JP7059600B2 - Image forming method, image forming apparatus, and printed matter manufacturing method - Google Patents

Description

The present invention relates to an image forming method, an image forming apparatus, and a method for manufacturing a printed matter.

Inkjet printers have advantages such as low noise, low running cost, and easy color printing, and are therefore widely used in general households as digital signal output devices.
In recent years, the technique of inkjet image formation has been developed not only for household use but also for packaging materials such as foods, beverages and daily necessities.

In Japan, non-absorbent recording media such as plastic films are used for applications, and inks for that purpose have been developed. Examples of direct inkjet printing on such plastic films include packaging printing applications for foods and daily necessities. Since there are many opportunities to see printed matter at close range in these applications, extremely high image quality is required. However, when inkjet printing is performed on a non-absorbent recording medium, ink droplets may spread excessively and white characters (also called negative characters) may be crushed and become unreadable because penetration drying does not occur. ..

In order to deal with the above problems, for example, a technique has been proposed in which a reaction solution containing a flocculant and an ink containing a coloring material are sequentially applied to a recording medium (see, for example, Patent Document 1).

An object of the present invention is to provide a magenta image having less bleeding, excellent readability, and a high saturation, and an image forming method for expressing a secondary color of magenta.

The image forming method of the present invention as a means for solving the above-mentioned problems is carried out by a pretreatment liquid application step of applying a pretreatment liquid containing a polyvalent metal salt on a recording medium and an inkjet recording method on the recording medium. , At least including an ink applying step of applying magenta ink and yellow ink.
The magenta ink is C.I. I. Pigment Red 202 and C.I. I. It is a solid solution pigment made of Pigment Violet 19, and the recording medium is a non-absorbable recording medium.

INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide an image forming method for expressing magenta and a secondary color of magenta having low bleeding, excellent readability, and high saturation.

FIG. 1 is a schematic view showing an example of the image forming apparatus of the present invention. FIG. 2 is a schematic view showing an example of an ink container.

(Image forming method and image forming device)
The image forming method of the present invention includes a pretreatment liquid application step of applying a pretreatment liquid containing a polyvalent metal salt on a recording medium, and a pretreatment liquid application step.
Including an ink applying step of applying at least magenta ink and yellow ink on the recording medium by an inkjet recording method.
The magenta ink is C.I. I. Pigment Red 202 and C.I. I. A solid solution pigment consisting of Pigment Violet 19.
The recording medium is a non-absorbent recording medium, and preferably includes a surface modification step, a white ink applying step, and a heating step, and further includes other steps as necessary.

The image forming apparatus of the present invention includes a pretreatment liquid applying means for applying a pretreatment liquid containing a polyvalent metal salt on a recording medium, and a pretreatment liquid application means.
It has an ink applying means for applying at least magenta ink and yellow ink on the recording medium by an inkjet recording method.
The magenta ink is C.I. I. Pigment Red 202 and C.I. I. A solid solution pigment consisting of Pigment Violet 19.
The recording medium is a non-absorbent recording medium, and preferably has a surface modifying means, a white ink applying means, and a heating means, and further has other means as needed.

In the prior art, the image forming method of the present invention and the image forming apparatus of the present invention have the same as the first ink layer applied first when ink is applied to a non-absorbent recording medium coated with a reaction solution containing a flocculant. It is based on the finding that the saturation is lowered because an interface is formed between the second ink layers applied next and the ink layers do not mix with each other. Further, since this does not occur in the combination of the absorbent recording medium and the reaction solution, it is based on the finding that it is a peculiar problem caused by the combination of the non-absorbent recording medium and the reaction solution.
In addition, since warm colors such as red, orange, and yellow generally have the effect of increasing appetite, the use of highly saturated magenta ink as a food packaging material enhances the attractiveness of the product. It is also important, but it is based on the finding that high saturation cannot be expected with general magenta pigments when color mixing does not occur as described above.

As a result of diligent studies to solve the above problems, the present inventors have "a pretreatment liquid application step of applying a pretreatment liquid containing a polyvalent metal salt on a recording medium, and an inkjet recording on the recording medium. According to the method, the magenta ink comprises at least an ink applying step of applying magenta ink and yellow ink, and the magenta ink is a solid solution pigment composed of CI Pigment Red 202 and CI Pigment Violet 19, and the recording medium is the recording medium. It has been found that in "an image forming method which is a non-absorbent recording medium", it is possible to provide printed matter having less bleeding and high saturation of magenta and secondary colors of magenta. This is because the first ink layer (magenta ink layer) applied on the non-absorbent recording medium coated with the pretreatment liquid containing a polyvalent metal salt that destabilizes the dispersion of the coloring material in the ink is next. By forming an interface with the second ink layer (yellow ink layer) applied to the ink, it is possible to obtain a printed matter with less bleeding because the colors are not completely mixed, while the magenta ink containing a specific solid solution pigment is used. This is because high saturation can be expressed without mixing colors. On the other hand, when the pretreatment liquid was applied to the absorbent recording medium, the first ink (magenta ink) and the second ink (yellow ink) to be applied thereafter were mixed and bleeding occurred.

<Pretreatment liquid application step and pretreatment liquid application means>
The pretreatment liquid application step is a step of applying a pretreatment liquid containing a polyvalent metal salt onto a recording medium, and is carried out by the pretreatment liquid application means.

<< Pretreatment liquid >>
The pretreatment liquid contains a polyvalent metal salt, preferably contains water, and further contains other components as necessary.

-Multivalent metal salt-
The polyvalent metal salt has a function of destabilizing the dispersion of the coloring material in the ink, and promptly aggregates the pigment in the ink after dripping, suppresses color bleeding, and improves color development. be able to.
The cation in the polyvalent metal salt is not particularly limited and may be appropriately selected depending on the intended purpose. For example, aluminum (Al (III)), calcium (Ca (II)), magnesium (Mg (II)). )), Copper (Cu (II)), Iron (Fe (II) or Fe (III)), Zinc (Zn (II)), Tin (Sn (II) or Sn (IV)), Strontium (Sr (II)) )), Nickel (Ni (II)), Cobalt (Co (II)), Barium (Ba (II)), Lead (Pb (II)), Zirconium (Zr (IV)), Titanium (Ti (IV)) , Antimon (Sb (III)), Bismus (Bi (III)), Tantal (Ta (V)), Arsenic (As (III)), Cerium (Ce (III)), Lantern (La (III)), Ironium Examples thereof include ions such as (Y (III)), mercury (Hg (II)), and beryllium (Be (II)). Among these, calcium (Ca (II)) and magnesium (Mg (II)) are preferable.

The anion in the polyvalent metal salt is not particularly limited and may be appropriately selected depending on the intended purpose. For example, fluorine (F), chlorine (Cl), bromine (Br), iodine (I) and the like can be selected. Halogen element ions; Nitrate ion (NO _3- ), ^Sulfate ion ( ^{SO 4-2} ₎ ; Organic carboxylic acid ions such as formic acid, acetic acid, lactic acid, malonic acid, oxalic acid, maleic acid, benzoic acid; benzenesulphonic acid , Naftor sulphonic acid, organic sulphonic acid ions such as alkylbenzene sulphonic acid; ^{thiosian ion (SCN-, thiosulfate ion S 2 O 3-2-), phosphate ion (PO 4-3- ) ,} _{nitrite ion (} NO ^2- ) ) And so on. Among these, chloride ion (Cl ⁻ ), sulfate ion (SO _4-2 ) _{, and acetate ion nitrate ion (NO 3-} ^{) are} preferable from the viewpoint of cost and safety.

The polyvalent metal salt is not particularly limited and may be appropriately selected depending on the intended purpose. For example, aluminum chloride, calcium chloride, nickel chloride, calcium acetate, aluminum nitrate, magnesium nitrate, magnesium chloride, calcium nitrate, etc. Examples thereof include magnesium hydroxide, aluminum nitrate, magnesium sulfate, and ammonium gyoban. More specifically, calcium acetate monohydrate, calcium nitrate / tetrahydrate, calcium chloride hexahydrate, magnesium sulfate (anhydrous), aluminum nitrate nine hydrate, nickel chloride hexahydrate and the like can be mentioned. Be done. These may be used alone or in combination of two or more. Among these, calcium acetate monohydrate, calcium nitrate / tetrahydrate, calcium chloride hexahydrate, and magnesium sulfate (anhydrous) are preferable.

The content of the polyvalent metal salt is preferably 1% by mass or more and 10% by mass or less, more preferably 1% by mass or more and 5% by mass or less, and 1% by mass or more and 4% by mass with respect to the total amount of the pretreatment liquid. The following is more preferable.

-water-
As the water, pure water such as ion-exchanged water, ultra-filtered water, reverse osmosis water, distilled water, or ultrapure water can be used.

-Other ingredients-
Examples of the other components include organic solvents, surfactants, antifoaming agents, antiseptic and antifungal agents, pH adjusters, antiseptic and antifungal agents, and rust preventives.
The organic solvent, surfactant, defoaming agent, pH adjuster, antiseptic / antifungal agent, and rust preventive are not particularly limited and may be appropriately selected depending on the intended purpose. The same material as can be used.

<< Recording medium >>
As the recording medium, a non-absorbable recording medium is used.
The non-absorbent recording medium means a recording medium having a surface having at least one of low water permeability, absorbency, and adsorptivity, and is open to the outside even if there are many cavities inside. Not including materials are included.
More quantitatively, it refers to a recording medium having a water absorption amount of 10 mL / m ² or less from the start of contact to 30 msec ^1/2 in the Bristow method.

Examples of the non-absorbent recording medium include polypropylene film, polyethylene terephthalate (PET) film, nylon film and the like. Examples of the polypropylene film include P-2002, P-2161 and P-4166 (all of which are P-2002). Examples thereof include Toyobo Co., Ltd.), PA-20, PA-30, PA-20W (all manufactured by SUNTOX), FOA, FOS, FOR (all manufactured by Futamura Chemical Co., Ltd.).
Examples of the polyethylene terephthalate (PET) film include E-5100, E-5102 (all manufactured by Toyobo Co., Ltd.), P60, P375 (all manufactured by Toray Industries, Inc.), G2, G2P2, K, SL (all manufactured by Toyobo Co., Ltd.). All of them are manufactured by Teijin DuPont Film Co., Ltd.).
Examples of the nylon film include Harden films N-1100, N-1102, N-1200 (all manufactured by Toyobo Co., Ltd.), ON, NX, MS, NK (all manufactured by Unitika Ltd.) and the like. Be done.

The method for applying the pretreatment liquid is not particularly limited and may be appropriately selected depending on the intended purpose. For example, an inkjet method, a blade coating method, a gravure coating method, a gravure offset coating method, a bar coating method, and a roll coating method. , Knife coat method, air knife coat method, comma coat method, U comma coat method, AKKU coat method, smoothing coat method, micro gravure coat method, reverse roll coat method, 4 roll coat method, 5 roll coat method, dip coat Examples include the method, the curtain coat method, the slide coat method, and the die coat method.

<Ink applying process and ink applying means>
The ink applying step is a step of applying at least magenta ink and yellow ink onto the recording medium by an inkjet recording method, and is carried out by the ink applying means.
The recording medium is a non-absorbable recording medium, and examples of the non-absorbent recording medium include those described above.
Examples of the inkjet recording method include a method using various inkjet nozzles for ejecting ink.
The order of applying magenta ink and applying yellow ink is not particularly limited and can be appropriately selected according to the purpose. However, from the viewpoint of obtaining a printed matter with less bleeding, yellow ink is applied after applying magenta ink. It is preferable to do so.

<< Magenta Ink >>
The magenta ink is C.I. I. Pigment Red 202 and C.I. I. It is a solid solution pigment composed of Pigment Violet 19, preferably containing acrylic resin particles, and further containing other components as necessary.

-Solid solution pigment-
A solid solution is a mixed crystal (crystallized state in a mixed state) of a plurality of pigment molecules.
The amount of solid solution produced can be confirmed by observing the peak intensity of 2θ = with respect to the Bragg angle (2θ ± 0.2 °) of CuKα rays (wavelength: 1.541 Å) with respect to X-rays. The amount of the solid solution produced can be adjusted by appropriately adjusting the mixing conditions and the like when producing the solid solution from the pigment mixture.
Examples of the pigment constituting the solid solution pigment include C.I. I. Pigment Red 202 and C.I. I. Pigment Violet 19 is used.

The mass ratio (A: B) of the pigment A and the pigment B, which are the two types of pigments constituting the solid solution pigment, is preferably 20:80 to 80:20, preferably 30:70 to 20:20 from the viewpoint of color development. It is more preferable that it is 70:30.

-Acrylic resin particles-
Since the acrylic resin particles affect the smoothness and transparency of the film, they are effective in improving the saturation and the suppression of bleeding.
Examples of the acrylic resin particles include acrylic resin particles, styrene-acrylic resin particles, and crosslinked styrene-acrylic resin particles.
As the acrylic resin particles, those synthesized as appropriate may be used, or commercially available products may be used.
Examples of the commercially available resin particles include Microgel E-1002, E-5002 (styrene-acrylic resin particles, manufactured by Nippon Paint Co., Ltd.), Boncoat 4001 (acrylic resin fine particles, manufactured by DIC Co., Ltd.), and Boncoat 5454 (styrene). -Acrylic resin particles, manufactured by DIC Co., Ltd.), SAE-1014 (styrene-acrylic resin particles, manufactured by Nippon Zeon Co., Ltd.), Cybinol SK-200 (acrylic resin particles, manufactured by Saiden Chemical Co., Ltd.), Primal AC-22, AC -61 (Acrylic resin particles, manufactured by Roam & Haas), Nanokrill SBCX-2821, 3689 (Acrylic silicone resin particles, manufactured by Toyo Ink Co., Ltd.) and the like can be mentioned.
The content of the acrylic resin particles with respect to the magenta ink is preferably 0.5% by mass or more and 20% by mass or less. Within this numerical range, a sufficient amount of resin can be secured, a flat film can be obtained, and the film thickness does not become too large and transparency can be ensured, so that the saturation is improved.

<< Yellow Ink >>
The yellow ink contains a yellow pigment and, if necessary, other components.

Examples of the yellow pigment include C.I. I. 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 and the like. These may be used alone or in combination of two or more.
Among these, C.I. I. Pigment Yellow 13, C.I. I. Pigment Yellow 74, C.I. I. Pigment Yellow 155 is preferred.

Hereinafter, components other than the solid solution pigment and acrylic resin particles in magenta ink and the yellow pigment in yellow ink will be described.

<Ink>
Hereinafter, the organic solvent, water, coloring material, resin, additive, etc. used for the ink will be described.

<Organic solvent>
The organic solvent used in the present invention is not particularly limited, and a water-soluble organic solvent can be used. Examples thereof include ethers such as polyhydric alcohols, 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, for example, ethylene glycol, diethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, and 1,4-butane. Diol, 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, 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- Polyhydric alcohols such as 1,3-pentanediol and petriol, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, tetraethylene glycol monomethyl ether, propylene glycol monoethyl Polyhydric alcohol alkyl ethers such as ethers, polyhydric alcohol aryl ethers such as ethylene glycol monophenyl ether and ethylene glycol monobenzyl ether, 2-pyrrolidone, N-methyl-2-pyrrolidone, N-hydroxyethyl-2-pyrrolidone. , 1,3-Dimethyl-2-imidazolidinone, ε-caprolactam, γ-butyrolactone and other nitrogen-containing heterocyclic compounds, formamide, N-methylformamide, N, N-dimethylformamide, 3-methoxy-N, N- Amidos such as dimethylpropionamide, 3-butoxy-N, N-dimethylpropionamide, amines such as monoethanolamine, diethanolamine and triethylamine, sulfur-containing compounds such as dimethylsulfoxide, sulfolane and thiodiethanol, propylene carbonate and ethylene carbonate. And so on.
It is preferable to use an organic solvent having a boiling point of 250 ° C. or lower because it not only functions as a wetting agent but also has good drying properties.

The content of the organic solvent in the ink is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 10% by mass or more and 60% by mass or less from the viewpoint of ink drying property and ejection reliability. More preferably, it is 20% by mass or more and 60% by mass or less.

<Surfactant>
As the surfactant, any of a silicone-based surfactant, a fluorine-based surfactant, an amphoteric surfactant, a nonionic surfactant, and an anionic surfactant can be used.
The silicone-based surfactant is not particularly limited and may be appropriately selected depending on the intended purpose. Among them, those that do not decompose even at high pH are preferable, and examples thereof include side chain modified polydimethylsiloxane, double-ended modified polydimethylsiloxane, single-ended modified polydimethylsiloxane, side chain double-ended modified polydimethylsiloxane, and the like. Those having an oxyethylene group and a polyoxyethylene polyoxypropylene group are particularly preferable because they exhibit good properties as an aqueous surfactant. Further, as the silicone-based surfactant, a polyether-modified silicone-based surfactant can also be used, and examples thereof include compounds in which a polyalkylene oxide structure is introduced into the Si portion side chain of dimethylsiloxane.
Examples of the fluorine-based surfactant include a perfluoroalkyl sulfonic acid compound, a perfluoroalkyl carboxylic acid compound, a perfluoroalkyl phosphate ester compound, a perfluoroalkyl ethylene oxide adduct, and a perfluoroalkyl ether group in the side chain. Polyoxyalkylene ether polymer compounds are particularly preferred because they have low foaming properties. Examples of the perfluoroalkyl sulfonic acid compound include perfluoroalkyl sulfonic acid and perfluoroalkyl sulfonic acid salt. Examples of the perfluoroalkylcarboxylic acid compound include perfluoroalkylcarboxylic acid and perfluoroalkylcarboxylic acid salt. The polyoxyalkylene ether polymer compound having a perfluoroalkyl ether group in the side chain includes a sulfate ester salt of a polyoxyalkylene ether polymer having a perfluoroalkyl ether group in the side chain and a perfluoroalkyl ether group in the side chain. Examples thereof include salts of polyoxyalkylene ether polymers. The counter ions of the salts in these fluorine-based surfactants include Li, Na, K, NH ₄ , NH ₃ CH ₂ CH ₂ OH, NH ₂ (CH ₂ CH ₂ OH) ₂ , and NH (CH ₂ CH ₂ OH). ₃ etc. can be mentioned.
Examples of the amphoteric tenside include laurylaminopropionate, lauryl dimethyl betaine, stearyl dimethyl betaine, and lauryl dihydroxyethyl betaine.
Examples of the nonionic surfactant include polyoxyethylene alkyl phenyl ether, polyoxyethylene alkyl ester, polyoxyethylene alkyl amine, polyoxyethylene alkyl amide, polyoxyethylene propylene block polymer, sorbitan fatty acid ester, and polyoxyethylene sorbitan. Examples thereof include a fatty acid ester and an ethylene oxide adduct of acetylene alcohol.
Examples of the anionic surfactant include polyoxyethylene alkyl ether acetate, dodecylbenzene sulfonate, lauryl salt, polyoxyethylene alkyl ether sulfate salt and the like.
These may be used alone or in combination of two or more.

<Water>
As the water, pure water such as ion-exchanged water, ultra-filtered water, reverse osmosis water, distilled water, or ultrapure water can be used.
The content of water in the ink is not particularly limited and may be appropriately selected depending on the intended purpose, but from the viewpoint of ink drying property and ejection reliability, it is preferably 10% by mass or more and 90% by mass or less, and 20% by mass. % Or more and 60% by mass or less are more preferable.

<Color material>
The color material other than the solid solution pigment of the magenta ink and the yellow pigment of the yellow ink is not particularly limited, and pigments and dyes can be used.
As the pigment, an inorganic pigment or an organic pigment can be used. These may be used alone or in combination of two or more. Further, a mixed crystal may be used.
As the pigment, for example, a black pigment, a cyan pigment, a white pigment, a green pigment, an orange pigment, a glossy color pigment such as gold or silver, a metallic pigment, or the like can be used.
As inorganic pigments, carbon black produced by known methods such as contact method, furnace method, thermal method, in addition to titanium oxide, iron oxide, calcium carbonate, barium sulfate, aluminum hydroxide, barium yellow, cadmium red, and chrome yellow. Can be used.
Examples of organic pigments include azo pigments and polycyclic pigments (for example, phthalocyanine pigments, perylene pigments, perinone pigments, anthraquinone pigments, quinacridone pigments, dioxazine pigments, indigo pigments, thioindigo pigments, isoindolinone pigments, quinofuralone pigments, etc.). , Dye chelate (for example, basic dye type chelate, acid dye type chelate, etc.), nitro pigment, nitroso pigment, aniline black and the like can be used. Among these pigments, those having a good affinity with a solvent are preferably used. In addition, resin hollow particles and inorganic hollow particles can also be used.
As a specific example of the pigment, for black, carbon black (CI pigment black 7) such as furnace black, lamp black, acetylene black, channel black, etc., or copper, iron (CI pigment black 11) , Metals such as titanium oxide, and organic pigments such as aniline black (CI pigment black 1).
Further, for color, C.I. I. Pigment Orange 5, 13, 16, 17, 36, 43, 51, C.I. I. Pigment Blue 1, 2, 15 (phthalocyanine blue), 15: 1, 15: 2, 15: 3, 15: 4 (phthalocyanine blue), 16, 17: 1, 56, 60, 63, C.I. I. Pigment Green 1, 4, 7, 8, 10, 17, 18, 36, and the like.

The dye is not particularly limited, and acid dyes, direct dyes, reactive dyes, and basic dyes can be used, and one type may be used alone or two or more types may be used in combination. ..
As the dye, for example, C.I. I. Acid Yellow 17, 23, 42, 44, 79, 142; C.I. I. Acid Red 52,80,82,249,254,289; C.I. I. Acid Blue 9,45,249; C.I. I. Acid Black 1, 2, 24, 94; C.I. I. Hood Blacks 1 and 2; C.I. I. Direct Yellow 1,12,24,33,50,55,58,86,132,142,144,173; C.I. I. Direct Red 1,4,9,80,81,225,227; C.I. I. Direct Blue 1,2,15,71,86,87,98,165,199,202; C.I. I. Dylekdo Black 19,38,51,71,154,168,171,195; C.I. I. Reactive Red 14, 32, 55, 79, 249; C.I. I. Reactive Black 3, 4, 35 can be mentioned.

As other trace additives, for example, an antifoaming agent, an antiseptic antifungal agent, an anticorrosive agent and the like may be contained.

<Defoamer>
The defoaming agent is not particularly limited, and examples thereof include a silicone-based defoaming agent, a polyether-based defoaming agent, and a fatty acid ester-based defoaming agent. These may be used alone or in combination of two or more. Among these, a silicone-based defoaming agent is preferable because it has an excellent defoaming effect.

<Preservatives and fungicides>
The antiseptic and antifungal agent is not particularly limited, and examples thereof include 1,2-benzisothiazolin-3-one and the like.

<Rust inhibitor>
The rust preventive is not particularly limited, and examples thereof include acidic sulfites and sodium thiosulfate.

<< Surface modification process and surface modification treatment means >>
The surface modification step is a step of surface modifying the non-absorbent recording medium, and is carried out by the surface modification means. By surface-modifying the non-absorbent recording medium, there is an advantage that the pretreatment liquid can be applied more uniformly.
The surface modifying means may be provided inside the image forming apparatus or outside the image forming apparatus, but is preferably provided inside the image forming apparatus from the viewpoint of handling by dividing the apparatus.
Examples of the surface modification treatment include corona treatment, plasma treatment, frame treatment, ultraviolet irradiation treatment and the like. Among these, the corona treatment, the plasma treatment, and the frame treatment are preferable, the output stability is excellent, and the corona treatment is particularly preferable because the surface treatment can be uniformly performed on the recording surface.

<< White ink applying process and white ink applying means >>
The white ink applying step is a step of applying white ink onto a non-absorbent recording medium by an inkjet recording method, and is carried out by a white ink applying means.
The white ink contains a white colorant and, if necessary, other components.
The white colorant is not particularly limited as long as it exhibits white color, and can be appropriately selected depending on the intended purpose. Examples thereof include inorganic white pigments, organic white pigments, and hollow resin particles. These may be used alone or in combination of two or more. Among these, inorganic white pigments and hollow resin particles are preferable.

-Inorganic white pigment-
Examples of the inorganic white pigment include sulfates of alkaline earth metals such as barium sulfate, carbonates of alkaline earth metals such as calcium carbonate, fine powder silicic acid, silicas such as synthetic silicates, calcium silicate, and the like. Alumina, alumina hydrate, titanium oxide, zinc oxide, talc, clay and the like can be mentioned. These may be used alone or in combination of two or more. Among these, titanium oxide is preferable.

-Hollow resin particles-
The hollow resin particles have a cavity inside, and the outer shell thereof is formed of a resin having liquid permeability. Therefore, when the hollow resin particles are present in the ink, the internal cavities are filled with the aqueous medium.
Since the hollow resin particles filled with the aqueous medium have a specific gravity substantially equal to that of the external aqueous medium, dispersion stability can be maintained without settling in the ink. This makes it possible to improve the storage stability and ejection stability of the ink.

The other components are the same as those of the yellow ink.
As the non-absorbable recording medium, the same one as in the pretreatment liquid application step can be used.
Examples of the inkjet recording method include a method using various inkjet nozzles for ejecting ink.
The order of the white ink applying step and the ink applying step is not particularly limited and may be appropriately selected depending on the intended purpose, but it is preferable to apply magenta ink and yellow ink after applying the white ink.

<< Heating process and heating means >>
The heating step is a step of heating the non-absorbent recording medium after applying the ink, and is carried out by a heating means.
Examples of the heating means include a heater, a heating roller, a hot air blower, and the like.
The heating temperature is preferably 40 ° C. or higher and 100 ° C. or lower, and more preferably 50 ° C. or higher and 90 ° C. or lower. When the heating temperature is 40 ° C. or higher and 120 ° C. or lower, damage due to heat of the non-absorbent recording medium can be prevented.

<< Other processes and other means >>
The other steps are not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include a control step.
The other means are not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include control means.

<Recording device, recording method>
The ink of the present invention can be suitably used for various recording devices by an inkjet recording method, for example, a printer, a facsimile device, a copying device, a printer / fax / copier multifunction device, a three-dimensional modeling device, and the like.
In the present invention, the recording device and the recording method are devices capable of ejecting ink, various processing liquids, and the like to a recording medium, and a method for recording using the device. The recording medium means a medium to which ink and various treatment liquids can adhere even temporarily.
This recording device can include not only a head portion for ejecting ink, but also means related to feeding, transporting, and discharging paper of a recording medium, a pretreatment device, a device called a posttreatment device, and the like. ..
The recording device 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, 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 printing, during printing, after printing, and the like.
Further, the recording device and the recording method are not limited to those in which significant images such as characters and figures are visualized by ink. For example, those that form patterns such as geometric patterns and those that form three-dimensional images are also included.
Further, the recording device includes both a serial type device that moves the discharge head and a line type device that does not move the discharge head, unless otherwise specified.
Further, as this recording device, it is possible to use not only a desktop type but also a wide recording device capable of printing on an A0 size recording medium, or, for example, continuous paper wound in a roll shape as a recording medium. A continuous book printer is also included.
An example of the recording device will be described with reference to FIGS. 1 and 2. FIG. 1 is a perspective explanatory view of the device. FIG. 2 is a perspective explanatory view of the main tank. The image forming apparatus 400 as an example of the recording apparatus is a serial type image forming apparatus. A mechanism portion 420 is provided in the exterior 401 of the image forming apparatus 400. Each ink storage portion 411 of the main tank 410 (410k, 410c, 410m, 410y) for each color of black (K), cyan (C), magenta (M), and yellow (Y) is, for example, a package of an aluminum laminated film or the like. It is formed of members. The ink container 411 is housed in, for example, a plastic container case 414. As a result, the main tank 410 is used as an ink cartridge for each color.
On the other hand, a cartridge holder 404 is provided behind the opening when the cover 401c of the main body of the apparatus is opened. A main tank 410 is detachably attached to the cartridge holder 404. As a result, each ink ejection port 413 of the main tank 410 and the ejection head 434 for each color communicate with each other via the supply tube 436 for each color, and ink can be ejected from the ejection head 434 to the recording medium.

This recording device can include not only a portion for ejecting ink but also a device called a pretreatment device, a posttreatment device, and the like.
As one aspect of the pretreatment apparatus and the posttreatment apparatus, it has a pretreatment liquid and a posttreatment liquid as in the case of inks such as black (K), cyan (C), magenta (M), and yellow (Y). There is an embodiment in which a liquid accommodating portion and a liquid discharge head are added, and a pretreatment liquid or a posttreatment liquid is discharged by an inkjet recording method.
As another aspect of the pretreatment device and the posttreatment device, there is a mode in which a pretreatment device and a posttreatment device by, for example, a blade coating method, a roll coating method, and a spray coating method are provided other than the inkjet recording method.

The method of using the ink is not limited to the inkjet recording method, and can be widely used. In addition to the inkjet recording method, examples thereof include a blade coating method, a gravure coating method, a bar coating method, a roll coating method, a dip coating method, a curtain coating method, a slide coating method, a die coating method, and a spray coating method.

(Manufacturing method of printed matter)
The method for producing a printed matter of the present invention forms an image on a non-absorbent recording medium by the image forming method of the present invention.
The printed matter produced by the method for producing a printed matter has less bleeding, is excellent in readability, has high saturation, and can express magenta and a secondary color of magenta.

The use of the ink of the present invention is not particularly limited and may be appropriately selected depending on the intended purpose, and can be applied to, for example, printed matter, paints, coating materials, base materials and the like. Further, it can be used not only as an ink to form two-dimensional characters and images, but also as a three-dimensional modeling material for forming a three-dimensional stereoscopic image (three-dimensional model).
As the three-dimensional modeling apparatus for modeling the three-dimensional object, a known one can be used, and is not particularly limited, but for example, an apparatus provided with ink accommodating means, supply means, ejection means, drying means and the like is used. be able to. The three-dimensional model includes a three-dimensional model obtained by overcoating with ink. Further, a molded product obtained by processing a structure in which ink is applied on a base material such as a recording medium is also included. The molded product is, for example, a sheet-shaped or film-shaped recorded material or structure that has been subjected to molding processing such as heat stretching or punching, and is, for example, an automobile, OA equipment, or electricity. -Suitably used for molding after decorating the surface of electronic devices, meters of cameras, panels of operation parts, etc.

Further, in the terms of the present invention, image formation, recording, printing, printing, etc. are all synonymous.
Recording media, media, and printed matter are all synonymous.

Hereinafter, examples of the present invention will be described, but the present invention is not limited to these examples.

(Preparation Examples 1 to 6 of Pretreatment Liquid)
<Preparation of pretreatment liquid>
After blending according to the formulations shown in Table 1, the mixture was mixed and stirred, and filtered through a filter (Minisalt manufactured by Sartorius) having an average pore size of 5 μm to prepare pretreatment liquids 1 to 6.

＊エマルゲンＬＳ－１０６：高級アルコール系エーテル型非イオン性界面活性剤、花王株式会社製
＊プロキセルＬＶ：防腐防カビ剤、ロンザジャパン株式会社製

* Emargen LS-106: higher alcohol-based ether type nonionic surfactant, manufactured by Kao Co., Ltd. * Proxel LV: antiseptic and antifungal agent, manufactured by Lonza Japan Co., Ltd.

(Preparation Example 1 of Magenta Pigment Dispersion)
-Preparation of Magenta Pigment Dispersion 1-
After premixing the mixture of the following formulation, it was circulated and dispersed for 7 hours in a disc type bead mill (manufactured by Simmal Enterprises Co., Ltd., KDL type, media: using zirconia balls having a diameter of 0.3 mm) to magenta pigment dispersion 1 (Magenta pigment dispersion 1 (). Pigment concentration: 15% by mass) was obtained.
・ C. I. Pigment Red 202: C.I. I. Pigment Violet 19 = 20: 80 (mass ratio) solid solution pigment ・ ・ ・ 15 parts by mass ・ Acrylic polymer dispersant Disperbyk-2010 ・ ・ ・ 5 parts by mass (manufactured by BYK Japan)
・ Ion-exchanged water ・ ・ ・ 80 parts by mass

(Preparation Example 2 of Magenta Pigment Dispersion)
-Preparation of magenta pigment dispersion 2-
After premixing the following formulation mixture, it is circulated and dispersed for 7 hours in a disc-type bead mill (manufactured by Simmal Enterprises Co., Ltd., KDL type, media: using zirconia balls with a diameter of 0.3 mm) for magenta pigment dispersion 2 (pigment). Concentration: 15% by mass) was obtained.
・ C. I. Pigment Red 202: C.I. I. Pigment Violet 19 = 40: 60 (mass ratio) solid solution pigment ・ ・ ・ 15 parts by mass ・ Acrylic polymer dispersant Disperbyk-2010 ・ ・ ・ 5 parts by mass (manufactured by BYK Japan)
・ Ion-exchanged water ・ ・ ・ 80 parts by mass

(Preparation Example 3 of Magenta Pigment Dispersion)
-Preparation of Magenta Pigment Dispersion 3-
After premixing the following premix, magenta pigment dispersion 3 (pigment) was circulated and dispersed for 7 hours in a disc-type bead mill (manufactured by Simmal Enterprises Co., Ltd., KDL type, media: using zirconia balls with a diameter of 0.3 mm). Concentration: 15% by mass) was obtained.
・ C. I. Pigment Red 202: C.I. I. Pigment Violet 19 = 60: 40 (mass ratio) solid solution pigment ・ ・ ・ 15 parts by mass ・ Acrylic polymer dispersant Disperbyk-2010 ・ ・ ・ 5 parts by mass (manufactured by BYK Japan)
・ Ion-exchanged water ・ ・ ・ 80 parts by mass

(Preparation Example 4 of Magenta Pigment Dispersion)
-Preparation of Magenta Pigment Dispersion 4-
After premixing the following premix, magenta pigment dispersion 4 (pigment) was circulated and dispersed for 7 hours in a disc-type bead mill (manufactured by Simmal Enterprises Co., Ltd., KDL type, media: using zirconia balls with a diameter of 0.3 mm). Concentration: 15% by mass) was obtained.
・ C. I. Pigment Red 202: C.I. I. Pigment Violet 19 = 80: 20 (mass ratio) solid solution pigment ・ ・ ・ 15 parts by mass ・ Acrylic polymer dispersant Disperbyk-2010 ・ ・ ・ 5 parts by mass (manufactured by BYK Japan)
・ Ion-exchanged water ・ ・ ・ 80 parts by mass

(Preparation Example 5 of Magenta Pigment Dispersion)
-Preparation of Magenta Pigment Dispersion 5-
After premixing the following premixed mixture, it is circulated and dispersed for 7 hours in a disc type bead mill (manufactured by Simmal Enterprises Co., Ltd., KDL type, media: using zirconia balls having a diameter of 0.3 mm) for magenta pigment dispersion 5 (pigment). Concentration: 15% by mass) was obtained.
・ C. I. Pigment Red 202: C.I. I. Pigment Violet 19 = 10: 90 (mass ratio) solid solution pigment ・ ・ ・ 15 parts by mass ・ Acrylic polymer dispersant Disperbyk-2010 ・ ・ ・ 5 parts by mass (manufactured by BYK Japan)
・ Ion-exchanged water ・ ・ ・ 80 parts by mass

(Preparation Example 6 of Magenta Pigment Dispersion)
-Preparation of magenta pigment dispersion 6-
After premixing the following premix, magenta pigment dispersion 6 (pigment) was circulated and dispersed for 7 hours in a disc-type bead mill (manufactured by Simmal Enterprises Co., Ltd., KDL type, media: using zirconia balls with a diameter of 0.3 mm). Concentration: 15% by mass) was obtained.
・ C. I. Pigment Red 202: C.I. I. Pigment Violet 19 = 90: 10 (mass ratio) solid solution pigment ・ ・ ・ 15 parts by mass ・ Acrylic polymer dispersant Disperbyk-2010 ・ ・ ・ 5 parts by mass (manufactured by BYK Japan)
・ Ion-exchanged water ・ ・ ・ 80 parts by mass

(Preparation Example 7 of Magenta Pigment Dispersion)
-Preparation of magenta pigment dispersion 7-
After premixing the following formulation mixture, it is circulated and dispersed for 7 hours in a disc type bead mill (manufactured by Simmal Enterprises Co., Ltd., KDL type, media: using zirconia balls having a diameter of 0.3 mm) for magenta pigment dispersion 7 (pigment). Concentration: 15% by mass) was obtained.
・ C. I. Pigment Red 202 ... 15 parts by mass-Acrylic polymer dispersant Disperbyk-2010 ... 5 parts by mass (manufactured by BYK Japan)
・ Ion-exchanged water ・ ・ ・ 80 parts by mass

(Preparation Example 1 of Yellow Pigment Dispersion)
-Preparation of Yellow Pigment Dispersion 1-
After premixing the following formulation mixture, it is circulated and dispersed for 7 hours in a disc type bead mill (manufactured by Symmal Enterprises Co., Ltd., KDL type, media: using zirconia balls having a diameter of 0.3 mm) to disperse the yellow pigment dispersion 1 (pigment). Concentration: 15% by mass) was obtained.
・ C. I. Pigment Yellow 13 ... 15 parts by mass-Acrylic polymer dispersant Disperbyk-2010 ... 5 parts by mass (manufactured by BYK Japan)
・ Ion-exchanged water ・ ・ ・ 80 parts by mass

(Preparation Example 2 of Yellow Pigment Dispersion)
-Preparation of yellow pigment dispersion 2-
After premixing the following formulation mixture, it was circulated and dispersed for 7 hours in a disc-type bead mill (manufactured by Simmal Enterprises Co., Ltd., KDL type, media: using zirconia balls with a diameter of 0.3 mm) to disperse the yellow pigment dispersion 2 (Yellow pigment dispersion 2 (). Pigment concentration: 15% by mass) was obtained.
・ C. I. Pigment Yellow 74 ... 15 parts by mass-Acrylic polymer dispersant Disperbyk-2010 ... 5 parts by mass (manufactured by BYK Japan)
・ Ion-exchanged water ・ ・ ・ 80 parts by mass

(Preparation Example 3 of Yellow Pigment Dispersion)
-Preparation of yellow pigment dispersion 3-
After premixing the following formulation mixture, it is circulated and dispersed for 7 hours in a disc type bead mill (manufactured by Symmal Enterprises Co., Ltd., KDL type, media: using zirconia balls having a diameter of 0.3 mm) to disperse the yellow pigment dispersion 3 (pigment). Concentration: 15% by mass) was obtained.
・ C. I. Pigment Yellow 155 ... 15 parts by mass-Acrylic polymer dispersant Disperbyk-2010 ... 5 parts by mass (manufactured by BYK Japan)
・ Ion-exchanged water ・ ・ ・ 80 parts by mass

(Preparation Example 4 of Yellow Pigment Dispersion)
-Preparation of yellow pigment dispersion 4-
After premixing the following formulation mixture, it is circulated and dispersed for 7 hours in a disc type bead mill (manufactured by Symmal Enterprises Co., Ltd., KDL type, media: using zirconia balls having a diameter of 0.3 mm) to disperse the yellow pigment dispersion 4 (pigment). Concentration: 15% by mass) was obtained.
・ C. I. Pigment Yellow 1 ... 15 parts by mass-Acrylic polymer dispersant Disperbyk-2010 ... 5 parts by mass (manufactured by BYK Japan)
・ Ion-exchanged water ・ ・ ・ 80 parts by mass

(Preparation example of acrylic resin emulsion A)
900 g of ion-exchanged water and 1 g of sodium lauryl sulfate were charged in a reaction vessel equipped with a stirrer, a reflux condenser, a dropping device, and a thermometer, and the temperature was raised to 70 ° C. while stirring with nitrogen.
Keep the internal temperature at 70 ° C., add 4 g of potassium persulfate as a polymerization initiator, and after dissolution, stir 450 g of ion-exchanged water, 3 g of sodium lauryl sulfate, 20 g of acrylamide, 365 g of styrene, 545 g of butyl acrylate, and 10 g of methacrylic acid in advance. The emulsion prepared by adding to the bottom was continuously added dropwise into the reaction solution over 4 hours.
After completion of the dropping, aging was carried out for 3 hours.
After cooling the obtained aqueous emulsion to room temperature, ion-exchanged water and an aqueous sodium hydroxide solution were added to adjust the solid content to 30% by mass and pH 8, to obtain an acrylic resin emulsion A.

(Preparation example of polyester urethane resin emulsion A)
In a reaction vessel containing a stirrer, a reflux condenser, and a thermometer, 1,500 g of polylite OD-X-2420 (polyester polyol manufactured by DIC Corporation), 220 g of 2,2-dimethylolpropionic acid (DMPA), and 1,347 g of N-methylpyrrolidone (NMP) was charged in a nitrogen atmosphere and heated to 60 ° C. to dissolve DMPA.
Next, 1,445 g of 4,4'-dicyclohexylmethane diisocyanate and 2.6 g of dibutyltin dilaurylate (catalyst) were added and heated to 90 ° C., and a urethanization reaction was carried out over 5 hours to obtain an isocyanate-terminated urethane prepolymer. Obtained.
The reaction mixture was cooled to 80 ° C., and 4,340 g of the mixture was further added and mixed with 149 g of triethylamine, and the mixture was 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, 626 g of a 35% by mass 2-methyl-1,5-pentanediamine aqueous solution was added, a chain extension reaction was carried out, and the solvent was distilled off so that the solid content concentration became 30% by mass. Then, the obtained resin emulsion was dispersed and treated with a paint conditioner (manufactured by Red Devil Co., Ltd., the speed can be adjusted in the range of 50 rpm to 1,425 rpm), the solid content concentration was 40.0% by mass, and the glass transition point (Tg) was 10 ° C. The polyester-based urethane resin emulsion A of the above was obtained.
The glass transition point (Tg) was measured by DSC (Thermo plus EVO2 / DSC manufactured by Rigaku Corporation).

(Manufacturing example of magenta ink and yellow ink)
The formulations shown in Tables 2-1 and 2-2 and Table 3 are mixed and stirred, and filtered through a polypropylene filter having an average pore size of 0.2 μm to cause magenta inks 1 to 11 and yellow inks 1 to 4. Was produced.

＊プロキセルＬＶ：防腐防カビ剤、ロンザジャパン株式会社製

* Proxel LV: Antiseptic and antifungal agent, manufactured by Lonza Japan Co., Ltd.

＊プロキセルＬＶ：防腐防カビ剤、ロンザジャパン株式会社製

* Proxel LV: Antiseptic and antifungal agent, manufactured by Lonza Japan Co., Ltd.

＊プロキセルＬＶ：防腐防カビ剤、ロンザジャパン株式会社製

* Proxel LV: Antiseptic and antifungal agent, manufactured by Lonza Japan Co., Ltd.

(Examples 1 to 12 and Comparative Examples 1 to 3)
<Image formation method>
Polyethylene terephthalate (PET) film (manufactured by Toyobo Co., Ltd., Espet E-5100, thickness 25 μm, single-sided) as a non-absorbable recording medium by combining the recording medium, pretreatment liquid, magenta ink, and yellow ink shown in Table 4. (Only the printed surface is surface-modified by corona treatment), and the pretreatment liquid is applied to My Paper (plain paper, manufactured by Ricoh Co., Ltd.) as an absorbent medium with a roll coater in a predetermined amount (3 g / m ² ). ), And after coating, it was dried at 80 ° C. for 2 minutes with a blower constant temperature incubator DKM300 manufactured by Yamato Scientific Co., Ltd. (Drying 1).
The amount of water absorbed from the start of contact to 30 msec ^1/2 in the Bristow method of polyethylene terephthalate (PET) film (manufactured by Toyobo Co., Ltd., Espet E-5100) is 0 to 5 mL / m ² .
An inkjet printer (device name: IPSiO GXe5500 remodeling machine, manufactured by Ricoh Co., Ltd.) filled with each ink was prepared in advance, and magenta ink was applied to the recording medium coated and dried with the pretreatment liquid. After that, yellow ink was applied, and solid patch images of magenta ink and yellow ink were printed adjacent to each other, and then dried at 80 ° C. for 2 minutes with a blower constant temperature incubator DKM300 manufactured by Yamato Scientific Co., Ltd. ( Drying 2).
In the evaluation of saturation, magenta ink and yellow ink are superposed to form a secondary color (red) image, and then, at 80 ° C. with a blower constant temperature incubator DKM300 manufactured by Yamato Scientific Co., Ltd. It was dried for 2 minutes (drying 3).

(Example 13)
In Example 1, a pretreatment liquid was placed on the non-corona treated surface (opposite to the printed surface) side of a polyethylene terephthalate (PET) film (manufactured by Toyobo Co., Ltd., Espet E-5100, thickness 25 μm) as a non-absorbable recording medium. The image was formed in the same manner as in Example 1 except that magenta ink and yellow ink were applied.

(Example 14)
In Example 1, a polyethylene terephthalate (PET) film subjected to frame treatment was used as a non-absorbent recording medium, a pretreatment liquid was applied to the frame-treated surface, and magenta ink and yellow ink were applied. Image formation was performed in the same manner as in Example 1.

(Example 15)
In Example 1, image formation was performed in the same manner as in Example 1 except that drying 1, drying 2 and drying 3 were left at room temperature (25 ° C.) for 8 hours.

<Evaluation method of color boundary bleeding>
The color boundary bleeding of the image obtained by the combination of the recording medium, the pretreatment liquid, the magenta ink, and the yellow ink shown in Table 4 was visually evaluated according to the following evaluation criteria. It should be noted that up to B is a practical level.
[Evaluation criteria]
A: No color border bleeding B: Slight bleeding between some colors C: Slight bleeding between most colors D: Severe bleeding, degrading image quality Are

<Saturation>
Saturation value measured with a reflective color spectroscopic densitometer (manufactured by X-Rite) and saturation value of standard color (Japan color ver.2) (yellow: 91.34, magenta: 74.55) , Cyan: 62.82) was calculated and evaluated according to the following evaluation criteria. It should be noted that up to B is a practical level.
[Evaluation criteria]
A: 1.0 or more B: 0.8 or more and less than 1.0 C: 0.7 or more and less than 0.8 D: less than 0.7

Examples of aspects of the present invention are as follows.
<1> A pretreatment liquid application step of applying a pretreatment liquid containing a polyvalent metal salt on a recording medium, and a pretreatment liquid application step.
Including an ink applying step of applying at least magenta ink and yellow ink on the recording medium by an inkjet recording method.
The magenta ink is C.I. I. Pigment Red 202 and C.I. I. A solid solution pigment consisting of Pigment Violet 19.
This is an image forming method characterized in that the recording medium is a non-absorbable recording medium.
<2> The image forming method according to <1>, wherein in the ink applying step, magenta ink is applied onto the non-absorbent recording medium and then the yellow ink is applied.
<3> The image forming method according to any one of <1> to <2>, wherein the polyvalent metal salt contained in the pretreatment liquid is at least one of a calcium salt and a magnesium salt.
<4> Any of the above <1> to <3> in which the mass ratio (A: B) of the pigment A and the pigment B, which are the two types of pigments constituting the solid solution pigment, is 20:80 to 80:20. This is the image forming method described in the above.
<5> The magenta ink contains acrylic resin particles, and the magenta ink contains acrylic resin particles.
The image forming method according to any one of <1> to <4>, wherein the content of the acrylic resin particles with respect to the magenta ink is 0.5% by mass or more and 20% by mass or less.
<6> The yellow ink is C.I. I. Pigment Yellow 13, C.I. I. Pigment Yellow 74, and C.I. I. The image forming method according to any one of <1> to <5>, which comprises at least one yellow pigment selected from Pigment Yellow 155.
<7> Further, a surface modification step of surface modifying the non-absorbent recording medium and a surface modification step.
The image forming method according to any one of <1> to <6>, which comprises a white ink applying step of applying white ink onto the non-absorbent recording medium by an inkjet recording method.
<8> The image forming method according to <7>, wherein the surface modification step is any one of corona discharge, frame treatment, and plasma treatment.
<9> The image forming method according to any one of <1> to <8>, which comprises a heating step of heating the non-absorbent recording medium after applying ink.
<10> A pretreatment liquid applying means for applying a pretreatment liquid containing a polyvalent metal salt on a recording medium, and
It has an ink applying means for applying at least magenta ink and yellow ink on the recording medium by an inkjet recording method.
The magenta ink is C.I. I. Pigment Red 202 and C.I. I. A solid solution pigment consisting of Pigment Violet 19.
The image forming apparatus is characterized in that the recording medium is a non-absorbable recording medium.
<11> The image forming apparatus according to <10>, wherein the polyvalent metal salt contained in the pretreatment liquid is at least one of a calcium salt and a magnesium salt.
<12> Any of the above <10> to <11> in which the mass ratio (A: B) of the pigment A and the pigment B, which are the two types of pigments constituting the solid solution pigment, is 20:80 to 80:20. The image forming apparatus according to the above.
<13> The magenta ink contains acrylic resin particles, and the magenta ink contains acrylic resin particles.
The image forming apparatus according to any one of <10> to <12>, wherein the content of the acrylic resin particles with respect to the magenta ink is 0.5% by mass or more and 20% by mass or less.
<14> The yellow ink is C.I. I. Pigment Yellow 13, C.I. I. Pigment Yellow 74, and C.I. I. The image forming apparatus according to any one of <10> to <13>, which contains at least one pigment selected from Pigment Yellow 155.
<15> Further, a surface modifying means for surface modifying the non-absorbent recording medium and a surface modifying means.
A white ink applying means for applying white ink to the non-absorbent recording medium by an inkjet recording method,
The image forming apparatus according to any one of <10> to <14>.
<16> The image forming apparatus according to <15>, wherein the surface modifying means uses any of corona discharge, frame processing, and plasma processing.
<17> The image forming apparatus according to any one of <10> to <16>, which has a heating means for heating the non-absorbent recording medium after applying ink.
<18> A method for producing a printed matter, which comprises forming an image on a non-absorbent recording medium by the image forming method according to any one of <1> to <9>.

According to the image forming method according to any one of <1> to <9>, the image forming apparatus according to any one of <10> to <17>, and the printed matter manufacturing method according to <18>. , The conventional problems can be solved and the object of the present invention can be achieved.

Japanese Unexamined Patent Publication No. 2015-71738

400 Image forming device 401 Image forming device exterior 401c Device body cover 404 Cartridge holder 410 Main tank 410k, 410c, 410m, 410y For each color of black (K), cyan (C), magenta (M), yellow (Y) Main tank 411 Ink storage unit 413 Ink discharge port 414 Storage container case 420 Mechanical unit 434 Discharge head 436 Supply tube

Claims (10)

A pretreatment liquid application step of applying a pretreatment liquid containing a polyvalent metal salt on a recording medium, and a pretreatment liquid application step.
It includes an ink applying step of applying at least magenta ink and yellow ink on the recording medium to which the pretreatment liquid is applied by an inkjet recording method.
In the ink applying step, after applying the magenta ink, the yellow ink is applied, and the ink is applied.
The magenta ink is C.I. I. Pigment Red 202 and C.I. I. A solid solution pigment consisting of Pigment Violet 19.
An image forming method, characterized in that the recording medium is a non-absorbable recording medium. The image forming method according to claim 1, wherein the polyvalent metal salt contained in the pretreatment liquid is at least one of a calcium salt and a magnesium salt. The image formation according to any one of claims 1 to 2, wherein the mass ratio (A: B) of the pigment A and the pigment B, which are the two types of pigments constituting the solid solution pigment, is 20:80 to 80:20. Method. The magenta ink contains acrylic resin particles and contains
The image forming method according to any one of claims 1 to 3, wherein the content of the acrylic resin particles with respect to the magenta ink is 0.5% by mass or more and 20% by mass or less. The yellow ink is C.I. I. Pigment Yellow 13, C.I. I. Pigment Yellow 74, and C.I. I. The image forming method according to any one of claims 1 to 4, which comprises at least one yellow pigment selected from Pigment Yellow 155. Further, a surface modification step of surface modifying the non-absorbent recording medium and a surface modification step.
The image forming method according to any one of claims 1 to 5, further comprising a white ink applying step of applying white ink onto the non-absorbent recording medium by an inkjet recording method. The image forming method according to claim 6, wherein the surface modification step is any one of corona discharge, frame treatment, and plasma treatment. The image forming method according to any one of claims 1 to 7, further comprising a heating step of heating the non-absorbent recording medium after applying ink. A pretreatment liquid applying means for applying a pretreatment liquid containing a polyvalent metal salt on a recording medium,
It has an ink applying means for applying at least magenta ink and yellow ink on a recording medium to which the pretreatment liquid is applied by an inkjet recording method.
The yellow ink is applied after the magenta ink is applied by the ink applying means.
The magenta ink is C.I. I. Pigment Red 202 and C.I. I. A solid solution pigment consisting of Pigment Violet 19.
An image forming apparatus, wherein the recording medium is a non-absorbable recording medium. A method for producing a printed matter, which comprises forming an image on a non-absorbent recording medium by the image forming method according to any one of claims 1 to 8.

Images