JP7262246B2 - Printed matter manufacturing method - Google Patents

Description

TECHNICAL FIELD Embodiments of the present invention relate to a method of manufacturing printed matter.

In the inkjet recording method, droplets of highly fluid inkjet ink are ejected from fine nozzles to record an image on a base material placed facing the nozzles, enabling high-speed printing with low noise. Therefore, it has spread rapidly in recent years. The inks used in such an inkjet recording method include water-based inks containing water as the main solvent, ultraviolet curable inks (UV inks) containing a high content of polymerizable monomers as the main component, and high inks containing wax as the main component. A so-called non-aqueous ink containing a non-aqueous solvent as a main solvent is known together with a hot-melt ink (solid ink) that contains a content.

Since water-based inks use water as a main solvent, they have a low impact on the environment, and since the solvent is easily volatilized, they are excellent in drying properties of printed matter. On the other hand, depending on the type of base material, water-based inks may not sufficiently penetrate the base material, resulting in a problem of image fixability.

Japanese Patent Laid-Open No. 2003-100001 discloses that in a liquid ejecting method in which a medium is coated with a pretreatment liquid and then ink is ejected onto the medium, the order of stacking a plurality of pretreatment liquids having different permeability is changed according to the type of the medium. discloses stabilizing the permeability and wetting and spreading properties of the pretreatment liquid regardless of the characteristics of the medium, and improving the wetting and spreading properties of the pretreatment liquid while increasing the reactivity between the pretreatment liquid and the ink. ing.
In Patent Document 1, the first pretreatment liquid and the second pretreatment liquid each contain a reaction component such as a flocculant and a solution component, and the reaction component is contained between the first pretreatment liquid and the second pretreatment liquid. are the same but have different permeability.

JP 2017-94672 A

Patent Document 1 discloses that a highly permeable medium is coated with a highly permeable pretreatment liquid and then coated with a lowly permeable pretreatment liquid. It is disclosed that a low amount of pretreatment liquid remains on the surface of the medium without permeating the medium, improving reactivity and spreading properties with the ink.
In order to improve the fixability of the image to the base material, it is preferable that the water-based ink penetrates into the base material and the coloring material spreads to the inside of the base material. In the method of leaving two types of pretreatment agents on the surface of the medium as disclosed in Patent Document 1, image fixability may be a problem.

An object of an embodiment of the present invention is to provide a method for manufacturing a printed matter that can manufacture a printed matter with excellent fixability.

According to one embodiment of the present invention, a step of applying a pretreatment liquid A containing a resin and a pretreatment liquid B containing a coagulant onto a substrate by an inkjet method, respectively; A step of applying aqueous inkjet ink onto the substrate after applying the liquid B by an inkjet method, wherein the pretreatment liquid A and the pretreatment liquid B are applied to the substrate in a certain order. Landing time difference ΔT _X between two dots that is the shortest distance between dots in the main scanning direction, of the pretreatment liquid that is ejected and lands on the base material first, out of the pretreatment liquid A and the pretreatment liquid B. , and an impact time difference ΔT _Y between two dots having the shortest distance between the dots in a direction crossing the main scanning direction is 10 ms or more.

According to the method for producing a printed matter according to the embodiment of the present invention, it is possible to produce a printed matter having excellent fixability.

FIG. 1 is a top view schematically showing an example of a serial print head unit. FIG. 2 is a top view schematically showing another example of a serial print head unit. FIG. 3 is a top view schematically showing another example of a serial print head unit. FIG. 4 is an explanatory diagram for explaining a conventional printing method using a serial printing head unit.

Embodiments of the present invention will be described in detail below, but it goes without saying that the present invention is not limited to these embodiments, and various modifications and changes may be made. Hereinafter, "aqueous inkjet ink" may be simply referred to as "ink" or "aqueous ink".

A method for producing a printed matter according to an embodiment of the present invention includes a step of applying a pretreatment liquid A containing a resin and a pretreatment liquid B containing a flocculant onto a substrate by an inkjet method (hereinafter, sometimes referred to as step 1). ), and a step of applying a water-based inkjet ink on the substrate by an inkjet method after applying the pretreatment liquid A and the pretreatment liquid B (hereinafter sometimes referred to as step 2), and pretreatment The liquid A and the pretreatment liquid B are discharged so as to land on the substrate in a certain order, and the pretreatment liquid that first lands on the substrate among the pretreatment liquid A and the pretreatment liquid B is ejected in the main scanning direction. At least one of the landing time difference ΔT _X between the two dots with the shortest distance between the dots in the direction crossing the main scanning direction and the landing time difference ΔT _Y between the two dots with the shortest distance between the dots in the direction crossing the main scanning direction is 10 ms. The above is the method for manufacturing a printed matter.

With this printed matter manufacturing method, it is possible to manufacture printed matter having excellent fixability.
The resin-containing pretreatment liquid A can partially or wholly bond with the ink film to enhance the effect of anchoring the ink film to the substrate. The pretreatment liquid B containing an aggregating agent can cause the ink and/or the pretreatment liquid A to aggregate. In addition, if the order of landing of the pretreatment liquid A and the pretreatment liquid B on the substrate is constant, the dot density will vary due to variations in the permeability of the ink to the substrate, and the dot density will vary due to variations in the cohesion of the ink. Variation in diameter can be reduced. Further, of the pretreatment liquid A and the pretreatment liquid B, the pretreatment liquid that lands first on the base material has a landing time difference ΔT _X between the two dots at which the distance between the dots is the shortest in the main scanning direction, and the main The pretreatment liquid is ejected so that at least one of the landing time difference ΔT _Y between two dots having the shortest distance between the dots in the direction crossing the scanning direction is 10 ms or more, so that the pretreatment liquid lands first on the substrate. can be landed on the substrate with a relatively low landing density. As a result, the penetration speed of the pretreatment liquid that lands on the base material first can be increased, and the pretreatment liquid that lands on the base material later can also easily permeate the base material, allowing the ink to penetrate into the base material. Since it becomes easy to aggregate inside a base material, it can make it easy to obtain an anchor effect. These can improve the fixability of the printed image to the substrate.

<Base material>
In the printed matter manufacturing method of the embodiment, the substrate is not particularly limited. Examples of the base material include printing paper such as plain paper, coated paper, and special paper, cloth, wood base material, metal base material, glass base material, resin base material, etc., but a base material having permeability is preferable.
Cloth is preferred as the substrate. The cloth is not particularly limited, but includes, for example, natural fibers such as cotton, silk, wool, and hemp; chemical fibers such as polyester, acrylic, polyurethane, nylon, rayon, cupra, and acetate; or blended fibers thereof. It can be cloth. The fabric may be woven, knitted, non-woven, or the like.

<Pretreatment liquid A>
The pretreatment liquid A preferably contains a resin. The resin can function as an adhesion promoter.
As the resin, for example, a water-dispersible resin, a water-soluble resin, or a combination thereof can be used.

As the resin, a nonionic resin is preferable from the viewpoint of improving fixability, and a cationic resin, a nonionic resin, or a combination thereof is preferable from the viewpoint of improving uniformity of image density.

From the viewpoint of improving fixability, the resin preferably contains a water-dispersible resin. When the resin is contained in the pretreatment liquid A in a dispersed form, fixability is easily improved.

The water-dispersible resin may have a hydrophilic functional group such as a self-emulsifying resin, or may be surface-treated such as by attaching a hydrophilic dispersant to the surface of the resin particles. The water-dispersible resin can be dispersed in particulate form without dissolving in water to form an oil-in-water (O/W) emulsion.
As the water-dispersible resin, it is preferable to use a resin that forms a transparent coating film.
The water-dispersible resin can be blended, for example, as an oil-in-water resin emulsion when the pretreatment liquid A is produced.

As the water-dispersible resin, any of an anionic water-dispersible resin, a cationic water-dispersible resin, and a nonionic water-dispersible resin may be used.

The anionic water-dispersible resin may be a resin having an anionic functional group such as a self-emulsifying resin, or may be a resin particle surface treated such as by adhering an anionic dispersant. good. Typical anionic functional groups include a carboxy group, a sulfo group and the like. Examples of anionic dispersants include anionic surfactants.
The anionic water-dispersible resin is preferably negatively charged resin particles whose surfaces are negatively charged. The surface charge amount of the resin particles is preferably −20 to −500 μeq/g, more preferably −20 to −100 μeq/g.
The surface charge amount of the resin particles can be evaluated with a particle charge meter. By measuring the amount of anions or cations required to neutralize the sample, the amount of surface charge can be calculated. As the particle charge meter, a colloidal particle charge meter "Model CAS" manufactured by Nihon Luft Co., Ltd. can be used.

The cationic water-dispersible resin may have a cationic functional group, such as a self-emulsifying resin, or may be surface-treated, such as by attaching a cationic dispersant to the surface of the resin particles. It's okay. Cationic functional groups are typically primary, secondary or tertiary amino groups, pyridine groups, imidazole groups, benzimidazole groups, triazole groups, benzotriazole groups, pyrazole groups, or benzopyrazole groups. etc. Cationic dispersants include acrylic polymers containing primary, secondary, tertiary or quaternary amino groups, polyethyleneimine, cationic polyvinyl alcohol resins, cationic water-soluble multi-branched polyesteramide resins and the like.
The cationic water-dispersible resin is preferably positively charged resin particles whose surfaces are positively charged. The surface charge amount of the resin particles is preferably 20 to 500 μeq/g, more preferably 20 to 100 μeq/g.

The nonionic water-dispersible resin may be a resin having a nonionic functional group, such as a self-emulsifying resin, or a surface-treated resin such as a nonionic dispersant attached to the surface of the resin particles. good. Nonionic functional groups typically include polyoxyalkylene glycol groups, carboxyl groups, hydroxyl groups, and the like. Examples of nonionic dispersants include nonionic surfactants.
The nonionic water-dispersible resin is preferably resin particles whose surfaces are hardly charged. The surface charge amount of the resin particles is preferably −20 to 20 μeq/g, more preferably −10 to 10 μeq/g.

Among these water-dispersible resins, nonionic water-dispersible resins are preferable from the viewpoint of improving fixability. Since the nonionic water-dispersible resin mixes with both the flocculant and the ink without aggregating, the pretreatment and the entire ink layer easily form a continuous film, and strong fixability can be easily obtained. Cationic water-dispersible resins, nonionic water-dispersible resins, or combinations thereof are preferred from the viewpoint of improving fixability and uniformity of image density.

Examples of water-dispersible resins include ethylene-vinyl chloride copolymer resins, (meth)acrylic resins, styrene-maleic anhydride copolymer resins, urethane resins, vinyl acetate-(meth)acrylic copolymer resins, and vinyl acetate. - ethylene copolymer resins, styrene-(meth)acrylic copolymer resins, polyester resins, olefin resins, vinyl chloride resins, vinyl acetate resins, water-dispersible melamine resins, amide resins, silicone resins, composite resins thereof, etc. In the above, a hydrophilic functional group may be introduced into these resins, or the surface of the resin particles may be subjected to a surface treatment such as adhering a hydrophilic dispersant. Here, "(meth)acrylic resin" refers to resins containing acrylic units, resins containing methacrylic units, and resins containing acrylic units and methacrylic units.

Among these water-dispersible resins, water-dispersible urethane resins are preferable from the viewpoint of improving fixability.
Since urethane resins generally have high flexibility, when a cloth is used as a base material, the urethane resin easily withstands the elongation of the cloth and easily maintains good fixability. In addition, since it is easy to form hydrogen bonds with the cloth base material, the fibers of the cloth base material can be bonded together with a resin to reduce the elongation of the cloth and bring it closer to the elongation of the ink. Moreover, since the urethane resin has high flexibility, the fibers adhered by the urethane resin are difficult to separate from each other.
For example, it is preferable that the resin contains a water-dispersible urethane resin and the substrate is a cloth substrate.

As the water-dispersible urethane resin, a cationic or nonionic water-dispersible urethane resin is more preferable, and a nonionic water-dispersible urethane resin is even more preferable.

Examples of commercially available water-dispersible resin emulsions include "Superflex 500M" (trade name) (nonionic urethane resin emulsion) and "Superflex 740" (anionic urethane resin emulsion) manufactured by Daiichi Kogyo Seiyaku Co., Ltd. emulsion), Murayama Chemical Laboratory Co., Ltd. “Simplex PUE-C200B” (trade name) (cationic urethane resin emulsion), Japan Coating Resin Co., Ltd. “Movinyl 7720” (trade name) (nonionic water-dispersible acrylic resin emulsion) and the like.

The water-dispersible resin can be used alone or in combination of two or more.
The content of the water-dispersible resin is preferably 1% by mass or more, more preferably 3% by mass or more, and even more preferably 5% by mass or more, relative to the total mass of the pretreatment liquid A. On the other hand, the amount of the water-dispersible resin in the pretreatment liquid A is preferably 30% by mass or less, preferably 20% by mass or less, more preferably 15% by mass or less, relative to the total mass of the pretreatment liquid A. The amount of the water-dispersible resin in the pretreatment liquid A is, for example, preferably 1 to 30% by mass, more preferably 3 to 20% by mass, more preferably 5 to 15% by mass, relative to the total mass of the pretreatment liquid A. preferable.

Examples of water-soluble resins include polyvinyl alcohol, polyacrylic acid, neutralized polyacrylic acid, acrylic acid/maleic acid copolymer, acrylic acid/sulfonic acid copolymer, and styrene/maleic acid copolymer. be done.

A water-soluble resin can be used individually by 1 type or in combination of multiple types.
The amount of the cross-linking agent in pretreatment liquid A is, for example, preferably 1 to 30% by mass, more preferably 3 to 20% by mass, and even more preferably 5 to 15% by mass, relative to the total mass of pretreatment liquid A.

These resins can be used individually by 1 type or in combination of multiple types.

The total amount of the resin in the pretreatment liquid A is preferably 1% by mass or more, more preferably 3% by mass or more, and even more preferably 5% by mass or more, relative to the total mass of the pretreatment liquid A. On the other hand, the total amount of the resin in the pretreatment liquid A is preferably 30% by mass or less, preferably 20% by mass or less, and more preferably 15% by mass or less with respect to the total mass of the pretreatment liquid A. The total amount of the resin in the pretreatment liquid A is, for example, preferably 1 to 30% by mass, more preferably 3 to 20% by mass, and even more preferably 5 to 15% by mass, relative to the total mass of the pretreatment liquid A.

The pretreatment liquid A can further contain water. For example, pretreatment liquid A preferably contains water as a main solvent. Examples of water include, but are not particularly limited to, ion-exchanged water, distilled water, ultrapure water, and deionized water.
Water is contained in the pretreatment liquid A in an amount of preferably 10% by mass or more, more preferably 30% by mass or more, and even more preferably 50% by mass or more relative to the total amount of the pretreatment liquid A. The content of water in the pretreatment liquid A may be, for example, 95% by mass or less, or may be 90% by mass or less with respect to the total amount of the pretreatment liquid A. The content of water in pretreatment liquid A is, for example, preferably 10 to 95% by mass, more preferably 30 to 90% by mass, and even more preferably 40 to 80% by mass relative to the total amount of pretreatment liquid A.

The pretreatment liquid A may contain a water-soluble organic solvent together with water or instead of water.
As the water-soluble organic solvent, a water-soluble organic solvent that is liquid at room temperature and soluble in water is preferable from the viewpoint of viscosity adjustment and moisturizing effect. For example, methanol, ethanol, 1-propanol, isopropanol, 1-butanol, 2-butanol, isobutanol, 1,3-propanediol, 1,3-butanediol, 1,2-butanediol, 1,2-pentanediol , 1,2-hexanediol, 2-methyl-2-propanol and other lower alcohols; ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, pentaethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, etc. Glycols; glycerin; acetins (monoacetin, diacetin, triacetin); diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol monoethyl ether acetate, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monopropyl Ether, triethylene glycol monobutyl ether, tripropylene glycol monobutyl ether, triethylene glycol monohexyl ether, tetraethylene glycol monomethyl ether, tetraethylene glycol monoethyl ether, tetraethylene glycol monobutyl ether, tetraethylene glycol dimethyl ether, tetraethylene glycol diethyl ether derivatives of glycols such as triethanolamine, 1-methyl-2-pyrrolidone, β-thiodiglycol, sulfolane can be used. Polyethylene glycol having an average molecular weight of 200, 300, 400, 600, etc., having an average molecular weight in the range of 190 to 630, Diol-type polypropylene glycol having an average molecular weight, such as an average molecular weight of 400, in a range of 200 to 600, Average molecular weight of 300, 700, etc. A low molecular weight polyalkylene glycol such as a triol type polypropylene glycol having an average molecular weight in the range of 250 to 800 can also be used.

A water-soluble organic solvent can be used individually by 1 type or in combination of 2 or more types.
The amount of the water-soluble organic solvent in the pretreatment liquid A is, for example, preferably 1% by mass or more, more preferably 5% by mass or more, relative to the total amount of the pretreatment liquid A. The amount of the water-soluble organic solvent in the pretreatment liquid A is, for example, preferably 40% by mass or less, preferably 20% by mass or less, relative to the total amount of the pretreatment liquid A. The amount of the water-soluble organic solvent in pretreatment liquid A is, for example, preferably 1 to 50% by mass, more preferably 10 to 40% by mass, relative to the total amount of pretreatment liquid A.

The total amount of water and water-soluble organic solvent in pretreatment liquid A (when only one of them is included, the amount, the same applies hereinafter) is preferably 50% by mass or more, preferably 70% by mass, relative to the total amount of pretreatment liquid A. % or more, and may be 80 mass % or more. On the other hand, the total amount of water and water-soluble organic solvent in the pretreatment liquid A may be, for example, 99% by mass or less or 95% by mass or less with respect to the total amount of the pretreatment liquid A. The total amount of water and water-soluble organic solvent in pretreatment liquid A is, for example, preferably 50 to 99% by mass, more preferably 70 to 95% by mass, and 80 to 90% by mass relative to the total amount of pretreatment liquid A. may be

The pretreatment liquid A preferably contains a surfactant.
As surfactants, for example, ionic surfactants, nonionic surfactants, or combinations thereof can be used. As the ionic surfactant, any of cationic surfactants, anionic surfactants, amphoteric surfactants and the like may be used. As the surfactant, a nonionic surfactant is preferred. The HLB value of the surfactant is preferably 5-20.

Examples of nonionic surfactants include acetylene glycol-based surfactants, silicone-based surfactants, polyoxyethylene alkyl ether-based surfactants, polyoxypropylene alkyl ether-based surfactants, and polyoxyethylene alkylphenyl ethers. surfactant, polyoxypropylene alkylphenyl ether surfactant, polyoxyethylene fatty acid ester surfactant, polyoxypropylene fatty acid ester surfactant, sorbitan fatty acid ester surfactant, polyoxyethylene sorbitan fatty acid ester surfactants, polyoxyethylene sorbitol fatty acid ester surfactants, glycerin fatty acid ester surfactants, and the like. These may be used alone or in combination of two or more.
Among these, acetylene glycol-based surfactants, silicone-based surfactants, or combinations thereof can be preferably used, with silicone-based surfactants being more preferred.

Among silicone-based surfactants, polyether-modified silicone-based surfactants, alkyl/aralkyl-co-modified silicone-based surfactants, acrylic silicone-based surfactants, and the like can be preferably used. Examples of commercially available silicone-based surfactants include the Silface SAG series ("Silface SAG002" (trade name)) manufactured by Nissin Chemical Industry Co., Ltd., and the like.

Examples of nonionic surfactants include Air Products' Surfynol series ("Surfinol 104E", "Surfinol 104H", "Surfinol 420", "Surfinol 440", "Surfinol 465", "Surfinol 485" etc. (all trade names)) and Nissin Chemical Co., Ltd. "OLFINE E1004", "OLFINE E1010", "OLFINE E1020" etc. (all trade names); Kao Emulgen series manufactured by Co., Ltd. (“Emulgen 102KG”, “Emulgen 103”, “Emulgen 104P”, “Emulgen 105”, “Emulgen 106”, “Emulgen 108”, “Emulgen 120”, “Emulgen 147”, “Emulgen 150” , “EMULGEN 220”, “EMULGEN 350”, “EMULGEN 404”, “EMULGEN 420”, “EMULGEN 705”, “EMULGEN 707”, “EMULGEN 709”, “EMULGEN 1108”, “EMULGEN 4085”, “EMULGEN 2025G” etc.) and other polyoxyethylene alkyl ether-based surfactants.

You may use surfactant individually by 1 type or in combination of 2 or more types.
The surfactant content is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, relative to the total amount of pretreatment liquid A. The surfactant content is preferably 10% by mass or less, more preferably 5% by mass or less, relative to the total amount of pretreatment liquid A. The surfactant is preferably, for example, 0.1 to 10% by mass, more preferably 0.5 to 5% by mass, relative to the total amount of pretreatment liquid A.

The pretreatment liquid A may further contain a cross-linking component to cross-link the resin component. As the cross-linking component, for example, a cross-linking component that may be contained in the ink described later can be selected and used. When a cross-linking component is added, the content of the cross-linking component is preferably 0.1 to 5% by mass, more preferably 1 to 3% by mass, based on the total amount of pretreatment liquid A.

The pretreatment liquid A may further contain arbitrary components such as defoaming agents, pH adjusters, antioxidants, preservatives, infrared absorbers, and ultraviolet absorbers.

The method for producing the pretreatment liquid A is not particularly limited, and it can be produced appropriately by a known method. For example, it can be prepared by putting all the components together or separately into a stirrer such as a three-one motor, dispersing them, and optionally passing them through a filter such as a membrane filter.

<Pretreatment liquid B>
The pretreatment liquid B preferably contains a flocculating agent.
The aggregating agent preferably has a function of reducing the dispersibility or solubility of the coloring material in the water-based ink to aggregate the coloring material.
Examples of flocculants include cationic resins, polyvalent metal salts, organic acids, and low-polar solvents.

The cationic resin may be either a cationic water-soluble resin or a cationic water-dispersible resin, or may be used in combination. As the cationic resin, a cationic water-soluble resin is preferred.

Examples of cationic water-soluble resins include polyethyleneimine (PEI), polyvinylamine, polyallylamine and salts thereof, polyvinylpyridine, and cationic acrylamide copolymers. More specifically, for example, polydiallyldimethylammonium chloride or the like can be used.

Examples of commercially available cationic water-soluble resins include the Sharoll series manufactured by Daiichi Kogyo Seiyaku Co., Ltd. (“Sharoll DC-303P”, “Sharoll DC-902P”, etc. (both trade names)), Senka Co., Ltd. Unisense series (“Unisense FCA1000L”, “Unisense FPA100L”, etc. (both trade names)), Osaka Organic Chemical Industry Co., Ltd. HC polymer series (“HC polymer 1S”, “HC polymer 1N”, “HC polymer 1NS” , “HC Polymer 2”, “HC Polymer 2L” (all are trade names)), and the like.

Commercial products of polyethyleneimine include, for example, Epomin series manufactured by Nippon Shokubai Co., Ltd. “Epomin SP-006”, “Epomin SP-012”, “Epomin SP-018”, “Epomin SP-200”, etc. name); "Lupasol FG", "Lupasol G20 Waterfree", "Lupasol PR 8515" (all trade names) manufactured by BASF Japan Ltd., and the like.
Commercial products of polyallylamine include, for example, allylamine polymers "PAA-01", "PAA-03", and "PAA-05" (all trade names) manufactured by Nitto Boseki Co., Ltd., and allylamine hydrochloride weight. "PAA-HCL-01", "PAA-HCL-03", and "PAA-HCL-05" (all trade names), which are coalescence, and "PAA-SA" (trade name), which is an allylamine amide sulfate polymer etc.

As the cationic water-dispersible resin, for example, one or more cationic water-dispersible resins that can be used in the pretreatment liquid A can be selected and used.

As the cationic water-dispersible resin, it is preferable to use a resin that forms a transparent coating film. Further, when manufacturing the treatment liquid, it can be blended as an oil-in-water type resin emulsion.

The cationic resin may be used singly or in combination of two or more.
The amount of the cationic resin in the pretreatment liquid B is preferably 1% by mass or more, more preferably 3% by mass or more, and even more preferably 5% by mass or more, relative to the total mass of the pretreatment liquid B. On the other hand, the amount of the cationic resin in the pretreatment liquid B is preferably 30% by mass or less, preferably 20% by mass or less, more preferably 15% by mass or less, relative to the total mass of the pretreatment liquid B. The amount of the cationic resin in pretreatment liquid B is, for example, preferably 1 to 30% by mass, more preferably 3 to 20% by mass, and even more preferably 5 to 15% by mass, relative to the total mass of pretreatment liquid B. .

Examples of polyvalent metal salts include halides, nitrates, sulfates, acetates, fatty acid salts, lactates, and chlorates of divalent or higher metals. As the halide, chloride, bromide, iodide and the like are preferable. Examples of divalent or higher metals include divalent alkaline earth metals such as Ca, Mg, Sr, and Ba; divalent metals such as Ni, Zn, Cu, and Fe(II); Among them, alkaline earth metals are preferred.
More specific examples of polyvalent metal salts include calcium chloride, calcium nitrate, magnesium chloride, magnesium nitrate, copper nitrate, calcium acetate, and magnesium acetate.

Polyvalent metal salts may be used singly or in combination of two or more.
The amount of the polyvalent metal salt in the pretreatment liquid B is preferably 1% by mass or more, more preferably 3% by mass or more, and even more preferably 5% by mass or more, relative to the total mass of the pretreatment liquid B. On the other hand, the amount of the polyvalent metal salt in the pretreatment liquid B is preferably 30% by mass or less, preferably 20% by mass or less, and more preferably 15% by mass or less relative to the total mass of the pretreatment liquid B. The amount of the polyvalent metal salt in the pretreatment liquid B is, for example, preferably 1 to 30% by mass, more preferably 3 to 20% by mass, more preferably 5 to 15% by mass, relative to the total mass of the pretreatment liquid B. preferable.

Examples of organic acids include formic acid, acetic acid, oxalic acid, citric acid, malic acid, ascorbic acid and the like.

As the flocculant, it is preferable to use an organic acid that is liquid at 23°C. By applying the flocculant to the substrate surface as a liquid, it is possible to reduce the influence of friction. Further, when the pretreatment liquid A is applied using an ink jet method, non-ejection of the print head can be prevented for a long period of time by using a liquid organic acid as the aggregating agent.
As the organic acid that is liquid at 23°C, acetic acid and lactic acid can be preferably used, and lactic acid is more preferred.

The boiling point of the organic acid is preferably 120°C or higher.
In step 2, the ink-filled recording head performs printing while moving over the base material to which each pretreatment liquid has been applied. By using an organic acid with a boiling point of 120°C or higher, it becomes difficult for the organic acid to volatilize from the base material to which each pretreatment liquid has been applied, so that the volatilized organic acid does not come into contact with the water-based ink in the nozzles of the recording head. Therefore, it is possible to prevent deterioration of the water-based ink due to the organic acid at the nozzle portion. Therefore, it is possible to suppress ejection failure of water-based ink from the print head.

You may use an organic acid individually by 1 type or in combination of 2 or more types.
The amount of the organic acid in the pretreatment liquid B is preferably 1% by mass or more, more preferably 3% by mass or more, and more preferably 5% by mass or more, relative to the total mass of the pretreatment liquid B. On the other hand, the amount of the organic acid in the pretreatment liquid B is preferably 30% by mass or less, preferably 20% by mass or less, and more preferably 15% by mass or less relative to the total mass of the pretreatment liquid B. The amount of the organic acid in the pretreatment liquid B is, for example, preferably 1 to 30% by mass, more preferably 3 to 20% by mass, and even more preferably 5 to 15% by mass, relative to the total mass of the pretreatment liquid B.

Preferred examples of low-polar solvents include aliphatic ester solvents, glycol ether solvents, and acetate solvents.
As the low-polarity solvent, for example, a solvent having an SP value of 10 (cal/cm3) ^1/2 or less is preferable.
Here, the SP value is an SP value obtained by the Fedors formula, and more specifically, a value calculated by the following formula proposed by Fedors. In the following formula, Δei is the vaporization energy of the i-component atom or atomic group, and Δvi is the molar volume of the i-component atom or atomic group (Hansen Solubility Parameters: A User's Handbook, Second Edition, Charles M. Hansen, CRC Press, 2007).
δ = [(sum Δei)/(sum Δvi)] ^1/2

Low polar solvents may be used alone or in combination of two or more.
The amount of the low-polar solvent in the pretreatment liquid B is, for example, preferably 1 to 30% by mass, more preferably 3 to 20% by mass, and even more preferably 5 to 15% by mass, relative to the total mass of the pretreatment liquid B. .

Among these, cationic resins, polyvalent metal salts, organic acids, or combinations thereof are preferred from the viewpoint of cohesiveness with respect to ink and pretreatment liquid A and image density.
From the viewpoint of improving fixability and improving image density, the aggregating agent preferably contains at least one selected from the group consisting of cationic resins, polyvalent metal salts, and organic acids. From the viewpoint of improving fixability, the flocculant more preferably contains an organic acid. If the pretreatment liquid A contains an organic acid, the content of carboxy groups in the pretreatment liquid A tends to increase. It can be improved further.

From the viewpoint of improving image density uniformity and fixing performance, it is preferable that the pretreatment liquid B contains an aggregating agent that causes the ink to coagulate but the resin of the pretreatment liquid A does not coagulate.
When the pretreatment liquid A does not aggregate with the pretreatment liquid B, the aggregating agent in the pretreatment liquid B is not used due to the aggregation of the pretreatment liquid A, so the ink aggregation performance of the pretreatment liquid B is less likely to decrease. Image density uniformity can be improved.
In addition, when the pretreatment liquid A is B and does not aggregate with the pretreatment liquid B, it is easy to obtain a continuous film, and therefore, it is possible to obtain even better fixability.
Specifically, for example, the pretreatment liquid A contains a cationic resin, a nonionic resin, or a combination thereof, and the pretreatment liquid B contains a cationic resin, a polyvalent metal salt, an organic acid, or a combination thereof. preferably included.
The flocculant of the pretreatment liquid B is preferably different from the resin of the pretreatment liquid A.

These flocculants can be used singly or in combination.

The total amount of the coagulant in the pretreatment liquid B is preferably 1% by mass or more, more preferably 3% by mass or more, and even more preferably 5% by mass or more, relative to the total mass of the pretreatment liquid B. On the other hand, the total amount of the coagulant in the pretreatment liquid B is preferably 30% by mass or less, preferably 20% by mass or less, and more preferably 15% by mass or less with respect to the total mass of the pretreatment liquid B. The total amount of the flocculant in the pretreatment liquid B is, for example, preferably 1 to 30% by mass, more preferably 3 to 20% by mass, and even more preferably 5 to 15% by mass, relative to the total mass of the pretreatment liquid B. .

The pretreatment liquid B can further contain water. For example, pretreatment liquid B preferably contains water as a main solvent. Examples of water include, but are not particularly limited to, ion-exchanged water, distilled water, ultrapure water, and deionized water.
Water is contained in the pretreatment liquid B in an amount of preferably 10% by mass or more, more preferably 30% by mass or more, and even more preferably 50% by mass or more relative to the total amount of the pretreatment liquid A. The content of water in the pretreatment liquid A may be, for example, 95% by mass or less, or may be 90% by mass or less, relative to the total amount of the pretreatment liquid B. The content of water in the pretreatment liquid B is, for example, preferably 10 to 95% by mass, more preferably 30 to 90% by mass, and even more preferably 50 to 90% by mass relative to the total amount of the pretreatment liquid B.

The pretreatment liquid B may contain a water-soluble organic solvent together with water or instead of water.
As the water-soluble organic solvent, a water-soluble organic solvent that is liquid at room temperature and soluble in water is preferable from the viewpoint of viscosity adjustment and moisturizing effect. As the water-soluble organic solvent, for example, one or more water-soluble organic solvents that can be used for the pretreatment liquid A can be selected and used.

A water-soluble organic solvent can be used individually by 1 type or in combination of 2 or more types.
The amount of the water-soluble organic solvent in the pretreatment liquid B is preferably 1% by mass or more, more preferably 5% by mass or more, relative to the total amount of the pretreatment liquid B, for example. The amount of the water-soluble organic solvent in the pretreatment liquid B is preferably 40% by mass or less, preferably 20% by mass or less, relative to the total amount of the pretreatment liquid B, for example. The amount of the water-soluble organic solvent in the pretreatment liquid B is, for example, preferably 1 to 40% by mass, more preferably 5 to 20% by mass, relative to the total amount of the pretreatment liquid B.

The total amount of water and water-soluble organic solvent in pretreatment liquid B (when only one of them is included, the amount, the same applies hereinafter) is preferably 50% by mass or more, and 70% by mass relative to the total amount of pretreatment liquid B. % or more, and may be 80 mass % or more. On the other hand, the total amount of water and water-soluble organic solvent in the pretreatment liquid B may be, for example, 99% by mass or less or 95% by mass or less with respect to the total amount of the pretreatment liquid B. The total amount of water and water-soluble organic solvent in pretreatment liquid B is, for example, preferably 50 to 99% by mass, more preferably 70 to 95% by mass, and 80 to 90% by mass relative to the total amount of pretreatment liquid B. may be

The pretreatment liquid B preferably contains a surfactant.
As the surfactant, for example, the same surfactants as those that can be blended in the pretreatment liquid A can be used.

You may use surfactant individually by 1 type or in combination of 2 or more types.
The amount of the surfactant is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, relative to the total amount of the pretreatment liquid B. The surfactant content is preferably 10% by mass or less, more preferably 5% by mass or less, relative to the total amount of the pretreatment liquid B. The surfactant is preferably, for example, 0.1 to 10% by mass, more preferably 0.5 to 5% by mass, relative to the total amount of pretreatment liquid B.

When the pretreatment liquid B contains a resin component, the pretreatment liquid B may further contain a cross-linking component in order to cross-link the resin component. As the cross-linking component, for example, a cross-linking component that may be contained in the ink described later can be selected and used. When a cross-linking component is added, the content of the cross-linking component is preferably 0.1 to 5% by mass, more preferably 1 to 3% by mass, based on the total amount of pretreatment liquid A.

The pretreatment liquid B may further contain arbitrary components such as defoaming agents, pH adjusters, antioxidants, preservatives, infrared absorbers, and ultraviolet absorbers.

The method for producing the pretreatment liquid B is not particularly limited, and it can be produced as appropriate by a known method. For example, it can be prepared by putting all the components together or separately into a stirrer such as a three-one motor, dispersing them, and optionally passing them through a filter such as a membrane filter.

<Aqueous inkjet ink>
The water-based inkjet ink preferably contains a coloring material.
The coloring material may be either a pigment or a dye, and the pigment or dye may be used alone, or both may be used in combination. A pigment can be preferably used as the colorant from the viewpoint of the weather resistance and water resistance of the printed matter.

A non-white pigment, a white pigment, or a combination thereof can be used as the pigment.

Examples of non-white pigments include organic pigments such as azo, phthalocyanine, dye, condensed polycyclic, nitro, and nitroso pigments (Brilliant Carmine 6B, Lake Red C, Watching Red, Disazo Yellow, Hansa Yellow, phthalocyanine blue, phthalocyanine green, alkali blue, aniline black, etc.); metals such as cobalt, iron, chromium, copper, zinc, lead, titanium, vanadium, manganese, nickel, metal oxides and sulfides; Inorganic pigments such as Prussian blue, and carbon blacks such as furnace carbon black, lamp black, acetylene black and channel black can be used.

When using a substrate having a color, surface shape, etc., such as cloth, as the substrate, a base layer is formed using white ink using a white pigment in order to hide the color, etc. of the substrate, and then the base layer is formed. There is a method of forming an image from above.
Examples of white pigments include inorganic pigments such as titanium oxide, zinc white, zinc sulfide, antimony oxide, and zirconium oxide. In addition to inorganic pigments, hollow resin fine particles and polymer fine particles can also be used. Among them, it is preferable to use titanium oxide from the viewpoint of hiding power.

The volume-based average particle size of the pigment is preferably 50 to 500 nm, more preferably 50 to 200 nm.

A self-dispersing pigment whose surface is modified with a hydrophilic functional group may also be used. Examples of commercially available self-dispersing pigments include CAB-O-JET series manufactured by Cabot Corporation (“CAB-O-JET200”, “CAB-O-JET300”, “CAB-O-JET250C”, “CAB-O- JET260M", "CAB-O-JET270", etc. (all trade names)), Orient Chemical Co., Ltd. "BONJET BLACK CW-1S", "BONJET BLACK CW-2", "BONJET BLACK CW-3", etc. (any are also trade names).
Microencapsulated pigments, which are pigments coated with resin, may also be used.
A pigment dispersion in which the pigment is pre-dispersed with a pigment dispersant may also be used. Examples of commercially available pigment dispersions dispersed with a pigment dispersant include HOSTAJET series (trade name) manufactured by Clariant Co., Ltd., FUJI SP series (trade name) manufactured by Fuji Pigment Co., Ltd., and the like. A pigment dispersion dispersed with a pigment dispersant, which will be described later, may also be used.

One pigment may be used alone, or two or more pigments may be used in combination.
The solid content of the pigment is preferably about 0.1 to 30% by mass, more preferably 0.1 to 15% by mass, based on the total amount of the ink, although it varies depending on the type.

The ink may further contain a pigment dispersant to stably disperse the pigment in water.
Examples of pigment dispersants include commercially available TEGO Disperse series (“TEGO Disperse 740W”, “TEGO Disperse 750W”, “TEGO Disperse 755W”, “TEGO Disperse 757W”, “TEGO Disperse 757W”, “TEGO Disperse” manufactured by EVONIK). Disperse 760W" (both trade names)), Solsperse series manufactured by Nippon Lubrizol Co., Ltd. 44000", "Solsperse 46000" (both trade names)), Joncryl series manufactured by Johnson Polymer ("Joncryl 57", "Joncryl 60", "Joncrill 62", "Joncrill 63", "John Kuril 71", "Jon Kuril 501" (both trade names)), BYK's "DISPERBYK-102", "DISPERBYK-185", "DISPERBYK-190", "DISPERBYK-193", "DISPERBYK-199" ( All are trade names) and the like.
As the surfactant-type dispersant, for example, Kao Corporation Demoll series (“Demor EP”, “Demor N”, “Demor RN”, “Demor NL”, “Demor RNL”, “Demor T-45” (all trade names)), Emulgen series manufactured by Kao Corporation ("Emulgen A-60", "Emulgen A-90", "Emulgen A-500", "Emulgen B-40", nonionic surfactants such as "Emulgen L-40" and "Emulgen 420" (both trade names).

Pigment dispersants may be used alone or in combination of two or more.
The amount of the pigment dispersant in the ink varies depending on the type and is not particularly limited, but in general, the mass ratio of the solid content to the total amount of the ink is in the range of 0.005 to 0.5 per 1 part of the pigment. preferably.

As the dye, those commonly used in the technical field of printing can be used without particular limitation. Specific examples include basic dyes, acid dyes, direct dyes, soluble vat dyes, acid mordant dyes, mordant dyes, reactive dyes, vat dyes, sulfur dyes, etc. Among these, water-soluble dyes, reduction dyes, etc. Water-soluble substances can be used. More specific examples include azo dyes, rhodamine dyes, methine dyes, azomethine dyes, xanthene dyes, quinone dyes, triphenylmethane dyes, diphenylmethane dyes, and methylene blue. These dyes may be used alone or in combination of two or more.

One type of dye may be used alone, or two or more types may be used in combination.
Although the dye differs depending on the type, from the viewpoint of color development, etc., the solid content is preferably 0.1 to 30% by mass, more preferably 0.5 to 15% by mass, more preferably 1 to 10% by mass, based on the total amount of the aqueous ink. % is more preferred.

The ink preferably contains water. The ink preferably contains a coloring material and water.
Water is not particularly limited as long as it functions as a solvent for ink, and examples thereof include ion-exchanged water, distilled water, ultrapure water, and deionized water.
Water is preferably 20% by mass or more, more preferably 30% by mass or more, still more preferably 50% by mass or more, and even more preferably 60% by mass or more, relative to the total amount of ink. On the other hand, water is preferably 95% by mass or less, more preferably 90% by mass or less, even more preferably 80% by mass or less, and even more preferably 70% by mass or less, relative to the total amount of the ink. Water is, for example, preferably 20 to 95% by mass, more preferably 30 to 90% by mass, and preferably 40 to 80% by mass, relative to the total amount of ink.

The ink may contain a water-soluble organic solvent in addition to water.
As the water-soluble organic solvent, it is possible to use an organic compound that is liquid at room temperature and is soluble or miscible with water. is preferred.
As the water-soluble organic solvent, for example, one or more of the water-soluble organic solvents described in the pretreatment liquid A can be selected and used.
The water-soluble organic solvent is preferably 1 to 80% by mass, more preferably 5 to 60% by mass, may be 10 to 50% by mass, and may be 20 to 40% by mass, relative to the total amount of the ink.

The ink can include water-dispersible resins, water-soluble resins, or combinations thereof. By including at least one of a water-dispersible resin and a water-soluble resin, the ink can sufficiently fix the colorant to the base material, and thus high colorability can be obtained with a small amount of the colorant.

The water-dispersible resin is not particularly limited, and for example, one or more water-dispersible resins that can be used for the resin of the pretreatment liquid A can be selected and used.
As the water-dispersible resin, any of an anionic water-dispersible resin, a cationic water-dispersible resin, and a nonionic water-dispersible resin may be used, but an anionic water-dispersible resin is preferred.
As the water-dispersible resin, a water-dispersible urethane resin is more preferable, and an anionic water-dispersible urethane resin is more preferable.

The water-soluble resin is not particularly limited, and for example, one or more water-soluble resins that can be used for the resin of the pretreatment liquid A can be selected and used.

The total amount of the water-soluble resin and the water-dispersible resin is preferably 0.1 to 15, more preferably 1 to 5, and even more preferably 2 to 4, based on the mass ratio of the solid content to 1 part of the coloring material. By setting the content of the resin within this range, it is possible to sufficiently ensure the fixability and image quality of the image printed on the surface of the substrate.
When the ratio of the resin to the coloring material 1 is 0.5 or more, the fixability of the image can be further improved. When the ratio of the resin to the coloring material is 7 or less, the on-press stability of the water-based ink can be improved.

The total amount of the water-dispersible resin and the water-soluble resin is preferably 0.1% by mass or more, more preferably 1% by mass or more, and even more preferably 5% by mass or more, in solid content, relative to the total amount of the ink.
Also, the total amount of the water-soluble resin and the water-dispersible resin is preferably 20% by mass or less, more preferably 15% by mass or less, relative to the total amount of the aqueous ink.
The total amount of the water-dispersible resin and the water-soluble resin is preferably 0.1 to 20% by mass, more preferably 1 to 20% by mass, more preferably 5 to 15% by mass, in terms of solid content, relative to the total amount of the ink. Even more preferable.

The ink may contain a surfactant. Addition of a surfactant is preferable because it makes it easier to stably eject the ink in an inkjet method and facilitates appropriate control of the penetration of the ink into the substrate.

As the surfactant, for example, the same surfactants as those that can be blended in the pretreatment liquid A can be used.

You may use surfactant individually by 1 type or in combination of 2 or more types.
The surfactant content is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, relative to the total amount of the ink. On the other hand, the surfactant content is preferably about 10% by mass or less, more preferably about 5% by mass or less, even more preferably 4% by mass or less, and even more preferably 3% by mass or less, relative to the total amount of the ink. The amount of the surfactant is, for example, preferably 0.1 to 10% by mass, more preferably 0.1 to 5% by mass, still more preferably 0.1 to 4% by mass, and 0.5% by mass, based on the total amount of the ink. ~3% by mass is more preferred.

The ink may contain a cross-linking component in order to cross-link the resin component to strengthen the coating film and further improve fixability. Examples of cross-linking components include blocked isocyanates, oxazoline group-containing compounds, (poly)carbodiimides, aziridines, and the like.
The cross-linking component is preferably 0.1 to 5% by mass, more preferably 1 to 3% by mass, relative to the total amount of the ink.

In addition to the above components, optional components such as antifoaming agents, pH adjusters, antioxidants, preservatives, infrared absorbers, and ultraviolet absorbers may be added to the ink.

The pH of the ink is preferably 7.0 to 10.0, more preferably 7.5 to 9.0, from the viewpoint of storage stability of the ink.

The viscosity of the ink can be adjusted as appropriate, but from the viewpoint of ejection properties, the viscosity at 23° C. is preferably 1 to 30 mPa·s.

The method for producing the ink is not particularly limited, and the ink can be produced as appropriate by a known method. For example, it can be prepared by putting all the components together or separately into a stirrer such as a three-one motor, dispersing them, and optionally passing them through a filter such as a membrane filter.

<Manufacturing method of printed matter>
A method of producing a printed matter using pretreatment liquid A, pretreatment liquid B, and water-based ink will be described below.
First, step 1 according to one embodiment will be described. In step 1, the pretreatment liquid A and the pretreatment liquid B are each applied onto the substrate by an inkjet method.

The inkjet method is not particularly limited, and a method using a general recording head can be used. For example, a serial type using a serial type recording head or a line head type using a line head type recording head can be used, but the serial type is preferable.

If the nozzle portion for ejecting the pretreatment liquid B containing the aggregating agent and the nozzle portion for ejecting the water-based ink are arranged close to each other, there is no problem in the configuration in which only the nozzle portion for ejecting the water-based ink is arranged. A mist containing an aggregating agent may be generated from the nozzle portion that ejects the pretreatment liquid B and adhere to the nozzle portion that ejects the water-based ink. As a result, the water-based ink aggregates in the nozzle portion, causing nozzle clogging, which may cause ejection failure. In the line-head type inkjet recording apparatus, even if one nozzle in a line-shaped nozzle array fails to eject ink, the image is greatly affected. Therefore, when using the pretreatment liquid B containing a flocculant, it is preferable to use a serial inkjet recording apparatus.

In the case of the serial type, it is easy to increase the penetration rate of the pretreatment liquid that lands first into the base material, and the pretreatment liquid that lands later also easily penetrates the base material, making it easier for the ink to coagulate inside the base material. , the anchor effect can be more easily obtained.

In one embodiment, the pretreatment liquid A and the pretreatment liquid B are preferably discharged so as to land on the substrate in a certain order. According to this, it is possible to improve the fixability and the uniformity of the image density.
Specifically, a method in which the pretreatment liquid A is first discharged onto the substrate and then the pretreatment liquid B is discharged, and the pretreatment liquid A and the pretreatment liquid B land on the substrate in this order. can be Alternatively, a method may be employed in which the pretreatment liquid B is first ejected onto the substrate, then the pretreatment liquid A is ejected, and the pretreatment liquid B and the pretreatment liquid A land on the substrate in this order. .

The pretreatment liquid A and the pretreatment liquid B land on the base material in a certain order over the entire recording area of the base material to which the water-based ink is applied, thereby suppressing changes in the permeability of the ink to the base material. be able to. For example, in the case of serial printing, bi-directional printing increases productivity. On the other hand, in the case of serial bidirectional printing, if the landing order of the two types of pretreatment liquids changes between the forward pass and the return pass, the permeation of the ink into the base material is likely to be affected. For example, the case where the pretreatment liquid A aggregates the ink but the pretreatment liquid B does not aggregate will be described.

When the pretreatment liquid A hits first and the pretreatment liquid B hits second on the substrate, the ink and the pretreatment liquid B come into direct contact on the surface of the substrate, and the ink spreads on the substrate surface. Agglomeration is likely to occur. Therefore, the ink tends to remain on the surface of the substrate, and the image density tends to be high. On the other hand, when the pretreatment liquid B lands first and the pretreatment liquid A second on the substrate, the pretreatment liquid B is pushed by the pretreatment liquid A that lands on the substrate later. Since the ink penetrates to the inside of the material, and the ink also penetrates to the depth of the substrate where it can come into contact with the flocculant, compared to the case where the pretreatment liquid A hits first and the pretreatment liquid B hits second, the image Concentration tends to be low. Mixture of these two cases may cause deterioration of fixability and non-uniformity of image density.

On the other hand, when the pretreatment liquid A and the pretreatment liquid B land on the base material in a certain order, it is possible to reduce variations in the permeability of the ink to the base material. As a result, fixability can be improved, and uniformity of image density can also be improved.

The pretreatment liquid A and the pretreatment liquid B may be ejected in a certain order so as to land on the substrate, and the order is not limited. Then, the pretreatment liquid B is preferably discharged so as to land on the substrate in this order.
When the pretreatment liquid A lands first, the pretreatment liquid B and the ink that lands later tend to coagulate on the surface of the base material, which tends to increase the image density and improve the uniformity of the image density.

A method of ejecting the pretreatment liquid A and the pretreatment liquid B so as to land on the base material in a certain order is not particularly limited. For example, it is possible to use the methods described in the examples using the serial ink jet system and the examples using the line head ink jet system, which will be described later.

In one embodiment, of the pretreatment liquid A and the pretreatment liquid B, the landing time difference ΔT between two dots at which the distance between the dots is the shortest in the main scanning direction of at least the pretreatment liquid that lands on the base material first. _X (hereinafter, also referred to as “landing time difference ΔT _X ” or “ΔT _X ”), and landing time difference ΔT _Y (hereinafter, “ At least one of the impact time difference ΔT _Y ” or “ΔT _Y ”) (hereinafter also referred to as “impact time difference ΔT” or “ΔT”) is preferably 10 ms or more. At least one of ΔT _Y and ΔT _X (landing time difference ΔT) of the dots formed with the pretreatment liquid that first lands on the base material, out of pretreatment liquid A and pretreatment liquid B, is set to 10 ms or more, The permeability of the two pretreatment liquids can be increased, the anchoring effect of the ink film can be easily obtained, and the fixability of the image can be improved.
Here, the "main scanning direction (hereinafter also referred to as main scanning direction X)" is the direction in which dots are continuously ejected. becomes the longitudinal direction of The "direction intersecting the main scanning direction (hereinafter also referred to as direction Y)" is a direction that intersects the main scanning direction at right angles as long as the direction intersects the main scanning direction in which dots are continuously ejected. or a direction intersecting the main scanning direction at an angle other than a right angle. In a typical inkjet recording apparatus, the base material is conveyed in a direction perpendicular to the main scanning direction X, and two dots with the shortest distance between the dots in the direction perpendicular to the main scanning direction X land.

Resins tend to have poor permeability. For example, water-dispersible resins tend to be particulate and difficult to permeate, and water-soluble resins tend to thicken due to volatilization of water and become difficult to permeate. However, by setting the landing time difference ΔT to 10 ms or more, it is possible to increase the permeability of the two pretreatment liquids even when the pretreatment liquid containing resin is used.

The impact time difference ΔT is preferably 10 ms or more, more preferably 20 ms or more, and even more preferably 100 ms or more.
On the other hand, the impact time difference ΔT is preferably within 30 seconds, more preferably within 5 seconds, and even more preferably within 3 seconds. If the time exceeds 30 seconds, drying and/or film formation of the pretreatment liquid that first lands on the substrate may begin, resulting in poor permeability.
For example, the impact time difference ΔT is preferably 10 ms to 5 s, more preferably 20 ms to 3 s.

At least one of the landing time differences _ΔTx and _ΔTY may be 10 ms or more, or both may be 10 ms or more. Preferred ranges for each of the impact time differences _ΔTx and _ΔTY are the same as those for ΔT described above.

The method for setting the landing time difference ΔT to 10 ms or more is not particularly limited. For example, ejection may be performed in a serial manner.

In the case of serial ejection, for example, the landing time difference _ΔTx between two dots that have the shortest distance between the dots in the main scanning direction X may be set to 10 ms or more. In this case, for example, by controlling the moving speed of the serial print head in the main scanning direction X, ΔT _X can be adjusted to 10 ms or more. Alternatively, for example, the impact time difference _ΔTX can be adjusted to 10 ms or more by controlling the impact position of the serial printhead in the main scanning direction X to be at least a predetermined distance. Furthermore, you may combine these.

In the case of serial ejection, for example, the impact time difference ΔT _Y between two dots having the shortest distance between the dots in the direction Y intersecting the main scanning direction may be 10 ms or more. In this case, for example, by using a serial ink jet recording apparatus that conveys the substrate in a direction perpendicular to the main scanning direction, the pretreatment liquid is applied to the first liquid while scanning the serial type recording head in the main scanning direction X. line, move the base material by one line in the conveying direction, and then similarly discharge the pretreatment liquid onto the next second line on the base material. By controlling the movement speed, etc., the impact time difference ΔT _Y can be adjusted to 10 ms or more.

The impact time difference _ΔTX and the impact time difference ΔT _Y may be controlled independently or in combination.

Measurement of the landing time difference ΔTX between two dots with the shortest distance between dots in _the main scanning direction and the landing time difference ΔT _Y between two dots with the shortest distance between dots in the direction crossing the main scanning direction. As a method, it can be calculated from the ejection speed of the inkjet droplets, the transport speed or the serial driving speed, and the ejection order.

For example, in the case of using a serial print head, the landing time difference ΔT _X is typically determined by the ejection of two droplets with the shortest distance between dots, which are continuously ejected from the nozzle portion of the print head. Approximately match the interval.

In the case of using a serial type recording head, when the recording head ejects the pretreatment liquid in both directions, the recording head ejects the pretreatment liquid to the first line on the base material in the forward pass, After the material has moved by one line in the conveying direction, the recording head ejects the pretreatment liquid onto the second line on the substrate in the return pass. In the vicinity of the turning point, the impact time difference between adjacent dots in the direction Y intersecting the main scanning direction is minimized. Therefore, in this configuration, the landing time difference ΔT _Y substantially matches the transport time for one line of the base material.

Further, in the case of using a serial type recording head, when the recording head ejects the pretreatment liquid in one direction, the recording head ejects the pretreatment liquid to the first line on the base material in the forward pass, While the material moves by one line in the conveying direction, the recording head returns to the starting point of the forward pass without ejecting the pretreatment liquid on the return pass, and then the recording head dispenses the pretreatment liquid onto the next second line on the substrate on the return pass. For ejection, typically, the shorter of the time taken for the substrate to move by one line in the transport direction and the time taken for the recording head to return to the start point of the forward pass on the return pass, is approximately equal to the landing time difference ΔT _Y. match.

In addition, since the line head type recording head ejects droplets from the linear recording head while the substrate moves in the transport direction, the droplet ejection interval and ΔT _Y in the transport direction of the substrate are substantially the same. do. In addition, in the line head type recording head, in the normal ejection method, the droplets land on the base material at substantially the same timing in the main scanning direction X. Therefore, setting the landing time difference ΔT _Y to 10 ms or more is a simpler control method. preferred because

For both the pretreatment liquid A and the pretreatment liquid B, it is more preferable that at least one of the landing time difference _ΔTX and the landing time difference _ΔTY (landing time difference ΔT) is 10 ms or more. That is, it is preferable that both the landing time difference ΔT of the pretreatment liquid that lands first on the substrate and the landing time difference ΔT of the pretreatment liquid that lands next on the substrate are 10 ms or more. Note that the landing time difference ΔT of the pretreatment liquid that lands first on the substrate may be 10 ms or more, and the landing time difference ΔT of the pretreatment liquid that lands next on the substrate may be less than 10 ms.

It is preferable that the pretreatment liquid A and the pretreatment liquid B are applied at least to the recording area to which the ink is to be applied. The pretreatment liquid A and the pretreatment liquid B may, for example, be applied only to areas printed with water-based ink, or may be applied to areas other than areas printed with water-based ink. The pretreatment liquid A and the pretreatment liquid B may be applied to part or all of the substrate.
The amounts of the pretreatment liquids A and B applied to the substrate are not particularly limited. For example, when a cloth is used as the base material, the amounts of the pretreatment liquids A and B to be applied are preferably 0.1 g/m ² to 50 g/m ² , preferably 1 g/m ² , as the non-volatile content per application area. ~20 g/ ^m2 is more preferred, and 2 to 20 g/ ^m2 is more preferred.

Next, step 2 according to one embodiment will be described. In step 2, after applying the pretreatment liquid A and the pretreatment liquid B, a water-based inkjet ink is applied onto the substrate by an inkjet method.
The method of ejecting the water-based inkjet ink in step 2 is not particularly limited as long as it is an inkjet method. Either the line head type or the serial type may be used, but the serial type is preferred.
Moreover, it is preferable to perform the process 1 and the process 2 with the same inkjet recording device.

The amount of the ink to be applied to the substrate is not particularly limited. For example, when fabric is used as the substrate, the amount of non-volatile matter per unit area of the fabric is 0.1 g/m ² to 50 g/m ² from the viewpoint of texture. is preferred, 1 g/m ² to 30 g/m ² is more preferred, and 2 to 20 g/m ² is more preferred.

The inkjet recording apparatus used in step 1 and/or step 2 may be of any type, such as a piezo system, an electrostatic system, or a thermal system. Alternatively, it is preferable that droplets of the pretreatment liquid can be ejected and the ejected droplets can adhere to the substrate.

Steps 1 and 2 will be described more specifically using an example using a serial ink jet method and an example using a line head type ink jet method.

A serial ink jet recording apparatus is mounted movably in the main scanning direction X, and includes a serial recording head having a nozzle portion, and a conveying device that conveys a substrate to a position facing the recording head. While moving the serial recording head in the main scanning direction X, an operation of ejecting ink from the nozzles and an operation of moving the substrate in the conveying direction Y intersecting the main scanning direction are repeated to obtain an image on the substrate. can be recorded.

An example of a serial inkjet recording apparatus includes a recording head unit that can move in the main scanning direction X and a conveying device that conveys a substrate in the conveying direction Y. The recording head unit includes a first recording head, a second recording head, and a second recording head. and a third recording head. The recording head unit can be reciprocated in the main scanning direction X by a drive belt. In this example, for example, one of the pretreatment liquid A and the pretreatment liquid B is supplied to the first recording head, the other of the pretreatment liquid A and the pretreatment liquid B is supplied to the second recording head, and the water-based ink is supplied to the second recording head. is supplied to the third recording head, and the pretreatment liquid A, the pretreatment liquid B, and the water-based ink are ejected from the respective recording heads, so that an image can be recorded by layering these on the base material. can.

The substrate conveying device has the recording head unit fixed to the inkjet recording apparatus, and moves the substrate in the conveying direction Y using a conveying roller or the like to pass through a position facing the recording head unit. good. Further, the substrate conveying device may be one in which the substrate is fixedly mounted on the mounting portion, and the recording head unit is moved to relatively convey the substrate in the conveying direction Y. good. Preferably, the substrate is conveyed in a direction perpendicular to the main scanning direction of the recording head unit.
The recording apparatus may also include a heating device for heating the substrate during printing or at any stage before or after printing. By heating the substrate with the heating device, drying of each pretreatment liquid and water-based ink can be accelerated. Further, when each pretreatment liquid and water-based ink contain a resin component, the formation of a resin film can be promoted.
The recording device may also include an input device for inputting image data to be printed. The input device can include an external input section for receiving image data captured from a scanner or a personal computer. Based on this image data, the ejection of water-based ink from each print head can be controlled, and each pretreatment liquid can be ejected in advance to the print area where the water-based ink is to be ejected.

A serial inkjet recording apparatus according to one embodiment includes, for example, a first recording head to which one of pretreatment liquid A and pretreatment liquid B is supplied, and the other of pretreatment liquid A and pretreatment liquid B to which the other is supplied. A serial type recording head unit having a second recording head and a third recording head to which water-based ink is supplied, and one of the pretreatment liquid A and the pretreatment liquid B is supplied from the first recording head to the base material. a step of applying the other of the pretreatment liquid A and the pretreatment liquid B from the second recording head to the recording area of the substrate; and a step of applying the water-based ink from the third recording head to the recording area of the substrate. The steps of applying to the regions can be performed in this order. According to this, one of the pretreatment liquid A and the pretreatment liquid B, the other of the pretreatment liquid A and the pretreatment liquid B, and the water-based ink are laminated in this order on the base material, and the pretreatment liquid A and the pretreatment liquid B are laminated in this order. The pretreatment liquid B is deposited on the base material in a certain order to obtain a printed material on which an image is recorded.

As a specific method, the first printhead, the second printhead, and the third printhead are arranged in this order in the main scanning direction of the printhead unit, and the printhead unit is arranged in the main scanning direction. While moving in one direction, one of the pretreatment liquids A and B from the first recording head, the other of the pretreatment liquids A and B from the second recording head, and from the third recording head Aqueous inks can be applied to the recording areas of the substrate in this order.

FIG. 1 shows a top view schematically showing an example of a serial print head unit according to one embodiment.
In the printhead unit 100 shown in FIG. 1, the first printhead 11, the second printhead 12, and the second printhead 12 are arranged along the main scanning direction X from the downstream side of the outward path (from left to right in the figure; the same shall apply hereinafter). 3 recording heads 13 are arranged in a row in this order. The third recording head 13 has four recording heads 13K, 13C, 13M, and 13Y for each of the four water-based inks of black (K), cyan (C), magenta (M), and yellow (Y). Prepare. 2 and 4, which will be described later, are the same with reference numerals 13K, 13C, 13M, 13Y, and 100. FIG.
Then, the pretreatment liquid A is supplied to the first recording head 11 , the pretreatment liquid B is supplied to the second recording head 12 , and the water-based ink is supplied to the third recording head 13 . in the forward direction of the main scanning direction X, the pretreatment liquid A is discharged from the first recording head 11, the pretreatment liquid B is discharged from the second recording head 12, and the pretreatment liquid B is discharged from the third recording head 13. By ejecting the water-based ink, the pretreatment liquid A, the pre-treatment liquid B, and the water-based ink can be applied in this order onto the substrate. That is, the pretreatment liquid A and the pretreatment liquid B land on the substrate in this order.
In the configuration of the recording head unit 100, the application order is only in the forward pass in the main scanning direction X, and the application order is reversed in the return pass. Therefore, in order to obtain this application order, it is preferable to perform printing only in the forward pass and not to perform ejection in the reverse pass.

As another specific method, the first printhead and the second printhead are arranged in a row in the main scanning direction of the printhead unit, and the third printhead is arranged between the first printhead and the second printhead. A step of placing one of the pretreatment liquid A and the pretreatment liquid B from the first recording head on the downstream side of the substrate conveyance direction with respect to the recording head and applying one of the pretreatment liquid A and the pretreatment liquid B to the recording area of the substrate; The step of applying the other of the pretreatment liquid A and the pretreatment liquid B from the head to the recording area of the substrate is performed in this order, then the substrate is moved in the conveying direction with respect to the recording head unit, and the pretreatment liquid A and the pretreatment liquid B are applied. A step of applying water-based ink from a third recording head to the recording area of the base material treated with the pretreatment liquid B can be performed.

FIG. 2 shows a top view schematically showing another example of the serial print head unit according to one embodiment.
In FIG. 2, the print head unit 100 includes a first print head 11 supplied with the pretreatment liquid A and a second print head 12 supplied with the pretreatment liquid B. A second head including a first head row arranged in the direction X and a third recording head 13 supplied with water-based ink downstream of the first head row in the substrate transport direction Y. column.
Then, while moving the recording head unit 100 in the main scanning direction X, the pretreatment liquid A is ejected from the first recording head 11 and the pretreatment liquid B is ejected from the second recording head 12; is moved in the transport direction Y, and the operation of ejecting water-based ink from the third recording head 13 onto the recording area on the substrate to which the pretreatment liquid A and the pretreatment liquid B are applied is repeated. Pretreatment liquid A, pretreatment liquid B, and water-based ink can be applied thereon in this order.
In the configuration of the recording head unit 100, the application order is only in the forward pass (from left to right in the drawing) in the main scanning direction X, and the application order is reversed in the return pass. Therefore, in order to obtain this application order, it is preferable to perform printing only in the forward pass and not to apply the ink in the return pass.

FIG. 3 shows a top view schematically showing still another example of the serial print head unit according to one embodiment.
FIG. 3 shows an example in which the arrangement of the first recording head 11 and the second recording head 12 is different from that in FIG. In FIG. 3, the first recording head 11 and the second recording head are spaced apart. More specifically, the first printhead 11 is positioned on one side of the printhead unit 100 with respect to the main scanning direction X, and the second printhead 12 is positioned on the other side of the printhead unit with respect to the main scanning direction X. located on the side. More preferably, the first recording head 11 and the second recording head 12 are arranged so as not to overlap in the transport direction Y with the third recording head 13 that ejects water-based ink. With such an arrangement, the mist derived from the coagulant of the pretreatment liquid B can be prevented from adhering to the nozzles for ejecting the pretreatment liquid A and the nozzles for ejecting the water-based ink. This makes it possible to further prevent nozzle clogging of the first recording head 11 and the third recording head 13 .

In the recording head unit shown in FIGS. 1 to 3, for example, the pretreatment liquid B is supplied to the first recording head 11, the pretreatment liquid A is supplied to the second recording head 12, and the first recording head 11 The pretreatment liquid B may be ejected from the second recording head 12 and the pretreatment liquid A may be ejected from the second recording head 12 .

When ejection is performed in the forward and backward passes of a serial print head unit, according to the conventional printing method, the ejection order of the two types of pretreatment liquid and the water-based ink is switched between the forward pass and the return pass of the print head unit. On the material, the stacking order of the two types of pretreatment liquids is changed for each line adjacent to the conveying direction Y of the base material. FIG. 4 shows an explanatory diagram for explaining this conventional recording method.
In FIG. 4, (a) shows the arrangement of the print head unit 100 from above, and the case where the pretreatment liquid A is ejected from the first print head 11 in each pass is indicated by hatched circles, and the second white circles indicate the case where the pretreatment liquid B is ejected from the recording head 12 of . (b) shows the surface of the substrate from above, and shows the case where the pretreatment liquid A and the pretreatment liquid B are laminated in this order on each line along the main scanning direction of the recording head unit 100. FIG. From the left in the figure, hatched circles and white circles indicate the order, and the reverse order of lamination is indicated from the left in the figure by white circles and hatched circles.
In FIG. 4, as shown in FIG. 4A, in the first pass of the forward pass, the first recording head 11 moves ahead of the second recording head 12, so that the pretreatment liquid A is applied onto the base material. Then, the pretreatment liquid B is discharged. Then, as shown in (b) of the drawing, the pretreatment liquid A and the pretreatment liquid B are laminated in this order on the substrate.
In the second pass of the return path, since the second recording head 12 moves ahead of the first recording head 11, the pretreatment liquid A is ejected onto the substrate next to the pretreatment liquid B, and the pretreatment liquid A is ejected onto the substrate. Pretreatment liquid B and pretreatment liquid A are laminated in this order.
In the third pass of the forward pass, the pretreatment liquid A and the pretreatment liquid B are laminated in this order on the base material in the same manner as in the first pass.
In the printed matter obtained, the stacking order of the two types of pretreatment liquids is changed in the lines adjacent to each other in the transport direction of the base material. If the landing order of the two kinds of pretreatment liquids is not constant as described above, the penetration of the ink into the base material becomes uneven, and there is a problem that the fixability of the image on the printed matter is deteriorated.

In the printing method according to one embodiment, along the main scanning direction X of the print head unit, the first print head is provided on the downstream side of the forward pass, the second print head is provided on the upstream side, and the print head unit is moved on the forward pass. When moving the print head unit, the pretreatment liquid A is first ejected from the first print head, and then the pretreatment liquid B is ejected from the second print head. and the pretreatment liquid B are preferably not discharged. As a result, the pretreatment liquid A and the pretreatment liquid B are laminated in this order on the substrate over the entire recording area of the substrate. That is, in FIG. 2, it is preferable to repeat only the ejection of the first pass of the forward pass and not perform the ejection of the second pass of the return pass. In FIG. 2, by repeating only the second pass of the return pass without performing the first pass and the third pass of the forward pass, the pretreatment liquid B and the pretreatment liquid A are deposited on the substrate. They are stacked in order.
In the case of using the recording head unit 100 shown in FIGS. 2 and 3, after the pretreatment liquid A and the pretreatment liquid B are ejected so as to be laminated on the substrate, the third recording head 13 applies each pretreatment liquid. An image can be recorded by conveying the substrate so as to face the area and ejecting water-based ink from the third recording head 13 .

Alternatively, the pretreatment liquid A and the pretreatment liquid B may be applied in both directions of the forward and backward passes using a serial ink jet recording apparatus. This method can further improve productivity compared to the case where the pretreatment liquid A and the pretreatment liquid B are ejected in one of the forward and backward passes in the main scanning direction and not ejected in the other. In the following description, the order of movement in the forward and backward passes in the main scanning direction is not particularly limited, and the order of the forward and backward passes may be reversed. Also, in the following description, the order in which the pretreatment liquid A and the pretreatment liquid B are applied may be reversed.

As an example of a bidirectional printing method, a print head unit in which a first print head and a second print head are arranged in the main scanning direction X is used, and in a forward pass in the main scanning direction, printing from the first print head to the second print head is performed. 1 pretreatment liquid is applied onto the substrate, and in the return pass in the main scanning direction, the pretreatment liquid B is applied onto the substrate from the second recording head so as to overlap the pretreatment liquid A applied in the forward pass. There is a way.
In the example shown in FIG. 1, the aqueous ink can be applied onto the substrate from the third recording head so as to overlap the pretreatment liquid B while moving the recording head unit in the outward path in the main scanning direction. In the example shown in FIG. 2 or 3, after the treatment liquid B is applied, the substrate is moved in the transport direction Y, and the recording head unit is moved in the main scanning direction so as to overlap the pretreatment liquid B. Aqueous ink can be applied onto the substrate from the third recording head.

Another example of the bidirectional recording method is a recording head unit in which a first recording head is arranged on the upstream side with respect to the conveyance direction Y of the base material, and a second recording head is arranged on the downstream side thereof. is used to apply the pretreatment liquid A onto the substrate from the first recording head in the forward pass in the main scanning direction X, move the substrate in the conveying direction, and apply the pretreatment liquid A in the return pass in the main scanning direction. The pretreatment liquid B can be applied onto the substrate from the second recording head so as to overlap.
In order to apply the two pretreatment liquids more efficiently, in the return pass in the main scanning direction, the pretreatment liquid B is applied onto the substrate from the second recording head, and the pretreatment liquid A is applied from the first recording head. may be applied onto the substrate. Similarly, in the forward pass in the main scanning direction, the pretreatment liquid A may be applied onto the substrate from the first recording head, and the pretreatment liquid B may be applied onto the substrate from the second recording head.
In the configuration in which the first printhead and the second printhead are arranged in the transport direction, a printhead unit in which the third printhead is arranged further downstream of the second printhead in the transport direction is used. After applying the treatment liquid B, the base material is moved in the transport direction, and while the recording head unit is moved in the main scanning direction, the aqueous ink is applied from the third recording head so as to overlap the pretreatment liquid B. can be applied onto the substrate.

As still another example of the bidirectional recording method, a first recording head and a second recording head are arranged in the main scanning direction X, and the substrate is conveyed to each of the first recording head and the second recording head. A recording head unit in which a plurality of nozzles are formed in a row along the direction Y can be used. While reciprocating the recording head unit in the main scanning direction, the substrate is moved in the transport direction, and the pretreatment liquid A is applied onto the substrate from the upstream nozzle of the first recording head in the transport direction. A plurality of lines are formed, the substrate is continuously moved in the transport direction, and the ink is applied from the downstream nozzle of the second recording head in the transport direction to the upstream nozzle of the previous first recording head. A second pretreatment liquid may be applied onto the substrate so as to overlap the pretreatment liquid A, thereby forming a plurality of lines in which the pretreatment liquid A and the pretreatment liquid B are laminated in this order. can.
In the example shown in FIG. 1, a third recording head in which a plurality of nozzles are formed in a row along the transport direction is used, and a third recording head located further downstream in the transport direction than the nozzles of the second recording head is used. The water-based ink can be applied onto the substrate from the nozzles of the recording head in such a manner as to overlap the pretreatment liquid B applied from the nozzles on the upstream side in the transport direction.
In the example shown in FIG. 2 or FIG. 3, after the pretreatment liquid B is applied, the substrate is moved in the transport direction Y, and the recording head unit is moved in the main scanning direction so as to overlap the pretreatment liquid B. Then, the aqueous ink can be applied onto the substrate from the third recording head.

Specifically, in the recording head unit shown in FIGS. 1 to 3, the first recording head 11 and the second recording head 12 each have a plurality of nozzles formed in a row along the substrate conveyance direction Y. Two-way granting can be performed with a configuration such as In each printhead, a plurality of nozzles are arranged in the transport direction Y so as to be spaced apart from each other.
First, the recording head unit 100 ejects droplets of the first pretreatment liquid so as to correspond to one dot from one nozzle on the upstream side of the substrate conveyance direction Y of the first recording head 11 . is moved in the forward direction in the main scanning direction X, and dots are continuously landed in the main scanning direction X to apply the pretreatment liquid A in a line shape with a width of 1 dot. Next, the base material is moved in the transport direction Y, and droplets ejected from one nozzle adjacent to the downstream side in the transport direction Y with respect to the previous nozzle of the first recording head 11 are The line-shaped pretreatment liquid A is landed on the substrate so as to be adjacent to the upstream side of the substrate in the conveying direction Y, and the line-shaped pretreatment liquid A is applied in the same manner as the line-shaped pretreatment liquid A. of the pretreatment liquid B is applied. At this time, on the substrate, two dots adjacent to each other in the transportation direction Y of the substrate determine the time for the recording head unit to move in the transportation direction Y, the moving speed of the recording head unit, the turn-around time of the recording head unit, and the like. By controlling, the landing time difference ΔT _Y can be set to 10 ms or more.
Also, two or more nozzles arranged continuously in the transport direction Y among the plurality of nozzles of the first recording head are used in one pass, and are spaced apart in the transport direction Y corresponding to the interval between the nozzles. Then, in the same manner as described above, each previous line of pretreatment liquid A is applied to the upstream side of the substrate in the conveying direction Y in a line. of the pretreatment liquid A can be applied. With this method, the image recording amount per pass of the recording head unit can be increased, and productivity can be further improved.

Next, the pretreatment liquid B can be ejected from the nozzles of the second recording head 12 to land on the substrate so as to overlap the dots of the pretreatment liquid A that have landed on the substrate, thereby forming dots.
For example, the pretreatment liquid A is ejected from the nozzle of the first recording head 11 on the upstream side in the conveying direction Y of the base material and applied to one line-shaped recording area. While moving in the conveying direction Y, the pretreatment liquid B is ejected from the nozzles of the second recording head 12 which is located downstream in the conveying direction Y of the base material with respect to the positions of the nozzles of the first recording head 11 . may be granted.

Next, in the example shown in FIG. 1, a third recording head in which a plurality of nozzles are formed in a row along the conveying direction is used to convey the substrate in the conveying direction Y, while the second recording head Water-based ink is ejected onto the base material from the nozzles of the third recording head located further downstream in the transport direction than the nozzles so as to overlap the dots formed by overlapping the pretreatment liquid A and the pretreatment liquid B. Dots can be formed by landing on the substrate.
In the example shown in FIG. 2 or FIG. 3, while the base material is conveyed in the conveying direction Y, the aqueous ink is applied from the third recording head 13 so that the pretreatment liquid A and the pretreatment liquid B overlap the dots formed by overlapping. Dots can be formed by ejecting ink and making it land on the substrate.
By repeating the above operation, pretreatment liquid A, pretreatment liquid B, and water-based ink are applied in this order onto the substrate, and pretreatment liquid A and pretreatment liquid B land on the substrate in a certain order. can do.

In the bidirectional printing described above, when recording an image with resolution N times the resolution of the recording head, N lines are formed in an area corresponding to the interval between nozzles adjacent to each other in the conveying direction Y of the base material. can be done by where N is a positive integer.
Specifically, when printing an image of 1200 dpi using a print head of 300 dpi, it is preferable to form four dots in an area corresponding to the interval between adjacent nozzles in the transport direction Y of the print head. Therefore, it is preferable to form four lines in a region corresponding to the interval between nozzles adjacent to each other in the transport direction Y of the substrate.

The line head type ink jet recording method includes a line head type recording head which is arranged in the width direction of the base material which intersects, preferably perpendicular to the conveying direction of the base material, and which has a plurality of nozzle rows in the width direction of the base material. can be performed using
An example of a line head type ink jet recording apparatus includes a conveying device that conveys a substrate in the conveying direction Y, and at least three recording heads arranged in a line in a direction X that intersects the conveying direction Y of the substrate. Prepare. In this example, for example, the at least three recording heads are a first recording head to which the pretreatment liquid A is supplied from the upstream side along the conveying direction Y of the substrate, and a first recording head to which the pretreatment liquid B is supplied. A second printhead and a third printhead with shared aqueous ink are provided in that order. Then, pretreatment liquid A, pretreatment liquid B, and water-based ink are ejected from the respective nozzle rows, so that an image can be recorded by layering these on the substrate in this order. The pretreatment liquid A may be supplied from the first print head and the pretreatment liquid B may be supplied from the second print head, and the application order of the pretreatment liquid A and the pretreatment liquid B may be reversed.
In the line head type inkjet recording apparatus, by determining the arrangement order of the recording heads to which the two types of pretreatment liquids and the water-based ink are respectively supplied, the substrates for the two types of pre-treatment liquids and the water-based ink are determined. It is possible to determine the order of grant to In this way, the pretreatment liquid A and the pretreatment liquid B can be discharged in a certain order so as to land on the substrate.

It is preferable that the printed matter manufacturing method includes, after step 2, a step of heating the substrate (hereinafter sometimes referred to as a heating step). As a result, the ink is dried, and the water-dispersible resin is formed into a film, making it easy to form a strong ink film.

The heating temperature in the heating step of heating the substrate after step 2 is preferably 70° C. or higher, more preferably 100° C. or higher. On the other hand, the heating temperature in this heating step is preferably 200° C. or less. The heating temperature in this heating step is more preferably 70 to 200.degree.

In the method for producing a printed matter, in step 1, while two pretreatment liquids are applied and/or between steps 1 and 2, the pretreatment liquid such as a step of heating the substrate is dried. A step may be included. However, in the method for producing a printed matter of the present embodiment, in step 1, the application of the pretreatment liquid, which lands on the substrate later, of the pretreatment liquid A and the pretreatment liquid B, and the application of the inkjet ink It is also preferable to use a wet-on-wet method.
Applying the pretreatment liquid that lands on the base material afterward and applying the ink in a wet-on-wet manner allows the two pretreatment liquids to mix appropriately, making it easier to improve the uniformity of the image density. can.
The pretreatment liquid that lands first on the base material can easily permeate into the base material as if pushed by the pretreatment liquid that lands on the base material later. Cheap.

EXAMPLES The present invention will be described in more detail below based on examples, but the present invention is not limited only to these examples. "%" means "% by mass" unless otherwise specified. The blending amount of each component in the table is also shown in "% by mass".

<Preparation of pretreatment liquid and ink>
The raw materials listed in Tables 1 to 3 were mixed and stirred at 100 rpm for 30 minutes using a mix rotor. After stirring, the mixture was filtered through a 5 μm nylon syringe filter to prepare Ink 1, pretreatment solutions A1 to A4, and pretreatment solutions B1 to B3. The blending amount of each raw material in the table is shown in % by mass. The blending amount of each raw material in the table is the amount including the volatile matter for the component containing the volatile matter.

The raw materials listed in Tables 1 to 3 are as follows.

Superflex 500M: Emulsion of nonionic water-dispersible urethane resin manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd. Movinyl 7720: Emulsion of nonionic water-dispersible acrylic resin manufactured by Japan Coating Resin Co., Ltd. Simplex PUE-C200B: Murayama Chemical Laboratory Co., Ltd. Cationic water-dispersible urethane resin emulsion Super Flex 740: Dai-ichi Kogyo Seiyaku Co., Ltd. anionic water-dispersible urethane resin emulsion Olfin E1010: Nissin Chemical Co., Ltd. acetylene glycol-based surfactant Silface SAG002: Japan Silicone-based surfactant manufactured by Shinkagaku Kogyo Co., Ltd.

Lactic acid: Fujifilm Wako Pure Chemical Co., Ltd. Calcium chloride: Fujifilm Wako Purechemical Co., Ltd. Charol DC-303P: Daiichi Kogyo Seiyaku Co., Ltd., cationic water-soluble resin, active ingredient content 41% (polydiallyldimethylammonium chloride)
Diethylene glycol: manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd. Dipropylene glycol: manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd. 1,2-butanediol: manufactured by Tokyo Chemical Industry Co., Ltd.

CAB-O-JET300: carbon black pigment dispersion manufactured by Cabot Corporation Takenate WB3936: isocyanate cross-linking agent manufactured by Mitsui Chemicals, Inc. Glycerin: manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd. Ethylene glycol: manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.

Two kinds of pretreatment liquids were mixed and cohesiveness was evaluated. Specifically, in the combinations shown in Table 1, 10 g each of pretreatment solutions A-1 to A-4 were mixed with 10 g each of pretreatment solutions B-1 to B-3, and whether or not aggregation occurred was determined. observed visually. Table 1 shows the results.

<Manufacture of printed matter>
Using a 100% polyester cloth as the base material, using the pretreatment liquid and ink 1 shown in Tables 4 to 6, printing was performed according to the following procedure to obtain a printed matter printed with a single-color solid image of 200 mm × 200 mm. rice field.

In Examples 1 to 11 and Comparative Examples 1 to 3, a serial ink jet printer using a recording head with a resolution of 300 dpi was used. The arrangement position of the serial type recording head unit is as shown in FIG. In FIG. 2, the first recording head 11 is supplied with the first pretreatment liquid, the second recording head 12 is supplied with the second pretreatment liquid, and the third recording head is supplied with the black ink. Ink 1 was supplied to the recording head 13K.

In Examples 1 to 11, in the combinations shown in Tables 4 to 5, the first pretreatment liquid and the second pretreatment liquid were discharged in this order so as to land on the substrate, After applying the pretreatment liquid, ink 1 was applied to the substrate to produce a printed matter.

Specifically, using a 300 dpi recording head, the first pretreatment liquid, the second pretreatment liquid, and the water-based ink are each ejected by bidirectional printing at 1200 dpi x 1200 dpi to form a single-color solid image of 200 mm x 200 mm. printed. The movement of the substrate by one line in the transport direction Y was made to correspond to a quarter of the distance between the nozzles in the transport direction Y. In addition, the impact time difference ΔT _Y between adjacent lines in the transport direction Y of the substrate of the penetrating liquid on the substrate was 10 ms or more.

A plurality of nozzles are formed in the first recording head 11, the second recording head 12, and the third recording head 13 along the conveying direction Y of the base material. The second recording head 12 ejects penetrant liquid from three consecutive nozzles on the upstream side in the transport direction Y, and transports the substrate while reciprocating the recording head unit in the main scanning direction X. The first pretreatment liquid was discharged onto the substrate so that four rows of lines were formed in the distance between the nozzles adjacent to each other in the transport direction Y.
At this time, when nozzle a, nozzle b, and nozzle c are arranged from the upstream side in the transport direction Y, the first line of the first pretreatment liquid is formed from each of the three nozzles in the forward pass in the main scanning direction X. bottom. Next, the substrate is conveyed so that the first line of penetrant liquid discharged from the previous nozzle a is adjacent to the upstream side in the conveying direction Y of the first line of penetrant liquid in the return pass in the main scanning direction X from the nozzle b. A second line was formed by discharging the pretreatment liquid onto the substrate. In the formation of the second line, the first pretreatment liquid was also discharged from the nozzles a and c at similar intervals. By repeating this operation, four lines of the first pretreatment liquid were formed in the distance between nozzles adjacent to each other in the conveying direction Y of the substrate.

The base material is continuously transported in the transport direction Y, and the area where the four lines of the first pretreatment liquid are formed is the three ahead of the second recording head 12 with respect to the transport direction Y. At a position facing the nozzles of the first recording head 11 downstream of the nozzles, the substrate is moved while reciprocating the recording head unit in the main scanning direction, and the first pretreatment liquid The second pretreatment liquid is discharged onto the base material from the first recording head 11 so as to overlap each of the four lines, and the first pretreatment liquid and the second pretreatment liquid are discharged in this order. A stacked 4 line was formed. The discharge method of the second pretreatment liquid is the same as that of the first pretreatment liquid.
Furthermore, the base material is continuously transported in the transport direction Y, and the 4-line region formed by laminating the first pretreatment liquid and the second pretreatment liquid is formed on the downstream side in the transport direction Y. At a position facing the third recording head 13, while moving the recording head unit in the main scanning direction, water-based ink is ejected from the third recording head 13. An image was formed by laminating the treatment liquid and the water-based ink in this order.

In Comparative Example 1, the pretreatment liquid B-2 was applied as the first liquid, and the water-based ink 1 was applied without applying the pretreatment liquid as the second liquid.
In Comparative Example 2, the pretreatment liquid A-3 was applied as the first liquid, and the water-based ink 1 was applied without applying the pretreatment liquid as the second liquid.
In Comparative Example 3, the two kinds of pretreatment liquids shown in Table 6 are applied in the method shown in FIG. In the return pass, the pretreatment liquid B-2, the pretreatment liquid A-2, and the ink were ejected so as to land in this order to produce a printed matter.

The printed matter of Comparative Example 4 was produced by a line head type inkjet printer in which the same recording heads as used in the production of the printed matter of Examples 1 to 11 and Comparative Examples 1 to 3 were staggered and set at 1200 dpi in the main scanning direction. The pretreatment liquids listed in Table 6 were ejected in the order listed in Table 6 onto the substrate (100% polyester cloth), and then ink 1 was ejected to form a 200 mm × 200 mm single-color solid image. printed. The pretreatment liquid and ink were ejected at an ejection frequency of 15 k, a conveying speed of 38 m/min, and 1200 dpi in the sub-scanning direction.

In each of Examples 1 to 11 and Comparative Examples 1 to 4, ink 1 was used on the substrate to perform inkjet printing, followed by heat pressing at 180° C. for 1 minute.

Table 4 shows the landing time difference ΔT _X between two dots at which the distance between dots is the shortest in the main scanning direction, and the main The “ΔT” column indicates whether or not at least one of the landing time differences ΔT _Y between two dots having the shortest distance between the dots in the direction crossing the scanning direction is 10 ms or more. "10 ms or more" indicates that at least one of ΔT _X and ΔT _Y of the pretreatment liquid that first lands on the substrate (ΔT) is 10 ms or more, and "less than 10 ms" indicates that Both ΔT _X and ΔT _Y of the pretreatment liquid that lands are less than 10 ms.
Since only one type of pretreatment liquid was used in Comparative Examples 1 and 2, the used pretreatment liquid is shown. In Comparative Example 3, although the landing order was not constant, ΔT was 10 ms or more for both of the two types of pretreatment liquids.

<Evaluation of fixability>
According to the method specified in JIS L0849, the printed material was rubbed using a type II friction tester, and the contamination of the rubbed cloth was evaluated using a contamination gray scale. Evaluation criteria are shown below. The results are shown in Tables 4-6.
AA: Dry friction contamination grade 3 or higher A: Dry friction contamination grade 2-3 B: Dry friction contamination grade 2 C: Dry friction contamination grade 2 or less

<Evaluation of Image Density Uniformity>
Image density uniformity was evaluated as follows. The printed materials of Examples and Comparative Examples obtained as described above were visually observed from a distance of 50 cm, and evaluated according to the following evaluation criteria. The results are shown in Tables 4-6.
A: Not much unevenness in image density is observed. B: There is unevenness in image density compared to A. C: Clear unevenness in image density is observed.

All of the prints of Examples were excellent in fixability. On the other hand, in Comparative Examples 1 and 2, pretreatment liquid A and pretreatment liquid B were produced using only one of pretreatment liquid A containing a resin and pretreatment liquid B containing a flocculant. The shortest distance between dots in the main scanning direction of the printed matter of Comparative Example 3, which is not ejected so as to land on the substrate in a certain order, and the pretreatment liquid that is ejected onto the substrate first Comparative Example 4 _in which both the landing time difference ΔT _X between two dots of All of the prints were inferior in fixability.

REFERENCE SIGNS LIST 11 first recording head 12 second recording head 13 third recording head 100 recording head unit

Claims (8)

a step of applying a pretreatment liquid A containing a resin and a pretreatment liquid B containing a flocculant to a recording area on a base material by an inkjet method;
After applying the pretreatment liquid A and the pretreatment liquid B, a step of applying a water-based inkjet ink to the recording area on the substrate by an inkjet method,
The inkjet method for applying the pretreatment liquid A and the pretreatment liquid B is a serial inkjet method,
The pretreatment liquid A and the pretreatment liquid B are ejected so as to land on the base material in a certain order over the entire recording area of the base material ,
A landing time difference ΔT _X between two dots having the shortest distance between dots in the main scanning direction, of the pretreatment liquid A and B, which hits the substrate first , and A method for producing printed matter, wherein at least one of landing time difference ΔT _Y between two dots having the shortest distance between dots in a direction crossing the main scanning direction is 10 ms or more. 2. The method for producing a printed matter according to claim 1, wherein the resin of the pretreatment liquid A contains a water-dispersible resin. 3. The method for producing printed matter according to claim 2, wherein the water-dispersible resin includes at least one selected from the group consisting of cationic water-dispersible resins and nonionic water-dispersible resins. 4. The method for producing printed matter according to claim 3, wherein the water-dispersible resin includes a nonionic water-dispersible resin. The method for producing a printed matter according to any one of claims 2 to 4, wherein the water-dispersible resin includes a water-dispersible urethane resin. The method for producing a printed matter according to any one of claims 1 to 5, wherein the flocculant contains an organic acid. The pretreatment liquid A and the pretreatment liquid B are discharged so as to land on the substrate in the order of the pretreatment liquid A and then the pretreatment liquid B. A method for producing the described printed matter. Among the pretreatment liquid A and the pretreatment liquid B, ejection of the pretreatment liquid to be ejected onto the substrate later and ejection of the water-based inkjet ink are both performed by a wet-on-wet method. Item 8. A method for producing a printed matter according to any one of items 1 to 7 .

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