WO2023181583A1 - 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 PDFInfo
- Publication number
- WO2023181583A1 WO2023181583A1 PCT/JP2023/000102 JP2023000102W WO2023181583A1 WO 2023181583 A1 WO2023181583 A1 WO 2023181583A1 JP 2023000102 W JP2023000102 W JP 2023000102W WO 2023181583 A1 WO2023181583 A1 WO 2023181583A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- ink
- inkjet recording
- recording method
- post
- acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Ceased
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M7/00—After-treatment of prints, e.g. heating, irradiating, setting of the ink, protection of the printed stock
- B41M7/009—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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41J—TYPEWRITERS; SELECTIVE PRINTING MECHANISMS, i.e. MECHANISMS PRINTING OTHERWISE THAN FROM A FORME; CORRECTION OF TYPOGRAPHICAL ERRORS
- B41J2/00—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed
- B41J2/005—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed characterised by bringing liquid or particles selectively into contact with a printing material
- B41J2/01—Ink jet
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- 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
-
- 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
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- 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
- B41M5/0017—Application of ink-fixing material, e.g. mordant, precipitating agent, on the substrate prior to printing, e.g. by ink-jet printing, coating or spraying
-
- 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
- B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
- B41M5/52—Macromolecular coatings
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- 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
- B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
- B41M5/52—Macromolecular coatings
- B41M5/5218—Macromolecular coatings characterised by inorganic additives, e.g. pigments, clays
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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
- C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
- C09D11/037—Printing inks characterised by features other than the chemical nature of the binder characterised by the pigment
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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
- C09D11/32—Inkjet printing inks characterised by colouring agents
- C09D11/322—Pigment inks
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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
- C09D11/30—Inkjet printing inks
- C09D11/38—Inkjet printing inks characterised by non-macromolecular additives other than solvents, pigments or dyes
-
- 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
- C09D11/54—Inks based on two liquids, one liquid being the ink, the other liquid being a reaction solution, a fixer or a treatment solution for the ink
Definitions
- the present disclosure relates to an inkjet recording method.
- Japanese Patent Laid-Open No. 2017-124561 discloses an image forming method in which an image is formed by ejecting droplets onto a recording medium, and in which a post-processing liquid is applied at least on the image of the recording medium on which the image has been formed.
- This document describes an image forming method characterized by ejecting a post-processing liquid, specifying an area that overlaps with an area on a recording medium where an image is to be formed, and ejecting a post-processing liquid onto the specified area.
- JP 2020-164333A discloses a post-processing unit that performs post-processing on a recording medium recorded with water-based ink, a mounting unit on which a recording medium to be post-processed in the post-processing unit is placed, and a recording medium.
- a deformation suppressing means for suppressing deformation of the recording medium in the storage unit due to a predetermined parameter related to recording processing for the recording medium; and a control section for controlling the deformation suppressing means based on the predetermined parameter.
- a post-processing device that includes information based on conditions.
- an inkjet recording method that can suppress the occurrence of cracks when an image recorded material is folded. .
- the present disclosure includes the following aspects.
- the paper base material includes a pulp layer and a coating layer disposed on at least one surface of the pulp layer,
- the coating layer includes at least one white pigment selected from the group consisting of calcium carbonate and kaolin, and a binder, A coat layer is arranged on the A side, and the dry coating amount of the coat layer arranged on the A side is 15 g/m 2 to 50 g/m 2 ,
- An inkjet recording method in which no coat layer is disposed on the B side, or, if it is disposed, the dry coating amount
- the infrared rays are near infrared rays having a maximum wavelength in the range of 800 nm to 1,400 nm.
- the post-treatment liquid has a surface tension of 22.5 mN/m to 40.0 mN/m.
- the post-treatment liquid is applied in an amount per unit area of 10 g/m 2 to 55 g/m 2 , as described in any one of ⁇ 1> to ⁇ 3>. inkjet recording method.
- ⁇ 5> The inkjet recording method according to any one of ⁇ 1> to ⁇ 4>, wherein the surfactant includes a nonionic surfactant.
- ⁇ 6> The inkjet recording method according to any one of ⁇ 1> to ⁇ 5>, wherein the surfactant has an HLB value of 8.0 to 14.0.
- ⁇ 7> The inkjet recording method according to any one of ⁇ 1> to ⁇ 6>, wherein the paper base material has a basis weight of 180 g/m 2 to 600 g/m 2 .
- ⁇ 8> Before the step of applying the ink, a step of applying a pre-treatment liquid on the A side, The inkjet recording method according to any one of ⁇ 1> to ⁇ 7>, wherein in the step of applying ink, ink is applied onto side A to which the pretreatment liquid has been applied. ⁇ 9> The inkjet recording method according to ⁇ 8>, wherein the pretreatment liquid contains an organic acid.
- an inkjet recording method that can suppress the occurrence of cracks when an image recording material is folded.
- a numerical range indicated using “ ⁇ ” means a range that includes the numerical values listed before and after " ⁇ " as the minimum and maximum values, respectively.
- the upper limit or lower limit described in a certain numerical range may be replaced with the upper limit or lower limit of another numerical range described stepwise.
- the upper limit or lower limit described in a certain numerical range may be replaced with the value shown in the Examples.
- the amount of each component in the composition refers to the total amount of the multiple substances present in the composition. means.
- a combination of two or more preferred embodiments is a more preferred embodiment.
- the term "process" is used not only to refer to an independent process, but also to include a process that is not clearly distinguishable from other processes, as long as the intended purpose of the process is achieved. It will be done.
- image refers to films in general, and “image recording” refers to the formation of images (i.e., films). Further, the concept of "image” in this specification also includes a solid image.
- (meth)acrylate is a concept that includes both acrylate and methacrylate
- (meth)acryloyl group is a concept that includes both acryloyl group and methacryloyl group
- (meth)acryloyl group is a concept that includes both acryloyl group and methacryloyl group.
- acrylic acid is a concept that includes both acrylic acid and methacrylic acid.
- the inkjet recording method includes a step of applying ink containing a colorant and water onto side A, which is one side of a paper base material, by an inkjet recording method, and a step of applying ink containing a colorant and water to side A, which is one side of a paper base material.
- a step of irradiating infrared rays having a maximum wavelength in the range of 800 nm to 3,000 nm and a step of applying a post-treatment liquid containing water and a surfactant on the other side B of the paper base material.
- the paper base material includes a pulp layer and a coating layer disposed on at least one surface of the pulp layer, the coating layer being selected from the group consisting of calcium carbonate and kaolin.
- a coating layer containing at least one white pigment and a binder is disposed on the A side, and the dry coating amount of the coating layer disposed on the A side is 15 g/m 2 to 50 g/m 2
- the coating layer is not disposed on the B side, or if it is disposed, the dry coating amount of the coating layer disposed on the B side is 10 g/m 2 or less.
- Infrared rays have high energy density and high drying efficiency. However, if infrared rays are applied to the ink-applied side (Side A) after applying ink to the paper base material, even the water contained in the paper base material will evaporate, making the image recording material itself brittle. When the image recording material was folded, the coat layer and the lower pulp layer tended to crack. Particularly in areas on the paper base material where ink is not applied, water volatilization tends to progress. Further, when applying a plurality of inks having different hues, the degree of drying varies depending on the inks due to differences in absorption spectra of the inks.
- black ink absorbs more infrared rays, so water volatilizes more easily in areas to which black ink is applied. In areas to which no ink was applied and areas to which black ink was applied, cracks tended to occur more easily when the image recording material was folded.
- post-treatment containing water and a surfactant is applied to the surface (B side) opposite to the surface (A side) to which the ink is applied of the paper base material. Apply liquid. By permeating the post-treatment liquid into the B side of the paper base material, it is possible to suppress the occurrence of cracks when the image recording material is folded.
- JP 2020-164333A does not include any description regarding a post-treatment liquid containing water and a surfactant. In both Japanese Patent Application Laid-Open Nos. 2017-124561 and 2020-164333, bending of the image recording material is not assumed.
- the inkjet recording method includes a step of applying an ink containing a pigment and water on side A, which is one side of the paper base material, by an inkjet recording method, and a step on the other side of the paper base material.
- a step of applying a post-treatment liquid containing water and a surfactant onto the B side That is, side A of the paper base material is the side to which ink is applied.
- the B side of the paper base material is the side to which the post-treatment liquid is applied.
- the paper base material used in the inkjet recording method according to the present disclosure includes a pulp layer and a coat layer disposed on at least one surface of the pulp layer.
- the pulp layer is a layer whose main component is pulp.
- the main component refers to a component that accounts for 50% by mass or more of the components constituting the pulp layer.
- the type of pulp is not particularly limited, from the viewpoint of strength, it is preferable that the pulp layer contains chemical pulp.
- chemical pulp include hardwood kraft pulp (LKP) and softwood kraft pulp (NKP).
- the pulp may be bleached pulp or unbleached pulp.
- LKP and NKP may each be bleached pulp or unbleached pulp.
- pulps other than NKP and LKP include stone ground pulp (SGP), pressurized stone ground pulp (PGW), refiner ground pulp (RGP), thermoground pulp (TGP), and chemical ground pulp (CGP).
- Mechanical pulp such as , ground wood pulp (GP), thermomechanical pulp (TMP); used tea paper, used kraft envelope paper, used magazine paper, used newspaper paper, used leaflet paper, used office paper, used cardboard paper, white paper used paper, used Kent paper, imitation waste paper, Examples include disintegrated paper pulp (DIP) produced from waste paper such as land debentures; and pulp produced chemically or mechanically from non-wood fibers such as kenaf, hemp, and reed.
- DIP disintegrated paper pulp
- the coating layer may be arranged on both surfaces of the pulp layer, or may be arranged only on one surface of the pulp layer.
- a coat layer is disposed on the A side, and the dry coating amount of the coat layer disposed on the A side is 15 g/m 2 to 50 g/m 2 .
- No coat layer is disposed on the B side, or if it is disposed, the dry coating amount of the coat layer disposed on the B side is 10 g/m 2 or less. Therefore, when coat layers are arranged on both sides of the pulp layer, the side on which the coat layer with a large dry coating amount is arranged is side A (i.e., the side to which ink is applied).
- the side on which the coat layer with a small dry coating amount is disposed is the B side (that is, the side to which the post-treatment liquid is applied).
- the side on which the coat layer is arranged is the A side (i.e., the side to which ink is applied), and the coat layer is arranged
- the side that is not coated is the B side (that is, the side to which the post-treatment liquid is applied).
- the dry coating amount of the coating layer disposed on the B side is 10 g/m 2 or less, the post-processing liquid easily penetrates, and when the image recorded material is folded, The occurrence of cracks is suppressed.
- the dry coating weight of the coating layer disposed on the A side is preferably 15 g/m 2 to 40 g/m 2 , and 15 g/m 2 to 30 g from the viewpoint of the vividness of the finished image recording material. / More preferably, it is m2 .
- the dry coating amount of the coating layer disposed on the B side is preferably 7 g/m 2 or less, more preferably 4 g/m 2 or less, from the viewpoint of suppressing cracking when folded.
- the dry coating amount of the coating layer disposed on the B side may be 0 g/m 2 .
- the dry coating amount of the coat layer disposed on the B-side side is 0 g/m 2 , it means that the coat layer is disposed only on one side of the pulp layer.
- the coating layer includes at least one white pigment selected from the group consisting of calcium carbonate and kaolin, and a binder.
- the type of binder contained in the coating layer is not particularly limited, and examples include starch, styrene-butadiene copolymer, acrylic resin, polyvinyl acetate, and polyvinyl alcohol.
- the content of the white pigment is not particularly limited, and is, for example, 50% by mass to 95% by mass based on the total amount of the coating layer.
- the content of the binder is not particularly limited, and is, for example, 5% by mass to 50% by mass based on the total amount of the coating layer.
- the basis weight of the paper base material is not particularly limited, but is preferably from 180 g/m 2 to 600 g/m 2 , more preferably from 250 g/m 2 to 400 g/m 2 .
- the thickness of the paper base material is not particularly limited, but is preferably 150 ⁇ m to 750 ⁇ m, more preferably 200 ⁇ m to 500 ⁇ m. The thicker the paper base material, the more likely it is that cracks will occur when the image recording material is folded. According to the inkjet recording method according to the present disclosure, even if the basis weight of the paper base material is within the above range, that is, even if the thickness of the paper base material is thick, when the image recording material is folded, The occurrence of cracks is suppressed.
- Basis weight means the mass per 1 m 2 of paper base material. Basis weight is measured by the method described in JIS P8124:2011.
- Commercially available products can be used as the paper base material.
- Commercially available products include, for example, “OK Ball”, “UF Coat”, and “NEW Pigeon” manufactured by Oji Materia Co., Ltd.; “NEW Ultra H”, “Birite Card”, and “NEW” manufactured by Nippon Paper Industries Co., Ltd.
- the inkjet recording method includes a step of applying ink containing a colorant and water onto side A, which is one side of a paper base material, using an inkjet recording method (hereinafter also referred to as "ink application step"). )including.
- the ink applied in the ink application step contains water.
- the content of water is preferably 40% by mass or more, more preferably 50% by mass or more, and even more preferably 60% by mass or more, based on the total amount of ink. Further, the upper limit of the water content is not particularly limited, but is preferably 95% by mass or less, more preferably 90% by mass or less, and even more preferably 80% by mass or less.
- the ink applied in the ink application step contains at least one colorant.
- Colorants include dyes and pigments. Among these, from the viewpoint of durability such as heat resistance, light resistance, and water resistance, the colorant is preferably a pigment.
- a pigment dispersion liquid is a liquid obtained by dispersing a pigment in a liquid medium using a pigment dispersant, and includes at least a pigment, a dispersant, and a liquid medium. Details of the dispersant will be described later. Further, the liquid medium may be water or an organic solvent.
- the pigment may be an organic pigment or an inorganic pigment.
- organic pigments include azo pigments, polycyclic pigments, dye chelates, nitro pigments, nitroso pigments, and aniline black.
- the organic pigment is preferably an azo pigment or a polycyclic pigment.
- azo pigments include azo lakes, insoluble azo pigments, condensed azo pigments, and chelate azo pigments.
- polycyclic pigments include phthalocyanine pigments, perylene pigments, perinone pigments, anthraquinone pigments, quinacridone pigments, dioxazine pigments, indigo pigments, thioindigo pigments, isoindolinone pigments, and quinophthalone pigments.
- the dye chelate include basic dye-type chelates and acidic dye-type chelates.
- inorganic pigments include titanium oxide, iron oxide, calcium carbonate, barium sulfate, aluminum hydroxide, barium yellow, cadmium red, chrome yellow, and carbon black.
- pigments for example, "Encyclopedia of Pigments” edited by Seishiro Ito (published in 2000), W. Herbst, K. Examples include pigments described in “Industrial Organic Pigments” by Hunger, JP 2002-12607, JP 2002-188025, JP 2003-26978, and JP 2003-342503.
- the volume average particle diameter of the pigment is preferably 10 nm to 200 nm, more preferably 20 nm to 180 nm, and even more preferably 30 nm to 150 nm.
- the volume average particle diameter is 200 nm or less, color reproducibility becomes good and ejection performance improves when an image is recorded by an inkjet recording method. Further, when the volume average particle diameter is 10 nm or more, light resistance becomes good.
- the particle size distribution of the pigment is not particularly limited, and may be either a wide particle size distribution or a monodisperse particle size distribution. Further, two or more types of pigments having a monodisperse particle size distribution may be mixed and used.
- the volume average particle size and particle size distribution of the pigment are values measured by a particle size distribution measuring device (for example, Microtrac UPA (registered trademark) EX150 manufactured by Nikkiso Co., Ltd.).
- a particle size distribution measuring device for example, Microtrac UPA (registered trademark) EX150 manufactured by Nikkiso Co., Ltd.).
- the content of the colorant is preferably 1% by mass to 20% by mass, more preferably 1% by mass to 10% by mass, based on the total amount of ink.
- the ink applied in the ink application step contains a pigment
- the ink preferably contains a pigment dispersant in order to disperse the pigment in water.
- a pigment dispersant is a compound that has the function of dispersing pigments.
- the pigment can be dispersed in water by adsorbing the pigment dispersant onto the surface of the pigment and covering at least a portion of the surface of the pigment. Note that when a self-dispersing pigment that can be dispersed in water even in the absence of a pigment dispersant is used as a pigment, the ink does not need to contain a pigment dispersant.
- the form of the pigment dispersant contained in the ink is not particularly limited, and may be any of random polymers, block polymers, and graft polymers. Further, the pigment dispersant may be a polymer having a crosslinked structure. Among these, the pigment dispersant is preferably a polymer having a crosslinked structure. When the pigment dispersant is a polymer having a crosslinked structure, it is considered that the pigment dispersant is difficult to detach from the surface of the pigment, and the dispersion stability of the pigment is high.
- a polymer refers to a compound having a weight average molecular weight of 1000 or more.
- weight average molecular weight means a value measured by gel permeation chromatography (GPC).
- GPC gel permeation chromatography
- HLC registered trademark
- 8020GPC manufactured by Tosoh Corporation
- TSKgel registered trademark
- Super Multipore HZ-H 4 mm ID x 15 cm
- THF tetrahydrofuran
- the measurement is performed using an RI detector with a sample concentration of 0.45% by mass, a flow rate of 0.35 ml/min, a sample injection amount of 10 ⁇ l, and a measurement temperature of 40° C.
- the calibration curve is "standard sample TSK standard, polystyrene” manufactured by Tosoh Corporation: "F-40", “F-20”, “F-4", “F-1”, "A-5000”, "A- 2500'', ⁇ A-1000'', and 8 samples of ⁇ n-propylbenzene''.
- the content of the dispersant relative to the pigment content is preferably 0.5 to 3.0 on a mass basis, more preferably 1.0 to 2.0, from the viewpoint of dispersion stability. preferable.
- the ink applied in the ink application step preferably contains at least one organic solvent from the viewpoint of improving ejection properties.
- organic solvents examples include glycerin, 1,2,6-hexanetriol, trimethylolpropane, alkanediol (e.g., ethylene glycol, 1,2-propanediol), 1,3-propanediol, 1,3-butane Diol, 1,4-butanediol, 2-butene-1,4-diol, 2-ethyl-1,3-hexanediol, 2-methyl-2,4-pentanediol, 1,2-octanediol, 1, 2-hexanediol, 1,2-pentanediol, 4-methyl-1,2-pentanediol, etc.), polyalkylene glycol (e.g.
- diethylene glycol triethylene glycol, tetraethylene glycol, pentaethylene glycol, dipropylene glycol, poly polyhydric alcohols such as oxyethylene polyoxypropylene glycol, etc.
- Polyalkylene glycol ether e.g., diethylene glycol monoalkyl ether, triethylene glycol monoalkyl ether, tripropylene glycol monoalkyl ether, polyoxypropylene glyceryl ether, etc.
- Examples include alkyl alcohols having 1 to 4 carbon atoms, 2-pyrrolidone, and N-methyl-2-pyrrolidone.
- the content of the organic solvent is preferably 0.5% to 30% by mass, more preferably 1% to 20% by mass, and 1% to 15% by mass based on the total amount of the ink. It is particularly preferable that there be.
- the ink applied in the ink application step preferably contains at least one type of water-soluble resin from the viewpoint of improving ejection properties.
- water-soluble in a water-soluble resin means a property in which the amount dissolved in 100 g of water at 25° C. is 1 g or more.
- the water-soluble resin preferably contains a water-soluble resin X1 containing an alkyl group having 1 to 3 carbon atoms, an anionic group, and a cyclic structure.
- the proportion of water-soluble resin X1 in the total amount of the water-soluble resin is preferably 50% by mass to 100% by mass, and preferably 60% by mass to 100% by mass. is more preferable, and even more preferably 80% by mass to 100% by mass.
- the alkyl group having 1 to 3 carbon atoms in the water-soluble resin More preferred is a methyl group.
- the water-soluble resin X1 may contain only one type of alkyl group having 1 to 3 carbon atoms, or may contain two or more types of alkyl groups having 1 to 3 carbon atoms.
- the alkyl group having 1 to 3 carbon atoms in the water-soluble resin X1 may be introduced into the structure of the water-soluble resin X1 by polymerizing a polymerizable monomer containing an alkyl group having 1 to 3 carbon atoms. That is, the water-soluble resin X1 may include a structural unit derived from a polymerizable monomer containing an alkyl group having 1 to 3 carbon atoms.
- the polymerizable monomer containing an alkyl group having 1 to 3 carbon atoms is a (meth)acrylic acid alkyl ester in which the alkyl group in the alkyl ester structure has 1 to 3 carbon atoms [hereinafter referred to as "(meth)acrylic acid C1-3 Also referred to as “alkyl esters”] are preferred.
- the (meth)acrylic acid C1-3 alkyl ester is methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, or i-propyl (meth)acrylate. be.
- the (meth)acrylic acid C1-3 alkyl ester methyl (meth)acrylate or ethyl (meth)acrylate is preferable, and methyl (meth)acrylate is more preferable.
- methacrylic acid C1-3 alkyl ester is preferable.
- the number of (meth)acrylic acid C1-3 alkyl ester units in the water-soluble resin X1 may be one type or two or more types. It may be.
- the content of (meth)acrylic acid C1-3 alkyl ester units in the water-soluble resin X1 is preferably 3% by mass to 80% by mass, and 3% by mass to 50% by mass, based on the total amount of the water-soluble resin X1. More preferably, it is 5% by mass to 50% by mass.
- the number of anionic groups contained in the water-soluble resin X1 may be only one, or two or more.
- the water-soluble resin X1 may contain both an acid group and a salt of an acid group as anionic groups.
- Salts of acid groups are those in which the acid groups (e.g., carboxy groups, salts of sulfo groups, and salts of phosphate groups) are neutralized by a neutralizing agent. It can be formed by Neutralization of acid groups may be performed before polymerizing the polymerizable monomer containing acid groups or after polymerizing the polymerizable monomer.
- neutralizing agents for neutralizing acid groups include inorganic bases such as alkali metal hydroxides and alkaline earth metal hydroxides, and organic bases such as organic amines.
- alkali metals include potassium (K) and sodium (Na).
- alkaline earth metals include calcium (Ca) and magnesium (Mg).
- alkali metal hydroxides include potassium hydroxide and sodium hydroxide.
- alkaline earth metal hydroxides include calcium hydroxide and magnesium hydroxide.
- organic amines include ammonia, primary amines (e.g., ethylamine, monoethanolamine, etc.), secondary amines (e.g., diethylamine, ethylenediamine, etc.), tertiary amines (e.g., triethylamine, triethanolamine, isopropylethylamine, etc.). pyrrolidine, piperidine, etc.), and quaternary ammonium salts.
- the neutralizing agent is preferably an alkali metal hydroxide or an organic amine, more preferably an alkali metal hydroxide or an organic amine having a boiling point of 80° C. or higher.
- organic amines having a boiling point of 80°C or higher include ethylenediamine (117°C), triethylamine (90°C), monoethanolamine (170°C), triethanolamine (208°C), isopropylethylamine (127°C), and pyrrolidine. (87°C), and piperidine (106°C).
- the water-soluble resin X1 contains at least one of a carboxy group and a salt of a carboxy group as an anionic group.
- the ratio of the salt of the carboxy group to the total of the carboxy group and the salt of the carboxy group (mol%; hereinafter also referred to as degree of neutralization) is preferably 40 mol% or more, preferably 50 mol% or more, and 60 mol% or more. More preferably mol % or more, and even more preferably 80 mol % or more.
- the upper limit of the degree of neutralization can be 100 mol%.
- the anionic group that can be contained in the water-soluble resin X1 can be added to the structure of the water-soluble resin may be introduced. That is, the water-soluble resin X1 may include a structural unit derived from a polymerizable monomer containing an anionic group. As the polymerizable monomer containing an anionic group, (meth)acrylic acid is particularly preferred.
- water-soluble resin It is preferably 5% by mass to 40% by mass, more preferably 8% by mass to 20% by mass, based on the total amount of X1.
- the cyclic structure in the water-soluble resin X1 preferably includes at least one of an aromatic ring and an aliphatic ring, and more preferably includes an aromatic ring.
- the water-soluble resin X1 may contain only one type of cyclic structure, or may contain two or more types of cyclic structures.
- an aromatic ring means a cyclic unsaturated ring having aromatic properties.
- aromatic rings include; Examples include aromatic hydrocarbon rings such as a benzene ring, naphthalene ring, anthracene ring, and pyrene ring; and heteroaromatic rings such as a pyridine ring, pyrrole ring, furan ring, thiophene ring, imidazolyl ring, and acridone ring.
- the aromatic ring is preferably an aromatic hydrocarbon ring.
- the aromatic ring can be introduced into the structure of the water-soluble resin X1 by polymerization of a polymerizable monomer containing the aromatic ring.
- the polymerizable monomer containing an aromatic ring is preferably a polymerizable monomer containing an aromatic ring and an ethylenically unsaturated double bond, and more preferably a vinyl polymerizable monomer containing an aromatic ring.
- polymerizable monomers containing aromatic rings examples include styrene, methylstyrene, divinylbenzene, vinylpyridine, diallyl phthalate, and (meth)acrylates containing aromatic rings (e.g., benzyl acrylate, phenoxyethyl acrylate, etc.) .
- the polymerizable monomer containing an aromatic ring may be unsubstituted or may be a substituted polymerizable monomer substituted with a substituent.
- substituents include halogen atoms, alkyl groups, carboxylic acid groups, and hydroxyl groups.
- the halogen atom include a chlorine atom, a bromine atom, and an iodine atom.
- the alkyl group is preferably an alkyl group having 1 to 12 carbon atoms (preferably 1 to 8 carbon atoms), such as a methyl group, an ethyl group, a propyl group, a butyl group, and a hexyl group.
- the alkyl group may be unsubstituted or may have the same substituent as above.
- structural units derived from polymerizable monomers containing aromatic rings that may be included in the water-soluble resin X1 include specific examples of structural units derived from polymerizable monomers containing aromatic rings that may be included in the pigment dispersion resin described above. The same is true.
- the content of structural units derived from polymerizable monomers containing cyclic structures (for example, aromatic rings) in water-soluble resin X1 is preferably 50% to 85% by mass, and 60% to 80% by mass, based on the total amount of water-soluble resin Mass% is more preferred.
- Water-soluble resin X1 has a structural unit derived from (meth)acrylic acid C1-3 alkyl ester [that is, (meth)acrylic acid alkyl ester in which the alkyl group in the alkyl ester structure has 1 to 3 carbon atoms]; It is particularly preferable to include a structural unit derived from (meth)acrylic acid and a structural unit derived from a polymerizable monomer containing a cyclic structure. The preferable content of each structural unit in this embodiment is as described above.
- a structural unit derived from (meth)acrylic acid refers to a structural unit obtained by polymerization of (meth)acrylic acid (i.e., a structural unit containing a carboxy group) and a structural unit derived from (meth)acrylic acid. It includes both a structural unit obtained by polymerization and neutralization (i.e., a structural unit containing a salt of a carboxy group) (here, neutralization may be performed before or after polymerization).
- the weight average molecular weight of the water-soluble resin X1 is preferably 5,000 to 100,000. When the weight average molecular weight of the water-soluble resin X1 is within the above range, image bleeding and blocking are further suppressed. In addition, the ink ejectability is better.
- the weight average molecular weight of the water-soluble resin X1 is more preferably 10,000 to 80,000, and even more preferably 10,000 to 30,000, from the viewpoint of ink ejection properties.
- the ink applied in the ink application step preferably contains a surfactant.
- the type of surfactant is not particularly limited, and may be any of anionic surfactants, cationic surfactants, betaine surfactants, and nonionic surfactants.
- the content of the surfactant is preferably 0.1% by mass to 5% by mass, more preferably 0.5% by mass to 3% by mass, based on the total amount of the ink.
- the ink applied in the ink application process may contain wax, colloidal silica, antifoaming agent, co-sensitizer, ultraviolet absorber, antioxidant, anti-fading agent, conductive salt, basic compound, etc. as necessary. It may also contain additives.
- the surface tension of the ink applied in the ink applying step is preferably 60 mN/m or less, more preferably 20 mN/m to 50 mN/m, and even more preferably 25 mN/m to 45 mN/m. .
- the surface tension of the ink is measured at a temperature of 25° C. using a surface tension meter, for example, an automatic surface tension meter manufactured by Kyowa Kaimen Kagaku Co., Ltd. (product name “DY-300”).
- the viscosity of the ink applied in the ink applying step is preferably 1.2 mPa ⁇ s to 15.0 mPa ⁇ s, more preferably 2.0 mPa ⁇ s to 13.0 mPa ⁇ s, and 2. More preferably, it is 5 mPa ⁇ s to 10.0 mPa ⁇ s or less.
- the viscosity of the ink is measured at a temperature of 30° C. using a rotational viscometer, for example, “VISCOMETER TV-22” manufactured by Toki Sangyo Co., Ltd.
- the pH of the ink applied in the ink applying step is preferably 6.0 to 11.0, more preferably 7.0 to 10.0, from the viewpoint of storage stability of the ink. More preferably, it is 0 to 9.0.
- the pH of the ink is measured at a temperature of 25° C. using a pH meter, for example, “WM-50EG” manufactured by Toa DDK.
- Inkjet recording method The inkjet recording method is not particularly limited as long as it can record an image, and any known method can be used. Inkjet recording methods include, for example, a charge control method that uses electrostatic attraction to eject ink, a drop-on-demand method (pressure pulse method) that uses the vibration pressure of a piezo element, and a method that converts electrical signals into acoustic beams to eject ink.
- the acoustic inkjet method uses radiation pressure to eject ink by irradiating the ink with water, and the thermal inkjet method (bubble jet (registered trademark)) uses the pressure generated by heating the ink to form bubbles. .
- the inkjet heads used in the inkjet recording method include the shuttle method, which uses a short serial head and performs recording while scanning the head in the width direction of the substrate, and the shuttle method, in which recording elements are arranged to cover the entire side of the substrate.
- the shuttle method which uses a short serial head and performs recording while scanning the head in the width direction of the substrate
- the shuttle method in which recording elements are arranged to cover the entire side of the substrate.
- One example is the line method using a line head.
- a pattern can be formed on the entire surface of the substrate by scanning the substrate in a direction that intersects with the direction in which the recording elements are arranged, eliminating the need for a conveyance system such as a carriage that scans the short head.
- the line method eliminates the need for complicated scanning control between carriage movement and the base material, and only the base material moves, making it possible to achieve higher recording speeds than with the shuttle method.
- the amount of ink droplets ejected from the inkjet head is preferably 1 pL (picoliter) to 100 pL, more preferably 1 pL to 10 pL, and even more preferably 1 pL to 5 pL.
- the inkjet recording method includes a step of irradiating infrared rays having a maximum wavelength in the range of 800 nm to 3,000 nm (hereinafter also referred to as "infrared irradiation step") to side A to which ink has been applied. .
- the ink applied in the ink application step is dried.
- the maximum wavelength in infrared rays means the wavelength at which the radiant energy density is maximum.
- the maximum wavelength is calculated from the radiator temperature according to "Planck's radiation law.” For example, when the radiator is a filament, the maximum wavelength at a filament temperature of 1,200°C is 2,415 nm, and at 3,500°C is 828 nm.
- the infrared rays are preferably near infrared rays having a maximum wavelength in the range of 800 nm to 1,400 nm.
- the irradiation energy of infrared rays is not particularly limited, but from the viewpoint of drying properties, it is preferably 50 kJ/m 2 to 500 kJ/m 2 , more preferably 60 kJ/m 2 to 400 kJ/m 2 , and 70 kJ/m 2 Particularly preferred is 2 to 300 kJ/m 2 .
- the method of irradiation with infrared rays is not particularly limited, and for example, irradiation can be performed using a device such as a normal infrared lamp, a xenon flash lamp, a xenon lamp, a xenon short arc lamp, a near-infrared halogen heater, an infrared LED, an infrared laser, etc. can.
- a device such as a normal infrared lamp, a xenon flash lamp, a xenon lamp, a xenon short arc lamp, a near-infrared halogen heater, an infrared LED, an infrared laser, etc. can.
- the inkjet recording method includes a step of applying a post-treatment liquid containing water and a surfactant onto the B side, which is the other side of the paper base material (hereinafter also referred to as "post-treatment liquid application step"). including.
- the post-treatment liquid applied in the post-treatment liquid application step contains water.
- the content of water is preferably 90% by mass or more, more preferably 95% by mass or more, and even more preferably 98% by mass or more, based on the total amount of the post-treatment liquid. Further, the upper limit of the water content is not particularly limited, and is, for example, 99.95% by mass.
- the post-treatment liquid applied in the post-treatment liquid application step contains at least one type of surfactant.
- the type of surfactant is not particularly limited, and may be any of anionic surfactants, cationic surfactants, betaine surfactants, and nonionic surfactants.
- anionic surfactants include fatty acid salts, alkyl sulfate ester salts, alkylbenzene sulfonates, alkylnaphthalene sulfonates, dialkyl sulfosuccinates, alkyl phosphate ester salts, naphthalene sulfonic acid formalin condensates, and polyoxy Examples include ethylene alkyl sulfate salts.
- cationic surfactants include alkyltrimethylammonium salts, dialkyldimethylammonium salts, alkylpyridinium salts, alkyl quaternary ammonium salts, alkyldimethylbenzylammonium salts, alkylisoquinolinium salts, dialkylmorphonium salts, and Oxyethylene alkyl amines, alkyl amine salts, polyamine fatty acid derivatives, amyl alcohol fatty acid derivatives, benzalkonium chloride, and benzethonium chloride are mentioned.
- betaine surfactants include coconut alkyl dimethylamine oxide and fatty acid amidopropyl dimethylamine oxide.
- nonionic surfactants include polyoxyethylene higher alkyl ethers, polyoxyethylene higher alkyl phenyl ethers, higher fatty acid diesters of polyoxyethylene glycol, acetylene glycol surfactants, silicone surfactants, and fluorine-based surfactants. Examples include surfactants.
- the surfactant is preferably a nonionic surfactant.
- the post-processing liquid contains a nonionic surfactant, the post-processing liquid easily permeates into the B side of the paper base material, which is highly effective in suppressing the occurrence of cracks when the image recording material is folded.
- the surfactant preferably has an HLB (Hydrophile-Lipophile Balance) value of 8.0 to 14.0, more preferably 9.0 to 13.0.
- HLB Hydrophile Balance
- the weighted average value of the HLB values of each surfactant is within the above range.
- Mw is the molecular weight of the hydrophilic group
- Mo is the molecular weight of the hydrophobic group.
- the catalog value is preferentially adopted as the HLB value.
- the post-treatment liquid applied in the post-treatment liquid application step may contain additives such as co-sensitizers, ultraviolet absorbers, antioxidants, anti-fading agents, conductive salts, basic compounds, etc., as necessary. It's okay.
- the surface tension of the post-treatment liquid applied in the post-treatment liquid application step is preferably 20.0 mN/m to 45.0 mN/m, more preferably 22.5 mN/m to 40.0 mN/m. It is preferably 25.0 mN/m to 35.0 mN/m, and more preferably 25.0 mN/m to 35.0 mN/m.
- the method for measuring the surface tension of the post-treatment liquid is the same as the method for measuring the surface tension of the ink.
- the post-processing liquid When the surface tension of the post-processing liquid is within the above range, the post-processing liquid easily permeates into the B side of the paper base material, which is highly effective in suppressing the occurrence of cracks when the image recording material is folded.
- the method of applying the post-treatment liquid is not particularly limited, and examples thereof include known methods such as a coating method, a dipping method, a flexographic printing method, and an inkjet recording method.
- the amount of post-treatment liquid applied per unit area is preferably 3 g/m 2 to 70 g/m 2 , more preferably 10 g/m 2 to 55 g/m 2 .
- the applied amount is 3 g/m 2 or more, the occurrence of cracks when the image recording material is folded is further suppressed.
- the applied amount is 70 g/m 2 or less, the breaking strength of the image recording material is high, and it is possible to suppress the image recording material from being torn within the apparatus.
- the post-processing liquid is applied after the post-processing liquid application step in order to suppress the occurrence of cracks when the image recording material is folded by infiltrating the post-processing liquid into the paper base material. It is preferable not to provide a step of heating and drying.
- Pre-treatment liquid application step In the inkjet recording method according to the present disclosure, from the viewpoint of improving the scratch resistance of the image, the step of applying a pretreatment liquid on the A side before the ink application step (hereinafter also referred to as "pretreatment liquid application step") ) is preferably included.
- pretreatment liquid application step in the ink application step, ink is applied onto the A side to which the pretreatment liquid has been applied.
- the pretreatment liquid applied in the pretreatment liquid application step preferably contains a flocculant.
- the aggregating agent is not particularly limited as long as it is a component that aggregates components in the ink.
- the flocculant is preferably at least one selected from the group consisting of polyvalent metal compounds, organic acids, metal complexes, and cationic polymers, and more preferably contains an organic acid.
- polyvalent metal compounds examples include alkaline earth metals in group 2 of the periodic table (e.g., magnesium, calcium), transition metals in group 3 of the periodic table (e.g., lanthanum), and metals in group 13 of the periodic table (e.g., lanthanum). Examples include salts of aluminum) and lanthanides (eg neodymium).
- metal salts are preferably organic acid salts, nitrates, chlorides, or thiocyanates described below.
- polyvalent metal compounds include calcium salts or magnesium salts of organic acids (for example, formic acid, acetic acid, benzoic acid, etc.); calcium salts or magnesium salts of nitric acid; calcium chloride, magnesium chloride, or calcium salts of thiocyanate; Preferably it is a magnesium salt.
- the polyvalent metal compound is dissociated into a polyvalent metal ion and a counter ion in the pretreatment liquid.
- organic acids include organic compounds having an acidic group.
- acidic groups include phosphoric acid groups, phosphonic acid groups, phosphinic acid groups, sulfuric acid groups, sulfonic acid groups, sulfinic acid groups, and carboxy groups.
- the acidic group is preferably a phosphoric acid group or a carboxy group, and more preferably a carboxy group.
- At least a portion of the acidic group is dissociated in the pretreatment liquid.
- organic compounds having a carboxyl group examples include (meth)acrylic acid, poly(meth)acrylic acid, acetic acid, formic acid, benzoic acid, glycolic acid, malonic acid, malic acid (preferably DL-malic acid), maleic acid, Succinic acid, glutaric acid, pimelic acid, adipic acid, fumaric acid, citric acid, tartaric acid, phthalic acid, 4-methylphthalic acid, lactic acid, pyrrolidonecarboxylic acid, pyronecarboxylic acid, pyrrolecarboxylic acid, furancarboxylic acid, pyridinecarboxylic acid, Coumaric acid, thiophenecarboxylic acid and nicotinic acid are mentioned.
- the organic compound having a carboxy group is preferably a dicarboxylic acid or higher (hereinafter also referred to as polycarboxylic acid), and more preferably a dicarboxylic acid.
- the polyvalent carboxylic acid is preferably malonic acid, malic acid, maleic acid, succinic acid, glutaric acid, pimelic acid, adipic acid, fumaric acid, tartaric acid, 4-methylphthalic acid, or citric acid. , malonic acid, malic acid, tartaric acid, succinic acid, glutaric acid, pimelic acid, adipic acid or citric acid.
- the organic acid preferably has a low pKa (eg, 1.0 to 5.0). This reduces the surface charge of particles such as pigments and resin particles in the ink, which are stabilized by weakly acidic functional groups such as carboxyl groups, by bringing them into contact with an organic acid with a lower pKa, thereby improving dispersion stability. can be lowered.
- pKa eg, 1.0 to 5.0
- the organic acid has a low pKa, high solubility in water, and a valence of two or more. Further, it is more preferable that the organic acid has a high buffering capacity in a pH region lower than the pKa of a functional group (for example, a carboxy group, etc.) that stabilizes the dispersion of particles in the ink.
- a functional group for example, a carboxy group, etc.
- the metal complex contains at least one metal element selected from the group consisting of zirconium, aluminum, and titanium.
- the metal complex is selected from the group consisting of acetate, acetylacetonate, methylacetoacetate, ethyl acetoacetate, octylene glycolate, butoxyacetylacetonate, lactate, lactate ammonium salt, and triethanolaminate as a ligand.
- a metal complex containing at least one of the following is preferred.
- the metal complex may be a commercially available product.
- a variety of organic ligands, particularly polydentate ligands capable of forming metal chelate catalysts, are commercially available. Therefore, the metal complex may be a metal complex prepared by combining a commercially available organic ligand and a metal.
- the metal complex examples include zirconium tetraacetylacetonate (for example, "Orgatix ZC-150" manufactured by Matsumoto Fine Chemical Co., Ltd.), zirconium monoacetylacetonate (for example, “Orgatix ZC-540” manufactured by Matsumoto Fine Chemical Co., Ltd.), zirconium Bisacetylacetonate (for example, "Orgatics ZC-550” manufactured by Matsumoto Fine Chemicals), zirconium monoethylacetoacetate (for example, “Orgatics ZC-560” manufactured by Matsumoto Fine Chemicals), zirconium acetate (for example, "Orgatics ZC-560” manufactured by Matsumoto Fine Chemicals) "Orgatix ZC-115"), titanium diisopropoxy bis(acetylacetonate) (for example, "Orgatix TC-100" manufactured by Matsumoto Fine Chemical Co., Ltd.), titanium tetraacetylacetonate (for example, "Orgat
- metal complexes include titanium lactate ammonium salt (for example, “Orgatix TC-300” manufactured by Matsumoto Fine Chemical Co., Ltd.), titanium lactate (for example, “Orgatix TC-310, 315" manufactured by Matsumoto Fine Chemical Co., Ltd.), and titanium triethanolamine.
- they are esters (for example, “Orgatics TC-400” manufactured by Matsumoto Fine Chemicals), or zirconyl chloride compounds (for example, "Orgatics ZC-126" manufactured by Matsumoto Fine Chemicals).
- the pretreatment liquid may be in a form containing one or more cationic polymers as an aggregation component.
- the cationic polymer is a homopolymer of a cationic monomer having a primary to tertiary amino group or a quaternary ammonium base, or a copolymer or condensation polymer of a cationic monomer and a non-cationic monomer. It is preferable.
- the cationic polymer may be used in the form of a water-soluble polymer or water-dispersible latex particles.
- Examples of the cationic polymer include polyvinylpyridine salt, polyalkylaminoethyl acrylate, polyalkylaminoethyl methacrylate, polyvinylimidazole, polyethyleneimine, polybiguanide, polyguanide, polyallylamine, and derivatives thereof.
- the weight average molecular weight of the cationic polymer is preferably smaller from the viewpoint of the viscosity of the pretreatment liquid.
- it is preferably 1,000 to 500,000, more preferably 1,500 to 200,000, and even more preferably 2,000 to 100,000.
- a weight average molecular weight of 1000 or more is advantageous from the viewpoint of aggregation rate.
- a weight average molecular weight of 500,000 or less is advantageous in terms of ejection reliability. However, this does not apply when the pretreatment liquid is applied to the recording medium by a method other than the inkjet recording method.
- the number of flocculants contained in the pretreatment liquid may be one type, or two or more types.
- the content of the flocculant is preferably 0.1% by mass to 40% by mass, more preferably 0.1% by mass to 30% by mass, and 1% by mass to 30% by mass, based on the total amount of the pretreatment liquid. It is more preferably 20% by weight, and particularly preferably 1% to 10% by weight.
- the pretreatment liquid applied in the pretreatment liquid application step preferably contains water.
- the content of water is not particularly limited, and is, for example, 40% by mass to 70% by mass.
- the pretreatment liquid applied in the pretreatment liquid application step may contain a flocculant and other components other than water, if necessary.
- Other components that may be contained in the pretreatment liquid include organic solvents, resin particles, surfactants, solid wetting agents, colloidal silica, inorganic salts, anti-fading agents, emulsion stabilizers, penetration enhancers, ultraviolet absorbers, and preservatives.
- the pH of the pretreatment liquid is preferably 0.1 to 4.5, more preferably 0.2 to 4.0, from the viewpoint of the aggregation rate of the ink.
- the method for measuring the pH of the pretreatment liquid is the same as the method for measuring the pH of the ink.
- the viscosity of the pretreatment liquid is preferably from 0.5 mPa ⁇ s to 10 mPa ⁇ s, more preferably from 1 mPa ⁇ s to 5 mPa ⁇ s, from the viewpoint of the aggregation rate of the ink.
- the viscosity is a value measured at 25°C using a viscometer.
- the method for measuring the viscosity of the pretreatment liquid is the same as the method for measuring the viscosity of the ink.
- the surface tension of the pretreatment liquid is preferably 60 mN/m or less, more preferably 20 mN/m to 50 mN/m, and even more preferably 30 mN/m to 45 mN/m.
- the method for measuring the surface tension of the pretreatment liquid is the same as the method for measuring the surface tension of the ink.
- the method for applying the pretreatment liquid is not particularly limited, and examples thereof include known methods such as a coating method, a dipping method, and an inkjet recording method.
- Examples of the coating method include known coating methods using a bar coater, extrusion die coater, air doctor coater, blade coater, rod coater, knife coater, squeeze coater, reverse roll coater, and the like.
- the pretreatment liquid applied onto the paper base material may be heated and dried.
- means for heating and drying the pretreatment liquid include known heating means such as a heater, known blowing means such as a dryer, and means combining these.
- Methods for heating and drying the pretreatment liquid include, for example, applying heat with a heater etc. from the side opposite to the side to which the pretreatment liquid was applied to the paper base material, and applying heat to the paper base material from the side opposite to the side to which the pretreatment liquid was applied.
- a method of applying warm air or hot air to the treated surface a method of applying heat with an infrared heater from the side of the paper base material to which the pretreatment liquid has been applied, or the side opposite to the side to which the pretreatment liquid has been applied;
- One example is a method that combines multiple methods.
- the heating temperature during heat drying of the pretreatment liquid is preferably 35°C or higher, more preferably 40°C or higher.
- the upper limit of the heating temperature is not particularly limited, and is, for example, 120°C.
- the heating drying time is not particularly limited, but is preferably from 0.5 seconds to 60 seconds, more preferably from 0.5 seconds to 20 seconds, even more preferably from 0.5 seconds to 10 seconds.
- ⁇ Aqueous solution of water-soluble resin PL-1 Aqueous solution of water-soluble resin prepared by the following method ⁇ 1,2-propanediol/acetylene glycol surfactant: Product name "Olfine E1020", manufactured by Nissin Chemical Industry Co., Ltd.
- PEG6000 Product name "Polyethylene Glycol 6000”, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.
- Aqueous dispersion of ester wax Product name "Cellosol 524", manufactured by Chukyo Yushi Co., Ltd., solid content concentration 30% by mass
- Aqueous dispersion of colloidal silica Product name “Snowtex XS”, manufactured by Nissan Chemical Industries, Ltd., solid content concentration 20% by mass
- Defoaming agent Product name “BYK-024”, manufactured by BYK-Chemie Japan Co., Ltd.
- Pretreatment liquid 1 having a pH of 4.3 was obtained by mixing the components shown below and filtering the mixture using a 1 ⁇ m filter.
- ⁇ malonic acid ...10.90% by mass ⁇ Citric acid
- ⁇ Diethylene glycol monobutyl ether ...2.00% by mass
- ⁇ Potassium hydroxide ...7.30% by mass
- ⁇ Defoaming agent product name "BYK-038", manufactured by BYK-Chemie Japan Co., Ltd.
- ⁇ Acetylene glycol surfactant 1 Product name "OLFINE E1010", manufactured by Nissin Chemical Industry Co., Ltd.
- ⁇ Acetylene glycol surfactant 2 Product name “OLFINE E1020”, manufactured by Nissin Chemical Industry Co., Ltd.
- Pretreatment liquid 1 was applied to the A side of the paper base material using a coating bar so that the application amount was 1.5 g/m 2 . Two seconds after coating, warm air at a temperature of 100°C and a wind speed of 15 m/sec was applied to the coated surface for 5 seconds from a height of 10 cm to dry it. Note that in Example 29, the pretreatment liquid application step was not performed.
- Inkjet head 1,200 dpi (dots per inch) / 20 inch wide piezo full line head arranged for 4 colors
- Droplet ejection volume 1.5 pL (picoliter) of each color per pixel
- Drive frequency 60kHz (base material conveyance speed: 1,270mm/sec)
- Example 24 Infrared irradiation process Two seconds after the ink is applied on side A, use a near infrared lamp with a maximum wavelength of 830 nm to irradiate near infrared rays with an irradiation energy of 250 kJ/m 2 on side A. did. In Example 24, an infrared lamp having a maximum wavelength of 2,400 nm was used instead of the near-infrared lamp.
- Post-treatment liquid application step Three seconds after irradiation with near-infrared rays or infrared rays, a surface is coated on the B side of the paper base material using a flexo printing method so that the applied amount becomes the amount listed in Table 3. The post-processing liquid described in 3 was applied to obtain an image record. Note that in Comparative Example 1, the post-treatment liquid application step was not performed.
- a scratch test was conducted using a Gakushin type friction tester (manufactured by Yasuda Seiki Seisakusho). The image recording material was fixed on the test piece stand 30 seconds after the application of the post-treatment liquid was completed. An unused paper base material (product name: UF Coat, weight: 310 g/m 2 , manufactured by Oji Materia Co., Ltd.)) is used as the friction element, and the coating layer of the unused paper base material It was fixed so that it faced the surface being recorded. A friction element was placed on the test piece, and a load of 240 g/cm 2 was applied from above the friction element and rubbed 10 times. The image of the rubbed area was visually observed, and the scratch resistance was evaluated based on the state of scratches and peeling in the image of the rubbed area. The evaluation criteria are as follows. A value of 3 or more is at a level that poses no practical problem.
- the type and basis weight of the paper base material are listed.
- the pretreatment liquid application step it was written as “Y” if it was carried out, and "N” if it was not carried out.
- the infrared irradiation process the types of irradiation light are described.
- the post-treatment liquid application step the type, application amount, and surface tension of the post-treatment liquid, as well as the classification, HLB value, and content of the surfactant contained in the post-treatment liquid are described. Note that in Comparative Example 1, the post-treatment liquid application step was not performed, so “-” was written in the column for the post-treatment liquid application step. In Comparative Example 2, since water was used as the post-treatment liquid in the post-treatment liquid application step, "-” was written in the column regarding the surfactant contained in the post-treatment liquid.
- Examples 1 to 29 include a step of applying ink containing a colorant and water on side A of a paper base material using an inkjet recording method, and A step of irradiating the surface with infrared rays having a maximum wavelength in the range of 800 nm to 3,000 nm, and a step of applying a post-treatment liquid containing water and a surfactant onto the B side of the paper base material.
- the paper base material includes a pulp layer and a coat layer disposed on at least one surface of the pulp layer, and the coat layer includes at least one member selected from the group consisting of calcium carbonate and kaolin.
- a coating layer is arranged on the A side, and the dry coating amount of the coating layer arranged on the A side is 15 g/m 2 to 50 g/m 2 , Since no coating layer was disposed on the B side, it was possible to suppress the occurrence of cracks when the image recording material was folded.
- Comparative Example 1 it was found that cracks occurred when the image recording material was folded because the post-treatment liquid application step was not performed.
- Comparative Example 3 since a double-sided coated paper with a dry coating amount of more than 10 g/m 2 of the coat layer was used as the paper base material, it was found that cracks occurred when the image recording material was folded.
- Example 1 since near-infrared rays were irradiated in the infrared irradiation step, it was found that the scratch resistance of the image was excellent compared to Example 24.
- Example 1 since the surface tension of the post-treatment liquid was 22.5 mN/m or more, it was found that compared to Example 14, it was more effective in suppressing the occurrence of cracks when the image recording material was folded. Ta. In Example 1, since the surface tension of the post-treatment liquid was 40.0 mN/m or less, it was found that compared to Example 5, it was more effective in suppressing the occurrence of cracks when the image recording material was folded. Ta.
- Example 1 the amount of post-treatment liquid applied per unit area was 10 g/m2 or more, so compared to Example 15, it was more effective in suppressing the occurrence of cracks when the image recording material was folded. I understand. In Example 1, since the amount of post-treatment liquid applied per unit area was 55 g/m 2 or less, it was found that the strength of the image recording material was excellent compared to Example 20.
- Example 1 since the surfactant contained a nonionic surfactant, it was found that the effect of suppressing the occurrence of cracks when the image recording material was folded was higher than that in Examples 21 to 23. Ta.
- Example 8 to 11 since the HLB value of the surfactant is 8.0 or more, the effect of suppressing the occurrence of cracks when the image recording material is folded is higher than in Example 7. I understand. In Examples 8 to 11, since the HLB value of the surfactant is 14.0 or more, the effect of suppressing the occurrence of cracks when the image recording material is folded is higher than in Example 12. I understand.
- Example 1 since the pretreatment liquid application step was performed, it was found that the scratch resistance of the image was excellent compared to Example 29.
- Pretreatment liquid 2 with a pH of 7.1 was obtained by mixing the components shown below and filtering the mixture using a 1 ⁇ m filter.
- ⁇ Calcium formate ...4.90% by mass
- ⁇ Calcium lactate pentahydrate ...3.80% by mass
- ⁇ Olfine E1010...0.20% by mass ⁇ BYK-024...0.01% by mass ⁇ Ion exchange water ...91.09% by mass
- Pretreatment liquid 3 having a pH of 7.4 was obtained by mixing the components shown below and filtering the mixture using a 1 ⁇ m filter.
- ⁇ Calcium formate ...10.10% by mass
- ⁇ Calcium lactate pentahydrate ...8.10% by mass
- ⁇ Olfine E1010...0.20% by mass ⁇ BYK-024...0.01% by mass ⁇ Ion exchange water ...81.59% by mass
- Example 31 Image recordings were obtained in the same manner as in Example 1, except that Pretreatment Liquid 1 was changed to Pretreatment Liquid 2 and Pretreatment Liquid 3, respectively. Evaluation was performed in the same manner as in Example 1. The evaluation results are shown in Table 4.
- Example 3 Similarly to Example 1, in Examples 30 and 31, it was possible to suppress the occurrence of cracks when the image recording material was folded.
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Abstract
Description
紙基材の一方の面であるA面上に、インクジェット記録方式にて、着色剤及び水を含むインクを付与する工程と、
インクが付与されたA面に対して、800nm~3,000nmの範囲に極大波長を有する赤外線を照射する工程と、
紙基材の他方の面であるB面上に、水及び界面活性剤を含む後処理液を付与する工程と、をこの順に含み、
紙基材は、パルプ層と、パルプ層の少なくとも一方の面上に配置されたコート層と、を含み、
コート層は、炭酸カルシウム及びカオリンからなる群より選択される少なくとも1種の白色顔料と、バインダーと、を含み、
A面側にコート層が配置され、A面側に配置されているコート層の乾燥塗工量が、15g/m2~50g/m2であり、
B面側にはコート層が配置されないか、又は、配置される場合には、B面側に配置されているコート層の乾燥塗工量が、10g/m2以下である、インクジェット記録方法。
<2>
赤外線は、800nm~1,400nmの範囲に極大波長を有する近赤外線である、<1>に記載のインクジェット記録方法。
<3>
後処理液は、表面張力が22.5mN/m~40.0mN/mである、<1>又は<2>に記載のインクジェット記録方法。
<4>
後処理液を付与する工程では、後処理液を、単位面積当たりの付与量を10g/m2~55g/m2の範囲として付与する、<1>~<3>のいずれか1つに記載のインクジェット記録方法。
<5>
界面活性剤は、ノニオン系界面活性剤を含む、<1>~<4>のいずれか1つに記載のインクジェット記録方法。
<6>
界面活性剤は、HLB値が8.0~14.0である、<1>~<5>のいずれか1つに記載のインクジェット記録方法。
<7>
紙基材は、坪量が180g/m2~600g/m2である、<1>~<6>のいずれか1つに記載のインクジェット記録方法。
<8>
インクを付与する工程の前に、A面上に、前処理液を付与する工程を含み、
インクを付与する工程では、前処理液が付与されたA面上に、インクを付与する、<1>~<7>のいずれか1つに記載のインクジェット記録方法。
<9>
前処理液は、有機酸を含む、<8>に記載のインクジェット記録方法。
本明細書に段階的に記載されている数値範囲において、ある数値範囲で記載された上限値又は下限値は、他の段階的な記載の数値範囲の上限値又は下限値に置き換えてもよい。また、本明細書に記載されている数値範囲において、ある数値範囲で記載された上限値又は下限値は、実施例に示されている値に置き換えてもよい。
本明細書において、2以上の好ましい態様の組み合わせは、より好ましい態様である。
本明細書において、「工程」という語は、独立した工程だけでなく、他の工程と明確に区別できない場合であっても、その工程の所期の目的が達成されれば、本用語に含まれる。
本開示に係るインクジェット記録方法は、紙基材の一方の面であるA面上に、インクジェット記録方式にて、着色剤及び水を含むインクを付与する工程と、インクが付与されたA面に対して、800nm~3,000nmの範囲に極大波長を有する赤外線を照射する工程と、紙基材の他方の面であるB面上に、水及び界面活性剤を含む後処理液を付与する工程と、をこの順に含み、紙基材は、パルプ層と、パルプ層の少なくとも一方の面上に配置されたコート層と、を含み、コート層は、炭酸カルシウム及びカオリンからなる群より選択される少なくとも1種の白色顔料と、バインダーと、を含み、A面側にコート層が配置され、A面側に配置されているコート層の乾燥塗工量が、15g/m2~50g/m2であり、B面側にはコート層が配置されないか、又は、配置される場合には、B面側に配置されているコート層の乾燥塗工量が、10g/m2以下である。
本開示に係るインクジェット記録方法は、紙基材の一方の面であるA面上に、インクジェット記録方法にて、顔料及び水を含むインクを付与する工程と、紙基材の他方の面であるB面上に、水及び界面活性剤を含む後処理液を付与する工程と、を含む。すなわち、紙基材のA面は、インクが付与される面である。紙基材のB面は、後処理液が付与される面である。
パルプは晒パルプであってもよく、未晒パルプであってもよい。LKP及びNKPはそれぞれ、晒パルプであってもよく、未晒パルプであってもよい。
m2であることがより好ましい。
本開示に係るインクジェット記録方法は、紙基材の一方の面であるA面上に、インクジェット記録方式にて、着色剤及び水を含むインクを付与する工程(以下、「インク付与工程」ともいう)を含む。
インク付与工程で付与されるインクは、水を含む。
アゾ顔料としては、例えば、アゾレーキ、不溶性アゾ顔料、縮合アゾ顔料、及びキレートアゾ顔料が挙げられる。
多環式顔料としては、例えば、フタロシアニン顔料、ぺリレン顔料、ぺリノン顔料、アントラキノン顔料、キナクリドン顔料、ジオキサジン顔料、インジゴ顔料、チオインジゴ顔料、イソインドリノン顔料、及びキノフタロン顔料が挙げられる。
染料キレートとしては、例えば、塩基性染料型キレート、及び酸性染料型キレートが挙げられる。
ポリアルキレングリコールエーテル(例えば、ジエチレングリコールモノアルキルエーテル、トリエチレングリコールモノアルキルエーテル、トリプロピレングリコールモノアルキルエーテル、ポリオキシプロピレングリセリルエーテル等);
炭素原子数1~4のアルキルアルコール、2-ピロリドン、及びN-メチル-2-ピロリドンが挙げられる。
水溶性樹脂X1は、炭素数1~3のアルキル基を1種のみ含んでいてもよいし2種以上含んでいてもよい。
即ち、水溶性樹脂X1は、炭素数1~3のアルキル基を含む重合性モノマー由来の構造単位を含んでもよい。
(メタ)アクリル酸C1-3アルキルエステルとしては、(メタ)アクリル酸メチル又は(メタ)アクリル酸エチルが好ましく、(メタ)アクリル酸メチルがより好ましい。
また、(メタ)アクリル酸C1-3アルキルエステルとしては、メタクリル酸C1-3アルキルエステルが好ましい。
水溶性樹脂X1における(メタ)アクリル酸C1-3アルキルエステル単位の含有量は、水溶性樹脂X1の全量に対し、3質量%~80質量%であることが好ましく、3質量%~50質量%であることがより好ましく、5質量%~50質量%であることが更に好ましい。
水溶性樹脂X1におけるアニオン性基としては、酸基(例えば、カルボキシ基、スルホ基、リン酸基等)、及び、酸基の塩(例えば、カルボキシ基の塩、スルホ基の塩、リン酸基の塩)が挙げられる。
水溶性樹脂X1に含まれるアニオン性基は、1種のみであってもよいし、2種以上であってもよい。
水溶性樹脂X1は、アニオン性基として、酸基と酸基の塩とを両方含んでいてもよい。
酸基の中和は、酸基を含む重合性モノマーを重合させる前に行ってもよいし、上記重合性モノマーを重合させた後に行ってもよい。
酸基を中和するための中和剤としては、アルカリ金属の水酸化物、アルカリ土類金属の水酸化物等の無機塩基、及び、有機アミン等の有機塩基が挙げられる。
アルカリ金属としては、例えば、カリウム(K)、及びナトリウム(Na)が挙げられる。
アルカリ土類金属としては、例えば、カルシウム(Ca)及びマグネシウム(Mg)が挙げられる。
アルカリ金属の水酸化物としては、例えば、水酸化カリウム及び水酸化ナトリウムが挙げられる。
アルカリ土類金属の水酸化物としては、水酸化カルシウム及び水酸化マグネシウムが挙げられる。
有機アミンとしては、例えば、アンモニア、1級アミン(例えば、エチルアミン、モノエタノールアミン等)、2級アミン(例えば、ジエチルアミン、エチレンジアミン等)、3級アミン(例えば、トリエチルアミン、トリエタノールアミン、イソプロピルエチルアミン、ピロリジン、ピペリジン等)、4級アンモニウム塩が挙げられる。中でも、有機アミンとしては、保存安定性の観点から、沸点が80℃以上である有機アミンが好ましい。
保存安定性の観点から、中和剤としては、アルカリ金属の水酸化物又は有機アミンが好ましく、アルカリ金属の水酸化物又は沸点が80℃以上である有機アミンがより好ましい。
沸点が80℃以上である有機アミンとしては、例えば、エチレンジアミン(117℃)、トリエチルアミン(90℃)、モノエタノールアミン(170℃)、トリエタノールアミン(208℃)、イソプロピルエチルアミン(127℃)、ピロリジン(87℃)、及びピペリジン(106℃)が挙げられる。
この場合、カルボキシ基及びカルボキシ基の塩の合計に対するカルボキシ基の塩の割合(モル%;以下、中和度ともいう)は、好ましくは40モル%以上であり、50モル%以上が好ましく、60モル%以上がより好ましく、80モル%以上が更に好ましい。
また、中和度の上限は、100モル%とすることができる。
即ち、水溶性樹脂X1は、アニオン性基を含む重合性モノマー由来の構造単位を含んでもよい。
アニオン性基を含む重合性モノマーとしては、(メタ)アクリル酸が特に好ましい。
水溶性樹脂X1は、環状構造を1種のみ含んでいてもよいし2種以上含んでいてもよい。
芳香環としては、例えば;
ベンゼン環、ナフタレン環、アントラセン環、ピレン環等の芳香族炭化水素環;及び
ピリジン環、ピロール環、フラン環、チオフェン環、イミダゾリル環、アクリドン環等の複素芳香族環が挙げられる。
中でも、芳香環は、芳香族炭化水素環であることが好ましい。
芳香環を含む重合性モノマーとしては、芳香環及びエチレン性不飽和二重結合を含む重合性モノマーが好ましく、芳香環を含むビニル重合性モノマーがより好ましい。
芳香環を含む重合性モノマーの例としては、スチレン、メチルスチレン、ジビニルベンゼン、ビニルピリジン、ジアリルフタレート、及び、芳香環を含む(メタ)アクリレート(例えば、ベンジルアクリレート、フェノキシエチルアクリレート等)が挙げられる。
ハロゲン原子としては、塩素原子、臭素原子、及びヨウ素原子が挙げられる。
アルキル基としては、炭素数1~12(好ましくは炭素数1~8)のアルキル基が好ましく、例えば、メチル基、エチル基、プロピル基、ブチル基、及びヘキシル基が挙げられる。アルキル基は、無置換でもよいし、上記と同様の置換基を有していてもよい。
この態様における各構造単位の好ましい含有量は、それぞれ、前述したとおりである。
上記態様において、「(メタ)アクリル酸に由来する構造単位」の概念は、(メタ)アクリル酸の重合によって得られる構造単位(即ち、カルボキシ基を含む構造単位)と、(メタ)アクリル酸の重合及び中和によって得られる構造単位(即ち、カルボキシ基の塩を含む構造単位)(ここで、中和は、重合前に行っても重合後に行ってもよい)と、の両方を包含する。
水溶性樹脂X1の重量平均分子量としては、インクの吐出性の点で、10,000~80,000がより好ましく、10,000~30,000がさらに好ましい。
インクジェット記録方式は、画像を記録し得る方式であれば特に限定されず、公知の方式を用いることができる。インクジェット記録方式としては、例えば、静電誘引力を利用してインクを吐出させる電荷制御方式、ピエゾ素子の振動圧力を利用するドロップオンデマンド方式(圧力パルス方式)、電気信号を音響ビームに変えインクに照射して放射圧を利用してインクを吐出させる音響インクジェット方式、及び、インクを加熱して気泡を形成し、生じた圧力を利用するサーマルインクジェット(バブルジェット(登録商標))方式が挙げられる。
本開示に係るインクジェット記録方法は、インクが付与されたA面に対して、800nm~3,000nmの範囲に極大波長を有する赤外線を照射する工程(以下、「赤外線照射工程」ともいう)を含む。
本開示に係るインクジェット記録方法は、紙基材の他方の面であるB面上に、水及び界面活性剤を含む後処理液を付与する工程(以下、「後処理液付与工程」ともいう)を含む。
た、水の含有量の上限値は特に限定されず、例えば、99.95質量%である。
HLB=7+11.7log(Mw/Mo)
ここで、Mwは親水基の分子量、Moは疎水基の分子量である。
本開示において、HLB値は、カタログ値が確認できる場合には、カタログ値を優先して採用する。
本開示に係るインクジェット記録方法では、画像の耐擦過性を向上させる観点から、インク付与工程の前に、A面上に、前処理液を付与する工程(以下、「前処理液付与工程」ともいう)を含むことが好ましい。前処理液付与工程を含む場合、インク付与工程では、前処理液が付与されたA面上に、インクを付与する。
多価金属化合物としては、周期表の第2族のアルカリ土類金属(例えば、マグネシウム、カルシウム)、周期表の第3族の遷移金属(例えば、ランタン)、周期表の第13族の金属(例えば、アルミニウム)及びランタニド類(例えば、ネオジム)の塩が挙げられる。
有機酸としては、酸性基を有する有機化合物が挙げられる。
金属錯体は、金属元素として、ジルコニウム、アルミニウム、及びチタンからなる群より選択される少なくとも1種を含むことが好ましい。
「オルガチックスZC-550」)、ジルコニウムモノエチルアセトアセテート(例えば、マツモトファインケミカル社製「オルガチックスZC-560」)、ジルコニウムアセテート(例えば、マツモトファインケミカル社製「オルガチックスZC-115」)、チタンジイソプロポキシビス(アセチルアセトネート)(例えば、マツモトファインケミカル社製「オルガチックス TC-100」)、チタンテトラアセチルアセトネート(例えば、マツモトファインケミカル社製「オルガチックス TC-401」)、チタンジオクチロキシビス(オクチレングリコレート)(例えば、マツモトファインケミカル社製「オルガチックス TC-200」)、チタンジイソプロポキシビス(エチルアセトアセテート(例えば、マツモトファインケミカル社製「オルガチックス TC-750」)、ジルコニウムテトラアセチルアセトネート(例えば、マツモトファインケミカル社製「オルガチックス ZC-700」)、ジルコニウムトリブトキシモノアセチルアセトネート(例えば、マツモトファインケミカル社製「オルガチックス ZC-540」)、ジルコニウムモノブトキシアセチルアセトネート ビス(エチルアセトアセテート)(例えば、マツモトファインケミカル社製「オルガチックス ZC-570」))、ジルコニウムジブトキシ ビス(エチルアセトアセテート)(例えば、マツモトファインケミカル社製「オルガチックス ZC-580」)、アルミニウムトリスアセチルアセトネート(例えば、マツモトファインケミカル社製「オルガチックス AL-80」)、チタンラクテートアンモニウム塩(例えば、マツモトファインケミカル社製「オルガチックス TC-300」)、チタンラクテート(例えば、マツモトファインケミカル社製「オルガチックス TC-310、315」)、チタントリエタノールアミネート(マツモトファインケミカル社製「オルガチックス TC-400」)、及び塩化ジルコニル化合物(例えば、マツモトファインケミカル社製「オルガチックス ZC-126」)が挙げられる。
また、前処理液は、凝集成分として1種又は2種以上のカチオン性ポリマーを含む形態であってもよい。カチオン性ポリマーは、第一級~第三級アミノ基、又は第四級アンモニウム塩基を有するカチオン性モノマーの単独重合体、カチオン性モノマーと非カチオン性モノマーとの共重合体又は縮重合体であることが好ましい。カチオン性ポリマーとしては、水溶性ポリマー又は水分散性ラテックス粒子のいずれの形態で用いてもよい。
カチオン性ポリマーとしては、例えば、ポリビニルピリジン塩、ポリアルキルアミノエチルアクリレート、ポリアルキルアミノエチルメタクリレート、ポリビニルイミダゾール、ポリエチレンイミン、ポリビグアニド、ポリグアニド、ポリアリルアミン及びこれらの誘導体が挙げられる。
表1に記載の各成分を、表1に記載の含有量(質量%)となるよう混合した。その後、1μmフィルターを用いて粗大粒子を除去し、シアンインクC1、マゼンタインクM1、イエローインクY1、及びブラックインクK1を得た。各インクにおける顔料平均粒子径、pH、粘度、表面張力、及び電気伝導度を表1に示す。
・マゼンタ顔料分散液:製品名「Pro-jet Magenta APD1000」、FUJIFILM Imaging Colorants社製、顔料濃度14.0質量%
・イエロー顔料分散液:製品名「Pro-jet Yellow TP APD1000」、FUJIFILM Imaging Colorants社製、顔料濃度15.4質量%
・ブラック顔料分散液:製品名「Pro-jet Black APD1000)」、FUJIFILM Imaging Colorants社製、顔料濃度14.0質量%
・1,2-プロパンジオール
・アセチレングリコール系界面活性剤:製品名「オルフィンE1020」、日信化学工業社製
・PEG6000:製品名「ポリエチレングリコール6000」、富士フイルム和光純薬社製
・エステルワックスの水分散液:製品名「セロゾール524」、中京油脂社製、固形分濃度30質量%
・コロイダルシリカの水分散液:製品名「スノーテックスXS」、日産化学工業社製、固形分濃度20質量%
・消泡剤:製品名「BYK-024」、ビックケミー・ジャパン社製
攪拌機、温度計、還流冷却管、及び窒素ガス導入管を備えた500ミリリットル三口フラスコに、1,2-プロパンジオール(35g)を仕込んで、窒素気流下で90℃まで昇温した。ここに、重合開始剤であるジメチル-2,2’-アゾビス(2-メチルプロピオネート)(製品名「V-601」、富士フイルム和光純薬株式会社製)5.55g、メタクリル酸(MAA)10.7g、メチルメタクリレート(MMA)69.3g、イソボルニルメタクリレート(IBOMA)20.0g、ドデシルメルカプタン1.63g、及び1,2-プロパンジオール65.00gを混合した混合溶液を、等速で2時間かけて滴下した。混合溶液の滴下完了後、1時間攪拌した。続いて、得られた反応混合物に、V-601を1.85gと、1,2-プロパンジオール24.62gとを混合した混合溶液を加え、さらに1.5時間攪拌した。得られた反応混合物に、1,2-プロパンジオール120.21gを添加した後、50質量%水酸化ナトリウム水溶液8.56gを滴下ロートで滴下し、水溶性樹脂PL-1の水溶液(固形分濃度30質量%)を得た。
水溶性樹脂PL-1〔MAA/MMA/IBOMA〕は、酸価が60mgKOH/gであり、重量平均分子量(Mw)が15,000であった。
以下に示す各成分を混合し、1μmフィルターを用いてろ過することにより、pH4.3の前処理液1を得た。
・マロン酸 … 10.90質量%
・クエン酸 … 13.40質量%
・ジエチレングリコールモノブチルエーテル … 2.00質量%
・水酸化カリウム … 7.30質量%
・消泡剤(製品名「BYK-038」、ビックケミー・ジャパン社製) … 0.05質量%
・重量平均分子量25,000のポリアクリル酸(製品名「ポリアクリル酸25,000
」、富士フイルム和光純薬社製) … 0.95質量%
・イオン交換水 … 65.40質量%
表2に記載の界面活性剤及び水を、表2に記載の含有量(質量%)となるよう混合した。その後、1μmフィルターを用いてろ過し、後処理液PT-1~PT-17を得た。界面活性剤の種類、分類、及びHLB値を表2に示す。
・アセチレングリコール系界面活性剤2:製品名「オルフィンE1020」、日信化学工業社製
・ポリオキシエチレンラウリルエーテル1:製品名「エマルゲン102KG」、花王社製
・ポリオキシエチレンラウリルエーテル2:製品名「エマルゲン103」、花王社製
・ポリオキシエチレンラウリルエーテル3:製品名「エマルゲン105」、花王社製
・ポリオキシエチレンラウリルエーテル4:製品名「エマルゲン108」、花王社製
・ポリオキシエチレンラウリルエーテル5:製品名「エマルゲン109P」、花王社製
・ポリオキシエチレンラウリルエーテル6:製品名「エマルゲン120」、花王社製
・ポリオキシエチレンラウリルエーテル7:製品名「エマルゲン150」、花王社製
・シリコーン系界面活性剤:製品名「BYK-347」、ビックケミー・ジャパン社製
・アルキルベンゼンスルホン酸:製品名「パイオニンA-40」、竹本油脂社製
・ラウリルトリメチルアンモニウムクロリド:製品名「パイオニンB-111」、竹本油脂社製
・脂肪酸アミドプロピルジメチルアミンオキシド:製品名「パイオニンC-151」、竹本油脂社製
実施例1~実施例29、比較例1~2では、紙基材として、片面コート紙(製品名「UFコート」、王子マテリア社製)を用いた。各実施例で用いた紙基材の坪量は、表3に記載のとおりである。紙基材において、コート層が配置されている側の面を「A面」、コート層が配置されていな側の面を「B面」とした。A面側に配置されているコート層の乾燥塗工量は、約18g/m2であった。
比較例3では、紙基材として、両面コート紙(製品名「ボンアイボリー+」、王子マテリア社製、坪量:310g/m2)を用いた。両面に配置されているコート層の乾燥塗工量はいずれも、約18g/m2であった。
紙基材のA面に、付与量が1.5g/m2となるように塗布バーを用いて前処理液1を付与した。塗工してから2秒後に、温度100℃、風速15m/秒の温風を10cmの高さから塗工面に5秒間当てて、乾燥させた。なお、実施例29では、前処理液付与工程を
行わなかった。
前処理液を乾燥してから3秒後に、紙基材の前処理液1が塗工された面(A面)上に、ブラックインクK1、シアンインクC1、マゼンタインクM1、イエローインクY1を、この順に、下記の条件でシングルパス方式にて吐出し、画像を記録した。
インクジェットヘッド:1,200dpi(dot per inch)/20inch幅のピエゾフルラインヘッドが4色分配置されたヘッド
打滴量:1ピクセル当たり各色1.5pL(ピコリットル)
駆動周波数:60kHz(基材搬送速度:1,270mm/秒)
A面上にインクが付与されてから2秒後に、極大波長が830nmである近赤外線ランプを用い、A面に対して、250kJ/m2の照射エネルギーで近赤外線を照射した。
なお、実施例24では、近赤外線ランプの代わりに、極大波長が2,400nmである赤外線ランプを用いた。
近赤外線又は赤外線を照射してから3秒後に、紙基材のB面に、付与量が表3に記載の量となるように、フレキソ印刷法にて、表3に記載の後処理液を付与し、画像記録物を得た。なお、比較例1では、後処理液付与工程を行わなかった。
得られた画像記録物を用いて、耐擦過性、耐折性、及び強度の評価を行った。評価方法は、以下のとおりである。評価結果を表3に示す。
学振形摩擦試験機(安田精機製作所製)を用いて、擦過試験を行った。
試験片台に、後処理液の付与が終了してから30秒後の画像記録物を固定した。
摩擦子に、未使用の紙基材(製品名:UFコート、米坪:310g/m2、王子マテリア社製))を、未使用の紙基材のコート層が、画像記録物の画像が記録されている面と対向するように、固定した。
摩擦子を、試験片の上に置き、摩擦子の上から、240g/cm2の荷重をかけて、10回擦った。擦られた部分の画像を目視で観察し、擦られた部分の画像における傷及び剥がれの状態に基づいて、耐擦過性を評価した。評価基準は、以下のとおりである。3以上は、実用上問題ないレベルである。
4:擦られた部分の画像に、傷が僅かに認められた。
3:擦られた部分の画像が僅かに剥がれ、極細い傷が認められた。
2:擦られた部分の画像が剥がれ、傷が目立っていた。
1:擦られた部分の画像が剥がれ、紙基材の一部が露出していた。
後処理液の付与が終了してから30秒後に、画像が記録されている面が外側となるように、画像記録物を180°折り曲げた。画像記録物を元の状態に戻した後、折り曲げられた部分を目視で観察し、割れの状態に基づいて、耐折性を評価した。評価基準は、以下のとおりである。3以上は、実用上問題ないレベルである。
5:折り曲げられた部分には、割れが認められなかった。
4:折り曲げられた部分に、割れが僅かに認められた。
3:折り曲げられた部分に、割れが少し認められた。
2:折り曲げられた部分において、割れが目立っていた。
1:折り曲げられた部分が、完全に割れていた。
後処理液の付与が終了してから10分後に、テンシロン万能材料試験機(製品名「FTF-1250」、オリエンテック社製)を用いて、22℃、相対湿度60%の環境下で、画像記録物の破断強度を測定した。
また、画像記録前の紙基材の破断強度を、同様の方法で、測定した。
下記式に基づいて、強度を算出した。
強度(%)=(画像記録物の破断強度/紙基材の破断強度)×100
なお、強度が50%未満であると、装置内で、画像記録物が破れる等の問題が生じる場合がある。
して、画像の耐擦過性に優れることが分かった。
実施例1では、後処理液の表面張力が40.0mN/m以下であるため、実施例5と比較して、画像記録物を折り曲げた際の割れの発生を抑制する効果が高いことが分かった。
実施例1では、後処理液の単位面積当たりの付与量を55g/m2以下としたため、実施例20と比較して、画像記録物の強度に優れることが分かった。
実施例8~実施例11では、界面活性剤のHLB値が14.0以上であるため、実施例12と比較して、画像記録物を折り曲げた際の割れの発生を抑制する効果が高いことが分かった。
以下に示す各成分を混合し、1μmフィルターを用いてろ過することにより、pH7.1の前処理液2を得た。
・ギ酸カルシウム … 4.90質量%
・乳酸カルシウム五水和物 … 3.80質量%
・オルフィンE1010 … 0.20質量%
・BYK-024 … 0.01質量%
・イオン交換水 … 91.09質量%
以下に示す各成分を混合し、1μmフィルターを用いてろ過することにより、pH7.4の前処理液3を得た。
・ギ酸カルシウム … 10.10質量%
・乳酸カルシウム五水和物 … 8.10質量%
・オルフィンE1010 … 0.20質量%
・BYK-024 … 0.01質量%
・イオン交換水 … 81.59質量%
前処理液1を、前処理液2及び前処理液3にそれぞれ変更したこと以外は、実施例1と同様の方法で、画像記録物を得た。実施例1と同様の方法で、評価を行った。評価結果を表4に示す。
Claims (9)
- 紙基材の一方の面であるA面上に、インクジェット記録方式にて、着色剤及び水を含むインクを付与する工程と、
前記インクが付与されたA面に対して、800nm~3,000nmの範囲に極大波長を有する赤外線を照射する工程と、
前記紙基材の他方の面であるB面上に、水及び界面活性剤を含む後処理液を付与する工程と、をこの順に含み、
前記紙基材は、パルプ層と、前記パルプ層の少なくとも一方の面上に配置されたコート層と、を含み、
前記コート層は、炭酸カルシウム及びカオリンからなる群より選択される少なくとも1種の白色顔料と、バインダーと、を含み、
前記A面側に前記コート層が配置され、前記A面側に配置されている前記コート層の乾燥塗工量が、15g/m2~50g/m2であり、
前記B面側には前記コート層が配置されないか、又は、配置される場合には、前記B面側に配置されている前記コート層の乾燥塗工量が、10g/m2以下である、インクジェット記録方法。 - 前記赤外線は、800nm~1,400nmの範囲に極大波長を有する近赤外線である、請求項1に記載のインクジェット記録方法。
- 前記後処理液は、表面張力が22.5mN/m~40.0mN/mである、請求項1又は請求項2に記載のインクジェット記録方法。
- 前記後処理液を付与する工程では、前記後処理液を、単位面積当たりの付与量を10g/m2~55g/m2の範囲として付与する、請求項1~請求項3のいずれか1項に記載のインクジェット記録方法。
- 前記界面活性剤は、ノニオン系界面活性剤を含む、請求項1~請求項4のいずれか1項に記載のインクジェット記録方法。
- 前記界面活性剤は、HLB値が8.0~14.0である、請求項1~請求項5のいずれか1項に記載のインクジェット記録方法。
- 前記紙基材は、坪量が180g/m2~600g/m2である、請求項1~請求項6のいずれか1項に記載のインクジェット記録方法。
- 前記インクを付与する工程の前に、前記A面上に、前処理液を付与する工程を含み、
前記インクを付与する工程では、前記前処理液が付与されたA面上に、前記インクを付与する、請求項1~請求項7のいずれか1項に記載のインクジェット記録方法。 - 前記前処理液は、有機酸を含む、請求項8に記載のインクジェット記録方法。
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