Image recorded material and method for producing the same, and laminate and method for producing the same

Abstract

To provide: an image recorded material excellent in lamination strength when a base material for lamination is laminated on an image; a method for producing the image recorded material; a laminate; and a method for manufacturing the laminate.SOLUTION: The method for producing the image recorded material includes: a step of preparing a pretreatment liquid containing water and an aggregating agent which is at least one selected from the group consisting of an organic acid, an organic acid salt, a polyvalent metal compound, and a metal complex; a step of preparing a first ink containing a first pigment, a first resin, water, and a surfactant 1, in which a content of the surfactant 1 is 0.01% by mass to 0.8% by mass with respect to a total amount of the first ink; a step of preparing a second ink containing a second pigment, a second resin, water, and a surfactant 2, in which a content of the surfactant 2 is 0.8% by mass to 5% by mass with respect to a total amount of the second ink; and an image recording step of applying the pretreatment liquid, the first ink, and the second ink in this order onto an impermeable base material to record an image; wherein in the image recording step, the image is recorded under a condition that an overlapping region in which a region to which the pretreatment liquid is applied, a region to which the first ink is applied, and a region to which the second ink is applied overlap each other in plan view is generated, and a ratio of a total applied mass of the first resin and the second resin per unit area to an applied mass of the aggregating agent per unit area is 16.0 or more and 30.0 or less in the overlapping region. The image recorded material, the laminate, and a method for manufacturing the laminate are also described.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present disclosure relates to an image-recorded material and a method for producing the same, and a laminated material and a method for producing the same. [Background technology]

[0002] In recent years, research has been conducted into a technique for recording an image using ink and a pretreatment liquid (also called a reaction liquid, etc.) containing an aggregating agent that aggregates components in the ink.

[0003] For example, Patent Document 1 discloses an inkjet recording method that reduces the odor of a reactant and can obtain high-quality recorded material, the inkjet recording method comprising a recording step of adhering a reaction liquid and one or more inkjet ink compositions to a low-absorbency or non-absorbency recording medium, wherein the reaction liquid contains a reactant that is a carboxylic acid or a carboxylate that reacts with a component of the inkjet ink composition, and the inkjet ink composition contains a resin and water, and the reaction liquid and the inkjet ink composition are adhered so that, in an adhesion region of the inkjet ink composition on the low-absorbency or non-absorbency recording medium, when the adhesion amount of the region with the highest adhesion amount of the resin per unit area is taken as 100%, the mass ratio of the adhesion amount of the resin to the adhesion amount of the reactant (the resin / the reactant) in the adhesion region where the adhesion amount of the resin is 20% or more and 100% or less is 1.5 or more and 16 or less.

[0004] Furthermore, Patent Document 2 discloses an inkjet recording method capable of obtaining recorded matter with excellent image quality and abrasion resistance, the inkjet recording method comprising: a reaction liquid applying step of applying a reaction liquid containing an aggregating agent that aggregates components of an aqueous ink composition to a recording area of ​​a recording medium; and an ink composition applying step of ejecting an aqueous ink composition containing a pigment dispersion containing a surface-treated pigment and water from an inkjet head to apply it to the recording area of ​​the recording medium, wherein the recording area has a region in which the amount of the aqueous ink composition applied is 2 to 20 times the amount of the reaction liquid applied. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Japanese Patent Application Laid-Open No. 2015-217591 [Patent Document 2] Japanese Patent Application Publication No. 2018-165029 Summary of the Invention [Problem to be solved by the invention]

[0006] However, after an image is recorded on a non-permeable substrate to obtain an image recording material, a laminating substrate may be laminated onto the image in the image recording material, and in this case, it may be necessary to improve the lamination strength between the image recording material and the laminating substrate.

[0007] An object of one aspect of the present disclosure is to provide an image recording material comprising a non-permeable substrate and an image recorded on the non-permeable substrate, which image recording material has excellent lamination strength when a lamination substrate is laminated onto the image, and a method for manufacturing an image recording material that can produce the image recording material. Another aspect of the present disclosure is to provide a laminated body that includes the image recorded matter and a substrate for lamination laminated onto the image of the image recorded matter, and that has excellent lamination strength between the image and the substrate for lamination, and a method for producing the laminated body. The purpose is to provide. [Means for solving the problem]

[0008] Specific means for solving the problems include the following aspects. <1> preparing a pretreatment liquid containing water and at least one flocculant selected from the group consisting of an organic acid, an organic acid salt, a polyvalent metal compound, and a metal complex; preparing a first ink containing a first pigment, a first resin, and water; preparing a second ink containing a second pigment, a second resin, and water, the second ink having a surface tension lower than that of the first ink; an image recording step of applying a pretreatment liquid, a first ink, and a second ink in this order onto an impermeable substrate to record an image; Including, The image recording process is a method for manufacturing an image recording product, in which an image is recorded under conditions in which an overlapping region is created in which an area to which a pretreatment liquid is applied, an area to which a first ink is applied, and an area to which a second ink is applied overlap in a planar view, and under conditions in which, in the overlapping region, the ratio of the applied mass of aggregating agent per unit area to the total applied mass of the first resin and the second resin per unit area is 16.0 or more and 30.0 or less. <2> The above ratio is between 16.0 and 25.0 <1> 1. A method for producing an image recorded material according to claim 1. <3> the content of organic solvents with a boiling point of 220°C or higher relative to the total amount of the first ink is 5% by mass or less, The content of organic solvents with a boiling point of 220°C or higher relative to the total amount of the second ink is 5% by mass or less. <1> or <2> 1. A method for producing an image recorded material according to claim 1. <4> The pretreatment liquid contains a resin, the first resin includes resin particles; The glass transition temperature of the resin contained in the pretreatment liquid is lower than the glass transition temperature of the resin particles contained in the first resin. <1> ~ <3> 10. A method for producing an image recorded matter according to any one of the above items. <5> the first resin includes resin particles; the second resin includes resin particles; In the overlapping region, the glass transition temperature of the resin particles contained in the first resin and the resin particles contained in the second resin, which has a larger applied mass per unit area, is defined as Ta, and the glass transition temperature of the resin particles contained in the second resin, which has a smaller applied mass per unit area, is defined as Tb, where Ta and Tb satisfy the relationship 0°C≦Ta-Tb≦30°C. <1> ~ <4> 10. A method for producing an image recorded matter according to any one of the above items. <6> When the viscosity of the mixture of the pretreatment liquid and the first ink is A1, and the viscosity of the mixture of the pretreatment liquid and the second ink is A2, A1 and A2 satisfy the relationship A1-A2>0 mPa s. <1> ~ <3> 10. A method for producing an image recorded matter according to any one of the above items. <7> <1> ~ <6> a step of obtaining an image recorded material by the method for producing an image recorded material according to any one of the above items; a step of laminating a lamination substrate onto the image-recorded side of the image-recorded product to obtain a laminate; A method for producing a laminate comprising the steps of: <8> an impermeable substrate; and an image recorded on the impermeable substrate; the image includes a pretreatment layer in contact with the non-permeable substrate and containing a flocculant, a first layer in contact with the pretreatment layer and containing a first pigment and a first resin, and a second layer in contact with the first layer and containing a second pigment and a second resin, and includes an overlapping region in which the pretreatment layer, the first layer, and the second layer overlap in a planar view; the flocculant is at least one selected from the group consisting of an organic acid, an organic acid salt, a polyvalent metal compound, and a metal complex; In the overlapping area, the ratio of the first density per unit area to the mass of flocculant per unit area An image recording material in which the ratio of the total mass of the resin to the total mass of the second resin is 16.0 or more and 30.0 or less. <9> <8> and an image recording material according to the above item (1), a lamination substrate laminated onto the image of the image recording material; A laminate body comprising: [Effects of the Invention]

[0009] According to one aspect of the present disclosure, there is provided an image recording material comprising a non-permeable substrate and an image recorded on the non-permeable substrate, which has excellent lamination strength when a lamination substrate is laminated onto the image, and a method for manufacturing an image recording material that can produce the image recording material. According to another aspect of the present disclosure, there is provided a laminated body comprising the image recording material and a laminating substrate laminated onto the image of the image recording material, and having excellent lamination strength between the image and the laminating substrate, and a method for manufacturing a laminated body capable of manufacturing the laminated body. DETAILED DESCRIPTION OF THE INVENTION

[0010] In the present disclosure, a numerical range expressed using "to" means a range that includes the numerical values ​​before and after "to" as the lower and upper limits. In the present disclosure, when a plurality of substances corresponding to each component are present in the composition, the amount of each component in the composition means the total amount of the plurality of substances present in the composition, unless otherwise specified. In the numerical ranges described in stages in this disclosure, the upper or lower limit value described in a certain numerical range may be replaced by the upper or lower limit value of another numerical range described in stages, or may be replaced by a value shown in an example. In the present disclosure, 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. In the present disclosure, combinations of preferred aspects are more preferred aspects.

[0011] In the present disclosure, the term "image" refers to a film formed in general by applying a pretreatment liquid, a first ink, and a second ink in this order onto a non-permeable substrate, and the terms "image recording" and "image recording" refer to the formation of a film and film formation, respectively. Additionally, the concept of "image" in this disclosure also includes solid images.

[0012] [Method for producing image recording material] The method for producing an image recording material according to the present disclosure includes: preparing a pretreatment liquid containing water and at least one flocculant selected from the group consisting of an organic acid, an organic acid salt, a polyvalent metal compound, and a metal complex; preparing a first ink containing a first pigment, a first resin, and water; preparing a second ink containing a second pigment, a second resin, and water, the second ink having a surface tension lower than that of the first ink; an image recording step of applying a pretreatment liquid, a first ink, and a second ink in this order onto an impermeable substrate to record an image; Including, In the image recording process, an image is recorded under conditions in which an overlapping region is created in which the region to which the pretreatment liquid is applied, the region to which the first ink is applied, and the region to which the second ink is applied overlap in a planar view, and under conditions in which, in the overlapping region, the ratio of the total applied mass of the first resin and the second resin per unit area to the applied mass of the coagulant per unit area (hereinafter also referred to as "application mass ratio [(first resin + second resin) / coagulant]" or "application amount ratio [resin / coagulant]") is 16.0 or more and 30.0 or less.

[0013] According to the method for manufacturing an image recording material disclosed herein, it is possible to manufacture an image recording material that comprises a non-permeable substrate and an image recorded on the non-permeable substrate, and that has excellent lamination strength when a lamination substrate is laminated onto the image. Here, the lamination strength refers to the peel strength when peeling the laminate substrate and the image recording material in a laminated body formed by the above lamination (i.e., a laminated body having a layered structure of "lamination substrate / image recording material" (more specifically, a layered structure of "lamination substrate / image / non-permeable substrate").

[0014] The reason why the method for producing an image recorded matter according to the present disclosure exhibits the above-mentioned effects is presumed to be as follows. In order to improve the lamination strength of the laminate, it is necessary to first improve the adhesion between the non-permeable substrate and the image, and then to improve the adhesion between the image and the substrate for lamination. In the image recording step of the method for producing an image-recorded product according to the present disclosure, a pretreatment liquid, a first ink, and a second ink are applied in this order onto a non-permeable substrate. That is, a pretreatment liquid is applied onto the non-permeable substrate, a first ink is applied onto the applied pretreatment liquid, and a second ink is applied onto the applied first ink. The pretreatment liquid, the first ink, and the second ink are applied under conditions (i.e., application arrangements) that create overlapping regions in which the area to which the pretreatment liquid is applied, the area to which the first ink is applied, and the area to which the second ink is applied overlap in a planar view. As a result, on the non-permeable substrate, the components of the first ink (mainly the first resin) and the components of the second ink (mainly the second resin) applied onto the pretreatment liquid act as an aggregating agent, which is a component of the pretreatment liquid, to aggregate, thereby forming an image. Here, in the overlapping region, by setting the applied mass ratio [(first resin + second resin) / aggregating agent] to 30.0 or less, it is believed that insufficient aggregation of the first resin and the second resin is suppressed, and that a decrease in adhesion between the non-permeable substrate and the image due to insufficient aggregation is suppressed. Furthermore, in the overlapping region, by setting the applied mass ratio [(first resin + second resin) / aggregating agent] to 16.0 or more, excessive aggregation of the first resin and the second resin is suppressed, and unevenness of the image surface and / or unevenness of the image thickness due to excessive aggregation is suppressed. As a result, it is thought that a decrease in adhesion between the image and the laminating substrate due to unevenness of the image surface and / or unevenness of the image thickness is suppressed. Furthermore, because the surface tension of the second ink is lower than that of the first ink, the wetting and spreading properties of the second ink on the first ink are improved in the overlapping region, which in turn reduces unevenness in the image surface and / or variations in image thickness, and is thought to prevent a decrease in adhesion between the image and the laminating substrate due to unevenness in the image surface and / or variations in image thickness. As described above, the manufacturing method of the image recording material disclosed herein ensures adhesion between the non-permeable substrate and the image, and also ensures adhesion between the image and the substrate for lamination, which is thought to result in ensuring lamination strength.

[0015] Hereinafter, each step that may be included in the method for producing an image recorded matter of the present disclosure will be described.

[0016] <Preparing the pretreatment liquid> The step of preparing a pretreatment liquid (hereinafter also referred to as the "pretreatment liquid preparation step") is a step of preparing a pretreatment liquid containing water and a flocculant that is at least one selected from the group consisting of an organic acid, an organic acid salt, a polyvalent metal compound, and a metal complex. The pretreatment liquid preparation step may be a step of simply preparing a pretreatment liquid that has been produced in advance, or may be a step of producing a pretreatment liquid. There are no particular limitations on the method for producing the pretreatment liquid, and any known method for mixing the components can be used.

[0017] (water) The pretreatment liquid 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 is preferably 90% by mass or less based on the total amount of the pretreatment liquid, although this depends on the amounts of other components.

[0018] (flocculant) The pretreatment liquid is prepared by preparing a flocculant that is at least one selected from the group consisting of organic acids, organic acid salts, polyvalent metal compounds, and metal complexes. The aggregating agent is a component that aggregates components (for example, the first resin and the second resin) in the inks (that is, the first ink and the second ink; the same applies hereinafter).

[0019] -Organic acid- The organic acid includes an organic compound having an acidic group. Examples of the acidic group include a phosphoric acid group, a phosphonic acid group, a phosphinic acid group, a sulfuric acid group, a sulfonic acid group, a sulfinic acid group, and a carboxy group. From the viewpoint of the aggregation rate of the ink, the acidic group is preferably a phosphate group or a carboxy group, and more preferably a carboxy group. It is preferable that at least a portion of the acidic groups be dissociated in the pretreatment liquid.

[0020] Preferred organic compounds having a carboxy group include polyacrylic acid, acetic acid, formic acid, benzoic acid, glycolic acid, malonic acid, malic acid (preferably DL-malic acid), maleic acid, succinic acid, glutaric acid, fumaric acid, citric acid, tartaric acid, phthalic acid, adipic acid, pimelic acid, 4-methylphthalic acid, lactic acid, pyrrolidonecarboxylic acid, pyronecarboxylic acid, pyrrolecarboxylic acid, furancarboxylic acid, pyridinecarboxylic acid, coumaric acid, thiophenecarboxylic acid, nicotinic acid, pimelic acid, etc. These compounds may be used alone or in combination of two or more.

[0021] As the organic compound having a carboxy group, from the viewpoint of the aggregation speed of the ink, a divalent or higher carboxylic acid (hereinafter also referred to as a polyvalent carboxylic acid) is preferable. Examples of polycarboxylic acids include: Dicarboxylic acids or tricarboxylic acids are preferred, More preferred are glutaric acid, malonic acid, succinic acid, adipic acid, pimelic acid, malic acid, maleic acid, fumaric acid, tartaric acid, or citric acid; More preferred are glutaric acid, malonic acid, succinic acid, adipic acid, pimelic acid, malic acid, fumaric acid, tartaric acid, or citric acid; More preferred are glutaric acid, malonic acid, succinic acid, adipic acid, or pimelic acid.

[0022] The organic acid preferably has a low pKa (for example, 1.0 to 5.0). This reduces the surface charge of particles such as pigments and polymer particles in the ink, which are stabilized by weakly acidic functional groups such as carboxyl groups, by contacting them with an organic acidic compound with a lower pKa, thereby lowering dispersion stability.

[0023] The organic acid preferably has a low pKa, high solubility in water, and a valence of 2 or more, and more preferably is a divalent or trivalent acidic substance that has a high buffering capacity in a pH range lower than the pKa of the functional group (e.g., carboxyl group) that stabilizes the dispersion of the particles in the ink.

[0024] -Organic acid salt- Examples of organic acid salts include salts of the organic acids exemplified above. Organic acid salts include those containing alkaline earth metals from Group 2 of the periodic table (e.g., magnesium, calcium), transition metals from Group 3 of the periodic table (e.g., lanthanum), cations from Group 13 of the periodic table (e.g., aluminum), and lanthanides (e.g., neodymium). As the organic acid salt, an organic acid salt containing an alkaline earth metal is preferred, and an organic acid salt containing calcium (e.g., calcium lactate, calcium acetate, etc.) or an organic acid salt containing magnesium (e.g., magnesium lactate, magnesium acetate, etc.) is preferred.

[0025] -Polyvalent metal compounds- Examples of polyvalent metal compounds include salts (excluding organic acid salts) containing at least one selected from the group consisting of alkaline earth metals of Group 2 of the periodic table (e.g., magnesium, calcium), transition metals of Group 3 of the periodic table (e.g., lanthanum), cations from Group 13 of the periodic table (e.g., aluminum), and lanthanides (e.g., neodymium). The polyvalent metal compound is preferably a nitrate, chloride, or thiocyanate. Particularly preferred polyvalent metal compounds are calcium or magnesium nitrate, calcium chloride, magnesium chloride, or calcium or magnesium thiocyanate. It is preferable that the polyvalent metal compound is at least partially dissociated into polyvalent metal ions and counter ions in the pretreatment liquid.

[0026] -Metal complexes- The metal complex is preferably a metal complex containing at least one metal element selected from the group consisting of zirconium, aluminum, and titanium. The metal complex is preferably a metal complex containing, as a ligand, at least one selected from the group consisting of acetate, acetylacetonate, methylacetoacetate, ethylacetoacetate, octylene glycolate, butoxyacetylacetonate, lactate, lactate ammonium salt, and triethanolamine.

[0027] As the metal complex, various metal complexes are commercially available, and in the present disclosure, commercially available metal complexes may be used. In addition, various organic ligands, particularly various multidentate ligands capable of forming metal chelate catalysts, are commercially available. Therefore, a metal complex prepared by combining a commercially available organic ligand with a metal may be used.

[0028] There is no particular limitation on the content of the flocculant. From the viewpoint of the aggregation speed of the ink, the content of the aggregating agent relative to the total amount of 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 particularly preferably 1% by mass to 10% by mass.

[0029] (resin) The pretreatment liquid preferably contains at least one resin. When the pretreatment liquid contains a resin, the adhesion of the image is further improved.

[0030] When the pretreatment liquid contains a resin, the glass transition temperature (Tg) of the resin contained in the pretreatment liquid is preferably 0°C or higher, more preferably 10°C or higher, even more preferably 20°C or higher, and even more preferably 30°C or higher. When the pretreatment liquid contains a resin, the glass transition temperature (Tg) of the resin contained in the pretreatment liquid is preferably 120° C. or lower, more preferably 100° C. or lower, and even more preferably is preferably 80°C or less, more preferably 70°C or less.

[0031] In this disclosure, the glass transition temperature of a resin means a value measured using differential scanning calorimetry (DSC). The glass transition temperature is specifically measured according to the method described in JIS K 7121 (1987) or JIS K 6240 (2011). The glass transition temperature in the present disclosure is the extrapolated glass transition onset temperature (hereinafter sometimes referred to as Tig). The method for measuring the glass transition temperature will now be described in more detail. When determining the glass transition temperature, the temperature is maintained at approximately 50°C lower than the expected glass transition temperature of the resin until the apparatus stabilizes, and then the temperature is heated at a heating rate of 20°C / min to a temperature approximately 30°C higher than the temperature at which the glass transition ends, and a differential thermal analysis (DTA) curve or DSC curve is prepared. The extrapolated glass transition onset temperature (Tig), i.e., the glass transition temperature in the present disclosure, is determined as the temperature at the intersection of a line drawn by extending the low-temperature baseline of a DTA curve or a DSC curve toward a higher temperature and a tangent drawn at the point where the gradient of the curve in the stepwise change portion of the glass transition is maximum.

[0032] When the pretreatment liquid contains two or more resins, the glass transition temperature (Tg) of the resins in the pretreatment liquid means the weighted average of the glass transition temperatures of the individual resins.

[0033] Examples of resins that can be contained in the pretreatment liquid include acrylic resins, polyester resins, polyolefin resins, polyurethane resins, polyurea resins, polyamide resins, polycarbonate resins, and polystyrene resins. The resin that can be contained in the pretreatment liquid preferably includes a polyester resin or an acrylic resin, and more preferably includes a polyester resin.

[0034] In the present disclosure, acrylic resin refers to a polymer (homopolymer or copolymer) of raw material monomers containing at least one selected from the group consisting of acrylic acid, derivatives of acrylic acid (e.g., acrylic acid esters), methacrylic acid, and derivatives of methacrylic acid (e.g., methacrylic acid esters). In the present disclosure, the polyester resin refers to a polymer compound containing an ester bond in the main chain. Examples of the polyester resin include a polycondensation product of a polycarboxylic acid (e.g., a dicarboxylic acid) and a polyalcohol (e.g., a diol). In the present disclosure, polyolefin resin refers to a polymer (homopolymer or copolymer) of raw material monomers containing olefin. Examples of polyolefin resins include polymers of one type of olefin, copolymers of two or more types of olefin, and copolymers of one or more types of olefin and one or more other monomers. Examples of olefins include α-olefins having 2 to 30 carbon atoms. In the present disclosure, polyurethane resin refers to a polymer compound containing a urethane bond. In the present disclosure, a polyurea resin refers to a polymer compound containing a urea bond. In the present disclosure, a polyamide resin refers to a polymer compound containing an amide bond. In the present disclosure, polycarbonate resin means a polymeric compound containing carbonate bonds. In the present disclosure, polystyrene resin refers to a polymer of raw material monomers including styrene.

[0035] The resin that can be contained in the pretreatment liquid may be a water-soluble resin or a water-insoluble resin, but a water-insoluble resin is preferred.

[0036] In the present disclosure, "water solubility" refers to the property of dissolving 1 g or more in 100 g of water at 25° C. Preferably, "water solubility" refers to the property of dissolving 3 g or more (more preferably 10 g or more) in 100 g of water at 25° C. In the present disclosure, "water-insoluble" refers to the property of dissolving less than 1 g in 100 g of water at 25°C. Preferably, "water-insoluble" refers to the property of dissolving less than 0.5 g in 100 g of water at 25°C.

[0037] The pretreatment liquid preferably contains resin particles. The resin particles are preferably made of a water-insoluble resin. The resin particles are preferably acrylic resin particles, polyester resin particles, a mixture of acrylic resin particles and polyester resin particles, or composite particles containing an acrylic resin and a polyester resin. As the resin particles, those similar to the resin particles that can be contained in the first ink, which will be explained in the section "Step of preparing the first ink" below, are also preferred.

[0038] The weight average molecular weight (Mw) of the resin in the resin particles is preferably 1,000 to 300,000, more preferably 2,000 to 200,000, and even more preferably 5,000 to 100,000.

[0039] In the present disclosure, unless otherwise specified, the weight average molecular weight (Mw) refers to a value measured by gel permeation chromatography (GPC). Measurement by gel permeation chromatography (GPC) was performed using an HLC (registered trademark)-8020GPC (Tosoh Corporation) as the measuring device, three TSKgel (registered trademark) Super Multipore HZ-H columns (4.6 mm ID × 15 cm, Tosoh Corporation), and THF (tetrahydrofuran) as the eluent. The measurement conditions were a sample concentration of 0.45% by mass, a flow rate of 0.35 mL / min, a sample injection volume of 10 μL, and a measurement temperature of 40°C, and an RI detector was used. The calibration curve is prepared from eight samples of "Standard Sample TSK Standard, Polystyrene" from Tosoh Corporation: "F-40", "F-20", "F-4", "F-1", "A-5000", "A-2500", "A-1000", and "n-propylbenzene".

[0040] The volume average particle size of the resin particles is preferably from 1 nm to 300 nm, more preferably from 3 nm to 200 nm, and even more preferably from 5 nm to 150 nm.

[0041] When preparing the pretreatment liquid, a commercially available aqueous dispersion of resin particles may be used. Commercially available aqueous dispersions of resin particles include PESRESIN A124GP, PESRESIN A645GH, PESRESIN A615GE, PESRESIN A520 (all manufactured by Takamatsu Oil & Fats Co., Ltd.), Eastek 1100, Eastek 1200 (all manufactured by Eastman Chemical Co., Ltd.), Pluscoat RZ570, Pluscoat Z687, Pluscoat Z565, Pluscoat RZ570, Pluscoat Z690 (all manufactured by Goo Chemical Industry Co., Ltd.), Vylonal MD1200 (manufactured by Toyobo Co., Ltd.), and EM57DOC (manufactured by Daicel FineChem Ltd.).

[0042] When the pretreatment liquid contains resin particles, the content of the resin particles relative to the total amount of the pretreatment liquid is preferably 0.5% by mass to 30% by mass, more preferably 1% by mass to 20% by mass, and particularly preferably 1% by mass to 15% by mass.

[0043] (Water-soluble organic solvent) The pretreatment liquid preferably contains at least one water-soluble organic solvent. As the water-soluble organic solvent, any known solvent can be used without any particular limitation. Examples of water-soluble organic solvents include polyhydric alcohols such as glycerin, 1,2,6-hexanetriol, trimethylolpropane, alkanediols (e.g., ethylene glycol, propylene glycol (1,2-propanediol), 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), and polyalkylene glycols (e.g., diethylene glycol, triethylene glycol, tetraethylene glycol, pentaethylene glycol, dipropylene glycol, and polyoxyethylene polyoxypropylene glycol); polyhydric alcohol ethers such as polyalkylene glycol ethers (e.g., diethylene glycol monoalkyl ether, triethylene glycol monoalkyl ether, tripropylene glycol monoalkyl ether, polyoxypropylene glyceryl ether, etc.); C1-C4 alkyl alcohols, glycol ethers, 2-pyrrolidone, and N-methyl-2-pyrrolidone; etc. Among these, from the viewpoint of suppressing transfer of components, polyhydric alcohols or polyhydric alcohol ethers are preferred, and alkanediols, polyalkylene glycols, or polyalkylene glycol ethers are more preferred.

[0044] When the pretreatment liquid contains a water-soluble organic solvent, the content of the water-soluble organic solvent relative to the total amount of the pretreatment liquid is preferably 0.5% by mass to 30% by mass, more preferably 1% by mass to 20% by mass, and particularly preferably 1% by mass to 15% by mass.

[0045] The water-soluble organic solvent that can be contained in the pretreatment liquid is preferably a water-soluble organic solvent having a boiling point of less than 220°C. From the viewpoint of the drying property of the pre-treatment liquid, it is preferable that the pre-treatment liquid does not contain an organic solvent with a boiling point of 220°C or higher, or that the content of the organic solvent with a boiling point of 220°C or higher is 5% by mass or less (more preferably 3% by mass or less, and even more preferably 1% by mass or less) of the total amount of the pre-treatment liquid. For specific examples of water-soluble organic solvents with a boiling point of less than 220° C. and organic solvents with a boiling point of 220° C. or higher, see the section below titled "Step of Preparing First Ink."

[0046] (Other ingredients) The pretreatment liquid may contain other components in addition to those described above, if necessary. Other components that can be contained in the pretreatment liquid include known additives such as surfactants, solid wetting agents, silicic acid compounds (e.g., colloidal silica), inorganic salts, anti-fading agents, emulsion stabilizers, penetration enhancers, UV absorbers, preservatives, anti-fungal agents, pH adjusters, viscosity adjusters, rust inhibitors, chelating agents, and water-soluble polymer compounds other than water-soluble cationic polymers (e.g., the water-soluble polymer compounds described in paragraphs 0026 to 0080 of JP 2013-001854 A). As for other components that can be contained in the pretreatment liquid, reference can also be made to the components that can be contained in the first ink, which will be described later.

[0047] (Physical properties of pretreatment liquid) From the viewpoint of the aggregation speed of the ink, the pH of the pretreatment liquid at 25° C. is preferably 0.1 to 3.5. When the pH of the pretreatment liquid is 0.1 or more, the roughness of the non-permeable substrate is further reduced, and the image The adhesion of the part is further improved. When the pH of the pretreatment liquid is 3.5 or less, the aggregation rate is further improved, the coalescence of ink dots (ink dots) on the surface of the non-permeable substrate is further suppressed, and roughness of the image is further reduced. The pH of the pretreatment liquid at 25° C. is more preferably 0.2 to 2.0. The conditions for measuring the pH of the pretreatment liquid at 25° C. are the same as the conditions for measuring the pH of the ink at 25° C. described above.

[0048] When the pretreatment liquid contains an aggregating agent, the viscosity of the pretreatment liquid is preferably in the range of 0.5 mPa·s to 10 mPa·s, and more preferably in the range of 1 mPa·s to 5 mPa·s, from the viewpoint of the aggregation speed of the ink.

[0049] Unless otherwise specified, the viscosity in this disclosure is a value measured at 25°C using a viscometer. As the viscometer, for example, a VISCOMETER TV-22 type viscometer (manufactured by Toki Sangyo Co., Ltd.) is used.

[0050] 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.

[0051] Unless otherwise specified, the surface tension in this disclosure is a value measured at a temperature of 25°C. The surface tension is measured, for example, using an Automatic Surface Tentiometer CBVP-Z (manufactured by Kyowa Interface Science Co., Ltd.).

[0052] <Step of Preparing First Ink> The step of preparing the first ink (hereinafter also referred to as the "first ink preparation step") is a step of preparing the first ink containing a first pigment, a first resin, and water. The first ink preparation step may be a step of simply preparing a first ink that has been manufactured in advance, or may be a step of manufacturing the first ink. There are no particular limitations on the method for producing the first ink, and any known method for mixing the components can be used.

[0053] (water) The first ink contains water. The content of water relative to the total amount of the first ink is preferably 30% by mass or more, more preferably 40% by mass or more, and even more preferably 50% by mass or more. The upper limit of the water content is preferably 90% by mass or less, and more preferably 80% by mass or less, relative to the total amount of the first ink, although this depends on the amounts of other components.

[0054] (First pigment) The first ink contains a first pigment. The first pigment refers to all pigment components contained in the first ink (that is, one or more pigments). The first pigment is not particularly limited, and may be an organic pigment or an inorganic pigment.

[0055] Examples of organic pigments include azo pigments, polycyclic pigments (e.g., phthalocyanine pigments, perylene pigments, perinone pigments, anthraquinone pigments, quinacridone pigments, dioxazine pigments, diketopyrrolopyrrole pigments, thioindigo pigments, isoindolinone pigments, quinophthalone pigments, pigments, etc.), dye chelates, nitro pigments, nitroso pigments, aniline black, etc. Examples of inorganic pigments include white inorganic pigments, iron oxide, barium yellow, cadmium red, chrome yellow, carbon black, etc. Preferred embodiments of the white inorganic pigment will be described later. Examples of the first pigment include the pigments described in paragraphs 0096 to 0100 of JP-A No. 2009-241586.

[0056] The first ink containing a chromatic pigment or a black pigment as the first pigment can be used as, for example, a color ink (for example, cyan ink, magenta ink, yellow ink, etc.) or a black ink.

[0057] Furthermore, when the first pigment contains a white pigment (for example, a white inorganic pigment), the first ink can also be used as, for example, a white ink (hereinafter also referred to as "white ink"). Furthermore, when the first pigment contains a white pigment and a pigment of a color other than white, the first ink can be used as an ink in which a chromatic color is added to white.

[0058] Examples of white inorganic pigments include titanium dioxide (TiO), barium sulfate, calcium carbonate, aluminum hydroxide, silica, zinc oxide, zinc sulfide, mica, talc, pearl, etc. Among the white inorganic pigments, titanium dioxide, barium sulfate, calcium carbonate, or zinc oxide is preferred, and titanium dioxide is more preferred.

[0059] The average primary particle diameter of the white inorganic pigment is, for example, 150 nm to 400 nm. When the average primary particle size is 150 nm or more, the hiding power is further improved. Here, the hiding power means the property of covering and hiding the base with an image (for example, a white image). When the average primary particle diameter is 400 nm or less, the ejection properties of the first ink are further improved. The average primary particle size of the white inorganic pigment is preferably 250 nm to 350 nm, and more preferably 250 nm to 300 nm.

[0060] The average primary particle size of the white inorganic pigment is a value measured using a transmission electron microscope (TEM), such as a 1200EX transmission electron microscope manufactured by JEOL Ltd. Specifically, ink diluted 1,000 times was dropped onto a Cu200 mesh (manufactured by JEOL Ltd.) with a carbon film attached, and the ink was then dried. After that, the circular equivalent diameters of 300 non-overlapping, independent particles were measured from an image magnified 100,000 times using a TEM, and the simple average of the obtained measurements was used as the average primary particle diameter.

[0061] The content of the first pigment is preferably 1% to 20% by mass, more preferably 1% to 15% by mass, and even more preferably 1% to 10% by mass, relative to the total amount of the first ink.

[0062] (First resin) The first ink contains a first resin. Here, the first resin refers to all resin components contained in the first ink (that is, one or more types of resin). In the image recording process described below, when the first resin in the first ink comes into contact with the aggregating agent in the pretreatment liquid on the non-permeable substrate, the resin particles in the first ink aggregate, thereby improving the adhesion of the image.

[0063] The first resin is not particularly limited, but is preferably an acrylic resin, a polyester resin, The resin is a polyurethane resin or a polyolefin resin.

[0064] The content of the first resin relative to the total amount of the first ink is preferably 1% by mass to 30% by mass, more preferably 2% by mass to 20% by mass, even more preferably 2% by mass to 15% by mass, and even more preferably 2% by mass to 10% by mass.

[0065] Specific examples of the first resin include a pigment dispersion resin for dispersing the first pigment, and resin particles that are particles made of resin.

[0066] -Pigment dispersion resin- The first resin may include a pigment dispersing resin. When the first resin contains a pigment dispersing resin, the first ink contains a resin-coated pigment having a structure in which at least a portion of the surface of the first pigment is coated with the pigment dispersing resin. The pigment dispersing resin is preferably a water-insoluble resin.

[0067] The pigment dispersing resin is preferably an acrylic resin. Examples of pigment dispersing resins include those described in International Publication No. 2013 / 180074, Japanese Patent No. 5863600, JP-A No. 2018-28080, JP-A No. 2017-149906, and JP-A No. 2016-193981. Pigment dispersing resins are also called "resin dispersants." Furthermore, as a combination of the first pigment and the pigment dispersing resin, a resin-coated pigment in which a pigment is coated with a crosslinked water-soluble resin may be used, for example, as described in Japanese Patent No. 5404669. In this case, the resin-coated pigment can be prepared by using, for example, an acrylic resin having a carboxy group as the water-soluble resin and a difunctional or higher epoxy compound as the crosslinking agent.

[0068] From the viewpoint of adsorptivity to the pigment, the pigment dispersing resin preferably contains an alicyclic structure or an aromatic ring structure, and more preferably contains an aromatic ring structure. The alicyclic structure is preferably an alicyclic hydrocarbon structure having 5 to 10 carbon atoms, and a cyclohexane ring structure, a dicyclopentanyl ring structure, a dicyclopentenyl ring structure, a norbornane ring structure, an isobornane ring structure, a norbornene ring structure, an isobornene ring structure, or an adamantane ring structure is preferred. The aromatic ring structure is preferably a naphthalene ring or a benzene ring, more preferably a benzene ring. The amount of the alicyclic structure or aromatic ring structure is, for example, preferably 0.01 mol to 1.5 mol, and more preferably 0.1 mol to 1 mol, per 100 g of resin contained in the resin particles.

[0069] From the viewpoint of pigment dispersing performance, the pigment dispersing resin preferably has an ionic group in its structure. The ionic group may be either an anionic group or a cationic group, but an anionic group is preferred. The anionic group is not particularly limited, but is preferably a carboxy group, a salt of a carboxy group, a sulfo group, or a salt of a sulfo group.

[0070] The acid value of the resin dispersant is preferably 30 mgKOH / g to 100 mgKOH / g, more preferably 30 mgKOH / g to 85 mgKOH / g, and even more preferably 50 mgKOH / g to 85 mgKOH / g, from the viewpoints of pigment dispersibility and storage stability. Here, the acid value is defined as the mass (mg) of KOH required to completely neutralize 1 g of resin, and is measured by the method described in JIS standard (JIS K 0070, 1992). is.

[0071] The weight average molecular weight (Mw) of the pigment dispersing resin is preferably 30,000 or more, more preferably 30,000 to 150,000, even more preferably 30,000 to 100,000, and still more preferably 30,000 to 80,000.

[0072] When the first resin contains a pigment dispersion resin, the content of the pigment dispersion resin is preferably 1% by mass to 25% by mass, more preferably 1% by mass to 20% by mass, even 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 first ink.

[0073] When the first resin contains a pigment dispersing resin, the ratio of the pigment dispersing resin (D) to the pigment (P) (i.e., the D / P ratio) is preferably 0.05 to 3, more preferably 0.05 to 2, even more preferably 0.05 to 1, and still more preferably 0.05 to 0.7.

[0074] -Resin particles- The first resin may include resin particles. Here, the resin particles are distinguished from the pigment dispersion resin described above in that they are particles made of resin. The resin constituting the resin particles is preferably a water-insoluble resin. When the first resin contains resin particles, when the resin particles in the first ink come into contact with the aggregating agent in the pretreatment liquid on the non-permeable substrate, the resin particles in the first ink aggregate, causing the first ink to thicken. Therefore, when the first resin contains resin particles, the strength and adhesion of the image are improved compared to when the first resin does not contain resin particles. Furthermore, when the first resin contains resin particles, the increase in viscosity of the first ink is more suppressed and the deterioration of the ejection properties of the first ink is more suppressed compared to when the first resin contains the same mass of water-soluble resin.

[0075] There is no particular limitation on the glass transition temperature of the resin particles (that is, the glass transition temperature of the resin in the resin particles). From the viewpoint of further improving the strength of the image, the glass transition temperature (Tg) of the resin particles is preferably 20°C or higher, more preferably 50°C or higher, and even more preferably 80°C or higher. From the viewpoint of the manufacturing suitability of the resin particles, the glass transition temperature (Tg) of the resin particles is preferably 150°C or lower, and more preferably 130°C or lower.

[0076] In the method for producing an image recorded matter according to the present disclosure, from the viewpoint of further improving the adhesion of the image, The pretreatment liquid contains a resin, the first resin in the first ink contains resin particles; The glass transition temperature of the resin contained in the pretreatment liquid is preferably lower than the glass transition temperature of the resin particles contained in the first resin. In this case, the value obtained by subtracting the glass transition temperature of the resin contained in the pretreatment liquid from the glass transition temperature of the resin particles contained in the first resin is preferably 20°C or higher, more preferably 30°C or higher, and even more preferably 40°C or higher. There is no particular upper limit to this value, but examples of upper limits include 100°C, 150°C, and 200°C.

[0077] The resin particles are preferably particles made of an acrylic resin (hereinafter also referred to as acrylic resin particles), particles made of a polyester resin (hereinafter also referred to as polyester resin particles), particles made of a polyurethane resin (hereinafter also referred to as polyurethane resin particles), or particles made of a polyolefin. The particles are made of polyolefin resin (hereinafter also referred to as polyolefin resin particles).

[0078] The resin particles contained in the first ink preferably contain acrylic resin particles, from the viewpoint of further improving the adhesion and abrasion resistance of the image. When the resin particles contained in the first ink include acrylic resin particles, the ratio of the acrylic resin particles to the resin particles contained in the first ink is preferably 60% by mass or more, more preferably 80% by mass or more, and even more preferably 90% by mass or more. When the proportion of acrylic resin particles in the resin particles contained in the first ink is 60% by mass or more, the adhesion of the image is further improved.

[0079] The resin particles are preferably self-dispersing resin particles. Examples of the self-dispersing resin particles include the self-dispersing polymer particles described in paragraphs 0062 to 0076 of JP 2016-188345 A and paragraphs 0109 to 0140 of WO 2013 / 180074 A.

[0080] The resin in the resin particles preferably contains an alicyclic structure or an aromatic ring structure, and more preferably contains an alicyclic structure. The alicyclic structure is preferably an alicyclic hydrocarbon structure having 5 to 10 carbon atoms, and a cyclohexane ring structure, a dicyclopentanyl ring structure, a dicyclopentenyl ring structure, a norbornane ring structure, an isobornane ring structure, a norbornene ring structure, an isobornene ring structure, or an adamantane ring structure is preferred. The aromatic ring structure is preferably a naphthalene ring or a benzene ring, more preferably a benzene ring. The amount of the alicyclic structure or aromatic ring structure is, for example, preferably 0.01 mol to 1.5 mol, and more preferably 0.1 mol to 1 mol, per 100 g of resin in the resin particles.

[0081] The resin in the resin particles preferably has an ionic group in its structure, from the viewpoint of further improving the water dispersibility of the resin particles. The ionic group may be either an anionic group or a cationic group, but an anionic group is preferred. The anionic group is not particularly limited, but is preferably a carboxy group, a salt of a carboxy group, a sulfo group, or a salt of a sulfo group.

[0082] As the resin in the resin particles, More preferably, the acrylic resin contains at least one selected from the group consisting of a benzyl (meth)acrylate unit, a phenoxyethyl (meth)acrylate unit, and an alicyclic structure-containing (meth)acrylate unit, and a (meth)acrylic acid unit, More preferred is an acrylic resin containing at least one selected from the group consisting of benzyl (meth)acrylate units, phenoxyethyl (meth)acrylate units, and alicyclic structure-containing (meth)acrylate units, (meth)acrylic acid units, alkyl (meth)acrylate units containing an alkyl group having 1 to 4 carbon atoms, and alkyl (meth)acrylate units containing an alkyl group having 5 to 12 carbon atoms.

[0083] The alicyclic structure-containing (meth)acrylate is preferably at least one selected from alkyl (meth)acrylates having a cycloalkyl group having 3 to 10 carbon atoms (for example, cyclohexyl (meth)acrylate), isobornyl (meth)acrylate, adamantyl (meth)acrylate, and dicyclopentanyl (meth)acrylate; At least one selected from isobornyl (meth)acrylate, adamantyl (meth)acrylate, and dicyclopentanyl (meth)acrylate is more preferred.

[0084] The acid value of the resin in the resin particles is preferably 25 mgKOH / g to 100 mgKOH / g, more preferably 30 mgKOH / g to 90 mgKOH / g, and even more preferably 35 mgKOH / g to 80 mgKOH / g, from the viewpoints of self-dispersibility, aggregation during image recording, and the like.

[0085] The molecular weight of the resin in the resin particles is preferably 1,000 to 300,000, more preferably 2,000 to 200,000, and even more preferably 5,000 to 100,000, in terms of weight average molecular weight. The weight average molecular weight is measured by gel permeation chromatography (GPC), the details of which are as described above.

[0086] The volume average particle size of the 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.

[0087] When the first ink contains resin particles, the content of the resin particles relative to the total amount of the first ink is preferably 1% by mass to 25% by mass, more preferably 2% by mass to 20% by mass, even more preferably 2% by mass to 15% by mass, and even more preferably 2% by mass to 10% by mass.

[0088] (Water-soluble organic solvent with a boiling point below 220°C) The first ink preferably contains at least one water-soluble organic solvent with a boiling point of less than 220°C. This further improves the lamination strength of the image recorded product. In this disclosure, boiling point means the boiling point at 1 atmosphere (101325 Pa).

[0089] Examples of water-soluble organic solvents with a boiling point of less than 220°C include 1,2-propanediol (also known as propylene glycol; PG) (boiling point 188°C), 1,3-propanediol (boiling point 213°C), propylene glycol monomethyl ether (boiling point 121°C), ethylene glycol (boiling point 197°C), ethylene glycol monomethyl ether (boiling point 124°C), propylene glycol monoethyl ether (boiling point 133°C), ethylene glycol monoethyl ether (boiling point 135°C), propylene glycol monopropyl ether ( boiling point 149°C), ethylene glycol monopropyl ether (boiling point 151°C), propylene glycol monobutyl ether (boiling point 170°C), ethylene glycol monobutyl ether (boiling point 171°C), 2-ethyl-1-hexanol (boiling point 187°C), dipropylene glycol monomethyl ether (boiling point 188°C), diethylene glycol dimethyl ether (boiling point 162°C), diethylene glycol diethyl ether (boiling point 188°C), dipropylene glycol dimethyl ether (boiling point 175°C), and the like.

[0090] When the first ink contains a water-soluble organic solvent with a boiling point of less than 220°C, the content of the water-soluble organic solvent with a boiling point of less than 220°C is preferably 1% by mass to 50% by mass, more preferably 5% by mass to 40% by mass, even more preferably 10% by mass to 40% by mass, and even more preferably 15% by mass to 35% by mass, relative to the total amount of the ink.

[0091] (Organic solvents with a boiling point of 220°C or higher) The content of organic solvents with a boiling point of 220°C or higher (hereinafter also referred to as "high boiling point solvents") in the first ink is preferably 5% by mass or less, which further improves the lamination strength of the image-recorded product and the adhesion of the image. Here, "the content of organic solvents with a boiling point of 220° C. or higher in the first ink is 5% by mass or less" means that the first ink does not contain organic solvents with a boiling point of 220° C. or higher (i.e., the first ink This means that the content of organic solvents with a boiling point of 220°C or higher in the first ink is 0% by mass, or even if they are contained, the content of organic solvents with a boiling point of 220°C or higher is 5% by mass or less relative to the total amount of the first ink. The content of organic solvents with a boiling point of 220°C or higher in the first ink is more preferably 3% by mass or less, even more preferably 2% by mass or less, even more preferably 1% by mass or less, and even more preferably 0% by mass.

[0092] The meaning of "the content of organic solvents with a boiling point of 220°C or higher in the second ink is 5% by mass or less" described below is the same as "the content of organic solvents with a boiling point of 220°C or higher in the first ink is 5% by mass or less", and the preferred content of high-boiling point solvents in the second ink is the same as the preferred content of high-boiling point solvents in the first ink.

[0093] Examples of organic solvents with a boiling point of 220°C or higher include glycerin (boiling point 290°C), 1,2-hexanediol (HDO) (boiling point 223°C), diethylene glycol (boiling point 245°C), diethylene glycol monobutyl ether (boiling point 230°C), triethylene glycol (boiling point 285°C), dipropylene glycol (boiling point 232°C), tripropylene glycol (boiling point 267°C), trimethylolpropane (boiling point 295°C), 2-pyrrolidone (boiling point 245°C), tripropylene glycol monomethyl ether (boiling point 243°C), and triethylene glycol monomethyl ether (boiling point 248°C).

[0094] (surfactant) The first ink may contain at least one surfactant. Examples of the surfactant include a nonionic surfactant, a cationic surfactant, an anionic surfactant, and a betaine surfactant.

[0095] Preferred surfactants include acetylene glycol surfactants, which are a type of nonionic surfactant. As the acetylene glycol surfactant, for example, the acetylene glycol surfactants described in paragraphs 0070 to 0080 of WO 2017 / 149917 can be used. Examples of acetylene glycol surfactants include: a polyalkylene oxide adduct (preferably a polyethylene oxide adduct) of 2,4,7,9-tetramethyl-5-decyne-4,7-diol; a polyalkylene oxide adduct (preferably a polyethylene oxide adduct) of 3,6-dimethyl-4-octyne-3,6-diol; a polyalkylene oxide adduct (preferably a polyethylene oxide adduct) of 2,5,8,11-tetramethyl-6-dodecyne-5,8-diol; Examples include polyalkylene oxide adducts (preferably polyethylene oxide adducts) of 2,5-dimethyl-3-hexyne-2,5-diol. Commercially available acetylene glycol surfactants include the Surfynol series (e.g., Surfynol 420, Surfynol 440, Surfynol 465, Surfynol 485), the Olfin series (e.g., Olfin E1010, Olfin E1020), and the Dynol series (e.g., Dynol 604) manufactured by Air Products Co., Ltd. or Nissin Chemical Industry Co., Ltd.; and Acetylenol manufactured by Kawaken Fine Chemicals Co., Ltd. Commercially available acetylene glycol surfactants are also provided by The Dow Chemical Company, General Aniline Company, and others.

[0096] As the surfactant, the compounds listed as surfactants on pages 37-38 of JP-A-59-157636 and Research Disclosure No. 308119 (1989) can be used. Further examples include fluorine (alkyl fluoride) surfactants and silicone surfactants described in JP-A Nos. 2003-322926, 2004-325707 and 2004-309806.

[0097] When the first ink contains a surfactant, the content of the surfactant in the first ink is adjusted appropriately in consideration of the surface tension of the first ink. The content of the surfactant in the first ink is preferably 0.01% to 5% by mass, more preferably 0.05% to 3% by mass, and even more preferably 0.1% to 2% by mass, relative to the total amount of the first ink.

[0098] (Silicate compounds) The first ink may contain at least one silicate compound. When the first ink contains a silicate compound, the ejection stability of the first ink from the inkjet head can be further improved. As the silicic acid compound, for example, the compounds described in paragraphs 0058 to 0075 of Japanese Patent No. 5430316 can be used. The silicate compounds are: Silicates (e.g., sodium silicate, potassium silicate, calcium silicate, magnesium silicate, ammonium salts of silicic acid, etc.) or anhydrous silicic acid (silica) are preferred; Silica is more preferred, Colloidal silica is more preferred. As the colloidal silica, commercially available products may be used. Specific examples of commercially available products include Snowtex S, Snowtex XS, Snowtex 20, Snowtex 30, Snowtex 40, Snowtex N, Snowtex C, and Snowtex O (all manufactured by Nissan Chemical Industries, Ltd.).

[0099] The content of the silicate compound in the first ink is preferably 0.0001% by mass to 1% by mass, more preferably 0.0005% by mass to 0.5% by mass, even more preferably 0.001% by mass to 0.5% by mass, and even more preferably 0.01% by mass to 0.3% by mass, relative to the total amount of the first ink.

[0100] (Other ingredients) The first ink may contain other components in addition to the above components. Examples of other components include known additives such as urea, urea derivatives, wax, anti-fading agents, emulsion stabilizers, penetration enhancers, ultraviolet absorbers, preservatives, anti-mold agents, pH adjusters, antifoaming agents, viscosity adjusters, dispersion stabilizers, and chelating agents.

[0101] (Preferable physical properties of the first ink) The viscosity (25° C.) of the first ink is preferably 1.2 mPa·s or more and 15.0 mPa·s or less, more preferably 2 mPa·s or more and less than 13 mPa·s, and more preferably 2.5 mPa·s or more and less than 10 mPa·s.

[0102] The surface tension of the first ink (at 25° C.) is preferably 25 mN / m to 50 mN / m, more preferably 30 mN / m to 45 mN / m, and even more preferably 30 mN / m to 40 mN / m.

[0103] The pH of the first ink at 25°C is preferably 6 to 11, more preferably 7 to 10, and even more preferably 7 to 9. The pH of the first ink at 25° C. is measured using a commercially available pH meter.

[0104] <Step of preparing the second ink> The process of preparing the second ink (hereinafter also referred to as the "second ink preparation process") is a process of preparing a second ink that contains a second pigment, a second resin, and water and has a surface tension lower than that of the first ink. The second ink preparation step may be a step of simply preparing a second ink that has been manufactured in advance, or may be a step of manufacturing the second ink.

[0105] The second ink is an ink similar to the first ink, except that the surface tension of the second ink is smaller than that of the first ink, and the preferred aspects of the second ink are also similar to the preferred aspects of the first ink.

[0106] Specific examples and preferred aspects of the second pigment contained in the second ink are the same as the specific examples and preferred aspects of the first pigment contained in the first ink. The hue of the second pigment is preferably different from the hue of the first pigment. Furthermore, it is preferable that the hue of the second ink is different from the hue of the first ink.

[0107] One specific embodiment of the method for producing an image recorded product of the present disclosure comprises: the hue of the first ink is a hue other than white (preferably a chromatic color or black, for example, cyan, magenta, yellow, black, etc.); In this embodiment, the hue of the second ink is white (see Examples below). In this embodiment, it is preferable that the first pigment contained in the first ink is a chromatic pigment and / or a black pigment, and the second pigment contained in the second ink is a white pigment. In this embodiment, for example, a transparent substrate is used as the non-permeable substrate, and a colored image (i.e., a chromatic image or a black image; for example, a pattern image such as letters or figures) is recorded on the non-permeable substrate using a first ink. Then, a white image (e.g., a solid image) is recorded on the non-permeable substrate with the colored image recorded thereon so as to cover the colored image. In this case, when observed from the non-image-recorded side (i.e., the side without an image recorded) of the non-permeable substrate, the colored image recorded with the first ink against the white image recorded with the second ink can be seen through the non-permeable substrate. On the other hand, when observed from the image-recorded side (i.e., the side with an image recorded) of the non-permeable substrate, the white image recorded with the second ink conceals the colored image and the non-permeable substrate, making them difficult to see. In this embodiment, the area of ​​the white image formed by the second ink tends to be larger than the area of ​​the colored image formed by the first ink in order to cover up the colored image formed by the first ink. As a result, in this embodiment, the effect of suppressing unevenness in the image surface and / or unevenness in image thickness (i.e., the effect of the surface tension of the second ink being smaller than that of the first ink, and the effect of the applied mass ratio [(first resin + second resin) / coagulant] being 16.0 or more) is more effectively exerted, and the laminate strength is further improved.

[0108] The above embodiment may also include an embodiment in which, for example, a multicolored image is recorded by applying multiple colored inks (e.g., four types: cyan ink, magenta ink, yellow ink, and black ink) to an area of ​​an impermeable substrate to which a pretreatment liquid has been applied, and a white ink (white ink) is applied as a second ink to cover the multicolored image, thereby recording a white image. In this case, the relationship between all of the multiple colored inks and the white ink serving as the second ink does not necessarily have to satisfy the conditions of the method for producing an image-recorded product of the present disclosure; it is sufficient that the relationship between at least one of the multiple colored inks and the white ink serving as the second ink satisfies the conditions of the method for producing an image-recorded product of the present disclosure. In this case, among the multiple colored inks, the colored ink that satisfies the conditions of the method for producing an image-recorded product of the present disclosure corresponds to the first ink.

[0109] The content of high boiling point solvents (i.e., organic solvents with a boiling point of 220°C or higher) in the second ink is also The content is preferably 5% by mass or less, which further improves the lamination strength of the image recording material and the adhesion of the image. From the viewpoint of further improving the lamination strength and image adhesion of the image recording material, it is more preferable that the content of organic solvents with a boiling point of 220°C or higher relative to the total amount of the first ink is 5% by mass or less, and that the content of organic solvents with a boiling point of 220°C or higher relative to the total amount of the second ink is 5% by mass or less.

[0110] (Surface tension difference [first ink - second ink]) As described above, the surface tension of the second ink is smaller than the surface tension of the first ink. As mentioned above, the surface tension of the first ink and the surface tension of the second ink are both values ​​measured at a temperature of 25° C. Examples of the surface tension measuring device are also as mentioned above. In other words, the value obtained by subtracting the surface tension of the second ink from the surface tension of the first ink (hereinafter referred to as the "surface tension difference [first ink - second ink]" or simply "surface tension difference") is greater than 0 mN / m. This improves the wetting and spreading of the second ink on the first ink applied to the non-permeable substrate, suppressing unevenness of the image surface and / or variations in image thickness, thereby improving adhesion between the image and the substrate for lamination and improving lamination strength in the laminate. From the viewpoint of further improving the laminate strength, the surface tension difference [first ink - second ink] is preferably 2.0 mN / m or more, more preferably 3.0 mN / m or more, and even more preferably 4.0 mN / m or more. There is no particular upper limit to the difference in surface tension (first ink - second ink), but the upper limit is, for example, 10.0 mN / m.

[0111] Specific examples and preferred aspects of the second resin contained in the second ink are the same as the specific examples and preferred aspects of the first resin contained in the first ink. For example, the second resin preferably contains resin particles, which further improves the adhesion between the layer made of the second ink (hereinafter also referred to as the "second ink layer") and the layer made of the first ink (hereinafter also referred to as the "first ink layer") and / or the layer made of the pretreatment liquid (hereinafter also referred to as the "pretreatment layer"), thereby further improving the laminate strength.

[0112] (Glass transition temperature difference (Ta-Tb)) A preferred embodiment of the method for producing an image recorded matter according to the present disclosure is one in which the first resin contains resin particles and the second resin contains resin particles. In this preferred embodiment, in an overlapping region (i.e., an overlapping region where a region to which the pretreatment liquid is applied, a region to which the first ink is applied, and a region to which the second ink is applied overlap in a planar view) of the resin particles contained in the first resin and the resin particles contained in the second resin, when the glass transition temperature of the resin particle with a larger applied mass per unit area is defined as Ta and the glass transition temperature of the resin particle with a smaller applied mass per unit area is defined as Tb, it is preferable that Ta and Tb satisfy the relationship 0°C≦Ta−Tb≦30°C. By ensuring that "0°C≦Ta-Tb" (i.e., Tb≦Ta), the film strength of the entire image (i.e., an image having a layer structure of second ink layer / first ink layer / pretreatment layer) is further improved, and as a result, the laminate strength is further improved. By satisfying "Ta-Tb≦30°C" (i.e., "Ta-Tb" is 30°C or less), the adhesion between the second ink layer and the first ink layer is further improved, resulting in further improved laminate strength. "Ta-Tb" is preferably 25°C or lower, more preferably 20°C or lower.

[0113] (Mixture viscosity difference (A1-A2)) A preferred embodiment of the method for producing an image recording material according to the present disclosure is one in which, when the viscosity of a mixture obtained by mixing a pretreatment liquid and a first ink is A1 (hereinafter also referred to as "mixture viscosity A1") and the viscosity of a mixture obtained by mixing a pretreatment liquid and a second ink is A2 (hereinafter also referred to as "mixture viscosity A2"), A1 and A2 satisfy A1-A2>0 mPa s. When A1-A2 > 0 mPa s is satisfied, the wetting and spreading properties of the second ink applied onto the first ink are improved, which in turn reduces unevenness of the image surface and / or variations in image thickness, thereby improving adhesion between the image and the laminating substrate and increasing lamination strength.

[0114] From the viewpoint of further improving the laminate strength, "A1-A2" is preferably 10 mPa·s or more, more preferably 20 mPa·s or more, and even more preferably 25 mPa·s or more. There is no particular limitation on the upper limit of "A1-A2", but the upper limit is, for example, preferably 50 mPa·s or less, and more preferably 40 mPa·s or less.

[0115] Here, the mixture viscosity A1 refers to a value measured as follows. The pretreatment liquid and the first ink are mixed at a liquid temperature of 25° C. such that the mass ratio of the pretreatment liquid to the first ink (i.e., the mass ratio [pretreatment liquid / first ink]) is 0.1. The viscosity of the resulting mixture is measured at a liquid temperature of 25° C. within 30 minutes after the completion of mixing the aggregating agent and the first ink. The viscosity is measured using a viscometer such as a VISCOMETER TV-22 type viscometer (manufactured by Toki Sangyo Co., Ltd.). The mixture viscosity A2 refers to a value measured in the same manner as the mixture viscosity A1, except that the first ink was replaced with the second ink.

[0116] <Image recording process> The image recording step is a step of applying the pretreatment liquid, the first ink, and the second ink in this order onto the non-permeable substrate to record an image. In the image recording process, the pretreatment liquid, the first ink, and the second ink are applied in this order to record an image under conditions (i.e., application arrangement) such that an overlapping region is created where the region to which the pretreatment liquid is applied, the region to which the first ink is applied, and the region to which the second ink is applied overlap in a planar view, and under conditions (i.e., application amounts) such that in the overlapping region, the ratio of the total applied mass of the first resin and the second resin per unit area to the applied mass of the coagulant per unit area (i.e., applied mass ratio [(first resin + second resin) / coagulant]) is 16.0 or more and 30.0 or less. The image recording process will be described in detail below.

[0117] (Order of application of pretreatment liquid, first ink, and second ink) In the image recording process, the pretreatment liquid, the first ink, and the second ink are applied in this order onto the non-permeable substrate. That is, in the image recording process, a pretreatment liquid is applied onto a non-permeable substrate, a first ink is applied onto the applied pretreatment liquid, and a second ink is applied onto the applied first ink. On a non-permeable substrate, the aggregating agent, which is a component of the pretreatment liquid, aggregates the components (e.g., the first resin) in the first ink applied onto the pretreatment liquid, and also aggregates the components (e.g., the second resin) in the second ink applied onto the first ink via the first ink. As a result, an image having a layer structure of "second ink layer / first ink layer / pretreatment layer ( / non-permeable substrate)" is formed on the non-permeable substrate. Here, the pretreatment layer, the first ink layer, and the second ink layer refer to the layer derived from the pretreatment liquid, the layer derived from the first ink, and the layer derived from the second ink, respectively.

[0118] The first ink may be applied onto a pretreatment liquid that has been heated and dried (preferable conditions will be described later). Alternatively, it may be applied onto a pre-treatment liquid that has not been heated and dried. From the viewpoint of suppressing bleeding, it is preferable that the first ink be applied onto the pretreatment liquid that has been heated and dried. Preferred conditions for heating and drying the pretreatment liquid will be described later.

[0119] The second ink may be applied onto the first ink that has been dried by heating (preferable conditions will be described later), or onto the first ink that has not been dried by heating. Even in an embodiment in which the second ink is applied onto a first ink that has not been heated and dried, bleeding and color mixing are suppressed because the first ink has already been thickened by the action of the pretreatment liquid at the time the second ink is applied. From the viewpoints of suppressing bleeding and improving the efficiency of image recording, the image recording step is preferably a step of applying a pretreatment liquid onto a non-permeable substrate and drying it by heating, and then applying the first ink and the second ink in this order onto the pretreatment liquid that has been dried by heating.

[0120] (Application arrangement of pretreatment liquid, first ink, and second ink) In the image recording process, the pretreatment liquid, the first ink, and the second ink are applied under conditions (i.e., application arrangement) such that an overlapping region is created in which the region to which the pretreatment liquid is applied, the region to which the first ink is applied, and the region to which the second ink is applied overlap in a planar view, to record an image. In the image recording process, the pretreatment liquid, the first ink, and the second ink may be applied under conditions (that is, application arrangements) that result in overlapping regions and regions other than the overlapping regions. For example, a first ink may be applied in a pattern onto an area to which the pretreatment liquid has been applied to form a patterned first ink layer, and then a second ink may be applied (for example, solidly) to an area spanning the first ink layer and an area other than the first ink layer (for example, an area covering the entire first ink layer and its periphery) to form a second ink layer. In this case, the area where the first ink layer is present corresponds to the above-mentioned "overlapping area," and the area where the first ink layer is not present but the second ink layer is present, and the area where neither the first ink layer nor the second ink layer is present correspond to the above-mentioned "area other than the overlapping area."

[0121] (Amounts of pretreatment liquid, first ink, and second ink applied) In the image recording process, the pretreatment liquid, the first ink, and the second ink are applied to the overlapping region to record an image under conditions (i.e., application amounts) such that the ratio of the total applied mass of the first resin and the second resin per unit area to the applied mass of the coagulant per unit area (i.e., applied mass ratio [(first resin + second resin) / coagulant]) is 16.0 or more and 30.0 or less. As described above, by setting the applied mass ratio [(first resin + second resin) / aggregant] in the overlapping region to 16.0 or more, excessive aggregation of the first resin and the second resin is suppressed in the overlapping region, and unevenness of the surface (i.e., the surface of the second ink layer) of the image (i.e., an image having a layer structure of second ink layer / first ink layer / pretreatment layer; the same applies below) and / or variations in image thickness due to excessive aggregation are suppressed. As a result, adhesion between the image and the lamination substrate is improved, and laminate strength is improved. As described above, by setting the mass ratio [(first resin + second resin) / aggregating agent] in the overlapping region to 30.0 or less, insufficient aggregation of the first resin and the second resin in the overlapping region is suppressed, resulting in improved adhesion between the impermeable substrate and the image, and improved laminate strength.

[0122] The applied mass ratio in the overlapping region [(first resin + second resin) / coagulant] is calculated based on the applied mass of coagulant per unit area in the overlapping region, the applied mass of the first resin per unit area in the overlapping region, and the applied mass of the second resin per unit area in the overlapping region. The applied mass of coagulant per unit area in the overlapping region (unit: g / m 2 ) is calculated based on, for example, the mass of the pretreatment liquid applied per unit area in the overlapping region and the content (mass %) of the flocculant relative to the total amount of the pretreatment liquid. The applied mass of the first resin per unit area in the overlapping region (unit: g / m 2 ) is calculated based on, for example, the mass of the first ink applied per unit area in the overlap region and the content (mass %) of the first resin relative to the total amount of the first ink. The mass of the second resin per unit area in the overlapping region (unit: g / m 2 ) is calculated based on, for example, the mass of the second ink applied per unit area in the overlap region and the content (mass %) of the second resin relative to the total amount of the second ink.

[0123] From the viewpoint of further improving the laminate strength, the applied mass ratio [(first resin+second resin) / coagulant] is preferably 16.0 or more and 25.0 or less, and more preferably 16.0 or more and 20.0 or less. From the viewpoint of further improving the laminate strength, the lower limit of the applied mass ratio [(first resin+second resin) / coagulant] is preferably 16.1, and more preferably 16.2.

[0124] The applied mass of coagulant per unit area in the overlapping region (unit: g / m 2) is preferably 0.040 to 0.100, and more preferably 0.045 to 0.075. The applied mass of pretreatment liquid per unit area in the overlapping region (unit: g / m 2 ) is preferably 1.0 to 2.0, more preferably 1.2 to 1.8.

[0125] The total applied mass of the first and second resins per unit area in the overlapping region (unit: g / m 2 ) is preferably 1.00 to 2.50, more preferably 1.00 to 2.00. The total applied mass of the first ink and the second ink per unit area in the overlapping region (unit: g / m 2 ) is preferably 14.0 to 30.0, more preferably 14.5 to 28.0.

[0126] The applied mass of the first resin per unit area in the overlapping region (unit: g / m 2 ) is preferably 0.45 to 1.00, more preferably 0.48 to 0.90. The applied mass of the first ink per unit area in the overlapping region (unit: g / m 2 ) is preferably 7.0 to 13.0, preferably 7.0 to 12.0, and more preferably 7.0 to 11.5.

[0127] The mass of the second resin per unit area in the overlapping region (unit: g / m 2 ) is preferably 0.40 to 2.00, preferably 0.40 to 1.30, and more preferably 0.50 to 1.10. The applied mass of the second ink per unit area in the overlapping region (unit: g / m 2 ) is preferably 7.0 to 20.0, preferably 7.0 to 18.0, and more preferably 7.0 to 16.0.

[0128] (Non-permeable base material) In the image recording process, the pretreatment liquid, the first ink, and the second ink are applied onto a non-permeable substrate. An impermeable substrate refers to a substrate that has a water absorption rate (mass %, 24 hours) of less than 0.2 according to ASTM test method ASTM D570. The impermeable substrate is not particularly limited, but a resin substrate is preferred. The resin substrate is not particularly limited, and examples thereof include substrates made of thermoplastic resins. Examples of the resin substrate include a substrate obtained by molding a thermoplastic resin into a sheet or film shape. The resin substrate is preferably a substrate containing polypropylene, polyethylene terephthalate, nylon, polyethylene, or polyimide.

[0129] The resin substrate may be a transparent resin substrate. Here, "transparent" means that the transmittance of visible light with a wavelength of 400 nm to 700 nm is 80% or more (preferably 90% or more). In the above-mentioned embodiment in which the hue of the first ink is a hue other than white (preferably a chromatic color or black, such as cyan, magenta, yellow, or black) and the hue of the second ink is white, if the non-permeable substrate is a transparent resin substrate, the colored image made by the first ink against the white image made by the second ink can be viewed through the non-permeable substrate from the non-image recording side (i.e., the side on which no image is recorded) of the non-permeable substrate. The resin substrate may be colored.

[0130] The shape of the resin substrate is not particularly limited, but is preferably a sheet-like resin substrate, and from the viewpoint of productivity of the recording medium, more preferably a sheet-like resin substrate that can be wound up to form a roll. The thickness of the resin substrate is preferably 10 μm to 200 μm, and more preferably 10 μm to 100 μm.

[0131] The resin substrate may be subjected to a surface treatment in order to improve the surface energy. Examples of surface treatments include, but are not limited to, corona treatment, plasma treatment, flame treatment, heat treatment, abrasion treatment, light irradiation treatment (UV treatment), and flame treatment.

[0132] (Application of pre-treatment liquid) In the image recording process, the pretreatment liquid can be applied to the non-permeable substrate by a known method such as a coating method, an ink jet method, or a dipping method. Examples of the coating method include known coating methods using a bar coater (for example, a wire bar coater), an extrusion die coater, an air doctor coater, a blade coater, a rod coater, a knife coater, a squeeze coater, a reverse roll coater, a gravure coater, a flexo coater, and the like. The inkjet method will be described in detail later.

[0133] In the image recording process, the non-permeable substrate may be heated before the pretreatment liquid is applied. The heating temperature is preferably set to 20°C to 50°C, more preferably 25°C to 40°C, for the temperature of the non-permeable substrate.

[0134] In the image recording step, after the application of the pretreatment liquid and before the application of the first ink, the pretreatment liquid may be dried by heating. Examples of 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. Examples of methods for heating and drying the pretreatment liquid include: a method of applying heat using a heater or the like from the side opposite to the surface of the non-permeable substrate to which the pretreatment liquid has been applied; a method of applying warm or hot air to the surface of a non-permeable substrate to which a pretreatment liquid has been applied; a method of applying heat by an infrared heater to the surface of the non-permeable substrate to which the pretreatment liquid has been applied or to the side opposite to the surface to which the pretreatment liquid has been applied; A combination of these methods, etc.

[0135] The heating temperature during 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 the upper limit is preferably 100°C, more preferably 90°C, and even more preferably 70°C. The heat drying time is not particularly limited, but is preferably 0.5 seconds to 60 seconds, more preferably 0.5 seconds to 20 seconds, and particularly preferably 0.5 seconds to 10 seconds.

[0136] (Application of first ink) In the image recording process, the first ink can be applied onto the pretreatment liquid (i.e., the pretreatment layer) by applying a known method such as a coating method, an inkjet method, or a dipping method, but is preferably applied by an inkjet method. There are no particular limitations on the method for ejecting the first ink in the inkjet method, and any of the well-known methods may be used, such as 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 piezoelectric element, an acoustic inkjet method that converts an electric signal into an acoustic beam and irradiates the ink with it, thereby ejecting the ink using radiation pressure, and a thermal inkjet (Bubble Jet (registered trademark)) method that heats the ink to form bubbles and uses the resulting pressure. As an ink jet method, in particular, the method described in Japanese Patent Laid-Open No. 54-59936 can be effectively used, in which ink subjected to the action of thermal energy undergoes a sudden change in volume, and the force caused by this state change causes the ink to be ejected from a nozzle. As the inkjet method, the method described in paragraphs 0093 to 0105 of JP-A No. 2003-306623 can also be applied.

[0137] The application of the first ink by the inkjet method is carried out by ejecting the first 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 printing, and the line method, which uses a line head in which printing elements are arranged to cover the entire area of ​​one side of the recording medium. The line method allows for image recording over 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 eliminates the need for a transport system, such as a carriage that scans a short head, as in the shuttle method. Furthermore, 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.

[0138] The first ink is preferably applied using an inkjet head having a resolution of 300 dpi or more (more preferably 600 dpi, and even more preferably 800 dpi), where dpi stands for dots per inch, and 1 inch is 2.54 cm.

[0139] The volume of droplets of the first ink ejected from the nozzles of the inkjet head is preferably 1 pL (picoliter) to 10 pL, and more preferably 1.5 pL to 6 pL, from the viewpoint of obtaining a high-definition image. Furthermore, from the viewpoint of improving image unevenness and continuous gradation, it is also effective to eject droplets of different amounts in combination.

[0140] In the image recording process, the first ink applied onto the pretreatment liquid (i.e., the pretreatment layer) may be heated and dried, and then the second ink may be applied onto the heated and dried first ink. The preferred conditions for the heat drying when heat drying is performed are the same as the preferred conditions for the heat drying after application of the second ink, which will be described later. As described above, in the image recording process, the second ink may be applied onto the first ink without heating and drying the first ink applied onto the pretreatment liquid (i.e., pretreatment layer). At the stage of applying the second ink, the first ink has already been thickened by the action of the coagulant. This is because.

[0141] Furthermore, the non-permeable substrate may be heated in advance before the first ink is applied. This heating may also serve as a heat drying of the pretreatment liquid. The heating temperature may be set appropriately, but the temperature of the non-permeable substrate is preferably set to 20°C to 50°C, and more preferably 25°C to 40°C.

[0142] (Application of second ink) In the image recording process, the second ink can be applied onto the first ink (i.e., the first ink layer) by applying a known method such as a coating method, an inkjet method, or a dipping method, but is preferably applied by an inkjet method. The inkjet method that can be applied to apply the second ink is the same as the inkjet method that can be applied to apply the first ink, and the preferred embodiments are also the same.

[0143] In the image recording step, after the second ink is applied, the first ink (that is, the first ink layer) and the second ink (that is, the second ink layer) on the non-permeable substrate may be dried by heating. Examples of means for performing heat drying include known heating means such as a heater, known air blowing means such as a dryer, and a combination of these. Examples of methods for heat drying include: a method of applying heat using a heater or the like from the side opposite to the surface of the non-permeable substrate on which the first ink and the second ink are applied; a method of applying warm or hot air to the surface of the non-permeable substrate on which the first ink and the second ink have been applied, and a method of applying heat using an infrared heater from the surface of the non-permeable substrate on which the first ink and the second ink have been applied or from the side opposite to the surface on which the inks have been applied; A combination of these methods, etc. The heating temperature during heat drying is preferably 55° C. or higher, more preferably 60° C. or higher, and particularly preferably 65° C. or higher. There is no particular upper limit to the heating temperature, but the upper limit can be, for example, 100° C., and preferably 90° C. The heat drying time is not particularly limited, but is preferably 3 to 60 seconds, more preferably 5 to 30 seconds, and particularly preferably 5 to 20 seconds.

[0144] [Method for manufacturing laminated body] As described above, according to the method for manufacturing an image recording material disclosed herein, it is possible to manufacture an image recording material that comprises a non-permeable substrate and an image recorded on the non-permeable substrate, and that has excellent lamination strength when a lamination substrate is laminated onto the image. Therefore, the method for manufacturing an image recording material of the present disclosure is suitable for use in manufacturing a laminated body comprising the image recording material and a lamination substrate laminated on the side of the image recording material on which the image is located. The method for producing the laminated body will now be described.

[0145] The method for producing a laminate according to the present disclosure includes: A step of obtaining an image recorded material by the method for producing an image recorded material 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 arranged to obtain a laminate; Includes:

[0146] According to the method for producing a laminated body of the present disclosure, it is possible to produce a laminated body having excellent lamination strength (i.e., peel strength) between an image-recorded material and a substrate for lamination.

[0147] For the process of obtaining an image recording, the image recording method of the present disclosure described above can be referred to. The step of obtaining a laminated body is a step of laminating a substrate for lamination onto the side of the image-recorded product on which the image is arranged, to obtain a laminated body.

[0148] 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 may be, for example, a substrate formed from a thermoplastic resin in the form of a sheet. The resin substrate preferably contains polypropylene, polyethylene terephthalate, nylon, polyethylene, or polyimide.

[0149] The shape of the resin substrate is not particularly limited, but a sheet-like resin substrate is preferred. The thickness of the resin substrate is preferably 10 μm to 200 μm, and more preferably 10 μm to 100 μm.

[0150] In this step, the substrate for lamination may be laminated directly onto the image-side of the image-recorded product, or may be laminated via another layer (for example, an adhesive layer).

[0151] When the substrate for lamination is directly laminated onto the image side of the image recorded product, the lamination can be carried out by a known method such as thermocompression bonding or heat fusion bonding.

[0152] Furthermore, when laminating a substrate for lamination onto the side of the image-recorded product on which the image is arranged via an adhesive layer, the lamination can be carried out, for example, by applying an adhesive to the side of the image-recorded product on which the image is recorded, then placing the substrate for lamination on the side, and then bonding the image-recorded product and the substrate for lamination together. Furthermore, lamination via an adhesive layer on the image-bearing side of the image-recorded product can also be carried out by a method such as extrusion lamination (i.e., sandwich lamination).

[0153] In the embodiment in which the image-recorded product is laminated on the image-bearing side via an adhesive layer, the adhesive layer preferably contains an isocyanate compound. When the adhesive layer contains an isocyanate compound, the adhesion between the adhesive layer and the ink-derived layer of the image is further improved, and therefore the laminate strength can be further improved.

[0154] [Image Recordings] An image recording according to an example of the present disclosure includes: an impermeable substrate; and an image recorded on the impermeable substrate; the image includes a pretreatment layer in contact with the non-permeable substrate and containing a flocculant, a first layer in contact with the pretreatment layer and containing a first pigment and a first resin, and a second layer in contact with the first layer and containing a second pigment and a second resin, and includes an overlapping region in which the pretreatment layer, the first layer, and the second layer overlap in a planar view; the flocculant is at least one selected from the group consisting of an organic acid, an organic acid salt, a polyvalent metal compound, and a metal complex; In the overlapping region, the ratio of the total mass of the first resin and the second resin per unit area to the mass of the flocculant per unit area is 16.0 or more and 30.0 or less.

[0155] The image recorded matter according to this example has excellent lamination strength when a lamination substrate is laminated on the image.

[0156] The image recording material according to this example is preferably manufactured by the manufacturing method of the image recording material according to the present disclosure. In this case, the first layer corresponds to the first ink layer after drying, and the second layer corresponds to the second ink layer after drying. The first layer corresponds to the ink layer. However, the solvent may remain in each of the first layer, the second layer, and the pretreatment layer. The preferred aspects of each component in the image recorded matter according to this example are the same as the preferred aspects of each component explained in the section on the method for producing an image recorded matter of the present disclosure.

[0157] [Laminated body] A laminate according to one example of the present disclosure includes the image recorded matter of the present disclosure described above and a lamination substrate laminated onto the image of the image recorded matter. The laminate according to this example has excellent laminate strength.

[0158] In the laminated body of this example, the laminating substrate may be laminated directly to the side of the image-recorded material on which the image is recorded, or may be laminated via another layer (adhesive layer). The laminate according to this example is preferably manufactured by the laminate manufacturing method of the present disclosure. The preferred embodiments of the substrate for lamination and the adhesive layer are the same as those described in the section on the method for producing the laminate. [Example]

[0159] Examples of the present disclosure will be described below, but the present disclosure is not limited to the following examples. Unless otherwise specified, "%" and "parts" hereinafter refer to % by mass and parts by mass, respectively. "Tg" means the glass transition temperature, and the Tg difference (Ta-Tb) means the above-mentioned glass transition temperature difference (Ta-Tb). Ion-exchanged water was used as "water."

[0160] <Preparing the pretreatment solution> Pretreatment solutions PC1, PC2, and PC3 were prepared as follows.

[0161] (Preparation of pretreatment solution PC1) The components shown below were mixed to prepare pretreatment solution PC1.

[0162] -Composition of pretreatment solution PC1- Glutaric acid (Fujifilm Wako Pure Chemical Industries, Ltd.; flocculant (organic acid)) …4% by mass Resin particles PC1 (Tg50℃) ... 5% by mass as the solid content of the following resin particles PC1 1,2-propanediol (Fujifilm Wako Pure Chemical Industries, Ltd.; water-soluble organic solvent) …10% by mass ·water … The remaining amount that makes up 100% by mass

[0163] -Preparation of aqueous dispersion of resin particles PC1 (Tg 50°C)- As an aqueous dispersion of resin particles PC1 (Tg 50°C), "Pesresin A-520" (a 30 mass % aqueous dispersion of polyester resin particles (Tg 50°C) as resin particles PC1) manufactured by Takamatsu Oil & Fat Co., Ltd. was prepared.

[0164] (Preparation of pretreatment solution PC2) Glutaric acid as a flocculant was mixed with the same mass of calcium acetate (Fujifilm Wako Pure Chemical Industries, Ltd.; Pretreatment liquid PC2 was prepared in the same manner as pretreatment liquid PC1, except that the flocculant was changed to organic acid salt.

[0165] (Preparation of pretreatment solution PC3) A resin-free pretreatment liquid PC3 was prepared in the same manner as the preparation of pretreatment liquid PC1, except that the aqueous dispersion of resin particles PC1 was not used and the amount of water was adjusted so that the glutaric acid content was 4 mass %.

[0166] <Preparation of the first ink and the second ink> Inks A to H were prepared as first inks, and inks I to M were prepared as second inks. The first inks are all cyan inks, and the second inks are all white inks. Details are shown below.

[0167] (Preparation of Ink A) Ink A, the first ink, was prepared as follows.

[0168] -Synthesis of pigment dispersing resin 1- A 1000 mL three-neck flask equipped with a stirrer and condenser was charged with 88 g of methyl ethyl ketone and heated to 72°C under a nitrogen atmosphere. A solution of 0.85 g of dimethyl 2,2'-azobisisobutyrate, 60 g of benzyl methacrylate, 10 g of methacrylic acid, and 30 g of methyl methacrylate dissolved in 50 g of methyl ethyl ketone was added dropwise over 3 hours. After the addition was completed and the mixture was allowed to react for another hour, a solution of 0.42 g of dimethyl 2,2'-azobisisobutyrate dissolved in 2 g of methyl ethyl ketone was added, and the temperature was raised to 78°C and heated for 4 hours. The resulting reaction solution was reprecipitated twice in a large excess of hexane, and the precipitated resin was dried. In this way, 96 g of pigment dispersion resin 1, a benzyl methacrylate / methyl methacrylate / methacrylic acid copolymer (60 / 30 / 10 [mass ratio]), was obtained. The composition of the resulting pigment dispersion resin 1 was: 1 The weight average molecular weight (Mw) was confirmed by H-NMR and calculated as polystyrene by GPC, and was 44600. Furthermore, the acid value was determined by the method described in JIS standard (JISK0070:1992), and was found to be 65.2 mgKOH / g.

[0169] -Preparation of pigment dispersion C- A mixture of 4 parts of CI Pigment Blue 15:3 (Dainichiseika Color & Chemicals Mfg. Co., Ltd.), 2 parts of the pigment dispersion resin 1 obtained above, 42 parts of methyl ethyl ketone, 5.5 parts of 1N aqueous NaOH solution, and 87.2 parts of water was dispersed in a bead mill using 0.1 mm diameter zirconia beads at 2500 rpm (revolutions per minute) for 6 hours. The resulting dispersion was concentrated under reduced pressure at 55°C until the methyl ethyl ketone was sufficiently removed. After further removal of some of the water, the mixture was centrifuged (using a 50 mL centrifuge tube) at 8000 rpm for 30 minutes in a high-speed centrifugal chiller 7550 (Kubota Manufacturing Co., Ltd.). The precipitate was removed and the supernatant was recovered. In this way, pigment dispersion C containing a resin-coated pigment in which the cyan pigment was at least partially coated with pigment dispersing resin 1 was obtained.

[0170] -Preparation of aqueous dispersion of resin particles 1 (Tg 100°C)- A 2-liter three-neck flask equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen gas inlet tube was charged with 560.0 g of methyl ethyl ketone and heated to 87°C. Next, while maintaining a reflux state in the reaction vessel (hereinafter, the reflux state was maintained until the end of the reaction), 336.4 g of methyl methacrylate and 6 g of isobornyl methacrylate were added to the methyl ethyl ketone in the reaction vessel. A mixed solution consisting of 9.6 g of ethanol, 116.0 g of 2-ethylhexyl methacrylate, 58 g of methacrylic acid, 108 g of methyl ethyl ketone, and 2.32 g of "V-601" (a polymerization initiator manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.; dimethyl 2,2'-azobis(2-methylpropionate)) was added dropwise at a constant rate so that the addition was completed within 2 hours. After the addition was completed, the mixture was stirred for 1 hour, and then the solution after stirring for 1 hour was subjected to the operation of the following step (1). Step (1): A solution consisting of 1.16 g of "V-601" and 6.4 g of methyl ethyl ketone was added and stirred for 2 hours.

[0171] Subsequently, the operation of the above step (1) was repeated four times, and then a solution consisting of 1.16 g of "V-601" and 6.4 g of methyl ethyl ketone was further added and stirred for 3 hours (the operation up to this point is referred to as "reaction"). After the reaction was completed, the temperature of the solution was lowered to 65°C, 163.0 g of isopropanol was added, and the mixture was allowed to cool, thereby obtaining a polymerization solution (solid concentration 41.0%) containing a methyl methacrylate / isobornyl methacrylate / 2-ethylhexyl methacrylate / methacrylic acid (=58 / 12 / 20 / 10 [mass ratio]) copolymer. The copolymer had a weight average molecular weight (Mw) of 35,000 and an acid value of 65.1 (mgKOH / g).

[0172] Next, 317.3 g of the obtained polymerization solution (solid content concentration: 41.0 mass%) was weighed, and 46.4 g of isopropanol, 1.65 g of a 20% aqueous maleic anhydride solution (a water-soluble acidic compound, equivalent to 0.3 mass% of maleic acid relative to the copolymer), and 40.77 g of a 2 mol / L aqueous NaOH solution were added, and the temperature of the liquid in the reaction vessel was raised to 70°C. Next, 380 g of water was added dropwise to the solution heated to 70° C. at a rate of 10 mL / min to carry out aqueous dispersion (dispersion step). The temperature of the liquid in the reaction vessel was then maintained at 70°C under reduced pressure for 1.5 hours to distill off a total of 287.0 g of isopropanol, methyl ethyl ketone, and water (solvent removal step). 0.278 g of Proxel GXL(S) (Arch Chemicals Japan) (440 ppm of benzoisothiazolin-3-one relative to the polymer solids) was added to the resulting liquid. The resulting liquid was filtered through a 1 μm filter, and the filtrate was collected to obtain an aqueous dispersion of resin particles 1 with a solid content concentration of 26.5 mass %. Resin particles 1 had a Tg of 100° C. and a volume average particle size of 10 nm.

[0173] -Preparation of Ink A- Ink A having the following composition was prepared using pigment dispersion C, an aqueous dispersion of resin particles 1, 1,2-propanediol (hereinafter also referred to as "PG"; a water-soluble organic solvent with a boiling point of less than 220°C), a surfactant (Olfine (registered trademark) E1010 manufactured by Nissin Chemical Industry Co., Ltd.), colloidal silica (Snowtex (registered trademark) XS (solid content 20% by mass) manufactured by Nissan Chemical Industries, Ltd.), and water.

[0174] -Composition of Ink A- Cyan pigment: 4% by mass Pigment dispersion resin 1... 2% by mass 1,2-propanediol (PG; a water-soluble organic solvent with a boiling point of less than 220°C)... 25% by mass Surfactant (Olfine (registered trademark) E1010 manufactured by Nissin Chemical Industry Co., Ltd.)... 0.5% by mass ·Resin particles 1...5% by mass Colloidal silica (Nissan Chemical Industries, Ltd.'s Snowtex (registered trademark) XS (silica solid content 20% by mass))... 0.06% by mass as silica solid content Water: The remaining amount to make the total 100% by mass

[0175] (Preparation of Inks B to H) Inks B to H were prepared as first inks in the same manner as ink A, except that the ink compositions were changed as shown in Table 1. In Table 1, HDO is 1,2-hexanediol, a high-boiling point solvent (i.e., an organic solvent with a boiling point of 220°C or higher); Resin particles 2 are resin particles synthesized as follows: The resin particles 3 are synthesized as follows.

[0176] -Preparation of aqueous dispersion of resin particles 2 (Tg 80°C)- An aqueous dispersion of resin particles 2 with a solids concentration of 26.5% by mass was obtained in the same manner as the aqueous dispersion of resin particles 1, except that the amount of each monomer was changed so that the copolymerization ratio [methyl methacrylate / isobornyl methacrylate / 2-ethylhexyl methacrylate / methacrylic acid] in the copolymer was 42 / 11 / 37 / 10 [mass ratio], the weight average molecular weight (Mw) was 35,000, and the acid value was 65.1 (mgKOH / g). The Tg of the resin particles 2 was 80° C., and the volume average particle size was 10 nm.

[0177] -Preparation of aqueous dispersion of resin particles 3 (Tg 120°C)- An aqueous dispersion of resin particles 3 with a solids concentration of 26.5% by mass was obtained in the same manner as the aqueous dispersion of resin particles 1, except that the amount of each monomer was changed so that the copolymerization ratio [methyl methacrylate / isobornyl methacrylate / 2-ethylhexyl methacrylate / methacrylic acid] in the copolymer was 70 / 16 / 4 / 10 [mass ratio], the weight average molecular weight (Mw) was 35,000, and the acid value was 65.1 (mgKOH / g). The Tg of the resin particles 3 was 120° C., and the volume average particle size was 10 nm.

[0178] (Preparation of Ink I) The second ink was prepared as follows.

[0179] -Synthesis of pigment dispersing resin 2- Pigment dispersing resin 2 was synthesized as follows. Dipropylene glycol was added to a three-neck flask equipped with a stirrer and a condenser in an amount equal to the total amount of the monomers described below, and heated to 85° C. under a nitrogen atmosphere. Solution 1 was prepared by mixing 9.1 molar equivalents of stearyl methacrylate, 34.0 molar equivalents of benzyl methacrylate, 31.9 molar equivalents of hydroxyethyl methacrylate, 25.0 molar equivalents of methacrylic acid, and 0.8 molar equivalents of 2-mercaptopropionic acid, while Solution 2 was prepared by dissolving 1% by mass of t-butylperoxy-2-ethylhexanoate (Perbutyl O, manufactured by NOF Corporation) relative to the total amount of monomers in 20% by mass of dipropylene glycol relative to the total amount of monomers. 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, the reaction was continued for another 2 hours, and then the temperature was raised to 95°C and the mixture was heated and stirred for 3 hours to allow all unreacted monomer to react. The disappearance of the monomer was monitored by nuclear magnetic resonance ( 1 This was confirmed by H-NMR. The resulting reaction solution was heated to 70° C., and 20.0 molar equivalents of dimethylethanolamine as an amine compound was added, followed by the addition of propylene glycol and stirring to obtain a 30% by mass solution of pigment dispersing resin 2. The components of the resulting polymer are: 1 The weight average molecular weight (Mw) was determined by GPC and was found to be 22,000. The mass ratio of each constituent unit in the pigment dispersion resin 2 is The ratio of structural units derived from benzyl methacrylate / structural units derived from hydroxyethyl methacrylate / structural units derived from methacrylic acid was 20 / 39 / 27 / 14. However, this mass ratio does not include dimethylaminoethanol.

[0180] -Preparation of pigment dispersion W- A ready mill, model LSG-4U-08 (manufactured by Imex Co., Ltd.), was used to prepare pigment dispersion W as follows. A zirconia container was charged with 45 parts by mass of titanium dioxide particles (TiO2 particles; average primary particle diameter: 210 nm, product name: PF-690, manufactured by Ishihara Sangyo Kaisha, Ltd.) as a white pigment (white inorganic pigment), 15 parts by mass of a 30% by mass solution of the above-mentioned pigment dispersion resin 2, and 40 parts by mass of ultrapure water. Furthermore, 40 parts by mass of 0.5 mm diameter zirconia beads (manufactured by TORAY, Toraceram beads) were added and gently mixed with a spatula. The zirconia container containing the resulting mixture was placed in a ball mill and dispersed at 1000 rpm for 5 hours. After dispersion was complete, the beads were removed by filtration using a filter cloth, yielding pigment dispersion W with a TiO2 concentration of 45% by mass.

[0181] -Preparation of Ink I- Ink I having the following composition was prepared using pigment dispersion W, an aqueous dispersion of resin particles 3, 1,2-propanediol (PG; a water-soluble organic solvent with a boiling point of less than 220°C), a surfactant (Olfine (registered trademark) E1010 manufactured by Nissin Chemical Industry Co., Ltd.), colloidal silica (Snowtex (registered trademark) XS (solid content 20% by mass) manufactured by Nissan Chemical Industries, Ltd.), and water.

[0182] -Composition of Ink I- ·White pigment (TiO2)…8% by mass Pigment dispersing resin 2... 0.5% by mass 1,2-propanediol (PG; a water-soluble organic solvent with a boiling point of less than 220°C)... 25% by mass Surfactant (Olfine (registered trademark) E1010 manufactured by Nissin Chemical Industry Co., Ltd.)... 1.2% by mass ·Resin particles 3...6% by mass Colloidal silica (Nissan Chemical Industries, Ltd.'s Snowtex (registered trademark) XS (silica solid content 20% by mass))... 0.06% by mass as silica solid content Water: The remaining amount to make the total 100% by mass

[0183] (Preparation of Inks J to M) Inks J to M were prepared as second inks in the same manner as ink I, except that the ink compositions were changed as shown in Table 1.

[0184] [Table 1]

[0185] [Examples 1 to 21, Comparative Examples 1 to 8] The pretreatment liquid, first ink, and second ink were used in the combinations shown in Table 2, and the following measurements, image recording, and evaluations were carried out.

[0186] <Measurement of each ink> The surface tension and mixture viscosity A1 of the first inks (inks A to H) were measured by the methods described above. The Tg (°C) of the first resin in each of the first inks (inks A to H) was also determined. The surface tension and mixture viscosity A2 of the second inks (inks I to M) were measured by the methods described above. The Tg (°C) of the second resin in each of the second inks (inks I to M) was also determined. Based on the results obtained, the surface tension difference (i.e., the surface tension of the first ink minus the surface tension of the second ink), the mixture viscosity difference (A1-A2) (mPa·s), and the Tg difference (Ta-Tb) (°C) were calculated for each example. The results are shown in Table 2.

[0187] <Production of image recording material> A polyethylene terephthalate (PET) substrate ("FE2001" manufactured by Futamura Chemical Co., Ltd., thickness 12 μm, width 540 mm, length 4000 m) was prepared as an impermeable substrate (hereinafter simply referred to as "substrate") on which an image was recorded.

[0188] a conveying mechanism for conveying the substrate; a wire bar coater for applying a pretreatment liquid, a first inkjet head for applying the first ink, and a second inkjet head for applying the second ink, which are arranged in this order from the upstream side in a transport direction of the substrate; An image recording device equipped with the above was prepared. Both the first inkjet head and the second inkjet head were 1200 dpi / 20 inch wide piezo full line heads, where dpi stands for dots per inch. The first inkjet head and the second inkjet head were both arranged such that the nozzle arrangement direction was inclined at 75.7° with respect to the direction perpendicular to the transport direction of the substrate (ie, the width direction of the substrate). A liquid-repellent film containing a fluorine compound is provided on the ink ejection surface of each of the inkjet heads (i.e., the first inkjet head and the second inkjet head). 17 It is a monolayer (SAM film) of C2H4SiCl3.

[0189] The substrate, the pretreatment liquid, the first ink, and the second ink were set in the image recording device, and the pretreatment liquid, the first ink, and the second ink were applied to the substrate under conditions (i.e., application arrangement) such that an overlapping region was formed in which the region to which the pretreatment liquid was applied, the region to which the first ink was applied, and the region to which the second ink was applied overlapped in plan view, thereby recording an image. Details are shown below.

[0190] The substrate was moved at a constant speed of 500 mm / sec, and the pretreatment liquid was applied to the substrate using a wire bar coater. The amount of pretreatment liquid applied was the amount shown in the "Amount of pretreatment liquid applied" column in Table 2 (unit: g / m 2 The amount of flocculant added to the pretreatment liquid was the amount shown in the "Amount of flocculant added" column in Table 2 (unit: g / m 2 )

[0191] "Pretreatment liquid application amount" (unit: g / m 2 ) is the value obtained by dividing the mass of the applied pretreatment liquid by the area of ​​the region to which the pretreatment liquid is applied. "Amount of flocculant applied" (unit: g / m 2 ) is the "amount of pre-treatment liquid applied" (unit: g / m 2 ) and the content (mass %) of the flocculant relative to the total amount of the pretreatment liquid.

[0192] At the location where application of the pretreatment liquid was completed, drying of the pretreatment liquid was started using a dryer at 50°C 1.5 seconds after application of the pretreatment liquid to this location was completed, and drying was completed 3.5 seconds after application of the pretreatment liquid was completed, resulting in a drying time of 2 seconds.

[0193] While the substrate, on which the pretreatment liquid had dried, was moved at a constant stage speed of 50 mm / sec, a first ink was ejected from a first inkjet head to apply a solid image onto the dried pretreatment liquid, and a second ink was ejected from a second inkjet head to apply a solid image onto the applied first ink. During this process, the second ink was applied to the entire first ink applied to the substrate. That is, the overlapping regions in the present examples and comparative examples coincide with the regions to which the first ink and the second ink were applied, respectively. Next, the first ink and the second ink were dried at 70° C. for 10 seconds. As a result, a solid image having a layered structure in which a cyan solid film made of the first ink was layered on a white solid film made of the second ink was obtained, i.e., an image recorded product was obtained that included a substrate and the solid image provided on the substrate.

[0194] Here, the ejection conditions for both the first ink and the second ink were an ejection frequency of 24 kHz and a resolution of 1200 dpi×1200 dpi (dots per inch). The droplet volume of each of the first ink and the second ink when ejecting each of the first ink and the second ink was adjusted according to the application amount of each of the first ink and the second ink. For example, in Example 1, the droplet volume of the first ink was set to 3.0 pL (application amount of the first ink: 7.0 g / m 2 ), and the droplet volume of the second ink was 3.3 pL (corresponding to the application amount of the second ink of 7.8 g / m 2 (corresponding to). The first ink and the second ink were both degassed through a degassing filter and kept at a temperature of 30°C.

[0195] The amounts of the first ink and the second ink applied are shown in the "Amount of First Ink Applied" and "Amount of Second Ink Applied" columns in Table 2 (both units are g / m 2 The amounts of the first resin and the second resin applied were the amounts shown in the "Amount of First Resin Applied" and "Amount of Second Resin Applied" columns in Table 2 (units are g / m). 2 )

[0196] "First ink application amount" (unit: g / m 2 ) is the mass of the first ink applied to the overlap region divided by the area of ​​the overlap region. "First resin application amount" (unit: g / m 2 ) is the "first ink application amount" (unit: g / m 2 ) and the content (mass %) of the first resin relative to the total amount of the first ink. "Second ink application amount" (unit: g / m 2 ) is the mass of the second ink applied to the overlap region divided by the area of ​​the overlap region. "Amount of second resin applied" (unit: g / m 2 ) is the "second ink application amount" (unit: g / m 2 ) and the content (mass %) of the second resin relative to the total amount of the second ink.

[0197] Based on the amount of flocculant applied, the amount of the first resin applied, and the amount of the second resin applied, the applied mass ratio [(first resin + second resin) / flocculant] (i.e., the ratio of the applied mass of flocculant per unit area to the total applied mass of the first resin and the second resin per unit area) was calculated. The obtained applied mass ratio [(first resin + second resin) / flocculant] is shown in the column "Applied amount ratio [resin / flocculant]" in Table 2.

[0198] <Evaluation> The above image recording material was evaluated as follows.

[0199] (Laminate strength (L strength)) From the image recorded product obtained above, a region of 500 mm length x 500 mm width (hereinafter also referred to as laminate strength evaluation region) having a solid image provided on the entire surface was cut out to provide a laminate strength evaluation sample. A dry laminating adhesive (main agent TM-320 (isocyanate compound) / curing agent CAT-13B (alcohol compound), manufactured by Toyo-Morton Co., Ltd.) was applied onto the solid image of the laminate strength evaluation sample using a bar coater, dried at 70°C for 10 seconds, and then a non-oriented polypropylene (CPP) film (trade name: Pylen P1128, manufactured by Toyobo Co., Ltd., thickness 25 μm) was placed on top of it as a laminating substrate. In this state, the laminating substrate and the laminate strength evaluation sample were bonded together to obtain a laminate.

[0200] The resulting laminate was aged at 40°C for 48 hours. A sample piece measuring 100 mm in length and 15 mm in width was cut out from the aged laminate. Next, the laminate substrate and the laminate strength evaluation sample were manually peeled off in a region of 30 mm from one longitudinal end of the sample piece, while the laminate substrate and the laminate strength evaluation sample remained stuck together in the remaining region of 70 mm. Next, a tensile test was conducted in which the peeled portion of the sample piece, the substrate for lamination, and the peeled portion of the sample for evaluating laminate strength, were pulled in opposite directions, perpendicular to the remaining 70 mm region (the region where the substrate for lamination and the sample for evaluating laminate strength remained bonded together). By this tensile test, the peel strength for peeling the laminate strength evaluation sample from the laminating substrate in the remaining 70 mm long region was determined, and the obtained peel strength was taken as the laminate strength. Based on the obtained laminate strength, the laminate strength between the laminate strength evaluation sample (i.e., the image-recorded product) and the substrate for lamination was evaluated according to the following evaluation criteria, thereby evaluating the laminate strength between the image in the image-recorded product and the substrate for lamination (hereinafter also referred to as "L strength"). The results are shown in Table 2. The tensile test was carried out using a tensile tester (TENSILON RTM-25 manufactured by Orientec Co., Ltd.).

[0201] -Evaluation criteria for laminate strength (L strength)- 5: The lamination strength between the image-recorded material and the lamination substrate is 2N / 15mm or more. 4: The lamination strength between the image-recorded material and the lamination substrate is 1.5 N / 15 mm or more and less than 2 N / 15 mm. 3: The lamination strength between the image-recorded material and the lamination substrate is 1 N / 15 mm or more and less than 1.5 N / 15 mm. 2: The lamination strength between the image-recorded material and the lamination substrate is 0.5 N / 15 mm or more and less than 1 N / 15 mm. 1: The lamination strength between the image-recorded material and the lamination substrate is less than 0.5 N / 15 mm.

[0202] <Evaluation of Adhesion> The adhesion of the image was evaluated by attaching a piece of Cellotape (registered trademark, No. 405, manufactured by Nichiban Co., Ltd., width 12 mm, hereinafter simply referred to as "tape") to the solid image in the image recording material obtained above, and then peeling off the tape piece. Specifically, the tape was applied and peeled off in the following manner. The tape was taken out at a constant speed and cut into pieces of approximately 75 mm in length to obtain tape strips. The obtained tape piece was placed on the solid image, and a central area of ​​12 mm wide and 25 mm long of the tape piece was stuck with a finger and rubbed firmly with a fingertip. Within 5 minutes of applying the tape, the edge of the tape was grasped and peeled off at an angle as close to 60° as possible in 0.5 to 1.0 seconds. The presence or absence of any applied matter on the peeled tape piece and the presence or absence of peeling of the solid image on the recording medium were visually observed, and the adhesion of the image was evaluated according to the following evaluation criteria. The results are shown in Table 2. In the following evaluation criteria, the most excellent adhesion is ranked as "5".

[0203] -Adhesion evaluation criteria- 5: No deposits were found on the tape piece, and no peeling of the image on the recording medium was found. 4: A small amount of colored matter was observed on the tape piece, but no peeling of the image on the recording medium was observed. 3: A small amount of colored matter was observed on the tape piece, and the image on the recording medium was slightly peeled off, but this was within the range acceptable for practical use. 2: Colored matter was observed on the tape piece, and peeling of the image on the recording medium was observed, exceeding the practically acceptable range. 1: Colored matter was observed on the tape piece, the image on the recording medium was almost completely peeled off, and the recording medium was visible.

[0204] [Table 2]

[0205] -Explanation of Table 2- The units for the amount of pretreatment liquid applied, the amount of coagulant applied, the amount of first ink applied, the amount of first resin applied, and the amount of second ink applied are all g / m. 2 is. The amount (%) of high-boiling point solvent in the first ink refers to the content (mass %) of high-boiling point solvent (specifically, 1,2-hexanediol (HDO)) relative to the total amount of the first ink, and the amount (%) of high-boiling point solvent (specifically, 1,2-hexanediol (HDO)) in the second ink refers to the content (mass %) of high-boiling point solvent relative to the total amount of the second ink. The surface tension difference refers to the surface tension of the first ink minus the surface tension of the second ink. The ratio of the amount of resin to the amount of flocculant is the ratio of the mass of the resin to the amount of flocculant (i.e., the first resin + the second resin) / flocculant). , the ratio of the total applied mass of the first resin and the second resin per unit area to the applied mass of the flocculant per unit area). Ta - Tb is the value obtained by subtracting Tb from Ta, where Ta is the glass transition temperature of the resin particles contained in the first resin and the resin particles contained in the second resin that have a larger applied mass per unit area in the overlapping region, and Tb is the glass transition temperature of the resin particles contained in the second resin that have a smaller applied mass per unit area. A1-A2 is the value obtained by subtracting A2 from A1, where A1 is the viscosity of the mixture obtained by mixing the pretreatment liquid and the first ink, and A2 is the viscosity of the mixture obtained by mixing the pretreatment liquid and the second ink. The method for measuring A1-A2 is as described above.

[0206] As shown in Table 2, the image recording materials of Examples 1 to 21 obtained by applying the pretreatment liquid, the first ink, and the second ink using a first ink and a second ink whose difference in surface tension (i.e., the value obtained by subtracting the surface tension of the second ink from the surface tension of the first ink) was greater than 0 mN / m and under conditions in which the application amount ratio [resin / coagulant] was 16.0 or more and 30.0 or less, were excellent in lamination strength (L strength) and image adhesion. In contrast, the image-recorded products of Comparative Examples 1, 6, and 7, which were produced under conditions where the applied amount ratio [resin / aggregating agent] was less than 16.0, had excellent image adhesion but reduced lamination strength, presumably because excessive aggregation of the resin caused unevenness on the image surface and / or variations in thickness. Furthermore, the image-recorded products of Comparative Examples 2, 5, and 8, which were produced under conditions where the applied amount ratio [resin / coagulant] was greater than 30.0, exhibited reduced adhesion and laminate strength. This is thought to be because insufficient coagulation of the resin reduced the adhesion of the image, which is the basis for laminate strength. Furthermore, the image recording materials of Comparative Examples 3 and 4, which were produced using first and second inks with a surface tension difference of 0 mN / m or less, had excellent image adhesion but reduced lamination strength. This is thought to be due to insufficient spreading of the second ink, which resulted in unevenness on the image surface and / or variations in thickness.

[0207] Among Examples 1, 2, 6 and 7, Examples 1 and 2 in which the ratio of the amount of resin / coagulant applied was 16.0 or more and 25.0 or less were superior in lamination strength and image adhesion.

[0208] Among Examples 1, 13, and 14, Example 1, in which the first ink did not contain a high-boiling point solvent (i.e., an organic solvent with a boiling point (bp) of 220°C or higher), and Example 13, in which the first ink contained a high-boiling point solvent but the content of the high-boiling point solvent was 5% by mass or less, had superior laminate strength and adhesion. Of Examples 1, 15, and 16, Example 1, in which the second ink did not contain a high-boiling point solvent (i.e., an organic solvent with a boiling point of 220°C or higher), and Example 15, in which the second ink contained a high-boiling point solvent but the content of the high-boiling point solvent was 5% by mass or less, had superior laminate strength and adhesion.

[0209] Comparing Examples 1 and 20, Example 1, in which the pretreatment liquid contained a resin and the Tg of the resin contained in the pretreatment liquid was lower than the Tg of the resin particles in the first resin, was superior in lamination strength and adhesion compared to Example 20, in which the pretreatment liquid did not contain a resin. Comparing Examples 5 and 21, Example 5, in which the pretreatment liquid contained a resin and the Tg of the resin contained in the pretreatment liquid was lower than the Tg of the resin particles in the first resin, had better laminate strength and adhesion.

[0210] Of Examples 1 and 18, Example 1, which satisfied the relationship 0°C≦Ta−Tb≦30°C, was superior in lamination strength and adhesion.

[0211] Among Examples 1 and 19, Example 1, which satisfies A1-A2>0 mPa·s, is a laminate. The strength was superior.

[0212] Although examples using cyan ink as the first ink and white ink as the second ink have been described above, the present disclosure is not limited to the aspects of these examples. For example, it goes without saying that the same effects as those of the above-mentioned group of examples can be obtained if the first ink is changed to an ink other than cyan ink (e.g., magenta ink, yellow ink, black ink, etc.), if a multi-color image is recorded using cyan ink as the first ink and at least one ink other than cyan ink, and if at least one ink other than white ink is used as the second ink.

Claims

1. preparing a pretreatment liquid containing water and at least one flocculant selected from the group consisting of an organic acid, an organic acid salt, a polyvalent metal compound, and a metal complex; preparing a first ink containing a first pigment, a first resin, water, and a surfactant 1, the content of the surfactant 1 being 0.01% by mass to 0.8% by mass relative to the total amount of the first ink; preparing a second ink containing a second pigment, a second resin, water, and a surfactant 2, the content of the surfactant 2 being 0.8% by mass to 5% by mass relative to the total amount of the second ink; an image recording step of applying the pretreatment liquid, the first ink, and the second ink in this order onto a non-permeable substrate to record an image; Including, The image recording process is a method for manufacturing an image recorded product, in which the image is recorded under conditions such that an overlapping region is formed in which an area to which the pretreatment liquid is applied, an area to which the first ink is applied, and an area to which the second ink is applied overlap in a planar view, and under conditions such that in the overlapping region, the ratio of the applied mass of the coagulant per unit area to the total applied mass of the first resin and the second resin per unit area is 16.0 or more and 30.0 or less.

2. The method for producing an image recorded matter according to claim 1, wherein the ratio is 16.0 or more and 25.0 or less.

3. the first ink contains an organic solvent having a boiling point of 220° C. or higher in an amount of 5 mass % or less relative to the total amount of the first ink; 3. The method for producing an image recorded matter according to claim 1, wherein the second ink contains an organic solvent having a boiling point of 220°C or higher in an amount of 5% by mass or less relative to the total amount of the second ink.

4. the pretreatment liquid contains a resin, the first resin includes resin particles; 4. The method for producing an image recorded matter according to claim 1, wherein the glass transition temperature of the resin contained in the pretreatment liquid is lower than the glass transition temperature of the resin particles contained in the first resin.

5. the first resin includes resin particles; the second resin includes resin particles; 5. The method for producing an image recorded matter according to claim 1, wherein, when Ta is a glass transition temperature of the resin particles contained in the first resin and the resin particles contained in the second resin, which have a larger applied mass per unit area in the overlapping region, and Tb is a glass transition temperature of the resin particles contained in the second resin, which have a smaller applied mass per unit area, Ta and Tb satisfy the relationship 0°C≦Ta−Tb≦30°C.

6. 4. The method for producing an image recorded matter according to claim 1, wherein A1 and A2 satisfy A1-A2>0 mPa s, where A1 is a viscosity of a mixture obtained by mixing the pretreatment liquid and the first ink, and A2 is a viscosity of a mixture obtained by mixing the pretreatment liquid and the second ink.

7. 4. The method for producing an image recorded matter according to claim 1, wherein the pretreatment liquid contains a resin, and the resin is at least one selected from the group consisting of an acrylic resin, a polyester resin, a polyolefin resin, a polyurethane resin, a polyurea resin, a polyamide resin, a polycarbonate resin, and a polystyrene resin, and is a water-insoluble resin.

8. a step of obtaining an image recorded matter by the method for producing an image recorded matter according to any one of claims 1 to 7; a step of laminating a substrate for lamination onto the side of the image-recorded product on which the image is recorded to obtain a laminate; A method for producing a laminate comprising the steps of:

9. an impermeable substrate; and an image recorded on the impermeable substrate; the image includes a pretreatment layer in contact with the non-permeable substrate and containing a flocculant, a first layer in contact with the pretreatment layer and containing a first pigment and a first resin, and a second layer in contact with the first layer and containing a second pigment and a second resin, and includes an overlapping region in which the pretreatment layer, the first layer, and the second layer overlap in a planar view; the flocculant is at least one selected from the group consisting of an organic acid, an organic acid salt, a polyvalent metal compound, and a metal complex; In the overlapping region, the ratio of the total mass of the first resin and the second resin per unit area to the mass of the aggregating agent per unit area is 16.0 or more and 30.0 or less.

10. The image recording material according to claim 9; a lamination substrate laminated onto the image of the image recording material; A laminate body comprising:

Images