制することで良好な流動性が保たれ、初筆性が良好となるので、上記範囲で用いるものとなる。
In the present invention, it is necessary that the content ratio of polyvinylpyrrolidone and xanthan gum used, that is, polyvinylpyrrolidone/xanthan gum (mass ratio), is 1 to 9, preferably 2 to 8.
If this ratio is less than 1 or more than 9, the effects of the present invention cannot be exhibited. The reason for this range of blending ratio (1 to 9) is that although both polyvinylpyrrolidone and xanthan gum are thickeners for ink, they have different physical properties. When these are used in combination, they do not cancel each other's physical properties and maintain good fluidity by suppressing the agglomeration of colored resin particles while having shear thinning properties, resulting in good initial brushability. It shall be used within the above range.
〈水性ボールペン用インク組成物〉
本発明の水性ボールペン用インク組成物には、少なくとも、平均粒子径が０．５～６μｍの着色樹脂粒子と、キサンタンガム及びポリビニルピロリドンを含有し、前記ポリビニルピロリドン／キサンタンガムの質量比が１～９であることを特徴とするものであり、その他に、上記着色樹脂粒子以外に汎用の着色剤、水溶性溶剤が含有される。
用いることができる着色剤としては、水溶性染料、本発明の効果を損なわない範囲で顔料、例えば、無機顔料、有機顔料等も適宜量必要に応じて使用できる。
水溶性染料としては、直接染料、酸性染料、食用染料、塩基性染料のいずれも本発明の効果を損なわない範囲で適宜量用いることができる。
<Ink composition for water-based ballpoint pen>
The aqueous ballpoint pen ink composition of the present invention contains at least colored resin particles having an average particle diameter of 0.5 to 6 μm, xanthan gum and polyvinylpyrrolidone, and the mass ratio of polyvinylpyrrolidone/xanthan gum is 1 to 9. In addition to the above-mentioned colored resin particles, it contains a general-purpose coloring agent and a water-soluble solvent.
As colorants that can be used, water-soluble dyes and pigments such as inorganic pigments and organic pigments can also be used as needed in appropriate amounts within a range that does not impair the effects of the present invention.
As water-soluble dyes, any of direct dyes, acid dyes, food dyes, and basic dyes can be used in an appropriate amount within a range that does not impair the effects of the present invention.
用いることができる水溶性溶剤としては、例えば、エチレングリコール、ジエチレングリコール、トリエチレングリコール、プロピレングリコール、ポリエチレングリコール、３－ブチレングリコール、チオジエチレングリコール、グリセリン等のグリコール類や、
エチレングリコールモノメチルエーテル、ジエチレングリコールモノメチルエーテル、単独或いは混合して使用することができる。この水溶性溶剤の含有量は、インク組成物全量に対して、５～４０％とすることが望ましい。
Examples of water-soluble solvents that can be used include glycols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, polyethylene glycol, 3-butylene glycol, thiodiethylene glycol, and glycerin;
Ethylene glycol monomethyl ether and diethylene glycol monomethyl ether can be used alone or in combination. The content of this water-soluble solvent is preferably 5 to 40% based on the total amount of the ink composition.
本発明の水性ボールペン用インク組成物には、少なくとも、上記平均粒子径が０．５～６μｍの着色樹脂粒子と、キサンタンガム及びポリビニルピロリドンを含有し、前記ポリビニルピロリドン／キサンタンガムの質量比が１～９であることを特徴とするものであり、上記着色樹脂粒子以外の着色剤、水溶性溶剤の他、残部として溶媒である水（水道水、精製水、蒸留水、イオン交換水、純水等）の他、本発明の効果を損なわない範囲で、分散剤、潤滑剤、ｐＨ調整剤、防錆剤、防腐剤もしくは防菌剤などを適宜含有することができる。 The aqueous ballpoint pen ink composition of the present invention contains at least colored resin particles having an average particle diameter of 0.5 to 6 μm, xanthan gum and polyvinylpyrrolidone, and the mass ratio of polyvinylpyrrolidone/xanthan gum is 1 to 9. In addition to a coloring agent other than the colored resin particles mentioned above, a water-soluble solvent, and the remainder water as a solvent (tap water, purified water, distilled water, ion-exchanged water, pure water, etc.) In addition, a dispersant, a lubricant, a pH adjuster, a rust preventive, a preservative, an antibacterial agent, and the like may be appropriately contained within a range that does not impair the effects of the present invention.
用いることができる分散剤としては、ノニオン、アニオン界面活性剤や水溶性樹脂が用いられる。好ましくは水溶性高分子が用いられる。
潤滑剤としては、顔料の表面処理剤にも用いられる多価アルコールの脂肪酸エステル、糖の高級脂肪酸エステル、ポリオキシアルキレン高級脂肪酸エステル、アルキル燐酸エステルなどのノニオン系や、高級脂肪酸アミドのアルキルスルホン酸塩、アルキルアリルスルホン酸塩などのアニオン系、ポリアルキレングリコールの誘導体やフッ素系界面活性剤、ポリエーテル変性シリコーンなどが挙げられる。
As dispersants that can be used, nonionic and anionic surfactants and water-soluble resins are used. Preferably, water-soluble polymers are used.
As lubricants, nonionic lubricants such as fatty acid esters of polyhydric alcohols, higher fatty acid esters of sugars, polyoxyalkylene higher fatty acid esters, and alkyl phosphate esters, which are also used as surface treatment agents for pigments, and alkyl sulfonic acids of higher fatty acid amides are used. Examples include salts, anionic substances such as alkylaryl sulfonates, derivatives of polyalkylene glycol, fluorine-based surfactants, and polyether-modified silicones.
ｐＨ調整剤としては、アンモニア、尿素、モノエタノーアミン、ジエタノールアミン、トリエタノールアミンや、トリポリリン酸ナトリウム、炭酸ナトリウムなとの炭酸やリン酸のアルカリ金属塩、水酸化ナトリウムなどのアルカリ金属の水和物などが挙げられる。また、防錆剤としては、ベンゾトリアゾール、トリルトリアゾール、ジシクロへキシルアンモニウムナイトライト、サポニン類など、防腐剤もしくは防菌剤としては、フェノール、ナトリウムオマジン、安息香酸ナトリウム、チアゾリン系化合物、ベンズイミダゾール系化合物などが挙げられる。
上記分散剤、潤滑剤、ｐＨ調整剤、防錆剤、防腐剤もしくは防菌剤などの各成分は、１種単独で使用してもよく、２種以上を併用してもよい。また、これらの市販品があればそれを使用することができる
Examples of pH adjusters include ammonia, urea, monoethanolamine, diethanolamine, triethanolamine, alkali metal salts of carbonic acid and phosphoric acid such as sodium tripolyphosphate and sodium carbonate, and alkali metal hydrates such as sodium hydroxide. Examples include. In addition, rust inhibitors include benzotriazole, tolyltriazole, dicyclohexylammonium nitrite, saponins, etc. Preservatives or antibacterial agents include phenol, sodium omazine, sodium benzoate, thiazoline compounds, benzimidazole, etc. Examples include compound compounds.
Each component such as the above-mentioned dispersant, lubricant, pH adjuster, rust preventive, antiseptic, or antibacterial agent may be used alone or in combination of two or more. You can also use these commercially available products if you have them.
本発明の水性ボールペン用インク組成物は、少なくとも、上記平均粒子径が０．５～６μｍの着色樹脂粒子と、キサンタンガムと、ポリビニルピロリドンと、水溶性溶剤、その他の各成分をボールペン用インクの用途に応じて適宜組み合わせ、前記ポリビニルピロリドン／キサンタンガムの質量比が１～９となるように配合せしめて、ホモミキサー、ホモジナイザーもしくはディスパー等の攪拌機により撹拌混合することにより、更に必要に応じて、ろ過や遠心分離によってインク組成物中の粗大粒子を除去すること等によって水性ボールペン用インク組成物を調製することができる。
水性ボールペンでは、該水性ボールペン用インク組成物を、直径が０．１８～２．０ｍｍのボールを備えた水性ボールペン体に充填することにより作製することができる。
用いる水性ボールペン体として、直径が上記範囲のボールを備えたものであれば、特に限定されず、特に、上記水性インク組成物をポリプロピレンチューブのインク収容管に充填し、先端のステンレスチップ（ボールは超鋼合金）を有するリフィールの水性ボールペンに仕上げたものが望ましい。
The aqueous ballpoint pen ink composition of the present invention contains at least the above-mentioned colored resin particles having an average particle diameter of 0.5 to 6 μm, xanthan gum, polyvinylpyrrolidone, a water-soluble solvent, and other components for use in ballpoint pen ink. The polyvinylpyrrolidone/xanthan gum mass ratio is 1 to 9, and the mixture is stirred and mixed using a stirrer such as a homomixer, a homogenizer, or a disper. If necessary, filtration or An aqueous ballpoint pen ink composition can be prepared by removing coarse particles in the ink composition by centrifugation.
A water-based ballpoint pen can be produced by filling the aqueous ballpoint pen ink composition into an aqueous ballpoint pen body equipped with a ball having a diameter of 0.18 to 2.0 mm.
The aqueous ballpoint pen body to be used is not particularly limited as long as it has a ball with a diameter within the above range.In particular, the aqueous ink composition is filled into an ink storage tube of a polypropylene tube, A refillable water-based ballpoint pen with a super steel alloy) is desirable.
本発明の水性ボールペン用インク組成物は、他の水性インク組成物の製造方法と比べて特に変わるところはなく製造することができる。
すなわち、本発明の水性ボールペン用インク組成物は、少なくとも、上記平均粒子径が０．５～６μｍの着色樹脂粒子と、キサンタンガム及びポリビニルピロリドン、その他の成分を含有せしめ、前記ポリビニルピロリドン／キサンタンガムの質量比が１～９となる
ようにミキサー等、更に、例えば、強力な剪断を加えることができるビーズミル、ホモミキサー、ホモジナイザー等を用いて撹拌条件を好適な条件に設定等して混合撹拌することによって、水性ボールペン用インク組成物を製造することができる。
また、本発明の水性ボールペン用インク組成物のｐＨ（２５℃）は、使用性、安全性、インク自身の安定性、インク収容体とのマッチング性の点からｐＨ調整剤などにより５～１０に調整されることが好ましく、更に好ましくは、６～９．５とすることが望ましい。
The aqueous ballpoint pen ink composition of the present invention can be produced without any particular difference compared to other methods for producing aqueous ink compositions.
That is, the aqueous ballpoint pen ink composition of the present invention contains at least colored resin particles having an average particle diameter of 0.5 to 6 μm, xanthan gum, polyvinylpyrrolidone, and other components, and the mass of the polyvinylpyrrolidone/xanthan gum By using a mixer or the like, for example, a bead mill that can apply strong shear, a homomixer, a homogenizer, etc., set the stirring conditions to suitable conditions so that the ratio is 1 to 9, and mix and stir. , an aqueous ballpoint pen ink composition can be produced.
In addition, the pH (25°C) of the aqueous ballpoint pen ink composition of the present invention is adjusted to 5 to 10 by using a pH adjuster etc. from the viewpoint of usability, safety, stability of the ink itself, and matching with the ink container. It is preferably adjusted, more preferably from 6 to 9.5.
本発明の水性ボールペン用インク組成物は、ボールペンチップなどのペン先部を備えたボールペンに搭載される。
本発明における水性ボールペンとしては、上記組成の水性ボールペン用インク組成物をボールペン用インク収容体（リフィール）に収容すると共に、該インク収容体内に収容された水性インク組成物とは相溶性がなく、かつ、該水性インク組成物に対して比重が小さい物質、例えば、ポリブテン、シリコーンオイル、鉱油等がインク追従体として収容されるものが挙げられる。
なお、水性ボールペンの構造は、特に限定されず、例えば、軸筒自体をインク収容体として該軸筒内に上記構成の水性ボールペン用インク組成物を充填したコレクター構造（インク保持機構）を備えた直液式のボールペンであってもよいものである。
The aqueous ballpoint pen ink composition of the present invention is installed in a ballpoint pen equipped with a pen tip such as a ballpoint pen tip.
In the aqueous ballpoint pen of the present invention, an ink composition for an aqueous ballpoint pen having the above composition is accommodated in an ink container (refill) for a ballpoint pen, and is not compatible with the aqueous ink composition accommodated in the ink container; Further, examples include those in which a substance having a small specific gravity relative to the aqueous ink composition, such as polybutene, silicone oil, mineral oil, etc., is accommodated as an ink follower.
The structure of the aqueous ballpoint pen is not particularly limited, and for example, the aqueous ballpoint pen may have a collector structure (ink holding mechanism) in which the barrel itself is used as an ink container and the ink composition for an aqueous ballpoint pen having the above structure is filled in the barrel. A direct liquid type ballpoint pen may also be used.
このように構成される本発明の水性ボールペン用インク組成物にあっては、少なくとも、上記平均粒子径が０．５～６μｍの着色樹脂粒子と、キサンタンガム及びポリビニルピロリドンを含有し、前記ポリビニルピロリドン／キサンタンガムの質量比が１～９であることを特徴とするものであり、例えば、熱変色マイクロカプセル（熱変色性粒子）のような平均粒子径０．５μｍ超過となる大きい着色樹脂粒子の場合には、一般的な染料・顔料と比較してインク中での流動性が低く、それに伴い静から動、或いは動から静状態への応答性がやや鈍く、ボールペンのような動作の切り替えが頻繁で、インクに対する剪断力の変化が大きい筆記具においては、その特性が描線に現れやすく、特に筆記を休止した直後の書き出しに時にインクが出渋る現象、すなわち、初筆性の低下が見られるものであつたが、本発明では、書き出し時のインクが出渋る現象である初筆性の低下がない水性ボールペン用インク組成物が得られるものとなる。 The aqueous ballpoint pen ink composition of the present invention configured as described above contains at least colored resin particles having an average particle diameter of 0.5 to 6 μm, xanthan gum and polyvinylpyrrolidone, and contains the polyvinylpyrrolidone/ It is characterized in that the mass ratio of xanthan gum is 1 to 9, and for example, in the case of large colored resin particles with an average particle diameter exceeding 0.5 μm, such as thermochromic microcapsules (thermochromic particles). Compared to general dyes and pigments, they have lower fluidity in ink, and as a result, their responsiveness from static to dynamic or dynamic to static states is somewhat slow, and they frequently switch between movements like a ballpoint pen. In writing instruments that have large changes in the shear force applied to ink, this characteristic tends to appear in the lines drawn, and in particular, there is a phenomenon in which the ink is sometimes difficult to draw when starting to write immediately after a pause in writing, that is, a decrease in first-time writing ability is observed. However, according to the present invention, an ink composition for an aqueous ballpoint pen can be obtained that does not cause a decrease in initial writing performance, which is a phenomenon in which ink is difficult to dispense at the beginning of writing.
次に、用いる着色樹脂粒子の製造例１～３、水性ボールペン用インク組成物の実施例１～８及び比較例１～４により本発明を更に詳細に説明するが、本発明は下記実施例等に限定されるものではない。また、製造例１～３で得た着色樹脂粒子などの平均粒子径（Ｄ５０：μｍ）は、日機装株式会社の粒子径分布解析装置ＨＲＡ９３２０－Ｘ１００を用いて測定した。 Next, the present invention will be explained in more detail with reference to Production Examples 1 to 3 of the colored resin particles used, Examples 1 to 8 of the aqueous ballpoint pen ink compositions, and Comparative Examples 1 to 4. It is not limited to. Further, the average particle size (D50: μm) of the colored resin particles obtained in Production Examples 1 to 3 was measured using a particle size distribution analyzer HRA9320-X100 manufactured by Nikkiso Co., Ltd.
〔製造例１：着色性樹脂粒子；熱変色性粒子の製造〕
ロイコ色素として、ＥＴＡＣ（山田化学工業社製）１質量部（以下、単に「部」という）、顕色剤として、ビスフェノールＡ２部、及び変色性温度調整剤として、ミリスチン酸
ミリスチル２４部を１００℃に加熱溶融して、均質な組成物２７部を得た。上記で得た
組成物２７部の均一な熱溶液にカプセル膜剤として、イソシアネート１０部 及びポリオ
ール１０部を加えて攪拌混合した。次いで、保護コロイドとして１２％ポリビニルアルコール水溶液６０部を用いて、２５℃で乳化して分散液を調製した。次いで、５％の多価アミン５部を用いて、８０℃で６０分間処理してコアシェル型のマイクロカプセルを得た。
この着色樹脂粒子の平均粒子径（Ｄ５０）は、３．５μｍであった。
[Production Example 1: Colored resin particles; Production of thermochromic particles]
As a leuco dye, 1 part by mass (hereinafter simply referred to as "part") of ETAC (manufactured by Yamada Chemical Industry Co., Ltd.), 2 parts of bisphenol A as a color developer, and 24 parts of myristyl myristate as a discoloration temperature regulator at 100°C. The mixture was heated and melted to obtain 27 parts of a homogeneous composition. To a homogeneous hot solution of 27 parts of the composition obtained above were added 10 parts of isocyanate and 10 parts of polyol as capsule membrane agents and mixed with stirring. Next, 60 parts of a 12% polyvinyl alcohol aqueous solution was used as a protective colloid and emulsified at 25° C. to prepare a dispersion. Next, the mixture was treated with 5 parts of 5% polyvalent amine at 80° C. for 60 minutes to obtain core-shell type microcapsules.
The average particle diameter (D50) of the colored resin particles was 3.5 μm.
〔製造例２：着色性樹脂粒子；ウレタン系黒色粒子〕
油相溶液として、酢酸エチル１２．５質量部を６０℃に加温しながら、油溶性黒染料（Ｏｉｌ Ｂｌａｃｋ ８６０、オリヱント化学工業社製）３．５質量部及びテルペンフェ
ノール樹脂（ＹＳポリスターＮ１２５ ヤスハラケミカル社製）０．５質量部を加えて十分に溶解させた。次いで、ここにプレポリマーとしてのヘキサメチレンジイソシアネートのイソシアヌレート変性体（ＴＬＡ－１００、旭化成社製）８質量部を加えて、油相溶液を作製した。
水相溶液としては、蒸留水２００質量部を６０℃に加温しながら、ここに分散剤としてのポリビニルアルコール（ＰＶＡ－２０５、クラレ社製）１５質量部を溶解して、水相溶液を作製した。
６０℃の水相溶液に油相溶液を投入し、ホモジナイザーで６時間撹拌することにより乳化混合して重合を完了した。
得られた分散体を遠心処理することで着色性樹脂粒子（ウレタン系黒色粒子）を得た。この着色樹脂粒子の平均粒子径（Ｄ５０）は、１．４μｍであった。
[Production Example 2: Colored resin particles; urethane black particles]
As an oil phase solution, while heating 12.5 parts by mass of ethyl acetate to 60°C, 3.5 parts by mass of oil-soluble black dye (Oil Black 860, manufactured by Orient Chemical Industry Co., Ltd.) and terpene phenol resin (YS Polyster N125, manufactured by Yasuhara Chemical Co., Ltd.) were added. 0.5 parts by mass (manufactured by Co., Ltd.) was added and sufficiently dissolved. Next, 8 parts by mass of an isocyanurate modified hexamethylene diisocyanate (TLA-100, manufactured by Asahi Kasei Corporation) as a prepolymer was added thereto to prepare an oil phase solution.
An aqueous phase solution was prepared by heating 200 parts by mass of distilled water to 60°C and dissolving 15 parts by mass of polyvinyl alcohol (PVA-205, manufactured by Kuraray Co., Ltd.) as a dispersant therein. did.
The oil phase solution was added to the aqueous phase solution at 60° C., and stirred with a homogenizer for 6 hours to emulsify and mix to complete polymerization.
Colored resin particles (urethane black particles) were obtained by centrifuging the obtained dispersion. The average particle diameter (D50) of the colored resin particles was 1.4 μm.
〔製造例３：着色性樹脂粒子；ウレタン系白色粒子〕
油相溶液として、ミリスチン酸ミリスチル９．６部を６０℃に加温しながら、酸化チタン２．４部を加えて十分に分散させた。次いで、メチレンジフェニル －４，４´－ジイ
ソシアネート（３モル）のトリメチロールプロパン（１モル）付加物（ Ｄ－１０９、三
井化学社製）９部を加え、更にエチレングリコールモノベンジルエーテル２部を加えた。水相溶液としては、蒸留水６００部に対して、ポリビニルアルコール（ＰＶＡ－２０５、クラレ社製）１５部を溶解し、これに前記油相溶液を投入し、ホモジナイザーで乳化混合して重合を完了した。得られた分散体を遠心処理することでマイクロカプセルを回収し、マイクロカプセル顔料を得た。この着色樹脂粒子の平均粒子径（Ｄ５０）は、０．６μｍであった。
[Production Example 3: Colored resin particles; urethane-based white particles]
As an oil phase solution, 9.6 parts of myristyl myristate was heated to 60° C. while 2.4 parts of titanium oxide was added thereto and sufficiently dispersed. Next, 9 parts of trimethylolpropane (1 mol) adduct of methylene diphenyl-4,4'-diisocyanate (3 mol) (D-109, manufactured by Mitsui Chemicals) were added, and further 2 parts of ethylene glycol monobenzyl ether were added. Ta. For the aqueous phase solution, 15 parts of polyvinyl alcohol (PVA-205, manufactured by Kuraray Co., Ltd.) was dissolved in 600 parts of distilled water, the oil phase solution was added thereto, and the mixture was emulsified with a homogenizer to complete the polymerization. did. The obtained dispersion was centrifuged to collect microcapsules, thereby obtaining a microcapsule pigment. The average particle diameter (D50) of the colored resin particles was 0.6 μm.
〔実施例１～８及び比較例１～４〕
製造例１～３の着色性樹脂粒子を用いると共に、下記表１に示す配合組成のキサンタンガム、ポリビニルピロリドンなどにより、常法により、各水性ボールペン用インク組成物を調整した。
上記実施例１～８及び比較例１～４で得られた水性ボールペン用インク組成物について、下記方法により水性ボールペンを作製して、下記評価方法で初筆性について評価を行った。
これらの結果を下記表１に示す。
[Examples 1 to 8 and Comparative Examples 1 to 4]
In addition to using the colored resin particles of Production Examples 1 to 3, ink compositions for aqueous ballpoint pens were prepared by a conventional method using xanthan gum, polyvinylpyrrolidone, and the like having the composition shown in Table 1 below.
Regarding the ink compositions for aqueous ballpoint pens obtained in Examples 1 to 8 and Comparative Examples 1 to 4 above, aqueous ballpoint pens were prepared by the following method, and first-time writing properties were evaluated by the following evaluation method.
These results are shown in Table 1 below.
（水性ボールペンを作製）
上記で得られた各インク組成物を用いて水性ボールペンを作製した。具体的には、ボールペン〔三菱鉛筆株式会社製、商品名：シグノＵＭ－１００〕の軸を使用し、内径４．０ｍｍ、長さ１１３ｍｍのポリプロピレン製インク収容管とステンレス製チップ（超硬合金ボール、ボール径０．７ｍｍ）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水性インクを充填し、インク後端に鉱油を主成分とするインク追従体を装填し、水性ボールペンを作製した。
(Making a water-based ballpoint pen)
Aqueous ballpoint pens were produced using each of the ink compositions obtained above. Specifically, we used the shaft of a ballpoint pen [manufactured by Mitsubishi Pencil Co., Ltd., product name: Signo UM-100], a polypropylene ink storage tube with an inner diameter of 4.0 mm and a length of 113 mm, and a stainless steel tip (carbide ball). A refill consisting of a ball diameter of 0.7 mm) and a joint connecting the storage tube and the tip is filled with each of the above water-based inks, an ink follower whose main component is mineral oil is loaded at the rear end of the ink, and a water-based ballpoint pen is inserted. Created.
〔初筆性の評価方法〕
上記で得た各水性ボールペンについて、キャップをしない状態で、２５℃、５０％ＲＨ下で６０分放置後、ＰＰＣ用紙に直線を筆記し、下記評価基準で初筆性を評価した。
評価基準：
Ａ：書き始めから問題なく筆記可能
Ｂ：書き始めから０ｍｍ超、５ｍｍ未満のカスレが確認される
Ｃ：書き始めから５ｍｍ以上のカスレが確認される
[How to evaluate first-time writing]
Each of the water-based ballpoint pens obtained above was left uncapped at 25° C. and 50% RH for 60 minutes, then a straight line was drawn on PPC paper, and the first-time writing performance was evaluated using the following evaluation criteria.
Evaluation criteria:
A: Can be written without any problem from the beginning of writing. B: Fading of more than 0 mm and less than 5 mm is confirmed from the beginning of writing. C: Fading of 5 mm or more is confirmed from the beginning of writing.
上記表１の結果から明らかなように、本発明範囲となる実施例１～８の水性ボールペン用インク組成物は、本発明の範囲外となる比較例１～４に較べ、初筆性に優れることが確認された。
これに対して、比較例１～４を見ると、比較例１及び２は、キサンタンガム、ポリビニルピロリドン単独配合であり、また、比較例３及び４はポリビニルピロリドン／キサンタンガムの質量比が１～９の範囲を外れる場合であり、これらの場合は書き始めから初筆性が悪くなることが確認された。
以上の実施例１～８及び比較例１～４の各評価結果を総合してみると、本発明範囲となる実施例１～８の水性ボールペン用インク組成物とすることにより、初めて、初筆性が著しく向上し、特有の作用効果が発揮できることが判った。
As is clear from the results in Table 1 above, the water-based ballpoint pen ink compositions of Examples 1 to 8, which fall within the scope of the present invention, have superior initial writing properties compared to Comparative Examples 1 to 4, which fall outside the scope of the present invention. This was confirmed.
On the other hand, looking at Comparative Examples 1 to 4, Comparative Examples 1 and 2 contain xanthan gum and polyvinylpyrrolidone alone, and Comparative Examples 3 and 4 have a polyvinylpyrrolidone/xanthan gum mass ratio of 1 to 9. These are cases where the writing is out of range, and it has been confirmed that in these cases, the initial writing quality is poor from the beginning of writing.
Comprehensively, the evaluation results of Examples 1 to 8 and Comparative Examples 1 to 4 above show that the ink compositions for aqueous ballpoint pens of Examples 1 to 8, which fall within the scope of the present invention, are effective for first-time writing. It was found that the properties were significantly improved and unique effects could be exhibited.
水性ボールペンに好適なインク組成物が得られる。 An ink composition suitable for water-based ballpoint pens is obtained.
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