JPH10181190A - Ink jet recording medium and its manufacture - Google Patents

Ink jet recording medium and its manufacture

Info

Publication number
JPH10181190A
JPH10181190A JP8347736A JP34773696A JPH10181190A JP H10181190 A JPH10181190 A JP H10181190A JP 8347736 A JP8347736 A JP 8347736A JP 34773696 A JP34773696 A JP 34773696A JP H10181190 A JPH10181190 A JP H10181190A
Authority
JP
Japan
Prior art keywords
pigment
jet recording
ink jet
aggregate
ink
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
Application number
JP8347736A
Other languages
Japanese (ja)
Inventor
Nami Riyuu
波 劉
Masami Kubota
雅美 久保田
Shiyunichirou Mukouyoshi
俊一郎 向吉
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
New Oji Paper Co Ltd
Original Assignee
Oji Paper Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Oji Paper Co Ltd filed Critical Oji Paper Co Ltd
Priority to JP8347736A priority Critical patent/JPH10181190A/en
Priority to EP97310557A priority patent/EP0850777B1/en
Priority to DE69707631T priority patent/DE69707631T2/en
Priority to US08/997,881 priority patent/US5958168A/en
Publication of JPH10181190A publication Critical patent/JPH10181190A/en
Priority to US09/664,740 priority patent/US6270837B1/en
Pending legal-status Critical Current

Links

Landscapes

  • Application Of Or Painting With Fluid Materials (AREA)
  • Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
  • Paper (AREA)
  • Ink Jet Recording Methods And Recording Media Thereof (AREA)

Abstract

PROBLEM TO BE SOLVED: To prevent thickening of coating liquid and to obtain excellent glossiness, ink absorptivity, printing density and moisture and water resistance after printing by comminuting and dispersing aggregate pigment of pigment-containing coating liquid coating or impregnating a support in cationic resin-containing liquid, and forming specific aggregate mean particle size or less. SOLUTION: The ink jet recording medium coating or impregnating a support with pigment-containing coating liquid contains pigment obtained by comminuting and dispersing aggregate pigment in cation-containing liquid and comminuting it to mean particle size of 500nm or less. Uniform dispersion liquid is obtained by, for example, comminuting aggregate of silica of about 1 to 50μm by mechanical force, adding cationic resin before forming colloidal fine particle dispersion liquid, dispersing together with the aggregate such as silica, and then comminuting by the force. The dispersion liquid has satisfactory dispersing stability, coating suitability, excellent glossiness, printing density, and moisture and water resistance after printing.

Description

【発明の詳細な説明】DETAILED DESCRIPTION OF THE INVENTION

【0001】[0001]

【発明の属する技術分野】本発明はインクジェット記録
体に関し、特に、光沢性、インク吸収性、印字濃度、耐
水性等に優れるインクジェット記録体及びその製造方法
に関する。
BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an ink jet recording medium, and more particularly to an ink jet recording medium having excellent gloss, ink absorbency, print density, water resistance, and the like, and a method for producing the same.

【0002】[0002]

【従来の技術】インクジェット記録方式は、ノズルから
高速で射出したインク液滴を、被記録材に付着させて記
録する方式であり、フルカラー化が容易なことや印字騒
音が低い等の特徴を有する。この方式では、使用される
インクは多量の溶媒を含んでいるので、高い記録濃度を
得るためには、大量のインクを用いる必要がある。ま
た、インク液滴は連続的に射出されるので、最初の液滴
が吸収されないうちに次の液滴が射出され、インク液滴
が融合してインクのドットが接合するという不都合が生
じやすい。従って、このインクジェット記録方式で使用
される記録体としては、印字ドットの濃度が高く、色調
が明るく鮮やかであること、インクの吸収が速くて印字
ドットが重なった場合においてもインクの滲みがないこ
と等が要求される。最近、インクジェットプリンターの
急速な普及に対応して、印刷分野では、各種出版物や包
装等の用途で、高光沢のある写真並の印刷物が求められ
ている。特に、カラー記録の場合は、ドットの形状(真
円状)、ドットのシャープさ、インクの吸収、定着速
度、インク吸収容量等のインク受理性の点からフィルム
や塗工紙タイプのニーズが高い。
2. Description of the Related Art An ink jet recording system is a system in which ink droplets ejected from a nozzle at a high speed are adhered to a recording material for recording, and has features such as easy full-color printing and low printing noise. . In this method, since the ink used contains a large amount of solvent, it is necessary to use a large amount of ink in order to obtain a high recording density. In addition, since the ink droplets are continuously ejected, the next droplet is ejected before the first droplet is absorbed, which is likely to cause a disadvantage that the ink droplets are fused and ink dots are joined. Therefore, the recording medium used in the ink jet recording method has a high print dot density, a bright and vivid color tone, and has a high ink absorption, and does not have ink bleeding even when the print dots overlap. Etc. are required. In recent years, in response to the rapid spread of inkjet printers, in the printing field, high-gloss photographic prints have been required for various publications and packaging applications. In particular, in the case of color recording, the need for a film or coated paper type is high in terms of ink acceptability such as dot shape (circular shape), dot sharpness, ink absorption, fixing speed, and ink absorption capacity. .

【0003】一般のインクジェット用インクは水溶性で
あるため、印字後の耐湿・耐水性が劣る欠点を有する。
耐湿・耐水性を改良する目的で、紙や記録層中にカチオ
ン樹脂を配合するのが一般的である。例えば、特公平2
−035673号公報等に開示されたようにインクジェ
ット記録用紙に顔料やカチオン樹脂を内填させ、インク
中のアニオン性染料を定着させることによって印字後の
耐湿・耐水性を改良する報告がある。さらに、インクジ
ェット記録紙の印字画質(ドットのシャープさをコント
ロール等)、印字濃度を高めるために、シリカ、アルミ
ナなどの顔料を含有する塗工層を設ける塗工紙が挙げら
れる(例えば:特願平7−260198号公報等)。し
かし、これらの塗工紙は一般的にミクロンオーダーの顔
料とカチオン樹脂及び接着剤(バインダー)を主成分と
して構成され、顔料の存在によってインクが吸収され、
吸収されたインク中の染料はカチオン樹脂によって定着
されるが、使用される顔料の粒径が大きく、透明性が必
ずしも充分ではなく、表面がざらつきやすく、高光沢、
高印字濃度のインクジェット記録体を得ることが困難で
あった。
[0003] Since general ink-jet inks are water-soluble, they suffer from poor moisture and water resistance after printing.
In general, a cationic resin is blended in paper or a recording layer for the purpose of improving moisture resistance and water resistance. For example, Tokuhei 2
As disclosed in JP-035673A and the like, there is a report of improving moisture resistance and water resistance after printing by filling a pigment or a cationic resin into an ink jet recording paper and fixing an anionic dye in the ink. Further, there is a coated paper provided with a coating layer containing a pigment such as silica or alumina in order to increase the print quality (control of dot sharpness, etc.) and print density of the ink jet recording paper (for example: Japanese Patent Application JP-A-7-260198). However, these coated papers are generally composed of pigments of micron order, a cationic resin and an adhesive (binder) as main components, and the presence of the pigment allows the ink to be absorbed.
The dye in the absorbed ink is fixed by the cationic resin, but the pigment used has a large particle size, transparency is not always sufficient, the surface is easily rough, high gloss,
It was difficult to obtain an ink jet recording medium having a high printing density.

【0004】[0004]

【発明が解決しようとする課題】光沢、印字濃度を改良
する目的で、本発明者らは機械的分散法でミクロンオー
ダーのシリカなどの微粒子を粉砕、500nm以下のコ
ロイド状粒子を作成し(特願平8−102494号公報
等)、それを用いることによって高光沢、高印字濃度の
インクジェット記録体を得ることが可能であることを明
らかにした。しかし、シリカなどのコロイド状粒子はア
ニオン性を有するため、そのままでは染料に対して定着
力がなく、印字後の耐湿・耐水性が劣る欠点を有してい
た。一方、カチオン樹脂を添加すると増粘が起こり、透
明性や表面平滑性が著しく低下する恐れがある。また、
カチオン樹脂を添加すると塗工液が増粘し、塗工が困難
になる問題があった。本発明は上記の問題を解決し、よ
り光沢性、インク吸収性、印字濃度、印字後の耐湿・耐
水性に優れるインクジェット記録体を提供することを目
的としている。
For the purpose of improving gloss and print density, the present inventors pulverized fine particles such as silica having a micron order by a mechanical dispersion method, and prepared colloidal particles having a size of 500 nm or less. Japanese Patent Application Laid-Open No. Hei 8-102494), and it has been clarified that an ink jet recording medium having high gloss and high print density can be obtained by using the same. However, since colloidal particles such as silica have an anionic property, they have no fixing power to dyes as they are, and have a defect that moisture resistance and water resistance after printing are inferior. On the other hand, when a cationic resin is added, the viscosity increases, and the transparency and the surface smoothness may be significantly reduced. Also,
When a cationic resin is added, the coating liquid thickens, and there is a problem that coating becomes difficult. SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned problems and to provide an ink jet recording medium that is more excellent in glossiness, ink absorbency, print density, and moisture resistance and water resistance after printing.

【0005】[0005]

【課題を解決するための手段】本発明は以下の様態を含
むがこれらに限るものではない。 [1]支持体に顔料含有塗液を塗布若しくは含浸してな
るインクジェット記録体であり、該塗液が、凝集体顔料
をカチオン樹脂含有液中で粉砕分散し凝集体平均粒径を
500nm以下とした顔料を含有する塗液であることを
特徴とするインクジェット記録体。 [2] カチオン樹脂含有液が更に水溶性樹脂を含む
[1]記載のインクジェット記録体。 [3] 凝集体顔料が非晶質シリカを含む[1]または
[2]記載のインクジェット記録体。 [4]支持体に記録層を設けたインクジェット記録体の
製造方法において、少なくとも1層の記録層は顔料を含
有し、成形面に塗工成膜された後、支持体上に(或いは
他の記録層が既に支持体上に設けられている場合は、そ
の記録層上に)転写されるインクジェット記録体の製造
方法であり、且つ前記顔料は凝集体顔料をカチオン樹脂
含有液中で粉砕分散し、凝集体平均粒径を500nm以
下とした顔料であることを特徴とするインクジェット記
録体の製造方法。 [5] 粉砕分散した凝集体平均粒径が300nm以下
であることを特徴とする[1]〜[3]のいずれかに記
載のインクジェット記録体。
The present invention includes, but is not limited to, the following aspects. [1] An ink jet recording material obtained by coating or impregnating a support with a pigment-containing coating liquid, wherein the coating liquid is obtained by pulverizing and dispersing an aggregate pigment in a cationic resin-containing liquid to have an average aggregate particle diameter of 500 nm or less. An ink-jet recording material, which is a coating liquid containing a pigment. [2] The ink jet recording medium according to [1], wherein the cationic resin-containing liquid further contains a water-soluble resin. [3] The ink jet recording material according to [1] or [2], wherein the aggregate pigment contains amorphous silica. [4] In the method for producing an ink jet recording medium provided with a recording layer on a support, at least one recording layer contains a pigment, and after being coated and formed on a molding surface, is formed on a support (or another When the recording layer is already provided on the support, the method is a method for producing an ink jet recording material to be transferred onto the recording layer), and the pigment is obtained by grinding and dispersing an aggregate pigment in a cationic resin-containing liquid. And a pigment having an average aggregate particle size of 500 nm or less. [5] The ink jet recording material according to any one of [1] to [3], wherein the average particle size of the pulverized and dispersed aggregate is 300 nm or less.

【0006】[6] 凝集体顔料をカチオン樹脂含有液
中で粉砕分散し、凝集体平均粒径を粉砕前の値以下であ
り且つ500nm以下とした顔料を含有するインクジェ
ット記録体。 [7] 支持体に顔料含有塗液を塗布若しくは含浸する
インクジェット記録体の製造方法において、該塗液が、
凝集体顔料をカチオン樹脂含有液中で粉砕分散し凝集体
平均粒径を500nm以下とした顔料を含有する塗液で
あることを特徴とするインクジェット記録体の製造方
法。
[6] An ink jet recording medium containing a pigment in which the aggregate pigment is pulverized and dispersed in a liquid containing a cationic resin, and the average particle diameter of the aggregate is not more than the value before pulverization and not more than 500 nm. [7] In a method for producing an ink jet recording medium, in which a support is coated or impregnated with a pigment-containing coating liquid, the coating liquid is
A method for producing an ink jet recording material, which is a coating liquid containing a pigment in which an aggregate pigment is pulverized and dispersed in a cationic resin-containing liquid so that the average particle diameter of the aggregate is 500 nm or less.

【0007】[8] 支持体に顔料含有塗液を塗布若し
くは含浸するインクジェット記録体の製造方法におい
て、該塗液が、凝集体顔料をカチオン樹脂含有液中で粉
砕分散し凝集体平均粒径を粉砕前の値以下であり且つ5
00nm以下とした顔料を含有する塗液であることを特
徴とするインクジェット記録体の製造方法。 [9] 凝集体顔料をカチオン樹脂含有液中で粉砕分散
し、凝集体平均粒径を500nm以下とした顔料を含有
するインクジェット記録体。
[8] In a method for producing an ink jet recording medium, wherein a pigment-containing coating liquid is applied to or impregnated on a support, the coating liquid is obtained by pulverizing and dispersing an aggregate pigment in a cationic resin-containing liquid to reduce the average particle diameter of the aggregate. Less than the value before grinding and 5
A method for producing an ink jet recording medium, which is a coating liquid containing a pigment having a diameter of not more than 00 nm. [9] An ink jet recording medium containing a pigment obtained by pulverizing and dispersing an aggregate pigment in a liquid containing a cationic resin to have an average aggregate particle diameter of 500 nm or less.

【0008】[0008]

【発明の実施の形態】一般に、ミクロンオーダーの顔料
とカチオン性樹脂、バインダーを混合して分散する際
に、分散液中の顔料が多少の増粘を起こしても、塗工し
て得られる塗工層には特に影響しないが、平均粒径が5
00nm以下のコロイド状粒子になると分散液中に顔料
が凝集すると、塗工層の透明性が著しく低下するだけで
なく、表面がざらつきやすく、平滑性が優れる光沢面を
得ることが困難である。シリカ等の粒子は水中でアニオ
ン性であり、勿論、凝集体(1次粒子により構成される
2次粒子や3次粒子)により構成されるシリカコロイド
状粒子もアニオン性である。アニオン性のシリカ微粒子
はインク中の染料に対して定着性がなく、印字後の耐湿
・耐水性が劣る。印字後の耐湿・耐水性を上げるため
に、カチオン性樹脂等の添加が不可欠である。しかし、
アニオン性のシリカコロイド状粒子にカチオン樹脂を添
加すると直ちに凝集が起こり、光沢、透明性を有する記
録層を得ることが困難である。
DESCRIPTION OF THE PREFERRED EMBODIMENTS In general, when mixing and dispersing a micron-order pigment with a cationic resin and a binder, even if the pigment in the dispersion slightly thickens, a coating obtained by coating is obtained. The average particle size is 5
When the colloidal particles having a size of not more than 00 nm are agglomerated with the pigment in the dispersion, not only the transparency of the coating layer is remarkably reduced, but also it is difficult to obtain a glossy surface having a rough surface and excellent smoothness. Particles such as silica are anionic in water, and of course, silica colloidal particles composed of aggregates (secondary particles and tertiary particles composed of primary particles) are also anionic. The anionic silica fine particles have no fixing property to the dye in the ink, and have poor moisture resistance and water resistance after printing. In order to increase the moisture resistance and water resistance after printing, it is essential to add a cationic resin or the like. But,
When a cationic resin is added to the anionic silica colloidal particles, aggregation occurs immediately, and it is difficult to obtain a glossy and transparent recording layer.

【0009】そこで、発明者らは鋭意検討を重ねた結
果、500nmを越え、例えば1μm程度〜50μm程
度のシリカ等の凝集体を機械力で粉砕し、コロイド状の
微粒子分散液を作成する前に、カチオン樹脂を添加し、
シリカなどの凝集体と一緒に分散した後、機械力で粉砕
する。作成したシリカコロイド状微粒子分散液はカチオ
ン樹脂を含有するにも関わらず、均一な分散液を得るこ
とができることがわかった。この方法で作成した塗料で
塗工すると、高光沢、高印字濃度、印字後の耐湿・耐水
性が良好なインクジェット記録体が得られる。理由は定
かではないが、カチオン樹脂の存在下でシリカなどの凝
集体を粉砕分散すると、分散途中でカチオン樹脂のシリ
カ表面への吸着がすすみ、500nm以下のコロイド状
粒子になる時点で吸着が平行状態に達し、つまり、シリ
カ粒子の表面が殆どカチオン樹脂で覆われる状態になっ
ているのではないかと思われる。
Accordingly, the present inventors have conducted intensive studies, and as a result, before agglomerating aggregates such as silica having a diameter of more than 500 nm, for example, silica of about 1 μm to about 50 μm, with mechanical force, to prepare a colloidal fine particle dispersion. , Adding a cationic resin,
After being dispersed together with aggregates such as silica, the mixture is pulverized by mechanical force. It was found that the prepared silica colloidal fine particle dispersion could obtain a uniform dispersion despite containing a cationic resin. When applied with a paint prepared by this method, an ink jet recording medium having high gloss, high print density, and good moisture resistance and water resistance after printing can be obtained. Although the reason is not clear, when the aggregates such as silica are pulverized and dispersed in the presence of the cationic resin, the adsorption of the cationic resin to the silica surface proceeds during the dispersion, and the adsorption becomes parallel at the time when the colloidal particles of 500 nm or less are formed. It is considered that the state has been reached, that is, the surface of the silica particles is almost completely covered with the cationic resin.

【0010】凝集体顔料をカチオン樹脂と他の水溶性樹
脂の存在下で機械的手法により分散し、凝集体の平均粒
径が500nm以下になるように粉砕分散して得られる
分散液は分散安定性が良好で、その分散液の塗工適性が
よく、より光沢、印字濃度の優れるインクジェット記録
体が得られる。
The dispersion obtained by dispersing the aggregate pigment by a mechanical method in the presence of a cationic resin and another water-soluble resin and pulverizing and dispersing the aggregate so that the average particle diameter of the aggregate is 500 nm or less is obtained. An ink jet recording medium having good properties, good coating suitability of the dispersion, and excellent gloss and print density can be obtained.

【0011】本発明は凝集体をカチオン樹脂の存在下で
凝集体の平均粒径が500nm以下になるように粉砕分
散した顔料を含有することを特徴とするインクジェット
記録体に関する。本発明の顔料の好ましい分散体はコロ
イド状やスラリー状である。本発明のインクジェット記
録体は高光沢を有し、且つ優れたインク吸収性、高印字
濃度、印字後の耐湿・耐水性を兼ね備えたものである。
The present invention relates to an ink jet recording material containing a pigment obtained by pulverizing and dispersing an aggregate in the presence of a cationic resin so that the average particle size of the aggregate is 500 nm or less. Preferred dispersions of the pigment of the present invention are colloidal or slurry. The ink jet recording medium of the present invention has high gloss, excellent ink absorbency, high print density, and moisture and water resistance after printing.

【0012】本発明において、支持体としては特に限定
されず、透明または不透明支持体が使用でき、例えば、
セロハン、ポリエチレン、ポリプロピレン、軟質ポリ塩
化ビニル、硬質ポリ塩化ビニル、ポリエステル等のプラ
スチックフィルム類、上質紙、アート紙、コート紙、キ
ャスト塗工紙、箔紙、クラフト紙、ポリエチレンラミネ
ート紙、含浸紙、蒸着紙、水溶性紙等の紙類、金属フォ
イル、合成紙などが適宜使用される。
In the present invention, the support is not particularly limited, and a transparent or opaque support can be used.
Cellophane, polyethylene, polypropylene, soft polyvinyl chloride, hard polyvinyl chloride, polyester and other plastic films, fine paper, art paper, coated paper, cast coated paper, foil paper, kraft paper, polyethylene laminated paper, impregnated paper, Paper such as vapor-deposited paper and water-soluble paper, metal foil, synthetic paper and the like are appropriately used.

【0013】本発明の記録層は単層または複層よりな
る。先ず、記録層が単層により構成される場合、記録層
中に少なくとも下記に例示するような顔料を含有する。
顔料としては、たとえば、非晶質シリカ等のシリカ、ク
レー、焼成クレー、酸化亜鉛、酸化錫、硫酸マグネシウ
ム、酸化アルミニウム、水酸化アルミニウム、擬ベーマ
イト、炭酸カルシウム、サチンホワイト、珪酸アルミニ
ウム、スメクタイト、ゼオライト、珪酸マグネシウム、
炭酸マグネシウム、酸化マグネシウム、珪藻土等、一般
塗工紙分野で公知公用の各種顔料を用い、下記のような
方法によって調製する。
The recording layer of the present invention comprises a single layer or multiple layers. First, when the recording layer is composed of a single layer, the recording layer contains at least a pigment as exemplified below.
Examples of the pigment include silica such as amorphous silica, clay, calcined clay, zinc oxide, tin oxide, magnesium sulfate, aluminum oxide, aluminum hydroxide, pseudoboehmite, calcium carbonate, satin white, aluminum silicate, smectite, and zeolite. , Magnesium silicate,
It is prepared by the following method using various pigments known and used in the general coated paper field, such as magnesium carbonate, magnesium oxide, and diatomaceous earth.

【0014】まず、顔料を水などで分散し、カチオン樹
脂を添加後、機械的方法で顔料の平均粒径が500nm
以下、さらに、高印字濃度を得るためには平均粒径が好
ましくは10〜300nmの2次粒子(分散体)まで粉
砕し、分散する。平均粒径500nm以下の凝集体を得
るためには一般市販の1〜50μの凝集粒子を機械的手
段で強い力を与えることにより得られる。つまり、br
eaking down法(塊状原料を細分化する方
法)によって得られる。機械的手段としては、超音波、
高速回転ミル、ローラミル、容器駆動媒体ミル、媒体攪
拌ミル、ジェットミル、擂解機、サンドグラインダー等
の機械的手法が挙げられる。本発明でいう平均粒径はす
べて電子顕微鏡(SEMとTEM)で観察した粒径であ
る(マーチン径の平均値。「微粒子ハンドブック」、朝
倉書店、p52参照、1991年)。尚,凝集体を形成
する一次粒子の平均粒径は3nmから40nmが好まし
い。一次粒径が小さいと吸収能が低下する恐れがあり,
逆に大きいとインク記録層の透明性が低下する恐れがあ
る。
First, the pigment is dispersed in water or the like, and after adding a cationic resin, the pigment has an average particle diameter of 500 nm by a mechanical method.
Hereinafter, in order to further obtain a high printing density, the particles are pulverized and dispersed to secondary particles (dispersions) having an average particle diameter of preferably 10 to 300 nm. In order to obtain an aggregate having an average particle size of 500 nm or less, a commercially available aggregate of 1 to 50 μm is obtained by applying a strong force by mechanical means. That is, br
It can be obtained by an eak- ing down method (a method of pulverizing a bulk material). Ultrasonic,
Mechanical methods such as a high-speed rotation mill, a roller mill, a container driving medium mill, a medium stirring mill, a jet mill, a grinder, and a sand grinder are exemplified. All the average particle diameters referred to in the present invention are the particle diameters observed with an electron microscope (SEM and TEM) (Average Martin diameter; see "Fine Particle Handbook", Asakura Shoten, p. 52, 1991). The average particle size of the primary particles forming the aggregate is preferably from 3 nm to 40 nm. If the primary particle size is small, the absorption capacity may decrease,
Conversely, if it is large, the transparency of the ink recording layer may be reduced.

【0015】粉砕しやすさや分散安定性の面から、非晶
質シリカ、ゼオライト、炭酸カルシウムが好ましい。勿
論、上記に示す方法で得られた分散体以外に、他の市販
各種顔料(例えば:シリカ、コロイダルシリカ、アルミ
ナ、炭酸カルシウム、プラスチックピグメントなど)を
記録層の透明性、光沢性を損なわない範囲で併用しても
よい。これによりインク吸収性を改良することもでき
る。
Amorphous silica, zeolite and calcium carbonate are preferred from the viewpoint of easiness of pulverization and dispersion stability. Of course, in addition to the dispersion obtained by the method described above, other commercially available pigments (eg, silica, colloidal silica, alumina, calcium carbonate, plastic pigment, etc.) may be used in a range that does not impair the transparency and gloss of the recording layer. May be used together. This can also improve the ink absorbency.

【0016】添加されるカチオン樹脂は特に限定するも
のではないが、水溶性或いは水性エマルジョンタイプな
どが好ましく使用される。例えばジシアンジアミド・ホ
ルマリン重縮合物に代表されるジシアン系カチオン樹
脂、ジシアンジアミド・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チオン樹脂、エピクロルヒ
ドリン・ジメチルアミン付加重合物、ジメチルジアリル
アンモニウムクロライド・SO2 共重合物、ジアリルア
ミン塩・SO2 共重合物、ジメチルジアリルアンモニウ
ムクロライド重合物、アリルアミン塩の重合物、ジアル
キルアミノエチル(メタ)アクリレート4級塩重合物、
アクリルアミド−ジアリルアミン塩共重合体等のポリカ
チオン系カチオン樹脂等が挙げられる。なお、カチオン
樹脂の添加量としては顔料100重量部に対し、1〜3
0重量部、より好ましくは3〜20重量部の範囲で調節
される。勿論、粉砕分散前に少量添加して、所望の粒径
になるまで粉砕分散した後、カチオン樹脂を更に追加し
てもよい。カチオン樹脂は単独或いは併用して用いられ
る。その他、一般塗工紙製造において使用される分散
剤、増粘剤、消泡剤、着色剤、帯電防止剤、防腐剤等の
各種助剤が粉砕分散前、粉砕分散中、または粉砕分散後
に適宜添加される。
The cationic resin to be added is not particularly limited, but a water-soluble or aqueous emulsion type is preferably used. For example dicyan cationic resins represented by dicyandiamide-formalin polycondensate, polyamine-based cationic resins represented by dicyandiamide-diethylenetriamine polycondensate, epichlorohydrin-dimethylamine addition polymer, dimethyldiallylammonium chloride-SO 2 copolymer, Diallylamine salt / SO 2 copolymer, dimethyldiallylammonium chloride polymer, allylamine salt polymer, dialkylaminoethyl (meth) acrylate quaternary salt polymer,
A polycationic cation resin such as an acrylamide-diallylamine salt copolymer is exemplified. The amount of the cationic resin added is 1 to 3 with respect to 100 parts by weight of the pigment.
0 parts by weight, more preferably in the range of 3 to 20 parts by weight. Of course, a cationic resin may be further added after adding a small amount before the pulverization / dispersion and pulverization / dispersion until a desired particle size is obtained. The cationic resin is used alone or in combination. In addition, various auxiliaries such as dispersants, thickeners, antifoaming agents, coloring agents, antistatic agents, preservatives, etc. used in the production of general coated paper are appropriately dispersed before grinding, during grinding dispersion, or after grinding dispersion. Is added.

【0017】本発明の記録層に接着剤(バインダー)の
添加が不可欠である。接着剤(バインダー)としては、
水溶性樹脂(たとえばポリビニルアルコール(以下PV
Aと称す)、カゼイン、大豆蛋白、合成タンパク質類、
でんぷん、カルボキシメチルセルロースやメチルセルロ
ース等のセルロース誘導体)、スチレン−ブタジエン共
重合体、メチルメタクリレート−ブタジエン共重合体の
共役ジエン系重合体ラテックス、アクリル系重合体ラテ
ックス、スチレン−酢酸ビニル共重合体等のビニル系共
重合体ラテックスなどの一般に塗工紙に用いられている
公知の接着剤(バインダー)が単独或いは併用して用い
られる。接着剤は水溶性樹脂が好ましい。理由は定かで
はないが、水溶性樹脂はラッテクスと違って、水溶液中
でシリカ等の顔料表面の一部を覆うことが可能であるた
めか、カチオン樹脂がより添加しやすいのではないかと
思われる。接着剤は顔料粉砕分散前・中・後のどの段階
に一部或いは全量を添加してもよいが、好ましくは顔料
粉砕前に一部の接着剤をカチオン樹脂と一緒に顔料中に
添加する。粉砕前の接着剤の添加量は全添加量の5〜5
0%、好ましくは10〜40%である。接着剤を粉砕前
に全量添加すると粉砕中に接着剤が1次粒子間に吸い込
まれ、インク吸収容量が低下する恐れがある。
It is essential to add an adhesive (binder) to the recording layer of the present invention. As an adhesive (binder),
Water-soluble resin (for example, polyvinyl alcohol (hereinafter referred to as PV)
A), casein, soy protein, synthetic proteins,
Starch, cellulose derivatives such as carboxymethylcellulose and methylcellulose), styrene-butadiene copolymer, conjugated diene-based polymer latex of methyl methacrylate-butadiene copolymer, acrylic polymer latex, vinyl such as styrene-vinyl acetate copolymer A known adhesive (binder) generally used for coated paper, such as a system copolymer latex, is used alone or in combination. The adhesive is preferably a water-soluble resin. Although the reason is not clear, it seems that the water-soluble resin, unlike latex, can cover a part of the pigment surface such as silica in the aqueous solution, or the cationic resin may be more easily added. . The adhesive may be partially or entirely added at any stage before, during, or after the pulverization and dispersion of the pigment. Preferably, a part of the adhesive is added to the pigment together with the cationic resin before the pulverization of the pigment. The amount of adhesive added before pulverization is 5-5 of the total amount
0%, preferably 10 to 40%. If the entire amount of the adhesive is added before the pulverization, the adhesive may be sucked between the primary particles during the pulverization, and the ink absorption capacity may be reduced.

【0018】記録層の顔料と接着剤(バインダー)の固
形分重量比は特に限定しないが顔料100重量部に対し
5〜200重量部、好ましくは10〜100重量部の範
囲に調節される。接着剤(バインダー)の添加量が多い
と、粒子間の細孔が小さくなり、インク吸収速度が得ら
れにくい。一方、接着剤(バインダー)が少ないと塗工
層にひび割れが入りやすい。記録層の塗工量は特に限定
するものではないが、1〜100g/m2 、好ましくは
5〜70g/m2 に調節する。少ないと均一塗膜が得ら
れにくく、多くても効果が飽和し、また、塗膜にひび割
れが生じやすくなる。
The weight ratio of the solid content of the pigment and the adhesive (binder) in the recording layer is not particularly limited, but is adjusted in the range of 5 to 200 parts by weight, preferably 10 to 100 parts by weight, per 100 parts by weight of the pigment. If the amount of the adhesive (binder) is large, the pores between the particles become small, and it is difficult to obtain an ink absorption rate. On the other hand, if the amount of the adhesive (binder) is small, the coating layer tends to crack. The coating amount of the recording layer is not particularly limited, 1~100g / m 2, preferably adjusted to 5 to 70 g / m 2. If the amount is small, it is difficult to obtain a uniform coating film, and if the amount is large, the effect is saturated, and the coating film is easily cracked.

【0019】支持体に2層以上の記録層を有する構成で
は、少なくとも1層が上記に示す方法で得られた500
nm以下のコロイド状顔料を含有する層である。他の記
録層の基本的な構成は単層記録層と同様の組成物により
構成される。つまり前記例示された様な顔料と接着剤含
有層や,接着剤として例示した高分子含有層とすること
ができる。本発明の記録層を平滑な成形面に塗工成膜し
た後、支持体或いは他の記録層上に転写するとより優れ
た光沢が得られる。成形面に使用される材料としては、
例えば高表面平滑性を有するセロハン、ポリエチレン、
ポリプロピレン、軟質ポリ塩化ビニル、硬質ポリ塩化ビ
ニル、ポリエステル等のプラスチックフィルム類、ポリ
エチレンラミネート紙、グラシン紙、含浸紙、蒸着紙等
の紙類、金属フォイル、合成紙等可とう性を有するシー
ト類及び無機ガラス、金属、プラスチック等の高平滑表
面を有するドラムや板類が適宜使用される。特に、製造
工程及び成形面と記録層の剥離適性等の観点から、高分
子フィルム(ポリエチレン、ポリプロピレン、ポリエス
テル等)、高平滑表面を有する金属ドラムが好ましい。
In the structure having two or more recording layers on the support, at least one layer is obtained by the method described above.
This is a layer containing a colloidal pigment of nm or less. The basic configuration of the other recording layers is composed of the same composition as the single-layer recording layer. That is, a layer containing a pigment and an adhesive as exemplified above or a layer containing a polymer exemplified as an adhesive can be used. When the recording layer of the present invention is coated on a smooth molding surface and then transferred onto a support or another recording layer, more excellent gloss can be obtained. As the material used for the molding surface,
For example, cellophane with high surface smoothness, polyethylene,
Flexible films such as plastic films such as polypropylene, soft polyvinyl chloride, hard polyvinyl chloride, and polyester; papers such as polyethylene laminated paper, glassine paper, impregnated paper, and vapor-deposited paper; metal foils; synthetic paper; Drums and plates having a highly smooth surface such as inorganic glass, metal, and plastic are appropriately used. In particular, a polymer film (polyethylene, polypropylene, polyester, or the like) or a metal drum having a highly smooth surface is preferable from the viewpoints of the manufacturing process and the suitability for separation between the molding surface and the recording layer.

【0020】成形面は光沢を付与する目的では平滑であ
る方が好ましく、成形面の表面粗さ(JIS B−06
01)は、Raが0.5μm以下が好ましく、より好ま
しくはRaが0.05μm以下である。尚、表面粗さを
コントロールして、セミグロス調、マット調などの風合
いをもたせることも可能である。成形面は無処理のまま
でよいが、記録層と支持体(或いは他の記録層)の接着
力よりも、成形面と記録層の接着力を小さく制御するた
め、成形面の塗工面にシリコーンやフッ素樹脂等の剥離
性を有する化合物を塗工して使用することが可能であ
る。
The molded surface is preferably smooth for the purpose of imparting gloss, and the surface roughness of the molded surface (JIS B-06)
01), Ra is preferably 0.5 μm or less, more preferably Ra is 0.05 μm or less. In addition, it is also possible to give a texture such as semi-gloss tone or matte tone by controlling the surface roughness. The molding surface may be left untreated. However, in order to control the adhesive force between the molding surface and the recording layer to be smaller than the adhesive force between the recording layer and the support (or another recording layer), the coating surface of the molding surface is coated with silicone. It is possible to coat and use a compound having releasability, such as fluorine or a fluororesin.

【0021】本発明の記録層用塗工コーターとしてはブ
レードコーター、エアーナイフコーター、ロールコータ
ー、バーコーター、グラビアコーター、ロッドブレード
コーター、リップコーター、カーテンコーター、ダイコ
ータ等の各種公知の塗工装置またはサイズプレス等の含
浸装置が挙げられる。本発明のインクジェット記録方法
で使用されるインクとしては、像を形成するための色素
と該色素を溶解または分散するための液媒体を必須成分
とし、必要に応じて各種分散剤、界面活性剤、粘度調整
剤、比抵抗調整剤、pH調整剤、防かび剤、記録剤の溶
解または分散安定化剤等を添加して調整される。
Examples of the coating coater for the recording layer of the present invention include various known coating apparatuses such as a blade coater, an air knife coater, a roll coater, a bar coater, a gravure coater, a rod blade coater, a lip coater, a curtain coater, a die coater and the like. An impregnating device such as a size press may be used. As the ink used in the inkjet recording method of the present invention, a dye for forming an image and a liquid medium for dissolving or dispersing the dye are essential components, and various dispersants, surfactants, if necessary, It is adjusted by adding a viscosity adjusting agent, a specific resistance adjusting agent, a pH adjusting agent, a fungicide, a dissolution or dispersion stabilizer of the recording agent, and the like.

【0022】インクに使用される記録剤としては直接染
料、酸性染料、塩基性染料、反応性染料、食用色素、分
散染料、油性染料及び各種顔料等があげられるが、従来
公知のものは特に制限なく使用することができる。この
ような色素の含有量は、液媒体成分の種類、インクに要
求される特性などに依存して決定されるが、本発明にお
けるインクの場合も、従来のインク中におけるような配
合、即ち、0.1〜20重量%程度の割合になるような
使用で特に問題はない。本発明で用いられるインクの溶
媒としては、水及び水溶性の各種有機溶剤、例えば、メ
チルアルコール、エチルアルコール、n−プロピルアル
コール、イソプロピルアルコール、n−ブチルアルコー
ル、イソブチルアルコール等の炭素数1〜4のアルキル
アルコール類、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、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グリ
コール類、エチレングリコール、、ポロピレングリコー
ル、ブチレングリコール、トリエチレングリコール、チ
オジグリコール、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個のアルキレングリ
コール類、ジメチルホルムアミド等のアミド類、テトラ
ヒドロフラン等のエーテル類、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
(エチル)エーテル、トリエチレングリコールモノメチ
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
類などが挙げられる。
Examples of the recording agent used in the ink include direct dyes, acid dyes, basic dyes, reactive dyes, edible dyes, disperse dyes, oil dyes, and various pigments. Can be used without. The content of such a dye is determined depending on the type of the liquid medium component, the characteristics required for the ink, and the like, but in the case of the ink of the present invention, the composition as in the conventional ink, that is, There is no particular problem in use at a ratio of about 0.1 to 20% by weight. Examples of the solvent for the ink used in the present invention include water and various water-soluble organic solvents, for example, having 1 to 4 carbon atoms such as methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, and isobutyl alcohol. Alkyl alcohols, ketones or ketone alcohols such as acetone and diacetone alcohol, polyalkylene glycols such as polyethylene glycol and polypropylene glycol, ethylene glycol, propylene glycol, butylene glycol, triethylene glycol, thiodiglycol, Alkylene glycols having 2 to 6 alkylene groups such as xylene glycol and diethylene glycol, amides such as dimethylformamide, ethers such as tetrahydrofuran, and glycerin Ethylene glycol methyl ether, diethylene glycol methyl (ethyl) ether, lower alkyl ethers of polyhydric alcohols such as triethylene glycol monomethyl ether and the like.

【0023】[0023]

【実施例】以下に実施例を挙げて、本発明をより具体的
に説明するが、勿論これらに限定されるものではない。
また、例中の部及び%は特に断らない限り、水を除いた
固形分であり、それぞれ重量部及び重量%を示す。尚、
分散体粒径測定法は下記による。TEM(透過型電子顕
微鏡、H−300,日立製作所製)により観察した。分
散体を0.5%に薄めた後、コロジオン膜上に滴下し、
風乾した後、観察に用いた。電子顕微鏡倍率は2万倍、
5万倍、10万倍より適宜選択した。
The present invention will be described in more detail with reference to the following Examples, but it should be understood that the present invention is by no means restricted thereto.
Unless otherwise specified, parts and% in the examples are solid contents excluding water, and represent parts by weight and% by weight, respectively. still,
The dispersion particle size measurement method is as follows. Observation was performed with a TEM (transmission electron microscope, H-300, manufactured by Hitachi, Ltd.). After diluting the dispersion to 0.5%, it is dropped on the collodion film,
After air drying, it was used for observation. Electron microscope magnification is 20,000 times,
It was appropriately selected from 50,000 times and 100,000 times.

【0024】実施例1 平均粒径3μの合成非晶質シリカ(日本シリカ工業社
製、商品名:Nipsil HD−2、1次粒子径:1
1nm、以下HD−2とも称す)50部に、水950
部、ポリアクリル酸ナトリウム(東亞合成化学工業社
製、商品名:A−9、以下A−9とも称す)2部を添加
し、ホモミキサーにより分散しながら、カチオン樹脂と
してジアリルジメチルアンモニウムクロライド−アクリ
ルアミド共重合物(日東紡績社製、商品名:PAS−J
−81、以下単にPAS−J−81とも称す)5部を添
加した。続いて、サンドグラインダーにより粉砕分散し
た後、圧力式ホモジナイザーでさらに粉砕分散し、平均
粒子径が120nmになるまでサンドグラインダーと圧
力式ホモジナイザーの粉砕分散操作を繰り返した。得ら
れた水分散体中に予め作成した10%のポリビニールア
ルコール水溶液(クラレ社製、商品名:PVA117、
以下PVA117とも称す)25部(固形分換算、以下
同様)を添加し、均一になるまで攪拌した後、乾燥塗工
量が20g/m2 となるように市販塗工紙(王子製紙社
製、商品名:OKコート、127.9g/m 2 )をラミ
ネートしたもの(エクストルージョンラミネート法によ
り塗工紙表面に15μmのポリエチレンをラミネート加
工したもの、以下単にラミネート塗工紙とも称す)に塗
工乾燥し、本発明のインクジェット記録体を製造した。
Example 1 Synthetic amorphous silica having an average particle size of 3 μm (Nippon Silica Industry Co., Ltd.)
Product name: Nipsil HD-2, primary particle size: 1
1 nm, hereinafter also referred to as HD-2) 50 parts with water 950
Part, sodium polyacrylate (Toagosei Chemical Industry Co., Ltd.)
(Trade name: A-9, hereinafter also referred to as A-9)
And while dispersing with a homomixer,
To diallyldimethylammonium chloride-acryl
Luamide copolymer (trade name: PAS-J, manufactured by Nitto Boseki Co., Ltd.)
-81, hereinafter simply referred to as PAS-J-81).
Added. Then, pulverize and disperse with a sand grinder
After that, further pulverized and dispersed with a pressure homogenizer, average
Sand grinder and pressure until particle size reaches 120nm
The grinding and dispersing operation of the force homogenizer was repeated. Get
10% polyvinyl alcohol in a water dispersion
Aqueous solution of rucol (manufactured by Kuraray, trade name: PVA117
25 parts (in terms of solid content, hereinafter also referred to as PVA117)
Add the same) and stir until uniform, then dry coat
20g / mTwoCommercially available coated paper (Oji Paper Co., Ltd.)
Product name: OK coat, 127.9 g / m TwoLami)
(By extrusion lamination)
15μm polyethylene laminated on the surface of coated paper
(Hereinafter simply referred to as laminated coated paper)
After drying, the ink jet recording medium of the present invention was manufactured.

【0025】実施例2 平均粒径3μの合成非晶質シリカ(日本シリカ工業社
製、商品名:Nipsil HD−2、1次粒子径:1
1nm)50部に、水800部、ポリアクリル酸ナトリ
ウム(東亞合成化学工業社製、商品名:A−9)2部を
添加し、ホモミキサーにより分散しながら、予め作成し
た10%のポリビニルアルコール(クラレ社製、商品
名:PVA117)水溶液5部(固形分換算)、前出の
カチオン樹脂ジアリルジメチルアンモニウムクロライド
−アクリルアミド共重合物(日東紡績社製、商品名:P
AS−J−81)5部を添加した。続いてサンドグライ
ンダーにより粉砕分散した後、圧力式ホモジナイザーで
さらに粉砕分散し、平均粒子径が120nmになるまで
サンドグラインダーと圧力式ホモジナイザーの粉砕分散
操作を繰り返した。得られた水分散体中に予め作成した
上記10%のポリビニールアルコール(PVA−11
7)水溶液20部(固形分換算)を添加し、均一になる
まで攪拌した後、塗工量が20g/m2 となるように前
記と同様のラミネート塗工紙に塗工乾燥し、本発明のイ
ンクジェット記録体を製造した。
Example 2 Synthetic amorphous silica having an average particle diameter of 3 μm (trade name: Nipsil HD-2, manufactured by Nippon Silica Industry Co., Ltd., primary particle diameter: 1)
1 nm) 50 parts of water, 800 parts of water and 2 parts of sodium polyacrylate (trade name: A-9, manufactured by Toagosei Chemical Industry Co., Ltd.) are added, and dispersed with a homomixer, and 10% of polyvinyl alcohol prepared in advance is dispersed. (Kuraray Co., Ltd., trade name: PVA117) 5 parts of an aqueous solution (in terms of solid content), the cationic resin diallyldimethylammonium chloride-acrylamide copolymer (trade name: P, manufactured by Nitto Boseki Co., Ltd.)
AS-J-81). Subsequently, after pulverized and dispersed by a sand grinder, the mixture was further pulverized and dispersed by a pressure homogenizer, and the pulverization and dispersion operation of the sand grinder and the pressure homogenizer was repeated until the average particle diameter became 120 nm. The above 10% polyvinyl alcohol (PVA-11) previously prepared in the obtained aqueous dispersion.
7) After adding 20 parts (in terms of solid content) of an aqueous solution and stirring until the mixture becomes uniform, the mixture was coated on the same laminated coated paper as above so as to have a coating amount of 20 g / m 2 and dried. Was manufactured.

【0026】実施例3 実施例2と同様の塗工液を用い、塗工量が20g/m2
となるようにPETフィルム(東レ社製、ルミラーT、
75μm、表面粗さRa =0.02μm)に塗工乾燥し
た。続いて、温度80℃、線圧:30Kg/cmのカレ
ンダーの条件下で記録層と前記と同様のラミネート塗工
紙のラミネート面が対面するように圧着した後、PET
フィルムを剥がし、本発明のインクジェット記録体を製
造した。 比較例1 平均粒径3μの合成非晶質シリカ(日本シリカ工業社
製、商品名:Nipsil HD−2、1次粒子径:1
1nm)50部に、水950部、ポリアクリル酸ナトリ
ウム(東亞合成化学工業社製、商品名:A−9)2部を
添加し、ホモミキサーにより分散しながら、前出のカチ
オン樹脂(日東紡績社製、商品名:PAS−J−81)
5部、予め作成した10%のポリビニルアルコール(前
出の商品名:PVA117)25部(固形分換算)を添
加した。顔料が均一になるまで攪拌を続き、得られた水
分散体の平均粒子径は3μmであった。この塗料を用
い、塗工量が20g/m2 となるように前記と同様のラ
ミネート塗工紙に塗工乾燥し、インクジェット記録体を
製造した。 比較例2 平均粒径3μの合成非晶質シリカ(日本シリカ工業社
製、商品名:Nipsil HD−2、1次粒子径:1
1nm)50部に、水950部を添加し、サンドグライ
ンダーにより粉砕分散した後、圧力式ホモジナイザーで
さらに粉砕分散し、平均粒子径が120nmになるまで
サンドグラインダーと圧力式ホモジナイザーの分散操作
を繰り返した。得られた水分散体中に予め作成した10
%のポリビニルアルコール(前出の商品名:PVA11
7)25部(固形分換算)と前出のカチオン樹脂(日東
紡績社製、商品名:PAS−J−81)5部を添加し、
塗工液が均一になるまで攪拌し(塗液はカチオン樹脂の
添加により増粘した)、塗工量が20g/m2 となるよ
うに前記と同様のラミネート塗工紙に塗工乾燥し、イン
クジェット記録体を製造した。
Example 3 Using the same coating liquid as in Example 2, the coating amount was 20 g / m 2.
PET film (Lumilar T, manufactured by Toray Industries, Inc.)
(75 μm, surface roughness R a = 0.02 μm). Subsequently, the recording layer was pressure-bonded under the conditions of a calendar at a temperature of 80 ° C. and a linear pressure of 30 Kg / cm so that the laminated surface of the same laminated coated paper as described above faces PET.
The film was peeled off to produce the ink jet recording medium of the present invention. Comparative Example 1 Synthetic amorphous silica having an average particle diameter of 3 μm (manufactured by Nippon Silica Industry Co., Ltd., trade name: Nipsil HD-2, primary particle diameter: 1)
950 parts of water and 2 parts of sodium polyacrylate (trade name: A-9, manufactured by Toagosei Chemical Industry Co., Ltd.) are added to 50 parts of 1 nm), and the above-mentioned cationic resin (Nitto Boseki) is dispersed with a homomixer. (Product name: PAS-J-81)
5 parts, and 25 parts (in terms of solid content) of 10% polyvinyl alcohol (the above-mentioned trade name: PVA117) prepared in advance were added. Stirring was continued until the pigment became uniform, and the average particle diameter of the obtained aqueous dispersion was 3 μm. Using this paint, it was coated on the same laminated coated paper as above so as to have a coating amount of 20 g / m 2 and dried to produce an ink jet recording medium. Comparative Example 2 Synthetic amorphous silica having an average particle diameter of 3 μm (manufactured by Nippon Silica Industry Co., Ltd., trade name: Nipsil HD-2, primary particle diameter: 1)
(1 nm) To 50 parts of water, 950 parts of water was added, and the mixture was pulverized and dispersed by a sand grinder, further pulverized and dispersed by a pressure homogenizer, and the dispersion operation of the sand grinder and the pressure homogenizer was repeated until the average particle diameter became 120 nm. . 10 prepared in advance in the obtained aqueous dispersion.
% Polyvinyl alcohol (the above-mentioned trade name: PVA11)
7) 25 parts (in terms of solid content) and 5 parts of the aforementioned cationic resin (trade name: PAS-J-81, manufactured by Nitto Boseki Co., Ltd.) were added,
The mixture was stirred until the coating liquid became uniform (the coating liquid was thickened by the addition of the cationic resin), and was coated and dried on the same laminated coated paper as described above so that the coating amount was 20 g / m 2 . An ink jet recording medium was manufactured.

【0027】比較例3 平均粒径3μの合成非晶質シリカ(日本シリカ工業社
製、商品名:Nipsil HD−2、1次粒子径:1
1nm)50部に、水950部を添加、サンドグライン
ダーにより粉砕分散した後、圧力式ホモジナイザーでさ
らに粉砕分散し、平均粒子径が120nmになるまでサ
ンドグラインダーと圧力式ホモジナイザーの粉砕分散操
作を繰り返した。得られた水分散体に予め作成した10
%のポリビニルアルコール(前出の商品名:PVA11
7)25部(固形分換算)を添加し、塗工量が20g/
2 となるように前記と同様のラミネート塗工紙に塗工
乾燥し、インクジェット記録体を製造した。
Comparative Example 3 Synthetic amorphous silica having an average particle diameter of 3 μm (manufactured by Nippon Silica Industry Co., Ltd., trade name: Nipsil HD-2, primary particle diameter: 1)
1 nm) 950 parts of water was added to 50 parts, pulverized and dispersed by a sand grinder, further pulverized and dispersed by a pressure homogenizer, and the pulverization and dispersion operation of the sand grinder and the pressure homogenizer was repeated until the average particle diameter became 120 nm. . 10 prepared in advance in the obtained aqueous dispersion
% Polyvinyl alcohol (the above-mentioned trade name: PVA11)
7) 25 parts (in terms of solid content) were added, and the coating amount was 20 g /
It was coated and dried on the same laminated coated paper as described above so as to obtain m 2 , thereby producing an ink jet recording medium.

【0028】[評価方法]実施例、比較例で得られたイ
ンクジェット記録体のインク吸収性、光沢性、印字耐水
性等は以下に示す方法で評価した。光沢性とインク吸収
性については市販のインクジェットプリンター(キヤノ
ン社製、商標:BJC−600J)で記録を行った場合
のベタ部分の光沢度、インク吸収性、印字濃度を示す。 [印字耐水性]インクジェット用記録体に印字した後、
24時間放置後、水滴を落とし、30分後に水滴を拭き
取り、水滴に浸漬されたの状況を観察する。(○:イン
クの滲みが殆どなかった。△:インクの滲みがあり、印
字部の濃度が薄くなった。×:インクが殆どとれた。)
[Evaluation Methods] The ink absorbency, glossiness, print water resistance and the like of the ink jet recording materials obtained in Examples and Comparative Examples were evaluated by the following methods. The gloss and the ink absorbency indicate the gloss, ink absorbency, and print density of a solid portion when recording is performed with a commercially available inkjet printer (trade name: BJC-600J, manufactured by Canon Inc.). [Water resistance to printing] After printing on an inkjet recording medium,
After standing for 24 hours, water drops are dropped, and after 30 minutes, the water drops are wiped off, and the state of immersion in the water drops is observed. (A: There was almost no ink bleeding. B: There was ink bleeding, and the density of the printed portion was low. C: Most of the ink was removed.)

【0029】[インク吸収性]イエロー、マゼンタ、シ
アンの各単色を印字し、印字直後から5秒毎にプリント
した印字面に上質紙を貼合せ、インクが上質紙に転写す
るかどうかを観察する。(○:10秒未満、△:10〜
30秒、×:30秒以上)。インクが乾燥するまでの時
間が10秒未満のものはインク吸収性に優れる。
[Ink Absorbency] Print each single color of yellow, magenta, and cyan, attach fine wood to the printed surface every 5 seconds immediately after printing, and observe whether the ink is transferred to the fine wood. . (○: less than 10 seconds, Δ: 10
30 seconds, x: 30 seconds or more). When the time until the ink dries is less than 10 seconds, the ink absorbency is excellent.

【0030】[印字濃度]黒ベタ部の印字濃度をマクベ
ス反射濃度計(Macbeth、RD−920)を用い
て測定した。表中に示した数字は5回測定の平均値であ
る。 [印字部の光沢感(照り感)]印字部の光沢感は印字部
に対して20°の横角度から目視し、以下のように4段
評価した。 ◎:銀塩方式のカラー写真と同レベルの照り感がある。 ○:カラー写真よりは劣るが、高い照り感がある。 △:塗工紙印刷品並。 ×:一般PPC並。
[Print Density] The print density of the solid black portion was measured using a Macbeth reflection densitometer (Macbeth, RD-920). The numbers shown in the table are the average values of five measurements. [Glossiness of print portion (shininess)] The glossiness of the print portion was visually observed from a lateral angle of 20 ° with respect to the print portion, and evaluated in four steps as follows. :: There is the same level of shine as a silver halide color photograph. :: Inferior to color photograph, but with high shine. Δ: comparable to coated paper print product. X: comparable to general PPC.

【0031】[0031]

【表1】 [Table 1]

【0032】[0032]

【発明の効果】表1から明らかなように、本発明の構成
により得られたインクジェット記録体はインク吸収性が
良好で、かつ印字後も光沢性、印字濃度、耐水性とも優
れるインクジェット記録体である。
As is evident from Table 1, the ink jet recording medium obtained by the constitution of the present invention is an ink jet recording medium having good ink absorbability and excellent gloss, print density and water resistance even after printing. is there.

Claims (4)

【特許請求の範囲】[Claims] 【請求項1】支持体に顔料含有塗液を塗布若しくは含浸
してなるインクジェット記録体であり、該塗液が、凝集
体顔料をカチオン樹脂含有液中で粉砕分散し凝集体平均
粒径を500nm以下とした顔料を含有する塗液である
ことを特徴とするインクジェット記録体。
1. An ink jet recording material comprising a support and a pigment-containing coating liquid applied or impregnated thereon, wherein the coating liquid is obtained by pulverizing and dispersing an aggregate pigment in a cationic resin-containing liquid to have an average particle diameter of 500 nm. An ink jet recording material, which is a coating liquid containing a pigment described below.
【請求項2】カチオン樹脂含有液が更に水溶性樹脂を含
む請求項1記載のインクジェット記録体。
2. The ink jet recording medium according to claim 1, wherein the cationic resin-containing liquid further contains a water-soluble resin.
【請求項3】凝集体顔料が非晶質シリカを含む請求項1
または2記載のインクジェット記録体。
3. The method of claim 1, wherein the aggregate pigment comprises amorphous silica.
Or the ink-jet recording material according to 2.
【請求項4】支持体に記録層を設けたインクジェット記
録体の製造方法において、少なくとも1層の記録層は顔
料を含有し、成形面に塗工成膜された後、支持体上に
(或いは他の記録層が既に支持体上に設けられている場
合は、その記録層上に)転写されるインクジェット記録
体の製造方法であり、且つ前記顔料は凝集体顔料をカチ
オン樹脂含有液中で粉砕分散し、凝集体平均粒径を50
0nm以下とした顔料であることを特徴とするインクジ
ェット記録体の製造方法。
4. A method for producing an ink jet recording medium having a recording layer provided on a support, wherein at least one recording layer contains a pigment, and after being coated and formed on a molding surface, is formed on the support (or If another recording layer is already provided on the support, the method is a method for producing an ink jet recording material to be transferred onto the recording layer), and the pigment is obtained by grinding an aggregate pigment in a liquid containing a cationic resin. Disperse, and agglomerate average particle size is 50
A method for producing an ink jet recording material, which is a pigment having a diameter of 0 nm or less.
JP8347736A 1996-12-26 1996-12-26 Ink jet recording medium and its manufacture Pending JPH10181190A (en)

Priority Applications (5)

Application Number Priority Date Filing Date Title
JP8347736A JPH10181190A (en) 1996-12-26 1996-12-26 Ink jet recording medium and its manufacture
EP97310557A EP0850777B1 (en) 1996-12-26 1997-12-23 Methods of making ink jet recording material
DE69707631T DE69707631T2 (en) 1996-12-26 1997-12-23 Manufacturing method of an ink jet recording material
US08/997,881 US5958168A (en) 1996-12-26 1997-12-24 Ink jet recording material and method of producing same
US09/664,740 US6270837B1 (en) 1996-12-26 2000-09-19 Ink jet recording material and method of producing same

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP8347736A JPH10181190A (en) 1996-12-26 1996-12-26 Ink jet recording medium and its manufacture

Related Child Applications (1)

Application Number Title Priority Date Filing Date
JP2002227199A Division JP3680824B2 (en) 2002-08-05 2002-08-05 Dispersion-stabilized coating liquid for ink jet recording body and ink jet recording body using the same

Publications (1)

Publication Number Publication Date
JPH10181190A true JPH10181190A (en) 1998-07-07

Family

ID=18392244

Family Applications (1)

Application Number Title Priority Date Filing Date
JP8347736A Pending JPH10181190A (en) 1996-12-26 1996-12-26 Ink jet recording medium and its manufacture

Country Status (1)

Country Link
JP (1) JPH10181190A (en)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1251013A2 (en) 2001-04-19 2002-10-23 Fuji Photo Film Co., Ltd. Inkjet recording sheet
EP1306226A2 (en) 2001-10-26 2003-05-02 Fuji Photo Film Co., Ltd. Ink-jet recording sheet
EP1491351A1 (en) 2003-06-27 2004-12-29 Mitsubishi Paper Mills Limited Ink-jet recording material and method for preparing the same
JP2005220010A (en) * 2004-01-07 2005-08-18 Mitsubishi Paper Mills Ltd Silica dispersion liquid and inkjet recording material obtained by using the same
EP1396526A3 (en) * 2002-09-09 2006-06-07 Oji Paper Company Limited Aqueous dispersion comprising inorganic pigment-cationic resin composite fine particles and ink jet recording material containing same
DE112004002698T5 (en) 2004-02-03 2008-09-04 Mitsubishi Paper Mills Limited Ink jet recording material
US8257803B2 (en) 2007-09-07 2012-09-04 Fujifilm Corporation Inkjet recording medium and inkjet recording method

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1251013A2 (en) 2001-04-19 2002-10-23 Fuji Photo Film Co., Ltd. Inkjet recording sheet
US6777039B2 (en) 2001-04-19 2004-08-17 Fuji Photo Film Co., Ltd. Inkjet recording sheet
EP1306226A2 (en) 2001-10-26 2003-05-02 Fuji Photo Film Co., Ltd. Ink-jet recording sheet
EP1396526A3 (en) * 2002-09-09 2006-06-07 Oji Paper Company Limited Aqueous dispersion comprising inorganic pigment-cationic resin composite fine particles and ink jet recording material containing same
EP1491351A1 (en) 2003-06-27 2004-12-29 Mitsubishi Paper Mills Limited Ink-jet recording material and method for preparing the same
JP2005220010A (en) * 2004-01-07 2005-08-18 Mitsubishi Paper Mills Ltd Silica dispersion liquid and inkjet recording material obtained by using the same
JP4648708B2 (en) * 2004-01-07 2011-03-09 三菱製紙株式会社 Silica dispersion
DE112004002698T5 (en) 2004-02-03 2008-09-04 Mitsubishi Paper Mills Limited Ink jet recording material
US8257803B2 (en) 2007-09-07 2012-09-04 Fujifilm Corporation Inkjet recording medium and inkjet recording method

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