JP2004352909A - Water-base ink composition for ballpoint pen and water-base ballpoint pen produced by using the same - Google Patents
Water-base ink composition for ballpoint pen and water-base ballpoint pen produced by using the same Download PDFInfo
- Publication number
- JP2004352909A JP2004352909A JP2003153945A JP2003153945A JP2004352909A JP 2004352909 A JP2004352909 A JP 2004352909A JP 2003153945 A JP2003153945 A JP 2003153945A JP 2003153945 A JP2003153945 A JP 2003153945A JP 2004352909 A JP2004352909 A JP 2004352909A
- Authority
- JP
- Japan
- Prior art keywords
- ink
- water
- ballpoint pen
- ink composition
- base
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 37
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000000839 emulsion Substances 0.000 claims abstract description 13
- 239000002245 particle Substances 0.000 claims abstract description 13
- 239000003960 organic solvent Substances 0.000 claims abstract description 5
- 238000003860 storage Methods 0.000 claims description 14
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 11
- 229920001451 polypropylene glycol Polymers 0.000 claims description 5
- 239000003086 colorant Substances 0.000 claims description 4
- 229940053010 pen-aqueous Drugs 0.000 claims 1
- -1 polyethylene Polymers 0.000 abstract description 21
- 239000004743 Polypropylene Substances 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 5
- 229920001155 polypropylene Polymers 0.000 abstract description 5
- 230000002265 prevention Effects 0.000 abstract description 5
- 239000004698 Polyethylene Substances 0.000 abstract description 3
- 229920000573 polyethylene Polymers 0.000 abstract description 3
- 206010013642 Drooling Diseases 0.000 abstract 1
- 208000008630 Sialorrhea Diseases 0.000 abstract 1
- 238000004040 coloring Methods 0.000 abstract 1
- 239000000463 material Substances 0.000 abstract 1
- 239000000976 ink Substances 0.000 description 113
- 239000000049 pigment Substances 0.000 description 30
- 229910052751 metal Inorganic materials 0.000 description 9
- 239000002184 metal Substances 0.000 description 9
- 239000007787 solid Substances 0.000 description 9
- 239000001993 wax Substances 0.000 description 9
- 235000014113 dietary fatty acids Nutrition 0.000 description 8
- 239000000194 fatty acid Substances 0.000 description 8
- 229930195729 fatty acid Natural products 0.000 description 8
- 229920005989 resin Polymers 0.000 description 8
- 239000011347 resin Substances 0.000 description 8
- 239000000047 product Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 6
- 230000003449 preventive effect Effects 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 150000004665 fatty acids Chemical class 0.000 description 4
- 230000004044 response Effects 0.000 description 4
- 238000007665 sagging Methods 0.000 description 4
- 239000004094 surface-active agent Substances 0.000 description 4
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- 239000012736 aqueous medium Substances 0.000 description 3
- DMSMPAJRVJJAGA-UHFFFAOYSA-N benzo[d]isothiazol-3-one Chemical compound C1=CC=C2C(=O)NSC2=C1 DMSMPAJRVJJAGA-UHFFFAOYSA-N 0.000 description 3
- 239000004202 carbamide Substances 0.000 description 3
- XCJYREBRNVKWGJ-UHFFFAOYSA-N copper(II) phthalocyanine Chemical compound [Cu+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 XCJYREBRNVKWGJ-UHFFFAOYSA-N 0.000 description 3
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- 239000002562 thickening agent Substances 0.000 description 3
- SVTBMSDMJJWYQN-UHFFFAOYSA-N 2-methylpentane-2,4-diol Chemical compound CC(O)CC(C)(C)O SVTBMSDMJJWYQN-UHFFFAOYSA-N 0.000 description 2
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- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- 229910001369 Brass Inorganic materials 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 2
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- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
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- 239000002253 acid Substances 0.000 description 2
- 239000012190 activator Substances 0.000 description 2
- 150000005215 alkyl ethers Chemical class 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
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- 239000003945 anionic surfactant Substances 0.000 description 2
- 239000002199 base oil Substances 0.000 description 2
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 2
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- 230000007423 decrease Effects 0.000 description 2
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- XLLIQLLCWZCATF-UHFFFAOYSA-N ethylene glycol monomethyl ether acetate Natural products COCCOC(C)=O XLLIQLLCWZCATF-UHFFFAOYSA-N 0.000 description 2
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- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
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Abstract
Description
【０００１】
【発明の属する技術分野】
本発明はボールペン用水性インキ組成物及びそれを用いた水性ボールペンに関する。更に詳細には、ペン先を外気に長時間晒しても、ペン先の乾燥に起因するカスレや筆記不能の発生を抑えるような耐ドライアップ性（キャップオフ性能）及び垂れ下がり防止性能に優れたボールペン用水性インキ組成物及びそれを用いた水性ボールペンに関する。
【０００２】
【従来の技術】
従来より、ボールペン用水性インキをインキ収容管内に直接収容し、該インキの後端にインキ逆流防止体を備えたボールペンが多数市場に出回っている。そのうち、キャップを要しない構造のボールペン、所謂ノック式のボールペンにおいては、収容されるインキが比較的高い粘度であればインキの垂れ下がりをある程度防止できるものの、低粘度のインキを用いると垂れ下がりを生じ易くなる。
前記ボールペン用水性インキにおいては、更にキャップオフ性能が重要であり、ペン先乾燥防止剤として尿素及び／又はその誘導体の増量等が試みられてきた（例えば、特許文献１参照）。
しかしながら、尿素及び／又は尿素誘導体は吸水性能の高さがキャップオフ性能を発現させるため、これらのキャップオフ性能付与剤を過剰に添加したインキは高湿度条件下で放置した場合、ペン先部分において局部的に水分を吸収することになる。そのため、水性ボールペンにこのようなインキを適用した場合、水分吸収によりペン先部分のインキ粘度が低下し、インキがペン先部分に溜まる「垂れ下がり」、或いは溜まったインキが落下する「ボタ落ち」現象が発生してしまう。
【０００３】
【特許文献１】
特公平５−５４８７５号公報
【０００４】
【発明が解決しようとする課題】
本発明は前記問題を解決するものであって、即ち、垂れ下がりとキャップオフ性の相反する機能を満足させ、筆記性能に優れたボールペン用水性インキ組成物及びそれを用いた水性ボールペンを提供しようとするものである。
【０００５】
【課題を解決するための手段】
本発明は、少なくとも水と、着色剤と、水溶性有機溶剤とからなるインキ組成物中に、酸化ポリエチレン又は酸化ポリプロピレンから選ばれるワックスエマルジョンを含有してなり、前記ワックスエマルジョンの平均粒子径が０．１μｍ以下であるボールペン用水性インキ組成物を要件とする。
更には、前記ワックスエマルジョンをインキ組成物中０．１〜５．０重量％の範囲で含有してなることを要件とする。
更には、前記ボールペン用水性インキ組成物を、ボールペンチップを直接又は中継部材を介して取り付けたインキ収容管内に直接充填し、且つ、インキ組成物後端面にインキ逆流防止体を配設した水性ボールペンを要件とする。
【０００６】
【発明の実施の形態】
本発明に用いられるポリエチレン又はポリプロピレンワックスは、水性媒体中で安定的に分散させるため、化学的に酸化された細かい粒子径の酸化ポリエチレン又は酸化ポリプロピレンワックスである。従って、前記酸化ポリエチレン又は酸化ポリエチレンから選ばれるワックスエマルジョンは、平均粒子径が０．１μｍ以下と粒子径が小さく、インキ中で安定的に存在すると共に、垂れ下がり防止性能に優れる。
前記ワックスエマルジョンは、平均粒子径が０．１μｍ以下であり、経時安定性を満足させるが、０．１μｍを越えると比重が軽いためインキ中で分離するため所期の性能を満足させ難くなる。
また、キャップオフ性能については、ペン先で前記ワックスエマルジョンが析出して被膜を形成してインキの蒸発を抑制し、筆記時の衝撃により被膜が破壊されてインキ出が回復するものと推察される。
【０００７】
前記酸化ポリエチレンとしては、ジョンソンポリマー社製、商品名：ジョンワックス２６、明成化学（株）製、商品名：メイカテックスＰＥＮＯ、メイカテックスＨ６００等が使用できる。
また、酸化ポリプロピレンとしては、明成化学（株）製、商品名：メイカテックスＡＰ−１５５０等を使用できる。
【０００８】
前記酸化ポリエチレン又は酸化ポリプロピレンから選ばれるワックスエマルジョンはインキ組成物全量に対して０．１〜５．０重量％、好ましくは０．５〜３．０重量％の範囲で配合される。０．１重量％未満では垂れ下がり防止効果が得られ難く、５．０重量％を越えるとインキの粘度が上昇して泣き出しやボテの原因になったり、追従性を妨げることがある。更には耐ドライアップ性を悪化させてしまうこともある。
【０００９】
前記着色剤は、水性媒体に溶解もしくは分散可能な染料及び顔料が全て使用可能であり、その具体例を以下に例示する。
酸性染料としては、
ニューコクシン（Ｃ．Ｉ．１６２５５）、
タートラジン（Ｃ．Ｉ．１９１４０）、
アシッドブルーブラック１０Ｂ（Ｃ．Ｉ．２０４７０）、
ギニアグリーン（Ｃ．Ｉ．４２０８５）、
ブリリアントブルーＦＣＦ（Ｃ．Ｉ．４２０９０）、
アシッドバイオレット６ＢＮ（Ｃ．Ｉ．４３５２５）、
ソルブルブルー（Ｃ．Ｉ．４２７５５）、
ナフタレングリーン（Ｃ．Ｉ．４４０２５）、
エオシン（Ｃ．Ｉ．４５３８０）、
フロキシン（Ｃ．Ｉ．４５４１０）、
エリスロシン（Ｃ．Ｉ．４５４３０）、
ニグロシン（Ｃ．Ｉ．５０４２０）、
アシッドフラビン（Ｃ．Ｉ．５６２０５）等が用いられる。
【００１０】
塩基性染料としては、
クリソイジン（Ｃ．Ｉ．１１２７０）、
メチルバイオレットＦＮ（Ｃ．Ｉ．４２５３５）、
クリスタルバイオレット（Ｃ．Ｉ．４２５５５）、
マラカイトグリーン（Ｃ．Ｉ．４２０００）、
ビクトリアブルーＦＢ（Ｃ．Ｉ．４４０４５）、
ローダミンＢ（Ｃ．Ｉ．４５１７０）、
アクリジンオレンジＮＳ（Ｃ．Ｉ．４６００５）、
メチレンブルーＢ（Ｃ．Ｉ．５２０１５）等が用いられる。
【００１１】
直接染料としては、
コンゴーレッド（Ｃ．Ｉ．２２１２０）、
ダイレクトスカイブルー５Ｂ（Ｃ．Ｉ．２４４００）、
バイオレットＢＢ（Ｃ．Ｉ．２７９０５）、
ダイレクトディープブラックＥＸ（Ｃ．Ｉ．３０２３５）、
カヤラスブラックＧコンク（Ｃ．Ｉ．３５２２５）、
ダイレクトファストブラックＧ（Ｃ．Ｉ．３５２５５）、
フタロシアニンブルー（Ｃ．Ｉ．７４１８０）等が用いられる。
【００１２】
前記顔料としては、カーボンブラック、群青などの無機顔料や銅フタロシアニンブルー、ベンジジンイエロー等の有機顔料の他、予め界面活性剤や樹脂を用いて微細に安定的に水媒体中に分散された水分散顔料製品等が用いられ、例えば、Ｃ．Ｉ．Ｐｉｇｍｅｎｔ Ｂｌｕｅ １５：３Ｂ〔品名：Ｓａｎｄｙｅ Ｓｕｐｅｒ Ｂｌｕｅ ＧＬＬ、顔料分２４％、山陽色素株式会社製〕、
Ｃ．Ｉ． Ｐｉｇｍｅｎｔ Ｒｅｄ １４６〔品名：Ｓａｎｄｙｅ Ｓｕｐｅｒ Ｐｉｎｋ ＦＢＬ、顔料分２１．５％、山陽色素株式会社製〕、
Ｃ．Ｉ．Ｐｉｇｍｅｎｔ Ｙｅｌｌｏｗ ８１〔品名：ＴＣ Ｙｅｌｌｏｗ ＦＧ、顔料分約３０％、大日精化工業株式会社製〕、
Ｃ．Ｉ．Ｐｉｇｍｅｎｔ Ｒｅｄ ２２０／１６６〔品名：ＴＣ Ｒｅｄ ＦＧ、顔料分約３５％、大日精化工業株式会社製〕等を挙げることができる。
また、水溶性樹脂を用いた水分散顔料としては、
Ｃ．Ｉ．Ｐｉｇｍｅｎｔ Ｂｌａｃｋ ７〔商品名：ＷＡ ｃｏｌｏｒ Ｂｌａｃｋ Ａ２５０、顔料分１５％、大日精化工業（株）製〕、
Ｃ．Ｉ．Ｐｉｇｍｅｎｔ Ｇｒｅｅｎ ７〔商品名：ＷＡ−Ｓ ｃｏｌｏｒ Ｇｒｅｅｎ、顔料分８％、大日精化工業（株）製〕、
Ｃ．Ｉ．Ｐｉｇｍｅｎｔ Ｖｉｏｌｅｔ ２３〔商品名：マイクロピグモ ＷＭＶＴ−５、顔料分２０％、オリエント化学工業（株）製〕、
Ｃ．Ｉ．Ｐｉｇｍｅｎｔ Ｙｅｌｌｏｗ ８３〔商品名：エマコールＮＳイエロー４６１８、顔料分３０％、山陽色素（株）製〕が挙げられる。
【００１３】
蛍光顔料としては、各種蛍光染料を樹脂マトリックス中に固溶体化した合成樹脂微細粒子状の蛍光顔料が使用できる。その他、金属光沢顔料、蓄光性顔料、二酸化チタン、シリカ、炭酸カルシウム等の白色顔料、可逆熱変色性組成物を内包したカプセル顔料、香料や香料を内包したカプセル顔料等を例示できる。
前記金属光沢顔料としては、アルミニウムや真鍮等の金属粉、芯物質として天然雲母、合成雲母、ガラス片、アルミナ、透明性フィルム片の表面を酸化チタン等の金属酸化物で被覆したパール顔料、金属蒸着膜の片面又は両面に透明又は着色透明フィルムを設けた金属光沢フィルム片を細かく裁断したもの、透明性樹脂層を複数積層した虹彩性フィルムを細かく裁断したものを例示できる。
なお、前記アルミニウムや真鍮等の金属粉を用いる場合、前記金属粉の表面を透明性樹脂や着色透明性樹脂で被覆したものが好適に用いられ、インキ組成物中での安定性に優れる。
【００１４】
また、着色剤として顔料を用いた場合、必要に応じて顔料分散剤を添加できる。
前記顔料分散剤としてはアニオン、ノニオン等の界面活性剤、ポリアクリル酸、スチレンアクリル酸等のアニオン性高分子、ＰＶＰ、ＰＶＡ等の非イオン性高分子等が用いられる。
【００１５】
前記水溶性有機溶剤としては、例えば、エタノール、プロパノール、ブタノール、グリセリン、ソルビトール、トリエタノールアミン、ジエタノールアミン、モノエタノールアミン、エチレングリコール、ジエチレングリコール、チオジエチレングリコール、ヘキシレングリコール、１，３−ブタンジオール、ネオプレングリコール、ポリエチレングリコール、プロピレングリコール、ブチレングリコール、エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、エチレングリコールモノブチルエーテル、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテル、ジエチレングリコールモノブチルエーテル、プロピレングリコールモノメチルエーテル、プロピレングリコールモノエチルエーテル、プロピレングリコールモノブチルエーテル、エチレングリコールモノメチルエーテルアセテート、スルフォラン、２−ピロリドン、Ｎ−メチル−２−ピロリドン等が挙げられる。
前記水溶性有機溶剤は１種又は２種以上を併用することもできる。
【００１６】
上記成分以外に、耐乾燥性を妨げない範疇でアルキッド樹脂、アクリル樹脂、スチレンマレイン酸共重合物、セルローズ誘導体、ポリビニルピロリドン、ポリビニルアルコール、デキストリン等の水溶性樹脂を１種又は２種以上添加したり、尿素、ノニオン系界面活性剤、ソルビット、マンニット、ショ糖、ぶどう糖、還元デンプン加水分解物、ピロリン酸ナトリウム等の湿潤剤を１種又は２種以上添加することもできる。
その他、必要に応じてｐＨ調整剤、防錆剤、防腐剤或いは防黴剤、潤滑剤を添加することができる。
前記ｐＨ調整剤としては、炭酸ナトリウム、リン酸ナトリウム、水酸化ナトリウム、酢酸ソーダ等の無機塩類、トリエタノールアミンやジエタノールアミン等の水溶性のアミン化合物等の有機塩基性化合物等が挙げられる。
前記防錆剤としては、ベンゾトリアゾール及びその誘導体、トリルトリアゾール、ジシクロヘキシルアンモニウムナイトライト、ジイソプロピルアンモニウムナイトライト、チオ硫酸ナトリウム、エチレンジアミン四酢酸塩、サポニン、ジアルキルチオ尿素等が挙げられる。
前記防腐剤或いは防黴剤としては、石炭酸、１、２−ベンズイソチアゾリン−３−オンのナトリウム塩、安息香酸ナトリウム、デヒドロ酢酸ナトリウム、ソルビン酸カリウム、パラオキシ安息香酸プロピル、２，３，５，６−テトラクロロ−４−（メチルスルフォニル）ピリジン等が挙げられる。
前記潤滑剤としては、金属石鹸、ポリアルキレングリコール脂肪酸エステル、エチレンオキサイド付加型カチオン活性剤、リン酸エステル系活性剤、チオカルバミン酸塩、ジメチルジチオカルバミン酸塩等が挙げられる。
その他、溶剤の浸透性を向上させるフッ素系界面活性剤やノニオン、アニオン、カチオン系界面活性剤、ジメチルポリシロキサン等の消泡剤を添加することもできる。
【００１７】
前記インキ組成物をインキ収容管内に直接充填し、且つ、インキ組成物後端面にインキ逆流防止体を配設するタイプのボールペンに用いる場合、インキ中に気体が混入していると、経時により気体が集まって気泡が発生し、筆記時のインキ出に悪影響を与えると共に、筆記先端部に気泡が存在すると筆記不能になる虞れがあるため、アスコルビン酸、アスコルビン酸誘導体、α−トコフェロール、カテキン、カテキン誘導体、合成ポリフェノール、コウジ酸、アルキルヒドロキシルアミン、オキシム誘導体、α−グルコシルルチン、ホスホン酸塩、ホスフィン酸塩、亜硫酸塩、スルホキシル酸塩、亜ジチオン酸塩、チオ硫酸塩、二酸化チオ尿素、ホルムアミジンスルフィン酸、グルタチオン等を添加して化学的に気泡を除去することが好ましい。
【００１８】
本発明のボールペン用水性インキ組成物には、所望により公知の剪断減粘性付与剤、例えば、水に可溶乃至分散性の、キサンタンガム、ウェランガム、構成単糖がグルコースとガラクトースの有機酸修飾ヘテロ多糖体であるサクシノグリカン（平均分子量約１００乃至８００万）、グアーガム、ローカストビーンガム及びその誘導体、ヒドロキシエチルセルロース、アルギン酸アルキルエステル類、メタクリル酸のアルキルエステルを主成分とする分子量１０万〜１５万の重合体、グリコマンナン、寒天やカラゲニン等の海藻より抽出されるゲル化能を有する増粘多糖類、ベンジリデンソルビトール及びベンジリデンキシリトール又はこれらの誘導体、架橋性アクリル酸重合体、無機質微粒子、ポリグリセリン脂肪酸エステル、ポリオキシエチレンソルビタン脂肪酸エステル、ポリエチレングリコール脂肪酸エステル、ポリオキシエチレンヒマシ油、ポリオキシエチレンラノリン・ラノリンアルコール・ミツロウ誘導体、ポリオキシエチレンアルキルエーテル・ポリオキシプロピレンアルキルエーテル、ポリオキシエチレンアルキルフェニルエーテル、脂肪酸アミド等のＨＬＢ値が８〜１２のノニオン系界面活性剤、ジアルキル又はジアルケニルスルホコハク酸の塩類等を例示でき、単独或いは混合して使用することができる。
更に、Ｎ−アルキル−２−ピロリドンとアニオン系界面活性剤の混合物、ポリビニルアルコールとアクリル系樹脂の混合物を用いることもできる。
インキの剪断減粘性とは静止状態あるいは応力の低い時は高粘度で流動し難い性質を有し、応力が増大すると低粘度化して良流動性を示すレオロジー特性を言うものであり、チクソトロピー性あるいは擬似可塑性とも呼ばれる液性を意味している。よって、インキ組成物は筆記時の高剪断応力下においては三次元構造が一時的に破壊されインキの粘度が低下し、筆記先端部のインキは筆記に適した低粘度インキとなり、紙面に転移される。非筆記時にはインキの粘度が高くなり、インキの漏出を防止したり、インキの分離、逆流を防ぐことができる。又、インキ物性を経時的に安定に保つことができる。
【００１９】
インキ収容管内に直接収容されるインキの粘性特性として、ＥＭ型回転粘度計の１００ｒｐｍにおける測定粘度（２０℃）が、３〜１６０ｍＰａ・ｓの範囲にあり、且つ剪断減粘性指数〔粘度計による剪断応力値（Ｔ）及び剪断速度（ｊ）値の流動学的測定により導かれる、実験式（Ｔ＝Ｋｊ ｎ ：但し、Ｋ及びｎは計算された定数である）を適用して計算されるｎ値〕が、０．９〜０．９９の範囲から選ばれる剪断減粘性水性インキ、Ｂ型回転粘度計の６０ｒｐｍにおける測定粘度（２０℃）が、１〜２０ｍＰａ・ｓの範囲にあり、且つ、剪断減粘性指数が０．９〜０．９９の範囲にある剪断減粘性水性インキ、或いは、Ｂ型回転粘度計の６０ｒｐｍにおける測定粘度（２０℃）が、１〜２０ｍＰａ・ｓの範囲にある非剪断減粘性水性インキが好適である。
【００２０】
本発明のボールペン用水性インキ組成物を充填する筆記具自体の構造、形状は特に限定されるものではなく、従来より汎用のものが適用でき、例えば、軸筒内にインキ組成物を充填したインキ収容管を有し、該インキ収容管はボールを先端部に装着したボールペンチップに連通しており、さらにインキの端面には逆流防止用のインキ逆流防止体が密接しているボールペンや、ボールペンチップが外気に晒された状態で軸筒内に収納されており、ノック式、回転式、スライド式等の出没機構を有するボールペン等が例示できる。
【００２１】
前記ボールペンチップは、従来より汎用のチップ機構、例えば、金属を切削加工して内部にボール受け座とインキ導出部を形成したもの、金属製パイプの先端近傍の内面に複数の内方突出部を外面からの押圧変形により設け、前記内方突出部の相互間に、中心部から径方向外方に放射状に延びるインキ流出間隙を形成したもの等を適用でき、特に押圧変形によるチップは、ボール後端との接触面積が比較的小であり、低筆記圧でのスムーズな筆記感を与えることができる。
前記ボールペンチップに抱持されるボールは、超硬合金、ステンレス鋼、ルビー、セラミック等の外径０．３〜１．５ｍｍのボールが有効であり、前記チップのボール抱持部の内径とボールとの径方向の可動距離は１０〜５０μｍ、ボールの軸方向の可動距離は１０〜３０μｍの範囲であることが好ましい。
なお、前記ボールペンチップには、チップ内にボールの後端を前方に弾発する弾発部材を配して、非筆記時にはチップ先端の内縁にボールを押圧させて密接状態とし、筆記時には筆圧によりボールを後退させてインキを流出可能に構成することが好ましく、不使用時のインキ漏れを抑制できる。
前記弾発部材は、金属細線のスプリング、前記スプリングの一端にストレート部（ロッド部）を備えたもの、線状プラスチック加工体等を例示でき、１５〜４５ｇの弾発力により、押圧可能に構成して適用される。
【００２２】
前記ボールペンチップと直接、或いは、接続部材を介して連結されるインキ収容管は、汎用の筒状成形部材、例えば、ポリエチレン、ポリプロピレン、ポリエチレンテレフタレート等の熱可塑性樹脂による成形部材が適用され、インキの低蒸発性、生産性の面で好適に用いられる。
又、前記インキ収容管は、２．５〜１０ｍｍの内径を有するものが好適に用いられる。
更に、前記インキ収容管として透明、着色透明、或いは半透明の成形体を用いることにより、インキ色やインキ残量等を確認できる。
前記インキ収容管はレフィルの形態として軸筒内に収容したり、先端部にチップを装着した軸筒自体をインキ収容管として、前記軸筒内に直接インキを充填してもよい。
【００２３】
前記インキ収容管に収容したインキの後端にはインキ逆流防止体が充填される。
前記インキ逆流防止体は、ポリブテン、α−オレフィンオリゴマー、シリコーン油、精製鉱油等の従来より公知の不揮発性液体或いは難揮発性液体からなる基油に、シリカ、珪酸アルミニウム、膨潤性雲母、脂肪酸アマイド等の増粘剤を添加したものが適用される。
前記基油としては、ポリブテン又はシリコーン油が好適に用いられ、増粘剤としては脂肪酸アマイド又はシリカが好適に用いられる。
本発明に用いられるインキ逆流防止体は、インキ粘度がＥＭ型回転粘度計の１００ｒｐｍにおける測定粘度（２０℃）が、３〜１６０ｍＰａ・ｓの範囲にあり、且つ剪断減粘性指数が、０．９〜０．９９の範囲にある剪断減粘性水性インキ、Ｂ型回転粘度計の６０ｒｐｍにおける測定粘度（２０℃）が、１〜２０ｍＰａ・ｓの範囲にあり、且つ剪断減粘性指数が、０．９〜０．９９の範囲にある剪断減粘性水性インキ、或いは、Ｂ型回転粘度計の６０ｒｐｍにおける測定粘度（２０℃）が、１〜２０ｍＰａ・ｓの範囲にある非剪断減粘性水性インキを用いる場合、粘弾性測定におけるｔａｎδが１を越える点（ω）が２０ｒａｄ／ｓ≦ω≦４５０ｒａｄ／ｓの範囲にあることが好ましい。
これを詳しく説明すると、前記インキは静置状態での粘度が低く、剪断減粘指数を０．１〜０．６程度に調整した従来の剪断減粘性水性インキと比べて耐衝撃性に劣る。よって、インキ収容管後部からインキの漏れ出しを生じ易く、筆記不能になったり、商品価値を損なう虞がある。
よって、インキの後端に配置されるインキ逆流防止体に耐衝撃性を付与して前述した不具合を解消する必要がある。
前記粘弾性測定におけるｔａｎδが１を越える点（ω）が２０ｒａｄ／ｓ≦ω≦４５０ｒａｄ／ｓの範囲にあるインキ逆流防止体は粘弾性を示し、弾性応答と粘性応答の中間的な性質を示す。
粘弾性測定は、レオメーターの振動法により測定し、ｔａｎδとは損失弾性率の値を貯蔵弾性率の値で割ったものであり、この値が低い（ｔａｎδ＜１）と、弾性特性が高く、且つ、粘性特性が低くなる。一方、この値が高い（ｔａｎδ＞１）と、弾性特性が低く、且つ、粘性特性が高くなる。
前述の粘弾性測定において、角周波数（ｒａｄ／ｓ）が２０以上の領域は筆記具に落下等の衝撃を加えた状態に近い領域となる。
従って、２０ｒａｄ／ｓでｔａｎδが１を越える粘弾性を示すインキ逆流防止体は、粘性応答の強さに依存して耐衝撃性を満足させることができる。
前記ｔａｎδが１を越える点は２０ｒａｄ／ｓ以上であるが、４５０ｒａｄ／ｓを越えると弾性応答が強くなってインキ追従性を損ないがちであり、インキ出に乏しくなる。
よって、インキ逆流防止体のｔａｎδが１を越える点（ω）を２０ｒａｄ／ｓ≦ω≦４５０ｒａｄ／ｓの範囲に調整することにより、耐衝撃性と筆記性能を共に満足させることができる。
なお、インキ逆流防止体には、樹脂成形による固体栓を併用することもできる。
【００２４】
【実施例】
以下に実施例を説明するが、本発明はこれらの実施例に限定されるものではない。以下の表に実施例及び比較例のボールペン用水性インキの組成と粘度を示す。
なお，表中の組成の数値は重量部を示す。
実施例１〜４、比較例１〜４、６〜９のインキ粘度は２０℃でＢ型回転粘度計〔東京計器（株）製、ＢＬ、ＢＬアダプター使用）を用いて、６０ｒｐｍにて測定した。
実施例５、及び、比較例５のインキ粘度は２０℃でＥＭＤ型回転粘度計〔東機産業（株）製、ＲＥ−８０Ｒ、標準ロータ使用）を用いて、１００ｒｐｍにて測定した。
前記実施例２、４、及び、比較例２，４，９のインキの剪断減粘指数は０．９７であり、実施例５のインキの剪断減粘指数は０．３であり、比較例５のインキの剪断減粘指数は０．３であった。
【００２５】
【表１】
【表２】
表中の原料の内容について注番号に沿って説明する。
（１）オリエント化学工業（株）製、商品名：フィスコブラック８８６、有効成分１５％
（２）アイゼン保土谷（株）製、Ｃ．Ｉ．４５４１０、商品名：フロキシン
（３）住友化学工業（株）製、Ｃ．Ｉ．４２６５５、商品名：アシッドブルーＰＧ
（４）ジョンソンポリマー社製、商品名：ジョンワックス２６、粒子径０．０７μｍ、固形分２５％
（５）明成化学（株）製、商品名：メイカテックスＰＥＮＯ、粒子径０．１μｍ以下、固形分２５％
（６）明成化学（株）製、商品名：メイカテックスＨ６００、粒子径０．０４μｍ、固形分２５％
（７）明成化学（株）製、商品名：メイカテックスＡＰ−１５５０、粒子径０．１μｍ以下、固形分４０％
（８）太陽化学（株）製、商品名：サンカラ６３４
（９）ＢＡＳＦ社製、商品名：ルビスコールＫ−３０、分子量４００００
（１０）三晶（株）製、商品名：レオザン
（１１）１，２−ベンズチアゾリン−３−オン、アビシア（株）製、商品名：プロキセルＸＬ−２
（１２）リン酸エステル系界面活性剤、第一工業製薬（株）製、商品名：プライサーフＡＬ
（１３）エレメンティスジャパン社製、商品名：ＳＬＩＰ−ＡＩＤ ６３５Ｅ、粒子径０．１〜１μｍ、固形分３５％
（１４）ジョンソンポリマー社製、商品名：ジョンクリル７８０、粒子径０．１μｍ、固形分４８％、最低造膜温度５０℃以上
（１５）クラリアント社製、商品名：モビニール９７２、粒子径０．１μｍ以上、固形分５０％、最低造膜温度２２０℃以上
（１６）日本エスエスシー（株）製、商品名：カネビノールＫＤ５、粒子径０．０２μｍ、固形分３５％、最低造膜温度６５℃以上
【００２８】
インキ逆流防止体の調製
基油としてポリブテン８５部中に、増粘剤として脂肪酸アマイド１５部を添加した後、３本ロールにて混練してインキ逆流防止体を得た。
なお、前記インキ逆流防止体は、２０℃でレオメーター〔Ｐａａｒ Ｐｈｙｓｉｃａ社製、ＤＳＲ４０００、２°のコーンプレート（直径２５ｍｍ）使用〕を用いて測定した結果、１００ｒａｄ／ｓでｔａｎδが１を越えるものであった。
【００２９】
水性ボールペンの作製
前記各インキ組成物を直径０．５ｍｍのボールを抱持するステンレススチール製チップがポリプロピレン製パイプ（内径３．８ｍｍ）の一端に嵌着されたボールペンレフィルに充填し、その後端に前記インキ逆流防止体を配設した後、前記ボールペンレフィルを軸筒に組み込み、水性ボールペンを作製した。
【００３０】
前記各水性ボールペンにより以下のテストを行った。
垂れ下がり試験
キャップを外した水性ボールペンを、ペン先（ボールペンチップ）非接触状態で下向き（倒立）に保持し、温度２０℃、相対湿度９０％の雰囲気下に２０時間放置した後、ペン先の外観を目視で観察し、以下の基準で評価した。
キャップオフ試験
組み立て後、筆記可能であることを確認した水性ボールペンを、ペン先を露出した状態で室温（２０℃）、湿度５５〜７５％ＲＨの条件下に横置き、１０日間放置後、ＪＩＳ Ｐ３２０１筆記用紙Ａに手書きで丸を一行に１２個連続筆記し、何行目から正常に筆記できるかを調べ、以下の基準で評価した。
インキ安定性試験
各インキ組成物を室温（２０℃）及び５０℃で７日間放置した後、インキの状態を目視により観察した。
【００３１】
試験結果を以下の表に示す。
【表３】
尚、テスト結果の評価の記号の内容は以下のとおり。
垂れ下がり試験
○：インキの漏れだし（垂れ下がり）が認められない。
△：チップ先端にインキの小滴が認められる。
×：チップ先端に、大きいインキ滴が認められる、或いはチップ先端から漏れたインキが落下している。
キャップオフ試験
○：即筆記可能
△：１行以内で筆記可能となる
×：１行以内で筆記できない。
インキ安定性試験
○：異常なし。
×：エマルジョンが浮いたり、沈降している。
【００３３】
【発明の効果】
本発明は、垂れ下がり防止効果とキャップオフ効果を共に備えた、筆記性能に優れたボールペン用水性インキ組成物及びそれを用いた水性ボールペンを提供できる。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to an aqueous ink composition for a ballpoint pen and an aqueous ballpoint pen using the same. More specifically, a ball-point pen with excellent dry-up resistance (cap-off performance) and droop prevention performance that suppresses the occurrence of blurring and writing failure due to drying of the pen tip even when the pen tip is exposed to the open air for a long time. The present invention relates to an aqueous ink composition for use and an aqueous ballpoint pen using the same.
[0002]
[Prior art]
2. Description of the Related Art Conventionally, a large number of ballpoint pens having a water-based ink for ballpoint pens directly housed in an ink storage tube and provided with an ink backflow preventer at the rear end of the ink have been on the market. Among them, a ball-point pen having a structure that does not require a cap, a so-called knock-type ball-point pen, can prevent ink dripping to a certain extent if the contained ink has a relatively high viscosity. However, if a low-viscosity ink is used, dripping tends to occur. Become.
In the water-based ink for a ball-point pen, the cap-off performance is further important, and an attempt has been made to increase the amount of urea and / or a derivative thereof as a pen tip drying inhibitor (for example, see Patent Document 1).
However, urea and / or urea derivatives exhibit cap-off performance because of their high water-absorbing performance. Therefore, when an ink containing these cap-off performance-imparting agents in excess is left under a high humidity condition, the ink may have a pen tip portion. Water will be absorbed locally. Therefore, when such an ink is applied to a water-based ball-point pen, the ink viscosity at the pen tip decreases due to the absorption of water, and the ink hangs down at the pen tip, or the accumulated ink falls, or the "dropping" phenomenon occurs. Will occur.
[0003]
[Patent Document 1]
Japanese Patent Publication No. 5-54575
[Problems to be solved by the invention]
The present invention is intended to solve the above-mentioned problems, that is, to provide a water-based ink composition for a ball-point pen which satisfies the opposing functions of sag and cap-off properties and has excellent writing performance, and a water-based ball-point pen using the same. Is what you do.
[0005]
[Means for Solving the Problems]
The present invention comprises, in an ink composition comprising at least water, a colorant, and a water-soluble organic solvent, a wax emulsion selected from polyethylene oxide or polypropylene oxide, and the wax emulsion has an average particle size of 0. A water-based ink composition for ballpoint pens having a size of 0.1 μm or less is required.
Furthermore, it is required that the wax emulsion be contained in the ink composition in a range of 0.1 to 5.0% by weight.
Furthermore, an aqueous ballpoint pen in which the ballpoint pen-based water-based ink composition is directly filled into an ink storage tube to which a ballpoint pen tip is attached directly or via a relay member, and an ink backflow preventer is provided on a rear end face of the ink composition. Is required.
[0006]
BEST MODE FOR CARRYING OUT THE INVENTION
The polyethylene or polypropylene wax used in the present invention is a chemically oxidized polyethylene oxide or polypropylene oxide wax having a fine particle diameter to be stably dispersed in an aqueous medium. Accordingly, the above-mentioned polyethylene oxide or a wax emulsion selected from polyethylene oxide has a small average particle diameter of 0.1 μm or less, is stable in the ink, and is excellent in anti-sagging performance.
The wax emulsion has an average particle size of 0.1 μm or less and satisfies the stability over time. However, if it exceeds 0.1 μm, the specific gravity is too small to separate in the ink, so that it is difficult to satisfy the desired performance.
Regarding the cap-off performance, it is speculated that the wax emulsion precipitates at the pen tip to form a film to suppress the evaporation of the ink, and the impact at the time of writing breaks the film to recover the ink ejection. .
[0007]
As the polyethylene oxide, Johnson Polymer Co., Ltd., trade name: John Wax 26, manufactured by Meisei Chemical Co., Ltd., trade names: Maycatex PENO, Maycatex H600, etc. can be used.
Further, as the oxidized polypropylene, Maycatex AP-1550 (trade name, manufactured by Meisei Chemical Co., Ltd.) can be used.
[0008]
The wax emulsion selected from the above-mentioned polyethylene oxide or polypropylene oxide is blended in an amount of 0.1 to 5.0% by weight, preferably 0.5 to 3.0% by weight, based on the total amount of the ink composition. If the amount is less than 0.1% by weight, the effect of preventing sagging is hardly obtained. If the amount exceeds 5.0% by weight, the viscosity of the ink increases, which may cause tearing, dents, or obstruction of followability. Further, dry-up resistance may be deteriorated.
[0009]
As the colorant, all dyes and pigments that can be dissolved or dispersed in an aqueous medium can be used, and specific examples thereof are shown below.
As acid dyes,
New coccin (CI. 16255),
Tartrazine (CI. 19140),
Acid Blue Black 10B (CI. 20470),
Guinea Green (CI. 42085),
Brilliant blue FCF (CI. 42090),
Acid Violet 6BN (CI. 43525),
Soluble Blue (C.I. 42755),
Naphthalene green (CI.44025),
Eosin (C.I. 45380),
Phloxine (CI. 45410),
Erythrosine (CI. 45430),
Nigrosine (C.I. 50420),
Acid flavin (CI. 56205) and the like are used.
[0010]
As basic dyes,
Chrysoidin (CI. 11270),
Methyl violet FN (CI. 42535),
Crystal violet (CI. 42555),
Malachite green (CI.42000),
Victoria Blue FB (CI.44045),
Rhodamine B (CI. 45170),
Acridine orange NS (CI. 46005),
Methylene blue B (CI. 52015) and the like are used.
[0011]
As a direct dye,
Congo Red (CI. 22120),
Direct Sky Blue 5B (CI. 24400),
Violet BB (CI. 27905),
Direct deep black EX (CI. 30235),
Kayalas Black G Conch (CI. 35225),
Direct Fast Black G (CI. 35255),
Phthalocyanine blue (CI. 74180) and the like are used.
[0012]
As the pigment, carbon black, inorganic pigments such as ultramarine blue, and organic pigments such as copper phthalocyanine blue and benzidine yellow, as well as an aqueous dispersion finely and stably dispersed in an aqueous medium using a surfactant or a resin in advance. Pigment products and the like are used. I. Pigment Blue 15: 3B [product name: Sandy Super Blue GLL, pigment content 24%, Sanyo Dyeing Co., Ltd.],
C. I. Pigment Red 146 [product name: Sandy Super Pink FBL, pigment content 21.5%, manufactured by Sanyo Dyeing Co., Ltd.],
C. I. Pigment Yellow 81 [product name: TC Yellow FG, pigment content: about 30%, manufactured by Dainichi Seika Kogyo Co., Ltd.],
C. I. Pigment Red 220/166 [product name: TC Red FG, pigment content: about 35%, manufactured by Dainichi Seika Kogyo Co., Ltd.] and the like.
In addition, as a water-dispersed pigment using a water-soluble resin,
C. I. Pigment Black 7 (trade name: WA color Black A250, pigment content 15%, manufactured by Dainichi Seika Kogyo Co., Ltd.),
C. I. Pigment Green 7 (trade name: WA-S color Green, pigment content 8%, manufactured by Dainichi Seika Kogyo Co., Ltd.),
C. I. Pigment Violet 23 (trade name: MicroPigmo WMVT-5, pigment content 20%, manufactured by Orient Chemical Industry Co., Ltd.),
C. I. Pigment Yellow 83 (trade name: Emacol NS Yellow 4618, pigment content: 30%, manufactured by Sanyo Dyeing Co., Ltd.).
[0013]
As the fluorescent pigment, a synthetic resin fine particle-shaped fluorescent pigment in which various fluorescent dyes are made into a solid solution in a resin matrix can be used. Other examples include metal luster pigments, luminous pigments, white pigments such as titanium dioxide, silica, calcium carbonate, capsule pigments containing a reversible thermochromic composition, capsule pigments containing fragrances and fragrances, and the like.
Examples of the metallic luster pigment include metal powders such as aluminum and brass, natural mica, synthetic mica, glass flakes, alumina, and pearl pigments in which the surface of a transparent film piece is coated with a metal oxide such as titanium oxide as a core substance, metal Examples thereof include finely cut pieces of a metallic glossy film provided with a transparent or colored transparent film on one or both sides of a vapor-deposited film, and finely cut pieces of an iris film having a plurality of laminated transparent resin layers.
When the metal powder such as aluminum or brass is used, a metal powder whose surface is coated with a transparent resin or a colored transparent resin is preferably used, and is excellent in stability in the ink composition.
[0014]
When a pigment is used as a colorant, a pigment dispersant can be added as needed.
Examples of the pigment dispersant include surfactants such as anions and nonions, anionic polymers such as polyacrylic acid and styrene acrylic acid, and nonionic polymers such as PVP and PVA.
[0015]
Examples of the water-soluble organic solvent include ethanol, propanol, butanol, glycerin, sorbitol, triethanolamine, diethanolamine, monoethanolamine, ethylene glycol, diethylene glycol, thiodiethylene glycol, hexylene glycol, 1,3-butanediol, and neoprene. Glycol, polyethylene glycol, propylene glycol, butylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoe Ether, propylene glycol monobutyl ether, ethylene glycol monomethyl ether acetate, sulfolane, 2-pyrrolidone, N- methyl-2-pyrrolidone.
The water-soluble organic solvents may be used alone or in combination of two or more.
[0016]
In addition to the above components, one or more water-soluble resins such as an alkyd resin, an acrylic resin, a styrene-maleic acid copolymer, a cellulose derivative, polyvinylpyrrolidone, polyvinyl alcohol, and dextrin are added as long as the drying resistance is not impaired. Alternatively, one or more humectants such as urea, nonionic surfactant, sorbite, mannitol, sucrose, glucose, reduced starch hydrolyzate, sodium pyrophosphate and the like can be added.
In addition, a pH adjuster, a rust inhibitor, a preservative, a fungicide, or a lubricant can be added as necessary.
Examples of the pH adjuster include inorganic salts such as sodium carbonate, sodium phosphate, sodium hydroxide, and sodium acetate; and organic basic compounds such as water-soluble amine compounds such as triethanolamine and diethanolamine.
Examples of the rust preventive include benzotriazole and its derivatives, tolyltriazole, dicyclohexylammonium nitrite, diisopropylammonium nitrite, sodium thiosulfate, ethylenediaminetetraacetate, saponin, dialkylthiourea and the like.
Examples of the preservative or antifungal agent include sodium carbonate of 1,2-benzisothiazolin-3-one, sodium benzoate, sodium dehydroacetate, potassium sorbate, propyl paraoxybenzoate, 2,3,5,6 -Tetrachloro-4- (methylsulfonyl) pyridine and the like.
Examples of the lubricant include metal soap, polyalkylene glycol fatty acid ester, ethylene oxide addition type cationic activator, phosphate activator, thiocarbamate, dimethyldithiocarbamate and the like.
In addition, it is also possible to add a fluorine-based surfactant for improving the permeability of the solvent, a nonionic, anionic or cationic surfactant, and an antifoaming agent such as dimethylpolysiloxane.
[0017]
When the ink composition is used for a ballpoint pen in which the ink composition is directly filled into an ink storage tube and an ink backflow prevention member is provided on the rear end face of the ink composition, if gas is mixed in the ink, the gas is gradually removed. Are gathered to generate air bubbles, which adversely affects the ink output during writing, and may cause inability to write if air bubbles are present at the writing tip, so ascorbic acid, ascorbic acid derivatives, α-tocopherol, catechin, Catechin derivative, synthetic polyphenol, kojic acid, alkylhydroxylamine, oxime derivative, α-glucosylrutin, phosphonate, phosphinate, sulfite, sulfoxylate, dithionite, thiosulfate, thiourea dioxide, form It is preferable to chemically remove bubbles by adding amidine sulfinic acid, glutathione, etc. .
[0018]
The aqueous ink composition for a ballpoint pen of the present invention may optionally contain a known shear-thinning agent, for example, water-soluble or dispersible, xanthan gum, welan gum, and a monosaccharide composed of an organic acid-modified heteropolysaccharide of glucose and galactose. Succinoglycan (average molecular weight of about 1-8 million), guar gum, locust bean gum and its derivatives, hydroxyethylcellulose, alginic acid alkyl esters, and methacrylic acid alkyl esters having a molecular weight of 100,000-150,000. Polymers, glycomannans, thickening polysaccharides having gelling ability extracted from seaweeds such as agar and carrageenan, benzylidene sorbitol and benzylidene xylitol or derivatives thereof, crosslinkable acrylic acid polymers, inorganic fine particles, polyglycerin fatty acid esters , Polyoxye Rensorbitan fatty acid ester, polyethylene glycol fatty acid ester, polyoxyethylene castor oil, polyoxyethylene lanolin, lanolin alcohol, beeswax derivative, polyoxyethylene alkyl ether, polyoxypropylene alkyl ether, polyoxyethylene alkyl phenyl ether, fatty acid amide, etc. Nonionic surfactants having an HLB value of 8 to 12, salts of dialkyl or dialkenyl sulfosuccinic acid, and the like can be exemplified, and these can be used alone or in combination.
Further, a mixture of N-alkyl-2-pyrrolidone and an anionic surfactant, and a mixture of polyvinyl alcohol and an acrylic resin can also be used.
The shear thinning property of ink is a rheological property that has a high viscosity and is difficult to flow when the ink is in a static state or at a low stress, and has a low viscosity when the stress is increased, indicating good flowability. It means liquidity, also called pseudoplasticity. Therefore, under the high shear stress during writing, the ink composition temporarily breaks the three-dimensional structure and the viscosity of the ink decreases, and the ink at the writing tip becomes a low-viscosity ink suitable for writing and is transferred to the paper surface. You. At the time of non-writing, the viscosity of the ink becomes high, so that it is possible to prevent the leakage of the ink, the separation of the ink, and the backflow. Further, the physical properties of the ink can be stably maintained over time.
[0019]
As viscosity characteristics of the ink directly stored in the ink storage tube, the viscosity measured at 100 rpm (20 ° C.) of the EM-type rotational viscometer is in the range of 3 to 160 mPa · s, and the shear thinning index [shear by viscometer] N calculated by applying an empirical formula (T = Kj n, where K and n are calculated constants), derived from rheological measurements of stress (T) and shear rate (j) values Value] is a shear-thinning aqueous ink selected from the range of 0.9 to 0.99, the viscosity measured at 60 rpm (20 ° C.) of a B-type rotational viscometer is in the range of 1 to 20 mPa · s, and A shear-thinning water-based ink having a shear-thinning index in the range of 0.9 to 0.99, or a non-shearing type in which the viscosity measured at 60 rpm (20 ° C.) of a B-type rotary viscometer is in the range of 1 to 20 mPa · s. Shear thinning aqueous in It is preferred.
[0020]
The structure and shape of the writing implement itself for filling the water-based ink composition for a ballpoint pen of the present invention are not particularly limited, and a general-purpose one can be applied conventionally, for example, an ink container filled with an ink composition in a barrel. The ink storage tube has a tube, and the ink storage tube communicates with a ballpoint pen tip having a ball mounted on the tip, and a ballpoint pen or a ballpoint pen, in which an ink backflow prevention body for backflow prevention is in close contact with the end surface of the ink, is provided. A ball-point pen, which is housed in a shaft cylinder in a state of being exposed to the outside air, and has a retractable mechanism such as a knock type, a rotary type, and a slide type, can be exemplified.
[0021]
The ball-point pen tip is a general-purpose tip mechanism, for example, a metal cutting machine in which a ball receiving seat and an ink lead-out portion are formed inside, and a plurality of inwardly projecting portions on the inner surface near the tip of a metal pipe. An ink discharge gap extending radially outward from a center portion is formed between the inwardly projecting portions by pressing deformation from the outer surface. The contact area with the edge is relatively small, and a smooth writing feeling at a low writing pressure can be provided.
As the ball held by the ballpoint pen tip, a ball having an outer diameter of 0.3 to 1.5 mm such as cemented carbide, stainless steel, ruby, or ceramic is effective. Is preferably in the range of 10 to 50 μm, and the movable distance in the axial direction of the ball is preferably in the range of 10 to 30 μm.
The ballpoint pen tip is provided with a resilient member that repels the rear end of the ball forward in the chip, and presses the ball against the inner edge of the tip of the tip during non-writing to make a close contact, and at writing time by writing pressure. It is preferable that the ball is retracted so that the ink can flow out, so that ink leakage when not in use can be suppressed.
Examples of the resilient member include a thin metal wire spring, a member having a straight portion (rod portion) at one end of the spring, and a linear plastic processed body. The resilient member is configured to be capable of being pressed by a resilient force of 15 to 45 g. Applied.
[0022]
The ink storage tube connected directly to the ball-point pen tip or via a connection member is a general-purpose cylindrical molded member, for example, a molded member made of a thermoplastic resin such as polyethylene, polypropylene, and polyethylene terephthalate is applied. It is preferably used in terms of low evaporation and productivity.
The ink container preferably has an inner diameter of 2.5 to 10 mm.
Further, by using a transparent, colored transparent or translucent molded body as the ink storage tube, the ink color, the remaining ink amount, and the like can be confirmed.
The ink storage tube may be housed in a shaft cylinder in the form of a refill, or the shaft cylinder having a tip mounted at its tip may be used as an ink storage tube to directly fill the shaft cylinder with ink.
[0023]
The back end of the ink stored in the ink storage tube is filled with an ink backflow preventer.
The ink backflow preventer is prepared by adding a conventionally known non-volatile liquid or a non-volatile liquid such as polybutene, α-olefin oligomer, silicone oil, refined mineral oil or the like to silica, aluminum silicate, swellable mica, fatty acid amide. What added the thickeners, such as, is applied.
Polybutene or silicone oil is preferably used as the base oil, and fatty acid amide or silica is suitably used as the thickener.
The ink backflow preventive used in the present invention has an ink viscosity measured at 100 rpm by an EM type rotational viscometer (20 ° C.) in the range of 3 to 160 mPa · s, and a shear thinning index of 0.9. The shear-thinning aqueous ink in the range of 0.99 to 0.99, the viscosity measured at 60 rpm (20 ° C.) of a B-type rotary viscometer is in the range of 1 to 20 mPa · s, and the shear-thinning index is 0.9. When using a shear-thinning aqueous ink in the range of 0.99 to 0.99 or a non-shear-thinning aqueous ink having a viscosity measured at 60 rpm (20 ° C) of a B-type rotational viscometer in the range of 1 to 20 mPa · s. The point (ω) where tan δ exceeds 1 in the viscoelasticity measurement is preferably in the range of 20 rad / s ≦ ω ≦ 450 rad / s.
More specifically, the ink has a low viscosity in a stationary state, and is inferior in impact resistance to a conventional shear-thinning aqueous ink in which the shear-thinning index is adjusted to about 0.1 to 0.6. Therefore, the ink easily leaks from the rear portion of the ink storage tube, which may make writing impossible or impair the commercial value.
Therefore, it is necessary to impart impact resistance to the ink backflow preventive disposed at the rear end of the ink to solve the above-mentioned problem.
The ink backflow preventive in which the point (ω) where tan δ exceeds 1 in the viscoelasticity measurement is in the range of 20 rad / s ≦ ω ≦ 450 rad / s exhibits viscoelasticity, and exhibits an intermediate property between elastic response and viscous response. .
Viscoelasticity is measured by a rheometer vibration method. Tan δ is a value obtained by dividing the value of the loss modulus by the value of the storage modulus. When this value is low (tan δ <1), the elastic property is high. In addition, the viscosity characteristics are reduced. On the other hand, when this value is high (tan δ> 1), the elastic properties are low and the viscosity properties are high.
In the viscoelasticity measurement described above, a region where the angular frequency (rad / s) is 20 or more is a region close to a state where an impact such as dropping is applied to the writing instrument.
Therefore, an ink backflow preventive having viscoelasticity with tan δ exceeding 1 at 20 rad / s can satisfy impact resistance depending on the strength of the viscous response.
The point where the tan δ exceeds 1 is 20 rad / s or more. However, when the tan δ exceeds 450 rad / s, the elastic response tends to be strong and ink followability tends to be impaired, resulting in poor ink output.
Therefore, by adjusting the point (ω) at which tan δ of the ink backflow preventer exceeds 1 in the range of 20 rad / s ≦ ω ≦ 450 rad / s, both the impact resistance and the writing performance can be satisfied.
It should be noted that a solid stopper formed by resin molding may be used in combination with the ink backflow preventer.
[0024]
【Example】
Examples will be described below, but the present invention is not limited to these examples. The following table shows the compositions and viscosities of the aqueous inks for ballpoint pens of the examples and comparative examples.
In addition, the numerical value of the composition in a table shows a weight part.
The ink viscosities of Examples 1 to 4, Comparative Examples 1 to 4, and 6 to 9 were measured at 20 rpm at 60 rpm using a B-type rotational viscometer (BL, BL adapter manufactured by Tokyo Keiki Co., Ltd.). .
The ink viscosities of Example 5 and Comparative Example 5 were measured at 20 ° C. at 100 rpm using an EMD type rotational viscometer (manufactured by Toki Sangyo Co., Ltd., RE-80R, using a standard rotor).
The inks of Examples 2, 4 and Comparative Examples 2, 4, and 9 had a shear thinning index of 0.97, and the ink of Example 5 had a shear thinning index of 0.3. The ink had a shear thinning index of 0.3.
[0025]
[Table 1]
[Table 2]
The contents of the raw materials in the table will be described along the note numbers.
(1) Orient Chemical Co., Ltd., trade name: FISCO Black 886, active ingredient 15%
(2) Eisen Hodogaya Co., Ltd., C.I. I. 45410, trade name: Phloxine (3) manufactured by Sumitomo Chemical Co., Ltd., C.I. I. 42655, Product name: Acid Blue PG
(4) Johnson Polymer Co., Ltd., trade name: John Wax 26, particle size 0.07 μm, solid content 25%
(5) Made by Meisei Chemical Co., Ltd., trade name: Maycatex PENO, particle size 0.1 μm or less, solid content 25%
(6) Meisei Chemical Co., Ltd., trade name: Maycatex H600, particle size 0.04 μm, solid content 25%
(7) Trade name: Maycatex AP-1550, manufactured by Meisei Chemical Co., Ltd., particle size 0.1 μm or less, solid content 40%
(8) Taiyo Chemical Co., Ltd., trade name: Sankara 634
(9) BASF, trade name: Luviscol K-30, molecular weight 40000
(10) Sansei Corporation, trade name: Leozan (11) 1,2-benzthiazolin-3-one, Avicia Corporation, trade name: Proxel XL-2
(12) Phosphate ester surfactant, manufactured by Daiichi Kogyo Seiyaku Co., Ltd., trade name: Price Surf AL
(13) Product name: SLIP-AID 635E, particle diameter 0.1-1 μm, solid content 35%, manufactured by Elementis Japan
(14) Johnson Polymer Co., Ltd., trade name: John Krill 780, particle size 0.1 μm, solid content 48%, minimum film formation temperature 50 ° C. or more. (15) Clariant Co., trade name: Movinyl 972, particle size 0. 1 μm or more, solid content 50%, minimum film-forming temperature 220 ° C. or more (16) manufactured by Japan SSC Co., Ltd., trade name: Kanebinol KD5, particle diameter 0.02 μm, solid content 35%, minimum film-forming temperature 65 ° C. or more [0028]
Preparation of Ink Backflow Preventor In 85 parts of polybutene as a base oil, 15 parts of a fatty acid amide as a thickener was added and kneaded with three rolls to obtain an ink backflow preventer.
The ink backflow preventive was measured at 20 ° C. using a rheometer (manufactured by Paar Physica, DSR4000, using a 2 ° cone plate (diameter: 25 mm)). As a result, tan δ exceeded 1 at 100 rad / s. Met.
[0029]
Preparation of Water-based Ballpoint Pen Each of the above ink compositions was filled into a ballpoint pen refill fitted with a stainless steel tip holding a ball having a diameter of 0.5 mm into one end of a polypropylene pipe (inner diameter: 3.8 mm), and then into the rear end. After arranging the ink backflow preventer, the ballpoint pen refill was incorporated into a barrel to produce an aqueous ballpoint pen.
[0030]
The following tests were performed with each of the aqueous ballpoint pens.
An aqueous ballpoint pen with the hanging test cap removed is held downward (inverted) in a non-contact state with the penpoint (ballpoint pen tip) and left for 20 hours in an atmosphere at a temperature of 20 ° C. and a relative humidity of 90%. Was visually observed and evaluated according to the following criteria.
After assembling the cap-off test, the aqueous ball-point pen confirmed to be writable was placed sideways under the condition of room temperature (20 ° C.) and a humidity of 55 to 75% RH with the pen tip exposed, and after standing for 10 days, JIS Twelve circles were continuously written on a P3201 writing paper A by hand by hand, and it was checked from which line the writing could be started normally, and evaluated based on the following criteria.
Ink stability test Each ink composition was allowed to stand at room temperature (20 ° C.) and 50 ° C. for 7 days, and then the state of the ink was visually observed.
[0031]
The test results are shown in the table below.
[Table 3]
The contents of the test result evaluation symbols are as follows.
Sagging test ：: No leakage of ink (sagging) is observed.
Δ: Small ink droplets are observed at the tip of the chip.
×: A large ink droplet is observed at the tip of the chip, or ink leaked from the tip of the chip is dropped.
Cap-off test ○: Immediate writing possible Δ: Writable within 1 line ×: Not writable within 1 line
Ink stability test ：: No abnormality.
×: The emulsion is floating or settling.
[0033]
【The invention's effect】
INDUSTRIAL APPLICABILITY The present invention can provide a water-based ink composition for a ballpoint pen having both a sag preventing effect and a cap-off effect, and excellent in writing performance, and an aqueous ballpoint pen using the same.
Claims (3)
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| JP2003153945A JP4308583B2 (en) | 2003-05-30 | 2003-05-30 | Water-based ballpoint pen |
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| JP2003153945A JP4308583B2 (en) | 2003-05-30 | 2003-05-30 | Water-based ballpoint pen |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006193688A (en) * | 2005-01-17 | 2006-07-27 | Mitsubishi Pencil Co Ltd | Ink composition for water-based ballpoint pen and water-based ballpoint pen |
| JP2006206823A (en) * | 2005-01-31 | 2006-08-10 | Mitsubishi Pencil Co Ltd | Ink composition for use in writing utensil, and ballpoint pen |
| JP2009286818A (en) * | 2008-05-27 | 2009-12-10 | Pilot Ink Co Ltd | Water-based ink composition for ballpoint pen and ballpoint pen having the same therein |
| JP2013103986A (en) * | 2011-11-14 | 2013-05-30 | Mitsubishi Pencil Co Ltd | Ink composition for ballpoint pen |
-
2003
- 2003-05-30 JP JP2003153945A patent/JP4308583B2/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006193688A (en) * | 2005-01-17 | 2006-07-27 | Mitsubishi Pencil Co Ltd | Ink composition for water-based ballpoint pen and water-based ballpoint pen |
| JP2006206823A (en) * | 2005-01-31 | 2006-08-10 | Mitsubishi Pencil Co Ltd | Ink composition for use in writing utensil, and ballpoint pen |
| JP2009286818A (en) * | 2008-05-27 | 2009-12-10 | Pilot Ink Co Ltd | Water-based ink composition for ballpoint pen and ballpoint pen having the same therein |
| JP2013103986A (en) * | 2011-11-14 | 2013-05-30 | Mitsubishi Pencil Co Ltd | Ink composition for ballpoint pen |
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| JP4308583B2 (en) | 2009-08-05 |
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