JP2005015671A - Nonaqueous inkjet ink - Google Patents
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- JP2005015671A JP2005015671A JP2003184061A JP2003184061A JP2005015671A JP 2005015671 A JP2005015671 A JP 2005015671A JP 2003184061 A JP2003184061 A JP 2003184061A JP 2003184061 A JP2003184061 A JP 2003184061A JP 2005015671 A JP2005015671 A JP 2005015671A
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【0001】
【発明の属する技術分野】本発明は、耐水性、耐光性、吐出性、定着性に優れた非水性インクジェットインキに関する。
【0002】
【従来の技術】従来、インクジェットインキとしては、酸性染料、直接染料、塩基性染料等の水溶性染料をグリコール系溶剤と水に溶解したもの(特許文献1、特許文献2、特許文献3)がよく用いられている。しかし、水溶性染料としては、インキの安定性を得るため、水に対する溶解性の高いものが一般的に用いられる。したがって、インクジェット記録物は、一般的に耐水性が悪く、水をこぼしたりすると容易に記録部分の染料のにじみを生じるという問題があった。
【0003】このような耐水性の不良を改良するため、染料の構造を変えたり、塩基性の強いインキを調製することが試みられている(特許文献4)。また、記録紙とインキとの反応をうまく利用して耐水性の向上を図ることも行われている(特許文献5、特許文献6、特許文献7、特許文献8)。これらの方法は、特定の記録紙については著しい効果をあげているが、記録紙の制約を受けるという点で汎用性に欠け、また特定の記録紙以外を用いた場合には、水溶性染料を使用するインキでは記録物の充分な耐水性が得られないことが多い。
【0004】また、耐水性の良好なインキとしては、油溶性染料を高沸点溶剤に分散ないし溶解したもの、油溶性染料を揮発性の溶剤に溶解したものがあるが、染料は耐光性等の諸耐性で顔料に劣るため、着色剤として顔料を用いたインキが望まれている。そして最近では顔料を用いたインキでも、流動パラフィンや脂肪族炭化水素などの難揮発性溶剤や、エタノール、メチルエチルケトン、酢酸エチルなどの揮発性溶剤に分散させたものが実用化されはじめている。しかし、難揮発性溶剤では被印刷物への印字後の乾燥性や定着性に問題が有り、揮発性溶剤ではノズルの乾燥といった問題を抱えている。
【0005】
【特許文献1】
特開昭53−614112号公報
【特許文献2】
特開昭54−89811号公報
【特許文献3】
特開昭55−65269号公報
【特許文献4】
特開昭56−57862号公報
【特許文献5】
特開昭50−49004号公報
【特許文献6】
特開昭57−36692号公報
【特許文献7】
特開昭59−20696号公報
【特許文献8】
特開昭59−146889号公報
【0006】
【発明が解決しようとする課題】本発明は、耐水性、耐光性、吐出性、定着性に優れた非水性インクジェットインキの提供を目的とする。
【0007】
【課題を解決するための手段】本発明者らは、種々の有機溶剤を非水性インクジェットインキとして検討した結果、特定の性質を有する有機溶剤を混合して使用することによって、耐水性、耐光性、吐出性に優れた非水性インクジェットインキが得られることを見出し、本発明に至った。
【0008】すなわち本発明は、少なくとも2種類以上の有機溶剤、顔料および樹脂からなる非水性インクジェットインキにおいて、有機溶剤として20℃の蒸気圧が0.3mmHg以上、かつ1気圧での沸点が140℃以上である有機溶剤A、および20℃の蒸気圧が0.3mmHg未満、かつ1気圧での沸点が250℃未満である有機溶剤Bを含むことを特徴とする非水性インクジェットインキに関する。
【0009】さらに本発明は、有機溶剤Aと有機溶剤Bの重量混合比が有機溶剤A:有機溶剤B=80:20〜5:95である上記非水性インクジェットインキに関する。
【0010】さらに本発明は、有機溶剤Aが下記一般式(1)、一般式(2)または一般式(3)で示される化合物から選ばれる少なくとも一種である上記非水性インクジェットインキに関する。
(式中、R1はエチレン基またはプロピレン基、R2は炭素数1〜4のアルキル基、R3は水素原子または炭素数1〜3のアルキル基、R4はメチル基、エチル基またはヒドロキシエチル基、R5は炭素数1〜8のアルキル基、nは1または2を表す。)
【0011】さらに本発明は、有機溶剤Bが下記一般式(4)または一般式(5)で示される化合物から選ばれる少なくとも一種である上記非水性インクジェットインキに関する。
(式中、R6はエチレン基またはプロピレン基、R7は炭素数1〜4のアルキル基、mは1〜3の整数を表す。)
【0012】さらに本発明は、分散剤を含む上記非水性インクジェットインキに関する。
【0013】
【発明の実施の形態】本発明に使用する有機溶剤は、20℃の蒸気圧が0.3mmHg以上、かつ1気圧での沸点が140℃以上である有機溶剤Aと、20℃の蒸気圧が0.3mmHg未満、かつ1気圧での沸点が250℃未満である有機溶剤Bを混合して使用するが、混合した有機溶剤の全体の性質としては、有機溶剤Aと有機溶剤Bの境となる20℃での蒸気圧0.3mmHgが非常に重要となる。この蒸気圧が0.3mmHgより高くなるにつれてインキ中の溶剤が揮発しやすくなり、沸点が140℃未満となるとノズル乾燥の危険性が著しく高くなる。また、蒸気圧が0.3mmHgより低くなるとインキ中の溶剤が揮発しにくくなり、沸点が250℃以上となると、印刷物が乾燥しなくなり、定着性も低下してしまう。
【0014】本発明ではこのような乾燥のバランスをとることが非常に重要であり、有機溶剤Aおよび有機溶剤Bの重量混合比は80:20〜5:95が好ましく、さらに好ましくは60:40〜20:80が良い。有機溶剤Aおよび有機溶剤Bのどちらか一方でインキを調製したとしてもインクジェットインキとしては好適ではない。
【0015】有機溶剤Aの具体例としては、酢酸ヘキシル、酢酸オクチル、プロピレングリコールモノメチルエーテルアセテート、プロピレングリコールモノエチルエーテルアセテート、ジエチレングリコールジメチルエーテル、ジエチレングリコールジエチルエーテル、シクロヘキサノン、乳酸プロピル、乳酸ブチル等があげられるが、20℃での蒸気圧が0.3mmHg以上、かつ1気圧での沸点が140℃以上であり、一般式(1)、一般式(2)、一般式(3)で表される有機溶剤であれば、この限りではない。また有機溶剤Aとしては、これらの有機溶剤を単独で使用しても、2種類以上使用しても良く、混合して使用した場合は粘度調整等の効果も期待できる。
【0016】有機溶剤Bの具体例としては、エチレングリコールモノブチルエーテルアセテート、ジエチレングリコールモノブチルエーテルアセテート、ジエチレングリコールモノエチルエーテルアセテート、プロピレングリコールモノブチルエーテル、ジプロピレングリコールモノメチルエーテル、トリプロピレングリコールモノメチルエーテル、ジエチレングリコールモノブチルエーテル等があげられるが、20℃の蒸気圧が0.3mmHg未満、かつ1気圧での沸点が250℃未満であり、一般式(4)、一般式(5)で表される有機溶剤であれば、この限りではない。また有機溶剤Bも、有機溶剤Aと同様に、これらの有機溶剤を単独で使用しても、2種類以上使用しても良く、混合して使用した場合は粘度調整等の効果も期待できる。
【0017】本発明に使用される顔料は、印刷インキ、塗料等に使用される種々の顔料が使用できる。このような顔料をカラーインデックスで示すと、ピグメントブラック7、ピグメントブルー15,15:1,15:3,15:4,15:6,60、ピグメントグリーン7,36、ピグメントレッド9,48,49,52,53,57,97,122,149,168,177,178,179,206,207,209,242,254,255、ピグメントバイオレット19,23,29,30,37,40,50、ピグメントイエロー12,13,14,17,20,24,74,83,86,93,94,95,109,110,117,120,125,128,137,138,139,147,148,150,151,154,155,166,168,180,185、ピグメントオレンジ36,43,51,55,59,61,71,74等があげられる。また、カーボンブラックについては中性、酸性、塩基性等のあらゆるカーボンブラックを使用することができる。
【0018】本発明では被印刷物への定着性を付与するために樹脂を添加する。使用できる樹脂としては、アクリル系樹脂、スチレン−アクリル系樹脂、スチレン−マレイン酸系樹脂、ロジン系樹脂、ロジンエステル系樹脂、エチレン−酢ビ系樹脂、石油樹脂、クマロンインデン系樹脂、テルペンフェノール系樹脂、フェノール樹脂、ウレタン樹脂、メラミン樹脂、尿素樹脂、エポキシ系樹脂、セルロース系樹脂、塩酢ビ系樹脂、キシレン樹脂、アルキッド樹脂、脂肪族炭化水素樹脂、ブチラール樹脂、マレイン酸樹脂、フマル酸樹脂等が挙げられる。樹脂の具体例としては、荒川化学社製のスーパーエステル75、エステルガムHP、マルキッド 33、安原社製のYS ポリスター T80、三井化学社製のHiretts HRT200X、ジョンソンポリマー社製のジョンクリル586、ダウケミカルズ社製のユーカーソリューションビニル樹脂VYHD、VYHH、VMCA等を例示することができる。
【0019】本発明に使用される分散剤は、水酸基含有カルボン酸エステル、長鎖ポリアミノアマイドと高分子量酸エステルの塩、高分子量ポリカルボン酸の塩、長鎖ポリアミノアマイドと極性酸エステルの塩、高分子量不飽和酸エステル、高分子共重合物、変性ポリウレタン、変性ポリアクリレート、ポリエーテルエステル型アニオン系活性剤、ナフタレンスルホン酸ホルマリン縮合物塩、芳香族スルホン酸ホルマリン縮合物塩、ポリオキシエチレンアルキルリン酸エステル、ポリオキシエチレンノニルフェニルエーテル、ステアリルアミンアセテート等を用いることができる。
【0020】分散剤の具体例としては、BYK Chemie社製「Anti−Terra−U(ポリアミノアマイド燐酸塩)」、「Anti−Terra−203/204(高分子量ポリカルボン酸塩)」、「Disperbyk−101(ポリアミノアマイド燐酸塩と酸エステル)、107(水酸基含有カルボン酸エステル)、110、111(酸基を含む共重合物)、130(ポリアマイド)、161、162、163、164、165、166、170(高分子共重合物)」、「400」、「Bykumen」(高分子量不飽和酸エステル)、「BYK−P104、P105(高分子量不飽和酸ポリカルボン酸)」、「P104S、240S(高分子量不飽和酸ポリカルボン酸とシリコン系)」、「Lactimon(長鎖アミンと不飽和酸ポリカルボン酸とシリコン)」が挙げられる。
【0021】また、Efka CHEMICALS社製「エフカ44、46、47、48、49、54、63、64、65、66、71、701、764、766」、「エフカポリマー100(変性ポリアクリレート)、150(脂肪族系変性ポリマー)、400、401、402、403、450、451、452、453(変性ポリアクリレート)、745(銅フタロシアニン系)」、共栄社化学社製「フローレン TG−710(ウレタンオリゴマー)、「フローノンSH−290、SP−1000」、「ポリフローNo.50E、No.300(アクリル系共重合物)」、楠本化成社製「ディスパロン KS−860、873SN、874(高分子分散剤)、#2150(脂肪族多価カルボン酸)、#7004(ポリエーテルエステル型)」が挙げられる。
【0022】さらに、花王社製「デモールRN、N(ナフタレンスルホン酸ホルマリン縮合物ナトリウム塩)、MS、C、SN−B(芳香族スルホン酸ホルマリン縮合物ナトリウム塩)、EP」、「ホモゲノールL−18(ポリカルボン酸型高分子)、「エマルゲン920、930、931、935、950、985(ポリオキシエチレンノニルフェニルエーテル)、「アセタミン24(ココナッツアミンアセテート)、86(ステアリルアミンアセテート)」、アビシア社製「ソルスパーズ5000(フタロシアニンアンモニウム塩系)、13940(ポリエステルアミン系)、17000(脂肪酸アミン系)、24000」、日光ケミカル社製「ニッコール T106(ポリオキシエチレンソルビタンモノオレート)、MYS−IEX(ポリオキシエチレンモノステアレート)、Hexagline 4−0(ヘキサグリセリルテトラオレート)」等が挙げられる。
【0023】分散剤は、インキ中での顔料の充分な分散安定性を得るため、インキ中に0.1〜10重量%含まれることが好ましい。
【0024】本発明の非水性インクジェットインキは印刷物の用途によって可塑剤、表面調整剤、紫外線防止剤、光安定化剤、酸化防止剤等の種々の添加剤を使用することができる。
【0025】本発明の非水性インクジェットインキは、まず有機溶剤A、または有機溶剤Bの単一もしくは混合溶剤に分散剤を溶解し、そこに顔料を投入して撹拌混合した後、横型サンドミル等の分散機によって顔料分散体を調製する。次に、得られた顔料分散体と樹脂とを有機溶剤A、または有機溶剤Bにてインクジェットインキとして適した粘度まで希釈溶解して製造される。使用する分散剤や樹脂の性質によって有機溶剤A、または有機溶剤Bの組み合わせを自由に選択することができる。すなわち、顔料の分散時には分散剤が溶解しやすく、顔料の湿潤性の良いものを使用し、希釈してインキを製造する際には樹脂の溶解性の良いものや被印刷物への適性の良いものを選択してより優れたインクジェットインキを製造することができる。
【0026】
【実施例】以下、実施例をあげて本発明を具体的に説明するが、本発明は実施例に特に限定されるものではない。なお、実施例中、「部」は「重量部」を表す。
【0027】[実施例1]有機溶剤Bとしてエチレングリコールモノブチルエーテルアセテート(沸点192℃、蒸気圧0.25mmHg)50部に、分散剤としてBYK Chemie社製「Disperbyk−111」15部を溶解し、顔料として東洋インキ製造社製「LIONOL BLUE FG−7351」35部を投入し、撹拌混合後、横型サンドミルを用いて4時間分散を行い、顔料分散体Aを得た。この顔料分散体Aを用いて下記のような配合にて有機溶剤と樹脂とを混合溶解し、定性濾紙No.5C(ADVANTEC社製)にて濾過してインクジェットインキを調製した。
【0028】[実施例2]有機溶剤Bとしてジエチレングリコールモノエチルエーテルアセテート(沸点217℃、0.05mmHg)50部、分散剤としてアビシア社製「ソルスパーズ24000」18部、顔料としてデグサ社製カーボンブラック「プリンテックス45」32部を撹拌混合後、横型サンドミルにて3時間分散して顔料分散体Bを得た。この顔料分散体Bを用いて下記のような配合にて有機溶剤と樹脂とを混合溶解し、定性濾紙No.5C(ADVANTEC社製)にて濾過してインクジェットインキを調製した。
【0029】[実施例3]有機溶剤Aとして乳酸ブチル(沸点188℃、0.4mmHg)42部、分散剤としてBYK Chemie社製「Disperbyk−111」20部、顔料としてクラリアント社製「HostapermYellow H4G」38部を撹拌混合後、横型サンドミルにて4時間分散して分散体Cを得た。この顔料分散体Cを用いて下記のような配合にて有機溶剤と樹脂とを混合溶解し、定性濾紙No.5C(ADVANTEC社製)にて濾過してインクジェットインキを調製した。
【0030】[実施例4]有機溶剤Aとして乳酸プロピル(沸点170℃、1.0mmHg)50部、分散剤としてアビシア社製「ソルスパーズ17000」15部、顔料としてチバスペシャルティーケミカルズ社製「Cromophtal Pink PT」35部を撹拌混合後、横型サンドミルにて3時間分散し、顔料分散体Dを得た。この顔料分散体Dを用いて下記のような配合にて有機溶剤と樹脂とを混合溶解し、定性濾紙No.5C(ADVANTEC社製)にて濾過してインクジェットインキを調製した。
【0031】[比較例1]実施例1で作成した顔料分散体Aを用いて下記のような配合にて有機溶剤と樹脂とを混合溶解し、定性濾紙No.5C(ADVANTEC社製)にて濾過してインクジェットインキを調製した。
【0032】[比較例2]実施例2で作成した顔料分散体Bを用いて下記のような配合にて有機溶剤と樹脂とを混合溶解し、定性濾紙No.5C(ADVANTEC社製)にて濾過してインクジェットインキを調製した。
【0033】[比較例3]実施例3で作成した顔料分散体Cを用いて下記のような配合にて有機溶剤と樹脂とを混合溶解し、定性濾紙No.5C(ADVANTEC社製)にて濾過してインクジェットインキを調製した。
【0034】[比較例4]実施例4で作成した顔料分散体Dを用いて下記のような配合にて有機溶剤と樹脂とを混合溶解し、定性濾紙No.5C(ADVANTEC社製)にて濾過してインクジェットインキを調製した。
【0035】実施例1〜4、比較例1〜4で得られた非水性インクジェットインキについて、次のような項目について評価した。(1)粘度、(2)保存安定性、(3)吐出性、(4)乾燥性、(5)定着性、(6)耐水性。それぞれの測定法を以下に示す。
【0036】(1)粘度:インキを25℃に調製し、ビスコメイトVM−100A(山一電機製、超音波振動式粘度計)にて測定した。
【0037】(2)保存安定性:インキをポリプロピレン製のボトル型容器に入れ、70℃の恒温機に2週間保存、経時促進させた後、経時前後でのインキの粘度変化について測定した。この時の粘度測定は(1)の粘度測定と同様の方法で実施した。粘度の変化率が±10%以内なら○、±10%を越えたら×とした。
【0038】(3)吐出性:インキをIP−6500(セイコーアイ・インフォテック社製、大判インクジェットプリンタ)にて光沢塩ビシートMD5(メタマーク社製)に5m連続記録し、ドット抜けを観察。ドット抜けしたノズルの数が全ノズルに対して何%あるかについて、0%の場合は○、0%〜5%の場合は△、5%より多い場合は×とした。
【0039】(4)乾燥性:インキをIP−6500(セイコーアイ・インフォテック社製、大判インクジェットプリンタ)にて光沢塩ビシートMD5(メタマーク社製)にベタ印字し、印字面を指で触り、インキが指に付着しなくなる時間によって評価。印字の際、プリンタに設置されたヒーターの温度は、プリンタヘッドの手前を35℃、プリンタヘッドの後部(印字後の乾燥部分)を40℃として評価した。印字直後にインキが付着しなければ○、印字直後にインキが付着しても、10分後にインキが付着しなくなっていれば△、10分以上経過してもインキが付着するものは×とした。
【0040】(5)定着性:インキをIP−6500(セイコーアイ・インフォテック社製、大判インクジェットプリンタ)にて光沢塩ビシートMD5(メタマーク社製)にベタ印字し、記録物を40℃で3分間乾燥させ、ラビングテスター(テスター産業製、型式AB301)にて試験用布片(金巾3号)にて加重200g、100往復のラビング試験を塩ビシートの印字面にて実施した。試験用布片にインキが全く付着しないものを○、試験用布片にインキがやや付着するが、塩ビシートの印字面の濃度が殆ど変化しないものは△、塩ビシートの印字面のインキも殆ど剥がれてしまうものは×とした。
【0041】(6)耐水性:インキをIP−6500(セイコーアイ・インフォテック社製、大判インクジェットプリンタ)にて光沢塩ビシートMD5(メタマーク社製)にベタ印字し、記録物を40℃で3分間乾燥させた後、塩ビシートを1分間水道水に浸漬し、指で印字面を擦ってインキが全く剥がれなければ○、インキが剥がれてしまえば×とした。
【0042】実施例1〜4、比較例1〜4の溶剤組成、および評価結果を下記の表1にまとめた。
【0043】
【表1】
【0044】実施例1〜4のインキは保存安定性、吐出性、乾燥性、定着性、耐水性の全ての評価項目において良好な結果が得られたが、比較例1〜4のインキは乾燥性のバランスが悪く、吐出性が悪化するものや、殆ど乾燥しないインキとなってしまった。
【0045】
【発明の効果】本発明により、耐水性、耐光性、吐出性、定着性に優れた非水性インクジェットインキを提供することができた。[0001]
BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a non-aqueous ink jet ink excellent in water resistance, light resistance, ejection property and fixing property.
[0002]
2. Description of the Related Art Conventional ink-jet inks include water-soluble dyes such as acid dyes, direct dyes, and basic dyes dissolved in a glycol solvent and water (Patent Document 1, Patent Document 2, and Patent Document 3). It is often used. However, water-soluble dyes that are highly soluble in water are generally used in order to obtain ink stability. Therefore, the ink-jet recorded matter generally has poor water resistance, and there is a problem that when the water is spilled, the dye in the recorded portion easily bleeds.
[0003] In order to improve such poor water resistance, attempts have been made to change the structure of the dye or to prepare a highly basic ink (Patent Document 4). In addition, water resistance is improved by making good use of the reaction between recording paper and ink (Patent Document 5, Patent Document 6, Patent Document 7, and Patent Document 8). Although these methods have a remarkable effect for specific recording paper, they are not versatile in that they are restricted by the recording paper, and when other than specific recording paper is used, a water-soluble dye is used. Ink used often does not provide sufficient water resistance of recorded matter.
In addition, examples of inks having good water resistance include those obtained by dispersing or dissolving oil-soluble dyes in high-boiling solvents, and those obtained by dissolving oil-soluble dyes in volatile solvents. Since various resistances are inferior to pigments, inks using pigments as colorants are desired. Recently, even inks using pigments have been put into practical use in which they are dispersed in volatile solvents such as liquid paraffin and aliphatic hydrocarbons, and volatile solvents such as ethanol, methyl ethyl ketone, and ethyl acetate. However, a hardly volatile solvent has a problem in drying and fixing properties after printing on a printing material, and a volatile solvent has a problem of drying a nozzle.
[0005]
[Patent Document 1]
JP-A-53-614112 [Patent Document 2]
JP-A-54-89811 [Patent Document 3]
JP-A-55-65269 [Patent Document 4]
JP-A-56-57862 [Patent Document 5]
JP 50-49004 A [Patent Document 6]
JP 57-36692 A [Patent Document 7]
JP 59-20696 [Patent Document 8]
Japanese Patent Laid-Open No. 59-146889
SUMMARY OF THE INVENTION An object of the present invention is to provide a non-aqueous ink jet ink which is excellent in water resistance, light resistance, dischargeability and fixability.
[0007]
As a result of studying various organic solvents as non-aqueous ink-jet inks, the present inventors have found that water resistance and light resistance can be obtained by using a mixture of organic solvents having specific properties. The present inventors have found that a non-aqueous inkjet ink excellent in dischargeability can be obtained, and have reached the present invention.
That is, the present invention is a non-aqueous ink jet ink composed of at least two kinds of organic solvents, pigments and resins, and the organic solvent has a vapor pressure of 20 ° C. of 0.3 mmHg or more and a boiling point of 140 ° C. at 1 atm. The present invention relates to a non-aqueous inkjet ink comprising the organic solvent A as described above and an organic solvent B having a vapor pressure of less than 0.3 mmHg at 20 ° C. and a boiling point of less than 250 ° C. at 1 atm.
The present invention further relates to the above non-aqueous ink-jet ink wherein the weight mixing ratio of the organic solvent A and the organic solvent B is organic solvent A: organic solvent B = 80: 20 to 5:95.
The present invention further relates to the above non-aqueous ink-jet ink wherein the organic solvent A is at least one selected from the compounds represented by the following general formula (1), general formula (2) or general formula (3).
(Wherein R 1 is an ethylene group or propylene group, R 2 is an alkyl group having 1 to 4 carbon atoms, R 3 is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, R 4 is a methyl group, an ethyl group or a hydroxy group) An ethyl group, R 5 represents an alkyl group having 1 to 8 carbon atoms, and n represents 1 or 2.)
The present invention further relates to the above non-aqueous ink-jet ink wherein the organic solvent B is at least one selected from the compounds represented by the following general formula (4) or general formula (5).
(In the formula, R 6 represents an ethylene group or a propylene group, R 7 represents an alkyl group having 1 to 4 carbon atoms, and m represents an integer of 1 to 3).
The present invention further relates to the above non-aqueous ink-jet ink containing a dispersant.
[0013]
BEST MODE FOR CARRYING OUT THE INVENTION The organic solvent used in the present invention has an organic solvent A having a vapor pressure at 20 ° C. of 0.3 mmHg or more and a boiling point at 1 atm of 140 ° C. or more, and a vapor pressure at 20 ° C. An organic solvent B having a boiling point of less than 0.3 mmHg and a boiling point of less than 250 ° C. at less than 250 ° C. is used as a mixture. The entire property of the mixed organic solvent is a boundary between the organic solvent A and the organic solvent B. A vapor pressure of 0.3 mmHg at 20 ° C. is very important. As the vapor pressure becomes higher than 0.3 mmHg, the solvent in the ink tends to volatilize, and when the boiling point is less than 140 ° C., the risk of nozzle drying becomes extremely high. Further, when the vapor pressure is lower than 0.3 mmHg, the solvent in the ink is less likely to volatilize, and when the boiling point is 250 ° C. or higher, the printed matter is not dried and the fixability is also lowered.
In the present invention, it is very important to balance such drying, and the weight mixing ratio of the organic solvent A and the organic solvent B is preferably 80:20 to 5:95, more preferably 60:40. ~ 20: 80 is good. Even if the ink is prepared with either the organic solvent A or the organic solvent B, it is not suitable as an inkjet ink.
Specific examples of the organic solvent A include hexyl acetate, octyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, cyclohexanone, propyl lactate and butyl lactate. An organic solvent represented by the general formula (1), the general formula (2), or the general formula (3) having a vapor pressure at 20 ° C. of 0.3 mmHg or more and a boiling point at 1 atm of 140 ° C. or more. This is not the case, if any. In addition, as the organic solvent A, these organic solvents may be used alone or in combination of two or more. When mixed and used, effects such as viscosity adjustment can be expected.
Specific examples of the organic solvent B include ethylene glycol monobutyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, diethylene glycol monobutyl ether, and the like. However, if the vapor pressure at 20 ° C. is less than 0.3 mmHg, the boiling point at 1 atm is less than 250 ° C., and the organic solvent is represented by general formula (4) or general formula (5), This is not the case. Moreover, the organic solvent B may use these organic solvents individually or may be used two or more types similarly to the organic solvent A, and when mixed and used, effects such as viscosity adjustment can be expected.
As the pigment used in the present invention, various pigments used in printing inks, paints and the like can be used. When these pigments are represented by color index, Pigment Black 7, Pigment Blue 15, 15: 1, 15: 3, 15: 4, 15: 6, 60, Pigment Green 7, 36, Pigment Red 9, 48, 49 , 52, 53, 57, 97, 122, 149, 168, 177, 178, 179, 206, 207, 209, 242, 254, 255, pigment violet 19, 23, 29, 30, 37, 40, 50, pigment Yellow 12, 13, 14, 17, 20, 24, 74, 83, 86, 93, 94, 95, 109, 110, 117, 120, 125, 128, 137, 138, 139, 147, 148, 150, 151 , 154, 155, 166, 168, 180, 185, pigment orange 36, 43, 51, 55, 59 61,71,74, and the like. As for carbon black, any carbon black such as neutral, acidic and basic can be used.
In the present invention, a resin is added in order to impart fixability to the substrate. Usable resins include acrylic resin, styrene-acrylic resin, styrene-maleic resin, rosin resin, rosin ester resin, ethylene-vinyl acetate resin, petroleum resin, coumarone indene resin, terpene phenol Resin, phenol resin, urethane resin, melamine resin, urea resin, epoxy resin, cellulose resin, vinyl acetate resin, xylene resin, alkyd resin, aliphatic hydrocarbon resin, butyral resin, maleic acid resin, fumaric acid Examples thereof include resins. Specific examples of the resin include Superester 75 manufactured by Arakawa Chemical Co., Ltd., Ester Gum HP, Malkid 33, YS Polystar T80 manufactured by Yasuhara Co., Ltd., Hirtts HRT200X manufactured by Mitsui Chemicals, Inc., John Crill 586 manufactured by Johnson Polymer Co., Ltd., Dow Chemicals For example, Uker solution vinyl resins VYHD, VYHH, VMCA and the like manufactured by the company can be exemplified.
The dispersant used in the present invention includes a hydroxyl group-containing carboxylic acid ester, a salt of a long-chain polyaminoamide and a high molecular weight acid ester, a salt of a high molecular weight polycarboxylic acid, a salt of a long chain polyaminoamide and a polar acid ester, High molecular weight unsaturated acid ester, high molecular weight copolymer, modified polyurethane, modified polyacrylate, polyether ester type anionic activator, naphthalenesulfonic acid formalin condensate salt, aromatic sulfonic acid formalin condensate salt, polyoxyethylene alkyl Phosphate ester, polyoxyethylene nonylphenyl ether, stearylamine acetate and the like can be used.
Specific examples of the dispersant include "Anti-Terra-U (polyaminoamide phosphate)", "Anti-Terra-203 / 204 (high molecular weight polycarboxylate)" manufactured by BYK Chemie, "Disperbyk- 101 (polyaminoamide phosphate and acid ester), 107 (hydroxyl group-containing carboxylic acid ester), 110, 111 (copolymer containing an acid group), 130 (polyamide), 161, 162, 163, 164, 165, 166, 170 (polymer copolymer) "," 400 "," Bykumen "(high molecular weight unsaturated acid ester)," BYK-P104, P105 (high molecular weight unsaturated acid polycarboxylic acid) "," P104S, 240S (high Molecular weight unsaturated acid polycarboxylic acid and silicon system ”,“ Lactimon (long chain amine and Saturated acid polycarboxylic acid and silicon) ”.
Further, "Efka CHEMICALS""Efka 44, 46, 47, 48, 49, 54, 63, 64, 65, 66, 71, 701, 764, 766", "Efka Polymer 100 (modified polyacrylate), 150" (Aliphatic modified polymer), 400, 401, 402, 403, 450, 451, 452, 453 (modified polyacrylate), 745 (copper phthalocyanine-based) "," Floren TG-710 (urethane oligomer) "manufactured by Kyoeisha Chemical Co., Ltd. , “Flonon SH-290, SP-1000”, “Polyflow No. 50E, No. 300 (acrylic copolymer)”, “Disparon KS-860, 873SN, 874 (polymer dispersing agent) manufactured by Enomoto Kasei Co., Ltd. # 2150 (aliphatic polycarboxylic acid), # 7004 (polyether ester type) "And the like.
Further, "Demol RN, N (Naphthalenesulfonic acid formalin condensate sodium salt), MS, C, SN-B (aromatic sulfonic acid formalin condensate sodium salt), EP", "Homogenol L-" manufactured by Kao Corporation. 18 (polycarboxylic acid type polymer), “Emulgen 920, 930, 931, 935, 950, 985 (polyoxyethylene nonylphenyl ether)”, “Acetamine 24 (coconut amine acetate), 86 (stearyl amine acetate)”, Avicia "Solspers 5000 (phthalocyanine ammonium salt type), 13940 (polyesteramine type), 17000 (fatty acid amine type), 24000" manufactured by Nikko Chemical Co., Ltd. "Nikkor T106 (polyoxyethylene sorbitan monooleate), MYS-IEX (Polyester)" Reoxyethylene monostearate), Hexagline 4-0 (hexaglyceryl tetraoleate) "and the like.
The dispersant is preferably contained in the ink in an amount of 0.1 to 10% by weight in order to obtain sufficient dispersion stability of the pigment in the ink.
In the non-aqueous ink jet ink of the present invention, various additives such as a plasticizer, a surface conditioner, an ultraviolet ray inhibitor, a light stabilizer and an antioxidant can be used depending on the use of the printed matter.
In the non-aqueous ink jet ink of the present invention, first, a dispersant is dissolved in a single solvent or a mixed solvent of an organic solvent A or an organic solvent B, a pigment is added thereto, and the mixture is stirred and mixed. A pigment dispersion is prepared by a disperser. Next, the obtained pigment dispersion and resin are diluted and dissolved in an organic solvent A or an organic solvent B to a viscosity suitable as an inkjet ink. The combination of the organic solvent A or the organic solvent B can be freely selected depending on the properties of the dispersant and resin used. In other words, when the pigment is dispersed, the dispersant is easy to dissolve, and the pigment has good wettability. When diluted to produce ink, the resin has good solubility and is suitable for printing. A more excellent ink-jet ink can be produced by selecting.
[0026]
EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not particularly limited to the examples. In the examples, “part” represents “part by weight”.
Example 1 In an organic solvent B, 50 parts of ethylene glycol monobutyl ether acetate (boiling point 192 ° C., vapor pressure 0.25 mmHg) and 15 parts of “Disperbyk-111” manufactured by BYK Chemie as a dispersant were dissolved. 35 parts of “LIONOL BLUE FG-7351” manufactured by Toyo Ink Manufacturing Co., Ltd. was added as a pigment, stirred and mixed, and then dispersed for 4 hours using a horizontal sand mill to obtain Pigment Dispersion A. Using this pigment dispersion A, an organic solvent and a resin were mixed and dissolved in the following composition. The ink was filtered through 5C (manufactured by ADVANTEC) to prepare an inkjet ink.
[Example 2] 50 parts of diethylene glycol monoethyl ether acetate (boiling point 217 ° C., 0.05 mmHg) as the organic solvent B, 18 parts of “Solspers 24000” manufactured by Avisia as a dispersant, and carbon black “available from Degussa as a pigment” 32 parts of Printex 45 "was stirred and mixed, and then dispersed in a horizontal sand mill for 3 hours to obtain Pigment Dispersion B. Using this pigment dispersion B, an organic solvent and a resin were mixed and dissolved in the following composition. The ink was filtered through 5C (manufactured by ADVANTEC) to prepare an inkjet ink.
Example 3 42 parts of butyl lactate (boiling point 188 ° C., 0.4 mmHg) as the organic solvent A, 20 parts of “Disperbyk-111” manufactured by BYK Chemie, and “Hostaperm Yellow H4G” manufactured by Clariant as the pigment After stirring and mixing 38 parts, dispersion C was obtained by dispersing for 4 hours in a horizontal sand mill. Using this pigment dispersion C, an organic solvent and a resin were mixed and dissolved in the following composition. The ink was filtered through 5C (manufactured by ADVANTEC) to prepare an inkjet ink.
Example 4 50 parts of propyl lactate (boiling point: 170 ° C., 1.0 mmHg) as organic solvent A, 15 parts of “Solspers 17000” manufactured by Avisia as a dispersant, and “Chrophtal Pink” manufactured by Ciba Specialty Chemicals as a pigment. 35 parts of “PT” was stirred and mixed, and then dispersed in a horizontal sand mill for 3 hours to obtain Pigment Dispersion D. Using this pigment dispersion D, an organic solvent and a resin were mixed and dissolved in the following composition. The ink was filtered through 5C (manufactured by ADVANTEC) to prepare an inkjet ink.
[Comparative Example 1] Using Pigment Dispersion A prepared in Example 1, an organic solvent and a resin were mixed and dissolved in the following composition. The ink was filtered through 5C (manufactured by ADVANTEC) to prepare an inkjet ink.
[Comparative Example 2] Using the pigment dispersion B prepared in Example 2, an organic solvent and a resin were mixed and dissolved in the following composition. The ink was filtered through 5C (manufactured by ADVANTEC) to prepare an inkjet ink.
[Comparative Example 3] Using Pigment Dispersion C prepared in Example 3, an organic solvent and a resin were mixed and dissolved in the following composition. The ink was filtered through 5C (manufactured by ADVANTEC) to prepare an inkjet ink.
[Comparative Example 4] Using the pigment dispersion D prepared in Example 4, an organic solvent and a resin were mixed and dissolved in the following composition. The ink was filtered through 5C (manufactured by ADVANTEC) to prepare an inkjet ink.
The following items were evaluated for the non-aqueous inkjet inks obtained in Examples 1 to 4 and Comparative Examples 1 to 4. (1) Viscosity, (2) Storage stability, (3) Ejectability, (4) Dryability, (5) Fixability, (6) Water resistance. Each measurement method is shown below.
(1) Viscosity: The ink was prepared at 25 ° C. and measured with Viscomate VM-100A (manufactured by Yamaichi Denki, ultrasonic vibration viscometer).
(2) Storage stability: The ink was placed in a polypropylene bottle-type container, stored in a thermostat at 70 ° C. for 2 weeks, and allowed to accelerate with time, and the change in viscosity of the ink before and after aging was measured. The viscosity measurement at this time was carried out by the same method as the viscosity measurement of (1). If the rate of change in viscosity was within ± 10%, it was rated as ○, and if it exceeded ± 10%, it was marked as ×.
(3) Dischargeability: Ink was recorded continuously for 5 m on glossy vinyl chloride sheet MD5 (made by Metamark) using IP-6500 (manufactured by Seiko I Infotech, large format ink jet printer), and dot missing was observed. Regarding the percentage of the number of missing nozzles with respect to all the nozzles, it was evaluated as 0 for 0%, Δ for 0% to 5%, and x for more than 5%.
(4) Drying property: The ink is solid-printed on glossy PVC sheet MD5 (made by Metamark) using IP-6500 (manufactured by Seiko I Infotech, large format ink jet printer), and the printed surface is touched with a finger. Evaluation is based on the time that ink does not adhere to fingers. During printing, the temperature of the heater installed in the printer was evaluated as 35 ° C. before the printer head and 40 ° C. at the rear of the printer head (the dried portion after printing). ◯ if ink does not adhere immediately after printing, △ if ink does not adhere after 10 minutes even if ink adheres immediately after printing .
(5) Fixability: The ink was solid-printed on glossy PVC sheet MD5 (made by Metamark) with IP-6500 (manufactured by Seiko I Infotech, large format ink jet printer), and the recorded matter was printed at 40 ° C. It was dried for a minute, and a rubbing test with a load of 200 g and 100 reciprocations was carried out on the printed surface of the PVC sheet with a test cloth (gold width 3) using a rubbing tester (model AB301, manufactured by Tester Sangyo). ○ when ink does not adhere to the test cloth at all, ink adheres slightly to the test cloth, but when the density of the printed surface of the PVC sheet hardly changes, △, and most of the ink on the printed surface of the PVC sheet What peeled off was set as x.
(6) Water resistance: The ink was solid-printed on glossy PVC sheet MD5 (made by Metamark) using IP-6500 (manufactured by Seiko I Infotech, large format ink jet printer), and the recorded matter was printed at 40 ° C. After drying for a minute, the vinyl chloride sheet was immersed in tap water for 1 minute, and the print surface was rubbed with a finger to indicate that the ink was not removed at all.
The solvent compositions and evaluation results of Examples 1 to 4 and Comparative Examples 1 to 4 are summarized in Table 1 below.
[0043]
[Table 1]
The inks of Examples 1 to 4 gave good results in all the evaluation items of storage stability, dischargeability, drying property, fixing property and water resistance, but the inks of Comparative Examples 1 to 4 were dried. The ink balance was poor, and the ink jetting property deteriorated or the ink hardly dried.
[0045]
According to the present invention, a non-aqueous ink-jet ink excellent in water resistance, light resistance, dischargeability and fixability can be provided.
Claims (5)
(式中、R1はエチレン基またはプロピレン基、R2は炭素数1〜4のアルキル基、R3は水素原子または炭素数1〜3のアルキル基、R4はメチル基、エチル基またはヒドロキシエチル基、R5は炭素数1〜8のアルキル基、nは1または2を表す。)The non-aqueous inkjet ink according to claim 1 or 2, wherein the organic solvent A is at least one selected from compounds represented by the following general formula (1), general formula (2), or general formula (3).
(Wherein R 1 is an ethylene group or propylene group, R 2 is an alkyl group having 1 to 4 carbon atoms, R 3 is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, R 4 is a methyl group, an ethyl group or a hydroxy group) An ethyl group, R 5 represents an alkyl group having 1 to 8 carbon atoms, and n represents 1 or 2.)
(式中、R6はエチレン基またはプロピレン基、R7は炭素数1〜4のアルキル基、mは1〜3の整数を表す。)The non-aqueous inkjet ink according to any one of claims 1 to 3, wherein the organic solvent B is at least one selected from the compounds represented by the following general formula (4) or general formula (5).
(In the formula, R 6 represents an ethylene group or a propylene group, R 7 represents an alkyl group having 1 to 4 carbon atoms, and m represents an integer of 1 to 3).
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JP2008233435A (en) * | 2007-03-19 | 2008-10-02 | Seiko Epson Corp | Ink for color filter, color filter, image display device and electronic equipment |
WO2015046555A1 (en) * | 2013-09-30 | 2015-04-02 | 大日本塗料株式会社 | Metallic ink composition for inkjet printing for polyvinyl chloride substrate |
JP2015067767A (en) * | 2013-09-30 | 2015-04-13 | 大日本塗料株式会社 | Metallic ink composition for inkjet printing for polyvinyl chloride substrate |
US10023754B2 (en) | 2013-09-30 | 2018-07-17 | Dai Nippon Toryo Co., Ltd. | Metallic ink composition for inkjet printing for polyvinyl chloride substrate |
JP2015071681A (en) * | 2013-10-02 | 2015-04-16 | 東洋インキScホールディングス株式会社 | Solvent-based inkjet ink |
US9783689B2 (en) | 2013-10-02 | 2017-10-10 | Toyo Ink Sc Holdings Co., Ltd. | Solvent-based inkjet ink |
JP2015134934A (en) * | 2015-03-30 | 2015-07-27 | 大日本塗料株式会社 | Metallic ink composition for inkjet printing for polyvinyl chloride substrate |
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