JP2022086999A - Process liquid, method for producing printed material and device for producing printed material - Google Patents

Abstract

To provide a process liquid that improves the scratch resistance of an image and prevents the blurring of the image, while offering high storage stability and discharge stability.SOLUTION: A process liquid contains nonionic acrylic resin particles and a polyvalent metal salt. The nonionic acrylic resin particles have a volume average particle size of 100 nm or more and 300 nm or less. The content of the nonionic acrylic resin particles is more than 2.0 mass%. The average reflectance of light with a wavelength of 400 nm or more and 700 nm or less is 70% or more.SELECTED DRAWING: None

Description

The present invention relates to a treatment liquid, a method for producing a printed matter, and an apparatus for producing a printed matter.

In recent years, even in the fields of commercial printing and industrial printing, where analog printing such as offset printing and flexographic printing is the mainstream, the need for inkjet printers has increased as digital printing that can print a wide variety of designs in small quantities without the need for plates. There is.

In commercial printing, pamphlets, catalogs, posters, manuals, etc., and in industrial printing, labels, packages, textiles, corrugated cardboard, etc. are the main printing items.
Especially in the field of industrial printing, small-lot, high-mix designs are preferred and are used for product sales promotion.

In this way, when producing a wide variety of printed matter in small quantities by digital printing, various types of printed matter are handled as printing substrates, but the surface characteristics differ depending on the printing substrate, and the quality of the printed matter is affected. May affect.
Therefore, it is known to apply a pretreatment liquid that enhances the acceptability of ink to various substrates before applying the ink in order to produce printed matter of the same quality.
Further, the pretreatment liquid is required to have not only the appearance of the printed matter but also the ejection property of the pretreatment liquid itself in order to improve the scratch resistance of the image and to eject the pretreatment liquid by inkjet.

For example, it has been proposed to reduce the penetration of ink into the substrate and improve the color development property by using a pretreatment liquid (see, for example, Patent Document 1).

An object of the present invention is to provide a treatment liquid having excellent storage stability and ejection stability while improving the scratch resistance and bleeding prevention performance of an image.

The treatment liquid of the present invention as a means for solving the above-mentioned problems contains nonionic acrylic resin particles and a polyvalent metal salt, and the volume average particle diameter of the nonionic acrylic resin particles is 100 nm or more and 300 nm. The content of the nonionic acrylic resin particles is more than 2.0% by mass, and the average reflectance for a wavelength of 400 nm or more and 700 nm or less is 70% or more.

According to the present invention, it is possible to provide a treatment liquid having excellent storage stability and ejection stability while improving the scratch resistance and bleeding prevention performance of an image.

FIG. 1 is a perspective explanatory view showing an example of a printed matter manufacturing apparatus of the present invention. FIG. 2 is a perspective explanatory view showing an example of a main tank in the printed matter manufacturing apparatus of the present invention. FIG. 3 is a conceptual diagram showing an example of a printed matter manufacturing apparatus using the treatment liquid of the present invention.

(Treatment liquid)
The treatment liquid of the present invention contains nonionic acrylic resin particles and a polyvalent metal salt, and the volume average particle diameter of the nonionic acrylic resin particles is 100 nm or more and 300 nm or less, and the nonionic acrylic resin. The content of the particles is more than 2.0% by mass, the average reflectance for a wavelength of 400 nm or more and 700 nm or less is 70% or more, and if necessary, it contains a coloring material, water, and other components.
In the present invention, when the "treatment liquid" is used before image formation, it may be referred to as "pretreatment liquid" or the like.

In the conventional technique, the scratch resistance is insufficient when a strong load is applied, the image is peeled off from the base material, the image is bleeding, and as a result, a clear image cannot be obtained. was there.

As a result of diligent studies by the present inventors, the acrylic resin contains nonionic acrylic resin particles and a polyvalent metal salt, and the volume average particle diameter of the acrylic resin particles is 100 nm or more and 300 nm or less. By using a treatment liquid having a particle content of more than 2.0% by mass and an average reflectance of 70% or more for a wavelength of 400 nm or more and 700 nm or less, the scratch resistance and bleeding prevention performance of the image are improved. It has been found that a treatment liquid having excellent storage stability and discharge stability can be obtained.
Here, the "average reflectance" is calculated using a spectrophotometer (U-3900H, manufactured by Hitachi High-Tech Science Co., Ltd.) using a value measured by the treatment liquid under the following measurement conditions. Three measurement samples are prepared, and the average value of the measurement results of these measurement samples is taken as the average reflectance.
<Measurement conditions>
Measurement mode: Wavelength scan Data mode:% R
Starting wavelength: 800 nm
End wavelength: 200 nm
Scan speed: 300 nm / min
Sampling interval: 0.5 nm
Slit: 2 nm
The reflectance of the reflected light when irradiated with light having a wavelength of 400 nm or more and 700 nm was measured.

By applying the treatment liquid of the present invention to the substrate before applying the ink, the scratch resistance of the ink film can be improved. This is because the treatment liquid contains acrylic resin particles having a volume average particle diameter of 100 nm or more and 300 nm or less, which has the effect of improving the adhesion between the substrate and the ink film and smoothing the surface of the ink film. Further, from the viewpoint of adhesion to the substrate, the acrylic resin particles are contained in an amount of more than 2% by mass.
Further, by containing the polyvalent metal salt in the treatment liquid, the pigment in the ink is aggregated at the same time as the ink droplets land, so that bleeding between colors does not occur and a clear image can be obtained (image bleeding). Suppression).
Further, when the treatment liquid applied in advance is cloudy or colored, it affects the color appearance of the image formed by the ink film, so that the treatment liquid is required to have transparency. From this point of view, when the average reflectance of the treatment liquid with respect to light having a wavelength of 400 nm or more and 700 nm or less is 70% or more, an image with good color development can be obtained without giving dullness or turbidity to the image. Further, when the average reflectance is 70% or more, it means that the smoothness of the surface of the particles contained in the treatment liquid is high. Therefore, when the average reflectance is 70% or more, the effect of smoothing the surface of the formed ink film is high, and the scratch resistance can be improved.
Further, the storage stability is ensured because the acrylic resin particles in the treatment liquid are not the charge-repulsive type resin particles generally used but the nonionic resin particles dispersed by steric hindrance. It was found by the study of the present invention that in the case of anionic resin particles among the charge repulsion type, they instantly aggregate when mixed with a polyvalent metal salt. Furthermore, in the case of cationic resin particles, storage stability is sufficiently ensured when left at room temperature, but thickening is observed when the particles are allowed to stand under heating in an accelerated test in anticipation of long-term storage stability. It was found by the examination of the present inventions.

The average reflectance is 70% or more, preferably 80% or more and 100% or less, and more preferably 90% or more and 100% or less. When the average reflectance is 90% or more and 100% or less, a vivid image without dullness can be obtained.

<Nonionic acrylic resin particles>
The nonionic resin particles in the present invention refer to resin particles that can be dispersed by steric repulsion without utilizing electric charges by neutralizing acidic or basic functional groups.
Specifically, after isolating the solid content from the liquid composition by centrifugation, an acidic functional group such as a carboxyl group or a sulfo group, or an amino group is used by pyrolysis GC-MS (for example, GC-17A manufactured by Shimadzu Corporation). Refers to resin particles in which a monomer containing a basic functional group such as a group is not detected.

The nonionic acrylic resin particles in the present invention may be any as long as the chemical structure contains a polymer of an acrylic acid ester or a methacrylic acid ester, for example, a homopolymer containing an acrylic acid ester or a methacrylic acid ester. Examples thereof include nonionic acrylic resin particles containing a copolymer (block copolymer, random copolymer) and the like.
Examples of the homopolymer include acrylic resin particles.
Examples of the copolymer include styrene-acrylic resin particles, vinyl acetate-acrylic resin particles, silicone-acrylic resin particles, urethane-acrylic resin particles and the like.

The volume average particle diameter of the nonionic acrylic resin particles is 100 nm or more and 300 nm or less, preferably 100 nm or more and 250 nm or less, more preferably 100 nm or more and 200 nm or less, and further preferably 100 nm or more and 170 nm or less. When the volume average particle diameter of the nonionic acrylic resin particles is 100 nm or more and 170 nm or less, the scratch resistance can be further improved.
The volume average particle size of the nonionic acrylic resin particles can be measured using, for example, a particle size analyzer (Nanotrack Wave-UT151, manufactured by Microtrac Bell Co., Ltd.).

The content of the nonionic acrylic resin particles is more than 2% by mass, preferably more than 2% by mass and less than 15% by mass, and more preferably 3% by mass or more and 10% by mass or less, based on the total amount of the treatment liquid. It is more preferably 5% by mass or more and 8% by mass or less. When the content of the nonionic acrylic resin particles is 3% by mass or more and 10% by mass or less, the scratch resistance can be improved.

As the nonionic acrylic resin particles, those synthesized as appropriate may be used, or commercially available products may be used. Examples of the commercially available product include Vinibran 1225, Vinibran 1245L, Vinibran SS1008, Vinibran 2648, Vinibran 2685 (all manufactured by Nisshin Chemical Industry Co., Ltd.), AQ4790 (manufactured by Daicel FineChem Co., Ltd.) and the like.

<Multivalent metal salt>
By containing the polyvalent metal salt in the treatment liquid, the coloring material (for example, pigment) in the ink can be quickly aggregated after being dropped, color bleeding can be suppressed, and color development can be improved.

The arsenic 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)) and 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)), Zinc (Zr (IV)), Titanium (Ti (IV)) , Antimon (Sb (III)), Bismus (Bi (III)), Tantal (Ta (V)), Arsenic (As (III)), Cerium (Ce (III)), Lantern (La (III)), Zinc 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; benzenesulfonic acid , Naftor sulfonic acid, alkylbenzene sulfonic acid and other organic sulfonic acid ions; ^{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, titanium compound, chromium compound, copper compound, cobalt compound, strontium compound, barium compound, iron compound, aluminum compound and calcium. Examples include salts of compounds and magnesium compounds. Among these, salts with one or more selected from the group consisting of calcium compounds, magnesium compounds, nickel compounds, and aluminum compounds are preferable because they can effectively aggregate coloring materials (for example, pigments). Salts with alkaline earth metals such as calcium and magnesium are more preferred.
Specific examples of the polyvalent metal salt include calcium carbonate, calcium nitrate, calcium chloride, calcium acetate, calcium sulfate, magnesium chloride, magnesium acetate, magnesium sulfate, barium sulfate, zinc sulfide, zinc carbonate, aluminum silicate, and silicic acid. Calcium, magnesium silicate, aluminum hydroxide and the like can be mentioned.

The content of the polyvalent metal salt is preferably 1% by mass or more and 40% by mass or less, more preferably 2% by mass or more and 30% by mass or less, based on the total amount of the treatment liquid. When the content of the polyvalent metal salt is 2% by mass or more and 30% by mass or less, bleeding of the image is reduced and the sharpness of the image can be improved.

<Color material>
The coloring material 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 yellow pigment, a magenda pigment, a cyan pigment, a white pigment, a green pigment, an orange pigment, a bright color pigment such as gold or silver, a metallic pigment, or the like can be used.
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, or a thermal method. Black can be used.
Examples of the organic pigment include azo pigments, polycyclic pigments (for example, phthalocyanine pigments, perylene pigments, perinone pigments, anthraquinone pigments, quinacridone pigments, dioxazine pigments, indigo pigments, thioindigo pigments, isoindolinone pigments, quinophthalone pigments and the like. ), 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 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 Calcium 6B), 60: 1, 63: 1, 63: 2, 64: 1, 81, 83, 88, 101 (Bengara), 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 Greens 1, 4, 7, 8, 10, 17, 18, 36, etc.
The dye is not particularly limited, and acid dyes, direct dyes, reactive dyes, and basic dyes can be used, 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 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. Dilekdo 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.

The content of the coloring material is not particularly limited and may be appropriately selected depending on the intended purpose. It is preferably less than 0.1% by mass and 0.01% by mass or more with respect to the total amount of the treatment liquid. It is more preferably less than 1% by mass, more preferably 0.05% by mass or more and less than 0.1% by mass.

<Water>
The water is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include ion-exchanged water, ultrafiltration water, reverse osmosis water, pure water such as distilled water, and ultrapure water. .. These may be used alone or in combination of two or more.
The content of water in the treatment liquid is not particularly limited and may be appropriately selected depending on the intended purpose, but from the viewpoint of dryness and discharge reliability of the treatment liquid, it is 10% by mass or more and 90% by mass or less. It is preferably 20% by mass or more and 60% by mass or less, more preferably.

<Other ingredients>
The other components are not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include organic solvents, surfactants, antifoaming agents, antifungal preservatives and rust preventives.

<< Organic Solvent >>
The organic solvent 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-. Butanediol, 2,3-butanediol, 3-methyl-1,3-butanediol, triethylene glycol, polyethylene glycol, polypropylene glycol, 1,2-pentanediol, 1,3-pentanediol, 1,4-pentane Dire, 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 mono Polyhydric alcohol alkyl ethers such as ethyl ether, polyhydric alcohol aryl ethers such as ethylene glycol monophenyl ether and ethylene glycol monobenzyl ether, 2-pyrrolidone, N-methyl-2-pyrrolidone, N-hydroxyethyl-2- Nitrogen-containing heterocyclic compounds such as pyrrolidone, 1,3-dimethyl-2-imidazolidinone, ε-caprolactam, γ-butyrolactone, formamide, N-methylformamide, N, N-dimethylformamide, 3-methoxy-N, N -Amids 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, carbonic acid. Examples include ethylene.
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 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 drying property and discharge reliability of the treatment liquid. 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. Of these, 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 fluorosurfactant 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 as side chains. The polyoxyalkylene ether polymer compound having is particularly preferable because it has a small foaming property.
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, lauryldimethylbetaine, stearyldimethylbetaine, and lauryldihydroxyethylbetaine.
Examples of the nonionic surfactant include polyoxyethylene alkylphenyl ether, polyoxyethylene alkyl ester, polyoxyethylene alkylamine, polyoxyethylene alkylamide, polyoxyethylene propylene block polymer, sorbitan fatty acid ester, and polyoxyethylene. Examples thereof include sorbitan fatty acid ester and 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.

The content of the surfactant in the treatment liquid is not particularly limited and may be appropriately selected depending on the intended purpose. However, the total amount of the treatment liquid is excellent in terms of wettability and image quality. On the other hand, 0.001% by mass or more and 5% by mass or less is preferable, and 0.05% by mass or more and 5% by mass or less is more preferable.

<< Antifoaming agent >>
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.

<< Antiseptic and Antifungal Agent >>
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.

(Printed matter manufacturing method and printed matter manufacturing equipment)
The method for producing a printed matter of the present invention comprises a treatment liquid applying step of applying the processing liquid of the present invention to the base material, an ink applying step of applying ink containing a coloring material to the base material, and after applying the ink. It includes a drying step of drying the substrate, and further includes other steps as needed.
The printed matter manufacturing apparatus of the present invention comprises a treatment liquid applying means for applying the processing liquid of the present invention to the base material, an ink applying means for applying ink containing a coloring material to the base material, and after applying the ink. It has a drying means for drying the substrate, and further has other means as needed.
When the treatment liquid of the present invention is used as a pretreatment liquid to be used before image formation, the ink applying step of applying the ink containing the coloring material to the base material is the ink application to the base material to which the treatment liquid is applied. It becomes a process.
The ink applying step of applying the ink containing the coloring material to the base material includes applying the ink to the base material having a region to which the treatment liquid is applied, and applying the treatment liquid. In the base material having the region, the ink may be applied to the region to which the treatment liquid is not applied.

The method for producing a printed matter of the present invention can be suitably carried out by the printing matter manufacturing apparatus of the present invention, the treatment liquid applying step can be suitably carried out by the treatment liquid applying means, and the ink applying step can be carried out. The ink applying means can be suitably carried out, the drying step can be preferably carried out by the drying means, and the other steps can be preferably carried out by the other means.

<Treatment liquid application process and treatment liquid application means>
The treatment liquid application step is a step of applying the treatment liquid of the present invention to the substrate.
The treatment liquid applying means is a means for applying the treatment liquid of the present invention to a substrate.

The base material is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include recording media described later.

The treatment liquid application means is not particularly limited as long as the treatment liquid can be applied to the substrate, and can be appropriately selected depending on the intended purpose.
Examples of the method for applying the treatment liquid to the substrate include an inkjet method (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, and an air knife coating method. , Commer 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 method, curtain coat method, slide coat Examples include the law and the die coat method.
Among these, the inkjet method (method) is preferable. When coating by the inkjet method, it is particularly preferable because it can be uniformly applied over the entire substrate and the minimum required amount can be applied by adjusting the droplet size. Further, since the treatment liquid is uniformly applied to the surface of the substrate by the inkjet method, the acrylic resin particles and the polyvalent metal salt are uniformly present on the surface of the substrate without being unevenly distributed, so that the position in the plane of the substrate. There is no variation in scratch resistance and image sharpness. By doing so, a high quality image can be obtained.

The amount of the treatment liquid applied to the substrate is preferably 3 g / m ² or more and 20 g / m ² or less, and more preferably 6 g / m ² or more and 10 g / m ² or less. When the amount of the treatment liquid applied to the substrate is 3 g / m ² or more and 20 g / m ² or less, the scratch resistance is excellent and the effect of suppressing image bleeding can be improved.

<Ink applying process and ink applying means>
The ink applying step is a step of applying ink containing a coloring material to the base material.
The ink applying means is a step of applying ink containing a coloring material to the base material.

The ink applying means is not particularly limited and may be appropriately selected depending on the intended purpose.
For example, inkjet method (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, Examples thereof include a smoothing coat method, a microgravure coat method, a reverse roll coat method, a 4-roll coat method, a 5-roll coat method, a dip coat method, a curtain coat method, a slide coat method, and a die coat method.

[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. Dire, 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-caprolactum, nitrogen-containing heterocyclic compounds such as γ-butyrolactone, 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.

Polyol compounds having 8 or more carbon atoms and glycol ether compounds are also preferably used. Specific examples of the polyol compound having 8 or more carbon atoms include 2-ethyl-1,3-hexanediol and 2,2,4-trimethyl-1,3-pentanediol.
Specific examples of the glycol ether compound include polyhydric alcohol 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; Examples thereof include polyhydric alcohol aryl ethers such as ethylene glycol monophenyl ether and ethylene glycol monobenzyl ether.

The polyol compound having 8 or more carbon atoms and the glycol ether compound can improve the permeability of ink when paper is used as a recording medium.

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. , 20% by mass or more and 60% by mass or less are more preferable.

-water-
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 coloring material 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 yellow pigment, a magenda pigment, a cyan pigment, a white pigment, a green pigment, an orange pigment, a bright color pigment such as gold or silver, a metallic pigment, or the like can be used.
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, or a thermal method. Black can be used.
Examples of the organic pigment include azo pigments, polycyclic pigments (for example, phthalocyanine pigments, perylene pigments, perinone pigments, anthraquinone pigments, quinacridone pigments, dioxazine pigments, indigo pigments, thioindigo pigments, isoindolinone pigments, quinophthalone pigments and the like. ), 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 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 (Permanent Red 2B (Ca)), 48: 3, 48: 4, 49: 1, 52: 2, 53: 1, 57: 1 (Brilliant Carmin 6B), 60: 1, 63: 1, 63: 2, 64: 1, 81, 83, 88, 101 (Bengara), 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 Greens 1, 4, 7, 8, 10, 17, 18, 36, etc.
The dye is not particularly limited, and acid dyes, direct dyes, reactive dyes, and basic dyes can be used, 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 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. Dilekdo 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.

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 viewpoint of improving the image density, good fixing property and ejection stability. % Or less.

In order to disperse the pigment to obtain an ink, a method of introducing a hydrophilic functional group into the pigment to obtain a self-dispersing pigment, a method of coating the surface of the pigment with a resin and dispersing it, and a method of dispersing using a dispersant are used. How to make it, etc.
As a method of introducing a hydrophilic functional group into the pigment to obtain a self-dispersing pigment, for example, by adding a functional group such as a sulfone group or a carboxyl group to the pigment (for example, carbon), the pigment can be dispersed in water. The method can be mentioned.
Examples of the method of coating the surface of the pigment with a resin and dispersing the pigment include a method of encapsulating the pigment in microcapsules so that the pigment can be dispersed in water. This can be rephrased as a resin-coated pigment. In this case, it is not necessary that all the pigments blended in the ink are coated with the resin, and the uncoated pigments and the partially coated pigments are dispersed in the ink as long as the effect of the present invention is not impaired. May be.
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 represented by a surfactant.
As the dispersant, for example, an anionic surfactant, a cationic surfactant, an amphoteric surfactant, a nonionic surfactant and the like can be used depending on the pigment.
RT-100 (nonionic surfactant) manufactured by Takemoto Oil & Fat Co., Ltd. and a naphthalene sulfonic acid Na formalin condensate can also be suitably used as a dispersant.
The dispersant may be used alone or in combination of two or more.

-Pigment dispersion-
It is possible to obtain an ink by mixing a material such as water or an organic solvent with the pigment. It is also possible to produce an ink by mixing a material such as water or an organic solvent with a pigment dispersion obtained by mixing a pigment and other water or a dispersant.
The pigment dispersion is obtained by mixing and dispersing water, a pigment, a pigment dispersant, and other components as necessary, and adjusting the particle size. It is good to use a disperser for dispersion.
The particle size of the pigment in the pigment dispersion is not particularly limited, but the maximum frequency is 20 nm in terms of the maximum number because the dispersion stability of the pigment is good and the image quality such as ejection stability and image density is also high. It is preferably 500 nm or more, and more preferably 20 nm or more and 150 nm or less. The particle size of the pigment can be measured using a particle size analyzer (Nanotrack Wave-UT151, manufactured by Microtrac Bell Co., Ltd.).
The content of the pigment in the pigment dispersion is not particularly limited and may be appropriately selected depending on the intended purpose. However, good ejection stability can be obtained and the image density is increased by 0.1 mass. % Or more and 50% by mass or less are preferable, and 0.1% by mass or more and 30% by mass or less are more preferable.
It is preferable that the pigment dispersion is degassed by filtering coarse particles with a filter, a centrifuge, or the like, if necessary.

-resin-
The type of the resin contained in the ink is not particularly limited and may be appropriately selected depending on the intended purpose. For example, urethane-based resin, polyester-based resin, acrylic-based resin, vinyl acetate-based resin, styrene-based resin. , Butadiene resin, styrene-butadiene resin, vinyl chloride resin, acrylic styrene resin, acrylic silicone resin and the like.
Resin particles made of these resins may be used. It is possible to obtain ink by mixing resin particles with a material such as a coloring material or an organic solvent in the state of a resin emulsion in which water is used as a dispersion medium. As the resin particles, those synthesized as appropriate may be used, or commercially available products may be used. Further, these may be used alone or in combination of two or more kinds of resin particles.

The volume average particle diameter of the resin particles is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 10 nm or more and 1,000 nm or less from the viewpoint of obtaining good fixability and high image hardness. 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 size can be measured using, for example, a particle size analyzer (Nanotrack Wave-UT151, manufactured by Microtrack Bell Co., Ltd.).

The content of the resin is not particularly limited and may be appropriately selected depending on the intended purpose. However, from the viewpoint of fixability and storage stability of the ink, 1% by mass or more and 30% by mass with respect to the total amount of the ink. The following is preferable, and 5% by mass or more and 20% by mass or less is more preferable.

The particle size of the solid content in the ink is not particularly limited and can be appropriately selected according to the purpose, but from the viewpoint of improving image quality such as ejection stability and image density, the maximum frequency in terms of the maximum number of inks. Is preferably 20 nm or more and 1000 nm or less, and 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 Microtrac Bell Co., Ltd.).

-Additive-
If necessary, a surfactant, an antifoaming agent, an antiseptic / antifungal agent, a rust preventive agent, a pH adjuster and the like may be added to the ink.

--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. Of these, 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 fluorosurfactant 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 as side chains. The polyoxyalkylene ether polymer compound having is particularly preferable because it has a small foaming property. 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, lauryldimethylbetaine, stearyldimethylbetaine, and lauryldihydroxyethylbetaine.
Examples of the nonionic surfactant include polyoxyethylene alkylphenyl ether, polyoxyethylene alkyl ester, polyoxyethylene alkylamine, polyoxyethylene alkylamide, polyoxyethylene propylene block polymer, sorbitan fatty acid ester, and polyoxyethylene. Examples thereof include sorbitan fatty acid ester and 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.

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。）
上記のポリエーテル変性シリコーン系界面活性剤としては、市販品を用いることができ、例えば、ＫＦ－６１８、ＫＦ－６４２、ＫＦ－６４３（信越化学工業株式会社）、ＥＭＡＬＥＸ－ＳＳ－５６０２、ＳＳ－１９０６ＥＸ（日本エマルジョン株式会社）、ＦＺ－２１０５、ＦＺ－２１１８、ＦＺ－２１５４、ＦＺ－２１６１、ＦＺ－２１６２、ＦＺ－２１６３、ＦＺ－２１６４（東レ・ダウコーニング・シリコーン株式会社）、ＢＹＫ－３３、ＢＹＫ－３８７（ビックケミー株式会社）、ＴＳＦ４４４０、ＴＳＦ４４５２、ＴＳＦ４４５３（東芝シリコン株式会社）などが挙げられる。 The silicone-based surfactant is not particularly limited and may be appropriately selected depending on the intended purpose. For example, side chain-modified polydimethylsiloxane, double-ended modified polydimethylsiloxane, one-ended modified polydimethylsiloxane, side. Examples thereof include polydimethylsiloxane modified at both ends of the chain, and a polyether-modified silicone-based surfactant having a polyoxyethylene group or a polyoxyethylene polyoxypropylene group as a modifying group exhibits good properties as an aqueous surfactant, and is particularly effective. preferable.
As such a surfactant, an appropriately synthesized one may be used, or a commercially available product may be used. As commercially available products, for example, they can be obtained from Big Chemie Co., Ltd., Shin-Etsu Chemical Co., Ltd., Toray Dow Corning Silicone Co., Ltd., Nippon Emulsion Co., Ltd., Kyoeisha Chemical Co., Ltd. and the like.
The above-mentioned polyether-modified silicone-based surfactant is not particularly limited and may be appropriately selected depending on the intended purpose. For example, a polyalkylene oxide structure represented by the general formula (S-1) is dimethylpoly. Examples thereof include those introduced into the Si part side chain of siloxane.

General formula (S-1)
(However, in the general formula (S-1), m, n, a, and b each independently represent an integer, R represents an alkylene group, and R'represents an alkyl group.)
Commercially available products can be used as the above-mentioned polyether-modified silicone-based surfactant, for example, KF-618, KF-642, KF-643 (Shinetsu Chemical Industry Co., Ltd.), EMALEX-SS-5602, SS- 1906EX (Nippon Emulsion Co., Ltd.), FZ-2105, FZ-2118, FZ-2154, FZ-2161, FZ-2162, FZ-2163, FZ-2164 (Toray Dow Corning Silicone Co., Ltd.), BYK-33, BYK-387 (Big Chemie Co., Ltd.), TSF4440, TSF4452, TSF4453 (Toshiba Silicon Co., Ltd.) and the like can be mentioned.

一般式（Ｆ－１）
上記一般式（Ｆ－１）で表される化合物において、水溶性を付与するためにｍは０～１０の整数が好ましく、ｎは０～４０の整数が好ましい。
一般式（Ｆ－２）
Ｃ_ｎＦ_{２ｎ＋１－}ＣＨ_２ＣＨ（ＯＨ）ＣＨ_２－Ｏ－（ＣＨ_２ＣＨ_２Ｏ）_ａ－Ｙ
上記一般式（Ｆ－２）で表される化合物において、ＹはＨ、又はＣｍＦ_２ｍ＋１でｍは１～６の整数、又はＣＨ_２ＣＨ（ＯＨ）ＣＨ_２－ＣｍＦ_２ｍ＋１でｍは４～６の整数、又はＣｐＨ_２ｐ＋１でｐは１～１９の整数である。ｎは１～６の整数である。ａは４～１４の整数である。
上記のフッ素系界面活性剤としては市販品を使用してもよい。
この市販品としては、例えば、サーフロンＳ－１１１、Ｓ－１１２、Ｓ－１１３、Ｓ－１２１、Ｓ－１３１、Ｓ－１３２、Ｓ－１４１、Ｓ－１４５（いずれも、旭硝子株式会社製）；フルラードＦＣ－９３、ＦＣ－９５、ＦＣ－９８、ＦＣ－１２９、ＦＣ－１３５、ＦＣ－１７０Ｃ、ＦＣ－４３０、ＦＣ－４３１（いずれも、住友スリーエム株式会社製）；メガファックＦ－４７０、Ｆ－１４０５、Ｆ－４７４（いずれも、大日本インキ化学工業株式会社製）；ゾニール（Ｚｏｎｙｌ）ＴＢＳ、ＦＳＰ、ＦＳＡ、ＦＳＮ－１００、ＦＳＮ、ＦＳＯ－１００、ＦＳＯ、ＦＳ－３００、ＵＲ、キャプストーンＦＳ－３０、ＦＳ－３１、ＦＳ－３１００、ＦＳ－３４、ＦＳ－３５（いずれも、Ｃｈｅｍｏｕｒｓ社製）；ＦＴ－１１０、ＦＴ－２５０、ＦＴ－２５１、ＦＴ－４００Ｓ、ＦＴ－１５０、ＦＴ－４００ＳＷ（いずれも、株式会社ネオス社製）、ポリフォックスＰＦ－１３６Ａ，ＰＦ－１５６Ａ、ＰＦ－１５１Ｎ、ＰＦ－１５４、ＰＦ－１５９（オムノバ社製）、ユニダインＤＳＮ－４０３Ｎ（ダイキン工業株式会社製）などが挙げられ、これらの中でも、良好な印字品質、特に発色性、紙に対する浸透性、濡れ性、均染性が著しく向上する点から、Ｃｈｅｍｏｕｒｓ社製のＦＳ－３１００、ＦＳ－３４、ＦＳ－３００、株式会社ネオス社製のＦＴ－１１０、ＦＴ－２５０、ＦＴ－２５１、ＦＴ－４００Ｓ、ＦＴ－１５０、ＦＴ－４００ＳＷ、オムノバ社製のポリフォックスＰＦ－１５１Ｎ及びダイキン工業株式会社製のユニダインＤＳＮ－４０３Ｎが特に好ましい。 As the fluorine-based surfactant, a compound having 2 to 16 carbon atoms substituted with fluorine is preferable, and a compound having 4 to 16 carbon atoms substituted with fluorine is more preferable.
Examples of the fluorosurfactant include a perfluoroalkyl phosphate ester compound, a perfluoroalkyl ethylene oxide adduct, and a polyoxyalkylene ether polymer compound having a perfluoroalkyl ether group in the side chain. Among these, the polyoxyalkylene ether polymer compound having a perfluoroalkyl ether group in the side chain is preferable because it has less foaming property, and is particularly a fluorine-based compound represented by the general formula (F-1) and the general formula (F-2). Surfactants are preferred.

General formula (F-1)
In the compound represented by the general formula (F-1), m is preferably an integer of 0 to 10 and n is preferably an integer of 0 to 40 in order to impart water solubility.
General formula (F-2)
C _n F _{2n + 1-} CH ₂ CH (OH) CH ₂ -O- (CH ₂ CH ₂ O) _a -Y
In the compound represented by the above general formula (F-2), Y is H or CmF _{2m + 1} and m is an integer of 1 to 6, or CH ₂ CH (OH) CH ₂ -CmF _{2m + 1} and m is 4 to 6. It is an integer, or CpH _{2p + 1} and p is an integer of 1 to 19. n is an integer of 1 to 6. a is an integer of 4 to 14.
Commercially available products may be used as the above-mentioned fluorine-based surfactant.
Examples of this commercially available product include Surflon S-111, S-112, S-113, S-121, S-131, S-132, S-141, and S-145 (all manufactured by Asahi Glass Co., Ltd.); Full Lard FC-93, FC-95, FC-98, FC-129, FC-135, FC-170C, FC-430, FC-431 (all manufactured by Sumitomo 3M Co., Ltd.); Megafuck F-470, F -1405, F-474 (all manufactured by Dainippon Ink and Chemicals Co., Ltd.); Zonyl TBS, FSP, FSA, FSN-100, FSN, FSO-100, FSO, FS-300, UR, Capstone FS-30, FS-31, FS-3100, FS-34, FS-35 (all manufactured by Chemours); FT-110, FT-250, FT-251, FT-400S, FT-150, FT- 400SW (all manufactured by Neos Co., Ltd.), Polyfox PF-136A, PF-156A, PF-151N, PF-154, PF-159 (manufactured by Omniova), Unidyne DSN-403N (manufactured by Daikin Industries, Ltd.) Among these, FS-3100, FS-34, and FS- 300, FT-110, FT-250, FT-251, FT-400S, FT-150, FT-400SW manufactured by Neos Co., Ltd., Polyfox PF-151N manufactured by Omniova Co., Ltd. and Unidyne DSN manufactured by Daikin Kogyo Co., Ltd. -403N is particularly preferable.

The content of the surfactant in the ink is not particularly limited and may be appropriately selected depending on the intended purpose. However, 0.001 is obtained from the viewpoints of excellent wettability and ejection stability and improvement of image quality. It is preferably by mass% or more and 5% by mass or less, and more preferably 0.05% by mass or more and 5% by mass or less.

－－Antifoaming agent －－
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.

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

--PH regulator ---
The pH adjusting agent is not particularly limited as long as the pH can be adjusted to 7 or more, and examples thereof include amines such as diethanolamine and triethanolamine.

The physical characteristics of the ink are not particularly limited and may be appropriately selected depending on the intended purpose. For example, the viscosity, surface tension, pH and the like are preferably in the following ranges.
The viscosity of the ink at 25 ° C. is preferably 5 mPa · s or more and 30 mPa · s or less, 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, for the viscosity, for example, a rotary viscometer (RE-80L manufactured by Toki Sangyo Co., Ltd.) can be used. As the measurement conditions, it is possible to measure at 25 ° C. with a standard cone rotor (1 ° 34'× R24), a sample liquid volume of 1.2 mL, a rotation speed of 50 rpm, and 3 minutes.
The surface tension of the ink is preferably 35 mN / m or less, and more preferably 32 mN / m or less at 25 ° C. from the viewpoint that the ink is preferably leveled on the recording medium and the drying time of the ink is shortened.
The pH of the ink is preferably 7 to 12, and more preferably 8 to 11 from the viewpoint of preventing corrosion of the metal member that comes into contact with the liquid.

[recoding media]
The recording medium used for recording is not particularly limited, and examples thereof include plain paper, glossy paper, special paper, cloth, film, transparency sheet, and general-purpose printing paper.

The recording medium is not limited to that used as a general recording medium, and wallpaper, flooring, building materials such as tiles, cloth for clothing such as T-shirts, textiles, leather and the like can be appropriately used. Further, ceramics, glass, metal, or the like can be used by adjusting the configuration of the path for transporting the recording medium.

[Recorded material]
The ink recording material of the present invention comprises an image formed by using the ink of the present invention on a recording medium.
It can be recorded by an inkjet recording device and an inkjet recording method to obtain a recorded material.

[Recording device, recording method]
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 of recording using the device. The recording medium means a medium to which ink and various treatment liquids can adhere even temporarily.
This recording device may 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 by the member L. 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 device and the posttreatment device, 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 ink jet 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.

FIG. 3 is a schematic view showing an example of a printed matter manufacturing apparatus using the treatment liquid of the present invention. The printed matter manufacturing apparatus 100 shown in FIG. 3 has a processing liquid applying means 111 and an ink applying means 121. The printed matter manufacturing apparatus 100 may further be provided with the drying means 131.
In the printed matter manufacturing apparatus 100 shown in FIG. 3, by transporting the recording medium 201 by the transport belt 301 in the direction of the arrow in FIG. 3, the treatment liquid application means 111 can perform the treatment liquid application step, and the ink application can be performed. The ink applying step can be performed by the means 121, and the drying step can be performed by the drying means 131.

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.

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, paint, coating material, base material 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.

<Drying process and drying means>
The drying step is a step of drying the base material after applying the ink.
The drying means is a means for drying the base material after applying the ink.

The drying means is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include an IR (far infrared ray) drying device, a drying oven, and a hot plate. Among these, an IR (far infrared) drying device is preferable. When the drying means is an IR (far-infrared) drying device, the nonionic acrylic resin particles in the treatment liquid are directly heated by IR heating, film formation occurs, and the substrate, the treatment liquid layer, and the ink film adhere to each other. The strength is increased and the scratch resistance can be improved.

The drying temperature in the drying step is not particularly limited and may be appropriately selected depending on the intended purpose, and is preferably 50 ° C. or higher and 200 ° C. or lower. The drying temperature may be the set temperature of the drying means used in the drying step, and examples thereof include a temperature when the temperature of the base material is measured in contact or non-contact.
The drying time in the drying step is not particularly limited and may be appropriately selected depending on the intended purpose, and is preferably 0.01 minutes or more and 1 minute or less.

<Other processes and other means>
The other steps are not particularly limited and may be appropriately selected depending on the intended purpose.
The other means are not particularly limited and may be appropriately selected depending on the intended purpose.

Hereinafter, examples of the present invention will be described, but the present invention is not limited to these examples. In the following examples, unless otherwise specified, the treatment liquid and the ink were prepared and evaluated under the conditions of room temperature of 25 ° C. and humidity of 60% RH.

<Preparation of resin particle dispersion liquid 1>
45 parts by mass of styrene, 50 parts by mass of 2-ethylhexyl acrylate, 3 parts by mass of Emulgen 985 (manufactured by Kao Co., Ltd.), 2.75 parts by mass of VA-086 (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.), 52 parts by mass of ion-exchanged water. The mixture consisting of parts was emulsified using a homomixer to obtain a uniform milky white emulsion.
In a 250 mL flask equipped with a stirrer, a thermometer, a nitrogen gas introduction tube, and a reflux tube, 58 parts by mass of ion-exchanged water and 2 parts by mass of Emulgen 920 (manufactured by Kao Co., Ltd.) were charged, and 5 parts by mass of styrene was further added. And stirred to obtain an emulsified and dispersed liquid. The temperature was raised to 70 ° C. while introducing nitrogen into the flask, and 0.25 parts by mass of VA-086 was added to initiate polymerization. After 1 hour from the start of the polymerization, the temperature of the system was raised to 80 ° C., and then the emulsion prepared in advance was continuously added dropwise over 3 hours. After aging at 70 ° C. for 2 hours after completion of the dropping, the residual monomer was removed by a conventional method, and then the solid content concentration was adjusted to 35% by mass to obtain a resin particle dispersion liquid 1. The volume average particle diameter of the obtained resin particles was 200 nm. The volume average particle diameter of the resin particles was measured using a particle size analyzer (Nanotrack Wave-UT151, manufactured by Microtrac Bell Co., Ltd.).

<Preparation of resin particle dispersion liquid 2>
In the production of the resin particle dispersion liquid 1, the resin particle dispersion liquid 2 was obtained in the same manner except that the amount was 985 parts by mass of Emargen. The volume average particle diameter of the obtained resin particles was 100 nm.

<Preparation of resin particle dispersion liquid 3>
In the production of the resin particle dispersion liquid 1, the resin particle dispersion liquid 3 was obtained in the same manner except that the amount was 985 by mass of Emargen 985. The volume average particle diameter of the obtained resin particles was 300 nm.

<Preparation of resin particle dispersion liquid 4>
In the production of the resin particle dispersion liquid 1, the resin particle dispersion liquid 4 was obtained in the same manner except that the emulsion was added dropwise over 4.5 hours as 5 parts by mass of Emargen 985. The volume average particle diameter of the obtained resin particles was 70 nm.

<Preparation of resin particle dispersion liquid 5>
In the production of the resin particle dispersion liquid 1, the resin particle dispersion liquid 5 was obtained in the same manner except that the amount was 0.75 parts by mass of Emargen 985. The volume average particle diameter of the obtained resin particles was 350 nm.

[Preparation of treatment liquid 1]
The treatment liquid 1 was prepared with the following composition, mixed and stirred, and filtered through a 5 μm filter (Mini-Sart from Sartorius).
・ 1,2-Propanediol: 20 parts by mass ・ Ethylene glycol monobutyl ether: 10 parts by mass ・ Emargen LS-106 (manufactured by Kao Co., Ltd., surfactant): 0.5 parts by mass ・ Magnesium sulfate: 2 parts by mass ・ Resin Particle dispersion 1: 3 parts by mass, Proxel LV (Abyssia preservative) :: 0.1 parts by mass, ion-exchanged water: 64.4 parts by mass Average reflectance of the treated liquid 1 after filtration at a wavelength of 400-700 nm Was 95%. For the average reflectance, use a spectrophotometer (U-3900H, manufactured by Hitachi High-Tech Science Co., Ltd.), dilute the sample 1,000 times with ion-exchanged water, and measure the sample three times under the following measurement conditions. Calculated.
<Measurement conditions>
Measurement mode: Wavelength scan Data mode:% R
Starting wavelength: 800 nm
End wavelength: 200 nm
Scan speed: 300 nm / min
Sampling interval: 0.5 nm
Slit: 2 nm
The reflectance of the reflected light when irradiated with light having a wavelength of 400 nm or more and 700 nm was measured.

[Preparation of treatment liquids 2 to 16]
Treatment liquids 2 to 16 were prepared based on the formulations shown in Tables 1 and 2. The numerical values in the table indicate mass%.

The contents of each component shown in Tables 1 and 2 are as follows.
-Multivalent metal salt-
・ Magnesium sulfate (Mg sulfate): manufactured by Nakaraitesk Co., Ltd. ・ Magnesium acetate (Mg acetate): manufactured by Nakaraitesk Co., Ltd. ・ Calcium carbonate (Ca carbonate): manufactured by Nakaraitesk Co., Ltd. Company-manufactured by calcium acetate (Ca acetate): Nakaraitesk Co., Ltd.-Calcium silicate (Al silicate): manufactured by Nichias Co., Ltd.-Aluminum hydroxide (Al hydroxide): manufactured by Tomoe Kogyo Co., Ltd.-Facial active agent-
-Polyoxyalkylene alkyl ether: Emargen LS-106, Kao Co., Ltd.-Silicone-based surfactant: BYK-333, Tetsutani Co., Ltd.-siloxane surfactant: TEGO-WET-270, Ebonic Co., Ltd.-siloxane surfactant Agent: TEGO-WET-280, Ebonic-Acetylene Glycol Surfactant: Surfinol 420, Nissin Chemical Industry Co., Ltd.-Acetylene Glycol Surfactant: Surfinol PSA336, Nissin Chemical Industry Co., Ltd.-Acetylene Glycol Surfactant: Surfinol 440, manufactured by Nissin Chemical Industry Co., Ltd. ・ Fluorine-based surfactant: FS-300, manufactured by Sigma Aldrich Co., Ltd.-Acrylic resin-
-Nonionic acrylic resin particles: Vinibran 1225, manufactured by Nisshin Chemical Industry Co., Ltd.-Nonionic acrylic resin particles: Vinibran 1245L, manufactured by Nisshin Chemical Industry Co., Ltd.-Anionic acrylic resin particles: Cybinol SK-200, Saiden Made by Chemical Co., Ltd. ・ Cationic acrylic resin particles: Viniblanc 2678, manufactured by Nissin Chemical Industry Co., Ltd.-Organic solvent-
・ 1,2-Propanediol ・ 1,3-Butanediol ・ Ethylene glycol monobutyl ether ・ 3-Methoxy-3-monomethyl-1-butanol-Dye-
・ Blue No. 1: Asako Fragrance Chemical Co., Ltd.-Antibacterial agent-
・ Proxel LV: Made by Lonza

<Preparation Example 1 of Pigment Dispersion Liquid>
<< Preparation of Black Pigment Dispersion >>
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 with a diameter of 0.3 mm) to disperse the black pigment dispersion (pigment concentration). : 15% by mass) was obtained.
-Carbon black pigment (trade name: Monarch800, manufactured by Cabot): 15 parts by mass-Acrylic polymer dispersant Disperbyk-2010 (manufactured by BYK Japan): 5 parts by mass-Ion-exchanged water: 80 parts by mass

<Preparation Example 2 of Pigment Dispersion Liquid>
<< Preparation of cyan pigment dispersion >>
Cyan pigment dispersion (pigment solid content concentration: 15% by mass) in the same manner as in Preparation Example 1 of the pigment dispersion except that the carbon black pigment was changed to Pigment Blue 15: 3 in Preparation Example 1 of the pigment dispersion. ) Was obtained.

<Preparation Example 3 of Pigment Dispersion Liquid>
<< Preparation of Magenta Pigment Dispersion >>
In Preparation Example 1 of the pigment dispersion, a magenta pigment dispersion (pigment solid content concentration: 15% by mass) was used in the same manner as in Preparation Example 1 of the pigment dispersion except that the carbon black pigment was changed to Pigment Red 269. Obtained.

<Preparation Example 4 of Pigment Dispersion Liquid>
<< Preparation of yellow pigment dispersion >>
In Preparation Example 1 of the pigment dispersion, a yellow pigment dispersion (pigment solid content concentration: 15% by mass) was used in the same manner as in Preparation Example 1 of the pigment dispersion except that the carbon black pigment was changed to Pigment Yellow 74. Obtained.

[Preparation of ink 1]
The following formulations were mixed and stirred, and filtered through a polypropylene filter having an average pore size of 0.8 μm to prepare ink 1.
・ Black pigment dispersion: 20 parts by mass ・ Surfinol 420 (manufactured by Evonik, nonionic surfactant): 0.5 parts by mass ・ Superflex 210 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.): 6 parts by mass ・ Proxel LV (Made by Abyssia, preservative): 0.1 parts by mass, 1,2-propanediol: 15 parts by mass, ethylene glycol monobutyl ether: 10 parts by mass, ion-exchanged water: 48.4 parts by mass

[Preparation of inks 2-9]
Inks 2-9 were prepared based on the formulations shown in Table 3. The numerical values in the table indicate mass%.

The contents of each component shown in Table 3 are as follows.
-Surfactant-
・ Acetylene glycol surfactant: Surfinol 420, manufactured by Nisshin Chemical Industry Co., Ltd. ・ Acetylene glycol surfactant: Surfinol PSA336, manufactured by Nisshin Chemical Industry Co., Ltd. ・ Acetylene glycol surfactant: Surfinol 440, Nisshin Chemical Co., Ltd. Acetylene glycol surfactant manufactured by Kogyo Co., Ltd .: Surfinol 465, acetylene glycol surfactant manufactured by Nisshin Chemical Industry Co., Ltd .: Surfinol 485, siloxane surfactant manufactured by Nisshin Chemical Industry Co., Ltd .: TEGO-WET- 270, Ebonic, Fluorosurfactant: FS-300, Sigma Aldrich-Binder Resin-
-Urethane resin: Superflex 210 (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.)
-Acrylic resin: Boncoat CF-6140 (manufactured by DIC Corporation)
-Styrene acrylic resin: Viniblanc 2685 (manufactured by Nissin Chemical Industry Co., Ltd.)
-Vinyl chloride resin: Viniblanc 735 (manufactured by Nissin Chemical Industry Co., Ltd.)
-Polyester resin: Elitel KA-5034 (manufactured by Unitika Ltd.)
-Organic solvent-
・ 1,2-Propanediol ・ 1,3-Butanediol ・ 1,3-Propanediol ・ Glycerin ・ Ethylene glycol monobutyl ether ・ 3-methoxy-3-monomethyl-1-butanol ・ Dipropylene glycol monomethyl ether-Antibacterial agent-
・ Proxel LV: Made by Lonza

Next, using each of the obtained treatment liquids and inks, "storage stability", "ejection stability", "scratch resistance", and "image bleeding" were evaluated as follows. The results are shown in Tables 4 to 6.

<Evaluation of storage stability of treatment liquid>
The prepared treatment liquid was placed in a closed container and allowed to stand in a constant temperature bath at 60 ° C. for 1 week, and the storage stability of the treatment liquid was evaluated based on the following evaluation criteria from the change in viscosity before and after storage. A and B were set as the allowable range.
[Evaluation criteria]
A: The viscosity change rate is within 5%.
B: The viscosity change rate is more than 5% and within 10%.
C: The viscosity change rate is more than 10% and within 20%.
D: The rate of change in viscosity exceeds 20%, or agglomerates are generated.

<Evaluation of discharge stability of treatment liquid>
The prepared treatment liquid was filled in an inkjet printer (device name: IPSiO GXe5500 remodeling machine, manufactured by Ricoh Co., Ltd.), and the ejection stability after decapping was evaluated.
First, in an environment of 25 ° C. and 30% RH, head cleaning was executed from the printer maintenance command, and a test chart was printed to confirm that all channels of the nozzle were in the ejection state.
Next, after leaving the head cap removed for 5 minutes, the test chart was printed again. The number of non-ejection channels was counted from the test chart before and after leaving, and the judgment was made according to the following criteria. It should be noted that it is suitable for practical use when the number of non-ejection channels is less than 10 (evaluations A and B).
[Evaluation criteria]
A: Number of non-discharge channels is 1 or less B: Number of non-discharge channels is 2 or more and less than 10 C: Number of non-discharge channels is 10 or more

<Scratch resistance evaluation>
The prepared treatment liquid is coated with a white ball JET STAR (tsubo) so that the adhesion amount (g / m ² ) shown in Tables 3 to 5 is obtained by an inkjet method using Ricoh IPSiO GXe5500 or a method using a bar coater. After coating on an amount of 270 g / m ² , manufactured by Nippon Paper Industries, Ltd., it was dried at 70 ° C. for 2 minutes.
Another Ricoh IPSiO GXe5500 was filled with the prepared ink, and a solid image of the ink was printed on the dried substrate and dried at 70 ° C. for 2 minutes.
A dry cotton (Kanakin No. 3) cut into 6 cm ² was rubbed 100 times back and forth with a load of 400 g on the solid image, and the scratch resistance was visually judged according to the following evaluation criteria. The evaluations A and B were set as the allowable range.
[Evaluation criteria]
A: The image density does not change even after rubbing 100 times or more B: Some scratches remain after rubbing 100 times, but it does not affect the image density C: The image density decreases while rubbing 100 times D: Image density decreases after scratching 50 times or less

<Evaluation of image bleeding (collapsed negative characters)>
The prepared treatment liquid is coated with a white ball JET STAR (tsubo) so that the adhesion amount (g / m ² ) shown in Tables 3 to 5 is obtained by an inkjet method using Ricoh IPSiO GXe5500 or a method using a bar coater. After coating on an amount of 270 g / m ² , manufactured by Nippon Paper Industries, Ltd., it was dried at 70 ° C. for 2 minutes.
Another Ricoh IPSiO GXe5500 was filled with the prepared ink, and a Gothic white character chart was printed on the dried substrate and dried at 70 ° C. for 2 minutes.
The readability of the characters in the obtained image was visually judged and evaluated according to the following evaluation criteria. Evaluations A and B were set as the allowable range.
[Evaluation criteria]
A: 3pt Gothic is readable B: 3pt is unreadable but 4pt is readable C: 4pt is unreadable but 5pt is readable D: 5pt is unreadable

Examples of aspects of the present invention are as follows.
<1> Containing nonionic acrylic resin particles and a multivalent metal salt,
The volume average particle diameter of the nonionic acrylic resin particles is 100 nm or more and 300 nm or less.
The content of the nonionic acrylic resin particles is more than 2.0% by mass, and the content is more than 2.0% by mass.
It is a treatment liquid characterized by having an average reflectance of 70% or more for a wavelength of 400 nm or more and 700 nm or less.
<2> The treatment liquid according to <1>, wherein the content of the nonionic acrylic resin particles is 3% by mass or more and 10% by mass or less.
<3> Further contains a coloring material,
The treatment liquid according to any one of <1> to <2>, wherein the content of the coloring material is less than 0.1% by mass.
<4> The treatment liquid application step of applying the treatment liquid according to any one of <1> to <3> to the substrate, and the treatment liquid application step.
An ink applying step of applying ink containing a coloring material to the base material, and
A method for producing a printed matter, which comprises a drying step of drying the substrate after applying the ink.
<5> The method for producing a printed matter according to <4>, wherein the ink is applied to the substrate by an inkjet method.
<6> The method for producing a printed matter according to any one of <4> to <5>, wherein the treatment liquid is applied to the substrate by an inkjet method.
<7> The method for producing a printed matter according to any one of <4> to <6>, wherein the amount of the treatment liquid applied to the substrate is 3 g / m ² or more and 20 g / m ² or less.
<8> The method for producing a printed matter according to any one of <4> to <7>, wherein the drying in the drying step is IR (far infrared) drying.
<9> The treatment liquid applying means for applying the treatment liquid according to any one of <1> to <3> to the substrate, and the treatment liquid application means.
An ink applying means for applying ink containing a coloring material to the base material,
It is an apparatus for producing a printed matter, which comprises a drying means for drying the base material after applying the ink.

According to the treatment liquid according to any one of <1> to <3>, the method for producing a printed matter according to any one of <4> to <8>, and the printed matter manufacturing apparatus according to <9>. , The conventional problems can be solved and the object of the present invention can be achieved.

100 Printed matter manufacturing equipment 111 Processing liquid application means 121 Ink application means 131 Drying means 201 Recording medium 301 Conveyance belt 400 Image formation device 401 Image formation device exterior 401c Device body cover 404 Cartridge holder 410 Main tank 410k, 410c, 410m, 410y Main tank for each color of black (K), cyan (C), magenta (M), yellow (Y) 411 Ink storage unit 413 Ink discharge port 414 Storage container case 420 Mechanical unit 434 Discharge head 436 Supply tube

Japanese Unexamined Patent Publication No. 2019-11528

Claims (9)

Contains nonionic acrylic resin particles and a multivalent metal salt,
The volume average particle diameter of the nonionic acrylic resin particles is 100 nm or more and 300 nm or less.
The content of the nonionic acrylic resin particles is more than 2.0% by mass, and the content is more than 2.0% by mass.
A treatment liquid having an average reflectance of 70% or more for a wavelength of 400 nm or more and 700 nm or less. The treatment liquid according to claim 1, wherein the content of the nonionic acrylic resin particles is 3% by mass or more and 10% by mass or less. It also contains coloring material,
The treatment liquid according to any one of claims 1 to 2, wherein the content of the coloring material is less than 0.1% by mass. The process of applying the treatment liquid according to any one of claims 1 to 3 to the substrate, and the treatment liquid application step.
An ink applying step of applying ink containing a coloring material to the base material, and
A method for producing a printed matter, which comprises a drying step of drying the substrate after applying the ink. The method for producing a printed matter according to claim 4, wherein the ink is applied to the substrate by an inkjet method. The method for producing a printed matter according to any one of claims 4 to 5, wherein the treatment liquid is applied to the substrate by an inkjet method. The method for producing a printed matter according to any one of claims 4 to 6, wherein the amount of the treatment liquid applied to the substrate is 3 g / m ² or more and 20 g / m ² or less. The method for producing a printed matter according to any one of claims 4 to 7, wherein the drying in the drying step is IR (far infrared) drying. A treatment liquid applying means for applying the treatment liquid according to any one of claims 1 to 3 to a base material,
An ink applying means for applying ink containing a coloring material to the base material,
A printed matter manufacturing apparatus comprising: a drying means for drying the substrate after applying the ink.

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