JP5608959B2 - Image recording liquid and recording apparatus - Google Patents

Description

The present invention relates to an image recording liquid, about your and recording apparatus.

  As one of methods for recording images and data using ink, there is an ink jet recording method. The principle of the ink jet recording system is to record on paper, cloth, film, etc. by discharging liquid or molten solid ink from a nozzle, slit, porous film or the like. As for the method for ejecting ink, the so-called charge control method in which ink is ejected using electrostatic attraction, the so-called drop-on-demand method (pressure pulse method) in which ink is ejected using the vibration pressure of a piezo element. Various methods have been proposed, such as a so-called thermal ink jet method, in which ink is ejected using pressure generated by the formation and growth of bubbles due to high heat. By these methods, extremely high-definition images and data are A record is obtained.

  In order to perform high-quality recording on various recording media such as penetrating media and non-penetrating media, recording methods using ink, including this ink jet recording method, are recorded on an intermediate transfer member and then transferred to the recording medium. A method has been proposed.

  For example, Patent Document 1 proposes a method for recording while supplying a plurality of types of powder mixtures onto an intermediate, such as polymers having different water absorption, water absorbing polymers having different sizes, and water absorbing polymers having different crosslinking degrees. Yes.

  Patent Document 2 proposes a method of recording while supplying solid particles (particles of polysaccharide polymer, alginic acid, carrageenan, etc.) that thicken the ink by contact with the ink on the intermediate.

  Further, in Patent Document 3, a hydrophobic resin particle layer is formed on an intermediate, and ink (for example, an SD type dye ink slow dry type (Slow Dry type)) is held in the voids of the hydrophobic resin particle layer. A method of transferring to a recording medium has been proposed.

  Patent Document 4 proposes a method in which a gap type ink absorption layer in which inorganic particles, a hydrophilic polymer, and the like are wet-coated is provided on an intermediate body (sheet), and dye ink is ejected thereon and transferred to a recording medium. Has been.

  Patent Document 5 discloses a porous ink absorbing layer formed by drying at a temperature not higher than the minimum film-forming temperature (MFT) of thermoplastic resin particles, which contains thermoplastic resin particles and non-thermoplastic particles. Inkjet intermediate transfer media having been proposed.

  In Patent Document 6, a powder that is thickened by contact with a liquid using a high electric resistance material is supplied onto an intermediate transfer body, and then an image is formed by bringing the liquid into contact with the powder to form an image on the intermediate transfer body. There has been proposed a recording apparatus for transferring a thickened image onto a transfer medium.

  Patent Document 7 discloses a liquid ejected from a liquid ejecting apparatus by previously forming a powder that shows solubility or swelling with respect to a droplet and can increase the viscosity of the droplet on an intermediate transfer member. A recording apparatus has been proposed in which droplets reach the intermediate transfer member, and the powder is dissolved or swollen by the droplets, and the droplets whose viscosity has been increased by the powder are transported to the transfer section by the intermediate transfer member and transferred onto the recording paper. .

  In Patent Document 8, before ink or flying ink droplets on a printing plate are transferred to an intermediate transfer member, a liquid is attached to the surface of the intermediate transfer member, and after ink is attached to the liquid, A recording method has been proposed in which ink on a transfer body is transferred to a printing medium together with a liquid.

  In Patent Document 9, an image is formed on the surface of an image carrier using oil-based ink using an electrostatic field by utilizing an electrostatic field, and a printed matter is created by contact-transferring the image formed on the image carrier onto a printing medium. An ink jet printing method characterized by the above has been proposed.

In Patent Document 10, a step of applying a first material that reduces the fluidity of the colored ink to the intermediate transfer member, and a coloring ink is applied from the recording head to the intermediate transfer member to which the first material is applied. And forming the ink image, transferring the ink image to a recording medium, and applying the second material for improving the scratch resistance of the image to the intermediate transfer body before the transferring step. Has been proposed.
JP 2000-343808 A JP 2000-94654 A JP 2003-57967 A JP 2002-370347 A JP 2002-321443 A JP 2001-321443 A Japanese Patent Laid-Open No. 11-188858 Japanese Patent Application Laid-Open No. 2001-212956 JP 2001-315426 A JP 2005-170036 A

An object of the present invention, the image formation is performed for a variety of recording media, the image recording liquid high-definition image free from uneven printing is formed, to provide a contact and recording apparatus.

The above problem is solved by the following means. That is,
The invention according to claim 1
In an image recording method of recording an image by supplying a stimulus after ejecting ink to a liquid cured layer and curing the cured layer, the liquid is used as a liquid for forming the cured layer. The liquid for image recording containing the curable material hardened | cured by the irritation | stimulation from, and the water-absorbing resin particle which the inorganic particle adhered to the surface.

The invention according to claim 2
The image recording liquid according to claim 1, wherein the inorganic particles are silica particles.

The invention according to claim 3
The image recording liquid according to claim 1, wherein the inorganic particles are inorganic particles whose surfaces have been subjected to a hydrophobic treatment.

The invention according to claim 4
The image recording liquid according to claim 1, wherein the inorganic particles are inorganic particles having a hydrophilic surface.

The invention according to claim 5
5. The image recording liquid according to claim 3, wherein the inorganic particles include at least two kinds of inorganic particles whose surfaces are hydrophobized and inorganic particles whose surfaces are hydrophilized. 6.

The invention according to claim 6
An intermediate transfer member, supply means for supplying the image recording liquid according to any one of claims 1 to 5 onto the intermediate transfer member, and the image recording member supplied onto the intermediate transfer member Discharge means for discharging aqueous ink containing an aqueous solvent onto a liquid cured layer formed of liquid , and transfer means for transferring the cured layer on which the aqueous ink has been ejected from the intermediate transfer member to a recording medium. And a stimulus supply means for supplying a stimulus for curing the layer to be cured.

The invention according to claim 7 provides:
A supply means for supplying the image recording liquid according to any one of claims 1 to 5 onto a recording medium, and a liquid form formed by the image recording liquid supplied onto the recording medium The recording apparatus includes: a discharge unit that discharges a water-based ink containing an aqueous solvent to a layer to be cured; and a stimulus supply unit that supplies a stimulus for curing the layer to be cured.

According to the first and second aspects of the invention, it is possible to provide an image recording liquid in which images are formed on various recording media and a high-definition image without printing unevenness is formed.

  According to the invention of claim 3, the affinity for a recording medium having a liquid absorbing layer is improved, ink bleeding at the time of ink liquid absorption is suppressed, and the gap between the water absorbent resin particles is filled, so that an intermediate transfer member is obtained. There is an effect that the image quality is improved.

  According to the invention of claim 4, the ink outflow from the water-absorbent resin particles is prevented, the permeability of the ink between the water-absorbent resin particles is improved, and an interface with the water-absorbent resin particles is formed, There is an effect that the familiarity of ink is suppressed.

  According to the invention of claim 5, the resin compatibility with the ink and the affinity between the water-absorbing resin particles are adjusted, and the ink permeability at the interface of the water-absorbing resin particles is suppressed by adjusting the blending ratio. In addition to improving the image quality on the transfer body, maintaining the image quality until curing and fixing, and further suppressing the bleeding of ink components to areas other than the image forming area when transferring onto the recording medium, and curing from the intermediate transfer body There is an effect of improving releasability.

According to the sixth aspect of the present invention, it is possible to provide a recording apparatus in which images are formed on various recording media and a high-definition image without printing unevenness is formed. In addition, since the intermediate transfer system is used, the image storability is excellent, and the effect of improving the retention of the transferred image on the recording medium of the cured layer and shortening the drying time is achieved.

According to the seventh aspect of the present invention, it is possible to provide a recording apparatus in which images are formed on various recording media and a high-definition image without printing unevenness is formed. In addition, since it is an indirect recording method, it has a simple configuration, versatility suitable for various papers, and effects such as image formation at high speed and low cost.

Hereinafter, preferred embodiments will be described in detail.
Note that the image recording liquid shown in the following preferred embodiment is an image recording method for recording an image by supplying a stimulus after discharging ink to a liquid cured layer to cure the cured layer. It includes a curable material that is used as a liquid for forming the cured layer and is cured by an external stimulus, and water-absorbing resin particles having inorganic particles attached to the surface thereof.
The image recording liquid is supplied to an intermediate transfer member, a recording medium, or the like to form a liquid cured layer, and then an aqueous ink containing an aqueous solvent is ejected onto the cured layer to form an image.

  Hereinafter, preferred embodiments will be described with reference to the drawings. In addition, the same code | symbol is provided to the member which has the substantially same function throughout all the drawings, and the overlapping description may be abbreviate | omitted.

(First embodiment)
FIG. 1 is a configuration diagram illustrating a recording apparatus according to the first embodiment.

As shown in FIG. 1, the recording apparatus 101 according to the first embodiment includes, for example, an intermediate transfer drum 10, a curable material and water-absorbing resin particles that are cured on the intermediate transfer drum 10 by an external stimulus (energy). A solution supply device 12 for supplying a curable solution (image recording liquid ) 12A containing silica particles to form a cured layer 12B formed by the curable solution 12A, and an aqueous solvent on the cured layer 12B An ink jet recording head 14 that discharges aqueous ink droplets 14A to form an image T, and a cured layer 12B on which the image T is formed by applying pressure to the intermediate transfer drum 10 on the recording medium P are disposed on the recording medium P. And a stimulus supply device 18 for supplying a stimulus for curing the layer to be cured 12B transferred onto the recording medium P.

  Further, downstream of the transfer device 16 in the rotation direction of the intermediate transfer drum 10, removal of the residue of the cured layer 12B remaining on the surface of the intermediate transfer drum 10 and foreign matters other than the residue (paper dust of the recording medium P, etc.) A cleaning device 20 for removing the deposits such as) is disposed.

The intermediate transfer drum 10 may have a configuration including, for example, a cylindrical substrate and a surface layer coated on the surface of the substrate. The intermediate transfer drum 10 has a width (length in the axial direction) equal to or greater than the width of the recording medium P.
Examples of the material of the cylindrical base include aluminum, stainless steel (SUS), and copper.
Examples of the material for the surface layer include various resins [for example, polyimide, polyamideimide, polyester, polyurethane, polyamide, polyethersulfone, fluorine resin, etc.], various rubbers (for example, nitrile rubber, ethylene propylene rubber, Chloroprene rubber, isoprene rubber, styrene rubber, butadiene rubber, butyl rubber, chlorosulfonated polyethylene, urethane rubber, epichlorohydrin rubber, acrylic rubber, silicone rubber, fluorine rubber, etc.). The surface layer may have a single layer structure or a stacked structure.

  The solution supply device 12 is formed of, for example, a supply roller 12D that supplies the curable solution 12A to the intermediate transfer drum 10 and a supplied curable solution 12A in a housing 12C that stores the curable solution 12A. And a blade 12E that defines the layer thickness of the cured layer 12B.

  The solution supply device 12 may be configured such that the supply roller 12 </ b> D continuously contacts the intermediate transfer drum 10 or is separated from the intermediate transfer drum 10. Further, the solution supply device 12 may supply the curable solution 12A to the housing 12C from an independent solution supply system (not shown) so that the supply of the curable solution 12A is not interrupted.

  Here, the “curable material curable by external stimulus (energy)” contained in the curable solution 12A means a material that is cured by an external stimulus and becomes a “curable resin”. Specific examples include curable monomers, curable macromers, curable oligomers, and curable prepolymers. Details thereof will be described later.

  The “water-absorbing resin particles” contained in the curable solution 12A mean a material that absorbs an aqueous solvent. Details thereof will be described later.

  The solution supply device 12 is not limited to the above-described configuration, and a known supply method (coating method: for example, bar coater coating, spray coating, ink jet coating, air knife coating, blade coating, roll coating) An apparatus using a method such as application) is applied.

  The inkjet recording head 14 includes, for example, a recording head 14K for discharging black ink, a recording head 14C for discharging cyan ink, and a magenta ink from the upstream side in the rotation direction of the intermediate transfer drum 10. The recording head 14 </ b> M and the recording head 14 </ b> Y for ejecting yellow ink are configured to include recording heads for each color. Of course, the configuration of the recording head 14 is not limited to the above configuration, and may be configured by only the recording head 14K, or may be configured by only the recording head 14C, the recording head 14M, and the recording head 14Y.

  For example, each recording head 14 is preferably a line type ink jet recording head having a width equal to or larger than the width of the recording medium P, but a conventional scanning ink jet recording head may be used. The ink ejection method of each recording head 14 is not limited as long as it is a method capable of ejecting ink, such as a piezoelectric element driving type and a heating element driving type.

  For example, the recording heads 14 are arranged in series in the order of the recording head 14K, the recording head 14C, the recording head 14M, and the recording head 14Y from the upstream side in the rotation direction of the intermediate transfer drum 10.

  Each recording head 14 is arranged such that the distance between the surface of the intermediate transfer drum 10 and the nozzle surface of the head is, for example, about 0.3 to 0.7 mm. Each recording head 14 is disposed, for example, such that its longitudinal direction intersects (preferably orthogonally intersects) the rotational direction of the intermediate transfer drum.

  The transfer device 16 includes a pressure roll 16 </ b> A disposed so as to be pressed against the intermediate transfer drum 10. The pressure roll 16A is configured similarly to the material configuration of the intermediate transfer drum 10, for example.

  The stimulus supply device 18 is selected according to the type of curable material contained in the curable solution 12A to be applied. Specifically, for example, when an ultraviolet curable material that is cured by irradiation with ultraviolet rays is applied, the stimulus supply device 18 irradiates ultraviolet rays to the curable solution 12A (the cured layer 12B formed thereby) with ultraviolet rays. Apply the device. Further, when an electron beam curable material that is cured by electron beam irradiation is applied, an electron beam irradiation device that irradiates the curable solution 12A (the cured layer 12B formed thereby) with an electron beam is used as the stimulus supply device 18. Apply. Moreover, when applying the thermosetting material hardened | cured by provision of heat, the heat provision apparatus which provides heat to the curable solution 12A (the to-be-hardened layer 12B formed by this) is applied as the stimulus supply apparatus 18. FIG.

  Here, as the ultraviolet irradiation device, for example, a metal halide lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a deep ultraviolet lamp, a lamp that uses a microwave to excite a mercury lamp from the outside without an electrode, an ultraviolet laser, a xenon lamp, a UV-LED, etc. Applies.

  Here, the ultraviolet irradiation condition is not particularly limited as long as the curable solution 12A containing the ultraviolet curable material (the cured layer 12B formed thereby) is sufficiently cured, and is ultraviolet curable. Although it may be selected according to the material type, the thickness of the layer to be cured 12B, etc., for example, irradiation with 2s at a high-pressure mercury lamp 120 W / cm output density is performed.

  Further, as an electron beam irradiation device, for example, there are a scanning type / curtain type, etc. The curtain type draws thermoelectrons generated in a filament by a grid in a vacuum chamber, and further, by a high voltage (for example, 70 to 300 kV), It is a device that accelerates at once, becomes an electron flow, passes through the window foil, and is released to the atmosphere side. The wavelength of an electron beam is generally smaller than 1 nm and has a large energy and ranges up to several MeV, but energy of several tens to several hundreds keV is applied when the wavelength of the electron beam is on the order of pm.

  Here, the irradiation condition of the electron beam is not particularly limited as long as the curable solution 12A containing the electron beam curable material (the cured layer 12B formed thereby) is sufficiently cured. For example, the electron dose is 5 to 100 kGy level or the like, although it can be selected according to the type of the linear curable material, the thickness of the layer 12B to be cured, and the like.

  Moreover, as a heat provision apparatus, a halogen lamp, a ceramic heater, a nichrome wire heater, a microwave heating, an infrared lamp etc. are applied, for example. As the heat applying device, an electromagnetic induction heating device can also be applied.

  Here, the heat application condition is not particularly limited as long as it can sufficiently cure the curable solution 12A containing the thermosetting material (the cured layer 12B formed thereby), Although it can be selected according to the thermosetting material type, the thickness of the layer 12B to be cured, etc., for example, in air, it is 5 min in a 200 ° C. environment.

  Note that the fully cured state means a state in which the curable paper 12B is superimposed on the cured layer cured by the stimulation supply device 18 and a permeable paper (plain paper) is superimposed and no transfer occurs even when a load of 200 g is applied. Say.

  As the recording medium P, a permeation medium (for example, plain paper, coated paper, etc.) and a non-penetration medium (for example, art paper, resin film, etc.) are applied. The recording medium is not limited to these, and includes other industrial products such as semiconductor substrates.

  Hereinafter, an image recording process of the recording apparatus 101 according to the present embodiment will be described.

  In the recording apparatus 101 according to the present embodiment, the intermediate transfer drum 10 is rotationally driven. First, the solution supply device 12 supplies the curable solution 12A to the surface of the intermediate transfer drum 10 to form the cured layer 12B.

  The thickness of the curable layer 12B is desirably 0.5 μm or more and 50 μm or less.

  Further, for example, if the thickness of the cured layer 12B is set such that the ink droplet 14A does not reach the lowermost layer of the cured layer 12B, the ink droplet 14A exists in the cured layer 12B after transfer to the recording medium P. The area where the area is not exposed and the ink droplet 14A does not exist functions as a protective layer after curing.

  Next, the ink droplets 14 </ b> A are ejected by the inkjet recording head 14, and the ink droplets 14 </ b> A are applied to the cured layer 12 </ b> B supplied on the intermediate transfer drum 10. The ink jet recording head 14 applies ink droplets 14A to predetermined positions of the cured layer 12B based on predetermined image information.

  At this time, the ink droplets 14A are ejected by the inkjet recording head 14 on the intermediate transfer drum 10 which is a rigid body. That is, the ink droplets 14A are ejected to the cured layer 12B in a state where the drum surface is not bent.

  Next, the recording medium P is sandwiched between the intermediate transfer drum 10 by the transfer device 16 and pressure is applied to the cured layer 12B, so that the cured layer 12B on which the image is formed by the ink droplets 14A is formed on the recording medium P. Transcribed.

  Next, the target layer 12B is cured by the stimulus supply device 18 so that the image T formed by the ink droplets 14A is fixed on the recording medium P by the curable resin. Thereby, a curable resin layer (image layer) including the image T by the ink droplet 14A is formed on the recording medium P.

  Then, the residue and foreign matter of the cured layer 12B remaining on the surface of the intermediate transfer drum 10 after the cured layer 12B is transferred to the recording medium P are removed by the cleaning device 20, and again on the intermediate transfer drum 10, The curable solution 12A is supplied by the solution supply device 12 to form the curable layer 12B, and the image recording process is repeated.

As described above, the recording apparatus 101 according to the present embodiment performs image recording.
The surface roughness of the surface of the curable resin layer (image layer) is preferably Rz of 10 μm or less, and more preferably 5 μm or less, from the viewpoint of obtaining a highly glossy image. Further, Rmax is preferably 20 μm or less, and more preferably 15 μm or less. The roughness Rz can be measured according to JIS-B0601 (1994), and the roughness Rmax can be measured according to JIS-B0601 (1982).

(Second Embodiment)
FIG. 2 is a configuration diagram illustrating a recording apparatus according to the second embodiment.

  As shown in FIG. 2, the recording apparatus 102 according to the second embodiment has a configuration in which an intermediate transfer belt 22 is disposed instead of the intermediate transfer drum 10 in the first embodiment.

  For example, the intermediate transfer belt 22 is rotatably supported by two support rolls 22A and a pressure roll 16B (transfer device 16) while applying tension from the inner peripheral surface side.

The intermediate transfer belt 22 has a width (length in the axial direction) equal to or greater than the width of the recording medium P.
The intermediate transfer belt 22 includes, for example, various resins [for example, polyimide, polyamideimide, polyester, polyurethane, polyamide, polyethersulfone, fluorine resin, and the like] and various rubbers (for example, nitrile rubber, ethylene propylene rubber, chloroprene). Rubber, isoprene rubber, styrene rubber, butadiene rubber, butyl rubber, chlorosulfonated polyethylene, urethane rubber, epichlorohydrin rubber, acrylic rubber, silicone rubber, fluorine rubber, etc.). The intermediate transfer belt 22 may be made of a metal material such as stainless steel. The intermediate transfer belt 22 may have a single layer configuration or a stacked configuration of two or more layers. The intermediate transfer belt 22 may have a surface layer made of a releasable and elastic material such as fluororesin and silicone rubber.

  Each recording head 14 is on a non-bent region of the intermediate transfer belt 22 that is rotationally supported under tension, and the distance between the surface of the intermediate transfer belt 22 and the nozzle surface of the head 14 is, for example, 0.7 to 1.5 mm. It is arranged to the extent.

  The transfer device 16 includes a pair of pressure rolls 16A and 16B arranged to face each other with the intermediate transfer belt 22 interposed therebetween.

  In the recording apparatus 102 according to the present embodiment, ink droplets 14 </ b> A are ejected by the inkjet recording head 14, and the ink droplets 14 </ b> A are applied to the cured layer 12 </ b> B formed on the intermediate transfer belt 22.

  At this time, the ejection of the ink droplets 14A by the ink jet recording head 14 is performed on a non-bent region in the intermediate transfer belt 22 that is rotated and supported by tension. That is, the ink droplets 14A are ejected to the cured layer 12B with the belt surface not deflected.

  Since other than these are the same as in the first embodiment, description thereof is omitted.

(Third embodiment)
FIG. 3 is a configuration diagram illustrating a recording apparatus according to the third embodiment.

  As shown in FIG. 3, the recording apparatus 103 according to the third embodiment is configured so that, in the first embodiment, before the layer to be cured 12 </ b> B formed with the ink droplets 14 </ b> A is transferred to the recording medium P, A second stimulus supply device 24 for supplying a stimulus for semi-curing the layer 12B is further arranged.

  For example, the second stimulus supply device 24 is disposed downstream of the inkjet recording head 14 in the rotation direction of the intermediate transfer drum 10 and upstream of the transfer device 16.

  Similar to the stimulus supply device 18, the second stimulus supply device 24 is selected according to the type of curable material contained in the curable solution 12 </ b> A to be applied. Specifically, for example, when an ultraviolet curable material is applied, the second stimulus supply device 24 is an ultraviolet irradiation device that irradiates the curable solution 12A (the cured layer 12B formed thereby) with ultraviolet rays. To do. Moreover, when applying an electron beam curable material, the electron beam irradiation apparatus which irradiates an electron beam to the curable solution 12A (cured layer 12B formed by this) as the 2nd stimulus supply apparatus 24 is applied. Further, when a thermosetting material is applied, a heat applying device that applies heat to the curable solution 12 </ b> A (the cured layer 12 </ b> B formed thereby) is applied as the second stimulus supply device 24.

  The ultraviolet irradiation conditions, electron beam irradiation conditions, and heat application conditions in the second stimulus supply device 24 are such that the cured layer 12B on the intermediate transfer drum 10 to which the ink droplets 14A are applied by the ink jet recording head 14 is changed from uncured to half. There is no particular limitation as long as it is a condition in which the image is transferred to the recording medium P by the transfer device 16 in a cured state, and can be selected according to the curable material type, the thickness of the layer to be cured, and the like.

  In the present embodiment, the second stimulus supply device 24 is arranged on the downstream side of the ink jet recording head 14 and the upstream side of the transfer device 16, but the second stimulus supply device 24 is arranged on the ink jet recording head. You may arrange | position upstream from 14. When the second stimulus supply device 24 is disposed on the upstream side of the ink jet recording head 14, after the cured layer 12 </ b> B is semi-cured to increase the viscosity, the ink droplet 14 </ b> A is ejected to the cured layer 12 </ b> B by the ink jet recording head 14. The Accordingly, since the diffusion of the ink droplets 14A in the cured layer 12B is further suppressed, a higher definition image is formed.

  Here, the “semi-cured state” means that the curable material has not reached the “sufficiently cured state”, but is cured more than when it is supplied to the intermediate transfer member and is not in a completely liquid state. State. One method for confirming the “semi-cured state” is as follows. Specifically, when permeable paper (for example, plain paper) is superimposed on the cured layer 12B, the cured layer 12B is not transferred to the paper side at all when no load is applied, and when a 200 g load is applied. When a part of the image is transferred, it is determined as a “half-cured state”. However, the load is easy to see and varies depending on the state of the contact area, the roll, the belt load state, and the like. Although it has the feature of improving transferability to paper by adhesive transfer in a semi-cured state, transfer / image forming ability can be achieved without increasing the curing rate if it has a certain level of retention after image formation even in an uncured state. Have.

  In the recording apparatus 103 according to the present embodiment described above, the ink droplets 14A are ejected by the ink jet recording head 14, and the ink droplets 14A are applied to the cured layer 12B supplied onto the intermediate transfer drum 10, and then the second. The stimulus supply device 24 semi-cures the layer 12B to be cured. Then, the cured layer 12B is transferred to the recording medium P by the transfer device 16. During this transfer, the cured layer 12B is transferred to the recording medium P in a semi-cured state, that is, in a state having some rigidity.

  Since other than these are the same as in the first embodiment, description thereof is omitted.

(Fourth embodiment)
FIG. 4 is a configuration diagram illustrating a recording apparatus according to the fourth embodiment.

  As shown in FIG. 4, the recording apparatus 104 according to the fourth embodiment has a form (direct recording method) in which an image is directly formed on a recording medium P.

  The recording device 104 supplies, for example, a curable solution 12A containing a curable material and water-absorbing resin particles that are cured on the recording medium P by an external stimulus (energy) and is formed of the curable solution 12A. The solution supply device 12 for forming the cured layer 12B, the inkjet recording head 14 for ejecting aqueous ink droplets 14A containing an aqueous solvent to form the image T on the cured layer 12B, and the stimulus for curing the cured layer 12B. And a stimulation supply device 18 for supply.

  The recording apparatus 104 includes a conveyance belt 13 that conveys the recording medium P. As the conveyance belt 13, for example, an endless belt similar to the intermediate transfer belt 22 in the second embodiment is used. For example, the transport belt 13 is rotatably supported by three support rolls 13A while applying tension from the inner peripheral surface side. The conveyor belt 13 conveys the recording medium P sent from a storage container (not shown) or the like in the direction of the arrow by rotating.

  In the recording apparatus 104, first, the solution supply apparatus 12 supplies the curable solution 12A on the surface of the recording medium P conveyed by the conveyance belt 13 to form the cured layer 12B. Next, based on predetermined image information, the ink droplets 14A are ejected by the ink jet recording head 14, and the image T is formed by applying the ink droplets 14A to the cured layer 12B formed on the recording medium P. Finally, the curable resin layer (image layer) including the image T formed by the ink droplets 14 </ b> A is formed on the recording medium P by curing the curable layer 12 </ b> B by the stimulus supply device 18.

  Since other than these are the same as in the first embodiment, description thereof is omitted.

  In any of the above-described recording apparatuses, the curable solution 12A is applied to the intermediate transfer drum 10, the intermediate transfer belt 22, or the recording medium P to form the curable layer 12B. Then, after applying the ink droplets 14A to the cured layer 12B to form the image T (in the first to third embodiments, after being further transferred to the recording medium P), the image T was formed. The cured layer 12B is completely cured. At this time, the curable material contained in the curable layer 12B is cured to become a “curable resin”. Therefore, regardless of whether the recording medium P is a non-penetrable medium or a permeable medium, image formation is performed on various recording media P.

  In particular, since the recording apparatus according to the first to third embodiments employs an intermediate transfer method, the object to be cured on the intermediate transfer body (intermediate transfer drum 10 and intermediate transfer belt 22) on which the image T is formed is used. The layer 12B undergoes a process of being transferred to the recording medium P. Therefore, for example, when the thickness of the curable layer 12B is set to such an extent that the ink droplets 14A do not reach the lowermost layer of the curable layer 12B, the curable layer 12B transferred to the recording medium P has a region where the ink droplets 14A exist ( The area where the image T is not exposed and the area where the ink droplets 14A are not present functions as a protective layer after curing, thereby improving the image storage stability.

  On the other hand, the recording apparatus according to the fourth embodiment employs a method (direct recording method) in which the curable solution 12A is directly supplied to the recording medium P, and thus has a simple configuration, higher speed, and lower cost. Thus, image formation is performed.

  In any of the recording apparatuses according to any of the above embodiments, the curable solution 12A contains a curable material that is cured by an external stimulus and water-absorbing resin particles having inorganic particles attached to the surface. The aqueous solvent contained in the aqueous ink droplet 14A is absorbed by the water-absorbing resin particles, and the ink droplet 14A received by the cured layer 12B is fixed in the cured layer 12B to form an image.

  Hereinafter, the curable material will be described.

  Examples of the curable material include an ultraviolet curable material, an electron beam curable material, and a thermosetting material. The UV curable material is easy to cure, has a faster curing speed than other materials, and is easy to handle. The electron beam curable material does not require a polymerization initiator, and it is easy to control the coloration of the cured layer. Thermoset materials are cured without the need for extensive equipment. In addition, a curable material is not restricted to these, For example, the curable material hardened | cured with moisture, oxygen, etc. can also be applied.

Examples of the “ultraviolet curable resin” obtained by curing the ultraviolet curable material include acrylic resin, methacrylic resin, urethane resin, polyester resin, maleimide resin, epoxy resin, oxetane resin, polyether resin, and polyvinyl ether resin. Etc.
Examples of the ultraviolet curable material that serves as the precursor of the ultraviolet curable resin include an ultraviolet curable monomer, an ultraviolet curable macromer, an ultraviolet curable oligomer, and an ultraviolet curable prepolymer.
The curable solution 12A desirably contains an ultraviolet polymerization initiator for causing the ultraviolet curing reaction to proceed. Furthermore, the curable solution 12A may contain a reaction aid, a polymerization accelerator, and the like for further proceeding the polymerization reaction as necessary.

  Here, examples of the ultraviolet curable monomer include alcohol / polyhydric alcohol / amino alcohol acrylic ester, alcohol / polyhydric alcohol methacrylate, acrylic aliphatic amide, acrylic alicyclic amide, acrylic aromatic Radical curable materials such as aromatic amides; and cationic curable materials such as epoxy monomers, oxetane monomers, and vinyl ether monomers. Examples of the ultraviolet curable macromer, the ultraviolet curable oligomer, and the ultraviolet curable prepolymer include those obtained by polymerizing these monomers at a predetermined polymerization degree, epoxy, urethane, polyester, polyether skeleton, acryloyl group, Examples include radical curable materials such as epoxy acrylate, urethane acrylate, polyester acrylate, polyether acrylate, urethane methacrylate, and polyester methacrylate to which a methacryloyl group is added.

When the curing reaction is a type that proceeds by radical reaction, examples of the ultraviolet polymerization initiator include benzophenone, thioxanthone, benzyl dimethyl ketal, α-hydroxyketone, α-hydroxyalkylphenone, α-aminoketone, α-aminoalkyl. Examples include phenone, monoacylphosphine oxide, bisacylphosphine oxide, hydroxybenzophenone, aminobenzophenone, titanocene type, oxime ester type, and oxyphenylacetate type.
When the curing reaction is a type that proceeds by a cationic reaction, examples of the ultraviolet polymerization initiator include arylsulfonium salts, aryldiazonium salts, diaryliodonium salts, triarylsulfonium salts, allene-ion complex derivatives, and triazine-based initiators. Etc.

Examples of the “electron beam curable resin” obtained by curing the electron beam curable material include acrylic resin, methacrylic resin, urethane resin, polyester resin, polyether resin, and silicone resin.
Examples of the electron beam curable material used as the precursor of the electron beam curable resin include an electron beam curable monomer, an electron beam curable macromer, an electron beam curable oligomer, and an electron beam curable prepolymer. Can be mentioned.

  Here, examples of the electron beam curable monomer, the electron beam curable macromer, the electron beam curable oligomer, and the electron beam curable prepolymer include the same materials as the ultraviolet curable material.

Examples of the “thermosetting resin” obtained by curing the thermosetting material include an epoxy resin, a polyester resin, a phenol resin, a melamine resin, a urea resin, and an alkyd resin.
Examples of the thermosetting material that serves as the precursor of the thermosetting resin include thermosetting monomers, thermosetting macromers, thermosetting oligomers, and thermosetting prepolymers.

Here, examples of the thermosetting monomer include polyalcohols such as phenol, formaldehyde, bisphenol A, epichlorohydrin, cyanuric amide, urea and glycerin, acids such as phthalic anhydride, maleic anhydride, and adipic acid. It is done. Examples of the thermosetting macromer, thermosetting oligomer, and thermosetting prepolymer include those obtained by polymerizing these monomers at a predetermined polymerization degree, epoxy prepolymers, and polyester prepolymers.
Further, a curing agent may be added during the polymerization.

  Further, the curable solution 12A may include a thermal polymerization initiator for causing the thermosetting reaction to proceed. Examples of the thermal polymerization initiator include acids such as protonic acid / Lewis acid, alkali catalysts, and metal catalysts.

As described above, the curable material may be anything as long as it is cured (for example, cured by the progress of the polymerization reaction) by external energy such as ultraviolet rays, electron beams, and heat.
Among the curable materials, a material having a high curing speed (for example, a material having a high polymerization reaction speed) is desirable in view of speeding up image recording. Examples of such a curable material include a radiation curable curable material (the above-described ultraviolet curable material, electron beam curable material, and the like).

  The curable material may be modified with Si, fluorine, or the like in consideration of wettability with the intermediate transfer member or the like. Moreover, it is desirable that the curable material contains a polyfunctional prepolymer in consideration of the curing speed and the degree of curing.

  Further, from the viewpoint of forming a high-definition image, it is desirable that the curable material has a small shrinkage due to the curing reaction. Furthermore, from the viewpoint of suppressing shrinkage due to the curing reaction, it is desirable that the curable material is not too flexible. The viscosity of the curable material is desirably 5 mPa · s or more.

  Next, the water absorbent resin particles will be described.

The water absorbent resin particles may be anything as long as they absorb an aqueous solvent.
Here, “absorbing an aqueous solvent” means that the liquid absorption is 100 ml / 100 g or more. “Liquid absorption” means the amount of liquid (ml) absorbed by 100 g of water absorbent resin particles, and is measured as follows.
Specifically, after leaving the water-absorbing resin particles in the water layer, wait until water penetrates the entire sample, immediately pull up the water-absorbing sample, leave it on the mesh for 5 minutes, measure the mass, and absorb the water. The difference from the resin particles was taken as the liquid absorption. Moreover, the method according to JISK5101-13-1 may be used.
Specifically, the liquid absorption amount of the water absorbent resin particles with respect to the aqueous solvent is desirably, for example, 100 ml / 100 g or more, and more desirably 200 ml / 100 g or more.

  The particle diameter (volume average particle diameter) of the water-absorbent resin particles is preferably in the range of 0.5 μm to 5 μm, and more preferably 0.5 μm to 3 μm.

  The volume average particle diameter is a volume average particle diameter measured using a particle size distribution analyzer (manufactured by NIKKSO) MT3200 using an aqueous dispersion of water absorbent resin particles and THF (tetrahydrofuran). The numerical value described in is a value measured by the method.

Specific examples of the water-absorbent resin particles include polyacrylic acid and sulfonic acid and salts thereof, polymethacrylic acid and salts thereof, and (meth) acrylic acid ester- (meth) acrylic acid and salts thereof. Copolymer, copolymer composed of styrene- (meth) acrylic acid and its salt, copolymer composed of styrene- (meth) acrylic ester- (meth) acrylic acid and its salt, styrene- (meth) A copolymer comprising an ester formed from an acrylate ester-carboxylic acid and an alcohol having an aliphatic or aromatic substituent having a salt structure thereof and (meth) acrylic acid, (meth) acrylate ester-carboxylic acid And an ester formed from an alcohol having an aliphatic or aromatic substituent having a salt structure thereof and (meth) acrylic acid Copolymer formed, ethylene- (meth) acrylic acid copolymer, butadiene- (meth) acrylic acid ester- (meth) acrylic acid and its salt, butadiene- (meth) acrylic acid A copolymer composed of an ester formed from an ester-carboxylic acid and an alcohol having an aliphatic or aromatic substituent having a salt structure thereof and (meth) acrylic acid, polymaleic acid and a salt thereof, styrene-maleic acid and Examples thereof include copolymers composed of the salts, sulfonic acid-modified products of the respective resins, phosphoric acid-modified products of the respective resins, and the like. Desirably, polyacrylic acid and a salt thereof, a copolymer composed of styrene- (meth) acrylic acid and a salt thereof, and a copolymer composed of styrene- (meth) acrylic acid ester- (meth) acrylic acid and a salt thereof. A copolymer composed of an ester produced from (meth) acrylic acid and an alcohol having an aliphatic or aromatic substituent having a styrene- (meth) acrylic acid ester-carboxylic acid and a salt structure thereof; And a copolymer composed of (meth) acrylic acid ester- (meth) acrylic acid and a salt thereof. These resins may be uncrosslinked or crosslinked.
In the crosslinked particles, the ink swellability can be limited by the degree of crosslinking, and image bleeding and thickening due to excess ink components, stability during line formation, and the like can be controlled. In addition, the non-crosslinked particles also increase the compatibility with the monomer, and even if the blending amount is suppressed, the ink component has excellent permeability between the stable image formation and the particles. These cross-linked particles and non-cross-linked particles may be used in combination, and have the advantage of being able to control image forming, density stability, and color mixing suppression ability according to the droplet ejection density, and the resin viscosity can also be adjusted The coating viscosity can be controlled to some extent by the blending ratio.

  Conventionally, when an uncrosslinked resin is used, swelling and ink deterioration due to ink permeation, compatibility with water-absorbent resin particles and reduction of ink permeation due to absorption of monomer components, decrease in density, and transfer It had drawbacks such as image deterioration and curability reduction. However, by adhering inorganic particles, which will be described later, to the surface, the affinity with the water-absorbing resin particles is suppressed and the ink spreading during ink ejection is prevented, so that the image quality on the intermediate transfer member can be improved. can get.

  These water-absorbing resin particles are produced by suspension polymerization, emulsion polymerization, solution polymerization, etc., and can be used as they are, subjected to pulverization processes such as ball mills, sand mills, freeze pulverization, and reprecipitation with solvents. Also good.

  The content of the water-absorbent resin particles is desirably in the range of 10 to 200 parts by mass with respect to 100 parts by mass of the curable material, and in the range of 10 to 50 parts by mass. Is particularly desirable.

  Next, inorganic particles will be described.

Examples of the inorganic particles attached to the surface of the water-absorbent resin particles include silica, titania, metatitanic acid, zinc oxide, zirconia, magnesia, calcium carbonate, magnesium carbonate, calcium phosphate, cerium oxide, strontium titanate, etc. Silica is preferred.
Of the silica, monodispersed spherical silica is particularly preferably used. Since monodispersed spherical silica is monodispersed and spherical, it can be suitably dispersed on the surface of the water-absorbent resin particles, and a stable spacer effect can be obtained. The definition of the monodispersion can be discussed in terms of the standard deviation with respect to the average particle diameter including aggregates, and the standard deviation is preferably number average particle diameter × 0.22 or less. Further, the definition of sphere can be discussed by Wadell's degree of sphericity, and the degree of sphericity is preferably 0.6 or more, and more preferably 0.8 or more.

  The monodispersed spherical silica can be obtained by a sol-gel method that is a wet method. The particle size can be freely controlled by the hydrolysis of the sol-gel method, the mass ratio of alkoxysilane, ammonia, alcohol, water in the condensation polymerization step, the reaction temperature, the stirring rate, and the supply rate. Monodisperse and spherical shapes can also be achieved by making this technique.

Specifically, tetramethoxysilane is dropped and stirred while applying temperature using ammonia water as a catalyst in the presence of water and alcohol. Next, the silica sol suspension obtained by the reaction is centrifuged to separate into wet silica gel, alcohol and aqueous ammonia. A solvent is added to wet silica gel to form a silica sol again, and a hydrophobizing agent is added to hydrophobize the silica surface. Next, the target monodispersed spherical silica can be obtained by removing the solvent from the hydrophobized silica sol, drying, and sieve. Further, the silica thus obtained may be treated again. Next, the solvent can be removed from the hydrophobized silica sol and dried.
In addition, the manufacturing method of the said silica is not limited to this manufacturing method.

Silica is preferably further surface-treated.
Dry methods such as spray drying, which sprays treatment agents or solutions containing treatment agents on particles suspended in the gas phase, and wet methods and treatments in which particles are immersed in a solution containing treatment agents and dried. It can process by the mixing method etc. which mix an agent and particle | grains with a mixer. Further, after the surface treatment, a step of washing with a solvent and removing a residual treatment agent or a low-boiling residue may be added.

  As the hydrophobizing agent, a general coupling agent, silicone oil, fatty acid, fatty acid metal salt, or the like can be used, but it is preferable to perform surface treatment including a silane coupling agent from the viewpoint of production stability. .

The said silane compound can use a water-soluble thing.
As such a silane compound, chemical structural formula R _a SiX _4-a (wherein, a is an integer of 0 to 3, R represents an organic group such as a hydrogen atom, an alkyl group, and an alkenyl group; Represents a hydrolyzable group such as a chlorine atom, a methoxy group, and an ethoxy group.), And any type of chlorosilane, alkoxysilane, silazane, and a special silylating agent is used. It is also possible.
Specifically, methyltrichlorosilane, dimethyldichlorosilane, trimethylchlorosilane, phenyltrichlorosilane, diphenyldichlorosilane, tetramethoxysilane, methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, diphenyldimethoxysilane, tetraethoxysilane, Methyltriethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane, diphenyldiethoxysilane, isobutyltrimethoxysilane, decyltrimethoxysilane, hexamethyldisilazane, N, O- (bistrimethylsilyl) acetamide, N, N-bis (Trimethylsilyl) urea, tert-butyldimethylchlorosilane, vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxy Silane, γ-methacryloxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-mercapto Representative examples include propyltrimethoxysilane and γ-chloropropyltrimethoxysilane.
As the hydrophobizing agent, dimethyldimethoxysilane, hexamethyldisilazane, methyltrimethoxysilane, isobutyltrimethoxysilane, and decyltrimethoxysilane are particularly preferable.

  Specific examples of silicone oil include, for example, organosiloxane oligomers; cyclic compounds such as octamethylcyclotetrasiloxane or decamethylcyclopentasiloxane, tetramethylcyclotetrasiloxane, tetravinyltetramethylcyclotetrasiloxane, Or a branched organosiloxane can be mentioned. Further, a highly reactive silicone oil in which a modifying group is introduced into a side chain or one end or both ends, a side chain piece end, or both side chain ends may be used. Examples of the modifying group include alkoxy, carboxyl, carbinol, higher fatty acid modification, phenol, epoxy, methacryl, amino and the like, but are not particularly limited. Further, it may be a silicone oil having several kinds of modifying groups such as amino / alkoxy modification.

  Further, dimethyl silicone oil, these modified silicone oils, and other surface treatment agents may be mixed or used in combination (such as silane coupling agents (including HMDS), etc.). ). Examples of the treating agent used in combination include silane coupling agents, titanate coupling agents, aluminate coupling agents, various silicone oils, fatty acids, fatty acid metal salts, esterified products thereof, rosin acid, and the like. .

In addition, as a method of hydrophilizing the silica surface, partial treatment by surface hydrophobization treatment with dimethyldichlorosilane, hexamethylsilazane, aminosilane, alkylsilane, octamethyltetracyclosiloxane, etc. using a silicone coupling treatment, Alternatively, a method of controlling the particle shape and hydrophilicity by mixing with untreated silica particles, a method of adjusting the compatibility by adding silicone oil, modified silicone oil or the like can be used.
Hydrophilic treatment agent, aminosilazane, anionic treatment agent such as cationic coupling carboxylic acid group with quaternary ammonium salt, etc., inorganic materials are mixed with aluminum hydroxide, sodium metaphosphate, zirconia, alumina and stearic acid And metal oxides such as titanium dioxide, zinc oxide, and magnesium oxide.

  In addition to the above, it is also preferable to perform treatment with a coupling agent having a fluorine functional group on the silica surface.

  In addition, as the silica to be adhered to the surface of the water-absorbent resin particles, it is preferable to adhere two or more kinds of silica subjected to different treatments among the above surface treatments. In particular, it is preferable to use two or more kinds of silica including silica subjected to the hydrophobic treatment and silica subjected to a hydrophilic treatment.

  As a method for adhering the inorganic particles to the surface of the water absorbent resin particles, (1) before preparing the curable solution 12A, the inorganic particles are added to the water absorbent resin particles in advance and stirred to obtain the surface of the water absorbent resin particles. (2) A method of adding (internally adding) inorganic particles in the stage of producing water-absorbing resin particles, (3) At the time of preparing the curable solution 12A, the curable material and the water-absorbing resin particles are combined. Examples of the method include adding inorganic particles when mixing. Among these, the method (1) is particularly preferable from the viewpoint of reliably adhering to the surface of the water-absorbent resin particles.

  Note that the background color of the obtained image can be adjusted by adjusting the color of the inorganic particles, and the color of the inorganic particles is preferably colorless, light or white.

  The particle size (average particle size) of the inorganic particles is preferably 5 μm or less, and more preferably 0.01 μm or more and 0.5 μm or less. In addition, the said particle size represents the volume average particle diameter measured using the particle size distribution measuring machine (product made from NIKKSO) MT3200 Coulter counter using the aqueous dispersion system of an inorganic particle and THF (tetrahydrofuran), and is described in this specification. Is a value measured by this method.

  As addition amount of the said inorganic particle, 0.1 mass% or more and 10 mass% or less are preferable with respect to a water-absorbent resin particle, and 0.1 mass% or more and 5 mass% or less are more preferable.

In addition to the curable material and the water-absorbing resin particles, the curable solution 12A includes other components (hereinafter referred to as “other immobilizing components”) that immobilize the ink components on or inside the cured layer 12B. May be included).
In this embodiment, water-absorbing resin particles and other immobilizing components are mixed in advance with the curable solution 12A. For example, a solution containing water-absorbing resin particles and other immobilizing components is separately prepared, Water-absorbing resin particles and other immobilizing components may be included in the cured layer 12B by ejecting the solution to the cured layer 12B by means of ejecting a solution or the like. The step of discharging the solution containing water-absorbing resin particles and other immobilization components to the curable layer 12B is desirably performed before the ink droplets 14A are discharged to the curable layer 12B by the inkjet recording head 14.

  Examples of the other immobilization component include, but are not limited to, a component that adsorbs an ink component (for example, a coloring material), a component that aggregates or thickens an ink component (for example, a coloring material), and the like. is not.

  Examples of components that adsorb ink components (for example, coloring materials) include silica, alumina, and zeolite. Examples of the ratio of the component include a range of about 0 to 30% by mass.

  Examples of the component that agglomerates or thickens the ink component (for example, the coloring material) include an aggregating agent such as an inorganic electrolyte, an organic acid, an inorganic acid, and an organic amine.

  Inorganic electrolytes include alkali metal ions such as lithium ion, sodium ion and potassium ion, and aluminum ion, barium ion, calcium ion, copper ion, iron ion, magnesium ion, manganese ion, nickel ion, tin ion, titanium ion and zinc. Polyvalent metal ions such as ions and organics such as hydrochloric acid, odorous acid, hydroiodic acid, sulfuric acid, nitric acid, phosphoric acid, thiocyanic acid, and acetic acid, succinic acid, lactic acid, fumaric acid, citric acid, salicylic acid, benzoic acid, etc. Examples thereof include carboxylic acids and salts of organic sulfonic acids.

  Specific examples include lithium chloride, sodium chloride, potassium chloride, sodium bromide, potassium bromide, sodium iodide, potassium iodide, sodium sulfate, potassium nitrate, sodium acetate, potassium oxalate, sodium citrate, potassium benzoate and the like. Alkali metal salts and aluminum chloride, aluminum bromide, aluminum sulfate, aluminum nitrate, sodium aluminum sulfate, potassium aluminum sulfate, aluminum acetate, barium chloride, barium bromide, barium iodide, barium oxide, barium nitrate, thiocyanate Barium acid, calcium chloride, calcium bromide, calcium iodide, calcium nitrite, calcium nitrate, calcium dihydrogen phosphate, calcium thiocyanate, calcium benzoate, calcium acetate, salicyl Calcium, calcium tartrate, calcium lactate, calcium fumarate, calcium citrate, copper chloride, copper bromide, copper sulfate, copper nitrate, copper acetate, iron chloride, iron bromide, iron iodide, iron sulfate, iron nitrate, oxalic acid Iron, iron lactate, iron fumarate, iron citrate, magnesium chloride, magnesium bromide, magnesium iodide, magnesium sulfate, magnesium nitrate, magnesium acetate, magnesium lactate, manganese chloride, manganese sulfate, manganese nitrate, manganese dihydrogen phosphate , Manganese acetate, manganese salicylate, manganese benzoate, manganese lactate, nickel chloride, nickel bromide, nickel sulfate, nickel nitrate, nickel acetate, tin sulfate, titanium chloride, zinc chloride, zinc bromide, zinc sulfate, zinc nitrate, thiocyanate Examples thereof include salts of polyvalent metals such as zinc acid and zinc acetate.

  Specific examples of organic acids include arginic acid, citric acid, glycine, glutamic acid, succinic acid, tartaric acid, cysteine, oxalic acid, fumaric acid, phthalic acid, maleic acid, malonic acid, lysine, malic acid, and general formula Examples thereof include compounds represented by (1) and derivatives of these compounds.

Here, in the formula, X represents O, CO, NH, NR ₁ , S, or SO ₂ . R ₁ represents an alkyl group, and R ₁ is preferably CH ₃ , C ₂ H ₅ , or C ₂ H ₄ OH. X is preferably CO, NH, NR ₁ , or O, and more preferably CO, NH, or O.
R represents an alkyl group, and R is preferably CH ₃ , C ₂ H ₅ , or C ₂ H ₄ OH. In addition, R may be included in the formula or may not be included.
M represents a hydrogen atom, an alkali metal or an amine. M is preferably H, Li, Na, K, monoethanolamine, diethanolamine, triethanolamine or the like, more preferably H, Na, or K, and still more preferably a hydrogen atom. n is an integer of 3 to 7. n is preferably a case where the heterocyclic ring is a 6-membered ring or a 5-membered ring, and more preferably a 5-membered ring. m is 1 or 2. The compound represented by the general formula (1) may be a saturated ring or an unsaturated ring as long as it is a heterocyclic ring. l is an integer of 1 to 5.

  Specifically, the compound represented by the general formula (1) has a furan, pyrrole, pyrroline, pyrrolidone, pyrone, pyrrole, thiophene, indole, pyridine, quinoline structure, and further has a carboxyl group as a functional group. Compounds. Specifically, 2-pyrrolidone-5-carboxylic acid, 4-methyl-4-pentanolide-3-carboxylic acid, furan carboxylic acid, 2-benzofuran carboxylic acid, 5-methyl-2-furan carboxylic acid, 2,5 -Dimethyl-3-furancarboxylic acid, 2,5-furandicarboxylic acid, 4-butanolide-3-carboxylic acid, 3-hydroxy-4-pyrone-2,6-dicarboxylic acid, 2-pyrone-6-carboxylic acid, 4-pyrone-2-carboxylic acid, 5-hydroxy-4-pyrone-5-carboxylic acid, 4-pyrone-2,6-dicarboxylic acid, 3-hydroxy-4-pyrone-2,6-dicarboxylic acid, thiophenecarboxylic Acid, 2-pyrrolecarboxylic acid, 2,3-dimethylpyrrole-4-carboxylic acid, 2,4,5-trimethylpyrrole-3-propionic acid, 3-hydroxy-2-yne Carboxylic acid, 2,5-dioxo-4-methyl-3-pyrroline-3-propionic acid, 2-pyrrolidinecarboxylic acid, 4-hydroxyproline, 1-methylpyrrolidine-2-carboxylic acid, 5-carboxy-1-methyl Pyrrolidine-2-acetic acid, 2-pyridinecarboxylic acid, 3-pyridinecarboxylic acid, 4-pyridinecarboxylic acid, pyridinedicarboxylic acid, pyridinetricarboxylic acid, pyridinepentacarboxylic acid, 1,2,5,6-tetrahydro-1-methyl Examples include nicotinic acid, 2-quinolinecarboxylic acid, 4-quinolinecarboxylic acid, 2-phenyl-4-quinolinecarboxylic acid, 4-hydroxy-2-quinolinecarboxylic acid, and 6-methoxy-4-quinolinecarboxylic acid. .

  As the organic acid, desirably, citric acid, glycine, glutamic acid, succinic acid, tartaric acid, phthalic acid, pyrrolidone carboxylic acid, pyrone carboxylic acid, pyrrole carboxylic acid, furan carboxylic acid, pyridine carboxylic acid, coumaric acid, thiophene carboxylic acid, Nicotinic acid, or derivatives of these compounds, or salts thereof. More desirably, pyrrolidone carboxylic acid, pyrone carboxylic acid, pyrrole carboxylic acid, furan carboxylic acid, pyridine carboxylic acid, coumaric acid, thiophene carboxylic acid, nicotinic acid, or derivatives of these compounds, or salts thereof. More desirable is pyrrolidone carboxylic acid, pyrone carboxylic acid, furan carboxylic acid, coumaric acid, or a compound derivative thereof, or a salt thereof.

  The organic amine compound may be any of primary, secondary, tertiary and quaternary amines and salts thereof. Specific examples include tetraalkylammonium, alkylamine, benzalkonium, alkylpyridium, imidazolium, polyamine, and derivatives or salts thereof. Specifically, amylamine, butylamine, propanolamine, propylamine, ethanolamine, ethylethanolamine, 2-ethylhexylamine, ethylmethylamine, ethylbenzylamine, ethylenediamine, octylamine, oleylamine, cyclooctylamine, cyclobutylamine, cyclohexane Propylamine, cyclohexylamine, diisopropanolamine, diethanolamine, diethylamine, di-2-ethylhexylamine, diethylenetriamine, diphenylamine, dibutylamine, dipropylamine, dihexylamine, dipentylamine, 3- (dimethylamino) propylamine, dimethylethylamine, dimethyl Ethylenediamine, dimethyloctylamine, 1,3-dimethylbutylamine, dimethyl 1,3-propanediamine, dimethylhexylamine, amino-butanol, amino-propanol, amino-propanediol, N-acetylaminoethanol, 2- (2-aminoethylamino) -ethanol, 2-amino-2- Ethyl-1,3-propanediol, 2- (2-aminoethoxy) ethanol, 2- (3,4-dimethoxyphenyl) ethylamine, cetylamine, triisopropanolamine, triisopentylamine, triethanolamine, trioctylamine, Tritylamine, bis (2-aminoethyl) 1,3-propanediamine, bis (3-aminopropyl) ethylenediamine, bis (3-aminopropyl) 1,3-propanediamine, bis (3-aminopropyl) methylamine, Bis (2-ethylhexyl ) Amine, bis (trimethylsilyl) amine, butylamine, butylisopropylamine, propanediamine, propyldiamine, hexylamine, pentylamine, 2-methyl-cyclohexylamine, methyl-propylamine, methylbenzylamine, monoethanolamine, laurylamine, Nonylamine, trimethylamine, triethylamine, dimethylpropylamine, propylenediamine, hexamethylesidiamine, tetraethylenepentamine, diethylethanolamine, tetramethylammonium chloride, tetraethylammonium bromide, dihydroxyethyl stearylamine, 2-heptadecenyl-hydroxyethylimidazoline, lauryl Dimethylbenzylammonium chloride, cetylpyridinium mouth Ride, stearamide methylbiridium chloride, diallyldimethylammonium chloride polymer, diallylamine polymer, monoallylamine polymer and the like can be mentioned.

  More desirably, triethanolamine, triisopropanolamine, 2-amino-2-ethyl-1,3-propanediol, ethanolamine, propanediamine, propylamine and the like are used.

Among these flocculants, polyvalent metal salts (Ca (NO ₃ ), Mg (NO ₃ ), Al (OH) ₃ , polyaluminum chloride and the like are preferably used.

  The flocculant may be used alone or in combination of two or more. Moreover, as content of a flocculant, the range of 0.01 mass% or more and 30 mass% or less is mentioned.

  Further, the curable solution 12A may contain water or an organic solvent for dissolving or dispersing main components (monomer, macromer, oligomer, prepolymer, polymerization initiator, etc.) that contribute to the curing reaction. . However, the ratio of the main component and the water-absorbent resin particles is, for example, 10% by mass or more, desirably 60% by mass or more, and more desirably 80% by mass or more.

  Further, the curable solution 12A may contain various color materials for the purpose of controlling the coloring of the cured layer.

  In addition, the curable solution 12A preferably contains a thermoplastic resin for the purpose of adjusting the viscosity. Examples of the thermoplastic resin include acrylic resins, urethane resins, polyester resins, polyols (polypropylene glycol, glycerol, trimethylpropanol, polyethers, polycarbonate, polystyrene, polyethylene, polypropylene, fluorine resin, synthetic rubbers, and the like. And a mixture thereof.

Note that the viscosity of the curable material 12A is 5 mPa · s or more and 30000 mPa · s or less from the viewpoint that the water-absorbent resin particles are well exposed on the surface of the curable layer 12B after the ink is discharged to the curable layer 12B. It is desirable that it is 10 mPa · s or more and 10,000 mPa · s or less. The viscosity of the curable solution 12A is preferably higher than the viscosity of the ink.
The above viscosity is a viscosity (mPa · s) measured at a shear rate of 2.25 to 750 (1 / s) and 15 ° C. using a TV-22 (manufactured by Toki Sangyo) as a viscometer. . The viscosity shear rate described in this specification is expressed as 10 s ⁻¹ .

  Moreover, the curable solution 12A containing a curable material is preferably low-volatile or nonvolatile at room temperature (25 ° C.). Here, low volatility means that the boiling point is 200 ° C. or higher under atmospheric pressure. Nonvolatile means that the boiling point is 300 ° C. or higher under atmospheric pressure. The same applies hereinafter.

  Hereinafter, the ink applied to the embodiment will be described.

  As the ink, an aqueous ink containing an aqueous solvent as a solvent is used. As the ink, an ultraviolet curable ink is also used.

  Examples of the water-based ink include an ink in which a water-soluble dye or pigment is dispersed or dissolved in an aqueous solvent as a recording material.

  First, the recording material will be described. As the recording material, a color material is mainly used. As the color material, either a dye or a pigment can be used, but a pigment is preferable. As the pigment, either an organic pigment or an inorganic pigment can be used. Examples of the black pigment include carbon black pigments such as furnace black, lamp black, acetylene black, and channel black. In addition to black, cyan, magenta and yellow primary pigments, special color pigments such as red, green, blue, brown and white, metallic luster pigments such as gold and silver, colorless or light body pigments, plastic pigments, etc. May be used. In addition, a newly synthesized pigment may be used for the present invention.

  Further, particles having silica, alumina, polymer beads or the like as a core and having a dye or pigment fixed on the surface thereof, an insoluble raked product of a dye, a colored emulsion, a colored latex, or the like can also be used as a pigment.

  Specific examples of black pigments include Raven7000, Raven5750, Raven5250, Raven5000 ULTRAII, Raven3500, Raven2000, Raven1500, Raven1250, Raven1200, Raven1125, Raven10, Raven10, Raven10 Regal 330R, Regal 660R, Mogul L, Black Pearls L, Monarch 700, Monarch 800, Monarch 880, Monarch 900, Monarch 1000, Monarch 1100, Monarch 1300, Monarch 140 0 (manufactured by Cabot Corporation), Color Black FW1, Color Black FW2, Color Black FW2V, Color Black 18, Color Black FW200, Color Black S150, Color Black P160, Color Black P160, Color Black FW2V, Color Black FW200, Color Black FW200 Printex 140V, Special Black 6, Special Black 5, Special Black 4A, Special Black 4 (manufactured by Degussa), No. 25, no. 33, no. 40, no. 47, no. 52, no. 900, no. 2300, MCF-88, MA600, MA7, MA8, MA100 (manufactured by Mitsubishi Chemical Corporation) and the like can be mentioned, but are not limited thereto.

  Specific examples of the cyan pigment include C.I. I. Pigment Blue-1, -2, -3, -15, -15: 1, -15: 2, -15: 3, -15: 4, -16, -22, -60, and the like. It is not limited.

  Specific examples of the magenta color pigment include C.I. I. Pigment Red-5, -7, -12, -48, -48: 1, -57, -112, -122, -123, -146, -168, -177, -184, -202, C.I. I. Pigment Violet-19 etc. are mentioned, However, It is not limited to these.

  Specific examples of yellow pigments include C.I. I. Pigment Yellow-1, -2, -3, -12, -13, -14, -16, -17, -73, -74, -75, -83, -93, -95, -97, -98, -114, -128, -129, -138, -151, -154, -180, and the like, but are not limited thereto.

  Here, when a pigment is used as the color material, it is desirable to use a pigment dispersant together. Examples of the pigment dispersant that can be used include a polymer dispersant, an anionic surfactant, a cationic surfactant, an amphoteric surfactant, and a nonionic surfactant.

  As the polymer dispersant, a polymer having a hydrophilic structure portion and a hydrophobic structure portion is preferably used. As the polymer having a hydrophilic structure portion and a hydrophobic structure portion, a condensation polymer and an addition polymer can be used. Examples of the condensation polymer include known polyester dispersants. Examples of the addition polymer include addition polymers of monomers having an α, β-ethylenically unsaturated group. Desired polymer dispersion by copolymerizing a monomer having an α, β-ethylenically unsaturated group having a hydrophilic group and a monomer having an α, β-ethylenically unsaturated group having a hydrophobic group An agent is obtained. A homopolymer of a monomer having an α, β-ethylenically unsaturated group having a hydrophilic group can also be used.

  Monomers having an α, β-ethylenically unsaturated group having a hydrophilic group include monomers having a carboxyl group, a sulfonic acid group, a hydroxyl group, a phosphoric acid group, such as acrylic acid, methacrylic acid, and crotonic acid. , Itaconic acid, itaconic acid monoester, maleic acid, maleic acid monoester, fumaric acid, fumaric acid monoester, vinyl sulfonic acid, styrene sulfonic acid, sulfonated vinyl naphthalene, vinyl alcohol, acrylamide, methacryloxyethyl phosphate, bismethacrylic acid Examples include roxyethyl phosphate, methacrylooxyethyl phenyl acid phosphate, ethylene glycol dimethacrylate, and diethylene glycol dimethacrylate.

  Examples of the monomer having an α, β-ethylenically unsaturated group having a hydrophobic group include styrene derivatives such as styrene, α-methylstyrene, vinyltoluene, vinylcyclohexane, vinylnaphthalene, vinylnaphthalene derivatives, alkyl acrylate esters, Examples include methacrylic acid alkyl esters, methacrylic acid phenyl esters, methacrylic acid cycloalkyl esters, crotonic acid alkyl esters, itaconic acid dialkyl esters, maleic acid dialkyl esters, and the like.

  Examples of desirable copolymers used as polymer dispersants include styrene-styrene sulfonic acid copolymers, styrene-maleic acid copolymers, styrene-methacrylic acid copolymers, styrene-acrylic acid copolymers, Vinyl naphthalene-maleic acid copolymer, vinyl naphthalene-methacrylic acid copolymer, vinyl naphthalene-acrylic acid copolymer, alkyl acrylate ester-acrylic acid copolymer, alkyl methacrylate ester-methacrylic acid copolymer, styrene -Methacrylic acid alkyl ester-Methacrylic acid copolymer, Styrene-Acrylic acid alkyl ester-Acrylic acid copolymer, Styrene-Methacrylic acid phenyl ester-Methacrylic acid copolymer, Styrene-Methacrylic acid cyclohexyl ester-Methacrylic acid copolymer Etc. . Moreover, you may copolymerize the monomer which has a polyoxyethylene group and a hydroxyl group with these polymers.

  Examples of the polymer dispersant include those having a weight average molecular weight of 2,000 to 50,000.

  These pigment dispersants may be used alone or in combination of two or more. The amount of the pigment dispersant added varies greatly depending on the pigment, so it cannot be generally stated.

  A pigment that can be self-dispersed in water can also be used as the color material. A pigment that is self-dispersible in water refers to a pigment that has many water-solubilizing groups on the pigment surface and disperses in water without the presence of a pigment dispersant. Specifically, it can be self-dispersed in water by subjecting ordinary so-called pigments to surface modification treatments such as acid / base treatment, coupling agent treatment, polymer graft treatment, plasma treatment, oxidation / reduction treatment, etc. Pigments are obtained.

  Further, as pigments that can be self-dispersed in water, in addition to pigments obtained by subjecting the above pigments to surface modification treatment, Cab-o-jet-200, Cab-o-jet-300, IJX- manufactured by Cabot Corporation Commercially available self-dispersing pigments such as 157, IJX-253, IJX-266, IJX-273, IJX-444, IJX-55, Cabot 260, Microjet Black CW-1, CW-2 manufactured by Orient Chemical Co., etc. can also be used.

  The self-dispersing pigment is preferably a pigment having at least sulfonic acid, sulfonate, carboxylic acid, or carboxylate as a functional group on the surface thereof. More desirably, the pigment has at least a carboxylic acid or a carboxylate as a functional group on the surface.

  Furthermore, a pigment coated with a resin can also be used. This is called a microcapsule pigment, and not only commercially available microcapsule pigments manufactured by Dainippon Ink and Chemicals, Inc., or Toyo Ink, but also microcapsule pigments produced for the present invention may be used. it can.

  Further, a resin-dispersed pigment in which a high molecular substance is physically adsorbed or chemically bonded to the pigment can also be used.

  Other recording materials include hydrophilic anionic dyes, direct dyes, cationic dyes, reactive dyes, dyes such as polymer dyes and oil-soluble dyes, wax powders / resin powders and emulsions colored with dyes, Fluorescent dyes and fluorescent pigments, infrared absorbers, ultraviolet absorbers, magnetic materials such as ferromagnetic materials represented by ferrite and magnetite, semiconductors and photocatalysts represented by titanium oxide and zinc oxide, and other organic and inorganic electrons Examples include material particles.

  The content (concentration) of the recording material is, for example, in the range of 5% by mass to 30% by mass with respect to the ink.

  Examples of the volume average particle diameter of the recording material include a range of 10 nm to 1000 nm.

  The volume average particle diameter of the recording material refers to the particle diameter of the recording material itself, or the particle diameter to which the additive has adhered when an additive such as a dispersant is attached to the recording material. A Microtrac UPA particle size analyzer 9340 (manufactured by Leeds & Northrup) was used as the volume average particle diameter measuring apparatus. The measurement was performed according to a predetermined measurement method with 4 ml of ink placed in a measurement cell. As input values at the time of measurement, the viscosity of the ink was used as the viscosity, and the density of the dispersed particles was used as the density of the recording material.

  Next, the aqueous solvent will be described. Examples of the aqueous solvent include water. In particular, ion exchange water, ultrapure water, distilled water, and ultrafiltered water are preferably used. A water-soluble organic solvent may be used together with the aqueous solvent. As the water-soluble organic solvent, polyhydric alcohols, polyhydric alcohol derivatives, nitrogen-containing solvents, alcohols, sulfur-containing solvents and the like are used.

  Specific examples of the water-soluble organic solvent include polyhydric alcohols such as ethylene glycol, diethylene glycol, propylene glycol, butylene glycol, triethylene glycol, 1,5-pentanediol, 1,2-hexanediol, 1,2, Examples thereof include sugar alcohols such as 6-hexanetriol, glycerin, trimethylolpropane, and xylitol, and sugars such as xylose, glucose, and galactose.

  Polyhydric alcohol derivatives include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monobutyl ether, dipropylene glycol monobutyl ether, diglycerin. And ethylene oxide adducts.

Examples of nitrogen-containing solvents include pyrrolidone, N-methyl-2-pyrrolidone, cyclohexyl pyrrolidone, and triethanolamine. Examples of alcohols include alcohols such as ethanol, isopropyl alcohol, butyl alcohol, and benzyl alcohol.
Examples of the sulfur-containing solvent include thiodiethanol, thiodiglycerol, sulfolane, dimethyl sulfoxide and the like.

  In addition, as the water-soluble organic solvent, propylene carbonate, ethylene carbonate, or the like can be used.

  One type of water-soluble organic solvent may be used, or two or more types may be used. As content of a water-soluble organic solvent, the range of 1 mass% or more and 70 mass% or less is mentioned, for example.

  Next, other additives will be described. In addition, a surfactant can be added to the ink as necessary.

  Examples of these surfactants include various anionic surfactants, nonionic surfactants, cationic surfactants, amphoteric surfactants, and the like. Desirably, anionic surfactants and nonionic surfactants are used. An activator is used.

Specific examples of the surfactant are listed below.
Examples of the anionic surfactant include alkylbenzene sulfonate, alkylphenyl sulfonate, alkylnaphthalene sulfonate, higher fatty acid salt, sulfate of higher fatty acid ester, sulfonate of higher fatty acid ester, sulfuric acid of higher alcohol ether. Ester salts and sulfonates, higher alkyl sulfosuccinates, polyoxyethylene alkyl ether carboxylates, polyoxyethylene alkyl ether sulfates, alkyl phosphates, polyoxyethylene alkyl ether phosphates can be used, preferably , Dodecylbenzenesulfonate, isopropylnaphthalenesulfonate, monobutylphenylphenol monosulfonate, monobutylbiphenylsulfonate, monobutylbiphenylsulfonate, dibutylphenylsulfonate Nord disulfonic acid salts and the like are used.

  Nonionic surfactants include polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyoxyethylene fatty acid esters, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene sorbitol fatty acid esters, glycerin fatty acid esters, poly Oxyethylene glycerin fatty acid ester, polyglycerin fatty acid ester, sucrose fatty acid ester, polyoxyethylene alkylamine, polyoxyethylene fatty acid amide, alkyl alkanolamide, polyethylene glycol polypropylene glycol block copolymer, acetylene glycol, polyoxyethylene adduct of acetylene glycol Desirably, polyoxyethylene nonyl pheny is preferable. Ether, polyoxyethylene octyl phenyl ether, polyoxyethylene dodecyl phenyl ether, polyoxyethylene alkyl ether, polyoxyethylene fatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, fatty acid alkylolamide, polyethylene glycol polypropylene glycol block copolymer Acetylene glycol and polyoxyethylene adducts of acetylene glycol are used.

  In addition, silicone surfactants such as polysiloxane oxyethylene adducts, fluorine surfactants such as perfluoroalkyl carboxylates, perfluoroalkyl sulfonates, and oxyethylene perfluoroalkyl ethers, spicrispolic acid and rhamnolipids Biosurfactants such as lysolecithin can also be used.

  These surfactants may be used alone or in combination. The hydrophilic / hydrophobic balance (HLB) of the surfactant is, for example, in the range of 3 to 20 in consideration of solubility.

  The amount of these surfactants added is, for example, in the range of 0.001 to 5 mass%, desirably 0.01 to 3 mass%.

  In addition, the ink has other properties such as penetrants for adjusting penetrability, polyethyleneimine, polyamines, polyvinyl pyrrolidone, polyethylene glycol, ethylcellulose, carboxymethylcellulose, etc. In order to adjust pH, compounds of alkali metals such as potassium hydroxide, sodium hydroxide, lithium hydroxide, etc., pH buffer, antioxidant, antifungal agent, viscosity adjuster, conductive agent as necessary UV absorbers, chelating agents, and the like can also be added.

Next, preferred characteristics of the ink will be described. First, the surface tension of the ink is, for example, in the range of 20 mN / m to 45 mN / m.
Here, as the surface tension, a value measured in an environment of 23 ° C. and 55% RH using a Wilhelmy type surface tension meter (manufactured by Kyowa Interface Science Co., Ltd.) was adopted.

The viscosity of the ink is 1.5 mPa · s or more and 30 mPa · s or less, preferably 1.5 mPa · s or more and 20 mPa · s or less. The viscosity of the ink is preferably lower than the viscosity of the curable solution.
Here, as the viscosity, a value measured using a rheomat 115 (manufactured by Contraves) as a measuring device under the conditions of a measurement temperature of 23 ° C. and a shear rate of 1400 s ⁻¹ was adopted.

  The ink is not limited to the above configuration. In addition to the recording material, for example, a functional material such as a liquid crystal material or an electronic material may be included.

  As described above, in the embodiment, the ink droplets 14A are selectively ejected based on the image data from the inkjet recording heads 14 of black, yellow, magenta, and cyan so that a full color image is recorded on the recording medium P. However, the present invention is not limited to recording characters and images on a recording medium. That is, the apparatus according to the present invention can be applied to all the droplet discharge (jetting) apparatuses used industrially.

  Hereinafter, an example is given and it demonstrates more concretely. However, it is not limited to these embodiments.

Example 1
Using a recording apparatus (see FIG. 2) having the same configuration as in the second embodiment, a curable solution is supplied to the intermediate transfer belt by a solution supply apparatus to form a cured layer, and recording is performed on the cured layer. Each ink was ejected by a head to form an image. Then, after the layer to be cured was transferred to the recording medium by the transfer device, the stimulus was supplied by the stimulus supply device, the layer to be cured was cured, printed, and evaluated. The conditions are as follows.

Intermediate transfer belt: a polyimide endless belt with a thickness of 0.1 mm, a belt width of 350 mm, and an outer diameter of Φ168 mm coated with a fluorine-based resin (process speed: 400 mm / s)
Solution supply device: Erichsen coater (coating gap of cured layer = 7 μm, film thickness 12 μm)
Each recording head: Piezo type recording head (resolution resolution 600 dpi (dpi: number of dots per inch, the same applies hereinafter))
Transfer device (pressure roll): A steel pipe with a diameter of 30 mm coated with a fluorine resin (pressing force against the intermediate transfer belt: 1 kG)
・ Stimulation supply device: 160W halogen lamp, 5 seconds ・ Recording media: Art paper (OK Kanfuji), plain paper (FX-P paper, manufactured by Fuji Xerox Co., Ltd.)

  Moreover, the curable solution and the ink of each color used what was produced as follows.

-Curing solution 1-
First, a silica particle Aerosil A130 (Japan, manufactured by Nippon Shokubai Co., Ltd., Aquaric cs7s, ball milled to a center particle diameter of 7 μm / water-absorbent resin particles) subjected to hydrophilization treatment is used. Aerosil (particle size: 16 nm) was externally mixed with a sample mill so as to be 2% by mass to obtain water-absorbing resin particles having silica attached to the surface.
Then
・ Silicone modified acrylic (manufactured by Toshiba Silicone Co., Ltd., HC1102 / curable material)
70 parts by weight ・ Acryloyl morphylin acrylate (manufactured by Kojin Co., Ltd., ACMO, curable material)
30 parts by mass of the material was mixed, and the water-absorbent resin particles having the silica adhered thereto were mixed so that the content with respect to the whole was 40% by mass. In this way, “curable solution 1” was obtained.

-Black ink 1-
Black pigment dispersion (Solsperse 13940 (manufactured by Noveon: dispersing agent) added to carbon black and dispersed in Isopar L) (pigment concentration 15% by mass): 40 parts by mass Isopar L (ExxonMobil, Inc.): 20 mass 26 parts by weight of ethyl oleate

  Isopar G (manufactured by ExxonMobil) and 5 parts by mass of oleyl alcohol were added to the above composition to adjust the viscosity to obtain “Black Ink 1”. The viscosity was 6.5 mPa · s.

-Cyan ink 1-
-Cyan pigment dispersion (Solsperse 16000 (manufactured by Noveon: dispersant) added to phthalocyanine pigment and dispersed in Isopar M) (pigment concentration: 10% by mass): 50 parts by mass-Isopar M (ExxonMobil, manufactured by): 20 mass Parts / soybean oil: 20 parts by mass

  Isopar G (manufactured by ExxonMobil) and 8 parts by mass of oleyl alcohol were added to the above composition to adjust the viscosity to obtain “Cyan Ink 1”. The viscosity was 7.5 mPa · s.

-Magenta ink 1-
・ Magenta pigment dispersion (Solsperse 34750 (manufactured by Noveon): Dispersant) is added to quinacridone pigment and dispersed in Isopar M) (pigment concentration 15% by mass): 30 parts by mass • Isozol (manufactured by Nippon Oil Corporation): 12 mass Parts / ethyl soybean oil: 15 parts by mass / oleyl alcohol: 30 parts by mass

Isopar G (manufactured by ExxonMobil) and 10 parts by mass of oleyl alcohol were added to the above composition to adjust the viscosity to obtain “magenta ink 1”. The viscosity was 8.8 mPa · s.

-Yellow ink 1-
・ Yellow pigment dispersion (Pigment Yellow 74 with Disperbyk
-101 (by Big Chemie: Dispersant added and dispersed in Isopar G) (pigment concentration 18% by mass): 25 parts by mass, Isopar M (ExxonMobil, Inc.): 40 parts by mass, butyl oleate: 15 parts by mass

  Isopar G (manufactured by ExxonMobil) and 5 parts by mass of oleyl alcohol were added to the above composition to adjust the viscosity to obtain “Yellow Ink 1”. The viscosity was 6.7 mPa · s.

  The “curable solution 1” was coated on the intermediate transfer belt by an Erichsen coater with a coating gap of 7 μm to form a “cured layer” having a thickness of 12 μm. Thereafter, the four inks were printed on the “cured layer” by the recording head (resolution: 600 dpi). After that, the intermediate transfer belt and art paper (OK Kanto) and plain paper (FX-P paper, manufactured by Fuji Xerox Co., Ltd.) are brought into close contact with each other, and the “cured layer” is roll-pressure-transferred onto the art paper and plain paper at a load of 1 kG. The paper was cured by UV irradiation with a 160 W halogen lamp for 5 seconds to form an image.

(Example 2)
In Example 1, Aerosil A130 (inorganic particles) used for the curable solution 1 was changed to “Silica particles R972 hydrophobized with silicone oil (manufactured by Nippon Aerosil Co., Ltd., particle size 16 nm)” and HC1102 (curable material). Is changed to “silicone-modified acrylic (manufactured by Toshiba Silicone, HC1101 / curable material)”, and ACMO (curable material) is changed to “PEG400 diacrylate (manufactured by Daicel)”, by the method described in Example 1. A curable solution was obtained.
Further, an image was formed by the method described in Example 1 except that the coating gap by the Erichsen coater was changed to 12 μm and the film thickness was changed to 23 μm.

(Example 3)
In Example 1, Aerosil A130 (inorganic particles) used for the curing agent solution 1 was mixed with 50% by mass of “Aerosil A130 and RX200 hydrophobized with hexamethylsilazane (made by Nippon Aerosil Co., Ltd., particle size 12 nm). A cured solution was obtained by the method described in Example 1 except for changing to “thing”. This was applied to form an image having a film thickness of 18 μm.

(Comparative Example 1)
A curable solution was obtained by the method described in Example 1 except that Aerosil A130 (inorganic particles) was not used in Example 1.
Moreover, as a coating method of the curable solution, an image was formed by the method described in Example 1 except that after spreading the liquid at a thickness of 7 μm, particle dispersal spraying was performed and the film thickness was changed to 10 μm.

[Evaluation]
-Measurement of surface gloss G75 °-
(Murakami Color Giken Co., Ltd.) Using a digital precision gloss meter, the surface gloss (unit: gloss) of the formed image (after curing) at an incident angle of 75 ° was measured.

-Measurement of surface roughness Rz and Rmax-
By the above-described method, the surface roughness Rz and Rmax of the formed image (after curing) were measured.

-Measurement of contact angle-
The contact angle of water on the surface was measured with a contact angle meter CA-X (manufactured by Kyowa Interface Science).

-Transfer efficiency-
The transfer efficiency (%) of the cured layer to the recording medium was measured by the following method.
The mass of the intermediate transfer belt per unit area (10 × 10 cm) is measured in advance, and is obtained from the mass of the coating film when the curable solution is applied thereon, and the mass of the intermediate transfer belt after being transferred to a sheet and cured. It was.

-Evaluation of printing unevenness-
The degree of occurrence of printing unevenness in the formed image was evaluated according to the following criteria.
○: The density of the image patch is measured, and there is little in-plane density unevenness at 3 locations (parts with different droplet ejection densities) (0.05 or less)
Δ: The density of the image patch is measured and the density unevenness is 0.1 or less. X: The density of the image patch is measured and the density unevenness exceeds 0.1.

1 is a configuration diagram illustrating a recording apparatus according to a first embodiment. It is a block diagram which shows the recording device which concerns on 2nd Embodiment. It is a block diagram which shows the recording device which concerns on 3rd Embodiment. It is a block diagram which shows the recording device which concerns on 4th Embodiment.

Explanation of symbols

DESCRIPTION OF SYMBOLS 10 Intermediate transfer drum 12 Solution supply apparatus 12A Curing solution 12B Curing layer 12C Case 12D Supply roller 12E Blade 13 Conveying belt 13A Support roll 14 Inkjet recording head 16 Transfer apparatus 16A Pressure roll 16B Pressure roll 18 Stimulation supply apparatus 20 Cleaning device 22 Intermediate transfer belt 22A Support roll 24 Second stimulus supply device 101 Recording device 102 Recording device 103 Recording device 104 Recording device

Claims (7)

In an image recording method of recording an image by supplying a stimulus after ejecting ink to a liquid cured layer to cure the cured layer and being used as a liquid for forming the cured layer,
An image recording liquid comprising: a curable material that is cured by an external stimulus; and water-absorbing resin particles having inorganic particles attached to a surface thereof.   The image recording liquid according to claim 1, wherein the inorganic particles are silica particles.   The image recording liquid according to claim 1, wherein the inorganic particles are inorganic particles whose surfaces have been subjected to a hydrophobic treatment.   The image recording liquid according to claim 1, wherein the inorganic particles are inorganic particles whose surfaces have been subjected to a hydrophilic treatment.   The liquid for image recording according to claim 3 or 4, wherein at least two kinds of inorganic particles whose surfaces are hydrophobized and inorganic particles whose surfaces are hydrophilized are used. An intermediate transfer member;
Supply means for supplying the image recording liquid according to any one of claims 1 to 5 onto the intermediate transfer member;
Discharging means for discharging aqueous ink containing an aqueous solvent to a liquid cured layer formed of the image recording liquid supplied on the intermediate transfer member;
Transfer means for transferring the cured layer onto which the water-based ink has been discharged from the intermediate transfer member to a recording medium;
A stimulus supply means for supplying a stimulus for curing the cured layer;
A recording apparatus. Supply means for supplying the image recording liquid according to any one of claims 1 to 5 onto a recording medium;
Discharging means for discharging aqueous ink containing an aqueous solvent to a liquid cured layer formed of the image recording liquid supplied on the recording medium;
A stimulus supply means for supplying a stimulus for curing the cured layer;
A recording apparatus.