Image forming method and method for producing printed matter

Abstract

To provide an image formation method which enables formation of an image having excellent adhesion to a non-penetrable substrate using a treatment liquid excellent in discharge stability.SOLUTION: An image formation method includes: a treatment liquid imparting step of imparting a treatment liquid (containing no organic solvent having a boiling point of 200°C or higher at normal pressure) containing a polyvalent metal salt, a resin TA, a resin TB different from the resin TA, and a silicone-based surface active agent, to a non-penetrable substrate by an inkjet method; and an ink imparting step of imparting ink containing a coloring material, an organic solvent and a resin onto the treatment liquid.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to an image forming method. law, and a method for producing printed matter. [Background technology]

[0002] In recent years, even in the fields of commercial and industrial printing, where analog printing such as offset printing and flexography are currently the norm, there has been a growing need for inkjet printers as a form of digital printing that does not require plates and can print a wide variety of designs in small quantities.

[0003] In commercial printing, the main printing items include pamphlets, catalogs, posters, manuals, etc., while in industrial printing, the main printing items include labels, packages, textiles, cardboard, etc. In particular, in the field of industrial printing, designs that are produced in small quantities and in a wide variety of products are preferred and are used to promote product sales.

[0004] When producing a wide variety of printed materials in small quantities using digital printing in this way, various types of printing substrates are used. However, the surface characteristics of each substrate vary, which can affect the quality of the printed material. In order to produce printed matter of the same quality on various substrates, it is known to apply a pretreatment liquid that enhances ink receptivity before applying ink. In addition, the pretreatment liquid is required to improve not only the appearance of the printed matter but also the adhesion of the image to the printing substrate and to have ejection stability of the pretreatment liquid itself. As such a pretreatment liquid, for example, a method has been proposed in which the use of a pretreatment liquid reduces the penetration of the ink into the substrate and improves color development and abrasion resistance (see, for example, Patent Documents 1 and 2). Summary of the Invention [Problem to be solved by the invention]

[0005] An object of the present invention is to provide an image forming method capable of forming an image having excellent adhesion to a non-permeable substrate by using a treatment liquid having excellent ejection stability. [Means for solving the problem]

[0006] As a means for solving the above problems, the image forming method of the present invention comprises the steps of: A, the resin T A Resin T different from B and a treatment liquid containing a silicone surfactant ( However, it does not include organic solvents with a boiling point of 200°C or higher under normal pressure) on a non-permeable substrate. a process of applying a treatment liquid to the substrate by an inkjet method; and an ink applying step of applying an ink having the above-mentioned characteristic onto the treatment liquid. Resin T A Glass transition temperature Tg A Tg A ≦-15° C., and said resin T B Glass transition temperature Tg B 30℃≦Tg B is . Effect of the Invention

[0007] According to the present invention, it is possible to provide an image forming method capable of forming an image having excellent adhesion to a non-permeable substrate by using a treatment liquid having excellent ejection stability. [Brief description of the drawings]

[0008] [Figure 1] FIG. 1 is a perspective explanatory view showing an example of a printing production apparatus of the present invention. [Diagram 2] FIG. 2 is a perspective explanatory view showing an example of a main tank in the printing production apparatus of the present invention. [Diagram 3] FIG. 3 is a schematic diagram showing an example of an image forming apparatus used in the image forming method of the present invention. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0009] (Image forming method and image forming apparatus) In the image forming method of the present invention, a polyvalent metal salt, a resin T A , the resin T A Resin T different from B and a silicone-based surfactant (but does not include an organic solvent having a boiling point of 200° C. or higher under normal pressure) to a non-permeable substrate by an inkjet method; and an ink-applying step of applying an ink containing a colorant, an organic solvent, and a resin onto the treatment liquid, and further including other steps as necessary. The image forming apparatus of the present invention is A , the resin T A Resin T different from B and a silicone-based surfactant (but does not include an organic solvent having a boiling point of 200°C or higher under normal pressure); treatment liquid application means that applies the treatment liquid contained in the treatment liquid container to a non-permeable substrate by an inkjet method; an ink container that contains an ink containing a colorant, an organic solvent, and a resin; and ink application means that applies the ink contained in the ink container onto the treatment liquid, and may further have other means as necessary.

[0010] The conventional techniques have had a problem in that the adhesion of the formed image to the substrate is insufficient, and the image may peel off from the substrate. Furthermore, when a resin is added to the pretreatment liquid in order to improve adhesion, there is a problem in that the resin dries near the nozzle, which can lead to nozzle clogging and unstable meniscus control, thereby deteriorating ejection stability.

[0011] As a result of intensive research, the present inventors have found that polyvalent metal salts, resin T A , the resin T A Resin T different from BThe inventors have found that by preparing a treatment liquid containing a silicone-based surfactant (but not containing an organic solvent having a boiling point of 200°C or higher under normal pressure), it is possible to obtain a treatment liquid having excellent discharge stability while improving the wettability of the treatment liquid to a non-permeable substrate and the adhesion of an image to the substrate. Furthermore, by including a polyvalent metal salt in the treatment liquid, the pigment in the ink is aggregated at the same time as the ink droplets land, so that bleeding between colors does not occur and a clear image can be obtained (suppression of image bleeding). However, "not containing organic solvents having a boiling point of 200°C or higher under normal pressure" does not exclude cases where organic solvents having a boiling point of 200°C or higher under normal pressure are contained as impurities, but means that the content of organic solvents having a boiling point of 200°C or higher under normal pressure is 1 mass% or less.

[0012] Since the treatment liquid is applied to the non-permeable substrate before the ink is applied, the treatment liquid is sometimes referred to as a pretreatment liquid.

[0013] <Treatment liquid application step and treatment liquid application means> The treatment liquid application step is a step of applying the treatment liquid to a non-permeable substrate by an inkjet method. The treatment liquid applying unit applies the treatment liquid contained in a treatment liquid storage unit to a non-permeable substrate by an ink jet method. The treatment liquid storage unit is not particularly limited, and a known ink jet cartridge or the like can be used.

[0014] - Processing fluid - The treatment liquid contains a polyvalent metal salt, a resin T A , the resin T A Resin T different from B and a silicone surfactant, and may further contain water and an organic solvent (however, organic solvents having a boiling point of 200° C. or higher under normal pressure are not included) as necessary. The organic solvent, surfactant, defoamer, pH adjuster, antiseptic / fungal agent, and rust inhibitor may be the same as those used in ink, and other materials used in known treatment liquids may be used. The organic solvent, antibacterial agent, etc. may be the same as those used in the ink described below, and may also be materials used in other known treatment liquids. However, this does not include organic solvents with a boiling point of 200°C or higher under normal pressure.

[0015] --Polyvalent metal salts (flocculants)-- The polyvalent metal salt functions as a flocculating agent. The polyvalent metal salt quickly aggregates the pigment in the recording liquid after it is dropped, suppresses color bleeding, and improves color development. The polyvalent metal salt is not particularly limited and can be appropriately selected depending on the purpose. For example, a divalent metal salt is preferable. Examples of the divalent metal salt include calcium carbonate, calcium nitrate, calcium chloride, calcium acetate, calcium sulfate, magnesium chloride, magnesium acetate, magnesium sulfate, etc. These may be used alone or in combination of two or more. The content of the polyvalent metal salt is preferably 1% by mass or more, more preferably 3% by mass or more, and even more preferably 6% by mass or more, based on the total amount of the treatment liquid. There is no particular upper limit to the content of the polyvalent metal salt, and it can be appropriately selected depending on the purpose.

[0016] --Resin T A -- Resin T A The resin is not particularly limited and can be appropriately selected depending on the purpose. Examples of the resin include urethane resins, polyester resins, acrylic resins, vinyl acetate resins, styrene resins, butadiene resins, styrene-butadiene resins, vinyl chloride resins, acrylic styrene resins, and acrylic silicone resins.

[0017] Resin T A The glass transition temperature Tg A is Tg A≦-15°C, and preferably −40°C≦Tg A It is more preferred that it is ≦−15° C. The treatment liquid contains a resin and a silicone surfactant with a Tg of -15°C or less, and does not contain an organic solvent with a boiling point of 200°C or more, so that the ink wets and spreads immediately after landing on the non-permeable substrate, and a treatment film is formed immediately. Therefore, by applying the treatment liquid of the present invention to the substrate before applying the ink, the adhesion between the substrate and the ink film can be increased.

[0018] Resin T A The form of the resin particles is not particularly limited and can be appropriately selected according to the purpose, and examples thereof include resin particles. The resin particles are dispersed in water as a dispersion medium in a resin emulsion state, and can be mixed with materials such as a polyvalent metal salt and an organic solvent to obtain a treatment liquid. The resin particles may be appropriately synthesized or may be commercially available.

[0019] The commercially available resin particles include, for example, Hydran WLI-611 (manufactured by DIC Corporation, Tg A : -15℃), Superflex E2000 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., Tg A : -38℃), Superflex 500M (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., Tg A : -39℃), Vinybran 1245L (manufactured by Nissin Chemical Industry Co., Ltd., Tg A : -13℃), Vinybran 4003 (manufactured by Nissin Chemical Industry Co., Ltd., Tg A : -15℃). The volume average particle size of the resin particles is not particularly limited and can be appropriately selected depending on the purpose. From the viewpoint of obtaining good adhesion and high image hardness, the volume average particle size is preferably from 10 nm to 1,000 nm, more preferably from 10 nm to 200 nm, and particularly preferably from 10 nm to 100 nm.

[0020] The volume average particle size can be measured, for example, using a particle size analyzer (Nanotrac Wave-UT151, manufactured by Microtrac-Bell Co., Ltd.).

[0021] Resin T A The content of is not particularly limited and can be appropriately selected depending on the purpose. From the viewpoints of adhesion of the image to be formed and storage stability of the treatment liquid, the content is preferably from 1 mass % to 30 mass % and more preferably from 5 mass % to 20 mass % of the total amount of the treatment liquid.

[0022] --Resin T B -- Resin T B As for the resin T contained in the same treatment liquid, A As long as the resin is different from the above, it is not particularly limited and can be appropriately selected depending on the purpose. Examples of the resin include urethane resin, polyester resin, acrylic resin, vinyl acetate resin, styrene resin, butadiene resin, styrene-butadiene resin, vinyl chloride resin, acrylic styrene resin, and acrylic silicone resin.

[0023] Resin T B The glass transition temperature Tg B 30℃≦Tg B Preferably, 30° C.≦Tg B It is more preferable that the temperature is ≦50° C. By including a resin having a Tg of 30° C. or higher in the treatment liquid, it is possible to improve the adhesion while ensuring the discharge stability.

[0024] Resin T B The form of the resin particles is not particularly limited and can be appropriately selected according to the purpose, and examples thereof include resin particles. The resin particles are dispersed in water as a dispersion medium in a resin emulsion state, and can be mixed with materials such as a polyvalent metal salt and an organic solvent to obtain a treatment liquid. The resin particles may be appropriately synthesized or may be commercially available.

[0025] The commercially available resin particles include, for example, UW-550CS (manufactured by Taisei Fine Chemical Co., Ltd. (core-shell acrylic resin), Tg B: 40°C), Vinyblan 1008 (manufactured by Nissin Chemical Industry Co., Ltd., Tg B : 30℃), Vinybran GV-6181 (manufactured by Nissin Chemical Industry Co., Ltd., Tg B : 30℃), Vinybran 1017-AD (manufactured by Nissin Chemical Industry Co., Ltd., Tg B :31℃).

[0026] The volume average particle size can be measured, for example, using a particle size analyzer (Nanotrac Wave-UT151, manufactured by Microtrac-Bell Co., Ltd.).

[0027] Resin T B The content of is not particularly limited and can be appropriately selected depending on the purpose. From the viewpoints of adhesion of the image to be formed and storage stability of the treatment liquid, the content is preferably from 1 mass % to 30 mass % and more preferably from 5 mass % to 20 mass % of the total amount of the treatment liquid.

[0028] --Silicone surfactants-- The silicone surfactant is not particularly limited and can be appropriately selected depending on the purpose. Examples of the silicone surfactant include side-chain modified polydimethylsiloxane, both-end modified polydimethylsiloxane, one-end modified polydimethylsiloxane, and both-end side-chain modified polydimethylsiloxane. Polyether-modified silicone surfactants having a polyoxyethylene group or a polyoxyethylene polyoxypropylene group as a modifying group are particularly preferred because they exhibit good properties as an aqueous surfactant. Such surfactants may be appropriately synthesized or commercially available products, such as those available from BYK-Chemie Co., Ltd., Shin-Etsu Chemical Co., Ltd., Dow Corning Toray Silicone Co., Ltd., Nippon Emulsion Co., Ltd., and Kyoeisha Chemical Co., Ltd. The polyether-modified silicone surfactant is not particularly limited and can be appropriately selected depending on the purpose. For example, it can be a surfactant represented by the general formula (S-1) in which a polyalkylene oxide structure is introduced into the Si part side chain of dimethylpolysiloxane. JPEG0007647405000001.jpg66151 General formula (S-1) (In the general formula (S-1), m, n, a, and b each independently represent an integer, R represents an alkylene group, and R' represents an alkyl group.) As the polyether-modified silicone surfactant, commercially available products can be used, such as KF-618, KF-642, KF-643 (Shin-Etsu Chemical Co., Ltd.), EMALEX-SS-5602, SS-1906EX (Nihon Emulsion Co., Ltd.), FZ-2105, FZ-2118, FZ-2154, FZ-2161, FZ-2162, FZ-2163, FZ-2164 (Toray Dow Corning Silicone Co., Ltd.), BYK-33, BYK-387 (BYK-Chemie Co., Ltd.), TSF4440, TSF4452, TSF4453 (Toshiba Silicone Co., Ltd.), WET-270 (Evonik), and SAG503A (Nissin Chemical Industry Co., Ltd.).

[0029] The content of the surfactant in the treatment liquid is not particularly limited and may be appropriately selected depending on the purpose. From the viewpoints of excellent wettability and ejection stability and improved image quality, the content is preferably from 0.001% by mass to 5% by mass, and more preferably from 0.05% by mass to 5% by mass.

[0030] --Other ingredients-- The other components are not particularly limited and can be appropriately selected depending on the purpose.

[0031] The non-permeable substrate, which is the recording medium used in the present invention, is a substrate having a surface with low water permeability and absorbency, and includes materials that have many cavities inside but are not open to the outside. More quantitatively, in the Bristow method, 1 / 2 Water absorption up to 10mL / m 2 The term "substrate" refers to a substrate that is: As the impermeable substrate, for example, polyvinyl chloride resin film, polyethylene terephthalate (PET) film, polypropylene, polyethylene, polycarbonate film, nylon film, and the like can be suitably used. Examples of the polypropylene film include P-2002, P-2161, and P-4166 manufactured by Toyobo Co., Ltd., PA-20, PA-30, and PA-20W manufactured by Suntox Co., Ltd., and FOA, FOS, and FOR manufactured by Futamura Chemical Co., Ltd. Examples of the polyethylene terephthalate film include E-5100 and E-5102 manufactured by Toyobo, P60 and P375 manufactured by Toray, and G2, G2P2, K and SL manufactured by Teijin DuPont Films. Examples of the nylon film include Harden Film N-1100, N-1102, and N-1200 manufactured by Toyobo Co., Ltd., and ON, NX, MS, and NK manufactured by Unitika Co., Ltd.

[0032] <Ink application process and ink application means> The ink application step is a step of applying ink onto the treatment liquid. The ink applying unit applies the ink, which is contained in an ink storage unit and contains a coloring material, an organic solvent, and a resin, onto the treatment liquid. The ink storage container is not particularly limited and can be appropriately selected depending on the purpose.

[0033] -ink- The organic solvent, water, coloring material, resin, additives, etc. used in the ink will be described below.

[0034] -Organic solvents- The organic solvent used in the present invention is not particularly limited, and any water-soluble organic solvent can be used. Examples of the organic solvent include polyhydric alcohols, ethers such as polyhydric alcohol alkyl ethers and polyhydric alcohol aryl ethers, nitrogen-containing heterocyclic compounds, amides, amines, and sulfur-containing compounds. Specific examples of the water-soluble organic solvent include ethylene glycol, diethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 3-methyl-1,3-butanediol, triethylene glycol, polyethylene glycol, polypropylene glycol, 1,2-pentanediol, 1,3-pentanediol, 1,4-pentanediol, 2,4-pentanediol, 1,5-pentanediol, and the like. polyhydric alcohols such as pentanediol, 1,2-hexanediol, 1,6-hexanediol, 1,3-hexanediol, 2,5-hexanediol, 1,5-hexanediol, glycerin, 1,2,6-hexanetriol, 2-ethyl-1,3-hexanediol, ethyl-1,2,4-butanetriol, 1,2,3-butanetriol, 2,2,4-trimethyl-1,3-pentanediol, and petriol, ethylene glycol monoethyl ether, and ethylene glycol monobutyl ether. polyhydric alcohol alkyl ethers such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, tetraethylene glycol monomethyl ether, and propylene glycol monoethyl ether; polyhydric alcohol aryl ethers such as ethylene glycol monophenyl ether and ethylene glycol monobenzyl ether; nitrogen-containing heterocyclic compounds such as 2-pyrrolidone, N-methyl-2-pyrrolidone, N-hydroxyethyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, ε-caprolactam, and γ-butyrolactone; amides such as formamide, N-methylformamide, N,N-dimethylformamide, 3-methoxy-N,N-dimethylpropionamide, and 3-butoxy-N,N-dimethylpropionamide; amines such as monoethanolamine, diethanolamine, and triethylamine; sulfur-containing compounds such as dimethyl sulfoxide, sulfolane, and thiodiethanol; propylene carbonate, and ethylene carbonate. It is preferable to use an organic solvent having a boiling point of 250° C. or less, since this not only functions as a wetting agent but also provides good drying properties.

[0035] Polyol compounds having 8 or more carbon atoms and glycol ether compounds are also suitably used. Specific examples of polyol compounds having 8 or more carbon atoms include 2-ethyl-1,3-hexanediol and 2,2,4-trimethyl-1,3-pentanediol. Specific examples of the glycol ether compound include polyhydric alcohol alkyl ethers such as ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, tetraethylene glycol monomethyl ether, and propylene glycol monoethyl ether; and polyhydric alcohol aryl ethers such as ethylene glycol monophenyl ether and ethylene glycol monobenzyl ether. Polyol compounds having 8 or more carbon atoms and glycol ether compounds can improve the permeability of ink when paper is used as the recording medium.

[0036] The content of the organic solvent in the ink is not particularly limited and can be appropriately selected depending on the purpose. From the viewpoints of the drying property and ejection reliability of the ink, however, the content is preferably from 10% by mass to 60% by mass, and more preferably from 20% by mass to 60% by mass.

[0037] -Coloring materials- The coloring material is not particularly limited, and pigments and dyes can be used. The pigment may be an inorganic pigment or an organic pigment. These may be used alone or in combination of two or more. Mixed crystals may also be used. Examples of pigments that can be used include black pigments, yellow pigments, magenta pigments, cyan pigments, white pigments, green pigments, orange pigments, glossy pigments such as gold and silver pigments, and metallic pigments. As inorganic pigments, titanium oxide, iron oxide, calcium carbonate, barium sulfate, aluminum hydroxide, barium yellow, cadmium red, chrome yellow, as well as carbon black produced by known methods such as the contact method, furnace method, and thermal method can be used. As organic pigments, azo pigments, polycyclic pigments (e.g., phthalocyanine pigments, perylene pigments, perinone pigments, anthraquinone pigments, quinacridone pigments, dioxazine pigments, indigo pigments, thioindigo pigments, isoindolinone pigments, quinophthalone pigments, etc.), dye chelates (e.g., basic dye chelates, acid dye chelates, etc.), nitro pigments, nitroso pigments, aniline black, etc. can be used. Among these pigments, those having good affinity with the solvent are preferably used. In addition, resin hollow particles and inorganic hollow particles can also be used. Specific examples of pigments for black colors include carbon blacks (CI Pigment Black 7) such as furnace black, lamp black, acetylene black, and channel black; metals such as copper, iron (CI Pigment Black 11), and titanium oxide; and organic pigments such as aniline black (CI Pigment Black 1). In addition, for color, CI Pigment Yellow 1, 3, 12, 13, 14, 17, 24, 34, 35, 37, 42 (yellow iron oxide), 53, 55, 74, 81, 83, 95, 97, 98, 100, 101, 104, 108, 109, 110, 117, 120, 138, 150, 153, 155, 180, 185, 213, CI Pigment Yellow Range 5, 13, 16, 17, 36, 43, 51, CI Pigment Red 1, 2, 3, 5, 17, 22, 23, 31, 38, 48:2, 48:2 (Permanent Red 2B (Ca)), 48:3, 48:4, 49:1, 52:2, 53:1, 57:1 (Brilliant Carmine 6B), 60:1, 63:1, 63:2, 64:1, 81, 83, 88 , 101 (red oxide), 104, 105, 106, 108 (cadmium red), 112, 114, 122 (quinacridone magenta), 123, 146, 149, 166, 168, 170, 172, 177, 178, 179, 184, 185, 190, 193, 202, 207, 208, 209, 213, 219, 224, 254, 264, CI Pigment Violet 1 (Rhodamine Lake), 3, 5:1, 16, 19, 23, 38; CI Pigment Blue 1, 2, 15 (Phthalocyanine Blue), 15:1, 15:2, 15:3, 15:4 (Phthalocyanine Blue), 16, 17:1, 56, 60, 63; CI Pigment Green 1, 4, 7, 8, 10, 17, 18, 36, etc. The dye is not particularly limited, and acid dyes, direct dyes, reactive dyes, and basic dyes can be used. One type of dye may be used alone, or two or more types may be used in combination. Examples of the dyes include CI Acid Yellow 17, 23, 42, 44, 79, 142, CI Acid Red 52, 80, 82, 249, 254, 289, CI Acid Blue 9, 45, 249, CI Acid Black 1, 2, 24, 94, CI Food Black 1, 2, CI Direct Yellow 1, 12, 24, 33, 50, 55, 58, 86, 132, 142, 144, 173, CI Direct Red 1, 4, 9, 80, 81, 225, 227, CI Direct Blue 1, 2, 15, 71, 86, 87, 98, 165, 199, 202, CI Directed Black 19, 38, 51, 71, 154, 168, 171, 195, and CI Reactive Red. 14, 32, 55, 79, 249, and CI Reactive Black 3, 4, and 35.

[0038] The content of the coloring material in the ink is preferably from 0.1% to 15% by mass, and more preferably from 1% to 10% by mass, from the viewpoints of improving image density, good adhesion, and ejection stability.

[0039] Methods for dispersing a pigment to obtain an ink include a method of introducing a hydrophilic functional group into the pigment to make it a self-dispersing pigment, a method of dispersing the pigment by coating the surface of the pigment with a resin, and a method of dispersing the pigment using a dispersant. As a method for introducing a hydrophilic functional group into a pigment to make it a self-dispersing pigment, for example, a method in which a functional group such as a sulfone group or a carboxyl group is added to a pigment (e.g., carbon) to make it dispersible in water can be mentioned. As a method for dispersing a pigment by coating its surface with a resin, there is a method in which the pigment is encapsulated in a microcapsule to make it dispersible in water. This can be called a resin-coated pigment. In this case, it is not necessary for all of the pigments blended in the ink to be coated with a resin, and uncoated or partially coated pigments may be dispersed in the ink as long as the effect of the present invention is not impaired. Examples of the method for dispersing using a dispersant include a method for dispersing using a known low molecular weight dispersant or a polymeric dispersant, typified by a surfactant. As the dispersant, for example, anionic surfactants, cationic surfactants, amphoteric surfactants, nonionic surfactants, etc. can be used depending on the pigment. RT-100 (nonionic surfactant) manufactured by Takemoto Oil Co., Ltd. and sodium naphthalenesulfonate formalin condensate can also be suitably used as dispersants. The dispersants may be used alone or in combination of two or more.

[0040] [Pigment dispersion] It is possible to obtain ink by mixing a pigment with materials such as water or an organic solvent, or it is also possible to manufacture ink by mixing a pigment with other materials such as water and a dispersant to prepare a pigment dispersion, and then mixing the resulting mixture with materials such as water or an organic solvent. The pigment dispersion is obtained by mixing and dispersing water, a pigment, a pigment dispersant, and other components as required, and adjusting the particle size. Dispersion is preferably performed using a dispersing machine. The particle size of the pigment in the pigment dispersion is not particularly limited, but the maximum frequency in terms of the maximum number is preferably 20 nm or more and 500 nm or less, more preferably 20 nm or more and 150 nm or less, in order to improve the dispersion stability of the pigment and the image quality such as ejection stability and image density. The particle size of the pigment can be measured using a particle size analyzer (Nanotrac Wave-UT151, manufactured by Microtrac Bell Co., Ltd.). The content of the pigment in the pigment dispersion is not particularly limited and can be appropriately selected depending on the purpose. From the viewpoints of obtaining good ejection stability and increasing image density, the content is preferably 0.1% by mass or more and 50% by mass or less, and more preferably 0.1% by mass or more and 30% by mass or less. It is preferable that the pigment dispersion is degassed, if necessary, by filtering coarse particles using a filter, a centrifugal separator, or the like.

[0041] -resin- The type of resin contained in the ink is not particularly limited and can be appropriately selected depending on the purpose. Examples of the resin include urethane-based resins, polyester-based resins, acrylic-based resins, vinyl acetate-based resins, styrene-based resins, butadiene-based resins, styrene-butadiene-based resins, vinyl chloride-based resins, acrylic styrene-based resins, and acrylic silicone-based resins. Resin particles made of these resins may be used. The resin particles may be dispersed in water as a dispersion medium to form a resin emulsion, and then mixed with materials such as coloring materials and organic solvents to obtain an ink. The resin particles may be appropriately synthesized or may be commercially available. These may be used alone or in combination of two or more types of resin particles.

[0042] The volume average particle size of the resin particles is not particularly limited and can be appropriately selected depending on the purpose. From the viewpoint of obtaining good adhesion and high image hardness, however, it is preferably from 10 nm to 1,000 nm, more preferably from 10 nm to 200 nm, and particularly preferably from 10 nm to 100 nm. The volume average particle size can be measured, for example, using a particle size analyzer (Nanotrac Wave-UT151, manufactured by Microtrac-Bell Co., Ltd.).

[0043] The resin content is not particularly limited and can be selected appropriately depending on the purpose. From the viewpoints of adhesion and storage stability of the ink, however, the resin content is preferably from 1% by mass to 30% by mass, and more preferably from 5% by mass to 20% by mass, of the total amount of the ink.

[0044] -water- The water content in the ink is not particularly limited and can be appropriately selected depending on the purpose. From the viewpoint of the drying property and ejection reliability of the ink, however, it is preferably from 10% to 90% by mass, and more preferably from 20% to 60% by mass.

[0045] The particle size of the solid content in the ink is not particularly limited and can be appropriately selected depending on the purpose, but in terms of improving image quality such as ejection stability and image density, the maximum frequency in terms of maximum number is preferably 20 nm or more and 1000 nm or less, more preferably 20 nm or more and 150 nm or less. The solid content includes resin particles, pigment particles, etc. The particle size can be measured using a particle size analyzer (Nanotrac Wave-UT151, manufactured by Microtrac Bell Co., Ltd.).

[0046] -Additives- If necessary, surfactants, antifoaming agents, antiseptics, antifungals, rust inhibitors, pH adjusters, etc. may be added to the ink.

[0047] -Surfactants- As the surfactant, any of silicone-based surfactants, fluorine-based surfactants, amphoteric surfactants, nonionic surfactants, and anionic surfactants can be used. Silicone surfactants are not particularly limited and can be appropriately selected according to purpose.Among them, those that do not decompose even at high pH are preferred, such as side chain modified polydimethylsiloxane, both end modified polydimethylsiloxane, one end modified polydimethylsiloxane, side chain both end modified polydimethylsiloxane, etc., and those having polyoxyethylene group or polyoxyethylene polyoxypropylene group as modified group are particularly preferred because they show good properties as aqueous surfactants.In addition, polyether modified silicone surfactants can also be used as the silicone surfactant, such as a compound in which a polyalkylene oxide structure is introduced into the Si part side chain of dimethylsiloxane. As the fluorosurfactant, for example, perfluoroalkyl sulfonic acid compounds, perfluoroalkyl carboxylic acid compounds, perfluoroalkyl phosphate compounds, perfluoroalkyl ethylene oxide adducts, and polyoxyalkylene ether polymer compounds having perfluoroalkyl ether groups on the side chain are particularly preferred because they have low foaming properties. As the perfluoroalkyl sulfonic acid compounds, for example, perfluoroalkyl sulfonic acid, perfluoroalkyl sulfonate, etc. are included. As the perfluoroalkyl carboxylic acid compounds, for example, perfluoroalkyl carboxylic acid, perfluoroalkyl carboxylate, etc. are included. As the polyoxyalkylene ether polymer compounds having perfluoroalkyl ether groups on the side chain, for example, sulfate ester salts of polyoxyalkylene ether polymers having perfluoroalkyl ether groups on the side chains, salts of polyoxyalkylene ether polymers having perfluoroalkyl ether groups on the side chains, etc. are included. As counter ions of the salts in these fluorosurfactants, Li, Na, K, NH4, NH3CH2CH2OH, NH2(CH2CH2OH)2, NH(CH2CH2OH)3, etc. are included. Examples of amphoteric surfactants include lauryl aminopropionate, lauryl dimethyl betaine, stearyl dimethyl betaine, and lauryl dihydroxyethyl betaine. Examples of nonionic surfactants include polyoxyethylene alkylphenyl ethers, polyoxyethylene alkyl esters, polyoxyethylene alkylamines, polyoxyethylene alkylamides, polyoxyethylene propylene block polymers, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, and ethylene oxide adducts of acetylene alcohol. Examples of the anionic surfactant include polyoxyethylene alkyl ether acetates, dodecylbenzene sulfonates, laurates, and polyoxyethylene alkyl ether sulfates. These may be used alone or in combination of two or more.

[0048] The silicone surfactant is not particularly limited and can be appropriately selected depending on the purpose. Examples of the silicone surfactant include side-chain modified polydimethylsiloxane, both-end modified polydimethylsiloxane, one-end modified polydimethylsiloxane, and both-end side-chain modified polydimethylsiloxane. Polyether-modified silicone surfactants having a polyoxyethylene group or a polyoxyethylene polyoxypropylene group as a modifying group are particularly preferred because they exhibit good properties as an aqueous surfactant. Such surfactants may be appropriately synthesized or commercially available products, such as those available from BYK-Chemie Co., Ltd., Shin-Etsu Chemical Co., Ltd., Dow Corning Toray Silicone Co., Ltd., Nippon Emulsion Co., Ltd., and Kyoeisha Chemical Co., Ltd. The polyether-modified silicone surfactant is not particularly limited and can be appropriately selected depending on the purpose. For example, it can be a surfactant represented by the general formula (S-1) in which a polyalkylene oxide structure is introduced into the Si part side chain of dimethylpolysiloxane. JPEG0007647405000002.jpg66151 General formula (S-1) (In the general formula (S-1), m, n, a, and b each independently represent an integer, R represents an alkylene group, and R' represents an alkyl group). As the polyether-modified silicone surfactant, commercially available products can be used, such as KF-618, KF-642, KF-643 (Shin-Etsu Chemical Co., Ltd.), EMALEX-SS-5602, SS-1906EX (Nihon Emulsion Co., Ltd.), FZ-2105, FZ-2118, FZ-2154, FZ-2161, FZ-2162, FZ-2163, FZ-2164 (Dow Corning Toray Silicone Co., Ltd.), BYK-33, BYK-387 (BYK-Chemie Co., Ltd.), TSF4440, TSF4452, TSF4453 (Toshiba Silicon Co., Ltd.), and the like.

[0049] The content of the surfactant in the ink is not particularly limited and can be appropriately selected depending on the purpose. From the viewpoints of excellent wettability and ejection stability and improved image quality, the content is preferably from 0.001% by mass to 5% by mass, and more preferably from 0.05% by mass to 5% by mass.

[0050] - Defoaming agent - The defoaming agent is not particularly limited, and examples thereof include silicone-based defoaming agents, polyether-based defoaming agents, and fatty acid ester-based defoaming agents. These may be used alone or in combination of two or more. Among these, silicone-based defoaming agents are preferred because of their excellent foam breaking effect.

[0051] -Preservative and fungicidal agent- The antiseptic and antifungal agent is not particularly limited, and examples thereof include 1,2-benzisothiazolin-3-one.

[0052] -Rust inhibitor- The rust inhibitor is not particularly limited, and examples thereof include acid sulfite and sodium thiosulfate.

[0053] -pH adjuster- There are no particular limitations on the pH adjuster, so long as it is capable of adjusting the pH to 7 or higher, and examples of the pH adjuster include amines such as diethanolamine and triethanolamine.

[0054] The physical properties of the ink are not particularly limited and can be appropriately selected depending on the purpose. For example, it is preferable that the viscosity, surface tension, pH, etc. are within the following ranges. The viscosity of the ink at 25°C is preferably from 5 mPa·s to 30 mPa·s, more preferably from 5 mPa·s to 25 mPa·s, in order to improve print density and character quality and to obtain good ejection properties. Here, the viscosity can be measured using, for example, a rotational viscometer (RE-80L manufactured by Toki Sangyo Co., Ltd.). The measurement conditions are 25°C, a standard cone rotor (1°34' x R24), a sample liquid volume of 1.2 mL, a rotation speed of 50 rpm, and 3 minutes. The surface tension of the ink is preferably 35 mN / m or less, and more preferably 32 mN / m or less at 25° C., in order to ensure that the ink is appropriately leveled on the recording medium and the drying time of the ink is shortened. The pH of the ink is preferably from 7 to 12, and more preferably from 8 to 11, from the viewpoint of preventing corrosion of metal members that come into contact with the ink.

[0055] <Other processes> The other steps are not particularly limited and can be appropriately selected depending on the purpose.

[0056] [Recordings] The ink recorded matter of the present invention comprises an image formed on a recording medium using the ink of the present invention. A recorded matter can be obtained by recording using an inkjet recording apparatus and an inkjet recording method.

[0057] [Recording device, recording method] The ink of the present invention can be suitably used in various recording devices using the ink jet recording method, such as printers, facsimile machines, copying machines, printer / fax / copier combination machines, and three-dimensional modeling devices. In the present invention, the recording apparatus and recording method refer to an apparatus capable of ejecting ink, various treatment liquids, etc. onto a recording medium, and a method of recording using the apparatus. The recording medium refers to an object onto which ink or various treatment liquids can be attached even temporarily. This recording device can include not only a head portion that ejects ink, but also means related to feeding, transporting, and discharging the recording medium, as well as other devices called pre-processing devices and post-processing devices. The recording apparatus and the recording method may have a heating means used in the heating step and a drying means used in the drying step. The heating means and the drying means include, for example, a means for heating and drying the printed surface and the back surface of the recording medium. The heating means and the drying means are not particularly limited, but for example, a hot air heater and an infrared heater can be used. Heating and drying can be performed before, during, or after printing. In addition, the recording device and recording method are not limited to those that visualize meaningful images such as characters and figures with ink. For example, those that form patterns such as geometric designs and those that create three-dimensional images are also included. Furthermore, unless otherwise specified, the recording apparatus includes both a serial type apparatus in which the ejection head moves and a line type apparatus in which the ejection head does not move. Furthermore, this recording device includes not only desktop types, but also wide-width recording devices capable of printing on A0-sized recording media, and continuous-feed printers that can use continuous paper wound into a roll as a recording medium. An example of a recording device will be described with reference to Figs. 1 and 2. Fig. 1 is a perspective view of the device. Fig. 2 is a perspective view of a main tank. An image forming device 400 as an example of a recording device is a serial type image forming device. A mechanism unit 420 is provided inside an exterior 401 of the image forming device 400. Each ink storage unit 411 of the main tanks 410 (410k, 410c, 410m, 410y) for each color of black (K), cyan (C), magenta (M), and yellow (Y) is formed by a packaging member L such as an aluminum laminate film. The ink storage unit 411 is stored in a storage container case 414 made of plastic, for example. As a result, the main tanks 410 are used as ink cartridges of each color. On the other hand, a cartridge holder 404 is provided at the back side of the opening when the cover 401c of the apparatus body is opened. A main tank 410 is detachably attached to the cartridge holder 404. As a result, each ink outlet 413 of the main tank 410 communicates with an ejection head 434 for each color via a supply tube 436 for each color, and ink can be ejected from the ejection head 434 to a recording medium.

[0058] This recording apparatus can include not only a portion that ejects ink, but also devices called pre-processing devices and post-processing devices. As an embodiment of the pre-treatment device and post-treatment device, a liquid storage section having a pre-treatment liquid and a liquid ejection head, similar to the case of inks such as black (K), cyan (C), magenta (M), and yellow (Y), and the like, are added, and the pre-treatment liquid and the post-treatment liquid are ejected by an inkjet recording method. As another embodiment of the pre-treatment device and the post-treatment device, there is an embodiment in which a pre-treatment device and a post-treatment device using a method other than the inkjet recording method, for example, a blade coating method, a roll coating method, or a spray coating method, are provided.

[0059] The ink application method is not limited to the inkjet recording method, and can be widely used.Other than the inkjet recording method, for example, blade coating method, gravure coating method, gravure offset coating method, bar coating method, roll coating method, knife coating method, air knife coating method, comma coating method, U comma coating method, AKKU coating method, smoothing coating method, microgravure coating method, reverse roll coating method, four-roll coating method, five-roll coating method, dip coating method, curtain coating method, slide coating method, die coating method, etc. can be mentioned. Fig. 3 is a schematic diagram showing an example of an image forming apparatus used in the image forming method of the present invention. The image forming apparatus 100 in Fig. 3 has a means for applying a treatment liquid (a treatment liquid application device), a discharge means for discharging ink (ink discharge head 4), and a conveyor belt 7.

[0060] (Set of treatment liquid and ink) The treatment liquid and ink set of the present invention contains a polyvalent metal salt, a resin T A , the resin T A Resin T different from B and a treatment liquid containing a silicone surfactant (but not containing an organic solvent with a boiling point of 200°C or higher); The ink includes a coloring material, an organic solvent, and a resin, and may further include other components as required. The treatment liquid and the ink in the set of treatment liquid and ink of the present invention are the same as the treatment liquid and the ink in the image forming method of the present invention.

[0061] (Manufacturing method of printed matter) The method for producing a printed matter of the present invention comprises the steps of: A , the resin T A Resin T different from B and a silicone-based surfactant (but does not include an organic solvent having a boiling point of 200° C. or higher under normal pressure) to a non-permeable substrate by an inkjet method; and an ink-applying step of applying an ink containing a colorant, an organic solvent, and a resin onto the treatment liquid, and further including other steps as necessary. The method for producing the printed matter of the present invention is the same as the image forming method of the present invention.

[0062] In the present invention, the terms image formation, recording, printing, printing, etc. are all synonymous.

[0063] Recording medium, media, and printed material are all synonymous. EXAMPLES

[0064] Examples of the present invention will be described below, but the present invention is not limited to these examples. In the following examples, unless otherwise specified, the preparation and evaluation of inks were carried out under conditions of room temperature of 25°C and relative humidity of 60% RH. In the examples, "parts" refers to "parts by mass", and "%" refers to "% by mass" except in the evaluation criteria.

[0065] <Preparation of cyan pigment dispersion (dispersant-dispersed type)> A cyan pigment dispersion was obtained in the same manner as described in "Method A" of "Pigment surface modification treatment" in JP2012-207202A. Specifically, 20 g of CI Pigment Blue 15:3 (product name: Chromofine Blue, manufactured by Dainichi Seikagaku Chemical Industry Co., Ltd.), 20 mmol of a compound represented by the following structural formula (5), and 200 mL of ion-exchanged water are mixed in a Silverson mixer (6,000 rpm (0.6% by mass)) at room temperature to obtain a slurry. 20 mmol of nitric acid was added if the pH of the resulting slurry was higher than 4. After 30 minutes, sodium nitrite (20 mmol) dissolved in a small amount of ion-exchanged water was slowly added to the above slurry. The mixture was then heated to 60° C. with stirring and reacted for 1 hour, yielding a modified pigment in which a compound represented by the following structural formula (5) was added to the surface of the CI Pigment Blue 15:3. Next, the pH was adjusted to 10 with an aqueous NaOH solution, and after 30 minutes, a modified pigment dispersion was obtained. The modified pigment dispersion and ion-exchanged water were subjected to ultrafiltration using a dialysis membrane, and further subjected to ultrasonic dispersion, to obtain a cyan pigment dispersion (self-dispersing type) having a bisphosphonic acid group as a hydrophilic functional group with a pigment concentration of 15 mass%.

[0066] [ka] ...Structural formula (5)

[0067] <Preparation of black pigment dispersion (dispersant-dispersed type)> A black pigment dispersion with a pigment concentration of 15% by mass was prepared in the same manner as in the preparation of the cyan pigment dispersion, except that 20 g of CI Pigment Blue 15:3 was replaced with 20 g of carbon black (NIPEX160, manufactured by Degussa).

[0068] <Preparation of magenta pigment dispersion (dispersant-dispersed type)> A magenta pigment dispersion with a pigment concentration of 15% by mass was prepared in the same manner as in the preparation of the cyan pigment dispersion, except that 20 g of CI Pigment Blue 15:3 was changed to 20 g of CI Pigment Red 122 (product name: Toner Magenta EO02, manufactured by Clariant Japan Co., Ltd.).

[0069] <Preparation of Yellow Pigment Dispersion (Dispersant Dispersion Type)> A yellow pigment dispersion with a pigment concentration of 15% by mass was prepared in the same manner as in the preparation of the cyan pigment dispersion, except that 20 g of CI Pigment Blue 15:3 was changed to 20 g of CI Pigment Yellow 74 (product name: First Yellow 531, manufactured by Dainichiseika Color & Chemicals Mfg. Co., Ltd.).

[0070] (Resin particle preparation example 1) <Preparation of polycarbonate-based urethane resin particle liquid> A reaction vessel equipped with a stirrer, a reflux condenser, and a thermometer was charged with 1,500 g of polycarbonate diol (a reaction product of 1,6-hexanediol and dimethyl carbonate (number average molecular weight (Mn): 1,200), 220 g of 2,2-dimethylolpropionic acid (hereinafter sometimes referred to as "DMPA"), and 1,347 g of N-methylpyrrolidone (hereinafter sometimes referred to as "NMP") under a nitrogen stream, and the mixture was heated to 60°C to dissolve the DMPA. Next, 1,445 g of 4,4'-dicyclohexylmethane diisocyanate and 2.6 g of dibutyltin dilaurate (catalyst) were added, and the mixture was heated to 90°C and subjected to a urethane reaction for 5 hours to obtain an isocyanate-terminated urethane prepolymer. The reaction mixture was cooled to 80°C, and 149 g of triethylamine was added thereto. 4,340 g was extracted from the mixture and added to a mixed solution of 5,400 g of water and 15 g of triethylamine under strong stirring. Next, 1,500 g of ice was added, and 626 g of a 35% by mass aqueous solution of 2-methyl-1,5-pentanediamine was added to carry out a chain extension reaction, and the solvent was distilled off so that the solid content concentration became 40% by mass, thereby obtaining a polycarbonate-based urethane resin particle liquid. The glass transition temperature (hereinafter, sometimes referred to as "Tg") of the resin of the obtained polycarbonate-based urethane resin particle liquid was measured, and Tg was -20°C.

[0071] (Resin Particle Preparation Example 2) <Preparation of Polyester-Based Urethane Resin Particle Liquid> A polyester-based urethane resin particle liquid having a solid content concentration of 30% by mass was obtained in the same manner as in Preparation Example 1 of Resin Particles, except that in Preparation Example 2 of Resin Particles, the polyether polyol ("PTMG1000", manufactured by Mitsubishi Chemical Corporation, weight average molecular weight: 1,000) was changed to a polyester polyol ("Polylite OD-X-2251", manufactured by DIC Corporation, weight average molecular weight: 2,000). The obtained polyester-based urethane resin particle liquid had a Tg of 57° C. as measured in the same manner as in Preparation Example 1 of the polycarbonate-based urethane resin particle liquid.

[0072] (Preparation example of ink 1) Ink 1 was prepared by adding 15% by mass of the black pigment dispersion (pigment solids concentration: 15% by mass), 25% by mass of the polycarbonate-based urethane resin particle liquid of Preparation Example 1 (solids concentration: 40% by mass), 15% by mass of the polyester-based urethane resin particle liquid of Preparation Example 2 (solids concentration: 30% by mass), 23% by mass of 1,2-propanediol (manufactured by Tokyo Chemical Industry Co., Ltd.), 10% by mass of 3-methoxy-3-methyl-1-butanol (manufactured by Kuraray Co., Ltd.), 5% by mass of 2,3-butanediol (manufactured by Tokyo Chemical Industry Co., Ltd.), 3% by mass of 2-ethylhexyl alcohol (manufactured by Tokyo Chemical Industry Co., Ltd.), 1% by mass of a polyether-modified surfactant (product name: WET-270: manufactured by TEGO), 0.1% by mass of Proxel LV (product name: Arch Chemicals Japan Co., Ltd.) as a preservative, and high purity water to the remaining amount, mixing and stirring, and filtering through a polypropylene filter having an average pore size of 1.0 μm.

[0073] (Preparation examples of inks 2 to 6) Inks 2 to 6 were prepared in the same manner as in Example 1 so as to have the compositions shown in Table 1.

[0074] [Table 1]

[0075] (Preparation examples of treatment solutions 1 to 18) Based on the compositions shown in Tables 2 to 5, materials were mixed by a conventionally known method to prepare treatment solutions 1 to 18.

[0076] [Table 2]

[0077] [Table 3]

[0078] [Table 4]

[0079] [Table 5]

[0080] The details of each component in Tables 2 to 5 are as follows. [Polyvalent metal salts] Calcium acetate: Nacalai Tesque, Inc. Magnesium acetate: Nacalai Tesque, Inc. Aluminum silicate: Fujifilm Wako Pure Chemical Industries, Ltd. [resin] Nonionic urethane resin: Superflex E2000, manufactured by Daiichi Kogyo Co., Ltd., volume average particle size: 700 nm, solid content: 50%, Tg: 38°C Nonionic vinyl acetate resin: Vinyblan 4003, manufactured by Nissin Chemical Industry Co., Ltd., solid content: 50%, Tg: -15°C Nonionic vinyl acetate resin: Vinybran GV-6181, manufactured by Nissin Chemical Industry Co., Ltd., solid content concentration: 50%, Tg: 30°C Nonionic vinyl acetate resin: Vinyblan 1225, manufactured by Nissin Chemical Industry Co., Ltd., solid content: 45%, Tg: 9°C Core-shell cationic acrylic resin: UW-550CS, Taisei Fine Chemical Co., Ltd., solid content: 34%, Tg: 40℃ [Surfactants] Silicone surfactant: WET-270, manufactured by Evonik Silicone surfactant: SAG503A, manufactured by Nissin Chemical Industry Co., Ltd. Olefin-based surfactant: Olefin EXP.4300 (registered trademark), manufactured by Nissin Chemical Industry Co., Ltd. [solvent] 1,2-Propanediol, boiling point: 187℃ 3-Methoxy-3-methyl-1-butanol, boiling point: 174°C Glycerin, boiling point: 290℃

[0081] (Examples 1 to 17 and Comparative Examples 1 to 6) Using the prepared inks and treatment liquids in the combinations shown in Tables 6 to 9, the "ejection stability of the treatment liquid" and the "adhesion" of the resulting images were evaluated.

[0082] <Discharge stability of treatment liquid> The prepared treatment liquid was filled into an inkjet printer (device name: modified IPSiO GXe5500, manufactured by Ricoh Co., Ltd.), and the ejection stability after decap was evaluated. First, in an environment of 25°C and 30% RH, head cleaning was performed using the printer's maintenance command, and a test chart was printed to confirm that all nozzle channels were in an ejection state. Next, the head was left uncapped for 5 minutes, and then the test chart was printed again. The number of non-ejection channels was counted from the test chart before and after leaving it, and judged according to the following criteria. Note that for practical use, the number of non-ejection channels is less than 10 (evaluation A or B). [Evaluation Criteria] AA: Number of non-ejecting channels is 1 or less A: The number of non-discharge channels is 2 or more and less than 10 B: The number of non-ejecting channels is 10 or more and less than 20 C: 20 or more non-ejecting channels

[0083] <Adhesion> The ink was filled into an inkjet printer (device name: modified IPSiO GXe5500, manufactured by Ricoh Co., Ltd.). A halftone image (treatment liquid) was printed on a PET substrate (manufactured by HiFi Industrial Film) with a volume of 21 pL per drop of treatment liquid and a print rate of 10 to 90% at a resolution of 600 × 600 dpi. Thereafter, the print was passed through a hot air drying unit at 70° C. to dry and fix the image (processing liquid). Next, ink was applied to the PET substrate on which the image (treatment liquid) had been printed, and an image was printed. A solid color image with a 100% gradation and a resolution of 600 x 600 dpi was printed with a volume of 21 pL per drop of ink. The print was then passed through a hot air drying unit at 70°C to dry and fix the image (ink). A solid image formed on a PET recording medium was subjected to a checkerboard peel test using a cloth adhesive tape (Nichiban Co., Ltd., 123LW-50), and the number of remaining squares out of 100 test squares was counted, and the "adhesion" to the recording medium was evaluated based on the following evaluation criteria. A rating of B or higher is desirable for practical use. [Evaluation Criteria] AA: 98 or more remaining squares A: 90 or more but less than 98 remaining squares B: 70 to less than 90 remaining squares C: Less than 70 remaining squares

[0084] [Table 6]

[0085] [Table 7]

[0086] [Table 8]

[0087] [Table 9]

[0088] For example, aspects of the present invention are as follows. <1> Polyvalent metal salts, resin T A , the resin T A Resin T different from B and a treatment liquid application step of applying a treatment liquid containing a silicone surfactant (but not containing an organic solvent having a boiling point of 200° C. or higher under normal pressure) to a non-permeable substrate by an inkjet method; an ink applying step of applying an ink containing a coloring material, an organic solvent, and a resin onto the treatment liquid; The image forming method is characterized by comprising: <2> Resin T A Glass transition temperature Tg A is Tg A ≦-15°C, Resin T B Glass transition temperature Tg B 30℃≦Tg B The above <1> 2. The image forming method according to claim 1 . <3> The polyvalent metal salt includes at least one of a magnesium salt and a calcium salt. <1> from <2> 13. The image forming method according to claim 12, wherein <4> Polyvalent metal salts, resin T A , the resin T A Resin T different from B and a treatment liquid containing a silicone surfactant (but not containing an organic solvent with a boiling point of 200°C or higher); and an ink containing a coloring material, an organic solvent, and a resin. <5> Polyvalent metal salts, resin T A , the resin T A Resin T different from B and a treatment liquid application step of applying a treatment liquid containing a silicone surfactant (but not containing an organic solvent having a boiling point of 200° C. or higher under normal pressure) to a non-permeable substrate by an inkjet method; an ink applying step of applying an ink containing a coloring material, an organic solvent, and a resin onto the treatment liquid; A method for producing a printed matter comprising the steps of: <6> Polyvalent metal salts, resin T A , the resin T A Resin T different from B a processing liquid storage section containing a processing liquid containing a silicone surfactant (but not containing an organic solvent having a boiling point of 200° C. or higher under normal pressure); a treatment liquid applying means for applying the treatment liquid contained in the treatment liquid storage unit to the non-permeable substrate by an ink jet method; an ink storage section containing an ink containing a coloring material, an organic solvent, and a resin; an ink applying unit that applies the ink contained in the ink container onto the treatment liquid; The image forming apparatus is characterized by having the following features.

[0089] The above <1> from <3> The image forming method according to any one of the preceding claims. <4> A set of the treatment liquid and the ink according to <5> The method for producing the printed matter described in <6> According to the image forming apparatus described in the above, the conventional problems can be solved and the object of the present invention can be achieved. [Explanation of symbols]

[0090] 400 Image forming device 401 Exterior of image forming device 401c Device body cover 404 Cartridge Holder 410 Main Tank 410k, 410c, 410m, 410y Main tanks for black (K), cyan (C), magenta (M), and yellow (Y) 411 Ink storage unit 413 Ink outlet 414 Storage container case 420 Mechanism Department 434 Discharge Head 436 Supply Tube [Prior art documents] [Patent documents]

[0091] [Patent Document 1] JP 2018-154118 A [Patent Document 2] Patent No. 6814365

Claims

1. Polyvalent metal salt, resin T Ａ , the resin T Ａ Resin T different from Ｂ and a treatment liquid application step of applying a treatment liquid containing a silicone surfactant (but not containing an organic solvent having a boiling point of 200° C. or higher under normal pressure) to a non-permeable substrate by an inkjet method; an ink applying step of applying an ink containing a coloring material, an organic solvent, and a resin onto the treatment liquid; Including, The glass transition temperature Tg of the resin T is Tg≦−15° C.; The image forming method according to claim 1, wherein the glass transition temperature Tg B of the resin T B is 30° C. or less.

2. The image forming method according to claim 1 , wherein the polyvalent metal salt includes at least one of a magnesium salt and a calcium salt.

3. Polyvalent metal salt, resin T Ａ , the resin T Ａ Resin T different from Ｂ and a treatment liquid application step of applying a treatment liquid containing a silicone surfactant (but not containing an organic solvent having a boiling point of 200° C. or higher under normal pressure) to a non-permeable substrate by an inkjet method; an ink applying step of applying an ink containing a coloring material, an organic solvent, and a resin onto the treatment liquid; The glass transition temperature Tg of the resin T is Tg≦−15° C.; The method for producing a printed matter, wherein the glass transition temperature Tg B of the resin T B is 30° C.≦Tg B .

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