JP2008095089A - Ink for inkjet recording, ink set for inkjet recording, ink-medium set for inkjet recording, ink cartridge, inkjet-recording method, inkjet recording apparatus - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an ink for inkjet recording having high ejection stability and storage stability, capable of inexpensively obtaining printed matter like commercially printed matter, an ink set, an ink medium set, an ink cartridge, an inkjet recording method and an inkjet recording apparatus. <P>SOLUTION: The ink for inkjet recording for recording on a substrate including a cellulose pulp as the principal component comprises water, a water-soluble organic solvent, a water dispersible resin (A) and a pigment (P1) as a coloring agent (B). Its surface tension at 25°C is 20 to 35 mN/m and its viscosity at 25°C is 5 mPa s or higher. The ink contains one or more kinds of a fluorine-based surfactant and/or a silicon-based surfactant as the surfactant. (A) and (B) are present in the ink by 5 to 40 wt.% in total, and the weight ratio (A)/(B) of (A) and (B) is 0.5 to 4. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  INK JET RECORDING INK, INK JET RECORDING INK SET, INK JET RECORDING INK-MEDIA SET, INK CARTRIDGE, INK JET RECORDING METHOD The present invention relates to an ink jet recording apparatus.

  Inkjet recording is known as an excellent recording method in which a recording material is not relatively selected, and research and development have been actively conducted on recording apparatuses, recording methods, recording materials, and the like. However, inks for inkjet recording have so far mainly used water as a main component and water-based dyes. This is because it is easy to obtain color materials with a high extinction coefficient and high color purity, and it is easy to make multiple colors of ink to widen the color specification range, as well as long-term ink storage stability and ink stability against heat. In particular, it is also mainstream in the current ink jet recording because it has various advantages that it is possible to make ink that is less likely to cause kogation.

  On the other hand, conventional inkjet paper, especially inkjet glossy media, can be classified into a swollen type and a void type, but recently, a void type that is excellent in ink drying speed has become mainstream. This gap type is mainly provided with an ink absorbing layer having a gap for taking ink on a substrate, and further provided with a porous glossy layer if necessary. As disclosed in Patent Document 1 (Japanese Patent Laid-Open No. 2005-212327) and Patent Document 2 (Japanese Patent Laid-Open No. 11-78225), a coating liquid in which silica or alumina hydrate is dispersed is further applied on a substrate. Alternatively, it is obtained by applying a plurality of layers and applying a gloss layer containing a large amount of colloidal silica as required. This type of paper is designed with an emphasis on matching with the mainstream dye inks, and is already widely used as inkjet paper, especially glossy paper. When these papers are used, high-definition output with high gloss can be obtained, but on the other hand, the raw materials are very expensive and the manufacturing process is complicated, so the manufacturing cost is also comparable to that of general glossy coated paper for commercial printing. Then it is very expensive. For this reason, applications tend to be limited to cases where high-quality output is required, such as photo output, and it is difficult to use in commercial printing fields that require a large amount of output at low cost, such as flyers, catalogs, and brochures. It is. In recent years, the number of colors of ink used for printing for further image quality tends to increase, and the required ink absorption capacity tends to increase. In order to increase the ink absorption capacity of the media, it is sufficient to increase the thickness of the ink receiving layer (coat layer). However, as the thickness is increased, an expensive material is used and the unit price of the media is increased.

As the pigment constituting the ink absorbing layer (receiving layer), a material having a small refractive index and low concealability, that is, a material capable of keeping the transparency of the layer high and having a large oil absorption (specific surface area) is used. There is a need. Therefore, at present, not a cheap white pigment such as calcium carbonate or kaolin, but an expensive low refractive index and high oil absorption pigment such as silica or alumina hydrate must be used in a large amount. This is because if a pigment with low transparency and high concealability is used in the ink absorbing layer, the color material in the ink soaked in the ink absorbing layer is concealed by these highly concealing pigments, and the concentration is expressed. It is because it will not do. In fact, when ink-jet printing with a dye ink on paper using such a highly concealed pigment, the density is low only as a result of the color material existing near the surface layer no matter how much the amount of ink to be applied is increased. The image will not have contrast. If a material having a small oil absorption amount is used, the ink cannot be absorbed in time and beading is likely to occur.
For these reasons, recently, the use of organic fine particles having a small refractive index as disclosed in Patent Document 3 (Japanese Patent Laid-Open No. 2003-25717) has been attempted to achieve both refractive index and whiteness. However, the production cost of organic fine particles is also high, and it is still difficult to obtain an inexpensive receiving paper that matches the dye ink.

The design concept for the long-term storage stability of the resulting image is also low in resistance to dye molecules themselves, ultraviolet rays and ozone. In addition, the mainstream is to protect the dye with an antioxidant or stabilizer previously added to the image receiving layer of the media. For this reason, the penetration depth is secured (compensated) by using a large amount of ink having a relatively low color material density, and image reliability is maintained. Accordingly, the amount of ink necessary for outputting an image naturally increases, and it is difficult not only to reduce the size of the cartridge, but also to increase the printing cost.
In view of the above, in inkjet recording, it is very difficult to provide inexpensive dedicated paper or a printing method capable of high-quality output.

  On the other hand, in recent years, pigment inks for inkjet recording have attracted attention. Since pigments are insoluble in water, it is common to use fine particles that are dispersed in a solvent. However, pigment inks for inkjet are pigment inks in which pigments are dispersed in water from the viewpoint of safety. Is the mainstream. In general, water-based pigment inks tend to cause aggregation and precipitation of pigment particles compared to dye inks, and various dispersion conditions and additives are necessary to achieve long-term storage stability comparable to dye inks. In addition to being difficult to use with a thermal head because of the cause of gating, the colorant color range of color materials is inferior to that of dyes. From the viewpoint of storage stability and water resistance, much attention has been paid. Ink jet printers using this pigment ink may have the color material of ink close to that of general commercial printing ink, and the texture of the printed material can be brought close to that of commercial printing. When printing on coated paper for commercial printing with ink, the drying of the ink will not be in time, and due to this poor drying property, the image will blur, the pigment will not fix at all after drying, rubbing will occur, etc. Similarly, the reality is that it can only deal with printing on media with high ink absorbability such as plain paper and inkjet paper. This is because the design philosophy relating to the formation of inkjet images is not different from the philosophy of using dye inks, and color material pigments are only taken from the viewpoint of dyes with high light resistance. This is because no consideration is given.

JP 2005-212327 A Japanese Patent Application Laid-Open No. 11-078225 JP 2003-025717 A

The present invention has been made in order to solve the following problems in view of the above circumstances.
That is, the object of the present invention is to adopt a selective combination of the specific inkjet recording medium and the specific inkjet pigment ink shown in the present invention, so that the print quality is low, the print quality is good, the density, the gloss Ideal ink jet recording ink, ink jet recording ink set, ink jet recording excellent in reliability such as excellent image reliability, printed matter close to commercial printed matter, and high ejection stability and storage stability An ink media set, an ink cartridge, an ink jet recording method, and an ink jet recording apparatus are provided.

The above problems are solved by the present invention described below.
(1) “At least one surface or both surfaces on a support mainly composed of cellulose pulp has a single layer or multiple layers of a colorant pigment permeation preventive layer (barrier layer), and the barrier layer has a refractive index of 1. A pigment containing at least 30% by weight or more of an inorganic pigment (P2) other than 5 or more of alumina hydrate, and having a pigment (P2) content of less than 1.5 in the barrier layer of 10% by weight or less An ink for ink jet recording suitable for ink jet recording on an ink jet recording medium for ink, comprising pigment (P1) as water, a water-soluble organic solvent, a water dispersible resin (A) and a colorant (B) Ink-jet recording ink comprising a surface tension at 25 ° C. of 20 to 35 mN / m and a viscosity at 25 ° C. of 5 mPa · s or more. Containing at least one kind of a basic surfactant and / or a silicon surfactant, the water-dispersible resin (A) and the colorant (B) are present in the ink in a total amount of 5 to 40% by weight, and Ink for inkjet recording, wherein the weight ratio (A) / (B) of the water dispersible resin (A) and the colorant (B) is from 0.5 to 4, "
(2) The above-mentioned (1), wherein the water-dispersible resin (A) contains at least one of an anionic self-emulsifying ether polyurethane resin emulsion and an acrylic-silicone resin emulsion. Ink-jet recording ink according to item ",
(3) “Inkjet recording according to item (1) or (2), wherein the fluorosurfactant has the following structural formula (1) or (2): For ink:

（式中、Ｒｆはフッ素含有基を表わす。ｍ，ｎ，及びｐは整数を表わす。）

(In the formula, Rf represents a fluorine-containing group. M, n, and p represent integers.)

（式中、ｍ^１は０〜１０の整数を表わし、ｎ^１は１〜４０の整数を表わす。）」、
（４）「前記シリコン系界面活性剤が下記構造式（３）を有するものであることを特徴とする前記第（１）項又は第（２）項に記載のインクジェット記録用インク：

(Wherein m ¹ represents an integer of 0 to 10 and n ¹ represents an integer of ¹ to 40) ”,
(4) “Ink for ink jet recording according to item (1) or (2), wherein the silicon-based surfactant has the following structural formula (3):

（式中、ｍ^２，ｎ^２，ａ及びｂは整数を表わす。Ｒは置換若しくは無置換のアルキル基、又はアリール基を表わす。）」、
（５）「前記水溶性有機溶剤が、グリセリン、トリメチロールプロパン、エチレングリコール、ジエチレングリコール、トリエチレングリコール、プロピレングリコール、ジプロピレングリコール、トリプロピレングリコール、１，３−ブタンジオール、２，３−ブタンジオール、１，４−ブタンジオール、３−メチル−１，３−ブタンジオール、１，５−ペンタンジオール、１，６−ヘキサンジオール、２−メチル−２，４−ヘキサンジオール、２−ピロリドン、Ｎ−メチル−２−ピロリドン、Ｎ−ヒドロキシエチル−２−ピロリドン、テトラメチル尿素、尿素の中から選ばれた少なくとも１種類以上であることを特徴とする前記第（１）項乃至第（４）項のいずれかに記載のインクジェット記録用インク」、
（６）「前記インクジェット記録用インクが、ブラックインクとカラーインクとからなることを特徴とするインクジェット記録用インクセット」、
（７）「インクジェット記録用インクと、インクジェット記録メディアとのインクジェット記録用インクメディアセットであって、該インクは、水、水溶性有機溶剤、水分散性樹脂（Ａ）および着色剤（Ｂ）として顔料（Ｐ１）を含んでなり、かつ、２５℃における表面張力が２０〜３５ｍＮ／ｍ、２５℃における粘度が５ｍＰａ・ｓ以上であり、該インク中に、界面活性剤としてフッ素系界面活性剤及び／又はシリコン系界面活性剤を一種類以上含有し、前記水分散性樹脂（Ａ）および着色剤（Ｂ）は、インク中に合計５〜４０重量％存在し、かつ、水分散性樹脂（Ａ）と着色剤（Ｂ）の重量比率（Ａ）／（Ｂ）が０．５〜４のインクであり、該インクジェット記録メディアは、セルロースパルプを主成分とした支持体上の少なくとも一方の面又は両面に、一層もしくは多層の色材顔料浸透防止層（バリア層）を有し、該バリア層は、屈折率１．５以上のアルミナ水和物以外の無機顔料（Ｐ２）を少なくとも３０重量％以上含有し、かつ該バリア層中の屈折率１．５未満の顔料の含有率が１０重量％以下の記録メディアであることを特徴とするインクジェット記録用インク―メディアセット」、
（８）「前記第（１）項乃至第（５）項のいずれかに記載のインク又は前記第（６）項に記載のインクセットを容器中に収容してなることを特徴とするインクカートリッジ」、
（９）「前記第（７）項に記載のインクジェット記録用インク―メディアセットを用いるインクジェット記録方法であって、１５ｇ／ｍ^２以下のインク付着量で記録することを特徴とするインクジェット記録方法」、
（１０）「前記インクに刺激を印加し、該インクを飛翔させて前記記録メディアに画像を形成するインク飛翔工程を少なくとも含むことを特徴とする前記第（９）項に記載のインクジェット記録方法」、
（１１）「前記刺激が、熱、圧力、振動及び光から選択される少なくとも１種であることを特徴とする前記第（１０）項に記載のインクジェット記録方法」、
（１２）「水、水溶性有機溶剤、水分散性樹脂（Ａ）および着色剤（Ｂ）として顔料（Ｐ１）を含んでなり、かつ、２５℃における表面張力が２０〜３５ｍＮ／ｍ、２５℃における粘度が５ｍＰａ・ｓ以上であり、該インク中に、界面活性剤としてフッ素系界面活性剤及び／又はシリコン系界面活性剤を一種類以上含有し、前記水分散性樹脂（Ａ）および着色剤（Ｂ）は、インク中に合計５〜４０重量％存在し、かつ、水分散性樹脂（Ａ）と着色剤（Ｂ）の重量比率（Ａ）／（Ｂ）が０．５〜４のインクジェット記録用インクと、セルロースパルプを主成分とした支持体上の少なくとも一方の面又は両面に、一層もしくは多層の色材顔料浸透防止層（バリア層）を有し、該バリア層は、屈折率１．５以上のアルミナ水和物以外の無機顔料（Ｐ２）を少なくとも３０重量％以上含有し、かつ該バリア層中の屈折率１．５未満の顔料の含有率が１０重量％以下のインクジェット記録メディアと、該インクジェット記録用インクを収納せるインクカートリッジとを搭載し、該インクジェット記録用インクを該記録メディアに向けて飛翔させ１５ｇ／ｍ^２以下のインク付着量で印字するインク飛翔手段を有することを特徴とするインクジェット記録装置」、
（１３）「前記第（１）項乃至第（５）項のいずれかに記載のインクジェット記録用インク又は前記第（６）項に記載のインクジェット記録用インクセットを、記録ヘッドから液滴として吐出させて用紙に画像を記録する装置であって、該用紙が、セルロースパルプを主成分とした支持体上の少なくとも一方の面又は両面に、一層もしくは多層の色材顔料浸透防止層（バリア層）を有し、該バリア層は、屈折率１．５以上のアルミナ水和物以外の無機顔料（Ｐ２）を少なくとも３０重量％以上含有し、かつ該バリア層中の屈折率１．５未満の顔料の含有率が１０重量％以下のインクジェット記録メディアであり、該用紙を反転させて両面印刷可能とするユニットを備えることを特徴としたインクジェット記録装置」。

(Wherein m ² , n ² , a and b represent integers. R represents a substituted or unsubstituted alkyl group or an aryl group) ”
(5) "The water-soluble organic solvent is glycerin, trimethylolpropane, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,3-butanediol, 2,3-butanediol. 1,4-butanediol, 3-methyl-1,3-butanediol, 1,5-pentanediol, 1,6-hexanediol, 2-methyl-2,4-hexanediol, 2-pyrrolidone, N- Item (1) to Item (4), characterized in that it is at least one selected from methyl-2-pyrrolidone, N-hydroxyethyl-2-pyrrolidone, tetramethylurea and urea. Ink for ink-jet recording according to any one of "
(6) "Inkjet recording ink set, wherein the inkjet recording ink comprises a black ink and a color ink",
(7) “Inkjet recording ink media set of inkjet recording ink and inkjet recording medium, wherein the ink is used as water, a water-soluble organic solvent, a water-dispersible resin (A), and a colorant (B). A pigment (P1), a surface tension at 25 ° C. of 20 to 35 mN / m, a viscosity at 25 ° C. of 5 mPa · s or more, and a fluorosurfactant as a surfactant in the ink; And / or one or more types of silicon surfactants, the water-dispersible resin (A) and the colorant (B) are present in the ink in a total amount of 5 to 40% by weight, and the water-dispersible resin (A ) And the colorant (B) in a weight ratio (A) / (B) of 0.5 to 4, and the ink jet recording medium is at least one on a support mainly composed of cellulose pulp. One or multiple layers of colorant pigment permeation preventive layer (barrier layer) are provided on the surface or both surfaces, and the barrier layer contains at least 30 wt.% Of inorganic pigment (P2) other than alumina hydrate having a refractive index of 1.5 or more. Ink for ink-jet recording, wherein the content of the pigment having a refractive index of less than 1.5 in the barrier layer is 10% by weight or less ”,
(8) An ink cartridge comprising the container according to any one of the items (1) to (5) or the ink set according to the item (6). "
(9) “Inkjet recording method using the ink-recording ink-media set according to item (7), wherein recording is performed with an ink adhesion amount of 15 g / m ² or less” ,
(10) “Inkjet recording method according to item (9), including at least an ink flying step of applying a stimulus to the ink and causing the ink to fly to form an image on the recording medium” ,
(11) “The inkjet recording method according to (10), wherein the stimulus is at least one selected from heat, pressure, vibration, and light”;
(12) “Water, a water-soluble organic solvent, a water-dispersible resin (A) and a colorant (B) containing the pigment (P1), and a surface tension at 25 ° C. of 20 to 35 mN / m, 25 ° C. The ink has a viscosity of 5 mPa · s or more, and the ink contains at least one fluorine-based surfactant and / or silicon-based surfactant as a surfactant, and the water-dispersible resin (A) and the colorant (B) is a total of 5 to 40% by weight in the ink, and the weight ratio (A) / (B) of the water-dispersible resin (A) to the colorant (B) is 0.5 to 4 At least one surface or both surfaces of a recording ink and a support mainly composed of cellulose pulp have a single layer or multiple layers of a colorant pigment permeation preventive layer (barrier layer), and the barrier layer has a refractive index of 1 .5 or more inorganic pigments other than alumina hydrate (P ) At least 30% by weight and the content of the pigment having a refractive index of less than 1.5 in the barrier layer is 10% by weight or less, and an ink cartridge for storing the ink for ink jet recording An ink jet recording apparatus comprising: an ink jetting unit that is mounted and jets the ink for ink jet recording toward the recording medium and performs printing with an ink adhesion amount of 15 g / m ² or less;
(13) “Ejecting the inkjet recording ink according to any one of (1) to (5) or the inkjet recording ink set according to (6) as droplets from a recording head An apparatus for recording an image on a sheet, wherein the sheet is a single layer or multiple layers of a colorant pigment permeation preventive layer (barrier layer) on at least one surface or both surfaces on a support mainly composed of cellulose pulp. And the barrier layer contains at least 30% by weight or more of an inorganic pigment (P2) other than alumina hydrate having a refractive index of 1.5 or more, and the pigment having a refractive index of less than 1.5 in the barrier layer An ink jet recording apparatus comprising: a unit that is an ink jet recording medium having a content ratio of 10% by weight or less, and capable of performing duplex printing by inverting the paper.

  According to the present invention, conventional problems can be solved, and by combining the ink jet recording medium and the ink jet ink shown in the present invention, the cost is low, the print quality is good, and the density, gloss, and image reliability are excellent. Ink-jet recording ink, ink-jet recording ink set, ink-jet recording ink-media set, ink with excellent reliability, such as high-ejection stability and storage stability. A cartridge, an ink jet recording method, and an ink jet recording apparatus can be provided.

  The ink jet recording ink, ink jet recording ink set, ink jet recording ink-media set, ink cartridge, ink jet recording method, and ink jet recording apparatus of the present invention will be described in detail below.

[Recording media]
First, with regard to media, in general, ink-jet-coated paper (ink-jet media) for realizing high-quality images has an ink receiving layer (coat layer) formed of an inorganic pigment (P2), or the vicinity thereof. And the ink receiving layer itself is designed to form an image by absorbing ink (ink permeation). This is closely related to the fact that inkjet recording technology has been developed mainly for dye inks.

  The dye in the liquid is originally a coloring material that presupposes that it penetrates into affinity substances and binds to them (covalent bond, ionic bond, van der Waals bond), whereas pigment in ink (P1) has no bonding force (or small) and needs to be bonded by an adhesive (binder). Accordingly, in the case of ink jet recording using dye ink, the receiving layer substance is only “dyed”. In order to obtain a high-definition and high-quality image by creating a technical idea of how to uniformly dye the receiving layer using inkjet ink and how much more receiving layer material can be dyed. In addition, a technique for making the receptor layer soaked, a technique for binding to the receptor layer substance more firmly, and a technique for achieving both ink absorbability and color development have been developed.

  As mentioned above, the current mainstream of inkjet paper is a method for realizing a porous, highly transparent absorption layer. To achieve this, a material with a low refractive index and a large specific surface area is inevitably used. In the present situation, it is necessary to rely on expensive materials such as silica and alumina hydrate and very elaborate manufacturing methods. Of course, the printing cost is very expensive, and it is difficult to apply to mass printing.

  In view of the above, we have conducted intensive research on a low-cost inkjet recording method, and combined a specific pigment ink with high penetrability with a specific medium with low ink absorbency, which is the opposite of conventional methods. As a result, a low-cost image forming method based on a new design concept has been invented.

  In other words, printing is performed using a small amount of ultra-high-penetration pigment ink on a recording medium in which ink absorption (penetration) is suppressed so that the colorant pigment (P1) in the ink does not penetrate as much as possible. Only the solvent to be formed (water or organic solvent) is selectively soaked into the support, and only the coloring material (pigment) in the ink is efficiently retained on the surface of the media, so that even with a small amount of ink, sufficient concentration and drying properties can be obtained. It was found that both can be achieved.

  In addition, the medium of which the ink absorbency is controlled to be low according to the present invention is provided with a specific colorant pigment permeation preventive layer (barrier layer) on a support mainly composed of cellulose pulp, that is, a so-called paper substrate (for example, applied). ). By making this barrier layer resemble the appearance of a printing paper, it is possible to obtain a printed material that is close to the texture of a general commercial printed material. In order to suppress the permeability of the ink, it has been found that arbitrary permeability (barrier properties) can be obtained by limiting the pore size, diameter, thickness, etc. of the barrier layer.

  This barrier layer needs to have a certain thickness or less in order to promote separation of the colorant pigment (P1) and the ink solvent in the ink, and the thickness needs to be 10 μm or less, more preferably 5 μm. The following is desirable. If it is thicker than this, it takes time for the ink solvent to permeate, and beading, bleeding and the like are likely to occur, and image quality is lowered, and the drying property is deteriorated, so that offset and the like are likely to occur. In addition, on the necessity of making the barrier layer thin, in order to prevent color material show-through (the color of the printed color material can be seen through the back side) and the like, in contrast to conventional inkjet media in the barrier layer, It is necessary to contain a large amount of inorganic pigment having a high refractive index and a high hiding property. To this end, it is necessary to contain 30% by weight or more of an inorganic pigment (P2) having a refractive index of 1.5 or more in the layer. The barrier layer may contain silica, which is a low-refractive-index material with low concealment properties used in conventional ink jet media. However, when a large amount of highly transparent pigment (P2) is contained, the settling is worsened. However, in order to increase the cost, the amount of silica or the like needs to be 10% by weight or less. From the above, by using a white pigment having a high refractive index as the white pigment constituting the barrier layer, it is possible to reduce the set-off even when the barrier layer thickness is reduced, and to further reduce the cost. I found it.

  There are some alumina hydrates as pigments with a high refractive index, but if they contain too much oil absorption such as alumina hydrate, the ink solvent will not easily migrate from the barrier layer to the substrate. . Alumina hydrate that has absorbed a large amount of solvent is not desirable in the present invention because it causes blurring of the image due to discoloration or pigment migration during long-term storage.

  The function required for the barrier layer in the present invention is to separate the pigment (P1) and the solvent in the ink and to allow only the solvent to penetrate into the substrate. For this purpose, the barrier layer has micropores (pores). It is desirable. If there is no pore in the barrier layer, the penetration of the solvent component in the ink becomes slow, and the phenomenon that the ink does not dry easily occurs. However, if the pore diameter is too large or the number of pores is too large, the function of separating the colorant pigment (P1) in the ink will be reduced, resulting in a decrease in image density, or the color present on the media surface after printing. The material pigment (P1) migrates inside the media over time, causing a color change. Therefore, the pore diameter needs to be 1 μm or less, and the area of the pore on the media surface is preferably 40% or less.

  The measurement of the bore diameter and the area occupied by the pore can be performed by surface observation by SEM imaging. Based on the surface photograph, the image of the pore portion is binarized, and the diameter and area ratio can be obtained. In the present invention, JEM Electrolytic Radiation Scanning Electron Microscope JSM-7400F was used as the SEM, and Pop Imaging (Ver. 3.51) (with) Digital Being Kids was used for image processing.

[ink]
Further, the ink conditions essential for the present invention must be very penetrable, the surface tension at 25 ° C. is 20 to 35 mN / m, and the viscosity at 25 ° C. is 5 mPa · s or more. The ink contains at least one fluorine-based surfactant and / or silicon-based surfactant as a surfactant, and the water-dispersible resin (A) and the colorant (B) are added to the ink in total. It was found that 5 to 40% by weight and the weight ratio (A) / (B) of the water-dispersible resin (A) and the colorant (B) was 0.5 to 4.

In the following, the components of the ink essential to the present invention will be described.
In the ink of the present invention, the weight ratio of the colorant (B) to the water-dispersible resin (A) is kept low, and one type of fluorosurfactant and / or silicon surfactant is used as the surfactant. By containing the above, improving wettability and permeability, and by containing at least one or more of an anionic self-emulsifying ether polyurethane resin emulsion and an acrylic-silicone resin emulsion in the water-dispersible resin. The printed material close to commercial printing with high fixability to the inexpensive medium of the present invention is achieved by a combination of specific ink and specific media.

The water-dispersible resin (A) that can be used in the present invention can be suitably used by at least one selected from a polyurethane resin emulsion and an acrylic-silicone resin emulsion, or a combination thereof, and can be used as an ink adjustment raw material. Or after the ink preparation of the present invention, it exists as an O / W type emulsion.
When at least one selected from the above is used, these emulsions are present in the ink in a total amount of 1 to 40% by weight, preferably 1 to 20% by weight.

  In polyurethane resin emulsions, normal polyurethane resins that are relatively hydrophilic are emulsified using an emulsifier on the outside, and functional groups that function as an emulsifier are introduced into the resin itself by means such as copolymerization. There is an emulsion type emulsion. In the combination of the pigment (P1) that can be used in the ink of the present invention, an anionic self-emulsifying type polyurethane resin emulsion is always excellent in dispersion stability. In this case, the polyurethane resin is preferably an ether type rather than a polyester type or a polycarbonate type in terms of fixability and dispersion stability of the pigment (P1). The reason is not clear, but many non-ether types have poor solvent resistance, and tend to cause aggregation and increase in viscosity when the ink is stored at high temperature.

  The average particle diameter of the ether polyurethane resin emulsion is 300 nm or less, preferably 100 nm, more preferably 80 nm or less. In particular, by setting the average particle size to 100 nm or less, the reliability of the ink jet printer, such as the stability of ink ejection after being left for a long time, is improved.

  The glass transition point of the ether polyurethane resin emulsion is preferably in the range of −50 ° C. to 150 ° C. More preferably, it is the range of -10 degreeC-100 degreeC. The reason is not clear, but when the glass transition point exceeds 150 ° C, the film formation property of the ether polyurethane resin emulsion is glassy and hard, but the pigment particles and the ether polyurethane resin emulsion land on the image support at the same time. On the other hand, the scratch resistance of the printed part is surprisingly fragile. On the other hand, at 150 ° C. or lower, the film formation property of the ether polyurethane resin emulsion is rubbery and soft, but it can be excellent in scratch resistance. However, when the temperature is lower than −50 ° C., the film is too soft and the scratch resistance is inferior. From the above points, with the same addition amount, the glass transition point is −50 ° C. to 150 ° C. from the viewpoint of scratch resistance of the printed matter. The range of was found to be preferable. In addition, the glass transition point of resin as used in the field of this invention can be measured with the measuring method of either DSC (differential scanning calorimeter) or TMA (thermomechanical analysis).

The ether polyurethane resin emulsion preferably has a minimum film-forming temperature of room temperature or lower, more preferably 25 ° C. or lower. When the film formation of the ether polyurethane resin emulsion is carried out at room temperature or lower, particularly 25 ° C. or lower, the binding of paper fibers automatically proceeds without any special treatment such as heating or drying of the image-formed image support. This is preferable.
Here, the “minimum film-forming temperature (MFT)” means that the aqueous emulsion particles obtained by dispersing the ether-based polyurethane resin emulsion particles in water are thinly cast on a metal plate such as aluminum to raise the temperature. Is defined as the lowest temperature at which a transparent continuous film is formed.

Next, the acrylic-silicone resin emulsion that can be used in the present invention will be described.
The acrylic-silicone resin emulsion of the present invention is a silicon-modified acrylic resin emulsion that can be obtained by polymerizing an acrylic monomer and a silane compound in the presence of an emulsifier.
As acrylic monomers, acrylic acid ester monomers such as methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate, acryloylmorpholine, N, N′-dimethylaminoethyl acrylate, Methacrylic acid ester monomers such as methyl methacrylate, ethyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, 2-hydroxyethyl methacrylate, N, N′-dimethylaminoethyl methacrylate, N-methylolacrylamide, methoxymethylacrylamide, etc. And carboxylic acid-containing monomers such as maleic acid acrylate, maleic acid, fumaric acid, itaconic acid, acrylic acid and methacrylic acid.

  Examples of the emulsifier of the present invention include alkylbenzene sulfonic acid or its salt, dialkyl sulfosuccinic acid ester or its salt, alkyl naphthalene sulfonic acid or its salt, formalin condensate of alkyl naphthalene sulfonate, higher fatty acid salt, higher fatty acid Ester sulfonate, ethylenediamine polyoxypropylene-polyoxyethylene condensate, sorbitan fatty acid ester or salt thereof, aromatic or aliphatic phosphate ester or salt thereof, dodecylbenzene sulfonate, dodecyl sulfate, lauryl sulfate , Dialkylsulfosuccinate, polyoxyethylene alkylphenyl ether sulfate, polyoxyethyne alkylpropenyl phenyl ether sulfate, alkylphenyl ether disulfonate, polyoxyethylene Alkyl phosphate, polyoxyethylene alkyl ether acetate, polyoxyethylene lanolin alcohol ether, polyoxyethylene lanolin fatty acid ester, lauryl alcohol ethoxylate, lauryl ether sulfate ester, lauryl ether phosphate ester, sorbitan fatty acid ester, fatty acid diethanolamine And a formalin condensate of naphthalene sulfonic acid. Here, examples of the salt include sodium and ammonium.

  Moreover, the reactive emulsifier which has an unsaturated double bond can also be used as an emulsifier of this invention. Examples of reactive emulsifiers include Adekari Soap SE, NE, PP (Asahi Denka Kogyo), Latemul S-180 (Kao), Eleminol JS-2, Eleminol RS-30 (Sanyo Kasei Kogyo), Aqualon RN-20 ( Daiichi Kogyo Seiyaku) and the like.

Examples of the silane compound of the present invention include tetramethoxysilane, methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, diphenyldimethoxysilane, tetraethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, and phenyltriethoxysilane. , Diphenyldiethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, decyltrimethoxysilane, decyltrimethoxysilane, trifluoropropyltrimethoxysilane, and the like.
Moreover, the monomer generally known as a silane coupling agent can also be used, for example, vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, p-styryltrimethoxysilane, 3 -Methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, -methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, N-2 (aminoethyl) ) 3-aminopropylmethyldimethoxysilane, N-2 (aminoethyl) 3-aminopropyltrimethoxysilane, N-2 (aminoethyl) 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-amino Propyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, N-phenyl-3-aminopropyltrimethoxysilane, N- (vinylbenzyl) -2-aminoethyl-3 Aminopropyltrimethoxysilane hydrochloride, 3-ureidopropyltriethoxysilane, 3-chloropropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, bis (triethoxysilylpropyl) tetra Examples thereof include sulfide and 3-isocyanatopropyltriethoxysilane.

  In the present invention, the hydrolyzable silyl group is a silyl group containing a hydrolyzable group. Examples of the hydrolyzable group include an alkoxy group, a mercapto group, a halogen group, an amide group, an acetoxy group, an amino group, and an isopropenoxy group. Groups and the like.

  The silyl group is hydrolyzed to become a silanol group, and the silanol group is dehydrated and condensed to form a siloxane bond. In the silicon-modified acrylic resin used in the ink of the present invention, it is preferable that the hydrolyzable silyl group disappears by hydrolysis through a polymerization reaction. If the hydrolyzable silyl group remains, the storage stability when used as an ink is deteriorated, which is not preferable.

  The average particle diameter of the resin fine particles is preferably 10 nm to 300 nm, more preferably 40 nm to 200 nm. When the average particle size is synthesized so as to be less than 10 nm, the viscosity of the resin emulsion increases, and it becomes difficult to obtain an ink viscosity that can be ejected by a printer. When the average particle diameter exceeds 300 nm, particles are clogged in the nozzles of the printer, resulting in ejection failure.

  The amount of silicon derived from the silicon-modified acrylic resin contained in the ink of the present invention is preferably 100 ppm or more and 400 ppm or less. When the amount of silicon is less than 100 ppm, a coating film excellent in scratch resistance and marker resistance cannot be obtained, and when the amount of silicon is more than 400 ppm, the tendency to hydrophobicity increases and the stability in aqueous ink decreases.

  The minimum film-forming temperature of the silicon-modified acrylic resin used in the ink of the present invention is preferably 20 ° C. or lower. If the minimum film forming temperature is higher than 20 ° C., sufficient fixability cannot be obtained. That is, if the print portion is rubbed or traced with a marker, the pigment is removed and the print medium is soiled.

Next, the water-dispersible resin (A) and the colorant (B) of the present invention are present in the ink in a total amount of 5 to 40% by weight, and the water-dispersible resin (A) and the colorant (B). An explanation will be given below regarding the weight ratio (A) / (B) being 0.5 to 4.
High fixability with respect to inexpensive media used in the present invention and printed matter close to commercial printed matter can be achieved by the combination of the specific ink and specific media described in this specification. As an important constituent requirement, the present invention finds that the total solid content and ratio of the water-dispersible resin (A) and the colorant (B) in the ink are essential requirements for achieving the object. It was.

  In other words, the total solid content must be 5 to 40% by weight in the ink, and if it is less than 5% by weight, it is insufficient for the media used in the present invention, such as fixability. If the amount exceeds 40% by weight, the viscosity becomes too high, which adversely affects reliability such as ink ejection properties. More preferably, it is 5 to 20% by weight. Depending on the type of the color material described later, resin dispersion and resin-coated pigment can also be used, and the resin dispersant and coating resin at that time are also the above water-dispersible resin (A ) And the resin solid content (A).

  In addition, regarding the weight ratio (A) / (B) of the water-dispersible resin (A) and the colorant (B) being 0.5 to 4, the media used in this patent is less than 0.5. This is because, for example, the fixing property is insufficient, and if it is larger than 4, the density of the coloring material with respect to the resin is too low, resulting in a decrease in image quality such as a decrease in density and a decrease in image uniformity. For this reason, with respect to the media used in the present invention, the water-dispersible resin (A) and the colorant (B) are 5 to 40 weights in total in the ink as an important constituent element of the ink used in the present invention. %, And the weight ratio (A) / (B) of the water-dispersible resin (A) and the colorant (B) is 0.5 to 4.

Next, components constituting the ink of the present invention and the composition thereof will be described.
Specific examples of the water-soluble organic solvent of the present invention include the following.
Ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, tetraethylene glycol, polyethylene glycol, polypropylene glycol, 1,3-butanediol, 2-methyl-1,3-butanediol, 3- Methyl-1,3-butanediol, 2,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, glycerol, 1,2,6-hexanetriol, 1, Polyhydric alcohols such as 2,4-butanetriol, 1,2,3-butanetriol, 2-methyl-2,4-pentanediol, petriol, 3-methoxy-3-methyl-1-butanediol;
Polyhydric alcohol alkyl ethers such as ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, tetraethylene glycol monomethyl ether, propylene glycol monoethyl ether;
Polyhydric alcohol aryl ethers such as ethylene glycol monophenyl ether, ethylene glycol monobenzyl ether, dipropylene glycol monobutyl ether, tripropylene glycol monobutyl ether, diethylene glycol isobutyl ether, triethylene glycol isobutyl ether, diethylene glycol isopropyl ether;
Nitrogen-containing heterocyclic compounds such as 2-pyrrolidone, N-methyl-2-pyrrolidone, N-hydroxyethyl-2-pyrrolidone, 1,3-dimethylimidazolidinone, ε-caprolactam, γ-butyrolactone;
Amides such as formamide, N-methylformamide, N, N-dimethylformamide;
Amines such as monoethanolamine, diethanolamine, triethanolamine, monoethylamine, diethylamine, triethylamine;
Sulfur-containing compounds such as dimethyl sulfoxide, sulfolane, thiodiethanol, thiodiglycol;
Propylene carbonate, ethylene carbonate and the like.

  Among these organic solvents, glycerin, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,3-butanediol, 2-methyl-1,3-butanediol, 3-methyl -1,3-butanediol, 2,3-butanediol, 1,4-butanediol, 1,5-pentanediol, tetraethylene glycol, 1,6-hexanediol, 2-methyl-2,4-pentanediol Polyethylene glycol, 1,2,4-butanetriol, 1,2,6-hexanetriol, thiodiglycol, 2-pyrrolidone, N-methyl-2-pyrrolidone, N-hydroxyethyl-2-pyrrolidone, 1, 3-dimethyl-2-imidazolidinone is preferred Arbitrariness. These are excellent in solubility and prevention of poor jetting characteristics due to water evaporation.

The pigment ink essential to the present invention contains at least water, a particulate colorant, a colorant fixing agent, and a water-soluble organic solvent, and includes a wetting agent, a surfactant, and, if necessary, other Contains ingredients.
In particular, for the purpose of the present invention, the use of a fluorine-based and / or silicon-based surfactant as a surfactant, and the weight ratio of the colorant (B) to the water-dispersible resin (A) are kept low. In addition, the water-dispersible resin contains at least one kind of anionic self-emulsifying type ether polyurethane resin emulsion and acrylic-silicone resin emulsion, so that it has high fixability to the inexpensive medium of the present invention. Prints close to commercial prints are achieved with the combination of ink and media.
It was found that the weight ratio (A) / (B) of the colorant (B) to the water-dispersible resin (A) is 0.5 to 4, more preferably 1 to 3.

Examples of the colorant (B) include dyes such as oil-soluble dyes and disperse dyes, and pigment (P1). In the present invention, a pigment (P1) having good water resistance and weather resistance is used.
Examples of the pigment (P1) used in the present invention include carbon black as a black pigment, and examples of the color pigment include anthraquinone, phthalocyanine blue, phthalocyanine green, diazo, monoazo, pyranthrone, perylene, heterocyclic yellow, quinacridone and (thio). ) Indigoid included. Representative examples of phthalocyanine blue include copper phthalocyanine blue and its derivatives (Pigment Blue 15). Representative examples of quinacridone include Pigment Orange 48, Pigment Orange 49, Pigment Red 122, Pigment Red 192, Pigment Red 202, Pigment Red 206, Pigment Red 207, Pigment Red 209, Pigment Violet 19 and Pigment Violet 42. Representative examples of anthraquinones include pigment red 43, pigment red 194 (perinone red), pigment red 216 (brominated pyrantrone red) and pigment red 226 (pyrantron red). Representative examples of pyrerin are Pigment Red 123 (Bell Million), Pigment Red 149 (Scarlet), Pigment Red 179 (Maroon), Pigment Red 190 (Red), Pigment Violet, Pigment Red 189 (Yellow Shade Red) and Pigment Red. 224. Representative examples of thioindigoid include Pigment Red 86, Pigment Red 87, Pigment Red 88, Pigment Red 181, Pigment Red 198, Pigment Violet 36 and Pigment Violet 38. Representative examples of heterocyclic yellow include pigment yellow 117 and pigment yellow 138. Examples of other suitable colored pigments are described in The Color Index, 3rd edition (The Society of Dyers and Colorists, 1982).

  In the pigment (P1) used in the ink of the present invention, at least one hydrophilic group is bonded to the pigment surface directly or through another atomic group, and can be stably dispersed without using a dispersant. Pigments that can be used can be used. As the pigment having a hydrophilic group introduced on the surface thereof used in the present invention, those having ionicity are preferable, and those having an anionic charge or those having a cationic charge are suitable.

Examples of the anionic hydrophilic group, for _{example, -COOM, -SO 3 M, -PO} 3 HM, -PO 3 M 2, -SO 2 NH 2, -SO 2 NHCOR ( where, M in the formula is a hydrogen atom, R represents an alkyl group having 1 to 12 carbon atoms, a phenyl group which may have a substituent, or a naphthyl group which may have a substituent. It is done. In the present invention, it is particularly preferable to use those in which —COOM and —SO ₃ M are bonded to the pigment surface. Examples of a method for obtaining an anionically charged pigment include a method of oxidizing a pigment with sodium hypochlorite, a method of sulfonation, and a method of reacting a diazonium salt, but the present invention is not limited thereto. I don't mean.

  For example, a quaternary ammonium group can be used as the hydrophilic group bonded to the surface of the color pigment charged with a cation. More preferably, a pigment in which at least one of the quaternary ammonium groups listed below is bonded to the pigment surface is used.

In the pigment (P1) used in the ink of the present invention, a pigment dispersion in which a pigment is dispersed in an aqueous medium with a dispersant can also be used. As a preferable dispersant, a known dispersant used for preparing a pigment dispersion can be used, and examples thereof include the following.
Polyacrylic acid, polymethacrylic acid, acrylic acid-acrylonitrile copolymer, vinyl acetate-acrylic acid ester copolymer, acrylic acid-acrylic acid alkyl ester copolymer, styrene-acrylic acid copolymer, styrene-methacrylic acid copolymer Polymer, styrene-acrylic acid-alkyl acrylate ester copolymer, styne-methacrylic acid-alkyl acrylate copolymer, styrene-α-methylstyrene-acrylic acid copolymer, styrene-α-methylstyrene-acrylic Acid copolymer-alkyl acrylate ester copolymer, styrene-maleic acid copolymer, vinyl naphthalene-maleic acid copolymer, vinyl acetate-ethylene copolymer, vinyl acetate-fatty acid vinyl ethylene copolymer, vinyl acetate -Maleic acid ester copolymer, vinyl acetate Rotonic acid copolymer, vinyl acetate-acrylic acid copolymer, etc.

  Further, the nonionic or anionic activator dispersant used to disperse the pigment (P1) can be appropriately selected according to the pigment type or the ink formulation, but the nonionic surfactant is polyoxyethylene lauryl ether. , Polyoxyethylene myristyl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene alkyl ethers such as polyoxyethylene oleyl ether, polyoxyethylene such as polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether Alkyl phenyl ether, polyoxyethylene α-naphthyl ether, polyoxyethylene β-naphthyl ether, polyoxyethylene monostyryl phenyl ether, polyoxyethylene disty Examples include rylphenyl ether, polyoxyethylene alkyl naphthyl ether, polyoxyethylene monostyryl naphthyl ether, polyoxyethylene distyryl naphthyl ether, polyoxyethylene polyoxypropylene block copolymer, and the like. Also used are surfactants in which a part of polyoxyethylene in the above surfactant is replaced with polyoxypropylene, and surfactants condensed with a compound having an aromatic ring such as polyoxyethylene alkylphenyl ether with formalin. it can.

  The HLB of the nonionic surfactant is preferably from 12 to 19.5, more preferably from 13 to 19. If the HLB is less than 12, the compatibility of the surfactant with the dispersion medium is poor and the dispersion stability tends to deteriorate. If the HLB exceeds 19.5, the surfactant is difficult to adsorb on the pigment (P1). Again, the dispersion stability tends to deteriorate.

  Anionic surfactants include polyoxyethylene alkyl ether sulfate, polyoxyethylene alkyl phenyl ether sulfate, polyoxyethylene monostyryl phenyl ether sulfate, polyoxyethylene distyryl phenyl ether sulfate, polyoxyethylene alkyl ether phosphorus Acid salt, polyoxyethylene alkyl phenyl ether phosphate, polyoxyethylene monostyryl phenyl ether phosphate, polyoxyethylene distyryl phenyl ether phosphate, polyoxyethylene alkyl ether carboxylate, polyoxyethylene alkyl phenyl ether Carboxylate, polyoxyethylene monostyryl phenyl ether carboxylate, polyoxyethylene distyryl phenyl ether carboxylate, naphthalene Phosphonate formalin condensate, melanin sulfonate formalin condensate, dialkyl sulfosuccinate ester salt, sulfosuccinic acid alkyl disalt, polyoxyethylene alkyl sulfosuccinic acid disalt, alkyl sulfoacetate, α-olefin sulphonate, alkylbenzene sulfone Acid salts, alkylnaphthalene sulfonates, alkyl sulfonates, N-acyl amino acid salts, acylated peptides, soaps, and the like. Among these, polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxy Particularly preferred is the sulfate or phosphate of ethylene distyryl phenyl ether.

  The addition amount of the surfactant-based dispersant is preferably 10% by weight or more and 50% by weight or less of the pigment (P1). When the addition amount of the surfactant-based dispersant is less than 10% by weight of the pigment (P1), the storage stability of the pigment dispersion and the ink is lowered or the dispersion takes an extremely long time. Since the viscosity of the liquid becomes too high, the discharge stability tends to decrease.

Furthermore, a resin-coated colorant can also be suitably used as the colorant (B), which will be described below.
It consists of a polymer emulsion in which a polymer fine particle contains a water-insoluble or hardly soluble coloring material. In the present specification, “containing a color material” means either or both of a state in which a color material is enclosed in polymer fine particles and a state in which the color material is adsorbed on the surface of the polymer fine particles. In this case, it is not necessary that all of the color material blended in the ink of the present invention is encapsulated or adsorbed in the polymer fine particles, and the color material is dispersed in the emulsion as long as the effect of the present invention is not impaired. Also good. The coloring material is not particularly limited as long as it is water-insoluble or hardly water-soluble and can be adsorbed by the polymer. In this specification, water-insoluble or poorly water-soluble means that the coloring material does not dissolve 10 parts by weight or more with respect to 100 parts by weight of water at 20 ° C. This means that no separation or sedimentation is observed. Examples of the coloring material include dyes such as oil-soluble dyes and disperse dyes, pigments, and the like. Oil-soluble dyes and disperse dyes are preferable from the viewpoint of good adsorption and encapsulation, but pigments are preferably used from the light resistance of the obtained image.

In addition, the colorant used in the present invention is preferably dissolved in an organic solvent, for example, a ketone solvent in an amount of 2 g / liter or more, preferably 20 to 600 g / liter from the viewpoint of efficiently impregnating the polymer fine particles. Is more preferable. As the polymer that forms the polymer emulsion, for example, vinyl polymers, polyester polymers, polyurethane polymers, and the like can be used. Particularly preferred polymers are vinyl polymers and polyester polymers, and specific examples thereof include those disclosed in JP-A Nos. 2000-53897 and 2001-139849. Moreover, 10-200 mass parts is preferable with respect to 100 mass parts of said polymers, and, as for the compounding quantity of the said coloring agent, 25-150 mass parts is more preferable. The average particle diameter of the polymer fine particles containing the colorant is preferably 0.16 μm or less in the ink.
The content of the polymer fine particles is preferably 8 to 20% by mass, more preferably 8 to 12% by mass in solid content in the recording ink.

An example of the water-soluble dye of the present invention is shown below. Those having excellent water resistance and light resistance are preferably used.
Specific examples of these dyes include acid dyes and food dyes such as C.I. I. Acid Yellow 17, 23, 42, 44, 79, 142; C.I. I. Acid Red 1, 8, 13, 14, 18, 26, 27, 35, 37, 42, 52, 82, 87, 89, 92, 97, 106, 111, 114, 115, 134, 186, 249, 254 289; I. Acid Blue 9, 29, 45, 92, 249; I. Acid Black 1, 2, 7, 24, 26, 94; I. Food Yellow 3, 4; I. Food red 7, 9, 14; I. Food black 1, 2 etc. are mentioned.
Examples of direct dyes include C.I. I. Direct yellow 1, 12, 24, 26, 33, 44, 50, 86, 120, 132, 142, 144; I. Direct red 1, 4, 9, 13, 17, 20, 28, 31, 39, 80, 81, 83, 89, 225, 227; I. Direct orange 26, 29, 62, 102; I. Direct Blue 1, 2, 6, 15, 22, 25, 71, 76, 79, 86, 87, 90, 98, 163, 165, 199, 202; I. Direct black 19, 22, 32, 38, 51, 56, 71, 74, 75, 77, 154, 168, 171 and the like can be mentioned.
Examples of basic dyes include C.I. I. Basic yellow 1, 2, 11, 13, 14, 15, 19, 21, 23, 24, 25, 28, 29, 32, 36, 40, 41, 45, 49, 51, 53, 63, 64, 65, 67, 70, 73, 77, 87, 91; C.I. I. Basic Red 2, 12, 13, 14, 15, 18, 22, 23, 24, 27, 29, 35, 36, 38, 39, 46, 49, 51, 52, 54, 59, 68, 69, 70, 73, 78, 82, 102, 104, 109, 112; I. Basic blue 1, 3, 5, 7, 9, 21, 22, 26, 35, 41, 45, 47, 54, 62, 65, 66, 67, 69, 75, 77, 78, 89, 92, 93, 105, 117, 120, 122, 124, 129, 137, 141, 147, 155; I. Basic black 2, 8 etc. are mentioned.
Examples of reactive dyes include C.I. I. Reactive black 3, 4, 7, 11, 12, 17; I. Reactive yellow 1,5,11,13,14,20,21,22,25,40,47,51,55,65,67; I. Reactive Red 1, 14, 17, 25, 26, 32, 37, 44, 46, 55, 60, 66, 74, 79, 96, 97; I. Reactive blue 1, 2, 7, 14, 15, 23, 32, 35, 38, 41, 63, 80, 95 etc. are mentioned.

In the present invention, the wettability and penetrability to the recording paper can be remarkably improved by using a surfactant, particularly a fluorine-based and / or silicon-based surfactant in the ink.
Fluorosurfactants include perfluoroalkyl sulfonates, perfluoroalkyl carboxylates, perfluoroalkyl phosphates, perfluoroalkyl ethylene oxide adducts, perfluoroalkyl betaines, perfluoroalkylamine oxide compounds, etc. However, commercially available fluorine-based compounds include Surflon S-111, S-112, S-113, S121, S131, S132, S-141, and S-145 (manufactured by Asahi Glass Co., Ltd.), Fullrad FC. -93, FC-95, FC-98, FC-129, FC-135, FC-170C, FC-430, FC-431, FC-4430 (manufactured by Sumitomo 3M Limited), MegaFuck F-470, F-1405 , F474 (Dainippon Ink Chemical Co., Ltd.), Zonyl Can be used in S-300, FSN, (manufactured by Du Pont) FSN-100, FSO, EFTOP EF-351,352,801,802 (manufactured by JEMCO Co., Ltd.) is readily available present invention. Among these, Zonyl FS-300, FSN, FSN-100, and FSO (manufactured by DuPont), which are particularly excellent in reliability and color development, can be preferably used.

  More preferably, the fluorosurfactant represented by the following structural formulas (1) and (2) has high fixability and commercial properties for the inexpensive media of the present invention due to the properties of wettability and permeability. A printed matter close to a printed matter is achieved by a combination of ink and media using the above-mentioned fluorosurfactant.

（式中、Ｒｆはフッ素含有基を表わす。ｍ，ｎ，及びｐは整数を表わす。）

(In the formula, Rf represents a fluorine-containing group. M, n, and p represent integers.)

（式中、ｍ^１は０〜１０の整数を表わし、ｎ^１は１〜４０の整数を表わす。）

(In the formula, m ¹ represents an integer of 0 to 10, and n ¹ represents an integer of ¹ to 40.)

  The silicon surfactant is particularly preferably a linear block copolymer in which dimethylpolysiloxane and polyalkylene oxide represented by the following structural formula (3) are alternately and repeatedly bonded. Dow Corning Silicone Co., Ltd. can be easily obtained and used in the present invention.

（式中、ｍ^２，ｎ^２，ａ及びｂは整数を表わす。Ｒは置換若しくは無置換のアルキル基、又はアリール基を表わす。）
前記界面活性剤は、単独または二種以上を混合して用いることができる。

(In the formula, m ² , n ² , a and b represent integers. R represents a substituted or unsubstituted alkyl group or an aryl group.)
The surfactants can be used alone or in admixture of two or more.

  Further, surfactants that can be used in combination with the above fluorine-based and / or silicon-based surfactants include interfacial polyoxyethylene alkyl ether acetate, dialkyl sulfosuccinate, polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl. Examples include ethers, polyoxyethylene polyoxypropylene block copolymers, polyoxyethylene alkyl esters, polyoxyethylene sorbitan fatty acid esters, and acetylene glycol surfactants. More specifically, as the anionic surfactant, polyoxyethylene alkyl ether acetate and / or dialkylsulfosuccinic acid having a branched alkyl chain of 5 to 7 carbon chains can be used to improve wettability with respect to plain paper. It becomes good. Further, the surfactants mentioned here can exist stably in the ink of the present invention without inhibiting the dispersion state.

  Examples of the polyol having 7 to 11 carbon atoms used as a penetrant in the present invention include 2-ethyl-1,3-hexanediol and 2,2,4-trimethyl-1,3-pentanediol. The addition amount is preferably 0.1% to 20% by weight, more preferably 0.5% to 10% by weight. If the amount added is less than the lower limit, the ink will have poor penetrability to the paper, and will be rubbed by rollers during transport, causing smudges, or when reversing for double-sided printing, ink will adhere to the transport belt and smear will occur. Or high-speed printing or double-sided printing. If the addition amount is greater than or equal to the upper limit, the print dot diameter increases, the line width of the characters becomes wider, and the image sharpness decreases.

Examples of the additive include an antifungal agent, an antirust agent, and a pH adjuster.
By using 1,2-benzisothiazolin-3-one as an antifungal agent, it is possible to provide an ink having an excellent antifungal effect while ensuring reliability such as storage stability and ejection stability. In particular, in combination with the wetting agent of the present invention, even if the addition amount is conventionally difficult to suppress the generation of bacteria and sputum, the effect can be sufficiently exerted, by suppressing the addition amount In addition, since phenomena such as particle aggregation and ink thickening can be prevented, ink performance can be exhibited over a long period of time. The amount of 1,2-benzisothiazolin-3-one added is preferably 0.01 to 0.04 parts by weight of the total amount of ink as the active ingredient. If it is less than 0.01 part by weight, the anti-mold property is slightly lowered. In the case of 0.04 parts or more, particle aggregation occurs when the ink is stored for a long period of time (for example, 2 years at room temperature, 1 to 3 months at 50 to 60 ° C.), or the ink viscosity is initial. Long-term storage stability problems such as a 50% to 100% increase in viscosity occur, and the initial printing performance cannot be maintained.

As the pH adjuster, any substance can be used as long as the pH can be adjusted to 7 or more without adversely affecting the ink to be prepared.
Examples include amines such as diethanolamine and triethanolamine, hydroxides of alkali metal elements such as lithium hydroxide, sodium hydroxide, and potassium hydroxide, ammonium hydroxide, quaternary ammonium hydroxide, and quaternary phosphonium. Other examples include aminopropanediol derivatives such as hydroxides, carbonates of alkali metals such as lithium carbonate, sodium carbonate, and potassium carbonate. Aminopropanediol derivatives are water-soluble organic basic compounds such as 1-amino-2,3-propanediol, 1-methylamino-2,3-propanediol, 2-amino-2-methyl-1, Examples include 3-propanediol and 2-amino-2-ethyl-1,3-propanediol, and 2-amino-2-ethyl-1,3-propanediol is a preferred example.

Examples of the rust inhibitor include acidic sulfite, sodium thiosulfate, ammonium thiodiglycolate, diisopropylammonium nitrite, pentaerythritol tetranitrate, and dicyclohexylammonium nitrite.
Depending on the purpose, a water-soluble ultraviolet absorber, a water-soluble infrared absorber, or the like can be added.

[Inkjet recording]
In the present invention, it is necessary to strictly limit the total amount of ink in order to prevent the colorant from penetrating into the ink and efficiently distribute it in the vicinity of the surface of the medium while ensuring the drying property of the ink. When a large amount of ink is used as in conventional inkjet recording, the colorant pigment separation ability of the barrier layer cannot catch up, and the ink colorant pigment penetrates along with the ink solvent, or the solvent component of the ink penetrates. This is because it is not in time and drastically hinders drying. It has been found that the maximum total amount of ink required to exhibit the function of the barrier layer is 15 g / m ² , desirably 12 g / m ² or less. The amount of ink can be easily adjusted by the amount of penetrant (EHD) and the amount of fluorine-based surfactant added. Also, by reducing the total amount of ink required for printing, the capacity of the ink cartridge can be reduced compared to conventional ink jet printers, and the apparatus can be made compact. Further, if the cartridge size is the same as the conventional one, the replacement frequency of the ink cartridge can be reduced, and printing at a lower cost is possible. Basically, the smaller the total amount of ink, the more effective the pigment separation ability of the barrier layer is. However, if the amount is too small, there is a side effect that the image dot diameter after printing becomes too small. It is desirable to set the total amount of ink within this range.

In the present invention, the total amount of ink was measured using a gravimetric method. Specifically, a 5 cm × 20 cm rectangle was printed on Type 6200 (manufactured by Ricoh), which is PPC paper, the weight was measured immediately after printing, the weight before printing was subtracted, and the value was multiplied by 100 to obtain the total amount of ink.
The highly penetrating ink of the present invention can also be printed on conventional void-type inkjet dedicated media. However, since the ink absorption speed is too high compared with the case of printing on the recording medium of the present invention, the solvent penetrates before the dots spread out after the ink droplets have landed on the medium surface, and the dot diameter becomes small. End up. As a result, a decrease in density and an increase in graininess are likely to occur. Therefore, in order to create a high-quality image, it is necessary to print at a higher resolution than that of the recording medium of the present invention, resulting in a decrease in printing speed and an increase in ink consumption. Therefore, it is preferable to use the recording medium of the present invention.

[Recording media]
Examples of the inorganic pigment (P2) of the barrier layer used in the present invention include magnesium carbonate, talc, kaolin, illite, clay, calcium carbonate, calcium sulfite, titanium white, magnesium carbonate, and titanium dioxide. Among these pigments (P2), the thickness of the barrier layer can be reduced by using a pigment having a refractive index as high as possible. However, from the viewpoint of cost, it is preferable to use calcium carbonate or kaolin. These pigments can be used in combination as long as the effects of the present invention are not impaired, and can also be used in combination with other pigments not listed. Kaolin is preferable because it has excellent glossiness and can have a texture close to that of paper for offset printing. Kaolin includes delaminated kaolin, calcined kaolin, engineered kaolin by surface modification, etc., but considering gloss development, the proportion of particle size of 2 μm or less has a particle size distribution of 80% by weight or more. It is desirable that kaolin accounts for 50% by weight or more of the entire kaolin. The blending amount of kaolin is preferably 50 parts by weight or more. If it is less than 50 parts by weight, it is difficult to expect a sufficient effect on the glossiness. The upper limit is not particularly limited, but considering the fluidity of kaolin, particularly thickening under high shear force, less than 90 parts by weight is more preferable from the viewpoint of coating suitability.

  These high refractive index pigments (P2) may be used in combination with low refractive index silica or organic pigments. Examples of organic pigments include water-soluble dispersions such as styrene / acrylic copolymer particles, styrene / butadiene copolymer particles, polystyrene particles, and polyethylene particles. Two or more of these organic pigments may be mixed. Since organic pigments are excellent in glossiness and their specific gravity is smaller than inorganic pigments, a coating layer with high bulkiness and high glossiness and good surface coverage can be obtained. If the amount is less than 5 parts by weight, the above effect is not achieved, and if it exceeds 5 parts by weight, the back-through tends to occur, which is not economical from the viewpoint of cost. Organic pigments include solid, hollow, and donut types in terms of their forms, but the average particle size is 0.2 to 3 in view of the balance of gloss development, surface coverage, and fluidity of the coating liquid. A hollow type having a porosity of 40% or more is more preferable.

The binder of the colorant pigment penetration preventing layer (barrier layer) used in the present invention is particularly strong as long as it is a water-based resin or emulsion that has strong adhesion to the pigment and base paper constituting the barrier layer and does not cause blocking. It is not limited.
Examples of such an aqueous binder include starches such as polyvinyl alcohol, oxidized starch, esterified starch, enzyme-modified starch and cationized starch, casein, soy proteins, carboxymethylcellulose, and hydroxyethylcellulose. , Styrene-acrylic copolymer resin, isobutylene-maleic anhydride copolymer resin, acrylic emulsion, vinyl acetate emulsion, vinylidene chloride emulsion, polyester emulsion, styrene-butadiene copolymer latex, acrylonitrile-butadiene copolymer latex, etc. Can be mentioned. Among these, it is preferable to use starch or styrene-butadiene copolymer latex from the viewpoint of cost. Styrene-butadiene copolymer latex contains styrene and butadiene as monomers, and is commonly used for paper coating in which other monomers are copolymerized as necessary or the copolymer is modified by chemical reaction. Copolymer latex may be used. As other monomers, vinyl monomers such as acrylic acid, methacrylic acid, acrylic acid or alkyl esters of methacrylic acid, acrylonitrile, maleic acid, fumaric acid, and vinyl acetate are often used. Further, it may contain a crosslinking agent such as methylolated melamine, methylolated urea, methylolated hydroxypropylene urea, isocyanate, etc., or a copolymer containing units such as N-methylolacrylamide and having a self-crosslinking property. Also good. These may be used individually by 1 type and may use 2 or more types together.

  The amount of the aqueous binder added (binder) in the barrier layer used in the present invention is preferably 50 to 70% by weight, more preferably 55 to 60% by weight based on the total solid content of the coating layer. If the amount is too small, the adhesive strength becomes insufficient, and there is a concern that the strength of the ink receiving layer will decrease, the internal bond strength will decrease, and powder will fall off.

  Other components can be added to the barrier layer of the present invention as necessary, as long as the objects and effects of the present invention are not impaired. In addition to various auxiliary agents blended in ordinary coated paper pigments, such as dispersants, thickeners, water retention agents, antifoaming agents, water-proofing agents, etc. as other components, pH adjusters, preservatives, oxidation agents Additives such as inhibitors and cationic organic compounds may be used.

  There is no restriction | limiting in particular as surfactant used for a barrier layer, According to the objective, it can select suitably, All using an anionic surfactant, a cationic active agent, an amphoteric active agent, and a nonionic surfactant should be used. Among these, nonionic active agents are particularly preferable among these.

  Examples of the nonionic activator include higher alcohol ethylene oxide adducts, alkylphenol ethylene oxide adducts, fatty acid ethylene oxide adducts, polyhydric alcohol fatty acid ester ethylene oxide adducts, higher aliphatic amine ethylene oxide adducts, and fatty acid amides. Ethylene oxide adduct, fat ethylene oxide adduct, polypropylene glycol ethylene oxide adduct, fatty acid ester of glycerol, fatty acid ester of pentaerythritol, fatty acid ester of sorbitol and sorbitan, fatty acid ester of sucrose, alkyl ether of polyhydric alcohol, And fatty acid amides of alkanolamines. These may be used individually by 1 type and may use 2 or more types together.

  There is no restriction | limiting in particular as said polyhydric alcohol, According to the objective, it can select suitably, For example, glycerol, a trimethylol propane, a pentaerythritol, sorbitol, sucrose etc. are mentioned. As the ethylene oxide adduct, those obtained by substituting a part of ethylene oxide with an alkylene oxide such as propylene oxide or butylene oxide are also effective as long as water solubility can be maintained. The substitution rate is preferably 50% or less. 4-15 are preferable and, as for HLB (hydrophilic new oil ratio) of the said nonionic activator, 7-13 are more preferable.

The cationic organic compound is not necessarily added, but is not particularly limited and can be appropriately selected and used depending on the purpose.
Examples of the cationic organic compound include dimethylamine / epichlorohydrin polycondensate, dimethylamine / ammonia / epichlorohydrin condensate, poly (trimethylaminoethyl methacrylate / methyl sulfate), diallylamine hydrochloride / acrylamide copolymer, (Diallylamine hydrochloride / sulfur dioxide), polyallylamine hydrochloride, poly (allylamine hydrochloride / diallylamine hydrochloride), acrylamide / diallylamine copolymer, polyvinylamine copolymer, dicyandiamide, dicyandiamide / ammonium chloride / urea / formaldehyde condensate , Polyalkylene polyamine dicyandiamide ammonium salt condensate, dimethyl diallyl ammonium chloride, polydiallyl methylamine hydrochloride, poly (diallyl dimethyl ester) Ruammonium chloride), poly (diallyldimethylammonium chloride / sulfur dioxide), poly (diallyldimethylammonium chloride / diallylamine hydrochloride derivative), acrylamide / diallyldimethylammonium chloride copolymer, acrylate / acrylamide / diallylamine hydrochloride copolymer Products, ethyleneimine derivatives such as polyethyleneimine and acrylicamine polymer, and polyethyleneimine alkylene oxide modified products. These may be used individually by 1 type and may use 2 or more types together.

  As the support used in the present invention, chemical pulp, mechanical pulp, waste paper recovered pulp and the like are mixed and used at an arbitrary ratio, and an internal sizing agent, a yield improver, a paper strength enhancer, etc., if necessary. The raw material added with a long net former or a gap type twin wire former, or a hybrid former in which the latter half of the long net part is composed of twin wires is used.

Pulp used in the support of the present invention is virgin chemical pulp (CP), for example, hardwood bleached kraft pulp, softwood bleached kraft pulp, hardwood unbleached kraft pulp, softwood unbleached kraft pulp, hardwood bleached sulfite pulp, softwood bleached Virgin chemical pulp and virgin mechanical pulp (MP), such as ground Virgin mechanical pulp produced mainly by mechanically treating wood and other fiber raw materials such as pulp, chemiground pulp, chemimechanical pulp, and semi-chemical pulp may be included.
Waste paper pulp may also be used, and the raw paper pulp raw material is white, ruled white, cream white, card, white, medium white as shown in the waste paper standard for quality promotion of the Waste Paper Recycling Promotion Center. , Imitation, fair-skinned, Kent, white art, special top-off, separate top-off, newspaper, magazine, etc. Specifically, printer paper such as non-coating computer paper, thermal paper, and pressure-sensitive paper as information-related paper; OA waste paper such as PPC paper; coating of art paper, coated paper, finely coated paper, matte paper, etc. Paper: high quality paper, color quality, notebook, notepaper, wrapping paper, fancy paper, medium quality paper, newsprint, reprint paper, supermarket paper, imitation paper, pure white roll paper, uncoated paper such as milk carton, etc. Examples of used paper and paperboard include chemical pulp paper and high-yield pulp-containing paper. These may be used individually by 1 type and may use 2 or more types together.

The waste paper pulp is generally produced from a combination of the following four steps.
(1) For disaggregation, waste paper is treated with mechanical force and chemicals with a pulper to loosen it into a fibrous form, and the printing ink is peeled off from the fiber.
(2) Dust removal removes foreign matters (plastics, etc.) and dust contained in waste paper with a screen, cleaner or the like.
(3) In the deinking, the printing ink that has been peeled off from the fiber using a surfactant is removed from the system by a flotation method or a cleaning method.
(4) Bleaching increases the whiteness of the fiber using an oxidizing action or a reducing action.
When mixing the used paper pulp, the mixing ratio of the used paper pulp in the total pulp is preferably 40% or less from the viewpoint of curling after recording.

  As a filler that can be used for the support of the present invention, calcium carbonate is effective. However, inorganic fillers such as kaolin, calcined clay, pyrophyllite, sericite, talc, and other inorganic fillers, satin white, and barium sulfate. Organic pigments such as calcium sulfate, zinc sulfide, plastic pigment and urea resin can also be used in combination.

The internal sizing agent used for the support in the present invention is not particularly limited, and can be appropriately selected from known internal sizing agents used for inkjet recording paper. Examples of preferable internal sizing agents include rosin emulsion sizing agents. Examples of the internally added sizing agent used for making the support include, for example, a neutral rosin sizing agent used for neutral papermaking, alkenyl succinic anhydride (ASA), alkyl ketene dimer (AKD), and petroleum resin. Examples include sizing agents. Among these, neutral rosin sizing agents or alkenyl succinic anhydrides are particularly suitable. The alkyl ketene dimer may be added in a small amount because of its high size effect, but the friction coefficient on the surface of the recording paper (medium) decreases and becomes slippery. There is.
The amount of the internally added sizing agent is 0.1 to 0.7 parts by weight with respect to 100 parts by weight of the absolutely dry pulp, but is not limited thereto.

  As the internal filler used for the support, for example, a conventionally known pigment is used as a white pigment. Examples of the white pigment include light calcium carbonate, heavy calcium carbonate, kaolin, clay, talc, calcium sulfate, barium sulfate, titanium dioxide, zinc oxide, zinc sulfide, zinc carbonate, satin white, aluminum silicate, diatomaceous earth, White inorganic pigments such as calcium silicate, magnesium silicate, synthetic silica, aluminum hydroxide, alumina, lithopone, zeolite, magnesium carbonate, magnesium hydroxide; styrene plastic pigment, acrylic plastic pigment, polyethylene, microcapsule, urea resin And organic pigments such as melamine resin. These may be used individually by 1 type and may use 2 or more types together.

<Manufacturing method of barrier layer>
Although it does not prescribe | regulate especially as a method of providing a barrier layer by application | coating to the support body of this invention, it sprays by the method of apply | coating directly, the method of transferring what was once applied on the other base material to a base paper, spray etc. Methods can be used. Examples of the direct coating method include a roll coater method, an air knife coater method, a gate roll coater method, a size press method, a shim sizer method, a rod metering size press coater, etc., a film transfer method, a blade coater method by a fountain or roll application, etc. Can be mentioned.

The barrier layer can be dried using, for example, a hot air drying furnace, a thermal drum, or the like. Further, in order to smooth the surface or increase the strength of the surface, surface finishing may be performed with a calendar device (super calendar, soft calendar, gloss calendar, etc.).
The barrier layer in the present invention can be provided by coating as described above. However, as a result of intensive research by the present inventors, the barrier of the present invention is obtained by polishing the surface of an existing printing coated paper. It turns out that it can also be a layer. This is because the film thickness of the coat layer is reduced by polishing, and the film thickness is reduced to the film thickness shown in the present invention. Presumed to be functional.
Existing coated paper for printing is coated paper used for commercial printing such as so-called art paper (A0, A1), A2 coated paper, A3 coated paper, B2 coated paper, lightweight coated paper, and fine coated paper. This is used for offset printing, gravure printing, and the like.

  As specific products, art paper includes OK Kanto N, OK Kanto-R40N, SA Kanto N, Satin Kanto N, Satin Kanto N-R40N, Ultra Satin Kanto N, Ultra OK Kanto N, Kanto One Side (Oji Paper), NPi Special Art, NPi Super Art, NPi Super Dal, NPi Dal Art (Nippon Paper Industries), Utrillo Super Art, Utrillo Super Dal, Utrillo Premium (Dao Paper), Fine Art A, Tokuhishi Art, Super Matte Art A, High Grade Dull Art A (Mitsubishi Paper), Thunderbird Super Art N, Thunderbird Super Art MN, Thunderbird Special Art, Thunderbird Dull Art N (Chuetsu Pulp) and the like.

  As A2 coated paper, OK top coat + (plus), OK top coat S, OK Casablanca, OK Casablanca V, OK Trinity, OK Trinity NaVi, New Age, New Age W, OK Top Coat Mat N, OK Royal Coat, OK Top Coat Dull, Z Coat, OK Bulk Princess, OK Bulk King, OK Bulk King Satin, OK Top Coat +, OK Non Wrinkle, OK Court V, OK Court N Green 100, OK Matt Court Green 100, New Age Green 100 , Z Coat Green 100 (Oji Paper), Aurora Coat, Shiraoi Mat, Imperial Mat, Silver Diamond, Recycle Coat 100, Cycle Mat 100 (Nippon Paper Industries), Mu Coat, Mu White, Mu Mat, White Mu Mat (North) Papermaking), Thunderbird Coat N, Regina Thunderbird Coat 100, Thunderbird Mat Coat N, Regina Thunderbird Mat 100 (Chuetsu Pulp Industries), Pearl Coat, White Pearl Coat N, New V Mat, White New V Mat, Pearl Coat REW, White Pearl Examples thereof include coat NREW, new V mat REW, white new V mat REW (Mitsubishi Paper).

  As A3 coated (lightweight coated) paper, OK Coat L, Royal Coat L, OK Coat LR, OK White L, OK Royal Coat LR, OK Coat L Green 100, OK Matt Coat L Green 100 (Oji Paper), Easter DX , Recycle Coat L100, Aurora L, Recycle Mat L100, <SSS> Energy White (Nippon Paper), Utrillo Coat L, Matisse Coat (Dao Paper), High Alpha, Alpha Matt, (N) Kinmari L, Kinmari HiL (Hokuetsu) Papermaking), N pearl coat L, N pearl coat LREW, swing mat REW (Mitsubishi Paper), Super Emine, Emine, Chaton (Chuetsu Pulp Industries), and the like.

  Examples of the B2 coat (medium coat) paper include OK medium coat, (F) MCOP, OK Astro Ross, OK Astro Dal, OK Astro mat (Oji Paper), King O (Nippon Paper Industries), and the like.

  Finely coated papers include OK Royal Light S Green 100, OK Everlight Coat, OK Everlight R, OK Evergreen, Clean Hit MG, OK Fine Coating Super Eco G, Eco Green Dull, OK Fine Coating Matte Eco G100 , OK Starlight Coat, OK Soft Royal, OK Bright, Clean Hit G, Yamayuri Bright, Yamayuri Bright G, OK Aqua Light Coat, OK Royal Light S Green 100, OK Bright (Rough / Shiny), Snow Mat, Snow Mat DX , OK Bulk Princess, OK Bulk Yuri (Oji Paper), Piraine DX, Pegasus Hyper 8, Aurora S, Andes DX, Super Andes DX, Space DX, Seine DX, Special Gravure DX, Pegasus, Silver Pegasus, Pegasus Harmony, Greenland X100, Super Greenland DX100, <SSS> Energy Soft, <SSS> Energy Light, EE Henry (Nippon Paper Industries), Canto Excel, Excel Super B, Excel Super C, Canto Excel Bar, Utrillo Excel, Heine Excel, Dante Excel ( Daio Paper), Cosmo Ace (Daiso Showa Paperboard), Semi Upper L, High Beta, High Gamma, Shiromari L, Hamming, White Hamming, Semi Upper HiL, Shiromari HiL (Hokuetsu Paper), Ruby Light HREW, Pearl Soft, Ruby Light H (Mitsubishi Paper), Chaton, Aliso, Smash (Chuetsu Pulp Industries), Star Cherry, Cherry Super (Maruzumi Paper) and the like.

  As a coating layer formulation for general commercial printing paper, a binder (resin, emulsion, starch, etc.) in a ratio of about 10 to 15 parts per 100 parts of inorganic pigment (kaolin, charcoal) Many are seen. Here, the existence of the pigment in the coating layer, and in the extreme, the concentration gradient of the pigment in the coating layer are considered. (1) Clear layer formed on the outermost surface of the coating film as seen in the case of so-called paints. (2) The binder component can permeate into the base paper and have an asymmetric concentration distribution in the upper layer and the lower layer. Even if the literature on the gloss of coated paper) is investigated, there are not many cases being discussed. It is presumed that it is difficult to make a clear layer because the compounding ratio of the resin is relatively low compared to general paints and the resin does not contain enough to precipitate on the surface.

  In a technical discussion with engineers involved in the manufacture of commercial coated paper, the binder function is a technology that prevents the layers from peeling off during printing or to prevent the powder from falling off during cutting. Because many people have an idea, and the amount of resin increases, it tends to hinder coating production, so some people want to keep the minimum amount of binder in this type of paper. It can be seen.

  Regarding (2) above, the resin ratio of the coating layer actually decreases (rather than the composition of the coating solution) in the process of the resin of the coating solution penetrating into the base paper, or at the interface between the coating layer and the base paper. There seems to be a phenomenon of forming a layer, but no example (even in the literature) has confirmed that the layer itself has a gradient. However, there may be an example in which a resin-rich layer can be formed at the interface between the coating layer and the base paper. In this case, it is predicted that the resin concentration is higher in the lower layer.

  As the method of polishing the outermost layer of these coated papers, a method using a sandpaper or lapping paper, a method using a wire brush, a method using a polishing roller or an endless polishing belt, or a sandblasting method is used. However, it is not limited to these methods.

During the production of these coated papers, polishing may be performed by providing an optional polishing step after the coating step, such as immediately after drying, before and after performing a calendar process, a slitting step, and a packaging step, or before printing. The user may perform polishing using a polishing apparatus. It is also possible to incorporate these polishing apparatuses into a printer and perform polishing for each printing.
In the polishing, the entire surface of the paper may be polished, but only an area where ink jet printing is desired can be selectively polished.
For example, it is possible to use offset printing or gravure printing in advance on the above-mentioned general printing paper, polishing only a place where inkjet printing is necessary, and printing in that area.
According to this method, hybrid printing, which was previously performed using both inkjet printing and general printing paper, can be performed using the above-mentioned general printing paper. It becomes. According to this method, address printing or the like by ink jet printing, which has been difficult in general printing until now, becomes possible.

These polishing apparatuses may be incorporated in a printer unit, but a polishing apparatus may be independently prepared as a separate unit.
Further, as a special coated paper, if it already satisfies the conditions of the present invention, it can be used as a medium of the present invention. In particular, a coating layer having a high air permeability can be used. Examples of the coating layer having high air permeability include some coated paper for electrophotography and coated paper for gravure printing. Specific examples include POD gloss coat (Oji Paper), FL gravure (Nippon Paper), and Ace (Nippon Paper). These have a large number of pores in the coating layer and can be used as media having the barrier layer of the present invention.

  The ink in the ink media set of the present invention is an ink jet head that uses a piezoelectric element as pressure generating means for pressurizing ink in the ink flow path, and deforms the diaphragm that forms the wall surface of the ink flow path. A so-called piezo-type device that discharges ink droplets by changing the product (see Japanese Patent Laid-Open No. 2-51734), or a so-called thermal device that generates bubbles by heating ink in an ink flow path using a heating resistor. Type (see Japanese Patent Application Laid-Open No. 61-59911), the diaphragm and the electrode forming the wall surface of the ink flow path are arranged opposite to each other, and the diaphragm is deformed by the electrostatic force generated between the diaphragm and the electrode Thus, any ink jet such as an electrostatic type that discharges ink droplets by changing the volume of the ink flow path (see JP-A-6-71882) can be used. It can be satisfactorily used in the printer for mounting a head.

  As described above, the recording medium in the ink-media set is used in combination with the ink in the ink-media set. The combination of the specific recording medium and the specific ink can be preferably used in various fields, and can be preferably used in an image recording apparatus (printer or the like) using an ink jet recording method. The ink cartridge, ink recording material, ink jet recording apparatus, and ink jet recording method can be used particularly suitably.

[ink cartridge]
The ink cartridge of the present invention contains the ink or ink set in the ink-media set of the present invention in a container, and further includes other members and the like appropriately selected as necessary.
The container is not particularly limited, and its shape, structure, size, material and the like can be appropriately selected according to the purpose. For example, at least an ink bag formed of an aluminum laminate film, a resin film, or the like Preferred examples include those possessed.

Next, the ink cartridge will be described with reference to FIGS. Here, FIG. 1 is a view showing an example of the ink cartridge of the present invention, and FIG. 2 is a view including a case (exterior) of the ink cartridge of FIG.
As shown in FIG. 1, the ink cartridge (200) is filled into the ink bag (241) from the ink inlet (242) and exhausted, and then the ink inlet (242) is closed by fusion. In use, the needle of the apparatus main body is pierced into the ink discharge port (243) made of a rubber member and supplied to the apparatus.
The ink bag (241) is formed of a packaging member such as a non-permeable aluminum laminate film. As shown in FIG. 2, the ink bag (241) is usually housed in a plastic cartridge case (244) and is detachably mounted on various ink jet recording apparatuses.
The ink cartridge of the present invention contains the ink in the ink-media set of the present invention, and can be used by being detachably mounted on various ink jet recording apparatuses, and can be detachably mounted on the ink jet recording apparatus of the present invention described later. It is particularly preferable to use it mounted on.

[Inkjet recording method, inkjet recording apparatus]
The ink jet recording apparatus of the present invention includes at least ink flying means, and further includes other means appropriately selected as necessary, for example, stimulus generation means, control means, and the like.
The inkjet recording method of the present invention includes at least an ink flying process, and further includes other processes appropriately selected as necessary, for example, a stimulus generation process, a control process, and the like.
The ink jet recording method of the present invention can be preferably carried out by the ink jet recording apparatus of the present invention, and the ink flying step can be suitably carried out by the ink flying means. Moreover, the said other process can be suitably performed by the said other means.

The ink flying step is a step of recording an image on a recording medium in the ink-media set by applying a stimulus to the ink in the ink-media set of the present invention.
The ink flying means is means for applying a stimulus to the ink in the ink-media set of the present invention and causing the ink to fly to record an image on a recording medium in the ink-media set. The ink flying means is not particularly limited, and examples thereof include various nozzles for ejecting ink.

In the present invention, it is preferable that at least a part of the liquid chamber portion, the fluid resistance portion, the vibration plate, and the nozzle member of the ink jet head is formed of a material containing at least one of silicon and nickel.
The nozzle diameter of the inkjet nozzle is preferably 30 μm or less, and preferably 1 to 20 μm.
In addition, it is preferable that a sub tank for supplying ink is provided on the ink jet head, and the sub tank is replenished with ink from an ink cartridge through a supply tube.
In the inkjet recording method of the present invention, the maximum ink adhesion amount is preferably 8 to ²⁰ g / m ² at a resolution of 300 dpi or more.

The stimulus can be generated by, for example, the stimulus generating means, and the stimulus is not particularly limited and can be appropriately selected according to the purpose, and includes heat, pressure, vibration, light, and the like. . These may be used individually by 1 type and may use 2 or more types together. Among these, heat and pressure are preferable.
Examples of the stimulus generating means include a heating device, a pressurizing device, a piezoelectric element, a vibration generating device, an ultrasonic oscillator, a light, and the like. Specifically, for example, a piezoelectric actuator such as a piezoelectric element, Examples thereof include a thermal actuator that uses a phase change caused by film boiling of a liquid using an electrothermal transducer such as a heating resistor, a shape memory alloy actuator that uses a metal phase change caused by a temperature change, and an electrostatic actuator that uses an electrostatic force.

  The mode of the ink flying in the ink-media set is not particularly limited, and varies depending on the type of the stimulus. For example, when the stimulus is “heat”, a recording signal is output to the ink in the recording head. The thermal energy corresponding to is applied using, for example, a thermal head, bubbles are generated in the ink by the thermal energy, and the ink is ejected and ejected as droplets from the nozzle holes of the recording head by the pressure of the bubbles. The method etc. are mentioned. Further, when the stimulus is “pressure”, for example, by applying a voltage to a piezoelectric element bonded to a position called a pressure chamber in an ink flow path in the recording head, the piezoelectric element bends and the volume of the pressure chamber is increased. And a method of ejecting and ejecting the ink as droplets from the nozzle holes of the recording head.

  The size of the droplets of ink to be ejected is preferably 1 to 40 pl, the speed of ejection and ejection is preferably 5 to 20 m / s, and the driving frequency is 1 kHz or more. The resolution is preferably 300 dpi or more.

  The control means is not particularly limited as long as the movement of each means can be controlled, and can be appropriately selected according to the purpose. Examples thereof include devices such as sequencers and computers.

  One mode for carrying out the ink jet recording method of the present invention by the ink jet recording apparatus of the present invention will be described with reference to the drawings. The ink jet recording apparatus shown in FIG. 3 has an apparatus main body (101), a paper feed tray (102) for loading paper mounted on the apparatus main body (101), and an image mounted on the apparatus main body (101). A paper discharge tray (103) for stocking the formed paper and an ink cartridge loading section (104) are provided. On the upper surface of the ink cartridge loading section (104), an operation section (105) such as operation keys and a display is arranged. The ink cartridge loading section (104) has an openable / closable front cover (115) for attaching and detaching the ink cartridge (200).

  As shown in FIGS. 4 and 5, a guide rod (131), which is a guide member horizontally mounted on left and right side plates (not shown), and a stay (132) are provided in the apparatus main body (101). 133) is slidably held in the main scanning direction, and is moved and scanned in the direction of the arrow in FIG. 5 by a main scanning motor (not shown).

The carriage (133) includes a recording head (134) including four inkjet recording heads that eject recording ink droplets of each color of yellow (Y), cyan (C), magenta (M), and black (Bk). Are arranged in a direction crossing the main scanning direction and the ink droplet discharge direction is directed downward.
As an inkjet recording head constituting the recording head (134), a piezoelectric actuator such as a piezoelectric element, a thermal actuator that utilizes a phase change caused by liquid film boiling using an electrothermal transducer such as a heating resistor, and a temperature change A shape memory alloy actuator using a metal phase change, an electrostatic actuator using an electrostatic force, or the like provided as an energy generating means for discharging recording ink can be used.
The carriage (133) is equipped with a sub tank (135) for each color for supplying ink of each color to the recording head (134). The sub-tank (135) is supplied with the recording ink of the present invention from the ink cartridge (200) of the present invention loaded in the ink cartridge loading section (104) via a recording ink supply tube (not shown). Is done.

  On the other hand, as a paper feeding unit for feeding the paper (142) stacked on the paper stacking unit (pressure plate) (141) of the paper feed tray (102), 1 sheet (142) is fed from the paper stacking unit (141). A half-moon roller (sheet feeding roller 143) that separates and feeds the sheets one by one and a separation pad (144) made of a material having a large friction coefficient are provided opposite to the sheet feeding roller (143). The roller (143) is urged.

  A conveying belt (151) for electrostatically adsorbing and conveying the paper (142) as a conveying unit for conveying the paper (142) fed from the paper feeding unit below the recording head (134). A counter roller (152) for conveying the paper (142) sent from the paper supply unit via the guide (145) between the conveying belt (151) and a paper (substantially vertically upward) ( 142) and a leading guide roller 153 urged toward the conveying belt (151) by the holding member (154). (155) and a charging roller (156) which is a charging means for charging the surface of the conveyor belt (151).

  The conveyance belt (151) is an endless belt, is stretched between the conveyance roller (157) and the tension roller (158), and can circulate in the belt conveyance direction. The transport belt (151) includes, for example, a surface layer serving as a sheet adsorbing surface formed of a resin material having a thickness of about 40 μm that is not subjected to resistance control, for example, a copolymer of tetrafluoroethylene and ethylene (ETFE), It has the same material as the surface layer and a back layer (medium resistance layer, earth layer) that has been subjected to resistance control by carbon. On the back side of the conveyance belt (151), a guide member (161) is arranged corresponding to the printing area by the recording head (134). As a paper discharge unit for discharging the paper (142) recorded by the recording head (134), a separation claw (171) for separating the paper (142) from the transport belt (151), and paper discharge A roller (172) and a paper discharge roller (173) are provided, and a paper discharge tray (103) is arranged below the paper discharge roller (172).

  A double-sided paper feeding unit (181) is detachably attached to the back surface of the apparatus main body (101). The double-sided paper feeding unit (181) takes in the paper (142) returned by the reverse rotation of the transport belt (151), reverses it, and feeds it again between the counter roller (152) and the transport belt (151). . A manual paper feed unit (182) is provided on the upper surface of the double-sided paper feed unit (181).

  In this ink jet recording apparatus, the sheet (142) is separated and fed one by one from the sheet feeding unit, and the sheet (142) fed substantially vertically upward is guided by the guide (145) and the transport belt (151). ) And the counter roller (152). Further, the leading end is guided by the conveying guide (153) and pressed against the conveying belt (151) by the leading end pressure roller (155), and the conveying direction is changed by about 90 °.

At this time, the conveyance belt (151) is charged by the charging roller (156), and the sheet (142) is electrostatically adsorbed to the conveyance belt (151) and conveyed. Therefore, by driving the recording head (134) according to the image signal while moving the carriage (133), ink droplets are ejected onto the stopped sheet (142) to record one line, and the sheet ( 142) is carried a predetermined amount, and then the next line is recorded. Upon receiving a recording end signal or a signal that the rear end of the paper (142) has reached the recording area, the recording operation is finished and the paper (142) is discharged to the paper discharge tray (103).
When a near-end ink remaining amount in the sub tank (135) is detected, a required amount of ink is supplied from the ink cartridge (200) to the sub tank (135).

  In this ink jet recording apparatus, when the ink in the ink cartridge (200) of the present invention is used up, the casing of the ink cartridge (200) can be disassembled and only the ink bag inside can be replaced. Further, the ink cartridge (200) can supply ink stably even when the ink cartridge (200) is vertically placed and has a front loading configuration. Therefore, even when the upper part of the apparatus main body (101) is closed and installed, for example, even when it is stored in a rack or an object is placed on the upper surface of the apparatus main body (101), the ink The cartridge (1) can be easily replaced.

Here, an example is described in which the present invention is applied to a serial (shuttle type) ink jet recording apparatus that is scanned by a carriage, but the present invention can be similarly applied to a line type ink jet recording apparatus having a line type head.
Further, the ink jet recording apparatus and the ink jet recording method of the present invention can be applied to various types of recording by the ink jet recording method. For example, the ink jet recording apparatus, the facsimile apparatus, the copying apparatus, the printer / fax / copier multifunction machine, etc. It can be particularly preferably applied.

Hereinafter, an inkjet head to which the present invention is applied will be described.
FIG. 6 is an enlarged view of elements of an ink jet head to which the present invention is applied, and FIG. 7 is an enlarged cross-sectional view of the main part of the head in the direction between channels.
This ink-jet head has an ink supply port (not shown) (supplying ink from the front surface direction to the back direction (back surface direction of the paper) in FIG. 6) and a frame (engraved to form a common liquid chamber (12) ( 10), a fluid resistance portion (21), a flow path plate (20) in which a carving to be a pressurized liquid chamber (22) and a communication port (23) communicating with the nozzle (31) are formed, and a nozzle (31) A nozzle plate (30) to be formed, a diaphragm (60) having a convex part (61), a diaphragm part (62) and an ink inlet (63), and an adhesive layer (70) on the diaphragm (60) A laminated piezoelectric element (50) joined and a base (40) fixing the laminated piezoelectric element (50) are provided. The base (40) is made of a barium titanate ceramic, and the laminated piezoelectric elements (50) are arranged in two rows and joined.
The laminated piezoelectric element (50) includes a lead zirconate titanate (PZT) piezoelectric layer (51) having a thickness of 10 to 50 μm / layer and a silver / palladium (AgPd) layer having a thickness of several μm / layer. Electrode layers (52) are alternately stacked. The internal electrode layer (52) is connected to the external electrode (53) at both ends.
The laminated piezoelectric element (50) is divided on comb teeth by half-cut dicing, and is used as a drive unit (56) and a support unit (57) (non-drive unit) one by one (FIG. 7).
The outer end of one of the two external electrodes (53) (connected to one end of the internal electrode layer (52) in the front or back direction (back side of the paper) in the figure) is divided by half-cut dicing. Further, the length is limited by processing such as notches, and these become a plurality of individual electrodes (54). The other is conductive without being divided by dicing, and becomes a common electrode (55).
An FPC (80) is soldered to the individual electrode (54) of the drive unit. Further, the common electrode (55) is provided with an electrode layer at the end of the laminated piezoelectric element, and is wound around to join the Gnd electrode of the FPC (80). A driver IC (not shown) is mounted on the FPC (80), thereby controlling application of drive voltage to the drive unit (56).

The diaphragm (60) is an island-shaped convex portion (island) that joins the thin film diaphragm portion (62) and the laminated piezoelectric element (50) that becomes the drive portion (56) formed in the central portion of the diaphragm portion (62). Part) (61), a thick film part including a beam joined to a support part (not shown), and an opening to be an ink inflow port (63) are formed by stacking two Ni plating films by electroforming. . The diaphragm portion has a thickness of 3 μm and a width of 35 μm (one side).
The island-shaped convex part (61) of the diaphragm (60) and the movable part (56) of the laminated piezoelectric element (50), and the connection between the diaphragm (60) and the frame (10) are bonded layers including a gap material ( 70) is bonded by patterning.

The flow path plate (20) uses a silicon single crystal substrate, is engraved to be a fluid resistance portion (21), a pressurized liquid chamber (22), and a through-hole to be a communication port (23) at a position relative to the nozzle (31). Was patterned by an etching method.
The portion left by etching becomes the partition wall (24) of the pressurized liquid chamber (22). Further, in this head, a portion for narrowing the etching width was provided, and this was used as the fluid resistance portion (21).

The nozzle plate (30) is formed of a metal material, for example, an Ni plating film by an electroforming method, and has a large number of nozzles (31) that are fine discharge ports for causing ink droplets to fly. The internal shape (inner shape) of the nozzle (31) is formed in a horn shape (may be a substantially cylindrical shape or a substantially frustum shape). The diameter of the nozzle (31) is about 20 to 35 μm as the diameter on the ink droplet outlet side. The nozzle pitch of each row was 150 dpi.
The ink ejection surface (nozzle surface side) of the nozzle plate (30) is provided with a water repellent treatment layer that has been subjected to a water repellent surface treatment (not shown). Ink, such as PTFE-Ni eutectoid plating, electrodeposition coating of fluororesin, vapor-deposited fluororesin (for example, fluorinated pitch, etc.), baking after solvent application of silicone resin and fluororesin A water repellent film selected according to the physical properties is provided to stabilize the ink droplet shape and flight characteristics so that high quality image quality can be obtained. Among these, for example, various materials are known as the fluororesin, but a modified perfluoropolyoxetane (manufactured by Daikin Industries, Ltd., trade name: OPTOOL DSX) has a thickness of 30 to 100 mm. Thus, good water repellency can be obtained by vapor deposition.
The frame (10) that forms the engraving that becomes the ink supply port and the common liquid chamber (12) is made by resin molding.

In the ink jet head configured as described above, a driving waveform (pulse voltage of 10 to 50 V) is applied to the driving unit (56) according to the recording signal, thereby causing displacement in the stacking direction in the driving unit (56). The pressurized liquid chamber (22) is pressurized through the nozzle plate (30) to increase the pressure, and ink droplets are ejected from the nozzle (31).
Thereafter, the ink pressure in the pressurized liquid chamber (22) decreases with the end of ink droplet ejection, and negative pressure is generated in the pressurized liquid chamber (22) due to the inertia of the ink flow and the discharge process of the drive pulse. Then, the process proceeds to the ink filling process. At this time, the ink supplied from the ink tank flows into the common liquid chamber (12), passes from the common liquid chamber (12) through the ink inflow port (63), passes through the fluid resistance portion (21), and reaches the pressurized liquid chamber ( 22) is filled.
The fluid resistance portion (21) is effective in damping the residual pressure vibration after ejection, but is resistant to the maximum filling (refill) due to surface tension. By appropriately selecting the fluid resistance portion, it is possible to balance the attenuation of the residual pressure and the refill time, and to shorten the time (drive cycle) until the transition to the next ink droplet ejection operation.

Examples of the present invention will be described below, but the present invention is not limited to these examples.
Preparation Example 1 (Surface-treated carbon black pigment dispersion)
90 g of carbon black with a CTAB specific surface area of 150 m ² / g and DBP oil absorption of 100 ml / 100 g is added to 3000 ml of 2.5N normal sodium sulfate solution, stirred at a temperature of 60 ° C. and a speed of 300 rpm, and reacted for 10 hours for oxidation treatment. Was done. The reaction solution was filtered, and the carbon black separated by filtration was neutralized with a sodium hydroxide solution and subjected to ultrafiltration. The obtained carbon black was washed with water, dried, and dispersed in pure water to 20% by weight.

Preparation Example 2 (Surface-treated yellow pigment dispersion)
As a yellow pigment, C.I. I. Pigment Yellow 128 was subjected to low-temperature plasma treatment to prepare a pigment into which a carboxylic acid group was introduced. A dispersion of this in ion-exchanged water was desalted and concentrated with an ultrafiltration membrane to obtain a yellow pigment dispersion having a pigment concentration of 15%.

Preparation Example 3 (Preparation of surface-treated magenta pigment)
According to the procedure of Preparation Example 2, a surface-modified magenta pigment was prepared. I. Instead of Pigment Yellow 128, Pigment Red 122 was used. Similar to the above example, the obtained surface-modified colored pigment is easily dispersed in an aqueous medium upon stirring, and desalted and concentrated with an ultrafiltration membrane to obtain a magenta pigment dispersion having a pigment concentration of 15%. .

Adjustment Example 4 (Adjustment of surface-treated cyan pigment)
According to the procedure of Preparation Example 2, a surface-modified cyan pigment was prepared. I. Instead of CI Pigment Yellow 128, C.I. I. Pigment cyan 15: 3 was used. Similar to the above example, the obtained surface-modified colored pigment was easily dispersed in an aqueous medium upon stirring and desalted and concentrated with an ultrafiltration membrane to obtain a cyan pigment dispersion having a pigment concentration of 15%. .

Synthesis Example 1 (Preparation of polymer dispersion)
After sufficiently replacing the inside of the 1 L flask equipped with a mechanical stirrer, thermometer, nitrogen gas inlet tube, reflux tube and dropping funnel with nitrogen gas, 11.2 g of styrene, 2.8 g of acrylic acid, 12.0 g of lauryl methacrylate, 4.0 g of polyethylene glycol methacrylate, 4.0 g of styrene macromer (manufactured by Toagosei Co., Ltd., trade name: AS-6) and 0.4 g of mercaptoethanol were charged, and the temperature was raised to 65 ° C. Next, styrene 100.8 g, acrylic acid 25.2 g, lauryl methacrylate 108.0 g, polyethylene glycol methacrylate 36.0 g, hydroxyethyl methacrylate 60.0 g, styrene macromer (manufactured by Toagosei Co., Ltd., trade name: AS-6) A mixed solution of 36.0 g, mercaptoethanol 3.6 g, azobisdimethylvaleronitrile 2.4 g and methyl ethyl ketone 18 g was dropped into the flask over 2.5 hours. After completion of dropping, a mixed solution of 0.8 g of azobisdimethylvaleronitrile and 18 g of methyl ethyl ketone was dropped into the flask over 0.5 hours. After aging at 65 ° C. for 1 hour, 0.8 g of azobisdimethylvaleronitrile was added, and further aging was performed for 1 hour. After completion of the reaction, 364 g of methyl ethyl ketone was added to the flask to obtain 800 g of a polymer solution having a concentration of 50%.

Preparation Example 5 (Preparation of phthalocyanine pigment-containing polymer fine particle dispersion)
After 28 g of the polymer solution prepared in Synthesis Example 1, 26 g of phthalocyanine pigment, 13.6 g of 1 mol / L potassium hydroxide solution, 20 g of methyl ethyl ketone, and 30 g of ion-exchanged water were sufficiently stirred, they were kneaded using a three-roll mill. The obtained paste was put into 200 g of ion-exchanged water and stirred sufficiently, and then methyl ethyl ketone and water were distilled off using an evaporator to obtain a cyan polymer fine particle dispersion.

Preparation Example 6 (Preparation of dimethylquinacridone pigment-containing polymer fine particle dispersion)
A magenta polymer fine particle dispersion was obtained in the same manner as in Synthesis Example 1 except that the phthalocyanine pigment of Synthesis Example 1 was changed to Pigment Red 122.

Preparation Example 7 (Preparation of monoazo yellow pigment-containing polymer fine particle dispersion)
A yellow polymer fine particle dispersion was obtained in the same manner as in Synthesis Example 1 except that the phthalocyanine pigment of Synthesis Example 1 was changed to Pigment Yellow 74.

Adjustment Example 8 (Adjustment of carbon black pigment-containing polymer fine particle dispersion)
A black polymer fine particle dispersion was obtained in the same manner as in Synthesis Example 1 except that the phthalocyanine pigment in Synthesis Example 1 was changed to carbon black.

Preparation Example 9 (Preparation of phthalocyanine pigment dispersion)
C. I. Pigment Cyan 15: 3 150 g, R = alkyl group, m = 10, n = 40 pigment dispersant polyethylene ethylene β-naphthyl ether 110 g represented by the following structural formula (4), pionine A-51-B (Takemoto 2 g of oil and fat, dispersant) and 738 g of distilled water were mixed and this mixture was pre-dispersed, and then 20 hours in a disk type bead mill (Shinmaru Enterprises KDL type, media: 0.3 mmφ zirconia ball used) Circulating dispersion was performed to obtain a phthalocyanine pigment dispersion.

（式中、Ｒは１〜２０のアルキル基、アリル基またはアラルキル基を表わし、ｍは０〜７の整数を表わし、ｎは２０〜２００の整数を表わす。）

(In the formula, R represents an alkyl group of 1 to 20, an allyl group or an aralkyl group, m represents an integer of 0 to 7, and n represents an integer of 20 to 200.)

Preparation Example 10 (Preparation of dimethylquinacridone pigment dispersion)
In adjustment example 9, C.I. I. Pigment Cyan 15: 3 is changed to C.I. A dimethylquinacridone pigment dispersion was obtained in the same manner as in Preparation Example 9 except that the pigment was changed to I Pigment Red 122.

Preparation Example 11 (Preparation of monoazo yellow pigment dispersion)
In adjustment example 9, C.I. I. Pigment Cyan 15: 3 is changed to C.I. A monoazo yellow pigment dispersion was obtained in the same manner as in Preparation Example 9 except that the pigment was changed to I Pigment Yellow 74.

Below, the synthesis example of acrylic-silicone-type resin emulsion is shown among water-dispersible resin (A) used by this invention.
Synthesis Example 2 (Synthesis 1 of silicon-modified acrylic resin fine particles containing no reactive silyl group)
After fully replacing the inside of the flask equipped with a mechanical stirrer, thermometer, nitrogen gas inlet tube, reflux tube and dropping funnel with nitrogen gas, 10 g of Aqualon RN-20 (Daiichi Kogyo Seiyaku), 1 g of potassium persulfate and pure 286 g of water was charged and the temperature was raised to 65 ° C. Next, 150 g of methyl methacrylate, 100 g of 2-ethylhexyl acrylate, 20 g of acrylic acid, 20 g of vinyltriethoxysilane, 10 g of Aqualon RN-20, 4 g of potassium persulfate 10 g of Aqualon RN-20, 4 g of potassium persulfate and pure water 398.3 g of the mixed solution was dropped into the flask over 2.5 hours. The mixture was further heated and aged at 80 ° C. for 3 hours and then cooled, and the pH was adjusted to 7 to 8 with potassium hydroxide. The particle diameter of the resin measured using Microtrac UPA was 130 nm. The minimum film forming temperature (MTF) was 0 ° C.

Synthesis Example 3 (Synthesis 2 of silicon-modified acrylic resin fine particles not containing reactive silyl group 2)
After fully replacing the inside of the flask equipped with a mechanical stirrer, thermometer, nitrogen gas inlet tube, reflux tube and dropping funnel with nitrogen gas, 10 g of Aqualon RN-20 (Daiichi Kogyo Seiyaku), 1 g of potassium persulfate and pure 286 g of water was charged and the temperature was raised to 65 ° C. Next, 150 g of methyl methacrylate, 100 g of 2-ethylhexyl acrylate, 20 g of acrylic acid, 40 g of hexyltrimethoxysilane, 10 g of Aqualon RN-20, 10 g of potassium persulfate 10 g of Aqualon RN-20, 4 g of potassium persulfate and pure water 398.3 g of the mixed solution was dropped into the flask over 3 hours. The mixture was further heated and aged at 80 ° C. for 3 hours and then cooled, and the pH was adjusted to 7 to 8 with potassium hydroxide. The particle diameter of the resin measured using Microtrac UPA was 148 nm. The minimum film forming temperature (MTF) was 0 ° C.

Synthesis Example 4 (Synthesis of reactive silyl group-containing silicon-modified acrylic resin fine particles)
The examples described in JP-A-6-157861 were re-examined, and silicon-modified acrylic resin fine particles containing reactive silyl groups were synthesized.
After fully replacing the inside of the flask equipped with a mechanical stirrer, thermometer, nitrogen gas inlet tube, reflux tube and dropping funnel with nitrogen gas, 100 g of pure water, 3 g of sodium dodecylbenzenesulfonate and 1 g of polyethylene glycol nonylphenyl ether were added. First, 1 g of ammonium persulfate and 0.2 g of sodium hydrogen sulfite were added, and the temperature was raised to 60 ° C. Next, 30 g of butyl acrylate, 40 g of methyl methacrylate, 19 g of butyl methacrylate, 10 g of vinylsilanetriol potassium salt and 1 g of 3-methacryloxypropylmethyldimethoxysilane were dropped into the flask over 3 hours. At this time, polymerization was carried out by adjusting the polymerization reaction solution to pH 7 with an aqueous ammonia solution. The particle diameter of the resin measured using Microtrac UPA (microparticle size measurement apparatus manufactured by Microtrac) was 160 nm.

Examples and Comparative Examples of the present invention are shown below, but the present invention is not limited to these. In addition, the amount of each component described in the examples is based on weight.
An ink composition having the following formulation was prepared and adjusted with a 10% aqueous solution of lithium hydroxide so that the pH was 9. Then, it filtered with the membrane filter with an average hole diameter of 0.8 micrometer, and obtained the ink composition.

  Hereinafter, the present invention will be described in more detail with reference to ink production examples, but the present invention is not limited to the following ink production examples. In addition, the amount (%) of each component described below is based on weight.

(Ink Production Example 1) Black ink 1
Carbon black produced in Preparation Example 1 8 wt% (as solid content)
Acrylic-silicone resin emulsion of Synthesis Example 2 4 wt% (as solid content)
Diethylene glycol 18wt%
Glycerin 6wt%
2-pyrrolidone 2wt%
Zonyl FSN-100 1wt%
(Fluorosurfactant manufactured by DuPont)
2,2,4-Trimethyl-1,3-pentanediol 2wt%
Ion exchange water was added to make 100%.

(Ink Production Example 2) Yellow ink 1
Yellow pigment dispersion prepared in Preparation Example 2 5 wt% (as solid content)
Acrylic-silicone resin emulsion of Synthesis Example 1 10 wt% (as solid content)
1,3-butanediol 20wt%
Glycerin 8wt%
2-pyrrolidone 2wt%
Zonyl FSN-100 1wt%
(Fluorosurfactant manufactured by DuPont)
2,2,4-Trimethyl-1,3-pentanediol 2wt%
Ion exchange water was added to make 100%.

(Ink Production Example 3) Magenta ink 1
Magenta pigment dispersion prepared in Preparation Example 5 wt% (as solid content)
Acrylic-silicone resin emulsion of Synthesis Example 3 15 wt% (as solid content)
Triethylene glycol isobutyl ether 4wt%
Glycerin 15wt%
Zonyl FS-300 2wt%
(Fluorosurfactant manufactured by DuPont)
2-ethyl-1,3-hexanediol 2wt%
Ion exchange water was added to make 100%.

(Ink Production Example 4) Cyan ink 1
Cyan pigment dispersion prepared in Preparation Example 5 5% by weight (as solid content)
Acrylic-silicone resin emulsion of Synthesis Example 4 15 wt% (as solid content)
3-methyl-1,3-butanediol 15 wt%
Glycerin 15wt%
Zonyl FS-300 2wt%
(Fluorosurfactant manufactured by DuPont)
2-ethyl-1,3-hexanediol 2wt%
Ion exchange water was added to make 100%.

(Ink Production Example 5) Cyan ink 2
Cyan pigment dispersion prepared in Preparation Example 5 5% by weight (as solid content)
W-5025 (Mitsui Takeda Chemicals Urethane Resin Emulsion)
10wt% (as solid content)
1,6-hexanediol 20wt%
Glycerin 8wt%
SS-2801 1wt%
(Nihon Unicar's silicone surfactant)
2-ethyl-1,3-hexanediol 2wt%
Ion exchange water was added to make 100%.

(Ink Production Example 6) Magenta ink 2
Magenta pigment dispersion prepared in Preparation Example 5 5 wt% (as solid content)
W-5661 (Mitsui Takeda Chemicals Urethane Resin Emulsion)
10wt% (as solid content)
1,5-pentanediol 15wt%
Glycerin 15wt%
SS-2803 1wt%
(Nihon Unicar's silicone surfactant)
2-ethyl-1,3-hexanediol 2wt%
Ion exchange water was added to make 100%.

(Ink Production Example 7) Yellow ink 2
Yellow pigment dispersion prepared in Preparation Example 7 4 wt% (as solid content)
Acrylic-silicone resin emulsion of Synthesis Example 3 15 wt% (as solid content)
2-methyl-2,4-pentanediol 10wt%
Glycerin 10wt%
Fullrad FC4430 1wt%
(Fluorosurfactant manufactured by Sumitomo 3M)
2,2,4-Trimethyl-1,3-pentanediol 3wt%
Ion exchange water was added to make 100%.

(Ink Production Example 8) Black ink 2
Black pigment dispersion prepared in Preparation Example 8 8% by weight (as solid content)
Acrylic-silicone resin emulsion of Synthesis Example 2 12 wt% (as solid content)
1,6-hexanediol 20wt%
Glycerin 8wt%
SS-2801 1wt%
(Nihon Unicar's silicone surfactant)
2-ethyl-1,3-hexanediol 2wt%
Ion exchange water was added to make 100%.

(Ink Production Example 9) Cyan ink 3
Cyan pigment dispersion prepared in Preparation Example 4 4 wt% (as solid content)
W-5025 (Mitsui Takeda Chemicals Urethane Resin Emulsion)
10wt% (as solid content)
1,3-butanediol 20wt%
Glycerin 8wt%
Zonyl FSO 1.5wt%
(Fluorosurfactant manufactured by DuPont)
2-ethyl-1,3-hexanediol 2wt%
Ion exchange water was added to make 100%.

(Ink Production Example 10) Magenta ink 3
Magenta pigment dispersion prepared in Preparation Example 7 7 wt% (as solid content)
W-5661 (Mitsui Takeda Chemicals Urethane Resin Emulsion)
10wt% (as solid content)
1,5-pentanediol 15wt%
Glycerin 15wt%
SS-2803 1wt%
(Nihon Unicar's silicone surfactant)
2-ethyl-1,3-hexanediol 2wt%
Ion exchange water was added to make 100%.

(Ink Production Example 11) Yellow ink 3
Yellow pigment dispersion prepared in Preparation Example 6 6% by weight (as solid content)
Acrylic-silicone resin emulsion of Synthesis Example 3 15 wt% (as solid content)
2-methyl-2,4-pentanediol 10wt%
Glycerin 10wt%
Megafuck F470 1wt%
(Fluorosurfactant manufactured by Dainippon Ink, Inc.)
2,2,4-Trimethyl-1,3-pentanediol 3wt%
Ion exchange water was added to make 100%.

(Ink Production Example 12) Cyan ink 4
Cyan pigment dispersion prepared in Preparation Example 5 5% by weight (as solid content)
W-5025 (Mitsui Takeda Chemicals Urethane Resin Emulsion)
10wt% (as solid content)
1,6-hexanediol 20wt%
Glycerin 8wt%
SS-2801 0.5wt%
(Nihon Unicar's silicone surfactant)
Structural formula (1) PF-151N 0.5 wt%
(Fluorosurfactant manufactured by OMNOVA)
2-ethyl-1,3-hexanediol 2wt%
Ion exchange water was added to make 100%.

(Ink Production Example 13) Magenta ink 4
Magenta pigment dispersion prepared in Preparation Example 5 5 wt% (as solid content)
W-5661 (Mitsui Takeda Chemicals Urethane Resin Emulsion)
10wt% (as solid content)
1,5-pentanediol 15wt%
Glycerin 15wt%
SS-2803 0.5wt%
(Nihon Unicar's silicone surfactant)
Structural formula (1) PF-151N 0.5 wt%
(Fluorosurfactant manufactured by OMNOVA)
2-ethyl-1,3-hexanediol 2wt%
Ion exchange water was added to make 100%.

(Ink Production Example 14) Yellow ink 4
Yellow pigment dispersion prepared in Preparation Example 7 4 wt% (as solid content)
Acrylic-silicone resin emulsion of Synthesis Example 3 15 wt% (as solid content)
2-methyl-2,4-pentanediol 10wt%
Glycerin 10wt%
FX-2105 0.5wt%
(Nihon Unicar's silicone surfactant)
Structural formula (1) PF-151N 0.5 wt%
(Fluorosurfactant manufactured by OMNOVA)
2,2,4-Trimethyl-1,3-pentanediol 3wt%
Ion exchange water was added to make 100%.

(Ink Production Example 15) Black ink 4
Black pigment dispersion prepared in Preparation Example 8 8% by weight (as solid content)
Acrylic-silicone resin emulsion of Synthesis Example 2 12 wt% (as solid content)
1,6-hexanediol 20wt%
Glycerin 8wt%
SS-2801 0.5wt%
(Nihon Unicar's silicone surfactant)
Structural formula (1) PF-151N 0.5 wt%
(Fluorosurfactant manufactured by OMNOVA)
2-ethyl-1,3-hexanediol 2wt%
Ion exchange water was added to make 100%.

(Comparative Production Example 1) Comparative Pigment Cyan Ink In the ink production example 5, a cyan ink was obtained in the same manner as the ink production example 5 except that the urethane resin emulsion W-5025 was not added.

(Comparative Production Example 2) Comparative Pigment Magenta Ink In Magenta ink was obtained in the same manner as Ink Production Example 6 except that the urethane resin emulsion W-5661 was not used in Ink Production Example 6.

(Comparative Production Example 3) Comparative Pigment Yellow Ink Ink Production Example 7 was the same as Ink Production Example 7 except that the acrylic-silicone resin emulsion of Synthesis Example 3 was not used.

(Comparative Production Example 4) Comparative Pigment Black Ink In the ink production example 8, the acrylic-silicone resin emulsion of Synthesis Example 2 was not added, and acetylene glycol surfactant Surfynol 465 (Air Products) was replaced with SS-2801 ( A black ink was obtained in the same manner as in Ink Production Example 8 except that it was used in place of Nippon Unicar Company.

(Comparative Production Examples 5 to 8) -Preparation of dye ink-
Each component shown below was mixed, sufficiently stirred and dissolved, and then filtered under pressure using a fluoropore filter (trade name: manufactured by Sumitomo Electric Co., Ltd.) having a pore size of 0.45 μm to prepare a dye ink set.
Dye ink composition:
(Dye type)
Comparative Production Example 5: Yellow C.I. I. Direct yellow 86
Comparative Production Example 6: Cyan C.I. I. Direct Blue 199
Comparative Production Example 7: Magenta C.I. I. Acid Red 285
Comparative Production Example 8: Black C.I. I. Direct black 154
(Ink formulation)
Each above dye 4wt%
Glycerin 7wt%
Thiodiglycol 7wt%
Urea 7wt%
F470 (Dainippon Ink Co., Ltd.) 1wt%
Ion exchange water was added to make 100%.

Hereinafter, Table 1 shows an ink production example and a comparative production example, and the ink composition will be described.
The ink surface tension, viscosity, and weight specific gravity ratio (A) / (B) of the colorant (B) to the water-dispersible resin (A) are described in the table.

次に、表２に実施例及び比較例の評価インクセットを示す。

Next, Table 2 shows evaluation ink sets of Examples and Comparative Examples.

Next, base paper (media) production will be described below.
<Manufacture of base paper>
(Base Paper Production Example 1) -Production of Support 1-
・ LBKP 71.23 wt%
・ NBKP 17.81wt%
・ Light calcium carbonate (trade name: TP-121, manufactured by Okutama Kogyo Co., Ltd.) 8.90 wt%
・ Aluminum sulfate 0.89wt%
・ Amphoteric starch (trade name: Cato3210, manufactured by NSC Japan) 0.89wt%
-Neutral rosin sizing agent (trade name: NeuSize M-10, manufactured by Harima Kasei Co., Ltd.) 0.27 wt%
・ Yield improver (trade name: NR-11LS, manufactured by Hymo Co.) 0.01 wt%
A 0.3% by mass slurry of the above composition was made with a long paper machine and machine calendered to prepare a support 1 having a basis weight of 79 g / m ² . In addition, in the size press process of the papermaking process, the oxidized starch aqueous solution was applied so that the solid content was 1.0 g / m ² per side.

(Paper Example 1)
70 parts of kaolin (refractive index 1.6, ultra white 90 (manufactured by Engelhard)) having a particle diameter of 2 μm or less as a pigment and having a particle diameter of 2 μm or less as a pigment is prepared on the support 1 produced in Base Paper Production Example 1. .1 μm heavy calcium carbonate (refractive index 1.6 CALSHITEC Brilliant-15 (Shiraishi Kogyo Co., Ltd.) 30 parts, styrene-butadiene copolymer emulsion 8 having a glass transition temperature (Tg) of −5 ° C. as an adhesive 8 Part, phosphoric esterified starch 1 part, 0.5 parts of calcium stearate as an auxiliary agent was added, and water was further added to prepare a coating solution having a solid content concentration of 60%.
This coating solution was coated on both sides of the above base paper using a blade coater so that the coating layer thickness per side was 1 μm, dried with hot air, and then subjected to supercalendering. Got.

A drop-on-demand printer prototype having 300 dpi and a nozzle resolution of 384 nozzles was used for this recording paper 1 using the ink compositions and ink sets described in Tables 1 and 2 and the recording paper 1 as a recording medium. Printing was performed at an image resolution of 600 dpi. The maximum droplet size was 18 pl, and the total amount of secondary colors was regulated to 140%, and the amount of adhesion was regulated. During solid printing, solid images and characters were printed so that the total amount of ink in 300 dots square did not exceed 15 g / m ² . The image quality and image reliability of the obtained image were evaluated. The results are shown in Table 3. Those marked with “x” in the evaluation result are inappropriate as an inkjet image.

(Paper Example 2)
Inkjet recording was carried out in the same manner as in Paper Example 1 except that the coating layer thickness per side of Paper Example 1 was 10 μm and “Recording Paper 2” was obtained.

(Paper Example 3)
Paper implementation except that 100 parts (solid content) of TA-100 (anatase type titanium oxide, refractive index 2.5, manufactured by Fuji Titanium Industry Co., Ltd.) was obtained as the inorganic pigment of the coating liquid of paper example 1 to obtain “recording paper 3”. Inkjet recording was carried out in the same manner as in Example 2.

(Paper Example 4)
"Recording paper 4" with 100 parts of inorganic pigment of the coating liquid of paper example 1 TP-221 (light calcium carbonate refractive index 1.6 (1.59), manufactured by Okutama Kogyo) and a coating layer thickness of 5 μm Inkjet recording was carried out in the same manner as in Example 1 except that the above was obtained.

(Paper Example 5)
Except for using the space DX (containing kaolin with a refractive index of 1.6 / calcium carbonate with a refractive index of 1.6, manufactured by Nippon Paper Industries Co., Ltd.) (“Recording paper 5”) of the coated paper for gravure printing as the recording medium of the paper Example 1. Inkjet recording was carried out in the same manner as in paper example 1.

(Paper Example 6)
Except for using POD gloss of electrophotographic coated paper (containing kaolin refractive index 1.6 / calcium carbonate refractive index 1.6, manufactured by Oji Paper Co., Ltd.) ("Recording Paper 6") as the recording medium of Paper Example 1. Inkjet recording was carried out in the same manner as in paper example 1.

(Paper Example 7)
The surface of the electrophotographic coated paper POD gloss (containing kaolin refractive index 1.6 / calcium carbonate refractive index 1.6, made by Oji Paper) is polished 20 times with wrapping paper, and the coating layer thickness is 5. Inkjet recording was carried out in the same manner as in Example 5 except that the recording medium was 1 μm (“Recording Paper 7”).

(Paper Comparison Example 3)
Ink set 2 in the present invention / Chrispia (manufactured by Epson)
Image evaluation was carried out as Comparative Example 3 except that the recording medium was changed to Chrispier (a glossy paper for ink jet made by Epson, which is regarded as higher grade than the coated paper in the present invention) which is a glossy paper for ink jet photography. From the following results, in the system (image processing, ink adhesion amount) in the printer, the density and gloss are reduced and the scratching property is also reduced. Therefore, the effect of the present invention is that the specific ink and the specific recording are effective. It is understood that the effect is not exhibited unless it is a combination of media.

Evaluation items and evaluation methods are shown below.
(Evaluation items and measurement methods)
(1) Image quality Back-through The image density of the back side of the green solid image part of the example and the comparative example was measured, and the value obtained by subtracting the density of the background part was used as the back-through density. Considering this concentration and visual judgment, the evaluation was made according to the following criteria.
〔Evaluation criteria〕
A: Print-through density is 0.1 or less, and uniform printing is achieved without occurrence of minute print-through.
A: The print-through density is 0.15 or less, and the print is uniform without occurrence of minute print-through.
(Triangle | delta): Although the back-through density is 0.15 or less, generation | occurrence | production of minute back-through is recognized.
X: Generation | occurrence | production of a serious through-through is recognized.
2. Beading The degree of beading in the green solid image portions of Examples and Comparative Examples was visually observed, and the rank was evaluated according to the following criteria.
〔Evaluation criteria〕
5: Uniform printing without occurrence of beading.
4: The occurrence of beading is slightly observed, but it is at a level that does not matter at all.
3: The occurrence of beading is recognized, but the image quality is not impaired.
2: The occurrence of beading is clearly observed.
1: Significant beading is observed.
3. Evaluation of Image Density The optical density of the magenta image portions of Examples and Comparative Examples was measured with X-Rite 932 and evaluated according to the following criteria.
〔Evaluation criteria〕
◎: Magenta image density 1.6 or more ○: Magenta image density 1.3 or more Δ: Magenta image density 1.0 or more ×: Magenta image density less than 1.0 Evaluation of glossiness The degree of glossiness of the image portions of Examples and Comparative Examples was visually observed and evaluated according to the following criteria.
〔Evaluation criteria〕
A: High gloss.
○: Glossy.
X: A glossiness is not recognized.

(2) Image reliability <Evaluation of scratch resistance>
As an evaluation image, a black, cyan, magenta, yellow, red, green, and blue square (3 cm × 3 cm) was used. After printing for 24 hours, use a clock meter (CM-1 type), and attach white cotton cloth (JISL 0803 cotton 3) to the friction piece with double-sided adhesive foam tape (# 4016 t = 1.6, manufactured by 3M). The density of the color material that was rubbed back and forth and adhered to the cotton cloth was measured using a spectrocolorimetric densitometer (Model-938 manufactured by X-Rite).
〔Evaluation criteria〕
◎: Color material concentration attached to cotton cloth is less than 0.05 ○: Color material concentration attached to cotton cloth is 0.05 or more and less than 0.1 ×: Color material concentration attached to cotton cloth is 0.1 or more 3 shows.

It is the schematic which shows an example of the ink cartridge of this invention. FIG. 2 is a schematic view including a case (exterior) of the ink cartridge of FIG. 1. FIG. 4 is a perspective explanatory view showing a state where an ink cartridge loading unit cover of the ink jet recording apparatus is opened. It is a schematic block diagram explaining the whole structure of an inkjet recording device. It is a schematic enlarged view which shows an example of the inkjet head of this invention. It is an element enlarged view showing an example of an ink jet head of the present invention. It is a principal part expanded sectional view which shows an example of the inkjet head of this invention.

Explanation of symbols

(About Figures 1 and 2)
200 Ink cartridge 241 Ink bag 242 Ink inlet 243 Ink outlet 244 Cartridge exterior (case)
(About FIGS. 3-5)
101 apparatus main body 102 paper feed tray 103 paper discharge tray 104 ink cartridge loading unit 105 operation unit 111 upper cover 112 front surface 115 front cover 131 guide rod 132 stay 133 carriage 134 recording head 135 sub tank 141 paper placement unit 142 paper 143 paper supply roller 144 Separator Pad 145 Guide 151 Conveyor Belt 152 Counter Roller 153 Conveyor Guide 154 Pressing Member 155 Tip Pressure Roller 156 Charging Roller 157 Conveying Roller 158 Densation Roller 161 Guide Member 171 Separation Claw 172 Discharge Roller 173 Discharge Roller 181 Double-sided Paper Feed Unit 182 Manual paper feed unit
DESCRIPTION OF SYMBOLS 10 Frame 12 Common liquid chamber 20 Flow path plate 21 Fluid resistance part 22 Pressurized liquid chamber 23 Communication port 24 Partition 30 Nozzle plate 31 Nozzle 40 Base 50 Multilayer piezoelectric element 51 Piezoelectric layer 52 Internal electrode layer 53 External electrode 54 Individual electrode 55 Common Electrode 56 Drive part (movable part)
57 Supporting part 60 Diaphragm 61 Island-like convex part 62 Diaphragm part 63 Ink inlet 70 Adhesive layer 80 FPC
90 Ink repellent layer

Claims (13)

At least one surface or both surfaces on a support mainly composed of cellulose pulp has a single or multi-layer color material pigment permeation prevention layer (barrier layer), and the barrier layer is an alumina having a refractive index of 1.5 or more. Inkjet recording for pigment inks containing at least 30% by weight or more of inorganic pigment (P2) other than hydrate, and the content of pigment (P2) having a refractive index of less than 1.5 in the barrier layer is 10% by weight or less An ink jet recording ink suitable for ink jet recording on a medium, comprising water, a water-soluble organic solvent, a water dispersible resin (A) and a pigment (P1) as a colorant (B) A recording ink having a surface tension at 25 ° C. of 20 to 35 mN / m and a viscosity at 25 ° C. of 5 mPa · s or more. Contains one or more activators and / or silicon surfactants, and the water-dispersible resin (A) and the colorant (B) are present in the ink in a total of 5 to 40% by weight, and are water-dispersible. An ink for ink jet recording, wherein the weight ratio (A) / (B) of the resin (A) and the colorant (B) is from 0.5 to 4. The inkjet recording according to claim 1, wherein the water-dispersible resin (A) contains at least one of an anionic self-emulsifying ether polyurethane resin emulsion and an acrylic-silicon resin emulsion. ink. The ink for inkjet recording according to claim 1 or 2, wherein the fluorosurfactant has the following structural formula (1) or structural formula (2).

(In the formula, Rf represents a fluorine-containing group. M, n, and p represent integers.)

(In the formula, m ¹ represents an integer of 0 to 10, and n ¹ represents an integer of ¹ to 40.) The ink for inkjet recording according to claim 1 or 2, wherein the silicon-based surfactant has the following structural formula (3).

(In the formula, m ² , n ² , a and b represent integers. R represents a substituted or unsubstituted alkyl group or an aryl group.) The water-soluble organic solvent is glycerin, trimethylolpropane, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,3-butanediol, 2,3-butanediol, 1,4 -Butanediol, 3-methyl-1,3-butanediol, 1,5-pentanediol, 1,6-hexanediol, 2-methyl-2,4-hexanediol, 2-pyrrolidone, N-methyl-2- The ink for inkjet recording according to any one of claims 1 to 4, wherein the ink is at least one selected from pyrrolidone, N-hydroxyethyl-2-pyrrolidone, tetramethylurea, and urea. An ink set for ink jet recording, wherein the ink for ink jet recording comprises a black ink and a color ink. An ink medium set for ink jet recording comprising an ink for ink jet recording and an ink jet recording medium, the ink comprising pigment (P1) as water, a water-soluble organic solvent, a water dispersible resin (A) and a colorant (B) And a surface tension at 25 ° C. of 20 to 35 mN / m, a viscosity at 25 ° C. of 5 mPa · s or more, and a fluorine-based surfactant and / or a silicon-based surfactant as a surfactant in the ink. One or more surfactants are contained, and the water-dispersible resin (A) and the colorant (B) are present in the ink in a total amount of 5 to 40% by weight, and the water-dispersible resin (A) and the colorant are present. (B) The weight ratio (A) / (B) is an ink having a weight ratio of 0.5 to 4, and the inkjet recording medium has at least one surface on a support mainly composed of cellulose pulp or On the surface, there is a single layer or multilayer colorant pigment permeation prevention layer (barrier layer), and the barrier layer contains at least 30% by weight or more of inorganic pigment (P2) other than alumina hydrate having a refractive index of 1.5 or more. An ink-media set for ink-jet recording, characterized in that it is a recording medium containing and having a content of a pigment having a refractive index of less than 1.5 in the barrier layer of 10% by weight or less. An ink cartridge comprising the ink according to any one of claims 1 to 5 or the ink set according to claim 6 contained in a container. An ink jet recording method using the ink-media set for ink jet recording according to claim 7, wherein recording is performed with an ink adhesion amount of 15 g / m ² or less. The inkjet recording method according to claim 9, further comprising an ink flying step of applying a stimulus to the ink and causing the ink to fly to form an image on the recording medium. The inkjet recording method according to claim 10, wherein the stimulus is at least one selected from heat, pressure, vibration, and light. Water, a water-soluble organic solvent, a water-dispersible resin (A), and a pigment (P1) as a colorant (B), and a surface tension at 25 ° C. of 20 to 35 mN / m and a viscosity at 25 ° C. of 5 mPa S or more, and the ink contains at least one fluorine-based surfactant and / or silicon-based surfactant as a surfactant, and the water-dispersible resin (A) and the colorant (B) are A total of 5 to 40% by weight of the ink in an ink jet recording ink, and the weight ratio (A) / (B) of the water-dispersible resin (A) to the colorant (B) is 0.5 to 4; , Having at least one surface or both surfaces on the support mainly composed of cellulose pulp, a single layer or multiple layers of colorant pigment permeation prevention layer (barrier layer), and the barrier layer has a refractive index of 1.5 or more Little inorganic pigment (P2) other than alumina hydrate An ink jet recording medium containing at least 30% by weight and containing 10% by weight or less of a pigment having a refractive index of less than 1.5 in the barrier layer, and an ink cartridge for storing the ink for ink jet recording. An ink jet recording apparatus comprising ink jetting means for causing the ink jet recording ink to fly toward the recording medium and printing with an ink adhesion amount of 15 g / m ² or less. An apparatus for recording an image on paper by discharging the ink for ink jet recording according to any one of claims 1 to 5 or the ink set for ink jet recording according to claim 6 as droplets from a recording head, The paper has one or more layers of a colorant pigment permeation preventive layer (barrier layer) on at least one surface or both surfaces of a support mainly composed of cellulose pulp, and the barrier layer has a refractive index of 1.5. An ink jet recording medium comprising at least 30% by weight or more of the inorganic pigment (P2) other than the above-mentioned alumina hydrate and having a pigment content of less than 1.5 in the barrier layer of 10% by weight or less. An ink jet recording apparatus comprising: a unit that reverses the paper to enable double-sided printing.

Images