Method for producing printed matter

Abstract

To provide a method for manufacturing a printed matter capable of manufacturing the printed matter having good unevenness.SOLUTION: A method for producing a printed material, the method comprising: applying an unevenness-providing liquid to a substrate, the unevenness-providing liquid containing a hollow resin particle having a concave portion on an outer surface thereof and water; and applying a fixing liquid to the substrate after the unevenness-providing liquid is applied, the fixing liquid containing a cationic water-dispersible resin and water.SELECTED DRAWING: None

Description

[Technical Field]

[0001] FIELD OF THE INVENTION An embodiment of the present invention relates to a method for producing a printed matter. [Background technology]

[0002] Texture includes the visual and sensory qualities of a material, as well as the feel of its surface. Examples of imparting visual texture include coloring, which can be realized by handwriting, printing, inkjet printing, and the like. There are many different types of sensory textures, and they can be achieved in a variety of ways. For example, a rough texture can be achieved by embossing, a glossy texture by polishing, coating, or plating, and a brushed texture by flocking. The impression that a color gives changes dramatically when the sensory texture, such as the roughness of a textured surface or the smoothness of a glossy surface, changes. This type of design that considers coloring and sensory texture together is called CMF design, an acronym for Color, Material, and Finish. In recent years, designers have been requesting expressions that combine color and texture.

[0003] Patent Document 1 discloses the use of an ultraviolet-curable oligomer having a specific viscosity in an inkjet ink, in order to provide an inkjet ink, a printed material, and a method for producing a printed material that are capable of producing delicate images and thick projections, can adapt to large deformations in the substrate, and are less likely to crack. Patent Document 2 discloses a method for producing a three-dimensional printed matter having a three-dimensional pattern by applying ink containing at least a resin to each layer so that a colored layer is on the lower layer and a clear layer is on the upper layer, in order to provide a simple method for producing a three-dimensional printed matter having a three-dimensional pattern printed thereon. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Publication No. 2020-193302 [Patent Document 2] Japanese Patent Application Publication No. 2019-72914 Summary of the Invention [Problem to be solved by the invention]

[0005] An object of one embodiment of the present invention is to provide a method for producing a printed matter that can produce a printed matter having good unevenness. [Means for solving the problem]

[0006] One embodiment of the present invention relates to a method for producing a printed matter, which includes applying a roughness-imparting liquid containing hollow resin particles having recesses on their outer surfaces and water to a substrate, and after applying the roughness-imparting liquid, applying a fixing liquid containing a cationic water-dispersible resin and water to the substrate. [Effects of the Invention]

[0007] According to one embodiment of the present invention, it is possible to provide a method for producing a printed matter that can produce a printed matter having good unevenness. [Brief explanation of the drawings]

[0008] [Figure 1] 1 is a photograph showing the shape of an example of a hollow resin particle having a recess on its outer surface. DETAILED DESCRIPTION OF THE INVENTION

[0009] Hereinafter, an embodiment of the present invention will be described in detail, but it goes without saying that the present invention is not limited to these embodiments and various modifications and changes may be made.

[0010] A method for producing a printed matter according to one embodiment includes applying to a substrate a roughness-imparting liquid containing hollow resin particles having recesses on their outer surfaces (hereinafter sometimes referred to as hollow resin particles A) and water (hereinafter sometimes referred to as "Step 1"), and after applying the roughness-imparting liquid, applying to the substrate a fixing liquid containing a cationic water-dispersible resin and water (hereinafter sometimes referred to as "Step 2").

[0011] According to the method for producing a printed matter of the embodiment, a printed matter with good unevenness can be produced by applying a roughness-imparting liquid containing hollow resin particles having recesses on their outer surfaces to a substrate, and then applying a fixing liquid containing a cationic water-dispersible resin.

[0012] In the method for producing a printed matter according to the embodiment, steps 1 and 2 may be repeated. By repeating the application of the roughness-imparting liquid and the application of the fixing liquid after the application of the roughness-imparting liquid, the roughness can be adjusted depending on the number of times. Furthermore, the method for producing a printed matter according to the embodiment may further include a step of applying a water-based ink containing a colorant (hereinafter, sometimes simply referred to as "water-based ink" or "ink") to the substrate after applying the fixer. This method makes it possible to produce a printed matter that expresses texture and color.

[0013] <Base material> In the method for producing a printed matter according to an embodiment, the substrate is not particularly limited. For example, any of absorbent substrates such as calcium silicate board, humidity conditioner, and diatomaceous earth, and substrates with poor absorbency such as metal and MDF (medium density fiberboard) may be used.

[0014] <Unevenness-imparting liquid> The roughness-imparting liquid may contain hollow resin particles (hollow resin particles A) having recesses on their outer surfaces, and water.

[0015] FIG. 1 is a photograph showing an example of the shape of hollow resin particles A having a recess on the outer surface. The hollow resin particles A are hollow particles having an internal cavity and also have a recess on the outer surface. The hollow resin particles A are preferably not spherical or nearly spherical, and are preferably short in at least one direction when an orthogonal three-dimensional coordinate system is applied to the three-dimensional shape of the particles. The shape of the hollow resin particles A when viewed from one direction is not particularly limited, and may be, for example, a circle, an ellipse, a polygon such as a square or a hexagon, or a random (irregular) shape. Examples of the shape of the hollow resin particles A include shapes such as those illustrated in FIG. 1. When viewed from one direction, the hollow resin particles A preferably have a shape with a recess in the center. Examples of hollow resin particles A include those having a bowl-like shape due to the recess, and those having a disk-like shape with recesses formed in the center of both sides, like red blood cells.

[0016] Because hollow resin particles A have depressions on their outer surfaces, they are easier to layer evenly on a substrate than particles without depressions on their outer surfaces. As a result, the more particles there are on the substrate surface, the more bulky they become, making them suitable for imparting unevenness. Furthermore, as the solvent contained in hollow resin particles A evaporates, the upper surfaces of some of the particles become more depressed, which is expected to facilitate layering.

[0017] The hollow resin particles A preferably have fine pores on the surface through which the solvent can enter and exit. When the hollow resin particles A have fine pores on the surface through which the solvent can enter and exit, it is presumed that when a fixer or aqueous ink is applied, the solvent in the fixer or aqueous ink is absorbed into the fine pores on the surface of the hollow resin particles A, which may contribute to improved workability and improved image quality, such as reduced bleeding.

[0018] The hollow resin particles A are preferably resin particles that can be dispersed in an aqueous solvent. The hollow resin particles A are preferably those that can be dispersed in water in a particulate form without dissolving in water to form an oil-in-water (O / W) emulsion. The hollow resin particles A can be blended as a resin emulsion when producing the roughness-imparting liquid.

[0019] The type of resin for the hollow resin particles A is not particularly limited, but examples thereof include acrylic resins such as polymers of acrylic acid esters and methacrylic acid esters, or copolymers of these with styrene or the like (e.g., styrene-acrylic resins), etc. These may be used alone or in combination of two or more.

[0020] Commercially available resin emulsions containing hollow resin particles A include "FUJI SP WHITE 1185" (trade name) manufactured by Fuji Pigment Co., Ltd.

[0021] The content of the hollow resin particles A in the roughness-imparting liquid is preferably 0.01 to 30% by mass with respect to the total amount of the roughness-imparting liquid.

[0022] The roughening liquid may contain water. The water is not particularly limited, but it is preferable that the water contains as few ionic components as possible. In particular, from the viewpoint of storage stability of the roughness-imparting liquid, it is preferable that the content of polyvalent metal ions such as calcium is small. As the water, for example, ion-exchanged water, distilled water, ultrapure water, etc. may be used.

[0023] The roughening liquid may contain a binder resin for fixing the particles. The binder resin is preferably a water-dispersible resin that can be dispersed in water to form an emulsion. Examples of the water-dispersible resin include polyurethane resin and acrylic resin. The water-dispersible resin can be blended as a resin emulsion in the production of the roughness-imparting liquid.

[0024] The binder resin may be used alone or in combination of two or more. The content of the binder resin in the roughness-imparting liquid is preferably 5 to 10% by mass with respect to the total amount of the roughness-imparting liquid.

[0025] The roughness-imparting liquid preferably contains a water-soluble organic solvent. The water-soluble organic solvent may be an organic compound that is liquid at room temperature and soluble in water. It is preferable to use a water-soluble organic solvent that is uniformly mixed with an equal volume of water at 20°C under 1 atmosphere. Examples of the water-soluble organic solvent include lower alcohols such as methanol, ethanol, 1-propanol, isopropanol, 1-butanol, 2-butanol, isobutanol, and 2-methyl-2-propanol; glycols such as ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, and polypropylene glycol; glycerins such as glycerin, diglycerin, triglycerin, and polyglycerin; acetins such as monoacetin and diacetin; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, and diethylene glycol monomethyl ether. Examples of suitable water-soluble organic solvents include glycol ethers such as ethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monopropyl ether, triethylene glycol monobutyl ether, tetraethylene glycol monomethyl ether, tetraethylene glycol monoethyl ether, tetraethylene glycol dimethyl ether, and tetraethylene glycol diethyl ether; triethanolamine, 1-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, β-thiodiglycol, and sulfolane. The boiling point of the water-soluble organic solvent is preferably 100° C. or higher, and more preferably 150° C. or higher.

[0026] The above-mentioned water-soluble organic solvents may be used alone or in combination of two or more kinds as long as they form a single phase with water.

[0027] The roughening liquid preferably contains a surfactant. The surfactant may be an anionic surfactant, a cationic surfactant, an amphoteric surfactant, a nonionic surfactant, or a combination thereof, and more preferably a nonionic surfactant. In addition, either a low-molecular-weight surfactant or a high-molecular-weight surfactant may be used.

[0028] Examples of nonionic surfactants include ester surfactants such as glycerin fatty acid esters and fatty acid sorbitan esters; ether surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers and polyoxypropylene alkyl ethers; ether ester surfactants such as polyoxyethylene sorbitan fatty acid esters; acetylene surfactants; silicone surfactants; fluorine surfactants, etc. Among these, acetylene surfactants such as acetylene glycol surfactants and silicone surfactants are preferably used.

[0029] The blending amount of the surfactant in the roughness-imparting liquid is preferably 0.1 to 5.0% by mass with respect to the total amount of the roughness-imparting liquid.

[0030] The roughening liquid may contain other components as appropriate.

[0031] <Fixer> The fixer may contain a cationic water-dispersible resin and water.

[0032] A fixer containing a cationic water-dispersible resin can fix the roughness-imparting liquid more easily than a treatment liquid containing, for example, a polycondensate of a cationic aliphatic amine and epihalohydrin, and is also less likely to cause cracks, making it easier to obtain better image quality.

[0033] Cationic water-dispersible resins are resin particles with a positively charged surface that can disperse in particulate form without dissolving in water to form an oil-in-water (O / W) emulsion. Like self-emulsifying resins, the resin may have cationic functional groups present on the particle surface, or the resin particles may be surface-treated, for example, by attaching a cationic dispersant to the surface. Typical examples of cationic functional groups include primary, secondary, or tertiary amino groups, pyridine groups, imidazole groups, benzimidazole groups, triazole groups, benzotriazole groups, pyrazole groups, and benzopyrazole groups. Examples of cationic dispersants include primary, secondary, tertiary, or quaternary amino group-containing acrylic polymers, polyethyleneimines, cationic polyvinyl alcohol resins, and cationic water-soluble hyperbranched polyesteramide resins.

[0034] Examples of water-dispersible resins include acrylic resins, and these resins can be given a positive surface charge by introducing a cationic functional group into them or by surface treating them with a cationic dispersant or the like. The water-dispersible resin can be blended as a resin emulsion when producing the fixing solution.

[0035] The cationic water-dispersible resin preferably contains large particles having a median diameter of 1 μm or more and 10 μm or less as measured by dynamic light scattering. When a large-particle cationic water-dispersed resin is used, the roughness-imparting liquid is easily aggregated and fixed at the same time. Therefore, it is easy to apply additional roughness-imparting liquid in a wet state. Repeated application of the roughness-imparting liquid and the fixing liquid in a wet state makes it easy to obtain the desired amount of convexity.

[0036] Unless otherwise specified, the median diameter of a water-dispersible resin measured by dynamic light scattering is the volume-based particle size value (median diameter) in the particle size distribution measured by dynamic light scattering. A nanoparticle analyzer, nano Partica SZ-100 (Horiba, Ltd.), or the like, can be used as a dynamic light scattering particle size distribution measuring device. In the fixing solution, water-dispersible resin particles may exist in the form of independent particles or in the form of aggregates of independent particles. The median diameter measured by dynamic light scattering is defined as the "average particle size."

[0037] As the large-particle cationic water-dispersible resin, it is also preferable to use, for example, a polymer complex obtained by combining a polymer having an anionic functional group, such as a carboxy group or a sulfo group, with a polymer having a cationic functional group, such as an amino group or an amide group, in the form of a core-shell structured composite organic particle, in which the core portion is an anionic polymer and the shell portion is a cationic polymer.

[0038] The anionic polymer of the composite organic particles may be, for example, a polymer containing (meth)acrylic acid as a repeating unit, more specifically, a styrene-(meth)acrylic acid copolymer. It may also contain a vinyl compound copolymerizable with styrene and (meth)acrylic acid. The cationic polymer (basic polymer) of the composite organic particles is, for example, a polymer containing a nitrogen-containing monomer, such as a homopolymer or copolymer containing a nitrogen-containing heterocyclic compound as a repeating unit, such as N-vinylpyrrolidone, N-vinylcaprolactam, N-vinyloxazolidone, or N-vinylimidazole. As the comonomer that forms the copolymer, for example, one or more common vinyl compounds such as styrene, (meth)acrylic acid ester, vinyl acetate, or acrylamide can be selected and used.

[0039] In this case, the ratio of anionic polymer to cationic polymer used is preferably 1 part anionic polymer to 3 to 10 parts cationic polymer by weight, in order to make the charge on the particle surface cationic.

[0040] Examples of commercially available products of such composite organic particles include "PP-15" and "PP-17" (both manufactured by Meisei Chemical Industry Co., Ltd.).

[0041] The fixing solution may contain one or more cationic water-dispersible resins. The amount of the cationic water-dispersible resin may be, for example, 2 to 50% by mass based on the total amount of the fixing solution.

[0042] The fixer may include water. The water is not particularly limited, but it is preferable that the water contains as few ionic components as possible. In particular, from the viewpoint of storage stability of the fixer, it is preferable that the content of polyvalent metal ions such as calcium is small. As the water, for example, ion-exchanged water, distilled water, ultrapure water, etc. may be used.

[0043] The fixer may contain a surfactant. The surfactant may be an anionic surfactant, a cationic surfactant, an amphoteric surfactant, a nonionic surfactant, or a combination thereof, and more preferably a nonionic surfactant. In addition, either a low-molecular-weight surfactant or a high-molecular-weight surfactant may be used. The surfactant may be selected from those described above for the roughness-imparting liquid, and the fixing liquid may contain one of these surfactants alone or two or more of them in combination. The fixer may optionally contain other ingredients.

[0044] <Water-based ink> Examples of water-based inks containing coloring materials include magenta ink, cyan ink, yellow ink, and black ink.

[0045] The coloring material may be, for example, a pigment, a dye, or a combination thereof. From the viewpoint of weather resistance, it is preferable that the water-based ink contains a pigment.

[0046] Pigments can be used in the present invention, including organic pigments such as azo pigments, phthalocyanine pigments, polycyclic pigments, and dye lake pigments, as well as inorganic pigments such as carbon black and metal oxides. Examples of azo pigments include soluble azo lake pigments, insoluble azo pigments, and condensed azo pigments. Examples of phthalocyanine pigments include metal phthalocyanine pigments and metal-free phthalocyanine pigments. Examples of polycyclic pigments include quinacridone pigments, perylene pigments, perinone pigments, isoindoline pigments, isoindolinone pigments, dioxazine pigments, thioindigo pigments, anthraquinone pigments, quinophthalone pigments, metal complex pigments, and diketopyrrolopyrroles (DPPs). Examples of carbon black include furnace carbon black, lamp black, acetylene black, and channel black. Examples of metal oxides include titanium oxide and zinc oxide. These pigments can be used alone or in combination.

[0047] From the viewpoints of ejection stability and storage stability, the average particle size of the pigment particles in the ink is preferably 300 nm or less, more preferably 150 nm or less, and even more preferably 100 nm or less, as the volume-based average value in the particle size distribution measured by dynamic light scattering.

[0048] A self-dispersing pigment may be blended as the pigment. The self-dispersing pigment is a pigment in which hydrophilic functional groups have been introduced onto the surface of the pigment by chemical or physical treatment.

[0049] Preferred examples of self-dispersing pigments that can be used include the CAB-O-JET series manufactured by Cabot Corporation, such as "CAB-O-JET200," "CAB-O-JET300," "CAB-O-JET250C," "CAB-O-JET260M," "CAB-O-JET270," "CAB-O-JET450C," "CAB-O-JET465M," and "CAB-O-JET470Y," and products manufactured by Orient Chemical Industries Co., Ltd., such as "BONJET BLACK CW-1," "BONJET BLACK CW-2," "BONJET BLACK CW-3," and "BONJET BLACK CW-4" (all trade names). As the pigment, a microencapsulated pigment in which the pigment is coated with a resin may be used.

[0050] A pigment dispersion in which a pigment is dispersed in advance with a pigment dispersant may be used, or a pigment dispersion in which a pigment is dispersed with a pigment dispersant described below may be used.

[0051] The content of the coloring material may be, for example, 0.1 to 25% by mass relative to the total amount of the water-based ink, from the viewpoint of print density and ink viscosity.

[0052] When the aqueous ink contains a pigment, a pigment dispersant, typically a polymer dispersant or a surfactant-type dispersant, can be used to stably disperse the pigment in the ink.

[0053] The water-based ink preferably contains water. The water is not particularly limited, but it is preferable that the water contains as few ionic components as possible. In particular, from the viewpoint of storage stability of the ink, it is preferable that the content of polyvalent metal ions such as calcium is low. As the water, for example, ion-exchanged water, distilled water, ultrapure water, etc. may be used.

[0054] The aqueous ink may contain a water-soluble organic solvent, which may be an organic compound that is liquid at room temperature and dissolves in water, and is preferably a water-soluble organic solvent that is uniformly miscible with an equal volume of water at 20°C under 1 atmosphere. The water-soluble organic solvent can be selected from those explained above for the roughening liquid.

[0055] These water-soluble organic solvents may be used alone or in combination of two or more kinds as long as they form a single phase with water.

[0056] The water-based ink preferably contains a surfactant.

[0057] The surfactant may be an anionic surfactant, a cationic surfactant, an amphoteric surfactant, a nonionic surfactant, or a combination thereof, and more preferably a nonionic surfactant. In addition, either a low-molecular-weight surfactant or a high-molecular-weight surfactant may be used. The surfactant can be selected from those described above for the roughness-imparting liquid, and the aqueous ink may contain one surfactant alone or two or more surfactants in combination.

[0058] The surfactant preferably has an active ingredient content of 0.1 to 5.0% by mass relative to the total amount of the aqueous ink.

[0059] The water-based ink may contain a binder resin for fixing the coloring material. The binder resin is preferably a water-dispersible resin that can be dispersed in water to form an emulsion. Examples of the water-dispersible resin include polyurethane resin and acrylic resin. The water-dispersible resin can be blended as a resin emulsion when producing the aqueous ink.

[0060] The binder resin may be used alone or in combination of two or more. The content of the binder resin in the aqueous ink is preferably 5 to 10% by mass.

[0061] The water-based ink may contain other components as appropriate, such as a pH adjuster and a preservative. The aqueous ink can be preferably used as an aqueous inkjet ink.

[0062] <Manufacturing method for printed matter> As described above, the method for producing a printed matter can include applying a roughness-imparting liquid to a substrate ("Step 1"), and, after applying the roughness-imparting liquid, applying a fixing liquid to the substrate ("Step 2").

[0063] In step 1, the method for applying the roughness-imparting liquid to the substrate is not particularly limited, and examples thereof include an inkjet method. In the case of an inkjet method, the inkjet method is not particularly limited, and any method such as a piezoelectric method, an electrostatic method, or a thermal method may be used. When an inkjet printing device is used, it is preferable to eject droplets of the roughness-imparting liquid from an inkjet head based on a digital signal and allow the ejected droplets to adhere to the substrate.

[0064] In order to control the unevenness on the substrate, it is preferable to apply the unevenness-imparting liquid in a relatively large amount. The amount of the unevenness-imparting liquid to be applied is, for example, 10 to 400 g / m 2 For example, 50 g / m 2 It is also desirable that the amount of the roughness-imparting liquid to be applied can be easily controlled. The head that ejects the roughness-imparting liquid preferably has a wide print width per head. The head may be capable of ejecting droplets of 10 pL to 50 pL or more. The print width per head may be, for example, approximately 108 mm. For example, the RC1536 series manufactured by SII Printec Inc. may be used as the head.

[0065] In step 2, it is preferable to apply the fixing liquid to the substrate while the unevenness-imparting liquid is in a wet state. Because the unevenness-imparting liquid is in a wet state and has an uneven shape, the fixing liquid is preferably applied by non-contact air spray application, and particularly preferably by micro-mist or dry-mist application. It is preferable to apply a small amount of the fixing liquid using a micro-mist or the like.

[0066] While ordinary air sprays can typically apply liquid in droplets of about 20 to 150 μm, micromist and dry mist sprays can spray droplets ranging from a few microns to as large as about 20 μm, with an average particle diameter of about 10 μm, allowing the fixer to be applied evenly with less impact to the unevenness-imparting liquid that is in a wet state on the substrate. The distance at which the fixer is applied can be any distance that facilitates uniform application, but a distance of about 20 to 30 cm is preferred.

[0067] Known principles for applicators that generate micro mist and dry mist include air spray types (two-liquid spray nozzles) with increased nozzle flow rate and pressure, which enable application with smaller droplets than regular air sprays, airless spray types (single-liquid spray nozzles), rotary types with increased rotation speeds (rotational centrifugal force), and ultrasonic vibration types. Furthermore, with ultrasonic vibration types, if chemical resistance of the fixer (such as corrosion resistance) is required, a double-chamber structure (separating the water used by the ultrasonic vibrator from the container for the fixer) can be used.

[0068] In the method for producing a printed matter, steps 1 and 2 may be repeated. For example, after steps 1 and 2 are performed, steps 1 and 2 may be performed one or more times. By repeating the application of the roughness-imparting liquid and the application of the fixing liquid after the application of the roughness-imparting liquid, it is possible to adjust the roughness depending on the number of times steps 1 and 2 are performed.

[0069] The method for producing a printed matter may include other steps. The method for producing a printed matter may further include, for example, a step of applying an aqueous ink containing a colorant to the substrate after step 2. Such a production method makes it possible to produce a printed matter in which unevenness and color are expressed. For example, after performing steps 1 and 2, or after performing steps 1 and 2, a step of applying an aqueous ink containing a colorant to the substrate may be further performed. When a step of heating and drying the substrate, which will be described later, is performed, for example, after step 2, it is preferable to perform a step of heating and drying the substrate, and then perform a step of applying an aqueous ink containing a colorant.

[0070] The method for applying the aqueous ink is preferably an inkjet method. The inkjet method is not particularly limited and may be any method such as a piezoelectric method, an electrostatic method, or a thermal method. When an inkjet printing device is used, it is preferable to eject droplets of the aqueous ink from an inkjet head based on a digital signal and allow the ejected droplets to adhere to the substrate.

[0071] One type of water-based ink may be applied, or two or more types of water-based ink may be applied. It is preferable to apply full color.

[0072] The method for producing a printed matter may include a step of heating and drying the substrate, for example, after step 2. When steps 1 and 2 are repeatedly performed, it is preferable to perform a step of heating and drying the substrate, for example, after performing the final step 2. The method for producing a printed matter may include, for example, a drying step after the step of applying the aqueous ink. For example, the substrate to which the aqueous ink has been applied may be left to dry at room temperature for a certain period of time. [Example]

[0073] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to the following examples. In the following description, "%" indicates "% by mass" unless otherwise specified.

[0074] <Production of Texture-Providing Liquid 1> The following materials were mixed in the following proportions so that the total amount was 100% by mass, and then filtered through a membrane filter with a pore size of 5 μm to obtain roughness-imparting liquid 1. "FUJI SP WHITE 1185" (trade name) (emulsion of hollow resin particles with recesses on the outer surface, manufactured by Fuji Pigment Co., Ltd., acrylic resin, average particle size 0.45 μm, non-volatile content 29.6% by mass): 50.7% by mass, "Movinyl 966A" (product name) (water-dispersible resin emulsion, manufactured by Japan Coating Resin Co., Ltd., acrylic resin, non-volatile content concentration 45.0% by mass): 16.7% by mass "Surfynol 440" (product name, manufactured by Nissin Chemical Industry Co., Ltd., acetylene glycol surfactant, active ingredient 100% by mass): 1.0% by mass Glycerin (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.): 10% by mass Water: remainder

[0075] <Production of Texture-Providing Liquid 2> The following materials were mixed in the following ratios, and then filtered through a membrane filter with a pore size of 5 μm to obtain a roughness-imparting liquid 2.

[0076] "SANSUI A-170" (trade name) (manufactured by Sansui Co., Ltd., spherical hollow resin particle dispersion, non-volatile content concentration 17.0% by mass): 58.8% by mass "Movinyl 966A" (product name) (water-dispersible resin emulsion, manufactured by Japan Coating Resin Co., Ltd., acrylic resin, non-volatile content concentration 45.0% by mass): 11.1% by mass Glycerin (Fujifilm Wako Pure Chemical Industries, Ltd.): 10.0% by mass Ethylene glycol (Fujifilm Wako Pure Chemical Industries, Ltd.): 5.0% by mass Diethylene glycol monoethyl ether (Fujifilm Wako Pure Chemical Industries, Ltd.): 1.0% by mass Trimethylolpropane (Tokyo Chemical Industry Co., Ltd.): 1.0% by mass "Surfynol 440" (trade name) (manufactured by Nissin Chemical Industry Co., Ltd., acetylene glycol surfactant, non-volatile content 100% by mass): 1.0% by mass Water: 12.1% by mass

[0077] <Fixing solution manufacturing> The following materials were premixed in the ratios shown below, and then dispersed in a homogenizer for 1 minute to obtain a fixing solution.

[0078] "PP-17" (product name, manufactured by Meisei Chemical Industry Co., Ltd., cationic water-dispersible composite organic particles, average particle size approximately 2.5 μm, non-volatile content 26%): 38.5% by mass "Polysol AE-803" (product name, manufactured by Showa Denko K.K., cationic water-based acrylic resin emulsion, average particle size 419 nm, non-volatile content 45%): 22.2% by mass "Silface SAG503A" (product name, manufactured by Nissin Chemical Industry Co., Ltd., silicone surfactant, non-volatile content 100%): 1.0% by mass "Olfine E1010" (product name, manufactured by Nissin Chemical Industry Co., Ltd., acetylene glycol surfactant, non-volatile content 100%): 1.0% by mass Water: 37.3% by mass

[0079] <Production of processing solution> The following materials were mixed so that the total amount was 100% by mass, stirred at 100 rpm for 30 minutes using a mix rotor, and filtered through a 5 μm nylon syringe filter to obtain a treatment liquid.

[0080] "Unisense KHE104L" (trade name, manufactured by Senka Corporation, dimethylamine-epichlorohydrin polycondensate, resin concentration 20%): 10.0% by mass "PAS-H-1L" (product name, manufactured by Nittobo Medical Co., Ltd., diallyldimethylammonium chloride polymer, molecular weight 8500, resin content 28%): 10.7% by mass "Surflon S-243" (product name, manufactured by AGC Seimi Chemical Co., Ltd., nonionic fluorine-based surfactant, non-volatile content 100%): 1.0% by mass "Silface SAG503A" (product name) (manufactured by Nissin Chemical Industry Co., Ltd., silicone surfactant, non-volatile content 100% by mass): 1.0% by mass Diethylene glycol: 30.0% by mass 1,2-butanediol: 3.0% by mass Triethylamine: 0.5% by mass Ion-exchanged water: Remaining

[0081] <Production of water-based ink> Table 1 shows the formulations of four types of aqueous inks (Aqueous Ink K, Aqueous Ink C, Aqueous Ink M, and Aqueous Ink Y). The amounts of pigment dispersion and resin emulsion shown in Table 1 are the total amounts formulated as a dispersion or emulsion. The materials listed in Table 1 were premixed in the proportions shown in Table 1, then dispersed in a homogenizer for 1 minute, and then filtered through a membrane filter with a pore size of 3 μm to obtain four types of color inks: Aqueous Ink K, Aqueous Ink C, Aqueous Ink M, and Aqueous Ink Y.

[0082] Details of the raw materials listed in Table 1 are as follows:

[0083] "CAB-O-JET 300" (product name): Cabot Corporation, water-based self-dispersing carbon black dispersion, pigment 15.0% by mass (black) "CAB-O-JET 450C" (product name): Cabot Corporation, water-based self-dispersing pigment dispersion, pigment 15.0% by mass (cyan) "CAB-O-JET 465M" (product name): Cabot Corporation, water-based self-dispersing pigment dispersion, pigment 24.0% by mass (magenta) "CAB-O-JET 470Y" (product name): Cabot Corporation, water-based self-dispersing pigment dispersion, pigment 15.0% by weight (yellow)

[0084] "Superflex 470" (product name): Daiichi Kogyo Seiyaku Co., Ltd., water-based polyurethane resin emulsion, non-volatile content 38.0% by mass

[0085] "Surfynol 485" (product name): Nissin Chemical Industry Co., Ltd., acetylene glycol surfactant

[0086] Glycerin: Fujifilm Wako Pure Chemical Industries, Ltd. Ethylene glycol: Fujifilm Wako Pure Chemical Industries, Ltd.

[0087] [Table 1]

[0088] <Production of printed materials> Table 2 shows the substrates used in producing the printed matter in Examples 1 and 2 and Comparative Examples 1 to 3, the roughness-imparting liquid used in step 1 and the amount applied per time, the fixing liquid or processing liquid used in step 2 and the amount applied per time, and the number of times steps 1 and 2 were performed.

[0089] Details of the "absorbent substrate" and "non-absorbent substrate" used as the substrate are as follows: The substrate was tilted at a 45° angle, and two drops of water were dropped onto it using a dropper with a total length of 135 mm and an inner diameter x outer diameter of 1.7 mm x 3.1 mm. The distance traveled by the water droplets after two seconds was measured; a substrate with a travel distance of 10 cm / 2 s or less was defined as an absorbent substrate, and a substrate with a travel distance of 15 cm / 2 s or more was defined as a non-absorbent substrate with poor water absorbency. "Absorbent substrate": calcium silicate board (water droplet travel distance measured by the above method: 5.5 cm / 2 s). "Non-absorbent substrate": MDF (water droplet travel distance measured by the above method: 15 cm / 2 s).

[0090] For Examples 1 and 2 and Comparative Examples 1 to 3, the base materials shown in the table were used and Step 1 and Step 2 were carried out the number of times shown in the table. In Comparative Example 3, Step 2 was not carried out. Details of Steps 1 and 2 are as follows. Step 1: Using a roughening liquid or particle-containing liquid, apply approximately 380 g / m using an RC1536 head manufactured by SII Printec Co., Ltd. 2 Print a star-shaped solid image. Step 2: After step 1, fixer or processing solution was applied in a wet state using a Honstek two-liquid nozzle electric micro-mist spray gun at a rate of approximately 5 g / m. 2 In Comparative Example 3, step 2 is not carried out.

[0091] If steps 1 and 2 are performed twice, steps 1 and 2 are performed, and then steps 1 and 2 are performed again in a wet state. If steps 1 and 2 are performed four times, steps 1 and 2 are performed, and then steps 1 and 2 are performed again in a wet state, and then steps 1 and 2 are performed again, and then steps 1 and 2 are performed again.

[0092] Next, the ink was dried by heating at 80°C for 5 minutes in a batch-type electric dryer. After that, a mixed color solid image was printed using water-based ink K, water-based ink C, water-based ink M, and water-based ink Y at a rate of approximately 5 g / m using a 508 head manufactured by SII Printec Co., Ltd. 2 The ink was printed using the amount of ink, and then the ink was left to dry at room temperature (23°C) for 1 hour to obtain a printed matter.

[0093] <Evaluation> The following evaluations were carried out, and the results are shown in Table 2.

[0094] 1.Irregularity performance The table shows the amount of protrusion (mm) from the substrate and the cracking condition of the protrusions for the printed matter obtained when steps 1 and 2 were performed twice and four times. When there were no cracks and the difference in height between when steps 1 and 2 were performed twice and four times was 0.2 mm or more, the unevenness performance was rated A, and when this was not the case, the unevenness performance was rated B.

[0095] 2. Image quality The image quality when the mixed color solid image is formed uniformly and without bleeding is designated as A, and the image quality when this is not the case is designated as B.

[0096] [Table 2]

Claims

[Claim 1] applying a roughness-imparting liquid containing hollow resin particles having recesses on their outer surfaces and water to a substrate; and applying a fixing liquid containing a cationic water-dispersible resin and water to the substrate after applying the roughness-imparting liquid.

Images