JPS63104878A - Recording material and ink jet recording method using the same - Google Patents
Recording material and ink jet recording method using the sameInfo
- Publication number
- JPS63104878A JPS63104878A JP61250032A JP25003286A JPS63104878A JP S63104878 A JPS63104878 A JP S63104878A JP 61250032 A JP61250032 A JP 61250032A JP 25003286 A JP25003286 A JP 25003286A JP S63104878 A JPS63104878 A JP S63104878A
- Authority
- JP
- Japan
- Prior art keywords
- ink
- particles
- layer
- recording
- recording material
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
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- 238000000034 method Methods 0.000 title claims description 59
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- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 210000001685 thyroid gland Anatomy 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- VRVDFJOCCWSFLI-UHFFFAOYSA-K trisodium 3-[[4-[(6-anilino-1-hydroxy-3-sulfonatonaphthalen-2-yl)diazenyl]-5-methoxy-2-methylphenyl]diazenyl]naphthalene-1,5-disulfonate Chemical compound [Na+].[Na+].[Na+].COc1cc(N=Nc2cc(c3cccc(c3c2)S([O-])(=O)=O)S([O-])(=O)=O)c(C)cc1N=Nc1c(O)c2ccc(Nc3ccccc3)cc2cc1S([O-])(=O)=O VRVDFJOCCWSFLI-UHFFFAOYSA-K 0.000 description 1
- 238000011179 visual inspection Methods 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
- 238000004078 waterproofing Methods 0.000 description 1
- 230000037303 wrinkles Effects 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 239000011667 zinc carbonate Substances 0.000 description 1
- 235000004416 zinc carbonate Nutrition 0.000 description 1
- 229910000010 zinc carbonate Inorganic materials 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
- B41M5/52—Macromolecular coatings
- B41M5/5218—Macromolecular coatings characterised by inorganic additives, e.g. pigments, clays
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、被記録材およびそれを用いたインクジェット
記録方法に関し、更に詳しくは優れた色彩発色性、イン
クドツト形状等の諸特性を有する高画質記録画像を与え
る改良された被記録材および該被記録材を使用するイン
クジェット記録方法に関する。[Detailed Description of the Invention] [Field of Industrial Application] The present invention relates to a recording material and an inkjet recording method using the same, and more specifically, to a recording material with high image quality having various characteristics such as excellent color development and ink dot shape. The present invention relates to an improved recording material that provides a recorded image and an inkjet recording method using the recording material.
インクジェット記録方法は、種々の記録液（以下インク
と云う）吐出方式（例えば、静電吸引方式、圧電素子を
用いてインクには機械的振動または変位を与える方式、
インクを加熱して発砲させ、その圧力を利用する方式等
）により、インクの小滴を発生させ、これを飛翔させ、
それらの一部もしくは全部を、紙などの被記録材に付着
させて記録を行うものであるが、騒音の発生が少なく、
高速印字、多色印字の行える記録方法として注目されて
いる。Inkjet recording methods include various recording liquid (hereinafter referred to as ink) ejection methods (for example, electrostatic suction method, method of applying mechanical vibration or displacement to ink using a piezoelectric element,
(methods such as heating ink to cause it to explode and using the resulting pressure) to generate small droplets of ink and make them fly;
Recording is performed by attaching some or all of them to a recording material such as paper, but it generates little noise.
It is attracting attention as a recording method that allows high-speed printing and multicolor printing.
インクジェット記録用のインクとしては、安全性、印刷
適正の面から主に水系のものが使用されており、一方、
被記録材としては、従来通常の紙が一般的に使用されて
きた。このような紙に液状のインクを用いて記録を行う
場合には、−・般にインクが記録用紙上で滲んで印字が
ぼけたりしないことが必要であり、またインクが記録後
可及的速やかに乾燥して不意に紙面を汚染しないことが
望ましい。Water-based inks are mainly used for inkjet recording due to safety and printing suitability.
Conventionally, ordinary paper has been generally used as the recording material. When recording on such paper using liquid ink, it is generally necessary that the ink does not bleed onto the recording paper and cause the print to become blurred, and that the ink is used as soon as possible after recording. It is desirable to dry the paper quickly so as not to accidentally contaminate the paper surface.
そして、とりわけ二色以上の異色のインクを用いる多色
インクジェット記録方式においては、１）インクの被記
録材への吸収が速やかであった場合でも、後で付着した
インクが前に付着したインクと混合したり、インクドツ
トを乱したり、流れ出したりしないこと、
２）インク液滴が被記録材上で拡散し、インクドツトの
径が必要以上に大きくならないこと３）インクドツトの
形状が真円に近く、またその周辺が滑らかであること。Particularly in multicolor inkjet recording systems that use two or more different color inks, 1) even if the ink is quickly absorbed into the recording material, the ink that adheres later may be different from the ink that adhered earlier; 2) The ink droplets should not spread on the recording material and the diameter of the ink dot should not become larger than necessary. 3) The shape of the ink dot should be close to a perfect circle. Also, the surrounding area should be smooth.
４）インクドツトの濃度が高く、ドツト周辺がぼけない
こと、
５）被記録材の白色度が高く、インクドツトのコントラ
ストが大きいこと。4) The density of the ink dots is high and the periphery of the dots is not blurred. 5) The whiteness of the recording material is high and the contrast of the ink dots is large.
６）インクの色が、被記録材のいかんにより変化しない
こと、
７）被記録材の寸法変動（例えば、しわ、のび）が記録
前後で少いこと、
８）記録画像が、水や空気中の酸化性気体ならびに光に
対して十分な抵抗性をもつこと、９）被記録材の塗工層
や基材からの粉落ちが少いこと、
等の諸要求を満足させる必要がある。6) The color of the ink does not change depending on the recording material, 7) There is little dimensional variation (e.g. wrinkles, spread) of the recording material before and after recording, 8) The recorded image does not change in water or air. It is necessary to satisfy various requirements such as 9) sufficient resistance to oxidizing gases and light, and 9) little powder falling off from the coating layer or base material of the recording material.
これらの要求を満たすために、従来からいくつかの提案
がなされてきた。例えば、インク吸収性やインクドツト
のよ＠みを改良するために特開昭５３−４９１１３号公
報には、木材パルプ抄製シートに水溶性高分子を含浸さ
せてなるインクジェット記録用紙が開示されている。塗
工紙の例としては、特開昭５５−５８３０号公報に支持
体上にインク吸収性の塗層を設けたインクジェット記録
用シートが、特開昭５５−１１８２９号公報にはインク
１及収性の異なる２層以上の層構成を有するインクジェ
ット記録用シートがそれぞれ開示されている。特開昭５
５−１１８２９号公報に於ける技術思想は、シート上に
おけるインクドツトの広がりを小さく、しかもシート中
へインクを深く浸透させることによって、反射光、透過
光のいずれの方式によっても同様に画質の良い画像を得
ることを目的としている。Several proposals have been made to meet these demands. For example, in order to improve ink absorbency and the appearance of ink dots, Japanese Patent Application Laid-Open No. 53-49113 discloses an inkjet recording paper made of a sheet made of wood pulp impregnated with a water-soluble polymer. . Examples of coated paper include an inkjet recording sheet with an ink-absorbing coating layer on a support as disclosed in JP-A-55-5830, and an ink-jet recording sheet as disclosed in JP-A-55-11829. Inkjet recording sheets each having a layer structure of two or more layers having different properties are disclosed. Japanese Patent Application Publication No. 5
The technical idea in Publication No. 5-11829 is to minimize the spread of ink dots on the sheet and allow the ink to deeply penetrate into the sheet, thereby producing images of high quality using both reflected light and transmitted light methods. The purpose is to obtain.
更に、特開昭５６−９９６９３号公報に記載のインクジ
ェット用被記録材は、ハロゲン化第四級アンモニウム等
を含有させて耐水性を付与している。Further, the inkjet recording material described in JP-A-56-99693 contains quaternary ammonium halide and the like to impart water resistance.
また、インクジェット用被記録材として合成無定形シリ
カを含有する記録用紙が提案されており、（特開昭５５
−５１５８３号公報）、この被記録材は、インクジェッ
ト用被記録材として、記録剤の色彩発色性が優れる等の
利点を有するものであるが、粒子の形状が不均一でしか
も粒径の分布が広いためドツト形状が乱れたり、インク
吸収性を向上させようとすると塗層強度が低下し粉落ち
が発生するという不都合がある。In addition, recording paper containing synthetic amorphous silica has been proposed as a recording material for inkjet recording (Japanese Patent Laid-Open No. 55
-51583 Publication), this recording material has advantages as a recording material for inkjet, such as excellent color development, but the shape of the particles is non-uniform and the distribution of particle sizes is poor. Since the dots are wide, there are disadvantages in that the shape of the dots becomes disordered, and when trying to improve ink absorption, the strength of the coating layer decreases and powder falls off.
上記の如く、従来より被記録材のインクジェット記録適
正を向上させるべく努力がなされてきたが、高速印字、
高画質を要求される用途に対しては十分な特性を有する
ものではない。As mentioned above, efforts have been made to improve the suitability of recording materials for inkjet recording.
It does not have sufficient characteristics for applications requiring high image quality.
そこで、本発明の目的は、上記の技術分野において従来
技術が解決し得なかった諸課題を満足させることにあり
、特にインクジェット記録方式による複数のカラーイン
クを用いたカラー画像の記録における上記諸要求、特に
色彩発色性、発色濃度、インク吸収性およびドツト形状
を向上させる被記録材及びそれを用いたインクジェット
記録方法を提供することにある。SUMMARY OF THE INVENTION Therefore, an object of the present invention is to satisfy the various problems that the prior art could not solve in the above-mentioned technical field, and in particular, the above-mentioned demands in recording color images using a plurality of color inks using an inkjet recording method. Another object of the present invention is to provide a recording material that improves color development, color density, ink absorption, and dot shape, and an inkjet recording method using the same.
上記の目的は、以下の本発明によって達成される。 The above object is achieved by the present invention as follows.
即ち本発明の第１の構成は、粒子を含む２層シリカを含
有することを特徴とする被記録材である。That is, the first configuration of the present invention is a recording material characterized by containing two-layer silica containing particles.
更に本発明の第２の構成は、被記録材に対して、記録剤
として水溶性染料を含む記録液を以って記録を行うイン
クジェット記録方法にを含むことを特徴とするインクジ
ェット記録方法である。Furthermore, a second aspect of the present invention is an inkjet recording method comprising: recording on a recording material using a recording liquid containing a water-soluble dye as a recording agent. .
（作用）
次に本発明を更に詳細に説明すると、本発明の主たる特
徴は、上記の層構成を有する被記録材に対して、水溶性
染料を記録剤とするインクにより記録を行うことによっ
て、これらのインクにより形成された画像の色彩発色性
、発色濃度、インク吸収性およびドツト形状を著しく向
上させうろことを知見した点である。(Function) Next, to explain the present invention in more detail, the main feature of the present invention is that by recording on a recording material having the above-mentioned layer structure with an ink containing a water-soluble dye as a recording agent, It has been found that the color development, color density, ink absorption and dot shape of images formed with these inks are significantly improved.
本発明者は、インクジェット記録用被記録材、とりわけ
インク受容層の層構成ならびに粒子や結着剤等のインク
受容層の構成要素に関して鋭意研究の結果、画像の色彩
発色性、発色濃度、インク吸収性、塗層強度、インクド
ツト径およびインクドツト形状は相互に密接に関係して
おり、単一のインク受容層を有する被記録材ではこれら
の諸特性のすべてを同時に満足することは困難であると
の知見を得るに至った。As a result of extensive research into recording materials for inkjet recording, particularly the layer structure of the ink-receiving layer, and constituent elements of the ink-receiving layer such as particles and binders, the inventors have discovered that the color development properties of images, color development density, ink absorption, etc. The properties, coating layer strength, ink dot diameter, and ink dot shape are closely related to each other, and it is difficult to satisfy all of these properties at the same time with a recording material having a single ink-receiving layer. I came to know something.
例えば、単一のインク受容層を有する被記録材において
、インク吸収性の向上の為に結着剤を減量すると、塗層
強度が低下したり、インクドツト径が小さくなり過ぎた
り、発色濃度が低下するなどの欠点を有する。For example, in a recording material with a single ink-receiving layer, if the amount of binder is reduced to improve ink absorption, the coating layer strength may decrease, the ink dot diameter may become too small, or the color density may decrease. It has disadvantages such as:
他方、記録装置とのマツチングならびに記録画像の高画
質化という観点から考えると、被記録材に対して十分な
インク吸収性、最適なインクドツト径、優れた色彩発色
性ならびに高い発色濃度が要求されることは言うまでも
ない。On the other hand, from the perspective of matching with recording devices and improving the quality of recorded images, the recording material is required to have sufficient ink absorption, an optimal ink dot diameter, excellent color development, and high color density. Needless to say.
本発明者は、被記録材に複数のインク受容層を設け、各
層の粒子の種類ならびに粒子径その他を適切に遭択する
ことにより、例えばインク吸収性とインクドツト径を゛
はぼ独立にコントロールすることが可能となるとの知見
を得た。The present inventor provides a recording material with a plurality of ink-receiving layers, and by appropriately selecting the type and particle size of particles in each layer, for example, ink absorbency and ink dot diameter can be controlled almost independently. We obtained the knowledge that this is possible.
さらに、発色濃度について研究の結果、被記録材上に形
成された画像を画像側から入射する光によって観察する
所謂反射光方式に於いては、画像を形成する記録剤（染
料）が、インク受容層の表面近傍の極めて限られた厚み
の範囲に存在し、しかもインク受容層における光散乱が
少ない場合が最も発色濃度が高くなるとの知見を得るに
至った。Furthermore, as a result of research on color density, it has been found that in the so-called reflected light method, in which an image formed on a recording material is observed using light incident from the image side, the recording material (dye) that forms the image is It has been found that the color density is highest when the ink exists in a very limited thickness range near the surface of the layer and when there is little light scattering in the ink receiving layer.
本発明者はこのような知見に基づいて本発明の目的を達
成したものである。The present inventor achieved the object of the present invention based on such knowledge.
次に本発明を主として特徴づける被記録材について説明
すると、本発明の被記録材は、粒子を含む２層以上のイ
ンク受容層を有し、該インク受容層の少なくとも１層が
粒子として球状シリカを含有することを特徴とするシー
トであり、このような構成と後記の如き構成のインクと
によって本発明の目的が達成されたものである。Next, to explain the recording material that mainly characterizes the present invention, the recording material of the present invention has two or more ink-receiving layers containing particles, and at least one layer of the ink-receiving layer is composed of spherical silica particles as particles. The object of the present invention is achieved by such a structure and an ink having a structure as described below.
本発明の被記録材の一具体例を第１図に示す。A specific example of the recording material of the present invention is shown in FIG.
この例では基材３上に最表層１（第１層）および第２層
２からなるインク受容層が設けられており、各インク受
容層には粒子４および粒子５がそれぞれ含有されている
。そして粒子４の粒子径は粒子５のそれよりも小さい。In this example, an ink receiving layer consisting of an outermost layer 1 (first layer) and a second layer 2 is provided on a substrate 3, and each ink receiving layer contains particles 4 and particles 5, respectively. The particle diameter of particle 4 is smaller than that of particle 5.
例えば、本発明の被記録材の一態様である第１図の如き
被記録材において各インク受容層の働きを説明すると以
下のようになる。For example, in the recording material shown in FIG. 1, which is one embodiment of the recording material of the present invention, the function of each ink receiving layer will be explained as follows.
種々の吐出方式によって発生したインク滴は被記録材の
インク受容層の表面に接触し、吸収される。この例では
、最表層の粒子径が第２層の粒子径よりも小さいので、
最表層の粒子間の空隙は第２層のそれよりも小さく、９
インク吸収速度は最表層の方が若干遅くなる。したがっ
て、第２層のみを設けた被記録材に比して、インクの横
方向への広がりが大きくなるので、インクドツトも大き
くなる。Ink droplets generated by various ejection methods come into contact with the surface of the ink receiving layer of the recording material and are absorbed. In this example, the particle size of the outermost layer is smaller than the particle size of the second layer, so
The voids between particles in the outermost layer are smaller than those in the second layer, 9
The ink absorption speed is slightly slower on the outermost layer. Therefore, compared to a recording material provided with only the second layer, the spread of the ink in the lateral direction becomes larger, and the ink dots also become larger.
このようにして、最表層の粒子の径を選択することによ
ってインクドツト径を最適な大きさにすることが可能と
なる。また、インク受容層表面の平滑性が向上するので
表面の塗層強度（耐引っかき性）が改善される。In this way, by selecting the diameter of the particles in the outermost layer, it is possible to make the ink dot diameter optimal. Furthermore, since the smoothness of the surface of the ink-receiving layer is improved, the strength of the coating layer (scratch resistance) on the surface is improved.
粒子内部の平均細孔径が３０〜４００人の範囲にある合
成球状シリカを使用した場合には、二次粒子表面におけ
る光の幾何散乱ならびに粒子内部における光散乱が小さ
く、しかも二次粒子の表面付近において染料分子の毛管
凝縮が起こり染料分子が最表層に多く存在するようにな
るので、発色濃度が向上するほか、二次粒子間の空隙の
形状および大きさの均一性が高いために、他の無定形の
粒子の場合に比して、ドツト形状が改善される。When synthetic spherical silica with an average pore diameter within the particle range of 30 to 400 pores is used, the geometric scattering of light on the surface of the secondary particles and the light scattering inside the particles are small, and moreover, the pore size near the surface of the secondary particles is small. In addition, capillary condensation of dye molecules occurs and many dye molecules are present in the outermost layer, which improves the color density. The dot shape is improved compared to the case of amorphous particles.
最表層を通過したインクは第２層のインク受容層に吸収
されるが、この第２層は粒子径が大きいために、インク
の吸収に適した空隙を形成するので、インクを高速かつ
多量に吸収することができる。第２層の粒子としては多
孔質粒子が好ましいが、球状であるためにインク受容層
の空隙率が大きくなる合成球状シリカが特に好ましい。The ink that has passed through the outermost layer is absorbed by the second ink-receiving layer, but because the particle size of this second layer is large, it forms voids suitable for absorbing ink, so ink can be applied quickly and in large quantities. Can be absorbed. Porous particles are preferable as the particles of the second layer, and synthetic spherical silica is particularly preferable because of its spherical shape, which increases the porosity of the ink-receiving layer.
上記の例では、最表層の粒子の粒径は、最表層に隣接し
て内側に存在する第２層の粒子よりも小さいものであっ
たが、要求される特性その他によっては最表層の粒子の
粒径が第２層の粒子のそれよりも大きくなることもある
。また場合によっては、さらに第３層、第４層のインク
受容層を設けることもできる。本発明で使用する粒子は
、その平均径が０．５μｍ〜４０μｍの範囲にあるもの
が好ましいが、各層において粒子の平均径の差が少なく
とも１μｍ、好ましくは２μｍ以上必要である。In the above example, the particle size of the particles in the outermost layer was smaller than the particles in the second layer adjacent to the outermost layer, but depending on the required characteristics and other factors, the particle size of the particles in the outermost layer The particle size may be larger than that of the particles of the second layer. Further, depending on the case, third and fourth ink receiving layers may be further provided. The particles used in the present invention preferably have an average diameter in the range of 0.5 μm to 40 μm, but the difference in the average diameter of the particles in each layer must be at least 1 μm, preferably 2 μm or more.
本発明の被記録材は、従来公知の普通紙。The recording material of the present invention is conventionally known plain paper.
加工紙９合成紙、プラスチックフィルム等を基材とし、
該基材上に上記のインク受容層を設けることによって得
られる。基材が粒子を含む場合には、基材がインク受容
層を兼ねることもできる。Processed paper 9 Synthetic paper, plastic film, etc. are used as base materials,
It can be obtained by providing the above ink-receiving layer on the base material. When the base material contains particles, the base material can also serve as an ink-receiving layer.
本発明で使用する粒子としては、後記の球状シリカの他
に、例えば、タルク、クレー、カオリン、ケイソウ上。In addition to the spherical silica described below, examples of the particles used in the present invention include talc, clay, kaolin, and diatom.
炭酸カルシウム、硫酸カルシウム、硫酸バリウム、酸化
チタン、酸化亜鉛、炭酸亜鉛、ケイ酸アルミニウム、ケ
イ酸カルシウム。Calcium carbonate, calcium sulfate, barium sulfate, titanium oxide, zinc oxide, zinc carbonate, aluminum silicate, calcium silicate.
ケイ酸マグネシウム、水酸化アルミニウム、ａ化アルミ
ニウム、合成無定形シリカ、コロイダルシリカ等の無機
顔料類、及び熱可塑性樹脂、熱硬化性樹脂等の有機顔料
、例えば、ポリエチレン。Inorganic pigments such as magnesium silicate, aluminum hydroxide, aluminum a-oxide, synthetic amorphous silica, colloidal silica, and organic pigments such as thermoplastic resins and thermosetting resins, such as polyethylene.
ポリメタクリレート、エラストマー、エチレン−′酢酸
ビニル重合体、スチレンーアクリル共重合体、ポリエス
テル、ポリアクリル、ポリビニルエーテル等の樹脂粉体
及び広義のエマルジョンのうち少なくとも１種が所望に
より使用される。At least one of resin powders such as polymethacrylate, elastomer, ethylene-vinyl acetate polymer, styrene-acrylic copolymer, polyester, polyacrylic, polyvinyl ether, and a broad emulsion may be used as desired.
本発明で使用する球状シリカとしては、内部表面積を持
つ合成球状シリカが使用しつる。As the spherical silica used in the present invention, synthetic spherical silica having an internal surface area is used.
本発明で云う球状とは同一の二次粒子における最短径の
最長径に対する比が０．６以上であり、特に好ましくは
０．８以上であることを意味する。In the present invention, spherical means that the ratio of the shortest diameter to the longest diameter of the same secondary particle is 0.6 or more, particularly preferably 0.8 or more.
本発明で使用する球状シリカは、例えば下記の如くシリ
カゲルおよびポーラスシリカ（多孔質シリカ）を球状に
成形させることにより製造される。The spherical silica used in the present invention is produced, for example, by molding silica gel and porous silica into a spherical shape as described below.
シリカゲルは反応性に富むオルトケイ酸５ｔ（ＯＨ）４
が３次元的に重合したもので、構造的には二酸化ケイ素
のポリマーＳ ｉ ０２ ・ｎＨ２Ｏと考えられる。Silica gel is highly reactive orthosilicic acid 5t (OH)4
It is three-dimensionally polymerized, and structurally it is considered to be a silicon dioxide polymer S i 02 .nH2O.
オルトケイ酸の製造法としては四塩化ケイ素あるいはケ
イ酸ナトリウムを用いる方法がある。As a method for producing orthosilicic acid, there is a method using silicon tetrachloride or sodium silicate.
また、シリカゲルは水ガラス（Ｎａ２Ｓｉ０３とＮａ２
Ｓ ｉ２０５が主成分）のアルカリを中和し、ゲル化
させた後に脱水することによっても製造される。In addition, silica gel is water glass (Na2Si03 and Na2
It is also produced by neutralizing the alkali of Si205 (main component), gelling it, and then dehydrating it.
いずれの方法にせよ、重合反応時のオルトケイ酸の濃度
１反応液のｐＨ，溶媒組成、攪拌速度などを変えること
によりシリカゲルの粒子径と細孔径を調節することがで
きる。球状、のシリカゲルは重合反応液を油層に分解さ
せてゲル化させるか、乾燥した空気中にスプレーしてゲ
ル化させる等の方法によって製造することができる。In either method, the particle size and pore size of the silica gel can be adjusted by changing the pH, solvent composition, stirring speed, etc. of the reaction solution with a concentration of orthosilicic acid during the polymerization reaction. Spherical silica gel can be produced by decomposing a polymerization reaction solution into an oil layer and gelling it, or by spraying it into dry air and gelling it.
上記の操作では通常のゲルしか得られないが、ケイ酸ナ
トリウムン容ン夜中にデキストラン、長鎖脂肪酸、可溶
性デンプン、ＭｇＯなどの多孔質形成剤を加えてゲル化
を行い、次にそれらを溶媒抽出や加水分解により除去す
ることによりポーラスシリカを製造することができる。The above procedure can only yield a normal gel, but gelation is performed by adding porosity-forming agents such as dextran, long-chain fatty acids, soluble starch, and MgO to the sodium silicate container overnight, and then adding them to a solvent. Porous silica can be produced by removing it by extraction or hydrolysis.
もう一つのポーラスシリカの製造法としては、粒度分布
の狭いシリカゾルをゲル化する方法がある。Another method for producing porous silica is to gel a silica sol with a narrow particle size distribution.
以上のような方法で種々の孔径をもつポーラスシリカが
製造可能である。Porous silica having various pore sizes can be produced by the method described above.
なお、本発明では、インクジェット記録画像の保存性改
良等の為に、上記製法のいずれかの工程において、Ａｎ
、Ｍｇ、Ｚｎ、Ｃａ等の金属を例えば、複合ケイ酸塩等
の形で包含させたり、各種無機物や有機物ならびに有機
金属化合物による表面処理を施した球状シリカを使用す
ることもできる。In the present invention, in order to improve the storage stability of inkjet recorded images, An
It is also possible to use spherical silica containing metals such as , Mg, Zn, and Ca in the form of a composite silicate, or surface-treated with various inorganic substances, organic substances, and organometallic compounds.
上記の製法により製造される球状シリカは、粉砕、分級
という過程を経て製造される合成無定形シリカに比して
、粒子の形状が滑らかであり、しかも粒子径の均一性が
高い。したがって球状シリカをインクジェット記録用紙
に適用した場合には、インク付着部における光の散乱の
減少、ならびに毛管径の均一性の向上により記録画像の
発色濃度ならびにドツト形状が改善されるという利点が
ある。Spherical silica produced by the above production method has smoother particle shapes and higher uniformity in particle size than synthetic amorphous silica produced through the process of pulverization and classification. Therefore, when spherical silica is applied to inkjet recording paper, there are advantages in that the color density and dot shape of recorded images are improved by reducing the scattering of light at the ink adhesion area and improving the uniformity of the capillary diameter. .
本発明で使用される球状シリカは、二次粒子の平均径が
０．５μｍ〜３５μｍの範囲にあるものが好ましく、特
に好ましくは２μｍ〜３０μｍ１最適には２μｍ〜１５
μｍの範囲にあるものである。平均径が前記範囲よりも
大きい場合、解像度の低下、インクドツト形状の悪化に
よりザラツキ感の大計な画像となる。The spherical silica used in the present invention preferably has an average diameter of secondary particles in the range of 0.5 μm to 35 μm, particularly preferably 2 μm to 30 μm, and most preferably 2 μm to 15 μm.
It is in the μm range. If the average diameter is larger than the above range, the resolution will drop and the shape of the ink dots will deteriorate, resulting in a rough image with a grainy feel.
インクドツト形状については粒子径が小さい方が好まし
いが、粒子径が０．５μｍよりも小さい場合、とりわけ
０．２〜０．４μｍでは散乱係数が大きくなり、発色濃
度の低下をきたすので好ましくない。Regarding the shape of the ink dots, it is preferable that the particle size is small, but if the particle size is smaller than 0.5 .mu.m, especially 0.2 to 0.4 .mu.m, the scattering coefficient becomes large and the coloring density decreases, which is not preferable.
一方、球状シリカ内部の平均細孔径（細孔ニー次粒子間
の空隙）についても最適な範囲があり、本発明において
は平均細孔径が３０人〜４００人の範囲にある球状シリ
カが好ましい。On the other hand, there is also an optimum range for the average pore diameter (voids between pore secondary particles) inside the spherical silica, and in the present invention, spherical silica having an average pore diameter in the range of 30 to 400 pores is preferred.
細孔径が大きい程、球状シリカの二次粒子内部の細孔容
積が大籾くなるのでインク吸収容量が大となるが、細孔
径が４００人よりも大きい場合には二次粒子の表層付近
における染料分子の毛管凝縮が起こりにくくなるために
発色濃度が低下する。The larger the pore size, the larger the pore volume inside the secondary particles of spherical silica, which increases the ink absorption capacity. However, if the pore size is larger than 400, Color density is reduced because capillary condensation of dye molecules becomes less likely to occur.
細孔径が３０人よりも小さい場合にはインク吸収容量が
小さいのでやはり好ましくない。If the pore diameter is smaller than 30 pores, the ink absorption capacity is small, which is also not preferable.
本発明の被記録材のインク受容層は、上記粒子と結着剤
と主成分とする塗工液を基材上に塗布し、乾燥させるこ
とによって製造される。The ink-receiving layer of the recording material of the present invention is produced by applying a coating liquid containing the above-mentioned particles and a binder as main components onto a substrate and drying the coating liquid.
使用する結着剤は、粒子同志及び／又は粒子と基材ある
いはインク受容層とを結着する機能を有するものであれ
ば従来公知の材料がいずれも使用でき、例えば、ポリビ
ニルアルコール。As the binder used, any conventionally known material can be used as long as it has the function of binding particles to each other and/or particles to a substrate or an ink receiving layer, such as polyvinyl alcohol.
アクリル樹脂、スチレン−アクリル共重合体。Acrylic resin, styrene-acrylic copolymer.
エチレン−酢酸ビニル共重合体、デンプン。Ethylene-vinyl acetate copolymer, starch.
ポリビニルブチラール、ゼラチン、カゼイン。Polyvinyl butyral, gelatin, casein.
アイオノマー、アラビアゴム、カルボキシメチルセルロ
ース、ポリビニルピロリドン、ポリアクリルアミド、フ
ェノール、メラニン、エポキシ。Ionomer, gum arabic, carboxymethylcellulose, polyvinylpyrrolidone, polyacrylamide, phenol, melanin, epoxy.
スチレン−ブタジェンゴム等の樹脂のうち１ ｆｆｆｉ
以上が所望により使用で診る。とりわけ、結着剤として
珪素含有変性ポリビニルアルコールを使用した場合、イ
ンク吸収性と塗層強度の両立が可能となるので、特に好
ましい。結着剤は粒子１００部に対して３部〜１５０部
、好ましくは１０部〜１００部が使用されるが粒子の結
着に十分な量で、且つ、インク受容層の空隙を小さくし
すぎなければその比率は特に限定されるものではない。1 fffi of resins such as styrene-butadiene rubber
The above may be used as desired. In particular, it is particularly preferable to use silicon-containing modified polyvinyl alcohol as the binder, since it is possible to achieve both ink absorbency and coating strength. The binder is used in an amount of 3 parts to 150 parts, preferably 10 parts to 100 parts, based on 100 parts of the particles, but the amount must be sufficient to bind the particles, and the voids in the ink receiving layer must not be too small. The ratio of bastard is not particularly limited.
塗工液の他の成分としては、分散剤、蛍光染料、ＰＨ調
整剤、消泡剤、潤滑剤、防腐剤。Other components of the coating liquid include a dispersant, fluorescent dye, PH adjuster, antifoaming agent, lubricant, and preservative.
界面活性剤、耐水化剤の各種添加剤を挙げることができ
る。Various additives such as surfactants and waterproofing agents can be mentioned.
これらの添加剤のうち耐水化剤については、水に溶解し
た時、解離してカチオン性を呈する従来公知の千ツマ−
、オリゴマーあるいはポリマーはいずれも使用で籾るが
、好ましくは４級アンモニウム基を有するポリジアリル
アミン話導体である。Among these additives, the water resistance agent is a conventionally known additive that dissociates and exhibits cationic properties when dissolved in water.
, oligomers or polymers may be used, but polydiallylamine conductors having quaternary ammonium groups are preferred.
塗工液の固形分は約１〜５０重量％になる量が好適であ
り、該塗工液は、公知の手法、例えばロールコータ−法
、フレートコ−’；ｔ−法、ｘアナイフコーター法等に
より、通常１〜５０ｇ／ ｍ ２程度（乾燥塗工量）の
量を基材上に塗工する。好ましくは２〜３５ ｇ ／
ｍ ２程度（乾燥塗工量）塗工する。The solid content of the coating liquid is preferably about 1 to 50% by weight, and the coating liquid can be coated by a known method such as a roll coater method, a plate coater method, a t-method, or a knife coater method. The amount of coating is usually about 1 to 50 g/m 2 (dry coating amount) on the substrate. Preferably 2-35 g/
Apply approximately 2 m (dry coating amount).
本発明の被記録材の各インク受容層の厚さは、インク吸
収性、インクドツト径、発色濃度等の被記録材に要求さ
れる諸特性に対して決められるべきものであるが、最表
層では３〜３０Ａｔｍ。The thickness of each ink-receiving layer of the recording material of the present invention should be determined based on the various properties required of the recording material, such as ink absorption, ink dot diameter, and color density. 3-30 Atm.
第２層以下のインク受容層では５〜１００μｍの範囲の
厚さとするのが好ましい。The thickness of the second and subsequent ink-receiving layers is preferably in the range of 5 to 100 μm.
基材上にインク受容層を設けただけの被記録材は、その
ままでも本発明における被記録材として使用できるが、
例えば、スーパーカレンダーなどで表面に平滑性を与え
ることも可能である。A recording material in which an ink receiving layer is simply provided on a base material can be used as it is as a recording material in the present invention, but
For example, it is possible to impart smoothness to the surface using a supercalender.
次に、本発明の記録方法において使用するインクは水溶
性染料および液媒体、その他の添加剤からなる記録液で
あり、２５℃における表面張力が、好ましくは３０〜７
０ｄｙｎｅ／ ｃ ｍ 、より好ましくは４０〜６５
ｄ ｙ ｎ ｅ／ｃｍ、６通には４０〜６０ ｄ ’ｆ
ｎ ｅ ／ Ｃｍの範囲内にあるものである。この範
囲よりも低い表面張力のインクを使用して印字を行った
場合には、被記録材に対する濡れ性は良いが、印字ドツ
トの広がりが大きくなる。一方、上記表面張力により高
い表面張力のインクを使用した場合には、被記録材に対
する濡れ性が悪くなり、その結果インクの吸収性及びド
ツト濃度の低下が起こり好ましくない。Next, the ink used in the recording method of the present invention is a recording liquid consisting of a water-soluble dye, a liquid medium, and other additives, and has a surface tension of preferably 30 to 7 at 25°C.
0dyne/cm, more preferably 40-65
d y n e/cm, 40-60 d 'f for 6 letters
It is within the range of ne/Cm. When printing is performed using an ink with a surface tension lower than this range, the wettability to the recording material is good, but the spread of the printed dots becomes large. On the other hand, if an ink with a higher surface tension is used, the wettability of the ink to the recording material will deteriorate, resulting in a decrease in ink absorbency and dot density, which is undesirable.
本発明の記録方法に使用されるインクの必須成分である
水溶性染料としては、直接染料、酸性染料あるいは、食
品用色素等の水溶性染料が好ましく用いられる。As the water-soluble dye which is an essential component of the ink used in the recording method of the present invention, water-soluble dyes such as direct dyes, acid dyes, and food colorants are preferably used.
例えば、直接染料としては、ｃ、ｒ、ダイレクトブラッ
ク２，４，９，１１，１４．１７゜１９．２２，２７，
３２，３６，３８，４１゜４Ｂ、４９，５１．５６，６
２，７１，７４゜７５．７７．７８，８０，１０５，１
０６゜１０７．１０８，１１２，１１３，１１７゜１３
２．１４６，１５４，１９４；
Ｃ，１，ダイレクトイエロー１．２．４．８゜１１．１
２，２４．２６，２７，２８，３３゜３４．３９，４１
，４２，４４，４８，５０゜５１．５８，７２，８５，
８６，８７，８８゜９８．１００，１１０゜
Ｃ，！、ダイレクトオレンジ６．８，１０゜２６．２９
，３９，４１，４９，５１，１０２；Ｃ，１，ダイレク
トレッド１，２，４，８．９゜１１．１３，１７，２０
．２３，２４，２８゜３１、 ３３． ３７． ３９．
４４． ４６． ４７゜４８． ５１．−５９． ６
２． ６３． ７３． ７５゜７７、 ８０． ８１．
８３． ８４． ８５． ９０゜９４、 ９９． １
０１． １０８． １１０． １４５゜１８９、 １９
７． ２２０． ２２４． ２２５゜２２６、 ２２７
． ２３０；
Ｃ，！、ダイレクトバイオレット１，７，９゜１２．３
５，４８，５１．９０，９４゜Ｃ，！、ダイレクトブル
ー１．２．６．８゜１５．２２．２５，３４，６９，７
０，７１゜７２．７５，７６．７８，８０．８１，８２
゜８３．８６，９０，９８，１０６，１０８゜１１ ．
１２０，１２３，１５８，１６３゜１６５．１９２，１
９３，１９４，１９５゜１９６．１９９，２００，２０
１，２０２゜２０３．２０７，２１８．２３６，２３７
゜２３９．２４６，２５８゜
Ｃ，！、ダイレクトグリーン１，６，８，２８゜３３．
３７，６３，６４゜
Ｃ，！、ダイレクトブラウンＩＡ、２，６゜２５、 ２
７． ４４． ５Ｂ、 ９５． １００． １０１、
１０６． １１２． １７３． １９４． １９５゜
２０９、 ２１０． ２１１ 。For example, direct dyes include c, r, direct black 2, 4, 9, 11, 14.17° 19.22, 27,
32, 36, 38, 41° 4B, 49, 51. 56, 6
2,71,74°75.77.78,80,105,1
06゜107.108,112,113,117゜13
2.146,154,194; C, 1, Direct Yellow 1.2.4.8°11.1
2,24.26,27,28,33゜34.39,41
,42,44,48,50°51.58,72,85,
86,87,88°98.100,110°C,! , Direct Orange 6.8, 10°26.29
, 39, 41, 49, 51, 102; C, 1, Direct Red 1, 2, 4, 8.9° 11.13, 17, 20
．． 23, 24, 28°31, 33. 37. 39.
44. 46. 47°48. 51. -59. 6
2. 63. 73. 75°77, 80. 81.
83. 84. 85. 90°94, 99. 1
01. 108. 110. 145°189, 19
7. 220. 224. 225°226, 227
．． 230; C,! , Direct Violet 1,7,9°12.3
5,48,51.90,94°C,! , Direct Blue 1.2.6.8゜15.22.25,34,69,7
0,71°72.75,76.78,80.81,82
゜83.86,90,98,106,108゜11.
120,123,158,163゜165.192,1
93,194,195°196.199,200,20
1,202°203.207,218.236,237
゜239.246,258゜C,! , Direct Green 1, 6, 8, 28° 33.
37,63,64°C,! , Direct Brown IA, 2,6°25, 2
7. 44. 5B, 95. 100. 101,
106. 112. 173. 194. 195°209, 210. 211.
酸性染料としては、Ｃ，１，アシッドブラック１．２，
７，１６，１７，２４，２６，２８゜３１．４１，４８
，５２，５８，６０，６３゜９４．１０７，１０９，１
１２，１１８，１１９．１２１，１２２，１３１，１５
５．ｔｓａ；Ｃ，１，アシッドイエロー１．３，４，７
゜１１．１２，１３，１４．１？、１８，１９゜２３．
２５，２９，３４，３６，３８，４０゜４１．４２，４
４，４９，５３．５５，５９゜６１．７１，７２，７６
．７Ｂ、９９，１１１゜１１４．１１６，１２２，１３
５，１６１゜１７２：
Ｃ，！、アシッノドレンジ７．８，１０，３３゜５６．
６４；
Ｃ，！、アシッドレッド１，４，６，８，１３゜１４．
１５，１８，１９．２１．２６．２７゜３０、 ３２．
３４． ３５． ３７． ４０． ４２゜５１、 ５
２． ５４． ５７． ８０． ８２． ８３゜８５、
８７． ８８． ８９． ９２． ９４． ９７゜１
０６、 １０８． １１０． １１９． １２９゜１３
１、 １３３． １３４． １３５． １５４゜１５５
、 １７２． １７６、 １８０． １８４゜１８６、
１８７． ２４３． ２４９． ２５４゜２５６、
２６０． ２８９． ３１７． ３１８゜Ｃ，１，アシ
ッドバイオレット７．１１，１５゜３４．４１．４３，
４９，７５゜
Ｃ，！、アシッドブルー１．７，９，２２゜２３．２５
，２７，２９，４０，４１，４３゜４５．４９，５１，
５３，５５，５６，５９゜６２．７８，８０，８１，９
０，９２，９３゜１０２．１０４，１１１，１１３，１
１７゜１２０．１２４，１２６，１４５，１６７゜１７
１．１７５，１８３，２２９，２３４゜２３６；
ン
Ｃ，１，アシッドグリ−’ｌｔ３，９，１２，１６゜１
９、 ２０． ２５． ２７． ４１ 。As acidic dyes, C,1, acid black 1.2,
7,16,17,24,26,28゜31.41,48
,52,58,60,63゜94.107,109,1
12,118,119.121,122,131,15
5. tsa; C, 1, acid yellow 1.3, 4, 7
゜11.12,13,14.1? , 18, 19° 23.
25, 29, 34, 36, 38, 40° 41.42, 4
4,49,53.55,59゜61.71,72,76
．． 7B, 99,111°114.116,122,13
5,161°172: C,! , Ashi no Drange 7.8, 10, 33° 56.
64; C,! , Acid Red 1, 4, 6, 8, 13° 14.
15, 18, 19. 21. 26. 27° 30, 32.
34. 35. 37. 40. 42°51, 5
2. 54. 57. 80. 82. 83°85,
87. 88. 89. 92. 94. 97°1
06, 108. 110. 119. 129°13
1, 133. 134. 135. 154°155
, 172. 176, 180. 184°186,
187. 243. 249. 254°256,
260. 289. 317. 318°C, 1, acid violet 7.11, 15° 34.41.43,
49,75°C,! , acid blue 1.7, 9, 22° 23.25
,27,29,40,41,43°45.49,51,
53,55,56,59゜62.78,80,81,9
0,92,93°102.104,111,113,1
17゜120.124,126,145,167゜17
1.175,183,229,234゜236; N C, 1, Acid Green'lt3, 9, 12, 16゜1
9, 20. 25. 27. 41.
Ｃ０！、アシッドブラウン４，１４゜
更に食品用色素としては、
Ｃ，１，フードブラック２；
Ｃ，１，フードイエロー３，４．５゜
Ｃ，１，フードレッド２，３，７，９，１４゜５２．８
７，９２，９４，１０２，１０４゜１０５．１０６゜
Ｃ，１，フードバイオレット２；
Ｃ６■、フードブルー１．２；
Ｃ，１，フードグリーン２．３等が挙げられるが、もち
ろんこれらに限定されるものではない。C0! , Acid Brown 4,14°Further food colorings include C,1, Food Black 2; C,1, Food Yellow 3,4.5°C,1, Food Red 2,3,7,9,14° 52.8
7,92,94,102,104゜105.106゜C,1, Food Violet 2; C6■, Food Blue 1.2; C,1, Food Green 2.3, etc., but of course it is limited to these. It is not something that will be done.
これらの水溶性染料は、一般に水または水と有ｍ溶剤か
らなる溶媒体中に溶解して使用するものであり、これら
の溶媒体成分としては、好ましくは水と水溶性の各種有
機溶剤等との混合物が使用されるが、インク中の水分含
有量が、２゜乃至９０重景％の範囲内となるよう調整す
るのが好ましい。These water-soluble dyes are generally used by dissolving them in a solvent body consisting of water or water and an organic solvent, and these solvent components preferably include water and various water-soluble organic solvents. Although a mixture of the following is used, it is preferable to adjust the water content in the ink to be within the range of 2° to 90% by weight.
上記水溶性の有機溶剤としては、例えはメチルアルコー
ル、エチルアルコール、ｎ−プロビルアルコール、イソ
プロピルアルコール、ｎ−ブチルアルコール、５ｅｃ−
ブチルアルコール。Examples of the water-soluble organic solvent include methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, 5ec-
butyl alcohol.
ｔｅｒｔ−ブチルアルコール、イソブチルアルコール等
の炭素原子数が１〜４のアルキルアルコール類；ジメヂ
ルホルムアミド、ジメチルアセトアミド等のアミド類；
アセトン、ジアセトンアルコール等のケトンまたはケト
ンアルコール類；テトラヒドロフラン、ジオキサン等の
エーテル類；ポリエチレングリコール、ポリプロピレン
グリコール等のポリアルキレンゲリコール類；エチレン
グリコール、プロピレングリコール、１，２゜６−ヘキ
サンドリオール、チオグリコール、ヘキシレングリコー
ル、ジエチレングリコール等のアルキレン基が２〜６個
の炭素原子を含むアルキレングリコール類；グリセリン
：エチレングリコールメチルエーテル、ジエチレングリ
コールメチル（またはエチル）エーテル、トリエチレン
グリコールモノメチル（またはエチル）エーテル等の多
価アルコールの低級アルキルエーテル類等が挙げられる
。Alkyl alcohols having 1 to 4 carbon atoms such as tert-butyl alcohol and isobutyl alcohol; Amides such as dimethylformamide and dimethylacetamide;
Ketones or ketone alcohols such as acetone and diacetone alcohol; ethers such as tetrahydrofuran and dioxane; polyalkylene glycols such as polyethylene glycol and polypropylene glycol; ethylene glycol, propylene glycol, 1,2゜6-hexandriol, Alkylene glycols in which the alkylene group contains 2 to 6 carbon atoms, such as thioglycol, hexylene glycol, diethylene glycol; glycerin: ethylene glycol methyl ether, diethylene glycol methyl (or ethyl) ether, triethylene glycol monomethyl (or ethyl) ether and lower alkyl ethers of polyhydric alcohols.
これらの多くの水溶性有機溶剤の中でも、ジエチレング
リコール等の多価アルコール、トリエチレングリコール
モノメチル（またはエチル）エーテル等の多価アルコー
ルの低級アルキルエーテル類が好ましいものである。多
価アルコール類は、インク中の水が蒸発し、水溶性染料
が析出することに基づくノズルの目詰まり現象を防止す
るための潤滑剤としての効果が大きいため、特に好まし
いものである。Among these many water-soluble organic solvents, polyhydric alcohols such as diethylene glycol and lower alkyl ethers of polyhydric alcohols such as triethylene glycol monomethyl (or ethyl) ether are preferred. Polyhydric alcohols are particularly preferred because they are highly effective as lubricants to prevent nozzle clogging caused by evaporation of water in the ink and precipitation of water-soluble dyes.
インクには可溶化剤を加えることもできる。Solubilizing agents can also be added to the ink.
代表的な可溶化剤は、含窒素複素環式ケトン類であり、
その目的とする作用は、水溶性染料の溶媒体に対する溶
解性を飛躍的に向上させることＬｙ７゜
にある。例えば、Ｎ−メチル−２ヒロリドン、１．３−
ジメチル−２−イミダゾリジノンが好ましく用いられる
。Typical solubilizers are nitrogen-containing heterocyclic ketones,
The intended effect is to dramatically improve the solubility of the water-soluble dye in the solvent. For example, N-methyl-2hydrolidone, 1.3-
Dimethyl-2-imidazolidinone is preferably used.
このような成分から調整されるインクは、それ自体で記
録特性（信号応答性、液滴形成の安定性、吐出安定性、
長時間の連続記録性、長時間の記録休止後の吐出安定性
）、保存安定性、被記録材への定着性に優れたものであ
るが、これらの特性を更に改善するために、各種添加剤
を更に含有させてもよい。例えばポリビニルアルコール
、セルロース類等の水溶性樹脂等の粘度調整剤；カチオ
ン、アニオンまたはノニオン系の各種界面活性剤；ジェ
タノールアミン、トリエタノールアミン等の表面張力調
整剤−緩衝液によるｐＨ調整剤等を挙げることができる
。Ink prepared from these components has its own recording properties (signal response, droplet formation stability, ejection stability,
It has excellent long-term continuous recording performance (long-term continuous recording performance, ejection stability after long recording pauses), storage stability, and fixation to recording materials, but in order to further improve these properties, various additives are added. An agent may be further included. For example, viscosity regulators such as water-soluble resins such as polyvinyl alcohol and cellulose; various cationic, anionic or nonionic surfactants; surface tension regulators such as jetanolamine and triethanolamine; pH regulators using buffers, etc. can be mentioned.
また、インクを帯電させるタイプのインクジェット記録
方法に使用されるインクを調合するためには、塩化リチ
ウム、塩化アンモニウム。In addition, lithium chloride and ammonium chloride are used to formulate ink used in inkjet recording methods that charge the ink.
塩化ナトリウム等の無機塩類等の比抵抗調整剤が添加さ
れる。尚、熱エネルギーの作用によって、インクを吐出
させるタイプのインクジェット記録方式に適用する場合
には、熱的な物性値（例えば、比熱、熱膨張係数、熱伝
導率等）が調整されることもある。A resistivity adjuster such as an inorganic salt such as sodium chloride is added. When applied to an inkjet recording method that ejects ink through the action of thermal energy, the thermal properties (e.g., specific heat, coefficient of thermal expansion, thermal conductivity, etc.) may be adjusted. .
本発明において、前記の記録用紙に上記のインクを付与
して記録を行なうための記録方法は、インクをノズルよ
り効果的に離脱させて、射程体である被記録材にインク
を付与し得る方式であればいかなる方式でもよく、それ
らの方式の代表的なものは、例えばアイイーイーイー
トランスアクション オン インダストリイ アプリケ
イションズ（ＩＥＥＥ Ｔｒａｎｓ ａｃｔｉｏｎ
ｓ ｏｎ １ｎｄｕｓｔｒｙ Ａｐｐｌｉｃａｔ
ｉｏｎｓ）、Ｖｏｌ、 ＩＡ−１３，Ｎｏ、１（１
９７７年２．３月号）、日経エレクトロニクスの１９７
６年４月１９日号、１９７３年１月２９日号および１９
７４年５月６日号に記載されている。これらに記載の方
式は、本発明の方法に好適なものであり、その幾つかを
説明すると、先ず静電吸引方式があり、この方式では、
ノズルとノズルの数ｍｍ前方に置いた加速電極との間に
強電界を与えて、ノズルよりインクを粒子化して次々に
引出し、引出したインクが偏向電極間を飛翔する間に情
報信号を偏向電極に与えて記録する方式と、インク粒子
を偏向することなく、情報信号に対応してインク粒子を
噴射する方式とがあり、いずれも本発明の方法に有効で
ある。In the present invention, the recording method for performing recording by applying the above-mentioned ink to the above-mentioned recording paper is a method in which the ink can be effectively released from a nozzle and the ink can be applied to the recording material, which is a projectile object. Any method may be used, and representative methods include, for example, IEEE.
Transaction on Industry Applications (IEEE Transaction on Industry Applications)
s on 1 industry Application
ions), Vol. IA-13, No. 1 (1
February/March 977 issue), Nikkei Electronics 197
April 19, 1973 issue, January 29, 1973 issue and 19
It is listed in the May 6, 1974 issue. The methods described above are suitable for the method of the present invention.To explain some of them, there is an electrostatic attraction method, in which:
A strong electric field is applied between the nozzle and an accelerating electrode placed a few mm in front of the nozzle, and the ink is turned into particles and drawn out one after another from the nozzle.While the drawn ink flies between the deflection electrodes, an information signal is sent to the deflection electrode. There are two methods: a method in which ink particles are ejected in response to an information signal without deflecting the ink droplets, and both methods are effective for the method of the present invention.
第２の方式としては、小型ポンプでインクに高圧を加え
、ノズルを水晶撮勅子等で機械的に振動させることによ
り、強制的に微小インク粒子を噴射する方式であり、噴
射されたインク粒子は噴射と同時に、情報信号に応じて
帯電させる。The second method is to apply high pressure to the ink with a small pump and mechanically vibrate the nozzle with a crystal camera, etc., to forcibly eject microscopic ink particles. Simultaneously with the injection, the fuel is charged in accordance with the information signal.
帯電したインク粒子は偏向電極板間を通過する際、帯電
量に応じて偏向される。この方式を利用した別の方式と
してマイクロドツトインクジェット方式と称される方式
もあり、この方式では、インク圧力、励振条件をある範
囲の適正値に保ち、ノズル先端より大小二種類のインク
小滴を廃生し、この中小径小滴のみを記録により利用す
るものである。この方式の特徴は、従来並の太いノズル
口径でも微小小滴群を得ることができる。When the charged ink particles pass between the deflection electrode plates, they are deflected according to the amount of charge. Another method using this method is called the microdot inkjet method. In this method, ink pressure and excitation conditions are maintained at appropriate values within a certain range, and two types of ink droplets, large and small, are ejected from the nozzle tip. Only the small and medium diameter droplets are used for recording purposes. The feature of this method is that it is possible to obtain a group of minute droplets even with a conventionally large nozzle diameter.
第３の方式としてはピエゾ素子方式があり、この方式で
は、インクに加える圧力手段として、他方式の如くポン
プの様な機械的手段でなく、ピエゾ素子を利用する。ピ
エゾ素子に電気信号を与えて機械的変位を生じさせるこ
とにより、インクに圧力を加え、ノズルより噴射させる
方式である。A third method is a piezo element method, in which a piezo element is used as a pressure means for applying pressure to the ink, rather than a mechanical means such as a pump as in other methods. This method applies an electric signal to a piezo element to cause mechanical displacement, thereby applying pressure to the ink and ejecting it from a nozzle.
また、特開昭５４−５９９３６号公報に記載されている
方法で、熱エネルギーの作用を受けたインクが急激な体
積変化を生じ、この状態変化による作用力によって、イ
ンクをノズルから吐出させるインクジェット方式も有効
に使用することができる。In addition, an inkjet method is disclosed in Japanese Patent Application Laid-Open No. 54-59936, in which ink subjected to the action of thermal energy undergoes a sudden change in volume, and the acting force due to this state change causes the ink to be ejected from a nozzle. can also be used effectively.
本発明に於いて、例えばインク受容層の最表層に熱可塑
性樹脂粒子を含有せしめ、インクジェット記録後に最表
層を加熱して透明化し、光沢のある画像を形成すること
もできる。In the present invention, for example, thermoplastic resin particles may be contained in the outermost layer of the ink-receiving layer, and the outermost layer may be heated to become transparent after inkjet recording to form a glossy image.
（実施例）
以下、実施例および比較例に従って本発明を更に詳細に
説明する。尚、文中、部または％とあるのは特に断りの
ない限り重量基準である。(Examples) Hereinafter, the present invention will be explained in more detail according to Examples and Comparative Examples. In the text, parts and percentages are based on weight unless otherwise specified.
本発明は、下記の実施例に限定されるものではない。The present invention is not limited to the following examples.
実施例１〜３．比較例１
基材として一般上質紙（銀環（商標名）；坪量８１．４
ｇ／ｍ’、山陽国策バルブ＠製）を使用し、この基材上
に下記組成の塗工液を第２層のインク受容層の乾燥塗工
量が２０ｇ／ｍ’、最表層の乾燥塗工量が６ ｇ ／
ｍ ’となるようにそれぞれバーコーターにより塗工し
、常法により乾燥させ、さらに軽くスーパーカレンダー
掛けをして本発明の被記録材ならびに比較例１の被記録
材を得た。Examples 1-3. Comparative Example 1 General high-quality paper (Ginrin (trade name); basis weight 81.4
g/m', manufactured by Sanyo Kokusaku Valve@), and applied a coating solution with the following composition onto this substrate, with a dry coating amount of 20 g/m' for the second ink-receiving layer and a dry coating amount of the outermost layer. The amount of work is 6 g/
The recording material of the present invention and the recording material of Comparative Example 1 were obtained by coating each coated material using a bar coater so as to obtain a coating film of m', drying by a conventional method, and then applying a light supercalender.
実施例１
（第２層）
（最表層）
実施例２
（第２層）
（最表層）
実施例３
（第２層）
（最表層）
比較例１
（第２層）
（最表層）
上記の被記録材に対して、下記４種類のインクを用いて
、発熱抵抗体によりバブルを発生させ、その圧力でイン
クを吐出させるオンデマンド型インクジェット記録ヘッ
ド（オリフィスサイズ２０Ｘ２５μｍ、ノズル本ａ１２
８本、駆動電圧２４．５Ｖ、周波数２ＫＨｚ）を有する
記録装置を使用してインクジェット記録を行ない、イン
クジェット記！３適性の評価を行なった。Example 1 (Second layer) (Top layer) Example 2 (Second layer) (Top layer) Example 3 (Second layer) (Top layer) Comparative example 1 (Second layer) (Top layer) The above An on-demand inkjet recording head (orifice size 20 x 25 μm, nozzle size A12) uses the following four types of ink on the recording material, generates bubbles with a heating resistor, and uses the resulting pressure to eject the ink.
Inkjet recording is performed using a recording device with 8 ink jets, a driving voltage of 24.5 V, and a frequency of 2 KHz. 3 Aptitude evaluation was conducted.
イエローインク
Ｃ，１，ダイレクトイエロー８６ ２部ジエチレング
リコール ３０部水
７０部マゼンタインク
Ｃ，１，アシッドレッド３５ ３部ジエチレング
リコール ３０部水
７０部シアンインク
Ｃ，１，ダイレクトブルー８６ ４部ジエチレング
リコール ３０部水
７０部ブラックインク
Ｃ，１，フードブラック２ ４部ジエチレン
グリコール ３０部水
７０部（１） ドツト
径
印字ドラ１−２０個の直径を実体顕微鏡で測定し、平均
値を示した。Yellow Ink C, 1, Direct Yellow 86 2 parts diethylene glycol 30 parts water
70 parts Magenta Ink C, 1, Acid Red 35 3 parts diethylene glycol 30 parts water
70 parts Cyan ink C, 1, Direct Blue 86 4 parts diethylene glycol 30 parts water
70 parts Black Ink C, 1, Food Black 2 4 parts diethylene glycol 30 parts water
70 parts (1) Dot diameter The diameters of 1 to 20 printing drums were measured using a stereomicroscope, and the average value is shown.
（２）ドツト形状
印字ドツトを実体顕微鏡で観察して、はぼ円形のものを
○、円径が多少くずれたものを△、不定形のものを×と
した。(2) Printed dot shape The dots were observed with a stereomicroscope. Those with a round shape were marked as ○, those with a somewhat distorted diameter were marked as △, and those with an irregular shape were marked as ×.
（３）色彩発色性
インクジェット記録画像の色の鮮明さを目視により比較
し、最も良いものを◎、最も悪いものを×とし、◎、○
、△、×のランク分けをした。(3) Color development Compare the color sharpness of the inkjet recorded images by visual inspection, and mark the best one as ◎, and the worst as ×, ◎, ○.
, △, and × were ranked.
（４）発色濃度
シアンのベタ印字部をマクベス濃度計ＲＤ−９１８型で
測定した。(4) Color density: The cyan solid printed area was measured using a Macbeth densitometer model RD-918.
（５）インク吸収性
ブラックのベタ印字後、１秒間で吸収するインク量で表
わした。(5) Ink absorbability It is expressed as the amount of ink absorbed in 1 second after solid black printing.
数値の大きいもの程インク吸収性が良い。The larger the number, the better the ink absorption.
その結果を表１に示す。The results are shown in Table 1.
比較例２〜４
基材として一般上質紙〔鎖環（商標名）；坪量ａ１．４
ｇ／ｍ’ ）を使用し、この基材上に下記組成の塗工液
を、乾燥塗工量が２６ｇ／ｍ’となるようにバーコータ
ーにより塗工し、常ン去により乾燥させ、さらに軽くス
ーパーカレンダー掛けをして、比較例２〜４の被記録材
を得た。Comparative Examples 2 to 4 General wood-free paper [chain ring (trade name); basis weight a1.4
g/m'), a coating solution with the following composition was applied onto this substrate using a bar coater so that the dry coating amount was 26 g/m', and the coating was dried by constant evaporation. The recording materials of Comparative Examples 2 to 4 were obtained by light supercalendering.
（塗工液組成） 使用した粒子は以下に示すものである。(Coating liquid composition) The particles used are shown below.
比較例２
合成無定形シリカ
（富士デヴイソン■製、サイロイド６２ｏ）比較例３
タルク
（富士タルク工業製、ＬＭ−Ｓｌ、平均径２．３μｍ）
比較例４
メチルメタクリレート樹脂
（松本油脂製薬味製品、マツモトマイクロス壺エアーＭ
−１００，平均径１０μｍ）
上記比較例２〜４の被記録材に対して、実施例１〜３と
同様にインクジェット記録を行い、インクジェット記録
適性の評価を行った。その結果を表１に示す。Comparative Example 2 Synthetic amorphous silica (manufactured by Fuji Davison ■, Thyroid 62o) Comparative Example 3 Talc (manufactured by Fuji Talc Industries, LM-Sl, average diameter 2.3 μm) Comparative Example 4 Methyl methacrylate resin (Matsumoto Yushi Pharmaceutical Flavor Products, Matsumoto Micros pot air M
-100, average diameter 10 μm) Inkjet recording was performed on the recording materials of Comparative Examples 2 to 4 in the same manner as in Examples 1 to 3, and the suitability for inkjet recording was evaluated. The results are shown in Table 1.
実施例４
実施例１の被記録材上に、さらに下記組成の塗工液を乾
燥塗工量が３ ｇ ／ ｍ ２となるようにバーコータ
ーにより塗工し、常法により乾燥させて本発明の実施例
４の被記録材を得た。この被記録材に対して実施例１〜
３と同様にインクジェット記録を行った後、１４０℃、
２分間という条件で加熱し、インク受容層の、最表層を
透明化させ、光沢１８のある画像を得た。この画像につ
いても前記と同様の評価を行った。その結果を表１に示
す。Example 4 A coating solution having the following composition was further applied on the recording material of Example 1 using a bar coater so that the dry coating amount was 3 g/m 2 and dried by a conventional method to obtain the coating composition of the present invention. A recording material of Example 4 was obtained. Example 1 to this recording material
After performing inkjet recording in the same manner as in 3, the temperature was 140°C.
Heating was carried out for 2 minutes to make the outermost layer of the ink-receiving layer transparent, and an image with gloss of 18 was obtained. This image was also evaluated in the same way as above. The results are shown in Table 1.
（塗工液組成）
〔効果〕
本発明の記録方法、すなわち水溶性染料を含む記録液を
用いて、インク受容層の少なくとも１層が球状シリカを
含有し、且つ好ましくは各層に含まれる粒子の平均径が
異なっている２層以上のインク受容層を有する被記録材
に記録を行なうことにより、
記録液が速やかに被記録材内部に吸収され、ドツト形状
の乱れが小さく、色彩発色性に優れ、発色濃度の高い鮮
明な記録画像が得られる。とりわけ記録液の表面張力が
３０〜７０ｃｉｙｎ／ｃｍのとき、色彩発色性、発色濃
度、ドツト形状を同時に満足する優れた効果を有する。(Coating liquid composition) [Effect] By using the recording method of the present invention, that is, a recording liquid containing a water-soluble dye, at least one layer of the ink-receiving layer contains spherical silica, and preferably the particles contained in each layer are By recording on a recording material that has two or more ink-receiving layers with different average diameters, the recording liquid is quickly absorbed into the recording material, resulting in less disturbance in dot shape and excellent color development. , clear recorded images with high color density can be obtained. In particular, when the surface tension of the recording liquid is 30 to 70 ciyn/cm, an excellent effect can be obtained that satisfies color development, color density, and dot shape at the same time.
従って、球状シリカをインク受容層に含有する本発明の
被記録材は、高画質を要求されるインクジェット記録に
好適なものである。Therefore, the recording material of the present invention containing spherical silica in the ink receiving layer is suitable for ink jet recording which requires high image quality.
第１図は本発明の被記録材の一実施態様を示す断面図で
ある。FIG. 1 is a sectional view showing one embodiment of the recording material of the present invention.
Claims (11)
る被記録材に於いて、 該インク受容層の少なくとも１層が粒子として球状シリ
カを含有することを特徴とする被記録材。(1) A recording material having an ink receiving layer consisting of two or more layers containing particles, characterized in that at least one layer of the ink receiving layer contains spherical silica as particles.
れぞれ異なっている特許請求の範囲第１項記載の被記録
材。(2) The recording material according to claim 1, wherein the particles contained in each layer of the ink receiving layer have different average diameters.
ある特許請求の範囲第２項記載の被記録材。(3) The recording material according to claim 2, wherein the difference in average diameter of particles contained in each layer is 1 μm or more.
層にある特許請求の範囲第１項記載の被記録材。(4) The recording material according to claim 1, wherein the layer containing spherical silica is the outermost layer of the ink receiving layer.
ｍの範囲にあり、且つ二次粒子内部の平均細孔径が３０
〜４００Åの範囲にある特許請求の範囲第１項記載の被
記録材。(5) The average diameter of secondary particles of spherical silica is 0.5 to 35μ
m range, and the average pore diameter inside the secondary particles is 30
The recording material according to claim 1, which has a thickness in the range of ~400 Å.
囲にある特許請求の範囲第１項記載の被記録材。(6) The recording material according to claim 1, wherein the outermost layer of the ink-receiving layer has a thickness in the range of 3 to 30 μm.
囲にある特許請求の範囲第１項記載の被記録材。(7) The recording material according to claim 1, wherein the thickness of the lower layer of the ink-receiving layer is in the range of 5 to 100 μm.
む記録液を以て記録を行うインクジェット記録方法に於
いて、該被記録材が２層以上からなるインク受容層を有
し、且つ少なくとも１層に粒子として球状シリカを含む
ことを特徴とするインクジェット記録方法。(8) In an inkjet recording method in which recording is performed on a recording material using a recording liquid containing a water-soluble dye as a recording agent, the recording material has an ink receiving layer consisting of two or more layers, and at least An inkjet recording method characterized in that one layer contains spherical silica as particles.
μｍの範囲にあり、且つ二次粒子内部の平均細孔径が３
０〜４００Åの範囲にある特許請求の範囲第８項記載の
インクジェット記録方法。(9) The average diameter of the secondary particles of the spherical silica is 0.5 to 35
μm range, and the average pore diameter inside the secondary particles is 3
The inkjet recording method according to claim 8, wherein the inkjet recording method has a thickness in the range of 0 to 400 Å.
０ｄｙｎｅ／ｃｍの範囲にある特許請求の範囲第８項記
載のインクジェット記録方法。(10) The surface tension of the recording liquid at 25°C is 30 to 7
The inkjet recording method according to claim 8, wherein the inkjet recording method is in the range of 0 dyne/cm.
囲にある特許請求の範囲第８項記載のインクジェット記
録方法。(11) The inkjet recording method according to claim 8, wherein the water content of the recording liquid is in the range of 20 to 90% by weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61250032A JPS63104878A (en) | 1986-10-21 | 1986-10-21 | Recording material and ink jet recording method using the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61250032A JPS63104878A (en) | 1986-10-21 | 1986-10-21 | Recording material and ink jet recording method using the same |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS63104878A true JPS63104878A (en) | 1988-05-10 |
Family
ID=17201816
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61250032A Pending JPS63104878A (en) | 1986-10-21 | 1986-10-21 | Recording material and ink jet recording method using the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63104878A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01283182A (en) * | 1988-05-11 | 1989-11-14 | Canon Inc | Ink jet recording method |
| JPH0825800A (en) * | 1994-07-20 | 1996-01-30 | Canon Inc | Ink jet recording method |
| JPH08104054A (en) * | 1994-10-04 | 1996-04-23 | Canon Inc | Ink jet recording method |
| EP0781666A1 (en) * | 1995-12-27 | 1997-07-02 | Tomoegawa Paper Co. Ltd. | Ink jet recording sheet containing silica |
| EP0878322A2 (en) * | 1997-05-15 | 1998-11-18 | Oji Paper Company Limited | Ink jet recording material and process for producing the same |
| US6548149B1 (en) | 1996-04-24 | 2003-04-15 | Oji Paper Co., Ltd. | Ink jet recording material and process for producing same |
-
1986
- 1986-10-21 JP JP61250032A patent/JPS63104878A/en active Pending
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01283182A (en) * | 1988-05-11 | 1989-11-14 | Canon Inc | Ink jet recording method |
| JPH0825800A (en) * | 1994-07-20 | 1996-01-30 | Canon Inc | Ink jet recording method |
| JPH08104054A (en) * | 1994-10-04 | 1996-04-23 | Canon Inc | Ink jet recording method |
| EP0781666A1 (en) * | 1995-12-27 | 1997-07-02 | Tomoegawa Paper Co. Ltd. | Ink jet recording sheet containing silica |
| US6548149B1 (en) | 1996-04-24 | 2003-04-15 | Oji Paper Co., Ltd. | Ink jet recording material and process for producing same |
| EP0878322A2 (en) * | 1997-05-15 | 1998-11-18 | Oji Paper Company Limited | Ink jet recording material and process for producing the same |
| EP0878322A3 (en) * | 1997-05-15 | 1998-11-25 | Oji Paper Company Limited | Ink jet recording material and process for producing the same |
| EP1038691A1 (en) * | 1997-05-15 | 2000-09-27 | Oji Paper Co., Ltd. | A process for producing an ink jet recording material |
| US6465086B1 (en) | 1997-05-15 | 2002-10-15 | Oji Paper Co., Ltd. | Ink jet recording material and process for producing same |
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