JP7069741B2 - Recording method and recording device - Google Patents

Description

The present invention relates to a recording method and a recording device.

In printing for industrial use, a method of ejecting water-based ink onto a non-permeable substrate such as a film by an inkjet recording method to form an image is known. In such a recording method using water-based ink, the water-based ink is more likely to be repelled on the impermeable substrate than in the recording method using non-water-based ink. Therefore, there is a problem that an image cannot be formed and a problem that color unevenness occurs in the formed image.

In Patent Document 1, the surface modification of the recording surface of a recording medium having low ink absorption or non-absorption of ink is performed to solve the above-mentioned problems, and the wet tension index of the recording surface is 40 mN / m or more. For inkjet recording, which contains a reaction liquid adhering step of adhering a reaction liquid containing a flocculant to a recording surface after a step, a surface modification step, and a coloring material and water after the reaction liquid adhering step. It is disclosed that an image is formed by a recording method including an image recording step of recording an image on a recording surface using an ink composition.

However, when a large amount of ink is continuously printed on a non-permeable substrate, the conventional recording method is inferior in wetting and spreading of the ink to the recording medium, and the ink dries in the nozzle during long-term printing. Therefore, there is a problem that streaks in the image occur due to insufficient wet spread and poor ejection.

The invention according to claim 1 is a recording method in which an ink containing a coloring material and water is applied from an ink applying means, and a surface treatment layer containing a polyvalent metal compound and a resin is formed on a non-permeable substrate. An ink that applies the ink to the surface treatment layer from the ink application means after the surface treatment layer forming step, the humidification step of humidifying between the ink application means and the surface treatment layer by the humidification means, and the humidification step. The humidifying step is a step of adjusting the relative humidity between the ink applying means and the surface treatment layer to 65% RH or more and 90% RH or less, and the surface treatment layer forming step is a step. , Water, the polyvalent metal compound, and a surface treatment liquid containing the resin are applied to the impermeable substrate and then dried to form the surface treatment layer. The ink application means is a line. A type of inkjet ejection means, the inkjet ejection means vibrates the interface of the ink in the nozzle in a nozzle that does not eject the ink, the polyvalent metal compound contains calcium acetate, and the resin is acetic acid . The humidifying means , which comprises a vinyl-acrylic resin, is a recording method provided on the upstream side of the ink applying means with respect to the transport direction of the impermeable base material.

The recording method of the present invention has the effect of suppressing streaks generated in an image when printed for a long time.

FIG. 1 is a schematic side view showing a recording device according to an embodiment of the present invention. FIG. 2 is a schematic side view showing the recording device used in the seventh embodiment.

<< Recording device >>
In the present application, the recording device is a humidifying means for humidifying between a surface treatment layer forming means for forming a surface treatment layer containing a polyvalent metal compound and a resin on an impermeable substrate, an ink applying means, and the surface treatment layer. And an ink applying means for applying an ink containing a coloring material and water to the surface treatment layer from the ink applying means. Further, the recording device can also include means for supplying, transporting, and discharging the impermeable base material, as well as a pretreatment device, a posttreatment device, a drying device, and the like, if necessary.

A recording device according to an embodiment of the present invention will be described with reference to FIG. FIG. 1 is a schematic side view showing a recording device according to an embodiment of the present invention. The recording device 100 shown in FIG. 1 is a full-line type (hereinafter, also referred to as “line type”) inkjet recording device. The recording device 100 includes an unwinding device 101, an impermeable base material 102, a corona treatment device 103, a surface treatment liquid applying device 104, a surface treatment liquid drying device 105, a humidifying device 106, and an inkjet ejection head 107. A platen 108, an ink drying device 109, and a winding device 110.

<Unwinding means>
The unwinding device 101 is rotationally driven to supply the impermeable base material 102 housed in a roll shape to the transport path in the recording device 100.

The impermeable base material 102 is a film-like base material that is continuous in the transport direction of the recording device, and is transported along a transport path between the unwinding device 101 and the winding device 110. Further, the length of the impermeable base material 102 in the transport direction is at least longer than the length of the transport path of the impermeable base material 102 provided between the unwinding device 101 and the winding device 110. Since the substrate that is continuous in the transport direction of the recording device is used in this way, the recording device of the present application continuously prints for a long time.

<Corona processing means>
The corona processing device 103 performs corona discharge on the impermeable base material 102 to modify the surface of the impermeable base material 102. As the means for performing the corona treatment, various known means can be used.

The surface treatment liquid applying device 104 rotationally drives the roller to which the surface treatment liquid is attached so as to come into contact with the impermeable base material 102, and applies the surface treatment liquid to the surface of the impermeable base material 102. The means for applying the surface treatment liquid is not limited to the means for bringing the roller to which the surface treatment liquid is attached into contact with the impermeable base material 102, and for example, spin coating, spray coating, gravure roll coating, reverse roll coating, etc. Various known means such as bar coat and inkjet can be used.

<Surface treatment liquid drying means>
The surface treatment liquid drying device 105 blows warm air onto the surface treatment liquid applied to the surface of the impermeable base material 102 to dry the surface treatment liquid to form a surface treatment layer. The means for drying the surface treatment liquid is not limited to the means for blowing warm air, and for example, various known means such as a means for contacting the back surface of the impermeable base material 102 with a heating roller, a flat heater, or the like to dry the surface treatment liquid. Can be used.

<Humidification means>
The humidifying device 106 humidifies between the inkjet ejection head 107 and the surface treatment layer provided on the impermeable substrate 102. As a result, the vicinity of the inkjet ejection head 107, more specifically, the vicinity of the nozzle provided in the inkjet ejection head 107, and more specifically, the inside of the nozzle provided in the inkjet ejection head 107 is humidified. Further, the vicinity of the impermeable base material 102, more specifically, the vicinity of the surface treatment layer provided on the impermeable base material 102 is humidified. It is air that the humidifying device 106 humidifies.
The humidifying device 106 is provided at a position away from the inkjet discharge head 107 and the impermeable base material 102, and the humidified air is discharged to the inkjet discharge head 107 and the surface treatment layer provided on the impermeable base material 102. And supply between. In other words, the humidifying device 106 supplies humidified air to the inkjet ejection head 107 and the surface treatment layer provided on the impermeable substrate 102. The position of the humidifying device 106 is between the inkjet ejection head 107 and the surface treatment layer provided on the impermeable substrate 102, at a position adjacent to the inkjet ejection head 107, and the entire printing apparatus is humidified. The position where it can be performed is mentioned, but it is not particularly limited.
Further, the humidifying means humidifies the inside of the space including the nozzle provided in the inkjet ejection head 107 and the impermeable base material 102 and substantially surrounded by the members constituting the recording device. It is preferably a means (hereinafter, a humidified space surrounded by a member so as to include a nozzle provided in the inkjet ejection head 107 and a non-permeable base material 102 is also referred to as a “humidifying region”). Even if the member forming the humidified region is provided with an opening in which the impermeable base material 102 is introduced into the humidified region, an opening in which the impermeable base material 102 is discharged from the humidified region, or the like. Often, even in such cases, the humidified area shall be "substantially surrounded" by the members constituting the recording device.
Examples of the humidifying device 106 include a means for spraying water as a mist, a means for generating water vapor, a means for blowing air near the nozzle while generating mist and water vapor, and the like, specifically, a steam type, a fan type, and the like. Various known humidifying devices such as an ultrasonic type can be used.

<Ink applying means>
The inkjet ejection head 107 has a plurality of nozzle rows in which a plurality of nozzles are arranged, and is provided so that the ink ejection direction from the nozzles faces the transport path of the impermeable base material 102. As a result, the inkjet ejection head 107 sequentially ejects liquids of each color of magenta (M), cyan (C), yellow (Y), and black (K) onto the surface treatment layer on the impermeable substrate 102. .. The color of the ejected ink is not limited to these, and may be a color such as white, gray, silver, gold, green, blue, orange, or violet.
Further, the inkjet ejection head 107 is a line-type inkjet ejection head, and the “line-type inkjet ejection head” is provided with nozzles for ejecting ink over the entire width in the transport direction of the impermeable substrate 102. It is an inkjet ejection head. The inkjet ejection head is not limited to the line type, but may be a serial type.
Further, in the inkjet ejection head 107, the means for applying a stimulus to the ink to eject the ink can be appropriately selected depending on the intended purpose, for example, a pressurizing device, a piezoelectric element, a vibration generator, an ultrasonic oscillator, and the like. Lights and the like. Specific examples thereof include piezoelectric actuators such as piezoelectric elements, shape memory alloy actuators that use metal phase changes due to temperature changes, and electrostatic actuators that use electrostatic force. Among these, in particular, by applying a voltage to the piezoelectric element adhered to a position called a pressure chamber (also referred to as a liquid chamber) in the ink flow path in the inkjet ejection head, the piezoelectric element bends and the pressure chamber is formed. The ink in the pressure chamber is pressurized by reducing the volume of the pressure chamber, and the means for ejecting the ink as droplets from the nozzle of the inkjet ejection head is preferable. Further, in a plurality of nozzles capable of ejecting such ink, in some nozzles in which ink is not ejected due to the shape of the formed image, a minute voltage that is not ejected to the piezoelectric element is applied to the inside of the nozzle. It is preferable to vibrate the interface of the ink. The interface of the ink in the nozzle is the interface of the ink in contact with the atmosphere or gas.

<Transporting means>
The platen 108 guides the impermeable substrate 102 so that it is transported along the transport path.

<Ink drying means>
The ink drying device 109 blows warm air onto the ink applied to the surface treatment layer on the impermeable substrate 102 to dry the ink. The means for drying the ink is not limited to the means for blowing warm air, and various known means such as a means for contacting the back surface of the impermeable base material 102 with a heating roller, a flat heater, or the like to dry the ink are used. be able to.

<Winding means>
The take-up device 110 winds up and stores the impermeable base material 102 on which an image is formed by applying ink in a roll shape by rotationally driving the base material 102.

<< Recording method >>
In the present application, the recording method is a surface treatment layer forming step of forming a surface treatment layer containing a polyvalent metal compound and a resin on a non-permeable substrate, and a humidification step of humidifying between the ink applying means and the surface treatment layer. After the humidification step, the ink applying step includes an ink applying step of applying an ink containing a coloring material and water to the surface treatment layer from the ink applying means. Further, the recording method can also include, if necessary, a step related to supply, transportation, and discharge of the impermeable substrate, a pretreatment step, a posttreatment step, a drying step, and the like.

A recording method according to an embodiment of the present invention will be described with reference to FIG. The recording method using the recording apparatus 100 shown in FIG. 1 includes a corona treatment step, a surface treatment layer forming step, a humidification step, an ink applying step, and an ink drying step.

<Corona processing process>
The corona treatment step is a step of performing corona treatment on the non-permeable base material 102 transported through the step of unwinding the non-permeable base material 102 by corona discharge to perform surface modification. Performing the corona treatment before the surface treatment layer forming step described below is preferable because the adhesion of the surface treatment layer to the impermeable substrate 102 is improved. Further, various conditions (discharge amount, etc.) when the corona treatment step is performed are not particularly limited.
In the recording method of the present application, instead of the corona treatment, atmospheric pressure plasma treatment, frame treatment, ultraviolet irradiation treatment, and the like can be performed. Further, it is not necessary to provide the corona treatment.

<Surface treatment layer forming process>
In the surface treatment layer forming step, a surface treatment liquid containing water, a polyvalent metal compound, and a resin is applied to the impermeable base material 102 transported through the step of unwinding the non-permeable base material 102. This is a step of forming a surface treatment layer containing a polyvalent metal compound and a resin by drying. After the surface treatment layer forming step, ink is applied to the surface treatment layer on the impermeable substrate 102, and the polyvalent metal salt contained in the surface treatment layer reacts with the coloring material contained in the applied ink to form a surface. The coloring material can be aggregated on the treated layer. As a result, it is possible to suppress the occurrence of color boundary bleeding and the like in the image formed by the ink, and an excellent image can be obtained.
The amount of the surface treatment liquid applied to the impermeable substrate 102 is not particularly limited, but is preferably 0.01 g / m ² or more and 2.0 g / m ² or less, and 0.02 g / m ² or more 1 It is more preferably 1.6 g / m ² or less. When it is 0.01 g / m ² or more, the coloring material is more likely to aggregate. Further, when the content is 2.0 g / m ² or less, the drying time of the surface treatment liquid can be shortened, so that the recording speed can be increased.
Further, in the surface treatment layer forming step shown in FIG. 1, the surface treatment liquid applied to the impermeable substrate 102 is dried using the surface treatment liquid drying device 105 to form the surface treatment layer, which is special. The surface treatment layer may be formed by natural drying without using a drying means. Further, by sufficiently drying the surface treatment liquid and then performing the ink application step described later, the shape of the ink droplets when the ink is applied to the surface treatment layer becomes uniform and the ink bleeding is suppressed. Will be done.

<Humidification process>
The humidifying step is a step of humidifying between the inkjet ejection head 107 and the surface treatment layer provided on the impermeable substrate 102. In other words, the humidification step is a step of supplying air humidified to the inkjet discharge head 107 and the surface treatment layer provided on the impermeable base material 102 by blowing air, a formed flow path, or the like. .. As a result, the vicinity of the inkjet ejection head 107, more specifically, the vicinity of the nozzle provided in the inkjet ejection head 107, and more specifically, the inside of the nozzle provided in the inkjet ejection head 107 is humidified. By humidifying the vicinity of the inkjet ejection head 107, it is possible to suppress ink drying due to evaporation of water from the ink in the nozzle, and it is possible to suppress streaks generated in the image due to ejection defects. Similarly, the vicinity of the surface treatment layer is humidified by humidifying between the inkjet ejection head 107 and the surface treatment layer provided on the impermeable substrate 102. Since the surface treatment layer contains a polyvalent metal salt having hydrophilicity and a resin, moisture is adsorbed on the surface treatment layer by humidifying the vicinity of the surface treatment layer, and the surface treatment layer is imparted to the surface treatment layer after the humidification step. The ink tends to get wet and spread. By wetting and spreading the ink, it is possible to suppress the occurrence of streaks in the image. The streak is a streak-like image defect that occurs due to nozzle clogging or defective ejection and extends along the paper transport direction. In order to efficiently humidify the surface treatment layer, it is preferable that the humidifying device 106 is provided on the upstream side of the inkjet ejection head 107 with respect to the transport direction of the impermeable base material 102. Further, the humidifying step is preferably a step of humidifying the above-mentioned humidifying region.
Further, the humidification step is preferably a step of setting the relative humidity between the ink applying means and the surface treatment layer to 65% RH or more and 90% RH or less, and is a step of setting 70% RH or more and 85% RH or less. Is more preferable. When the relative humidity is in this range, it is possible to better suppress the generation of streaks in the image. The "relative humidity between the ink applying means and the surface treatment layer" is an intermediate point on a straight line in which the distance between the opening (nozzle) for applying ink in the ink applying means and the surface treatment layer is the shortest. However, when the recording device is provided with the above-mentioned humidifying area, the measurement can be performed at any place in the humidifying area.

<Ink application process>
The ink application step is a step of applying an ink containing a coloring material and water to the surface treatment layer on the impermeable substrate 102 that has undergone the above-mentioned surface treatment layer forming step and humidification step. As a result, the ink reacts with the polyvalent metal compound in the surface treatment layer while wetting and spreading, and the coloring material in the ink aggregates, so that streaks in the image are suppressed and color boundary bleeding in the image occurs. It can be suppressed and an excellent image can be obtained.
Further, in the surface treatment layer forming step shown in FIG. 1, an inkjet ejection head 107, which is a line-type inkjet ejection head, is used. Since it is necessary to perform a large amount of printing at high speed in printing for industrial use, an inkjet recording method using a line-type inkjet ejection head is preferable as in the recording method shown in FIG. However, since printing for industrial use is performed continuously for a long time, when a line type head is used, the ink dries in some nozzles where the ink is not ejected for a long time, resulting in ejection failure. Sometimes. Therefore, when a line-type inkjet ejection head is used, it is preferable to execute a humidification step capable of suppressing ink drying in the nozzle as compared with the case where a serial-type inkjet ejection head is used. Even when a serial type inkjet ejection head is used, there may be nozzles in which ink is not ejected for a long time. Therefore, the ink application step in the present application is a case where a serial type inkjet ejection head is used. Do not exclude.
Further, in the ink applying step, it is preferable to vibrate the interface of the ink in the nozzle in the nozzle that does not eject the ink. By vibrating the interface of the ink in the nozzle, the ink in the nozzle and the ink in the ink flow path in the inkjet ejection head such as the pressure chamber communicating with the nozzle can be made uniform, and the inside of the nozzle can be made uniform. It is possible to suppress the drying of the ink in. This makes it possible to further suppress the generation of streaks in the image due to nozzle clogging.

<Ink drying process>
The ink drying step is a step of drying the applied ink after the ink applying step. The drying is preferably performed to the extent that the recording medium is not sticky. In the drying step shown in FIG. 1, the applied ink is dried by the ink drying device 109, but it may be naturally dried without using any special drying means.

<< Impermeable Substrate >>
The non-permeable base material refers to a base material having a surface having a low water permeability, absorbency and / or adsorptivity, and includes a base material having a large number of cavities inside but not opening to the outside. More quantitatively, in the Bristow method, it refers to a substrate having a water absorption amount of 10 mL / m ² or less from the start of contact to 30 msec ^1/2 .
Among the non-permeable substrates, polypropylene film film, polyethylene terephthalate film, and nylon film are preferable because the ink adheres well. Further, among these, polypropylene film film and polyethylene terephthalate film are particularly desirable because they have little change in characteristics with respect to humidification.
Examples of the polypropylene film include P-2002, P-2161, P-4166 manufactured by Toyobo Co., Ltd., PA-20, PA-30, PA-20W manufactured by SUNTOX Co., Ltd., FOA, FOS, FOR manufactured by Futamura Chemical Co., Ltd. and the like. ..
Examples of the polyethylene terephthalate film include E-5100 and E-5102 manufactured by Toyobo Co., Ltd., P60 and P375 manufactured by Toray Industries, Inc., G2, G2P2, K and SL manufactured by Teijin DuPont Film Co., Ltd.
Examples of the nylon film include Harden films N-1100, N-1102, N-1200 manufactured by Toyobo Co., Ltd., ON, NX, MS, NK manufactured by Unitika Ltd. and the like.
When a permeable base material is used instead of the non-permeable base material, the surface treatment liquid permeates the inside of the permeable base material non-uniformly. Therefore, it is not possible to form a uniform surface treatment layer formed by uniformly applying the surface treatment liquid to the surface of the base material, and therefore, when a permeable base material is used, streaks generated in the image are suppressed. It becomes difficult to do.

<< Surface treatment liquid >>
The surface treatment liquid that forms the surface treatment layer by being applied to the impermeable substrate contains a polyvalent metal compound, a resin, and water, and if necessary, contains an organic solvent, a surfactant, and other components. ..

<Multivalent metal compound>
The polyvalent metal compound can improve the water absorption of the surface treatment layer in the humidification step, thereby suppressing streaks generated in the image. Further, the polyvalent metal compound aggregates the coloring material contained in the ink.
Examples of the polyvalent metal compound include titanium compounds, chromium compounds, copper compounds, cobalt compounds, strontium compounds, barium compounds, iron compounds, aluminum compounds, calcium compounds, magnesium compounds, nickel compounds, and salts thereof (multivalent). Metal salt).
Among these, at least one selected from the group consisting of calcium compounds, magnesium compounds, nickel compounds, and salts thereof is preferable. In particular, when the polyvalent metal compound is a salt of a calcium compound (calcium salt), aggregation of the resin contained in the surface treatment liquid can be suppressed, so that the stability of the surface treatment liquid becomes better.
Specific examples of the polyvalent metal compound 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 calcium silicate. , Magnesium silicate, aluminum hydroxide and the like. Of these, calcium acetate is preferred.
The concentration of the polyvalent metal compound with respect to the total amount of the surface treatment liquid is preferably 0.05 mol / kg or more and 0.5 mol / kg or less. When the concentration is within this range, aggregation of the resin contained in the surface treatment liquid can be suppressed, so that excellent storage stability can be obtained, water absorption is improved in the humidification step, and it occurs in the image. Streaks can be suppressed.
Similar to the polyvalent metal compound, a cationic polymer is known as a material having a function of aggregating a coloring material contained in an ink. However, the liquid containing the cationic polymer and the resin is inferior in the hygroscopic property in the humidification step as compared with the surface treatment liquid of the present application containing the polyvalent metal compound and the resin. Therefore, it is preferable to use a polyvalent metal compound.

<Resin>
When the resin is at least one selected from a polyolefin resin, a polyvinyl acetate resin, a polyvinyl chloride resin, a urethane resin, a styrene butadiene resin, and a copolymer of these resins, the surface treatment layer has various impermeables. It is preferable because strong adhesion to the sex substrate can be obtained. Further, it is more preferable that the ethylene-vinyl acetate copolymer resin, the ethylene-vinyl acetate-vinyl chloride copolymer resin, and the olefin-modified urethane resin are used. Further, the resin is preferably in the form of resin particles that can be dispersed in water.
The amount of the resin added is preferably 0.5% by mass or more and 20% by mass or less as a solid content with respect to the total amount of the surface treatment liquid. When it is 0.5% by mass or more, the resin can sufficiently coat the impermeable substrate, so that the adhesion of the surface treatment layer to the impermeable substrate is improved and the bleeding of ink droplets is suppressed. be able to. Further, when it is 20% by mass or less, the film thickness of the surface treatment layer does not become too thick, so that the decrease in adhesion is suppressed.

<Water>
The content of water in the surface treatment liquid is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 10% by mass or more and 90% by mass or less, more preferably 50% by mass or more and 90% by mass or less. It is particularly preferably 60% by mass or more and 90% by mass or less.

<Organic solvent>
The organic solvent used for the surface treatment liquid 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 polyhydric alcohols include, for example, ethylene glycol, diethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, and 1,4-butane. Didiol, 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- Examples thereof include 1,3-pentanediol and petriol.
Examples of the polyhydric alcohol alkyl ethers 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, etc. can be mentioned.
Examples of the polyhydric alcohol aryl ethers include ethylene glycol monophenyl ether and ethylene glycol monobenzyl ether.
Examples of the nitrogen-containing heterocyclic compound include 2-pyrrolidone, N-methyl-2-pyrrolidone, N-hydroxyethyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, ε-caprolactam, and γ-butyrolactone. Can be mentioned.
Examples of the amides include formamide, N-methylformamide, N, N-dimethylformamide, 3-methoxy-N, N-dimethylpropionamide, 3-butoxy-N, N-dimethylpropionamide and the like.
Examples of amines include monoethanolamine, diethanolamine, triethylamine and the like.
Examples of sulfur-containing compounds include dimethyl sulfoxide, sulfolane, and thiodiethanol.
Examples of other organic solvents include propylene carbonate and ethylene carbonate.
It is preferable to use an organic solvent having a boiling point of 250 ° C. or lower because it not only functions as a wetting agent but also has good drying properties.

The content of the organic solvent in the surface treatment liquid is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 5% by mass or more and 60% by mass or less, and more preferably 5% by mass or more and 50% by mass or less. preferable.

<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. Examples of the silicone-based surfactant include side-chain modified polydimethylsiloxane, double-ended modified polydimethylsiloxane, one-ended modified polydimethylsiloxane, and side-chain double-ended modified polydimethylsiloxane. Those having a polyoxyethylene group and a polyoxyethylene polyoxypropylene group as the modifying 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 in the side chain. Polyoxyalkylene ether polymer compounds are particularly preferred because they have low foaming properties. Examples of the perfluoroalkyl sulfonic acid compound include perfluoroalkyl sulfonic acid and perfluoroalkyl sulfonic acid salt. Examples of the perfluoroalkylcarboxylic acid compound include perfluoroalkylcarboxylic acid and perfluoroalkylcarboxylic acid salt. Examples of the polyoxyalkylene ether polymer compound having a perfluoroalkyl ether group in the side chain include a sulfate ester salt of a polyoxyalkylene ether polymer having a perfluoroalkyl ether group in the side chain and a poly having a perfluoroalkyl ether group in the side chain. Examples thereof include salts of oxyalkylene ether polymers. The counterions of the salts in these fluorine-based surfactants are Li, Na, K, NH ₄ , NH ₃ CH ₂ CH ₂ OH, NH ₂ (CH ₂ CH ₂ OH) ₂ , 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 sorbitan. Examples thereof include fatty acid esters and ethylene oxide adducts of acetylene alcohols.
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.

（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 chain. Examples thereof include both-terminal modified polydimethylsiloxane, and a polyether-modified silicone-based surfactant having a polyoxyethylene group and a polyoxyethylene polyoxypropylene group as modifying groups is particularly preferable because it exhibits good properties as an aqueous surfactant. ..
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.

(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.

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。

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 perfluoroalkylethylene 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.

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.

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 The Chemours Company); 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 Co., Ltd.) Among these, FS-3100, FS-34, FS- of The Chemours Co., Ltd. from the viewpoint of remarkably improving good print quality, especially color development, permeability to paper, wettability, and leveling property. 300, FT-110, FT-250, FT-251, FT-400S, FT-150, FT-400SW manufactured by Neos Co., Ltd., Polyfox PF-151N manufactured by Omninova, and Unidyne DSN-manufactured by Daikin Industries Co., Ltd. 403N is particularly preferable.

The content of the surfactant in the surface treatment liquid is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 0.001% by mass or more and 5% by mass or less, preferably 0.05% by mass or more. More preferably, it is 5% by mass or less.

<< Ink >>
The ink contains a coloring material and water, and if necessary, contains resin particles, an organic solvent, a surfactant, and other components. Since the organic solvent and the surfactant used for the ink are the same as the organic solvent and the surfactant used in the surface treatment liquid, the description thereof will be omitted.

<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.
As the pigment, for example, a black pigment, a yellow pigment, a magenta pigment, a cyan pigment, a white pigment, a green pigment, an orange pigment, a glossy color pigment such as gold or silver, a metallic pigment, or the like can be used.
As inorganic pigments, carbon black produced by known methods such as contact method, furnace method, thermal method, in addition to titanium oxide, iron oxide, calcium carbonate, barium sulfate, aluminum hydroxide, barium yellow, cadmium red, and chrome yellow. Can be used.
Examples of organic pigments include azo pigments and polycyclic pigments (for example, phthalocyanine pigments, perylene pigments, perinone pigments, anthraquinone pigments, quinacridone pigments, dioxazine pigments, indigo pigments, thioindigo pigments, isoindolinone pigments, quinophthalone pigments, etc.). , Dye chelate (for example, basic dye type chelate, acid dye type chelate, etc.), nitro pigment, nitroso pigment, aniline black and the like can be used. Among these pigments, those having a good affinity with a solvent are preferably used. In addition, resin hollow particles and inorganic hollow particles can also be used.
As a specific example of the pigment, for black, carbon black (CI pigment black 7) such as furnace black, lamp black, acetylene black, channel black, 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 a 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. It is as follows.

As a method of dispersing the pigment to obtain an ink, a method of introducing a hydrophilic functional group into the pigment to obtain a self-dispersible 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. The method, etc. can be mentioned.
As a method of introducing a hydrophilic functional group into a pigment to obtain a self-dispersing pigment, for example, a method of adding a functional group such as a sulfone group or a carboxyl group to a pigment (for example, carbon) so that the pigment can be dispersed in water. 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 a 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.
As the dispersant, 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 the 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 or more 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 less, 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, but is 0.1% by mass from the viewpoint of obtaining good ejection stability and increasing the image density. 50% by mass or more is preferable, and 0.1% by mass or more and 30% by mass or less is more preferable.
It is preferable to degas the pigment dispersion by filtering the coarse particles with a filter, a centrifuge, or the like, if necessary.

<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.

<Resin particles>
The type of resin of the resin particles contained in the ink is not particularly limited and may be appropriately selected depending on the intended purpose. For example, urethane resin, polyester resin, acrylic resin, vinyl acetate resin, styrene resin, butadiene resin. , Styrene-butadiene resin, vinyl chloride resin, acrylic styrene resin, acrylic silicone resin and the like, and can be used alone or in combination. Among these, acrylic resin, urethane resin, and polyester resin are preferable.

As the resin particles, those synthesized as appropriate may be used, or commercially available products may be used. Examples of commercially available resin particles include Microgel E-1002, E-5002 (styrene-acrylic resin particles, manufactured by Nippon Paint Co., Ltd.) and Boncoat 4001 (acrylic resin particles, manufactured by Dainippon Ink and Chemicals Co., Ltd.). , Boncoat 5454 (styrene-acrylic resin particles, manufactured by Dainippon Ink and Chemicals Co., Ltd.), SAE-1014 (styrene-acrylic resin particles, manufactured by Nippon Zeon Co., Ltd.), Cybinol SK-200 (acrylic resin particles, manufactured by Saiden Co., Ltd.) Chemical Co., Ltd.), Primal AC-22, AC-61 (acrylic resin particles, manufactured by Roam & Haas), Nanokrill SBCX-2821, 3689 (acrylic silicone resin particles, manufactured by Toyo Ink Mfg. Co., Ltd.), # Examples thereof include 3070 (methyl methacrylate polymer resin particles, manufactured by Gokoku Dye Co., Ltd.).

The content of the resin particles is preferably 1% by mass or more and 30% by mass or less, more preferably 5% by mass or more and 20% by mass or less, based on the total amount of the ink.

The glass transition temperature of the resin particles is preferably −50 ° C. or higher and 100 ° C. or lower.

The volume average particle size of the resin particles is not particularly limited and may be appropriately selected depending on the intended purpose. However, from the viewpoint of obtaining good fixability and high image hardness, 10 nm or more and 1,000 nm or less are preferable. More than 200 nm is more preferable, and 10 nm or more and 100 nm or less is particularly preferable. The volume average particle size can be measured using, for example, a particle size analyzer (Nanotrack Wave-UT151, manufactured by Microtrac Bell Co., Ltd.).

Hereinafter, examples of the present invention will be described, but the present invention is not limited to these examples. In the following description, "part" means "part by mass".

<Example of preparation of surface treatment liquid>
(Example of Production of Surface Treatment Liquid P-1)
The following prescription mixture was filtered through a 5 μm filter (trade name: Minisalt, manufactured by Sartorius) to obtain a surface treatment liquid P-1.
・ 1,2-Propanediol 10 parts ・ Emargen LS-106 (surfactant, manufactured by Kao Co., Ltd.) 1 part ・ Calcium acetate monohydrate 1.76 parts ・ Vinyl acetate-acrylic resin particles (trade name: Viniblanc 1225, Nissin Chemical Co., Ltd.) 10 parts (solid content concentration 45%)
・ Proxel LV (preservative, manufactured by Abyssia) 0.1 parts ・ Ion exchanged water 77.14 parts

(Example of Fabrication of Surface Treatment Liquid P-2)
The following prescription mixture was filtered through a 5 μm filter (trade name: Minisalt, manufactured by Sartorius) to obtain a surface treatment liquid P-2.
・ 1,2-Propanediol 10 parts ・ Emargen LS-106 (surfactant, manufactured by Kao Co., Ltd.) 1 part ・ Calcium chloride hexahydrate 1.76 parts ・ Vinyl acetate-acrylic resin particles (trade name: Viniblanc 1225, Nissin Chemical Co., Ltd.) 10 parts (solid content concentration 45%)
・ Proxel LV (preservative, manufactured by Abyssia) 0.1 parts ・ Ion exchanged water 77.14 parts

(Example of Fabrication of Surface Treatment Liquid P-3)
The following prescription mixture was filtered through a 5 μm filter (trade name: Minisalt, manufactured by Sartorius) to obtain a surface treatment liquid P-3.
・ 1,2-Propanediol 10 parts ・ Emargen LS-106 (surfactant, manufactured by Kao Co., Ltd.) 1 part ・ Magnesium sulfate (anhydrous) 1.76 parts ・ Vinyl acetate-acrylic resin particles (trade name: Vinibran 1225, Japan) Made by Shinkagaku Co., Ltd.) 10 parts (solid content concentration 45%)
・ Proxel LV (preservative, manufactured by Abyssia) 0.1 parts ・ Ion exchanged water 77.14 parts

(Example of Fabrication of Surface Treatment Liquid P-4)
The following prescription mixture was filtered through a 5 μm filter (trade name: Minisalt, manufactured by Sartorius) to obtain a surface treatment liquid P-4.
・ 1,2-Propanediol 10 parts ・ Emargen LS-106 (surfactant, manufactured by Kao Corporation) 1 part ・ Vinyl acetate-acrylic resin particles (trade name: Vinibran 1225, manufactured by Nissin Chemical Co., Ltd.) 10 parts (solid content) Concentration 45%)
・ Proxel LV (preservative, manufactured by Abyssia) 0.1 part ・ Ion exchanged water 78.9 parts

(Example of Fabrication of Surface Treatment Liquid P-5)
The following prescription mixture was filtered through a 5 μm filter (trade name: Minisalt, manufactured by Sartorius) to obtain a surface treatment liquid P-5.
・ 1,2-Propanediol 10 parts ・ Emargen LS-106 (surfactant, manufactured by Kao) 1 part ・ Calcium acetate monohydrate 1.76 parts ・ Proxel LV (preservative, manufactured by Abyssia) 0.1 Part ・ Ion-exchanged water 87.14 parts

<Example of Fabrication of Pigment Dispersion>
(Example of Fabrication of Black Pigment Dispersion)
Carbon black manufactured by Cabot Corporation: 100 g of Black Pearls (registered trademark) is added to 3000 mL of a 2.5 N (specified) sodium hypochlorite solution, stirred at a temperature of 60 ° C. and a rate of 300 rpm, and reacted for 10 hours. Oxidation treatment was carried out to obtain a reaction solution containing a pigment having a carboxylic acid group on the surface of carbon black. The obtained reaction solution was filtered, the filtered carbon black was neutralized with a sodium hydroxide solution, and the mixture was subjected to ultrafiltration to obtain a dispersion. Next, ultrafiltration was performed with a dialysis membrane using the dispersion and ion-exchanged water, and ultrasonic dispersion was further performed to obtain a concentrated black pigment dispersion having a pigment solid content concentration of 15% by mass.

(Example of Fabrication of Cyan Pigment Dispersion)
Pigment Blue 15: 4 (trade name: SMART Cyan 3154BA, manufactured by SENSIENT) was used instead of carbon black in the preparation of the black pigment dispersion, except that the pigment solid content concentration was the same as in the preparation of the black pigment dispersion. A cyan pigment dispersion having a concentration of 15% by mass was obtained.

(Example of Fabrication of Magenta Pigment Dispersion)
Pigment Red 122 (trade name: Pigment Red 122, manufactured by Sun Chemical Co., Ltd.) was used in the preparation of the black pigment dispersion, except that Pigment Red 122 (trade name: Pigment Red 122, manufactured by Sun Chemical Co., Ltd.) was used in the same manner as in the preparation of the black pigment dispersion. A magenta pigment dispersion having a value of 15% by mass was obtained.

(Example of Fabrication of Yellow Pigment Dispersion)
In the preparation of the black pigment dispersion, the pigment solid content concentration was 15 in the same manner as in the preparation of the black pigment dispersion, except that Pigment Yellow 74 (trade name: SMART Yellow 3074BA, manufactured by SENSIENT) was used instead of carbon black. A yellow pigment dispersion having a mass% was obtained.

<Ink production example>
(Example of manufacturing black ink)
The following raw materials were sequentially dispersed and stirred, and filtered with a membrane filter to prepare black ink.
・ 20 parts of black pigment dispersion ・ Resin emulsion (trade name: Viniplan ADH-893D, manufactured by Nissin Chemical Co., Ltd.) 5 parts ・ Surfactant (trade name: Softanol EP-5035, manufactured by Nippon Catalyst Co., Ltd.) 2 parts ・ Preservative (Proxel LV, manufactured by Abyssia) 0.1 part, 1,2-propanediol 30 parts, 3-methyl-1,3-butanediol 5 parts, ion-exchanged water 37.9 parts

(Cyan ink production example)
In the production of the black ink, the cyan ink was produced in the same manner as in the production of the black ink, except that the cyan pigment dispersion was used instead of the black pigment dispersion.

(Example of manufacturing magenta ink)
In the production of the black ink, the magenta ink was produced in the same manner as in the production of the black ink, except that the magenta pigment dispersion was used instead of the black pigment dispersion.

(Example of manufacturing yellow ink)
In the production of the black ink, the yellow ink was produced in the same manner as in the production of the black ink, except that the yellow pigment dispersion was used instead of the black pigment dispersion.

<Example 1>
The produced black, cyan, magenta, and yellow inks were filled in the ink container of the modified machine of the inkjet recording device (trade name: VC-60,000, manufactured by Ricoh Co., Ltd.) for printing. The modified machine of the inkjet recording device has each configuration similar to that of FIG. 1, and a corona processing device and a humidifying device are provided at the same positions as those of FIG. Using the modified machine of this inkjet recording device, continuous printing was performed under the following printing conditions.
(Printing conditions)
-Print length: 2000m
-Printing speed: 50 (m / min)
-Resolution: 1200 x 1200 dpi
-Printed image: A solid image of black, cyan, magenta, and yellow was formed so that a solid image of a predetermined color adjacent to a solid image of another color formed a color boundary.-Immune substrate: OPP 20um film (trade name: Pyrene P2161, manufactured by Toyo Boseki Co., Ltd.)
・ Corona treatment device: Operated ・ Surface treatment liquid to be applied: Surface treatment liquid P-1
-Means for applying the surface treatment liquid to the impermeable substrate: Roll coater-Means for drying the surface treatment liquid: Hot air and heating rollers (both at 80 ° C)
-Humidifying device: Operate (a humidifying area is provided and water vapor is supplied between the inkjet head and the surface treatment layer).
・ Installation position of the humidifying device: Upstream from the position of the inkjet head (IJ head) in the transport path ・ The inkjet head that sets and uses the humidifying device so that the relative humidity between the inkjet head and the surface treatment layer is 77% RH. : Inkjet head corresponding to black, cyan, magenta, and yellow inks ・ Fine drive conditions for non-ejection nozzles (vibration conditions of the ink interface in the nozzles): 2 kHz (20% output with respect to piezo voltage during ejection)
-Ink drying means: hot air and heating rollers (both 80 ° C)

<Examples 2 to 10, Comparative Examples 1 to 5>
In Example 1, the printing conditions were changed as shown in Table 1 below, and Examples 2 to 10 and Comparative Examples 1 to 5 were printed.
In Example 7, printing was performed using the printing apparatus shown in FIG. FIG. 2 is a schematic side view showing the recording device used in the seventh embodiment. The recording device used in Example 7 is the same as the recording device used in Example 1 except for the installation position of the humidifying device. As shown in FIG. 2, the humidifying device 106-1 of the seventh embodiment is provided at the same position as the position of the inkjet head in the transport path.
The permeable base material of Comparative Example 5 is Lumi Art Gloss 90 gsm (manufactured by Stora Enso).

Next, after printing of Examples 1 to 10 and Comparative Examples 1 to 5, the characteristics of the printed image at the start of printing and the printed image at the end of printing for 2000 m are determined according to the following method and evaluation criteria. evaluated. The results are shown in Table 2.

[Evaluation of streak suppression]
The printed image at the start of printing and the printed image at the end of printing for 2000 m were visually observed, and the degree of occurrence of streaks was evaluated according to the following criteria. It was judged that the case where the evaluation was B or higher was practical.
-Evaluation criteria-
A: No streaks are observed B: Streaks cannot be visually observed, but streaks can be observed with a loupe C: Streaks can be visually observed in a part of the image D: Streaks can be visually observed in the entire image

[Evaluation of bleeding at color boundaries]
The color boundaries between solid images of different colors were visually observed, and the degree of bleeding was evaluated according to the following criteria. A case where the evaluation was B or higher was judged to be preferable.
-Evaluation criteria-
A: No bleeding at the color boundary is observed B: No bleeding at the color boundary can be visually observed, but can be observed with a loupe C: Blurring can be visually observed at a part of the color boundary D: The entire color boundary is visually observed You can observe the bleeding

100 Recording device 101 Unwinding device 102 Impermeable base material 103 Corona treatment device 104 Surface treatment liquid application device 105 Surface treatment liquid drying device 106 Humidifying device 106-1 Humidifying device 107 Ink jet ejection head 108 Platen 109 Ink drying device 110 Winding Device

JP-A-2015-143003

Claims (3)

A recording method in which an ink containing a coloring material and water is applied from an ink applying means.
A surface treatment layer forming step of forming a surface treatment layer containing a polyvalent metal compound and a resin on a non-permeable substrate,
A humidifying step of humidifying between the ink applying means and the surface treatment layer by a humidifying means,
After the humidification step, the ink applying means comprises an ink applying step of applying the ink to the surface treatment layer.
The humidification step is a step of adjusting the relative humidity between the ink applying means and the surface treatment layer to 65% RH or more and 90% RH or less.
The surface treatment layer forming step is a step of applying a surface treatment liquid containing water, the polyvalent metal compound, and the resin to the impermeable substrate and then drying the surface treatment layer to form the surface treatment layer.
The ink applying means is a line-type inkjet ejection means.
The inkjet ejection means vibrates the interface of the ink in the nozzle in a nozzle that does not eject the ink.
The polyvalent metal compound contains calcium acetate and contains
The resin contains vinyl acetate-acrylic resin and contains
The humidifying means is a recording method provided on the upstream side of the ink applying means with respect to the transport direction of the impermeable base material. The recording method according to claim 1, wherein the non-permeable substrate has a water absorption amount of 10 mL / m ² or less from the start of contact to 30 msec ^1/2 in the Bristow method. A recording device that applies color materials and ink containing water from an ink applying means.
A surface treatment layer forming means for forming a surface treatment layer containing a polyvalent metal compound and a resin on a non-permeable substrate,
A humidifying means for humidifying between the ink applying means and the surface treatment layer,
It has an ink applying means for applying the ink to the surface treatment layer from the ink applying means.
The humidifying means is a means for reducing the relative humidity between the ink applying means and the surface treatment layer to 65% RH or more and 90% RH or less.
The surface treatment layer forming means is a means for forming the surface treatment layer by applying a surface treatment liquid containing water, the polyvalent metal compound, and the resin to the impermeable substrate and then drying the surface treatment liquid.
The ink applying means is a line-type inkjet ejection means.
The inkjet ejection means vibrates the interface of the ink in the nozzle in a nozzle that does not eject the ink.
The polyvalent metal compound contains calcium acetate and contains
The resin contains vinyl acetate-acrylic resin and contains
The humidifying means is a recording device provided on the upstream side of the ink applying means with respect to the transport direction of the impermeable base material.

Images