JP2006028370A - Ink composition for writing tool - Google Patents
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- JP2006028370A JP2006028370A JP2004210193A JP2004210193A JP2006028370A JP 2006028370 A JP2006028370 A JP 2006028370A JP 2004210193 A JP2004210193 A JP 2004210193A JP 2004210193 A JP2004210193 A JP 2004210193A JP 2006028370 A JP2006028370 A JP 2006028370A
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- 239000000203 mixture Substances 0.000 title claims abstract description 70
- 239000002245 particle Substances 0.000 claims abstract description 128
- 239000003094 microcapsule Substances 0.000 claims abstract description 55
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000002904 solvent Substances 0.000 claims abstract description 29
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000006185 dispersion Substances 0.000 claims abstract description 27
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 19
- 229920005989 resin Polymers 0.000 claims abstract description 13
- 239000011347 resin Substances 0.000 claims abstract description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 11
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910021647 smectite Inorganic materials 0.000 claims abstract description 10
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 5
- 239000003784 tall oil Substances 0.000 claims abstract description 5
- 239000011787 zinc oxide Substances 0.000 claims abstract description 5
- XPXMKIXDFWLRAA-UHFFFAOYSA-N hydrazinide Chemical compound [NH-]N XPXMKIXDFWLRAA-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000000944 linseed oil Substances 0.000 claims abstract description 4
- 235000021388 linseed oil Nutrition 0.000 claims abstract description 4
- 229920000728 polyester Polymers 0.000 claims abstract description 3
- 230000005484 gravity Effects 0.000 claims description 21
- 239000000049 pigment Substances 0.000 claims description 21
- 239000000463 material Substances 0.000 claims description 17
- 238000004040 coloring Methods 0.000 claims description 12
- 239000002270 dispersing agent Substances 0.000 claims description 10
- -1 acrylic compound Chemical class 0.000 claims description 7
- 239000002952 polymeric resin Substances 0.000 claims description 3
- 229920003002 synthetic resin Polymers 0.000 claims description 3
- 235000004443 Ricinus communis Nutrition 0.000 claims description 2
- 239000004359 castor oil Substances 0.000 abstract description 2
- 235000019438 castor oil Nutrition 0.000 abstract description 2
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- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 abstract 1
- 239000000976 ink Substances 0.000 description 74
- 238000000034 method Methods 0.000 description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 17
- 238000003756 stirring Methods 0.000 description 14
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- 238000011156 evaluation Methods 0.000 description 11
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 8
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- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 206010068516 Encapsulation reaction Diseases 0.000 description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 2
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 description 2
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 2
- 238000012695 Interfacial polymerization Methods 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- PRXRUNOAOLTIEF-ADSICKODSA-N Sorbitan trioleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@@H](OC(=O)CCCCCCC\C=C/CCCCCCCC)[C@H]1OC[C@H](O)[C@H]1OC(=O)CCCCCCC\C=C/CCCCCCCC PRXRUNOAOLTIEF-ADSICKODSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 238000005354 coacervation Methods 0.000 description 2
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- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 2
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- 229940057995 liquid paraffin Drugs 0.000 description 2
- 239000012860 organic pigment Substances 0.000 description 2
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- 239000012463 white pigment Substances 0.000 description 2
- MJYQFWSXKFLTAY-OVEQLNGDSA-N (2r,3r)-2,3-bis[(4-hydroxy-3-methoxyphenyl)methyl]butane-1,4-diol;(2r,3r,4s,5s,6r)-6-(hydroxymethyl)oxane-2,3,4,5-tetrol Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O.C1=C(O)C(OC)=CC(C[C@@H](CO)[C@H](CO)CC=2C=C(OC)C(O)=CC=2)=C1 MJYQFWSXKFLTAY-OVEQLNGDSA-N 0.000 description 1
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- LOXRGHGHQYWXJK-UHFFFAOYSA-N 1-octylsulfanyloctane Chemical compound CCCCCCCCSCCCCCCCC LOXRGHGHQYWXJK-UHFFFAOYSA-N 0.000 description 1
- SDGKUVSVPIIUCF-UHFFFAOYSA-N 2,6-dimethylpiperidine Chemical compound CC1CCCC(C)N1 SDGKUVSVPIIUCF-UHFFFAOYSA-N 0.000 description 1
- BJCIHMAOTRVTJI-UHFFFAOYSA-N 2-butoxy-n,n-dibutyl-5-(2,4,4-trimethylpentan-2-yl)aniline Chemical compound CCCCOC1=CC=C(C(C)(C)CC(C)(C)C)C=C1N(CCCC)CCCC BJCIHMAOTRVTJI-UHFFFAOYSA-N 0.000 description 1
- WBIQQQGBSDOWNP-UHFFFAOYSA-N 2-dodecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O WBIQQQGBSDOWNP-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- 229910002012 Aerosil® Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 1
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- 241000047703 Nonion Species 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 239000004147 Sorbitan trioleate Substances 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- GTVWRXDRKAHEAD-UHFFFAOYSA-N Tris(2-ethylhexyl) phosphate Chemical compound CCCCC(CC)COP(=O)(OCC(CC)CCCC)OCC(CC)CCCC GTVWRXDRKAHEAD-UHFFFAOYSA-N 0.000 description 1
- 239000007874 V-70 Substances 0.000 description 1
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- 230000000996 additive effect Effects 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
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- 239000003429 antifungal agent Substances 0.000 description 1
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- 238000000149 argon plasma sintering Methods 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000007869 azo polymerization initiator Substances 0.000 description 1
- 230000000740 bleeding effect Effects 0.000 description 1
- 239000002775 capsule Substances 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 150000001733 carboxylic acid esters Chemical class 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
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- 239000011362 coarse particle Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000011246 composite particle Substances 0.000 description 1
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- 150000004696 coordination complex Chemical class 0.000 description 1
- 239000006071 cream Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
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- 229940060296 dodecylbenzenesulfonic acid Drugs 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 235000004426 flaxseed Nutrition 0.000 description 1
- IVJISJACKSSFGE-UHFFFAOYSA-N formaldehyde;1,3,5-triazine-2,4,6-triamine Chemical compound O=C.NC1=NC(N)=NC(N)=N1 IVJISJACKSSFGE-UHFFFAOYSA-N 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 1
- 239000001863 hydroxypropyl cellulose Substances 0.000 description 1
- 235000010977 hydroxypropyl cellulose Nutrition 0.000 description 1
- 230000001771 impaired effect Effects 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
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 229940053080 isosol Drugs 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
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- 229910052757 nitrogen Inorganic materials 0.000 description 1
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- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
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- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 150000003021 phthalic acid derivatives Chemical class 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
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
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- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
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- 239000000992 solvent dye Substances 0.000 description 1
- 235000019337 sorbitan trioleate Nutrition 0.000 description 1
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- JOUDBUYBGJYFFP-FOCLMDBBSA-N thioindigo Chemical compound S\1C2=CC=CC=C2C(=O)C/1=C1/C(=O)C2=CC=CC=C2S1 JOUDBUYBGJYFFP-FOCLMDBBSA-N 0.000 description 1
- 239000003799 water insoluble solvent Substances 0.000 description 1
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Images
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- Inks, Pencil-Leads, Or Crayons (AREA)
Abstract
Description
本発明は、隠蔽性が高く鮮明な筆跡を長期に亘り維持することができる筆記具用インキ組成物に関する。 The present invention relates to an ink composition for a writing instrument that has a high concealability and can maintain a clear handwriting over a long period of time.
一般に、酸化チタンは、その優れた光散乱効果により、白色度、隠蔽度を付与することができる顔料であり、白色顔料及び隠蔽型修正液として使用されている。その使用方法としては、酸化チタンそのものを水や有機溶媒からなる液体媒体中に分散させた水性又は油性などのインキ組成物を調製し、修正液や筆記具用インキなどとして使用されている。
しかしながら、酸化チタン自身の比重は、３．８〜４．１と非常に大きく、分散体中の粒子径を小さくしても沈降及び分離現象が発生する大きな欠点を有している。
In general, titanium oxide is a pigment that can impart whiteness and concealment due to its excellent light scattering effect, and is used as a white pigment and concealment type correction liquid. As its use method, an aqueous or oil-based ink composition in which titanium oxide itself is dispersed in a liquid medium composed of water or an organic solvent is prepared and used as a correction liquid, a writing instrument ink, or the like.
However, the specific gravity of titanium oxide itself is very large, such as 3.8 to 4.1, and has a serious drawback that sedimentation and separation occur even if the particle size in the dispersion is reduced.
このような欠点を解消するものとして、筆記具用インキでは、例えば、酸化チタンとサクシノグルカンからなる高分子多糖類と水とより少なくともなる水性インキ組成物（例えば、特許文献１参照）や、酸化チタンとオレイン酸を必須成分として含むボールペン用水性インキ（例えば、特許文献２参照）、また、必須成分として酸化チタンを内包したマイクロカプセル顔料と、水と、水溶性有機溶剤とから少なくともな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）が知られている。 In order to eliminate such drawbacks, in the ink for writing instruments, for example, an aqueous ink composition (for example, see Patent Document 1) comprising at least a high molecular weight polysaccharide composed of titanium oxide and succinoglucan and water, or oxidation. Water-based ink for ballpoint pens containing titanium and oleic acid as essential components (for example, see Patent Document 2), and for ballpoint pens comprising at least a microcapsule pigment containing titanium oxide as essential components, water, and a water-soluble organic solvent A water-based ink composition (see, for example, Patent Document 3) is known.
しかしながら、上記特許文献１及び２に記載される水性インキ組成物では、当初は酸化チタンの沈降分離が若干抑制されるが、時間がたつにつれ沈降及び分離現象が生じるなどの点に未だ課題があるものである。また、上記特許文献３に記載される水性インキ組成物は、沈降及び分離現象は幾分解消されるものであるが、マイクロカプセル顔料製造時の隠蔽性粒子の脱落があったり、隠蔽性粒子の粒子径の均一化が難しく、更に、マイクロカプセルの粒子径の均一化及びマイクロカプセル内の粒子数の均一化が難しく、安定な品質を有するマイクロカプセル顔料を得ることが難しい点に未だ課題があるものである。
本発明は、上記従来技術の課題に鑑み、これを解消しようとするものであり、従来の白色顔料である酸化チタン粒子より比重が低く、白色性及び隠蔽性に優れる品質の安定なマイクロカプセル粒子を使用して、隠蔽性が高く鮮明な筆跡を長期に亘り維持することができる筆記具用インキ組成物を提供することを目的とする。 The present invention has been made in view of the above-mentioned problems of the prior art, and is intended to solve this problem. The microcapsule particles have a specific gravity lower than that of conventional white pigment titanium oxide particles and have excellent whiteness and hiding properties. An object of the present invention is to provide an ink composition for a writing instrument that can maintain a clear handwriting with high concealability over a long period of time.
本発明者らは、上記従来の課題等を解決するために、鋭意研究を重ねた結果、マイクロカプセル粒子中に酸化チタンなどの隠蔽性粒子、特定成分等を溶媒に分散した分散体を封入せしめたものを用いることにより、上記目的の筆記具用インキ組成物が得られることを見い出し、本発明を完成するに至ったのである。 As a result of intensive studies to solve the above-described conventional problems, the present inventors have encapsulated a dispersion in which concealing particles such as titanium oxide and a specific component are dispersed in a solvent in microcapsule particles. As a result, it was found that the ink composition for a writing instrument having the above-mentioned purpose can be obtained by using the above-mentioned one, and the present invention has been completed.
すなわち、本発明は、次の（１）〜（１０）に存する。
（１） 隠蔽性粒子、構造粘性付与剤が溶媒に分散されている分散体が封入されたマイクロカプセル粒子を含有することを特徴とする筆記具用インキ組成物。
（２） 隠蔽性粒子が酸化チタン、酸化亜鉛及び中空樹脂粒子の中から選ばれる少なくとも１種である上記（１）記載の筆記具用インキ組成物。
（３） 構造粘性付与剤がスメクタイト、変性スメクタイト、ヒマシ油変性誘導体、シリカ、アミノアマイド、ポリエステル変性体、アクリル化合物、アクリル化合物、アマニ油及びトール油の中から選ばれる少なくとも１種である上記（１）又は（２）記載の筆記具用インキ組成物。
（４） 溶媒の少なくとも１種類が比重１．０以下の溶媒である上記（１）〜（３）の何れか一つに記載の筆記具用インキ組成物。
（５） 分散体中に分散剤を含有する上記（１）〜（４）の何れか一つに記載の筆記具用インキ組成物。
（６） 分散体中に染料、顔料の着色性を有する色材の少なくとも１種を含有する上記（１）〜（５）の何れか一つに記載の筆記具用インキ組成物。
（７） マイクロカプセル粒子の壁材が高分子樹脂からなる上記（１）〜（６）の何れか一つに記載の筆記具用インキ組成物。
（８） マイクロカプセル粒子の粒径が１〜２００μｍである上記（１）〜（７）の何れか一つに記載の筆記具用インキ組成物。
（９） ＥＬＤ粘度計における２５℃、５０ｒｐｍの筆記具用インキ組成物の粘度が、３〜５０ｍＰａ・ｓである上記（１）〜（８）の何れか一つに記載の筆記具用インキ組成物。
（１０） 筆記具用インキ組成物がサインペン用インキ組成物である上記（１）〜（９）の何れか一つに記載の筆記具用インキ組成物。
That is, the present invention resides in the following (1) to (10).
(1) An ink composition for a writing instrument comprising microcapsule particles encapsulating a dispersion in which concealing particles and a structural viscosity imparting agent are dispersed in a solvent.
(2) The ink composition for a writing instrument according to the above (1), wherein the concealable particles are at least one selected from titanium oxide, zinc oxide and hollow resin particles.
(3) The above structural viscosity imparting agent is at least one selected from smectite, modified smectite, castor oil modified derivative, silica, aminoamide, polyester modified, acrylic compound, acrylic compound, linseed oil and tall oil ( The ink composition for writing instruments according to 1) or (2).
(4) The ink composition for a writing instrument according to any one of (1) to (3), wherein at least one of the solvents is a solvent having a specific gravity of 1.0 or less.
(5) The ink composition for a writing instrument according to any one of (1) to (4), wherein the dispersion contains a dispersant.
(6) The ink composition for a writing instrument as described in any one of (1) to (5) above, wherein the dispersion contains at least one kind of coloring material having a coloring property of a dye or a pigment.
(7) The ink composition for a writing instrument according to any one of (1) to (6), wherein the wall material of the microcapsule particles is made of a polymer resin.
(8) The ink composition for a writing instrument according to any one of (1) to (7), wherein the particle size of the microcapsule particles is 1 to 200 μm.
(9) The ink composition for a writing instrument according to any one of the above (1) to (8), wherein the viscosity of the ink composition for a writing instrument at 25 ° C. and 50 rpm in an ELD viscometer is 3 to 50 mPa · s.
(10) The ink composition for a writing instrument according to any one of (1) to (9), wherein the ink composition for a writing instrument is an ink composition for a sign pen.
本発明によれば、経時安定性に優れると共に、隠蔽性が高く鮮明な筆跡を長期に亘り維持することができる筆記具用インキ組成物が提供される。 ADVANTAGE OF THE INVENTION According to this invention, while being excellent in stability over time, the ink composition for writing instruments which can maintain a clear handwriting with high concealability over a long period of time is provided.
以下に、本発明の実施形態を詳しく説明する。
本発明の筆記具用インキ組成物は、隠蔽性粒子、構造粘性付与剤が溶媒に分散されている分散体が封入されたマイクロカプセル粒子を含有することを特徴とするものである。
本発明におけるマイクロカプセル粒子Ａとしては、例えば、図１に示すように、隠蔽性粒子１０、構造粘性付与剤を溶媒に分散させた分散体１２をマイクロカプセル２０内に封入した粒子が挙げられる。
Hereinafter, embodiments of the present invention will be described in detail.
The ink composition for a writing instrument of the present invention is characterized in that it contains microcapsule particles encapsulating a dispersion in which concealing particles and a structural viscosity imparting agent are dispersed in a solvent.
Examples of the microcapsule particles A in the present invention include particles in which a
用いることができる隠蔽性粒子１０としては、隠蔽性及び白色性を発揮せしめる粒子であれば特に限定されるものでないが、例えば、酸化チタン、酸化亜鉛及び中空樹脂粒子の中から選ばれる少なくとも１種（各単独又は２種以上、以下同様）が挙げられる。これらの粒子は、粒子表面が有機チタネート等で親油性表面処理されている隠蔽性粒子であってよいものである。
好ましくは、隠蔽性が高く鮮明な筆跡を発揮せしめうる点から、用いる隠蔽性粒子としては、酸化チタン単独の使用、酸化チタンと中空樹脂粒子や異方性樹脂粒子等との併用が挙げられる。なお、隠蔽性粒子中の酸化チタンの含有量は、５０重量％（以下、単に「％」という）以上とすることが望ましい。図１中の隠蔽性粒子は、酸化チタン粒子１０と中空樹脂粒子１０ａとの併用型である。
また、隠蔽性やカプセルに内包せしめるという点から、用いる隠蔽性粒子は、平均粒子径が０．０５〜２０μｍの使用が好ましく、特に好ましくは、平均粒子径が０．１〜１０μｍの隠蔽性粒子が望ましい。
The
Preferably, the concealable particles to be used include the use of titanium oxide alone and the combined use of titanium oxide and hollow resin particles, anisotropic resin particles, and the like because they have high concealability and can exhibit clear handwriting. The content of titanium oxide in the concealing particles is preferably 50% by weight (hereinafter simply referred to as “%”) or more. The concealable particles in FIG. 1 are a combined type of
Further, from the viewpoint of concealability and encapsulation, the concealable particles used preferably have an average particle size of 0.05 to 20 μm, and particularly preferably, the concealable particles have an average particle size of 0.1 to 10 μm. Is desirable.
具体的に用いることができる隠蔽性粒子として、酸化チタンとしてはルチル型、アナターゼ型等の酸化チタンが使用でき、例えば、ＫＲ−３８０（チタン工業社製、平均粒径０．５μｍ、親油性処理ＴｉＯ２）、ＩＴＴ−２ ＣＲ−５０（日光ケミカルズ社製、平均粒径０．３μｍ、有機チタネート処理ＴｉＯ２）、ＩＴＴ−７ ＴＴＯ−Ｓ−３（日光ケミカルズ社製、平均粒径０．０５μｍ、有機チタネート処理微粒子ＴｉＯ２）などが挙げられる。
酸化亜鉛としては、例えば、ＮＡＮＯＦＩＮＥ Ｐ−２（堺化学工業社製、平均粒径０．０５μｍ）などが挙げられる。
中空樹脂粒子は、樹脂粒子中に中空部があるものであり、例えば、ＳＸ８６６（Ａ）（ＪＳＲ社製、平均粒径０．３μｍ、架橋スチレンアクリル中空粒子）などが挙げられる。
これらの隠蔽性粒子の形状は、特に限定されず、例えば、球状、楕円状、針状などが挙げられる。
これらの隠蔽性粒子の合計含有量は、分散性、隠蔽性の点から、マイクロカプセル粒子全量に対して、好ましくは、５〜８０％、更に好ましくは、１０〜７０％とすることが望ましい。
この隠蔽性粒子の含有量が５％未満であると、隠蔽性が不十分となり、また、８０％を超えると、マイクロカプセル自体の比重が大きくなり、結果として沈降しやすくなり、好ましくない。
As the concealable particles that can be specifically used, titanium oxides such as rutile type and anatase type can be used as titanium oxide. For example, KR-380 (manufactured by Titanium Industry Co., Ltd., average particle size 0.5 μm, lipophilic treatment). TiO 2 ), ITT-2 CR-50 (Nikko Chemicals, average particle size 0.3 μm, organic titanate-treated TiO 2 ), ITT-7 TTO-S-3 (Nikko Chemicals, average particle size 0.05 μm) And organic titanate-treated fine particles TiO 2 ).
Examples of zinc oxide include NANOFINE P-2 (manufactured by Sakai Chemical Industry Co., Ltd., average particle size 0.05 μm).
The hollow resin particle has a hollow portion in the resin particle, and examples thereof include SX866 (A) (manufactured by JSR, average particle size 0.3 μm, crosslinked styrene acrylic hollow particle).
The shape of these concealing particles is not particularly limited, and examples thereof include a spherical shape, an elliptical shape, and a needle shape.
The total content of these concealing particles is preferably 5 to 80%, more preferably 10 to 70%, based on the total amount of the microcapsule particles, from the viewpoint of dispersibility and concealing property.
When the content of the concealing particles is less than 5%, the concealing property becomes insufficient, and when it exceeds 80%, the specific gravity of the microcapsule itself is increased, and as a result, it tends to settle, which is not preferable.
用いることができる溶媒としては、例えば、芳香族系炭化水素、流動パラフィン、ヘキサン、シクロヘキサン、ケロシン、アイソパー、パラフィン系炭化水素等の脂肪族炭化水素類、ハロゲン化炭化水素類、リン酸エステル類、フタル酸エステル類、カルボン酸エステル類、塩素化パラフィン、Ｎ，Ｎ−ジブチル−２−ブトキシ−５−ターシャリオクチルアニリン等の少なくとも１種が挙げられるが、これらに限定されるものではない。
好ましくは、マイクロカプセルの比重をカプセル分散媒と等しくするために、溶媒の少なくとも１種類が比重１．０以下、更に好ましくは、用いる溶媒の全てが比重１．０以下、特に比重０．９以下の溶媒、具体的には、ノルマルパラフィン（比重０．７４５）、イソパラフィン（比重０．７１０）、流動パラフィン（比重０．８３）、キシレン（比重０．８６）、ジオクチルスルフィド（ＤＯＳ、比重０．９１）、トリス（２−エチルへキシル）フォスフェート（ＴＯＰ、比重０．９２）などの非水溶性溶媒が挙げられる。
これらの溶媒の含有量としては、用いる隠蔽性粒子や後述する好ましく用いる分散剤種によって適宜決定されるが、分散性、隠蔽性の点から、マイクロカプセル粒子全量に対して、好ましくは、２０〜９５％、更に好ましくは、３０〜９０％とすることが望ましい。
この溶媒の含有量が２０％未満であると、マイクロカプセルの比重が大きくなり、分散が難しくなり、また、９５％を超えると、隠蔽性が低下して、好ましくない。
Examples of the solvent that can be used include aromatic hydrocarbons, liquid paraffin, hexane, cyclohexane, kerosene, isopar, paraffin hydrocarbons and other aliphatic hydrocarbons, halogenated hydrocarbons, phosphate esters, Examples thereof include, but are not limited to, phthalic acid esters, carboxylic acid esters, chlorinated paraffin, N, N-dibutyl-2-butoxy-5-tertiaryoctylaniline, and the like.
Preferably, in order to make the specific gravity of the microcapsules equal to that of the capsule dispersion medium, at least one of the solvents has a specific gravity of 1.0 or less, more preferably, all of the solvents used have a specific gravity of 1.0 or less, particularly a specific gravity of 0.9 or less. Specifically, normal paraffin (specific gravity 0.745), isoparaffin (specific gravity 0.710), liquid paraffin (specific gravity 0.83), xylene (specific gravity 0.86), dioctyl sulfide (DOS, specific gravity 0. 91) and water-insoluble solvents such as tris (2-ethylhexyl) phosphate (TOP, specific gravity 0.92).
The content of these solvents is appropriately determined depending on the concealing particles to be used and the types of dispersants that are preferably used, which will be described later. From the viewpoint of dispersibility and concealing properties, the total amount of microcapsule particles is preferably 20 to 20 95%, more preferably 30 to 90%.
If the content of this solvent is less than 20%, the specific gravity of the microcapsules becomes large and dispersion becomes difficult, and if it exceeds 95%, the concealability is lowered, which is not preferable.
用いる構造粘性付与剤は、上記有機溶剤等の溶媒に分散又は溶解して使用するものであり、例えば、スメクタイト、変性スメクタイト、ヒマシ油変性誘導体、シリカ、アミノアマイド、ポリエステル変性体、アクリル化合物、アマニ油、トール油などの少なくとも１種が挙げられる。
これらの構造粘性付与剤の含有量としては、用いる隠蔽性粒子種によって適宜決定されるが、沈降防止、インキ粘度の点から、マイクロカプセル粒子全量に対して、好ましくは、０．１〜４０％、更に好ましくは、０．２〜３０％とすることが望ましい。
この構造粘性付与剤の含有量が０．１％未満であると、十分な粘性付与ができず、また、４０％を超えると、必要以上となり、酸化チタンなどの隠蔽性粒子が少なくなり、好ましくない。
The structural viscosity-imparting agent used is dispersed or dissolved in a solvent such as the above organic solvent. For example, smectite, modified smectite, castor oil-modified derivative, silica, aminoamide, polyester-modified product, acrylic compound, flaxseed Examples thereof include at least one of oil and tall oil.
The content of these structural viscosity-imparting agents is appropriately determined depending on the concealing particle type to be used, but is preferably 0.1 to 40% based on the total amount of microcapsule particles from the viewpoint of sedimentation prevention and ink viscosity. More preferably, the content is 0.2 to 30%.
When the content of this structural viscosity imparting agent is less than 0.1%, sufficient viscosity cannot be imparted. When the content exceeds 40%, it is more than necessary, and concealing particles such as titanium oxide are reduced. Absent.
本発明のマイクロカプセル粒子は、上記構造粘性付与剤が分散又は溶解された溶媒中に、酸化チタン等の隠蔽性粒子が分散され、この混合物がマイクロカプセル内に閉じ込められたものである。
本発明では、更なる分散性向上の目的の点から、分散体中には、分散剤を含有せしめることが好ましい。
用いることができる分散剤としては、高級脂肪酸、水溶性高分子、界面活性剤や高分子界面活性剤、例えば、ノニオン系界面活性剤、アニオン系界面活性剤、カチオン系界面活性剤、両性系界面活性剤、高分子型界面活性剤などの少なくとも１種が挙げられるが、これらに限定されるものではない。
これらの分散剤の含有量としては、用いる隠蔽性粒子や溶媒種によって適宜決定されるが、分散安定性やインキ粘度の点から、マイクロカプセル粒子全量に対して、好ましくは、０．１〜３０％、更に好ましくは、０．５〜２０％とすることが望ましい。
The microcapsule particles of the present invention are those in which concealing particles such as titanium oxide are dispersed in a solvent in which the structural viscosity imparting agent is dispersed or dissolved, and this mixture is confined in the microcapsules.
In the present invention, from the viewpoint of further improving dispersibility, it is preferable that a dispersant is contained in the dispersion.
Dispersants that can be used include higher fatty acids, water-soluble polymers, surfactants and polymer surfactants such as nonionic surfactants, anionic surfactants, cationic surfactants, and amphoteric interfaces. Examples include, but are not limited to, at least one of an activator and a polymer surfactant.
The content of these dispersants is appropriately determined depending on the concealing particles and solvent types to be used. From the viewpoint of dispersion stability and ink viscosity, it is preferably 0.1 to 30 with respect to the total amount of microcapsule particles. %, More preferably 0.5 to 20%.
また、分散体中には、染料、顔料の着色性を有する色材、例えば、顔料としては、アゾ系顔料、縮合ポリアゾ系顔料、フタロシアニン系顔料、金属錯塩顔料、チオインジゴ顔料、染料レーキ顔料、蛍光顔料等の有機顔料及びカーボンブラック、酸化チタン等の無機顔料が挙げられ、更に、表面を樹脂コーティングで加工した加工顔料、例えば、マイクロリスＡタイプ各種、ＡＳブラック、ＡＳブルー、ＩＫレッド等の少なくとも１種が挙げられ、また、染料としては、例えば、油溶性染料、スピリットソルブル染料等のソルベント染料、ロイコ染料などの少なくとも１種を挙げることができる。
これらの色材の含有量は、マイクロカプセル粒子全量に対して、好ましくは、０〜３０％、更に好ましくは、１〜２０％とすることが望ましい。
これらの色材を含有せしめることにより、更に、被筆記体の色相を隠蔽し良好に発色するマーキング性能を有した筆記具用インキ組成物を提供することができるものとなる。
In addition, in the dispersion, a coloring material having a coloring property of a dye and a pigment, for example, an azo pigment, a condensed polyazo pigment, a phthalocyanine pigment, a metal complex pigment, a thioindigo pigment, a dye lake pigment, a fluorescent pigment Organic pigments such as pigments and inorganic pigments such as carbon black and titanium oxide, and further processed pigments whose surfaces are processed with resin coatings, such as various types of microlith A type, AS black, AS blue, IK red, etc. Examples of the dye include at least one of an oil-soluble dye, a solvent dye such as a spirit solver dye, and a leuco dye.
The content of these coloring materials is preferably 0 to 30%, more preferably 1 to 20%, based on the total amount of microcapsule particles.
By including these coloring materials, it is possible to provide an ink composition for a writing instrument that has a marking performance that conceals the hue of the writing material and colors well.
本発明において、マイクロカプセル粒子は、上述の隠蔽性粒子、構造粘性付与剤、分散剤や色材を溶媒に分散させた分散体を界面重合法、液中硬化被膜法、コアセルベーション法、インサイチュウー重合法、有機溶媒からの相分離法などのマイクロカプセル化法により形成されるマイクロカプセル内に封入することにより得られるものである。
好ましくは、界面重合法、コアセルベーション法、インサイチュウー重合法により、マイクロカプセル粒子を形成することが望ましい。
また、壁材を強固にする点から、マイクロカプセル粒子の壁材２１が、架橋を可能とするモノマー、ポリマーあるいは架橋材を含む重合物などから形成される高分子樹脂の壁材から形成されることが望ましい。
In the present invention, the microcapsule particles include the above-described concealing particles, a structural viscosity imparting agent, a dispersion obtained by dispersing a dispersant or a coloring material in a solvent, an interfacial polymerization method, a submerged cured coating method, a coacervation method, an in situ method. It is obtained by encapsulating in a microcapsule formed by a microencapsulation method such as a Wu polymerization method or a phase separation method from an organic solvent.
Preferably, the microcapsule particles are formed by an interfacial polymerization method, a coacervation method, or an in situ polymerization method.
Further, in order to strengthen the wall material, the
得られるマイクロカプセル粒子Ａの平均粒径は、隠蔽性や筆記具用インキとしての流出量の点から、好ましくは、１〜２００μｍ、更に好ましくは、１０〜１００μｍとすることが望ましい。
このマイクロカプセル粒子の平均粒径が１μｍ未満であると、内包できる隠蔽性粒子が少なく結果としてマイクロカプセルとしての隠蔽性が低下し、また、この平均粒径が２００μｍを超えると、粒子間の隙間が大きくなり、結果として隠蔽性が低下し、好ましくない。
なお、上記好適な範囲となる平均粒径のマイクロカプセル粒子は、重合時の撹拌速度等を調整することにより容易に得ることができる。
The average particle size of the obtained microcapsule particles A is preferably 1 to 200 μm, more preferably 10 to 100 μm, from the viewpoint of concealability and the amount of outflow as ink for writing instruments.
When the average particle size of the microcapsule particles is less than 1 μm, the number of concealable particles that can be included is small, and as a result, the concealability as a microcapsule decreases. When the average particle size exceeds 200 μm, the gap between the particles Is increased, resulting in a decrease in concealment.
In addition, the microcapsule particles having an average particle diameter within the above preferable range can be easily obtained by adjusting the stirring speed at the time of polymerization.
本発明の筆記具用インキ組成物は、隠蔽性粒子、構造粘性付与剤が溶媒に分散されている分散体が封入されたマイクロカプセル粒子を含有するものであり、当該必須成分の他、インキ種（水性、油性、ゲルインキ）により、各種の筆記具用インキ各成分（溶剤、樹脂、上述の色材）等を配合することができ、更に、本発明の効果を損なわない範囲で、任意成分（添加剤）、例えば、アニオン系、ノニオン系、カチオン系などの界面活性剤、乾燥防止剤、防錆剤、防黴剤、沈降抑制剤などを適宜必要に応じて含有することができる。
このマイクロカプセル粒子の含有量は、インキ種（水性、油性、ゲルインキ）、用途（ボールペン用、サインペン用等）により変動するものであるが、筆記具用インキ組成物全量に対して、１〜５０％含有せしめることが好ましく、更に好ましくは、５〜４０％とすることが望ましい。
このマイクロカプセル粒子の含有量が１％未満であると、所定の白色度や隠蔽性が得られず、一方、５０％を超えて含有されると、インキ組成物の経時的な安定性が低下し、凝集及び沈降が起こることがあり、好ましくない。
The ink composition for a writing instrument of the present invention contains microcapsule particles in which a dispersion in which a concealing particle and a structural viscosity-imparting agent are dispersed in a solvent is contained. Various components for ink for writing instruments (solvent, resin, the above-mentioned coloring material) and the like can be blended with water-based, oil-based, gel ink), and optional components (additives) as long as the effects of the present invention are not impaired. ), For example, surfactants such as anionic, nonionic, cationic, and the like, drying inhibitors, rust inhibitors, antifungal agents, precipitation inhibitors, and the like can be appropriately contained as necessary.
The content of the microcapsule particles varies depending on the ink type (water-based, oil-based, gel ink) and application (for ballpoint pens, sign pens, etc.), but is 1 to 50% with respect to the total amount of the ink composition for writing instruments. It is preferable to make it contain, More preferably, it is desirable to set it as 5 to 40%.
If the content of the microcapsule particles is less than 1%, the predetermined whiteness or hiding property cannot be obtained. On the other hand, if the content exceeds 50%, the stability of the ink composition with time decreases. However, aggregation and sedimentation may occur, which is not preferable.
本発明の筆記具用インキ組成物は、上記特性のマイクロカプセル粒子、各インキ成分（溶剤、樹脂、色材、添加剤）等を用いて従来公知の筆記具用インキ組成物の製造方法を適用して製造することができる。すなわち、マイクロカプセル粒子、色材、樹脂、溶剤、添加剤を分散混合機、撹拌機を用いて、混合することによって目的の筆記具用の水性インキ、油性インキ、ゲルインキ組成物等を得ることができる。
なお、製造時、有機顔料などの粗大粒子を除去するためにフィルター、遠心分離機等を用いることなど必要に応じて使用できる。
また、上記マイクロカプセル粒子を水性インキに用いる場合は、必要に応じて水の粘性調整剤を含有することができる。用いることができる粘性調整剤としては、変性スメクタイト〔ベントンＳＤ−１（ＮＬケミカルズ社製）〕、合成スメクタイト〔ルーセンタイトＳＷＮ（コープケミカル社製）〕、結晶性セルロース〔ゼオラスクリーム（旭化成社製）〕、ヒドロキシエチルセルロース、ヒドロキシプロピルセルロース、ポリビニルピロリドン、ポリビニルアルコールなどの少なくとも１種を用いることができる。
これらの粘性調整剤の含有量は、水性インキ組成物全量に対して、好ましくは、０．１〜１０％、更に好ましくは、０．１〜５％とすることが望ましい。この粘性調整剤の含有量が０．１％未満であると、十分な粘性付与ができず、また、１０％を超えると、インキ粘度が大きくなり、筆記具用水性インキとして適さず、好ましくない。
The ink composition for a writing instrument of the present invention applies a conventionally known method for producing an ink composition for a writing instrument using microcapsule particles having the above characteristics, each ink component (solvent, resin, coloring material, additive) and the like. Can be manufactured. That is, by mixing microcapsule particles, coloring materials, resins, solvents, and additives using a dispersion mixer and a stirrer, water-based inks, oil-based inks, gel ink compositions, etc. for the intended writing instrument can be obtained. .
In addition, a filter, a centrifuge, etc. can be used as needed, such as using a filter to remove coarse particles such as organic pigments during production.
Moreover, when using the said microcapsule particle for water-based ink, the viscosity modifier of water can be contained as needed. Examples of the viscosity modifier that can be used include modified smectite [Benton SD-1 (manufactured by NL Chemicals)], synthetic smectite [Lucentite SWN (manufactured by Corp Chemical)], crystalline cellulose [Zeolas cream (manufactured by Asahi Kasei Co., Ltd.)]. ], At least one of hydroxyethyl cellulose, hydroxypropyl cellulose, polyvinyl pyrrolidone, polyvinyl alcohol and the like can be used.
The content of these viscosity modifiers is preferably 0.1 to 10%, more preferably 0.1 to 5%, based on the total amount of the water-based ink composition. If the content of the viscosity modifier is less than 0.1%, sufficient viscosity cannot be imparted, and if it exceeds 10%, the ink viscosity becomes large and is not suitable as a water-based ink for writing instruments.
本発明の筆記具用インキ組成物の粘度は、好ましくは、流出量やインキ安定性の点から、ＥＬＤ粘度計における２５℃、５０ｒｐｍの粘度が、３〜５０ｍＰａ・ｓ、更に好ましくは、３〜３０ｍＰａ・ｓとすることが望ましい。
この粘度が５０ｍＰａ・ｓｅｃを越えて粘度が高くなると、筆感が重くなり、滑らかに書きづらくなり、逆に、３ｍＰａ・ｓｅｃ未満であると、著しいペン先での顔料沈降、滲み等があり、好ましくない。
The viscosity of the ink composition for a writing instrument according to the present invention is preferably 3 to 50 mPa · s, more preferably 3 to 30 mPa, at 25 ° C. and 50 rpm in an ELD viscometer, from the viewpoint of the outflow amount and ink stability.・ S is desirable.
If this viscosity exceeds 50 mPa · sec, the writing feel becomes heavier and it becomes difficult to write smoothly, and conversely, if it is less than 3 mPa · sec, there is significant pigment sedimentation and bleeding at the pen tip, It is not preferable.
本発明において、筆記具用インキ組成物は、ボールペン用、サインペン用、筆ペン用の水性インキ、油性インキ、ゲルインキ等に好適に用いることができるものであり、本発明の筆記具用インキ組成物を充填する筆記具の構造としては、上記筆記具用インキ組成物が充填され本発明の効果が発揮できるように筆記できるものであれば、その構造は特に限定されるものではない。
好ましくは、低粘度であり、隠蔽性を有する複合粒子を長期間安定と分散せしめる点から、本発明の筆記具用インキ組成物を吸蔵するインキ吸蔵体を収容した中綿式筆記具用のサインペン用インキとして好適に用いることができる。
In the present invention, the ink composition for writing instruments can be suitably used for water-based inks, oil-based inks, gel inks, etc. for ballpoint pens, sign pens, brush pens, etc., and is filled with the ink composition for writing instruments of the present invention. The structure of the writing instrument is not particularly limited as long as it can be written so that the ink composition for a writing instrument is filled and the effects of the present invention can be exhibited.
Preferably, as a sign pen ink for a batting type writing instrument containing an ink occlusion body that occludes the ink composition for a writing instrument of the present invention, since the composite particles having a low viscosity and having a concealing property are stably dispersed for a long period of time. It can be used suitably.
このように構成される本発明の筆記具用インキ組成物が、何故これまでの発明と比較して優れているという理由としては、以下のように推察される。
従来、酸化チタン顔料を使用した筆記具用インキ組成物は、その比重の大きさのため、インキ組成物中に長期的安定に分散させることができなかった。これに対して、本発明の筆記具用インキ組成物は、隠蔽性粒子、構造粘性付与剤が溶媒に分散されている分散体が封入された比重が小さく、隠蔽性、白色性があるマイクロカプセル粒子を含有せしめることにより、長期に安定で沈降しない白色性、隠蔽性が高く鮮明な筆跡を長期に亘り維持することができる筆記具用インキ組成物を提供することができるものとなる。
また、特開２０００−２６５１０５号公報に記載される酸化チタンを内包したマイクロカプセル顔料を含有するボールペン用水性インキ組成物は、沈降及び分離現象は幾分解消されるものであるが、マイクロカプセル顔料製造時の隠蔽性粒子の脱落があったり、隠蔽性粒子の粒子径の均一化が難しく、更に、マイクロカプセルの粒子径の均一化及びマイクロカプセル内の粒子数の均一化が難しいものであるが、本発明では、酸化チタン等の隠蔽性粒子と共に、構造粘性付与剤を溶媒、特に比重１以下の溶媒に分散した分散体を用いているので、隠蔽性粒子の脱落がなく、隠蔽性粒子の粒子径の均一化、更に、マイクロカプセルの粒子径の均一化及び粒子数の均一化が達成された安定な品質を有するマイクロカプセル粒子を用いることとなるため、単に酸化チタンを内包したマイクロカプセル顔料に較べ、優れた機能、すなわち、今までにない長期に安定で沈降しない白色性、隠蔽性が高く鮮明な筆跡を長期に亘り維持することができる筆記具用インキ組成物が得られるものとなる。
The reason why the ink composition for a writing instrument of the present invention configured as described above is superior to the conventional invention is presumed as follows.
Conventionally, an ink composition for a writing instrument using a titanium oxide pigment cannot be stably dispersed in the ink composition for a long period of time because of its large specific gravity. On the other hand, the ink composition for a writing instrument of the present invention is a microcapsule particle having a small specific gravity in which a dispersion in which a concealing particle and a structural viscosity imparting agent are dispersed in a solvent is enclosed, and having a concealing property and whiteness. Thus, it is possible to provide an ink composition for a writing instrument that can maintain a clear and white handwriting that is stable and does not settle for a long period of time and has a clear and clear handwriting over a long period of time.
In addition, the water-based ink composition for ballpoint pens containing a microcapsule pigment encapsulating titanium oxide described in JP-A-2000-265105 has a slightly reduced sedimentation and separation phenomenon. Although the concealable particles may fall off during production, the particle size of the concealable particles is difficult to make uniform, and further, the particle size of the microcapsules and the number of particles in the microcapsules are difficult to make uniform. In the present invention, since a dispersion in which a structural viscosity imparting agent is dispersed in a solvent, particularly a solvent having a specific gravity of 1 or less is used together with the concealing particles such as titanium oxide, the concealing particles are not dropped off. The use of microcapsule particles having a stable quality in which the particle size is uniformed, and the microcapsule particle size is uniformized and the number of particles is uniformized. Compared to microcapsule pigments that simply contain titanium oxide, it has excellent functions, ie, whiteness that does not settle for a long period of time and does not settle, and high writing ability that can maintain a clear handwriting over a long period of time. An ink composition is obtained.
次に、実施例及び比較例により、本発明を更に詳細に説明するが、本発明は下記実施例等に限定されるものではない。 EXAMPLES Next, although an Example and a comparative example demonstrate this invention further in detail, this invention is not limited to the following Example etc.
〔実施例１〜５及び比較例１〜４〕
下記表１に示す各配合組成（隠蔽性粒子、溶媒、分散剤、構造粘性付与剤）を混合撹拌後、超音波分散機で３０分間分散しマイクロカプセル粒子内包用の隠蔽性粒子分散液を調製した。
用いた隠蔽性粒子（Ａ−１〜Ａ−４）、溶媒（Ｂ−１〜Ｂ−２）、分散剤（Ｃ−１〜Ｃ−２）、構造粘性付与剤（Ｄ−１〜Ｄ−３）は、下記の材料を用いた。
隠蔽性粒子Ａ：
Ａ−１：平均粒径０．５μｍの酸化チタン（ＫＲ−３８０、チタン工業社製、親油性処理ＴｉＯ２、球状）
Ａ−２：平均粒径０．３μｍの酸化チタン（ＩＴＴ−２ ＣＲ−５０、日光ケミカルズ社製、有機チタネート処理ＴｉＯ２、球状）
Ａ−３：平均粒径０．０５μｍの酸化チタン（ＩＴＴ−７ ＴＴＯ−Ｓ−３、日光ケミカルズ社製、有機チタネート処理微粒子ＴｉＯ２、球状）
Ａ−４：平均粒径０．３μｍの中空粒子〔ＳＸ８６６（Ａ）、ＪＳＲ社製、架橋スチレンアクリル中空粒子、球状〕
溶媒Ｂ:
Ｂ−１：ノルマルパラフィン（比重０．７４５、ノルマルパラフィンＨ、新日本石油社製）
Ｂ−２：イソパラフィン（比重０．７１０、日石アイソゾール、新日本石油社製）
分散剤Ｃ：
Ｃ−１：ステアリン酸
Ｃ−２：ソルビタントリオレート（ノニオンＯＰ−８５Ｒ、日本油脂社製）
構造粘性付与剤Ｄ：
Ｄ−１：シリカ（ＡＥＲＯＳＩＬ Ｒ９７２、デグサ社製）
Ｄ−２：アマニ油（アラキード６７０１−６０、荒川化学社製）
Ｄ−３：トール油（アラキード１４６５−６０、荒川化学社製）
[Examples 1 to 5 and Comparative Examples 1 to 4]
Each compounding composition (hiding particles, solvent, dispersant, structural viscosity imparting agent) shown in Table 1 below is mixed and stirred, and then dispersed for 30 minutes with an ultrasonic disperser to prepare a hiding particle dispersion for inclusion in microcapsule particles. did.
Used concealing particles (A-1 to A-4), solvents (B-1 to B-2), dispersants (C-1 to C-2), structural viscosity imparting agents (D-1 to D-3) ) Used the following materials.
Hiding particles A:
A-1: Titanium oxide having an average particle size of 0.5 μm (KR-380, manufactured by Titanium Industry Co., Ltd., lipophilically treated TiO 2 , spherical)
A-2: Titanium oxide having an average particle size of 0.3 μm (ITT-2 CR-50, manufactured by Nikko Chemicals, organic titanate-treated TiO 2 , spherical)
A-3: Titanium oxide having an average particle diameter of 0.05 μm (ITT-7 TTO-S-3, manufactured by Nikko Chemicals, organic titanate-treated fine particles TiO 2 , spherical)
A-4: Hollow particles having an average particle size of 0.3 μm [SX866 (A), manufactured by JSR, cross-linked styrene acrylic hollow particles, spherical shape]
Solvent B:
B-1: Normal paraffin (specific gravity 0.745, normal paraffin H, manufactured by Nippon Oil Corporation)
B-2: Isoparaffin (specific gravity 0.710, Nisseki Isosol, manufactured by Nippon Oil Corporation)
Dispersant C:
C-1: Stearic acid C-2: Sorbitan trioleate (Nonion OP-85R, manufactured by NOF Corporation)
Structural viscosity-imparting agent D:
D-1: Silica (AEROSIL R972, manufactured by Degussa)
D-2: Linseed oil (Arachid 6701-60, Arakawa Chemical Co., Ltd.)
D-3: Tall oil (Arachid 1465-60, manufactured by Arakawa Chemical Co., Ltd.)
得られた各マイクロカプセル粒子内包用隠蔽性粒子分散液を下記のＡ〜Ｄに示す方法でマイクロカプセル化スラリー（ＭＣ１〜５）を調製した。
方法Ａ：
５重量％のゼラチン水溶液２００ｇと５重量％のアラビアゴム水溶液２００ｇを撹拌しながら混合し、５０℃に昇温し、水酸化ナトリウム水溶液で溶液のｐＨを９．０に調整した。この水溶液に隠蔽性粒子分散液２００ｇをゆっくり撹拌しながら添加した。次いで、ホモミキサーで回転数５０００ｒｐｍ、５分の条件で処理した後、再び所定の撹拌条件（撹拌棒３００ｒｐｍ）で酢酸水溶液を用いてｐＨを４．０まで低下させ、ゼラチン／アラビアゴムコアセルベートを形成させた後、３０分かけて約５℃まで冷却した。次に、ホルマリン３５％水溶液１０ｇを添加し、５０℃まで昇温し、約２次間硬化反応を実施し、マイクロカプセルスラリーを調製した。
Microcapsulated slurries (MC1 to MC5) were prepared from the obtained concealable particle dispersions for encapsulating microcapsule particles by the methods shown in A to D below.
Method A:
200 g of a 5 wt% aqueous gelatin solution and 200 g of a 5 wt% aqueous gum arabic solution were mixed with stirring, the temperature was raised to 50 ° C., and the pH of the solution was adjusted to 9.0 with an aqueous sodium hydroxide solution. To this aqueous solution, 200 g of the hiding particle dispersion was added with slow stirring. Next, after processing with a homomixer at a rotational speed of 5000 rpm for 5 minutes, the pH was lowered to 4.0 using an aqueous acetic acid solution again under the predetermined stirring conditions (stirring bar 300 rpm) to form a gelatin / gum arabic coacervate Then, it was cooled to about 5 ° C. over 30 minutes. Next, 10 g of a formalin 35% aqueous solution was added, the temperature was raised to 50 ° C., and a secondary curing reaction was carried out to prepare a microcapsule slurry.
方法Ｂ：
隠蔽性粒子分散液２００ｇに１０ｇのヘキサメチレンジイソシアネート（ＨＤＩ）を溶解させた後、直ちに５重量％のゼラチン水溶液３００ｇに、ホモミキサーで回転数５０００ｒｐｍで撹拌しながら添加し、乳化液を調製した。次に、温度を５０℃に加温しながら所定の撹拌条件（撹拌棒３００ｒｐｍ）で２時間撹拌を続けた後、系の温度を５℃まで冷却した。次に、水酸化ナトリウムでｐＨを９．０に調整した後、グルタルアルデヒド２５％水溶液を１０ｇ添加し、５０℃まで昇温し、約２時間でカプセル化反応を終了せしめて、マイクロカプセルスラリーを調製した。
Method B:
After dissolving 10 g of hexamethylene diisocyanate (HDI) in 200 g of the concealable particle dispersion, it was immediately added to 300 g of a 5 wt% gelatin aqueous solution while stirring with a homomixer at a rotational speed of 5000 rpm to prepare an emulsion. Next, stirring was continued for 2 hours under predetermined stirring conditions (stirring rod 300 rpm) while heating the temperature to 50 ° C, and then the temperature of the system was cooled to 5 ° C. Next, after adjusting the pH to 9.0 with sodium hydroxide, 10 g of a 25% aqueous solution of glutaraldehyde was added, the temperature was raised to 50 ° C., and the encapsulation reaction was completed in about 2 hours. Prepared.
方法Ｃ：
隠蔽性粒子分散液２００ｇにスチレン１６ｇとジビニルベンゼン４ｇ、アゾ系重合開始剤（Ｖ−７０、和光純薬社製）０．１ｇを溶解させた後、５重量％のゼラチン水溶液３００ｇに、ホモミキサーで回転数５０００ｒｐｍで撹拌しながら添加し、乳化液を調製した。次に、窒素パージ雰囲気下で温度６０℃に加温し所定の撹拌条件（撹拌棒３００ｒｐｍ）で６時間撹拌を続けた後、系の温度を５℃まで冷却した。次に、水酸化ナトリウムでｐＨを９．０に調整した後、グルタルアルデヒド２５％水溶液を１０ｇ添加し、５０℃まで昇温し、約２時間でカプセル化反応を終了せしめて、マイクロカプセルスラリーを調製した。
Method C:
In 200 g of the concealable particle dispersion, 16 g of styrene, 4 g of divinylbenzene, and 0.1 g of an azo polymerization initiator (V-70, manufactured by Wako Pure Chemical Industries, Ltd.) were dissolved, and then the homomixer was added to 300 g of a 5% by weight gelatin aqueous solution. Were added with stirring at a rotational speed of 5000 rpm to prepare an emulsion. Next, under a nitrogen purge atmosphere, the temperature was raised to 60 ° C. and stirring was continued for 6 hours under predetermined stirring conditions (stirring bar 300 rpm), and then the temperature of the system was cooled to 5 ° C. Next, after adjusting the pH to 9.0 with sodium hydroxide, 10 g of a 25% aqueous solution of glutaraldehyde was added, the temperature was raised to 50 ° C., and the encapsulation reaction was completed in about 2 hours. Prepared.
方法Ｄ：
隠蔽性粒子分散液２００ｇを５重量％のアラビアゴムと０．５重量％のドデシルベンゼンスルホン酸を含む水溶液３００ｇに、ホモミキサーで５０００ｒｐｍで撹拌しながら、添加し、乳化液を調製した。次に、温度を８０℃に加温しながら４０重量％のメラミンホルマリンポリマー水溶液５０ｇを添加し、リン酸でｐＨを４．０に調整した後、所定の反応条件で、約２時間でカプセル化反応を終了せしめて、マイクロカプセルスラリーを調製した。
Method D:
200 g of the concealable particle dispersion was added to 300 g of an aqueous solution containing 5% by weight of gum arabic and 0.5% by weight of dodecylbenzenesulfonic acid while stirring with a homomixer at 5000 rpm to prepare an emulsion. Next, 50 g of 40% by weight melamine formalin polymer aqueous solution is added while heating the temperature to 80 ° C., and the pH is adjusted to 4.0 with phosphoric acid, followed by encapsulation in about 2 hours under predetermined reaction conditions. The reaction was terminated and a microcapsule slurry was prepared.
〔筆記具用インキ組成物の調整〕
（実施例１〜５、比較例４）
上記方法Ａ〜Ｄのマイクロカプセル化方法で得られた各マイクロカプセルスラリー（ＭＣスラリー、ＭＣ１〜５）の濃度が３０重量％になるように、下記表２に示す配合組成で筆記具用インキを調製した。
なお、ＭＣスラリー１〜５の平均粒径は、コールターカウンター（べックマンコールター社製）により測定した値である。
（比較例１〜３）
各ＭＣスラリーの代わりに、ＭＣスラリー濃度が同じ（３０重量％）になるように直接隠蔽性粒子（表１の比較１〜３の組成割合で３０重量％）を添加し、筆記具用インキ組成物を調製した。このとき隠蔽性粒子（顔料）の分散にはペイントシェーカーを用いた。
[Adjustment of ink composition for writing instruments]
(Examples 1-5, Comparative Example 4)
The ink for writing instruments is prepared with the composition shown in Table 2 below so that the concentration of each microcapsule slurry (MC slurry, MC1-5) obtained by the microencapsulation methods A to D is 30% by weight. did.
In addition, the average particle diameter of MC slurry 1-5 is the value measured with the Coulter counter (made by Beckman Coulter).
(Comparative Examples 1-3)
Instead of each MC slurry, directly concealing particles (30 wt% in the composition ratios of comparisons 1 to 3 in Table 1) were added so that the MC slurry concentration was the same (30 wt%), and the ink composition for writing instruments Was prepared. At this time, a paint shaker was used for dispersing the concealing particles (pigments).
得られた各筆記具用インキ組成物の粘度、沈降性、隠蔽性、経時保存後の隠蔽性、筆記性を下記評価方法で評価した。
これらの結果を下記表２に示す。
The viscosity, sedimentation property, concealing property, concealing property after storage over time, and writing property of each ink composition for writing instruments thus obtained were evaluated by the following evaluation methods.
These results are shown in Table 2 below.
（粘度の測定方法）
得られた各実施例及び比較例の水性インキ組成物の２５℃条件下におけるＥＬＤ型粘度計〔ＴＶ−２０（トキメック社製）〕で５０ｒｐｍの粘度を測定した。
(Measurement method of viscosity)
Viscosity at 50 rpm was measured with an ELD type viscometer [TV-20 (manufactured by Tokimec)] under the conditions of 25 ° C. of the obtained water-based ink compositions of Examples and Comparative Examples.
（沈降性の評価方法）
得られた各実施例及び比較例の筆記具用インキ組成物を、直径２ｃｍ、長さ２０ｃｍの沈降管に充填し、室温（２５℃）下で１ヶ月放置し、沈降性を目視で下記の評価基準で評価した。
評価基準：
○：分離、凝集はなく、沈降は認められない。
△：上層部に若干の濃淡の変化が認められる。
×：分離又は凝集があり、沈降が明確に認められる。
(Evaluation method for sedimentation)
The obtained ink compositions for writing instruments of each Example and Comparative Example were filled in a settling tube having a diameter of 2 cm and a length of 20 cm, and left for 1 month at room temperature (25 ° C.). Evaluated by criteria.
Evaluation criteria:
○: There is no separation or aggregation, and no sedimentation is observed.
Δ: A slight change in shading is observed in the upper layer.
X: There is separation or aggregation, and sedimentation is clearly recognized.
（隠蔽性の評価方法）
得られた各インキを黒画用紙に１００μｍのバーコーターで塗布し、白色度を目視で下記の評価基準で評価した。
評価基準：
○：白色である。
△：やや黒味を帯びた白色である。
×：隠蔽が弱く黒味を強く感じる。
(Concealment evaluation method)
Each ink obtained was applied to black paper with a 100 μm bar coater, and the whiteness was visually evaluated according to the following evaluation criteria.
Evaluation criteria:
○: White.
Δ: Slightly blackish white.
X: The concealment is weak and the blackness is felt strongly.
（経時保存後の隠蔽性の評価方法）
得られた各インキ組成物を三菱鉛筆社製ＰＷＢ−７Ｍ（中綿タイプマーキングペン）の軸に６ｇ充填し、ペン先を上向きの状態で２５℃で１ヵ月保存した後の筆記描線の隠蔽性を目視で下記の評価基準で評価した。
評価基準：
○：白色である。
△：やや黒味を帯びた白色である。
×：隠蔽が弱く黒味を強く感じる。
(Method for evaluating concealment after storage over time)
The obtained ink composition is filled with 6 g of the shaft of PWB-7M (batting type marking pen) manufactured by Mitsubishi Pencil Co., Ltd., and the writing line is concealed after being stored for one month at 25 ° C. with the pen tip facing upward. The following evaluation criteria were evaluated visually.
Evaluation criteria:
○: White.
Δ: Slightly blackish white.
X: The concealment is weak and the blackness is felt strongly.
（筆記性の評価方法）
また、得られた各インキ組成物を三菱鉛筆社製ＰＷＢ−７Ｍ（中綿タイプマーキングペン）の軸に６ｇ充填し、紙面に筆記して、下記評価基準で筆記性を評価した。
評価基準：
○：良好に筆記できる。
△：ややカスレを感じる。
×：筆記できない、あるいは、著しくカスレを感じる。
(Writing evaluation method)
Moreover, 6 g of each obtained ink composition was filled in the axis | shaft of PWB-7M (batting type marking pen) by Mitsubishi Pencil Co., Ltd., and it wrote on the paper surface and evaluated the writing property on the following evaluation criteria.
Evaluation criteria:
○: Can be written well.
Δ: Slightly blurry.
×: Cannot be written or feels noticeable.
上記表１及び２の結果から明らかなように、本発明の範囲となる実施例１〜５は、本発明の範囲外となる比較例１〜４に比べて、沈降もなく、筆記性、隠蔽性に優れ、加えて経時安定性にも優れたものであることが判明した。 As is clear from the results of Tables 1 and 2, Examples 1 to 5 which are within the scope of the present invention have no sedimentation, writability and concealment compared with Comparative Examples 1 to 4 which are outside the scope of the present invention. In addition, it has been found that it is excellent in stability with time.
Ａ マイクロカプセル粒子
１０ 隠蔽性粒子
１２ 分散体
A
Claims (10)
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| JP2004210193A JP4756836B2 (en) | 2004-07-16 | 2004-07-16 | Ink composition for writing instruments |
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| JP2004210193A JP4756836B2 (en) | 2004-07-16 | 2004-07-16 | Ink composition for writing instruments |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007291304A (en) * | 2006-04-21 | 2007-11-08 | Marujiyuu Kasei Kk | Ink composition for marking pen |
| WO2017119480A1 (en) | 2016-01-06 | 2017-07-13 | 三菱鉛筆株式会社 | Microcapsule pigment and water-based ink composition for writing utensil |
| JP2017122168A (en) * | 2016-01-06 | 2017-07-13 | 三菱鉛筆株式会社 | Aqueous ink composition for writing instruments |
| JP2017122167A (en) * | 2016-01-06 | 2017-07-13 | 三菱鉛筆株式会社 | Microcapsule pigment |
| KR102668466B1 (en) * | 2016-01-06 | 2024-05-24 | 미쓰비시 엔피쯔 가부시키가이샤 | Microcapsule pigment and aqueous ink composition for writing instruments |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09208871A (en) * | 1996-02-05 | 1997-08-12 | Brother Ind Ltd | Ink for ink jet recording |
| JP2000265105A (en) * | 1999-03-11 | 2000-09-26 | Pilot Ink Co Ltd | Aqueous white or pastel tone ink composition for ball- point pen |
| JP2003128974A (en) * | 2001-10-29 | 2003-05-08 | Pilot Ink Co Ltd | Eraser-erasable water-based writing ink composition and writing tool charged therewith |
| JP2003138194A (en) * | 2001-10-31 | 2003-05-14 | Tombow Pencil Co Ltd | Water-based ink composition erasable with eraser, writing implement using the same and method of producing the rubber-erasable water-based ink composition |
| JP2004149601A (en) * | 2002-10-29 | 2004-05-27 | Mitsubishi Pencil Co Ltd | Decolorizing ink composition for writing tool |
-
2004
- 2004-07-16 JP JP2004210193A patent/JP4756836B2/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09208871A (en) * | 1996-02-05 | 1997-08-12 | Brother Ind Ltd | Ink for ink jet recording |
| JP2000265105A (en) * | 1999-03-11 | 2000-09-26 | Pilot Ink Co Ltd | Aqueous white or pastel tone ink composition for ball- point pen |
| JP2003128974A (en) * | 2001-10-29 | 2003-05-08 | Pilot Ink Co Ltd | Eraser-erasable water-based writing ink composition and writing tool charged therewith |
| JP2003138194A (en) * | 2001-10-31 | 2003-05-14 | Tombow Pencil Co Ltd | Water-based ink composition erasable with eraser, writing implement using the same and method of producing the rubber-erasable water-based ink composition |
| JP2004149601A (en) * | 2002-10-29 | 2004-05-27 | Mitsubishi Pencil Co Ltd | Decolorizing ink composition for writing tool |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007291304A (en) * | 2006-04-21 | 2007-11-08 | Marujiyuu Kasei Kk | Ink composition for marking pen |
| WO2017119480A1 (en) | 2016-01-06 | 2017-07-13 | 三菱鉛筆株式会社 | Microcapsule pigment and water-based ink composition for writing utensil |
| JP2017122168A (en) * | 2016-01-06 | 2017-07-13 | 三菱鉛筆株式会社 | Aqueous ink composition for writing instruments |
| JP2017122167A (en) * | 2016-01-06 | 2017-07-13 | 三菱鉛筆株式会社 | Microcapsule pigment |
| KR20180099801A (en) | 2016-01-06 | 2018-09-05 | 미쓰비시 엔피쯔 가부시키가이샤 | Microcapsule pigment and aqueous ink composition for writing instrument |
| KR102668466B1 (en) * | 2016-01-06 | 2024-05-24 | 미쓰비시 엔피쯔 가부시키가이샤 | Microcapsule pigment and aqueous ink composition for writing instruments |
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