JP4833438B2 - Ink for inkjet printer - Google Patents

Description

【００９２】
実施例１
１００ｍｌプラスチック製ポリビンに、
合成例１のシリコーン系グラフトポリマー １２．６部
顔料としてＦａｓｔｏｇｅｎ Ｂｌｕｅ ＴＧＲ
（大日本インキ化学工業社製の銅フタロシアニンブルー顔料） ５．７部
フタロシアニン顔料誘導体としてソルスパース５０００
（ゼネカ社製） ０．３部
メチルエチルケトン １１．４部
３００μｍφジルコニアビーズ １００部
を計り取り、ペイントシェーカー（エイシン社）で２時間分散し、その後、
メチルエチルケトン ３０．０部
を追加して分散スラリーを得た。
【００９３】
次に、環状メチルシロキサン溶媒ＫＦ９９５（信越化学社製）を５５部及び鎖状ジメチルシロキサン溶媒ＫＦ９６Ｌ−５ＣＳ（信越化学社製）３０部を秤取し、３００ｃｃナスフラスコに入れ、マグネチックスターラーで攪拌した。攪拌しながら、前記分散スラリー５０部をゆっくりと滴下し、顔料表面にシリコーン系グラフトポリマーを析出させた。
【００９４】
さらに、
合成例１のシリコーン系グラフトポリマー １０．５部
メチルエチルケトン ４．５部
を混合したポリマー溶液をゆっくりと滴下し、シリコーン系グラフトポリマーを有機溶媒中に自己分散させた。
【００９５】
滴下後、メチルエチルケトンを減圧蒸留にて脱溶媒し、顔料濃度５．１０％の分散液を得た。得られた分散液組成物は、分散粒径が０．２２０μｍ（コールター社製のレーザードップラー方式の粒度分布計Ｎ４ ＰＬＵＳで測定）、３３５００Ｇの遠心力を５時間かけ上澄みの吸光度（日本分光社製のＶ−５７０型紫外・可視分光光度計で測定）から樹脂吸着量を求めたところ、粒状物質１００部に対して１５７．１部のシリコーン系グラフトポリマーが吸着されていた。
【００９６】
さらに、環状メチルシロキサン溶媒ＫＦ９９５を２．０部加え全量１００部とし、口径１μｍのフィルターでろ過し、顔料濃度５％の油性インクジェットプリンター用インクとした。
【００９７】
このインクは、下記の表３に示すとおり、粒径が小さく、保存試験後の変化もなく沈降も見られなかった。また、印字物は耐擦過性、耐水性や耐光性に優れ、インクの引火点も高く安全性も高かった。さらに、印字安定性も非常に優れていた。
【００９８】
比較例１
市販の油性インクジェットプリンター用インク（セイコーインストゥルメント社製）を用いて、下記の表３に示す各種試験を行った結果、粒径が小さく、保存試験後の変化もなく沈降も見られなかった。しかし、印字物の耐擦過性は、印字後１週間経って指で擦ってインクが剥がれてしまうほど非常に悪かった。
【００９９】
比較例２
１００ｍｌプラスチック製ポリビンに、
合成例６のシリコーン系グラフトポリマー １３．０部
顔料としてＦａｓｔｏｇｅｎ Ｂｌｕｅ ＴＧＲ
（大日本インキ化学工業社製の銅フタロシアニンブルー顔料） ５．７部
フタロシアニン顔料誘導体としてソルスパース５０００
（ゼネカ社製） ０．３部
メチルエチルケトン １１．０部
３００μｍφジルコニアビーズ １００部
を計り取り、ペイントシェーカー（エイシン社）で２時間分散し、その後、
メチルエチルケトン ３０．０部
を追加して分散スラリーを得た。
【０１００】
次に、環状メチルシロキサン溶媒ＫＦ９９５（信越化学社製）を６０部及び鎖状ジメチルシロキサン溶媒ＫＦ９６Ｌ−５ＣＳ（信越化学社製）３０部を秤取し、３００ｃｃナスフラスコに入れ、マグネチックスターラーで攪拌した。攪拌しながら、前記分散スラリー５０部をゆっくりと滴下し、顔料表面にシリコーン系グラフトポリマーを析出させた。
【０１０１】
滴下後、メチルエチルケトンを減圧蒸留にて脱溶媒し、顔料濃度５．０８％の分散液を得た。得られた分散液組成物は、分散粒径が０．１９１μｍ（コールター社製のレーザードップラー方式の粒度分布計Ｎ４ ＰＬＵＳで測定）、３３５００Ｇの遠心力を５時間かけ上澄みの吸光度（日本分光社製のＶ−５７０型紫外・可視分光光度計で測定）から樹脂吸着量を求めたところ、粒状物質１００部に対して８６．２部のシリコーン系グラフトポリマーが吸着されていた。
【０１０２】
さらに、環状メチルシロキサン溶媒ＫＦ９９５を１．６部加え全量１００部とし、口径１μｍのフィルターでろ過し、顔料濃度５％の油性インクジェットプリンター用インクとした。
【０１０３】
このインクは、下記の表３に示すとおり、粒径が小さく、保存試験後の変化もなく沈降も見られなかった。しかし、印字物の耐擦過性は、印字後１週間経って指で擦ってインクが剥がれてしまうほど非常に悪かった。
【０１０４】
実施例２
１００ｍｌプラスチック製ポリビンに、
合成例２のシリコーン系グラフトポリマー １３．５部
顔料としてＦａｓｔｏｇｅｎ Ｂｌｕｅ ＴＧＲ
（大日本インキ化学工業社製の銅フタロシアニンブルー顔料） ５．７部
フタロシアニン顔料誘導体としてソルスパース５０００
（ゼネカ社製） ０．３部
メチルエチルケトン １０．５部
３００μｍφジルコニアビーズ １００部
を計り取り、ペイントシェーカー（エイシン社）で２時間分散し、その後、
メチルエチルケトン ３０．０部
を追加して分散スラリーを得た。
【０１０５】
次に、環状メチルシロキサン溶媒ＫＦ９９５（信越化学社製）を５５部及び鎖状ジメチルシロキサン溶媒ＫＦ９６Ｌ−５ＣＳ（信越化学社製）３０部を秤取し、３００ｃｃナスフラスコに入れ、マグネチックスターラーで攪拌した。攪拌しながら、前記分散スラリー５０部をゆっくりと滴下し、顔料表面にシリコーン系グラフトポリマーを析出させた。
【０１０６】
さらに、
合成例２のシリコーン系グラフトポリマー １１．２部
メチルエチルケトン ３．８部
を混合したポリマー溶液をゆっくりと滴下し、シリコーン系グラフトポリマーを有機溶媒中に自己分散させた。
【０１０７】
滴下後、メチルエチルケトンを減圧蒸留にて脱溶媒し、顔料濃度５．０３％の分散液を得た。得られた分散液組成物は、分散粒径が０．１８０μｍ（コールター社製のレーザードップラー方式の粒度分布計Ｎ４ ＰＬＵＳで測定）、３３５００Ｇの遠心力を５時間かけ上澄みの吸光度（日本分光社製のＶ−５７０型紫外・可視分光光度計で測定）から樹脂吸着量を求めたところ、粒状物質１００部に対して１６２．２部のシリコーン系グラフトポリマーが吸着されていた。
【０１０８】
さらに、環状メチルシロキサン溶媒ＫＦ９９５を０．６部加え全量１００部とし、口径１μｍのフィルターでろ過し、顔料濃度５％の油性インクジェットプリンター用インクとした。
【０１０９】
このインクは、下記の表３に示すとおり、粒径が小さく、保存試験後の変化もなく沈降も見られなかった。また、印字物は耐擦過性、耐水性や耐光性に優れ、インクの引火点も高く安全性も高かった。さらに、印字安定性も非常に優れていた。
【０１１０】
実施例３
１００ｍｌプラスチック製ポリビンに、
合成例３のシリコーン系グラフトポリマー １３．０部
顔料としてＦａｓｔｏｇｅｎ Ｂｌｕｅ ＴＧＲ
（大日本インキ化学工業社製の銅フタロシアニンブルー顔料） ５．７部
フタロシアニン顔料誘導体としてソルスパース５０００
（ゼネカ社製） ０．３部
メチルエチルケトン １１．０部
３００μｍφジルコニアビーズ １００部
を計り取り、ペイントシェーカー（エイシン社）で２時間分散し、その後、
メチルエチルケトン ３０．０部
を追加して分散スラリーを得た。
【０１１１】
次に、環状メチルシロキサン溶媒ＫＦ９９５（信越化学社製）を５５部及び鎖状ジメチルシロキサン溶媒ＫＦ９６Ｌ−５ＣＳ（信越化学社製）３０部を秤取し、３００ｃｃナスフラスコに入れ、マグネチックスターラーで攪拌した。攪拌しながら、前記分散スラリー５０部をゆっくりと滴下し、顔料表面にシリコーン系グラフトポリマーを析出させた。
【０１１２】
さらに、
合成例３のシリコーン系グラフトポリマー １０．８部
メチルエチルケトン ４．２部
を混合したポリマー溶液をゆっくりと滴下し、シリコーン系グラフトポリマーを有機溶媒中に自己分散させた。
【０１１３】
滴下後、メチルエチルケトンを減圧蒸留にて脱溶媒し、顔料濃度５．０５％の分散液を得た。得られた分散液組成物は、分散粒径が０．１４７μｍ（コールター社製のレーザードップラー方式の粒度分布計Ｎ４ ＰＬＵＳで測定）、３３５００Ｇの遠心力を５時間かけ上澄みの吸光度（日本分光社製のＶ−５７０型紫外・可視分光光度計で測定）から樹脂吸着量を求めたところ、粒状物質１００部に対して１６３．５部のシリコーン系グラフトポリマーが吸着されていた。
【０１１４】
さらに、環状メチルシロキサン溶媒ＫＦ９９５を１．０部加え全量１００部とし、口径１μｍのフィルターでろ過し、顔料濃度５％の油性インクジェットプリンター用インクとした。
【０１１５】
このインクは、下記の表３に示すとおり、粒径が小さく、保存試験後の変化もなく沈降も見られなかった。また、印字物は耐擦過性、耐水性や耐光性に優れ、インクの引火点も高く安全性も高かった。さらに、印字安定性も非常に優れていた。
【０１１６】
実施例４
１００ｍｌプラスチック製ポリビンに、
合成例３のシリコーン系グラフトポリマー １３．０部
顔料としてＭａｇｅｎｔａ ＲＴ−３５５Ｄ
（チバ・スペシャリティケミカル社製のキナクリドン顔料） ６．０部
メチルエチルケトン １１．０部
３００μｍφジルコニアビーズ １００部
を計り取り、ペイントシェーカー（エイシン社）で２時間分散し、その後、
メチルエチルケトン ３０．０部
を追加して分散スラリーを得た。
【０１１７】
次に、環状メチルシロキサン溶媒ＫＦ９９５（信越化学社製）を５５部及び鎖状ジメチルシロキサン溶媒ＫＦ９６Ｌ−５ＣＳ（信越化学社製）３０部を秤取し、３００ｃｃナスフラスコに入れ、マグネチックスターラーで攪拌した。攪拌しながら、前記分散スラリー５０部をゆっくりと滴下し、顔料表面にシリコーン系グラフトポリマーを析出させた。
【０１１８】
さらに、
合成例３のシリコーン系グラフトポリマー １０．８部
メチルエチルケトン ４．２部
を混合したポリマー溶液をゆっくりと滴下し、シリコーン系グラフトポリマーを有機溶媒中に自己分散させた。
【０１１９】
滴下後、メチルエチルケトンを減圧蒸留にて脱溶媒し、顔料濃度５．０１％の分散液を得た。得られた分散液組成物は、分散粒径が０．１６３μｍ（コールター社製のレーザードップラー方式の粒度分布計Ｎ４ ＰＬＵＳで測定）、３３５００Ｇの遠心力を５時間かけ上澄みの吸光度（日本分光社製のＶ−５７０型紫外・可視分光光度計で測定）から樹脂吸着量を求めたところ、粒状物質１００部に対して１６１．２部のシリコーン系グラフトポリマーが吸着されていた。
【０１２０】
さらに、環状メチルシロキサン溶媒ＫＦ９９５を０．２部加え全量１００部とし、口径１μｍのフィルターでろ過し、顔料濃度５％の油性インクジェットプリンター用インクとした。
【０１２１】
このインクは、下記の表３に示すとおり、粒径が小さく、保存試験後の変化もなく沈降も見られなかった。また、印字物は耐擦過性、耐水性や耐光性に優れ、インクの引火点も高く安全性も高かった。さらに、印字安定性も非常に優れていた。
【０１２２】
実施例５
１００ｍｌプラスチック製ポリビンに、
合成例３のシリコーン系グラフトポリマー １３．０部
顔料としてＹｅｌｌｏｗ Ｐ−ＨＧ
（クラリアント社製のベンズイミダゾロン顔料） ６．０部
メチルエチルケトン １１．０部
３００μｍφジルコニアビーズ １００部
を計り取り、ペイントシェーカー（エイシン社）で２時間分散し、その後、
メチルエチルケトン ３０．０部
を追加して分散スラリーを得た。
【０１２３】
次に、環状メチルシロキサン溶媒ＫＦ９９５（信越化学社製）を５５部及び鎖状ジメチルシロキサン溶媒ＫＦ９６Ｌ−５ＣＳ（信越化学社製）３０部を秤取し、３００ｃｃナスフラスコに入れ、マグネチックスターラーで攪拌した。攪拌しながら、前記分散スラリー５０部をゆっくりと滴下し、顔料表面にシリコーン系グラフトポリマーを析出させた。
【０１２４】
さらに、
合成例３のシリコーン系グラフトポリマー １０．８部
メチルエチルケトン ４．２部
を混合したポリマー溶液をゆっくりと滴下し、シリコーン系グラフトポリマーを有機溶媒中に自己分散させた。
【０１２５】
滴下後、メチルエチルケトンを減圧蒸留にて脱溶媒し、顔料濃度５．０２％の分散液を得た。得られた分散液組成物は、分散粒径が０．１９２μｍ（コールター社製のレーザードップラー方式の粒度分布計Ｎ４ ＰＬＵＳで測定）、３３５００Ｇの遠心力を５時間かけ上澄みの吸光度（日本分光社製のＶ−５７０型紫外・可視分光光度計で測定）から樹脂吸着量を求めたところ、粒状物質１００部に対して１６８．１部のシリコーン系グラフトポリマーが吸着されていた。
【０１２６】
さらに、環状メチルシロキサン溶媒ＫＦ９９５を０．４部加え全量１００部とし、口径１μｍのフィルターでろ過し、顔料濃度５％の油性インクジェットプリンター用インクとした。
【０１２７】
このインクは、下記の表３に示すとおり、粒径が小さく、保存試験後の変化もなく沈降も見られなかった。また、印字物は耐擦過性、耐水性や耐光性に優れ、インクの引火点も高く安全性も高かった。さらに、印字安定性も非常に優れていた。
【０１２８】
実施例６
１００ｍｌプラスチック製ポリビンに、
合成例３のシリコーン系グラフトポリマー １３．０部
顔料としてＰｒｉｎｔｅｘ ７０
（デグサ社製のカーボンブラック顔料） ５．９部
フタロシアニン顔料誘導体としてソルスパース５０００
（ゼネカ社製） ０．１部
メチルエチルケトン １１．０部
３００μｍφジルコニアビーズ １００部
を計り取り、ペイントシェーカー（エイシン社）で２時間分散し、その後、
メチルエチルケトン ３０．０部
を追加して分散スラリーを得た。
【０１２９】
次に、環状メチルシロキサン溶媒ＫＦ９９５（信越化学社製）を５５部及び鎖状ジメチルシロキサン溶媒ＫＦ９６Ｌ−５ＣＳ（信越化学社製）３０部を秤取し、３００ｃｃナスフラスコに入れ、マグネチックスターラーで攪拌した。攪拌しながら、前記分散スラリー５０部をゆっくりと滴下し、顔料表面にシリコーン系グラフトポリマーを析出させた。
【０１３０】
さらに、
合成例３のシリコーン系グラフトポリマー １０．８部メチルエチルケトン ４．２部を混合したポリマー溶液をゆっくりと滴下し、シリコーン系グラフトポリマーを有機溶媒中に自己分散させた。
【０１３１】
滴下後、メチルエチルケトンを減圧蒸留にて脱溶媒し、顔料濃度５．０２％の分散液を得た。得られた分散液組成物は、分散粒径が０．１９０μｍ（コールター社製のレーザードップラー方式の粒度分布計Ｎ４ ＰＬＵＳで測定）、３３５００Ｇの遠心力を５時間かけ上澄みの吸光度（日本分光社製のＶ−５７０型紫外・可視分光光度計で測定）から樹脂吸着量を求めたところ、粒状物質１００部に対して１６７．８部のシリコーン系グラフトポリマーが吸着されていた。
【０１３２】
さらに、環状メチルシロキサン溶媒ＫＦ９９５を０．４部加え全量１００部とし、口径１μｍのフィルターでろ過し、顔料濃度５％の油性インクジェットプリンター用インクとした。
【０１３３】
このインクは、下記の表３に示すとおり、粒径が小さく、保存試験後の変化もなく沈降も見られなかった。また、印字物は耐擦過性、耐水性や耐光性に優れ、インクの引火点も高く安全性も高かった。さらに、印字安定性も非常に優れていた。
【０１３４】
実施例７
１００ｍｌプラスチック製ポリビンに、
合成例３のシリコーン系グラフトポリマー １３．０部
顔料としてＦａｓｔｏｇｅｎ Ｂｌｕｅ ＴＧＲ
（大日本インキ化学工業社製の銅フタロシアニンブルー顔料） ５．７部
フタロシアニン顔料誘導体としてソルスパース５０００
（ゼネカ社製） ０．３部
メチルエチルケトン １１．０部
３００μｍφジルコニアビーズ １００部
を計り取り、ペイントシェーカー（エイシン社）で２時間分散し、その後、
メチルエチルケトン ３０．０部
を追加して分散スラリーを得た。
【０１３５】
次に、環状メチルシロキサン溶媒ＫＦ９９５（信越化学社製）を５５部及び鎖状ジメチルシロキサン溶媒ＫＦ９６Ｌ−５ＣＳ（信越化学社製）３０部を秤取し、３００ｃｃナスフラスコに入れ、マグネチックスターラーで攪拌した。攪拌しながら、前記分散スラリー５０部をゆっくりと滴下し、顔料表面にシリコーン系グラフトポリマーを析出させた。
【０１３６】
さらに、
合成例４のシリコーン系グラフトポリマー １０．２部
メチルエチルケトン ４．８部
を混合したポリマー溶液をゆっくりと滴下し、シリコーン系グラフトポリマーを有機溶媒中に自己分散させた。
【０１３７】
滴下後、メチルエチルケトンを減圧蒸留にて脱溶媒し、顔料濃度５．０７％の分散液を得た。得られた分散液組成物は、分散粒径が０．１８５μｍ（コールター社製のレーザードップラー方式の粒度分布計Ｎ４ ＰＬＵＳで測定）、３３５００Ｇの遠心力を５時間かけ上澄みの吸光度（日本分光社製のＶ−５７０型紫外・可視分光光度計で測定）から樹脂吸着量を求めたところ、粒状物質１００部に対して１６４．５部のシリコーン系グラフトポリマーが吸着されていた。
【０１３８】
さらに、環状メチルシロキサン溶媒ＫＦ９９５を１．４部加え全量１００部とし、口径１μｍのフィルターでろ過し、顔料濃度５％の油性インクジェットプリンター用インクとした。
【０１３９】
このインクは、下記の表３に示すとおり、粒径が小さく、保存試験後の変化もなく沈降も見られなかった。また、印字物は耐擦過性、耐水性や耐光性に優れ、インクの引火点も高く安全性も高かった。さらに、印字安定性も非常に優れていた。
【０１４０】
実施例８
１００ｍｌプラスチック製ポリビンに、
合成例３のシリコーン系グラフトポリマー １３．０部
顔料としてＦａｓｔｏｇｅｎ Ｂｌｕｅ ＴＧＲ
（大日本インキ化学工業社製の銅フタロシアニンブルー顔料） ５．７部
フタロシアニン顔料誘導体としてソルスパース５０００
（ゼネカ社製） ０．３部
メチルエチルケトン １１．０部
３００μｍφジルコニアビーズ １００部
を計り取り、ペイントシェーカー（エイシン社）で２時間分散し、その後、
メチルエチルケトン ３０．０部
を追加して分散スラリーを得た。
【０１４１】
次に、環状メチルシロキサン溶媒ＫＦ９９５（信越化学社製）を５５部及び鎖状ジメチルシロキサン溶媒ＫＦ９６Ｌ−５ＣＳ（信越化学社製）３０部を秤取し、３００ｃｃナスフラスコに入れ、マグネチックスターラーで攪拌した。攪拌しながら、前記分散スラリー５０部をゆっくりと滴下し、顔料表面にシリコーン系グラフトポリマーを析出させた。
【０１４２】
さらに、
合成例５のシリコーン系グラフトポリマー １０．９部
メチルエチルケトン ４．１部
を混合したポリマー溶液をゆっくりと滴下し、シリコーン系グラフトポリマーを有機溶媒中に自己分散させた。
【０１４３】
滴下後、メチルエチルケトンを減圧蒸留にて脱溶媒し、顔料濃度５．０１％の分散液を得た。得られた分散液組成物は、分散粒径が０．２０８μｍ（コールター社製のレーザードップラー方式の粒度分布計Ｎ４ ＰＬＵＳで測定）、３３５００Ｇの遠心力を５時間かけ上澄みの吸光度（日本分光社製のＶ−５７０型紫外・可視分光光度計で測定）から樹脂吸着量を求めたところ、粒状物質１００部に対して１６６．６部のシリコーン系グラフトポリマーが吸着されていた。
【０１４４】
さらに、環状メチルシロキサン溶媒ＫＦ９９５を０．２部加え全量１００部とし、口径１μｍのフィルターでろ過し、顔料濃度５％の油性インクジェットプリンター用インクとした。
【０１４５】
このインクは、下記の表３に示すとおり、粒径が小さく、保存試験後の変化もなく沈降も見られなかった。また、印字物は耐擦過性、耐水性や耐光性に優れ、インクの引火点も高く安全性も高かった。さらに、印字安定性も非常に優れていた。
【０１４６】
実施例９
１００ｍｌプラスチック製ポリビンに、
合成例３のシリコーン系グラフトポリマー １３．０部
顔料としてＦａｓｔｏｇｅｎ Ｂｌｕｅ ＴＧＲ
（大日本インキ化学工業社製の銅フタロシアニンブルー顔料） ５．７部
フタロシアニン顔料誘導体としてソルスパース５０００
（ゼネカ社製） ０．３部
メチルエチルケトン １１．０部
３００μｍφジルコニアビーズ １００部
を計り取り、ペイントシェーカー（エイシン社）で２時間分散し、その後、
メチルエチルケトン ３０．０部
を追加して分散スラリーを得た。
【０１４７】
次に、鎖状ジメチルシロキサン溶媒ＫＦ９６Ａ−２ＣＳ（信越化学社製）を５５部及び鎖状ジメチルシロキサン溶媒ＫＦ９６Ｌ−５ＣＳ（信越化学社製）３０部を秤取し、３００ｃｃナスフラスコに入れ、マグネチックスターラーで攪拌した。攪拌しながら、前記分散スラリー５０部をゆっくりと滴下し、顔料表面にシリコーン系グラフトポリマーを析出させた。
【０１４８】
さらに、
合成例３のシリコーン系グラフトポリマー １０．８部
メチルエチルケトン ４．２部
を混合したポリマー溶液をゆっくりと滴下し、シリコーン系グラフトポリマーを有機溶媒中に自己分散させた。
【０１４９】
滴下後、メチルエチルケトンを減圧蒸留にて脱溶媒し、顔料濃度５．３５％の分散液を得た。得られた分散液組成物は、分散粒径が０．１５６μｍ（コールター社製のレーザードップラー方式の粒度分布計Ｎ４ ＰＬＵＳで測定）、３３５００Ｇの遠心力を５時間かけ上澄みの吸光度（日本分光社製のＶ−５７０型紫外・可視分光光度計で測定）から樹脂吸着量を求めたところ、粒状物質１００部に対して１５８．２部のシリコーン系グラフトポリマーが吸着されていた。
【０１５０】
さらに、環状メチルシロキサン溶媒ＫＦ９６Ａ−２ＣＳを６．５部加え全量１００部とし、口径１μｍのフィルターでろ過し、顔料濃度５％の油性インクジェットプリンター用インクとした。
【０１５１】
このインクは、下記の表３に示すとおり、粒径が小さく、保存試験後の変化もなく沈降も見られなかった。また、印字物は耐擦過性、耐水性や耐光性に優れ、インクの引火点も高く安全性も高かった。さらに、印字安定性も非常に優れていた。
【０１５２】
前記実施例１〜実施例９及び比較例１〜比較例２で得られた分散液組成物の特性を下記の表２に要約して示す。
【０１５３】
【表２】
表２ 分散液組成物の特性

【０１５４】
前記実施例１〜実施例９及び比較例１〜比較例２で得られた油性インクジェットプリンター用インクの特性を下記の表３に要約して示す。なお、下記の表３において、「粒径」はコールター社製のレーザードップラー方式の粒度分布計Ｎ４ＰＬＵＳで測定した分散平均粒径(μｍ)を示す。「粘度」は東機産業社製Ｒ型粘度計で回転数１００ｒｐｍで測定した値（ｍＰａ・ｓ）である。「保存試験」は６０ｃｃガラス製容器にインクを４０ｇ計り取り密閉して、６０℃の恒温槽に２週間放置することにより実施した。「沈降物」の欄において、○は沈降物が認められなかった場合を示し、×は沈降物が認められた場合を示す。「耐擦過性」はバーコーターＮｏ．４を用いて、エプソン社製フォト光沢紙に展色することにより測定した。「耐擦過性」の欄において、○は展色３０秒後に指で強く擦ってもインクが剥がれなかった場合を示し、×は展色後数時間或いは数日経ってから指で擦るとインクが剥がれた場合を示す。「印字試験」はシャープ社製カラーファクシミリ用ＵＸ−ＩＫ４インクカートリッジに詰めてシャープ社製カラーファクシミリでＡ４用紙に印字することにより実施した。「印字安定性」は電子工業協会の印字パターンを連続印字することにより評価した。「印字安定性」の欄において、○は連続１０００枚以上安定して印字できた場合を示し、△はクリーニングを必要としたが連続１０００枚以上印字できた場合を示し、×は目詰まりを起こし印字できなくなった場合を示す。「耐水性」は印字物を水中に浸して、滲みが発生するか否かを目視で観察した。「耐水性」の欄において、○は全く滲まなかった場合を示し、×は少し滲んだ場合を示す。「安全性」の欄において、○は引火点が７０℃以上であることを示し、×は引火点が７０℃未満であることを示す。
【０１５５】
【表３】
表３ 油性インクジェットプリンター用インクの特性

【０１５６】
【発明の効果】
以上説明したように、本発明の油性インクジェットプリンター用インクは、印字物の耐擦過性を向上させるとともに、顔料と有機溶媒の利用により耐水性や耐光性とといった印字品質の向上もできた。また、顔料の沈降や保存安定性といった分散安定性を高める改良もなされた。さらに、安全性の高い高沸点のシリコーン系有機溶媒を使用することにより、インクの安全性も高めることができた。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to an ink for an ink jet printer in which a pigment is dispersed in an organic solvent. More specifically, the present invention relates to an ink for an ink jet printer having excellent scratch resistance and high dispersion stability.
[0002]
[Prior art]
Conventionally, in the ink field for inkjet printers in which a pigment is dispersed in an organic solvent, the pigment is dispersed using a dispersant, and various improvements in printing characteristics and storage stability have been made. For example, Japanese Patent Application Laid-Open Nos. 04-161467 and 04-248879 describe inks containing pigments, resins, and dispersants in silicone organic solvents, and exhibit excellent print quality by exhibiting quick drying. It has been shown to get.
[0003]
Japanese Patent Application Laid-Open No. 05-25417 discloses that an inkjet ink in which colored resin particles are dispersed in a nonpolar insulating organic solvent is free from bleeding on a recording paper and has excellent print drying properties, and is free from nozzle clogging. It is described as having excellent scratch resistance.
[0004]
However, ink for inkjet printers dispersed in a commercially available pigment-type organic solvent causes the ink to peel off when the printed matter comes into contact with or rubs against other things, and the print quality deteriorates. Not satisfied with sex.
[0005]
In addition, when the above-mentioned silicone-based organic solvent is used, there is no suitable dispersant for finely dispersing the pigment, and the dispersed particle diameter of the pigment is as large as 0.5 to 5 μm. Quality will deteriorate. Further, when colored resin particles are used, similarly, the colored resin particles are pulverized and dispersed, so that the dispersed particle size largely sinks and the print quality is deteriorated.
[0006]
Accordingly, an object of the present invention is to provide an ink for an ink jet printer in which a pigment is dispersed in an organic solvent, which has excellent scratch resistance and high dispersion stability.
[0007]
[Means for Solving the Problems]
The object is to use a silicone-based graft polymer having a glass transition temperature in a range of 0 ° C. to −50 ° C. as the silicone-based polymer in an ink for an inkjet printer including an organic solvent, a pigment, and a silicone-based polymer. Solved.
[0008]
According to the study by the present inventors, the ink resistance for ink jet printers can be improved by using a silicone-based graft polymer having a glass transition temperature in the range of 0 ° C. to −50 ° C. in the ink for ink jet printers. It was discovered that it can be improved. Furthermore, the silicone-based graft polymer is dispersed in an organic solvent in the form of particles having a size of 0.01 μm to 0.3 μm while adsorbed on the pigment surface. It has been discovered that the dispersion average particle size can be reduced, pigment settling can be prevented, and dispersion stability can be enhanced.
[0009]
DETAILED DESCRIPTION OF THE INVENTION
The ink for an ink jet printer of the present invention basically contains a pigment, an organic solvent, and a silicone-based graft polymer having a glass transition temperature in the range of 0 ° C. to −50 ° C. as essential components.
[0010]
When the glass transition temperature of the silicone-based graft polymer of the present invention is higher than 0 ° C., it is not preferable because the adhesiveness of the polymer is small, and it is difficult to fix the pigment on the recording medium. On the other hand, a glass transition temperature lower than −50 ° C. is not preferable because the polymer is too soft and the printed surface is easily damaged, resulting in problems such as reduced print quality. The glass transition temperature of the silicone-based graft polymer used in the ink for an ink jet printer of the present invention is in the range of −20 ° C. to −40 ° C. in consideration of the fixing property to the recording medium and the adhesion to the printer head. Is more preferable.
[0011]
The silicone-based graft polymer of the present invention is preferably adsorbed on the surface of pigment particles, and the polymer-adsorbed pigment is preferably dispersed in an organic solvent in the form of particles having a particle size in the range of 0.01 μm to 0.3 μm. . In particular, it is more preferable that the silicone-based graft polymer of the present invention is self-dispersed with a particle size in the range of 0.01 μm to 0.3 μm. A particularly preferred particle size is in the range of 0.015 μm to 0.1 μm.
[0012]
As used herein, the term “self-dispersing” means that the silicone-based graft polymer is not dissolved in an organic solvent, and only a silicone-based graft polymer is used without a protective colloid or surfactant that protects the special dispersion. Means that For example, there is a phenomenon in which, after the silicone-based graft polymer is dissolved in an organic solvent that dissolves the resin solution and the organic solvent that does not dissolve the silicone-based graft polymer is mixed, it does not form a large lump but is dispersed in a granular form. The particle size of the silicone-based graft polymer can be measured by a general known particle size distribution measuring device, for example, a laser type or light scattering type particle size distribution meter or a centrifugal sedimentation type particle size distribution meter.
[0013]
The particle diameter of the pigment to which the silicone-based graft polymer is adsorbed in the ink for an ink jet printer of the present invention is preferably 0.01 to 0.3 μm, more preferably 0.01 to 0.2 μm in consideration of a decrease in print quality. More preferred. Further preferable ranges are 0.01 to 0.1 μm, 0.05 to 0.25 μm, 0.1 to 0.3 μm, or 0.08 to 0.16 μm.
[0014]
The particle size distribution of the primary particle diameter of the pigment in the ink of the present invention is preferably in the range of 0.01 μm to 0.29 μm, and more preferably in the range of 0.01 μm to 0.2 μm from the point of precipitation of the pigment. The particle size distribution of the pigment is, for example, a method in which the crude pigment is dry-ground with a ball mill or the like together with a grinding medium such as a ball, a method in which the crude pigment is ground in a kneader with ethylene glycol and a salt, 0.01 μm by a method of wet pulverization with a pulverization medium, a method of precipitation after dissolving a crude pigment in a specific solvent (for example, a method of precipitation by dissolving water in sulfuric acid and then adding water or adding it in water), etc. It can be controlled within a range of ˜0.29 μm.
[0015]
The pigment adsorbed by the silicone-based graft polymer in the ink of the present invention preferably has a charge from the viewpoint of dispersion stability. For example, as the charge of the pigment, the absolute value of the ζ potential is preferably 10 to 300 mV, and more preferably 15 to 200 mV.
[0016]
  Can be used in the ink for inkjet printers of the present inventionExamples of the pigment include inorganic pigments and organic pigments.These pigments can be used alone or in combination of two or more.
[0017]
Examples of inorganic pigments include carbon black, titanium oxide, zinc white, zinc oxide, tripone, iron oxide, aluminum oxide, silicon dioxide, kaolinite, montmorillonite, talc, barium sulfate, calcium carbonate, silica, alumina, cadmium red, Bengala, molybdenum red, chrome vermilion, molybdate orange, yellow lead, chrome yellow, cadmium yellow, yellow iron oxide, titanium yellow, chromium oxide, pyridian, cobalt green, titanium cobalt green, cobalt chrome green, ultramarine blue, ultramarine blue , Bitumen, cobalt blue, cerulean blue, manganese violet, cobalt violet, mica and the like. Carbon black is particularly preferred.
[0018]
Examples of organic pigments include C.I. I. Quinacridone pigments such as CI Pigment Red 122, Red 202, Red 207, Red 209, and Violet 19; I. Quinacridone quinone pigments such as CI Pigment Orange 48 and Orange 49; I. Dioxazine pigments such as CI Pigment Violet 23 and Violet 37; I. Pigment Blue 15, Blue 15: 1, Blue 15: 2, Blue 15: 3, Blue 15: 4, Blue 15: 6, Blue 16, Blue 68, Green 7, Green 36, etc. Phthalocyanine pigments; I. Anthrapyrimidine pigments such as C.I. Pigment Yellow 108; I. Ansanthrone pigments such as CI Pigment Orange 77 and Red 168; I. Indanthrone pigments such as CI Pigment Blue 60; I. Flavanthrone pigments such as C.I. Pigment Yellow 24; I. Anthraquinone pigments such as CI Pigment Yellow 196 and Red 177; I. Perylene pigments such as CI Pigment Red 123, Red 149, Red 178, Red 179, Red 190, and Red 224; I. Perinone pigments such as CI Pigment Yellow 196 and Orange 43; I. Quinophthalone pigments such as CI Pigment Yellow 138; I. Diketopyrrolopyrrole pigments such as CI Pigment Orange 71, Orange 73, Red 254, Red 255, Red 264, and Red 272; I. Thioindigo pigments such as CI Pigment Red 88, Red 181 and Brown 27; I. CI indoline pigments such as CI Pigment Yellow 139, Yellow 185, Orange 69, and Red 260; I. CI indolinone pigments such as CI Pigment Yellow 109, Yellow 110 and Yellow 173; I. Azomethine pigments such as CI Pigment Yellow 101, Yellow 129, Orange 65; I. Benzimidazolone pigments such as CI Pigment Yellow 151, Yellow 154, Yellow 175, Yellow 180, Yellow 181, Yellow 181, Orange 36, Red 175, Red 176, and Red 185; I. Pigment yellow 1, yellow 65, yellow 73, yellow 74, yellow 116, red 3, red 48: 1, red 48: 2, red 48: 3, red 53: 1, red C. 57: 1, monoazo pigments such as Red 115; I. Disazo pigments such as CI Pigment Yellow 12, Yellow 13, Yellow 17, Yellow 81, Yellow 81, Yellow 83, Orange 16; I. Examples thereof include condensed azo pigments such as CI Pigment Yellow 93, Yellow 95, Yellow 128, Red 144, Red 144, Red 166, Red 220, and Red 221. The pigment may be a powdery, granular, or massive dry pigment, or a wet cake or slurry.
[0020]
In the ink for an ink jet printer of the present invention, it is particularly preferable to use at least one pigment selected from the group consisting of an organic pigment and carbon black as the pigment.
[0021]
In the ink for an ink jet printer of the present invention, the amount of the silicone-based graft polymer with respect to the pigment is preferably in the range of 5 to 3000 parts by weight of the silicone-based graft polymer with respect to 100 parts by weight of the pigment. Furthermore, it is more preferable that the amount of the silicone graft polymer adsorbed on the pigment is in the range of 20 to 1000 parts by weight of the silicone graft polymer with respect to 100 parts by weight of the pigment. If the amount of the silicone-based graft polymer is 5 parts by weight or more, the dispersion stability is good, and if it is 3000 parts by weight or less, the content of the pigment in the dispersion composition does not decrease. Sufficient pigment concentration can be obtained. In the ink for an ink jet printer of the present invention, a more preferable range of the amount of the silicone-based graft polymer relative to the pigment is in the range of 30 to 1000 parts by weight with respect to 100 parts by weight of the pigment.
[0022]
Although the exact mechanism of adsorption of the silicone-based graft polymer to the pigment is not clear, chemical bonding (for example, introduction of the basic site of the pigment surface and the acidic site of the silicone-based graft polymer by the electron mechanism, or the pigment surface) Acid-base bonds such as carboxyl groups introduced into silicone-based graft polymers and ionic bonds formed by salt formation of divalent or higher metal ions and silicone-based graft polymers, active groups on the pigment surface A covalent bond that polymerizes to a group), physical adsorption (for example, adsorption by cohesive force in which a silicone-based graft polymer becomes insoluble in a solvent and aggregates, mechanical adsorption in which a pigment and a silicone-based graft polymer are dispersed by a disperser), or Physicochemical adsorption (for example, dispersing silicone-based graft polymer and pigment, pigment The silicone graft polymer is adsorbed on the pigment surface by adsorbing the silicone graft polymer to the surface while reacting the active group on the pigment surface with the silicone graft polymer or by appropriately combining them. It seems to be.
[0023]
The method for measuring the amount of the silicone-based graft polymer adsorbed on the pigment is determined by a known and generally used method. For example, after adjusting the non-volatile content concentration in the ink to 5%, the ink is centrifuged until the supernatant becomes transparent, and the concentration can be measured indirectly by measuring the silicone graft polymer concentration in the supernatant.
[0024]
As an organic solvent that can be used in the ink for an ink jet printer of the present invention, the polarity is small, 10⁹Those having an electrical resistivity of Ω · cm or more are preferred. The upper limit of electrical resistivity is generally 10¹⁸It is about Ω · cm. Suitable organic solvents for such purposes include, for example, aliphatic hydrocarbon solvents such as hexane and mineral spirits; silicone organic solvents such as dialkylpolysiloxanes and cyclic polydialkylsiloxanes; olive oil, safflower oil, sunflower Vegetable oils such as oil, soybean oil and linseed oil; aromatic hydrocarbon solvents such as benzene, toluene and xylene; ester solvents such as butyl acetate; alcohol solvents such as methanol and butanol; methyl ethyl ketone and isobutyl Examples thereof include ketone solvents such as methyl ketone; aprotic polar solvents such as dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone and pyridine. These solvents can be used alone or in admixture of two or more. Among these solvents, considering the influence on the human body, silicone-based organic solvents are preferable, and methylpolysiloxane and cyclic methylpolysiloxane are more preferable. In view of safety such as ignition, a silicone-based organic solvent having a boiling point of 200 ° C. or higher is preferable.
[0025]
The ratio of the organic solvent in the ink for an ink jet printer of the present invention is preferably in the range of 50 to 10,000 parts by weight, more preferably in the range of 100 to 3000 parts by weight with respect to 100 parts by weight of the pigment. When the organic solvent is less than 50 parts by weight with respect to 100 parts by weight of the pigment, it is not preferable because the viscosity becomes too high and printing becomes impossible. On the other hand, when the organic solvent is more than 10,000 parts by weight with respect to 100 parts by weight of the pigment, it is not preferable because problems such as the color of the printed matter becoming too light occur.
[0026]
The silicone-based graft polymer preferably has a polar group for finely dispersing the pigment and improving the dispersion stability of the pigment. The polar group suitable for such purpose is not particularly limited, and examples thereof include a basic group, an acidic group, a hydroxyl group, etc. In particular, when the pigment is finely dispersed, and when the crosslinking reaction is performed, Hydroxyl groups are preferred. The basic group is not particularly limited, and examples thereof include primary, secondary, tertiary, and quaternary amino groups. Examples of the acidic group include, but are not limited to, a carboxyl group, a sulfonic acid group, a phosphonic acid group, and the like, but the acid strength is particularly weak because the dispersion composition hardly causes aggregation and the reaction rate of the crosslinking reaction. A carboxyl group is more preferred.
[0027]
The acid value of the silicone-based graft polymer is preferably in the range of 5 to 100 KOHmg / g. When the acid value is 5 KOHmg / g or more, the affinity with the pigment is increased, whereby a fine ink for an ink jet printer can be obtained, and the dispersion stability is improved. Moreover, if 100 KOHmg / g is made below, it will suppress that the acid strength of a silicone type graft polymer becomes strong, will make self-dispersion easy to occur, will prevent gelatinization at the time of a synthesis | combination, and will make it easy to synthesize | combine.
[0028]
The hydroxyl value of the silicone-based graft polymer is preferably in the range of 5 to 100 KOHmg / g. When the hydroxyl value is 5 KOHmg / g or more, the affinity with the pigment is increased, a fine ink for an ink jet printer can be obtained, and the dispersion stability is improved. Moreover, if it is set to 100 KOHmg / g or less, it will suppress that the acid strength of a silicone type graft polymer becomes strong, will make self-dispersion easy to occur, will prevent the gelatinization at the time of a synthesis | combination, and will make it easy to synthesize | combine.
[0029]
The amine value of the silicone-based graft polymer is preferably in the range of 5 to 100 KOHmg / g. When the amine value is 5 KOHmg / g or more, the affinity with the pigment is increased, and a fine ink for an ink jet printer can be obtained, whereby the dispersion stability is improved. Moreover, if it is set to 100 KOHmg / g or less, it will suppress that the acid strength of a silicone type graft polymer becomes strong, will make self-dispersion easy to occur, will prevent gelatinization at the time of a synthesis | combination, and will make it easy to synthesize | combine.
[0030]
The number average molecular weight of the silicone-based graft polymer is preferably in the range of 2000 to 50000. If the number average molecular weight is 2000 or more, the pigment can be finely dispersed and the precipitation of the pigment can be prevented. Further, if the molecular weight is 50000 or less, it can be easily dissolved in a solvent, and the viscosity of the ink for an ink jet printer can be suppressed from becoming too high. A more preferable range is 3000 to 30000.
[0031]
Examples of the silicone graft polymer include acrylic, polyester, polyurethane, epoxy, and amino polymer compounds. These polymer compounds can be used alone or in combination of two or more. Among these types, acrylic polymer compounds are more preferable because of ease of synthesis and grafting and ease of introduction of polar groups.
[0032]
In view of ease of self-dispersion in an organic solvent, a grafted acrylic polymer compound is particularly preferred. This facilitates self-dispersion by branching the part adsorbing to the pigment and the part having affinity for the organic solvent on the branch. That is, since the terminal ends of the graft trunks are not solvated, self-dispersion is facilitated.
[0033]
The grafted acrylic polymer compound preferably has a graft part molecular weight in the range of 500 to 10,000, more preferably 1000 to 8,000. As the graft part, silicone is preferable because of its good affinity for the solvent.
[0034]
Examples of the method for producing a silicone-based graft polymer include those obtained by reacting a monomer having a polar group, a macromonomer, and a monomer having silicone in a non-reactive solvent in the presence or absence of a catalyst, Among these, those obtained by polymerizing a monomer having a polar group and a silicone-based macromonomer as essential components are preferable. Also preferred is a method in which an acrylic polymer having a reactive group is synthesized and then reacted with a reactive silicone and grafted. The silicone-based graft polymer is preferably not polymerized even when polymerized, but is preferably dissolved or dispersed in a fine state, and those having a particle size of 0.01 μm to 0.3 μm are particularly preferable.
[0035]
Among the polar group-containing acrylic monomers used in the present invention, preferred monomers having an acidic group as a polar group include acrylic acid, methacrylic acid, crotonic acid, ethacrylic acid, propylacrylic acid, isopropylacrylic acid, and itaconic acid. , Monomers having a carboxyl group such as fumaric acid, acroyloxyethyl phthalate, acroyloxy succinate, sulfonic acid groups such as 2-ethyl acrylate, 2-methacrylate 2-ethyl acrylate, butyl acrylamide sulfonate, etc. Monomers having a phosphonic acid group such as 2-methacrylic acid 2-ethyl phosphonate, acrylic acid 2-ethyl phosphonate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, hydroxypropyl acrylate, Monomers mentioned with such hydroxyl Le hydroxypropyl, and more preferably monomers having inter alia carboxyl group or a hydroxyl group.
[0036]
Monomers having a basic group include monomers having a primary amino group such as acrylic amide, aminoethyl acrylate, aminopropyl acrylate, methacrylic acid amide, aminoethyl methacrylate, aminopropyl methacrylate, acrylic Methylaminoethyl acrylate, methylaminopropyl acrylate, ethylaminoethyl acrylate, ethylaminopropyl acrylate, methylaminoethyl methacrylate, methylaminopropyl methacrylate, ethylaminoethyl methacrylate, ethylaminopropyl methacrylate, etc. Monomers having secondary amino groups, dimethylaminoethyl acrylate, diethylaminoethyl acrylate, dimethylaminopropyl acrylate, diethylaminopropyl acrylate, dimethyl methacrylate Monomers having tertiary amino groups such as noethyl, diethylaminoethyl methacrylate, dimethylaminopropyl methacrylate, diethylaminopropyl methacrylate, dimethylaminoethyl methyl chloride salt, dimethylaminoethyl methyl methacrylate salt, acrylic acid Monomers having a quaternary amino group such as dimethylaminoethylbenzyl chloride salt and dimethylaminoethylbenzyl chloride methacrylate are preferred.
[0037]
The silicone-based macromonomer that introduces the graft part is a polyether-based polyester that adds a siloxane oxide to a hydroxyalkylene monomethacrylate using a cationic catalyst, and a polyester containing a polybasic acid and a hydroxyl group-containing silicone, and then glycidyl methacrylate and ester Particularly preferred are esterified ester-based materials and water glass in which the starting material is subjected to methoxylation followed by introduction of methacrylate at the terminal.
[0038]
As the silicone-based macromonomer, a macromer in which dimethylsiloxane is bonded to a methacryloyl group directly or via an alkyl group is particularly preferable. For example, X-22-174DX (manufactured by Shin-Etsu Chemical Co., Ltd.), AK-5, AK-30, And AK-32 (manufactured by Toagosei Co., Ltd.).
[0039]
Other preferred monomers that can be polymerized include methyl acrylate, ethyl acrylate, isopropyl acrylate, acrylate-n-propyl, acrylate-n-butyl, acrylate-t-butyl, benzyl acrylate, methyl methacrylate. , Ethyl methacrylate, isopropyl methacrylate, methacrylate-n-propyl, methacrylate-n-butyl, isobutyl methacrylate, tert-butyl methacrylate, tridecyl methacrylate, benzyl methacrylate, 2-ethylhexyl acrylate, methacrylic acid 2-ethylhexyl, octyl acrylate, octyl methacrylate, lauryl acrylate, lauryl methacrylate, cetyl acrylate, cetyl methacrylate, stearyl acrylate, stearyl methacrylate, behenyl acrylate, behe (Meth) acrylic acid esters such as methyl methacrylate; styrene monomers such as styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, p-tert-butylstyrene; benzyl itaconate Itaconic acid esters such as dimethyl maleate, etc .; Fumarate esters such as dimethyl fumarate; Acrylonitrile, methacrylonitrile, vinyl acetate; 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, Hydroxyl group-containing monomers such as hydroxypropyl acrylate and hydroxypropyl methacrylate; aminoethyl acrylate, aminopropyl acrylate, methacrylamide, aminoethyl methacrylate, aminopropyl methacrylate And amino group-containing monomers such as dimethylaminoethyl acrylate and dimethylaminoethyl methacrylate; and α-olefins such as ethylene.
[0040]
Catalysts include peroxides such as t-butyl peroxybenzoate, di-t-butyl peroxide, cumene perhydroxide, acetyl peroxide, benzoyl peroxide, lauroyl peroxide; azobisisobutylnitrile, azobis-2 An azo compound such as 1,4-dimethylvaleronitrile, azobiscyclohexanecarbonitrile or the like is preferable.
[0041]
Non-reactive solvents include aliphatic hydrocarbon solvents such as hexane and mineral spirits; aromatic hydrocarbon solvents such as benzene, toluene and xylene; ester solvents such as butyl acetate; methanol and butanol Alcohol solvents such as: ketone solvents such as methyl ethyl ketone and isobutyl methyl ketone; aprotic polar solvents such as dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone and pyridine are preferable. These solvents may be used in combination.
[0042]
The reaction method is preferably a known general method such as bulk polymerization, solution polymerization, suspension polymerization, emulsion polymerization, redox polymerization, etc. Among them, solution polymerization is more preferable because the reaction method is simple.
[0043]
The reaction conditions vary depending on the polymerization initiator and the solvent, but the reaction temperature is 180 ° C. or lower, preferably 30 to 150 ° C., and the reaction time is 30 minutes to 40 hours, preferably 2 hours to 30 hours.
[0044]
As described above, the present invention adsorbs a silicone-based graft polymer to a pigment, stabilizes the dispersion of the pigment, and prevents sedimentation. From the viewpoint of dispersion stability in various solvents, the silicone-based graft polymer is used. If the graft polymer is crosslinked and adsorbed on the particulate material, the dispersion stability can be further improved.
[0045]
The cross-linking method is preferably an ester bond, an amino bond, a urethane bond, an ether bond or a C—C bond by radical reaction, and an ester bond is particularly preferable from the viewpoint of reaction rate, reaction time, stability during dispersion of particulate matter, and the like. .
[0046]
As a method of crosslinking the self-dispersing silicone-based graft polymer, a method using a crosslinking agent and a method of introducing a functional group for crosslinking into the polymer compound to be self-dispersed are preferable.
[0047]
As the cross-linking agent, those which react with polar groups in the silicone-based graft polymer are preferable. Amino resins such as melamine resin, benzoguanamine resin and urea resin, tolylene diisocyanate-based prepolymer, polyfunctional aromatic polyisocyanate, diphenylmethane Isocyanate, hexamethylene diisocyanate prepolymer, isocyanate resin such as xylylene isocyanate prepolymer and lysine isocyanate prepolymer, epoxy resin such as bisphenol A and acrylic resin having glycidyl group, Ti, Al, Zr Chelate compounds such as Of these, amino resins and epoxy resins are particularly preferred from the viewpoints of reaction rate and reaction temperature. Since the acrylic polymer compound has only one type of functional group, a crosslinking agent may be required.
[0048]
The crosslinking functional group introduced into the silicone-based graft polymer is preferably an amino group, a hydroxyl group, a methoxy group, or a glycidyl group. Among these, a hydroxyl group and a glycidyl group are particularly preferable from the viewpoint of reaction rate and reaction temperature.
[0049]
As a method of introducing a functional group for crosslinking, a method of polymerizing or condensing using a monomer having a functional group for crosslinking, a polyhydric alcohol, hydroxyamine, polyamine, or the like at the time of synthesis of a polymer compound having an acidic group, A method of synthesizing a prepolymer of a polymer compound having a group and then introducing a crosslinking functional group by polymerization, condensation or addition reaction is preferred. Needless to say, the polymer compound self-disperses after the introduction of the functional group for crosslinking.
[0050]
Monomers having a functional group for crosslinking used in the synthesis of the silicone-based graft polymer include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, glycerol monomethacrylate, polyethylene glycol mono Hydroxyl-containing monomers such as methacrylate, propylene glycol monomethacrylate, polyethylene glycol monoacrylate, propylene glycol monoacrylate; glycidyl group-containing monomers such as glycidyl acrylate and glycidyl methacrylate; methoxy group containing methoxypolyethylene glycol acrylate and methoxypolyethylene glycol methacrylate Ami such as monomer, acrylamide, methacrylamide, etc. Is preferably a group containing monomer, among others glycidyl group-containing monomer is caused to react after hydroxyl group, and more preferable because of improving the charge of particulate material.
[0051]
  In the method of synthesizing a prepolymer of a silicone-based graft polymer and then introducing a functional group for crosslinking by polymerization, condensation or addition reaction, a compound having a functional group for crosslinking for introduction by polymerization, condensation or addition reaction Need only have two or more reactive groups, and polyhydric alcohols, polyamines, hydroxyamines, bisphenol A, and polyisocyanates are preferred. As a method for controlling the glass transition temperature of the silicone-based graft polymer in the range of 0 ° C. to −50 ° C., the composition ratio of monomers having a known glass transition temperature and the glass transition temperature are expressed by the following formula (1). By using and controlling, the silicone type graft polymer which has the target glass transition temperature can be obtained.
    1 / Tg = (w₁/ Tg₁+w ₂ / Tg ₂ + ... + w_n/ Tg_n(1)
(In the above formula, Tg₁~ Tg_nIs the glass transition temperature of each monomer(K)And w₁~ W_nIs the mass fraction of each monomer.K means Kelvin temperature scale.)
[0052]
In the ink for an ink jet printer of the present invention, in addition to the basic essential components of the pigment, the organic solvent, and the silicone-based graft polymer, a surfactant may be contained as necessary.
[0053]
The surfactant is used for improving the surface tension of the ink and the wettability of the pigment, preventing drying at the head, and preventing bleeding on the paper. Examples of the surfactant used in the inkjet printer ink of the present invention include an anionic surfactant, a cationic surfactant, a nonionic surfactant, and an amphoteric surfactant. Among these, particularly preferred surfactants are anionic surfactants and nonionic surfactants.
[0054]
Examples of the anionic surfactant include fatty acid salts such as sodium stearate soap, potassium oleate soap and semi-cured beef tallow fatty acid sodium soap, alkyl sulfates such as sodium lauryl sulfate, triethanolamine lauryl sulfate and sodium higher alcohol sulfate, Alkyl benzene sulfonates such as sodium dodecylbenzene sulfonate, alkyl naphthalene sulfonates such as sodium alkyl naphthalene sulfonate, alkyl sulfosuccinates such as sodium dialkyl sulfosuccinate, alkyl diphenyl ether disulfonates such as sodium alkyl diphenyl ether disulfonate, Alkyl phosphates such as potassium alkyl phosphate, sodium polyoxyethylene lauryl ether sulfate and polyoxyethylene alkyl sulfate trie Polyoxyethylene alkyl sulfate ester salts such Noruamin, alkyl aryl sulfates such as polyoxyethylene alkyl phenyl ether sodium sulfate, polyoxyethylene alkyl phosphate, naphthalene sulfonic acid formalin condensates preferred.
[0055]
Examples of cationic surfactants include alkylamine salts such as coconut amine acetate and stearylamine acetate, quaternary ammonium salts such as lauryltrimethylammonium chloride, stearyltrimethylammonium chloride and alkylbenzyldimethylammonium chloride, laurylbetaine and stearylbetaine. Amine oxides such as alkylbetaines such as lauryldimethylamine oxide are preferred.
[0056]
Nonionic surfactants include polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene alkyl ethers such as polyoxyethylene oleyl ether and polyoxyethylene higher alcohol ether, polyoxyethylene octyl Polyoxyethylene alkyl allyl ethers such as phenyl ether and polyoxyethylene nonylphenyl ether, polyoxyethylene derivatives, oxyethylene / oxypropylene block copolymers, sorbitan fatty acid esters, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate , Polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan tristearate Non-ionic surfactants such as polyoxyethylene sorbitan fatty acid esters such as polyoxyethylene sorbitan monooleate and polyoxyethylene sorbitan trioleate, polyoxyethylene sorbitol fatty acid esters such as polyoxyethylene sorbitol tetraoleate, and glycerin fatty acid esters Agents are preferred.
[0057]
  The viscosity of the ink for an ink jet printer of the present invention is 1-20.mPa · sThe range of is preferable. 1mPa · sIf this is the case, leakage of the ink from the cartridge is prevented, and 20mPa · sIf it is set below, the flying property of the ink is stabilized. Furthermore, considering high-speed response, 2-15mPa · sIs more preferable.
[0058]
The ink for an inkjet printer of the present invention includes, for example, a dispersion in which a pigment (for example, an organic pigment) is dispersed in an organic solvent in which the silicone-based graft polymer is dissolved using a self-dispersing silicone-based graft polymer; After the silicone-based graft polymer is precipitated and adsorbed on the pigment by mixing with an organic solvent in which the system-based graft polymer does not dissolve, further solvent substitution, addition of various additives, pigment concentration adjustment or filtration are performed as necessary. Etc. can be manufactured.
[0059]
More specifically, a dispersion process A in which a pigment (for example, an organic pigment) is dispersed in an organic solvent in which the silicone graft polymer is dissolved using a silicone graft polymer, and the silicone in the dispersion obtained in the dispersion process A Injecting an organic solvent in which the graft polymer does not dissolve or injecting and mixing the dispersion obtained in dispersion step A into an organic solvent in which the silicone graft polymer does not dissolve, precipitates the silicone graft polymer The dispersion composition was prepared by a production method comprising a mixing step B for allowing the pigment to be adsorbed to the pigment, a crosslinking step C for fixing the silicone-based graft polymer by crosslinking, if necessary, and a concentration step D for distilling the solvent if necessary. After the product is manufactured, various additives are added, the pigment concentration is adjusted, or filtration is performed.
[0060]
In dispersion step A, after dissolving the silicone-based graft polymer in an organic solvent and adding a pigment, if necessary, using a dispersion medium such as glass beads, steel beads or zirconia beads, a bead mill such as a dyno mill or a DSP-mill, A dispersion is obtained by dispersing with a disperser such as a roll mill, sand mill, attritor, kneader or nanomizer. Furthermore, various additives such as a surfactant, a pigment dispersant, a pigment derivative, and a charge generator may be added as necessary.
[0061]
The dispersion conditions for dispersing with a disperser depend on the type of pigment and the type of disperser, but considering the economy and the like, the temperature is in the range of 0 ° C. to 150 ° C. and the dispersion time is preferably as short as possible. If it is the range of time-10 hours / kg, it is preferable at the point of productivity. The dispersed particle size after dispersion is preferably submicron or less in terms of volume average diameter, and more preferably 0.5 microns or less in consideration of sedimentation aggregation.
[0062]
The method for measuring the dispersed particle size is not particularly limited, but a known and commonly used method is used, and for example, it is measured by a particle size distribution measuring apparatus of a laser scattering method or a centrifugal sedimentation method. Further, a crosslinking agent for crosslinking the silicone graft polymer is mixed before or after dispersion. In particular, it is preferable to mix after dispersion because there is no influence of reaction or the like at the time of dispersion. The ratio of the cross-linking agent is not particularly limited as long as it can be cross-linked to fix the silicone-based graft polymer to the pigment, but is preferably in the range of 2 to 100 parts by weight with respect to 100 parts by weight of the silicone-based graft polymer. A range of parts by weight is more preferred.
[0063]
Next, in the mixing step B, an organic solvent in which the silicone graft polymer does not dissolve is added to the dispersion produced in the dispersion step A, or an organic solvent in which the silicone graft polymer does not dissolve in the dispersion obtained in the dispersion step A. Add slowly to solvent and mix. In this case, the dispersion is uniformly mixed using a simple stirrer such as a three-one motor, a magnetic stirrer, a disper, or a homogenizer at or after the addition. Further, using a mixer such as a line mixer, the organic solvent in which the silicone-based graft polymer is not dissolved and the dispersion produced in the dispersion step A are mixed at once. Further, after the addition, a dispersing machine such as a bead mill or a high-pressure spray mill may be used for the purpose of making the precipitated particles finer.
[0064]
The organic solvent in which the silicone graft polymer does not dissolve is not particularly limited as long as the silicone graft polymer does not dissolve, but an organic solvent having a solubility parameter of 7.8 or less is particularly preferable. Examples of the organic solvent having a solubility parameter of 7.8 or less include aliphatic hydrocarbons such as hexane, mineral spirits, Isopar series manufactured by Exxon Chemical Co., etc., and silicone such as dialkylpolysiloxane and cyclic polydialkylsiloxane. And vegetable oils such as olive oil, safflower oil, sunflower oil, soybean oil and linseed oil, and diethyl ether. The ratio of the organic solvent used here is preferably in the range of 0 to 10,000 parts by weight with respect to 100 parts by weight of the silicone-based graft polymer in order to increase the pigment concentration in the produced dispersion composition.
[0065]
In the crosslinking step C in which the silicone-based graft polymer is immobilized by crosslinking, the crosslinking method is not particularly limited, and examples thereof include a crosslinking method by heating, ultraviolet rays, electron beams, and the like. In particular, the heating method is preferred because of the reactivity or the ability to react with a simple apparatus. The temperature for crosslinking by heating is not particularly limited as long as the dispersion state of the pigment is not destroyed, but is preferably 200 ° C. or less, more preferably 180 ° C. or less.
[0066]
The concentration step D is performed according to the pigment concentration and ink characteristics. Further, the concentration step may be performed before the crosslinking step C. Examples of a method for concentrating the solvent include a general atmospheric pressure or vacuum distillation method. For example, when an inkjet ink is formed using a silicone solvent, the organic solvent that dissolves the silicone graft polymer is concentrated by atmospheric or vacuum distillation using a solvent having a boiling point lower than that of the silicone solvent. On the contrary, when an inkjet ink is prepared using an organic solvent that dissolves the silicone-based graft polymer, a silicone solvent having a boiling point lower than that of the organic solvent that dissolves the silicone-based graft polymer is used and concentrated by distillation under normal pressure or reduced pressure. .
[0067]
Further, the ink for an ink jet printer of the present invention is adjusted to a predetermined granular material concentration or binder concentration by adding a binder and / or an organic solvent depending on the use. Examples of the binder include natural proteins, celluloses, polyvinyl alcohol, polyacrylamide, aromatic amide, polyacrylic acid, polyvinyl ether, polyvinyl pyrrolidone, acrylic, polyester, alkyd, urethane, amide resin, melamine resin, ether resin, fluorine. A synthetic polymer such as a resin, a styrene acrylic resin, and a styrene maleic resin, a photosensitive resin, a thermosetting resin, an ultraviolet curable resin, an electron beam curable resin, or the like is preferable.
[0068]
If necessary, the ink for an inkjet printer of the present invention is a peel inhibitor, a leveling agent, a charge adjusting agent such as a metal soap or lecithin, a wetting agent, an antiseptic, a deodorant, a fragrance, a pigment dispersant, a pigment derivative, etc. Can be further blended.
[0069]
The method of adjusting the binder, organic solvent and various additives by adding them to the ink for ink jet printers of the present invention may use a simple stirrer such as a disper, and does not require a conventional disperser. Energy saving and low cost production.
[0070]
A printer to which the ink for an ink jet printer of the present invention is applied includes a recording head having a plurality of ink discharge ports and energy conversion means for converting electrical energy into ink discharge energy corresponding to the plurality of discharge ports. It is an inkjet printer provided. For example, it is a thermal method such as a known general piezo method or a bubble jet printer. In particular, since an organic solvent is used, a piezo printer is preferable in consideration of safety.
[0071]
【Example】
Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. In the following description, “parts” and “%” mean “parts by weight” and “% by weight” unless otherwise specified. Moreover, the reagent 1 grade made from a Wako Purechemical company was used for all the reagents without a cautionary statement.
[0072]
Synthesis Example 1 (Preparation of silicone graft polymer)
19.5 parts of n-butyl methacrylate
19.5 parts of lauryl methacrylate
Styrene 13.0 parts
Methacrylic acid 9.0 parts
2-hydroxyethyl methacrylate 13.0 parts
X-22-174DX (manufactured by Shin-Etsu Chemical Co., Ltd.) 26.0 parts
Perbutyl O (Nippon Yushi Co., Ltd. peroxyester) 8.0 parts
Methyl ethyl ketone 100.0 parts
These components were mixed to prepare a solution.
[0073]
Next, 100 parts of methyl ethyl ketone (reagent grade 1 of Wako Pure Chemical Industries, Ltd.) was weighed into a reaction vessel equipped with a nitrogen introduction tube, and the temperature was raised to 80 ° C. while sealing with nitrogen. The said solution was dripped over 2 hours, and it was made to react at 80 degreeC after completion | finish of dripping for 14 hours. The solution after the reaction had a non-volatile content of 47.5%, a glass transition temperature of −6.0 ° C. (measured with a thermal decomposition apparatus manufactured by Mac Science), an acid value of 57.2 KOH mg / g, and a hydroxyl value of 55.3 KOH mg / g. And a silicone-based graft polymer having a number average molecular weight of 7400.
[0074]
One part of this silicone graft polymer was diluted with a cyclic methylsiloxane solvent KF995 (manufactured by Shin-Etsu Chemical Co., Ltd.). When 1.8 parts of a cyclic methylsiloxane solvent was added, it was self-dispersed to obtain a dispersion having an average particle size of 0.092 μm (measured with a Laser Doppler type particle size distribution meter N4 PLUS manufactured by Coulter).
[0075]
Synthesis Example 2 (Preparation of silicone graft polymer)
9.7 parts of n-butyl methacrylate
29.3 parts lauryl methacrylate
Methacrylic acid 9.0 parts
2-hydroxyethyl methacrylate 26.0 parts
X-22-174DX (manufactured by Shin-Etsu Chemical Co., Ltd.) 26.0 parts
Perbutyl O (Nippon Yushi Co., Ltd. peroxyester) 8.0 parts
Methyl ethyl ketone 22.2 parts
These components were mixed to prepare a solution.
[0076]
Next, 100 parts of methyl ethyl ketone (reagent grade 1 of Wako Pure Chemical Industries, Ltd.) was weighed into a reaction vessel equipped with a nitrogen introduction tube, and the temperature was raised to 80 ° C. while sealing with nitrogen. The said solution was dripped over 2 hours, and it was made to react at 80 degreeC after completion | finish of dripping for 14 hours. The solution after the reaction had a non-volatile content of 44.5%, a glass transition temperature of −26.0 ° C. (measured with a thermal decomposition apparatus manufactured by Mac Science), an acid value of 58.2 KOH mg / g, and a hydroxyl value of 111.3 KOH mg / g. And a silicone-based graft polymer having a number average molecular weight of 7400.
[0077]
One part of this silicone graft polymer was diluted with a cyclic methylsiloxane solvent KF995 (manufactured by Shin-Etsu Chemical Co., Ltd.). When 1.9 parts of a cyclic methylsiloxane solvent was added, it was self-dispersed to obtain a dispersion having an average particle size of 0.046 μm (measured with a Laser Doppler type particle size distribution analyzer N4 PLUS manufactured by Coulter).
[0078]
Synthesis Example 3 (Preparation of silicone graft polymer)
n-Butyl acrylate 22.7 parts
29.3 parts lauryl methacrylate
Methacrylic acid 9.0 parts
2-hydroxyethyl methacrylate 13.0 parts
X-22-174DX (manufactured by Shin-Etsu Chemical Co., Ltd.) 26.0 parts
Perbutyl O (Nippon Yushi Co., Ltd. peroxyester) 8.0 parts
Methyl ethyl ketone 22.2 parts
These components were mixed to prepare a solution.
[0079]
Next, 100 parts of methyl ethyl ketone (reagent grade 1 of Wako Pure Chemical Industries, Ltd.) was weighed into a reaction vessel equipped with a nitrogen introduction tube, and the temperature was raised to 80 ° C. while sealing with nitrogen. The said solution was dripped over 2 hours, and it was made to react at 80 degreeC after completion | finish of dripping for 14 hours. The solution after the reaction had a non-volatile content of 46.3%, a glass transition temperature of −44.0 ° C. (measured with a thermal decomposition apparatus manufactured by Mac Science), an acid value of 58.0 KOHmg / g, and a hydroxyl value of 55.3 KOHmg / g. This was a silicone-based graft polymer having a number average molecular weight of 12,000.
[0080]
One part of this silicone graft polymer was diluted with a cyclic methylsiloxane solvent KF995 (manufactured by Shin-Etsu Chemical Co., Ltd.). When 3.5 parts of a cyclic methylsiloxane solvent was added, it was self-dispersed to obtain a dispersion having an average particle size of 0.026 μm (measured with a laser Doppler type particle size distribution analyzer N4 PLUS manufactured by Coulter).
[0081]
Synthesis Example 4 (Preparation of silicone graft polymer)
n-Butyl acrylate 22.7 parts
29.3 parts lauryl methacrylate
9.0 parts of acrylic acid
2-hydroxyethyl methacrylate 13.0 parts
X-22-174DX (manufactured by Shin-Etsu Chemical Co., Ltd.) 26.0 parts
Perbutyl O (Nippon Yushi Co., Ltd. peroxyester) 8.0 parts
Methyl ethyl ketone 22.2 parts
These components were mixed to prepare a solution.
[0082]
Next, 100 parts of methyl ethyl ketone (reagent grade 1 of Wako Pure Chemical Industries, Ltd.) was weighed into a reaction vessel equipped with a nitrogen introduction tube, and the temperature was raised to 80 ° C. while sealing with nitrogen. The said solution was dripped over 2 hours, and it was made to react at 80 degreeC after completion | finish of dripping for 14 hours. The solution after the reaction had a non-volatile content of 49.2%, a glass transition temperature of −45.8 ° C. (measured with a thermal decomposition apparatus manufactured by Mac Science), an acid value of 58.4 KOHmg / g, and a hydroxyl value of 55.7 KOHmg / g. This was a silicone-based graft polymer having a number average molecular weight of 13,000.
[0083]
One part of this silicone graft polymer was diluted with a cyclic methylsiloxane solvent KF995 (manufactured by Shin-Etsu Chemical Co., Ltd.). When 3.7 parts of a cyclic methylsiloxane solvent was added, it was self-dispersed to obtain a dispersion having an average particle size of 0.032 μm (measured with a Laser Doppler type particle size distribution meter N4 PLUS manufactured by Coulter).
[0084]
Synthesis Example 5 (Preparation of silicone graft polymer)
n-Butyl acrylate 22.7 parts
40.3 parts of lauryl methacrylate
Methacrylic acid 9.0 parts
2-hydroxyethyl methacrylate 13.0 parts
X-22-174DX (manufactured by Shin-Etsu Chemical Co., Ltd.) 15.0 parts
Perbutyl O (Nippon Yushi Co., Ltd. peroxyester) 8.0 parts
Methyl ethyl ketone 22.2 parts
These components were mixed to prepare a solution.
[0085]
Next, 100 parts of methyl ethyl ketone (reagent grade 1 of Wako Pure Chemical Industries, Ltd.) was weighed into a reaction vessel equipped with a nitrogen introduction tube, and the temperature was raised to 80 ° C. while sealing with nitrogen. The said solution was dripped over 2 hours, and it was made to react at 80 degreeC after completion | finish of dripping for 14 hours. The solution after the reaction had a non-volatile content of 45.9%, a glass transition temperature of −42.9 ° C. (measured with a thermal decomposition apparatus manufactured by Mac Science), an acid value of 58.1 KOHmg / g, and a hydroxyl value of 55.4 KOHmg / g. And a silicone-based graft polymer having a number average molecular weight of 14,000.
[0086]
One part of this silicone graft polymer was diluted with a cyclic methylsiloxane solvent KF995 (manufactured by Shin-Etsu Chemical Co., Ltd.). When 2.2 parts of a cyclic methylsiloxane solvent was added, it was self-dispersed to obtain a dispersion having an average particle size of 0.092 μm (measured with a laser Doppler type particle size distribution meter N4 PLUS manufactured by Coulter).
[0087]
Synthesis Example 6 (Preparation of silicone-based graft polymer)
n-butyl methacrylate 16.1 parts
Lauryl methacrylate 10.0 parts
Styrene monomer 35.0 parts
6.9 parts of methacrylic acid
Glycidyl methacrylate 12.0 parts
X-22-174DX (manufactured by Shin-Etsu Chemical Co., Ltd.) 20.0 parts
Perbutyl O (Nippon Yushi Co., Ltd. peroxyester) 8.0 parts
These components were mixed to prepare a solution.
[0088]
Next, 100 parts of methyl ethyl ketone (reagent grade 1 of Wako Pure Chemical Industries, Ltd.) was weighed into a reaction vessel equipped with a nitrogen introduction tube, and the temperature was raised to 80 ° C. while sealing with nitrogen. The said solution was dripped over 2 hours, and it was made to react at 80 degreeC after completion | finish of dripping for 14 hours. The solution after the reaction was a silicone-based graft having a non-volatile content of 46.3%, a glass transition temperature of 11.4 ° C. (measured with a thermal decomposition apparatus manufactured by Mac Science), an acid value of 44.7 KOH mg / g, and a number average molecular weight of 8400. It was a polymer.
[0089]
One part of this silicone graft polymer was diluted with a cyclic methylsiloxane solvent KF995 (manufactured by Shin-Etsu Chemical Co., Ltd.). When 3.9 parts of a cyclic methylsiloxane solvent was added, it was self-dispersed to obtain a dispersion having an average particle size of 0.062 μm (measured with a laser Doppler type particle size distribution analyzer N4 PLUS manufactured by Coulter).
[0090]
The characteristics of the silicone graft polymers obtained in Synthesis Examples 1 to 6 are summarized in Table 1 below.
[0091]
[Table 1]
Table 1 Properties of synthetic silicone graft polymers

[0092]
Example 1
To 100ml plastic polybin,
12.6 parts of the silicone-based graft polymer of Synthesis Example 1
Fastogen Blue TGR as a pigment
(Copper phthalocyanine blue pigment manufactured by Dainippon Ink & Chemicals, Inc.) 5.7 parts
Solsperse 5000 as phthalocyanine pigment derivative
(Zeneca) 0.3 parts
Methyl ethyl ketone 11.4 parts
300 μmφ zirconia beads 100 parts
Measure and disperse with paint shaker (Aisin) for 2 hours,
Methyl ethyl ketone 30.0 parts
Was added to obtain a dispersion slurry.
[0093]
Next, 55 parts of cyclic methylsiloxane solvent KF995 (manufactured by Shin-Etsu Chemical Co., Ltd.) and 30 parts of chain dimethylsiloxane solvent KF96L-5CS (manufactured by Shin-Etsu Chemical Co., Ltd.) are weighed and placed in a 300 cc eggplant flask and stirred with a magnetic stirrer. did. While stirring, 50 parts of the dispersion slurry was slowly added dropwise to deposit a silicone graft polymer on the pigment surface.
[0094]
further,
10.5 parts of silicone graft polymer of Synthesis Example 1
Methyl ethyl ketone 4.5 parts
The polymer solution mixed with was slowly dropped and the silicone-based graft polymer was self-dispersed in an organic solvent.
[0095]
After the dropwise addition, methyl ethyl ketone was desolvated by distillation under reduced pressure to obtain a dispersion having a pigment concentration of 5.10%. The obtained dispersion composition has a dispersion particle size of 0.220 μm (measured with a laser Doppler type particle size distribution meter N4 PLUS manufactured by Coulter, Inc.), and the absorbance of the supernatant (produced by JASCO Corporation) with a centrifugal force of 33500 G for 5 hours. The amount of the resin adsorbed was determined from the V-570 type ultraviolet / visible spectrophotometer, and 157.1 parts of the silicone-based graft polymer were adsorbed to 100 parts of the particulate material.
[0096]
Further, 2.0 parts of cyclic methylsiloxane solvent KF995 was added to make a total amount of 100 parts, and the mixture was filtered with a filter having a diameter of 1 μm to obtain an ink for an oil-based inkjet printer having a pigment concentration of 5%.
[0097]
As shown in Table 3 below, this ink had a small particle size, no change after the storage test, and no sedimentation. The printed matter was excellent in scratch resistance, water resistance and light resistance, and had a high flash point and high safety. Furthermore, the printing stability was very good.
[0098]
Comparative Example 1
As a result of conducting various tests shown in Table 3 below using a commercially available oil-based ink jet printer ink (manufactured by Seiko Instruments Inc.), the particle size was small, no change was observed after the storage test, and no sedimentation was observed. . However, the scratch resistance of the printed matter was so bad that the ink was removed by rubbing with a finger one week after printing.
[0099]
Comparative Example 2
To 100ml plastic polybin,
13.0 parts of silicone-based graft polymer of Synthesis Example 6
Fastogen Blue TGR as a pigment
(Copper phthalocyanine blue pigment manufactured by Dainippon Ink & Chemicals, Inc.) 5.7 parts
Solsperse 5000 as phthalocyanine pigment derivative
(Zeneca) 0.3 parts
Methyl ethyl ketone 11.0 parts
300 μmφ zirconia beads 100 parts
Measure and disperse with paint shaker (Aisin) for 2 hours,
Methyl ethyl ketone 30.0 parts
Was added to obtain a dispersion slurry.
[0100]
Next, 60 parts of cyclic methylsiloxane solvent KF995 (manufactured by Shin-Etsu Chemical Co., Ltd.) and 30 parts of chain dimethylsiloxane solvent KF96L-5CS (manufactured by Shin-Etsu Chemical Co., Ltd.) are weighed, put into a 300 cc eggplant flask, and stirred with a magnetic stirrer. did. While stirring, 50 parts of the dispersion slurry was slowly added dropwise to deposit a silicone graft polymer on the pigment surface.
[0101]
After dropwise addition, methyl ethyl ketone was desolvated by distillation under reduced pressure to obtain a dispersion having a pigment concentration of 5.08%. The obtained dispersion composition has a dispersed particle size of 0.191 μm (measured with a laser Doppler type particle size distribution meter N4 PLUS manufactured by Coulter, Inc.), and the absorbance of the supernatant (produced by JASCO Corporation) with a centrifugal force of 33500 G for 5 hours. The amount of the resin adsorbed was determined from the V-570 type ultraviolet / visible spectrophotometer of No. 5), and 86.2 parts of the silicone-based graft polymer was adsorbed to 100 parts of the particulate material.
[0102]
Furthermore, 1.6 parts of cyclic methylsiloxane solvent KF995 was added to make a total amount of 100 parts, and the mixture was filtered with a filter having a diameter of 1 μm to obtain an ink for an oil-based inkjet printer having a pigment concentration of 5%.
[0103]
As shown in Table 3 below, this ink had a small particle size, no change after the storage test, and no sedimentation. However, the scratch resistance of the printed matter was so bad that the ink was removed by rubbing with a finger one week after printing.
[0104]
Example 2
To 100ml plastic polybin,
13.5 parts of silicone-based graft polymer of Synthesis Example 2
Fastogen Blue TGR as a pigment
(Copper phthalocyanine blue pigment manufactured by Dainippon Ink & Chemicals, Inc.) 5.7 parts
Solsperse 5000 as phthalocyanine pigment derivative
(Zeneca) 0.3 parts
Methyl ethyl ketone 10.5 parts
300 μmφ zirconia beads 100 parts
Measure and disperse with paint shaker (Aisin) for 2 hours,
Methyl ethyl ketone 30.0 parts
Was added to obtain a dispersion slurry.
[0105]
Next, 55 parts of cyclic methylsiloxane solvent KF995 (manufactured by Shin-Etsu Chemical Co., Ltd.) and 30 parts of chain dimethylsiloxane solvent KF96L-5CS (manufactured by Shin-Etsu Chemical Co., Ltd.) are weighed and placed in a 300 cc eggplant flask and stirred with a magnetic stirrer. did. While stirring, 50 parts of the dispersion slurry was slowly added dropwise to deposit a silicone graft polymer on the pigment surface.
[0106]
further,
11.2 parts of silicone graft polymer of Synthesis Example 2
3.8 parts of methyl ethyl ketone
The polymer solution mixed with was slowly dropped and the silicone-based graft polymer was self-dispersed in an organic solvent.
[0107]
After the dropwise addition, methyl ethyl ketone was desolvated by distillation under reduced pressure to obtain a dispersion having a pigment concentration of 5.03%. The obtained dispersion composition has a dispersion particle size of 0.180 μm (measured with a laser Doppler type particle size distribution meter N4 PLUS manufactured by Coulter, Inc.), and the absorbance of the supernatant (produced by JASCO Corporation) with a centrifugal force of 33500 G for 5 hours. The amount of the resin adsorbed was determined from the V-570 type ultraviolet / visible spectrophotometer, and 162.2 parts of the silicone-based graft polymer was adsorbed to 100 parts of the particulate material.
[0108]
Furthermore, 0.6 part of cyclic methylsiloxane solvent KF995 was added to make a total amount of 100 parts, and the mixture was filtered through a filter having a diameter of 1 μm to obtain an ink for an oil-based inkjet printer having a pigment concentration of 5%.
[0109]
As shown in Table 3 below, this ink had a small particle size, no change after the storage test, and no sedimentation. The printed matter was excellent in scratch resistance, water resistance and light resistance, and had a high flash point and high safety. Furthermore, the printing stability was very good.
[0110]
Example 3
To 100ml plastic polybin,
13.0 parts of silicone-based graft polymer of Synthesis Example 3
Fastogen Blue TGR as a pigment
(Copper phthalocyanine blue pigment manufactured by Dainippon Ink & Chemicals, Inc.) 5.7 parts
Solsperse 5000 as phthalocyanine pigment derivative
(Zeneca) 0.3 parts
Methyl ethyl ketone 11.0 parts
300 μmφ zirconia beads 100 parts
Measure and disperse with paint shaker (Aisin) for 2 hours,
Methyl ethyl ketone 30.0 parts
Was added to obtain a dispersion slurry.
[0111]
Next, 55 parts of cyclic methylsiloxane solvent KF995 (manufactured by Shin-Etsu Chemical Co., Ltd.) and 30 parts of chain dimethylsiloxane solvent KF96L-5CS (manufactured by Shin-Etsu Chemical Co., Ltd.) are weighed and placed in a 300 cc eggplant flask and stirred with a magnetic stirrer. did. While stirring, 50 parts of the dispersion slurry was slowly added dropwise to deposit a silicone graft polymer on the pigment surface.
[0112]
further,
10.8 parts of silicone graft polymer of Synthesis Example 3
Methyl ethyl ketone 4.2 parts
The polymer solution mixed with was slowly dropped and the silicone-based graft polymer was self-dispersed in an organic solvent.
[0113]
After the dropwise addition, methyl ethyl ketone was desolvated by distillation under reduced pressure to obtain a dispersion having a pigment concentration of 5.05%. The obtained dispersion composition has a dispersed particle size of 0.147 μm (measured with a laser Doppler type particle size distribution meter N4 PLUS manufactured by Coulter, Inc.), and the absorbance of the supernatant (produced by JASCO Corporation) with a centrifugal force of 33500 G for 5 hours. The amount of the resin adsorbed was determined from the V-570 type ultraviolet / visible spectrophotometer, and 163.5 parts of the silicone-based graft polymer was adsorbed to 100 parts of the particulate material.
[0114]
Further, 1.0 part of cyclic methylsiloxane solvent KF995 was added to make a total amount of 100 parts, and the mixture was filtered with a filter having a diameter of 1 μm to obtain an ink for an oil-based inkjet printer having a pigment concentration of 5%.
[0115]
As shown in Table 3 below, this ink had a small particle size, no change after the storage test, and no sedimentation. The printed matter was excellent in scratch resistance, water resistance and light resistance, and had a high flash point and high safety. Furthermore, the printing stability was very good.
[0116]
Example 4
To 100ml plastic polybin,
13.0 parts of silicone-based graft polymer of Synthesis Example 3
Magenta RT-355D as pigment
(Quinacridone pigment manufactured by Ciba Specialty Chemicals) 6.0 parts
Methyl ethyl ketone 11.0 parts
300 μmφ zirconia beads 100 parts
Measure and disperse with paint shaker (Aisin) for 2 hours,
Methyl ethyl ketone 30.0 parts
Was added to obtain a dispersion slurry.
[0117]
Next, 55 parts of cyclic methylsiloxane solvent KF995 (manufactured by Shin-Etsu Chemical Co., Ltd.) and 30 parts of chain dimethylsiloxane solvent KF96L-5CS (manufactured by Shin-Etsu Chemical Co., Ltd.) are weighed and placed in a 300 cc eggplant flask and stirred with a magnetic stirrer. did. While stirring, 50 parts of the dispersion slurry was slowly added dropwise to deposit a silicone graft polymer on the pigment surface.
[0118]
further,
10.8 parts of silicone graft polymer of Synthesis Example 3
Methyl ethyl ketone 4.2 parts
The polymer solution mixed with was slowly dropped and the silicone-based graft polymer was self-dispersed in an organic solvent.
[0119]
After the dropwise addition, methyl ethyl ketone was desolvated by distillation under reduced pressure to obtain a dispersion having a pigment concentration of 5.01%. The obtained dispersion composition has a dispersed particle size of 0.163 μm (measured with a laser Doppler type particle size distribution meter N4 PLUS manufactured by Coulter, Inc.), and the absorbance of the supernatant (produced by JASCO Corporation) with a centrifugal force of 33500 G for 5 hours. The amount of the resin adsorbed was determined from the V-570 type ultraviolet / visible spectrophotometer of No. 5), and 161.2 parts of the silicone-based graft polymer was adsorbed to 100 parts of the particulate material.
[0120]
Further, 0.2 part of cyclic methylsiloxane solvent KF995 was added to make a total amount of 100 parts, and the mixture was filtered through a filter having a diameter of 1 μm to obtain an ink for an oil-based inkjet printer having a pigment concentration of 5%.
[0121]
As shown in Table 3 below, this ink had a small particle size, no change after the storage test, and no sedimentation. The printed matter was excellent in scratch resistance, water resistance and light resistance, and had a high flash point and high safety. Furthermore, the printing stability was very good.
[0122]
Example 5
To 100ml plastic polybin,
13.0 parts of silicone-based graft polymer of Synthesis Example 3
Yellow P-HG as a pigment
(Clariant benzimidazolone pigment) 6.0 parts
Methyl ethyl ketone 11.0 parts
300 μmφ zirconia beads 100 parts
Measure and disperse with paint shaker (Aisin) for 2 hours,
Methyl ethyl ketone 30.0 parts
Was added to obtain a dispersion slurry.
[0123]
Next, 55 parts of cyclic methylsiloxane solvent KF995 (manufactured by Shin-Etsu Chemical Co., Ltd.) and 30 parts of chain dimethylsiloxane solvent KF96L-5CS (manufactured by Shin-Etsu Chemical Co., Ltd.) are weighed and placed in a 300 cc eggplant flask and stirred with a magnetic stirrer. did. While stirring, 50 parts of the dispersion slurry was slowly added dropwise to deposit a silicone graft polymer on the pigment surface.
[0124]
further,
10.8 parts of silicone graft polymer of Synthesis Example 3
Methyl ethyl ketone 4.2 parts
The polymer solution mixed with was slowly dropped and the silicone-based graft polymer was self-dispersed in an organic solvent.
[0125]
After the dropwise addition, methyl ethyl ketone was desolvated by distillation under reduced pressure to obtain a dispersion having a pigment concentration of 5.02%. The obtained dispersion composition has a dispersed particle size of 0.192 μm (measured with a laser Doppler type particle size distribution meter N4 PLUS manufactured by Coulter, Inc.), and the absorbance of the supernatant (produced by JASCO Corporation) with a centrifugal force of 33500 G for 5 hours. The amount of the resin adsorbed was determined from the V-570 type ultraviolet / visible spectrophotometer of No. 5), and 168.1 parts of the silicone-based graft polymer were adsorbed to 100 parts of the particulate material.
[0126]
Furthermore, 0.4 part of cyclic methylsiloxane solvent KF995 was added to make a total amount of 100 parts, and the mixture was filtered with a filter having a diameter of 1 μm to obtain an ink for an oil-based inkjet printer having a pigment concentration of 5%.
[0127]
As shown in Table 3 below, this ink had a small particle size, no change after the storage test, and no sedimentation. The printed matter was excellent in scratch resistance, water resistance and light resistance, and had a high flash point and high safety. Furthermore, the printing stability was very good.
[0128]
Example 6
To 100ml plastic polybin,
13.0 parts of silicone-based graft polymer of Synthesis Example 3
Printex 70 as pigment
(Degussa carbon black pigment) 5.9 parts
Solsperse 5000 as phthalocyanine pigment derivative
(Manufactured by Zeneca) 0.1 parts
Methyl ethyl ketone 11.0 parts
300 μmφ zirconia beads 100 parts
Measure and disperse with paint shaker (Aisin) for 2 hours,
Methyl ethyl ketone 30.0 parts
Was added to obtain a dispersion slurry.
[0129]
Next, 55 parts of cyclic methylsiloxane solvent KF995 (manufactured by Shin-Etsu Chemical Co., Ltd.) and 30 parts of chain dimethylsiloxane solvent KF96L-5CS (manufactured by Shin-Etsu Chemical Co., Ltd.) are weighed and placed in a 300 cc eggplant flask and stirred with a magnetic stirrer. did. While stirring, 50 parts of the dispersion slurry was slowly added dropwise to deposit a silicone graft polymer on the pigment surface.
[0130]
further,
Silicone graft polymer of Synthesis Example 3 A polymer solution in which 4.2 parts of methyl ethyl ketone was mixed was slowly added dropwise, and the silicone graft polymer was self-dispersed in an organic solvent.
[0131]
After the dropwise addition, methyl ethyl ketone was desolvated by distillation under reduced pressure to obtain a dispersion having a pigment concentration of 5.02%. The obtained dispersion composition has a dispersed particle size of 0.190 μm (measured with a laser Doppler type particle size distribution meter N4 PLUS manufactured by Coulter, Inc.), and the absorbance of the supernatant (produced by JASCO Corporation) with a centrifugal force of 33500 G for 5 hours. The amount of the resin adsorbed was determined from the V-570 type ultraviolet / visible spectrophotometer, and 167.8 parts of the silicone-based graft polymer was adsorbed to 100 parts of the particulate material.
[0132]
Furthermore, 0.4 part of cyclic methylsiloxane solvent KF995 was added to make a total amount of 100 parts, and the mixture was filtered with a filter having a diameter of 1 μm to obtain an ink for an oil-based inkjet printer having a pigment concentration of 5%.
[0133]
As shown in Table 3 below, this ink had a small particle size, no change after the storage test, and no sedimentation. The printed matter was excellent in scratch resistance, water resistance and light resistance, and had a high flash point and high safety. Furthermore, the printing stability was very good.
[0134]
Example 7
To 100ml plastic polybin,
13.0 parts of silicone-based graft polymer of Synthesis Example 3
Fastogen Blue TGR as a pigment
(Copper phthalocyanine blue pigment manufactured by Dainippon Ink & Chemicals, Inc.) 5.7 parts
Solsperse 5000 as phthalocyanine pigment derivative
(Zeneca) 0.3 parts
Methyl ethyl ketone 11.0 parts
300 μmφ zirconia beads 100 parts
Measure and disperse with paint shaker (Aisin) for 2 hours,
Methyl ethyl ketone 30.0 parts
Was added to obtain a dispersion slurry.
[0135]
Next, 55 parts of cyclic methylsiloxane solvent KF995 (manufactured by Shin-Etsu Chemical Co., Ltd.) and 30 parts of chain dimethylsiloxane solvent KF96L-5CS (manufactured by Shin-Etsu Chemical Co., Ltd.) are weighed and placed in a 300 cc eggplant flask and stirred with a magnetic stirrer. did. While stirring, 50 parts of the dispersion slurry was slowly added dropwise to deposit a silicone graft polymer on the pigment surface.
[0136]
further,
10.2 parts of silicone graft polymer of Synthesis Example 4
4.8 parts of methyl ethyl ketone
The polymer solution mixed with was slowly dropped and the silicone-based graft polymer was self-dispersed in an organic solvent.
[0137]
After the dropwise addition, methyl ethyl ketone was desolvated by distillation under reduced pressure to obtain a dispersion having a pigment concentration of 5.07%. The obtained dispersion composition has a dispersed particle size of 0.185 μm (measured with a laser Doppler type particle size distribution meter N4 PLUS manufactured by Coulter, Inc.), and the absorbance of the supernatant (produced by JASCO Corporation) with a centrifugal force of 33500 G for 5 hours. The amount of the resin adsorbed was determined from the V-570 type ultraviolet / visible spectrophotometer), and 164.5 parts of the silicone-based graft polymer was adsorbed to 100 parts of the particulate material.
[0138]
Further, 1.4 parts of cyclic methylsiloxane solvent KF995 was added to make a total amount of 100 parts, and the mixture was filtered with a filter having a diameter of 1 μm to obtain an ink for an oil-based inkjet printer having a pigment concentration of 5%.
[0139]
As shown in Table 3 below, this ink had a small particle size, no change after the storage test, and no sedimentation. The printed matter was excellent in scratch resistance, water resistance and light resistance, and had a high flash point and high safety. Furthermore, the printing stability was very good.
[0140]
Example 8
To 100ml plastic polybin,
13.0 parts of silicone-based graft polymer of Synthesis Example 3
Fastogen Blue TGR as a pigment
(Copper phthalocyanine blue pigment manufactured by Dainippon Ink & Chemicals, Inc.) 5.7 parts
Solsperse 5000 as phthalocyanine pigment derivative
(Zeneca) 0.3 parts
Methyl ethyl ketone 11.0 parts
300 μmφ zirconia beads 100 parts
Measure and disperse with paint shaker (Aisin) for 2 hours,
Methyl ethyl ketone 30.0 parts
Was added to obtain a dispersion slurry.
[0141]
Next, 55 parts of cyclic methylsiloxane solvent KF995 (manufactured by Shin-Etsu Chemical Co., Ltd.) and 30 parts of chain dimethylsiloxane solvent KF96L-5CS (manufactured by Shin-Etsu Chemical Co., Ltd.) are weighed and placed in a 300 cc eggplant flask and stirred with a magnetic stirrer. did. While stirring, 50 parts of the dispersion slurry was slowly added dropwise to deposit a silicone graft polymer on the pigment surface.
[0142]
further,
10.9 parts of silicone graft polymer of Synthesis Example 5
Methyl ethyl ketone 4.1 parts
The polymer solution mixed with was slowly dropped and the silicone-based graft polymer was self-dispersed in an organic solvent.
[0143]
After the dropwise addition, methyl ethyl ketone was desolvated by distillation under reduced pressure to obtain a dispersion having a pigment concentration of 5.01%. The obtained dispersion composition has a dispersion particle size of 0.208 μm (measured with a laser Doppler type particle size distribution meter N4 PLUS manufactured by Coulter, Inc.), and the absorbance of the supernatant (produced by JASCO Corporation) with a centrifugal force of 33500 G for 5 hours. The amount of the resin adsorbed was determined from the V-570 type ultraviolet / visible spectrophotometer), and 166.6 parts of the silicone-based graft polymer were adsorbed to 100 parts of the particulate material.
[0144]
Further, 0.2 part of cyclic methylsiloxane solvent KF995 was added to make a total amount of 100 parts, and the mixture was filtered through a filter having a diameter of 1 μm to obtain an ink for an oil-based inkjet printer having a pigment concentration of 5%.
[0145]
As shown in Table 3 below, this ink had a small particle size, no change after the storage test, and no sedimentation. The printed matter was excellent in scratch resistance, water resistance and light resistance, and had a high flash point and high safety. Furthermore, the printing stability was very good.
[0146]
Example 9
To 100ml plastic polybin,
13.0 parts of silicone-based graft polymer of Synthesis Example 3
Fastogen Blue TGR as a pigment
(Copper phthalocyanine blue pigment manufactured by Dainippon Ink & Chemicals, Inc.) 5.7 parts
Solsperse 5000 as phthalocyanine pigment derivative
(Zeneca) 0.3 parts
Methyl ethyl ketone 11.0 parts
300 μmφ zirconia beads 100 parts
Measure and disperse with paint shaker (Aisin) for 2 hours,
Methyl ethyl ketone 30.0 parts
Was added to obtain a dispersion slurry.
[0147]
Next, 55 parts of chain dimethylsiloxane solvent KF96A-2CS (manufactured by Shin-Etsu Chemical Co., Ltd.) and 30 parts of chain dimethylsiloxane solvent KF96L-5CS (manufactured by Shin-Etsu Chemical Co., Ltd.) are weighed and placed in a 300 cc eggplant flask. Stir with a stirrer. While stirring, 50 parts of the dispersion slurry was slowly added dropwise to deposit a silicone graft polymer on the pigment surface.
[0148]
further,
10.8 parts of silicone graft polymer of Synthesis Example 3
Methyl ethyl ketone 4.2 parts
The polymer solution mixed with was slowly dropped and the silicone-based graft polymer was self-dispersed in an organic solvent.
[0149]
After the dropwise addition, methyl ethyl ketone was desolvated by distillation under reduced pressure to obtain a dispersion having a pigment concentration of 5.35%. The obtained dispersion composition has a dispersion particle size of 0.156 μm (measured with a laser Doppler type particle size distribution meter N4 PLUS manufactured by Coulter, Inc.), and the absorbance of the supernatant (produced by JASCO Corporation) with a centrifugal force of 33500 G for 5 hours. The amount of the resin adsorbed was determined from the V-570 type ultraviolet / visible spectrophotometer, and 158.2 parts of the silicone-based graft polymer was adsorbed to 100 parts of the particulate material.
[0150]
Furthermore, 6.5 parts of cyclic methylsiloxane solvent KF96A-2CS was added to make a total amount of 100 parts, and the mixture was filtered through a filter having a 1 μm aperture to obtain an oil-based inkjet printer ink having a pigment concentration of 5%.
[0151]
As shown in Table 3 below, this ink had a small particle size, no change after the storage test, and no sedimentation. The printed matter was excellent in scratch resistance, water resistance and light resistance, and had a high flash point and high safety. Furthermore, the printing stability was very good.
[0152]
The properties of the dispersion compositions obtained in Examples 1 to 9 and Comparative Examples 1 to 2 are summarized in Table 2 below.
[0153]
[Table 2]
Table 2 Dispersion composition characteristics

[0154]
The characteristics of the inks for oil-based ink jet printers obtained in Examples 1 to 9 and Comparative Examples 1 to 2 are summarized in Table 3 below. In Table 3 below, “particle size” indicates a dispersion average particle size (μm) measured by a laser Doppler type particle size distribution analyzer N4PLUS manufactured by Coulter. “Viscosity” is a value (mPa · s) measured at a rotation speed of 100 rpm with an R-type viscometer manufactured by Toki Sangyo Co., Ltd. The “storage test” was carried out by weighing 40 g of ink in a 60 cc glass container, sealing it, and leaving it in a constant temperature bath at 60 ° C. for 2 weeks. In the column of “sediment”, “◯” indicates the case where no sediment is observed, and “x” indicates the case where sediment is observed. “Abrasion resistance” is a bar coater no. 4 was used to develop the color on a glossy photo paper made by Epson. In the “Abrasion resistance” column, ○ indicates the case where the ink did not come off even after rubbing with a finger after 30 seconds of color development. The case where it peeled off is shown. The “printing test” was carried out by filling a UX-IK4 ink cartridge for color facsimile manufactured by Sharp and printing on A4 paper with a color facsimile manufactured by Sharp. “Printing stability” was evaluated by continuously printing a printing pattern of the Japan Electronics Industry Association. In the “printing stability” column, “◯” indicates a case where 1000 or more continuous sheets can be stably printed, “Δ” indicates a case where cleaning is necessary but 1000 or more continuous sheets can be printed, and “×” indicates clogging. Indicates when printing is no longer possible. In “water resistance”, the printed matter was immersed in water, and whether or not bleeding occurred was visually observed. In the column of “Water resistance”, “◯” indicates a case where no bleeding occurred, and “X” indicates a case where it slightly blotted. In the column of “safety”, “◯” indicates that the flash point is 70 ° C. or higher, and “X” indicates that the flash point is lower than 70 ° C.
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[Table 3]
Table 3 Characteristics of oil-based inkjet printer ink

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【The invention's effect】
As described above, the ink for an oil-based inkjet printer of the present invention can improve the scratch resistance of the printed matter and improve the printing quality such as water resistance and light resistance by using a pigment and an organic solvent. In addition, improvements have been made to improve dispersion stability, such as sedimentation and storage stability of pigments. Furthermore, the safety of the ink could be improved by using a high-boiling silicone organic solvent with high safety.

Claims (25)

  An inkjet printer ink comprising an organic solvent, a pigment, and a silicone polymer, wherein the silicone polymer is a silicone graft polymer having a glass transition temperature in the range of 0 ° C to -50 ° C. Ink for printers.   The particle size of the silicone-based graft polymer is in the range of 0.01 µm to 0.3 µm, and the primary particle size of the pigment is in the range of 0.01 µm to 0.29 µm. Ink for inkjet printers.   The ink for an ink jet printer according to claim 1, wherein the silicone-based graft polymer is adsorbed within a range of 5 to 3000 parts by weight with respect to 100 parts by weight of the pigment.   The silicone-based graft polymer is dispersed in the form of particles in an organic solvent while adsorbed on the surface of the pigment, and the dispersion-average particle size of the silicone-based graft polymer adsorbing pigment is within a range of 0.01 to 0.3 μm. The ink for an ink jet printer according to claim 1, wherein: 2. The ink for an ink jet printer according to claim 1, wherein the pigment is selected from the group consisting of an inorganic pigment and an organic pigment .   6. The ink for an ink jet printer according to claim 1, wherein the pigment has a charge having an absolute value of ζ potential in a range of 10 to 300 mV.   The pigment is at least one pigment selected from the group consisting of organic pigments and carbon black, and the silicone-based graft polymer is adsorbed on at least a part of the outer surface of the pigment and 0 in the organic solvent. 6. The ink for an ink jet printer according to claim 5, wherein the ink is dispersed in the form of particles having a particle size in the range of 0.01 μm to 0.3 μm. The organic solvent is a low-polarity solvent and has an electric resistivity of 10 ⁹ Ω · cm or more, and the organic solvent is blended at a ratio in the range of 50 to 10,000 parts by weight with respect to 100 parts by weight of the pigment. The ink for an ink jet printer according to claim 1, wherein the ink is used.   The ink for an ink jet printer according to claim 1 or 8, wherein the organic solvent is a silicone organic solvent.   The ink for an inkjet printer according to claim 9, wherein the silicone-based organic solvent has a methylpolysiloxane and / or a cyclic methylpolysiloxane structure.   The ink for an inkjet printer according to claim 1, wherein the silicone-based graft polymer has a polar group.   The ink for an inkjet printer according to claim 11, wherein the polar group is selected from at least a carboxyl group, a hydroxyl group, and an amino group.   2. The ink for an ink jet printer according to claim 1, wherein an acid value of the silicone-based graft polymer is in a range of 5 to 100 KOH mg / g.   2. The ink for an ink jet printer according to claim 1, wherein the silicone-based graft polymer has a hydroxyl value in a range of 5 to 100 KOH mg / g.   2. The ink for an ink jet printer according to claim 1, wherein the silicone-based graft polymer has an amine value in the range of 5 to 100 KOH mg / g.   2. The ink for an ink jet printer according to claim 1, wherein the number average molecular weight of the silicone-based graft polymer is 2000 or more and 50000 or less.   2. The ink for an ink jet printer according to claim 1, wherein the silicone-based graft polymer is an acrylic polymer compound.   The ink for an inkjet printer according to claim 1, wherein the molecular weight of the graft portion of the silicone-based graft polymer is in the range of 500 to 10,000.   2. The ink for an ink jet printer according to claim 1, wherein the silicone-based graft polymer is crosslinked and further adsorbed on the pigment.   The ink for an ink jet printer according to claim 19, wherein the cross-linking is an ester bond.   The ink for an ink jet printer according to claim 1, wherein the silicone-based graft polymer has two or more functional groups for crosslinking capable of crosslinking with acidic groups.   The ink for an inkjet printer according to claim 21, wherein the functional group for crosslinking is a glycidyl group or a hydroxyl group.   An ink jet printer having a recording head having a plurality of ink discharge ports and energy conversion means for converting electrical energy into ink discharge energy corresponding to the plurality of discharge ports. Item 2. An ink for an ink jet printer according to Item 1.   From the group consisting of binders, organic solvents, anionic, cationic and nonionic surfactants, antiseptics, deodorants, anti-skinning agents, perfumes, pigment dispersants, pigment derivatives, leveling agents, charge control agents and wetting agents. The ink for an ink jet printer according to claim 1, further comprising at least one additional additive selected. 2. The ink for an ink jet printer according to claim 1, wherein the ink has a viscosity within a range of 1 to 20 mPa · s .