JP2023090210A - Printing method, set of treatment liquid and ink, and method for manufacturing printed matter - Google Patents

Abstract

To provide a printing method which is excellent in initial discharge stability of ink and scratch resistance of a formed image, and can suppress occurrence of bleeding and cracking of an image.SOLUTION: A printing method includes a treatment liquid applying step of applying a treatment liquid containing a polyvalent metal salt and a resin A to a base material, and an ink applying step of applying, onto the treatment liquid, ink which contains a coloring material, an organic solvent having a boiling point of 290°C or higher, a silicone-based surface active agent, and a resin B and the content of the organic solvent having a boiling point of 290°C or higher is 0.5 mass% or more, with respect to the total amount of the ink.SELECTED DRAWING: None

Description

The present invention relates to a printing method, a set of treatment liquid and ink, and a method of producing a printed matter.

In recent years, inkjet printers have been used not only for home use, but also for industrial uses such as cloth, plastic film, wallpaper, and window film.

In the inkjet method, dye ink, solvent ink, and ultraviolet curing ink (UV ink) are generally used.
In recent years, there is also a method of applying a treatment liquid to a base material before printing such an ink, and applying ink on top of the applied treatment liquid.
The ink and treatment liquid used in such a method include, for example, an inkjet ink containing a pigment, a water-soluble organic solvent, a surfactant, and water, and a treatment containing a coagulant and a compound having 3 or more hydroxyl groups. A liquid and an ink set containing it have been proposed (see, for example, Patent Document 1).

SUMMARY OF THE INVENTION An object of the present invention is to provide a printing method which is excellent in the initial ejection stability of the ink and the abrasion resistance of the formed image, and which can suppress the occurrence of blurring and cracking of the image.

The printing method of the present invention as a means for solving the above problems comprises a treatment liquid application step of applying a treatment liquid containing a polyvalent metal salt and resin A to a substrate; An ink containing an organic solvent, a silicone-based surfactant, and a resin B and having a content of the organic solvent having a boiling point of 290° C. or higher is 0.5% by mass or more with respect to the total amount of the ink is applied on the treatment liquid. and a step of applying ink to the ink.

According to the present invention, it is possible to provide a printing method that is excellent in the initial ejection stability of the ink and in the abrasion resistance of the formed image, and in which the occurrence of blurring and cracking of the image can be suppressed.

FIG. 1 is a perspective explanatory view showing an example of the printed matter manufacturing apparatus of the present invention. FIG. 2 is a perspective explanatory view showing an example of the main tank in the printed matter manufacturing apparatus of the present invention. FIG. 3 is a schematic diagram showing an example of an image forming apparatus used in the image forming method of the present invention.

(Printing method and printing device)
The printing method of the present invention includes a treatment liquid application step of applying a treatment liquid containing a polyvalent metal salt and resin A to a substrate, a coloring material, an organic solvent having a boiling point of 290 ° C. or higher, a silicone surfactant, and and an ink application step of applying an ink containing resin B and having a content of the organic solvent having a boiling point of 290° C. or higher of 0.5% by mass or more with respect to the total amount of the ink onto the treatment liquid. , and further include other steps as necessary.
The printing apparatus according to the printing method of the present invention comprises: a treatment liquid container containing a treatment liquid containing a polyvalent metal salt and a resin A; and a treatment liquid for applying the treatment liquid contained in the treatment liquid container to a substrate. It contains an imparting means, a coloring material, an organic solvent having a boiling point of 290° C. or higher, a silicone surfactant, and a resin B, and the content of the organic solvent having a boiling point of 290° C. or higher is 0 with respect to the total amount of ink. an ink containing section containing ink of 5% by mass or more, ink application means for applying the ink contained in the ink containing section onto the treatment liquid, and other means as necessary. have

In the prior art, when forming a coating film of water-based inkjet ink using an inkjet recording apparatus, the amount of solvent or the amount of activator may cause initial ejection failure of ink droplets, and the scratch resistance of the formed coating film may be poor. The inventors have found that there is a problem that the .

As a result of extensive studies by the present inventors, it was found that a treatment liquid containing a polyvalent metal salt and resin A, a coloring material, an organic solvent having a boiling point of 290°C or higher, a silicone surfactant, and resin B. In addition, by using the ink in combination with the ink in which the content of the organic solvent having a boiling point of 290° C. or higher is 0.5% by mass or more based on the total amount of the ink, the ink ejection stability is excellent and the formed image is have excellent fixability to the base material, and can suppress the occurrence of image bleeding and cracking.

Since the treatment liquid is applied to the substrate before applying the ink, the treatment liquid is sometimes referred to as a pretreatment liquid.

<Treatment Liquid Application Step and Treatment Liquid Application Means>
The treatment liquid application step is a step of applying a treatment liquid containing a polyvalent metal salt and resin A to a substrate.
The treatment liquid application means is a means for applying the treatment liquid contained in the treatment liquid container containing the treatment liquid containing the polyvalent metal salt and the resin A to the substrate. The treatment liquid container is not particularly limited, and a known inkjet cartridge or the like can be used.

-Processing liquid-
The treatment liquid contains the polyvalent metal salt and the resin A, and if necessary, may contain water, an organic solvent, a surfactant, and other components.
The organic solvent, the surfactant, and the other components (e.g., antifoaming agent, pH adjuster, antiseptic/antifungal agent, antirust agent, antibacterial agent) use the same materials as those used for the ink described later. In addition, materials used for known processing liquids can be used. As the organic solvent for the treatment liquid, any organic solvent that can be used in the ink described later can be appropriately selected without specifying the boiling point.

-- Polyvalent metal salt (coagulant) --
The polyvalent metal salt functions as a flocculating agent.
The polyvalent metal salt reacts with the components in the ink to suppress image bleeding and the like, thereby forming a high-quality image.
In addition, the polyvalent metal salt causes the pigment in the ink to quickly coagulate after droplet deposition, thereby suppressing color bleeding and improving color developability.

The polyvalent metal salt is not particularly limited and may be appropriately selected depending on the purpose. Examples include titanium salts, chromium salts, copper salts, cobalt salts, strontium salts, barium salts, iron salts, aluminum salts, Calcium salts, potassium salts, magnesium salts and the like. These may be used singly or in combination of two or more.
Among these, divalent metal salts are preferred, and calcium salts, magnesium salts and the like are more preferred.
Examples of the calcium salt include calcium carbonate, calcium nitrate, calcium chloride, calcium acetate, calcium sulfate, magnesium chloride, magnesium acetate, and magnesium sulfate. These may be used singly or in combination of two or more.

The content of the polyvalent metal salt is preferably 0.1% by mass or more and less than 5% by mass, more preferably 0.1% by mass or more and 3% by mass or less, relative to the total amount of the treatment liquid. When the content of the polyvalent metal salt is 0.1% by mass or more and less than 5% by mass with respect to the total amount of the treatment liquid, the effect of suppressing bleeding and cracking of the formed image is improved. be able to. In addition, when the content of the polyvalent metal salt is 0.1% by mass or more and 3% by mass or less with respect to the total amount of the treatment liquid, the image feasibility (bleeding between colors, cracking of the coating film, etc.) It is possible to improve the fact that it is established as an image without

--Resin A--
The resin A is not particularly limited and can be appropriately selected depending on the intended purpose. resins, acrylic styrene resins, acrylic silicone resins, and the like. Among these, urethane resins and acrylic resins are preferred. When the resin A is a urethane resin or an acrylic resin, it is possible to improve the adhesion to the substrate, the adhesion to the image formed by the ink described later, and the adhesion to the substrate.

The form of the resin A is not particularly limited and can be appropriately selected depending on the intended purpose. Examples thereof include resin particles.
It is possible to obtain a treatment liquid by mixing the resin particles in a state of a resin emulsion in which water is dispersed as a dispersion medium with a material such as a polyvalent metal salt or an organic solvent.
As the resin particles, appropriately synthesized ones may be used, or commercially available products may be used. As the resin A, one type may be used alone, or two or more types may be used in combination.

Examples of the commercially available resin fine particles include Xw-Um12 (polyurethane resin, manufactured by Mitsui Chemicals, Inc.), Xw-Um3A (polyurethane resin, manufactured by Mitsui Chemicals, Inc.), W6110 (polyurethane resin, manufactured by Mitsui Chemicals, Inc., Solid content concentration: 35 mass%), Superflex 300 (polyurethane resin, manufactured by Daiichi Kogyo Seiyaku Co., Ltd., solid content concentration: 30 mass%), Xw-Um7 (polyurethane resin, manufactured by Mitsui Chemicals, Inc., solid content concentration: 30% by mass), Movinyl 6800 (acrylic resin, manufactured by Japan Coating Resin Co., Ltd., solid content concentration: 45% by mass), Movinyl 6969D (acrylic resin, manufactured by Japan Coating Resin Co., Ltd., solid content concentration: 40% by mass), Movinyl 6750 (acrylic resin, manufactured by Japan Coating Resin Co., Ltd., solid concentration: 50% by mass), Movinyl 6810 (acrylic resin, manufactured by Japan Coating Resin Co., Ltd., solid content concentration: 40% by mass), and the like.
The volume average particle diameter of the resin particles is not particularly limited and can be appropriately selected according to the intended purpose. It is more preferably 10 nm or more and 500 nm or less, and particularly preferably 10 nm or more and 300 nm or less.
The volume average particle diameter can be measured, for example, using a particle size analyzer (Nanotrack Wave-UT151, manufactured by Microtrack Bell Co., Ltd.).

The content of the resin A is not particularly limited and can be appropriately selected according to the purpose. 2% by mass or more and 10% by mass or less is preferable, and 4% by mass or more and 8% by mass or less is more preferable. When the content of the resin A is 2% by mass or more and 10% by mass or less with respect to the total amount of the treatment liquid, the adhesion to the substrate and the adhesion to the formed image can be improved.

As the resin A, a urethane resin having a glass transition temperature Tg of preferably −70° C. or more and 0° C. or less, more preferably −55° C. or more and −5° C. or less. The temperature of the acrylic resin is preferably 0° C. or higher and 100° C. or lower, more preferably 0° C. or higher and 80° C. or lower. When the Tg of the treatment liquid is −55° C. or more and −5° C. or less in the case of the urethane resin, and 0° C. or more and 80° C. or less in the case of the acrylic resin, it is possible to improve the adhesion while ensuring ejection stability. .

--Other Ingredients--
The other components are not particularly limited and can be appropriately selected depending on the purpose.

As a method for applying the treatment liquid, any known method can be used without particular limitation. For example, inkjet method, 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 , micro gravure coating, reverse roll coating, four-roll coating, five-roll coating, dip coating, curtain coating, slide coating, die coating and the like.
The treatment liquid can be used as a pretreatment liquid before applying color ink.

The substrate is not particularly limited as long as it is conventionally used as a recording medium, and can be appropriately selected according to the purpose.

[recoding media]
The recording medium is not particularly limited, and plain paper, glossy paper, special paper, cloth, and the like can be used.
The non-permeable substrate is a substrate having a surface with low water permeability and low absorbency, and includes materials that do not open to the outside even if there are many cavities inside. , refers to a substrate having a water absorption of 10 mL/m ² or less from the start of contact to 30 msec ^1/2 in the Bristow method.
As the impermeable substrate, for example, plastic films such as vinyl chloride resin films, polyethylene terephthalate (PET) films, polypropylene, polyethylene and polycarbonate films can be suitably used.
In addition, it is not limited to those used as general recording media, and wallpaper, floor materials, building materials such as tiles, cloth for clothing such as T-shirts, textiles, leather, etc. can be used as appropriate. Ceramics, glass, metal, etc. can also be used by adjusting the configuration of the path for conveying the recording medium.

<Ink Application Step and Ink Application Means>
The ink application step contains a coloring material, an organic solvent having a boiling point of 290° C. or higher, a silicone surfactant, and a resin B, and the content of the organic solvent having a boiling point of 290° C. or higher is and applying an ink of 0.5% by mass or more onto the treatment liquid.
The ink application unit contains a coloring material, an organic solvent having a boiling point of 290° C. or higher, a silicone surfactant, and a resin B, and the content of the organic solvent having a boiling point of 290° C. or higher is , means for applying the ink contained in the ink container containing 0.5% by mass or more of ink onto the treatment liquid. The ink storage container is not particularly limited and can be appropriately selected according to the purpose.

-ink-
The coloring material, the organic solvent having a boiling point of 290° C. or higher, the silicone-based surfactant, the resin B, water, and other components used in the ink are described below.

--coloring material--
The coloring material is not particularly limited, and pigments and dyes can be used.
An inorganic pigment or an organic pigment can be used as the pigment. These may be used individually by 1 type, and may use 2 or more types together. Mixed crystals may also be used.
Examples of the pigments that can be used include black pigments, yellow pigments, magenta pigments, cyan pigments, white pigments, green pigments, orange pigments, glossy color pigments such as gold and silver, and metallic pigments.
As the inorganic pigment, in addition to titanium oxide, iron oxide, calcium carbonate, barium sulfate, aluminum hydroxide, barium yellow, cadmium red, and chrome yellow, carbon produced by a known method such as a contact method, a furnace method, a thermal method, etc. Black can be used.
Examples of the organic pigment include 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 (eg, basic dye chelates, acid dye chelates, etc.), nitro pigments, nitroso pigments, aniline black, and the like. 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 the pigments for black include carbon blacks (C.I. Pigment Black 7) such as furnace black, lamp black, acetylene black and channel black, or copper and iron (C.I. Pigment Black 11). ), metals such as titanium oxide, and organic pigments such as aniline black (C.I. Pigment Black 1).
Further, for color, 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, C.I. I. Pigment Orange 5, 13, 16, 17, 36, 43, 51, C.I. I. 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 red), 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, C.I. I. Pigment Violet 1 (rhodamine lake), 3, 5:1, 16, 19, 23, 38, 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, etc.
The dyes are not particularly limited, and acid dyes, direct dyes, reactive dyes, and basic dyes can be used, and may be used singly or in combination of two or more. . Examples of the dye include 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. Food Black 1, 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. Directed Black 19, 38, 51, 71, 154, 168, 171, 195, C.I. I. Reactive Red 14, 32, 55, 79, 249, C.I. I. and Reactive Black 3,4,35.

The content of the coloring material in the ink is preferably 0.1% by mass or more and 15% by mass or less, more preferably 1% by mass or more and 10% by mass, from the viewpoints of improvement in image density, good fixability and ejection stability. % or less.

In order to obtain an ink by dispersing the pigment, there are a method of introducing a hydrophilic functional group into the pigment to make it a self-dispersing pigment, a method of coating the surface of the pigment with a resin to disperse it, and a method of dispersing using a dispersant. and the like.
As a method of making the self-dispersing pigment by introducing a hydrophilic functional group into the pigment, for example, by adding a functional group such as a sulfone group or a carboxyl group to the pigment (for example, carbon), it is possible to disperse it in water. method.
Examples of the method of coating the surface of the pigment with a resin to disperse it include a method of encapsulating the pigment in microcapsules to make it dispersible in water. This can be rephrased as a resin-coated pigment. In this case, all the pigments mixed in the ink need not be coated with a resin, and uncoated pigments or partially coated pigments may be dispersed in the ink as long as the effects of the present invention are not impaired. may be A resin-coated pigment is preferable from the viewpoint of ejection reliability and coating film fastness.
Examples of the method of dispersing using the dispersant include a method of dispersing using a known low-molecular-weight dispersant and high-molecular-weight dispersant typified by surfactants.
As the dispersant, for example, an anionic surfactant, a cationic surfactant, an amphoteric surfactant, a nonionic surfactant, etc. can be used depending on the pigment.
RT-100 (nonionic surfactant) manufactured by Takemoto Yushi Co., Ltd. and sodium naphthalenesulfonate formalin condensate can also be suitably used as a dispersant.
The dispersant may be used singly or in combination of two or more.

[Pigment dispersion]
Inks can be obtained by mixing materials such as water and organic solvents with the pigments. Ink can also be produced by mixing a pigment with water, a dispersant, and the like to form a pigment dispersion, and then mixing materials such as water and an organic solvent.
The pigment dispersion is obtained by mixing and dispersing water, a pigment, a pigment dispersant, and optionally other components, and adjusting the particle size. Dispersion should be carried out using a disperser.
The particle diameter of the pigment in the pigment dispersion is not particularly limited, but the dispersion stability of the pigment is improved, and the image quality such as ejection stability and image density is improved. 500 nm or less is preferable, and 20 nm or more and 150 nm or less is more preferable. The particle size of the pigment can be measured using a particle size analyzer (Nanotrack Wave-UT151, manufactured by Microtrack Bell Co., Ltd.).
The content of the pigment in the pigment dispersion is not particularly limited and can be appropriately selected according to the purpose. % or more and 50 mass % or less is preferable, and 0.1 mass % or more and 30 mass % or less is more preferable.
The pigment dispersion is preferably degassed by filtering coarse particles with a filter, a centrifugal separator, or the like, if necessary.

--Organic solvent having a boiling point of 290°C or higher--
The organic solvent having a boiling point of 290° C. or higher is not particularly limited and can be appropriately selected depending on the intended purpose. Examples thereof include benzyl benzoate, glycerin (glycerol) and triethanolamine. Containing an organic solvent having a boiling point of 290° C. or higher can improve the continuous ejection stability of the ink.
The content of the organic solvent having a boiling point of 290° C. or higher is 0.5% by mass or more, preferably 0.5% by mass or more and 5% by mass or less, relative to the total amount of the ink. When the content of the organic solvent having a boiling point of 290° C. or higher is 0.5% by mass or more with respect to the total amount of the ink, the initial ejection property of the ink and the scratch resistance of the formed image are improved. When the content is 0.5% by mass or more and 5% by mass or less, the continuous ejection stability of the ink and the drying property of the ink can be improved.

Note that the ink may contain other organic solvents.

---Other organic solvents---
The other organic solvent is not particularly limited and can be appropriately selected depending on the intended purpose. For example, a water-soluble organic solvent can be used.
Examples of the water-soluble organic solvent include polyhydric alcohols, ethers such as polyhydric alcohol alkyl ethers and polyhydric alcohol aryl ethers, nitrogen-containing heterocyclic compounds, amides, amines, sulfur-containing compounds, and the like. is mentioned.
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-pentane Diol, 2,4-pentanediol, 1,5-pentanediol, 1,2-hexanediol, 1,6-hexanediol, 1,3-hexanediol, 2,5-hexanediol, 1,5-hexanediol , 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, polyhydric alcohols such as 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 ether Polyhydric alcohol alkyl ethers such as ethylene glycol monophenyl ether, polyhydric alcohol aryl ethers such as ethylene glycol monobenzyl ether, 2-pyrrolidone, N-methyl-2-pyrrolidone, N-hydroxyethyl-2-pyrrolidone, Nitrogen-containing heterocyclic compounds such as 1,3-dimethyl-2-imidazolidinone, ε-caprolactam, γ-butyrolactone, formamide, N-methylformamide, N,N-dimethylformamide, 3-methoxy-N,N-dimethyl Amides such as propionamide and 3-butoxy-N,N-dimethylpropionamide, amines such as monoethanolamine, diethanolamine and triethylamine, sulfur-containing compounds such as dimethylsulfoxide, sulfolane and thiodiethanol, propylene carbonate, ethylene carbonate, etc. is mentioned.
It is preferable to use an organic solvent having a boiling point of 250° C. or less because it not only functions as a wetting agent but also provides good drying properties.

Polyol compounds having 8 or more carbon atoms and glycol ether compounds are also preferably 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 glycol ether compounds include polyhydric alcohol alkyls 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. Ethers; polyhydric alcohol aryl ethers such as ethylene glycol monophenyl ether, ethylene glycol monobenzyl ether, and the like.
A polyol compound having 8 or more carbon atoms and a glycol ether compound can improve ink permeability when paper is used as a recording medium.

The content of the other organic solvent is not particularly limited and can be appropriately selected according to the purpose. 60% by mass or less is preferable, and 20% by mass or more and 60% by mass or less is more preferable.

--Silicone surfactant--
The silicone-based surfactant is not particularly limited and can be appropriately selected depending on the intended purpose.
The silicone-based surfactant is not particularly limited and can be appropriately selected depending on the intended purpose. Examples include polydimethylsiloxane modified at both chain ends, and polyether-modified silicone-based surfactants having polyoxyethylene groups or polyoxyethylene-polyoxypropylene groups as modifying groups exhibit excellent properties as water-based surfactants. preferable.

Among the above silicone-based surfactants, those that do not decompose even at high pH are preferable. etc., and those having a polyoxyethylene group or a polyoxyethylene polyoxypropylene group as a modifying group are particularly preferred because they exhibit good properties as water-based surfactants.

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 side chain of the Si portion of dimethylsiloxane.

As such a surfactant, an appropriately synthesized one may be used, or a commercially available product may be used. Commercially available products are available from, for example, BYK Chemie Co., Ltd., Shin-Etsu Chemical Co., Ltd., Dow Corning Toray Silicone Co., Ltd., Nihon Emulsion Co., Ltd., Kyoeisha Chemical Co., Ltd., and the like.

一般式（Ｓ－１）
（但し、一般式（Ｓ－１）式中、ｍ、ｎ、ａ、及びｂは、それぞれ独立に、整数を表わし、Ｒは、アルキレン基を表し、Ｒ’は、アルキル基を表す。） The above polyether-modified silicone-based surfactant is not particularly limited and can be appropriately selected according to the purpose. Examples include those introduced into the side chain of the Si portion of siloxane.

General formula (S-1)
(However, in 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.)

Commercially available products can be used as the above polyether-modified silicone-based surfactants. 1906EX (Japan 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 Corporation), TSF4440, TSF4452, TSF4453 (Toshiba Silicon Co., Ltd.) and the like.

The content of the silicone-based surfactant is preferably 0.001% by mass or more and 5% by mass or less, more preferably 0.05% by mass or more and 5% by mass or less, and 0.1% by mass, based on the total amount of the ink. % or more and 3 mass % or less is more preferable. When the content of the silicone-based surfactant is 0.001% by mass or more and 5% by mass or less relative to the total amount of the ink, wettability and ejection stability can be improved, and image quality can be improved. Further, when the content of the silicone-based surfactant is 0.1% by mass or more and 3% by mass or less with respect to the total amount of the ink, the initial ejection stability of the ink and the scratch resistance of the formed image are improved. can be made

In addition, the ink may contain a surfactant other than the silicone surfactant.

---Other surfactants---
The other surfactants are not particularly limited and can be appropriately selected depending on the intended purpose. Either can be used.
Examples of the fluorine-based surfactant include perfluoroalkylsulfonic acid compounds, perfluoroalkylcarboxylic acid compounds, perfluoroalkylphosphoric acid ester compounds, perfluoroalkylethylene oxide adducts, and perfluoroalkyl ether groups in side chains. A polyoxyalkylene ether polymer compound having a low foaming property is particularly preferred. Examples of the perfluoroalkylsulfonic acid compound include perfluoroalkylsulfonic acid and perfluoroalkylsulfonate. Examples of the perfluoroalkylcarboxylic acid compounds include perfluoroalkylcarboxylic acids and perfluoroalkylcarboxylic acid salts. As the polyoxyalkylene ether polymer compound having a perfluoroalkyl ether group in a side chain, a sulfate ester salt of a polyoxyalkylene ether polymer having a perfluoroalkyl ether group in a side chain, and a perfluoroalkyl ether group in a side chain Examples thereof include salts of polyoxyalkylene ether polymers. Counter ions _of salts _in these fluorosurfactants include Li, Na, _K , _NH4 , _NH3CH2CH2OH , _NH2 ( _CH2CH2OH ) _{2 ,} and NH( _CH2CH2OH ). ₃ and the like.
Examples of the amphoteric surfactant include laurylaminopropionate, lauryldimethylbetaine, stearyldimethylbetaine, lauryldihydroxyethylbetaine and the like.
Examples of nonionic surfactants include polyoxyethylene alkylphenyl ether, polyoxyethylene alkyl ester, polyoxyethylene alkylamine, polyoxyethylene alkylamide, polyoxyethylene propylene block polymer, sorbitan fatty acid ester, and polyoxyethylene. Examples include sorbitan fatty acid esters and ethylene oxide adducts of acetylene alcohol.
Examples of the anionic surfactant include polyoxyethylene alkyl ether acetate, dodecylbenzene sulfonate, laurate, polyoxyethylene alkyl ether sulfate, and the like.
These may be used individually by 1 type, or may use 2 or more types together.

--Resin B--
The resin B is not particularly limited and can be appropriately selected depending on the intended purpose. resins, vinyl chloride resins, acrylic styrene resins, acrylic silicone resins, and the like.
As the resin B, resin particles made of these resins may be used. Ink can be obtained by mixing resin particles in a resin emulsion state in which water is dispersed as a dispersion medium with a material such as a coloring material or an organic solvent.
As the resin particles, appropriately synthesized ones may be used, or commercially available products may be used.
Moreover, these may be used individually by 1 type, or may be used in combination of 2 or more types of resin particles.
From the viewpoint of fixability to the base material, it is preferable to contain a urethane resin or an acrylic resin.

The content of the resin B is preferably 1% by mass or more and 30% by mass or less, more preferably 2% by mass or more and 10% by mass or less, and even more preferably 2% by mass or more and 6% by mass or less, relative to the total amount of the ink. When the content of the resin B is 1% by mass or more and 30% by mass or less with respect to the total amount of the ink, the storage stability of the ink and the fixability of the formed image can be improved. Moreover, when the content of the resin B is 2% by mass or more and 10% by mass or less with respect to the total amount of the ink, the ejection stability and the fixability of the formed image can be improved. Furthermore, when the content of the resin B is 2% by mass or more and 6% by mass or less with respect to the total amount of the ink, the viscosity of the ink can be kept within an appropriate range, and the ejection stability can be improved. can.

As an embodiment of the resin B, resin particles may be used. Ink can be obtained by mixing the resin particles in a state of a resin emulsion in which water is dispersed as a dispersion medium with a material such as a coloring material or an organic solvent. As the resin particles, appropriately synthesized ones may be used, or commercially available products may be used. Moreover, these may be used individually by 1 type, or may be used in combination of 2 or more types of resin particles.

The volume average particle diameter of the resin particles is not particularly limited and can be appropriately selected according to the intended purpose. It is more preferably 10 nm or more and 200 nm or less, and particularly preferably 10 nm or more and 100 nm or less.
The volume average particle diameter can be measured, for example, using a particle size analyzer (Nanotrack Wave-UT151, manufactured by Microtrack Bell Co., Ltd.).

The particle size of the solid content in the ink is not particularly limited and can be appropriately selected according to the purpose. 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, and the like. The particle size can be measured using a particle size analyzer (Nanotrack Wave-UT151, manufactured by Microtrack Bell Co., Ltd.).

--water--
The content of water is not particularly limited and can be appropriately selected according to the intended purpose.

--Other Ingredients--
The other components are not particularly limited and can be appropriately selected depending on the intended purpose.

--- Defoamer ---
The antifoaming agent is not particularly limited, and examples thereof include silicone antifoaming agents, polyether antifoaming agents, and fatty acid ester antifoaming agents. These may be used individually by 1 type, or may use 2 or more types together. Among these, silicone-based antifoaming agents are preferred because of their excellent foam breaking effect.

--- Antiseptic and antifungal agent ---
The antiseptic and antifungal agent is not particularly limited, and examples thereof include 1,2-benzisothiazolin-3-one.

---anti-rust---
The rust inhibitor is not particularly limited, and examples thereof include acidic sulfites and sodium thiosulfate.

--- pH adjuster ---
The pH adjuster is not particularly limited as long as it can adjust the pH to 7 or higher, and examples thereof include amines such as diethanolamine and triethanolamine.

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

<Other steps and other means>
The other steps are not particularly limited and can be appropriately selected depending on the purpose, and examples thereof include a drying step.
The other means are not particularly limited and can be appropriately selected depending on the purpose, and examples thereof include drying means.

<<Drying process and drying means>>
The drying step is a step of drying the treatment liquid and the ink.
The drying means is means for drying the treatment liquid and the ink.
In the drying step, particularly when the recording medium is a non-permeable substrate, the drying temperature during recording is set at 50 to improve the fixability to the non-permeable substrate and to suppress the occurrence of bleeding. °C or higher is preferred. The upper limit of the drying temperature during recording is not particularly limited and can be appropriately selected according to the purpose. Furthermore, from the viewpoint of the wettability of the ink to the substrate, the temperature is preferably 90° C. or less. The drying temperature before and after recording is not particularly limited and can be appropriately selected according to the purpose. The following are preferred.

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

[Recording device, recording method]
The ink of the present invention can be suitably used for various inkjet recording apparatuses, such as printers, facsimile machines, copiers, printer/facsimile/copier complex machines, stereolithography machines, and the like.
In the present invention, a recording apparatus and a recording method refer to an apparatus capable of ejecting ink, various treatment liquids, and the like onto a recording medium, and a method of performing recording using the apparatus. A recording medium means a medium to which ink or various processing liquids can adhere even temporarily.
This recording apparatus can include not only a head portion for ejecting ink, but also means for feeding, conveying, and discharging a recording medium, and other devices called pre-processing devices and post-processing devices. .
The recording apparatus and recording method may have heating means used in the heating process and drying means used in the drying process. The heating means and drying means include, for example, means for heating and drying the printing surface and the back surface of the recording medium. The heating means and drying means are not particularly limited, but for example, hot air heaters and infrared heaters can be used. Heating and drying can be performed before, during, or after printing. The heating temperature is preferably 40° C. or higher and 120° C. or lower, more preferably 50° C. or higher and 120° C. or lower from the viewpoint of fixability, and further preferably 50° C. or higher and 90° C. or lower from the viewpoint of not impairing the flexibility of the leather. .
Also, the recording apparatus and recording method are not limited to those that visualize significant images such as characters and graphics with ink. For example, it includes those that form patterns such as geometric patterns, and those that form three-dimensional images.
In addition, unless otherwise specified, the recording apparatus includes both a serial type apparatus in which the ejection head is moved and a line type apparatus in which the ejection head is not moved.
Furthermore, this recording device can be used not only as a desktop type, but also as a wide recording device that can print on A0 size recording media, and for example, can use continuous paper wound into a roll as a recording medium. A continuous feed printer is also included.
An example of a recording apparatus will be described with reference to FIGS. 1 and 2. FIG. FIG. 1 is a perspective explanatory view of the device. FIG. 2 is a perspective explanatory view of the main tank. An image forming apparatus 400 as an example of a recording apparatus is a serial image forming apparatus. A mechanical unit 420 is provided inside the exterior 401 of the image forming apparatus 400 . Each ink container 411 of the main tank 410 (410k, 410c, 410m, 410y) for each color of black (K), cyan (C), magenta (M), and yellow (Y) is packed with, for example, an aluminum laminated film. It is made up of members. The ink containing portion 411 is contained, for example, in a container case 414 made of plastic. Thus, the main tank 410 is used as an ink cartridge for each color.
On the other hand, a cartridge holder 404 is provided on the far side of the opening when the cover 401c of the apparatus main body is opened. A main tank 410 is detachably attached to the cartridge holder 404 . As a result, each ink discharge port 413 of the main tank 410 communicates with the ejection head 434 for each color via the supply tube 436 for each color, and ink can be ejected from the ejection head 434 onto the printing medium.

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 aspect of the pre-treatment device and the post-treatment device, it has a pre-treatment liquid and a post-treatment liquid in the same manner as in the case of inks such as black (K), cyan (C), magenta (M), and yellow (Y). There is a mode in which a liquid container and a liquid ejection head are added, and the pretreatment liquid and the posttreatment liquid are ejected by an inkjet recording method.
As another aspect of the pre-treatment device and the post-treatment device, there is an aspect in which a pre-treatment device and a post-treatment device using a method other than the inkjet recording method, such as a blade coating method, a roll coating method, and a spray coating method, are provided.

Examples of methods for applying the ink include an inkjet method, a blade coating method, a gravure coating method, a gravure offset coating method, a bar coating method, a roll coating method, a knife coating method, an air knife coating method, a comma coating method, a U comma Coating method, AKKU coating method, smoothing coating method, micro gravure coating method, reverse roll coating method, 4-roll coating method, 5-roll coating method, dip coating method, curtain coating method, slide coating method, die coating method, etc. be done.

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 of FIG. 3 has means for applying treatment liquid (treatment liquid coating device 21 ), ejection means for ejecting ink (ink ejection head 22 ), and transport belt 23 . The image forming apparatus 100 prints on the recording medium 11 .

(Set treatment liquid and ink)
The treatment liquid and ink set of the present invention includes a treatment liquid containing a polyvalent metal salt and a resin,
It contains a coloring material, an organic solvent with a boiling point of 290°C or higher, a silicone surfactant, and a resin, and the content of the organic solvent with a boiling point of 290°C or higher is 0.5% by mass or more relative to the total amount of the ink. and an ink that is
The treatment liquid and ink in the treatment liquid and ink set of the present invention are the same as the treatment liquid and ink in the printing method of the present invention.

(Printed Matter Manufacturing Method and Printed Matter Manufacturing Apparatus)
The method for producing a printed matter of the present invention includes a treatment liquid application step of applying a treatment liquid containing a polyvalent metal salt and a resin to a substrate, a coloring material, an organic solvent having a boiling point of 290 ° C. or higher, and a silicone surfactant. and an ink application step of applying an ink containing a resin and having a content of the organic solvent having a boiling point of 290° C. or higher of 0.5% by mass or more with respect to the total amount of the ink onto the treatment liquid. and optionally other steps.
Further, the printed matter manufacturing apparatus according to the printed matter manufacturing method of the present invention includes: a processing liquid container containing a processing liquid containing a polyvalent metal salt and resin A; A treatment liquid applying means for applying to the material, a coloring material, an organic solvent having a boiling point of 290 ° C. or higher, a silicone surfactant, and a resin B, and the content of the organic solvent having a boiling point of 290 ° C. or higher is an ink containing section containing ink of 0.5% by mass or more with respect to the total amount; and an ink applying means for applying the ink contained in the ink containing section onto the treatment liquid; have other means depending on
The method for producing printed matter of the present invention is the same as the printing method of the present invention.
The printed matter manufacturing apparatus is the same as the printing apparatus.

In the present invention, the terms image formation, recording, printing, and printing are all synonymous.

The terms recording medium, medium, and printed material are all synonymous.

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 inks were prepared and evaluated under the conditions of a room temperature of 25° C. and a relative humidity of 60% RH. In addition, "parts" in the examples represent "parts by mass", and "%" represents "% by mass" except for those in the evaluation criteria.

<Preparation example of treatment liquid a>
The materials of the following formulation were mixed, and the total amount was adjusted to 100 parts by mass with ion-exchanged water, followed by mixing and stirring. After that, it was filtered through a filter having an average pore size of 5 μm (manufactured by Sartorius, trade name: Minizart) to obtain a treatment liquid a.
[Prescription]
・ 1,2-propanediol (trade name: propylene glycol, manufactured by ADEKA Corporation)
: 35 parts by mass 3-methoxy-3-methyl-1-butanol (trade name: Solfit, manufactured by Kuraray Co., Ltd.): 30 parts by mass Polyurethane resin (1) (trade name: Xw-Um12, Mitsui Chemicals, Inc. made)
: 6.0 parts by mass SAG-503A (silicone surfactant, manufactured by Nissin Chemical Industry Co., Ltd.): 0.5 parts by mass Magnesium acetate-hydrate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.): 0. 5 parts by mass, deionized water: remaining amount (total: 100 parts by mass)

<Preparation examples of treatment liquids b to r>
Treatment liquids b to r were prepared in the same manner as in Preparation Example of Treatment Liquid a, except that the formulations in Preparation Example of Treatment Liquid a were changed to those shown in Tables 1 to 3. In addition, content of resin in a table|surface shows solid content.

Next, preparation examples of pigment dispersions used in ink will be described.

[Preparation example of black pigment dispersion]
11.2 g of styrene, 2.8 g of acrylic acid, 12 g of lauryl methacrylate, 4 g of polyethylene glycol methacrylate, 4 g of styrene macromer and 0.4 g of mercaptoethanol were mixed and heated to 65°C.
Then 100.8 g styrene, 25.2 g acrylic acid, 108 g lauryl methacrylate, 36 g polyethylene glycol methacrylate, 60 g hydroxylethyl methacrylate, 36 g styrene macromer, 3.6 g mercaptoethanol, 2.4 g azobismethylvaleronitrile, and 18 g methyl ethyl ketone. was dropped into the flask over 2.5 hours.
After dropping, a mixed solution of 0.8 g of azobismethylvaleronitrile and 18 g of methyl ethyl ketone was dropped into the flask over 0.5 hours.
After aging at 65° C. for 1 hour, 0.8 g of azobismethylvaleronitrile was added and further aged for 1 hour.
After completion of the reaction, 364 g of methyl ethyl ketone was added to the flask to obtain 800 g of polymer solution A having a solid concentration of 50%.
Then, 28 g of polymer solution A, 42 g of carbon black (Black Pearls 1000, manufactured by Cabot Corporation), 13.6 g of 1 mol / L potassium hydroxide aqueous solution, 20 g of methyl ethyl ketone, and 13.6 g of water were sufficiently stirred, followed by roll milling. kneaded with
The obtained paste was put into 200 g of pure water and stirred sufficiently, then the methyl ethyl ketone was removed by an evaporator, and the mixture was pressure-filtered through a polyvinylidene fluoride membrane filter with an average pore size of 5 μm. A styrene-acrylic resin-coated black pigment dispersion having a solid content concentration of 20% was obtained.

[Preparation example of cyan pigment dispersion]
In the black pigment dispersion preparation example, the solid content concentration was 20% in the same manner as in the black pigment dispersion preparation example, except that Pigment Blue 15:4 (SMART Cyan 3154BA manufactured by SENSIENT) was used instead of carbon black. of styrene-acrylic resin-coated cyan pigment dispersion was obtained.

[Preparation Example of Magenta Pigment Dispersion]
In the preparation example of the black pigment dispersion, a solid content concentration of 20% was prepared in the same manner as in the preparation example of the black pigment dispersion, except that Pigment Red 122 (Pigment Red 122 manufactured by Sun Chemical Co.) was used instead of carbon black. A styrene-acrylic resin-coated magenta pigment dispersion was obtained.

[Preparation example of yellow pigment dispersion]
In the black pigment dispersion preparation example, in the same manner as in the black pigment dispersion preparation example, except that Pigment Yellow 74 (SMART Yellow 3074BA manufactured by SENSIENT) is used instead of carbon black. - An acrylic resin-coated yellow pigment dispersion was obtained.

<Preparation Example of Ink A>
The ingredients of the following formulation are mixed, and the total amount is adjusted to 100 parts by mass with ion-exchanged water, followed by mixing and stirring. After that, the mixture was filtered through a filter having an average pore size of 5 μm (manufactured by Sartorius, trade name: Minizart) to obtain Ink A.
[Ink prescription]
・ Black pigment dispersion: 20 parts by mass ・ 1,2-propanediol (trade name: propylene glycol, manufactured by ADEKA Co., Ltd.)
: 15 parts by mass 1,3-butanediol (manufactured by Tokyo Chemical Industry Co., Ltd.) : 4 parts by mass 2-ethyl-1,3-hexanediol (trade name: EHD, manufactured by Kuraray Co., Ltd.)
: 1 part by mass 3-methoxy-3-methyl-1-butanol (trade name: Solfit, manufactured by Kuraray Co., Ltd.) : 5 parts by mass 3-methoxy-N,N-dimethylpropionamide (trade name: M100, Idemitsu Kosan Co., Ltd.): 10 parts by mass Polyurethane resin (2) (trade name: Xw-Um3A, manufactured by Mitsui Chemicals, Inc.)
: 4.0 parts by mass Polyurethane resin (3) (trade name: W6110, manufactured by Mitsui Chemicals, Inc., polyurethane resin, solid content concentration: 35% by mass) : 6.0 parts by mass Triton HW1000, poly(oxyethylene) = Alkyl ether (manufactured by Dow Chemical Company, non-silicone surfactant): 0.2 parts by mass SAG-503A (manufactured by Nissin Chemical Industry Co., Ltd., silicone surfactant): 1.0 parts by mass Ion-exchanged water : Remaining amount (total: 100 parts by mass)

<Preparation example of inks B to R>
Inks B to R were prepared in the same manner as in Ink A Preparation Example, except that the formulations in Ink A Preparation Example were changed to those shown in Tables 4 to 6. In addition, content of resin in a table|surface shows solid content.
The polyurethane resin (5) used in Inks C, H, M and Q was prepared by the following method.

[Preparation example of polyurethane resin (5)]
200.4 g of polyester polyol (trade name: Polylite OD-X-2251, manufactured by DIC Corporation, average molecular weight 2,000) in a nitrogen-purged container equipped with a thermometer, a nitrogen gas inlet tube, and a stirrer, 15.7 g of 2,2-dimethylolpropionic acid, 48.0 g of isophorone diisocyanate, 77.1 g of methyl ethyl ketone as an organic solvent, and 0.06 g of DMTDL (dibutyltin dilaurate) as a catalyst were reacted.
After the reaction was continued for 4 hours, 30.7 g of methyl ethyl ketone was supplied as a dilution solvent, and the reaction was further continued.
When the average molecular weight of the reaction product reached the range of 20,000 to 60,000, 1.4 g of methanol was added to terminate the reaction, thereby obtaining an organic solvent solution of urethane resin.
Next, 13.4 g of a 48% by mass potassium hydroxide aqueous solution is added to the organic solvent solution of the urethane resin to neutralize the carboxyl groups of the urethane resin, and then 715.3 g of water is added and sufficiently stirred. A polyester-based urethane resin emulsion (polyurethane resin (5)) having a solid content concentration of 30% by mass was obtained by aging and removing the solvent.
The minimum film-forming temperature (MFT) of the obtained polyurethane resin (5) was 74° C. as measured by a "film-forming temperature tester" (manufactured by Imoto Seisakusho Co., Ltd.).

Details of the materials used in the treatment liquid and ink are as follows.
[resin]
・ Polyurethane resin (1) (trade name: Xw-Um12, manufactured by Mitsui Chemicals, Inc.)
・ Polyurethane resin (2) (trade name: Xw-Um3A, manufactured by Mitsui Chemicals, Inc.)
・ Polyurethane resin (3) (trade name: W6110, manufactured by Mitsui Chemicals, Inc., solid content concentration: 35% by mass)
・ Polyurethane resin (4) (trade name: Superflex 300, manufactured by Daiichi Kogyo Seiyaku Co., Ltd., solid content concentration: 30% by mass)
・ Polyurethane resin (6) (trade name: Xw-Um7, manufactured by Mitsui Chemicals, Inc., solid content concentration: 30% by mass)
・ Acrylic resin (1) (trade name: Movinyl 6800, manufactured by Japan Coating Resin Co., Ltd., solid content concentration: 45% by mass)
・ Acrylic resin (2) (trade name: Movinyl 6969D, manufactured by Japan Coating Resin Co., Ltd., solid content concentration: 40% by mass)
・ Acrylic resin (3) (trade name: Movinyl 6750, manufactured by Japan Coating Resin Co., Ltd., solid content concentration: 50% by mass)
・ Acrylic resin (4) (trade name: Movinyl 6810, manufactured by Japan Coating Resin Co., Ltd., solid content concentration: 40% by mass)
[Organic solvent]
・ 1,2-propanediol (trade name: propylene glycol, manufactured by ADEKA Corporation)
・ 1,3-propanediol (manufactured by ADEKA Co., Ltd.)
・ 1,3-butanediol (manufactured by Tokyo Chemical Industry Co., Ltd.)
・2-ethyl-1,3-hexanediol (trade name: EHD, manufactured by Kuraray Co., Ltd.)
・ 3-methyl-1,5-pentanediol (manufactured by Tokyo Chemical Industry Co., Ltd.)
・ 3-Methoxy-1-butanol (trade name: MB, manufactured by Daicel Corporation)
・ 3-Methoxy-3-methyl-1-butanol (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)
・ 3-Methoxy-N,N-dimethylpropionamide (trade name: Equamid M100, manufactured by Idemitsu Kosan Co., Ltd.)
・ 3-butoxy N, N-dimethylpropionamide (manufactured by Tokyo Chemical Industry Co., Ltd.)
[Organic solvent having a boiling point of 290°C or higher]
・Triethanolamine (manufactured by Sigma-Aldrich)
・Glycerin (manufactured by Sakamoto Yakuhin Kogyo Co., Ltd.)
[Surfactant]
・Triton HW1000 (poly(oxyethylene) = alkyl ether, Dow Chemical Company, non-silicone surfactant)
· BYK348 (manufactured by BYK-Chemie Japan Co., Ltd., silicone surfactant)
・ SAG-503A (manufactured by Nissin Chemical Industry Co., Ltd., silicone surfactant)
[Flocculant (metal salt)]
・ Calcium acetate hydrate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)
・ Magnesium acetate hydrate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)
・Aluminum chloride (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)
・Sodium chloride (manufactured by Fuso Pharmaceutical Industry Co., Ltd.)

(Examples 1 to 11 and Comparative Examples 1 to 8)
Using the combination of Tables 7 and 8, "initial ejection stability of ink" using the prepared ink, "image scratch resistance", "image bleeding" and "image formed using the treatment liquid and ink" Image cracking" was evaluated as follows.

<Initial ejection stability of ink>
An inkjet ejection head installed in an ejection evaluation device (EV2500, manufactured by Genesis) is filled with the prepared ink, and ejection is started after performing a maintenance operation.
The ejection of ink droplets was observed with the camera of the evaluation device, and the number of nozzles not ejecting ink droplets (total: 320 in one row) was counted as non-ejecting nozzles. The initial ejection stability of the ink was evaluated based on the following evaluation criteria. In addition, ◯ and ⊚ are levels at which practical use is possible.
[Evaluation criteria]
A: The number of non-ejection nozzles is 0 or more and 5 or less (Ejection rate: 97% or more and 100% or less)
○: The number of ejection failure nozzles is 6 or more and 10 or less (ejection rate: 94.5% or more and less than 97%)
×: The number of ejection failure nozzles is 11 or more (ejection rate: less than 94.5%)

[Image formation]
In Examples 1 to 11 and Comparative Examples 1 to 8, the black portion of an inkjet printer (device name: Ri100, manufactured by Ricoh Co., Ltd.) was filled with the ink, and the magenta portion was filled with the treatment liquid. Polyester felt (average thickness 2 mm), non-woven fabric (average thickness 0.3 mm), PET (average thickness 0.2 mm) were used as the substrates. / ^m2 solid image was printed.
Next, a solid image with an ink adhesion amount of about 13.0 g/m ² was printed, and the printed matter was dried with a hot air dryer at 80° C. to perform fixing.

<Scratch resistance of image>
The image obtained on the polyester felt was cut out to a size of 2.5 cm × 20 cm, installed in a dyeing friction fastness tester (model: AR-2, manufactured by Intec Co., Ltd.), a load of 200 g, a white cloth (Kanakin No. 3), at a reciprocating speed of 30 times/min, after reciprocating 25 times in the case of dry rubbing and 5 times in the case of wet rubbing, the state of the image and white cloth was observed and evaluated according to the following criteria.
If the evaluation results are "○" and "⊚", the level is practically usable. In the evaluation criteria, "image abnormality" means a state in which the image is scratched or the image (coating film) is peeled off from the recording medium.
[Evaluation criteria]
⊚: No abnormalities in both the cotton cloth and the image ○: The cotton cloth is colored, but no noticeable image abnormality
×: The cotton cloth is colored and the base material is exposed

<Image bleeding (color boundary bleeding)>
After applying the pretreatment liquid on the base material, after printing an image in which the respective colors are adjacent to each other, the state of bleeding at the color boundaries was visually confirmed. It should be noted that evaluation results of "○" and "⊚" are levels at which practical use is possible.
[Evaluation criteria]
◎: No bleeding at all ○: Rattling at the color boundary, color shading observed closely (rattling, shading width of 1.0 mm or less)
△: Rattling at the color boundary, easy to see the shade of the color

<Image Crack>
After applying the pretreatment liquid on the base material, an ink film is formed, and the state of the image after the drying process is confirmed and evaluated based on the following evaluation criteria. In addition, if the evaluation result is "○", it is a level at which practical use is possible.
[Evaluation criteria]
〇: No cracks occurred on the image ×: Cracks occurred on the image

Embodiments of the present invention are, for example, as follows.
<1> A treatment liquid application step of applying a treatment liquid containing a polyvalent metal salt and resin A to a substrate;
It contains a coloring material, an organic solvent with a boiling point of 290°C or higher, a silicone surfactant, and resin B, and the content of the organic solvent with a boiling point of 290°C or higher is 0.5% by mass with respect to the total amount of the ink. an ink application step of applying the above ink onto the treatment liquid;
A printing method comprising:
<2> The printing method according to <1>, wherein the content of the organic solvent having a boiling point of 290° C. or higher is 0.5% by mass or more and 5% by mass or less with respect to the total amount of the ink.
<3> The printing method according to any one of <1> to <2>, wherein the content of the silicone-based surfactant is 0.1% by mass or more and 3% by mass or less with respect to the total amount of the ink. .
<4> The printing method according to any one of <1> to <3>, wherein the resin A contains at least one of a urethane resin and an acrylic resin.
<5> The printing method according to any one of <1> to <4>, wherein the content of the resin A is 2% by mass or more and 10% by mass or less with respect to the total amount of the treatment liquid.
<6> The printing method according to any one of <1> to <5>, wherein the polyvalent metal salt contains at least one of calcium salt and magnesium salt.
<7> The printing method according to any one of <1> to <6>, wherein the content of the polyvalent metal salt is 0.1% by mass or more and 3% by mass or less with respect to the total amount of the treatment liquid. .
<8> a treatment liquid containing a polyvalent metal salt and a resin;
It contains a coloring material, an organic solvent with a boiling point of 290°C or higher, a silicone surfactant, and a resin, and the content of the organic solvent with a boiling point of 290°C or higher is 0.5% by mass or more relative to the total amount of the ink. and a set of the treatment liquid and the ink.
<9> The treatment liquid and ink set according to <8> above, wherein the content of the organic solvent having a boiling point of 290° C. or higher is 0.5% by mass or more and 5% by mass or less with respect to the total amount of the ink. .
<10> A treatment liquid application step of applying a treatment liquid containing a polyvalent metal salt and a resin to a substrate;
It contains a coloring material, an organic solvent with a boiling point of 290°C or higher, a silicone surfactant, and a resin, and the content of the organic solvent with a boiling point of 290°C or higher is 0.5% by mass or more relative to the total amount of the ink. an ink application step of applying the ink onto the treatment liquid;
A method for producing a printed matter, comprising:

The printing method according to any one of <1> to <7>, the setting of the treatment liquid and ink according to any one of <8> to <9>, and the method for producing a printed matter according to <10>. According to the above, various problems in the conventional art can be solved and the object of the present invention can be achieved.

400 Image forming apparatus 401 Exterior of image forming apparatus 401c Cover of apparatus main body 404 Cartridge holder 410 Main tank 410k, 410c, 410m, 410y For black (K), cyan (C), magenta (M), and yellow (Y) main tank 411 ink storage unit 413 ink discharge port 414 storage container case 420 mechanism unit 434 ejection head 436 supply tube

JP 2019-019187 A

Claims (10)

a treatment liquid application step of applying a treatment liquid containing a polyvalent metal salt and resin A to a substrate;
It contains a coloring material, an organic solvent with a boiling point of 290°C or higher, a silicone surfactant, and resin B, and the content of the organic solvent with a boiling point of 290°C or higher is 0.5% by mass with respect to the total amount of the ink. an ink application step of applying the above ink onto the treatment liquid;
A printing method comprising: The printing method according to claim 1, wherein the content of the organic solvent having a boiling point of 290°C or higher is 0.5% by mass or more and 5% by mass or less with respect to the total amount of the ink. The printing method according to any one of claims 1 and 2, wherein the content of the silicone-based surfactant is 0.1% by mass or more and 3% by mass or less with respect to the total amount of the ink. The printing method according to any one of claims 1 to 3, wherein the resin A contains at least one of urethane resin and acrylic resin. The printing method according to any one of claims 1 to 4, wherein the content of the resin A is 2% by mass or more and 10% by mass or less with respect to the total amount of the treatment liquid. 6. The printing method according to any one of claims 1 to 5, wherein the polyvalent metal salt contains at least one of calcium salt and magnesium salt. The printing method according to any one of claims 1 to 6, wherein the content of the polyvalent metal salt is 0.1% by mass or more and 3% by mass or less with respect to the total amount of the treatment liquid. a treatment liquid containing a polyvalent metal salt and a resin;
It contains a coloring material, an organic solvent with a boiling point of 290°C or higher, a silicone surfactant, and a resin, and the content of the organic solvent with a boiling point of 290°C or higher is 0.5% by mass or more relative to the total amount of the ink. and a set of treatment liquid and ink. 9. The treatment liquid and ink set according to claim 8, wherein the content of the organic solvent having a boiling point of 290[deg.] C. or higher is 0.5% by mass or more and 5% by mass or less with respect to the total amount of the ink. A treatment liquid application step of applying a treatment liquid containing a polyvalent metal salt and a resin to a substrate;
It contains a coloring material, an organic solvent with a boiling point of 290°C or higher, a silicone surfactant, and a resin, and the content of the organic solvent with a boiling point of 290°C or higher is 0.5% by mass or more relative to the total amount of the ink. an ink application step of applying the ink onto the treatment liquid;
A method for producing a printed matter, comprising:

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