JP2022128806A - Method for producing printed material - Google Patents

Abstract

To improve fixability of an image onto a printed material, the image quality of the printed material, and the back-side ink density of it.SOLUTION: An inkjet recording method discharges ink containing a colorant and water, a process liquid A containing a permeation promoting component, a process liquid B containing a fixation component, and a process liquid C containing a flocculation component for flocculating the ink. The process liquids and the ink land on a substrate in the order of the process liquid A, the process liquid B, the process liquid C, and the ink.SELECTED DRAWING: None

Description

One embodiment of the present invention relates 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. Non-aqueous ink can be classified into solvent ink (solvent-based ink) whose main solvent is a volatile organic solvent, and oil-based ink (oil-based ink) whose main solvent is a low-volatile or non-volatile organic solvent.

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 substrate, water-based inks may not sufficiently penetrate the substrate, resulting in problems of image quality and image fixability.

Patent Document 1 proposes a method of using two types of pretreatment liquids with different penetrability to increase reactivity with ink regardless of the type of medium and also to improve wetting and spreading properties of the pretreatment liquid. ing.

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 the embodiments of the present invention is to improve the fixability of an image on a printed matter, the image quality of the printed matter, and the density on the back side of the printed matter.

In one embodiment of the present invention, an ink containing a coloring material and water, a treatment liquid A containing a permeation promoting component, a treatment liquid B containing a fixing component, and a treatment liquid C containing an aggregating component for aggregating the ink are combined. The present invention relates to an inkjet recording method for discharging, wherein the treatment liquid and the ink are deposited on a substrate in the order of the treatment liquid A, the treatment liquid B, the treatment liquid C, and the ink.

According to one embodiment of the present invention, it is possible to improve the fixability of an image on a printed matter, the image quality of the printed matter, and the density on the back surface of the printed matter.

An embodiment of the present invention will be described in detail below, but it goes without saying that the present invention is not limited to the following embodiment, and various modifications and changes may be made.

An inkjet recording method according to an embodiment of the present invention comprises an ink containing a coloring material and water, a treatment liquid A containing a permeation promoting component, a treatment liquid B containing a fixing component, and a treatment liquid containing an aggregating component for aggregating the ink. C, and the treatment liquid and the inks land on the substrate in the order of treatment liquid A, treatment liquid B, treatment liquid C, and ink.
When this inkjet recording method is used, it is possible to improve the image quality of the printed matter and the fixability of the image to the printed matter.
In addition, the density on the back side of the printed matter can be increased, and it can be preferably applied to applications requiring visibility from the back side of the printed matter.

The treatment liquid A containing a permeation promoting component helps the ink permeate into the base material, thereby enhancing the anchoring effect of the ink within the base material and improving the back surface density.
The treatment liquid B containing a fixing component functions as a binder for the colorant of the ink on the base material, and has the effect of improving the fixability of the colorant within the base material.
The treatment liquid C containing an aggregating component that agglomerates ink (hereinafter, may be simply referred to as “aggregating component”) has the effect of suppressing ink bleeding and improving image quality.
By ejecting the treatment liquid A first, the penetration promoting component in the treatment liquid A facilitates the penetration of the treatment liquid B, the treatment liquid C, and the ink into the substrate, and the coloring material reaches the inside of the substrate. can penetrate. As a result, fixability is improved when stress such as rubbing is applied to the base material. In addition, since the ink permeates into the base material, the back surface density is also improved.
By ejecting the treatment liquid B secondly, the fixing component in the treatment liquid B penetrates into the substrate, and when the ink that has landed after the treatment liquids A to C has penetrated into the substrate, it penetrates. The ink can be fixed in the substrate. As a result, the fixability improved by the treatment liquid A is further improved.
When the treatment liquid C is discharged thirdly, since the treatment liquid A is applied first, the aggregation component of the treatment liquid C applied later is easily drawn into the substrate, and the aggregation in the treatment liquid C occurs. Only a portion of the components remain on the substrate surface and all the rest reach the interior of the substrate. Since the aggregating component is present both on the surface and inside of the base material, when the ink is ejected onto the base material, the bleeding of the ink is suppressed, and the action of the treatment liquid A allows the ink to reach the inside of the base material. can be made In the case of inkjet inks, especially those containing pigments as colorants, improving the density on the back side of the printed matter may be an issue. It is possible to achieve both improvement and image quality improvement.

"Base material"
The method for producing a printed matter according to one embodiment can preferably record images on various substrates.
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, and the like. Among them, cloth is preferable.
Examples of cloth include natural fibers such as cotton, silk, wool and hemp; chemical fibers such as polyester, acrylic, polyurethane, nylon, rayon, cupra and acetate; and blended fibers thereof. Also, the cloth may be a woven fabric, a knitted fabric, a non-woven fabric, or the like.

"Treatment liquid A"
The treatment liquid A preferably contains a permeation promoting component.
As the penetration promoting component, for example, a surfactant, a water-soluble organic solvent having an SP value of 14 (cal/cm ³ ) ^1/2 or less, or a combination thereof can be preferably used.

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

Surfactants include ionic surfactants and nonionic surfactants, and nonionic surfactants are preferably used.

The surfactant may be either a low-molecular-weight surfactant or a high-molecular-weight surfactant (generally refers to those having a molecular weight of about 2000 or more). It can be preferably used.
The HLB value of the surfactant is preferably 5-20.

Examples of surfactants include acetylene glycol-based surfactants, silicone-based surfactants, polyoxyethylene-based surfactants, fluorine-based surfactants, and higher alcohol-based surfactants.
Among these surfactants, silicone-based surfactants, acetylene glycol-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 "Silface SAG Series" (trade name) manufactured by Nissin Chemical Industry Co., Ltd., "BYK-349" (trade name) manufactured by BYK-Chemie Japan Co., Ltd., and the like. .

Examples of commercially available acetylene glycol-based surfactants include "Surfinol 104E, 104H", which are acetylene glycols, and "Surfinol 420, 440, 465, 485", which are structures in which ethylene oxide is added to acetylene glycol (all of the above trade name, manufactured by Air Products and Chemicals), acetylene glycol "OLFINE E-1004, E-1010, E-1020, PD-002W, PD-004, EXP.4001, EXP.4200, EXP.4123, EXP. 4300” (both trade names, manufactured by Nissin Chemical Industry Co., Ltd.), “acetylenol E00, E00P” of acetylene glycol, and “acetylenol E40, E100” of structures obtained by adding ethylene oxide to acetylene glycol (both trade names , manufactured by Kawaken Fine Chemicals Co., Ltd.) and the like. Examples of commercially available acetylene glycol-based surfactants include "Surfinol PSA-336" (trade name, manufactured by Nissin Chemical Industry Co., Ltd.).

Other nonionic surfactants include, for example, Kao Corporation's Emulgen series "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" and the like polyoxyethylene alkyl ether surfactants.

The above surfactants may be used alone or in combination of two or more.
The amount of the surfactant is preferably 0.5% by mass or more, more preferably 1% by mass or more, and even more preferably 2% by mass or more, relative to the total amount of the treatment liquid A.
The surfactant content is preferably 10% by mass or less, more preferably 8% by mass or less, relative to the total amount of the treatment liquid A.

Examples of water-soluble organic solvents having an SP value of 14 (cal/cm ³ ) ^1/2 or less include 1,2-butanediol (SP value 12.8), 1,6-hexanediol (SP value 13.5 ), 1,2-propanediol (SP value 13.5), glycerin (SP value 16.4), dipropylene glycol (SP value 13.6), diethylene glycol monoethyl ether (SP value 10.9), diethylene glycol mono Butyl ether (SP value 10.5), diethylene glycol monophenyl ether (SP value 11.7), diethylene glycol benzyl ether (SP value 11.5), ethylene glycol propyl ether (SP value 11.1), diethylene glycol monoethyl acetate (SP value 9.3), tripropylene glycol dimethyl ether (SP value 8.4), N-methyl-2-pyrrolidone (SP value 11.2), and the like.
The units of SP values in parentheses are (cal/cm ³ ) ^1/2 .

Although the lower limit of the SP value of the water-soluble organic solvent is not particularly limited, it is preferably 9 (cal/cm ³ ) ^1/2 or more.

The above water-soluble organic solvents may be used alone or in combination of two or more.
The water-soluble organic solvent as the permeation promoting component is preferably 1% by mass or more, more preferably 10% by mass or more, and even more preferably 30% by mass or more, relative to the total amount of the treatment liquid A.
The water-soluble organic solvent as the permeation promoting component is preferably 100% by mass or less, more preferably 80% by mass or less, and even more preferably 60% by mass or less, relative to the total amount of the treatment liquid A. Since the water-soluble organic solvent as the permeation promoting component functions as both a permeation promoting component and a solvent, the treatment liquid A may contain the water-soluble organic solvent as the permeation promoting component as a single component.

The permeation promoting components described above may be used alone, or two or more of them may be used in combination. When using two or more penetration enhancers, it is preferable to select two or more penetration enhancers so as not to impair each other's actions, and to adjust the blending ratio thereof. In addition, the permeability of the treatment liquid A can be further enhanced by including a surfactant as a permeation promoting component. Further, it is preferable to use a combination of a surfactant and a water-soluble organic solvent having an SP value of 14 (cal/cm ³ ) ^1/2 or less as a penetration promoting component.
The permeation promoting component is preferably 0.5% by mass or more, more preferably 10% by mass or more, and still more preferably 30% by mass or more with respect to the entire treatment liquid A. When a surfactant is used as the permeation promoting component, the permeability of the treatment liquid A can be more effectively improved even in a small amount.
Although the penetration promoting component is not limited to this, it is preferably 100% by mass or less, more preferably 80% by mass or less, and even more preferably 60% by mass or less with respect to the entire treatment liquid A.
For example, the penetration promoting component is preferably 0.5 to 100% by mass, more preferably 10 to 80% by mass, even more preferably 30 to 60% by mass, relative to the entire treatment liquid A.

The treatment liquid A can further contain substances such as solvents, fixing resins, surfactants, cross-linking agents, pH adjusters, antioxidants, infrared absorbers, preservatives, and the like. Solvents include water, water-soluble organic solvents, combinations thereof, and the like. As the water-soluble organic solvent, for example, a water-soluble organic solvent that can be blended as the permeation promoting component may be selected and used. Alternatively, it may be used by selecting from water-soluble organic solvents that can be blended with the ink described later.

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

"Treatment liquid B"
The treatment liquid B preferably contains a fixing component.
As the fixing component, a water-dispersible resin is preferable, and a nonionic water-dispersible resin is more preferable.

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 a resin containing an acrylic unit, a resin containing a methacrylic unit, and a resin containing both an acrylic unit and a methacrylic unit (the same shall apply hereinafter).

Among these water-dispersible resins, water-dispersible urethane resins are preferable from the viewpoint of improving fixability.

As the water-dispersible urethane resin, a nonionic water-dispersible urethane resin is preferred.

Examples of commercially available water-dispersible resin emulsions include "Superflex 500M" (trade name) (nonionic urethane resin emulsion) and "Superflex 740" (anionic urethane resin) 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 dispersion (meth)acrylic resin emulsion), and "PRINT RITE DP-375" (trade name) manufactured by Lubrizol (cationic water-dispersible resin emulsion).

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 treatment liquid B. On the other hand, the content of the water-dispersible resin 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 treatment liquid B. The water-dispersible resin is, for example, preferably 1 to 30% by mass, more preferably 3 to 20% by mass, even more preferably 5 to 15% by mass, relative to the total mass of the treatment liquid A.

The fixing component is preferably 1% by mass or more, more preferably 3% by mass or more, and even more preferably 5% by mass or more with respect to the total mass of the treatment liquid B. On the other hand, the fixing component 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 treatment liquid B. The fixing component 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 treatment liquid B.

The treatment liquid B can further contain substances such as solvents, fixing resins, surfactants, cross-linking agents, pH adjusters, antioxidants, infrared absorbers, preservatives, and the like. Solvents include water, water-soluble organic solvents, combinations thereof, and the like. As the water-soluble organic solvent, for example, a water-soluble organic solvent that can be blended with the treatment liquid A as a permeation promoting component may be selected and used. Alternatively, it may be used by selecting from water-soluble organic solvents that can be blended with the ink described later. The surfactant may be selected from, for example, surfactants that can be blended with the treatment liquid A described above as a permeation promoting component.

The method for producing the treatment liquid B is not particularly limited, and the treatment liquid B can be produced by the same method as for the treatment liquid A described above.

"Treatment liquid C"
The treatment liquid C preferably contains an aggregation component (“aggregation component”) that aggregates the ink.
Aggregating components include, for example, organic acids, cationic water-dispersible resins, and cationic water-soluble resins (hereinafter, cationic water-dispersible resins and cationic water-soluble resins may be collectively referred to as "cationic resins"). ), metal salts, low-polar solvents, and the like. Among these, organic acids are more preferred.

The organic acid is an organic compound exhibiting acidity, and specifically, an organic compound having an acidic group such as a carboxy group, a phenolic hydroxy group, or a sulfo group can be preferably used. Among them, a carboxy group is preferable from the viewpoint of facilitating the formation of a hydrogen bond, which will be described later.
The organic acid can interact with the substrate, such as hydrogen bonding, to further improve the adhesion to the substrate. In addition, the organic acid can improve the adhesion to the components of the ink on the base material through interaction such as hydrogen bonding, and can further improve the fixability of the image.
Further, when the ink contains a cross-linking agent, the organic acid becomes insoluble when the organic acid and the cross-linking agent come into contact with each other on the substrate, so that the water resistance of the image can be improved.
Examples of organic acids include carboxylic acids such as formic acid, acetic acid, oxalic acid and succinic acid, hydroxycarboxylic acids such as lactic acid, glyceric acid, tartaric acid, citric acid and malic acid, ascorbic acid and sulfonic acid.

The boiling point of the organic acid is preferably 120°C or higher.
In an inkjet recording apparatus, a recording head filled with water-based ink performs printing while moving over a base material to which each treatment liquid is 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 treatment liquid is applied, so that the volatilized organic acid does not come into contact with the water-based ink in the nozzle portion of the recording head. , 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 nozzle portion.

The above organic acids may be used alone or in combination of two or more.
The organic acid is preferably 1% by mass or more, more preferably 3% by mass or more, relative to the total amount of the treatment liquid B.
The organic acid content is preferably 30% by mass or less, more preferably 20% by mass or less, relative to the total amount of the treatment liquid B.

A polyvalent metal salt is preferred as the metal salt. 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 Mg, Ca, Sr, and Ba; divalent metals such as Ni, Zn, Cu, and Fe(II); Examples include trivalent metals, among which alkaline earth metals are preferred.
More specific examples include calcium chloride, calcium nitrate, magnesium chloride, magnesium nitrate, magnesium sulfate, copper nitrate, calcium acetate, magnesium acetate, manganese chloride and the like.

The above metal salts may be used alone or in combination of two or more.
The metal salt is preferably 1% by mass or more, more preferably 3% by mass or more, relative to the total amount of the treatment liquid B.
The content of the polyvalent metal salt is preferably 30% by mass or less, more preferably 20% by mass or less, relative to the total amount of the treatment liquid B.

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

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.

Commercially available cationic water-soluble resins include, for example, polydiallyldimethylammonium chloride such as Sharoll series "DC-303P, DC-902P (both trade names)" manufactured by Daiichi Kogyo Seiyaku Co., Ltd., Uni Sense Series "FCA1000L, FPA100L (both trade names)", Osaka Organic Chemical Industry Co., Ltd. HC Polymer Series "1S, 1N, 1NS, 2, 2L (both trade names)", Daiichi Kogyo Seiyaku Co., Ltd. "F -2997D” (trade name).

Moreover, a water-soluble resin having an amino group can be preferably used as the cationic water-soluble resin.
As the water-soluble resin having an amino group, for example, polyethyleneimine, polyvinylamine, polyallylamine and salts thereof, basic polymers such as polyvinylpyridine, or derivatives thereof can be used. Among them, polyethyleneimine or polyallylamine is preferable.

Commercial products of polyethyleneimine include, for example, Nippon Shokubai Co., Ltd. Epomin series "SP-006, SP-012, SP-018, SP-200 (all trade names)"; BASF Japan Co., Ltd. "Lupasol FG" , Lupasol G20 Waterfree, and Lupasol PR 8515 (both trade names).
In addition, as commercial products of polyallylamine, for example, Nitto Boseki Co., Ltd. "PAA-01, PAA-03, PAA-05 which are allylamine polymers, PAA-HCL-01 which is allylamine hydrochloride polymer, PAA- HCL-03, PAA-HCL-05, and PAA-SA which is an allylamine amide sulfate polymer (all trade names).

As the cationic water-dispersible resin, the surface of the resin particles is positively charged, and the resin particles are positively charged. can form an emulsion of The resin may have a cationic functional group present on the particle surface like a self-emulsifying resin, or may be surface-treated such as by attaching a cationic dispersant to the resin particle surface. Cationic functional groups are typically primary, secondary or tertiary amino groups, pyridine groups, imidazole groups, benzimidazole groups, triazole groups, benzotriazole groups, pyrazole groups, benzopyrazole groups, etc. is mentioned. Cationic dispersants include primary, secondary, tertiary or quaternary amino group-containing acrylic polymers, polyethyleneimine, cationic polyvinyl alcohol resins, cationic water-soluble multi-branched polyesteramide resins and the like.
The surface charge amount of the cationic water-dispersible 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. Specifically, the surface charge amount is preferably 20 to 500 μeq/g, more preferably 20 to 100 μeq/g. As the particle charge meter, a colloidal particle charge meter "Model CAS" manufactured by Nihon Luft Co., Ltd. can be used.

As the cationic water-dispersible resin, it is preferable to use a resin that forms a transparent coating film. Moreover, when producing the treatment liquid, it can be blended as an oil-in-water resin emulsion.
Examples of cationic water-dispersible resins include urethane resins, (meth)acrylic resins, styrene/(meth)acrylic resins, polyester resins, olefin resins, vinyl chloride resins, vinyl acetate resins, melamine resins, amide resins, ethylene- In vinyl chloride copolymer resins, styrene-maleic anhydride copolymer resins, vinyl acetate-(meth)acrylic copolymer resins, vinyl acetate-ethylene copolymer resins, and composite resins thereof, cations are added to these resins. A positive functional group may be introduced, or the surface may be treated with a cationic dispersant or the like to impart a positive surface charge.

In the water-dispersible resin emulsion, the average particle diameter of the water-dispersible resin particles forming the emulsion (average particle diameter measured on a volume basis by a dynamic light scattering method) prevents the texture of the substrate surface from changing, The average particle size of the water-dispersible resin particles is preferably 300 nm or less, more preferably 200 nm or less, to be suitable for ejection from an inkjet recording apparatus, and preferably 10 μm or less in order to prevent falling off from the substrate surface. , 150 nm or less.
The average particle size of the water-dispersible resin particles is not particularly limited, but is preferably 1 nm or more, more preferably 5 nm or more, and even more preferably 10 nm or more, from the viewpoint of the water scratch resistance of the ink.

Commercially available cationic water-dispersible resins include, for example, “PRINTRITE DP-375” manufactured by Lubrizol, “Superflex 620, 650” manufactured by Daiichi Kogyo Seiyaku Co., Ltd., “PP-” manufactured by Meisei Chemical Industry Co., Ltd. 15, PP-17”, “Polysol AP-1350” manufactured by Showa Denko Co., Ltd., “Boncoat SFC-55” manufactured by DIC Corporation, “Aquatex AC-3100” manufactured by Japan Coating Resin Co., Ltd., etc. .

The above cationic resins may be used alone or in combination of two or more.
The content of the cationic resin is preferably 1% by mass or more, more preferably 3% by mass or more, relative to the total amount of the treatment liquid C.
The content of the cationic resin is preferably 30% by mass or less, more preferably 20% by mass or less, relative to the total amount of the treatment liquid C.

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.

Low polar solvents may be used alone or in combination of two or more.
The amount of the low-polar solvent in the treatment liquid C 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 treatment liquid C.

The above aggregation components may be used alone or in combination of two or more. When two or more kinds of aggregating components are used, it is preferable to select two or more kinds of aggregating components so as not to impair each other's actions, and to adjust the mixing ratio thereof. For example, it is preferable to use a combination of aggregation components exhibiting the same ionicity.
The total amount of aggregated components 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 entire treatment liquid C.
The total amount of aggregated components is preferably 30% by mass or less, more preferably 20% by mass or less, and even more preferably 15% by mass or less with respect to the entire treatment liquid C.
For example, the aggregation component is preferably 1 to 30% by mass, more preferably 3 to 20% by mass, and even more preferably 5 to 15% by mass with respect to the entire treatment liquid C.

The treatment liquid C can further contain substances such as solvents, fixing resins, surfactants, cross-linking agents, pH adjusters, antioxidants, infrared absorbers, preservatives, and the like. Solvents include water, water-soluble organic solvents, combinations thereof, and the like. As the water-soluble organic solvent, for example, a water-soluble organic solvent that can be blended with the treatment liquid A as a permeation promoting component may be selected and used. Alternatively, it may be used by selecting from water-soluble organic solvents that can be blended with the ink described later. The surfactant may be selected from, for example, surfactants that can be blended with the treatment liquid A described above as a permeation promoting component.

The method for producing the treatment liquid C is not particularly limited, and the treatment liquid C can be produced by the same method as for the treatment liquid A described above.

"ink"
The ink preferably contains a coloring material and water.

As the colorant, either a pigment or a dye may be used, and each of them 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.
For example, when using a substrate having a color, surface shape, etc., such as cloth, as the substrate, a base layer is formed using a white ink using a white pigment in order to hide the color, etc. of the substrate. , there is a method of recording an image from above.
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; carbon blacks such as furnace carbon black, lamp black, acetylene black, channel black, and the like can be used.

Examples of white pigments that can be used 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 solid resin fine particles can also be used. Among them, titanium oxide can be preferably used from the viewpoint of hiding power. As the titanium oxide, it is preferable to use one surface-treated with alumina or silica in order to suppress the photocatalytic action.
The volume-based average particle diameter of the pigment is preferably 50 nm or more from the viewpoint of color development, preferably 500 nm or less, more preferably 200 nm or less from the viewpoint of ejection stability. For example, the average particle size of the pigment is preferably 50-500 nm, more preferably 50-200 nm.

A self-dispersing pigment whose surface is modified with a hydrophilic functional group may also be used. Commercial products of self-dispersing pigments include, for example, CAB-O-JET series manufactured by Cabot Corporation "CAB-O-JET200, CAB-O-JET300, CAB-O-JET250C, CAB-O-JET260M, CAB-O-JET270 ”, “BONJET BLACK CW-1S, CW-2, CW-3” manufactured by Orient Chemical Co., Ltd. (all are trade names).
A microencapsulated pigment, which is a pigment coated with a resin, may also be used.
A pigment dispersion in which a pigment is previously dispersed using a pigment dispersant may also be used. Commercially available pigment dispersions include, for example, "HOSTAJET series" manufactured by Clariant Co., Ltd., and "FUJI SP series" manufactured by Fuji Pigment Co., Ltd. (both are trade names). Further, a pigment dispersion in which a pigment is dispersed using a pigment dispersant, which will be described later, may be used.

One of the above pigments may be used alone, or two or more thereof may be used in combination.
The solid content of the pigment is preferably 0.1 to 30% by mass, more preferably 0.5 to 15% by mass, more preferably 1 to 10% by mass, from the viewpoint of color development, etc., although it varies depending on the type. is more preferred.

The ink may further contain a pigment dispersant to stably disperse the pigment in water.
As pigment dispersants, for example, commercial products such as TEGO Disperse series "TEGO Disperse 740W, TEGO Disperse 750W, TEGO Disperse 755W, TEGO Disperse 757W, TEGO Disperse 760W" manufactured by EVONIK, and Nippon Lubrizol are available. Solsperse series "Solsperse 20000, Solsperse 27000, Solsperse 41000, Solsperse 41090, Solsperse 43000, Solsperse 44000, Solsperse 46000" manufactured by Co., Ltd., Joncryl series "Joncryl 57, Joncryl 60, Joncryl 62" manufactured by Johnson Polymer Co., Ltd. , Joncryl 63, Joncryl 71, Joncryl 501", BYK's "DISPERBYK-102, DISPERBYK-185, DISPERBYK-190, DISPERBYK-193, DISPERBYK-199" (all trade names).
As the surfactant-type dispersant, for example, Kao Corporation's DEMOLL series "DEMOLL EP, DEMOLL N, DEMOLL RN, DEMOLL NL, DEMOLL RNL, DEMOLL T-45" (all trade names) and the like. Active agents, nonionic interfaces such as Emulgen series manufactured by Kao Corporation "Emulgen A-60, Emulgen A-90, Emulgen A-500, Emulgen B-40, Emulgen L-40, Emulgen 420" (all trade names) active agents.

Pigment dispersants may be used alone or in combination of two or more.
The pigment dispersant varies depending on its type and is not particularly limited, but in general, it should be blended in a range of 0.005 to 0.5 with respect to 1 of the pigment in terms of the mass ratio of the solid content to the total amount of the ink. is preferred.

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.

The above dyes may be used singly or in combination of two or more.
The solid content of the dye is preferably 0.1 to 30% by mass, more preferably 0.5 to 15% by mass, more preferably 1 to 10% by mass, from the viewpoint of color development, etc., although it varies depending on the type. is more preferred.

The ink preferably contains water. Water is not particularly limited as long as it functions as a solvent for ink, and distilled water, ion-exchanged water, deionized water, and the like can be used.
Water is preferably 20% by mass or more, more preferably 30% by mass or more, and even more preferably 40% by mass or more, relative to the total amount of ink.
Water may be 95% by mass or less, or 90% by mass or less, relative to the total amount of ink, depending on the amount of coloring material and the like added.

The ink may contain a water-soluble organic solvent in addition to or instead of 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.

Examples of water-soluble organic solvents include methanol, ethanol, 1-propanol, isopropanol, 1-butanol, 2-butanol, isobutanol, 1,3-propanediol, 1,3-butanediol, and 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 Glycols such as glycol and tripropylene glycol; glycerin; acetins (monoacetin, diacetin); diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol monoethyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, Ethylene 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, Tetra Glycol derivatives such as ethylene glycol diethyl ether; triethanolamine, 1-methyl-2-pyrrolidone, β-thiodiglycol, sulfolane and the like can be used.
Furthermore, as the water-soluble organic solvent, for example, 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, and having an average molecular weight of 400, etc., having an average molecular weight in the range of 200 to 600 Low-molecular-weight polyalkylene glycols such as diol-type polypropylene glycol and triol-type polypropylene glycol having an average molecular weight in the range of 250 to 800, such as average molecular weights of 300 and 700, 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 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. When blending two or more water-soluble organic solvents, the total amount is preferably within this range.

The ink may further contain a surfactant.
Surfactants are roughly classified into ionic surfactants such as cationic surfactants, anionic surfactants and amphoteric surfactants, and nonionic surfactants. In addition, both low-molecular-weight surfactants and high-molecular-weight surfactants (generally refers to those having a molecular weight of about 2000 or more) may be used, but low-molecular-weight surfactants can be preferably used. . The HLB value of the surfactant is preferably 5-20.
The surfactant may be selected from, for example, surfactants that can be blended with the treatment liquid A described above as a permeation promoting component.

The amount of active ingredients in the surfactant is preferably 0.1% by weight or more, more preferably 0.5% by weight or more, relative to the total amount of the ink. On the other hand, the amount of the surfactant is preferably 5% by weight or less, more preferably 4% by weight or less, and even more preferably 3% by weight or less, in terms of the amount of active ingredient with respect to the total amount of the ink.

The ink preferably contains a water-dispersible resin as a fixing resin.
Typical types of water-dispersible resins include urethane resins, (meth)acrylic resins, styrene/(meth)acrylic resins, polyester resins, olefin resins, vinyl chloride resins, vinyl acetate resins, melamine resins, and amide resins. , ethylene-vinyl chloride copolymer resin, styrene-(meth)acrylic resin, styrene-maleic anhydride copolymer resin, vinyl acetate-(meth)acrylic copolymer resin, vinyl acetate-ethylene copolymer resin, silicone resin etc., and composite resins thereof.

Examples of commercially available water-dispersible resin emulsions include "Superflex 500M" (trade name) (nonionic urethane resin emulsion) and "Superflex 740" (anionic urethane resin) 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 dispersion (meth)acrylic resin emulsion), "Movinyl 966A" (trade name) (water-dispersible styrene-(meth)acrylic resin emulsion), and the like.

The water-dispersible resin is preferably 0.1 to 15, more preferably 1 to 10, with respect to 1 part of the coloring material in terms of mass ratio of the solid content to the total amount of the ink. 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 0.1 or more, the fixability of the image can be further improved. When the ratio of the resin to the coloring material is 15 or less, the on-press stability of the ink can be further improved.

The solid content of the water-dispersible resin is preferably 0.1% by mass or more, more preferably 1% by mass or more, and even more preferably 5% by mass, based on the total amount of the ink.
Moreover, the water-dispersible resin is preferably 20% by mass or less, more preferably 10% by mass or less, relative to the total amount of the ink.
For example, the water-dispersible resin is preferably 0.1 to 20% by mass, more preferably 1 to 20% by mass, and may be 5 to 10% by mass, based on the total amount of the ink.

In addition to the above components, optional components such as cross-linking components, moisturizing agents, antifoaming agents, pH adjusters, antioxidants, preservatives, surface tension reducing agents, and ultraviolet absorbers may be added to the ink. good too.

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 throwing all the components into a known dispersing machine such as a bead mill in batches or in portions to disperse them, and if desired, passing them through a known filtering machine such as a membrane filter. For example, after preparing a mixed liquid by uniformly mixing the total amount of water and a coloring material in advance and dispersing it with a dispersing machine, the remaining components are added to this dispersion liquid and it is passed through a filter. can be done.

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

"Recording method"
The inkjet recording method of the embodiment is an inkjet recording method in which ink, treatment liquid A, treatment liquid B, and treatment liquid C are ejected. It is preferable that the liquid C and the ink land on the substrate in this order.
The ink, the treatment liquid A, the treatment liquid B, and the treatment liquid C are each preferably ejected by an inkjet method.

A control method for landing the treatment liquid A, the treatment liquid B, and the treatment liquid C on the substrate in this order is not particularly limited. For example, in a serial system in which one printhead unit includes a plurality of printheads and scans the printhead unit in a direction intersecting with the conveying direction of the base material, the following ejection method can be used.
For example, in the print head unit, each of the print heads for treatment liquid A, treatment liquid B, and treatment liquid C spreads the treatment liquid A, When the treatment liquid B and the treatment liquid C are arranged in this order, the treatment liquid A, the treatment liquid B and the treatment liquid C are ejected in this order on the forward pass in the scanning direction of the print head unit, and are not ejected on the return pass. A method of only moving the print head unit; within the print head unit, each of the print heads for treatment liquid A, treatment liquid B, and treatment liquid C moves from the downstream side of the outward path in the scanning direction of the print head unit (advancing direction of the outward path). When the treatment liquid C, the treatment liquid B, and the treatment liquid A are arranged in this order (from the head side), only the treatment liquid A is ejected in the forward pass in the scanning direction of the print head unit, and the treatment liquid B and the treatment liquid are ejected in the return pass. A method of ejecting treatment liquids in the order of liquid C and the like can be mentioned.

For example, when the treatment liquids A to C are applied bidirectionally to the substrate using a serial recording head unit arranged in the scanning direction of the recording head unit, in the first pass of the forward pass, the treatment liquids A, B, If the treatment liquid C is discharged in this order, and in the second pass of the return pass, the treatment liquid C, the treatment liquid B, and the treatment liquid A are discharged in this order, the treatment liquids A to A are discharged for each line corresponding to the pass in the conveying direction of the substrate. The landing order of C on the substrate is changed, which may cause image unevenness.
Therefore, the treatment liquid A, the treatment liquid B, the treatment liquid C, and the ink are deposited on the recording area of the base material in a predetermined order, and the treatment liquid A, the treatment liquid B, the treatment liquid C, and the ink are deposited in the entire recording area. It is preferable that the stacking order of the layers is the same.

By controlling the amounts of the penetration promoting component and the cohesive component, the back surface density can be further improved. The ratio of the amount of the penetration promoting component and the amount of the aggregation component is preferably 3 or less or less than 3 of the penetration promoting component per 1 penetration promoting component, and 1.5 of the permeation promoting component per 1.5 It is more preferable to have On the other hand, in comparison between the amount of the penetration promoting component and the amount of the aggregation component, it is preferable that the amount of the aggregation component is equal to or greater than the amount of the penetration promoting component or larger than the amount of the penetration promoting component. The ratio of the amount of the penetration promoting component and the amount of the flocculating component is preferably larger than the amount of the penetration promoting component: the amount of the flocculating component = 1:3, and the amount of the penetration promoting component: the amount of the flocculating component = 1:1. .5 is more desirable. The ratio of the amount of penetration enhancing component to the amount of aggregation component may be, for example, amount of penetration enhancing component: amount of aggregation component = 1:1 to 1:3 or 1:1 to 1: (less than 3).

EXAMPLES The present invention will be described in detail below with reference to Examples, but the present invention is not limited only to these Examples.

"Preparation of treatment liquid"
Tables 1 to 3 show the formulations of treatment solutions A1 to A4, B1 to B4, and C1 to C3. In addition, Table 4 shows the formulations of inks 1 and 2. The raw materials were mixed according to the mixing ratio shown in the table, and stirred with a mixing rotor at 100 rpm for 30 minutes. After filtration through a nylon syringe filter with a pore size of 5 μm, treatment solutions A1 to A4, B1 to B4 and C1 to C3, and inks 1 and 2 were obtained.

The materials used are as follows.

BYK-349: BYK-Chemie Japan Co., Ltd., silicone-based surfactant (penetration promoting component)
Silface SAG002: manufactured by Nissin Chemical Industry Co., Ltd., silicone-based surfactant (penetration promoting component)
Surfynol PSA-336: manufactured by Nissin Chemical Industry Co., Ltd., acetylene glycol-based surfactant (penetration promoting component)

Superflex 500M: Daiichi Kogyo Seiyaku Co., Ltd., water-dispersible ester-based urethane resin emulsion, nonionic Movinyl 7720: Japan Coating Resin Co., Ltd., water-dispersible (meth)acrylic resin emulsion, nonionic PRINT RITE DP-375: Lubrizol, cationic water-dispersible resin emulsion Superflex 740: Daiichi Kogyo Seiyaku Co., Ltd., water-dispersible carbonate-based urethane resin emulsion, cationic

Succinic acid: FUJIFILM Wako Pure Chemical Co., Ltd., organic acid Manganese chloride: FUJIFILM Wako Pure Chemical Co., Ltd., metal salt F-2997D: Daiichi Kogyo Seiyaku Co., Ltd., cationic water-soluble resin

Triethylene glycol: manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd., water-soluble organic solvent Dipropylene glycol: manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd., water-soluble organic solvent 1,2-butanediol: manufactured by Tokyo Chemical Industry Co., Ltd., water-soluble Organic solvent diethylene glycol monoethyl ether: manufactured by Tokyo Chemical Industry Co., Ltd., water-soluble organic solvent 1,2,4-butanetriol: manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd., water-soluble organic solvent

CAB-O-JET300: manufactured by Cabot Japan Co., Ltd., carbon black pigment dispersion Movinyl 966A: manufactured by Japan Coating Resin Co., Ltd., water-dispersible styrene-(meth)acrylic resin emulsion Ethylene glycol: manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd., water-soluble organic solvent

"printing"
Printing was carried out according to the following procedure using combinations of treatment liquids and inks shown in Tables 5 to 7 to obtain prints. In Tables 5 to 7, "treatment liquid and ink discharge order" indicates the order of landing on the substrate. For example, in Example 1, treatment liquid A1, treatment liquid B1, treatment liquid C1, and ink 1 are caused to land on the substrate in this order.
A cloth made of 100% polyester was used as the base material.
As a printer, using a modified inkjet printer MMP-8130 manufactured by Mastermind Co., Ltd., a solid image and 10-point fine print were inkjet-printed on the base material, and then heat-pressed at 180° C. for 2 minutes.

"evaluation"
"Image quality", "fixability" and "back surface density" were determined according to the following criteria.

1. Image Quality We checked whether or not the 10-point fine print portion was crushed. For those with crushing, the OD value of the solid image area was measured by "X-Rite eXact" manufactured by X-Rite, and evaluated according to the following criteria.
The results are shown in Tables 5-7.
A: There is no crushing of fine characters of 10 points or less.
B: Fine print of 10 points or less is partially crushed, and the OD value is 1.15 or more C: All fine print of 10 points or less is crushed, and the OD value is 1.1 or more and less than 1.15 D: 10 points The following fine print is partially crushed and the OD value is less than 1.1

2. Fixability According to the method specified in JIS L0849, a solid portion in the printed material was rubbed using a type II friction tester, and contamination of the rubbed cloth was evaluated using a contamination gray scale. Evaluation criteria are shown below. The results are shown in Tables 5-7.
A: Dry friction stain fastness level 3 or higher
B: Dry rubbing stain fastness level 2 or higher and less than grade 3 C: Dry rubbing stain fastness grade 2 D: Dry rubbing stain fastness grade less than grade 2

3. Back side density The OD value of the back side of the solid image area was measured by "X-Rite eXact" manufactured by X-Rite, and evaluated according to the following criteria. The results are shown in Tables 5-7.
A: OD value is 0.4 or more B: OD value is 0.35 or more and less than 0.4 C: OD value is 0.3 or more and less than 0.35 D: OD value is less than 0.3

Examples 1 to 16 all showed good results in terms of image, fixability and back surface density.

The processing liquids used in Examples 1 and 3 and Examples 2 and 4 are all the same. However, in Examples 3 and 4, the amount of permeation enhancing component relative to the amount of flocculating component is lower than in Examples 1 and 2. Therefore, in Examples 3 and 4, the penetrating power of the coloring material into the substrate was lower than in Examples 1 and 2, and the back surface density was lower than in Examples 1 and 2.

The fixability of Examples 5 and 6 is lower than that of Examples 1 and 2. It is considered that this is caused by changing the aggregation component of the treatment liquid C from the organic acid. The organic acid tends to interact with the substrate as well as the components in the ink, and tends to improve the fixability of the ink. It is conceivable that the fixability of Examples 5 and 6 was lower than that of Examples 1 and 2 as a result of this effect becoming less likely to occur in Examples 5 and 6. In addition, the reason why the back surface densities of Examples 7 and 8 were lower than those of Examples 5 and 6 is considered to be that the amount of the permeation promoting component relative to the amount of the cohesive component was smaller as described above.

The reason why the fixability of Examples 9 and 10 was lower than that of Examples 1 and 2 is that the water-dispersibility of the fixing component of the treatment liquid B is aggregated when mixed with a cationic water-dispersible resin or aggregating component. It is conceivable that it was made of resin. When the fixing component is a cationic water-dispersible resin, it reacts with the ink to cause aggregation. At this time, if not only the treatment liquid C but also the treatment liquid B contains a component that agglomerates the ink on the base material, the amount of ink remaining on the base material surface increases. As a result, the ink could not be fixed in the substrate, and the fixability of Example 9 was lower than that of Examples 1 and 2. Furthermore, when the fixing component is a water-dispersible resin that reacts with the cohesive component, the cohesive component cannot fully react with the ink, resulting in deterioration of fixability. As a result, it is conceivable that the fixability of Example 10 was lower than those of Examples 1 and 2. Further, it is considered that the reason why the back surface densities of Examples 11 and 12 were lower than those of Examples 9 and 10 was that the amount of the permeation promoting component relative to the amount of the cohesive component was smaller as described above.

The reason why the fixability and back surface density of Examples 13 and 14 were lower than those of Examples 1 and 2 is considered to be that the penetration promoting component of the treatment liquid A was an active agent other than the silicone surfactant. By using a surfactant other than the silicone-based surfactant, it becomes difficult for the fixing component, the aggregation component, and the ink component to permeate into the substrate. As a result, an ink layer is formed on the surface of the substrate, and the ink layer is likely to be subjected to rubbing stress. Fixability deteriorates because rubbing stress is likely to be applied. Furthermore, it is conceivable that the density on the back surface was also lowered because the ink components became difficult to permeate. In addition, it is considered that the reason why the concentrations of the back surfaces of Examples 15 and 16 were lower than those of Examples 13 and 14 was that the amount of the permeation promoting component relative to the amount of the cohesive component was smaller as described above.

Claims (1)

an ink containing a coloring material and water;
a treatment liquid A containing a penetration promoting component;
a treatment liquid B containing a fixing component;
An inkjet recording method for ejecting a treatment liquid C containing an aggregating component for aggregating the ink,
An inkjet recording method, wherein the treatment liquid and the ink land on a substrate in the order of the treatment liquid A, the treatment liquid B, the treatment liquid C, and the ink.