Classifications

• • 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
  • B41J2/21—Ink jet for multi-colour printing
  • B41J2/2107—Ink jet for multi-colour printing characterised by the ink properties
  • B41J2/2114—Ejecting specialized liquids, e.g. transparent or processing liquids
  • B41J2/2117—Ejecting white liquids
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
  • B41J—TYPEWRITERS; SELECTIVE PRINTING MECHANISMS, i.e. MECHANISMS PRINTING OTHERWISE THAN FROM A FORME; CORRECTION OF TYPOGRAPHICAL ERRORS
  • B41J11/00—Devices or arrangements  of selective printing mechanisms, e.g. ink-jet printers or thermal printers, for supporting or handling copy material in sheet or web form
  • B41J11/0015—Devices or arrangements  of selective printing mechanisms, e.g. ink-jet printers or thermal printers, for supporting or handling copy material in sheet or web form for treating before, during or after printing or for uniform coating or laminating the copy material before or after printing
• • 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
  • B41J2/21—Ink jet for multi-colour printing
  • B41J2/2107—Ink jet for multi-colour printing characterised by the ink properties
  • B41J2/2114—Ejecting specialized liquids, e.g. transparent or processing liquids
• • 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
  • 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
  • B41M5/0041—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
  • B41M7/0027—After-treatment of prints, e.g. heating, irradiating, setting of the ink, protection of the printed stock using protective coatings or layers by lamination or by fusion of the coatings or layers
• • 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
  • C09D11/102—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions other than those only involving unsaturated carbon-to-carbon bonds
• • 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
  • C09D11/106—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • C09D11/107—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds from unsaturated acids or derivatives thereof
• • 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
• • 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
  • C09D11/30—Inkjet printing inks
  • C09D11/40—Ink-sets specially adapted for multi-colour inkjet 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
  • C09D11/54—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

• This disclosure relates to a pretreatment liquid for inkjet inks, an ink set, an image recording method, a method for manufacturing a laminated body, an image recording material, and a laminated body.
• Patent Document 1 discloses a pretreatment liquid for inkjet recording that is excellent in image fixing properties, storage stability, and lamination strength to a non-absorbent substrate and enables high-quality printing.
• the pretreatment liquid for inkjet recording contains water-insoluble resin fine particles, a flocculant, a crosslinking agent, and water, and the water-insoluble resin fine particles contain composite resin particles in which a polyolefin-based resin is contained in a polyurethane-based resin.
• Patent document 1 JP 2019-177510 A
• a laminate is produced by applying an inkjet ink pretreatment liquid and an inkjet ink in this order to a non-permeable substrate to record an image, and then laminating a substrate onto the image in the image recorded.
• This laminate may be required to have boil resistance (i.e., resistance to boiling treatment).
• An object of one embodiment of the present disclosure is to provide a pretreatment liquid for inkjet ink that can improve the boil resistance of a laminated body when a laminate is produced by applying a pretreatment liquid for inkjet ink and an inkjet ink in this order onto a non-permeable substrate to record an image, obtaining an image recorded matter, and laminating a substrate for lamination onto the image in the obtained image recorded matter.
• Another problem to be solved by another embodiment of the present disclosure is to provide an ink set including the above-mentioned pretreatment liquid for ink-jet ink, as well as an image recording method, a method for producing a laminated body, an image recorded matter, and a laminated body, all of which use the above-mentioned pretreatment liquid.
• a pretreatment liquid for inkjet ink comprising water, a flocculant, a nonionic urethane resin, and a crosslinking agent.
• a content of the crosslinking agent relative to a total amount of the nonionic urethane resin is 2.0% by mass to 50% by mass.
• ⁇ 4> The pretreatment liquid for ink-jet ink according to any one of ⁇ 1> to ⁇ 3>, wherein the content of the crosslinking agent in the total amount of the pretreatment liquid for ink-jet ink is 0.10% by mass to 5.00% by mass.
• ⁇ 6> The ink set according to ⁇ 5>, wherein the resin having a carboxy group contained in the inkjet ink includes a urethane resin having a carboxy group.
• ⁇ 7> The ink set according to ⁇ 5> or ⁇ 6>, wherein the ink-jet ink is a white ink containing a white pigment.
• An image recording method comprising: ⁇ 9> The image recording method according to ⁇ 8>, wherein the resin having a carboxy group contained in the inkjet ink includes a urethane resin having a carboxy group.
• ⁇ 10> The image recording method according to ⁇ 8> or ⁇ 9>, wherein the ink-jet ink is a white ink containing a white pigment.
• ⁇ 11> The image recording method according to any one of ⁇ 8> to ⁇ 10>, wherein an amount of the crosslinking agent in the inkjet ink pretreatment liquid applied onto the non-permeable substrate is 1.0% by mass to 30% by mass with respect to an amount of the resin having a carboxy group in the inkjet ink applied onto the non-permeable substrate.
• a method for producing a laminate comprising the steps of: ⁇ 13>
• An image display device comprising: an impermeable substrate; and an image disposed on the impermeable substrate; The image is a pretreatment layer disposed on the non-permeable substrate and containing a flocculant, a nonionic urethane resin, and a crosslinking agent; an ink layer disposed on the pretreatment layer and containing a pigment and a resin having a carboxy group; Including, Image recording.
• a laminate body comprising:
• a pretreatment liquid for inkjet ink that can improve the boil resistance of a laminated body when a laminate is produced by applying a pretreatment liquid for inkjet ink and an inkjet ink in this order onto a non-permeable substrate to record an image to obtain an image recorded matter, and then laminating a substrate for lamination onto the image in the obtained image recorded matter.
• an ink set including the above-mentioned pretreatment liquid for ink-jet ink, as well as an image recording method, a method for producing a laminated body, an image recorded product, and a laminated body, all of which use the above-mentioned pretreatment liquid.
• a numerical range indicated using “to” means a range that includes the numerical values before and after “to” 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 in a certain numerical range.
• the upper limit or lower limit described in a certain numerical range may be replaced with a value shown in the examples.
• the amount of each component in a composition means the total amount of the multiple substances present in the composition when multiple substances corresponding to each component are present in the composition, unless otherwise specified.
• a combination of two or more preferred aspects is a more preferred aspect.
• the term "process” includes not only an independent process but also a process that cannot be clearly distinguished from other processes, as long as the intended purpose of the process is achieved.
• image refers to a film formed by applying a pretreatment liquid and an ink in this order
• image recording refers to the formation of an image (i.e., a film).
• image in this specification also includes a solid image.
• (meth)acrylate is a concept that encompasses both acrylate and methacrylate.
• (meth)acrylic is a concept that encompasses both acrylic and methacrylic.
• boiling treatment refers to a treatment in which an object (specifically, a laminate) is immersed in water at 60 to 100°C and heated for a certain period of time (e.g., 10 to 120 minutes).
• pretreatment liquid for inkjet ink contains water, a flocculant, a nonionic urethane resin, and a crosslinking agent.
• the pretreatment liquid disclosed herein can improve the boil resistance of a laminated body when a pretreatment liquid and an inkjet ink (hereinafter also simply referred to as "ink") are applied in this order onto a non-permeable substrate to record an image and obtain an image recording, and a lamination substrate is laminated onto the image in the obtained image recording to produce a laminated body.
• a pretreatment liquid and an inkjet ink hereinafter also simply referred to as "ink”
• the reason why the above-mentioned effect of improving the boil resistance of the laminated body is obtained is considered to be that when a pretreatment liquid and an ink are applied in this order to a non-permeable substrate to record an image, a component in the ink (e.g., a resin having a carboxyl group) is crosslinked by a crosslinking agent in the pretreatment liquid, and a hydrophobic image is obtained because the pretreatment liquid contains a nonionic urethane resin. That is, it is considered that the water absorption of the laminated body during boil treatment is suppressed (i.e., the boil resistance of the laminated body is improved) because the laminated body contains the above-mentioned hydrophobic image.
• a component in the ink e.g., a resin having a carboxyl group
• the above-mentioned boil resistance effect is also believed to be due to the excellent flexibility (i.e., ability to conform to deformation of the non-permeable substrate) of the image in the laminate.
• the reason why the image has excellent flexibility i.e., ability to conform to deformation of the non-permeable substrate) is believed to be because the pretreatment liquid contains a urethane resin.
• the nonionic urethane resin in the pretreatment liquid improves the hydrophobicity of the image by being nonionic, and improves the flexibility of the image by being a urethane resin, and as a result, it is believed that the effect of improving the boil resistance of the laminate is obtained.
• the pretreatment liquid of the present disclosure contains water.
• the water content is preferably 50% by mass or more, and more preferably 60% by mass or more, based on the total amount of the pretreatment liquid.
• the upper limit of the water content although it depends on the amounts of other components, is preferably 90% by mass or less, and more preferably 80% by mass or less, based on the total amount of the pretreatment liquid.
• the pretreatment liquid of the present disclosure contains at least one flocculant.
• the aggregating agent in the pretreatment liquid contributes to improving image quality by aggregating the components in the inkjet ink when an image is recorded by applying the pretreatment liquid and the inkjet ink in this order onto a non-permeable substrate.
• the flocculant for example, the flocculants described in paragraphs 0122 to 0130 of WO 2020/195360 can be used.
• Organic acids includes an organic compound having an acidic group.
• Acidic groups include phosphate groups, phosphonate groups, phosphinate groups, sulfate groups, sulfonic acid groups, sulfinic acid groups, and carboxy groups.
• the acidic group is preferably a phosphate group or a carboxy group, and more preferably a carboxy group.
• the acidic groups are at least partially dissociated in the pretreatment solution.
• Organic compounds having a carboxy group 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, pyrrolidone carboxylic acid, pyrone carboxylic acid, pyrrole carboxylic acid, furan carboxylic acid, pyridine carboxylic acid, coumaric acid, thiophene carboxylic acid, and nicotinic acid.
• the organic compound having a carboxy group is preferably a divalent or higher carboxylic acid (hereinafter also referred to as a polyvalent carboxylic acid), and more preferably a dicarboxylic acid.
• the polycarboxylic 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, and more preferably 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 (for example, 1.0 to 5.0). This allows the surface charge of the pigment, resin particles, and other particles in the ink, which are stabilized in dispersion by weakly acidic functional groups such as carboxyl groups, to be reduced by contacting them with an organic acid with an even lower pKa, thereby decreasing the dispersion stability.
• pKa for example, 1.0 to 5.0
• the organic acid has a low pKa, high solubility in water, and a valence of 2 or more. It is also more preferable that the organic acid has a high buffering capacity in a pH range lower than the pKa of the functional group (e.g., carboxy group) that stabilizes the dispersion of the particles in the ink.
• the functional group e.g., carboxy group
• the polyvalent metal compound includes a polyvalent metal salt.
• the polyvalent metal salt includes organic acid polyvalent metal salts and inorganic acid polyvalent metal salts.
• organic acid polyvalent metal salt polyvalent metal salts of the above-mentioned organic acids (for example, formic acid, acetic acid, benzoic acid, etc.) are preferred.
• the inorganic acid polyvalent metal salt is preferably a polyvalent metal nitrate, a polyvalent metal hydrochloride, or a polyvalent metal thiocyanate.
• polyvalent metal salts examples include salts of alkaline earth metals of Group 2 of the periodic table (e.g., magnesium, calcium), salts of transition metals of Group 3 of the periodic table (e.g., lanthanum), salts of metals of Group 13 of the periodic table (e.g., aluminum), and salts of lanthanides (e.g., neodymium).
• a calcium salt, a magnesium salt, or an aluminum salt is preferable, and a calcium salt or a magnesium salt is more preferable.
• organic acid polyvalent metal salts are preferred, and organic acid calcium salts or organic acid magnesium salts are more preferred.
• the polyvalent metal compound is dissociated into polyvalent metal ions and counter ions in the pretreatment liquid.
• the metal complex may contain, as a metal element, at least one selected from the group consisting of zirconium, aluminum, and titanium.
• the metal complex is, for example, a metal complex containing at least one ligand selected from the group consisting of acetate, acetylacetonate, methylacetoacetate, ethylacetoacetate, octylene glycolate, butoxyacetylacetonate, lactate, lactate ammonium salt, and triethanolamine.
• the metal complex may be a commercially available product.
• a variety of organic ligands, particularly a variety of multidentate ligands, capable of forming metal chelate catalysts, are commercially available.
• the metal complex may be a metal complex prepared by combining a commercially available organic ligand with a metal.
• the content of the coagulant in the pretreatment liquid is preferably 0.1% by mass to 40% by mass, more preferably 0.1% by mass to 30% by mass, even more preferably 1% by mass to 20% by mass, and even more preferably 1% by mass to 10% by mass, based on the total amount of the pretreatment liquid.
• the flocculant preferably contains at least one selected from the group consisting of an organic acid and an organic acid polyvalent metal salt as the polyvalent metal compound.
• the ratio of the total amount of the organic acid and the organic acid polyvalent metal salt to the total amount of the flocculant is preferably 50% by mass to 100% by mass, more preferably 60% by mass to 100% by mass, and even more preferably 80% by mass to 100% by mass.
• the flocculant contains an organic acid.
• the content of the organic acid in the total amount of the flocculant is preferably 50% by mass to 100% by mass, more preferably 60% by mass to 100% by mass, and further preferably 80% by mass to 100% by mass.
• the pretreatment liquid of the present disclosure contains at least one nonionic urethane resin.
• the nonionic urethane resin contributes to improving the boil resistance of the laminate.
• the nonionic urethane resin improves the hydrophobicity of the image by being nonionic (i.e., not having ionicity), and improves the flexibility of the resulting image (i.e., ability to conform to deformation of the non-permeable substrate) by being a urethane resin.
• the improved hydrophobicity and flexibility of the image results in improved boil resistance of the laminate.
• a nonionic urethane resin means a urethane resin that does not have ionicity (i.e., anionic or cationic).
• a urethane resin refers to a polymer containing urethane bonds.
• the urethane resin is synthesized, for example, by reacting a diol compound with a diisocyanate compound.
• diol compound and the diisocyanate compound for details of the diol compound and the diisocyanate compound, reference can be made to the descriptions in paragraphs 0031 to 0036 of JP-A-2001-247787, for example.
• the nonionic urethane resin is preferably a polyester-based urethane resin having an ester bond in the main chain, a polycarbonate-based urethane resin having a carbonate bond in the main chain, or a polyether-based urethane resin having an ether bond in the main chain.
• the nonionic urethane resin may be a water-soluble urethane resin that dissolves in water, or may be urethane resin particles that exist in a dispersed state in water.
• the nonionic urethane resin is preferably urethane resin particles.
• the average particle diameter of the nonionic urethane resin is preferably 1 nm to 200 nm, more preferably 3 nm to 200 nm, and even more preferably 50 nm to 150 nm, from the viewpoint of storage stability of the pretreatment liquid.
• the average particle diameter is determined by measuring the volume average particle diameter by dynamic light scattering using a particle size distribution measuring device, for example, a product name "Nanotrac UPA-EX150" manufactured by Nikkiso Co., Ltd.
• the weight average molecular weight of the nonionic urethane resin is not particularly limited, but is preferably 1,000 to 300,000, more preferably 2,000 to 200,000, and even more preferably 10,000 to 150,000.
• the weight average molecular weight (Mw) is measured by gel permeation chromatography (GPC).
• GPC gel permeation chromatography
• HLC-8220GPC manufactured by Tosoh Corporation
• TSKgel SuperHZM-H TSKgel SuperHZ4000
• TSKgel SuperHZ2000 all trade names manufactured by Tosoh Corporation
• THF tetrahydrofuran
• the conditions are 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, and a differential refractive index detector is used.
• the calibration curve will be created from eight samples of "Standard sample TSK standard, polystyrene” manufactured by Tosoh Corporation: "F-40", “F-20”, “F-4", "F-1", "A-5000”, “A-2500”, "A-1000", and "n-propylbenzene”.
• the glass transition temperature of the nonionic urethane resin is preferably -55°C to 50°C, more preferably -55°C to 20°C, and even more preferably -55°C to 0°C.
• the glass transition temperature is measured using a differential scanning calorimeter, for example, a product named "DSC-60" manufactured by Shimadzu Corporation.
• the nonionic urethane resin preferably has a breaking elongation of 300% to 1300%, and more preferably 600% to 1300%.
• the breaking elongation of the nonionic urethane resin is 300% to 1300%, the internal stress caused by the boil treatment can be reduced, and the boil resistance of the laminate is further improved.
• the breaking elongation is measured by the following method.
• a nonionic urethane resin aqueous solution or dispersion is added to a Teflon (registered trademark) container with a bottom area of 50 mm x 100 mm and a height of 30 mm, and the solution is dried at 25 ° C. for 24 hours, and then dried at 80 ° C. for 6 hours to obtain a resin film with a thickness of 500 ⁇ m.
• a 10 mm x 50 mm sample is cut out from the resin film, and a tensile test is performed using a precision universal testing machine (product name "Autograph AG-IS", manufactured by Shimadzu Corporation), and the breaking elongation is measured according to JIS K6251:2017.
• the nonionic urethane resin may be a commercially available product.
• Examples of commercially available products include the Superflex series manufactured by Daiichi Kogyo Seiyaku Co., Ltd. and the PUE series manufactured by Murayama Chemical Laboratory Co., Ltd.
• the content of the nonionic urethane resin is preferably 1% by mass to 25% by mass, more preferably 5% by mass to 20% by mass, and even more preferably 5% by mass to 15% by mass, based on the total amount of the pretreatment liquid.
• the pretreatment liquid may contain a resin other than the nonionic urethane resin.
• the ratio of the nonionic urethane resin to the total amount of resin components in the pretreatment liquid is preferably 50% by mass to 100% by mass, more preferably 80% by mass to 100% by mass, and even more preferably 90% by mass to 100% by mass.
• the pretreatment liquid of the present disclosure contains at least one crosslinking agent.
• a cross-linking agent refers to a compound having at least one cross-linking group.
• the crosslinking group in the crosslinking agent include a carbodiimide group, an oxazoline group, an aziridine group (also known as an ethyleneimino group), an epoxy group, an isocyanate group, an aldehyde group, an N-methylol group, an acryloyl group, a vinyl sulfone group, an active halogen group, a glyoxal group, and a group having a melamine structure.
• the crosslinking agent preferably contains a compound having at least one of a carbodiimide group and an oxazoline group. This can further improve the boil resistance of the laminate.
• the compound having a carbodiimide group commercially available products can also be used.
• Examples of commercially available compounds having a carbodiimide group include Carbodilite V-02, SV-02, V-02-L2, V-04, V-06, E-01, E-02, E-03A, and SW-12G, all manufactured by Nisshinbo Chemical Co., Ltd.
• the compound having an oxazoline group commercially available products can also be used.
• Commercially available compounds having an oxazoline group include, for example, Epocross series K-1010E, K-2010E, K-1020E, K-2020E, K-1030E, K-2030E, WS-300, WS-500, WS-700, and RPS-1005 manufactured by Nippon Shokubai Co., Ltd.
• the compound having an epoxy group commercially available products can also be used.
• Commercially available examples of the compound having an epoxy group include Denacol EX-321, EX-821, EX-830, EX-850, and EX-851, all of which are manufactured by Nagase ChemteX Corporation.
• crosslinking agents that are compounds containing an aziridine group (also known as an ethyleneimino group) include Chemitite PZ-33 and DZ-22E manufactured by Nippon Shokubai Co., Ltd.
• the content of the crosslinking agent relative to the total amount of the nonionic urethane resin is preferably 1.0 mass% to 80 mass%, more preferably 2.0 mass% to 60 mass%, even more preferably 2.0 mass% to 50 mass%, and still more preferably 2.5 mass% to 50 mass%.
• the boil resistance of the laminate is further improved, which is believed to be because the action of the crosslinking agent is more effectively exerted.
• the boil resistance of the laminate is improved because the flexibility of the resulting image (i.e., its ability to conform to a non-permeable substrate) is improved.
• the content of the crosslinking agent relative to the total amount of the nonionic urethane resin is 80 mass % or less, the storage stability of the pretreatment liquid is further improved.
• the content of the crosslinking agent relative to the total amount of the pretreatment liquid is preferably 0.10 mass % to 10.00 mass %, more preferably 0.10 mass % to 8.00 mass %, even more preferably 0.10 mass % to 5.00 mass %, still more preferably 0.20 mass % to 5.00 mass %, and still more preferably 0.25 mass % to 5.00 mass %.
• the content of the crosslinking agent relative to the total amount of the pretreatment liquid is 0.10% by mass or more, the boil resistance of the laminate is further improved, which is believed to be because the action of the crosslinking agent is more effectively exerted.
• the boil resistance of the laminate is further improved, which is believed to be because the flexibility of the obtained image (i.e., its ability to conform to a non-permeable substrate) is further improved.
• the content of the crosslinking agent relative to the total amount of the pretreatment liquid is 10.00% by mass or less, the storage stability of the pretreatment liquid is further improved.
• the pretreatment liquid of the present disclosure may contain at least one organic solvent.
• organic solvent is not limited, and examples thereof include: Monoalcohols having 1 to 4 carbon atoms; Diols such as 1,3-propanediol, 1,3-butanediol, 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, and 4-methyl-1,2-pentanediol; Triols such as glycerin, 1,2,6-hexanetriol, and trimethylolpropane; Alkylene glycols such as ethylene glycol and propylene glycol; Alkylene glycol monoalkyl ethers such as ethylene glycol monoalkyl ether and propylene glycol monoalkyl ether; polyalkylene glycols
• the content of the organic solvent is preferably 1% to 20% by mass, and more preferably 3% to 10% by mass, based on the total amount of the pretreatment liquid.
• the pretreatment liquid of the present disclosure may contain at least one surfactant.
• the type of surfactant is not particularly limited, and may be any of anionic surfactants, cationic surfactants, betaine surfactants, and nonionic surfactants.
• surfactants include acrylic surfactants, fluorine-based surfactants, and silicone-based surfactants.
• the surfactant content is preferably 0.1% to 5% by mass, and more preferably 0.2% to 1% by mass, based on the total amount of the pretreatment liquid.
• the pretreatment liquid of the present disclosure may contain other components in addition to those described above, as necessary.
• Other components that can be contained in the pretreatment liquid include known additives such as a solid wetting agent, colloidal silica, inorganic salts, anti-fading agents, emulsion stabilizers, penetration enhancers, UV absorbers, preservatives, antifungal agents, pH adjusters, viscosity adjusters, rust inhibitors, chelating agents, and water-soluble polymer compounds (for example, the water-soluble polymer compounds described in paragraphs 0026 to 0080 of JP2013-001854A).
• the pH of the pretreatment liquid is preferably 2.0 to 7.0, and more preferably 2.0 to 4.0.
• the pH is measured at 25° C. using a pH meter, for example, a pH meter manufactured by Toa DKK Corporation (model number "HM-31").
• the viscosity of the pretreatment liquid is preferably 0.5 mPa ⁇ s to 10 mPa ⁇ s, and more preferably 1 mPa ⁇ s to 5 mPa ⁇ s.
• the viscosity is measured at 25°C using a viscometer.
• the viscosity is measured at 25°C using a viscometer, for example, a TV-22 type viscometer manufactured by Toki Sangyo Co., Ltd.
• 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 surface tension is a value measured at a temperature of 25°C.
• the surface tension is measured at 25°C using a surface tensiometer, for example, an automatic surface tensiometer (product name "CBVP-Z”) manufactured by Kyowa Interface Science Co., Ltd., using the plate method.
• the ink set of the present disclosure comprises: An ink set for ink jet recording on a non-permeable substrate, comprising: The pretreatment liquid of the present disclosure described above, An ink-jet ink (hereinafter simply referred to as "ink") containing water, a pigment, and a resin having a carboxy group; Includes.
• the ink set of the present disclosure contains the pretreatment liquid of the present disclosure described above, and therefore has the same effects as the pretreatment liquid of the present disclosure described above.
• the ink set of the present disclosure includes an ink containing water, a pigment, and a resin having a carboxy group.
• the ink set of the present disclosure may contain only one type of ink, or two or more types of ink.
• the ink contains water.
• the water content is preferably 10% by mass or more, more preferably 20% by mass or more, even more preferably 30% by mass or more, and particularly preferably 50% by mass or more, based on the total amount of the ink.
• the upper limit of the water content relative to the total amount of the ink is appropriately determined depending on the contents of other components, but is, for example, 99% by mass, preferably 95% by mass, and more preferably 90% by mass.
• the ink contains at least one resin having a carboxy group.
• the resin having a carboxy group contained in the ink preferably includes a urethane resin having a carboxy group.
• the urethane resin having a carboxy group that may be contained in the ink is preferably a polyester-based urethane resin having a carboxy group and an ester bond in the main chain, a polycarbonate-based urethane resin having a carboxy group and a carbonate bond in the main chain, or a polyether-based urethane resin having a carboxy group and an ether bond in the main chain.
• the urethane resin having a carboxy group that can be contained in the ink may be a water-soluble urethane resin, or a water-insoluble urethane resin (i.e., urethane resin particles).
• the urethane resin is preferably urethane resin particles.
• the average particle size of the urethane resin particles is preferably 1 nm to 200 nm, more preferably 3 nm to 200 nm, and even more preferably 5 nm to 50 nm, from the viewpoint of ejection stability.
• the average particle size of the urethane resin particles in the ink can be measured in the same manner as the average particle size of the urethane resin particles in the pretreatment liquid.
• the weight average molecular weight (Mw) of the urethane resin having a carboxy group that can be contained in the ink is not particularly limited, but is preferably from 1,000 to 300,000, more preferably from 2,000 to 200,000, and even more preferably from 10,000 to 150,000.
• the weight average molecular weight of the urethane resin having a carboxy group that can be contained in the ink can be measured in the same manner as the weight average molecular weight of the nonionic urethane resin in the pretreatment liquid.
• the urethane resin having a carboxy group that can be contained in the ink may be a commercially available product.
• commercially available products include the Superflex series manufactured by Daiichi Kogyo Seiyaku Co., Ltd., the Permarin UA series and U-coat series manufactured by Sanyo Chemical Industries, Ltd., the Takelac series manufactured by Mitsui Chemicals, Inc., and the PUE series manufactured by Murayama Chemical Laboratory.
• the content of the urethane resin having a carboxyl group that can be contained in the ink is preferably 1% by mass to 25% by mass, more preferably 2% by mass to 20% by mass, and even more preferably 5% by mass to 20% by mass, based on the total amount of the ink.
• Pigment dispersing resin containing carboxyl groups may include a pigment dispersing resin having a carboxy group.
• examples of the pigment dispersing resin having a carboxy group include pigment dispersing resins described below that have a carboxy group.
• the content of the resin having a carboxy group in the ink is preferably 1.0% by mass to 10.0% by mass, more preferably 3.0% by mass to 9.0% by mass, and even more preferably 4.0% by mass to 8.0% by mass, based on the total mass of the ink.
• the resin having a carboxy group in the ink is a urethane resin having a carboxy group and a pigment dispersion resin having a carboxy group
• the content of the resin having a carboxy group in the ink referred to here is the total amount of the urethane resin having a carboxy group and the pigment dispersion resin having a carboxy group.
• the ink contains at least one pigment.
• the pigment contained in the ink may be a white pigment or a colored pigment.
• the ink may be a white ink containing a white pigment, or a colored ink containing a colored pigment.
• color pigment means a chromatic pigment or a black pigment.
• colored ink means chromatic ink (e.g., cyan ink, magenta ink, yellow ink, etc.) or black ink.
• the ink is preferably a white ink containing a white pigment.
• the concealing property of an image means the property of covering and concealing the surface on which the image is recorded (for example, the surface of a non-permeable substrate, the surface of an image formed as a base, etc.).
• white pigments examples include inorganic pigments such as titanium dioxide, barium sulfate, calcium carbonate, silica, zinc oxide, zinc sulfide, mica, talc, and pearls.
• the white pigment is preferably titanium dioxide, barium sulfate, calcium carbonate, or zinc oxide, and more preferably titanium dioxide.
• the average primary particle diameter of the white pigment is preferably 150 nm or more, and more preferably 200 nm or more. From the viewpoint of ink ejection, the average primary particle diameter of the white pigment is preferably 400 nm or less, and more preferably 350 nm or less.
• the average primary particle diameter of the white pigment is a value measured using a transmission electron microscope (TEM). Specifically, 50 randomly selected white pigment particles present within the field of view observed with the TEM are measured and averaged to obtain the primary particle diameters of the 50 particles.
• TEM transmission electron microscope
• a 1200EX transmission electron microscope manufactured by JEOL Ltd. can be used as the transmission electron microscope.
• the content of the white pigment is preferably 2% by mass to 25% by mass, more preferably 5% by mass to 25% by mass, and even more preferably 10% by mass to 20% by mass, based on the total amount of ink.
• the ink may contain a color pigment in addition to, or instead of, a white pigment.
• a color pigment the type and content of the color pigment can be found in the section on the second ink described below.
• the ink may contain at least one pigment dispersing resin.
• a pigment dispersing resin means a resin having a function of dispersing a pigment.
• the pigment dispersing resin may be a random copolymer or a block copolymer.
• the pigment dispersing resin may have a crosslinked structure.
• the ink may be prepared using a pigment dispersion that contains a pigment and a pigment dispersing resin.
• the pigment dispersing resin is preferably a random copolymer.
• the random copolymer preferably contains a structural unit derived from a hydrophobic monomer and a structural unit derived from a monomer containing an anionic group (hereinafter referred to as an "anionic group-containing monomer").
• anionic group-containing monomer a monomer containing an anionic group
• the content ratio (x:y) of the structural unit x derived from the hydrophobic monomer and the structural unit y derived from the anionic group-containing monomer is preferably 8:1 to 1:1.
• the structural unit derived from the hydrophobic monomer contained in the random copolymer may be of only one type, or may be of two or more types.
• the structural unit derived from the anionic group-containing monomer contained in the random copolymer may be of only one type, or of two or more types.
• the hydrophobic monomer preferably includes a monomer having a hydrocarbon group with 4 or more carbon atoms, more preferably includes an ethylenically unsaturated monomer having a hydrocarbon group with 4 or more carbon atoms, and even more preferably includes a (meth)acrylate having a hydrocarbon group with 4 or more carbon atoms.
• the hydrocarbon group may be any of a linear hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group.
• the number of carbon atoms in the hydrocarbon group is more preferably 6 or more, and even more preferably 10 or more.
• the upper limit of the number of carbon atoms in the hydrocarbon group is, for example, 20.
• Examples of (meth)acrylates having a chain hydrocarbon group with 4 or more carbon atoms include n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, octyl (meth)acrylate, lauryl (meth)acrylate, and stearyl (meth)acrylate.
• the number of carbon atoms in the chain hydrocarbon group is more preferably 6 or more, even more preferably 8 or more, and particularly preferably 12 or more.
• the ethylenically unsaturated monomer having a chain hydrocarbon group with 4 or more carbon atoms is preferably lauryl (meth)acrylate or stearyl (meth)acrylate.
• Examples of (meth)acrylates having an alicyclic hydrocarbon group having 4 or more carbon atoms include (meth)acrylic acid (bicyclo[2.2.1]heptyl-2), 1-adamantyl (meth)acrylate, 2-adamantyl (meth)acrylate, 3-methyl-1-adamantyl (meth)acrylate, 3,5-dimethyl-1-adamantyl (meth)acrylate, 3-ethyladamantyl (meth)acrylate, 3-methyl-5-ethyl-1-adamantyl (meth)acrylate, 3,5,8-triethyl-1-adamantyl (meth)acrylate, 3,5-dimethyl-8-ethyl-1-adamantyl (meth)acrylate, 2-methyl-2-adamantyl (meth)acrylate, 2-ethyl-2-adamantyl (meth)acrylate, acrylate, 3-hydroxy-1-adamantyl (meth)acrylate, octa
• the number of carbon atoms in the alicyclic hydrocarbon group is more preferably 6 or more.
• the ethylenically unsaturated monomer having an alicyclic hydrocarbon group having 4 or more carbon atoms is preferably isobornyl (meth)acrylate or cyclohexyl (meth)acrylate.
• Examples of (meth)acrylates having an aromatic hydrocarbon group with 4 or more carbon atoms include 2-naphthyl (meth)acrylate, phenoxyethyl (meth)acrylate, and benzyl (meth)acrylate. Of these, benzyl (meth)acrylate is preferred as an ethylenically unsaturated monomer having an aromatic hydrocarbon group with 4 or more carbon atoms.
• the hydrophobic monomer may further include a (meth)acrylate having a hydrocarbon group having 1 to 3 carbon atoms.
• Examples of (meth)acrylates having a hydrocarbon group with 1 to 3 carbon atoms include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, and hydroxyethyl (meth)acrylate.
• the structural units derived from hydrophobic monomers contained in the pigment dispersion resin preferably include structural units derived from (meth)acrylates having a chain-like hydrocarbon group with 4 or more carbon atoms, and structural units derived from (meth)acrylates having an aromatic hydrocarbon group with 4 or more carbon atoms.
• anionic group in the anionic group-containing monomer examples include a carboxy group, a salt of a carboxy group, a sulfo group, a salt of a sulfo group, a phosphoric acid group, a salt of a phosphoric acid group, a phosphonic acid group, and a salt of a phosphonic acid group.
• Counter ions in salts include alkali metal ions such as sodium ion, potassium ion, and lithium ion; alkaline earth metal ions such as calcium ion and magnesium ion; and ammonium ion.
• the anionic group is preferably a carboxy group or a salt of a carboxy group.
• Carboxy group-containing monomers include, for example, (meth)acrylic acid, ⁇ -carboxyethyl acrylate, fumaric acid, itaconic acid, maleic acid, and crotonic acid.
• the anionic group-containing monomer is preferably (meth)acrylic acid or ⁇ -carboxyethyl acrylate, and more preferably (meth)acrylic acid.
• the ratio of the white pigment content to the pigment dispersion resin content is preferably 1:0.04 to 1:3, more preferably 1:0.05 to 1:1, and even more preferably 1:0.05 to 1:0.5, by mass.
• the acid value of the pigment dispersing resin is preferably 100 mgKOH/g or more, and more preferably 120 mgKOH/g or more.
• the acid value of the pigment dispersing resin is preferably 300 mgKOH/g or less, and more preferably 230 mgKOH/g or less.
• the content of the pigment dispersion resin is preferably 0.1% to 10% by mass, more preferably 0.3% to 5% by mass, and even more preferably 0.5% to 2.5% by mass, relative to the total amount of the ink.
• the ink preferably contains an organic solvent. This improves the ejection stability.
• the organic solvent contained in the color ink may be one type or two or more types.
• the organic solvent may be the same as the organic solvent contained in the pretreatment liquid. From the viewpoint of ejection stability, the organic solvent preferably contains at least one selected from the group consisting of alkylene glycols and alkylene glycol monoalkyl ethers.
• the organic solvent content is preferably 10% to 40% by mass, and more preferably 15% to 30% by mass, relative to the total amount of the ink.
• the ink may contain additives such as surfactants, water-soluble resins, co-sensitizers, ultraviolet absorbers, antioxidants, anti-fading agents, conductive salts, and basic compounds, as necessary.
• additives such as surfactants, water-soluble resins, co-sensitizers, ultraviolet absorbers, antioxidants, anti-fading agents, conductive salts, and basic compounds, as necessary.
• the pH of the ink (25° C.) is preferably from 7 to 10, and more preferably from 7.5 to 9.5.
• the pH of the color ink can be measured in the same manner as the pH of the pretreatment liquid.
• the viscosity of the ink (30°C) is preferably 0.5 mPa ⁇ s to 30 mPa ⁇ s, more preferably 2 mPa ⁇ s to 20 mPa ⁇ s, more preferably 2 mPa ⁇ s to 15 mPa ⁇ s, and even more preferably 3 mPa ⁇ s to 10 mPa ⁇ s.
• the viscosity of the colored ink can be measured in the same manner as the viscosity of the pretreatment liquid.
• the surface tension of the ink 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 surface tension can be measured in the same manner as in the pretreatment liquid.
• the ink set of the present disclosure comprises:
• the white ink (hereinafter also referred to as the "first ink”) is an ink-jet ink containing water, a white pigment, and a resin having a carboxy group.
• a color ink (hereinafter also referred to as "second ink”) which is an ink-jet ink containing water, a color pigment, and a resin having a carboxy group; may include:
• the ink set may include two or more types of white ink, and may also include two or more types of colored ink (for example, a combination of cyan ink, magenta ink, yellow ink, and black ink, etc.).
• a pretreatment liquid according to the present disclosure a pretreatment liquid according to the present disclosure; a first ink as a white ink, which is an ink-jet ink containing water, a white pigment, and a resin having a carboxy group; a second ink as a color ink, which is an inkjet ink containing water, a color pigment, and a resin having a carboxy group;
• a first ink as a white ink, which is an ink-jet ink containing water, a white pigment, and a resin having a carboxy group
• a second ink as a color ink, which is an inkjet ink containing water, a color pigment, and a resin having a carboxy group
• a preferred embodiment of the second ink is similar to the preferred embodiment of the first ink (i.e., white ink) except that the second ink contains a color pigment as an essential component.
• the preferred aspects of the type and content of each component in the second ink are the same as the preferred aspects of the type and content of each component in the first ink.
• the color pigment may be any of organic and inorganic pigments that are commonly available on the market. Examples of color pigments include those described in "Encyclopedia of Pigments” edited by Seijiro Ito (published in 2000), “Industrial Organic Pigments” by W. Herbst and K. Hunger, and JP-A Nos. 2002-12607, 2002-188025, 2003-26978, and 2003-342503.
• the color pigment may be a water-insoluble pigment that can be dispersed in water by the aid of a dispersant, or may be a self-dispersing pigment.
• a self-dispersing pigment is a pigment that can be dispersed in water without the use of a dispersant.
• the self-dispersing pigment is a compound in which at least one type selected from the group consisting of hydrophilic groups such as a carbonyl group, a hydroxyl group, a carboxyl group, a sulfo group, and a phosphate group, and salts thereof, is chemically bonded to the surface of the pigment directly or via another group.
• the type of color pigment is not particularly limited, and examples include cyan pigments, magenta pigments, yellow pigments, and black pigments.
• the content of the color pigment is preferably 1% by mass to 20% by mass, more preferably 1% by mass to 15% by mass, and even more preferably 1% by mass to 10% by mass, relative to the total amount of the second ink.
• the image recording method of the present disclosure includes: A step of applying a pretreatment liquid of the present disclosure onto a non-permeable substrate (hereinafter also referred to as a "pretreatment liquid application step”); a step of applying, by an inkjet method, an ink containing water, a pigment, and a resin having a carboxy group (i.e., an inkjet ink; the same applies hereinafter) onto an area on the non-permeable substrate to which the pretreatment liquid has been applied (hereinafter also referred to as an "ink application step”); Includes.
• the image recording method disclosed herein uses the pretreatment liquid disclosed herein described above, and therefore has the same effects as the pretreatment liquid disclosed herein described above.
• the ink used in the ink application step is the same as the ink described in the section on the ink set of the present disclosure, and the preferred embodiments are also the same.
• the resin having a carboxy group contained in the ink used in the ink application step preferably contains a urethane resin having a carboxy group.
• the ink used in the ink application step is preferably a white ink containing a white pigment.
• the amount (g/m 2 ) of the crosslinking agent in the pretreatment liquid applied onto the non-permeable substrate is preferably 0.3% by mass to 50.0% by mass, more preferably 1.0% by mass to 30.0% by mass, even more preferably 1.0% by mass to 25.0% by mass, and still more preferably 1.0% by mass to 22.0% by mass, relative to the amount (g/m 2 ) of the resin having a carboxy group in the ink applied onto the non-permeable substrate.
• the ratio (mass %) of the amount of crosslinking agent (g/ m2 ) in the pretreatment liquid applied to the non-permeable substrate to the amount of resin having a carboxy group (g/ m2 ) in the ink applied to the non-permeable substrate is also referred to as the "application amount ratio [crosslinking agent in pretreatment liquid/resin having a carboxy group in ink]".
• the ratio of the amounts applied [crosslinking agent in the pretreatment liquid/resin having a carboxy group in the ink] is 0.3% by mass or more, the boiling resistance of the laminate is further improved, which is believed to be because the action of the crosslinking agent is more effectively exerted.
• the boil resistance of the laminate is improved because the flexibility of the obtained image (i.e., its ability to conform to a non-permeable substrate) is improved.
• the pretreatment liquid application step is a step of applying the pretreatment liquid in the ink set of the present disclosure (i.e., the pretreatment liquid of the present disclosure) onto a non-permeable substrate.
• the non-permeability of a non-permeable substrate refers to a property in which the water absorption rate in 24 hours measured in accordance with ASTM D570-98 (2016) is 2.5% or less.
• the unit of water absorption rate, "%" is based on mass.
• the water absorption rate is preferably 1.0% or less, and more preferably 0.5% or less.
• non-permeable substrate examples include glass, metals (e.g., aluminum, zinc, copper, etc.) and resins (e.g., polyvinyl chloride, cellulose diacetate, cellulose triacetate, cellulose propionate, cellulose butyrate, cellulose acetate butyrate, cellulose nitrate, polyethylene terephthalate, polyethylene, polystyrene, polypropylene, polycarbonate, polyvinyl acetal, nylon, acrylic resin, etc.).
• metals e.g., aluminum, zinc, copper, etc.
• resins e.g., polyvinyl chloride, cellulose diacetate, cellulose triacetate, cellulose propionate, cellulose butyrate, cellulose acetate butyrate, cellulose nitrate, polyethylene terephthalate, polyethylene, polystyrene, polypropylene, polycarbonate, polyvinyl acetal, nylon, acrylic resin, etc.
• the material of the impermeable substrate is preferably a resin.
• the impermeable substrate is preferably a resin substrate.
• the material of the non-permeable substrate is polypropylene, polyethylene, polyethylene terephthalate, nylon, acrylic resin, or polyvinyl chloride.
• the shape of the non-permeable substrate is preferably a sheet (film) or plate.
• non-permeable substrates having such shapes include glass plates, metal plates, resin sheets (resin films), plastic-laminated paper, metal-laminated or vapor-deposited paper, and metal-laminated or vapor-deposited plastic sheets (plastic films).
• non-permeable resin substrates examples include resin sheets (resin films), and specific examples include soft packaging materials for packaging food products, etc., and floor guide panels in mass retailers.
• impermeable substrates include textiles (woven fabrics) and nonwoven fabrics made of impermeable fibers.
• the thickness of the non-permeable substrate is preferably 0.1 ⁇ m to 1,000 ⁇ m, more preferably 0.1 ⁇ m to 800 ⁇ m, and even more preferably 1 ⁇ m to 500 ⁇ m.
• the non-permeable substrate may be subjected to a hydrophilization treatment.
• hydrophilization treatments include, but are not limited to, corona treatment, plasma treatment, frame treatment, heat treatment, abrasion treatment, light irradiation treatment (e.g., UV treatment), and flame treatment.
• Corona treatment can be performed, for example, using a Corona Master (product name "PS-10S", manufactured by Shinko Electric Measuring Instruments).
• the conditions for the corona treatment may be appropriately selected depending on the type of non-permeable substrate, etc.
• the impermeable substrate may be a transparent impermeable substrate.
• having transparency means that the transmittance of visible light with a wavelength of 400 nm to 700 nm is 80% or more (preferably 90% or more).
• the impermeable substrate is a transparent impermeable substrate, the image can be easily viewed through the impermeable substrate from the non-image recording surface side of the impermeable substrate.
• the non-permeable substrate is a transparent non-permeable substrate
• the second ink as a colored ink
• an ink as a white ink
• it is easy to view a colored image e.g., a pattern image such as letters, figures, etc.
• a white image e.g., a solid image
• 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.
• coating methods 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, etc.
• the amount of the pretreatment liquid applied to the non-permeable substrate is preferably 0.5 g/m 2 to 5.0 g/m 2 , and more preferably 1.0 g/m 2 to 4.0 g/m 2 .
• the pretreatment liquid application step may include applying the pretreatment liquid onto the non-permeable substrate, and heating and drying the pretreatment liquid applied onto the non-permeable substrate.
• Means for heating and drying the pretreatment liquid include known heating means such as a heater, known air blowing means such as a dryer, and a combination of these.
• Methods for heating and drying the pretreatment liquid include, for example, a method of applying heat with a heater or the like from the side opposite to the side of the non-permeable substrate to which the pretreatment liquid has been applied, a method of applying warm or hot air to the side of the non-permeable substrate to which the pretreatment liquid has been applied, a method of applying heat with an infrared heater to the side of the non-permeable substrate to which the pretreatment liquid has been applied or the side opposite to the side to which the pretreatment liquid has been applied, and a combination of these methods.
• the heating temperature during the heating and drying of the pretreatment liquid is preferably 35°C or higher, and more preferably 40°C or higher. There is no particular upper limit to the heating temperature, but 100°C is preferred, 90°C is more preferred, and 70°C is even more preferred.
• the heat drying time is not particularly limited, but is preferably 0.5 to 60 seconds, more preferably 0.5 to 20 seconds, and even more preferably 0.5 to 10 seconds.
• the ink application step is a step of applying ink by inkjet recording onto the area of the non-permeable substrate to which the pretreatment liquid has been applied.
• the components in the ink are aggregated on the non-permeable substrate by the action of the aggregating agent in the pretreatment liquid, thereby forming an image.
• ink ejection method used in inkjet recording
• any of the well-known methods may be used, such as a charge control method that utilizes electrostatic attraction to eject ink, a drop-on-demand method (pressure pulse method) that utilizes the vibration pressure of a piezoelectric element, an acoustic inkjet method in which an electric signal is converted into an acoustic beam and irradiated onto the ink to eject ink using radiation pressure, and a thermal inkjet (Bubble Jet (registered trademark)) method in which ink is heated to form bubbles and the resulting pressure is utilized.
• a charge control method that utilizes electrostatic attraction to eject ink
• drop-on-demand method pressure pulse method
• acoustic inkjet method in which an electric signal is converted into an acoustic beam and irradiated onto the ink to eject ink using radiation pressure
• thermal inkjet Bubble Jet (registered trademark)
• JP-A-54-59936 As an inkjet recording method, in particular, the method described in JP-A-54-59936 can be effectively used, in which ink subjected to the action of thermal energy undergoes a sudden change in volume, and the ink is ejected from the nozzles by the force caused by this state change.
• the method described in paragraphs 0093 to 0105 of JP-A-2003-306623 can also be used.
• Ink is applied to a non-permeable substrate using the inkjet recording method by ejecting the ink from the nozzles of an inkjet head.
• Inkjet head methods include the shuttle method, in which a short serial head is scanned across the width of the recording medium to perform recording, and the line method, which uses a line head in which recording elements are arranged to cover the entire area of one side of the recording medium.
• an image can be recorded on the entire surface of a recording medium by scanning the recording medium in a direction intersecting the arrangement direction of the recording elements.
• the line method does not require a transport system such as a carriage that scans a short head as in the shuttle method. Also, compared to the shuttle method, the line method does not require complex scanning control of the carriage movement and the recording medium, and only the recording medium moves. Therefore, the line method achieves faster image recording speeds than the shuttle method.
• the ink be applied using an inkjet head with a resolution of 300 dpi or more (more preferably 600 dpi or more, and even more preferably 800 dpi or more).
• dpi stands for dots per inch, and 1 inch is 2.54 cm.
• the amount of ink ejected is preferably 1 pL (picoliter) to 10 pL, and more preferably 1.5 pL to 6 pL.
• the amount of ink applied to the area of the non-permeable substrate to which the pretreatment liquid has been applied is preferably 3.0 g/m 2 to 15.0 g/m 2 , and more preferably 5.0 g/m 2 to 12.0 g/m 2 .
• the ink application step includes applying ink by an inkjet method onto an area of the non-permeable substrate to which the pretreatment liquid has been applied; Heating and drying the applied ink; may include:
• the method of heat drying is not particularly limited, and examples thereof include infrared (IR) drying, hot air drying, and heat drying using a heating device (for example, a heater, a hot plate, a heating furnace, etc.).
• the heat drying method may be a combination of two or more of these methods.
• the heat drying can be carried out by heating the ink from at least one of the image recording surface side and the non-image recording surface side of the non-permeable substrate.
• the heating temperature in the heat drying of the ink is preferably 35° C. or higher, more preferably 40° C. or higher, even more preferably 50° C. or higher, and even more preferably 60° C. or higher.
• the upper limit of the heating temperature is not particularly limited, but is preferably 100°C, and more preferably 90°C.
• the heating time for heating and drying the ink is not particularly limited, but is preferably 1 to 180 seconds, more preferably 1 to 120 seconds, and even more preferably 1 to 60 seconds.
• An example of the image recording method of the present disclosure in the case of using ink of two or more colors is the image recording method using the first ink (i.e., white ink) and the second ink (i.e., colored ink) described above.
• the image recording method according to this embodiment includes the steps of: applying a pretreatment solution of the present disclosure onto a non-permeable substrate; applying the first ink (i.e., white ink) and the second ink (i.e., colored ink) described above to the region of the non-permeable substrate to which the pretreatment liquid has been applied by an inkjet recording method; Includes.
• the process of applying the pretreatment liquid onto the non-permeable substrate is as described above.
• a multi-color image can be recorded using a first ink (i.e., white ink) and a second ink (i.e., colored ink).
• a multi-color image is a colored image (such as a pattern image of characters, figures, etc.) against a white image (such as a solid image) as a background.
• the order in which the first ink (i.e., white ink) and the second ink (i.e., colored ink) are applied may not matter. For example, when the image is viewed from the image recording surface side, the first ink (i.e., white ink) and the second ink (i.e., colored ink) are applied in this order.
• the second ink i.e., colored ink
• the first ink i.e., white ink
• the method of applying each of the first ink and the second ink by the inkjet recording method is as described above.
• the step of applying the first ink and the second ink may include heating and drying the ink after application of at least one of the first ink and the second ink.
• the preferred conditions for heating and drying are as described above.
• an embodiment of this process may include applying the second ink (i.e., colored ink), applying the first ink (i.e., white ink), and drying in that order.
• the second ink may or may not be heated and dried between applications of the second ink.
• the method for producing a laminate according to the present disclosure includes: A step of obtaining an image recorded matter comprising a non-permeable substrate and an image disposed on the non-permeable substrate by the image recording method of the present disclosure described above; A step of laminating a substrate for lamination onto the side of the image recorded product on which the image is disposed to obtain a laminate; Includes.
• the method for producing a laminated body of the present disclosure includes the image recording method of the present disclosure described above, and therefore has the same effects as the image recording method of the present disclosure described above. Specifically, a laminated body with excellent boil resistance can be obtained.
• the step of obtaining a laminate is a step of obtaining a laminate by laminating a substrate for lamination onto the side of the image recorded product on which the image is disposed.
• the lamination can be performed by, for example, a method of laminating a substrate on the side of the image recorded product on which the image is disposed via another layer (e.g., an adhesive layer), or a method of laminating a substrate on the side of the image recorded product on which the image is disposed, with the substrate being passed through a laminator to be laminated, etc. In the latter case, a commercially available laminator can be used.
• the lamination temperature when laminating is not particularly limited.
• the temperature may be in the range of 20°C or higher.
• the temperature of the laminating rolls may be in the range of 20°C to 80°C.
• the pressure of the laminating roll pair may be appropriately selected according to need.
• the substrate for lamination is preferably a resin substrate.
• the resin substrate is not particularly limited, but examples thereof include substrates made of thermoplastic resins.
• the resin substrate is a substrate obtained by molding a thermoplastic resin into a sheet shape.
• the resin substrate preferably comprises polypropylene, polyethylene terephthalate, nylon, polyethylene, or polyimide.
• the shape of the resin substrate is not particularly limited, but a sheet-shaped resin substrate is preferable.
• the thickness of the resin substrate is preferably 10 ⁇ m to 200 ⁇ m, and more preferably 10 ⁇ m to 100 ⁇ m.
• the lamination substrate may be laminated directly onto the side of the image recording material on which the image is disposed, or may be laminated via another layer (e.g., an adhesive layer).
• lamination When laminating a substrate directly onto the side of an image recording material on which an image is placed, lamination can be performed by known methods such as heat compression bonding or heat fusion bonding.
• the lamination can be performed, for example, by a method in which an adhesive is applied to the side of the image recording material on which the image is disposed, the substrate for lamination is placed thereon, and then the image recording material and the substrate for lamination are attached to each other.
• the lamination can also be performed by a method such as extrusion lamination (i.e., sandwich lamination).
• the adhesive layer preferably contains an isocyanate.
• the adhesive layer contains an isocyanate, the adhesion between the adhesive layer and the image is improved, and the boil resistance can be further improved.
• the image recording of the present disclosure is a non-permeable substrate; and an image disposed on the non-permeable substrate;
• the image is a pretreatment layer disposed on the non-permeable substrate and containing a flocculant, a nonionic urethane resin, and a crosslinking agent; an ink layer disposed on the pretreatment layer and containing a pigment and a resin having a carboxy group; Includes.
• the image recorded matter of the present disclosure can be produced by the image recording method of the present disclosure. Therefore, a laminate having excellent boil resistance can be produced.
• components in the pretreatment layer and the ink layer please refer to the components of the pretreatment liquid and the components of the ink described above.
• the laminate of the present disclosure is The image recording material of the present disclosure described above; a lamination substrate laminated onto an image of an image recording material; Equipped with.
• the laminate of the present disclosure can be produced by the method for producing the laminate of the present disclosure. Therefore, it has excellent boil resistance.
• the preferred embodiments of the substrate for lamination are as described above.
• pretreatment solution - Flocculant listed in Table 1 Amount (% by mass) listed in Table 1
• Resin listed in Table 1 Amount (% by mass) listed in Table 1 (content as resin solid content)
• Crosslinking agent shown in Table 1 Amount (% by mass) shown in Table 1 ⁇ BYK-024 (BYK, antifoaming agent) ... 0.01% by mass
• Dimethylaminoethanol 0.1% by mass Surfynol 104 (manufactured by Nissin Chemical Industry Co., Ltd., surfactant) ... 0.5% by mass Water: The remaining amount to make the total pretreatment liquid 100% by mass
• the “%” in each amount in Table 1 means mass %.
• crosslinking agent shown in Table 1 Details of the crosslinking agent shown in Table 1 are as follows.
• SV-2 Carbodilite SV-02 (manufactured by Nisshinbo Chemical Co., Ltd., a compound having a carbodiimide group)
• WS-500 Epocross WS-500 (manufactured by Nippon Shokubai Co., Ltd., a compound having an oxazoline group)
• PZ-33 Chemitite PZ-33 (manufactured by Nippon Shokubai Co., Ltd., a compound having an aziridine group)
• the details of the resins shown in Table 1 are as follows.
• the resin emulsion means a dispersion liquid containing a resin, and the resin exists as resin particles in the liquid.
• SF 500M Superflex 500M (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., a resin emulsion containing nonionic urethane resin).
• the glass transition temperature (Tg) of the nonionic urethane resin is ⁇ 39° C., and the breaking elongation is 1100%.
• PUE-1370 PUE-1370 (manufactured by Murayama Chemical Laboratory, a resin emulsion containing nonionic urethane resin).
• the glass transition temperature (Tg) of the nonionic urethane resin is ⁇ 59° C., and the breaking elongation is 1200%.
• UA-200 Permarine UA-200 (manufactured by Sanyo Chemical Industries, a resin emulsion containing anionic urethane resin).
• SF 620 Superflex 620 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., a resin emulsion containing a cationic urethane resin).
• A615-GE... PES Resin A615-GE (manufactured by Takamatsu Oil Co., Ltd., a resin emulsion containing anionic polyester).
• a pigment dispersion resin W was synthesized.
• Solution 1 was added dropwise to the three-neck flask over 4 hours, and solution 2 was added dropwise over 5 hours. After the dropwise addition was completed, the reaction was allowed to proceed for an additional 2 hours, and then the temperature was raised to 95° C. and the mixture was heated and stirred for 3 hours to react all of the unreacted monomers. The disappearance of the monomers was confirmed by a nuclear magnetic resonance ( 1 H-NMR) method.
• the resulting reaction solution was heated to 70° C., and 12.0 g of dimethylethanolamine was added as an amine compound, followed by the addition of propylene glycol and stirring to obtain a 30% by mass solution of pigment dispersion resin W.
• the structural units of the resulting pigment dispersion resin W were confirmed by 1 H-NMR, and the weight average molecular weight (Mw) determined by GPC was 28,000.
• the acid value of the pigment dispersion resin W was 200 mg KOH/g.
• the pigment dispersion resin W is a resin having a carboxy group.
• the zirconia container containing the obtained mixture was placed in a ready mill (model LSG-4U-08 (manufactured by IMEX Co., Ltd.)) and dispersed at a rotation speed of 1000 rpm (revolutions per minute) for 5 hours. After completion of dispersion, the beads were removed by filtration using a filter cloth, and a pigment dispersion W having a white pigment concentration of 45% by mass was obtained.
• the amount of resin with carboxyl groups in the ink refers to the total amount (mass % of the total amount of ink) of pigment dispersion resin W and urethane resin with carboxyl groups in Permarin UA-200.
• An image was recorded using the pretreatment liquid and white ink.
• An inkjet recording apparatus was prepared that was equipped with a transport system for continuously transporting a long substrate, a wire bar coater for applying a pretreatment liquid to the substrate, and an inkjet head for applying a white ink.
• a substrate a polyethylene terephthalate (PET) substrate ("FE2001” manufactured by Futamura Chemical Co., Ltd., thickness 12 ⁇ m, width 780 mm, length 4000 m; hereinafter referred to as "non-permeable substrate A”) was prepared.
• PET polyethylene terephthalate
• the above pretreatment liquid was applied to the non-permeable substrate A by a wire bar coater so as to be about 2.0 g/m 2 , and then dried at 50° C. for 2 seconds.
• a white ink was ejected from an inkjet head and applied in the form of a solid image onto the surface of the non-permeable substrate A to which the pretreatment liquid had been applied.
• the applied white ink was dried with hot air at 80° C. for 30 seconds to record a solid image, thereby obtaining an image record.
• Inkjet head 1200 dpi/30 inch width piezo full line head
• Ink ejection volume from inkjet head 3.0 pL (picoliters)
• Driving frequency 41 kHz (substrate conveying speed: 50 m/min)
• the viscosity of the pre-treatment liquid that had been prepared and then allowed to stand at 25° C. for 1 hour (hereinafter referred to as “viscosity before storage”), and the viscosity of the pre-treatment liquid that had been prepared and then stored in a sealed state at 60° C. for 14 days (hereinafter referred to as “viscosity after storage”) were measured.
• the viscosity before and after storage was measured using a VISCOMETER TV-22 (manufactured by Toki Sangyo Co., Ltd.) at 25° C. and 100 rpm (revolutions per minute).
• a sealed state refers to a state in which the contents are sealed in a container, and when the contents are stored at 50°C for 14 days, the amount of weight loss of the contents is less than 1% by weight.
• the viscosity increase rate was calculated by subtracting the viscosity before storage from the viscosity after storage. The smaller the degree of increase in viscosity, the more excellent the storage stability.
• the evaluation criteria are as follows:
• the resulting laminate was aged at 40° C. for 48 hours. Two sample pieces, each 200 mm long and 200 mm wide, were cut out from the aged laminate. The cut out sample pieces were overlapped and heat sealed on three sides to obtain a bag. The obtained bag was filled with pure water and then heat sealed.
• the sealed bag was placed in an autoclave (small sterilizer) for retort foods (product name "SR-240", manufactured by Tommy Seiko Co., Ltd.) and boiled at 95°C for 40 minutes. After the boiling treatment, the bag was taken out and the condition of the bag was visually observed. Specifically, the boiling resistance was evaluated based on the presence or absence of deformation of the bag and lifting of the laminate. The evaluation criteria are as follows: The term "laminate lifting" refers to a state in which lifting occurs due to peeling of an image or a laminate substrate.
• each of the Examples in which a pretreatment liquid containing water, a flocculant, a nonionic urethane resin, and a crosslinking agent was used produced a laminate (i.e., a laminate obtained by applying the pretreatment liquid and the inkjet ink in this order onto a non-permeable substrate to record an image, and laminating a substrate for lamination onto the image in the obtained image recorded substrate) that had excellent boil resistance.
• Comparative Example 1 in which the pretreatment liquid does not contain a crosslinking agent; Comparative Example 2, in which the pretreatment liquid contains an anionic urethane resin instead of a nonionic urethane resin; Comparative Example 3 in which the pretreatment liquid contained a cationic urethane resin instead of a nonionic urethane resin; Comparative Example 4 in which the pretreatment liquid contains a polyester resin instead of a nonionic urethane resin; and Comparative Example 5: Pretreatment liquid does not contain resin In both cases, the boil resistance of the laminate decreased.
• Examples 7, 8, 20, 21, 24, and 25 show that when the crosslinking agent in the pretreatment liquid contains a compound having at least one of a carbodiimide group and an oxazoline group (Examples 7, 8, 20, and 21), the boil resistance of the laminate is further improved.
• Example 8 shows that when the content of the crosslinking agent relative to the total amount of nonionic urethane resin is between 2.0% by mass and 50% by mass (Example 8), the boil resistance of the laminate is improved and the storage stability of the pretreatment liquid is improved.
• the reason that the boil resistance of the laminate is improved when the content of the crosslinking agent relative to the total amount of nonionic urethane resin is 50% by mass or less is thought to be because the flexibility of the image (i.e., its ability to conform to non-permeable substrates) is improved.
• Example 8 shows that when the content of the crosslinking agent relative to the total amount of the pretreatment liquid is 0.10% by mass to 5.00% by mass (Example 8), the boil resistance of the laminate is improved and the storage stability of the pretreatment liquid is improved.
• Example 2 shows that when the application amount ratio [crosslinker in pretreatment liquid/resin having a carboxy group in ink] (i.e., the ratio (mass %) of the application amount (g/ m2 ) of the crosslinker in the pretreatment liquid applied to the non-permeable substrate to the application amount (g/ m2 ) of the resin having a carboxy group in the ink applied to the non-permeable substrate) is 1.0 mass % or more (Example 2), the boil resistance of the laminate is further improved.
• the application amount ratio [crosslinker in pretreatment liquid/resin having a carboxy group in ink] i.e., the ratio (mass %) of the application amount (g/ m2 ) of the crosslinker in the pretreatment liquid applied to the non-permeable substrate to the application amount (g/ m2 ) of the resin having a carboxy group in the ink applied to the non-permeable substrate
• Example 5 shows that when the application amount ratio [crosslinking agent in the pretreatment liquid/resin having a carboxy group in the ink] is 30 mass % or less (Example 5), the boil resistance of the laminated body is further improved.
• Example 101 Evaluation of multi-color images
• Colored inks (specifically, cyan ink, magenta ink, yellow ink, and black ink) having the compositions shown in Table 2 were prepared.
• each component indicates its content (mass %) in the corresponding ink, and the "balance" which is the amount of water indicates the remaining amount to make the total 100 mass %.
• the details of the components after PG (1,2-propanediol) are the same as those of the white ink described above.
• APD4000C etc. in Table 2 are pigment dispersions, and the details are as follows.
• the amount of pigment dispersion is shown as the solid content (total amount of pigment and pigment dispersant).
• ⁇ APD4000C Project Cyan APD4000 (FUJIFILM Imaging Cyan pigment dispersion manufactured by Colorants, pigment concentration: 20% by weight APD4000M .
• Projet Magenta APD4000 manufactured by FUJIFILM Imaging Colorants, magenta pigment dispersion, pigment concentration: 20% by mass)
• APD1000R ...
• APD4000Y Projet Yellow APD4000 (manufactured by FUJIFILM Imaging Colorants, yellow pigment dispersion, pigment concentration: 20% by mass)
• APD4000K Projet Black APD4000 (manufactured by FUJIFILM Imaging Colorants, black pigment dispersion, pigment concentration: 15% by mass)
• Image recording A Image recording is carried out in the order of application of a pretreatment liquid, drying, application of a cyan ink, application of a white ink, and drying.
• Image recording B Image recording is carried out in the order of application of a pretreatment liquid, drying, application of cyan ink, application of magenta ink, application of yellow ink, application of black ink, application of white ink, and drying.
• Image recording C Image recording is performed in the order of application of a pretreatment liquid, drying, application of a cyan ink, drying, application of a white ink, and drying.
• Image recording D Image recording carried out in the order of application of a pretreatment liquid, drying, application of a cyan ink, application of a magenta ink, application of a yellow ink, application of a black ink, drying, application of a white ink, and drying.

Landscapes

• Chemical & Material Sciences (AREA)
• Life Sciences & Earth Sciences (AREA)
• Engineering & Computer Science (AREA)
• Materials Engineering (AREA)
• Wood Science & Technology (AREA)
• Organic Chemistry (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Ink Jet (AREA)
• Ink Jet Recording Methods And Recording Media Thereof (AREA)

Priority Applications (4)

Applications Claiming Priority (2)

Related Child Applications (1)

Publications (1)

Family

ID=92421429

Family Applications (1)

Country Status (5)

Citations (5)

Family Cites Families (11)

• 2024
  • 2024-01-11 EP EP24756520.3A patent/EP4667231A1/en active Pending
  • 2024-01-11 JP JP2025500721A patent/JPWO2024171668A1/ja active Pending
  • 2024-01-11 WO PCT/JP2024/000495 patent/WO2024171668A1/ja not_active Ceased
  • 2024-01-11 CN CN202480012728.8A patent/CN120693256A/zh active Pending
• 2025
  • 2025-08-14 US US19/299,663 patent/US20250368847A1/en active Pending

Patent Citations (5)

Non-Patent Citations (1)

Also Published As

Similar Documents

Legal Events