JP2007230215A - Liquid-ejecting head, image-forming apparatus, device for ejecting liquid droplet, and recording method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a high-quality liquid-ejecting head which improves the jointing precision and dimensional precision without causing brittleness and heat shrinkage during heat treatment. <P>SOLUTION: When a nozzle plate 2 is formed by a Ni-electroforming (electrocasting) method, thallium is added to the Ni-electroforming bath to form a metal material containing nickel and thallium, and the brittleness and the heat shrinkage in the liquid ejecting head, are reduced by making a peak intensity for a (200) face of nickel higher than the peak intensity for a (111) face of nickel as measured by means of X-ray diffraction analysis. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a liquid ejection head and an image forming apparatus, and more particularly to a liquid ejection head having a surface subjected to water repellency treatment, an image forming apparatus including the liquid ejection head, an apparatus for ejecting liquid droplets, and a recording method.

  As an image forming apparatus such as a printer, a facsimile, a copying apparatus, and a multifunction machine of these, for example, an ink jet recording apparatus is known. The ink jet recording apparatus uses a liquid discharge head as a recording head, and is a recording medium such as recording paper (hereinafter referred to as “paper”, but the material is not limited to paper, and the recording medium, transfer paper, transfer material, Recording is also performed by ejecting ink droplets as a recording liquid (also referred to as image formation, printing, printing, printing, etc.).

  By the way, as the liquid ejection head, for example, a nozzle that ejects droplets having a size of several μm to several tens of μm, a liquid chamber that communicates with the nozzle, a diaphragm that forms a wall surface of the liquid chamber, and a diaphragm Equipped with a piezoelectric actuator such as a piezoelectric element that pressurizes the recording liquid in the liquid chamber, a nozzle that discharges droplets, a liquid chamber that communicates with the nozzle, and electrothermal conversion of the recording liquid in the liquid chamber such as a heating resistor A device equipped with a thermal actuator that pressurizes using phase change due to film boiling using an element, a nozzle that discharges droplets, a liquid chamber that communicates with the nozzle, a diaphragm that forms the wall surface of the liquid chamber, and vibration A device including an electrostatic actuator that pressurizes a recording liquid in a liquid chamber by displacing a vibration plate by an electrostatic force generated between electrodes facing the plate is known.

Here, as a flow path forming member that forms or forms a flow path of the liquid discharge head, for example, as a nozzle forming member that forms a nozzle hole that becomes a nozzle, an electric current as described in Patent Documents 1 to 4 is used. A metal material containing nickel by a casting method, an organic polymer resin material drilled by excimer laser processing as described in Patent Document 5, SUS or the like as described in Patent Document 6 There is a metal plate punched with a punch press.
Japanese Patent Application Laid-Open No. 2003-025590 JP 2004-030636 A JP 2001-038915 A JP 2005-178227 A JP 2000-318160 A Japanese Patent No. 2998754

  By the way, when a flow path forming member for forming a flow path such as a nozzle plate, a flow path plate, or a vibration plate is formed by an electroforming method, usually an organic additive having an S element in the molecule or a benzene ring skeleton In order to improve the wettability, the primer heat treatment process is applied in order to improve the bondability with the dissimilar member in the step of bonding the flow path forming member. When heat treatment for forming an oxidation protective film such as a thermal oxide film is performed, there is a problem that sulfur embrittlement and thermal shrinkage occur.

  When such sulfur embrittlement and thermal shrinkage occur, it becomes impossible to join the flow path forming member with high accuracy, and the yield decreases. Further, when the flow path forming member is a nozzle plate, the nozzle hole accuracy is lowered, and problems such as the required droplet ejection characteristics (droplet ejection speed, droplet ejection volume) cannot be obtained.

  SUMMARY An advantage of some aspects of the invention is that it provides a high-quality liquid ejection head, an image forming apparatus including the liquid ejection head, an apparatus for ejecting liquid droplets, and a recording method.

  In order to solve the above problems, in the liquid discharge head according to the present invention, the flow path forming member that forms the flow path of the recording liquid is formed of a metal material containing nickel, and nickel (200) measured by X-ray analysis. The peak intensity at the surface is superior to the peak intensity at the nickel (111) surface.

  Here, the metal material forming the flow path forming member can be configured to contain thallium, and the thallium content preferably does not exceed 1 mass%.

  Further, the flow path forming member can be configured to contain cobalt, and the cobalt content preferably does not exceed 1 mass%.

  Further, the flow path forming member may be configured to contain manganese, and the manganese content preferably does not exceed 1 mass%.

  In the liquid discharge head according to the present invention, the flow path forming member that forms the flow path of the recording liquid is formed of a metal material containing nickel and thallium.

  Here, it is preferable that the peak intensity on the nickel (200) plane measured by X-ray analysis is superior to the peak intensity on the nickel (111) plane.

  In the liquid discharge head according to the present invention, when the peak intensity on the nickel (111) plane measured by X-ray diffraction is I (111) and the peak intensity on the nickel (200) plane is I (200), nickel The intensity ratio of the crystal orientation plane represented by the ratio of the peak intensity at the nickel (200) plane to the peak intensity at the (111) plane is in the relationship of I (200) / I (111)> 1.0. It is preferable.

  Further, it is preferable that the flow path forming member contains sulfur, and the content of this sulfur does not exceed 0.1 mass%.

  Further, the flow path forming member may be a nozzle plate in which a nozzle is formed, a flow path plate in which a liquid chamber is formed, or a vibration plate in which a wall surface of the liquid chamber is formed. Furthermore, it can have a configuration in which at least two members, a nozzle plate in which a nozzle is formed, a flow path plate in which a liquid chamber is formed, and a vibration plate in which the wall surface of the liquid chamber is formed, are integrally formed. .

  Further, the flow path forming member can be formed by electroforming. The flow path forming member preferably has a Vickers hardness (HV) in the range of 250 (Hv) to 500 (Hv). Further, the head can be configured as a side shooter head in which the droplet discharge direction and the recording liquid flow channel direction are different.

  An image forming apparatus according to the present invention includes any one of the liquid ejection heads according to the present invention as a recording head that ejects droplets of a recording liquid.

  Here, the recording liquid is an ink containing a dye as a color material, the recording liquid is an ink containing a pigment as a color material, the recording liquid is an ink containing polymer particles containing pigment particles as a color material, and the recording liquid is benzo The ink may contain triazole.

  An apparatus for ejecting droplets according to the present invention includes the liquid ejection head according to the present invention.

  The recording method according to the present invention is configured to perform recording on a recording medium by discharging recording liquid droplets from the liquid discharge head according to the present invention.

Here, the recording medium may be a recording medium having a support and a coating layer on at least one surface of the support. Further, the amount of transferred onto the recording medium of the recording liquid at a contact time of 100ms measured by a dynamic scanning absorptometer at 23 ° C. 50% RH is 4~15ml / ^{m 2,} and the recording of the recording liquid at a contact time 400ms It can be set as the structure whose transfer amount to a medium is 7-20 ml / m < ² >. Alternatively, recording of pure water at a contact time of 100 ms measured at 23 ° C. and 50% RH with a contact time of 100 ms is 4 to 26 ml / m ² and pure water is recorded at a contact time of 400 ms. It can be set as the structure whose transfer amount to a medium is 5-29 ml / m < ² >.

The recording medium is composed of at least a base material and a coating layer, and the solid content of the coating layer is 0.5 to 20.0 g / m ^{2. The} recording medium has a basis weight. 50-250 g / m < ² >, the recording medium is supercalendered, the recording medium contains a pigment, the pigment is kaolin, the recording medium contains a pigment, and the pigment is heavy carbonic acid The structure may be calcium, the recording medium may contain an aqueous resin, or the aqueous resin may be a water-soluble resin or a water-dispersible resin.

  The recording liquid contains at least water, a colorant, and a wetting agent, the recording liquid has a surface tension of 15 to 40 mN / m at 25 ° C., and the recording liquid is a dispersible colorant as a colorant. The dispersion colorant has an average particle size of 0.01 to 0.16 μm, the recording liquid has a viscosity at 25 ° C. of 1 to 30 mPa · sec, and the recording liquid is a surfactant. And the surfactant is a fluorosurfactant.

  According to the liquid ejection head of the present invention, the flow path forming member that forms the flow path of the recording liquid is formed of a metal material containing nickel, and has a peak intensity on the nickel (200) plane measured by X-ray analysis. Since it has a configuration superior to the peak intensity on the nickel (111) surface, it is not affected by brittleness and heat shrinkage in the heat treatment process, and the bonding accuracy is improved or the dimensional accuracy is improved. A quality liquid discharge head can be obtained.

  According to the liquid discharge head of the present invention, the flow path forming member that forms the flow path of the recording liquid is formed of a metal material containing nickel and thallium. 200) plane strength is superior to the nickel (111) plane peak strength, and is not affected by brittleness and thermal shrinkage in the heat treatment process, thereby improving the bonding accuracy. Alternatively, the dimensional accuracy is improved and a high quality liquid discharge head can be obtained.

  According to the image forming apparatus of the present invention, since the liquid ejection head according to the present invention is provided, a high-quality image can be formed. According to the apparatus for ejecting liquid droplets according to the present invention, since the liquid ejection head according to the present invention is provided, an apparatus for ejecting liquid droplets having a high-quality liquid ejection head can be obtained.

  According to the recording method of the present invention, recording is performed by ejecting droplets from the liquid ejection head according to the present invention, so that a high-quality image can be recorded.

  Embodiments of the present invention will be described below with reference to the accompanying drawings. A first embodiment of a liquid discharge head according to the present invention will be described with reference to FIGS. 1 is an exploded perspective view of the head, FIG. 2 is a cross-sectional view of the head along the longitudinal direction of the liquid chamber, and FIG. 3 is a cross-sectional view of the head along the lateral direction of the liquid chamber.

  The liquid discharge head includes, for example, a flow path plate 1 formed of a single crystal silicon substrate, a nozzle plate 2 that is a nozzle forming member bonded to the upper surface of the flow path plate 1, and a lower surface of the flow path plate 1. A pressure liquid chamber 6 having a vibration plate 3, and a nozzle 4 for discharging droplets thereby communicates via a communication path 5, a fluid resistance portion 7, and communicates with the liquid chamber 6 via the fluid resistance portion 7. The communication portion 8 is formed, and a recording liquid (for example, ink) is supplied from a common liquid chamber 10 formed in a frame member 17 described later through a supply port 9 formed in the diaphragm 3 to the communication portion 8.

  In this liquid ejection head, the flow path plate 1, the nozzle plate 2, and the vibration plate 3 are all flow path forming members that form a flow path of ink that is a recording liquid.

  Then, on the outer side of the diaphragm 3 that forms the wall surface of the liquid chamber 6 (on the side opposite to the liquid chamber 6), via a connecting portion (not shown) formed on the diaphragm 3 corresponding to each pressurized liquid chamber 6. Thus, the upper end surface of the laminated piezoelectric element 12 as a driving element (actuator means, pressure generating means) is joined. Further, the lower end surface of the multilayer piezoelectric element 12 is joined to the base member 13.

  Here, the piezoelectric element 12 is formed by alternately laminating piezoelectric material layers 21 and internal electrodes 22a and 22b, and the internal electrodes 22a and 22b are respectively drawn out to the end faces and connected to the end face electrodes (external electrodes) 23a and 23b. Then, a voltage is applied to the end face electrodes 23a and 23b to cause displacement in the stacking direction.

  Then, in order to give a drive signal to the piezoelectric element 12, an FPC cable 15 is connected by solder bonding, ACF (anisotropic conductive film) bonding or wire bonding, and the FPC cable 15 is selectively connected to each piezoelectric element 12. A drive circuit (driver IC) (not shown) for applying a drive waveform is mounted.

  In the lateral direction of the liquid chamber (the direction in which the nozzles 4 are arranged), as shown in FIG. 3, a bi-pitch structure in which the piezoelectric elements 12 and the column portions 12A are alternately arranged can be used, or as shown in FIG. Thus, it can also be set as the normal pitch structure which does not provide the support | pillar part 12. FIG.

  This head is configured to pressurize the ink in the liquid chamber 6 by using the displacement in the d33 direction as the piezoelectric direction of the piezoelectric element 12, and the side in which the liquid droplet ejection direction is different from the recording liquid flow direction in the liquid chamber 6. The configuration is such that droplets are ejected by the shooter method. By adopting the side shooter system, the size of the piezoelectric element 12 becomes approximately the size of the head, and the miniaturization of the piezoelectric element 12 can be directly linked to the miniaturization of the head, and the head can be easily miniaturized.

  Further, a frame member 17 formed by injection molding with an epoxy resin or polyphenylene sulfite is joined to the outer peripheral side of the actuator portion composed of the piezoelectric element 12, the base member 13, the FPC 15, and the like. The frame member 17 is formed with the above-described common liquid chamber 10 and a supply port 19 for supplying recording liquid to the common liquid chamber 10 from the outside. And a recording liquid supply source such as a recording liquid cartridge.

  Here, the flow path plate 1 is formed by anisotropically etching a single crystal silicon substrate having a crystal plane orientation (110), for example, with an alkaline etching solution such as an aqueous potassium hydroxide solution (KOH), so Groove portions constituting the through hole, the fluid resistance portion 7, the communication portion 8 and the like serving as the pressurized fluid chamber 6 are formed. The pressurized liquid chambers 6 are separated from each other by a partition wall 6a.

  The nozzle plate 2 is formed from a nickel (Ni) metal plate, and is manufactured by an electroforming method (electroforming). In this nozzle plate 3, nozzles 4 having a diameter of 10 to 35 μm are formed corresponding to the respective pressure chambers 6, and bonded to the flow path plate 1 with an adhesive. The liquid droplet discharge side surface (surface in the discharge direction: discharge surface or surface opposite to the liquid chamber 6 side) of the nozzle plate 3 is subjected to water repellent treatment.

  The diaphragm 3 is formed from a nickel (Ni) metal plate, and is manufactured by an electroforming method (electroforming). The diaphragm 3 has a portion corresponding to the pressurized liquid chamber 6 as a thin portion for easy deformation, and a connecting portion (not shown) for joining to the piezoelectric element 12 is provided at the center.

  The piezoelectric element 12 is formed by dividing a laminated piezoelectric element member by joining a base member 13 and then performing groove processing with a dicing saw or the like. The column portion 12A when the bi-pitch structure shown in FIG. 3 is used is a piezoelectric element member formed by grooving, but only functions as a column because no drive voltage is applied.

  In the liquid ejection head configured as described above, for example, when driven by a punching method, a drive pulse voltage of 20 to 50 V is selectively applied to the plurality of piezoelectric elements 2 according to an image recorded from a control unit (not shown). By applying, the piezoelectric element 12 to which the pulse voltage is applied is displaced to deform the vibration plate 3 in the direction of the nozzle plate 2, and pressurize the liquid in the liquid chamber 6 by changing the volume (volume) of the liquid chamber 6. Thus, droplets are ejected from the nozzles 4 of the nozzle plate 2. As the liquid droplets are discharged, the pressure in the liquid chamber 6 decreases, and a slight negative pressure is generated in the liquid chamber 6 due to the inertia of the liquid flow at this time. Under this state, the application of voltage to the piezoelectric element 12 is turned off, so that the diaphragm 2 returns to the original position and the liquid chamber 6 has the original shape, so that further negative pressure is generated. At this time, the recording liquid is filled from the common liquid chamber 10 into the liquid chamber 6, and droplets are ejected from the nozzles 4 in response to the next drive pulse application.

  In addition to the above-described pushing, the liquid ejection head may be a pulling method (a method in which the diaphragm 3 is released from the pulled state and pressurized with a restoring force), a pull-pushing method (the diaphragm 3 is placed at an intermediate position). It is also possible to drive by pulling from this position and then extruding.

Therefore, details of the nozzle plate 2 and the diaphragm 3 which are one of the flow path forming members in the liquid discharge head will be described.
These nozzle plate 2 and diaphragm 3 are formed of a metal material containing nickel and thallium by electroforming. The content of thallium does not exceed 1% by mass of the Ni electroformed film, and particularly preferably does not exceed 0.1% by mass. As will be described later, thallium is necessary to make the peak intensity on the nickel (200) plane measured by X-ray analysis superior to the peak intensity on the nickel (111) plane. It is not preferable for producing gloss, and it is difficult to maintain the pH within a required range. Within this range, it becomes easy to balance with other materials used for the electroforming bath.

  The manufacture of the nozzle plate 2 by electroforming (electroforming) will be described with reference to FIG. 5. At least the surface of a conductive member, for example, an electroformed support substrate such as a silicon substrate having a Ti film formed on the surface A pattern 32 of an electrical insulating film such as a dry film resist (DRF) is formed on the surface 31, and an electrode such as Ni, Ni—Co, or Ni—Mn is formed on the surface of the conductive support substrate 31 by an electroforming bath. After casting and depositing and forming the electroformed film 33, the pattern 32 of the electrical insulating film is removed, and the electroformed film (electroformed film) 33 is peeled off from the electroformed support substrate 31 to perform electroforming. The coating 33 is used as the nozzle plate 2.

  Similarly, the diaphragm 3 is manufactured by electroforming, and an electroformed film repeatedly formed on the electroformed support substrate is used as the diaphragm.

As an electroforming bath used in such an electroforming method, a sulfamic acid bath is generally used, and a brightening agent (1, 3, 6) is used for the purpose of crystal refinement, electrocast film gloss, and stress reduction. -Sodium trinaphthalenesulfonate, saccharin), anodic solubilizer (Ni chloride, Ni bromide), pH buffer. Usually, the electroforming bath temperature is preferably about 50 ° C., and the current density is preferably 1 A / dm ^{2 to} 10 A / dm ² .

  The anodic solubilizer serves to remove, for example, an oxide film of Ni pellets used for the anode electrode. Since electroforming is generally preferably performed at a pH of 4 to 6, boric acid, formic acid or the like is used.

  For example, a Ni electrolyte containing 200 to 400 g / L of Ni sulfamate, 0 to 10 g / L of Ni chloride, and 30 g / L of boric acid can be used. Thereto, 1,3,6-trinaphthalene sodium sulfonate or saccharin is added so that the sulfur content of the Ni electroformed film is 0.1% by mass or less. At this time, in order to suppress sulfur brittleness, the sulfur content is preferably as close to zero as possible, and the sulfur content is preferably 0.01% by mass or less.

  Here, as described above, thallium is added to the Ni electroforming bath, but by adding cobalt and manganese in the form of cobalt sulfate or manganese sulfamate, the nozzle plate 2 and the diaphragm 3 are made of nickel and cobalt. Alternatively, it may be formed of a metal material containing nickel and manganese.

  In this case, the addition amount of cobalt or manganese should preferably not exceed 1% by mass of the Ni electroformed film, and more preferably 0.1% by mass of the Ni electroformed film.

  Appropriate amounts of cobalt and manganese are considered to suppress sulfur embrittlement during heat treatment, and it is thought that sulfur-manganese compounds and sulfur-cobalt compounds are formed. Therefore, a very high current density is required, and problems such as a decrease in toughness and an increase in heat shrinkage due to heat treatment may occur. Moreover, when there are few addition amounts of manganese and cobalt with respect to sulfur, it becomes impossible to suppress embrittlement.

  Compared to these cobalt and manganese, the standard electrode potential of thallium described above is relatively close to the standard electrode potential of Ni, so it can be deposited efficiently and can be used even at a low current density. it can.

  Here, an electroformed film containing thallium under the above conditions (Example 1) and an electroformed film not containing thallium (Comparative Examples 1 and 2) were manufactured. The X-ray diffraction intensity was measured using an analyzer. When the peak intensity on the nickel (111) plane measured by X-ray diffraction is I (111) and the peak intensity on the nickel (200) plane is I (200), the peak intensity on the nickel (111) plane is The intensity ratio of the crystal orientation plane expressed by the ratio of the peak intensity on the nickel (200) plane is expressed as I (200) / I (111). Moreover, about each of these electroformed films | membranes, the heat shrink amount at the time of heat-processing and Vickers hardness were also measured. These results are shown in Table 1.

  As can be seen from Table 1, in the electroformed film containing nickel and thallium, the peak intensity on the nickel (200) plane is more preferentially oriented than the peak intensity on the nickel (111) plane. In particular, the Ni electroformed film satisfying the condition that the strength ratio is I (200) / I (111) ≧ 3.0 is Vickers hardness (HV) after heat treatment at 350 ° C. for 1 hour. Hardly changes, and the amount of shrinkage after heat treatment (heat shrinkage amount) is 23 ppm compared to before heat treatment, so that it does not become brittle and heat shrinkage hardly occurs.

  On the other hand, in the Ni electroformed film containing no thallium (and cobalt and manganese), when the heat treatment is performed at 275 ° C. for 1 hour, the change in Vickers hardness exceeds 20% and the heat The amount of shrinkage also exceeds 200 ppm. Furthermore, when heat treatment is performed at 350 ° C. for 1 hour, the change in Vickers hardness exceeds 30% and the amount of thermal shrinkage also exceeds 400 ppm. For this reason, the Ni electroformed film becomes brittle and a flow path forming member with high dimensional accuracy cannot be obtained.

  Thus, the flow path forming member that forms the flow path of the recording liquid is formed of a metal material containing nickel, and the peak intensity at the nickel (200) plane measured by X-ray analysis is the peak at the nickel (111) plane. By adopting a configuration superior to strength, it is possible to suppress the embrittlement of sulfur, reduce the embrittlement and heat shrinkage caused by the heat treatment process, and increase the heat treatment process with other components. Precision bonding can be performed. Further, an oxidation protective film (ink-resistant liquid contact film, etc.) such as a thermal oxide film by heat treatment can be formed on the surface of the flow path constituent member in contact with the recording liquid without causing shrinkage or embrittlement of the flow path forming member. . Thereby, a liquid discharge head having excellent droplet discharge characteristics can be obtained. Further, since the decrease in Vickers hardness is small, there is little warpage (stress), and high-precision joining is possible in this respect as well.

  In addition, the flow path forming member that forms the flow path of the recording liquid is made of a metal material containing nickel and thallium, so that it is easily measured by X-ray analysis without increasing the current density. Since the flow path forming member in which the peak intensity on the nickel (200) surface is superior to the peak intensity on the nickel (111) surface can be formed, as described above, the droplet discharge characteristics are excellent and the accuracy is high. A good liquid discharge head can be obtained.

  And by applying this invention to a nozzle plate, there is little thermal contraction by heat processing and the precision of a nozzle diameter can be improved. Further, by applying the present invention to the diaphragm, there is little heat shrinkage due to heat treatment, and the accuracy of the diaphragm component can be improved. Furthermore, in the above embodiment, the example in which the present invention is applied to the nozzle plate and the vibration plate as the flow path forming member is described. However, the present invention can also be applied to the flow path plate, and heat shrinkage due to heat treatment is caused. A highly accurate flow path plate can be obtained without using an expensive member such as silicon.

  Further, by forming the flow path forming member by electroforming, for example, as shown in FIG. 6, the member 41 in which the nozzle plate and the flow path plate are integrally formed, or the vibration plate 53 and the flow path plate 52. Can be obtained, and the present invention can also be applied to such a member. With this configuration, the number of heat treatment steps for bonding is reduced, and the cost can be reduced.

  Next, an example of an image forming apparatus including the apparatus for ejecting liquid droplets according to the present invention provided with the liquid ejection head according to the present invention will be described with reference to FIGS. 8 is an explanatory side view for explaining the overall configuration of the image forming apparatus, and FIG. 9 is an explanatory plan view of a main part of the apparatus.

  In this image forming apparatus, a carriage 103 is slidably held in a main scanning direction by a guide rod 101 and a guide rail 102 that are horizontally mounted on left and right side plates (not shown), and a driving pulley 106A is driven by a main scanning motor 104. And the driven pulley 106B are moved and scanned in the direction indicated by the arrow (main scanning direction) via the timing belt 105.

  For example, four independent ink jet recording liquid droplets (ink droplets) of black (K), cyan (C), magenta (M), and yellow (Y) are recorded on the carriage 103. The recording head 107 composed of the liquid ejection heads 107k, 107c, 107m, and 107y is arranged in a direction along the main scanning direction, and is mounted with the droplet ejection direction facing downward. In addition, although the independent liquid discharge head is used here, it is also possible to employ a configuration in which one or a plurality of heads having a plurality of nozzle rows for discharging recording liquid droplets of each color are used. Further, the number of colors and the arrangement order are not limited to this.

  The carriage 103 is equipped with a sub tank 108 for each color for supplying each color ink to the recording head 107. Ink is supplied to the sub tank 108 from a main tank (ink cartridge) (not shown) via an ink supply tube 109.

  On the other hand, as a sheet feeding unit for feeding a recording medium (sheet) 112 loaded on a sheet stacking unit (pressure plate) 111 such as a sheet feeding cassette 110, the sheets 112 are separated and fed from the sheet stacking unit 111 one by one. Opposite to the half-moon roller (feed roller) 113 and the feed roller 113 to be fed, a separation pad 114 made of a material having a large friction coefficient is provided, and this separation pad 114 is urged toward the feed roller 113 side.

  As a transport unit for transporting the paper 112 fed from the paper feed unit below the recording head 107, a transport belt 121 for electrostatically attracting and transporting the paper 112, and a paper feed unit A counter roller 122 for transporting the paper 112 fed through the guide 115 while sandwiching it between the transport belt 121 and the paper 112 fed substantially vertically upward is changed by about 90 ° and copied on the transport belt 121. And a pressure roller 125 </ b> A and a tip pressure roller 125 </ b> B urged toward the conveyance belt 121 by the pressing member 124. In addition, a charging roller 126 that is a charging unit for charging the surface of the conveyance belt 121 is provided.

  Here, the conveyance belt 121 is an endless belt, is stretched between the conveyance roller 127 and the tension roller 128, and the conveyance roller 127 is rotated from the sub-scanning motor 131 via the timing belt 132 and the timing roller 133. By doing so, it is configured to go around in the belt conveyance direction (sub-scanning direction). A guide member 129 is disposed on the back side of the conveyance belt 121 in correspondence with the image forming area formed by the recording head 107.

  The charging roller 126 is arranged so as to contact the surface layer of the conveyor belt 121 and rotate following the rotation of the conveyor belt 121, and applies 2.5N to both ends of the shaft as a pressing force.

  Further, as a paper discharge unit for discharging the paper 112 recorded by the recording head 107, a separation unit for separating the paper 112 from the conveying belt 121, a paper discharge roller 152 and a paper discharge roller 153, and paper discharge A paper discharge tray 154 for stocking the paper 112 to be printed.

  A double-sided paper feeding unit 155 is detachably mounted on the back. The double-sided paper feeding unit 155 takes in the paper 112 returned by the reverse rotation of the transport belt 121, reverses it, and feeds it again between the counter roller 122 and the transport belt 121.

  Further, as shown in FIG. 14, a maintenance / recovery mechanism 156 for maintaining and recovering the state of the nozzles of the recording head 107 is disposed in a non-printing area on one side of the carriage 103 in the scanning direction.

  The maintenance / recovery machine 156 includes a cap 157 for capping each nozzle surface of the recording head 107, a wiper blade 158 which is a blade member for wiping the nozzle surface, and a discharge unit for discharging the thickened recording liquid. An empty discharge receiver 159 for receiving droplets when performing empty discharge for discharging droplets that do not contribute to recording is provided.

Next, ink as a recording liquid used in the recording method according to the present invention for recording on a recording medium (paper) by ejecting droplets from the liquid ejection head according to the present invention will be described.
The ink used in the recording method according to the present invention contains at least water, a colorant, and a wetting agent, and further contains a penetrating agent, a surfactant, and, if necessary, other components.

  Here, the ink has a surface tension at 25 ° C. of 15 to 40 mN / m, and more preferably 20 to 35 mN / m. When the surface tension is less than 15 / m, the liquid ejection head according to the present invention is too wet with the nozzle plate (nozzle plate) to form ink droplets (particle formation), or used in the recording method according to the present invention. Bleeding on the recording medium becomes significant, and stable ink ejection may not be obtained. If it exceeds 40 mN / m, ink penetration into the recording medium does not occur sufficiently and beading or drying occurs. The time may be prolonged.

  The surface tension can be measured at 25 ° C. using a platinum plate using, for example, a surface tension measuring device (CBVP-Z, manufactured by Kyowa Interface Science Co., Ltd.).

As the ink color material, any of pigments and dyes can be used, or they can be used in combination. In the case of using a pigment, it is relatively easy to form a high-quality image having excellent weather resistance and water resistance with respect to plain paper as compared with a dye.

[Pigment]
As the pigment, those listed below are preferably used. Moreover, you may use these pigments in mixture of multiple types.

  Examples of organic pigments include azo, phthalocyanine, anthraquinone, quinacridone, dioxazine, indigo, thioindigo, perylene, isoindolenone, aniline black, azomethine, rhodamine B lake pigment, and carbon black. It is done.

  Examples of inorganic pigments include iron oxide, titanium oxide, calcium carbonate, barium sulfate, aluminum hydroxide, barium yellow, bitumen, cadmium red, chrome yellow, and metal powder.

  The particle diameter of these pigments is preferably 0.01 to 0.30 [mu] m. If the particle diameter is 0.01 [mu] m or less, the light resistance and feathering are deteriorated because the particle diameter approaches that of the dye. On the other hand, if it is 0.30 μm or more, clogging of the discharge port or clogging with a filter in the printer occurs, and the discharge stability cannot be obtained. It is more preferable from a viewpoint of clogging and discharge stability that it is 0.01-0.16 micrometer.

  The carbon black used in the black pigment ink is carbon black produced by the furnace method and the channel method, the primary particle size is 15 to 40 millimicrons, the specific surface area by the BET method is 50 to 300 square meters / g, The DBP oil absorption is preferably 40 to 150 ml / 100 g, the volatile content is 0.5 to 10%, and the pH value is 2 to 9. As such a thing, for example, no. 2300, no. 900, MCF-88, no. 33, no. 40, no. 45, no. 52, MA7, MA8, MA100, no. 2200B (Mitsubishi Chemical Corporation), Raven700, 5750, 5250, 5000, 3500, 1255 (Columbia), Regal400R, 330R, 660R, MoguL, Monarch700, 800, 880, 900, 1000, 1100, 1300, Monarch 1400 (manufactured by Cabot), color black FW1, FW2, FW2V, FW18, FW200, S150, S160, S170, Printex 35, U, the same V, the same 140U, the same 140V, the special black 6, the same 5, the same 4A, the same 4 (manufactured by Degussa) and the like can be used, but are not limited thereto.

Specific examples of color pigments are listed below.
Examples of organic pigments include azo, phthalocyanine, anthraquinone, quinacridone, dioxazine, indigo, thioindigo, perylene, isoindolenone, aniline black, azomethine, rhodamine B lake pigment, and carbon black. Examples of inorganic pigments include iron oxide, titanium oxide, calcium carbonate, barium sulfate, aluminum hydroxide, barium yellow, bitumen, cadmium red, chrome yellow, and metal powder.

Specific examples according to color are as follows.
Examples of pigments that can be used for yellow ink include C.I. I. Pigment Yellow 1, 2, 2, 3, 12, 14, 16, 17, 17, 73, 74, 75, 83, 93, 95, 97, 98, 114, 128, 129, 151, 154, etc., but are not limited thereto.

  Examples of pigments that can be used in magenta ink include C.I. I. Pigment Red 5, 7, 12, 48 (Ca), 48 (Mn), 57 (Ca), 57: 1, 112, 123, 168, 184, 202, etc. However, it is not limited to these.

  Examples of pigments that can be used for cyan ink include C.I. I. Pigment blue 1, 2, 3, 15: 3, 15:34, 16, 22, 22, 60, C.I. I. Examples thereof include, but are not limited to, Bat Blue 4 and 60.

  In addition, the pigment contained in each ink used in the present invention may be newly produced for the present invention.

  The pigments listed above can be made into an inkjet recording liquid by dispersing them in an aqueous medium using a polymer dispersant or a surfactant. As a dispersant for dispersing such organic pigment powder, a normal water-soluble resin or a water-soluble surfactant can be used.

  Specific examples of water-soluble resins include styrene, styrene derivatives, vinyl naphthalene derivatives, aliphatic alcohol esters of α, β-ethylenically unsaturated carboxylic acids, acrylic acid, acrylic acid derivatives, maleic acid, maleic acid derivatives, itacon. Examples thereof include block copolymers consisting of at least two monomers selected from acids, itaconic acid derivatives, fumaric acid, fumaric acid derivatives, etc., random copolymers, or salts thereof.

  These water-soluble resins are alkali-soluble resins that are soluble in an aqueous solution in which a base is dissolved. Among them, a resin having a weight average molecular weight of 3000 to 20000 is used as a dispersion when used in an inkjet recording liquid. It is particularly preferred because of the advantages that it can be reduced in viscosity and can be easily dispersed.

The simultaneous use of the polymer dispersant and the self-dispersing pigment is a preferable combination because an appropriate dot diameter can be obtained. The reason is not clear, but it is thought as follows.
By containing the polymer dispersant, the penetration into the recording paper is suppressed. On the other hand, since the aggregation of the self-dispersing pigment is suppressed by containing the polymer dispersant, the self-dispersing pigment can smoothly spread in the lateral direction. Therefore, it is considered that the dots spread widely and thinly and ideal dots can be formed.

  Moreover, the following are mentioned as a specific example of the water-soluble surfactant which can be used as a dispersing agent. For example, anionic surfactants include higher fatty acid salts, alkyl sulfates, alkyl ether sulfates, alkyl ester sulfates, alkyl aryl ether sulfates, alkyl sulfonates, sulfosuccinates, alkyl allyls and alkyl naphthalene sulfonic acids. Examples thereof include salts, alkyl phosphates, polyoxyethylene alkyl ether phosphate esters, and alkyl allyl ether phosphates. Examples of the cationic surfactant include alkylamine salts, dialkylamine salts, tetraalkylammonium salts, benzalkonium salts, alkylpyridinium salts, imidazolinium salts, and the like.

  Furthermore, examples of the amphoteric surfactant include dimethylalkyl lauryl betaine, alkyl glycine, alkyl di (aminoethyl) glycine, imidazolinium betaine and the like. Nonionic surfactants include polyoxyethylene alkyl ether, polyoxyethylene alkyl allyl ether, polyoxyethylene polyoxypropylene glycol, glycerin ester, sorbitan ester, sucrose ester, glycerin ester polyoxyethylene ether, sorbitan Examples thereof include polyoxyethylene ethers of esters, polyoxyethylene ethers of sorbitol esters, fatty acid alkanolamides, polyoxyethylene fatty acid amides, amine oxides, and polyoxyethylene alkylamines.

  Further, the pigment can be provided with dispersibility by coating with a resin having a hydrophilic group and encapsulating the pigment.

  As a method for coating a water-insoluble pigment with an organic polymer and microencapsulating, all conventionally known methods can be used. Conventionally known methods include chemical production methods, physical production methods, physicochemical methods, mechanical production methods, and the like. Specifically, interfacial polymerization method, in-situ polymerization method, submerged cured coating method, coacervation (phase separation) method, submerged drying method, melt dispersion cooling method, air suspension coating method, spray drying method , Acid precipitation method, phase inversion emulsification method and the like.

  The interfacial polymerization method is a method in which two types of monomers or two types of reactants are separately dissolved in a dispersed phase and a continuous phase, and both substances are reacted at the interface between the two to form a wall film. The in-situ polymerization method is a method in which a liquid or gas monomer and catalyst, or two reactive substances are supplied from either one of the continuous phase core particles to cause a reaction to form a wall film. The in-liquid cured coating method is a method of forming a wall film by insolubilizing droplets of a polymer solution containing core material particles in a liquid with a curing agent or the like.

  The coacervation (phase separation) method is a method in which a polymer dispersion in which core material particles are dispersed is separated into a coacervate (concentrated phase) and a dilute phase having a high polymer concentration to form a wall film. . In the liquid drying method, a liquid in which a core material is dispersed in a wall membrane material solution is prepared, and the dispersion is put into a liquid in which the continuous phase of this dispersion liquid is not miscible to form a composite emulsion to dissolve the wall membrane material. In this method, the wall film is formed by gradually removing the medium.

  The melt dispersion cooling method uses a wall film material that melts into a liquid state when heated and solidifies at room temperature. This material is heated and liquefied, and the core material particles are dispersed in it and cooled to fine particles. This is a method of forming a wall film. The suspension-in-air coating method is a method of forming a wall membrane by suspending powder core material particles in the air with a fluidized bed and suspending them in an air stream while spraying and mixing the coating solution of the wall membrane material. It is.

  The spray drying method is a method in which an encapsulated stock solution is sprayed and brought into contact with hot air to evaporate and dry volatile components to form a wall film. The acid precipitation method means that at least a part of the anionic group of the organic polymer compound containing an anionic group is neutralized with a basic compound to give water solubility and kneading in an aqueous medium together with a coloring material. After that, neutralization or acidification with an acidic compound is performed, and organic compounds are precipitated and fixed to a coloring material, and then neutralized and dispersed. The phase inversion emulsification method refers to a mixture containing an anionic organic polymer having dispersibility in water and a coloring material as an organic solvent phase, and water is added to the organic solvent phase or This is a method of charging the organic solvent phase.

  Examples of organic polymers (resins) used as the material constituting the microcapsule wall membrane material include polyamide, polyurethane, polyester, polyurea, epoxy resin, polycarbonate, urea resin, melamine resin, phenol resin, and polysaccharide. , Gelatin, gum arabic, dextran, casein, protein, natural rubber, carboxypolymethylene, polyvinyl alcohol, polyvinylpyrrolidone, polyvinyl acetate, polyvinyl chloride, polyvinylidene chloride, cellulose, ethyl cellulose, methyl cellulose, nitrocellulose, hydroxyethyl cellulose, acetic acid Cellulose, polyethylene, polystyrene, (meth) acrylic acid polymer or copolymer, (meth) acrylic acid ester polymer or copolymer, (meth) acrylic acid (Meth) acrylic acid ester copolymer, styrene- (meth) acrylic acid copolymer, styrene-maleic acid copolymer, sodium alginate, fatty acid, paraffin, beeswax, water wax, hardened beef tallow, carnauba wax, albumin, etc. .

  Among these, organic polymers having an anionic group such as a carboxylic acid group or a sulfonic acid group can be used. Nonionic organic polymers include, for example, polyvinyl alcohol, polyethylene glycol monomethacrylate, polypropylene glycol monomethacrylate, methoxypolyethylene glycol monomethacrylate or their (co) polymers, and 2-oxazoline cationic ring-opening polymers. Is mentioned. In particular, a complete saponified product of polyvinyl alcohol is particularly preferable because it has low water solubility and is easily dissolved in hot water but difficult to dissolve in cold water.

  Further, the amount of the organic polymer constituting the wall membrane material of the microcapsule is 1% by weight or more and 20% by weight or less based on the water-insoluble colorant such as an organic pigment or carbon black. By setting the amount of the organic polymer within the above range, the content of the organic polymer in the capsule is relatively low so that the pigment develops due to the organic polymer covering the pigment surface. Can be suppressed. If the amount of the organic polymer is less than 1% by weight, it is difficult to exert the effect of encapsulation. Conversely, if the amount exceeds 20% by weight, the color developability of the pigment is significantly reduced. In consideration of other characteristics, the amount of the organic polymer is preferably in the range of 5 to 10% by weight based on the water-insoluble colorant.

  That is, since a part of the color material is exposed without being substantially covered, it is possible to suppress a decrease in color developability, and conversely, a part of the color material is not substantially exposed without being exposed. Since it is coated, it is possible to simultaneously exhibit the effect that the pigment is coated. The number average molecular weight of the organic polymers is preferably 2000 or more from the viewpoint of capsule production. Here, “substantially exposed” means not the partial exposure associated with defects such as pinholes and cracks, but a state where it is intentionally exposed.

  Furthermore, if an organic pigment or self-dispersing carbon black, which is a self-dispersing pigment, is used as a colorant, the dispersibility of the pigment is improved even if the content of the organic polymer in the capsule is relatively low. In addition, since sufficient storage stability of the ink can be secured, it is more preferable for the present invention.

  It is preferable to select an organic polymer suitable for the microencapsulation method. For example, in the case of interfacial polymerization, polyester, polyamide, polyurethane, polyvinyl pyrrolidone, epoxy resin and the like are suitable. In the case of using the in-situ polymerization method, a polymer or copolymer of (meth) acrylic acid ester, (meth) acrylic acid- (meth) acrylic acid ester copolymer, styrene- (meth) acrylic acid copolymer, Polyvinyl chloride, polyvinylidene chloride, polyamide and the like are suitable. In the case of the liquid curing method, sodium alginate, polyvinyl alcohol, gelatin, albumin, epoxy resin and the like are suitable. In the case of the coacervation method, gelatin, celluloses, casein and the like are suitable. In addition, in order to obtain a fine and uniform microencapsulated pigment, it is possible to use all conventionally known encapsulation methods other than those described above.

  When the phase inversion method or the acid precipitation method is selected as the microencapsulation method, anionic organic polymers are used as the organic polymers constituting the wall membrane material of the microcapsules. The phase inversion method is a composite or composite of an anionic organic polymer having self-dispersibility or solubility in water and a colorant such as a self-dispersion organic pigment or self-dispersion carbon black, or a self-dispersion method. A mixture of a colorant such as a dispersible organic pigment or self-dispersing carbon black, a curing agent, and an anionic organic polymer is used as an organic solvent phase, and water is added to the organic solvent phase, or the organic solvent is submerged in water. In this method, a solvent phase is introduced and microencapsulation is performed while self-dispersion (phase inversion emulsification) is performed. In the above phase inversion method, there is no problem even if the organic solvent phase is mixed with a recording liquid vehicle or additives. In particular, it is more preferable to mix a liquid medium of a recording liquid because a dispersion liquid for recording liquid can be directly produced.

  On the other hand, in the acid precipitation method, a part or all of the anionic group of the anionic group-containing organic polymer is neutralized with a basic compound, and a colorant such as a self-dispersing organic pigment or self-dispersing carbon black, A water-containing cake obtained by a production method comprising a step of kneading in an aqueous medium and a step of neutralizing and acidifying an acidic compound to precipitate an anionic group-containing organic polymer and fixing it to a pigment, This is a method of microencapsulation by neutralizing a part or all of an anionic group using a compound. By doing in this way, the aqueous dispersion containing the anionic microencapsulated pigment which is fine and contains many pigments can be manufactured.

  Examples of the solvent used for microencapsulation as described above include alkyl alcohols such as methanol, ethanol, propanol and butanol; aromatic hydrocarbons such as benzol, toluol and xylol; methyl acetate Esters such as ethyl acetate and butyl acetate; Chlorinated hydrocarbons such as chloroform and ethylene dichloride; Ketones such as acetone and methyl isobutyl ketone; Ethers such as tetrahydrofuran and dioxane; Cellosolves such as methyl cellosolve and butyl cellosolve Etc. The microcapsules prepared by the above method are once separated from these solvents by centrifugation or filtration, and then stirred and redispersed with water and the necessary solvent, and used for the intended present invention. A recording liquid that can be used is obtained. The average particle diameter of the encapsulated pigment obtained by the above method is preferably 50 nm to 180 nm.

  By coating the resin in this way, the pigment adheres firmly to the printed material, whereby the scratching property of the printed material can be improved.

〔dye〕
As the dye used in the recording liquid, dyes classified into acid dyes, direct dyes, basic dyes, reactive dyes, and food dyes in the color index and having excellent water resistance and light resistance are used. These dyes may be used as a mixture of a plurality of types, or may be used as a mixture with other color materials such as pigments as necessary. These colorants are added within a range that does not impair the effects of the present invention.

(A) As an acid dye and a food dye,
C. I. Acid Yellow 17, 23, 42, 44, 79, 142
C. I. Acid Red 1,8,13,14,18,26,27,35,37,42,52,82,87,89,92,97,106,111,114,115,134,186,249,254 289
C. I. Acid Blue 9, 29, 45, 92, 249
C. I. Acid Black 1, 2, 7, 24, 26, 94
C. I. Food Yellow 3, 4
C. I. Food Red 7, 9, 14
C. I. Food Black 1, 2

(B) As a direct dye,
C. I. Direct yellow 1,12,24,26,33,44,50,86,120,132,142,144
C. I. Direct Red 1,4,9,13,17,20,28,31,39,80,81,83,89,225,227
C. I. Direct orange 26, 29, 62, 102
C. I. Direct blue 1,2,6,15,22,25,71,76,79,86,87,90,98,163,165,199,202
C. I. Direct black 19, 22, 32, 38, 51, 56, 71, 74, 75, 77, 154, 168, 171

(C) As a basic dye,
C. I. Basic yellow 1, 2, 11, 13, 14, 15, 19, 21, 23, 24, 25, 28, 29, 32, 36, 40, 41, 45, 49, 51, 53, 63, 64, 65 67, 70, 73, 77, 87, 91
C. I. Basic Red 2,12,13,14,15,18,22,23,24,27,29,35,36,38,39,46,49,51,52,54,59,68,69,70 73, 78, 82, 102, 104, 109, 112
C. I. Basic blue 1,3,5,7,9,21,22,26,35,41,45,47,54,62,65,66,67,69,75,77,78,89,92,93 , 105, 117, 120, 122, 124, 129, 137, 141, 147, 155
C. I. Basic Black 2,8

(D) As a reactive dye,
C. I. Reactive Black 3, 4, 7, 11, 12, 17
C. I. Reactive Yellow 1,5,11,13,14,20,21,22,25,40,47,51,55,65,67
C. I. Reactive Red 1,14,17,25,26,32,37,44,46,55,60,66,74,79,96,97
C. I. Reactive Blue 1, 2, 7, 14, 15, 23, 32, 35, 38, 41, 63, 80, 95, etc. can be used.

[Additives and physical properties common to dyes and pigments]
In order to make the recording liquid used in the image forming apparatus according to the present invention have the desired physical properties or to prevent clogging of the nozzles of the recording head due to drying, a water-soluble organic solvent is used in addition to the colorant. It is preferable to do. The water-soluble organic solvent includes a wetting agent and a penetrating agent. The wetting agent is added for the purpose of preventing clogging of the nozzles of the recording head due to drying.

  Specific examples of the wetting agent include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, propylene glycol, 1,3-butanediol, 1,3-propanediol, and 2-methyl-1,3-propane. Diol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, glycerin, 1,2,6-hexanetriol, 2-ethyl-1,3-hexanediol, 1,2 Polyhydric alcohols such as 1,4-butanetriol, 1,2,3-butanetriol, and petriol, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene Polyhydric alcohol alkyl ethers such as glycol monobutyl ether, triethylene glycol monobutyl ether, tetraethylene glycol monomethyl ether and propylene glycol monoethyl ether, polyhydric alcohol aryl ethers such as ethylene glycol monophenyl ether and ethylene glycol monobenzyl ether Forehead: Nitrogen-containing heterocyclic compounds such as N-methyl-2-pyrrolidone, N-hydroxyethyl-2-pyrrolidone, 2-pyrrolidone, 1,3-dimethylimidazolidinone, ε-caprolactam; formamide, N-methylformamide, Amides such as formamide and N, N-dimethylformamide; monoethanolamine, diethanolamine, triethanolamine, monoethylamine, diethylamine, triethyl And amines such as ruamine, sulfur-containing compounds such as dimethyl sulfoxide, sulfolane and thiodiethanol, propylene carbonate, ethylene carbonate, and γ-butyrolactone. These solvents are used alone or in combination with water.

  Further, the penetrant is added for the purpose of improving the wettability between the recording liquid and the recording material and adjusting the penetration speed. As the penetrant, those represented by the following formulas (I) to (IV) are preferable. That is, a polyoxyethylene alkylphenyl ether surfactant of formula (I) below, an acetylene glycol surfactant of formula (II), a polyoxyethylene alkyl ether surfactant of formula (III) below and formula (IV) The polyoxyethylene polyoxypropylene alkyl ether-based surfactant (1) can reduce the surface tension of the liquid, so that the wettability can be improved and the penetration rate can be increased.

（Ｒは分岐していても良い炭素数６〜１４の炭化水素鎖、ｋは５〜２０）

(R is an optionally branched hydrocarbon chain having 6 to 14 carbon atoms, k is 5 to 20)

（ｍ、ｎは０〜４０）

(M and n are 0 to 40)

（Ｒは分岐していても良い炭素数６〜１４の炭化水素鎖、ｎは５〜２０）

(R is an optionally branched hydrocarbon chain having 6 to 14 carbon atoms, n is 5 to 20)

（Ｒは炭素数６〜１４の炭化水素鎖、ｍ、ｎは２０以下の数）

(R is a hydrocarbon chain having 6 to 14 carbon atoms, m and n are numbers of 20 or less)

Other than the compounds of the above formulas (I) to (IV), for example, diethylene glycol monophenyl ether, ethylene glycol monophenyl ether, ethylene glycol monoallyl ether, diethylene glycol monophenyl ether, diethylene glycol monobutyl ether, propylene glycol monobutyl ether, tetraethylene glycol chlorophenyl Use alkyl and aryl ethers of polyhydric alcohols such as ethers, nonionic surfactants such as polyoxyethylene polyoxypropylene block copolymers, fluorine-based surfactants, lower alcohols such as ethanol and 2-propanol However, diethylene glycol monobutyl ether is particularly preferable.

  However, the surfactant is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include anionic surfactants, nonionic surfactants, amphoteric surfactants, and fluorosurfactants. Can be mentioned.

  Examples of the anionic surfactant include polyoxyethylene alkyl ether acetate, dodecylbenzene sulfonate, laurate, polyoxyethylene alkyl ether sulfate salt, and the like.

  Examples of nonionic surfactants include acetylene glycol surfactants, polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyoxyethylene alkyl esters, polyoxyethylene sorbitan fatty acid esters, and the like.

  Examples of the acetylene glycol surfactant include 2,4,7,9-tetramethyl-5-decyne-4,7-diol, 3,6-dimethyl-4-octyne-3,6-diol, 3, 5-dimethyl-1-hexyn-3-ol and the like. Examples of commercially available acetylene glycol surfactants include Surfynol 104, 82, 465, 485, and TG manufactured by Air Products (USA).

  Examples of amphoteric surfactants include lauryl aminopropionate, lauryl dimethyl betaine, stearyl dimethyl betaine, and lauryl dihydroxyethyl betaine. Specific examples include lauryl dimethylamine oxide, myristyl dimethylamine oxide, stearyl dimethylamine oxide, dihydroxyethyl lauryl amine oxide, polyoxyethylene coconut oil alkyl dimethyl amine oxide, dimethyl alkyl (coconut) betaine, dimethyl lauryl betaine, and the like. It is done.

  Among these surfactants, surfactants represented by the following general formulas (V), (VI), (VII), (VIII), (IX), and (X) are preferable.

ただし、前記一般式（Ｖ）中、Ｒ１は、アルキル基を表し、炭素数６〜１４の分岐していてもよいアルキル基を表す。ｈは、３〜１２の整数を表す。Ｍは、アルカリ金属イオン、第４級アンモニウム、第４級ホスホニウム、及びアルカノールアミンから選択されるいずれかを表す。

However, in the said general formula (V), R1 represents an alkyl group and represents the C6-C14 alkyl group which may be branched. h represents an integer of 3 to 12. M represents one selected from alkali metal ions, quaternary ammonium, quaternary phosphonium, and alkanolamine.

ただし、前記一般式（ＶＩ）中、Ｒ２は、アルキル基を表し、炭素数５〜１６の分岐していてもよいアルキル基を表す。Ｍは、アルカリ金属イオン、第４級アンモニウム、第４級ホスホニウム、及びアルカノールアミンから選択されるいずれかを表す。

However, in said general formula (VI), R2 represents an alkyl group and represents the C5-C16 alkyl group which may be branched. M represents one selected from alkali metal ions, quaternary ammonium, quaternary phosphonium, and alkanolamine.

ただし、上記一般式（ＶＩＩ）中、Ｒ３は、炭化水素基を表し、例えば、分岐していてもよい炭素数６〜１４のアルキル基を表す。ｋは５〜２０の整数を表す。

However, in said general formula (VII), R3 represents a hydrocarbon group, for example, the C6-C14 alkyl group which may be branched. k represents an integer of 5 to 20.

ただし、上記一般式（ＶＩＩＩ）中、Ｒ４は、炭化水素基を表し、例えば、炭素数６〜１４のアルキル基を表す。ｊは、５〜２０の整数を表す。

However, in said general formula (VIII), R4 represents a hydrocarbon group, for example, a C6-C14 alkyl group. j represents an integer of 5 to 20.

ただし、上記一般式（ＩＸ）中、Ｒ^６は、炭化水素基を表し、例えば、炭素数６〜１４の分岐していてもよいアルキル基を表す。Ｌ及びｐは、１〜２０の整数を表す。

However, in the general formula (IX), R ⁶ represents a hydrocarbon group, for example, represents an alkyl group which may be branched having 6 to 14 carbon atoms. L and p represent an integer of 1 to 20.

ただし、上記一般式（Ｘ）中、ｑ及びｒは０〜４０の整数を表す。

However, q and r represent the integer of 0-40 in the said general formula (X).

  Hereinafter, the surfactants of the structural formulas (V) and (VI) are specifically shown in free acid form. First, examples of the surfactant (V) include those represented by the following (V-1) to (V-6).

  Next, examples of the surfactant (VI) include those represented by the following (VI-1) to (VI-4).

  As the fluorosurfactant, those represented by the following general formula (A) are suitable.

ただし、前記一般式（Ａ）中、ｍは、０〜１０の整数を表す。ｎは、１〜４０の整数を表す。

However, in said general formula (A), m represents the integer of 0-10. n represents an integer of 1 to 40.

  Examples of the fluorine-based surfactant include a perfluoroalkyl sulfonic acid compound, a perfluoroalkyl carboxylic compound, a perfluoroalkyl phosphate compound, a perfluoroalkyl ethylene oxide adduct, and a perfluoroalkyl ether group in the side chain. And polyoxyalkylene ether polymer compounds. Among these, the polyoxyalkylene ether polymer compound having a perfluoroalkyl ether group in the side chain has a low foaming property, and the bioaccumulation property of a fluorine compound that has been regarded as a problem in recent years is low and highly safe. Particularly preferred.

  Here, examples of the perfluoroalkyl sulfonic acid compound include perfluoroalkyl sulfonic acid, perfluoroalkyl sulfonate, and the like.

  Moreover, as a perfluoroalkyl carboxylic compound, perfluoroalkyl carboxylic acid, perfluoroalkyl carboxylate, etc. are mentioned, for example.

Examples of the perfluoroalkyl phosphate compound include perfluoroalkyl phosphate esters, perfluoroalkyl phosphate salts, and the like.
The polyoxyalkylene ether polymer compound having a perfluoroalkyl ether group in the side chain includes a polyoxyalkylene ether polymer having a perfluoroalkyl ether group in the side chain, and a polyoxyalkylene having a perfluoroalkyl ether group in the side chain. Examples thereof include sulfuric acid ester salts of ether polymers and salts of polyoxyalkylene ether polymers having a perfluoroalkyl ether group in the side chain.

Counter ions of salts in these fluorinated _{surfactants, Li, Na, K, NH4} , NH 3 CH 2 CH 2 OH, NH 2 (CH 2 CH 2 OH) 2, NH (CH 2 CH 2 OH) 3 Etc.

As a fluorine-type surfactant, what was synthesize | combined suitably may be used and a commercial item may be used.
Examples of commercially available products include Surflon S-111, S-112, S-113, S-121, S-131, S-132, S-141, and S-145 (all manufactured by Asahi Glass Co., Ltd.), Fullrad FC- 93, FC-95, FC-98, FC-129, FC-135, FC-170C, FC-430, FC-431 (all manufactured by Sumitomo 3M), MegaFuck F-470, F1405, F-474 ( All manufactured by Dainippon Ink and Chemicals), Zonyl TBS, FSP, FSA, FSN-100, FSN, FSO-100, FSO, FS-300, UR (all manufactured by DuPont), FT-110, FT-250 FT-251, FT-400S, FT-150, FT-400SW (all manufactured by Neos Co., Ltd.), PF-151N (manufactured by Omninova), and the like. It is done. Among these, Zonyl FS-300, FSN, FSN-100, and FSO (manufactured by DuPont) are particularly preferable from the viewpoints of reliability and color development improvement.

  The other components are not particularly limited and may be appropriately selected as necessary. For example, resin emulsion, pH adjuster, antiseptic / antifungal agent, rust inhibitor, antioxidant, ultraviolet absorber, oxygen absorber Agents, light stabilizers, and the like.

  The resin emulsion is obtained by dispersing resin fine particles in water as a continuous phase, and may contain a dispersant such as a surfactant as necessary.

  The content of resin fine particles as a dispersed phase component (content of resin fine particles in the resin emulsion) is generally preferably 10 to 70% by mass. Further, the particle diameter of the resin fine particles is preferably 10 to 1000 nm, more preferably 20 to 300 nm, particularly considering use in an ink jet recording apparatus.

  The resin fine particle component of the dispersed phase is not particularly limited and can be appropriately selected depending on the purpose. For example, acrylic resin, vinyl acetate resin, styrene resin, butadiene resin, styrene-butadiene resin, Examples include vinyl chloride resins, acrylic styrene resins, acrylic silicone resins, and among these, acrylic silicone resins are particularly preferable.

As a resin emulsion, what was synthesize | combined suitably may be used and a commercial item may be used.
Commercially available resin emulsions include, for example, Microgel E-1002, E-5002 (styrene-acrylic resin emulsion, manufactured by Nippon Paint Co., Ltd.), Boncoat 4001 (acrylic resin emulsion, manufactured by Dainippon Ink & Chemicals, Inc.) Boncoat 5454 (styrene-acrylic resin emulsion, manufactured by Dainippon Ink & Chemicals, Inc.), SAE-1014 (styrene-acrylic resin emulsion, manufactured by Nippon Zeon Co., Ltd.), Cybinol SK-200 (acrylic resin emulsion, Seiden) Chemical Co., Ltd.), Primal AC-22, AC-61 (acrylic resin emulsion, manufactured by Rohm and Haas), Nanoacryl SBCX-2821, 3689 (acrylic silicone resin emulsion, Toyo Ink Manufacturing Co., Ltd.) Company Ltd.), # 3070 (methyl methacrylate polymer resin emulsion, manufactured by Mikuni Color Ltd.).

  The addition amount of the resin fine particle component in the resin emulsion in the ink is preferably 0.1 to 50% by mass, more preferably 0.5 to 20% by mass, and still more preferably 1 to 10% by mass. If the addition amount is less than 0.1% by mass, the effect of improving clogging resistance and ejection stability may not be sufficient, and if it exceeds 50% by mass, the storage stability of the ink may be reduced. There is.

  The surface tension of the recording liquid used in the image forming apparatus according to the present invention is preferably 10 to 60 N / m, and 15 to 40 N from the viewpoint of achieving both wettability with the recording medium and droplet formation. More preferably, it is / m.

  Similarly, the viscosity of the recording liquid is preferably in the range of 1.0 to 30 mPa · s, and from the viewpoint of ejection stability, it is preferably in the range of 5.0 to 10 mPa · s.

  The pH of the recording liquid is preferably in the range of 3 to 11, and more preferably in the range of 6 to 10 from the viewpoint of preventing corrosion of the metal member in contact with the liquid.

  Further, by containing an antiseptic / antifungal agent in the recording liquid, it is possible to suppress the growth of bacteria and to improve the storage stability and the image quality stability. As antiseptic / antifungal agents, benzotriazole, sodium dehydroacetate, sodium sorbate, sodium 2-pyridinethiol-1-oxide, isothiazoline compounds, sodium benzoate, sodium pentachlorophenol, and the like can be used.

  Further, by containing a rust preventive agent in the recording liquid, a film can be formed on the metal surface in contact with the head or the like to prevent corrosion. As the rust inhibitor, for example, acidic sulfite, sodium thiosulfate, ammonium thiodiglycolate, diisopropylammonium nitrite, pentaerythritol tetranitrate, dicyclohexylammonium nitrite and the like can be used.

  Further, by containing an antioxidant in the recording liquid, even when radical species that cause corrosion are generated, the antioxidant can be prevented by eliminating the radical species, thereby preventing corrosion.

  Typical examples of the antioxidant include phenolic compounds and amine compounds. Examples of the phenolic compounds include hydroquinone and gallate compounds, 2,6-di-tert-butyl-p-cresol, and stearyl. -Β- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 2,2'-methylenebis (4-methyl-6-tert-butylphenol), 2,2'-methylenebis (4-ethyl- 6-tert-butylphenol), 4,4′-thiobis (3-methyl-6-tert-butylphenol), 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-4-hydroxybenzyl) benzene, Hindered materials such as lith (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, tetrakis [methylene-3 (3 ′, 5′-di-tert-butyl-4-hydroxyphenyl) propionate] methane Phenol compounds are exemplified, and amine compounds include N, N′-diphenyl-p-phenylenediamine, phenyl-β-naphthylamine, phenyl-α-naphthylamine, N, N′-β-naphthyl-p-phenylene. Examples include diamine, N, N′-diphenylethylenediamine, phenothiazine, N, N′-di-sec-butyl-p-phenylenediamine, 4,4′-tetramethyl-diaminodiphenylmethane, and the like. Further, as the latter, sulfur compounds and phosphorus compounds are representative, but as sulfur compounds, dilauryl thiodipropionate, distearyl thiodipropionate, lauryl stearyl thiodipropionate, dithiol. Examples include myristyl thiodipropionate, distearyl β, β′-thiodibutyrate, 2-mercaptobenzimidazole, dilauryl sulfide and the like, and phosphorus compounds include triphenyl phosphite, trioctadecyl phosphite, tridecyl. Examples include phosphite, trilauryl trithiophosphite, diphenylisodecyl phosphite, trinonylphenyl phosphite, distearyl pentaerythritol phosphite.

  Examples of the pH adjuster contained in the recording liquid include hydroxides of alkali metal elements such as lithium hydroxide, sodium hydroxide, and potassium hydroxide, ammonium hydroxide, quaternary ammonium hydroxide, and quaternary phosphonium. Examples include hydroxides, carbonates of alkali metals such as lithium carbonate, sodium carbonate and potassium carbonate, amines such as diethanolamine and triethanolamine, boric acid, hydrochloric acid, nitric acid, sulfuric acid and acetic acid.

  Examples of the UV absorber include benzophenone UV absorbers, benzotriazole UV absorbers, salicylate UV absorbers, cyanoacrylate UV absorbers, nickel complex salt UV absorbers, and the like.

  Examples of the benzophenone-based ultraviolet absorber include 2-hydroxy-4-n-octoxybenzophenone, 2-hydroxy-4-n-dodecyloxybenzophenone, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2,2 ′, 4,4′-tetrahydroxybenzophenone, and the like.

  Examples of the benzotriazole ultraviolet absorber include 2- (2′-hydroxy-5′-tert-octylphenyl) benzotriazole, 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- ( 2'-hydroxy-4'-octoxyphenyl) benzotriazole, 2- (2'-hydroxy-3'-tert-butyl-5'-methylphenyl) -5-chlorobenzotriazole, and the like.

  Examples of salicylate-based ultraviolet absorbers include phenyl salicylate, p-tert-butylphenyl salicylate, p-octylphenyl salicylate, and the like.

  Examples of the cyanoacrylate ultraviolet absorber include ethyl-2-cyano-3,3′-diphenyl acrylate, methyl-2-cyano-3-methyl-3- (p-methoxyphenyl) acrylate, and butyl-2-cyano. -3-methyl-3- (p-methoxyphenyl) acrylate, and the like.

  Examples of the nickel complex ultraviolet absorber include nickel bis (octylphenyl) sulfide, 2,2′-thiobis (4-tert-octylferrate) -n-butylamine nickel (II), 2,2′-thiobis ( 4-tert-octylferrate) -2-ethylhexylamine nickel (II), 2,2′-thiobis (4-tert-octylferrate) triethanolamine nickel (II), and the like.

  The ink in the ink media set of the present invention comprises at least water, a colorant, and a wetting agent, and if necessary, a penetrating agent, a surfactant, and, if necessary, other components dispersed or dissolved in an aqueous medium, Produced by stirring and mixing as necessary. The dispersion can be performed by, for example, a sand mill, a homogenizer, a ball mill, a paint shaker, an ultrasonic disperser, etc., and stirring and mixing are performed by a stirrer using a normal stirring blade, a magnetic stirrer, a high-speed disperser, or the like. be able to.

  There is no restriction | limiting in particular as coloring of an ink, According to the objective, it can select suitably, Yellow, magenta, cyan, black etc. are mentioned. When recording is performed using an ink set in which two or more of these colorings are used in combination, a multicolor image can be formed. When recording is performed using an ink set in which all colors are combined, a full color image is formed. be able to.

  In the image forming apparatus configured as described above, the sheets 112 are separated and fed one by one from the sheet feeding unit, and the sheet 112 fed substantially vertically upward is guided by the guide 115, and includes the conveyance belt 121 and the counter roller 122. The leading end is guided by the conveying guide 123 and pressed against the conveying belt 121 by the leading end pressure roller 125, and the conveying direction is changed by approximately 90 °.

  At this time, a positive voltage output and a negative output are alternately repeated from the AC bias supply unit to the charging roller 126 by a control circuit (not shown), that is, a charging voltage pattern in which an alternating voltage is applied and the conveying belt 121 alternates. That is, plus and minus are alternately charged in a band shape with a predetermined width in the sub-scanning direction which is the circumferential direction. When the paper 112 is fed onto the conveyance belt 121 charged alternately with plus and minus, the paper 112 is attracted to the conveyance belt 121 by electrostatic force, and the paper 112 is conveyed in the sub-scanning direction by the circular movement of the conveyance belt 121. Is done.

  Therefore, by driving the recording head 107 according to the image signal while moving the carriage 103 in the forward and backward directions, ink droplets are ejected onto the stopped paper 112 to record one line, and the paper 112 is After transporting a predetermined amount, the next line is recorded. Upon receiving a recording end signal or a signal that the trailing edge of the paper 112 has reached the recording area, the recording operation is finished, and the paper 112 is discharged onto the paper discharge tray 154.

  In the case of double-sided printing, when recording on the front surface (surface to be printed first) is completed, the recording belt 112 is fed into the double-sided paper feeding unit 155 by rotating the conveyor belt 121 in the reverse direction. The paper 112 is reversed (with the back surface being the printing surface), and is fed again between the counter roller 122 and the conveyor belt 121. The timing is controlled, and the sheet is conveyed onto the conveyor bell 121 as described above. After recording on the back side, the sheet is discharged to the discharge tray 154.

  Further, during printing (recording) standby, the carriage 103 is moved to the maintenance / recovery mechanism 155 side, and the nozzle surface of the recording head 107 is capped by the cap 157 so that the nozzles are kept in a wet state. To prevent. In addition, the recording liquid is sucked from the nozzle in a state where the recording head 107 is capped by the cap 157 (referred to as “nozzle suction” or “head suction”), and a recovery operation is performed to discharge the thickened recording liquid or bubbles. Wiping is performed by the wiper blade 158 in order to clean and remove ink adhering to the nozzle surface of the recording head 107 by this recovery operation. In addition, an idle ejection operation for ejecting ink not related to recording is performed before the start of recording or during recording. Thereby, the stable ejection performance of the recording head 107 is maintained.

  As described above, since the image forming apparatus including the apparatus for ejecting liquid droplets includes the recording head constituted by the liquid ejection head according to the present invention, a high quality image can be formed.

  Here, when the recording liquid to be used is a dye-based ink using a dye as a coloring material, the heat treatment temperature for forming the ink-resistant liquid contact film is increased, but it contains thallium. It is difficult to receive heat shrinkage due to heat treatment, and the head component dimensions can be formed with high accuracy. In addition, in the case of a pigment-based ink using a pigment as a coloring material, the heat treatment temperature for forming the ink-resistant liquid contact film is lower than that when a dye-based ink is used. Furthermore, it is hard to receive, and the component dimensions of the head can be formed with high accuracy.

  Furthermore, in the case of a pigment-based ink coated with a resin, since a heat treatment process for forming an ink-resistant liquid contact film is not required, it is not subject to thermal shrinkage, so that the head component dimensions can be accurately formed. Can do. In addition, when benzotriazole, which is a rust preventive agent, is contained in the ink, it becomes possible to lower the heat treatment temperature for forming the ink-resistant liquid contact film, and the head component dimensions can be accurately formed. it can.

Next, as a liquid discharge head, a head of a side shooter type in which the droplet discharge direction and the direction of the recording liquid flow path (liquid chamber) are different is the same as the liquid discharge head of the above-described embodiment. An example of a thermal head whose energy generating means (driving element) is an electrothermal converter will be described with reference to FIG.
This liquid ejection head has a flow path on a substrate 512 having an ejection energy generator 511 (electrodes for applying an ejection signal to the generator and a protective layer provided on the generator as needed are omitted). A flow path forming member 515 constituting the side wall of 513 is laminated, and a nozzle plate 516 having a nozzle 514 formed thereon is laminated on the flow path forming member 515. In this head, as indicated by a one-dot chain line 517, the direction of ink flow to the ejection energy operating portion in the flow path 513 is perpendicular to the opening center axis of the nozzle 514.

  With such a head configuration, the energy from the ejection energy generator 511 can be more efficiently converted into the formation of ink droplets and the kinetic energy of the flight, and the meniscus can be quickly restored by supplying ink. This is particularly effective when a heating element is used as the discharge energy generator. In addition, a so-called cavitation phenomenon in which the discharge energy generating body is gradually destroyed by the impact when bubbles that are a problem in the edge shooter disappear can be avoided by the side shooter method. That is, in the side shooter system, when bubbles grow and reach the nozzle, the bubbles are brought into the atmosphere, and the bubbles do not contract due to a temperature drop, so the life of the head is relatively long.

  Even in a head having no vibration plate such as this liquid discharge head, by applying the present invention to a nozzle plate, a flow path plate, etc., the embrittlement and heat shrinkage in the heat treatment process are reduced, A highly accurate liquid discharge head can be obtained.

  In the above embodiment, the present invention has been described with reference to an example in which the present invention is applied to an image forming apparatus having a printer configuration. However, the present invention is not limited to this. For example, the present invention may be applied to an image forming apparatus such as a printer / fax / copier multifunction machine. it can. Further, the present invention can be applied to an image forming apparatus using a recording liquid or a fixing processing liquid that is a liquid other than ink.

  Next, the recording method according to the present invention will be described. In the recording method according to the present invention, an image is recorded on a recording medium (paper) by ejecting liquid droplets from the liquid ejection head according to the present invention as in the image forming apparatus described above.

  Here, first, the relationship between the nozzle plate (nozzle plate), the recording liquid (here, ink), and the recording medium (referred to as media) of the liquid ejection head according to the present invention will be described. As described above, the liquid according to the present invention. The nozzle plate of the ejection head is excellent in water repellency and ink repellency. Therefore, even when ink having a low surface tension is used, ink droplets can be well formed (particulate). This is because the nozzle plate is not too wet and the ink meniscus is formed normally. When the meniscus is formed normally, the ink is not pulled in one direction when the ink is ejected, and as a result, there is little ink ejection bending and an image with high dot position accuracy can be obtained.

  When printing on paper (media) with low absorbency, the quality of the dot position is noticeable in image quality. In other words, since it is difficult for ink to spread on paper with low absorbency, if the dot position accuracy is as low as possible, a portion where the ink cannot be filled in the paper, that is, a white portion is generated. This portion that cannot be filled up leads to uneven image density and reduced image density, and appears in the degradation of image quality.

  However, since the nozzle plate of the liquid ejection head according to the present invention has high dot position accuracy even when using low surface tension ink, the ink can fill the paper even when using paper with low absorbency. Prints with high image quality can be obtained without unevenness or image density reduction.

The recording medium (recording medium) used in the recording method according to the present invention will be described below.
The recording medium has a support and a coating layer on at least one surface of the support, and further has other layers as necessary.

As the recording medium, the transfer amount of the ink as the recording liquid to the recording medium at a contact time of 100 ms measured with a dynamic scanning absorption meter is 4 to 15 ml / m ² , more preferably 6 to 14 ml / m ^2. What is m ² is used. Similarly, a transfer amount of pure water to a recording medium at a contact time of 100 ms measured with a dynamic scanning absorption meter is preferably 4 to 26 ml / m ² , more preferably 8 to 25 ml / m ² . . As a recording medium, if the transfer amount of ink and pure water at a contact time of 100 ms is too small, beading is likely to occur. If it is too large, the ink dot diameter after recording is smaller than the desired diameter. May be too much.

As the recording medium, the amount of ink transferred to the recording medium at a contact time of 400 ms measured with a dynamic scanning absorption meter is 7 to 20 ml / m ² , more preferably 8 to 19 ml / m ^2. Is used. Similarly, the transfer amount of pure water to a recording medium at a contact time of 400 ms measured with a dynamic scanning absorption meter is 5 to 29 ml / m ² , more preferably 10 to 28 ml / m ² . . As a recording medium, if the transfer amount at a contact time of 400 ms is too small, the drying property is insufficient, and thus spur marks are likely to occur. If it is too much, bleeding is likely to occur. In some cases, the gloss of the image portion tends to be low.

  Here, the above-mentioned dynamic scanning absorption meter (DSA, Papa Technical Journal, Vol. 48, May 1994, pp. 88-92, Shigenori Kusaka) It is a device that can measure accurately. This dynamic scanning absorptiometer reads the liquid absorption speed directly from the movement of the meniscus in the capillary, makes the sample disk-shaped, and then scans the liquid absorption head in a spiral pattern according to a preset pattern. Is automatically changed by a method in which the number of necessary points is measured with one sample. A liquid supply head for a paper sample is connected to a capillary via a Teflon (registered trademark) tube, and the position of the meniscus in the capillary is automatically read by an optical sensor. Specifically, the transfer amount of pure water or ink was measured using a dynamic scanning absorption meter (K350 series D type, manufactured by Kyowa Seiko Co., Ltd.). The transfer amount at the contact time of 100 ms and the contact time of 400 ms can be obtained by interpolation from the measured value of the transfer amount at the contact time adjacent to each contact time. The measurement was performed at 23 ° C. and 50% RH.

-Support-
The support is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include paper based on wood fibers, and sheet-like materials such as non-woven fabrics mainly composed of wood fibers and synthetic fibers. .

  Here, there is no restriction | limiting in particular as paper, According to the objective, it can select suitably according to the objective, For example, wood pulp, waste paper pulp, etc. are used. Examples of the wood pulp include hardwood bleached kraft pulp (LBKP), softwood bleached kraft pulp (NBKP), NBSP, LBSP, GP, and TMP.

  As the raw material of waste paper pulp, the white paper, ruled white, cream white, card, special white, medium white, imitation, fair white, Kent, white art, as shown in the used paper standard quality standard table of the Waste Paper Recycling Promotion Center , Special upper deadline, separate upper deadline, newspaper, magazine and so on. Specifically, printer paper such as non-coating computer paper, thermal paper, and pressure-sensitive paper as information-related paper; OA waste paper such as PPC paper; coating of art paper, coated paper, finely coated paper, matte paper, etc. Paper: High quality paper, color quality, notebook, notepaper, wrapping paper, fancy paper, medium quality paper, newsprint, reprint paper, super paper, imitation paper, pure white roll paper, uncoated paper such as milk carton, etc. Examples of used paper and paperboard include chemical pulp paper and high-yield pulp-containing paper. These may be used individually by 1 type and may use 2 or more types together.

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

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

  Examples of the internal sizing agent used for making the support include neutral rosin sizing agents used for neutral papermaking, alkenyl succinic anhydride (ASA), alkyl ketene dimer (AKD), petroleum Examples thereof include resin-based sizing agents. Among these, a neutral rosin sizing agent or alkenyl succinic anhydride is particularly preferable. The alkyl ketene dimer may be added in a small amount because of its high size effect, but the friction coefficient on the surface of the recording paper (media) is low and slippery, which is not preferable from the viewpoint of transportability during ink jet recording. There is.

-Coating layer-
The coating layer contains a pigment and a binder (binder), and further contains a surfactant and other components as necessary.

Here, as the pigment, an inorganic pigment or a combination of an inorganic pigment and an organic pigment can be used.
Examples of inorganic pigments include kaolin, talc, heavy calcium carbonate, light calcium carbonate, calcium sulfite, amorphous silica, titanium white, magnesium carbonate, titanium dioxide, aluminum hydroxide, calcium hydroxide, magnesium hydroxide, and water. Examples include zinc oxide and chlorite. Among these, kaolin is particularly preferable because it has excellent glossiness and can be made close to a paper for offset printing.

  The kaolin includes delaminated kaolin, calcined kaolin, engineered kaolin by surface modification, etc., but considering the gloss development, the particle size distribution with a particle size of 2 μm or less is 80% by mass or more. It is preferable that the kaolin which has occupies 50 mass% or more of the whole kaolin.

  The amount of kaolin added is preferably 50 parts by mass or more with respect to 100 parts by mass of the total pigment in the coating layer. When the addition amount is less than 50 parts by mass, a sufficient effect on glossiness may not be obtained. The upper limit of the addition amount is not particularly limited, but is preferably 90 parts by mass or less from the viewpoint of coating suitability in consideration of the fluidity of kaolin, particularly the thickening under high shear force.

  Examples of organic pigments include water-soluble dispersions such as styrene-acrylic copolymer particles, styrene-butadiene copolymer particles, polystyrene particles, and polyethylene particles. Two or more of these organic pigments may be mixed.

  The amount of the organic pigment added is preferably 2 to 20 parts by mass with respect to 100 parts by mass of the total pigment in the coating layer. Since the organic pigment is excellent in gloss expression and its specific gravity is smaller than that of an inorganic pigment, it is possible to obtain a coating layer that is bulky, high gloss, and has good surface coverage. When the addition amount is less than 2 parts by mass, the above effect is not obtained. When the addition amount exceeds 20 parts by mass, the fluidity of the coating liquid deteriorates, leading to a decrease in coating operability, and economical from the viewpoint of cost. is not.

  The organic pigment has a solid type, a hollow type, a donut type and the like in its form, but the average particle size is 0.2 to 0.2 in view of the balance of gloss development, surface coverage, and fluidity of the coating liquid. A hollow type having a porosity of 40% or more is more preferable.

As the binder, it is preferable to use an aqueous resin.
Here, as the aqueous resin, at least one of a water-soluble resin and a water-dispersible resin is preferably used. There is no restriction | limiting in particular as water-soluble resin, According to the objective, it can select suitably, For example, modified products of polyvinyl alcohol, such as polyvinyl alcohol, anion modified polyvinyl alcohol, cation modified polyvinyl alcohol, acetal modified polyvinyl alcohol; Polyurethane Polyvinylpyrrolidone and polyvinylpyrrolidone and vinyl acetate copolymer, vinylpyrrolidone and dimethylaminoethyl / methacrylic acid copolymer, quaternized vinylpyrrolidone / dimethylaminoethyl / methacrylic acid copolymer, vinylpyrrolidone and methacrylic acid Modified products of polyvinylpyrrolidone such as a copolymer of amidopropyltrimethylammonium chloride; cellulose such as carboxymethylcellulose, hydroxyethylcellulose, droxypropylcellulose; Modified products of cellulose such as thiolated hydroxyethyl cellulose; synthetic resins such as polyester, polyacrylic acid (ester), melamine resin, or modified products thereof, polyester and polyurethane copolymer; poly (meth) acrylic acid, poly ( Examples thereof include (meth) acrylamide, oxidized starch, phosphate esterified starch, self-modified starch, cationized starch, or various modified starches, polyethylene oxide, sodium polyacrylate, and sodium alginate. These may be used individually by 1 type and may use 2 or more types together.

  Among these, polyvinyl alcohol, cation-modified polyvinyl alcohol, acetal-modified polyvinyl alcohol, polyester, polyurethane, a copolymer of polyester and polyurethane, and the like are particularly preferable from the viewpoint of ink absorbability.

  The water-dispersible resin is not particularly limited and may be appropriately selected depending on the intended purpose. For example, polyvinyl acetate, ethylene-vinyl acetate copolymer, polystyrene, styrene- (meth) acrylate copolymer , (Meth) acrylic acid ester polymer, vinyl acetate- (meth) acrylic acid (ester) copolymer, styrene-butadiene copolymer, ethylene-propylene copolymer, polyvinyl ether, silicone-acrylic copolymer , Etc. Further, it may contain a crosslinking agent such as methylolated melamine, methylolated urea, methylolated hydroxypropylene urea, or isocyanate, or may be a copolymer containing units such as N-methylolacrylamide and having a self-crosslinking property. A plurality of these water-based resins can be used simultaneously.

  2-100 mass parts is preferable with respect to 100 mass parts of said pigments, and, as for the addition amount of aqueous resin, 3-50 mass parts is more preferable. The amount of the aqueous resin added is determined so that the liquid absorption characteristics of the recording medium fall within a desired range.

  When a water-dispersible colorant is used as the colorant, the cationic organic compound is not necessarily added, but is not particularly limited and can be appropriately selected and used depending on the purpose. For example, a primary to tertiary amine, quaternary ammonium salt monomer or oligomer that reacts with a sulfonic acid group, a carboxyl group, an amino group, or the like in a direct dye or acidic dye in water-soluble ink to form an insoluble salt. A polymer etc. are mentioned, Among these, an oligomer or a polymer is preferable.

  Examples of the cationic organic compound include dimethylamine / epichlorohydrin polycondensate, dimethylamine / ammonia / epichlorohydrin condensate, poly (trimethylaminoethyl methacrylate / methyl sulfate), diallylamine hydrochloride / acrylamide copolymer. , Poly (diallylamine hydrochloride / sulfur dioxide), polyallylamine hydrochloride, poly (allylamine hydrochloride / diallylamine hydrochloride), acrylamide / diallylamine copolymer, polyvinylamine copolymer, dicyandiamide, dicyandiamide / ammonium chloride / urea / formaldehyde Condensate, polyalkylene polyamine dicyandiamide ammonium salt condensate, dimethyldiallylammonium chloride, polydiallylmethylamine hydrochloride, poly (diallyl) Methylammonium chloride), poly (diallyldimethylammonium chloride / sulfur dioxide), poly (diallyldimethylammonium chloride / diallylamine hydrochloride derivative), acrylamide / diallyldimethylammonium chloride copolymer, acrylate / acrylamide / diallylamine hydrochloride copolymer Products, ethyleneimine derivatives such as polyethyleneimine and acrylicamine polymer, and polyethyleneimine alkylene oxide modified products. These may be used individually by 1 type and may use 2 or more types together.

  Among these, low molecular weight cationic organic compounds such as dimethylamine / epichlorohydrin polycondensate and polyallylamine hydrochloride and other relatively high molecular weight cationic organic compounds such as poly (diallyldimethylammonium chloride) It is preferable to use in combination. By using in combination, the image density can be improved and feathering can be further reduced as compared with the case of single use.

  The cation equivalent of the cationic organic compound by colloid titration method (using polyvinyl potassium sulfate and toluidine blue) is preferably 3 to 8 meq / g. If the cation equivalent is within this range, good results can be obtained within the above dry adhesion range. In the measurement of the cation equivalent by the colloid titration method, the cationic organic compound is diluted with distilled water so that the solid content becomes 0.1% by mass, and the pH is not adjusted.

The dry adhesion amount of the cationic organic compound is preferably 0.3 to 2.0 g / m ² . When the dry adhesion amount of the cationic organic compound is less than 0.3 g / m 2, sufficient image density improvement and feathering reduction effects may not be obtained.

  The surfactant is not particularly limited and may be appropriately selected depending on the intended purpose. Any of anionic, cationic, amphoteric and nonionic surfactants can be used. . Of these, nonionic active agents are particularly preferred. By adding a surfactant, the water resistance of the image is improved, the image density is increased, and bleeding is improved.

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

  The polyhydric alcohol is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include glycerol, trimethylolpropane, pentaerythritol, sorbitol, and sucrose. As the ethylene oxide adduct, a product obtained by substituting a part of ethylene oxide with an alkylene oxide such as propylene oxide or butylene oxide is also effective as long as water solubility can be maintained. The substitution rate is preferably 50% or less. 4-15 are preferable and, as for HLB (hydrophilic / lipophilic ratio) of the said nonionic activator, 7-13 are more preferable.

  0-10 mass parts is preferable with respect to 100 mass parts of said cationic organic compounds, and, as for the addition amount of surfactant, 0.1-1.0 mass part is more preferable.

  Other components can be added to the coating layer as needed, as long as the object and effect of the present invention are not impaired. Examples of the other components include additives such as alumina powder, pH adjuster, preservative, and antioxidant.

  There is no restriction | limiting in particular as a formation method of this coating layer, According to the objective, it can select suitably, It can carry out by the method of impregnating or apply | coating a coating layer liquid on the said support body. The impregnation or coating method of the coating layer liquid is not particularly limited and can be appropriately selected according to the purpose. For example, a conventional size press, a gate roll size press, a film transfer size press, a blade coater, a rod coater, It can be applied with various coating machines such as an air knife coater and curtain coater. Among these, from the viewpoint of cost, a method of impregnating or adhering with a conventional size press, a gate roll size press, a film transfer size press or the like installed in a paper machine and finishing on-machine is preferable.

There is no restriction | limiting in particular in the adhesion amount of this coating layer liquid, Although it can select suitably according to the objective, 0.5-20 g / m < ² > is preferable at a solid content, and 1-15 g / m < ² > is more. preferable. In addition, after impregnation or application | coating, you may make it dry as needed, As temperature of drying in this case, there is no restriction | limiting in particular, Although it can select suitably according to the objective, About 100-250 degreeC is. preferable.

  As the recording medium used in the recording method according to the present invention, a back layer may be formed on the back surface of the support, between the support and the coating layer, and other layers may be formed between the support and the back layer. A protective layer can also be provided on the coating layer. Each of these layers may be a single layer or a plurality of layers.

  The recording medium used in the recording method according to the present invention is a commercially available coated paper for offset printing, coated paper for gravure printing, etc., as long as the liquid absorption property is within the range of the present invention. Also good.

The basis weight of the recording medium used in the recording method according to the present invention is preferably 50 to 250 g / m ² . If it is less than 50 g / m ² , there is no stiffness, and a conveyance failure such as a recording medium being clogged in the middle of the conveyance path tends to occur. If it exceeds 250 g / m ² , the stiffness becomes too large, so that the recording medium cannot be bent at the curved portion in the middle of the conveyance path, and the conveyance failure such as the recording medium being clogged is likely to occur.

  Next, specific examples will be described. Note that the present invention is not limited to these examples.

(Preparation Example 1)
-Preparation of copper phthalocyanine pigment-containing polymer fine particle dispersion-
The inside of the 1 L flask equipped with a mechanical stirrer, thermometer, nitrogen gas inlet tube, reflux tube, and dropping funnel was sufficiently replaced with nitrogen gas, and then 11.2 g of styrene, 2.8 g of acrylic acid, and 12.0 g of lauryl methacrylate. Then, 4.0 g of polyethylene glycol methacrylate, 4.0 g of styrene macromer (manufactured by Toa Gosei Co., Ltd., trade name: AS-6) and 0.4 g of mercaptoethanol were charged, and the temperature was raised to 65 ° C. Next, styrene 100.8 g, acrylic acid 25.2 g, lauryl methacrylate 108.0 g, polyethylene glycol methacrylate 36.0 g, hydroxyethyl methacrylate 60.0 g, styrene macromer (manufactured by Toagosei Co., Ltd., trade name: AS-6) A mixed solution of 36.0 g, mercaptoethanol 3.6 g, azobisdimethylvaleronitrile 2.4 g, and methyl ethyl ketone 18 g was dropped into the flask over 2.5 hours.

  After completion of dropping, a mixed solution of 0.8 g of azobisdimethylvaleronitrile and 18 g of methyl ethyl ketone was dropped into the flask over 0.5 hours. After aging at 65 ° C. for 1 hour, 0.8 g of azobisdimethylvaleronitrile was added and further aging was performed for 1 hour. After completion of the reaction, 364 g of methyl ethyl ketone was added to the flask to obtain 800 g of a polymer solution having a concentration of 50% by mass. Next, a part of the polymer solution was dried and measured by gel permeation chromatography (standard: polystyrene, solvent: tetrahydrofuran). The weight average molecular weight (Mw) was 15,000.

Next, 28 g of the obtained polymer solution, 26 g of copper phthalocyanine pigment, 13.6 g of 1 mol / L potassium hydroxide aqueous solution, 20 g of methyl ethyl ketone, and 30 g of ion-exchanged water were sufficiently stirred. Thereafter, the mixture was kneaded 20 times using a three-roll mill (manufactured by Noritake Company, trade name: NR-84A). The obtained paste was put into 200 g of ion-exchanged water, and after sufficiently stirring, methyl ethyl ketone and water were distilled off using an evaporator to obtain 160 g of a blue polymer fine particle dispersion having a solid content of 20.0% by mass. .
About the obtained polymer microparticles | fine-particles, the average particle diameter (D50%) measured with the particle size distribution analyzer (Microtrac UPA, Nikkiso Co., Ltd.) was 93 nm.

(Preparation Example 2)
-Preparation of polymer fine particle dispersion containing dimethylquinacridone pigment-
In Preparation Example 1, the copper phthalocyanine pigment was changed to C.I. I. A red-purple polymer fine particle dispersion was prepared in the same manner as in Preparation Example 1, except that the pigment red 122 was used.
About the obtained polymer microparticles | fine-particles, the average particle diameter (D50%) measured with the particle size distribution analyzer (Microtrac UPA, Nikkiso Co., Ltd.) was 127 nm.

(Preparation Example 3)
-Preparation of monoazo yellow pigment-containing polymer fine particle dispersion-
In Preparation Example 1, the copper phthalocyanine pigment was changed to C.I. I. A yellow polymer fine particle dispersion was prepared in the same manner as in Preparation Example 1, except that the pigment yellow 74 was changed.
About the obtained polymer microparticles | fine-particles, the average particle diameter (D50%) measured with the particle size distribution analyzer (Microtrac UPA, Nikkiso Co., Ltd.) was 76 nm.

(Preparation Example 4)
-Preparation of carbon black dispersion treated with sulfonating agent-
150 g of commercially available carbon black pigment (manufactured by Degussa, “Printex # 85”) was mixed well in 400 ml of sulfolane, finely dispersed with a bead mill, 15 g of amidosulfuric acid was added, and the mixture was stirred at 140 to 150 ° C. for 10 hours. The obtained slurry was put into 1000 ml of ion-exchanged water, and a surface-treated carbon black wet cake was obtained with a centrifuge at 12,000 rpm. The obtained carbon black wet cake is redispersed in 2,000 ml of ion exchange water, adjusted to pH with lithium hydroxide, desalted and concentrated with an ultrafiltration membrane, and a carbon black dispersion having a pigment concentration of 10% by mass. And filtering with a nylon filter having an average pore diameter of 1 μm to obtain a carbon black dispersion.
About the obtained carbon black dispersion, the average particle diameter (D50%) measured with the particle size distribution analyzer (Microtrac UPA, Nikkiso Co., Ltd.) was 80 nm.

(Production Example 1)
-Production of cyan ink-
Copper phthalocyanine pigment-containing polymer fine particle dispersion 20.0% by mass of Preparation Example 1, 3-methyl-1,3-butanediol 23.0% by mass, glycerin 8.0% by mass, 2-ethyl-1,3-hexane 2.0% by mass of diol, 2.5% by mass of FS-300 (manufactured by DuPont) as a fluorosurfactant, 0.2% by mass of Proxel LV (manufactured by Avecia) as an antiseptic / antifungal agent, 2-amino Appropriate amounts of 2-ethyl-1,3-propanediol 0.5% by mass and ion-exchanged water were added to obtain 100% by mass, followed by filtration through a membrane filter having an average pore size of 0.8 μm. A cyan ink was prepared as described above.

(Production Example 2)
-Magenta ink production-
Dimethylquinacridone pigment-containing polymer fine particle dispersion 20.0% by mass of Preparation Example 2, 3-methyl-1,3-butanediol 22.5% by mass, glycerin 9.0% by mass, 2-ethyl-1,3-hexane 2.0% by mass of diol, 2.5% by mass of FS-300 (manufactured by DuPont) as a fluorosurfactant, 0.2% by mass of Proxel LV (manufactured by Avecia) as an antiseptic / antifungal agent, 2-amino Appropriate amounts of 2-ethyl-1,3-propanediol 0.5% by mass and ion-exchanged water were added to obtain 100% by mass, followed by filtration through a membrane filter having an average pore size of 0.8 μm. A magenta ink was prepared as described above.

(Production Example 3)
-Preparation of yellow ink-
Monoazo yellow pigment-containing polymer fine particle dispersion of Preparation Example 2 20.0% by mass, 3-methyl-1,3-butanediol 24.5% by mass, glycerin 8.0% by mass, 2-ethyl-1,3-hexane 2.0% by mass of diol, 2.5% by mass of FS-300 (manufactured by DuPont) as a fluorosurfactant, 0.2% by mass of Proxel LV (manufactured by Avecia) as an antiseptic / antifungal agent, 2-amino Appropriate amounts of 2-ethyl-1,3-propanediol 0.5% by mass and ion-exchanged water were added to obtain 100% by mass, followed by filtration through a membrane filter having an average pore size of 0.8 μm. Thus, a yellow ink was prepared.

(Production Example 4)
-Preparation of black ink-
Carbon black dispersion of Preparation Example 4 20.0% by mass, 2-methyl-1,3-butanediol 22.5% by mass, glycerin 7.5% by mass, 2-pyrrolidone 2.0% by mass, 2-ethyl- 2.0 mass% of 1,3-hexanediol, 2.5 mass% of FS-300 (manufactured by DuPont) as a fluorosurfactant, 0.2 mass of Proxel LV (manufactured by Avecia) as an antiseptic and fungicidal agent %, 2-amino-2-ethyl-1,3-propanediol 0.5% by mass and ion exchanged water are added in an appropriate amount to 100% by mass, and then filtered through a membrane filter having an average pore size of 0.8 μm. It was. A black ink was prepared as described above.

  Next, the surface tension and viscosity of each of the inks of Production Examples 1 to 4 obtained were measured as follows. The results are shown in Table 1.

<Measurement of viscosity>
The viscosity was measured at 25 ° C. using a R-500 viscometer (manufactured by Toki Sangyo Co., Ltd.) under conditions of cone 1 ° 34 ′ × R24, 60 rpm, 3 minutes later.

<Measurement of surface tension>
The surface tension is a static surface tension measured at 25 ° C. using a platinum plate using a surface tension measuring device (CBVP-Z, manufactured by Kyowa Interface Science Co., Ltd.).

-Production of support-
A 0.3 mass% slurry having the following composition was made with a long paper machine to prepare a support having a basis weight of 79 g / m ² . In addition, in the size press process of the papermaking process, the oxidized starch aqueous solution was applied so that the solid content was 1.0 g / m ² per side.
-Hardwood bleached kraft pulp (LBKP) ... 80 parts by mass-Softwood bleached kraft pulp (NBKP) ... 20 parts by mass-Light calcium carbonate (trade name: TP-121, manufactured by Okutama Kogyo Co., Ltd.) ... 10 parts by mass 1.0 part by mass-Amphoteric starch (trade name: Cato3210, manufactured by Nippon NSC Co., Ltd.) ... 1.0 part by mass-Neutral rosin sizing agent (trade name: NeuSize M-10, manufactured by Harima Kasei Co., Ltd.) ... 0. 3 parts by mass-Yield improver (trade name: NR-11LS, manufactured by Hymo Co., Ltd.) ... 0.02 parts by mass

(Production Example 1)
-Production of recording medium 1-
70 parts by mass of clay having a particle diameter of 2 μm or less as a pigment of 97% by mass, 30 parts by mass of heavy calcium carbonate having an average particle diameter of 1.1 μm, and styrene having a glass transition temperature (Tg) of −5 ° C. as an adhesive -Add 8 parts by weight of butadiene copolymer emulsion, 1 part by weight of phosphate esterified starch, and 0.5 parts by weight of calcium stearate as an auxiliary agent, and then add water to obtain a coating solution having a solid content concentration of 60% by weight. Prepared.

The obtained coating solution was applied to both sides using a blade coater so that the solid content per side of the prepared support was 8 g / m ² , dried with hot air, and then subjected to a step super calender treatment. As a result, “Recording medium 1” was produced.

(Production Example 2)
-Production of recording medium 2-
70 parts by mass of clay having a particle diameter of 2 μm or less as a pigment of 97% by mass, 30 parts by mass of heavy calcium carbonate having an average particle diameter of 1.1 μm, and styrene having a glass transition temperature (Tg) of −5 ° C. as an adhesive -Addition of 7 parts by mass of butadiene copolymer emulsion, 0.7 parts by mass of phosphoric acid esterified starch, 0.5 parts by mass of calcium stearate as an auxiliary agent, and further water to add a coating solution having a solid content concentration of 60% by mass Was prepared.

The obtained coating solution is coated on both sides with a blade coater so that the solid content per side of the prepared support is 8 g / m ² , dried with hot air, and then subjected to a step super calendar process. "Recording medium 2" was produced.

Example 1
-Ink set, recording media, and image recording-
“Ink set 1” consisting of black ink of Production Example 4, yellow ink of Production Example 3, magenta ink of Production Example 2 and cyan ink of Production Example 1 was prepared by a conventional method.
Using the obtained ink set 1 and the recording medium 1 described above, printing is performed at an image resolution of 600 dpi and a maximum ink droplet of 18 pl using a drop-on-demand printer prototype having 300 dpi, nozzle resolution 384, and nozzles. It was. The amount of secondary color was regulated to 140% and the amount of adhesion was regulated, and solid images and characters were printed to obtain an image print.

(Example 2)
-Ink set, recording media, and image recording-
In Example 1, except that the recording medium 2 was used as a recording medium, printing was performed in the same manner as in Example 1 to obtain an image print.

(Example 3)
-Ink set, recording media, and image recording-
In Example 1, a coated paper for gravure printing (trade name; space DX, basis weight = 56 g / m ² , manufactured by Nippon Paper Industries Co., Ltd.) (hereinafter referred to as “recording medium 3”) was used as the recording medium. Except for the above, printing was performed in the same manner as in Example 1 to obtain an image print.

(Comparative Example 1)
-Ink set, recording media, and image recording-
In Example 1, commercially available offset coated paper (trade name: Aurora coat, basis weight = 104.7 g / m ² , manufactured by Nippon Paper Industries Co., Ltd., hereinafter referred to as “recording medium 4”) as a recording medium. Except for the use, printing was performed in the same manner as in Example 1 to obtain an image print.

(Comparative Example 2)
-Ink set, recording media, and image recording-
In Example 1, except that commercially available matte coated paper for inkjet (trade name: Superfine exclusive paper, manufactured by Seiko Epson Corporation, hereinafter referred to as “recording medium 5”) was used as the recording medium. In the same manner as in Example 1, printing was carried out to obtain an image print.

  Next, with respect to the recording medium 1, the recording medium 2, the recording medium 3, the recording medium 4, and the recording medium 5, pure water by a dynamic scanning absorption meter and The amount of cyan ink transferred was measured. The results are shown in Table 3.

<Measurement of transfer amount of pure water and cyan ink by dynamic scanning absorption meter>
For each recording medium, the transfer amount of pure water or cyan ink was measured at 25 ° C. and 50% RH using a dynamic scanning absorption meter (K350 series D type, manufactured by Kyowa Seiko Co., Ltd.). The transfer amount at the contact time of 100 ms and the contact time of 400 ms was determined by interpolation from the measured value of the transfer amount at the contact time adjacent to each contact time.

  Next, for each of the obtained image prints of Examples 1 to 3, beading, bleeding, spur marks, and gloss were evaluated as follows. The results are shown in Table 4.

<Beading>
The degree of beading of the green solid image portion of each image print was visually observed and evaluated according to the following criteria.
〔Evaluation criteria〕
Rank 4: There is no occurrence of beading and uniform printing.
Rank 3: Slight beading is observed.
Rank 2: The occurrence of beading is clearly recognized.
Rank 1: Significant beading is observed.

<Evaluation of bleed>
The degree of bleed of black letters in the yellow of each image print was visually observed and evaluated according to the following criteria.
〔Evaluation criteria〕
A: Clear printing without bleeding.
○: Slight bleeding is observed.
X: The blur has occurred so that the outline of the character is not clear.

<Evaluation of spur marks>
The degree of spurs on each image print was visually observed and evaluated according to the following criteria.
〔Evaluation criteria〕
A: Not recognized at all.
○: Slightly recognized.
X: Spur marks are clearly recognized.

<Evaluation of glossiness>
The 60 ° specular gloss (JIS Z8741) of the cyan solid image portion of each image print was measured.

From the results of Table 4, at least a water, a colorant, and a wetting agent are included, and an ink having a surface tension at 25 ° C. of 20 to 35 mN / m and a contact time of 100 ms measured with a dynamic scanning absorption meter. a recording transfer amount is 4~15ml / ^{m 2} to the media of the ink, and transfer amount of the recording medium of the ink at a contact time of 400ms is a combination of a recording medium is 7~20ml / ^{m 2} As compared with Comparative Examples 1 and 2, Examples 1 to 3 showed that evaluation results for achieving beading suppression, bleed suppression, no spur trace, and high glossiness at a high level at the same time were obtained.

1 is an exploded perspective view showing a first embodiment of a liquid ejection head according to the present invention. It is sectional explanatory drawing along the liquid chamber longitudinal direction of the head. It is sectional explanatory drawing of the bipitch structure along the liquid chamber transversal direction of the head. It is sectional explanatory drawing of the normal pitch structure along the liquid chamber transversal direction of the head. It is a plane explanatory view of the nozzle plate of the head. It is sectional explanatory drawing which shows an example of the member which integrally formed the nozzle plate and the flow-path board. It is a cross-sectional explanatory view showing an example of a member in which a diaphragm and a flow path plate are integrally formed. 1 is an overall configuration diagram illustrating an example of an image forming apparatus according to the present invention. Similarly it is principal part plane explanatory drawing. It is principal part cross-sectional explanatory drawing used for description of the other example of the liquid discharge head which concerns on this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 ... Channel plate 2 ... Nozzle plate 3 ... Vibrating plate 4 ... Nozzle 6 ... Liquid chamber 12 ... Piezoelectric element 13 ... Base member 17 ... Frame member 103 ... Carriage 107 ... Recording head

Claims (40)

  In a liquid discharge head comprising a nozzle for discharging a recording liquid droplet, a liquid chamber in communication with the nozzle, and energy generating means for generating energy for pressurizing the recording liquid in the liquid chamber, the flow of the recording liquid The flow path forming member that forms the path is made of a metal material containing nickel, and the peak intensity on the nickel (200) plane measured by X-ray analysis is superior to the peak intensity on the nickel (111) plane. A liquid discharge head characterized by the above.   The liquid discharge head according to claim 1, wherein the metal material forming the flow path forming member contains thallium.   3. The liquid discharge head according to claim 2, wherein the thallium content does not exceed 1% by mass.   The liquid discharge head according to claim 1, wherein the flow path forming member contains cobalt.   5. The liquid discharge head according to claim 4, wherein the cobalt content does not exceed 1% by mass.   The liquid discharge head according to claim 1, wherein the flow path forming member contains manganese.   5. The liquid discharge head according to claim 4, wherein the manganese content does not exceed 1% by mass.   In a liquid discharge head comprising a nozzle for discharging a recording liquid droplet, a liquid chamber in communication with the nozzle, and energy generating means for generating energy for pressurizing the recording liquid in the liquid chamber, the flow of the recording liquid A liquid discharge head, wherein the flow path forming member forming the path is formed of a metal material containing nickel and thallium.   9. The liquid discharge head according to claim 8, wherein the peak intensity on the nickel (200) plane measured by X-ray analysis is superior to the peak intensity on the nickel (111) plane.   10. The liquid discharge head according to claim 1, wherein the peak intensity on the nickel (111) plane measured by X-ray diffraction is I (111), and the peak intensity on the nickel (200) plane is I (200). ), The intensity ratio of the crystal orientation plane represented by the ratio of the peak intensity at the nickel (200) plane to the peak intensity at the nickel (111) plane is I (200) / I (111)> 1. A liquid discharge head having a relationship of 0.   11. The liquid discharge head according to claim 1, wherein the flow path forming member contains sulfur, and the sulfur content does not exceed 0.1 mass%. .   12. The liquid discharge head according to claim 1, wherein the flow path forming member is a nozzle plate on which the nozzle is formed.   13. The liquid discharge head according to claim 1, wherein the flow path forming member is a flow path plate that forms the liquid chamber.   14. The liquid discharge head according to claim 1, wherein the flow path forming member is a vibration plate that forms a wall surface of the liquid chamber.   15. The liquid discharge head according to claim 1, wherein at least two members: a nozzle plate in which the nozzle is formed, a flow path plate in which the liquid chamber is formed, and a vibration plate in which the wall surface of the liquid chamber is formed. And a liquid discharge head characterized in that these two members are integrally formed.   16. The liquid discharge head according to claim 1, wherein the flow path forming member is formed by an electroforming method.   17. The liquid discharge head according to claim 1, wherein the flow path forming member has a Vickers hardness (HV) in a range of 250 (Hv) to 500 (Hv). .   18. The liquid ejection head according to claim 1, wherein the liquid ejection head is a side shooter type head in which the ejection direction of the droplet and the direction of the flow path of the recording liquid are different.   19. An image forming apparatus comprising a recording head for discharging recording liquid droplets, wherein the recording head is the liquid discharging head according to claim 1.   20. The image forming apparatus according to claim 19, wherein the recording liquid is an ink containing a dye as a color material.   20. The image forming apparatus according to claim 19, wherein the recording liquid is an ink containing a pigment as a color material.   20. The image forming apparatus according to claim 19, wherein the recording liquid is ink containing polymer fine particles containing pigment particles as a color material.   The image forming apparatus according to claim 19, wherein the recording liquid is an ink containing benzotriazole.   An apparatus for ejecting liquid droplets from a liquid ejection head, comprising the liquid ejection head according to claim 1.   19. A recording method, wherein recording is performed on a recording medium by ejecting recording liquid droplets from the liquid ejection head according to claim 1.   26. The recording method according to claim 25, wherein the recording medium is a recording medium having a support and a coating layer on at least one surface of the support. 27. The recording method according to claim 25 or 26, wherein a transfer amount of the recording liquid to the recording medium at a contact time of 100 ms measured at 23 ° C. and 50% RH is 4 to 15 ml / m ^2. And a transfer amount of the recording liquid to the recording medium at a contact time of 400 ms is 7 to 20 ml / m ² . 27. The recording method according to claim 25 or 26, wherein the transfer amount of pure water to the recording medium at a contact time of 100 ms measured at 23 ° C. and 50% RH is 4 to 26 ml / m ² . And a transfer amount of pure water to the recording medium at a contact time of 400 ms is 5 to 29 ml / m ² . 26. The recording method according to claim 25, wherein the recording medium is composed of at least a base material and a coating layer, and a solid content adhesion amount of the coating layer is 0.5 to 20.0 g / m < ² >. And a recording method. 26. The recording method according to claim 25, wherein the recording medium has a basis weight of 50 to 250 g / m < ² >.   26. The recording method according to claim 25, wherein the recording medium is subjected to a super calendar process.   32. The recording method according to claim 25, wherein the recording medium contains a pigment, and the pigment is kaolin.   32. The recording method according to claim 25, wherein the recording medium contains a pigment, and the pigment is heavy calcium carbonate.   34. A recording method according to claim 25, wherein the recording medium contains an aqueous resin.   35. The recording method according to claim 34, wherein the aqueous resin is a water-soluble resin or a water-dispersible resin.   36. The recording method according to claim 25, wherein the recording liquid contains at least water, a colorant, and a wetting agent.   37. A recording method according to claim 25, wherein the recording liquid has a surface tension at 25 [deg.] C. of 15 to 40 mN / m.   38. The recording method according to claim 25, wherein the recording liquid contains a dispersible colorant as a colorant, and the average particle diameter of the dispersible colorant is 0.01 to 0.16 [mu] m. And a recording method.   39. The recording method according to claim 25, wherein the recording liquid has a viscosity at 25 [deg.] C. of 1 to 30 mPa.sec.   40. The recording method according to claim 25, wherein the recording liquid contains a surfactant, and the surfactant is a fluorinated surfactant.

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