WO2004003092A1 - Non-aqueous ink composition and method for preparation thereof - Google Patents

Non-aqueous ink composition and method for preparation thereof Download PDF

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Publication number
WO2004003092A1
WO2004003092A1 PCT/JP2003/007935 JP0307935W WO2004003092A1 WO 2004003092 A1 WO2004003092 A1 WO 2004003092A1 JP 0307935 W JP0307935 W JP 0307935W WO 2004003092 A1 WO2004003092 A1 WO 2004003092A1
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Prior art keywords
ink
ink composition
silica particles
silica
pigment
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PCT/JP2003/007935
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French (fr)
Japanese (ja)
Inventor
Toshihiro Endo
Hiroyuki Ogawa
Teruaki Okawa
Osamu Matsumoto
Yasuo Yamamoto
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Riso Kagaku Corporation
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Publication of WO2004003092A1 publication Critical patent/WO2004003092A1/en

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    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00Inks
    • C09D11/30Inkjet printing inks
    • C09D11/36Inkjet printing inks based on non-aqueous solvents

Definitions

  • the present invention relates to an ink composition for use in a printer for performing recording, and more particularly to a low-viscosity non-aqueous ink composition and a method for producing the same.
  • the ink jet recording system is a printing system that ejects liquid ink with high fluidity from fine nozzles and prints it by attaching it to a recording medium such as paper.It is a relatively inexpensive device with high resolution and high quality. The system is capable of printing images at high speed and with low noise, and is a system that is rapidly spreading recently.
  • the inks used in this ink jet recording system are broadly classified into aqueous type inks and non-aqueous type inks.
  • the water-based ink is obtained by dissolving a water-soluble dye in a glycol-based solvent and water, etc. and dispersing a solid pigment in a glycol-based solvent and water to improve light resistance and image bleeding. Is also used. Further, it is better that the ink liquid ejection speed is high in order to print at high speed, and it has been proposed to add silica particles to an aqueous solvent in order to increase the ink liquid ejection speed (Japanese Patent Laid-Open Publication No. Heisei 9 (1999) -207). 5-1 1 7 5 6 2 publication). However, in any case, there is a problem that the water-based type ink generally has poor water resistance.
  • non-aqueous type inks have the advantage of being superior in water resistance.
  • This non-aqueous type ink mainly includes a solvent-based ink mainly composed of a volatile solvent and a non-volatile solvent mainly.
  • Oil-based ink In particular, the latter oil-based ink has the feature that the number of times of cleaning during printing is small because nozzle clogging is unlikely to occur, and is more suitable as ink for high-speed inkjet printers.
  • Oil-based inks have the problem of causing ink bleeding or strike-through when a dye soluble in a solvent is used as a coloring agent.
  • a pigment is used as a coloring agent and the dispersibility of this pigment is improved to improve the dispersibility of the nozzle Clogging is suppressed.
  • a silica particle table is used as a method for improving the dispersibility of the pigment. It has been proposed that a color pigment be physically bonded to the surface (Japanese Patent Application Laid-Open No. 2003-49096).
  • stencil printing In the field of stencil printing, in which stencil printing is performed using a stencil sheet and ink is supplied from a perforated portion formed in the stencil sheet to print on a printing material such as paper, the stencil printing is performed on one side of a porous support.
  • a stencil printing system that uses a stencil sheet coated with a porous resin film to close the pores of the porous resin film corresponding to the non-image area to form an opaque non-inking part (Japanese Patent Application No. 2000-01) — 283600) or a stencil printing system using a microporous stencil made of an inelastic resin film (Japanese Patent Application Laid-Open No. 2002-21040) has been proposed. .
  • These stencil printing systems have received great attention because the use of low-viscosity inks can dramatically improve the drying properties of inks compared to conventional systems.
  • a stencil system is called a low-viscosity stencil system).
  • Inks used in such a low-viscosity stencil system include water-based inks, water-in-oil emulsion inks, and non-aqueous inks.However, ink dries on the plate or printing drum, causing clogging. Because of the difficulty, oil-based ink is often selected. '
  • Both the ink jet recording system and the low viscosity stencil system require the use of low viscosity ink, and when an image is formed on a permeable recording medium such as paper (hereinafter referred to as recording paper), Due to the low viscosity of the ink, the coloring material moves to near the back side of the recording paper, and there is a problem that an image can be seen through from the back side, that is, so-called strike-through occurs. In particular, this tendency is remarkable in plain paper in which the voids between the fibers of the paper are large, since the coloring material easily moves.
  • the present invention has been made in view of the above circumstances, and has excellent water resistance and high quality images with little strikethrough and little image bleeding even on recording paper that has not been subjected to special processing, so-called plain paper. To provide a low-viscosity ink composition that can be formed It is assumed that.
  • the non-aqueous ink composition of the present invention contains at least a solvent, a color pigment, and a dispersant,
  • the solid particles having substantially no coloring ability for preventing the coloring pigment from moving from the front surface to the back surface of the recording paper during printing on the recording paper are referred to as recording particles in a process in which ink penetrates into the recording paper.
  • the fact that the coloring pigment contained in the ink stays in the fiber of the paper and prevents it from moving from the front surface to the back surface of the recording paper, and is itself a solid particle having no function of coloring the recording paper. means.
  • the shape is not necessarily required to be particulate, and for example, it may be fine fibrous.
  • the solid particles are bonded to the color pigment, the interaction between the silica particles is hindered by the bonded color pigment, so that the ink remaining in the fiber voids of the paper does not have a thickening effect and the fiber voids are not generated.
  • the solid particles combined with the coloring pigment are removed because the remaining ink escapes to the back of the paper.
  • the solid particles are preferably, for example, silicon particles. More preferably, the sily particles are contained in the ink composition in an amount of 1 to 10% by weight. In this case, the average particle diameter of the silica particles is desirably 300 nm or less. Further, the average particle size of the silica particles is preferably 0.1 to 10 times the average particle size of the color pigment.
  • the non-aqueous ink composition of the present invention includes the solvent, the dispersant, and the silica particles, and includes a silica particle dispersion liquid that does not include the color pigment, the solvent, the dispersant, and the color pigment. It is preferably obtained by mixing with a color pigment dispersion liquid containing no silica particles.
  • the dispersant contained in the silica particle dispersion is a polyesteramine-based polymer dispersant, and the content of the polyesteramine-based polymer dispersant with respect to the silicic acid particles is a weight ratio. Is preferably 0.1 or more.
  • the method for producing a non-aqueous ink composition according to the present invention includes the step of: After preparing a silica particle dispersion liquid containing power particles and not containing the color pigment, and a color pigment dispersion liquid containing the solvent, the dispersant and the color pigment, and containing no silica particles, respectively, It is characterized by mixing a silica particle dispersion and the above-mentioned color pigment dispersion.
  • strike-through occurs more easily as the color material contained in the ink moves from the recording surface of the recording paper to the back surface.
  • strike-through is remarkable in printing and recording inks having low viscosity and small dispersion of pigment particles, and plain paper with large voids between fibers.
  • the coloring pigment moves from the recording paper surface to the back surface during printing on the recording paper. Since the ink contains solid particles that have substantially no coloring ability, the solid particles stay in the fibers of the recording paper and are contained in the ink during the process of ink penetration into the recording paper. This prevents color pigments from moving from the front side to the back side of the recording paper, and has no function of coloring the recording paper itself, so that strikethrough can be effectively prevented.
  • the coloring pigment also moves in the horizontal direction of the recording paper.However, since the solid particles stay in the fibers of the recording paper, the movement of the coloring pigment in the horizontal direction can be prevented. As a result, bleeding of an image can be reduced, and a high-quality printed matter can be obtained.
  • the solid particles are not bonded to the color pigment, most of the solvent is absorbed by the fibers of the paper when the ink is transferred to the paper, and the silica particles ( (Solid) ink remains.
  • the ink viscosity increases due to the interaction between the silica particles (hydrogen cross-linking of silanol groups), and the ink is prevented from passing through the fiber voids of the paper to the back side, and the strike-through effect is suppressed. Can be prevented.
  • the above-mentioned strikethrough can be effectively prevented by containing 1 to 10% by weight in the ink composition, and the ink jet recording can be performed. High-quality image formation with less image bleeding is possible in systems and low-viscosity stencil systems.
  • the non-aqueous ink composition of the present invention contains the solvent, the dispersant, and the silica particles, and includes the silica particle dispersion liquid that does not include the color pigment, and includes the solvent, the dispersant, and the color pigment.
  • the non-aqueous ink composition of the present invention is a non-aqueous ink composition containing at least a solvent, a coloring pigment, and a dispersant, and having a viscosity of not more than 30 mPas at 23 ° C. It contains particles.
  • solid particles include inorganic fine particles such as silica, clay, talc, clay, diatomaceous earth, calcium carbonate, barium carbonate, barium sulfate, titanium oxide, alumina white, silica, myriki, and aluminum hydroxide.
  • organic fine particles such as polyacrylate, polyurethane, polyester, polyethylene, polypropylene, polychlorinated biel, polyvinylidene chloride, polystyrene, polysiloxane, phenolic resin, epoxy resin, and benzoguanamine resin, or copolymers thereof. Fine particles composed of a body are used. It is desirable that these solid particles have high wettability with respect to the solvent to be used. However, even if the solid particles have low wettability by appropriately selecting a dispersant, they can be used.
  • the above solid particles may be used alone or in an appropriate combination.
  • the amount of solid particles to be added varies depending on the type of solid particles. However, it is desirable to contain 1 to 4% by weight.
  • the amount is less than 1% by weight, the effect of preventing the color pigment from moving from the front surface to the back surface of the recording paper is reduced, and the effect of preventing strike-through is reduced.
  • the larger the amount of addition the greater the effect of reducing strike-through, but if added too much, the viscosity of the ink increases, making it difficult to eject ink from the head in an ink jet recording system, or in the stencil system. Poor ink permeability of stencil paper causes poor image formation Live.
  • the added amount of the silica particles is too large, the ink viscosity particularly in a stationary state increases, and the thixotropic property increases. This thixotropic property means that the particle size is 1 ⁇ !
  • the ink not exhibit thixotropic properties, more specifically, by setting the viscosity at a shear stress of 100 (lZs) to within twice the shear stress at a shear stress of 100 (lZs), It enables stable image formation regardless of the environment where the ink is placed.
  • the polar solvent described below and further suitably selecting the dispersing agent described later, it becomes possible to add more silica particles without developing thixotropic properties. Even when such a method is employed, it is not preferable to add too much silicic acid particles because the thixotropic properties are exhibited. Therefore, when solid particles other than silica particles are used, the addition amount can be adjusted from these viewpoints.
  • strike-through can be further reduced by setting the average particle diameter of the silica particles in the ink to 300 nm or less.
  • the average particle size of the silica particles is preferably 300 nm or less, more preferably 200 nm or less, and further preferably 150 nm or less.
  • the average particle diameter of the silica particles is preferably 0.1 to 10 times the average particle diameter of the color pigment. If the average particle size of the silica particles is smaller than 0.1 times the average particle size of the color pigment, or if the average particle size of the silica particles is larger than 10 times the average particle size of the color pigment, strikethrough occurs. More likely to happen.
  • the solvent used in the non-aqueous ink composition of the present invention may be a polar solvent or a non-polar solvent.
  • the polar solvent include ester solvents, alcohol solvents, and higher fatty acid solvents. , Ether-based solvents and their mixed solvents can be used You.
  • the polar solvent is selected to be a single phase when mixed with a non-polar solvent.
  • Ester solvents alcohol solvents such as isomiri stino oleanol, isopalmitino real alcohol, isostearyl alcohol, oleyl alcohol, etc., isononanoic acid , Isomiristinic acid, hexadecanoic acid, isopalmitic acid, oleic acid, isostearic acid, etc., higher fatty acid solvents, getyl glycol monobutyl ether, ethylene daryl monobutyl ether, propylene glycol monobutynoate ether, propylene glycol diethylene glycol Examples include ether solvents such as butyl ether.
  • Non-polar solvents include non-polar solvents such as naphthenic solvents, paraffinic solvents, and isoparaffinic solvents.
  • non-polar solvents such as naphthenic solvents, paraffinic solvents, and isoparaffinic solvents.
  • a polar solvent or a non-polar solvent may be used alone, or two or more types may be appropriately selected and used, or a polar solvent and a non-polar solvent may be appropriately used in combination. Is also possible.
  • Dispersing agents include carboxylic acid esters containing hydroxyl groups and long-chain polyaminoamides.
  • dispersing agent examples include “Anti_Terra_U (polyaminoamide phosphate)” manufactured by BYK Chemie and “Anti-Terra—203322 (high molecular weight polycarboxylic acid). Salt), ”Disperbyk—101 (polyaminoamide phosphate and acid ester), 107 (hydroxyl-containing carboxylic acid ester), 110 (copolymer containing acid group), 130 ( (Polyamide), 161, 162, 163, 164, 165, 1666, 170 (polymer copolymer) "," 400 ",” Bykum “ en (high molecular weight unsaturated acid ester) "," BYK_P104, PI05 (high molecular weight unsaturated acid polycarboxylic acid) ",” P104S, 240S (high molecular weight unsaturated) Acid polycarboxylic acid and silicone) and Lactimon (long-chain amine, unsaturated acid polycarboxylic acid and silicon).
  • DISVALON KS-860, 873 SN, 874 polymer dispersant
  • # 2150 aliphatic polycarboxylic acid
  • # 7004 polyetherester type
  • DA-703-50 polyester acid Amide amine salt
  • color pigments those generally used in the printing technical field can be used irrespective of inorganic pigments and organic pigments.
  • Conventionally known pigments such as a system pigment and a metal complex pigment can be used without any particular limitation.
  • the above pigments may be used alone or in an appropriate combination, and are desirably contained in the range of 0.01 to 20% by weight based on the whole ink composition.
  • the non-aqueous ink composition of the present invention can be manufactured by a conventionally known manufacturing method.However, silica particles and a coloring pigment are separately prepared as a dispersion, and then mixed with each other to obtain silica particles.
  • a non-aqueous ink composition in which the color pigment is not physically bound can be obtained. That is, a silica particle dispersion liquid containing a solvent, a dispersant, and silica particles and containing no color pigment, and a color pigment dispersion liquid containing a solvent, a dispersant, and a color pigment but containing no silica particles were prepared. Mix It is preferable to obtain a non-aqueous ink composition in total.
  • the solid particles and the coloring pigment can be dispersed by a conventionally known dispersing means such as a bead mill.
  • Solsperse 139400 polymer dispersant: Abyssia
  • a vegetable fatty acid ester solvent : Mitsubishi Chemical Corporation
  • 5 parts by weight were added and premixed. Thereafter, the mixture was dispersed in a bead mill with a residence time of about 20 minutes to obtain a pigment dispersion.
  • 56 parts by weight of a vegetable fatty acid ester solvent and 20 parts by weight of a naphthenic solvent are mixed, and 4 parts by weight of Solsperse 139400 as a dispersing agent are dissolved therein, and further, aerogel as silica particles is dissolved.
  • Example 3 An ink was obtained in the same manner as in Example 1 except that aerogel RY200 (produced by AEROSIL Co., Ltd.) was used as the silica particles. -(Example 3)
  • An ink was obtained in the same manner as in Example 1 except that aerogel R812 (manufactured by Nippon Aerosil Co., Ltd.) was used as the silica particles.
  • An ink was obtained in the same manner as in Example 1 except that aerogel OX50 (manufactured by Nippon Aerosil Co., Ltd.) was used as the silica particles.
  • Example 7 An ink was obtained in the same manner as in Example 1 except that the composition of the silica dispersion was changed as shown in Table 1.
  • An ink was obtained in the same manner as in Example 1 except that the composition of the silica dispersion was as shown in Table 1 and the pigment was changed to Pigment Yellow (manufactured by Dainichi Seika).
  • An ink was obtained in the same manner as in Example 8, except that the residence time of the sily dispersion was 60 minutes.
  • Example 1 An ink was obtained in the same manner as in Example 1 except that aerogel R972 was used as the sily particles, and the mixing of the shiri force dispersion was as shown in Table 1.
  • Table 1 shows the ink formulations of Examples 1 to 10 and Comparative Examples 1 and 3, and a summary of the ink viscosities, pigment particle diameters, and silica particle diameters.
  • the pigment dispersion is diluted with a solvent so that the pigment concentration becomes 0.1%, printed on plain paper (“Ideal Paper Thick S”, manufactured by Riso Kagaku Kogyo Co., Ltd.), and the printed portion is scanned with a scanning electron microscope.
  • the pigment particles which can be observed on paper fibers were selected arbitrarily, and the diameter (the direction in which the length becomes the longest) of the pigment particles was measured, and the average value was defined as the particle diameter.
  • the silica dispersion is diluted with a solvent so that the silica concentration is 0.1%, and this is printed on plain paper (“Ideal Paper Thick s” manufactured by Riso Kagaku Kogyo Co., Ltd.). Observe the letter-shaped part with a scanning electron microscope, select 100 silica particles that can be observed on the paper fiber, measure the diameter of the silica particles (the direction in which the length becomes the longest), and calculate the average value of the particles. Diameter.
  • 00 value is 0.13 or more and less than 0.20
  • X: 00 value is 0.20 or more
  • the ink compositions of Examples 1 to 10 have a viscosity at 30 ° C of 30 mPas or less, and are therefore suitable for ink jet recording systems and low viscosity stencil systems. Even if it is used, there will be no problem when ink ejection from the head becomes difficult or the ink permeability of the stencil paper becomes poor, resulting in poor image formation.Silica particles are used as solid particles. Since it was contained, it became possible to effectively prevent strikethrough.
  • the average particle diameter of the silica particles is about 300 nm or less, the show-through reduction effect and the image formation are good.
  • Example 5 some breakthrough of force with an average particle diameter of 300 nm or less was observed. This is because the added amount of silica particles is as low as 0.5 part by weight.
  • Example 10 although strike-through was slightly observed even though the average particle size was 300 nm or less, the average particle size of the silica particles was less than 0.1 times the particle size of the color pigment. For.
  • the color pigment is printed from the surface of the recording paper when printing on the recording paper. Since the ink contains solid particles that have substantially no coloring ability that prevents it from moving to the back surface, the solid particles are converted into fibers of the recording paper during the process of ink penetration into the recording paper. The color pigment contained in the ink stays in the ink and is prevented from moving from the front side to the back side of the recording paper, and the solid particles themselves do not have the function of coloring the recording paper. It became possible to prevent.
  • the non-aqueous ink composition of the present invention may contain, for example, various additives other than the solvent, the color pigment, the dispersant, and the solid particles.
  • various additives other than the solvent, the color pigment, the dispersant, and the solid particles In Examples, silica particles are used as the solid particles.
  • solid particles other than the above are used, the strike-through reduction effect of the present invention and high-quality image formation without image bleeding can be realized.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)
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  • Ink Jet Recording Methods And Recording Media Thereof (AREA)

Abstract

A non-aqueous ink composition containing a solvent, a coloring pigment and a dispersant and having a viscosity at 23°C of 30 mPa · s or less, characterized in that it further comprises solid particles which have substantially no coloring ability and are capable of preventing the movement of the coloring pigment, during the printing onto a recording paper, from the front surface of the recording paper to the backside thereof. The non-aqueous ink composition has a low viscosity and allows the formation of an image having high quality being reduced in strike-through and oozing and thus of high quality, even when use is made of a recording paper not being specially processed, that is, an ordinary paper.

Description

明 細 書 非水系ィンク組成物及びその製造方法 [技術分野]  Description Non-aqueous ink composition and method for producing the same [Technical Field]
本発明は、 記録を行うプリンタに供するインク組成物に関し、 特に低粘度の非 水系ィンク組成物、 及びその製造方法に関するものである。  The present invention relates to an ink composition for use in a printer for performing recording, and more particularly to a low-viscosity non-aqueous ink composition and a method for producing the same.
[背景技術]  [Background technology]
ィンクジェッ ト記録システムは、 流動性の高い液体ィンクを微細なノズルから 噴射し、 紙等の記録媒体に付着させて印刷を行う印刷システムであり、 比較的安 価な装置で高解像度、 高品位の画像を、 高速かつ低騒音で印刷可能という特徴を 有し、 最近急速に普及しつつあるシステムである。  The ink jet recording system is a printing system that ejects liquid ink with high fluidity from fine nozzles and prints it by attaching it to a recording medium such as paper.It is a relatively inexpensive device with high resolution and high quality. The system is capable of printing images at high speed and with low noise, and is a system that is rapidly spreading recently.
このインクジエツ ト記録システムに用いられるインクは、 大きく水系タイプィ ンクと非水系タイプインクに分けられる。 水系タイプインクは、 水溶性染料をグ リ コール系溶剤と水等に溶解したものであり、 耐光性や画像滲み等を向上させる ため、 固体の顔料をグリコール系溶剤と水等に分散させたものも用いられる。 さ らに、 高速で印字するためにはインク液吐出速度が速い方がよいため、 このイン ク液吐出速度を早くするために水性溶剤にシリカ粒子を添加することが提案され ている (特開平 5 - 1 1 7 5 6 2号公報) 。 しかし、 いずれにしても水系タイプ ィンクは一般的に耐水性が悪いという問題がある。  The inks used in this ink jet recording system are broadly classified into aqueous type inks and non-aqueous type inks. The water-based ink is obtained by dissolving a water-soluble dye in a glycol-based solvent and water, etc. and dispersing a solid pigment in a glycol-based solvent and water to improve light resistance and image bleeding. Is also used. Further, it is better that the ink liquid ejection speed is high in order to print at high speed, and it has been proposed to add silica particles to an aqueous solvent in order to increase the ink liquid ejection speed (Japanese Patent Laid-Open Publication No. Heisei 9 (1999) -207). 5-1 1 7 5 6 2 publication). However, in any case, there is a problem that the water-based type ink generally has poor water resistance.
これに対し、 非水系タイプィンクは耐水性に優れているという利点を有してお り、 この非水系タイプインクは、 揮発性溶剤を主体とする溶剤系インクと、 不揮 発性溶剤を主体とするオイル系ィンクに分けられる。 特に後者のオイル系ィンク は、 ノズルの目詰まりが生じにくいため印刷中のク リ一ユングの回数が少なくて 済むといった特徴を有し、 高速インクジェッ トプリンタ用インクとしてより適し たものである。 オイル系ィンクは溶剤に溶解する染料を着色剤として用いると、 ィンク滲みや裏抜け等が発生するという問題が生じるため、 顔料を着色剤として 用いるとともに、 この顔料の分散性を向上させることによってノズルの目詰まり を抑制している。 顔料の分散性を向上させる方法と しては、 例えばシリカ粒子表 面に着色顔料を物理的に結合させることが提案されている (特開 2 0 0 3— 4 9 0 9 6号公報) 。 On the other hand, non-aqueous type inks have the advantage of being superior in water resistance. This non-aqueous type ink mainly includes a solvent-based ink mainly composed of a volatile solvent and a non-volatile solvent mainly. Oil-based ink. In particular, the latter oil-based ink has the feature that the number of times of cleaning during printing is small because nozzle clogging is unlikely to occur, and is more suitable as ink for high-speed inkjet printers. Oil-based inks have the problem of causing ink bleeding or strike-through when a dye soluble in a solvent is used as a coloring agent.Therefore, a pigment is used as a coloring agent and the dispersibility of this pigment is improved to improve the dispersibility of the nozzle Clogging is suppressed. As a method for improving the dispersibility of the pigment, for example, a silica particle table is used. It has been proposed that a color pigment be physically bonded to the surface (Japanese Patent Application Laid-Open No. 2003-49096).
また、 孔版印刷原紙を用いて製版を行い、 原紙に形成された穿孔部からインク を供給して紙などの被印刷体に印刷を行う孔版印刷の分野では、 多孔性支持体の 一方の面上に、 多孔性樹脂膜を塗工した孔版原紙を使用し、 非画線部に対応する 多孔性樹脂膜の孔を閉塞させてィンキ非透過部を形成させる孔版印刷システム (特願 2 0 0 1— 2 8 3 6 0 0号) 、 あるいは非弾性樹脂フィルムからなる微多 孔性孔版原紙を用いた孔版印刷システム (特開 2 0 0 2— 2 1 4 0号公報) が提 案されている。 これらの孔版印刷システムは、 低粘度インクを使用することによ つて、 インクの乾燥性を従来のシステムより飛躍的に向上できることから大きな 注目を集めている (以下、 これらの低粘度インクを使用する孔版システムを低粘 度孔版システムという) 。  In the field of stencil printing, in which stencil printing is performed using a stencil sheet and ink is supplied from a perforated portion formed in the stencil sheet to print on a printing material such as paper, the stencil printing is performed on one side of a porous support. In addition, a stencil printing system that uses a stencil sheet coated with a porous resin film to close the pores of the porous resin film corresponding to the non-image area to form an opaque non-inking part (Japanese Patent Application No. 2000-01) — 283600) or a stencil printing system using a microporous stencil made of an inelastic resin film (Japanese Patent Application Laid-Open No. 2002-21040) has been proposed. . These stencil printing systems have received great attention because the use of low-viscosity inks can dramatically improve the drying properties of inks compared to conventional systems. A stencil system is called a low-viscosity stencil system).
このような低粘度孔版システムに用いられるィンクとしては、 水系タイプイン ク、 油中水系エマルシヨンタイプインクや非水系タイプインクがあるが、 版や印 刷ドラムでインクが乾燥し目詰まりが発生しにくいという理由から、 オイル系ィ ンクが選択されることが多い。 '  Inks used in such a low-viscosity stencil system include water-based inks, water-in-oil emulsion inks, and non-aqueous inks.However, ink dries on the plate or printing drum, causing clogging. Because of the difficulty, oil-based ink is often selected. '
上記のインクジエツ ト記録システムや低粘度孔版システムは、 いずれも低粘度 インクの使用が必要であり、 紙などのように浸透性がある記録媒体 (以下、 記録 紙という) に画像を形成した場合、 インクの粘度が低いことに起因して、 記録紙 の裏側近くまで色材が移動し、 裏側から画像が透けて見える、 いわゆる裏抜けが 発生するという問題がある。 特に紙の繊維間の空隙が大きい普通紙では色材が移 動しやすいため、 この傾向が顕著である。  Both the ink jet recording system and the low viscosity stencil system require the use of low viscosity ink, and when an image is formed on a permeable recording medium such as paper (hereinafter referred to as recording paper), Due to the low viscosity of the ink, the coloring material moves to near the back side of the recording paper, and there is a problem that an image can be seen through from the back side, that is, so-called strike-through occurs. In particular, this tendency is remarkable in plain paper in which the voids between the fibers of the paper are large, since the coloring material easily moves.
このような問題を解決するために、 記録紙の表面に顔料等を塗工するなどの特 殊な加工を施すことによって色材を記録紙表面に留め、 裏抜けを低減させる方法 が提案されているが、 このような特殊な加工を施した塗工紙やインクジェッ ト専 用紙などの使用は印刷コス トが高くなるといつた問題がある。  In order to solve such a problem, a method has been proposed in which the coloring material is fixed to the recording paper surface by performing a special process such as applying a pigment or the like to the recording paper surface to reduce strikethrough. However, the use of such specially processed coated paper or inkjet paper has a problem when the printing cost increases.
本発明は上記事情に鑑みなされたものであり、 耐水性に優れ、 特殊加工が施さ れていない記録紙、 いわゆる普通紙に対しても、 裏抜けが少なくかつ画像滲みの 少ない、 高品位な画像形成が可能な低粘度のインク組成物を提供することを目的 とするものである。 The present invention has been made in view of the above circumstances, and has excellent water resistance and high quality images with little strikethrough and little image bleeding even on recording paper that has not been subjected to special processing, so-called plain paper. To provide a low-viscosity ink composition that can be formed It is assumed that.
[発明の開示]  [Disclosure of the Invention]
本発明の非水系インク組成物は、 少なく とも溶剤、 着色顔料、 分散剤を含み、 The non-aqueous ink composition of the present invention contains at least a solvent, a color pigment, and a dispersant,
2 3 °Cにおける粘度が 3 O m P a · s以下の非水系インク組成物であって、 記録 紙への印刷時に前記着色顔料が前記記録紙表面から裏面へ移動することを阻止す る実質的に着色能を有さない固体粒子を含有したことを特徴とするものである。 記録紙への印刷時に前記着色顔料が前記記録紙表面から裏面へ移動することを 阻止する実質的に着色能を有さない固体粒子とは、 インクが記録紙内部に浸透す る過程において、 記録紙の繊維に留まってィンクに含有されている着色顔料が記 録紙表面から裏面へ移動することを阻止し、 かつそれ自体は記録紙を着色する機 能を有さない固体粒子であることを意味する。 従って、 そのような機能を有して いればその形状は必ずしも粒子状である必要はなく、 例えば微細な繊維状であつ てもよい。 但し、 固体粒子が着色顔料と結合していると、 結合した着色顔料によ つてシリカ粒子間の相互作用が妨害され、 用紙の繊維空隙に残ったインクの増粘 効果が発生せず、 繊維空隙に残ったインクが用紙の裏面に抜けてしまうため着色 顔料と結合している固体粒子は除かれる。 - 固体粒子としては、例えば、 シリ力粒子であることが好ましい。 シリ力粒子は、 インク組成物中に 1〜 1 0重量%含有することがより好ましい。また、その場合、 シリカ粒子の平均粒子径は 3 0 0 n m以下であることが望ましい。 さらに、 前記 シリカ粒子の平均粒子径は前記着色顔料の平均粒子径の 0 . 1〜 1 0倍であるこ とが好ましい。 23 A non-aqueous ink composition having a viscosity of 3 OmPas or less at 23 ° C, which substantially prevents the coloring pigment from moving from the front surface to the back surface of the recording paper during printing on recording paper. It is characterized by containing solid particles having no specific coloring ability. The solid particles having substantially no coloring ability for preventing the coloring pigment from moving from the front surface to the back surface of the recording paper during printing on the recording paper are referred to as recording particles in a process in which ink penetrates into the recording paper. The fact that the coloring pigment contained in the ink stays in the fiber of the paper and prevents it from moving from the front surface to the back surface of the recording paper, and is itself a solid particle having no function of coloring the recording paper. means. Therefore, as long as it has such a function, the shape is not necessarily required to be particulate, and for example, it may be fine fibrous. However, if the solid particles are bonded to the color pigment, the interaction between the silica particles is hindered by the bonded color pigment, so that the ink remaining in the fiber voids of the paper does not have a thickening effect and the fiber voids are not generated. The solid particles combined with the coloring pigment are removed because the remaining ink escapes to the back of the paper. -The solid particles are preferably, for example, silicon particles. More preferably, the sily particles are contained in the ink composition in an amount of 1 to 10% by weight. In this case, the average particle diameter of the silica particles is desirably 300 nm or less. Further, the average particle size of the silica particles is preferably 0.1 to 10 times the average particle size of the color pigment.
本発明の非水系ィンク組成物は、 前記溶剤と前記分散剤と前記シリカ粒子を含 み、 前記着色顔料を含まないシリカ粒子分散液と、 前記溶剤と前記分散剤と前記 着色顔料を含み、 前記シリカ粒子を含まない着色顔料分散液とを混合して得られ ることが好ましい。 この場合、 前記シリカ粒子分散液に含まれる前記分散剤がポ リエステルァミン系の高分子分散剤であり、 かつ前記シリ力粒子に対する前記ポ リエステルアミン系の高分子分散剤の含有量が重量比で 0 . 1以上であることが 好ましい。  The non-aqueous ink composition of the present invention includes the solvent, the dispersant, and the silica particles, and includes a silica particle dispersion liquid that does not include the color pigment, the solvent, the dispersant, and the color pigment. It is preferably obtained by mixing with a color pigment dispersion liquid containing no silica particles. In this case, the dispersant contained in the silica particle dispersion is a polyesteramine-based polymer dispersant, and the content of the polyesteramine-based polymer dispersant with respect to the silicic acid particles is a weight ratio. Is preferably 0.1 or more.
本発明の非水系ィンク組成物の製造方法は、 前記溶剤と前記分散剤と前記シリ 力粒子を含み、 前記着色顔料を含まないシリカ粒子分散液と、 前記溶剤と前記分 散剤と前記着色顔料を含み、 前記シリカ粒子を含まない着色顔料分散液とをそれ ぞれ調製した後、 前記シリカ粒子分散液と前記着色顔料分散液を混合することを 特徴とするものである。 The method for producing a non-aqueous ink composition according to the present invention includes the step of: After preparing a silica particle dispersion liquid containing power particles and not containing the color pigment, and a color pigment dispersion liquid containing the solvent, the dispersant and the color pigment, and containing no silica particles, respectively, It is characterized by mixing a silica particle dispersion and the above-mentioned color pigment dispersion.
裏抜けは、 インク中に含有される色材が記録紙の記録表面から裏面に移動し易 いほど発生し易い。 特に、 粘度が低くかつ顔料粒子が小さく分散された印刷,記 録用インクや、 繊維間の空隙が大きい普通紙では裏抜けが顕著である。  The strike-through occurs more easily as the color material contained in the ink moves from the recording surface of the recording paper to the back surface. In particular, strike-through is remarkable in printing and recording inks having low viscosity and small dispersion of pigment particles, and plain paper with large voids between fibers.
本発明の非水系インク組成物は、 2 3 °Cにおける粘度が 3 O m P a · s以下の 非水系ィンク組成物において、 記録紙への印刷時に着色顔料が記録紙表面から裏 面へ移動することを阻止する、 実質的に着色能を有さない固体粒子を含有したの で、 インクが記録紙内部に浸透する過程において、 固体粒子が記録紙の繊維に留 まってィンクに含有されている着色顔料が記録紙表面から裏面へ移動することを 阻止し、 かつそれ自体は記録紙を着色する機能を有さないため、 裏抜けを効果的 に防止することが可能となる。 また、 記録紙表面上では、 着色顔料が記録紙の水 平方向にも移動するが、 固体粒子が記録紙の繊維に留まっていることによって、 着色顔料の水平方向への移動も阻止することが可能となるため、 画像の滲みも低 減させることが可能となり高品位な印刷物を得ることができる。  In the non-aqueous ink composition of the present invention, in a non-aqueous ink composition having a viscosity at 23 ° C. of 3 OmPas or less, the coloring pigment moves from the recording paper surface to the back surface during printing on the recording paper. Since the ink contains solid particles that have substantially no coloring ability, the solid particles stay in the fibers of the recording paper and are contained in the ink during the process of ink penetration into the recording paper. This prevents color pigments from moving from the front side to the back side of the recording paper, and has no function of coloring the recording paper itself, so that strikethrough can be effectively prevented. In addition, on the surface of the recording paper, the coloring pigment also moves in the horizontal direction of the recording paper.However, since the solid particles stay in the fibers of the recording paper, the movement of the coloring pigment in the horizontal direction can be prevented. As a result, bleeding of an image can be reduced, and a high-quality printed matter can be obtained.
特に、 本発明の非水系ィンク組成物は固体粒子が着色顔料と結合していないた め、 インクが用紙に転移すると溶剤の大部分が用紙の繊維に吸収され、 繊維空隙 間にはシリカ粒子 (固体) の割合が大きくなつたインクが残る。 このような状態 になると、 シリカ粒子間の相互作用 (シラノール基の水素架橋結合) によりイン ク粘度が増大し、 用紙の繊維空隙を通り抜けてィンクが裏面へ抜けることが抑制 され、 裏抜けを効果的に防止することが可能となる。  In particular, in the non-aqueous ink composition of the present invention, since the solid particles are not bonded to the color pigment, most of the solvent is absorbed by the fibers of the paper when the ink is transferred to the paper, and the silica particles ( (Solid) ink remains. In such a state, the ink viscosity increases due to the interaction between the silica particles (hydrogen cross-linking of silanol groups), and the ink is prevented from passing through the fiber voids of the paper to the back side, and the strike-through effect is suppressed. Can be prevented.
なお、 固体粒子と して、 シリカ粒子を用いた場合、 インク組成物中に 1〜 1 0 重量%含有することによって、 上記裏抜けを効果的に防止することが可能となる とともに、 ィンクジェッ ト記録システムや低粘度孔版システムにおいて画像滲み の少ない、 高品位な画像形成が可能となる。  When silica particles are used as the solid particles, the above-mentioned strikethrough can be effectively prevented by containing 1 to 10% by weight in the ink composition, and the ink jet recording can be performed. High-quality image formation with less image bleeding is possible in systems and low-viscosity stencil systems.
また、 その場合、 シリカ粒子の平均粒子径を 3 0 0 n m以下とすることによつ て、 さらにシリカ粒子の平均粒子径を着色顔料の平均粒子径の 0 . 1 ~ 1 0倍と することによって、 上記裏抜けをさらに効果的に防止することが可能となる。 なお、 本発明の非水系インク組成物を、 前記溶剤と前記分散剤と前記シリカ粒 子を含み、 前記着色顔料を含まないシリカ粒子分散液と、 前記溶剤と前記分散剤 と前記着色顔料を含み、 前記シリ力粒子を含まない着色顔料分散液とをそれぞれ 調製した後、 前記シリカ粒子分散液と前記着色顔料分散液を混合して得ると、 非 水系ィンク組成物中のシリ力粒子と着色顔料の粒子の大きさをそれぞれ制御する ことが容易となり、 裏抜けや画像の滲みの抑制効果をより得やすくなる。 In this case, by setting the average particle diameter of the silica particles to 300 nm or less, the average particle diameter of the silica particles is further reduced to 0.1 to 10 times the average particle diameter of the color pigment. By doing so, it is possible to more effectively prevent the strikethrough. The non-aqueous ink composition of the present invention contains the solvent, the dispersant, and the silica particles, and includes the silica particle dispersion liquid that does not include the color pigment, and includes the solvent, the dispersant, and the color pigment. After preparing the color pigment dispersion liquid not containing the sily particles, respectively, mixing the silica particle dispersion and the color pigment dispersion to obtain the silica particles dispersion and the color pigment in the non-aqueous ink composition It is easy to control the size of each particle, and the effect of suppressing strikethrough and image bleeding can be more easily obtained.
[発明を実施するための好ましい態様]  [Preferred embodiment for carrying out the invention]
本発明の非水系インク組成物は、 少なく とも溶剤、 着色顔料、 分散剤を含み、 2 3 °Cにおける粘度が 3 0 m P a · s以下の非水系インク組成物であって、 所定 の固体粒子を含有したものである。  The non-aqueous ink composition of the present invention is a non-aqueous ink composition containing at least a solvent, a coloring pigment, and a dispersant, and having a viscosity of not more than 30 mPas at 23 ° C. It contains particles.
固体粒子としては、 例えばシリカ、 白土、 タルク、 クレー、 ケイソゥ土、 炭酸 カルシウム、 炭酸バリ ゥム、 硫酸バリ ゥム、 酸化チタン、 アルミナホワイ ト、 力 ォリン、 マイ力、 水酸化アルミニウム等の無機微粒子のほか、 ポリアクリル酸ェ ステル、 ポリ ウレタン、 ポリエステル、 ポリエチレン、 ポリプロピレン、 ポリ塩 化ビエル、 ポリ塩化ビニリデン、 ポリスチレン、 ポリシロキサン、 フエソール樹 脂、 エポキシ樹脂、 ベンゾグアナミン樹脂等の有機微粒子またはこれらの共重合 体からなる微粒子などが用いられる。 これらの 固体粒子は、 使用する溶剤に対 してぬれ性が高いものであることが望ましいが、 分散剤を適宜選択することによ つてぬれ性が低いものであっても用いることができる。  Examples of solid particles include inorganic fine particles such as silica, clay, talc, clay, diatomaceous earth, calcium carbonate, barium carbonate, barium sulfate, titanium oxide, alumina white, silica, myriki, and aluminum hydroxide. In addition, organic fine particles such as polyacrylate, polyurethane, polyester, polyethylene, polypropylene, polychlorinated biel, polyvinylidene chloride, polystyrene, polysiloxane, phenolic resin, epoxy resin, and benzoguanamine resin, or copolymers thereof. Fine particles composed of a body are used. It is desirable that these solid particles have high wettability with respect to the solvent to be used. However, even if the solid particles have low wettability by appropriately selecting a dispersant, they can be used.
上記の固体粒子は、 単独で用いてもよいし、 適宜組み合わせて使用することも 可能である。 固体粒子の添加量は、 固体粒子の種類によって異なるが、 例えば、 シリ力粒子の場合にはィンク組成物全体に対して 1〜 1 0重量%の範囲、 より好 ましくは 1〜 7重量%、 さらには 1〜4重量%含有させることが望ましい。  The above solid particles may be used alone or in an appropriate combination. The amount of solid particles to be added varies depending on the type of solid particles. However, it is desirable to contain 1 to 4% by weight.
1重量%未満の場合には、 着色顔料が記録紙表面から裏面へ移動することを阻 止する効果が少なくなるため、 裏抜け防止効果が低減する。 一方、 添加量は多い 方が裏抜けの低減効果が大きいが、 あまりに多く添加するとインク粘度が増大し、 ィンクジェッ ト記録システムにおいてはへッ ドからのィンク吐出が困難となった り、 孔版システムでは孔版原紙のインク透過性が悪くなつて、 画像形成不良が発 生する。 また、 シリカ粒子の添加量があまりに多いと、 特に静置状態におけるィ ンク粘度が増大し、 チキソ トロピー性が増大する。 このチキソ トロピー性とは、 粒径 1 μ π!〜 l n mのコロイ ド粒子と呼ばれる微粒子を液体に分散させることに より発現するもので、 この分散液に加わるずり応力が静置状態などのように小さ いときは粘度が増大し、 攪拌したときなどのようにずり応力が大きいときは粘度 が低下する性質である。 特に、 インクジェッ ト記録システムにおいては、 インク 粘度とインク吐出量および吐出速度には密接な関係があり、 ィンクにチキソト口 ピー性が発現すると、 インクの置かれた環境、 状況によってインクの粘度が変化 して、 安定したインク吐出ができなくなる。 よって、 インクにチキソトロピー性 を発現させない程度、 より具体的には、 ずり応力 1 0 ( l Z s ) での粘度がずり 応力 1 0 0 ( l Z s ) での 2倍以内とすることによって、 インクの置かれた環境 に関係なく、 安定した画像形成を行うことが可能となる。 なお、 後述する極性溶 剤を適宜選択することによって、 さらには、 後述する分散剤を適宜選択すること によって、 チキソトロピー性を発現させずに、 より多くのシリカ粒子を添加する ことが可能となる。 このような手法をとつた場合でも、 1 0重量%よりもあまり に多くシリ力粒子を添加するとチキソ ト口ピー性が発現するため好まし-くない。 従って、 シリカ粒子以外の固体粒子を用いる場合には、 これらの観点から添加量 を調整することが可能である。 When the amount is less than 1% by weight, the effect of preventing the color pigment from moving from the front surface to the back surface of the recording paper is reduced, and the effect of preventing strike-through is reduced. On the other hand, the larger the amount of addition, the greater the effect of reducing strike-through, but if added too much, the viscosity of the ink increases, making it difficult to eject ink from the head in an ink jet recording system, or in the stencil system. Poor ink permeability of stencil paper causes poor image formation Live. On the other hand, if the added amount of the silica particles is too large, the ink viscosity particularly in a stationary state increases, and the thixotropic property increases. This thixotropic property means that the particle size is 1 μπ! This is manifested by dispersing fine particles called colloid particles of ~ 1 nm in a liquid.When the shear stress applied to this dispersion is small, such as in a static state, the viscosity increases, and when it is stirred, When the shear stress is large as in the above, the viscosity decreases. In particular, in an ink jet recording system, there is a close relationship between ink viscosity and the amount and speed of ink ejection, and if ink has thixotropic properties, the viscosity of the ink changes depending on the environment and conditions in which the ink is placed. As a result, stable ink ejection cannot be performed. Therefore, by making the ink not exhibit thixotropic properties, more specifically, by setting the viscosity at a shear stress of 100 (lZs) to within twice the shear stress at a shear stress of 100 (lZs), It enables stable image formation regardless of the environment where the ink is placed. In addition, by appropriately selecting the polar solvent described below, and further suitably selecting the dispersing agent described later, it becomes possible to add more silica particles without developing thixotropic properties. Even when such a method is employed, it is not preferable to add too much silicic acid particles because the thixotropic properties are exhibited. Therefore, when solid particles other than silica particles are used, the addition amount can be adjusted from these viewpoints.
シリカ粒子の場合、 記録紙の種類によって多少異なるが、 インク中のシリカ粒 子の平均粒子径を 3 0 0 n m以下とすることによってより裏抜けを低減させるこ とができる。 シリカ粒子の平均粒子径は 3 0 0 n m以下とすることが好ましく、 より好ましくは 2 0 0 n m以下、 さらには 1 5 0 n m以下であることが望ましい。 また、 シリカ粒子の平均粒子径は着色顔料の平均粒子径の 0 . 1〜 1 0倍であ ることが好ましい。 シリカ粒子の平均粒子径が着色顔料の平均粒子径の 0 . 1倍 よりも小さい場合、 あるいはシリカ粒子の平均粒子径が着色顔料の平均粒子径の 1 0倍よりも大きい場合には裏抜けが起こりやすくなる。  In the case of silica particles, though it varies slightly depending on the type of recording paper, strike-through can be further reduced by setting the average particle diameter of the silica particles in the ink to 300 nm or less. The average particle size of the silica particles is preferably 300 nm or less, more preferably 200 nm or less, and further preferably 150 nm or less. The average particle diameter of the silica particles is preferably 0.1 to 10 times the average particle diameter of the color pigment. If the average particle size of the silica particles is smaller than 0.1 times the average particle size of the color pigment, or if the average particle size of the silica particles is larger than 10 times the average particle size of the color pigment, strikethrough occurs. More likely to happen.
本発明の非水系インク組成物に用いる溶剤は、 極性溶剤であっても、 非極性溶 剤であってもよく、 極性溶剤と しては、 エステル系溶剤、 アルコール系溶剤、 高 級脂肪酸系溶剤、 エーテル系溶剤およびこれらの混合溶剤等を用いることができ る。 極性溶剤は、 非極性溶剤と混合した時に、 単一の相となるものから選択され る。 The solvent used in the non-aqueous ink composition of the present invention may be a polar solvent or a non-polar solvent. Examples of the polar solvent include ester solvents, alcohol solvents, and higher fatty acid solvents. , Ether-based solvents and their mixed solvents can be used You. The polar solvent is selected to be a single phase when mixed with a non-polar solvent.
具体的には、 ラウリル酸メチル、 ラウリル酸イソプロピル、 ミ リスチン酸イソ プロピル、 ノ、。ノレミチン酸イソプロピル、 ノヽ0ノレミチン酸イソステアリル、 ォレイン 酸メチル、 ォレイン酸ェチル、 ォレイン酸イソプロピル、 ォレイン酸ブチル、 リ ノール酸メチル、 リノール酸イソブチル、 リ ノール酸ェチル、 イソステアリン酸 イソプロピル、 大豆油メチル、 大豆油イソブチル、 トール油メチル、 トール油ィ ソブチル、 アジピン酸ジイソプロピル、 セバシン酸ジイソプロピル、 セバシン酸 ジェチル、 モノ力プリン酸プロピレングリコール、 トリ 2ェチルへキサン酸トリ メチロールプロパン、 トリ 2ェチルへキサン酸グリセリルなどのエステル系溶剤、 イ ソ ミ リ スチノレアノレコーノレ、 イ ソパルミチノレアルコーノレ、 イ ソステアリルアルコ ール、 ォレイルアルコールなどのアルコール系溶剤、 イソノナン酸、 イソミ リス チン酸、 へキサデカン酸、 イソパルミチン酸、 ォレイン酸、 イソステアリン酸な どの高級脂肪酸系溶剤、 ジェチルグリ コールモノブチルエーテル、 エチレンダリ コールモノブチルエーテル、 プロピレングリ コーノレモノブチノレエーテノレ、 プロピ レングリコールジブチルエーテルなどのエーテル系溶剤があげられる。 - 非極性溶剤としては、 ナフテン系溶剤、 パラフィン系溶剤、 イソパラフィン系 溶剤等の非極性溶剤があげられる。 具体的には、 ェクソン社の I s o p a r G、 I s o p a r H、 I s o p a r L、 I s o p a r M E x x o 1 D 40 , E x x o l D 8 0、 E x x o 1 D 1 0 0, E x x o 1 D 1 30N E x x o l D 1 40、 日本石油社の AF_4、 A F - 5 , A F - 6 , AF— 7、 0号ソノレベン ト L、 0 号ソルベン M、 0号ソルベント H、 テク リーン N— 1 6、 テク リーン N— 20、 テク リーン N— 2 2、 日石アイソゾーノレ 30 0、 日石ァイソゾール 400、 S石 ナフテゾール 、 日石ナフテゾールM、 石ナフテゾール 1、 サン石油社のサン セン、 サンパー等を好ましくあげることができる。 Specifically, methyl laurate, isopropyl laurate, isopropyl myristate, and phenol. Noremichin isopropyl, Nono 0 Noremichin isostearyl, methyl Orein acid, Orein acid Echiru, Orein isopropyl, butyl Orein acid, Li Nord methyl, isobutyl linoleate, Li Nord acid Echiru, isopropyl isostearate, soybean oil methyl, large Soybean oil isobutyl, tall oil methyl, tall oil isobutyl, diisopropyl adipate, diisopropyl sebacate, getyl sebacate, propylene glycol monopotassium, trimethylolpropane triethylhexane, glyceryl trihexyl hexate, etc. Ester solvents, alcohol solvents such as isomiri stino oleanol, isopalmitino real alcohol, isostearyl alcohol, oleyl alcohol, etc., isononanoic acid , Isomiristinic acid, hexadecanoic acid, isopalmitic acid, oleic acid, isostearic acid, etc., higher fatty acid solvents, getyl glycol monobutyl ether, ethylene daryl monobutyl ether, propylene glycol monobutynoate ether, propylene glycol diethylene glycol Examples include ether solvents such as butyl ether. -Non-polar solvents include non-polar solvents such as naphthenic solvents, paraffinic solvents, and isoparaffinic solvents. Specifically, Ekuson's I sopar G, I sopar H, I sopar L, I sopar ME xxo 1 D 40, E xxol D 8 0, E xxo 1 D 1 0 0, E xxo 1 D 1 30 N E xxol D 140, Nippon Oil Company's AF_4, AF-5, AF-6, AF-7, No. 0 Sonorevent L, No. 0 Solven M, No. 0 Solvent H, Techleen N-- 16, Techleen N-- 20, Techlin N-22, Nisseki Isozonole 300, Nisseki Aisosol 400, S Stone Naphthesol, Nisseki Naphthesol M, Stone Naphthesol 1, Sanseng Co., Ltd., Sansen, Samper and the like.
上記の溶剤は、 例えば、 極性溶剤あるいは非極性溶剤をそれぞれ単独で、 ある いはそれぞれから 2種類以上を適宜選択して用いてもよいし、 極性溶剤と非極性 溶剤を適宜組み合わせて使用することも可能である。  As the above solvent, for example, a polar solvent or a non-polar solvent may be used alone, or two or more types may be appropriately selected and used, or a polar solvent and a non-polar solvent may be appropriately used in combination. Is also possible.
分散剤としては、 水酸基含有カルボン酸エステル、 長鎖ポリアミノアマイ ドと 高分子量酸エステルの塩、 高分子量ポリカルボン酸の塩、 長鎖ポリアミノアマイ ドと極性酸エステルの塩、 高分子量不飽和酸エステル、 高分子共重合物、 変性ポ リ ウレタン、変性ポリアタリ レート、ポリエーテルエステル型ァニオン系活性剤、 ナフタレンスルホン酸ホルマリン縮合物塩、 芳香族スルホン酸ホルマリン縮合物 塩、 ポリオキシエチレンアルキルリ ン酸エステル、 ポリオキシエチレンノ -ルフ ェ-ルエーテル、 ポリエステルポリアミン、 ステアリルアミンアセテー ト等を用 いることができる。 Dispersing agents include carboxylic acid esters containing hydroxyl groups and long-chain polyaminoamides. High-molecular-weight acid ester salt, high-molecular-weight polycarboxylic acid salt, long-chain polyaminoamide and polar acid ester salt, high-molecular-weight unsaturated acid ester, polymer copolymer, modified polyurethane, modified polyatalylate, poly Ether ester type anionic surfactant, naphthalene sulfonic acid formalin condensate, aromatic sulfonic acid formalin condensate, polyoxyethylene alkyl phosphate, polyoxyethylene phenol ether, polyester polyamine, stearylamine ace Tates and the like can be used.
分散剤の具体例としては、 B YK C h e m i e社製 「A n t i _T e r r a _ U (ポリアミノァマイ ドリン酸塩) 」 、 「A n t i — T e r r a— 2 0 3 2 0 4 (高分子量ポリカルボン酸塩) 」 、 「D i s p e r b y k— 1 0 1 (ポリアミ ノアマイ ドリン酸塩と酸エステル) 、 1 0 7 (水酸基含有カルボン酸エステル) 、 1 1 0 (酸基を含む共重合物) 、 1 3 0 (ポリアマイ ド) 、 1 6 1、 1 6 2、 1 6 3、 1 6 4、 1 6 5、 1 6 6、 1 7 0 (高分子共重合物) 」 、 「4 0 0」 、 「B y k um e n (高分子量不飽和酸エステル) 」 、 「B YK_ P 1 0 4、 P I 0 5 (高分子量不飽和酸ポリカルボン酸) 」 、 「P 1 0 4 S、 2 4 0 S (高分子量不 飽和酸ポリカルボン酸とシリコン系) 」 、 「L a c t i m o n (長鎖アミンと不 飽和酸ポリカルボン酸とシリ コン) 」 が挙げられる。  Specific examples of the dispersing agent include “Anti_Terra_U (polyaminoamide phosphate)” manufactured by BYK Chemie and “Anti-Terra—203322 (high molecular weight polycarboxylic acid). Salt), ”Disperbyk—101 (polyaminoamide phosphate and acid ester), 107 (hydroxyl-containing carboxylic acid ester), 110 (copolymer containing acid group), 130 ( (Polyamide), 161, 162, 163, 164, 165, 1666, 170 (polymer copolymer) "," 400 "," Bykum " en (high molecular weight unsaturated acid ester) "," BYK_P104, PI05 (high molecular weight unsaturated acid polycarboxylic acid) "," P104S, 240S (high molecular weight unsaturated) Acid polycarboxylic acid and silicone) and Lactimon (long-chain amine, unsaturated acid polycarboxylic acid and silicon).
また、 E f k a C HEM I C A L S社製 「エフ力 4 4、 4 6、 4 7、 4 8、 4 9、 5 4、 6 3、 6 4、 6 5、 6 6、 7 1、 7 0 1、 7 6 4、 7 6 6」 、 「エフ 力ポリマー 1 0 0 (変性ポリアクリ レート) 、 1 5 0 (脂肪族系変性ポリマー) 、 4 0 0、 4 0 1、 4 0 2、 4 0 3、 4 5 0、 4 5 1、 4 5 2、 4 5 3 (変性ポリ アタ リ レート) 、 7 4 5 (銅フタロシアニン系) 」 、 共栄社化学社製 「フローレ ン TG— 7 1 0 (ウレタンオリ ゴマー) 」 、 「フローレン DO PA— 1 5 B (ァ ク リルオリ ゴマー) 」 、 「フローレン S H— 2 9 0、 S P— 1 0 0 0」 、 「ポリ フロー N o . 5 0 E、 N o . 3 0 0 (アタリル系共重合物) 」 、 楠本化成社製 「デ イスバロン K S— 8 6 0、 8 7 3 S N、 8 7 4 (高分子分散剤) 、 # 2 1 5 0 (脂 肪族多価カルボン酸) 、 # 7 0 0 4 (ポリエーテルエステル型) 」 「DA— 7 0 3 - 5 0 (ポリエステル酸ァマイ ドアミン塩) 」 が挙げられる。  In addition, `` Efka C HEMICALS Co., Ltd.``F force 44, 46, 47, 48, 49, 54, 63, 64, 65, 66, 71, 701, 7 6 4, 7 6 6 ”,“ F-Polymer 100 (modified polyacrylate), 150 (aliphatic modified polymer), 400, 401, 402, 400, 45 0, 451, 4552, 4553 (denatured poly acrylate), 745 (copper phthalocyanine), Kyoeisha Chemical Co., Ltd., "Floren TG—710 (urethane oligomer)", "Floren DO PA-15B (acrylic oligomer)", "Floren SH-290, SP-100", "Polyflow No.500E, No.300 (Atalyl) ) Kusumoto Kasei Co., Ltd. “DISVALON KS-860, 873 SN, 874 (polymer dispersant), # 2150 (aliphatic polycarboxylic acid), # 7004 (polyetherester type) "DA-703-50 (polyester acid Amide amine salt) ”.
さらに、 花王社製 「デモール RN、 N (ナフタレンスルホン酸ホルマリ ン縮合 物ナトリ ウム塩) 、 MS. C、 S N- B (芳香族スルホン酸ホルマリン縮合物ナ トリ ゥム塩) 、 E P」 、 「ホモゲノール L— 1 8 (ポリカルボン酸型高分子) 」 、 「エマノレゲン 9 2 0、 9 30、 9 3 1、 9 3 5、 9 5 0、 9 8 5 (ポリオキシェ チレンノニノレフェニルエーテノレ) 」 、 「ァセタミ ン 24 (ココナッツアミ ンァセ テー ト) 、 8 6 (ステアリルアミンアセテート) 」 、 アビシァ社製 「ソルスパー ス 5 00 0 (フタロシアニンアンモニゥム塩系) 、 1 3 94 0 (ポリエステルァ ミン系) 、 1 7 000、 1 8000 (脂肪酸アミン系) 、 2 2000、 2400 0、 2 8 000」 、 日光ケミカル社製 「ニッコール T 1 06 (ポリオキシェチレ ンソルビタンモノォレート) 、 MY S— I E X (ポリオキシエチレンモノステア レート) 、 H e x a g l i n e 4— O (へキサグリセリルテ トラオレート) 」 等 があげられる。 Furthermore, Kao's “Demol RN, N (formalin naphthalenesulfonic acid condensation) Sodium salt), MS.C, SN-B (sodium salt of aromatic sulfonic acid formalin condensate), EP "," Homogenol L-18 (polycarboxylic acid type polymer) "," Emanoregen 920, 930, 931, 935, 955, 985 (polyoxyethylennoninolephenyl phenyl), `` acetamin 24 (coconut amine acetate), 86 (stearylamine) Acetate), Abyssia's "Sol Sperse 500 000 (phthalocyanine ammonium salt)", 139400 (polyesteramine), 17 000, 18000 (fatty acid amine), 22000, 2400 , 28 000 ”, Nikko Chemical's“ Nikkor T106 (polyoxyethylene sorbitan monooleate), MYS—IEX (polyoxyethylene monostearate), Hexagline 4-O (hexaglyceryl tetraolate) ” etc And the like.
着色顔料としては、 無機顔料、 有機顔料を問わず、 印刷技術分野で一般に用い られているものを使用することができる。 具体的には、 例えば、 カーボンブラッ ク、 カ ドミ ウムレッ ド、 モリブデンレッ ド、 クロムイェロー、 カ ドミ ウムイエロ 一、 チタンイェロー、 酸化クロム、 ピリ ジアン、 コバルトグリーン、 ウルトラマ リンブノレ一、 プノレシアンブル一、 コバノレトブルー、 ァゾ系顔料、 フタ口'シァニン 系顔料、 キナタリ ドン系顔料、 イソインドリノン系顔料、 ジォキサジン系顔料、 スレン系顔料、 ペリ レン系顔料、 ペリ ノン系顔料、 チォインジゴ系顔料、 キノフ タ口ン系顔料、 金属錯体顔料などの従来公知の顔料を特に限定することなく用い ることができる。  As the color pigments, those generally used in the printing technical field can be used irrespective of inorganic pigments and organic pigments. Specifically, for example, carbon black, cadmium red, molybdenum red, chrome yellow, cadmium yellow, titanium yellow, chromium oxide, pyridian, cobalt green, ultra limb benzole, puno ressible blue, kobanoleto blue , Azo-based pigments, lid-based cyanine-based pigments, quinatalidone-based pigments, isoindolinone-based pigments, dioxazine-based pigments, selen-based pigments, perylene-based pigments, perinone-based pigments, thioindigo-based pigments, quinofata-based pigments Conventionally known pigments such as a system pigment and a metal complex pigment can be used without any particular limitation.
上記顔料は、 単独で用いてもよいし、 適宜組み合わせて使用することも可能で あり、 インク組成物全体に対して 0. 0 1〜 20重量%の範囲で含有させること が望ましい。  The above pigments may be used alone or in an appropriate combination, and are desirably contained in the range of 0.01 to 20% by weight based on the whole ink composition.
本発明の非水系ィンク組成物は、 従来公知の製造方法によって製造することが 可能であるが、 シリカ粒子と着色顔料を別々に分散液として調製した後に、 これ を混合することによって、 シリカ粒子と着色顔料が物理的に結合していない状態 の非水系インク組成物とすることができる。 すなわち、 溶剤と分散剤とシリカ粒 子を含み、 着色顔料を含まないシリカ粒子分散液と、 溶剤と分散剤と着色顔料を 含み、 シリカ粒子を含まない着色顔料分散液をそれぞれ調製し、 その後これを混 合して非水系ィンク組成物を得ることが好ましい。なお、固体粒子や着色顔料は、 ビーズミル等の従来公知の分散手段によって分散することができる。 The non-aqueous ink composition of the present invention can be manufactured by a conventionally known manufacturing method.However, silica particles and a coloring pigment are separately prepared as a dispersion, and then mixed with each other to obtain silica particles. A non-aqueous ink composition in which the color pigment is not physically bound can be obtained. That is, a silica particle dispersion liquid containing a solvent, a dispersant, and silica particles and containing no color pigment, and a color pigment dispersion liquid containing a solvent, a dispersant, and a color pigment but containing no silica particles were prepared. Mix It is preferable to obtain a non-aqueous ink composition in total. The solid particles and the coloring pigment can be dispersed by a conventionally known dispersing means such as a bead mill.
以下に、 本発明を実施例により さらに具体的に説明する。  Hereinafter, the present invention will be described more specifically with reference to examples.
(実施例 1 )  (Example 1)
植物性脂肪酸エステル溶剤 8重量部に分散剤と してソルスパース 1 3 9 4 0 (ポリエステルァミン系の高分子分散剤 : アビシァ社製) を 3重量部溶解し、 力 一ポンプラック (M A— 8 : 三菱化学社製) 5重量部を添加してプレミ ックスし た。 その後ビーズミルにて滞留時間約 2 0分間で分散し、 顔料分散液を得た。 一 方、植物性脂肪酸エステル溶剤 5 6重量部、ナフテン系溶剤 2 0重量部を混合し、 これに分散剤と してソルスパース 1 3 9 4 0を 4重量部溶解し、 さらにシリカ粒 子としてァェロジェル R 9 7 2 (日本ァエロジル社製) 4重量部を添加してプレ ミックスし、 その後、 ビーズミルにて滞留時間約 2 0分間で分散し、 シリカ分散 液を得た。 得られた顔料分散液とシリカ分散液を混合してィンクを得た。  Dissolve 3 parts by weight of Solsperse 139400 (polyesteramine-based polymer dispersant: Abyssia) as a dispersing agent in 8 parts by weight of a vegetable fatty acid ester solvent. : Mitsubishi Chemical Corporation) 5 parts by weight were added and premixed. Thereafter, the mixture was dispersed in a bead mill with a residence time of about 20 minutes to obtain a pigment dispersion. On the other hand, 56 parts by weight of a vegetable fatty acid ester solvent and 20 parts by weight of a naphthenic solvent are mixed, and 4 parts by weight of Solsperse 139400 as a dispersing agent are dissolved therein, and further, aerogel as silica particles is dissolved. 4 parts by weight of R972 (manufactured by Nippon Aerosil Co., Ltd.) were added and premixed, and then dispersed in a bead mill with a residence time of about 20 minutes to obtain a silica dispersion. The obtained pigment dispersion and silica dispersion were mixed to obtain an ink.
(実施例 2 )  (Example 2)
シリカ粒子と してァェロジェル R Y 2 0 0 (曰本ァエロジル社製) を用いた以 外は実施例 1と同様にしてィンクを得た。 - (実施例 3 )  An ink was obtained in the same manner as in Example 1 except that aerogel RY200 (produced by AEROSIL Co., Ltd.) was used as the silica particles. -(Example 3)
シリカ粒子と してァェロジェル R 8 1 2 (日本ァエロジル社製) を用いた以外 は実施例 1 と同様にしてィンクを得た。  An ink was obtained in the same manner as in Example 1 except that aerogel R812 (manufactured by Nippon Aerosil Co., Ltd.) was used as the silica particles.
(実施例 4 )  (Example 4)
シリカ粒子と してァェロジェル O X 5 0 (日本ァエロジル社製) を用いた以外 は実施例 1 と同様にしてィンクを得た。  An ink was obtained in the same manner as in Example 1 except that aerogel OX50 (manufactured by Nippon Aerosil Co., Ltd.) was used as the silica particles.
(実施例 5 )  (Example 5)
シリカ分散液の配合を表 1に記載のとおりにした以外は実施例 1 と同様にして インクを得た。  An ink was obtained in the same manner as in Example 1 except that the composition of the silica dispersion was changed as shown in Table 1.
(実施例 6 )  (Example 6)
シリカ分散液の配合を表 1に記載のとおりにした以外は実施例 1 と同様にして インクを得た。  An ink was obtained in the same manner as in Example 1 except that the composition of the silica dispersion was changed as shown in Table 1.
(実施例 7 ) シリカ分散液の配合を表 1に記載のとおりにした以外は実施例 1 と同様にして ィンクを得た。 (Example 7) An ink was obtained in the same manner as in Example 1 except that the composition of the silica dispersion was changed as shown in Table 1.
(実施例 8 )  (Example 8)
シリカ分散液の配合を表 1に記載のとおり とし、顔料をピグメントイェロー(大 日精化社製) に換えた以外は実施例 1 と同様にしてインクを得た。  An ink was obtained in the same manner as in Example 1 except that the composition of the silica dispersion was as shown in Table 1 and the pigment was changed to Pigment Yellow (manufactured by Dainichi Seika).
(実施例 9 )  (Example 9)
シリカ分散液の配合を表 1に記載のとおり と した以外は実施例 3と同様にして インクを得た。  An ink was obtained in the same manner as in Example 3, except that the formulation of the silica dispersion was as shown in Table 1.
(実施例 1 0 )  (Example 10)
シリ力分散液の滞留時間を 6 0分と した以外は実施例 8と同様にしてィンクを 得た。  An ink was obtained in the same manner as in Example 8, except that the residence time of the sily dispersion was 60 minutes.
(比較例 1 )  (Comparative Example 1)
実施例 1 と同様にして得た顔料分散液に、 植物性脂肪酸エステル 6 2重量部、 ナフテン系溶剤 2 0重量部を混合しインクを得た。  62 parts by weight of a vegetable fatty acid ester and 20 parts by weight of a naphthenic solvent were mixed with the pigment dispersion obtained in the same manner as in Example 1 to obtain an ink.
(比較例 2 )  (Comparative Example 2)
シリ力粒子としてァェロジェル R 9 7 2を用い、 シリ力分散液の配合を表 1に 記載のとおりにした以外は実施例 1 と同様にしてインクを得た。  An ink was obtained in the same manner as in Example 1 except that aerogel R972 was used as the sily particles, and the mixing of the shiri force dispersion was as shown in Table 1.
(比較例 3 )  (Comparative Example 3)
シリカ分散液の配合を表 1に記載のとおり とした以外は実施例 3と同様にして インクを得た。  An ink was obtained in the same manner as in Example 3, except that the formulation of the silica dispersion was as shown in Table 1.
実施例 1〜 1 0、 比較例 1および 3のインクの配合、 およびインク粘度、 顔料 粒子径、 シリカ粒子径をまとめたものを表 1に示す。 Table 1 shows the ink formulations of Examples 1 to 10 and Comparative Examples 1 and 3, and a summary of the ink viscosities, pigment particle diameters, and silica particle diameters.
【表 1 】 【table 1 】
Figure imgf000013_0001
Figure imgf000013_0001
表 1に記載したィンク粘度、 顔料粒子径およびシリカ粒子径は以下のように測 定した  The ink viscosity, pigment particle size and silica particle size described in Table 1 were measured as follows.
12 26 くインク粘度の測定 > 12 26 Measurement of ink viscosity>
ハーケ社製レオメータ R S 7 5を使用し、 直径 6 c mコーンを用いて、 2 3 °C において、 60秒間でずり応力を 0. 7〜 1 00 ( l Z s ) まで上昇させたとき の、 ずり応力が 1 0 0 ( 1/ s ) のときの粘度を測定した。  Shear when the shear stress was increased from 0.7 to 100 (lZs) in 60 seconds at 23 ° C using a 6 cm diameter cone with a Haake Rheometer RS75. The viscosity when the stress was 100 (1 / s) was measured.
<顔料粒子径の測定 > <Measurement of pigment particle size>
顔料濃度が 0. 1 %となるように顔料分散液を溶剤で希釈し、 これを普通紙(理 想科学工業社製 「理想用紙厚口 S」 ) に印字し、 印字部分を走査型電子顕微鏡で 観察し、 紙の繊維上に観察できる顔料粒子を任意に 1 00個選び、 顔料粒子の直 径 (長さが最も長くなる方向) を測定し、 その平均値を粒子径とした。  The pigment dispersion is diluted with a solvent so that the pigment concentration becomes 0.1%, printed on plain paper (“Ideal Paper Thick S”, manufactured by Riso Kagaku Kogyo Co., Ltd.), and the printed portion is scanned with a scanning electron microscope. The pigment particles which can be observed on paper fibers were selected arbitrarily, and the diameter (the direction in which the length becomes the longest) of the pigment particles was measured, and the average value was defined as the particle diameter.
くシリカ粒子径の測定 > Measurement of silica particle size>
顔料粒子径と同様に、 シリカ濃度が 0. 1 %となるようにシリカ分散液を溶剤 で希釈し、 これを普通紙 (理想科学工業社製 「理想用紙厚口 s」 ) に印字し、 印 字部分を走査型電子顕微鏡で観察し、 紙の繊維上に観察できるシリカ粒子を任意 に 1 00個選び、 シリカ粒子の直径 (長さが最も長くなる方向) を測定し、 その 平均値を粒子径とした。  As with the pigment particle size, the silica dispersion is diluted with a solvent so that the silica concentration is 0.1%, and this is printed on plain paper (“Ideal Paper Thick s” manufactured by Riso Kagaku Kogyo Co., Ltd.). Observe the letter-shaped part with a scanning electron microscope, select 100 silica particles that can be observed on the paper fiber, measure the diameter of the silica particles (the direction in which the length becomes the longest), and calculate the average value of the particles. Diameter.
(評価方法) - くインクジェッ トシステムによる裏抜けおよび画像性 >  (Evaluation method)-strike-through and image quality by using the inkjet system>
普通紙 (理想科学工業社製 「理想用紙厚口 S」 ) に、 2 c m角のベタをインク ジェッ トにより印刷し、 24時間放置後、 ベタ部の裏側を OD計 (マクベス社製) で測定し、 以下のように評価した。  Print a 2cm square solid on plain paper (Riso Kagaku Kogyo “Ideal Paper Thickness S”) with an ink jet, leave it for 24 hours, and measure the back side of the solid part with an OD meter (Macbeth) And evaluated as follows.
〇 : OD値が 0. 1 3未満  〇: OD value is less than 0.13
: 00値が0. 1 3以上0. 20未満  : 00 value is 0.13 or more and less than 0.20
X : OD値が 0. 20以上  X: OD value is 0.20 or more
また、 画像性を以下のように評価した。 In addition, the image quality was evaluated as follows.
〇 :画像のかすれなし  〇: No blurring of image
X :画像のかすれ発生 (インク吐出不良)  X: Image blurring (ink ejection failure)
<低粘度孔版システムによる裏抜けおよび画像性 >  <Breakthrough and image quality with low viscosity stencil system>
多孔性支持体 (和紙) の一方の面上に、 平均気孔径 5. ? !!^ 密度。. 3 9 g/ c m3である多孔性樹脂層を有する孔版原紙を用いて、 デジタル孔版印刷機 (R P 3 7 9 0 :理想科学工業社製) を使用して、 普通紙 (理想科学工業社製「理 想用紙厚口 S」 ) に印刷し、 24時間放置後、 ベタ部の裏側を OD計 (マクベス 社製) で測定し、 以下のように評価した。 Average pore size on one side of porous support (Japanese paper) 5.? ! ! ^ Density. 3. Digital stencil printing machine using stencil paper having a porous resin layer of 9 g / cm 3 (RP 3790: Riso Kagaku Kogyo Co., Ltd.), print on plain paper (Riso Kagaku Kogyo Co., Ltd., “Ideal Paper Thick S”), leave it for 24 hours, then OD the solid back. A total (Macbeth) was used and evaluated as follows.
〇: OD値が 0. 1 3未満  〇: OD value is less than 0.13
/ : 00値が0. 1 3以上0. 2 0未満  /: 00 value is more than 0.13 and less than 0.20
X : 00値が0. 2 0以上  X: 00 value is 0.20 or more
また、 画像性を以下のように評価した。 In addition, the image quality was evaluated as follows.
〇:画像のかすれなし  〇: No blurring of image
X :画像のかすれ発生 (インク転移不良)  X: Blurring of the image (poor ink transfer)
以上の評価方法により実施例 1〜実施例 8および比較例 1および 2のインクを 評価した。 結果を表 2に示す。 The inks of Examples 1 to 8 and Comparative Examples 1 and 2 were evaluated by the above evaluation methods. Table 2 shows the results.
漭啉 I ¾ 漭 啉 I ¾
Figure imgf000016_0001
Figure imgf000016_0001
表 2から明らかなように、 実施例 1〜 1 0のインク組成物は、 2 3 °Cにおける 粘度が 3 0 m P a · s以下であるため、 インクジェッ ト記録システムや低粘度孔 版システムに用いても、 ヘッ ドからのインク吐出が困難となったり、 孔版原紙の ィンク透過性が悪くなって、 画像形成不良が発生するといつた問題が生じること がなく、 固体粒子と してシリカ粒子を含有したので、 裏抜けを効果的に防止する ことが可能となった。 As is clear from Table 2, the ink compositions of Examples 1 to 10 have a viscosity at 30 ° C of 30 mPas or less, and are therefore suitable for ink jet recording systems and low viscosity stencil systems. Even if it is used, there will be no problem when ink ejection from the head becomes difficult or the ink permeability of the stencil paper becomes poor, resulting in poor image formation.Silica particles are used as solid particles. Since it was contained, it became possible to effectively prevent strikethrough.
また、 記録紙表面上では、 固体粒子が記録紙の繊維に留まっていることによつ て、 着色顔料の水平方向への移動も阻止することができるため、 画像の滲みも低 減することが可能となり高品位な印刷物を得ることができた。 実際、 印刷物の断 面を光学顕微鏡で観察すると、 シリカ粒子を添加した実施例 1〜 1 0では、 シリ 力粒子を含有していない比較例 1に比べて、 着色顔料の紙裏側への移動量が少な いことが観察された。 また、 この効果は顔料粒子径の大きさに関係なく認められ た。 なお、 シリカ粒子の添加量は、 多い方が裏抜けの低減効果が大きいものの、 添加量を 1 5重量部とした比較例 2では、インク粘度が増大し( 3 8 m P a · s ) , インクジェッ ト記録システムにおいてはへッ ドからのィンク吐出が困難となり、 孔版システムでは孔版原紙のインク透過性が困難となった。 比較例 3では、 ポリ エステルァミン系の高分子分散剤の含有量がシリ力粒子に対して重量比で 0 . 0 5と少ないために、 シリカ粒子の分散状態が安定したシリカ分散液が得られなか つた。  In addition, since the solid particles stay on the recording paper fibers on the recording paper surface, the movement of the coloring pigment in the horizontal direction can be prevented, so that the bleeding of the image can be reduced. It became possible and high quality printed matter was obtained. In fact, when the cross section of the printed matter was observed with an optical microscope, it was found that in Examples 1 to 10 in which the silica particles were added, the amount of the colored pigment moved to the back side of the paper as compared with Comparative Example 1 in which no silica particles were contained. Was observed to be low. This effect was observed regardless of the pigment particle size. Although the larger the amount of silica particles added, the greater the effect of reducing strike-through, the ink viscosity increased (38 mPa · s) in Comparative Example 2 in which the added amount was 15 parts by weight. In the inkjet recording system, it was difficult to discharge ink from the head, and in the stencil system, the ink permeability of the stencil paper became difficult. In Comparative Example 3, since the content of the polyesteramine-based polymer dispersant was as small as 0.05 in terms of the weight ratio with respect to the silicic acid particles, a silica dispersion in which the dispersion state of the silica particles was stable could not be obtained. I got it.
シリカ粒子の平均粒子径は、 概ね 3 0 0 n m以下であると裏抜け低減効果、 画 像形成が良好である。 なお、 実施例 5では、 平均粒子径が 3 0 0 n m以下である 力 裏抜けが若干認められた。 これは、 シリカ粒子の添加量が 0 . 5重量部と低 いためである。 また、 実施例 1 0でも、 平均粒子径が 3 0 0 n m以下であるのに 裏抜けが若干認められたが、 これはシリカ粒子の平均粒子径が着色顔料の粒子径 の 0 . 1倍未満のためである。  When the average particle diameter of the silica particles is about 300 nm or less, the show-through reduction effect and the image formation are good. In Example 5, some breakthrough of force with an average particle diameter of 300 nm or less was observed. This is because the added amount of silica particles is as low as 0.5 part by weight. Also, in Example 10, although strike-through was slightly observed even though the average particle size was 300 nm or less, the average particle size of the silica particles was less than 0.1 times the particle size of the color pigment. For.
以上のように、 本発明のインク組成物は、 2 3 °Cにおける粘度が 3 O m P a · s以下の非水系ィンク組成物において、 記録紙への印刷時に着色顔料が記録紙表 面から裏面へ移動することを阻止する実質的に着色能を有さない固体粒子を含有 したので、 インクが記録紙内部に浸透する過程において、 固体粒子が記録紙の繊 維に留まってィンクに含有されている着色顔料が記録紙表面から裏面へ移動する ことを阻止し、 かつ固体粒子自体は記録紙を着色する機能を有さないため、 裏抜 けを効果的に防止することが可能となった。 As described above, in the ink composition of the present invention, in a non-aqueous ink composition having a viscosity of 3 OmPas or less at 23 ° C, the color pigment is printed from the surface of the recording paper when printing on the recording paper. Since the ink contains solid particles that have substantially no coloring ability that prevents it from moving to the back surface, the solid particles are converted into fibers of the recording paper during the process of ink penetration into the recording paper. The color pigment contained in the ink stays in the ink and is prevented from moving from the front side to the back side of the recording paper, and the solid particles themselves do not have the function of coloring the recording paper. It became possible to prevent.
なお、 本発明の非水系インク組成物は、 溶剤、 着色顔料、 分散剤、 固体粒子以 外の、 例えば各種添加剤を含有していてもよく、 さらに、 実施例では固体粒子と してシリカ粒子を用いたが、 これ以外の固体粒子を用いても同様に、 本発明の裏 抜け低減効果や、 画像滲みのない高品位な画像形成を実現することができる。  The non-aqueous ink composition of the present invention may contain, for example, various additives other than the solvent, the color pigment, the dispersant, and the solid particles.In Examples, silica particles are used as the solid particles. However, even if solid particles other than the above are used, the strike-through reduction effect of the present invention and high-quality image formation without image bleeding can be realized.

Claims

請求の範囲 The scope of the claims
1 . 少なく とも溶剤、 着色顔料、 分散剤を含み、 2 3 °Cにおける粘度が 3 0 m P a · s以下の非水系インク組成物であって、 記録紙への印刷時に前記着色顔 料が前記記録紙表面から裏面へ移動することを阻止する実質的に着色能を有さな い固体粒子を含有したことを特徴とする非水系ィンク組成物。  1. A non-aqueous ink composition containing at least a solvent, a coloring pigment, and a dispersing agent and having a viscosity of 30 mPas or less at 23 ° C, wherein the coloring pigment is used for printing on recording paper. A non-aqueous ink composition comprising solid particles having substantially no coloring ability for preventing the recording paper from moving from the front surface to the back surface.
2 . 前記固体粒子がシリカ粒子であることを特徴とする請求の範囲第 1項記 載の非水系ィンク組成物。  2. The non-aqueous ink composition according to claim 1, wherein the solid particles are silica particles.
3 . 前記シリ力粒子をィンク組成物中に 1〜 1 0重量%含有することを特徴 とする請求の範囲第 2項記載の非水系ィンク組成物。  3. The non-aqueous ink composition according to claim 2, wherein the ink composition contains 1 to 10% by weight of the silica particles.
4 . 前記シリカ粒子の平均粒子径が 3 0 0 n m以下であることを特徴とする 請求の範囲第 3項記載の非水系ィンク組成物。  4. The non-aqueous ink composition according to claim 3, wherein the silica particles have an average particle diameter of 300 nm or less.
5 . 前記シリカ粒子の平均粒子径が前記着色顔料の平均粒子径の 0 . 1〜 1 0倍であることを特徴とする請求の範囲第 2項、 第 3項または第 4項記載の非水 系ィンク組成物。  5. The non-aqueous liquid according to claim 2, wherein the average particle diameter of the silica particles is 0.1 to 10 times the average particle diameter of the coloring pigment. Based ink composition.
6 . 前記溶剤と前記分散剤と前記シリカ粒子を含み、 前記着色顔料を含まな いシリカ粒子分散液と、 前記溶剤と前記分散剤と前記着色顔料を含み、 前記シリ 力粒子を含まない着色顔料分散液とを混合して得られることを特徴とする請求の 範囲 2〜 5いずれか 1項記載の非水系ィンク組成物。  6. A silica particle dispersion containing the solvent, the dispersant, and the silica particles, and not containing the color pigment, and a color pigment containing the solvent, the dispersant, and the color pigment, but not containing the silica particles. The non-aqueous ink composition according to any one of claims 2 to 5, wherein the composition is obtained by mixing with a dispersion.
7 . 前記シリカ粒子分散液に含まれる前記分散剤がポリエステルァミン系の 高分子分散剤であり、 かつ前記シリカ粒子に対する前記ポリエステルァミン系の 高分子分散剤の含有量が重量比で 0 . 1以上であることを特徴とする請求の範囲 第 6項記載の非水系ィンク組成物。  7. The dispersant contained in the silica particle dispersion is a polyesteramine-based polymer dispersant, and the content of the polyesteramine-based polymer dispersant with respect to the silica particles is 0. 7. The non-aqueous ink composition according to claim 6, wherein the composition is 1 or more.
8 . 前記溶剤と前記分散剤と前記シリカ粒子を含み、 前記着色顔料を含まな いシリカ粒子分散液と、 前記溶剤と前記分散剤と前記着色顔料を含み、 前記シリ 力粒子を含まない着色顔料分散液とをそれぞれ調製した後に、 前記シリカ粒子分 散液と前記着色顔料分散液を混合することを特徴とする非水系ィンク組成物の製 造方法。  8. A silica particle dispersion containing the solvent, the dispersant, and the silica particles, and not containing the color pigment, and a color pigment containing the solvent, the dispersant, and the color pigment, but not containing the silica particles. A method for producing a non-aqueous ink composition, comprising: preparing a dispersion liquid and then mixing the silica particle dispersion liquid and the color pigment dispersion liquid.
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JP4674053B2 (en) * 2004-03-31 2011-04-20 理想科学工業株式会社 Non-aqueous inkjet ink
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