JP2013094970A - Inkjet printing method and ink set - Google Patents
Inkjet printing method and ink set Download PDFInfo
- Publication number
- JP2013094970A JP2013094970A JP2011236770A JP2011236770A JP2013094970A JP 2013094970 A JP2013094970 A JP 2013094970A JP 2011236770 A JP2011236770 A JP 2011236770A JP 2011236770 A JP2011236770 A JP 2011236770A JP 2013094970 A JP2013094970 A JP 2013094970A
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- JP
- Japan
- Prior art keywords
- pretreatment liquid
- solvent
- printing
- ink
- mass
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
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- 239000011133 lead Substances 0.000 description 1
- MOUPNEIJQCETIW-UHFFFAOYSA-N lead chromate Chemical compound [Pb+2].[O-][Cr]([O-])(=O)=O MOUPNEIJQCETIW-UHFFFAOYSA-N 0.000 description 1
- 229940049918 linoleate Drugs 0.000 description 1
- FMMOOAYVCKXGMF-UHFFFAOYSA-N linoleic acid ethyl ester Natural products CCCCCC=CCC=CCCCCCCCC(=O)OCC FMMOOAYVCKXGMF-UHFFFAOYSA-N 0.000 description 1
- 235000010187 litholrubine BK Nutrition 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
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- UFWIBTONFRDIAS-UHFFFAOYSA-N naphthalene-acid Natural products C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 1
- 125000004957 naphthylene group Chemical group 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
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- 125000003367 polycyclic group Chemical group 0.000 description 1
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- 229920000570 polyether Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
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- PZQSQRCNMZGWFT-QXMHVHEDSA-N propan-2-yl (z)-octadec-9-enoate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC(C)C PZQSQRCNMZGWFT-QXMHVHEDSA-N 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- ULWHHBHJGPPBCO-UHFFFAOYSA-N propane-1,1-diol Chemical compound CCC(O)O ULWHHBHJGPPBCO-UHFFFAOYSA-N 0.000 description 1
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- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
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- 239000013225 prussian blue Substances 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- IZMJMCDDWKSTTK-UHFFFAOYSA-N quinoline yellow Chemical compound C1=CC=CC2=NC(C3C(C4=CC=CC=C4C3=O)=O)=CC=C21 IZMJMCDDWKSTTK-UHFFFAOYSA-N 0.000 description 1
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- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 238000006277 sulfonation reaction Methods 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
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- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
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- 150000003568 thioethers Chemical class 0.000 description 1
- JOUDBUYBGJYFFP-FOCLMDBBSA-N thioindigo Chemical compound S\1C2=CC=CC=C2C(=O)C/1=C1/C(=O)C2=CC=CC=C2S1 JOUDBUYBGJYFFP-FOCLMDBBSA-N 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
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- 229910052720 vanadium Inorganic materials 0.000 description 1
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Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41J—TYPEWRITERS; SELECTIVE PRINTING MECHANISMS, i.e. MECHANISMS PRINTING OTHERWISE THAN FROM A FORME; CORRECTION OF TYPOGRAPHICAL ERRORS
- B41J2/00—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed
- B41J2/005—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed characterised by bringing liquid or particles selectively into contact with a printing material
- B41J2/01—Ink jet
- B41J2/21—Ink jet for multi-colour printing
- B41J2/2107—Ink jet for multi-colour printing characterised by the ink properties
- B41J2/2114—Ejecting specialized liquids, e.g. transparent or processing liquids
Landscapes
- Ink Jet (AREA)
- Ink Jet Recording Methods And Recording Media Thereof (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
Abstract
Description
本発明は、インクジェット記録システムの使用に適したインクジェット印刷方法およびインクジェット用前処理液とインクがセットされたインクセットに関するものである。 The present invention relates to an inkjet printing method suitable for use in an inkjet recording system, and an ink set in which an inkjet pretreatment liquid and ink are set.
インクジェット印刷システムにおいては、近年、記録媒体の制約を受けずに高速でフルカラー印刷が行えることが益々要求されている。この要求に応えるためには、ラインヘッド方式のインクジェットプリンタの使用が適しており、その場合、普通紙への浸透が早く、かつ、印刷濃度が高く、滲みや裏抜けの少ない高画質な印刷画像の得られるインクが必要となる。 In recent years, inkjet printing systems are increasingly required to be able to perform full-color printing at high speed without being restricted by recording media. In order to meet this demand, the use of a line head type ink jet printer is suitable. In that case, high-quality printed images with quick penetration into plain paper, high print density, and less bleeding and back-through. Ink obtained is required.
インクジェット印刷方式に用いられるインクジェットインクは、水性インクと非水性インクに大別される。水性インクは溶媒として水を含有するため、特に印刷媒体として普通紙を用いた場合、溶媒は印刷媒体に容易に浸透するが、色材は印刷媒体の表面に留まり易いため、高濃度・高画質の印刷画像が得られ易いという利点を有する。一方、水を含有するために、印刷媒体がカールやコックリングを起こし易く、印刷媒体の搬送性に悪影響を及ぼし、高速印刷の弊害となるという問題がある。 Ink jet inks used in the ink jet printing system are roughly classified into water-based inks and non-water-based inks. Since water-based ink contains water as a solvent, especially when plain paper is used as a printing medium, the solvent easily penetrates into the printing medium, but the coloring material tends to stay on the surface of the printing medium, so it has a high density and high image quality. The print image can be easily obtained. On the other hand, since water is contained, there is a problem that the print medium is likely to curl and cockling, adversely affects the transportability of the print medium, and becomes a problem of high-speed printing.
非水性インクは、主として高揮発性の有機溶剤を溶媒として含有する溶剤インクと、主として低揮発性の有機溶剤を溶媒として含有する油性インクに大別される。溶剤インクは、乾燥性に優れているが、溶媒が大量に揮発するため使用環境が制限される。一方で、油性インクは印刷媒体として普通紙を用いた場合、印刷媒体への浸透性および乾燥性に優れ、水性インクおよび溶剤インクよりも溶媒が揮発し難いため、インクノズルにおける目詰まりが生じにくく、インクノズルのクリーニング回数が少なくて済むといった利点があり、高速印刷、特にラインヘッド方式の高速インクジェット印刷に適している。 Non-aqueous inks are roughly classified into solvent inks mainly containing a highly volatile organic solvent as a solvent and oily inks mainly containing a low volatile organic solvent as a solvent. The solvent ink is excellent in drying properties, but the use environment is limited because a large amount of the solvent is volatilized. On the other hand, oil-based inks, when plain paper is used as the printing medium, are excellent in permeability and drying properties to the printing medium, and the solvent is less likely to evaporate than aqueous inks and solvent inks. There is an advantage that the number of times of cleaning the ink nozzles is small, and it is suitable for high-speed printing, in particular, high-speed inkjet printing of a line head type.
しかし、油性インクは印刷媒体上での色材と溶媒の離脱性が悪く、特に印刷媒体として普通紙を用いた場合、色材と溶媒が一緒に印刷媒体の繊維間隙に浸透し易く、画像濃度の低下、裏抜けの増大、印刷ドットの滲みが生じ、印刷画像の画質が悪化するという問題がある。 However, oil-based inks have poor detachment of the color material and solvent on the print medium. Especially when plain paper is used as the print medium, the color material and the solvent easily penetrate together into the fiber gap of the print medium, and the image density There is a problem in that the image quality of the printed image is deteriorated due to a decrease in image quality, an increase in show-through, and bleeding of printed dots.
従来から、色材を紙表面に留め、印刷ドットの滲みを抑制するために、無機粒子や定着樹脂で構成されたインク受容層を表面に備えた専用紙は各種存在する。しかし、普通紙で同様の効果を得るには、印刷時に色材を紙表面に留める手段が必要となる。水性インクでは、色材を溶媒と一緒に浸透させずに普通紙表面に留める方法として、インクに重ねて処理液を吐出し、インクと処理液に含まれる物質を紙表面で反応させることにより色材を凝集させ、浸透しにくくする方法が既に提案されている（特許文献１、２および３）。また、カチオン性の無機粒子を含む前処理液を印刷前に普通紙表面に処理し、アニオン性染料を含む水性インクを反応させて定着させる方法も提案されている（特許文献４）。しかし、これらの方法は色材を紙表面に留め、印刷ドットの滲みを抑制するという効果は有するものの、処理液とインク両方が水分を多く含むため、特に普通紙に対する印刷においては印刷媒体がカールやコックリングを起こし易く、高速印刷への弊害となるという問題がある。 2. Description of the Related Art Conventionally, there are various types of dedicated papers that have an ink receiving layer made of inorganic particles or a fixing resin on the surface in order to keep the color material on the paper surface and suppress bleeding of printed dots. However, in order to obtain the same effect with plain paper, a means for keeping the color material on the paper surface during printing is required. In the case of water-based inks, as a method of keeping the coloring material on the surface of plain paper without penetrating with the solvent, the processing liquid is discharged on top of the ink, and the ink and the substances contained in the processing liquid are reacted on the paper surface. Methods for aggregating materials and making them difficult to penetrate have already been proposed (Patent Documents 1, 2, and 3). Further, a method has been proposed in which a pretreatment liquid containing cationic inorganic particles is treated on the surface of plain paper before printing, and a water-based ink containing an anionic dye is reacted and fixed (Patent Document 4). However, although these methods have the effect of retaining the coloring material on the paper surface and suppressing bleeding of the printing dots, both the treatment liquid and the ink contain a lot of moisture, so that the printing medium is curled especially when printing on plain paper. And cockling are likely to occur, which is a problem for high-speed printing.
非水性インクでは、特許文献５に、アニオン性官能基を有する高分子化合物を含む第１のインクと、１級および／または２級アミノ基を有する高分子化合物を含む第２のインクとを重ねて吐出し、紙表面で両物質を反応させることにより、色材を凝集させ、浸透しにくくする方法が提案されている。しかし、この方法では常に２種のインクを一定量重ねて印刷する必要があるため、画像率が高い印刷物を多枚数印刷する場合、インクを大量に消費するという課題がある。 In the non-aqueous ink, Patent Document 5 overlaps a first ink containing a polymer compound having an anionic functional group and a second ink containing a polymer compound having a primary and / or secondary amino group. In other words, a method has been proposed in which the coloring material is agglomerated and hardly permeated by causing both substances to react with each other on the paper surface. However, in this method, since it is necessary to always print a certain amount of two kinds of inks, there is a problem that a large amount of ink is consumed when printing a large number of printed materials with a high image rate.
本発明者らは特許文献６において、特定の平均粒子径を有する無機粒子と所定の割合で水溶性有機溶剤と水とを含む前処理液を印刷媒体へ塗布した後、油性インクを印刷媒体上へ吐出させることにより印刷を行う油性インクジェット印刷方法を提案している。この印刷方法によれば、前処理液で印刷媒体の表面を処理することで、印刷媒体の表面が目止めされて、印刷された油性インク中の色材が印刷媒体上に留まるとともに、色材の印刷媒体への浸透が抑制され、印刷濃度が向上すると同時に裏抜けと滲みを防止することが可能である。 In Patent Document 6, the present inventors applied a pretreatment liquid containing inorganic particles having a specific average particle diameter, a water-soluble organic solvent and water at a predetermined ratio to a print medium, and then applied oil-based ink onto the print medium. Has proposed an oil-based ink jet printing method in which printing is performed by discharging the ink to the surface. According to this printing method, the surface of the print medium is treated by treating the surface of the print medium with the pretreatment liquid, and the color material in the printed oil-based ink stays on the print medium. Can be prevented from penetrating into the print medium, the printing density can be improved, and at the same time, it is possible to prevent see-through and bleeding.
ラインヘッド式のインクジェット印刷システムにおいて前処理を行う場合、印刷の高速性が要求されるため、前処理された印刷媒体を長時間乾燥することは難しい。短時間で乾燥させるためには、前処理された印刷媒体に対して高熱を送風する方法、加熱ロールを印刷媒体に接触させて乾燥する方法などが考えられるが、システムへの負荷、消費電力の増加が懸念されるため好ましくない。乾燥速度を速めるために、前処理液の溶媒として高揮発性の有機溶剤を使用することもできるが、使用環境が制限されるため好ましくない。 When the pretreatment is performed in the line head type ink jet printing system, it is difficult to dry the pretreated printing medium for a long time because high speed printing is required. In order to dry in a short time, a method of blowing high heat to the pre-processed print medium, a method of bringing a heating roll into contact with the print medium and drying can be considered, but the load on the system and power consumption are considered. This is not preferable because there is a concern about an increase. In order to increase the drying speed, a highly volatile organic solvent can be used as the solvent for the pretreatment liquid, but this is not preferable because the use environment is limited.
上記特許文献６の印刷方法の場合、前処理液が水溶性有機溶剤と水とを所定の割合で含有するので、前処理液で印刷媒体の表面を処理した場合でも、印刷媒体にカール等の変形を生じさせることは軽減され、印刷媒体の搬送性を良好に保つことが可能である。しかし、前処理液を印刷媒体へ塗布した後、直ちに油性インクを印刷媒体上へ吐出させるといったさらなる高速性に対応できることが望まれる。また、特許文献６の印刷方法に用いられるインクは油性インクであるが、水分量の多い水性インクの場合にも高速搬送に対応できることが望まれる。 In the case of the printing method of Patent Document 6, since the pretreatment liquid contains a water-soluble organic solvent and water in a predetermined ratio, even when the surface of the print medium is treated with the pretreatment liquid, the printing medium has a curl or the like. It is possible to reduce the occurrence of deformation and to maintain good transportability of the print medium. However, it is desirable to be able to cope with higher speed such that oil-based ink is immediately ejected onto the print medium after the pretreatment liquid is applied to the print medium. Moreover, although the ink used for the printing method of patent document 6 is oil-based ink, it is desired that it can respond to high-speed conveyance also in the case of water-based ink with much water content.
本発明は上記事情に鑑みなされたものであり、前処理液を印刷媒体へ塗布した後、長時間の乾燥や高負荷の乾燥システム無しに、インクを印刷媒体上へ吐出させても印刷媒体にカール等の変形を生じさせることがなく、印刷媒体の搬送性が良好に確保できるとともに、滲みや裏抜けを抑制して印刷物の印刷濃度を高めることが可能なインクジェット印刷方法およびインクセット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 after applying the pretreatment liquid to the print medium, the ink can be ejected onto the print medium without drying for a long time or a high-load drying system. Provided are an ink jet printing method and an ink set that do not cause deformation such as curling, can ensure good transportability of a print medium, and can suppress bleeding and back-through and increase the print density of printed matter. It is for the purpose.
本発明のインクジェット印刷方法は、前処理液を印刷媒体へ塗布した後、少なくとも顔料および溶剤を含んでなるインクを前記印刷媒体上へ吐出させることにより印刷を行うインクジェット印刷方法において、前記前処理液が少なくとも無機粒子と水と溶剤を含んでなり、前記無機粒子のレーザー光回折散乱法により測定される平均粒子径が１〜２０μｍであって、該無機粒子を前記前処理液全量に対して２０質量％よりも多く含み、前記前処理液中の水分量が前記前処理液全量に対して５５質量％以下であり、溶解度パラメータ（以下、ＳＰ値ともいう）が８．５（ｃａｌ／ｃｍ3）1/2以上、１２．０（ｃａｌ／ｃｍ3）1/2以下の溶剤を前記前処理液全量に対して１５質量％以上２５質量％以下の範囲で含むことを特徴とするものである。 The inkjet printing method of the present invention is the inkjet printing method in which printing is performed by discharging an ink containing at least a pigment and a solvent onto the printing medium after the pretreatment liquid is applied to the printing medium. Comprises at least inorganic particles, water, and a solvent, the average particle diameter of the inorganic particles measured by a laser light diffraction scattering method is 1 to 20 μm, and the inorganic particles are added to the total amount of the pretreatment liquid. The water content in the pretreatment liquid is more than 55% by mass with respect to the total amount of the pretreatment liquid, and the solubility parameter (hereinafter also referred to as SP value) is 8.5 (cal / cm 3). ) 1/2 or more and 12.0 (cal / cm 3 ) 1/2 or less of the solvent is contained in a range of 15 to 25% by mass with respect to the total amount of the pretreatment liquid. .
前記前処理液を、該前処理液量が１０〜１５ｇ／ｍ2となるように前記印刷媒体に塗工することが好ましい。
前記インクはラインヘッド方式のインクジェットプリンタにより前記印刷媒体上へ吐出されることが好ましい。
It is preferable to apply the pretreatment liquid onto the print medium so that the amount of the pretreatment liquid is 10 to 15 g / m 2 .
The ink is preferably ejected onto the print medium by a line head type ink jet printer.
本発明のインクセットは、前処理液を印刷媒体へ塗布した後、少なくとも顔料および溶剤を含んでなるインクを前記印刷媒体上へ吐出させることにより印刷を行うインクジェット印刷に使用するインクセットであって、少なくとも顔料および溶剤を含んでなるインクと、少なくとも無機粒子と水と溶剤を含んでなる前処理液とからなり、前記無機粒子のレーザー光回折散乱法により測定される平均粒子径が１〜２０μｍであって、該無機粒子を前記前処理液全量に対して２０質量％よりも多く含み、前記前処理液中の水分量が前記前処理液全量に対して５５質量％以下であり、ＳＰ値が８．５（ｃａｌ／ｃｍ3）1/2以上、１２．０（ｃａｌ／ｃｍ3）1/2以下の溶剤を前記前処理液全量に対して１５質量％以上２５質量％以下の範囲で含むことを特徴とするものである。 The ink set of the present invention is an ink set used for ink jet printing in which printing is performed by ejecting an ink containing at least a pigment and a solvent onto the print medium after applying a pretreatment liquid to the print medium. And an ink containing at least a pigment and a solvent, and a pretreatment liquid containing at least inorganic particles, water and a solvent, and the average particle diameter of the inorganic particles measured by a laser light diffraction scattering method is 1 to 20 μm. The inorganic particles are contained in an amount of more than 20% by mass with respect to the total amount of the pretreatment liquid, the water content in the pretreatment liquid is 55% by mass or less with respect to the total amount of the pretreatment liquid, and the SP value Is 8.5 (cal / cm 3 ) 1/2 or more and 12.0 (cal / cm 3 ) 1/2 or less of the solvent in the range of 15% by mass to 25% by mass with respect to the total amount of the pretreatment liquid. Including It is characterized by.
前記前処理液が１０〜１５ｇ／ｍ2の塗布量で使用されるように用意されていることが好ましい。
前記インクはラインヘッド方式のインクジェットプリンタにより前記印刷媒体上へ吐出されることが好ましい。
It is preferable that the pretreatment liquid is prepared so as to be used at a coating amount of 10 to 15 g / m 2 .
The ink is preferably ejected onto the print medium by a line head type ink jet printer.
本発明のインクジェット印刷方法およびインクセットは、前処理液が、レーザー光回折散乱法により測定される平均粒子径が１〜２０μｍの無機粒子を、前処理液全量に対して２０質量％よりも多く含むので、印刷媒体の表面が目止めされ、印刷されたインク中の顔料の浸透が抑制されるために、顔料が印刷媒体表面上に留まり、印刷濃度が向上すると同時に裏抜けと滲みが防止することができる。また、ＳＰ値が８．５（ｃａｌ／ｃｍ3）1/2以上、１２．０（ｃａｌ／ｃｍ3）1/2以下の溶剤を前処理液全量に対して１５質量％以上２５質量％以下の範囲にすることで、前処理液を印刷媒体へ塗布した後、長時間の乾燥や高負荷の乾燥システム無しにインクを印刷しても、印刷ドットの滲みを十分に抑制でき、写真画像や文字の滲みのない、シャープで高濃度な印刷画像を得ることができる。 In the inkjet printing method and the ink set of the present invention, the pretreatment liquid contains more than 20% by mass of inorganic particles having an average particle diameter of 1 to 20 μm as measured by a laser diffraction diffraction method with respect to the total amount of the pretreatment liquid. As a result, the surface of the print medium is sealed, and the penetration of the pigment in the printed ink is suppressed, so that the pigment stays on the surface of the print medium, and the print density is improved and at the same time, the strikethrough and bleeding are prevented. be able to. Further, a solvent having an SP value of 8.5 (cal / cm 3 ) 1/2 or more and 12.0 (cal / cm 3 ) 1/2 or less is 15% by mass or more and 25% by mass or less based on the total amount of the pretreatment liquid. In this range, after applying the pretreatment liquid to the print medium, even if the ink is printed without drying for a long time or a high-load drying system, bleeding of printed dots can be sufficiently suppressed, and photographic images and A sharp and high-density printed image without blurring of characters can be obtained.
さらに、上記の所定範囲のＳＰ値を有する溶剤の含有量を１５質量％以上２５質量％以下の範囲にするとともに、前処理液中の水分量を５５質量％以下とすることで、前処理液で印刷媒体の表面を処理した場合でも、処理直後の印刷媒体のカール等の変形を抑制することができ、印刷媒体の搬送性が良好に保たれるので、高速印刷および後工程を阻害することがない。また、前処理後に印刷した印刷物の数時間経過後の変形も抑制することができるため、高品質の印刷物を得ることができる。 Further, the content of the solvent having the SP value in the above predetermined range is in the range of 15% by mass or more and 25% by mass or less, and the water content in the pretreatment liquid is 55% by mass or less, whereby the pretreatment liquid Even when the surface of the printing medium is processed in step 1, it is possible to suppress deformation such as curling of the printing medium immediately after the processing, and to maintain good transportability of the printing medium, thereby hindering high-speed printing and subsequent processes. There is no. Moreover, since the deformation | transformation after several hours progress of the printed matter printed after the pre-processing can also be suppressed, a high quality printed matter can be obtained.
以下、本発明のインクジェット印刷方法およびインクセットについて詳細に説明する。まず、本発明のインクジェット印刷方法およびインクセットにおける前処理液について説明する。 Hereinafter, the ink jet printing method and the ink set of the present invention will be described in detail. First, the pretreatment liquid in the inkjet printing method and ink set of the present invention will be described.
本発明における前処理液は、少なくとも無機粒子と水と溶剤を含んでなる。
無機粒子は、レーザー光回折散乱法により測定される平均粒子径が１〜２０μｍの範囲の無機粒子である。ここで、レーザー光回折散乱法により測定される平均粒子径は、レーザー光回折散乱粒度分布測定装置により測定され、詳細には商品名：ＳＡＬＤ−２０００Ａ（株式会社島津製作所製）により、レーザー光波長；６８０ｎｍ、測定温度；２５℃、分散媒；水の条件により測定される。平均粒子径が１μｍより小さい場合であっても、平均粒子径が２０μｍより大きい場合であっても、印刷媒体に対する目止め作用が発揮されず、印刷濃度の向上効果が十分に得られない。
The pretreatment liquid in the present invention comprises at least inorganic particles, water, and a solvent.
The inorganic particles are inorganic particles having an average particle diameter in the range of 1 to 20 μm as measured by a laser light diffraction / scattering method. Here, the average particle diameter measured by the laser light diffraction / scattering method is measured by a laser light diffraction / scattering particle size distribution measuring device, and in detail, according to the trade name: SALD-2000A (manufactured by Shimadzu Corporation), the laser light wavelength. Measured at 680 nm, measurement temperature; 25 ° C., dispersion medium; water. Even when the average particle diameter is smaller than 1 μm or when the average particle diameter is larger than 20 μm, the sealing action on the printing medium is not exhibited, and the effect of improving the printing density cannot be sufficiently obtained.
無機粒子としては、体質顔料として使用される無機粒子を使用することができ、例えば、シリカ、炭酸カルシウム、硫酸バリウム、酸化チタン、アルミナホワイト、水酸化アルミニウム、白土、タルク、クレー、ケイソウ土、カオリン、マイカなどの無機粒子を好ましく挙げることができる。 As the inorganic particles, inorganic particles used as extender pigments can be used. For example, silica, calcium carbonate, barium sulfate, titanium oxide, alumina white, aluminum hydroxide, white clay, talc, clay, diatomaceous earth, kaolin Inorganic particles such as mica can be preferably mentioned.
無機粒子は前処理液全量に対して２０質量％よりも多く含み、好ましくは２０〜５０質量％、さらには２５〜３５質量％の範囲であることが好ましい。無機粒子の含有量が２０質量％よりも少ないと、印刷媒体に対する目止め作用を十分に得るためには前処理液の塗工量を多くしなければならず、処理された印刷媒体の乾燥性が低下し、用紙変形が大きくなり印刷ドットの滲みも大きくなるため、高速印刷に適さなくなる。特に、インクとして水性インクを用いる場合にはさらに紙に転移する水分量が多くなるため印刷媒体の乾燥性がより低下することになって、用紙変形が大きくなる。 The inorganic particles are contained in an amount of more than 20% by mass with respect to the total amount of the pretreatment liquid, preferably 20 to 50% by mass, and more preferably 25 to 35% by mass. If the content of the inorganic particles is less than 20% by mass, the coating amount of the pretreatment liquid must be increased in order to obtain a sufficient sealing action on the printing medium, and the drying property of the treated printing medium is increased. Decreases, paper deformation increases and printing dot bleeding increases, making it unsuitable for high-speed printing. In particular, when water-based ink is used as the ink, the amount of moisture transferred to the paper is further increased, so that the drying property of the printing medium is further reduced, and the paper deformation is increased.
前処理液は、前処理液量が１０〜１５ｇ／ｍ2となるように印刷媒体に塗工することが好ましく、より好ましくは１１〜１４ｇ／ｍ2、さらに好ましくは１２〜１３ｇ／ｍ2の範囲であることが望ましい。前処理液量が１０ｇ／ｍ2よりも少ないと、印刷媒体の表面の目止め効果が低減し、印刷されたインク中の顔料が浸透しやすくなり、印刷濃度が低下する。一方、前処理液量が１５ｇ／ｍ2よりも多いと、印刷媒体の用紙変形が大きくなり高速印刷時の搬送性を阻害する恐れがある。また、印刷ドットの滲みが小さくなりすぎ、解像度３００×３００ｄｐｉ程度の印刷の際に、ベタを形成するのに十分なドットサイズにならない。そのため、裏抜けは抑制されるが高濃度の印刷物が得られない。 The pretreatment liquid is preferably applied to the print medium so that the amount of the pretreatment liquid is 10 to 15 g / m 2 , more preferably 11 to 14 g / m 2 , and still more preferably 12 to 13 g / m 2 . A range is desirable. When the amount of the pretreatment liquid is less than 10 g / m 2 , the sealing effect on the surface of the printing medium is reduced, the pigment in the printed ink is likely to permeate, and the printing density is lowered. On the other hand, if the amount of the pretreatment liquid is more than 15 g / m 2 , the paper deformation of the printing medium becomes large, and there is a possibility that the transportability during high-speed printing may be hindered. In addition, the blur of printed dots becomes too small, and the dot size is not sufficient to form a solid when printing with a resolution of about 300 × 300 dpi. For this reason, show-through is suppressed, but a high-density printed matter cannot be obtained.
前処理液中の水分量は前処理液全量に対して５５質量％以下であることが必要である。ここで水分量とは、前処理液に溶媒として含まれる水の他、樹脂や分散剤、その他の添加剤等に含まれる水分量を合わせたものである。水分量が５５質量％よりも多くなると、前処理液で印刷媒体の表面を処理した場合でも、処理直後の印刷媒体のカール等の変形を抑制することが困難となり、印刷媒体の搬送性が悪くなって高速印刷を行うことが難しくなる。前処理液中の水分量はより好ましくは３０〜５０質量％の範囲、さらには３５〜４５質量％の範囲であることが好ましい。水分量が３０質量％よりも少なくなると、前処理液が乾燥しやすくなり、印刷画像の濃度が低下し裏抜けが悪化する怖れがある。 The amount of water in the pretreatment liquid needs to be 55% by mass or less with respect to the total amount of the pretreatment liquid. Here, the moisture content refers to a combination of the moisture content contained in the resin, dispersant, other additives, etc. in addition to the water contained in the pretreatment liquid as a solvent. When the water content is more than 55% by mass, even when the surface of the print medium is treated with the pretreatment liquid, it becomes difficult to suppress deformation such as curling of the print medium immediately after the treatment, and the transportability of the print medium is poor. It becomes difficult to perform high-speed printing. The amount of water in the pretreatment liquid is more preferably in the range of 30 to 50% by mass, and further preferably in the range of 35 to 45% by mass. If the water content is less than 30% by mass, the pretreatment liquid is likely to be dried, and the density of the printed image may be lowered and the back-through may be worsened.
溶剤は、ＳＰ値が８．５（ｃａｌ／ｃｍ3）1/2以上、１２．０（ｃａｌ／ｃｍ3）1/2以下の溶剤（以下、特定溶剤ともいう）の含有量が、前処理液全量に対して１５質量％以上２５質量％以下の範囲であることが必要である。特定溶剤の含有量が２５質量％よりも多い場合、前処理液を塗布後の印刷媒体の乾燥性が低下し、印刷ドットが大きく滲んでしまい、シャープで高濃度な印刷画像が得られなくなる。一方で、特定溶剤の含有量が１５質量％よりも少ない場合、印刷媒体のカール等の変形が十分に抑制されず、印刷媒体の搬送不良が生じる恐れがある。
なお、ＳＰ値は、Ｆｅｄｏｒｓの提唱した下記式（１）の計算方法で算出した値である。
δ=[Σ(ΔＥ１)/Σ(ΔＶ１)]１／２ ・・・式（１）
ΔＥ１：各単位官能基当たりの凝集エネルギー
ΔＶ１：各単位官能基当たりの分子容
The solvent has a SP value of 8.5 (cal / cm 3 ) 1/2 or more and a content of 12.0 (cal / cm 3 ) 1/2 or less (hereinafter also referred to as a specific solvent). It is necessary to be in the range of 15% by mass or more and 25% by mass or less with respect to the total amount of liquid. When the content of the specific solvent is more than 25% by mass, the drying property of the printing medium after applying the pretreatment liquid is lowered, the printing dots are greatly blurred, and a sharp and high-density printed image cannot be obtained. On the other hand, when the content of the specific solvent is less than 15% by mass, deformation such as curling of the printing medium is not sufficiently suppressed, and there is a possibility that conveyance failure of the printing medium may occur.
The SP value is a value calculated by the calculation method of the following formula (1) proposed by Fedors.
δ = [Σ (ΔE1) / Σ (ΔV1)] 1/2 (1)
ΔE1: Cohesive energy per unit functional group ΔV1: Molecular volume per unit functional group
ＳＰ値の範囲は、８．５（ｃａｌ／ｃｍ3）1/2以上、１２．０（ｃａｌ／ｃｍ3）1/2以下であることが好ましく、より好ましくは８．５（ｃａｌ／ｃｍ3）1/2以上、１０．０（ｃａｌ／ｃｍ3）1/2以下であることが望ましい。ＳＰ値が８．５（ｃａｌ／ｃｍ3）1/2未満の場合、特定溶剤の含有量が２５質量％以下であっても、水に対する溶解性が低下し、前処理液の分散安定性が悪化してしまい、均一な塗工ができなくなる。一方、ＳＰ値が１２．０（ｃａｌ／ｃｍ3）1/2よりも大きくなると特定溶剤の含有量が１５質量％以上であっても、印刷媒体のカール等の変形が十分に抑制されず、印刷媒体の搬送不良が生じる怖れがある。 The range of the SP value is preferably 8.5 (cal / cm 3 ) 1/2 or more and 12.0 (cal / cm 3 ) 1/2 or less, more preferably 8.5 (cal / cm 3). ) 1/2 or more and 10.0 (cal / cm 3 ) 1/2 or less are desirable. When the SP value is less than 8.5 (cal / cm 3 ) 1/2 , even when the content of the specific solvent is 25% by mass or less, the solubility in water is reduced, and the dispersion stability of the pretreatment liquid is improved. It becomes worse and uniform coating cannot be performed. On the other hand, when the SP value is larger than 12.0 (cal / cm 3 ) 1/2 , even if the content of the specific solvent is 15% by mass or more, deformation such as curling of the printing medium is not sufficiently suppressed, There is a risk of poor transport of print media.
特定溶剤としては、１，２−ヘキサンジオール（ＳＰ値＝１１．５）、ジエチレングリコール−ｍ−エチルエーテル（ＳＰ値＝１０．９）、ジエチレングリコール−ｍ−ブチルエーテル（ＳＰ値＝１０．７）、トリエチレングリコール−ｍ−メチルエーテル（ＳＰ値＝１１．０）、トリエチレングリコール−ｍ−エチルエーテル（ＳＰ値＝１０．８）、トリエチレングリコール−ｍ−ブチルエーテル（ＳＰ値＝１０．５）、ジプロピレングリコール−ｍ−メチルエーテル（ＳＰ値＝１０．６）、トリプロピレングリコール−ｍ−メチルエーテル（ＳＰ値＝１０．２）、３−メトキシ−３−メチル−１−ブタノール（ＳＰ値＝１０．５）、ジエチレングリコールモノエチルエーテルアセテート（ＳＰ値＝８．７）等を好ましく挙げることができる。これらの溶剤は前処理液全量に対して１５質量％以上２５質量％以下の範囲であれば２種類以上を適宜混合して用いることができる。 Specific solvents include 1,2-hexanediol (SP value = 11.5), diethylene glycol-m-ethyl ether (SP value = 10.9), diethylene glycol-m-butyl ether (SP value = 10.7), triethylene glycol Ethylene glycol-m-methyl ether (SP value = 11.0), triethylene glycol-m-ethyl ether (SP value = 10.8), triethylene glycol-m-butyl ether (SP value = 10.5), di Propylene glycol-m-methyl ether (SP value = 10.6), tripropylene glycol-m-methyl ether (SP value = 10.2), 3-methoxy-3-methyl-1-butanol (SP value = 10. 5), diethylene glycol monoethyl ether acetate (SP value = 8.7) can be preferably mentioned. . These solvents can be used by appropriately mixing two or more of them in the range of 15% by mass or more and 25% by mass or less with respect to the total amount of the pretreatment liquid.
前処理液には特定溶剤以外の溶剤を含んでいてもよい。この場合、特定溶剤と特定溶剤以外の溶剤との質量比（（特定溶剤以外の溶剤の含有量（質量％））／（特定溶剤の含有量（質量％））は０．４以下であることが好ましい。特定溶剤以外の溶剤を質量比０．４よりも多く含むと、用紙変形を抑制する効果が低下する怖れがある。特定溶剤以外の溶剤としては、エチレングリコール（ＳＰ値＝１４．２）、ジエチレングリコール（ＳＰ値＝１２．１）、プロピレングリコール（ＳＰ値１３．３）ブチレングリコール（ＳＰ値＝１３．８）などのグリコール類、グリセリン（ＳＰ値＝１６．５）、1,3-プロパンジオール(ＳＰ値＝１３．５)、ブタンジオール（ＳＰ値＝１３．６）などのジオール類などを用いることができる。 The pretreatment liquid may contain a solvent other than the specific solvent. In this case, the mass ratio of the specific solvent and the solvent other than the specific solvent ((content of the solvent other than the specific solvent (mass%)) / (content of the specific solvent (mass%)) is 0.4 or less. If the solvent contains a solvent other than the specific solvent in a mass ratio of more than 0.4, the effect of suppressing the deformation of the paper may be reduced, and the solvent other than the specific solvent may be ethylene glycol (SP value = 14. 2), glycols such as diethylene glycol (SP value = 12.1), propylene glycol (SP value 13.3) butylene glycol (SP value = 13.8), glycerin (SP value = 16.5), 1,3 -Diols such as propanediol (SP value = 13.5) and butanediol (SP value = 13.6) can be used.
本発明で使用する前処理液には、その性状に悪影響を与えない限り、上記溶剤、無機粒子以外に、例えば、分散剤、界面活性剤、定着剤、防腐剤等の他の成分を添加できる。特に、定着剤は、前処理液塗工層の耐久性を付与し、さらに印刷画像の滲みを防止するために有用である。定着剤としては、各種の水溶性高分子または水分散性の高分子粒子などが使用可能である。高分子の種類としては、アクリル酸系共重合体、アクリル／スチレン共重合体、ポリウレタン、ポリエステル、ポリビニルアルコール、ポリ塩化ビニル、ポリ酢酸ビニル、スチレン−ブタジエンゴム（ＳＢＲ）、デンプン、アルキド樹脂、ポリアクリルアミド、ポリビニルアセタール等が好ましい。 In the pretreatment liquid used in the present invention, other components such as a dispersant, a surfactant, a fixing agent, and an antiseptic can be added in addition to the solvent and the inorganic particles as long as the properties are not adversely affected. . In particular, the fixing agent is useful for imparting durability of the pretreatment liquid coating layer and preventing bleeding of the printed image. As the fixing agent, various water-soluble polymers or water-dispersible polymer particles can be used. Examples of the polymer include acrylic acid copolymer, acrylic / styrene copolymer, polyurethane, polyester, polyvinyl alcohol, polyvinyl chloride, polyvinyl acetate, styrene-butadiene rubber (SBR), starch, alkyd resin, poly Acrylamide, polyvinyl acetal and the like are preferable.
本発明で使用する前処理液は、例えばビーズミル等の公知の分散機に全成分を一括または分割して投入して分散させ、所望により、メンブレンフィルター等の公知のろ過機を通すことにより調製できる。例えば、予め溶剤の一部と顔料の全量を均一に混合させた混合液を調製して分散機にて分散させた後、この分散液に残りの成分を添加してろ過機を通すことにより調製することができる。 The pretreatment liquid used in the present invention can be prepared by, for example, supplying all components into a known disperser such as a bead mill in a batch or divided and dispersing, and if necessary, passing through a known filter such as a membrane filter. . For example, after preparing a mixed liquid in which a part of the solvent and the whole amount of the pigment are uniformly mixed in advance and dispersing with a disperser, the remaining components are added to this dispersion and the mixture is passed through a filter. can do.
本発明のインクジェット印刷方法あるいはインクセットにおけるインクについて説明する。インクとしては油性インク、水性インクのいずれも用いることができる。まず、油性インクについて説明する。 The ink in the inkjet printing method or ink set of the present invention will be described. As the ink, either oil-based ink or water-based ink can be used. First, the oil-based ink will be described.
本発明で使用する油性インクは、溶剤および顔料から主として構成される。
溶剤は、インクの溶媒すなわちビヒクルとして機能するものであれば特に限定されず、揮発性溶剤および難揮発性溶剤の何れであってもよい。しかしながら、本発明では環境上の観点から、溶剤は、難揮発性溶剤を主体として含有することが好ましい。難揮発性溶剤の沸点は、２００℃以上が好ましく、より好ましくは２４０℃以上である。
The oil-based ink used in the present invention is mainly composed of a solvent and a pigment.
The solvent is not particularly limited as long as it functions as an ink solvent, that is, a vehicle, and may be any of a volatile solvent and a hardly volatile solvent. However, in the present invention, from the environmental viewpoint, the solvent preferably contains a hardly volatile solvent as a main component. The boiling point of the hardly volatile solvent is preferably 200 ° C. or higher, more preferably 240 ° C. or higher.
溶剤としては、非極性有機溶剤および極性有機溶剤の何れの有機溶剤も使用できる。これらは、単独で使用してもよく、または、単一の相を形成する限り、２種以上組み合わせて使用できる。本発明では、非極性有機溶剤および極性有機溶剤を組み合わせて使用することが好ましく、２０〜８０質量％の非極性溶剤と８０〜２０質量％の極性溶剤とから溶剤を構成することが好ましく、３０〜４５質量％の非極性溶剤と７０〜５５質量％の極性溶剤とから溶剤を構成することがより好ましい。 As the solvent, any organic solvent such as a nonpolar organic solvent and a polar organic solvent can be used. These may be used alone or in combination of two or more as long as they form a single phase. In the present invention, a nonpolar organic solvent and a polar organic solvent are preferably used in combination, and the solvent is preferably composed of 20 to 80% by mass of a nonpolar solvent and 80 to 20% by mass of a polar solvent. More preferably, the solvent is composed of ˜45 mass% nonpolar solvent and 70 ˜55 mass% polar solvent.
非極性有機溶剤としては、ナフテン系、パラフィン系、イソパラフィン系等の石油系炭化水素溶剤を使用でき、具体的には、ドデカンなどの脂肪族飽和炭化水素類、エクソンモービル社製「アイソパー、エクソール」（いずれも商品名）、新日本石油社製「ＡＦソルベント」（商品名）、サン石油社製「サンセン、サンパー」（いずれも商品名）等が挙げられる。これらは、単独で、または、２種以上組み合わせて用いることができる。 As the nonpolar organic solvent, petroleum hydrocarbon solvents such as naphthenic, paraffinic, and isoparaffinic solvents can be used. Specifically, aliphatic saturated hydrocarbons such as dodecane, “Isoper, Exol” manufactured by ExxonMobil Co., Ltd. (All are trade names), “AF Solvent” (trade name) manufactured by Shin Nippon Oil Co., Ltd., “Sansen, Thumper” (all trade names) manufactured by Sun Oil Co., Ltd., and the like. These can be used alone or in combination of two or more.
極性有機溶剤としては、エステル系溶剤、アルコール系溶剤、脂肪酸系溶剤、エーテル系溶剤などが挙げられる。これらは、単独で、または、２種以上組み合わせて用いることができる。 Examples of the polar organic solvent include ester solvents, alcohol solvents, fatty acid solvents, ether solvents, and the like. These can be used alone or in combination of two or more.
エステル系溶剤としては、例えば、１分子中の炭素数が５以上、好ましくは９以上、より好ましくは１２乃至３２の高級脂肪酸エステル類が挙げられ、例えば、イソノナン酸イソデシル、イソノナン酸イソトリデシル、イソノナン酸イソノニル、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、パルミチン酸イソプロピル、パルミチン酸イソオクチル、パルミチン酸ヘキシル、パルミチン酸イソステアリル、イソパルミチン酸イソオクチル、オレイン酸メチル、オレイン酸エチル、オレイン酸イソプロピル、オレイン酸ブチル、オレイン酸ヘキシル、リノール酸メチル、リノール酸イソブチル、リノール酸エチル、ステアリン酸ブチル、ステアリン酸ヘキシル、ステアリン酸イソオクチル、イソステアリン酸イソプロピル、ピバリン酸２−オクチルドデシル、大豆油メチル、大豆油イソブチル、トール油メチル、トール油イソブチル、アジピン酸ジイソプロピル、セバシン酸ジイソプロピル、セバシン酸ジエチル、モノカプリン酸プロピレングリコール、トリ２エチルヘキサン酸トリメチロールプロパン、トリ２エチルヘキサン酸グリセリルなどが挙げられる。 Examples of the ester solvent include higher fatty acid esters having 5 or more, preferably 9 or more, and more preferably 12 to 32 carbon atoms in one molecule. For example, isodecyl isononanoate, isotridecyl isononanoate, and isononanoic acid. Isononyl, methyl laurate, isopropyl laurate, isopropyl myristate, isopropyl palmitate, isooctyl palmitate, hexyl palmitate, isostearyl palmitate, isooctyl isopalmitate, methyl oleate, ethyl oleate, isopropyl oleate, oleic acid Butyl, hexyl oleate, methyl linoleate, isobutyl linoleate, ethyl linoleate, butyl stearate, hexyl stearate, isooctyl stearate, isopate isostearate Pill, 2-octyldodecyl pivalate, soybean oil methyl, soybean oil isobutyl, tall oil methyl, tall oil isobutyl, diisopropyl adipate, diisopropyl sebacate, diethyl sebacate, propylene glycol monocaprate, trimethylol tri-2-ethylhexanoate Examples thereof include propane and glyceryl tri-2-ethylhexanoate.
アルコール系溶剤としては、例えば、１分子中の炭素数が１２以上の脂肪族高級アルコール類が挙げられ、具体的には、イソミリスチルアルコール、イソパルミチルアルコール、イソステアリルアルコール、オレイルアルコールなどの高級アルコールが挙げられる。
脂肪酸系溶剤としては、例えば、１分子中の炭素数が４以上、好ましくは９乃至２２の脂肪酸類が挙げられ、イソノナン酸、イソミリスチン酸、ヘキサデカン酸、イソパルミチン酸、オレイン酸、イソステアリン酸などが挙げられる、
Examples of the alcohol solvent include aliphatic higher alcohols having 12 or more carbon atoms in one molecule. Specifically, higher alcohols such as isomyristyl alcohol, isopalmityl alcohol, isostearyl alcohol, and oleyl alcohol. Examples include alcohol.
Examples of the fatty acid solvent include fatty acids having 4 or more, preferably 9 to 22 carbon atoms in one molecule, such as isononanoic acid, isomyristic acid, hexadecanoic acid, isopalmitic acid, oleic acid, and isostearic acid. Can be mentioned,
エーテル系溶剤としては、ジエチルグリコールモノブチルエーテル、エチレングリコールモノブチルエーテル、プロピレングリコールモノブチルエーテル、プロピレングリコールジブチルエーテルなどのグリコールエーテル類の他、グリコールエーテル類のアセタートなどが挙げられる。 Examples of ether solvents include glycol ethers such as diethyl glycol monobutyl ether, ethylene glycol monobutyl ether, propylene glycol monobutyl ether, propylene glycol dibutyl ether, and acetates of glycol ethers.
顔料としては、有機顔料、無機顔料を問わず、印刷の技術分野で一般に用いられているものを使用でき、特に限定されない。具体的には、カーボンブラック、カドミウムレッド、クロムイエロー、カドミウムイエロー、酸化クロム、ビリジアン、チタンコバルトグリーン、ウルトラマリンブルー、プルシアンブルー、コバルトブルー、アゾ系顔料、フタロシアニン系顔料、キナクリドン系顔料、イソインドリノン系顔料、ジオキサジン系顔料、スレン系顔料、ペリレン系顔料、チオインジゴ系顔料、キノフタロン系顔料、金属錯体顔料などが好適に使用できる。これらの顔料は単独で用いてもよいし、２種以上組み合わせて使用してもよい。
顔料は、油性インク全量に対して０．０１〜２０質量％の範囲で含有されることが好ましい。
The pigment is not particularly limited, and may be any organic pigment or inorganic pigment that is commonly used in the technical field of printing. Specifically, carbon black, cadmium red, chrome yellow, cadmium yellow, chromium oxide, viridian, titanium cobalt green, ultramarine blue, Prussian blue, cobalt blue, azo pigment, phthalocyanine pigment, quinacridone pigment, isoindo Rinone pigments, dioxazine pigments, selenium pigments, perylene pigments, thioindigo pigments, quinophthalone pigments, metal complex pigments and the like can be suitably used. These pigments may be used alone or in combination of two or more.
The pigment is preferably contained in the range of 0.01 to 20% by mass with respect to the total amount of the oil-based ink.
油性インク中における顔料の分散を良好にするために、油性インクに顔料分散剤を添加することが好ましい。本発明で使用できる顔料分散剤としては、顔料を溶剤中に安定して分散させるものであれば特に限定されないが、例えば、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、変性ポリアクリレート、ポリエーテルエステル型アニオン系活性剤、ナフタレンスルホン酸ホルマリン縮合物塩、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ニルフェニルエーテル、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が好適に使用され、そのうち、高分子分散剤を使用するのが好ましい。 In order to improve the dispersion of the pigment in the oil-based ink, it is preferable to add a pigment dispersant to the oil-based ink. The pigment dispersant that can be used in the present invention is not particularly limited as long as the pigment is stably dispersed in a solvent. For example, a hydroxyl group-containing carboxylic acid ester, a salt of a long-chain polyaminoamide and a high molecular weight acid ester, High molecular weight polycarboxylic acid salt, long chain polyaminoamide and polar acid ester salt, high molecular weight unsaturated acid ester, high molecular weight copolymer, modified polyurethane, modified polyacrylate, polyether ester type anionic active agent, naphthalene sulfone Acid formalin condensate salt, polyoxyethylene alkyl phosphate ester, polyoxyethylene nonylphenyl ether, polyester polyamine, stearylamine acetate and the like are preferably used, and among them, a polymer dispersant is preferably used.
顔料分散剤の具体例としては、日本ルーブリゾール社製「ソルスパース５０００（フタロシアニンアンモニウム塩系）、１３９４０（ポリエステルアミン系）、１７０００、１８０００（脂肪酸アミン系）、１１２００、２２０００、２４０００、２８０００」（いずれも商品名）、Ｅｆｋａ ＣＨＥＭＩＣＡＬＳ社製「エフカ４００、４０１、４０２、４０３、４５０、４５１、４５３（変性ポリアクリレート）、４６，４７，４８，４９，４０１０，４０５５（変性ポリウレタン）」（いずれも商品名）、花王社製「デモールＰ、ＥＰ、ポイズ５２０、５２１、５３０、ホモゲノールＬ−１８（ポリカルボン酸型高分子界面活性剤）」（いずれも商品名）、楠本化成社製「ディスパロンＫＳ−８６０、ＫＳ−８７３Ｎ４（高分子ポリエステルのアミン塩）」（いずれも商品名）、第一工業製薬社製「ディスコール２０２、２０６、ＯＡ−２０２、ＯＡ−６００（多鎖型高分子非イオン系）」（いずれも商品名）等が挙げられる。 Specific examples of the pigment dispersant include “Solsperse 5000 (phthalocyanine ammonium salt type), 13940 (polyesteramine type), 17000, 18000 (fatty acid amine type), 11200, 22000, 24000, 28000” manufactured by Nippon Lubrizol (any) Product name), "Fuka 400, 401, 402, 403, 450, 451, 453 (modified polyacrylate), 46, 47, 48, 49, 4010, 4055 (modified polyurethane)" manufactured by Efka CHEMICALS (both products) Name), “Demol P, EP, Poise 520, 521, 530, Homogenol L-18 (polycarboxylic acid type polymer surfactant)” manufactured by Kao Corporation (all trade names), “Disparon KS-” manufactured by Enomoto Kasei Co., Ltd. 860, KS-873N4 (polymer polyester (All trade names), “Dacol 202, 206, OA-202, OA-600 (multi-chain polymer nonionic)” (all trade names) manufactured by Daiichi Kogyo Seiyaku Co., Ltd. Etc.
上記顔料分散剤のうち、ポリエステル鎖からなる側鎖を複数備える櫛形構造のポリアミド系分散剤が好ましく使用される。ポリエステル鎖からなる側鎖を複数備える櫛形構造のポリアミド系分散剤とは、ポリエチレンイミンのような主鎖に多数の窒素原子を備え、窒素原子を介してアミド結合した側鎖を複数備える化合物であって、側鎖がポリエステル鎖であるものをいい、例えば、特開平５−１７７１２３号公報に開示されているような、ポリエチレンイミンなどのポリアルキレンイミンからなる主鎖一分子当り３〜８０個のポリ（カルボニル―Ｃ３〜Ｃ６―アルキレンオキシ）鎖がアミド架橋によって側鎖として結合している構造の分散剤が挙げられる。なお、かかる櫛形構造のポリアミド系分散剤としては、上記日本ルーブリゾール社製ソルスパース１１２００、ソルスパース２８０００（何れも商品名）が該当する。
顔料分散剤の含有量は、上記顔料を十分に上記有機溶剤中に分散可能な量であれば足り、適宜設定できる。
Among the pigment dispersants, a comb-type polyamide dispersant having a plurality of side chains made of polyester chains is preferably used. The comb-type polyamide dispersant having a plurality of side chains composed of a polyester chain is a compound having a plurality of nitrogen atoms in the main chain, such as polyethyleneimine, and a plurality of side chains amide-bonded via the nitrogen atoms. The side chain is a polyester chain. For example, as disclosed in JP-A No. 5-177123, 3 to 80 poly per molecule of the main chain composed of polyalkyleneimine such as polyethyleneimine. Examples thereof include a dispersant having a structure in which a (carbonyl-C3-C6-alkyleneoxy) chain is bonded as a side chain by an amide bridge. Examples of the comb-type polyamide-based dispersant include Solsperse 11200 and Solsperse 28000 (both trade names) manufactured by Nippon Lubrizol Corporation.
The content of the pigment dispersant is sufficient as long as the pigment can be sufficiently dispersed in the organic solvent, and can be appropriately set.
油性インクには、インクの性状に悪影響を与えない限り、上記有機溶剤、顔料、顔料分散剤以外に、例えば、染料、界面活性剤、定着剤、防腐剤等の他の成分を添加できる。 In addition to the organic solvent, the pigment, and the pigment dispersant, other components such as a dye, a surfactant, a fixing agent, and an antiseptic can be added to the oil-based ink as long as the properties of the ink are not adversely affected.
油性インクは、例えばビーズミル等の公知の分散機に全成分を一括または分割して投入して分散させ、所望により、メンブレンフィルター等の公知のろ過機を通すことにより調製できる。例えば、予め溶剤の一部と顔料の全量を均一に混合させた混合液を調製して分散機にて分散させた後、この分散液に残りの成分を添加してろ過機を通すことにより調製することができる。 The oil-based ink can be prepared by, for example, supplying all components into a known disperser such as a bead mill in a batch or divided and dispersing the mixture, and if desired, passing it through a known filter such as a membrane filter. For example, after preparing a mixed liquid in which a part of the solvent and the whole amount of the pigment are uniformly mixed in advance and dispersing with a disperser, the remaining components are added to this dispersion and the mixture is passed through a filter. can do.
本発明で使用する水性インクは、溶剤および顔料から主として構成される。
溶剤としては水溶性有機溶剤が使用される。水溶性有機溶剤としては、具体的には、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、テトラエチレングリコール、ペンタ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、などのグリコール類、グリセリン、アセチン類、トリエチレングリコールモノメチルエーテル、トリエチレングリコールモノブチルエーテル、テトラエチレングリコールモノメチルエーテル、テトラエチレングリコールジメチルエーテル、テトラエチレングリコールジエチルエーテルなどのグリコール誘導体、トリエタノールアミン、１−メチル−２−ピロリドン、β−チオグリコール、スルホランなどを用いることができる。これらの水溶性有機溶剤は単独で、または２種類以上を組み合わせて使用することができる。水溶性有機溶剤は、インク全量に対し１〜８０質量％含まれていることが好ましく、１０〜６０質量％含まれていることがより好ましい。
The aqueous ink used in the present invention is mainly composed of a solvent and a pigment.
A water-soluble organic solvent is used as the solvent. Specific examples of water-soluble organic solvents include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, pentaethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, and other glycols, glycerin, acetins, Glycol derivatives such as triethylene glycol monomethyl ether, triethylene glycol monobutyl ether, tetraethylene glycol monomethyl ether, tetraethylene glycol dimethyl ether, tetraethylene glycol diethyl ether, triethanolamine, 1-methyl-2-pyrrolidone, β-thioglycol, Sulfolane and the like can be used. These water-soluble organic solvents can be used alone or in combination of two or more. The water-soluble organic solvent is preferably contained in an amount of 1 to 80% by mass, more preferably 10 to 60% by mass, based on the total amount of the ink.
顔料としては、たとえば、アゾ系、フタロシアニン系、染料系、縮合多環系、ニトロ系、ニトロソ系等の有機顔料（ブリリアントカーミン６Ｂ、レーキレッドＣ、ウォッチングレッド、ジスアゾイエロー、ハンザイエロー、フタロシアニンブルー、フタロシアニングリーン、アルカリブルー、アニリンブラック等）；コバルト、鉄、クロム、銅、亜鉛、鉛、チタン、バナジウム、マンガン、ニッケル等の金属類、金属酸化物および硫化物、ならびに黄土、群青、紺青等の無機顔料、ファーネスカーボンブラック、ランプブラック、アセチレンブラック、チャンネルブラック等のカーボンブラック類を用いることができる。これらの顔料は、いずれか１種が単独で用いられるほか、２種以上が組み合わせて使用されてもよい。 Examples of the pigment include organic pigments such as azo, phthalocyanine, dye, condensed polycyclic, nitro, and nitroso (brilliant carmine 6B, lake red C, watching red, disazo yellow, hanza yellow, phthalocyanine blue, Phthalocyanine green, alkali blue, aniline black, etc.); metals such as cobalt, iron, chromium, copper, zinc, lead, titanium, vanadium, manganese, nickel, metal oxides and sulfides, and ocher, ultramarine, bitumen, etc. Carbon blacks such as inorganic pigments, furnace carbon black, lamp black, acetylene black and channel black can be used. Any one of these pigments may be used alone, or two or more of these pigments may be used in combination.
さらに、化学的または物理的処理により顔料の表面に親水性官能基が導入された自己分散性顔料を用いることが好ましい。自己分散性顔料に導入させる親水性官能基としては、イオン性を有するものが好ましく、顔料表面をアニオン性またはカチオン性に帯電させることにより、静電反発力によって顔料粒子を水中に安定に分散させることができる。アニオン性官能基としては、スルホン酸基、カルボキシル基、カルボニル基、ヒドロキシル基、ホスホン酸基等が好ましい。カチオン性官能基としては、第４級アンモニウム基、第４級ホスホニウム基などが好ましい。 Furthermore, it is preferable to use a self-dispersing pigment in which a hydrophilic functional group is introduced on the surface of the pigment by chemical or physical treatment. As the hydrophilic functional group to be introduced into the self-dispersing pigment, those having ionicity are preferable, and the pigment particles are stably dispersed in water by electrostatic repulsion by charging the pigment surface anionic or cationic. be able to. As the anionic functional group, a sulfonic acid group, a carboxyl group, a carbonyl group, a hydroxyl group, a phosphonic acid group and the like are preferable. As the cationic functional group, a quaternary ammonium group, a quaternary phosphonium group and the like are preferable.
これらの親水性官能基は、顔料表面に直接結合させてもよいし、他の原子団を介して結合させてもよい。他の原子団としては、アルキレン基、フェニレン基、ナフチレン基などが挙げられるが、これらに限定されることはない。顔料表面の処理方法としては、ジアゾ化処理、スルホン化処理、次亜塩素酸処理、フミン酸処理、真空プラズマ処理などが挙げられる。
顔料はインク全量に対し１〜３０質量％含まれていることが好ましく、１〜１５質量％含まれていることがより好ましい。
These hydrophilic functional groups may be directly bonded to the pigment surface or may be bonded via other atomic groups. Examples of other atomic groups include, but are not limited to, an alkylene group, a phenylene group, and a naphthylene group. Examples of the treatment method for the pigment surface include diazotization treatment, sulfonation treatment, hypochlorous acid treatment, humic acid treatment, and vacuum plasma treatment.
The pigment is preferably contained in an amount of 1 to 30% by mass and more preferably 1 to 15% by mass with respect to the total amount of the ink.
インクセットのインクに含まれる水分散性樹脂は、水に安定に分散させるために必要な親水成分が導入された自己乳化型のものでもよいし、外部乳化剤の使用により水分散性となるものでもよい。水分散性樹脂としては、アクリル樹脂、スチレン−アクリル樹脂、ウレタン樹脂、酢酸ビニル樹脂、アクリル−酢酸ビニル樹脂等を好ましく挙げることができ、これらは単独であるいは２種以上を適宜組み合わせて使用することができる。より具体的には、例えば、第一工業製薬株式会社製のスーパーフレックスシリーズのなかのスーパーフレックス４６０、４６０ｓ、４７０、５００Ｍ、６１０、７００、株式会社アデカ製アデカボンタイターシリーズのなかのアデカボンタイターＨＵＸ−３８０、２９０Ｋ、２９０Ｈ、三井化学ポリウレタン株式会社製タケラックＷ−５１２Ａ６等が挙げられる。これらは、ウレタン骨格を有する水分散性樹脂である。また、ニチゴー・モビニール株式会社製モビニール９６５、モビニール８０５５Ａ等が挙げられる。これらは、スチレン−アクリル樹脂である。水分散性樹脂は、インク全量に対し１〜１５質量％含まれていることが好ましく、３〜１０質量％含まれていることがより好ましい。 The water dispersible resin contained in the ink of the ink set may be a self-emulsifying type into which a hydrophilic component necessary for stable dispersion in water is introduced, or may be water dispersible by using an external emulsifier. Good. Preferred examples of the water-dispersible resin include acrylic resins, styrene-acrylic resins, urethane resins, vinyl acetate resins, acrylic-vinyl acetate resins, and these may be used alone or in combination of two or more. Can do. More specifically, for example, Superflex 460, 460s, 470, 500M, 610, 700 in the Superflex series manufactured by Daiichi Kogyo Seiyaku Co., Ltd., Adekabon titer in the Adekabon titer series manufactured by Adeka Co., Ltd. HUX-380, 290K, 290H, Takelac W-512A6 manufactured by Mitsui Chemicals Polyurethane Co., Ltd. and the like. These are water-dispersible resins having a urethane skeleton. Moreover, Nichigo Movinyl Co., Ltd. made Movinyl 965, Movinyl 8055A, etc. are mentioned. These are styrene-acrylic resins. The water-dispersible resin is preferably contained in an amount of 1 to 15% by mass and more preferably 3 to 10% by mass with respect to the total amount of ink.
水は、粘度調整の観点から、インク中に２０〜８０質量％含まれていることが好ましく、３０〜７０質量％含まれていることがより好ましい。
インクの粘度は、吐出ヘッドのノズル径や吐出環境等によってその適性範囲は異なるが、一般に、２３℃において１〜３０ｍＰａ・ｓであることが好ましく、３〜１５ｍＰａ・ｓであることがより好ましく、さらには約５ｍＰａ・ｓ程度であることが、インクジェット記録装置用としては望ましい。ここで粘度は、２３℃において０．１Ｐａ／ｓの速度で剪断応力を０Ｐａから増加させたときの１０Ｐａにおける値を表す。
From the viewpoint of adjusting the viscosity, water is preferably contained in the ink in an amount of 20 to 80% by mass, and more preferably 30 to 70% by mass.
The viscosity of the ink varies depending on the nozzle diameter of the discharge head, the discharge environment, and the like, but in general, it is preferably 1 to 30 mPa · s at 23 ° C., more preferably 3 to 15 mPa · s, Further, about 5 mPa · s is desirable for an inkjet recording apparatus. Here, the viscosity represents a value at 10 Pa when the shear stress is increased from 0 Pa at a rate of 0.1 Pa / s at 23 ° C.
水性インクには、必要に応じて、本発明の目的を阻害しない範囲内で、当該分野において通常用いられている各種添加剤を含ませることができる。具体的には、顔料分散剤、消泡剤、表面張力低下剤等として、アニオン界面活性剤、カチオン界面活性剤、両性界面活性剤、非イオン界面活性剤、または高分子系、シリコーン系、フッ素系の界面活性剤をインクに含有させることができる。
水性インクは、上記油性インクと同様の方法で調製することができる。
If necessary, the water-based ink may contain various additives that are usually used in the art as long as the object of the present invention is not impaired. Specifically, an anionic surfactant, a cationic surfactant, an amphoteric surfactant, a nonionic surfactant, or a polymer, silicone, fluorine, as a pigment dispersant, an antifoaming agent, a surface tension reducing agent, etc. System surfactants can be included in the ink.
The water-based ink can be prepared by the same method as the oil-based ink.
本発明のインクジェット印刷方法は、前処理液を印刷媒体へ塗布した後、インクを印刷媒体上へ吐出させることにより行われる。前処理液の印刷媒体への塗布は、刷毛、ローラー、バーコーター等を使用して印刷媒体の表面を均一にコーティングすることによって行ってもよく、または、インクジェット印刷およびグラビア印刷などの印刷手段によって画像を印刷することで行ってもよい。例えば、塗工ローラーを印字部より手前に配置し、印刷媒体全面に前処理液を塗布した後、直ちにこれに重ねてインクを連続的に吐出させることにより印刷を行うことができる。このように、本発明では、前処理液を印刷媒体に塗布した後、塗布された処理液が乾燥する前に直ちにインクを吐出させることが可能である。 The ink jet printing method of the present invention is carried out by applying a pretreatment liquid to a print medium and then discharging ink onto the print medium. The pretreatment liquid may be applied to the printing medium by uniformly coating the surface of the printing medium using a brush, roller, bar coater, or the like, or by printing means such as inkjet printing and gravure printing. This may be done by printing an image. For example, it is possible to perform printing by disposing a coating roller in front of the printing unit, applying a pretreatment liquid to the entire surface of the printing medium, and then immediately discharging ink on the printing medium. As described above, in the present invention, after the pretreatment liquid is applied to the print medium, it is possible to immediately eject ink before the applied treatment liquid dries.
本発明のインクジェット印刷方法を容易に実施できるように、上記前処理液と油性インクまたは水性インクを少なくとも含むインクセットを構成して販売すると好都合である。ここでインクセットとは、前処理液カートリッジとインクカートリッジが複数一体になっているインクカートリッジ自体はもちろんのこと、単独の前処理液カートリッジとインクカートリッジを複数組み合わせて使用する場合も含み、さらに、前処理液カートリッジとインクカートリッジと記録ヘッドを一体としたものも含まれる。 It is advantageous to configure and sell an ink set including at least the pretreatment liquid and the oil-based ink or the water-based ink so that the ink jet printing method of the present invention can be easily carried out. Here, the ink set includes not only an ink cartridge itself in which a plurality of pretreatment liquid cartridges and ink cartridges are integrated, but also a case where a plurality of single pretreatment liquid cartridges and ink cartridges are used in combination. A unit in which a pretreatment liquid cartridge, an ink cartridge, and a recording head are integrated is also included.
本発明において、印刷媒体は、特に限定されるものではなく、普通紙、光沢紙、特殊紙、布、フィルム、ＯＨＰシートなどが使用できる。とりわけ、本発明によれば、普通紙に印刷する場合でも、顔料が印刷用紙に浸透せずに印刷用紙の表面に留まるので、印字濃度が向上し、裏抜けや滲みが低減し、また、印刷中の印刷用紙のカールが防止され、高速印刷を阻害しないという大きなメリットが得られる。
以下に本発明を実施例によりさらに詳細に説明する。
In the present invention, the printing medium is not particularly limited, and plain paper, glossy paper, special paper, cloth, film, OHP sheet and the like can be used. In particular, according to the present invention, even when printing on plain paper, the pigment stays on the surface of the printing paper without penetrating the printing paper, so that the printing density is improved, and the back-through and bleeding are reduced. The curling of the printing paper inside is prevented, and a great merit that high-speed printing is not hindered is obtained.
Hereinafter, the present invention will be described in more detail with reference to examples.
（前処理液の作製）
表１および２に示す各成分を表１および２に示す割合でプレミックスし、その後、超音波分散機にて１分間分散し、得られた分散液を前処理液とした。なお、表１および２の無機粒子の数値はレーザー光回折散乱法により測定される平均粒子径、溶媒の数値はＳＰ値である。
(Preparation of pretreatment liquid)
Each component shown in Tables 1 and 2 was premixed in the proportions shown in Tables 1 and 2, and then dispersed for 1 minute with an ultrasonic disperser, and the resulting dispersion was used as a pretreatment liquid. In addition, the numerical value of the inorganic particle of Table 1 and 2 is an average particle diameter measured by a laser beam diffraction scattering method, and the numerical value of a solvent is SP value.
尚、表１記載の原材料の詳細は下記のとおりである。
シーホスターＫＥ−Ｐ１００：株式会社日本触媒製シリカ粒子
ミズカシルＰ−７３、Ｐ−７５８Ｃ、Ｐ−７８Ｆ：水澤化学工業株式会社製シリカ粒子
ソルスパース２７０００：日本ルーブリゾール社製高分子分散剤
ＪＭＲ−１０Ｍ：日本酢ビ・ポバール株式会社製ポリビニルアルコール
モビニール９６６Ａ：日本合成化学株式会社製スチレン／アクリル系エマルション樹脂
スラウト３３：日本エンバイロケミカル株式会社製防腐剤
サーフィノールＤＦ−５８：日信化学工業株式会社製シリコーン変性消泡剤
アロンＳＤ−１０東亞合成株式会社製分散剤「アロンＳＤ−１０（商品名）」（ポリアクリル酸系共重合体・固形分４０％）
エリーテルＫＺＴ−０５０７：ユニチカ株式会社製「エリーテＫＺＴ−０５０７（商品名）」（ポリエステル樹脂エマルション・固形分３０％）
The details of the raw materials listed in Table 1 are as follows.
Seahoster KE-P100: Silica particles Mizukasil P-73, P-758C, P-78F manufactured by Nippon Shokubai Co., Ltd .: Silica particles Solsperse 27000 manufactured by Mizusawa Chemical Co., Ltd. Polyvinyl alcohol mobile vinyl 966A manufactured by Nippon Vinyl Chemical Poval Co., Ltd .: Styrene / acrylic emulsion resin slout 33 manufactured by Nippon Synthetic Chemical Co., Ltd .: Preservative Surfynol DF-58 manufactured by Nippon Enviro Chemical Co., Ltd. Dispersant “Aron SD-10 (trade name)” manufactured by Toagosei Co., Ltd. (polyacrylic acid copolymer / solid content 40%)
Elite KZT-0507: "Elite KZT-0507 (trade name)" (polyester resin emulsion, solid content 30%) manufactured by Unitika Ltd.
（油性インクの作製）
表３に示す各成分を表３に示す割合でプレミックスし、その後、ビーズミル（直径（φ）０．５ｍｍのジルコニアビーズ使用）にて分散し、得られた分散液をメンブレンフィルター（開口径３μｍ）でろ過し、油性インクを得た。なお、表３記載の原材料の詳細は下記のとおりである。
カーボンブラック：三菱化学社製カーボンブラック ＭＡ−１１（商品名）
ソルスパース２８０００（商品名）：ルーブリゾール社製顔料分散剤
オレイン酸メチル：花王株式会社製エキセパールＭ−ＯＬ
ミリスチン酸イソプロピル：花王株式会社製エキセパールＩＰＭ
炭化水素溶剤：新日本石油製ノルマルパラフィンＨ
(Production of oil-based ink)
Each component shown in Table 3 was premixed at the ratio shown in Table 3, and then dispersed in a bead mill (using zirconia beads having a diameter (φ) of 0.5 mm), and the resulting dispersion was subjected to a membrane filter (opening diameter: 3 μm). ) To obtain an oil-based ink. The details of the raw materials listed in Table 3 are as follows.
Carbon black: Carbon black MA-11 (trade name) manufactured by Mitsubishi Chemical Corporation
Solsperse 28000 (trade name): Pigment dispersant manufactured by Lubrizol Co., Ltd. Methyl oleate: Exepal M-OL manufactured by Kao Corporation
Isopropyl myristate: EXOPARL IPM manufactured by Kao Corporation
Hydrocarbon solvent: normal paraffin H manufactured by Nippon Oil Corporation
（実施例１〜８および比較例１〜６）
表３に記載の油性インクを、理想科学工業株式会社製インクジェットプリンタ「ＨＣ５５００（商品名）」の吐出経路に導入し、印刷用紙として理想科学工業株式会社製「理想用紙薄口（商品名）」を用い、この印刷用紙の片面全面に表１および２に記載の前処理液を、塗工液量が１１〜１２ｇ／ｍ2になるように、バーコーターで塗布した後、３０秒後に印刷用紙の処理表面上に油性インクを吐出させ、ベタ画像および複数の細線を印刷した。印刷は、解像度３００×３００ｄｐｉにて、１ドット当りのインク量が３６ｐｌの吐出条件で行った。
(Examples 1-8 and Comparative Examples 1-6)
The oil-based ink listed in Table 3 was introduced into the ejection path of an inkjet printer “HC5500 (trade name)” manufactured by Riso Kagaku Co., Ltd. The pretreatment liquid described in Tables 1 and 2 was applied to the entire surface of one side of the printing paper with a bar coater so that the amount of the coating liquid was 11 to 12 g / m 2 , and 30 seconds later. Oil-based ink was ejected onto the treated surface, and a solid image and a plurality of fine lines were printed. Printing was performed at a resolution of 300 × 300 dpi under an ejection condition where the ink amount per dot was 36 pl.
（評価）
（印刷物の印刷濃度）
上記で得られた印刷物を１晩放置後、ベタ画像の表面の印刷画像濃度（ＯＤ）を、光学濃度計（ＲＤ９２０：マクベス社製）を用いて測定した。
◎：１．３０≦ＯＤ
○：１．２５≦ＯＤ＜１．３０
×：ＯＤ＜１．２５
(Evaluation)
(Print density of printed matter)
The printed matter obtained above was allowed to stand overnight, and then the printed image density (OD) of the surface of the solid image was measured using an optical densitometer (RD920: manufactured by Macbeth Co.).
A: 1.30 ≦ OD
○: 1.25 ≦ OD <1.30
×: OD <1.25
（印刷物の裏抜け）
上記で得られた印刷物を１晩放置後、ベタ画像の裏面の印刷画像濃度（ＯＤ）を、光学濃度計（ＲＤ９２０：マクベス社製）を用いて測定した。得られた測定値から印刷用紙の非印刷部のＯＤ値を差し引いた値ΔＯＤを、印刷物の裏抜けとした。
○：ΔＯＤ＜０．１０
×：０．１０≦ΔＯＤ
(Background of printed matter)
The printed matter obtained above was allowed to stand overnight, and the printed image density (OD) of the back side of the solid image was measured using an optical densitometer (RD920: manufactured by Macbeth Co.). A value ΔOD obtained by subtracting the OD value of the non-printing portion of the printing paper from the obtained measured value was regarded as the back side of the printed matter.
○: ΔOD <0.10
×: 0.10 ≦ ΔOD
（印刷物の滲み）
上記で得られた印刷物を１晩放置後、細線が複数並んだ画像を印刷した印刷物を目視で観察し、線の太り・滲みの度合いを、下記基準で評価した。
○：滲みがない
△：やや滲んでいる
×：大きく滲んでいる
(Bleed of printed matter)
The printed matter obtained above was allowed to stand overnight, and then the printed matter on which an image having a plurality of fine lines was printed was visually observed, and the degree of line thickening / bleeding was evaluated according to the following criteria.
○: No bleeding △: Slightly blurred ×: Largely blurred
（用紙変形）
理想用紙薄口を１０ｃｍ×１５ｃｍにカットしたものの一辺を台紙に両面テープで固定し、この用紙の片面全面に表１および２に記載の前処理液を、塗工液量が１１〜１２ｇ／ｍ2になるようにバーコーターで塗布した後、印刷した印刷物の用紙変形量を、前処理液を塗布してから３０秒後と１日後について下記の基準で評価した。なお、用紙変形量は環境の影響を受けやすいため、室温２３℃、湿度５０％の環境で評価した。下記変形量は、用紙が静置面から見て凸に変形した場合の最も高い部分の値を正の変形量、凹に変形した場合の最も高い部分の値を負の変形量として評価したものである。
前処理液塗布後３０秒の用紙変形量
◎：−２０ｍｍ≦用紙変形量＜２０ｍｍ
○：−２６ｍｍ≦用紙変形量＜−２０ｍｍ，２０ｍｍ≦用紙変形量＜２６ｍｍ
×：用紙変形量＜−２６ｍｍ、２６ｍｍ＜用紙変形量
前処理液塗布後に印刷した印刷物の１日後の用紙変形量
◎：−２ｍｍ≦用紙変形量≦２ｍｍ
○：−９ｍｍ≦用紙変形量＜−２ｍｍ，２ｍｍ≦用紙変形量＜９ｍｍ
×：用紙変形量＜−９ｍｍ、９ｍｍ＜用紙変形量
評価結果を前処理液の構成とともに表４および表５に示す。
(Paper deformation)
One side of an ideal paper thin end cut to 10 cm × 15 cm is fixed to a backing sheet with double-sided tape, and the pretreatment liquid described in Tables 1 and 2 is applied to the entire surface of one side of the paper with a coating liquid amount of 11 to 12 g / m 2. After coating with a bar coater, the amount of paper deformation of the printed product was evaluated according to the following criteria for 30 seconds and 1 day after the pretreatment liquid was applied. Since the amount of deformation of the sheet is easily influenced by the environment, the evaluation was performed in an environment at a room temperature of 23 ° C. and a humidity of 50%. The amount of deformation shown below is evaluated as a positive deformation amount when the paper is deformed convexly when viewed from the stationary surface, and a negative deformation amount when the paper is deformed concavely. It is.
Paper deformation amount 30 seconds after applying pretreatment liquid ◎: −20 mm ≦ paper deformation amount <20 mm
○: −26 mm ≦ paper deformation <−20 mm, 20 mm ≦ paper deformation <26 mm
×: Paper deformation amount <−26 mm, 26 mm <Paper deformation amount The paper deformation amount one day after the printed matter printed after applying the pretreatment liquid ◎: −2 mm ≦ paper deformation amount ≦ 2 mm
○: −9 mm ≦ paper deformation <−2 mm, 2 mm ≦ paper deformation <9 mm
×: Paper deformation amount <−9 mm, 9 mm <paper deformation amount evaluation results are shown in Tables 4 and 5 together with the composition of the pretreatment liquid.
表４に示すように、実施例１〜８は、前処理液を印刷媒体へ塗布した後、３０秒後にインクを印刷しても、印刷ドットの滲みを十分に抑制でき、写真画像や文字の滲みのない、シャープで高濃度な印刷画像を得ることができた。また、処理直後の印刷媒体のカール等の変形が抑制されるとともに、前処理液処理後に印刷した印刷物の数時間経過後の変形も抑制することができており、高品質の印刷物が得られた。 As shown in Table 4, in Examples 1 to 8, even after printing the pretreatment liquid on the printing medium and printing the ink 30 seconds later, bleeding of the printed dots can be sufficiently suppressed, and photographic images and characters A sharp and high density printed image without blurring could be obtained. In addition, deformation such as curling of the printing medium immediately after the treatment is suppressed, and deformation after several hours of the printed matter printed after the pretreatment liquid treatment can be suppressed, and a high-quality printed matter was obtained. .
一方、前処理剤を使用していない比較例１は、用紙変形は生じなかったが、印刷媒体に対する目止め効果がないため、裏抜けが顕著で、結果印刷濃度が低く、滲みも生じた。シリカ粒子を含んでいてもその含有量が少ない比較例２は、印刷画像が悪かった。水分量が５５質量％よりも多い比較例３は、印刷画像の裏抜けおよび滲みが悪く、用紙変形が生じた。特定溶剤を含まない、または本発明の範囲より少ない量を含む比較例４および５は、印刷画像は比較的良好であったが、用紙変形が生じた。特定溶剤の含有量が本発明の範囲より多い比較例６は、用紙変形は良好であったが印刷画像が悪かった。シリカ粒子の含有量は本発明の範囲内であるが、粒子の平均粒子径が本発明の範囲外である比較例７は、用紙変形は良好であったが、印刷濃度が低かった。 On the other hand, in Comparative Example 1 in which no pretreatment agent was used, paper deformation did not occur, but since there was no sealing effect on the print medium, the show-through was significant, resulting in low print density and bleeding. In Comparative Example 2, which contains silica particles but has a small content, the printed image was poor. In Comparative Example 3 having a moisture content of more than 55% by mass, the print image had poor penetration and bleeding, and paper deformation occurred. In Comparative Examples 4 and 5, which did not contain a specific solvent or contained less than the scope of the present invention, the printed image was relatively good, but paper deformation occurred. In Comparative Example 6 in which the content of the specific solvent was larger than the range of the present invention, the paper deformation was good, but the printed image was bad. Although the content of the silica particles is within the range of the present invention, Comparative Example 7 in which the average particle size of the particles is outside the range of the present invention has good paper deformation, but the printing density is low.
（水性インクの作製）
表６に示す各成分を表６に示す割合でミックスし、その後、得られた分散液をメンブレンフィルター（開口径３μｍ）でろ過し、水性インクを得た。なお、表６記載の原材料の詳細は下記のとおりである。
ＣＡＢ−Ｏ−ＪＥＴ３００（商品名）：ＣＡＢＯＴ社製自己分散カーボンブラック分散体
サーフィノール４６５（商品名）：エアープロダクツ社製浸透剤
(Preparation of water-based ink)
Each component shown in Table 6 was mixed in the ratio shown in Table 6, and then the obtained dispersion was filtered through a membrane filter (opening diameter: 3 μm) to obtain an aqueous ink. The details of the raw materials listed in Table 6 are as follows.
CAB-O-JET300 (trade name): Self-dispersing carbon black dispersion Surfynol 465 (trade name) manufactured by CABOT: Penetration agent manufactured by Air Products
（実施例９〜１１および比較例７〜９）
表６に記載の水性インクを、印刷用紙として理想科学工業株式会社製「理想用紙薄口（商品名）」を１０×１５ｃｍにカットしたものを用い、この印刷用紙の片面全面に表１および２に記載の前処理液を、塗工液量が１２〜１３ｇ／ｍ2になるようにバーコーターで塗布した後、３０秒後に印刷用紙の処理表面上に表６に記載の水性インクを、インク転移量として１１ｇ／ｍ2になるようにベタ画像をインクジェット印刷した。
(Examples 9-11 and Comparative Examples 7-9)
Using the water-based inks listed in Table 6 with “ideal paper thin mouth (product name)” manufactured by Riso Kagaku Co., Ltd. cut to 10 × 15 cm as printing paper, the entire surface of one side of this printing paper is shown in Tables 1 and 2. After applying the pretreatment liquid described above with a bar coater so that the coating liquid amount is 12 to 13 g / m 2 , 30 seconds later, the aqueous ink described in Table 6 was transferred onto the treated surface of the printing paper. A solid image was inkjet printed so that the amount was 11 g / m 2 .
（評価）
（印刷物の印刷濃度）
上記で得られた印刷物を１晩放置後、ベタ画像の表面の印刷画像濃度（ＯＤ）を、光学濃度計（ＲＤ９２０：マクベス社製）を用いて測定した。
◎：１．３０≦ＯＤ
○：１．２５≦ＯＤ＜１．３０
×：ＯＤ＜１．２５
(Evaluation)
(Print density of printed matter)
The printed matter obtained above was allowed to stand overnight, and then the printed image density (OD) of the surface of the solid image was measured using an optical densitometer (RD920: manufactured by Macbeth Co.).
A: 1.30 ≦ OD
○: 1.25 ≦ OD <1.30
×: OD <1.25
（印刷物の裏抜け）
上記で得られた印刷物を１晩放置後、ベタ画像の裏面の印刷画像濃度（ＯＤ）を、光学濃度計（ＲＤ９２０：マクベス社製）を用いて測定した。得られた測定値から印刷用紙の非印刷部のＯＤ値を差し引いた値ΔＯＤを、印刷物の裏抜けとした。
○：ΔＯＤ＜０．１２
×：０．１２≦ΔＯＤ
(Background of printed matter)
The printed matter obtained above was allowed to stand overnight, and the printed image density (OD) of the back side of the solid image was measured using an optical densitometer (RD920: manufactured by Macbeth Co.). A value ΔOD obtained by subtracting the OD value of the non-printing portion of the printing paper from the obtained measured value was regarded as the back side of the printed matter.
○: ΔOD <0.12
×: 0.12 ≦ ΔOD
（用紙変形）
理想用紙薄口を１０ｃｍ×１５ｃｍにカットしたものの一辺を台紙に両面テープで固定し、この用紙の片面全面に表１および２に記載の前処理液を、塗工液量が１１〜１２ｇ／ｍ2になるようにバーコーターで塗布した後、印刷した印刷物の用紙変形量を、前処理液を塗布してから３０秒後と１日後について下記の基準で評価した。なお、用紙変形量は環境の影響を受けやすいため、室温２３℃、湿度５０％の環境で評価した。下記変形量は、用紙が静置面から見て凸に変形した場合の最も高い部分の値を正の変形量、凹に変形した場合の最も高い部分の値を負の変形量として評価したものである。
前処理液塗布後３０秒の用紙変形量
◎：−２０ｍｍ≦用紙変形量＜２０ｍｍ
○：−２５ｍｍ≦用紙変形量＜−２０ｍｍ，２０ｍｍ≦用紙変形量＜２５ｍｍ
×：用紙変形量＜−２５ｍｍ、２５ｍｍ＜用紙変形量
前処理液塗布後に印刷した印刷物の１日後の用紙変形量
◎：−２ｍｍ≦用紙変形量≦２ｍｍ
○：−９ｍｍ≦用紙変形量＜−２ｍｍ，２ｍｍ≦用紙変形量＜９ｍｍ
×：用紙変形量＜−９ｍｍ、９ｍｍ＜用紙変形量
評価結果を前処理液の構成とともに表７に示す。
(Paper deformation)
One side of an ideal paper thin end cut to 10 cm × 15 cm is fixed to a backing sheet with double-sided tape, and the pretreatment liquid described in Tables 1 and 2 is applied to the entire surface of one side of the paper with a coating liquid amount of 11 to 12 g / m 2. After coating with a bar coater, the amount of paper deformation of the printed product was evaluated according to the following criteria for 30 seconds and 1 day after the pretreatment liquid was applied. Since the amount of deformation of the sheet is easily influenced by the environment, the evaluation was performed in an environment at a room temperature of 23 ° C. and a humidity of 50%. The amount of deformation shown below is evaluated as a positive deformation amount when the paper is deformed convexly when viewed from the stationary surface, and a negative deformation amount when the paper is deformed concavely. It is.
Paper deformation amount 30 seconds after applying pretreatment liquid ◎: −20 mm ≦ paper deformation amount <20 mm
○: −25 mm ≦ paper deformation <−20 mm, 20 mm ≦ paper deformation <25 mm
×: Paper deformation amount <−25 mm, 25 mm <Paper deformation amount The paper deformation amount one day after the printed matter printed after applying the pretreatment liquid ◎: −2 mm ≦ paper deformation amount ≦ 2 mm
○: −9 mm ≦ paper deformation <−2 mm, 2 mm ≦ paper deformation <9 mm
×: Paper deformation amount <−9 mm, 9 mm <paper deformation amount evaluation results are shown in Table 7 together with the composition of the pretreatment liquid.
表７に示すように、実施例９〜１１は、前処理液を印刷媒体へ塗布した後、３０秒後に水性インクを印刷しても、裏抜けのない高濃度な印刷画像を得ることができた。また、処理直後の印刷媒体のカール等の変形が抑制され、前処理液処理後に印刷した印刷物の数時間経過後の変形も抑制することができており、高品質の印刷物が得られた。一方、前処理剤を使用していない比較例１は前処理液処理直後に用紙変形が生じ、印刷媒体に対する目止め効果がないため、裏抜けが顕著で、結果印刷濃度が低かった。シリカ粒子の含有量が本発明の範囲外である比較例８は、印刷濃度が低く、裏抜けや印刷画像の滲みが悪かった。比較例９は特許文献６に記載の前処理液であるが、水性インクに対しては用紙変形の抑制効果が低いことがわかる。一方、比較例８は特定溶剤の含有量および水分量は本発明の範囲であったものの、シリカ粒子の濃度が低いために用紙変形の抑制効果が低く、印刷画像の品質も悪くなった。 As shown in Table 7, in Examples 9 to 11, a high-density print image without back-through can be obtained even when aqueous ink is printed 30 seconds after the pretreatment liquid is applied to the print medium. It was. Further, deformation such as curling of the printing medium immediately after the treatment was suppressed, and deformation after several hours of the printed matter printed after the pretreatment liquid treatment could be suppressed, and a high quality printed matter was obtained. On the other hand, in Comparative Example 1 in which no pretreatment agent was used, paper deformation occurred immediately after the treatment with the pretreatment liquid, and there was no sealing effect on the print medium. Therefore, the showthrough was remarkable and the resulting print density was low. In Comparative Example 8 in which the content of the silica particles was outside the range of the present invention, the printing density was low, and the show-through and bleeding of the printed image were bad. Comparative Example 9 is the pretreatment liquid described in Patent Document 6, but it can be seen that the effect of suppressing sheet deformation is low for aqueous ink. On the other hand, in Comparative Example 8, although the content of the specific solvent and the water content were within the scope of the present invention, the effect of suppressing paper deformation was low due to the low concentration of silica particles, and the quality of the printed image was also deteriorated.
以上のように、本発明のインクジェット印刷方法およびインクセットは、所定粒子径の無機粒子を２０質量％よりも多く、所定範囲のＳＰ値を有する溶剤の含有量を１５質量％以上２５質量％以下の範囲にするとともに、前処理液中の水分量を５５質量％以下とすることで、印刷媒体の表面が目止めされ、印刷されたインク中の顔料の浸透が抑制されるために、顔料が印刷媒体表面上に留まって高濃度な印刷画像を得ることができ、前処理液処理直後の印刷媒体のカール等の変形を抑制することができるので高速印刷が可能となり、高品質の印刷物を得ることができる。 As described above, the inkjet printing method and the ink set of the present invention have an inorganic particle having a predetermined particle diameter of more than 20% by mass and a solvent content having a SP value in a predetermined range of 15% by mass to 25% by mass. When the water content in the pretreatment liquid is 55% by mass or less, the surface of the print medium is sealed, and the penetration of the pigment in the printed ink is suppressed. A high density printed image can be obtained by staying on the surface of the printing medium, and deformation such as curling of the printing medium immediately after the pretreatment liquid treatment can be suppressed, enabling high-speed printing and obtaining a high-quality printed matter. be able to.
Claims (3)
前記前処理液が少なくとも無機粒子と水と溶剤を含んでなり、前記無機粒子のレーザー光回折散乱法により測定される平均粒子径が１〜２０μｍであって、該無機粒子を前記前処理液全量に対して２０質量％よりも多く含み、前記前処理液中の水分量が前記前処理液全量に対して５５質量％以下であり、溶解度パラメータ（ＳＰ値）が８．５（ｃａｌ／ｃｍ3）1/2以上、１２．０（ｃａｌ／ｃｍ3）1/2以下の溶剤を前記前処理液全量に対して１５質量％以上２５質量％以下の範囲で含むことを特徴とするインクジェット印刷方法。 In an inkjet printing method for performing printing by applying an ink containing at least a pigment and a solvent onto the printing medium after applying the pretreatment liquid to the printing medium,
The pretreatment liquid comprises at least inorganic particles, water, and a solvent, the average particle diameter of the inorganic particles measured by a laser light diffraction scattering method is 1 to 20 μm, and the total amount of the inorganic particles is the pretreatment liquid. The water content in the pretreatment liquid is 55 mass% or less with respect to the total amount of the pretreatment liquid, and the solubility parameter (SP value) is 8.5 (cal / cm 3). ) 1/2 or more and 12.0 (cal / cm 3 ) 1/2 or less of the solvent in a range of 15 to 25% by mass with respect to the total amount of the pretreatment liquid .
少なくとも顔料および溶剤を含んでなるインクと、少なくとも無機粒子と水と溶剤を含んでなる前処理液とからなり、前記無機粒子のレーザー光回折散乱法により測定される平均粒子径が１〜２０μｍであって、該無機粒子を前記前処理液全量に対して２０質量％よりも多く含み、前記前処理液中の水分量が前記前処理液全量に対して５５質量％以下であり、溶解度パラメータ（ＳＰ値）が８．５（ｃａｌ／ｃｍ3）1/2以上、１２．０（ｃａｌ／ｃｍ3）1/2以下の溶剤を前記前処理液全量に対して１５質量％以上２５質量％以下の範囲で含むことを特徴とするインクセット。 An ink set used for ink jet printing in which printing is performed by ejecting an ink containing at least a pigment and a solvent onto the printing medium after applying the pretreatment liquid to the printing medium,
It comprises an ink comprising at least a pigment and a solvent, and a pretreatment liquid comprising at least inorganic particles, water and a solvent, and the average particle diameter of the inorganic particles measured by a laser light diffraction scattering method is 1 to 20 μm. The inorganic particles are contained in an amount of more than 20% by mass with respect to the total amount of the pretreatment liquid, the water content in the pretreatment liquid is 55% by mass or less with respect to the total amount of the pretreatment liquid, and the solubility parameter ( SP value) is not less than 8.5 (cal / cm 3 ) 1/2 and not more than 12.0 (cal / cm 3 ) 1/2 of 15% by mass to 25% by mass with respect to the total amount of the pretreatment liquid. An ink set comprising:
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2015145117A (en) * | 2014-02-04 | 2015-08-13 | 株式会社リコー | Image forming apparatus and image forming method |
| JP2015229241A (en) * | 2014-06-03 | 2015-12-21 | 株式会社リコー | Image forming method and image forming apparatus |
| JP2016145312A (en) * | 2015-01-29 | 2016-08-12 | 富士フイルム株式会社 | Ink set and image forming method |
| JP2017019918A (en) * | 2015-07-09 | 2017-01-26 | 株式会社リコー | Ink set, ink cartridge, ink jet recording device and inkjet recording method |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2015145117A (en) * | 2014-02-04 | 2015-08-13 | 株式会社リコー | Image forming apparatus and image forming method |
| JP2015229241A (en) * | 2014-06-03 | 2015-12-21 | 株式会社リコー | Image forming method and image forming apparatus |
| JP2016145312A (en) * | 2015-01-29 | 2016-08-12 | 富士フイルム株式会社 | Ink set and image forming method |
| JP2017019918A (en) * | 2015-07-09 | 2017-01-26 | 株式会社リコー | Ink set, ink cartridge, ink jet recording device and inkjet recording method |
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