WO2022071452A1 - インクジェット記録方法 - Google Patents

インクジェット記録方法 Download PDF

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Publication number
WO2022071452A1
WO2022071452A1 PCT/JP2021/036014 JP2021036014W WO2022071452A1 WO 2022071452 A1 WO2022071452 A1 WO 2022071452A1 JP 2021036014 W JP2021036014 W JP 2021036014W WO 2022071452 A1 WO2022071452 A1 WO 2022071452A1
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WIPO (PCT)
Prior art keywords
ink
mass
group
polymer
image
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Ceased
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PCT/JP2021/036014
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English (en)
French (fr)
Japanese (ja)
Inventor
昭太 鈴木
紘平 竹下
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Fujifilm Corp
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Fujifilm Corp
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Publication date
Application filed by Fujifilm Corp filed Critical Fujifilm Corp
Priority to EP21875748.2A priority Critical patent/EP4223538B1/en
Priority to JP2022554073A priority patent/JP7542640B2/ja
Priority to CN202180065536.XA priority patent/CN116323222B/zh
Publication of WO2022071452A1 publication Critical patent/WO2022071452A1/ja
Priority to US18/186,196 priority patent/US12291642B2/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • 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
    • C09D11/38—Inkjet printing inks characterised by non-macromolecular additives other than solvents, pigments or dyes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/0041—Digital printing on surfaces other than ordinary paper
    • B41M5/0047—Digital printing on surfaces other than ordinary paper by ink-jet printing
    • 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
    • C09D11/30—Inkjet printing inks
    • C09D11/32—Inkjet printing inks characterised by colouring agents
    • C09D11/322—Pigment inks
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/0011—Pre-treatment or treatment during printing of the recording material, e.g. heating, irradiating
    • 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
    • B41M7/009—After-treatment of prints, e.g. heating, irradiating, setting of the ink, protection of the printed stock using thermal means, e.g. infrared radiation, heat

Definitions

  • This disclosure relates to an inkjet recording method.
  • Patent Document 1 describes a chain polymer containing water and specific structural units and hydrophilic groups as an inkjet ink composition capable of forming an image having excellent adhesion to a plastic substrate and having excellent dispersion stability.
  • the inkjet ink composition containing the particles containing the polymerizable group and the particles containing the polymerizable group is disclosed.
  • Patent Document 2 describes a solvent, a polymerizable compound, and a photopolymerization initiator from the head toward the recording medium as an inkjet recording method having excellent curability, filling property, adhesion, and ejection stability.
  • the second step of evaporating the solvent contained in the mold ink composition and the third step of irradiating the image toward the image after the second step are included, and when the irradiation is started in the third step, the above Disclosed is an inkjet recording method in which the content of the polymerizable compound contained in the photocurable ink composition constituting the image after the second step is 20 to 90% by mass with respect to the total mass of the ink composition. ing.
  • Patent Document 3 describes an active energy ray-curable composition, which cures with high sensitivity even when irradiated with low-power active energy rays, has less exudation of a surfactant, and has excellent stability over time.
  • the energy ray-curable ink composition comprises (A) a polymerizable compound having an ethylenically unsaturated bond and substantially insoluble in water, and (B) an acrylate group, a methacrylate group, an acrylamide group, and a methacrylamide group.
  • Patent Document 3 also discloses an inkjet recording method using the above-mentioned active energy ray-curable composition.
  • inkjet ink is ejected from an inkjet recording head to a recording medium.
  • the inkjet ink contains at least a coloring material, a photoreactive resin, and water, and the inkjet ink is ejected to a recording medium and then before the step of irradiating with active energy rays.
  • An inkjet recording method is disclosed, which comprises concentrating a volatile component contained in an ink by a drying means or permeation into a recording medium.
  • Patent Document 1 Japanese Patent Application Laid-Open No. 6584677
  • Patent Document 2 Japanese Patent Application Laid-Open No. 6047904
  • Patent Document 3 Japanese Patent Application Laid-Open No. 2011-208088
  • Patent Document 4 Japanese Patent Application Laid-Open No. 2008-194827
  • the image quality of the image is improved.
  • the time from the impact of the ink to the start of irradiation of the active energy ray is shortened (for example, 1.00 seconds or less).
  • An object of one aspect of the present disclosure is to provide an inkjet recording method capable of recording an image having excellent image quality and abrasion resistance.
  • the polymerizable monomer M contains water and particles containing the polymer P and the polymerizable monomer M, and the polymerizable monomer M contains a monomer (M-1) having a viscosity at 25 ° C. of 500 mPa ⁇ s or less.
  • the time from the time when the ink lands on the substrate to the start of irradiation with the active energy rays is 1.00 seconds or less.
  • the total solid content of the particles in the ink at the time when the irradiation with the active energy rays is started is 3% by mass or more 20 with respect to the total amount of the ink at the time when the irradiation with the active energy rays is started.
  • ⁇ 4> The inkjet recording according to any one of ⁇ 1> to ⁇ 3>, wherein in the application step, the temperature of the surface of the base material on the side where the ink lands is 30 ° C to 70 ° C. Method.
  • ⁇ 5> Before the application step, a preheating step of heating the base material is included, and In the application step, at least one of heating the base material and applying the ink is satisfied.
  • the content of the liquid component in the ink after irradiation with the active energy ray is 10% by mass or more with respect to the content of the liquid component in the ink before irradiation with the active energy ray.
  • the inkjet recording method according to any one of ⁇ 5>. ⁇ 7> The inkjet recording method according to any one of ⁇ 1> to ⁇ 6>, further comprising a drying step of heating and drying the ink irradiated with the active energy rays. ⁇ 8> In the drying step, the content of the liquid component in the heat-dried ink is 2.0% by mass to 50% by mass with respect to the content of the liquid component in the ink before heat-drying.
  • an inkjet recording method capable of recording an image having excellent image quality and abrasion resistance is provided.
  • the numerical range indicated by using “-" means a range including the numerical values before and after "-" as the minimum value and the maximum value, respectively.
  • the amount of each component in the composition is the total amount of the plurality of substances present in the composition, unless otherwise specified, when a plurality of substances corresponding to each component are present in the composition. means.
  • the upper limit value or the lower limit value described in one numerical range may be replaced with the upper limit value or the lower limit value of another numerical range described stepwise. Further, it may be replaced with the value shown in the embodiment.
  • process is included in this term not only as an independent process but also as long as the intended purpose of the process is achieved even if it cannot be clearly distinguished from other processes. ..
  • "*" in the chemical formula represents a binding position.
  • the concept of "image” includes not only a pattern image (for example, a character, a symbol, or a graphic) but also a solid image.
  • "light” is a concept including active energy rays such as ⁇ -rays, ⁇ -rays, electron rays, ultraviolet rays, and visible rays.
  • active energy rays such as ⁇ -rays, ⁇ -rays, electron rays, ultraviolet rays, and visible rays.
  • exposure irradiation with active energy rays
  • ultraviolet rays may be referred to as "UV (Ultra Violet) light”.
  • UV light generated from an LED (Light Emitting Diode) light source may be referred to as "LED light”.
  • (meth) acrylic acid is a concept that includes both acrylic acid and methacrylic acid
  • (meth) acrylate is a concept that includes both acrylate and methacrylate
  • (meth) acrylate is a concept.
  • Acryloyl group is a concept that includes both an acryloyl group and a methacryloyl group.
  • the inkjet recording method (hereinafter, also simply referred to as “recording method”) in the present disclosure refers to the method.
  • a monomer (M) containing water and particles containing the polymer P and the polymerizable monomer M (hereinafter, also referred to as “specific particles”), wherein the polymerizable monomer M has a viscosity at 25 ° C. of 500 mPa ⁇ s or less.
  • an inkjet ink containing water and particles containing a polymer and a polymerizable monomer is landed on a substrate, and the landed inkjet ink is cured by irradiation with active energy rays.
  • the time from ink landing to the start of exposure is shortened (specifically, if it is set to 1.00 seconds or less), the image quality of the image does not improve, and the image quality is not improved. It became clear that the wear resistance of the image may also decrease. The reason for this phenomenon is considered as follows.
  • the polymerizable monomer is exuded from the particles to some extent at the start of exposure, and the polymerizable monomer exuded from the particles polymerizes at the time of exposure, so that the particles are interleaved with each other. It is considered important that the curing at the site (that is, the connection between the particles) proceeds. It is considered that excellent film (image) strength is obtained and the wear resistance of the image is improved by the progress of curing between the particles. Further, it is considered that the ink on the substrate can be thickened by the progress of curing between the particles, which can improve the image quality of the image.
  • the time from the ink landing to the start of exposure is 1.00 seconds or less, it is considered that the ink at the start of exposure may have insufficient exudation of the polymerizable monomer from the particles.
  • the curing mainly proceeds in the particles, and the curing between the particles (that is, the connection between the particles) becomes insufficient, and as a result, the image quality and wear resistance of the image may deteriorate. ..
  • the ink used in the recording method of the present disclosure contains specific particles containing the polymer P and the polymerizable monomer M.
  • the polymerizable monomer M contains a monomer (M-1) having a viscosity at 25 ° C. of 500 mPa ⁇ s or less.
  • the content of the monomer (M-1) is 25% by mass to 80% by mass with respect to the total solid content of the specific particles.
  • the monomer (M-1) having a low viscosity that is, 500 mPa ⁇ s or less
  • a certain amount that is, 25% by mass or more
  • the monomer (M) is transferred from the particles after the ink is landed.
  • -1) is effectively exuded, and thus the curing between the particles (that is, the connection between the particles) is sufficiently promoted.
  • an image having excellent image quality and abrasion resistance can be obtained even though the time from the ink landing to the start of exposure is 1.00 seconds or less.
  • the content of the monomer (M-1) of 80% by mass or less contributes to the ejection property of the ink from the inkjet head, but is caused by the effect of the ejection property, and further improves the image quality and wear resistance. Can also contribute.
  • the total solid content of the specific particles means the total amount of the specific particles excluding the solvent (that is, water and organic solvent). When the specific particles do not contain a solvent, the total solid content of the specific particles is equal to the total amount of the specific particles.
  • the time from the ink landing to the start of exposure is 1.00 seconds or less.
  • the content of the monomer (M-1) is 25% by mass or more with respect to the total solid content of the specific particles, but also the time from the ink landing to the start of exposure is 1.00 seconds.
  • the following itself also contributes to improving the image quality of the image. It is considered that the reason for this is that the ink landing on the base material is exposed to some extent quickly (that is, within 1.00 seconds), so that the movement of the ink landing on the base material can be suppressed.
  • This step is a step of preparing the ink used for the recording method of the present disclosure.
  • the ink contains water and particles containing the polymer P and the polymerizable monomer M (that is, specific particles), and the polymerizable monomer M has a viscosity at 25 ° C. of 500 mPa ⁇ s or less (M-). 1) is contained, and the content of the monomer (M-1) is 25% by mass to 80% by mass with respect to the total solid content of the specific particles.
  • This step may be a step of producing the above-mentioned ink, or may be a step of simply preparing the above-mentioned ink manufactured in advance. Preferred embodiments of the ink used in the recording method of the present disclosure will be described later.
  • the applying step is a step of applying the ink onto the substrate by an inkjet method.
  • the base material used in the recording method of the present disclosure is not particularly limited and may be a non-permeable base material or a permeable base material, but a non-permeable base material is preferable.
  • the non-permeable substrate refers to a substrate having a water absorption rate (unit: mass%, measurement time: 24 hours) of less than 10 in ASTM D570 of the ASTM test method.
  • the water absorption rate of the impermeable substrate is preferably 5 or less.
  • the impermeable substrate examples include, for example. Paper laminated with plastic (eg polyethylene, polypropylene, polystyrene, etc.), Metal plate (eg metal plate such as aluminum, zinc, copper), Plastic film (for example, Polyvinyl Chloride (PVC) resin, cellulose diacetate, cellulose triacetate, cellulose propionate, cellulose butyrate, cellulose acetate butyrate, cellulose nitrate, polyethylene terephthalate (PET), polyethylene (PE) : Polyethylene), Polyethylene (PS: Polystyrene), Polypropylene (PP: Polypropylene), Polycarbonate (PC: Polycarbonate), Polyvinylacetal, Acrylic resin and other films), Paper on which the above-mentioned metals are laminated or vapor-deposited, A plastic film on which the above-mentioned metals are laminated or vapor-deposited, leather, And so on.
  • plastic eg polyethylene, polypropylene, polystyrene, etc.
  • leather examples include natural leather (also referred to as "genuine leather"), synthetic leather (for example, PVC (polyvinyl chloride) leather, PU (polyurethane) leather), and the like.
  • synthetic leather for example, PVC (polyvinyl chloride) leather, PU (polyurethane) leather
  • paragraphs 0163 to 0165 of JP2009-05875A can be referred to.
  • a film on leather as a non-permeable substrate (eg, seats for vehicles, bags, shoes, wallets, etc.) or plastic films
  • excellent wear resistance against the formed film are required.
  • excellent wear resistance and adhesion may be required for the formed film. According to the film forming method of the present disclosure, such a requirement can be satisfied.
  • the base material may be surface-treated from the viewpoint of improving the surface energy.
  • Examples of the surface treatment include, but are not limited to, corona treatment, plasma treatment, frame treatment, heat treatment, wear treatment, light irradiation treatment (UV treatment), and flame treatment.
  • Ink application conditions, etc. Ink application by the inkjet method can be performed by ejecting ink from an inkjet head in a known inkjet recording device.
  • the inkjet head a piezo type inkjet head is preferable.
  • the resolution of the inkjet head is preferably 300 dpi or more, more preferably 600 dpi or more, and further preferably 800 dpi or more.
  • dpi dot per inch
  • dpi represents the number of dots per 2.54 cm (1 inch).
  • the amount of ink ejected from the inkjet head is preferably 1 pL (picolitre) to 100 pL, more preferably 3 pL to 80 pL, and 3 pL to 50 pL. Is even more preferable.
  • the temperature of the surface of the base material on which the ink lands is preferably 20 ° C to 80 ° C, more preferably 25 ° C to 75 ° C, still more preferably 30 ° C to 70 ° C. More preferably, it is 40 ° C to 70 ° C.
  • the temperature of the surface of the base material on the side where the ink lands is 20 ° C to 80 ° C, the image quality and wear resistance of the image are further improved. The reason is considered to be that the effect of exuding the monomer (M-1) from the specific particles is more likely to be obtained.
  • the recording method of the present disclosure may satisfy at least one of including a preheating step of heating the base material before the applying step and heating of the base material and applying ink in the applying step. preferable. This further improves the image quality and wear resistance of the image. The reason is considered to be that the effect of exuding the monomer (M-1) from the specific particles is more likely to be obtained. Further, when the recording method of the present disclosure satisfies at least one of the above, the temperature of the surface of the base material can be easily adjusted to the above-mentioned preferable temperature.
  • the heating means for heating the base material is not particularly limited, and for example, a heat drum, warm air, an infrared lamp, an infrared LED, and the like.
  • examples include infrared heaters, heat ovens, hot plates, infrared lasers, infrared dryers and the like.
  • the irradiation step is a step of irradiating the ink applied on the substrate with active energy rays (in other words, a step of exposing the ink applied on the substrate).
  • active energy rays in this step, the polymerizable monomer M in the ink is polymerized and the ink is cured, and an image is obtained.
  • the monomer (M-1) effectively exudes from the specific particles, whereby the curing between the specific particles (that is, the connection between the specific particles) is sufficiently sufficient. As a result, an image having excellent image quality and wear resistance is obtained.
  • the active energy ray examples include ultraviolet rays (UV light), visible light, electron beam and the like, and among these, UV light is preferable.
  • Irradiation of the active energy rays to the ink applied on the base material may be performed in a state where the base material and the ink applied on the base material are heated.
  • the irradiation conditions and basic irradiation methods for the active energy rays the irradiation conditions and irradiation methods disclosed in paragraph 0023 of Japanese Patent Application Laid-Open No. 60-132767 and Japanese Patent Application Laid-Open No. 2014-132081 can be applied. ..
  • the time from the time when the ink lands to the start of irradiation with the active energy ray is short (that is, 1.00 seconds or less).
  • the ink application and the irradiation of the active energy ray in such an embodiment are carried out by using an inkjet recording apparatus including a unit including an irradiation inkjet head of the active energy ray and an active energy radiation source arranged in the vicinity of the inkjet head. Is preferable.
  • the active energy ray from the active energy radiation source of the unit is as fast as 1.00 seconds or less after the impact. Can be irradiated.
  • Light sources for irradiating active energy rays include mercury lamps, metal halide lamps, high-pressure mercury lamps, medium-pressure mercury lamps, low-pressure mercury lamps, ultraviolet fluorescent lamps, gas lasers, solid-state lasers, LEDs (light emitting diodes), and LDs (laser diodes). And so on.
  • the light source for irradiating active energy rays is a metal halide lamp, a high-pressure mercury lamp, a medium-pressure mercury lamp, a low-pressure mercury lamp, or an ultraviolet LED (hereinafter, also referred to as UV-LED), which is a light source for irradiating ultraviolet rays. Is preferable.
  • the peak wavelength of ultraviolet rays is, for example, preferably 200 nm to 405 nm, more preferably 220 nm to 400 nm, and even more preferably 340 nm to 400 nm.
  • the peak wavelength of the light (LED light) from the LED light source is preferably 200 nm to 600 nm, more preferably 300 nm to 450 nm, further preferably 320 nm to 420 nm, and 340 nm to 405 nm. Is more preferable, and 355 nm, 365 nm, 385 nm, 395 nm or 405 nm is even more preferable.
  • Examples of the UV-LED include a UV-LED manufactured by Nichia Kagaku Co., Ltd., which has a main emission spectrum having a wavelength between 365 nm and 420 nm. Also mentioned in US Pat. No. 6,084,250 are UV-LEDs capable of emitting active radiation centered between 300 nm and 370 nm. Further, by combining several UV-LEDs, it is possible to irradiate ultraviolet rays in different wavelength ranges.
  • the irradiation energy (that is, the exposure amount) of the active energy ray is preferably 20 mJ / cm 2 or more, more preferably 100 mJ / cm 2 or more, further preferably 300 mJ / cm 2 or more, and 500 mJ. It is particularly preferably / cm 2 or more, and most preferably 900 mJ / cm 2 or more.
  • the upper limit of the exposure amount is not particularly limited, and the upper limit may be 5 J / cm 2 or 1,500 mJ / cm 2 .
  • the maximum illuminance of the LED on the substrate is preferably 10 mW / cm 2 to 8,000 mW / cm 2 , more preferably 20 mW / cm 2 to 5,000 mW / cm 2 , and 30 mW / cm 2 to 3000 mW / cm 2 . More preferably, 50 mW / cm 2 to 1000 mW / cm 2 is even more preferable.
  • the irradiation time of the active energy ray is preferably 0.01 seconds to 120 seconds, more preferably 0.1 seconds to 90 seconds.
  • the time from the ink impact to the start of exposure (that is, the time from the time when the ink lands on the substrate to the start of irradiation with active energy rays) is 1.00 seconds or less. .. As described above, the time from the ink landing to the start of exposure is 1.00 seconds or less, which contributes to the improvement of the image quality of the image.
  • the lower limit of the time from the ink landing to the start of exposure is not particularly limited, and examples of the lower limit include 0.01 seconds, 0.05 seconds, and 0.10 seconds.
  • the total solid content of the specific particles in the ink at the start of exposure is preferably relative to the total amount of ink. It is 3% by mass or more and less than 20% by mass.
  • the total solid content of the specific particles in the ink at the start of exposure is less than 20% by mass, the ink applied on the substrate is in an insufficiently dried state (specifically, water and / or a water-soluble organic solvent).
  • the ink in an insufficiently dried state is irradiated with active energy rays at a timing (in a state where the liquid component is contained in an amount of more than 80% by mass).
  • the activation energy ray irradiation of such an embodiment the exudation of the monomer (M-1) and the curing between specific particles can be more effectively realized, so that the image quality and the abrasion resistance of the image are further improved.
  • the total solid content of the specific particles in the ink at the start of exposure is preferably 4% by mass to 19% by mass, more preferably 5% by mass to 15% by mass.
  • the total solid content of the specific particles in the ink at the start of exposure is, for example, Total solid content of specific particles in the ink before ejection from the inkjet head, The time from ink landing to the start of exposure, The temperature of the surface of the substrate, It can be adjusted by adjusting etc.
  • the total solid content of the specific particles in the ink at the start of exposure is determined as follows. That is, the total solid content (mass%) of the specific particles in the ink before ejection is regarded as the total solid content (mass%) of the specific particles in the ink at the time of landing on the base material. The total solid content (mass%) of the specific particles in the ink at the time of landing on the substrate, Ink drying speed (vol% / s) determined using a contact angle meter, The time from ink landing to the start of exposure, Based on the above, the total solid content of the specific particles in the ink at the start of exposure is determined.
  • the drying speed (vol% / s) of the ink is measured using a contact angle meter.
  • the ink drying rate (vol% / s) is obtained as described in (1) to (4) below.
  • an FTA-1000 type contact angle meter manufactured by FTA and a hot water circulation type temperature control stage are used as the apparatus.
  • the temperature control stage is heated to a predetermined temperature, and the time change of the droplet volume is measured for each of 0.5 ⁇ L (droplet radius 492 ⁇ m) and 1 ⁇ L (droplet radius 620 ⁇ m) of the ink droplets up to 20 seconds. ..
  • the time change of the droplet volume is obtained based on the time change of the contact angle.
  • the drying rate (vol% / s) at each droplet amount is calculated from the slope of the obtained linear relationship (time vs. droplet volume).
  • Equation (A) [In the formula (A), J represents the drying rate (vol% / s), DGAS represents the diffusion coefficient of the gas phase, Cv represents the vapor concentration on the surface of the droplet, and Ca represents the vapor of the atmosphere. The concentration is represented, R is represented by the droplet radius, and L is represented by the thickness of the vapor diffusion layer.] (Source: “Applications and Materials of Inkjet Printers 2", CMC Publishing 2007) (3) The DGAS (Cv-Ca) and L obtained in (2) above are substituted into the formula (A), and the obtained formula is used to make J (droplet radius 13.4 ⁇ m) of the ink droplet 10 pL. Drying rate) is calculated.
  • the liquid component that is, water and a water-soluble organic solvent
  • the liquid component that is, water and a water-soluble organic solvent
  • the amount of evaporation is calculated.
  • Identification in the ink at the start of exposure based on the obtained evaporation amount and the total solid content of the specific particles in the ink at the time of landing on the substrate (that is, the total solid content of the specific particles in the ink before ejection).
  • the volume of the ink droplet is a value other than 10 pL
  • the total solid content of the specific particles in the ink at the start of exposure can be obtained in the same manner as when the volume is 10 pL.
  • the irradiation condition of the active energy ray is that the irradiation energy of the active energy ray is 300 mJ / cm 2 or more and the active energy ray is emitted.
  • the content of the liquid component in the ink after irradiation is preferably 10% by mass or more, preferably 20% by mass or more and 70% by mass with respect to the content of the liquid component in the ink before irradiation with the active energy ray. % Or less, more preferably 25% by mass or more and 60% by mass or less.
  • the content of the liquid component in the ink after irradiation with the active energy ray is referred to as the "residual amount of the liquid component in the irradiation step" with respect to the content of the liquid component in the ink before irradiation with the active energy ray. Also called.
  • the remaining amount of the liquid component in the irradiation step was obtained by determining the content of the liquid component in the ink before irradiation with the active energy ray and the content of the liquid component in the ink after irradiation with the active energy ray. Calculate based on the value.
  • the content of the liquid component in the ink before irradiation with the active energy ray is as follows.
  • the sample obtained by performing the steps from the step of preparing the above ink to the above applying step in the actual inkjet recording method is a sample for measuring the content of the liquid component in the ink before irradiation with the active energy ray (hereinafter referred to as a sample before irradiation). It is referred to as).
  • a sample before irradiation a sample before irradiation
  • the base material shall not be heated when the ink is applied during the preparation of the measurement sample.
  • the content of the liquid component in the ink before irradiation with the active energy rays is the ink before heat drying described later (that is, the image) except that the pre-irradiation sample was used instead of the image recording material 1 described later.
  • the content of the liquid component in the ink after irradiation with the active energy ray is as follows.
  • the sample obtained by performing the steps from the step of preparing the above ink to the above irradiation step in the actual inkjet recording method is a sample for measuring the content of the liquid component in the ink after irradiation with active energy rays (hereinafter referred to as a sample after irradiation). It is referred to as).
  • the image formed in the applying step is a solid image of a square of 4 cm ⁇ 4 cm, and the active energy rays are not irradiated except in the irradiation step, and the ink is applied in the actual inkjet recording method.
  • the content of the liquid component in the ink after irradiation with the active energy rays is the ink before heat drying described later (that is, the image) except that the sample after irradiation is used instead of the image recording material 1 described later.
  • the mass of water in the ink of the sample after irradiation is quantified by the Karl Fischer titration method.
  • the content mass of the water-soluble organic solvent obtained above and the content mass of water are totaled, and the obtained value is taken as the content of the liquid component in the ink after irradiation with the active energy ray.
  • the base material is changed to an OPP (stretched polypropylene) base material to prepare a pre-irradiation sample and a post-irradiation sample, and the prepared pre-irradiation sample and post-irradiation sample, and the OPP base material as a blank are used.
  • OPP unstretched polypropylene
  • the recording method of the present disclosure further preferably includes a drying step of heating and drying the ink (that is, the image) irradiated with the active energy rays.
  • the heating means for heating the ink is not particularly limited, and examples thereof include a heat drum, hot air, an infrared lamp, an infrared LED, an infrared heater, a heat oven, a hot plate, an infrared laser, and an infrared dryer. Be done.
  • the heating temperature in the heat drying is preferably 40 ° C. or higher, more preferably 40 ° C. to 200 ° C., further preferably 40 ° C. to 100 ° C., further preferably 40 ° C. to 80 ° C., still more preferably 45 ° C. to 70 ° C.
  • the heating temperature refers to the temperature of the ink on the substrate, and can be measured by a thermograph using an infrared thermography device H2640 (manufactured by Nippon Avionics Co., Ltd.).
  • the heating time can be appropriately set in consideration of the heating temperature, the composition of the ink, the printing speed, and the like.
  • the heating time is preferably 5 seconds or more, more preferably 5 seconds to 20 minutes, more preferably 10 seconds to 10 minutes, still more preferably 20 seconds to 5 minutes.
  • the content of the liquid component in the heat-dried ink (hereinafter, also referred to as “residual amount of the liquid component in the drying step”) with respect to the content of the liquid component in the ink before being heat-dried is preferably. It is 50% by mass or less, more preferably 2.0% by mass to 50% by mass, and further preferably 2.0% by mass to 40% by mass.
  • residual amount of the liquid component in the drying step is 50% by mass or less, the image quality and wear resistance of the image are further improved.
  • the residual amount of the liquid component in the drying step is 2.0% by mass or more, the adhesion of the image to the substrate is further improved.
  • the residual amount of the liquid component in the drying step can be adjusted by adjusting the heating conditions (for example, heating temperature and heating time) in the drying step.
  • the liquid component means water and a water-soluble organic solvent.
  • the content of the liquid component in the ink before heat-drying means the mass of the liquid component in the ink before heat-drying (that is, the total mass of water and the water-soluble organic solvent).
  • the content of the liquid component in the heat-dried ink means the mass of the liquid component in the heat-dried ink (that is, the total mass of water and the water-soluble organic solvent).
  • the residual amount of the liquid component in the drying step (that is, the content of the liquid component in the heat-dried ink (% by mass) with respect to the content of the liquid component in the ink before the heat-drying) is the content before the heat-drying.
  • the content of the liquid component in the ink and the content of the liquid component in the heat-dried ink are obtained as follows, and are obtained based on the obtained values.
  • image record 1 an image after the end of exposure and before heat-drying
  • An example of the method for measuring the content of the water-soluble organic solvent using the image recording material 1 is shown below.
  • This example is an example when the water-soluble organic solvent is propylene glycol (PG).
  • PG propylene glycol
  • Each test piece is subjected to an extraction operation in which 1 mL of solution A is immersed for 24 hours.
  • the extract obtained by the extraction operation is filtered through a syringe and then diluted 10-fold.
  • the mass content of the water-soluble organic solvent is quantified by gas chromatography (GC) under the following GC conditions.
  • GC gas chromatography
  • FIG. 1 An example of a method for measuring the water content using the image recording material 1 is shown below.
  • Three 24 mm ⁇ 30 mm rectangular test pieces are collected from the image recording material 1.
  • the water content (mass standard) of each test piece is measured by the Karl Fischer titration method using the trace moisture measuring device CA-200 manufactured by Mitsubishi Chemical Analytical Co., Ltd. and the heating eviction unit (VA-230).
  • VA-230 heating eviction unit
  • Aquamicron AKX is used as the anode liquid
  • Aquamicron CxU is used as the cathode liquid.
  • the mass of the blank the mass of the base material having the same volume as the base material in each test piece is measured.
  • the content of the liquid component in the heat-dried ink (that is, the image) is also determined by the same method as the content of the liquid component in the ink (that is, the image) before the heat-drying. Based on the content of the liquid component in the heat-dried ink (ie, image) and the content of the liquid component in the ink (ie, image) before heat-drying, the residual amount of liquid component in the drying step (ie, image). The content (% by mass) of the liquid component in the heat-dried ink is determined with respect to the content of the liquid component in the ink before being heat-dried.
  • an image recording material is prepared by changing the base material to an OPP (stretched polypropylene) base material, and the prepared image recording material and the OPP base material as a blank are used to determine the residual amount of liquid component in the drying step. It was measured.
  • OPP unstretched polypropylene
  • the ink in the recording method of the present disclosure contains water and particles containing the polymer P and the polymerizable monomer M (hereinafter, also referred to as “specific particles”) and is polymerizable.
  • the monomer M contains a monomer (M-1) having a viscosity at 25 ° C. of 500 mPa ⁇ s or less, and the content of the monomer (M-1) is 25% by mass to 80% by mass with respect to the total solid content of the specific particles. %.
  • the ink contains at least one specific particle (that is, a particle containing the polymer P and the polymerizable monomer M).
  • the inclusion of the polymer P and the polymerizable monomer M in the specific particles contributes to the ejection property of the ink from the inkjet head (hereinafter, also simply referred to as “ink ejection property”). ..
  • a preferred embodiment of the ink in the present disclosure is that the polymerizable monomer M stays in the specific particles in the ink before being applied onto the substrate, and the polymerizable monomer M is contained in the ink applied on the substrate. It is an embodiment that exudes from specific particles.
  • the specific particles contain at least one polymerizable monomer M.
  • the polymerizable monomer M connects the specific particles to each other and contributes to improving the abrasion resistance and the image quality of the image.
  • the polymerizable monomer M contained in the specific particles may be only one kind or two or more kinds.
  • the compound described in paragraphs 097 to 0105 of International Publication No. 2016/052053 may be used.
  • the molecular weight of the polymerizable monomer M is preferably 100 to 4000, more preferably 100 to 2000, still more preferably 100 to 1000, still more preferably 100 to 900, still more preferably 100 to 800. It is particularly preferably 150 to 750.
  • a radically polymerizable monomer As the polymerizable monomer M that can be contained in the specific particles, a radically polymerizable monomer is more preferable.
  • the radically polymerizable monomer has a radically polymerizable group in its molecular structure.
  • the preferred embodiment of the radically polymerizable group of the radically polymerizable monomer is the same as the above-mentioned preferred embodiment of the radically polymerizable group that the polymer P can contain.
  • the radically polymerizable monomer examples include acrylate compounds, methacrylate compounds, styrene compounds, vinylnaphthalene compounds, N-vinyl heterocyclic compounds, unsaturated polyesters, unsaturated polyethers, unsaturated polyamides, and unsaturated urethanes.
  • the radically polymerizable monomer is preferably a compound having an ethylenically unsaturated group.
  • the specific particles may contain only one type of radically polymerizable monomer or may contain two or more types of radically polymerizable monomers.
  • acrylate compound examples include 2-hydroxyethyl acrylate, butoxyethyl acrylate, carbitol acrylate, cyclohexyl acrylate, tetrahydrofurfuryl acrylate, benzyl acrylate, tridecyl acrylate, 2-phenoxyethyl acrylate (PEA), and bis (4-acryloxypoly).
  • methacrylate compound examples include methyl methacrylate, n-butyl methacrylate, allyl methacrylate, glycidyl methacrylate, benzyl methacrylate, dimethylaminomethyl methacrylate, methoxypolyethylene glycol methacrylate, methoxytriethylene glycol methacrylate, hydroxyethyl methacrylate, phenoxyethyl methacrylate, cyclohexyl methacrylate and the like.
  • Monofunctional methacrylate compound examples include methyl methacrylate, n-butyl methacrylate, allyl methacrylate, glycidyl methacrylate, benzyl methacrylate, dimethylaminomethyl methacrylate, methoxypolyethylene glycol methacrylate, methoxytriethylene glycol methacrylate, hydroxyethyl methacrylate, phenoxyethyl methacrylate, cyclohexyl methacrylate
  • bifunctional methacrylate compounds such as polyethylene glycol dimethacrylate, polypropylene glycol dimethacrylate, 2,2-bis (4-methacryloxypolyethoxyphenyl) propane, and tetraethylene glycol dimethacrylate.
  • styrene compound examples include styrene, p-methylstyrene, p-methoxystyrene, ⁇ -methylstyrene, p-methyl- ⁇ -methylstyrene, ⁇ -methylstyrene, p-methoxy- ⁇ -methylstyrene and the like.
  • vinylnaphthalene compound examples include 1-vinylnaphthalene, methyl-1-vinylnaphthalene, ⁇ -methyl-1-vinylnaphthalene, 4-methyl-1-vinylnaphthalene, 4-methoxy-1-vinylnaphthalene and the like.
  • N-vinyl heterocyclic compound examples include N-vinylcarbazole, N-vinylpyrrolidone, N-vinylethylacetamide, N-vinylpyrrole, N-vinylphenothiazine, N-vinylacetonylide, N-vinylethylacetamide, and N-vinylsuccinic acid.
  • examples thereof include imide, N-vinylphthalimide, N-vinylcaprolacttam, N-vinylimidazole and the like.
  • Examples of other radically polymerizable monomers include N-vinylamides such as allylglycidyl ether, diallyl phthalate, triallyl trimellitate, and N-vinylformamide.
  • the less than bifunctional radically polymerizable monomers include 1,6-hexanediol diacrylate (HDDA), 1,9-nonanediol diacrylate (NDDA), and 1,10-decanediol.
  • Diacrylate (DDDA), 3-Methylpentadiol diacrylate (3MPDDA), neopentyl glycol diacrylate, tricyclodecanedimethanol diacrylate, diethylene glycol diacrylate, tetraethylene glycol diacrylate, dipropylene glycol diacrylate, tripropylene glycol
  • TPGDA diacrylate
  • cyclohexanone dimethanol diacrylate alkoxylated hexanediol diacrylate
  • polyethylene glycol diacrylate and polypropylene glycol diacrylate
  • trifunctional or higher functional radical polymerizable monomer examples include trimethylolpropane triacrylate, pentaerythritol triacrylate, dipentaerythritol tetraacrylate, trimethylolpropane tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, and ethoxylated.
  • the specific particles may contain a combination of a radically polymerizable monomer having less than two functionalities and a radically polymerizable monomer having three or more functionalities.
  • a radically polymerizable monomer mainly having a bifunctionality or less improves the adhesion between the film and the substrate
  • a radically polymerizable monomer having a trifunctionality or more mainly improves the hardness of the film.
  • the combination of the bifunctional or lower radically polymerizable monomer and the trifunctional or higher functional radically polymerizable monomer is a combination of a bifunctional acrylate compound and a trifunctional acrylate compound, a bifunctional acrylate compound and a pentafunctional acrylate compound.
  • At least one of the radically polymerizable monomers that can be contained in the specific particles is also referred to as a radically polymerizable monomer having a cyclic structure (hereinafter, also referred to as “cyclic radically polymerizable monomer”). It is preferable to say).
  • cyclic radically polymerizable monomer examples include cyclohexyl acrylate, tetrahydrofurfuryl acrylate, benzyl acrylate, isobornyl acrylate, dicyclopentenyl acrylate, dicyclopentenyloxyethyl acrylate, dicyclopentanyl acrylate, ethoxylated isocyanuric acid triacrylate, and ⁇ .
  • -Caprolactone-modified tris- (2-acryloxyethyl) isocyanurate and the like.
  • bifunctional or higher functional cyclic radically polymerizable monomers described below may also be mentioned.
  • At least one of the radically polymerizable monomers that can be contained in the specific particles has one or more cyclic structures and two or more (meth) in one molecule.
  • a polymerizable monomer containing an acryloyl group hereinafter, also referred to as "bifunctional or higher functional cyclic radical polymerizable monomer" is preferable.
  • Tricyclodecanedimethanol di (meth) acrylate Bisphenol A Ethylene Oxide (EO) Adduct Di (Meta) Acrylate, Bisphenol A Propylene Oxide (PO) Adduct Di (Meta) Acrylate, Ethoxybisphenol A di (meth) acrylate, Alkoxylated dimethylol tricyclodecandi (meth) acrylate, Alkoxyated cyclohexanone dimethanol di (meth) acrylate, Cyclohexanone dimethanol di (meth) acrylate, etc. may be mentioned.
  • EO Ethylene Oxide
  • PO Propylene Oxide
  • the ratio of the bifunctional or higher functional cyclic radically polymerizable monomer to the entire radically polymerizable monomer is preferably 10% by mass to 100% by mass, preferably 30% by mass to 100% by mass. More preferably, 40% by mass to 100% by mass is particularly preferable.
  • the content of the polymerizable monomer M (that is, the total polymerizable monomer in the specific particles) with respect to the total solid content of the specific particles is such that the content of the monomer (M-1) is 25% by mass with respect to the total solid content of the specific particles.
  • the content of the polymerizable monomer M with respect to the total solid content of the specific particles is 25% by mass to 90% by mass, more preferably 25% by mass to 80% by mass, and further preferably 25% by mass to 75% by mass. More preferably, 25% by mass to 70% by mass is further preferable.
  • the content of the polymerizable monomer M with respect to the total amount of the ink is preferably 0.3% by mass to 20% by mass, more preferably 0.5% by mass to 15% by mass, still more preferably 1% by mass to 10% by mass.
  • the polymerizable monomer M contains a monomer (M-1) having a viscosity at 25 ° C. (hereinafter, also simply referred to as “viscosity”) of 500 mPa ⁇ s or less.
  • the monomer (M-1) is a relatively low-viscosity polymerizable monomer having the above-mentioned viscosity, and is a polymerizable monomer that easily exudes from specific particles.
  • the viscosity of the monomer (M-1) is a value measured using a viscometer. As the viscometer, for example, VISCOMETER TV-22 (Toki Sangyo Co., Ltd.) can be used.
  • the monomer (M-1) may be a polymerizable monomer having a viscosity at 25 ° C. of 500 mPa ⁇ s or less.
  • the lower limit of the viscosity of the monomer (M-1) is not particularly limited, but the lower limit is, for example, 10 mPa ⁇ s.
  • the monomer (M-1) one having 500 mPa ⁇ s or less can be appropriately selected and used from the radically polymerizable monomers exemplified above.
  • M-1 for example, Pentaerythritol tetraacrylate, Tricyclodecanedimethanol diacrylate, Glycerin propoxytriacrylate, 1,12-dodecanediol dimetallilate, Dicyclopentenyloxyethyl methacrylate, 2-Phenoxyethyl acrylate, Dicyclopentanyl acrylate, 1,6-Hexanediol diacrylate, 1,9-Nonanediol diacrylate, 1,10-decanediol diacrylate, And so on.
  • Pentaerythritol tetraacrylate Tricyclodecanedimethanol diacrylate
  • Glycerin propoxytriacrylate 1,12-dodecanediol dimetallilate
  • Dicyclopentenyloxyethyl methacrylate 2-Phenoxyethyl acrylate
  • Dicyclopentanyl acrylate 1,6-Hexanediol di
  • the content of the monomer (M-1) is 25% by mass to 80% by mass with respect to the total solid content of the specific particles.
  • the image quality and wear resistance of the image are improved.
  • the content of the monomer (M-1) is 25% by mass or more with respect to the total solid content of the specific particles, in the ink applied on the substrate, from the specific particles before exposure.
  • the polymerizable monomer M (particularly, the monomer (M-1)) easily exudes.
  • the ink containing the exuded polymerizable monomer M (particularly the monomer (M-1)) is exposed, curing (linkage between the specific particles) between the specific particles proceeds.
  • the strength of the entire film is increased, the abrasion resistance of the image is improved, and the thickening of the ink is promoted, and the image quality of the image is improved.
  • the content of the monomer (M-1) is 80% by mass or less with respect to the total solid content of the specific particles, the content of the polymer P in the specific particles is secured, and as a result, the ink ejection property is secured. Is improved.
  • the content of the monomer (M-1) with respect to the total solid content of the specific particles is preferably 75% by mass or less, more preferably 70% by mass or less.
  • the polymerizable monomer M is other than the monomer (M-1) as long as it satisfies the condition that "the content of the monomer (M-1) is 25% by mass to 80% by mass with respect to the total solid content of the specific particles".
  • a polymerizable monomer hereinafter, also referred to as “monomer (M-2)” may be contained.
  • the ratio of the monomer (M-1) to the total amount of the polymerizable monomer M contained in the specific particles is preferably 50% by mass to 100% by mass. It is more preferably 60% by mass to 100% by mass, and further preferably 80% by mass to 100% by mass.
  • the content of the monomer (M-1) is preferably 0.3% by mass to 20% by mass, preferably 0.5% by mass or more, based on the total amount of the ink. 15% by mass is more preferable, and 1% by mass to 10% by mass is further preferable.
  • the monomer (M-1) preferably contains a monomer (M1A) having a viscosity at 25 ° C. of 150 mPa ⁇ s or less.
  • the monomer (M1A) is a polymerizable monomer that easily exudes from specific particles among the monomers (M-1). Therefore, when the monomer (M-1) contains the monomer (M1A), the image quality and wear resistance of the image are further improved.
  • the monomer (M1A) may be a polymerizable monomer having a viscosity at 25 ° C. of 150 mPa ⁇ s or less.
  • the lower limit of the viscosity of the monomer (M1A) is not particularly limited, but the lower limit is, for example, 10 mPa ⁇ s.
  • those having 150 mPa ⁇ s or less can be appropriately selected and used from the radically polymerizable monomers exemplified above.
  • M1A for example Tricyclodecanedimethanol diacrylate, Glycerin propoxytriacrylate, 1,12-dodecanediol dimetallilate, Dicyclopentenyloxyethyl methacrylate, 2-Phenoxyethyl acrylate, Dicyclopentanyl acrylate, 1,6-Hexanediol diacrylate, 1,9-Nonanediol diacrylate, 1,10-decanediol diacrylate, And so on.
  • M1A for example Tricyclodecanedimethanol diacrylate, Glycerin propoxytriacrylate, 1,12-dodecanediol dimetallilate, Dicyclopentenyloxyethyl methacrylate, 2-Phenoxyethyl acrylate, Dicyclopentanyl acrylate, 1,6-Hexanediol diacrylate, 1,9-Nonanediol diacrylate, 1,10-decanedi
  • the monomer (M-1) may contain a polymerizable monomer other than the monomer (M1A) (hereinafter, also referred to as “monomer (M2A)”). From the viewpoint of further improving the image quality and wear resistance of the image, the ratio of the monomer (M1A) to the total amount of the monomer (M-1) is preferably 50% by mass to 100% by mass, more preferably 60% by mass. % To 100% by mass, more preferably 80% by mass to 100% by mass.
  • the ratio of the monomer (M1A) to the total amount of the polymerizable monomer M contained in the specific particles is preferably 50% by mass to 100% by mass, more preferably. Is 60% by mass to 100% by mass, more preferably 80% by mass to 100% by mass.
  • the content of the monomer (M1A) is preferably 0.3% by mass to 20% by mass, preferably 0.5% by mass to 15% by mass, based on the total amount of the ink. More preferably, 1% by mass to 10% by mass is further preferable.
  • Examples of the radically polymerizable monomer as the polymerizable monomer M include JP-A-7-159983, JP-A-7-313999, JP-A-8-224982, JP-A-10-863, and JP-A-9-134011. Examples thereof include radically polymerizable monomers described in JP-A, JP-A-2004-514014, and the like. Examples of commercially available products of radically polymerizable monomers include AH-600 (bifunctional), AT-600 (bifunctional), UA-306H (six-functional), UA-306T (six-functional), and UA-306I (six-functional).
  • UA-510H (10 functionalities), UF-8001G (bifunctional), DAUA-167 (bifunctional), light acrylate NPA (bifunctional), light acrylate 3EG-A (bifunctional) (above, Kyoeisha Chemical Co., Ltd.
  • radically polymerizable monomers include NPGPODA (neopentyl glycol propylene oxide adduct diacrylate), SR531, SR285, SR256 (above, Sartmer), A-DHP (dipentaerythritol hexaacrylate, Shin Nakamura Chemical Industry Co., Ltd.). )), Aronix (registered trademark) M-156 (Toa Synthetic Co., Ltd.), V-CAP (BASF), Viscort # 192 (Osaka Organic Chemical Industry Co., Ltd.) and the like can be preferably used. ..
  • the specific particles contain at least one polymer P.
  • the polymer P plays a role of retaining the polymerizable monomer M in the specific particles in the ink before being ejected from the inkjet head, thereby contributing to improving the ejection property of the ink.
  • the polymer P may be a chain polymer or a crosslinked polymer.
  • the chain polymer means a polymer having no crosslinked structure
  • the crosslinked polymer means a polymer having a crosslinked structure.
  • the chain polymer may have a cyclic structure or a branched structure.
  • Japanese Patent No. 6584677 can be referred to.
  • Preferred embodiments of the specific particles when the polymer P is a crosslinked polymer include microcapsules containing a shell made of the crosslinked polymer P and a core containing a polymerizable monomer.
  • specific particles containing the crosslinked polymer P for example, Japanese Patent No. 6510681 can be referred to.
  • the weight average molecular weight (Mw) of the polymer P is preferably 3000 to 200,000, more preferably 4000 to 150,000, still more preferably 5000 to 100,000, still more preferably, from the viewpoint of further improving the ejection property of the ink. Is 8000 to 80,000, more preferably 10,000 to 50,000. When the Mw of the polymer P is 3000 or more, the wear resistance of the image is further improved. When the Mw of the polymer P is 200,000 or less, the ink ejection property is further improved.
  • the number average molecular weight (Mn) and the weight average molecular weight (Mw) mean values calculated in terms of polystyrene by gel permeation chromatography (GPC).
  • GPC gel permeation chromatography
  • the glass transition temperature (Tg) of the polymer P is not particularly limited. From the viewpoint of improving the motility of the polymer P and further improving the image quality of the image (specifically, suppressing the graininess of the image), the Tg of the polymer P is preferably 120 ° C. or lower, more preferably 100 ° C. It is less than or equal to, more preferably 80 ° C. or lower, still more preferably 70 ° C. or lower. On the other hand, the Tg of the polymer P is preferably 0 ° C. or higher, more preferably 10 ° C. or higher, still more preferably 20 ° C. or higher, still more preferably 30 ° C. or higher.
  • the glass transition temperature (Tg) of a polymer means a value measured using differential scanning calorimetry (DSC).
  • DSC differential scanning calorimetry
  • the specific measurement of the glass transition temperature is carried out according to the method described in JIS K 7121 (1987) or JIS K 6240 (2011).
  • the glass transition temperature in the present disclosure is an extrapolated glass transition start temperature (hereinafter, may be referred to as Tig).
  • Tig extrapolated glass transition start temperature
  • the method for measuring the glass transition temperature will be described more specifically.
  • the extra glass transition start temperature (Tig) that is, the glass transition temperature in the present disclosure, is a straight line extending the baseline on the low temperature side of the DTA curve or DSC curve to the high temperature side and the curve of the stepwise change portion of the glass transition. It is calculated as the temperature of the intersection with the tangent line drawn at the point where the gradient becomes maximum.
  • the glass transition temperature (Tg) of the polymer P means a weighted average value of the glass transition temperatures of the individual polymers P.
  • the polymer P examples include urethane polymer, urethane urea polymer, urea polymer, acrylic polymer, polyester, polyolefin, polystyrene, polycarbonate, polyamide and the like.
  • the urethane polymer means a polymer containing urethane bonds and not containing urea bonds
  • the urea polymer means a polymer containing urea bonds and not containing urethane bonds
  • the urethane urea polymer means urethane. It means a polymer containing a bond and a urethane bond.
  • the acrylic polymer is at least one selected from the group consisting of acrylic acid, a derivative of acrylic acid (for example, acrylic acid ester), methacrylic acid, and a derivative of methacrylic acid (for example, methacrylic acid ester). It means a polymer (homogeneous polymer or copolymer) of the raw material monomer contained.
  • the polymer P preferably contains a bond U which is at least one of a urethane bond and a urea bond.
  • the polymer P is preferably a urethane polymer, a urethane urea polymer, or a urea polymer.
  • the bond U preferably contains a urethane bond.
  • the polymer P preferably contains a urethane bond and does not contain a urea bond, or preferably contains a urethane bond and a urea bond.
  • the polymer P preferably contains at least one hydrophilic group. This contributes to the dispersion stability of the specific particles in the ink, and as a result, the storage stability of the ink is further improved.
  • the hydrophilic group is preferably an anionic group or a nonionic group, and more preferably an anionic group.
  • the anionic group is more effective in improving the storage stability of the ink. That is, the anionic group (particularly preferably at least one selected from the group consisting of a carboxy group and a salt of the carboxy group) sufficiently exerts the effect of improving the storage stability of the ink even when its molecular weight is small. Can be.
  • nonionic group examples include a group having a polyether structure, and a monovalent group containing a polyalkyleneoxy group is preferable.
  • the anionic group may or may not be neutralized.
  • the unneutralized anionic group include a carboxy group, a sulfo group, a sulfate group, a phosphonic acid group, a phosphoric acid group and the like.
  • the neutralized anionic group means an anionic group in the form of a "salt" (eg, a salt of a carboxy group (eg-COONa)).
  • Examples of the neutralized anionic group include a carboxy group salt, a sulfo group salt, a sulfate group salt, a phosphonic acid group salt, a phosphoric acid group salt, and the like.
  • Neutralization can be carried out using, for example, an alkali metal hydroxide (eg, sodium hydroxide, potassium hydroxide, etc.) or an organic amine (eg, triethylamine, etc.).
  • Anionic groups are preferred Selected from the group consisting of carboxy group, carboxy group salt, sulfo group, sulfo group salt, sulfate group, sulfate group salt, phosphonic acid group, phosphonic acid group salt, phosphoric acid group, and phosphoric acid group salt. At least one is more preferred At least one selected from the group consisting of a carboxy group, a salt of a carboxy group, a sulfo group and a salt of a sulfo group is more preferable.
  • an alkali metal salt or an organic amine salt is preferable, and an alkali metal salt is preferable. Is more preferable.
  • an alkali metal in the alkali metal salt K or Na is preferable.
  • the polymer P contains an anionic group (for example, at least one selected from the group consisting of a carboxy group and a salt of a carboxy group) as a hydrophilic group
  • the anionic group contained in 1 g of the polymer P for example, for example, when the total number of millimoles of the carboxy group and the salt of the carboxy group) is taken as the acid value of the polymer P, the acid value of the polymer P is 0.10 mmol / g to 2.00 mmol / g from the viewpoint of dispersion stability. It is preferably 0.30 mmol / g to 1.50 mmol / g, and more preferably 0.30 mmol / g to 1.50 mmol / g.
  • the degree of neutralization of the anionic group in the polymer P is preferably 50% to 100%, more preferably 70% to 90%.
  • the degree of neutralization is the sum of "the number of unneutralized anionic groups (for example, carboxy group) and the number of neutralized anionic groups (for example, salt of carboxy group)" in the polymer P.
  • the ratio of "the number of neutralized anionic groups” to "" ie, ratio [number of neutralized anionic groups / (number of unneutralized anionic groups + neutralized anion) Number of sex groups)]).
  • the degree of neutralization of the anionic group in the polymer P can be measured by neutralization titration.
  • the specific particles include not only the polymer P but also the above-mentioned polymerizable monomer M (that is, a compound containing a polymerizable group).
  • the polymerizable monomer M contributes to improving the wear resistance of the film. Therefore, the polymer P does not necessarily have to contain a polymerizable group. However, from the viewpoint of further improving the wear resistance of the film, the polymer P may contain a polymerizable group.
  • a photopolymerizable group or a thermally polymerizable group is preferable.
  • a photopolymerizable group a radically polymerizable group is preferable, a group containing an ethylenic double bond is more preferable, and a (meth) acryloyl group, an allyl group, a styryl group, or a vinyl group is further preferable.
  • a (meth) acryloyl group is particularly preferable from the viewpoint of radical polymerization reactivity and the hardness of the film to be formed.
  • thermopolymerizable group an epoxy group, an oxetanyl group, an aziridinyl group, an azetidinyl group, a ketone group, an aldehyde group, or a blocked isocyanate group is preferable.
  • the polymer P may contain only one type of polymerizable group, or may contain two or more types. The inclusion of the polymerizable group in the polymer P can be confirmed, for example, by Fourier transform infrared spectroscopy (FT-IR) analysis.
  • FT-IR Fourier transform infrared spectroscopy
  • the polymer P may contain other structures other than those described above (ie, bonded U, hydrophilic groups, and polymerizable groups). Other structures include polysiloxane bonds (ie, divalent polysiloxane groups), monovalent polysiloxane groups, monovalent fluorinated hydrocarbon groups, divalent fluorinated hydrocarbon groups and the like.
  • the polymer P preferably contains a structural unit derived from an isocyanate compound (hereinafter, also referred to as “NCO”) and a structural unit derived from a compound containing an active hydrogen group.
  • NCO isocyanate compound
  • the polymer P of the above preferred embodiment contains a bond U formed by a reaction between an isocyanate group of an isocyanate compound and an active hydrogen group of a compound containing an active hydrogen group.
  • the active hydrogen group is preferably a hydroxy group, a primary amino group, or a secondary amino group.
  • a urethane group is formed by a reaction between an isocyanate group and a hydroxy group.
  • a urea group is formed by a reaction between an isocyanate group and a primary amino group or a secondary amino group.
  • the isocyanate compound which is a raw material of the polymer P having the above preferable structure and the compound containing an active hydrogen group may be hereinafter referred to as a raw material compound.
  • the isocyanate compound as a raw material compound may be only one kind or two or more kinds.
  • the compound containing an active hydrogen group as a raw material compound may be only one kind or two or more kinds.
  • the isocyanate compounds as the raw material compound a bifunctional or higher functional isocyanate compound is preferable.
  • a compound containing an active hydrogen group as a raw material compound a compound containing two or more active hydrogen groups is preferable.
  • At least one of the isocyanate compound and the compound containing an active hydrogen group preferably contains a hydrophilic group. This facilitates the production of the polymer P containing a hydrophilic group.
  • at least a part of the hydrophilic groups in the finally obtained polymer P may be a group in which the hydrophilic group in the raw material compound is neutralized.
  • a more preferable embodiment is an embodiment in which at least one of the raw material compounds containing an active hydrogen group is a compound containing an active hydrogen group and a hydrophilic group.
  • the polymer P contains a polymerizable group
  • at least one of the raw material compound, the isocyanate compound and the compound containing an active hydrogen group contains a polymerizable group. This facilitates the production of the polymer P containing a polymerizable group.
  • a more preferable embodiment is an embodiment in which at least one of the raw material compounds containing an active hydrogen group is a compound containing an active hydrogen group and a polymerizable group.
  • the polymer P may be a chain polymer or a crosslinked polymer.
  • the chain polymer as the polymer P can be produced by reacting a bifunctional isocyanate compound with a compound containing two active hydrogen groups.
  • the crosslinked polymer as the polymer P can be produced by reacting a trifunctional or higher functional isocyanate compound with a compound containing two or more active hydrogen groups.
  • the crosslinked polymer as the polymer P can also be produced by reacting a bifunctional isocyanate compound with a compound containing three or more active hydrogen groups.
  • the isocyanate compound is preferably a bifunctional or higher functional isocyanate compound, and more preferably a bifunctional to hexafunctional isocyanate compound.
  • the polymer P contains the following structural unit (P1), which is a structural unit derived from the bifunctional isocyanate compound.
  • L 1 represents a divalent organic group having 1 to 20 carbon atoms
  • * represents a bond position
  • L 1 include residues obtained by removing two isocyanate groups (NCO groups) from the bifunctional isocyanate compound according to the following specific examples.
  • bifunctional isocyanate compound examples are as follows. However, the bifunctional isocyanate compound is not limited to the following specific examples.
  • bifunctional isocyanate compound a bifunctional isocyanate compound derived from the above specific example can also be used.
  • Duranate (registered trademark) D101, D201, A101 (manufactured by Asahi Kasei Corporation) and the like can be mentioned.
  • the trifunctional or higher functional isocyanate compound is a compound containing at least one selected from the group consisting of bifunctional isocyanate compounds and three or more active hydrogen groups (for example, a trifunctional or higher functional polyol compound and a trifunctional or higher functional group). It is preferably a reaction product of at least one selected from the group consisting of the polyamine compound of the above and the polythiol compound of trifunctionality or higher.
  • the number of moles (number of molecules) of a bifunctional isocyanate compound to be reacted with a compound containing three or more active hydrogen groups is the number of moles of active hydrogen groups (equivalent to active hydrogen groups) in a compound containing three or more active hydrogen groups. Number), 0.6 times or more is preferable, 0.6 times to 5 times is more preferable, 0.6 times to 3 times is further preferable, and 0.8 times to 2 times is further preferable.
  • bifunctional isocyanate compound for forming a trifunctional or higher functional isocyanate compound examples include the bifunctional isocyanate compound according to the above-mentioned specific example.
  • Examples of the compound containing three or more active hydrogen groups for forming a trifunctional or higher functional isocyanate compound include the compounds described in paragraphs 0057 to 0058 of International Publication No. 2016/052053.
  • Examples of the trifunctional or higher functional isocyanate compound include an adduct-type trifunctional or higher-functional isocyanate compound, an isocyanurate-type trifunctional or higher-functional isocyanate compound, and a biuret-type trifunctional or higher-functionality isocyanate compound.
  • Commercially available products of adduct-type trifunctional or higher functional isocyanate compounds include Takenate® D-102, D-103, D-103H, D-103M2, P49-75S, D-110N, D-120N, D-.
  • biuret-type trifunctional or higher functional isocyanate compounds include Takenate (registered trademark) D-165N, NP1100 (above, Mitsui Chemicals, Inc.), and Death Module (registered trademark) N3200 (Sumika Bayer Urethane Co., Ltd.). ), Duranate (registered trademark) 24A-100 (Asahi Kasei Corporation) and the like.
  • At least one of the isocyanate compounds as a raw material compound may be an isocyanate compound containing a hydrophilic group.
  • isocyanate compounds containing hydrophilic groups reference is made to paragraphs 0112 to 0118 and 0252 to 0254 of WO 2016/052053.
  • isocyanate compounds as a raw material compound may be an isocyanate compound containing a polymerizable group.
  • isocyanate compounds containing polymerizable groups reference can be made to paragraphs 804 to 089, 0203, and 0205 of International Publication No. 2016/052053.
  • the compound containing an active hydrogen group is preferably a compound containing two or more active hydrogen groups.
  • the compound containing two or more active hydrogen groups is more preferably a polyol compound (that is, a compound having two or more hydroxy groups) or a polyamine compound (that is, a compound having two or more amino groups).
  • the polymer P preferably contains at least one of the following structural units (P0).
  • L 0 represents a divalent organic group and represents * Represents the bond position Y 1 and Y 2 independently represent an oxygen atom, a sulfur atom, or an ⁇ NR 1 ⁇ group, respectively.
  • R 1 represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms. * Represents the bond position.
  • the divalent organic group represented by L0 may be a group consisting of a carbon atom and a hydrogen atom, contains a carbon atom and a hydrogen atom, and has a hetero atom (for example, for example). It may be a group containing an oxygen atom, a nitrogen atom, a sulfur atom, etc.).
  • the divalent organic group represented by L 0 may contain at least one of a hydrophilic group and a polymerizable group. Specific examples of L 0 include residues obtained by removing two active hydrogen groups from specific examples of compounds containing active hydrogen groups, which will be described later.
  • R 1 a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms is preferable, and a hydrogen atom or a hydrocarbon group having 1 to 3 carbon atoms is more preferable.
  • Y 1 and Y 2 are each independently preferably an oxygen atom or an ⁇ NR 1 ⁇ group, and more preferably an oxygen atom.
  • nC 7 H 15 , nC 9 H 19 , nC 11 H 23 , and nC 17 H 35 are normal heptyl group, normal nonyl group, normal undesyl group, and normal heptadecyl, respectively.
  • Compound (16) PPG is polypropylene glycol, and n is a repeat number.
  • Compound (16-2) PEG is polyethylene glycol, and n is a repeat number.
  • Compound (17) PEs are polyester diols, n is a repeat number, and Ra and the two Rbs are independently divalent hydrocarbon groups having 2 to 25 carbon atoms. The n Ras in compound (17) PEs may be the same or different.
  • the (n + 1) Rbs in compound (17) PEs may be the same or different.
  • Compound (18) PC is a polycarbonate diol, n is a repetition number, and (n + 1) Rc independently have 2 to 12 carbon atoms (preferably 3 to 8, more preferably 3 to 6). ) Is an alkylene group.
  • the (n + 1) Rc in compound (18) PC may be the same but different.
  • Compound (19) PCL is a polycaprolactone diol, n and m are repetition numbers, respectively, and Rd is an alkylene group having 2 to 25 carbon atoms.
  • Examples of the compound containing an active hydrogen group include compounds containing an active hydrogen group and a polymerizable group.
  • a compound containing an active hydrogen group and a polymerizable group is suitable as a compound for introducing a polymerizable group into the polymer P (hereinafter, also referred to as a “compound for introducing a polymerizable group”).
  • the diol compound as a compound containing an active hydrogen group and a polymerizable group will be shown, but the compound containing an active hydrogen group and a polymerizable group is not limited to the following specific examples.
  • Examples of the compound containing an active hydrogen group include compounds containing an active hydrogen group and a hydrophilic group.
  • the compound containing an active hydrogen group and a hydrophilic group is suitable as a compound for introducing a hydrophilic group into the polymer P (hereinafter, also referred to as “a compound for introducing a hydrophilic group”).
  • the polymer P preferably contains the following structural unit (P2).
  • L 21 represents a trivalent organic group having 1 to 20 carbon atoms.
  • L 22 represents a single bond or a divalent organic group having 1 to 20 carbon atoms.
  • a 1 represents a carboxy group, a salt of a carboxy group, a sulfo group, or a salt of a sulfo group. * Represents the bond position.
  • the number of carbon atoms in the trivalent organic group having 1 to 20 carbon atoms represented by L 21 is preferably 2 to 20, more preferably 3 to 20, and even more preferably 4 to 20.
  • the trivalent organic group represented by L 21 at least one carbon atom in the trivalent hydrocarbon group or the trivalent hydrocarbon group is a hetero atom (preferably an oxygen atom, a sulfur atom, or a trivalent hydrocarbon group). Groups replaced with (nitrocarbon atoms) are preferred.
  • the number of carbon atoms in the divalent organic group having 1 to 20 carbon atoms represented by L 22 is preferably 1 to 10, and more preferably 1 to 6.
  • the divalent organic group represented by L 22 at least one carbon atom in the divalent hydrocarbon group (preferably an alkylene group) or the divalent hydrocarbon group (preferably an alkylene group) is used. Groups replaced with an oxygen atom or a sulfur atom (preferably an oxygen atom) are preferred.
  • L 22 may be a single bond.
  • the compound containing an active hydrogen group and a hydrophilic group is not limited to the following specific examples.
  • the carboxy group and the sulfo group in the following specific examples may be neutralized (that is, a salt of the carboxy group and a salt of the sulfo group, respectively).
  • the content of the polymer P with respect to the total solid content of the specific particles is preferably 10% by mass to 90% by mass, more preferably 20% by mass to 80% by mass, further preferably 30% by mass to 70% by mass, and 40% by mass to 40% by mass. 60% by mass is more preferable.
  • the content of the polymer P with respect to the total amount of the ink is preferably 0.3% by mass to 20% by mass, more preferably 0.5% by mass to 15% by mass, still more preferably 1% by mass to 10% by mass.
  • the specific particles may contain at least one of the radical polymerization initiators.
  • the radical polymerization initiator means a compound that absorbs light to generate a radical.
  • the specific particles When the specific particles contain a radically polymerizable monomer as the polymerizable monomer, the specific particles preferably contain at least one kind of a radical polymerization initiator. As a result, the wear resistance and adhesion of the formed film are further improved. The reason for this is considered to be that the distance between the radically polymerizable group in the radically polymerizable monomer and the radical polymerization initiator becomes short, and the curing sensitivity of the film (hereinafter, also simply referred to as “sensitivity”) is improved.
  • the radical polymerization initiator for example, solubility in water
  • a radical polymerization initiator having a temperature of 1.0% by mass or less at 25 ° C.
  • the range of choices of the radical polymerization initiator to be used is widened, and the range of choices of the light source to be used is also widened. Therefore, the curing sensitivity can be improved as compared with the conventional case.
  • radical polymerization initiator which are highly sensitive but have low dispersibility in water or have low solubility
  • examples of the radical polymerization initiator described above include carbonyl compounds and acylphosphine oxide compounds described below. , Acylphosphine oxide compounds are preferred.
  • a substance having low solubility in water can be contained in the specific particles so that the aqueous dispersion and ink of the present disclosure, which are water-based compositions, contain the substance. can.
  • the aqueous dispersion and the ink in which the specific particles contain a radical polymerization initiator are also excellent in storage stability as compared with the conventional photocurable composition. It is considered that the reason for this is that the inclusion of the radical polymerization initiator in the specific particles suppresses the aggregation or precipitation of the radical polymerization initiator.
  • radical polymerization initiator for example, the description in paragraphs 0091 to 0094 of International Publication No. 2016/052053 can be appropriately referred to.
  • a carbonyl compound such as an aromatic ketone or (b) an acylphosphine oxide compound is more preferable, and specifically, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (for example, IRGACURE® 819) manufactured by BASF, 2- (dimethylamine) -1- (4-morpholinophenyl) -2-benzyl-1-butanone (eg, IRGACURE® 369 manufactured by BASF).
  • an acylphosphine oxide compound is preferable, and a monoacylphosphine oxide compound (particularly preferably 2,4) is preferable as the radical polymerization initiator from the viewpoint of improving sensitivity and compatibility with LED light.
  • a monoacylphosphine oxide compound particularly preferably 2,4
  • 6-trimethylbenzoyl-diphenyl-phosphine oxide or bisacylphosphine oxide compounds (particularly preferably bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide).
  • the wavelength of the LED light is preferably 355 nm, 365 nm, 385 nm, 395 nm, or 405 nm.
  • Specific particles of the embodiment containing a radical polymerization initiator include, for example, an oil phase component containing a polymer P (or a raw material compound for producing the polymer P), a radically polymerizable monomer, and a photopolymerization initiator, and an aqueous phase component. It can be produced by emulsifying a mixture of and.
  • the content of the radical polymerization initiator is preferably 0.1% by mass to 15% by mass, more preferably 0.5% by mass to 10% by mass, still more preferably, with respect to the total solid content of the specific particles. Is 1% by mass to 6% by mass.
  • the specific particles may contain at least one of the sensitizers.
  • the specific particles preferably contain at least one kind of sensitizer.
  • the specific particles contain a sensitizer, the decomposition of the photopolymerization initiator by irradiation with active energy rays can be further promoted.
  • a sensitizer is a substance that absorbs a specific active energy ray and becomes an electronically excited state. The sensitizer in the electron-excited state comes into contact with the photopolymerization initiator and causes actions such as electron transfer, energy transfer, and heat generation. This promotes chemical changes in the photopolymerization initiator, that is, decomposition, radicals, acid or base production, and the like.
  • Examples of the sensitizer include benzophenone, thioxanthone, isopropylthioxanthone, anthraquinone, 3-acylcoumarin derivative, terphenyl, styrylketone, 3- (aroylmethylene) thiazolin, eosin, eosin, rhodamine, erythrosin and the like. ..
  • Examples of the sensitizer include a compound represented by the general formula (i) described in JP-A-2010-24276, a compound represented by the general formula (I) described in JP-A-6-107718, and the like. Can also be suitably used.
  • the sensitizer at least one selected from thioxanthone, isopropylthioxanthone, and benzophenone is preferable from the viewpoint of compatibility with LED light and reactivity with a photopolymerization initiator, and from thioxanthone and isopropylthioxanthone. At least one selected is more preferred, and isopropylthioxanthone is even more preferred.
  • the specific particles contain a sensitizer, the sensitizer may be contained alone or in combination of two or more.
  • the content of the sensitizer is preferably 0.1% by mass to 20% by mass, and 0.2% by mass to 15% by mass, based on the solid content of the specific particles. Is more preferable, and 0.3% by mass to 10% by mass is further preferable.
  • Specific particles containing a photopolymerization initiator and a sensitizer are, for example, an oil phase component containing a polymer P (or a raw material compound for producing the polymer P), a radically polymerizable monomer, a photopolymerization initiator and a sensitizer. It can be produced by emulsifying a mixture of the water phase component and the aqueous phase component.
  • the specific particles may contain other components other than the above-mentioned components.
  • Other components include, for example, a group consisting of a polysiloxane bond (that is, a divalent polysiloxane group), a monovalent polysiloxane group, a monovalent fluorinated hydrocarbon group, and a divalent fluorinated hydrocarbon group. Examples include compounds containing at least one selected from.
  • the ink in the present disclosure can be produced by producing an aqueous dispersion of specific particles containing the above-mentioned specific particles and water, and adding other components to the obtained aqueous dispersion as necessary. Further, since the ink in the present disclosure is a form of an aqueous dispersion of specific particles, depending on the composition of the ink, it is directly as an aqueous dispersion of specific particles (that is, without adding other components). Ink can also be produced. There is no particular limitation on the method for producing an aqueous dispersion of specific particles. Examples of the method for producing an aqueous dispersion of specific particles include the following production methods A and B.
  • the production method A includes a step of mixing and emulsifying an oil phase component containing an organic solvent, a polymer P, and a polymerizable monomer and an aqueous phase component containing water to obtain an aqueous dispersion of specific particles.
  • the production method A is suitable as a method for producing an aqueous dispersion of specific particles containing the polymer P of the embodiment which is a chain polymer.
  • publicly known documents such as Japanese Patent No. 6584677 can be referred to.
  • the production method B contains an organic solvent, a raw material compound of the polymer P (for example, a trifunctional or higher isocyanate compound, a compound having two or more active hydrogen groups, etc.), an oil phase component containing a polymerizable monomer, and water. It has a step of obtaining an aqueous dispersion of specific particles by mixing and emulsifying an aqueous phase component.
  • the production method B is suitable as a method for producing an aqueous dispersion of specific particles (for example, microcapsules) containing the polymer P of the embodiment which is a crosslinked polymer.
  • publicly known documents such as International Publication No. 2016/052053 can be referred to.
  • the total solid content of the specific particles in the ink is preferably 2% by mass to 30% by mass, more preferably 3% by mass to 25% by mass, and further preferably 4% by mass to 20% by mass, based on the total amount of the ink. It is by mass, more preferably 5% by mass to 15% by mass.
  • the total solid content of the specific particles with respect to the total amount of the ink in the present disclosure is 2% by mass or more, the image quality and wear resistance of the image are further improved.
  • the total solid content of the specific particles with respect to the total amount of the ink in the present disclosure is 30% by mass or less, the image quality and wear resistance of the image are further improved.
  • the total solid content of the specific particles in the ink referred to here means the total solid content of the specific particles in the ink before ejection (that is, ejected from the inkjet head).
  • volume average dispersed particle diameter of specific particles The volume average dispersed particle size of the specific particles in the ink is not particularly limited, but is preferably 0.01 ⁇ m to 10 ⁇ m, more preferably 0.01 ⁇ m to 5 ⁇ m, and 0. It is more preferably 05 ⁇ m to 1 ⁇ m, further preferably 0.05 ⁇ m to 0.5 ⁇ m, and even more preferably 0.05 ⁇ m to 0.3 ⁇ m.
  • volume average dispersed particle size refers to a value measured by a light scattering method. The volume average dispersed particle diameter of a specific particle is measured by the light scattering method using, for example, LA-960 (HORIBA, Ltd.).
  • the ink in the present disclosure contains water.
  • the content of water with respect to the total amount of the ink in the present disclosure is preferably 10% by mass or more, more preferably 20% by mass or more, still more preferably 30% by mass or more, and particularly preferably 50% by mass or more. be.
  • the upper limit of the water content with respect to the total amount of the ink in the present disclosure is appropriately determined depending on the content of other components, but is, for example, 99% by mass, preferably 95% by mass, and more preferably 90% by mass. be.
  • the ink in the present disclosure contains at least one water-soluble organic solvent. This ensures the ink ejection property from the inkjet head.
  • the "water-soluble” in the “water-soluble organic solvent” means the property of dissolving 1 g or more with respect to 100 g of water at 25 ° C.
  • the amount of the water-soluble organic solvent dissolved in 100 g of water at 25 ° C. is preferably 5 g or more, more preferably 10 g or more.
  • the content of the water-soluble organic solvent with respect to the total amount of the ink is preferably 1% by mass to 50% by mass, more preferably 5% by mass to 30% by mass, and further preferably 8% by mass to 15% by mass. , More preferably 10% by mass to 20% by mass.
  • the content of the water-soluble organic solvent is 1% by mass or more, the ejection property of the ink is further improved.
  • the content of the water-soluble organic solvent is 50% by mass or less, the storage stability of the ink is further improved.
  • water-soluble organic solvent examples include as follows.
  • -Alcohols eg, methanol, ethanol, propanol, isopropanol, butanol, isobutanol, secondary butanol, tertiary butanol, pentanol, hexanol, cyclohexanol, benzyl alcohol, etc.
  • -Polyhydric alcohols eg, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, butylene glycol, hexanediol, pentanediol, glycerin, hexanetriol, thiodiglycol, 2- Methylpropanediol, etc.
  • -Polyvalent alcohol ethers eg, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol
  • Water-soluble organic solvent (S-1) having a boiling point of 190 ° C. or lower contains at least one water-soluble organic solvent (S-1) having a boiling point of 190 ° C. or lower (hereinafter, also simply referred to as “water-soluble organic solvent (S-1)”). It is preferable to do so. This further improves the blocking resistance of the recorded image.
  • excellent blocking resistance means a property that blocking of an image (that is, a phenomenon in which a contacted object adheres to an image when the contacted object is superimposed on the image) is suppressed.
  • the boiling point means the boiling point under 1 atm (101325 Pa).
  • water-soluble organic solvent (S-1) examples include propylene glycol (boiling point 188 ° C.), propylene glycol monomethyl ether (boiling point 121 ° C.), ethylene glycol monomethyl ether (boiling point 124 ° C.), and propylene glycol monoethyl ether (boiling point 133 ° C.).
  • the ratio of the water-soluble organic solvent (S-1) to the water-soluble organic solvent in the ink in the present disclosure is preferably 50% by mass or more, more preferably 60% by mass or more. , More preferably 70% by mass or more.
  • the ratio of the water-soluble organic solvent (S-1) having a boiling point of 190 ° C. or lower to the water-soluble organic solvent in the ink in the present disclosure may be 100% by mass or less than 100% by mass. good.
  • the content of the water-soluble organic solvent (S-1) is preferably 1% by mass to 35% by mass, more preferably, with respect to the total amount of the ink. Is 5% by mass to 30% by mass, more preferably 8% by mass to 15% by mass, still more preferably 10% by mass to 20% by mass.
  • the water-soluble organic solvent in the ink in the present disclosure may contain at least one water-soluble organic solvent having a boiling point of more than 190 ° C.
  • water-soluble organic solvent having a boiling point of more than 190 ° C. examples include 2-methyl-1,3-propanediol (MP dial) (boiling point of 214 ° C.), ethylene glycol (boiling point of 196 ° C.), and 1,2-blancdiol.
  • the ink in the present disclosure may be an ink containing at least one kind of coloring material (so-called “colored ink”) or an ink containing no coloring material (so-called “clear ink”).
  • the coloring material is contained outside the specific particles (that is, the specific particles do not contain the coloring material).
  • the coloring material is not particularly limited, and can be arbitrarily selected and used from known coloring materials such as pigments, water-soluble dyes, and disperse dyes. Among these, it is more preferable to contain a pigment from the viewpoint of excellent weather resistance and excellent color reproducibility.
  • the pigment is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include known organic pigments and inorganic pigments.
  • the pigments include resin particles dyed with a dye, a commercially available pigment dispersion, a surface-treated pigment (for example, a pigment dispersed in water, a liquid compound, an insoluble resin or the like as a dispersion medium, and a resin. , Pigment surface treated with pigment derivative, etc.).
  • examples of the organic pigment and the inorganic pigment include yellow pigment, red pigment, magenta pigment, blue pigment, cyan pigment, green pigment, orange pigment, purple pigment, brown pigment, black pigment, white pigment and the like.
  • a pigment dispersant may be used if necessary.
  • a pigment is used as the coloring material, a self-dispersing pigment having a hydrophilic group on the surface of the pigment particles may be used as the pigment.
  • paragraphs 0180 to 0200 of JP-A-2014-040529 and paragraphs 0122 to 0129 of International Publication No. 2016/052053 can be appropriately referred to.
  • the content of the coloring material is preferably 0.1% by mass to 20% by mass, more preferably 0.5% by mass to 10% by mass, and 0, based on the total amount of the ink. .5% by mass to 5% by mass is particularly preferable.
  • the ink in the present disclosure may contain other components other than those described above, if necessary. Other components may or may not be contained in the specific particles.
  • the ink in the present disclosure may be contained in the specific particles, or may contain a surfactant, a polymerization inhibitor, an ultraviolet absorber, or the like as a component that may not be contained in the specific particles. Further, the ink in the present disclosure may contain a water-soluble polymerizable monomer, a water-soluble photopolymerization initiator, a water-soluble resin, and the like in addition to the specific particles, if necessary.
  • paragraphs 0134 to 0157 of International Publication No. 2016/052053 can be referred to.
  • the method for producing the ink in the present disclosure is not particularly limited, but is preferable.
  • an aqueous dispersion of specific particles is produced by a step of producing an aqueous dispersion of specific particles by the above-mentioned method for producing an aqueous dispersion (production method A or production method B).
  • production method A or production method B There is also an embodiment of directly producing an ink (that is, a method in which no other component is added to an aqueous dispersion of specific particles).
  • the ink in the present disclosure preferably has a viscosity of 3 mPa ⁇ s to 15 mPa ⁇ s, more preferably 3 mPa ⁇ s to 13 mPa ⁇ s, when the ink is set to 25 ° C. to 50 ° C.
  • the ink in the present disclosure preferably has a viscosity of 50 mPa ⁇ s or less when the temperature of the ink is 25 ° C.
  • the viscosity of the ink is a value measured using a viscometer.
  • VISCOMETER TV-22 Toki Sangyo Co., Ltd.
  • part represents a mass part unless otherwise specified.
  • Neostan U-600 inorganic bismuth catalyst manufactured by Nitto Kasei Co., Ltd .; hereinafter also referred to as "U-600”
  • U-600 inorganic bismuth catalyst manufactured by Nitto Kasei Co., Ltd .; hereinafter also referred to as "U-600”
  • ethyl acetate (114.39 g) and isopropyl alcohol (82.84 g) were added thereto, and the mixture was stirred at 70 ° C. for 3 hours.
  • the temperature was lowered to 50 ° C., diisopropylethylamine (9.36 g) was added, and the mixture was stirred for 1 hour.
  • the reaction solution was allowed to cool to room temperature, and the concentration was adjusted with ethyl acetate to obtain a 30% by mass solution of the polymer P1 (the solvent was a mixed solution of ethyl acetate / isopropyl alcohol).
  • the polymer P1 had an Mw of 12,000 and an acid value of 0.68 mmol / g.
  • the reaction solution was allowed to cool to room temperature, and the concentration was adjusted with methyl ethyl ketone to obtain a 30% by mass solution of the polymer P2 (solvent was a mixed solution of methyl ethyl ketone / isopropyl alcohol).
  • the polymer P2 had an Mw of 12,000 and an acid value of 0.68 mmol / g.
  • the reaction solution was allowed to cool to room temperature, and the concentration was adjusted with methyl ethyl ketone to obtain a 30% by mass solution of the polymer P3 (solvent was a mixed solution of methyl ethyl ketone / isopropyl alcohol).
  • the polymer P3 had an Mw of 12,000 and an acid value of 0.68 mmol / g.
  • the reaction solution was allowed to cool to room temperature, and the concentration was adjusted with methyl ethyl ketone to obtain a 30% by mass solution of the polymer P4 (solvent was a mixed solution of methyl ethyl ketone / isopropyl alcohol).
  • solvent was a mixed solution of methyl ethyl ketone / isopropyl alcohol.
  • the polymer P4 had an Mw of 12,000 and an acid value of 0.68 mmol / g.
  • Example 1 ⁇ Preparation of aqueous dispersion of specific particles> -Preparation of oil phase components- 30% by weight solution of polymer P1 (66.7 g), SR295 (21.5 g) as the polymerizable monomer M, IRGACURE® 819 (1.5 g) as a photopolymerization initiator, ITX (isopropylthioxanthone) (0.25 g) as a sensitizer and ethyl acetate (36.7 g) was mixed and stirred at room temperature for 30 minutes to obtain an oil phase component.
  • polymer P1 (66.7 g)
  • SR295 21.5 g
  • IRGACURE® 819 1.5 g
  • ITX isopropylthioxanthone
  • ethyl acetate 36.7 g
  • SR295 is a tetrafunctional radically polymerizable monomer, specifically pentaerythritol tetraacrylate (molecular weight 352). SR295 is classified into a monomer (M-1), and among the monomers (M-1), it is classified into a monomer (M1B) (that is, a monomer (M-1) other than the monomer (M1A)) (see Table 1). ).
  • IRGACURE® 819 is an acylphosphine oxide-based radical polymerization initiator, specifically, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide.
  • aqueous dispersion of specific particles The oil phase component and the aqueous phase component were mixed, and the obtained mixture was emulsified at room temperature at 7000 rpm (revolution per minute) for 30 minutes to obtain an emulsion.
  • the obtained emulsion is added to distilled water (60 g), the obtained liquid is heated to 50 ° C., and the mixture is stirred at 50 ° C. for 5 hours to obtain a solvent (ethyl acetate and isopropyl alcohol in Example 1). ) Distilled.
  • the liquid from which the solvent was distilled off was diluted with distilled water so that the total solid content was 20% by mass to obtain an aqueous dispersion of specific particles.
  • the volume average dispersed particle diameter of the specific particles was 70 nm.
  • the total solid content of the specific particles in the above ink (that is, the ink before ejection) is 10% by mass. In this example, this value was regarded as the total solid content of the specific particles in the ink at the time of impact (see Table 1).
  • the base material As the PVC film (base material), "AVERY (registered trademark) 400 GLOSS WHITE PERMANENT" manufactured by Avery Dennison was used.
  • the base material was heated so that the temperature of the surface to which the ink was applied (that is, the surface on which the ink landed) was 50 ° C. (preheating step). This preheating was performed using a platen heater provided in the DMP-2850 on the upstream side in the substrate transport direction with respect to the inkjet head.
  • the ink was sprayed onto the heated substrate from the inkjet head of the inkjet recording device to apply the ink (applying step).
  • the ink ejection conditions were 900 dpi (dots per inch) and 1 dot 10 pL.
  • the ink was applied while maintaining the heating of the base material, so that the ink landed on the surface of the base material kept at 50 ° C.
  • the maintenance of heating of the base material during ink application was performed using a platen heater provided below the inkjet head (that is, the ink application region) in DMP-2850.
  • the ink applied on the substrate is irradiated with UV light (peak wavelength 395 nm) from a 395 nm LED lamp (product name “PEL UV CURE UNIT”, manufactured by PRINTED ELECTRONICS) arranged in the vicinity of the inkjet head (that is,). (Exposure) (irradiation step).
  • the irradiation energy of UV light was 1000 mJ / cm 2 .
  • the time from ink landing to exposure (that is, the time from the time when the ink landed on the substrate to the start of UV light irradiation) was adjusted to be 0.10 seconds (see Table 1).
  • the exposed ink was heated and dried at 50 ° C. for 180 seconds to obtain an image (drying step). The heating and drying of the ink was performed by bringing the surface of the substrate opposite to the ink-applied surface into contact with the hot plate.
  • Total solid content of specific particles in the ink at the start of exposure Using an FTA-1000 type contact angle meter manufactured by FTA and a hot water circulation type temperature control stage, the total solid content (mass%) of the specific particles in the ink at the start of exposure was determined by the above-mentioned method.
  • the remaining amount of liquid component (mass%) in the irradiation step that is, the liquid component in the ink after irradiation with the active energy ray with respect to the content of the liquid component in the ink before irradiation with the active energy ray). Content (% by mass)) was determined.
  • the residual amount of liquid component (% by mass) in the drying step that is, the content of the liquid component in the heat-dried ink in the drying step with respect to the content of the liquid component in the ink before being heat-dried). (Mass%)) was calculated.
  • image quality Using the above ink stored at room temperature for 1 day or less after preparation, the character images shown in FIG. 1 were recorded at 5 point, 6 point, and 7 point sizes under the above image recording conditions. Character images of each size were observed with a craft loupe (manufactured by Etsumi) at a magnification of 10 times. Based on the observed results, the fineness of the image was evaluated according to the following evaluation criteria. In the following evaluation criteria, the one with the best image quality is A.
  • A The character image shown in FIG. 1 having a size of 5 points was formed without crushing and bleeding.
  • B The character image shown in FIG. 1 having a size of 6 points was formed without crushing and bleeding (except when it corresponds to A).
  • C The character image shown in FIG. 1 having a size of 7 points was formed without crushing and bleeding (except when it corresponds to A and B).
  • D The character image shown in FIG. 1 having a size of 7 points was formed by being crushed or bleeding.
  • a solid image was recorded on a substrate (PVC film) under the conditions of the above image recording using the above ink stored at room temperature within 1 day after preparation.
  • a rubbing test under the following conditions was carried out on the solid image formed on the above substrate.
  • As the canvas a dry canvas was used.
  • Test equipment Paperboard wear resistance tester (JIS P-8136) Japan T.K. M. C. Type of canvas Co., Ltd .: Canvas No. 6 (manufactured by Takeyari Co., Ltd.) Number of rubbing: 500 times Load: 500gf
  • transfer OD concentration of cyan color transferred to the canvas after the rubbing test
  • IPA abrasion resistance
  • a solid image was recorded on a substrate (PVC film) under the conditions of the above image recording using the above ink stored at room temperature within 1 day after preparation.
  • a cross-hatch test was carried out on the obtained solid image in accordance with ISO2409 (2013) (cross-cut method), and the adhesion of the solid image to the substrate was evaluated according to the following evaluation criteria.
  • the cut interval was set to 1 mm, and 25 square grids of 1 mm square were formed.
  • the rank with the best adhesion of the solid image is A.
  • the rate (%) of the lattice peeling is a value obtained by the following formula.
  • Ink ejection property The ink stored within 1 day at room temperature after preparation was ejected from the inkjet head of the inkjet recording apparatus for 30 minutes, and then the ejection was stopped. After 5 minutes had passed from the stop of ejection, the ink was ejected again from the head on the substrate to form a solid image of 5 cm ⁇ 5 cm. These images were visually observed to confirm the presence or absence of missing dots due to the occurrence of non-ejection nozzles, etc., and the ink ejection property was evaluated according to the following evaluation criteria. In the following evaluation criteria, the one with the best ink ejection property is A.
  • Examples 2 to 4 In the preparation of the aqueous dispersion of specific particles, a 30% by mass solution (66.7 g) of the polymer P1, a 30% by mass solution (66.7 g) of the polymer P2, a 30% by mass solution (66.7 g) of the polymer P3, and the like. And by changing to each of the 30% by mass solution (66.7 g) of the polymer P4, the same operation as in Example 1 was performed except that the polymer P1 in the specific particles was changed to each of the polymers P2 to P4. rice field. The results are shown in Tables 1 and 2.
  • Examples 5 and 18 to 20 and Comparative Example 1 The same operation as in Example 1 was performed except that the type of the polymerizable monomer M was changed as shown in Table 1. In Examples 18 to 20, two kinds of polymerizable monomers M were used at the contents shown in Table 1. In Comparative Example 1, a monomer (M-2) (that is, a polymerizable monomer M other than the monomer (M-1)) was used. The results are shown in Tables 1 and 2.
  • Examples 6, 7, 12, and 13 Same as Example 5 except that the temperature of the base material at the time of ink landing and the temperature of the base material at the time of applying ink are changed to the temperatures shown in the “Temperature of the base material at the time of ink landing” in Table 1. The operation of was performed. The results are shown in Tables 1 and 2.
  • Examples 8 and 9 and Comparative Example 4 The same operation as in Example 5 was performed except that the time from ink landing to the start of exposure was changed as shown in Table 1. The results are shown in Tables 1 and 2.
  • Examples 10 and 11 and Comparative Examples 2 and 3 The same operation as in Example 5 was performed except that the total amounts of the polymerizable monomer M and the polymer P were not changed and the contents of the polymerizable monomer M and the polymer P were changed as shown in Table 1. rice field. The results are shown in Tables 1 and 2.
  • Example 14 The temperature of the base material at the time of ink landing and the temperature of the base material at the time of applying ink are changed to the temperatures shown in the "Temperature of the base material at the time of ink landing" in Table 1, and the exposure is started from the ink landing. The same operation as in Example 5 was performed except that the time until was changed as shown in Table 1. The results are shown in Tables 1 and 2.
  • Example 15 and 16 The same operation as in Example 5 was performed except that the temperature for heating and drying after exposure (hereinafter, also referred to as the heating temperature after exposure) was changed as shown in Table 1. The results are shown in Tables 1 and 2.
  • Example 17 The same operation as in Example 16 was carried out except that the residual amount of the liquid component in the drying step was changed as shown in Table 1 by shortening the heating and drying time after the exposure. The results are shown in Tables 1 and 2.
  • the meaning of the abbreviation of the polymerizable monomer M is as follows.
  • SR295 Pentaerythritol tetraacrylate. Made by Sartmer.
  • SR833S Tricyclodecanedimethanol diacrylate. Made by Sartmer.
  • OTA480 Glycerin propoxytriacrylate. Made by Daisel Ornex.
  • CD595 1,10-decanediol diacrylate.
  • FA512M Dicyclopentenyloxyethyl methacrylate. Made by Hitachi Kasei Kogyo Co., Ltd.
  • SR444 Pentaerythritol triacrylate. Sartmer.
  • the polymerizable monomer M contains a monomer (M-1) having a viscosity at 25 ° C. of 500 mPa ⁇ s or less, and contains a monomer (M-).
  • An ink having a content of 1) of 25% by mass to 80% by mass with respect to the total solid content of the particles is applied onto the substrate, and the ink applied on the substrate is subjected to the period from the impact of the ink to the start of exposure.
  • the active energy rays were irradiated at the timing when the time became 1.00 seconds or less, and an image was obtained. According to each example, an image having excellent image quality and wear resistance was obtained.
  • the results of the comparative example are as follows.
  • the polymerizable monomer M contained a monomer (M-2) having a viscosity of more than 500 mPa ⁇ s instead of the monomer (M-1)
  • the image quality and abrasion resistance of the image were deteriorated.
  • Comparative Example 2 in which the content of the monomer (M-1) was less than 25% by mass with respect to the total solid content of the particles, the image quality and wear resistance of the image were deteriorated.
  • Comparative Example 3 in which the content of the monomer (M-1) was more than 80% by mass with respect to the total solid content of the particles, the image quality and wear resistance of the image were deteriorated.
  • Comparative Example 4 in which the time from the ink landing to the start of exposure was more than 1.00 seconds, the image quality of the image was deteriorated.
  • Example 9 From the results of Examples 9 and 14, it can be seen that the image quality and abrasion resistance of the image are further improved in Example 9 in which the content of the specific particles in the ink at the start of exposure is 3% by mass or more and less than 20% by mass. ..

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