WO2016190410A1 - 記録物及び画像形成方法 - Google Patents

記録物及び画像形成方法 Download PDF

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Publication number
WO2016190410A1
WO2016190410A1 PCT/JP2016/065687 JP2016065687W WO2016190410A1 WO 2016190410 A1 WO2016190410 A1 WO 2016190410A1 JP 2016065687 W JP2016065687 W JP 2016065687W WO 2016190410 A1 WO2016190410 A1 WO 2016190410A1
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WO
WIPO (PCT)
Prior art keywords
toner particles
toner
image
curable liquid
ether
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2016/065687
Other languages
English (en)
French (fr)
Japanese (ja)
Inventor
徹 椛島
修平 ▲高▼橋
田村　修一
信一郎 吉川
俊彦 杉本
エリト 町田
伊藤　淳二
石塚　二郎
中山　雄二
幸司 雨宮
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Canon Inc
Original Assignee
Canon Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Canon Inc filed Critical Canon Inc
Priority to CN201680030737.5A priority Critical patent/CN107710077B/zh
Priority to EP16800114.7A priority patent/EP3306401B1/en
Publication of WO2016190410A1 publication Critical patent/WO2016190410A1/ja
Priority to US15/386,645 priority patent/US10372053B2/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G9/00—Developers
    • G03G9/08—Developers with toner particles
    • G03G9/0825—Developers with toner particles characterised by their structure; characterised by non-homogenuous distribution of components
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B3/00—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form
    • B32B3/10—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by a discontinuous layer, i.e. formed of separate pieces of material
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G13/00—Electrographic processes using a charge pattern
    • G03G13/06—Developing
    • G03G13/10—Developing using a liquid developer, e.g. liquid suspension
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G15/00—Apparatus for electrographic processes using a charge pattern
    • G03G15/06—Apparatus for electrographic processes using a charge pattern for developing
    • G03G15/08—Apparatus for electrographic processes using a charge pattern for developing using a solid developer, e.g. powder developer
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G9/00—Developers
    • G03G9/08—Developers with toner particles
    • G03G9/0819—Developers with toner particles characterised by the dimensions of the particles
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G9/00—Developers
    • G03G9/08—Developers with toner particles
    • G03G9/0827—Developers with toner particles characterised by their shape, e.g. degree of sphericity
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G9/00—Developers
    • G03G9/08—Developers with toner particles
    • G03G9/087—Binders for toner particles
    • G03G9/08702—Binders for toner particles comprising macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • G03G9/08722—Polyvinylalcohols; Polyallylalcohols; Polyvinylethers; Polyvinylaldehydes; Polyvinylketones; Polyvinylketals
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G9/00—Developers
    • G03G9/08—Developers with toner particles
    • G03G9/09—Colouring agents for toner particles
    • G03G9/0906—Organic dyes
    • G03G9/0918—Phthalocyanine dyes
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G9/00—Developers
    • G03G9/08—Developers with toner particles
    • G03G9/12—Developers with toner particles in liquid developer mixtures
    • G03G9/122—Developers with toner particles in liquid developer mixtures characterised by the colouring agents
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G9/00—Developers
    • G03G9/08—Developers with toner particles
    • G03G9/12—Developers with toner particles in liquid developer mixtures
    • G03G9/125—Developers with toner particles in liquid developer mixtures characterised by the liquid
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G9/00—Developers
    • G03G9/08—Developers with toner particles
    • G03G9/12—Developers with toner particles in liquid developer mixtures
    • G03G9/13—Developers with toner particles in liquid developer mixtures characterised by polymer components
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G9/00—Developers
    • G03G9/08—Developers with toner particles
    • G03G9/12—Developers with toner particles in liquid developer mixtures
    • G03G9/13—Developers with toner particles in liquid developer mixtures characterised by polymer components
    • G03G9/132—Developers with toner particles in liquid developer mixtures characterised by polymer components obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G9/00—Developers
    • G03G9/08—Developers with toner particles
    • G03G9/12—Developers with toner particles in liquid developer mixtures
    • G03G9/135—Developers with toner particles in liquid developer mixtures characterised by stabiliser or charge-controlling agents
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G9/00—Developers
    • G03G9/08—Developers with toner particles
    • G03G9/12—Developers with toner particles in liquid developer mixtures
    • G03G9/135—Developers with toner particles in liquid developer mixtures characterised by stabiliser or charge-controlling agents
    • G03G9/1355—Ionic, organic compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G2215/00—Apparatus for electrophotographic processes
    • G03G2215/01—Apparatus for electrophotographic processes for producing multicoloured copies
    • G03G2215/0103—Plural electrographic recording members
    • G03G2215/0119—Linear arrangement adjacent plural transfer points
    • G03G2215/0122—Linear arrangement adjacent plural transfer points primary transfer to an intermediate transfer belt
    • G03G2215/0125—Linear arrangement adjacent plural transfer points primary transfer to an intermediate transfer belt the linear arrangement being horizontal or slanted
    • G03G2215/0129—Linear arrangement adjacent plural transfer points primary transfer to an intermediate transfer belt the linear arrangement being horizontal or slanted horizontal medium transport path at the secondary transfer
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
    • Y10T428/24802—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
    • Y10T428/24802—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.]
    • Y10T428/24893—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.] including particulate material
    • Y10T428/24901—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.] including particulate material including coloring matter

Definitions

  • the present invention relates to a recorded matter and an image forming method.
  • Patent Document 1 discloses a technique for improving the fixability by pressing and heating a recording liquid (developer) with a heat roller before curing with ultraviolet light.
  • the object of the present invention is made in view of the above problems, and the toner image (recording liquid) is sufficiently fixed on the recording medium even when high speed image formation is performed, and sufficient saturation and lightness Providing a recorded matter having a toner image of Another object of the present invention is to provide an image forming method by which such recorded matter can be obtained.
  • the present invention recoding media, Toner particles containing colorant particles, and A recorded matter comprising a cured resin which contains the toner particles and fixes a toner image constituted of the toner particles on the recording medium.
  • the average circularity of the toner particles is 0.70 or more and 0.99 or less, The toner particles are not exposed from the surface of the cured resin,
  • the recording material is characterized in that the average distance between wall surfaces of the adjacent toner particles is 10 nm or more and less than 125 nm.
  • the present invention is An electrostatic latent image forming step of forming an electrostatic latent image on an image carrier; Developing the electrostatic latent image with a recording liquid containing toner particles containing an colorant particle and an energy curable liquid, thereby forming a toner image composed of the toner particles on an image carrier; A transfer step of transferring the toner image composed of the toner particles and the energy curable liquid onto the recording medium from the image carrier; It is an image forming method including a fixing step of fixing the toner image on the recording medium without applying pressure by applying energy to the energy curable liquid and curing the energy curable liquid.
  • FIG. 1 is a schematic view of an image forming apparatus according to a first embodiment.
  • FIG. 1 is a schematic view of a fixing device according to a first embodiment.
  • FIG. 2 is a cross-sectional conceptual diagram before fixing according to Embodiment 1.
  • FIG. 2 is a cross-sectional conceptual view after fixing according to Embodiment 1.
  • (A) to (c) are cross-sectional conceptual diagrams showing the dispersibility of the pigment contained in toner particles according to Examples.
  • FIG. 6 is an exposed cross-sectional view of toner particles according to Comparative Example 1;
  • A A cross-sectional conceptual diagram showing an embodiment in which toner particles contain a pigment
  • (b) a conceptual diagram showing an embodiment in which a pigment is directly dispersed in a cured resin
  • (c) (A) and (b) are cross-sectional conceptual diagrams comparing the shapes of toner particles.
  • (A) to (c) are conceptual diagrams of the distance between wall surfaces of toner particles according to Embodiment 2.
  • FIG. (A) to (c) are conceptual diagrams of colorant particle distance according to Example 2.
  • FIG. It is a figure which shows the experimental data of lightness and saturation.
  • FIG. 6 is a view showing the relationship between the average of the distance between wall surfaces of toner particles and the saturation.
  • FIG. 6 is a view showing the influence of the average of the distance between wall surfaces of toner particles on the spectral reflectance.
  • the descriptions of “more than or equal to or less than xxx” or “ ⁇ to xxx” representing a numerical range mean a numerical range including the lower limit and the upper limit which are endpoints, unless otherwise noted.
  • the recorded matter of the present invention is recoding media, Toner particles containing colorant particles, and A recorded matter comprising a cured resin which contains the toner particles and fixes a toner image constituted of the toner particles on the recording medium.
  • the average circularity of the toner particles is 0.70 or more and 0.99 or less, The toner particles are not exposed from the surface of the cured resin,
  • the average distance between wall surfaces of adjacent toner particles is 10 nm or more and less than 125 nm.
  • the image forming method of the present invention is An electrostatic latent image forming step of forming an electrostatic latent image on an image carrier; Developing the electrostatic latent image with a recording liquid containing toner particles containing an colorant particle and an energy curable liquid, thereby forming a toner image composed of the toner particles on an image carrier; A transfer step of transferring the toner image composed of the toner particles and the energy curable liquid onto the recording medium from the image carrier; The method may further include a fixing step of fixing the toner image on the recording medium without applying pressure by applying energy to the energy curable liquid and curing the energy curable liquid.
  • the recording liquid (and the energy curable liquid contained in the recording liquid) preferably contains a cationically polymerizable monomer.
  • FIG. 1 is an example of an image forming apparatus using the image forming method of the present invention, and is a schematic view of an image forming apparatus according to a first embodiment described later. More specifically, FIG. 1 is a cross-sectional view (schematic view) of a printer adopting an electrophotographic method, which is a type of image forming apparatus, and is a cross-sectional view along the sheet conveyance direction. In the following description, a printer adopting an electrophotographic method is also referred to simply as a "printer".
  • FIG. 1 is a schematic view (cross-sectional view) of the image forming apparatus according to the first embodiment
  • FIG. 2 is a schematic view (cross-sectional view) of the fixing device according to the first embodiment.
  • Y, M, C and K respectively mean for yellow, magenta, cyan and black.
  • Y, M, C and K in the code may be omitted.
  • the image forming apparatus 100 has a photosensitive drum (electrophotographic photosensitive member) 20 as an image carrier, and around the photosensitive drum 20, a charging device (primary charger) 30, a developing device, a transfer device (intermediate transfer belt) ) And a cleaning device are arranged.
  • the recording medium 16 is supplied to the contact portion (transfer nip portion) between the transfer device and the photosensitive drum 20 at an appropriate timing.
  • each photosensitive drum 20 (20Y, 20M, 20C, 20K) is 84 mm.
  • Each photosensitive drum 20 is rotationally driven at a circumferential speed (process speed) of 750 mm / sec in the direction of arrow A in FIG. Then, the surface of each photosensitive drum 20 is uniformly charged by the charging device 30 in the process of rotating. Then, an electrostatic latent image separated into each color corresponding to the image exposure pattern is formed on the surface of each photosensitive drum 20 by the exposure light 40 irradiated from the exposure device (not shown) (electrostatic latent image Formation process).
  • the developing device has a recording liquid containing negatively charged (negatively charged) toner particles and an energy curable liquid (carrier liquid), carries the recording liquid on the developing sleeve and conveys it to the photosensitive drum 20.
  • the toner particles in the recording liquid are caused to adhere to the electrostatic latent image on the photosensitive drum 20 by the developing electric field formed by the voltage (developing bias) applied to the developing sleeve and the surface potential of the photosensitive drum 20, and electrostatic latent
  • the image is visualized as a toner image (development step).
  • the toner image is primarily transferred onto the intermediate transfer belt 70 at the contact portion 60 between the photosensitive drum 20 and the primary transfer roller 61.
  • the recording medium 16 is carried by the conveyance belt 80 and supplied to the contact portion between the intermediate transfer belt 70 and the secondary transfer outer roller 81 at an appropriate timing.
  • the secondary transfer inner roller 86 is opposed to the secondary transfer outer roller 81 via the intermediate transfer belt 70 (and the recording medium 16).
  • the toner image is secondarily transferred from the intermediate transfer belt 70 onto the recording medium 16.
  • the toner image composed of toner particles and the energy curable liquid are transferred from the photosensitive drum 20 onto the recording medium 16 (transfer step).
  • the recording medium 16 carrying the recording liquid 15 containing the unfixed toner image and the energy curable liquid is conveyed by the conveyance belt 80 to the irradiation position of the irradiation device 11 which is a fixing device.
  • the energy curable liquid is cured by the heat from the pretreatment device (not shown) for promoting the curing reaction of the energy curable liquid and the energy of the ultraviolet light irradiated from the irradiation device 11 to become a cured resin.
  • the unfixed toner image is fixed on the recording medium 16 by the cured resin (fixing step).
  • the fixing step the toner image is fixed on the recording medium without pressure.
  • the recording medium 16 is discharged out of the image forming apparatus.
  • the pretreatment device may not be used depending on the curability of the energy curable liquid. In the present invention, it is preferable not to heat in the fixing step.
  • the temperature in the fixing step is preferably equal to or less than the glass transition temperature (Tg) from the viewpoint of preventing deformation of the toner particles.
  • Tg glass transition temperature
  • the energy curable liquid is an ultraviolet curable liquid
  • the fixing step irradiates the energy curable liquid with ultraviolet rays to cure the energy curable liquid, thereby applying a toner image without pressure.
  • FIG. 1 is a schematic diagram taking four stations as an example, the present invention can also be applied to one station or a plurality of color imaging systems.
  • the recording liquid contains toner particles and an energy curable liquid (carrier liquid).
  • FIG. 3 is a cross-sectional view of a toner particle (constituted toner image) and an energy curable liquid after being transferred onto a recording medium and before being fixed.
  • the toner particles 301 contain colorant particles 303 that emit a color. Further, the toner particles 301 contain a binder resin (toner resin) 305 for binding the colorant particles 303. Further, the toner particles 301 may contain other materials such as a charge control agent (not shown) as well as the binder resin 305 and the colorant particles 303.
  • the method for producing toner particles 301 includes coacervation in which colorant particles are dispersed, monomers for binder resin are gradually polymerized, and toner particles are formed while encapsulating colorant particles in toner particles. Be Alternatively, a method such as a pulverization method may be used in which the binder resin or the like is melted and the colorant particles are contained inside the binder resin.
  • Example 1 The developer production method of Example 1 is shown below.
  • 39.6 parts by mass of an ⁇ -caprolactone self-polycondensate having a number average molecular weight of 8500 having a carboxyl group at the terminal is charged and held at about 80 ° C. for 2 hours to react the carbodiimide group with the carboxyl group,
  • the toluene is distilled off to obtain a pigment dispersant (solid content 100%) having a number average molecular weight of about 13,000.
  • ⁇ Pigment dispersion process 10 parts by mass of pigment (carbon black MA-7; manufactured by Mitsubishi Chemical Co., Ltd.), 10 parts by mass of pigment dispersant, 80 parts by mass of solvent (tetrahydrofuran, THF): 80 parts by mass are mixed, and paint shaker is used using steel beads of 5 mm in diameter The mixture was kneaded for 1 hour to obtain a kneaded product 1.
  • pigment carbon black MA-7; manufactured by Mitsubishi Chemical Co., Ltd.
  • solvent tetrahydrofuran, THF
  • Kneaded material 1 60 parts by mass, polyester resin 1 [(molar ratio); polyoxypropylene (2.0) -2,2-bis (4-hydroxyphenyl) propane: terephthalic acid: trimellit obtained above Acid: 50: 40: 10, Tg: 59 ° C., Tm: 105 ° C., SP value: 11.2 (cal / cm 3 ) 1/2 , acid value: 18 KOH mg / g, weight average molecular weight: 2.5 ⁇ 10 4 ] 50% THF solution: 80 parts by mass, Toner particle dispersant (Aispar PB-817; manufactured by Ajinomoto Co., Ltd.): 12 parts by mass, a high-speed dispersing machine (manufactured by Primix, T.K. Robotics / T.K. The mixture was mixed with a homodisper 2.5 type wing and mixed at 40 ° C. with stirring to obtain a pigment dispersion 1.
  • ⁇ Mixing process> A small amount of 200 parts by mass of dodecyl vinyl ether (DDVE) was added to the pigment dispersion liquid 1 (100 parts by mass) obtained above while stirring at high speed (rotation number 25000 rpm) using a homogenizer (manufactured by IKA: UltraTarax T50) Each mixture was added to obtain mixed solution 1. At the end of the mixing step, the binder resin was in a state of phase separation.
  • DDVE dodecyl vinyl ether
  • ⁇ Liquid developer preparation process> The obtained toner particle dispersion 1 (10 parts by mass) is subjected to centrifugation, and the supernatant liquid is removed by decantation, replaced with fresh DDVE having the same mass as the removed supernatant liquid, redispersed, and resorcile S 0.10 parts by mass of hydrogenated lecithin (manufactured by Nikko Chemicals Co., Ltd.), 10 parts by mass of dodecyl vinyl ether as a polymerizable liquid monomer, 80 parts by mass of cyclohexane dimethanol divinyl ether, represented by the following formula (A-1) 0.30 parts by mass of a photopolymerization initiator and 1 part by mass of KAYAKURE-DETX-S (manufactured by Nippon Kayaku Co., Ltd.) were added to obtain an ultraviolet-curable liquid developer 1. The time required for production was less than 12 hours.
  • binder resin used for the toner particles examples include polyester resin, epoxy resin, styrene acrylic resin, and the like.
  • colorant particles used for the toner particles general organic or inorganic pigments can be used. Further, in order to enhance the dispersibility of toner particles, a dispersant can be used in the production process, and a synergist can also be used.
  • the content of the colorant in the toner particles is preferably 5 parts by mass or more and 100 parts by mass or less with respect to 100 parts by mass of the binder resin.
  • the pigment include carbon black. Moreover, the following are mentioned as a pigment which exhibits a blue or cyan color. C. I. Pigment blue 2, 3, 15: 2, 15: 3, 15: 4, 16, 17; C.I.
  • the toner particles preferably contain a pigment dispersant. It is also possible to use a synergist corresponding to various pigments as a dispersion aid.
  • the preferred pigment dispersant and pigment dispersion aid content is 0.01 to 50% by mass in the toner particles.
  • the pigment dispersant known ones can be used.
  • hydroxyl group-containing carboxylic acid ester, salt of long chain polyaminoamide and high molecular weight acid ester, salt of high molecular weight polycarboxylic acid, high molecular weight unsaturated examples thereof include acid esters, polymer copolymers, modified polyacrylates, aliphatic polyvalent carboxylic acids, naphthalene sulfonic acid formalin condensates, polyoxyethylene alkyl phosphate esters, and pigment derivatives.
  • Other examples include commercially available polymer dispersants such as Lubrizol's Solsperse series.
  • the energy curable liquid 302 preferably contains a charge control agent that causes the surface of the toner particles to have a charge, a photopolymerization initiator that generates an acid upon irradiation with ultraviolet light, and a monomer that bonds with the acid.
  • the acid bonding monomer is preferably a vinyl ether compound that polymerizes by a cationic polymerization reaction.
  • the energy curable liquid 302 may further contain a sensitizer separately from the photopolymerization initiator.
  • the energy curable liquid 302 may contain a charge control aid, other additives, and the like.
  • the monomer contained in the energy curable liquid 302 (cationically polymerizable monomer, ultraviolet curing agent) is a monofunctional monomer having one vinyl ether group (compound represented by the following formula (1)) and two vinyl ether groups. It is what mixed a certain bifunctional monomer (compound shown by following formula (2)).
  • the photopolymerization initiator contained in the energy curable liquid 302 is a compound represented by the following formula (3), and is 0.3 mass based on the total mass of the above-mentioned monomer (cationic polymerizable monomer / ultraviolet curing agent) % Is included. By using this photopolymerization initiator, a high-resistance liquid recording liquid can be obtained unlike the case where an ionic photoacid generator is used, while enabling good fixation.
  • R 3 and R 4 are bonded to each other to form a ring structure.
  • x represents an integer of 1 to 8
  • y represents an integer of 3 to 17.
  • a 5- or 6-membered ring can be exemplified.
  • succinimide structure, phthalimide structure, norbornene dicarboximide structure, naphthalene dicarboximide structure, cyclohexane dicarboximide structure, epoxycyclohexene dicarboximide structure and the like can be mentioned.
  • these ring structures include, as a substituent, an alkyl group having 1 to 4 carbon atoms, an alkyloxy group having 1 to 4 carbon atoms, an alkylthio group having 1 to 4 carbon atoms, an aryl group having 6 to 10 carbon atoms, carbon It may have an aryloxy group of 6 to 10, an arylthio group of 6 to 10 carbon atoms, and the like.
  • a linear alkyl group (RF1) in which a hydrogen atom is substituted with a fluorine atom a branched alkyl group (RF2), a cycloalkyl group (RF3), and an aryl group ( RF4).
  • the content of the photopolymerization initiator is not particularly limited, but is preferably 0.01 to 5 parts by mass with respect to 100 parts by mass of the cationically polymerizable monomer (preferably a vinyl ether compound).
  • the above cationically polymerizable monomers are dodecyl vinyl ether, dipropylene glycol divinyl ether, dicyclopentadiene vinyl ether, cyclohexane dimethanol divinyl ether, tricyclodecane vinyl ether, trimethylolpropane trivinyl ether, 2-ethyl-1,3-hexanediol divinyl ether 2,4-Diethyl-1,5-pentanediol divinyl ether, 2-butyl-2-ethyl-1,3-propanediol divinyl ether, neopentyl glycol divinyl ether, pentaerythritol tetravinyl ether and 1,2-decanediol
  • it is at least one compound selected from the group consisting of divinyl ethers.
  • FIG. 4 is a cross-sectional conceptual view after fixing after irradiating the energy curable liquid with ultraviolet light.
  • the energy curable liquid 302 is irradiated with a predetermined amount of ultraviolet light, for example, ultraviolet light having a wavelength of about 365 to 410 nm, the energy curable liquid 302 undergoes a polymerization reaction to be cured.
  • the fixing device will be described.
  • the energy curable liquid is an ultraviolet curable liquid
  • irradiating the ultraviolet curable liquid (carrier) with ultraviolet light for example, a device having a mercury lamp, ultraviolet laser, UV-LED or the like can be used. .
  • Total irradiation energy of ultraviolet rays is preferably 0.1 mJ / cm 2 or more 1000 mJ / cm 2 or less.
  • an LED Light Emitting Diode
  • What is important in the ultraviolet curing reaction is the first law of photochemistry (Grotthuss-Drapper's law), that is, "photochemical change is caused only by absorbed light in the amount of projected light.” That is, in ultraviolet curing, matching of the absorption wavelength of the photopolymerization initiator with the emission wavelength of the ultraviolet irradiation device is important.
  • an LED light source having peak illumination at wavelengths such as 365 ⁇ 5 nm, 385 ⁇ 5 nm, and 405 ⁇ 5 nm is mainly present, and therefore, it is preferable that the photopolymerization initiator be absorbed in these wavelength regions.
  • the LEDs that emit ultraviolet light may be arranged in a line in the long side direction, or may be arranged in a plurality of lines.
  • the maximum illuminance at the position of the surface of the conveyed object at a position directly below the LED is referred to as peak illuminance.
  • the irradiation energy received per unit area is the total amount of photons (“integrated light quantity (mJ / cm 2 )”) reaching the surface.
  • the integrated illuminance (mW / cm 2 ) of each wavelength of the ultraviolet irradiation device described above is the integration of the irradiation time (s) ((mW / cm 2 ) ⁇ (s)). The faster the transport speed of the transported recording medium, the shorter the irradiation time.
  • the “integrated light amount (mJ / cm 2 )” that determines the curability is decreased, and the energy curable liquid is less likely to be cured. Therefore, the optimization of the ultraviolet curing agent (cationic polymerizable monomer) or the illuminance (mW / cm 2 ) of the ultraviolet irradiation device is high, so that the higher the speed, the smaller the integrated light quantity for curing the energy curable liquid. It is preferred to select a light source.
  • the toner particles 301 can be considered not to be cured by ultraviolet light. As shown in FIG. 4, after being irradiated with ultraviolet light, the toner particles 301 are contained in a cured resin that is a cured product of the energy curable liquid.
  • the experimental conditions can correspond suitably to the viscosity of the recording liquid of about 0.5 to 50 mPa ⁇ s and the resistance of about 1 ⁇ 10 10 to 1 ⁇ 10 13 ⁇ ⁇ cm.
  • an image forming apparatus adopting an electrophotographic method was used for output, and the color tone of the image was evaluated. The color is calculated by comparing the saturation and lightness using a spectral reflection densitometer.
  • the CIE L * a * b * (CIE LAB) adopted this time is an almost complete color space, and is formulated by the International Commission on Illumination (CIE).
  • each coordinate is marked with an asterisk ( * ).
  • the saturation C * was calculated from the following formula.
  • L * adopts the result of the measuring apparatus.
  • C * ((a * ) 2 + (b * ) 2 ) 1/2
  • a Gretag Macbeth manufactured by X-Rite
  • the volume average particle diameter of the toner particles is preferably 0.2 ⁇ m or more and 5 ⁇ m or less, and in the present embodiment, 1 ⁇ m is used.
  • the ratio (PB ratio P: B) of the pigment (P) to the binder resin (B) in the toner particles is preferably in the range of 1: 1 to 1: 8 by mass ratio, and the present embodiment So, I adopted 1: 4.
  • the volume average particle size of the pigment is preferably 0.05 ⁇ m or more and 0.400 ⁇ m or less, and in the present embodiment, the one having a particle size of 0.075 nm was used.
  • the ratio of the toner particles (T) to the carrier liquid (energy curable liquid) (D) is preferably 20% to 80% on a mass basis, In the present embodiment, 55% is adopted.
  • the refractive index of the carrier liquid is preferably 1.40 or more and 1.65 or less, and in the present embodiment, 1.51 was used.
  • the refractive index between the toner particles and the curing resin is preferably 1.45 or more and 1.70 or less, and in the present embodiment, 1.56 was adopted.
  • the thickness of the cured resin containing the toner image on the surface of the recording medium is preferably 0.5 ⁇ m or more and 4 ⁇ m or less in the case of a single color, and was 1.5 ⁇ m in the present embodiment.
  • the wavelength of ultraviolet light used for curing is 385 ⁇ 5 nm.
  • the energy at the surface of the recording medium was set to be 1400 mW / cm 2 .
  • the distance between the recording medium and the UV-LED device was set to 10 mm.
  • the conveyance speed of the recording medium was set to 1000 mm / s.
  • Coated paper (OKTOP 157) was used as a recording medium.
  • the irradiation width of the ultraviolet fixing device was set to about 30 mm on the surface of the recording medium.
  • the integrated energy of ultraviolet irradiation was set to be 100 mJ / cm 2 . In the experiments in this embodiment, no pressure heating and fixing was performed (no pressure and no heating).
  • the shape (average circularity) of the toner particles is preferably 0.70 or more and 0.99 or less. In this embodiment, the one of 0.98 was used.
  • the carrier liquid (energy curable liquid) contained 100 ppm of a cationic polymerization inhibitor with respect to the total mass of the carrier liquid (energy curable liquid).
  • the viscosity of the recording liquid was adjusted to 5 mPa ⁇ s, and the resistance was adjusted to 1 ⁇ 10 11 ⁇ ⁇ cm.
  • the average circularity of toner particles contained in the cured resin is 0.70 or more and 0.99 or less. Preferably, it is 0.80 or more and 0.99 or less, more preferably 0.90 or more and 0.99 or less.
  • the average circularity can be achieved, for example, by applying energy to the energy curable liquid without applying pressure when the energy curable liquid is cured and the toner image is fixed on the recording medium.
  • the image processing software (Image-J) is used to set the threshold value and pick up the toner area.
  • the image processing software calculates the area and equivalent circle diameter of one particle, and the circumferential length of one particle.
  • the cross-section having the largest diameter of the volume average particle diameter of toner particles ⁇ 10% is selected and measured. 100 toner particle cross sections are measured, and their arithmetic mean value is adopted.
  • a resin film which does not absorb a transparent or opaque liquid used for soft packaging can be used as the recording medium.
  • the resin of the resin film include polyethylene terephthalate, polyester, polyimide, polypropylene, polystyrene, polycarbonate and the like.
  • FIG. 5 (a) to 5 (c) are cross-sectional conceptual diagrams showing the dispersibility (distribution state) of the pigment (colorant particles / coloring material) 303 contained in the toner particles 301.
  • FIG. As described above, the toner particles 301 contain the colorant particles 303 in order to develop a color. However, if the distribution of the colorant particles 303 is different, the lightness and saturation change due to the influence of light reflection and scattering. Saturation: C less than 40, B greater than or equal to 40 and less than 60, A greater than or equal to 60, As for the lightness, C less than 30, B more than 30 and less than 35, and A more than 35 were used. The results are shown in Table 1. In the present invention, B or more is acceptable.
  • the method of producing toner particles is as follows.
  • the toner particles of Examples 1-1 to 1-3 were produced according to the above-mentioned “Method of producing developer of Example 1”.
  • the content of the pigment dispersant (hydroxyl group-containing carboxylic acid ester) in the toner particles is 15% by mass with respect to the total mass of the toner particles in Example 1-1, and 5% by mass in Example 1-2. In Example 1-3, the concentration was 30% by mass.
  • the pigment dispersant acts to surround the pigment itself and make it difficult for the pigments to get close to each other.
  • Example 1-1 In the toner particles of Example 1-1, the distance between the pigments was kept uniform, and the pigments did not aggregate in the center of the toner particles, and the pigments did not approach too close to the wall of the toner particles. In the toner particles of Example 1-2, since the amount of the dispersing agent is smaller than that of Example 1-1, the pigment is aggregated at the center of the toner particles as compared with Example 1-1. In the toner particles of Example 1-3, since the dispersant is more than that of Example 1-1, the distance between the pigments is longer than that of Example 1-1, and compared with Example 1-1, the pigment has a wall surface of the toner particles. Was approaching.
  • Example 1-1 In the toner particles of Example 1-1 (FIG. 5a), primary incident light passes through the cured resin and reaches the toner particle surface as secondary incident light.
  • the refractive index of the surface of the toner particles that is, the difference between the refractive index of the material of the surface of the toner particles and the curing resin, the light is dispersed as secondary reflection, scattering and tertiary incident light.
  • the colorant particles When light reaches the colorant particles, it absorbs or reflects depending on the color characteristics.
  • the dispersion state of the colorant particles was uniform, the light reached the colorant particles on average and the saturation increased.
  • the light passed through the gaps between the colorant particles and had a high probability of reaching the ground, so the lightness was also high.
  • Examples 1-2 and 1-3 and Comparative Example 1 In the toner particles of Example 1-2 (FIG. 5B), the light passes through the gaps between the colorant particles and the probability that the light reaches the base is high, so the light reaches the surface of the colorant particles although the brightness is high. Because of the difficulty, the saturation was lower than that of the toner particle of Example 1-1. In the toner particles of Example 1-3 (FIG. 5C), the light is likely to hit the surface of the colorant particles, and thus the saturation is enhanced, but the light is hard to reach the base, so the lightness of the toner particles of Example 1-1 is increased. It was lower than that.
  • the cross section of the image on the surface of the recording medium, paper was observed.
  • the procedure for obtaining a cross-sectional image is specifically as follows.
  • the cross section of the image on the surface of the recording medium paper was observed using a transmission electron microscope (SEM) to measure the exposure amount.
  • the procedure for obtaining a cross-sectional image is specifically as follows. First, the output medium is sandwiched and fixed with an epoxy curing resin, and the cross section is cut with a microtome.
  • the cross-sectional state of the image can be observed by placing a cut sample with a thickness of about 5 mm on a double-sided conductive tape and photographing using a scanning electron microscope (SEM) JSM-7500F.
  • SEM scanning electron microscope
  • Image processing Image-J is used to delineate toner particles.
  • the image surface interface is plotted, and a moving average line is calculated from the plotted points.
  • the area (exposed area) of the portion of the toner particles located outside the moving average line is calculated.
  • the area (exposed area) outside the moving average line was 10% or more of the toner particle area, it was judged that the toner particles were exposed from the surface of the cured resin.
  • 100 toner particles present at the image surface interface were selected, and the arithmetic mean value of the exposed area was adopted.
  • gloss (glossiness) of the image was measured at an incident angle of 60 degrees using a gloss measurement device (HANDY GLOSSMETER PG-1 manufactured by Nippon Denshi Kogyo Co., Ltd.).
  • gloss (glossiness) is 30 degrees or more, it is considered as gloss "A”, and when less than 30 degrees, it is designated as gloss "C”.
  • the saturation and the lightness are the same as described above.
  • the recording medium is OK top-coated paper, and the surface roughness (ten-point average roughness) Rz of the recording medium is 2 ⁇ m.
  • Rz was about 2 ⁇ m, which was almost the same as the surface roughness of the recording medium, that is, the gloss was about 35 degrees.
  • Comparative Example 1 (FIG. 6), Rz increased to 3.5 ⁇ m, the gloss decreased to 10 °, and the difference between the gloss of the white area and the gloss of the image area increased.
  • the carrier liquid be cured without being vaporized. That is, it is desirable to reduce the amount of vaporization of the carrier liquid to the atmosphere as much as possible or to reduce the time from toner image formation to ultraviolet curing.
  • the carrier liquid is apt to be vaporized and thus tends to be exposed.
  • Example 1-4 Comparative Example 2
  • toner particles and their binder resins
  • pigments are used as curing resins such as carriers.
  • Table 3 shows the results of evaluation of color development in such a case.
  • the recorded matter of Example 1-4 is obtained in the same manner as in Example 1-1 except that the pigment is changed to pigment blue 15: 3.
  • the carrier liquid of Example 1, the pigment dispersant, and pigment blue 15: 3 as a pigment are used as a select coater (film thickness without using an image forming apparatus adopting an electrophotographic method.
  • 1.5 ⁇ m It is obtained by coating with Matsuo Sangyo OSP-1.5 # 0.7 PO. 08 H 4 S 1.5) and curing with ultraviolet light.
  • ⁇ Distributed state The cross section of the image is measured using the SEM described above, and the center position of the pigment (cyan pigment) is detected, and the distance between each pigment (the distance between the first cyan and the second cyan, the first cyan and The distance between the third cyan and the distance between the second cyan and the third cyan were measured. A histogram of frequency against distance was calculated and the variance was calculated.
  • the particle size of the toner particles is 1 ⁇ m
  • the particle size of the pigment is 0.1 ⁇ m
  • the total number of pigments is eight.
  • four pigments (pigments 0 to 3) and pigments 4 to 7 are dispersed in one toner.
  • the respective distances were calculated based on the pigment 0.
  • the average value was 0.79 ⁇ m
  • the standard deviation was 0.47.
  • the average value is 0.57 ⁇ m
  • the standard deviation is 0.18.
  • the toner particles had substantially the same saturation as in Example 1-4 in which the colorant particles were contained. However, in Comparative Example 2, compared to Example 1-4, the light was less likely to reach the background, so the brightness did not increase. As described above, in Example 1-4, the toner particles containing the colorant particles in the binder resin are formed into an island shape in the cured resin after the toner particles are contained in the cured resin, thereby further enhancing the lightness and the saturation. It is possible to raise it.
  • Example 1-5 Comparative Example 3 ⁇ Shape of Toner Particles> The case where the toner particles are deformed after fixing will be described with reference to FIG. Cross sections of the recorded matter of Example 1-5 and FIG. 8A were obtained in the same manner as Example 1-1.
  • FIG. 8A shows the case where the toner is not deformed
  • FIG. 8B shows the case where the toner is deformed by heat or pressure.
  • the recording material obtained in Example 1-1 was heated at a temperature of 150 ° C., a total pressure g 100 N, a longitudinal width of 325 mm, and a nip width by a rigid body heat roller and a pressure roller. This is an example of passing paper at 8 mm.
  • the change in shape was evaluated using the average degree of circularity as an index.
  • the experimental results are shown in Table 4.
  • the measuring method of average roundness is as above-mentioned.
  • Table 4 the difference of the above-mentioned average circularity is compared. The difference is the rate of change of the degree of circularity obtained from the image cross section relative to the degree of circularity of the toner in the supply bottle.
  • the degree of circularity in the supply bottle is 0.98
  • the cross-sectional shape is 0.97, so the rate of change is about 2%.
  • Comparative Example 3 to which heat pressure was applied, the degree of circularity decreased to 0.68. It has fallen 31% in proportion.
  • the toner shape is maintained if the change rate is less than 15%, and it is determined that the toner shape is changed if the change rate is 15% or more.
  • FIG. 11 shows experimental data of lightness and saturation. Each point in FIG. 11 is a measurement result obtained under the following conditions.
  • Example 1-5 in the range of about 50 to 65 of saturation, high lightness could be obtained at the same saturation as compared with Comparative Example 3 (FIG. 8b). In addition, it was confirmed that the same tendency was observed when the saturation was 50 or less and 65 or more.
  • the colorant particles are dispersed like islands in the toner particles, and the toner particles are contained in the cured resin and are not exposed to the outside of the cured resin, It has the effect of increasing the lightness and saturation.
  • the values in the present embodiment are merely an example, and optimization is preferably performed under the respective setting conditions.
  • Example 2 Examples 2-1 and 2-2, Comparative Example 4 Next, an embodiment regarding the distance between wall surfaces of toner particles (the closest distance between wall surfaces) will be described.
  • FIGS. 9A to 9C are cross sections when the particle diameter of toner particles is changed while the amount of colorant particles per unit area is the same.
  • Reference numeral 312 denotes a distance between wall surfaces of toner particles.
  • Table 5 The results of evaluating the lightness and saturation in the same manner as in Example 1 are shown in Table 5. (Production method of recorded matter of Examples 2-1 and 2-2, Comparative example 4) An image was output by the electrophotographic method as in the first embodiment. The method of producing the developer is as described above.
  • the toner particle dispersant contributes to particle formation, it is possible to control the particle size and the degree of circularity by changing the content of the toner particle dispersant.
  • Ajispar PB 817 manufactured by Ajinomoto Co., Ltd.
  • Solsparse 11200, 13940, 17000, 18000 manufactured by Nippon Lubrizol Corporation
  • the toner particle dispersant is contained in 100 parts by mass of the binder resin as shown in FIG. 9 (a) (Embodiment 2-1) 5 parts by mass, and FIG. 9 (b) (Example 2-2) 0.5 parts by mass, and 20 parts by mass of FIG. 9 (c) (Comparative Example 4) were added to prepare a developer.
  • ⁇ Particle size of toner particles> In the cross-sectional image of the toner particles obtained as described above, light is irradiated to the toner particles using a particle shape / particle size analyzer FPIA-3000 manufactured by Sysmex, and the cross-sectional area is measured by the detected value. The volume average particle diameter of 500 toner particles was calculated. The toner particles having a volume average particle diameter of 1 ⁇ m or more as “large”, and 0.5 ⁇ m or more and less than 1 ⁇ m as “medium”, and less than 0.5 ⁇ m as “small”.
  • the procedure for obtaining a cross-sectional image is specifically as follows. First, the output medium is sandwiched and fixed with an epoxy curing resin, and the cross section is cut with a microtome. The cut sample, about 5 mm in thickness, is placed on a double-sided conductive tape and photographed using a scanning electron microscope (SEM) JSM-7500F. The point is taken by giving the contrast between the developer and the surrounding carrier at an acceleration voltage (for example, 15 kv).
  • the image processing software (Image-J) is used to set a threshold and pick up the toner area.
  • the image processing software calculates the area and equivalent circle diameter of one particle, and the central coordinates of the equivalent circle diameter of one particle in the window of the image software.
  • the central coordinates are similarly calculated for adjacent particles.
  • the outer peripheral point of the circle equivalent diameter that intersects the center line is plotted.
  • the distance between the wall surfaces is measured in the window by software. Measure the distance between wall surfaces of 100 pairs of adjacent particles, and adopt the arithmetic mean value.
  • the average distance between wall surfaces is "small" less than 75 nm, "medium” 75 nm or more and 125 nm or less, "large” 125 nm or more and less than 150 nm.
  • ⁇ Film thickness> The cross section of the toner particles was observed using an SEM, and the average value of the distance from the recording medium to the upper surface of the cured product of the developer (recording liquid) was calculated.
  • the film thickness was 2 ⁇ m or more as “large”, 1 ⁇ m or more and less than 2 ⁇ m as “medium”, and less than 1 ⁇ m as “small”.
  • FIG. 12 shows the results of the same examination as in Example 1 for Examples 2-1, 2-2 and Comparative Example 4. It can be seen that the saturation decreases as the average of the distance between the wall surfaces of the toner particles increases. From the above, it is preferable that the average of the distance between the wall surfaces of adjacent toner particles is less than 125 nm. In addition, regarding the minimum value of the distance between wall surfaces of the toner particles, the mechanical barrier of the surface of the toner particles contained in the energy curable liquid is often on average about 10 nm or more (adhered to the surface of the toner particles The average size of the charge control agent is often about 10 nm). Therefore, it is preferable that the average of the distance between the wall surfaces of adjacent toner particles is 10 nm or more.
  • the average of the distance between the wall surfaces of the adjacent toner particles is more preferably 75 nm or more and less than 125 nm.
  • the distance between the wall surfaces can be controlled in two directions. For example, by increasing the amount of toner with respect to the carrier, the bulk density is increased and the distance between wall surfaces is decreased. Conversely, the distance between the wall surfaces can be increased by reducing the amount of toner with respect to the carrier liquid. For example, assuming that the toner and carrier amounts are D and the toner amount is T (mass%), the TD ratio is 75%, the wall distance is 10 nm, the TD ratio is 66%, and the wall distance is 200 nm.
  • FIG. 13 shows the spectral sensitivity (spectral reflectance) at each distance.
  • the reflectance for each wavelength was measured using a Gretag Macbeth (X-Rite) spectrophotometer.
  • the average distance between wall surfaces is 170 nm “large”, 140 nm (comparative example 4) "large”, 100 nm (example 2-1) “medium”, 40 nm (example 2-2) "small””.
  • FIG. 12 it can be seen that the absorption and reflectance distribution change with the average of the distance between the wall surfaces of the toner particles.
  • the reflectance when the average distance between wall surfaces is "large” and “large” is lower than the reflectance when "small” and "medium” are Is clear.
  • Examples 2-4 to 2-6 The color developability when the amount of colorant particles is changed will be described using FIG.
  • the degree of color development is approximately determined by the amount of pigment per unit area.
  • the film thickness can be increased to ensure that the toner particles are present in multiple layers so that a suitable color can be obtained.
  • the consumption of the binder resin and the cured resin (curable liquid) increases.
  • Example 2-6 of Table 6 when the amount of pigment contained in one toner particle is small, the film thickness is increased, and saturation and lightness are improved by forming toner particles in multiple layers. It was possible. As described above, even if the film thickness is changed according to the amount of the pigment contained in one toner particle, the lightness and the saturation can be obtained by setting the average of the distance between the wall surfaces of the toner particles to a value within a predetermined range. It can be kept high.
  • Irradiator 15 Recording Liquid 16 Recording Medium 17 Hardening Resin 20
  • Photosensitive Drum 30 Charging Device (Primary Charger) 40 exposure light 61 primary transfer roller 70 transfer device (intermediate transfer belt) 80 transport belt 81 secondary transfer outer roller 86 secondary transfer inner roller 301 toner particles 302 energy curable liquid (carrier liquid) 303 Colorant particles (colorant) 305 binder resin 308 primary incident light 309 secondary incident light 310 secondary reflected light 311 secondary scattered light 312 distance between wall surfaces of toner particles 320 exposed portion

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