JP3895533B2 - Ink jet recording material and method for producing the same - Google Patents

Description

式中、ＸはＯまたはＮを表し、Ｙは炭素数２〜６の線状橋かけ基を表す。Ｒ₁、Ｒ₂は独立してＨ、炭素数１〜１０の置換または無置換のアルキル基を表す。Ｚは(ＮＲ₃Ｒ₄Ｒ₅)⁺であり、ｎは０〜２の整数を表す。Ｒ₃、Ｒ₄、Ｒ₅は独立してＨまたは炭素数１〜４のアルキル基を表す。
【００３４】
一般式１で好ましくは、Ｘ−Ｙ−Ｏで乳酸、グリコール酸、リンゴ酸、クエン酸、酒石酸、糖酸、グルコン酸、グリセリン酸、またはマンデル酸の構造を形成する場合である。
【００３５】
チタンキレート化合物の具体例としては、ジヒドロキシビス（ラクタト）チタン、ジヒドロキシビス（ラクタト）チタンのモノアンモニウム塩、ジヒドロキシビス（ラクタト）チタンのジアンモニウム塩、ジイソプロポキシビス（ラクタト）チタン、ジヒドロキシビス（マラト）チタン、ジイソプロポキシビス（メチルラクタト）チタン、ジイソプロポキシビス（エチルラクタト）チタン、ジイソプロポキシビス（ｎ−プロピルラクタト）チタン、ジイソブトキシビス（メチルラクタト）チタン、ジイソプロポキシビス（アセチルアセトナト）チタン、ジイソプロポキシ（２−エチル−１，３−ヘキサンジオラト）チタン、ジ−ｎ−ブトキシビス（トリエタノールアミナト）チタン、オキソビス（ラクタト）チタン、オキソビス（モノアンモニウムオキザラト）チタン等が挙げられる。
【００３６】
チタンキレート化合物は、合成して使用しても良いが、市販品を好適に使用することができる。以下に代表的な市販品の例を挙げるが、本発明がこれらに限定されるものではない。例えば、オルガチックスＴＣ−３００、オルガチックスＴＣ−３１０、オルガチックスＴＣ−４００（以上、（株）マツモト交商）、Ｔ−５０、ＴＬＡ−Ａ−５０、ＴＬＡ−ＡＡ−５０、ＴＯＡ−３０、ＴＡＴ（以上、日本曹達（株））、ＴＡＡ、ＴＥＡＡ（以上、三菱ガス化学（株））等を挙げることができる。
【００３７】
特開２０００−４３４０３号公報には、インク受理層にチタニウムラクテート化合物やチタニウムグリコレート化合物を含有し、ファイル保管時や粘着テープ貼付時の白紙部黄変を改良したインクジェット記録用紙が開示されている。しかし、気相法シリカを非吸水性支持体上等に多量に塗布する場合や親水性バインダー量を少なくした場合に問題となるインク受容層のひび割れや表面剥離についての記載はない。
【００３８】
チタンキレート化合物のインク受容層中の含有量は、気相法シリカ、または気相法シリカと他の顔料を併用している場合には顔料全体に対して０．０１〜１０重量％、好ましくは０．１〜５重量％である。チタンキレート化合物の含有量が０．０１重量％未満では、チタンキレート化合物によるインク受容層表面のひび割れ、防止、表面光沢、表面剥離性、インク吸収性改善の効果が十分ではない。また、１０重量％より多くの量を含有させると、かえって表面光沢、表面剥離性、インク吸収性が低下したり、画像が変色し色再現性が低下したりすることがある。
【００３９】
チタンキレート化合物をインク受容層に含有させる方法としては、インク受容層塗布液中にチタンキレート化合物を含有させて塗布する方法、インク受容層塗布液とチタンキレート化合物含有塗布液を別層として同時塗布する方法、インク受容層を塗布した後、乾燥前にチタンキレート化合物含有液を噴霧あるいは上塗りすることによってインク受容層にチタンキレート化合物を浸透させる方法等がある。好ましくは、インク受容層塗布液中にチタンキレート化合物を含有させて塗布する方法である。
【００４０】
インク受容層塗布液中にチタンキレート化合物を含有させる場合、チタンキレート化合物は塗布前であればどの段階で塗布液に添加しても構わないが、本発明者らが添加方法、添加順序等を検討した結果、まず気相法シリカとチタンキレート化合物を含有する分散液を作成し、次に親水性バインダーと混合することによって、インク受容層表面のひび割れ、表面光沢が更に改良されることを見出した。この時、気相法シリカとチタンキレート化合物を含有する分散液は、気相法シリカとチタンキレート化合物を混合後、気相法シリカの説明で挙げた分散機で分散して製造しても良いし、予め分散機を用いて製造した気相法シリカ分散液とチタンキレート化合物を混合して製造しても良い。
【００４１】
特に、予め分散機を用いて製造した気相法シリカ分散液とチタンキレート化合物を混合して分散液を作成する場合、気相法シリカ分散液とチタンキレート化合物を混合後、２０〜７０℃で１０分〜２４時間撹拌した後、親水性バインダーと混合することにより、ひび割れ、表面光沢がより向上する。この時、好ましくは３０〜６０℃で１〜１２時間撹拌する。温度が２０℃よりも低いと、塗布液が高粘度となり撹拌が困難となる場合があり、７０℃を越えると塗布液からの水分蒸発が激しくなり好ましくない。また撹拌時間が１０分以下では撹拌の効果が十分ではなく、２４時間を超えると、理由は定かではないが、インク受容層表面のひび割れ、光沢がかえって低下する。この時の撹拌方法としては、高剪断あるいは高速撹拌の必要はなく、公知の方法を使用することができる。例えば、マグネチックスターラー、メカニカルスターラー、プロペラ撹拌機、タービン式撹拌機、ディスパー、ホモミキサー等を使用することができる。
【００４２】
本発明のインク受容層は、カチオン性化合物を含有するのが好ましい。本発明に用いられるカチオン性化合物としては、耐水性改良の目的で用いられるカチオン性化合物が挙げられ、例えばカチオン性ポリマーや水溶性金属化合物が挙げられる。
【００４３】
カチオン性ポリマーとしては、ポリエチレンイミン、ポリジアリルアミン、ポリアリルアミン、特開昭５９−２０６９６号、同５９−３３１７６号、同５９−３３１７７号、同５９−１５５０８８号、同６０−１１３８９号、同６０−４９９９０号、同６０−８３８８２号、同６０−１０９８９４号、同６２−１９８４９３号、同６３−４９４７８号、同６３−１１５７８０号、同６３−２８０６８１号、特開平１−４０３７１号、同６−２３４２６８号、同７−１２５４１１号、同１０−１９３７７６号公報等に記載された１〜３級アミノ基、４級アンモニウム塩基を有するポリマーが好ましく用いられる。これらのカチオン性ポリマーの分子量は、５，０００以上が好ましく、更に５，０００〜１０万程度が好ましい。
【００４４】
これらのカチオン性ポリマーの使用量は無機微粒子に対して１〜１０重量％、好ましくは２〜８重量％である。
【００４５】
また、カチオン性化合物として、無機系の含アルミニウムカチオンポリマーである塩基性ポリ水酸化アルミニウム化合物が挙げられる。塩基性ポリ水酸化アルミニウム化合物とは、主成分が下記の一般式１、２又は３で示され、例えば［Ａｌ₆（ＯＨ）₁₅］³⁺、［Ａｌ₈（ＯＨ）₂₀］⁴⁺、［Ａｌ₁₃（ＯＨ）₃₄］⁵⁺、［Ａｌ₂₁（ＯＨ）₆₀］³⁺、等のような塩基性で高分子の多核縮合イオンを安定に含んでいる水溶性のポリ水酸化アルミニウムである。
【００４６】
［Ａｌ₂（ＯＨ）_nＣｌ_6-n］_m ・・式１
［Ａｌ（ＯＨ）₃］_nＡｌＣｌ₃ ・・式２
Ａｌ_n（ＯＨ）_mＣｌ_(3n-m) ０＜ｍ＜３ｎ ・・式３
【００４７】
これらのものは多木化学（株）よりポリ塩化アルミニウム（ＰＡＣ）の名で水処理剤として、浅田化学（株）よりポリ水酸化アルミニウム（Ｐａｈｏ）の名で、また、（株）理研グリーンよりピュラケムＷＴの名で、また他のメーカーからも同様の目的を持って上市されており、各種グレードの物が容易に入手できる。本発明ではこれらの市販品をそのままでも使用できるが、ｐＨが不適当に低い物もあり、その場合は適宜ｐＨを調節して用いることも可能である。
【００４８】
本発明において、上記水溶性の金属化合物のインク受容層中の含有量は、０．１ｇ／m²〜１０ｇ／m²、好ましくは０．２ｇ／m²〜５ｇ／m²である。
【００４９】
上記したカチオン性化合物は２種以上を併用することができる。例えば、カチオン性ポリマーと含アルミニウムカチオンポリマーを併用してもよい。
【００５０】
本発明におけるインク受容層は、皮膜の脆弱性を改良するために各種油滴を含有することが好ましいが、そのような油滴としては室温における水に対する溶解性が０．０１重量％以下の疎水性高沸点有機溶媒（例えば、流動パラフィン、ジオクチルフタレート、トリクレジルホスフェート、シリコンオイル等）や重合体粒子（例えば、スチレン、ブチルアクリレート、ジビニルベンゼン、ブチルメタクリレート、ヒドロキシエチルメタクリレート等の重合性モノマーを一種以上重合させた粒子）を含有させることができる。そのような油滴は好ましくは親水性バインダーに対して１０〜５０重量％の範囲で用いることができる。
【００５１】
本発明において、インク受容層の耐水性、塗布性を改良するため他の架橋剤（硬膜剤）を併用しても良い。架橋剤の具体的な例としては、ホルムアルデヒド、グルタルアルデヒドの如きアルデヒド系化合物、ジアセチル、クロルペンタンジオンの如きケトン化合物、ビス（２−クロロエチル）尿素、２−ヒドロキシ−４，６−ジクロロ−１，３，５−トリアジン、米国特許第３，２８８，７７５号記載の如き反応性のハロゲンを有する化合物、ジビニルスルホン、米国特許第３，６３５，７１８号記載の如き反応性のオレフィンを持つ化合物、米国特許第２，７３２，３１６号記載の如きＮ−メチロール化合物、米国特許第３，１０３，４３７号記載の如きイソシアナート類、米国特許第３，０１７，２８０号、同２，９８３，６１１号記載の如きアジリジン化合物類、米国特許第３，１００，７０４号記載の如きカルボジイミド系化合物類、米国特許第３，０９１，５３７号記載の如きエポキシ化合物、ムコクロル酸の如きハロゲンカルボキシアルデヒド類、ジヒドロキシジオキサンの如きジオキサン誘導体、クロム明ばん、硫酸ジルコニウム、ほう酸及びほう酸塩の如き無機架橋剤等が挙げられる。
【００５２】
本発明において、インク受容層には、更に、界面活性剤、着色染料、着色顔料、インク染料の定着剤、水溶性金属化合物、紫外線吸収剤、酸化防止剤、顔料の分散剤、消泡剤、レベリング剤、防腐剤、蛍光増白剤、粘度安定剤、ｐＨ調節剤などの公知の各種添加剤を添加することもできる。
【００５３】
本発明において、気相法シリカを含有するインク受容層は、好ましくはｐＨ３〜５に調整される。インク受容層のｐＨは膜面ｐＨとして測定できる。膜面ｐＨは、Ｊ．ＴＡＰＰＩ紙パルプ試験方法Ｎ０．４９に記載の方法に従って、蒸留水を用い、３０秒後に測定した表面ｐＨである。
【００５４】
インク受容層のｐＨは、塗布液の段階で調整するのが好ましいが、塗布液のｐＨと塗布乾燥された状態での膜面ｐＨとは必ずしも一致しないため、塗布液と膜面ｐＨとの関係を予め実験等によって求めておくことが所定の膜面ｐＨにするために必要である。インク受容層塗布液のｐＨは、酸またはアルカリを適当に組み合わせて行われる。酸としては、塩酸、硝酸、硫酸、リン酸等の無機酸、酢酸、クエン酸、コハク酸等の有機酸が用いられ、アルカリとしては、水酸化ナトリウム、アンモニア水、炭酸カリウム、リン酸三ナトリウム、または弱アルカリとして、弱酸のアルカリ金属塩が用いられる。
【００５５】
本発明において、インク受容層を塗布するための塗布方法は、特に限定されず、公知の塗布方法を用いることができる。例えば、スライドビード方式、カーテン方式、エクストルージョン方式、エアナイフ方式、ロールコーティング方式、ケッドバーコーティング方式、バーコート方式、ディップコート方式等がある。
【００５６】
本発明において、インク受容層は、１層であっても複数層で構成されていてもよい。複数層の場合、機能によって層を分けてもよい。複数層の場合、その内の少なくとも１層が本発明のインク受容層の構成であり、本発明のインク受容層は最外層または支持体に最も近い層であることが好ましい。
【００５７】
本発明において、支持体上にインク受容層が塗布された後の好ましい乾燥条件は、塗布後１５℃以下の温度（より好ましくは１０℃以下の温度）で１０秒以上冷却し、最高温度が６０℃以下（より好ましくは５５℃以下）で乾燥することである。この乾燥条件を用いることによって、更にひび割れ及び表面剥離が防止できる。
【００５８】
【実施例】
以下、実施例により本発明を詳しく説明するが、本発明の内容は実施例に限られるものではない。なお、実施例中、部とは、重量部を表す。
【００５９】
実施例１
＜ポリオレフィン樹脂被覆支持体の作製＞
広葉樹晒クラフトパルプ（ＬＢＫＰ）と針葉樹晒サルファイトパルプ（ＮＢＳＰ）の１：１混合物をカナディアン スタンダード フリーネスで３００ｍｌになるまで叩解し、パルプスラリーを調製した。これにサイズ剤としてアルキルケテンダイマーを対パルプ０．５重量％、強度剤としてポリアクリルアミドを対パルプ１．０重量％、カチオン化澱粉を対パルプ２．０重量％、ポリアミドエピクロロヒドリン樹脂を対パルプ０．５重量％添加し、水で希釈して１％スラリーとした。このスラリーを長網抄紙機で坪量１７０ｇ／m²になるように抄造し、ポリオレフィン樹脂被覆紙の原紙とした。抄造した原紙に、密度０．９１８ｇ／ｃｍ³の低密度ポリエチレン１００重量％の樹脂に対して、１０重量％のアナターゼ型チタンを均一に分散したポリエチレン樹脂組成物を３２０℃で溶融し、２００ｍ／分で厚さ３０μｍになるように押出被覆した。もう一方の面には密度０．９６２ｇ／ｃｍ³の高密度ポリエチレン樹脂７０重量部と密度０．９１８の低密度ポリエチレン樹脂３０重量部のブレンド樹脂組成物を同様に３２０℃で溶融し、厚さ３０μｍになるように押出コーティングし、粗面加工されたクーリングロールを用いて押出被覆した。
【００６０】
上記ポリオレフィン樹脂被覆紙表面に高周波コロナ放電処理を施した後、下記組成の下引き層をゼラチンが５０ｍｇ／m²となるように塗布乾燥して支持体を作成した。
【００６１】
＜下引き層＞
石灰処理ゼラチン １００部
スルフォコハク酸−２−エチルヘキシルエステル塩 ２部
クロム明ばん １０部
【００６２】
＜チタンキレートＡの合成＞
テトライソプロポキシチタン、乳酸、エタノール各１部を混合し、チタンキレートＡを合成した。
【００６３】
＜インク受容層塗布液の調製＞
気相法シリカとジアリルジメチルアンモニウムクロライドホモポリマーを含有するシリカ分散液に、撹拌下上記チタンキレートＡの溶液を添加した。続けてポリビニルアルコール溶液を添加し、下記に示す成分を含有するインク受容層塗布液を調製した。この塗布液を上記支持体上に、気相法シリカの塗布量が固形分で、１９ｇ／m²になるようにロッドバーで塗布した。塗布後の乾燥条件は、塗布後先ず５℃で６０秒間冷却し、最高温度が４０℃で乾燥した。
【００６４】
＜インク受容層塗布液Ａ＞
気相法シリカ １００部
（平均一次粒径7nm、BET法による比表面積300m²/g）
ジアリルジメチルアンモニウムクロライドホモポリマー ４部
（第一工業製薬（株）製、シャロールDC902P、分子量9000）
チタンキレートＡ １部
ポリビニルアルコール ２３部
（ケン化度88%、平均重合度3500）
界面活性剤 ０．３部
【００６５】
実施例２
シリカ分散液にチタンキレートＡ溶液を添加後、室温で１時間撹拌を続けて、次にポリビニルアルコール溶液を添加した以外は実施例１と同様にしてインクジェット記録材料を作成した。
【００６６】
実施例３
シリカ分散液にチタンキレートＡ溶液を添加後、５０℃で１時間撹拌を続けて、次にポリビニルアルコール溶液を添加した以外は実施例１と同様にしてインクジェット記録材料を作成した。
【００６７】
実施例４
チタンキレートＡの添加量を２部に変更し、シリカ分散液にチタンキレートＡ溶液を添加後、５０℃で４時間撹拌を続けて、次にポリビニルアルコール溶液を添加した以外は実施例１と同様にしてインクジェット記録材料を作成した。
【００６８】
実施例５
気相法シリカとジアリルジメチルアンモニウムクロライドホモポリマーを含有するシリカ分散液に、撹拌下ポリビニルアルコール溶液を添加し、次に上記チタンキレートＡの溶液を添加して、実施例１と同じ成分を含有するインク受容層塗布液を調製した。実施例１と同様に塗布、乾燥を行いインクジェット記録材料を作成した。
【００６９】
実施例６
ポリビニルアルコール溶液に、撹拌下上記チタンキレートＡの溶液を添加し、次に気相法シリカとジアリルジメチルアンモニウムクロライドホモポリマーを含有するシリカ分散液を添加して、実施例１と同じ成分を含有するインク受容層塗布液を調製した。塗布液調製の際に、凝集物の発生が見られた。実施例１と同様に塗布、乾燥を行いインクジェット記録材料を作成した。
【００７０】
比較例１
チタンキレートＡを添加しない以外は、実施例１と同様にしてインクジェット記録材料を作成した。
【００７１】
上記のようにして作製したインクジェット記録材料について下記の評価を行った。その結果を表１に示す。
【００７２】
＜ひび割れ＞
塗布面を目視及びルーペで観察し、ひび割れ状態を以下の基準で評価した。
○：全くひび割れなし。
△：僅かにひび割れが認められる。
×：明らかにひび割れが分かる。
【００７３】
＜光沢＞
未プリントのインクジェット記録シート表面の光沢を目視で判定。
○：光沢が非常に高く良好。
△：光沢がやや劣る。
×：光沢が低い。
【００７４】
＜インク受容層の表面剥離性＞
セイコーエプソン社製インクジェットプリンターＰＭ８００を用いて黒色印字後、１０時間以上風乾し、印字部表面に、接着テープを貼り、急速に剥離したときの剥離状況を目視観察し、以下の基準で評価した。
○：全く剥離せず。
△：僅かに剥離有り。
×：かなりの面積が剥離する。
【００７５】
＜インク吸収性＞
インクジェットプリンターで、Ｃ、Ｍ、Ｙをベタ印字して、印字直後にＰＰＣ用紙を印字部に重ねて軽く圧着し、ＰＰＣ用紙に転写したインク量の程度を目視で観察し、下記の基準で評価した。
○：転写しない。
△：少し転写する。
×：かなり転写する。
【００７６】
【表１】

【００７７】
上記結果より、チタンキレート化合物が記録材料の表面ひび割れを防止し、表面光沢、表面剥離性、インク吸収性を改善することが分かる。特に、チタンキレート化合物を気相法シリカ分散液と混合し、しばらく撹拌した後、親水性バインダーと混合することによって、他の混合方法よりもその効果が大きくなることが分かる。
【００７８】
実施例７
気相法シリカとジアリルジメチルアンモニウムクロライドホモポリマーを含有するシリカ分散液に、撹拌下上記チタンキレートＡの溶液を添加した。室温下で１時間撹拌を継続した後、ポリビニルアルコール溶液を添加し、下記に示す成分を含有するインク受容層塗布液を調製した。この塗布液を上記支持体上に、気相法シリカの塗布量が固形分で、１９ｇ／m²になるようにロッドバーで塗布した。塗布後の乾燥条件は、塗布後先ず５℃で６０秒間冷却し、最高温度が４０℃で乾燥した。
【００７９】
＜インク受容層塗布液Ｂ＞
気相法シリカ １００部
（平均一次粒径12nm、BET法による比表面積200m²/g）
ジアリルジメチルアンモニウムクロライドホモポリマー ３部
（第一工業製薬（株）製、シャロールDC902P、分子量9000）
チタンキレートＡ １部
ポリビニルアルコール ２５部
（ケン化度88%、平均重合度3500）
界面活性剤 ０．３部
【００８０】
参考例１
ポリビニルアルコールの添加量を３５部に変えた以外は実施例７と同様にしてインクジェット記録材料を作成した。
【００８１】
比較例２
チタンキレートＡを添加しない以外は、実施例７と同様にしてインクジェット記録材料を作成した。
【００８２】
比較例３
チタンキレートＡを添加しない以外は、参考例１と同様にしてインクジェット記録材料を作成した。
【００８３】
上記のようにして作製したインクジェット記録材料について、実施例１と同様に評価を行った。結果を表２に示す。
【００８４】
【表２】

【００８５】
上記結果より、チタンキレート化合物が記録材料の表面ひび割れを防止し、表面光沢、表面剥離性、インク吸収性を改善することが分かる。また、親水性バインダー量の少ないほうが、インク吸収性が良好であることが分かる。
【００８６】
実施例９
気相法シリカとジアリルジメチルアンモニウムクロライドホモポリマーを含有するシリカ分散液に、撹拌下チタンラクテート（商品名：TC-310、（株）マツモト交商）を添加した。室温下で１時間撹拌を継続した後、ポリビニルアルコール溶液を添加し、さらに他の添加剤を添加して下記に示す成分を含有するインク受容層塗布液を調製した。この塗布液を上記支持体上に、気相法シリカの塗布量が固形分で、１９ｇ／m²になるようにスライド塗布装置で塗布した。塗布後の乾燥条件は、塗布後先ず５℃で２０秒間冷却し、最高温度が５０℃で乾燥した。
【００８７】
＜インク受容層塗布液Ｃ＞
気相法シリカ １００部
（平均一次粒径7nm、BET法による比表面積300m²/g）
ジアリルジメチルアンモニウムクロライドホモポリマー ４部
（第一工業製薬（株）製、シャロールDC902P、分子量9000）
チタンラクテート １部
（商品名：TC-310、（株）マツモト交商）
ポリビニルアルコール ２３部
（ケン化度88%、平均重合度3500）
塩基性ポリ水酸化アルミニウム ４部
（商品名：ピュラケムWT、（株）理研グリーン製）
界面活性剤 ０．３部
【００８８】
比較例４
チタンラクテートを添加しない以外は、実施例９と同様にしてインクジェット記録材料を作成した。
【００８９】
上記のようにして作製したインクジェット記録材料について、実施例１と同様に評価を行った。結果を表３に示す。
【００９０】
【表３】

【００９１】
上記結果も、チタンキレート化合物が記録材料の表面ひび割れを防止し、表面光沢、表面剥離性、インク吸収性を改善することを支持している。
【００９２】
【発明の効果】
本発明によれば、インク受容層に気相法シリカを使用し、高い光沢、高いインク吸収性を維持し、かつインク受容層のひび割れや表面剥離が防止されたインクジェット記録材料が提供できる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to an inkjet recording material having an ink receiving layer and a method for producing the same, and more specifically, the ink receiving layer contains vapor phase silica, has no cracks on the surface of the ink receiving layer, has high gloss, The present invention relates to an ink jet recording material excellent in ink absorbability and a method for producing the same.
[0002]
[Prior art]
As a recording material used in the ink jet recording method, a porous ink absorbing layer comprising a pigment such as amorphous silica and a hydrophilic binder such as polyvinyl alcohol on a support called ordinary paper or ink jet recording paper. The recording material provided is known.
[0003]
For example, JP-A Nos. 55-51583, 56-157, 57-107879, 57-107880, 59-230787, 62-160277, 62-184879, 62-183382 And a recording material obtained by applying a silicon-containing pigment such as silica to a paper support together with an aqueous binder has been proposed.
[0004]
JP-B-3-56552, JP-A-2-188287, JP-A-10-81064, JP-A-10-119423, JP-A-10-175365, JP-A-10-203006, JP-A-10-217601, Japanese Patent Laid-Open Nos. 11-20300, 11-20306, 11-34481, etc. disclose a technique for improving gloss and ink absorbency by using vapor phase silica.
[0005]
Conventionally, paper has been generally used as the recording material support described above, and the paper itself has a role as an ink absorbing layer. In recent years, photo-like recording materials are demanded, and recording materials using a paper support have problems such as gloss, texture, water resistance, cockling after printing (wrinkles or undulations), resin films and water resistance. For example, resin-coated paper (polyolefin resin-coated paper) in which a polyolefin resin such as polyethylene is laminated on both sides of paper has been used. However, since these non-water-absorbing supports cannot absorb ink unlike paper supports, the ink absorbability of the ink receiving layer provided on the support is important. Compared with the recording material, the recording material of the non-water-absorbing support had to apply a large amount of pigment. By increasing the coating amount of the pigment, cracks were liable to occur during drying, and the quality was significantly reduced.
[0006]
The above-mentioned gas phase method silica is a fine particle having an average primary particle size of several nanometers to several tens of nanometers, so that high ink absorbency and high gloss can be obtained. is there. In particular, when taking advantage of this feature (high gloss) to obtain a photo-like recording material together with a non-water-absorbing support, a large amount of vapor-phase silica has to be applied, which has caused the problem of cracking. .
[0007]
In addition, when the amount of the hydrophilic binder with respect to the vapor phase method silica is reduced in order to increase the ink absorbability, there is a problem that cracks are more likely to occur. In addition, there is a problem that the surface layer peels when the surface of the ink receiving layer is rubbed or the adhesive tape is peeled off.
[0008]
[Problems to be solved by the invention]
Accordingly, an object of the present invention is to provide an ink jet recording material containing gas phase method silica in an ink receiving layer, which has high ink absorbability and gloss, cracks and surface peeling, and a method for producing the same.
[0009]
[Means for Solving the Problems]
The above object of the present invention is to provide an inkjet recording material having at least one ink receiving layer on a support, wherein the ink receiving layer has vapor phase silica having an average primary particle size of 30 nm or less, a hydrophilic binder, and The invention has been achieved by an ink jet recording material characterized by containing a titanium chelate compound.
[0010]
In particular, the ink receiving layer is 10 g / m²It is preferable to contain the above gas phase method silica and to contain a hydrophilic binder in an amount of 30% by weight or less based on the gas phase method silica. Furthermore, it is preferable to use a non-water-absorbing support as the support.
[0011]
Also, an inkjet recording characterized in that a coating liquid is prepared by mixing a dispersion containing a vapor phase silica and a titanium chelate compound and a hydrophilic binder, and the coating liquid is coated on a support and dried. Achieved by the method of manufacturing the material.
[0012]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the present invention will be described in detail.
Examples of the support used in the present invention include non-water-absorbing polyethylene, polypropylene, polyvinyl chloride, polyethylene terephthalate films, resin-coated paper, etc., water-absorbing fine paper, art paper, coated paper, cast coating Paper or the like is used. The thickness of these supports is preferably about 50 to 250 μm. A non-water-absorbing support is preferable from the viewpoint of surface gloss and wrinkle prevention.
[0013]
A particularly preferred support is a polyolefin resin-coated paper support (hereinafter referred to as resin-coated paper). The moisture content of the resin-coated paper is not particularly limited, but is preferably in the range of 5.0 to 9.0%, more preferably in the range of 6.0 to 9.0% from the curling property.
[0014]
The base paper constituting the resin-coated paper is not particularly limited, and commonly used paper can be used, but smooth base paper such as that used for a photographic support is more preferable. As the pulp constituting the base paper, natural pulp, recycled pulp, synthetic pulp or the like is used alone or in combination of two or more. This base paper is blended with additives such as sizing agent, paper strength enhancer, filler, antistatic agent, fluorescent whitening agent, and dye generally used in papermaking.
[0015]
Further, a surface sizing agent, surface paper strengthening agent, fluorescent brightening agent, antistatic agent, dye, anchor agent and the like may be applied on the surface.
[0016]
In addition, the thickness of the base paper is not particularly limited, but preferably has a good surface smoothness such as a paper that is compressed by applying a pressure during or after paper making using a calendar or the like, and has a basis weight of 30 to 250 g / m²Is preferred.
[0017]
Examples of the polyolefin resin that coats the base paper include olefin homopolymers such as low-density polyethylene, high-density polyethylene, polypropylene, polybutene, and polypentene, or copolymers composed of two or more olefins such as ethylene-propylene copolymer, and the like. A mixture having various densities and melt viscosity indexes (melt index) can be used alone or in combination.
[0018]
In addition, in the resin of the resin-coated paper, white pigments such as titanium oxide, zinc oxide, talc and calcium carbonate, fatty acid amides such as stearic acid amide and arachidic acid amide, zinc stearate, calcium stearate, aluminum stearate, stearin Fatty acid metal salts such as magnesium acid, antioxidants such as Irganox 1010 and Irganox 1076, blue pigments and dyes such as cobalt blue, ultramarine blue, cecilian blue and phthalocyanine blue, magenta such as cobalt violet, fast violet and manganese purple It is preferable to add various additives such as pigments and dyes, fluorescent brighteners and ultraviolet absorbers in appropriate combinations.
[0019]
As a main production method of resin-coated paper, it is produced by a so-called extrusion coating method in which a polyolefin resin is cast on a traveling base paper in a heated and melted state, and both surfaces thereof are coated with the resin. Moreover, it is preferable to subject the base paper to an activation treatment such as corona discharge treatment or flame treatment before coating the resin on the base paper. Basically, it is not necessary to coat the back surface with resin, but it is preferable to coat resin from the viewpoint of curling prevention. The back surface is usually a matte surface, and an active treatment such as corona discharge treatment or flame treatment can be applied to the front surface or both the front and back surfaces as necessary. Moreover, there is no restriction | limiting in particular as thickness of a resin coating layer, Generally, it coats on the surface or both surfaces by the thickness of 5-50 micrometers.
[0020]
In the present invention, the polyolefin resin-coated paper support in which various backing layers are coated in the present invention within a range not deteriorating the effect of the present invention for writing property, antistatic property, anti-curl property and the like. include. The backing layer is preferably mainly composed of a binder, and the coating amount is 100 to 500 mg / m in solid content.²Is preferred. The backing layer can contain a suitable combination of hydrophilic binder, latex, organic pigment, inorganic pigment, inorganic antistatic agent, organic antistatic agent, curing agent, surfactant and the like.
[0021]
The ink jet recording material of the present invention has an ink receiving layer mainly containing gas phase method silica on the aforementioned support. The gas phase method silica mainly contains the gas phase method silica of 50% by weight or more, preferably 60% by weight or more, more preferably 65% by weight or more based on the total solid content of the ink receiving layer. is there.
[0022]
The silica fine particles used in the present invention are obtained by a gas phase method. Synthetic silica is classified into a wet method and a gas phase method. In general, silica fine particles often refer to wet process silica. As the wet method silica, (1) silica sol obtained through metathesis by an acid of sodium silicate or through an ion exchange resin layer, or (2) colloidal silica obtained by heating and aging this silica sol, (3) gelling the silica sol By changing the production conditions, silica gel in which primary particles of several microns to 10 microns are converted into three-dimensional secondary particles having siloxane bonds, and (4) silica sol, sodium silicate, sodium aluminate, etc. There are synthetic silicic acid compounds mainly composed of silicic acid, such as those obtained by heating to form a silicic acid.
[0023]
Vapor phase silica used in the present invention is also called a dry method as opposed to a wet method, and is generally made by a flame hydrolysis method. Specifically, a method of making silicon tetrachloride by burning with hydrogen and oxygen is generally known, but silanes such as methyltrichlorosilane and trichlorosilane can be used alone or silicon tetrachloride instead of silicon tetrachloride. Can be used in a mixed state. Vapor phase method silica is commercially available as Aerosil from Nippon Aerosil Co., Ltd., and as QS type from Tokuyama Co., Ltd., and can be obtained.
[0024]
The average particle diameter of the primary particles of the vapor-phase process silica used in the present invention is 30 nm or less, and in order to obtain higher gloss, it is 3 to 15 nm and the specific surface area by the BET method is 200 m.²/ G or more (preferably 200 to 500 m²/ G) is preferably used. The BET method referred to in the present invention is one of powder surface area measurement methods by vapor phase adsorption, and is a method for determining the total surface area, that is, the specific surface area of a 1 g sample from the adsorption isotherm. Usually, nitrogen gas is often used as the adsorbed gas, and the most frequently used method is to measure the amount of adsorption from the change in pressure or volume of the gas to be adsorbed. The most prominent expression for expressing the isotherm of multimolecular adsorption is the Brunauer, Emmett, and Teller formula, called the BET formula, which is widely used for determining the surface area. The adsorption amount is obtained based on the BET equation, and the surface area is obtained by multiplying the area occupied by one adsorbed molecule on the surface.
[0025]
In the present invention, the amount of vapor phase silica contained in the ink receiving layer is 10 g / m 2.²Or more, preferably 13 to 30 g / m²The range of is more preferable. If the content of the vapor phase silica exceeds the above range, cracks are likely to occur, and if the content is low, the ink absorbency decreases. For dispersing the vapor phase process silica, a generally known disperser such as a high-pressure homogenizer or a ball mill can be used.
[0026]
Various known hydrophilic binders can be used as the hydrophilic binder. For example, gelatin and derivatives thereof, polyvinylpyrrolidone, pullulan, polyvinyl alcohol and derivatives thereof, polyethylene glycol, carboxymethylcellulose, hydroxyethylcellulose, dextran, dextrin, polyacrylic acid and salts thereof, agar, carrageenan, xanthene gum, locust bean gum, alginic acid Gum arabic, polyalkylene oxide copolymers described in JP-A-7-197826 and JP-A-7-9757, water-soluble polyvinyl butyral, or carboxy groups and sulfones described in JP-A-62-245260. A vinyl monomer having an acid group or a copolymer thereof may be mentioned.
[0027]
Among the above hydrophilic binders, hydrophilic binders that are highly transparent and can provide higher ink permeability are preferably used. As this hydrophilic binder, polyvinyl alcohol and cation-modified polyvinyl alcohol are preferably used.
[0028]
Particularly preferred among the polyvinyl alcohols are those having a degree of saponification of 80% or more or those completely saponified. Polyvinyl alcohol having an average degree of polymerization of 500 to 5000 is preferred.
[0029]
The cation-modified polyvinyl alcohol has a primary to tertiary amino group or a quaternary ammonium group in the main chain or side chain of the polyvinyl alcohol as described in, for example, JP-A-61-10383. Polyvinyl alcohol.
[0030]
The above-mentioned hydrophilic binder is preferably used in a small ratio with respect to the inorganic fine particles from the viewpoint of ink absorbability. However, when the amount of the hydrophilic binder decreases, when it is applied and dried, cracks and surface peeling tend to occur. . One feature of the present invention is that cracking and surface peeling can be prevented even when the amount of the hydrophilic binder is within a limited range of 30% by weight or less based on the inorganic fine particles. In the present invention, the amount of the hydrophilic binder is preferably 10 to 30% by weight, more preferably 15 to 28% by weight with respect to the inorganic fine particles.
[0031]
The titanium chelate compound used in the present invention means that titanium takes two electrons from atoms having a free electron pair, such as O and N, in addition to four main valence bonds, and forms two bonds. It is the compound which became.
[0032]
A typical preferred titanium chelate compound is represented by the following general formula 1.
[0033]
[Chemical 1]

In the formula, X represents O or N, and Y represents a linear bridging group having 2 to 6 carbon atoms. R₁, R₂Independently represents H, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms. Z is (NR_ThreeR_FourR_Five)⁺And n represents an integer of 0-2. R_Three, R_Four, R_FiveIndependently represents H or an alkyl group having 1 to 4 carbon atoms.
[0034]
In the general formula 1, X-Y-O preferably forms a structure of lactic acid, glycolic acid, malic acid, citric acid, tartaric acid, sugar acid, gluconic acid, glyceric acid, or mandelic acid.
[0035]
Specific examples of the titanium chelate compound include dihydroxybis (lactato) titanium, monoammonium salt of dihydroxybis (lactato) titanium, diammonium salt of dihydroxybis (lactato) titanium, diisopropoxybis (lactato) titanium, dihydroxybis ( Malato) titanium, diisopropoxy bis (methyl lactato) titanium, diisopropoxy bis (ethyl lactato) titanium, diisopropoxy bis (n-propyl lactato) titanium, diisobutoxy bis (methyl lactato) titanium, diisopropoxy bis (acetylacetate) Nato) titanium, diisopropoxy (2-ethyl-1,3-hexanediolato) titanium, di-n-butoxybis (triethanolaminato) titanium, oxobis (lactato) titanium, oxobis (monoammo) Umuokizarato) titanium, and the like.
[0036]
The titanium chelate compound may be synthesized and used, but a commercially available product can be suitably used. Although the example of a typical commercial item is given to the following, this invention is not limited to these. For example, Olga Chicks TC-300, Olga Chicks TC-310, Olga Chicks TC-400 (above, Matsumoto Kosho Co., Ltd.), T-50, TLA-A-50, TLA-AA-50, TOA-30, TAT (above, Nippon Soda Co., Ltd.), TAA, TEAA (above, Mitsubishi Gas Chemical Co., Ltd.) and the like can be mentioned.
[0037]
Japanese Patent Application Laid-Open No. 2000-43403 discloses an ink jet recording paper that contains a titanium lactate compound or a titanium glycolate compound in the ink receiving layer, and has improved blanking of the white paper portion during file storage or adhesive tape application. . However, there is no description of cracking or surface peeling of the ink receiving layer, which becomes a problem when a large amount of gas phase method silica is applied on a non-water-absorbing support or when the amount of the hydrophilic binder is reduced.
[0038]
The content of the titanium chelate compound in the ink-receiving layer is 0.01 to 10% by weight, preferably 0.01% to 10% by weight, based on the total amount of the pigment when vapor phase method silica or vapor phase method silica and other pigments are used in combination. 0.1 to 5% by weight. When the content of the titanium chelate compound is less than 0.01% by weight, the effect of improving the crack, prevention, surface gloss, surface peelability, and ink absorbability of the ink receiving layer surface by the titanium chelate compound is not sufficient. On the other hand, if it contains more than 10% by weight, the surface gloss, surface peelability and ink absorbability may be lowered, or the image may be discolored and the color reproducibility may be lowered.
[0039]
As a method of including the titanium chelate compound in the ink receiving layer, a method of applying the titanium chelate compound in the ink receiving layer coating liquid, a method of simultaneously coating the ink receiving layer coating liquid and the titanium chelate compound-containing coating liquid as separate layers And a method of infiltrating the titanium chelate compound into the ink receiving layer by spraying or overcoating a liquid containing the titanium chelate compound before drying after applying the ink receiving layer. Preferably, the ink-receiving layer coating solution contains a titanium chelate compound for coating.
[0040]
When the titanium chelate compound is contained in the ink-receiving layer coating solution, the titanium chelate compound may be added to the coating solution at any stage as long as it is before coating. As a result of investigation, it was found that the cracking and surface gloss of the ink receiving layer surface can be further improved by first preparing a dispersion containing vapor-phase silica and a titanium chelate compound and then mixing with a hydrophilic binder. It was. At this time, the dispersion containing the vapor phase silica and the titanium chelate compound may be produced by mixing the vapor phase silica and the titanium chelate compound and then dispersing them with the disperser mentioned in the description of the vapor phase silica. The vapor phase silica dispersion previously produced using a disperser and a titanium chelate compound may be mixed and produced.
[0041]
In particular, when preparing a dispersion by mixing a gas phase method silica dispersion prepared in advance using a disperser and a titanium chelate compound, the gas phase method silica dispersion and the titanium chelate compound are mixed at 20 to 70 ° C. After stirring for 10 minutes to 24 hours, cracking and surface gloss are further improved by mixing with a hydrophilic binder. At this time, it is preferably stirred at 30 to 60 ° C. for 1 to 12 hours. If the temperature is lower than 20 ° C., the coating solution may become highly viscous and stirring may be difficult, and if it exceeds 70 ° C., moisture evaporation from the coating solution becomes violent. If the stirring time is 10 minutes or less, the stirring effect is not sufficient. If the stirring time exceeds 24 hours, the reason is not clear, but the crack and gloss of the ink receiving layer surface are lowered. As a stirring method at this time, there is no need for high shearing or high-speed stirring, and a known method can be used. For example, a magnetic stirrer, mechanical stirrer, propeller stirrer, turbine stirrer, disper, homomixer, or the like can be used.
[0042]
The ink receiving layer of the present invention preferably contains a cationic compound. Examples of the cationic compound used in the present invention include a cationic compound used for the purpose of improving water resistance, and examples thereof include a cationic polymer and a water-soluble metal compound.
[0043]
Examples of the cationic polymer include polyethyleneimine, polydiallylamine, polyallylamine, JP-A-59-20696, 59-33176, 59-33177, 59-1555088, 60-11389, 60- 49990, 60-83882, 60-109894, 62-198493, 63-49478, 63-115780, 63-280681, JP-A-1-40371, 6-234268 No. 7, 7-125411, 10-193976, etc., a polymer having a primary to tertiary amino group or a quaternary ammonium base is preferably used. The molecular weight of these cationic polymers is preferably 5,000 or more, and more preferably about 5,000 to 100,000.
[0044]
The amount of these cationic polymers used is 1 to 10% by weight, preferably 2 to 8% by weight, based on the inorganic fine particles.
[0045]
Examples of the cationic compound include a basic polyaluminum hydroxide compound that is an inorganic aluminum-containing cationic polymer. The basic polyaluminum hydroxide compound has a main component represented by the following general formula 1, 2 or 3, for example, [Al₆(OH)₁₅]³⁺, [Al₈(OH)₂₀]⁴⁺, [Al₁₃(OH)₃₄]⁵⁺, [Al_{twenty one}(OH)₆₀]³⁺It is a water-soluble polyaluminum hydroxide containing a basic and high-molecular polynuclear condensed ion such as.
[0046]
[Al₂(OH)_nCl_6-n]_m                        ..Formula 1
[Al (OH)_Three]_nAlCl_Three                       ..Formula 2
Al_n(OH)_mCl_(3n-m)    0 <m <3n ・ ・ Formula 3
[0047]
These are water treatment agents from Taki Chemical Co., Ltd. under the name of polyaluminum chloride (PAC), from Asada Chemical Co., Ltd. under the name of polyaluminum hydroxide (Paho), and from Riken Green Co., Ltd. It is marketed under the name of Purachem WT and from other manufacturers for the same purpose, and various grades can be easily obtained. In the present invention, these commercially available products can be used as they are, but there are also products having an inappropriately low pH, and in that case, the pH can be appropriately adjusted and used.
[0048]
In the present invention, the content of the water-soluble metal compound in the ink receiving layer is 0.1 g / m.²-10g / m², Preferably 0.2 g / m²~ 5g / m²It is.
[0049]
Two or more of the above cationic compounds can be used in combination. For example, a cationic polymer and an aluminum-containing cationic polymer may be used in combination.
[0050]
The ink receiving layer in the present invention preferably contains various oil droplets in order to improve the brittleness of the film. Such oil droplets have a hydrophobicity of 0.01% by weight or less in water at room temperature. High-boiling organic solvents (for example, liquid paraffin, dioctyl phthalate, tricresyl phosphate, silicone oil, etc.) and polymer particles (for example, styrene, butyl acrylate, divinylbenzene, butyl methacrylate, hydroxyethyl methacrylate, etc.) One or more kinds of polymerized particles) can be contained. Such oil droplets can be preferably used in the range of 10 to 50% by weight based on the hydrophilic binder.
[0051]
In the present invention, other crosslinking agents (hardeners) may be used in combination in order to improve the water resistance and coating properties of the ink receiving layer. Specific examples of the crosslinking agent include aldehyde compounds such as formaldehyde and glutaraldehyde, ketone compounds such as diacetyl and chloropentanedione, bis (2-chloroethyl) urea, 2-hydroxy-4,6-dichloro-1, 3,5-triazine, a compound having a reactive halogen as described in US Pat. No. 3,288,775, divinyl sulfone, a compound having a reactive olefin as described in US Pat. No. 3,635,718, N-methylol compounds as described in Japanese Patent No. 2,732,316, isocyanates as described in US Pat. No. 3,103,437, US Pat. Nos. 3,017,280 and 2,983,611 described Aziridine compounds such as US Pat. No. 3,100,704, carbodiimide compounds, US Examples include epoxy compounds as described in U.K. 3,091,537, halogen carboxaldehydes such as mucochloric acid, dioxane derivatives such as dihydroxydioxane, chromium alum, zirconium sulfate, boric acid, and inorganic crosslinking agents such as borate. .
[0052]
In the present invention, the ink receiving layer further includes a surfactant, a coloring dye, a coloring pigment, an ink dye fixing agent, a water-soluble metal compound, an ultraviolet absorber, an antioxidant, a pigment dispersant, an antifoaming agent, Various known additives such as leveling agents, preservatives, optical brighteners, viscosity stabilizers and pH adjusters can also be added.
[0053]
In the present invention, the ink receiving layer containing vapor phase method silica is preferably adjusted to pH 3-5. The pH of the ink receiving layer can be measured as the film surface pH. The film surface pH Surface pH measured after 30 seconds using distilled water according to the method described in TAPPI paper pulp test method N0.49.
[0054]
The pH of the ink receiving layer is preferably adjusted at the stage of the coating solution, but the pH of the coating solution does not always match the film surface pH in the coated and dried state, so the relationship between the coating solution and the film surface pH. Is required in advance to obtain a predetermined film surface pH. The pH of the ink receiving layer coating solution is determined by appropriately combining acid or alkali. As the acid, inorganic acids such as hydrochloric acid, nitric acid, sulfuric acid and phosphoric acid, and organic acids such as acetic acid, citric acid and succinic acid are used. As the alkali, sodium hydroxide, aqueous ammonia, potassium carbonate and trisodium phosphate are used. Alternatively, an alkali metal salt of a weak acid is used as the weak alkali.
[0055]
In the present invention, a coating method for coating the ink receiving layer is not particularly limited, and a known coating method can be used. For example, there are a slide bead method, a curtain method, an extrusion method, an air knife method, a roll coating method, a Ked bar coating method, a bar coating method, a dip coating method, and the like.
[0056]
In the present invention, the ink receiving layer may be composed of a single layer or a plurality of layers. In the case of multiple layers, the layers may be divided according to function. In the case of a plurality of layers, at least one of them is the constitution of the ink receiving layer of the present invention, and the ink receiving layer of the present invention is preferably the outermost layer or the layer closest to the support.
[0057]
In the present invention, preferable drying conditions after the ink-receiving layer is coated on the support are cooled for 10 seconds or more at a temperature of 15 ° C. or lower (more preferably 10 ° C. or lower) after coating, and the maximum temperature is 60. The drying is performed at a temperature not higher than ° C. (more preferably not higher than 55 ° C.). By using this drying condition, cracking and surface peeling can be further prevented.
[0058]
【Example】
EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, the content of this invention is not restricted to an Example. In addition, a part represents a weight part in an Example.
[0059]
Example 1
<Preparation of polyolefin resin-coated support>
A 1: 1 mixture of hardwood bleached kraft pulp (LBKP) and softwood bleached sulfite pulp (NBSP) was beaten to 300 ml with Canadian Standard Freeness to prepare a pulp slurry. As a sizing agent, alkyl ketene dimer is 0.5% by weight of pulp, polyacrylamide is 1.0% by weight of pulp, and cationized starch is 2.0% by weight of pulp, and polyamide epichlorohydrin resin is used as a sizing agent. 0.5% by weight of pulp was added and diluted with water to make a 1% slurry. The slurry is basis weight 170 g / m with a long paper machine.²Was made into a base paper for polyolefin resin-coated paper. Density 0.918g / cm on the base paper^ThreeA polyethylene resin composition in which 10% by weight of anatase-type titanium is uniformly dispersed is melted at 320 ° C. with respect to 100% by weight of low-density polyethylene, and extrusion-coated so as to have a thickness of 30 μm at 200 m / min. . The other surface has a density of 0.962 g / cm^ThreeA blended resin composition of 70 parts by weight of a high-density polyethylene resin and 30 parts by weight of a low-density polyethylene resin having a density of 0.918 is similarly melted at 320 ° C., extrusion coated to a thickness of 30 μm, and roughened. Extrusion coating was performed using a cooling roll.
[0060]
After subjecting the polyolefin resin-coated paper surface to a high-frequency corona discharge treatment, an undercoat layer having the following composition has a gelatin content of 50 mg / m 2.²A support was prepared by coating and drying.
[0061]
<Underlayer>
100 parts of lime processed gelatin
Sulfosuccinic acid-2-ethylhexyl ester salt 2 parts
Chrome Alum 10 copies
[0062]
<Synthesis of titanium chelate A>
Titanium chelate A was synthesized by mixing 1 part each of tetraisopropoxy titanium, lactic acid, and ethanol.
[0063]
<Preparation of ink receiving layer coating solution>
The above-mentioned titanium chelate A solution was added to a silica dispersion containing vapor-phase process silica and diallyldimethylammonium chloride homopolymer with stirring. Subsequently, a polyvinyl alcohol solution was added to prepare an ink-receiving layer coating solution containing the following components. The coating liquid is applied on the above support, and the coating amount of the vapor phase method silica is 19 g / m in solid content.²It applied with a rod bar so that it might become. As for the drying conditions after coating, the coating was first cooled at 5 ° C. for 60 seconds and dried at a maximum temperature of 40 ° C.
[0064]
<Ink-receiving layer coating solution A>
Gas phase method silica 100 parts
(Average primary particle size 7nm, specific surface area 300m by BET method²/ g)
Diallyldimethylammonium chloride homopolymer 4 parts
(Daiichi Kogyo Seiyaku Co., Ltd., Charol DC902P, molecular weight 9000)
Titanium chelate A 1 part
23 parts of polyvinyl alcohol
(Saponification degree 88%, average polymerization degree 3500)
Surfactant 0.3 part
[0065]
Example 2
After adding the titanium chelate A solution to the silica dispersion, stirring was continued at room temperature for 1 hour, and then an inkjet recording material was prepared in the same manner as in Example 1 except that the polyvinyl alcohol solution was added.
[0066]
Example 3
After adding the titanium chelate A solution to the silica dispersion, stirring was continued for 1 hour at 50 ° C., and then an inkjet recording material was prepared in the same manner as in Example 1 except that the polyvinyl alcohol solution was added.
[0067]
Example 4
The addition amount of titanium chelate A was changed to 2 parts, and after adding the titanium chelate A solution to the silica dispersion, stirring was continued at 50 ° C. for 4 hours, and then the polyvinyl alcohol solution was added, and then the same as in Example 1. Thus, an ink jet recording material was prepared.
[0068]
Example 5
To a silica dispersion containing vapor-phase process silica and diallyldimethylammonium chloride homopolymer, a polyvinyl alcohol solution is added with stirring, and then the titanium chelate A solution is added to contain the same components as in Example 1. An ink receiving layer coating solution was prepared. Coating and drying were carried out in the same manner as in Example 1 to prepare an ink jet recording material.
[0069]
Example 6
To the polyvinyl alcohol solution, the titanium chelate A solution is added with stirring, and then a silica dispersion containing vapor-phase silica and diallyldimethylammonium chloride homopolymer is added to contain the same components as in Example 1. An ink receiving layer coating solution was prepared. During the preparation of the coating solution, generation of aggregates was observed. Coating and drying were carried out in the same manner as in Example 1 to prepare an ink jet recording material.
[0070]
Comparative Example 1
An ink jet recording material was prepared in the same manner as in Example 1 except that the titanium chelate A was not added.
[0071]
The ink jet recording material produced as described above was evaluated as follows. The results are shown in Table 1.
[0072]
<Crack>
The coated surface was observed visually and with a magnifying glass, and the cracked state was evaluated according to the following criteria.
○: No crack at all.
Δ: Slight cracking is observed.
X: Clearly cracked.
[0073]
<Glossy>
The gloss of the unprinted inkjet recording sheet surface is judged visually.
○: Good gloss is very high.
Δ: The gloss is slightly inferior.
X: Low gloss.
[0074]
<Surface peelability of ink receiving layer>
After black printing using an ink-jet printer PM800 manufactured by Seiko Epson Corporation, the paper was air-dried for 10 hours or more, an adhesive tape was applied to the surface of the printed part, and the peeled state when peeled rapidly was visually observed and evaluated according to the following criteria.
○: No peeling at all.
Δ: Slightly peeled.
X: A considerable area peels off.
[0075]
<Ink absorbability>
C, M, and Y are solid printed with an inkjet printer, and immediately after printing, the PPC paper is placed on the printing part and lightly pressed, and the degree of ink transferred to the PPC paper is visually observed and evaluated according to the following criteria: did.
○: Not transferred.
Δ: Slightly transferred.
X: Pretty transferred.
[0076]
[Table 1]

[0077]
From the above results, it can be seen that the titanium chelate compound prevents surface cracking of the recording material and improves surface gloss, surface peelability, and ink absorbability. In particular, it can be seen that mixing the titanium chelate compound with the gas phase method silica dispersion, stirring for a while, and then mixing with the hydrophilic binder increases the effect compared to other mixing methods.
[0078]
Example 7
The above-mentioned titanium chelate A solution was added to a silica dispersion containing vapor-phase process silica and diallyldimethylammonium chloride homopolymer with stirring. After stirring for 1 hour at room temperature, a polyvinyl alcohol solution was added to prepare an ink-receiving layer coating solution containing the following components. The coating liquid is applied on the above support, and the coating amount of the vapor phase method silica is 19 g / m in solid content.²It applied with a rod bar so that it might become. As for the drying conditions after coating, the coating was first cooled at 5 ° C. for 60 seconds and dried at a maximum temperature of 40 ° C.
[0079]
<Ink-receiving layer coating solution B>
Gas phase method silica 100 parts
(Average primary particle size 12nm, specific surface area 200m by BET method²/ g)
Diallyldimethylammonium chloride homopolymer 3 parts
(Daiichi Kogyo Seiyaku Co., Ltd., Charol DC902P, molecular weight 9000)
Titanium chelate A 1 part
25 parts of polyvinyl alcohol
(Saponification degree 88%, average polymerization degree 3500)
Surfactant 0.3 part
[0080]
  Reference example 1
  An ink jet recording material was prepared in the same manner as in Example 7 except that the amount of polyvinyl alcohol added was changed to 35 parts.
[0081]
Comparative Example 2
An ink jet recording material was prepared in the same manner as in Example 7 except that the titanium chelate A was not added.
[0082]
  Comparative Example 3
  Except for not adding titanium chelate A,Reference example 1An ink jet recording material was prepared in the same manner as described above.
[0083]
The inkjet recording material produced as described above was evaluated in the same manner as in Example 1. The results are shown in Table 2.
[0084]
[Table 2]

[0085]
From the above results, it can be seen that the titanium chelate compound prevents surface cracking of the recording material and improves surface gloss, surface peelability, and ink absorbability. In addition, it can be seen that the smaller the amount of the hydrophilic binder, the better the ink absorbability.
[0086]
Example 9
Titanium lactate (trade name: TC-310, Matsumoto Co., Ltd.) was added to a silica dispersion containing vapor-phase process silica and diallyldimethylammonium chloride homopolymer with stirring. After stirring for 1 hour at room temperature, a polyvinyl alcohol solution was added, and other additives were further added to prepare an ink receiving layer coating solution containing the components shown below. The coating liquid is applied on the above support, and the coating amount of the vapor phase method silica is 19 g / m in solid content.²It apply | coated with the slide application device so that it might become. As for the drying conditions after coating, the coating was first cooled at 5 ° C. for 20 seconds and dried at a maximum temperature of 50 ° C.
[0087]
<Ink-receiving layer coating solution C>
Gas phase method silica 100 parts
(Average primary particle size 7nm, specific surface area 300m by BET method²/ g)
Diallyldimethylammonium chloride homopolymer 4 parts
(Daiichi Kogyo Seiyaku Co., Ltd., Charol DC902P, molecular weight 9000)
Titanium lactate 1 part
(Product name: TC-310, Matsumoto Kosho Co., Ltd.)
23 parts of polyvinyl alcohol
(Saponification degree 88%, average polymerization degree 3500)
4 parts of basic polyaluminum hydroxide
(Product name: Purachem WT, manufactured by Riken Green Co., Ltd.)
Surfactant 0.3 part
[0088]
Comparative Example 4
An ink jet recording material was prepared in the same manner as in Example 9 except that no titanium lactate was added.
[0089]
The inkjet recording material produced as described above was evaluated in the same manner as in Example 1. The results are shown in Table 3.
[0090]
[Table 3]

[0091]
The above results also support that the titanium chelate compound prevents surface cracking of the recording material and improves surface gloss, surface peelability, and ink absorbability.
[0092]
【The invention's effect】
According to the present invention, it is possible to provide an ink jet recording material that uses vapor phase silica for the ink receiving layer, maintains high gloss and high ink absorbency, and prevents cracking and surface peeling of the ink receiving layer.

Claims (1)

In the ink-jet recording material having an ink-receiving layer of at least one layer on a support, the ink receiving layer an average particle size of less fumed silica mosquito 30nm of the primary particles, 30% by weight relative to the fumed silica jet recording material characterized by containing the following parent aqueous binder, and a titanium chelate compound.