JP4086417B2 - Recording medium for pigment ink and recording method - Google Patents

Recording medium for pigment ink and recording method Download PDF

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JP4086417B2
JP4086417B2 JP16571899A JP16571899A JP4086417B2 JP 4086417 B2 JP4086417 B2 JP 4086417B2 JP 16571899 A JP16571899 A JP 16571899A JP 16571899 A JP16571899 A JP 16571899A JP 4086417 B2 JP4086417 B2 JP 4086417B2
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weight
ink
coating solution
recording medium
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JP2000351267A (en
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卓也 中尾
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Mitsubishi Paper Mills Ltd
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Mitsubishi Paper Mills Ltd
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Description

【0001】
【発明の属する技術分野】
本発明は、顔料インク用記録媒体、特にインクジェット記録方式に適した記録媒体、およびその記録方法に関する。
【0002】
【従来の技術】
近年、電子スチールカメラまたはコンピュータの普及とともに、それらの画像を紙面等に記録するためのハードコピー技術が急速に発達した。それらのハードコピーの究極の目標は銀塩写真であり、特に色再現性、色濃度、解像度、光沢、耐候性などをいかに銀塩写真に近づけるかが開発の課題となっている。
ハードコピーの記録方式には、昇華熱転写方式、インクジェット方式、静電転写方式等がある。なかでもインクジェット方式によるプリンタは、低価格でフルカラー化が容易なことや印字媒体が豊富なことから近年急速に普及している。この方式は、ノズルから被記録材に向けてインク液滴を高速で射出するものであり、インク中に多量の溶媒を含む。このため、インクジェットプリンタ用の記録媒体は速やかにインクを吸収し、しかも優れた発色性を有することが要求される。
【0003】
また、インクジェット記録方式では、これまで染料を溶媒に溶解したタイプのインクを用いることが多かったが、顔料を水などの溶媒に分散させたタイプのインク(顔料インク)を用いるものも知られている。顔料インクを用いたインクジェット記録物は退色、変色性が小さく特に耐久性・耐候性に優れる長所があるが、顔料インクの吸収性と定着性の点で問題があった。
【0004】
【発明が解決しようとする課題】
本発明は、顔料インクの吸収性と定着性が良好で、優れた光沢性と発色性を示すとともに耐水性および耐候性の高い顔料インク用記録媒体および記録方法の提供を目的とする。
【0005】
【課題を解決するための手段】
本発明は、基材上にインク受容層を有し、その上層に、平均粒子径が10〜200nmである酸化物粒子としてポリ塩化アルミニウムで処理したシリカ粒子を含みかつpH3〜11である塗工液から形成される層が積層された顔料インク用記録媒体を提供する。
【0006】
【発明の実施の形態】
本発明で使用される基材としては、特に限定されず種々のものを使用できる。例えば、プラスチック類、具体的には、ポリエチレンテレフタレートなどのポリエステル系樹脂、ポリカーボネート系樹脂、ポリテトラフルオロエチレンなどのフッ素系樹脂など、さらに各種の紙類、布、ガラス、金属、タイル等のセラミックスなどが使用できる。これらの基材には、アルミナ水和物の多孔質層の接着強度を向上させるなどの目的で、コロナ放電処理や各種アンダーコートをも行いうる。基材の形態も限定されないが、通常は厚さが0.01〜1mmのシートまたはフィルムが使用される。
基材として透明プラスチックフィルムを使用した場合には、OHP(オーバーヘッドプロジェクタ)用シートなどにも使用できる透明な記録物が得られる。基材として、白色顔料を含んだ不透明プラスチックフィルムや、紙などを使用した場合には、銀塩写真に匹敵する記録物が得られる。
【0007】
本発明の顔料インク用記録媒体(以下、本記録媒体という)では、基材上にインク受容層を有し、その上層に、平均粒子径が10〜200nmである酸化物粒子を含みかつpH3〜11である塗工液(以下、本塗工液という)から形成される層が積層されていることが必要である。
【0008】
本記録媒体の基材上のインク受容層としては、特に制限はないがベーマイトを含む多孔質層であるとインク吸収性の点で好ましい。ここで、ベーマイトは、Al23・nH2O(n=1〜1.5)の組成式で表されるアルミナ水和物の凝集体である。
【0009】
また本塗工液に含まれる酸化物粒子としては、表面をアルミニウム塩で処理したシリカ粒子が使用される。シリカ粒子の表面処理に使用されるアルミニウム塩としては、ポリ塩化アルミニウムを用いる。ポリ塩化アルミニウムは、化学式が[Al2(OH)nCl6-n]m(1≦n≦6、1≦m≦10)で表される化合物である。例えば多木化学社製のタキバイン#1500やPAC250Aなどの商品名で市販されているものが挙げられる。なお、表面処理方法としては、例えば、シリカ粒子を含むシリカゾルに、ポリ塩化アルミニウムを添加する方法が挙げられる。
【0010】
酸化物粒子の平均粒子径は10〜200nmであることが必要である。ここで酸化物粒子の平均粒子径とは、酸化物粒子が塗工液中で凝集している場合には凝集粒子の平均粒子径をいい、また酸化物粒子が塗工液中で1次粒子で分散している場合には1次粒子の平均粒子径をいう。酸化物粒子の平均粒子径が、10nm未満になるとインク吸収性が不足し、逆に200nmを超えると記録媒体の光沢が損なわれる。より好ましくは酸化物粒子の平均粒子径が10〜100nmである。なお、酸化物粒子形状が球状であると、表面の耐擦傷性が得られることから好ましい。
【0011】
本塗工液のpHは3〜11であることが必要である。pHが11を超えると顔料の定着性が低下し、pHが3未満であると製造上の取扱性の点で問題がある。
本塗工液は、酸化物粒子100重量部に対してバインダーを5〜40重量部含むと酸化物粒子の定着性やインクの発色性の点で好ましい。バインダー量が5重量部未満では酸化物粒子の定着性が低下する。一方、バインダー量が増えるとインク定着時のドット径が大きくなり、顔料インクによる表面の被覆率が増して高い発色性が得られるが、40重量部を超えるとインクの吸収性が阻害されるため好ましくない。本塗工液のバインダー量としては、5〜25重量部がさらに好ましい。
【0012】
本塗工液の溶媒としては、水系、非水系のいずれも採用できるが、取扱性の点などから水系が好ましい。水系の場合、バインダーとしては次のような水溶性高分子物質が適宜使用される。すなわち、ポリビニルアルコール、ポリビニルピロリドン、でんぷん類、セルロース誘導体、親水性ウレタン樹脂、アクリル樹脂、アクリル酸とビニルアルコールとの共重合物などである。また非水系の場合、バインダーとしてはカルボキシル化スチレン/ブタジエン共重合体やポリアミド樹脂などが適宜使用できる。なお、本塗工液は、消泡剤、分散剤などの表面処理剤と併用してもよい。
【0013】
インク受容層上に積層される、本塗工液から形成される層(以下、塗工液形成層という)の細孔特性は、平均細孔半径が5nmに満たない場合、細孔半径1〜100nmについての全細孔容積が0.35cm3/gに満たない場合、または比表面積が50m2/gに満たない場合は、塗工量が3g/m2以上の塗工層を形成するとインク吸収性が不足するため好ましくない。より好ましい細孔特性は、比表面積に関しては100m2/g以上、細孔半径1〜200nmについての全細孔容積に関しては0.4cm3/g以上である。なお、これらの細孔特性は、窒素吸脱着法により測定する。ここでいう平均細孔半径とは、細孔半径1〜100nmについての全細孔容積をVcm3/g、比表面積をAm2/gとしたときに、2V/A×103(nm)により計算して求めた値である。
【0014】
インク受容層上に、塗工液形成層を積層する方法としては、本塗工液をインク受容層上に塗布し乾燥する方法が好ましい。塗布には、ロールコータ、エアナイフコータ、ブレードコータ、ロッドコータ、バーコータ、コンマコータ、ダイコータ、グラビアコータ等が好ましく採用できる。
本記録媒体の光沢度は、JIS Z8741において方法3として規定される60°鏡面光沢度が40%以上であることが好ましい。
【0015】
本発明において、使用される顔料としては、従来公知のものも含めて各種有機または無機顔料が使用できる。例えば、アゾ系、アントラキノン系、キナクリドン系、イソインドリノン系、ジオキサジン系、ペリノン系、インジゴ系、キノフタロン系、ジケトピロロピロール系、酸化チタン系、酸化鉄系、複合酸化物系、硫化物系、ケイ酸塩系、炭酸塩系、金属錯体系、カーボンブラック等の顔料が挙げられる。これらの顔料は、インク中での粒径が各々数百nm〜数μm程度の微粒子であることが望ましい。
【0016】
【実施例】
凝集粒子の平均粒子径190nm、pH3.5のベーマイトゾル100重量部(固形分換算)にポリビニルアルコール(クラレ社製、商品名PVA124)9重量部、ホウ酸0.02重量部を加え、さらに水を加えて固形分18重量%の塗工液を調製した。この塗工液を膜厚100μmのポリエチレンテレフタレートフィルムに乾燥時の塗工層の膜厚が30μmになるよう塗工後140℃で乾燥してインク受容層を形成し、試験用基材フィルムとした。以下、実施例(例1、例9、例10)、参考例(例2〜6)と比較例(例7、例8)を示す。
【0017】
[例1]
容量2リットルのガラス製反応器に、平均粒子径17nmの球状シリカ粒子が分散したシリカゾル(触媒化成工業社製、商品名カタロイドSI−40)198gおよびイオン交換水1402gを入れ、80℃に昇温した。80℃になったところで、撹拌しながら、ポリ塩化アルミニウム(多木化学社製、商品名タキバイン#1500)85.9gを、約10分間かけて徐々に添加した。
【0018】
添加終了後、さらに1時間、撹拌しながら80℃に保持した。ついで、この反応液を、イオン交換水を添加しながら液の量を一定に保ちつつ、濾液の電導度が50μS/cm以下に低下するまで限外濾過することにより精製し、ポリ塩化アルミニウム処理したシリカ粒子(以下、シリカ処理品という)を得た。なお、シリカ処理品の凝集粒子の平均粒子径は129nmであった。
【0019】
シリカ処理品100重量部に対しポリビニルアルコール(クラレ社製、商品名R1130)10重量部と水を加え、消泡剤(サンノプコ社製、商品名SNデフォーマ485)を塗工液全量に対して100ppm添加し、濃度5重量%、pH4の塗工液を調製した。この塗工液を試験用基材フィルムのインク受容層上にバーコータで乾燥重量が1g/m2となるよう塗工し、120℃で乾燥した。なお、塗工液形成層の細孔特性を測定したところ、比表面積163(m2/g)、平均細孔半径5.5(nm)、細孔半径1〜200nmについての全細孔容積0.45(cm3/g)であった。
【0020】
[例2]
平均粒子径33nmのアルミナ超微粒子(シーアイ化成社製、商品名ナノテック)100重量部とポリビニルアルコール(クラレ社製、商品名R1130)10重量部に水を加え、消泡剤(サンノプコ社製、商品名SNデフォーマ485)を塗工液全量に対して100ppm添加し、濃度5重量%、pH5の塗工液を調製した。この塗工液を試験用基材フィルムのインク受容層上にバーコータで乾燥重量が1g/m2となるよう塗工し、120℃で乾燥した。
【0021】
[例3]
平均粒子径12nmの球状シリカ粒子が分散したシリカゾル(触媒化成工業社製、商品名カタロイドI−30)100重量部(固形分換算)にポリビニルアルコール(クラレ社製、商品名R1130)10重量部と水を加え、さらに消泡剤(サンノプコ社製、商品名SNデフォーマ485)を塗工液全量に対して100ppm添加し、濃度5重量%、pH9の塗工液を調製した。この塗工液を試験用基材フィルムのインク受容層上にバーコータで乾燥重量が1g/m2となるよう塗工し、120℃で乾燥した。
【0022】
[例4]
平均粒子径45nmの球状シリカ粒子が分散したシリカゾル(触媒化成工業社製、商品名カタロイドSI−45)100重量部(固形分換算)とポリビニルアルコール(クラレ社製、商品名R1130)10重量部に水を加え、さらに消泡剤(サンノプコ社製、商品名SNデフォーマ485)を塗工液全量に対して100ppm添加し、濃度5重量%、pH9の塗工液を調製した。この塗工液を試験用基材フィルムのインク受容層上にバーコータで乾燥重量が1g/m2となるよう塗工し、120℃で乾燥した。
【0023】
[例5]
平均粒子径80nmの球状シリカ粒子が分散したシリカゾル(触媒化成工業社製、商品名カタロイドSI−80)100重量部(固形分換算)とポリビニルアルコール(クラレ社製、商品名R1130)10重量部に水を加え、消泡剤(サンノプコ社製、商品名SNデフォーマ485)を塗工液全量に対して100ppm添加し、濃度5重量%、pH9の塗工液を調製した。この塗工液を例1のフィルムのインク受容層上にバーコータで乾燥重量が1g/m2となるよう塗工し、120℃で乾燥した。
【0024】
[例6]
平均粒子径45nmの球状シリカ粒子が分散したシリカゾル(日産化成社製、商品名スノーテックスOL)100重量部(固形分換算)、ポリビニルアルコール(クラレ社製、商品名R1130)10重量部に水を加え、消泡剤(サンノプコ社製、商品名SNデフォーマ485)を塗工液全量に対して100ppm添加し、濃度5重量%、pH3の塗工液を調製した。この塗工液を試験用基材フィルムのインク受容層上にバーコータで乾燥重量が1g/m2となるよう塗工し、120℃で乾燥した。
【0025】
[例7]
例1の塗工液に硝酸を添加して、塗工液のpHを2に調整すること以外は、例1と同様にした。
【0026】
[例8]
例1の塗工液にNaOHを添加して、塗工液のpHを12に調整すること以外は、例1と同様にした。
【0027】
[例9]
例1で調製したシリカ処理品100重量部とポリビニルアルコール(クラレ社製、商品名R1130)20重量部に水を加え、さらに消泡剤(サンノプコ社製、商品名SNデフォーマ485)を塗工液全量に対して100ppm添加し、濃度5重量%、pH4の塗工液を調製した。この塗工液を試験用基材フィルムのインク受容層上にバーコータで乾燥重量が1g/m2となるよう塗工し、120℃で乾燥した。
【0028】
[例10]
例1で調製したシリカ処理品100重量部とポリビニルアルコール(クラレ社製、商品名R1130)35重量部に水を加え、さらに消泡剤(サンノプコ社製、商品名SNデフォーマ485)を塗工液全量に対して100ppm添加し、濃度5重量%、pH4の塗工液を調製した。この塗工液を試験用基材フィルムのインク受容層上にバーコータで乾燥重量が1g/m2となるよう塗工し、120℃で乾燥した。
例1〜例10の塗工液の調製内容を表1に示す。表1で、PVA濃度は酸化物粒子100重量部に対する値である。
【0029】
[試験方法]
本塗工液のpHは、pHメーター(東亜電波社製、商品名HM−12P)を用いて測定した。凝集粒子の平均粒子径は、粒度分析計(日機装社製、商品名マイクロトラックUPA)で測定した。また塗工液形成層の比表面積、細孔容積、平均細孔半径を窒素吸脱着装置(コールター社製、商品名オムニソープ100型)を用いて測定した。
【0030】
JIS Z8741に規定される60°鏡面光沢度は、ハンディーグロスメーターPG−1M(日本電飾社製)で測定した。印字は、インクジェットプロッタ(ローランド社製、商品名CJ70)でシアン、マゼンタ、イエロー、ブラック、レッド、グリーン、ブルーの各7色の顔料インクをべた印字した。ドット径はCMYK4色の平均値で示した。色濃度はグレタグSPM100−IIで測定し、CMYK4色の平均値で示した。色濃度の数値は、大きいほど良い。
【0031】
定着性は、印字されたフィルムを水に浸して顔料印字部を指でこすり、顔料の脱落の有無を目視で観察した。なお、定着性の試験は、印字直後のフィルムと、印字後1時間放置し、さらに140℃×2分間の熱処理したフィルムの2種類について実施した。結果は顔料の脱落が認められないものを○、色によって一部脱落が起こったものを△、全色脱落してしまったものを×とした。
【0032】
【表1】

Figure 0004086417
【0033】
【表2】
Figure 0004086417
【0034】
【発明の効果】
本記録媒体は、顔料インクの吸収性と定着性が良好で、優れた光沢性、発色性を示すとともに、耐水性および耐候性の高いインクジェットプリンタ用記録媒体として好適なものである。また印字後に熱処理することで顔料インクの定着性が向上できる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a recording medium for pigment ink, particularly a recording medium suitable for an ink jet recording system, and a recording method thereof.
[0002]
[Prior art]
In recent years, with the widespread use of electronic still cameras or computers, hard copy technology for recording these images on paper has rapidly developed. The ultimate goal of these hard copies is silver salt photography. In particular, how to bring color reproducibility, color density, resolution, gloss, weather resistance, etc. closer to silver salt photography is a development issue.
Hard copy recording methods include a sublimation heat transfer method, an ink jet method, and an electrostatic transfer method. In particular, inkjet printers have been rapidly spreading in recent years because they are inexpensive and easy to achieve full color, and because there are abundant print media. In this method, ink droplets are ejected from a nozzle toward a recording material at a high speed, and a large amount of solvent is contained in the ink. For this reason, a recording medium for an ink jet printer is required to quickly absorb ink and to have excellent color developability.
[0003]
Ink jet recording methods have often used ink of a type in which a dye is dissolved in a solvent. However, ink jet recording methods in which a pigment is dispersed in a solvent such as water (pigment ink) are also known. Yes. Inkjet recordings using pigment inks have the advantages of small fading and discoloration, and particularly excellent durability and weather resistance, but there are problems with the absorption and fixing properties of pigment inks.
[0004]
[Problems to be solved by the invention]
An object of the present invention is to provide a recording medium and a recording method for pigment ink, which have good absorbability and fixability of the pigment ink, exhibit excellent gloss and color developability, and have high water resistance and weather resistance.
[0005]
[Means for Solving the Problems]
The present invention is a coating having an ink receiving layer on a substrate, and containing silica particles treated with polyaluminum chloride as oxide particles having an average particle size of 10 to 200 nm and having a pH of 3 to 11 on the upper layer. Provided is a pigment ink recording medium in which layers formed from a liquid are laminated.
[0006]
DETAILED DESCRIPTION OF THE INVENTION
The base material used in the present invention is not particularly limited, and various materials can be used. For example, plastics, specifically polyester resins such as polyethylene terephthalate, polycarbonate resins, fluorine resins such as polytetrafluoroethylene, and various papers, cloths, glass, metals, ceramics such as tiles, etc. Can be used. These substrates can be subjected to corona discharge treatment and various undercoats for the purpose of improving the adhesive strength of the porous layer of alumina hydrate. Although the form of the substrate is not limited, a sheet or film having a thickness of 0.01 to 1 mm is usually used.
When a transparent plastic film is used as the substrate, a transparent recorded material that can be used for an OHP (overhead projector) sheet or the like can be obtained. When an opaque plastic film containing white pigment or paper is used as the substrate, a recorded matter comparable to a silver salt photograph can be obtained.
[0007]
The recording medium for pigment ink of the present invention (hereinafter referred to as the present recording medium) has an ink-receiving layer on a substrate, and includes oxide particles having an average particle diameter of 10 to 200 nm on the upper layer and a pH of 3 The layer formed from the coating liquid 11 (hereinafter referred to as the present coating liquid) is required to be laminated.
[0008]
The ink receiving layer on the substrate of the recording medium is not particularly limited, but a porous layer containing boehmite is preferable from the viewpoint of ink absorbability. Here, boehmite is an aggregate of alumina hydrate represented by a composition formula of Al 2 O 3 .nH 2 O (n = 1 to 1.5).
[0009]
Further, as the oxide particles contained in the present coating liquid, silica particles whose surface is treated with an aluminum salt are used . Shi The aluminum salt used in the surface treatment of the silica particles, using poly aluminum chloride. Polyaluminum chloride is a compound represented by the chemical formula [Al 2 (OH) n Cl 6-n ] m (1 ≦ n ≦ 6, 1 ≦ m ≦ 10). For example, what is marketed by brand names, such as Takibine # 1500 and PAC250A by Taki Chemical Co., Ltd. is mentioned. As the surface treatment method, for example, a silica sol containing silica particles, a method of adding a polychlorinated aluminum and the like.
[0010]
The average particle diameter of the oxide particles needs to be 10 to 200 nm. Here, the average particle diameter of the oxide particles refers to the average particle diameter of the aggregated particles when the oxide particles are aggregated in the coating liquid, and the primary particles in the coating liquid. Means the average particle size of primary particles. If the average particle diameter of the oxide particles is less than 10 nm, the ink absorbability is insufficient, and conversely if it exceeds 200 nm, the gloss of the recording medium is impaired. More preferably, the average particle diameter of the oxide particles is 10 to 100 nm. It is preferable that the oxide particles have a spherical shape because surface scratch resistance can be obtained.
[0011]
The pH of this coating liquid needs to be 3-11. When the pH exceeds 11, the fixability of the pigment is lowered, and when the pH is less than 3, there is a problem in terms of handling in production.
When the coating liquid contains 5 to 40 parts by weight of a binder with respect to 100 parts by weight of the oxide particles, it is preferable in terms of fixability of the oxide particles and color development of the ink. When the amount of the binder is less than 5 parts by weight, the fixability of the oxide particles is lowered. On the other hand, when the amount of the binder is increased, the dot diameter at the time of ink fixing is increased and the surface coverage with the pigment ink is increased to obtain a high color development property. However, when the amount exceeds 40 parts by weight, the ink absorbability is inhibited. It is not preferable. As a binder amount of this coating liquid, 5-25 weight part is further more preferable.
[0012]
As the solvent for this coating solution, both aqueous and non-aqueous solvents can be adopted, but an aqueous system is preferred from the viewpoint of handling. In the case of an aqueous system, the following water-soluble polymer substances are appropriately used as the binder. That is, polyvinyl alcohol, polyvinyl pyrrolidone, starches, cellulose derivatives, hydrophilic urethane resins, acrylic resins, copolymers of acrylic acid and vinyl alcohol, and the like. In the case of a non-aqueous system, a carboxylated styrene / butadiene copolymer, a polyamide resin, or the like can be appropriately used as the binder. In addition, you may use this coating liquid together with surface treatment agents, such as an antifoamer and a dispersing agent.
[0013]
When the average pore radius is less than 5 nm, the pore characteristics of a layer formed on the ink receiving layer and formed from the present coating liquid (hereinafter referred to as coating liquid forming layer) When the total pore volume for 100 nm is less than 0.35 cm 3 / g, or the specific surface area is less than 50 m 2 / g, an ink is formed by forming a coating layer with a coating amount of 3 g / m 2 or more. It is not preferable because the absorbency is insufficient. More preferable pore characteristics are 100 m 2 / g or more for the specific surface area and 0.4 cm 3 / g or more for the total pore volume for the pore radius of 1 to 200 nm. These pore characteristics are measured by a nitrogen adsorption / desorption method. Here, the average pore radius is 2 V / A × 10 3 (nm) when the total pore volume with respect to the pore radius of 1 to 100 nm is Vcm 3 / g and the specific surface area is Am 2 / g. It is a value obtained by calculation.
[0014]
As a method of laminating the coating liquid forming layer on the ink receiving layer, a method of applying the present coating liquid on the ink receiving layer and drying it is preferable. For coating, a roll coater, an air knife coater, a blade coater, a rod coater, a bar coater, a comma coater, a die coater, a gravure coater or the like can be preferably employed.
As for the glossiness of this recording medium, the 60 ° specular glossiness defined as Method 3 in JIS Z8741 is preferably 40% or more.
[0015]
In the present invention, as the pigment used, various organic or inorganic pigments including those conventionally known can be used. For example, azo, anthraquinone, quinacridone, isoindolinone, dioxazine, perinone, indigo, quinophthalone, diketopyrrolopyrrole, titanium oxide, iron oxide, complex oxide, sulfide , Silicate-based, carbonate-based, metal complex-based, and carbon black pigments. These pigments are desirably fine particles each having a particle size in the ink of about several hundred nm to several μm.
[0016]
【Example】
9 parts by weight of polyvinyl alcohol (trade name PVA124, manufactured by Kuraray Co., Ltd.) and 0.02 part by weight of boric acid are added to 100 parts by weight (in terms of solid content) of boehmite sol having an average particle diameter of 190 nm and pH 3.5. Was added to prepare a coating solution having a solid content of 18% by weight. This coating solution was applied to a polyethylene terephthalate film having a thickness of 100 μm so that the thickness of the coating layer when dried was 30 μm, and then dried at 140 ° C. to form an ink receiving layer, which was used as a test base film. . Examples (Examples 1, 9 and 10) , Reference Examples (Examples 2 to 6) and Comparative Examples (Examples 7 and 8) are shown below.
[0017]
[Example 1]
A glass reactor having a capacity of 2 liters was charged with 198 g of silica sol (catalyst chemical industry, trade name Cataloid SI-40) in which spherical silica particles having an average particle diameter of 17 nm were dispersed and 1402 g of ion-exchanged water, and the temperature was raised to 80 ° C. did. When the temperature reached 80 ° C., 85.9 g of polyaluminum chloride (manufactured by Taki Chemical Co., Ltd., trade name Takibine # 1500) was gradually added over about 10 minutes while stirring.
[0018]
After completion of the addition, the mixture was kept at 80 ° C. with stirring for another hour. Next, the reaction solution was purified by ultrafiltration until the conductivity of the filtrate decreased to 50 μS / cm or less while adding the ion-exchanged water while keeping the amount of the solution constant, and treated with polyaluminum chloride. Silica particles (hereinafter referred to as a silica-treated product) were obtained. The average particle size of the aggregated particles of the silica-treated product was 129 nm.
[0019]
10 parts by weight of polyvinyl alcohol (trade name R1130, manufactured by Kuraray Co., Ltd.) and water are added to 100 parts by weight of the silica-treated product, and an antifoaming agent (trade name SN deformer 485, manufactured by San Nopco) is added to 100 ppm of the total amount of the coating liquid. This was added to prepare a coating solution having a concentration of 5% by weight and pH 4. This coating solution was applied onto the ink receiving layer of the test substrate film with a bar coater so that the dry weight was 1 g / m 2 and dried at 120 ° C. When the pore characteristics of the coating liquid forming layer were measured, the total pore volume was 0 for a specific surface area of 163 (m 2 / g), an average pore radius of 5.5 (nm), and a pore radius of 1 to 200 nm. .45 (cm 3 / g).
[0020]
[Example 2]
Water was added to 100 parts by weight of alumina ultrafine particles having an average particle size of 33 nm (trade name Nanotech, manufactured by C-I Kasei Co., Ltd.) and 10 parts by weight of polyvinyl alcohol (trade name, R1130, manufactured by Kuraray Co., Ltd.), and an antifoaming agent (manufactured by San Nopco, product) No. SN deformer 485) was added at 100 ppm with respect to the total amount of the coating solution to prepare a coating solution having a concentration of 5% by weight and pH 5. This coating solution was applied onto the ink receiving layer of the test substrate film with a bar coater so that the dry weight was 1 g / m 2 and dried at 120 ° C.
[0021]
[Example 3]
10 parts by weight of polyvinyl alcohol (made by Kuraray Co., Ltd., trade name R1130) and 100 parts by weight (converted to solid content) of silica sol (catalyst chemical industry, trade name Cataloid I-30) in which spherical silica particles having an average particle size of 12 nm are dispersed, Water was added, and an antifoaming agent (manufactured by San Nopco, trade name SN deformer 485) was added at 100 ppm with respect to the total amount of the coating solution to prepare a coating solution having a concentration of 5% by weight and pH 9. This coating solution was applied onto the ink receiving layer of the test substrate film with a bar coater so that the dry weight was 1 g / m 2 and dried at 120 ° C.
[0022]
[Example 4]
To 100 parts by weight of silica sol (trade name Cataloid SI-45, manufactured by Catalyst Kasei Kogyo Co., Ltd.) in which spherical silica particles having an average particle size of 45 nm are dispersed (in terms of solid content) and 10 parts by weight of polyvinyl alcohol (product name: R1130, manufactured by Kuraray Co., Ltd.) Water was added, and an antifoaming agent (manufactured by San Nopco, trade name SN deformer 485) was added at 100 ppm with respect to the total amount of the coating solution to prepare a coating solution having a concentration of 5% by weight and pH 9. This coating solution was applied onto the ink receiving layer of the test substrate film with a bar coater so that the dry weight was 1 g / m 2 and dried at 120 ° C.
[0023]
[Example 5]
To 100 parts by weight (converted to solid content) of silica sol in which spherical silica particles having an average particle diameter of 80 nm are dispersed (catalyst chemical industry, trade name: Cataloid SI-80) and polyvinyl alcohol (trade name: R1130, trade name: 10 parts by weight) Water was added, and 100 ppm of an antifoaming agent (trade name SN deformer 485, manufactured by San Nopco) was added to the total amount of the coating solution to prepare a coating solution having a concentration of 5% by weight and pH 9. This coating solution was applied onto the ink receiving layer of the film of Example 1 with a bar coater so that the dry weight was 1 g / m 2 and dried at 120 ° C.
[0024]
[Example 6]
Water is added to 100 parts by weight of silica sol (trade name Snowtex OL, manufactured by Nissan Kasei Co., Ltd.) in which spherical silica particles having an average particle diameter of 45 nm are dispersed, and 10 parts by weight of polyvinyl alcohol (trade name R1130, manufactured by Kuraray Co., Ltd.). In addition, an antifoaming agent (manufactured by San Nopco, trade name SN deformer 485) was added at 100 ppm with respect to the total amount of the coating solution to prepare a coating solution having a concentration of 5% by weight and pH 3. This coating solution was applied onto the ink receiving layer of the test substrate film with a bar coater so that the dry weight was 1 g / m 2 and dried at 120 ° C.
[0025]
[Example 7]
The procedure of Example 1 was repeated except that nitric acid was added to the coating solution of Example 1 to adjust the pH of the coating solution to 2.
[0026]
[Example 8]
Example 1 was repeated except that NaOH was added to the coating solution of Example 1 to adjust the pH of the coating solution to 12.
[0027]
[Example 9]
Water is added to 100 parts by weight of the silica-treated product prepared in Example 1 and 20 parts by weight of polyvinyl alcohol (trade name R1130, manufactured by Kuraray Co., Ltd.), and an antifoaming agent (trade name SN deformer 485, manufactured by San Nopco) is further applied as a coating solution. 100 ppm was added to the total amount to prepare a coating solution having a concentration of 5% by weight and pH 4. This coating solution was applied onto the ink receiving layer of the test substrate film with a bar coater so that the dry weight was 1 g / m 2 and dried at 120 ° C.
[0028]
[Example 10]
Water is added to 100 parts by weight of the silica-treated product prepared in Example 1 and 35 parts by weight of polyvinyl alcohol (trade name R1130, manufactured by Kuraray Co., Ltd.), and an antifoaming agent (trade name SN deformer 485, manufactured by San Nopco) is further applied as a coating solution. 100 ppm was added to the total amount to prepare a coating solution having a concentration of 5% by weight and pH 4. This coating solution was applied onto the ink receiving layer of the test substrate film with a bar coater so that the dry weight was 1 g / m 2 and dried at 120 ° C.
The contents of preparation of the coating liquids of Examples 1 to 10 are shown in Table 1. In Table 1, the PVA concentration is a value relative to 100 parts by weight of the oxide particles.
[0029]
[Test method]
The pH of this coating solution was measured using a pH meter (trade name HM-12P, manufactured by Toa Denpa Inc.). The average particle diameter of the aggregated particles was measured with a particle size analyzer (trade name: Microtrac UPA, manufactured by Nikkiso Co., Ltd.). In addition, the specific surface area, pore volume, and average pore radius of the coating liquid forming layer were measured using a nitrogen adsorption / desorption device (trade name Omni Soap 100 type, manufactured by Coulter Inc.).
[0030]
The 60 ° specular glossiness defined in JIS Z8741 was measured with a handy gloss meter PG-1M (manufactured by Nippon Denshoku Co., Ltd.). Printing was carried out using an inkjet plotter (trade name: CJ70, manufactured by Roland Corporation), and printed with seven pigment inks of cyan, magenta, yellow, black, red, green, and blue. The dot diameter is shown as an average value of four colors of CMYK. The color density was measured with Gretag SPM100-II and indicated as the average value of CMYK four colors. The larger the color density value, the better.
[0031]
The fixability was determined by immersing the printed film in water and rubbing the pigment printed part with a finger and visually observing whether or not the pigment was removed. The fixability test was carried out for two types: a film immediately after printing and a film that was left for 1 hour after printing and then heat-treated at 140 ° C. for 2 minutes. As a result, the case where the pigments were not removed was marked with ◯, the case where some of the colors had fallen off was marked with Δ, and the case where all the colors were dropped off was marked with ×.
[0032]
[Table 1]
Figure 0004086417
[0033]
[Table 2]
Figure 0004086417
[0034]
【The invention's effect】
This recording medium is suitable as a recording medium for an ink jet printer having good absorbability and fixing property of pigment ink, excellent glossiness and color developability, and high water resistance and weather resistance. Further, the fixing property of the pigment ink can be improved by heat treatment after printing.

Claims (3)

基材上にインク受容層を有し、その上層に、平均粒子径が10〜200nmである酸化物粒子としてポリ塩化アルミニウムで処理したシリカ粒子を含みかつpH3〜11である塗工液から形成される層が積層された顔料インク用記録媒体。An ink-receiving layer is formed on a substrate, and the upper layer is formed from a coating solution containing silica particles treated with polyaluminum chloride as oxide particles having an average particle diameter of 10 to 200 nm and having a pH of 3 to 11. A recording medium for pigment ink in which layers are laminated. 塗工液が酸化物粒子100重量部に対してバインダーを5〜40重量部含むものである請求項に記載の顔料インク用記録媒体。The recording medium for pigment ink according to claim 1 , wherein the coating liquid contains 5 to 40 parts by weight of a binder with respect to 100 parts by weight of the oxide particles. インク受容層がベーマイトを含む多孔質層である請求項1または2に記載の顔料インク用記録媒体。The recording medium for pigment ink according to claim 1 or 2 , wherein the ink receiving layer is a porous layer containing boehmite.
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