JP4170109B2 - Support for recording material, method for producing the same, and recording material - Google Patents

Description

【０１４１】
ここで、上記式（１）において、Ｒ^１０は非置換又は置換の好ましくは炭素数１〜８の一価炭化水素基であり、好ましくは炭素数１〜８のアルキル基又は炭素数２〜３のアルケニル基であり、特にメチル基であることが好ましい。ａ，ｅはそれぞれ０又は１、ｂ，ｄはそれぞれ１〜４の整数、ｃは０〜８の整数である。また、ｘは１以上の整数、好ましくは１０〜３０である。
【０１４２】
このような（Ａ）成分としては、下記式（２）で示すものを挙げることができる。
【０１４３】
【化２】

【０１４４】
前記（Ｂ）成分において、≡ＳｉＨ基を有するオルガノポリシロキサンとしては、ケイ素原子に結合した水素原子を分子中に少なくとも２個有するオルガノハイドロジェンポリシロキサンを挙げることができる。
【０１４５】
また、本発明で用いるフルオロカーボンシロキサンゴム組成物においては、（Ａ）成分のフルオロカーボンポリマーが脂肪族不飽和基を有するものであるときには、硬化剤として上述したオルガノハイドロジェンポリシロキサンを使用することができる。即ち、この場合には、フルオロカーボンシロキサン中の脂肪族不飽和基と、オルガノハイドロジェンポリシロキサン中のケイ素原子に結合した水素原子との間で生ずる付加反応によって硬化物が形成されるものである。
【０１４６】
このようなオルガノハイドロジェンポリシロキサンとしては、付加硬化型のシリコーンゴム組成物に使用される種々のオルガノハイドロジェンポリシロキサンを使用することができる。
【０１４７】
上述したオルガノハイドロジェンポリシロキサンは、一般にその≡ＳｉＨ基の数が、（Ａ）成分のフルオロカーボンシロキサン中の脂肪族不飽和炭化水素基１個に対して、少なくとも１個、特に１〜５個となるような割合で配合することが好適である。
【０１４８】
また、≡ＳｉＨ基を有するフルオロカーボンとしては、上記式（１）の単位又は式（１）においてＲ^１０がジアルキルハイドロジェンシロキシ基であり、かつ末端がジアルキルハイドロジェンシロキシ基又はシリル基等の≡ＳｉＨ基であるものが好ましく、下記式（３）で示すものを挙げることができる。
【０１４９】
【化３】

【０１５０】
前記（Ｃ）成分の充填剤としては、一般的なシリコーンゴム組成物に使用されている種々の充填剤を用いることができる。例えば、煙霧質シリカ、沈降性シリカ、カーボン粉末、二酸化チタン、酸化アルミニウム、石英粉末、タルク、セリサイト及びベントナイト等の補強性充填剤、アスベスト、ガラス繊維、有機繊維等の繊維質充填剤などを例示することができる。
【０１５１】
前記（Ｄ）成分の触媒としては、付加反応用触媒として公知とされている塩化白金酸、アルコール変性塩化白金酸、塩化白金酸とオレフィンとの錯体、白金黒又はパラジウムをアルミナ、シリカ、カーボンなどの担体に担持したもの、ロジウムとオレフィンとの錯体、クロロトリス（トリフェニルフォスフィン）ロジウム（ウィルキンソン触媒）、ロジウム（ＩＩＩ）アセチルアセトネートなどのような周期律表第ＶＩＩＩ族元素又はその化合物が例示されるが、これらの錯体はアルコール系、エーテル系、炭化水素などの溶剤に溶解して用いることが好ましい。
【０１５２】
本発明で用いるフルオロカーボンシロキサンゴム組成物においては、耐溶剤性を向上させるという本発明の目的を損なわない範囲において、種々の配合剤を添加することができる。例えば、ジフェニルシランジオール、低重合度の分子鎖末端水酸基封鎖ジメチルポリシロキサン、ヘキサメチルジシラザン等の分散剤、酸化第一鉄、酸化第二鉄、酸化セリウム、オクチル酸鉄等の耐熱性向上剤、顔料等の着色剤、などを必要に応じて配合することができる。
【０１５３】
前記本発明の定着用ベルトは、耐熱性樹脂製又は金属製のベルト本体の表面を上記フルオロカーボンシロキサンゴム組成物で被覆し、加熱硬化することによって得られるが、必要に応じて更に、ｍ−キシレンヘキサフロライド、ベンゾトリフロライド等の溶剤で希釈して塗工液とし、スプレーコート、ディップコート及びナイフコート等の一般的なコーティング法によって塗布することができる。また、加熱硬化の温度、時間は適宜選定することができ、通常温度１００〜５００℃、時間５秒〜５時間の範囲でベルト本体の種類及び製造方法などに応じて選択される。
【０１５４】
前記定着ベルトの表面に形成するフルオロカーボンシロキサンゴム層の厚さは特に限定されるものではないが、トナーの剥離性或いはトナー成分のオフセットを防止して画像の良好な定着性を得るために２０〜５００μｍが好ましく、４０〜２００μｍがより好ましい。
【０１５５】
本発明の電子写真用受像シートに画像を形成する方法は、定着ベルトを使用した電子写真方法であれば、上記した画像形成方法に制限されるものではない。通常の電子写真法であれば、いずれも適用することができる。
【０１５６】
＜インクジェット記録用材料＞
前記インクジェット記録用材料としては、例えば、前記本発明の記録材料用支持体上に、水性インク（色材として染料又は顔料を用いたもの）及び油性インク等の液状インクや、常温では固体であり、溶融液状化させて印画に供する固体状インク等を受容できる前記色材受容層を有し、更に必要に応じて適宜選択したその他の層、例えば、バック層、保護層、中間層、下塗り層、クッション層、帯電調節（防止）層、反射層、色味調製層、保存性改良層、接着防止層、アンチカール層、平滑化層などを有してなる。これらの各層は単層構造であってもよいし、積層構造であってもよい。
【０１５７】
〔色材受容層〕
前記色材受容層は、ポリマー微粒子を少なくとも含有し、更に、水溶性樹脂、架橋剤、媒染剤等を含有する。
【０１５８】
−ポリマー微粒子−
前記色材受容層がポリマー微粒子を含有することにより多孔質構造が得られ、これによりインクの吸収性能が向上する。特に、該ポリマー微粒子の色材受容層における固形分含有量が５０質量％以上、より好ましくは６０質量％を超えていると、更に良好な多孔質構造を形成することが可能となり、十分なインク吸収性を備えたインクジェット記録用シートが得られるので好ましい。ここで、ポリマー微粒子の色材受容層における固形分含有量とは、色材受容層を構成する組成物中の水以外の成分に基づき算出される含有量である。
【０１５９】
前記ポリマー微粒子（ラテックス）としては、各種ポリマーの親水性溶媒分散体の形態で用いることができる。具体的には、アクリル系ポリマー、エステル系ポリマー、ウレタン系ポリマー、アミド系ポリマー、オレフィン系ポリマー、塩化ビニリデン系ポリマー、エポキシ系ポリマー、アミド系ポリマー及びこれらの変性物や共重合体等の水分散体を用いることができる。これらの中でも、アクリル系ポリマー、オレフィン系ポリマー、ウレタン系ポリマーの使用が好ましく、インク吸収性、塗膜強度の点から、オレフィン系ポリマー及びアクリル系ポリマーが好ましい。
【０１６０】
前記オレフィン系ポリマーとしては、ビニルモノマーとジオレフィン類のコポリマーからなるポリマーが好ましい。前記ビニルモノマーとしては、例えば、スチレン、アクリルニトリル、メタクリルニトリル、アクリル酸メチル、メタクリル酸メチル、酢酸ビニル等が好ましく用いられる。前記ジオレフィン類としては例えば、ブタジエン、イソプレン、クロロプレンなどが好ましく用いられる。
また、これら成分に加えて、不飽和カルボン酸（例えば、アクリル酸、メタクリル酸、イタコン酸、無水マレイン酸、もしくはこれらのアルキルエステル、アクロレイン、メタクロレイン、アクリル酸グリシジル、メタクリル酸グリシジル、アクリル酸−２−ヒドロキシルエチル、メタクリル酸−２−ヒドロキシルエチル、アクリル酸アリル、Ｎ−メチロールアクリルアミド、ビニルイソシアネート等の架橋可能な成分を加えることもできる。
【０１６１】
前記アクリル系ポリマーとしては、例えば、炭素原子数が１〜１８の直鎖又は分岐の脂肪族基、フェニル基、アラルキル基、ヒドロキシル基を有する脂肪族基等のアクリル酸又はメタクリル酸エステル類、アクリルニトリル、炭素原子数が１〜１８のアルキル基のＮ−又はＮ，Ｎ−アクリルアミド、及びアクリル酸又はメタクリル酸及びこれらの塩の単独重合体もしくは共重合体、或いは前記モノマーと、スチレンスルホン酸やビニルスルホン酸及びそれらの塩、イタコン酸、マレイン酸、フマル酸及びそれらの塩、無水イタコン酸、無水マレイン酸等の酸無水物、ビニルイソシアネート、アリルイソシアネート、ビニルメチルエーテル、酢酸ビニル、スチレン、ジビニルベンゼン等との共重合体などが挙げられる。
【０１６２】
通常これらのポリマー微粒子は乳化重合法によって得られる。そこで用いられる界面活性剤、重合開始剤等については、常法で用いられるものを用いればよい。ポリマー微粒子の合成法に関しては、米国特許第２，８５２，３６８号、同２，８５３，４５７号、同３，４１１，９１１号、同３，４１１，９１２号、同４，１９７，１２７号、ベルギー特許第６８８，８８２号、同６９１，３６０号、同７１２，８２３号、特公昭４５−５３３１号、特開昭６０−１８５４０号、同５１−１３０２１７号、同５８−１３７８３１号、同５５−５０２４０号、等の各公報に詳しく記載されている。
【０１６３】
前記ポリマー微粒子の平均粒径は１０〜１００ｎｍが好ましく、３０〜８０ｎｍがより好ましい。
【０１６４】
−水溶性樹脂−
前記インクジェット記録用シートでは、その色材受容層が、前記ポリマー微粒子と共に水溶性樹脂を含有するのが好ましい。
【０１６５】
前記水溶性樹脂としては、例えば、親水性構造単位としてヒドロキシ基を有する樹脂であるポリビニルアルコール系樹脂〔ポリビニルアルコール（ＰＶＡ）、アセトアセチル変性ポリビニルアルコール、カチオン変性ポリビニルアルコール、アニオン変性ポリビニルアルコール、シラノール変性ポリビニルアルコール、ポリビニルアセタール等〕、セルロース系樹脂〔メチルセルロース（ＭＣ）、エチルセルロース（ＥＣ）、ヒドロキシエチルセルロース（ＨＥＣ）、カルボキシメチルセルロース（ＣＭＣ）、ヒドロキシプロピルセルロース（ＨＰＣ）、ヒドロキシエチルメチルセルロース、ヒドロキシプロピルメチルセルロース等〕、キチン類、キトサン類、デンプン、エーテル結合を有する樹脂〔ポリエチレンオキサイド（ＰＥＯ）、ポリプロピレンオキサイド（ＰＰＯ）、ポリエチレングリコール（ＰＥＧ）、ポリビニルエーテル（ＰＶＥ）等〕、カルバモイル基を有する樹脂〔ポリアクリルアミド（ＰＡＡＭ）、ポリビニルピロリドン（ＰＶＰ）、ポリアクリル酸ヒドラジド等〕等が挙げられる。
また、解離性基としてカルボキシル基を有するポリアクリル酸塩、マレイン酸樹脂、アルギン酸塩、ゼラチン類等も挙げることができる。
【０１６６】
以上の中でも、特にポリビニルアルコール系樹脂が好ましい。該ポリビニルアルコールの例としては、特公平４−５２７８６号、特公平５−６７４３２号、特公平７−２９４７９号、特許第２５３７８２７号、特公平７−５７５５３号、特許第２５０２９９８号、特許第３０５３２３１号、特開昭６３−１７６１７３号、特許第２６０４３６７号、特開平７−２７６７８７号、特開平９−２０７４２５号、特開平１１−５８９４１号、特開２０００−１３５８５８号、特開２００１−２０５９２４号、特開２００１−２８７４４４号、特開昭６２−２７８０８０号、特開平９−３９３７３号、特許第２７５０４３３号、特開２０００−１５８８０１号、特開２００１−２１３０４５号、特開２００１−３２８３４５号、特開平８−３２４１０５号、特開平１１−３４８４１７号等の公報に記載されたものなどが挙げられる。
また、ポリビニルアルコール系樹脂以外の水溶性樹脂の例としては、特開平１１−１６５４６１号公報の〔００１１〕〜〔００１４〕に記載の化合物なども挙げられる。
これら水溶性樹脂はそれぞれ単独で用いても良く、２種以上を併用して用いてもよい。
【０１６７】
前記水溶性樹脂の含有量は、前記色材受容層の全固形分質量に対して、９〜４０質量％が好ましく、１２〜３３質量％がより好ましい。
【０１６８】
インクジェット記録において、上述のようにして得られた多孔質の色材受容層は、毛細管現象によって急速にインクを吸収し、インク滲みの発生しない真円性の良好なドットを形成することができる。
【０１６９】
−ポリマー微粒子と水溶性樹脂との質量含有比−
ポリマー微粒子（ｘ）と水溶性樹脂（ｙ）との質量含有比〔ＰＢ比（ｘ：ｙ）〕は、色材受容層の膜構造及び膜強度にも大きな影響を与える。即ち、質量含有比〔ＰＢ比〕が大きくなると、空隙率、細孔容積、表面積（単位質量当り）が大きくなるが、密度や強度は低下する傾向にある。
【０１７０】
前記色材受容層は、前記質量含有比〔ＰＢ比（ｘ：ｙ）〕としては、該ＰＢ比が大き過ぎることに起因する、膜強度の低下や乾燥時のひび割れを防止し、且つ該ＰＢ比が小さ過ぎることによって、該空隙が樹脂によって塞がれ易くなり、空隙率が減少することでインク吸収性が低下するのを防止する観点から、５／１〜２０／１が好ましく、１０／１〜２０／１がより好ましい。
【０１７１】
インクジェットプリンターの搬送系を通過する場合、記録用シートに応力が加わることがあるので、色材受容層は十分な膜強度を有していることが必要である。またシート状に裁断加工する場合、色材受容層の割れや剥がれ等を防止する上でも、色材受容層には十分な膜強度を有していることが好ましい。
【０１７２】
−架橋剤−
前記インクジェット記録用シートの色材受容層は、前記水溶性樹脂を含む塗布層が更に前記水溶性樹脂を架橋し得る架橋剤を含むことが好ましく、特に前記ポリマー微粒子と前記水溶性樹脂とを併用し、更に該架橋剤と水溶性樹脂との架橋反応によって硬化された多孔質層である態様が好ましい。
【０１７３】
前記の水溶性樹脂、特にポリビニルアルコールの架橋には、ホウ素化合物が好ましい。該ホウ素化合物としては、硼砂、硼酸、硼酸塩（例えば、オルト硼酸塩、ＩｎＢＯ_３、ＳｃＢＯ_３、ＹＢＯ_３、ＬａＢＯ_３、Ｍｇ_３(ＢＯ_３)_２、Ｃｏ_３(ＢＯ_３)_２、二硼酸塩（例えば、Ｍｇ_２Ｂ_２Ｏ_５、Ｃｏ_２Ｂ_２Ｏ_５）、メタ硼酸塩（例えば、ＬｉＢＯ_２、Ｃａ(ＢＯ_２)_２、ＮａＢＯ_２、ＫＢＯ_２）、四硼酸塩（例えば、Ｎａ_２Ｂ_４Ｏ_７・１０Ｈ_２Ｏ）、五硼酸塩（例えば、ＫＢ_５Ｏ_８・４Ｈ_２Ｏ、Ｃａ_２Ｂ_６Ｏ_１１・７Ｈ_２Ｏ、ＣｓＢ_５Ｏ_５）等を挙げることができる。中でも、速やかに架橋反応を起こすことができる点で、硼砂、硼酸、硼酸塩が好ましく、特に硼酸が好ましい。
【０１７４】
前記水溶性樹脂の架橋剤として、ホウ素化合物以外の下記化合物を使用することもできる。
例えば、ホルムアルデヒド、グリオキザール、グルタールアルデヒド等のアルデヒド系化合物；ジアセチル、シクロペンタンジオン等のケトン系化合物；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、２，４−ジクロロ−６−Ｓ−トリアジン・ナトリウム塩等の活性ハロゲン化合物；ジビニルスルホン酸、１，３−ビニルスルホニル−２−プロパノール、Ｎ，Ｎ’−エチレンビス（ビニルスルホニルアセタミド）、１，３，５−トリアクリロイル−ヘキサヒドロ−Ｓ−トリアジン等の活性ビニル化合物；ジメチロ−ル尿素、メチロールジメチルヒダントイン等のＮ−メチロール化合物；メラミン樹脂（例えば、メチロールメラミン、アルキル化メチロールメラミン）；エポキシ樹脂；１，６−ヘキサメチレンジイソシアネート等のイソシアネート系化合物；米国特許明細書第３０１７２８０号、同第２９８３６１１号に記載のアジリジン系化合物；米国特許明細書第３１００７０４号に記載のカルボキシイミド系化合物；グリセロールトリグリシジルエーテル等のエポキシ系化合物；１，６−ヘキサメチレン−Ｎ，Ｎ’−ビスエチレン尿素等のエチレンイミノ系化合物；ムコクロル酸、ムコフェノキシクロル酸等のハロゲン化カルボキシアルデヒド系化合物；２，３−ジヒドロキシジオキサン等のジオキサン系化合物；乳酸チタン、硫酸アルミ、クロム明ばん、カリ明ばん、酢酸ジルコニル、酢酸クロム等の金属含有化合物、テトラエチレンペンタミン等のポリアミン化合物、アジピン酸ジヒドラジド等のヒドラジド化合物、オキサゾリン基を２個以上含有する低分子又はポリマー等である。
前記の橋剤は、一種単独で用いてもよいし、２種以上を組み合わせて用いてもよい。
【０１７５】
前記架橋硬化は、ポリマー微粒子、水溶性樹脂等を含有する塗布液（以下、「塗布液Ａ」ということがある）及び／又は下記塩基性溶液に架橋剤を添加し、かつ、（１）前記塗布液を塗布して塗布層を形成すると同時、又は（２）前記塗布液を塗布して形成される塗布層の乾燥途中であって該塗布層が減率乾燥を示す前のいずれかのときに、ｐＨ８以上の塩基性溶液（以下、「塗布液Ｂ」ということがある）を前記塗布層に付与することにより行うことが好ましい。
前記架橋剤の付与は、ホウ素化合物を例にすると下記のように行われることが好ましい。即ち、色材受容層が、ポリマー微粒子、ポリビニルアルコールを含む水溶性樹脂を含有する塗布液（塗布液Ａ）を塗布した塗布層を架橋硬化させた層である場合、架橋硬化は、（１）前記塗布液を塗布して塗布層を形成すると同時、（２）前記塗布液を塗布して形成される塗布層の乾燥塗中であって該塗布層が減率乾燥を示す前のいずれかのときに、ｐＨ８以上の塩基性溶液（塗布液Ｂ）を前記塗布層に付与することにより行われる。架橋剤たるホウ素化合物は、塗布液Ａ、又は塗布液Ｂのいずれかに含有すればよく、塗布液Ａ及び塗布液Ｂの両方に含有させておいてもよい。
架橋剤の使用量は、水溶性樹脂に対して、１〜５０質量％が好ましく、５〜４０質量％がより好ましい。
【０１７６】
−媒染剤−
本発明においては、形成画像の耐水性及び耐経時ニジミの向上を図るために、色材受容層に媒染剤が含有されるのが好ましい。
前記媒染剤としては、有機媒染剤としてカチオン性のポリマー（カチオン性媒染剤）、又は無機媒染剤が好ましい。前記媒染剤を色材受容層中に存在させることにより、アニオン性染料を色材として有する液状インクとの間で相互作用し色材を安定化し、耐水性及び耐経時ニジミを向上させることができる。有機媒染剤及び無機媒染剤はそれぞれ単独種で使用しても良いし、有機媒染剤及び無機媒染剤を併用してもよい。
【０１７７】
前記媒染剤は、ポリマー微粒子と水溶性樹脂を含む前記塗布液Ａに添加する方法、又はポリマー微粒子との間で凝集を生ずる懸念がある場合は、前記塗布液Ｂに含有させ塗布する方法を利用できる。
【０１７８】
前記カチオン性媒染剤としては、カチオン性基として、第１級〜第３級アミノ基、又は第４級アンモニウム塩基を有するポリマー媒染剤が好適に用いられるが、カチオン性の非ポリマー媒染剤も使用することができる。これら媒染剤は、色材受容層のインク吸収性良化の観点から、質量平均分子量が５００〜１０００００の化合物が好ましい。
前記ポリマー媒染剤としては、第１級〜第３級アミノ基及びその塩、又は第４級アンモニウム塩基を有する単量体（媒染モノマー）の単独重合体や、該媒染モノマーと他のモノマー（以下、「非媒染モノマー」という。）との共重合体又は縮重合体として得られるものが好ましい。また、これらのポリマー媒染剤は、水溶性ポリマー又は水分散性ラテックス粒子のいずれの形態でも使用できる。
【０１７９】
前記単量体（媒染モノマー）としては、例えば、トリメチル−ｐ−ビニルベンジルアンモニウムクロライド、トリメチル−ｍ−ビニルベンジルアンモニウムクロライド、トリエチル−ｐ−ビニルベンジルアンモニウムクロライド、トリエチル−ｍ−ビニルベンジルアンモニウムクロライド、Ｎ，Ｎ−ジメチル−Ｎ−エチル−Ｎ−ｐ−ビニルベンジルアンモニウムクロライド、Ｎ，Ｎ−ジエチル−Ｎ−メチル−Ｎ−ｐ−ビニルベンジルアンモニウムクロライド、Ｎ，Ｎ−ジメチル−Ｎ−ｎ−プロピル−Ｎ−ｐ−ビニルベンジルアンモニウムクロライド、Ｎ，Ｎ−ジメチル−Ｎ−ｎ−オクチル−Ｎ−ｐ−ビニルベンジルアンモニウムクロライド、Ｎ，Ｎ−ジメチル−Ｎ−ベンジル−Ｎ−ｐ−ビニルベンジルアンモニウムクロライド、Ｎ，Ｎ−ジエチル−Ｎ−ベンジル−Ｎ−ｐ−ビニルベンジルアンモニウムクロライド、Ｎ，Ｎ−ジメチル−Ｎ−（４−メチル）ベンジル−Ｎ−ｐ−ビニルベンジルアンモニウムクロライド、Ｎ，Ｎ−ジメチル−Ｎ−フェニル−Ｎ−ｐ−ビニルベンジルアンモニウムクロライド；トリメチル−ｐ−ビニルベンジルアンモニウムブロマイド、トリメチル−ｍ−ビニルベンジルアンモニウムブロマイド、トリメチル−ｐ−ビニルベンジルアンモニウムスルホネート、トリメチル−ｍ−ビニルベンジルアンモニウムスルホネート、トリメチル−ｐ−ビニルベンジルアンモニウムアセテート、トリメチル−ｍ−ビニルベンジルアンモニウムアセテート、Ｎ，Ｎ，Ｎ−トリエチル−Ｎ−２−（４−ビニルフェニル）エチルアンモニウムクロライド、Ｎ，Ｎ，Ｎ−トリエチル−Ｎ−２−（３−ビニルフェニル）エチルアンモニウムクロライド、Ｎ，Ｎ−ジエチル−Ｎ−メチル−Ｎ−２−（４−ビニルフェニル）エチルアンモニウムクロライド、Ｎ，Ｎ−ジエチル−Ｎ−メチル−Ｎ−２−（４−ビニルフェニル）エチルアンモニウムアセテート；Ｎ，Ｎ−ジメチルアミノエチル（メタ）アクリレート、Ｎ，Ｎ−ジエチルアミノエチル（メタ）アクリレート、Ｎ，Ｎ−ジメチルアミノプロピル（メタ）アクリレート、Ｎ，Ｎ−ジエチルアミノプロピル（メタ）アクリレート、Ｎ，Ｎ−ジメチルアミノエチル（メタ）アクリルアミド、Ｎ，Ｎ−ジエチルアミノエチル（メタ）アクリルアミド、Ｎ，Ｎ−ジメチルアミノプロピル（メタ）アクリルアミド、Ｎ，Ｎ−ジエチルアミノプロピル（メタ）アクリルアミドのメチルクロライド、エチルクロライド、メチルブロマイド、エチルブロマイド、メチルアイオダイド若しくはエチルアイオダイドによる４級化物、又はそれらのアニオンを置換したスルホン酸塩、アルキルスルホン酸塩、酢酸塩若しくはアルキルカルボン酸塩等が挙げられる。
【０１８０】
具体的には、モノメチルジアリルアンモニウムクロライド、トリメチル−２−（メタクリロイルオキシ）エチルアンモニウムクロライド、トリエチル−２−（メタクリロイルオキシ）エチルアンモニウムクロライド、トリメチル−２−（アクリロイルオキシ）エチルアンモニウムクロライド、トリエチル−２−（アクリロイルオキシ）エチルアンモニウムクロライド、トリメチル−３−（メタクリロイルオキシ）プロピルアンモニウムクロライド、トリエチル−３−（メタクリロイルオキシ）プロピルアンモニウムクロライド、トリメチル−２−（メタクリロイルアミノ）エチルアンモニウムクロライド、トリエチル−２−（メタクリロイルアミノ）エチルアンモニウムクロライド、トリメチル−２−（アクリロイルアミノ）エチルアンモニウムクロライド、トリエチル−２−（アクリロイルアミノ）エチルアンモニウムクロライド、トリメチル−３−（メタクリロイルアミノ）プロピルアンモニウムクロライド、トリエチル−３−（メタクリロイルアミノ）プロピルアンモニウムクロライド、トリメチル−３−（アクリロイルアミノ）プロピルアンモニウムクロライド、トリエチル−３−（アクリロイルアミノ）プロピルアンモニウムクロライド；Ｎ，Ｎ−ジメチル−Ｎ−エチル−２−（メタクリロイルオキシ）エチルアンモニウムクロライド、Ｎ，Ｎ−ジエチル−Ｎ−メチル−２−（メタクリロイルオキシ）エチルアンモニウムクロライド、Ｎ，Ｎ−ジメチル−Ｎ−エチル−３−（アクリロイルアミノ）プロピルアンモニウムクロライド、トリメチル−２−（メタクリロイルオキシ）エチルアンモニウムブロマイド、トリメチル−３−（アクリロイルアミノ）プロピルアンモニウムブロマイド、トリメチル−２−（メタクリロイルオキシ）エチルアンモニウムスルホネート、トリメチル−３−（アクリロイルアミノ）プロピルアンモニウムアセテート等を挙げることができる。
その他、共重合可能なモノマーとしては、Ｎ−ビニルイミダゾール、Ｎ−ビニル−２−メチルイミダゾール等も挙げられる。
【０１８１】
また、アリルアミン、ジアリルアミン又はその誘導体、塩なども利用できる。このような化合物の例としてはアリルアミン、アリルアミン塩酸塩、アリルアミン酢酸塩、アリルアミン硫酸塩、ジアリルアミン、ジアリルアミン塩酸塩、ジアリルアミン酢酸塩、ジアリルアミン硫酸塩、ジアリルメチルアミン及びこの塩（該塩としては、例えば、塩酸塩、酢酸塩、硫酸塩など）、ジアリルエチルアミン及びこの塩（該塩としては、例えば、塩酸塩、酢酸塩、硫酸塩など）、ジアリルジメチルアンモニウム塩（該塩の対アニオンとしてはクロライド、酢酸イオン硫酸イオンなど）が挙げられる。尚、これらのアリルアミン及びジアリルアミン誘導体はアミンの形態では重合性が劣るので塩の形で重合し、必要に応じて脱塩することが一般的である。
また、Ｎ−ビニルアセトアミド、Ｎ−ビニルホルムアミドなどの単位を用い、重合後に加水分解によってビニルアミン単位とすること、及びこれを塩にしたものも利用できる。
【０１８２】
前記非媒染モノマーとしては、第１級〜第３級アミノ基及びその塩、又は第４級アンモニウム塩基等の塩基性或いはカチオン性部分を含まず、インクジェットインク中の染料と相互作用を示さない、或いは相互作用が実質的に小さいモノマーを意味する。
前記非媒染モノマーとしては、例えば、（メタ）アクリル酸アルキルエステル；（メタ）アクリル酸シクロヘキシル等の（メタ）アクリル酸シクロアルキルエステル；（メタ）アクリル酸フェニル等の（メタ）アクリル酸アリールエステル；（メタ）アクリル酸ベンジル等のアラルキルエステル；スチレン、ビニルトルエン、α−メチルスチレン等の芳香族ビニル類；酢酸ビニル、プロピオン酸ビニル、バーサチック酸ビニル等のビニルエステル類；酢酸アリル等のアリルエステル類；塩化ビニリデン、塩化ビニル等のハロゲン含有単量体；（メタ）アクリロニトリル等のシアン化ビニル；エチレン、プロピレン等のオレフィン類、等が挙げられる。
【０１８３】
前記（メタ）アクリル酸アルキルエステルとしては、アルキル部位の炭素数が１〜１８の（メタ）アクリル酸アルキルエステルが好ましく、例えば、（メタ）アクリル酸メチル、（メタ）アクリル酸エチル、（メタ）アクリル酸プロピル、（メタ）アクリル酸イソプロピル、（メタ）アクリル酸ｎ−ブチル、（メタ）アクリル酸イソブチル、（メタ）アクリル酸ｔ−ブチル、（メタ）アクリル酸ヘキシル、（メタ）アクリル酸オクチル、（メタ）アクリル酸２−エチルヘキシル、（メタ）アクリル酸ラウリル、（メタ）アクリル酸ステアリル等が挙げられる。これらの中でも、メチルアクリレート、エチルアクリレート、メチルメタアクリレート、エチルメタアクリレート、ヒドロキシエチルメタアクリレートが好ましい。
前記非媒染モノマーは、一種単独で又は二種以上を組み合わせて使用できる。
【０１８４】
前記ポリマー媒染剤としては、例えば、ポリジアリルジメチルアンモニウムクロライド、ポリメタクリロイルオキシエチル−β−ヒドロキシエチルジメチルアンモニウムクロライド、ポリエチレンイミン、ポリアリルアミン及びその誘導体、ポリアミド−ポリアミン樹脂、カチオン化でんぷん、ジシアンジアミドホルマリン縮合物、ジメチル−２−ヒドロキシプロピルアンモニウム塩重合物、ポリアミジン、ポリビニルアミン、ジシアンジアミド−ホルマリン重縮合物に代表されるジシアン系カオチン樹脂、ジシアンアミド−ジエチレントリアミン重縮合物に代表されるポリアミン系カオチン樹脂、エピクロルヒドリン−ジメチルアミン付加重合物、ジメチルジアリンアンモニウムクロリド−ＳＯ_２共重合物、ジアリルアミン塩−ＳＯ_２共重合物、第４級アンモニウム塩基置換アルキル基をエステル部分に有する（メタ）アクリレート含有ポリマー、第４級アンモニウム塩基置換アルキル基を有するスチリル型ポリマー等も好ましいものとして挙げることができる。
【０１８５】
前記ポリマー媒染剤としては、例えば、特開昭４８−２８３２５号、同５４−７４４３０号、同５４−１２４７２６号、同５５−２２７６６号、同５５−１４２３３９号、同６０−２３８５０号、同６０−２３８５１号、同６０−２３８５２号、同６０−２３８５３号、同６０−５７８３６号、同６０−６０６４３号、同６０−１１８８３４号、同６０−１２２９４０号、同６０−１２２９４１号、同６０−１２２９４２号、同６０−２３５１３４号、特開平１−１６１２３６号の各公報、米国特許２４８４４３０、同２５４８５６４号、同３１４８０６１号、同３３０９６９０号、同４１１５１２４号、同４１２４３８６号、同４１９３８００号、同４２７３８５３号、同４２８２３０５号、同４４５０２２４号、特開平１−１６１２３６号、同１０−８１０６４号、同１０−１１９４２３号、同１０−１５７２７７号、同１０−２１７６０１号、同１１−３４８４０９号、特開２００１−１３８６２１号、同２０００−４３４０１号、同２０００−２１１２３５号、同２０００−３０９１５７号、同２００１−９６８９７号、同２００１−１３８６２７号、特開平１１−９１２４２号、同８−２０８７号、同８−２０９０号、同８−２０９１号、同８−２０９３号、同８−１７４９９２号、同１１−１９２７７７号、特開２００１−３０１３１４号、特公平５‐３５１６２号、同５-３５１６３号、同５‐３５１６４号、同５-８８８４６号、特開平７-１１８３３３号、特開２０００-３４４９９０号、特許第２６４８８４７号、同２６６１６７７号等の各公報に記載のもの等が挙げられる。これらの中でもポリアリルアミン及びその誘導体が特に好ましい。
【０１８６】
前記有機媒染剤としては、特に、経時滲みの防止の観点から、質量平均分子量が１０００００以下のポリアリルアミン及びその誘導体が好ましい。
【０１８７】
前記ポリアリルアミン又はその誘導体としては、公知の各種アリルアミン重合体及びその誘導体が使用できる。このような誘導体としては、ポリアリルアミンと酸との塩（酸としては塩酸、硫酸、リン酸、硝酸などの無機酸、メタンスルホン酸、トルエンスルホン酸、酢酸、プロピオン酸、桂皮酸、（メタ）アクリル酸などの有機酸、或いはこれらの組合せや、アリルアミンの一部分のみを塩にしたもの）、ポリアリルアミンの高分子反応による誘導体、ポリアリルアミンと他の共重合可能なモノマーとの共重合体（該モノマーの具体例としては（メタ）アクリル酸エステル類、スチレン類、（メタ）アクリルアミド類、アクリロニトリル、ビニルエステル類等）が挙げられる。
【０１８８】
前記ポリアリルアミン及びその誘導体の具体例としては、特公昭６２−３１７２２号、特公平２−１４３６４号、特公昭６３−４３４０２号、同６３−４３４０３号、同６３−４５７２１号、同６３−２９８８１号、特公平１−２６３６２号、同２−５６３６５号、同２−５７０８４号、同４−４１６８６号、同６−２７８０号、同６−４５６４９号、同６−１５５９２号、同４−６８６２２号、特許第３１９９２２７号、同３００８３６９号、特開平１０−３３０４２７号、同１１−２１３２１号、特開２０００−２８１７２８号、同２００１−１０６７３６号、特開昭６２−２５６８０１号、特開平７−１７３２８６号、同７−２１３８９７号、同９−２３５３１８号、同９−３０２０２６号、同１１−２１３２１号、ＷＯ９９／２１９０１号、ＷＯ９９／１９３７２号、特開平５−１４０２１３号、特表平１１−５０６４８８号等の各公報に記載の化合物が挙げられる。
【０１８９】
前記媒染剤としては、無機媒染剤を用いることも可能で、多価の水溶性金属塩や疎水性金属塩化合物が挙げられる。
無機媒染剤の具体例としては、マグネシウム、アルミニウム、カルシウム、スカンジウム、チタン、バナジウム、マンガン、鉄、ニッケル、銅、亜鉛、ガリウム、ゲルマニウム、ストロンチウム、イットリウム、ジルコニウム、モリブデン、インジウム、バリウム、ランタン、セリウム、プラセオジミウム、ネオジミウム、サマリウム、ユーロピウム、ガドリニウム、ジスロプロシウム、エルビウム、イッテルビウム、ハフニウム、タングステン、ビスマスから選択される金属の塩又は錯体が挙げられる。
【０１９０】
具体的には、酢酸カルシウム、塩化カルシウム、ギ酸カルシウム、硫酸カルシウム、酢酸バリウム、硫酸バリウム、リン酸バリウム、塩化マンガン、酢酸マンガン、ギ酸マンガンニ水和物、硫酸マンガンアンモニウム六水和物、塩化第二銅、塩化アンモニウム銅（II）二水和物、硫酸銅、塩化コバルト、チオシアン酸コバルト、硫酸コバルト、硫酸ニッケル六水和物、塩化ニッケル六水和物、酢酸ニッケル四水和物、硫酸ニッケルアンモニウム六水和物、アミド硫酸ニッケル四水和物、硫酸アルミニウム、アルミニウムミョウバン、塩基性ポリ水酸化アルミニウム、亜硫酸アルミニウム、チオ硫酸アルミニウム、ポリ塩化アルミニウム、硝酸アルミニウム九水和物、塩化アルミニウム六水和物、臭化第一鉄、塩化第一鉄、塩化第二鉄、硫酸第一鉄、硫酸第二鉄、フェノールスルホン酸亜鉛、臭化亜鉛、塩化亜鉛、硝酸亜鉛六水和物、硫酸亜鉛、四塩化チタン、テトライソプロピルチタネート、チタンアセチルアセトネート、乳酸チタン、ジルコニウムアセチルアセトネート、酢酸ジルコニル、硫酸ジルコニル、炭酸ジルコニウムアンモニウム、ステアリン酸ジルコニル、オクチル酸ジルコニル、硝酸ジルコニル、オキシ塩化ジルコニウム、ヒドロキシ塩化ジルコニウム、酢酸クロム、硫酸クロム、硫酸マグネシウム、塩化マグネシウム六水和物、クエン酸マグネシウム九水和物、りんタングステン酸ナトリウム、クエン酸ナトリウムタングステン、１２タングストリん酸ｎ水和物、１２タングストけい酸２６水和物、塩化モリブデン、１２モリブドリん酸ｎ水和物、硝酸ガリウム、硝酸ゲルマニウム、硝酸ストロンチウム、酢酸イットリウム、塩化イットリウム、硝酸イットリウム、硝酸インジウム、硝酸ランタン、塩化ランタン、酢酸ランタン、安息香酸ランタン、塩化セリウム、硫酸セリウム、オクチル酸セリウム、硝酸プラセオジミウム、硝酸ネオジミウム、硝酸サマリウム、硝酸ユーロピウム、硝酸ガドリニウム、硝酸ジスプロシウム、硝酸エルビウム、硝酸イッテルビウム、塩化ハフニウム、硝酸ビスマス等が挙げられる。
【０１９１】
前記無機媒染剤としては、アルミニウム含有化合物、チタン含有化合物、ジルコニウム含有化合物、元素周期律表第ＩＩＩＢ族シリーズの金属化合物（塩又は錯体）が好ましい。
色材受容層に含まれる前記媒染剤量は、０．０１ｇ／ｍ^２〜５ｇ／ｍ^２が好ましく、０．１ｇ／ｍ^２〜３ｇ／ｍ^２がより好ましい。
【０１９２】
−その他の成分−
前記インクジェット記録用シートには、更に必要に応じて、各種の公知の添加剤、例えば、酸、紫外線吸収剤、酸化防止剤、蛍光増白剤、モノマー、重合開始剤、重合禁止剤、滲み防止剤、防腐剤、粘度安定剤、消泡剤、界面活性剤、帯電防止剤、マット剤、カール防止剤、耐水化剤等を含有することができる。
【０１９３】
＜銀塩写真感光材料＞
前記銀塩写真感光材料としては、例えば、前記本発明の記録材料用支持体上に、少なくともＹＭＣに発色する画像形成層を設けた構成を有し、焼付露光されたハロゲン化銀写真用シートを複数の処理槽内を浸漬しながら通過することにより、発色現像、漂白定着、水洗を行い、乾燥するハロゲン化銀写真方式、等が挙げられる。
【０１９４】
＜熱転写受像材料＞
前記熱転写材料としては、例えば、前記本発明の記録材料用支持体上に、少なくとも熱発色層を設けた構成を有し、感熱ヘッドによる加熱と紫外線による定着の繰り返しにより画像を形成するサーモオートクローム方式（ＴＡ方式）において用いられる感熱発色記録材料等が挙げられる。
【０１９５】
＜感熱発色記録材料＞
前記感熱発色記録材料としては、例えば、前記本発明の記録材料用支持体上に、少なくとも画像形成層としての熱溶融性インク層を設けた構成を有し、感熱ヘッドにより加熱して熱溶融性インク層からインクを感熱転写記録用受像シート上に溶融転写する方式などが挙げられる。
【０１９６】
＜昇華転写受像材料＞
前記昇華転写受像材料としては、前記本発明の記録材料用支持体上に、少なくとも熱拡散性色素（昇華性色素）を含有するインク層を設けた構成を有し、感熱ヘッドにより加熱してインク層から熱拡散性色素を感熱転写記録受像シート上に転写する昇華転写方式などが挙げられる。
【０１９７】
【実施例】
以下に本発明の実施例について説明するが、本発明はこれらの実施例に何ら限定されるものではない。
なお、以下の実施例及び比較例において、「％」及び「部」は質量基準である。
【０１９８】
（実施例１）
−支持体の調製−
広葉樹晒クラフトパルプ（ＬＢＫＰ）をディスクリファイナーで３００ｍｌ（カナダ標準ろ水度、Ｃ．Ｆ．Ｓ．）まで叩解し、平均質量繊維長０．５８ｍｍに調整した。このパルプ紙料に対して、パルプの質量に基づいて、以下の割合で添加剤を添加した。
添加剤の種類 量（％）
カチオンスターチ １．２
アルキルケテンダイマー（ＡＫＤ） ０．４
アニオンポリアクリルアミド ０．２
エポキシ化脂肪酸アミド（ＥＦＡ） ０．２
ポリアミドポリアミンエピクロルヒドリン ０．３
注）ＡＫＤは、アルキルケテンダイマー（アルキル部分は、ベヘン酸を主体とする脂肪酸由来のものである）を意味し、ＥＦＡは、エポキシ化脂肪酸アミド（脂肪酸部分は、ベヘン酸を主体とする脂肪酸由来のものである）を意味する。
【０１９９】
得られたパルプ紙料を、長網抄紙機により坪量１５０ｇ／ｍ^２の原紙を作製した。なお、長網抄紙機の乾燥ゾーンの中間で原紙の表面（トナー受像層を塗布する面）にゲートロールコーターにより、固形分で３ｇ／ｍ^２となるようにポリエチレンソープフリーエマルジョンを塗布し乾燥した。
抄紙工程の最後で、トナー受像層を形成する側の表面に金属ロールが接するようにカレンダー処理して密度を１．０１ｇ／ｃｍ^３に調整し、支持体を得た。なお、金属ロールの表面温度は１４０℃であった。
【０２００】
（実施例２〜５及び比較例１〜３）
表１に示したように、原紙に使用する表面処理剤、カレンダー処理の温度条件を変更した以外は実施例１と同様にして実施例２〜５及び比較例１〜３の支持体を作製した。
【０２０１】
得られた実施例１〜５及び比較例１〜３の各支持体について、下記方法によりコブサイズ度、ベック平滑度、及び表面平滑性を測定した。結果を表１に示す。
【０２０２】
＜コブサイズ度＞
ＪＩＳ Ｐ８１４０に従って測定した。
＜ベック平滑度＞
ＪＩＳ Ｐ ８１１９に従って測定した。
＜表面平滑性＞
表面形状測定装置サーフコム５７０Ａ−３ＤＦ（株式会社東京精密製）を用いて、下記測定及び解析条件に基づき、カットオフ５ｍｍ〜６ｍｍ条件下での前記支持体の画像形成層を設ける側の中心面平均粗さ（ＳＲａ）を測定した。
−測定及び解析条件−
・走査方向：サンプルのＭＤ方向
・測定長さ：抄紙（Ｘ）方向５０ｍｍ、その垂直（Ｙ）方向３０ｍｍ
・測定ピッチ：Ｘ方向０．１ｍｍ、Ｙ方向０．１ｍｍ
・走査速度：３０ｍｍ／ｓｅｃ
・バンドパスフィルター：５ｍｍ〜６ｍｍ
また、各支持体の画像形成層を設ける側の表面に水を２０℃で２分間接触させた前後におけるＳＲａの変化（ΔＳＲａ）を測定した。
【０２０３】
【表１】

＊ポリエチレンソープフリーエマルジョン（融点＝１０４℃、ユニチカ製）
＊石油樹脂／ワックスエマルジョン（融点＝６５℃、日本ＰＭＣ製）
＊カルボキシ変性ＰＶＡ（クラレ製）
＊酸化澱粉（日本食品化工製）
＊ポリアクリルアミド（荒川化学工業製）
【０２０４】
（実施例６〜１０及び比較例３〜４）
−電子写真用受像シートの作製−
得られた各支持体を用いて、下記のようにして電子写真用受像シートを作製した。
前記支持体の熱ロールの接した面（トナー受像層を設ける側）に下記組成のトナー受像層塗布液及びバック層塗布液をバーコーターにて塗布した。
【０２０５】
−トナー受像層用の塗布液の調製−
（二酸化チタン分散液）
下記の成分を混合し、日本精機製作所製ＮＢＫ−２を用いて分散させ、二酸化チタン分散液（二酸化チタン顔料４０質量％）を作製した。
二酸化チタン
（タイペーク（登録商標）Ａ−２２０、石原産業製） ４０．０ｇ
ＰＶＡ１０２ ２．０ｇ
イオン交換水 ５８．０ｇ
【０２０６】
−トナー受像層用塗布液−
下記成分を混合し、攪拌して、トナー受像層用塗布液を調製した。
上記二酸化チタン分散液 １５．５ｇ
カルナバワックス分散液
（セロゾール５２４、中京油脂製） １５．０ｇ
ポリエステル樹脂水分散物
（固形分３０質量％、ＫＺＡ−７０４９、ユニチカ製） １００．０ｇ
増粘剤(アルコックスＥ３０、明成化学製) ２．０ｇ
アニオン界面活性剤（ＡＯＴ） ０．５ｇ
イオン交換水 ８０ｍｌ
得られたトナー受像層用塗布液の粘度は、４０ｍＰａ・ｓであり、表面張力は３４ｍＮ／ｍであった。
【０２０７】
−バック層用塗布液の調製−
下記の成分を混合し、攪拌して、バック層用塗布液を調製した。
アクリル樹脂水分散物
(固形分３０質量％、ハイロスＸＢＨ−９９７Ｌ、星光化学製) １００．０ｇ
マット剤
（テクポマーＭＢＸ−１２、積水化成品工業製） ５．０ｇ
離型剤(ハイドリンＤ３３７、中京油脂製) １０．０ｇ
増粘剤（ＣＭＣ） ２．０ｇ
アニオン界面活性剤（ＡＯＴ） ０．５ｇ
イオン交換水 ８０ｍｌ
バック層用の塗布液の粘度は、３５ｍＰａ・ｓであり、表面張力は、３３ｍＮ／ｍであった。
【０２０８】
＜バック層及びトナー受像層の塗工＞
得られた支持体の裏面に、上記バック層用の塗布液をバーコーターで塗布し、次いで、支持体の表面に、上記トナー受像層用の塗布液を、バック層の場合と同様に、バーコーターで塗布した。
塗布量は、バック層については、乾燥質量で９ｇ／ｍ^２であり、トナー受像層については、乾燥質量１２ｇになるように、トナー受像層用塗布液及びバック層用塗布液を塗布した。
バック層及びトナー受像層は、塗布後、オンラインで熱風により乾燥した。乾燥は、バック面及びトナー受像面ともに塗布後２分以内に乾燥するように、乾燥風量及び温度を調整した。乾燥点は、塗布表面温度が乾燥風の湿球温度と同じ温度となる点とした。
乾燥後、カレンダー処理を行った。カレンダー処理は、グロスカレンダーを用い、金属ローラを４０℃に保温した状態で、圧力１４７Ｎ／ｃｍ（１５ｋｇｆ／ｃｍ）にて行った。
【０２０９】
＜評価＞
得られた電子写真用受像シートを、Ａ４サイズに裁断し、プリント用画像とした。使用したプリンターは、図１に示す定着ベルト系としたことを除いて、富士ゼロックス製カラーレーザープリンター（ＤｏｃｕＣｏｌｏｒ １２５０−ＰＦ）を用いた。
即ち、図１に示す定着ベルト系１では、加熱ローラ３と、テンションローラ５とにわたって定着ベルト２が懸架され、テンションローラ５には、その上方で、定着ベルト２を介して、クリーニングローラ６が設けられ、更に、加熱ローラ３の下方には、定着ベルト２を介して、加圧ローラ４が設けられている。トナー潜像を有する電子写真用受像シートは、図１において、右側から、加熱ローラ３と、加圧ローラ４との間に挿入され、定着され、次いで、定着ベルト２に載って移動し、クリーニングローラ６で清浄化される。
この定着ベルト系においては、定着ベルト２の搬送速度は、３０ｍｍ／秒であり、加熱ローラ３と加圧ローラ４との間のニップ圧力は、０．２ＭＰａ（２ｋｇｆ／ｃｍ^２）であり、加熱ローラ３の設定温度は、１５０℃であり、これが定着温度に相当する。なお、加圧ローラ４の設定温度は、１２０℃に設定した。
【０２１０】
＜画質＞
各電子写真用受像シートについて、女の人のポートレイト画像を上記画像形成方法により絵出し、下記の評価基準で評価した。結果を表２に示す。
〔評価基準〕
Ａ：最良
Ｂ：良、使用可（許容範囲内）
Ｃ：劣る、使用不可（実用上使用不可）
Ｄ：著しく劣る、使用不可
【０２１１】
＜光沢性＞
プリント後の電子写真用受像シート（電子写真プリント）における光沢性を目視観察し、下記基準で評価した。結果を表２に示す。
〔評価基準〕
Ａ：最良
Ｂ：良、使用可（許容範囲内）
Ｃ：劣る、使用不可（実用上使用不可）
Ｄ：著しく劣る、使用不可
【０２１２】
【表２】

【０２１３】
表２の結果から、実施例１〜５の支持体を用いた実施例６〜１０の電子写真用受像シートは、比較例４〜６に比べて優れた画質及び光沢を有し、鮮明な画像が得られることが認められる。
【０２１４】
【発明の効果】
本発明によれば、従来に比べて、優れた表面平滑性及び耐水性を有する記録材料用支持体が得られる。該記録材料用支持体を記録材料の支持体として用いることにより、画質及び光沢に優れた画像を形成することができる記録材料を提供できる。
【図面の簡単な説明】
【図１】図１は、実施例で使用したプリンターにおける定着ベルト系の概要構成図である。
【符号の説明】
１ 定着ベルト系
２ 定着ベルト
３ 加熱ローラ
４ 加圧ローラ
５ テンションローラ
６ クリーニングローラ[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a recording material support having superior surface smoothness and water resistance, a method for efficiently producing the recording material support, an image quality using the recording material support, and The present invention relates to a recording material capable of forming an image having excellent gloss.
[0002]
[Prior art]
Conventionally, in order to obtain a high-quality image on a support for various recording materials such as an electrophotographic image receiving material, a thermosensitive color recording material, an ink jet recording material, a sublimation transfer image receiving material, a silver salt photographic photosensitive material, and a thermal transfer image receiving material. High surface smoothness and water resistance are required, and various studies have been made.
[0003]
On the other hand, in general commercial printing and high-grade printing, offset printing is the mainstream, and coated paper such as art paper and coated paper is used. This is because the surface of the coated paper is very smooth, so the ink transferability is good, the image reproducibility is high, the image gloss is high, and the color reproducibility is good. is there.
[0004]
However, the coating layer of the coated paper contains a large amount of pigment and has high hygroscopicity. Therefore, when the coated paper itself is used as an electrophotographic image-receiving sheet, when the image is fixed by heat, the water vapor in the coated paper expands, and a blister (coating) is formed between the base paper and the coating layer. Layer swelling). For this reason, there is a problem that the image is rough and a precise image quality such as a photograph cannot be obtained (see, for example, Patent Documents 1 and 2).
In addition, these conventional coated papers also have a problem that gloss is inferior when image information such as a face or a landscape is output as a photograph. Therefore, to date, the use of coated paper as an electrophotographic image-receiving sheet has usually been rarely performed.
[0005]
[Patent Document 1]
JP-A-4-212168
[Patent Document 2]
Japanese Patent Laid-Open No. 8-21645
[Problems to be solved by the invention]
The present invention aims to solve the above-described problems and solve the following problems. That is, the present invention uses a recording material support having superior surface smoothness and water resistance, a method for efficiently producing the recording material support, and the recording material support. An object of the present invention is to provide a recording material capable of forming an image excellent in image quality and gloss.
[0006]
[Means for Solving the Problems]
  Means for solving the above problems are as follows. That is,
  <1> In a support for an electrophotographic image receiving material containing at least a base paper,
  A calendar having a metal roll having a surface temperature of 110 ° C. or more and 150 ° C. or less after applying a coating liquid containing a surface treatment agent comprising a soap-free latex or a soap-free emulsion on the surface of the base paper on which the toner image-receiving layer is provided. Calendar processing,
  The degree of bump size (30 seconds) on the side of the support on which the toner image-receiving layer is provided is 10 g / m²An electrophotographic image-receiving material support characterized by the following.
  <2> In a support for an electrophotographic image receiving material containing at least a base paper,
  A calendar having a metal roll having a surface temperature of 110 ° C. or more and 150 ° C. or less after applying a coating liquid containing a surface treatment agent comprising a soap-free latex or a soap-free emulsion on the surface of the base paper on which the toner image-receiving layer is provided. Calendar processing,
  The average surface roughness (SRa) measured under conditions of 5 mm to 6 mm cut-off on the side of the support on which the toner image receiving layer is provided is 0.7 μm or less, and the side of the support on which the toner image receiving layer is provided. A support for an electrophotographic image-receiving material, wherein the change in SRa (ΔSRa) before and after contact of water with the surface at 20 ° C. for 2 minutes is −0.1 μm to +0.1 μm.
  <3>The coating amount of the coating solution containing the surface treatment agent is 0.5 to 3.5 g / m in solid content. ² The support for an electrophotographic image receiving material according to any one of <1> to <2>.
  <4>in front<1> to <1> in which the Beck smoothness of the support on the side where the toner image-receiving layer is provided is 100 seconds or more.3The support for an electrophotographic image receiving material according to any one of the above.
  <5> The base paper has a freeness of 200 to 440 ml C.I. S. F. <1> to <1> containing a pulp stock4The support for an electrophotographic image receiving material according to any one of the above.
  <6> From <1> above, wherein the base paper contains a pulp stock having a mass average fiber length of 0.45 to 0.65 mm5The support for an electrophotographic image receiving material according to any one of the above.
  <7> At least the surface of the base paper on which the toner image-receiving layer is provided has a water repellent, a sizing agent,And water resistance?<1> to <1> in which at least one selected from the above is applied or impregnated6The support for an electrophotographic image receiving material according to any one of the above.
  <8> The support for an electrophotographic image receiving material according to <7>, wherein the sizing agent is contained in an amount of 0.3% by mass or more per pulp mass of the base paper.
  <9> From <1> to <8> A method for producing a support for an electrophotographic image-receiving material according to any one of
  A calendar having a metal roll having a surface temperature of 110 ° C. or more and 150 ° C. or less after applying a coating liquid containing a surface treatment agent comprising a soap-free latex or a soap-free emulsion on the surface of the base paper on which the toner image-receiving layer is provided. Calendar processingA method for producing a support for an electrophotographic image-receiving material.
  <10An electrophotographic image receiving material having a support for an electrophotographic image receiving material containing at least a base paper, and a toner image receiving layer on the support,
  <1> to <1> as the support8The electrophotographic image-receiving material support according to any one of the above is used.
[0007]
The recording material support of the present invention comprises at least a base paper, and at least the image forming layer on the surface of the recording material support on the surface on which the image forming layer is provided. 30 seconds) is 10g / m²It is as follows. (2) The average surface roughness (SRa) measured under conditions of a cutoff of 5 mm to 6 mm on the side of the support on which the image forming layer is provided is 0.7 μm or less, and the image forming layer of the support is The change in SRa (ΔSRa) before and after contacting the surface on the side to be provided with water at 20 ° C. for 2 minutes is −0.1 μm to +0.1 μm. As a result, it is excellent in surface smoothness and water resistance, and in particular, a support in a recording material such as an electrophotographic image receiving material, an ink jet recording material, a silver salt photographic photosensitive material, a sublimation transfer image receiving material, a thermosensitive color recording material, a thermal transfer image receiving material. A support for a recording material suitable for the above is obtained.
[0008]
The method for producing a recording material support of the present invention comprises a coating liquid containing at least one surface treatment agent selected from a soap-free latex and a soap-free emulsion on the surface of the base paper on which an image forming layer is provided. After applying, calender treatment. Thereby, it is possible to efficiently produce a recording material support having excellent surface smoothness and water resistance.
[0009]
The recording material of the present invention uses the recording material support of the present invention as a support. As a result, it is excellent in image quality and gloss even with any recording material selected from electrophotographic image receiving materials, ink jet recording materials, silver salt photographic photosensitive materials, sublimation transfer image receiving materials, heat-sensitive color recording materials and thermal transfer image receiving materials. Images can be formed.
[0010]
DETAILED DESCRIPTION OF THE INVENTION
(Recording material support)
The recording material support of the present invention is a recording material support containing at least a base paper, and has a degree of bump size (30 seconds), a center surface average roughness (SRa), and SRa on the side of the support on which an image forming layer is provided. At least one condition selected from the change (ΔSRa) is optimized.
[0011]
-Base paper-
The base paper is not particularly limited and may be appropriately selected depending on the intended purpose. Specifically, it is a high-quality paper, for example, “Photographic Engineering Basics—Silver Salt Photography” edited by the Japan Photography Society, Ltd. The paper etc. of a corona company publication (Showa 54) (223)-(240) page are mentioned as a suitable thing.
[0012]
In order to impart a desired centerline average roughness to the surface of the base paper, for example, as described in JP-A-58-68037, a fiber length distribution (for example, a 24 mesh screen residue and , 42 mesh screen residue is preferably 20 to 45% by mass and 24 mesh screen residue is preferably 5% by mass or less). Further, the center line average roughness can be adjusted by applying heat and pressure to the surface with a machine calendar, a super calendar, or the like.
[0013]
The base paper is not particularly limited as long as it is a known material used for the support for image recording materials, and can be appropriately selected from various materials according to the purpose. For example, natural paper such as conifers and hardwoods can be selected. Examples thereof include synthetic pulp made of synthetic resin such as pulp, polyethylene, and polypropylene, or a mixture of natural pulp and synthetic pulp.
[0014]
The pulp that can be used as the raw material of the base paper is hardwood bleached kraft pulp (LBKP) from the viewpoint of improving the surface smoothness, rigidity and dimensional stability (curling property) of the base paper to a balanced and sufficient level at the same time. Although desirable, softwood bleached kraft pulp (NBKP), hardwood sulfite pulp (LBSP) and the like can also be used.
A beater, refiner, or the like can be used for beating the pulp.
The Canadian standard freeness of the pulp can control the shrinkage of the paper in the paper making process, so 200-440 ml C.I. S. F. Is more preferred, 250-380 ml C.I. S. F. Is more preferable.
In the pulp slurry obtained after beating the pulp (hereinafter sometimes referred to as “pulp paper material”), various additives such as a filler, a dry paper strength enhancer, a sizing agent, A wet paper strength enhancer, a fixing agent, a pH adjuster, and other agents are added.
[0015]
Examples of the filler include calcium carbonate, clay, kaolin, white clay, talc, titanium oxide, diatomaceous earth, barium sulfate, aluminum hydroxide, and magnesium hydroxide.
Examples of the dry paper strength enhancer include cationized starch, cationized polyacrylamide, anionized polyacrylamide, amphoteric polyacrylamide, and carboxy-modified polyvinyl alcohol.
[0016]
Examples of the wet paper strength enhancer include polyamine polyamide epichlorohydrin, melamine resin, urea resin, and epoxidized polyamide resin.
Examples of the fixing agent include polyvalent metal salts such as aluminum sulfate and aluminum chloride, and cationic polymers such as cationized starch.
Examples of the pH adjuster include caustic soda and sodium carbonate.
As said other chemical | medical agent, an antifoamer, dye, a slime control agent, a fluorescent whitening agent, etc. are mentioned, for example.
Furthermore, a softening agent etc. can also be added as needed. As the softening agent, for example, those described in New Handbook for Paper Processing (Edited by Paper Medicine Time), pages 554 to 555 (issued in 1980) can be used.
[0017]
There is no restriction | limiting in particular in the process liquid used for the said surface size process, According to the objective, it can select suitably, For example, water-soluble polymer, a water-resistant substance, a pigment, dye, fluorescent whitening agent etc. It may be included.
Examples of the water-soluble polymer include cationized starch, polyvinyl alcohol, carboxy-modified polyvinyl alcohol, carboxymethyl cellulose, hydroxyethyl cellulose, cellulose sulfate, gelatin, casein, sodium polyacrylate, styrene-maleic anhydride copolymer sodium salt. And sodium polystyrene sulfonate.
[0018]
Examples of the water-resistant substance include latex / emulsions such as styrene-butadiene copolymer, ethylene-vinyl acetate copolymer, polyethylene, vinylidene chloride copolymer, polyamide polyamine epichlorohydrin, and the like.
Examples of the pigment include calcium carbonate, clay, kaolin, talc, barium sulfate, and titanium oxide.
[0019]
The base paper has a longitudinal Young's modulus (Ea) and a transverse Young's modulus (Eb) ratio (Ea / Eb) of 1.5 to 2.0 in terms of improving rigidity and dimensional stability (curling property). It is preferable that it exists in the range. When the Ea / Eb value is less than 1.5 or more than 2.0, the recording material is liable to deteriorate in rigidity and curl property, which is not preferable.
[0020]
In general, it is known that the “strain” of paper differs based on the difference in the mode of beating, and after the beating, the elasticity (rate) of the paper made by papermaking represents the degree of “strain” of the paper. Can be used as an additional factor. In particular, the elastic modulus of paper is measured by measuring the speed of sound propagating through the paper, using the relationship between the dynamic elastic modulus and density, which indicates the physical properties of the viscoelastic material of the paper, and using an ultrasonic vibration element. Can be obtained from the following equation.
E = ρc²(1-n²)
[However, in the above formula, E means a dynamic elastic modulus. ρ means density. c means the speed of sound in the paper. n means Poisson's ratio.
[0021]
In the case of normal paper, since n = about 0.2, even if it is calculated by the following formula, it can be calculated without much difference.
E = ρc²
That is, if the density and sound speed of paper can be measured, the elastic modulus can be easily obtained. In the above equation, when measuring the speed of sound, various known devices such as Sonic Tester SST-110 (manufactured by Nomura Corporation) can be used.
[0022]
There is no restriction | limiting in particular in the thickness of the said base paper, According to the objective, it can select suitably, Usually, 30-500 micrometers is preferable, 50-300 micrometers is more preferable, 100-250 micrometers is still more preferable. There is no restriction | limiting in particular in the basic weight of the said base paper, According to the objective, it can select suitably, For example, 50-250 g / m²Is preferable, 100-200 g / m²Is more preferable.
[0023]
In the present invention, the degree of bump size (30 seconds) on the surface of the support on the side where the image forming layer is provided is 10 g / m.²5 g / m²The following is preferred. The lower limit is 0.5 g / m.²Degree. The intended object of the present invention can be sufficiently achieved by using such a support having a large degree of bump size (30 seconds).
The degree of bump sizing (30 seconds) is measured by the water absorption test based on the degree of bump sizing method defined in JIS P 8140. Specifically, the degree of bump sizing is a measure of the amount of water absorbed when pure water is brought into contact with the support for 30 seconds.
[0024]
Such hump sizing degree (30 seconds) is 10 g / m²In order to achieve the following, specific examples are shown, but one of the following methods or a combination of these methods can be adjusted.
(1) A water repellent, a sizing agent, and a water-resistant agent are impregnated or coated on the surface of the base paper on which the image forming layer is formed.
Examples of the water repellent include silicone compounds, modified silicones, cured silicones, carbowaxes, and the like.
Examples of the sizing agent include fatty acid salts, rosin derivatives such as rosin and maleated rosin, paraffin wax and the like, and further higher fatty acids such as alkyl ketene dimer, alkenyl succinic anhydride (ASA), and epoxidized fatty acid amide. Among them, alkyl ketene dimers and epoxidized fatty acid amides are particularly preferable.
There is no restriction | limiting in particular in the addition amount of the said sizing agent, According to the objective, it can select suitably, 0.3 mass% or more is preferable with respect to the pulp mass of a base paper, and 0.5 mass% is more preferable.
Examples of the water-proofing agent include latex / emulsions such as styrene-butadiene copolymer, ethylene-vinyl acetate copolymer, polyethylene, vinylidene chloride copolymer, and polyamide polyamine epichlorohydrin.
The method for applying or impregnating the surface of the base paper with a water repellent, a sizing agent, and a water proofing agent is not particularly limited and may be appropriately selected depending on the intended purpose. For example, a horizontal size press, a size bath, a gate roll Examples include a coater, a film transfer coater, a rod coater, a bill blade coater, a spray coater, an air knife coater, and a curtain coater. Among these, a gate roll coater and a curtain coater are preferable.
[0025]
(2) A surface treatment agent is applied or impregnated on the side of the base paper on which the image forming layer is formed.
There is no restriction | limiting in particular as said surface treating agent, Although it can select suitably according to the objective, Any surface treating agent chosen from a soap free emulsion and a soap free latex can be used conveniently.
[0026]
Examples of the emulsion include hydrocarbon waxes such as paraffin wax and microcrystalline wax; oxygen-containing waxes such as carnauba wax and montan wax oxidized paraffin; petroleum resins, coumarone indene resins, terpene resins, and carboxylic acid adducts thereof. Hydrocarbon resins of polyethylene; polyolefins such as polyethylene and polypropylene; various emulsions such as acrylic, acrylic styrene and polyester; other emulsions such as alkyl ketene dimers and epoxidized fatty acid amides, etc., particularly soap-free emulsions are preferred. . As the soap-free emulsion, acrylic and polyolefin soap-free emulsions are preferably used. These acrylic soap-free emulsions include acrylate ester homopolymers, copolymers of acrylate and methacrylate, vinyl acetate, styrene, acrylonitrile, acrylic acid, and the like. The polyolefin soap-free emulsion includes ethylene vinyl acetate copolymer emulsion, ethylene acrylic acid copolymer, ionomer and the like.
[0027]
The aqueous medium is mainly water, but it is preferable to add a water-soluble organic solvent to water. Examples of the water-soluble organic solvent include ethylene glycol, propylene glycol, butylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol (average molecular weight of about 190 to 400), glycerin, alkyl ethers of the above glycols, N-methylpyrrolidone, 1, Examples include 3-dimethylimidazolinone, thiodiglycol, 2-pyrrolidone, sulfolane, dimethyl sulfoxide, diethanolamine, triethanolamine, ethanol, and isopropanol.
[0028]
If necessary, the soap-free emulsion coating solution may further include, for example, a matting agent, a pigment, a plasticizer, a release agent, a lubricant, a thickener, an antistatic agent, a fluorescent whitening agent, a color adjusting dye, These various additives can be arbitrarily blended.
[0029]
Examples of the latex include various latexes such as SBR, MBR, PVdc, etc., and soap-free latex is particularly preferable. As the soap-free latex, core / shell type latex particles obtained by an emulsion polymerization method not using an emulsifier (surfactant) are suitable (for example, “Synthesis / design of acrylic resin and development of new applications” (Chubu). Management Development Center Publishing Department, issued July 1, 1985) 279-281).
Examples of the method for producing such soap-free latex include a seed method, a reactive emulsifier method, an oligomer method, and the like.
The seed method is a method in which a water-dispersible polymer is prepared in advance, a monomer is added as a seed polymer, and polymerization is performed.
In the seed method, usually, a seed polymer forms a core part, and a polymerized polymer forms a shell part according to polymerization of a monomer to form a core / shell structure.
[0030]
The reactive emulsifier method is a method in which a compound (reactive emulsifier) having an ethylenically unsaturated bond and an anionic or nonionic hydrophilic group in the molecule is used in the same manner as a conventional emulsifier. However, the reactive emulsifier used is taken into the polymer to be produced and does not remain as an emulsifier.
As the reactive emulsifier, various reactive emulsifiers are known, and acrylic acid derivatives (JP 55-11252, JP 56-28208, etc.) and itaconic acid derivatives (JP 51-51). -30284, etc.), maleic acid derivatives (JP 51-30284, JP 56-29657 etc.), fumaric acid derivatives (JP 51-30285, JP 51-30284). Publication etc.).
Specifically, as a seed polymer suitable for producing the core / shell type latex resin composition, a seed polymer prepared by any of an emulsion polymerization method, a suspension polymerization method, and a dispersion polymerization method is used. can do. Among these, it is appropriate to use a seed polymer prepared by an emulsion polymerization method. Even if an emulsifier is used in the emulsion polymerization method, the amount of the emulsifier can be greatly reduced by the separation and purification process. Further, even if the seed polymer contains an emulsifier, the seed polymer is taken into the core / shell structure and does not exist on the surface of the core / shell structure, so that it is hardly affected by humidity. On the other hand, for the seed polymer prepared by the suspension polymerization method or the dispersion polymerization method, a complicated process for removing the dispersant, the solvent and the like is required.
Specifically, the seed polymer is preferably a water-soluble polymer, such as polyacrylate or a copolymer thereof, gelatin, tragacanth gum, starch, methyl cellulose, hydroxyethyl cellulose, carboxymethyl cellulose, polyvinyl alcohol, polyvinyl Pyrrolidone and the like can be used.
[0031]
In the seed method, as the monomer to be added in the presence of the seed polymer, various ethylenically unsaturated monomers can be used as long as they can be radically polymerized. In this case, the monomer may be the same as or different from the monomer used to produce the seed polymer.
[0032]
Examples of the monomer include (meth) acrylic acid ester monomers, monovinyl aromatic monomers, (meth) vinyl ester monomers, vinyl ether monomers, monoolefin monomers, diolefin monomers, halogenated olefin monomers, polyvinyl Preferable examples include system monomers.
[0033]
Examples of the (meth) acrylic monomer include (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, (meth) acrylate-2-ethylhexyl, ( Methacrylic acid cyclohexyl, phenyl (meth) acrylate, methyl (meth) acrylate, β-hydroxyethyl acrylate, γ-aminoacrylate propyl, stearyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, etc. These mixtures are preferably exemplified.
Examples of the vinyl aromatic monomer include styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, p-methoxystyrene, p-phenylstyrene, p-chlorostyrene, p-ethylstyrene, p- Butylstyrene, pt-butylstyrene, p-hexylstyrene, p-octylstyrene, p-nonylstyrene, p-decylstyrene, p-dodecylstyrene, 2,4-dimethylstyrene, 3,4-dichlorostyrene, etc. Or a derivative thereof, or a mixture thereof.
[0034]
Examples of the vinyl ester monomers include vinyl acetate, vinyl propionate, vinyl benzoate, and the like.
Examples of the vinyl ether monomer include vinyl methyl ether, vinyl ethyl ether, vinyl isobutyl ether, vinyl phenyl ether, and the like.
Examples of the olefin monomer include monoolefin monomers such as ethylene, propylene, isobutylene, 1-butene, 1-pentene, and 4-methyl-1-pentene, and diolefin monomers such as butadiene, isoprene, and chloroprene. Can be mentioned.
Furthermore, a crosslinkable monomer may be added to improve the properties of the seed polymer. Examples of the crosslinkable monomer include those having two or more unsaturated bonds such as divinylbenzene, divinylnaphthalene, divinyl ether, diethylene glycol methacrylate, ethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, and diallyl phthalate.
[0035]
In the seed method, a radical polymerization initiator can be used. The radical polymerization initiator can be appropriately used as long as it is water-soluble. Examples of such polymerization initiators include persulfates (potassium persulfate, ammonium persulfate, etc.), azo compounds (4,4′-azobis-4-cyanovaleric acid and its salts, 2,2′-azobis ( 2-amidinopropane) salts), peroxide compounds, and the like.
[0036]
Furthermore, the said polymerization initiator is good also as a redox-type initiator combining with a reducing agent as needed. By using the redox initiator, the polymerization activity increases, the polymerization temperature can be lowered, and the polymerization time can be expected to be shortened.
Any temperature may be selected as long as the polymerization temperature is equal to or higher than the lowest radical generation temperature of the polymerization initiator, but for example, a range of 50 ° C to 80 ° C is usually used. However, it is also possible to polymerize at room temperature or lower by using a polymerization initiator that starts at room temperature, for example, a combination of hydrogen peroxide and a reducing agent (ascorbic acid or the like).
[0037]
In the core / shell type latex particles, the number average molecular weight [(Mn (c)) of the core is preferably 30,000 to 500,000, and more preferably 40000 to 400,000.
On the other hand, the number average molecular weight [Mn (s)] of the shell is preferably 4000 to 30000, and more preferably 5000 to 20000.
[0038]
In the core / shell type latex particles, the mass ratio of the core to the shell is preferably 10:90 to 90:10, and more preferably 20:80 to 80:20. If the mass ratio of the core to the shell is out of this range, it is difficult to sufficiently exhibit the characteristics of the core / shell structure, and the characteristics are close to those of a simple continuous film.
The average particle size of the core / shell type latex particles is preferably 0.2 μm or less, and more preferably 0.1 μm or less. In addition, the minimum of an average particle diameter is about 0.04 micrometer, for example. When the average particle diameter exceeds 0.2 μm, the characteristics of the core / shell structure cannot be utilized.
[0039]
If necessary, the soap-free latex coating solution may further include, for example, matting agents, pigments, plasticizers, release agents, lubricants, thickeners, antistatic agents, fluorescent whitening agents, and color-adjusting dyes. These various additives can be arbitrarily blended.
[0040]
The glass transition temperature (Tg) of the resin in the soap-free latex or soap-free emulsion is preferably 30 ° C. or higher, and more preferably 50 ° C. or higher. The amount of the soap-free latex or soap-free emulsion applied or impregnated is 0.5 to 10 g / m in solid content.²1-5 g / m²Is more preferable.
[0041]
In the present invention, the center surface average roughness (SRa) measured under conditions of a cutoff of 5 mm to 6 mm on the side of the support on which the image forming layer is provided is 0.7 μm or less, preferably 0.5 μm or less, The lower limit is about 0.2 μm. In addition, as the center plane average roughness (SRa) at a wavelength of 5 mm to 6 mm decreases, the surface of the support looks flat when viewed.
Here, the center surface average roughness (SRa) is an average roughness obtained by three-dimensionally scanning the roughness of a certain plane, and is obtained by scanning the linear roughness of the plane. This is a concept different from the line average roughness (Ra). The center plane average roughness (SRa) is determined using, for example, a surface profile measuring device Surfcom 570A-3DF (manufactured by Tokyo Seimitsu Co., Ltd.) based on the following measurement and analysis conditions under the conditions of a cutoff of 5 mm to 6 mm. Average roughness (SRa) can be measured.
-Measurement and analysis conditions-
・ Scanning direction: MD direction of sample
・ Measurement length: 50 mm in papermaking (X) direction, 30 mm in its vertical (Y) direction
・ Measurement pitch: 0.1 mm in the X direction, 0.1 mm in the Y direction
・ Scanning speed: 30mm / sec
・ Band pass filter: 5mm ~ 6mm
[0042]
While satisfying the condition of the center surface average roughness (SRa), the change in SRa (ΔSRa) before and after contacting the surface of the support on the side where the image forming layer is provided at 20 ° C. for 2 minutes is −0. It is 1 μm to +0.1 μm, and −0.05 μm to +0.05 μm is preferable.
Here, the method of bringing the side of the support on which the image forming layer is provided into contact with water can be carried out according to the Cobb sizing method water absorption test defined in JIS P 8140.
When the center plane average roughness (SRa) exceeds 0.7 μm and (ΔSRa) is out of the range of −0.1 μm to +0.1 μm, the smoothness of the surface of the support is impaired, resulting in high image quality. Can not get a good image.
[0043]
In the present invention, the Beck smoothness of the surface of the support on the side where the image forming layer is provided is preferably 100 seconds or more, and more preferably 150 seconds or more. If the Beck smoothness is less than 100 seconds, the image quality of the toner image becomes poor, which is not preferable. The upper limit is not particularly limited, but is practically about 600 seconds, preferably about 500 seconds.
Here, the Beck smoothness is a smoothness defined by JIS P 8119.
[0044]
In order to achieve the surface smoothness (center surface average roughness (SRa), (ΔSRa) and Beck smoothness range) of the support, specifically shown by Examples and the like, One of them or a combination of these methods can be adjusted.
(1) Adjustment of beating conditions
The beating conditions are adjusted to adjust the pulp mass average fiber length after beating preferably to 0.45 to 0.65 mm, and more preferably to 0.50 to 0.65 mm.
(2) Surface calendar treatment
The surface of the support on the side where the image forming layer is provided is calendered to increase the density of the base paper. For example, the density of the base paper is preferably 0.80 to 1.15 g / cm.³More preferably, 0.90 to 1.10 g / cm³Is appropriate.
The surface temperature of the metal roll in the calendar treatment is preferably 110 ° C. or higher, more preferably 150 ° C. or higher, and further preferably 250 ° C. or higher. The upper limit temperature is suitably about 300 ° C., for example.
[0045]
The calendar treatment using the metal surface can be performed, for example, by using a pair of calendar rolls in which at least one roll is a metal roll.
Examples of such a calender roll include a soft calender roll composed of a combination of a metal roll and a synthetic resin roll, and a machine calender roll composed of a pair of metal rolls. Among these, a soft calender roll is suitable, and a long nip shoe calender composed of a metal roll and a shoe roll with a synthetic resin belt can take a long nip width of 50 to 270 mm. This is preferable because the contact area increases.
In addition, the said calendar process can be used even if it combines the said calendar process individually or.
[0046]
Regardless of the type of calendar apparatus, the calendar process is preferably performed so that the metal roll is in contact with the image forming surface, and the calendar process is preferably performed, so that the sheet is in contact with a metal roll having a surface temperature of 110 ° C. or more, More preferably, a calendar process is performed. It is more preferable to pass the paper so that a metal roll of 150 ° C. or higher is in contact with it and perform a calendar process. When the paper is passed so that the metal roll is in contact with the image forming surface and the calendar process is not performed, the density of the base paper does not increase and the smoothness is not sufficiently improved, so a high quality image similar to a silver salt photograph is formed. I can't.
As a nip pressure at the time of carrying out the soft calendar process of the said base paper, 100 kN / m or more is preferable, for example, and 100-600 kN / m is more preferable.
[0047]
(Method for producing support for recording material)
The recording material support manufacturing method of the present invention is a recording material support manufacturing method including at least a base paper, and is selected from a soap-free latex and a soap-free emulsion on the image forming surface side of the base paper. After applying a coating solution containing at least one surface treatment agent, it is calendered.
A coating liquid containing at least one surface treatment agent selected from a soap-free latex and a soap-free emulsion on the surface of the base paper on which the image forming layer is provided is 0.5 to 10 g / m in solid content.²It is preferable to apply.
In the calendering process, the coating layer is calendered using a calender having a metal roll having a surface temperature of 110 ° C. or higher. The calendar treatment is performed using at least one calendar, and the surface temperature is more preferably 150 ° C. or higher.
[0048]
According to the method for producing a recording material support of the present invention, a recording material support excellent in surface smoothness and water resistance can be produced efficiently.
[0049]
(Recording material)
The recording material of the present invention has a support for recording material containing at least a base paper, an image forming layer on the support, and the support for recording material of the present invention is used as the support. The image forming layer corresponds to an emulsion layer that develops YMC in the case of silver salt photography. In the case of inkjet, it corresponds to an ink receiving layer that receives and holds ink. In the case of electrophotography, it corresponds to a toner image receiving layer.
The recording material varies depending on the use and type of the recording material, such as an electrophotographic image receiving material, a heat sensitive color recording material, an ink jet recording material, a sublimation transfer image receiving material, a silver salt photographic photosensitive material, a thermal transfer image receiving material, etc. Is mentioned.
Hereinafter, each recording material will be described in detail.
[0050]
<Image receiving material for electrophotography>
The electrophotographic image-receiving material has the recording material support of the present invention and at least one toner image-receiving layer provided on at least one surface of the support, and other layers appropriately selected as necessary. For example, surface protection layer, intermediate layer, undercoat layer, cushion layer, charge control (prevention) layer, reflection layer, color adjustment layer, storage stability improvement layer, adhesion prevention layer, anti-curl layer, smoothing layer, etc. Do it. Each of these layers may have a single layer structure or a laminated structure.
[0051]
[Toner image receiving layer]
The toner image receiving layer is a toner image receiving layer for receiving color or black toner and forming an image. The toner image receiving layer receives a toner for forming an image from a developing drum or an intermediate transfer body by (static) electricity, pressure, etc. in a transfer process, and fixes it by heat, pressure, etc. in a fixing process. Have
[0052]
The toner image-receiving layer needs to be a low-transparency toner image-receiving layer having a light transmittance of 78% or less from the viewpoint of making the electrophotographic image-receiving paper of the present invention feel like a photograph. The rate is preferably 73% or less, and more preferably 72% or less.
The light transmittance can be measured by separately forming a coating film having the same thickness on a polyethylene terephthalate film (100 μm) and using the direct reading haze meter (Suga Test Instruments HGM-2DP). .
[0053]
The material of the toner image-receiving layer contains at least a thermoplastic resin and, if necessary, other components.
[0054]
-Thermoplastic resin-
The thermoplastic resin is not particularly limited as long as it can be deformed under temperature conditions such as fixing and can accept the toner, and can be appropriately selected according to the purpose. And a copolymer resin such as polyester resin, styrene, styrene-butyl acrylate, etc., and preferably contains 20% by mass or more of a copolymer resin such as polyester resin, styrene, styrene-butyl acrylate. Is more preferable. Further, styrene, styrene-butyl acrylate copolymer, styrene-acrylic acid ester copolymer, styrene-methacrylic acid ester copolymer and the like are more preferable.
[0055]
Examples of the thermoplastic resin include (a) a resin having an ester bond, (b) a polyurethane resin, (c) a polyamide resin, (d) a polysulfone resin, (e) a polyvinyl chloride resin, etc. ) Polyvinyl butyral, (to) polycaprolactone resin, (h) polyolefin resin, and the like.
[0056]
Examples of the resin having an ester bond (b) include terephthalic acid, isophthalic acid, maleic acid, fumaric acid, phthalic acid, adipic acid, sebacic acid, azelaic acid, abietic acid, succinic acid, trimellitic acid, and pyromellitic acid. Dicarboxylic acid components such as acids (these dicarboxylic acid components may be substituted with sulfonic acid groups, carboxyl groups, etc.) and diether derivatives of ethylene glycol, diethylene glycol, propylene glycol, bisphenol A, bisphenol A (for example, Bisphenol A ethylene oxide 2 adducts, bisphenol A propylene oxide 2 adducts, etc.), bisphenol S, 2-ethylcyclohexyldimethanol, neopentyl glycol, cyclohexyldimethanol, glycerin, etc. Polyacrylic acid ester resins such as polyester resins, polymethyl methacrylate, polybutyl methacrylate, polymethyl acrylate, polybutyl acrylate, etc. obtained by condensation with the alcohol component (these alcohol components may be substituted with hydroxyl groups, etc.) Alternatively, polymethacrylic acid ester resin, polycarbonate resin, polyvinyl acetate resin, styrene acrylate resin, styrene-methacrylic acid ester copolymer resin, vinyl toluene acrylate resin, and the like can be given.
Specific examples include those described in JP-A Nos. 59-101395, 63-7971, 63-7972, 63-7773, and 60-294862.
[0057]
Examples of commercially available polyester resins include Toyobo's Byron 290, Byron 200, Byron 280, Byron 300, Byron 103, Byron GK-140, Byron GK-130; Kao's Tufton NE-382, Tufton U- 5, ATR-2009, ATR-2010; Elitel UE3500, UE3210, XA-8153 manufactured by Unitika; Polyester TP-220, R-188 manufactured by Nippon Synthetic Chemical Co., Ltd.
Commercially available products of the acrylic resin include Mitsubishi Rayon Co., Ltd. Dianal SE-5437, SE-5102, SE-5377, SE-5649, SE-5466, SE-5482, HR-169, 124, HR-1127. , HR-116, HR-113, HR-148, HR-131, HR-470, HR-634, HR-606, HR-607, LR-1065, 574, 143, 396, 637, 162, 469, 216 , BR-50, BR-52, BR-60, BR-64, BR-73, BR-75, BR-77, BR-79, BR-80, BR-83, BR-85, BR-87, BR -88, BR-90, BR-93, BR-95, BR-100, BR-101, BR-102, BR-105, BR-106, BR-107, BR- 08, BR-112, BR-113, BR-115, BR-116, BR-117; Sreck P SE-0020, SE-0040, SE-0070, SE-0100, SE-1010, SE- manufactured by Sekisui Chemical Co., Ltd. 1035; Sanyo Chemical Industries Himer ST95, ST120; FM601 manufactured by Mitsui Chemicals.
[0058]
Examples of the (e) polyvinyl chloride resin include polyvinylidene chloride resin, vinyl chloride-vinyl acetate copolymer resin, vinyl chloride-vinyl propionate copolymer resin, and the like.
Examples of the (f) polyvinyl butyral include cellulose resins such as polyol resin, ethyl cellulose resin, and cellulose acetate resin. Examples of commercially available products include those manufactured by Denki Kagaku Kogyo Co., Ltd. and Sekisui Chemical Co., Ltd. The polyvinyl butyral has a polyvinyl butyral content of 70% by mass or more, an average polymerization degree of 500 or more is preferable, an average polymerization degree of 1000 or more is more preferable, and a commercially available product is Denka Butyral manufactured by Denki Kagaku Kogyo Co., Ltd. 3000-1, 4000-2, 5000A, 6000C; manufactured by Sekisui Chemical Co., Ltd. S-REC BL-1, BL-2, BL-3, BL-S, BX-L, BM-1, BM-2, BM-5 , BM-S, BH-3, BX-1, BX-7, and the like.
Examples of the (g) polycaprolactone resin include styrene-maleic anhydride resin, polyacrylonitrile resin, polyether resin, epoxy resin, phenol resin, and the like.
Examples of the (h) polyolefin resin include polyethylene resins, polypropylene resins, copolymer resins of olefins such as ethylene and propylene and other vinyl monomers, acrylic resins, and the like.
[0059]
The said thermoplastic resin may be used individually by 1 type, may be 2 or more types, In addition to these, these mixtures, these copolymers, etc. can also be used.
[0060]
The thermoplastic resin is preferably one that can satisfy the following properties of the toner image-receiving layer in the state where the toner image-receiving layer is formed, more preferably one that can satisfy the above-mentioned properties of the toner image-receiving layer even with the resin alone. It is also preferable to use two or more resins having different layer properties.
[0061]
As the thermoplastic resin, those having a larger molecular weight than the thermoplastic resin used in the toner are preferable. However, the molecular weight described above is not necessarily preferable depending on the relationship between the thermodynamic properties of the thermoplastic resin used in the toner and the resin used in the toner image-receiving layer. For example, when the softening temperature of the resin used in the toner image receiving layer is higher than that of the thermoplastic resin used in the toner, the molecular weight is the same or the resin used in the toner image receiving layer is the same. Smallness may be preferred.
[0062]
It is also preferable to use a mixture of resins having the same composition and different average molecular weights as the thermoplastic resin. Further, as the relationship with the molecular weight of the thermoplastic resin used in the toner, the relationship disclosed in JP-A-8-334915 is preferable.
The molecular weight distribution of the thermoplastic resin is preferably wider than the molecular weight distribution of the thermoplastic resin used in the toner.
Examples of the thermoplastic resin include JP-B-5-127413, JP-A-8-194394, JP-A-8-334915, JP-A-8-334916, JP-A-9-171265, and JP-A-10. Those satisfying the physical properties disclosed in the publication No. 221877 / etc. Are preferred.
[0063]
The thermoplastic resin used for the toner image-receiving layer is particularly preferably an aqueous resin such as a water-soluble resin or a water-dispersible resin for the following reasons (i) to (ii).
(I) The organic solvent is not discharged in the coating and drying process, and is excellent in environmental suitability and work suitability.
(Ii) Many release agents such as wax are difficult to dissolve in a solvent at room temperature, and are often dispersed in a solvent (water, organic solvent) in advance. Moreover, the water dispersion form is more stable and has better manufacturing process suitability. Furthermore, the water-based coating is more likely to cause the wax to bleed onto the surface during the coating and drying process, and the effects of the release agent (offset resistance, adhesion resistance, etc.) can be easily obtained.
[0064]
As the water-based resin, if it is a water-soluble resin or a water-decomposable resin, its composition, bond structure, molecular structure, molecular weight, molecular weight distribution, and form are not specified. Examples of the water-based group of the polymer include a sulfonic acid group, a hydroxyl group, a carboxylic acid group, an amino group, an amide group, or an ether group.
Examples of the water-soluble resin include Research Disclosure No. 17,643, page 26, No. 18,716, page 651, No. 307,105, pages 873-874, and JP-A No. 64-13546. 71) to those described on pages (75) to (75).
Specifically, for example, vinyl pyrrolidone-vinyl acetate copolymer, styrene-vinyl pyrrolidone copolymer, styrene-maleic anhydride copolymer, water-soluble polyester, water-soluble acrylic, water-soluble polyurethane, water-soluble nylon, water-soluble An epoxy resin can be used. Further, the gelatin may be selected from so-called demineralized gelatin in which the content of lime-processed gelatin, acid-processed gelatin, calcium, or the like is reduced in accordance with various purposes, and is preferably used in combination. Commercially available water-soluble polyester as various water-soluble polyester plus coats manufactured by Tateo Chemical Industry Co., Ltd .; Dainippon Ink and Chemicals Finetex ES Series; Water-soluble acrylic as Jurimer AT Series; Dainippon Ink and Chemicals Fine Tex 6161, K-96; Seiko Chemical Industries high loss NL-1189, BH-997L and the like.
[0065]
Examples of water-dispersible resins include water-dispersed resins such as water-dispersed acrylic resins, water-dispersed polyester resins, water-dispersed polystyrene resins, and water-dispersed urethane resins; acrylic resin emulsions, polyvinyl acetate emulsions, and SBR (styrene / butadiene). -Rubber) Emulsions such as emulsions, resins and emulsions in which the thermoplastic resins (a) to (h) above are dispersed in water, or their copolymers, mixtures, and cationically modified ones are appropriately selected. Two or more types can be combined.
Commercially available products of the water-dispersible resin include, for example, Toyobo's Bironal series, Takamatsu Yushi pesresin A series, Kao Tufton UE series, Nippon Synthetic Polyester WR series, Unitika Eliere series, and acrylic series. Then, high loss XE, KE, PE series manufactured by Seiko Chemical Industry, Jurimer ET series manufactured by Nippon Pure Chemical Co., Ltd. and the like can be mentioned.
The film formation temperature (MFT) of the polymer used is preferably room temperature or higher for storage before printing, and preferably 100 ° C. or lower for fixing of toner particles.
[0066]
The content of the thermoplastic resin is preferably 50% by mass or more, and more preferably 50 to 90% by mass with respect to the total amount of the toner image-receiving layer.
[0067]
As a component other than the thermoplastic resin in the toner image receiving layer, the light transmittance of the toner image receiving layer can be easily adjusted within the numerical range, and in particular, the whiteness of the toner image receiving layer can be adjusted. Colorants such as pigments and dyes are preferred, and pigments are particularly preferred. In addition, the other components include various additives added for the purpose of improving the thermodynamic properties of the toner image-receiving layer, such as a mold release agent, a plasticizer, a filler, a crosslinking agent, a charge control agent, and an emulsification agent. And dispersions.
[0068]
-Colorant-
Examples of the colorant include fluorescent whitening agents, white pigments, colored pigments, and dyes.
The fluorescent whitening agent is a compound that absorbs in the near ultraviolet region and emits fluorescence at 400 to 500 nm, and various known fluorescent whitening agents can be used without particular limitation. Examples of the optical brightener include K.I. Preferable examples include the compounds described in “The Chemistry of Synthetic Dies” edited by Veen Rataraman, Vol. Specific examples include stilbene compounds, coumarin compounds, biphenyl compounds, benzoxazoline compounds, naphthalimide compounds, pyrazoline compounds, carbostyryl compounds, and the like. Examples thereof include white fur fur PSN, PHR, HCS, PCS, B manufactured by Sumitomo Chemical, and UVITEX-OB manufactured by Ciba-Geigy.
[0069]
An inorganic pigment (titanium oxide, calcium carbonate, etc.) can be used as the white pigment. Examples of colored pigments include various pigments and azo pigments described in JP-A-63-44653 (Azo lake; Carmine 6B, Red 2B, Insoluble azo; Monoazo yellow, Disazo yellow, Pyrazolo orange, Vulcan orange, Condensed azo type) Chromophthalier, chromophthaled red), polycyclic pigments (phthalocyanine series; copper phthalocyanine blue, copper phthalocyanine green, dioxazine series; dioxazine violet, isoindolinone series; isoindolinone yellow, slen series; perylene, perinone, Flavantron, thioindigo, lake pigment (malachite green, rhodamine B, rhodamine G, Victoria blue B) or inorganic pigment (oxide, titanium dioxide, bengara, sulfate; precipitated barium sulfate, carbonate; precipitated calcium carbonate, Hydrous succinate, anhydrous succinate, metal powder: aluminum powder, bronze powder, zinc powder, carbon black, chrome lead, bitumen, etc. These may be used alone, Two or more of these may be used in combination, and among these, titanium oxide is particularly preferable as the pigment.
[0070]
Various known dyes can be used as the dye. Examples of oil-soluble dyes include anthraquinone compounds and azo compounds. Specific examples of water-insoluble dyes include C.I. I. Vat violet 1, C.I. I. Vat violet 2, C.I. I. Vat violet 9, C.I. I. Vat violet 13, C.I. I. Vat violet 21, C.I. I. Vat Blue 1, C.I. I. Vat Blue 3, C.I. I. Vat Blue 4, C.I. I. Vat Blue 6, C.I. I. Vat Blue 14, C.I. I. Vat Blue 20, C.I. I. Vat dyes such as Vat Blue 35, C.I. I. Dispers Violet 1, C.I. I. Disperse Violet 4, C.I. I. Disperse Violet 10, C.I. I. Disperse Blue 3, C.I. I. Disperse Blue 7, C.I. I. Disperse dyes such as Disperse Blue 58, C.I. I. Solvent Violet 13, C.I. I. Solvent Violet 14, C.I. I. Solvent Violet 21, C.I. I. Solvent Violet 27, C.I. I. Solvent Blue 11, C.I. I. Solvent Blue 12, C.I. I. Solvent Blue 25, C.I. I. There are oil-soluble dyes such as Solvent Blue 55.
[0071]
Further, a colored coupler used in silver salt photography can also be preferably used.
[0072]
The content of the colorant is 0.1 to 8 g / m with respect to the total amount of the toner image receiving layer.²Is preferably 0.5 to 5 g / m²Is more preferable.
The content is 0.1 g / m²If it is less than 1, the light transmittance in the toner image-receiving layer is increased, while 8 g / m.²Exceeding may cause poor handling such as cracking and adhesion resistance.
[0073]
-Release agent-
The release agent of the present invention is blended in the toner image receiving layer in order to prevent offset of the toner image receiving layer. The release agent used in the present invention is heated and melted at the fixing temperature, deposited on the surface of the toner image-receiving layer, unevenly distributed on the surface of the toner image-receiving layer, and further cooled and solidified to be released onto the surface of the toner image-receiving layer. The type is not limited as long as it forms a layer of the mold material.
Examples of the release agent exhibiting such effects include at least one release agent selected from the group consisting of silicone compounds, fluorine compounds, waxes, and matting agents. Preferably, at least one release agent selected from the group consisting of silicone oil, polyethylene wax, carnauba wax, and silicone particles and polyethylene wax particles is used.
[0074]
As the release agent, for example, compounds described in “Summary and Application of Revision Wax” by Kosho Shobo and Silicone Handbook published by Nikkan Kogyo Shimbun Co., Ltd. can be used. JP-B-59-38581, JP-B-4-32380, Patent Nos. 2838498, 2949558, JP-A-50-117433, 52-52640, 57-148755, 61-62056. 61-62057, 61-118760, JP-A-2-42451, 3-41465, 4-212175, 4-214570, 4-263267, 5-34966, 5-119514, 6-59502, 6-161150, 6-175396, 6-219040, 6-230600, 6-295093, 7-36210, 7 -43940, 7-56387, 7-56390, 7-64335, 7-199682, 7-223362 7-287413, 8-184992, 8-227180, 8-248671, 8-248799, 8-248801, 8-278663, 9-152939, 9 -160278, 9-185181, 9-319139, 9-319143, 10-20549, 10-48889, 10-198069, 10-207116, 11-2917 No. 11-44969, No. 11-65156, No. 11-73049, No. 11-194542, and the silicone compounds, fluorine compounds, and waxes used in the toners are also preferably used. . Further, a plurality of these compounds can be used in combination.
[0075]
Specifically, as the silicone compound, an unmodified silicone oil (specifically, dimethylsiloxane oil, methyl hydrogen silicone oil, phenylmethyl silicone oil, commercially available KF- manufactured by Shin-Etsu Chemical Co., Ltd.) is used as the silicone compound. 96, KF-96L, KF-96H, KF-99, KF-50, KF-54, KF-56, KF-965, KF-968, KF-994, KF-995, HIVAC F-4, F-5 Toray Dow Corning Silicone SH200, SH203, SH490, SH510, SH550, SH710, SH704, SH705, SH7028A, SH7036, SM7060, SM7001, SM7706, SH7036, SH8710, SH1107, SH8627; TSF400, TSF401, TSF404, TSF405, TSF431, TSF433, TSF434, TSF437, TSF450 series, TSF451 series, TSF456, TSF458 series, TSF483, TSF484, TSF4045, TSF4300, TSF4600, YF33Y, F-3800 YF-3802, YF-3804, YF-3807, YF-3897, XF-3905, XS69-A1753, TEX100, TEX101, TEX102, TEX103, TEX104, TSW831, etc., amino-modified silicone oil (Shin-Etsu Chemical Co., Ltd. as a commercial product) KF-857, KF-858, KF-859, KF-861, KF-864, KF-880, Toray Dowco SF8417, SM8709 made by silicone, TSF4700, TSF4701, TSF4702, TSF4703, TSF4704, TSF4705, TSF4706, TEX150, TEX151, TEX154, etc. 880, Toshiba Silicone TSF4770, XF42-A9248, etc.), carbinol modified silicone oil (Toshiba Silicone XF42-B0970 etc. as a commercial product), vinyl modified silicone oil (Toshiba Silicone XF40-A1987 etc. as a commercial product), epoxy modified Silicone oil (Toray Dow Corning Silicone SF8411, SF8413; Toshiba Corn TSF3965, TSF4730, TSF4732, XF42-A4439, XF42-A4438, XF42-A5041, XC96-A4462, XC96-A4463, XC96-A4464, TEX170, etc., polyether-modified silicone oil (KF manufactured by Shin-Etsu Chemical Co., Ltd. as a commercial product) -351 (A), KF-352 (A), KF-353 (A), KF-354 (A), KF-355 (A), KF-615 (A), KF-618, KF-945 (A ); Toray Dow Corning Silicone SH3746, SH3771, SF8421, SF8419, SH8400, SF8410; Toshiba Silicone TSF4440, TSF4441, TSF4445, TSF4446, TSF4450, TSF4452, TSF445 , TSF4460, etc.), silanol-modified silicone oil, methacryl-modified silicone oil, mercapto-modified silicone oil, alcohol-modified silicone oil (commercially available products are Toray Dow Corning Silicone SF8427, SF8428, Toshiba Silicone TSF4750, TSF4751, XF42-B0970, etc. ), Alkyl-modified silicone oils (Toray Dow Corning Silicone SF8416, Toshiba Silicone TSF410, TSF411, TSF4420, TSF4421, TSF4422, TSF4450, XF42-334, XF42-A3160, XF42-A3161, etc.), fluorine-modified Silicone oil (commercially available Toray Dow Corning Silicone FS1265, Toshiba Silicon FQF501, etc.), silicone rubber and silicone fine particles (commercially available products are Toray Dow Corning Silicone SH851U, SH745U, SH55UA, SE4705U, SH502UA & B, SRX539U, SE6770U-P, DY38-038, DY38-047, Trefill F- 201, F-202, F-250, R-900, R-902A, E-500, E-600, E-601, E-506, BY29-119; Toshiba Silicone Tospearl 105, 120, 130, 145, 240, 3120, etc.), silicone-modified resins (specifically, olefin resins, polyester resins, vinyl resins, polyamide resins, cellulose resins, phenoxy resins, vinyl chloride-vinyl acetate resins, urethane resins, acrylic resins, styrene) As a commercial product, such as acrylic resins and compounds obtained by modifying these copolymer resins with silicones, Daiichi Seika's Dialomer SP203V, SP712, SP2105, SP3023; Nippon Oil & Fats Modiper FS700, FS710, FS720, FS730, FS770; Cymac US-270, US-350, US-352, US-380, US-413, US-450, Reseda GP-705, GS-30, GF-150, GF-300; SH997 manufactured by Toray Dow Corning Silicone SR2114, SH2104, SR2115, SR2202, DCI-2577, SR2317, SE4001U, SRX625B, SRX643, SRX439U, SRX488U, SH804, SH840, SR2107, SR211 YR3370, TSR1122, TSR102, TSR108, TSR116, TSR117, TSR125A, TSR127B, TSR144, TSR180, TSR187, YR47, YR3187, YR3224, YR3232, YR3286, TE1340 ), Reactive silicone compounds (specifically, there are addition reaction type, peroxide curing type, ultraviolet curing type, and TSR1500, TSR1510, TSR1511, TSR1515, TSR1520, YR3286, YR3340, PSA6574, manufactured by Toshiba Silicones as commercially available products) TPR6500, TPR6501, TPR6600, TPR6702, TPR6604, T PR6700, TPR6701, TPR6705, TPR6707, TPR6708, TPR6710, TPR6712, TPR6721, TPR6722, UV9300, UV9315, UV9425, UV9430, XS56-A2775, XS56-A2982, XS56-A3075, XS56-A3957, X56-A3957, X56 XS56-B1794, SL6100, SM3000, SM3030, SM3200, YSR3022, and the like.
[0076]
Examples of the fluorine compound include fluorine oil (Daikin Industries # 1, # 3, # 10, # 20, # 50, # 100, Unidyne TG-440, TG-452, TG-490, TG-560 as commercial products. TG-561, TG-590, TG-652, TG-670U, TG-991, TG-999, TG-3010, TG-3020, TG-3510; TF-100, MF-110, MF manufactured by Tochem Products -120, MF-130, MF-160, MF-160E; Asahi Glass Surflon S-111, S-112, S-113, S-121, S-131, S-132, S-141, S-145; FC-430, FC-431 made by Mitsui Fluorochemical, etc.), fluoro rubber (LS63U made by Toray Dow Corning Silicone as a commercial product) Fluorine-modified resins (Nippon Yushi Modiper F200, F220, F600, F2020, F3035; Dainichi Seika's Dialomer FF203, FF204; Asahi Glass Surflon S-381, S-383, S-393, SC- 101, SC-105, KH-40, SA-100; EF-351, EF-352, EF-801, EF-802, EF-601, TFE, TFEA, TFEMA, PDFOH manufactured by Tochem Products; THV manufactured by Sumitomo 3M -200P, etc.), fluorine sulfonic acid compounds (commercially available products EF-101, EF-102, EF-103, EF-104, EF-105, EF-112, EF-121, EF-122A, EF manufactured by Tochem Products) -122B, EF-122C, EF-123A, EF-123B, E -125M, EF-132, EF-135M, EF-305, FBSA, KFBS, LFBS, etc., fluorosulfonic acid, fluorinated acid compounds and salts (specifically, hydrofluoric acid, dilute hydrofluoric acid, borofluoric acid, borofluoride) Zinc, nickel borofluoride, tin borofluoride, lead borofluoride, copper borofluoride, silicic acid, potassium fluoride titanate, perfluorocaprylic acid, ammonium perfluorooctanoate, etc., inorganic fluoride (specifically fluoride) Aluminum, potassium silicofluoride, potassium fluoride zirconate, zinc fluoride tetrahydrate, calcium fluoride, lithium fluoride, barium fluoride, tin fluoride, potassium fluoride, acidic potassium fluoride, magnesium fluoride, fluoride Titanic acid, zirconic fluoride, ammonium hexafluorophosphate, potassium hexafluorophosphate Etc.).
[0077]
Examples of the wax include synthetic hydrocarbons, modified waxes, hydrogenated waxes, and natural waxes.
[0078]
Examples of the synthetic hydrocarbon include polyethylene wax (as commercially available products Polylon A, 393, H-481, manufactured by Chukyo Yushi Co., Ltd., Sanyo Kasei Sun Wax E-310, E-330, E-250P, LEL-250, LEL-800, LEL-400P, etc.), polypropylene wax (commercially available from Sanyo Chemical Co., Ltd., Biscol 330-P, 550-P, 660-P), Fischer-Tropsch wax (commercially available from Nippon Seiki FT100, FT-0070, etc.), acid amide Compound or acid imide compound (specifically stearic acid amide, phthalic anhydride imide, etc., commercially available products such as Chukyo Yushi Cellosol 920, B-495, Hymicron G-270, G-110, Hydrin D-757) Etc.
[0079]
Examples of the modified wax include amine-modified polypropylene (QN-7700 manufactured by Sanyo Chemical Co., Ltd. as a commercial product), acrylic acid-modified, fluorine-modified, olefin-modified wax, and urethane-type wax (NPS-6010 and HAD-5090 manufactured by Nippon Seiki as commercial products). Etc.), alcohol type waxes (NPS-9210, NPS-9215, OX-1949, XO-020T, etc., manufactured by Nippon Seiki) and the like.
[0080]
Examples of the hydrogenated wax include hydrogenated castor oil (such as a castor wax manufactured by Ito Oil Co., Ltd.), castor oil derivatives (dehydrated castor oil DCO, DCO Z-1, DCO Z-3, castor oil fatty acid manufactured by Ito Oil Co., Ltd. as commercial products). CO-FA, ricinoleic acid, dehydrated castor oil fatty acid DCO-FA, dehydrated castor oil fatty acid epoxy ester D-4 ester, castor oil-based urethane acrylate CA-10, CA-20, CA-30, castor oil derivative MINERASOL S-74 , S-80, S-203, S-42X, S-321, special castor oil-based condensed fatty acid MINERASOLRC-2, RC-17, RC-55, RC-335, special castor oil-based condensed fatty acid ester MINERASOL LB-601 , LB-603, LB-604, LB-702, LB-70 , # 11, L-164, etc.), stearic acid (such as 12-hydroxystearic acid made by Ito Oil as a commercial product), lauric acid, myristic acid, palmitic acid, behenic acid, sebacic acid (made by Ito Oil as commercial products) Sebacic acid, etc.), undecylenic acid (such as undecylenic acid made by Ito Oil as a commercial product), heptylic acid (such as heptyl acid from Ito Oil as a commercial product), maleic acid, highly maleated oil (made by Ito Oil as a commercial product) HIMALIN DC-15, LN-10, 00-15, DF-20, SF-20, etc.), blown oil (commercially available from Celonol # 10, # 30, # 60, R-40, S-40 manufactured by Ito Oil) 7), and cyclopentadiene oil (commercially available products such as CP oil and CP oil-S manufactured by Ito Oil Co., Ltd.).
[0081]
The natural wax is preferably at least one selected from plant waxes, animal waxes, mineral waxes and petroleum waxes, particularly preferably plant waxes.
[0082]
Examples of the plant wax include carnauba wax (commercially available products such as EMUSTAR-0413 manufactured by Nippon Seiki, Cerosol 524 manufactured by Chukyo Yushi), castor oil (refined castor oil manufactured by Ito Oil Co., Ltd. as a commercial product), rapeseed oil, large Soybean oil, wax, cotton wax, rice wax, sugarcane wax, candelilla wax, Japan wax, jojoba oil, among these, especially excellent in offset resistance, adhesion resistance, paper penetration, gloss and cracks Carnauba wax having a melting point of 70 to 95 ° C. is particularly preferred in that it is difficult to provide an electrophotographic image-receiving sheet capable of forming a high-quality image.
Examples of the animal wax include beeswax, lanolin, spermaceti, stew wax (whale oil), and wool wax.
[0083]
Examples of the mineral wax include, for example, montan wax, montan ester wax, ozokerite, ceresin, fatty acid ester (commercially available products are Sansizer DOA, AN-800, DINA, DIDA, DOZ, DOS, TOTM, TITM manufactured by Shin Nippon Rika). , E-PS, nE-PS, E-PO, E-4030, E-6000, E-2000H, E-9000H, TCP, C-1100, etc.) Polyethylene wax as a synthetic hydrocarbon (commercially available from Chukyo Yushi Co., Ltd.) Polylon A, 393, H-481; Sanyo Kasei Sun Wax E-310, E-330, E-250P, LEL-250, LEL-800, LEL-400P, etc.), Polypropylene wax (commercially available Sanyo Kasei Biscol) 330-P, 550-P, 660-P) etc. It is. Among these, in particular, it has an excellent offset resistance, adhesion resistance, paper permeability, glossiness, is resistant to cracking, and can provide an electrophotographic image-receiving sheet capable of forming a high-quality image. Is particularly preferably a montan wax having a temperature of 70 to 95 ° C.
[0084]
As the petroleum wax, paraffin wax (Nippon Seiki paraffin wax 155, 150, 140, 135, 130, 125, 120, 115, HNP-3, HNP-5, HNP-9, HNP-10, HNP-11, HNP-12, HNP-14G, SP-0160, SP-0145, SP-1040, SP-1035, SP-3040, SP-3035, NPS-8070, NPS-L-70, OX-2151, OX-2251, EMUSTAR-0384, EMUSTAR-0136; Cellosol 686, 428, 651-A, A, H-803, B-460, E-172, 866, K-133, Hydrin D-337, E -139; 125 ° paraffin, 125 ° FD, 130 ° paraffin made by Mitsubishi Oil 135 ° paraffin, 135 ° H, 140 ° paraffin, 140 ° N, 145 ° paraffin, paraffin wax M, etc., microcrystalline wax (commercially available from Nippon Seiki Hi-Mic-2095, Hi-Mic-3090, Hi -Mic-1080, Hi-Mic-1070, Hi-Mic-2065, Hi-Mic-1045, Hi-Mic-2045, EMUSTAR-0001, EMUSTAR-042X; Chukyo Yushi Cellosol 967, M; 155 microwax, 180 microwax, etc.), Petrolatum (commercially available products manufactured by Nippon Seiki OX-1749, OX-0450, OX-0650B, OX-0153, OX-261BN, OX-0551, OX-0550, OX-0750B , JP-1500 JP-056R, such as JP-011P) and the like.
[0085]
Content (g / m) of the natural wax in the toner image-receiving layer (surface)²) As 0.1 to 4 g / m²Is preferably 0.2 to 2 g / m²Is more preferable. The content is 0.1 g / m²If it is less than 4 g / m, the offset resistance and adhesion resistance may be particularly insufficient.²If it exceeds 1, the amount of wax is too large, and the image quality of the formed image may be inferior.
[0086]
The melting point (° C.) of the natural wax is preferably 70 to 95 ° C., more preferably 75 to 90 ° C., particularly in terms of offset resistance and paper passing properties.
[0087]
Examples of the matting agent include various known ones. Solid particles used as a matting agent can be classified into inorganic particles and organic particles. Specific examples of the material for the inorganic matting agent include oxides (for example, silicon dioxide, titanium oxide, magnesium oxide, aluminum oxide), alkaline earth metal salts (for example, barium sulfate, calcium carbonate, magnesium sulfate), halogens Examples include silver halide (eg, silver chloride, silver bromide) and glass.
[0088]
Examples of the inorganic matting agent include West German Patent 2529321, British Patent 760775, 1260772, U.S. Patent 1201905, 2192241, 3030562, 3030649, 3257206, 3322555, and 3353958. No. 3,370,951, No. 3,411,907, No. 3,437,484, No. 3523022, No. 3,615,554, No. 3,635,714, No. 3769020, No. 40212245, and No. 4029504.
[0089]
The material of the organic matting agent includes starch, cellulose ester (for example, cellulose acetate propionate), cellulose ether (for example, ethyl cellulose) and synthetic resin. The synthetic resin is preferably water-insoluble or poorly water-soluble. Examples of water-insoluble or poorly water-soluble synthetic resins include, for example, poly (meth) acrylic acid esters (for example, polyalkyl (meth) acrylate, polyalkoxyalkyl (meth) acrylate, polyglycidyl (meth) acrylate), poly (meth) acrylate, (Meth) acrylamide, polyvinyl ester (for example, polyvinyl acetate), polyacrylonitrile, polyolefin (for example, polyethylene), polystyrene, benzoguanamine resin, formaldehyde condensation polymer, epoxy resin, polyamide, polycarbonate, phenol resin, polyvinyl carbazole, polyvinylidene chloride, Etc.
You may use the copolymer which combined the monomer used for the above polymer.
[0090]
In the case of the copolymer, a small amount of hydrophilic repeating units may be contained. Examples of the monomer forming the hydrophilic repeating unit include acrylic acid, methacrylic acid, α, β-unsaturated dicarboxylic acid, hydroxyalkyl (meth) acrylate, sulfoalkyl (meth) acrylate and styrene sulfonic acid.
Examples of the organic matting agent include British Patent No. 1055713, U.S. Pat. Nos. 3,262,782, 3,443,946, 3,516,832, 3,539,344, 3,591,379, 3,754,924, 3,767,448, JP-A-49-106821, JP-A-57-14835 Are described in the above.
Two or more kinds of solid particles may be used in combination. The average particle size of the solid particles is, for example, preferably 1 to 100 μm, and more preferably 4 to 30 μm. The amount of solid particles used is 0.01 to 0.5 g / m.²Is preferred, 0.02-0.3 g / m²Is more preferable.
[0091]
As the release agent added to the toner image-receiving layer of the present invention, these derivatives, oxides, purified products, and mixtures can also be used. Moreover, these may have a reactive substituent.
[0092]
The melting point (° C.) of the release agent is preferably 70 to 95 ° C., and more preferably 75 to 90 ° C., particularly in terms of offset resistance and paper passing properties.
The release agent is preferably a water-dispersed release agent, particularly in terms of compatibility when an aqueous thermoplastic resin is used as the thermoplastic resin of the toner image receiving layer.
[0093]
The content of the release agent is preferably 0.1 to 10% by mass, more preferably 0.3 to 8.0% by mass, and further 0.5 to 5.0% by mass with respect to the total amount of the toner image-receiving layer. preferable.
[0094]
-Plasticizer-
As the plasticizer, known plasticizers for resins can be used without particular limitation. The plasticizer has a function of adjusting the flow or softening of the toner image-receiving layer by heat and / or pressure when fixing the toner.
Examples of the plasticizer include "Chemical Handbook" (edited by the Chemical Society of Japan, Maruzen), "Plasticizer -Theory and Application-" (written by Koichi Murai, Koshobo), "Research on plasticizer", "Research on plasticizer" "Lower" (edited by Polymer Chemistry Association), "Handbook Rubber and Plastic Compounded Chemicals" (edited by Rubber Digest Co., Ltd.), etc.
[0095]
Some of the plasticizers are described as high-boiling organic solvents and thermal solvents. For example, JP-A-59-83154, 59-178451, 59-178453, and 59-178454. 59-178455, 59-178457, 62-174754, 62-245253, 61-209444, 61-200538, 62-8145, 62-9348, 62-30247, 62-136646, 62-174754, 62-245253, 61-209444, 61-200538, 62-8145, 62-9348, 62- Esters such as those described in publications such as 30247, 62-136646, and JP-A-2-235694 (examples) For example, phthalic acid esters, phosphoric acid esters, fatty acid esters, abietic acid esters, adipic acid esters, sebacic acid esters, azelaic acid esters, benzoic acid esters, butyric acid esters, epoxidized fatty acid esters , Glycolic acid esters, propionic acid esters, trimellitic acid esters, citric acid esters, sulfonic acid esters, carboxylic acid esters, succinic acid esters, maleic acid esters, fumaric acid esters, phthalic acid esters And stearic acid esters), amides (for example, fatty acid amides, sulfoamides, etc.), ethers, alcohols, lactones, polyethyleneoxy compounds, and the like.
The plasticizer can be used by mixing with a resin.
[0096]
A relatively low molecular weight polymer can be used as the plasticizer. In this case, the molecular weight of the plasticizer is preferably lower than the molecular weight of the binder resin to be plasticized, and the molecular weight is preferably 15000 or less, more preferably 5000 or less. In the case of a polymer plasticizer, the polymer is preferably the same type as the binder resin to be plasticized. For example, a low molecular weight polyester is preferable for plasticizing a polyester resin. Furthermore, oligomers can also be used as plasticizers. In addition to the compounds listed above, commercially available products include, for example, Adeka Sizer PN-170, PN-1430 manufactured by Asahi Denka Kogyo; P. HALL products PARAPLEX-G-25, G-30, G-40; Rika Hercules products Ester gum 8L-JA, Ester R-95, Pentaline 4851, FK115, 4820, 830, Louisol 28-JA, Picolastic A75, Pico Examples include Tex LC and Crystallex 3085.
[0097]
The plasticizer relieves stress and strain (physical strain such as elastic force and viscosity, strain due to mass balance of molecules, binder main chain, pendant, etc.) generated when toner particles are embedded in the toner image receiving layer. Can be used arbitrarily to The plasticizer may be in a micro-dispersed state in the toner image-receiving layer, may be in a phase-separated microscopically in a sea-island shape, or may be in a sufficiently mixed and dissolved state with other components such as a binder.
The content of the plasticizer in the toner image-receiving layer is preferably 0.001 to 90% by mass, more preferably 0.1 to 60% by mass, and still more preferably 1 to 40% by mass.
The plasticizer adjusts smoothness (improves transportability due to reduced frictional force), improves fixing unit offset (detachment of toner and layers from the fixing unit), adjusts curl balance, and adjusts charging (toner electrostatic image It may be used for the purpose of forming).
[0098]
-Filler-
As said filler, an organic or inorganic filler is mentioned, A well-known thing can be used as a reinforcing agent for binder resin, a filler, and a reinforcing material. The filler should be selected with reference to "Handbook Rubber / Plastic Compounding Chemicals" (edited by Rubber Digest Co., Ltd.), "New Edition Plastic Compounding Agent Fundamentals and Applications" (Taiseisha), "Filler Handbook" (Taiseisha), etc. Can do.
Moreover, various inorganic fillers (or pigments) can be used as the filler. Examples of the inorganic pigment include silica, alumina, titanium dioxide, zinc oxide, zirconium oxide, mica-like iron oxide, white lead, lead oxide, cobalt oxide, strontium chromate, molybdenum pigment, smectite, magnesium oxide, calcium oxide, carbonic acid Examples include calcium and mullite. As the filler, silica and alumina are particularly preferable. These fillers may be used alone or in combination of two or more. The filler preferably has a small particle size. If the particle size is large, the surface of the toner image-receiving layer tends to be roughened.
[0099]
The silica includes spherical silica and amorphous silica. The silica can be synthesized by a dry method, a wet method, or an airgel method. The surface of the hydrophobic silica particles may be surface-treated with a trimethylsilyl group or silicone. As silica, colloidal silica is preferable. As an average particle diameter of a silica, 4-120 nm is preferable and 4-90 nm is more preferable.
The silica is preferably porous. The average pore diameter of the porous silica is preferably 50 to 500 nm. Moreover, the average pore volume per mass of the porous silica is preferably, for example, 0.5 to 3 ml / g.
[0100]
The alumina includes anhydrous alumina and alumina hydrate. As the crystal form of anhydrous alumina, α, β, γ, δ, ζ, η, θ, κ, ρ, or χ can be used. Alumina hydrate is preferred over anhydrous alumina. As the alumina hydrate, a monohydrate or a trihydrate can be used. Monohydrates include pseudoboehmite, boehmite and diaspore. Trihydrates include dibsite and bayerite. As an average particle diameter of an alumina, 4-300 nm is preferable and 4-200 nm is more preferable. Alumina is preferably porous. The average pore diameter of porous alumina is preferably 50 to 500 nm. The average pore volume per mass of the porous alumina is preferably about 0.3 to 3 ml / g.
[0101]
The alumina hydrate can be synthesized by a sol-gel method in which ammonia is added to an aluminum salt solution to precipitate or a method in which an alkali aluminate is hydrolyzed. Anhydrous alumina can be obtained by dehydrating alumina hydrate by heating.
It is preferable that the said filler is 5-2000 mass% based on the dry mass of the binder of the layer to add.
[0102]
-Crosslinking agent-
The cross-linking agent can be blended in order to adjust the storage stability, thermoplasticity, etc. of the toner image-receiving layer. As such a crosslinking agent, an epoxy group as a reactive group, an isocyanate group, an aldehyde group, an active halogen group, an active methylene group, an acetylene group, or a compound having two or more known reactive groups in the molecule is used.
[0103]
As the cross-linking agent, a compound having two or more groups capable of forming a bond by hydrogen bond, ionic bond, coordination bond or the like can be used. As the crosslinking agent, known compounds can be used as coupling agents for resins, curing agents, polymerization agents, polymerization accelerators, coagulants, film-forming agents, film-forming aids, and the like. Examples of coupling agents include, for example, chlorosilanes, vinyl silanes, epoxy silanes, aminosilanes, alkoxyaluminum chelates, titanate coupling agents, etc., and "Handbook Rubber / Plastic Compounding Chemicals" (Rubber Digest Co., Ltd.) Ed.) Or the like can be used.
[0104]
-Charge control agent-
The toner image-receiving layer of the present invention preferably contains a charge adjusting agent in order to adjust toner transfer, adhesion, etc., and to prevent charge adhesion of the toner image-receiving layer. Conventionally known various charge control agents can be used as the charge control agent. Examples of such a charge control agent include cationic surfactants, surfactants such as anionic surfactants, amphoteric surfactants, and nonionic surfactants, as well as polymer electrolytes and conductive metal oxides. Things can be used. For example, quaternary ammonium salts, polyamine derivatives, cation-modified polymethyl methacrylate, cationic antistatic agents such as cation-modified polystyrene, anionic antistatic agents such as alkyl phosphates and anionic polymers, fatty acid esters, polyethylene oxide, etc. Nonionic antistatic agents may be mentioned, but are not limited thereto.
[0105]
When the toner has a negative charge, for example, a cation or nonion is preferable as the charge adjusting agent to be blended in the toner image receiving layer.
Examples of the conductive metal oxide include ZnO and TiO.₂, SnO₂, Al₂O₃, In₂O₃, SiO₂, MgO, BaO, MoO₃Etc. These conductive metal oxides may be used alone or in combination with these composite oxides. In addition, the metal oxide may further contain a different element, for example, Al, In, etc. with respect to ZnO, such as TiO.₂Nb, Ta, etc., SnO₂Can contain (doping) Sb, Nb, a halogen element, or the like.
[0106]
-Other additives-
The material that can be used in the toner image-receiving layer of the present invention can contain various additives for improving the stability of the output image and improving the stability of the toner image-receiving layer itself. Additives for this purpose include various known antioxidants, anti-aging agents, deterioration inhibitors, ozone deterioration inhibitors, ultraviolet absorbers, metal complexes, light stabilizers, preservatives, fungicides, etc. Can be mentioned.
[0107]
Examples of the antioxidant include a chroman compound, a coumaran compound, a phenol compound (eg, hindered phenol), a hydroquinone derivative, a hindered amine derivative, and a spiroindane compound. The antioxidant is described in JP-A No. 61-159644.
[0108]
Examples of the antiaging agent include those described in “Handbook Rubber / Plastic Compounding Chemicals Revised 2nd Edition” (1993, Rubber Digest Co.) p76-121.
[0109]
Examples of the ultraviolet absorber include a benzotriazole compound (described in US Pat. No. 3,533,794), a 4-thiazolidone compound (described in US Pat. No. 3,352,681), a benzophenone compound (described in Japanese Patent Application Laid-Open No. 46-2784), and Examples thereof include ultraviolet absorbing polymers (described in JP-A-62-260152).
[0110]
Examples of the metal complex include the specifications of U.S. Pat. Nos. 1 and 74272 are appropriate.
Further, ultraviolet absorbers and light stabilizers described in "Handbook Rubber / Plastic Compounding Chemicals Revised Second Edition" (1993, Rubber Digest Co., Ltd.) p122-137 are also preferably used.
[0111]
[Physical properties of toner image-receiving layer]
The toner image-receiving layer has a 180 degree peel strength at a fixing temperature with the fixing member of preferably 0.1 N / 25 mm or less, and more preferably 0.041 N / 25 mm or less. The 180 degree peel strength can be measured according to the method described in JIS K6887 using the surface material of the fixing member.
The toner image receiving layer preferably has high whiteness. The whiteness is preferably 85% or more as measured by the method defined in JISP 8123. Further, in the wavelength range of 440 nm to 640 nm, the spectral reflectance is preferably 85% or more, and the difference between the maximum spectral reflectance and the minimum spectral reflectance in the same wavelength region is preferably within 5%. Furthermore, the spectral reflectance is preferably 85% or more in the wavelength region of 400 nm to 700 nm, and the difference between the maximum spectral reflectance and the minimum spectral reflectance in the same wavelength region is more preferably within 5%.
As the whiteness, specifically, CIE 1976 (L^*a^*b^*) In color space, L^*The value is preferably 80 or more, more preferably 85 or more, and still more preferably 90 or more. The white color is preferably as neutral as possible. The white color is L^*a^*b^*In space, (a^*)²+ (B^*)²The value of is preferably 50 or less, more preferably 18 or less, and still more preferably 5 or less.
[0112]
The toner image receiving layer preferably has high gloss. As the glossiness, the 45 ° glossiness is preferably 60 or more, more preferably 75 or more, and still more preferably 90 or more in the entire region from white without toner to black having the maximum density.
However, the glossiness is preferably 110 or less. If it exceeds 110, it becomes like metallic luster, which is not preferable as image quality.
In addition, the said glossiness can be measured based on JISZ8741.
[0113]
The toner image receiving layer preferably has high smoothness. As the smoothness, the arithmetic average roughness (Ra) is preferably 3 μm or less, more preferably 1 μm or less, and even more preferably 0.5 μm or less in the entire region from white without toner to black having the maximum density.
The arithmetic average roughness can be measured based on JIS B 0601, B 0651, B 0652.
[0114]
The toner image-receiving layer preferably has one physical property among the following items, more preferably a plurality of items, and most preferably all physical properties.
(1) Tm (melting temperature) of the toner image-receiving layer is 30 ° C. or higher and Tm + 20 ° C. or lower of the toner.
(2) The toner image receiving layer has a viscosity of 1 × 10⁵The temperature at which CP becomes 40 ° C. or higher is lower than that of toner.
(3) The storage elastic modulus (G ′) at the fixing temperature of the toner image receiving layer is 1 × 10.²~ 1x10⁵Pa, loss elastic modulus (G ″) is 1 × 10²~ 1x10⁵Pa.
(4) The loss tangent (G ″ / G ′), which is the ratio of the loss elastic modulus (G ″) at the fixing temperature of the toner image receiving layer and the storage elastic modulus (G ′), is 0.01 to 10.
(5) The storage elastic modulus (G ′) at the fixing temperature of the toner image-receiving layer is −50 to +2500 with respect to the storage elastic modulus (G ″) at the fixing temperature of the toner.
(6) The inclination angle of the molten toner on the toner image-receiving layer is 50 degrees or less, particularly 40 degrees or less.
The toner image-receiving layer preferably satisfies the physical properties disclosed in Japanese Patent No. 2788358, Japanese Patent Application Laid-Open Nos. 7-248637, 8-305067, 10-239889, and the like. .
[0115]
The physical property (1) can be measured by a differential scanning calorimeter (DSC). The physical properties (2) to (3) can be measured using, for example, a flow tester CFT-500 or 500D manufactured by Shimadzu Corporation. The physical properties (5) to (7) can be measured using a rotational rheometer (for example, a dynamic analyzer RADII manufactured by Rheometric). The physical property (8) can be measured by a method disclosed in JP-A-8-334916 using a contact angle measuring device manufactured by Kyowa Interface Science Co., Ltd.
[0116]
As the toner image-receiving layer, 1 × 10⁶~ 1x10¹⁵Ω / cm²It is preferable to have a surface electrical resistance in the range of (under conditions of 25 ° C. and 65% RH).
The surface resistance is 1 × 10⁶Ω / cm²If it is less than 1, the amount of toner when the toner is transferred to the toner image-receiving layer is not sufficient, and the density of the resulting toner image tends to be low. On the other hand, the surface electrical resistance is 1 × 10¹⁵Ω / cm²Exceeding this amount generates more charge than necessary during transfer, and the toner is not sufficiently transferred, resulting in a low image density, and electrostatic charge is easily deposited during handling of the electrophotographic image receiving sheet. Misfeeds, double feeds, discharge marks, toner transfer missing, etc. may occur during copying.
Here, the measurement of the surface electrical resistance is based on JIS K 6911, the sample is conditioned for 8 hours or more in an environment of a temperature of 20 ° C. and a humidity of 65%, and R8340 manufactured by Advantest Co., Ltd. It is obtained by measuring after using for 1 minute after energization under the condition of an applied voltage of 100V.
[0117]
The thickness of the toner image-receiving layer is suitably ½ or more, preferably 1 to 3 times the particle diameter of the toner used. The toner image receiving layer preferably has a thickness disclosed in JP-A-5-216322 and JP-A-7-301939. Specifically, the thickness of the toner image receiving layer is, for example, preferably 1 to 50 μm, and more preferably 5 to 15 μm.
[0118]
(toner)
The electrophotographic image-receiving sheet of the present invention is used by allowing a toner image-receiving layer to receive toner during printing or copying.
The toner contains at least a binder resin and a colorant, and if necessary, a release agent and other components.
[0119]
-Toner binder resin-
Examples of the binder resin include styrenes such as styrene and parachlorostyrene; vinyl esters such as vinyl naphthalene, vinyl chloride, vinyl bromide, vinyl fluoride, vinyl acetate, vinyl propionate, vinyl benzoate, and vinyl butyrate; Methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, dodecyl acrylate, n-octyl acrylate, 2-chloroethyl acrylate, phenyl acrylate, methyl α-chloroacrylate, methyl methacrylate, methacryl Methylene aliphatic carboxylic acid esters such as ethyl acetate and butyl methacrylate; Vinyl nitriles such as acrylonitrile, methacrylonitrile, and acrylamide; Vinyl ethers such as vinyl methyl ether, vinyl ethyl ether, and vinyl isobutyl ether Tells; N-vinyl compounds such as N-vinyl pyrrole, N-vinyl carbazole, N-vinyl indole, N-vinyl pyrrolidone; single weight of vinyl monomers such as vinyl carboxylic acids such as methacrylic acid, acrylic acid and cinnamic acid Copolymers, copolymers thereof, and various polyesters can be used, and various waxes can be used in combination.
Among these resins, it is preferable to use resins of the same system as those used for the toner image receiving layer of the present invention.
[0120]
-Toner Colorant-
As the colorant, those usually used in toners can be used without limitation. For example, carbon black, chrome yellow, hansa yellow, benzidine yellow, sren yellow, quinoline yellow, permanent orange GTR, pyrazolone. Orange, Vulcan Orange, Watch Young Red, Permanent Red, Brilliantamine 3B, Brilliantamine 6B, Daypon Oil Red, Pyrazolone Red, Risor Red, Rhodamine B Lake, Lake Red C, Rose Bengal, Aniline Blue, Ultramarine Blue, Calco Examples include various pigments such as oil blue, methylene blue chloride, phthalocyanine blue, phthalocyanine green, and malachite green oxalelate. Acridine, xanthene, azo, benzoquinone, azine, anthraquinone, thioindico, dioxazine, thiazine, azomethine, indico, thioindico, phthalocyanine, aniline black, polymethine, triphenyl Examples include various dyes such as methane, diphenylmethane, thiazine, thiazole, and xanthene. These colorants may be used alone or in combination of two or more.
The content of the colorant is preferably in the range of 2 to 8% by mass. If the content of the colorant is 2% by mass or more, the coloring power is not weakened. On the other hand, if it is 8% by mass or less, the transparency is not impaired, which is preferable.
[0121]
-Toner release agent-
As the mold release agent, all known waxes can be used in principle, but polar waxes containing nitrogen such as relatively low molecular weight high crystalline polyethylene wax, Fischer-Tropsch wax, amide wax, urethane compound, etc. Etc. are particularly effective. The molecular weight of the polyethylene wax is preferably 1000 or less, and more preferably 300 to 1000.
[0122]
The compound having a urethane bond is suitable because even if it has a low molecular weight, the solid state can be maintained and the melting point can be set high for the molecular weight due to the strength of cohesive force due to the polar group. The preferred range of molecular weight is 300-1000. The raw materials are a combination of diisocyanate compounds and monoalcohols, a combination of monoisocyanic acid and monoalcohol, a combination of dialcohols and monoisocyanic acid, a combination of trialcohols and monoisocyanic acid, triisocyanic acid Various combinations such as combinations of compounds and monoalcohols can be selected, but in order not to increase the molecular weight, it is preferable to combine a compound of a polyfunctional group and a monofunctional group, and an equivalent functional group amount. It is important to ensure that
[0123]
Specific examples of the raw material compound include monoisocyanate compounds such as dodecyl isocyanate, phenyl isocyanate and derivatives thereof, naphthyl isocyanate, hexyl isocyanate, benzyl isocyanate, butyl isocyanate, and allyl isocyanate. It is done.
Examples of the diisocyanate compound include tolylene diisocyanate, 4,4'diphenylmethane diisocyanate, toluene diisocyanate, 1,3-phenylene diisocyanate, hexamethylene diisocyanate, 4-methyl-m-phenylene diisocyanate, and isophorone diisocyanate. Can be mentioned.
As the monoalcohol, it is possible to use very common alcohols such as methanol, ethanol, propanol, butanol, pentanol, hexanol, and heptanol.
Among the raw material compounds, as the dialcohols, a number of glycols such as ethylene glycol, diethylene glycol, triethylene glycol, trimethylene glycol; as the trialcohols, trimethylolpropane, triethylolpropane, trimethanolethane, etc. can be used. However, it is not necessarily limited to this range.
[0124]
These urethane compounds can be mixed with a resin and a colorant at the time of kneading and used as a kneaded and pulverized toner as in a normal release agent. Also, when used in the emulsion polymerization aggregation melting toner described above, it is dispersed in water together with a polymer electrolyte such as an ionic surfactant, a polymer acid or a polymer base, and heated to a melting point or higher to produce a homogenizer or pressure discharge. A fine dispersion is obtained by applying strong shearing with a mold disperser to prepare a release agent particle dispersion of 1 μm or less, which can be used together with a resin particle dispersion, a colorant dispersion and the like.
[0125]
-Toner and other components-
Further, the toner of the present invention may contain other components such as an internal additive, a charge control agent, and inorganic fine particles. As the internal additive, a magnetic material such as a metal such as ferrite, magnetite, reduced iron, cobalt, nickel, manganese, an alloy, or a compound containing these metals can be used.
[0126]
As the charge control agent, various commonly used charge control agents such as quaternary ammonium salt compounds, nigrosine compounds, dyes composed of complexes of aluminum, iron, chromium, and triphenylmethane pigments may be used. it can. A material that is difficult to dissolve in water is preferable from the viewpoint of controlling the ionic strength that affects the stability during aggregation and melting and reducing wastewater contamination.
[0127]
Examples of the inorganic fine particles include silica, alumina, titania, calcium carbonate, magnesium carbonate, tricalcium phosphate, and the like. Usually, all external additives on the toner surface are used. It is preferable to use by dispersing with a molecular base.
[0128]
Furthermore, a surfactant can be used for emulsion polymerization, seed polymerization, pigment dispersion, resin particle dispersion, release agent dispersion, aggregation, and stabilization thereof. For example, anionic surfactants such as sulfate ester, sulfonate, phosphate, and soap, cationic surfactants such as amine salt type and quaternary ammonium salt type, polyethylene glycol type, alkylphenol It is also effective to use a nonionic surfactant such as an ethylene oxide adduct system or a polyhydric alcohol system in combination. As a dispersing means at that time, a general means such as a rotary shear type homogenizer, a ball mill having a media, a sand mill, a dyno mill or the like can be used.
[0129]
An external additive may be further added to the toner as necessary. Examples of the external additive include inorganic powder and organic particles. Examples of the inorganic particles include SiO.₂TiO₂, Al₂O₃, CuO, ZnO, SnO₂, Fe₂O₃, MgO, BaO, CaO, K₂O, Na₂O, ZrO₂, CaO · SiO₂, K₂O. (TiO₂)_n, Al₂O₃・ 2SiO₂, CaCO₃, MgCO₃, BaSO₄, MgSO₄Etc. can be illustrated. Moreover, as said organic particle, resin powder, such as powders, such as fatty acid or its derivative (s), these metal salts, fluorine resin, a polyethylene resin, an acrylic resin, can be used. For example, the average particle size of these powders is preferably 0.01 to 5 μm, and more preferably 0.1 to 2 μm.
[0130]
The method for producing the toner is not particularly limited, and (i) a step of forming aggregated particles in a dispersion obtained by dispersing resin particles to prepare an aggregated particle dispersion, (ii) in the aggregated particle dispersion. A step of adding and mixing a fine particle dispersion in which fine particles are dispersed to adhere the fine particles to the aggregated particles to form adhered particles; and (iii) heating and fusing the adhered particles to form toner particles. It is preferable that the toner is manufactured by a toner manufacturing method including the steps.
[0131]
-Toner physical properties-
The volume average particle diameter of the toner of the present invention is preferably from 0.5 μm to 10 μm.
If the volume average particle size of the toner is too small, there may be an adverse effect on toner handling (replenishability, cleaning properties, fluidity, etc.), and particle productivity may be reduced. On the other hand, if the volume average particle diameter of the toner is too large, the image quality and resolution due to graininess and transferability may be adversely affected.
The toner of the present invention preferably satisfies the above-mentioned toner volume average particle size range, and the volume average particle size distribution index (GSDv) is preferably 1.3 or less.
The ratio (GSDv / GSDn) of the volume average particle size distribution index (GSDv) to the number average particle size distribution index (GSDn) is preferably 0.95 or more.
In addition, the toner of the present invention satisfies the volume average particle diameter range of the toner, and the average value of the shape factor represented by the following formula is preferably 1.00 to 1.50.
Shape factor = (π × L²) / (4 × S)
(However, L represents the maximum length of toner particles, and S represents the projected area of toner particles.)
When the toner satisfies the above conditions, it is effective for image quality, particularly graininess, and resolution, and it is difficult for transfer and omission to occur, and handling properties are not adversely affected even if the average particle size is not small. Become.
[0132]
The storage elastic modulus G ′ (measured at an angular frequency of 10 rad / sec) at 150 ° C. of the toner itself is suitably 10 to 200 Pa from the viewpoint of improving the image quality and preventing the offset property in the fixing process.
[0133]
[Image forming apparatus and image forming method]
A method for forming an image on the electrophotographic image receiving sheet is not particularly limited. It can be applied to various electrophotographic methods.
For example, a color image can be preferably formed on the electrophotographic image-receiving sheet. The color image can be formed using an electrophotographic apparatus capable of forming a full color image. A typical electrophotographic apparatus has an image receiving paper transport section, a latent image forming section, and a developing section disposed in the vicinity of the latent image forming section. Depending on the model, a latent image is formed at the center of the apparatus main body. A toner image intermediate transfer portion adjacent to the image receiving portion and the image receiving paper transport portion.
[0134]
Furthermore, as a method for improving the image quality, an adhesive transfer or heat-assisted transfer system is known instead of or in combination with electrostatic transfer or bias roller transfer. For example, Japanese Patent Laid-Open Nos. 63-113576 and 5-341666 describe specific structures thereof. In particular, a method using a heat-assisted transfer type intermediate transfer belt is preferable when a toner having a small particle diameter is used. As the intermediate belt, for example, an endless belt made of electroformed nickel, having a silicone or fluorine-based thin film on the surface and imparting a peeling property is used. Further, it is preferable to provide a cooling device for the intermediate belt after toner transfer to the electrophotographic image receiving sheet or in the latter half of the transfer. The cooling device cools the toner below the softening temperature or glass transition temperature of the binder used therein, and efficiently transfers the toner to the electrophotographic image-receiving sheet so that it can be peeled off from the intermediate belt.
[0135]
Fixing is an important process that affects the gloss and smoothness of the final image. As the fixing method, fixing by a heat and pressure roller, belt fixing using a belt, and the like are known, but the belt fixing method is preferable from the viewpoint of the image quality such as gloss and smoothness. Regarding the belt fixing method, for example, an oilless type belt fixing method described in JP-A-11-352819, secondary transfer and fixing described in JP-A-11-231671 and JP-A-5-341666 are performed. Methods to achieve at the same time are known.
[0136]
The surface of the fixing belt is preferably subjected to a surface treatment of a silicone type, a fluorine type or a combination thereof in order to prevent toner releasability or toner component offset. Further, it is preferable to provide a belt cooling device in the latter half of the fixing so that the electrophotographic image-receiving sheet is peeled off favorably. The cooling temperature is preferably not higher than the softening point of the polymer of the toner image-receiving layer in the toner binder and / or electrophotographic image-receiving sheet, or the glass transition point. On the other hand, in the initial fixing stage, it is preferable to raise the temperature to a temperature at which the toner image-receiving layer or toner of the electrophotographic image-receiving sheet is sufficiently softened. Specifically, the cooling temperature is preferably 70 ° C. or lower and 30 ° C. or higher practically, and more preferably 180 ° C. or lower and 100 ° C. or higher in the initial fixing stage.
[0137]
Here, it is appropriate that the fixing belt used in the image forming apparatus is an endless belt formed using, for example, polyimide, electroformed nickel, aluminum, or the like as a base material.
It is preferable that a thin film made of at least one selected from the group consisting of silicone rubber, fluororubber, silicone resin, and fluororesin is formed on the surface of the fixing belt. Among these, a mode in which a fluorocarbon siloxane rubber layer having a uniform thickness is provided on the surface of the fixing belt, a silicone rubber layer having a uniform thickness on the surface of the fixing belt, and the silicone rubber layer An embodiment in which a layer made of a fluorocarbon siloxane rubber having a uniform thickness is provided on the surface is preferable.
[0138]
The fluorocarbon siloxane rubber preferably has a perfluoroalkyl ether group and / or a perfluoroalkyl group in the main chain.
Such a fluorocarbon siloxane rubber includes (A) a fluorocarbon siloxane having the following general formula (1) as a main component and an aliphatic unsaturated group, and (B) two or more ≡SiH groups in one molecule. Organopolysiloxane and / or fluorocarbon siloxane, wherein the content of the ≡SiH group is 1 to 4 times the molar amount of the aliphatic unsaturated group in the fluorocarbon siloxane rubber composition, (C) filling A cured product of a fluorocarbon siloxane rubber composition containing an agent and (D) an effective amount of a catalyst is preferably used.
[0139]
The (A) component fluorocarbon polymer is mainly composed of a fluorocarbon siloxane having a repeating unit represented by the following general formula (1) and has an aliphatic unsaturated group.
[0140]
[Chemical 1]

[0141]
Here, in the above formula (1), R¹⁰Is an unsubstituted or substituted monovalent hydrocarbon group having preferably 1 to 8 carbon atoms, preferably an alkyl group having 1 to 8 carbon atoms or an alkenyl group having 2 to 3 carbon atoms, particularly a methyl group. Is preferred. a and e are each 0 or 1, b and d are each an integer of 1 to 4, and c is an integer of 0 to 8. Moreover, x is an integer greater than or equal to 1, Preferably it is 10-30.
[0142]
Examples of the component (A) include those represented by the following formula (2).
[0143]
[Chemical 2]

[0144]
In the component (B), examples of the organopolysiloxane having an ≡SiH group include organohydrogenpolysiloxanes having at least two hydrogen atoms bonded to silicon atoms in the molecule.
[0145]
In the fluorocarbon siloxane rubber composition used in the present invention, when the fluorocarbon polymer as the component (A) has an aliphatic unsaturated group, the above-described organohydrogenpolysiloxane can be used as a curing agent. . That is, in this case, a cured product is formed by an addition reaction that occurs between an aliphatic unsaturated group in the fluorocarbon siloxane and a hydrogen atom bonded to a silicon atom in the organohydrogenpolysiloxane.
[0146]
As such organohydrogenpolysiloxane, various organohydrogenpolysiloxanes used in addition-curable silicone rubber compositions can be used.
[0147]
The above-mentioned organohydrogenpolysiloxane generally has at least one ≡SiH group, particularly 1 to 5 with respect to one aliphatic unsaturated hydrocarbon group in the fluorocarbon siloxane of component (A). It is suitable to mix | blend in such a ratio.
[0148]
Further, the fluorocarbon having an ≡SiH group may be a unit of the above formula (1) or R¹⁰Is preferably a dialkylhydrogensiloxy group and the terminal is a ≡SiH group such as a dialkylhydrogensiloxy group or a silyl group, and examples thereof include those represented by the following formula (3).
[0149]
[Chemical 3]

[0150]
As the filler of the component (C), various fillers used in general silicone rubber compositions can be used. For example, fumed silica, precipitated silica, carbon powder, titanium dioxide, aluminum oxide, quartz powder, reinforcing fillers such as talc, sericite and bentonite, fibrous fillers such as asbestos, glass fiber, organic fiber, etc. It can be illustrated.
[0151]
As the catalyst of the component (D), chloroplatinic acid, alcohol-modified chloroplatinic acid, complexes of chloroplatinic acid and olefin, platinum black or palladium, which are known as addition reaction catalysts, alumina, silica, carbon, etc. Examples are those supported on the above-mentioned carriers, complex of rhodium and olefin, group VIII element of periodic table such as chlorotris (triphenylphosphine) rhodium (Wilkinson catalyst), rhodium (III) acetylacetonate, etc. However, these complexes are preferably used by being dissolved in a solvent such as an alcohol, ether, or hydrocarbon.
[0152]
In the fluorocarbon siloxane rubber composition used in the present invention, various compounding agents can be added as long as the object of the present invention to improve solvent resistance is not impaired. For example, dispersants such as diphenylsilane diol, low-molecular-degree molecular chain terminal hydroxyl-blocked dimethylpolysiloxane, hexamethyldisilazane, etc., heat resistance improvers such as ferrous oxide, ferric oxide, cerium oxide, and iron octylate In addition, colorants such as pigments can be blended as necessary.
[0153]
The fixing belt of the present invention is obtained by coating the surface of a heat resistant resin or metal belt body with the fluorocarbon siloxane rubber composition, followed by heat curing. It can be diluted with a solvent such as hexafluoride or benzotrifluoride to form a coating solution, which can be applied by a general coating method such as spray coating, dip coating or knife coating. The temperature and time for heat curing can be selected as appropriate, and are selected according to the type of belt body and the manufacturing method, etc., in the range of normal temperature 100 to 500 ° C. and time 5 seconds to 5 hours.
[0154]
The thickness of the fluorocarbon siloxane rubber layer formed on the surface of the fixing belt is not particularly limited. However, in order to obtain good image fixing properties by preventing toner releasability or toner component offset. 500 micrometers is preferable and 40-200 micrometers is more preferable.
[0155]
The method for forming an image on the electrophotographic image-receiving sheet of the present invention is not limited to the above-described image forming method as long as it is an electrophotographic method using a fixing belt. Any ordinary electrophotographic method can be applied.
[0156]
<Inkjet recording material>
Examples of the ink jet recording material include liquid inks such as water-based inks (using dyes or pigments as coloring materials) and oil-based inks on the recording material support of the present invention, and solids at room temperature. The colorant receiving layer capable of receiving a solid ink or the like that is melted and liquefied and used for printing, and other layers appropriately selected as necessary, for example, a back layer, a protective layer, an intermediate layer, and an undercoat layer , A cushion layer, a charge control (prevention) layer, a reflection layer, a tint preparation layer, a storage stability improving layer, an adhesion prevention layer, an anti-curl layer, a smoothing layer, and the like. Each of these layers may have a single layer structure or a laminated structure.
[0157]
(Color material receiving layer)
The color material receiving layer contains at least polymer fine particles, and further contains a water-soluble resin, a crosslinking agent, a mordant and the like.
[0158]
-Polymer fine particles-
A porous structure is obtained when the colorant receiving layer contains fine polymer particles, thereby improving the ink absorption performance. In particular, if the solid content of the polymer fine particles in the colorant receiving layer is 50% by mass or more, more preferably more than 60% by mass, it becomes possible to form a more favorable porous structure, and sufficient ink This is preferable because an ink jet recording sheet having absorbency can be obtained. Here, the solid content in the colorant receiving layer of the polymer fine particles is a content calculated based on components other than water in the composition constituting the colorant receiving layer.
[0159]
The polymer fine particles (latex) can be used in the form of a hydrophilic solvent dispersion of various polymers. Specifically, water dispersion of acrylic polymers, ester polymers, urethane polymers, amide polymers, olefin polymers, vinylidene chloride polymers, epoxy polymers, amide polymers and their modified products and copolymers. The body can be used. Among these, acrylic polymers, olefin polymers, and urethane polymers are preferably used, and olefin polymers and acrylic polymers are preferable from the viewpoint of ink absorbability and coating film strength.
[0160]
As the olefin polymer, a polymer comprising a copolymer of a vinyl monomer and a diolefin is preferable. As the vinyl monomer, for example, styrene, acrylonitrile, methacrylonitrile, methyl acrylate, methyl methacrylate, vinyl acetate and the like are preferably used. As the diolefins, for example, butadiene, isoprene, chloroprene and the like are preferably used.
In addition to these components, unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, maleic anhydride, or alkyl esters thereof, acrolein, methacrolein, glycidyl acrylate, glycidyl methacrylate, acrylic acid- Crosslinkable components such as 2-hydroxylethyl, methacrylic acid-2-hydroxylethyl, allyl acrylate, N-methylolacrylamide, and vinyl isocyanate can also be added.
[0161]
Examples of the acrylic polymer include acrylic acid or methacrylic acid esters such as a linear or branched aliphatic group having 1 to 18 carbon atoms, an aliphatic group having a phenyl group, an aralkyl group, or a hydroxyl group, acrylic Nitriles, N- or N, N-acrylamides of alkyl groups having 1 to 18 carbon atoms, and homopolymers or copolymers of acrylic acid or methacrylic acid and their salts, or the monomers, styrene sulfonic acid, Vinylsulfonic acid and salts thereof, itaconic acid, maleic acid, fumaric acid and salts thereof, acid anhydrides such as itaconic anhydride and maleic anhydride, vinyl isocyanate, allyl isocyanate, vinyl methyl ether, vinyl acetate, styrene, divinyl Examples thereof include copolymers with benzene and the like.
[0162]
Usually, these polymer fine particles are obtained by an emulsion polymerization method. The surfactants, polymerization initiators, etc. used there may be those used in conventional methods. Regarding the method for synthesizing the polymer fine particles, U.S. Pat. Nos. 2,852,368, 2,853,457, 3,411,911, 3,411,912, 4,197,127, Belgian Patent Nos. 688,882, 691,360, 712,823, JP-B 45-5331, JP-A-60-18540, 51-130217, 58-137831, 55- It is described in detail in each publication such as No. 50240.
[0163]
The average particle size of the polymer fine particles is preferably 10 to 100 nm, and more preferably 30 to 80 nm.
[0164]
-Water-soluble resin-
In the ink jet recording sheet, the color material receiving layer preferably contains a water-soluble resin together with the polymer fine particles.
[0165]
Examples of the water-soluble resin include a polyvinyl alcohol-based resin (polyvinyl alcohol (PVA), acetoacetyl-modified polyvinyl alcohol, cation-modified polyvinyl alcohol, anion-modified polyvinyl alcohol, silanol-modified resin that has a hydroxyl group as a hydrophilic structural unit). Polyvinyl alcohol, polyvinyl acetal, etc.], cellulose resins [methyl cellulose (MC), ethyl cellulose (EC), hydroxyethyl cellulose (HEC), carboxymethyl cellulose (CMC), hydroxypropyl cellulose (HPC), hydroxyethyl methyl cellulose, hydroxypropyl methyl cellulose, etc.] , Chitins, chitosans, starch, resins with ether linkages [polyethylene oxide (PEO), Propylene oxide (PPO), polyethylene glycol (PEG), poly ether (PVE)], and resins having carbamoyl groups [polyacrylamide (PAAM), polyvinyl pyrrolidone (PVP), polyacrylic acid hydrazide, etc.] and the like.
Moreover, the polyacrylic acid salt which has a carboxyl group as a dissociable group, maleic acid resin, alginate, gelatins, etc. can be mentioned.
[0166]
Among these, polyvinyl alcohol resin is particularly preferable. Examples of the polyvinyl alcohol include Japanese Patent Publication No. 4-52786, Japanese Patent Publication No. 5-67432, Japanese Patent Publication No. 7-29479, Japanese Patent No. 2537827, Japanese Patent Publication No. 7-57553, Japanese Patent No. 2502998, and Japanese Patent No. 3053231. JP-A-63-176173, JP-A-2604367, JP-A-7-276787, JP-A-9-207425, JP-A-11-58941, JP-A-2000-135858, JP-A-2001-205924, JP 2001-287444, JP 62-278080, JP 9-39373, JP 2750433, JP 2000-158801, JP 2001-213045, JP 2001-328345, JP 8 -324105, JP-A-11-348417, etc. Etc., and the like.
Examples of water-soluble resins other than polyvinyl alcohol resins include the compounds described in JP-A No. 11-165461, [0011] to [0014].
These water-soluble resins may be used alone or in combination of two or more.
[0167]
The content of the water-soluble resin is preferably 9 to 40% by mass, and more preferably 12 to 33% by mass with respect to the total solid content of the colorant receiving layer.
[0168]
In ink jet recording, the porous colorant receiving layer obtained as described above can absorb ink rapidly by capillary action and form dots with good roundness without ink bleeding.
[0169]
-Mass content ratio of polymer fine particles and water-soluble resin-
The mass content ratio [PB ratio (x: y)] of the polymer fine particles (x) and the water-soluble resin (y) greatly affects the film structure and film strength of the colorant receiving layer. That is, as the mass content ratio [PB ratio] increases, the porosity, pore volume, and surface area (per unit mass) increase, but the density and strength tend to decrease.
[0170]
The colorant-receiving layer prevents a decrease in film strength and cracks during drying caused by the PB ratio being too large as the mass content ratio [PB ratio (x: y)], and the PB When the ratio is too small, the voids are easily blocked by the resin, and from the viewpoint of preventing the ink absorbency from being lowered due to the decrease in the void ratio, 5/1 to 20/1 is preferable. 1-20 / 1 is more preferable.
[0171]
Since stress may be applied to the recording sheet when passing through the conveyance system of the ink jet printer, the color material receiving layer needs to have sufficient film strength. In the case of cutting into a sheet shape, it is preferable that the color material receiving layer has sufficient film strength in order to prevent the color material receiving layer from being cracked or peeled off.
[0172]
-Crosslinking agent-
The colorant-receiving layer of the ink jet recording sheet preferably contains a crosslinking agent capable of further crosslinking the water-soluble resin in the coating layer containing the water-soluble resin, and particularly the polymer fine particles and the water-soluble resin are used in combination. Furthermore, an embodiment in which the porous layer is cured by a crosslinking reaction between the crosslinking agent and the water-soluble resin is preferable.
[0173]
Boron compounds are preferred for crosslinking the water-soluble resin, particularly polyvinyl alcohol. Examples of the boron compound include borax, boric acid, borates (for example, orthoborate, InBO).₃, ScBO₃, YBO₃, LaBO₃, Mg₃(BO₃)₂, Co₃(BO₃)₂Diborate (eg Mg₂B₂O₅, Co₂B₂O₅), Metaborates (eg LiBO)₂, Ca (BO₂)₂, NaBO₂, KBO₂), Tetraborate (eg, Na₂B₄O₇・ 10H₂O), pentaborate (for example, KB)₅O₈・ 4H₂O, Ca₂B₆O₁₁・ 7H₂O, CsB₅O₅And the like. Of these, borax, boric acid, and borate are preferable, and boric acid is particularly preferable in that a crosslinking reaction can be promptly caused.
[0174]
As the crosslinking agent for the water-soluble resin, the following compounds other than the boron compound may be used.
For example, aldehyde compounds such as formaldehyde, glyoxal and glutaraldehyde; ketone compounds such as diacetyl and cyclopentanedione; bis (2-chloroethylurea) -2-hydroxy-4,6-dichloro-1,3,5- Active halogen compounds such as triazine and 2,4-dichloro-6-S-triazine sodium salt; divinylsulfonic acid, 1,3-vinylsulfonyl-2-propanol, N, N′-ethylenebis (vinylsulfonylacetamide) ), Active vinyl compounds such as 1,3,5-triacryloyl-hexahydro-S-triazine; N-methylol compounds such as dimethylolurea and methyloldimethylhydantoin; melamine resins (for example, methylolmelamine, alkylated methylolmelamine) Epoxy resin; 1,6 Isocyanate compounds such as hexamethylene diisocyanate; Aziridine compounds described in US Pat. Nos. 3,017,280 and 2998611; Carboximide compounds described in US Pat. No. 3,100,704; Epoxys such as glycerol triglycidyl ether Compounds; ethyleneimino compounds such as 1,6-hexamethylene-N, N′-bisethyleneurea; halogenated carboxaldehyde compounds such as mucochloric acid and mucophenoxycyclolic acid; dioxane such as 2,3-dihydroxydioxane Compounds: titanium lactate, aluminum sulfate, chromium alum, potash alum, metal-containing compounds such as zirconyl acetate and chromium acetate, polyamine compounds such as tetraethylenepentamine, hydrazide compounds such as adipic acid dihydrazide, oxy It is a small molecule or polymer or the like containing gelsolin group two or more.
The above bridging agents may be used alone or in combination of two or more.
[0175]
In the crosslinking curing, a crosslinking agent is added to a coating solution containing polymer fine particles, a water-soluble resin and the like (hereinafter sometimes referred to as “coating solution A”) and / or the following basic solution, and (1) At the same time as the coating layer is formed by coating the coating solution, or (2) anytime during the drying of the coating layer formed by coating the coating solution and before the coating layer exhibits reduced-rate drying Further, it is preferable to carry out by applying a basic solution having a pH of 8 or more (hereinafter sometimes referred to as “coating liquid B”) to the coating layer.
The application of the cross-linking agent is preferably performed as follows when a boron compound is taken as an example. That is, when the colorant receiving layer is a layer obtained by crosslinking and curing a coating layer coated with a coating solution (coating solution A) containing a water-soluble resin containing polymer fine particles and polyvinyl alcohol, the crosslinking and curing is (1) At the same time as the coating layer is formed by applying the coating solution, (2) any one of the coating layers formed by coating the coating solution during dry coating and before the coating layer exhibits reduced-rate drying Sometimes, it is carried out by applying a basic solution (coating solution B) having a pH of 8 or higher to the coating layer. The boron compound as a cross-linking agent may be contained in either the coating solution A or the coating solution B, and may be contained in both the coating solution A and the coating solution B.
1-50 mass% is preferable with respect to water-soluble resin, and, as for the usage-amount of a crosslinking agent, 5-40 mass% is more preferable.
[0176]
-Mordant-
In the present invention, a mordant is preferably contained in the colorant receiving layer in order to improve the water resistance and aging resistance of the formed image.
As the mordant, a cationic polymer (cationic mordant) or an inorganic mordant is preferable as the organic mordant. When the mordant is present in the colorant receiving layer, it can interact with the liquid ink having an anionic dye as the colorant to stabilize the colorant and improve water resistance and aging resistance. The organic mordant and the inorganic mordant may be used alone, respectively, or the organic mordant and the inorganic mordant may be used in combination.
[0177]
A method of adding the mordant to the coating liquid A containing polymer fine particles and a water-soluble resin, or a method of adding the mordant to the coating liquid B and applying it when there is a concern of aggregation between the polymer fine particles can be used. .
[0178]
As the cationic mordant, a polymer mordant having a primary to tertiary amino group or a quaternary ammonium base as a cationic group is preferably used, but a cationic non-polymer mordant may also be used. it can. These mordants are preferably compounds having a mass average molecular weight of 500 to 100,000 from the viewpoint of improving ink absorbability of the colorant receiving layer.
Examples of the polymer mordant include a homopolymer of a monomer having a primary to tertiary amino group and a salt thereof, or a quaternary ammonium base (mordant monomer), and the mordant monomer and other monomers (hereinafter, What is obtained as a copolymer or condensation polymer with "non-mordant monomer") is preferred. Moreover, these polymer mordants can be used in any form of a water-soluble polymer or water-dispersible latex particles.
[0179]
Examples of the monomer (mordanting monomer) include trimethyl-p-vinylbenzylammonium chloride, trimethyl-m-vinylbenzylammonium chloride, triethyl-p-vinylbenzylammonium chloride, triethyl-m-vinylbenzylammonium chloride, N , N-dimethyl-N-ethyl-Np-vinylbenzylammonium chloride, N, N-diethyl-N-methyl-Np-vinylbenzylammonium chloride, N, N-dimethyl-Nn-propyl-N -P-vinylbenzylammonium chloride, N, N-dimethyl-Nn-octyl-Np-vinylbenzylammonium chloride, N, N-dimethyl-N-benzyl-Np-vinylbenzylammonium chloride, N, N-die Ru-N-benzyl-Np-vinylbenzylammonium chloride, N, N-dimethyl-N- (4-methyl) benzyl-Np-vinylbenzylammonium chloride, N, N-dimethyl-N-phenyl-N -P-vinylbenzylammonium chloride; trimethyl-p-vinylbenzylammonium bromide, trimethyl-m-vinylbenzylammonium bromide, trimethyl-p-vinylbenzylammonium sulfonate, trimethyl-m-vinylbenzylammonium sulfonate, trimethyl-p-vinylbenzyl Ammonium acetate, trimethyl-m-vinylbenzylammonium acetate, N, N, N-triethyl-N-2- (4-vinylphenyl) ethylammonium chloride, N, N, N-trie Ru-N-2- (3-vinylphenyl) ethylammonium chloride, N, N-diethyl-N-methyl-N-2- (4-vinylphenyl) ethylammonium chloride, N, N-diethyl-N-methyl- N-2- (4-vinylphenyl) ethylammonium acetate; N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylate, N , N-diethylaminopropyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylamide, N, N-diethylaminoethyl (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide, N, N-diethylamino Propyl (meth) acrylamide methyl Examples include chloride, ethyl chloride, methyl bromide, ethyl bromide, quaternized product of methyl iodide or ethyl iodide, or sulfonate, alkyl sulfonate, acetate or alkyl carboxylate substituted with anions thereof. .
[0180]
Specifically, monomethyldiallylammonium chloride, trimethyl-2- (methacryloyloxy) ethylammonium chloride, triethyl-2- (methacryloyloxy) ethylammonium chloride, trimethyl-2- (acryloyloxy) ethylammonium chloride, triethyl-2- (Acryloyloxy) ethylammonium chloride, trimethyl-3- (methacryloyloxy) propylammonium chloride, triethyl-3- (methacryloyloxy) propylammonium chloride, trimethyl-2- (methacryloylamino) ethylammonium chloride, triethyl-2- (methacryloyl) Amino) ethylammonium chloride, trimethyl-2- (acryloylamino) ethylammoni Muchloride, triethyl-2- (acryloylamino) ethylammonium chloride, trimethyl-3- (methacryloylamino) propylammonium chloride, triethyl-3- (methacryloylamino) propylammonium chloride, trimethyl-3- (acryloylamino) propylammonium chloride, Triethyl-3- (acryloylamino) propylammonium chloride; N, N-dimethyl-N-ethyl-2- (methacryloyloxy) ethylammonium chloride, N, N-diethyl-N-methyl-2- (methacryloyloxy) ethylammonium Chloride, N, N-dimethyl-N-ethyl-3- (acryloylamino) propylammonium chloride, trimethyl-2- (methacryloylo) ) Ethyl ammonium bromide, it may be mentioned trimethyl-3- (acryloylamino) propyl ammonium bromide, trimethyl-2- (methacryloyloxy) ethyl ammonium sulfonate, trimethyl-3- (acryloylamino) propylammonium acetate.
In addition, examples of the copolymerizable monomer include N-vinylimidazole and N-vinyl-2-methylimidazole.
[0181]
In addition, allylamine, diallylamine or a derivative thereof, a salt, and the like can be used. Examples of such compounds include allylamine, allylamine hydrochloride, allylamine acetate, allylamine sulfate, diallylamine, diallylamine hydrochloride, diallylamine acetate, diallylamine sulfate, diallylmethylamine and salts thereof (for example, Hydrochloride, acetate, sulfate, etc.), diallylethylamine and salts thereof (for example, hydrochloride, acetate, sulfate, etc.), diallyldimethylammonium salt (chloride, acetic acid as counter anions of the salt) Ion sulfate ions, etc.). In addition, since these allylamines and diallylamine derivatives are inferior in polymerizability in the form of amines, they are generally polymerized in the form of salts and desalted as required.
Further, it is also possible to use a unit such as N-vinylacetamide or N-vinylformamide, which is converted into a vinylamine unit by hydrolysis after polymerization, and a salt thereof.
[0182]
The non-mordant monomer does not include a basic or cationic moiety such as a primary to tertiary amino group and a salt thereof, or a quaternary ammonium base, and does not exhibit an interaction with a dye in an inkjet ink. Alternatively, it means a monomer having a substantially small interaction.
Examples of the non-mordant monomer include (meth) acrylic acid alkyl ester; (meth) acrylic acid cycloalkyl ester such as cyclohexyl (meth) acrylate; (meth) acrylic acid aryl ester such as phenyl (meth) acrylate; Aralkyl esters such as (meth) benzyl acrylate; Aromatic vinyls such as styrene, vinyl toluene and α-methylstyrene; Vinyl esters such as vinyl acetate, vinyl propionate and vinyl versatic acid; Allyl esters such as allyl acetate Halogen-containing monomers such as vinylidene chloride and vinyl chloride; vinyl cyanide such as (meth) acrylonitrile; olefins such as ethylene and propylene; and the like.
[0183]
The (meth) acrylic acid alkyl ester is preferably a (meth) acrylic acid alkyl ester having 1 to 18 carbon atoms in the alkyl moiety, such as methyl (meth) acrylate, ethyl (meth) acrylate, (meth) Propyl acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, Examples include 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, and the like. Among these, methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate, and hydroxyethyl methacrylate are preferable.
The non-mordant monomers can be used singly or in combination of two or more.
[0184]
Examples of the polymer mordant include polydiallyldimethylammonium chloride, polymethacryloyloxyethyl-β-hydroxyethyldimethylammonium chloride, polyethyleneimine, polyallylamine and derivatives thereof, polyamide-polyamine resin, cationized starch, dicyandiamide formalin condensate, Dimethyl-2-hydroxypropylammonium salt polymer, polyamidine, polyvinylamine, dicyandiamide-formalin polycondensate, dicyanamide-cachin resin, dicyanamide-diethylenetriamine polycondensate, polyamine-type katine resin, epichlorohydrin-dimethylamine Addition polymer, dimethyldialin ammonium chloride-SO₂Copolymer, diallylamine salt-SO₂A copolymer, a (meth) acrylate-containing polymer having a quaternary ammonium base-substituted alkyl group in the ester portion, a styryl polymer having a quaternary ammonium base-substituted alkyl group, and the like can also be mentioned as preferable examples.
[0185]
Examples of the polymer mordant include, for example, JP-A Nos. 48-28325, 54-74430, 54-124726, 55-22766, 55-142339, 60-23850, 60-23835. No. 60-23852 No. 60-23853 No. 60-57836 No. 60-60643 No. 60-118834 No. 60-122940 No. 60-122941 No. 60-122942 No. JP-A-60-235134, JP-A-1-161236, U.S. Pat. No. 4,450,224, JP-A-1-161236 10-81064, 10-119423, 10-157277, 10-217601, 11-348409, JP-A-2001-138621, 2000-43401, 2000-212235, 2000-309157, 2001-96897, 2001-138627, JP-A-11-91242, 8-2087, 8-2090, 8-2091, 8-2093, 8-174992, 11-192777, JP-A-2001-301314, JP-B-5-35162, JP-A-5-35163, JP-A-5-35164, JP-A-5-88846, JP-A-7-118333, JP-A 2000-344990, Japanese Patent Nos. 2648847, 2666177, etc. It is. Among these, polyallylamine and derivatives thereof are particularly preferable.
[0186]
As the organic mordant, polyallylamine having a mass average molecular weight of 100,000 or less and derivatives thereof are particularly preferable from the viewpoint of preventing bleeding with time.
[0187]
As the polyallylamine or a derivative thereof, various known allylamine polymers and derivatives thereof can be used. Examples of such derivatives include salts of polyallylamine and acids (acids include inorganic acids such as hydrochloric acid, sulfuric acid, phosphoric acid and nitric acid, methanesulfonic acid, toluenesulfonic acid, acetic acid, propionic acid, cinnamic acid, (meth) An organic acid such as acrylic acid, or a combination thereof, a salt of only a part of allylamine), a derivative of polyallylamine by a polymer reaction, a copolymer of polyallylamine and another copolymerizable monomer Specific examples of the monomer include (meth) acrylic acid esters, styrenes, (meth) acrylamides, acrylonitrile, vinyl esters and the like.
[0188]
Specific examples of the polyallylamine and derivatives thereof include JP-B-62-31722, JP-B-2-14364, JP-B-63-43402, JP-A-63-43403, JP-A-63-45721, and JP-A-63-29881. No. 1-226362, No. 2-56365, No. 2-57084, No. 4-41686, No. 6-2780, No. 6-45649, No. 6-15592, No. 4-68622, Patent Nos. 3199227, 3008369, JP-A-10-330427, JP-A-11-21321, JP-A-2000-281728, JP-A-2001-106636, JP-A-62-256801, JP-A-7-173286, 7-213897, 9-235318, 9-302026, 11-21321, WO99 / 219 No. 1, No. WO99 / 19 372, JP-A-5-140213, compounds described in JP Kohyo No. 11-506488, and the like.
[0189]
As the mordant, an inorganic mordant can be used, and examples thereof include polyvalent water-soluble metal salts and hydrophobic metal salt compounds.
Specific examples of inorganic mordants include magnesium, aluminum, calcium, scandium, titanium, vanadium, manganese, iron, nickel, copper, zinc, gallium, germanium, strontium, yttrium, zirconium, molybdenum, indium, barium, lanthanum, cerium, Examples thereof include salts or complexes of metals selected from praseodymium, neodymium, samarium, europium, gadolinium, dysproprosium, erbium, ytterbium, hafnium, tungsten, and bismuth.
[0190]
Specifically, calcium acetate, calcium chloride, calcium formate, calcium sulfate, barium acetate, barium sulfate, barium phosphate, manganese chloride, manganese acetate, manganese formate dihydrate, manganese ammonium sulfate hexahydrate, second chloride Copper, ammonium chloride (II) chloride dihydrate, copper sulfate, cobalt chloride, cobalt thiocyanate, cobalt sulfate, nickel sulfate hexahydrate, nickel chloride hexahydrate, nickel acetate tetrahydrate, nickel ammonium sulfate Hexahydrate, nickel amidosulfate tetrahydrate, aluminum sulfate, aluminum alum, basic polyaluminum hydroxide, aluminum sulfite, aluminum thiosulfate, polyaluminum chloride, aluminum nitrate nonahydrate, aluminum chloride hexahydrate , Ferrous bromide, ferrous chloride, ferric chloride, sulfuric acid Iron, ferric sulfate, zinc phenolsulfonate, zinc bromide, zinc chloride, zinc nitrate hexahydrate, zinc sulfate, titanium tetrachloride, tetraisopropyl titanate, titanium acetylacetonate, titanium lactate, zirconium acetylacetonate, Zirconyl acetate, zirconyl sulfate, ammonium zirconium carbonate, zirconyl stearate, zirconyl octylate, zirconyl nitrate, zirconium oxychloride, zirconium hydroxychloride, chromium acetate, chromium sulfate, magnesium sulfate, magnesium chloride hexahydrate, magnesium citrate nine water Japanese, sodium phosphotungstate, sodium tungsten citrate, 12 tungstophosphoric acid n hydrate, 12 tungstosilicic acid 26 hydrate, molybdenum chloride, 12 molybdophosphoric acid n hydrate, gallium nitrate, glass Germanium acid, strontium nitrate, yttrium acetate, yttrium chloride, yttrium nitrate, indium nitrate, lanthanum nitrate, lanthanum chloride, lanthanum acetate, lanthanum benzoate, cerium chloride, cerium sulfate, cerium octylate, praseodymium nitrate, neodymium nitrate, samarium nitrate, Examples include europium nitrate, gadolinium nitrate, dysprosium nitrate, erbium nitrate, ytterbium nitrate, hafnium chloride, and bismuth nitrate.
[0191]
As the inorganic mordant, an aluminum-containing compound, a titanium-containing compound, a zirconium-containing compound, and a metal compound (salt or complex) of Group IIIB of the Periodic Table of Elements are preferable.
The amount of the mordant contained in the colorant receiving layer is 0.01 g / m.²~ 5g / m²Is preferably 0.1 g / m²~ 3g / m²Is more preferable.
[0192]
-Other ingredients-
The ink jet recording sheet may further include various known additives such as acids, ultraviolet absorbers, antioxidants, fluorescent brighteners, monomers, polymerization initiators, polymerization inhibitors, and bleeding prevention as necessary. Agents, preservatives, viscosity stabilizers, antifoaming agents, surfactants, antistatic agents, matting agents, anti-curling agents, water-proofing agents, and the like.
[0193]
<Silver photographic material>
As the silver salt photographic light-sensitive material, for example, a silver halide photographic sheet having a structure in which an image forming layer that develops color at least on YMC is provided on the support for recording material of the present invention, and subjected to printing exposure. Examples of the silver halide photographic system include color development, bleach-fixing, washing with water, and drying by passing through a plurality of processing tanks while immersing.
[0194]
<Thermal transfer image receiving material>
As the thermal transfer material, for example, a thermoautochrome having a structure in which at least a thermal coloring layer is provided on the recording material support of the present invention, and forming an image by repeated heating with a thermal head and fixing with ultraviolet rays Examples thereof include heat-sensitive color recording materials used in the system (TA system).
[0195]
<Thermosensitive color recording material>
The heat-sensitive color recording material has, for example, a structure in which at least a heat-meltable ink layer as an image forming layer is provided on the support for recording material of the present invention, and is heated and melted by a heat-sensitive head. Examples include a method of melting and transferring ink from an ink layer onto an image receiving sheet for thermal transfer recording.
[0196]
<Sublimation transfer image receiving material>
The sublimation transfer image receiving material has a structure in which an ink layer containing at least a heat diffusible dye (sublimation dye) is provided on the support for recording material of the present invention, and is heated by a thermal head to produce ink. Examples include a sublimation transfer method in which a heat diffusible dye is transferred from a layer onto a thermal transfer recording image-receiving sheet.
[0197]
【Example】
Examples of the present invention will be described below, but the present invention is not limited to these examples.
In the following examples and comparative examples, “%” and “parts” are based on mass.
[0198]
Example 1
-Preparation of support-
Hardwood bleached kraft pulp (LBKP) was beaten with a disc refiner to 300 ml (Canadian Standard Freeness, CFS) and adjusted to an average mass fiber length of 0.58 mm. Additives were added to the pulp stock at the following ratio based on the mass of the pulp.
Type of additive Amount (%)
Cationic starch 1.2
Alkyl ketene dimer (AKD) 0.4
Anionic polyacrylamide 0.2
Epoxidized fatty acid amide (EFA) 0.2
Polyamide polyamine epichlorohydrin 0.3
Note) AKD means alkyl ketene dimer (the alkyl part is derived from a fatty acid mainly composed of behenic acid), and EFA is an epoxidized fatty acid amide (the fatty acid part is derived from a fatty acid mainly composed of behenic acid). Is).
[0199]
The obtained pulp paper stock was basis weight 150 g / m by a long net paper machine.²A base paper was prepared. A solid content of 3 g / m on the surface of the base paper (the surface on which the toner image-receiving layer is applied) in the middle of the drying zone of the long paper machine using a gate roll coater.²A polyethylene soap-free emulsion was applied and dried.
At the end of the papermaking process, a calender treatment was performed so that the metal roll was in contact with the surface on the side where the toner image-receiving layer was formed, and the density was 1.01 g / cm³To obtain a support. The surface temperature of the metal roll was 140 ° C.
[0200]
(Examples 2-5 and Comparative Examples 1-3)
As shown in Table 1, the substrates of Examples 2 to 5 and Comparative Examples 1 to 3 were prepared in the same manner as in Example 1 except that the surface treatment agent used for the base paper and the temperature condition of the calendar treatment were changed. .
[0201]
About each obtained support body of Examples 1-5 and Comparative Examples 1-3, the Cobb sizing degree, the Beck smoothness, and the surface smoothness were measured with the following method. The results are shown in Table 1.
[0202]
<Cobb sizing degree>
Measured according to JIS P8140.
<Beck smoothness>
Measured according to JIS P 8119.
<Surface smoothness>
Using a surface shape measuring device Surfcom 570A-3DF (manufactured by Tokyo Seimitsu Co., Ltd.), based on the following measurement and analysis conditions, the center plane average on the side where the image forming layer of the support is provided under the conditions of 5 mm to 6 mm cutoff Roughness (SRa) was measured.
-Measurement and analysis conditions-
・ Scanning direction: MD direction of sample
・ Measurement length: 50 mm in papermaking (X) direction, 30 mm in its vertical (Y) direction
・ Measurement pitch: 0.1 mm in the X direction, 0.1 mm in the Y direction
・ Scanning speed: 30mm / sec
・ Band pass filter: 5mm ~ 6mm
Further, the change in SRa (ΔSRa) before and after the surface of each support on which the image forming layer was provided was brought into contact with water at 20 ° C. for 2 minutes was measured.
[0203]
[Table 1]

* Polyethylene soap-free emulsion (melting point = 104 ° C, manufactured by Unitika)
* Petroleum resin / wax emulsion (melting point = 65 ° C, manufactured by Japan PMC)
* Carboxy modified PVA (Kuraray)
* Oxidized starch
* Polyacrylamide (Arakawa Chemical Industries)
[0204]
(Examples 6 to 10 and Comparative Examples 3 to 4)
-Production of electrophotographic image-receiving sheet-
Using each of the obtained supports, an electrophotographic image-receiving sheet was produced as follows.
A toner image-receiving layer coating solution and a back-layer coating solution having the following composition were applied to the surface of the support in contact with the heat roll (side on which the toner image-receiving layer was provided) with a bar coater.
[0205]
-Preparation of coating solution for toner image-receiving layer-
(Titanium dioxide dispersion)
The following components were mixed and dispersed using NBK-2 manufactured by Nippon Seiki Seisakusho to prepare a titanium dioxide dispersion (titanium dioxide pigment 40% by mass).
titanium dioxide
(Taipek (registered trademark) A-220, manufactured by Ishihara Sangyo) 40.0 g
PVA102 2.0g
Ion exchange water 58.0g
[0206]
-Toner image-receiving layer coating solution-
The following components were mixed and stirred to prepare a toner image-receiving layer coating solution.
15.5 g of the above titanium dioxide dispersion
Carnauba wax dispersion
(Cerosol 524, manufactured by Chukyo Yushi) 15.0 g
Polyester resin water dispersion
(Solid content 30% by mass, KZA-7049, manufactured by Unitika) 100.0 g
Thickener (Alcox E30, Meisei Chemical) 2.0g
Anionic surfactant (AOT) 0.5g
Ion exchange water 80ml
The resulting toner image-receiving layer coating solution had a viscosity of 40 mPa · s and a surface tension of 34 mN / m.
[0207]
-Preparation of coating solution for back layer-
The following components were mixed and stirred to prepare a back layer coating solution.
Acrylic resin water dispersion
(Solid content 30% by mass, Hiloss XBH-997L, manufactured by Seiko Chemical) 100.0 g
Matting agent
(Tepomer MBX-12, manufactured by Sekisui Plastics) 5.0 g
Release agent (Hydrin D337, manufactured by Chukyo Yushi) 10.0 g
Thickener (CMC) 2.0g
Anionic surfactant (AOT) 0.5g
Ion exchange water 80ml
The viscosity of the coating solution for the back layer was 35 mPa · s, and the surface tension was 33 mN / m.
[0208]
<Coating of Back Layer and Toner Image Receiving Layer>
The back layer coating liquid is applied to the back surface of the obtained support with a bar coater, and then the toner image receiving layer coating liquid is applied to the surface of the support in the same manner as in the back layer. It was applied with a coater.
The coating amount is 9 g / m in dry mass for the back layer.²The toner image-receiving layer was coated with a toner image-receiving layer coating solution and a back layer coating solution so that the dry mass was 12 g.
The back layer and toner image-receiving layer were dried online with hot air after coating. For drying, the amount of drying air and the temperature were adjusted so that both the back surface and the toner image-receiving surface were dried within 2 minutes after coating. The drying point was the point at which the coating surface temperature was the same as the wet bulb temperature of the drying air.
After drying, a calendar process was performed. The calendering process was performed at a pressure of 147 N / cm (15 kgf / cm) using a gloss calender and keeping the metal roller at 40 ° C.
[0209]
<Evaluation>
The obtained electrophotographic image-receiving sheet was cut into A4 size to obtain a print image. The printer used was a color laser printer (DocuColor 1250-PF) manufactured by Fuji Xerox, except that the fixing belt system shown in FIG. 1 was used.
That is, in the fixing belt system 1 shown in FIG. 1, the fixing belt 2 is suspended over the heating roller 3 and the tension roller 5, and the cleaning roller 6 is interposed above the tension roller 5 via the fixing belt 2. Further, a pressure roller 4 is provided below the heating roller 3 via the fixing belt 2. The electrophotographic image-receiving sheet having the toner latent image is inserted between the heating roller 3 and the pressure roller 4 from the right side in FIG. 1, fixed, and then moved on the fixing belt 2 for cleaning. It is cleaned with a roller 6.
In this fixing belt system, the conveyance speed of the fixing belt 2 is 30 mm / second, and the nip pressure between the heating roller 3 and the pressure roller 4 is 0.2 MPa (2 kgf / cm 2).²The set temperature of the heating roller 3 is 150 ° C., which corresponds to the fixing temperature. The set temperature of the pressure roller 4 was set to 120 ° C.
[0210]
<Image quality>
About each electrophotographic image-receiving sheet, a portrait image of a woman was drawn by the image forming method described above and evaluated according to the following evaluation criteria. The results are shown in Table 2.
〔Evaluation criteria〕
A: Best
B: Good, usable (within tolerance)
C: Inferior, unusable (practically unusable)
D: Remarkably inferior, not usable
[0211]
<Glossiness>
The glossiness of the electrophotographic image-receiving sheet (electrophotographic print) after printing was visually observed and evaluated according to the following criteria. The results are shown in Table 2.
〔Evaluation criteria〕
A: Best
B: Good, usable (within tolerance)
C: Inferior, unusable (practically unusable)
D: Remarkably inferior, not usable
[0212]
[Table 2]

[0213]
From the results in Table 2, the electrophotographic image-receiving sheets of Examples 6 to 10 using the supports of Examples 1 to 5 have superior image quality and gloss as compared with Comparative Examples 4 to 6, and are clear images. It is recognized that can be obtained.
[0214]
【The invention's effect】
According to the present invention, it is possible to obtain a recording material support having superior surface smoothness and water resistance as compared with the prior art. By using the recording material support as a recording material support, a recording material capable of forming an image excellent in image quality and gloss can be provided.
[Brief description of the drawings]
FIG. 1 is a schematic configuration diagram of a fixing belt system in a printer used in an embodiment.
[Explanation of symbols]
1 Fixing belt system
2 Fixing belt
3 Heating roller
4 Pressure roller
5 Tension roller
6 Cleaning roller

Claims (10)

In a support for an electrophotographic image-receiving material containing at least a base paper,
A calendar having a metal roll having a surface temperature of 110 ° C. or more and 150 ° C. or less after applying a coating liquid containing a surface treatment agent comprising a soap-free latex or a soap-free emulsion on the surface of the base paper on which the toner image-receiving layer is provided. Calendar processing,
A support for an electrophotographic image-receiving material, wherein the degree of bump size (30 seconds) on the side of the support on which the toner image-receiving layer is provided is 10 g / m ² or less. In a support for an electrophotographic image-receiving material containing at least a base paper,
A calendar having a metal roll having a surface temperature of 110 ° C. or more and 150 ° C. or less after applying a coating liquid containing a surface treatment agent comprising a soap-free latex or a soap-free emulsion on the surface of the base paper on which the toner image-receiving layer is provided. Calendar processing,
The average surface roughness (SRa) measured under conditions of 5 mm to 6 mm cut-off on the side of the support on which the toner image receiving layer is provided is 0.7 μm or less, and the side of the support on which the toner image receiving layer is provided. A support for an electrophotographic image-receiving material, characterized in that the change in SRa (ΔSRa) before and after contact with water at 20 ° C. for 2 minutes is −0.1 μm to +0.1 μm. The coating amount of the coating solution containing the surface treatment agent is 0.5 to 3.5 g / m in solid content. ² The support for an electrophotographic image-receiving material according to any one of claims 1 to 2. Electrophotographic image-receiving material support according to any one of claims 1 to 3 before SL side Bekk smoothness to provide a toner image-receiving layer of the support is not less than 100 seconds. The base paper has a freeness of 200 to 440 ml C.I. S. F. The support for an electrophotographic image-receiving material according to any one of claims 1 to 4 , which comprises a pulp stock material. The support for an electrophotographic image receiving material according to any one of claims 1 to 5 , wherein the base paper contains a pulp stock having a mass average fiber length of 0.45 to 0.65 mm. On the side of the surface provided with at least a toner image-receiving layer of the base paper, electronic according to any of the water repellent agent, sizing agent, and from claim 1 which has been coated or impregnated with at least one selected water-proofing agent or al 6 Support for photographic image receiving material.   The support for an electrophotographic image receiving material according to claim 7, wherein the sizing agent is contained in an amount of 0.3% by mass or more per pulp mass of the base paper. A method for producing a support for an electrophotographic image-receiving material according to any one of claims 1 to 8 ,
A calendar having a metal roll having a surface temperature of 110 ° C. or more and 150 ° C. or less after applying a coating liquid containing a surface treatment agent comprising a soap-free latex or a soap-free emulsion on the surface of the base paper on which the toner image-receiving layer is provided. A method for producing a support for an electrophotographic image-receiving material, characterized by performing a calendar process . An electrophotographic image receiving material having a support for electrophotographic image receiving material containing at least a base paper and a toner image receiving layer on the support,
An electrophotographic image receiving material comprising the support for an electrophotographic image receiving material according to any one of claims 1 to 8 as the support.

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