EP3594004B1 - Ink-jet recording method and actinic ray curable ink-jet ink set - Google Patents

Ink-jet recording method and actinic ray curable ink-jet ink set Download PDF

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Publication number
EP3594004B1
EP3594004B1 EP19184770.6A EP19184770A EP3594004B1 EP 3594004 B1 EP3594004 B1 EP 3594004B1 EP 19184770 A EP19184770 A EP 19184770A EP 3594004 B1 EP3594004 B1 EP 3594004B1
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EP
European Patent Office
Prior art keywords
ink
jet
print layer
recording method
gelling agent
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EP19184770.6A
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German (de)
English (en)
French (fr)
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EP3594004A1 (en
Inventor
Yusuke KUROGI
Go Yamaguchi
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Konica Minolta Inc
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Konica Minolta Inc
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M3/00—Printing processes to produce particular kinds of printed work, e.g. patterns
    • B41M3/008—Sequential or multiple printing, e.g. on previously printed background; Mirror printing; Recto-verso printing; using a combination of different printing techniques; Printing of patterns visible in reflection and by transparency; by superposing printed artifacts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M7/00—After-treatment of prints, e.g. heating, irradiating, setting of the ink, protection of the printed stock
    • B41M7/0081—After-treatment of prints, e.g. heating, irradiating, setting of the ink, protection of the printed stock using electromagnetic radiation or waves, e.g. ultraviolet radiation, electron beams

Definitions

  • the present invention relates to an ink-jet recording method and an actinic ray curable ink-jet ink set. More particularly, the present invention relates to an ink-jet recording method in which the adhesion between the upper layer and the colored ink is excellent even when a white ink or a clear ink is used for undercoating.
  • Ink-jet printing techniques have been used in various fields of printing since images may be formed easily at low cost.
  • a suitable combination of inks is selected from yellow ink, magenta ink, cyan ink and black ink according to the color to be formed, and a full color image may be obtained by overprinting the selected inks.
  • An actinic ray curable ink-jet ink is used as one of the measures against the above problems.
  • an actinic ray for example, an ultraviolet ray is irradiated and cured to form an image.
  • the actinic ray curable ink-jet image forming method has been attracting attention in recent years because an image having high abrasion resistance and adhesiveness may be formed even on a recording medium having no ink absorbability.
  • a white ink having a shielding property is used.
  • a method of forming a color image (colored image) and enhancing the visibility of the color image is adopted.
  • titanium oxide having high hiding power is widely used as a white pigment used for a white ink (see, for example, Patent Document 1: WO 2015/156267 and Patent Document 2: WO 2016/098678 ).
  • a clear ink may be used to make the surface of the non-absorptive recording medium uniform.
  • a gelling agent may be added to the white ink and the clear ink in order to suppress the coalescence of the droplets or to impart a certain texture formed by the gelling agent.
  • the amount of the gelling agent is too small, the coalescence of the droplets is not prevented, and when the amount of the gelling agent is too large, the gelling agent is excessively deposited on the surface, and the droplets does not sufficiently level.
  • titanium oxide is more polar than pigments in colored ink, and is less likely to interact with the gelling agent, and the gelling agent is likely to precipitate on the surface.
  • Patent Document 3 discloses an ink-jet recording method using an actinic ray curable ink-jet ink set having a first active ray curable ink and a second active ray curable ink, wherein irradiation of both inks is carried out in a two-step curing process for each of the first and second ink.
  • An object of the present invention is to provide an ink-jet recording method and an actinic ray curable ink-jet ink set which achieve excellent adhesion between the upper layer and the colored ink even when a white ink or a clear ink is used for undercoating.
  • This method contains: forming a lower print layer with a white ink or a clear ink; forming an upper print layer with a colored ink containing a colorant; and controlling an oxygen concentration when curing the lower print layer and the upper print layer by collectively irradiating with actinic rays.
  • An ink-jet recording method reflecting an aspect of the present invention is an ink-jet recording method using an actinic ray curable ink-jet ink set having a first ink-jet ink containing at least titanium oxide and a gelling agent, and a second ink-jet ink containing a colorant other than titanium oxide, the ink-jet recording method comprising the steps of:
  • An ink-jet recording method using reflecting another aspect of the present invention is an ink-jet recording method using an actinic ray curable ink-jet ink set having a first ink-jet ink containing a gelling agent without containing a colorant, and a second ink-jet ink containing a colorant other than titanium oxide, the ink-jet recording method comprising the steps of:
  • a lower print layer is formed by printing a first ink-jet ink containing titanium oxide and a gelling agent, that is, a white ink; thereafter, un upper print layer is formed on the lower print layer by printing a second inkjet ink containing a colorant other than titanium oxide, i.e., a colored ink; and the lower print layer and the upper print layer are simultaneously irradiated with oxygen at a concentration of 10% or less.
  • oxygen concentration By reducing the oxygen concentration, the curability of the colored ink is improved, and the curing shrinkage degree of the colored ink and the curing shrinkage degree of the white ink may be made equal.
  • the adhesion between the lower print layer containing a white ink and the upper print layer containing a colored ink may be improved.
  • An ink-jet recording method reflecting an aspect of the present invention is an ink-jet recording method using an actinic ray curable ink-jet ink set, wherein the actinic ray curable ink-jet ink set have a first ink-jet ink containing at least titanium oxide and a gelling agent (hereinafter it may be called simply as "a first ink”), and a second ink-jet ink containing a colorant other than titanium oxide (hereinafter it may be called simply as "a second ink”).
  • a first ink containing at least titanium oxide and a gelling agent
  • a second ink-jet ink containing a colorant other than titanium oxide
  • the ink-jet recording method comprises the steps of: forming a lower print layer by printing the first inkjet ink; forming an upper print layer on the lower print layer by printing the second ink-jet ink; and curing the lower print layer and the upper print layer simultaneously by irradiating them by with actinic rays with controlling an oxygen concentration in an atmosphere to which the actinic rays are irradiated to be 10 volume% or less in the step of curing the lower print layer and the upper print layer.
  • An ink-jet recording method reflecting another aspect of the present invention is an ink-jet recording method using an actinic ray curable ink-jet ink set, wherein the actinic ray curable ink-jet ink set have a third ink-jet ink containing a gelling agent without containing a colorant (hereinafter it may be called simply as "a third ink", it has to be noted that in the corresponding set of claims 10-16 and 18 the "third ink” for clarity reasons has been replaced again by another "first ink”), and a second ink-jet ink containing a colorant other than titanium oxide.
  • the ink-jet recording method comprises the steps of: forming a lower print layer by printing the third ink-jet ink; forming an upper print layer on the lower print layer by printing the second ink-jet ink; and curing the lower print layer and the upper print layer simultaneously by irradiating them with actinic rays with controlling an oxygen concentration in an atmosphere to which the actinic rays are irradiated to be 10 volume% or less in the step of curing the lower print layer and the upper print layer. That is, in the other ink-jet recording method of the present invention, the adhesion between the upper layer and the colored ink becomes excellent even when the clear ink is used for the undercoating.
  • the second ink-jet ink further contains a gelling agent from the viewpoint that the coalescence of droplets may be suppressed.
  • the gelling agent in the first inkjet ink or the gelling agent in the third inkjet ink is in the range of 50 to 90 mass% with respect to the gelling agent of the second inkjet ink.
  • the gelling agent in the first ink-jet ink is contained in the range of 0.4 to 2.4 mass% with respect to the total mass of the first ink-jet ink, or the gelling agent in the third ink-jet ink is contained in the range of 0.4 to 2.4 mass% with respect to the total mass of the third ink-jet ink.
  • the first or the third ink-jet ink and the second ink-jet ink contain monomer A having an acrylic equivalent (molecular weight / number of acrylic groups) of less than 170, and that the addition amount of the component derived from the monomer A in the first ink-jet ink or the third ink-jet ink is 60 to 90 mass% with respect to the component derived from the monomer A in the second ink-jet ink.
  • the degree of curing and shrinkage of the lower print layer and the upper print layer may be made comparable, and the adhesion between the lower print layer and the upper print layer becomes better.
  • the first or the third ink-jet ink and the second ink-jet ink contain monomer B having an acrylic equivalent (molecular weight / number of acrylic groups) of 170 or more, and that the addition amount of the component derived from the monomer B in the second ink-jet ink is in the range of 60 to 90 mass% with respect to the component derived from the monomer B in the first or the third ink-jet ink.
  • the degree of curing and shrinkage of the lower print layer and the upper print layer may be made comparable, and the adhesion between the lower print layer and the upper print layer becomes better.
  • the titanium oxide is surface-modified with alumina, and the amount of the alumina surface-modified to the titanium oxide is in the range of 0.3 to 0.8 mass% with respect to the titanium oxide before surface modification (or untreated).
  • the film deterioration with time due to the photocatalytic effect of titanium oxide may be suppressed, and the adhesion between the lower print layer and the upper print layer may be maintained for a long time.
  • the first ink-jet ink preferably contains 200 mass ppm or less of sodium (Na) ion with respect to the titanium oxide.
  • the sodium ion may combine with the residual fatty acid in the gelling agent to form a metal soap to cause gelation failure or to precipitate in an inkjet head to cause a failure.
  • the sodium ion content By setting the sodium ion content to less than 200 mass ppm, poor gelation may be suppressed, and deposition in an ink-jet head may also be prevented.
  • the gelling agent contains a compound having a structure represented by at least Formula (G1) or Formula (G2) (described later) from the viewpoint of better adhesion between the lower print layer and the upper print layer.
  • An actinic ray curable ink-jet ink set used in the ink-jet recording method of the present invention comprises: a first ink-jet ink containing titanium oxide and a gelling agent; and a second ink-jet ink containing a colorant other than titanium oxide.
  • An actinic ray curable ink-jet ink set used in another ink-jet recording method of the present invention contains: a third ink-jet ink containing a gelling agent and containing no colorant; and a second colorant containing a colorant other than titanium oxide.
  • the ink-jet recording method is an ink-jet recording method using an actinic ray curable ink-jet ink set.
  • the actinic ray curable ink-jet ink set has a first ink containing titanium oxide and a gelling agent, and a second ink containing a colorant other than titanium oxide.
  • This ink-jet recording method comprises the steps of: forming a lower print layer by printing the first ink-jet ink; forming an upper print layer on the lower print layer by printing the second ink-jet ink; and curing the lower print layer and the upper print layer by irradiating them with actinic rays.
  • an oxygen concentration in an atmosphere to which the actinic rays are irradiated is controlled to be 10 volume% or less in the step of curing the lower print layer and the upper print layer.
  • the ink-jet recording method uses an actinic ray curable inkjet ink set having a third ink-jet ink containing a gelling agent without containing a colorant, and a second ink-jet ink containing a colorant other than titanium oxide.
  • the ink-jet recording method comprising the steps of: forming a lower print layer by printing the third ink-jet ink; forming an upper print layer on the lower print layer by printing the second ink-jet ink; and curing the lower print layer and the upper print layer by irradiating them with actinic rays.
  • an oxygen concentration in an atmosphere to which the actinic rays are irradiated is controlled to be 10 volume% or less in the step of curing the lower print layer and the upper print layer.
  • the first ink which is a white ink containing titanium oxide
  • the ink-jet recording method according to the second embodiment is a method using a third ink which is a clear ink containing no colorant, instead of the aforesaid first ink as the lower print layer.
  • Others are basically the same as the ink-jet recording method according to the first embodiment.
  • the oxygen concentration at the time of actinic ray irradiation in the step of curing the lower print layer and the upper print layer, by setting the oxygen concentration at the time of actinic ray irradiation to be 10% or less, the oxygen inhibition of the second ink is less likely to occur, and the curability of the second ink is improved.
  • the degree of cure and expansion of the second ink may be made equal to that of the third ink, and the adhesion between the upper print layer and the lower print layer may be improved.
  • the second and third inks may be sufficiently cured even with a smaller amount of light.
  • the first or the third ink is printed (landed) on the recording medium to form the lower print layer. At this time, it is essential that the first or the third ink droplet lands on a position on the recording medium corresponding to the image to be formed.
  • the ejection stability may be enhanced by discharging the first or the third ink droplet from the ink-jet head in a heated state.
  • the temperature of the first or the third ink at the time of ejection is preferably in the range of 35 to 100 °C, and from the viewpoint of further enhancing the ejection stability, it is more preferably in the range of 35 to 80 °C.
  • ejection is performed at an ink temperature such that the viscosity of the first or the third ink is preferably in the range of 3 to 20 mPa ⁇ s, more preferably in the range of 8 to 13 mPa ⁇ s.
  • An example of a method of heating the first or the third ink to a predetermined temperature include a method to heat to a predetermined temperature at least one of an ink tank constituting the head carriage, an ink supply system such as a supply pipe and an ink chamber in the front chamber immediately before the head, a pipe with a filter, and a piezo head.
  • an amount of the droplet of the first or the third ink when ejected is preferably in the range of 2 to 20 pL.
  • the discharge system from the ink-jet head may be either an on-demand system or a continuous system.
  • Examples of the on-demand system include: electro-mechanical conversion systems including single cavity type, double cavity type, bender type, piston type, shear mode type and shared wall type; electro-thermal conversion systems including thermal ink-jet type and bubble jet (registered trademark).
  • the second ink is printed (landed) on the lower print layer to form the upper print layer.
  • the second ink droplet lands on the lower print layer at a position corresponding to the image to be formed.
  • the temperature and viscosity of the second ink at the time of ejection, the method of heating the second ink, the amount of droplets, and the ejection method are the same as the case described for the first or the third ink in the step of forming the lower print layer described above.
  • the lower print layer and the upper print layer are irradiated with actinic rays to cure the lower print layer and the upper print layer.
  • the oxygen concentration in the atmosphere to which irradiates actinic rays are irradiated is made to be 10 volume% or less.
  • the first and the second inks or the second and the third inks landed in the previous step are irradiated with actinic rays to form a cured film constituting an image.
  • actinic rays By irradiating the first and the second inks or the second and the third inks with actinic rays, the first and the second inks or the second and the third inks are cured to form a cured film.
  • the oxygen concentration in the atmosphere to which actinic rays are applied is preferably 10 volume% or less, more preferably 5% by volume% or less.
  • the oxygen concentration at the time of actinic ray irradiation is preferably 10 volume% or less, more preferably 5% by volume% or less.
  • Examples of means for setting the oxygen concentration to 10% or less include gas replacement using a nitrogen gas.
  • an ink-jet recording apparatus 100 is equipped with a transport unit 120 for transporting the recording medium 200, an ink-jet head 110 for discharging the ink onto a transported recording medium 200, and an irradiation unit 130 for irradiating the ink with actinic rays, and an oxygen concentration adjustment unit 140 for adjusting the oxygen concentration of the atmosphere surrounding the surface of the recording medium 200 on which the ink has landed when the irradiation unit 130 emits the actinic rays.
  • the configuration of the oxygen concentration adjustment unit 140 is not particularly limited as long as the oxygen concentration of the atmosphere may be set to 0.1 volume% or more and 10.0 volume% or less.
  • the oxygen concentration adjustment unit 140 is connected to an external exhaust device. It is equipped with an exhaust pipe 141 capable of sucking and exhausting the gas near the surface of the recording medium and a supply pipe 142 that generates a gas with a low oxygen concentration such as a nitrogen gas generator and located in the downstream of the exhaust pipe 141. At this time, the exhaust gas amount from the exhaust pipe 141 and the gas supply amount from the supply pipe 142 may be adjusted to make the oxygen concentration of the atmosphere in the range of 0.1 to 10.0 volume%.
  • the exhaust pipe 141 and the supply pipe 142 are continuous in FIG.
  • the supply pipe 142 is preferably in the vicinity of the irradiation unit 130, and may be provided continuously with the irradiation unit 130, for example.
  • the exhaust pipe 141 and the supply pipe 142 are not essential components, and for example, only the supply pipe 142 may be used as illustrated in FIG. 2 .
  • the oxygen concentration adjustment unit 140 may be configured to include a partition wall 145 surrounding the irradiating unit 130 and the transporting unit 120.
  • the oxygen concentration in the space partitioned by the partition wall 145 and the transport unit 120 may be made in the range of 0.1 to 10.0 volumes%.
  • an oxygen concentration measuring device 148 may be provided in the space (for example, on the partition wall 145) to adjust the exhaust amount and the supply amount while measuring the oxygen concentration in the space.
  • Examples of actinic rays that may be applied to the first and the second inks or the second and the third inks include electron beams, ultraviolet rays, ⁇ -rays, ⁇ -rays, and X rays. Among these, from the viewpoint of ease of handling and less influence on the human body, it is preferable to irradiate ultraviolet rays.
  • the light source is preferably a light emitting diode (LED) from the viewpoint of suppressing the occurrence of curing failure of the ink due to melting of the first and the second inks or the second and the third inks by radiant heat of the light source.
  • Examples of the LED light sources that enables to irradiate ultraviolet light to form a cured film include watercooled LED, 395 nm, manufactured by Phoseon Technology.
  • the LED light source is configured to emit ultraviolet light in the range of 370 to 410 nm at a peak illuminance of 0.5 to 10 W/cm 2 on the image surface. It is more preferable to be configured to set in the range of 1 to 5 W/cm 2 . Alternatively, it is preferable that the light amount irradiated to the image is set to be less than 350 mJ/cm 2 .
  • the transport speed of the recording medium is preferably in the range of 30 to 120 m/min from the viewpoint of high speed recording.
  • the recording medium used in the ink jet recording method according to the first and the second embodiments of the present invention may be any as long as an image may be formed by the first, the second and the third inks according to the present invention.
  • the recording medium include non-absorptive recording media composed of plastics such as polyester, polyvinyl chloride, polyethylene, polyurethane, polypropylene, acrylic resin, polycarbonate, polystyrene, acrylonitrile-butadiene-styrene copolymer, polyethylene terephthalate and polybutadiene terephthalate; non-absorptive inorganic recording media composed of metals and glasses; and papers (for example, coated paper for printing, and coated paper B for printing). Among them, it is preferably used for an OK top coat paper and a Mali coat paper for which coating with overcoat liquid is required.
  • Ink droplets are deposited on the recording medium by discharging the ink droplets from the ink-jet recording head. It is preferable that the temperature of the recording medium is set in the range of 20 to 50 °C when the ink droplets land in order to form a high quality image with good repeatability.
  • An actinic ray curable ink-jet ink set according to the first embodiment of the present invention (hereinafter, also simply referred to as an ink set) is an actinic ray curable ink-jet ink set used in the ink-jet recording method according to the first embodiment. It includes a first ink containing titanium oxide and a gelling agent, and a second ink containing a colorant other than titanium oxide.
  • an actinic ray curable ink-jet ink set according to the second embodiment of the present invention (hereinafter, also simply referred to as an ink set) is an actinic ray curable ink-jet ink used in the ink-jet recording method according to the second embodiment. It includes a third ink containing a gelling agent and containing no colorant, and a second ink containing a colorant other than titanium oxide.
  • the ink set according to the first embodiment includes the first ink which is a white ink containing titanium oxide.
  • the ink set according to the second embodiment is an ink set provided with a third ink containing a gelling agent without containing a colorant (namely, a clear ink) instead of the first ink in the ink set according to the first embodiment.
  • the other configuration of the second ink is the same as that of the ink set according to the first embodiment.
  • the first ink contains titanium oxide and a gelling agent.
  • the second ink contains a colorant other than titanium oxide.
  • the third ink contains a gelling agent and does not contain a colorant.
  • the first to the third inks preferably contain a photopolymerizable compound and a photopolymerization initiator. Further, it is preferable that at least the first ink and the third ink contain a gelling agent, and it is preferable that all of the first to the third inks contain a gelling agent.
  • the first ink preferably contains titanium oxide as a white pigment, and 50 mass% or more of the titanium oxide is preferably rutile titanium dioxide.
  • the titanium oxide applied to the present invention is preferably surface-modified (surface-treated) with alumina, silica, zinc, zirconia, or an organic substance, and particularly preferably surface-modified with alumina.
  • Specific methods for surface-modifying titanium oxide with alumina include, for example, the following methods. First, titanium oxide is dispersed in water to form a slurry. At this time, a dispersant may be added. Further, separately from the titanium oxide slurry, dilute sulfuric acid aqueous solution is dropped to an aqueous solution of sodium aluminate (sodium aluminate (Na[Al(OH) 4 ])) to adjust the pH to 10.5 to 11.8; thus an aluminum compound solution is prepared. Next, addition and mixing of the titanium oxide slurry obtained above to the aluminum compound solution is started.
  • sodium aluminate sodium aluminate
  • stirring is performed using a stirrer, and stirring is continued after addition of the titanium oxide slurry to deposit aluminum oxide hydrate on the titanium dioxide surface.
  • neutralization treatment is performed using a dilute aqueous sulfuric acid solution to adjust the pH of the slurry to 8.15.
  • the slurry after surface treatment is filtered with a membrane filter followed by washing, the collected cake (filtered matter) is dried, and crushed using a commercially available automatic mortar to obtain a surface-modified titanium oxide pigment powder.
  • the surface modification amount of the alumina surface-modified to titanium oxide is preferably in the range of 0.3 to 0.8 mass% with respect to the titanium oxide before (or untreated) the surface modification. By this, it is possible to suppress the film deterioration over time due to the photocatalytic effect of titanium oxide, and maintain the adhesion between the lower print layer and the upper print layer for a long time.
  • the surface modification amount of the surface modified alumina to titanium oxide may be determined from the value of the ratio of the amount of alumina to titanium oxide (Al 2 O 3 /TiO 2 ) based on the analysis result of aluminum element by inductively coupled plasma atomic emission spectrometry (I. C. P.).
  • the surface modification of titanium oxide is carried out, it is preferable to carry out sufficient washing treatment.
  • the washing treatment is insufficient, a large amount of sodium (Na) ions of the sodium aluminate may remain on the surface of the titanium oxide, and when the amount of sodium ions is large, the sodium acid is associated with the residual fatty acid in the gelling agent, and may form metal soaps.
  • This metal soap is a factor that causes gelation failure of the gelling agent. Or, it may be deposited and cause problems in the ink jet head and cause problem. Therefore, it is preferable to set the sodium ion in the first ink to 200 mass ppm or less with respect to titanium oxide. That is, in other words, the amount of alumina surface-modified to titanium oxide is preferably in the range of 0.3 to 0.8 mass% with respect to titanium oxide before surface modification.
  • the sodium ion content in the first ink may be measured using ICP-AES (SPS 3520 UV, manufactured by SII Nano Technology Inc.). Details will be described below.
  • the average particle diameter of the titanium oxide particles according to the present invention is preferably in the range of 50 to 500 nm, and more preferably in the range of 100 to 300 nm.
  • the effects of the present invention are remarkably exhibited.
  • suppression of nozzle clogging in the ink-jet head, storage stability of the first ink (in particular, suppression of sedimentation), and hiding power to the print substrate may be sufficiently exhibited.
  • the titanium oxide particles applicable to the present invention are also commercially available. Examples thereof are CR-50, CR-57, CR-58, CR-67, CR-Super-70, CR-80, CR-90, CR-90-2, CR-93, CR-95, CR-EL, R- 550, R-580, R-630, R-670, R-680, R-780, R-820, R-830, R-850, R-930, R-980, PF-736, PF-737, and PF-742 (made by Ishihara Sangyo Kaisha, Ltd); and SR-41, R-5N, R-7E, R-11P, R-21, R-25, R-32, R-42, R-44, R-45M, R-62N, R-310, R- 650, TCR-52, GTR-100, D-918, and FTR-700 (made by Sakai Chemical Industry Co., Ltd.).
  • the addition amount of titanium oxide in the first ink according to the present invention is preferably in the range of 5.0 to 35 mass%, more preferably 10 to 20 mass%, with respect to the total mass of the first ink.
  • white pigments other than the titanium oxide according to the present invention may be used in combination as needed.
  • white pigments applicable to the present invention for example, inorganic white pigments, organic white pigments, and white hollow polymer fine particles may be used.
  • examples of the inorganic white pigment include, sulfates of alkaline earth metals such as barium sulfate, carbonates of alkaline earth metals such as calcium carbonate, silica such as fine powder silicic acid and synthetic silicates, calcium silicate, alumina, alumina hydrates, zinc oxide, talc, and clay.
  • the second ink according to the present invention further includes a colorant other than titanium oxide.
  • the colorant other than titanium oxide may be a dye or a pigment without limitation, but from the viewpoint of having satisfactory dispersibility in the constituent components of the ink and having excellent weather resistance, a pigment is preferred.
  • a pigment is preferred.
  • the pigment examples thereof include organic pigments or inorganic pigments assigned the numbers that are described in the Color Index.
  • red or magenta pigments examples include: Pigment Red 3, 5, 19, 22, 31, 38, 43, 48:1, 48:2, 48:3, 48:4, 48:5, 49:1, 53:1, 57:1, 57:2, 58:4, 63:1, 81, 81:1, 81:2, 81:3, 81:4, 88, 104, 108, 112, 122, 123, 144, 146, 149, 166, 168, 169, 170, 177, 178, 179, 184, 185, 208, 216, 226, and 257; Pigment Violet 3, 19, 23, 29, 30, 37, 50, and 88; and Pigment Orange 13, 16, 20, and 36 and the mixture thereof.
  • blue or cyan pigments examples include Pigment Blue 1, 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 17-1, 22, 27, 28, 29, 36, and 60 and the mixture thereof.
  • green pigments examples include Pigment Green 7, 26, 36, and 50 and the mixture thereof.
  • yellow pigments examples include Pigment Yellow 1, 3, 12, 13, 14, 17, 34, 35, 37, 55, 74, 81, 83, 93, 94, 95, 97, 108, 109, 110, 137, 138, 139, 153, 154, 155, 157, 166, 167, 168, 180, 185, and 193 and the mixture thereof.
  • black pigments examples include Pigment Black 7, 28, and 26 and the mixture thereof.
  • Examples of commercially available pigment products include CHROMOFINE YELLOW 2080, 5900, 5930, AF-1300, and 2700L; CHROMOFINE ORANGE 3700L and 6730; CHROMOFINE SCARLET 6750; CHROMOFINE MAGENTA 6880, 6886, 6891N, 6790, and 6887; CHROMOFINE VIOLET RE; CHROMOFINE RED 6820 and 6830; CHROMOFINE BLUE HS-3, 5187, 5108, 5197, 5085N, SR-5020, 5026, 5050,4920, 4927, 4937, 4824, 4933GN-EP, 4940, 4973, 5205, 5208, 5214, 5221, and 5000P; CHROMOFINE GREEN 2GN, 2GO, 2G-550D, 5310, 5370, and 6830; CHROMOFINE BLACK A-1103; SEIKA FAST YELLOW 10 GH, A-3,
  • dyes conventionally known yellow dyes, magenta dyes, cyan dyes, and black dyes may be applied.
  • dispersion methods used to prepare the first and second inks are as follows. Dispersion of titanium oxide and the pigment are made by ball mill, sand mill, attritor, roll mill, agitator, HENSCHEL mixer, colloid mill, ultrasonic homogenizer, pearl mill, wet jet mill, or paint shaker.
  • the dispersion conditions of the pigment it is preferable that the dispersion is performed so that the volume average particle diameter of pigment particles becomes in the range of 0.08 to 0.5 ⁇ m, and the maximum particle diameter becomes in the range of 0.3 to 10 ⁇ m, more preferably in the range of 0.3 to 3 ⁇ m.
  • the dispersion of the pigment may be adjusted by the selection of the pigment, the dispersing agent and the dispersing medium, the dispersing conditions, and the filtering conditions to obtain a pigment dispersion having a desired particle size.
  • the first and the second ink according to the present invention may further include a dispersant in order to increase dispersibility of the pigment.
  • the dispersant include hydroxyl group-containing carboxylic acid esters, salts of long-chain polyaminoamides and high-molecular weight acid esters, salts of high-molecular weight polycarboxylic acids, salts of long-chain polyaminoamides and polar acid esters, high molecular weight unsaturated acid esters, polymer copolymerization products, modified polyurethanes, modified polyacrylates, polyether ester type-anionic active agents, naphthalenesulfonic acid-formalin condensate salts, aromatic sulfonic acid-formalin condensate salts, polyoxyethylene alkyl phosphoric acid esters, polyoxyethylene nonyl phenyl ethers, and stearyl amine acetates.
  • Examples of commercially available dispersant products include SOLSPERSE series of Avecia Biotechnology
  • the first ink according to the present invention contains a gelling agent, and the gelling agent in the first ink is contained in the range of 50 to 90 mass% with respect to the gelling agent in the second ink. It is preferable in view of the fact that the curing and shrinkage of the lower print layer and the upper print layer may be made comparable and the adhesion between the lower print layer and the upper print layer becomes better.
  • the third ink according to the present invention contains a gelling agent, and the gelling agent in the third ink is in the range of 50 to 90 mass% with respect to the gelling agent in the second ink. It is preferable that the lower printing layer and the upper printing layer have the same curing and shrinkage degree, and the adhesion between the lower printing layer and the upper printing layer is further improved.
  • the gelling agent in the first ink is preferably in the range of 0.4 to 2.4 mass% with respect to the total mass of the first ink.
  • the gelling agent in the third ink is also preferably in the range of 0.4 to 2.4 mass% with respect to the total mass of the third ink.
  • the content of the gelling agent is 0.4 mass% or more, the pinning property of the first ink or the third ink may be sufficiently enhanced, and a higher definition image may be formed.
  • the content of the gelling agent is 2.4 mass% or less, precipitation of the gelling agent from the surface of the formed image may be suppressed, and the adhesiveness of the formed image may be improved.
  • At least the first and third inks contain a gelling agent from the viewpoint of suppressing excessive wetting and spreading of the ink droplets landed on the recording medium and making it easy to obtain a high-definition image.
  • the gelling agent is an organic substance which becomes solid at normal temperature and becomes a liquid when heated, and is an additive having a function of causing the ink to reversibly undergo a sol-gel phase transition depending on the temperature.
  • the structure thus formed may be referred to as a "card-house structure".
  • the card-house structure can retain the unreacted radically polymerizable compound and the unreacted photopolymerization initiator, thereby enhancing the pinning property of the ink droplet. As a result, the unity of adjacent ink droplets may be suppressed.
  • the actinic ray curable ink-jet ink containing the gelling agent is crystallized and has a high viscosity, so that the molecular motion of the photopolymerization initiator is easily suppressed.
  • storage stability is less likely to be lost even when the ink is stored for a long time at room temperature.
  • Examples of a gelling agent suitable for forming a card-house structure are: aliphatic ketone compounds; aliphatic ester compounds; petroleum-based waxes such as paraffin wax, microcrystalline wax, and petrolatum; plant waxes such as candelilla wax, carnauba wax, rice wax, wood wax, jojoba oil, jojoba solid wax, and jojoba esters; animal waxes such as beeswax, lanolin and whale wax; mineral waxes such as montan wax and hydrogenated waxes; hardened castor oil or hardened castor oil derivatives; modified waxes such as montan wax derivatives, paraffin wax derivatives, microcrystalline wax derivatives, and polyethylene wax derivatives; higher fatty acids such as behenic acid, arachidic acid, stearic acid, palmitic acid, myristic acid, lauric acid, oleic acid, and erucic acid; higher alcohols such as stearyl alcohol and behenyl alcohol; hydroxystea
  • the gelling agent preferably contains a linear or branched hydrocarbon group having a carbon number of 9 to 25 from the viewpoint of easily forming the above-mentioned "card-house structure".
  • aliphatic ketones having a structure represented by Formula (G1) and aliphatic esters having a structure represented by Formula (G2) are particularly preferable.
  • R 1 to R 4 each independently represent a linear or branched hydrocarbon group having a carbon number in the range of 9 to 25.
  • the hydrocarbon group is preferably an alkyl group.
  • the hydrocarbon group represented by R 1 and R 2 in the Formula (G1) is not particularly limited, but is preferably a linear or branched hydrocarbon group having 12 to 25 carbon atoms. More preferably, it is an alkyl group having 12 to 25 carbon atoms containing a linear or a branched moiety.
  • Examples of the aliphatic ketone compound represented by Formula (G2) include 18-pentatriacontanone (C17-C17), Diglyceryl ketone (C24-C24), dibehenyl ketone (C22-C22), distearyl ketone (C18-C18), dieicosyl ketone (C20-C20), dipalmityl ketone (C16-C16), dimyristyl Ketone (C14-C14), dilauryl ketone (C12-C12), lauryl myristyl ketone (C12-C14), lauryl palmityl ketone (C12-C16), myristyl palmityl ketone (C14-C16), myristyl palmityl ketone (C14-C16), myristyl palmityl ketone (C14-C16), myristyl stearyl ketone (C14 -C18), myristyl beheny
  • Examples of commercially available products of the compound represented by Formula (G1) include 18-Pentatriacontanon (manufactured by Alfa Aeser Co., Ltd.), Hentriacontan-16-on (manufactured by Alfa Aeser Co., Ltd.), and KAO-WAX T1 (manufactured by Kao Corp.).
  • the aliphatic ketone contained in the ink may be one kind or a mixture of two or more kinds.
  • the hydrocarbon group represented by R 3 and R 4 in Formula (G2) is not particularly limited, but is preferably a linear or branched hydrocarbon group having 12 to 25 carbon atoms. More preferably, it is an alkyl group having 12 to 25 carbon atoms containing a linear or branched moiety.
  • Examples of the aliphatic ester compound represented by Formula (G2) include behenyl behenate (C21-C22), icosyl icosanoate (C19-C20), stearyl stearate (C17-C18), palmityl stearate (C17-C16), lauryl stearate (C17-C12), cetyl palmitate (C15-C16), stearyl palmitate (C15-C18), myristyl myristate (C13-C14), cetyl myristate (C13-C16), octyl dodecyl myristate (C13-C20), lauryl laurate (C11-C12), cetyl caprate (C9-C16), stearyl oleate (C17-C18), stearyl erucate (C21-C18), stearyl linolate (C17-C18), behenyl oleate (C18-C22),
  • the figures in the parentheses indicate carbon atom numbers.
  • the numbers in the parentheses indicate the number of carbon atoms, and the number of carbon atoms indicates the number of carbon atoms of each of two hydrocarbon groups separated by a carbonyloxy group.
  • Examples of commercially available products of the compound represented by General Formula 2 include UNISTAR M-2222SL (manufactured by NOF Corp.), EXCEPARL SS (manufactured by Kao Corp., melting point: 60° C), EMALEX CC-18 (manufactured by Nihon-Emulsion Co., Ltd.), AMREPS PC (manufactured by Kokyu Alcohol Kogyo Co., Ltd.), EXCEPARL MY-M (manufactured by Kao Corp.), SPERMACETI (manufactured by NOF Corp.), and EMALEX CC-10 (manufactured by Nihon Emulsion Co., Ltd.). Since many of these commercially available products are mixtures of two or more kinds, the commercially available products may also be used after being subjected to separation and purification as necessary.
  • the gelling agent contained in the first to the third inks may one kind or a mixture of two or more kinds.
  • the photopolymerizable compound according to the present invention has a function of polymerizing by actinic ray and curing the ink.
  • the photopolymerizable compound may be any of a monomer, a polymerizable oligomer, a prepolymer or a mixture thereof.
  • only one type of photopolymerizable compound may be contained, or two or more types may be contained.
  • the actinic rays mentioned here are, for example, energy rays such as electron beams, ultraviolet rays, ⁇ -rays, ⁇ -rays, and X rays, and preferably ultraviolet rays and electron beams.
  • the actinic ray curable compound is a radical polymerizable compound or a cationic polymerizable compound, and is preferably a radical polymerizable compound.
  • the content of the photopolymerizable compound is, for example, preferably in the range of 1 to 97 mass% with respect to the total mass of the ink according to the present invention from the viewpoint of film properties such as curability and flexibility. More preferably, it is in the range of 95 mass%.
  • an unsaturated carboxylic acid ester is preferable, and (meth) acrylate is more preferable.
  • (meth) acrylate means acrylate or methacrylate
  • (meth) acryloyl group means acryloyl group or methacryloyl group
  • (meth) acryl is acryl or methacryl.
  • Examples of the (meth)acrylate compound include monofunctional monomers such as isoamyl (meth)acrylate, stearyl (meth)acrylate, lauryl (meth)acrylate, octyl (meth)acrylate, decyl (meth)acrylate, isomyristyl (meth)acrylate, isostearyl (meth)acrylate, 2-ethylhexyl diglycol (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 2-(meth)acryloyloxyethylhexahydrophthalic acid, butoxyethyl (meth)acrylate, ethoxydiethylene glycol (meth)acrylate, methoxydiethylene glycol (meth)acrylate, methoxypolyethylene glycol (meth)acrylate, methoxypropylene glycol (meth)acrylate, phenoxyethyl (meth)acrylate, tetrahydrofurfuryl (me
  • modified product examples include ethylene oxide modified (EO modified) acrylate having an ethylene oxide group inserted, and propylene oxide modified (PO modified) acrylate having a propylene oxide inserted.
  • EO modified ethylene oxide modified
  • PO modified propylene oxide modified
  • the photopolymerizable compound preferably has a molecular weight in the range of 280 to 1,500.
  • the first to the third inks according to the present invention preferably contain a monomer A having an acrylic equivalent (molecular weight / number of acrylic groups) of less than 170.
  • the first ink to the third inks preferably contain a monomer B having an acrylic equivalent (molecular weight / number of acrylic groups) of 170 or more.
  • the addition amount of the component derived from the monomer A in the first ink is preferably in the range of 60 to 90 mass% with respect to the component derived from the monomer A in the second ink.
  • the third ink also contains a monomer A having an acrylic equivalent (molecular weight / number of acrylic groups) less than 170, and the addition amount of the component derived from the monomer A in the third ink is preferably in the range of 60 to 90 mass% with respect to the component derived from the monomer A in the second ink. Furthermore, the addition amount of the component derived from the monomer B in the second ink is preferably in the range of 60 to 90 mass% with respect to the component derived from the monomer B in the first ink or the third ink.
  • the addition amount of the component derived from the monomer A in the first ink or the third ink and the addition amount of the component derived from the monomer B in the second ink are made to fall within the above range. Thereby the curing shrinkage of the lower print layer and the upper print layer may be made comparable, and the adhesion between the lower print layer and the upper print layer becomes better.
  • Examples of the monomer A include tripropylene glycol (TPG) diacrylate, dipropylene glycol (DPG) diacrylate, neopentyl glycol hydroxypivalate (NPG) diacrylate, polyethylene glycol (PEG) # 200 dimethacrylate, 1,6-hexanediol (HD) diacrylate acrylate dimer acid esterification, 1,6-hexanediol diacrylate, 1,10-decanediol diacrylate, acrylate ester (dioxane glycol diacrylate), tricyclodecane dimethanol diacrylate, EO modified (3) trimethylpropane (TMP) triacrylate, PO modified (3) trimethylpropane (TMP) triacrylate, EO modified (4) pentaerythritol tetraacrylate, glycerinpropoxy acrylate, tris(2-hydroxyethyl)isocyanurate triacrylate, tetramethylolmethane tri
  • 3PO-modified trimethylolpropane triacrylate (EM2381, manufactured by Choko Chemical Co., Ltd., acrylic equivalent: 156.8667)
  • tripropylene glycol diacrylate (APG-200, manufactured by Shin-Nakamura Chemical Co., Ltd., acrylic equivalent: 150.2000).
  • 3PO-modified trimethylolpropane triacrylate and tripropylene glycol diacrylate are preferable.
  • Examples of the monomer B include polyethylene glycol (PEG) #400 dimethacrylate, polyethylene glycol (PEG) #600 dimethacrylate, polyethylene glycol (PEG) #400 diacrylate, polyethylene glycol (PEG) #600 diacrylate, alkoxylated neopentyl glycol (NPG) diacrylate, EO modified (4) 1,6-hexanediol (HD) diacrylate, EO modified (6) trimethylpropane (TMP) triacrylate, and EO modified (9) trimethylpropane (TMP) triacrylate.
  • Commercially available products of such monomer B include polyethylene glycol #400 diacrylate (A-400, manufactured by Shin-Nakamura Chemical Co., Ltd., acrylic equivalent 254.0000), among which polyethylene glycol #400 diacrylate is preferable.
  • Examples of the cationic polymerizable compound include epoxy compounds, vinyl ether compounds, and oxetane compounds.
  • the cationic polymerizable compound may be included alone in the ink, or two or more kinds thereof may be included in the ink.
  • epoxy compounds examples include aromatic epoxides, alicyclic epoxides, and aliphatic epoxides, and in order to increase curability, aromatic epoxides and alicyclic epoxides are preferred.
  • the aromatic epoxide may be a di- or poly-glycidyl ether obtainable by reacting a polyhydric phenol or an alkylene oxide adduct thereof with epichlorohydrin.
  • Examples of the polyhydric phenol or an alkylene oxide adduct thereof to be reacted include bisphenol A or an alkylene oxide adduct thereof.
  • the alkylene oxide in the alkylene oxide adduct may be ethylene oxide or propylene oxide.
  • the alicyclic epoxide may be a cycloalkane oxide-containing compound obtainable by epoxidizing a cycloalkane-containing compound with an oxidizing agent such as hydrogen peroxide or a peracid.
  • the cycloalkane in the cycloalkane oxide-containing compound may be cyclohexene or cyclopentene.
  • the aliphatic epoxide may be a di- or poly-glycidyl ether obtainable by allowing an aliphatic polyhydric alcohol or an alkylene oxide adduct thereof to react with epichlorohydrin.
  • Examples of the aliphatic polyhydric alcohol include alkylene glycols such as ethylene glycol, propylene glycol, and 1,6-hexanediol.
  • the alkylene oxide in the alkylene oxide adduct may be ethylene oxide or propylene oxide.
  • vinyl ether compound examples include monovinyl ethers such as ethyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, octadecyl vinyl ether, cyclohexyl vinyl ether, hydroxybutyl vinyl ether, 2-ethylhexyl vinyl ether, cyclohexanedimethanol monovinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, isopropenyl ether-o-propylene carbonate, dodecyl vinyl ether, diethylene glycol monovinyl ether, and octadecyl vinyl ether; and di- or tri-vinyl ether compounds such as ethylene glycol divinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether, propylene glycol divinyl ether, dipropylene glycol divinyl ether, butanediol divinyl
  • the oxetane compound is a compound having an oxetane ring, and examples thereof include the oxetane compounds described in Japanese Patent Application Publication ( JP-A) Nos. 2001-220526 , 2001-310937 , and 2005-255821 .
  • JP-A Japanese Patent Application Publication
  • cited are the compound represented by Formula (1) given in paragraph No. (0089) of JP-A No. 2005-255821 , the compound represented by Formula (2) given in paragraph No. (0092), the compound represented by Formula (7) in paragraph No. (0107), the compound represented by Formula (8) in paragraph No. (0109), and the compound represented by Formula (9) in paragraph No. (0116) of the same Patent Literature.
  • Formulas (1), (2) and (7) to (9) described in JP-A No. 2005-255821 are presented below.
  • R 1 , R 2 , R 3 , R 8 , R 9 and R 11 in Formulas (1), (2) and (7) to (9) are identical with the description described in JP-A 2005-255821 . The description will be omitted here.
  • the photopolymerization initiator when the first to the third inks according to the present invention contain a radical polymerizable compound as a photopolymerizable compound, it is preferable to apply a photo radical polymerization initiator, and when the first to the third inks contain a cationic polymerizable compound as the photo polymerizable compound, it is preferable to apply a photo cationic polymerization initiator.
  • Radical photopolymerization initiators include intramolecular bond cleavage type initiators and intramolecular hydrogen abstraction type initiators.
  • Examples of the intramolecular bond cleavage type photopolymerization initiators include acetophenone compounds such as diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyl dimethyl ketal, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 4-(2-hydroxyethoxy)phenyl (2-hydroxy-2-propyl)ketone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-2-morpholino(4-thiomethylphenyl)propan-1-one, and 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone; benzoins such as benzoin, benzoin methyl ether, and benzoin isopropyl ether; and acylphosphine oxide compounds such as 2,4,6-trimethylbenzoin diphenylphosphine oxide; benzil; and methyl phenyl gly
  • intramolecular hydrogen abstraction type photopolymerization initiators examples include benzophenone compounds such as benzophenone, o-benzoylbenzoic acid methyl-4-phenyl benzophenone, 4,4'-dichlorobenzophenone, hydroxybenzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, acrylated benzophenone, 3,3',4,4'-tetra(t-butylperoxycarbonyl)benzophenone, and 3,3'-dimethyl-4-methoxybenzophenone; thioxanthone compounds such as 2-isopropylthioxanthone, 2,4-dimethyl thioxanthone, 2,4-diethylthioxanthone, and 2,4-dichlorothioxanthone; aminobenzophenone compounds such as Michler's ketone and 4,4'-diethylaminobenzophenone; 10-butyl-2-chloroacridon
  • acyl phosphine oxide and acyl phosphonate are preferably used in view of reactivity.
  • bis(2,4,6-trimethylbenzoyl)-phenyl phosphine oxide and bis(2,6-dimethoxybenzoyl)-2,4,4-trimethyl-pentyl phosphine oxide.
  • a photoacid generator as a photocationic polymerization initiator.
  • photoacid generator examples include the compounds used in chemically amplified photoresists or photocationic polymerization (see Japanese Research Association for Organic Electronics Materials, Ed. “Imejingu yo Yuki Zairyo (Organic Materials for Imaging)", Bunshin Publishing Company (1993), pp. 187-192 ).
  • the suitable compounds for the present invention are describd in the following.
  • B(C 6 F 5 ) 4 - , PF 6 - , AsF 6 - , SbF 6 - , CF 3 SO 3 - salts of aromatic onium compounds such as diazonium, ammonium, iodonium, sulfonium, and phosphonium may be cited.
  • a halide which photo-generates a hydrogen halide may also be used.
  • the compounds described in paragraph No. (0138) of JP-A2005-255821 may be mentioned.
  • the content of the photopolymerization initiator in the first to the third inks is preferably in the range of 0.01 to 10 mass%, although it depends on the type of the actinic ray and the photopolymerizable.
  • the ink set of the present invention may further include a photopolymerization initiator aid and a polymerization inhibitor according to necessary.
  • the photopolymerization initiator aid may be a tertiary amine compound, and is preferably an aromatic tertiary amine compound.
  • aromatic tertiary amine compound examples include N,N-dimethylaniline, N,N-diethylaniline, N,N-dimethyl-p-toluidine, N,N-dimethylamino-p-benzoic acid ethyl ester, N,N-dimethylamino-p-benzoic acid isoamyl ethyl ester, N,N-dihydroxyethylaniline, triethylamine, and N,N-dimethylhexylamine.
  • N,N-dimethylamino-p-benzoic acid ethyl ester and N,N-dimethylamino-p-benzoic acid isoamyl ethyl ester are preferred. These compounds may be used singly, or two or more kinds may be used in combination.
  • polymerization inhibitor examples include (alkyl)phenol, hydroquinone, catechol, resorcin, p-methoxyphenol, t-butylcatechol, t-butylhydroquinone, pyrogallol, 1,1-picrylhydrazyl, phenothiazine, p-benzoquinone, nitrosobenzene, 2,5-di-tert-butyl-p-benzoquinone, dithiobenzoyl disulfide, picric acid, cupferron, aluminum N-nitrosophenylhydroxylamine, tri-p-nitrophenylmethyl, N-(3-oxyanilino-1,3-dimethylbutylidene)aniline oxide, dibutylcresol, cyclohexanone oxime cresol, guaiacol, o-isopropylphenol, butyraldoxime, methyl ethyl ketoxime, and cyclohexanone
  • the first to the third inks that constitute the ink set of the present invention may further contain other components as necessary.
  • the other components may be various additives or other resins.
  • the additives include surfactants, leveling agents, matting agents, ultraviolet absorbers, infrared absorbers, antibacterial agents, and basic compounds for enhancing the storage to stability of ink.
  • the basic compounds include basic alkali metal compounds, basic alkaline earth metal compounds, and basic organic compounds such as amines.
  • the other resins include resins for regulating the properties of a cured film, and examples thereof include polyester resins, polyurethane resins, vinyl resins, acrylic resins, and rubber resins.
  • the viscosity at 80 °C of each ink according to the present invention is preferably in the range of 3 to 20 mPa ⁇ s, and more preferably in the range of 8 to 13 mPa ⁇ s.
  • the viscosity at 25 °C of the ink according to the present invention is preferably 1000 mPa ⁇ s or more.
  • degelling and regelling in the range of 40 to 90 °C is preferable from the viewpoint of durability of the ink-jet head and in that it may be prevented from becoming mixed and bleeding due to the gel state at the time of landing.
  • the ink containing the gelling agent can undergo a sol-gel phase transition reversibly with temperature.
  • Sol-gel phase transition type actinic ray curable ink is a sol at a high temperature (for example, about 80 °C), so it may be ejected from an ink ejection recording head, but after being landed on a recording medium, it is naturally cooled to become a gel state. Thereby, the unity of adjacent ink droplets may be suppressed, and the image quality may be enhanced.
  • Viscosity of the ink at 80 °C, and viscosity and gelling temperature of the ink at 25 °C may be determined by measuring a change in dynamic viscoelasticity of the ink with temperature using a rheometer.
  • line recording system single pass recording system, line head system
  • serial recording system for an ink-jet recording apparatus of an actinic ray curable ink-jet system. It may be selected according to the resolution of the image to be obtained and the recording speed, but from the viewpoint of high speed recording, the line recording method (single pass recording method, line head method) is preferable.
  • the ink-jet recording method according to the first embodiment of the present invention is a method of using a first ink containing a gelling agent and a second ink. In this method, first, the first ink is discharged onto the recording medium to form the lower printing layer, and then the second ink is discharged onto the lower printing layer to form the upper printing layer.
  • the ink-jet recording method according to the second embodiment of the present invention is a method of using a third ink containing a gelling agent and containing no colorant, and a second ink. In this method, first, the third ink is ejected onto the recording medium to form the lower printing layer, and then the second ink is ejected onto the lower printing layer to form the upper printing layer.
  • the oxygen concentration in the atmosphere to which the actinic radiation is applied is made to be 10 volume% or less.
  • FIG. 4 and Fig. 5 illustrate a whole configuration diagram indicating an example of the configuration of the main part of a line recording type ink-jet recording apparatus applicable to the ink-jet recording method according to the first embodiment of the present invention.
  • illustration of the oxygen concentration adjustment unit described in FIG. 1 to FIG. 3 is omitted.
  • FIG. 4 is a schematic side view of the ink-jet recording apparatus (20), and FIG. 5 is a top view thereof.
  • the following inks are arranged from the upstream side with respect to the transport direction (arrow) of the recording medium (1): a white head carriage (2W) which discharges a first ink (W) containing a gelling agent from an ink head (5); a yellow head carriage (2Y) which discharges a yellow ink (Y) from an ink head (5); a magenta head carriage (2M) which discharges a magenta ink (M) from an ink head (5); a cyan head carriage (2C) which discharges a cyan ink (C) from an ink head (5); and a black head carriage (2K) which discharges a black ink (K) from an ink head (5).
  • a white head carriage (2W) which discharges a first ink (W) containing a gelling agent from an ink head (5)
  • a yellow head carriage (2Y) which discharges a yellow ink (Y) from an ink head (5)
  • a magenta head carriage (2M) which discharge
  • an actinic ray irradiation light source (4) is disposed to perform photocuring.
  • an ink-jet recording image (60) in which a lower print layer (52) containing a gelling agent and an upper print layer (54) are laminated on a recording medium (51) is formed.
  • the irradiation with actinic radiation is preferably performed within 10 seconds, preferably within 0.001 to 5 seconds, and more preferably within 0.01 to 2 seconds after all the ink droplets have been deposited on the recording medium.
  • the irradiation of the actinic light is preferably performed after the ink is ejected from all the ink heads accommodated in the head carriage.
  • a lower print layer (52) is formed using the first ink containing a gelling agent and titanium oxide
  • un upper print is performed using a second ink containing a colorant (for example, a colored pigment) other than titanium oxide to form an upper print layer (54). Therefore, as illustrated in FIG. 6 , in the upper print layer (54) having the colored pigment located on the surface, the interaction between the colored pigment particles (55) and the gelling agent (G) is strong, and the gelling agent (G) is formed on the surface of the colored pigment particles (55). And the crystallized regions (54A, 54B) rich in gelling agent in the surface region are a thin configuration.
  • titanium oxide (53) which constitutes a white ink, has a more hydrophilic particle surface compared to other colored pigments (yellow pigment, magenta pigment, cyan pigment, and black pigment). Therefore, the interaction with the coexisting gelling agent is weak. Therefore, the gelling agent is more easily deposited on the surface area (52A, 52B) of the lower print layer (52) compared to the upper print layer (54).
  • the image recording is performed by irradiating them with the actinic rays all together.
  • the oxygen concentration is reduced to 10 volume% or less when the actinic ray irradiation is performed, thereby reducing the oxygen concentration to obtain improvement of curability of the second ink.
  • the degree of cure shrinkage of the second ink may be made equal to the degree of cure shrinkage of the first ink.
  • the ink-jet recording apparatus illustrated in FIG. 4 and FIG. 5 may be applied to the ink-jet recording method according to the second embodiment of the present invention as well as the ink-jet recording method according to the first embodiment.
  • a clear color head carriage that discharges the third ink from the ink head may be provided.
  • the temperature of the ink in the ink head at the time of ejecting the ink from the ink head is preferably set to a temperature in the range of 10 to 30 °C higher than the gelation temperature of the ink in order to enhance the ink ejection property.
  • An amount of droplet ejected from each nozzle of the ink head is preferably in the range of 0.5 to 10 pL, although it depends on the viscosity of the ink. In order to discharge only to a desired region, it is more preferably in the range of 0.5 to 4.0 pL, and still more preferably in the range of 1.5 to 4.0 pL. Even when such an amount of ink is applied, since the sol-gel phase transition is performed in the ink according to the present invention, the ink does not spread excessively and may be ejected only to a desired location.
  • the ink droplets deposited on the recording medium are cooled and gelled rapidly due to the sol-gel phase transition.
  • the ink droplets may be pinned without being excessively spread.
  • oxygen is less likely to enter the ink surface deposited on the recording medium, and the curing of the ink surface is less likely to be inhibited by oxygen.
  • the ink droplets adhere to the recording medium. It is preferable that the temperature of the recording medium when the ink droplets adhere is set to a temperature lower than the gelation temperature of the ink by a range of 10 to 20 °C.
  • the acceleration voltage for electron beam irradiation is preferably in the range of 30 to 250 kV, and more preferably in the range of 30 to 100 kV, in order to achieve sufficient curing.
  • the electron beam irradiation dose is preferably in the range of 30 to 100 kGy, and more preferably in the range of 30 to 60 kGy.
  • the total ink film thickness after curing is preferably in the range of 2 to 25 ⁇ m.
  • the “total ink film thickness” is the maximum value of the ink film thickness drawn on the recording medium.
  • a white (W) dispersion 1 was obtained in the same manner as the preparation of the above black dispersion, except that titanium oxide (TCR-52; Sakai Chemical Industry Co., Ltd.) was used as a white pigment in place of the black pigment and the addition amount is changed to 60 mass parts.
  • titanium oxide TCR-52; Sakai Chemical Industry Co., Ltd.
  • a black dispersion, a white dispersion 1, a photopolymerizable compound (monomer A, monomer B), a polymerization initiator, a surfactant, a polymerization inhibitor and a gelling agent were mixed, and the mixture was stirred while heated to 80 °C.
  • black inks K1-1, K1-2, and K2-1 to K2-6, which are colored inks prepared, and white inks W1-1, W1-2, W2-1 to W2-6, W3-1 to W3-8 the respective ink sets configured by combining them were introduced into a Konica Minolta ink-jet head (KM1048).
  • black inks K1-1, K1-2, K2-1 to K2-6, which are colored inks, and clear inks C1-1, C2-1 to C2-6, C3-1 to C3-8 were similarly introduced into the Konica Minolta ink-jet head (KM1048).
  • the white ink W1-1 was printed as a solid image on an OK top coat paper (printing paper) as a printing substrate under the conditions of 100 nm x 100 nm printing width and 720 x 720 dpi resolution. Thereafter, the black ink K1-1 is similarly printed as a solid image, and ultraviolet light is applied to the white ink and the black ink printed under an oxygen concentration of 5% with energy of 350 mJ using an LED lamp manufactured by Kyocera Corporation as a UV irradiation light source. It was simultaneously irradiated and cured to form an Image 1.
  • Images 2 to 4 were formed in the same manner as formation of the Image 1, except that the oxygen concentration at the time of ultraviolet irradiation was changed as indicated in the following Table III.
  • Images 5 to 8 were formed in the same manner as formation of the Image 1, except that the white ink W1-1 was changed to W1-2, the black ink K1-1 was changed to K1-2, and the oxygen concentration at the time of ultraviolet irradiation was changed as indicated in the following Table III.
  • Images 101 to 104 were formed in the same manner as formation of the Image 1, except that the white ink W1-1 was changed to the clear ink C1-1, and the oxygen concentration at the time of ultraviolet irradiation was changed as indicated in the following Table III.
  • Images 11 to 16 were formed in the same manner as formation of the image 1, except that the white ink W1-1 was changed as indicated in the following Table IV, and the oxygen concentration at the time of ultraviolet irradiation was made to be 10%.
  • Images 111 to 116 were formed in the same manner as formation of the Image 101, except that the clear ink C1-1 was changed as indicated in the following Table IV, and the oxygen concentration at the time of ultraviolet irradiation was made to be 10%.
  • Images 21 to 26 were formed in the same manner as formation of the Image 11, except that the white ink W2-1 was changed to W1-1, and the black ink K1-1 was changed as indicated in the following Table V.
  • Images 121 to 126 were formed in the same manner as formation of the Image 111, except that the clear ink C2-1 was changed to C1-1, and the black ink K1-1 was changed as indicated in the following Table VI.
  • Example 3-1 Experiment in which the ratio of the gelling agent (white ink or clear ink / black ink) was changed (Formation of images 31 to 36)
  • Images 31 to 36 were formed in the same manner as formation of the Image 1, except that the white ink W1-1 was changed as indicated in the following Table VI, and the oxygen concentration at the time of ultraviolet irradiation was made to be 10%.
  • Images 131 to 136 were formed in the same manner as formation of the Image 101, except that the clear ink C1-1 was changed as indicated in the following Table VI, and the oxygen concentration at the time of ultraviolet irradiation was made to be 10%.
  • Images 141 to 145 were formed in the same manner as formation of the Image 131, except that the clear ink C3-1 was changed as indicated in the following Table VII.
  • Titanium oxide (TCR-52; Sakai Chemical Industry Co., Ltd.), which is a white pigment, was surface-modified according to the following method.
  • the surface modification amount of alumina surface-modified to titanium oxide was determined from the value of the ratio (Al 2 O 3 /TiO 2 ) of the quantity of the alumina to a titanium oxide based on the analysis of elemental aluminum by inductively coupled plasma atomic emission spectrometry (I. C. P.).
  • the content of sodium (Na) ion in the white ink was measured by ICP-AES (SPS 3520 UV, manufactured by SII Nano Technology Inc.).
  • White dispersions 2 to 7 were prepared in the same manner as preparation of the White dispersion 1, except that surface-modified titanium oxide was used as titanium oxide.
  • the amounts (mass%) of aluminum required for the surface modification to titanium oxide before (or untreated) the surface modification in each of the White dispersions 2 to 7 are as indicated in the following Table VIII.
  • White dispersion 2 photopolymerizable compound (monomer A, monomer B), polymerization initiator, surfactant, polymerization inhibitor and gelling agent were mixed with the composition (unit: mass%) described in the following Table VIII.
  • the mixture was stirred in the state heated at 80 °C. Next, in a heated state, the mixture is filtered using a Teflon (registered trademark) 3 ⁇ m membrane filter (Advantec Toyo Co., Ltd.), and the white ink W4-1 to W4-6 having the configuration described in Table VIII were prepared.
  • the white ink W4-1 was printed as a solid image on an OK top coat paper (printing paper) as a printing substrate under the conditions of printing width 100 nm x 100 nm and resolution 720 x 720 dpi.
  • the black ink K1-1 was similarly printed as a solid image, and 100 sheets of the printing were continuously printed. Then, the number of lacked head nozzles was measured. In the following evaluation criteria, ⁇ , ⁇ and ⁇ : were judged to be practically preferred ranks.
EP19184770.6A 2018-07-13 2019-07-05 Ink-jet recording method and actinic ray curable ink-jet ink set Active EP3594004B1 (en)

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JP3893833B2 (ja) 2000-02-09 2007-03-14 ブラザー工業株式会社 インクジェット記録方式用エネルギー線硬化型組成物
JP2001310937A (ja) 2000-04-27 2001-11-06 Hitachi Chem Co Ltd 硬化性オキセタン組成物およびその硬化方法ならびにその方法により得られる硬化物
JP4556414B2 (ja) 2003-10-22 2010-10-06 コニカミノルタホールディングス株式会社 インクジェット用インク及びそれを用いたインクジェット記録方法
JP4765256B2 (ja) 2004-03-11 2011-09-07 コニカミノルタホールディングス株式会社 活性光線硬化型インクジェットインクとそれを用いたインクジェット記録方法
JP4898618B2 (ja) * 2007-09-28 2012-03-21 富士フイルム株式会社 インクジェット記録方法
JP2010111790A (ja) 2008-11-07 2010-05-20 Konica Minolta Holdings Inc 活性光線硬化型インクジェット用インクとそれを用いたインクジェット記録方法
US9487010B2 (en) * 2010-12-15 2016-11-08 Electronics For Imaging, Inc. InkJet printer with controlled oxygen levels
JP6045422B2 (ja) * 2013-03-29 2016-12-14 富士フイルム株式会社 インクジェット記録用ホワイトインク組成物、インクジェット記録方法、及び、印刷物
EP3115220B1 (en) * 2014-03-07 2019-03-06 Konica Minolta, Inc. Image formation process
US9744779B2 (en) * 2014-04-10 2017-08-29 Konica Minolta, Inc. Active-light-ray-curable inkjet white ink and image forming method
JP6314810B2 (ja) * 2014-12-11 2018-04-25 コニカミノルタ株式会社 インクジェット記録方法およびインクジェット記録装置
JP6790829B2 (ja) 2014-12-15 2020-11-25 コニカミノルタ株式会社 活性光線硬化型インクジェットインク、インクジェット画像形成方法およびインクジェットインクを用いて画像が形成された記録媒体
JP6398813B2 (ja) * 2015-03-17 2018-10-03 コニカミノルタ株式会社 活性光線硬化型インクジェットインク、画像形成方法およびインクセット
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