JP3977625B2 - Ink backflow preventive composition for writing instrument and writing instrument incorporating the same - Google Patents
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【０００１】
【発明の属する技術分野】
本発明は筆記具用インキ逆流防止体組成物及びそれを内蔵した筆記具に関する。更に詳細には、筆記先端部と、高粘度乃至中粘度又は剪断減粘性インキが直接収容されたインキ収容管を備えた筆記具における、前記インキ収容管の開放側インキ端面に充填される筆記具用インキ逆流防止体組成物及び前記インキ逆流防止体組成物を内蔵した筆記具に関する。
【０００２】
【従来の技術】
この種の筆記具用インキ逆流防止体組成物は、正立（チップ上向き）或いは横置き状態で保管又は運搬された時に、インキがインキ収容管後端から漏出することを防止するインキ逆流防止性能、筆記の際インキの減少に伴って、ペン先方向へスムースに移動するインキ追従性能、インキに追従する際にインキ収容管壁面へのインキ及びインキ逆流防止体の付着を防止するビジブル性能及び筆記具本体を落下させたときのインキ飛び散りやインキ流出を防ぐ耐衝撃性能等が要求される。
【０００３】
従来、高粘度の油性インキを用いた油性ボールペン用のインキ逆流防止体としては鉱油と金属石鹸の混合物であるグリース等が適用されている。
又、中粘度或いは剪断減粘性を有する水性インキを用いた水性ボールペンに前記油性ボールペン用インキ逆流防止体を適用すると、インキへの追従不良や温度変化による粘度変化が大きいことによって水性インキの逆流を抑止できない等の不具合を生じるため、液状ポリブテン、鉱油、シリコーンオイル等の難揮発性有機液体に増粘剤を添加して高粘稠流体としたインキ逆流防止体が多数提案され、広く実用化されている。
【０００４】
【発明が解決しようとする課題】
例えば特開２０００−９６０３３号公報にはシリコーン油に疎水性シリカとポリ（オキシエチレン・オキシプロピレン）ポリオールを添加したインキ逆流防止体が開示されているが、増粘剤として疎水性シリカを用いると、経時によりインキ逆流防止体組成物中から、基油であるシリコーン油の低分子量成分と推定される液体成分が徐々に分離する現象が認められる。このような、組成物中の液体成分が分離するようなインキ逆流防止体が適用されたボールペンはチップ先端部が上向き状態（販売店での陳列ではこの状態となっている）で長期間放置された場合、分離した成分は比重がインキより小さいためにインキ収容管壁面を伝って上昇しインキ収容管の先端部分に溜まり、筆跡の濃度低下或いは筆記不良を発生させてしまう。
【０００５】
また特開平１０−６７１９６号公報には衝撃によるインキ逆流防止体の移動或いは飛び出しを防止する目的で、難揮発性流体および／または不揮発性流体よりなる基材と、平均粒径が１０〜２００μｍの粒子を含有するインキ逆流防止体が開示されている。
しかしながら前記の構成からなるインキ逆流防止体において、十分な耐衝撃性を得るためには前記粒子を２０〜６０容積％の割合で添加する必要があり、このような固形分の高比率の添加はインキ逆流防止体の高粘度化を招き、インキ追従性に支障を来たすこととなる。
【０００６】
更に前記従来のインキ逆流防止体は、ボールペン製造工程においてインキ収容管に充填する際、インキ逆流防止体に付加される剪断力により増粘剤によって形成された三次元構造が破壊され易く、一旦破壊された三次元構造は回復しなかったり、回復に非常に長時間を要したり、又、回復した後は元の粘度より高粘度となる現象がみられ、このことはボールペンの筆記性能を著しく低下させる原因となる。
【０００７】
【課題を解決するための手段】
本発明は前記した如きボールペン用インキ逆流防止体の欠点を解消するものであって、即ち、経時における液体分離が発生せず、インキ追従性、耐衝撃性に優れ、更に経時においても剪断力を付加された場合においても粘度変化が少なく、筆記具に最適なインキ逆流防止体を提供するものである。
【０００８】
即ち、本発明はインキの消費に従い前進するインキ逆流防止体であって、前記インキ逆流防止体が難揮発性有機液体Ａ中にゲル状粒子及び／又は固体粒子が分散されてなること又は前記インキ逆流防止体が増粘剤の添加により増粘された難揮発性有機液体Ａ中にゲル状粒子及び／又は固体粒子が分散されてなることを要件とする。
また、前記難揮発性有機液体Ａがポリブテン、α−オレフィン、エチレン−α−オレフィンコオリゴマー及び精製鉱油から選ばれた一種又は二種以上であること、或いは前記難揮発性有機液体Ａがシリコーンオイルであること、前記ゲル状粒子及び／又は固体粒子が難揮発性有機液体Ｂにゲル化剤を添加したものであること、前記難揮発性有機液体Ｂがポリブテン、α−オレフィン、エチレン−α−オレフィンコオリゴマー及び精製鉱油から選ばれた一種又は二種以上であること、或いは前記難揮発性有機液体Ｂがシリコーンオイルであること、前記ゲル状粒子及び／又は固体粒子がインキ逆流防止体組成物全量に対して３０〜９０重量％を占めること、前記ゲル状粒子及び固体粒子が球形、ラグビーボール形状、板状または不定形或いはそれらの混合物であること等を要件とする。
【０００９】
更には、ペン体が直接或いは中継部材を介して取付けられたインキ収容筒内に直接収容した筆記具用インキの後端に、前記したいずれかのインキ逆流防止体組成物を配設した筆記具、及び前記ペン体がボールペンチップである筆記具等を要件とする。
【００１０】
本発明に用いられる難揮発性有機液体Ａは従来からインキ逆流防止体組成物に汎用されているものが適宜選択されるが、インキとの不混和性、耐熱安定性、インキの主溶剤の蒸発防止等の特性を備えた材料であるポリブテン、α−オレフィン、エチレン−α−オレフィンコオリゴマー、精製鉱油、シリコーンオイル等が好適に用いられる。
【００１１】
前記難揮発性有機液体Ａは単独でゲル状粒子及び／又は固体粒子の分散媒として使用することもできるが、増粘剤を添加することにより粘度を調整して使用してもよい。前記難揮発性有機液体Ａ単独で、或いは増粘剤を添加した状態で５×１０−４〜２×１０−２ｍ２・ｓ−１、好ましくは１×１０−３〜１×１０−２ｍ２・ｓ−１の範囲の動粘度を示すものが用いられる。
【００１２】
前記増粘剤としては従来からインキ逆流防止体組成物の増粘剤として一般的に使用されてきた増粘剤を用いることができ、例えばアルミニウム石鹸、リチウム石鹸等の金属石鹸、ジベンジリデンソルビトール等のベンジリデンソルビトール誘導体、アシル化アミノ酸、微粒子シリカ、珪酸アルミニウム、脂肪酸アマイド、脂肪酸デキストリン、ポリエチレンワックス、１２−ヒドロキシステアリン酸、ベントナイト、モンモリロナイト等の有機粘土、ヒマシ硬化油等を例示することができる。これら増粘剤は単独でも二種以上を混合してもよいが、添加量はそれぞれの増粘剤の増粘効果により適宜調整され、流動性が失われない範囲で添加されるが、難揮発性有機液体Ａ１００重量部に対して０．２〜１０重量部、好ましくは０．２〜５重量部の増粘剤が添加される。
前記増粘剤以外に、必要に応じて、低分子量ポリプロピレン、α−オレフィン樹脂、界面活性剤等を添加することもできる。
【００１３】
ここで難揮発性有機液体Ａ中に分散されるゲル状粒子及び固体粒子について述べる。前記ゲル状粒子及び固体粒子は難揮発性有機液体Ｂにゲル化剤を添加したものである。本明細書中の「ゲル」とはコロイド化学の分野で古くから用いられてきた用語であり「慣用的にいえば、流動性をもつ液状コロイドをゾル、形状を維持する固状コロイドをゲルという。」〔日本化学会編「コロイド科学１．”基礎および分散・吸着”」、１９９５年（初版）〕。即ち、容易に弾性変形するが、流動性をもたず、固体状であり、例えば豆腐、ゼリー、コンニャクに代表されるような性状を示すものである。
また、固体粒子は前記「ゲル」と同様に難揮発性有機液体Ｂにゲル化剤を添加したものであるが、「ゲル」よりも更にゲル化が進行し、外力を付加されても弾性変形をせず、流動性ももたない固体の性状を示すものである。
【００１４】
前記ゲル状粒子及び固体粒子は上述のように、難揮発性有機液体Ｂにゲル化剤を添加したものであり、前記難揮発性有機液体Ｂの具体例としてはポリブテン、α−オレフィン、エチレン−α−オレフィンコオリゴマー、精製鉱油、シリコーンオイル等が例示でき、前記ゲル化剤としては金属石鹸、ベンジリデンソルビトール誘導体、アシル化アミノ酸、微粒子シリカ、珪酸アルミニウム、脂肪酸アマイド、ポリエチレンワックス、ヒマシ硬化油等を挙げることができる。
【００１５】
前記ゲル化剤の添加量はそれぞれのゲル化剤のゲル化能に依存する。従って使用される難揮発性有機液体Ｂがゲル化、或いは固体化するために必要な量を配合するが、難揮発性有機液体Ｂ１００重量部に対して０．３〜２０重量部、好ましくは０．５〜１５重量部のゲル化剤が添加される。
【００１６】
本発明のインキ逆流防止体組成物は高粘度の、或いは増粘剤により増粘された難揮発性有機液体Ａ中にゲル状粒子及び／又は固体粒子が分散されてなることを特徴としており、筆記によりインキが消費される時のインキ追従性には液体部分が作用し、落下等の衝撃を受けた場合にはゲル状粒子及び／又は固体粒子が作用することによりインキ追従性と耐衝撃性の両方の特性を満足することができる。また、高比率に分散されたゲル状粒子及び／又は固体粒子によって形成された毛細管構造に高粘度の、或いは増粘剤により増粘された難揮発性有機液体Ａが保持される構造となるため、液体の分離がほとんど認められないという効果も有する。
【００１７】
尚、難揮発性有機液体Ａとしてポリブテン、α−オレフィン、エチレン−α−オレフィンコオリゴマー、精製鉱油等の石油系有機液体を選択した場合は、難揮発性有機液体Ｂも石油系有機液体から選択され、難揮発性有機液体Ａとしてシリコーンオイルを使用する場合は難揮発性有機液体Ｂもシリコーンオイルを使用することが望ましい。
【００１８】
【発明の実施の形態】
本発明のインキ逆流防止体組成物は単独の或いは増粘剤により増粘された難揮発性有機液体Ａ中に、難揮発性有機液体Ｂにゲル化剤を添加することにより調製されたゲル及び／又は固体を投入し、プロペラ式攪拌機等、比較的剪断力の低い攪拌機で混合することにより得ることができる。
やや弱い剪断力により前記ゲル及び／又は固体は粗い粒子に粉砕され、難揮発性有機液体Ａ中に分散された状態になる。前記粉砕された粒子の平均粒子径が２２０μｍ〜１ｍｍ程度の範囲にあることにより良好なインキ逆流防止体特性を示す。
【００１９】
【実施例】
以下、実施例及び比較例に基づき本発明の効果を具体的に説明するが、本発明はこれらの実施例に限定されるものではない。
〔実施例１〕
組成物１−Ａ
ポリブテン３ＳＨ〔日本油脂（株）製、分子量７２０〕 ９８重量部
疎水性シリカ ２重量部
〔日本アエロジル工業（株）製：商品名ＡＥＲＯＳＩＬ Ｒ９７２〕
以上の成分を混合、３本ロールで分散処理を行ない高粘稠液体を得た。
組成物１−Ｂ
ポリブテン０６ＳＨ〔日本油脂（株）製、分子量４３０〕 ９５重量部
アルミニウム石鹸 ５重量部
〔日本油脂（株）製、商品名：アルミニウムステアレート６００〕
以上の成分を混合、１５０℃で攪拌溶解した後冷却し、均一ゲルを得た。
組成物１−Ａ・３０重量部と組成物１−Ｂ・７０重量部を混合し、３枚羽根を備えたスリーワンモーターで１分間攪拌することにより、実施例１のインキ逆流防止体を得た。
【００２０】
〔実施例２〕
組成物２−Ａ
ポリブテン３ＳＨ〔日本油脂（株）製：分子量７２０〕
組成物２−Ｂ
ポリブテン１５ＳＨ〔日本油脂（株）製：分子量４３０〕
９５重量部
アルミニウム石鹸
５重量部
〔日本油脂（株）製：アルミニウムステアレート６００〕
以上の成分を混合、１５０℃で攪拌溶解した後冷却し、均一ゲルを得た。
組成物２−Ａ・２０重量部と組成物２−Ｂ・８０重量部を混合し、３枚羽根を備えたスリーワンモーターで１分間攪拌することにより、実施例２のインキ逆流防止体を得た。
【００２１】
〔実施例３〕
組成物３−Ａ
ポリブテン３ＳＨ〔日本油脂（株）製：分子量７２０〕 ９８重量部
疎水性シリカ ２重量部
〔日本アエロジル工業（株）製、商品名：ＡＥＲＯＳＩＬ Ｒ９７２〕
以上の成分を混合、３本ロールで分散処理を行ない高粘稠液体を得た。
組成物３−Ｂ
ポリブテン０６ＳＨ〔日本油脂（株）製：分子量４３０〕 ９５重量部
１２−ヒドロキシステアリン酸 ５重量部
以上の成分を混合、１００℃で攪拌溶解した後冷却し、均一固体を得た。
組成物３−Ａ・５０重量部と組成物３−Ｂ・５０重量部を混合し、３枚羽根を備えたスリーワンモーターで１分間攪拌することにより、実施例３のインキ逆流防止体を得た。
【００２２】
〔実施例４〕
組成物４−Ａ
エチレン−α−オレフィンコオリゴマー ９８重量部
〔三井石油科学（株）製、商品名：ルーカントＨＣ−１５０〕
疎水性シリカ ２重量部
〔日本アエロジル工業（株）製、商品名：ＡＥＲＯＳＩＬ Ｒ９７４〕
以上の成分を混合、３本ロールで分散処理を行ない高粘稠液体を得た。
組成物４−Ｂ
精製鉱油〔出光興産（株）製：ダイナフレシアＷ３８０〕 ９５重量部
アルミニウム石鹸 ５重量部
〔日本油脂（株）製：アルミニウムステアレート６００〕
以上の成分を混合、１５０℃で攪拌溶解した後冷却し、均一ゲルを得た。
組成物４−Ａ・２０重量部と組成物４−Ｂ・８０重量部を混合し、３枚羽根を備えたスリーワンモーターで１分間攪拌することにより、実施例４のインキ逆流防止体を得た。
【００２３】
〔実施例５〕
組成物５−Ａ
シリコーンオイル
〔信越シリコーン（株）製、商品名：シリコーンＫＦ９６ ６０００〕
組成物５−Ｂ
シリコーンオイル ９０重量部
〔信越シリコーン（株）製、商品名：シリコーンＫＦ９６ １０００〕
疎水性シリカ １０重量部
〔日本アエロジル工業（株）製、商品名：ＡＥＲＯＳＩＬ ８０５〕
以上の成分を混合、三本ロールで分散処理を行ない、均一ゲルを得た。
組成物５−Ａ・３０重量部と組成物５−Ｂ・７０重量部を混合し、３枚羽根を備えたスリーワンモーターで１分間攪拌することにより、実施例５のインキ逆流防止体を得た。
【００２４】
〔比較例１〕
ポリブテン１５ＳＨ〔日本油脂（株）製：分子量４３０〕 ９７重量部
アルミニウム石鹸 ３重量部
〔日本油脂（株）製、商品名：アルミニウムステアレート６００〕
以上の成分を混合、１５０℃で攪拌溶解した後冷却したものを比較例１のインキ逆流防止体とした。
【００２５】
〔比較例２〕
ポリブテン３ＳＨ〔日本油脂（株）製：分子量７２０〕 ９８重量部
アシル化アミノ酸〔味の素（株）製、商品名：ＧＰ−１〕 ２重量部
以上の成分を混合、１５０℃で攪拌溶解した後冷却したものを比較例２のインキ逆流防止体とした。
【００２６】
〔比較例３〕
ポリブテン３ＳＨ〔日本油脂（株）製：分子量７２０〕 ９８重量部
疎水性シリカ ２重量部
〔日本アエロジル工業（株）製、商品名：ＡＥＲＯＳＩＬ Ｒ９７２〕
以上の成分を混合、３本ロールで分散処理したものを比較例３のインキ逆流防止体とした。
【００２７】
〔比較例４〕
シリコーンオイル ９０重量部
〔信越シリコーン（株）製、商品名：シリコーンＫＦ９６ １０００〕
疎水性シリカ １０重量部
〔日本アエロジル工業（株）製、商品名：ＡＥＲＯＳＩＬ ８０５〕
以上の成分を混合、３本ロールで分散処理したものを比較例４のインキ逆流防止体とした。
【００２８】
〔比較例５〕
シリコーンオイル ９０重量部
〔信越シリコーン（株）製、商品名：シリコーンＫＦ９６ ６０００〕
疎水性シリカ １０重量部
〔日本アエロジル工業（株）製、商品名：ＡＥＲＯＳＩＬ Ｒ９７２〕
以上の成分を混合、３本ロールで分散処理したものを比較例５のインキ逆流防止体とした。
【００２９】
〔比較例６〕
組成物６−Ａ
ポリブテン３ＳＨ〔日本油脂（株）製：分子量７２０〕 ９８重量部
疎水性シリカ ２重量部
〔日本アエロジル工業（株）製、商品名：ＡＥＲＯＳＩＬ Ｒ９７４〕
以上の成分を混合、３本ロールで分散処理を行ない高粘稠液体を得た。
組成物６−Ｂ
ポリブテン０６ＳＨ〔日本油脂（株）製、分子量４３０〕 ９５重量部
アルミニウム石鹸 ５重量部
〔日本油脂（株）製、商品名：アルミニウムステアレート６００〕
以上の成分を混合、１５０℃で攪拌溶解した後冷却し、均一ゲルを得た。
組成物６−Ａ・３０重量部と組成物６−Ｂ・７０重量部を混合し、三本ロールで分散処理を行ない、比較例６のインキ逆流防止体を得た。尚、平均粒子径は２０μｍ未満であった。
【００３０】
先端にボ−ルを備えた内径３．８ｍｍのポリプロピレン製インキ収容管に、２０℃における粘度が１００ｍＰａ・ｓの水性インキを充填し、開放側インキ端面に実施例１乃至５及び比較例１乃至６のインキ逆流防止体を配設したものを試験用ボールペンとし、以下の性能比較試験を行なった。
（１）追従性試験
試験用ボールペンを筆記角度７０度、筆記荷重１００ｇの条件に設定した螺旋式筆記試験機を用いて、筆記速度４ｍ／分及び８ｍ／分で筆記し、筆跡の状態を目視で観察し、以下の基準で評価した。
○：良好
△：８ｍ／分で線飛び発生
×：４ｍ／分で線飛び発生
【００３１】
（２）壁面付着試験
試験用ボールペンを筆記角度７０度、筆記荷重１００ｇ、筆記速度４ｍ／分の条件に設定した螺旋式筆記試験機を用いて、インキを全て消費するまで筆記し、インキ逆流防止体がインキ収容管内壁に付着しているかどうかを目視で観察し、以下の基準で評価した。
○：良好
△：インキ収容管内壁にインキ逆流防止体が少量付着
×：付着量大でインキ後端に逆流防止体がほとんど残っていない
【００３２】
（３）液体分離試験
試験用ボールペンのチップ先端部をゴム栓体で気密にシールし、ペン先上向き（正立）状態で５０℃環境下に３０日間放置した後、インキ逆流防止体から液体成分が分離していないか目視で観察し、以下の基準で評価した。
○：良好（液体の分離が認められない）
△：少量の液体が分離しインキ中に侵入している
【００３３】
（４）耐衝撃性試験
試験用ボールペンのチップ先端部をゴム栓体で気密にシールし、ペン先上向き（正立）状態で３０ｃｍの高さから３０回落下した後、正立状態で２４時間放置し、目視でインキ逆流防止体の外観を観察し、以下の基準で評価した。
○：良好
△：インキ逆流防止体後端部の形状が変化している
×：インキ逆流防止体及び／又はインキがパイプ後端から流出
性能比較試験結果を以下の表にまとめた。
【００３４】
【表１】
【発明の効果】
本発明は液体分離が極めて少なく、インキの消費に従って、インキ収容管内壁に付着することなくスムースに追従し、又、落下等の衝撃に対しても形状破壊を発生しない優れたインキ逆流防止体組成物及びそれを内蔵した筆記具を提供するものである。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to an ink backflow preventive composition for a writing instrument and a writing instrument incorporating the same. More specifically, in a writing instrument comprising a writing tip and an ink storage tube that directly stores high-viscosity, medium-viscosity, or shear-thinning ink, the ink for the writing instrument that fills the open ink end surface of the ink storage tube. The present invention relates to a backflow prevention body composition and a writing instrument incorporating the ink backflow prevention body composition.
[0002]
[Prior art]
This type of ink backflow preventive composition for writing instruments is an ink backflow prevention performance that prevents ink from leaking out from the rear end of the ink containing tube when stored or transported in an upright (chip upward) or sideways state, Ink following performance that moves smoothly in the direction of the pen nib as ink decreases during writing, visible performance that prevents adhesion of ink and ink backflow prevention body to the ink container wall surface when following ink, and writing instrument body Impact resistance performance to prevent ink splattering and ink outflow when the ink is dropped is required.
[0003]
Conventionally, grease, which is a mixture of mineral oil and metal soap, has been applied as an ink backflow preventer for oil-based ballpoint pens using high-viscosity oil-based inks.
Also, when the oil ballpoint pen ink backflow preventive body is applied to a waterborne ballpoint pen using a water-based ink having medium viscosity or shear thinning viscosity, the backflow of the water-based ink is reduced due to poor follow-up to the ink and large changes in viscosity due to temperature changes. In order to cause problems such as inability to inhibit, a number of ink backflow preventers that have been made into highly viscous fluids by adding thickeners to volatile organic liquids such as liquid polybutene, mineral oil, and silicone oil have been proposed and widely put into practical use. ing.
[0004]
[Problems to be solved by the invention]
For example, Japanese Patent Application Laid-Open No. 2000-96033 discloses an ink backflow preventer in which hydrophobic silica and poly (oxyethylene / oxypropylene) polyol are added to silicone oil. When hydrophobic silica is used as a thickener, In addition, a phenomenon is observed in which the liquid component presumed to be a low molecular weight component of the silicone oil as the base oil gradually separates from the ink backflow preventive composition over time. A ballpoint pen to which such an ink backflow prevention body that separates liquid components in the composition is applied is left for a long period of time with the tip end portion facing upward (this state is displayed at a store). In this case, since the separated component has a specific gravity smaller than that of the ink, the separated component rises along the wall surface of the ink storage tube and accumulates at the tip portion of the ink storage tube, resulting in a decrease in handwriting density or poor writing.
[0005]
Japanese Patent Application Laid-Open No. 10-67196 discloses a base material composed of a hardly volatile fluid and / or a non-volatile fluid and an average particle size of 10 to 200 μm for the purpose of preventing the movement or ejection of the ink backflow preventive body due to impact. An ink backflow preventer containing particles is disclosed.
However, in order to obtain sufficient impact resistance in the ink backflow preventer having the above-described configuration, it is necessary to add the particles at a ratio of 20 to 60% by volume. This will cause the ink backflow preventive body to become highly viscous and hinder ink followability.
[0006]
Furthermore, the conventional ink backflow preventer is easily destroyed when the ink containing tube is filled in the ballpoint pen manufacturing process, and the three-dimensional structure formed by the thickener is easily broken by the shearing force applied to the ink backflow preventer. The three-dimensional structure was not recovered, it took a very long time to recover, and after recovery, the phenomenon of higher viscosity than the original viscosity was observed, which markedly improved the writing performance of the ballpoint pen. It causes a decrease.
[0007]
[Means for Solving the Problems]
The present invention eliminates the drawbacks of the ink pen backflow preventer for ballpoint pens as described above, i.e., no liquid separation occurs over time, excellent ink followability and impact resistance, and further shear force over time. Even when added, there is little change in viscosity, and an ink backflow prevention body optimal for a writing instrument is provided.
[0008]
That is, the present invention provides a ink follower moving forward in accordance with consumption of the ink, said ink follower is formed by gelling particles and / or solid particles are dispersed in a less volatile organic liquid body A or the ink follower gelled particles and / or solid particles in the flame volatile organic liquid body in a which is thickened to a requirement that is dispersed by the addition of the thickener.
Further, the flame-volatile organic liquid body A is polybutene, alpha-olefin, ethylene -α- that olefin copolymers is oligomeric and refined mineral oil from selected one or two or more, or the flame volatile organic liquid body A is it is silicone oil, the possible gelling particles and / or solid particles is obtained by adding a gelling agent to the low volatility organic liquid body B, the flame volatile organic liquid body B is polybutene, alpha-olefin, ethylene -α- olefin co-oligomer and it purified is selected one or two or more mineral oil, or said flame volatile organic liquid body B is a silicone oil, the gelling particles and / or solid particles ink It accounts for 30 to 90% by weight with respect to the total amount of the backflow preventer composition, and the gel particles and solid particles are spherical, rugby ball, plate or amorphous, or The a requirement such that a mixture of.
[0009]
Furthermore, a writing instrument in which any one of the ink backflow preventive compositions described above is disposed at the rear end of the writing instrument ink that is directly accommodated in an ink accommodating cylinder attached directly or via a relay member, and A writing instrument in which the pen body is a ballpoint pen tip is a requirement.
[0010]
Slightly volatile organic liquid body A for use in the present invention from the prior although those generally used in ink follower composition is appropriately selected, the immiscibility of ink, heat stability, the main solvent of the ink Polybutene, α-olefin, ethylene-α-olefin co-oligomer, refined mineral oil, silicone oil and the like, which are materials having properties such as evaporation prevention, are preferably used.
[0011]
The flame volatile organic liquid body A is alone can be used as a dispersion medium for the gel-like particles and / or solid particles, it may be used to adjust the viscosity by adding a thickener. The flame volatile organic liquid body A in alone, or thickeners while adding 5 × 10 -4 ~2 × 10 -2 m 2 · s -1, preferably 1 × 10 -3 ~1 × 10 Those exhibiting a kinematic viscosity in the range of −2 m 2 · s −1 are used.
[0012]
As the thickener, it is possible to use a thickener that has been generally used as a thickener for an ink backflow preventive composition, such as metal soaps such as aluminum soap and lithium soap, dibenzylidene sorbitol, etc. Examples thereof include benzylidene sorbitol derivatives, acylated amino acids, fine particle silica, aluminum silicate, fatty acid amide, fatty acid dextrin, polyethylene wax, 12-hydroxystearic acid, bentonite, montmorillonite and other organic clays, castor hardened oil, and the like. These thickeners may be used alone or in admixture of two or more, but the amount added is adjusted as appropriate according to the thickening effect of each thickener and is added within the range where fluidity is not lost. 0.2 to 10 parts by weight with respect to sex organic liquid body A1 00 parts by weight, preferably added thickener 0.2 to 5 parts by weight.
In addition to the thickener, a low molecular weight polypropylene, an α-olefin resin, a surfactant, and the like can be added as necessary.
[0013]
Here we describe gelling particles and solid particles dispersed in the low volatility organic liquid body A. The gel-like particles and solid particles is obtained by adding a gelling agent to the low volatility organic liquid body B. The term “gel” in this specification is a term that has been used for a long time in the field of colloid chemistry. “Regularly speaking, a liquid colloid with fluidity is called a sol, and a solid colloid that maintains its shape is called a gel. [Chemical Society of Japan “Colloidal Science 1. Basics and Dispersion / Adsorption”, 1995 (first edition)]. That is, it is easily elastically deformed, but does not have fluidity and is in a solid state, and exhibits properties such as tofu, jelly, and konjac.
Although the solid particles is obtained by adding a gelling agent to the likewise sparingly volatile organic liquid body B and the "gel", further gelation than the "gel" proceeds, it is added to the external force elastic It shows the properties of a solid that is not deformed and has no fluidity.
[0014]
As the gel-like particles and solid particles described above, is obtained by adding a gelling agent to the low volatility organic liquid body B, polybutene Specific examples of the flame volatile organic liquid body B, alpha-olefin, Examples include ethylene-α-olefin co-oligomers, refined mineral oils, silicone oils, etc., and examples of the gelling agent include metal soaps, benzylidene sorbitol derivatives, acylated amino acids, fine particle silica, aluminum silicate, fatty acid amide, polyethylene wax, castor oil. Etc.
[0015]
The added amount of the gelling agent depends on the gelling ability of each gelling agent. Therefore slightly volatile organic liquid body B is gelled to be used or will be incorporated an amount required to solidify, 0.3 to 20 parts by weight with respect to B1 00 parts by weight low volatility organic liquid body, Preferably, 0.5 to 15 parts by weight of a gelling agent is added.
[0016]
Ink follower composition of the present invention is characterized in that gel-like particles and / or solid particles dispersed in a high viscosity, or slightly volatile organic liquid body in A, which is thickened by a thickener When ink is consumed by writing, the liquid part acts on the ink following ability, and when it receives an impact such as dropping, the gel-like particles and / or solid particles act to cause ink following ability and impact resistance. Both characteristics can be satisfied. Further, a structure in which a high viscosity, or slightly volatile organic liquid body A which has been thickened by the thickener is kept to a capillary structure formed by the gel-like particles and / or solid particles dispersed in a high proportion Therefore, there is an effect that almost no liquid separation is observed.
[0017]
Incidentally, as a sparingly volatile organic liquid body A polybutene, alpha-olefin, ethylene -α- olefin co-oligomer, if you choose the petroleum organic liquid such as refined mineral oils are less volatile organic liquid body B also petroleum is selected from the organic liquid, when using the silicone oil as a hardly volatile organic liquid body a, it is desirable to use a sparingly volatile organic liquid body B also silicone oils.
[0018]
DETAILED DESCRIPTION OF THE INVENTION
Ink follower composition of the present invention alone or sparingly volatile organic liquid body in A, which is thickened by a thickener, were prepared by adding a gelling agent to the low volatility organic liquid body B The gel and / or solid can be charged and mixed with a stirrer having a relatively low shearing force such as a propeller stirrer.
The gel and / or solid is ground to a coarse particle, the state of being dispersed in a less volatile organic liquid body A by rather weak shearing forces. When the average particle diameter of the pulverized particles is in the range of about 220 μm to 1 mm, good ink backflow prevention property is exhibited.
[0019]
【Example】
Hereinafter, although the effect of the present invention will be specifically described based on Examples and Comparative Examples, the present invention is not limited to these Examples.
[Example 1]
Composition 1-A
Polybutene 3SH [manufactured by NOF Corporation, molecular weight 720] 98 parts by weight hydrophobic silica 2 parts by weight [manufactured by Nippon Aerosil Co., Ltd .: trade name AEROSIL R972]
The above components were mixed and subjected to dispersion treatment with three rolls to obtain a highly viscous liquid.
Composition 1-B
Polybutene 06SH [Nippon Yushi Co., Ltd., molecular weight 430] 95 parts by weight Aluminum soap 5 parts by weight [Nippon Yushi Co., Ltd., trade name: Aluminum stearate 600]
The above components were mixed, dissolved by stirring at 150 ° C., and then cooled to obtain a uniform gel.
30 parts by weight of composition 1-A and 70 parts by weight of composition 1-B were mixed and stirred for 1 minute with a three-one motor equipped with three blades to obtain an ink backflow preventive body of Example 1. .
[0020]
[Example 2]
Composition 2-A
Polybutene 3SH [manufactured by NOF Corporation: molecular weight 720]
Composition 2-B
Polybutene 15SH [manufactured by NOF Corporation: molecular weight 430]
95 parts by weight aluminum soap 5 parts by weight [manufactured by NOF Corporation: aluminum stearate 600]
The above components were mixed, dissolved by stirring at 150 ° C., and then cooled to obtain a uniform gel.
20 parts by weight of composition 2-A and 80 parts by weight of composition 2-B were mixed and stirred for 1 minute with a three-one motor equipped with three blades to obtain an ink backflow preventer of Example 2. .
[0021]
Example 3
Composition 3-A
Polybutene 3SH [manufactured by NOF Corporation: molecular weight 720] 98 parts by weight hydrophobic silica 2 parts by weight [manufactured by Nippon Aerosil Kogyo Co., Ltd., trade name: AEROSIL R972]
The above components were mixed and subjected to dispersion treatment with three rolls to obtain a highly viscous liquid.
Composition 3-B
Polybutene 06SH [manufactured by Nippon Oil & Fats Co., Ltd .: molecular weight 430] 95 parts by weight 12-hydroxystearic acid 5 parts by weight The above components were mixed, stirred and dissolved at 100 ° C., and then cooled to obtain a uniform solid.
50 parts by weight of composition 3-A and 50 parts by weight of composition 3-B were mixed and stirred for 1 minute with a three-one motor equipped with three blades to obtain an ink backflow preventer of Example 3. .
[0022]
Example 4
Composition 4-A
98 parts by weight of ethylene-α-olefin co-oligomer [Mitsui Oil Chemicals, Inc., trade name: Lucant HC-150]
Hydrophobic silica 2 parts by weight [manufactured by Nippon Aerosil Co., Ltd., trade name: AEROSIL R974]
The above components were mixed and subjected to dispersion treatment with three rolls to obtain a highly viscous liquid.
Composition 4-B
Refined mineral oil [Idemitsu Kosan Co., Ltd .: Dyna Fresia W380] 95 parts by weight Aluminum soap 5 parts by weight [Nippon Yushi Co., Ltd .: Aluminum stearate 600]
The above components were mixed, dissolved by stirring at 150 ° C., and then cooled to obtain a uniform gel.
Ink backflow preventive body of Example 4 was obtained by mixing 20 parts by weight of composition 4-A and 80 parts by weight of composition 4-B and stirring for 1 minute with a three-one motor equipped with three blades. .
[0023]
Example 5
Composition 5-A
Silicone oil [made by Shin-Etsu Silicone Co., Ltd., trade name: Silicone KF96 6000]
Composition 5-B
90 parts by weight of silicone oil [manufactured by Shin-Etsu Silicone Co., Ltd., trade name: Silicone KF96 1000]
Hydrophobic silica 10 parts by weight [manufactured by Nippon Aerosil Co., Ltd., trade name: AEROSIL 805]
The above components were mixed and subjected to dispersion treatment with three rolls to obtain a uniform gel.
30 parts by weight of composition 5-A and 70 parts by weight of composition 5-B were mixed and stirred for 1 minute with a three-one motor equipped with three blades to obtain an ink backflow preventer of Example 5. .
[0024]
[Comparative Example 1]
Polybutene 15SH [Nippon Yushi Co., Ltd .: molecular weight 430] 97 parts by weight Aluminum soap 3 parts by weight [Nippon Yushi Co., Ltd., trade name: Aluminum stearate 600]
The above components were mixed, stirred and dissolved at 150 ° C., and then cooled, and used as the ink backflow preventer of Comparative Example 1.
[0025]
[Comparative Example 2]
Polybutene 3SH [manufactured by NOF Corporation: molecular weight 720] 98 parts by weight acylated amino acid [manufactured by Ajinomoto Co., Inc., trade name: GP-1] 2 parts by weight The above components were mixed, stirred and dissolved at 150 ° C., and then cooled. This was used as the ink backflow preventer of Comparative Example 2.
[0026]
[Comparative Example 3]
Polybutene 3SH [manufactured by NOF Corporation: molecular weight 720] 98 parts by weight hydrophobic silica 2 parts by weight [manufactured by Nippon Aerosil Kogyo Co., Ltd., trade name: AEROSIL R972]
A mixture of the above components and subjected to a dispersion treatment with three rolls was used as the ink backflow preventer of Comparative Example 3.
[0027]
[Comparative Example 4]
90 parts by weight of silicone oil [manufactured by Shin-Etsu Silicone Co., Ltd., trade name: Silicone KF96 1000]
Hydrophobic silica 10 parts by weight [manufactured by Nippon Aerosil Co., Ltd., trade name: AEROSIL 805]
The above components were mixed and dispersed with a three roll, and the ink backflow preventer of Comparative Example 4 was used.
[0028]
[Comparative Example 5]
90 parts by weight of silicone oil [manufactured by Shin-Etsu Silicone Co., Ltd., trade name: Silicone KF96 6000]
Hydrophobic silica 10 parts by weight [manufactured by Nippon Aerosil Co., Ltd., trade name: AEROSIL R972]
The above components were mixed and subjected to a dispersion treatment with three rolls to obtain an ink backflow preventer of Comparative Example 5.
[0029]
[Comparative Example 6]
Composition 6-A
Polybutene 3SH [manufactured by NOF Corporation: molecular weight 720] 98 parts by weight hydrophobic silica 2 parts by weight [manufactured by Nippon Aerosil Kogyo Co., Ltd., trade name: AEROSIL R974]
The above components were mixed and subjected to dispersion treatment with three rolls to obtain a highly viscous liquid.
Composition 6-B
Polybutene 06SH [Nippon Yushi Co., Ltd., molecular weight 430] 95 parts by weight Aluminum soap 5 parts by weight [Nippon Yushi Co., Ltd., trade name: Aluminum stearate 600]
The above components were mixed, dissolved by stirring at 150 ° C., and then cooled to obtain a uniform gel.
30 parts by weight of composition 6-A and 70 parts by weight of composition 6-B were mixed and subjected to dispersion treatment with three rolls to obtain an ink backflow preventer of Comparative Example 6. The average particle size was less than 20 μm.
[0030]
A polypropylene ink containing tube having an inner diameter of 3.8 mm provided with a ball at the tip was filled with water-based ink having a viscosity of 100 mPa · s at 20 ° C., and Examples 1 to 5 and Comparative Examples 1 to A test ballpoint pen was provided with the ink backflow preventer 6 and the following performance comparison test was performed.
(1) Follow-up test Using a spiral writing tester with a test ballpoint pen set to a writing angle of 70 degrees and a writing load of 100 g, writing was performed at writing speeds of 4 m / min and 8 m / min, and the state of the handwriting was visually observed. And evaluated according to the following criteria.
○: Good △: Line jump occurs at 8m / min ×: Line jump occurs at 4m / min [0031]
(2) Wall adhesion test Using a spiral writing tester with a test ballpoint pen set to a writing angle of 70 degrees, a writing load of 100 g, and a writing speed of 4 m / min. Whether or not the body adhered to the inner wall of the ink containing tube was visually observed and evaluated according to the following criteria.
○: Good △: A small amount of ink backflow prevention body adheres to the inner wall of the ink storage tube ×: A large amount of adhesion and almost no backflow prevention body remains at the rear end of the ink [0032]
(3) Liquid separation test The tip of the tip of the test ballpoint pen is hermetically sealed with a rubber stopper, and left for 30 days in a 50 ° C environment with the pen tip facing up (upright). Were visually observed to determine whether they were separated, and evaluated according to the following criteria.
○: Good (no separation of liquid is observed)
Δ: A small amount of liquid is separated and penetrates into the ink.
(4) Impact resistance test The tip of the test ballpoint pen is hermetically sealed with a rubber plug and dropped 30 times from a height of 30 cm in a pen tip upward (upright) state, and then in an upright state for 24 hours. The appearance of the ink backflow preventer was visually observed and evaluated according to the following criteria.
○: Good Δ: The shape of the rear end portion of the ink backflow prevention body has changed. ×: The ink backflow prevention body and / or the ink flowed out from the rear end of the pipe. The performance comparison test results are summarized in the following table.
[0034]
[Table 1]
【The invention's effect】
The present invention has an excellent ink backflow prevention body composition that has very little liquid separation, follows the consumption of ink, smoothly follows without adhering to the inner wall of the ink containing tube, and does not cause shape breakage even when dropped or other impacts An object and a writing instrument incorporating the object are provided.
Claims (11)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001323607A JP3977625B2 (en) | 2001-10-22 | 2001-10-22 | Ink backflow preventive composition for writing instrument and writing instrument incorporating the same |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001323607A JP3977625B2 (en) | 2001-10-22 | 2001-10-22 | Ink backflow preventive composition for writing instrument and writing instrument incorporating the same |
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| Publication Number | Publication Date |
|---|---|
| JP2003127582A JP2003127582A (en) | 2003-05-08 |
| JP3977625B2 true JP3977625B2 (en) | 2007-09-19 |
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| JP2001323607A Expired - Lifetime JP3977625B2 (en) | 2001-10-22 | 2001-10-22 | Ink backflow preventive composition for writing instrument and writing instrument incorporating the same |
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| EP1632359B1 (en) | 2003-05-27 | 2009-09-09 | Sakura Color Products Corporation | Method of producing applicator tip |
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