WO2013161298A1 - Encre pour jet d'encre durcissable par rayonnement actif et procédé de formation d'image l'utilisant - Google Patents

Encre pour jet d'encre durcissable par rayonnement actif et procédé de formation d'image l'utilisant Download PDF

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WO2013161298A1
WO2013161298A1 PCT/JP2013/002796 JP2013002796W WO2013161298A1 WO 2013161298 A1 WO2013161298 A1 WO 2013161298A1 JP 2013002796 W JP2013002796 W JP 2013002796W WO 2013161298 A1 WO2013161298 A1 WO 2013161298A1
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ink
curable inkjet
actinic ray
mass
inkjet ink
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PCT/JP2013/002796
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English (en)
Japanese (ja)
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晃央 前田
飯島　裕隆
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コニカミノルタ株式会社
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Priority to JP2014512368A priority Critical patent/JP6070698B2/ja
Publication of WO2013161298A1 publication Critical patent/WO2013161298A1/fr

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    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/10—Printing inks based on artificial resins
    • C09D11/101—Inks specially adapted for printing processes involving curing by wave energy or particle radiation, e.g. with UV-curing following the printing
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/30—Inkjet printing inks
    • C09D11/34—Hot-melt inks
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41J—TYPEWRITERS; SELECTIVE PRINTING MECHANISMS, i.e. MECHANISMS PRINTING OTHERWISE THAN FROM A FORME; CORRECTION OF TYPOGRAPHICAL ERRORS
    • B41J11/00—Devices or arrangements  of selective printing mechanisms, e.g. ink-jet printers or thermal printers, for supporting or handling copy material in sheet or web form
    • B41J11/0015—Devices or arrangements  of selective printing mechanisms, e.g. ink-jet printers or thermal printers, for supporting or handling copy material in sheet or web form for treating before, during or after printing or for uniform coating or laminating the copy material before or after printing
    • B41J11/002—Curing or drying the ink on the copy materials, e.g. by heating or irradiating
    • B41J11/0021—Curing or drying the ink on the copy materials, e.g. by heating or irradiating using irradiation
    • B41J11/00214—Curing or drying the ink on the copy materials, e.g. by heating or irradiating using irradiation using UV radiation

Definitions

  • the present invention relates to an actinic ray curable inkjet ink and an image forming method using the same.
  • the ink jet recording method is used in various printing fields because it can form an image easily and inexpensively.
  • As one of the ink jet recording methods there is an ultraviolet curable ink jet method in which droplets of ultraviolet curable ink jet ink are landed on a recording medium and then cured by irradiation with ultraviolet rays to form an image.
  • the ultraviolet curable ink jet method has been attracting attention in recent years because it can form an image having high scratch resistance and adhesion even on a recording medium having no ink absorbability.
  • the light source for curing the ultraviolet curable ink-jet ink is a light source with high radiant heat such as a metal halide lamp
  • the surface of the ink droplet cured by the ultraviolet rays is likely to melt, and the curing of the ink droplet surface is likely to occur.
  • the ink cannot be cured with a light source having a large radiant heat.
  • Patent Document 4 an ink-jet ink in which a trifunctional or higher acrylate monomer and an acrylamide derivative are added has been proposed (for example, Patent Document 4).
  • the curable monomer is enhanced with an acrylate monomer having three or more functions, and the ejection stability of the ink is enhanced with an acrylamide derivative.
  • the photopolymerizable compound having a (meth) acrylamide group in an ultraviolet curable inkjet ink containing a water-soluble solvent is also considered to add (Patent Document 5).
  • the present invention has been made in view of the above circumstances.
  • An actinic ray curable inkjet ink in which ink droplets after landing on a recording medium do not coalesce, the cured film has high adhesion to the recording medium, and the cured film also has excellent scratch resistance, and the same
  • An object is to provide an image forming method.
  • the first of the present invention relates to the actinic ray curable inkjet ink shown below.
  • An actinic ray curable inkjet ink that contains a gelling agent, a photopolymerizable compound, and a photopolymerization initiator and that reversibly undergoes sol-gel phase transition depending on temperature, and the content of the gelling agent is
  • the photopolymerizable compound is 0.5% by mass or more and less than 10% by mass with respect to the mass.
  • ClogP is in the range of ⁇ 4.0 to less than 1.0, and (meth) acrylamide group is present in the molecule.
  • An actinic ray curable inkjet ink comprising:
  • [5] The activity according to any one of [1] to [4], wherein the polymerizable compound B contains 3 or more and less than 25 a structure represented by (—CH 2 —CH 2 —O—) in the molecule.
  • Light curable inkjet ink [6] The actinic ray curable inkjet ink according to any one of [1] to [5], wherein the molecular weight of the polymerizable compound B is 300 or more and less than 800.
  • [7] The actinic ray curable inkjet ink according to any one of [1] to [6], wherein the polymerizable compound B has a ClogP value of 0 or more and less than 3.6.
  • the gelling agent is at least one selected from the group consisting of aliphatic ketone compounds, aliphatic monoester compounds, higher fatty acids, higher alcohols, fatty acid amides, and polyhydric alcohol fatty acid esters.
  • the second of the present invention relates to an image forming method described below.
  • ink droplets after landing on a recording medium are difficult to coalesce during image formation. Furthermore, the adhesion between the cured film (printed image) of the ink and the recording medium is high, and the scratch resistance of the cured film is also excellent. That is, it is possible to form a high-quality image with good adhesion to the recording medium and high hardness.
  • FIG. 2 is a diagram (top view) illustrating an example of a configuration of a main part of a line recording type inkjet recording apparatus. It is a figure which shows an example of a structure of the principal part of the inkjet recording device of a serial recording system.
  • the actinic ray curable inkjet ink of the present invention includes a gelling agent, a photopolymerizable compound, and a photopolymerization initiator.
  • a photopolymerizable compound is a compound which bridge
  • the actinic rays are, for example, electron beams, ultraviolet rays, ⁇ rays, ⁇ rays, and X-rays, and are preferably ultraviolet rays.
  • the actinic ray curable inkjet ink of the present invention contains at least the following polymerizable compound A and polymerizable compound B.
  • ClogP is in the range of ⁇ 1.0 or more and less than 4.0, the molecular weight is 200 or more and less than 1200, and the polymerizable compound B has a (meth) acrylate group in the molecule.
  • (meth) acrylate refers to both and / or “acrylate” and “methacrylate”
  • (meth) acryl refers to both and / or “acryl” and “methacryl”.
  • the “log P value” is a coefficient indicating the affinity of an organic compound for water and 1-octanol.
  • the 1-octanol / water partition coefficient P is a distribution equilibrium when a trace amount of compound is dissolved as a solute in a two-liquid solvent of 1-octanol and water, and is a ratio of the equilibrium concentration of the compound in each solvent. Their logarithm logP relative to the base 10 is indicated. That is, the “log P value” is a logarithmic value of the 1-octanol / water partition coefficient and is known as an important parameter representing the hydrophilicity / hydrophobicity of a molecule.
  • the “ClogP value” is a LogP value calculated by calculation.
  • the ClogP value can be calculated by a fragment method, an atomic approach method, or the like. More specifically, ClogP values can be calculated in the literature (C. Hansch and A. Leo, “Substituent Constants for Correlation Analysis in Chemistry and Biology” (John Wiley & Sons, New 69, New York fragment). Or the following commercially available software package 1 or 2 may be used.
  • Software Package 1 MedChem Software (Release 3.54, Aug. 1991, Medicinal Chemistry Project, Pomona College, Clarmont, CA)
  • Software package 2 Chem Draw Ultra ver. 8.0. (April 2003, CambridgeSoft Corporation, USA)
  • the numerical value of the ClogP value described in the present specification and the like is a “ClogP value” calculated using the software package 2.
  • the compatibility between the gelling agent and the photopolymerizable compound has not been studied in detail. Therefore, when the photopolymerizable compound and the gelling agent are difficult to be compatible, the ink ejection becomes unstable or the gelling agent has a desired gel structure (card house structure or fibrous network structure). There was a problem that the ink droplets that could not be formed were difficult to gel after landing. On the other hand, when the compatibility between the photopolymerizable compound and the gelling agent is too high, there is a problem that the gelling agent cannot be sufficiently crystallized after the ink has landed on the recording medium. Further, even when the gelling agent is compatible with the photopolymerizable compound in the initial stage of printing, the gelling agent gradually becomes incompatible with the continued printing, and the ink ejection property may be lowered.
  • the present inventors use a certain amount of the polymerizable compound A and a certain amount of the polymerizable compound B in combination with the gelling agent, so that the gelling agent is stably compatible, and the ink ejection property. And the gelling agent quickly crystallized after the ink landed on the recording medium, and it was found that coalescence of droplets could be suppressed. The reason is guessed as follows.
  • Polymerizable compound A ((meth) acrylamide compound) has a relatively high hydrophilicity.
  • the polymerizable compound B ((meth) acrylate compound) is relatively hydrophobic.
  • These polymerizable compound A and polymerizable compound B both have a (meth) acryloyl group and are easily compatible with each other.
  • the gelling agent contained in the actinic ray curable inkjet ink has both a hydrophobic part and a hydrophilic part in its molecular structure. The hydrophobic part and the hydrophilic part of the gelling agent tend to have affinity with the polymerizable compound B and the polymerizable compound A, respectively. Therefore, the gelling agent can exist stably in the sol ink.
  • the ink contains a highly hydrophilic polymerizable compound A
  • the gelling agent quickly precipitates and crystallizes. That is, coalescence of the droplets after landing is suppressed, and a high quality image is obtained.
  • the actinic ray curable inkjet ink of the present invention contains the polymerizable compound A (acrylamide compound), the adhesion between the cured ink (printed image) and the recording medium is good. Furthermore, the scratch resistance of the cured film is also increased. Furthermore, since the highly flexible polymerizable compound B is included, the flexibility (bending resistance) of the printed image is also improved.
  • the polymerizable compound A acrylamide compound
  • the polymerizable compound A is a (meth) acrylamide compound. As described above, when the polymerizable compound A is contained in the actinic ray curable inkjet ink, the adhesion between the cured ink and the recording medium is increased. Further, the scratch resistance of the ink cured film is also increased.
  • the ClogP value of the polymerizable compound A is ⁇ 4.0 or more and less than 1.0, preferably ⁇ 3.0 or more and less than 1.0.
  • the ClogP value of the polymerizable compound A is less than ⁇ 4.0, the hydrophilicity becomes excessively high, and the compatibility with the gelling agent and the polymerizable compound B decreases. Therefore, the solubility of the gelling agent becomes unstable, the ink ejection property becomes unstable, or a desired gel structure (card house structure or fibrous network structure) is not formed after landing on the recording medium, In some cases, dot coalescence cannot be suppressed.
  • the ClogP value of the polymerizable compound A is 1.0 or more, the adhesion between the printed image and the recording medium is hardly increased.
  • the number of (meth) acrylamide groups contained in the molecule of the polymerizable compound A is not particularly limited. Only one (meth) acrylamide group may be contained in the polymerizable compound A, and two or more (meth) acrylamide groups may be contained.
  • the molecular weight of the polymerizable compound A is not particularly limited, but is preferably 100 or more and less than 1000, and more preferably 100 or more and less than 500. Some acrylamide compounds having a molecular weight of 100 or less are harmful to living organisms. On the other hand, when the molecular weight of the acrylamide compound is 1000, the viscosity of the ink tends to be excessively high.
  • the polymerizable compound A include the following compounds.
  • the polymerizable compound A is not limited to the following compounds.
  • N N-dimethylacrylamide (molecular weight 99, ClogP value: -0.17), N, N-diethylacrylamide (molecular weight 127, ClogP value: 0.89), acryloylmorpholine (molecular weight 141, ClogP value: -0.07) ), N- (2-hydroxyethyl) acrylamide (molecular weight 115, ClogP value: -1.03), N-isopropylacrylamide (molecular weight 113, ClogP value: 0.25), diacetone acrylamide (molecular weight 169, ClogP value: 0.29), N-methylolacrylamide (molecular weight 101, ClogP value: ⁇ 0.93), N- [3- (dimethylamino) propyl] acrylamide (molecular weight 156, ClogP value: 0.20), N, N ′
  • the content of the polymerizable compound A is preferably 5% by mass or more and less than 50% by mass, more preferably 10 to 40% by mass with respect to the total mass of the actinic ray curable inkjet ink.
  • the content of the polymerizable compound A is 50% by mass or more, the hydrophilicity of the ink increases and the solubility of the gelling agent tends to become unstable. For this reason, ink ejection becomes unstable, or in the ink droplets after landing, the gel structure (card house structure or fibrous network structure) is not sufficiently formed, and it is difficult to suppress dot coalescence.
  • the amount of the polymerizable compound A is less than 5% by mass, the adhesion between the cured ink film and the recording medium is not sufficiently improved.
  • the polymerizable compound B is a (meth) acrylate compound.
  • the gelling agent is stably dissolved in the ink.
  • the flexibility of the ink cured film is increased.
  • the ClogP value of the polymerizable compound B is ⁇ 1.0 or more and less than 4.0, preferably 0 or more and less than 3.6.
  • the ClogP value of the (meth) acrylate compound is less than ⁇ 1.0, the polymerizable compound B and the gelling agent are hardly compatible.
  • the molecular weight of the polymerizable compound B is 200 or more and less than 1200, preferably 300 or more and less than 800. If the molecular weight of the polymerizable compound B is less than 200, the polymerizable compound B tends to volatilize in the ink jet recording apparatus, and ink ejection tends to become unstable. On the other hand, if the molecular weight of the (meth) acrylate compound exceeds 1200, the viscosity of the ink becomes excessively high, and ink ejection tends to become unstable.
  • the number of (meth) acrylate groups contained in the molecule of the polymerizable compound B is not particularly limited, it is preferable to have two or more (meth) acrylate groups in the molecule. Specifically, it is preferable to have 2, 3 or 4 (meth) acrylate groups from the viewpoint of the curability of the ink.
  • Preferred examples of the polymerizable compound B include the following compounds.
  • the polymerizable compound B is not limited to the following compounds. 4EO-modified pentaerythritol tetraacrylate (SR494, manufactured by Sartomer, molecular weight 528, ClogP value: 2.28), tetraethylene glycol diacrylate (V # 335HP, manufactured by Osaka Organic Chemical Co., Ltd., molecular weight 302, ClogP value: 1.15)
  • Polyethylene glycol # 400 diacrylate (NK ester A-400, manufactured by Shin-Nakamura Chemical Co., Ltd., molecular weight 508, Clog P value: 0.47), polyethylene glycol # 600 diacrylate (NK ester A-600, manufactured by Shin-Nakamura Chemical Co., Ltd.)
  • Molecular weight 708, ClogP value: -0.16) polyethylene glycol # 200 dimethacrylate (NK ester 4G, manufactured by Shin-Nakamura Chemical Co., Ltd., molecular
  • the structure represented by (—CH 2 —CH 2 —O—) is preferably contained in an amount of 3 or more and less than 25, more preferably 3 or more and less than 15.
  • the flexibility of the cured film of the ink is increased.
  • the structure of the polymerizable compound B contains 25 or more structures represented by (—CH 2 —CH 2 —O—)
  • the hydrophilicity of the polymerizable compound B tends to become excessively high, and the gelling agent There is a possibility that it becomes difficult to be compatible with.
  • polymerizable compound B is tetraethylene glycol diacrylate (V # 335HP, manufactured by Osaka Organic Chemical Co., Ltd., molecular weight 302, ClogP value: 1.15), polyethylene glycol # 400 diacrylate (NK ester A-400, Shin Nakamura).
  • the content of the polymerizable compound B is 10% by mass or more and less than 70% by mass, and more preferably 20 to 50% by mass with respect to the total mass of the actinic ray curable inkjet ink.
  • the content of the polymerizable compound B is 70% by mass or more, the amount of the polymerizable compound A having an acrylamide group is relatively small, and the adhesion to the recording medium is hardly increased.
  • the content of the polymerizable compound B is less than 10% by mass, the solubility of the gelling agent becomes unstable, and ink ejection tends to become unstable. Further, the flexibility of the printed image is not sufficiently increased, and the bendability of the printed matter is lowered.
  • the actinic ray curable inkjet ink may further contain a photopolymerizable compound other than the polymerizable compound A and the polymerizable compound B.
  • the other polymerizable compound can be a radical polymerizable compound.
  • the other polymerizable compound may be a compound (monomer, oligomer, polymer or mixture thereof) having an ethylenically unsaturated bond capable of radical polymerization.
  • One type of other polymerizable compound may be contained in the actinic ray curable inkjet ink, or two or more types may be contained.
  • Examples of other polymerizable compounds include unsaturated carboxylic acids and their salts, unsaturated carboxylic acid ester compounds, unsaturated carboxylic acid urethane compounds, unsaturated carboxylic acid amide compounds and their Examples include anhydrides, acrylonitrile, styrene, unsaturated polyesters, unsaturated polyethers, unsaturated polyamides, and unsaturated urethanes.
  • Examples of the unsaturated carboxylic acid include (meth) acrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid and the like.
  • polymerizable compounds are particularly preferably (meth) acrylate monomers and / or oligomers and other polymerizable oligomers.
  • Examples of (meth) acrylate monomers and / or oligomers include, for example, isoamyl (meth) acrylate, behenyl (meth) acrylate, stearyl (meth) acrylate, lauryl (meth) acrylate, octyl (meth) acrylate, decyl (meth) Acrylate, dodecyl (meth) acrylate, isooctyl (meth) acrylate, isomyristyl (meth) acrylate, isostearyl (meth) acrylate, 2-acryloyloxyethyl hexahydrophthalic acid, 2-acryloyloxyethyl succinic acid, 2- Acryloyloxyethylphthalic acid, 2-acryloyloxyethyl-2-hydroxyethyl-phthalic acid, lactone-modified flexible acrylate, 2-ethylhexyl (meth) acrylate, 2-
  • Examples of other polymerizable oligomers include epoxy acrylate, aliphatic urethane acrylate, aromatic urethane acrylate, polyester acrylate, linear acrylic oligomer, and the like.
  • the actinic ray curable inkjet ink of the present invention contains a gelling agent. Therefore, the ink undergoes a sol-gel phase transition reversibly depending on the temperature.
  • the sol-gel phase transition referred to in the present invention is a solution state having fluidity at a high temperature, but when cooled below the gelation temperature, the entire liquid is gelled and changes to a state in which the fluidity is lost. It refers to the phenomenon of returning to a fluid liquid state when heated above.
  • gelation means forming any of the following structures.
  • Lamella structure 2) Polymer network structure formed by non-covalent bond or hydrogen bond 3) Polymer network structure formed by physical aggregation state 4) Interaction such as aggregation structure of fine particles or precipitated microcrystal
  • Interaction such as aggregation structure of fine particles or precipitated microcrystal
  • the sol means a state in which the interaction formed by the gelation is eliminated and the liquid has fluidity.
  • the ink after landing on the recording medium is gelled, coalescence between adjacent dots is suppressed, and the image quality is improved. Further, when the ink gels, it becomes difficult for oxygen to diffuse into the ink droplets. Therefore, the photopolymerization of the photopolymerizable compound is less likely to be inhibited by oxygen and the curability of the ink is increased.
  • the amount of gelling agent added to the actinic radiation curable inkjet ink is 0.5% by mass or more and less than 10% by mass, and more preferably 1% by mass or more and less than 6% by mass with respect to the total mass of the ink.
  • the actinic ray curable inkjet ink contains two or more kinds of gelling agents, the total amount of the gelling agents is preferably in the above range.
  • the actinic ray curable ink-jet ink may not sufficiently undergo sol-gel phase transition.
  • the content of the gelling agent exceeds 10% by mass, the solubility of the gelling agent becomes unstable, and ink ejection tends to become unstable.
  • the gelling agent contained in the actinic ray curable ink jet may be either a wax or a hydrogen bonding gelling agent, but is preferably a wax from the viewpoint of sol-gel phase transition, and is particularly photopolymerizable. From the viewpoint of compatibility with the compound, a wax having a polar group in the molecule is preferable.
  • wax refers to an organic substance that is solid at room temperature and becomes liquid when heated.
  • the melting point of the wax is preferably 30 ° C. or higher and lower than 150 ° C.
  • the wax contained in the actinic radiation curable ink-jet ink is at least 1) dissolved in the photopolymerizable compound at a temperature higher than the gelation temperature, and 2) crystallized in the ink at a temperature lower than the gelation temperature. ,is required.
  • the structure in which the photopolymerizable compound is encapsulated in the space three-dimensionally surrounded by the plate crystal is sometimes referred to as “card house structure”.
  • the card house structure is formed, the liquid photopolymerizable compound can be held and ink droplets can be pinned. Thereby, coalescence of droplets can be suppressed.
  • the photopolymerizable compound and the wax are compatible.
  • the photopolymerizable compound and the wax are phase-separated, it may be difficult to form a card house structure.
  • the type of wax is not particularly limited.
  • Preferred examples of the wax include dibehenyl ketone, distearyl ketone, dipalmityl ketone, dimyristyl ketone, dilauryl ketone, palmityl stearyl ketone, stearyl behenyl ketone, 18-Pentriacontanon (for example, a reagent manufactured by Alfa Aeser), ketone Aliphatic ketone compounds such as wax (for example, Kao Wax T1 manufactured by Kao Corporation); behenyl behenate (for example, Unistar M-2222SL manufactured by NOF Corporation), stearyl stearate (for example, EXCEPARL SS manufactured by Kao Corporation), cetyl palmitate (For example, Amreps PC manufactured by Higher Alcohol Industry Co., Ltd.), fats such as palmitic acid stearate, myristyl myristate, lauryl laurate, myricyl cellotate, be
  • Monoester compounds such as paraffin wax, microcrystalline wax, petrolactam; plant waxes such as candelilla wax, carnauba wax, rice wax, wood wax, jojoba oil, jojoba solid wax, and jojoba ester; beeswax Animal waxes such as lanolin and whale wax; mineral waxes such as montan wax and hydrogenated wax; hardened castor oil or hardened castor oil derivative; montan wax derivative, paraffin wax derivative, microcrystalline wax derivative or polyethylene wax derivative, etc.
  • petroleum waxes such as paraffin wax, microcrystalline wax, petrolactam
  • plant waxes such as candelilla wax, carnauba wax, rice wax, wood wax, jojoba oil, jojoba solid wax, and jojoba ester
  • beeswax Animal waxes such as lanolin and whale wax
  • mineral waxes such as montan wax and hydrogenated wax
  • hardened castor oil or hardened castor oil derivative montan wax derivative, paraffin wax derivative
  • Modified waxes such as behenic acid, arachidic acid, stearic acid, palmitic acid, myristic acid, lauric acid, oleic acid, and erucic acid; stearyl alcohol, behenyl Higher alcohols such as alcohol; hydroxystearic acid such as 12-hydroxystearic acid; 12-hydroxystearic acid derivatives; lauric acid amide, stearic acid amide, behenic acid amide, oleic acid amide, erucic acid amide, ricinoleic acid amide, 12- Fatty acid amides such as hydroxystearic acid amide (eg Nikka Amide series manufactured by Nippon Kasei Co., Ltd.
  • hydroxystearic acid amide eg Nikka Amide series manufactured by Nippon Kasei Co., Ltd.
  • N-stearyl stearic acid amide N-oleyl palmitic acid amide
  • N-substituted fatty acid amides special fatty acid amides such as N, N′-ethylenebisstearylamide, N, N′-ethylenebis-12-hydroxystearylamide, and N, N′-xylylenebisstearylamide
  • dodecylamine tetradecyl Higher amines such as amine or octadecylamine
  • polyhydric alcohol fatty acid esters such as glycerin fatty acid ester, sorbitan fatty acid ester, propylene glycol fatty acid ester, ethylene glycol fatty acid ester, polyoxyethylene fatty acid ester (for example, EMALLEX series, Riken Vitamin manufactured by Nihon Emulsion Co., Ltd.) Riquemar series manufactured by Riken Vitamin Co.
  • waxes may be contained alone or in combination of two or more in the actinic ray curable inkjet ink.
  • Commercially available waxes are often a mixture of two or more types of waxes. Therefore, commercially available wax may be used after separation and purification as necessary.
  • the wax preferably has a polar group in the molecule.
  • the polar group is preferably a ketone group, —OH group, carboxyl group, amide group, carbonyl group, ester bond or the like.
  • the wax is preferably an aliphatic ketone compound, an aliphatic monoester compound, a higher fatty acid, a fatty acid amide, a higher alcohol, or a polyhydric alcohol fatty acid ester, and is an aliphatic ketone compound or an aliphatic monoester compound. More preferably.
  • the polar group may form hydrogen bonds with the acrylamide group, and the solubility of the wax may become excessively high.
  • the gelling agent may be a hydrogen bonding gelling agent.
  • the “hydrogen bonding gelling agent” refers to a compound that forms a fibrous metastable structure by intermolecular hydrogen bonding in ink and gels by encapsulating a solvent in the network of the fiber structure. .
  • hydrogen-bonding gelling agents examples include fatty acid inulins such as inulin stearate; fatty acid dextrins such as dextrin palmitate and dextrin myristate (such as the Leopard series manufactured by Chiba Flour Mills); glyceryl behenate; glyceryl behenate; Sunpolyglyceryl (Nisshin Oilio Co., Ltd.
  • Nomucoat series, etc. N-lauroyl-L-glutamic acid dibutylamide, N- (2-ethylhexanoyl) -L-glutamic acid dibutylamide and other amide compounds (available from Ajinomoto Fine Techno) ); 1,3: 2,4-bis-O-benzylidene-D-glucitol (Gelol D, available from Shin Nippon Chemical Co., Ltd.) and the like; JP-A 2005-126507, JP-A 2005-255821 Publication and JP2010-11790 Low molecular oil-gelling agent described in Japanese; and the like.
  • Photopolymerization initiator The actinic ray curable inkjet ink further contains a photopolymerization initiator.
  • Photopolymerization initiators include an intramolecular bond cleavage type and an intramolecular hydrogen abstraction type. Examples of intramolecular bond cleavage type photopolymerization initiators include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethyl ketal, 1- (4-isopropylphenyl) -2.
  • intramolecular hydrogen abstraction type photopolymerization initiators examples include benzophenone, methyl 4-phenylbenzophenone o-benzoylbenzoate, 4,4′-dichlorobenzophenone, hydroxybenzophenone, 4-benzoyl-4′-methyl-diphenyl.
  • Benzophenones such as sulfide, acrylated benzophenone, 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone, 3,3′-dimethyl-4-methoxybenzophenone; 2-isopropylthioxanthone, 2,4 -Thioxanthone series such as dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone; Aminobenzophenone series such as Michler ketone, 4,4'-diethylaminobenzophenone; 10-butyl-2-chloroacridone, 2-ethyl Anthraquinone, 9,10-phenanthrene Quinone, include camphor quinone and the like.
  • the content of the photopolymerization initiator in the actinic ray curable ink-jet ink is preferably 0.01% by mass to 10% by mass, although it depends on the type of actinic ray or photopolymerizable compound.
  • a photoacid generator may be contained in the photopolymerization initiator in the actinic ray curable inkjet ink.
  • photoacid generators include chemically amplified photoresists and compounds used for photocationic polymerization (Organic Electronics Materials Study Group, “Organic Materials for Imaging”, Bunshin Publishing (1993), 187. See page 192).
  • the actinic ray curable ink-jet ink may further contain a photopolymerization initiator auxiliary agent or a polymerization inhibitor, if necessary.
  • the photopolymerization initiator assistant may be a tertiary amine compound, preferably an aromatic tertiary amine compound.
  • aromatic tertiary amine compounds 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, N, N-dimethylhexylamine and the like are included.
  • N, N-dimethylamino-p-benzoic acid ethyl ester and N, N-dimethylamino-p-benzoic acid isoamyl ethyl ester are preferred. Only one kind of these compounds may be contained in the actinic ray curable inkjet ink, or two or more kinds thereof may be contained.
  • polymerization inhibitors include (alkyl) phenol, hydroquinone, catechol, resorcin, p-methoxyphenol, t-butylcatechol, t-butylhydroquinone, pyrogallol, 1,1-picrylhydrazyl, phenothiazine, p-benzoquinone , Nitrosobenzene, 2,5-di-t-butyl-p-benzoquinone, dithiobenzoyl disulfide, picric acid, cuperone, aluminum N-nitrosophenylhydroxylamine, tri-p-nitrophenylmethyl, N- (3-oxyanilino- 1,3-dimethylbutylidene) aniline oxide, dibutylcresol, cyclohexanone oxime cresol, guaiacol, o-isopropylphenol, butyraloxime, methyl ethyl ketoxime, cyclohexanone oxime
  • the actinic ray curable inkjet ink may contain a coloring material.
  • the colorant can be a dye or a pigment.
  • a pigment is more preferable because it has good dispersibility with respect to the components of the ink and is excellent in weather resistance.
  • the dye can be an oil-soluble dye or the like.
  • oil-soluble dyes include the following various dyes.
  • magenta dyes include MS Magenta VP, MS Magenta HM-1450, MS Magenta HSo-147 (above, manufactured by Mitsui Toatsu), AIZENSOT Red-1, AIZEN SOT Red-2, AIZEN SOTRed-3, AIZEN SOT Pink-1, SPIRON Red GEH SPECIAL (above, manufactured by Hodogaya Chemical Co., Ltd.), RESOLIN Red FB 200%, MACROLEX Red Violet R, MACROLEX ROT5B (above, manufactured by Bayer Japan Co., Ltd.), KAYASET Red B, KAYA 802 (above, Nippon Kayaku Co., Ltd.), PHLOXIN, ROSE Bengal, ACID Red (above, Manufactured by Iva Kasei), HSR-31, DIARESIN Red K (manufactured by Mitsubishi Kasei Corp
  • cyan dyes examples include MS Cyan HM-1238, MS Cyan HSo-16, Cyan HSo-144, MS Cyan VPG (manufactured by Mitsui Toatsu), AIZEN SOT Blue-4 (manufactured by Hodogaya Chemical Co., Ltd.), RESOLIN BR. Blue BGLN 200%, MACROLEX Blue RR, CERES Blue GN, SIRIUS SUPRATURQ. Blue Z-BGL, SIRIUS SUTRA TURQ. Blue FB-LL 330% (from Bayer Japan), KAYASET Blue FR, KAYASET Blue N, KAYASET Blue 814, Turq.
  • Blue GL-5 200 Light Blue BGL-5 200 (Nippon Kayaku Co., Ltd.), DAIWA Blue 7000, Olesol Fast Blue GL (Daiwa Kasei Co., Ltd.), DIARESIN Blue P (Mitsubishi Chemical Co., Ltd.) Blue 670, NEOPEN Blue 808, ZAPON Blue 806 (above, manufactured by BASF Japan Ltd.) and the like are included.
  • yellow dyes examples include MS Yellow HSm-41, Yellow KX-7, Yellow EX-27 (Mitsui Toatsu), AIZEN SOT Yellow-1, AIZEN SOT Yellow W-3, AIZEN SOT Yellow-6 (above, Hodogaya (Manufactured by Kagakusha), MACROLEX Yellow 6G, MACROLEX FLUOR.
  • black dyes examples include MS Black VPC (Mitsui Toatsu Co., Ltd.), AIZEN SOT Black-1, AIZEN SOT Black-5 (above, manufactured by Hodogaya Chemical Co., Ltd.), RESORIN Black GSN 200%, RESOLIN BlackBS (above, Bayer Japan), KAYASET Black AN (Nippon Kayaku), DAIWA Black MSC (Daiwa Kasei), HSB-202 (Mitsubishi Kasei), NEPTUNE Black X60, NEOPEN Black X58 (above, BASF) Japan product).
  • the pigment is not particularly limited, but may be, for example, an organic pigment or an inorganic pigment having the following numbers 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, 257, Pigment Violet 3, 19, 23, 29, 30, 37, 50, 88, Pigment Orange 13, 16, 20, 36, etc. are included.
  • Examples of blue or cyan pigments include Pigment Blue 1, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 17-1, 22, 27, 28, 29, 36. , 60 and the like.
  • Examples of green pigments include Pigment Green 7, 26, 36, and 50.
  • Examples of yellow pigments 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, 193 and the like.
  • Examples of the black pigment include Pigment Black 7, 28, 26 and the like.
  • Examples of commercially available pigments include chromofine yellow 2080, 5900, 5930, AF-1300, 2700L, chromofine orange 3700L, 6730, chromofine scarlet 6750, chromofine magenta 6880, 6886, 6891N, 6790, 6887, chromo Fine Violet RE, Chromo Fine Red 6820, 6830, Chromo Fine Blue HS-3, 5187, 5108, 5197, 5085N, SR-5020, 5026, 5050, 4920, 4927, 4937, 4824, 4933GN-EP, 4940, 4973, 5205, 5208, 5214, 5221, 5000P, Chromofine Green 2GN, 2GO, 2G-550D, 5310, 5370, 6830, Chromofine Black A-1103, Seika Fast Yellow 10GH, A-3, 2035, 2054, 2200, 2270, 2300, 2400 (B), 2500, 2600, ZAY
  • the pigment can be dispersed by, for example, a ball mill, sand mill, attritor, roll mill, agitator, Henschel mixer, colloid mill, ultrasonic homogenizer, pearl mill, wet jet mill, paint shaker, or the like.
  • the pigment is dispersed so that the average particle diameter of the pigment particles is preferably 0.08 to 0.5 ⁇ m, and the maximum particle diameter is preferably 0.3 to 10 ⁇ m, more preferably 0.3 to 3 ⁇ m. Is preferred.
  • the dispersion of the pigment is adjusted by the selection of the pigment, the dispersant, and the dispersion medium, the dispersion conditions, the filtration conditions, and the like.
  • the actinic ray curable inkjet ink may further contain a dispersant in order to enhance the dispersibility of the pigment.
  • the dispersant include a hydroxyl group-containing carboxylic acid ester, a salt of a long chain polyaminoamide and a high molecular weight acid ester, a salt of a high molecular weight polycarboxylic acid, a salt of a long chain polyaminoamide and a polar acid ester, a high molecular weight unsaturated acid ester , Polymer copolymer, modified polyurethane, modified polyacrylate, polyether ester type anionic activator, naphthalene sulfonic acid formalin condensate salt, aromatic sulfonic acid formalin condensate salt, polyoxyethylene alkyl phosphate ester, polyoxyethylene Nonylphenyl ether, stearylamine acetate and the like are included.
  • Examples of commercially available dispersants include Avecia's Solspers
  • the actinic ray curable inkjet ink may further contain a dispersion aid as necessary.
  • the dispersion aid may be selected according to the pigment.
  • the total amount of the dispersing agent and the dispersing aid is preferably 1 to 50% by mass with respect to the pigment.
  • the pigment may be dispersed in a solvent or the like, but is more preferably dispersed in the aforementioned photopolymerizable compound (particularly a monomer having a low viscosity).
  • the content of the pigment or dye is preferably from 0.1 to 20% by mass, more preferably from 0.4 to 10% by mass, based on the total mass of the actinic ray curable inkjet ink. This is because when the content of the pigment or dye is too small, the resulting image is not sufficiently colored, and when it is too large, the viscosity of the ink increases and the dischargeability from the ink jet recording apparatus decreases.
  • the actinic ray curable inkjet ink may further contain other components as necessary.
  • Other components may be various additives, other resins, and the like.
  • the additive include a surfactant, a leveling additive, a matting agent, an ultraviolet absorber, an infrared absorber, an antibacterial agent, and a basic compound for enhancing the storage stability of the ink.
  • basic compounds include basic alkali metal compounds, basic alkaline earth metal compounds, basic organic compounds such as amines, and the like.
  • other resins include resins for adjusting the physical properties of the cured film, such as polyester resins, polyurethane resins, vinyl resins, acrylic resins, rubber resins, and waxes. It is.
  • the actinic ray curable inkjet ink may contain water or an organic solvent as necessary.
  • the organic solvent is contained in the ink, effects such as easy penetration of the ink into the recording medium can be obtained.
  • organic solvent examples include, for example, glycerin, 1,2,6-hexanetriol, trimethylolpropane, ethylene glycol, propylene glycol, 1,3-butanediol, 2,3-butanediol, 2-ethyl-2- Methyl-1,3-propanediol, 3,3-dimethyl-1,2-butanediol, 2,2-diethyl-1,3-propanediol, 2-ethyl-1,3-hexanediol, 2,2, Alkanediols (polyhydric alcohols) such as 4-trimethyl-1,3-pentanediol; sugar alcohols; alkyl alcohols having 1 to 4 carbon atoms such as ethanol, methanol, butanol, propanol, isopropanol; ethylene glycol monomethyl ether , Ethylene glycol monoethyl ether, ethylene glycol Monobutyl
  • Actinic-light curable inkjet ink is an ink which reversibly changes sol-gel phase with temperature as described above. Since the sol-gel phase transition type actinic ray curable ink is a sol at a high temperature (for example, about 80 ° C.), it can be ejected from an ink jet recording head. When actinic ray curable inkjet ink is ejected at a high temperature, ink droplets (dots) land on the recording medium, and then naturally cool to gel. Thereby, coalescence of adjacent dots can be suppressed and image quality can be improved.
  • a high temperature for example, about 80 ° C.
  • the viscosity of the ink at a high temperature is not more than a certain level.
  • the viscosity of the actinic ray curable inkjet ink at 80 ° C. is preferably 3 to 20 mPa ⁇ s.
  • the viscosity of the ink at normal temperature after landing is a certain level or more.
  • the viscosity at 25 ° C. of the actinic ray curable inkjet ink is preferably 1000 mPa ⁇ s or more.
  • the gelation temperature of the sol-gel phase transition ink is preferably 40 ° C. or higher and 70 ° C. or lower, and more preferably 50 ° C. or higher and 65 ° C. or lower.
  • the gelation temperature is a temperature at which the fluidity decreases due to gelation in the process of cooling the ink in the sol state.
  • the viscosity at 80 ° C., the viscosity at 25 ° C. and the gelation temperature of the sol-gel phase transition type ink can be determined by measuring the temperature change of the dynamic viscoelasticity of the ink with a rheometer. Specifically, a temperature change curve of viscosity is obtained when the ink is heated to 100 ° C. and cooled to 20 ° C. under conditions of a shear rate of 11.7 (1 / s) and a temperature decrease rate of 0.1 ° C./s. . And the viscosity in 80 degreeC and the viscosity in 25 degreeC can be calculated
  • the gelation temperature is a temperature at which the viscosity changes greatly in the temperature change curve of the viscosity.
  • the gelation temperature can be a temperature at which the viscosity becomes 200 mPa ⁇ s.
  • the rheometer can be a stress control type rheometer Physica MCR series manufactured by Anton Paar.
  • the cone plate can have a diameter of 75 mm and a cone angle of 1.0 °.
  • Actinic ray curable inkjet ink is prepared by heating the above-mentioned photopolymerizable compound, gelling agent, photopolymerization initiator, colorant, and each optional component under heating. It can obtain by mixing in. It is preferable to filter the obtained liquid mixture with a predetermined filter.
  • the image forming method of the present invention is not particularly limited, but 1) a step of discharging the actinic radiation curable inkjet ink onto a recording medium, and 2) irradiating the ink landed on the recording medium with actinic rays to cure the ink. It is preferable to include the process.
  • the above-mentioned actinic ray curable inkjet ink accommodated in the inkjet recording head is ejected as droplets toward the recording medium through the nozzle.
  • the temperature of the inkjet ink accommodated in the ejection recording head is set to a temperature at which the gelling agent does not precipitate. That is, the temperature is such that the saturated dissolution amount of the gelling agent in the ink is greater than the amount of the gelling agent contained in the ink.
  • the temperature of the inkjet ink in the inkjet recording head is set to a temperature that is 10 to 30 ° C. higher than the gelation temperature.
  • the ink temperature in the ink jet recording head is less than (gelation temperature + 10) ° C.
  • the ink gels in the ink jet recording head or on the nozzle surface and the discharge property of ink droplets is likely to deteriorate.
  • the temperature of the ink in the ink jet recording head exceeds (gelation temperature + 30) ° C., the ink becomes too hot and the ink component may deteriorate.
  • the ink droplets landed on the recording medium are cooled and gelled quickly by the sol-gel phase transition. As a result, the ink droplets can be pinned without diffusing. Furthermore, it becomes difficult for oxygen to diffuse into the ink droplets. Therefore, in the step 2) described later, the photopolymerization of the photopolymerizable compound is less likely to be inhibited by oxygen, and the curability of the ink is increased, so that even a low light source such as an LED can be sufficiently cured.
  • the temperature of the recording medium when the ink droplets land is preferably set to a temperature that is 10 to 20 ° C. lower than the gelation temperature of the ink. If the temperature of the recording medium is too low, the ink droplets gel excessively and pinning, so that the ink droplets are not sufficiently leveled and the image gloss may be lowered. On the other hand, if the temperature of the recording medium is too high, the ink droplets are difficult to gel and adjacent dots may be mixed together. By appropriately adjusting the temperature of the recording medium, it is possible to achieve appropriate leveling and appropriate pinning so that adjacent dots of ink droplets do not mix with each other.
  • the recording medium may be paper or a resin film.
  • paper examples include coated paper for printing, coated paper B for printing, and the like.
  • the resin film examples include a polyethylene terephthalate film and a vinyl chloride film.
  • the conveyance speed of the recording medium is preferably 30 to 120 m / min.
  • the conveyance speed is too high, the image quality is deteriorated or the ink is not sufficiently cured.
  • Step 2 By irradiating the ink landed on the recording medium with an actinic ray, the photopolymerizable compound contained in the ink droplet is crosslinked or polymerized to cure the ink droplet.
  • the actinic ray to be irradiated may be appropriately selected depending on the type of the photopolymerizable compound, and may be ultraviolet rays or electron beams.
  • an ultraviolet light source a metal halide lamp or the like may be used.
  • an LED it is possible to suppress dissolution of the ink droplet surface by the radiant heat of the light source.
  • the light from the LED light source preferably has a peak illuminance of 1.0 to 10 W / cm 2 at a wavelength of 370 to 410 nm, and more preferably 1 to 5 W / cm 2 .
  • the peak illuminance is the illuminance on the surface of the recording medium.
  • the conveyance speed of the recording medium during light irradiation is preferably 30 to 120 m / min. The higher the conveyance speed, the less the influence of radiant heat, and the higher the image forming speed, which is preferable. However, if the conveying speed is too high, photocuring may be insufficient.
  • the temperature of the recording medium can be adjusted arbitrarily.
  • the temperature of the recording medium in the ejection process and the temperature of the recording medium in the curing process are not necessarily the same, and may be controlled independently.
  • Actinic ray curable inkjet recording apparatus An actinic ray curable inkjet recording apparatus is described.
  • Actinic ray curable ink jet recording apparatuses include a line recording method (single pass recording method) and a serial recording method.
  • the line recording method is preferable from the viewpoint of high-speed recording, although it may be selected according to the required image resolution and recording speed.
  • FIG. 1A and FIG. 1B are diagrams illustrating an example of a configuration of a main part of a line recording type ink jet recording apparatus.
  • FIG. 1A is a side view
  • FIG. 1B is a top view.
  • the inkjet recording apparatus 10 includes a head carriage 16 that accommodates a plurality of inkjet recording heads 14 and the entire width of the recording medium 12, and the head carriage 16 (the recording medium conveyance direction).
  • An actinic ray irradiation unit 18 disposed on the downstream side, and a temperature control unit 19 (19a and 19b) disposed on the lower surface of the recording medium 12.
  • the head carriage 16 is connected to an ink tank 31 for storing ink via an ink flow path 30.
  • the head carriage 16 is fixedly arranged so as to cover the entire width of the recording medium 12, and accommodates a plurality of inkjet recording heads 14 provided for each color.
  • Ink is supplied to the ink jet recording head 14.
  • the ink may be supplied directly or by an ink supply unit (not shown) from an ink cartridge (not shown) that is detachably attached to the inkjet recording apparatus 10.
  • a plurality of inkjet recording heads 14 are arranged in the transport direction of the recording medium 12 for each color.
  • the number of inkjet recording heads 14 arranged in the conveyance direction of the recording medium 12 is set according to the nozzle density of the inkjet recording head 14 and the resolution of the print image. For example, when an image having a resolution of 1440 dpi is formed using the inkjet recording head 14 having a droplet amount of 2 pl and a nozzle density of 360 dpi, the four ejection recording heads 14 are arranged so as to be shifted with respect to the conveyance direction of the recording medium 12. do it.
  • the two ink jet recording heads 14 may be arranged in a shifted manner.
  • dpi represents the number of ink droplets (dots) per 2.54 cm.
  • the actinic ray irradiation unit 18 covers the entire width of the recording medium 12 and is arranged on the downstream side of the head carriage 16 in the conveyance direction of the recording medium.
  • the actinic ray irradiation unit 18 irradiates the droplets ejected by the inkjet recording head 14 and landed on the recording medium 12 with actinic rays to cure the droplets.
  • examples of the active light irradiation unit 18 include a fluorescent tube (low pressure mercury lamp, germicidal lamp), a cold cathode tube, an ultraviolet laser, and an operating pressure of several hundred Pa to 1 MPa. These include low pressure, medium pressure, high pressure mercury lamps, metal halide lamps and LEDs. From the viewpoint of curability, ultraviolet irradiation means for irradiating ultraviolet rays having an illuminance of 100 mW / cm 2 or more; specifically, a high-pressure mercury lamp, a metal halide lamp, and an LED are preferable.
  • the ultraviolet irradiation means is particularly preferably an LED from the viewpoint of low power consumption and low radiant heat. Specific examples of the LED that is the ultraviolet irradiation means include 395 nm, water-cooled LED, etc. manufactured by Phoseon Technology.
  • examples of the actinic ray irradiating unit 18 include electron beam irradiating means such as a scanning method, a curtain beam method, and a broad beam method. Therefore, a curtain beam type electron beam irradiation means is preferable.
  • Examples of electron beam irradiation means include “Curetron EBC-200-20-30” manufactured by Nissin High Voltage Co., Ltd., “Min-EB” manufactured by AIT Co., Ltd., and the like.
  • the temperature controller 19 (19a and 19b) is disposed on the lower surface of the recording medium 12, and maintains the recording medium 12 at a predetermined temperature.
  • the temperature control unit 19 can be, for example, various heaters.
  • the recording medium 12 is conveyed between the head carriage 16 of the inkjet recording apparatus 10 and the temperature control unit 19a.
  • the recording medium 12 is adjusted to a predetermined temperature by the temperature control unit 19a.
  • high-temperature ink is ejected from the ink jet recording head 14 of the head carriage 16 to adhere (land) on the recording medium 12.
  • the actinic ray irradiating unit 18 irradiates the ink droplets attached on the recording medium 12 with an actinic ray to cure.
  • the temperature of the ink in the ink jet recording head 14 is set to a temperature higher by 10 to 30 ° C. than the gelation temperature of the ink in order to improve the ink ejectability. It is preferable. If the ink temperature in the ink jet recording head 14 is less than (gelation temperature + 10) ° C., the ink gels in the ink jet recording head 14 or on the nozzle surface, and the ink ejection properties tend to decrease. On the other hand, when the temperature of the ink in the inkjet recording head 14 exceeds (gelling temperature + 30) ° C., the ink becomes too high, and the ink component may be deteriorated.
  • the amount of droplets ejected from each nozzle of the inkjet recording head 14 is preferably 0.5 pl to 10 pl in order to form a high resolution image, although it depends on the resolution of the image. More preferably, it is 1 pl to 4.0 pl.
  • Irradiation of actinic rays from the actinic ray irradiating unit 18 is performed within 10 seconds after the ink droplets adhere on the recording medium, preferably from 0.001 seconds to suppress the adjacent ink droplets from being coalesced. It is preferable to carry out within 5 seconds, more preferably within 0.01 second to 2 seconds. Irradiation with actinic rays is preferably performed after ink is ejected from all the inkjet recording heads 14 accommodated in the head carriage 16. At this time, the temperature of the recording medium 12 is appropriately adjusted by the temperature controller 19b. The temperature of the recording medium 12 at this time may be the same as or different from the temperature of the recording medium 12 at the time of ink ejection; that is, the temperature adjusted by the temperature control unit 19a.
  • the acceleration voltage for electron beam irradiation is preferably 30 to 250 kV and more preferably 30 to 100 kV in order to perform sufficient curing.
  • the electron beam irradiation amount is preferably 30 to 100 kGy, and more preferably 30 to 60 kGy.
  • the total film thickness of the image after ink curing is preferably 2 to 25 ⁇ m.
  • the “total film thickness” is the maximum film thickness of the cured ink that has landed on the recording medium.
  • FIG. 2 is a diagram illustrating an example of a configuration of a main part of the serial recording type inkjet recording apparatus 20.
  • the inkjet recording apparatus 20 includes a plurality of inkjet recording heads that are narrower than the entire width of the recording medium, instead of the head carriage 16 that is fixedly arranged so as to cover the entire width of the recording medium. 2 can be configured except that a head carriage 26 that accommodates the head 24 and a guide portion 27 for moving the head carriage 26 in the width direction of the recording medium 12 are provided.
  • the head carriage 26 is ejected from the inkjet recording head 24 accommodated in the head carriage 26 while moving in the width direction of the recording medium 12 along the guide portion 27. After the head carriage 26 has completely moved in the width direction of the recording medium 12 (for each pass), the recording medium 12 is fed in the transport direction. Thereafter, the active light irradiation unit 28 irradiates the active light. Except for these operations, an image is recorded in substantially the same manner as the line recording type inkjet recording apparatus 10 described above.
  • actinic ray curable inkjet inks were prepared with the following components (photopolymerizable compound, gelling agent, photopolymerization initiator, polymerization inhibitor, and pigment dispersion).
  • Polymerizable compound B Polyethylene glycol diacrylate (NK ester A-400, manufactured by Shin-Nakamura Chemical Co., Ltd., molecular weight 508, EO unit amount 9, ClogP value: 0.47) 4EO-modified pentaerythritol tetraacrylate (SR494, manufactured by Sartomer, molecular weight 528, ClogP value: 2.28) 6EO-modified trimethylolpropane triacrylate (SR499, manufactured by Sartomer, molecular weight 560, ClogP value: 3.57) Tripropylene glycol diacrylate (APG-200, manufactured by Shin-Nakamura Chemical Co., Ltd., molecular weight 300, Clog P value: 2.21)
  • Wax behenic acid (Lunac BA, manufactured by Kao Corporation, molecular weight 340, Clog P value: 10.1) Palmitic acid amide (Diamid KP, Nippon Kasei Co., Ltd., molecular weight 255, ClogP value: 6.3) Aliphatic ketone (Kao wax T1, manufactured by Kao Corporation, Clog P value of 15 or more) Behenyl behenate (Unistar M-2222SL, NOF Corporation, Clog P value of 15 or more) ⁇ Hydrogen bondable gelling agent N-lauroyl-L-glutamic acid dibutyramide (GP-1, Ajinomoto Co., Inc., molecular weight 439, ClogP value: 5.4)
  • Pigment dispersion -Preparation of pigment dispersion 1 (K: black)
  • K black
  • a dispersant, a photopolymerizable compound, and a polymerization inhibitor are placed in a stainless beaker and heated on a hot plate at 65 ° C for 1 hour. The mixture was dissolved by heating and stirring. After cooling the obtained solution to room temperature, the following black pigment 1 was added, and it was put in a glass bottle together with 200 g of zirconia beads having a diameter of 0.5 mm and sealed. This was dispersed in a paint shaker for 5 hours. Thereafter, zirconia beads were removed to prepare Pigment Dispersion Liquid 1.
  • pigment dispersion 2 Dispersant, photopolymerizable compound, and polymerization inhibitor were placed in a stainless beaker at the composition ratio shown below, and dissolved by heating and stirring for 1 hour while heating on a 65 ° C hot plate. I let you. The resulting solution was cooled to room temperature, then the following black pigment 1 was added, sealed in a glass bottle with 200 g of zirconia beads having a diameter of 0.5 mm, and dispersed in a paint shaker for 5 hours. Thereafter, zirconia beads were removed to prepare pigment dispersion 2.
  • Pigment Dispersion 2 Dispersant: Azisper PB824 (Ajinomoto Fine Techno Co., Ltd.) 9 parts by weight Photopolymerizable compound: 1,9-nonanediol diacrylate (V # 260, Osaka Organic Chemical Co., Molecular weight 268, ClogP Value 5.22) 70 parts by mass Polymerization inhibitor: Irgastab UV10 (manufactured by Ciba Specialty Chemicals) 0.02 part by mass Black pigment 1: Pigment Black 7 (manufactured by Mitsubishi Chemical Corporation, # 52) 21 parts by mass
  • the actinic ray curable inkjet ink was loaded into a line type inkjet recording apparatus.
  • the temperature of the ink jet recording head of the ink jet recording apparatus was set to 80 ° C.
  • a piezo head having a nozzle diameter of 20 ⁇ m and a nozzle number of 512 nozzles (256 nozzles ⁇ 2 rows, staggered arrangement, 1 row nozzle pitch 360 dpi) was used.
  • the amount of one droplet was 2.5 pl
  • the droplet discharge speed was about 6 m / s
  • the resolution was 1440 dpi ⁇ 1440 dpi
  • the recording speed was 500 mm / s.
  • Image formation was performed in an environment of 23 ° C. and 55% RH. dpi represents the number of dots per 2.54 cm.
  • a solid image of 5 cm ⁇ 5 cm was printed from an inkjet recording apparatus on a PET (polyethylene terephthalate) film subjected to corona treatment immediately before printing. After the image was formed, the ink was cured by irradiating the image with ultraviolet light using an LED lamp (395 nm manufactured by Phoseon Technology, water-cooled LED) disposed in the downstream portion of the recording apparatus. The integrated light quantity during irradiation was 200 mJ.
  • the ink when a predetermined amount of the gelling agent, the polymerizable compound A, and the polymerizable compound B are included (Examples 1 to 12), the ink is generally stable.
  • the coating film was excellent in bending resistance and adhesion, and density unevenness was hardly generated in the image.
  • the gelling agent was an aliphatic ketone compound or an aliphatic monoester compound (Examples 4 to 6)
  • the scratch resistance was good.
  • the gelling agent is an aliphatic ketone compound or an aliphatic monoester compound
  • the scratch resistance is good. Since the ink has sufficiently undergone sol-gel phase transition, oxygen is not diffused within the ink droplets, and it is surmised that the photopolymerization has been sufficiently performed to increase the curing density.
  • the gelling agent was a hydrogen bonding gelling agent (Example 11)
  • the hydrogen bonding gelling agent is presumed to be slightly inferior in the pinning property of the ink as compared with the wax (for example, Example 1).
  • ink droplets after landing on a recording medium are difficult to coalesce. Further, the adhesion between the cured image and the recording medium is good. Therefore, it is suitable for production of various printed materials.

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  • Ink Jet (AREA)

Abstract

L'invention concerne une encre pour jet d'encre durcissable par rayonnement actif qui contient un agent de gélification, un composé photopolymérisable et un initiateur de photopolymérisation et qui subit une transition de phase sol-gel réversible induite par la température. La présente encre pour jet d'encre durcissable par rayonnement actif est caractérisée en ce que : la teneur en agent gélifiant vaut 0,5 % en masse ou plus mais moins de 10 % en masse par rapport à la masse totale de l'encre ; et le composé photopolymérisable contient (1) un composé photopolymérisable A qui présente un groupe (méth)acrylamide dans chaque molécule, tout en présentant un ClogP dans la plage de -4,0 (inclus) à 1,0 (exclus), et (2) un composé photopolymérisable B qui présente un groupe (méth)acrylate dans chaque molécule, tout en présentant un ClogP dans la plage de -1,0 (inclus) à 4,0 (exclus) et un poids moléculaire de 200 ou plus mais de moins de 1200. On empêche des gouttelettes de la présente encre pour jet d'encre durcissable par rayonnement actif de se combiner les unes aux autres après dépôt sur un support d'enregistrement ; et un film de revêtement de la présente encre montre une adhérence élevée sur le support d'enregistrement, tout en présentant une excellente résistance aux rayures.
PCT/JP2013/002796 2012-04-27 2013-04-24 Encre pour jet d'encre durcissable par rayonnement actif et procédé de formation d'image l'utilisant WO2013161298A1 (fr)

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WO2015152177A1 (fr) * 2014-04-03 2015-10-08 コニカミノルタ株式会社 Procédé de formation d'image
JPWO2013161328A1 (ja) * 2012-04-27 2015-12-24 コニカミノルタ株式会社 画像形成方法
WO2016125656A1 (fr) * 2015-02-05 2016-08-11 コニカミノルタ株式会社 Procédé de formation d'image par jet d'encre
WO2017010462A1 (fr) * 2015-07-13 2017-01-19 コニカミノルタ株式会社 Encre pour jet d'encre durcissable par rayons de lumière active, procédé de production d'un film durci, et procédé de formation d'une image pour jet d'encre
WO2017187905A1 (fr) * 2016-04-28 2017-11-02 コニカミノルタ株式会社 Procédé de formation d'image et appareil de formation d'image
US10829631B2 (en) 2017-09-29 2020-11-10 Ricoh Company, Ltd. Composition, accommodating unit, image forming device, and image forming method
WO2021090872A1 (fr) * 2019-11-08 2021-05-14 コニカミノルタ株式会社 Encre pour jet d'encre thermodurcissable et procédé d'impression

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JPWO2015152177A1 (ja) * 2014-04-03 2017-04-13 コニカミノルタ株式会社 画像形成方法
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JPWO2016125656A1 (ja) * 2015-02-05 2017-11-24 コニカミノルタ株式会社 インクジェット画像形成方法
JPWO2017010462A1 (ja) * 2015-07-13 2018-04-26 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、硬化膜の製造方法およびインクジェット画像形成方法
WO2017010462A1 (fr) * 2015-07-13 2017-01-19 コニカミノルタ株式会社 Encre pour jet d'encre durcissable par rayons de lumière active, procédé de production d'un film durci, et procédé de formation d'une image pour jet d'encre
WO2017187905A1 (fr) * 2016-04-28 2017-11-02 コニカミノルタ株式会社 Procédé de formation d'image et appareil de formation d'image
JPWO2017187905A1 (ja) * 2016-04-28 2019-02-28 コニカミノルタ株式会社 画像形成方法および画像形成装置
US10829631B2 (en) 2017-09-29 2020-11-10 Ricoh Company, Ltd. Composition, accommodating unit, image forming device, and image forming method
WO2021090872A1 (fr) * 2019-11-08 2021-05-14 コニカミノルタ株式会社 Encre pour jet d'encre thermodurcissable et procédé d'impression
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